Enhancing the efficiency of lithium intercalation in carbon nanotube bundles using surface functional groups.

Science.gov (United States)

Xiao, Shiyan; Zhu, Hong; Wang, Lei; Chen, Liping; Liang, Haojun

2014-08-14

The effect of surface functionalization on the ability and kinetics of lithium intercalation in carbon nanotube (CNT) bundles has been studied by comparing the dynamical behaviors of lithium (Li) ions in pristine and -NH2 functionalized CNTs via ab initio molecular dynamics simulations. It was observed that lithium intercalation has been achieved quickly for both the pristine and surface functionalized CNT bundle. Our calculations demonstrated for the first time that CNT functionalization improved the efficiency of lithium intercalation significantly at both low and high Li ion density. Moreover, we found that keeping the nanotubes apart with an appropriate distance and charging the battery at a rational rate were beneficial to achieve a high rate of lithium intercalation. Besides, the calculated adsorption energy curves indicated that the potential wells in the system of -NH2 functionalized CNT were deeper than that of the pristine CNT bundle by 0.74 eV, and a third energy minimum with a value of 2.64 eV existed at the midpoint of the central axis of the nanotube. Thus, it would be more difficult to remove Li ions from the nanotube interior after surface functionalization. The barrier for lithium diffusion in the interior of the nanotube is greatly decreased because of the surface functional groups. Based on these results, we would suggest to "damage" the nanotube by introducing defects at its sidewall in order to improve not only the capacity of surface functionalized CNTs but also the efficiency of lithium intercalation and deintercalation processes. Our results presented here are helpful in understanding the mechanism of lithium intercalation into nanotube bundles, which may potentially be applied in the development of CNT based electrodes.

Adsorption of Phosphate Ion in Water with Lithium-Intercalated Gibbsite

OpenAIRE

Riwandi Sihombing; Yuni Krisyuningsih Krisnandi; Rahma Widya; Siti Zahrotul Luthfiyah; Rika Tri Yunarti

2015-01-01

In order to enhance adsorption capacity of gibbsite (Al(OH)3 as an adsorbent for the adsorption of phosphate in water, gibbsite was modified through lithium-intercalation. The purification method of Tributh and Lagaly was applied prior to intercalation. The Li-Intercalation was prepared by the dispersion of gibbsite into LiCl solution for 24 hours. This intercalation formed an cationic clay with the structure of [LiAl2(OH)6]+ and exchangeable Cl- anions in the gibbsite interlayer. A phosphate...

Electrochemical-mechanical coupled modeling and parameterization of swelling and ionic transport in lithium-ion batteries

Science.gov (United States)

Sauerteig, Daniel; Hanselmann, Nina; Arzberger, Arno; Reinshagen, Holger; Ivanov, Svetlozar; Bund, Andreas

2018-02-01

The intercalation and aging induced volume changes of lithium-ion battery electrodes lead to significant mechanical pressure or volume changes on cell and module level. As the correlation between electrochemical and mechanical performance of lithium ion batteries at nano and macro scale requires a comprehensive and multidisciplinary approach, physical modeling accounting for chemical and mechanical phenomena during operation is very useful for the battery design. Since the introduced fully-coupled physical model requires proper parameterization, this work also focuses on identifying appropriate mathematical representation of compressibility as well as the ionic transport in the porous electrodes and the separator. The ionic transport is characterized by electrochemical impedance spectroscopy (EIS) using symmetric pouch cells comprising LiNi1/3Mn1/3Co1/3O2 (NMC) cathode, graphite anode and polyethylene separator. The EIS measurements are carried out at various mechanical loads. The observed decrease of the ionic conductivity reveals a significant transport limitation at high pressures. The experimentally obtained data are applied as input to the electrochemical-mechanical model of a prismatic 10 Ah cell. Our computational approach accounts intercalation induced electrode expansion, stress generation caused by mechanical boundaries, compression of the electrodes and the separator, outer expansion of the cell and finally the influence of the ionic transport within the electrolyte.

Conductive surface modification of cauliflower-like WO3 and its electrochemical properties for lithium-ion batteries

International Nuclear Information System (INIS)

Yoon, Sukeun; Woo, Sang-Gil; Jung, Kyu-Nam; Song, Huesup

2014-01-01

Highlights: • Synthesis of cauliflower-like carbon-decorated WO 3 . • Superior cyclability and rate capability for cauliflower-like carbon-decorated WO 3 . • Electrochemical reaction behavior of cauliflower-like carbon-decorated WO 3 with lithium. • In-situ XRD analysis during the first discharge–charge shows a complex reaction of intercalation and conversion of WO 3 . - Abstract: Cauliflower-like WO 3 was synthesized by a hydrothermal reaction without a surfactant, followed by firing, and was investigated as an anode material for lithium-ion battery applications. The scanning electron microscope (SEM) and transmission electron microscope (TEM) characterization indicated that WO 3 nanorods had an aggregation framework and built a cauliflower morphology. With the objective of understanding the charge–discharge process within a voltage range of 0–3 V vs. Li + /Li, in situ X-ray diffraction was used and a complex reaction of intercalation and conversion of WO 3 was revealed for the first time. The cauliflower-like WO 3 after being decorated with carbon provides a high gravimetric capacity of >635 mA h/g (Li 5.5 WO 3 ) with good cycling and a high rate capability when used as an anode in lithium-ion batteries. Based on our studies, we attribute the high electrochemical performance to the nanoscopic WO 3 particles and a conductive carbon layer, which makes them a potential candidate for lithium-ion batteries

Intercalation Pseudocapacitance in Ultrathin VOPO4 Nanosheets: Toward High-Rate Alkali-Ion-Based Electrochemical Energy Storage.

Science.gov (United States)

Zhu, Yue; Peng, Lele; Chen, Dahong; Yu, Guihua

2016-01-13

There is a growing need for energy storage devices in numerous applications where a large amount of energy needs to be either stored or delivered quickly. The present paper details the study of alkali-ion intercalation pseudocapacitance in ultrathin VOPO4 nanosheets, which hold promise in high-rate alkali-ion based electrochemical energy storage. Starting from bulk VOPO4·2H2O chunks, VOPO4 nanosheets were obtained through simple ultrasonication in 2-propanol. These nanosheets as the cathode exhibit a specific capacity of 154 and 136 mAh/g (close to theoretical value 166 mAh/g) for lithium and sodium storage devices at 0.1 C and 100 and ∼70 mAh/g at 5 C, demonstrating their high rate capability. Moreover, the capacity retention is maintained at 90% for lithium ion storage and 73% for sodium ion storage after 500 cycles, showing their reasonable stability. The demonstrated alkali-ion intercalation pseudocapacitance represents a promising direction for developing battery materials with promising high rate capability.

Electrochemical behavior of LiCoO2 as aqueous lithium-ion battery electrodes

KAUST Repository

Ruffo, Riccardo

2009-02-01

Despite the large number of studies on the behavior of LiCoO2 in organic electrolytes and its recent application as a positive electrode in rechargeable water battery prototypes, a little information is available about the lithium intercalation reaction in this layered compound in aqueous electrolytes. This work shows that LiCoO2 electrodes can be reversibly cycled in LiNO3 aqueous electrolytes for tens of cycles at remarkably high rates with impressive values specific capacity higher than 100 mAh/g, and with a coulomb efficiency greater than 99.7%. Stable and reproducible cycling measurements have been made using a simple cell design that can be easily applied to the study of other intercalation materials, assuming that they are stable in water and that their intercalation potential range matches the electrochemical stability window of the aqueous electrolyte. The experimental arrangement uses a three-electrode flooded cell in which another insertion compound acts as a reversible source and sink of lithium ions, i.e., as the counter electrode. A commercial reference electrode is also present. Both the working and the counter electrodes have been prepared as thin layers on a metallic substrate using the procedures typical for the study of electrodes for lithium-ion batteries in organic solvent electrolytes. © 2008 Elsevier B.V. All rights reserved.

Electrochemical performance of high specific capacity of lithium-ion cell LiV3O8//LiMn2O4 with LiNO3 aqueous solution electrolyte

International Nuclear Information System (INIS)

Zhao Mingshu; Zheng Qingyang; Wang Fei; Dai Weimin; Song Xiaoping

2011-01-01

Research highlights: → In this paper, the electrochemical performance of aqueous rechargeable lithium battery with LiV 3 O 8 and LiMn 2 O 4 in saturated LiNO 3 electrolyte is studied. → The electrochemical performance tests show that the specific capacity of LiMn 2 O 4 using as the cathode of ARLB is similar to that of ordinary lithium-ion battery with organic electrolyte, which works much better than the formerly reported. → In addition, the cell systems exhibit good cycling performance. Therefore, it has great potential comparing with other batteries such as lead acid batteries and alkaline manganese batteries. - Abstract: The electrochemical performance of aqueous rechargeable lithium battery (ARLB) with LiV 3 O 8 and LiMn 2 O 4 in saturated LiNO 3 electrolyte is studied. The results indicate that these two electrode materials are stable in the aqueous solution and no hydrogen or oxygen produced, moreover, intercalation/de-intercalation of lithium ions occurred within the range of electrochemical stability of water. The electrochemical performance tests show that the specific capacity of LiMn 2 O 4 using as the cathode of ARLB is similar to that of ordinary lithium-ion battery with organic electrolyte, which works much better than the formerly reported. In addition, the cell systems exhibit good cycling performance. Therefore, it has great potential comparing with other batteries such as lead acid batteries and alkaline manganese batteries.

Conductive surface modification of cauliflower-like WO{sub 3} and its electrochemical properties for lithium-ion batteries

Energy Technology Data Exchange (ETDEWEB)

Yoon, Sukeun, E-mail: skyoon@kongju.ac.kr [Division of Advanced Materials Engineering, Kongju National University, Chungnam 330-717 (Korea, Republic of); Woo, Sang-Gil [Advanced Batteries Research Center, Korea Electronics Technology Institute, Gyeonggi 463-816 (Korea, Republic of); Jung, Kyu-Nam [Energy Efficiency and Materials Research Division, Korea Institute of Energy Research, Daejeon 305-343 (Korea, Republic of); Song, Huesup, E-mail: hssong@kongju.ac.kr [Division of Advanced Materials Engineering, Kongju National University, Chungnam 330-717 (Korea, Republic of)

2014-11-15

Highlights: • Synthesis of cauliflower-like carbon-decorated WO{sub 3}. • Superior cyclability and rate capability for cauliflower-like carbon-decorated WO{sub 3}. • Electrochemical reaction behavior of cauliflower-like carbon-decorated WO{sub 3} with lithium. • In-situ XRD analysis during the first discharge–charge shows a complex reaction of intercalation and conversion of WO{sub 3}. - Abstract: Cauliflower-like WO{sub 3} was synthesized by a hydrothermal reaction without a surfactant, followed by firing, and was investigated as an anode material for lithium-ion battery applications. The scanning electron microscope (SEM) and transmission electron microscope (TEM) characterization indicated that WO{sub 3} nanorods had an aggregation framework and built a cauliflower morphology. With the objective of understanding the charge–discharge process within a voltage range of 0–3 V vs. Li{sup +}/Li, in situ X-ray diffraction was used and a complex reaction of intercalation and conversion of WO{sub 3} was revealed for the first time. The cauliflower-like WO{sub 3} after being decorated with carbon provides a high gravimetric capacity of >635 mA h/g (Li{sub 5.5}WO{sub 3}) with good cycling and a high rate capability when used as an anode in lithium-ion batteries. Based on our studies, we attribute the high electrochemical performance to the nanoscopic WO{sub 3} particles and a conductive carbon layer, which makes them a potential candidate for lithium-ion batteries.

Electrochemical performance of LiMSnO4 (M=Fe, In) phases with ramsdellite structure as anodes for lithium batteries

International Nuclear Information System (INIS)

Satya Kishore, M.V.; Varadaraju, U.V.; Raveau, B.

2004-01-01

LiMSnO 4 (M=Fe, In) compounds were synthesized by high temperature solid-state reaction method and the electrochemical studies were carried out vs. lithium metal. Lithium is reversibly intercalated and deintercalated in LiFeSnO 4 with a constant capacity of ∼90mAh/g. In situ X-ray diffraction data show that ramsdellite structure is stable for lithium intercalation and deintercalation in LiFeSnO 4 . Galvanostatic discharge/charge of LiFeSnO 4 in the voltage window 0.05-2.0V shows a reversible capacity of ∼100mAh/g. The observed capacity in LiFeSnO 4 is due to the two processes involving alloying/dealloying of Li 4.4 Sn and formation/decomposition of Li 2 O. In contrast, the new isotypic oxide LiInSnO 4 does not exhibit any lithium intercalation due to the absence of mixed valence for indium. Its reversible capacity is strongly dependent on the voltage window. LiInSnO 4 exhibits severe capacity fading on cycling in the voltage window 0.05-2.0V, but shows a stable capacity of ∼90mAh/g in the voltage range 0.75-2.0V

Different types of pre-lithiated hard carbon as negative electrode material for lithium-ion capacitors

International Nuclear Information System (INIS)

Zhang, Jin; Liu, Xifeng; Wang, Jing; Shi, Jingli; Shi, Zhiqiang

2016-01-01

Highlights: • Two types of HC materials with different properties as negative electrode. • Lithium ion intercalation plateau of HC affects electrochemical performance of LIC. • The electrochemical performance of LIC is operated at different potential ranges. • The selection of HC and appropriate potential range of LIC have been proposed. - ABSTRACT: Lithium-ion capacitors (LICs) are assembled with activated carbon (AC) cathode and pre-lithiated hard carbon (HC) anode. Two kinds of HC materials with different physical and electrochemical behaviors have been investigated as the negative electrodes for LIC. Compared with spherical HC, the irregular HC shows a distinct lithium ion intercalation plateau in the charge–discharge process. The existence of lithium ion intercalation plateau for irregular HC greatly affects the electrochemical behavior of HC negative electrode and AC positive electrode. The effect of working potential range on the electrochemical performance of LIC-SH and LIC-IH is investigated by the galvanostatic charging–discharging, electrochemical impedance tests and cycle performance testing. The charge–discharge potential range of the irregular HC negative electrode is lower than the spherical HC electrode due to the existence of lithium ion intercalation plateau, which is conducive to the sufficient utilization of the AC positive electrode. The working potential range of LIC should be controlled to realize the optimization of electrochemical performance of LIC. LIC-IH at the working potential range of 2.0-4.0 V exhibits the optimal electrochemical performance, high energy density up to 85.7 Wh kg −1 and power density as high as 7.6 kW kg −1 (based on active material mass of two electrodes), excellent capacity retention about 96.0% after 5000 cycles.

Investigation of the electrochemically active surface area and lithium diffusion in graphite anodes by a novel OsO4 staining method

Science.gov (United States)

Pfaffmann, Lukas; Birkenmaier, Claudia; Müller, Marcus; Bauer, Werner; Mitsch, Tim; Feinauer, Julian; Krämer, Yvonne; Scheiba, Frieder; Hintennach, Andreas; Schleid, Thomas; Schmidt, Volker; Ehrenberg, Helmut

2016-03-01

Negative electrodes of lithium-ion batteries generally consist of graphite-based active materials. In order to realize batteries with a high current density and therefore accelerated charging processes, the intercalation of lithium and the diffusion processes of these carbonaceous materials must be understood. In this paper, we visualized the electrochemical active surface area for three different anode materials using a novel OsO4 staining method in combination with scanning electron microscopy techniques. The diffusion behavior of these three anode materials is investigated by potentiostatic intermittent titration technique measurements. From those we determine the diffusion coefficient with and without consideration of the electrochemical active surface area.

Factors influencing charge capacity of vanadium pentoxide thin films during lithium ion intercalation/deintercalation cycles

International Nuclear Information System (INIS)

Alamarguy, D.; Castle, J. E.; Ibris, N.; Salvi, A. M.

2007-01-01

The intercalation of vanadium pentoxide by lithium ions leads to a change in optical properties, a process that is of value in thin-film electrochromic devices. In this study, films of V 2 O 5 , deposited on indium tin oxide (ITO) glass coupons by a sol-gel process, were challenged by increasing numbers of charge-discharge cycles ranging from 72 to 589 full cycles. The samples were characterized by x-ray photoelectron spectroscopy (XPS) and then examined in the deintercalated state by time-of-flight secondary ion mass spectroscopy (SIMS). XPS enabled measurement of the thickness and composition of the solid-electrolyte interface and provided evidence of the residual V 4+ concentration within the top few nanometers of the surface. The SIMS profile gave direct information on the thickness of the films and on the thickness loss caused by rinsing the samples after the electrochemical exposure. Determination, by SIMS, of the concentration of lithium ions has enabled a correction to be made for the amount of inactive material within the electrochemically active region of the film. The SIMS depth profiles for lithium in the four samples are similar, with a marked buildup of Li at the interface with the ITO. This interphase zone had a thickness of ∼27 nm and was electrochemically inactive, enabling a further correction to be made. Thus, by means of the XPS and the SIMS results the chemistry and thickness of the films could be fully characterized. The remaining inconsistency between capacity (between 35% and 100% of the anticipated charge) and number of cycles is ascribed to edge effects arising from the method used for production of the coupons

Materialographic preparation of lithium-carbon intercalation compounds; Materialographische Praeparation von Lithium-Kohlenstoff-Einlagerungsverbindungen

Energy Technology Data Exchange (ETDEWEB)

Druee, Martin; Seyring, Martin; Grasemann, Aaron [Jena Univ. (Germany). Otto Schott Institute of Materials Research; Rettenmayr, Markus [Center for Energy and Environmental Chemistry, Jena (Germany)

2016-12-15

The materialographic investigation of anode materials for rechargeable lithium ion batteries is a significant step in the understanding and development of electrode materials, but made dramatically more difficult due to the high reactivity of the materials involved. In this work a method is presented which permits the metallographic preparation of the lithium-carbon intercalation compounds used as anode materials in today's rechargeable lithium ion batteries, and which allows the details of their microstructures to be contrasted. After classic, but absolutely water free, preparation in a protective gas atmosphere, the final stage of preparation is carried out using both ion beam polishing and manual polishing on a stationary polishing disc, whereby no significant differences of the quality of the microstructural images obtained is apparent.

Electrochemical Modeling and Performance of a Lithium- and Manganese-Rich Layered Transition-Metal Oxide Positive Electrode

Energy Technology Data Exchange (ETDEWEB)

Dees, Dennis W.; Abraham, Daniel P; Lu, Wenquan; Gallagher, Kevin G.; Bettge, Martin; Jansen, Andrew N

2015-01-21

The impedance of a lithium- and manganese-rich layered transition-metal oxide (MR-NMC) positive electrode, specifically Li_1.2Ni_0.15Mn_0.55Co_0.1O₂, is compared to two other transition-metal layered oxide materials, specifically LiNi_0.8Co_0.15Al_0.05O₂ (NCA) and Li_1.05(Ni_1/3Co_1/3Mn_1/3)_0.95O₂ (NMC). A more detailed electrochemical impedance spectroscopy (EIS) study is conducted on the LMR-NMC electrode, which includes a range of states-of-charge (SOCs) for both current directions (i.e. charge and discharge) and two relaxation times (i.e. hours and one hundred hours) before the EIS sweep. The LMR-NMC electrode EIS studies are supported by half-cell constant current and galvanostatic intermittent titration technique (GITT) studies. Two types of electrochemical models are utilized to examine the results. The first type is a lithium ion cell electrochemical model for intercalation active material electrodes that includes a complex active material/electrolyte interfacial structure. In conclusion, the other is a lithium ion half-cell electrochemical model that focuses on the unique composite structure of the bulk LMR-NMC materials.

Classical molecular dynamics and quantum abs-initio studies on lithium-intercalation in interconnected hollow spherical nano-spheres of amorphous Silicon

DEFF Research Database (Denmark)

Bhowmik, Arghya; Malik, R.; Prakash, S.

2016-01-01

A high concentration of lithium, corresponding to charge capacity of ~4200 mAh/g, can be intercalated in silicon. Unfortunately, due to high intercalation strain leading to fracture and consequent poor cyclability, silicon cannot be used as anode in lithium ion batteries. But recently interconnec......A high concentration of lithium, corresponding to charge capacity of ~4200 mAh/g, can be intercalated in silicon. Unfortunately, due to high intercalation strain leading to fracture and consequent poor cyclability, silicon cannot be used as anode in lithium ion batteries. But recently...... interconnected hollow nano-spheres of amorphous silicon have been found to exhibit high cyclability. The absence of fracture upon lithiation and the high cyclability has been attributed to reduction in intercalation stress due to hollow spherical geometry of the silicon nano-particles. The present work argues...... that the hollow spherical geometry alone cannot ensure the absence of fracture. Using classical molecular dynamics and density functional theory based simulations; satisfactory explanation to the absence of fracture has been explored at the atomic scale....

Selective sodium intercalation into sodium nickel-manganese sulfate for dual Na-Li-ion batteries.

Science.gov (United States)

Marinova, Delyana M; Kukeva, Rosica R; Zhecheva, Ekaterina N; Stoyanova, Radostina K

2018-04-26

Double sodium transition metal sulfates combine in themselves unique intercalation properties with eco-compatible compositions - a specific feature that makes them attractive electrode materials for lithium and sodium ion batteries. Herein, we examine the intercalation properties of novel double sodium nickel-manganese sulfate, Na2Ni1/2Mn1/2(SO4)2, having a large monoclinic unit cell, through electrochemical and ex situ diffraction and spectroscopic methods. The sulfate salt Na2Ni1/2Mn1/2(SO4)2 is prepared by thermal dehydration of the corresponding hydrate salt Na2Ni1/2Mn1/2(SO4)2·4H2O having a blödite structure. The intercalation reactions on Na2Ni1-xMnx(SO4)2 are studied in two model cells: half-ion cell versus Li metal anode and full-ion cell versus Li4Ti5O12 anode by using lithium (LiPF6 dissolved in EC/DMC) and sodium electrolytes (NaPF6 dissolved in EC:DEC). Based on ex situ XRD and TEM analysis, it is found that sodium intercalation into Na2Ni1/2Mn1/2(SO4)2 takes place via phase separation into the Ni-rich monoclinic phase and Mn-rich alluaudite phase. The redox reactions involving participation of manganese and titanium ions are monitored by ex situ EPR spectroscopy. It has been demonstrated that manganese ions from the sulfate salt are participating in the electrochemical reaction, while the nickel ions remain intact. As a result, a reversible capacity of about 65 mA h g-1 is reached. The selective intercalation properties determine sodium nickel-manganese sulfate as a new electrode material for hybrid lithium-sodium ion batteries that is thought to combine the advantages of individual lithium and sodium batteries.

Lithium ion intercalation into thin film anatase

International Nuclear Information System (INIS)

Kundrata, I.; Froehlich, K.; Ballo, P.

2015-01-01

The aim of this work is to find the optimal parameters for thin film TiO 2 anatase grown by Atomic layer deposition (ALD) for use as electrode in lithium ion batteries. Two parameters, the optimal film thickness and growth conditions are aimed for. Optimal film thickness for achieving optimum between capacity gained from volume and capacity gained by changing of the intercalation constant and optimal growth conditions for film conformity on structured substrates with high aspect ratio. Here we presents first results from this ongoing research and discuss future outlooks. (authors)

Electrochemical properties of Super P carbon black as an anode active material for lithium-ion batteries

International Nuclear Information System (INIS)

Gnanamuthu, RM.; Lee, Chang Woo

2011-01-01

Highlights: → A novel attempt of Super P carbon black as an anode active material for lithium-ion batteries. → The first discharge capacity was approximately 1256 mAh g -1 and at the end of 20th cycling the capacity was 610 mAh g -1 at 0.1 C rate. → Coulombic efficiency of Super P carbon black electrode was maintained about 84% at the end of cycling. - Abstract: A new approach to investigate upon the electrochemical properties of Super P carbon black anode material is attempted and compared with conventional mesophase pitch-based carbon fibers (MPCFs) anode material for lithium-ion batteries. The prepared Super P carbon black electrodes are characterized using transmission electron microscope (TEM). The assembled 2032-type coin cells are electrochemically characterized by ac impedance spectroscopic and cyclic voltammetric methods. The electrochemical performance of charge and discharge was analyzed using a battery cycler at 0.1 C rate and cut-off potentials of 1.20 and 0.01 V vs. Li/Li + . The electrochemical test illustrates that the discharge capacity corresponding to Li intercalation into the Super P carbon black electrode is higher and coulombic efficiency is maintained approximately 84% at the end of the 20th cycling at room temperature.

Influence of water contamination and conductive additives on the intercalation of lithium into graphite

Energy Technology Data Exchange (ETDEWEB)

Joho, F; Rykart, B; Novak, P [Paul Scherrer Inst. (PSI), Villigen (Switzerland); Spahr, M E; Monnier, A [Timcal AG, Sins (Switzerland)

1999-08-01

The irreversible charge loss in the first cycle of lithium intercalation into graphite electrodes for lithium-ion batteries is discussed as a function of water contamination of the electrolyte solution. Furthermore, the improvement of the electrode cycle life due to conductive additives to graphite is demonstrated. (author) 5 figs., 3 refs.

Synthesis, characterisation and electrochemical intercalation kinetics of nanostructured aluminium-doped Li[Li0.2Mn0.54Ni0.13Co0.13]O2 cathode material for lithium ion battery

CSIR Research Space (South Africa)

Jafta, CJ

2012-08-01

Full Text Available is lower than that of the LMNC, but LMNCA shows a better stability with cycling and a better discharge capacity. The EIS results showed some variation in surface film resistance (Rf) and lithium intercalation/de-intercalation resistance (Rct) as a function...

First principles simulation of the electrochemical behaviour of lithium battery materials; Modelisation du comportement electrochimique de materiaux pour batteries au lithium a partir de calculs de premiers principes

Energy Technology Data Exchange (ETDEWEB)

Rocquefelte, X.

2001-10-01

The functioning of a positive electrode in a lithium battery is based on the reversible intercalation of lithium. In some cases, such a reaction can lead to important structural modifications and therefore to an amorphization of the material. A theoretical approach is presented here that leads to structural predictions and simulations of electrochemical behaviour of positive electrode materials. In the first part, DFT (Density Functional Theory) formalisms and the respective advantages of FLAPW (Full potential Linearized Augmented Plane Waves) and PP/PW (Pseudopotential / Plane Waves) methods are discussed. In the second part are given some fundamental electrochemistry considerations related to the intercalation process, thermodynamics aspects and relationships with electronic structure. Then, an approach combining experimental data and geometry optimisation of structural hypotheses is given. This approach was first applied to a model compound LiMoS{sub 2}, and has been then generalised to systems of industrial interest such as Li{sub x}V{sub 2}O{sub 5} (0 {<=} x {<=} 3). The simulated X-ray diagrams of the optimised structures for LiMoS{sub 2} and {omega} - Li{sub 3}V{sub 2}O{sub 5} are in good agreement with experimental data. In the case of Li{sub x}V{sub 2}O{sub 5}, the first discharge curves starting from {alpha} - V{sub 2}O{sub 5} and {gamma}' - V{sub 2}O{sub 5} were then successfully simulated. A chemical bond analysis was carried out to help understand the origin of the distortion in LiMoS{sub 2} and the voltage variations in the electrochemical curves of Li{sub x}V{sub 2}O{sub 5}. This study clearly demonstrates that an approach combining first-principle calculations and available experimental data is invaluable in the structure determination of poorly crystallized compounds. Such a procedure contributes to the understanding of the phase transitions induced by the lithium intercalation in vanadium oxide compounds and can really be used in the research

First principles simulation of the electrochemical behaviour of lithium battery materials; Modelisation du comportement electrochimique de materiaux pour batteries au lithium a partir de calculs de premiers principes

Energy Technology Data Exchange (ETDEWEB)

Rocquefelte, X

2001-10-01

The functioning of a positive electrode in a lithium battery is based on the reversible intercalation of lithium. In some cases, such a reaction can lead to important structural modifications and therefore to an amorphization of the material. A theoretical approach is presented here that leads to structural predictions and simulations of electrochemical behaviour of positive electrode materials. In the first part, DFT (Density Functional Theory) formalisms and the respective advantages of FLAPW (Full potential Linearized Augmented Plane Waves) and PP/PW (Pseudopotential / Plane Waves) methods are discussed. In the second part are given some fundamental electrochemistry considerations related to the intercalation process, thermodynamics aspects and relationships with electronic structure. Then, an approach combining experimental data and geometry optimisation of structural hypotheses is given. This approach was first applied to a model compound LiMoS{sub 2}, and has been then generalised to systems of industrial interest such as Li{sub x}V{sub 2}O{sub 5} (0 {<=} x {<=} 3). The simulated X-ray diagrams of the optimised structures for LiMoS{sub 2} and {omega} - Li{sub 3}V{sub 2}O{sub 5} are in good agreement with experimental data. In the case of Li{sub x}V{sub 2}O{sub 5}, the first discharge curves starting from {alpha} - V{sub 2}O{sub 5} and {gamma}' - V{sub 2}O{sub 5} were then successfully simulated. A chemical bond analysis was carried out to help understand the origin of the distortion in LiMoS{sub 2} and the voltage variations in the electrochemical curves of Li{sub x}V{sub 2}O{sub 5}. This study clearly demonstrates that an approach combining first-principle calculations and available experimental data is invaluable in the structure determination of poorly crystallized compounds. Such a procedure contributes to the understanding of the phase transitions induced by the lithium intercalation in vanadium oxide compounds and can really be used in the research of

Dynamic Electrochemical Impedance Spectroscopy of a Three-Electrode Lithium-Ion Battery during Pulse Charge and Discharge

International Nuclear Information System (INIS)

Huang, Jun; Ge, Hao; Li, Zhe; Zhang, Jianbo

2015-01-01

Highlights: • Dynamic EIS is performed on a three-electrode pouch cell; • Charge transfer resistance during insertion is generally larger than that during deinsertion due to the surface concentration change; • An inductive behavior is revealed at low frequencies due to the violation of stationary condition in DEIS measurement; • Electrochemical models of a single active particle in both time and frequency domain are developed. • The model predicts a positive correlation between the lower frequency limit and the DC current. - Abstract: The dynamic electrochemical impedance spectroscopy (DEIS) of a three-electrode pouch type lithium-ion battery is measured using a series of sine wave perturbations super-imposed on pulse charge and discharge. The DEIS reveals noticeable differences between charge and discharge at frequencies corresponding to the charge transfer reaction. The charge transfer resistance during intercalation is generally found to be larger than that during deintercalation for the battery chemistry in this study. This result is mainly attributed to the decreased Li ion concentration in the electrolyte during intercalation. At low frequencies, an abnormal inductive behavior is also observed. Such abnormality is found to result from the violation of stationary condition, i.e. the state of the battery under pulse charge or discharge deviates significantly from its initial condition for the perturbation of low frequencies. To analytically define the stationary condition, we develop electrochemical models of a single active particle in both time and frequency domain, which describes the transport of lithium ions in both active particle and electrolyte phase and the interfacial charge transfer reactions at their interface. The lower frequency limit is a key parameter to ensure a quasistationary state during the DEIS measurement. An explicit formulation of the stationary condition predicts a positive correlation between the lower frequency limit and

Li Storage of Calcium Niobates for Lithium Ion Batteries.

Science.gov (United States)

Yim, Haena; Yu, Seung-Ho; Yoo, So Yeon; Sung, Yung-Eun; Choi, Ji-Won

2015-10-01

New types of niobates negative electrode were studied for using in lithium-ion batteries in order to alternate metallic lithium anodes. The potassium intercalated compound KCa2Nb3O10 and proton intercalated compound HCa2Nb3O10 were studied, and the electrochemical results showed a reversible cyclic voltammetry profile with acceptable discharge capacity. The as-prepared KCa2Nb3O10 negative electrode had a low discharge capacity caused by high overpotential, but the reversible intercalation and deintercalation reaction of lithium ions was activated after exchanging H+ ions for intercalated K+ ions. The initial discharge capacity of HCa2Nb3O10 was 54.2 mAh/g with 92.1% of coulombic efficiency, compared with 10.4 mAh/g with 70.2% of coulombic efficiency for KCa2Nb3O10 at 1 C rate. The improved electrochemical performance of the HCa2Nb3O10 was related to the lower bonding energy between proton cation and perovskite layer, which facilitate Li+ ions intercalating into the cation site, unlike potassium cation and perovskite layer. Also, this negative material can be easily exfoliated to Ca2Nb3O10 layer by using cation exchange process. Then, obtained two-dimensional nanosheets layer, which recently expected to be an advanced electrode material because of its flexibility, chemical stable, and thin film fabricable, can allow Li+ ions to diffuse between the each perovskite layer. Therefore, this new type layered perovskite niobates can be used not only bulk-type lithium ion batteries but also thin film batteries as a negative material.

Electrical and electrochemical properties of niobium disulphide

Energy Technology Data Exchange (ETDEWEB)

Molenda, J.; Bak, T.; Marzec, J. [Academy of Min. and Metall., Cracow (Poland). Dept. of Chem. of Solids

1996-07-16

The electrical conductivity and thermoelectric power measurements of NbS{sub 2} pure and electrochemically doped with lithium, Li{sub x}NbS{sub 2}, were done as a function of temperature (77 to 300 K). The high absolute values of conductivity and their dependence on temperature together with low absolute values of thermoelectric power and their linear increase with temperature indicate metallic properties of niobium disulphide. In case of Li{sub x}NbS{sub 2} the obtained values of electrical conductivity are significantly lower as compared with the starting NbS{sub 2}. The temperature dependence of the thermo-electric power of intercalated niobium disulphide also indicates that metallic properties get worse as the concentration of lithium increases. The modification of the electronic structure of NbS{sub 2} due to lithium intercalation was proposed. The character of the discharge curves in the electrochemical Li/Li{sup +}/Li{sub x}NbS{sub 2} systems was correlated with the electronic properties of niobium disulphide. (orig.) 11 refs.

Effect of current pulses on Lithium intercalation batteries

NARCIS (Netherlands)

Jongh, de P.E.; Notten, P.H.L.

2002-01-01

The effect of (dis)charge pulses on lithium-ion batteries is evaluated using an electronic network model. Simulations give insight into the effect of the pulses on the internal processes such as diffusion, migration, electrochemical reactions, heat generation, etc. on time scales from microseconds

Lithium intercalation into layered LiMnO2

DEFF Research Database (Denmark)

Vitins, G.; West, Keld

1997-01-01

Recently Armstrong and Bruce(1) reported a layered modification of lithium manganese oxide, LiMnO2, isostructural with LiCoO2. LiMnO2 obtained by ion exchange from alpha-NaMnO2 synthesized in air is characterized by x-ray diffraction and by electrochemical insertion and extraction of lithium...... in a series of voltage ranges between 1.5 and 4.5 V relative to a lithium electrode. During cycling voltage plateaus at 3.0 and 4.0 V vs. Li develop, indicating that the material is converted from its original layered structure to a spinel structure. This finding is confirmed by x-ray diffraction. Contrary...... to expectations based on thermodynamics, insertion of larger amounts of lithium leads to a more complete conversion. We suggest that a relatively high mobility of manganese leaves Li and Mn randomly distributed in the close-packed oxygen lattice after a deep discharge. This isotropic Mn distribution can...

Intercalated Water and Organic Molecules for Electrode Materials of Rechargeable Batteries.

Science.gov (United States)

Lee, Hyeon Jeong; Shin, Jaeho; Choi, Jang Wook

2018-03-24

The intrinsic limitations of lithium-ion batteries (LIBs) with regard to safety, cost, and the availability of raw materials have promoted research on so-called "post-LIBs". The recent intense research of post-LIBs provides an invaluable lesson that existing electrode materials used in LIBs may not perform as well in post-LIBs, calling for new material designs compliant with emerging batteries based on new chemistries. One promising approach in this direction is the development of materials with intercalated water or organic molecules, as these materials demonstrate superior electrochemical performance in emerging battery systems. The enlarged ionic channel dimensions and effective shielding of the electrostatic interaction between carrier ions and the lattice host are the origins of the observed electrochemical performance. Moreover, these intercalants serve as interlayer pillars to sustain the framework for prolonged cycles. Representative examples of such intercalated materials applied to batteries based on Li + , Na + , Mg 2+ , and Zn 2+ ions and supercapacitors are considered, along with their impact in materials research. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electrochemical Performance of Electrospun carbon nanofibers as free-standing and binder-free anodes for Sodium-Ion and Lithium-Ion Batteries

International Nuclear Information System (INIS)

Jin, Juan; Shi, Zhi-qiang; Wang, Cheng-yang

2014-01-01

Highlights: • Electrospun carbon nanofiber webs were prepared by pyrolysis of polyacrylonitrile. • The webs as binder-free and current collector-free electrodes for SIBs and LIBs. • Different layer spacing and pore size for Li and Na lead different electrochemical behavior. • Electrochemical performances of the electrodes were high. - Abstract: A series of hard carbon nanofiber-based electrodes derived from electrospun polyacrylonitrile (PAN) nanofibers (PAN-CNFs) have been fabricated by stabilization in air at about 280 °C and then carbonization in N 2 at heat treatment temperatures (HTT) between 800 and 1500 °C. The electrochemical performances of the binder-free, current collector-free carbon nanofiber-based anodes in lithium-ion batteries and sodium-ion batteries are systematically investigated and compared. We demonstrate the presence of similar alkali metal insertion mechanisms in both cases, but just the differences of the layer spacing and pore size available for lithium and sodium ion lead the discharge capacity delivered at sloping region and plateau region to vary from the kinds of alkali elements. Although the anodes in sodium-ion batteries show poorer rate capability than that in lithium-ion batteries, they still achieve a reversible sodium intercalation capacity of 275 mAh g −1 and similar cycling stability due to the conductive 3-D network, weakly ordered turbostratic structure and a large interlayer spacing between graphene sheets. The feature of high capacity and stable cycling performance makes PAN-CNFs to be promising candidates as electrodes in rechargeable sodium-ion batteries and lithium-ion batteries

A facile electrochemical intercalation and microwave assisted exfoliation methodology applied to screen-printed electrochemical-based sensing platforms to impart improved electroanalytical outputs.

Science.gov (United States)

Pierini, Gastón D; Foster, Christopher W; Rowley-Neale, Samuel J; Fernández, Héctor; Banks, Craig E

2018-06-12

Screen-printed electrodes (SPEs) are ubiquitous with the field of electrochemistry allowing researchers to translate sensors from the laboratory to the field. In this paper, we report an electrochemically driven intercalation process where an electrochemical reaction uses an electrolyte as a conductive medium as well as the intercalation source, which is followed by exfoliation and heating/drying via microwave irradiation, and applied to the working electrode of screen-printed electrodes/sensors (termed EDI-SPEs) for the first time. This novel methodology results in an increase of up to 85% of the sensor area (electrochemically active surface area, as evaluated using an outer-sphere redox probe). Upon further investigation, it is found that an increase in the electroactive area of the EDI-screen-printed based electrochemical sensing platforms is critically dependent upon the analyte and its associated electrochemical mechanism (i.e. adsorption vs. diffusion). Proof-of-concept for the electrochemical sensing of capsaicin, a measure of the hotness of chillies and chilli sauce, within both model aqueous solutions and a real sample (Tabasco sauce) is demonstrated in which the electroanalytical sensitivity (a plot of signal vs. concentration) is doubled when utilising EDI-SPEs over that of SPEs.

Re-entrant lithium local environments and defect driven electrochemistry of Li- and Mn-rich Li-ion battery cathodes.

Science.gov (United States)

Dogan, Fulya; Long, Brandon R; Croy, Jason R; Gallagher, Kevin G; Iddir, Hakim; Russell, John T; Balasubramanian, Mahalingam; Key, Baris

2015-02-18

Direct observations of structure-electrochemical activity relationships continue to be a key challenge in secondary battery research. (6)Li magic angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy is the only structural probe currently available that can quantitatively characterize local lithium environments on the subnanometer scale that dominates the free energy for site occupation in lithium-ion (Li-ion) intercalation materials. In the present study, we use this local probe to gain new insights into the complex electrochemical behavior of activated 0.5(6)Li2MnO3·0.5(6)LiMn(0.5)Ni(0.5)O2, lithium- and manganese-rich transition-metal (TM) oxide intercalation electrodes. We show direct evidence of path-dependent lithium site occupation, correlated to structural reorganization of the metal oxide and the electrochemical hysteresis, during lithium insertion and extraction. We report new (6)Li resonances centered at ∼1600 ppm that are assigned to LiMn6-TM(tet) sites, specifically, a hyperfine shift related to a small fraction of re-entrant tetrahedral TMs (Mn(tet)), located above or below lithium layers, coordinated to LiMn6 units. The intensity of the TM layer lithium sites correlated with tetrahedral TMs loses intensity after cycling, indicating limited reversibility of TM migrations upon cycling. These findings reveal that defect sites, even in dilute concentrations, can have a profound effect on the overall electrochemical behavior.

The electrochemical performance and mechanism of cobalt (II) fluoride as anode material for lithium and sodium ion batteries

International Nuclear Information System (INIS)

Tan, Jinli; Liu, Li; Guo, Shengping; Hu, Hai; Yan, Zichao; Zhou, Qian; Huang, Zhifeng; Shu, Hongbo; Yang, Xiukang; Wang, Xianyou

2015-01-01

Highlights: •The as-prepared CoF 2 shows excellent electrochemical performance as anode material for lithium ion batteries. •The Li insertion/extraction mechanism of CoF 2 below 1.2 V was firstly proposed. •The electrochemical performance of CoF 2 as anode material in sodium ion batteries was firstly studied. -- Abstract: Cobalt (II) fluoride begins to enter into the horizons of people along with the research upsurge of metal fluorides. It is very significative and theoretically influential to make certain its electrochemical reaction mechanism. In this work, we discover a new and unrevealed reversible interfacial intercalation mechanism reacting below 1.2 V for cobalt (II) fluoride electrode material, which contributes a combined discharge capacity of about 400 mA h g −1 with the formation of SEI film at the initial discharge process. A highly reversible storage capacity of 120 mA h g −1 is observed when the cell is cycled over the voltage of 0.01-1.2 V at 0.2 C, and the low-potential voltage reaction process has a significant impact for the whole electrochemical process. Electrochemical analyses suggest that pure cobalt (II) fluoride shows better electrochemical performance when it is cycled at 3.2-0.01 V compared to the high range (1.0-4.5 V). So, we hold that cobalt (II) fluoride is more suitable to serve as anode material for lithium ion batteries. In addition, we also try to reveal the relevant performance and reaction mechanism, and realize the possibility of cobalt (II) fluoride as anode material for sodium ion batteries

Synthesis and characterization of high performance electrode materials for lithium ion batteries

Science.gov (United States)

Hong, Jian

Lithium-ion batteries have revolutionized portable electronics. Electrode reactions in these electrochemical systems are based on reversible intercalation of Li+ ions into the host electrode material with a concomitant addition/removal of electrons into the host. If such batteries are to find a wider market such as the automotive industry, less expensive and higher capacity electrode materials will be required. The olivine phase lithium iron phosphate has attracted the most attention because of its low cost and safety (high thermal and chemical stability). However, it is an intriguing fundamental problem to understand the fast electrochemical response from the poorly electronic conducting two-phase LiFePO4/FePO 4 system. This thesis focuses on determining the rate-limit step of LiFePO4. First, a LiFePO4 material, with vanadium substituting on the P-site, was synthesized, and found that the crystal structure change may cause high lithium diffusivity. Since an accurate Li diffusion coefficient cannot be measured by traditional electrochemical method in a three-electrode cell due to the phase transformation during measurement, a new method to measure the intrinsic electronic and ionic conductivity of mixed conductive LiFePO 4 was developed. This was based on the conductivity measurements of mixed conductive solid electrolyte using electrochemical impedance spectroscopy (EIS) and blocking electrode. The effects of ionic/electronic conductivity and phase transformation on the rate performance of LiFePO4 were also first investigated by EIS and other electrochemical technologies. Based on the above fundamental kinetics studies, an optimized LiFePO4 was used as a target to deposit 1mum LiFePO4 thin film at Oak Ridge National Laboratory using radio frequency (RF) magnetron sputtering. Similar to the carbon coated LiFePO4 powder electrode, the carbon-contained RF LiFePO4 film with no preferential orientation showed excellent capacity and rate capability both at 25°C and -20

Electrophoretic Nanocrystalline Graphene Film Electrode for Lithium Ion Battery

International Nuclear Information System (INIS)

Kaprans, Kaspars; Bajars, Gunars; Kucinskis, Gints; Dorondo, Anna; Mateuss, Janis; Gabrusenoks, Jevgenijs; Kleperis, Janis; Lusis, Andrejs

2015-01-01

Graphene sheets were fabricated by electrophoretic deposition method from water suspension of graphene oxide followed by thermal reduction. The formation of nanocrystalline graphene sheets has been confirmed by scanning electron microscopy, X-ray diffraction and Raman spectroscopy. The electrochemical performance of graphene sheets as anode material for lithium ion batteries was evaluated by cycling voltammetry, galvanostatic charge-discharge cycling, and electrochemical impedance spectroscopy. Fabricated graphene sheets exhibited high discharge capacity of about 1120 mAh·g −1 and demonstrated good reversibility of lithium intercalation and deintercalation in graphene sheet film with capacity retention over 85 % after 50 cycles. Results show that nanocrystalline graphene sheets prepared by EPD demonstrated a high potential for application as anode material in lithium ion batteries

Effect of pre-lithiation degrees of mesocarbon microbeads anode on the electrochemical performance of lithium-ion capacitors

International Nuclear Information System (INIS)

Zhang, Jin; Shi, Zhiqiang; Wang, Chengyang

2014-01-01

Highlights: • MCMB with different pre-lithiation capacity as negative electrode in LIC. • Pre-lithiation improves the electrochemical performance of LIC. • The optimal pre-lithiation capacity has been proposed. - Abstract: Lithium ion capacitors are assembled with pre-lithiated mesocarbon microbeads (LMCMB) anode and activated carbon (AC) cathode. The effect of pre-lithiation degrees on the crystal structure of MCMB electrode and the electrochemical capacitance behavior of LIC are investigated by X-ray diffraction (XRD) and the charge-discharge test of three-electrode cell. The structure of graphite still maintained when the pre-lithiation capacity is less than 200 mAh g −1 , phase transition takes place with the increase of pre-lithiation capacity from 250 mAh g −1 to 350 mAh g −1 . Pre-lithiation degrees of MCMB anode greatly affect the charge-discharge process and behavior, which impact on the electrochemical performance of LIC. The LIC with pre-lithiation capacity of 300 mAh g −1 has the optimal electrochemical performance. The energy density of LIC300 is up to 92.3 Wh kg −1 , the power density as high as 5.5 kW kg −1 and the capacity retention is 97.0% after 1000 cycles. The excellent electrochemical performance benefits from the appropriate pre-lithiation capacity of negative electrode. The appropriate pre-lithiation ensures the working voltage of negative electrode in low and relative stable charge-discharge platform corresponding to the mutual phase transition from the second stage graphite intercalation compound (LiC 12 ) to the first stage graphite intercalation compound (LiC 6 ). The stable charge-discharge platform of negative electrode is conductive to the sufficient utilization of AC positive electrode

Topotactic insertion of lithium in the layered structure Li4VO(PO4)2: The tunnel structure Li5VO(PO4)2

International Nuclear Information System (INIS)

Satya Kishore, M.; Pralong, V.; Caignaert, V.; Malo, S.; Hebert, S.; Varadaraju, U.V.; Raveau, B.

2008-01-01

A new V(III) lithium phosphate Li 5 VO(PO 4 ) 2 has been synthesized by electrochemical insertion of lithium into Li 4 VO(PO 4 ) 2 . This phase, which crystallizes in the space group I4/mcm, exhibits a tunnel structure closely related to the layered structure of Li 4 VO(PO 4 ) 2 and to the tunnel structure of VO(H 2 PO 4 ) 2 . The topotactic reactions that take place during lithium exchange and intercalation, starting from VO(H 2 PO 4 ) 2 and going to the final phase Li 5 VO(PO 4 ) 2 are explained on the basis of the flexible coordinations of V 4+ and V 3+ species. The electrochemical and magnetic properties of this new phase are also presented and explained on the basis of the structure dimensionality. - Graphical abstract: Electrochemical synthesis of a new 3D V(III) lithium phosphate, Li 5 VO(PO 4 ) 2 . Starting from the 2D Li 4 VO(PO 4 ) 2 , the topotactic reaction that take place during lithium intercalation is explained on the basis of the flexible coordinations of V 4+ and V 3+ species

Unique effect of mechanical crushing on the electrochemical intercalation of lithium in carbons of different morphologies; Effet unique du broyage mecanique sur l`intercalation electrochimique du lithium dans des carbones de morphologies differentes

Energy Technology Data Exchange (ETDEWEB)

Salver-Disma, F.; Tarascon, J.M. [Universite de Picardie, 80 - Amiens (France)

1996-12-31

Lithium ion batteries use an oxide as a positive electrode and a carbon material as a negative electrode. The performances of carbon electrodes have rapidly evolved during the last years thanks to the substitution of soft carbons of Conoco or MCMB-2510 type by graphites (F-399, MCMB-2528) and then by hard carbons. These high capacity carbons (700 mAh/g) have higher service life and volume capacity than graphites but their irreversible losses are greater (>20%). In this work, materials with similar electrochemical performances are prepared by mechanical crushing. Mechanical crushing allows to obtain a wide range of carbon materials with various morphologies, specific surfaces and levels of disorder. The formation of the passivation film is directly linked with the surface of materials. A reaction scheme of the reversible and irreversible capacities has been defined and has permitted to obtain compounds with reversible capacities of 720 mAh/g (2 lithium for 6 carbon). (J.S.)

Unique effect of mechanical crushing on the electrochemical intercalation of lithium in carbons of different morphologies; Effet unique du broyage mecanique sur l`intercalation electrochimique du lithium dans des carbones de morphologies differentes

Energy Technology Data Exchange (ETDEWEB)

Salver-Disma, F; Tarascon, J M [Universite de Picardie, 80 - Amiens (France)

1997-12-31

Lithium ion batteries use an oxide as a positive electrode and a carbon material as a negative electrode. The performances of carbon electrodes have rapidly evolved during the last years thanks to the substitution of soft carbons of Conoco or MCMB-2510 type by graphites (F-399, MCMB-2528) and then by hard carbons. These high capacity carbons (700 mAh/g) have higher service life and volume capacity than graphites but their irreversible losses are greater (>20%). In this work, materials with similar electrochemical performances are prepared by mechanical crushing. Mechanical crushing allows to obtain a wide range of carbon materials with various morphologies, specific surfaces and levels of disorder. The formation of the passivation film is directly linked with the surface of materials. A reaction scheme of the reversible and irreversible capacities has been defined and has permitted to obtain compounds with reversible capacities of 720 mAh/g (2 lithium for 6 carbon). (J.S.)

Nano-Sn embedded in expanded graphite as anode for lithium ion batteries with improved low temperature electrochemical performance

International Nuclear Information System (INIS)

Yan, Yong; Ben, Liubin; Zhan, Yuanjie; Huang, Xuejie

2016-01-01

Highlights: • Nano-Sn embedded in interlayers of expanded graphite is fabricated. • The graphene/nano-Sn/graphene stacked structure promotes cycling stability of Sn. • The Sn/EG shows improved low temperature electrochemical performance. • Chemical diffusion coefficients of the Sn/EG are obtained by GITT. • The Sn/EG exhibits faster Li-ion intercalation kinetics than graphite. - Abstract: Metallic tin (Sn) used as anode material for lithium ion batteries has long been proposed, but its low temperature electrochemical performance has been rarely concerned. Here, a Sn/C composite with nano-Sn embedded in expanded graphite (Sn/EG) is synthesized. The nano-Sn particles (∼30 nm) are uniformly distributed in the interlayers of expanded graphite forming a tightly stacked layered structure. The electrochemical performance of the Sn/EG, particularly at low temperature, is carefully investigated compared with graphite. At -20 °C, the Sn/EG shows capacities of 200 mAh g −1 at 0.1C and 130 mAh g −1 at 0.2C, which is much superior to graphite (<10 mAh g −1 ). EIS measurements suggest that the charge transfer impedance of the Sn/EG increases less rapidly than graphite with decreasing temperatures, which is responsible for the improved low temperature electrochemical performance. The Li-ion chemical diffusion coefficients of the Sn/EG obtained by GITT are an order of magnitude higher at room temperature than that at -20 °C. Furthermore, the Sn/EG exhibits faster Li-ion intercalation kinetics than graphite in the asymmetric charge/discharge measurements, which shows great promise for the application in electric vehicles charged at low temperature.

V sub 2 O sub 5 -based glasses as cathodes for lithium batteries

Energy Technology Data Exchange (ETDEWEB)

Levy, M; Duclot, M J; Rousseau, F [British Columbia Univ., Vancouver (Canada)

1989-05-01

The electronic conductivities of glasses in the TeO2-V2O5 and TeO2-V2O5-MoO3 systems have been determined in the 20-200 C temperature range to give simple Arrhenius relationships. Chemical and electrochemical lithium intercalations have been performed, showing that V2O5-based glasses are suitable positive electrode materials for lithium batteries. 20 refs.

Performance of titanium dioxide-based cathodes in a lithium polymer electrolyte cell

Energy Technology Data Exchange (ETDEWEB)

Macklin, W.J. (Applied Electrochemistry Dept., AEA Industry Technology, Harwell (United Kingdom)); Neat, R.J. (Applied Electrochemistry Dept., AEA Industry Technology, Harwell (United Kingdom))

Performance data on two polymorphs of titanium dioxide (anatase and rutile) operating in a lithium polymer electrolyte cell at 120 C are presented. On the first discharge lithium ions can be electrochemically inserted into both forms to an approximate composition LiTiO[sub 2]. However, only the rutile material cycles with a significant capacity ([proportional to] 0.5 Li/TiO[sub 2]) with an average cell voltage of 1.73 V corresponding to a theoretical energy density of [proportional to] 290 W h kg[sup -1]. Our results are in contrast to earlier work reported on the intercalation of lithium into these phases at room temperature, where only the anatase form was found to intercalate lithium. X-ray diffraction data indicate that the rutile form undergoes a structural change during the first discharge resulting in the formation of a hexagonal form of LiTiO[sub 2].

Lithium iron phosphate/carbon nanocomposite film cathodes for high energy lithium ion batteries

International Nuclear Information System (INIS)

Liu, Yanyi; Liu, Dawei; Zhang, Qifeng; Yu, Danmei; Liu, Jun; Cao, Guozhong

2011-01-01

This paper reports sol-gel derived nanostructured LiFePO4/carbon nanocomposite film cathodes exhibiting enhanced electrochemical properties and cyclic stabilities. LiFePO4/carbon films were obtained by spreading sol on Pt coated Si wafer followed by ambient drying overnight and annealing/pyrolysis at elevated temperature in nitrogen. Uniform and crack-free LiFePO4/carbon nanocomposite films were readily obtained and showed olivine phase as determined by means of X-Ray Diffractometry. The electrochemical characterization revealed that, at a current density of 200 mA/g (1.2 C), the nanocomposite film cathodes demonstrated an initial lithium-ion intercalation capacity of 312 mAh/g, and 218 mAh/g after 20 cycles, exceeding the theoretical storage capacity of conventional LiFePO4 electrode. Such enhanced Li-ion intercalation performance could be attributed to the nanocomposite structure with fine crystallite size below 20 nm as well as the poor crystallinity which provides a partially open structure allowing easy mass transport and volume change associated with Li-ion intercalation. Moreover the surface defect introduced by carbon nanocoating could also effectively facilitate the charge transfer and phase transitions.

Nanoscale visualization of redox activity at lithium-ion battery cathodes.

Science.gov (United States)

Takahashi, Yasufumi; Kumatani, Akichika; Munakata, Hirokazu; Inomata, Hirotaka; Ito, Komachi; Ino, Kosuke; Shiku, Hitoshi; Unwin, Patrick R; Korchev, Yuri E; Kanamura, Kiyoshi; Matsue, Tomokazu

2014-11-17

Intercalation and deintercalation of lithium ions at electrode surfaces are central to the operation of lithium-ion batteries. Yet, on the most important composite cathode surfaces, this is a rather complex process involving spatially heterogeneous reactions that have proved difficult to resolve with existing techniques. Here we report a scanning electrochemical cell microscope based approach to define a mobile electrochemical cell that is used to quantitatively visualize electrochemical phenomena at the battery cathode material LiFePO4, with resolution of ~100 nm. The technique measures electrode topography and different electrochemical properties simultaneously, and the information can be combined with complementary microscopic techniques to reveal new perspectives on structure and activity. These electrodes exhibit highly spatially heterogeneous electrochemistry at the nanoscale, both within secondary particles and at individual primary nanoparticles, which is highly dependent on the local structure and composition.

Classical molecular dynamics and quantum ab-initio studies on lithium-intercalation in interconnected hollow spherical nano-spheres of amorphous silicon

Energy Technology Data Exchange (ETDEWEB)

Bhowmik, A. [Atomic Scale Modelling and Materials, Department of Energy Conversion and Storage, Technical University of Denmark, Rios Campus, Frederiksborgvej 399, DK-4000 Roskilde (Denmark); Malik, R. [Department of Metallurgical and Materials Engineering, Indian Institute of Technology Kharagpur, 721302 (India); Prakash, S. [Defense Metallurgical Research Laboratory, Hyderabad (India); Sarkar, T.; Bharadwaj, M.D. [Center for Study of Science Technology and Policy, Bangalore 560094 (India); Aich, S. [Department of Metallurgical and Materials Engineering, Indian Institute of Technology Kharagpur, 721302 (India); Ghosh, S., E-mail: sudipto@metal.iitkgp.ernet.in [Department of Metallurgical and Materials Engineering, Indian Institute of Technology Kharagpur, 721302 (India)

2016-04-25

A high concentration of lithium, corresponding to charge capacity of ∼4200 mAh/g, can be intercalated in silicon. Unfortunately, due to high intercalation strain leading to fracture and consequent poor cyclability, silicon cannot be used as anode in lithium ion batteries. But recently interconnected hollow nano-spheres of amorphous silicon have been found to exhibit high cyclability. The absence of fracture upon lithiation and the high cyclability has been attributed to reduction in intercalation stress due to hollow spherical geometry of the silicon nano-particles. The present work argues that the hollow spherical geometry alone cannot ensure the absence of fracture. Using classical molecular dynamics and density functional theory based simulations; satisfactory explanation to the absence of fracture has been explored at the atomic scale. - Highlights: • Interconnected nanoshells of amorphous Si: best available lithium ion cell anode. • High cycle life not understood in the light of poor K{sub IC} of amorphous Si. • MD reveals: atomic density of interconnected structure is ∼16% less than bulk Si. • Leads to drastic reduction (DFT) in lithiation σ & metal like e{sup −} structure (high K{sub IC}). • Lowering of lithiation σ and increase in K{sub IC} result in high cycle life.

Electrochemical potassium-ion intercalation in NaxCoO2: a novel cathode material for potassium-ion batteries.

Science.gov (United States)

Sada, Krishnakanth; Senthilkumar, Baskar; Barpanda, Prabeer

2017-07-27

Reversible electrochemical potassium-ion intercalation in P2-type Na x CoO 2 was examined for the first time. Hexagonal Na 0.84 CoO 2 platelets prepared by a solution combustion synthesis technique were found to work as an efficient host for K + intercalation. They deliver a high reversible capacity of 82 mA h g -1 , good rate capability and excellent cycling performance up to 50 cycles.

Tunable Broadband Nanocarbon Transparent Conductor by Electrochemical Intercalation.

Science.gov (United States)

Wan, Jiayu; Xu, Yue; Ozdemir, Burak; Xu, Lisha; Sushkov, Andrei B; Yang, Zhi; Yang, Bao; Drew, Dennis; Barone, Veronica; Hu, Liangbing

2017-01-24

Optical transparent and electrical conducting materials with broadband transmission are important for many applications in optoelectronic, telecommunications, and military devices. However, studies of broadband transparent conductors and their controlled modulation are scarce. In this study, we report that reversible transmittance modulation has been achieved with sandwiched nanocarbon thin films (containing carbon nanotubes (CNTs) and reduced graphene oxide (rGO)) via electrochemical alkali-ion intercalation/deintercalation. The transmittance modulation covers a broad range from the visible (450 nm) to the infrared (5 μm), which can be achieved only by rGO rather than pristine graphene films. The large broadband transmittance modulation is understood with DFT calculations, which suggest a decrease in interband transitions in the visible range as well as a reduced reflection in the IR range upon intercalation. We find that a larger interlayer distance in few-layer rGO results in a significant increase in transparency in the infrared region of the spectrum, in agreement with experimental results. Furthermore, a reduced plasma frequency in rGO compared to few-layer graphene is also important to understand the experimental results for broadband transparency in rGO. The broadband transmittance modulation of the CNT/rGO/CNT systems can potentially lead to electrochromic and thermal camouflage applications.

Method for fabricating carbon/lithium-ion electrode for rechargeable lithium cell

Science.gov (United States)

Huang, Chen-Kuo (Inventor); Surampudi, Subbarao (Inventor); Attia, Alan I. (Inventor); Halpert, Gerald (Inventor)

1995-01-01

The method includes steps for forming a carbon electrode composed of graphitic carbon particles adhered by an ethylene propylene diene monomer binder. An effective binder composition is disclosed for achieving a carbon electrode capable of subsequent intercalation by lithium ions. The method also includes steps for reacting the carbon electrode with lithium ions to incorporate lithium ions into graphitic carbon particles of the electrode. An electrical current is repeatedly applied to the carbon electrode to initially cause a surface reaction between the lithium ions and to the carbon and subsequently cause intercalation of the lithium ions into crystalline layers of the graphitic carbon particles. With repeated application of the electrical current, intercalation is achieved to near a theoretical maximum. Two differing multi-stage intercalation processes are disclosed. In the first, a fixed current is reapplied. In the second, a high current is initially applied, followed by a single subsequent lower current stage. Resulting carbon/lithium-ion electrodes are well suited for use as an anode in a reversible, ambient temperature, lithium cell.

Theoretical study on the correlation between the nature of atomic Li intercalation and electrochemical reactivity in TiS2 and TiO2.

Science.gov (United States)

Kim, Yang-Soo; Kim, Hee-Jin; Jeon, Young-A; Kang, Yong-Mook

2009-02-12

The electronic structures of LiTiS(2) and LiTiO(2) (having alpha-NaFeO(2) structure) have been investigated using discrete variational Xalpha molecular orbital methods. The alpha-NaFeO(2) structure is the equilibrium structure for LiCoO(2), which is widely used as a commercial cathode material for lithium secondary batteries. This study especially focused on the charge state of Li ions and the magnitude of covalency around Li ions. When the average voltage of lithium intercalation was calculated using pseudopotential methods, the average intercalation voltage of LiTiO(2) (2.076 V) was higher than that of LiTiS(2) (1.958 V). This can be explained by the differences in Mulliken charge of lithium and the bond overlap population between the intercalated Li ions and anion in LiTiO(2) as well as LiTiS(2). The Mulliken charge, which is the ionicity of Li atom, was approximately 0.12 in LiTiS(2), and the bond overlap population (BOP) indicating the covalency between Ti and S was about 0.339. When compared with the BOP (0.6) of C-H, which is one of the most famous example of covalent bonding, the intercalated Li ions in LiTiS(2) tend to form a quite strong covalent bond with the host material. In contrast, the Mulliken charge of lithium was about 0.79, which means that Li is fully ionized and the BOP, the covalency between Ti and O, was 0.181 in LiTiO(2). Because of the high ionicity of Li and the weak covalency between Ti and the nearest anion, LiTiO(2) has a higher intercalation voltage than LiTiS(2).

Two-Step Electrochemical Intercalation and Oxidation of Graphite for the Mass Production of Graphene Oxide.

Science.gov (United States)

Cao, Jianyun; He, Pei; Mohammed, Mahdi A; Zhao, Xin; Young, Robert J; Derby, Brian; Kinloch, Ian A; Dryfe, Robert A W

2017-12-06

Conventional chemical oxidation routes for the production of graphene oxide (GO), such as the Hummers' method, suffer from environmental and safety issues due to their use of hazardous and explosive chemicals. These issues are addressed by electrochemical oxidation methods, but such approaches typically have a low yield due to inhomogeneous oxidation. Herein we report a two-step electrochemical intercalation and oxidation approach to produce GO on the large laboratory scale (tens of grams) comprising (1) forming a stage 1 graphite intercalation compound (GIC) in concentrated sulfuric acid and (2) oxidizing and exfoliating the stage 1 GIC in an aqueous solution of 0.1 M ammonium sulfate. This two-step approach leads to GO with a high yield (>70 wt %), good quality (>90%, monolayer), and reasonable oxygen content (17.7 at. %). Moreover, the as-produced GO can be subsequently deeply reduced (3.2 at. % oxygen; C/O ratio 30.2) to yield highly conductive (54 600 S m -1 ) reduced GO. Electrochemical capacitors based on the reduced GO showed an ultrahigh rate capability of up to 10 V s -1 due to this high conductivity.

Lithium storage properties of multiwall carbon nanotubes prepared by CVD

International Nuclear Information System (INIS)

Ahn, J.-O.; Andong National University,; Wang, G.X.; Liu, H.K.; Dou, S.X.

2003-01-01

Full text: Multiwall carbon nanotubes (MWCNTs) were synthesised by chemical vapour deposition (CVD) method using acetylene gas. The XRD pattern of as prepared carbon nanotubes showed that the d 002 value is 3.44 Angstroms. The morphology and microstructure of carbon nanotubes were characterized by HRTEM. Most of carbon nanotubes are entangled together to form bundles or ropes. The diameter of the carbon nanotubes is in the range of 10 ∼ 20 nm. There is a small amount of amorphous carbon particles presented in the sample. However, the yield of carbon nanotubes is more than 95%. Electrochemical properties of carbon nanotubes were characterised via a variety of electrochemical testing techniques. The result of CV test showed that the Li insertion potential is quite low, which is very close to O V versus Li + /Li reference electrode, whereas the potential for Li de-intercalation is in the range of 0.2-0.4 V. There exists a slight voltage hysteresis between Li intercalation and Li de-intercalation, which is similar to the other carbonaceous materials. The intensity of redox peaks of carbon nanotubes decrease with scanning cycle, indicating that the reversible Li insertion capacity gradually decreases. The carbon nanotubes electrode demonstrated a reversible lithium storage capacity of 340 mAh/g with good cyclability at moderate current density. Further improvement of Li storage capacity is possible by opening the end of carbon nanotubes to allow lithium insertion into inner graphene sheet of carbon nanotubes. The kinetic properties of lithium insertion in carbon nanotube electrodes were characterised by a.c. impedance measurements. It was found that the lithium diffusion coefficient d Li decreases with an increase of Li ion concentration in carbon nanotube host

Phosphate removal from water using lithium intercalated gibbsite.

