Synthesis and electrochemical properties of Li4Ti5O12

CSIR Research Space (South Africa)

Liu, GQ

2011-06-01

Full Text Available The spinel compound Li4Ti5O12 was synthesized by a solid state method. In this synthesizing process, anatase TiO2 and Li2CO3 were used as reactants. The influences of reaction temperature and calcination time on the properties of products were...

Insight into effects of graphene in Li4Ti5O12/carbon composite with high rate capability as anode materials for lithium ion batteries

International Nuclear Information System (INIS)

Ding, Y.; Li, G.R.; Xiao, C.W.; Gao, X.P.

2013-01-01

Li 4 Ti 5 O 12 /carbon composites have shown promising high rate capability as anode materials for lithium ion batteries. In this paper, unique effects of graphene in Li 4 Ti 5 O 12 /carbon composites on electrochemical performances are focused by means of comparing Li 4 Ti 5 O 12 /graphene with Li 4 Ti 5 O 12 /conductive carbon black (CCB) and Li 4 Ti 5 O 12 . The investigated anode materials are synthesized by a facile hydrothermal method. The amount of graphene or CCB in the Li 4 Ti 5 O 12 /carbon composites is about 3 wt% measured by thermogravimetric (TG) analysis. X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM) show that Li 4 Ti 5 O 12 /graphene consists of small sized Li 4 Ti 5 O 12 nanocrystals supported on graphene nanosheets, while Li 4 Ti 5 O 12 /CCB comprises Li 4 Ti 5 O 12 nanocrystal aggregates coated nearly by graphited carbon. The electrochemical performances of these samples as anode materials for lithium ion batteries are investigated by galvanostatic charge–discharge method. Li 4 Ti 5 O 12 /graphene provides a superior rate capability. At the high current density of 1600 mA g −1 , the reversible capacity after 200 cycles is still more than 120 mAh g −1 , which is about 40% higher than that of Li 4 Ti 5 O 12 /CCB. Cyclic voltammetry (CV) demonstrates that stronger pseudocapacitive effect occurs on Li 4 Ti 5 O 12 /graphene than on Li 4 Ti 5 O 12 /CCB. This derived from the structure features that graphene-supported small Li 4 Ti 5 O 12 nanocrystals provide more surface active sites for the lithium ion insertion/extraction. The strong pseudocapacitive effect is responsible for the improvements of capacity and high-rate capability. Further, electrochemical impedance spectra (EIS) show that Li 4 Ti 5 O 12 /graphene electrode have lower charge transfer resistance and smaller diffusion impedance, indicating the obvious advantages in electrode kinetics over Li 4 Ti 5 O 12 and Li 4 Ti 5 O 12

Study of surface reaction of spinel Li4Ti5O12 during the first lithium insertion and extraction processes using atomic force microscopy and analytical transmission electron microscopy.

Science.gov (United States)

Kitta, Mitsunori; Akita, Tomoki; Maeda, Yasushi; Kohyama, Masanori

2012-08-21

Spinel lithium titanate (Li(4)Ti(5)O(12), LTO) is a promising anode material for a lithium ion battery because of its excellent properties such as high rate charge-discharge capability and life cycle stability, which were understood from the viewpoint of bulk properties such as small lattice volume changes by lithium insertion. However, the detailed surface reaction of lithium insertion and extraction has not yet been studied despite its importance to understand the mechanism of an electrochemical reaction. In this paper, we apply both atomic force microscopy (AFM) and transmission electron microscopy (TEM) to investigate the changes in the atomic and electronic structures of the Li(4)Ti(5)O(12) surface during the charge-discharged (lithium insertion and extraction) processes. The AFM observation revealed that irreversible structural changes of an atomically flat Li(4)Ti(5)O(12) surface occurs at the early stage of the first lithium insertion process, which induces the reduction of charge transfer resistance at the electrolyte/Li(4)Ti(5)O(12) interface. The TEM observation clarified that cubic rock-salt crystal layers with a half lattice size of the original spinel structure are epitaxially formed after the first charge-discharge cycle. Electron energy loss spectroscopy (EELS) observation revealed that the formed surface layer should be α-Li(2)TiO(3). Although the transformation of Li(4)Ti(5)O(12) to Li(7)Ti(5)O(12) is well-known as the lithium insertion reaction of the bulk phase, the generation of surface product layers should be inevitable in real charge-discharge processes and may play an effective role in the stable electrode performance as a solid-electrolyte interphase (SEI).

Electrochemically active nanocomposites of Li4Ti5O12 2D nanosheets and SnO2 0D nanocrystals with improved electrode performance

International Nuclear Information System (INIS)

Han, Song Yi; Kim, In Young; Lee, Sang-Hyup; Hwang, Seong-Ju

2012-01-01

Electrochemically active nanocomposites consisting of Li 4 Ti 5 O 12 2D nanosheets and SnO 2 0D nanocrystals are synthesized by the crystal growth of tin dioxide on the surface of 2D nanostructured lithium titanate. According to powder X-ray diffraction and electron microscopic analyses, the rutile-structured SnO 2 nanocrystals are stabilized on the surface of spinel-structured Li 4 Ti 5 O 12 2D nanosheets. The homogeneous hybridization of tin dioxide with lithium titanate is confirmed by elemental mapping analysis. Ti K-edge X-ray absorption near-edge structure and Sn 3d X-ray photoelectron spectroscopy indicate the stabilization of tetravalent titanium ions in the spinel lattice of Li 4 Ti 5 O 12 and the formation of SnO 2 phase with tetravalent Sn oxidation state. The electrochemical measurements clearly demonstrate the promising functionality of the present nanocomposites as anode for lithium secondary batteries. The Li 4 Ti 5 O 12 –SnO 2 nanocomposites show larger discharge capacity and better cyclability than do the uncomposited Li 4 Ti 5 O 12 and SnO 2 phases, indicating the synergistic effect of nanocomposite formation on the electrode performance of Li 4 Ti 5 O 12 and SnO 2 . The present experimental findings underscore the validity of 2D nanostructured lithium titanate as a useful platform for the stabilization of nanocrystalline electrode materials and also for the improvement of their functionality.

Fabrication of Li4Ti5O12-TiO2 Nanosheets with Structural Defects as High-Rate and Long-Life Anodes for Lithium-Ion Batteries.

Science.gov (United States)

Xu, Hui; Chen, Jian; Li, Yanhuai; Guo, Xinli; Shen, Yuanfang; Wang, Dan; Zhang, Yao; Wang, Zengmei

2017-06-07

Development of high-power lithium-ion batteries with high safety and durability has become a key challenge for practical applications of large-scale energy storage devices. Accordingly, we report here on a promising strategy to synthesize a high-rate and long-life Li 4 Ti 5 O 12 -TiO 2 anode material. The novel material exhibits remarkable rate capability and long-term cycle stability. The specific capacities at 20 and 30 C (1 C = 175 mA g -1 ) reach 170.3 and 168.2 mA h g -1 , respectively. Moreover, a capacity of up to 161.3 mA h g -1 is retained after 1000 cycles at 20 C, and the capacity retention ratio reaches up to 94.2%. The extraordinary rate performance of the Li 4 Ti 5 O 12 -TiO 2 composite is attributed to the existence of oxygen vacancies and grain boundaries, significantly enhancing electrical conductivity and lithium insertion/extraction kinetics. Meanwhile, the pseudocapacitive effect is induced owing to the presence of abundant interfaces in the composite, which is beneficial to enhancing specific capacity and rate capability. Additionally, the ultrahigh capacity at low rates, greater than the theoretical value of spinel Li 4 Ti 5 O 12 , may be correlated to the lithium vacancies in 8a sites, increasing the extra docking sites of lithium ions.

High Performance Li4Ti5O12/Si Composite Anodes for Li-Ion Batteries

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Chunhui Chen

2015-08-01

Full Text Available Improving the energy capacity of spinel Li4Ti5O12 (LTO is very important to utilize it as a high-performance Li-ion battery (LIB electrode. In this work, LTO/Si composites with different weight ratios were prepared and tested as anodes. The anodic and cathodic peaks from both LTO and silicon were apparent in the composites, indicating that each component was active upon Li+ insertion and extraction. The composites with higher Si contents (LTO:Si = 35:35 exhibited superior specific capacity (1004 mAh·g−1 at lower current densities (0.22 A·g−1 but the capacity deteriorated at higher current densities. On the other hand, the electrodes with moderate Si contents (LTO:Si = 50:20 were able to deliver stable capacity (100 mAh·g−1 with good cycling performance, even at a very high current density of 7 A·g−1. The improvement in specific capacity and rate performance was a direct result of the synergy between LTO and Si; the former can alleviate the stresses from volumetric changes in Si upon cycling, while Si can add to the capacity of the composite. Therefore, it has been demonstrated that the addition of Si and concentration optimization is an easy yet an effective way to produce high performance LTO-based electrodes for lithium-ion batteries.

Lithium ion diffusion in Li4+xTi5O12: From ab initio studies

International Nuclear Information System (INIS)

Chen, Y.C.; Ouyang, C.Y.; Song, L.J.; Sun, Z.L.

2011-01-01

Highlights: → Li diffusion pathways in Li 4 Ti 5 O 12 and Li 7 Ti 5 O 12 are obtained from ab initio calculations. → Cooperative Li migration in Li 7+δ Ti 5 O 12 with very low energy barrier is proposed. → Li diffusion is faster in lithiated state than in delithiated state is confirmed theoretically. - Abstract: Lithium ion dynamics in Li 4+x Ti 5 O 12 spinel are investigated from first principles calculations. The diffusion pathways are optimized and the energy barriers of lithium migration under four types of dilute defect extremes: Li 4+δ Ti 5 O 12 , Li 4-δ Ti 5 O 12 , Li 7+δ Ti 5 O 12 and Li 7-δ Ti 5 O 12 (δ << 1) are calculated with the nudged elastic band method. Results show that lithium diffusion in the charged state (energy barriers are 1.0 and 0.7 eV for interstitial Li and Li vacancy diffusion, respectively) is much slower than in the discharged state (energy barriers are 0.13 and 0.35 eV for interstitial Li and Li vacancy diffusion, respectively). The diffusion coefficients are evaluated based on lattice gas model and hopping mechanism. The obtained results are compared with available experimental data within a two-phase co-existence framework.

Sodium storage capability of spinel Li4Mn5O12

International Nuclear Information System (INIS)

Zhang, Jiaolong; Wang, Wenhui; Li, Yingshun; Yu, Denis Y.W.

2015-01-01

Highlights: • Electrochemical behavior of spinel Li 4 Mn 5 O 12 is examined in Na-ion battery. • A capacity of 120.7 mAh g −1 is obtained during the first sodiation process. • Na storage performance is found to be strongly dependent on particle size. • Ion-exchange between Li ions and Na ions occurs in Li 4 Mn 5 O 12 structure upon cycling. • Loss of crystallinity with cycling, leading to capacity fading. - Abstract: Spinel Li 4 Mn 5 O 12 , a well-known 3 V Li-ion battery (LIB) material with excellent cycling stability and good rate capability, is examined as Na-ion battery (NIB) cathode for the first time. Electrochemical studies clearly show that Na ions can be reversibly inserted into and extracted from the three-dimensional spinel structure. However, unlike in LIB, the available capacity in NIB is strongly dependent on the particle size and current rate due to the sluggish Na-ion transport in solid phase. Cycle performance of Li 4 Mn 5 O 12 in NIB is also inferior to that in LIB. Ex-situ X-ray diffraction study indicates a gradual loss of crystallinity with cycling, and that the crystal lattice undergoes an irreversible expansion during the initial 20 cycles. Inductively coupled plasma spectroscopy shows a decrease of Li/Mn ratio in Li 4 Mn 5 O 12 with cycling. The results suggest that Li ions are removed from the material during the charging process. The charge-discharge mechanism is also discussed in the paper.

Li{sub 5}Cr{sub 9}Ti{sub 4}O{sub 24}: A new anode material for lithium-ion batteries

Energy Technology Data Exchange (ETDEWEB)

Lin, Chunfu, E-mail: linchunfu@hainu.edu.cn [Key Laboratory of Ministry of Education for Advanced Materials in Tropical Island Resources, College of Materials and Chemical Engineering, Hainan University, Haikou 570228, Hainan (China); Deng, Shengjue; Shen, Hong; Wang, Guizhen; Li, Yanfang; Yu, Lei; Lin, Shiwei; Li, Jianbao [Key Laboratory of Ministry of Education for Advanced Materials in Tropical Island Resources, College of Materials and Chemical Engineering, Hainan University, Haikou 570228, Hainan (China); Lu, Li, E-mail: luli@nus.edu.sg [Department of Mechanical Engineering, National University of Singapore, 9 Engineering Drive 1, Singapore 117576 (Singapore)

2015-11-25

Li{sub 4}Ti{sub 5}O{sub 12} suffers from its small theoretical capacity and low conductivity, limiting its practical applications in lithium-ion batteries. Although its conductivity has been improved, its theoretical capacity has not been increased so far. Here, for the first time, the capacity of Li{sub 4}Ti{sub 5}O{sub 12} is increased by combining Ti{sup 3+}/Ti{sup 4+} and Cr{sup 2+}/Cr{sup 3+} redox couples. Spinel Li{sub 5}Cr{sub 9}Ti{sub 4}O{sub 24} with a larger theoretical capacity of 323 mAh g{sup −1} is designed and fabricated through a facile solid-state reaction method. The as-fabricated Li{sub 5}Cr{sub 9}Ti{sub 4}O{sub 24} delivers a large initial discharge capacity of 311 mAh g{sup −1} between 3 and 0.001 V (vs. Li/Li{sup +}) at a current density of 62.5 mA g{sup −1}, which is larger than that of Li{sub 4}Ti{sub 5}O{sub 12}. Furthermore, it exhibits good (electronic and ionic) conductivity and a high rate performance. - Highlights: • Capacity of Li{sub 4}Ti{sub 5}O{sub 12} is increased by combining Ti{sup 3+}/Ti{sup 4+} and Cr{sup 2+}/Cr{sup 3+} couples. • Spinel Li{sub 5}Cr{sub 9}Ti{sub 4}O{sub 24} with a larger theoretical capacity of 323 mAh g{sup −1} is prepared. • Discharge and charge capacities of Li{sub 5}Cr{sub 9}Ti{sub 4}O{sub 24} are larger than those of Li{sub 4}Ti{sub 5}O{sub 12}. • Li{sub 5}Cr{sub 9}Ti{sub 4}O{sub 24} shows a large electronic conductivity and Li{sup +} diffusion coefficient. • Li{sub 5}Cr{sub 9}Ti{sub 4}O{sub 24} further exhibits an ultra-high rate performance and good cyclability.

Improved electrochemical properties of Li{sub 4}Ti{sub 5}O{sub 12}–Li{sub 0.33}La{sub 0.56}TiO{sub 3} composite anodes prepared by a solid-state synthesis

Energy Technology Data Exchange (ETDEWEB)

Zhu, Yan-Rong; Yuan, Jing; Zhu, Min [School of Chemistry and Chemical Engineering, Anhui University of Technology, Maanshan, Anhui 243002 (China); Hao, Guodong [College of Chemistry and Chemical Engineering, Mudanjiang Normal University, Mudanjiang, Heilongjiang 157012 (China); Yi, Ting-Feng, E-mail: tfyihit@163.com [School of Chemistry and Chemical Engineering, Anhui University of Technology, Maanshan, Anhui 243002 (China); Xie, Ying, E-mail: xieying@hlju.edu.cn [Key Laboratory of Functional Inorganic Material Chemistry, Ministry of Education, School of Chemistry and Materials Science, Heilongjiang University, Harbin, Heilongjiang 150080 (China)

2015-10-15

Li{sub 4}Ti{sub 5}O{sub 12}–Li{sub 0.33}La{sub 0.56}TiO{sub 3} composite anodes are successfully prepared by a facile solid state route. The structure, morphology and electrochemical performance of all samples are characterized by X-ray diffraction (XRD), Raman spectroscopy, scanning electron microscope (SEM), cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and charge–discharge tests, respectively. XRD reveals that the little La{sup 3+} ions enter into the lattice, and then make the crystal lattice of Li{sub 4}Ti{sub 5}O{sub 12} expand. SEM shows that all samples are composed of 1–2 μm primary particles with irregular shapes. CV and EIS imply that Li{sub 4}Ti{sub 5}O{sub 12}–Li{sub 0.33}La{sub 0.56}TiO{sub 3} composites have lower polarization, larger lithium-ion diffusion coefficient and smaller charge transfer resistance corresponding to a much higher conductivity than those of Li{sub 4}Ti{sub 5}O{sub 12} corresponding to the extraction of Li{sup +} ions. The improved electrochemical performance of Li{sub 4}Ti{sub 5}O{sub 12}–Li{sub 0.33}La{sub 0.56}TiO{sub 3} composites can be attributed to the enhanced transfer kinetics of both the lithium ions and electrons. Particularly, Li{sub 4}Ti{sub 5}O{sub 12}–Li{sub 0.33}La{sub 0.56}TiO{sub 3} (5 wt.%) composite shows a excellent high-rate capability and cycling stability. Therefore, the present Li{sub 4}Ti{sub 5}O{sub 12}–Li{sub 0.33}La{sub 0.56}TiO{sub 3} (5 wt.%) composite anode is capable of large-scale applications, such as electric vehicles and hybrid electric vehicles, requiring high energy, long life and excellent safety. - Highlights: • The electrochemical property of Li{sub 4}Ti{sub 5}O{sub 12}–Li{sub 0.33}La{sub 0.56}TiO{sub 3} down to 0 V is first reported. • Li{sub 0.33}La{sub 0.56}TiO{sub 3} modifying results in fast lithium insertion/extraction kinetics. • Li{sub 4}Ti{sub 5}O{sub 12}–Li{sub 0.33}La{sub 0.56}TiO{sub 3} (5 wt.%) exhibits a good fast charge

Electrochemical properties of spinel Li4Ti5O12 nanoparticles\

Czech Academy of Sciences Publication Activity Database

Senna, M.; Fabián, M.; Kavan, Ladislav; Zukalová, Markéta; Briančin, J.; Turianicová, E.; Bottke, P.; Wilkening, M.; Šepelák, V.

2016-01-01

Roč. 20, č. 10 (2016), s. 2673-2683 ISSN 1432-8488 R&D Projects: GA ČR GA15-06511S Institutional support: RVO:61388955 Keywords : Li4Ti5O12 * reactive precursor * Li-ion battery Subject RIV: CG - Electrochemistry Impact factor: 2.316, year: 2016

Effect of Carbon Coating on Li4TiO12 of Anode Material for Hybrid Capacitor.

Science.gov (United States)

Lee, Jong-Kyu; Lee, Byung-Gwan; Yoon, Jung-Rag

2015-11-01

The carbon-coated Li4Ti5O12 of anode material for hybrid capacitor was prepared by controlling carbonization time at 700 degrees C in nitrogen. With increasing of carbonization time, the discharge capacity and capacitance were decreased, while the equivalent series resistance was not changed remarkably. The rate capability and cycle performance of carbon-coated Li4Ti5O12 were larger than that of Li4Ti5O12. Carbon coating improved conductivity as well as Li-ion diffusion, and thus also resulted in good rate capabilities and cycle stability. The effects of carbon coating on the gas generation of hybrid capacitor were also discussed.

Zr doping effect with low-cost solid-state reaction method to synthesize submicron Li4Ti5O12 anode material

Science.gov (United States)

Seo, Inseok; Lee, Cheul-Ro; Kim, Jae-Kwang

2017-09-01

To improve the electrochemical properties, fine Zr-doping Li4Ti5O12 anode materials for rechargeable lithium batteries with a uniform particle size distribution were synthesized by a modified solid-state reaction using fine Li2CO3 and TiO2 (anatase) powders as precursors with a Li:Ti molar ratio of 4:5. The use of fine Li2CO3 and TiO2 (anatase) powders as precursors prevented the formation of ZrO2 at 0.1 mol Zr-doping. XRD analysis revealed that the substitution of Zr for Ti leads to the increase of lattice parameters, allowing improved Li diffusion. The discharge capacity retention increased slightly with Zr-doping and the 0.1 mol Zr-doped Li4Ti5O12 electrode achieved 99% retention of discharge capacity.

Effect of rigidity of porous structure on electrochemical behavior of pristine Li4Ti5O12 microspheres

International Nuclear Information System (INIS)

Jia, Zhenyong; Zhou, Qun; Li, Xiaowei; Fu, Yu; Ming, Hai; Zheng, Junwei

2015-01-01

Highlights: • Rigid porous framework of Li 4 Ti 5 O 12 microspheres can be fabricated by mutual molten growth of primary particles. • Well-confined nanosized tortuous channels are formed inside Li 4 Ti 5 O 12 microspheres. • Li 4 Ti 5 O 12 microspheres with rigid porous structures exhibit greatly enhanced electrochemical performance. - Abstract: Highly controllable porous architecture is desirable to tailor the physical and chemical properties of functional materials in advanced lithium ion batteries. Here, porous microspheres of spinel lithium titanate (Li 4 Ti 5 O 12 ), a promising alternative anode material for lithium ion batteries, are fabricated by mutual molten growth method in a controllable manner. The key role of the rigidity of the porous structure on the performance of the electrode materials in lithium ion batteries is demonstrated. Rigid framework of the materials is formed by second growth of the primary particles that fused together to generate an interconnected nanopore system inside the spheres, leading to better electrolyte diffusion and lower interparticle contact resistance, relative to the non-porous counterpart. The pristine Li 4 Ti 5 O 12 microspheres with uniform pore distribution and continuous framework exhibit high tap density, remarkable reversible capacity and rate capability, as well as excellent cycling stability. The present method is scalable and may provide a new approach to fabricate other candidate electrode materials for applications that require both high power and high volumetric energy density

Preparation of Li4Ti5O12 by solution ion-exchange of sodium titanate nanotube and evaluation of electrochemical performance

International Nuclear Information System (INIS)

Zhang, Jingwei; Zhang, Fenli; Li, Jiuhe; Cai, Wei; Zhang, Jiwei; Yu, Laigui; Jin, Zhensheng; Zhang, Zhijun

2013-01-01

Nano-sized spinel lithium titanate (Li 4 Ti 5 O 12 ) was synthesized using sodium titanate nanotube as precursor via a facile solution ion-exchange method in association with subsequent calcination treatment at relatively low temperature. The influences of precursors, ion-exchange condition, and calcination temperature on the microstructure and electrochemical performance of the products were studied. Results indicate that pure-phase Li 4 Ti 5 O 12 can be harvested from sodium titanate nanotube precursor through an ion-exchanging at room temperature and calcination at 500 °C. The products exhibit a better performance as Li-ion battery anode material than the counterparts prepared from protonic titanate nanotube (H-titanate) precursor. The reason may lie in that sodium titanate nanotube is easier than protonic titanate nanotube to synthesize lithium titanate without TiO 2 impurity, resulting in reduced electron transfer ability and Li-ion transport ability. The capacity of Li 4 Ti 5 O 12 prepared from sodium titanate nanotube is 146 mAh/g at 10 C, and it has only 0.7 % decay after 200 charge/discharge cycles

Effect of Acetylene Black Content in Li4Ti5O12 Xerogel Solid-State Anode Materials on Half-Cell Li-ion Batteries Performance

Science.gov (United States)

Abdurrahman, N. M.; Priyono, B.; Syahrial, A. Z.; Subhan, A.

2017-07-01

The effect of Acetylene Black (AB) additive contents in lithium titanate/Li4Ti5O12 (LTO) anode on Li-ion Batteries performance is studied in this work. The LTO active material for Li-ion batteries anode was successfully synthesized using sol-gel method to form TiO2 xerogel continued by mixing process with LiOH in ball-mill and then sintered to obtain spinel LTO. The LTO powder is characterized by X-Ray Diffraction (XRD), scanning electron microscopy-Energy Dispersive Spectroscopy (SEM-EDS), and Brunauer-Emmett-Teller (BET). The spinel LTO and TiO2 rutile were detected by XRD diffractogram. The LTO powder is in the form of agglomerates structure. This powder then was mixed with PVDF binder (10%wt) and AB additives with various amount from 10%wt (LTO2 Ac-1), 12%wt (LTO2 Ac-2), and 15%wt (LTO2 Ac-3) of total weight solid content to form electrode sheet. Half-cell coin battery was made with lithium metal foil as a counter electrode. Cyclic voltammetry (CV), Electrochemical-impedance spectroscopy (EIS), and charge discharge (CD) test used to examine the battery performance. The highest resistance value is obtained in LTO2 Ac-3 sample with 15%wt of AB. It might be caused by the formation of side reaction product on electrode surface at initial cycle due to high reactivity of LTO2 Ac-3 electrode. The highest initial capacity at CV test and CD test was obtained in LTO2 Ac-1 (10%wt AB) sample, due to the best proportion of active material content in the compound. While, in the charge-discharge test at high current rate, the best sample rate-capability performance belongs to LTO2 Ac-3 sample (15%wt AB), which still have 24.12 mAh/g of discharge capacity at 10 C with 71.34% capacity loss.

Electrochemistry and safety of Li 4Ti 5O 12 and graphite anodes paired with LiMn 2O 4 for hybrid electric vehicle Li-ion battery applications

Science.gov (United States)

Belharouak, Ilias; Koenig, Gary M.; Amine, K.

A promising anode material for hybrid electric vehicles (HEVs) is Li 4Ti 5O 12 (LTO). LTO intercalates lithium at a voltage of ∼1.5 V relative to lithium metal, and thus this material has a lower energy compared to a graphite anode for a given cathode material. However, LTO has promising safety and cycle life characteristics relative to graphite anodes. Herein, we describe electrochemical and safety characterizations of LTO and graphite anodes paired with LiMn 2O 4 cathodes in pouch cells. The LTO anode outperformed graphite with regards to capacity retention on extended cycling, pulsing impedance, and calendar life and was found to be more stable to thermal abuse from analysis of gases generated at elevated temperatures and calorimetric data. The safety, calendar life, and pulsing performance of LTO make it an attractive alternative to graphite for high power automotive applications, in particular when paired with LiMn 2O 4 cathode materials.

Structural and electrical properties of Li4Ti5O12 anode material for lithium-ion batteries

Science.gov (United States)

Vikram Babu, B.; Vijaya Babu, K.; Tewodros Aregai, G.; Seeta Devi, L.; Madhavi Latha, B.; Sushma Reddi, M.; Samatha, K.; Veeraiah, V.

2018-06-01

In this work we investigate Li4Ti5O12 (LTO) anode material synthesized by conventional solid state reaction method calcined at 850 °C for 16 h. Thermal analysis reveals the temperature dependence of the material properties. The phase composition, micro-morphology and elemental analysis of the compound are characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive spectra (EDS) respectively. The results of XRD pattern possessed cubic spinel structure with space group Fd-3m. The morphological features of the powder sample are in the range of 1.1 μm. The EDS spectra confirm the constituent elemental composition of the sample. Electrical conductivity measurement at different frequencies and temperatures had been carried out; and at room temperature it is found to be 5.96 × 10-7 S/cm. Besides, for the different frequencies applied, the activation energies were calculated and obtained to be in the range of 0.2-0.4 eV.

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.

Improving low-temperature performance of spinel LiNi0.5Mn1.5O4 electrode and LiNi0.5Mn1.5O4/Li4Ti5O12 full-cell by coating solid-state electrolyte Li-Al-Ti-P-O

Science.gov (United States)

Bi, Kun; Zhao, Shi-Xi; Huang, Chao; Nan, Ce-Wen

2018-06-01

Octahedral cathode materials LiNi0.5Mn1.5O4 (LNMO), with primary particles size of 300-600 nm are prepared through one-step co-precipitation. Then solid-state electrolyte Li2O-Al2O3-TiO2-P2O5 (LATP) was coated on LNMO to form continuous surface-modification layer. There is no obviously difference of structure, morphology between coated LATP LiNi0.5Mn1.5O4 (LATP-LNMO) and pristine LiNi0.5Mn1.5O4 (P-LNMO). Low-temperature electrochemical performance of P-LNMO and LATP-LNMO electrodes, including charge-discharge capacity, cycle performance, middle discharge voltage and electrochemical impedance spectra (EIS), were measured systematically with three electrode. The results reveal that LATP-LNMO electrode presents superior electrochemical performance at low temperature, compared to P-LNMO electrode. At -20 °C, the capacity retention of LATP-LNMO (61%) is much higher than that of P-LNMO (39%). According to EIS, the enhancement of performance of LATP-LNMO cathode at low temperature can be attribute to LATP coating, which not only promotes lithium-ion diffusion at electrode/electrolyte interface but also decreases the charge transfer resistance. Finally, the electrochemical performances of full cell of LATP-LNMO or P-LNMO cathode vs Li4Ti5O12 anode are investigated. The energy density can be achieved to 270 Wh·Kg-1 at -20 °C if using LATP-LNMO, which is much better than that of P-LNMO.

Nanostructured Li4Ti5O12 synthesized in a reverse micelle: A bridge between pseudocapacitor and lithium ion battery

International Nuclear Information System (INIS)

Wang Wei; Tu Jiguo; Wang Shubo; Hou Jungang; Zhu Hongmin; Jiao Shuqiang

2012-01-01

Nanoparticles of the Li–Ti–O precursors have been prepared using a reverse micelle method. Transmission electron microscopy (TEM) analysis showed that the precursor had an amorphous structure. The average diameter of the amorphous Li–Ti–O particles was approximately 5 nm (within a range of ±2 nm). X-ray diffraction measurement (XRD) results showed that the conversion of the amorphous precursor to crystalline spinel Li 4 Ti 5 O 12 occurred upon a heat treatment at 450 °C in an atmosphere. This is much lower than that for a standard solid-state reaction of Li 2 CO 3 and TiO 2 . An interesting result was that the spinel Li 4 Ti 5 O 12 synthesized at 450 °C, with a particle size of 10–20 nm, had a good pseudocapacitor performance. The charge/discharge testing indicated that the specific capacity, using the activated material of the spinel Li 4 Ti 5 O 12 synthesized at 450 °C, still remained 91 mAh g −1 even at a high charge/discharge rate of 40C after 100 cycles. In comparison, the Li 4 Ti 5 O 12 particles synthesized at 650 °C have been grown to be the size of 50–60 nm, which mostly indicated a battery performance with a remaining specific capacity of 116 mAh g −1 at a charge/discharge rate of 40C over 100 cycles. The significance in this work disclosed that the nanostructured Li 4 Ti 5 O 12 prepared as a reverse micelle could be a bridging material between pseudocapacitor and lithium ion battery.

