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.

NMR study of electrode materials for lithium ion-batteries; Etude par RMN de materiaux d'electrode pour batteries lithium-ion

Energy Technology Data Exchange (ETDEWEB)

Chazel, C.

2006-01-15

This work is devoted to the study of LiMO{sub 2} et LiM{sub 2}O{sub 4} (M: transition metal) intercalation compounds used as electrode material for lithium-ion batteries. Solid state NMR allows one to characterise the local environment of the lithium ions present in these phases by the use of the hyperfine interactions due to the presence of some electron spin density coming from localised electrons (Fermi-contact shift) or itinerant electrons (Knight shift) on the lithium nucleus. By following the transformation of the LiNiO{sub 2} layered phase into the LiNi{sub 2}O{sub 4} spinel material using lithium NMR, we studied the nature of the asymmetric signal observed for LiNiO{sub 2}, and the influence of the departure from the ideal stoichiometry; we showed a coupled ion/electron hopping in Li{sub X}NiO{sub 2} phases linked to Li/vacancy and Ni{sup 3+}/Ni{sup 4+} ordering, and finally showed the existence of structural defects within the LiNi{sub 2}O{sub 4} spinel phase obtained by thermal treatment of Li{sub 0.5}NiO{sub 2}. Lithium NMR of the intercalated materials obtained from the LiTi{sub 2}O{sub 4} and Li{sub 4}Ti{sub 5}O{sub 12} spinels showed a metallic behaviour for Li{sub 2}Ti{sub 2}O{sub 4} with a Knight shift of the NMR signal similar to that of LiTi{sub 2}O{sub 4}, and signals intermediate in nature between Knight and Fermi-contact shifts for Li{sub 7}Ti{sub 5}O{sub 12}. (author)

Ultrathin NiO/NiFe2O4 Nanoplates Decorated Graphene Nanosheets with Enhanced Lithium Storage Properties

International Nuclear Information System (INIS)

Du, Dejian; Yue, Wenbo; Fan, Xialu; Tang, Kun; Yang, Xiaojing

2016-01-01

Highlights: • Ultrathin NiO/NiFe 2 O 4 nanoplates derived from NiFe layered double hydroxides are fabricated on the graphene. • NiO/NiFe 2 O 4 nanoplates on the graphene show superior electrochemical performance compared to pure NiO/NiFe 2 O 4 aggregates. • The effects of the content and the particle size/component of NiO/NiFe 2 O 4 on the electrochemical performances are studied. • Graphene-encapsulated NiO/NiFe 2 O 4 is prepared and shows slightly decreased performance compared to graphene-based composite. - Abstract: As anode materials for lithium-ion batteries, bicomponent metal oxide composites show high reversible capacities; but the morphology and particle size of the composites are hardly controllable, which may reduce their electrochemical properties. In this work, ultrathin NiO/NiFe 2 O 4 nanoplates with a diameter of 5 ∼ 7 nm and a thickness of ∼2 nm are controllably fabricated on the graphene derived from NiFe layered double hydroxides (NiFe-LDHs), and exhibit superior electrochemical performance compared to pure NiO/NiFe 2 O 4 aggregates without graphene. The nanosized NiO and NiFe 2 O 4 plates are separated from each other and the graphene substrate can prevent the aggregation of NiO/NiFe 2 O 4 as well as enhance the electronic conductivity of the composite, which is beneficial to improving the electrochemical performance. Moreover, the effects of the content and the particle size/component of NiO/NiFe 2 O 4 on the electrochemical performances are also studied in order to achieve optimal performance. Ultrathin NiO/NiFe 2 O 4 nanoplates are further encapsulated by graphene nanosheets and show slightly decreased performance compared to those supported by graphene nanosheets. The different electrochemical behaviors of graphene-containing composites may be attributed to the different interactions between graphene nanosheets and NiO/NiFe 2 O 4 nanoplates.

Phase transition and hysteresis in a rechargeable lithium battery

Energy Technology Data Exchange (ETDEWEB)

Dreyer, Wolfgang [Weierstrass-Institut fuer Angewandte Analysis und Stochastik (WIAS) im Forschungsverbund Berlin e.V. (Germany); Gaberscek, Miran; Jamnik, Janko [Kemijski Institut Ljubljana Slovenija (Slovenia). L10 Lab. for Materials Electrochemistry

2007-07-01

We develop a model which describes the evolution of a phase transition that occurs in some part of a rechargeable lithium battery during the process of charging/discharging. The model is capable to simulate hysteretic behavior of the voltage - charge characteristics. During discharging of the battery, the interstitial lattice sites of a small crystalline host system are filled up with lithium atoms and these are released again during charging. We show within the context of a sharp interface model that two mechanical phenomena go along with a phase transition that appears in the host system during supply and removal of lithium. At first the lithium atoms need more space than it is available by the interstitial lattice sites, which leads to a maximal relative change of the crystal volume of about 6%. Furthermore there is an interface between two adjacent phases that has very large curvature of the order of magnitude 100 m, which evoke here a discontinuity of the normal component of the stress. In order to simulate the dynamics of the phase transitions and in particular the observed hysteresis we establish a new initial and boundary value problem for a nonlinear PDE system that can be reduced in some limiting case to an ODE system. (orig.)

Interconnected Ni_2P nanorods grown on nickel foam for binder free lithium ion batteries

International Nuclear Information System (INIS)

Li, Qin; Ma, Jingjing; Wang, Huijun; Yang, Xia; Yuan, Ruo; Chai, Yaqin

2016-01-01

Herein, we report a moderate and simple approach to synthesize nickel phosphide nanorods on nickel foam (Ni_2P/NF), which was employed as anode material for lithium ion batteries (LIBs). In this paper, interconnected Ni_2P nanorods were fabricated through hydrothermal treatment of NF and subsequently by high temperature phosphating. NF is not only regarded as nickel source and metal current collector, but also as a support to grow electro-active material (Ni_2P). Therefore, Ni_2P/NF could act as a self-supported working electrode for LIBs without any extra addition of cohesive binders. Moreover, benefiting from the conductive capacity of Ni_2P/NF, the active compound behaved superior lithium storage performance and cycling reversibility during electrochemical cycling process. The Ni_2P/NF delivered excellent reversibility of 507 mAh g"−"1 at the current density of 50 mA g"−"1 after 100 cycles. This work may provide a potential method for preparation of metal phosphides as promising materials for LIBs, hydrogen evolution reaction (HER) or other fields.