Science.gov (United States)

Wang, Shan-Li; Cheng, Chia-Yi; Tzou, Yu-Min; Liaw, Ren-Bao; Chang, Ta-Wei; Chen, Jen-Hshuan

2007-08-17

In this study, lithium intercalated gibbsite (LIG) was investigated for its effectiveness at removing phosphate from water and the mechanisms involved. LIG was prepared through intercalating LiCl into gibbsite giving a structure of [LiAl2(OH)6]+ layers with interlayer Cl- and water. The results of batch adsorption experiments showed that the adsorption isotherms at various pHs exhibited an L-shape and could be fitted well using the Langmuir model. The Langmuir adsorption maximum was determined to be 3.0 mmol g(-1) at pH 4.5 and decreased with increasing pH. The adsorption of phosphate was mainly through the displacement of the interlayer Cl- ions in LIG. In conjunction with the anion exchange reaction, the formation of surface complexes or precipitates could also readily occur at lower pH. The adsorption decreased with increasing pH due to decreased H(2)PO(4)(-)/HPO4(2-) molar ratio in solution and positive charges on the edge faces of LIG. Anion exchange is a fast reaction and can be completed within minutes; on the contrary, surface complexation is a slow process and requires days to reach equilibrium. At lower pH, the amount of adsorbed phosphate decreased significantly as the ionic strength was increased from 0.01 to 0.1M. The adsorption at higher pH showed high selectivity toward divalent HPO4(2-) ions with an increase in ionic strength having no considerable effect on the phosphate adsorption. These results suggest that LIG may be an effective scavenger for removal of phosphate from water.

Phosphate removal from water using lithium intercalated gibbsite

International Nuclear Information System (INIS)

Wang, S.-L.; Cheng, C.-Y.; Tzou, Y.-M.; Liaw, R.-B.; Chang, T.-W.; Chen, J.-H.

2007-01-01

In this study, lithium intercalated gibbsite (LIG) was investigated for its effectiveness at removing phosphate from water and the mechanisms involved. LIG was prepared through intercalating LiCl into gibbsite giving a structure of [LiAl 2 (OH) 6 ] + layers with interlayer Cl - and water. The results of batch adsorption experiments showed that the adsorption isotherms at various pHs exhibited an L-shape and could be fitted well using the Langmuir model. The Langmuir adsorption maximum was determined to be 3.0 mmol g -1 at pH 4.5 and decreased with increasing pH. The adsorption of phosphate was mainly through the displacement of the interlayer Cl - ions in LIG. In conjunction with the anion exchange reaction, the formation of surface complexes or precipitates could also readily occur at lower pH. The adsorption decreased with increasing pH due to decreased H 2 PO 4 - /HPO 4 2- molar ratio in solution and positive charges on the edge faces of LIG. Anion exchange is a fast reaction and can be completed within minutes; on the contrary, surface complexation is a slow process and requires days to reach equilibrium. At lower pH, the amount of adsorbed phosphate decreased significantly as the ionic strength was increased from 0.01 to 0.1 M. The adsorption at higher pH showed high selectivity toward divalent HPO 4 2- ions with an increase in ionic strength having no considerable effect on the phosphate adsorption. These results suggest that LIG may be an effective scavenger for removal of phosphate from water

Manganese oxide electrode with excellent electrochemical performance for sodium ion batteries by pre-intercalation of K and Na ions.

Science.gov (United States)

Feng, Mengya; Du, Qinghua; Su, Li; Zhang, Guowei; Wang, Guiling; Ma, Zhipeng; Gao, Weimin; Qin, Xiujuan; Shao, Guangjie

2017-05-22

Materials with a layered structure have attracted tremendous attention because of their unique properties. The ultrathin nanosheet structure can result in extremely rapid intercalation/de-intercalation of Na ions in the charge-discharge progress. Herein, we report a manganese oxide with pre-intercalated K and Na ions and having flower-like ultrathin layered structure, which was synthesized by a facile but efficient hydrothermal method under mild condition. The pre-intercalation of Na and K ions facilitates the access of electrolyte ions and shortens the ion diffusion pathways. The layered manganese oxide shows ultrahigh specific capacity when it is used as cathode material for sodium-ion batteries. It also exhibits excellent stability and reversibility. It was found that the amount of intercalated Na ions is approximately 71% of the total charge. The prominent electrochemical performance of the manganese oxide demonstrates the importance of design and synthesis of pre-intercalated ultrathin layered materials.

A fundamental approach to better understand the lithium insertion mechanisms in electrode materials; Une approche fondamentale pour mieux comprendre les mecanismes d`insertion du lithium dans les materiaux d`electrodes

Energy Technology Data Exchange (ETDEWEB)

Olivier-Fourcade, J.; Branci, C.; Sarradin, J.; Jumas, J.C. [Montpellier-2 Univ., 34 (France). Laboratoire de Physicochimie de la Matiere Condensee

1996-12-31

The development of rechargeable lithium batteries with a high mass capacity, made with non-toxic and low cost materials is an important industrial challenge. Morphological and structural modifications occurring in the electrode materials during charge-output cycles should not lower the electrochemical characteristics and the cycling properties of the battery. Thus the structure of electrode materials must be sufficiently deformable and stable to support the constraints linked with lithium intercalation and de-intercalation (ions and electrons absorption/extraction). The aim of this work is to explain some characteristics (mass capacity, ions and electrons mobility, cycling) using the relation between some mechanisms of lithium insertion (sites occupation, lattice reduction mods) and the nature of atoms and chemical bonds (covalence, ionicity). This approach is developed on 2-D models of crystallized and vitreous sulfur compounds (CdI{sub 2} type) with a large inter-sheet distance, and on 3-D spinel models with a huge number of vacant sites. The method is based on a correlation between experimental studies (XAFS, DX, Moessbauer, XPS) and theoretical calculations and on the electronic and electrochemical characteristics. The model proposed should allow to improve materials in a predictive way (type of substitution) or to imagine new materials. (J.S.) 15 refs.

A fundamental approach to better understand the lithium insertion mechanisms in electrode materials; Une approche fondamentale pour mieux comprendre les mecanismes d`insertion du lithium dans les materiaux d`electrodes

Energy Technology Data Exchange (ETDEWEB)

Olivier-Fourcade, J; Branci, C; Sarradin, J; Jumas, J C [Montpellier-2 Univ., 34 (France). Laboratoire de Physicochimie de la Matiere Condensee

1997-12-31

The development of rechargeable lithium batteries with a high mass capacity, made with non-toxic and low cost materials is an important industrial challenge. Morphological and structural modifications occurring in the electrode materials during charge-output cycles should not lower the electrochemical characteristics and the cycling properties of the battery. Thus the structure of electrode materials must be sufficiently deformable and stable to support the constraints linked with lithium intercalation and de-intercalation (ions and electrons absorption/extraction). The aim of this work is to explain some characteristics (mass capacity, ions and electrons mobility, cycling) using the relation between some mechanisms of lithium insertion (sites occupation, lattice reduction mods) and the nature of atoms and chemical bonds (covalence, ionicity). This approach is developed on 2-D models of crystallized and vitreous sulfur compounds (CdI{sub 2} type) with a large inter-sheet distance, and on 3-D spinel models with a huge number of vacant sites. The method is based on a correlation between experimental studies (XAFS, DX, Moessbauer, XPS) and theoretical calculations and on the electronic and electrochemical characteristics. The model proposed should allow to improve materials in a predictive way (type of substitution) or to imagine new materials. (J.S.) 15 refs.

Simulation of electrochemical behavior in Lithium ion battery during discharge process.

Science.gov (United States)

Chen, Yong; Huo, Weiwei; Lin, Muyi; Zhao, Li

2018-01-01

An electrochemical Lithium ion battery model was built taking into account the electrochemical reactions. The polarization was divided into parts which were related to the solid phase and the electrolyte mass transport of species, and the electrochemical reactions. The influence factors on battery polarization were studied, including the active material particle radius and the electrolyte salt concentration. The results showed that diffusion polarization exist in the positive and negative electrodes, and diffusion polarization increase with the conducting of the discharge process. The physicochemical parameters of the Lithium ion battery had the huge effect on cell voltage via polarization. The simulation data show that the polarization voltage has close relationship with active material particle size, discharging rate and ambient temperature.

A MEMS platform for in situ, real-time monitoring of electrochemically induced mechanical changes in lithium-ion battery electrodes

International Nuclear Information System (INIS)

Pomerantseva, Ekaterina; Jung, Hyun; Gnerlich, Markus; Baron, Sergio; Gerasopoulos, Konstantinos; Ghodssi, Reza

2013-01-01

We report the first successful demonstration of an optical microelectromechanical systems (MEMS) sensing platform for the in situ characterization of electrochemically induced reversible mechanical changes in lithium-ion battery (LIB) electrodes. The platform consists of an array of flexible membranes with a reflective surface on one side and a thin-film LIB electrode on the other side. The membranes deflect due to the active battery material volume change caused by lithium intercalation (expansion) and extraction (contraction). This deflection is monitored using the Fabry–Perot optical interferometry principle. The active material volume change causes high internal stresses and mechanical degradation of the electrodes. The stress evolution observed in a silicon thin-film electrode incorporated into this MEMS platform follows a ‘first elastic, then plastic’ deformation scheme. Understanding of the internal stresses in battery electrodes during discharge/charge is important for improving the reliability and cycle lifetime of LIBs. The developed MEMS platform presents a new method for in situ diagnostics of thin-film LIB electrodes to aid the development of new materials, optimization of electrode performance, and prevention of battery failure. (paper)

Structural and electrochemical study of the reaction of lithium with silicon nanowires

KAUST Repository

Chan, Candace K.; Ruffo, Riccardo; Hong, Seung Sae; Huggins, Robert A.; Cui, Yi

2009-01-01

The structural transformations of silicon nanowires when cycled against lithium were evaluated using electrochemical potential spectroscopy and galvanostatic cycling. During the charge, the nanowires alloy with lithium to form an amorphous Lix

Cycle aging studies of lithium nickel manganese cobalt oxide-based batteries using electrochemical impedance spectroscopy

NARCIS (Netherlands)

Maheshwari, Arpit; Heck, Michael; Santarelli, Massimo

2018-01-01

The cycle aging of a commercial 18650 lithium-ion battery with graphite anode and lithium nickel manganese cobalt (NMC) oxide-based cathode at defined operating conditions is studied by regular electrochemical characterization, electrochemical impedance spectroscopy (EIS) and post-mortem analysis.

Intercalated compounds of niobium and tantalum dicalcogenides

International Nuclear Information System (INIS)

Wypych, F.

1988-01-01

The synthesis of niobium and tantalum lamellar compounds and its intercalated derivatives is described. The intercalated compounds with lithium, with alkaline metal and with metals of the first-row transition are studied, characterized by X-ray diffraction. (C.G.C.) [pt

Nanocrystalline LiMn2O4 derived by HMTA-assisted solution combustion synthesis as a lithium-intercalating cathode material

International Nuclear Information System (INIS)

Fey, G.T.-K.; Cho, Y.-D.; Kumar, T. Prem

2006-01-01

Nanocrystalline LiMn 2 O 4 was synthesized by a self-sustaining solution combustion method with hexamethylenetetramine as a fuel. Ammonium nitrate was used as an additional oxidant-and-porogen. Thermal analytical studies showed the formation of LiMn 2 O 4 by a single-step decomposition process between 300 and 380 deg. C. The products were highly crystalline with an average crystallite size of ∼30 nm. Charge-discharge studies showed that the optimal heat treatment protocol was a 10 h calcination at 700 deg. C. A product obtained under these conditions from a precursor containing a 1:1 molar ratio of [LiNO 3 + Mn(NO 3 ) 2 ] and NH 4 NO 3 sustained 202 cycles between 3.0 and 4.3 V at a charge-discharge rate of 0.1 C before reaching an 80% charge retention cut-off value. Nanocrystalline particles provide small diffusion pathways that lead to an improvement in the lithium-ion intercalation kinetics and minimize surface distortions during cycling. These factors are believed to confer excellent electrochemical properties to the product

Electrochemical properties of ether-based electrolytes for lithium/sulfur rechargeable batteries

International Nuclear Information System (INIS)

Barchasz, Céline; Leprêtre, Jean-Claude; Patoux, Sébastien; Alloin, Fannie

2013-01-01

Highlights: ► Liquid electrolyte composition for lithium/sulfur secondary batteries. ► Carbonate-based electrolytes prove not to be compatible with the sulfur electrode. ► Poor electrochemical performances related to low polysulfide solubility. ► Increase in the discharge capacity using ether solvents with high solvating ability such as PEGDME. ► Evidence of DIOX polymerization during cycling. -- Abstract: The lithium/sulfur (Li/S) battery is a promising electrochemical system that has a high theoretical capacity of 1675 mAh g −1 . However, the system suffers from several drawbacks: poor active material conductivity, active material dissolution, and use of the highly reactive lithium metal electrode. In this study, we investigated the electrolyte effects on electrochemical performances of the Li/S cell, by acting on the solvent composition. As conventional carbonate-based electrolytes turned out to be unusable in Li/S cells, alternative ether solvents had to be considered. Different kinds of solvent structures were investigated by changing the ether/alkyl moieties ratio to vary the lithium polysulfide solubility. This allowed to point out the importance of the solvent solvation ability on the discharge capacity. As the end of discharge is linked to the positive electrode passivation, an electrolyte having high solvation ability reduces the polysulfide precipitation and delays the positive electrode passivation

Chemical vs. electrochemical extraction of lithium from the Li-excess Li(1.10)Mn(1.90)O4 spinel followed by NMR and DRX techniques.

Science.gov (United States)

Martinez, S; Sobrados, I; Tonti, D; Amarilla, J M; Sanz, J

2014-02-21

Lithium extraction from the Li-excess Li1.10Mn1.90O4 spinel has been performed by chemical and electrochemical methods in aqueous and in organic media, respectively. De-lithiated samples have been investigated by XRD, SEM, TG, (7)Li and (1)H MAS-NMR techniques. The comparative study has allowed demonstrating that the intermediate de-intercalated samples prepared during the chemical extraction by acid titration are similar to those prepared by the electrochemical way in a non-aqueous electrolyte. LiMn2O4 based spinel with a tailored de-lithiation degree can be prepared as a single phase by controlling the pH used in chemical extraction. (7)Li MAS-NMR spectroscopy has been used to follow the influence of the manganese oxidation state on tetra and octahedral Li-signals detected in Li-extracted samples. The oxidation of Mn(III) ions goes parallel to the partial dissolution of the spinel, following Hunter's mechanism. Based on this mechanism, a generalized chemical reaction has been proposed to explain the formation of intermediate Li(+) de-intercalated samples during acid treatment in aqueous media. By the (1)H MAS NMR study, no evidence of Li-H topotactic exchange in the bulk of the acid treated material was found.

MnO2 prepared by hydrothermal method and electrochemical performance as anode for lithium-ion battery.

Science.gov (United States)

Feng, Lili; Xuan, Zhewen; Zhao, Hongbo; Bai, Yang; Guo, Junming; Su, Chang-Wei; Chen, Xiaokai

2014-01-01

Two α-MnO2 crystals with caddice-clew-like and urchin-like morphologies are prepared by the hydrothermal method, and their structure and electrochemical performance are characterized by scanning electron microscope (SEM), X-ray diffraction (XRD), galvanostatic cell cycling, cyclic voltammetry, and electrochemical impedance spectroscopy (EIS). The morphology of the MnO2 prepared under acidic condition is urchin-like, while the one prepared under neutral condition is caddice-clew-like. The identical crystalline phase of MnO2 crystals is essential to evaluate the relationship between electrochemical performances and morphologies for lithium-ion battery application. In this study, urchin-like α-MnO2 crystals with compact structure have better electrochemical performance due to the higher specific capacity and lower impedance. We find that the relationship between electrochemical performance and morphology is different when MnO2 material used as electrochemical supercapacitor or as anode of lithium-ion battery. For lithium-ion battery application, urchin-like MnO2 material has better electrochemical performance.

Electrochemical insertion in solid media of alkali cations in carbonated host structures (polyacetylene, fullerene and graphite)

International Nuclear Information System (INIS)

Lemont, Sylvain

1994-01-01

This research thesis reports the investigation of electrochemical insertion of alkali cations in different host carbon containing structures (polyacetylene, fullerene, graphite). After a recall of the main characteristics of the three considered compounds, the author reports a bibliographical survey, describes the different compounds which can be used as solid electrolytes and explains the choice of the studied compounds with respect to their phase diagrams, ionic conductivity, electrochemical stability range. He describes the experimental methods, discusses the results obtained by intercalation of alkali cations (Li + , Na + , K + ) in polyacetylene. He discusses the electrochemical and structural results obtained on intercalation compounds of lithium and sodium ions in fullerene. The structures of several phases have been obtained by electron diffraction. Preliminary studies of electron energy loss spectrometry (EELS) are reported. The last part compares the results obtained on two types of graphite: pellets and spherules [fr

Electrochemically fabricated polypyrrole-cobalt-oxygen coordination complex as high-performance lithium-storage materials.

Science.gov (United States)

Guo, Bingkun; Kong, Qingyu; Zhu, Ying; Mao, Ya; Wang, Zhaoxiang; Wan, Meixiang; Chen, Liquan

2011-12-23

Current lithium-ion battery (LIB) technologies are all based on inorganic electrode materials, though organic materials have been used as electrodes for years. Disadvantages such as limited thermal stability and low specific capacity hinder their applications. On the other hand, the transition metal oxides that provide high lithium-storage capacity by way of electrochemical conversion reaction suffer from poor cycling stability. Here we report a novel high-performance, organic, lithium-storage material, a polypyrrole-cobalt-oxygen (PPy-Co-O) coordination complex, with high lithium-storage capacity and excellent cycling stability. Extended X-ray absorption fine structure and Raman spectroscopy and other physical and electrochemical characterizations demonstrate that this coordination complex can be electrochemically fabricated by cycling PPy-coated Co(3)O(4) between 0.0 V and 3.0 V versus Li(+)/Li. Density functional theory (DFT) calculations indicate that each cobalt atom coordinates with two nitrogen atoms within the PPy-Co coordination layer and the layers are connected with oxygen atoms between them. Coordination weakens the C-H bonds on PPy and makes the complex a novel lithium-storage material with high capacity and high cycling stability. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A Simple Synthesis of Two-Dimensional Ultrathin Nickel Cobaltite Nanosheets for Electrochemical Lithium Storage

International Nuclear Information System (INIS)

Zhu, Youqi; Cao, Chuanbao

2015-01-01

We report a simple microwave-assisted method to fabricate high-quality two-dimensional (2D) ultrathin NiCo 2 O 4 nanosheets with a geometrically graphene-like architecture. The unique large-area nanostructures represent an ultrahigh surface atomic ratio with almost all active elements exposed outside for surface-dependent electrochemical reaction processes. Experimental results reveal that the as-synthesized ultrathin NiCo 2 O 4 nanosheets show excellent electrochemical performances for lithium storage application. The ultrathin NiCo 2 O 4 nanosheets could deliver a high first discharge capacity (1287.1 mAh g −1 ) with initial Coulombic efficiency of 80.0% at 200 mA g −1 current density. The reversible lithium storage capacity still retains at 804.8 mAh g −1 in the 100th cycle, suggesting a good cycling stability. The excellent electrochemical properties of the as-synthesized NiCo 2 O 4 nanosheets could be ascribed to the unique ultrathin 2D architecture, which could offer large exposed active surface with more lithium-insertion channels and significantly reduce lithium ion diffusion distance. The cost-efficient synthesis and excellent lithium storage properties make the 2D NiCo 2 O 4 nanosheets as a promising anode material for high-performance lithium ion batteries

Electrochemical synthesis of birnessite-type layered manganese oxides for rechargeable lithium batteries

Science.gov (United States)

Nakayama, Masaharu; Kanaya, Taku; Lee, Jong-Won; Popov, Branko N.

Layered manganese dioxide (MnO 2) films intercalated with Li +, Na + or Mg 2+ ions were synthesized by a one-step electrochemical method. The electrodeposition was potentiostatically performed by applying an anodic potential of 1.0 V vs. Ag/AgCl in an aqueous MnSO 4 solution containing a perchlorate salt of the cation. The electrodeposited oxide films have a birnessite-type layered structure with alkali cations and water molecules between manganese oxide layers. The galvanostatic charge-discharge experiments performed in 1 M LiPF 6-DME/PC solution indicated that the Mg 2+-intercalated MnO 2 electrode exhibits an initial discharge capacity as large as 140 mAh g -1 and it shows a better capacity retention during cycling as compared with the Li +- or Na +-intercalated MnO 2 electrode.

AC impedance electrochemical modeling of lithium-ion positive electrodes

International Nuclear Information System (INIS)

Dees, D.; Gunen, E.; Abraham, D.; Jansen, A.; Prakash, J.

2004-01-01

Under Department of Energy's Advanced Technology Development Program,various analytical diagnostic studies are being carried out to examine the lithium-ion battery technology for hybrid electric vehicle applications, and a series of electrochemical studies are being conducted to examine the performance of these batteries. An electrochemical model was developed to associate changes that were observed in the post-test analytical diagnostic studies with the electrochemical performance loss during testing of lithium ion batteries. While both electrodes in the lithium-ion cell have been studied using a similar electrochemical model, the discussion here is limited to modeling of the positive electrode. The positive electrode under study has a composite structure made of a layered nickel oxide (LiNi 0.8 Co 0.15 Al 0.05 O 2 ) active material, a carbon black and graphite additive for distributing current, and a PVDF binder all on an aluminum current collector. The electrolyte is 1.2M LiPF 6 dissolved in a mixture of EC and EMC and a Celgard micro-porous membrane is used as the separator. Planar test cells (positive/separator/negative) were constructed with a special fixture and two separator membranes that allowed the placement of a micro-reference electrode between the separator membranes (1). Electrochemical studies including AC impedance spectroscopy were then conducted on the individual electrodes to examine the performance and ageing effects in the cell. The model was developed by following the work of Professor Newman at Berkeley (2). The solid electrolyte interface (SEI) region, based on post-test analytical results, was assumed to be a film on the oxide and an oxide layer at the surface of the oxide. A double layer capacity was added in parallel with the Butler-Volmer kinetic expression. The pertinent reaction, thermodynamic, and transport equations were linearized for a small sinusoidal perturbation (3). The resulting system of differential equations was solved

Influence of particle size and fluorination ratio of CFx precursor compounds on the electrochemical performance of C–FeF2 nanocomposites for reversible lithium storage

Directory of Open Access Journals (Sweden)

Ben Breitung

2013-11-01

Full Text Available Systematical studies of the electrochemical performance of CFx-derived carbon–FeF2 nanocomposites for reversible lithium storage are presented. The conversion cathode materials were synthesized by a simple one-pot synthesis, which enables a reactive intercalation of nanoscale Fe particles in a CFx matrix, and the reaction of these components to an electrically conductive C–FeF2 compound. The pretreatment and the structure of the utilized CFx precursors play a crucial role in the synthesis and influence the electrochemical behavior of the conversion cathode material. The particle size of the CFx precursor particles was varied by ball milling as well as by choosing different C/F ratios. The investigations led to optimized C–FeF2 conversion cathode materials that showed specific capacities of 436 mAh/g at 40 °C after 25 cycles. The composites were characterized by Raman spectroscopy, X-Ray diffraction measurements, electron energy loss spectroscopy and TEM measurements. The electrochemical performances of the materials were tested by galvanostatic measurements.

Lattice vibrations of materials for lithium rechargeable batteries II. Lithium extraction-insertion in spinel structures

International Nuclear Information System (INIS)

Julien, C.M.; Camacho-Lopez, M.A.

2004-01-01

Lithiated spinel manganese oxides with various amounts of lithium have been prepared through solid-state reaction and electrochemical intercalation and deintercalation. Local structure of the samples are studied using Raman scattering and Fourier transform infrared spectroscopy. We report vibrational spectra of lithiated manganese oxides Li x Mn 2 O 4 as a function of lithium concentration in the range 0.1≤x≤2.0. Raman and Fourier transform infrared (FTIR) spectral results indicated multiple-phase reactions when the lithium content is modified in the spinel lattice. Lattice dynamics of lithiated spinel manganese oxides have been interpreted using either a classical factor-group analysis or a local environment model. The structural modifications have been studied on the basis of vibrations of LiO 4 tetrahedral and MnO 6 octahedral units when Li/Mn≤0.5, and LiO 4 , LiO 6 , and MnO 6 structural units when Li/Mn>0.5

Lithium insertion in the two crystallographic forms of the binary-phase Mo15Se19

Science.gov (United States)

Tarascon, J. M.; Murphy, D. W.

1986-02-01

Compounds which can undergo topotactic insertion of lithium are of potential technological importance in secondary lithium batteries. In this paper we present the chemical and electrochemical insertion of lithium into the binary-phase Mo15Se19, which can exist in two crystallographic forms, denoted AA and BB, when prepared from In3Mo15Se19 and In2Mo15Se19, respectively. We show that both forms can reversibly accommodate up to eight lithium atoms, yielding two new series of compounds of formula LixMo15Se19. This behavior is consistent with the electronic structure of the host material predicted from band-structure calculations. The room-temperature phase diagram of both LixMo15Se19 systems as a function of x has been established using electrochemical test cells (based on Mo15Se19 as the cathode), and in situ x-ray measurements as the cells discharge. Both LixMo15Se19 systems contain three single-phase domains as a function of x: two hexagonal phases and an orthorhombic phase. The nature of the transitions between these single phases and the variation of the lattice parameters within a single-phase domain are reported. While the mechanism of intercalation of lithium is similar for both Mo15Se19 forms, there is a drastic difference in Li intercalation behavior for the parent indium phases In2Mo15Se19 and In3Mo15Se19. We found that In2Mo15Se19 can reversibly incorporate 6.4 lithium atoms while In3Mo15Se19 does not react. This behavior is explained on the basis of structural considerations.

Highly Reversible Electrochemical Insertion of Lithium, Accompanied With a Marked Color Change, Occuring in Microcrystalline Lithium Nickel Oxide Films

OpenAIRE

Campet, G.; Portier, J.; Morel, B.; Ferry, D.; Chabagno, J. M.; Benotmane, L.; Bourrel, M.

1992-01-01

Thin films of lithium-nickel oxide, whose texture consists of microcrystallites with an average grain size of 50 Å, permit highly reversible electrochemical insertion of lithium ions in Li+ conducting electrolytes. Therefore, the corresponding materials would be of great interest for energy storage applications. In addition, the lithium insertion/extraction reactions in the nickel-based layers are accompanied with a marked color change, making these films of interest for the devel...

A soft chemical route to multicomponent lithium transition metal oxide nanowires as promising cathode materials for lithium secondary batteries

International Nuclear Information System (INIS)

Park, Dae-Hoon; Lim, Seung-Tae; Hwang, Seong-Ju

2006-01-01

We have synthesized 1D nanowires of lithium nickel manganese oxides with two different crystal structures through the chemical oxidation reaction of solid-state precursor LiMn 0.5 Ni 0.5 O 2 under hydrothermal condition. According to X-ray diffraction and elemental analyses, the nanowires obtained by persulfate treatments at 65 and 120 deg. C crystallize with a hexagonal layered and an α-MnO 2 -type structure, respectively, in which nickel and manganese ions exist in octahedral sites. Electron microscopic analyses reveal that the platelike crystallites of the precursor are changed into nanowires with the diameter of ∼20 nm after the persulfate treatment. Thermal and infrared spectroscopic analyses clearly demonstrate that, in comparison with α-MnO 2 -structured nanowires, the hexagonal layered nanowires contain less water molecules in the lattice, which makes them suitable for the application as electrode materials for lithium secondary batteries. According to electrochemical measurements, the hexagonal layered nanowires show a larger discharge capacity and an excellent cyclability with respect to repeated Li intercalation-disintercalation process. X-ray diffraction and electron microscopic analyses on the samples subjected to electrochemical analysis reveal that the layered structure and 1D morphology of the nanowires are still maintained after the electrochemical cyclings, which is responsible for their excellent electrochemical performances

Tuning thermal conductivity in molybdenum disulfide by electrochemical intercalation

Science.gov (United States)

Zhu, Gaohua; Liu, Jun; Zheng, Qiye; Zhang, Ruigang; Li, Dongyao; Banerjee, Debasish; Cahill, David G.

2016-01-01

Thermal conductivity of two-dimensional (2D) materials is of interest for energy storage, nanoelectronics and optoelectronics. Here, we report that the thermal conductivity of molybdenum disulfide can be modified by electrochemical intercalation. We observe distinct behaviour for thin films with vertically aligned basal planes and natural bulk crystals with basal planes aligned parallel to the surface. The thermal conductivity is measured as a function of the degree of lithiation, using time-domain thermoreflectance. The change of thermal conductivity correlates with the lithiation-induced structural and compositional disorder. We further show that the ratio of the in-plane to through-plane thermal conductivity of bulk crystal is enhanced by the disorder. These results suggest that stacking disorder and mixture of phases is an effective mechanism to modify the anisotropic thermal conductivity of 2D materials. PMID:27767030

Electrical insulation properties of RF-sputtered LiPON layers towards electrochemical stability of lithium batteries

OpenAIRE

Vieira, E. M. F.; Ribeiro, J. F.; Silva, Maria Manuela; Barradas, N. P.; Alves, E.; Alves, A.; Correia, M. R.; Gonçalves, L. M.

2016-01-01

Electrochemical stability, moderate ionic conductivity and low electronic conductivity make the lithium phosphorous oxynitride (LiPON) electrolyte suitable for micro and nanoscale lithium batteries. The electrical and electrochemical properties of thin-film electrolytes can seriously compromise full battery performance. Here, radio-frequency (RF)-sputtered LiPON thin films were fabricated in nitrogen plasma under different working pressure conditions. With a slight decrease in ...

One-Step Synthesis of Titanium Oxyhydroxy-Fluoride Rods and Research on the Electrochemical Performance for Lithium-ion Batteries and Sodium-ion Batteries.

Science.gov (United States)

Li, Biao; Gao, Zhan; Wang, Dake; Hao, Qiaoyan; Wang, Yan; Wang, Yongkun; Tang, Kaibin

2015-12-01

Titanium oxyhydroxy-fluoride, TiO0.9(OH)0.9F1.2 · 0.59H2O rods with a hexagonal tungsten bronze (HTB) structure, was synthesized via a facile one-step solvothermal method. The structure, morphology, and component of the products were characterized by X-ray powder diffraction (XRD), thermogravimetry (TG), scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution TEM (HRTEM), inductively coupled plasma optical emission spectroscopy (ICP-OES), ion chromatograph, energy-dispersive X-ray (EDX) analyses, and so on. Different rod morphologies which ranged from nanoscale to submicron scale were simply obtained by adjusting reaction conditions. With one-dimension channels for Li/Na intercalation/de-intercalation, the electrochemical performance of titanium oxyhydroxy-fluoride for both lithium-ion batteries (LIBs) and sodium-ion batteries (SIBs) was also studied. Electrochemical tests revealed that, for LIBs, titanium oxyhydroxy-fluoride exhibited a stabilized reversible capacity of 200 mAh g(-1) at 25 mA g(-1) up to 120 cycles in the electrode potential range of 3.0-1.2 V and 140 mAh g(-1) at 250 mA g(-1) up to 500 cycles, especially; for SIBs, a high capacity of 100 mAh g(-1) was maintained at 25 mA g(-1) after 115 cycles in the potential range of 2.9-0.5 V.

Expansion of Lithium Ion Pouch Cell Batteries: Observations from Neutron Imaging

Science.gov (United States)

2012-12-21

detector over a given time period. The neutron beam intensity after passing through an object of thickness δ can be described by the Lambert- Beer Law...concentration, cLi, using the Beer -Lambert Law by assuming that the other material concentrations remain constant [7]. The shift in location of...and B. Fultz, " Thermodynamics of Lithium Intercalation into Graphites and Disordered Carbons," J. Electrochem. Soc., vol. 151, no. 3, pp. A422-A426

Effects of Capacity Ratios between Anode and Cathode on Electrochemical Properties for Lithium Polymer Batteries

International Nuclear Information System (INIS)

Kim, Cheon-Soo; Jeong, Kyung Min; Kim, Keon; Yi, Cheol-Woo

2015-01-01

The areal capacity ratio of negative to positive electrodes (N/P ratio) is the most important factor to design the lithium ion batteries with high performance in the consideration of balanced electrochemical reactions. In this study, the effect of N/P ratio (1.10, 1.20, and 1.30) on electrochemical properties has been investigated with a lithium polymer battery with PVdF-coated separator and 1.40 Ah of capacity. The N/P ratio is controlled by adjusting the anode thickness with a fixed anode density. The cell with an N/P ratio higher than 1.10 effectively suppresses the lithium plating at the 0.85C-rate charging at 25 °C and the cell with 1.20 of N/P ratio shows the enhanced cycle performance in comparison with other cells. Among the cells with differently designed N/P ratios, significant difference was not observed in the aging test with fully charged batteries at 25 and 45 °C. The effect of N/P ratio on electrochemical properties of lithium batteries can help to design the safe full cell without lithium plating

Electrochemical Model for Ionic Liquid Electrolytes in Lithium Batteries

International Nuclear Information System (INIS)

Yoo, Kisoo; Deshpande, Anirudh; Banerjee, Soumik; Dutta, Prashanta

2015-01-01

ABSTRACT: Room temperature ionic liquids are considered as potential electrolytes for high performance and safe lithium batteries due to their very low vapor pressure and relatively wide electrochemical and thermal stability windows. Unlike organic electrolytes, ionic liquid electrolytes are molten salts at room temperature with dissociated cations and anions. These dissociated ions interfere with the transport of lithium ions in lithium battery. In this study, a mathematical model is developed for transport of ionic components to study the performance of ionic liquid based lithium batteries. The mathematical model is based on a univalent ternary electrolyte frequently encountered in ionic liquid electrolytes of lithium batteries. Owing to the very high concentration of components in ionic liquid, the transport of lithium ions is described by the mutual diffusion phenomena using Maxwell-Stefan diffusivities, which are obtained from atomistic simulation. The model is employed to study a lithium-ion battery where the electrolyte comprises ionic liquid with mppy + (N-methyl-N-propyl pyrrolidinium) cation and TFSI − (bis trifluoromethanesulfonyl imide) anion. For a moderate value of reaction rate constant, the electric performance results predicted by the model are in good agreement with experimental data. We also studied the effect of porosity and thickness of separator on the performance of lithium-ion battery using this model. Numerical results indicate that low rate of lithium ion transport causes lithium depleted zone in the porous cathode regions as the porosity decreases or the length of the separator increases. The lithium depleted region is responsible for lower specific capacity in lithium-ion cells. The model presented in this study can be used for design of optimal ionic liquid electrolytes for lithium-ion and lithium-air batteries

Hydrogen Adsorption in Flame Synthesized and Lithium Intercalated Carbon Nanofibers--A Comparative Study.

Science.gov (United States)

Dhand, Vivek; Prasad, J Sarada; Rao, Venkateswer M; Kalluri, Sujith; Jain, Pawan Kumar; Sreedhar, B

2015-01-01

Carbon nanofibers (CNF) have been synthesized under partial combustion conditions in a flame reactor using different mixtures of hydrocarbon gases in the presence and absence of precursors. The hydrogen (H2) adsorption studies have been carried out using a high pressure Sievert's apparatus maintained at a constant temperature (24 degrees C). The flame synthesized CNFs showed high degree of H2 adsorption capacities at 100 atm pressure. The highest H2 capacities recorded have been 4.1 wt% [for CNF produced by liquefied petroleum gas (LPG)-Air (E-17)], 3.7 wt% [for nano carbons produced by Methane-Acetylene-Air (EMAC-4)] and 5.04 wt% for [Lithium intercalated sample (Li-EMAC-4)] respectively.

Lithium insertion in the two crystallographic forms of the binary-phase Mo15Se19

International Nuclear Information System (INIS)

Tarascon, J.M.; Murphy, D.W.

1986-01-01

Compounds which can undergo topotactic insertion of lithium are of potential technological importance in secondary lithium batteries. In this paper we present the chemical and electrochemical insertion of lithium into the binary-phase Mo 15 Se 19 , which can exist in two crystallographic forms, denoted AA and BB, when prepared from In 3 Mo 15 Se 19 and In 2 Mo 15 Se 19 , respectively. We show that both forms can reversibly accommodate up to eight lithium atoms, yielding two new series of compounds of formula Li/sub x/Mo 15 Se 19 . This behavior is consistent with the electronic structure of the host material predicted from band-structure calculations. The room-temperature phase diagram of both Li/sub x/Mo 15 Se 19 systems as a function of x has been established using electrochemical test cells (based on Mo 15 Se 19 as the cathode), and in situ x-ray measurements as the cells discharge. Both Li/sub x/Mo 15 Se 19 systems contain three single-phase domains as a function of x: two hexagonal phases and an orthorhombic phase. The nature of the transitions between these single phases and the variation of the lattice parameters within a single-phase domain are reported. While the mechanism of intercalation of lithium is similar for both Mo 15 Se 19 forms, there is a drastic difference in Li intercalation behavior for the parent indium phases In''Mo 15 Se 19 and In 3 Mo 15 Se 19 . We found that In 2 Mo 15 Se 19 can reversibly incorporate 6.4 lithium atoms while In 3 Mo 15 Se 19 does not react. This behavior is explained on the basis of structural considerations

Lithium batteries; Les accumulateurs au lithium

Energy Technology Data Exchange (ETDEWEB)

NONE

1996-12-31

This workshop on lithium batteries is divided into 4 sections dealing with: the design and safety aspects, the cycling, the lithium intercalation and its modeling, and the electrolytes. These 4 sections represent 19 papers and are completed by a poster session which corresponds to 17 additional papers. (J.S.)

Lithium batteries; Les accumulateurs au lithium

Energy Technology Data Exchange (ETDEWEB)

NONE

1997-12-31

This workshop on lithium batteries is divided into 4 sections dealing with: the design and safety aspects, the cycling, the lithium intercalation and its modeling, and the electrolytes. These 4 sections represent 19 papers and are completed by a poster session which corresponds to 17 additional papers. (J.S.)

Dopant-Modulating Mechanism of Lithium Adsorption and Diffusion at the Graphene /Li2S Interface

Science.gov (United States)

Guo, Lichao; Li, Jiajun; Wang, Huayu; Zhao, Naiqin; Shi, Chunsheng; Ma, Liying; He, Chunnian; He, Fang; Liu, Enzuo

2018-02-01

Graphene modification is one of the most effective routes to enhance the electrochemical properties of the transition-metal sulfide anode for Li-ion batteries and the Li2S cathode for Li-S batteries. Boron, nitrogen, oxygen, phosphorus, and sulfur doping greatly affect the electrochemical properties of Li2S /graphene . Here, we investigate the interfacial binding energy, lithium adsorption energy, interface diffusion barrier, and electronic structure by first-principles calculations to unveil the diverse effects of different dopants during interfacial lithiation reactions. The interfacial lithium storage follows the pseudocapacitylike mechanism with intercalation character. Two different mechanisms are revealed to enhance the interfacial lithium adsorption and diffusion, which are the electron-deficiency host doping and the vacancylike structure evolutions with bond breaking. The synergistic effect between different dopants with diverse doping effects is also proposed. The results give a theoretical basis for the materials design with doped graphene as advanced materials modification for energy storage.

Electrochemical Evaluation of Corrosion Inhibiting Layers Formed in a Defect from Lithium-Leaching Organic Coatings

NARCIS (Netherlands)

Visser, P.; Meeusen, M.; Gonzalez Garcia, Y.; Terryn, H.A.; Mol, J.M.C.

2017-01-01

This work presents the electrochemical evaluation of protective layers generated in a coating defect from lithium-leaching organic coatings on AA2024-T3 aluminum alloys as a function of neutral salt spray exposure time. Electrochemical impedance spectroscopy was used to study the electrochemical

Electrochemical reactivity of Co-Li2S nanocomposite for lithium-ion batteries

International Nuclear Information System (INIS)

Zhou, Yongning; Wu, Changliang; Zhang, Hua; Wu, Xiaojing; Fu, Zhengwen

2007-01-01

The fabrication of Co-Li 2 S nanocomposite thin film is reported by pulsed laser deposition (PLD) for the first time. Li 2 S-Co nanocomposite thin film is used as storing Li electrodes that have led to promising electrochemical activity and good electrochemical performance. The releasing Li process from the as-deposited Li 2 S-Co nanocomposite thin films is confirmed by the ex situ high resolution transmission electron microscopy (HR-TEM) and selected area electron diffraction (SAED) measurements and may come from the decomposition of Li 2 S with and without the interaction of metal Co into CoS 2 and S. The electrochemical reaction mechanism of Co-Li 2 S nanocomposite film electrode involving both the formation and decomposition of Li 2 S and the lithium extraction/insertion of CoS 2 after the initial charging process is proposed. Our results demonstrate the advantages of using Co-Li 2 S nanocomposite in storage lithium materials

Synthesis of layered LiMnO2 as an electrode for rechargeable lithium batteries

Science.gov (United States)

Armstrong, A. Robert; Bruce, Peter G.

1996-06-01

RECHARGEABLE lithium batteries can store more than twice as much energy per unit weight and volume as other rechargeable batteries1,2. They contain lithium ions in an electrolyte, which shuttle back and forth between, and are intercalated by, the electrode materials. The first commercially successful rechargeable lithium battery3, introduced by the Sony Corporation in 1990, consists of a carbon-based negative electrode, layered LiCoO2 as the positive electrode, and a non-aqueous liquid electrolyte. The high cost and toxicity of cobalt compounds, however, has prompted a search for alternative materials that intercalate lithium ions. One such is LiMn2O4, which has been much studied as a positive electrode material4-7 the cost of manganese is less than 1% of that of cobalt, and it is less toxic. Here we report the synthesis and electrochemical performance of a new material, layered LiMnO2, which is structurally analogous to LiCoO2. The charge capacity of LiMnO2 (~270mAhg-1) compares well with that of both LiCoO2 and LiMn2O4, and preliminary results indicate good stability over repeated charge-discharge cycles.

Atomic force microscopy study of anion intercalation into highly oriented pyrolytic graphite

Energy Technology Data Exchange (ETDEWEB)

Alliata, D; Haering, P; Haas, O; Koetz, R [Paul Scherrer Inst. (PSI), Villigen (Switzerland); Siegenthaler, H [University of Berne (Switzerland)

1999-08-01

In the context of ion transfer batteries, we studied highly oriented pyrolytic graphite (HOPG) in perchloric acid, as a model to elucidate the mechanism of electrochemical intercalation in graphite. Aim of the work is the local and time dependent investigation of dimensional changes of the host material during electrochemical intercalation processes on the nanometer scale. We used atomic force microscopy (AFM), combined with cyclic voltammetry, as in-situ tool of analysis during intercalation and expulsion of perchloric anions into the HOPG electrodes. According to the AFM measurements, the HOPG interlayer spacing increases by 32% when perchloric anions intercalate, in agreement with the formation of stage IV of graphite intercalation compounds. (author) 3 figs., 3 refs.

Disordered carbon negative electrode for electrochemical capacitors and high-rate batteries

International Nuclear Information System (INIS)

Ogihara, Nobuhiro; Igarashi, Yoshiyuki; Kamakura, Ayumu; Naoi, Katsuhiko; Kusachi, Yuki; Utsugi, Koji

2006-01-01

In order to understand the properties of high-rate capability and cycleability for a disordered carbon negative electrode in LiPF 6 /PC based electrolyte solution, the cell performance tests with various rates and depth of discharges (DODs) has been studied by spectroscopic and electrochemical analyses. From the charge-discharge measurements, a surface carbon-edge redox reaction occurring between a carbonyl (C edge =O) and a lithium alkoxide (C edge -OLi) that delivers a large capacity was found fast and high cycleability at only shallow DOD (2.0-0.4 V). The limited or shallow charge-discharge cycling utilizing such facile and reversible action of the C edge =O/C edge -OLi of the disordered carbon is suited to an application for an negative electrode of asymmetric hybrid capacitors. A deep DOD discharge (2.0-0.0 V) revealed the existence of some complex processes involving a lithium cluster deposition at pores or microvoids as well as a lithium ion intercalation at graphene layers. The cluster deposition at pores was found to be relatively fast and reproducible. The lithium ion intercalation at graphenes and the subsequent cluster deposition at microvoids were found to be slow and degrade the cycleability after 100 cycles because of the accumulation of a thick and low-ion-conductive solid electrolyte interface (SEI) film on surface

Coupled Mechanical-Electrochemical-Thermal Analysis of Failure Propagation in Lithium-ion Batteries

Energy Technology Data Exchange (ETDEWEB)

Zhang, Chao; Santhanagopalan, Shriram; Pesaran, Ahmad

2016-07-28

This is a presentation given at the 12th World Congress for Computational Mechanics on coupled mechanical-electrochemical-thermal analysis of failure propagation in lithium-ion batteries for electric vehicles.

Intercalation compounds of vanadium pentoxide hydrated with metalporphyrins and lanthanide ions

International Nuclear Information System (INIS)

Oliveira, Herenilton Paulino

1994-01-01

The lamellar structure of the vanadium pentoxide matrix allows the intercalation of organic molecules, ions and conductor polymers. It is important to emphasize that the vanadium oxide matrix is an intrinsic semiconductor and presents electrochromic properties. In the beginning of this work the method of synthesis and the electrochemical and electrochromic properties were extensively explored. The effect of alkaline metal and lanthanide ions on the structure of vanadium oxide matrix was studied by X-ray and infrared spectroscopy. Moreover, the influence of those ions in the electrochemical, spectro electrochemical and magnetic properties were studied. Finally, some intercalation compounds containing porphyrins were prepared and characterized by elemental analysis, X-ray diffraction, and electronic, vibrational, Moessbauer and X-ray fluorescence spectroscopy. The electrochemical and spectro electrochemical properties were investigated. And the performance of an iron porphyrin based intercalation compound as catalyst for molecular oxygen reduction was evaluated using the rotating ring-disc electrode technique. (author)

Chemical properties of various organic electrolytes for lithium rechargeable batteries. Pt. 1.. Characterization of passivating layer formed on graphite in alkyl carbonate solutions

Energy Technology Data Exchange (ETDEWEB)

Mori, Shoichiro; Asahina, Hitoshi; Suzuki, Hitoshi; Yonei, Ayako; Yokoto, Kiyomi [Tsukuba Research Center, Mitsubishi Chemical Corporation, Ibaraki (Japan)

1997-09-01

The characteristics and reaction mechanisms of the passivating film formed on the surface of graphite were investigated in ethylene carbonate-diethyl carbonate solutions containing LiClO{sub 4}, LiPF{sub 6} and LiN(SO{sub 2}CF{sub 3}){sub 2}. The electron consumption resulting on the irreversible capacity of graphite was almost equivalent to that used in the one-electron reduction of Li{sup +} found in the film. The electrochemical reactions in the first discharge process may be divided into the following steps: (i) `initial film formation step` from 1.4 to 0.55 V; (ii) `main film formation step` from 0.55 to 0.2 V, and (iii) `lithium intercalation step from 0.2 to 0.0 V. Most of the passivating film is formed together with the lithium intercalation reaction at step (ii). The passivating film formed at this step contained a significant amount of organic film such as EtOCO{sub 2}Li, (CH{sub 2}OCO{sub 2}Li){sub 2}, etc. Through the consecutive formation of passivating film at steps (i) and (ii), lithium intercalation into graphite proceeds smoothly without further decomposition of organic electrolyte. (orig.)

Effect of calcium on the electrochemical behavior of lithium anode in LiOH aqueous solution used for lithium–water battery

International Nuclear Information System (INIS)

Zhang Ziyan; Chen Kanghua; Ni Erfu

2012-01-01

The effect of minor addition of calcium to lithium anode on the electrochemical behavior of lithium anode in 4 M LiOH at 30 °C temperature is investigated by hydrogen collection, polarization curves and electrochemical impedance spectroscopy. The results show that the hydrogen evolution rate is marginally reduced with increasing calcium content. Addition of calcium to lithium mainly inhibits the anodic process. Minor addition of calcium to lithium slightly reduced the discharge current of lithium anode. Minor addition of calcium to lithium anode marginally enhances the hydrogen inhibition of lithium by the formation of calcium hydride combined with LiOH and LiOH·H 2 O formed on the anode surface.

Synthesis and Electrochemical Performance of a Lithium Titanium Phosphate Anode for Aqueous Lithium-Ion Batteries

KAUST Repository

Wessells, Colin

2011-01-01

Lithium-ion batteries that use aqueous electrolytes offer safety and cost advantages when compared to today\\'s commercial cells that use organic electrolytes. The equilibrium reaction potential of lithium titanium phosphate is -0.5 V with respect to the standard hydrogen electrode, which makes this material attractive for use as a negative electrode in aqueous electrolytes. This material was synthesized using a Pechini type method. Galvanostatic cycling of the resulting lithium titanium phosphate showed an initial discharge capacity of 115 mAh/g and quite good capacity retention during cycling, 84% after 100 cycles, and 70% after 160 cycles at a 1 C cycling rate in an organic electrolyte. An initial discharge capacity of 113 mAh/g and capacity retention of 89% after 100 cycles with a coulombic efficiency above 98% was observed at a C/5 rate in pH -neutral 2 M Li2 S O4. The good cycle life and high efficiency in an aqueous electrolyte demonstrate that lithium titanium phosphate is an excellent candidate negative electrode material for use in aqueous lithium-ion batteries. © 2011 The Electrochemical Society.

Electrochemical performance of a hybrid lithium-ion capacitor with a graphite anode preloaded from lithium bis(trifluoromethane)sulfonimide-based electrolyte

International Nuclear Information System (INIS)

Decaux, C.; Lota, G.; Raymundo-Piñero, E.; Frackowiak, E.; Béguin, F.

2012-01-01

A hybrid LiC capacitor combining a lithium-ion battery type (graphite) electrode and an electrical double-layer (activated carbon) one has been developed by preloading graphite from 2 mol L −1 lithium bis(trifluoromethane)sulfonimide (LiTFSI) organic electrolyte. The graphite intercalation compound was formed by applying ca. 10 successive charge/self-discharge pulses. The optimized hybrid device operates in the voltage range from 1.5 to 4.2 V and displays 60% higher gravimetric capacitance than an electric double-layer (EDL) capacitor using the same activated carbon for both electrodes. As a result, the energy density reaches 80 Wh kg −1 , which is four times higher than the value for the EDL capacitor with the same total mass of carbon.

Accomplishment of highly porous-lithium lanthanum titanate through microwave treatment

Energy Technology Data Exchange (ETDEWEB)

Lakshmi, D.; Nalini, B., E-mail: jyothsnalalin99@gmail.com [Department of Physics, Avinashilingam University for Women, Coimbatore, Tamilnadu (India); Abhilash, K. P.; Selvin, P. Christopher [Department of Physics, NGM college for arts and science, Pollachi, Tamilnadu (India)

2016-05-23

Perovskite structured (ABO{sub 3}) lithium lanthanum titanate (LLTO) is a successful electrolyte reported by several scientists in the recent past. It is believed that intercalation and de-intercalation of Li ions inside solid electrolyte can be improved by increasing the porosity of the material. Hence in this research work, an attempt is made to increase the porosity of the LLTO electrolyte by rapid-microwave synthesis route. The microwave prepared LLTO is compared with the sol-gel synthesized LLTO. The prepared samples are analyzed with XRD, SEM, PL and cyclic Voltammetry studies. Morphological analysis proves that microwave synthesized LLTO contains much pores compared to the Sol-gel LLTO. A remarkable difference in its electrochemical property is also demonstrated and analysed with cyclic voltammetric studies and the results are presented.

Synthesis of carbon-coated TiO 2 nanotubes for high-power lithium-ion batteries

Science.gov (United States)

Park, Sang-Jun; Kim, Young-Jun; Lee, Hyukjae

Carbon-coated TiO 2 nanotubes are prepared by a simple one-step hydrothermal method with an addition of glucose in the starting powder, and are characterized by morphological analysis and electrochemical measurement. A thin carbon coating on the nanotube surface effectively suppresses severe agglomeration of TiO 2 nanotubes during hydrothermal reaction and post calcination. This action results in better ionic and electronic kinetics when applied to lithium-ion batteries. Consequently, carbon-coated TiO 2 nanotubes deliver a remarkable lithium-ion intercalation/deintercalation performance, such as reversible capacities of 286 and 150 mAh g -1 at 250 and 7500 mA g -1, respectively.

Luminescent monolayer MoS{sub 2} quantum dots produced by multi-exfoliation based on lithium intercalation

Energy Technology Data Exchange (ETDEWEB)

Qiao, Wen [Collaborative Innovation Center of Advanced Microstructures, National Laboratory of Solid State Microstructures and Jiangsu Provincial Laboratory for NanoTechnology, Nanjing University, Nanjing 210093 (China); Yan, Shiming [Collaborative Innovation Center of Advanced Microstructures, National Laboratory of Solid State Microstructures and Jiangsu Provincial Laboratory for NanoTechnology, Nanjing University, Nanjing 210093 (China); College of Science, Henan University of Technology, Zhengzhou 450001 (China); Song, Xueyin; Zhang, Xing; He, Xueming [Collaborative Innovation Center of Advanced Microstructures, National Laboratory of Solid State Microstructures and Jiangsu Provincial Laboratory for NanoTechnology, Nanjing University, Nanjing 210093 (China); Zhong, Wei, E-mail: wzhong@nju.edu.cn [Collaborative Innovation Center of Advanced Microstructures, National Laboratory of Solid State Microstructures and Jiangsu Provincial Laboratory for NanoTechnology, Nanjing University, Nanjing 210093 (China); Du, Youwei [Collaborative Innovation Center of Advanced Microstructures, National Laboratory of Solid State Microstructures and Jiangsu Provincial Laboratory for NanoTechnology, Nanjing University, Nanjing 210093 (China)

2015-12-30

Graphical abstract: - Highlights: • A new preparation, multi-exfoliation method based on lithium (Li) intercalation, has been demonstrated for preparing monolayer molybdenum disulfide (MoS{sub 2}) quantum dots (QDs). • The advantage of this approach is that it is capable of producing monolayer MoS{sub 2} QDs in a large number, regardless of whether the raw material is bulk or nanoparticles. • The PL intensity excited at 300 nm can be enhanced by five times after ultrasonicated heating treatment. - Abstract: An effective multi-exfoliation method based on lithium (Li) intercalation has been demonstrated for preparing monolayer molybdenum disulfide (MoS{sub 2}) quantum dots (QDs). The cutting mechanism of MoS{sub 2} QDs may involve the complete breakup around the defects and edges during the reaction of Li{sub x}MoS{sub 2} with water and its following ultrasonication process. The multiply exfoliation make the MoS{sub 2} fragile and easier to break up. After the third exfoliation, a large number of monolayer MoS{sub 2} QDs is formed. The as-prepared MoS{sub 2} QDs show photoluminescence (PL) inactive due to the existence of 1T phase. After heating treatment, the PL intensity excited at 300 nm is enhanced by five times. The MoS{sub 2} QDs solution has an excitation-dependent luminescence emission which shifts to longer wavelengths when the excitation wavelength changes from 280 nm to 370 nm. The optical properties are explored based on the quantum confinement and edge effect.

Optimization of reserve lithium thionyl chloride battery electrochemical design parameters

Energy Technology Data Exchange (ETDEWEB)

Doddapaneni, N.; Godshall, N.A.

1987-01-01

The performance of Reserve Lithium Thionyl Chloride (RLTC) batteries was optimized by conducting a parametric study of seven electrochemical parameters: electrode compression, carbon thickness, presence of catalyst, temperature, electrode limitation, discharge rate, and electrolyte acidity. Increasing electrode compression (from 0 to 15%) improved battery performance significantly (10% greater carbon capacity density). Although thinner carbon cathodes yielded less absolute capacity than did thicker cathodes, they did so with considerably higher volume efficiencies. The effect of these parameters, and their synergistic interactions, on electrochemical cell peformance is illustrated. 5 refs., 9 figs., 3 tabs.

Optimization of reserve lithium thionyl chloride battery electrochemical design parameters

Science.gov (United States)

Doddapaneni, N.; Godshall, N. A.

The performance of Reserve Lithium Thionyl Chloride (RLTC) batteries was optimized by conducting a parametric study of seven electrochemical parameters: electrode compression, carbon thickness, presence of catalyst, temperature, electrode limitation, discharge rate, and electrolyte acidity. Increasing electrode compression (from 0 to 15 percent) improved battery performance significantly (10 percent greater carbon capacity density). Although thinner carbon cathodes yielded less absolute capacity than did thicker cathodes, they did so with considerably higher volume efficiencies. The effect of these parameters, and their synergistic interactions, on electrochemical cell performance is illustrated.

Ab initio density functional theory investigation of Li-intercalated silicon carbide nanotube bundles

International Nuclear Information System (INIS)

Moradian, Rostam; Behzad, Somayeh; Chegel, Raad

2009-01-01

We present the results of ab initio density functional theory calculations on the energetic, and geometric and electronic structure of Li-intercalated (6,6) silicon carbide nanotube (SiCNT) bundles. Our results show that intercalation of lithium leads to the significant changes in the geometrical structure. The most prominent effect of Li intercalation on the electronic band structure is a shift of the Fermi energy which occurs as a result of charge transfer from lithium to the SiCNTs. All the Li-intercalated (6,6) SiCNT bundles are predicted to be metallic representing a substantial change in electronic properties relative to the undoped bundle, which is a wide band gap semiconductor. Both inside of the nanotube and the interstitial space are susceptible for intercalation. The present calculations suggest that the SiCNT bundle is a promising candidate for the anode material in battery applications.

Ab initio density functional theory investigation of Li-intercalated silicon carbide nanotube bundles

Science.gov (United States)

Moradian, Rostam; Behzad, Somayeh; Chegel, Raad

2009-06-01

We present the results of ab initio density functional theory calculations on the energetic, and geometric and electronic structure of Li-intercalated ( 6,6) silicon carbide nanotube (SiCNT) bundles. Our results show that intercalation of lithium leads to the significant changes in the geometrical structure. The most prominent effect of Li intercalation on the electronic band structure is a shift of the Fermi energy which occurs as a result of charge transfer from lithium to the SiCNTs. All the Li-intercalated ( 6,6) SiCNT bundles are predicted to be metallic representing a substantial change in electronic properties relative to the undoped bundle, which is a wide band gap semiconductor. Both inside of the nanotube and the interstitial space are susceptible for intercalation. The present calculations suggest that the SiCNT bundle is a promising candidate for the anode material in battery applications.

Ab initio density functional theory investigation of Li-intercalated silicon carbide nanotube bundles

Energy Technology Data Exchange (ETDEWEB)

Moradian, Rostam [Physics Department, Faculty of Science, Razi University, Kermanshah (Iran, Islamic Republic of); Nano Science and Technology Research Center, Razi University, Kermanshah (Iran, Islamic Republic of); Computational Physical Science Research Laboratory, Department of Nano Science, Institute for Studies in Theoretical Physics and Mathematics (IPM), PO Box 19395-5531, Tehran (Iran, Islamic Republic of)], E-mail: moradian.rostam@gmail.com; Behzad, Somayeh; Chegel, Raad [Physics Department, Faculty of Science, Razi University, Kermanshah (Iran, Islamic Republic of)

2009-06-15

We present the results of ab initio density functional theory calculations on the energetic, and geometric and electronic structure of Li-intercalated (6,6) silicon carbide nanotube (SiCNT) bundles. Our results show that intercalation of lithium leads to the significant changes in the geometrical structure. The most prominent effect of Li intercalation on the electronic band structure is a shift of the Fermi energy which occurs as a result of charge transfer from lithium to the SiCNTs. All the Li-intercalated (6,6) SiCNT bundles are predicted to be metallic representing a substantial change in electronic properties relative to the undoped bundle, which is a wide band gap semiconductor. Both inside of the nanotube and the interstitial space are susceptible for intercalation. The present calculations suggest that the SiCNT bundle is a promising candidate for the anode material in battery applications.

Simultaneously Coupled Mechanical-Electrochemical-Thermal Simulation of Lithium-Ion Cells: Preprint

Energy Technology Data Exchange (ETDEWEB)

Zhang, Chao; Santhanagopalan, Shriram; Sprague, Michael A.; Pesaran, Ahmad A.

2016-08-01

Understanding the combined electrochemical-thermal and mechanical response of a system has a variety of applications, for example, structural failure from electrochemical fatigue and the potential induced changes of material properties. For lithium-ion batteries, there is an added concern over the safety of the system in the event of mechanical failure of the cell components. In this work, we present a generic multi-scale simultaneously coupled mechanical-electrochemical-thermal model to examine the interaction between mechanical failure and electrochemical-thermal responses. We treat the battery cell as a homogeneous material while locally we explicitly solve for the mechanical response of individual components using a homogenization model and the electrochemical-thermal responses using an electrochemical model for the battery. A benchmark problem is established to demonstrate the proposed modeling framework. The model shows the capability to capture the gradual evolution of cell electrochemical-thermal responses, and predicts the variation of those responses under different short-circuit conditions.

Electrochemical DNA biosensor for detection of porcine oligonucleotides using ruthenium(II) complex as intercalator label redox

Energy Technology Data Exchange (ETDEWEB)

Halid, Nurul Izni Abdullah; Hasbullah, Siti Aishah; Heng, Lee Yook; Karim, Nurul Huda Abd [School of Chemical Sciences and Food Technology, Universiti Kebangsaan Malaysia, 43600 UKM Bangi, Selangor Darul Ehsan (Malaysia); Ahmad, Haslina; Harun, Siti Norain [Chemistry Department, Faculty of Science, Universiti Putra Malaysia, 43400, Serdang, Selangor (Malaysia)

2014-09-03

A DNA biosensor detection of oligonucleotides via the interactions of porcine DNA with redox active complex based on the electrochemical transduction is described. A ruthenium(II) complex, [Ru(bpy){sub 2}(PIP)]{sup 2+}, (bpy = 2,2′bipyridine, PIP = 2-phenylimidazo[4,5-f[[1,10-phenanthroline]) as DNA label has been synthesized and characterized by 1H NMR and mass spectra. The study was carried out by covalent bonding immobilization of porcine aminated DNA probes sequences on screen printed electrode (SPE) modified with succinimide-acrylic microspheres and [Ru(bpy){sub 2}(PIP)]{sup 2+} was used as electrochemical redox intercalator label to detect DNA hybridization event. Electrochemical detection was performed by cyclic voltammetry (CV) and differential pulse voltammetry (DPV) over the potential range where the ruthenium (II) complex was active. The results indicate that the interaction of [Ru(bpy){sub 2}(PIP)]{sup 2+} with hybridization complementary DNA has higher response compared to single-stranded and mismatch complementary DNA.

An Electrochemical Impedance Spectroscopy Study on a Lithium Sulfur Pouch Cell

DEFF Research Database (Denmark)

Stroe, Daniel Loan; Knap, Vaclav; Swierczynski, Maciej Jozef

2016-01-01

The impedance behavior of a 3.4 Ah pouch Lithium-Sulfur cell was extensively characterized using the electrochemical impedance spectroscopy (EIS) technique. EIS measurements were performed at various temperatures and over the entire state-of-charge (SOC) interval without applying a superimposed DC...

Sub-10-nm Graphene Nanoribbons with Tunable Surface Functionalities for Lithium-ion Batteries

International Nuclear Information System (INIS)

Li, Yan-Sheng; Ao, Xiang; Liao, Jia-Liang; Jiang, Jianjun; Wang, Chundong; Chiang, Wei-Hung

2017-01-01

Highlights: •A green and scalable method to produce sub-10-nm GNR is present. •The surface functionality of sub-10-nm GNR is critical for the LIB properties. •The sub-10-nm GNR showed superior LIB capacity of 490.4 mAh g −1 after 100 cycles. -- Abstract: A systematic study to reveal the relationship between the surface oxygen-containing functionalities of sub-10-nm GNRs and their electrochemical properties for lithium-ion batteries has been presented. Sub-10-nm GNRs with controlled oxygen-containing groups were synthesized by a green and scalable intercalation-assisted unzipping SWCNTs. Detailed materials characterizations including TEM, XRD, Raman and XPS indicate that KNO 3 could be an effective intercalation agent to facilitate the SWCNT unzipping by reducing the strong Van der Waals force attraction of bundled SWCNT. The levels of surface functionalities of sub-10-nm GNR were tuned by carefully controlling the KMnO 4 concentration during the unzipping process. The electrochemical analysis suggests that the as-produced sub-10-nm GNR with 31.4 atomic percent (atom %) oxygen-containing functional groups showed the highest capacity of 490.4 mAh g −1 after 100 cycles. This work proposed that sub-10-nm GNRs with appropriate oxygen-functional groups can be a promising electrode material for high performance lithium-ion batteries.

Enhanced Lithium- and Sodium-Ion Storage in an Interconnected Carbon Network Comprising Electronegative Fluorine.

Science.gov (United States)

Hong, Seok-Min; Etacheri, Vinodkumar; Hong, Chulgi Nathan; Choi, Seung Wan; Lee, Ki Bong; Pol, Vilas G

2017-06-07

Fluorocarbon (C x F y ) anode materials were developed for lithium- and sodium-ion batteries through a facile one-step carbonization of a single precursor, polyvinylidene fluoride (PVDF). Interconnected carbon network structures were produced with doped fluorine in high-temperature carbonization at 500-800 °C. The fluorocarbon anodes derived from the PVDF precursor showed higher reversible discharge capacities of 735 mAh g -1 and 269 mAh g -1 in lithium- and sodium-ion batteries, respectively, compared to the commercial graphitic carbon. After 100 charge/discharge cycles, the fluorocarbon showed retentions of 91.3% and 97.5% in lithium (at 1C) and sodium (at 200 mA g -1 ) intercalation systems, respectively. The effects of carbonization temperature on the electrochemical properties of alkali metal ion storage were thoroughly investigated and documented. The specific capacities in lithium- and sodium-ion batteries were dependent on the fluorine content, indicating that the highly electronegative fluorine facilitates the insertion/extraction of lithium and sodium ions in rechargeable batteries.

Electrochemical performances of lithium ion battery using alkoxides of group 13 as electrolyte solvent

International Nuclear Information System (INIS)

Kaneko, Fuminari; Masuda, Yuki; Nakayama, Masanobu; Wakihara, Masataka

2007-01-01

Tris(methoxy polyethylenglycol) borate ester (B-PEG) and aluminum tris(polyethylenglycoxide) (Al-PEG) were used as electrolyte solvent for lithium ion battery, and the electrochemical property of these electrolytes were investigated. These electrolytes, especially B-PEG, showed poor electrochemical stability, leading to insufficient discharge capacity and rapid degradation with cycling. These observations would be ascribed to the decomposition of electrolyte, causing formation of unstable passive layer on the surface of electrode in lithium ion battery at high voltage. However, significant improvement was observed by the addition of aluminum phosphate (AlPO 4 ) powder into electrolyte solvent. AC impedance technique revealed that the increase of interfacial resistance of electrode/electrolyte during cycling was suppressed by adding AlPO 4 , and this suppression could enhance the cell capabilities. We infer that dissolved AlPO 4 components formed electrochemically stable layer on the surface of electrode

Novel sodium intercalated (NH4)2V6O16 platelets: High performance cathode materials for lithium-ion battery.

Science.gov (United States)

Fei, Hailong; Wu, Xiaomin; Li, Huan; Wei, Mingdeng

2014-02-01

A simple and versatile method for preparation of novel sodium intercalated (NH4)2V6O16 is developed via a simple hydrothermal route. It is found that ammonium sodium vanadium bronze displays higher discharge capacity and better rate cyclic stability than ammonium vanadium bronze as lithium-ion battery cathode material because of smaller charge transfer resistance, which would favor superior discharge capacity and rate performance. Crown Copyright © 2013. Published by Elsevier Inc. All rights reserved.