High rate performance of the carbon encapsulated Li4Ti5O12 for lithium ion battery

Science.gov (United States)

Cheng, Qi; Tang, Shun; Liang, Jiyuan; Zhao, Jinxing; Lan, Qian; Liu, Chang; Cao, Yuan-Cheng

Li4Ti5O12 (LTO) is attractive alternative anode material with excellent cyclic performance and high rate after coating modifications of the conductive materials. Anatase TiO2 and glucose were applied of the synthesis of the carbon coated LTO (C@LTO). XRD results showed that all the major diffractions from the spinel structure of LTO can be found in the C@LTO such as (1 1 1), (3 1 1), (4 0 0) but there are no observations of the Carbon diffraction peaks. Electrochemical Impedance Spectroscopy (EIS) data shows C@LTO resistance was nearly half of the LTO value. Rate performance showed that capacity of C@LTO was higher than that of the pure LTO from 0.1 C, 0.2 C, 1 C, 2 C, 5 C and 10 C, which indicates that this is a promising approach to prepare the high performance LTO anode.

Nanostructured lithium titanates (Li4Ti5O12) for lithium-ion batteries

CSIR Research Space (South Africa)

Wen, L

2016-07-01

Full Text Available Nanostructured lithium titanates (Li(sub4)Ti(sub5)O(sub12)) have been intensively investigated as anode materials of Li-ion batteries due to their many advantages, such as excellent performance, outstanding safety, and excellent cycle life...

Carbon coated Li4Ti5O12 nanorods as superior anode material for high rate lithium ion batteries

International Nuclear Information System (INIS)

Luo, Hongjun; Shen, Laifa; Rui, Kun; Li, Hongsen; Zhang, Xiaogang

2013-01-01

Highlights: •A novel approach has been developed to fabricate 1D Li 4 Ti 5 O 12 /C nanorods by a wet-chemical route. •Carbon coating layer effectively restrict the particle growth and enhance electronic conductivity. •The Li 4 Ti 5 O 12 /C nanorods exhibit remarkable rate capability and long cycle life. -- Abstract: We describe a novel approach for the synthesis of carbon coated Li 4 Ti 5 O 12 (Li 4 Ti 5 O 12 /C) nanorods for high rate lithium ion batteries. The carbon coated TiO 2 nanotubes using the glucose as carbon source are first synthesized by hydrothermal treatment. The commercial anatase TiO 2 powder is immersed in KOH sulotion and subsequently transforms into Li 4 Ti 5 O 12 /C in LiOH solution under hydrothermal condition. Field-emission scanning electron microscopy, transmission electron microscopy, X-ray diffraction, nitrogen adsorption/desorption and Raman spectra are performed to characterize their morphologies and structures. Compared with the pristine Li 4 Ti 5 O 12 , one-dimensional (1D) Li 4 Ti 5 O 12 /C nanostructures show much better rate capability and cycling stability. The 1D Li 4 Ti 5 O 12 /C architectures effectively restrict the particle growth and enhance their electronic conductivity, enabling fast ion and electron transport

Improved electrochemical performance of Li4Ti5O12 with a variable amount of graphene as a conductive agent for rechargeable lithium-ion batteries by solvothermal method

International Nuclear Information System (INIS)

Rai, Alok Kumar; Gim, Jihyeon; Kang, Sung-Won; Mathew, Vinod; Anh, Ly Tuan; Kang, Jungwon; Song, Jinju; Paul, Baboo Joseph; Kim, Jaekook

2012-01-01

We report on the solvothermal preparation of pure Li 4 Ti 5 O 12 and Li 4 Ti 5 O 12 /graphene (15 wt% and 30 wt%) nanocomposites anode for high-performance lithium-ion batteries. Structure and morphology studies of the nanocomposites by X-ray diffraction, field-emission scanning electron microscopy and field-emission transmission electron microscopy reveal Li 4 Ti 5 O 12 nanoparticles embedded onto the graphene nanosheets. On comparison to pure spinel Li 4 Ti 5 O 12 , the electrochemical performances of the Li 4 Ti 5 O 12 /graphene nanocomposites indicate higher capacities and enhanced cycle performances within the voltage domain of 1.0–2.5 V, under current rates as high as 10.4 C. The production of phase pure Li 4 Ti 5 O 12 nanoparticles ensures the short ion-diffusion paths while the presence of graphene facilitates improved structural network and hence enhanced electronic transport in the prepared nanocomposites. These factors eventually amount to impressive electrochemical properties. Highlights: ► A simple polyol-based approach to obtain the graphene nanosheets. ► Li 4 Ti 5 O 12 /graphene nanocomposites synthesis by polyol-based solvothermal process. ► Low temperature solvothermal strategy is one-step process to control nanoparticle sizes. ► The nanoparticles are well anchored onto the graphene nanosheets in the nanocomposites. ► Li 4 Ti 5 O 12 /graphene nanocomposites exhibit impressive electrochemical performances.

One-step argon/nitrogen binary plasma jet irradiation of Li4Ti5O12 for stable high-rate lithium ion battery anodes

Science.gov (United States)

Lan, Chun-Kai; Chuang, Shang-I.; Bao, Qi; Liao, Yen-Ting; Duh, Jenq-Gong

2015-02-01

Atmospheric pressure Ar/N2 binary plasma jet irradiation has been introduced into the manufacturing process of lithium ions batteries as a facile, green and scalable post-fabrication treatment approach, which enhanced significantly the high-rate anode performance of lithium titanate (Li4Ti5O12). Main emission lines in Ar/N2 plasma measured by optical emission spectroscopy reveal that the dominant excited high-energy species in Ar/N2 plasma are N2*, N2+, N∗ and Ar∗. Sufficient oxygen vacancies have been evidenced by high resolution X-ray photoelectron spectroscopy analysis and Raman spectra. Nitrogen doping has been achieved simultaneously by the surface reaction between pristine Li4Ti5O12 particles and chemically reactive plasma species such as N∗ and N2+. The variety of Li4Ti5O12 particles on the surface of electrodes after different plasma processing time has been examined by grazing incident X-Ray diffraction. Electrochemical impedance spectra (EIS) confirm that the Ar/N2 atmospheric plasma treatment facilitates Li+ ions diffusion and reduces the internal charge-transfer resistance. The as-prepared Li4Ti5O12 anodes exhibit a superior capacity (132 mAh g-1) and excellent stability with almost no capacity decay over 100 cycles under a high C rate (10C).

Rapid charge-discharge property of Li4Ti5O12-TiO2 nanosheet and nanotube composites as anode material for power lithium-ion batteries.

Science.gov (United States)

Yi, Ting-Feng; Fang, Zi-Kui; Xie, Ying; Zhu, Yan-Rong; Yang, Shuang-Yuan

2014-11-26

Well-defined Li4Ti5O12-TiO2 nanosheet and nanotube composites have been synthesized by a solvothermal process. The combination of in situ generated rutile-TiO2 in Li4Ti5O12 nanosheets or nanotubes is favorable for reducing the electrode polarization, and Li4Ti5O12-TiO2 nanocomposites show faster lithium insertion/extraction kinetics than that of pristine Li4Ti5O12 during cycling. Li4Ti5O12-TiO2 electrodes also display lower charge-transfer resistance and higher lithium diffusion coefficients than pristine Li4Ti5O12. Therefore, Li4Ti5O12-TiO2 electrodes display lower charge-transfer resistance and higher lithium diffusion coefficients. This reveals that the in situ TiO2 modification improves the electronic conductivity and electrochemical activity of the electrode in the local environment, resulting in its relatively higher capacity at high charge-discharge rate. Li4Ti5O12-TiO2 nanocomposite with a Li/Ti ratio of 3.8:5 exhibits the lowest charge-transfer resistance and the highest lithium diffusion coefficient among all samples, and it shows a much improved rate capability and specific capacity in comparison with pristine Li4Ti5O12 when charging and discharging at a 10 C rate. The improved high-rate capability, cycling stability, and fast charge-discharge performance of Li4Ti5O12-TiO2 nanocomposites can be ascribed to the improvement of electrochemical reversibility, lithium ion diffusion, and conductivity by in situ TiO2 modification.

Hierarchical carambola-like Li4Ti5O12-TiO2 composites as advanced anode materials for lithium-ion batteries

International Nuclear Information System (INIS)

Zhang, Yu; Zhang, Yun; Huang, Ling; Zhou, Zhongfu; Wang, Jingfeng; Liu, Heng; Wu, Hao

2016-01-01

Hierarchically structured Li 4 Ti 5 O 12 -TiO 2 (LTO-TiO 2 ) composites are synthesized using a facile hydrothermal approach upon reaction time control. With control over the time of hydrothermal reaction at 18 h, a hierarchical dual-phase LTO-TiO 2 composite with appropriate amount of anatase TiO 2 can be obtained, and it possesses a uniform carambola-like framework assembled by numerous ultrathin nanosheets, which enable a relatively large specific surface area, along with abundant interlayer channels to favor electrolyte penetration. When used as anode materials for lithium-ion batteries, such carambola-like LTO-TiO 2 composite exhibits remarkably improved capacity, high-rate capability, and cycling stability over other LTO-TiO 2 samples, which are synthesized at different time of hydrothermal reaction. Specifically, it deliveries a discharge capacity as high as 115.1 and 91.2 mAh g −1 at a very high current rate of 20 and 40C, respectively, while a stable reversible capacity of 171.7 mAh g −1 can be retained after 200 charge-discharge cycles at 1C, corresponding to 88.6% capacity retention. The excellent electrochemical performances benefit from the unique hierarchical carambola-like structure together with the mutually complementary intrinsic advantages between LTO and TiO 2 . The robust and porous nanosheets-assembled LTO-TiO 2 framework not only offers a shorter transport pathway for electron and Li-ion migration within this composite material, but also is able to alleviate the structure distortion during the fast Li-ion insertion/extraction process. The work described here shows that the hierarchical carambola-like LTO-TiO 2 composite is a promising anode material for high-power and long-life lithium-ion batteries.

Elaborate strategy for preparing Li4Ti5O12-based anode materials with significantly improved lithium storage: TiO2 nanodots in-situ decoration and hierarchical structure construction

Science.gov (United States)

Xu, Hui; Tian, Qinghua; Huang, Jun; Bao, Dongmei; Zhang, Zhengxi; Yang, Li

2017-11-01

Spinel Li4Ti5O12 (LTO) has attracted extensive attention as potential anode materials for power lithium-ion batteries due to its outstanding structural stability and remarkable safety. However, it's practical application yet be limited by such disadvantages of dissatisfied specific capacity, poor electron conductivity and low lithium-ion diffusion coefficient. Thus, design and preparation of LTO anodes with desirable performance is still a challenge. Herein, we have successfully and greatly improved the performance of LTO anodes, in terms of rate capability, life and specific capacity in particular via dot-to-face anatase TiO2in-situ decoration and hierarchical structure construction under a facile approach (directly using the tetrabutyl titanate as titanium source instead of specially prepared titanium oxide precursors). The as-prepared LTO-based anode (denoted as T-LTO) delivers an ultra-high reversible specific capacity of 196.5 mAh g-1 after 300 cycles at 20 mA g-1, and superior rate performance and even ultra-long life of more than 145.8 mAh g-1 at 28.5C between 1.0 and 3.0 V. The achieved outstanding electrochemical performance largely surpasses that of reportedly state-of-the-art LTO-based anode materials. This work may open up a broader vision into developing advanced LTO-based anode materials for lithium-ion batteries.

A new, high energy rechargeable lithium ion battery with a surface-treated Li1.2Mn0.54Ni0.13Co0.13O2 cathode and a nano-structured Li4Ti5O12 anode

International Nuclear Information System (INIS)

Liu, Xiaoyu; Huang, Tao; Yu, Aishui

2015-01-01

Through elaborate design, a new rechargeable lithium ion battery has been developed by comprising a surface-treated Li 1.2 Mn 0.54 Ni 0.13 Co 0.13 O 2 cathode and a nano-structured Li 4 Ti 5 O 12 anode. After precondition Na 2 S 2 O 8 treatment, the initial coulombic efficiency of Li 1.2 Mn 0.54 Ni 0.13 Co 0.13 O 2 cathode has been significantly increased and can be compatible with that of the nano-structured Li 4 Ti 5 O 12 anode. The optimization of structure and morphology for both active electrode materials result in their remarkable electrochemical performances in respective lithium half-cells. Ultimately, the rechargeable lithium ion full battery consisting of both electrodes delivers a specific capacity of 99.0 mAh g −1 and a practical energy density of 201 Wh kg −1 , based on the total weight of both active electrode materials. Furthermore, as a promising candidate in the lithium ion battery field, this full battery also achieves highly attractive electrochemical performance with high coulombic efficiency, excellent cycling stability and outstanding rate capability. Thus the proposed battery displays broad practical application prospects for next generation of high-energy lithium ion battery. - Highlights: • The Li 1.2 Mn 0.54 Ni 0.13 Co 0.13 O 2 cathode is surface-treated by Na 2 S 2 O 8 . • The nano-sized Li 4 Ti 5 O 12 anode is obtained by a solid-state method. • A new Li 1.2 Mn 0.54 Ni 0.13 Co 0.13 O 2 /Li 4 Ti 5 O 12 lithium ion battery is developed. • The battery shows high coulombic efficiency, specific capacity and energy density. • The battery shows high capacity retention rate and good high-rate capability

Synthesis and electrochemical properties of Li4Ti5O12 spheres and its application for hybrid supercapacitors

International Nuclear Information System (INIS)

Deng, SiXu; Li, JingWen; Sun, ShiBing; Wang, Hao; Liu, JingBing; Yan, Hui

2014-01-01

Highlights: • Li 4 Ti 5 O 12 (LTO) spheres are prepared by molten-salt and TiO 2 spheres as template. • The LTO spheres are potential for using as anode for AC//LTO hybrid capacitor. • The AC//LTO hybrid supercapacitor presents good electrochemical performance. - Abstract: There is a growing demand for hybrid supercapacitor systems to combine the advantages of both lithium-ion battery and supercapacitors for the application of electric vehicles. We describe in this paper one kind of hybrid supercapacitor comprising spherical Li 4 Ti 5 O 12 as negative electrode and activated carbon (AC) as positive electrode in the non-aqueous electrolyte. The Li 4 Ti 5 O 12 spheres were synthesized using a LiCl-KCl molten-salt method and TiO 2 spheres as the template. The Li 4 Ti 5 O 12 spheres revealed high discharge capacity (168 mAh g −1 at 0.2 C), and a good capacity retention with high coulombic efficiency after cycling, which can be potential anode material for lithium ion batteries and negative material for hybrid supercapacitor. The AC//LTO hybrid supercapacitor exhibits excellent capacity retention of 93% after 500 cycles and offers higher energy density and power density than the AC//AC symmetric supercapacitor. The presented AC//LTO hybrid supercapacitor could be a competitive candidate for the promising energy storage devices

Electrochemical behaviors of wax-coated Li powder/Li 4Ti 5O 12 cells

Science.gov (United States)

Park, Han Eol; Seong, Il Won; Yoon, Woo Young

The wax-coated Li powder specimen was effectively synthesized using the drop emulsion technique (DET). The wax layer on the powder was verified by SEM, Focused Ion Beam (FIB), EDX and XPS. The porosity of a sintered wax-coated Li electrode was measured by linear sweep voltammetry (LSV) and compared with that of a bare, i.e., un-coated Li electrode. The electrochemical behavior of the wax-coated Li powder anode cell was examined by the impedance analysis and cyclic testing methods. The cyclic behavior of the wax-coated Li powder anode with the Li 4Ti 5O 12 (LTO) cathode cell was examined at a constant current density of 0.35 mA cm -2 with the cut-off voltages of 1.2-2.0 V at 25 °C. Over 90% of the initial capacity of the cell remained even after the 300th cycle. The wax-coated Li powder was confirmed to be a stable anode material.

Highly-crystalline ultrathin gadolinium doped and carbon-coated Li4Ti5O12 nanosheets for enhanced lithium storage

Science.gov (United States)

Xu, G. B.; Yang, L. W.; Wei, X. L.; Ding, J. W.; Zhong, J. X.; Chu, P. K.

2015-11-01

Highly-crystalline gadolinium doped and carbon-coated ultrathin Li4Ti5O12 (LTO) nanosheets (denoted as LTO-Gd-C) as an anode material for Li-ion batteries (LIBs) are synthesized on large scale by controlling the amount of carbon precursor in the topotactic transformation of layered ultrathin Li1.81H0.19Ti2O5·xH2O (H-LTO) nanosheets at 700 °C. The characterizations of structure and morphology reveal that the gadolinium doped and carbon-coated ultrathin LTO nanosheets have high crystallinity with a thickness of about 10 nm. Gadolinium doping allows the spinel LTO products to be stabilized, thereby preserving the precursor's sheet morphology and single crystal structure. Carbon encapsulation serves dual functions by restraining crystal growth of the LTO primary nanoparticles in the LTO-Gd-C nanosheets and decreasing the external electron transport resistance. Owing to the synergistic effects rendered by ultrathin nanosheets with high crystallinity, gadolinium doping and carbon coating, the developed ultrathin LTO nanosheets possess excellent specific capacity, cycling performance, and rate capability compared with reference materials, when evaluated as an anode material for lithium ion batteries (LIBs). The simple and effective strategy encompassing nanoscale morphological engineering, surface modification, and doping improves the performance of LTO-based anode materials for high energy density and high power LIBs applied in large scale energy storage.

Chrystal structure properties of Al-doped Li{sub 4}Ti{sub 5}O{sub 12} synthesized by solid state reaction method

Energy Technology Data Exchange (ETDEWEB)

Sandi, Dianisa Khoirum, E-mail: dianisa875@gmail.com; Suryana, Risa, E-mail: rsuryana@staff.uns.ac.id [Department of Physics, Faculty of Mathematics and Natural Sciences, Sebelas Maret University (Indonesia); Priyono, Slamet, E-mail: slam013@lipi.go.id [Physics Research Center (P2F)-LIPI, Puspiptek Area, Serpong, Tangerang (Indonesia)

2016-02-08

This research aim is to analyze the effect of Aluminum (Al) doping in the structural properties of Al-doped Li{sub 4}Ti{sub 5}O{sub 12} as anode in lithium ion battery. Al-doped Li{sub 4}Ti{sub 5}O{sub 12} powders were synthesized by solid state reaction method. LiOH.H{sub 2}O, TiO{sub 2}, and Al{sub 2}O{sub 3} were raw materials. These materials were milled for 15 h, calcined at temperature of 750{sup o}C and sintered at temperature of 800{sup o}C. Mole percentage of doping Al (x) was varied at x=0; x=0.025; and x =0.05. Al-doped Li{sub 4}Ti{sub 5}O{sub 12} powders were synthesized by solid state reaction method. X-ray diffraction was employed to determine the structure of Li{sub 4}Ti{sub 5}O{sub 12}. The PDXL software was performed on the x-ray diffraction data to estimate the phase percentage, the lattice parameter, the unit cell volume, and the crystal density. Al-doped Li{sub 4}Ti{sub 5}O{sub 12} has cubic crystal structure. Al-doping at x=0 and x=0.025 does not change the phase as Li{sub 4}Ti{sub 5}O{sub 12} while at x=0.050 the phase changes to the LiTiAlO{sub 4}. The diffraction patterns show that the angle shifted to the right as the increase of x which indicated that Al substitute Ti site. Percentage of Li{sub 4}Ti{sub 5}O{sub 12} phase at x=0 and x=0.025 was 97.8% and 96.8%, respectively. However, the lattice parameters, the unit cell volume, and the crystal density does not change significantly at x=0; x=0.025; and x=0.050. Based on the percentage of Li{sub 4}Ti{sub 5}O{sub 12} phase, the Al-doped Li at x=0 and x=0.025 is promising as a lithium battery anode.

Graphene oxide-confined synthesis of Li4Ti5O12 microspheres as high-performance anodes for lithium ion batteries

International Nuclear Information System (INIS)

Zhang, Jiawei; Cai, Yurong; Wu, Jun; Yao, Juming

2015-01-01

This paper reports a graphene oxide (GO) confined strategy to synthesize reduced GO-coated lithium titanate (Li 4 Ti 5 O 12, LTO) microspheres using as-prepared TiO 2 microspheres and GO as raw materials. The obtained samples are characterized by X-ray diffraction, field emission scanning electron microscopy and spectrophotometer. Results show that the spherical LTO is formed with approximate 1 μm diameter after hydrothermal reactions, which is due to a confined effect of GO on the surface of TiO 2 spheres. Electrochemical tests reveal that the presence of rGO can increase the capacity and cycling stability of LTO anodes, especially at higher C rate. The 3 wt% rGO-coated LTO anodes present a higher reversible Li-ion storage with a specific discharge capacity of 131.6 mAh g −1 at 5 C and 97% retention even after 500 cycles, which are more excellent than those of pristine LTO. The GO-confined method is anticipated to synthesize other electrode materials with high electrochemical performances

Carbon coated Li{sub 4}Ti{sub 5}O{sub 12} nanorods as superior anode material for high rate lithium ion batteries

Energy Technology Data Exchange (ETDEWEB)

Luo, Hongjun; Shen, Laifa; Rui, Kun; Li, Hongsen; Zhang, Xiaogang, E-mail: azhangxg@nuaa.edu.cn

2013-09-25

Highlights: •A novel approach has been developed to fabricate 1D Li{sub 4}Ti{sub 5}O{sub 12}/C nanorods by a wet-chemical route. •Carbon coating layer effectively restrict the particle growth and enhance electronic conductivity. •The Li{sub 4}Ti{sub 5}O{sub 12}/C nanorods exhibit remarkable rate capability and long cycle life. -- Abstract: We describe a novel approach for the synthesis of carbon coated Li{sub 4}Ti{sub 5}O{sub 12} (Li{sub 4}Ti{sub 5}O{sub 12}/C) nanorods for high rate lithium ion batteries. The carbon coated TiO{sub 2} nanotubes using the glucose as carbon source are first synthesized by hydrothermal treatment. The commercial anatase TiO{sub 2} powder is immersed in KOH sulotion and subsequently transforms into Li{sub 4}Ti{sub 5}O{sub 12}/C in LiOH solution under hydrothermal condition. Field-emission scanning electron microscopy, transmission electron microscopy, X-ray diffraction, nitrogen adsorption/desorption and Raman spectra are performed to characterize their morphologies and structures. Compared with the pristine Li{sub 4}Ti{sub 5}O{sub 12}, one-dimensional (1D) Li{sub 4}Ti{sub 5}O{sub 12}/C nanostructures show much better rate capability and cycling stability. The 1D Li{sub 4}Ti{sub 5}O{sub 12}/C architectures effectively restrict the particle growth and enhance their electronic conductivity, enabling fast ion and electron transport.

Promotional role of Li4Ti5O12 as polysulfide adsorbent and fast Li+ conductor on electrochemical performances of sulfur cathode

Science.gov (United States)

Zeng, Tianbiao; Hu, Xuebu; Ji, Penghui; Shang, Biao; Peng, Qimeng; Zhang, Yaoyao; Song, Ruiqiang

2017-08-01

Lithium-sulfur (Li-S) batteries attract much attention due to its high specific capacity and energy density compared to lithium-ion batteries (LiBs). Herein, a novel composite named as (void/nano-Li4Ti5O12 pieces)@C [(v/n-L)@C] was designed and prepared as a sulfur host. Spinel Li4Ti5O12 here as a multifunctional additive played as polysulfide adsorbent agent and fast Li+ conductor, and carbon shell was designed as electronic conductor, as well as volume barrier to limit the volume expansion caused by sulfur. As-prepared (S/nano-Li4Ti5O12 pieces)@C [(S/n-L)@C] are core-shell spheres, which are about 200 nm in size. Nano-Li4Ti5O12 and sulfur were coated by the outer carbon shell with a thickness of about 20 nm. The experimental results show that electrochemical performances of (S/n-L)@C cathode were enhanced effectively compared to S@C cathode. At 0.5C and 1C, the discharge capacity of (S/n-L)@C was 33.5% and 40.1% higher than that of S@C at 500th cycle. Even at 2C, its capacity reached 600.9 mAh g-1 at 1000th cycle. Li+ conductivity of (S/n-L)@C was one order of magnitude higher than that of S@C, which was reach to 2.55 × 10-8 S cm-1. The experiment results indicate Li4Ti5O12 plays a promotional role on electrochemical performances of sulfur cathode, especially for stable cycling performance and high rate performance.

Preparation of Li4Ti5O12 electrode thin films by a mist CVD process with aqueous precursor solution

Directory of Open Access Journals (Sweden)

Kiyoharu Tadanaga

2015-03-01

Full Text Available Spinel Li4Ti5O12 thin films were prepared by a mist CVD process, using an aqueous solution of lithium nitrate and a water-soluble titanium lactate complex as the source of Li and Ti, respectively. In this process, mist particles ultrasonically atomized from a source aqueous solution were transferred by nitrogen gas to a heating substrate to prepare thin films. Scanning electron microscopy observation showed that thin films obtained by this process were dense and smooth, and thin films with a thickness of about 500 nm were obtained. In the X-ray diffraction analysis, formation of Li4Ti5O12 spinel phase was confirmed in the obtained thin film sintered at 700 °C for 4 h. The cell with the thin films as an electrode exhibited a capacity of about 110 mAh g−1, and the cell showed good cycling performance during 10 cycles.

Solid State Formation Mechanism of Li₄Ti₅O₁₂ from an Anatase TiO₂ Source

DEFF Research Database (Denmark)

Shen, Yanbin; Søndergaard, Martin; Christensen, Mogens

2014-01-01

Solid state synthesis of Li4Ti5O12 anode material for Li ion batteries typically results in products containing rutile TiO2 and Li2TiO3 impurities, and subsequent high calcination temperatures lead to particle growth that reduces capacity and rate ability. Here, the formation and growth of Li4Ti5O......12 particles by a solid-state reaction using anatase TiO2 with various crystallite sizes and Li2CO3 is investigated by in situ high temperature powder X-ray diffraction (HT-PXRD) and thermal gravimetry-differential thermal analysis (TG-DTA). The combined data provide insight into the origin...... crystallite sizes (∼50 nm, ∼30 nm, ∼20 nm, and amorphous) were explored, and decreasing crystallite sizes causes a reduced initial reaction temperature. Using anatase with a crystallite size of ∼20 nm resulted in phase pure Li4Ti5O12 at the lowest temperature (800 °C). PXRD and TG-DTA results also revealed...

Molecular dynamics simulations of spinels: LiMn2O4 and Li4Mn5O12 at high temperatures

International Nuclear Information System (INIS)

Ledwaba, R S; Matshaba, M G; Ngoepe, P E

2015-01-01

Energy storage technologies are critical in addressing the global challenge of clean sustainable energy. Spinel lithium manganates have attracted attention due to their electrochemical properties and also as promising cathode materials for lithium-ion batteries. The current study focused on the effects of high temperatures on the materials, in order to understand the sustainability in cases where the battery heats up to high temperature and analysis of lithium diffusion aids in terms of intercalation host compatibility. It is also essential to understand the high temperature behaviour and lithium ion host capability of these materials in order to perform the armorphization and recrystalization of spinel nano-architectures. Molecular dynamics simulations carried out to predict high temperature behaviour of the spinel systems. The NVE ensemble was employed, in the range 300 - 3000K. The melting temperature, lithium-ion diffusion and structural behaviour were monitored in both supercell systems. LiMn 2 O 4 indicated a diffusion rate that increased rapidly above 1500K, just before melting (∼1700K) and reached its maximum diffusion at 2.756 × 10 -7 cm 2 s -1 before it decreased. Li 4 Mn 5 O 12 indicated an exponential increase above 700K reaching 8.303 × 10 −7 cm 2 s −1 at 2000K and allowing lithium intercalation even above its melting point of around 1300K. This indicated better structural stability of Li 4 Mn 5 O 12 and capability to host lithium ions at very high temperatures (up to 3000 K) compared to LiMn 2 O 4 . (paper)

An infrared study of the surface chemistry of lithium titanate spinel (Li4Ti5O12)

International Nuclear Information System (INIS)

Snyder, Mark Q.; DeSisto, William J.; Tripp, Carl P.

2007-01-01

While there are numerous studies examining the performance of lithium titanate spinel (LTS) as a lithium-ion battery, little is known about the surface chemistry of this material. In this paper, diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy spectroscopy was used to study the type of surface groups present on LTS as a function of temperature. The surface was found to contain isolated and hydrogen-bonded TiOH groups and the dehydroxylation behavior with thermal treatment was similar to that of TiO 2 . In addition, hexamethyldisilazane (HMDZ) and pyridine were used to probe the reactivity of surface hydroxyl groups and the presence of Lewis acid sites, respectively. The reaction of HMDZ occurred with both LiOH and TiOH groups to form Li-O-Si and Ti-O-Si. In addition, the reaction of gaseous CO 2 with the Li + ions resulted in the formation of surface carbonate ions. The carbonate ions are removed by heating at 400 deg. C in air

Structural characterization and electrochemical behaviour of Li{sub (4−x)/3}Ti{sub (5−2x)/3}Mn{sub x}O{sub 4} solid solution with spinel-structure

Energy Technology Data Exchange (ETDEWEB)

Martín, P., E-mail: pmartinp@quim.ucm.es; López, M.L.; Pico, C.; Veiga, M.L.

2013-07-15

A series of new oxides Li{sub (4−x)/3}Ti{sub (5−2x)/3}Mn{sub x}O{sub 4} (0.1 ≤ x ≤ 0.9) have been synthesized by solid state reactions and characterized by thermal analysis and X-ray and neutron diffraction. In all phases, Li{sup +} cations mainly occupy tetrahedral sites and transition metals cations are located on the octahedral ones. These phases show a structural disorder–order transition associated to the proportion of manganese in the samples and to its oxidation state. All these factors have a marked influence on the electrochemical properties and the phase x = 0.1 shows the best characteristics to be used as anode in a solid state battery. - Highlights: • Lithium spinels anodes in batteries. • Influence of Ti/Mn ratio in the electrochemical behaviour. • Li{sub 1.3}Ti{sub 1.6}Mn{sub 0.1}O{sub 4}: a promising zero-strain material. • Influence of disorder–order transitions on the physical properties.