An ingenious design of lamellar Li1.2Mn0.54Ni0.13Co0.13O2 hollow nanosphere cathode for advanced lithium-ion batteries

International Nuclear Information System (INIS)

Zhang, Yao; Zhang, Wansen; Shen, Shuiyun; Yan, Xiaohui; Wu, Aiming; Wu, Ruofei; Zhang, Junliang

2017-01-01

Highlights: •Lamellar Li 1.2 Mn 0.54 Ni 0.13 Co 0.13 O 2 hollow nanospheres serve as a cathode for LIBs. •Unique lamella and hollow structures benefit the enhanced electrochemical performance. •Lamellar shells can provide a short lithium-ion diffusion pathway. •The sufficient void space can accommodate volumetric expansion and contraction. -- Abstract: Although very appealing in developing hollow structured lithium-rich layered transition-metal oxides as cathodes for lithium-ion batteries (LIBs), a great challenge lies in controlling the growth of transition metal elements with desired molar ratios while maintaining intact hollow structures during synthesis. Herein, we propose a scalable strategy to successfully synthesize novel lamellar Li 1.2 Mn 0.54 Ni 0.13 Co 0.13 O 2 hollow (L-LMOH) nanosphere cathode for advanced lithium-ion batteries (LIBs). It is proved that the employment of sulfonated polystyrene (SPS) gel nanospheres as the template plays a key role in the formation of flower-like SPS@ Ni-Co-Mn-precursor nanospheres with desired molar ratios, and a subsequently delicate control in the heating rate leads to the intact L-LMOH nanospheres. It is demonstrated that the use of L-LMOH nanosphere cathode not only delivers outstanding reversible discharge capacities of 281.7 mAh g −1 at a current density of 20 mA g −1 and 136.6 mAh g −1 at 2000 mA g −1 , but also possess superior cycling stability with a capacity reservation of 80% at 2000 mA g −1 after 200 continuous cycles. It is well analyzed that the ingenious design of both unique lamella and hollow architectures synergistically benefits the significantly enhanced rate capability and cycling stability.

NiCo2O4 surface coating Li[Ni0.03Mn1.97]O4 micro-/nano- spheres as cathode material for high-performance lithium ion battery

Science.gov (United States)

Ye, Pan; Dong, Hui; Xu, Yunlong; Zhao, Chongjun; Liu, Dong

2018-01-01

Here we report a novel transitional metal oxide (NiCo2O4) coated Li[Ni0.03Mn1.97]O4 micro-/nano- spheres as high-performance Li-ion battery cathode material. A thin layer of ∼10 nm NiCo2O4 was formed by simple wet-chemistry approach adjacent to the surface of Li[Ni0.03Mn1.97]O4 micro-/nano- spheres, leading to significantly enhanced battery electrochemical performance. The optimized sample(1 wt%) not only delivers excellent discharge capacity and cycling stability improvement at both room temperature and elevated temperatures, but also effectively prevents Mn dissolution while retaining its coating structure intact according to XRF and TEM results. The CV and EIS break-down analysis indicated a much faster electrochemical reaction kinetics, more reversible electrode process and greatly reduced charge transfer and Warburg resistance, clearly illustrating the dual role of NiCo2O4 coating to boost electron transport and Li+ diffusion, and alleviation of manganese dissolving. This approach may render as an efficient technique to realize high-performance lithium ion battery cathode material.

Lithium recycling and cathode material regeneration from acid leach liquor of spent lithium-ion battery via facile co-extraction and co-precipitation processes.

Science.gov (United States)

Yang, Yue; Xu, Shengming; He, Yinghe

2017-06-01

A novel process for extracting transition metals, recovering lithium and regenerating cathode materials based on facile co-extraction and co-precipitation processes has been developed. 100% manganese, 99% cobalt and 85% nickel are co-extracted and separated from lithium by D2EHPA in kerosene. Then, Li is recovered from the raffinate as Li 2 CO 3 with the purity of 99.2% by precipitation method. Finally, organic load phase is stripped with 0.5M H 2 SO 4 , and the cathode material LiNi 1/3 Co 1/3 Mn 1/3 O 2 is directly regenerated from stripping liquor without separating metal individually by co-precipitation method. The regenerative cathode material LiNi 1/3 Co 1/3 Mn 1/3 O 2 is miro spherical morphology without any impurities, which can meet with LiNi 1/3 Co 1/3 Mn 1/3 O 2 production standard of China and exhibits good electrochemical performance. Moreover, a waste battery management model is introduced to guarantee the material supply for spent battery recycling. Copyright © 2017 Elsevier Ltd. All rights reserved.

Lithium tantalate single crystal for pyroelectricity-based laser energy-meter: growth, application and phase transition study

International Nuclear Information System (INIS)

Bhaumik, Indranil; Ganesamoorthy, S.; Bhatt, R.; Karnal, A.K.; Gupta, P.K.

2009-01-01

Single crystals of lithium tantalate have been grown. Dielectric-spectroscopy study reveals phase transition in congruent lithium tantalate (CLT) single crystal is diffusive and frequency dependent in contrast to that in near stoichiometric lithium tantalate where it is sharper. The ac conductivity measurements show that the conductivity is lower for 0.5Mg-SLT as compared to 1.0Mg-SLT. This is explained in terms of a Li-vacancy model. Calculation of activation energy from the lnσ vs. 1000/T plot reveals that hopping of Li + ions becomes difficult for 0.5 Mg-SLT. The pyroelectric response of CLT for pulsed Nd:YAG laser output has been tested. (author)

Design of Nickel-Based Cation-Disordered Rock-Salt Oxides: The Effect of Transition Metal (M = V, Ti, Zr) Substitution in LiNi0.5M0.5O2 Binary Systems.