Structure dependent electrochemical performance of Li-rich layered oxides in lithium-ion batteries

Energy Technology Data Exchange (ETDEWEB)

Fu, Fang; Yao, Yuze; Wang, Haiyan; Xu, Gui-Liang; Amine, Khalil; Sun, Shi-Gang; Shao, Minhua

2017-04-08

Rational and precise control of the structure and dimension of electrode materials is an efficient way to improve their electrochemical performance. In this work, solvothermal or co-precipitation method is used to synthesize lithium-rich layered oxide materials of Li1.2Mn0.56Co0.12Ni0.12O2 (LLO) with various morphologies and structures, including microspheres, microrods, nanoplates, and irregular nanoparticles. These materials exhibit strong structure- dependent electrochemical properties. The porous hierarchical structured LLO microrods exhibit the best performance, delivering a discharge capacity of 264.6 mAh g(-1) at 0.5 C with over 91% retention after 100 cycles. At a high rate of 5 C, a high discharge capacity of 173.6 mAh g(-1) can be achieved. This work reveals the relationship between the morphologies and electrochemical properties of LLO cathode materials, and provides a feasible approach to fabricating robust and high-performance electrode materials for lithium-ion batteries.

Graphitized biogas-derived carbon nanofibers as anodes for lithium-ion batteries

International Nuclear Information System (INIS)

Cuesta, Nuria; Cameán, Ignacio; Ramos, Alberto; García, Ana B.

2016-01-01

The electrochemical performance as potential anodes for lithium-ion batteries of graphitized biogas-derived carbon nanofibers (BCNFs) is investigated by galvanostatic cycling versus Li/Li + at different electrical current densities. These graphitic nanomaterials have been prepared by high temperature treatment of carbon nanofibers produced in the catalytic decomposition of biogas. At low current density, they deliver specific capacities comparable to that of oil-derived micrometric graphite, the capacity retention values being mostly in the range 70-80% and cycling efficiency ∼ 100%. A clear tendency of the anode capacity to increase alongside the BCNFs crystal thickness was observed. Besides the degree of graphitic tri-dimensional structural order, the presence of loops between the adjacent edges planes on the graphene layers, the mesopore volume and the active surface area of the graphitized BCNFs were found to influence on battery reversible capacity, capacity retention along cycling and irreversible capacity. Furthermore, provided that the development of the crystalline structure is comparable, the graphitized BCNFs studied show better electrochemical rate performance than micrometric graphite. Therefore, this result can be associated with the nanometric particle size as well as the larger surface area of the BCNFs which, respectively, reduces the diffusion time of the lithium ions for the intercalation/de-intercalation processes, i.e. faster charge-discharge rate, and increases the contact area at the anode active material/electrolyte interface which may improve the Li + ions access, i.e. charge transfer reaction.

A flexible ligand-based wavy layered metal-organic framework for lithium-ion storage.

Science.gov (United States)

An, Tiance; Wang, Yuhang; Tang, Jing; Wang, Yang; Zhang, Lijuan; Zheng, Gengfeng

2015-05-01

A substantial challenge for direct utilization of metal-organic frameworks (MOFs) as lithium-ion battery anodes is to maintain the rigid MOF structure during lithiation/delithiation cycles. In this work, we developed a flexible, wavy layered nickel-based MOF (C20H24Cl2N8Ni, designated as Ni-Me4bpz) by a solvothermal approach of 3,3',5,5'-tetramethyl-4,4'-bipyrazole (H2Me4bpz) with nickel(II) chloride hexahydrate. The obtained MOF materials (Ni-Me4bpz) with metal azolate coordination mode provide 2-dimensional layered structure for Li(+) intercalation/extraction, and the H2Me4bpz ligands allow for flexible rotation feature and structural stability. Lithium-ion battery anodes made of the Ni-Me4bpz material demonstrate excellent specific capacity and cycling performance, and the crystal structure is well preserved after the electrochemical tests, suggesting the potential of developing flexible layered MOFs for efficient and stable electrochemical storage. Copyright © 2015 Elsevier Inc. All rights reserved.

Lithium alloys and metal oxides as high-capacity anode materials for lithium-ion batteries

International Nuclear Information System (INIS)

Liang, Chu; Gao, Mingxia; Pan, Hongge; Liu, Yongfeng; Yan, Mi

2013-01-01

Highlights: •Progress in lithium alloys and metal oxides as anode materials for lithium-ion batteries is reviewed. •Electrochemical characteristics and lithium storage mechanisms of lithium alloys and metal oxides are summarized. •Strategies for improving electrochemical lithium storage properties of lithium alloys and metal oxides are discussed. •Challenges in developing lithium alloys and metal oxides as commercial anodes for lithium-ion batteries are pointed out. -- Abstract: Lithium alloys and metal oxides have been widely recognized as the next-generation anode materials for lithium-ion batteries with high energy density and high power density. A variety of lithium alloys and metal oxides have been explored as alternatives to the commercial carbonaceous anodes. The electrochemical characteristics of silicon, tin, tin oxide, iron oxides, cobalt oxides, copper oxides, and so on are systematically summarized. In this review, it is not the scope to retrace the overall studies, but rather to highlight the electrochemical performances, the lithium storage mechanism and the strategies in improving the electrochemical properties of lithium alloys and metal oxides. The challenges and new directions in developing lithium alloys and metal oxides as commercial anodes for the next-generation lithium-ion batteries are also discussed

INTERPRETATION OF POTENTIAL INTERMITTENCE TITRATION TECHNIQUE EXPERIMENTS FOR VARIOUS Li-INTERCALATION ELECTRODES

Directory of Open Access Journals (Sweden)

M.D.Levi

2002-01-01

Full Text Available In this paper we compare two different approaches for the calculation of the enhancement factor Wi, based on its definition as the ratio of the chemical and the component diffusion coefficients for species in mixed-conduction electrodes, originated from the "dilute solution" or "lattice gas" models for the ion system. The former approach is only applicable for small changes of the ion concentration while the latter allows one to consider a broad range of intercalation levels. The component diffusion coefficient of lithium ions has been determined for a series of lithium intercalation anodes and cathodes. A new "enhancement factor" for the ion transport has been defined and its relations to the intercalation capacitance and the intercalation isotherm have been established. A correlation between the dependences of the differential capacitance and the partial ion conductivity on the potential has been observed. It is considered as a prove that the intercalation process is controlled by the availability of sites for Li-ion insertion rather than by the concurrent insertion of the counter-balancing electronic species.

Electrochemically cathodic exfoliation of graphene sheets in room temperature ionic liquids N-butyl, methylpyrrolidinium bis(trifluoromethylsulfonyl)imide and their electrochemical properties

International Nuclear Information System (INIS)

Yang, Yingchang; Lu, Fang; Zhou, Zhou; Song, Weixin; Chen, Qiyuan; Ji, Xiaobo

2013-01-01

Graphical abstract: Electrochemically cathodic exfoliation of graphite into few-layer graphene sheets in room temperature ionic liquids (RTILs) N-butyl, methylpyrrolidinium bis(trifluoromethylsulfonyl)-imide (BMPTF 2 N). -- Highlights: • Few-layer graphene sheets were prepared through electrochemically cathodic exfoliation in room temperature ionic liquids. • The mechanism of cathodic exfoliation in ionic liquids was proposed. • The derived activated graphene sheets show enhanced electrochemical properties. -- Abstract: Electrochemically cathodic exfoliation in room temperature ionic liquids N-butyl, methylpyrrolidinium bis(trifluoromethylsulfonyl)-imide (BMPTF 2 N) has been developed for few-layer graphene sheets, demonstrating low levels of oxygen (2.7 at% of O) with a nearly perfect structure (I D /I G 2 N involves the intercalation of ionic liquids cation [BMP] + under highly negatively charge followed by graphite expansion. Porous activated graphene sheets were also obtained by activation of graphene sheets in KOH. Transmission electron microscopy, X-ray photoelectron spectroscopy and Raman spectroscopy were used to characterize these graphene materials. The electrochemical performances of the graphene sheets and porous activated graphene sheets for lithium-ion battery anode materials were evaluated using cyclic voltammetry, galvanostatic charge–discharge cycling, and electrochemical impedance spectroscopy

Structural and Electrochemical Study of Vanadium-Doped TiO2 Ramsdellite with Superior Lithium Storage Properties for Lithium-Ion Batteries.

Science.gov (United States)

Pérez-Flores, Juan Carlos; Hoelzel, Markus; García-Alvarado, Flaviano; Kuhn, Alois

2016-04-04

Titanium-oxide-based materials are considered attractive and safe alternatives to carbonaceous anodes in Li-ion batteries. In particular, the ramsdellite form TiO2 (R) is known for its superior lithium-storage ability as the bulk material when compared with other titanates. In this work, we prepared V-doped lithium titanate ramsdellites with the formula Li0.5 Ti1-x Vx O2 (0≤x≤0.5) by a conventional solid-state reaction. The lithium-free Ti1-x Vx O2 compounds, in which the ramsdellite framework remains virtually unaltered, are easily obtained by a simple aqueous oxidation/ion-extraction process. Neutron powder diffraction is used to locate the Li channel site in Li0.5 Ti1-x Vx O2 compounds and to follow the lithium extraction by difference-Fourier maps. Previously delithiated Ti1-x Vx O2 ramsdellites are able to insert up to 0.8 Li(+) per transition-metal atom. The initial gravimetric capacities of 270 mAh g(-1) with good cycle stability under constant current discharge conditions are among the highest reported for bulk TiO2 -related intercalation compounds for the threshold of one e(-) per formula unit. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Comparison of reduction products from graphite oxide and graphene oxide for anode applications in lithium-ion batteries and sodium-ion batteries.

Science.gov (United States)

Sun, Yige; Tang, Jie; Zhang, Kun; Yuan, Jinshi; Li, Jing; Zhu, Da-Ming; Ozawa, Kiyoshi; Qin, Lu-Chang

2017-02-16

Hydrazine-reduced graphite oxide and graphene oxide were synthesized to compare their performances as anode materials in lithium-ion batteries and sodium-ion batteries. Reduced graphite oxide inherits the layer structure of graphite, with an average spacing between neighboring layers (d-spacing) of 0.374 nm; this exceeds the d-spacing of graphite (0.335 nm). The larger d-spacing provides wider channels for transporting lithium ions and sodium ions in the material. We showed that reduced graphite oxide as an anode in lithium-ion batteries can reach a specific capacity of 917 mA h g -1 , which is about three times of 372 mA h g -1 , the value expected for the LiC 6 structures on the electrode. This increase is consistent with the wider d-spacing, which enhances lithium intercalation and de-intercalation on the electrodes. The electrochemical performance of the lithium-ion batteries and sodium-ion batteries with reduced graphite oxide anodes show a noticeable improvement compared to those with reduced graphene oxide anodes. This improvement indicates that reduced graphite oxide, with larger interlayer spacing, has fewer defects and is thus more stable. In summary, we found that reduced graphite oxide may be a more favorable form of graphene for the fabrication of electrodes for lithium-ion and sodium-ion batteries and other energy storage devices.

Isolation of high quality graphene from Ru by solution phase intercalation

Science.gov (United States)

Koren, E.; Sutter, E.; Bliznakov, S.; Ivars-Barcelo, F.; Sutter, P.

2013-09-01

We introduce a method for isolating graphene grown on epitaxial Ru(0001)/α-Al2O3. The strong graphene/Ru(0001) coupling is weakened by electrochemically driven intercalation of hydrogen underpotentially deposited in aqueous KOH solution, which allows the penetration of water molecules at the graphene/Ru(0001) interface. Following these electrochemically driven processes, the graphene can be isolated by electrochemical hydrogen evolution and transferred to arbitrary supports. Raman and transport measurements demonstrate the high quality of the transferred graphene. Our results show that intercalation, typically carried out in vacuum, can be extended to solution environments for graphene processing under ambient conditions.

Novel lithium titanate-graphene hybrid containing two graphene conductive frameworks for lithium-ion battery with excellent electrochemical performance

Energy Technology Data Exchange (ETDEWEB)

Ruiyi, Li; Tengyuan, Chen; Beibei, Sun [School of Chemical and Material Engineering, Jiangnan University, Wuxi 214122 (China); Zaijun, Li [School of Chemical and Material Engineering, Jiangnan University, Wuxi 214122 (China); Key Laboratory of Food Colloids and Biotechnology, Ministry of Education, Wuxi 214122 (China); Zhiquo, Gu; Guangli, Wang; Junkang, Liu [School of Chemical and Material Engineering, Jiangnan University, Wuxi 214122 (China)

2015-10-15

Graphical abstract: We developed a new Novel lithium titanate-graphene nanohybrid containing two graphene conductive frameworks. The unique architecture creates fast electron transfer and rapid mass transport of electrolyte. The hybrid electrode provides excellent electrochemical performances for lithium-ion batteries, including high specific capacity, outstanding rate capability and intriguing cycling stability. - Highlights: • We reported a new LTO-graphene nanohybrid containing two graphene conductive frameworks. • One graphene framework greatly improves the electrical conductivity of LTO crystal. • Another graphene framework enhances electrical conductivity of between LTO crystals and electrolyte transport. • The unique architecture creates big tap density, ultrafast electron transfer and rapid mass transport. • The hybrid electrode provides excellent electrochemical performance for lithium-ion batteries. - ABSTRACT: The paper reported the synthesis of lithium titanate(LTO)-graphene hybrid containing two graphene conductive frameworks (G@LTO@G). Tetrabutyl titanate and graphene were dispersed in tertbutanol and heated to reflux state by microwave irradiation. Followed by adding lithium acetate to produce LTO precursor/graphene (p-LTO/G). The resulting p-LTO/G offers homogeneous morphology and ultra small size. All graphene sheets were buried in the spherical agglomerates composed of primitive particles through the second agglomeration. The p-LTO/G was calcined to LTO@graphene (LTO@G). To obtain G@LTO@G, the LTO@G was further hybridized with graphene. The as-prepared G@LTO@G shows well-defined three-dimensional structure and hierarchical porous distribution. Its unique architecture creates big tap density, fast electron transfer and rapid electrolyte transport. As a result, the G@LTO@G provides high specific capacity (175.2 mA h g{sup −1} and 293.5 mA cm{sup −3}), outstanding rate capability (155.7 mAh g{sup −1} at 10C) and intriguing cycling

An experimental and theoretical approach on the effect of presence of oxygen in milled graphite as lithium storage material

International Nuclear Information System (INIS)

Robledo, C.B.; Thomas, J.E.; Luque, G.; Leiva, E.P.M.; Cámara, O.; Barraco, D.; Visintin, A.

2014-01-01

The effect of milling time on the morphology of graphite is characterized by XRD, SEM, BET, FTIR and XPS and the electrochemical response of the resulting materials upon lithium-ion absorption is analyzed using different techniques. As milling time is increased, the particle size diminishes and the amount of oxygen content increases. Concomitantly, the capacity for lithium adsorption also increases because new adsorption sites become available due to more surface area and oxygen functional groups. These effects are interpreted using first-principles calculations, which show that the presence of oxygenated species promotes lithium adsorption at higher potentials. This capacity increase is probably not relevant for lithium-ion batteries since there is no intercalation process but rather an adsorption one, but may be of interest for supercapacitive applications. Diffusion coefficients of lithium for different graphite particle sizes are evaluated. The effects of diffusion, particle size and oxygen content are discussed

Design of a Sensitive and Selective Electrochemical Aptasensor for the Determination of the Complementary cDNA of miRNA-145 Based on the Intercalation and Electrochemical Reduction of Doxorubicin.

Science.gov (United States)

Mohamadi, Maryam; Mostafavi, Ali; Torkzadeh-Mahani, Masoud

2017-11-01

The aim of this research was the determination of a microRNA (miRNA) using a DNA electrochemical aptasensor. In this biosensor, the complementary complementary DNA (cDNA) of miRNA-145 (a sense RNA transcript) was the target strand and the cDNA of miRNA-145 was the probe strand. Both cDNAs can be the product of the reverse transcriptase-polymerase chain reaction of miRNA. The proposed aptasensor's function was based on the hybridization of target strands with probes immobilized on the surface of a working electrode and the subsequent intercalation of doxorubicin (DOX) molecules functioning as the electroactive indicators of any double strands that formed. Electrochemical transduction was performed by measuring the cathodic current resulting from the electrochemical reduction of the intercalated molecules at the electrode surface. In the experiment, because many DOX molecules accumulated on each target strand on the electrode surface, amplification was inherently easy, without a need for enzymatic or complicated amplification strategies. The proposed aptasensor also had the excellent ability to regenerate as a result of the melting of the DNA duplex. Moreover, the use of DNA probe strands obviated the challenges of working with an RNA probe, such as sensitivity to RNase enzyme. In addition to the linear relationship between the electrochemical signal and the concentration of the target strands that ranged from 2.0 to 80.0 nM with an LOD of 0.27 nM, the proposed biosensor was clearly capable of distinguishing between complementary (target strand) and noncomplementary sequences. The presented biosensor was successfully applied for the quantification of DNA strands corresponding to miRNA-145 in human serum samples.

Electrochemical reactivity of ilmenite FeTiO3, its nanostructures and oxide-carbon nanocomposites with lithium

International Nuclear Information System (INIS)

Tao, Tao; Glushenkov, Alexey M.; Rahman, Md Mokhlesur; Chen, Ying

2013-01-01

The electrochemical reactivity of the ball-milled ilmenite FeTiO 3 and ilmenite nanoflowers with lithium has been investigated. The electrode assembled with the ilmenite nanoflowers delivers better electrochemical performance than that of the milled material during charging and discharging in the potential range of 0.01 and 3 V vs. Li/Li + . The ilmenite nanoflowers demonstrate the capacity of ca. 650 mAh g −1 during the first discharge, and a reversible capacity of approximately 200 mAh g −1 in the course of the first 50 cycles. The possible reaction mechanism between ilmenite and lithium was studied using cyclic voltammetry and transmission electron microscopy. The first discharge involves the formation of an irreversible phase, which is either LiTiO 2 or LiFeO 2 . Subsequently, the extraction–insertion of lithium happens in a reversible manner. It was also observed that the lithium storage might be significantly improved if the electrode was prepared in the form of a nanocomposite of FeTiO 3 with carbon

Method for intercalating alkali metal ions into carbon electrodes

Science.gov (United States)

Doeff, Marca M.; Ma, Yanping; Visco, Steven J.; DeJonghe, Lutgard

1995-01-01

A low cost, relatively flexible, carbon electrode for use in a secondary battery is described. A method is provided for producing same, including intercalating alkali metal salts such as sodium and lithium into carbon.

Comparative electrochemical sodium insertion/extraction behavior in layered NaxVS2 and NaxTiS2

International Nuclear Information System (INIS)

Lee, Eungje; Sahgong, SunHye; Johnson, Christopher S.; Kim, Youngsik

2014-01-01

This study investigates the electrochemical sodium insertion/extraction of Na x VS 2 , and Na x TiS 2 in the voltage range where either intercalation (0.2 ≤ x ≤ 1) or displacement-conversion reaction (x > 1) occurs. Both Na x VS 2 and Na x TiS 2 showed good reversible capacities, as high as ∼160 mAh/g at an average voltage of ∼1.9 V vs. Na in the region for the intercalation reaction (0.2 ≤ x ≤ 1). When sodium (Na) insertion was forced further to the x > 1 composition, Na x VS 2 exhibited the direct displacement-conversion reaction at 0.3 V vs. Na without further Na intercalation, which contrasted with the wider lithium intercalation range of 0 < x ≤ 2 for Li x VS 2 . The displacement-conversion reaction for Na x VS 2 (x > 1) was reversible with a specific capacity of above 200 mAh/g up to 15 cycles, but the displacement reaction for Na x TiS 2 (x > 1) was not observed

Investigating the Intercalation Chemistry of Alkali Ions in Fluoride Perovskites

Energy Technology Data Exchange (ETDEWEB)

Yi, Tanghong; Chen, Wei; Cheng, Lei; Bayliss, Ryan D.; Lin, Feng; Plews, Michael R.; Nordlund, Dennis; Doeff, Marca M.; Persson, Kristin A.; Cabana, Jordi (LBNL); (SLAC); (UIC); (UCB)

2017-02-07

Reversible intercalation reactions provide the basis for modern battery electrodes. Despite decades of exploration of electrode materials, the potential for materials in the nonoxide chemical space with regards to intercalation chemistry is vast and rather untested. Transition metal fluorides stand out as an obvious target. To this end, we report herein a new family of iron fluoride-based perovskite cathode materials A_xK_1–xFeF₃ (A = Li, Na). By starting with KFeF₃, approximately 75% of K⁺ ions were subsequently replaced by Li⁺ and Na⁺ through electrochemical means. X-ray diffraction and Fe X-ray absorption spectroscopy confirmed the existence of intercalation of alkali metal ions in the perovskite structure, which is associated with the Fe^2+/3+ redox couple. A computational study by density functional theory showed agreement with the structural and electrochemical data obtained experimentally, which suggested the possibility of fluoride-based materials as potential intercalation electrodes. This study increases our understanding of the intercalation chemistry of ternary fluorides, which could inform efforts toward the exploration of new electrode materials.

Morphological, structural and electrochemical properties of lithium iron phosphates synthesized by Spray Pyrolysis

Energy Technology Data Exchange (ETDEWEB)

Gomez, L.S. [Universidad Carlos III de Madrid and IAAB, Avda. de la Universidad, 30, 28911 Leganes, Madrid (Spain); Meatza, I. de [Dpto. Energia, CIDETEC, Po Miramon 196, Parque Tecnologico de San Sebastian, 20009 Donostia-San Sebastian (Spain); Martin, M.I., E-mail: imartin@ietcc.csic.e [Universidad Carlos III de Madrid and IAAB, Avda. de la Universidad, 30, 28911 Leganes, Madrid (Spain); Bengoechea, M. [Dpto. Energia, CIDETEC, Po Miramon 196, Parque Tecnologico de San Sebastian, 20009 Donostia-San Sebastian (Spain); Cantero, I. [Dpto. I-D-i Nuevas Tecnologias, CEGASA, Artapadura, 11, 01013 Vitoria-Gasteiz (Spain); Rabanal, M.E., E-mail: mariaeugenia.rabanal@uc3m.e [Universidad Carlos III de Madrid and IAAB, Avda. de la Universidad, 30, 28911 Leganes, Madrid (Spain)

2010-03-01

In the field of materials for lithium ion batteries, the lithium iron phosphate LiFePO{sub 4} has been proven for use as a positive electrode due to its good resistance to thermal degradation and overcharge, safety and low cost. The use of nanostructured materials would improve its efficiency. This work shows the results of the synthesis of nanostructured materials with functional properties for lithium batteries through aerosol techniques. The Spray Pyrolysis method allows synthesizing nanostructured particles with spherical geometry, not agglomerates, with narrow distribution of particle size and homogeneous composition in respect to a precursor solution. Experimental techniques were focused on the morphological (SEM and TEM), structural (XRD and HRTEM-SAED), chemical (EDS) and electrochemical characterization.

Morphological, structural and electrochemical properties of lithium iron phosphates synthesized by Spray Pyrolysis

International Nuclear Information System (INIS)

Gomez, L.S.; Meatza, I. de; Martin, M.I.; Bengoechea, M.; Cantero, I.; Rabanal, M.E.

2010-01-01

In the field of materials for lithium ion batteries, the lithium iron phosphate LiFePO 4 has been proven for use as a positive electrode due to its good resistance to thermal degradation and overcharge, safety and low cost. The use of nanostructured materials would improve its efficiency. This work shows the results of the synthesis of nanostructured materials with functional properties for lithium batteries through aerosol techniques. The Spray Pyrolysis method allows synthesizing nanostructured particles with spherical geometry, not agglomerates, with narrow distribution of particle size and homogeneous composition in respect to a precursor solution. Experimental techniques were focused on the morphological (SEM and TEM), structural (XRD and HRTEM-SAED), chemical (EDS) and electrochemical characterization.

First-Principles Study of Lithium and Sodium Atoms Intercalation in Fluorinated Graphite

Directory of Open Access Journals (Sweden)

Fengya Rao

2015-06-01

Full Text Available The structure evolution of fluorinated graphite (CFx upon the Li/Na intercalation has been studied by first-principles calculations. The Li/Na adsorption on single CF layer and intercalated into bulk CF have been calculated. The better cycling performance of Na intercalation into the CF cathode, comparing to that of Li intercalation, is attributed to the different strength and characteristics of the Li-F and Na-F interactions. The interactions between Li and F are stronger and more localized than those between Na and F. The strong and localized Coulomb attraction between Li and F atoms breaks the C−F bonds and pulls the F atoms away, and graphene sheets are formed upon Li intercalation.

Synthesis of reduced graphene oxide intercalated ZnO quantum dots nanoballs for selective biosensing detection

Energy Technology Data Exchange (ETDEWEB)

Chen, Jing; Zhao, Minggang, E-mail: zhaomg@ouc.edu.cn; Li, Yingchun; Fan, Sisi; Ding, Longjiang; Liang, Jingjing; Chen, Shougang, E-mail: sgchen@ouc.edu.cn

2016-07-15

Highlights: • A MWCNTs/rGO/ZnO quantum dots intercalation nanoballs decorated 3D hierarchical architecture is fabricated on Ni foam. • Large numbers of ZnO quantum dots are intercalated by rGO sheets to construct hierarchical nanoballs. • Improved mechanical, kinetic and electrochemical properties are found. • The strong interfacial effect makes the material can be used for selective detection of dopamine, ascorbic acid and uric acid. - Abstract: ZnO quantum dots (QDs), reduced graphene oxide (rGO) and multi-walled carbon nanotubes (MWCNTs) are always used in sensors due to their excellent electrochemical characteristics. In this work, ZnO QDs were intercalated by rGO sheets with cross-linked MWCNTs to construct intercalation nanoballs. A MWCNTs/rGO/ZnO QDs 3D hierarchical architecture was fabricated on supporting Ni foam, which exhibited excellent mechanical, kinetic and electrochemical properties. The intercalation construction can introduce strong interfacial effects to improve the surface electronic state. The selectively determinate of uric acid, dopamine, and ascorbic acid by an electrode material using distinct applied potentials was realized.

Synthesis of reduced graphene oxide intercalated ZnO quantum dots nanoballs for selective biosensing detection

International Nuclear Information System (INIS)

Chen, Jing; Zhao, Minggang; Li, Yingchun; Fan, Sisi; Ding, Longjiang; Liang, Jingjing; Chen, Shougang

2016-01-01

Highlights: • A MWCNTs/rGO/ZnO quantum dots intercalation nanoballs decorated 3D hierarchical architecture is fabricated on Ni foam. • Large numbers of ZnO quantum dots are intercalated by rGO sheets to construct hierarchical nanoballs. • Improved mechanical, kinetic and electrochemical properties are found. • The strong interfacial effect makes the material can be used for selective detection of dopamine, ascorbic acid and uric acid. - Abstract: ZnO quantum dots (QDs), reduced graphene oxide (rGO) and multi-walled carbon nanotubes (MWCNTs) are always used in sensors due to their excellent electrochemical characteristics. In this work, ZnO QDs were intercalated by rGO sheets with cross-linked MWCNTs to construct intercalation nanoballs. A MWCNTs/rGO/ZnO QDs 3D hierarchical architecture was fabricated on supporting Ni foam, which exhibited excellent mechanical, kinetic and electrochemical properties. The intercalation construction can introduce strong interfacial effects to improve the surface electronic state. The selectively determinate of uric acid, dopamine, and ascorbic acid by an electrode material using distinct applied potentials was realized.

Electrochemical study of lithium insertion into carbon-rich polymer-derived silicon carbonitride ceramics

International Nuclear Information System (INIS)

Kaspar, Jan; Mera, Gabriela; Nowak, Andrzej P.; Graczyk-Zajac, Magdalena; Riedel, Ralf

2010-01-01

This paper presents the lithium insertion into carbon-rich polymer-derived silicon carbonitride (SiCN) ceramic synthesized by the thermal treatment of poly(diphenylsilylcarbodiimide) at three temperatures, namely 1100, 1300, and 1700 o C under 0.1 MPa Ar atmosphere. At lower synthesis temperatures, the material is X-ray amorphous, while at 1700 o C, the SiCN ceramic partially crystallizes. Anode materials prepared from these carbon-rich SiCN ceramics without any fillers and conducting additives were characterized using cyclic voltammetry and chronopotentiometric charging/discharging. We found that the studied silicon carbonitride ceramics demonstrate a promising electrochemical behavior during lithium insertion/extraction in terms of capacity and cycling stability. The sample synthesized at 1300 o C exhibits a reversible capacity of 392 mAh g -1 . Our study confirms that carbon-rich SiCN phases are electrochemically active materials in terms of Li inter- and deintercalation.

Spectroscopic and Electrochemical Properties of Lithium-Rich LiFePO4 Cathode Synthesized by Solid-State Reaction

Science.gov (United States)

Rosaiah, P.; Hussain, O. M.; Zhu, Jinghui; Qiu, Yejun

2017-08-01

Lithium iron phosphate (Li x FePO4) is synthesized by a solid-state reaction method. The structural, electrical and electrochemical properties are studied in detail. It is found that the increment of lithium concentration (up to x = 1.05) does not affect the structure of LiFePO4 but improves its electrical conductivity as well as electrochemical performance. Surface morphological studies exhibited the formation of rod-like nanoparticles with small size. Electric and dielectric properties are also investigated over a frequency range of 1 Hz-1 MHz at different temperatures. The conductivity increased with increasing temperature, which follows the Arrhenius relation with the activation energy of about 0.31 eV. And the electrochemical tests found that the Li1.05FePO4 cathode possessed improved discharge capacity with better cycling performance.

Impedance Simulation of a Li-Ion Battery with Porous Electrodes and Spherical Li+ Intercalation Particles

NARCIS (Netherlands)

Huang, R.W.J.M.; Chung, F.; Kelder, E.M.

2006-01-01

We present a semimathematical model for the simulation of the impedance spectra of a rechargeable lithium batteries consisting of porous electrodes with spherical Li+ intercalation particles. The particles are considered to have two distinct homogeneous phases as a result of the intercalation and

V2O5 xerogel-poly(ethylene oxide) hybrid material: Synthesis, characterization, and electrochemical properties

International Nuclear Information System (INIS)

Guerra, Elidia M.; Ciuffi, Katia J.; Oliveira, Herenilton P.

2006-01-01

In this work, we report the synthesis, characterization, and electrochemical properties of vanadium pentoxide xerogel-poly(ethylene oxide) (PEO) hybrid materials obtained by varying the average molecular weight of the organic component as well as the components' ratios. The materials were characterized by X-ray diffraction, ultraviolet/visible and infrared spectroscopies, thermogravimetric analysis, scanning electron microscopy, electron paramagnetic resonance, and cyclic voltammetry. Despite the presence of broad and low intensity peaks, the X-ray diffractograms indicate that the lamellar structure of the vanadium pentoxide xerogel is preserved, with increase in the interplanar spacing, giving evidence of a low-crystalline structure. We found that the electrochemical behaviour of the hybrid materials is quite similar to that found for the V 2 O 5 xerogel alone, and we verified that PEO leads to stabilization and reproducibility of the Li + electrochemical insertion/de-insertion into the V 2 O 5 xerogel structure, which makes these materials potential components of lithium ion batteries. - Graphical abstract: The synthesis, structural and electrochemical properties of vanadium pentoxide xerogel-poly(ethylene oxide) hybrid materials have been described. Despite the presence of broad and low intensity peaks, the X-ray diffractograms indicate that the lamellar structure of the vanadium pentoxide xerogel is preserved. The cyclic voltammetry technique demonstrated that PEO intercalation provides an improvement in the electrochemical properties, mainly with respect to the lithium electroinsertion process into the oxide matrix

Lithium-Ion Battery Power Degradation Modelling by Electrochemical Impedance Spectroscopy

DEFF Research Database (Denmark)

Stroe, Daniel-Ioan; Swierczynski, Maciej Jozef; Stroe, Ana-Irina

2017-01-01

This paper investigates the use of the electrochemical impedance spectroscopy (EIS) technique as an alternative to the DC pulses technique for estimating the power capability decrease of Lithium-ion batteries during calendar ageing. Based on results obtained from calendar ageing tests performed...... at different conditions during one to two years, a generalized model that estimates the battery power capability decrease as function of the resistance Rs increase (obtained from EIS) was proposed and successfully verified....

Solid-state chelation of metal ions by ethylenediaminetetraacetate intercalated in a layered double hydroxide.

Science.gov (United States)

Tarasov, Konstantin A; O'Hare, Dermot; Isupov, Vitaly P

2003-03-24

The solid-state chelation of transition metal ions (Co(2+), Ni(2+), and Cu(2+)) from aqueous solutions into the lithium aluminum layered double hydroxide ([LiAl(2)(OH)(6)]Cl x 0.5H(2)O or LDH) which has been pre-intercalated with EDTA (ethylenediaminetetraacetate) ligand has been investigated. The intercalated metal cations form [M(edta)](2)(-) complexes between the LDH layers as indicated by elemental analysis, powder X-ray diffraction, and IR and UV-vis spectroscopies. If metal chloride or nitrate salts are used in the reaction with the LDH then co-intercalation of either the Cl(-) or NO(3)(-) anions is observed. In the case of metal acetate salts the cations intercalate without the accompanying anion. This can be explained by the different intercalation selectivity of the anions in relation to the LDH. In the latter case the introduction of the positive charge into LDH structure was compensated for by the release from the solid of the equivalent quantity of lithium and hydrogen cations. Time-resolved in-situ X-ray diffraction measurements have revealed that the chelation/intercalation reactions proceed very quickly. The rate of the reaction found for nickel acetate depends on concentration as approximately k[Ni(Ac)(2)](3).

Diagnosis of Lithium-Ion Batteries State-of-Health based on Electrochemical Impedance Spectroscopy Technique

DEFF Research Database (Denmark)

Stroe, Daniel Ioan; Swierczynski, Maciej Jozef; Stan, Ana-Irina

2014-01-01

Lithium-ion batteries have developed into a popular energy storage choice for a wide range of applications because of their superior characteristics in comparison to other energy storage technologies. Besides modelling the performance behavior of Lithium-ion batteries, it has become of huge...... interest to accurately diagnose their state-of-health (SOH). At present, Lithium-ion batteries are diagnosed by performing capacity or resistance (current pulse) measurements; however, in the majority of the cases, these measurements are time consuming and result in changing the state of the battery...... as well. This paper investigates the use of the electrochemical impedance spectroscopy (EIS) technique for SOH diagnosis of Lithium-ion battery cells, instead of using the aforementioned techniques, since this new method allows for online and direct measurement of the battery cell response in any working...

Electrochemical performance of CuNCN for sodium ion batteries and comparison with ZnNCN and lithium ion batteries

Science.gov (United States)

Eguia-Barrio, A.; Castillo-Martínez, E.; Klein, F.; Pinedo, R.; Lezama, L.; Janek, J.; Adelhelm, P.; Rojo, T.

2017-11-01

Transition metal carbodiimides (TMNCN) undergo conversion reactions during electrochemical cycling in lithium and sodium ion batteries. Micron sized copper and zinc carbodiimide powders have been prepared as single phase as confirmed by PXRD and IR and their thermal stability has been studied in air and nitrogen atmosphere. CuNCN decomposes at ∼250 °C into CuO or Cu while ZnNCN can be stable until 400 °C and 800 °C in air and nitrogen respectively. Both carbodiimides were electrochemically analysed for sodium and lithium ion batteries. The electrochemical Na+ insertion in CuNCN exhibits a relatively high reversible capacity (300 mAh·g-1) which still indicates an incomplete conversion reaction. This incomplete reaction confirmed by ex-situ EPR analysis, is partly due to kinetic limitations as evidenced in the rate capability experiments and in the constant potential measurements. On the other hand, ZnNCN shows incomplete conversion reaction but with good capacity retention and lower hysteresis as negative electrode for sodium ion batteries. The electrochemical performance of these materials is comparable to that of other materials which operate through displacement reactions and is surprisingly better in sodium ion batteries in comparison with lithium ion batteries.

Electrochemical Characteristics and Li+ Ion Intercalation Kinetics of Dual-phase Li4Ti5O12/Li2TiO3 Composite in Voltage Range of 0−3 V

KAUST Repository

Bhatti, Humaira S

2016-04-20

Li4Ti5O12, Li2TiO3 and dual-phase Li4Ti5O12/Li2TiO3 composite were prepared by sol-gel method with average particle size of 1 µm, 0.3 µm and 0.4 µm, respectively. Though Li2TiO3 is electrochemically inactive, the rate capability of Li4Ti5O12/Li2TiO3 is comparable to Li4Ti5O12 at different current rates. Li4Ti5O12/Li2TiO3 also shows good rate performance of 90 mA h g-1 at high rate of 10 C in voltage range of 1−3 V, attributable to increased interfaces in the composite. While Li4Ti5O12 delivers capacity retention of 88.6 % at 0.2 C over 50 cycles, Li4Ti5O12/Li2TiO3 exhibits no capacity fading at 0.2 C (40 cycles) and capacity retention of 98.45 % at 0.5 C (50 cycles). This highly stable cycling performance is attributed to the contribution of Li2TiO3 in preventing undesirable reaction of Li4Ti5O12 with the electrolyte during cycling. CV curves of Li4Ti5O12/Li2TiO3 in 0−3 V range exhibit two anodic peaks at 1.51 V and 0.7−0.0 V, indicating two modes of lithium intercalation into the lattice sites of active material. Owing to enhanced intercalation/de-intercalation kinetics in 0−3 V, composite electrode delivers superior rate performance of 203 mAh/g at 2.85 C and 140 mAh/g at 5.7 C with good reversible capacity retention over 100 cycles.

Electrochemical Characteristics and Li+ Ion Intercalation Kinetics of Dual-phase Li4Ti5O12/Li2TiO3 Composite in Voltage Range of 0−3 V

KAUST Repository

Bhatti, Humaira S; Anjum, Dalaver H.; Ullah, Shafiq; Ahmed, Bilal; Habib, Amir; Karim, Altaf; Hasanain, Syed Khurshid

2016-01-01

Li4Ti5O12, Li2TiO3 and dual-phase Li4Ti5O12/Li2TiO3 composite were prepared by sol-gel method with average particle size of 1 µm, 0.3 µm and 0.4 µm, respectively. Though Li2TiO3 is electrochemically inactive, the rate capability of Li4Ti5O12/Li2TiO3 is comparable to Li4Ti5O12 at different current rates. Li4Ti5O12/Li2TiO3 also shows good rate performance of 90 mA h g-1 at high rate of 10 C in voltage range of 1−3 V, attributable to increased interfaces in the composite. While Li4Ti5O12 delivers capacity retention of 88.6 % at 0.2 C over 50 cycles, Li4Ti5O12/Li2TiO3 exhibits no capacity fading at 0.2 C (40 cycles) and capacity retention of 98.45 % at 0.5 C (50 cycles). This highly stable cycling performance is attributed to the contribution of Li2TiO3 in preventing undesirable reaction of Li4Ti5O12 with the electrolyte during cycling. CV curves of Li4Ti5O12/Li2TiO3 in 0−3 V range exhibit two anodic peaks at 1.51 V and 0.7−0.0 V, indicating two modes of lithium intercalation into the lattice sites of active material. Owing to enhanced intercalation/de-intercalation kinetics in 0−3 V, composite electrode delivers superior rate performance of 203 mAh/g at 2.85 C and 140 mAh/g at 5.7 C with good reversible capacity retention over 100 cycles.

Structural and Electrochemical Properties of Lithium Nickel Oxide Thin Films

Directory of Open Access Journals (Sweden)

Gyu-bong Cho

2014-01-01

Full Text Available LiNiO2 thin films were fabricated by RF magnetron sputtering. The microstructure of the films was determined by X-ray diffraction and field-emission scanning electron microscopy. The electrochemical properties were investigated with a battery cycler using coin-type half-cells. The LiNiO2 thin films annealed below 500°C had the surface carbonate. The results suggest that surface carbonate interrupted the Li intercalation and deintercalation during charge/discharge. Although the annealing process enhanced the crystallization of LiNiO2, the capacity did not increase. When the annealing temperature was increased to 600°C, the FeCrNiO4 oxide phase was generated and the discharge capacity decreased due to an oxygen deficiency in the LiNiO2 thin film. The ZrO2-coated LiNiO2 thin film provided an improved discharge capacity compared to bare LiNiO2 thin film suggesting that the improved electrochemical characteristic may be attributed to the inhibition of surface carbonate by ZrO2 coating layer.

Powder, paper and foam of few-layer graphene prepared in high yield by electrochemical intercalation exfoliation of expanded graphite.

Science.gov (United States)

Wu, Liqiong; Li, Weiwei; Li, Peng; Liao, Shutian; Qiu, Shengqiang; Chen, Mingliang; Guo, Yufen; Li, Qi; Zhu, Chao; Liu, Liwei

2014-04-09

A facile and high-yield approach to the preparation of few-layer graphene (FLG) by electrochemical intercalation exfoliation (EIE) of expanded graphite in sulfuric acid electrolyte is reported. Stage-1 H2SO4-graphite intercalation compound is used as a key intermediate in EIE to realize the efficient exfoliation. The yield of the FLG sheets (papers made of the FLG flakes retain excellent conductivity (≈24,500 S m(-1)). Three-dimensional (3D) graphene foams with light weight are fabricated from the FLG flakes by the use of Ni foams as self-sacrifice templates. Furthermore, 3D graphene/Ni foams without any binders, which are used as supercapacitor electrodes in aqueous electrolyte, provide the specific capacitance of 113.2 F g(-1) at a current density of 0.5 A g(-1), retaining 90% capacitance after 1000 cycles. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Nickel-Tin Electrode Materials for Nonaqueous Li-Ion Cells

Science.gov (United States)

Ehrlich, Grant M.; Durand, Christopher

2005-01-01

Experimental materials made from mixtures of nickel and tin powders have shown promise for use as the negative electrodes of rechargeable lithium-ion electrochemical power cells. During charging (or discharging) of a lithium-ion cell, lithium ions are absorbed into (or desorbed from, respectively) the negative electrode, typically through an intercalation or alloying process. The negative electrodes (for this purpose, designated as anodes) in state-of-the-art Li-ion cells are made of graphite, in which intercalation occurs. Alternatively, the anodes can be made from metals, in which alloying can occur. For reasons having to do with the electrochemical potential of intercalated lithium, metallic anode materials (especially materials containing tin) are regarded as safer than graphite ones; in addition, such metallic anode materials have been investigated in the hope of obtaining reversible charge/discharge capacities greater than those of graphite anodes. However, until now, each of the tin-containing metallic anode formulations tested has been found to be inadequate in some respect.

Preparation of the electrochemically formed spinel-lithium manganese oxides

Energy Technology Data Exchange (ETDEWEB)

Katakura, Katsumi; Wada, Kohei; Kajiki, Yoshiyuki; Yamamoto, Akiko [Department of Chemical Engineering, Nara National College of Technology, 22 Yata-cho Yamotokoriyama, Nara 639-1080 (Japan); Ogumi, Zempachi [Graduate School of Engineering, Kyoto University, Nishikyo-ku, Kyoto 615-8510 (Japan)

2009-04-01

Electrochemically formed spinel-lithium manganese oxides were synthesized from manganese hydroxides prepared by a cathodic electrochemical precipitation from various concentrations of manganese nitrate solutions. Two types of manganese hydroxides were formed from diluted and concentrated Mn(NO{sub 3}){sub 2} aqueous solutions. Uniform and equi-sized disk shaped Mn(OH){sub 2} crystals of 0.2-5 {mu}m in diameter were obtained on a Pt substrate after the electrochemical precipitation from lower concentration of ranging from 2 mmol dm{sup -3} to 2 mol dm{sup -3} Mn(NO{sub 3}){sub 2} aq., while the grass blade-like precipitate which is ascribed to manganese hydroxide with 20-80 {mu}m long and 1-5 {mu}m wide were formed from concentrated Mn(NO{sub 3}){sub 2} aq. Both manganese hydroxides gave the electrochemically formed spinel-LiMn{sub 2}O{sub 4} onto a Pt sheet, which is ready for electrochemical measurement, after calcination of the Li incorporated precipitate at 750 C without any additives. While the shape and size of the secondary particle frameworks (aggregates) of the electrochemically formed spinel-LiMn{sub 2}O{sub 4} can be controlled by the electrolysis conditions, the nanostructured primary crystals of 200 nm in diameter were obtained in all cases except that the fiber-like nanostructured spinel-LiMn{sub 2}O{sub 4} crystals with 200 nm in diameter were obtained from concentrated Mn(NO{sub 3}){sub 2} aq. Though these two types of electrochemically formed spinel-LiMn{sub 2}O{sub 4} showed well-shaped CVs even in higher scan rates, it would be suitable for high power density battery applications. These behaviors are assumed to be ascribed to the crystal size and shape of the processed spinel-LiMn{sub 2}O{sub 4}. (author)

Report on Contract W911NF-05-1-0339 (Clarkson University)

Science.gov (United States)

2012-11-30

2012 59.00 Josiah Jebaraj J. Muthuraj, Don H. Rasmussen, Ian I. Suni. Electrodeposition of CuGaSe[sub 2] from Thiocyanate-Containing Electrolytes...Roy. Kinetic aspects of Li intercalation in mechano-chemically processed cathode materials for lithium ion batteries: Electrochemical characterization...Dipankar Roy. Electrochemical features of ball-milled lithium manganate spinel for rapid-charge cathodes of lithium ion batteries, Journal of Solid State

Graphene-based Electrochemical Energy Conversion and Storage: Fuel cells, Supercapacitors and Lithium Ion Batteries

Energy Technology Data Exchange (ETDEWEB)

Hou, Junbo; Shao, Yuyan; Ellis, Michael A.; Moore, Robert; Yi, Baolian

2011-09-14

Graphene has attracted extensive research interest due to its strictly 2-dimensional (2D) structure, which results in its unique electronic, thermal, mechanical, and chemical properties and potential technical applications. These remarkable characteristics of graphene, along with the inherent benefits of a carbon material, make it a promising candidate for application in electrochemical energy devices. This article reviews the methods of graphene preparation, introduces the unique electrochemical behavior of graphene, and summarizes the recent research and development on graphene-based fuel cells, supercapacitors and lithium ion batteries. In addition, promising areas are identified for the future development of graphene-based materials in electrochemical energy conversion and storage systems.

The preparation and graphene surface coating NaTi_2(PO_4)_3 as cathode material for lithium ion batteries

International Nuclear Information System (INIS)

Li, Na; Wang, Yanping; Rao, Richuan; Dong, Xiongzi; Zhang, Xianwen; Zhu, Sane

2017-01-01

Graphical abstract: The NaTi_2(PO_4)_3/graphene composite is used directly as cathode electrode material for lithium-ion battery by using metal lithium as an anode electrode. Meanwhile, the electrochemical properties of the composite in this system is firstly studied in detail. The NaTi_2(PO_4)_3/graphene composite exhibits the better rate and cyclic performance than NaTi_2(PO_4)_3, which is ascribed to its stable 3-D framework and the enhanced electronic conduction resulting from the graphene sheets surface modification. - Highlights: • The graphene coated NaTi_2(PO_4)_3 was prepared by a simple sol-gel method followed by calcination. • The electrochemical properties of the NaTi_2(PO_4)_3/graphene composite was firstly studied in detail when used as cathode electrode material for lithium-ion batteries. • The electrochemical reaction mechanism of NaTi_2(PO_4)_3/graphene composite was investigated by ex situ XRD. - Abstract: The graphene coated NaTi_2(PO_4)_3 has been fabricated via a simple sol-gel process followed by calcination. The NaTi_2(PO_4)_3/graphene (NTP/G) composite is used directly as cathode electrode material for lithium-ion battery and the electrochemical properties of the composite in this system is firstly studied in detail. In the charge-discharge process, two Li"+ can occupy octahedral M (2) site and be reversibly intercalated into the 3D framework of NTP through the ion conduction channel where almost all of Na"+ are immobilized to sustain the framework. At 5C rate, the capacity retention of the NTP/G composite after 800 cycles is still up to 82.7%. The superior electrochemical properties of NTP/G is ascribed to its stable 3-D framework and the enhanced electronic conduction resulting from the graphene sheets surface modification.

High performance lithium insertion negative electrode materials for electrochemical devices

Energy Technology Data Exchange (ETDEWEB)

Channu, V.S. Reddy, E-mail: chinares02@gmail.com [SMC Corporation, College Station, TX 77845 (United States); Rambabu, B. [Solid State Ionics and Surface Sciences Lab, Department of Physics, Southern University and A& M College, Baton Rouge, LA 70813 (United States); Kumari, Kusum [Department of Physics, National Institute of Technology, Warangal (India); Kalluru, Rajmohan R. [The University of Southern Mississippi, College of Science and Technology, 730 E Beach Blvd, Long Beach, MS 39560 (United States); Holze, Rudolf [Institut für Chemie, AG Elektrochemie, Technische Universität Chemnitz, D-09107 Chemnitz (Germany)

2016-11-30

Highlights: • LiCrTiO{sub 4} nanostructures were synthesized for electrochemical applications by soft chemical synthesis followed by annealing. • The presence of Cr and Ti elements are confirmed from the EDS spectrum. • Oxalic acid assisted LiCrTiO{sub 4} electrode shows higher specific capacity (mAh/g). - Abstract: Spinel LiCrTiO{sub 4} oxides to be used as electrode materials for a lithium ion battery and an asymmetric supercapacitor were synthesized using a soft-chemical method with and without chelating agents followed by calcination at 700 °C for 10 h. Structural and morphological properties were studied with powder X-ray diffraction, scanning electron and transmission electron microscopy. Particles of 50–10 nm in size are observed in the microscopic images. The presence of Cr and Ti is confirmed from the EDS spectrum. Electrochemical properties of LiCrTiO{sub 4} electrode were examined in a lithium ion battery. The electrode prepared with oxalic acid-assisted LiCrTiO{sub 4} shows higher specific capacity.This LiCrTiO{sub 4} is also used as anode material for an asymmetric hybrid supercapacitor. The cell exhibits a specific capacity of 65 mAh/g at 1 mA/cm{sup 2}. The specific capacity decreases with increasing current densities.

Electrochemical characterization of silicon/graphene/MWCNT hybrid lithium-ion battery anodes produced via RF magnetron sputtering

Energy Technology Data Exchange (ETDEWEB)

Toçoğlu, Ubeyd, E-mail: utocoglu@sakarya.edu.tr; Hatipoğlu, Gizem; Alaf, Miraç; Kayış, Fuat; Akbulut, Hatem

2016-12-15

Graphical abstract: Silicon/graphene/MWCNT hybrid composite anodes were produced via RF magnetron sputtering technique. CR2016 type coin cells were assembled for electrochemical characterization of anodes. Electrochemical characterizations of anodes were conducted via galvanostatic charge/discharge, cyclic voltammetry and electrochemical impedance spectroscopy techniques. - Highlights: • Silicon/graphene/MWCNT hybrid negative lithium ion battery anodes were produced via magnetron sputtering. • Structural and electrochemical characterizations of composite anodes were conducted comprehensively. • The capacity values exhibited by composite anodes were found to be almost more than two times compared to thin film anodes after 100 cycles. - Abstract: In this study it was aimed to enhance cycling performance of silicon lithium ion battery anodes via producing flexible Silicon/Graphene/MWCNT composite structures. The volumetric expansions, which are the primary obstacle that hinders the practical usage of silicon anodes, were tried to suppress using flexible graphene/MWCNT paper substrates. Moreover to achieve lightweight and high electrical conductive anodes, the advantage of graphene was aimed to be exploited. Silicon/graphene/MWCNT flexible composite anodes were produced via radio frequency (RF) magnetron sputtering technique. Graphene/MWCNT papers were produced with vacuum filtration technique as substrate for sputtering process. At coating process of papers constant sputtering power was applied. Phase analysis was conducted with X-ray diffraction (XRD) technique and Raman spectroscopy. Field emission scanning electron microscopy (FESEM). Cyclic voltammetry (CV) tests were carried out to reveal reversible reactions between silicon and lithium. Galvanostatic charge/discharge technique was employed to determine the cyclic performance of anodes. Electrochemical impedance spectroscopy technique was used to understand the relation between cyclic performance and

Electrochemical characterization of silicon/graphene/MWCNT hybrid lithium-ion battery anodes produced via RF magnetron sputtering

International Nuclear Information System (INIS)

Toçoğlu, Ubeyd; Hatipoğlu, Gizem; Alaf, Miraç; Kayış, Fuat; Akbulut, Hatem

2016-01-01

Graphical abstract: Silicon/graphene/MWCNT hybrid composite anodes were produced via RF magnetron sputtering technique. CR2016 type coin cells were assembled for electrochemical characterization of anodes. Electrochemical characterizations of anodes were conducted via galvanostatic charge/discharge, cyclic voltammetry and electrochemical impedance spectroscopy techniques. - Highlights: • Silicon/graphene/MWCNT hybrid negative lithium ion battery anodes were produced via magnetron sputtering. • Structural and electrochemical characterizations of composite anodes were conducted comprehensively. • The capacity values exhibited by composite anodes were found to be almost more than two times compared to thin film anodes after 100 cycles. - Abstract: In this study it was aimed to enhance cycling performance of silicon lithium ion battery anodes via producing flexible Silicon/Graphene/MWCNT composite structures. The volumetric expansions, which are the primary obstacle that hinders the practical usage of silicon anodes, were tried to suppress using flexible graphene/MWCNT paper substrates. Moreover to achieve lightweight and high electrical conductive anodes, the advantage of graphene was aimed to be exploited. Silicon/graphene/MWCNT flexible composite anodes were produced via radio frequency (RF) magnetron sputtering technique. Graphene/MWCNT papers were produced with vacuum filtration technique as substrate for sputtering process. At coating process of papers constant sputtering power was applied. Phase analysis was conducted with X-ray diffraction (XRD) technique and Raman spectroscopy. Field emission scanning electron microscopy (FESEM). Cyclic voltammetry (CV) tests were carried out to reveal reversible reactions between silicon and lithium. Galvanostatic charge/discharge technique was employed to determine the cyclic performance of anodes. Electrochemical impedance spectroscopy technique was used to understand the relation between cyclic performance and

Mesoporous amorphous tungsten oxide electrochromic films: a Raman analysis of their good switching behavior

International Nuclear Information System (INIS)

Chatzikyriakou, Dafni; Krins, Natacha; Gilbert, Bernard; Colson, Pierre; Dewalque, Jennifer; Denayer, Jessica; Cloots, Rudi; Henrist, Catherine

2014-01-01

Graphical abstract: - Highlights: • Mesoporous films exhibit better electrochemical kinetics compared to the dense films. • Mesoporous films exhibit better reversibility compared to the dense films. • Li + cations disrupt WO 3 network in a reversible way in the mesoporous film. • Li + irreversibly intercalate in the voids of crystallites in the dense film. - Abstract: The intercalation and de-intercalation of lithium cations in electrochromic tungsten oxide thin films are significantly influenced by their structural and surface characteristics. In this study, we prepared two types of amorphous films via the sol-gel technique: one dense and one mesoporous in order to compare their response upon lithium intercalation and de-intercalation. According to chronoamperometric measurements, Li + intercalates/de-intercalates faster in the mesoporous film (24s/6s) than in the dense film (48s/10s). The electrochemical measurements (cyclic voltammetry and chronoamperometry) also showed worse reversibility for the dense film compared to the mesoporous film, giving rise to important Li + trapping and remaining coloration of the film. Raman analysis showed that the mesoporous film provides more accessible and various W-O surface bonds for Li + intercalation. On the contrary, in the first electrochemical insertion and de-insertion in the dense film, Li + selectively reacts with a few surface W-O bonds and preferentially intercalates into pre-existing crystallites to form stable irreversible Li x WO 3 bronze

Eco-friendly preparation of large-sized graphene via short-circuit discharge of lithium primary battery.

Science.gov (United States)

Kang, Shaohong; Yu, Tao; Liu, Tingting; Guan, Shiyou

2018-02-15

We proposed a large-sized graphene preparation method by short-circuit discharge of the lithium-graphite primary battery for the first time. LiC x is obtained through lithium ions intercalation into graphite cathode in the above primary battery. Graphene was acquired by chemical reaction between LiC x and stripper agents with dispersion under sonication conditions. The gained graphene is characterized by Raman spectrum, X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), Atomic force microscope (AFM) and Scanning electron microscopy (SEM). The results indicate that the as-prepared graphene has a large size and few defects, and it is monolayer or less than three layers. The quality of graphene is significant improved compared to the reported electrochemical methods. The yield of graphene can reach 8.76% when the ratio of the H 2 O and NMP is 3:7. This method provides a potential solution for the recycling of waste lithium ion batteries. Copyright © 2017 Elsevier Inc. All rights reserved.

Nanosized CoO Loaded on Copper Foam for High-Performance, Binder-Free Lithium-Ion Batteries.

Science.gov (United States)

Liao, Mingna; Zhang, Qilun; Tang, Fengling; Xu, Zhiwei; Zhou, Xin; Li, Youpeng; Zhang, Yali; Yang, Chenghao; Ru, Qiang; Zhao, Lingzhi

2018-03-22

The synthesis of nanosized CoO anodes with unique morphologies via a hydrothermal method is investigated. By adjusting the pH values of reaction solutions, nanoflakes (CoO-NFs) and nanoflowers (CoO-FLs) are successfully located on copper foam. Compared with CoO-FLs, CoO-NFs as anodes for lithium ion batteries present ameliorated lithium storage properties, such as good rate capability, excellent cycling stability, and large CoO nanoflakes; CoO nanoflowers; anodes; binder free; lithium ion batteriesreversible capacity. The initial discharge capacity is 1470 mA h g -1 , while the reversible capacity is maintained at 1776 m Ah g -1 after 80 cycles at a current density of 100 mA h g -1 . The excellent electrochemical performance is ascribed to enough free space and enhanced conductivity, which play crucial roles in facilitating electron transport during repetitive Li⁺ intercalation and extraction reaction as well as buffering the volume expansion.

Nanosized CoO Loaded on Copper Foam for High-Performance, Binder-Free Lithium-Ion Batteries

Directory of Open Access Journals (Sweden)

Mingna Liao

2018-03-01

Full Text Available The synthesis of nanosized CoO anodes with unique morphologies via a hydrothermal method is investigated. By adjusting the pH values of reaction solutions, nanoflakes (CoO-NFs and nanoflowers (CoO-FLs are successfully located on copper foam. Compared with CoO-FLs, CoO-NFs as anodes for lithium ion batteries present ameliorated lithium storage properties, such as good rate capability, excellent cycling stability, and large CoO nanoflakes; CoO nanoflowers; anodes; binder free; lithium ion batteriesreversible capacity. The initial discharge capacity is 1470 mA h g−1, while the reversible capacity is maintained at 1776 m Ah g−1 after 80 cycles at a current density of 100 mA h g−1. The excellent electrochemical performance is ascribed to enough free space and enhanced conductivity, which play crucial roles in facilitating electron transport during repetitive Li+ intercalation and extraction reaction as well as buffering the volume expansion.

Diode laser heat treatment of lithium manganese oxide films

International Nuclear Information System (INIS)

Pröll, J.; Kohler, R.; Mangang, A.; Ulrich, S.; Bruns, M.; Seifert, H.J.; Pfleging, W.

2012-01-01

The crystallization of lithium manganese oxide thin films prepared by radio frequency magnetron sputtering on stainless steel substrates under 10 Pa argon pressure is demonstrated by a laser annealing technique. Laser annealing processes were developed as a function of annealing time and temperature with the objective to form an electrochemically active lithium manganese oxide cathode. It is demonstrated, that laser annealing with 940 nm diode laser radiation and an annealing time of 2000 s at 600 °C delivers appropriate parameters for formation of a crystalline spinel-like phase. Characteristic features of this phase could be detected via Raman spectroscopy, showing the characteristic main Raman band at 627 cm -1 . Within cyclic voltammetric measurements, the two characteristic redox pairs for spinel lithium manganese oxide in the 4 V region could be detected, indicating that the film was well-crystallized and de-/intercalation processes were reversible. Raman post-analysis of a cycled cathode showed that the spinel-like structure was preserved within the cycling process but mechanical degradation effects such as film cracking were observed via scanning electron microscopy. Typical features for the formation of an additional surface reaction layer could be detected using X-ray photoelectron spectroscopy.

Suppressing propylene carbonate decomposition by coating graphite electrode foil with silver

International Nuclear Information System (INIS)

Gao, J.; Zhang, H.P.; Fu, L.J.; Zhang, T.; Wu, Y.P.; Takamura, T.; Wu, H.Q.; Holze, R.

2007-01-01

A method has been developed to suppress the decomposition of propylene carbonate (PC) by coating graphite electrode foil with a layer of silver. Results from electrochemical impedance measurements show that the Ag-coated graphite electrode presents lower charge transfer resistance and faster diffusion of lithium ions in comparison with the virginal one. Cyclic voltammograms and discharge-charge measurements suggest that the decomposition of propylene carbonate and co-intercalation of solvated lithium ions are prevented, and lithium ions can reversibly intercalate into and deintercalate from the Ag-coated graphite electrode. These results indicate that Ag-coating is a good way to improve the electrochemical performance of graphitic carbon in PC-based electrolyte solutions

Effects of synthetic parameters on structure and electrochemical performance of spinel lithium manganese oxide by citric acid-assisted sol-gel method

International Nuclear Information System (INIS)

Yi Tingfeng; Dai Changsong; Gao Kun; Hu Xinguo

2006-01-01

The spinel lithium manganese oxide cathode materials were prepared by citric acid-assisted sol-gel method at 623-1073 K in air. The effects of pH value, raw material, synthesis temperature and time on structure and electrochemical performance of spinel lithium manganese oxide are investigated by X-ray diffraction (XRD), scanning electronic microscope (SEM) and cyclic voltammetry (CV). XRD data results strongly suggest that the synthesis temperature is the dominating factors of the formation of spinel phase, and spinel lithium manganese oxide powder with various crystallites size can be obtained by controlling the sintering time. CV shows that spinel lithium manganese oxide powder formed about 973 K presents the best electrochemical performance with well separated two peaks and the highest peak current. Charge-discharge test indicates that spinel lithium manganese oxide powders calcined at higher temperatures have high discharge capacity and capacity loss, and sintered at lower temperatures has low discharge capacity and high capacity retention

Effects of synthetic parameters on structure and electrochemical performance of spinel lithium manganese oxide by citric acid-assisted sol-gel method

Energy Technology Data Exchange (ETDEWEB)

Yi Tingfeng [Department of Applied Chemistry, Harbin Institute of Technology, Harbin 150001 (China)]. E-mail: tfyihit@hit.edu.cn; Dai Changsong [Department of Applied Chemistry, Harbin Institute of Technology, Harbin 150001 (China); Gao Kun [Department of Applied Chemistry, Harbin Institute of Technology, Harbin 150001 (China); Hu Xinguo [Department of Applied Chemistry, Harbin Institute of Technology, Harbin 150001 (China)

2006-11-30

The spinel lithium manganese oxide cathode materials were prepared by citric acid-assisted sol-gel method at 623-1073 K in air. The effects of pH value, raw material, synthesis temperature and time on structure and electrochemical performance of spinel lithium manganese oxide are investigated by X-ray diffraction (XRD), scanning electronic microscope (SEM) and cyclic voltammetry (CV). XRD data results strongly suggest that the synthesis temperature is the dominating factors of the formation of spinel phase, and spinel lithium manganese oxide powder with various crystallites size can be obtained by controlling the sintering time. CV shows that spinel lithium manganese oxide powder formed about 973 K presents the best electrochemical performance with well separated two peaks and the highest peak current. Charge-discharge test indicates that spinel lithium manganese oxide powders calcined at higher temperatures have high discharge capacity and capacity loss, and sintered at lower temperatures has low discharge capacity and high capacity retention.

Effect of pore structure on anomalous behaviour of the lithium intercalation into porous V2O5 film electrode using fractal geometry concept

International Nuclear Information System (INIS)

Jung, Kyu-Nam; Pyun, Su-Il

2006-01-01

The effect of pore structure on anomalous behaviour of the lithium intercalation into porous V 2 O 5 film electrode has been investigated in terms of fractal geometry by employing ac-impedance spectroscopy combined with N 2 gas adsorption method and atomic force microscopy (AFM). For this purpose, porous V 2 O 5 film electrodes with different pore structures were prepared by the polymer surfactant templating method. From the analysis of N 2 gas adsorption isotherms and the triangulation analysis of AFM images, it was found that porous V 2 O 5 surfaces exhibited self-similar scaling properties with different fractal dimensions depending upon amount of the polymer surfactant in solution and the spatial cut-off ranges. All the ac-impedance spectra measured on porous V 2 O 5 film electrodes showed the non-ideal behaviour of the charge-transfer reaction and the diffusion reaction, which resulted from the interfacial capacitance dispersion and the frequency dispersion of the diffusion impedance, respectively. From the comparison between the surface fractal dimensions by using N 2 gas adsorption method and AFM, and the analysis of ac-impedance spectra by employing a constant phase element (CPE), it is experimentally confirmed that the lithium intercalation into porous V 2 O 5 film electrode is crucially influenced by the pore surface irregularity and the film surface irregularity

An in situ Raman study of the intercalation of supercapacitor-type electrolyte into microcrystalline graphite

International Nuclear Information System (INIS)

Hardwick, Laurence J.; Hahn, Matthias; Ruch, Patrick; Holzapfel, Michael; Scheifele, Werner; Buqa, Hilmi; Krumeich, Frank; Novak, Petr; Koetz, Ruediger

2006-01-01

An initial Raman study on the effects of intercalation for aprotic electrolyte-based electrochemical double-layer capacitors (EDLCs) is reported. In situ Raman microscopy is employed in the study of the electrochemical intercalation of tetraethylammonium (Et 4 N + ) and tetrafluoroborate (BF 4 - ) into and out of microcrystalline graphite. During cyclic voltammetry experiments, the insertion of Et 4 N + into graphite for the negative electrode occurs at an onset potential of +1.0 V versus Li/Li + . For the positive electrode, BF 4 - was shown to intercalate above +4.3 V versus Li/Li + . The characteristic G-band doublet peak (E 2g2 (i) (1578 cm -1 ) and E 2g2 (b) (1600 cm -1 )) showed that various staged compounds were formed in both cases and the return of the single G-band (1578 cm -1 ) demonstrates that intercalation was fully reversible. The disappearance of the D-band (1329 cm -1 ) in intercalated graphite is also noted and when the intercalant is removed a more intense D-band reappears, indicating possible lattice damage. For cation intercalation, such irreversible changes of the graphite structure are confirmed by scanning electron microscopy (SEM)

The investigation on electrochemical reaction mechanism of CuF2 thin film with lithium

International Nuclear Information System (INIS)

Cui Yanhua; Xue Mingzhe; Zhou Yongning; Peng Shuming; Wang Xiaolin; Fu Zhengwen

2011-01-01

Crystalline CuF 2 thin films were prepared by pulsed laser deposition under room temperature. The physical and electrochemical properties of the as-deposited thin films have been investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), galvanostatic cycling and cyclic voltammetry (CV). Reversible capacity of 544 mAh g -1 was achieved in the potential range of 1.0-4.0 V. A reversible couple of redox peaks at 3.0 V and 3.7 V was firstly observed. By using ex situ XRD and TEM techniques, an insertion process followed by a fully conversion reaction to Cu and LiF was revealed in the lithium electrochemical reaction of CuF 2 thin film electrode. The reversible insertion reaction above 2.8 V could provide a capacity of about 125 mAh g -1 , which makes CuF 2 a potential cathode material for rechargeable lithium batteries.

The use of odd random phase electrochemical impedance spectroscopy to study lithium-based corrosion inhibition by active protective coatings

NARCIS (Netherlands)

Meeusen, M.; Visser, P.; Fernández Macía, L.; Hubin, A.; Terryn, H.A.; Mol, J.M.C.