Kinetic analysis of the thermal decomposition of Li4Ti5O12 pellets

Directory of Open Access Journals (Sweden)

Hugo A. Mosqueda

2011-12-01

Full Text Available A single dynamic kinetic analysis, describing the surface decomposition of Li4Ti5O12 pellets, has been performed. Samples were analyzed by X-ray diffraction and scanning electron microscopy. The analyses were performed between 1000 and 1100°C and different times, perceiving the Li4Ti5O12 decomposition to Li2Ti3O7, with a loss of lithium. As expected, more rapid decomposition behaviour was found at higher temperatures. Finally, the activation energy for this decomposition of Li4Ti5O12 to Li2Ti3O7 was estimated to be equal to 383 kJ/mol.

Na insertion into nanocrystalline Li4Ti5O12 spinel: An electrochemical study

Czech Academy of Sciences Publication Activity Database

Zukalová, Markéta; Pitňa Lásková, Barbora; Klementová, Mariana; Kavan, Ladislav

2017-01-01

Roč. 245, AUG 2017 (2017), s. 505-511 ISSN 0013-4686 R&D Projects: GA ČR GA15-06511S; GA MŠk LM2015087 Institutional support: RVO:61388955 ; RVO:68378271 Keywords : Na insertion * Li4Ti5O12 * nanocrystalline Subject RIV: CG - Electrochemistry; BM - Solid Matter Physics ; Magnetism (FZU-D) OBOR OECD: Electrochemistry (dry cells, batteries, fuel cells, corrosion metals, electrolysis); Condensed matter physics (including formerly solid state physics, supercond.) (FZU-D) Impact factor: 4.798, year: 2016

Anomalous magnetoresistance in the spinel superconductor LiTi2O4.

Science.gov (United States)

Jin, K; He, G; Zhang, X; Maruyama, S; Yasui, S; Suchoski, R; Shin, J; Jiang, Y; Yu, H S; Yuan, J; Shan, L; Kusmartsev, F V; Greene, R L; Takeuchi, I

2015-05-20

LiTi2O4 is a unique compound in that it is the only known spinel oxide superconductor. The lack of high quality single crystals has thus far prevented systematic investigations of its transport properties. Here we report a careful study of transport and tunnelling spectroscopy in epitaxial LiTi2O4 thin films. An unusual magnetoresistance is observed which changes from nearly isotropic negative to prominently anisotropic positive as the temperature is decreased. We present evidence that shows that the negative magnetoresistance likely stems from the suppression of local spin fluctuations or spin-orbit scattering centres. The positive magnetoresistance suggests the presence of an orbital-related state, also supported by the fact that the superconducting energy gap decreases as a quadratic function of magnetic field. These observations indicate that the spin-orbital fluctuations play an important role in LiTi2O4 in a manner similar to high-temperature superconductors.

Ultrathin Li4Ti5O12 nanosheets as anode materials for lithium and sodium storage

Energy Technology Data Exchange (ETDEWEB)

Feng, Xuyong; Zou, Hailin; Xiang, Hongfa; Guo, Xin; Zhou, Tianpei; Wu, Yucheng; Xu, Wu; Yan, Pengfei; Wang, Chong M.; Zhang, Jiguang; Yu, Yan

2016-06-13

Two-dimensional Li4Ti5O12 (LTO) nanosheets are prepared via a surfactant assisted hydrothermal process. Polyether (P123) was added as the surfactant to modify the surface and control the microstructure of the hydrothermal products and thus affect the electrochemical performance of the as-synthesized LTO anode material. XRD results show that the addition of P123 can restrain the growth of Li2TiO3 during the hydrothermal process, thus affecting the morphology and enhancing the rate performance of the final products. With the addition of P123, the growth of LTO can be restrained and ultrathin LTO nanosheets can be obtained after high temperature sintering, which is beneficial for the charge transfer and Li+ ion diffusion. The rate performance of these two different LTO materials is very different because of their differences in phase composition and fine morphology. The P123-assisted nanostructured LTO sample (P-LTO) shows a much higher rate capability than the LTO sample without P123, with over 130 mAh g-1 capacity retained at the charge-discharge rate of 64C when used in a lithium battery. For intercalation of larger size Na+ ions, the P-LTO still exhibit a capacity of 115 mAh g-1 at a charge (de-sodiation process) rate of 10C and maintains 96% capacity after 400 cycles

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.

Gas swelling behaviour at different stages in Li4Ti5O12/LiNi1/3Co1/3Mn1/3O2 pouch cells

Science.gov (United States)

Liu, Wei; Liu, Haohan; Wang, Qian; Zhang, Jian; Xia, Baojia; Min, Guoquan

2017-11-01

Gas swelling behaviour is a major drawback of batteries that are based on Li4Ti5O12 anode materials and hinders their application. In this article, the morphology and electronic structure changes of Li4Ti5O12 electrodes at ageing and cycling stages are investigated using scanning electron microscopy, X-ray absorption near-edge structure and X-ray photoelectron spectroscopy. A simple method that uses an air bag to collect the generated gases was conducted and the gases were then characterised by gas chromatography/mass spectrometry. The results indicate that the charge transformation of Ti ions would aggravate the gas swelling behaviour. The solid electrolyte interphase (SEI) films form on the surface of the Li4Ti5O12 particles and become thicker with increasing charge state. The gas components change significantly during the ageing and cycling, indicating the complexity of the gas swelling mechanism.

Embedding nano-Li{sub 4}Ti{sub 5}O{sub 12} in hierarchical porous carbon matrixes derived from water soluble polymers for ultra-fast lithium ion batteries anodic materials

Energy Technology Data Exchange (ETDEWEB)

Lan, Chun-Kai; Bao, Qi; Huang, Yao-Hui; Duh, Jenq-Gong, E-mail: jgd@mx.nthu.edu.tw

2016-07-15

Li{sub 4}Ti{sub 5}O{sub 12}/hierarchical porous carbon matrixes composites are successfully prepared by a facile and fast polymers assisted sol–gel method, aiming to promote both electronic and ionic conductivity. As indicated by Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy analysis, three less expensive cost and available water soluble polymers (e.g. PAA, CMC, and SA) can homogeneously react with Li–Ti–O precursor to incorporate into interior of nano-scale lithium titanate and provide a continues conductive network after pyrolysis. In addition, the results of scanning electron microscopy and transmission electron microscopy also prove that the Li{sub 4}Ti{sub 5}O{sub 12} nanoparticles are firmly embedded in porous carbon matrix with no obvious agglomeration. EIS measurement and cyclic voltammetry further reveal that the facilitated electrode kinetics and better ionic transport of Li{sub 4}Ti{sub 5}O{sub 12}/hierarchical porous carbon matrixes composites than that of Li{sub 4}Ti{sub 5}O{sub 12}. The c-CMC-LTO exhibits a superior capacity of 92 mAh g{sup −1} and retains its initial value with no obviously capacity decay over 200 cycles under an ultra-high C rate (50 C). - Graphical abstract: Schematic illustrations of the formation process of embedding LTO into Carbon matrixes derived from water soluable polymers (upper) and the electrochemical reaction paths in LTO/Carbon composites during charging/discharging processes (lower). - Highlights: • Hierarchical porous carbon matrixes were used to improve the Li{sub 4}Ti{sub 5}O{sub 12} anodes. • Carbon matrixes could suppress the agglomeration of Li{sub 4}Ti{sub 5}O{sub 12} nanoparticles. • meso-nanoporous carbon structure was beneficial for filtration of electrolyte. • The c-CMC-LTO exhibited superior high rate capability and cycling durability.

Hierarchical carbon-coated acanthosphere-like Li4Ti5O12 microspheres for high-power lithium-ion batteries

Science.gov (United States)

Sha, Yujing; Xu, Xiaomin; Li, Li; Cai, Rui; Shao, Zongping

2016-05-01

In this work, carbon-coated hierarchical acanthosphere-like Li4Ti5O12 microspheres (denoted as AM-LTO) were prepared via a two-step hydrothermal process with low-cost glucose as the organic carbon source. The hierarchical porous microspheres had open structures with diameters of 4-6 μm, which consisted of a bunch of willow leaf-like nanosheets. Each nanosheet was comprised of Li4Ti5O12 nanoparticles that are 20 nm in size and coated by a thin carbon layer. When applied as the anode material for lithium-ion batteries (LIBs), the AM-LTO presented outstanding rate and cycling performance due to its unique morphologies. A high capacity of 145.6 mAh g-1 was achieved for AM-LTO at a rate of 40C (1C = 175 mAh g-1). In contrast, the sample synthesized without glucose as carbon source (denoted as S-LTO) experienced an obvious structural collapse during the hydrothermal reaction and presented a specific capacity of only 67 mAh g-1 at 1C, which further decreased to 14 mAh g-1 at 40C. Further morphological growth of the acanthosphere-like Li4Ti5O12 microspheres and their excellent performance as an anode in LIBs were also discussed in this work.

Structural characterisation and physical properties of Li MMnO 4 ( M=Cr, Ti) spinels

Science.gov (United States)

Arillo, M. A.; Cuello, G.; López, M. L.; Martín, P.; Pico, C.; Veiga, M. L.

2005-01-01

New spinel-type phases of general formula Li MMnO 4 ( M=Cr, Ti), derived from LiMn 2O 4 by substitution of Mn 3+ by Cr 3+ or Mn 4+ by Ti 4+, have been obtained and characterised. Neutron diffraction refinements confirm that both phases crystallise in the Fd3m space group, giving the cation distributions [Li] 8 a[CrMn] 16 dO 4 and [Li 0.66Ti 0.34] 8 a[Li 0.34MnTi 0.66] 16 dO 4. Electrical conductivity has been examined by various techniques showing that these materials behave as semiconductors. The electrochemical behaviour indicates different oxidation-reduction steps in both cases concomitant with the insertion/deinsertion of lithium in non-reversible processes. X-ray diffraction patterns show that the above process is topotactic in LiCrMnO 4. Magnetic data and neutron diffraction measurements show that no long-range magnetic ordering is present, suggesting a spin-glass transition for M=Cr at low temperature, while for M=Ti the presence of non-magnetic ions in the octahedral sublattice provokes an inherent magnetic frustration.

A new, high energy rechargeable lithium ion battery with a surface-treated Li{sub 1.2}Mn{sub 0.54}Ni{sub 0.13}Co{sub 0.13}O{sub 2} cathode and a nano-structured Li{sub 4}Ti{sub 5}O{sub 12} anode

Energy Technology Data Exchange (ETDEWEB)

Liu, Xiaoyu; Huang, Tao; Yu, Aishui, E-mail: asyu@fudan.edu.cn

2015-11-05

Through elaborate design, a new rechargeable lithium ion battery has been developed by comprising a surface-treated Li{sub 1.2}Mn{sub 0.54}Ni{sub 0.13}Co{sub 0.13}O{sub 2} cathode and a nano-structured Li{sub 4}Ti{sub 5}O{sub 12} anode. After precondition Na{sub 2}S{sub 2}O{sub 8} treatment, the initial coulombic efficiency of Li{sub 1.2}Mn{sub 0.54}Ni{sub 0.13}Co{sub 0.13}O{sub 2} cathode has been significantly increased and can be compatible with that of the nano-structured Li{sub 4}Ti{sub 5}O{sub 12} anode. The optimization of structure and morphology for both active electrode materials result in their remarkable electrochemical performances in respective lithium half-cells. Ultimately, the rechargeable lithium ion full battery consisting of both electrodes delivers a specific capacity of 99.0 mAh g{sup −1} and a practical energy density of 201 Wh kg{sup −1}, based on the total weight of both active electrode materials. Furthermore, as a promising candidate in the lithium ion battery field, this full battery also achieves highly attractive electrochemical performance with high coulombic efficiency, excellent cycling stability and outstanding rate capability. Thus the proposed battery displays broad practical application prospects for next generation of high-energy lithium ion battery. - Highlights: • The Li{sub 1.2}Mn{sub 0.54}Ni{sub 0.13}Co{sub 0.13}O{sub 2} cathode is surface-treated by Na{sub 2}S{sub 2}O{sub 8}. • The nano-sized Li{sub 4}Ti{sub 5}O{sub 12} anode is obtained by a solid-state method. • A new Li{sub 1.2}Mn{sub 0.54}Ni{sub 0.13}Co{sub 0.13}O{sub 2}/Li{sub 4}Ti{sub 5}O{sub 12} lithium ion battery is developed. • The battery shows high coulombic efficiency, specific capacity and energy density. • The battery shows high capacity retention rate and good high-rate capability.

High Tap Density Li4Ti5O12 Microspheres: Synthetic Conditions and Advanced Electrochemical Performance

KAUST Repository

Ming, Jun; Zheng, Junwei; Zhou, Qun; Ren, Jianxin; Ming, Hai; Jia, Zhenyong; Zhang, Yanqing

2017-01-01

Preparation of uniform spherical Li4Ti5O12 with high tap density is significant to achieve a high volumetric energy density in lithium-ion batteries. Herein, Li4Ti5O12 micro-spheres with variable tap-density and tunable size distribution were synthesized by a newly designed industrial spray drying approach. The slurry concentration, sintering time and sintering conditions after spray, the effect of Li/Ti molar ratio on the lithium ion (Li+) storage capability were investigated. A narrow particle size distribution around 10 μm and high tap-density close to 1.4 g cm-3 of the Li4Ti5O12 spheres can be obtained under the optimized conditions. The Li4Ti5O12 spheres can deliver much higher capacity of 168 mAh g-1 at 1 C-rate and show high capacity retention of 97.7% over 400 cycles. The synthetic conditions are confirmed to be critical for improving the electron conductivity and Li+ diffusivity by adjusting the crystal and spatial structures. As-prepared high performance Li4Ti5O12 is an ideal electrode for Li-ion batteries or capacitors; meanwhile the presented approach is also applicable for preparing other kind of spherical materials.

High Tap Density Li4Ti5O12 Microspheres: Synthetic Conditions and Advanced Electrochemical Performance

KAUST Repository

Ming, Jun

2017-03-17

Preparation of uniform spherical Li4Ti5O12 with high tap density is significant to achieve a high volumetric energy density in lithium-ion batteries. Herein, Li4Ti5O12 micro-spheres with variable tap-density and tunable size distribution were synthesized by a newly designed industrial spray drying approach. The slurry concentration, sintering time and sintering conditions after spray, the effect of Li/Ti molar ratio on the lithium ion (Li+) storage capability were investigated. A narrow particle size distribution around 10 μm and high tap-density close to 1.4 g cm-3 of the Li4Ti5O12 spheres can be obtained under the optimized conditions. The Li4Ti5O12 spheres can deliver much higher capacity of 168 mAh g-1 at 1 C-rate and show high capacity retention of 97.7% over 400 cycles. The synthetic conditions are confirmed to be critical for improving the electron conductivity and Li+ diffusivity by adjusting the crystal and spatial structures. As-prepared high performance Li4Ti5O12 is an ideal electrode for Li-ion batteries or capacitors; meanwhile the presented approach is also applicable for preparing other kind of spherical materials.

The 15th Internatonal Conference Quality in Resarch (Qir) 2017 Preparation and Ionic Conductivity of Li3.9Ca0.1Ti5O12 Using Waste Chicken Eggshells as ca Source for Anode Material of Lithium-Ion Batteries

Science.gov (United States)

Subhan, Achmad; Setiawan, Dedy; Ahmiatri Saptari, Sitti

2018-03-01

Li3.9Ca0.1Ti5O12 has been synthesized as anode material for lithium-ion batteries parallel with Li4Ti5O12 anode material using solid state reaction method in an air atmosphere. LiOH.H2O, TiO2, and waste chicken eggshells in the form of CaCO3 were chosen as sources of Li, Ti, and Ca respectively and prepared using stoichiometric. The phase structure, morphology, and electrochemical impedance of as-prepared samples were characterized using XRD, SEM, and EIS. The XRD characterization revealed that in Li3.9Ca0.1Ti5O12 sample, all amount of dopant had entered the lattice structure of Li4Ti5O12. The EDX image also detect the existence of Ca in the structure of Li3.9Ca0.1Ti5O12. The EIS characterization revealed that the Li3.9Ca0.1Ti5O12 sample had lower electrochemical impedance compared to the Li4Ti5O12 sample. The diffusion coefficient were obtained by Faraday’s method, and exhibited that the Li3.9Ca0.1Ti5O12 sample (1.46986 × 10-12 cm2/s) had higher ionic conductivity than the Li4Ti5O12 sample (4.40995 × 10-16 cm2/s). According to the cycle performance test, the Li3.9Ca0.1Ti5O12 sample also had higher charge-discharge capacity and stability compared to the Li4Ti5O12 sample.

Li_4Ti_5O_1_2/Ketjen Black with open conductive frameworks for high-performance lithium-ion batteries

International Nuclear Information System (INIS)

Zhang, Yang; Dong, Hui; Zhang, Huang; Liu, Yijun; Ji, Mandi; Xu, Yunlong; Wang, Qingqing; Luo, Lei

2016-01-01

Graphical abstract: The Li_4Ti_5O_1_2/Ketjen Black composites are synthesized via a simple hydrothermal method. As an anode for lithium ion battery, the composite exhibits ultrahigh capacity and excellent low temperature performance. - Highlights: • Mesoporous LTO/KB composites were synthesized via hydrothermal method. • KB is used as carbon template and conductive additive. • The LTO/KB electrode without carbon black was fabricated. • This as-prepared electrode shows excellent rate capacity performance. • LTO/KB composite exhibits ultrahigh cycle performance at low temperature. - Abstract: The Li_4Ti_5O_1_2/Ketjen Black composites are synthesized via a simple hydrothermal method. The materials are characterized by XRD, SEM, HR-TEM, EDS, galvanostatic charge/discharge test, CV and EIS. The results indicate that Li_4Ti_5O_1_2 (LTO) particles grow both in the pores and on the surface of mesoporous Ketjen Black (KB) forming open conductive frameworks and the Ketjen Black works as host forthe growth of Li_4Ti_5O_1_2 primary nanoparticles. The LTO/KB electrode is fabricated without extra carbon black conductive agents and exhibits excellent electrochemical performances, especially at low temperature. The improved performances can be attributed to the presence of mesoporous Ketjen Black conductive templates with high electronic conductivity and formed 3D frameworks beneficial to the lithium ion diffusion.

Li4Ti5O12/graphene nanoribbons composite as anodes for lithium ion batteries

CSIR Research Space (South Africa)

Medina IV, PA

2015-10-01

Full Text Available of GNRs was observed to have significantly improved the rate per- formance of LTO/GNTs. The specific capacities determined of the obtained composite at rates of 0.2, 0.5, 1, 2, and 5 C are 206.5, 200.9, 188, 178.1 and 142.3 mAh·g−1, respectively...- ated with unmodified Li4Ti5O12 is its poor rate per- formance, resulting from its inherent low electronic conductivity and moderate Li+ diffusion coefficient (Kavan et al. 2003; Wagemaker et al. 2008; Ouyang et al. 2007). Numerous strategies amongst...

Solid-state synthesis of Li_4Ti_5O_1_2 whiskers from TiO_2-B

International Nuclear Information System (INIS)

Yao, Wenjun; Zhuang, Wei; Ji, Xiaoyan; Chen, Jingjing; Lu, Xiaohua; Wang, Changsong

2016-01-01

Highlights: • The Li_4Ti_5O_1_2 whiskers were synthesized from TiO_2-B whiskers via a solid state reaction. • The TiO_2-B crystal structure for lithium diffusion is easier than anatase. • The separated diffusion and reaction process is crucial for the solid-state syntheses of Li_4Ti_5O_1_2 whiskers. - Abstract: In this work, Li_4Ti_5O_1_2 (LTO) was synthesized from the precursors of TiO_2-B and anatase whiskers, respectively. The synthesized LTO whiskers from TiO_2-B whiskers via a solid state reaction at 650 °C have a high degree of crystallinity with an average diameter of 300 nm. However, when anatase whiskers were used as the precursor, only particle morphology LTO was produced at 750 °C. The further analysis of the precursors, the intermediate products and the final products reveal that the crystal structure of the anatase hinders the diffusion of lithium, leading to a typical reaction–diffusion process. Under this condition, only particle morphology LTO can be produced. However, the crystal structure of the TiO_2-B is easy for lithium diffusion and the process is performed in two separated steps (i.e., diffusion and reaction), which makes it possible to decrease the solid-state reaction temperature down to 650 °C and then maintain the morphologies of whiskers.

Li insertion into Li4Ti5O12 spinel prepared by low temperature solid state route: Charge capability vs surface area

Czech Academy of Sciences Publication Activity Database

Zukalová, Markéta; Fabián, M.; Klusáčková, Monika; Klementová, Mariana; Pitňa Lásková, Barbora; Danková, Z.; Senna, M.; Kavan, Ladislav

2018-01-01

Roč. 265 (2018), s. 480-487 ISSN 0013-4686 R&D Projects: GA ČR GA15-06511S; GA MŠk LM2015087; GA MŠk 8F15003 Institutional support: RVO:61388955 ; RVO:68378271 Keywords : Li4Ti5O12 * Charge capacity * Solid state * Li insertion * Surface area Subject RIV: CG - Electrochemistry OBOR OECD: Electrochemistry (dry cells, batteries, fuel cells, corrosion metals, electrolysis) Impact factor: 4.798, year: 2016

Pseudocapacitive Behaviors of Li2FeTiO4/C Hybrid Porous Nanotubes for Novel Lithium-Ion Battery Anodes with Superior Performances.

Science.gov (United States)

Tang, Yakun; Liu, Lang; Zhao, Hongyang; Zhang, Yue; Kong, Ling Bing; Gao, Shasha; Li, Xiaohui; Wang, Lei; Jia, Dianzeng

2018-06-20

Hybrid nanotubes of cation disordered rock salt structured Li 2 FeTiO 4 nanoparticles embedded in porous CNTs were developed. Such unique hybrids with continuous 3D electron transportation paths and isolated small particles have been shown to be an ideal architecture that brought out enhanced electrochemical performances. Meanwhile, they exhibited improved extrinsic capacitive characteristics. In addition, we demonstrate a successful example to use cathode active material as anode for lithium-ion batteries (LIBs). More importantly, our hybrids had much superior electrochemical performances than most of the reported Li 4 Ti 5 O 12 -based nanocomposites. Therefore, it is concluded that Li 2 FeTiO 4 can be a prospective anode material for LIBs.

Deposition of Li{sub 4}Ti{sub 5}O{sub 12} and LiMn{sub 2}O{sub 4} films on the lithium-ion conductor of Li{sub 1.3}Al{sub 0.3}Ti{sub 1.7}(PO{sub 4}){sub 3} sintered pellet

Energy Technology Data Exchange (ETDEWEB)

Wu, Xian Ming, E-mail: xianmingwu@163.com [College of Chemistry and Chemical Engineering, Jishou University, Jishou Hunan 416000 (China); Xiangxi Minerals and New Materials Research and Service Center, Jishou Hunan 416000 (China); Chen, Shang [College of Chemistry and Chemical Engineering, Jishou University, Jishou Hunan 416000 (China); Xiangxi Minerals and New Materials Research and Service Center, Jishou Hunan 416000 (China); He, Ze Qiang; Chen, Shou Bin; Li, Run Xiu [College of Chemistry and Chemical Engineering, Jishou University, Jishou Hunan 416000 (China)

2015-08-31

LiMn{sub 2}O{sub 4} and Li{sub 4}Ti{sub 5}O{sub 12} films were deposited on the lithium-ion conductor of Li{sub 1.3}Al{sub 0.3}Ti{sub 1.7}(PO{sub 4}){sub 3} sintered pellet by spray technique. The effect of annealing temperature, annealing time, Li:Ti and Li:Mn molar ratio on the phase and crystallization of the films were investigated with X-ray diffraction. The LiMn{sub 2}O{sub 4}/Li{sub 1.3}Al{sub 0.3}Ti{sub 1.7}(PO{sub 4}){sub 3}/Li{sub 4}Ti{sub 5}O{sub 12} thin-film lithium-ion battery using Li{sub 1.3}Al{sub 0.3}Ti{sub 1.7}(PO{sub 4}){sub 3} sintered pellet as both electrolyte and substrate was also studied. The results show that the effect of annealing temperature, annealing time, Li:Ti and Li:Mn molar ratio has great effect on the phase and crystallization of Li{sub 4}Ti{sub 5}O{sub 12} and LiMn{sub 2}O{sub 4} films deposited on the Li{sub 1.3}Al{sub 0.3}Ti{sub 1.7}(PO{sub 4}){sub 3} sintered pellet. The optimal Li:Ti and Li:Mn molar ratio for the deposition of Li{sub 4}Ti{sub 5}O{sub 12} and LiMn{sub 2}O{sub 4} films on Li{sub 1.3}Al{sub 0.3}Ti{sub 1.7}(PO{sub 4}){sub 3} sintered pellet are 7.2:5 and 1.05:2, respectively. The optimal annealing temperature and time for the deposition of LiMn{sub 2}O{sub 4} film on Li{sub 1.3}Al{sub 0.3}Ti{sub 1.7}(PO{sub 4}){sub 3} sintered pellet are 650 °C and 10 min. While those for Li{sub 4}Ti{sub 5}O{sub 12} film are 700 °C and 10 min. The LiMn{sub 2}O{sub 4}/Li{sub 1.3}Al{sub 0.3}Ti{sub 1.7}(PO{sub 4}){sub 3}/Li{sub 4}Ti{sub 5}O{sub 12} thin-film battery offers a working voltage about 2.25 V and can be easily cycled. - Highlights: • LiMn{sub 2}O{sub 4} and Li{sub 4}Ti{sub 5}O{sub 12} films spray deposited on Li{sub 1.3}Al{sub 0.3}Ti{sub 1.7}(PO{sub 4}){sub 3} sintered pellet • Film crystal phase depends on the spray solution composition and annealing conditions. • Prepared thin-film lithium-ion battery employs sintered pellet as electrolyte and substrate. • LiMn{sub 2}O{sub 4}/Li{sub 1.3}Al{sub 0.3}Ti{sub 1

Order-disorder transition in the complex lithium spinel Li2CoTi3O8

International Nuclear Information System (INIS)

Reeves, Nik; Pasero, Denis; West, Anthony R.

2007-01-01

Li 2 CoTi 3 O 8 has an ordered Li 2 BB' 3 O 8 spinel structure, space group P4 3 32, at room temperature with 3:1 ordering of Ti and Li on the octahedral sites, and Li, Co disordered over the tetrahedral site. Rietveld refinement of variable temperature neutron powder diffraction data has shown an order-disorder phase transition in Li 2 CoTi 3 O 8 which commences at ∼500 deg. C with Li and Co mixing on the tetrahedral and 4-fold octahedral sites and is complete at a first order structural discontinuity at ∼915 deg. C. The fraction of Ti on the 12-fold octahedral site exhibits a small decrease with increasing temperature, which may suggest that the disordering involves all three cations. Above 930 deg. C, the structure, space group Fd3-barm, has Li, Co and Ti sharing a single-octahedral site and Li, Co sharing a tetrahedral site, although Co still exhibits a preference for tetrahedral coordination. A labelling scheme for ordered and partially ordered 3:1 spinels is devised which focuses on the occupancy of the Li,B cations. - Graphical abstract: Rietveld refinement of variable temperature neutron powder diffraction data shows an order-disorder phase transition in Li 2 CoTi 3 O 8 commencing at ∼500 deg. C with Li,Co mixing on tetrahedral and octahedral sites. This becomes complete at a first-order structural discontinuity at ∼915 deg. C. Above 930 deg. C, the structure, space group Fd3-barm, has Li, Co and Ti sharing a single-octahedral site and Li, Co sharing a tetrahedral site

Li_2ZrO_3-coated Li_4Ti_5O_1_2 with nanoscale interface for high performance lithium-ion batteries

International Nuclear Information System (INIS)

Zhang, Han; Liu, Yang; Wang, Ting; Yang, Yang; Shi, Shaojun; Yang, Gang

2016-01-01

Graphical abstract: - Highlights: • Zr doped and Li_2ZrO_3 coated Li_4Ti_5O_1_2 are prepared by a solid-state method. • Zr-doping and LZO coating are positive in improving lithium diffusion ability. • Li_2ZrO_3 coated Li_4Ti_5O_1_2 deliver 168.1 mAh g"−"1 higher than 150.2 mAh g"−"1 of Li_4Ti_5O_1_2. • Li_2ZrO_3 coated Li_4Ti_5O_1_2 remains 162 mAh g"−"1 after 100 cycles. • The lowest D_L_i"+ is 5.97 × 10"−"1"7 and 1.85 × 10"−"1"5 cm"2 s"−"1 of Li_4Ti_5O_1_2 before and after coating. - Abstract: Zr doped sample of Li_4Ti_4_._9_9Zr_0_._0_1O_1_2 (LZTO) and Li_2ZrO_3 (LZO) coated Li_4Ti_5O_1_2 (LTO) are prepared by a solid-state method. The lattice structure of LTO is remained after doping element of Zr and coating layer of LZO. The crystal structure and electrochemical performance of the material are investigated by X-ray diffractometry (XRD), high-resolution transmission electron microscopy (HRTEM), cyclic voltammetry (CV), galvanostatic intermittent titration technique (GITT) and charge-discharge tests, respectively. Zr-doping and LZO coating play the positive role in improving the diffusion ability of lithium cations. LZTO and LZO-LTO show much improved specific capacity and rate capability compared with pristine sample of LTO. LZO-LTO has the smallest voltage differential (ΔV) of the redox peaks because the coating of Li_2ZrO_3 is helpful for the diffusion ability of lithium ions during charge/discharge processes. LZTO and LZO-LTO as electrode deliver the initial capacities of 164.8, 168.1 mAh g"−"1, respectively, which are much higher than 150.2 mAh g"−"1 of intrinsic sample of LTO. Even at the current density of 2 A g"−"1, LTZO and LZO-LTO offer capacity of 96 and 106 mAh g"−"1, which are much higher than 33 mAh g"−"1 of LTO. The improved electrochemical performance is attributed to the improved diffusion ability of lithium. During the whole discharge process, the lowest value of LTO is 5.97 × 10"−"1"7 cm"2 s"−"1 that is

Depth profiling the solid electrolyte interphase on lithium titanate (Li4Ti5O12) using synchrotron-based photoelectron spectroscopy

DEFF Research Database (Denmark)

Nordh, Tim; Younesi, Reza; Brandell, Daniel

2015-01-01

The presence of a surface layer on lithium titanate (Li4Ti5O12, LTO) anodes, which has been a topic of debate in scientific literature, is here investigated with tunable high surface sensitive synchrotron-based photoelectron spectroscopy (PES) to obtain a reliable depth profile of the interphase...