Science.gov (United States)

Cambaz, Musa Ali; Vinayan, Bhaghavathi P; Euchner, Holger; Johnsen, Rune E; Guda, Alexander A; Mazilkin, Andrey; Rusalev, Yury V; Trigub, Alexander L; Gross, Axel; Fichtner, Maximilian

2018-06-20

Cation-disordered oxides have been ignored as positive electrode material for a long time due to structurally limited lithium insertion/extraction capabilities. In this work, a case study is carried out on nickel-based cation-disordered Fm3 ̅m LiNi 0.5 M 0.5 O 2 positive electrode materials. The present investigation targets tailoring the electrochemical properties for nickel-based cation-disordered rock-salt by electronic considerations. The compositional space for binary LiM +3 O 2 with metals active for +3/+4 redox couples is extended to ternary oxides with LiA 0.5 B 0.5 O 2 with A = Ni 2+ and B = Ti 4+ , Zr 4+ , and V +4 to assess the impact of the different transition metals in the isostructural oxides. The direct synthesis of various new unknown ternary nickel-based Fm3̅ m cation-disordered rock-salt positive electrode materials is presented with a particular focus on the LiNi 0.5 V 0.5 O 2 system. This positive electrode material for Li-ion batteries displays an average voltage of ∼2.55 V and a high discharge capacity of 264 mAhg -1 corresponding to 0.94 Li. For appropriate cutoff voltages, a long cycle life is achieved. The charge compensation mechanism is probed by XANES, confirming the reversible oxidation and reduction of V 4+ /V 5+ . The enhancement in the electrochemical performances within the presented compounds stresses the importance of mixed cation-disordered transition metal oxides with different electronic configuration.

Layered lithium manganese(0.4) nickel(0.4) cobalt(0.2) oxide(2) as cathode for lithium batteries

Science.gov (United States)

Ma, Miaomiao

The lithium ion battery occupies a dominant position in the portable battery market today. Intensive research has been carried out on every part of the battery to reduce cost, avoid environmental hazards, and improve battery performance. The commercial cathode material LiCoO2 has been partially replaced by LiNiyCo1- yO2 in the last two years, and mixed metal oxides have been introduced in the last quarter. From a resources point of view, only about 10 million tons of cobalt deposits are available from the world's minerals. However, there is about 500 times more manganese available than cobalt. Moreover, cobalt itself is not environmentally friendly. The purpose of this work is to find a promising alternative cathode material that can maintain good cycling performance, while at the same time reducing the cost and toxicity. When the cost is lowered, it is then possible to consider the larger scale use of lithium ion batteries in application such as hybrid electric vehicles (HEV). The research work presented in this thesis has focused on a specific composition of a layered lithium transition metal oxide, LiMn0.4Ni 0.4Co0.2O2 with the R3¯m structure. The presence of cobalt plays a critical role in minimizing transition metal migration to the lithium layer, and perhaps also in enhancing the electronic conductivity; however, cobalt is in limited supply and it is therefore more costly than nickel or manganese. The performance of LiMn0.4Ni0.4Co 0.2O2 was investigated and characterized utilizing various techniques an its performance compared with cobalt free LiMn0.5N i0.5O2, as well as with LiMn1/3Ni1/3Co 1/3O2, which is the most extensively studied replacement candidate for LiNiyCo1- yO2, and may be in SONY'S new hybrid cells. First, the structure and cation distribution in LiMn0.4Ni 0.4Co0.2O2 was studied by a combination of X-ray and neutron diffraction experiments. This combination study shows that about 3--5% nickel is present in the lithium layer, while manganese and

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

Science.gov (United States)

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

2015-05-01

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

Low-temperature structural phase transition in deuterated and protonated lithium acetate dihydrate

Energy Technology Data Exchange (ETDEWEB)

Schroeder, F., E-mail: schroeder@kristall.uni-frankfurt.d [Goethe-Universitaet Frankfurt am Main, Institut fuer Geowissenschaften, Abt. Kristallographie, Altenhoeferallee 1, 60438 Frankfurt am Main (Germany); Winkler, B.; Haussuehl, E. [Goethe-Universitaet Frankfurt am Main, Institut fuer Geowissenschaften, Abt. Kristallographie, Altenhoeferallee 1, 60438 Frankfurt am Main (Germany); Cong, P.T.; Wolf, B. [Goethe-Universitaet Frankfurt am Main, Physikalisches Institut, Max-von-Laue-Strasse 1, 60438 Frankfurt am Main (Germany); Avalos-Borja, M. [Instituto Potosino de Investigacion Cientifica y Tecnologica, A.C. Camino a la Presa San Jose 2055, Col. Lomas 4 seccion CP 78216, San Luis Potosi (Mexico); Quilichini, M.; Hennion, B. [Laboratoire Leon Brillouin, CEN Saclay, 91191 Gif-sur-Yvette (France)

2010-08-15

Heat capacity measurements of protonated lithium acetate dihydrate show a structural phase transition at T = 12 K. This finding is in contrast to earlier work, where it was thought that only the deuterated compound undergoes a low temperature structural phase transition. This finding is confirmed by low temperature ultrasound spectroscopy, where the structural phase transition is associated with a velocity decrease of the ultrasonic waves, i.e. with an elastic softening. We compare the thermodynamic properties of the protonated and deuterated compounds and discuss two alternatives for the mechanism of the phase transition based on the thermal expansion measurements.

The amorphous phase transition in irradiated NiTi alloy

International Nuclear Information System (INIS)

Brimhall, J.L.; Kissinger, H.E.; Pelton, A.R.

1985-01-01

Observed supralinear dose dependence for the amorphous transformation during irradiation of NiTi is compatible with a cascade overlap model for heavy ion (2.5 MeV Ni + , 6 MeV Ta +++ ) irradiations. A model based on total defect build-up, however, is necessary to explain the amorphous transition induced by electron irradiation and can also be applied to heavy ion irradiation. The cascade effects in this latter model are manifested by non-uniform defect distribution in the lattice. The defect build-up model requires a high activation energy for interstitial migration which is not incompatible with recent findings. The form of the temperature dependence can also be rationalized using a defect build-up model (amorphous phase transition, heavy-ion irradiation, electron irradiation, NiTi, defect build-up, cascade overlap). (author)

Synergetic interface between NiO/Ni3S2 nanosheets and carbon nanofiber as binder-free anode for highly reversible lithium storage

Science.gov (United States)

Jiang, Jialin; Ma, Chao; Yang, Yinbo; Ding, Jingjing; Ji, Hongmei; Shi, Shaojun; Yang, Gang

2018-05-01

A novel heterostructure of NiO/Ni3S2 nanoflake is synthesized and composited with carbon nanofibers (CNF) membrane. NiO/Ni3S2 nanoflakes are homogeneously dispersed in CNF network, herein, NiO/Ni3S2 like leaf and CNF like branch. Carbon nanofibers network efficiently prevents the pulverization and buffers the volume changes of NiO/Ni3S2, meanwhile, NiO/Ni3S2 nanoflakes through the conductive channels of carbon nanofibers own improved Li+ diffusion ability and structural stability. The capacity of NiO/Ni3S2/CNF reaches to 519.2 mA g-1 after 200 cycles at the current density of 0.5 A g-1 while NiO/Ni3S2 fades to 71 mAh g-1 after 40 cycles. Owing to the synergetic structure, the resultant binder-free electrode NiO/Ni3S2/carbon nanofibers shows an excellent reversible lithium storage capability.