2018-01-01

In this work, the study of the time-dependent behaviour of lithium carbonate based inhibitor technology for the active corrosion protection of aluminium alloy 2024-T3 is presented. Odd random phase electrochemical impedance spectroscopy (ORP-EIS) is selected as the electrochemical tool to study

Structural and electrochemical study of the reaction of lithium with silicon nanowires

KAUST Repository

Chan, Candace K.

2009-04-01

The structural transformations of silicon nanowires when cycled against lithium were evaluated using electrochemical potential spectroscopy and galvanostatic cycling. During the charge, the nanowires alloy with lithium to form an amorphous LixSi compound. At potentials <50 mV, a structural transformation occurs. In studies on micron-sized particles previously reported in the literature, this transformation is a crystallization to a metastable Li15Si4 phase. X-ray diffraction measurements on the Si nanowires, however, show that they are amorphous, suggesting that a different amorphous phase (LiySi) is formed. Lithium is removed from this phase in the discharge to form amorphous silicon. We have found that limiting the voltage in the charge to 70 mV results in improved efficiency and cyclability compared to charging to 10 mV. This improvement is due to the suppression of the transformation at low potentials, which alloys for reversible cycling of amorphous silicon nanowires. © 2008 Elsevier B.V. All rights reserved.

Study on the electrochemical of the metal deposition from ionic liquids for lithium, titanium and dysprosium

International Nuclear Information System (INIS)

Berger, Claudia A.

2017-01-01

The thesis was aimed to the characterization of electrochemically deposited film of lithium, titanium and dysprosium on Au(111) from different ionic liquids, finally dysprosium on neodymium-iron-boron magnate for industrial applications. The investigation of the deposits were performed using cyclic voltametry, in-situ scanning tunneling microscopy, electrochemical quartz microbalance, XPS and Auger electron spectroscopy. The sample preparation is described in detail. The deposition rate showed a significant temperature dependence.

Graphene-based electrochemical energy conversion and storage: fuel cells, supercapacitors and lithium ion batteries.

Science.gov (United States)

Hou, Junbo; Shao, Yuyan; Ellis, Michael W; Moore, Robert B; Yi, Baolian

2011-09-14

Graphene has attracted extensive research interest due to its strictly 2-dimensional (2D) structure, which results in its unique electronic, thermal, mechanical, and chemical properties and potential technical applications. These remarkable characteristics of graphene, along with the inherent benefits of a carbon material, make it a promising candidate for application in electrochemical energy devices. This article reviews the methods of graphene preparation, introduces the unique electrochemical behavior of graphene, and summarizes the recent research and development on graphene-based fuel cells, supercapacitors and lithium ion batteries. In addition, promising areas are identified for the future development of graphene-based materials in electrochemical energy conversion and storage systems. This journal is © the Owner Societies 2011

Lithium and sodium batteries with polysulfide electrolyte

KAUST Repository

Li, Mengliu; Ming, Jun; Li, Lain-Jong

2017-01-01

A battery comprising: at least one cathode, at least one anode, at least one battery separator, and at least one electrolyte disposed in the separator, wherein the anode is a lithium metal or lithium alloy anode or an anode adapted for intercalation

Electrochemical performances and capacity fading behaviors of activated carbon/hard carbon lithium ion capacitor

International Nuclear Information System (INIS)

Sun, Xianzhong; Zhang, Xiong; Liu, Wenjie; Wang, Kai; Li, Chen; Li, Zhao; Ma, Yanwei

2017-01-01

Highlights: • Three-electrode pouch cell is used to investigate the capacity fading of AC/HC LIC. • the electrode potential swing is critical for the cycleability of a LIC cell. • Different capacity fading behaviors are discussed. • A large-capacity LIC pouch cell has been assembled with a specific energy of 18.1 Wh kg −1 based on the total weight. - Abstract: Lithium ion capacitor (LIC) is one of the most promising electrochemical energy storage devices, which offers rapid charging-discharging capability and long cycle life. We have fabricated LIC pouch cells using an electrochemically-driven lithium pre-doping method through a three-electrode pouch cell structure. The active materials of cathode and anode of LIC cell are activated carbon and pre-lithiated hard carbon, respectively. The electrochemical performances and the capacity fading behaviors of LICs in the voltage range of 2.0 − 4.0 V have been studied. The specific energy and specific power reach 73.6 Wh kg −1 and 11.9 kW kg −1 based on the weight of the active materials in both cathode and anode, respectively. Since the cycling performance is actually determined by hard carbon anode, the anode potential swings are emphasized. The capacity fading of LIC upon cycling is proposed to be caused by the increases of internal resistance and the consumption of lithium stored in anode. Finally, a large-capacity LIC pouch cell has been assembled with a maximum specific energy of 18.1 Wh kg −1 and a maximum specific power of 3.7 kW kg −1 based on the weight of the whole cell.

The effects of electrode thickness on the electrochemical and thermal characteristics of lithium ion battery

International Nuclear Information System (INIS)

Zhao, Rui; Liu, Jie; Gu, Junjie

2015-01-01

Highlights: • A coupling model is developed to study the behaviors of Li-ion batteries. • Thick electrode battery (CEB) has high temperature response during discharge. • Thin electrode battery has a relative lower capacity fading rate. • Less heat is generated in thin electrode battery with even heat distribution. • CEBs underutilize active materials and stop discharge early at high rates. - Abstract: Lithium ion (Li-ion) battery, consisting of multiple electrochemical cells, is a complex system whose high electrochemical and thermal stability is often critical to the well-being and functional capabilities of electric devices. Considering any change in the specifications may significantly affect the overall performance and life of a battery, an investigation on the impacts of electrode thickness on the electrochemical and thermal properties of lithium-ion battery cells based on experiments and a coupling model composed of a 1D electrochemical model and a 3D thermal model is conducted in this work. In-depth analyses on the basis of the experimental and simulated results are carried out for one cell of different depths of discharge as well as for a set of cells with different electrode thicknesses. Pertinent results have demonstrated that the electrode thickness can significantly influence the battery from many key aspects such as energy density, temperature response, capacity fading rate, overall heat generation, distribution and proportion of heat sources

An Insoluble Benzoquinone-Based Organic Cathode for Use in Rechargeable Lithium-Ion Batteries.

Science.gov (United States)

Luo, Zhiqiang; Liu, Luojia; Zhao, Qing; Li, Fujun; Chen, Jun

2017-10-02

Application of organic electrode materials in rechargeable batteries has attracted great interest because such materials contain abundant carbon, hydrogen, and oxygen elements. However, organic electrodes are highly soluble in organic electrolytes. An organic electrode of 2,3,5,6-tetraphthalimido-1,4-benzoquinone (TPB) is reported in which rigid groups coordinate to a molecular benzoquinone skeleton. The material is insoluble in aprotic electrolyte, and demonstrates a high capacity retention of 91.4 % (204 mA h g -1 ) over 100 cycles at 0.2 C. The extended π-conjugation of the material contributes to enhancement of the electrochemical performance (155 mA h g -1 at 10 C). Moreover, density functional theory calculations suggest that favorable synergistic reactions between multiple carbonyl groups and lithium ions can enhance the initial lithium ion intercalation potential. The described approach may provide a novel entry to next-generation organic electrode materials with relevance to lithium-ion batteries. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Enhanced electrochemical properties of LiFePO4 (LFP) cathode using the carboxymethyl cellulose lithium (CMC-Li) as novel binder in lithium-ion battery.

Science.gov (United States)

Qiu, Lei; Shao, Ziqiang; Wang, Daxiong; Wang, Wenjun; Wang, Feijun; Wang, Jianquan

2014-10-13

Novel water-based binder CMC-Li is synthesized using cotton as raw material. The mechanism of the CMC-Li as a binder is reported. Electrochemical properties of batteries cathodes based on commercially available lithium iron phosphate (LiFePO4, LFP) and CMC-Li as a water-soluble binder are investigated. CMC-Li is a novel lithium-ion binder. Compare with conventional poly(vinylidene fluoride) (PVDF) binder, and the battery with CMC-Li as the binder retained 97.8% of initial reversible capacity after 200 cycles at 176 mAh g(-1), which is beyond the theoretical specific capacity of LFP. Constant current charge-discharge test results demonstrate that the LFP electrode using CMC-Li as the binder has the highest rate capability, follow closely by that using PVDF binder. The batteries have good electrochemical property, outstanding pollution-free and excellent stability. Copyright © 2014 Elsevier Ltd. All rights reserved.

Behavior of the monophosphate tungsten bronzes (PO2)4(WO3)2m (m = 7 and 8) in the course of electrochemical lithium insertion

International Nuclear Information System (INIS)

Martinez-de la Cruz, A.; Longoria Rodriguez, F.E.; Gonzalez, Lucy T.; Torres-Martinez, Leticia M.

2007-01-01

The electrochemical lithium insertion process has been studied in the family of monophosphate tungsten bronzes (PO 2 ) 4 (WO 3 ) 2m , where m = 7 and 8. Structural changes in the pristine oxides were followed as lithium insertion proceeded. Through potentiostatic intermittent technique the different processes which take place in the cathode during the discharge of the cell were analyzed. The nature of the bronzes Li x (PO 2 ) 4 (WO 3 ) 2m formed was determined by in situ X-ray diffraction experiments. These results have allowed establishing a correlation with the reversible/irreversible processes detected during the electrochemical lithium insertion

Temperature dependence of electrochemical properties of cross-linked poly(ethylene oxide)–lithium bis(trifluoromethanesulfonyl)imide–N-butyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide solid polymer electrolytes for lithium batteries

International Nuclear Information System (INIS)

Wetjen, Morten; Kim, Guk-Tae; Joost, Mario; Winter, Martin; Passerini, Stefano

2013-01-01

Highlights: ► Solid-state electrolyte for lithium batteries. ► Polymer electrolyte with improved mechanical properties by cross-linking. ► Enhanced performance of polymer electrolytes using water- and air-stable ionic liquids as co-salts. ► Polymer electrolyte with high rate capability at moderate temperatures. - Abstract: An advanced electrochemical characterization of cross-linked ternary solid polymer electrolytes (SPEs), prepared by a solvent-free hot-pressing process, is reported. Ionic conductivity, electrochemical stability window and limiting current measurements were performed as a function of the temperature by using both potentiodynamic and galvanostatic techniques. Additionally, the lithium cycleability was evaluated with respect to its dependence on both the operating temperature and the current density by using a new multi-rate Li-stripping-plating procedure. The results clearly indicate the beneficial effect of higher operating temperatures on the rate-capability, without major degradation of the electrochemical stability of the SPE. All-solid-state lithium metal polymer batteries (LMPBs), comprising a lithium metal anode, the cross-linked ternary solid polymer electrolyte and a LiFePO 4 composite cathode, were manufactured and investigated in terms of the interdependencies of the delivered capacity, operating temperature and discharge rate. The results prove quite exceptional delivered capacities both at medium current densities at ambient temperatures and even more impressive capacities above 160 mAh g −1 at high discharge rates (1 C) and temperatures above 60 °C.

Improved Electrochemical Performance of Biomass-Derived Nanoporous Carbon/Sulfur Composites Cathode for Lithium-Sulfur Batteries by Nitrogen Doping

International Nuclear Information System (INIS)

Geng, Zhen; Xiao, Qiangfeng; Wang, Dabin; Yi, Guanghai; Xu, Zhigang; Li, Bing; Zhang, Cunman

2016-01-01

A two-step method with high-efficiency is developed to prepare nitrogen doped activated carbons (NACs) with high surface area and nitrogen content. Based on the method, series of NACs with similar surface area and pore texture but different nitrogen content and nitrogen group species are successfully prepared. The influence of nitrogen doping on electrochemical performance of carbon/sulfur composites cathode is studied deeply under the conditions of similar surface area and pore texture. It presents the directly experimental demonstration that both nitrogen content and nitrogen group species play crucial roles on electrochemical performance of carbon/sulfur composites cathode. NAC/sulfur composites show the much improved cycling performance, which is about 3.5 times as that of nitrogen free carbon. Improved electrochemical performance is due to synergistic effects between nitrogen content and effective nitrogen groups, which enables effective trapping of lithium polysulfides within carbon framework. Besides, it is found that oxygen groups exist in carbon materials obviously influence electrochemical performance of cathode, which could be ignored in most of studies. Based on above, it can be concluded that enhanced chemisorption to lithium polysulfides by functional groups modification is the effective route to improve the electrochemical performance of Li-S battery.

Chemical and electrochemical lithium insertion into ternary transition metal sulfides MMo[sub 2]S[sub 4] (M: V, Cr, Fe)

Energy Technology Data Exchange (ETDEWEB)

Maffi, S.; Peraldo Bicelli, L. (Milan Polytechnic (Italy). Dept. of Applied Physical Chemistry CNR, Milan (Italy). Research Centre on Electrode Processes); Barriga, C.; Lavela, P.; Morales, J.; Tirado, J.L. (Cordoba Univ. (Spain). Dept. de Quimica Inorganica e Ingenieria Quimica)

1992-08-01

The effects of lithium insertion in MMo[sub 2]S[sub 4] (M: V, Cr, Fe) have been studied by means of chemical and electrochemical insertion methods. The reaction has a topotactic character and a higher degree of lithium insertion was found for the compound FeMo[sub 2]S[sub 4] which has a greater unit cell volume. For this compound the changes in lattice parameters with lithium content are also more pronounced. The voltage composition curves show a smooth voltage decrease with a quasi-plateau located at around 1.3 V. For discharge at lithium content higher than 0.8, the voltage decreases quickly followed by an extended plateau below 1 V, a region where electrolyte decomposition may occur. The X-ray powder diffraction patterns of the electrochemical lithiated compounds show that the original monoclinic structure is maintained up to 0.8 e[sup -] per mole, buth with a significant change in the intensity of the peaks, indicative of an alteration of cation distribution for this degree of insertion. For high lithium content, such disorder promotes the collapse of the structure, resulting in the loss of long-range order of the material. (orig.).

Understanding Mn-Based Intercalation Cathodes from Thermodynamics and Kinetics

Directory of Open Access Journals (Sweden)

Yin Xie

2017-07-01

Full Text Available A series of Mn-based intercalation compounds have been applied as the cathode materials of Li-ion batteries, such as LiMn2O4, LiNi1−x−yCoxMnyO2, etc. With open structures, intercalation compounds exhibit a wide variety of thermodynamic and kinetic properties depending on their crystal structures, host chemistries, etc. Understanding these materials from thermodynamic and kinetic points of view can facilitate the exploration of cathodes with better electrochemical performances. This article reviews the current available thermodynamic and kinetic knowledge on Mn-based intercalation compounds, including the thermal stability, structural intrinsic features, involved redox couples, phase transformations as well as the electrical and ionic conductivity.

Microporous carbon derived from polyaniline base as anode material for lithium ion secondary battery

International Nuclear Information System (INIS)

Xiang, Xiaoxia; Liu, Enhui; Huang, Zhengzheng; Shen, Haijie; Tian, Yingying; Xiao, Chengyi; Yang, Jingjing; Mao, Zhaohui

2011-01-01

Highlights: → Nitrogen-containing microporous carbon was prepared from polyaniline base by K 2 CO 3 activation, and used as anode material for lithium ion secondary battery. → K 2 CO 3 activation promotes the formation of amorphous and microporous structure. → High nitrogen content, and large surface area with micropores lead to strong intercalation between carbon and lithium ion, and thus improve the lithium storage capacity. -- Abstract: Microporous carbon with large surface area was prepared from polyaniline base using K 2 CO 3 as an activating agent. The physicochemical properties of the carbon were characterized by scanning electron microscope, X-ray diffraction, Brunauer-Emmett-Teller, elemental analyses and X-ray photoelectron spectroscopy measurement. The electrochemical properties of the microporous carbon as anode material in lithium ion secondary battery were evaluated. The first discharge capacity of the microporous carbon was 1108 mAh g -1 , whose first charge capacity was 624 mAh g -1 , with a coulombic efficiency of 56.3%. After 20 cycling tests, the microporous carbon retains a reversible capacity of 603 mAh g -1 at a current density of 100 mA g -1 . These results clearly demonstrated the potential role of microporous carbon as anode for high capacity lithium ion secondary battery.

Uniform second Li ion intercalation in solid state ϵ-LiVOPO4

International Nuclear Information System (INIS)

Wangoh, Linda W.; Quackenbush, Nicholas F.; Sallis, Shawn; Wiaderek, Kamila M.; Ma, Lu; Wu, Tianpin; Chapman, Karena W.; Lin, Yuh-Chieh; Ong, Shyue Ping; Wen, Bohua; Chernova, Natasha A.; Whittingham, M. Stanley; Guo, Jinghua; Lee, Tien-Lin; Schlueter, Christoph; Piper, Louis F. J.

2016-01-01

Full, reversible intercalation of two Li + has not yet been achieved in promising VOPO 4 electrodes. A pronounced Li + gradient has been reported in the low voltage window (i.e., second lithium reaction) that is thought to originate from disrupted kinetics in the high voltage regime (i.e., first lithium reaction). Here, we employ a combination of hard and soft x–ray photoelectron and absorption spectroscopy techniques to depth profile solid state synthesized LiVOPO 4 cycled within the low voltage window only. Analysis of the vanadium environment revealed no evidence of a Li + gradient, which combined with almost full theoretical capacity confirms that disrupted kinetics in the high voltage window are responsible for hindering full two lithium insertion. Furthermore, we argue that the uniform Li + intercalation is a prerequisite for the formation of intermediate phases Li 1.50 VOPO 4 and Li 1.75 VOPO 4 . The evolution from LiVOPO 4 to Li 2 VOPO 4 via the intermediate phases is confirmed by direct comparison between O K–edge absorption spectroscopy and density functional theory.

Fracture of crystalline silicon nanopillars during electrochemical lithium insertion

KAUST Repository

Lee, S. W.

2012-02-27

From surface hardening of steels to doping of semiconductors, atom insertion in solids plays an important role in modifying chemical, physical, and electronic properties of materials for a variety of applications. High densities of atomic insertion in a solid can result in dramatic structural transformations and associated changes in mechanical behavior: This is particularly evident during electrochemical cycling of novel battery electrodes, such as alloying anodes, conversion oxides, and sulfur and oxygen cathodes. Silicon, which undergoes 400% volume expansion when alloying with lithium, is an extreme case and represents an excellent model system for study. Here, we show that fracture locations are highly anisotropic for lithiation of crystalline Si nanopillars and that fracture is strongly correlated with previously discovered anisotropic expansion. Contrary to earlier theoretical models based on diffusion-induced stresses where fracture is predicted to occur in the core of the pillars during lithiation, the observed cracks are present only in the amorphous lithiated shell. We also show that the critical fracture size is between about 240 and 360 nm and that it depends on the electrochemical reaction rate.

Electrochemically oxidized electronic and ionic conducting nanostructured block copolymers for lithium battery electrodes.

Science.gov (United States)

Patel, Shrayesh N; Javier, Anna E; Balsara, Nitash P

2013-07-23

Block copolymers that can simultaneously conduct electronic and ionic charges on the nanometer length scale can serve as innovative conductive binder material for solid-state battery electrodes. The purpose of this work is to study the electronic charge transport of poly(3-hexylthiophene)-b-poly(ethylene oxide) (P3HT-PEO) copolymers electrochemically oxidized with lithium bis(trifluoromethanesulfonyl) imide (LiTFSI) salt in the context of a lithium battery charge/discharge cycle. We use a solid-state three-terminal electrochemical cell that enables simultaneous conductivity measurements and control over electrochemical doping of P3HT. At low oxidation levels (ratio of moles of electrons removed to moles of 3-hexylthiophene moieties in the electrode), the electronic conductivity (σe,ox) increases from 10(-7) S/cm to 10(-4) S/cm. At high oxidation levels, σe,ox approaches 10(-2) S/cm. When P3HT-PEO is used as a conductive binder in a positive electrode with LiFePO4 active material, P3HT is electrochemically active within the voltage window of a charge/discharge cycle. The electronic conductivity of the P3HT-PEO binder is in the 10(-4) to 10(-2) S/cm range over most of the potential window of the charge/discharge cycle. This allows for efficient electronic conduction, and observed charge/discharge capacities approach the theoretical limit of LiFePO4. However, at the end of the discharge cycle, the electronic conductivity decreases sharply to 10(-7) S/cm, which means the "conductive" binder is now electronically insulating. The ability of our conductive binder to switch between electronically conducting and insulating states in the positive electrode provides an unprecedented route for automatic overdischarge protection in rechargeable batteries.

A molybdenum disulfide/reduced oxide-graphene nanoflakelet-on-sheet structure for lithium ion batteries

Energy Technology Data Exchange (ETDEWEB)

Wang, Jiayu; Zhao, Xianmin; Fu, Yongsheng, E-mail: fuyongsheng0925@163.com; Wang, Xin, E-mail: wangx@njust.edu.cn

2017-03-31

Highlights: • Graphene/MoS{sub 2} hybrid was successfully prepared via a facile solvothermal method. • A novel nanoflakelet-on-sheet morphology was obtained by controlling solvent. • The hybrid showed high capacity, excellent cycling stability and rate capability. • The synergistic effect remarkably improved electrochemical properties. - Abstract: A MoS{sub 2} nanoflakelet/graphene hybrid (MoS{sub 2}/G) is designed and successfully synthesized via a simple and cost-effective strategy. It is found that the MoS{sub 2}/G hybrids prepared using and without using ethanol (EtOH) show different morphologies and EtOH plays a crucial role in the formation of MoS{sub 2} nanoflakelets on graphene. The resulting nanoflakelet-on-sheet structure can be used as a high-performance anode material for lithium ion batteries, because it not only offers plenty of pores and pathways for lithium ions to shuttle back and forth, but also withstands lithium ion intercalation/de-intercalation process without collapse or deformation. The MoS{sub 2}/G hybrid synthesized in EtOH/H{sub 2}O exhibits remarkable reversible capacities of 1902 mAh g{sup −1} and 1454 mAh g{sup −1} in the first discharging and charging cycle, respectively, with a high coulombic efficiency of 76.45%. The hybrid also shows excellent cycle and rate performance. The superior Li storage performance of the MoS{sub 2}/G hybrid is mainly attributed to the intrinsic properties of MoS{sub 2} nanoflakelets and the synergistic effect of the MoS{sub 2} nanoflakelets and graphene.

Structural, physical and electrochemical characteristics of a vanadium oxysulfide, a cathode material for lithium batteries

Science.gov (United States)

Ouvrard, G.; Tchangbédji, G.; Deniard, P.; Prouzet, E.

A vanadium oxysulfide is obtained by a reaction between water solutions of a vanadyl salt and sodium sulfide at room temperature. After drying under mild conditions, the formulation of this phase is V 2O 3S·3H 2O. Thermogravimetric analyses show that it is not possible to remove completely water without losing sulfur. This is in agreement with proton nuclear magnetic resonance experiments which prove that water molecules are tightly bonded to vanadium. Magnetic susceptibility and X-ray absorption spectroscopy measurements allow to define the oxidation states of vanadium and sulfur, (IV) and (-II) respectively. From extended X-ray absorption fine structure spectroscopy at the vanadium K edge and infrared spectroscopy, the local structure around vanadium can be defined as a distorted octahedron, with a vanadyl bond and an opposite sulfur atom. Magnetic susceptibility and X-ray absorption spectroscopy measurements on chemically lithiated compounds show a complex charge transfer from lithium to the host structure upon lithium intercalation. If it appears that vanadium atoms are reduced, a possible role of sulfur atoms in the redox process has to be considered. Cycling tests of lithium batteries whose positive consists of oxysulfide are promising with 70 cycles under a regime of {C}/{8}, without noticeable loss in capacity of 120 Ah/kg.

Current status of environmental, health, and safety issues of lithium ion electric vehicle batteries

Energy Technology Data Exchange (ETDEWEB)

Vimmerstedt, L.J.; Ring, S.; Hammel, C.J.

1995-09-01

The lithium ion system considered in this report uses lithium intercalation compounds as both positive and negative electrodes and has an organic liquid electrolyte. Oxides of nickel, cobalt, and manganese are used in the positive electrode, and carbon is used in the negative electrode. This report presents health and safety issues, environmental issues, and shipping requirements for lithium ion electric vehicle (EV) batteries. A lithium-based electrochemical system can, in theory, achieve higher energy density than systems using other elements. The lithium ion system is less reactive and more reliable than present lithium metal systems and has possible performance advantages over some lithium solid polymer electrolyte batteries. However, the possibility of electrolyte spills could be a disadvantage of a liquid electrolyte system compared to a solid electrolyte. The lithium ion system is a developing technology, so there is some uncertainty regarding which materials will be used in an EV-sized battery. This report reviews the materials presented in the open literature within the context of health and safety issues, considering intrinsic material hazards, mitigation of material hazards, and safety testing. Some possible lithium ion battery materials are toxic, carcinogenic, or could undergo chemical reactions that produce hazardous heat or gases. Toxic materials include lithium compounds, nickel compounds, arsenic compounds, and dimethoxyethane. Carcinogenic materials include nickel compounds, arsenic compounds, and (possibly) cobalt compounds, copper, and polypropylene. Lithiated negative electrode materials could be reactive. However, because information about the exact compounds that will be used in future batteries is proprietary, ongoing research will determine which specific hazards will apply.

Thermo-electrochemical model for forced convection air cooling of a lithium-ion battery module

International Nuclear Information System (INIS)

Tong, Wei; Somasundaram, Karthik; Birgersson, Erik; Mujumdar, Arun S.; Yap, Christopher

2016-01-01

Highlights: • Coupled thermal-electrochemical model for a Li-ion battery module resolving every functional layer in all cells. • Parametric analysis of forced convection air cooling of Li-ion battery module with a detailed multi-scale model. • Reversing/reciprocating airflow for Li-ion battery module thermal management provides uniform temperature distribution. - Abstract: Thermal management is critical for safe and reliable operation of lithium-ion battery systems. In this study, a one-dimensional thermal-electrochemical model of lithium-ion battery interactively coupled with a two-dimensional thermal-fluid conjugate model for forced convection air cooling of a lithium-ion battery module is presented and solved numerically. This coupled approach makes the model more unique and detailed as transport inside each cell in the battery module is solved for and thus covering multiple length and time scales. The effect of certain design and operating parameters of the thermal management system on the performance of the battery module is assessed using the coupled model. It is found that a lower temperature increase of the battery module can be achieved by either increasing the inlet air velocity or decreasing the distance between the cells. Higher air inlet velocity, staggered cell arrangement or a periodic reversal airflow of high reversal frequency results in a more uniform temperature distribution in the module. However, doing so increases the parasitic load as well as the volume of the battery module whence a trade-off should be taken into account between these parameters.

Electrochemical characterization of electrolytes and electrodes for lithium-ion batteries. Development of a new measuring method for electrochemical investigations on electrodes with the electrochemical quartz crystal microbalance (EQCM); Elektrochemische Charakterisierung von Elektrolyten und Elektroden fuer Lithium-Ionen-Batterien. Entwicklung einer neuen Messmethode fuer elektrochemische Untersuchungen an Elektroden mit der EQCM

Energy Technology Data Exchange (ETDEWEB)

Moosbauer, Dominik Johann

2010-11-09

In this work the conductivities of four different lithium salts, LiPF6, LiBF4, LiDFOB, and LiBOB in the solvent mixture EC/DEC (3/7) were investigated. Furthermore, the influence of eight ionic liquids (ILs) as additives on the conductivity and electrochemical stability of lithium salt-based electrolytes was studied. The investigated salts were the well-known lithium LiPF6 and LiDFOB. Conductivity studies were performed over the temperature range (238.15 to 333.15) K. The electrochemical stabilities of the solutions were determined at aluminum electrodes. The salt solubility of LiBF4 and LiDFOB in EC/DEC (3/7) was measured with the quartz crystal microbalance (QCM), a method developed in our group. Moreover, a method to investigate interactions between the electrolyte and electrode components with the electrochemical quartz crystal microbalance (EQCM) was developed. First, investigations of corrosion and passivation effects on aluminum with different lithium salts were performed and masses of deposited products estimated. Therefore, the quartzes were specially prepared with foils. Active materials of cathodes, in this work lithium iron phosphate (LiFePO4), were also investigated with the EQCM by a new method. [German] In dieser Arbeit wurden die Leitfaehigkeiten von vier unterschiedlichen Salzen, LiPF6, LiBF4, LiDFOB und LiBOB in dem Loesemittelgemisch EC/DEC (3/7) untersucht. Des Weiteren wurde der Einfluss von acht Ionischen Fluessigkeiten (ILs) als Additive fuer Lithium-Elektrolyte auf die elektrochemische Stabilitaet und die Leitfaehigkeit studiert. Die untersuchten Salze waren LiPF6 und LiDFOB. Die Leitfaehigkeitsmessungen wurden in einem Temperaturbereich von (238,15 bis 333,15) K durchgefuehrt. Die elektrochemischen Stabilitaeten der Elektrolyte fanden an Aluminium statt. Mit einer an der Arbeitsgruppe entwickelten neuen Methode wurden zudem die Salzloeslichkeiten von LiBF4 und LiDFOB in EC/DEC (3/7) mit der Quarzmikrowaage (QCM) bestimmt. Weiterhin wurden

Significantly enhanced electrochemical performance of lithium titanate anode for lithium ion battery by the hybrid of nitrogen and sulfur co-doped graphene quantum dots

International Nuclear Information System (INIS)

Ruiyi, Li; Yuanyuan, Jiang; Xiaoyan, Zhou; Zaijun, Li; Zhiguo, Gu; Guangli, Wang; Junkang, Liu

2015-01-01

Graphical abstract: The study reported a facile synthesis of Li4Ti5O12/nitrogen and sulfur co-doped graphene quantum dots (LTO/N,S-GQDs). The unique architecture and the introduction of N,S-GQDs create both ultrafast electron transfer and electrolyte transport. The as-prepared LTO/N,S-GQDs anode provides prominent advantage of specific capacity, high-rate performance and cycle stability. - Highlights: • We reported a new lithium titanate/nitrogen and sulfur co-doped graphene quantum dots hybrid • The synthesis creates a crystalline interconnected porous framework composed of nanoscale LTO • The unique architecture achieves to maximize the rate performance and enhance the power density • Introduction of N,S-GQDs greatly enhances the electron transfer and the storage lithium capacity • The hybrid anode provides an excellent electrochemical performance for lithium-ion batteries - ABSTRACT: The paper reported a facile synthesis of lithium titanate/nitrogen and sulfur co-doped graphene quantum dots(LTO/N,S-GQDs). Tetrabutyl titanate was dissolved in tertbutanol and heated to refluxing state by microwave irradiation. Then, lithium acetate was added into the mixed solution to produce LTO precursor. The precursor was hybridized with N,S-GQDs in ethanol. Followed by drying and thermal annealing at 500 °C in Ar/H_2 to obtain LTO/N,S-GQDs. The synthesis creates fully crystalline interconnected porous framework composed of nanoscale LTO crystals. The unique architecture achieves to maximize the high-rate performance and enhance the power density. More importantly, the introduction of N,S-GQDs don't almost influence on the electrolyte transport, but greatly improve the electron transfer and the storage lithium capacity. The LTO/N,S-GQDs anode exhibits remarkably enhanced electrochemical performance for lithium ion battery. The specific discharge capacity is 254.2 mAh g"−"1 at 0.1C and 126.5 mAh g"−"1 at 10C. The capacity remains 96.9% at least after 2000 cycles

Non-isothermal electrochemical model for lithium-ion cells with composite cathodes

Science.gov (United States)

Basu, Suman; Patil, Rajkumar S.; Ramachandran, Sanoop; Hariharan, Krishnan S.; Kolake, Subramanya Mayya; Song, Taewon; Oh, Dukjin; Yeo, Taejung; Doo, Seokgwang

2015-06-01

Transition metal oxide cathodes for Li-ion batteries offer high energy density and high voltage. Composites of these materials have shown excellent life expectancy and improved thermal performance. In the present work, a comprehensive non-isothermal electrochemical model for a Lithium ion cell with a composite cathode is developed. The present work builds on lithium concentration-dependent diffusivity and thermal gradient of cathode potential, obtained from experiments. The model validation is performed for a wide range of temperature and discharge rates. Excellent agreement is found for high and room temperature with moderate success at low temperatures, which can be attributed to the low fidelity of material properties at low temperature. Although the cell operation is limited by electronic conductivity of NCA at room temperature, at low temperatures a shift in controlling process is seen, and operation is limited by electrolyte transport. At room temperature, the lithium transport in Cathode appears to be the main source of heat generation with entropic heat as the primary contributor at low discharge rates and ohmic heat at high discharge rates respectively. Improvement in electronic conductivity of the cathode is expected to improve the performance of these composite cathodes and pave way for its wider commercialization.

Results from a Novel Method for Corrosion Studies of Electroplated Lithium Metal Based on Measurements with an Impedance Scanning Electrochemical Quartz Crystal Microbalance

Directory of Open Access Journals (Sweden)

Martin Winter

2013-07-01

Full Text Available A new approach to study the chemical stability of electrodeposited lithium on a copper metal substrate via measurements with a fast impedance scanning electrochemical quartz crystal microbalance is presented. The corrosion of electrochemically deposited lithium was compared in two different electrolytes, based on lithium difluoro(oxalato borate (LiDFOB and lithium hexafluorophosphate, both salts being dissolved in solvent blends of ethylene carbonate and diethyl carbonate. For a better understanding of the corrosion mechanisms, scanning electron microscopy images of electrodeposited lithium were also consulted. The results of the EQCM experiments were supported by AC impedance measurements and clearly showed two different corrosion mechanisms caused by the different salts and the formed SEIs. The observed mass decrease of the quartz sensor of the LiDFOB-based electrolyte is not smooth, but rather composed of a series of abrupt mass fluctuations in contrast to that of the lithium hexafluorophosphate-based electrolyte. After each slow decrease of mass a rather fast increase of mass is observed several times. The slow mass decrease can be attributed to a consolidation process of the SEI or to the partial dissolution of the SEI leaving finally lithium metal unprotected so that a fast film formation sets in entailing the observed fast mass increases.

Coupled Mechanical and Electrochemical Phenomena in Lithium-Ion Batteries

Science.gov (United States)

Cannarella, John

Lithium-ion batteries are complee electro-chemo-mechanical systems owing to a number of coupled mechanical and electrochemical phenomena that occur during operation. In this thesis we explore these phenomena in the context of battery degradation, monitoring/diagnostics, and their application to novel energy systems. We begin by establishing the importance of bulk stress in lithium-ion batteries through the presentation of a two-year exploratory aging study which shows that bulk mechanical stress can significantly accelerate capacity fade. We then investigate the origins of this coupling between stress and performance by investigating the effects of stress in idealized systems. Mechanical stress is found to increase internal battery resistance through separator deformation, which we model by considering how deformation affects certain transport properties. When this deformation occurs in a spatially heterogeneous manner, local hot spots form, which accelerate aging and in some cases lead to local lithium plating. Because of the importance of separator deformation with respect to mechanically-coupled aging, we characterize the mechanical properties of battery separators in detail. We also demonstrate that the stress state of a lithium-ion battery cell can be used to measure the cell's state of health (SOH) and state of charge (SOC)--important operating parameters that are traditionally difficult to measure outside of a laboratory setting. The SOH is shown to be related to irreversible expansion that occurs with degradation and the SOC to the reversible strains characteristic of the cell's electrode materials. The expansion characteristics and mechanical properties of the constituent cell materials are characterized, and a phenomenological model for the relationship between stress and SOH/SOC is developed. This work forms the basis for the development of on-board monitoring of SOH/SOC based on mechanical measurements. Finally we study the coupling between mechanical

Controllable synthesis of porous LiFePO4 for tunable electrochemical Li-insertion performance

International Nuclear Information System (INIS)

Tian, Xiaohui; Zhou, Yingke; Wu, Guan; Wang, Pengcheng; Chen, Jian

2017-01-01

Highlights: • A templated freeze-drying method is developed to prepare the porous LiFePO 4 . • The pore size and porosity can be controlled by adjusting the conditions. • The effects of the porous properties on the Li-insertion performances are studied. • The optimized composite presents excellent specific capacity and rate capability. - Abstract: A templated freeze-drying method is developed to prepare the porous LiFePO 4 materials with the controlled pore size and porosity, by conveniently adjusting the size and content of the template in the precursor solution. The morphology and structure of the porous LiFePO 4 materials are characterized and the relavant electrochemical lithium-insertion performances are systematically studied. It’s found that the porous characteristics play a critical role in the lithium-ion intercalation processes and significantly affect the power capability of LiFePO 4 . The optimized porous LiFePO 4 material presents remarkable specific capacity (167 mAh g −1 at 0.1 C), rate capability (151 mAh g −1 at 1 C and 110 mAh g −1 at 10 C) and cycling stability (99.3% retention after 300 cycles at 1 C). These findings demonstrate that the electrochemical performance of the electrode material can be purposely tuned and remarkably improved by the rational design and introduction of the suitable pores, which open up new strategies for the synthesis of advanced porous materials for the lithium-ion power battery applications.

Effect of Nickel Coated Multi-Walled Carbon Nanotubes on Electrochemical Performance of Lithium-Sulfur Rechargeable Batteries.

Science.gov (United States)

Wu, Xiao; Yao, Shanshan; Hou, Jinli; Jing, Maoxiang; Qian, Xinye; Shen, Xiangqian; Xiang, Jun; Xi, Xiaoming

2017-04-01

Conventional lithium-sulfur batteries suffer from severe capacity fade, which is induced by low electron conductivity and high dissolution of intermediated polysulfides. Recent studies have shown the metal (Pt, Au, Ni) as electrocatalyst of lithium polysulfides and improved the performance for lithium sulfur batteries. In this work, we present the nickel coated multi-walled carbon nanotubes (Ni-MWNTs) as additive materials for elemental sulfur positive electrodes for lithium-sulfur rechargeable batteries. Compared with MWNTs, the obtained Ni-MWNTs/sulfur composite cathode demonstrate a reversible specific capacity approaching 545 mAh after 200 cycles at a rate of 0.5C as well as improved cycling stability and excellent rate capacity. The improved electrochemical performance can be attributed to the fact the MWNTs shows a vital role on polysulfides adsorption and nickel has a catalytic effect on the redox reactions during charge–discharge process. Meanwhile, the Ni-MWNTs is a good electric conductor for sulfur cathode.

Le concept d'électrodes liquides de carbone appliqué au domaine des batteries en flux : étude et application aux matériaux d'intercalation du lithium

OpenAIRE

Parant , Hélène

2017-01-01

This project deals with flow batteries, which are very promising technologies for large scale energy storage, especially for intermittent energies. This work aims at developing new types of electrolytes with carbon particles to enhance power of batteries. This concept is called "liquid electrode" and is implemented in flow batteries with redox lithium intercalation particles in aqueous media. The first objective is to formulate the carbon electrolyte, with a good electronic conductivity (1-4 ...

A new lithium-ion battery internal temperature on-line estimate method based on electrochemical impedance spectroscopy measurement

Science.gov (United States)

Zhu, J. G.; Sun, Z. C.; Wei, X. Z.; Dai, H. F.

2015-01-01

The power battery thermal management problem in EV (electric vehicle) and HEV (hybrid electric vehicle) has been widely discussed, and EIS (electrochemical impedance spectroscopy) is an effective experimental method to test and estimate the status of the battery. Firstly, an electrochemical-based impedance matrix analysis for lithium-ion battery is developed to describe the impedance response of electrochemical impedance spectroscopy. Then a method, based on electrochemical impedance spectroscopy measurement, has been proposed to estimate the internal temperature of power lithium-ion battery by analyzing the phase shift and magnitude of impedance at different ambient temperatures. Respectively, the SoC (state of charge) and temperature have different effects on the impedance characteristics of battery at various frequency ranges in the electrochemical impedance spectroscopy experimental study. Also the impedance spectrum affected by SoH (state of health) is discussed in the paper preliminary. Therefore, the excitation frequency selected to estimate the inner temperature is in the frequency range which is significantly influenced by temperature without the SoC and SoH. The intrinsic relationship between the phase shift and temperature is established under the chosen excitation frequency. And the magnitude of impedance related to temperature is studied in the paper. In practical applications, through obtaining the phase shift and magnitude of impedance, the inner temperature estimation could be achieved. Then the verification experiments are conduced to validate the estimate method. Finally, an estimate strategy and an on-line estimation system implementation scheme utilizing battery management system are presented to describe the engineering value.

Low-crystallinity molybdenum sulfide nanosheets assembled on carbon nanotubes for long-life lithium storage: Unusual electrochemical behaviors and ascending capacities

Energy Technology Data Exchange (ETDEWEB)

Li, Xiaodan, E-mail: xiaodan_li@yeah.net [State Key Laboratory of Alternate Electrical Power System with Renewable Energy Sources, North China ElectricPower University, Beijing, 102206 (China); Wu, Gaoxiang, E-mail: wgxjimmy@126.com [State Key Laboratory of Alternate Electrical Power System with Renewable Energy Sources, North China ElectricPower University, Beijing, 102206 (China); Chen, Jiewei, E-mail: kzscjw@126.com [State Key Laboratory of Alternate Electrical Power System with Renewable Energy Sources, North China ElectricPower University, Beijing, 102206 (China); Li, Meicheng, E-mail: mcli@ncepu.edu.cn [State Key Laboratory of Alternate Electrical Power System with Renewable Energy Sources, North China ElectricPower University, Beijing, 102206 (China); Chongqing Materials Research Institute, Chongqing 400707 (China); Li, Wei, E-mail: wei.li@inl.int [International Iberian Nanotechnology Laboratory (INL), Braga 4715-330 (Portugal); Wang, Tianyue, E-mail: 1355796015@qq.com [State Key Laboratory of Alternate Electrical Power System with Renewable Energy Sources, North China ElectricPower University, Beijing, 102206 (China); Jiang, Bing, E-mail: BingJiang@ncepu.edu.cn [State Key Laboratory of Alternate Electrical Power System with Renewable Energy Sources, North China ElectricPower University, Beijing, 102206 (China); He, Yue, E-mail: 947667748@qq.com [State Key Laboratory of Alternate Electrical Power System with Renewable Energy Sources, North China ElectricPower University, Beijing, 102206 (China); Mai, Liqiang, E-mail: mlq518@whut.edu.cn [State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan 430070 (China)

2017-01-15

Highlights: • Low-crystallinity molybdenum sulfide coated on carbon nanotubes were synthesized. • This anode material has unusual electrochemical behaviors compared to typical MoS{sub 2}. • It exhibits noticable ascending trends in capacity and superior rate performance. • The ascending performance can effectively extend the circulation life of batteries. - Abstract: Low-crystallinity molybdenum sulfide (LCMS, Mo:S = 1:2.75) nanosheets synthesized by a facile and low temperature solvothermal method is now reported. The as-prepared LCMS anode material is composited of MoS{sub 2} layers mixed with amorphous MoS{sub 3}, which leads to an unusual electrochemical process for lithium storage compared to typical MoS{sub 2} anode. The existence of MoS{sub 3} and Mo (VI) provide strong adsorption and binding sites for polar polysulphides, which compels abundant sulfur to turn into new-formed MoS{sub 3} rather than diffuse into electrolyte. To fully utilize this novel electrochemical process, LCMS is decorated on carbon nanotubes, obtaining well-dispersed CNTs@LCMS. As electrode material for lithium storage, CNTs@LCMS exhibits a noticable ascending trend in capacity from 820 mA h g{sup −1} to 1350 mA h g{sup −1} at 100 mA g{sup −1} during 130 cycles. The persistent ascending capacity is ascribed to the increasing lithium storage caused by new-formed MoS{sub 3}, combined with the reduced volume change benifiting from well-dispersed CNTs@LCMS. Furthermore, the ascending performance is proved to be able to effectively extend the circulation life (up to 200%) for lithium-ion batteries by mathematical modeling and calculation. Accordingly, the CNTs@LCMS composite is a promising anode material for long-life lithium-ion batteries.

Nb2O5 hollow nanospheres as anode material for enhanced performance in lithium ion batteries

International Nuclear Information System (INIS)

Sasidharan, Manickam; Gunawardhana, Nanda; Yoshio, Masaki; Nakashima, Kenichi

2012-01-01

Graphical abstract: Nb 2 O 5 hollow nanosphere constructed electrode delivers high capacity of 172 mAh g −1 after 250 cycles and maintains structural integrity and excellent cycling stability. Highlights: ► Nb 2 O 5 hollow nanospheres synthesis was synthesized by soft-template. ► Nb 2 O 5 hollow nanospheres were investigated as anode material in Li-ion battery. ► Nanostructured electrode delivers high capacity of 172 mAh g −1 after 250 cycles. ► The electrode maintains the structural integrity and excellent cycling stability. ► Nanosized shell domain facilitates fast lithium intercalation/deintercalation. -- Abstract: Nb 2 O 5 hollow nanospheres of average diameter ca. ∼29 nm and hollow cavity size ca. 17 nm were synthesized using polymeric micelles with core–shell–corona architecture under mild conditions. The hollow particles were thoroughly characterized by transmission electron microscope (TEM), X-ray diffraction (XRD), infrared spectroscopy (FTIR), thermal (TG/DTA) and nitrogen adsorption analyses. Thus obtained Nb 2 O 5 hollow nanospheres were investigated as anode materials for lithium ion rechargeable batteries for the first time. The nanostructured electrode delivers high capacity of 172 mAh g −1 after 250 cycles of charge/discharge at a rate of 0.5 C. More importantly, the hollow particles based electrodes maintains the structural integrity and excellent cycling stability even after exposing to high current density 6.25 A g −1 . The enhanced electrochemical behavior is ascribed to hollow cavity coupled with nanosized Nb 2 O 5 shell domain that facilitates fast lithium intercalation/deintercalation kinetics.

Performances of a lithium-carbon ``lithium ion``battery for electric powered vehicle; Performances d`un accumulateur au lithium-carbone ``Lithium Ion`` pour vehicule electrique

Energy Technology Data Exchange (ETDEWEB)

Broussely, M.; Planchat, J.P.; Rigobert, G.; Virey, D.; Sarre, G. [SAFT, Advanced and Industrial Battery Group, 86 - Poitiers (France)

1996-12-31

The lithium battery, also called `lithium-carbon` or `lithium ion`, is today the most promising candidate that can reach the expected minimum traction performances of electric powered vehicles. Thanks to a more than 20 years experience on lithium generators and to a specific research program on lithium batteries, the SAFT company has developed a 100 Ah electrochemical system, and full-scale prototypes have been manufactured for this application. These prototypes use the Li{sub x}NiO{sub 2} lithiated graphite electrochemical pair and were tested in terms of their electrical performances. Energy characteristics of 125 Wh/kg and 265 Wh/dm{sup 3} could be obtained. The possibility of supplying a power greater than 200 W/kg, even at low temperature (-10 deg. C) has been demonstrated with these elements. A full battery set of about 20 kWh was built and its evaluation is in progress. It comprises the electronic control systems for the optimum power management during charge and output. (J.S.) 9 refs.

Performances of a lithium-carbon ``lithium ion``battery for electric powered vehicle; Performances d`un accumulateur au lithium-carbone ``Lithium Ion`` pour vehicule electrique

Energy Technology Data Exchange (ETDEWEB)

Broussely, M; Planchat, J P; Rigobert, G; Virey, D; Sarre, G [SAFT, Advanced and Industrial Battery Group, 86 - Poitiers (France)

1997-12-31

The lithium battery, also called `lithium-carbon` or `lithium ion`, is today the most promising candidate that can reach the expected minimum traction performances of electric powered vehicles. Thanks to a more than 20 years experience on lithium generators and to a specific research program on lithium batteries, the SAFT company has developed a 100 Ah electrochemical system, and full-scale prototypes have been manufactured for this application. These prototypes use the Li{sub x}NiO{sub 2} lithiated graphite electrochemical pair and were tested in terms of their electrical performances. Energy characteristics of 125 Wh/kg and 265 Wh/dm{sup 3} could be obtained. The possibility of supplying a power greater than 200 W/kg, even at low temperature (-10 deg. C) has been demonstrated with these elements. A full battery set of about 20 kWh was built and its evaluation is in progress. It comprises the electronic control systems for the optimum power management during charge and output. (J.S.) 9 refs.

Electrolytes for Wide Operating Temperature Lithium-Ion Cells

Science.gov (United States)

Smart, Marshall C. (Inventor); Bugga, Ratnakumar V. (Inventor)

2016-01-01

Provided herein are electrolytes for lithium-ion electrochemical cells, electrochemical cells employing the electrolytes, methods of making the electrochemical cells and methods of using the electrochemical cells over a wide temperature range. Included are electrolyte compositions comprising a lithium salt, a cyclic carbonate, a non-cyclic carbonate, and a linear ester and optionally comprising one or more additives.

Electrochemistry of Nanostructured Intercalation Hosts

International Nuclear Information System (INIS)

Smyrl, William H.

2009-01-01

We have shown that: (1) Li+ ions are inserted reversibly, without diffusion control, up to the level of at least 4 moles Li+ ions per mole for V2O5, in the aerogel (ARG) form (500 m2/g specific surface area) and aerogel-like (ARG-L) form (200 m2/g specific surface area)(6,7,1,2); (2) polyvalent cations (Al+3, Mg+2, Zn+2) may be intercalated reversibly into V2O5 (ARG) with high capacity (approaching 4 equivalents/mole V2O5 (ARG)) for each (5); (3) dopant cations such as Ag+ and Cu+2 increase the conductivity of V2O5 (XRG) up to three orders of magnitude(3), they are electrochemically active - showing reduction to the metallic-state in parallel to intercalation of Li+ ions - but are not released to the electrolyte upon oxidation and Li+ ion release (Cu+2 ions are reduced to Cu metal and reoxidized to Cu+2 in Li+ ion insertion/release cycles, but the copper ions are not released to the electrolyte over more than 400 cycles of the XRG form); (4) we have shown that Cu+2 ion (dopant) and Zn+2 ions (chemical insertion and dopant) occupy the same intercalation site inV2O5 xerogel and aerogel(4); and (5) the reversible intercalation of Zn+2, Mg+2, and Al+3 in the ARG(11) indicates that these cations are 'mobile', but that Cu+2 ions and Ag+ ions are 'immobile' in the xerogel, i.e., the latter ions are not exchanged with the electrolyte in Li+ ion intercalation cycling(3).

Low-cost carbon-silicon nanocomposite anodes for lithium ion batteries.

Science.gov (United States)

Badi, Nacer; Erra, Abhinay Reddy; Hernandez, Francisco C Robles; Okonkwo, Anderson O; Hobosyan, Mkhitar; Martirosyan, Karen S

2014-01-01

The specific energy of the existing lithium ion battery cells is limited because intercalation electrodes made of activated carbon (AC) materials have limited lithium ion storage capacities. Carbon nanotubes, graphene, and carbon nanofibers are the most sought alternatives to replace AC materials but their synthesis cost makes them highly prohibitive. Silicon has recently emerged as a strong candidate to replace existing graphite anodes due to its inherently large specific capacity and low working potential. However, pure silicon electrodes have shown poor mechanical integrity due to the dramatic expansion of the material during battery operation. This results in high irreversible capacity and short cycle life. We report on the synthesis and use of carbon and hybrid carbon-silicon nanostructures made by a simplified thermo-mechanical milling process to produce low-cost high-energy lithium ion battery anodes. Our work is based on an abundant, cost-effective, and easy-to-launch source of carbon soot having amorphous nature in combination with scrap silicon with crystalline nature. The carbon soot is transformed in situ into graphene and graphitic carbon during mechanical milling leading to superior elastic properties. Micro-Raman mapping shows a well-dispersed microstructure for both carbon and silicon. The fabricated composites are used for battery anodes, and the results are compared with commercial anodes from MTI Corporation. The anodes are integrated in batteries and tested; the results are compared to those seen in commercial batteries. For quick laboratory assessment, all electrochemical cells were fabricated under available environment conditions and they were tested at room temperature. Initial electrochemical analysis results on specific capacity, efficiency, and cyclability in comparison to currently available AC counterpart are promising to advance cost-effective commercial lithium ion battery technology. The electrochemical performance observed for

Electrolyte additives for lithium metal anodes and rechargeable lithium metal batteries: progresses and perspectives.

Science.gov (United States)

Zhang, Heng; Eshetu, Gebrekidan Gebresilassie; Judez, Xabier; Li, Chunmei; Rodriguez-Martínez, Lide M; Armand, Michel

2018-02-14

Lithium metal (Li°) - based rechargeable batteries (LMBs), such as Li° anode vs. intercalation and/or conversion type cathode batteries, lithium-sulphur (Li-S), and lithium-oxygen (O2)/air (Li-O2/air) are becoming increasingly important for electrifying the modern transportation system, enabling sustainable mobility in the near future. Though some rechargeable LMBs batteries (e.g., Li°/LiFePO4 batteries from Bolloré Bluecar®, Li-S batteries from OXIS Energy and Sion Power) are already commercially viable in niche applications, their large-scale deployment is still hampered due to the existence of a number of formidable challenges, including lithium dendrite growth, electrolyte instability towards high voltage intercalation type cathode, poor electronic and ionic conductivities of sulphur (S8) and O2, as well as their corresponding reduction products (e.g., Li2S and Li2O), dissolution and shuttling of polysulphide (PS) intermediates etc. This ultimately results in short cycle life, low coulombic/energy efficiency, poor safety, and a high self-discharge rate. Among other mitigating strategies, the use of electrolyte additives is considered as one of the most economical, and effective approach for circumventing these dilemmas. Set out to offer an in-depth insight into the rapidly growing research on the account of electrolyte additives for rechargeable LMBs, this review presents an overview of the various functional additives, that are being applied in Li-anode/intercalation cathode-based, Li-S and Li-O2 batteries. This review is believed to assess the status quo of the research and thereby arouse new thoughts and opportunities, opening new avenues for the practical realization of these appealing devices. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electrochemical Cell

DEFF Research Database (Denmark)

1999-01-01

The invention relates to a rechargeable electrochemical cell comprising a negative electrode, an electrolyte and a positive electrode in which the positive electrode structure comprises a lithium cobalt manganese oxide of the composition Li¿2?Co¿y?Mn¿2-y?O¿4? where 0 ... for capacity losses in lithium ion cells and lithium-alloy cells....

The preparation and graphene surface coating NaTi{sub 2}(PO{sub 4}){sub 3} as cathode material for lithium ion batteries

Energy Technology Data Exchange (ETDEWEB)

Li, Na; Wang, Yanping; Rao, Richuan; Dong, Xiongzi [Department of Chemical and Chemical Engineering, Hefei normal University, Hefei, Anhui 230601 (China); Zhang, Xianwen, E-mail: 18326056237@163.com [Institute of Advanced Energy Technology & Equipment, Hefei University of Technology, 193 Tunxi Road, Hefei, Anhui 230009 (China); Zhu, Sane, E-mail: sdjnlina@163.com [Department of Chemistry and Materials Engineering, Hefei University, Hefei, Anhui 230601 (China)

2017-03-31

Graphical abstract: The NaTi{sub 2}(PO{sub 4}){sub 3}/graphene composite is used directly as cathode electrode material for lithium-ion battery by using metal lithium as an anode electrode. Meanwhile, the electrochemical properties of the composite in this system is firstly studied in detail. The NaTi{sub 2}(PO{sub 4}){sub 3}/graphene composite exhibits the better rate and cyclic performance than NaTi{sub 2}(PO{sub 4}){sub 3}, which is ascribed to its stable 3-D framework and the enhanced electronic conduction resulting from the graphene sheets surface modification. - Highlights: • The graphene coated NaTi{sub 2}(PO{sub 4}){sub 3} was prepared by a simple sol-gel method followed by calcination. • The electrochemical properties of the NaTi{sub 2}(PO{sub 4}){sub 3}/graphene composite was firstly studied in detail when used as cathode electrode material for lithium-ion batteries. • The electrochemical reaction mechanism of NaTi{sub 2}(PO{sub 4}){sub 3}/graphene composite was investigated by ex situ XRD. - Abstract: The graphene coated NaTi{sub 2}(PO{sub 4}){sub 3} has been fabricated via a simple sol-gel process followed by calcination. The NaTi{sub 2}(PO{sub 4}){sub 3}/graphene (NTP/G) composite is used directly as cathode electrode material for lithium-ion battery and the electrochemical properties of the composite in this system is firstly studied in detail. In the charge-discharge process, two Li{sup +} can occupy octahedral M (2) site and be reversibly intercalated into the 3D framework of NTP through the ion conduction channel where almost all of Na{sup +} are immobilized to sustain the framework. At 5C rate, the capacity retention of the NTP/G composite after 800 cycles is still up to 82.7%. The superior electrochemical properties of NTP/G is ascribed to its stable 3-D framework and the enhanced electronic conduction resulting from the graphene sheets surface modification.

VO2 nanoparticles on edge orientated graphene foam for high rate lithium ion batteries and supercapacitors

Science.gov (United States)

Ren, Guofeng; Zhang, Ruibo; Fan, Zhaoyang

2018-05-01

With the fully exposed graphene edges, high conductivity and large surface area, edge oriented graphene foam (EOGF), prepared by deposition of perpendicular graphene network encircling the struts of Ni foam, is a superior scaffold to support active materials for electrochemical applications. With VO2 as an example, EOGF loaded VO2 nanoparticle (VO2/EOGF) electrode has high rate performance as cathode in lithium ion batteries (LIBs). In addition to the Li+ intercalation into the lattice, contribution of non-diffusion-limited pseudocapacitance to the capacity is prominent at high rates. VO2/EOGF based supercapacitor also exhibits fast response, with a characteristic frequency of 15 Hz when the phase angle reaches -45°, or a relaxation time constant of 66.7 ms. These results suggest the promising potential of EOGF as a scaffold in supporting active nanomaterials for electrochemical energy storage and other applications.

Electrodeposition of high-density lithium vanadate nanowires for lithium-ion battery

Science.gov (United States)

Hua, Kang; Li, Xiujuan; Fang, Dong; Yi, Jianhong; Bao, Rui; Luo, Zhiping

2018-07-01

Lithium vanadate nanowires have been electrodeposited onto a titanium (Ti) foil by a direct current electrodeposition without template. The morphology, crystal structure, and the effects of deposition voltage, temperature and time on the prepared samples were tested and presented. The as-prepared lithium vanadate nanowires/Ti composite can be used as electrode for lithium-ion battery. Electrochemical measurements showed that the electrode displayed a specific discharge capacitance as high as 235.1 mAh g-1 after 100 cycles at a current density of 30 mA g-1. This research provides a new pathway to explore high tap density vanadates nanowires on metals with enhanced electrochemical performance.

Electrochemical characteristics of nanostructured silicon anodes for lithium-ion batteries

International Nuclear Information System (INIS)

Astrova, E. V.; Li, G. V.; Rumyantsev, A. M.; Zhdanov, V. V.

2016-01-01

High-aspect periodic structures with thin vertical walls are studied as regards their applicability as negative electrodes of lithium-ion batteries. The nanostructures are fabricated from single-crystal silicon using photolithography, electrochemical anodization, and subsequent anisotropic shaping. The capacity per unit of the visible surface area of the electrode and the specific internal surface area are compared for structures of varied architecture: 1D (wires), 2D (zigzag walls), and 3D structures (walls forming a grid). Main attention is given to testing the endurance of anodes based on zigzag and grid structures, performed by galvanostatic cycling in half-cells with a lithium counter electrode. The influence exerted by the geometric parameters of the structures and by the testing mode on the degradation rate is determined. It is shown that the limiting factor of the lithiation and delithiation processes is diffusion. The endurance of an electrode dramatically increases when the charging capacity is limited to ∼1000 mA h/g. In this case, nanostructures with 300-nm-thick walls, which underwent cyclic testing at a rate of 0.36C, retain a constant discharge capacity and a Coulomb efficiency close to 100% for more than 1000 cycles.

Electrochemical characteristics of nanostructured silicon anodes for lithium-ion batteries

Energy Technology Data Exchange (ETDEWEB)

Astrova, E. V., E-mail: east@mail.ioffe.ru; Li, G. V.; Rumyantsev, A. M.; Zhdanov, V. V. [Russian Academy of Sciences, Ioffe Physical–Technical Institute (Russian Federation)

2016-02-15

High-aspect periodic structures with thin vertical walls are studied as regards their applicability as negative electrodes of lithium-ion batteries. The nanostructures are fabricated from single-crystal silicon using photolithography, electrochemical anodization, and subsequent anisotropic shaping. The capacity per unit of the visible surface area of the electrode and the specific internal surface area are compared for structures of varied architecture: 1D (wires), 2D (zigzag walls), and 3D structures (walls forming a grid). Main attention is given to testing the endurance of anodes based on zigzag and grid structures, performed by galvanostatic cycling in half-cells with a lithium counter electrode. The influence exerted by the geometric parameters of the structures and by the testing mode on the degradation rate is determined. It is shown that the limiting factor of the lithiation and delithiation processes is diffusion. The endurance of an electrode dramatically increases when the charging capacity is limited to ∼1000 mA h/g. In this case, nanostructures with 300-nm-thick walls, which underwent cyclic testing at a rate of 0.36C, retain a constant discharge capacity and a Coulomb efficiency close to 100% for more than 1000 cycles.

Uniform second Li ion intercalation in solid state ϵ-LiVOPO{sub 4}

Energy Technology Data Exchange (ETDEWEB)

Wangoh, Linda W.; Quackenbush, Nicholas F. [Department of Physics, Applied Physics and Astronomy, Binghamton University, Binghamton, New York 13902 (United States); Sallis, Shawn [Materials Science and Engineering, Binghamton University, Binghamton, New York 13902 (United States); Wiaderek, Kamila M.; Ma, Lu; Wu, Tianpin; Chapman, Karena W. [X-ray Science Division, Advanced Photon Source, Argonne National Laboratory, Argonne, Illinois 60439 (United States); Lin, Yuh-Chieh; Ong, Shyue Ping [Department of NanoEngineering, University of California San Diego, 9500 Gilman Drive 0448, La Jolla, California 92093 (United States); Wen, Bohua; Chernova, Natasha A.; Whittingham, M. Stanley [NECCES, Binghamton University, Binghamton, New York 13902 (United States); Guo, Jinghua [Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, California 94720 (United States); Lee, Tien-Lin; Schlueter, Christoph [Diamond Light Source Ltd., Harwell Science and Innovation Campus, Didcot, Oxfordshire OX11 0DE (United Kingdom); Piper, Louis F. J., E-mail: lpiper@binghamton.edu [Department of Physics, Applied Physics and Astronomy, Binghamton University, Binghamton, New York 13902 (United States); Materials Science and Engineering, Binghamton University, Binghamton, New York 13902 (United States)

2016-08-01

Full, reversible intercalation of two Li{sup +} has not yet been achieved in promising VOPO{sub 4} electrodes. A pronounced Li{sup +} gradient has been reported in the low voltage window (i.e., second lithium reaction) that is thought to originate from disrupted kinetics in the high voltage regime (i.e., first lithium reaction). Here, we employ a combination of hard and soft x–ray photoelectron and absorption spectroscopy techniques to depth profile solid state synthesized LiVOPO{sub 4} cycled within the low voltage window only. Analysis of the vanadium environment revealed no evidence of a Li{sup +} gradient, which combined with almost full theoretical capacity confirms that disrupted kinetics in the high voltage window are responsible for hindering full two lithium insertion. Furthermore, we argue that the uniform Li{sup +} intercalation is a prerequisite for the formation of intermediate phases Li{sub 1.50}VOPO{sub 4} and Li{sub 1.75}VOPO{sub 4}. The evolution from LiVOPO{sub 4} to Li{sub 2}VOPO{sub 4} via the intermediate phases is confirmed by direct comparison between O K–edge absorption spectroscopy and density functional theory.

Fabrication of lithium titanate/graphene composites with high rate capability as electrode materials for hybrid electrochemical supercapacitors

International Nuclear Information System (INIS)

Xue, Rong; Yan, Jingwang; Jiang, Liang; Yi, Baolian

2015-01-01

A lithium titanate (Li 4 Ti 5 O 12 )/graphene composite (LTO/graphene) is fabricated with a one-pot sol–gel method. Graphite oxide is dispersed in an aqueous solution of lithium acetate and tetrabutyl titanate followed by heat treatment in H 2 /Ar. The LTO/graphene composite with reduced aggregation and improved homogeneity is investigated as an anode material for electrochemical capacitors. Electron transport is improved by the conductive graphene network in the insulating Li 4 Ti 5 O 12 particles. The charge transfer resistance at the particle/electrolyte interface is reduced from 83.1 Ω to 55.4 Ω. The specific capacity of LTO/graphene composite is 126 mAh g −1 at 20C. The energy density and power density of a hybrid electrochemical supercapacitor with a LTO/graphene negative electrode and an activated carbon positive electrode are 120.8 Wh kg −1 and 1.5 kW kg −1 , respectively, which is comparable to that of conventional electrochemical double layer capacitors (EDLCs). The LTO/graphene composite fabricated by the one-pot sol–gel method is a promising anode material for hybrid electrochemical supercapacitors. - Highlights: • A Li 4 Ti 5 O 12 /graphene composite was fabricated with a one-pot sol–gel method. • The Li 4 Ti 5 O 12 /graphene composite showed a reduced aggregation and an improved homogeneity. • The Li 4 Ti 5 O 12 /graphene based hybrid supercapacitor exhibited higher energy and power densities

Study of sulfonated polyether ether ketone with pendant lithiated fluorinated sulfonic groups as ion conductive binder in lithium-ion batteries

Science.gov (United States)

Wei, Zengbin; Xue, Lixin; Nie, Feng; Sheng, Jianfang; Shi, Qianru; Zhao, Xiulan

2014-06-01

In an attempt to reduce the Li+ concentration polarization and electrolyte depletion from the electrode porous space, sulfonated polyether ether ketone with pendant lithiated fluorinated sulfonic groups (SPEEK-FSA-Li) is prepared and attempted as ionic conductivity binder. Sulfonated aromatic poly(ether ether ketone) exhibits strong adhesion and chemical stability, and lithiated fluorinated sulfonic side chains help to enhance the ionic conductivity and Li+ ion diffusion due to the charge delocalization over the sulfonic chain. The performances are evaluated by cyclic voltammetry, electrochemical impedance spectroscopy, charge-discharge cycle testing, 180° peel testing, and compared with the cathode prepared with polyvinylidene fluoride binder. The electrode prepared with SPEEK-FSA-Li binder forms the relatively smaller resistances of both the SEI and the charge transfer of lithium ion transport. This is beneficial to lithium ion intercalation and de-intercalation of the cathode during discharging-charging, therefore the cell prepared with SPEEK-FSA-Li shows lower charge plateau potential and higher discharge plateau potential. Compared with PVDF, the electrode with ionic binder shows smaller decrease in capacity with the increasing of cycle rate. Meanwhile, adhesion strength of electrode prepared with SPEEK-FSA-Li is more than five times greater than that with PVDF.

X-ray Spectroscopy and Imaging as Multiscale Probes of Intercalation Phenomena in Cathode Materials

Science.gov (United States)

Horrocks, Gregory A.; De Jesus, Luis R.; Andrews, Justin L.; Banerjee, Sarbajit

2017-09-01

Intercalation phenomena are at the heart of modern electrochemical energy storage. Nevertheless, as out-of-equilibrium processes involving concomitant mass and charge transport, such phenomena can be difficult to engineer in a predictive manner. The rational design of electrode architectures requires mechanistic understanding of physical phenomena spanning multiple length scales, from atomistic distortions and electron localization at individual transition metal centers to phase inhomogeneities and intercalation gradients in individual particles and concentration variances across ensembles of particles. In this review article, we discuss the importance of the electronic structure in mediating electrochemical storage and mesoscale heterogeneity. In particular, we discuss x-ray spectroscopy and imaging probes of electronic and atomistic structure as well as statistical regression methods that allow for monitoring of the evolution of the electronic structure as a function of intercalation. The layered α-phase of V2O5 is used as a model system to develop fundamental ideas on the origins of mesoscale heterogeneity.