Facile synthesis of hierarchically porous Li{sub 4}Ti{sub 5}O{sub 12} microspheres for high rate lithium ion batteries

Energy Technology Data Exchange (ETDEWEB)

Shen, L.F.; Luo, H.J.; Yuan, C.Z.; Su, X.F.; Xu, K.; Zhang, X.G. [Nanjing Univ. of Aeronautics and Astronautics (China). College of Material Science and Engineering

2010-07-01

Lithium-ion (Li-ion) batteries are used in electric vehicles (EVs) and hybrid electric vehicles (HEVs) due to their excellent energy storage capacity. Graphite is widely used as an anode material in EV and HEV applications. This study investigated the use of a lithium-titanium alloy (Li{sub 4}Ti{sub 5}O{sub 12}) designed to avoid reductions of the electrolyte on the surface of the electrode. The study showed that the composite material shows excellent cycling performance, excellent reversibility, structural stability, and Li-ion mobility in the charge-discharge process. A simple template-free hydrothermal method for fabricating Li{sub 4}Ti{sub 5}O{sub 12} hierarchical microspheres assembled by uniform nanoparticles was presented. The 1-step process produced microspheres with a high yield and uniform diameter. Details of the synthesis process, and the electrochemical and structural properties of the resulting materials were presented. 5 refs.

Solid-state synthesis of Li{sub 4}Ti{sub 5}O{sub 12} for high power lithium ion battery applications

Energy Technology Data Exchange (ETDEWEB)

Han, Seung-Woo [School of Materials Science and Engineering, Yeungnam University, Gyeongsan 712-749 (Korea, Republic of); Ryu, Ji Heon [Graduate School of Knowledge-Based Technology and Energy, Korea Polytechnic University, Siheung 429-793 (Korea, Republic of); Jeong, Joayoung [Cell Precedence Development Group, Samsung SDI, Yongin 446-577 (Korea, Republic of); Yoon, Dang-Hyok, E-mail: dhyoon@ynu.ac.kr [School of Materials Science and Engineering, Yeungnam University, Gyeongsan 712-749 (Korea, Republic of)

2013-09-05

Highlights: •High energy milling using 0.30 and 0.45 mm beads for Li{sub 4}Ti{sub 5}O{sub 12} synthesis. •Synthesis of 162 nm-sized pure Li{sub 4}Ti{sub 5}O{sub 12} by solid-state reaction. •Spray drying using fine starting materials to confer paste tackiness. •High capacity of 174 mAh/g and adequate rate properties for high power LIBs applications. -- Abstract: Li{sub 4}Ti{sub 5}O{sub 12} was synthesized by a solid-state reaction between Li{sub 2}CO{sub 3} and anatase TiO{sub 2} for applications to high power lithium ion batteries. The starting materials underwent 6 h of high energy milling using ZrO{sub 2} beads with two different sizes, 0.30 and 0.45 mm. The smaller ZrO{sub 2} beads resulted in finer starting materials. Spray drying was also performed on the 0.30 mm beads-treated particles to enhance the screen printability of a paste containing this powder. The finer starting materials showed a pure 162 nm-sized Li{sub 4}Ti{sub 5}O{sub 12} due to the decreased diffusion length for a solid-state reaction, whereas the 0.45 mm beads-treated starting materials resulted in a 242 nm-sized Li{sub 4}Ti{sub 5}O{sub 12} phase containing 2 wt.% of rutile TiO{sub 2} that had transformed from the anatase phase during heat treatment at 800 °C for 3 h. The finer Li{sub 4}Ti{sub 5}O{sub 12} showed higher charge capacity and better charge/discharge rates than the coarser particles, which highlights the importance of the primary particle size on the electrochemical properties of Li{sub 4}Ti{sub 5}O{sub 12} for high power applications. The fine Li{sub 4}Ti{sub 5}O{sub 12} particles had a discharge capacity of 174 mAh/g at 0.1 C and capacity retention of 80% at 10.0 C.

High-rate nano-crystalline Li{sub 4}Ti{sub 5}O{sub 12} attached on carbon nano-fibers for hybrid supercapacitors

Energy Technology Data Exchange (ETDEWEB)

Naoi, Katsuhiko; Isobe, Yusaku; Aoyagi, Shintaro [Institute of Symbiotic Science and Technology, Tokyo University of Agriculture and Technology, 2-24-16 Naka-cho, Koganei, Tokyo 184-8558 (Japan); Ishimoto, Shuichi [Institute of Symbiotic Science and Technology, Tokyo University of Agriculture and Technology, 2-24-16 Naka-cho, Koganei, Tokyo 184-8558 (Japan); Nippon Chemi-Con Corporation, 363 Arakawa, Takahagi-shi, Ibaraki 318-8505 (Japan)

2010-09-15

A lithium titanate (Li{sub 4}Ti{sub 5}O{sub 12})-based electrode which can operate at unusually high current density (300 C) was developed as negative electrode for hybrid capacitors. The high-rate Li{sub 4}Ti{sub 5}O{sub 12} electrode has a unique nano-structure consisting of unusually small nano-crystalline Li{sub 4}Ti{sub 5}O{sub 12} (ca. 5-20 nm) grafted onto carbon nano-fiber anchors (nc-Li{sub 4}Ti{sub 5}O{sub 12}/CNF). This nano-structured nc-Li{sub 4}Ti{sub 5}O{sub 12}/CNF composite are prepared by simple sol-gel method under ultra-centrifugal force (65,000 N) followed by instantaneous annealing at 900 C for 3 min. A model hybrid capacitor cell consisting of a negative nc-Li{sub 4}Ti{sub 5}O{sub 12}/CNF composite electrode and a positive activated carbon electrode showed high energy density of 40 Wh L{sup -1} and high power density of 7.5 kW L{sup -1} comparable to conventional EDLCs. (author)

Solid-state synthesis of Li{sub 4}Ti{sub 5}O{sub 12} whiskers from TiO{sub 2}-B

Energy Technology Data Exchange (ETDEWEB)

Yao, Wenjun [State Key Laboratory of Materials-Oriented Chemical Engineering, College of Chemical Engineering, Nanjing Tech University, No. 5 Xin Mofan Road, Nanjing 210009 (China); Zhuang, Wei [State Key Laboratory of Materials-Oriented Chemical Engineering, College of Chemical Engineering, Nanjing Tech University, No. 5 Xin Mofan Road, Nanjing 210009 (China); College of Biotechnology and Pharmaceutical Engineering, National Engineering Technique Research Center for Biotechnology, Nanjing Tech University, No. 30, Puzhu South Road, Nanjing 211816 (China); Ji, Xiaoyan [Division of Energy Science/Energy Engineering, Luleå University of Technology, Luleå 97187 Sweden (Sweden); Chen, Jingjing; Lu, Xiaohua [State Key Laboratory of Materials-Oriented Chemical Engineering, College of Chemical Engineering, Nanjing Tech University, No. 5 Xin Mofan Road, Nanjing 210009 (China); Wang, Changsong, E-mail: wcs@njtech.edu.cn [State Key Laboratory of Materials-Oriented Chemical Engineering, College of Chemical Engineering, Nanjing Tech University, No. 5 Xin Mofan Road, Nanjing 210009 (China)

2016-03-15

Highlights: • The Li{sub 4}Ti{sub 5}O{sub 12} whiskers were synthesized from TiO{sub 2}-B whiskers via a solid state reaction. • The TiO{sub 2}-B crystal structure for lithium diffusion is easier than anatase. • The separated diffusion and reaction process is crucial for the solid-state syntheses of Li{sub 4}Ti{sub 5}O{sub 12} whiskers. - Abstract: In this work, Li{sub 4}Ti{sub 5}O{sub 12} (LTO) was synthesized from the precursors of TiO{sub 2}-B and anatase whiskers, respectively. The synthesized LTO whiskers from TiO{sub 2}-B whiskers via a solid state reaction at 650 °C have a high degree of crystallinity with an average diameter of 300 nm. However, when anatase whiskers were used as the precursor, only particle morphology LTO was produced at 750 °C. The further analysis of the precursors, the intermediate products and the final products reveal that the crystal structure of the anatase hinders the diffusion of lithium, leading to a typical reaction–diffusion process. Under this condition, only particle morphology LTO can be produced. However, the crystal structure of the TiO{sub 2}-B is easy for lithium diffusion and the process is performed in two separated steps (i.e., diffusion and reaction), which makes it possible to decrease the solid-state reaction temperature down to 650 °C and then maintain the morphologies of whiskers.

True atomic-scale imaging of a spinel Li{sub 4}Ti{sub 5}O{sub 12}(111) surface in aqueous solution by frequency-modulation atomic force microscopy

Energy Technology Data Exchange (ETDEWEB)

Kitta, Mitsunori, E-mail: m-kitta@aist.go.jp; Kohyama, Masanori [Research Institute for Ubiquitous Energy Devices, National Institute of Advanced Industrial Science and Technology, 1-8-31 Midorigaoka, Ikeda, Osaka 563-8577 (Japan); Onishi, Hiroshi [Department of Chemistry, Graduate School of Science, Kobe University 1-1 Rokkodai, Nada, Kobe 657-8501 (Japan)

2014-09-15

Spinel-type lithium titanium oxide (LTO; Li{sub 4}Ti{sub 5}O{sub 12}) is a negative electrode material for lithium-ion batteries. Revealing the atomic-scale surface structure of LTO in liquid is highly necessary to investigate its surface properties in practical environments. Here, we reveal an atomic-scale image of the LTO(111) surface in LiCl aqueous solution using frequency-modulation atomic force microscopy. Atomically flat terraces and single steps having heights of multiples of 0.5 nm were observed in the aqueous solution. Hexagonal bright spots separated by 0.6 nm were also observed on the flat terrace part, corresponding to the atomistic contrast observed in the ultrahigh vacuum condition, which suggests that the basic atomic structure of the LTO(111) surface is retained without dramatic reconstruction even in the aqueous solution.

Novel peapoded Li4Ti5O12 nanoparticles for high-rate and ultralong-life rechargeable lithium ion batteries at room and lower temperatures

Science.gov (United States)

Peng, Liang; Zhang, Huijuan; Fang, Ling; Zhang, Yan; Wang, Yu

2016-01-01

In this paper, a novel peapod-like Li4Ti5O12-C composite architecture with high conductivity is firstly designed and synthesized to be used as anode materials for lithium-ion batteries. In the synthesis, Na2Ti3O7 nanotubes act as precursors and sacrificial templates, and glucose molecules serve as the green carbon source, thus the peapod-like Li4Ti5O12-C composite can be fabricated by a facile hydrothermal reaction and the subsequent solid-state process. Compared to the previous reports, the as-prepared samples obtained by our new strategy exhibit excellent electrochemical performances, such as outstanding rate capability (an extremely reversible capability of 148 mA h g-1, 125 mA h g-1 at 30 C and 90 C, respectively) as well as excellent cycling performance (about 5% capacity loss after 5000 cycles at 10 C with 152 mA h g-1 capacity retained). The low-temperature measurements also demonstrate that the electrochemical performances of the peapod-like Li4Ti5O12-C composite are remarkably improved at various rate currents (at the low-temperature of -25 °C, a high Coulombic efficiency of about 99% can be achieved after 500 cycles at 10 C).In this paper, a novel peapod-like Li4Ti5O12-C composite architecture with high conductivity is firstly designed and synthesized to be used as anode materials for lithium-ion batteries. In the synthesis, Na2Ti3O7 nanotubes act as precursors and sacrificial templates, and glucose molecules serve as the green carbon source, thus the peapod-like Li4Ti5O12-C composite can be fabricated by a facile hydrothermal reaction and the subsequent solid-state process. Compared to the previous reports, the as-prepared samples obtained by our new strategy exhibit excellent electrochemical performances, such as outstanding rate capability (an extremely reversible capability of 148 mA h g-1, 125 mA h g-1 at 30 C and 90 C, respectively) as well as excellent cycling performance (about 5% capacity loss after 5000 cycles at 10 C with 152 mA h g-1 capacity

Improving the fast discharge performance of high-voltage LiNi{sub 0.5}Mn{sub 1.5}O{sub 4} spinel by Cu{sup 2+}, Al{sup 3+}, Ti{sup 4+} tri-doping

Energy Technology Data Exchange (ETDEWEB)

Deng, Jicheng [Electronic Materials Research Laboratory, Key Laboratory of the Ministry of Education & International Center for Dielectric Research, Xi' an Jiaotong University, Xi' an (China); Shaanxi Engineering Research Center of Advanced Energy Materials & Devices, Xi' an Jiaotong University, Xi' an (China); Xu, Youlong, E-mail: ylxuxjtu@mail.xjtu.edu.cn [Electronic Materials Research Laboratory, Key Laboratory of the Ministry of Education & International Center for Dielectric Research, Xi' an Jiaotong University, Xi' an (China); Shaanxi Engineering Research Center of Advanced Energy Materials & Devices, Xi' an Jiaotong University, Xi' an (China); Xiong, Lilong; Li, Liang [Electronic Materials Research Laboratory, Key Laboratory of the Ministry of Education & International Center for Dielectric Research, Xi' an Jiaotong University, Xi' an (China); Sun, Xiaofei [Shaanxi Engineering Research Center of Advanced Energy Materials & Devices, Xi' an Jiaotong University, Xi' an (China); Zhang, Yuan [Electronic Materials Research Laboratory, Key Laboratory of the Ministry of Education & International Center for Dielectric Research, Xi' an Jiaotong University, Xi' an (China)

2016-08-25

The sluggish Li{sup +} ion diffusion coefficient at ∼4.7 V (vs. Li{sup +}/Li) greatly impairs the fast discharge performance of LiMn{sub 1.5}Ni{sub 0.5}O{sub 4} cathode material. Herein, a tri-doping strategy is proposed where Cu{sup 2+}, Al{sup 3+}, Ti{sup 4+} ions are partially substituted for Ni{sup 2+} and Mn{sup 4+}. Cu{sup 2+}, Al{sup 3+}, Ti{sup 4+} tri-doping effectively suppresses the Li{sub x}Ni{sub 1−x}O impurity phase, increases the cation mixing in the octahedral B-site in the spinel, enlarges the electronic conductivity, and enhances the structural stability. Most importantly, the Li{sup +} diffusion coefficients show a peculiar boost at 4.7 V by two orders of magnitude after tri-doping. Compared to the pristine LiMn{sub 1.5}Ni{sub 0.5}O{sub 4} (denoted P-LNM), the tri-doped Li[Ni{sub 0.455}Cu{sub 0.03}Al{sub 0.03}Mn{sub 1.455}Ti{sub 0.03}]O{sub 4} (denoted TD-LNM) exhibits much better fast discharge performance, delivering a specific capacity of ∼101 mAh g{sup −1} at 100 C discharge rate. - Graphical abstract: For the LiMn{sub 1.5}Ni{sub 0.5}O{sub 4} cathode material, the sluggish Li{sup +} ion diffusion coefficient around the ∼4.7 V (vs. Li{sup +}/Li) plateau greatly impair its fast discharge performance, which therefore limit its application in electric vehicles. Herein, a tri-doping strategy is proposed where Cu{sup 2+}, Al{sup 3+}, Ti{sup 4+} ions are partially substituted for Ni{sup 2+} and Mn{sup 4+}. After tri-doping, the Li{sup +} diffusion coefficient at 4.7 V (vs. Li{sup +}/Li) is boosted by two orders of magnitude. Compared to the pristine LiMn{sub 1.5}Ni{sub 0.5}O{sub 4} (denoted P-LNM), the tri-doped Li[Ni{sub 0.455}Cu{sub 0.03}Al{sub 0.03}Mn{sub 1.455}Ti{sub 0.03}]O{sub 4} (denoted TD-LNM) exhibits much better fast discharge performance, delivering a capacity of ∼101 mAh·g{sup −1} at 100 C discharge rate. - Highlights: • Cu, Al, Ti Tri-doping improves electronic conductivity of LiNi{sub 0.5}Mn{sub 1.5}O{sub 4}. • Cu

Li depletion effects on Li2TiO3 reaction with H2 in thermo-chemical environment relevant to breeding blanket for fusion power plants

International Nuclear Information System (INIS)

Alvani, Carlo; Casadio, Sergio; Contini, Vittoria; Giorgi, Rossella; Mancini, Maria Rita; Tsuchiya, Kunihiko; Kawamura, Hiroshi

2005-07-01

This is a report of the Working Group in the Subtask on Solid Breeder Blankets under the Implementing Agreement on a Co-operative Programme on Nuclear Technology of Fusion Reactors (International Energy Agency (IEA)). This Working Group (Task F and WG-F) was performed from 2000 to 2004 by a collaboration of European Union (EU) and Japan (JA). In this report, lithium depletion effects on the reaction of lithium titanate (Li 2 TiO 3 ) with hydrogen (H 2 ) in thermo-chemical environment were discussed. The reaction of Li 2 TiO 3 ceramics with H 2 was studied in a thermo-chemical environment simulating (excepting irradiation) that of the hottest pebble-bed zone of breeding-blanket actually designed for fusion power plants. This 'reduction' as performed at 900degC in Ar+0.1%H, purge gas (He+0.1%H 2 being the designed reference') was found to be enhanced by TiO 2 doping of the specimens of simulate 6 Li-burn-up expected to reach 20% at their end-of-life. The reaction rates, however, were so slow to be not significantly extrapolated to the breeder material service time (years). In Ar+3%H 2 , faster reaction rates allowed a better identification of the process evolution (kinetics) by Temperature-Programmed Reduction' (TPR) and 'Oxidation' (TPO), and combined TG-DTA thermal analysis. The reduction of pure Li 4/5 TiO 12/5 spinel phase to Li 4/5 TiO 12/5-y was found to reach in one day the steady state at the O-vacancy concentration y=0.2. Complimentary microscopy (SEM) and spectroscopy (XRD, XPS) techniques were used to characterize the reaction products among which the presence of the orthorhombic Li v TiO 2 (0 ≤ v ≤ 1/2) and Li 2 TiO 3 could be diagnosed. So that the complete spinel reduction to Li 1/2 TiO 2 was obtained according to a scheme involving the Li 1/2 TiO 2 -Li 4/5 TiO 12/5 spinel phase solid solution for which y=3v/(10-5v). The reduction rate of pure meta-titanate to Li 2 TiO 3-x was found much lower (x approx. = 0.01) and even possibly due to the presence

Highly-crystalline ultrathin Li4Ti5O12 nanosheets decorated with silver nanocrystals as a high-performance anode material for lithium ion batteries

Science.gov (United States)

Xu, G. B.; Li, W.; Yang, L. W.; Wei, X. L.; Ding, J. W.; Zhong, J. X.; Chu, Paul K.

2015-02-01

A novel composite of highly-crystalline ultrathin Li4Ti5O12 (LTO) nanosheets and Ag nanocrystals (denoted as LTO NSs/Ag) as an anode material for Li-ion batteries (LIBs) is prepared by hydrothermal synthesis, post calcination and electroless deposition. The characterizations of structure and morphology reveal that the LTO nanosheets have single-crystal nature with a thickness of about 10 nm and highly dispersed Ag nanocrystals have an average diameter of 5.8 nm. The designed LTO NSs/Ag composite takes advantage of both components, thereby providing large contact area between the electrolyte and electrode, low polarization of voltage difference, high electrical conductivity and lithium ion diffusion coefficient during electrochemical processes. The evaluation of its electrochemical performance demonstrates that the prepared LTO NSs/Ag composite has superior lithium storage performance. More importantly, this unique composite has an ability to deliver high reversible capacities with superlative cyclic capacity retention at different current rates, and exhibit excellent high-rate performance at a current rate as high as 30 C. Our results improve the current performance of LTO based anode material for LIBs.

On the synthesis, characterization, rationalization of the structure and the compositional formula of Ti-substituted Li0,5Fe2,5O4

International Nuclear Information System (INIS)

Widatallah, H.M.; Berry, F.J.; Moore, E.A.; Johnson, C.; Jartych, E.; Pekala, M.; Grabski, J.

2002-12-01

Spinel-related titanium-substituted Li 0.5 Fe 2.5 O 4 has been synthesised by heating a mixture of titanium-doped corundum-related α-Fe 2 O 3 with Li 2 CO 3 at 850 deg C which is ca. 250-350 deg C lower than temperatures at which the material is normally prepared conventionally. Moessbauer and magnetic measurements imply that the Ti 4+ ions substitute for octahedral Fe 3+ ions. Interatomic potential calculations support this substitution with the charge balance being maintained by Li + vacancies. This structural model leads to a compositional formula of the type Li (0.5-x) + Ti x 4+ Fe (2.5-x) 3+ O 4 which is shown to be more appropriate than the one generally used in the literature, namely Li (0.5+0.5x) + Ti x 4+ Fe (2.5-1.5x) 3+ O 4 . Some implications of the suggested formula are discussed including the possibility of the existence of a thermodynamically stable titanium ferrite of the form Ti 0.5 Fe 2 O 4 . (author)

Graphene supported Li{sub 2}SiO{sub 3}/Li{sub 4}Ti{sub 5}O{sub 12} nanocomposites with improved electrochemical performance as anode material for lithium-ion batteries

Energy Technology Data Exchange (ETDEWEB)

Wang, Qiufen, E-mail: grp2009wqf@163.com; Yang, Shuai; Miao, Juan, E-mail: miaojuan@hpu.edu.cn; Lu, Mengwei; Wen, Tao; Sun, Jiufang

2017-05-01

Highlights: • We synthesized Graphene supported Li{sub 2}SiO{sub 3}@Li{sub 4}Ti{sub 5}O{sub 12}. • The discharge capacity is 399.2 mAh g{sup −1} at the current density of 150 mA g{sup −1} after 200 cycles. • The charge rate capacities retain 89.1% at the current density from 150 mA g{sup −1} to 750 mA g{sup −1}. • The recovery rates of the charge capacities are 91.0% when returned the current density of 150 mA g{sup −1}. - Abstract: Graphene supported Li{sub 2}SiO{sub 3}@Li{sub 4}Ti{sub 5}O{sub 12} (GE@LSO/LTO) nanocomposites have been synthesized via a hydrothermal route and following calcination. LSO/LTO nanospheres are adhered to the graphene nanosheets with the size of 50–100 nm, in which both LSO and LTO particles are attached together. When tested as the anode for lithium ion batteries, the initial discharge and charge capacities of GE@LSO/LTO are 720.6 mAh g{sup −1} and 463.4 mAh g{sup −1} at the current density of 150 mA g{sup −1}. After 200 cycles, the discharge and charge capacities can be remained of 399.2 mAh g{sup −1} and 398.9 mAh g{sup −1}, respectively. Moreover, the charge rate capacities of GE@LSO/LTO composites retain 89.1% at the range of current density from 150 mA g{sup −1} to 750 mA g{sup −1}. And its recovery rates are 91.0% when the current density back to 150 mA g{sup −1}. In addition, the reversible capacity and cycle stability of GE@LSO/LTO are better than that of LTO and LSO/LTO. The reasons can be attributed to the synergistic effect between GE and LSO/LTO as well as the features of GE supports.

Li{sub 2}ZrO{sub 3}-coated Li{sub 4}Ti{sub 5}O{sub 12} with nanoscale interface for high performance lithium-ion batteries

Energy Technology Data Exchange (ETDEWEB)

Zhang, Han [Jiangsu Lab of Advanced Functional Material, Changshu Institute of Technology, Changshu, 215500 (China); School of Chemical Engineering & Technology, China University of Mining and Technology, Xuzhou 221116 (China); Liu, Yang [School of Chemical Engineering & Technology, China University of Mining and Technology, Xuzhou 221116 (China); Wang, Ting; Yang, Yang [Jiangsu Lab of Advanced Functional Material, Changshu Institute of Technology, Changshu, 215500 (China); Shi, Shaojun [School of Chemical Engineering & Technology, China University of Mining and Technology, Xuzhou 221116 (China); Yang, Gang, E-mail: gyang@cslg.edu.cn [Jiangsu Lab of Advanced Functional Material, Changshu Institute of Technology, Changshu, 215500 (China); School of Chemical Engineering & Technology, China University of Mining and Technology, Xuzhou 221116 (China)

2016-04-15

Graphical abstract: - Highlights: • Zr doped and Li{sub 2}ZrO{sub 3} coated Li{sub 4}Ti{sub 5}O{sub 12} are prepared by a solid-state method. • Zr-doping and LZO coating are positive in improving lithium diffusion ability. • Li{sub 2}ZrO{sub 3} coated Li{sub 4}Ti{sub 5}O{sub 12} deliver 168.1 mAh g{sup −1} higher than 150.2 mAh g{sup −1} of Li{sub 4}Ti{sub 5}O{sub 12}. • Li{sub 2}ZrO{sub 3} coated Li{sub 4}Ti{sub 5}O{sub 12} remains 162 mAh g{sup −1} after 100 cycles. • The lowest D{sub Li}{sup +} is 5.97 × 10{sup −17} and 1.85 × 10{sup −15} cm{sup 2} s{sup −1} of Li{sub 4}Ti{sub 5}O{sub 12} before and after coating. - Abstract: Zr doped sample of Li{sub 4}Ti{sub 4.99}Zr{sub 0.01}O{sub 12} (LZTO) and Li{sub 2}ZrO{sub 3} (LZO) coated Li{sub 4}Ti{sub 5}O{sub 12} (LTO) are prepared by a solid-state method. The lattice structure of LTO is remained after doping element of Zr and coating layer of LZO. The crystal structure and electrochemical performance of the material are investigated by X-ray diffractometry (XRD), high-resolution transmission electron microscopy (HRTEM), cyclic voltammetry (CV), galvanostatic intermittent titration technique (GITT) and charge-discharge tests, respectively. Zr-doping and LZO coating play the positive role in improving the diffusion ability of lithium cations. LZTO and LZO-LTO show much improved specific capacity and rate capability compared with pristine sample of LTO. LZO-LTO has the smallest voltage differential (ΔV) of the redox peaks because the coating of Li{sub 2}ZrO{sub 3} is helpful for the diffusion ability of lithium ions during charge/discharge processes. LZTO and LZO-LTO as electrode deliver the initial capacities of 164.8, 168.1 mAh g{sup −1}, respectively, which are much higher than 150.2 mAh g{sup −1} of intrinsic sample of LTO. Even at the current density of 2 A g{sup −1}, LTZO and LZO-LTO offer capacity of 96 and 106 mAh g{sup −1}, which are much higher than 33 mAh g{sup −1} of LTO

Electrochemical studies on electrospun Li(Li1/3Ti5/3)O4 grains as an anode for Li-ion batteries

International Nuclear Information System (INIS)

Wu Yongzhi; Reddy, M.V.; Chowdari, B.V.R.; Ramakrishna, S.

2012-01-01

Highlights: ► We report (Li(Li 1/3 Ti 5/3 )O 4 ) (LTO) obtained via electrospinning and followed by heat treatment. ► Electrochemical studies on nano-LTO showed a reversible capacity of 165(±3) mAh g −1 and 78(±3) mAh g −1 at a current rate of 0.2 C and 10 C, respectively. ► Electrode kinetics studies of LTO were carried out the end of 380 cycle using GITT and EIS techniques. - Abstract: Li(Li 1/3 Ti 5/3 )O 4 or (Li 4 Ti 5 O 12 ) (LTO) grains are prepared via electrospinning a solution containing lithium acetate, titanium tetra(IV)-isopropoxide, polyvinyl acetate and acetic acid in N,N-dimethyl-formamide, followed by a subsequent sintering process. The structures and morphology were characterized by X-ray diffraction, scanning and transmission microscopy. Coin-type cells were assembled to test the electrochemical performance was evaluated using galvanostatic cycling at room temperature, in the cycling range, 1.0–2.8 V. The Li-cycling results showed characteristic discharge-charge plateaus at 1.55 and 1.8 V vs. Li/Li + , respectively. Electrospun LTO showed a reversible capacity of 165(±3) mAh g −1 at the end of 10th cycle at a current rate of 0.2 C. The later studies on rate capacities and cycling performance of LTO grains demonstrate good rate performance and long term cycling stability. Galvanostatic Intermittent Titration Technique (GITT) and Electrochemical Impedance Spectroscopy (EIS) studied were carried out at end of 381st and 382nd cycle to understand the electrode kinetics.

Effects of the LiFePO4 content and the preparation method on the properties of (LiFePO4+AC/Li4Ti5O12 hybrid battery–capacitors

Directory of Open Access Journals (Sweden)

XUE BU HU

2010-09-01

Full Text Available Two composite cathode materials containing LiFePO4 and activated carbon (AC were synthesized by an in-situ method and a direct mixing technique, which are abbreviated as LAC and DMLAC, respectively. Hybrid battery–capacitors LAC/Li4Ti5O12 and DMLAC/Li4Ti5O12 were then assembled. The effects of the content of LiFePO4 and the preparation method on the cyclic voltammograms, the rate of charge–discharge and the cycle performance of the hybrid battery–capacitors were investigated. The results showed the overall electrochemical performance of the hybrid battery–capacitors was the best when the content of LiFePO4 in the composite cathode materials was in the range from 11.8 to 28.5 wt. %, while the preparation method had almost no impact on the electrochemical performance of the composite cathodes and hybrid battery–capacitors. Moreover, the hybrid battery–capacitor devices had a good cycle life performance at high rates. After 1000 cycles, the capacity loss of the DMLAC/Li4Ti5O12 hybrid battery–capacitor device at 4C was no more than 4.8 %. Moreover, the capacity loss would be no more than 9.6 % after 2000 cycles at 8C.