Designing new lithium-excess cathode materials from percolation theory: nanohighways in Li(x)Ni(2-4x/3)Sb(x/3)O2.

Science.gov (United States)

Twu, Nancy; Li, Xin; Urban, Alexander; Balasubramanian, Mahalingam; Lee, Jinhyuk; Liu, Lei; Ceder, Gerbrand

2015-01-14

Increasing lithium content is shown to be a successful strategy for designing new cathode materials. In layered Li(x)Ni(2-4x/3)Sb(x/3)O2 (x = 1.00-1.15), lithium excess improves both discharge capacity and capacity retention at 1C. Structural studies reveal a complex nanostructure pattern of Li-Sb and Ni-Sb ordering where the interface between these domains forms the correct local configuration for good lithium mobility. The <1 nm Li-Sb stripe domains and their interfaces thereby effectively act as nanohighways for lithium diffusion.

Countering the Segregation of Transition-Metal Ions in LiMn1/3 Co1/3 Ni1/3 O2 Cathode for Ultralong Life and High-Energy Li-Ion Batteries.

Science.gov (United States)

Luo, Dong; Fang, Shaohua; Tamiya, Yu; Yang, Li; Hirano, Shin-Ichi

2016-08-01

High-voltage layered lithium transition-metal oxides are very promising cathodes for high-energy Li-ion batteries. However, these materials often suffer from a fast degradation of cycling stability due to structural evolutions. It seriously impedes the large-scale application of layered lithium transition-metal oxides. In this work, an ultralong life LiMn1/3 Co1/3 Ni1/3 O2 microspherical cathode is prepared by constructing an Mn-rich surface. Its capacity retention ratio at 700 mA g(-1) is as large as 92.9% after 600 cycles. The energy dispersive X-ray maps of electrodes after numerous cycles demonstrate that the ultralong life of the as-prepared cathode is attributed to the mitigation of TM-ions segregation. Additionally, it is discovered that layered lithium transition-metal oxide cathodes with an Mn-rich surface can mitigate the segregation of TM ions and the corrosion of active materials. This study provides a new strategy to counter the segregation of TM ions in layered lithium transition-metal oxides and will help to the design and development of high-energy cathodes with ultralong life. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hydrothermal-synthesized NiO nanowall array for lithium ion batteries

International Nuclear Information System (INIS)

Yan, Xiaoyan; Tong, Xili; Wang, Jian; Gong, Changwei; Zhang, Mingang; Liang, Liping

2013-01-01

Graphical abstract: Freestanding NiO nanowall array is prepared via a hydrothermal synthesis method and shows noticeable Li battery performance with good cycle life and high capacity. Highlights: ► NiO nanowall array is prepared by a hydrothermal synthesis method. ► NiO nanowall array with high capacity as anode material for Li ion battery. ► Nanowall array structure is favorable for fast ion/electron transfer. -- Abstract: We report a self-supported NiO nanowall array prepared by a facile hydrothermal synthesis method. The microstructure and morphology of the sample are characterized by means of X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The hydrothermal-synthesized NiO nanowalls with thicknesses of ∼20 nm arrange vertically to the substrate forming a net-like nanowall array structure. As anode material for lithium ion batteries, the NiO nanowall array exhibits better electrochemical performances with higher coulombic efficiency and better cycling performance as compared to the dense NiO film. The NiO nanowall array shows an initial coulombic efficiency of 76%, as well as good cycling stability with a capacity of 567 mAh g −1 at 0.3 A g −1 after 50 cycles, higher than those of the dense polycrystalline NiO film (361 mAh g −1 ). The superior electrochemical performance is mainly due to the unique nanowall array structure with shorter diffusion length for mass and charge transport

Flexible free-standing porous graphene/Ni film electrode with enhanced rate capability for lithium-ion batteries

Energy Technology Data Exchange (ETDEWEB)

Cao, Hailiang; Zhou, Xufeng, E-mail: zhouxf@nimte.ac.cn; Shi, Junli; Liu, Zhaoping, E-mail: liuzp@nimte.ac.cn

2016-11-15

Flexible, lightweight and reliable lithium-ion batteries have attracted tremendous attention and research interest to meet the requirements of portable and bendable devices. Here, flexible, free-standing and porous graphene/Ni film with vertical nano-channels inside is prepared by metal etching of graphene film. Compared with dense graphene film, the porous graphene/Ni film employed as a binder-free anode in lithium-ion batteries exhibits higher capacity and much better rate capability, due to its unique interior channel architecture which is favorable for fast ion transport. At a high current density of 2 A g{sup −1}, it can reach a specific capacity of 117 mAh g{sup −1}. The porous film also shows low charge transfer resistance and good cycling stability. After 300 cycles at 1 A g{sup −1}, its specific capacity still remains at 147 mAh g{sup −1}, with high Coulombic efficiency of nearly 100%. Furthermore, the strategy developed here is very simple and of great importance to rational design of porous graphene film or graphene-based hybrids with various applications.

Flexible free-standing porous graphene/Ni film electrode with enhanced rate capability for lithium-ion batteries

International Nuclear Information System (INIS)

Cao, Hailiang; Zhou, Xufeng; Shi, Junli; Liu, Zhaoping

2016-01-01

Flexible, lightweight and reliable lithium-ion batteries have attracted tremendous attention and research interest to meet the requirements of portable and bendable devices. Here, flexible, free-standing and porous graphene/Ni film with vertical nano-channels inside is prepared by metal etching of graphene film. Compared with dense graphene film, the porous graphene/Ni film employed as a binder-free anode in lithium-ion batteries exhibits higher capacity and much better rate capability, due to its unique interior channel architecture which is favorable for fast ion transport. At a high current density of 2 A g"−"1, it can reach a specific capacity of 117 mAh g"−"1. The porous film also shows low charge transfer resistance and good cycling stability. After 300 cycles at 1 A g"−"1, its specific capacity still remains at 147 mAh g"−"1, with high Coulombic efficiency of nearly 100%. Furthermore, the strategy developed here is very simple and of great importance to rational design of porous graphene film or graphene-based hybrids with various applications.