Electrode nanomaterials for lithium-ion batteries

International Nuclear Information System (INIS)

Yaroslavtsev, A B; Kulova, T L; Skundin, A M

2015-01-01

The state-of-the-art in the field of cathode and anode nanomaterials for lithium-ion batteries is considered. The use of these nanomaterials provides higher charge and discharge rates, reduces the adverse effect of degradation processes caused by volume variations in electrode materials upon lithium intercalation and deintercalation and enhances the power and working capacity of lithium-ion batteries. In discussing the cathode materials, attention is focused on double phosphates and silicates of lithium and transition metals and also on vanadium oxides. The anode materials based on nanodispersions of carbon, silicon, certain metals, oxides and on nanocomposites are also described. The bibliography includes 714 references

Lanthanum Nitrate As Electrolyte Additive To Stabilize the Surface Morphology of Lithium Anode for Lithium-Sulfur Battery.

Science.gov (United States)

Liu, Sheng; Li, Guo-Ran; Gao, Xue-Ping

2016-03-01

Lithium-sulfur (Li-S) battery is regarded as one of the most promising candidates beyond conventional lithium ion batteries. However, the instability of the metallic lithium anode during lithium electrochemical dissolution/deposition is still a major barrier for the practical application of Li-S battery. In this work, lanthanum nitrate, as electrolyte additive, is introduced into Li-S battery to stabilize the surface of lithium anode. By introducing lanthanum nitrate into electrolyte, a composite passivation film of lanthanum/lithium sulfides can be formed on metallic lithium anode, which is beneficial to decrease the reducibility of metallic lithium and slow down the electrochemical dissolution/deposition reaction on lithium anode for stabilizing the surface morphology of metallic Li anode in lithium-sulfur battery. Meanwhile, the cycle stability of the fabricated Li-S cell is improved by introducing lanthanum nitrate into electrolyte. Apparently, lanthanum nitrate is an effective additive for the protection of lithium anode and the cycling stability of Li-S battery.

Improved performance and safety of lithium ion cells with the use of fluorinated carbonate-based electrolytes

Science.gov (United States)

Smart, M. C.; Ratnakumar, B. V.; Ryan, V. S.; Surampudi, S.; Prakashi, G. K. S.; Hu, J.; Cheung, I.

2002-01-01

There has been increasing interest in developing lithium-ion electrolytes that possess enhanced safety characteristics, while still able to provide the desired stability and performance. Toward this end, our efforts have been focused on the development of lithium-ion electrolytes which contain partially and fully fluorinated carbonate solvents. The advantage of using such solvents is that they possess the requisite stability demonstrated by the hydrocarbon-based carbonates, while also possessing more desirable physical properties imparted by the presence of the fluorine substituents, such as lower melting points, increased stability toward oxidation, and favorable SEI film forming Characteristics on carbon. Specifically, we have demonstrated the beneficial effect of electrolytes which contain the following fluorinated carbonate-based solvents: methyl 2,2,2-trifluoroethyl carbonate (MTFEC), ethyl-2,2,2 trifluoroethyl carbonate (ETFEC), propyl 2,2,2-trifluoroethyl carbonate (PTFEC), methyl-2,2,2,2',2',2' -hexafluoro-i-propyl carbonate (MHFPC), ethyl- 2,2,2,2',2',2' -hexafluoro-i-propyl carbonate (EHFPC), and di-2,2,2-trifluoroethyl carbonate (DTFEC). These solvents have been incorporated into multi-component ternary and quaternary carbonate-based electrolytes and evaluated in lithium-carbon and carbon-LiNio.8Coo.202 cells (equipped with lithium reference electrodes). In addition to determining the charge/discharge behavior of these cells, a number of electrochemical techniques were employed (i.e., Tafel polarization measurements, linear polarization measurements, and electrochemical impedance spectroscopy (EIS)) to further characterize the performance of these electrolytes, including the SEI formation characteristics and lithium intercalatiodde-intercalation kinetics. In addition to their evaluation in experimental cells, cyclic voltammetry (CV) and conductivity measurements were performed on select electrolyte formulations to further our understanding of the trends

In-Situ Observation of Solid Electrolyte Interphase Formation in Ordered Mesoporous Hard Carbon by Small-Angle Neutron Scattering

International Nuclear Information System (INIS)

Bridges, Craig A.; Paranthaman, Mariappan Parans; Sun, Xiao-Guang; Zhao, Jinkui; Dai, Sheng

2012-01-01

The aim of this work was to better understand the electrochemical processes occurring during the cycling of a lithium-ion half-cell containing ordered mesoporous hard carbon using time-resolved in situ small-angle neutron scattering (SANS). Utilizing electrolytes containing mixtures of deuterated (2H) and non-deuterated (1H) carbonates, we have addressed the challenging task of monitoring the formation and evolution of the solid-electrolyte interphase (SEI) layer. An evolution occurs in the SEI layer during discharge from a composition dominated by a higher scattering length density (SLD) lithium salt, to a lower SLD lithium salt for the ethylene carbonate/dimethyl carbonate (EC/DMC) mixture employed. By comparing half-cells containing different solvent deuteration levels, we show that it is possible to observe both SEI formation and lithium intercalation occurring concurrently at the low voltage region in which lithium intercalates into the hard carbon. These results demonstrate that SANS can be employed to monitor complicated electrochemical processes occurring in rechargeable batteries, in a manner that simultaneously provides information on the composition and microstructure of the electrode.

Safe and recyclable lithium-ion capacitors using sacrificial organic lithium salt

Science.gov (United States)

Jeżowski, P.; Crosnier, O.; Deunf, E.; Poizot, P.; Béguin, F.; Brousse, T.

2018-02-01

Lithium-ion capacitors (LICs) shrewdly combine a lithium-ion battery negative electrode capable of reversibly intercalating lithium cations, namely graphite, together with an electrical double-layer positive electrode, namely activated carbon. However, the beauty of this concept is marred by the lack of a lithium-cation source in the device, thus requiring a specific preliminary charging step. The strategies devised thus far in an attempt to rectify this issue all present drawbacks. Our research uncovers a unique approach based on the use of a lithiated organic material, namely 3,4-dihydroxybenzonitrile dilithium salt. This compound can irreversibly provide lithium cations to the graphite electrode during an initial operando charging step without any negative effects with respect to further operation of the LIC. This method not only restores the low CO2 footprint of LICs, but also possesses far-reaching potential with respect to designing a wide range of greener hybrid devices based on other chemistries, comprising entirely recyclable components.

Creation of nanosized holes in graphene planes for improvement of rate capability of lithium-ion batteries

Science.gov (United States)

Bulusheva, L. G.; Stolyarova, S. G.; Chuvilin, A. L.; Shubin, Yu V.; Asanov, I. P.; Sorokin, A. M.; Mel'gunov, M. S.; Zhang, Su; Dong, Yue; Chen, Xiaohong; Song, Huaihe; Okotrub, A. V.

2018-04-01

Holes with an average size of 2-5 nm have been created in graphene layers by heating of graphite oxide (GO) in concentrated sulfuric acid followed by annealing in an argon flow. The hot mineral acid acts simultaneously as a defunctionalizing and etching agent, removing a part of oxygen-containing groups and lattice carbon atoms from the layers. Annealing of the holey reduced GO at 800 °C-1000 °C causes a decrease of the content of residual oxygen and the interlayer spacing thus producing thin compact stacks from holey graphene layers. Electrochemical tests of the obtained materials in half-cells showed that the removal of oxygen and creation of basal holes lowers the capacity loss in the first cycle and facilitates intercalation-deintercalation of lithium ions. This was attributed to minimization of electrolyte decomposition reactions, easier desolvation of lithium ions near the hole boundaries and appearance of multiple entrances for the naked ions into graphene stacks.

Deuterium and lithium-6 MAS NMR studies of manganese oxide electrode materials

Science.gov (United States)

Paik, Younkee

Electrolytic manganese dioxide (EMD) is used world wide as the cathode materials in both lithium and alkaline primary (non-rechargeable) batteries. We have developed deuterium and lithium MAS NMR techniques to study EMD and related manganese oxides and hydroxides, where diffraction techniques are of limited value due to a highly defective nature of the structures. Deuterons in EMD, manganite, groutite, and deuterium-intercalated pyrolusite and ramsdellite were detected by NMR, for the first time, and their locations and motions in the structures were analyzed by applying variable temperature NMR techniques. Discharge mechanisms of EMD in alkaline (aqueous) electrolytes were studied, in conjunction with step potential electrochemical spectroscopic (SPECS) method, and five distinctive discharge processes were proposed. EMD is usually heat-treated at about 300--400°C to remove water to be used in lithium batteries. Details of the effects of heat-treatment, such as structural and compositional changes as a function of heat-treatment temperature, were studied by a combination of MAS NMR, XRD, and thermogravimetric analysis. Lithium local environments in heat-treated EMD (HEMD) that were discharged in lithium cells, were described in terms of related environments found in model compounds pyrolusite and ramsdellite where specific Li + sites were detected by MAS NMR and the hyperfine shift scale method of Grey et al. Acid-leaching of Li2MnO3 represents an approach for synthesizing new or modified manganese oxide electrode materials for lithium rechargeable batteries. Progressive removal of lithium from specific crystallographic sites, followed by a gradual change of the crystal structure, was monitored by a combination of NMR and XRD techniques.

Porous Co3O4 nanorods as anode for lithium-ion battery with excellent electrochemical performance

International Nuclear Information System (INIS)

Guo, Jinxue; Chen, Lei; Zhang, Xiao; Chen, Haoxin

2014-01-01

In this manuscript, porous Co 3 O 4 nanorods are prepared through a two-step approach which is composed of hydrothermal process and heating treatment as high performance anode for lithium-ion battery. Benefiting from the porous structure and 1-dimensional features, the product becomes robust and exhibits high reversible capability, good cycling performance, and excellent rate performance. - Graphical abstract: 1D porous Co 3 O 4 nanostructure as anode for lithium-ion battery with excellent electrochemical performance. - Highlights: • A two-step route has been applied to prepare 1D porous Co 3 O 4 nanostructure. • Its porous feature facilitates the fast transport of electron and lithium ion. • Its porous structure endows it with capacities higher than its theoretical capacity. • 1D nanostructure can tolerate volume changes during lithation/delithiation cycles. • It exhibits high capacity, good cyclability and excellent rate performance

Highly Reversible Lithium-ions Storage of Molybdenum Dioxide Nanoplates for High Power Lithium-ion Batteries.

Science.gov (United States)

Liu, Xiaolin; Yang, Jun; Hou, Wenhua; Wang, Jiulin; Nuli, Yanna

2015-08-24

Herein, MoO2 nanoplates have been facilely prepared through a hydrothermal process by using MoO3 microbelts as the intercalation host. The obtained MoO2 nanoplates manifest excellent electrochemical properties when the discharge cutoff voltage is simply set at 1.0 V to preclude the occurrence of conversion reactions. Its initial reversible capacity reaches 251 mAh g(-1), which is larger than that of Li4Ti5O12 , at a current rate of 0.2 C. The average capacity decay is only 0.0465 mAh g(-1) per cycle, with a coulombic efficiency of 99.5% (from the 50th cycle onward) for 2000 cycles at 1 C. Moreover, this MoO2 electrode demonstrates an outstanding high power performance. When the current rate is increased from 0.2 to 50 C, about 54% of the capacity is retained. The superior electrochemical performance can be attributed to the metallic conductivity of MoO2, short Li(+) diffusion distance in the nanoplates, and reversible crystalline phase conversion of the addition-type reaction of MoO2. The prepared MoO2 nanoplates may hopefully replace their currently used analogues, such as Li4Ti5O12 , in high power lithium-ion batteries. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Materials Compositions for Lithium Ion Batteries with Extended Thermal Stability

Science.gov (United States)

Kalaga, Kaushik

Advancements in portable electronics have generated a pronounced demand for rechargeable energy storage devices with superior capacity and reliability. Lithium ion batteries (LIBs) have evolved as the primary choice of portable power for several such applications. While multiple variations have been developed, safety concerns of commercial technologies limit them to atmospheric temperature operability. With several niche markets such as aerospace, defense and oil & gas demanding energy storage at elevated temperatures, there is a renewed interest in developing rechargeable batteries that could survive temperatures beyond 100°C. Instability of critical battery components towards extreme thermal and electrochemical conditions limit their usability at high temperatures. This study deals with developing material configurations for LIB components to stabilize them at such temperatures. Flammable organic solvent based electrolytes and low melting polymer based separators have been identified as the primary bottleneck for LIBs to survive increasing temperature. Furthermore, thermally activated degradation processes in oxide based electrodes have been identified as the reason for their limited lifetime. A quasi-solid composite comprising of room temperature ionic liquids (RTILs) and Clay was developed as an electrolyte/separator hybrid and tested to be stable up to 120°C. These composites facilitate complete reversible Li intercalation in lithium titanate (LTO) with a stable capacity of 120 mAh g-1 for several cycles of charge and discharge while simultaneously resisting severe thermal conditions. Modified phosphate based electrodes were introduced as a reliable alternative for operability at high temperatures in this study. These systems were shown to deliver stable reversible capacity for numerous charge/discharge cycles at elevated temperatures. Higher lithium intercalation potential of the developed cathode materials makes them interesting candidates for high voltage

Rechargeable Aqueous Zinc-Ion Battery Based on Porous Framework Zinc Pyrovanadate Intercalation Cathode

KAUST Repository

Xia, Chuan; Guo, Jing; Lei, Yongjiu; Liang, Hanfeng; Zhao, Chao; Alshareef, Husam N.

2017-01-01

metal pyrovanadate compounds. The zinc pyrovanadate nanowires show significantly improved electrochemical performance when used as intercalation cathode for aqueous zinc–ion battery. Specifically, the ZVO cathode delivers high capacities of 213 and 76 m

Graphene-supported SnO2 nanoparticles prepared by a solvothermal approach for an enhanced electrochemical performance in lithium-ion batteries.

Science.gov (United States)

Wang, Bei; Su, Dawei; Park, Jinsoo; Ahn, Hyojun; Wang, Guoxiu

2012-04-13

SnO2 nanoparticles were dispersed on graphene nanosheets through a solvothermal approach using ethylene glycol as the solvent. The uniform distribution of SnO2 nanoparticles on graphene nanosheets has been confirmed by scanning electron microscopy and transmission electron microscopy. The particle size of SnO2 was determined to be around 5 nm. The as-synthesized SnO2/graphene nanocomposite exhibited an enhanced electrochemical performance in lithium-ion batteries, compared with bare graphene nanosheets and bare SnO2 nanoparticles. The SnO2/graphene nanocomposite electrode delivered a reversible lithium storage capacity of 830 mAh g-1 and a stable cyclability up to 100 cycles. The excellent electrochemical properties of this graphene-supported nanocomposite could be attributed to the insertion of nanoparticles between graphene nanolayers and the optimized nanoparticles distribution on graphene nanosheets.

A rechargeable iodine-carbon battery that exploits ion intercalation and iodine redox chemistry.

Science.gov (United States)

Lu, Ke; Hu, Ziyu; Ma, Jizhen; Ma, Houyi; Dai, Liming; Zhang, Jintao

2017-09-13

Graphitic carbons have been used as conductive supports for developing rechargeable batteries. However, the classic ion intercalation in graphitic carbon has yet to be coupled with extrinsic redox reactions to develop rechargeable batteries. Herein, we demonstrate the preparation of a free-standing, flexible nitrogen and phosphorus co-doped hierarchically porous graphitic carbon for iodine loading by pyrolysis of polyaniline coated cellulose wiper. We find that heteroatoms could provide additional defect sites for encapsulating iodine while the porous carbon skeleton facilitates redox reactions of iodine and ion intercalation. The combination of ion intercalation with redox reactions of iodine allows for developing rechargeable iodine-carbon batteries free from the unsafe lithium/sodium metals, and hence eliminates the long-standing safety issue. The unique architecture of the hierarchically porous graphitic carbon with heteroatom doping not only provides suitable spaces for both iodine encapsulation and cation intercalation but also generates efficient electronic and ionic transport pathways, thus leading to enhanced performance.Carbon-based electrodes able to intercalate Li + and Na + ions have been exploited for high performing energy storage devices. Here, the authors combine the ion intercalation properties of porous graphitic carbons with the redox chemistry of iodine to produce iodine-carbon batteries with high reversible capacities.

The prospects of phosphorene as an anode material for high-performance lithium-ion batteries: a fundamental study.

Science.gov (United States)

Zhang, Congyan; Yu, Ming; Anderson, George; Dharmasena, Ruchira Ravinath; Sumanasekera, Gamini

2017-02-17

To completely understand lithium adsorption, diffusion, and capacity on the surface of phosphorene and, therefore, the prospects of phosphorene as an anode material for high-performance lithium-ion batteries (LIBs), we carried out density-functional-theory calculations and studied the lithium adsorption energy landscape, the lithium diffusion mobility, the lithium intercalation, and the lithium capacity of phosphorene. We also carried out, for the very first time, experimental measurement of the lithium capacity of phosphorene. Our calculations show that the lithium diffusion mobility along the zigzag direction in the valley of phosphorene was about 7 to 11 orders of magnitude faster than that along the other directions, indicating its ultrafast and anisotropic diffusivity. The lithium intercalation in phosphorene was studied by considering various Li n P 16 configurations (n = 1-16) including single-side and double-side adsorptions. We found that phosphorene could accommodate up to a ratio of one Li per P atom (i.e. Li 16 P 16 ). In particular, we found that, even at a high Li concentration (e.g. x = 1 in Li x P), there was no lithium clustering, and the structure of phosphorene (when fractured) is reversible during lithium intercalation. The theoretical value of the lithium capacity for a monolayer phosphorene is predicted to be above 433 mAh g -1 , depending on whether Li atoms are adsorbed on the single side or the double side of phosphorene. Our experimental measurement of the lithium capacity for few-layer phosphorene networks shows a reversible stable value of ∼453 mAh g -1 even after 50 cycles. Our results clearly show that phosphorene, compared to graphene and other two-dimensional materials, has great promise as a novel anode material for high-performance LIBs.

Lithium insertion in V{sub 2}O{sub 5}, M{sub x}V{sub 2}O{sub 5} (M = Fe, Cr, Al, La) mixed oxides; Insertion du lithium dans les oxydes mixtes de V{sub 2}O{sub 5}, M{sub x}V{sub 2}O{sub 5} (M = Fe, Cr, Al, La)

Energy Technology Data Exchange (ETDEWEB)

Gregoire, G.; Pecquenard, B.; Baffier, N. [Centre National de la Recherche Scientifique (CNRS), 75 - Paris (France). Laboratoire de Chimie Appliquee de l`Etat Solide; Soudan, P.; Farcy, J.; Pereira-Ramos, J.P. [Centre National de la Recherche Scientifique (CNRS), 94 - Ivry-sur-Seine (France). Laboratoire d`Electrochimie Catalyse et Synthese Organique

1996-12-31

V{sub 2}O{sub 5} based compounds are interesting low potential materials for rechargeable cathodes of lithium electrochemical generators. However, the ionic conductivity and the reversibility of electrochemical cycling of V{sub 2}O{sub 5} are limited by the possibilities of lithium insertion. This work shows that the doping of vanadium pentoxide by a M{sup 3+} trivalent transition element (M Fe, Al, Cr or La) allows to intercalate a more important amount of lithium and to improve the behaviour of the material during cycling. These materials of M{sub 0.11}V{sub 2}O{sub 5.16} formula are obtained by sol-gel synthesis. the electrochemical study of the Fe compound has shown that it is a mixed oxide with a behaviour similar to V{sub 2}O{sub 5}. The maximum capacity is of about 2 F/mole in the case of Fe, Al and Cr compounds and of about 1.7 F/mole in the case of La. The structural evolution of the Fe compound has been followed during the chemical insertion of Li and the same succession of phases ({alpha}, {epsilon}, {delta} and {gamma}) is observed as in Li{sub x}V{sub 2}O{sub 5} compounds but with a delay. The occurrence of the {gamma} phase, in particular, which is involved in recharging problems is delayed thanks to the (Fe-O){sub n} chains perpendicular to the (V{sub 2}O{sub 5}){sub n} layers. Abstract only. (J.S.) 3 refs.

Lithium insertion in V{sub 2}O{sub 5}, M{sub x}V{sub 2}O{sub 5} (M = Fe, Cr, Al, La) mixed oxides; Insertion du lithium dans les oxydes mixtes de V{sub 2}O{sub 5}, M{sub x}V{sub 2}O{sub 5} (M = Fe, Cr, Al, La)

Energy Technology Data Exchange (ETDEWEB)

Gregoire, G; Pecquenard, B; Baffier, N [Centre National de la Recherche Scientifique (CNRS), 75 - Paris (France). Laboratoire de Chimie Appliquee de l` Etat Solide; Soudan, P; Farcy, J; Pereira-Ramos, J P [Centre National de la Recherche Scientifique (CNRS), 94 - Ivry-sur-Seine (France). Laboratoire d` Electrochimie Catalyse et Synthese Organique

1997-12-31

V{sub 2}O{sub 5} based compounds are interesting low potential materials for rechargeable cathodes of lithium electrochemical generators. However, the ionic conductivity and the reversibility of electrochemical cycling of V{sub 2}O{sub 5} are limited by the possibilities of lithium insertion. This work shows that the doping of vanadium pentoxide by a M{sup 3+} trivalent transition element (M Fe, Al, Cr or La) allows to intercalate a more important amount of lithium and to improve the behaviour of the material during cycling. These materials of M{sub 0.11}V{sub 2}O{sub 5.16} formula are obtained by sol-gel synthesis. the electrochemical study of the Fe compound has shown that it is a mixed oxide with a behaviour similar to V{sub 2}O{sub 5}. The maximum capacity is of about 2 F/mole in the case of Fe, Al and Cr compounds and of about 1.7 F/mole in the case of La. The structural evolution of the Fe compound has been followed during the chemical insertion of Li and the same succession of phases ({alpha}, {epsilon}, {delta} and {gamma}) is observed as in Li{sub x}V{sub 2}O{sub 5} compounds but with a delay. The occurrence of the {gamma} phase, in particular, which is involved in recharging problems is delayed thanks to the (Fe-O){sub n} chains perpendicular to the (V{sub 2}O{sub 5}){sub n} layers. Abstract only. (J.S.) 3 refs.

Enhanced cycling stability of microsized LiCoO2 cathode by Li4Ti5O12 coating for lithium ion battery

International Nuclear Information System (INIS)

Yi, Ting-Feng; Shu, J.; Yue, Cai-Bo; Zhu, Xiao-Dong; Zhou, An-Na; Zhu, Yan-Rong; Zhu, Rong-Sun

2010-01-01

The effect of Li 4 Ti 5 O 12 (LTO) coating amount on the electrochemical cycling behavior of the LiCoO 2 cathode was investigated at the high upper voltage limit of 4.5 V. Li 4 Ti 5 O 12 (≤5 wt.%) is not incorporated into the host structure and leads to formation of uniform coating. The cycling performance of LiCoO 2 cathode is related with the amount of Li 4 Ti 5 O 12 coating. The initial capacity of the LTO-coated LiCoO 2 decreased with increasing Li 4 Ti 5 O 12 coating amount but showed enhanced cycling properties, compared to those of pristine material. The 3 wt.% LTO-coated LiCoO 2 has the best electrochemical performance, showing capacity retention of 97.3% between 2.5 V and 4.3 V and 85.1% between 2.5 V and 4.5 V after 40 cycles. The coulomb efficiency shows that the surface coating of Li 4 Ti 5 O 12 is beneficial to the reversible intercalation/de-intercalation of Li + . LTO-coated LiCoO 2 provides good prospects for practical application of lithium secondary batteries free from safety issues.

An activated microporous carbon prepared from phenol-melamine-formaldehyde resin for lithium ion battery anode

International Nuclear Information System (INIS)

Zhu, Yinhai; Xiang, Xiaoxia; Liu, Enhui; Wu, Yuhu; Xie, Hui; Wu, Zhilian; Tian, Yingying

2012-01-01

Highlights: ► Microporous carbon was prepared by chemical activation of phenol-melamine-formaldehyde resin. ► Activation leads to high surface area, well-developed micropores. ► Micropores lead to strong intercalation between carbon and lithium ion. ► Large surface area promotes to improve the lithium storage capacity. -- Abstract: Microporous carbon anode materials were prepared from phenol-melamine-formaldehyde resin by ZnCl 2 and KOH activation. The physicochemical properties of the obtained carbon materials were characterized by scanning electron microscope, X-ray diffraction, Brunauer–Emmett–Teller, and elemental analysis. The electrochemical properties of the microporous carbon as anode materials in lithium ion secondary batteries were evaluated. At a current density of 100 mA g −1 , the carbon without activation shows a first discharge capacity of 515 mAh g −1 . After activation, the capacity improved obviously. The first discharge capacity of the carbon prepared by ZnCl 2 and KOH activation was 1010 and 2085 mAh g −1 , respectively. The reversible capacity of the carbon prepared by KOH activation was still as high as 717 mAh g −1 after 20 cycles, which was much better than that activated by ZnCl 2 . These results demonstrated that it may be a promising candidate as an anode material for lithium ion secondary batteries.

Functional interface of polymer modified graphite anode

Science.gov (United States)

Komaba, S.; Ozeki, T.; Okushi, K.

Graphite electrodes were modified by polyacrylic acid (PAA), polymethacrylic acid (PMA), and polyvinyl alcohol (PVA). Their electrochemical properties were examined in 1 mol dm -3 LiClO 4 ethylene carbonate:dimethyl carbonate (EC:DMC) and propylene carbonate (PC) solutions as an anode of lithium ion batteries. Generally, lithium ions hardly intercalate into graphite in the PC electrolyte due to a decomposition of the PC electrolyte at ca. 0.8 V vs. Li/Li +, and it results in the exfoliation of the graphene layers. However, the modified graphite electrodes with PAA, PMA, and PVA demonstrated the stable charge-discharge performance due to the reversible lithium intercalation not only in the EC:DMC but also in the PC electrolytes since the electrolyte decomposition and co-intercalation of solvent were successfully suppressed by the polymer modification. It is thought that these improvements were attributed to the interfacial function of the polymer layer on the graphite which interacted with the solvated lithium ions at the electrode interface.

A comparative study on electrochemical performances of the electrodes with different nanocarbon conductive additives for lithium ion batteries

International Nuclear Information System (INIS)

Chen, Taiqiang; Pan, Likun; Liu, Xinjuan; Sun, Zhuo

2013-01-01

Three nanocarbon materials (0 D acetylene black (AB), 1 D carbon nanotubes (CNTs) and 2 D reduced graphene oxide (RGO)) were used as conductive additives (CAs) in the mesocarbon microbead anodes for lithium ion batteries. The electrochemical performances of the electrodes were investigated. The results show that the CAs have a significant impact on the electrode performance because they can influence the electron conduction and lithium ion transportation within the electrode. The electrode with RGO achieves a maximum capacity of 387 mAh g −1 after 50 cycles at a current density of 50 mA g −1 , much higher than those of the electrodes with AB (334 mAh g −1 ) and CNTs (319 mAh g −1 ). The improvement should be mainly ascribed to the “plane-to-point” conducting network formed in the electrode with 2 D RGO which can favor the electron conduction and enhance the lithium ion transportation. - Highlights: • Three carbon materials were used as additives in the electrodes of Li ion battery. • The electrochemical performances of the electrodes were comparatively investigated. • The carbon additives have a significant impact on the electrode performance. • RGO additive acts as a bridge to form a “plane-to-point” conducting network. • The electrode with RGO exhibits better performance than those with other additives

Fabrication of lithium titanate/graphene composites with high rate capability as electrode materials for hybrid electrochemical supercapacitors

Energy Technology Data Exchange (ETDEWEB)

Xue, Rong, E-mail: xuerongsmile@qq.com; Yan, Jingwang, E-mail: yanjw@dicp.ac.cn; Jiang, Liang, E-mail: jiangliang@dicp.ac.cn; Yi, Baolian, E-mail: blyi@dicp.ac.cn

2015-06-15

A lithium titanate (Li{sub 4}Ti{sub 5}O{sub 12})/graphene composite (LTO/graphene) is fabricated with a one-pot sol–gel method. Graphite oxide is dispersed in an aqueous solution of lithium acetate and tetrabutyl titanate followed by heat treatment in H{sub 2}/Ar. The LTO/graphene composite with reduced aggregation and improved homogeneity is investigated as an anode material for electrochemical capacitors. Electron transport is improved by the conductive graphene network in the insulating Li{sub 4}Ti{sub 5}O{sub 12} particles. The charge transfer resistance at the particle/electrolyte interface is reduced from 83.1 Ω to 55.4 Ω. The specific capacity of LTO/graphene composite is 126 mAh g{sup −1} at 20C. The energy density and power density of a hybrid electrochemical supercapacitor with a LTO/graphene negative electrode and an activated carbon positive electrode are 120.8 Wh kg{sup −1} and 1.5 kW kg{sup −1}, respectively, which is comparable to that of conventional electrochemical double layer capacitors (EDLCs). The LTO/graphene composite fabricated by the one-pot sol–gel method is a promising anode material for hybrid electrochemical supercapacitors. - Highlights: • A Li{sub 4}Ti{sub 5}O{sub 12}/graphene composite was fabricated with a one-pot sol–gel method. • The Li{sub 4}Ti{sub 5}O{sub 12}/graphene composite showed a reduced aggregation and an improved homogeneity. • The Li{sub 4}Ti{sub 5}O{sub 12}/graphene based hybrid supercapacitor exhibited higher energy and power densities.

Nb{sub 2}O{sub 5} hollow nanospheres as anode material for enhanced performance in lithium ion batteries

Energy Technology Data Exchange (ETDEWEB)

Sasidharan, Manickam [Department of Chemistry, Faculty of Science and Engineering, Saga University, 1 Honjo-machi, Saga 840-8502 (Japan); Gunawardhana, Nanda [Advanced Research Center, Saga University, 1341 Yoga-machi, Saga 840-0047 (Japan); Yoshio, Masaki, E-mail: yoshio@cc.saga-u.ac.jp [Advanced Research Center, Saga University, 1341 Yoga-machi, Saga 840-0047 (Japan); Nakashima, Kenichi, E-mail: nakashik@cc.saga-u.ac.jp [Department of Chemistry, Faculty of Science and Engineering, Saga University, 1 Honjo-machi, Saga 840-8502 (Japan)

2012-09-15

Graphical abstract: Nb{sub 2}O{sub 5} hollow nanosphere constructed electrode delivers high capacity of 172 mAh g{sup −1} after 250 cycles and maintains structural integrity and excellent cycling stability. Highlights: ► Nb{sub 2}O{sub 5} hollow nanospheres synthesis was synthesized by soft-template. ► Nb{sub 2}O{sub 5} hollow nanospheres were investigated as anode material in Li-ion battery. ► Nanostructured electrode delivers high capacity of 172 mAh g{sup −1} after 250 cycles. ► The electrode maintains the structural integrity and excellent cycling stability. ► Nanosized shell domain facilitates fast lithium intercalation/deintercalation. -- Abstract: Nb{sub 2}O{sub 5} hollow nanospheres of average diameter ca. ∼29 nm and hollow cavity size ca. 17 nm were synthesized using polymeric micelles with core–shell–corona architecture under mild conditions. The hollow particles were thoroughly characterized by transmission electron microscope (TEM), X-ray diffraction (XRD), infrared spectroscopy (FTIR), thermal (TG/DTA) and nitrogen adsorption analyses. Thus obtained Nb{sub 2}O{sub 5} hollow nanospheres were investigated as anode materials for lithium ion rechargeable batteries for the first time. The nanostructured electrode delivers high capacity of 172 mAh g{sup −1} after 250 cycles of charge/discharge at a rate of 0.5 C. More importantly, the hollow particles based electrodes maintains the structural integrity and excellent cycling stability even after exposing to high current density 6.25 A g{sup −1}. The enhanced electrochemical behavior is ascribed to hollow cavity coupled with nanosized Nb{sub 2}O{sub 5} shell domain that facilitates fast lithium intercalation/deintercalation kinetics.

Lithium and sodium batteries with polysulfide electrolyte

KAUST Repository

Li, Mengliu

2017-12-28

A battery comprising: at least one cathode, at least one anode, at least one battery separator, and at least one electrolyte disposed in the separator, wherein the anode is a lithium metal or lithium alloy anode or an anode adapted for intercalation of lithium ion, wherein the cathode comprises material adapted for reversible lithium extraction from and insertion into the cathode, and wherein the separator comprises at least one porous, electronically conductive layer and at least one insulating layer, and wherein the electrolyte comprises at least one polysulfide anion. The battery provides for high energy density and capacity. A redox species is introduced into the electrolyte which creates a hybrid battery. Sodium metal and sodium-ion batteries also provided.

Novel iron-cobalt derivatised lithium iron phosphate nanocomposite for lithium ion battery cathode

CSIR Research Space (South Africa)

Ikpo, CO

2013-01-01

Full Text Available Described herein is the electrochemical study conducted on lithium ion battery cathode material consisting of composite of lithium iron phosphate (LiFePO(sub4), iron-cobalt derivatised carbon nanotubes (FeCo-CNT) and polyaniline (PA) nanomaterials...

Investigations of the Electrochemical Stability of Aqueous Electrolytes for Lithium Battery Applications

KAUST Repository

Wessells, Colin

2010-01-01

The electrolytic stability windows of several aqueous electrolytes were investigated by a constant current method. The electrode potential range depended upon the value of the imposed current. The magnitude of this behavior varied with the salt solution, its concentration, and pH of the electrolyte. At a leakage current density of 50 μA/cm2, a 5 M solution of LiNO3 had an electrolytic window of 2.3 V, spanning from -0.55 to 1.75 V with respect to the standard hydrogen electrode. These results demonstrate the feasibility of operating lithium batteries at voltages appreciably above the theoretical decomposition voltage of water. © 2010 The Electrochemical Society.

NdFeB alloy as a magnetic electrode material for lithium-ion batteries

International Nuclear Information System (INIS)

Zhang, J.; Shui, J.L.; Zhang, S.L.; Wei, X.; Xiang, Y.J.; Xie, S.; Zhu, C.F.; Chen, C.H.

2005-01-01

The search for a reliable indicator of state of charge and even the remaining energy of a lithium-ion cell is of great importance for various applications. This study was an exploratory effort to use magnetic susceptibility as the indicator. In this work, for the first time the change of ac susceptibility of cells was in situ monitored during charge-discharge process. A strong permanent magnetic material, NdFeB alloy, was investigated as an anode material for rechargeable lithium batteries. Both original and partially oxidized NdFeB powders were made into electrodes. Structural characterization was performed on the NdFeB electrodes by means of X-ray diffraction (XRD) and scanning electron microscopy (SEM) analysis. An alloy (core)-oxide (shell) structure was found for those partially oxidized samples. The electrochemical cycling of cells made of the NdFeB electrodes against lithium was measured. The first lithium intercalation capacity of a treated NdFeB can be up to about 831 mAh/g, while a rather reversible capacity of up to 352 mAh/g can be obtained. With a specially designed cell, we were able to monitor in situ the change of relative ac susceptibility during charge and/or discharge steps. A clearly monotonous relationship is found between the ac susceptibility of a cell and its depth-of-discharge (DOD). A mechanism based on skin effect and eddy current change is proposed to explain this susceptibility versus DOD relationship

NdFeB alloy as a magnetic electrode material for lithium-ion batteries

Energy Technology Data Exchange (ETDEWEB)

Zhang, J. [Department of Materials Science and Engineering, University of Science and Technology of China, Anhui Hefei 230026 (China); Shui, J.L. [Department of Materials Science and Engineering, University of Science and Technology of China, Anhui Hefei 230026 (China); Zhang, S.L. [Department of Materials Science and Engineering, University of Science and Technology of China, Anhui Hefei 230026 (China); Wei, X. [Department of Materials Science and Engineering, University of Science and Technology of China, Anhui Hefei 230026 (China); Xiang, Y.J. [Department of Materials Science and Engineering, University of Science and Technology of China, Anhui Hefei 230026 (China); Xie, S. [Department of Materials Science and Engineering, University of Science and Technology of China, Anhui Hefei 230026 (China); Zhu, C.F. [Department of Materials Science and Engineering, University of Science and Technology of China, Anhui Hefei 230026 (China); Chen, C.H. [Department of Materials Science and Engineering, University of Science and Technology of China, Anhui Hefei 230026 (China)]. E-mail: cchchen@ustc.edu.cn

2005-04-05

The search for a reliable indicator of state of charge and even the remaining energy of a lithium-ion cell is of great importance for various applications. This study was an exploratory effort to use magnetic susceptibility as the indicator. In this work, for the first time the change of ac susceptibility of cells was in situ monitored during charge-discharge process. A strong permanent magnetic material, NdFeB alloy, was investigated as an anode material for rechargeable lithium batteries. Both original and partially oxidized NdFeB powders were made into electrodes. Structural characterization was performed on the NdFeB electrodes by means of X-ray diffraction (XRD) and scanning electron microscopy (SEM) analysis. An alloy (core)-oxide (shell) structure was found for those partially oxidized samples. The electrochemical cycling of cells made of the NdFeB electrodes against lithium was measured. The first lithium intercalation capacity of a treated NdFeB can be up to about 831 mAh/g, while a rather reversible capacity of up to 352 mAh/g can be obtained. With a specially designed cell, we were able to monitor in situ the change of relative ac susceptibility during charge and/or discharge steps. A clearly monotonous relationship is found between the ac susceptibility of a cell and its depth-of-discharge (DOD). A mechanism based on skin effect and eddy current change is proposed to explain this susceptibility versus DOD relationship.

A miniaturized silicon based device for nucleic acids electrochemical detection

Directory of Open Access Journals (Sweden)

Salvatore Petralia

2015-12-01

Full Text Available In this paper we describe a novel portable system for nucleic acids electrochemical detection. The core of the system is a miniaturized silicon chip composed by planar microelectrodes. The chip is embedded on PCB board for the electrical driving and reading. The counter, reference and work microelectrodes are manufactured using the VLSI technology, the material is gold for reference and counter electrodes and platinum for working electrode. The device contains also a resistor to control and measuring the temperature for PCR thermal cycling. The reaction chamber has a total volume of 20 μL. It is made in hybrid silicon–plastic technology. Each device contains four independent electrochemical cells.Results show HBV Hepatitis-B virus detection using an unspecific DNA intercalating redox probe based on metal–organic compounds. The recognition event is sensitively detected by square wave voltammetry monitoring the redox signals of the intercalator that strongly binds to the double-stranded DNA. Two approaches were here evaluated: (a intercalation of electrochemical unspecific probe on ds-DNA on homogeneous solution (homogeneous phase; (b grafting of DNA probes on electrode surface (solid phase.The system and the method here reported offer better advantages in term of analytical performances compared to the standard commercial optical-based real-time PCR systems, with the additional incomes of being potentially cheaper and easier to integrate in a miniaturized device. Keywords: Electrochemical detection, Real time PCR, Unspecific DNA intercalator

Metal-decored graphites as anode materials for use in lithium-ion accumulators

International Nuclear Information System (INIS)

Licht, Bjoern Karl

2015-01-01

Graphitic materials are currently the most frequently used anode materials for lithium ion batteries (LIB). This type of battery is considered to be the ideal application for energy storage in electromobility or in mobile devices that require a high power density. Although intercalated graphite has only about 8 % of the gravimetric energy density of lithium metal, these materials are preferred due to safety reasons. However, by chemical modification of the surface, the electrochemical performance of graphite can be enhanced. In the thesis presented at hand, a novel synthesis route for the preparation of homogenous metal depositions on graphite is shown. The reaction proceeds via a gas phase reaction by the thermal decomposition of metal carboxylates. The decomposition process was analyzed by thermogravimetry and gas phase analysis. In comparison to the unmodified graphite, copper-coated graphite shows in increased capacity and cycle stability when used as anode materials in LIBs. Special emphasis should be placed on an improved adhesion of the active material on the copper current collector. The proven catalytic activity of the metal depositions not only enables a use in battery devices but could also be innovating for catalytic processes such as chlorine-alkali electrolysis.

Synthesis and electrochemical performances of amorphous carbon-coated Sn Sb particles as anode material for lithium-ion batteries

Science.gov (United States)

Wang, Zhong; Tian, Wenhuai; Liu, Xiaohe; Yang, Rong; Li, Xingguo

2007-12-01

The amorphous carbon coating on the Sn-Sb particles was prepared from aqueous glucose solutions using a hydrothermal method. Because the outer layer carbon of composite materials is loose cotton-like and porous-like, it can accommodate the expansion and contraction of active materials to maintain the stability of the structure, and hinder effectively the aggregation of nano-sized alloy particles. The as-prepared composite materials show much improved electrochemical performances as anode materials for lithium-ion batteries compared with Sn-Sb alloy and carbon alone. This amorphous carbon-coated Sn-Sb particle is extremely promising anode materials for lithium secondary batteries and has a high potentiality in the future use.

Preparation and electrochemical performance of bramble-like ZnO array as anode materials for lithium-ion batteries

International Nuclear Information System (INIS)

Yan, Junfeng; Wang, Gang; Wang, Hui; Zhang, Zhiyong; Ruan, Xiongfei; Zhao, Wu; Yun, Jiangni; Xu, Manzhang

2015-01-01

A bramble-like ZnO array with a special three-dimensional (3D) nanostructure was successfully fabricated on Zn foil through a facile two-step hydrothermal process. A possible growth mechanism of the bramble-like ZnO array was proposed. In the first step of hydrothermal process, the crystal nucleus of Zn(OH) 4 2− generated by the zinc atoms and OH − ions fold together preferentially along the positive polar (0001) to form the needle-like ZnO array. In the second step of hydrothermal process, the crystal nuclei of Zn(OH) 4 2− adjust their posture to keep their c-axes vertical to the perching sites due to the sufficient environmental force and further grow preferentially along the (0001) direction so as to form bramble-like ZnO array. The electrochemical properties of the needle- and bramble-like ZnO arrays as anode materials for lithium-ion batteries were investigated and compared. The results show that the bramble-like ZnO material exhibits much better lithium storage properties than the needle-like ZnO sample. Reasons for the enhanced electrochemical performance of the bramble-like ZnO material were investigated

Characterization and electrochemical performance of lithium-active titanium dioxide inlaid LiNi0.5Co0.2Mn0.3O2 material prepared by lithium residue-assisted method

International Nuclear Information System (INIS)

Li, Lingjun; Chen, Zhaoyong; Song, Liubin; Xu, Ming; Zhu, Huali; Gong, Li; Zhang, Kaili

2015-01-01

Highlights: • LiTiO 2 -inlaid LiNi 0.5 Co 0.2 Mn 0.3 O 2 is prepared by lithium residue-assisted method. • The unique inlaid architecture inherits the advantages of coating and doping. • LiTiO 2 inlaying enhances the pristine at high cyclability and rate properties. • Excess LiTiO 2 modification results in low Li + diffusion coefficient. • The 3 mol% LiTiO 2 inlaid sample exhibits the best electrochemical performance. - Abstract: The lithium residues are consumed as raw materials to in-situ synthesize the LiTiO 2 -inlaid LiNi 0.5 Co 0.2 Mn 0.3 O 2 composites. The effects of various LiTiO 2 contents on the morphology, structure, and electrochemical properties of LiNi 0.5 Co 0.2 Mn 0.3 O 2 materials are investigated in detail. Energy dispersive spectrometer mapping, high-resolution transmission electron microscopy and fast Fourier transform analysis confirm that the spherical particles of LiNi 0.5 Co 0.2 Mn 0.3 O 2 are completely coated by crystalline LiTiO 2 phase; X-ray diffraction, cross-section SEM and corresponding EDS results indicate that Ti ions are also doped into the bulk LiNi 0.5 Co 0.2 Mn 0.3 O 2 with gradient distribution. Electrochemical tests show that the LiTiO 2 -inlaid samples exhibit excellent reversible capacity, enhanced cyclability, superior lithium diffusion coefficient and rate properties. Specially, the 3 mol% LiTiO 2 inlaid sample maintains 153.7 mA h g −1 with 94.4% capacity retention after 100 cycles between 2.7–4.4 V at 1 C, take 30% advantage than that of the pristine one (118.2 mA h g −1 ). This improvement can be attributed to the removal of lithium residues and suitable LiTiO 2 inlaying. The absence of lithium residue is helpful to retard the decomposition of LiPF 6 . While, suitable LiTiO 2 inlaying can protect the bulk from directly contacting the electrolyte, buffer the volume change of core and shell during cycles, increase the surface electronic conductivity and offer a 3D path for Li + diffusion from the bulk to

Effect of Different Binders on the Electrochemical Performance of Metal Oxide Anode for Lithium-Ion Batteries

Science.gov (United States)

Wang, Rui; Feng, Lili; Yang, Wenrong; Zhang, Yinyin; Zhang, Yanli; Bai, Wei; Liu, Bo; Zhang, Wei; Chuan, Yongming; Zheng, Ziguang; Guan, Hongjin

2017-10-01

When testing the electrochemical performance of metal oxide anode for lithium-ion batteries (LIBs), binder played important role on the electrochemical performance. Which binder was more suitable for preparing transition metal oxides anodes of LIBs has not been systematically researched. Herein, five different binders such as polyvinylidene fluoride (PVDF) HSV900, PVDF 301F, PVDF Solvay5130, the mixture of styrene butadiene rubber and sodium carboxymethyl cellulose (SBR+CMC), and polyacrylonitrile (LA133) were studied to make anode electrodes (compared to the full battery). The electrochemical tests show that using SBR+CMC and LA133 binder which use water as solution were significantly better than PVDF. The SBR+CMC binder remarkably improve the bonding capacity, cycle stability, and rate performance of battery anode, and the capacity retention was about 87% after 50th cycle relative to the second cycle. SBR+CMC binder was more suitable for making transition metal oxides anodes of LIBs.

Synthesis and electrochemical properties of high performance polyhedron sphere like lithium manganese oxide for lithium ion batteries

International Nuclear Information System (INIS)

Guo, Donglei; Wei, Xiuge; Chang, Zhaorong; Tang, Hongwei; Li, Bao; Shangguan, Enbo; Chang, Kun; Yuan, Xiao-Zi; Wang, Haijiang

2015-01-01

Graphical abstract: Polyhedron structured sphere-like LiMn 2 O 4 synthesized from β-MnO 2 nanorod precursor via a solid state reaction at a temperature of 800 °C exhibits excellent rate capability and cycling performance at both 25 °C and 55 °C. - Highlights: • Polyhedron sphere-like LiMn 2 O 4 was synthesized from β-MnO 2 nanorod precursor. • The polyhedron sphere-like LiMn 2 O 4 exhibits excellent rate capability and cycling performance. • The polyhedron sphere-like structure spinel LiMn 2 O 4 suppresses the dissolution of manganese ions. • The polyhedron sphere-like LiMn 2 O 4 has high diffusion coefficient of Li + . - Abstract: Polyhedron structured sphere-like lithium manganese oxide (LiMn 2 O 4 ) is successfully synthesized from β-MnO 2 nanorod precursor via a solid state reaction at a temperature of 800 °C. For comparison, LiMn 2 O 4 materials with nanorod and octahedron structures are also obtained from β-MnO 2 nanorod precursor at temperatures of 700 °C and 900 °C, respectively. The galvanostatic charge–discharge result shows that the polyhedron sphere-like LiMn 2 O 4 sample exhibits the best electrochemical performance at high rate and high temperature. After 100 cycles at 5 C, this electrode is able to maintain 94% of its capacity at 25 °C and 81% at 55 °C. This is attributed to that the polyhedron sphere-like spinel LiMn 2 O 4 can suppress the dissolution of manganese ions. Based on Brunauer Emmett Teller (BET), cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS), the polyhedron sphere-like LiMn 2 O 4 sample has the lowest BET surface area, largest diffusion coefficient of Li + and least charge transfer resistance. This study provides an insight into the capacity fading of LiMn 2 O 4 electrodes and the polyhedron structured sphere-like LiMn 2 O 4 can be a promising material for lithium ion batteries

Degradation Mechanisms of Electrochemically Cycled Graphite Anodes in Lithium-ion Cells

Science.gov (United States)

Bhattacharya, Sandeep

This research is aimed at developing advanced characterization methods for studying the surface and subsurface damage in Li-ion battery anodes made of polycrystalline graphite and identifying the degradation mechanisms that cause loss of electrochemical capacity. Understanding microstructural aspects of the graphite electrode degradation mechanisms during charging and discharging of Li-ion batteries is of key importance in order to design durable anodes with high capacity. An in-situ system was constructed using an electrochemical cell with an observation window, a large depth-of-field digital microscope and a micro-Raman spectrometer. It was revealed that electrode damage by removal of the surface graphite fragments of 5-10 mum size is the most intense during the first cycle that led to a drastic capacity drop. Once a solid electrolyte interphase (SEI) layer covered the electrode surface, the rate of graphite particle loss decreased. Yet, a gradual loss of capacity continued by the formation of interlayer cracks adjacent to SEI/graphite interfaces. Deposition of co-intercalation compounds, LiC6, Li2CO3 and Li2O, near the crack tips caused partial closure of propagating graphite cracks during cycling and reduced the crack growth rate. Bridging of crack faces by delaminated graphite layers also retarded crack propagation. The microstructure of the SEI layer, formed by electrochemical reduction of the ethylene carbonate based electrolyte, consisted of ˜5-20 nm sized crystalline domains (containing Li2CO3, Li2O 2 and nano-sized graphite fragments) dispersed in an amorphous matrix. During the SEI formation, two regimes of Li-ion diffusion were identified at the electrode/electrolyte interface depending on the applied voltage scan rate (dV/dt). A low Li-ion diffusion coefficient ( DLi+) at dV/dt microscopic information to the electrochemical performance, novel Li2CO3-coated electrodes were fabricated that were durable. The SEI formed on pre-treated electrodes reduced

Synthesis and Electrochemical Properties of Fe-doped V6O13 as Cathode Material for Lithium-ion Battery

Directory of Open Access Journals (Sweden)

YUAN Qi

2018-01-01

Full Text Available Fe-doped V6O13 was synthesized via a facile hydrothermal method after preparing precursor in order to improve the discharge capacity and cycle performance of V6O13 cathode material at high-lithium state. XRD, SEM and XPS were employed to characterize the phase, morphology and valence of the Fe-doped V6O13. Meanwhile, the electrochemical performance was analyzed and researched. Different morphologies and electrochemical performances of Fe-doped V6O13 were obtained via doping different contents of Fe3+ ion. The sample 0.02 presented the largest thickness of nanosheets (the thickness of 600-900nm and clearance between layers. The Fe-doped V6O13 has a better electrochemical performance than that of pure V6O13. The sample 0.02 exhibits the best electrochemical performance, the initial discharge specific capacity is 433mAh·g-1 and the capacity retention is 47.1% after 100 cycles.

Lithium manganese oxide spinel electrodes

Science.gov (United States)

Darling, Robert Mason

Batteries based oil intercalation eletrodes are currently being considered for a variety of applications including automobiles. This thesis is concerned with the simulation and experimental investigation of one such system: spinel LiyMn2O4. A mathematical model simulating the behavior of an electrochemical cell containing all intercalation electrode is developed and applied to Li yMn2O4 based systems. The influence of the exchange current density oil the propagation of the reaction through the depth of the electrode is examined theoretically. Galvanostatic cycling and relaxation phenomena on open circuit are simulated for different particle-size distributions. The electrode with uniformly sized particles shows the best performance when the current is on, and relaxes towards equilibrium most quickly. The impedance of a porous electrode containing a particle-size distribution at low frequencies is investigated with all analytic solution and a simplified version of the mathematical model. The presence of the particle-size distribution leads to an apparent diffusion coefficient which has all incorrect concentration dependence. A Li/1 M LiClO4 in propylene carbonate (PC)/ LiyMn 2O4 cell is used to investigate the influence of side reactions oil the current-potential behavior of intercalation electrodes. Slow cyclic voltammograms and self-discharge data are combined to estimate the reversible potential of the host material and the kinetic parameters for the side reaction. This information is then used, together with estimates of the solid-state diffusion coefficient and main-reaction exchange current density, in a mathematical model of the system. Predictions from the model compare favorably with continuous cycling results and galvanostatic experiments with periodic current interruptions. The variation with respect to composition of' the diffusion coefficient of lithium in LiyMn2O4 is estimated from incomplete galvanostatic discharges following open-circult periods. The

Intercalating graphene with clusters of Fe3O4 nanocrystals for electrochemical supercapacitors

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Ke, Qingqing; Tang, Chunhua; Liu, Yanqiong; Liu, Huajun; Wang, John

2014-04-01

A hierarchical nanostructure consisting of graphene sheets intercalated by clusters of Fe3O4 nanocystals is developed for high-performance supercapacitor electrode. Here we show that the negatively charged graphene oxide (GO) and positively charged Fe3O4 clusters enable a strong electrostatic interaction, generating a hierarchical 3D nanostructure, which gives rise to the intercalated composites through a rational hydrothermal process. The electrocapacitive behavior of the resultant composites is systematically investigated by cyclic voltammeter and galvanostatic charge-discharge techniques, where a positive synergistic effect between graphene and Fe3O4 clusters is identified. A maximum specific capacitance of 169 F g-1 is achieved in the Fe3O4 clusters decorated with effectively reduced graphene oxide (Fe3O4-rGO-12h), which is much higher than those of rGO (101 F g-1) and Fe3O4 (68 F g-1) at the current density of 1 Ag-1. Moreover, this intercalated hierarchical nanostructure demonstrates a good capacitance retention, retaining over 88% of the initial capacity after 1000 cycles.

Oxide Fiber Cathode Materials for Rechargeable Lithium Cells

Science.gov (United States)

Rice, Catherine E.; Welker, Mark F.

2008-01-01

LiCoO2 and LiNiO2 fibers have been investigated as alternatives to LiCoO2 and LiNiO2 powders used as lithium-intercalation compounds in cathodes of rechargeable lithium-ion electrochemical cells. In making such a cathode, LiCoO2 or LiNiO2 powder is mixed with a binder [e.g., poly(vinylidene fluoride)] and an electrically conductive additive (usually carbon) and the mixture is pressed to form a disk. The binder and conductive additive contribute weight and volume, reducing the specific energy and energy density, respectively. In contrast, LiCoO2 or LiNiO2 fibers can be pressed and sintered to form a cathode, without need for a binder or a conductive additive. The inter-grain contacts of the fibers are stronger and have fewer defects than do those of powder particles. These characteristics translate to increased flexibility and greater resilience on cycling and, consequently, to reduced loss of capacity from cycle to cycle. Moreover, in comparison with a powder-based cathode, a fiber-based cathode is expected to exhibit significantly greater ionic and electronic conduction along the axes of the fibers. Results of preliminary charge/discharge-cycling tests suggest that energy densities of LiCoO2- and LiNiO2-fiber cathodes are approximately double those of the corresponding powder-based cathodes.

Preparation and electrochemical properties of mesoporous NiCo2O4 double-hemisphere used as anode for lithium-ion battery.

Science.gov (United States)

Yang, Yue; Huang, Guo Yong; Sun, Hongyu; Ahmad, Mashkoor; Mou, Qinyao; Zhang, Hongmei

2018-06-19

NiCo 2 O 4 is a potential anode material for lithium ion battery due to its many advantages, such as high theoretical capacitance, low cost, and good electrochemical activity. In this study, mesoporous NiCo 2 O 4 double-hemisphere (3-5 μm) with high surface area (270.68 m 2 ·g -1 ) and excellent electrochemical performances has been synthesized through a facile precipitation method followed with thermal treatment process. The prepared NiCo 2 O 4 is pure phase and can be indexed as a face-centered-cubic with a typical spinel structure. Electrochemical tests show the prepared material has high specific capacities (910 mAh·g -1 at 100 mA·g -1 ), excellent cyclicity (908  mAh·g -1 at 100 mA·g -1 after 60 cycles) and remarkable high rate performance (after 100 cycles, 585 mAh·g -1 at 400 mAh·g -1 , 415 mAh·g -1 at 800 mAh·g -1 and 320 mAh·g -1 at 1600 mAh·g -1 with coulombic efficiencies of almost 100%). The excellent performances of prepared NiCo 2 O 4 are mainly caused by the unique double-hemisphere structure, which has large surface area, gives material more opportunity to contact with electrolyte and facilitates lithium ion spreading into the material along the radical direction, resulting in a promising application for next-generation lithium-ion batteries. Copyright © 2018 Elsevier Inc. All rights reserved.

Al2O3-coated porous separator for enhanced electrochemical performance of lithium sulfur batteries

International Nuclear Information System (INIS)

Zhang, Zhiyong; Lai, Yanqing; Zhang, Zhian; Zhang, Kai; Li, Jie

2014-01-01

Graphical abstract: Al2O3-coated separator with developed porous channels is prepared by coating Al2O3 polymer solution on routine separator. The batteries with Al2O3-coated separator exhibited a reversible capacity of as high as 593 mAh g-1 at the rate of 0.2 C after 50th charge/discharge cycle. The enhancement in the electrochemical performance could be attributed to the reduced charge transfer resistance after the introduction of Al2O3 coating layer. Besides, the Al2O3 coating layer, acting as a physical barrier for polysulfides, can effectively prevent polysulfides shuttling between the cathode and the anode. We believe that the Al2O3-coated separator is promising in the lithium sulfur battery applications. - Highlights: • Al 2 O 3 -coated separator is used as the separator of lithium sulfur battery. • The cell with Al 2 O 3 -coated separator exhibits excellent cycling stability and high rate capability. • Al 2 O 3 -coated separator is promising in the lithium sulfur battery applications. - Abstract: In this paper, Al 2 O 3 -coated separator with developed porous channels is prepared to improve the electrochemical performance of lithium sulfur batteries. It is demonstrated that the Al 2 O 3 -coating layer is quite effective in reducing shuttle effect and enhancing the stability of the sulfur electrode. The initial discharge capacity of the cell with Al 2 O 3 -coated separator can reach 967 mAh g −1 at the rate of 0.2 C. After 50th charge/discharge cycle, this cell can also deliver a reversible capacity of as high as 593.4 mAh g −1 . Significantly, the charge-transfer resistance of the electrode tends to be reducing after using Al 2 O 3 -coated separator. The improved cell performance is attributed to the porous architecture of the Al 2 O 3 -coating layer, which serves as an ion-conducting skeleton for trapping and depositing dissolved sulfur-containing active materials, as confirmed by scanning electron microscopy (SEM) and energy-dispersive X

The electron diffraction: a prime technique to characterize the behaviour of the Li{sub 1-x}C{sub y} / Li{sub x}NiO{sub 2} positive electrode; La diffraction electronique: une technique de choix pour caracteriser le comportement de l`electrode positive Li{sub 1-x}C{sub y} / Li{sub x}NiO{sub 2}

Energy Technology Data Exchange (ETDEWEB)

Peres, J.P.; Delmas, C.; Weill, F. [Centre National de la Recherche Scientifique (CNRS), 33 - Pessac (France). Institut de Chimie de la Matiere Condensee de Bordeaux; Broussely, M.; Perton, F.; Biensan, Ph. [SAFT, Advanced and Industrial Battery Group, 86 - Poitiers (France); Willmann, P. [Centre National d`Etudes Spatiales (CNES), 31 - Toulouse (France)

1996-12-31

LiNiO{sub 2} is one of the most promising material for positive electrodes of lithium-ion batteries. However, its behaviour during cycling and the existence of several phase transitions induced by the lithium ions de-intercalation process has not been explained so far. A transition electron microscopy study of various Li{sub x}NiO{sub 2} (0.25lithium ions and gaps during electrochemical charging. This study is in agreement with the potential levels of the electrochemical cycle and with the polarization phenomena during cycling. Abstract only. (J.S.)

The electron diffraction: a prime technique to characterize the behaviour of the Li{sub 1-x}C{sub y} / Li{sub x}NiO{sub 2} positive electrode; La diffraction electronique: une technique de choix pour caracteriser le comportement de l`electrode positive Li{sub 1-x}C{sub y} / Li{sub x}NiO{sub 2}

Energy Technology Data Exchange (ETDEWEB)

Peres, J P; Delmas, C; Weill, F [Centre National de la Recherche Scientifique (CNRS), 33 - Pessac (France). Institut de Chimie de la Matiere Condensee de Bordeaux; Broussely, M; Perton, F; Biensan, Ph [SAFT, Advanced and Industrial Battery Group, 86 - Poitiers (France); Willmann, P [Centre National d` Etudes Spatiales (CNES), 31 - Toulouse (France)

1997-12-31

LiNiO{sub 2} is one of the most promising material for positive electrodes of lithium-ion batteries. However, its behaviour during cycling and the existence of several phase transitions induced by the lithium ions de-intercalation process has not been explained so far. A transition electron microscopy study of various Li{sub x}NiO{sub 2} (0.25lithium ions and gaps during electrochemical charging. This study is in agreement with the potential levels of the electrochemical cycle and with the polarization phenomena during cycling. Abstract only. (J.S.)

Environmentally benign graphite intercalation compound composition for exfoliated graphite, flexible graphite, and nano-scaled graphene platelets

Science.gov (United States)

Zhamu, Aruna; Jang, Bor Z.

2014-06-17

A carboxylic-intercalated graphite compound composition for the production of exfoliated graphite, flexible graphite, or nano-scaled graphene platelets. The composition comprises a layered graphite with interlayer spaces or interstices and a carboxylic acid residing in at least one of the interstices, wherein the composition is prepared by a chemical oxidation reaction which uses a combination of a carboxylic acid and hydrogen peroxide as an intercalate source. Alternatively, the composition may be prepared by an electrochemical reaction, which uses a carboxylic acid as both an electrolyte and an intercalate source. Exfoliation of the invented composition does not release undesirable chemical contaminants into air or drainage.

N-doped graphene/graphite composite as a conductive agent-free anode material for lithium ion batteries with greatly enhanced electrochemical performance

International Nuclear Information System (INIS)

Guanghui, Wu; Ruiyi, Li; Zaijun, Li; Junkang, Liu; Zhiguo, Gu; Guangli, Wang

2015-01-01

Graphical abstract: The study reported a novel N-doped graphene/graphite anode material for lithium ion batteries. The composite exhibits a largely enhanced electrochemical performance. The study also provides an attractive approach for the fabrication of various graphite-based materials for high power batteries. Display Omitted -- Highlights: • The paper developed a new N-doped graphene/graphite composite for lithium ion battery • The composite contains a three-dimensional graphene framework with rich of open pores • The hybrid offers a higher electrical conductivity when compared with pristine graphite • The hybrid electrode provides a greatly enhanced electrochemical performance • The study provides a prominent approach for fabrication of graphite-based materials -- ABSTRACT: Present graphite anode cannot meet the increasing requirement of electronic devices and electric vehicles due to its low specific capacity, poor cycle stability and low rate capability. The study reported a promising N-doped graphene/graphite composite as a conductive agent-free anode material for lithium ion batteries. Herein, graphite oxide and urea were dispersed in ultrapure water and partly reduced by ascorbic acid. Followed by mixing with graphite and hydrothermal treatment to produce graphene oxide/graphite hydrogel. The hydrogel was dried and finally annealed in Ar/H 2 to obtain N-doped graphene/graphite composite. The result shows that all of graphite particles was dispersed in three-dimensional graphene framework with a rich of open pores. The open pore accelerates the electrolyte transport. The graphene framework works as a conductive agent and graphite particle connector and improves the electron transfer. Electrical conductivity of the composite reaches 5912 S m −1 , which is much better than that of the pristine graphite (4018 S m −1 ). The graphene framework also acts as an expansion absorber in the anodes of lithium ion battery to relieve the large strains

Advances of aqueous rechargeable lithium-ion battery: A review

Science.gov (United States)

Alias, Nurhaswani; Mohamad, Ahmad Azmin

2015-01-01

The electrochemical characteristic of the aqueous rechargeable lithium-ion battery has been widely investigated in efforts to design a green and safe technology that can provide a highly specific capacity, high efficiency and long life for high power applications such as the smart grid and electric vehicle. It is believed that the advantages of this battery will overcome the limitations of the rechargeable lithium-ion battery with organic electrolytes that comprise safety and create high fabrication cost issues. This review focuses on the opportunities of the aqueous rechargeable lithium-ion battery compared to the conventional rechargeable lithium-ion battery with organic-based electrolytes. Previously reported studies are briefly summarised, together with the presentation of new findings based on the conductivity, morphology, electrochemical performance and cycling stability results. The factors that influence the electrochemical performance, the challenges and potential of the aqueous rechargeable lithium-ion battery are highlighted in order to understand and maintained the excellent battery performance.

Synthesis and electrochemical properties of nanosized LiFeO2 particles with a layered rocksalt structure for lithium batteries

International Nuclear Information System (INIS)

Hirayama, Masaaki; Tomita, Hiroki; Kubota, Kei; Ido, Hidekazu; Kanno, Ryoji

2012-01-01

Highlights: ► 40-nm-sized O3-LiFeO 2 exhibits higher discharge capacities and rate characteristics than 400-nm-sized O3-LiFeO 2 . ► The cation disorder of Li and Fe ions might have affected the electrochemical activity of the O3-LiFeO 2 nanoparticles. ► A phase change from a layered structure to a cubic structure during electrochemical cycling. ► The new cubic phase allowed a stable electrochemical reaction between 4.5 and 1.0 V. -- Abstract: Layered rocksalt-type LiFeO 2 particles (O3-LiFeO 2 ) with average particle sizes of ca. 40 and 400 nm were synthesized by an ion exchange reaction from α-NaFeO 2 precursors. X-ray diffraction (XRD) patterns and scanning electron microscopy (SEM) images confirmed the formation of nanosized O3-LiFeO 2 . 40-nm LiFeO 2 exhibited a higher discharge capacity (115 mAh g −1 ) than 400-nm LiFeO 2 (80 mAh g −1 ), and also had better rate characteristics. The downsizing effect and cation disorder between the lithium and iron layers may have improved the electrochemical activity of the LiFeO 2 particles. Transmission electron microscopy (TEM) observation indicated a phase transition from O3-LiFeO 2 to a cubic lattice system during the electrochemical process. The cubic lithium iron oxide exhibited stable electrochemical reactions based on the Fe 2+ /Fe 3+ and Fe 2+ /Fe 0 redox couples at voltages between 4.5 and 1.0 V. The discharge capacities of 40-nm LiFeO 2 were ca. 115, 210, and 390 mAh g −1 under cutoff voltages of 4.5–2.0 V, 4.5–1.5 V, and 4.5–1.0 V, respectively.

Comparison of Lithium-Ion Anode Materials Using an Experimentally Verified Physics-Based Electrochemical Model

Directory of Open Access Journals (Sweden)

Rujian Fu

2017-12-01

Full Text Available Researchers are in search of parameters inside Li-ion batteries that can be utilized to control their external behavior. Physics-based electrochemical model could bridge the gap between Li+ transportation and distribution inside battery and battery performance outside. In this paper, two commercially available Li-ion anode materials: graphite and Lithium titanate (Li4Ti5O12 or LTO were selected and a physics-based electrochemical model was developed based on half-cell assembly and testing. It is found that LTO has a smaller diffusion coefficient (Ds than graphite, which causes a larger overpotential, leading to a smaller capacity utilization and, correspondingly, a shorter duration of constant current charge or discharge. However, in large current applications, LTO performs better than graphite because its effective particle radius decreases with increasing current, leading to enhanced diffusion. In addition, LTO has a higher activation overpotential in its side reactions; its degradation rate is expected to be much smaller than graphite, indicating a longer life span.