Spherical Li{sub 4}Ti{sub 5}O{sub 12} synthesized by spray drying from a different kind of solution

Energy Technology Data Exchange (ETDEWEB)

He Zhenjiang [School of Metallurgical Science and Engineering, Central South University, Changsha 410083 (China); Wang Zhixing, E-mail: zhixingwang163@163.com [School of Metallurgical Science and Engineering, Central South University, Changsha 410083 (China); Wu Feixiang; Guo Huajun; Li Xinhai; Xiong Xunhui [School of Metallurgical Science and Engineering, Central South University, Changsha 410083 (China)

2012-11-05

Highlights: Black-Right-Pointing-Pointer The precursor powders comprise hollow particles. Black-Right-Pointing-Pointer H{sub 2}O{sub 2} acts as coordination agent that reacts with the Ti to form a large anion. Black-Right-Pointing-Pointer Li{sub 4}Ti{sub 5}O{sub 12} powders can be synthesized at a low temperature of 700 Degree-Sign C. Black-Right-Pointing-Pointer The spherical Li{sub 4}Ti{sub 5}O{sub 12} powders show excellent electrochemical performance. Black-Right-Pointing-Pointer We hope our work will be helpful for other research groups. - Abstract: High energy density Li{sub 4}Ti{sub 5}O{sub 12} powders comprising of spherical nanocrystalline are synthesized by spray drying followed by solid-state calcination. The influences of Li/Ti atomic ratios (0.784, 0.800, 0.816, and 0.832) on the performance of Li{sub 4}Ti{sub 5}O{sub 12} are investigated by means of Thermogravimetric analysis (TGA), X-ray diffraction (XRD), scanning electron microscopy (SEM), Transmission electron microscope (TEM), Galvanostatic cell cycling, as well as Ac impedance spectroscopy. The results indicate that, when the spray-drying precursors at the Li/Ti molar ratio of 0.816 are calcined at 700 Degree-Sign C for 16 h in air, a pure LTO phase with a lithium-excess composition is obtained, which shows the best properties. Between 1.0 and 2.5 V (vs. Li/Li{sup +}), the initial discharge capacities of the powder are 174, 168, 163, 153, and 136 mAhg{sup -1} at a constant current density of 0.1, 0.5, 1, 2, and 5 C, respectively. After 100 cycles, the discharge capacities of the LTO powders remain 97, 95, and 99% of initial discharge capacities at current densities of 1, 2, and 5 C, respectively.

Cycling Performance of Li4Ti5O12 Electrodes in Ionic Liquid-Based Gel Polymer Electrolytes

International Nuclear Information System (INIS)

Kim, Jin Hee; Kim, Dong Won; Kang, Yong Ku

2012-01-01

We investigated the cycling behavior of Li 4 Ti 5 O 12 electrode in a cross-linked gel polymer electrolyte based on non-flammable ionic liquid consisting of 1-butyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl) imide and vinylene carbonate. The Li 4 Ti 5 O 12 electrodes in ionic liquid-based gel polymer electrolytes exhibited reversible cycling behavior with good capacity retention. Cycling data and electrochemical impedance spectroscopy analyses revealed that the optimum content of the cross-linking agent necessary to ensure both acceptable initial discharge capacity and good capacity retention was about 8 wt %

Phase-pure Nanocrystalline Li4Ti5O12 for Lithium ion Battery

Czech Academy of Sciences Publication Activity Database

Kalbáč, Martin; Zukalová, Markéta; Kavan, Ladislav

2003-01-01

Roč. 8, č. 1 (2003), s. 2-6 ISSN 1432-8488 R&D Projects: GA MŠk OC D14.10 Institutional research plan: CEZ:AV0Z4040901 Keywords : phase purity * Li4Ti5O12 * nanocrystalline materials Subject RIV: CG - Electrochemistry Impact factor: 1.195, year: 2003

700 F hybrid capacitors cells composed of activated carbon and Li4Ti5O12 microspheres with ultra-long cycle life

Science.gov (United States)

Ruan, Dianbo; Kim, Myeong-Seong; Yang, Bin; Qin, Jun; Kim, Kwang-Bum; Lee, Sang-Hyun; Liu, Qiuxiang; Tan, Lei; Qiao, Zhijun

2017-10-01

To address the large-scale application demands of high energy density, high power density, and long cycle lifetime, 700-F hybrid capacitor pouch cells have been prepared, comprising ∼240-μm-thick activated carbon cathodes, and ∼60-μm-thick Li4Ti5O12 anodes. Microspherical Li4Ti5O12 (M-LTO) synthesized by spray-drying features 200-400 nm primary particles and interconnected nanopore structures. M-LTO half-cells exhibits high specific capacities (175 mAhh g-1), good rate capabilities (148 mAhh g-1 at 20 C), and ultra-long cycling stabilities (90% specific capacity retention after 10,000 cycles). In addition, the obtained hybrid capacitors comprising activated carbon (AC) and M-LTO shows excellent cell performances, achieving a maximum energy density of 51.65 Wh kg-1, a maximum power density of 2466 W kg-1, and ∼92% capacitance retention after 10,000 cycles, thus meeting the demands for large-scale applications such as trolleybuses.

Crystallographic origin of cycle decay of the high-voltage LiNi0.5Mn1.5O4 spinel lithium-ion battery electrode.

Science.gov (United States)

Pang, Wei Kong; Lu, Cheng-Zhang; Liu, Chia-Erh; Peterson, Vanessa K; Lin, Hsiu-Fen; Liao, Shih-Chieh; Chen, Jin-Ming

2016-06-29

High-voltage spinel LiNi0.5Mn1.5O4 (LNMO) is considered a potential high-power-density positive electrode for lithium-ion batteries, however, it suffers from capacity decay after extended charge-discharge cycling, severely hindering commercial application. Capacity fade is thought to occur through the significant volume change of the LNMO electrode occurring on cycling, and in this work we use operando neutron powder diffraction to compare the structural evolution of the LNMO electrode in an as-assembled 18650-type battery containing a Li4Ti5O12 negative electrode with that in an identical battery following 1000 cycles at high-current. We reveal that the capacity reduction in the battery post cycling is directly proportional to the reduction in the maximum change of the LNMO lattice parameter during its evolution. This is correlated to a corresponding reduction in the MnO6 octahedral distortion in the spinel structure in the cycled battery. Further, we find that the rate of lattice evolution, which reflects the rate of lithium insertion and removal, is ∼9 and ∼10% slower in the cycled than in the as-assembled battery during the Ni(2+)/Ni(3+) and Ni(3+)/Ni(4+) transitions, respectively.

Enhanced high-potential and elevated-temperature cycling stability of LiMn2O4 cathode by TiO2 modification for Li-ion battery

International Nuclear Information System (INIS)

Yu Lihong; Qiu Xinping; Xi Jingyu; Zhu Wentao; Chen Liquan

2006-01-01

The surface of spinel LiMn 2 O 4 was modified with TiO 2 by a simple sol-gel method to improve its electrochemical performance at elevated temperatures and higher working potentials. Compared with pristine LiMn 2 O 4 , surface-modification improved the cycling stability of the material. The capacity retention of TiO 2 -modified LiMn 2 O 4 was more than 85% after 60 cycles at high potential cycles between 3.0 and 4.8 V at room temperature and near to 90% after 30 cycles at elevated temperature of 55 deg. C at 1C charge-discharge rate. SEM studies shows that the surface morphology of TiO 2 -modified LiMn 2 O 4 was different from that of pristine LiMn 2 O 4 . Powder X-ray diffraction indicated that spinel was the only detected phase in TiO 2 -modified LiMn 2 O 4 . Introduction of Ti into LiMn 2 O 4 changed the electronic structures of the particle surface. Therefore a surface solid compound of LiTi x Mn 2-x O 4 may be formed on LiMn 2 O 4 . The improved electrochemical performance of surface-modified LiMn 2 O 4 was attributed to the improved stability of crystalline structure and the higher Li + conductivity

Synthesis of graphitized carbon, nanodiamond and graphene supported Li_4Ti_5O_1_2 and comparison of their electrochemical performance as anodes for lithium ion batteries

International Nuclear Information System (INIS)

Yang, Shuai; Miao, Juan; Wang, Qiufen; Lu, Mengwei; Sun, Jiufang; Wen, Tao

2016-01-01

Highlights: • We synthesized graphitized carbon, nanodiamond and graphene supported Li_4Ti_5O_1_2, respectively. • The order of the capacities is LTO/GE > LTO/GC > LTO > LTO/ND after 500 cycles. • The rate capabilities and cycling stabilities are in the order of LTO/GE > LTO/ND > LTO/GC > LTO. - Abstract: Graphitized carbon (GC), nanodiamond (ND) and graphene (GE) supported Li_4Ti_5O_1_2 (LTO) composites have been synthesized via a solid-state reaction, respectively. The particle sizes of LTO/GC, LTO/ND and LTO/GE are smaller than pure LTO. When tested as the anode for lithium ion batteries, the discharge capacities of LTO, LTO/GC, LTO/ND and LTO/GE composites are 100.1 mAh g"−"1, 150.4 mAh g"−"1, 90.4 mAh g"−"1 and 218.3 mAh g"−"1 at the current density of 175 mA g"−"1 after 500 cycles. Their rate capacities retain 59.8%, 80.0%, 81.0% and 85.7% at the current density of 175 mA g"−"1, 438 mA g"−"1, 875 mA g"−"1 and 175 mA g"−"1, respectively. Moreover, the recovery rates of their rate capacities are 78.6%, 83.4%, 88.9% and 90.1% when returned to the current density of 175 mA g"−"1, respectively. The reasons can be attributed to the synergistic effect between GC (ND and GE) and LTO as well as the features of the different carbon supports. This strategy, with the carbon constituting a good supporting structure, is an effective way to improve the cycling performance of anode materials for lithium ion batteries.

Effect of freeze-drying and self-ignition process on the microstructural and electrochemical properties of Li{sub 4}Ti{sub 5}O{sub 12}

Energy Technology Data Exchange (ETDEWEB)

Jamin, Claire [GREEnMat/LCIS, Department of Chemistry, B6a, University of Liège, Sart-Tilman, 4000 Liège (Belgium); Traina, Karl [GREEnMat/LCIS, Department of Chemistry, B6a, University of Liège, Sart-Tilman, 4000 Liège (Belgium); APTIS, Department of Physics, B5a, University of Liège, Sart-Tilman, 4000 Liège (Belgium); Eskenazi, David [Chemical Engineering Laboratory, Department of Applied Chemistry, B6a, University of Liège, Sart-Tilman, 4000 Liège (Belgium); Krins, Natacha; Cloots, Rudi; Vertruyen, Bénédicte [GREEnMat/LCIS, Department of Chemistry, B6a, University of Liège, Sart-Tilman, 4000 Liège (Belgium); Boschini, Frédéric, E-mail: frederic.boschini@ulg.ac.be [GREEnMat/LCIS, Department of Chemistry, B6a, University of Liège, Sart-Tilman, 4000 Liège (Belgium); APTIS, Department of Physics, B5a, University of Liège, Sart-Tilman, 4000 Liège (Belgium)

2013-11-15

Graphical abstract: - Highlights: • Li{sub 4}Ti{sub 5}O{sub 12} is prepared by a method involving self-ignition of a freeze-dried gel. • Addition of NH{sub 4}NO{sub 3} modifies the self-ignition propagation mode. • Well-crystallized Li{sub 4}Ti{sub 5}O{sub 12} phase is obtained after only 2 h at 800 °C. • Li{sub 4}Ti{sub 5}O{sub 12} powder has 161 mAh g{sup −1} capacity and good retention at C/4 rate. - Abstract: Crystalline Li{sub 4}Ti{sub 5}O{sub 12} is synthesized by a method involving the freeze-drying and self-ignition of a gel prepared from titanium isopropoxide, lithium nitrate and hydroxypropylmethylcellulose (HPMC). This synthesis route yields crystalline Li{sub 4}Ti{sub 5}O{sub 12} particles after calcination at 800 °C for 2 h. In an alternative route, addition of ammonium nitrate shifts the self-ignition mode from wave-like propagation to simultaneous. Powders with different microstructures are thereby obtained. Electrochemical characterization shows that the best results for Li{sup +} intercalation/desintercalation are obtained for the powder prepared without ammonium nitrate addition. These results highlight the necessity for a control of the self-ignition mode to obtain adequate properties.

Spinel Li2CoTi3O8 nanometer obtained for application as pigment

International Nuclear Information System (INIS)

Costa de Camara, M. S.; Alves Pimentel, L.; Longo, E.; Nobrega Azevedo, L. da; Araujo Melo, D. M. de

2016-01-01

Pigments are used in ceramics, cosmetics, inks, and other applications widely materials. To this must be single and easily reproducible. Moreover, the pigments obtained in the nanoscale are more stable, reproducible and highlight color in small amounts compared with those obtained in micrometer scale. The mixed oxides with spinel structures AB 2 O 4 have important applications, including: pigments, refractories, catalytic and electronic ceramics. In this context, the aim of this work was the preparation of powder Li 2 CoTi 3 O 8 spinel phase with nanometer particle size of the polymeric precursor method (Pechini) and characterization by means of thermal analysis (TG/DTA) X-ray diffraction (XRD), refined by the Rietveld method, BET, transmission electron microscopy (TEM), Raman and colorimetric coordinates. The pigment was obtained by heat treatment of 400 degree centigrade to 1000 degree centigrade after pyrolysis at 300 degree centigrade/1 h for removing the organic material. Li 2 CoTi 3 O 8 desired spinel phase was obtained from 500 degree centigrade, and presenting stability nanometer to about 1.300 degree centigrade. Spinel green phase introduced at temperatures in the range of 400 degree centigrade and 500 degree centigrade, and 600 degree centigrade at temperatures between blue and 1000 degree centigrade. (Author)

Effects of carbon source and carbon content on electrochemical performances of Li{sub 4}Ti{sub 5}O{sub 12}/C prepared by one-step solid-state reaction

Energy Technology Data Exchange (ETDEWEB)

Hu Xuebu [College of Chemistry and Materials Science, Sichuan Normal University, Chengdu, Sichuan 610066 (China); Chengdu Institute of Organic Chemistry, Chinese Academy of Sciences, Chengdu, Sichuan 610041 (China); Lin Ziji [China National Quality Supervision and Inspection Center for Alcoholic Beverage Products and Processed Food, Luzhou, Sichuan 646100 (China); Yang Kerun [Chengdu Institute of Organic Chemistry, Chinese Academy of Sciences, Chengdu, Sichuan 610041 (China); Hua, Yongjian [China Aviation Lithium Battery Co. Ltd., Luoyang, Henan 471009 (China); Deng Zhenghua, E-mail: zhdeng@cioc.ac.cn [Chengdu Institute of Organic Chemistry, Chinese Academy of Sciences, Chengdu, Sichuan 610041 (China)

2011-05-30

Highlights: > A simple route to prepare the Li{sub 4}Ti{sub 5}O{sub 12}/C by one-step solid-state reaction. > Carbon source and carbon content are two important factors on the electrochemical performances of Li{sub 4}Ti{sub 5}O{sub 12}/C. > As-prepared Li{sub 4}Ti{sub 5}O{sub 12}/C under optimized conditions shows excellent electrochemical performances. - Abstract: Li{sub 4}Ti{sub 5}O{sub 12}/C composites were synthesized by one-step solid-state reaction method using four commonly used organic compounds or organic polymers as carbon source, i.e., polyacrylate acid (PAA), citric acid (CA), maleic acid (MA) and polyvinyl alcohol (PVA). The physical characteristics of Li{sub 4}Ti{sub 5}O{sub 12}/C composites were investigated by X-ray diffraction, electron microscopy, Raman spectroscopy, particle size distribution and thermogravimetry-derivative thermogravimetry techniques. Their electrochemical properties were characterized by cyclic voltammograms, electrochemical impedance spectra, constant current charge-discharge and rate charge-discharge. These analyses indicated that the carbon source and carbon content have a great effect on the physical and electrochemical performances of Li{sub 4}Ti{sub 5}O{sub 12}/C composites. An ideal carbon source and appropriate carbon content effectively improved the electrical contact between the Li{sub 4}Ti{sub 5}O{sub 12} particles, which enhanced the discharge capacity and rate capability of Li{sub 4}Ti{sub 5}O{sub 12}/C composites. PAA was the best carbon source for the synthesis of Li{sub 4}Ti{sub 5}O{sub 12}/C composites. When the carbon content was 3.49 wt.% (LiOH.H{sub 2}O/PAA molar ratio of 1), as-prepared Li{sub 4}Ti{sub 5}O{sub 12}/C showed the maximum discharge capacity. At 0.2 C, initial capacity of the optimized sample was 168.6 mAh g{sup -1} with capacity loss of 2.8% after 50 cycles. At 8 and 10 C, it showed discharge capacities of 143.5 and 132.7 mAh g{sup -1}, with capacity loss of 8.7 and 9.9% after 50 cycles

Adhesive PEG-based binder for aqueous fabrication of thick Li4Ti5O12 electrode

International Nuclear Information System (INIS)

Tran, Binh; Oladeji, Isaiah O.; Wang, Zedong; Calderon, Jean; Chai, Guangyu; Atherton, David; Zhai, Lei

2013-01-01

We report the first fully compressed Li 4 Ti 5 O 12 electrode designed by an aqueous process. An adhesive, elastomeric, and lithium ion conductive PEG-based copolymer is used as a binder for the aqueous fabrication thick, flexible, and densely packed Li 4 Ti 5 O 12 (LTO) electrodes. Self-adherent cathode films exceeding 200 μm in thickness and withholding high active mass loadings of 28 mg/cm 2 deliver 4.2 mAh/cm 2 at C/2 rate. Structurally defect-free electrodes are fabricated by casting aqueous cathode slurries onto nickel foam, dried, and hard-calendared at 10 tons/cm 2 . As a multifunctional material, the binder is synthesized by the copolymerization of poly(ethylene glycol) methyl ether methacrylate (PEGMA), methyl methacrylate (MMA), and isobutyl vinyl ether (IBVE) in optimal proportions. Furthermore, coordinating the binder with lithium salt is necessary for the electrode to function

The Formation of Lithiated Ti-Doped α-Fe2O3 Nanocrystalline Particles by Mechanical Milling of Ti-Doped Lithium Spinel Ferrite

International Nuclear Information System (INIS)

Widatallah, H. M.; Gismelseed, A. M.; Bouziane, K.; Berry, F. J.; Al Rawas, A. D.; Al-Omari, I. A.; Yousif, A. A.; Elzain, M. E.

2004-01-01

The milling of spinel-related Ti-doped Li 0.5 Fe 2.5 O 4 for different times is studied with XRD, Moessbauer spectroscopy and magnetic measurements. Milling converts the material to Li-Ti-doped α-Fe 2 O 3 nanocrystalline particles via an intermediate γ-LiFeO 2 -related phase. The role played by the dopant Ti-ion in the process is emphasized.

Synthesis of graphitized carbon, nanodiamond and graphene supported Li{sub 4}Ti{sub 5}O{sub 12} and comparison of their electrochemical performance as anodes for lithium ion batteries

Energy Technology Data Exchange (ETDEWEB)

Yang, Shuai; Miao, Juan, E-mail: miaojuan@hpu.edu.cn; Wang, Qiufen, E-mail: grp2009wqf@163.com; Lu, Mengwei; Sun, Jiufang; Wen, Tao

2016-12-15

Highlights: • We synthesized graphitized carbon, nanodiamond and graphene supported Li{sub 4}Ti{sub 5}O{sub 12}, respectively. • The order of the capacities is LTO/GE > LTO/GC > LTO > LTO/ND after 500 cycles. • The rate capabilities and cycling stabilities are in the order of LTO/GE > LTO/ND > LTO/GC > LTO. - Abstract: Graphitized carbon (GC), nanodiamond (ND) and graphene (GE) supported Li{sub 4}Ti{sub 5}O{sub 12} (LTO) composites have been synthesized via a solid-state reaction, respectively. The particle sizes of LTO/GC, LTO/ND and LTO/GE are smaller than pure LTO. When tested as the anode for lithium ion batteries, the discharge capacities of LTO, LTO/GC, LTO/ND and LTO/GE composites are 100.1 mAh g{sup −1}, 150.4 mAh g{sup −1}, 90.4 mAh g{sup −1} and 218.3 mAh g{sup −1} at the current density of 175 mA g{sup −1} after 500 cycles. Their rate capacities retain 59.8%, 80.0%, 81.0% and 85.7% at the current density of 175 mA g{sup −1}, 438 mA g{sup −1}, 875 mA g{sup −1} and 175 mA g{sup −1}, respectively. Moreover, the recovery rates of their rate capacities are 78.6%, 83.4%, 88.9% and 90.1% when returned to the current density of 175 mA g{sup −1}, respectively. The reasons can be attributed to the synergistic effect between GC (ND and GE) and LTO as well as the features of the different carbon supports. This strategy, with the carbon constituting a good supporting structure, is an effective way to improve the cycling performance of anode materials for lithium ion batteries.

Strong red-emission of Eu{sup 3+}:Li{sub 4}Ti{sub 5}O{sub 12} powders for phosphor applications

Energy Technology Data Exchange (ETDEWEB)

Yang, Yan [Kazuo Inamori School of Engineering, New York State College of Ceramics, Alfred University, Alfred, NY 14802 (United States); Jiménez, José A. [Department of Chemistry, University of North Florida, Jacksonville, FL 32224 (United States); Wu, Yiquan, E-mail: wuy@alfred.edu [Kazuo Inamori School of Engineering, New York State College of Ceramics, Alfred University, Alfred, NY 14802 (United States)

2016-08-15

The synthesis and photoluminescence properties of trivalent europium doped lithium titanate (Eu{sup 3+}:Li{sub 4}Ti{sub 5}O{sub 12}) with different Eu{sup 3+} concentrations (0.1 mol%, 0.3 mol%, 1.0 mol%, 3.0 mol%) are reported and analyzed as a phosphor. Europium (III) nitrate (Eu(NO{sub 3}){sub 3}) was employed as Eu{sup 3+} source, while lithium acetate dihydrate (CH{sub 3}COOLi·2H{sub 2}O) and titanium n-butoxide (Ti(OC{sub 4}H{sub 9}){sub 4}) were adopted as raw materials to synthesize the host lithium titanate with a Li:Ti stoichiometry of 4.5:1. Phase identification was performed using X-ray diffraction (XRD), and morphology was examined using scanning electron microscopy (SEM). Eu{sup 3+}:Li{sub 4}Ti{sub 5}O{sub 12} powders showed strong red emission at 612 nm, corresponding to the {sup 5}D{sub 0}–{sup 7}F{sub 2} transition, with the strongest excitation peak observed in the blue light region at 464 nm. Decay time analyses revealed relatively short lifetimes accompanying typical exponential decay rates. The effect of Eu{sup 3+} concentration (0.1 mol%, 0.3 mol%, 1.0 mol%, 3.0 mol%) on photoluminescence intensity and decay time was explored, and is reported here. It was determined that the CIE color coordinates (0.66, 0.34) of the doped Li{sub 4}Ti{sub 5}O{sub 12} powders were independent of Eu{sup 3+} concentration, and that the coordinates are very similar to the ideal red chromaticity (0.67, 0.33) designated by the National Television Standard Committee (NTSC) system.

Spray drying of spherical Li{sub 4}Ti{sub 5}O{sub 12}/C powders using polyvinyl pyrrolidone as binder and carbon source

Energy Technology Data Exchange (ETDEWEB)

Liu, Wei [Research Center for New Energy Technology, Shanghai Institute of Microsystem and Information Technology, Chinese Academy of Sciences, Shanghai 200050 (China); University of Chinese Academy of Sciences, Beijing 110049 (China); Shanghai Nanotechnology Promotion Center, Shanghai 200237 (China); Wang, Qian; Cao, Chunhui [Research Center for New Energy Technology, Shanghai Institute of Microsystem and Information Technology, Chinese Academy of Sciences, Shanghai 200050 (China); University of Chinese Academy of Sciences, Beijing 110049 (China); Han, Xuewu [Research Center for New Energy Technology, Shanghai Institute of Microsystem and Information Technology, Chinese Academy of Sciences, Shanghai 200050 (China); Zhang, Jian, E-mail: zjskycn@163.com [Research Center for New Energy Technology, Shanghai Institute of Microsystem and Information Technology, Chinese Academy of Sciences, Shanghai 200050 (China); Xie, Xiaohua, E-mail: xiaohuaxie@126.com [Research Center for New Energy Technology, Shanghai Institute of Microsystem and Information Technology, Chinese Academy of Sciences, Shanghai 200050 (China); Xia, Baojia [Research Center for New Energy Technology, Shanghai Institute of Microsystem and Information Technology, Chinese Academy of Sciences, Shanghai 200050 (China); University of Chinese Academy of Sciences, Beijing 110049 (China)

2015-02-05

Highlights: • The spherical Li{sub 4}Ti{sub 5}O{sub 12}/C granules were prepared by spray drying. • Polyvinyl pyrrolidone (PVP) was used as binder and carbon source. • Tap density and spherical structure increase with the increase of PVP content. • Li{sub 4}Ti{sub 5}O{sub 12}/C granules exhibits better rate capability and excellent cyclability. - Abstract: Polyvinyl pyrrolidone (PVP) was used as binder and carbon source to synthesize stable and spherical Li{sub 4}Ti{sub 5}O{sub 12}/C granules by spray drying. The effects of PVP content and atmospheres on the properties of Li{sub 4}Ti{sub 5}O{sub 12} were investigated. The obtained samples were characterized by X-ray diffraction, scanning electron microscopy, Raman spectroscopy, and electrochemical tests, respectively. The results indicate that the average particle size, tap density and degree of spherical structure increase accordingly to the increase of PVP content. However, the large secondary particle would deteriorate the rate capacity at high current density. The carbon coating could significantly improve the rate capacity, which is attributed to the smaller primary particle and higher electrical conductivity.

Robust Strategy for Crafting Li5Cr7Ti6O25@CeO2 Composites as High-Performance Anode Material for Lithium-Ion Battery.

Science.gov (United States)

Mei, Jie; Yi, Ting-Feng; Li, Xin-Yuan; Zhu, Yan-Rong; Xie, Ying; Zhang, Chao-Feng

2017-07-19

A facile strategy was developed to prepare Li 5 Cr 7 Ti 6 O 25 @CeO 2 composites as a high-performance anode material. X-ray diffraction (XRD) and Rietveld refinement results show that the CeO 2 coating does not alter the structure of Li 5 Cr 7 Ti 6 O 25 but increases the lattice parameter. Scanning electron microscopy (SEM) indicates that all samples have similar morphologies with a homogeneous particle distribution in the range of 100-500 nm. Energy-dispersive spectroscopy (EDS) mapping and high-resolution transmission electron microscopy (HRTEM) prove that CeO 2 layer successfully formed a coating layer on a surface of Li 5 Cr 7 Ti 6 O 25 particles and supplied a good conductive connection between the Li 5 Cr 7 Ti 6 O 25 particles. The electrochemical characterization reveals that Li 5 Cr 7 Ti 6 O 25 @CeO 2 (3 wt %) electrode shows the highest reversibility of the insertion and deinsertion behavior of Li ion, the smallest electrochemical polarization, the best lithium-ion mobility among all electrodes, and a better electrochemical activity than the pristine one. Therefore, Li 5 Cr 7 Ti 6 O 25 @CeO 2 (3 wt %) electrode indicates the highest delithiation and lithiation capacities at each rate. At 5 C charge-discharge rate, the pristine Li 5 Cr 7 Ti 6 O 25 only delivers an initial delithiation capacity of ∼94.7 mAh g -1 , and the delithiation capacity merely achieves 87.4 mAh g -1 even after 100 cycles. However, Li 5 Cr 7 Ti 6 O 25 @CeO 2 (3 wt %) delivers an initial delithiation capacity of 107.5 mAh·g -1 , and the delithiation capacity also reaches 100.5 mAh g -1 even after 100 cycles. The cerium dioxide modification is a direct and efficient approach to improve the delithiation and lithiation capacities and cycle property of Li 5 Cr 7 Ti 6 O 25 at large current densities.

Suppression of interfacial reactions between Li4Ti5O12 electrode and electrolyte solution via zinc oxide coating

International Nuclear Information System (INIS)

Han, Cuiping; He, Yan-Bing; Li, Hongfei; Li, Baohua; Du, Hongda; Qin, Xianying; Kang, Feiyu

2015-01-01

Graphical abstract: The Li 4 Ti 5 O 12 (LTO) based batteries have severe gassing behavior due to the strong interfacial reactions between LTO and the electrolyte solution, which hampers the practical application of LTO in high power LIBs. The ZnO coating on LTO particles as a barrier layer can effectively suppress the interfacial reactions between LTO and the electrolyte solution. Simultaneously, the ZnO coating significantly reduces the charge-transfer resistance and increases the lithium ion diffusion coefficient, which leads to great improvement of rate and cyclic performance of LTO electrode. - Highlights: • A ZnO coating layer was constructed on the LTO particles by a chemical process as a barrier layer between LTO and surrounding electrolyte solution. • The ZnO coating can effectively stabilize the electrode/electrolyte interface and suppress interfacial reactions between LTO and electrolyte solution. • The ZnO coating can improve the electronic conductivity and lithium ion diffusion coefficient, which contributes to a great improvement in cyclic and high rate capabilities of LTO electrode. • The ZnO coating on LTO may be an effective method to solve the gassing behavior of LTO based battery and promote its wide application in lithium ion power battery. - Abstract: Li 4 Ti 5 O 12 (LTO) based batteries have severe gassing behavior during charge/discharge and storage process. The interfacial reactions between LTO and electrolyte solution may be the main reason. In this work, the LTO spinel particles are modified with ZnO coating using a chemical process to reduce the surface reactivity of LTO particles. Results show that the ZnO coating can effectively stabilize the electrode/electrolyte interface and suppress the formation of a solid electrolyte interface (SEI) film. Simultaneously, this ZnO modification can improve the electronic conductivity and lithium ion diffusion coefficient, which contributes to a great improvement in cyclic and high rate

Spinel LiMn 2 O 4 Nanorods as Lithium Ion Battery Cathodes

KAUST Repository

Kim, Do Kyung

2008-11-12

Spinel LiMn 2O 4 is a low-cost, environmentally friendly, and highly abundant material for Li-ion battery cathodes. Here, we report the hydrothermal synthesis of single-crystalline β-MnO 2 nanorods and their chemical conversion into free-standing single-crystalline LiMn 2O 4 nanorods using a simple solid-state reaction. The LiMn 2O 4 nanorods have an average diameter of 130 nm and length of 1.2 μm. Galvanostatic battery testing showed that LiMn 2O 4 nanorods have a high charge storage capacity at high power rates compared with commercially available powders. More than 85% of the initial charge storage capacity was maintained for over 100 cycles. The structural transformation studies showed that the Li ions intercalated into the cubic phase of the LiMn 2O 4 with a small change of lattice parameter, followed by the coexistence of two nearly identical cubic phases in the potential range of 3.5 to 4.3V. © 2008 American Chemical Society.