In situ stress measurements during electrochemical cycling of lithium-rich cathodes

Science.gov (United States)

Nation, Leah; Li, Juchuan; James, Christine; Qi, Yue; Dudney, Nancy; Sheldon, Brian W.

2017-10-01

Layered lithium transition metal oxides (Li1+xM1-xO2, M = Ni, Mn, Co) are attractive cathode materials for lithium-ion batteries due to their high reversible capacity. However, they suffer from structural changes that lead to substantial voltage fade. In this study, we use stress as a novel way to track irreversible changes in Li1.2Mn0.55Ni0.125Co0.125O2 (LR-NMC) cathodes. A unique and unpredicted stress signature is observed during the first delithiation. Initially, a tensile stress is observed, consistent with volume contraction from lithium removal, however, the stress reverses and becomes compressive with continued charging beyond 4 V vs Li/Li+, indicating volume expansion; this phenomenon is present in the first cycle only. This irreversible stress during delithiation is likely to be at least partially due to oxygen loss and the resulting cation rearrangement. Raman spectroscopy provides evidence of the layered-to-spinel phase transition after cycling in the LR-NMC films, as well as recovery of the original spectra upon re-annealing in an oxygen environment.

Microwave assisted hydrothermal synthesis of Ni{sub 1.5}Co{sub 1.5}S{sub 4} as high-performance electrode material for lithium storage

Energy Technology Data Exchange (ETDEWEB)

Yuan, Dongxia; Wang, Xuxu; Yin, Dongming [State Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of Applied Chemistry, CAS, Changchun, 130022 (China); University of Chinese Academy of Sciences, Beijing, 100049 (China); Liang, Fei [State Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of Applied Chemistry, CAS, Changchun, 130022 (China); Wang, Limin, E-mail: lmwang@ciac.ac.cn [State Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of Applied Chemistry, CAS, Changchun, 130022 (China)

2017-08-31

Highlights: • Bimetallic nickel cobalt sulfide (Ni{sub 1.5}Co{sub 1.5}S{sub 4}) was prepared by an ultrafast microwave-assisted hydrothermal method. • The Ni{sub 1.5}Co{sub 1.5}S{sub 4} was studied as cathode materials for lithium ion batteries in the ether-based electrolyte in the voltage range of 1.0–3.0 V,. • Compared with its corresponding single metal sulfides, the Ni{sub 1.5}Co{sub 1.5}S{sub 4} exhibits superior electrochemical performance for lithium storage. - Abstract: Bimetallic nickel cobalt sulfide (Ni{sub 1.5}Co{sub 1.5}S{sub 4}) is successfully fabricated by an ultrafast and cost-effective microwave assisted hydrothermal method. When used as electrode material for lithium-ion batteries, Ni{sub 1.5}Co{sub 1.5}S{sub 4} exhibits the remarkable electrochemical performance in terms of superior cycling stability, excellent specific capacity and good rate capability. A high specific capacity of 443 mA h g{sup −1} after 200 charge-discharge cycles at a current density of 0.5 A g{sup −1} is achieved. Even at 1 A g{sup −1}, the sample still delivers a discharge capacity of 386 mA h g{sup −1} with a high columbic efficiency of 99.6% after 500 cycles.

Nonflammable perfluoropolyether-based electrolytes for lithium batteries

Science.gov (United States)

Wong, Dominica H. C.; Thelen, Jacob L.; Fu, Yanbao; Devaux, Didier; Pandya, Ashish A.; Battaglia, Vincent S.; Balsara, Nitash P.; DeSimone, Joseph M.

2014-01-01

The flammability of conventional alkyl carbonate electrolytes hinders the integration of large-scale lithium-ion batteries in transportation and grid storage applications. In this study, we have prepared a unique nonflammable electrolyte composed of low molecular weight perfluoropolyethers and bis(trifluoromethane)sulfonimide lithium salt. These electrolytes exhibit thermal stability beyond 200 °C and a remarkably high transference number of at least 0.91 (more than double that of conventional electrolytes). Li/LiNi1/3Co1/3Mn1/3O2 cells made with this electrolyte show good performance in galvanostatic cycling, confirming their potential as rechargeable lithium batteries with enhanced safety and longevity. PMID:24516123

Electrodeposited binder-free NiCo2O4@carbon nanofiber as a high performance anode for lithium ion batteries

Science.gov (United States)

Zhang, Jie; Chu, Ruixia; Chen, Yanli; Jiang, Heng; Zhang, Ying; Huang, Nay Ming; Guo, Hang

2018-03-01

Binder-free nickel cobaltite on a carbon nanofiber (NiCo2O4@CNF) anode for lithium ion batteries was prepared via a two-step procedure of electrospinning and electrodeposition. The CNF was obtained by annealing electrospun poly-acrylonitrile (PAN) in nitrogen (N2). The NiCo2O4 nanostructures were then grown on the CNF by electrodeposition, followed by annealing in air. Experimental results showed that vertically aligned NiCo2O4 nanosheets had uniformly grown on the surface of the CNF, forming an interconnected network. The NiCo2O4@CNF possessed considerable lithium storage capacity and cycling stability. It exhibited a high reversible capacity of 778 mAhg-1 after 300 cycles at a current density of 0.25 C (1 C = 890 mAg-1) with an average capacity loss rate of 0.05% per cycle. The NiCo2O4@CNF had considerable rate capacities, delivering a capacity of 350 mAhg-1 at a current density of 2.0 C. The outstanding electrochemical performance can be mainly attributed to the following: (1) The nanoscale structure of NiCo2O4 could not only shorten the diffusion path of lithium ions and electrons but also increase the specific surface area, providing more active sites for electrochemical reactions. (2) The CNF with considerable mechanical strength and electrical conductivity could function as an anchor for the NiCo2O4 nanostructure and ensure an efficient electron transfer. (3) The porous structure resulted in a high specific surface area and an effective buffer for the volume changes during the repeated charge-discharge processes. Compared with a conventional hydrothermal method, electrodeposition could significantly simplify the preparation of NiCo2O4, with a shorter preparation period and lower energy consumption. This work provides an alternative strategy to obtain a high performance anode for lithium ion batteries.