Electrochemical study of nanometric Si on carbon for lithium ion secondary batteries

Energy Technology Data Exchange (ETDEWEB)

Doh, Chil-Hoon; Lee, Jung-Hoon; Lee, Duck-Jun; Kim, Ju-Seok; Jin, Bong-Soo; Moon, Seong-In [Korea Electrotechnology Research Institute, Changwon 641-120 (Korea, Republic of); Hwang, Young-Ki [Kyungnam University, Masan 631-701 (Korea, Republic of); Park, Cheol-Wan, E-mail: chdoh@keri.re.k [Sodiff Advanced Materials Co. Ltd, Youngju 750-080 (Korea, Republic of)

2010-05-01

The electrochemical and thermochemical properties of a silicon-graphite composite anode for lithium ion batteries were evaluated. The electrochemical properties were varied by the condition of pretreatment. The electrochemical pretreatment of constant current (C/10) and constant potential for 24 h showed specific discharge and charge capacities of 941 and 781 mA h g{sup -1} to give a specific irreversible capacity of 161 mA h g{sup -1} and a coulombic efficiency of 83%. The initial cycle as the next cycle of pretreatment showed a specific charge capacity (Li desertion) of 698 mA h g{sup -1} and a coulombic efficiency of 95%. Coulombic efficiency at the fifth cycle was 97% to clear up almost all of the irreversible capacity. During the pretreatment cycle to the fourth cycle, the average specific charge capacity was 683 mA h g{sup -1} and the cumulative irreversible capacity was 264 mA h g{sup -1}. Exothermic heat values based on the specific capacity of the discharged (Li insertion) electrode of silicon-graphite composite for the temperature range of 50-300 {sup 0}C were 2.09 and 2.21 J mA{sup -1}h{sup -1} for 0 and 2 h as time of pretreatment in the case of just disassembled wet electrodes and 1.43 and 1.01 J mA{sup -1}h{sup -1} for 12 and 24 h as time of pretreatment in the case of dried electrodes, respectively.

Electrochemical lithium insertion in graphite containing dispersed tin-antimony alloys

Energy Technology Data Exchange (ETDEWEB)

Billaud, Denis; Nabais, Catarina; Mercier, Cedric [LCSM, Laboratoire de Chimie du Solide Mineral, Nancy University, BP 239, 54506 Vandoeuvre les Nancy Cedex (France); Schneider, Raphael [LCPME, Laboratoire de Chimie Physique et Microbiologie pour l' Environnement, Nancy University, Faculte de Pharmacie, BP 80 403, 54001 Nancy Cedex (France); Willmann, Patrick [CNES, Centre National d' Etudes Spatiales, 18, Avenue E. Belin, 31055 Toulouse Cedex (France)

2008-09-15

Graphite/SnSb composites were prepared by solution-phase reduction of SnCl{sub 2} and SbCl{sub 5} in the presence of graphite powder using either t-BuONa-activated NaH or t-BuOLi-activated LiH. Crude and washed materials were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM) and field emission gun-scanning electron microscopy (FEG-SEM). Electrochemical lithium insertion was carried out in both types of composites using voltammetry or galvanostatic charge/discharge techniques. It appeared that graphite-SnSb composites prepared using t-BuOLi-activated LiH as reductant displayed the highest reversible capacity (ca. 500 mA h g{sup -1}). This phenomenon is likely in relation with a better dispersion and grafting of metal particles on graphite, as suggested by FEG-SEM and TEM analyses. However, such dispersion appeared to increase significantly the irreversible capacity. (author)

Parallelized Genetic Identification of the Thermal-Electrochemical Model for Lithium-Ion Battery

Directory of Open Access Journals (Sweden)

Liqiang Zhang

2013-01-01

Full Text Available The parameters of a well predicted model can be used as health characteristics for Lithium-ion battery. This article reports a parallelized parameter identification of the thermal-electrochemical model, which significantly reduces the time consumption of parameter identification. Since the P2D model has the most predictability, it is chosen for further research and expanded to the thermal-electrochemical model by coupling thermal effect and temperature-dependent parameters. Then Genetic Algorithm is used for parameter identification, but it takes too much time because of the long time simulation of model. For this reason, a computer cluster is built by surplus computing resource in our laboratory based on Parallel Computing Toolbox and Distributed Computing Server in MATLAB. The performance of two parallelized methods, namely Single Program Multiple Data (SPMD and parallel FOR loop (PARFOR, is investigated and then the parallelized GA identification is proposed. With this method, model simulations running parallelly and the parameter identification could be speeded up more than a dozen times, and the identification result is batter than that from serial GA. This conclusion is validated by model parameter identification of a real LiFePO4 battery.

Quantum mechanic tunneling and efficiency of Faraday current-generating process in porous nanostructures

Directory of Open Access Journals (Sweden)

I.I. Grygorchak

2011-06-01

Full Text Available Thermodynamics and kinetics of lithium intercalation into C-SiO2 nanocomposites are investigated. Dependencies of both differential capacity and intercalation kinetics on the nanocomposite size are established. The processes are analyzed in terms of the impedance model. The obtained results are explained based on the quantum effect of interference blockade of electron tunneling into a nonmetallic nanoparticle. Propositions for the new electrochemical energy storage technology are presented.

Functional interface of polymer modified graphite anode

Energy Technology Data Exchange (ETDEWEB)

Komaba, S.; Ozeki, T.; Okushi, K. [Department of Applied Chemistry, Tokyo University of Science, 1-3 Kagurazaka, Shinjuku, Tokyo 162-8601 (Japan)

2009-04-01

Graphite electrodes were modified by polyacrylic acid (PAA), polymethacrylic acid (PMA), and polyvinyl alcohol (PVA). Their electrochemical properties were examined in 1 mol dm{sup -3} LiClO{sub 4} ethylene carbonate:dimethyl carbonate (EC:DMC) and propylene carbonate (PC) solutions as an anode of lithium ion batteries. Generally, lithium ions hardly intercalate into graphite in the PC electrolyte due to a decomposition of the PC electrolyte at ca. 0.8 V vs. Li/Li{sup +}, and it results in the exfoliation of the graphene layers. However, the modified graphite electrodes with PAA, PMA, and PVA demonstrated the stable charge-discharge performance due to the reversible lithium intercalation not only in the EC:DMC but also in the PC electrolytes since the electrolyte decomposition and co-intercalation of solvent were successfully suppressed by the polymer modification. It is thought that these improvements were attributed to the interfacial function of the polymer layer on the graphite which interacted with the solvated lithium ions at the electrode interface. (author)

Allylic ionic liquid electrolyte-assisted electrochemical surface passivation of LiCoO2 for advanced, safe lithium-ion batteries

Science.gov (United States)

Mun, Junyoung; Yim, Taeeun; Park, Jang Hoon; Ryu, Ji Heon; Lee, Sang Young; Kim, Young Gyu; Oh, Seung M.

2014-01-01

Room-temperature ionic liquid (RTIL) electrolytes have attracted much attention for use in advanced, safe lithium-ion batteries (LIB) owing to their nonvolatility, high conductivity, and great thermal stability. However, LIBs containing RTIL-electrolytes exhibit poor cyclability because electrochemical side reactions cause problematic surface failures of the cathode. Here, we demonstrate that a thin, homogeneous surface film, which is electrochemically generated on LiCoO2 from an RTIL-electrolyte containing an unsaturated substituent on the cation (1-allyl-1-methylpiperidinium bis(trifluoromethanesulfonyl)imide, AMPip-TFSI), can avert undesired side reactions. The derived surface film comprised of a high amount of organic species from the RTIL cations homogenously covered LiCoO2 with a <25 nm layer and helped suppress unfavorable thermal reactions as well as electrochemical side reactions. The superior performance of the cell containing the AMPip-TFSI electrolyte was further elucidated by surface, electrochemical, and thermal analyses. PMID:25168309

Lithium ion intercalation in thin crystals of hexagonal TaSe2 gated by a polymer electrolyte

Science.gov (United States)

Wu, Yueshen; Lian, Hailong; He, Jiaming; Liu, Jinyu; Wang, Shun; Xing, Hui; Mao, Zhiqiang; Liu, Ying

2018-01-01

Ionic liquid gating has been used to modify the properties of layered transition metal dichalcogenides (TMDCs), including two-dimensional (2D) crystals of TMDCs used extensively recently in the device work, which has led to observations of properties not seen in the bulk. The main effect comes from the electrostatic gating due to the strong electric field at the interface. In addition, ionic liquid gating also leads to ion intercalation when the ion size of the gate electrolyte is small compared to the interlayer spacing of TMDCs. However, the microscopic processes of ion intercalation have rarely been explored in layered TMDCs. Here, we employed a technique combining photolithography device fabrication and electrical transport measurements on the thin crystals of hexagonal TaSe2 using multiple channel devices gated by a polymer electrolyte LiClO4/Polyethylene oxide (PEO). The gate voltage and time dependent source-drain resistances of these thin crystals were used to obtain information on the intercalation process, the effect of ion intercalation, and the correlation between the ion occupation of allowed interstitial sites and the device characteristics. We found a gate voltage controlled modulation of the charge density waves and a scattering rate of charge carriers. Our work suggests that ion intercalation can be a useful tool for layered materials engineering and 2D crystal device design.

Co-estimation of state-of-charge, capacity and resistance for lithium-ion batteries based on a high-fidelity electrochemical model

International Nuclear Information System (INIS)

Zheng, Linfeng; Zhang, Lei; Zhu, Jianguo; Wang, Guoxiu; Jiang, Jiuchun

2016-01-01

Highlights: • The numerical solution for an electrochemical model is presented. • Trinal PI observers are used to concurrently estimate SOC, capacity and resistance. • An iteration-approaching method is incorporated to enhance estimation performance. • The robustness against aging and temperature variations is experimentally verified. - Abstract: Lithium-ion batteries have been widely used as enabling energy storage in many industrial fields. Accurate modeling and state estimation play fundamental roles in ensuring safe, reliable and efficient operation of lithium-ion battery systems. A physics-based electrochemical model (EM) is highly desirable for its inherent ability to push batteries to operate at their physical limits. For state-of-charge (SOC) estimation, the continuous capacity fade and resistance deterioration are more prone to erroneous estimation results. In this paper, trinal proportional-integral (PI) observers with a reduced physics-based EM are proposed to simultaneously estimate SOC, capacity and resistance for lithium-ion batteries. Firstly, a numerical solution for the employed model is derived. PI observers are then developed to realize the co-estimation of battery SOC, capacity and resistance. The moving-window ampere-hour counting technique and the iteration-approaching method are also incorporated for the estimation accuracy improvement. The robustness of the proposed approach against erroneous initial values, different battery cell aging levels and ambient temperatures is systematically evaluated, and the experimental results verify the effectiveness of the proposed method.

A New All-Solid-State Hyperbranched Star Polymer Electrolyte for Lithium Ion Batteries: Synthesis and Electrochemical Properties

International Nuclear Information System (INIS)

Wang, Ailian; Xu, Hao; Zhou, Qian; Liu, Xu; Li, Zhengyao; Gao, Rui; Wu, Na; Guo, Yuguo; Li, Huayi; Zhang, Liaoyun

2016-01-01

Highlights: • A new hyperbranched multi-arm star polymer was successfully synthesized. • The star polymer electrolyte has good thermal stability and forming-film property. • The ion conductivity electrolyte can reach 8.3 × 10"−"5 S cm"−"1 at room temperature. • The star polymer electrolyte has wide electrochemical windows of 4.7 V. - Abstract: A new hyperbranched multi-arm star polymer with hyperbranched polystyrene (HBPS) as core and polymethyl methacrylate-block-poly(ethylene glycol) methyl ether methacrylate(PMMA-b-PPEGMA) as arms was firstly synthesized by atom transfer radical polymerization. The obtained hyperbranched multi-arm star polymer (HBPS-(PMMA-b-PPEGMA)_x) exhibited good thermal stability with a thermal decomposition temperature of 372 °C. The transparent, free-standing, flexible polymer electrolyte film of the blending of HBPS-(PMMA-b-PPEGMA)_x and lithium bis(trifluoromethanesulfonyl) imide (LiTFSI) was successfully fabricated by a solution casting method. The ionic conductivity of the hyperbranched star polymer electrolyte with a molar ratio of [EO]/[Li] of 30 could reach 8.3 × 10"−"5 S cm"−"1 at 30 °C (with the content of PPEGMA of 83.7%), and 2.0 × 10"−"4 S cm"−"1 at 80 °C (with the content of PPEGMA of 51.6%). The effect of the concentration of lithium salts on ionic conductivity was also investigated. The obtained all-solid-state polymer electrolyte possessed a wide electrochemical stability window of 4.7 V (vs. Li"+/Li), and a lithium-ion transference number (t_L_i"+) up to 0.31. The interfacial impedance of the fabricated LiÔöépolymer electrolyteÔöéLi symmetric cell based on hyperbranched star multi-arm polymer electrolyte exhibited good interfacial compatibility between all-solid-state polymer electrolyte and electrodes. The excellent properties of the hyperbranched star polymer electrolyte made it attractive as solid-state polymer electrolyte for lithium-ion batteries.

Temperature-dependent electrochemical heat generation in a commercial lithium-ion battery

Science.gov (United States)

Bandhauer, Todd M.; Garimella, Srinivas; Fuller, Thomas F.

2014-02-01

Lithium-ion batteries suffer from inherent thermal limitations (i.e., capacity fade and thermal runaway); thus, it is critical to understand heat generation experienced in the batteries under normal operation. In the current study, reversible and irreversible electrochemical heat generation rates were measured experimentally on a small commercially available C/LiFePO4 lithium-ion battery designed for high-rate applications. The battery was tested over a wide range of temperatures (10-60 °C) and discharge and charge rates (∼C/4-5C) to elucidate their effects. Two samples were tested in a specially designed wind tunnel to maintain constant battery surface temperature within a maximum variation of ±0.88 °C. A data normalization technique was employed to account for the observed capacity fade, which was largest at the highest rates. The heat rate was shown to increase with both increasing rate and decreasing temperature, and the reversible heat rate was shown to be significant even at the highest rate and temperature (7.4% at 5C and 55 °C). Results from cycling the battery using a dynamic power profile also showed that constant-current data predict the dynamic performance data well. In addition, the reversible heat rate in the dynamic simulation was shown to be significant, especially for charge-depleting HEV applications.

Facile synthesis of Fe-incorporated CuO nanoarrays with enhanced electrochemical performance for lithium ion full batteries

Energy Technology Data Exchange (ETDEWEB)

Heng, Bojun [Institute of Nano-science and Technology, Central-China Normal University, Wuhan, 430079 (China); Department of Applied Physics, Wuhan University of Science and Technology, Wuhan, 430065 (China); Qing, Chen; Wang, Hai; Sun, Daming; Wang, Bixiao [Institute of Nano-science and Technology, Central-China Normal University, Wuhan, 430079 (China); Tang, Yiwen, E-mail: ywtang@phy.ccnu.edu.cn [Institute of Nano-science and Technology, Central-China Normal University, Wuhan, 430079 (China)

2015-11-15

CuO nanoarrays (CNAs) and Fe-incorporated CuO nanoarrays (FCNAs) were fabricated by hydrothermal method. Addition of Fe salt to the reaction mixture allowed the introduction of iron oxide onto the CNAs surface, which was characterized by XPS and HRTEM. Introducing Fe ion into reaction precursor significantly affected not only the morphologies of as-prepared products but also their electrochemical performance as anode for lithium ion full battery. The FCNAs electrodes showed higher specific capacity and better capacity retention at different current densities than that of CNAs. - Highlights: • Fe-incorporated CuO nanoarrays were fabricated by hydrothermal method. • Fe salt in reaction mixture leads to iron oxides forming on the surface of CuO. • Fe-incorporating improves the lithium ion battery performance of CuO anodes.

Electrochemical synthesis of 1D core-shell Si/TiO2 nanotubes for lithium ion batteries

Science.gov (United States)

Kowalski, Damian; Mallet, Jeremy; Thomas, Shibin; Nemaga, Abirdu Woreka; Michel, Jean; Guery, Claude; Molinari, Michael; Morcrette, Mathieu

2017-09-01

Silicon negative electrode for lithium ion battery was designed in the form of self-organized 1D core-shell nanotubes to overcome shortcomings linked to silicon volume expansion upon lithiation/delithiation typically occurring with Si nanoparticles. The negative electrode was formed on TiO2 nanotubes in two step electrochemical synthesis by means of anodizing of titanium and electrodeposition of silicon using ionic liquid electrolytes. Remarkably, it was found that the silicon grows perpendicularly to the z-axis of nanotube and therefore its thickness can be precisely controlled by the charge passed in the electrochemical protocol. Deposited silicon creates a continuous Si network on TiO2 nanotubes without grain boundaries and particle-particle interfaces, defining its electrochemical characteristics under battery testing. In the core-shell system the titania nanotube play a role of volume expansion stabilizer framework holding the nanostructured silicon upon lithiation/delithiation. The nature of Si shell and presence of titania core determine stable performance as negative electrode tested in half cell of CR2032 coin cell battery.

Electrochemical-thermal Modeling to Evaluate Active Thermal Management of a Lithium-ion Battery Module

International Nuclear Information System (INIS)

Bahiraei, Farid; Fartaj, Amir; Nazri, Gholam-Abbas

2017-01-01

Lithium-ion batteries are commonly used in hybrid electric and full electric vehicles (HEV and EV). In HEV, thermal management is a strict requirement to control the batteries temperature within an optimal range in order to enhance performance, safety, reduce cost, and prolong the batteries lifetime. The optimum design of a thermal management system depends on the thermo-electrochemical behavior of the batteries, operating conditions, and weight and volume constraints. The aim of this study is to investigate the effects of various operating and design parameters on the thermal performance of a battery module consisted of six building block cells. An electrochemical-thermal model coupled to conjugate heat transfer and fluid dynamics simulations is used to assess the effectiveness of two indirect liquid thermal management approaches under the FUDC driving cycle. In this study, a novel pseudo 3D electrochemical-thermal model of the battery is used. It is found that the cooling plate thickness has a significant effect on the maximum and gradient of temperature in the module. Increasing the Reynolds number decreases the average temperature but at the expense of temperature uniformity. The results show that double channel cooling system has a lower maximum temperature and more uniform temperature distribution compared to a single channel cooling system.

Exploration of artificial neural network [ANN] to predict the electrochemical characteristics of lithium-ion cells

Energy Technology Data Exchange (ETDEWEB)

Parthiban, Thirumalai; Ravi, R.; Kalaiselvi, N. [Central Electrochemical Research Institute (CECRI), Karaikudi 630006 (India)

2007-12-31

CoO anode, as an alternate to the carbonaceous anodes of lithium-ion cells has been prepared and investigated for electrochemical charge-discharge characteristics for about 50 cycles. Artificial neural networks (ANNs), which are useful in estimating battery performance, has been deployed for the first time to forecast and to verify the charge-discharge behavior of lithium-ion cells containing CoO anode for a total of 50 cycles. In this novel approach, ANN that has one input layer with one neuron corresponding to one input variable, viz., cycles [charge-discharge cycles] and a hidden layer consisting of three neurons to produce their outputs to the output layer through a sigmoid function has been selected for the present investigation. The output layer consists of two neurons, representing the charge and discharge capacity, whose activation function is also the sigmoid transfer function. In this ever first attempt to exploit ANN as an effective theoretical tool to understand the charge-discharge characteristics of lithium-ion cells, an excellent agreement between the calculated and observed capacity values was found with CoO anodes with the best fit values corresponding to an error factor of <1%, which is the highlight of the present study. (author)

Physico-Chemical and Electrochemical Properties of Nanoparticulate NiO/C Composites for High Performance Lithium and Sodium Ion Battery Anodes

Directory of Open Access Journals (Sweden)

Amaia Iturrondobeitia

2017-12-01

Full Text Available Nanoparticulate NiO and NiO/C composites with different carbon proportions have been prepared for anode application in lithium and sodium ion batteries. Structural characterization demonstrated the presence of metallic Ni in the composites. Morphological study revealed that the NiO and Ni nanoparticles were well dispersed in the matrix of amorphous carbon. The electrochemical study showed that the lithium ion batteries (LIBs, containing composites with carbon, have promising electrochemical performances, delivering specific discharge capacities of 550 mAh/g after operating for 100 cycles at 1C. These excellent results could be explained by the homogeneity of particle size and structure, as well as the uniform distribution of NiO/Ni nanoparticles in the in situ generated amorphous carbon matrix. On the other hand, the sodium ion battery (NIB with the NiO/C composite revealed a poor cycling stability. Post-mortem analyses revealed that this fact could be ascribed to the absence of a stable Solid Electrolyte Interface (SEI or passivation layer upon cycling.

Coupling of Mechanical Behavior of Lithium Ion Cells to Electrochemical-Thermal Models for Battery Crush; NREL (National Renewable Energy Laboratory)

Energy Technology Data Exchange (ETDEWEB)

Pesaran, Ahmad; Zhang, Chao; Santhanagopalan, Shriram; Sahraei, Elham; Wierzbiki, Tom

2015-06-15

Propagation of failure in lithium-ion batteries during field events or under abuse is a strong function of the mechanical response of the different components in the battery. Whereas thermal and electrochemical models that capture the abuse response of batteries have been developed and matured over the years, the interaction between the mechanical behavior and the thermal response of these batteries is not very well understood. With support from the Department of Energy, NREL has made progress in coupling mechanical, thermal, and electrochemical lithium-ion models to predict the initiation and propagation of short circuits under external crush in a cell. The challenge with a cell crush simulation is to estimate the magnitude and location of the short. To address this, the model includes an explicit representation of each individual component such as the active material, current collector, separator, etc., and predicts their mechanical deformation under different crush scenarios. Initial results show reasonable agreement with experiments. In this presentation, the versatility of the approach for use with different design factors, cell formats and chemistries is explored using examples.

Metallization and stiffness of the Li-intercalated MoS{sub 2} bilayer

Energy Technology Data Exchange (ETDEWEB)

Petrova, N.V. [Institute of Physics of National Academy of Sciences of Ukraine, Prospect Nauki 46, Kiev 03028 (Ukraine); Yakovkin, I.N., E-mail: yakov@iop.kiev.ua [Institute of Physics of National Academy of Sciences of Ukraine, Prospect Nauki 46, Kiev 03028 (Ukraine); Zeze, D.A. [School of Engineering & Computing Sciences, Durham University, Durham DH1 3LE (United Kingdom)

2015-10-30

Graphical abstract: The band structures, DOS, and Fermi surfaces for the MoS{sub 2} bilayer with adsorbed (a, c, e) and intercalated (b, d, f) Li (1 × 1) layer. - Highlights: • Adsorbed or intercalated Li monolayer makes the MoS{sub 2} surface metallic. • Increasing density of adsorbed Li leads to the nonmetal-to-metal transition in the layer. • Lithium inserted into MoS{sub 2} bilayers increases the interlayer interaction. - Abstract: Performed density-functional theory (DFT) calculations have shown that the Li adsorption on the MoS{sub 2} (0 0 0 1) surface, as well as Li intercalation into the space between MoS{sub 2} layers, transforms the semiconductor band structure of MoS{sub 2} into metallic. For the (√3 × √3) – R30° Li layer, the band structures of the MoS{sub 2} bilayer with adsorbed and intercalated Li are very similar, while for higher Li concentrations, the character of metallization for the adsorbed layer substantially differs from that of the MoS{sub 2}–Li–MoS{sub 2} layered system. In particular, for the adsorbed (1 × 1) Li monolayer, the increased density of the layer leads to the nonmetal-to-metal transition, which is evident from the appearance of the band crossing E{sub F} with an upward dispersion, pertinent to simple metals. It has been demonstrated that intercalated Li substantially increases the interlayer interaction in MoS{sub 2}. Specifically, the estimated 0.12 eV energy of the interlayer interaction in the MoS{sub 2} bilayer increases to 0.60 eV. This result is also consistent with results of earlier DFT calculations and available experimental results for alkali-intercalated graphene layers, which have demonstrated a substantial increase in the stiffness due to intercalation of alkalis.

Empirical Modeling of Lithium-ion Batteries Based on Electrochemical Impedance Spectroscopy Tests

International Nuclear Information System (INIS)

Samadani, Ehsan; Farhad, Siamak; Scott, William; Mastali, Mehrdad; Gimenez, Leonardo E.; Fowler, Michael; Fraser, Roydon A.

2015-01-01

Highlights: • Two commercial Lithium-ion batteries are studied through HPPC and EIS tests. • An equivalent circuit model is developed for a range of operating conditions. • This model improves the current battery empirical models for vehicle applications • This model is proved to be efficient in terms of predicting HPPC test resistances. - ABSTRACT: An empirical model for commercial lithium-ion batteries is developed based on electrochemical impedance spectroscopy (EIS) tests. An equivalent circuit is established according to EIS test observations at various battery states of charge and temperatures. A Laplace transfer time based model is developed based on the circuit which can predict the battery operating output potential difference in battery electric and plug-in hybrid vehicles at various operating conditions. This model demonstrates up to 6% improvement compared to simple resistance and Thevenin models and is suitable for modeling and on-board controller purposes. Results also show that this model can be used to predict the battery internal resistance obtained from hybrid pulse power characterization (HPPC) tests to within 20 percent, making it suitable for low to medium fidelity powertrain design purposes. In total, this simple battery model can be employed as a real-time model in electrified vehicle battery management systems

Electrochemical impedance characterization of FeSn2 electrodes for Li-ion batteries

International Nuclear Information System (INIS)

Chamas, M.; Lippens, P-E.; Jumas, J-C.; Hassoun, J.; Panero, S.; Scrosati, B.

2011-01-01

Highlights: → In this paper we study a tin based, FeSn 2 , high capacity lithium-alloying electrode. → The electrochemical performance of this electrode in lithium batteries is remarkably influenced by the current rate. → This aspect is investigated by electrochemical techniques such as galvanostatic cycling and impedance spectroscopy. → The results demonstrated that the good electrochemical behavior of the electrode at the higher currents is due to the formation of a stable solid electrolyte interphase (SEI) film. - Abstract: This work reports the electrochemical characterization of a micro-scale FeSn 2 electrode in a lithium battery. The electrode is proposed as anode material for advanced lithium ion batteries due to its characteristics of high capacity (500 mAh g -1 ) and low working voltage (0.6 V vs. Li). The electrochemical alloying process is studied by cyclic voltammetry and galvanostatic cycling while the interfacial properties are investigated by electrochemical impedance spectroscopy. The impedance measurements in combination with the galvanostatic cycling tests reveal relatively low overall impedance values and good electrochemical performance for the electrode, both in terms of delivered capacity and cycling stability, even at the higher C-rate regimes.

Effects of low-pressure nitrogen plasma treatment on the surface properties and electrochemical performance of the polyethylene separator used lithium-ion batteries

Science.gov (United States)

Li, Chun; Li, Hsiao-Ling; Li, Chi-Heng; Liu, Yu-Shuan; Sung, Yu-Ching; Huang, Chun

2018-01-01

In this paper, we describe the surface transition of the polyethylene (PE) separator used in lithium-ion batteries treated by low-pressure nitrogen plasma discharge. The nitrogen-plasma-treated PE separator was characterized by contact angle measurement, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and scanning electron microscopy. The electrochemical performance of the lithium ion batteries fabricated with the nitrogen-plasma-treated separator was also evaluated. Results showed that polar functionalization groups were induced on the PE surface by the nitrogen plasma discharge, causing the surface to become hydrophilic. The increases in surface wettability and surface free energy result in electrolyte retention improvement. Moreover, the nitrogen plasma-treated PE separator leads to superior performance in lithium-ion battery assembly.

The standard Gibbs free energy of formation of lithium manganese oxides at the temperatures of (680, 740 and 800) K

International Nuclear Information System (INIS)

Rog, G.; Kucza, W.; Kozlowska-Rog, A.

2004-01-01

The standard Gibbs free energy of formation of LiMnO 2 and LiMn 2 O 4 at the temperatures of (680, 740 and 800) K has been determined with the help of the solid-state galvanic cells involving lithium-β-alumina electrolyte. The equilibrium electrical potentials of cathode containing Li x Mn 2 O 4 spinel, in the composition ranges 0≤x≤1 and 1≤x≤2, vs. metallic lithium in the reversible intercalation galvanic cell have been calculated. The existence of two-voltage plateaus which appeared during charging and discharging processes in reversible intercalation of lithium into Li x Mn 2 O 4 spinel, has been discussed

Nanostructured Iron and Manganese Oxide Electrode Materials for Lithium Batteries: Influence of Chemical and Physical Properties on Electrochemistry

Science.gov (United States)

Durham, Jessica L.

The widespread use of portable electronics and growing interest in electric and hybrid vehicles has generated a mass market for batteries with increased energy densities and enhanced electrochemical performance. In order to address a variety of applications, commercially fabricated secondary lithium-ion batteries employ transition metal oxide based electrodes, the most prominent of which include lithium nickel manganese cobalt oxide (LiNixMn yCo1-x-yO2), lithium iron phosphate (LiFePO4), and lithium manganese oxide (LiMn 2O4). Transition metal oxides are of particular interest as cathode materials due to their robust framework for lithium intercalation, potential for high energy density, and utilization of earth-abundant elements (i.e. iron and manganese) leading to decreased toxicity and cost-effective battery production on industrial scales. Specifically, this research focuses on MgFe2O4, AgxMn8O16, and AgFeO 2 transition metal oxides for use as electrode materials in lithium-based batteries. The electrode materials are prepared via co-precipitation, reflux, and hydrothermal methods and characterized by several techniques (XRD, SEM, BET, TGA, DSC, XPS, Raman, etc.). The low-temperature syntheses allowed for precise manipulation of structural, compositional, and/or functional properties of MgFe2O4, AgxMn8 O16, and AgFeO2 which have been shown to influence electrochemical behavior. In addition, advanced in situ and ex situ characterization techniques are employed to study the lithiation/de-lithiation process and establish valid redox mechanisms. With respect to both chemical and physical properties, the influence of MgFe2O4 particle size and morphology on electrochemical behavior was established using ex situ X-ray absorption spectroscopy (XAS) and transmission electron microscopy (TEM) imaging. Based on composition, tunneled AgxMn8O16 nanorods, prepared with distinct Ag+ contents and crystallite sizes, display dramatic differences in ion-transport kinetics due to

Cathodic behaviours of a CrO sub 3 -graphite intercalation compound in non-aqueous solutions

Energy Technology Data Exchange (ETDEWEB)

Kurihara, M.; Miura, T.; Kishi, T. (Keio University, Tokyo (Japan). Faculty of Science)

1991-08-05

CrO{sub 3}-graphite intercalation compound (GIC) specimen was prepared by solvent method using acetic acid as a solvent and potassium permanganate as a catalyst, and its cathodic behavior in a lithium cell was studied in non-aqueous solutions (1 mol/dm{sup 3} LiClO{sub 4} in propylene carbonate (PC) or dimethylsulfoxide (DMSO)). Changes in electronic and layered lattice structures induced by cathodic reduction were measured by electron spin resonance method and X-ray diffraction one, respectively. As a result, electrochemical insertion of Li into CrO{sub 3}-GIC proceeded only in DMSO solution where reduction of Cr components was followed by that of graphite units. The amount of discharge electricity for CrO{sub 3}-GIC in DMSO solution was three times as large as that for graphite. Although the effect of non-aqueous solutions on the lithiation reaction was not yet clear fundamentally, it was expected that another electrolyte solutions are probably found out based on this experiments from which Li is inserted into CrO{sub 3}-GIC at higher discharge potentials. 22 refs., 9 figs., 1 tab.

Combined operando X-ray diffraction-electrochemical impedance spectroscopy detecting solid solution reactions of LiFePO4 in batteries.

Science.gov (United States)

Hess, Michael; Sasaki, Tsuyoshi; Villevieille, Claire; Novák, Petr

2015-09-08

Lithium-ion batteries are widely used for portable applications today; however, often suffer from limited recharge rates. One reason for such limitation can be a reduced active surface area during phase separation. Here we report a technique combining high-resolution operando synchrotron X-ray diffraction coupled with electrochemical impedance spectroscopy to directly track non-equilibrium intermediate phases in lithium-ion battery materials. LiFePO4, for example, is known to undergo phase separation when cycled under low-current-density conditions. However, operando X-ray diffraction under ultra-high-rate alternating current and direct current excitation reveal a continuous but current-dependent, solid solution reaction between LiFePO4 and FePO4 which is consistent with previous experiments and calculations. In addition, the formation of a preferred phase with a composition similar to the eutectoid composition, Li0.625FePO4, is evident. Even at a low rate of 0.1C, ∼20% of the X-ray diffractogram can be attributed to non-equilibrium phases, which changes our understanding of the intercalation dynamics in LiFePO4.

A DNA biosensor based on the electrocatalytic oxidation of amine by a threading intercalator

International Nuclear Information System (INIS)

Gao Zhiqiang; Tansil, Natalia

2009-01-01

An electrochemical biosensor for the detection of DNA based a peptide nucleic acid (PNA) capture probe (CP) modified indium tin oxide electrode (ITO) is described in this report. After hybridization, a threading intercalator, N,N'-bis[(3-propyl)-imidazole]-1,4,5,8-naphthalene diimide (PIND) imidazole complexed with Ru(bpy) 2 Cl (PIND-Ru, bpy = 2,2'-bipyridine), was introduced to the biosensor. PIND-Ru selectively intercalated to double-stranded DNA (ds-DNA) and became immobilized on the biosensor surface. Voltammetric tests showed highly stable and reversible electrochemical oxidation/reduction processes and the peak currents can directly be utilized for DNA quantification. When the tests were conducted in an amine-containing medium, Tris-HCl buffer for example, a remarkable improvement in the voltammetric response and noticeable enhancements of voltammetric and amperometric sensitivities were observed due to the electrocatalytic activity of the [Ru(bpy) 2 Cl] redox moieties. Electrocatalytic current was observed when as little as 3.0 attomoles of DNA was present in the sample solution

Biomass carbon micro/nano-structures derived from ramie fibers and corncobs as anode materials for lithium-ion and sodium-ion batteries

International Nuclear Information System (INIS)

Jiang, Qiang; Zhang, Zhenghao; Yin, Shengyu; Guo, Zaiping; Wang, Shiquan; Feng, Chuanqi

2016-01-01

Highlights: • Ramie fibers and corncobs are used as precursors to prepare the biomass carbons. • The ramie fiber carbon (RFC) took on morphology of 3D micro-rods. • The corncob carbon (CC) possessed a 2D nanosheets structure. • Both RFC and CC exhibited outstanding electrochemical performances in LIBs and SIBs systems. - Abstract: Three-dimensional (3D) rod-like carbon micro-structures derived from natural ramie fibers and two-dimensional (2D) carbon nanosheets derived from corncobs have been fabricated by heat treatment at 700 °C under argon atomsphere. The structure and morphology of the as-obtained ramie fiber carbon (RFC) and corncob carbon (CC) were characterized by X-ray diffraction (XRD), Raman spectroscopy, scanning electron microscopy (SEM) and transmission electron microscopy (TEM) technique. The electrochemical performances of the biomass carbon-based anode in lithium-ion batteries (LIBs) and sodium-ion batteries (SIBs) were investigated. When tested as anode material for lithium ion batteries, both the RFC microrods and CC nanosheets exhibited high capacity, excellent rate capability, and stable cyclability. The specific capacity were still as high as 489 and 606 mAhg −1 after 180 cycles when cycled at room temperature in a 3.0–0.01 V potential (vs. Li/Li + ) window at current density of 100 mAg −1 , respectively, which are much higher than that of graphite (375 mAhg −1 ) under the same current density. Although the anodes in sodium ion batteries showed poorer specific capability than that in lithium-ion batteries, they still achieve a reversible sodium intercalation capacity of 122 and 139 mAhg −1 with similar cycling stability. The feature of stable cycling performance makes the biomass carbon derived from natural ramie fibers and corncobs to be promising candidates as electrodes in rechargeable sodium-ion batteries and lithium-ion batteries.

Biomass carbon micro/nano-structures derived from ramie fibers and corncobs as anode materials for lithium-ion and sodium-ion batteries

Energy Technology Data Exchange (ETDEWEB)

Jiang, Qiang; Zhang, Zhenghao [Hubei Collaborative Innovation Center for Advanced Organic Chemical Materials, Ministry-of-Education Key Laboratory for Synthesis and Applications of Organic Functional Molecules, Hubei University, Wuhan 430062 (China); Yin, Shengyu [College of Environmental and Biological Engineering, Wuhan Technology and Business University, Wuhan 430065 (China); Guo, Zaiping [Hubei Collaborative Innovation Center for Advanced Organic Chemical Materials, Ministry-of-Education Key Laboratory for Synthesis and Applications of Organic Functional Molecules, Hubei University, Wuhan 430062 (China); Institute for Superconducting & Electronic Materials, University of Wollongong, NSW 2522 (Australia); Wang, Shiquan [Hubei Collaborative Innovation Center for Advanced Organic Chemical Materials, Ministry-of-Education Key Laboratory for Synthesis and Applications of Organic Functional Molecules, Hubei University, Wuhan 430062 (China); Feng, Chuanqi, E-mail: cfeng@hubu.edu.cn [Hubei Collaborative Innovation Center for Advanced Organic Chemical Materials, Ministry-of-Education Key Laboratory for Synthesis and Applications of Organic Functional Molecules, Hubei University, Wuhan 430062 (China)

2016-08-30

Highlights: • Ramie fibers and corncobs are used as precursors to prepare the biomass carbons. • The ramie fiber carbon (RFC) took on morphology of 3D micro-rods. • The corncob carbon (CC) possessed a 2D nanosheets structure. • Both RFC and CC exhibited outstanding electrochemical performances in LIBs and SIBs systems. - Abstract: Three-dimensional (3D) rod-like carbon micro-structures derived from natural ramie fibers and two-dimensional (2D) carbon nanosheets derived from corncobs have been fabricated by heat treatment at 700 °C under argon atomsphere. The structure and morphology of the as-obtained ramie fiber carbon (RFC) and corncob carbon (CC) were characterized by X-ray diffraction (XRD), Raman spectroscopy, scanning electron microscopy (SEM) and transmission electron microscopy (TEM) technique. The electrochemical performances of the biomass carbon-based anode in lithium-ion batteries (LIBs) and sodium-ion batteries (SIBs) were investigated. When tested as anode material for lithium ion batteries, both the RFC microrods and CC nanosheets exhibited high capacity, excellent rate capability, and stable cyclability. The specific capacity were still as high as 489 and 606 mAhg{sup −1} after 180 cycles when cycled at room temperature in a 3.0–0.01 V potential (vs. Li/Li{sup +}) window at current density of 100 mAg{sup −1}, respectively, which are much higher than that of graphite (375 mAhg{sup −1}) under the same current density. Although the anodes in sodium ion batteries showed poorer specific capability than that in lithium-ion batteries, they still achieve a reversible sodium intercalation capacity of 122 and 139 mAhg{sup −1} with similar cycling stability. The feature of stable cycling performance makes the biomass carbon derived from natural ramie fibers and corncobs to be promising candidates as electrodes in rechargeable sodium-ion batteries and lithium-ion batteries.

Effect of covalently bonded polysiloxane multilayers on the electrochemical behavior of graphite electrode in lithium ion batteries

Energy Technology Data Exchange (ETDEWEB)

Pan, Qinmin; Jiang, Yinghua [Department of Applied Chemistry, Harbin Institute of Technology, Harbin 150001 (China)

2008-03-15

Polysiloxane multilayers were covalently bonded to the surface of natural graphite particles via diazonium chemistry and silylation reaction. The as-prepared graphite exhibited excellent discharge-charge behavior as negative electrode materials in lithium ion batteries. The improvement in the electrochemical performance of the graphite electrodes was attributed to the formation of a stable and flexible passive film on their surfaces. It was also revealed that the chemical compositions of the multilayers exerted influence on the electrochemical behavior of the graphite electrodes. The result of this study presents a new strategy to the formation of elastic and strong passive film on the graphite electrode via molecular design. Owing to the diversity of polysilxoane multilayers, this method also enables researchers to control the surface chemistries of carbonaceous materials with flexibility. (author)

Comparative studies of laser annealing technique and furnace annealing by X-ray diffraction and Raman analysis of lithium manganese oxide thin films for lithium-ion batteries

International Nuclear Information System (INIS)

Pröll, J.; Weidler, P.G.; Kohler, R.; Mangang, A.; Heißler, S.; Seifert, H.J.; Pfleging, W.

2013-01-01

The structure and phase formations of radio frequency magnetron sputtered lithium manganese oxide thin films (Li 1.1 Mn 1.9 O 4 ) under ambient air were studied. The influence of laser annealing and furnace annealing, respectively, on the bulk structure and surface phases was compared by using ex-situ X-ray diffraction and Raman analysis. Laser annealing technique formed a dominant (440)-reflection, furnace annealing led to both, (111)- and (440)-reflections within a cubic symmetry (S.G. Fd3m (227)). Additionally, in-situ Raman and in-situ X-ray diffraction were applied for online detection of phase transformation temperatures. In-situ X-ray diffraction measurements clearly identified the starting temperature for the (111)- and (440)-reflections around 525 °C and 400 °C, respectively. The 2θ Bragg peak positions of the characteristic (111)- and (440)-reflections were in good agreement with those obtained through conventional furnace annealing. Laser annealing of lithium manganese oxide films provided a quick and efficient technique and delivered a dominant (440)-reflection which showed the expected electrochemical behavior of the well-known two-step de-/intercalation process of lithium-ions into the cubic spinel structure within galvanostatic testing and cyclic voltammetry. - Highlights: ► Formation of cubic spinel-like phase of Li–Mn–O thin films by rapid laser annealing ► Laser annealing at 680 °C and 100 s was demonstrated as quick crystallization method. ► 400 °C was identified as characteristic onset temperature for (440)-reflex formation

Preparation and enhanced properties of polyaniline/grafted intercalated ZnAl-LDH nanocomposites

Science.gov (United States)

Hu, Jinlong; Gan, Mengyu; Ma, Li; Zhang, Jun; Xie, Shuang; Xu, Fenfang; Shen, JiYue Zheng Xiaoyu; Yin, Hui

2015-02-01

The polymeric nanocomposites (PANI/AD-LDH) were prepared by in situ polymerization based on polyaniline (PANI) and decavanadate-intercalated and γ-aminopropyltriethoxysilane (APTS)-grafted ZnAl-layered double hydroxide (AD-LDH). FTIR and XRD studies confirm the grafting of APTS with decavanadate-intercalated LDH (D-LDH). The extent of grafting (wt%) has also been estimated on the basis of the residue left in nitrogen atmosphere at 800 °C in TGA. SEM and XPS studies show the partial exfoliation of grafted LDH in the PANI matrix and the interfacial interaction between PANI and grafted LDH, respectively. The grafted intercalated layered double hydroxide in reinforcing the properties of the PANI nanocomposites has also been investigated by open circuit potential (OCP), tafel polarization curves (TAF), electrochemical impendence spectroscopy (EIS), salt spray test and TGA-DTA. The experimental results indicate that the PANI/AD-LDH has a higher thermal stability and anticorrosion properties relative to the PANI.

Quantifying microstructural dynamics and electrochemical activity of graphite and silicon-graphite lithium ion battery anodes

Science.gov (United States)

Pietsch, Patrick; Westhoff, Daniel; Feinauer, Julian; Eller, Jens; Marone, Federica; Stampanoni, Marco; Schmidt, Volker; Wood, Vanessa

2016-09-01

Despite numerous studies presenting advances in tomographic imaging and analysis of lithium ion batteries, graphite-based anodes have received little attention. Weak X-ray attenuation of graphite and, as a result, poor contrast between graphite and the other carbon-based components in an electrode pore space renders data analysis challenging. Here we demonstrate operando tomography of weakly attenuating electrodes during electrochemical (de)lithiation. We use propagation-based phase contrast tomography to facilitate the differentiation between weakly attenuating materials and apply digital volume correlation to capture the dynamics of the electrodes during operation. After validating that we can quantify the local electrochemical activity and microstructural changes throughout graphite electrodes, we apply our technique to graphite-silicon composite electrodes. We show that microstructural changes that occur during (de)lithiation of a pure graphite electrode are of the same order of magnitude as spatial inhomogeneities within it, while strain in composite electrodes is locally pronounced and introduces significant microstructural changes.

Polyaniline/multi-walled carbon nanotubes composite with core-shell structures as a cathode material for rechargeable lithium-polymer cells

Energy Technology Data Exchange (ETDEWEB)

Liu, Pan [School of Marine Science and Technology, Harbin Institute of Technology, Weihai 264209 (China); Han, Jia-Jun, E-mail: hanjiajunhitweihai@163.com [School of Marine Science and Technology, Harbin Institute of Technology, Weihai 264209 (China); Jiang, Li-Feng [Dalian Chemical Institute of Chinese Academy of Sciences, Dalian 116011 (China); Li, Zhao-Yu; Cheng, Jin-Ning [School of Marine Science and Technology, Harbin Institute of Technology, Weihai 264209 (China)

2017-04-01

Highlights: • The polyaniline multi-walled carbon nanotubes composite with core-shell structures was synthetized via in situ chemical oxidative polymerization, and the materials were characterized by physical and chemical methods. • The PANI/WMCNTs was synthetized via in situ chemical oxidative polymerization with core-shell structures. • The WMCNTs highly enhanced the conductivity of composites. • The comopsites were more conducive to the intercalation and deintercalation of anions and cations. • The much better performance as the cathode for lithium-ion cells was acquired for the composites. • The composites are low cost and eco-friendly which have a good prospect in future. - Abstract: The aniline was polymerized onto functionalized multi-walled carbon nanotubes in order to obtain a cathode material with core-shell structures for lithium batteries. The structure and morphology of the samples were investigated by Fourier transform infrared spectroscopy analysis, scanning electron microscope, transmission electron microscope and X-ray diffraction. The electrochemical properties of the composite were characterized by the cyclic voltammetry, the charge/discharge property, coulombic efficiency, and ac impedance spectroscopy in detail. At a constant current density of 0.2 C, the first specific discharge capacity of the reduced and oxidized PANI/WMCNTs were 181.8 mAh/g and 135.1 mAh/g separately, and the capacity retention rates were corresponding to 76.75% and 86.04% for 100 cycles with 99% coulombic efficiency. It was confirmed that the CNTs obviously enhanced the conductivity and electrochemical performance of polyaniline, and compared with the pure PANI, the reduced composite possessed a quite good performance for the cathode of lithium batteries.

A comparative study of electrochemical performance of graphene sheets, expanded graphite and natural graphite as anode materials for lithium-ion batteries

International Nuclear Information System (INIS)

Bai, Li-Zhong; Zhao, Dong-Lin; Zhang, Tai-Ming; Xie, Wei-Gang; Zhang, Ji-Ming; Shen, Zeng-Min

2013-01-01

Highlights: • Graphene sheets (GSs), expanded graphite (EG) and natural graphite (NG) were comparatively investigated as anode materials for lithium-ion batteries. • The reversible capacity of GS electrode was almost twice that of EG electrode and three times that of NG electrode. • The first-cycle coulombic efficiency and capacity retention of NG were much bigger than those of GSs and EG. • GS and EG electrodes exhibited higher electrochemical activity and more favorable kinetic properties. -- Abstract: Three kinds of carbon materials, i.e., graphene sheets (GSs), expanded graphite (EG) and natural graphite (NG) were comparatively investigated as anode materials for lithium-ion batteries via scanning electron microscope, high-resolution transmission electron microscopy, X-ray diffraction, Fourier transform infrared spectroscopy, Raman spectroscopy and a variety of electrochemical testing techniques. The test results showed that the reversible capacities of GS electrode were 1130 and 636 mA h g −1 at the current densities of 0.2 and 1 mA cm −2 , respectively, which were almost twice those of EG electrode and three times those of NG electrode. The first-cycle coulombic efficiency and capacity retention of NG were much bigger than those of GSs and EG. The notable capacity fading observed in GSs and EG may be ascribed to the disorder-induced structure instability. The larger voltage hysteresis in GS and EG electrodes was not only related to the surface functional groups, but also to the active defects in GSs and EG, which results in greater hindrance and higher overvoltage during lithium extraction from electrode. The kinetics properties of GSs, EG and NG electrodes were compared by AC impedance measurements. GS and EG electrodes exhibited higher electrochemical activity and more favorable kinetic properties during charge and discharge process

The influence of the pyrolysis temperature on the electrochemical behavior of carbon-rich SiCN polymer-derived ceramics as anode materials in lithium-ion batteries

Science.gov (United States)

Reinold, Lukas Mirko; Yamada, Yuto; Graczyk-Zajac, Magdalena; Munakata, Hirokazu; Kanamura, Kiyoshi; Riedel, Ralf

2015-05-01

Within this study we report on the impact of the pyrolysis temperature on the structural and electrochemical properties of the poly(phenylvinylsilylcarbodiimide) derived silicon carbonitride (SiCN) ceramic. Materials pyrolysed at 800 °C and 1300 °C, SiCN 800 and SiCN 1300, are found amorphous. Raman spectroscopy measurements indicate the increase in ordering of the free carbon phase with increasing pyrolysis temperature which leads to lower capacity recovered by SiCN 1300. Significant hysteresis is found for materials pyrolysed at 800 °C during electrochemical lithium insertion/extraction. This feature is attributed to much higher hydrogen content in SiCN 800 sample. An aging of SiCN 800 reflected by a change of elemental composition upon contact to air and a strong film formation are attenuated at a higher pyrolysis temperature. Single particle microelectrode investigation on SiCN 800 and SiCN 1300 clarify different electrochemical behavior of the materials. Much lower charge transfer resistance of SiCN 1300 in comparison to SiCN 800 explains better high currents electrochemical performance. Lithium ions diffusion coefficient Dmin ranges from 3.2 10-9 cm2s-1 to 6.4 10-11 cm2s-1 and is independent on the potential.

Microwave exfoliated graphene oxide/TiO{sub 2} nanowire hybrid for high performance lithium ion battery

Energy Technology Data Exchange (ETDEWEB)

Ishtiaque Shuvo, Mohammad Arif; Rodriguez, Gerardo; Karim, Hasanul; Lin, Yirong [Department of Mechanical Engineering, University of Texas at El Paso, El Paso, Texas 79968 (United States); Islam, Md Tariqul; Noveron, Juan C. [Department of Chemistry, University of Texas at El Paso, El Paso, Texas 79968 (United States); Ramabadran, Navaneet [Department of Chemical Engineering, University of California at Santa Barbara, California 93106 (United States)

2015-09-28

Lithium ion battery (LIB) is a key solution to the demand of ever-improving, high energy density, clean-alternative energy systems. In LIB, graphite is the most commonly used anode material; however, lithium-ion intercalation in graphite is limited, hindering the battery charge rate and capacity. To date, one of the approaches in LIB performance improvement is by using porous carbon (PC) to replace graphite as anode material. PC's pore structure facilitates ion transport and has been proven to be an excellent anode material candidate in high power density LIBs. In addition, to overcome the limited lithium-ion intercalation obstacle, nanostructured anode assembly has been extensively studied to increase the lithium-ion diffusion rate. Among these approaches, high specific surface area metal oxide nanowires connecting nanostructured carbon materials accumulation have shown promising results for enhanced lithium-ion intercalation. Herein, we demonstrate a hydrothermal approach of growing TiO{sub 2} nanowires (TON) on microwave exfoliated graphene oxide (MEGO) to further improve LIB performance over PC. This MEGO-TON hybrid not only uses the high surface area of MEGO but also increases the specific surface area for electrode–electrolyte interaction. Therefore, this new nanowire/MEGO hybrid anode material enhances both the specific capacity and charge–discharge rate. Scanning electron microscopy and X-ray diffraction were used for materials characterization. Battery analyzer was used for measuring the electrical performance of the battery. The testing results have shown that MEGO-TON hybrid provides up to 80% increment of specific capacity compared to PC anode.

Electrochemical synthesis and characterization of stable colloidal suspension of graphene using two-electrode cell system

Energy Technology Data Exchange (ETDEWEB)

Danial, Wan Hazman, E-mail: hazmandanial@gmail.com; Majid, Zaiton Abdul, E-mail: zaiton@kimia.fs.utm.my; Aziz, Madzlan [Department of Chemistry, Faculty of Science, Universiti Teknologi Malaysia (UTM), 81310 Skudai, Johor (Malaysia); Chutia, Arunabhiram [Institute of Fluid Sciences, Tohoku University, Sendai 980-8577 (Japan); Sahnoun, Riadh [Ibnu Sina Institute for Fundamental Science Studies, Universiti Teknologi Malaysia (UTM), 81310 Skudai, Johor (Malaysia)

2015-07-22

The present work reports the synthesis and characterization of graphene via electrochemical exfoliation of graphite rod using two-electrode system assisted by Sodium Dodecyl Sulphate (SDS) as a surfactant. The electrochemical process was carried out with sequence of intercalation of SDS onto the graphite anode followed by exfoliation of the SDS-intercalated graphite electrode when the anode was treated as cathode. The effect of intercalation potential from 5 V to 9 V and concentration of the SDS surfactant of 0.1 M and 0.01 M were investigated. UV-vis Spectroscopic analysis indicated an increase in the graphene production with higher intercalation potential. Transmission Electron Microscopy (TEM) analysis showed a well-ordered hexagonal lattice of graphene image and indicated an angle of 60° between two zigzag directions within the honeycomb crystal lattice. Raman spectroscopy analysis shows the graphitic information effects after the exfoliation process.

Electrochemical reduction of graphited materials in LiClO{sub 4}-EC and LiClO{sub 4}-PC media: characterization of interface products by transmission electron microscopy; Reduction electrochimique de materiaux graphites en milieux LiCIO{sub 4}-EC et LiCIO{sub 4}-PC: caracterisation des produits d`interface par microscopie electronique a transmission

Energy Technology Data Exchange (ETDEWEB)

Billaud, D.; Naji, A.; Ghanbaja, J. [Universite Henri Poincare Nancy, 54 - Vandoeuvre-les-Nancy (France); Willmann, P. [Centre National d`Etudes Spatiales (CNES), 31 - Toulouse (France)

1996-12-31

The electrochemical intercalation of non-solvated lithium in different graphited materials has been performed in LiClO{sub 4}-ethylene carbonate (EC) medium. The irreversible capacity observed during the first output is mainly due to the formation of a passivation layer made of electrolyte reduction products. These products have been characterized for different electrode reduction potentials using transmission electron microscopy (image, diffraction) and electron energy loss spectroscopy (EELS). EC reduction on the electrode surface in presence of LiClO{sub 4} leads to the formation of Li{sub 2}CO{sub 3} for potentials close to 0.8 V vs Li{sup +}/Li. For lower potentials, the electrolyte reduction reaction goes on with the formation of different lithium alkyl-carbonates. In LiClO{sub 4}-propylene carbonate (PC) medium, the interface phenomena are different. The reduction of a graphite electrode is characterized by the exfoliation phenomenon which hinders lithium intercalation. On the contrary, the formation of the passivation layer by graphite reduction in LiClO{sub 4}-EC medium allows the cycling of the electrode in the LiClO{sub 4}-PC electrolyte. In this case, the irreversible capacity observed during the first output depends on the experimental conditions of formation of the passivation layer. Abstract only. (J.S.)

Electrochemical reduction of graphited materials in LiClO{sub 4}-EC and LiClO{sub 4}-PC media: characterization of interface products by transmission electron microscopy; Reduction electrochimique de materiaux graphites en milieux LiCIO{sub 4}-EC et LiCIO{sub 4}-PC: caracterisation des produits d`interface par microscopie electronique a transmission

Energy Technology Data Exchange (ETDEWEB)

Billaud, D; Naji, A; Ghanbaja, J [Universite Henri Poincare Nancy, 54 - Vandoeuvre-les-Nancy (France); Willmann, P [Centre National d` Etudes Spatiales (CNES), 31 - Toulouse (France)

1997-12-31

The electrochemical intercalation of non-solvated lithium in different graphited materials has been performed in LiClO{sub 4}-ethylene carbonate (EC) medium. The irreversible capacity observed during the first output is mainly due to the formation of a passivation layer made of electrolyte reduction products. These products have been characterized for different electrode reduction potentials using transmission electron microscopy (image, diffraction) and electron energy loss spectroscopy (EELS). EC reduction on the electrode surface in presence of LiClO{sub 4} leads to the formation of Li{sub 2}CO{sub 3} for potentials close to 0.8 V vs Li{sup +}/Li. For lower potentials, the electrolyte reduction reaction goes on with the formation of different lithium alkyl-carbonates. In LiClO{sub 4}-propylene carbonate (PC) medium, the interface phenomena are different. The reduction of a graphite electrode is characterized by the exfoliation phenomenon which hinders lithium intercalation. On the contrary, the formation of the passivation layer by graphite reduction in LiClO{sub 4}-EC medium allows the cycling of the electrode in the LiClO{sub 4}-PC electrolyte. In this case, the irreversible capacity observed during the first output depends on the experimental conditions of formation of the passivation layer. Abstract only. (J.S.)

Development of reliable lithium microreference electrodes for long-term in situ studies of lithium-based battery systems

NARCIS (Netherlands)

Zhou, J.; Notten, P.H.L.

2004-01-01

An in situ method to prepare lithium microreference electrodes has been developed. The microreference electrodes are made by electrochemical deposition of metallic lithium from both the positive and negative electrodes onto a copper wire positioned in-between the two Li-based battery electrodes. The

Layered materials with improved magnesium intercalation for rechargeable magnesium ion cells

Energy Technology Data Exchange (ETDEWEB)

Doe, Robert Ellis; Downie, Craig Michael; Fischer, Christopher; Lane, George Hamilton; Morgan, Dane; Nevin, Josh; Ceder, Gerbrand; Persson, Kristin Aslaug; Eaglesham, David

2016-07-26

Electrochemical devices which incorporate cathode materials that include layered crystalline compounds for which a structural modification has been achieved which increases the diffusion rate of multi-valent ions into and out of the cathode materials. Examples in which the layer spacing of the layered electrode materials is modified to have a specific spacing range such that the spacing is optimal for diffusion of magnesium ions are presented. An electrochemical cell comprised of a positive intercalation electrode, a negative metal electrode, and a separator impregnated with a nonaqueous electrolyte solution containing multi-valent ions and arranged between the positive electrode and the negative electrode active material is described.

Coupling of Mechanical Behavior of Lithium Ion Cells to Electrochemical-Thermal (ECT) Models for Battery Crush

Energy Technology Data Exchange (ETDEWEB)

Zhang, Chao; Santhanagopalan, Shriram; Pesaran, Ahmad; Sahraei, Elham; Wierzbicki, Tom

2016-06-14

Vehicle crashes can lead to crushing of the battery, damaging lithium ion battery cells and causing local shorts, heat generation, and thermal runaway. Simulating all the physics and geometries at the same time is challenging and takes a lot of effort; thus, simplifications are needed. We developed a material model for simultaneously modeling the mechanical-electrochemical-thermal behavior, which predicted the electrical short, voltage drop, and thermal runaway behaviors followed by a mechanical abuse-induced short. The effect of short resistance on the battery cell performance was studied.

A lattice-gas model of the ion current across the solid interface: fast-ion conductor - intercalate

International Nuclear Information System (INIS)

Nachev, I.; Balkanski, M.

1994-12-01

The transport of Lithium ions across the material interface: fast-ion conducting glass - intercalate is simulated by a non-trivial lattice-gas model. The model takes explicitly into account the influence of the Coulomb correlations, the site-blocking effect and the boundary conditions on the ion kinetics. Potential device applications of the model are pointed out by computing the current density of Lithium ions for material parameters of the real interface: doped ternary borate glass - Indium Selenide, which constitute the electrolyte and the cathode, respectively, of a thin-film microbattery with improved performance. (author). 10 refs, 4 figs

Effect of oxide ion concentration on the electrochemical oxidation of carbon in molten LiCl

International Nuclear Information System (INIS)

Yun, J. W.; Choi, I. K.; Park, Y. S.; Kim, W. H.

2001-01-01

The continuous measurement of lithium oxide concentration was required in DOR (Direct Oxide Reduction) process, which converts spent nuclear fuel to metal form, for the reactivity monitor and effective control of the process. The concentration of lithium oxide was measured by the electrochemical method, which was based on the phenomenon that carbon atoms of glassy carbon electrode electrochemically react with oxygen ions of lithium oxide in molten LiCl medium. From the results of electrode polarization experiments, the trend of oxidation rate of carbon atoms was classified into two different regions, which were proportional and non-proportional ones, dependent on the amount of lithium oxide. Below about 2.5 wt % Li 2 O, as the carbon atom ionization rate was fast enough for reacting with diffusing lithium oxide to the surface of carbon electrode. In this concentration range, the oxidation rate of carbon atoms was controlled by the diffusion of lithium oxide, and the concentration of lithium oxide could be measured by electrochemical method. But, above 2.5 wt % Li 2 O, the oxidation rate of carbon atoms was controlled by the applied electrochemical potential, because the carbon atom ionization rate was suppressed by the huge amounts of diffusing Li 2 O. Above this concentration, the electrochemical method was not applicable to determine the concentration of lithium oxide

Enhanced electrochemical properties of vanadium-doped titanium niobate as a new anode material for lithium-ion batteries

International Nuclear Information System (INIS)

Wen, Xiaoyan; Ma, Chenxiang; Du, Chenqiang; Liu, Jie; Zhang, Xinhe; Qu, Deyang; Tang, Zhiyuan

2015-01-01

The Vanadium-doped TiNb 2 O 7 (TNO) samples have been investigated as novel anode active materials for application in lithium-ion batteries. The samples are characterized by X-ray diffraction patterns (XRD), raman spectrum, scanning electron microscopy (SEM), transmission electron microscopy (TEM), galvanostatic charge-discharge tests, and cyclic voltammetry (CV) tests. The XRD results indicate that V-doping expands the lattice parameters of TiNb 2 O 7 samples and facilitates the enhanced lithium ion diffusion. SEM and TEM results show that lattice expansion caused by V-doping doesn’t significantly change the particle size distribution of TiNb 2 O 7 samples. The electrochemical measurements indicate that the TiNb 1.98 V 0.02 O 7 anode material displays a highly reversible capacity and excellent cycling stability. The initial discharge capacities of TiNb 1.98 V 0.02 O 7 are 298.48 mAh g −1 and 171.99 mAh g −1 at 0.3C and 10C, respectively, indicating that the TiNb 1.98 V 0.02 O 7 material can be utilized as a promising anode material for lithium-ion batteries.

Electrochemical performance of arc-produced carbon nanotubes as anode material for lithium-ion batteries

International Nuclear Information System (INIS)

Yang, Shubin; Song, Huaihe; Chen, Xiaohong; Okotrub, A.V.; Bulusheva, L.G.

2007-01-01

The effects of etching process on the morphology, structure and electrochemical performance of arc-produced multiwalled carbon nanotubes (CNTs) as anode material for lithium-ion batteries were systematically investigated by TEM and a variety of electrochemical testing techniques. It was found that the etched CNTs exhibited four times higher reversible capacity than that of raw CNTs, and possessed excellent cyclability with almost 100% capacity retention after 30 cycles. The kinetic properties of three kinds of CNTs electrodes involving the pristine (CNTs-1), etched (CNTs-2) as well as etch-carbonized samples (CNTs-3) were characterized via ac impedance measurement. It was indicated that, after 30 cycles the exchange current density i 0 of etched CNTs ((7.6-7.8) x 10 -3 A cm -2 ) was higher than that of the raw CNTs (5.9 x 10 -3 A cm -2 ), suggesting the electrochemical activity of CNTs was enhanced by the etching treatment. The storage characteristics of the CNTs electrodes at room temperature and 50 o C were particularly compared. It was found that the film resistance on CNTs electrode generally tended to become large with the elongation of storage time, especially storage at high temperature. In comparison with CNTs-1 and CNTs-3, CNTs-2 exhibited more distinctly increase of film resistance, which is related with the surface properties

Sulfur nanocrystals anchored graphene composite with highly improved electrochemical performance for lithium-sulfur batteries

Science.gov (United States)

Zhang, Jun; Dong, Zimin; Wang, Xiuli; Zhao, Xuyang; Tu, Jiangping; Su, Qingmei; Du, Gaohui

2014-12-01

Two kinds of graphene-sulfur composites with 50 wt% of sulfur are prepared using hydrothermal method and thermal mixing, respectively. Transmission Electron Microscopy (TEM) and Energy Dispersive X-ray Spectra mapping show that sulfur nanocrystals with size of ∼5 nm dispersed on graphene sheets homogeneously for the sample prepared by hydrothermal method (NanoS@G). While for the thermal mixed graphene-sulfur composite (S-G mixture), sulfur shows larger and uneven size (50-200 nm). X-ray Photoelectron Spectra (XPS) reveals the strong chemical bonding between the sulfur nanocrystals and graphene. Comparing with the S-G mixture, the NanoS@G composite shows highly improved electrochemical performance as cathode for lithium-sulfur (Li-S) battery. The NanoS@G composite delivers an initial capacity of 1400 mAh g-1 with the sulfur utilization of 83.7% at a current density of 335 mA g-1. The capacity keeps above 720 mAh g-1 over 100 cycles. The strong adherence of the sulfur nanocrystals on graphene immobilizes sulfur and polysulfides species and suppressed the "shuttle effect", resulting higher coulombic efficiency and better capacity retention. Electrochemical impedance also suggests that the strong bonding enabled rapid electronic/ionic transport and improved electrochemical kinetics, therefore good rate capability is obtained. These results demonstrate that the NanoS@G composite is a very promising candidate for high-performance Li-S batteries.

An electrochemical cell for in operando studies of lithium/sodium batteries using a conventional x-ray powder diffractometer

DEFF Research Database (Denmark)

Shen, Yanbin; Pedersen, Erik Ejler; Christensen, Mogens

2014-01-01

An electrochemical cell has been designed for powder X-ray diffraction (PXRD) studies of lithium ion batteries (LIB) and sodium ion batteries (SIB) in operando with high time resolution using conventional powder X-ray diffractometer. The cell allows for studies of both anode and cathode electrode...... to operate and maintain. Test examples on lithium insertion/extraction in two spinel-type LIB electrode materials (Li4Ti5O12 anode and LiMn2O4 cathode) are presented as well as first results on sodium extraction from a layered SIB cathode material (Na0.84Fe0.56Mn0.44O2)....

Silver-coated LiVPO4F composite with improved electrochemical performance as cathode material for lithium-ion batteries

Science.gov (United States)

Yang, Bo; Yang, Lin

2015-12-01

Nano-structured LiVPO4F/Ag composite cathode material has been successfully synthesized via a sol-gel route. The structural and physical properties, as well as the electrochemical performance of the material are compared with those of the pristine LiVPO4F. X-ray diffraction (XRD) and scanning electron microscopy (SEM) reveal that Ag particles are uniformly dispersed on the surface of LiVPO4F without destroying the crystal structure of the bulk material. An analysis of the electrochemical measurements show that the Ag-modified LiVPO4F material exhibits high discharge capacity, good cycle performance (108.5 mAh g-1 after 50th cycles at 0.1 C, 93% of initial discharge capacity) and excellent rate behavior (81.8 mAh g-1 for initial discharge capacity at 5 C). The electrochemical impedance spectroscopy (EIS) results reveal that the adding of Ag decreases the charge-transfer resistance (Rct) of LiVPO4F cathode. This study demonstrates that Ag-coating is a promising way to improve the electrochemical performance of the pristine LiVPO4F for lithium-ion batteries cathode material.