Spinel LiMn 2 O 4 Nanorods as Lithium Ion Battery Cathodes

KAUST Repository

Kim, Do Kyung; Muralidharan, P.; Lee, Hyun-Wook; Ruffo, Riccardo; Yang, Yuan; Chan, Candace K.; Peng, Hailin; Huggins, Robert A.; Cui, Yi

2008-01-01

Spinel LiMn 2O 4 is a low-cost, environmentally friendly, and highly abundant material for Li-ion battery cathodes. Here, we report the hydrothermal synthesis of single-crystalline β-MnO 2 nanorods and their chemical conversion into free-standing single-crystalline LiMn 2O 4 nanorods using a simple solid-state reaction. The LiMn 2O 4 nanorods have an average diameter of 130 nm and length of 1.2 μm. Galvanostatic battery testing showed that LiMn 2O 4 nanorods have a high charge storage capacity at high power rates compared with commercially available powders. More than 85% of the initial charge storage capacity was maintained for over 100 cycles. The structural transformation studies showed that the Li ions intercalated into the cubic phase of the LiMn 2O 4 with a small change of lattice parameter, followed by the coexistence of two nearly identical cubic phases in the potential range of 3.5 to 4.3V. © 2008 American Chemical Society.

Advanced LiTi2(PO4)3@N-doped carbon anode for aqueous lithium ion batteries

International Nuclear Information System (INIS)

He, Zhangxing; Jiang, Yingqiao; Meng, Wei; Zhu, Jing; Liu, Yang; Dai, Lei; Wang, Ling

2016-01-01

Highlights: • LiTi 2 (PO 4 ) 3 @N-doped carbon anode was prepared by in-situ coating approach for aqueous lithium ion batteries. • The well-proportioned N-doped carbon layer and loose nanoporous structure was obtained using urea as nitrogen source and pore former. • LiTi 2 (PO 4 ) 3 @N-doped carbon demonstrates excellent rate performance and good cycling stability. - Abstract: In this paper, LiTi 2 (PO 4 ) 3 @N-doped carbon anode has been synthesized by in situ carbon coating approach. The well-proportioned N-doped carbon layer and loose nanoporous structure was obtained by using urea as nitrogen source and pore former. LiTi 2 (PO 4 ) 3 @N-doped carbon as anode demonstrates much better rate capability than LiTi 2 (PO 4 ) 3 @carbon in ALIBs. The optimized anode delivers the discharge capacity of 93.7 mAh g −1 and 74.2 mAh g −1 at rates of 10C and 20C, 22.5 mAh g −1 and 50.0 mAh g −1 larger than that of LiTi 2 (PO 4 ) 3 @carbon. Moreover, LiTi 2 (PO 4 ) 3 @N-doped carbon exhibits excellent cycling performance with capacity retention of 84.3% at 5C after 1000 cycles. As verified, the well-proportioned N-doped carbon layer could reduce charge transfer resistance and improve electrical conductivity. The loose nanoporous structure could shorten pathway and facilitate diffusion for Li ion. Therefore, LiTi 2 (PO 4 ) 3 @N-doped carbon gets the superior electrochemical properties benefiting from those two characteristics.

Synthesis and electrochemistry of cubic rocksalt Li-Ni-Ti-O compounds in the phase diagram of LiNiO{sub 2}-LiTiO{sub 2}-Li[Li{sub 1/3}Ti{sub 2/3}]O{sub 2}

Energy Technology Data Exchange (ETDEWEB)

Zhang, Lianqi; Noguchi, Hideyuki; Li, Decheng; Muta, Takahisa; Wang, Xiaoqing; Yoshio, Masaki [Department of Applied Chemistry, Saga University, Saga 840-8052 (Japan); Taniguchi, Izumi [Department of Chemical Engineering, Tokyo Institute of Technology, 12-1, Ookayama-2, Meguro-ku, Tokyo 152-8552 (Japan)

2008-10-15

On the basis of extreme similarity between the triangle phase diagrams of LiNiO{sub 2}-LiTiO{sub 2}-Li[Li{sub 1/3}Ti{sub 2/3}]O{sub 2} and LiNiO{sub 2}-LiMnO{sub 2}-Li[Li{sub 1/3}Mn{sub 2/3}]O{sub 2}, new Li-Ni-Ti-O series with a nominal composition of Li{sub 1+z/3}Ni{sub 1/2-z/2}Ti{sub 1/2+z/6}O{sub 2} (0 {<=} z {<=} 0.5) was designed and attempted to prepare via a spray-drying method. XRD identified that new Li-Ni-Ti-O compounds had cubic rocksalt structure, in which Li, Ni and Ti were evenly distributed on the octahedral sites in cubic closely packed lattice of oxygen ions. They can be considered as the solid solution between cubic LiNi{sub 1/2}Ti{sub 1/2}O{sub 2} and Li[Li{sub 1/3}Ti{sub 2/3}]O{sub 2} (high temperature form). Charge-discharge tests showed that Li-Ni-Ti-O compounds with appropriate compositions could display a considerable capacity (more than 80 mAh g{sup -1} for 0.2 {<=} z {<=} 0.27) at room temperature in the voltage range of 4.5-2.5 V and good electrochemical properties within respect to capacity (more than 150 mAh g{sup -1} for 0 {<=} z {<=} 0.27), cycleability and rate capability at an elevated temperature of 50 C. These suggest that the disordered cubic structure in some cases may function as a good host structure for intercalation/deintercalation of Li{sup +}. A preliminary electrochemical comparison between Li{sub 1+z/3}Ni{sub 1/2-z/2}Ti{sub 1/2+z/6}O{sub 2} (0 {<=} z {<=} 0.5) and Li{sub 6/5}Ni{sub 2/5}Ti{sub 2/5}O{sub 2} indicated that charge-discharge mechanism based on Ni redox at the voltage of >3.0 V behaved somewhat differently, that is, Ni could be reduced to +2 in Li{sub 1+z/3}Ni{sub 1/2-z/2}Ti{sub 1/2+z/6}O{sub 2} while +3 in Li{sub 6/5}Ni{sub 2/5}Ti{sub 2/5}O{sub 2}. Reduction of Ti{sup 4+} at a plateau of around 2.3 V could be clearly detected in Li{sub 1+z/3}Ni{sub 1/2-z/2}Ti{sub 1/2+z/6}O{sub 2} with 0.27 {<=} z {<=} 0.5 at 50 C after a deep charge associated with charge compensation from oxygen ion during initial cycle

The Formation of Lithiated Ti-Doped {alpha}-Fe{sub 2}O{sub 3} Nanocrystalline Particles by Mechanical Milling of Ti-Doped Lithium Spinel Ferrite

Energy Technology Data Exchange (ETDEWEB)

Widatallah, H. M., E-mail: hisham@ictp.trieste.it [Khartoum University, Department of Physics (Sudan); Gismelseed, A. M.; Bouziane, K. [Sultan Qaboos University, Department of Physics (Oman); Berry, F. J. [Open University, Department of Chemistry (United Kingdom); Al Rawas, A. D.; Al-Omari, I. A.; Yousif, A. A.; Elzain, M. E. [Sultan Qaboos University, Department of Physics (Oman)

2004-12-15

The milling of spinel-related Ti-doped Li{sub 0.5}Fe{sub 2.5}O{sub 4} for different times is studied with XRD, Moessbauer spectroscopy and magnetic measurements. Milling converts the material to Li-Ti-doped {alpha}-Fe{sub 2}O{sub 3} nanocrystalline particles via an intermediate {gamma}-LiFeO{sub 2}-related phase. The role played by the dopant Ti-ion in the process is emphasized.

Li4Ti5O12/graphene nanoribbons composite as anodes for lithium ion batteries.

Science.gov (United States)

Medina, P A; Zheng, H; Fahlman, B D; Annamalai, P; Swartbooi, A; le Roux, L; Mathe, M K

2015-01-01

In this paper, we report the synthesis of a Li4Ti5O12/Graphene Nanoribbons (LTO/GNRs) composite using a solid-coating method. Electron microscope images of the LTO/GNRs composite have shown that LTO particles were wrapped around graphene nanoribbons. The introduction of GNRs was observed to have significantly improved the rate performance of LTO/GNTs. The specific capacities determined of the obtained composite at rates of 0.2, 0.5, 1, 2, and 5 C are 206.5, 200.9, 188, 178.1 and 142.3 mAh·g(-1), respectively. This is significantly higher than those of pure LTO (169.1, 160, 150, 106 and 71.1 mAh·g(-1), respectively) especially at high rate (2 and 5 C). The LTO/GNRs also shows better cycling stability at high rates. Enhanced conductivity of LTO/GNRs contributed from the GNR frameworks accelerated the kinetics of lithium intercalation/deintercalation in LIBs that also leads to excellent rate capacity of LTO/GNRs. This is attributed to its lower charge-transfer resistance (Rct = 23.38 Ω) compared with LTO (108.05 Ω), and higher exchange current density (j = 1.1 × 10(-3) mA cm(-2))-about 20 times than those of the LTO (j = 2.38 × 10(-4) mA cm(-2)).

A flexible mesoporous Li4Ti5O12-rGO nanocomposite film as free-standing anode for high rate lithium ion batteries

Science.gov (United States)

Zhu, Kunxu; Gao, Hanyang; Hu, Guoxin

2018-01-01

Advanced flexible electrode is crucial in the development of flexible energy storage devices for emerging wearable and portable electronics. Herein, a free-standing flexible mesoporous Li4Ti5O12-rGO (LTO-rGO) nanocomposite film is rationally designed and fabricated for lithium ion batteries (LIBs). This efficient synthesis involves the growth of lithium titanate hydrate (LTH) precursors on the graphene oxide (GO) by a hydrothermal reaction, assembly into LTH-GO film by vacuum filtration with some extra GO added, and subsequent conversion into LTO-rGO nanocomposite film through calcination. When rGO content in the LTO-rGO film is set, the addition sequence of GO is found to affect its textural and mechanical properties. The resultant free-standing LTO-rGO electrode, taking advantages of high Li4Ti5O12 loading of 73.9%, mesoporous layer-stacked channels with good electron/ion conductivity, good mechanical strength, and enlarged electrode/electrolyte contact area, delivers excellent electrochemical performance (e.g., specific capacity of 135.4 mAh g-1 at 40 C) over the electrode of conventional configuration. Moreover, no organic but all inorganic reagents are used in the synthesis, offering an eco-friendly, cost-efficient, and easily scalable way to fabricate binder-free flexible electrode for LIBs.

Investigation of various synthetic conditions for large-scale synthesis and electrochemical properties of Li{sub 3.98}Al{sub 0.06}Ti{sub 4.96}O{sub 12}/C as anode material

Energy Technology Data Exchange (ETDEWEB)

Dong, Guo-Hui, E-mail: dgh1516@gmail.com [Shanghai Shanshan Tech Co., Ltd., 3158 Jinhai Road, Shanghai 201209 (China); Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai 200240 (China); Liu, Hua-Jing; Zhou, Liang [Shanghai Shanshan Tech Co., Ltd., 3158 Jinhai Road, Shanghai 201209 (China); Shanghai Second Polytechnic University, 2360 Jinhai Road, Shanghai 201209 (China); Chong, Lina; Yang, Jun [Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai 200240 (China); Qiao, Yong-Min; Zhang, Dian-Hao [Shanghai Shanshan Tech Co., Ltd., 3158 Jinhai Road, Shanghai 201209 (China)

2014-12-05

Graphical abstract: A gel and spray-drying method is demonstrated for large-scale preparation of Li{sub 3.98}Al{sub 0.06}Ti{sub 4.96}O{sub 12}/C secondary microspheres via optimizing various synthetic conditions. The electrochemical performances of the Li{sub 3.98}Al{sub 0.06}Ti{sub 4.96}O{sub 12}/C microspheres are investigated. - Highlights: • Various synthetic conditions are investigated. • Materials can be produced at ∼1 kg scale by using our demonstrated synthesis method. • Li{sub 3.98}Al{sub 0.06}Ti{sub 4.96}O{sub 12}/C sample possesses high electronic conductivity and rate property, and excellent cycling performance. • Secondary micro-spherical Li{sub 3.98}Al{sub 0.06}Ti{sub 4.96}O{sub 12}/C sample has high tap density et al. - Abstract: Poor electronic conductivity is one of the biggest obstacles for practical application of lithium titanate as lithium-ion battery anode material. Utilizing the advantages of coating and doping techniques to optimize the conductive and rate performances of lithium titanate was reported in this work. Herein, the effects of various synthetic conditions including calcination temperatures and holding times, lithium overdoses, carbon contents, doping contents and doping elements on phase, primary particles’ size and electrochemical performance were comprehensively investigated. The optimal Li{sub 3.98}Al{sub 0.06}Ti{sub 4.96}O{sub 12}/C secondary microspheres were synthesized, which possessed high electronic conductivity, tap density, reversible capacity and first columbic efficiency, and excellent rate performances. Furthermore, the synthesized samples were characterized by various techniques.

Synthesis of graphitized carbon, nanodiamond and graphene supported Li4Ti5O12 and comparison of their electrochemical performance as anodes for lithium ion batteries

Science.gov (United States)

Yang, Shuai; Miao, Juan; Wang, Qiufen; Lu, Mengwei; Sun, Jiufang; Wen, Tao

2016-12-01

Graphitized carbon (GC), nanodiamond (ND) and graphene (GE) supported Li4Ti5O12 (LTO) composites have been synthesized via a solid-state reaction, respectively. The particle sizes of LTO/GC, LTO/ND and LTO/GE are smaller than pure LTO. When tested as the anode for lithium ion batteries, the discharge capacities of LTO, LTO/GC, LTO/ND and LTO/GE composites are 100.1 mAh g-1, 150.4 mAh g-1, 90.4 mAh g-1 and 218.3 mAh g-1 at the current density of 175 mA g-1 after 500 cycles. Their rate capacities retain 59.8%, 80.0%, 81.0% and 85.7% at the current density of 175 mA g-1, 438 mA g-1, 875 mA g-1 and 175 mA g-1, respectively. Moreover, the recovery rates of their rate capacities are 78.6%, 83.4%, 88.9% and 90.1% when returned to the current density of 175 mA g-1, respectively. The reasons can be attributed to the synergistic effect between GC (ND and GE) and LTO as well as the features of the different carbon supports. This strategy, with the carbon constituting a good supporting structure, is an effective way to improve the cycling performance of anode materials for lithium ion batteries.

Spinel Li{sub 2}CoTi{sub 3}O{sub 8} nanometer obtained for application as pigment; Espinela Li{sub 2}CoTi{sub 3}O{sub 8} nanometrica obtenida para aplicacion como pigmento

Energy Technology Data Exchange (ETDEWEB)

Costa de Camara, M. S.; Alves Pimentel, L.; Longo, E.; Nobrega Azevedo, L. da; Araujo Melo, D. M. de

2016-05-01

Pigments are used in ceramics, cosmetics, inks, and other applications widely materials. To this must be single and easily reproducible. Moreover, the pigments obtained in the nanoscale are more stable, reproducible and highlight color in small amounts compared with those obtained in micrometer scale. The mixed oxides with spinel structures AB{sub 2}O{sub 4} have important applications, including: pigments, refractories, catalytic and electronic ceramics. In this context, the aim of this work was the preparation of powder Li{sub 2}CoTi{sub 3}O{sub 8} spinel phase with nanometer particle size of the polymeric precursor method (Pechini) and characterization by means of thermal analysis (TG/DTA) X-ray diffraction (XRD), refined by the Rietveld method, BET, transmission electron microscopy (TEM), Raman and colorimetric coordinates. The pigment was obtained by heat treatment of 400 degree centigrade to 1000 degree centigrade after pyrolysis at 300 degree centigrade/1 h for removing the organic material. Li{sub 2}CoTi{sub 3}O{sub 8} desired spinel phase was obtained from 500 degree centigrade, and presenting stability nanometer to about 1.300 degree centigrade. Spinel green phase introduced at temperatures in the range of 400 degree centigrade and 500 degree centigrade, and 600 degree centigrade at temperatures between blue and 1000 degree centigrade. (Author)

Symmetry transition via tetravalent impurity and investigations on magnetic properties of Li0.5Fe2.5O4

Science.gov (United States)

Kounsalye, Jitendra S.; Kharat, Prashant B.; Chavan, Apparao R.; Humbe, Ashok V.; Borade, R. M.; Jadhav, K. M.

2018-04-01

The present study, deals with the phase symmetry transformation of lithium ferrite after introducing tetravalent (Ti4+) impurity. The sol-gel auto combustion technique was adopted for the synthesis of nanoparticle samples with generic chemical formula Li0.5Fe2.5O4 and Li0.55Ti0.10Fe2.35O4. The synthesized nanoparticles were characterized by X-ray diffraction (XRD) technique for structural analysis. The XRD patterns show the single phase cubic structure without any impurity phase but the P4332 to Fd-3m transformation was observed after introducing Ti4+ impurity. The Nano size of the synthesized particles was confirmed by crystallite size ( 20nm) calculated using Debye-Scherrer's formula. The Fourier transform infrared spectroscopy (FTIR) studies shows shifting of band frequencies which reflect the structural changes after tetravalent substitutional impurities. The magnetic properties were studied through pulse field hysteresis loop (M-H loop) technique at room temperature, the M-H loops showdecrease in magnetic properties afternonmagnetic Ti4+ ion substitution. This is attributed to transition of inverse spinel structure of lithium ferrite to random spinel structure.

STUDY OF THE INSERTION AND EXTRACTION MECHANISM OF Li3Mn0.5Ti0.25O3

Directory of Open Access Journals (Sweden)

JINHE JIANG

2017-12-01

Full Text Available The metal oxide [Li3Mn0.5Ti0.25O3] was synthesized by solid state reaction crystallization method in certain temperature. It was an inverse spinel type compound metal oxide. The extraction/insertion reaction of this material was studied by X-ray, saturation exchange capacity value and distribution coefficient (Kd measurement value. In terms of its composition and chemical metrology, this inverse spinel material is very comprehensive; it is worth noting that it can be inserted or extracted by other substitutional ions and changes in lithium and oxygen stoichiometry while maintaining their crystal structure. The metal oxide [Li3Mn0.5Ti0.25O3] is inorganic Li+ exchanger which has an ion-memory capacity. It has high exchange selectivity ability for Li+. This metal oxide can be used to separate or extract Li+ in aqueous solution. The experimental result has confirmed inverse spinel type compound metal oxide which was treated by acid could attain 9.7 mmol‧g-1 Li+ exchanged capacity.

Ab initio study of radiation effects on the Li4Ti5O12 electrode used in lithium-ion batteries

Science.gov (United States)

Samin, Adib; Kurth, Michael; Cao, Lei

2015-04-01

Lithium-ion batteries are currently in wide use owing to their high energy density and enhanced capabilities. Li4Ti5O12 is a promising anode material for lithium-ion batteries because of its advantageous properties. Lithium-ion batteries could be exposed to radiation occurring in various conditions such as during outer space exploration and nuclear accidents. In this study, we apply density functional theory to explore the effect of radiation damage on this electrode and, ultimately, on the performance of the battery. It was found that radiation could affect the structural stability of the material. Furthermore, the electrode was shown to undergo a transition from insulator to metal, following the defects due to radiation. In addition, the effect of radiation on the intercalation potential was found to be highly dependent on the nature of the defect induced.

Ab initio study of radiation effects on the Li4Ti5O12 electrode used in lithium-ion batteries

International Nuclear Information System (INIS)

th Avenue, Columbus, Ohio 43210 (United States))" data-affiliation=" (Nuclear Engineering Program, Department of Mechanical and Aerospace Engineering, The Ohio State University, 201 W 19th Avenue, Columbus, Ohio 43210 (United States))" >Samin, Adib; th Avenue, Columbus, Ohio 43210 (United States))" data-affiliation=" (Nuclear Engineering Program, Department of Mechanical and Aerospace Engineering, The Ohio State University, 201 W 19th Avenue, Columbus, Ohio 43210 (United States))" >Kurth, Michael; th Avenue, Columbus, Ohio 43210 (United States))" data-affiliation=" (Nuclear Engineering Program, Department of Mechanical and Aerospace Engineering, The Ohio State University, 201 W 19th Avenue, Columbus, Ohio 43210 (United States))" >Cao, Lei

2015-01-01

Lithium-ion batteries are currently in wide use owing to their high energy density and enhanced capabilities. Li 4 Ti 5 O 12 is a promising anode material for lithium-ion batteries because of its advantageous properties. Lithium-ion batteries could be exposed to radiation occurring in various conditions such as during outer space exploration and nuclear accidents. In this study, we apply density functional theory to explore the effect of radiation damage on this electrode and, ultimately, on the performance of the battery. It was found that radiation could affect the structural stability of the material. Furthermore, the electrode was shown to undergo a transition from insulator to metal, following the defects due to radiation. In addition, the effect of radiation on the intercalation potential was found to be highly dependent on the nature of the defect induced

Microwave-assisted synthesis of high-voltage nanostructured LiMn1.5Ni0.5O4 spinel: tuning the Mn3+ content and electrochemical performance

CSIR Research Space (South Africa)

Jafta, CJ

2013-08-01

Full Text Available on the Mn3+ concentration and electrochemistry of the LiMn1.5Ni0.5O4 spinel. It is shown that microwave is capable of tuning the Mn3+ content of the spinel for enhanced electrochemical performance (high capacity, high capacity retention, excellent rate...

Nanostructured Networks for Energy Storage: Vertically Aligned Carbon Nanotubes (VACNT as Current Collectors for High-Power Li4Ti5O12(LTO//LiMn2O4(LMO Lithium-Ion Batteries

Directory of Open Access Journals (Sweden)

Fabian Pawlitzek

2017-11-01

Full Text Available As a concept for electrode architecture in high power lithium ion batteries, self-supported nanoarrays enable ultra-high power densities as a result of their open pore geometry, which results in short and direct Li+-ion and electron pathways. Vertically aligned carbon nanotubes (VACNT on metallic current collectors with low interface resistance are used as current collectors for the chemical solution infiltration of electroactive oxides to produce vertically aligned carbon nanotubes decorated with in situ grown LiMn2O4 (LMO and Li4Ti5O12 (LTO nanoparticles. The production processes steps (catalyst coating, VACNT chemical vapor deposition (CVD, infiltration, and thermal transformation are all scalable, continuous, and suitable for niche market production to achieve high oxide loadings up to 70 wt %. Due to their unique transport structure, as-prepared nanoarrays achieve remarkably high power densities up to 2.58 kW kg−1, which is based on the total electrode mass at 80 C for LiMn2O4//Li4Ti5O12 full cells. The tailoring of LTO and LMO nanoparticle size (~20–100 nm and VACNT length (array height: 60–200 µm gives insights into the rate-limiting steps at high current for these kinds of nanoarray electrodes at very high C-rates of up to 200 C. The results reveal the critical structural parameters for achieving high power densities in VACNT nanoarray full cells.

Adiponitrile-Lithium Bis(trimethylsulfonyl)imide Solutions as Alkyl Carbonate-free Electrolytes for Li4 Ti5 O12 (LTO)/LiNi1/3 Co1/3 Mn1/3 O2 (NMC) Li-Ion Batteries.

Science.gov (United States)

Farhat, Douaa; Ghamouss, Fouad; Maibach, Julia; Edström, Kristina; Lemordant, Daniel

2017-05-19

Recently, dinitriles (NC(CH 2 ) n CN) and especially adiponitrile (ADN, n=4) have attracted attention as safe electrolyte solvents owing to their chemical stability, high boiling points, high flash points, and low vapor pressure. The good solvation properties of ADN toward lithium salts and its high electrochemical stability (≈6 V vs. Li/Li + ) make it suitable for safer Li-ions cells without performance loss. In this study, ADN is used as a single electrolyte solvent with lithium bis(trimethylsulfonyl)imide (LiTFSI). This electrolyte allows the use of aluminium collectors as almost no corrosion occurs at voltages up to 4.2 V. The physicochemical properties of the ADN-LiTFSI electrolyte, such as salt dissolution, conductivity, and viscosity, were determined. The cycling performances of batteries using Li 4 Ti 5 O 12 (LTO) as the anode and LiNi 1/3 Co 1/3 Mn 1/3 O 2 (NMC) as the cathode were determined. The results indicate that LTO/NMC batteries exhibit excellent rate capabilities with a columbic efficiency close to 100 %. As an example, cells were able to reach a capacity of 165 mAh g -1 at 0.1 C and a capacity retention of more than 98 % after 200 cycles at 0.5 C. In addition, electrodes analyses by SEM, X-ray photoelectron spectroscopy (XPS), and electrochemical impedance spectroscopy after cycling confirming minimal surface changes of the electrodes in the studied battery system. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Delithiation/relithiation process of LiCoMnO4 spinel as 5 V electrode material

Science.gov (United States)

Dräger, Christoph; Sigel, Florian; Indris, Sylvio; Mikhailova, Daria; Pfaffmann, Lukas; Knapp, Michael; Ehrenberg, Helmut

2017-12-01

In this work, the LiCoMnO4 spinel has been synthesized by a two-step sol-gel based method, followed by sintering at temperatures up to 750 °C in oxygen. After structural characterization of the pristine material via synchrotron and neutron diffraction, the material was characterized via SEM and 6Li-MAS-NMR spectroscopy. 6Li-MAS-NMR spectroscopy in different states of charge revealed, that manganese and cobalt are distributed homogenously throughout the material and the delithiation primary occurs from the manganese environments. It was also shown, that it is not possible to fully delithiate the material in a practical voltage range of an electrolyte. Electrochemical cycling results reveal that about 70% of the lithium can be extracted and reinserted electrochemically in the voltage window from 4.5 to 5.4 V against lithium from/into LiCoMnO4. In situ synchrotron powder diffraction results show that lithium extraction/insertion occurs via a single-phase mechanism over the whole range of lithium contents and that the discharge capacity is mainly restricted by the voltage-window of the electrolyte. Furthermore it was shown, that the delithiation occurs up to a potential of 5.6 V.

Negative oxides: negative electrode materials for new generation: Li-ion batteries; Les oxides de titane: materiaux d'electrodes negatives pour batteries Li-ion nouvelle generation

Energy Technology Data Exchange (ETDEWEB)

Kubiak, P.

2003-12-01

This work concerns the development of new anodic materials for powerful secondary batteries. We have studied three families of materials (potential {approx}-1.5 V vs Li): TiO{sub 2} anatase, Li{sub 2}Ti{sub 3}O{sub 7} ramsdellite and Li{sub 4}Ti{sub 5}O{sub 12} spinel. Many ways of synthesis have been tested and the influence of different parameters on purity and texture of compounds has been analysed. Titanium has been substituted by different elements in order to modify the structures. X-ray diffraction and Moessbauer spectroscopy have been used for the physicochemical characterisation of compounds. The studies of involved mechanisms and titanium partial substitutions have allowed linking the physicochemical characteristics to the performances. Electrochemical insertion of lithium into Li{sub 4}Ti{sub 5}O{sub 12} is characterised by a two-phase mechanism at constant potential (1.5 V). The insertion of three lithium (175 mAh.g{sup -1}) is based on the reversible transition spinel{r_reversible}NaCl. The presence of structural defects decreases the performances by modifying the displacement of the atoms into the network. A single-phase mechanism characterised by a topotactic insertion into the vacant sites of the network is observed for Li{sub 2}Ti{sub 3}O{sub 7}. This needs great network stability and can be improved by substitutions (Fe{sup III}). The succession of a two-phase and a single-phase mechanism into TiO{sub 2} does not allow optimising performances because substitutions improve the single-phase mechanism but prevent the two-phase mechanism. This study shows the interest of the Moessbauer spectroscopy for the hyperfine analysis of the redox mechanisms involved into the electrochemical reactions and the ability of lithium titanates to be used as anodic materials for powerful secondary batteries. (author)

Smart Construction of Integrated CNTs/Li4Ti5O12 Core/Shell Arrays with Superior High-Rate Performance for Application in Lithium-Ion Batteries.

Science.gov (United States)

Yao, Zhujun; Xia, Xinhui; Zhou, Cheng-Ao; Zhong, Yu; Wang, Yadong; Deng, Shengjue; Wang, Weiqi; Wang, Xiuli; Tu, Jiangping

2018-03-01

Exploring advanced high-rate anodes is of great importance for the development of next-generation high-power lithium-ion batteries (LIBs). Here, novel carbon nanotubes (CNTs)/Li 4 Ti 5 O 12 (LTO) core/shell arrays on carbon cloth (CC) as integrated high-quality anode are constructed via a facile combined chemical vapor deposition-atomic layer deposition (ALD) method. ALD-synthesized LTO is strongly anchored on the CNTs' skeleton forming core/shell structures with diameters of 70-80 nm the combined advantages including highly conductive network, large surface area, and strong adhesion are obtained in the CC-LTO@CNTs core/shell arrays. The electrochemical performance of the CC-CNTs/LTO electrode is completely studied as the anode of LIBs and it shows noticeable high-rate capability (a capacity of 169 mA h g -1 at 1 C and 112 mA h g -1 at 20 C), as well as a stable cycle life with a capacity retention of 86% after 5000 cycles at 10 C, which is much better than the CC-LTO counterpart. Meanwhile, excellent cycling stability is also demonstrated for the full cell with LiFePO 4 cathode and CC-CNTs/LTO anode (87% capacity retention after 1500 cycles at 10 C). These positive features suggest their promising application in high-power energy storage areas.

Smart Construction of Integrated CNTs/Li4Ti5O12 Core/Shell Arrays with Superior High‐Rate Performance for Application in Lithium‐Ion Batteries

Science.gov (United States)

Yao, Zhujun; Zhou, Cheng‐ao; Zhong, Yu; Wang, Yadong; Deng, Shengjue; Wang, Weiqi; Wang, Xiuli

2018-01-01

Abstract Exploring advanced high‐rate anodes is of great importance for the development of next‐generation high‐power lithium‐ion batteries (LIBs). Here, novel carbon nanotubes (CNTs)/Li4Ti5O12 (LTO) core/shell arrays on carbon cloth (CC) as integrated high‐quality anode are constructed via a facile combined chemical vapor deposition–atomic layer deposition (ALD) method. ALD‐synthesized LTO is strongly anchored on the CNTs' skeleton forming core/shell structures with diameters of 70–80 nm the combined advantages including highly conductive network, large surface area, and strong adhesion are obtained in the CC‐LTO@CNTs core/shell arrays. The electrochemical performance of the CC‐CNTs/LTO electrode is completely studied as the anode of LIBs and it shows noticeable high‐rate capability (a capacity of 169 mA h g−1 at 1 C and 112 mA h g−1 at 20 C), as well as a stable cycle life with a capacity retention of 86% after 5000 cycles at 10 C, which is much better than the CC‐LTO counterpart. Meanwhile, excellent cycling stability is also demonstrated for the full cell with LiFePO4 cathode and CC‐CNTs/LTO anode (87% capacity retention after 1500 cycles at 10 C). These positive features suggest their promising application in high‐power energy storage areas. PMID:29593977

Phosphidation of Li4Ti5O12 nanoparticles and their electrochemical and biocompatible superiority for lithium rechargeable batteries.