General access to metal oxide (Metal = Mn, Co, Ni) double-layer nanospheres for application in lithium ion batteries and supercapacitors

International Nuclear Information System (INIS)

Xia, Yuan; Wang, Gang; Zhang, Xing; Wang, Beibei; Wang, Hui

2016-01-01

Highlights: • A series of metal oxide double layer nanospheres were prepared. • The obtained materials show excellent performances in lithium ion batteries and supercapacitors. • The unique structure of double layers is beneficial for superior electrochemical performances. - Abstract: In this work, a series of metal oxide double-layer nanospheres (DLNs), such as Mn 2 O 3 , Co 3 O 4 , NiO, NiCo 2 O 4 , and MnCo 2 O 4 have been successfully synthesized through a general template method. The layers of nanospheres were assembled by different nanostructure units and the removing of the SiO 2 template formed a void of several ten nanometers between the double layers, resulting large specific surface areas for them. The energy storage performances of the as-prepared double-layer nanospheres were further investigated in lithium ion battery and supercapacitor systems. Based on their unique nanostructures, the double-layer nanospheres exhibit excellent electrochemical performance with long cycle stability and high specific capacities or capacitances. The best of these, DLNs-NiCo 2 O 4 can deliver a reversible capacity of 1107 mAh g −1 at 0.25C after 200 cycles in lithium ion battery system, and shows a capacitance of 1088 F g −1 with capacitance loss of less than 3% at 5 A g −1 after 5000 cycles in supercapacitors.

Experimental analysis on the performance of lithium based batteries for road full electric and hybrid vehicles

International Nuclear Information System (INIS)

Capasso, Clemente; Veneri, Ottorino

2014-01-01

Highlights: • Performance analysis for lithium storage technologies, such as Li[NiCoMn]O 2 and LiFePO 4 batteries. • Actual capacity of lithium technologies analyzed almost close to their nominal capacity also for high discharging current. • The charging efficiency for Li[NiCoMn]O 2 positively affects the regenerative breaking and fast recharging operations. • The analyzed battery packs follow dynamic power requirements on performed road driving cycles. • Experimental results demonstrate driving range is much higher when battery packs are based on lithium technology. - Abstract: This paper deals with an experimental evaluation regarding the real performance of lithium based energy storage systems for automotive applications. In particular real working operations of different lithium based storage system technologies, such as Li[NiCoMn]O 2 and LiFePO 4 batteries, are compared in this work from the point of view of their application in supplying full electric and hybrid vehicles, taking as a reference the well-known behavior of lead acid batteries. For this purpose, the experimental tests carried out in laboratory are firstly performed on single storage modules in stationary conditions. In this case the related results are obtained by means of a bidirectional cycle tester based on the IGBT technology, and consent to evaluate, compare and contrast charge/discharge characteristics and efficiency at constant values of current/voltage/power for each storage technology analyzed. Then, lithium battery packs are tested in supplying a 1.8 kW electric power train using a laboratory test bench, based on a 48 V DC bus and specifically configured to simulate working operations of electric vehicles on the road. For this other experimentation the test bench is equipped with an electric brake and acquisition/control system, able to represent in laboratory the real vehicle conditions and road characteristics on predefined driving cycles at different slopes. The obtained

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

Directory of Open Access Journals (Sweden)

Amaia Iturrondobeitia

2017-12-01

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

Isotope effect in glass-transition temperature and ionic conductivity of lithium-borate glasses

International Nuclear Information System (INIS)

Nagasaki, Takanori; Morishima, Ryuta; Matsui, Tsuneo

2002-01-01

The glass-transition temperature and the electrical conductivity of lithium borate (0.33Li 2 O-0.67B 2 O 3 ) glasses with various isotopic compositions were determined by differential thermal analysis and by impedance spectroscopy, respectively. The obtained glass-transition temperature as well as the vibrational frequency of B-O network structure was independent of lithium isotopic composition. This result indicates that lithium ions, which exist as network modifier, only weakly interact with B-O network structure. In addition, the glass-transition temperature increased with 10 B content although the reason has not been understood. The electrical conductivity, on the other hand, increased with 6 Li content. The ratio of the conductivity of 6 Li glass to that of 7 Li glass was found to be 2, being larger than the value (7/6) 1/2 calculated with the simple classical diffusion theory. This strong mass dependence could be explained by the dynamic structure model, which assumes local structural relaxation even far below the glass-transition temperature. Besides, the conductivity appeared to increase with the glass-transition temperature. Possible correlations between the glass-transition temperature and the electrical conductivity were discussed. (author)

Optimization of NiFe2O4/rGO composite electrode for lithium-ion batteries

Science.gov (United States)

Li, Chen; Wang, Xia; Li, Shandong; Li, Qiang; Xu, Jie; Liu, Xiaomin; Liu, Changkun; Xu, Yuanhong; Liu, Jingquan; Li, Hongliang; Guo, Peizhi; Zhao, Xiu Song

2017-09-01

The combination of carbon compositing and the proper choice of binders in one system offer an effective strategy for improving electrode performance for lithium ion batteries (LIBs). Here, we focus on the optimization of reduced graphene oxide content in NiFe2O4/reduced graphene oxide (abbreviated to NiFe2O4/rGO) composites and the proper choice of binders to enhance the cycling stability of the NiFe2O4 electrode. The NiFe2O4/rGO composites were fabricated by a hydrothermal-annealing method, in which the mean size of spinel NiFe2O4 nanoparticles was approximately 20 nm. When tested as anode materials for LIBs, the NiFe2O4/rGO electrodes with carboxymethylcellulose (CMC) binder exhibited excellent lithium-storage performance including high reversible capacity, good cycling durability and high-rate capability. The capacity could be retained as high as 1105 mAh g-1 at a current density of 100 mA g-1 for over 50 cycles, even cycled at higher current density of 1000 mA g-1, a capacity of 800 mAh g-1can be obtained, whereas the electrode with the polyvinylidene fluoride (PVDF) binder suffered from rapid capacity decay under the same test conditions. As a result, the NiFe2O4/rGO composites with CMC binder electrode in this work are promising as anodes for high-performance LIBs, resulting from the synergistic effect of optimal graphene content and proper choice of binder.