Effect of Ce addition on the mechanical and electrochemical properties of a lithium battery shell alloy

International Nuclear Information System (INIS)

Zhang, Junchao; Ding, Dongyan; Xu, Xinglong; Gao, Yongjin; Chen, Guozhen; Chen, Weigao; You, Xiaohua; Huang, Yuanwei; Tang, Jinsong

2014-01-01

Highlights: • Fabrication of Ce-free and Ce-containing Al–Cu–Mn–Fe–Mg alloy. • TEM, tensile and electrochemical characterization of the alloys. • Ce element greatly affects the precipitation of the alloy. • Ce element had great impact on the tensile strength and corrosion potential of the alloys. - Abstract: Due to severe application environment lithium battery shell of new-energy automotives requires increasing demands for using high performance aluminum alloys. In the present work, effect of Ce addition on the microstructure, tensile and electrochemical properties of an Al–Cu–Mn–Mg–Fe alloy were investigated through using X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), tensile tests and electrochemical tests. The experimental results indicated that the addition of Ce element could promote the precipitation of second phases. With addition of 0.36% Ce, high melting point Al 8 Cu 4 Ce phase and many Al 20 Cu 2 Mn 3 particles could be found. In addition, the precipitation of conventionally dominant phase of Al 2 Cu could be suppressed in alloy. The Ce addition was found to result in enhanced tensile strength and improved corrosion resistance

Effect of Ce addition on the mechanical and electrochemical properties of a lithium battery shell alloy

Energy Technology Data Exchange (ETDEWEB)

Zhang, Junchao [School of Materials Science and Engineering, Shanghai Jiao Tong University, Shanghai 200240 (China); Ding, Dongyan, E-mail: dyding@sjtu.edu.cn [School of Materials Science and Engineering, Shanghai Jiao Tong University, Shanghai 200240 (China); Xu, Xinglong [School of Materials Science and Engineering, Shanghai Jiao Tong University, Shanghai 200240 (China); Gao, Yongjin; Chen, Guozhen; Chen, Weigao; You, Xiaohua [Huafon NLM Al Co., Ltd, Shanghai 201506 (China); Huang, Yuanwei; Tang, Jinsong [Shanghai Huafon Materials Technology Institute, Shanghai 201203 (China)

2014-12-25

Highlights: • Fabrication of Ce-free and Ce-containing Al–Cu–Mn–Fe–Mg alloy. • TEM, tensile and electrochemical characterization of the alloys. • Ce element greatly affects the precipitation of the alloy. • Ce element had great impact on the tensile strength and corrosion potential of the alloys. - Abstract: Due to severe application environment lithium battery shell of new-energy automotives requires increasing demands for using high performance aluminum alloys. In the present work, effect of Ce addition on the microstructure, tensile and electrochemical properties of an Al–Cu–Mn–Mg–Fe alloy were investigated through using X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), tensile tests and electrochemical tests. The experimental results indicated that the addition of Ce element could promote the precipitation of second phases. With addition of 0.36% Ce, high melting point Al{sub 8}Cu{sub 4}Ce phase and many Al{sub 20}Cu{sub 2}Mn{sub 3} particles could be found. In addition, the precipitation of conventionally dominant phase of Al{sub 2}Cu could be suppressed in alloy. The Ce addition was found to result in enhanced tensile strength and improved corrosion resistance.

High-performance lithium-rich layered oxide materials: Effects of chelating agents on microstructure and electrochemical properties

International Nuclear Information System (INIS)

Li, Lingjun; Xu, Ming; Chen, Zhaoyong; Zhou, Xiang; Zhang, Qiaobao; Zhu, Huali; Wu, Chun; Zhang, Kaili

2015-01-01

The mechanisms and effects of three typical chelating agents, namely glucose, citric acid and sucrose on the sol-gel synthesis process, electrochemical degradation and structural evolution of 0.5Li 2 MnO 3 ·0.5LiNi 0.5 Co 0.2 Mn 0.3 O 2 (LLMO) materials are systematically compared for the first time. X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy and high-resolution transmission electron microscopy analysis indicate that the sample synthesized from sucrose owns well structure, homogenous distribution, low Ni 3+ concentration and good surface structural stability during cycling, respectively. Electrochemical tests further prove that the LLMO material obtained from sucrose maintains 258.4 mAh g −1 with 94.8% capacity retention after 100 cycles at 0.2 C. The superior electrochemical performance can be ascribed to the exceptional complexing mechanism of sucrose, compared to those of the glucose and citric acid. Namely, one mole sucrose can be hydrolyzed into two different monosaccharides and further chelates three M (Li, Ni, Co and Mn) ions to form a more uniform ion-chelated matrix during sol-gel process. This discovery is an important step towards understanding the selection criterion of chelating agents for sol-gel method, that chelating agent with excellent complexing capability is beneficial to the distribution, structural stability and electrochemical properties of advanced lithium-rich layered materials

NMR study of electrode materials for lithium ion-batteries; Etude par RMN de materiaux d'electrode pour batteries lithium-ion

Energy Technology Data Exchange (ETDEWEB)

Chazel, C.

2006-01-15

This work is devoted to the study of LiMO{sub 2} et LiM{sub 2}O{sub 4} (M: transition metal) intercalation compounds used as electrode material for lithium-ion batteries. Solid state NMR allows one to characterise the local environment of the lithium ions present in these phases by the use of the hyperfine interactions due to the presence of some electron spin density coming from localised electrons (Fermi-contact shift) or itinerant electrons (Knight shift) on the lithium nucleus. By following the transformation of the LiNiO{sub 2} layered phase into the LiNi{sub 2}O{sub 4} spinel material using lithium NMR, we studied the nature of the asymmetric signal observed for LiNiO{sub 2}, and the influence of the departure from the ideal stoichiometry; we showed a coupled ion/electron hopping in Li{sub X}NiO{sub 2} phases linked to Li/vacancy and Ni{sup 3+}/Ni{sup 4+} ordering, and finally showed the existence of structural defects within the LiNi{sub 2}O{sub 4} spinel phase obtained by thermal treatment of Li{sub 0.5}NiO{sub 2}. Lithium NMR of the intercalated materials obtained from the LiTi{sub 2}O{sub 4} and Li{sub 4}Ti{sub 5}O{sub 12} spinels showed a metallic behaviour for Li{sub 2}Ti{sub 2}O{sub 4} with a Knight shift of the NMR signal similar to that of LiTi{sub 2}O{sub 4}, and signals intermediate in nature between Knight and Fermi-contact shifts for Li{sub 7}Ti{sub 5}O{sub 12}. (author)

Systematic and reliable multiscale modelling of lithium batteries

Science.gov (United States)

Atalay, Selcuk; Schmuck, Markus

2017-11-01

Motivated by the increasing interest in lithium batteries as energy storage devices (e.g. cars/bycicles/public transport, social robot companions, mobile phones, and tablets), we investigate three basic cells: (i) a single intercalation host; (ii) a periodic arrangement of intercalation hosts; and (iii) a rigorously upscaled formulation of (ii) as initiated in. By systematically accounting for Li transport and interfacial reactions in (i)-(iii), we compute the associated chracteristic current-voltage curves and power densities. Finally, we discuss the influence of how the intercalation particles are arranged. Our findings are expected to improve the understanding of how microscopic properties affect the battery behaviour observed on the macroscale and at the same time, the upscaled formulation (iii) serves as an efficient computational tool. This work has been supported by EPSRC, UK, through the Grant No. EP/P011713/1.

A Multiscale Approach to Magnesium Intercalation Batteries: Safer, Lighter, and Longer-Lasting

Data.gov (United States)

National Aeronautics and Space Administration — Lithium-ion batteries are the gold-standard for electrochemical energy storage; however, the ceiling for their storage potential is constrained by the most...

An Ab Initio and Kinetic Monte Carlo Simulation Study of Lithium Ion Diffusion on Graphene

Directory of Open Access Journals (Sweden)

Kehua Zhong

2017-07-01

Full Text Available The Li+ diffusion coefficients in Li+-adsorbed graphene systems were determined by combining first-principle calculations based on density functional theory with Kinetic Monte Carlo simulations. The calculated results indicate that the interactions between Li ions have a very important influence on lithium diffusion. Based on energy barriers directly obtained from first-principle calculations for single-Li+ and two-Li+ adsorbed systems, a new equation predicting energy barriers with more than two Li ions was deduced. Furthermore, it is found that the temperature dependence of Li+ diffusion coefficients fits well to the Arrhenius equation, rather than meeting the equation from electrochemical impedance spectroscopy applied to estimate experimental diffusion coefficients. Moreover, the calculated results also reveal that Li+ concentration dependence of diffusion coefficients roughly fits to the equation from electrochemical impedance spectroscopy in a low concentration region; however, it seriously deviates from the equation in a high concentration region. So, the equation from electrochemical impedance spectroscopy technique could not be simply used to estimate the Li+ diffusion coefficient for all Li+-adsorbed graphene systems with various Li+ concentrations. Our work suggests that interactions between Li ions, and among Li ion and host atoms will influence the Li+ diffusion, which determines that the Li+ intercalation dependence of Li+ diffusion coefficient should be changed and complex.

Preparation and electrochemical performance of sulfur-alumina cathode material for lithium-sulfur batteries

International Nuclear Information System (INIS)

Dong, Kang; Wang, Shengping; Zhang, Hanyu; Wu, Jinping

2013-01-01

Highlights: ► Micron-sized alumina was synthesized as adsorbent for lithium-sulfur batteries. ► Sulfur-alumina material was synthesized via crystallizing nucleation. ► The Al 2 O 3 can provide surface area for the deposition of Li 2 S and Li 2 S 2 . ► The discharge capacity of the battery is improved during the first several cycles. - Abstract: Nano-sized sulfur particles exhibiting good adhesion with conducting acetylene black and alumina composite materials were synthesized by means of an evaporated solvent and a concentrated crystallization method for use as the cathodes of lithium-sulfur batteries. The composites were characterized and examined by X-ray diffraction, environmental scanning electron microscopy and electrochemical methods, such as cyclic voltammetry, electrical impedance spectroscopy and charge–discharge tests. Micron-sized flaky alumina was employed as an adsorbent for the cathode material. The initial discharge capacity of the cathode with the added alumina was 1171 mAh g −1 , and the remaining capacity was 585 mAh g −1 after 50 cycles at 0.25 mA cm −2 . Compared with bare sulfur electrodes, the electrodes containing alumina showed an obviously superior cycle performance, confirming that alumina can contribute to reducing the dissolution of polysulfides into electrolytes during the sulfur charge–discharge process

Status of the DOE battery and electrochemical technology program. III

International Nuclear Information System (INIS)

Roberts, R.

1982-02-01

This report reviews the status of the Department of Energy Subelement on Electrochemical Storage Systems. It emphasizes material presented at the Fourth US Department of Energy Battery and Electrochemical Contractors' Conference, held June 2-4, 1981. The conference stressed secondary batteries, however, the aluminum/air mechanically rechargeable battery and selected topics on industrial electrochemical processes were included. The potential contributions of the battery and electrochemical technology efforts to supported technologies: electric vehicles, solar electric systems, and energy conservation in industrial electrochemical processes, are reviewed. The analyses of the potential impact of these systems on energy technologies as the basis for selecting specific battery systems for investigation are noted. The battery systems in the research, development, and demonstration phase discussed include: aqueous mobile batteries (near term) - lead-acid, iron/nickel-oxide, zinc/nickel-oxide; advanced batteries - aluminum/air, iron/air, zinc/bromine, zinc/ferricyanide, chromous/ferric, lithium/metal sulfide, sodium/sulfur; and exploratory batteries - lithium organic electrolyte, lithium/polymer electrolyte, sodium/sulfur (IV) chloroaluminate, calcium/iron disulfide, lithium/solid electrolyte. Supporting research on electrode reactions, cell performance modeling, new battery materials, ionic conducting solid electrolytes, and electrocatalysis is reviewed. Potential energy saving processes for the electrowinning of aluminum and zinc, and for the electrosynthesis of inorganic and organic compounds are included

Electrochemical characteristics of polyacetylene in organic electrolytes

Energy Technology Data Exchange (ETDEWEB)

Padula, A.; Scrosati, B.

1985-01-15

The characteristics of the electrochemical doping process of polyacetylene have been investigated in lithium cells using lithium perchlorate in propylene carbonate as electrolytic solution. The kinetics of this process are controlled by the diffusion of the dopant species throughout the polymer. Therefore, polyacetylene samples with a highly porous, extended surface should be selected for the development of efficient, rechargeable lithium batteries. In line with this, we have considered foam-type polyacetylene electrodes which have a lower density than the 'classical' Shirakawa-type film electrodes. The electrochemical behaviour of the polyacetylene foam samples has been examined by cyclic voltametry response and constant current, charge-discharge cycles. The results are described in this work.

Effect of entropy change of lithium intercalation in cathodes and anodes on Li-ion battery thermal management

Energy Technology Data Exchange (ETDEWEB)

Viswanathan, Vilayanur V.; Choi, Daiwon; Wang, Donghai; Xu, Wu; Towne, Silas; Williford, Ralph E.; Zhang, Ji-Guang; Liu, Jun; Yang, Zhenguo [Pacific Northwest National Laboratory, P.O. Box 999, Richland, WA 99352 (United States)

2010-06-01

The entropy changes ({delta}S) in various cathode and anode materials, as well as in complete Li-ion batteries, were measured using an electrochemical thermodynamic measurement system (ETMS). LiCoO{sub 2} has a much larger entropy change than electrodes based on LiNi{sub x}Co{sub y}Mn{sub z}O{sub 2} and LiFePO{sub 4}, while lithium titanate based anodes have lower entropy change compared to graphite anodes. The reversible heat generation rate was found to be a significant portion of the total heat generation rate. The appropriate combinations of cathode and anode were investigated to minimize reversible heat generation rate across the 0-100% state of charge (SOC) range. In addition to screening for battery electrode materials with low reversible heat, the techniques described in this paper can be a useful engineering tool for battery thermal management in stationary and transportation applications. (author)

Synthesis of TiO2 by electrochemical method from TiCl4 solution as anode material for lithium-ion batteries

International Nuclear Information System (INIS)

Nur, Adrian; Purwanto, Agus; Jumari, Arif; Dyartanti, Endah R.; Sari, Sifa Dian Permata; Hanifah, Ita Nur

2016-01-01

Metal oxide combined with graphite becomes interesting composition. TiO 2 is a good candidate for Li ion battery anode because of cost, availability of sufficient materials, and environmentally friendly. TiO 2 gravimetric capacity varied within a fairly wide range. TiO 2 crystals form highly depends on the synthesis method used. The electrochemical method is beginning to emerge as a valuable option for preparing TiO 2 powders. Using the electrochemical method, the particle can easily be controlled by simply adjusting the imposed current or potential to the system. In this work, the effects of some key parameters of the electrosynthesis on the formation of TiO 2 have been investigated. The combination of graphite and TiO 2 particle has also been studied for lithium-ion batteries. The homogeneous solution for the electrosynthesis of TiO 2 powders was TiCl 4 in ethanol solution. The electrolysis was carried out in an electrochemical cell consisting of two carbon electrodes with dimensions of (5 × 2) cm. The electrodes were set parallel with a distance of 2.6 cm between the electrodes and immersed in the electrolytic solution at a depth of 2 cm. The electrodes were connected to the positive and negative terminals of a DC power supply. The electrosynthesis was performed galvanostatically at 0.5 to 2.5 hours and voltages were varied from 8 to 12 V under constant stirring at room temperature. The resulted suspension was aged at 48 hrs, filtered, dried directly in an oven at 150°C for 2 hrs, washed 2 times, and dried again 60 °C for 6 hrs. The particle product has been used to lithium-ion battery as anode. Synthesis of TiO 2 particle by electrochemical method at 10 V for 1 to 2.5 hrs resulted anatase and rutile phase

Electrode Materials for Lithium/Sodium-Ion Batteries

DEFF Research Database (Denmark)

Shen, Yanbin

2014-01-01

The synthesis of electrode materials for lithium/sodium ion batteries and their structural stability during lithium/sodium insertion/extraction are the two essential issues that have limited battery application in the fields requiring long cycle life and high safety. During her PhD studies, Yanbin...... Shen systematically investigated the controlled synthesis of electrode materials for lithium/sodium ion batteries. She also investigated their formation mechanisms and structural evolution during the operation of batteries using in situ/operando X-ray diffraction techniques. The research findings...... provide insights into formation mechanisms of Li4Ti5O12 anode material from both hydrothermal and solid-state reaction. The results also contribute to a thorough understanding of the intercalation and decay mechanisms of O3/P2 layered sodium cathode materials in sodium ion batteries....

New Insights on the Structure of Electrochemically Deposited Lithium Metal and Its Solid Electrolyte Interphases via Cryogenic TEM

Energy Technology Data Exchange (ETDEWEB)

Wang, Xuefeng; Zhang, Minghao; Alvarado, Judith; Wang, Shen; Sina, Mahsa; Lu, Bingyu; Bouwer, James; Xu, Wu [Energy; Xiao, Jie [Energy; Zhang, Ji-Guang [Energy; Liu, Jun [Energy; Meng, Ying Shirley

2017-11-02

Lithium metal has been considered as the “holy grail” anode material for rechargeable batteries though the dendritic growth and low Coulombic efficiency (CE) have crippled its practical use for decades. Its high chemical reactivity and low stability make it difficult to explore the intrinsic chemical and physical properties of the electrochemically deposited lithium (EDLi) and its accompanied solid electrolyte interphase (SEI). To prevent the dendritic growth and enhance the electrochemical reversibility, it is crucial to understand the nano- and meso- structures of EDLi. However, Li metal is very sensitive to beam damage and has low contrast for commonly used characterization techniques such as electron microscopy. Inspired by biological imaging techniques, this work demonstrates the power of cryogenic (cryo)- electron microscopy to reveal the detailed structure of EDLi and the SEI composition at the nano scale while minimizing beam damage during imaging. Surprisingly, the results show that the nucleation dominated EDLi (five minutes at 0.5 mA cm-2) is amorphous while there is some crystalline LiF present in the SEI. The EDLi grown from various electrolytes with different additives exhibits distinctive surface properties. Consequently, these results highlight the importance of the SEI and its relationship with the CE. Our findings not only illustrate the capabilities of cryogenic microscopy for beam (thermal)-sensitive materials, but it yields crucial structural information of the EDLi evolution with and without electrolyte additives.

Enhancing Near Zero Volt Storage Tolerance of Lithium-ion Batteries

Science.gov (United States)

Crompton, Kyle R.

There are inherent safety risks associated with inactive lithium ion batteries leading to greater restrictions and regulations on shipping and storage. Maintaining all cells of a lithium ion battery at near zero voltage with an applied fixed resistive load is one promising approach which can lessen (and potentially eliminate) the risk of a lithium ion battery entering thermal runaway when in an inactive state. However, in a conventional lithium ion cell, a near zero cell voltage can be damaging if the anode electrochemical potential increases to greater than the potential where dissolution of the standard copper current collector occurs (i.e. 3.1 V vs. Li/Li+ at room temperature). Past approaches to yield lithium ion cells that are resilient to a near zero volt state of charge involve use of secondary active materials or alternative current collectors which have anticipated tradeoffs in terms of cell performance and cost. In the the present dissertation work the approach of managing the amount of reversible lithium in a cell during construction to prevent the anode potential from increasing to greater than 3.1 V vs. Li/Li+ during near zero volt storage is introduced. Anode pre-lithiation was used in LiCoO 2/MCMB pouch cells to appropriately manage the amount of reversible lithium so that there is excess reversible lithium compared to the cathodes intercalation capacity (reversible lithium excess cell or RLE cell). RLE LiCoO 2/MCMB cells maintained 99% of their original capacity after three, 3-day and three, 7-day storage periods at near zero volts under fixed load. A LiCoO2/MCMB pouch cell fabricated with a pre-lithiated anode also maintained its original discharge performance after three, 3-day storage periods under fixed load at 45°C. The strong recharge performance after near zero volt storage is attributed to the anode potential remaining below the copper dissolution potential during near zero volt storage as informed by reference electrode measurements. Pulse

Layered lithium transition metal nitrides as novel anodes for lithium secondary batteries

International Nuclear Information System (INIS)

Liu Yu; Horikawa, Kumi; Fujiyosi, Minako; Imanishi, Nobuyuki; Hirano, Atsushi; Takeda, Yasuo

2004-01-01

We report the approach to overcome the deterrents of the hexagonal Li 2.6 Co 0.4 N as potential insertion anode for lithium ion batteries: the rapid capacity fading upon long cycles and the fully Li-rich state before cycling. Research reveals that the appropriate amount of Co substituted by Cu can greatly improve the cycling performance of Li 2.6 Co 0.4 N. It is attributed to the enhanced electrochemical stability and interfacial comparability. However, doped Cu leads to a slightly decreased capacity. High energy mechanical milling (HEMM) was found to effectively improve the reversible capacity associated with the electrochemical kinetics by modifying the active hosts' morphology characteristics. Moreover, the composite based on mesocarbon microbead (MCMB) and Li 2.6 Co 0.4 N was developed under HEMM. The composite demonstrates a high first cycle efficiency at 100% and a large reversible capacity of ca. 450 mAh g -1 , as well as a stable cycling performance. This work may contribute to a development of the lithium transition metal nitrides as novel anodes for lithium ion batteries

Raman spectral and electrochemical studies of lithium/electrolyte interfaces

Energy Technology Data Exchange (ETDEWEB)

Odziemkowski, M

1922-01-01

Cyclic voltammetry, corrosion potential-time transients and Normal Raman spectroscopy have been employed to characterize the lithium-lithium salt, organic solvent, interfacial region. An in-situ cutting technique was developed to expose lithium metal. In-situ optical and ex-situ scanning electron microscopy (SEM) have been used to examine the morphology of the lithium electrode surface during exposure at open circuit and after anodic polarization. The main reaction product detected by in-situ Raman spectroscopy in the system/lithium/LiAsF[sub 6], tetrahydrofuran (THF) electrolyte was polytetrahydrofuran (PTHF). The conditions for the polymerization reaction in the presence of lithium metal have been determined. Tetrahydrofuran (THF) decomposition reaction mechanisms are discussed. Decomposition reaction products have been determined as arsenic (II) oxide, As[sub 2]O[sub 3] (arsenolite) and arsenious oxyfluoride AsF[sub 2]-O-AsF[sub 2]. Potentiodynamic polarization measurements revealed a substantial shift of the corrosion potential towards positive values and only a moderate increase of anodic dissolution current for in-situ cut lithium metal. Corrosion potential-time merits have been measured. The following electrolytes have been investigated: LiAsF[sub 6], LiPF[sub 6], LiClO[sub 4], and Li(CF[sub 3]SO[sub 2])[sub 2]N in THF, 2Me-THF, and propylene carbonate (PC). The transients permit the ranking of the reactivity of the electrolytes. These measurements have shed light on understanding the stability of various stability and and solvents in contact with lithium. Compared to purified electrolytes, small amounts of water shift the corrosion potential towards even more positive values. Intensive anodic cycling of a Li electrode in unpurified LiAsF[sub 6]/THF electrolyte leads to the breakdown of a surface film/films. While at the open circuit potential (OCP), water in this same electrolyte leads to crack formation in the bulk lithium electrode.

Vinylene carbonate and tris(trimethylsilyl) phosphite hybrid additives to improve the electrochemical performance of spinel lithium manganese oxide/graphite cells at 60 °C

International Nuclear Information System (INIS)

Koo, Bonjae; Lee, Jeongmin; Lee, Yongwon; Kim, Jun Ki; Choi, Nam-Soon

2015-01-01

Highlights: •The combination of tris(trimethylsilyl) phosphite and vinylene carbonate improves the electrochemical performance of lithium manganese oxide/graphite cells at 60 °C. •Removal of hydrogen fluoride and water by tris(trimethylsilyl) phosphite suppresses manganese dissolution from lithium manganese oxide. -- Abstract: The organophosphorus compounds tris(trimethylsilyl) phosphite (TMSP) and vinylene carbonate (VC) have been considered for use as functional additives to improve the electrochemical performance of Li 1.1 Mn 1.86 Mg 0.04 O 4 (LMO)/graphite full cells. Our investigation reveals that the combination of VC and TMSP as additives enhances the cycling properties and storage performance of full cells at 60 °C. The unique functions of the TMSP additive in the VC electrolyte are investigated via ex situ X-ray photoelectron spectroscopy (XPS) and 19 F nuclear magnetic resonance (NMR) measurements. The TMSP additive effectively eliminates trace water and hydrogen fluoride (HF) and produces a protective film on the LMO cathode that alleviates manganese dissolution at 60 °C

Controlled Electrochemical Carboxylation of Graphene To Create a Versatile Chemical Platform for Further Functionalization

DEFF Research Database (Denmark)

Bjerglund Pedersen, Emil; Kongsfelt, Mikkel S.; Shimizu, Kyoko

An electrochemical approach is introduced for the versatile carboxylation of multilayered graphene in 0.1 M Bu4NBF4/MeCN. First, the graphene substrate is negatively charged at −1.9 V vs. Ag/AgI to allow for intercalation of Bu4N+. In the second step, the strongly activated and nucleophilic...... throughout the multilayered graphene structure, independent of the number of graphene sheets. This is assumed to be due to an opening of the entire graphene structure in response to the intercalation of Bu4N+. Hence, this electrochemical method offers a versatile procedure to make all graphene sheets...

Conductivity and electrochemical performance of LiFePO4 slurry in the lithium slurry battery

Science.gov (United States)

Feng, Caimei; Chen, Yongchong; Liu, Dandan; Zhang, Ping

2017-06-01

Lithium slurry battery is a new type of energy storage technique which uses the slurry of solid active materials, conductive additions and liquid electrolyte as the electrode. The proportion of conductive addition and the active material has significant influence on the conductivity and electrochemical performance of the slurry electrode. In the present work, slurries with different volume ratios of LiFePO4 (LFP) and Ketjenblack (KB) were investigated by the electrochemical workstation and charge-discharge testing system (vs. Li/Li+). Results show that the conductivity of the slurry increases linearly with the addition of KB, and the measured specific capacity of the slurry reaches its theoretical value when the volume ratio of KB to LFP is around 0.2. Based on this ratio, a slurry battery with higher loading of LFP (19.1 wt.% in the slurry) was tested, and a specific capacity of 165 mAh/g at 0.2 mA/cm2 and 102 mAh/g at 5 mA/cm2 was obtained for LFP.

Synchrotron-Radiation X-Ray Investigation of Li+/Na+ Intercalation into Prussian Blue Analogues

Directory of Open Access Journals (Sweden)

Yutaka Moritomo

2013-01-01

Full Text Available Prussian blue analogies (PBAs are promising cathode materials for lithium ion (LIB and sodium ion (SIB secondary batteries, reflecting their covalent and nanoporous host structure. With use of synchrotron-radiation (SR X-ray source, we investigated the structural and electronic responses of the host framework of PBAs against Li+ and Na+ intercalation by means of the X-ray powder diffraction (XRD and X-ray absorption spectroscopy (XAS. The structural investigation reveals a robust nature of the host framework against Li+ and Na+ intercalation, which is advantageous for the stability and lifetime of the batteries. The spectroscopic investigation identifies the redox processes in respective plateaus in the discharge curves. We further compare these characteristics with those of the conventional cathode materials, such as, LiCoO2, LiFePO4, and LiMn2O4.

Thermally Reduced Graphene Oxide Electrochemically Activated by Bis-Spiro Quaternary Alkyl Ammonium for Capacitors.

Science.gov (United States)

He, Tieshi; Meng, Xiangling; Nie, Junping; Tong, Yujin; Cai, Kedi

2016-06-08

Thermally reduced graphene oxide (RGO) electrochemically activated by a quaternary alkyl ammonium-based organic electrolytes/activated carbon (AC) electrode asymmetric capacitor is proposed. The electrochemical activation process includes adsorption of anions into the pores of AC in the positive electrode and the interlayer intercalation of cations into RGO in the negative electrode under high potential (4.0 V). The EA process of RGO by quaternary alkyl ammonium was investigated by X-ray diffraction and electrochemical measurements, and the effects of cation size and structure were extensively evaluated. Intercalation by quaternary alkyl ammonium demonstrates a small degree of expansion of the whole crystal lattice (d002) and a large degree of expansion of the partial crystal lattice (d002) of RGO. RGO electrochemically activated by bis-spiro quaternary alkyl ammonium in propylene carbonate/AC asymmetric capacitor exhibits good activated efficiency, high specific capacity, and stable cyclability.

Evidence of ion intercalation mediated band structure modification and opto-ionic coupling in lithium niobite

Science.gov (United States)

Shank, Joshua C.; Tellekamp, M. Brooks; Doolittle, W. Alan

2015-01-01

The theoretically suggested band structure of the novel p-type semiconductor lithium niobite (LiNbO2), the direct coupling of photons to ion motion, and optically induced band structure modifications are investigated by temperature dependent photoluminescence. LiNbO2 has previously been used as a memristor material but is shown here to be useful as a sensor owing to the electrical, optical, and chemical ease of lithium removal and insertion. Despite the high concentration of vacancies present in lithium niobite due to the intentional removal of lithium atoms, strong photoluminescence spectra are observed even at room temperature that experimentally confirm the suggested band structure implying transitions from a flat conduction band to a degenerate valence band. Removal of small amounts of lithium significantly modifies the photoluminescence spectra including additional larger than stoichiometric-band gap features. Sufficient removal of lithium results in the elimination of the photoluminescence response supporting the predicted transition from a direct to indirect band gap semiconductor. In addition, non-thermal coupling between the incident laser and lithium ions is observed and results in modulation of the electrical impedance.

Evidence of ion intercalation mediated band structure modification and opto-ionic coupling in lithium niobite

International Nuclear Information System (INIS)

Shank, Joshua C.; Tellekamp, M. Brooks; Doolittle, W. Alan

2015-01-01

The theoretically suggested band structure of the novel p-type semiconductor lithium niobite (LiNbO 2 ), the direct coupling of photons to ion motion, and optically induced band structure modifications are investigated by temperature dependent photoluminescence. LiNbO 2 has previously been used as a memristor material but is shown here to be useful as a sensor owing to the electrical, optical, and chemical ease of lithium removal and insertion. Despite the high concentration of vacancies present in lithium niobite due to the intentional removal of lithium atoms, strong photoluminescence spectra are observed even at room temperature that experimentally confirm the suggested band structure implying transitions from a flat conduction band to a degenerate valence band. Removal of small amounts of lithium significantly modifies the photoluminescence spectra including additional larger than stoichiometric-band gap features. Sufficient removal of lithium results in the elimination of the photoluminescence response supporting the predicted transition from a direct to indirect band gap semiconductor. In addition, non-thermal coupling between the incident laser and lithium ions is observed and results in modulation of the electrical impedance

Lithium-deficient Li YMn2O4 spinels (0.9 ≤ Y < 1): Lithium content, synthesis temperature, thermal behaviour and electrochemical properties

International Nuclear Information System (INIS)

Pascual, Laura; Perez-Revenga, M. Luz; Rojas, Rosa M.; Rojo, Jose M.; Amarilla, J. Manuel

2006-01-01

Lithium-deficient Li Y Mn 2 O 4 spinels (LD-Li Y Mn 2 O 4 ) with nominal composition (0.9 ≤ Y 2 O 3 and LiNO 3 at temperatures ranging from 700 deg. C to 850 deg. C. X-ray diffraction data show that LD-Li Y Mn 2 O 4 spinels are obtained as single phases in the range Y = 0.975-1 at 700 deg. C and 750 deg. C. Morphological characterization by transmission electron microscopy shows that the particle size of LD-Li Y Mn 2 O 4 spinels increases on decreasing the Li-content. The influence of the Li-content and the synthesis temperature on the thermal and electrochemical behaviours has been systematically studied. Thermal analysis studies indicate that the temperature of the first thermal effect in the differential thermal analysis (DTA)/thermogravimetric (TG) curves, T C1 , linearly increases on decreasing the Li-content. The electrochemical properties of LD-Li Y Mn 2 O 4 spinels, determined by galvanostatic cycling, notably change with the synthesis conditions. So, the first discharge capacity, Q disch. , at C rate increases on rising the Li-content and the synthesis temperature. The sample Li 0.975 Mn 2 O 4 synthesized at 700 deg. C has a Q disch. = 123 mAh g -1 and a capacity retention of 99.77% per cycle. This LD-Li Y Mn 2 O 4 sample had the best electrochemical characteristics of the series

Controllable synthesis of hollow bipyramid β-MnO(2) and its high electrochemical performance for lithium storage.

Science.gov (United States)

Chen, Wei-Min; Qie, Long; Shao, Qing-Guo; Yuan, Li-Xia; Zhang, Wu-Xing; Huang, Yun-Hui

2012-06-27

Three types of MnO2 nanostructures, viz., α-MnO2 nanotubes, hollow β-MnO2 bipyramids, and solid β-MnO2 bipyramids, have been synthesized via a simple template-free hydrothermal method. Cyclic voltammetry and galvanostatic charge/discharge measurements demonstrate that the hollow β-MnO2 bipyramids exhibit the highest specific capacity and the best cyclability; the capacity retains 213 mAh g(-1) at a current density of 100 mA g(-1) after 150 cycles. XRD patterns of the lithiated β-MnO2 electrodes clearly show the expansion of lattice volume caused by lithiation, but the structure keeps stable during lithium insertion/extraction process. We suggest that the excellent performance for β-MnO2 can be attributed to its unique electrochemical reaction, compact tunnel-structure and hollow architecture. The hollow architecture can accommodate the volume change during charge/discharge process and improve effective diffusion paths for both lithium ions and electrons.

Lithium-aluminum-iron electrode composition

Science.gov (United States)

Kaun, Thomas D.

1979-01-01

A negative electrode composition is presented for use in a secondary electrochemical cell. The cell also includes an electrolyte with lithium ions such as a molten salt of alkali metal halides or alkaline earth metal halides that can be used in high-temperature cells. The cell's positive electrode contains a a chalcogen or a metal chalcogenide as the active electrode material. The negative electrode composition includes up to 50 atom percent lithium as the active electrode constituent in an alloy of aluminum-iron. Various binary and ternary intermetallic phases of lithium, aluminum and iron are formed. The lithium within the intermetallic phase of Al.sub.5 Fe.sub.2 exhibits increased activity over that of lithium within a lithium-aluminum alloy to provide an increased cell potential of up to about 0.25 volt.

Low hydrogen containing amorphous carbon films - Growth and electrochemical properties as lithium battery anodes

Energy Technology Data Exchange (ETDEWEB)

Subramanian, V.; Masarapu, Charan; Wei, Bingqing [Department of Mechanical Engineering, University of Delaware, 130 Academy Street, Newark, DE 19716 (United States); Karabacak, Tansel [Department of Applied Science, University of Arkansas at Little Rock, 2801 South University Avenue, Little Rock, AR 72204 (United States); Teki, Ranganath [Department of Chemical and Biological Engineering, Rensselaer Polytechnic Institute, Troy, NY 12180 (United States); Lu, Toh-Ming [Department of Physics, Applied Physics, and Astronomy, Rensselaer Polytechnic Institute, Troy, NY 12180 (United States)

2010-04-02

Amorphous carbon films were deposited successfully on Cu foils by DC magnetron sputtering technique. Electrochemical performance of the film as lithium battery anode was evaluated across Li metal at 0.2 C rate in a non-aqueous electrolyte. The discharge curves showed unusually low irreversible capacity in the first cycle with a reversible capacity of {proportional_to}810 mAh g{sup -1}, which is at least 2 times higher than that of graphitic carbon. For the first time we report here an amorphous carbon showing such a high reversibility in the first cycle, which is very much limited to the graphitic carbon. The deposited films were extensively characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), atomic force microscopy (AFM) and step profilometer for the structural and surface properties. The hydrogen content of the synthesized films was studied using residual gas analysis (RGA). The low hydrogen content and the low specific surface area of the synthesized amorphous carbon film are considered responsible for such a high first cycle columbic efficiency. The growth mechanism and the reasons for enhanced electrochemical performance of the carbon films are discussed. (author)

Low hydrogen containing amorphous carbon films-Growth and electrochemical properties as lithium battery anodes

Science.gov (United States)

Subramanian, V.; Karabacak, Tansel; Masarapu, Charan; Teki, Ranganath; Lu, Toh-Ming; Wei, Bingqing

Amorphous carbon films were deposited successfully on Cu foils by DC magnetron sputtering technique. Electrochemical performance of the film as lithium battery anode was evaluated across Li metal at 0.2 C rate in a non-aqueous electrolyte. The discharge curves showed unusually low irreversible capacity in the first cycle with a reversible capacity of ∼810 mAh g -1, which is at least 2 times higher than that of graphitic carbon. For the first time we report here an amorphous carbon showing such a high reversibility in the first cycle, which is very much limited to the graphitic carbon. The deposited films were extensively characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), atomic force microscopy (AFM) and step profilometer for the structural and surface properties. The hydrogen content of the synthesized films was studied using residual gas analysis (RGA). The low hydrogen content and the low specific surface area of the synthesized amorphous carbon film are considered responsible for such a high first cycle columbic efficiency. The growth mechanism and the reasons for enhanced electrochemical performance of the carbon films are discussed.

Relevant Features of a Triethylene Glycol Dimethyl Ether-Based Electrolyte for Application in Lithium Battery.

Science.gov (United States)

Carbone, Lorenzo; Di Lecce, Daniele; Gobet, Mallory; Munoz, Stephen; Devany, Matthew; Greenbaum, Steve; Hassoun, Jusef

2017-05-24

Triethylene glycol dimethyl ether (TREGDME) dissolving lithium trifluoromethanesulfonate (LiCF 3 SO 3 ) is studied as a suitable electrolyte medium for lithium battery. Thermal and rheological characteristics, transport properties of the dissolved species, and the electrochemical behavior in lithium cell represent the most relevant investigated properties of the new electrolyte. The self-diffusion coefficients, the lithium transference numbers, the ionic conductivity, and the ion association degree of the solution are determined by pulse field gradient nuclear magnetic resonance and electrochemical impedance spectroscopy. The study sheds light on the determinant role of the lithium nitrate (LiNO 3 ) addition for allowing cell operation by improving the electrode/electrolyte interfaces and widening the voltage stability window. Accordingly, an electrochemical activation procedure of the Li/LiFePO 4 cell using the upgraded electrolyte leads to the formation of stable interfaces at the electrodes surface as clearly evidenced by cyclic voltammetry, impedance spectroscopy, and ex situ scanning electron microscopy. Therefore, the lithium battery employing the TREGDME-LiCF 3 SO 3 -LiNO 3 solution shows a stable galvanostatic cycling, a high efficiency, and a notable rate capability upon the electrochemical conditions adopted herein.

Characterization and electrochemical performance of lithium-active titanium dioxide inlaid LiNi{sub 0.5}Co{sub 0.2}Mn{sub 0.3}O{sub 2} material prepared by lithium residue-assisted method

Energy Technology Data Exchange (ETDEWEB)

Li, Lingjun [School of Physics and Electronic Science, Changsha University of Science and Technology, Changsha 410114 (China); Department of Mechanical and Biomedical Engineering, City University of Hong Kong, 83 Tat Chee Avenue, Kowloon (Hong Kong); Chen, Zhaoyong, E-mail: csullj@hotmail.com [School of Physics and Electronic Science, Changsha University of Science and Technology, Changsha 410114 (China); Song, Liubin [Hunan Provincial Key Laboratory of Materials Protection for Electric Power and Transportation, School of Chemistry and Biological Engineering, Changsha University of Science and Technology, Changsha 410004, Hunan (China); Xu, Ming; Zhu, Huali; Gong, Li [School of Physics and Electronic Science, Changsha University of Science and Technology, Changsha 410114 (China); Zhang, Kaili, E-mail: kaizhang@cityu.edu.hk [Department of Mechanical and Biomedical Engineering, City University of Hong Kong, 83 Tat Chee Avenue, Kowloon (Hong Kong)

2015-07-25

Highlights: • LiTiO{sub 2}-inlaid LiNi{sub 0.5}Co{sub 0.2}Mn{sub 0.3}O{sub 2} is prepared by lithium residue-assisted method. • The unique inlaid architecture inherits the advantages of coating and doping. • LiTiO{sub 2} inlaying enhances the pristine at high cyclability and rate properties. • Excess LiTiO{sub 2} modification results in low Li{sup +} diffusion coefficient. • The 3 mol% LiTiO{sub 2} inlaid sample exhibits the best electrochemical performance. - Abstract: The lithium residues are consumed as raw materials to in-situ synthesize the LiTiO{sub 2}-inlaid LiNi{sub 0.5}Co{sub 0.2}Mn{sub 0.3}O{sub 2} composites. The effects of various LiTiO{sub 2} contents on the morphology, structure, and electrochemical properties of LiNi{sub 0.5}Co{sub 0.2}Mn{sub 0.3}O{sub 2} materials are investigated in detail. Energy dispersive spectrometer mapping, high-resolution transmission electron microscopy and fast Fourier transform analysis confirm that the spherical particles of LiNi{sub 0.5}Co{sub 0.2}Mn{sub 0.3}O{sub 2} are completely coated by crystalline LiTiO{sub 2} phase; X-ray diffraction, cross-section SEM and corresponding EDS results indicate that Ti ions are also doped into the bulk LiNi{sub 0.5}Co{sub 0.2}Mn{sub 0.3}O{sub 2} with gradient distribution. Electrochemical tests show that the LiTiO{sub 2}-inlaid samples exhibit excellent reversible capacity, enhanced cyclability, superior lithium diffusion coefficient and rate properties. Specially, the 3 mol% LiTiO{sub 2} inlaid sample maintains 153.7 mA h g{sup −1} with 94.4% capacity retention after 100 cycles between 2.7–4.4 V at 1 C, take 30% advantage than that of the pristine one (118.2 mA h g{sup −1}). This improvement can be attributed to the removal of lithium residues and suitable LiTiO{sub 2} inlaying. The absence of lithium residue is helpful to retard the decomposition of LiPF{sub 6}. While, suitable LiTiO{sub 2} inlaying can protect the bulk from directly contacting the electrolyte

Highly flexible self-standing film electrode composed of mesoporous rutile TiO2/C nanofibers for lithium-ion batteries

International Nuclear Information System (INIS)

Zhao Bote; Cai Rui; Jiang Simin; Sha Yujing; Shao Zongping

2012-01-01

There is increasing interest in flexible, safe, high-power thin-film lithium-ion batteries which can be applied to various modern devices. Although TiO 2 in rutile phase is highly attractive as an anode material of lithium-ion batteries for its high thermal stability and theoretical capacity of 336 mA h g −1 and low price, its inflexibility and sluggish lithium intercalation kinetics of bulk phase strongly limit its practical application for particular in thin-film electrode. Here we show a simple way to prepare highly flexible self-standing thin-film electrodes composed of mesoporous rutile TiO 2 /C nanofibers with low carbon content ( 2 in as-fabricated nanofibers. Big size (10 cm × 4 cm), flexible thin film is obtained after heat treatment under 10%H 2 –Ar at 900 °C for 3 h. After optimization, the diameter of fibers can reach as small as ∼110 nm, and the as-prepared rutile TiO 2 films show high initial electrochemical activity with the first discharge capacity as high as 388 mA h g −1 . What is more, very stable reversible capacities of ∼122, 92, and 70 mA h g −1 are achieved respectively at 1, 5 and 10 C rates with negligible decay rate within 100 cycling times.

Strategies to optimize lithium-ion supercapacitors achieving high-performance: Cathode configurations, lithium loadings on anode, and types of separator

Science.gov (United States)

Cao, Wanjun; Li, Yangxing; Fitch, Brian; Shih, Jonathan; Doung, Tien; Zheng, Jim

2014-12-01

The Li-ion capacitor (LIC) is composed of a lithium-doped carbon anode and an activated carbon cathode, which is a half Li-ion battery (LIB) and a half electrochemical double-layer capacitor (EDLC). LICs can achieve much more energy density than EDLC without sacrificing the high power performance advantage of capacitors over batteries. LIC pouch cells were assembled using activated carbon (AC) cathode and hard carbon (HC) + stabilized lithium metal power (SLMP®) anode. Different cathode configurations, various SLMP loadings on HC anode, and two types of separators were investigated to achieve the optimal electrochemical performance of the LIC. Firstly, the cathode binders study suggests that the PTFE binder offers improved energy and power performances for LIC in comparison to PVDF. Secondly, the mass ratio of SLMP to HC is at 1:7 to obtain the optimized electrochemical performance for LIC among all the various studied mass ratios between lithium loading amounts and active anode material. Finally, compared to the separator Celgard PP 3501, cellulose based TF40-30 is proven to be a preferred separator for LIC.

Chemical, structural, and electrochemical characterization of 5 V spinel and complex layered oxide cathodes of lithium ion batteries

Science.gov (United States)

Tiruvannamalai Annamalai, Arun Kumar

2007-12-01

Lithium ion batteries have revolutionized the portable electronics market since their commercialization first by Sony Corporation in 1990. They are also being intensively pursued for electric and hybrid electric vehicle applications. Commercial lithium ion cells are currently made largely with the layered LiCoO 2 cathode. However, only 50% of the theoretical capacity of LiCoO 2 can be utilized in practical cells due to the chemical and structural instabilities at deep charge as well as safety concerns. These drawbacks together with the high cost and toxicity of Co have created enormous interest in alternative cathodes. In this regard, spinel LiMn2O4 has been investigated widely as Mn is inexpensive and environmentally benign. However, LiMn 2O4 exhibits severe capacity fade on cycling, particularly at elevated temperatures. With an aim to overcome the capacity fading problems, several cationic substitutions to give LiMn2-yMyO 4 (M = Cr, Fe, Co, Ni, and Cu) have been pursued in the literature. Among the cation-substituted systems, LiMn1.5Ni0.5O 4 has become attractive as it shows a high capacity of ˜ 130 mAh/g (theoretical capacity: 147 mAh/g) at around 4.7 V. With an aim to improve the electrochemical performance of the 5 V LiMn 1.5Ni0.5O4 spinel oxide, various cation-substituted LiMn1.5-yNi0.5-zMy+zO4 (M = Li, Mg, Fe, Co, and Zn) spinel oxides have been investigated by chemical lithium extraction. The cation-substituted LiMn1.5-yNi0.5-zM y+zO4 spinel oxides exhibit better cyclability and rate capability in the 5 V region compared to the unsubstituted LiMn1.5Ni 0.5O4 cathodes although the degree of manganese dissolution does not vary significantly. The better electrochemical properties of LiMn 1.5-yNi0.5-zMy+zO4 are found to be due to a smaller lattice parameter difference among the three cubic phases formed during the charge-discharge process. In addition, while the spinel Li1-xMn1.58Ni0.42O4 was chemically stable, the spinel Li1-xCo2O4 was found to exhibit both

Evidence of ion intercalation mediated band structure modification and opto-ionic coupling in lithium niobite

Energy Technology Data Exchange (ETDEWEB)

Shank, Joshua C.; Tellekamp, M. Brooks; Doolittle, W. Alan, E-mail: alan.doolittle@ece.gatech.edu [Department of Electrical and Computer Engineering, Georgia Institute of Technology, Atlanta, Georgia 30332 (United States)

2015-01-21

The theoretically suggested band structure of the novel p-type semiconductor lithium niobite (LiNbO{sub 2}), the direct coupling of photons to ion motion, and optically induced band structure modifications are investigated by temperature dependent photoluminescence. LiNbO{sub 2} has previously been used as a memristor material but is shown here to be useful as a sensor owing to the electrical, optical, and chemical ease of lithium removal and insertion. Despite the high concentration of vacancies present in lithium niobite due to the intentional removal of lithium atoms, strong photoluminescence spectra are observed even at room temperature that experimentally confirm the suggested band structure implying transitions from a flat conduction band to a degenerate valence band. Removal of small amounts of lithium significantly modifies the photoluminescence spectra including additional larger than stoichiometric-band gap features. Sufficient removal of lithium results in the elimination of the photoluminescence response supporting the predicted transition from a direct to indirect band gap semiconductor. In addition, non-thermal coupling between the incident laser and lithium ions is observed and results in modulation of the electrical impedance.

Obtention of superconductivity by room temperature electrochemical oxidation of La2CuO4

International Nuclear Information System (INIS)

Casan-Pastor, N.; Fuertes, A.; Gomez-Romero, P.

1993-01-01

The undoped oxide La2CuO4 has required traditionally synthesis under high pressure of oxygen (and high temperatures) to incorporate excess oxygen into its structure and become a superconductor. The electrochemical oxidation of this same oxide at room temperature and pressure constitutes a striking example of the use of an alternative driving force for the oxidation of oxides to become superconductors. Electrochemical treatment of oxides has been frequently applied to their reduction with cationic intercalation. Oxidations of these solid with the concomitant intercalation of anions into their lattice shows also great promises. The paper reports recent results in the electrochemical oxidation of La2CuO4 and other cuprates, showing also the important role of post-oxidation thermal treatments on the properties of the resulting solids

Effect of the capacity design of activated carbon cathode on the electrochemical performance of lithium-ion capacitors

International Nuclear Information System (INIS)

Shi, Zhiqiang; Zhang, Jin; Wang, Jing; Shi, Jingli; Wang, Chengyang

2015-01-01

Highlights: • MCMB with the optimal pre-lithiation capacity as negative electrode in LIC. • The capacity design of cathode affects the electrochemical performance of LIC. • The optimal designed capacity of positive electrode has been proposed. - ABSTRACT: Lithium-ion capacitors (LICs) are assembled with activated carbon (AC) cathode and pre-lithiated mesocarbon microbeads (MCMB) anode. The effect of AC cathode capacity design on the electrochemical performance of LIC is investigated by the galvanostatic charging-discharging and electrochemical impedance tests. As the designed capacity of AC positive electrode is lower than 50 mAh g −1 , the working potential of negative electrode is always in the low and stable plateau, which is conductive to the sufficient utilization and the working potential stability of positive electrode. When the designed capacity of positive electrode is higher than 50 mAh g −1 , the instability of negative electrode directly causes the reduced utilization and shortened working potential range of the positive electrode, which is responsible for the capacity attenuation and cycle performance deterioration of LIC. The positive electrode capacity design can realize the optimization of electrochemical performance of LIC. LIC50 exhibits the optimal electrochemical performance, high energy density up to 92.3 Wh kg −1 and power density as high as 5.5 kW kg −1 (based on active material mass of two electrodes), excellent capacity retention of 97.0 % after 1000 cycles. The power density and cycle performance of LIC can be further improved by reducing the AC positive electrode designed capacity

Preparation and electrochemical performance of sulfur-alumina cathode material for lithium-sulfur batteries

Energy Technology Data Exchange (ETDEWEB)

Dong, Kang [Faculty of Material Science and Chemistry, China University of Geosciences, 388 Lumo Road, 430074 Wuhan (China); Wang, Shengping, E-mail: spwang@cug.edu.cn [Faculty of Material Science and Chemistry, China University of Geosciences, 388 Lumo Road, 430074 Wuhan (China); Zhang, Hanyu; Wu, Jinping [Faculty of Material Science and Chemistry, China University of Geosciences, 388 Lumo Road, 430074 Wuhan (China)

2013-06-01

Highlights: ► Micron-sized alumina was synthesized as adsorbent for lithium-sulfur batteries. ► Sulfur-alumina material was synthesized via crystallizing nucleation. ► The Al{sub 2}O{sub 3} can provide surface area for the deposition of Li{sub 2}S and Li{sub 2}S{sub 2}. ► The discharge capacity of the battery is improved during the first several cycles. - Abstract: Nano-sized sulfur particles exhibiting good adhesion with conducting acetylene black and alumina composite materials were synthesized by means of an evaporated solvent and a concentrated crystallization method for use as the cathodes of lithium-sulfur batteries. The composites were characterized and examined by X-ray diffraction, environmental scanning electron microscopy and electrochemical methods, such as cyclic voltammetry, electrical impedance spectroscopy and charge–discharge tests. Micron-sized flaky alumina was employed as an adsorbent for the cathode material. The initial discharge capacity of the cathode with the added alumina was 1171 mAh g{sup −1}, and the remaining capacity was 585 mAh g{sup −1} after 50 cycles at 0.25 mA cm{sup −2}. Compared with bare sulfur electrodes, the electrodes containing alumina showed an obviously superior cycle performance, confirming that alumina can contribute to reducing the dissolution of polysulfides into electrolytes during the sulfur charge–discharge process.

Controlling the properties of graphene produced by electrochemical exfoliation

International Nuclear Information System (INIS)

Hofmann, Mario; D Nguyễn, Tuân; Chiang, Wan-Yu; Hsieh, Ya-Ping

2015-01-01

The synthesis of graphene with controllable electronic and mechanical characteristics is of significant importance for its application in various fields ranging from drug delivery to energy storage. Electrochemical exfoliation of graphite has yielded graphene with widely varying behavior and could be a suitable approach. Currently, however the limited understanding of the exfoliation process obstructs targeted modification of graphene properties. We here investigate the process of electrochemical exfoliation and the impact of its parameters on the produced graphene. Using in situ optical and electrical measurements we determine that solvent intercalation is the required first step and the degree of intercalation controls the thickness of the exfoliated graphene. Electrochemical decomposition of water into gas bubbles causes the expansion of graphite and controls the functionalization and lateral size of the exfoliated graphene. Both process steps proceed at different time scales and can be individually addressed through application of pulsed voltages. The potential of the presented approach was demonstrated by improving the performance of graphene-based transparent conductors by 30times. (paper)

Electrochemical properties of copper-based compounds with polyanion frameworks

Energy Technology Data Exchange (ETDEWEB)

Mizuno, Yoshifumi; Hata, Shoma; Suzuki, Kota; Hirayama, Masaaki; Kanno, Ryoji, E-mail: kanno@echem.titech.ac.jp

2016-03-15

The copper-based polyanion compounds Li{sub 6}CuB{sub 4}O{sub 10} and Li{sub 2}CuP{sub 2}O{sub 7} were synthesized using a conventional solid-state reaction, and their electrochemical properties were determined. Li{sub 6}CuB{sub 4}O{sub 10} showed reversible capacity of 340 mA g{sup −1} at the first discharge–charge process, while Li{sub 2}CuP{sub 2}O{sub 7} showed large irreversible capacity and thus low charge capacity. Ex situ X-ray diffraction (XRD) and X-ray absorption near edge structure (XANES) measurements revealed that the electrochemical Li{sup +} intercalation/deintercalation reaction in Li{sub 6}CuB{sub 4}O{sub 10} occurred via reversible Cu{sup 2+}/Cu{sup +} reduction/oxidation reaction. These differences in their discharge/charge mechanisms are discussed based on the strength of the Cu–O covalency via their inductive effects. - Graphical abstract: Electrochemical properties for Cu-based polyanion compounds were investigated. The electrochemical reaction mechanisms are strongly affected by their Cu–O covalentcy. - Highlights: • Electrochemical properties of Cu-based polyanion compounds were investigated. • The Li{sup +} intercalation/deintercalation reaction progressed in Li{sub 6}CuB{sub 4}O{sub 10}. • The electrochemical displacement reaction progressed in Li{sub 2}CuP{sub 2}O{sub 7}. • The strength of Cu–O covalency affects the reaction mechanism.

Combined operando X-ray diffraction–electrochemical impedance spectroscopy detecting solid solution reactions of LiFePO4 in batteries

Science.gov (United States)

Hess, Michael; Sasaki, Tsuyoshi; Villevieille, Claire; Novák, Petr

2015-01-01

Lithium-ion batteries are widely used for portable applications today; however, often suffer from limited recharge rates. One reason for such limitation can be a reduced active surface area during phase separation. Here we report a technique combining high-resolution operando synchrotron X-ray diffraction coupled with electrochemical impedance spectroscopy to directly track non-equilibrium intermediate phases in lithium-ion battery materials. LiFePO4, for example, is known to undergo phase separation when cycled under low-current-density conditions. However, operando X-ray diffraction under ultra-high-rate alternating current and direct current excitation reveal a continuous but current-dependent, solid solution reaction between LiFePO4 and FePO4 which is consistent with previous experiments and calculations. In addition, the formation of a preferred phase with a composition similar to the eutectoid composition, Li0.625FePO4, is evident. Even at a low rate of 0.1C, ∼20% of the X-ray diffractogram can be attributed to non-equilibrium phases, which changes our understanding of the intercalation dynamics in LiFePO4. PMID:26345306

Investigating the stability of cathode materials for rechargeable lithium ion batteries

Science.gov (United States)

Huang, Yiqing

Lithium ion batteries are widely used in portable electronic devices and electric vehicles. However, safety is one of the most important issues for the Li-ion batteries' use. Some cathode materials, such as LiCoO 2, are thermally unstable in the charged state. Upon decomposition these cathode materials release O2, which could react with organic electrolyte, leading to a thermal runaway. Thus understanding the stability of the cathode materials is critical to the safety of lithium ion batteries. Olivine-type LiMnPO4 is a promising cathode material for lithium ion batteries because of its high energy density. We have revealed the critical role of carbon in the stability and thermal behaviour of olivine MnPO 4 obtained by chemical delithiation of LiMnPO4. (Li)MnPO 4 samples with various particle sizes and carbon contents were studied. Carbon-free LiMnPO4 obtained by solid state synthesis in O 2 becomes amorphous upon delithiation. Small amounts of carbon (0.3 wt.%) help to stabilize the olivine structure, so that completely delithiated crystalline olivine MnPO4 can be obtained. Larger amount of carbon (2 wt.%) prevents full delithiation. Heating in air, O2, or N 2 results in structural disorder (cathode materials and the electrolyte. The thermal stability of electrochemically delithiated Li0.1N 0.8C0.15Al0.05O2 (NCA), FePO4 (FP), Mn0.8Fe0.2PO4 (MFP), hydrothermally synthesized VOPO4, LiVOPO4 and electrochemically lithiated Li2VOPO4 is investigated by differential scanning calorimetry (DSC) and thermogravimetric analysis, coupled with mass spectrometry (TGA-MS). The thermal stability is found in the order: NCA< VOPO4< MFP< FP=LiVOPO4=Li2VOPO4. Sealed capsule high pressure experiments show a phase transformation of VOPO4 → HVOPO4 → H2VOPO4 when VOPO4 reacts with electrolyte (1 M LiPF6 in EC: DMC=1:1) between 200 and 300 °C. Finally, we characterize the lithium storage and release mechanism of V2O5 aerogels by x-ray photoelectron spectroscopy (XPS). We study the

Hydrothermal synthesis of electrode materials pyrochlore tungsten trioxide film

Science.gov (United States)

Guo, Jingdong; Li, Yingjeng James; Stanley Whittingham, M.

Hydrothermal synthesis methods have been successfully used to prepare new transition-metal oxides for cathodes in electrochemical devices such as lithium batteries and electrochromic windows. The tungsten oxides were the first studied, but the method has been extended to the oxides of molybdenum, vanadium and manganese. Sodium tungsten oxide films with the pyrochlore structure have been prepared on gold/alumina and indium-doped tin oxide substrates. These films reversibly and rapidly intercalate lithium and hydrogen ions.

Lithium electrode and an electrical energy storage device containing the same

Science.gov (United States)

Lai, San-Cheng

1976-07-13

An improved lithium electrode structure comprises an alloy of lithium and silicon in specified proportions and a supporting current-collecting matrix in intimate contact with said alloy. The lithium electrode of the present invention is utilized as the negative electrode in a rechargeable electrochemical cell.

Lithium-ion batteries advances and applications

CERN Document Server

Pistoia, Gianfranco

2014-01-01

Lithium-Ion Batteries features an in-depth description of different lithium-ion applications, including important features such as safety and reliability. This title acquaints readers with the numerous and often consumer-oriented applications of this widespread battery type. Lithium-Ion Batteries also explores the concepts of nanostructured materials, as well as the importance of battery management systems. This handbook is an invaluable resource for electrochemical engineers and battery and fuel cell experts everywhere, from research institutions and universities to a worldwi

Novel Pyrrolinium-based Ionic Liquids for Lithium Ion Batteries: Effect of the Cation on Physicochemical and Electrochemical Properties

International Nuclear Information System (INIS)

Kim, Hyung-Tae; Kwon, Oh Min; Mun, Junyoung; Oh, Seung M.; Yim, Taeeun; Kim, Young Gyu

2017-01-01

Lithium ion batteries (LIBs) are one of the most promising energy conversion/storage systems, but the low thermal stability of the current electrolytes in LIBs should be improved to expand their potential applications. To enhance the safety properties of LIBs, novel pyrrolinium-based ionic liquids (ILs) were proposed as an alternative electrolyte to the current carbonate electrolyte, which have some task-specific functional groups, i.e., a planar C=N double bond, a C-O ether linkage, and no unstable C-H bond, designed to improve their electrochemical performances as well as the physicochemical properties. As a result, the pyrrolinium-based ILs exhibited much improved physicochemical and electrochemical properties compared to those of the known ILs. Among the prepared ILs, N-allyl-2-methoxypyrrolinium bis(fluorosulfonyl)imide (A(OMe)Pyrl-FSI, 4) showed the high ionic conductivity (10.2 mS cm −1 ), the very good cycling performance (99.3% of retention ratio after 50 cycles) with a LiFePO 4 electrode, and the much improved lithium ion transference number (0.19). IL 4 also had the remarkable rate capability at 5 C-rate with the retention ratio of 81.2% (124.8 mA h g −1 ), compared to the initial discharge capacity of 153.7 mA h g −1 at 0.1 C-rate. In addition, both their high thermal stability and non-flammability were also confirmed.

Preparation and electrochemical performances of cubic shape Cu2O as anode material for lithium ion batteries

International Nuclear Information System (INIS)

Zhang, C.Q.; Tu, J.P.; Huang, X.H.; Yuan, Y.F.; Chen, X.T.; Mao, F.

2007-01-01

Cubic and star-shaped crystalline Cu 2 O particles were synthesized by reducing the copper citrate complex solution with glucose. The microstructure and morphology of the Cu 2 O were characterized by means of X-ray diffraction (XRD) and scanning electron microscopy (SEM). The electrochemical properties of the Cu 2 O as anode materials for lithium ion batteries were measured by galvanostatic charge-discharge tests. The as-synthesized Cu 2 O particles were 1-2 μm with narrow distribution and the shape of Cu 2 O particles had an effect on the electrochemical properties. The cubic Cu 2 O particles delivered a higher reversible discharge capacity (390 mAh g -1 ) than the star-shaped Cu 2 O, and also exhibited good cyclability. The star-shaped Cu 2 O particles presented poor cyclability due to pulverization and deterioration after cycling, but the morphology of the cubic Cu 2 O particles was stable even after 50 cycles

Synthesis and electrochemical performance of surface-modified nano-sized core/shell tin particles for lithium ion batteries

International Nuclear Information System (INIS)

Schmuelling, Guido; Meyer, Hinrich-Wilhelm; Placke, Tobias; Winter, Martin; Oehl, Nikolas; Knipper, Martin; Kolny-Olesiak, Joanna; Plaggenborg, Thorsten; Parisi, Jürgen

2014-01-01

Tin is able to lithiate and delithiate reversibly with a high theoretical specific capacity, which makes it a promising candidate to supersede graphite as the state-of-the-art negative electrode material in lithium ion battery technology. Nevertheless, it still suffers from poor cycling stability and high irreversible capacities. In this contribution, we show the synthesis of three different nano-sized core/shell-type particles with crystalline tin cores and different amorphous surface shells consisting of SnO x and organic polymers. The spherical size and the surface shell can be tailored by adjusting the synthesis temperature and the polymer reagents in the synthesis, respectively. We determine the influence of the surface modifications with respect to the electrochemical performance and characterize the morphology, structure, and thermal properties of the nano-sized tin particles by means of high-resolution transmission electron microscopy, x-ray diffraction, and thermogravimetric analysis. The electrochemical performance is investigated by constant current charge/discharge cycling as well as cyclic voltammetry. (paper)

The preparation and electrochemical performances of LiFePO4-multiwalled nanotubes composite cathode materials for lithium ion batteries

International Nuclear Information System (INIS)

Feng Yan

2010-01-01

LiFePO 4 -MWCNTs (multi-walled carbon nanotubes) composite cathode materials were prepared by mixing LiFePO 4 and MWCNTs in ethanol followed by heat-treatment at 500 deg. C for 5 h. The structural, morphology and electrochemical performances of LiFePO 4 -MWCNTs composite materials were investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), galvanostatic charge-discharge cycle tests, cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The results indicated that MWCNTs adding improved the electronic conductivity, the discharge capacity, cycle stability and lithium ion diffusion kinetics of LiFePO 4 , but MWCNTs adding did not charge the orthorhombic olivine-type structure of LiFePO 4 . In all these prepared LiFePO 4 with x wt.% MWCNTs (x = 4, 7, 10) composites, 7 wt.% MWCNTs adding composite cathode shows the best electrochemical performance, which gets an initial discharge capacity of 152.7 mAh g -1 at 0.18 C discharge rates with capacity retention ratio of 97.77% after 100 cycles.

Synthesis and Electrochemical Performance of SiOC-Carbon Nanotube Composite Coatings

Science.gov (United States)

Bhandavat, Romil; Cologna, Marco; Raj, Rishi; Singh, Gurpreet

2012-02-01

Rechargeable battery anodes made from crystalline Si-based nanostructures have been shown to possess high experimental first cycle capacities (3000 mAh/g), but face challenges in sustaining these capacities beyond initial cycles mainly due to large volume expansion (400 percent) and chemical degradation (pulverization). Polymer-derived ceramic SiOC due to its high thermodynamic stability and nano domain structure could present a viable alternative. Additionally, functionalization of SiOC with carbon nanotubes could result in increased electronic and ionic conductivities in the ceramic. Here, we demonstrate synthesis and electrochemical characterization of SiOC-CNT composite coatings for use in Li-ion battery anode. Materials characterization performed using electron microscopy, Infrared (FT-IR), and X-ray photoelectron spectroscopy suggests non-covalent functionalization of CNT with oxygen moieties in SiOC. Sustained battery capacities of over 700 mAh/g and first cycle columbic efficiencies of about 75 percent were achieved. Future work will involve determination of lithium ion intercalation sites characterized by electron microscopy whereas cyclic voltammetry analysis will access the sequential change in anode chemistry.

High-Capacity and Long-Cycle Life Aqueous Rechargeable Lithium-Ion Battery with the FePO4 Anode.

Science.gov (United States)

Wang, Yuesheng; Yang, Shi-Ze; You, Ya; Feng, Zimin; Zhu, Wen; Gariépy, Vincent; Xia, Jiexiang; Commarieu, Basile; Darwiche, Ali; Guerfi, Abdelbast; Zaghib, Karim

2018-02-28

Aqueous lithium-ion batteries are emerging as strong candidates for a great variety of energy storage applications because of their low cost, high-rate capability, and high safety. Exciting progress has been made in the search for anode materials with high capacity, low toxicity, and high conductivity; yet, most of the anode materials, because of their low equilibrium voltages, facilitate hydrogen evolution. Here, we show the application of olivine FePO 4 and amorphous FePO 4 ·2H 2 O as anode materials for aqueous lithium-ion batteries. Their capacities reached 163 and 82 mA h/g at a current rate of 0.2 C, respectively. The full cell with an amorphous FePO 4 ·2H 2 O anode maintained 92% capacity after 500 cycles at a current rate of 0.2 C. The acidic aqueous electrolyte in the full cells prevented cathodic oxygen evolution, while the higher equilibrium voltage of FePO 4 avoided hydrogen evolution as well, making them highly stable. A combination of in situ X-ray diffraction analyses and computational studies revealed that olivine FePO 4 still has the biphase reaction in the aqueous electrolyte and that the intercalation pathways in FePO 4 ·2H 2 O form a 2-D mesh. The low cost, high safety, and outstanding electrochemical performance make the full cells with olivine or amorphous hydrated FePO 4 anodes commercially viable configurations for aqueous lithium-ion batteries.