Science.gov (United States)

Jo, Mi Ru; Nam, Ki Min; Lee, Youngmin; Song, Kyeongse; Park, Joon T; Kang, Yong-Mook

2011-11-07

Phosphidated-Li(4)Ti(5)O(12) shows high capacity with a significantly enhanced kinetics opening new possibilities for ultra-fast charge/discharge of lithium rechargeable batteries. The in vitro cytotoxicity test proves its fabulous cell viability, indicating that the toxicity problem of nanoparticles can be also solved by phosphidation. This journal is © The Royal Society of Chemistry 2011

Selection and Performance-Degradation Modeling of LiMO2/Li4Ti5O12 and LiFePO4/C Battery Cells as Suitable Energy Storage Systems for Grid Integration With Wind Power Plants

DEFF Research Database (Denmark)

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

2014-01-01

Advances in the development of energy storage technologies are making them attractive for grid integration together with wind power plants. Thus, the new system, the virtual power plant, is able to emulate the characteristics of today’s conventional power plants. However, at present, energy stora......-degradation models were developed for the two most suitable Li–ion chemistries for the primary frequency regulation service: LiMO2 /Li4Ti5O12 and LiFePO4/C....

Fabrication and tritium release property of Li2TiO3-Li4SiO4 biphasic ceramics

Science.gov (United States)

Yang, Mao; Ran, Guangming; Wang, Hailiang; Dang, Chen; Huang, Zhangyi; Chen, Xiaojun; Lu, Tiecheng; Xiao, Chengjian

2018-05-01

Li2TiO3-Li4SiO4 biphasic ceramic pebbles have been developed as an advanced tritium breeder due to the potential to combine the advantages of both Li2TiO3 and Li4SiO4. Wet method was developed for the pebble fabrication and Li2TiO3-Li4SiO4 biphasic ceramic pebbles were successfully prepared by wet method using the powders synthesized by hydrothermal method. The tritium release properties of the Li2TiO3-Li4SiO4 biphasic ceramic pebbles were evaluated. The biphasic pebbles exhibited good tritium release property at low temperatures and the tritium release temperature was around 470 °C. Because of the isotope exchange reaction between H2 and tritium, the addition of 0.1%H2 to purge gas He could significantly enhance the tritium gas release and the fraction of molecular form of tritium increased from 28% to 55%. The results indicate that the Li2TiO3-Li4SiO4 biphasic ceramic pebbles fabricated by wet method exhibit good tritium release property and hold promising potential as advanced breeder pebbles.

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

Complex titanates Sr_1_-_xPb_xLi_2Ti_6O_1_4 (0≤x≤1) as anode materials for high-performance lithium-ion batteries

International Nuclear Information System (INIS)

Qian, Shangshu; Yu, Haoxiang; Yan, Lei; Li, Peng; Lin, Xiaoting; Wu, Yaoyao; Long, Nengbing; Shui, Miao; Shu, Jie

2016-01-01

Highlights: • Sr_1_-_xPb_xLi_2Ti_6O_1_4 (0≤x≤1) is prepared by a simple solid state reaction. • Sr_0_._5Pb_0_._5Li_2Ti_6O_1_4 exhibits enhanced lithium storage capability. • Sr_0_._5Pb_0_._5Li_2Ti_6O_1_4 can deliver a capacity of 141.8 mAh g"−"1 at 700 mA g"−"1. • In-situ XRD is performed to study the reversibility of Sr_1_-_xPb_xLi_2Ti_6O_1_4. - Abstract: With the Pb doping content at Sr-site increasing, a series of Sr_1_-_xPb_xLi_2Ti_6O_1_4 (x = 0, 0.25, 0.50, 0.75, 1.0) are synthesized by a simple solid-state reaction. It is found that the reversible capacity and rate capability experience a parabolic course from SrLi_2Ti_6O_1_4 to PbLi_2Ti_6O_1_4. Among all the as-prepared samples, Sr_0_._5Pb_0_._5Li_2Ti_6O_1_4 shows the best cycling and rate properties. It delivers an initial charge capacity of 163.2 mAh g"−"1 at 100 mA g"−"1 with the capacity retention of 96.08% after 100 cycles. In addition, it can also deliver a reversible capacity of 141.8 mAh g"−"1 at 700 mA g"−"1. The superior electrochemical properties of Sr_0_._5Pb_0_._5Li_2Ti_6O_1_4 are attributed to the reduced charge transfer resistance and increased lithium-ion diffusion coefficient after doping. Besides, in-situ X-ray diffraction is also performed to investigate the lithium-ion insertion/extraction behaviors of SrLi_2Ti_6O_1_4, Sr_0_._5Pb_0_._5Li_2Ti_6O_1_4 and PbLi_2Ti_6O_1_4. The observed results confirm that Sr_0_._5Pb_0_._5Li_2Ti_6O_1_4 has good structural stability and reversibility for repeated lithium storage.

Ab initio study of radiation effects on the Li{sub 4}Ti{sub 5}O{sub 12} electrode used in lithium-ion batteries

Energy Technology Data Exchange (ETDEWEB)

Samin, Adib, E-mail: Samin.2@osu.edu, E-mail: cao.152@osu.edu; Kurth, Michael; Cao, Lei, E-mail: Samin.2@osu.edu, E-mail: cao.152@osu.edu [Nuclear Engineering Program, Department of Mechanical and Aerospace Engineering, The Ohio State University, 201 W 19" t" h Avenue, Columbus, Ohio 43210 (United States)

2015-04-15

Lithium-ion batteries are currently in wide use owing to their high energy density and enhanced capabilities. Li{sub 4}Ti{sub 5}O{sub 12} is a promising anode material for lithium-ion batteries because of its advantageous properties. Lithium-ion batteries could be exposed to radiation occurring in various conditions such as during outer space exploration and nuclear accidents. In this study, we apply density functional theory to explore the effect of radiation damage on this electrode and, ultimately, on the performance of the battery. It was found that radiation could affect the structural stability of the material. Furthermore, the electrode was shown to undergo a transition from insulator to metal, following the defects due to radiation. In addition, the effect of radiation on the intercalation potential was found to be highly dependent on the nature of the defect induced.

Hybrid microwave synthesis and characterization of the compounds in the Li-Ti-O system

Energy Technology Data Exchange (ETDEWEB)

Yang, Li Hong; Dong, Cheng; Guo, Juan [National Laboratory for Superconductivity, Institute of Physics and Beijing National Laboratory for Condensed Matter Physics, Chinese Academy of Science, P.O. Box 603, Beijing 100080 (China)

2008-01-03

Hybrid microwave synthesis has been applied for preparation of Li{sub 4}Ti{sub 5}O{sub 12}, Li{sub 2}Ti{sub 3}O{sub 7}, Li{sub 2}TiO{sub 3} and LiTiO{sub 2} for the first time. Stepwise heating was used for avoiding the instantaneous release of gas by-product and obtaining well-shaped samples. The samples were characterized by powder X-ray diffraction, energy-dispersive X-ray analysis and scanning electron microscopy. The obtained samples have relatively uniform particle sizes. The electrochemical performance of Li{sub 4}Ti{sub 5}O{sub 12} and Li{sub 2}Ti{sub 3}O{sub 7} were investigated. The first discharge capacity of Li{sub 4}Ti{sub 5}O{sub 12} was 150 mAh g{sup -1} and 141 mAh g{sup -1} after 27 cycles and a very flat discharge and charge curve of Li{sub 4}Ti{sub 5}O{sub 12} was shown at about 1.56 V. Similarly, Li{sub 2}Ti{sub 3}O{sub 7} exhibits good cycle performance. The initial discharge capacity is 118 mAh g{sup -1} and 30th cycle is still 112 mAh g{sup -1}. (author)

Performance-degradation model for Li4Ti5O12-based battery cells used in wind power applications

DEFF Research Database (Denmark)

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

2012-01-01

Energy storage systems based on Lithium-ion batteries have the potential to mitigate the negative impact of wind power grid integration on the power system stability, which is caused by the characteristics of the wind. This paper presents a performance model for a Li4Ti5O12/LiMO2 battery cell....... For developing the performance model an EIS-based electrical modelling approach was followed. The obtained model is able to predict with high accuracy charge and discharge voltage profiles for different ages of the battery cell and for different charging/discharging current rates. Moreover, the ageing behaviour...... of the battery cell was analysed for the case of accelerated cycling ageing with a certain mission profile....

In-situ synchrotron PXRD study of spinel LiMn2O4 nanocrystal formation

DEFF Research Database (Denmark)

Birgisson, Steinar; Jensen, Kirsten Marie Ørnsbjerg; Christiansen, Troels Lindahl

Many solvothermal reactions have a great potential for environmentally friendly and easily scalable way for producing nanocrystalline materials on an industrial scale. Here we study hydrothermal formation of spinel LiMn2O4 which is a well-known cathode material for Li-ion batteries. The LiMn2O4...... nanoparticles are formed by reducing KMnO4 in an aqueous solution containing Li-ions. The reducing agent is an alcohol (here ethanol) and the reaction takes place under high pressure and temperature. The LiMn2O4 nanocrystals are unstable towards further reduction to Mn3O4 nanocrystals. Possible reaction route...

Preparation of Li_4Ti_5O_1_2 nanosheets/carbon nanotubes composites and application of anode materials for lithium-ion batteries

International Nuclear Information System (INIS)

Zhang, Pengfei; Chen, Ming; Shen, Xiao; Wu, Qianhui; Zhang, Xiue; Huan, Long; Diao, Guowang

2016-01-01

Highlights: • LTO NSs/CNTs composites are synthesized by a facile and scalable strategy. • The incorporation of CNTs into LTO NSs forms a delicate conductive network. • LTO NSs/CNTs composites display excellent rate and cycling performances. • LTO NSs/CNTs show low polarization and large diffusion coefficient of Li"+. - Abstract: Li_4Ti_5O_1_2 nanosheets (LTO NSs)/carbon nanotubes (CNTs) composites are synthesized using a facile, reproducible, and scalable strategy. In the hydrothermal process, the introduction of CNTs significantly improves the rate performance of LTO NSs. The incorporation of CNTs into the LTO NSs forms a delicate conductive network for rapid electron and lithium ions transport, resulting in excellent rate performance and superior cycling performance. LTO NSs/7.5%-CNTs composites show the highest reversible capacity and high-rate capability (a reversible capability of 157, 145, 132, 118, and 105 mA h g"−"1 at 1, 2, 3, 4, 5 A g"−"1, respectively) with good cycling performance (approximate 6.9% capacity loss after 1000 cycles at 2 A g"−"1 with a capacity retention of 135 mA h g"−"1), which is apparently larger than pristine LTO NSs. The significantly improved rate capability and cycling performance of the LTO NSs/CNTs composites are mainly attributed to their the lower polarization of potential difference, the larger diffusion coefficient of lithium ion and smaller charge-transfer resistance than pure LTO NSs.

Water vapor concentration dependence and temperature dependence of Li mass loss from Li{sub 2}TiO{sub 3} with excess Li and Li{sub 4}SiO{sub 4}

Energy Technology Data Exchange (ETDEWEB)

Shimozori, Motoki [Interdisciplinary Graduate School of Engineering Science, Kyushu University, 6-1, Kasugakoen, Kasuga, Fukuoka 816-8580 (Japan); Katayama, Kazunari, E-mail: kadzu@nucl.kyushu-u.ac.jp [Interdisciplinary Graduate School of Engineering Science, Kyushu University, 6-1, Kasugakoen, Kasuga, Fukuoka 816-8580 (Japan); Hoshino, Tsuyoshi [Breeding Functional Materials Development Group, Department of Blanket Systems Research, Rokkasho Fusion Institute, Sector of Fusion Research and Development, Japan Atomic Energy Agency, 2-166 Obuch, Omotedate, Rokkasho-mura, Kamikita-gun, Aomori 039-3212 (Japan); Ushida, Hiroki; Yamamoto, Ryotaro; Fukada, Satoshi [Interdisciplinary Graduate School of Engineering Science, Kyushu University, 6-1, Kasugakoen, Kasuga, Fukuoka 816-8580 (Japan)

2015-10-15

Highlights: • Li mass loss from Li{sub 2.11}TiO{sub 3} increased proportionally to water vapor pressure. • Li mass loss from Li{sub 2.11}TiO{sub 3} at 600 °C was significantly smaller than expected. • Differences of Li mass loss behavior from Li{sub 2.11}TiO{sub 3} and Li{sub 4}SiO{sub 4} were shown. - Abstract: In this study, weight reduction of Li{sub 2}TiO{sub 3} with excess Li and Li{sub 4}SiO{sub 4} at elevated temperatures under hydrogen atmosphere or water vapor atmosphere was investigated. The Li mass loss for the Li{sub 2}TiO{sub 3} at 900 °C was 0.4 wt% under 1000 Pa H{sub 2} atmosphere and 1.5 wt% under 50 Pa H{sub 2}O atmosphere. The Li mass loss for the Li{sub 2}TiO{sub 3} increased proportionally to the water vapor pressure in the range from 50 to 200 Pa at 900 °C and increased with increasing temperature from 700 to 900 °C although Li mass loss at 600 °C was significantly smaller than expected. It was found that water vapor concentration dependence and temperature dependence of Li mass loss for the Li{sub 2}TiO{sub 3} and the Li{sub 4}SiO{sub 4} used in this work were quite different. Water vapor is released from the ceramic breeder materials into the purge gas due to desorption of adsorbed water and water formation reaction. The released water vapor possibly promotes Li mass loss with the formation of LiOH on the surface.

Electrochemical activity of Li{sub 2}FeTiO{sub 4} and Li{sub 2}MnTiO{sub 4} as potential active materials for Li ion batteries: A comparison with Li{sub 2}NiTiO{sub 4}

Energy Technology Data Exchange (ETDEWEB)

Kuezma, Mirjana; Dominko, Robert; Bele, Marjan; Jamnik, Janko [National Institute of Chemistry, Ljubljana (Slovenia); Meden, Anton [Faculty of Chemistry and Chemical Technology, University of Ljubljana (Slovenia); Makovec, Darko [Jozef Stefan Institute, Ljubljana (Slovenia); Gaberscek, Miran [National Institute of Chemistry, Ljubljana (Slovenia); Faculty of Chemistry and Chemical Technology, University of Ljubljana (Slovenia)

2009-04-01

We demonstrate, for the first time, a considerable electrochemical activity of two members of lithium transition element titanates: Li{sub 2}FeTiO{sub 4} and Li{sub 2}MnTiO{sub 4}. Both materials consist of 10-20 nm particles embedded in a conductive carbon coating. We show that not the coating but the small particle size is decisive for materials' activity. Li{sub 2}FeTiO{sub 4} shows a stable reversible capacity of up to 123 mA hg{sup -1} at C/20 and 60 C which is 83% of the theoretical value for exchange of 1 electron (148 mA hg{sup -1}). Li{sub 2}MnTiO{sub 4} could only be prepared in a nanosized form that contained about 30% of impurities. The capacity of the whole material (including impurities) is comparable to that of Li{sub 2}FeTiO{sub 4} but the cycling stability is much poorer. In contrast to the Fe and Mn analogues, the third member of the titanate family, Li{sub 2}NiTiO{sub 4}, shows a good electrochemistry even when the particle size is much larger (about 100 nm). During initial cycles at C/10 and 60 C, exchange of more than 1 electron per compound formula has been observed. The cycling stability at high temperatures, however, is poor. (author)

IN-SITU SYNCHROTRON PXRD STUDY OF SPINEL TYPE LiMn2O4 NANOCRYSTAL FORMATION

DEFF Research Database (Denmark)

Birgisson, Steinar; Jensen, Kirsten Marie Ørnsbjerg; Christiansen, Troels Lindahl

Many solvothermal reactions have a great potential for environmentally friendly and easily scalable way for producing nanocrystalline materials on an industrial scale. Here we study hydrothermal formation of spinel LiMn2O4 which is a well-known cathode material for Li-ion batteries. The LiMn2O4...... nanoparticles are formed by reducing KMnO4 in an aqueous solution containing Li-ions. The reducing agent is an alcohol (here ethanol) and the reaction takes place under high pressure and temperature. The LiMn2O4 nanocrystals are unstable towards further reduction to Mn3O4 nanocrystals. Proposed reaction route...

Li-ion batteries from LiFePO{sub 4} cathode and anatase/graphene composite anode for stationary energy storage

Energy Technology Data Exchange (ETDEWEB)

Choi, Daiwon; Wang, Donghai; Viswanathan, Vish V.; Wang, Wei; Nie, Zimin; Zhang, Ji-Guang; Graff, Gordon L.; Liu, Jun; Yang, Zhenguo [Pacific Northwest National Laboratory, 902 Battelle Boulevard, P.O. Box 999, Richland, WA 99352 (United States); Bae, In-Tae [Small Scale Systems Integration and Packaging Center, State University of New York at Binghamton, P.O. Box 6000, Binghamton, NY 13902 (United States); Duong, Tien [US Departments of Energy, 1000 Independence Ave., Washington, DC 20858 (United States)

2010-03-15

Li-ion batteries made from LiFePO{sub 4} cathode and anatase TiO{sub 2}/graphene composite anode were investigated for potential application in stationary energy storage. Fine-structured LiFePO{sub 4} was synthesized by a novel molten surfactant approach whereas anatase TiO{sub 2}/graphene nanocomposite was prepared via self-assembly method. The full cell that operated at 1.6 V demonstrated negligible fade even after more than 700 cycles at measured 1 C rate. While with relative lower energy density than traditional Li-ion chemistries interested for vehicle applications, the Li-ion batteries based on LiFePO{sub 4}/TiO{sub 2} combination potentially offers long life and low cost, along with safety, all which are critical to the stationary applications. (author)

Comparison of Nonlinear Filtering Methods for Estimating the State of Charge of Li4Ti5O12 Lithium-Ion Battery

Directory of Open Access Journals (Sweden)

Jianping Gao

2015-01-01

Full Text Available Accurate state of charge (SoC estimation is of great significance for the lithium-ion battery to ensure its safety operation and to prevent it from overcharging or overdischarging. To achieve reliable SoC estimation for Li4Ti5O12 lithium-ion battery cell, three filtering methods have been compared and evaluated. A main contribution of this study is that a general three-step model-based battery SoC estimation scheme has been proposed. It includes the processes of battery data measurement, parametric modeling, and model-based SoC estimation. With the proposed general scheme, multiple types of model-based SoC estimators have been developed and evaluated for battery management system application. The detailed comparisons on three advanced adaptive filter techniques, which include extend Kalman filter, unscented Kalman filter, and adaptive extend Kalman filter (AEKF, have been implemented with a Li4Ti5O12 lithium-ion battery. The experimental results indicate that the proposed model-based SoC estimation approach with AEKF algorithm, which uses the covariance matching technique, performs well with good accuracy and robustness; the mean absolute error of the SoC estimation is within 1% especially with big SoC initial error.

NaLaTi_2O_6 nanosheet as a potential anode material for lithium ion batteries

International Nuclear Information System (INIS)

Geng, Qiao; Cao, Liyun; Kong, Xingang; Xu, Zhanwei; Huang, Jianfeng; Li, Jiayin; Cheng, Yayi

2016-01-01

Highlights: • NaLaTi_2O_6 nanosheet was achieved by a simple one-step hydrothermal method. • NaLaTi_2O_6 was reported for the first time as an anode material. • NaLaTi_2O_6 shown a high discharge capacity of about 180 mAh/g at 100 mA/g. - Abstract: NaLaTi_2O_6 nanosheet was achieved by one-step hydrothermal method and was reported for the first time as an anode material for lithium ion batteries. The phase structure and morphology analysis reveals that pure pervoskite NaLaTi_2O_6 possesses nanosheet morphology with thickness of about 20 nm and length of several hundred nanometers. The electrochemical performances demonstrate that NaLaTi_2O_6 has a good lithium ion insertion/extraction ability with a discharge capacity of about 180 mAh/g, which is slightly larger than Li_4Ti_5O_1_2 theoretical capacity (175 mAh/g). Even more, after 1000 charge-discharge cycles at 100 mA/g, it still maintains a discharge capacity of 165 mAh/g, suggesting that NaLaTi_2O_6 could be explored as a potential anode material for lithium ion batteries.

Solid state opto-impedance of LiNiVO4 and LiMn2O4

International Nuclear Information System (INIS)

Kalyani, P; Sivasubramanian, S; Prabhu, S Naveen; Ragavendran, K; Kalaiselvi, N; Ranganathan, N G; Madhu, S; SundaraRaj, A; Manoharan, S P; Jagannathan, R

2005-01-01

Spinel type LiMn 2 O 4 and inverse spinel LiNiVO 4 systems serve as standard cathode materials or potential cathode systems for application in high energy density lithium-ion batteries. Upon photo-excitation using UV radiation of energy ∼5 eV, the LiNiVO 4 system shows significant modification in the solid state impedance pattern while the LiMn 2 O 4 system does not. This study has revealed a significant difference in the opto-impedance pattern for LiNiVO 4 with respect to LiMn 2 O 4 , which may be due to the different electronic processes involved. An attempt has been made to study this behaviour from the solid-state viewpoint

Synthesis and electrochemical properties of Li{sub 2}ZnTi{sub 3}O{sub 8} fibers as an anode material for lithium-ion batteries

Energy Technology Data Exchange (ETDEWEB)

Wang Li; Wu Lijuan; Li Zhaohui; Lei Gangtie [Key Laboratory of Environmentally Friendly Chemistry and Applications of Ministry of Education, College of Chemistry, Xiangtan University, Hunan 411105 (China); Xiao Qizhen, E-mail: qizhenxiao2004@yahoo.com.cn [Key Laboratory of Environmentally Friendly Chemistry and Applications of Ministry of Education, College of Chemistry, Xiangtan University, Hunan 411105 (China); College of Civil Engineering and Mechanics, Xiangtan University, Hunan 411105 (China); Zhang Ping [College of Civil Engineering and Mechanics, Xiangtan University, Hunan 411105 (China)

2011-06-01

Highlights: > A simple electrospinning method has been developed to fabricate Li{sub 2}ZnTi{sub 3}O{sub 8} fibers. > Li{sub 2}ZnTi{sub 3}O{sub 8} fibers as anode material for lithium-ion batteries. > A stable and reversible capacity of over 227 mAh g{sup -1} is achieved at a rate of 0.1 C. > Li{sub 2}ZnTi{sub 3}O{sub 8} anode exhibits good cycle performance and high rate capability. - Abstract: Li{sub 2}ZnTi{sub 3}O{sub 8} fibers are synthesized by thermally treating electrospun Zn(CH{sub 3}COO){sub 2}/LiOAc/TBT/PVP fibers and utilized as an energy storage material for rechargeable lithium-ion batteries. The material is characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, and thermal analysis. Scanning electron microscopy results show that the Li{sub 2}ZnTi{sub 3}O{sub 8} fibers have an average diameter of 200 nm. Electrochemical properties of the material are evaluated using cyclic voltammetry, galvanostatic cycling and electrochemical impedance spectroscopy. The results show that as-prepared Li{sub 2}ZnTi{sub 3}O{sub 8} has a high specific discharge capacity of 227.6 mAh g{sup -1} at the 2nd cycle. Its electrochemical performance at subsequent cycles shows good cycling capacity and rate capability. The obtained results thus strongly support that the electrospinning method is an effective method to prepare Li{sub 2}ZnTi{sub 3}O{sub 8} anode material with higher capacity and rate capability.

Electroactive ionic liquids based on 2,5-ditert-butyl-1,4-dimethoxybenzene and triflimide anion as redox shuttle for Li4Ti5O12/LiFePO4 lithium-ion batteries

Science.gov (United States)

Gélinas, Bruno; Bibienne, Thomas; Dollé, Mickael; Rochefort, Dominic

2017-12-01

In order to increase the solubility and oxidation potential of redox shuttles, electroactive ionic liquids (RILs) based on the modification of 1,4-dimethoxybenzene with triflimide anions were synthesized. We developed two synthetic routes to obtain these RILs in which the triflimide was either linked on the benzene ring or as a ether on 2,5-ditert-butyl-1,4-dimethoxybenzene (DDB). These RILs all have melting points below 100 °C, but above room temperature. The structural impact of electroactive anion was evaluated in this study by determining the redox potential and electrochemical stability. The electrochemical properties of these RILs were investigated by cyclic voltammetry and the diffusion coefficients were measured by double potential step chronoamperometry. The viscosity and ionic conductivity measurements of redox-active electrolyte were obtained at different temperatures and the RIL additives are shown to have a low impact on these electrolyte properties at concentrations up to 0.3 M. The charge-overcharge-discharge cycles of Li/LiFePO4 half-cells and Li4Ti5O12/LiFePO4 full cells with a 100% overcharge are presented using redox-active electrolyte (0.3 M concentration level) at 0.1 C rate. This study highlights the potential of electroactive ionic liquids as highly soluble and stable functional additives in Li-ion battery electrolytes.

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

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.

Solution based synthesis of mixed-phase materials in the Li{sub 2}TiO{sub 3}–Li{sub 4}SiO{sub 4} system

Energy Technology Data Exchange (ETDEWEB)

Hanaor, Dorian A.H., E-mail: dorian.hanaor@sydney.edu.au [School of Civil Engineering, University of Sydney, NSW 2006 (Australia); Kolb, Matthias H.H. [Institute for Applied Materials, Karlsruhe Institute of Technology, 76021 (Germany); Gan, Yixiang [School of Civil Engineering, University of Sydney, NSW 2006 (Australia); Kamlah, Marc; Knitter, Regina [Institute for Applied Materials, Karlsruhe Institute of Technology, 76021 (Germany)

2015-01-15

Highlights: • Investigation of phase stability in the quasi-binary Li{sub 2}TiO{sub 3}–Li{sub 4}SiO{sub 4} system. • Sol-based syntheses of mixed phase materials from organometallic precursors. • LiCl based synthesis results in greater lithium deficiency than LiOH synthesis. • The Li{sub 2}TiO{sub 3}–Li{sub 4}SiO{sub 4} quasi binary system appears to exhibit monotectic behaviour. • Mixed phase materials show liquid formation from melting of silicate material at 1100 °C. - Abstract: As candidate tritium breeder materials for use in the ITER helium cooled pebble bed, ceramic multiphasic compounds lying in the region of the quasi-binary lithium metatitanate–lithium orthosilicate system may exhibit mechanical and physical advantages relative to single phase materials. Here we present an organometallic solution-based synthesis procedure for the low-temperature fabrication of compounds in the Li{sub 2}TiO{sub 3}–Li{sub 4}SiO{sub 4} region and investigate phase stability and transformations through temperature varied X-ray diffraction and scanning calorimetry. Results demonstrate that the metatitanate and metasilicate phases Li{sub 2}TiO{sub 3} and Li{sub 2}SiO{sub 3} readily crystallise in nanocrystalline form at temperatures below 180 °C. Lithium deficiency in the region of 5% results from Li sublimation from Li{sub 4}SiO{sub 4} and/or from excess Li incorporation in the metatitanate phase and brings about a stoichiometry shift, with product compounds exhibiting mixed lithium orthosilicate/metasilicate content towards the Si rich region and predominantly Li{sub 2}TiO{sub 3} content towards the Ti rich region. Above 1150 °C the transformation of monoclinic to cubic γ-Li{sub 2}TiO{sub 3} disordered solid-solution occurs while the melting of silicate phases indicates a likely monotectic type system with a solidus line in the region 1050–1100 °C. Synthesis procedures involving a lithium chloride precursor are not likely to be a viable option for

Improved the lithium storage capability of BaLi2Ti6O14 by electroless silver coating

International Nuclear Information System (INIS)

Lin, Xiaoting; Wang, Pengfei; Li, Peng; Yu, Haoxiang; Qian, Shangshu; Shui, Miao; Wang, Dongjie; Long, Nengbing; Shu, Jie

2015-01-01

Highlights: • BaLi 2 Ti 6 O 14 /Ag is fabricated via a facile electroless deposition. • Highly dispersed Ag nanoparticles are successively coated on BaLi 2 Ti 6 O 14 . • BaLi 2 Ti 6 O 14 /Ag is used as anode material for lithium storage. • BaLi 2 Ti 6 O 14 /Ag exhibits improved lithium storage capability. - Abstract: To form BaLi 2 Ti 6 O 14 /Ag, highly dispersed Ag nanoparticles are successfully deposited on the surface of BaLi 2 Ti 6 O 14 by a simple chemical deposition method. The morphology, quantity and size of Ag nanoparticles in BaLi 2 Ti 6 O 14 /Ag composites are significantly influenced by the Ag coating contents. Electrochemical results show that Ag nanoparticles play a positive role in reducing redox polarization and improving electrical conductivity of BaLi 2 Ti 6 O 14 during lithiation/delithiation processes. Among all the as-obtained products, 6 wt.% Ag coated BaLi 2 Ti 6 O 14 shows the highest initial charge specific capacity of 160 mAh g −1 at the current density of 100 mA g −1 (1C), which is much higher than the 149.1 mAh g −1 for bare BaLi 2 Ti 6 O 14 . After 100 charge/discharge cycles, the reversible capacity can be maintained at 117.0 mAh g −1 . Moreover, this sample also shows excellent rate performance with high reversible charge capacities of 147.5, 139.7, 132.6, and 126.7 mAh g −1 at the rates of 2C, 3C, 4C and 5C, respectively. Compared with bare BaLi 2 Ti 6 O 14 , the superior electrochemical performance indicates that BaLi 2 Ti 6 O 14 /Ag can be a good anode material in lithium ion batteries.

A high energy and power Li-ion capacitor based on a TiO2 nanobelt array anode and a graphene hydrogel cathode.