Electrochemical performance of all-solid-state lithium secondary batteries with Li-Ni-Co-Mn oxide positive electrodes

International Nuclear Information System (INIS)

Kitaura, Hirokazu; Hayashi, Akitoshi; Tadanaga, Kiyoharu; Tatsumisago, Masahiro

2010-01-01

LiNi 1/3 Co 1/3 Mn 1/3 O 2 was applied as a promising material to the all-solid-state lithium cells using the 80Li 2 S.19P 2 S 5 .1P 2 O 5 (mol%) solid electrolyte. The cell showed the first discharge capacity of 115 mAh g -1 at the current density of 0.064 mA cm -2 and retained the reversible capacity of 110 mAh g -1 after 10 cycles. The interfacial resistance was observed in the impedance spectrum of the all-solid-state cell charged to 4.4 V (vs. Li) and the transition metal elements were detected on the solid electrolyte in the vicinity of LiNi 1/3 Co 1/3 Mn 1/3 O 2 by the TEM observations with EDX analyses. The electrochemical performance was improved by the coating of LiNi 1/3 Co 1/3 Mn 1/3 O 2 particles with Li 4 Ti 5 O 12 film. The interfacial resistance was decreased and the discharge capacity was increased from 63 to 83 mAh g -1 at 1.3 mA cm -2 by the coating. The electrochemical performance of LiNi 1/3 Co 1/3 Mn 1/3 O 2 was compared with that of LiCoO 2 , LiMn 2 O 4 and LiNiO 2 in the all-solid-state cells. The rate capability of LiNi 1/3 Co 1/3 Mn 1/3 O 2 was lower than that of LiCoO 2 . However, the reversible capacity of LiNi 1/3 Co 1/3 Mn 1/3 O 2 at 0.064 mA cm -2 was larger than that of LiCoO 2 , LiMn 2 O 4 and LiNiO 2 .

Toward Dendrite-Free Lithium Deposition via Structural and Interfacial Synergistic Effects of 3D Graphene@Ni Scaffold.

Science.gov (United States)

Xie, Keyu; Wei, Wenfei; Yuan, Kai; Lu, Wei; Guo, Min; Li, Zhihua; Song, Qiang; Liu, Xingrui; Wang, Jian-Gan; Shen, Chao

2016-10-05

Owing to its ultrahigh specific capacity and low electrochemical potential, lithium (Li) metal is regarded as one of the most attractive anode materials for next-generation lithium batteries. Nevertheless, the commercialization of Li-metal-based rechargeable batteries (LiMBs) has been retarded by the uncontrollable growth of Li dendrites, as well as the resulting poor cycle stability and safety hazards. In this work, a 3D graphene@Ni scaffold has been proposed to accomplish dendrite-free Li deposition via structural and interfacial synergistic effects. Due to the intrinsic high surface area used to reduce the effective electrode current density and the surface-coated graphene working as an artificial protection layer to provide high cycle stability as well as suppress the growth of Li dendrites, the Coulombic efficiencies of Li deposition on 3D graphene@Ni foam after 100 cycles can be sustained as high as 96, 98, and 92% at the current densities of 0.25, 0.5, and 1.0 mA cm -2 , respectively, which shows more excellent cycle stability than that of its planar Cu foil and bare Ni foam counterparts. The results obtained here demonstrate that the comprehensive consideration of multiaspect factors could be more help to enhance the performance of Li metal anode so as to achieve its real application in next-generation LiMBs.

Visualizing elemental deposition patterns on carbonaceous anodes from lithium ion batteries: A laser ablation-inductively coupled plasma-mass spectrometry study on factors influencing the deposition of lithium, nickel, manganese and cobalt after dissolution and migration from the Li1[Ni1/3Mn1/3Co1/3]O2 and LiMn1.5 Ni0.5O4 cathode

Science.gov (United States)

Schwieters, Timo; Evertz, Marco; Fengler, Alexander; Börner, Markus; Dagger, Tim; Stenzel, Yannick; Harte, Patrick; Winter, Martin; Nowak, Sascha

2018-03-01

In this study, laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) is applied to previously aged carbonaceous anodes from lithium ion batteries (LIBs). These electrodes are treated by cyclic aging in a lithium ion cell set-up against Li1[Ni1/3Mn 1/3Co1/3]O2 = NMC111 to elucidate factors that influence transition metal dissolution (TMD) of the cathode and subsequent deposition on the anode. The investigations are carried out by qualitatively visualizing the 7Li and TM patterns (60Ni, 55Mn and 59Co) of whole coin and pouch-bag electrodes. The lithium, as well as the TM amount, found on the anode, is directly correlated to the applied upper cut-off voltage (4.6, 4.7, 4.8 and 4.9 V) showing more deposition of Li and TMs at elevated voltages. While 7Li shows a more homogeneous pattern, the TM distribution is inhomogeneous but showing a similar pattern for all TMs of the same sample. An unequal pressure distribution, resulting in a nonparallel electrode alignment, on the electrode stack is identified to be responsible for the inhomogeneous TM deposition pattern. This uneven electrode orientation results in different diffusion pathways for the TM migration with regard to the spatial distances.

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

Energy Technology Data Exchange (ETDEWEB)

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

1996-12-31

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

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

Energy Technology Data Exchange (ETDEWEB)

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

1997-12-31

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

General Synthesis of Transition-Metal Oxide Hollow Nanospheres/Nitrogen-Doped Graphene Hybrids by Metal-Ammine Complex Chemistry for High-Performance Lithium-Ion Batteries.

Science.gov (United States)

Chen, Jiayuan; Wu, Xiaofeng; Gong, Yan; Wang, Pengfei; Li, Wenhui; Mo, Shengpeng; Peng, Shengpan; Tan, Qiangqiang; Chen, Yunfa

2018-02-09

We present a general and facile synthesis strategy, on the basis of metal-ammine complex chemistry, for synthesizing hollow transition-metal oxides (Co 3 O 4 , NiO, CuO-Cu 2 O, and ZnO)/nitrogen-doped graphene hybrids, potentially applied in high-performance lithium-ion batteries. The oxygen-containing functional groups of graphene oxide play a prerequisite role in the formation of hollow transition-metal oxides on graphene nanosheets, and a significant hollowing process occurs only when forming metal (Co 2+ , Ni 2+ , Cu 2+ , or Zn 2+ )-ammine complex ions. Moreover, the hollowing process is well correlated with the complexing capacity between metal ions and NH 3 molecules. The significant hollowing process occurs for strong metal-ammine complex ions including Co 2+ , Ni 2+ , Cu 2+ , and Zn 2+ ions, and no hollow structures formed for weak and/or noncomplex Mn 2+ and Fe 3+ ions. Simultaneously, this novel strategy can also achieve the direct doping of nitrogen atoms into the graphene framework. The electrochemical performance of two typical hollow Co 3 O 4 or NiO/nitrogen-doped graphene hybrids was evaluated by their use as anodic materials. It was demonstrated that these unique nanostructured hybrids, in contrast with the bare counterparts, solid transition-metal oxides/nitrogen-doped graphene hybrids, perform with significantly improved specific capacity, superior rate capability, and excellent capacity retention. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Room-temperature ferromagnetic transitions and the temperature dependence of magnetic behaviors in FeCoNiCr-based high-entropy alloys

Science.gov (United States)

Na, Suok-Min; Yoo, Jin-Hyeong; Lambert, Paul K.; Jones, Nicholas J.