Structural and electrochemical properties of SnO nanoflowers as an anode material for lithium ion batteries

International Nuclear Information System (INIS)

Iqbal, M. Zubair; Wang, Fengping; Zhao, Hailei; Rafique, M. Yasir; Wang, Jie; Li, Quanshui

2012-01-01

Graphical abstract: -- Novel self-assembled highly hierarchical SnO nanoflowers with acute edge petals have been successfully synthesized by a template-free hydrothermal growth method using SnCl 2 ·2H 2 O and KOH as precursors. Field emission scanning electron microscopy results show that the flower-like SnO architectureis in the range 4–7 μm. Furthermore, Raman modes at A 1g = 212 and B 1g = 114 cm −1 further testify to the existence of nanotetragonal phase SnO. The electrochemical results suggest that synthesized SnO nanoflowers are a promising anode material for lithium ion batteries.

Ion transport and phase transformation in thin film intercalation electrodes

Energy Technology Data Exchange (ETDEWEB)

Wunde, Fabian; Nowak, Susann; Muerter, Juliane; Hadjixenophontos, Efi; Berkemeier, Frank; Schmitz, Guido [Stuttgart Univ. (Germany). Inst. fuer Materialwissenschaft

2017-11-15

Thin film battery electrodes of the olivine structure LiFePO{sub 4} and the spinel phase LiMn{sub 2}O{sub 4} are deposited through ion-beam sputtering. The intercalation kinetics is studied by cyclo-voltammetry using variation of the cycling rate over 4 to 5 orders of magnitude. The well-defined layer geometry allows a detailed quantitative analysis. It is shown that LiFePO{sub 4} clearly undergoes phase separation during intercalation, although the material is nano-confined and very high charging rates are applied. We present a modified Randles-Sevcik evaluation adapted to phase-separating systems. Both the charging current and the overpotential depend on the film thickness in a systematic way. The analysis yields evidence that the grain boundaries are important short circuit paths for fast transport. They increase the electrochemical active area with increasing layer thickness. Evidence is obtained that the grain boundaries in LiFePO{sub 4} have the character of an ion-conductor of vanishing electronic conductivity.

Control oriented 1D electrochemical model of lithium ion battery

International Nuclear Information System (INIS)

Smith, Kandler A.; Rahn, Christopher D.; Wang, Chao-Yang

2007-01-01

Lithium ion (Li-ion) batteries provide high energy and power density energy storage for diverse applications ranging from cell phones to hybrid electric vehicles (HEVs). For efficient and reliable systems integration, low order dynamic battery models are needed. This paper introduces a general method to generate numerically a fully observable/controllable state variable model from electrochemical kinetic, species and charge partial differential equations that govern the discharge/charge behavior of a Li-ion battery. Validated against a 313th order nonlinear CFD model of a 6 Ah HEV cell, a 12th order state variable model predicts terminal voltage to within 1% for pulse and constant current profiles at rates up to 50 C. The state equation is constructed in modal form with constant negative real eigenvalues distributed in frequency space from 0 to 10 Hz. Open circuit potential, electrode surface concentration/reaction distribution coupling and electrolyte concentration/ionic conductivity nonlinearities are explicitly approximated in the model output equation on a local, electrode-averaged and distributed basis, respectively. The balanced realization controllability/observability gramian indicates that the fast electrode surface concentration dynamics are more observable/controllable than the electrode bulk concentration dynamics (i.e. state of charge)

Electrochemical Properties of LLTO/Fluoropolymer-Shell Cellulose-Core Fibrous Membrane for Separator of High Performance Lithium-Ion Battery

Science.gov (United States)

Huang, Fenglin; Liu, Wenting; Li, Peiying; Ning, Jinxia; Wei, Qufu

2016-01-01

A superfine Li0.33La0.557TiO3 (LLTO, 69.4 nm) was successfully synthesized by a facile solvent-thermal method to enhance the electrochemical properties of the lithium-ion battery separator. Co-axial nanofiber of cellulose and Poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) was prepared by a co-axial electrospinning technique, in which the shell material was PVDF-HFP and the core was cellulose. LLTO superfine nanoparticles were incorporated into the shell of the PVDF-HFP. The core–shell composite nanofibrous membrane showed good wettability (16.5°, contact angle), high porosity (69.77%), and super electrolyte compatibility (497%, electrolyte uptake). It had a higher ionic conductivity (13.897 mS·cm−1) than those of pure polymer fibrous membrane and commercial separator. In addition, the rate capability (155.56 mAh·g−1) was also superior to the compared separator. These excellent performances endowed LLTO composite nanofibrous membrane as a promising separator for high-performance lithium-ion batteries. PMID:28787873

The electrochemical generation of useful chemical species from lunar materials

Science.gov (United States)

Tsai, Kan J.; Kuchynka, Daniel J.; Sammells, Anthony F.

1989-01-01

The current status of work on an electrochemical technology for the simultaneous generation of oxygen and lithium from a Li2O containing molten salt (Li2O-LiCl-LiF) is discussed. The electrochemical cell utilizes an oxygen vacancy conducting solid electrolyte, yttria-stabilized zirconia, to effect separation between the oxygen evolving and lithium reduction half-cell reactions. The cell, which operates at 700 to 800 C, possesses rapid electrode kinetics at the lithium-alloy electrode with exchange current density values being greater than 60 mA/sq cm, showing high reversibility for this reaction. When used in the electrolytic mode, lithium produced at the negative electrode would be continuously removed from the cell for later use (under lunar conditions) as an easily storable reducting agent (compared to H2) for the chemical refining of lunar ores via the general reaction: 2Li + MO yields Li2O + M where MO represents a lunar ore. Emphasis to this time has been on the simulated lunar ore ilmenite (FeTiO3), which we have found becomes chemically reduced by Li at 432 C. Furthermore, both Fe2O3 and TiO2 have been reduced by Li to give the corresponding metal. This electrochemical approach provides a convenient route for producing metals under lunar conditions and oxygen for the continuous maintenance of human habitats on the Moon's surface. Because of the high reversibility of this electrochemical system, it has also formed the basis for the lithium-oxygen secondary battery. This secondary lithium-oxygen battery system posses the highest theoretical energy density yet investigated.

Studies on electrochemical lithium insertion in isostructural titanium niobate and tantalate phases with shear ReO3 structure

International Nuclear Information System (INIS)

Saritha, D.; Varadaraju, U.V.

2013-01-01

Graphical abstract: - Highlights: • Electrochemical lithium insertion into ReO 3 type phases TiNb 2 O 7 , TiTa 2 O 7 is feasible. • TiNb 2 O 7 exhibits good cycling behavior and high reversible capacity of 212 mAh g −1 . • TiTa 2 O 7 exhibits reversible capacity of 100 mAh g −1 . - Abstract: TiNb 2 O 7 and TiTa 2 O 7 phases are synthesized by solid-state reaction method and are investigated for electrochemical Li insertion/extraction. The electrochemical insertion of Li in these phases is characterized by both solid solution and two-phase regimes. The structure is stable toward Li insertion/extraction. The first cycle discharge capacity values are 307 mAh g −1 and 215 mAh g −1 in the voltage range of 3.0–1.0 V for TiNb 2 O 7 and TiTa 2 O 7 phases, respectively. The discharge capacities of TiNb 2 O 7 and TiTa 2 O 7 are 212 mAh g −1 and 100 mAh g −1 , respectively, after 20 cycles

A novel method for identification of lithium-ion battery equivalent circuit model parameters considering electrochemical properties

Science.gov (United States)

Zhang, Xi; Lu, Jinling; Yuan, Shifei; Yang, Jun; Zhou, Xuan

2017-03-01

This paper proposes a novel parameter identification method for the lithium-ion (Li-ion) battery equivalent circuit model (ECM) considering the electrochemical properties. An improved pseudo two-dimension (P2D) model is established on basis of partial differential equations (PDEs), since the electrolyte potential is simplified from the nonlinear to linear expression while terminal voltage can be divided into the electrolyte potential, open circuit voltage (OCV), overpotential of electrodes, internal resistance drop, and so on. The model order reduction process is implemented by the simplification of the PDEs using the Laplace transform, inverse Laplace transform, Pade approximation, etc. A unified second order transfer function between cell voltage and current is obtained for the comparability with that of ECM. The final objective is to obtain the relationship between the ECM resistances/capacitances and electrochemical parameters such that in various conditions, ECM precision could be improved regarding integration of battery interior properties for further applications, e.g., SOC estimation. Finally simulation and experimental results prove the correctness and validity of the proposed methodology.

Mathematical modeling of the electrochemical impedance spectroscopy in lithium ion battery cycling

International Nuclear Information System (INIS)

Xie, Yuanyuan; Li, Jianyang; Yuan, Chris

2014-01-01

Electrochemical impedance spectroscopy (EIS) has been widely utilized as an experimental method for understanding the internal mechanisms and aging effect of lithium ion battery. However, the impedance interpretation still has a lot of difficulties. In this study, a multi-physics based EIS simulation approach is developed to study the cycling effect on the battery impedance responses. The SEI film growth during cycling is coherently coupled with the complicated charge, mass and energy transport processes. The EIS simulation is carried out by applying a perturbation voltage on the electrode surface, and the numerical results on cycled cells are compared with the corresponding experimental data. The effect of electrical double layer, electrode open circuit potential as well as the diffusivity of binary electrolyte are simulated on battery impedance responses. The influence of different SEI growth rate, thermal conditions and charging-discharging rate during cycling are also studied. This developed method can be potentially utilized for interpretation and analysis of experimental EIS results

Electrochemical cell

Science.gov (United States)

Kaun, T.D.

An improved secondary electrochemical cell is disclosed having a negative electrode of lithium aluminum, a positive electrode of iron sulfide, a molten electrolyte of lithium chloride and potassium chloride, and the combination that the fully charged theoretical capacity of the negative electrode is in the range of 0.5 to 1.0 that of the positive electrode. The cell thus is negative electrode limiting during discharge cycling. Preferably, the negative electrode contains therein, in the approximate range of 1 to 10 volume % of the electrode, an additive from the materials of graphitized carbon, aluminum-iron alloy, and/or magnesium oxide.

Enhanced electrochemical properties of F-doped Li2MnSiO4/C for lithium ion batteries

Science.gov (United States)

Wang, Chao; Xu, Youlong; Sun, Xiaofei; Zhang, Baofeng; Chen, Yanjun; He, Shengnan

2018-02-01

The Li2MnSiO4 as a novel cathode material for lithium ion batteries, performs high specific capacity, high thermal stability, low cost and etc. However, it suffers from relatively low electronic conductivity and lithium ion diffusion rate. Herein, we successfully introduce fluorine to Li2MnSiO4 (Li2MnSiO4-xFx, x = 0.00, 0.01, 0.03 and 0.05) to overcome these obstacles. The results show that F doping not only enlarges the lattice parameters but also decreases the particle size, synergistically improving the lithium ion diffusion of Li2MnSiO4. Moreover, F doping increase electronic conductivity of Li2MnSiO4/C by inhibiting the formation of C-O bonds in the carbon layers. Meanwhile, F doping improves the crystallinity and stabilizes the crystal structure of Li2MnSiO4. Finally, the Li2MnSiO3.97F0.03/C with the best electrochemical performances delivers the initial specific discharge capacity of 279 mA h g-1 at 25mA g-1 current density from 1.5 V to 4.8 V. Also, it maintains a higher capacity (201 mA h g-1) than F-free Li2MnSiO4 (145 mA h g-1) after 50 cycles.

Graphene-supported SnO2 nanoparticles prepared by a solvothermal approach for an enhanced electrochemical performance in lithium-ion batteries

OpenAIRE

Wang, Bei; Su, Dawei; Park, Jinsoo; Ahn, Hyojun; Wang, Guoxiu

2012-01-01

SnO2 nanoparticles were dispersed on graphene nanosheets through a solvothermal approach using ethylene glycol as the solvent. The uniform distribution of SnO2 nanoparticles on graphene nanosheets has been confirmed by scanning electron microscopy and transmission electron microscopy. The particle size of SnO2 was determined to be around 5 nm. The as-synthesized SnO2/graphene nanocomposite exhibited an enhanced electrochemical performance in lithium-ion batteries, compared with bare graphene ...

Nanosized {alpha}-LiFeO{sub 2} as electrochemical supercapacitor electrode in neutral sulfate electrolytes

Energy Technology Data Exchange (ETDEWEB)

Santos-Pena, J., E-mail: iq2sanpe@uco.e [Departamento de Quimica Inorganica e Ingenieria Quimica, Edificio Marie Curie, Campus de Rabanales, Universidad de Cordoba, 14071 Cordoba (Spain); Crosnier, O.; Brousse, T. [Laboratoire de Genie des Materiaux et Procedes Associes, Ecole Polytechnique de l' Universite de Nantes, Site de la Chantrerie, rue Christian Pauc s/n, 44376 Nantes Cedex 3 (France)

2010-10-30

In this work we have explored the electrochemical properties of two lithiated iron oxide powders for supercapacitor purposes. These samples mainly consisted of {alpha}-LiFeO{sub 2} in nanosized or micrometric form. Electrolyte was an aqueous 0.5 M Li{sub 2}SO{sub 4} solution and voltage range studied was between 0 and -0.7 V vs. a Ag/AgCl reference electrode. As expected, electrochemical performance was dependent on the particle size. When electrolyte was deaerated a stable capacitance of {approx}50 F g{sup -1} is provided by the nanosized sample for several hundred cycles. Other sulfate based salts (Na{sub 2}SO{sub 4}, K{sub 2}SO{sub 4}, Cs{sub 2}SO{sub 4}) were investigated as electrolytes but only Li{sub 2}SO{sub 4} leads to a stable capacitance upon cycling, probably due to lithium intercalation. An hybrid cell consisting of this sample and MnO{sub 2} as negative and positive electrodes, respectively, delivered 0.3 F cm{sup -2} (10 F g{sup -1}). Although these values are lower than reported for other aqueous hybrid cell, {alpha}-LiFeO{sub 2}/MnO{sub 2} asymmetric capacitor is interesting from both, an economic and an environmental point of view.

Scalable integration of Li5FeO4 towards robust, high-performance lithium-ion hybrid capacitors.

Science.gov (United States)

Park, Min-Sik; Lim, Young-Geun; Hwang, Soo Min; Kim, Jung Ho; Kim, Jeom-Soo; Dou, Shi Xue; Cho, Jaephil; Kim, Young-Jun

2014-11-01

Lithium-ion hybrid capacitors have attracted great interest due to their high specific energy relative to conventional electrical double-layer capacitors. Nevertheless, the safety issue still remains a drawback for lithium-ion capacitors in practical operational environments because of the use of metallic lithium. Herein, single-phase Li5FeO4 with an antifluorite structure that acts as an alternative lithium source (instead of metallic lithium) is employed and its potential use for lithium-ion capacitors is verified. Abundant Li(+) amounts can be extracted from Li5FeO4 incorporated in the positive electrode and efficiently doped into the negative electrode during the first electrochemical charging. After the first Li(+) extraction, Li(+) does not return to the Li5FeO4 host structure and is steadily involved in the electrochemical reactions of the negative electrode during subsequent cycling. Various electrochemical and structural analyses support its superior characteristics for use as a promising lithium source. This versatile approach can yield a sufficient Li(+)-doping efficiency of >90% and improved safety as a result of the removal of metallic lithium from the cell. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electrochemical-thermal modeling and microscale phase change for passive internal thermal management of lithium ion batteries.

Energy Technology Data Exchange (ETDEWEB)

Fuller, Thomas F. (Georgia Institute of Technology, Atlanta, GA); Bandhauer, Todd (Georgia Institute of Technology, Atlanta, GA); Garimella, Srinivas (Georgia Institute of Technology, Atlanta, GA)

2012-01-01

A fully coupled electrochemical and thermal model for lithium-ion batteries is developed to investigate the impact of different thermal management strategies on battery performance. In contrast to previous modeling efforts focused either exclusively on particle electrochemistry on the one hand or overall vehicle simulations on the other, the present work predicts local electrochemical reaction rates using temperature-dependent data on commercially available batteries designed for high rates (C/LiFePO{sub 4}) in a computationally efficient manner. Simulation results show that conventional external cooling systems for these batteries, which have a low composite thermal conductivity ({approx}1 W/m-K), cause either large temperature rises or internal temperature gradients. Thus, a novel, passive internal cooling system that uses heat removal through liquid-vapor phase change is developed. Although there have been prior investigations of phase change at the microscales, fluid flow at the conditions expected here is not well understood. A first-principles based cooling system performance model is developed and validated experimentally, and is integrated into the coupled electrochemical-thermal model for assessment of performance improvement relative to conventional thermal management strategies. The proposed cooling system passively removes heat almost isothermally with negligible thermal resistances between the heat source and cooling fluid. Thus, the minimization of peak temperatures and gradients within batteries allow increased power and energy densities unencumbered by thermal limitations.

Bulletin of Materials Science | Indian Academy of Sciences

Indian Academy of Sciences (India)

... synthesized LiNi0.8Co0.2O2 and its performance as cathode in Li-ion cells ... Lithium batteries; intercalation compounds; electrochemical characterization; diffusion ... electron microscopic studies on the as-synthesized LiNi0.8Co0.2O2 sample ... phase transition is further supported by impedance spectroscopy that shows ...

Effect of the synthesis method on the microstructure, morphology and electrochemical characteristics of α-Fe2O3 anodes for Lithium ion batteries

International Nuclear Information System (INIS)

Uzunov, I.; Klissurski, D.; Uzunova, S.; Aleksandrova, A.

2009-01-01

Effect of the synthesis method and temperature on some structural characteristics and electrochemical behaviour was investigated for samples of α-Fe 2 O 3 prepared from different precursors. The phase composition, morphology and crystallinity of the obtained materials were determined by X-ray diffraction analysis (XRD) and scanning electron microscopy (SEM). The electrochemical behaviour of the synthesized samples was studied within voltage range 0.01-2.5V and various current densities. The electrochemical behaviour of the obtained active anode materials was found to depend mostly on the ratio between mean particle size (MPS) and mean coherent domain size (MCDS). It was found that the ratio depends on the synthesis method and calcination temperature. By optimization of the synthesis processes α-Fe 2 O 3 was prepared with optimal microstructure and particle size, a promising anode material for lithium ion batteries. (authors)

The Surface Coating of Commercial LiFePO4 by Utilizing ZIF-8 for High Electrochemical Performance Lithium Ion Battery

Science.gov (United States)

Xu, XiaoLong; Qi, CongYu; Hao, ZhenDong; Wang, Hao; Jiu, JinTing; Liu, JingBing; Yan, Hui; Suganuma, Katsuaki

2018-03-01

The requirement of energy-storage equipment needs to develop the lithium ion battery (LIB) with high electrochemical performance. The surface modification of commercial LiFePO4 (LFP) by utilizing zeolitic imidazolate frameworks-8 (ZIF-8) offers new possibilities for commercial LFP with high electrochemical performances. In this work, the carbonized ZIF-8 (CZIF-8) was coated on the surface of LFP particles by the in situ growth and carbonization of ZIF-8. Transmission electron microscopy indicates that there is an approximate 10 nm coating layer with metal zinc and graphite-like carbon on the surface of LFP/CZIF-8 sample. The N2 adsorption and desorption isotherm suggests that the coating layer has uniform and simple connecting mesopores. As cathode material, LFP/CZIF-8 cathode-active material delivers a discharge specific capacity of 159.3 mAh g-1 at 0.1C and a discharge specific energy of 141.7 mWh g-1 after 200 cycles at 5.0C (the retention rate is approximate 99%). These results are attributed to the synergy improvement of the conductivity, the lithium ion diffusion coefficient, and the degree of freedom for volume change of LFP/CZIF-8 cathode. This work will contribute to the improvement of the cathode materials of commercial LIB.[Figure not available: see fulltext.

Synthesis and Electrochemical Performance of a Lithium Titanium Phosphate Anode for Aqueous Lithium-Ion Batteries

KAUST Repository

Wessells, Colin; La Mantia, Fabio; Deshazer, Heather; Huggins, Robert A.; Cui, Yi

2011-01-01

Lithium-ion batteries that use aqueous electrolytes offer safety and cost advantages when compared to today's commercial cells that use organic electrolytes. The equilibrium reaction potential of lithium titanium phosphate is -0.5 V with respect

Lithium Insertion in LixMn2O4, 0

DEFF Research Database (Denmark)

West, Keld; Zachau-Christiansen, Birgit; Skaarup, Steen

1996-01-01

The electrochemical lithium insertion properties of highly crystalline LixMn2O4 are investigated in the approximate lithium insertion range 0 ... of the lithium insertion/extraction reactions is better at the higher voltages (versus Li/Li+), and particularly at the 4 V plateau. The lithium insertion/extraction reaction at the 1 V plateau although essentially reversible is associated with a significant voltage hysteresis....

Lithium-Ion Electrolytes Containing Flame Retardant Additives for Increased Safety Characteristics

Science.gov (United States)

Smart, Marshall C. (Inventor); Smith, Kiah A. (Inventor); Bugga, Ratnakumar V. (Inventor); Prakash, Surya G. (Inventor); Krause, Frederick Charles (Inventor)

2014-01-01

The invention discloses various embodiments of Li-ion electrolytes containing flame retardant additives that have delivered good performance over a wide temperature range, good cycle life characteristics, and improved safety characteristics, namely, reduced flammability. In one embodiment of the invention there is provided an electrolyte for use in a lithium-ion electrochemical cell, the electrolyte comprising a mixture of an ethylene carbonate (EC), an ethyl methyl carbonate (EMC), a fluorinated co-solvent, a flame retardant additive, and a lithium salt. In another embodiment of the invention there is provided an electrolyte for use in a lithium-ion electrochemical cell, the electrolyte comprising a mixture of an ethylene carbonate (EC), an ethyl methyl carbonate (EMC), a flame retardant additive, a solid electrolyte interface (SEI) film forming agent, and a lithium salt.

A Novel Battery Cathode Material Based on intercalation Chemistry: Redox Reactions of the 2,5-Dimercapto-1,3,4-Thiadiazole/V2O5 Xerogel System

National Research Council Canada - National Science Library

Shouji, Eiichi

1998-01-01

.... Elemental analysis gives a composition for the intercalation material of (POLYDMcT)0.25.V2O5.1.4H2O. The cyclic voltammetry and galvanostatic discharge behavior of the parent V2O5 xerogel and the new intercalation material are directly compared. The (POLYDMcT)0.25.V2O5.1.4H2O hybrid composite material is shown to have superior discharge behavior, making it an attractive candidate material for use as a cathode in lithium secondary batteries.

Preparation of octahedral CuO micro/nanocrystals and electrochemical performance as anode for lithium-ion battery

International Nuclear Information System (INIS)

Feng, Lili; Xuan, Zhewen; Bai, Yang; Zhao, Hongbo; Li, Li; Chen, Yashun; Yang, Xianqin; Su, Changwei; Guo, Junming; Chen, Xiaokai

2014-01-01

Highlights: • Octahedral cupric oxides with hollow structure were prepared. • No hard template was used in the preparation of hollow cupric oxides. • The cupric oxides show good reversible capacity. - Abstract: Herein we report that three octahedral CuO samples with hollow or solid structure are successfully prepared by firstly preparation of Cu 2 O products using a chemical reduction method, then by calcination in a muffle furnace at 300 °C for 3 h in air atmosphere. The obtained CuO samples serve as a good model system for the study as anodes for lithium ion batteries. All the three CuO samples have high discharge specific capacity and good cycling stability from the 2nd cycling to the 50th cycling. Octahedral CuO hollow crystals with 400 nm in size have the highest reversible capacity and the smallest resistance. So their electrochemical performances are partly related to their morphologies. The results suggest that the as-prepared CuO samples, especially the 400 nm hollow octahedral CuO crystals could be a promising material for the anode of lithium-ion battery

Preparation and electrochemical properties of nanocable-like Nb2O5/surface-modified carbon nanotubes composites for anode materials in lithium ion batteries

International Nuclear Information System (INIS)

Shi, Chongfu; Xiang, Kaixiong; Zhu, Yirong; Chen, Xianhong; Zhou, Wei; Chen, Han

2017-01-01

Highlights: •The acid pretreatment for CNTs is a key factor to fabricate nanocable-like Nb 2 O 5 /SMCNTs composites. •The polar functional groups can induce the symmetrical growth of Nb 2 O 5 nanoparticitles on the surface of SMCNTs. •SMCNTs can provide sufficient conductive contacts for composites and abundant active sites for electrochemical reaction. -- Abstract: Uniform nanocable-like Nb 2 O 5 /surface-modified carbon nanotubes (SMCNTs) composites for anode materials in lithium ion batteries were synthesized by hydrothermal method. It was indicated that Nb 2 O 5 nanoparticles were tightly and uniformly cultivated on carbon nanotubes when CNTs were pretreated with concentrated H 2 SO 4 . As a result, Nb 2 O 5 /SMCNTs composite materials showed remarkable electrochemical performance as anode materials for lithium-ion batteries. It delivered a high reversible capacity of 441 mA h g −1 cycled at the current density of 40 mA g −1 after 100 cycles and an excellent rate capacity of 185 mA h g −1 at the high current density of 5000 mA g −1 after 200 cycles.

Iron phosphate materials as cathodes for lithium batteries

CERN Document Server

Prosini, Pier Paolo

2011-01-01

""Iron Phosphate Materials as Cathodes for Lithium Batteries"" describes the synthesis and the chemical-physical characteristics of iron phosphates, and presents methods of making LiFePO4 a suitable cathode material for lithium-ion batteries. The author studies carbon's ability to increase conductivity and to decrease material grain size, as well as investigating the electrochemical behaviour of the materials obtained. ""Iron Phosphate Materials as Cathodes for Lithium Batteries"" also proposes a model to explain lithium insertion/extraction in LiFePO4 and to predict voltage profiles at variou

Electrochemical improvement of low-temperature petroleum cokes by chemical oxidation with H2O2 for their use as anodes in lithium ion batteries

International Nuclear Information System (INIS)

Concheso, A.; Santamaria, R.; Menendez, R.; Jimenez-Mateos, J.M.; Alcantara, R.; Lavela, P.; Tirado, J.L.

2006-01-01

The electrochemical performance of non-graphitized petroleum cokes has been improved by mild oxidation using hydrogen peroxide, a procedure used for the first time in these materials. For this purpose, various carbonisation temperatures and H 2 O 2 treatments were tested. For low sulfur content cokes, the aqueous oxidative treatment significantly increases the capacity values above 372 mAh/g during the first cycles. In contrast, cokes with a sulfur content of ca. 5%, did not shown a real improvement. The former results have been interpreted in terms of an effective oxidation of the particles surface, which removes unorganized carbon, where lithium can be irreversibly trapped. Moreover, a stable and less resistive passivating layer grows during the first discharge of lithium, as revealed by impedance spectroscopy. Therefore, chemical procedures, as mild oxidation, open an interesting field of research for the improvement of disordered carbons as anode materials in lithium ion batteries

Effect of calcination temperature on microstructure and electrochemical performance of lithium-rich layered oxide cathode materials

International Nuclear Information System (INIS)

Ma, Quanxin; Peng, Fangwei; Li, Ruhong; Yin, Shibo; Dai, Changsong

2016-01-01

Highlights: • A series of Li-rich layered oxide cathode materials (Li_1_._2Mn_0_._5_6Ni_0_._1_6Co_0_._0_8O_2) were successfully synthesized via a two-step synthesis method. • The effects of calcination temperature on the cathode materials were researched in detail. • A well-crystallized layered structure was obtained as the calcination temperature increased. • The samples calcined in a range of 850–900 °C exhibited excellent electrochemical performance. - Abstract: Lithium-rich layered oxide cathode materials (Li_1_._2Mn_0_._5_6Ni_0_._1_6Co_0_._0_8O_2 (LLMO)) were synthesized via a two-step synthesis method involving co-precipitation and high-temperature calcination. The effects of calcination temperature on the cathode materials were studied in detail. Structural and morphological characterizations revealed that a well-crystallized layered structure was obtained at a higher calcination temperature. Electrochemical performance evaluation revealed that a cathode material obtained at a calcination temperature of 850 °C delivered a high initial discharge capacity of 266.8 mAh g"−"1 at a 0.1 C rate and a capacity retention rate of 95.8% after 100 cycles as well as excellent rate capability. Another sample calcinated at 900 °C exhibited good cycling stability. It is concluded that the structural stability and electrochemical performance of Li-rich layered oxide cathode materials were strongly dependent on calcination temperatures. The results suggest that a calcination temperature in a range of 850–900 °C could promote electrochemical performance of this type of cathode materials.

Effect of calcination temperature on microstructure and electrochemical performance of lithium-rich layered oxide cathode materials

Energy Technology Data Exchange (ETDEWEB)

Ma, Quanxin; Peng, Fangwei; Li, Ruhong; Yin, Shibo; Dai, Changsong, E-mail: changsd@hit.edu.cn

2016-11-15

Highlights: • A series of Li-rich layered oxide cathode materials (Li{sub 1.2}Mn{sub 0.56}Ni{sub 0.16}Co{sub 0.08}O{sub 2}) were successfully synthesized via a two-step synthesis method. • The effects of calcination temperature on the cathode materials were researched in detail. • A well-crystallized layered structure was obtained as the calcination temperature increased. • The samples calcined in a range of 850–900 °C exhibited excellent electrochemical performance. - Abstract: Lithium-rich layered oxide cathode materials (Li{sub 1.2}Mn{sub 0.56}Ni{sub 0.16}Co{sub 0.08}O{sub 2} (LLMO)) were synthesized via a two-step synthesis method involving co-precipitation and high-temperature calcination. The effects of calcination temperature on the cathode materials were studied in detail. Structural and morphological characterizations revealed that a well-crystallized layered structure was obtained at a higher calcination temperature. Electrochemical performance evaluation revealed that a cathode material obtained at a calcination temperature of 850 °C delivered a high initial discharge capacity of 266.8 mAh g{sup −1} at a 0.1 C rate and a capacity retention rate of 95.8% after 100 cycles as well as excellent rate capability. Another sample calcinated at 900 °C exhibited good cycling stability. It is concluded that the structural stability and electrochemical performance of Li-rich layered oxide cathode materials were strongly dependent on calcination temperatures. The results suggest that a calcination temperature in a range of 850–900 °C could promote electrochemical performance of this type of cathode materials.

Characterization of positive electrode/electrolyte interphase in lithium batteries

Energy Technology Data Exchange (ETDEWEB)

Dupre, N.; Martin, J.F.; Soudan, P.; Guyomard, D. [Inst.des Materiaux Jean Rouxel, Nantes (France)

2008-07-01

Lithium batteries appear to be the most viable energy source for portable electronic devices because of their energy density. The solid electrolyte interphase (SEI) between the negative electrode and the electrolyte of a Li-ion battery monitors the overall battery behaviour in terms of irreversible capacity loss, charge transfer kinetics and storage properties. This paper reported on a study that examined the influence of the storage atmosphere and the formation of a protective surface layer on the electrochemical performance. The objective was to better understand the interfacial problems controlling the long term life duration and cyclability. The positive/electrolyte interphase evolution was followed upon aging/cycling using 7Li MAS NMR, XPS and impedance spectroscopy. This very novel and uncommon technique was used to characterize the growth and evolution of the surface of some electrode materials for lithium batteries, due to contact with the ambient atmosphere or electrolyte or along electrochemical cycling. LiFePO4 and LiMn0.5Ni0.5O2 were chosen for the studies because they are among the most promising candidates for positive electrodes for future lithium batteries. The reaction of LiMn0.5Ni0.5O2 with the ambient atmosphere or LiPF6 electrolyte is extremely fast and leads to an important amount of lithium-containing diamagnetic species. The NMR spectra provided valuable structural information on the interaction between the interphase and the active material after contact with electrolyte or along electrochemical cycling. MAS NMR was shown to be a very promising tool to monitor phenomena taking place at the interface between electrode and electrolyte in lithium batteries. The study showed the affect of the potential on the strength of the interaction between the surface layer and the active material and the partial removal of this layer along the electrochemical cycling. 11 refs.

Vanadium based amorphous mixed oxides used as negative electrodes of lithium batteries; Oxydes mixtes amorphes a base de vanadium comme electrodes negatives de batteries au lithium

Energy Technology Data Exchange (ETDEWEB)

Guyomard, D.; Leroux, F.; Sigala, C.; Le Gal La Salle, A.; Piffard, Y. [Institut des Materiaux de Nantes, 44 (France). Laboratoire de Chimie des Solides

1996-12-31

This paper presents recent results concerning the chemical and electrochemical synthesis, the electrochemical properties and the characterization of two new families of amorphous oxides of formula Li{sub x}MVO{sub 4} (1lithium and can be used as negative electrodes in high performance lithium-ion batteries. (J.S.) 19 refs.

Vanadium based amorphous mixed oxides used as negative electrodes of lithium batteries; Oxydes mixtes amorphes a base de vanadium comme electrodes negatives de batteries au lithium

Energy Technology Data Exchange (ETDEWEB)

Guyomard, D; Leroux, F; Sigala, C; Le Gal La Salle, A.; Piffard, Y [Institut des Materiaux de Nantes, 44 (France). Laboratoire de Chimie des Solides

1997-12-31

This paper presents recent results concerning the chemical and electrochemical synthesis, the electrochemical properties and the characterization of two new families of amorphous oxides of formula Li{sub x}MVO{sub 4} (1lithium and can be used as negative electrodes in high performance lithium-ion batteries. (J.S.) 19 refs.

Solvent-Directed Sol-Gel Assembly of 3-Dimensional Graphene-Tented Metal Oxides and Strong Synergistic Disparities in Lithium Storage

Energy Technology Data Exchange (ETDEWEB)

Ye, Jianchao; An, Yonghao; Montalvo, Elizabeth; Campbell, Patrick G.; Worsley, Marcus A.; Tran, Ich C.; Liu, Yuanyue; Wood, Brandon C.; Biener, Juergen; Jiang, Hanqing; Tang, Ming; Wang, Y. Morris

2016-03-21

Graphene/metal oxide (GMO) nanocomposites promise a broad range of utilities for lithium ion batteries (LIBs), pseudocapacitors, catalysts, and sensors. When applied as anodes for LIBs, GMOs often exhibit high capacity, improved rate capability and cycling performance. Numerous studies have attributed these favorable properties to a passive role played by the exceptional electronic and mechanical properties of graphene in enabling metal oxides (MOs) to achieve near-theoretical capacities. In contrast, the effects of MOs on the active lithium storage mechanisms of graphene remain enigmatic. Via a unique two-step solvent-directed sol-gel process, we have synthesized and directly compared the electrochemical performance of several representative GMOs, namely Fe2O3/graphene, SnO2/graphene, and TiO2/graphene. We observe that MOs can play an equally important role in empowering graphene to achieve large reversible lithium storage capacity. The magnitude of capacity improvement is found to scale roughly with the surface coverage of MOs, and depend sensitively on the type of MOs. We define a synergistic factor based on the capacity contributions. Our quantitative assessments indicate that the synergistic effect is most achievable in conversion-reaction GMOs (Fe2O3/graphene and SnO2/graphene) but not in intercalation-based TiO2/graphene. However, a long cycle stability up to 2000 cycles was observed in TiO2/graphene nanocomposites. We propose a surface coverage model to qualitatively rationalize the beneficial roles of MOs to graphene. Our first-principles calculations further suggest that the extra lithium storage sites could result from the formation of Li2O at the interface with graphene during the conversion-reaction. These results suggest an effective pathway for reversible lithium storage in graphene and shift design paradigms for graphene-based electrodes.

SnCo–CMK nanocomposite with improved electrochemical performance for lithium-ion batteries

Energy Technology Data Exchange (ETDEWEB)

Zeng, Lingxing [College of Environment Science and Engineering, Fujian Normal University, Fuzhou, Fujian 350007 (China); Fujian Key Laboratory of Pollution Control & Resource Reuse, Fuzhou, Fujian 350007 (China); Deng, Cuilin; Zheng, Cheng; Qiu, Heyuan [Institute of Advanced Energy Materials, Fuzhou University, Fuzhou, Fujian 350002 (China); Qian, Qingrong, E-mail: qrqian@fjnu.edu.cn [College of Environment Science and Engineering, Fujian Normal University, Fuzhou, Fujian 350007 (China); Fujian Key Laboratory of Pollution Control & Resource Reuse, Fuzhou, Fujian 350007 (China); Chen, Qinghua [College of Environment Science and Engineering, Fujian Normal University, Fuzhou, Fujian 350007 (China); Fujian Key Laboratory of Pollution Control & Resource Reuse, Fuzhou, Fujian 350007 (China); Wei, Mingdeng, E-mail: wei-mingdeng@fzu.edu.cn [Institute of Advanced Energy Materials, Fuzhou University, Fuzhou, Fujian 350002 (China)

2015-11-15

Highlights: • The SnCo–CMK nanocomposite was synthesized using mesoporous carbon as nano-reactor. • Ultrafine SnCo nanoparticles distribute both inside and outside of mesopore channels. • The SnCo–CMK nanocomposite is an alternative anode material for Li-ion intercalation. • A high reversible capacity of 562 mAh g{sup −1} is maintained after 60 cycles at 100 mA g{sup −1}. - Abstract: In the present work, SnCo–CMK nanocomposite was successfully synthesized for the first time via a simple nanocasting route by using mesoporous carbon as nano-reactor. The nanocomposite was then characterized by means of X-ray diffraction (XRD), thermogravimetric analysis (TG), N{sub 2} adsorption–desorption, scanning and transmission electron microscopy (SEM/TEM) respectively. Furthermore, the SnCo–CMK nanocomposite exhibited large reversible capacities, excellent cycling stability and enhanced rate capability when employed as an anode material for lithium-ion batteries. A large reversible capacity of 562 mA h g{sup −1} was obtained after 60 cycles at a current density of 0.1 A g{sup −1} which is attributed to the structure of ‘meso-nano’ SnCo–CMK composite. This unique structure ensures the intimate contact between CMK and SnCo nanoparticles, buffers the large volume expansion and prevents the aggregation of the SnCo nanoparticles during cycling, leading to the excellent cycling stability and enhanced rate capability.

Polymer Electrolytes for Lithium/Sulfur Batteries

Directory of Open Access Journals (Sweden)

The Nam Long Doan

2012-08-01

Full Text Available This review evaluates the characteristics and advantages of employing polymer electrolytes in lithium/sulfur (Li/S batteries. The main highlights of this study constitute detailed information on the advanced developments for solid polymer electrolytes and gel polymer electrolytes, used in the lithium/sulfur battery. This includes an in-depth analysis conducted on the preparation and electrochemical characteristics of the Li/S batteries based on these polymer electrolytes.

Lithium-aluminum-magnesium electrode composition

Science.gov (United States)

Melendres, Carlos A.; Siegel, Stanley

1978-01-01

A negative electrode composition is presented for use in a secondary, high-temperature electrochemical cell. The cell also includes a molten salt electrolyte of alkali metal halides or alkaline earth metal halides and a positive electrode including a chalcogen or a metal chalcogenide as the active electrode material. The negative electrode composition includes up to 50 atom percent lithium as the active electrode constituent and a magnesium-aluminum alloy as a structural matrix. Various binary and ternary intermetallic phases of lithium, magnesium, and aluminum are formed but the electrode composition in both its charged and discharged state remains substantially free of the alpha lithium-aluminum phase and exhibits good structural integrity.

High-Performance Lithium-Air Battery with a Coaxial-Fiber Architecture.

Science.gov (United States)

Zhang, Ye; Wang, Lie; Guo, Ziyang; Xu, Yifan; Wang, Yonggang; Peng, Huisheng

2016-03-24

The lithium-air battery has been proposed as the next-generation energy-storage device with a much higher energy density compared with the conventional lithium-ion battery. However, lithium-air batteries currently suffer enormous problems including parasitic reactions, low recyclability in air, degradation, and leakage of liquid electrolyte. Besides, they are designed into a rigid bulk structure that cannot meet the flexible requirement in the modern electronics. Herein, for the first time, a new family of fiber-shaped lithium-air batteries with high electrochemical performances and flexibility has been developed. The battery exhibited a discharge capacity of 12,470 mAh g(-1) and could stably work for 100 cycles in air; its electrochemical performances were well maintained under bending and after bending. It was also wearable and formed flexible power textiles for various electronic devices. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Low cost iodine intercalated graphene for fuel cells electrodes

Science.gov (United States)

Marinoiu, Adriana; Raceanu, Mircea; Carcadea, Elena; Varlam, Mihai; Stefanescu, Ioan

2017-12-01

On the theoretical predictions, we report the synthesis of iodine intercalated graphene for proton exchange membrane fuel cells (PEMFCs) applications. The structure and morphology of the samples were characterized by X-ray photoelectron spectroscopy (XPS) analysis, specific surface area by BET method, Raman investigations. The presence of elemental iodine in the form of triiodide and pentaiodide was validated, suggesting that iodine was trapped between graphene layers, leading to interactions with C atoms. The electrochemical performances of iodinated graphenes were tested and compared with a typical PEMFC configuration, containing different Pt/C loading (0.4 and 0.2 mg cm-2). If iodinated graphene is included as microporous layer, the electrochemical performances of the fuel cell are higher in terms of power density than the typical fuel cell. Iodine-doped graphenes have been successfully obtained by simple and cost effective synthetic strategy and demonstrated new insights for designing of a high performance metal-free ORR catalyst by a scalable technique.

Designer interphases for the lithium-oxygen electrochemical cell

KAUST Repository

Choudhury, Snehashis

2017-04-20

An electrochemical cell based on the reversible oxygen reduction reaction: 2Li+ + 2e− + O2 ↔ Li2O2, provides among the most energy dense platforms for portable electrical energy storage. Such Lithium-Oxygen (Li-O2) cells offer specific energies competitive with fossil fuels and are considered promising for electrified transportation. Multiple, fundamental challenges with the cathode, anode, and electrolyte have limited practical interest in Li-O2 cells because these problems lead to as many practical shortcomings, including poor rechargeability, high overpotentials, and specific energies well below theoretical expectations. We create and study in-situ formation of solid-electrolyte interphases (SEIs) based on bromide ionomers tethered to a Li anode that take advantage of three powerful processes for overcoming the most stubborn of these challenges. The ionomer SEIs are shown to protect the Li anode against parasitic reactions and also stabilize Li electrodeposition during cell recharge. Bromine species liberated during the anchoring reaction also function as redox mediators at the cathode, reducing the charge overpotential. Finally, the ionomer SEI forms a stable interphase with Li, which protects the metal in high Gutmann donor number liquid electrolytes. Such electrolytes have been reported to exhibit rare stability against nucleophilic attack by Li2O2 and other cathode reaction intermediates, but also react spontaneously with Li metal anodes. We conclude that rationally designed SEIs able to regulate transport of matter and ions at the electrolyte/anode interface provide a promising platform for addressing three major technical barriers to practical Li-O2 cells.

Designer interphases for the lithium-oxygen electrochemical cell

KAUST Repository

Choudhury, Snehashis; Wan, Charles Tai-Chieh; Al Sadat, Wajdi I.; Tu, Zhengyuan; Lau, Sampson; Zachman, Michael J.; Kourkoutis, Lena F.; Archer, Lynden A.

2017-01-01

An electrochemical cell based on the reversible oxygen reduction reaction: 2Li+ + 2e− + O2 ↔ Li2O2, provides among the most energy dense platforms for portable electrical energy storage. Such Lithium-Oxygen (Li-O2) cells offer specific energies competitive with fossil fuels and are considered promising for electrified transportation. Multiple, fundamental challenges with the cathode, anode, and electrolyte have limited practical interest in Li-O2 cells because these problems lead to as many practical shortcomings, including poor rechargeability, high overpotentials, and specific energies well below theoretical expectations. We create and study in-situ formation of solid-electrolyte interphases (SEIs) based on bromide ionomers tethered to a Li anode that take advantage of three powerful processes for overcoming the most stubborn of these challenges. The ionomer SEIs are shown to protect the Li anode against parasitic reactions and also stabilize Li electrodeposition during cell recharge. Bromine species liberated during the anchoring reaction also function as redox mediators at the cathode, reducing the charge overpotential. Finally, the ionomer SEI forms a stable interphase with Li, which protects the metal in high Gutmann donor number liquid electrolytes. Such electrolytes have been reported to exhibit rare stability against nucleophilic attack by Li2O2 and other cathode reaction intermediates, but also react spontaneously with Li metal anodes. We conclude that rationally designed SEIs able to regulate transport of matter and ions at the electrolyte/anode interface provide a promising platform for addressing three major technical barriers to practical Li-O2 cells.

Polymer electrolytes based on aromatic lithium sulfonyl-imide compounds; Electrolytes polymeres a base de sulfonylimidures de lithium aromatiques

Energy Technology Data Exchange (ETDEWEB)

Reibel, L.; Bayoudh, S. [Centre National de la Recherche Scientifique (CNRS), 67 - Strasbourg (France). Institut Charles Sadron; Baudry, P. [Electricite de France, 77 - Moret sur Loing (France). Direction des Etudes et Recherches; Majastre, H. [Bollore Technologies, 29 - Quimper (France); Herlem, G. [UFR de Sciences et Techniques, L.E.S., 25 - Besancon (France)

1996-12-31

This paper presents ionic conductivity results obtained with polymer electrolytes and also with propylene carbonate solutions. The domain of electrochemical activity of this salt has been determined using cycle volt-amperometry in propylene carbonate. Preliminary experiments on the stability of the polymer electrolyte with respect to the lithium electrode have been carried out for a possible subsequent use in lithium batteries. (J.S.) 4 refs.

Polymer electrolytes based on aromatic lithium sulfonyl-imide compounds; Electrolytes polymeres a base de sulfonylimidures de lithium aromatiques

Energy Technology Data Exchange (ETDEWEB)

Reibel, L; Bayoudh, S [Centre National de la Recherche Scientifique (CNRS), 67 - Strasbourg (France). Institut Charles Sadron; Baudry, P [Electricite de France, 77 - Moret sur Loing (France). Direction des Etudes et Recherches; Majastre, H [Bollore Technologies, 29 - Quimper (France); Herlem, G [UFR de Sciences et Techniques, L.E.S., 25 - Besancon (France)

1997-12-31

This paper presents ionic conductivity results obtained with polymer electrolytes and also with propylene carbonate solutions. The domain of electrochemical activity of this salt has been determined using cycle volt-amperometry in propylene carbonate. Preliminary experiments on the stability of the polymer electrolyte with respect to the lithium electrode have been carried out for a possible subsequent use in lithium batteries. (J.S.) 4 refs.

Graphene derived carbon confined sulfur cathodes for lithium-sulfur batteries: Electrochemical impedance studies

International Nuclear Information System (INIS)

Ganesan, Aswathi; Varzi, Alberto; Passerini, Stefano; Shaijumon, Manikoth M.

2016-01-01

Highlights: • Graphene-derived carbon (GDC) with distinctive porosity characteristics are prepared. • Effect of micro-/mesoporosity of GDC for improved Li-S battery performance is studied. • Impedance studies reveal insights into Li-S redox reactions and capacity fading phenomena. - Abstract: Sulfur nanocomposites are prepared by using graphene derived carbon (GDC), with controlled porosity characteristics, as confining matrix and are studied as efficient cathodes for lithium-sulfur (Li-S) batteries. To understand the effect of micro-/mesoporosity in porous carbon for the effective encapsulation of sulfur and polysulfides towards improved Li-S battery performance, two different GDC samples with controlled porosity characteristics, one with predominantly micropores (GDC-1) and a surface area of 1970 m 2 g −1 and the other with a surface area of 3239 m 2 g −1 , having more or less equal contribution of micro- and mesopores (GDC-2), are used to synthesize nanocomposite sulfur electrodes following melt diffusion process. Electrochemical studies are carried out by using cyclic voltammetry, galvanostatic charge/discharge cycling and electrochemical impedance spectroscopy (EIS). EIS spectra collected at different depth of discharge (DOD) in the first cycle as well as upon cycling give valuable insights into the Li-S redox reactions and capacity fading phenomena in these electrodes. The impedance response of GDC-S electrodes suggests a detrimental effect of the mesopores, where insoluble reaction products can easily accumulate, resulting in the loss of active material leading to capacity fading of Li-S cells.

Vanadium nitride as a novel thin film anode material for rechargeable lithium batteries

International Nuclear Information System (INIS)

Sun Qian; Fu Zhengwen

2008-01-01

Vanadium mononitride (VN) thin films have been successfully fabricated by magnetron sputtering. Its electrochemical behaviour with lithium was examined by galvanostatic cell cycling and cyclic voltammetry. The capacity of VN was found to be stable above 800 mAh g -1 after 50 cycles. By using ex situ X-ray diffraction, high-resolution transmission electron microscopy and selected area electron diffraction as well as in situ spectroelectrochemical measurements, the electrochemical reaction mechanism of VN with lithium was investigated. The reversible conversion reaction of VN into metal V and Li 3 N was revealed. The high reversible capacity and good stable cycle of VN thin film electrode made it a new promising lithium-ion storage material for future rechargeable lithium batteries

Insights into the electrochemical activity of nanosized α-LiFeO2

International Nuclear Information System (INIS)

Morales, J.; Santos-Pena, J.; Trocoli, R.; Franger, S.; Rodriguez-Castellon, E.

2008-01-01

In recent work [J. Morales, J. Santos-Pena, Electrochem. Commun. 9 (2007) 2116], we prepared nanosized α-LiFeO 2 with increased electrochemical activity in lithium cells relative to various lithium ferrite polymorphs. In this work, we studied the previous electrodes in different charge states in order to obtain a more accurate picture of the phenomena occurring during cycling. Exsitu X-ray photoelectron spectroscopy (XPS) measurements confirmed the oxidation/reduction of iron atoms during the charge/discharge process. The electrochemical impedance spectroscopy results suggested that the electrolyte is not oxidised during the first charge, but rather than a solid electrolyte interface is formed after one cycle. Also, thermal tests revealed that Fe(IV) present in the electrodes reacted with the electrolyte to form oxidised carbon species. Finally, α-LiFeO 2 was tested as a positive electrode material in a lithium battery under different regimes. Stabilised capacities up to 150 mAh g -1 were obtained under a C/4 regime. This lithium ferrite is therefore an attractive alternative to LiCoO 2

Synthesis and electrochemical performances of amorphous carbon-coated Sn-Sb particles as anode material for lithium-ion batteries

International Nuclear Information System (INIS)

Wang Zhong; Tian Wenhuai; Liu Xiaohe; Yang Rong; Li Xingguo

2007-01-01

The amorphous carbon coating on the Sn-Sb particles was prepared from aqueous glucose solutions using a hydrothermal method. Because the outer layer carbon of composite materials is loose cotton-like and porous-like, it can accommodate the expansion and contraction of active materials to maintain the stability of the structure, and hinder effectively the aggregation of nano-sized alloy particles. The as-prepared composite materials show much improved electrochemical performances as anode materials for lithium-ion batteries compared with Sn-Sb alloy and carbon alone. This amorphous carbon-coated Sn-Sb particle is extremely promising anode materials for lithium secondary batteries and has a high potentiality in the future use. - Graphical abstract: The amorphous carbon coating on the Sn-Sb particles was prepared from aqueous glucose solutions using a hydrothermal method. Because the outer layer carbon of composite materials is loose cotton-like and porous-like, it can accommodate the expansion and contraction of active materials to maintain the stability of the structure, and hinder effectively the aggregation of nano-sized alloy particles

Electrochemical Properties of LLTO/Fluoropolymer-Shell Cellulose-Core Fibrous Membrane for Separator of High Performance Lithium-Ion Battery

Directory of Open Access Journals (Sweden)

Fenglin Huang

2016-01-01

Full Text Available A superfine Li0.33La0.557TiO3 (LLTO, 69.4 nm was successfully synthesized by a facile solvent-thermal method to enhance the electrochemical properties of the lithium-ion battery separator. Co-axial nanofiber of cellulose and Poly(vinylidene fluoride-co-hexafluoropropylene (PVDF-HFP was prepared by a co-axial electrospinning technique, in which the shell material was PVDF-HFP and the core was cellulose. LLTO superfine nanoparticles were incorporated into the shell of the PVDF-HFP. The core–shell composite nanofibrous membrane showed good wettability (16.5°, contact angle, high porosity (69.77%, and super electrolyte compatibility (497%, electrolyte uptake. It had a higher ionic conductivity (13.897 mS·cm−1 than those of pure polymer fibrous membrane and commercial separator. In addition, the rate capability (155.56 mAh·g−1 was also superior to the compared separator. These excellent performances endowed LLTO composite nanofibrous membrane as a promising separator for high-performance lithium-ion batteries.

Electrochemical oxidation of organic carbonate based electrolyte solutions at lithium metal oxide electrodes

Energy Technology Data Exchange (ETDEWEB)

Imhof, R; Novak, P [Paul Scherrer Inst. (PSI), Villigen (Switzerland)

1999-08-01

The oxidative decomposition of carbonate based electrolyte solutions at practical lithium metal oxide composite electrodes was studied by differential electrochemical mass spectrometry. For propylene carbonate (PC), CO{sub 2} evolution was detected at LiNiO{sub 2}, LiCoO{sub 2}, and LiMn{sub 2}O{sub 4} composite electrodes. The starting point of gas evolution was 4.2 V vs. Li/Li{sup +} at LiNiO{sub 2}, whereas at LiCoO{sub 2} and LiMn{sub 2}O{sub 4}, CO{sub 2} evolution was only observed above 4.8 V vs. Li/Li{sup +}. In addition, various other volatile electrolyte decomposition products of PC were detected when using LiCoO{sub 2}, LiMn{sub 2}O4, and carbon black electrodes. In ethylene carbonate / dimethyl carbonate, CO{sub 2} evolution was only detected at LiNiO{sub 2} electrodes, again starting at about 4.2 V vs. Li/Li{sup +}. (author) 3 figs., 2 refs.

Lithium thionyl chloride battery

Energy Technology Data Exchange (ETDEWEB)

Saathoff, D.J.; Venkatasetty, H.V.

1982-10-19

The discharge rate and internal conductivity of electrochemical cell including a lithium anode, and a cathode and an electrolyte including LiAlCl4 and SOC2 is improved by the addition of an amount of a mixture containing AlCl3 and butyl pyridinium chloride.

Non-aqueous electrolytes for lithium ion batteries

Science.gov (United States)

Chen, Zonghai; Amine, Khalil

2015-11-12

The present invention is generally related to electrolytes containing anion receptor additives to enhance the power capability of lithium-ion batteries. The anion receptor of the present invention is a Lewis acid that can help to dissolve LiF in the passivation films of lithium-ion batteries. Accordingly, one aspect the invention provides electrolytes comprising a lithium salt; a polar aprotic solvent; and an anion receptor additive; and wherein the electrolyte solution is substantially non-aqueous. Further there are provided electrochemical devices employing the electrolyte and methods of making the electrolyte.

A Combined Thermodynamics & Computational Method to Assess Lithium Composition in Anode and Cathode of Lithium Ion Batteries

International Nuclear Information System (INIS)

Zhang, Wenyu; Jiang, Lianlian; Van Durmen, Pauline; Saadat, Somaye; Yazami, Rachid

2016-01-01

With aim to address the open question of accurate determination of lithium composition in anode and cathode at a defined state of charge (SOC) of lithium ion batteries (LIB), we developed a method combining electrochemical thermodynamic measurements (ETM) and computational data fitting protocol. It is a common knowledge that in a lithium ion battery the SOC of anode and cathode differ from the SOC of the full-cell. Differences are in large part due to irreversible lithium losses within cell and to electrode mass unbalance. This implies that the lithium composition range in anode and in cathode during full charge and discharge cycle in full-cell is different from the composition range achieved in lithium half-cells of anode and cathode over their respective full SOC ranges. To the authors knowledge there is no unequivocal and practical method to determine the actual lithium composition of electrodes in a LIB, hence their SOC. Yet, accurate lithium composition assessment is fundamental not only for understanding the physics of electrodes but also for optimizing cell performances, particularly energy density and cycle life.

High-capacity nanostructured germanium-containing materials and lithium alloys thereof

Science.gov (United States)

Graetz, Jason A.; Fultz, Brent T.; Ahn, Channing; Yazami, Rachid

2010-08-24

Electrodes comprising an alkali metal, for example, lithium, alloyed with nanostructured materials of formula Si.sub.zGe.sub.(z-1), where 0electrodes made from graphite. These electrodes are useful as anodes for secondary electrochemical cells, for example, batteries and electrochemical supercapacitors.

Lithium salt with a super-delocalized perfluorinated sulfonimide anion as conducting salt for lithium-ion cells: Physicochemical and electrochemical properties

Science.gov (United States)

Zhang, Heng; Han, Hongbo; Cheng, Xiaorong; Zheng, Liping; Cheng, Pengfei; Feng, Wenfang; Nie, Jin; Armand, Michel; Huang, Xuejie; Zhou, Zhibin

2015-11-01

Lithium salt with a super-delocalized imide anion, namely (trifluoromethane(S-trifluoromethanesulfonylimino)sulfonyl) (trifluoromethanesulfonyl)imide ([CF3SO(=NSO2CF3)2]-), [sTFSI]-), has been prepared and studied as conducting salt for Li-ion cells. The fundamental physicochemical and electrochemical properties of neat Li[sTFSI] and its carbonate-based liquid electrolyte have been characterized with various chemical and electrochemical tools. Li[sTFSI] shows a low melting point at 118 °C, and is thermally stable up to 300 °C without decomposition on the spectra of differential scanning calorimetry-thermogravimetry-mass spectrometry (DSC-TG-MS). The electrolyte of 1.0 M (mol dm-3) Li[sTFSI] in ethylene carbonate (EC)/ethyl-methyl-carbonate (EMC) (3:7, v/v) containing 0.3% water does not show any hydrolytic decomposition on the spectra of 1H and 19F NMR, after storage at 85 °C for 10 days. The conductivities of 1.0 M Li[sTFSI]-EC/EMC (3:7, v/v) are slightly lower than those of Li[(CF3SO2)2N] (LiTFSI), but higher than those of Li[(C2F5SO2)2N] (LiBETI). The electrochemical behavior of Al foil in the Li[sTFSI]-based electrolyte has been investigated by using cyclic voltammetry and chronoamperometry, and scanning electron microscope (SEM). It is illustrated that Al metal does not corrode in the high potential region (3-5 V vs. Li/Li+) in the Li[sTFSI]-based electrolyte. On Pt electrode, the Li[sTFSI]-based electrolyte is highly resistant to oxidation (ca. 5 V vs. Li/Li+), and is also resistant to reduction to allow Li deposition and stripping. The applicability of Li[sTFSI] as conducting salt for Li-ion cells has been tested using graphite/LiCoO2 cells. It shows that the cell with Li[sTFSI] displays better cycling performance than that with LiPF6.

Synthesis of One Dimensional Li2MoO4 Nanostructures and Their Electrochemical Performance as Anode Materials for Lithium-ion Batteries

International Nuclear Information System (INIS)

Liu, Xudong; Zhao, Yanming; Dong, Youzhong; Fan, Qinghua; Kuang, Quan; Liang, Zhiyong; Lin, Xinghao; Han, Wei; Li, Qidong; Wen, Mingming

2015-01-01

Highlights: • One dimensional Li 2 MoO 4 nanostructures including nanorods and nanotubes have been successfully fabricated via a simple sol-gel method firstly. • Possible crystal formation mechanisms are proposed for these one dimensional Li 2 MoO 4 nanostructures. • These one dimensional Li 2 MoO 4 nanostructure electrode materials present outstanding rate abilities and cycle capabilities in electrochemical performance compared to the carbon-free powder sample when evaluated as anode materials for Lithium-ion batteries. • The carbon-coated Li 2 MoO 4 nanotube electrode improves the charging/discharging capacities of graphite even after applying 60 cycles at very high current density. - Abstract: One dimensional Li 2 MoO 4 nanostructures including nanorods and nanotubes have been successfully fabricated via a simple sol-gel method adding Li 2 CO 3 and MoO 3 powders into distilled water with citric acid as an assistant agent and carbon source. Our experimental results show that the formation of the one dimensional nanostructure morphology is evaporation and crystallization process with self-adjusting into a rod-like hexagonal cross-section structure, while the citric acid played an important role during the formation of Li 2 MoO 4 nanotubes under the acidic environment by capping, stabilizing the {1010} facet of Li 2 MoO 4 structure and controlling the concentration of H + (pH value) of the aqueous solution. Finally, basic electrochemical performance of these one dimensional Li 2 MoO 4 nanostructures including nanorods and nanotubes evaluated as anode materials for lithium-ion batteries (LIBs) are discussed, for comparison, the properties of carbon-free powder sample synthesized by solid-state reaction are also displayed. Experimental results show that different morphology and carbon-coating on the surface have an important influence on electrochemical performance

Mathematical modeling of the lithium deposition overcharge reaction in lithium-ion batteries using carbon-based negative electrodes

International Nuclear Information System (INIS)

Arora, P.; Doyle, M.; White, R.E.

1999-01-01

Two major issues facing lithium-ion battery technology are safety and capacity grade during cycling. A significant amount of work has been done to improve the cycle life and to reduce the safety problems associated with these cells. This includes newer and better electrode materials, lower-temperature shutdown separators, nonflammable or self-extinguishing electrolytes, and improved cell designs. The goal of this work is to predict the conditions for the lithium deposition overcharge reaction on the negative electrode (graphite and coke) and to investigate the effect of various operating conditions, cell designs and charging protocols on the lithium deposition side reaction. The processes that lead to capacity fading affect severely the cycle life and rate behavior of lithium-ion cells. One such process is the overcharge of the negative electrode causing lithium deposition, which can lead to capacity losses including a loss of active lithium and electrolyte and represents a potential safety hazard. A mathematical model is presented to predict lithium deposition on the negative electrode under a variety of operating conditions. The Li x C 6 vertical bar 1 M LiPF 6 , 2:1 ethylene carbonate/dimethyl carbonate, poly(vinylidene fluoride-hexafluoropropylene) vert b ar LiMn 2 O 4 cell is simulated to investigate the influence of lithium deposition on the charging behavior of intercalation electrodes. The model is used to study the effect of key design parameters (particle size, electrode thickness, and mass ratio) on the lithium deposition overcharge reaction. The model predictions are compared for coke and graphite-based negative electrodes. The cycling behavior of these cells is simulated before and after overcharge to understand the hazards and capacity fade problems, inherent in these cells, can be minimized

Na-doped LiMnPO4 as an electrode material for enhanced lithium ...

Indian Academy of Sciences (India)

and electrochemical performance. Lithium manganese ... bond enables good thermal and cycling stability [4,5]. The ... Moreover, the surface morphologies are an essential factor ... work, electrochemically inactive cations were replaced par-.

Graphene-Based Composites as Cathode Materials for Lithium Ion Batteries

Directory of Open Access Journals (Sweden)

Libao Chen

2013-01-01

Full Text Available Owing to the superior mechanical, thermal, and electrical properties, graphene was a perfect candidate to improve the performance of lithium ion batteries. Herein, we review the recent advances in graphene-based composites and their application as cathode materials for lithium ion batteries. We focus on the synthesis methods of graphene-based composites and the superior electrochemical performance of graphene-based composites as cathode materials for lithium ion batteries.

Synthesis of TiO{sub 2} by electrochemical method from TiCl{sub 4} solution as anode material for lithium-ion batteries

Energy Technology Data Exchange (ETDEWEB)

Nur, Adrian, E-mail: adriannur@staff.uns.ac.id; Purwanto, Agus; Jumari, Arif; Dyartanti, Endah R.; Sari, Sifa Dian Permata; Hanifah, Ita Nur [Research Group of Advanced Material, Department of Chemical Engineering, Sebelas Maret University, Jl. Ir. Sutami 36 A Kentingan, Surakarta Indonesia 57126 (Indonesia)

2016-02-08

Metal oxide combined with graphite becomes interesting composition. TiO{sub 2} is a good candidate for Li ion battery anode because of cost, availability of sufficient materials, and environmentally friendly. TiO{sub 2} gravimetric capacity varied within a fairly wide range. TiO{sub 2} crystals form highly depends on the synthesis method used. The electrochemical method is beginning to emerge as a valuable option for preparing TiO{sub 2} powders. Using the electrochemical method, the particle can easily be controlled by simply adjusting the imposed current or potential to the system. In this work, the effects of some key parameters of the electrosynthesis on the formation of TiO{sub 2} have been investigated. The combination of graphite and TiO{sub 2} particle has also been studied for lithium-ion batteries. The homogeneous solution for the electrosynthesis of TiO{sub 2} powders was TiCl{sub 4} in ethanol solution. The electrolysis was carried out in an electrochemical cell consisting of two carbon electrodes with dimensions of (5 × 2) cm. The electrodes were set parallel with a distance of 2.6 cm between the electrodes and immersed in the electrolytic solution at a depth of 2 cm. The electrodes were connected to the positive and negative terminals of a DC power supply. The electrosynthesis was performed galvanostatically at 0.5 to 2.5 hours and voltages were varied from 8 to 12 V under constant stirring at room temperature. The resulted suspension was aged at 48 hrs, filtered, dried directly in an oven at 150°C for 2 hrs, washed 2 times, and dried again 60 °C for 6 hrs. The particle product has been used to lithium-ion battery as anode. Synthesis of TiO{sub 2} particle by electrochemical method at 10 V for 1 to 2.5 hrs resulted anatase and rutile phase.

Intercalation chemistry of zirconium 4-sulfophenylphosphonate

International Nuclear Information System (INIS)

Svoboda, Jan; Zima, Vítězslav; Melánová, Klára; Beneš, Ludvík; Trchová, Miroslava

2013-01-01

Zirconium 4-sulfophenylphosphonate is a layered material which can be employed as a host for the intercalation reactions with basic molecules. A wide range of organic compounds were chosen to represent intercalation ability of zirconium 4-sulfophenylphosphonate. These were a series of alkylamines from methylamine to dodecylamine, 1,4-phenylenediamine, p-toluidine, 1,8-diaminonaphthalene, 1-aminopyrene, imidazole, pyridine, 4,4′-bipyridine, poly(ethylene imine), and a series of amino acids from glycine to 6-aminocaproic acid. The prepared compounds were characterized by powder X-ray diffraction, thermogravimetry analysis and IR spectroscopy and probable arrangement of the guest molecules in the interlayer space of the host is proposed based on the interlayer distance of the prepared intercalates and amount of the intercalated guest molecules. - Graphical abstract: Nitrogen-containing organic compounds can be intercalated into the interlayer space of zirconium 4-sulfophenylphosphonate. - Highlights: • Zirconium 4-sulfophenylphosphonate was examined as a host material in intercalation chemistry. • A wide range of nitrogen-containing organic compounds were intercalated. • Possible arrangement of the intercalated species is described

Electrochemical performance of LiNi0.5Mn1.5O4 prepared by improved solid state method as cathode in hybrid supercapacitor

International Nuclear Information System (INIS)