Science.gov (United States)

Wang, Huanwen; Guan, Cao; Wang, Xuefeng; Fan, Hong Jin

2015-03-25

A novel hybrid Li-ion capacitor (LIC) with high energy and power densities is constructed by combining an electrochemical double layer capacitor type cathode (graphene hydrogels) with a Li-ion battery type anode (TiO(2) nanobelt arrays). The high power source is provided by the graphene hydrogel cathode, which has a 3D porous network structure and high electrical conductivity, and the counter anode is made of free-standing TiO(2) nanobelt arrays (NBA) grown directly on Ti foil without any ancillary materials. Such a subtle designed hybrid Li-ion capacitor allows rapid electron and ion transport in the non-aqueous electrolyte. Within a voltage range of 0.0-3.8 V, a high energy of 82 Wh kg(-1) is achieved at a power density of 570 W kg(-1). Even at an 8.4 s charge/discharge rate, an energy density as high as 21 Wh kg(-1) can be retained. These results demonstrate that the TiO(2) NBA//graphene hydrogel LIC exhibits higher energy density than supercapacitors and better power density than Li-ion batteries, which makes it a promising electrochemical power source. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

High-Performance Li-Ion Capacitor Based on an Activated Carbon Cathode and Well-Dispersed Ultrafine TiO2 Nanoparticles Embedded in Mesoporous Carbon Nanofibers Anode.

Science.gov (United States)

Yang, Cheng; Lan, Jin-Le; Liu, Wen-Xiao; Liu, Yuan; Yu, Yun-Hua; Yang, Xiao-Ping

2017-06-07

A novel Li-ion capacitor based on an activated carbon cathode and a well-dispersed ultrafine TiO 2 nanoparticles embedded in mesoporous carbon nanofibers (TiO 2 @PCNFs) anode was reported. A series of TiO 2 @PCNFs anode materials were prepared via a scalable electrospinning method followed by carbonization and a postetching method. The size of TiO 2 nanoparticles and the mesoporous structure of the TiO 2 @PCNFs were tuned by varying amounts of tetraethyl orthosilicate (TEOS) to increase the energy density and power density of the LIC significantly. Such a subtle designed LIC displayed a high energy density of 67.4 Wh kg -1 at a power density of 75 W kg -1 . Meanwhile, even when the power density was increased to 5 kW kg -1 , the energy density can still maintain 27.5 Wh kg -1 . Moreover, the LIC displayed a high capacitance retention of 80.5% after 10000 cycles at 10 A g -1 . The outstanding electrochemical performance can be contributed to the synergistic effect of the well-dispersed ultrafine TiO 2 nanoparticles, the abundant mesoporous structure, and the conductive carbon networks.

Li{sub 4}SiO{sub 4} based breeder ceramics with Li{sub 2}TiO{sub 3}, LiAlO{sub 2} and Li{sub X}La{sub Y}TiO{sub 3} additions, part II: Pebble properties

Energy Technology Data Exchange (ETDEWEB)

Kolb, M.H.H., E-mail: Matthias.kolb@kit.edu [Karlsruhe Institute of Technology, Institute for Applied Materials, PO Box 3640, 76021, Karlsruhe (Germany); Knitter, R. [Karlsruhe Institute of Technology, Institute for Applied Materials, PO Box 3640, 76021, Karlsruhe (Germany); Hoshino, T. [Breeding Functional Materials Development Group, Department of Blanket Systems Research, Rokkasho Fusion Institute, Fusion Energy Research and Development Directorate, National Institutes for Quantum and Radiological Science and Technology (QST) (Japan)

2017-02-15

Highlights: • The mechanical strength of Li{sub 4}SiO{sub 4}-based breeder pebbles can be improved by adding either LMT, LAO or LLTO as second phase. • The increase in strength is closely linked to a reduction of the open porosity of the pebbles. • All fabricated pebbles show a highly homogenous microstructure with mostly low closed porosity. • Adding LLTO, although it decomposes during sintering, greatly improves the strength of the pebbles. - Abstract: The pebble properties of novel two-phase Li{sub 4}SiO{sub 4} pebbles of 1 mm diameter with additions of Li{sub 2}TiO{sub 3}, LiAlO{sub 2} or Li{sub x}La{sub y}TiO{sub 3} are evaluated in this work as a function of the second phase concentration and the microstructure of the pebbles. The characterization focused on the mechanical strength, microstructure and open as well as closed porosity. Therefore crush load tests, SEM analyses as well as helium pycnometry and optical image analysis were performed, respectively. This work shows that generally additions of a second phase to Li{sub 4}SiO{sub 4} considerably improve the mechanical strength. It also shows that the fabrication processes have to be well-controlled to achieve high mechanical strengths. When Li{sub 2}TiO{sub 3} is added in different concentrations, the determinant for the crush load seems to be the open porosity of the pebbles. The strengthening effect of LiAlO{sub 2} compared to Li{sub 2}TiO{sub 3} is similar, while additions of Li{sub x}La{sub y}TiO{sub 3} increase the mechanical strength much more. Yet, Li{sub 4}SiO{sub 4} and Li{sub x}La{sub y}TiO{sub 3} react with each other to a number of different phases upon sintering. In general the pebble properties of all samples are favorable for use within a fusion breeder blanket.

Experimental and modeling analysis of thermal runaway propagation over the large format energy storage battery module with Li_4Ti_5O_1_2 anode

International Nuclear Information System (INIS)

Huang, Peifeng; Ping, Ping; Li, Ke; Chen, Haodong; Wang, Qingsong; Wen, Jennifer; Sun, Jinhua

2016-01-01

Highlights: • The heat generation and gas production of four main thermal-chemical reactions are detected. • The fire-impingement takes an unordinary thermal runaway propagation for battery module. • There is a “smoldering period” before the explosion of lithium ion battery module. • Semenov and Frank-Kamenetskii models are used to analysis and predict the onset of runaway. - Abstract: Insight of the thermal characteristics and potential flame spread over lithium-ion battery (LIB) modules is important for designing battery thermal management system and fire protection measures. Such thermal characteristics and potential flame spread are also dependent on the different anode and cathode materials as well as the electrolyte. In the present study, thermal behavior and flame propagation over seven 50 A h Li(Ni_1_/_3Mn_1_/_3Co_1_/_3)O_2/Li_4Ti_5O_1_2 large format LIBs arranged in rhombus and parallel layouts were investigated by directly heating one of the battery units. Such batteries have already been used commercially for energy storage while relatively little is known about its safety features in connection with potential runaway caused fire and explosion hazards. It was found in the present heating tests that fire-impingement resulted in elevated temperatures in the immediate vicinity of the LIBs that were in the range of between 200 °C and 900 °C. Such temperature aggravated thermal runaway (TR) propagation, resulting in rapid temperature rise within the battery module and even explosions after 20 min of “smoldering period”. The thermal runaway and subsequent fire and explosion observed in the heating test was attributed to the violent reduction of the cathode material which coexisted with the electrolyte when the temperature exceeded 260 °C. Separate laboratory tests, which measured the heat and gases generation from samples of the anode and cathode materials using C80 calorimeter, provided insight of the physical-chemistry processes inside the

A promising tritium breeding material: Nanostructured 2Li2TiO3-Li4SiO4 biphasic ceramic pebbles

Science.gov (United States)

Dang, Chen; Yang, Mao; Gong, Yichao; Feng, Lan; Wang, Hailiang; Shi, Yanli; Shi, Qiwu; Qi, Jianqi; Lu, Tiecheng

2018-03-01

As an advanced tritium breeder material for the fusion reactor blanket of the International Thermonuclear Experimental Reactor (ITER), Li2TiO3-Li4SiO4 biphasic ceramic has attracted widely attention due to its merits. In this paper, the uniform precursor powders were prepared by hydrothermal method, and nanostructured 2Li2TiO3-Li4SiO4 biphasic ceramic pebbles were fabricated by an indirect wet method at the first time. In addition, the composition dependence (x/y) of their microstructure characteristics and mechanical properties were investigated. The results indicated that the crush load of biphasic ceramic pebbles was better than that of single phase ceramic pebbles under identical conditions. The 2Li2TiO3-Li4SiO4 ceramic pebbles have good morphology, small grain size (90 nm), satisfactory crush load (37.8 N) and relative density (81.8 %T.D.), which could be a promising breeding material in the future fusion reactor.

Electrochemical performance of La2O3/Li2O/TiO2 nano-particle coated cathode material LiFePO4.

Science.gov (United States)

Wang, Hong; Yang, Chi; Liu, Shu-Xin

2014-09-01

Cathode material, LiFePO4 was modified by coating with a thin layer of La2O3/Li2O/TiO2 nano-particles for improving its performance for lithium ion batteries. The morphology and structure of the modified cathode material were characterized by powder X-ray diffraction, scanning electron microcopy and AES. The performance of the battery with the modified cathode material, including cycling stability, C-rate discharge was examined. The results show that the battery composed of the coated cathode materials can discharge at a large current density and show stable cycling performance in the range from 2.5 to 4.0 V. The rate of Li ion diffusion increases in the battery with the La2O3/Li2O/TiO2-coated LiFePO4 as a cathode and the coating layer may acts as a faster ion conductor (La(2/3-x)Li(3x)TiO3).

Electrochemical performance of LiNi0.5Mn1.5O4 prepared by improved solid state method as cathode in hybrid supercapacitor

International Nuclear Information System (INIS)

Wu Huiming; Rao, Ch. Venkateswara; Rambabu, B.

2009-01-01

The electrochemical performance of a hybrid asymmetric supercapacitor with activated carbon (AC) as anode and a lithium-ion intercalated compound LiNi 0.5 Mn 1.5 O 4 as cathode was studied. By using metal acetate precursors as starting materials in solid state reaction method, pure LiNi 0.5 Mn 1.5 O 4 was formed at low temperature. The role of precursors on the formation of material at low temperature and short period of time is presented. XRD confirms the cubic spinel structure (space group, Fd3m) and SEM shows the particles of size around 1 μm. The effect of the modified solid state reaction route on the structural and electrochemical properties was investigated. The fabricated hybrid supercapacitor, AC/LiNi 0.5 Mn 1.5 O 4 in a non-aqueous electrolyte 1.0 M LiPF 6 /EC-DMC exhibits a sloping voltage profile from 1.0 to 3.0 V and delivers a specific energy of ca. 56 Wh kg -1 . Moreover, it exhibits excellent cycling performance with less than 5% capacity loss over 1000 cycles.

Spinel-structured surface layers for facile Li ion transport and improved chemical stability of lithium manganese oxide spinel

Energy Technology Data Exchange (ETDEWEB)

Lee, Hae Ri [Center for Energy Convergence Research, Korea Institute of Science Technology, Hwarang-ro 14-gil 5, Seongbuk-gu, Seoul 136-791 (Korea, Republic of); Department of Chemical and Biological Engineering, Korea University, 145, Anam-ro, Seongbuk-gu, Seoul 136-701 (Korea, Republic of); Seo, Hyo Ree; Lee, Boeun; Cho, Byung Won [Center for Energy Convergence Research, Korea Institute of Science Technology, Hwarang-ro 14-gil 5, Seongbuk-gu, Seoul 136-791 (Korea, Republic of); Lee, Kwan-Young [Department of Chemical and Biological Engineering, Korea University, 145, Anam-ro, Seongbuk-gu, Seoul 136-701 (Korea, Republic of); Oh, Si Hyoung, E-mail: sho74@kist.re.kr [Center for Energy Convergence Research, Korea Institute of Science Technology, Hwarang-ro 14-gil 5, Seongbuk-gu, Seoul 136-791 (Korea, Republic of)

2017-01-15

Graphical abstract: Strategically-designed spinel-structured nano-scale surface layer, LiM{sub x}Mn{sup IV}{sub 1−x}O{sub 4}, featuring a high Li{sup +} ion conductivity and a good chemical stability was applied on Al-doped LiMn{sub 2}O{sub 4} spinel for the drastic improvement of the electrochemical performance at the elevated temperature as a promising cathode material for lithium rechargeable batteries. - Highlights: • Spinel-structured surface layer with a high Li-ion conductivity and a good chemical stability was prepared. • Simple wet process was developed to apply nano-scale surface layer on aluminum doped lithium manganese oxide spinel. • The properties of nano-scale surface layer were characterized by analytical tools including GITT, HR-TEM and XAS. • Materials with surface coating layer exhibit an excellent electrochemical performance at the elevated temperature. - Abstract: Li-ion conducting spinel-structured oxide layer with a manganese oxidation state close to being tetravalent was prepared on aluminum-doped lithium manganese oxide spinel for improving the electrochemical performances at the elevated temperatures. This nanoscale surface layer provides a good ionic conduction path for lithium ion transport to the core and also serves as an excellent chemical barrier for protecting the high-capacity core material from manganese dissolution into the electrolyte. In this work, a simple wet process was employed to prepare thin LiAlMnO{sub 4} and LiMg{sub 0.5}Mn{sub 1.5}O{sub 4} layers on the surface of LiAl{sub 0.1}Mn{sub 1.9}O{sub 4}. X-ray absorption studies revealed an oxidation state close to tetravalent manganese on the surface layer of coated materials. Materials with these surface coating layers exhibited excellent capacity retentions superior to the bare material, without undermining the lithium ion transport characteristics and the high rate performances.

Li{sub 4}SiO{sub 4} based breeder ceramics with Li{sub 2}TiO{sub 3}, LiAlO{sub 2} and Li{sub X}La{sub Y}TiO{sub 3} additions, part I: Fabrication

Energy Technology Data Exchange (ETDEWEB)

Kolb, M.H.H., E-mail: Matthias.kolb@kit.edu [Karlsruhe Institute of Technology, Institute for Applied Materials, PO Box 3640, 76021 Karlsruhe (Germany); Mukai, K.; Knitter, R. [Karlsruhe Institute of Technology, Institute for Applied Materials, PO Box 3640, 76021 Karlsruhe (Germany); Hoshino, T. [Breeding Functional Materials Development Group, Department of Blanket Systems Research, Rokkasho Fusion Institute, Fusion Energy Research and Development Directorate, National Institutes for Quantum and Radiological Science and Technology (QST) (Japan)

2017-02-15

Highlights: • This study shows that the emulsion method can easily be adapted to add different phases into Li4SiO4 breeder pebbles. • Slurries with various compositions to form LOS + LMT, LOS + LAO and LOS + LLTO were processed.The calculated activation behavior shows that samples with added LAO or LLTO qualify as low activation material. • Yet, the long-term activation of the LAO containing samples is problematic as hands-on level activity is not reached quickly. - Abstract: Wet-chemical fabrication processes are highly adaptable to a wide range of raw materials and are therefore well suited for evaluating new material compositions. Here the established emulsion method was modified to fabricate novel two-phase Li{sub 4}SiO{sub 4} pebbles of 1 mm diameter with additions of Li{sub 2}TiO{sub 3}, LiAlO{sub 2} or Li{sub x}La{sub y}TiO{sub 3}. As the lithium density of the latter two compounds is relatively low, only moderate contents were added. The Li{sub 2}TiO{sub 3} additions, however, cover the full compositional range. The fabrication process was characterized with regard to its constancy and aptness for the anticipated pebble compositions by optical pebble size measurements. Also the phase content and the elemental composition of the fabricated pebbles were analyzed by XRD and ICP-OES combined with XRF, respectively. This work shows that the emulsion method is an appropriate method to produce pebbles with the anticipated Li{sub 2}TiO{sub 3} and LiAlO{sub 2} concentrations in a Li{sub 4}SiO{sub 4} matrix. However, Li{sub 4}SiO{sub 4} and Li{sub x}La{sub y}TiO{sub 3} react with each other to a number of different phases. To evaluate the activation properties of the pebbles, FISPACT calculations with a DEMO relevant neutron source are applied as well. The addition of aluminum seems to be unfavorable for a fusion application, but moderate concentrations of lanthanum can be tolerated.

Nanoporous LiMn2O4 spinel prepared at low temperature as cathode material for aqueous supercapacitors

Science.gov (United States)

Wang, F. X.; Xiao, S. Y.; Gao, X. W.; Zhu, Y. S.; Zhang, H. P.; Wu, Y. P.; Holze, R.

2013-11-01

LiMn2O4 spinel was prepared by a hydrothermal method using α-MnO2 nanotubes as precursor at 180 °C, a temperature much lower than that in previously reported methods. It is nanoporous with a pore size of about 40-50 nm and a BET surface area of 9.76 m2 g-1. It exhibits a high specific capacitance of 189 F g-1 at 0.3 A g-1 as a cathode for an aqueous supercapacitor. Even at 12 A g-1, it still has a capacitance of 166 F g-1. After 1500 cycles, there is no evident capacity fading. The LiMn2O4 cathode can deliver an energy density of 31.9 Wh kg-1 at 3480 W kg-1 and even maintain 19.4 Wh kg-1 at about 5100 W kg-1 based on the mass of LiMn2O4.

Electronic, Structural, and Electrochemical Properties of LiNixCuyMn2-x-yO4 (0 < x < 0.5, 0 < y < 0.5) High-Voltage Spinel Materials

International Nuclear Information System (INIS)

Yang, Ming-Che; Xu, Bo; Cheng, Ju-Hsiang; Pan, Chun-Jern; Hwang, Bing-Joe; Meng, Ying S.

2011-01-01

First principles computation is carried out for investigating the electronic, structural, and electrochemical properties of LiM 1/2 Mn 3/2 O 4 (M = Ti, V, Cr, Fe, Co, Ni, and Cu). The computation results suggest that doping with Co or Cu can potentially lower Li diffusion barrier as compared to Ni doping. Our experimental research has focused on LiNi x Cu y Mn 2-x-y O 4 (0 x Cu y Mn 2-x-6 O 4 (0 0.25 Cu 0.25 Mn 1.50 O 4 , the proposed explanation of the voltage profile by the first principles computation was proven, a second plateau at 4.2 V originates from the oxidation of Cu 2+ to Cu 3+ , and the plateau at 4.95 V may originate from extra electrons provided by oxygen ions. Although the reversible discharge capacity decreases with increasing Cu amount, optimized composition such as LiCu 0.25 Ni 0.25 Mn 1.5 O 4 exhibits high capacities at high rates.

Process Design for Size-Controlled Flame Spray Synthesis of Li4Ti5O12 and Electrochemical Performance

Directory of Open Access Journals (Sweden)

Waser Oliver

2017-03-01

Full Text Available Inexpensive synthesis of electroceramic materials is required for efficient energy storage. Here the design of a scalable process, flame spray pyrolysis (FSP, for synthesis of size-controlled nanomaterials is investigated focusing on understanding the role of air entrainment (AE during their aerosol synthesis with emphasis on battery materials. The AE into the enclosed FSP reactor is analysed quantitatively by computational fluid dynamics (CFD and calculated temperatures are verified by Fourier transform infrared spectroscopy (FTIR. Various Li4Ti5O12 (LTO particle compositions are made and characterized by N2 adsorption, electron microscopy and X-ray diffraction while the electrochemical performance of LTO is tested at various charging rates. Increasing AE decreases recirculation in the enclosing tube leading to lower reactor temperatures and particle concentrations by air dilution as well as shorter and narrower residence time distributions. As a result, particle growth by coagulation - coalescence decreases leading to smaller primary particles that are mostly pure LTO exhibiting high C-rate performance with more than 120 mAh/g galvanostatic specific charge at 40C, outperforming commercial LTO. The effect of AE on FSP-made particle characteristics is demonstrated also in combustion synthesis of LiFePO4 and ZrO2.

Li4SiO4-Based Artificial Passivation Thin Film for Improving Interfacial Stability of Li Metal Anodes.

Science.gov (United States)

Kim, Ji Young; Kim, A-Young; Liu, Guicheng; Woo, Jae-Young; Kim, Hansung; Lee, Joong Kee

2018-03-14

An amorphous SiO 2 (a-SiO 2 ) thin film was developed as an artificial passivation layer to stabilize Li metal anodes during electrochemical reactions. The thin film was prepared using an electron cyclotron resonance-chemical vapor deposition apparatus. The obtained passivation layer has a hierarchical structure, which is composed of lithium silicide, lithiated silicon oxide, and a-SiO 2 . The thickness of the a-SiO 2 passivation layer could be varied by changing the processing time, whereas that of the lithium silicide and lithiated silicon oxide layers was almost constant. During cycling, the surface of the a-SiO 2 passivation layer is converted into lithium silicate (Li 4 SiO 4 ), and the portion of Li 4 SiO 4 depends on the thickness of a-SiO 2 . A minimum overpotential of 21.7 mV was observed at the Li metal electrode at a current density of 3 mA cm -2 with flat voltage profiles, when an a-SiO 2 passivation layer of 92.5 nm was used. The Li metal with this optimized thin passivation layer also showed the lowest charge-transfer resistance (3.948 Ω cm) and the highest Li ion diffusivity (7.06 × 10 -14 cm 2 s -1 ) after cycling in a Li-S battery. The existence of the Li 4 SiO 4 artificial passivation layer prevents the corrosion of Li metal by suppressing Li dendritic growth and improving the ionic conductivity, which contribute to the low charge-transfer resistance and high Li ion diffusivity of the electrode.

Synthesis and electrochemical characteristics of spinel LiMn2O4 via a precipitation spray-drying process

International Nuclear Information System (INIS)

Wu, H.M.; Tu, J.P.; Yuan, Y.F.; Li, Y.; Zhao, X.B.; Cao, G.S.

2005-01-01

Spinel LiMn 2 O 4 has been successfully synthesized using a precipitation spray-drying process. After the precursor was annealed at 750 deg. C for 10 h, the synthesized material was well-crystallized spinel particle, and exhibited uniform particle size distribution. From cyclic voltammetry results, there is an anomalous redox peaks (3.75/3.26 V). In the charge/discharge potential (versus Li) ranging from 3.2 to 4.5 V, it delivered a high initial discharge capacity of 123 mAh/g at a discharge rate of 60 μA/cm 2 (1/4 C rate). At a high discharge rate of 2.4 mA/cm 2 (10 C rate), the obtainable reversible capacity was 79 mAh/g. The simple procedure of precipitation spray-drying process is time and energy saving, and thus is promising for commercial application

Lithium Titanate Ceramic System as Electronic and Li-ion Mixed Conductors for Cathode Matrix in Lithium-Sulfur Battery

OpenAIRE

Ogihara, Hideki

2012-01-01

Lithium-Titanat-Spinell Li4/3Ti5/3O4, Ramsdellit Li2Ti3O7, und Spinell - Steinsalz abgeleitet Li4/3+xTi5/3O4 (0 kleiner/gleich x kleiner/gleich 1) wurden untersucht, um ein gemischtes (d.h. Li-Ionen und Elektronen) leitendes keramisches Material als eine Kathode-Matrix für alle Festköper-Lithium-Schwefel-Batterie zu entwickeln.

Solid state opto-impedance of LiNiVO{sub 4} and LiMn{sub 2}O{sub 4}

Energy Technology Data Exchange (ETDEWEB)

Kalyani, P; Sivasubramanian, S; Prabhu, S Naveen; Ragavendran, K; Kalaiselvi, N; Ranganathan, N G; Madhu, S; SundaraRaj, A; Manoharan, S P; Jagannathan, R [Central Electrochemical Research Institute, Karaikudi-630006, Tamil Nadu (India)

2005-04-07

Spinel type LiMn{sub 2}O{sub 4} and inverse spinel LiNiVO{sub 4} systems serve as standard cathode materials or potential cathode systems for application in high energy density lithium-ion batteries. Upon photo-excitation using UV radiation of energy {approx}5 eV, the LiNiVO{sub 4} system shows significant modification in the solid state impedance pattern while the LiMn{sub 2}O{sub 4} system does not. This study has revealed a significant difference in the opto-impedance pattern for LiNiVO{sub 4} with respect to LiMn{sub 2}O{sub 4}, which may be due to the different electronic processes involved. An attempt has been made to study this behaviour from the solid-state viewpoint.

About the Compatibility between High Voltage Spinel Cathode Materials and Solid Oxide Electrolytes as a Function of Temperature.

Science.gov (United States)

Miara, Lincoln; Windmüller, Anna; Tsai, Chih-Long; Richards, William D; Ma, Qianli; Uhlenbruck, Sven; Guillon, Olivier; Ceder, Gerbrand

2016-10-12

The reactivity of mixtures of high voltage spinel cathode materials Li 2 NiMn 3 O 8 , Li 2 FeMn 3 O 8 , and LiCoMnO 4 cosintered with Li 1.5 Al 0.5 Ti 1.5 (PO 4 ) 3 and Li 6.6 La 3 Zr 1.6 Ta 0.4 O 12 electrolytes is studied by thermal analysis using X-ray-diffraction and differential thermoanalysis and thermogravimetry coupled with mass spectrometry. The results are compared with predicted decomposition reactions from first-principles calculations. Decomposition of the mixtures begins at 600 °C, significantly lower than the decomposition temperature of any component, especially the electrolytes. For the cathode + Li 6.6 La 3 Zr 1.6 Ta 0.4 O 12 mixtures, lithium and oxygen from the electrolyte react with the cathodes to form highly stable Li 2 MnO 3 and then decompose to form stable and often insulating phases such as La 2 Zr 2 O 7 , La 2 O 3 , La 3 TaO 7 , TiO 2 , and LaMnO 3 which are likely to increase the interfacial impedance of a cathode composite. The decomposition reactions are identified with high fidelity by first-principles calculations. For the cathode + Li 1.5 Al 0.5 Ti 1.5 (PO 4 ) 3 mixtures, the Mn tends to oxidize to MnO 2 or Mn 2 O 3 , supplying lithium to the electrolyte for the formation of Li 3 PO 4 and metal phosphates such as AlPO 4 and LiMPO 4 (M = Mn, Ni). The results indicate that high temperature cosintering to form dense cathode composites between spinel cathodes and oxide electrolytes will produce high impedance interfacial products, complicating solid state battery manufacturing.

Topotactic oxidation pathway of ScTiO3 and high-temperature structure evolution of ScTiO3.5 and Sc4Ti3O12-type phases.

Science.gov (United States)

Shafi, Shahid P; Hernden, Bradley C; Cranswick, Lachlan M D; Hansen, Thomas C; Bieringer, Mario

2012-02-06

The novel oxide defect fluorite phase ScTiO(3.5) is formed during the topotactic oxidation of ScTiO(3) bixbyite. We report the oxidation pathway of ScTiO(3) and structure evolution of ScTiO(3.5), Sc(4)Ti(3)O(12), and related scandium-deficient phases as well as high-temperature phase transitions between room temperature and 1300 °Cusing in-situ X-ray diffraction. We provide the first detailed powder neutron diffraction study for ScTiO(3). ScTiO(3) crystallizes in the cubic bixbyite structure in space group Ia3 (206) with a = 9.7099(4) Å. The topotactic oxidation product ScTiO(3.5) crystallizes in an oxide defect fluorite structure in space group Fm3m (225) with a = 4.89199(5) Å. Thermogravimetric and differential thermal analysis experiments combined with in-situ X-ray powder diffraction studies illustrate a complex sequence of a topotactic oxidation pathway, phase segregation, and ion ordering at high temperatures. The optimized bulk synthesis for phase pure ScTiO(3.5) is presented. In contrast to the vanadium-based defect fluorite phases AVO(3.5+x) (A = Sc, In) the novel titanium analogue ScTiO(3.5) is stable over a wide temperature range. Above 950 °C ScTiO(3.5) undergoes decomposition with the final products being Sc(4)Ti(3)O(12) and TiO(2). Simultaneous Rietveld refinements against powder X-ray and neutron diffraction data showed that Sc(4)Ti(3)O(12) also exists in the defect fluorite structure in space group Fm3m (225) with a = 4.90077(4) Å. Sc(4)Ti(3)O(12) undergoes partial reduction in CO/Ar atmosphere to form Sc(4)Ti(3)O(11.69(2)).

Polyfluorinated boron cluster based salts: A new electrolyte for application in nonaqueous asymmetric AC/Li{sub 4}Ti{sub 5}O{sub 12} supercapacitors

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Ionica-Bousquet, C.M.; Munoz-Rojas, D.; Palacin, M.R. [Institut de Ciencia de Materials de Barcelona, CSIC, Campus UAB, E-08193 Bellaterra (Spain); Casteel, W.J. Jr.; Pearlstein, R.M.; Kumar, G. Girish; Pez, G.P. [Air Products and Chemicals, Inc., 7201 Hamilton Blvd., Allentown, PA 18195 (United States)

2011-02-01

Solutions of novel fluorinated lithium dodecaborate (Li{sub 2}B{sub 12}F{sub x}H{sub 12-x}) salts have been evaluated as electrolytes in nonaqueous asymmetric supercapacitors with Li{sub 4}Ti{sub 5}O{sub 12} as negative electrode, and activated carbon (AC) as positive electrode. The results obtained with these new electrolytes were compared with those obtained with cells built using standard 1 M LiPF{sub 6} dissolved in ethylene carbonate and dimethyl carbonate (EC:DMC; 1:1, v/v) as electrolyte. The specific energy, rate capability, and cycling performances of nonaqueous asymmetric cells based on these new electrolyte salts were studied. Cells assembled using the new fluoroborate salts show excellent reversibility, coulombic efficiency, rate capability and improved cyclability when compared with the standard electrolyte. These features confirm the suitability of lithium-fluoro-borate based salts to be used in nonaqueous asymmetric supercapacitors. (author)

Nature of the Electrochemical Properties of Sulphur Substituted LiMn2O4 Spinel Cathode Material Studied by Electrochemical Impedance Spectroscopy

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Monika Bakierska

2016-08-01

Full Text Available In this work, nanostructured LiMn2O4 (LMO and LiMn2O3.99S0.01 (LMOS1 spinel cathode materials were comprehensively investigated in terms of electrochemical properties. For this purpose, electrochemical impedance spectroscopy (EIS measurements as a function of state of charge (SOC were conducted on a representative charge and discharge cycle. The changes in the electrochemical performance of the stoichiometric and sulphur-substituted lithium manganese oxide spinels were examined, and suggested explanations for the observed dependencies were given. A strong influence of sulphur introduction into the spinel structure on the chemical stability and electrochemical characteristic was observed. It was demonstrated that the significant improvement in coulombic efficiency and capacity retention of lithium cell with LMOS1 active material arises from a more stable solid electrolyte interphase (SEI layer. Based on EIS studies, the Li ion diffusion coefficients in the cathodes were estimated, and the influence of sulphur on Li+ diffusivity in the spinel structure was established. The obtained results support the assumption that sulphur substitution is an effective way to promote chemical stability and the electrochemical performance of LiMn2O4 cathode material.

Checkerboard deposition of lithium manganese oxide spinel (LiMn2O4) by RF magnetron sputtering on a stainless steel in all-solid-state thin film battery