2018-05-01

High-entropy alloys (HEAs) containing multiple principle alloying elements exhibit unique properties so they are currently receiving great attention for developing innovative alloy designs. In FeCoNi-based HEAs, magnetic behaviors strongly depend on the addition of alloying elements, usually accompanied by structural changes. In this work, the effect of non-magnetic components on the ferromagnetic transition and magnetic behaviors in equiatomic FeCoNiCrX (X=Al, Ga, Mn and Sn) HEAs was investigated. Alloy ingots of nominal compositions of HEAs were prepared by arc melting and the button ingots were cut into discs for magnetic measurements as functions of magnetic field and temperature. The HEAs of FeCoNiCrMn and FeCoNiCrSn show typical paramagnetic behaviors, composed of solid solution FCC matrix, while the additions of Ga and Al in FeCoNiCr exhibit ferromagnetic behaviors, along with the coexistence of FCC and BCC phases due to spinodal decomposition. The partial phase transition in both HEAs with the additions of Ga and Al would enhance ferromagnetic properties due to the addition of the BCC phase. The saturation magnetization for the base alloy FeCoNiCr is 0.5 emu/g at the applied field of 20 kOe (TC = 104 K). For the HEAs of FeCoNiCrGa and FeCoNiCrAl, the saturation magnetization significantly increased to 38 emu/g (TC = 703 K) and 25 emu/g (TC = 277 K), respectively. To evaluate the possibility of solid solution FCC and BCC phases in FeCoNiCr-type HEAs, we introduced a parameter of valence electron concentration (VEC). The proposed rule for solid solution formation by the VEC was matched with FeCoNiCr-type HEAs.

Mitigating Voltage Decay of Li-Rich Cathode Material via Increasing Ni Content for Lithium-Ion Batteries.

Science.gov (United States)

Shi, Ji-Lei; Zhang, Jie-Nan; He, Min; Zhang, Xu-Dong; Yin, Ya-Xia; Li, Hong; Guo, Yu-Guo; Gu, Lin; Wan, Li-Jun

2016-08-10

Li-rich layered materials have been considered as the most promising cathode materials for future high-energy-density lithium-ion batteries. However, they suffer from severe voltage decay upon cycling, which hinders their further commercialization. Here, we report a Li-rich layered material 0.5Li2MnO3·0.5LiNi0.8Co0.1Mn0.1O2 with high nickel content, which exhibits much slower voltage decay during long-term cycling compared to conventional Li-rich materials. The voltage decay after 200 cycles is 201 mV. Combining in situ X-ray diffraction (XRD), ex situ XRD, ex situ X-ray photoelectron spectroscopy, and scanning transmission electron microscopy, we demonstrate that nickel ions act as stabilizing ions to inhibit the Jahn-Teller effect of active Mn(3+) ions, improving d-p hybridization and supporting the layered structure as a pillar. In addition, nickel ions can migrate between the transition-metal layer and the interlayer, thus avoiding the formation of spinel-like structures and consequently mitigating the voltage decay. Our results provide a simple and effective avenue for developing Li-rich layered materials with mitigated voltage decay and a long lifespan, thereby promoting their further application in lithium-ion batteries with high energy density.

Transit bus applications of lithium ion batteries : progress and prospects

Science.gov (United States)

2012-12-31

This report provides an overview of diverse transit bus applications of advanced Lithium Ion Batteries (LIBs). The report highlights and illustrates several FTA programs that fostered the successful development, demonstration, and deployment of fuel-...

Rapid synthesis of binary α-NiS–β-NiS by microwave autoclave for rechargeable lithium batteries

International Nuclear Information System (INIS)

Idris, Nurul Hayati; Rahman, Md Mokhlesur; Chou, Shu-Lei; Wang Jiazhao; Wexler, David; Liu, Hua-Kun

2011-01-01

Highlights: ► NiS has been synthesized by a rapid, one-pot, hydrothermal microwave autoclave method. ► The α-NiS–β-NiS sample synthesized at 160 °C yielded good electrochemical performance in terms of high reversible capacity (320 mAh g −1 at 0.1C up to 100 cycles). ► At high rates, the sample operated at a good fraction of its capacity. - Abstract: To reduce the reaction time, electrical energy consumption, and cost, binary α-NiS–β-NiS has been synthesized by a rapid, one-pot, hydrothermal autoclave microwave method within 15 min at temperatures of 160–180 °C. The microstructure and morphology of the α-NiS–β-NiS products were characterized by means of X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), and transmission electron microscopy (TEM). At 140 °C, pure hexagonal NiAs-type α-NiS phase was identified from the XRD patterns. With increasing reaction temperature (160–180 °C), the XRD evidence indicates that an increasing fraction of rhombohedral millerite-like β-NiS is formed as a secondary phase. The α-NiS–β-NiS sample synthesized at 160 °C yielded good electrochemical performance in term of high reversible capacity (320 mAh g −1 at 0.1C up to 100 cycles). Even at high rates, the sample operated at a good fraction of its capacity. The likely contributing factor to the superior electrochemical performance of the α-NiS–β-NiS sample could be related to the improved morphology. TEM imaging confirmed that needle-like protrusions connect the clusters of α-NiS particles, and the individual protrusions indicated a very high surface area including folded sheet morphology, which helps to dissipate the surface accumulation of Li + ions and facilitate rapid mobility. These factors help to enhance the amount of lithium intercalated within the material.

Evolution Of Lattice Structure And Chemical Composition Of The Surface Reconstruction Layer In Li1.2Ni0.2Mn0.6O2 Cathode Material For Lithium Ion Batteries

Energy Technology Data Exchange (ETDEWEB)

Yan, Pengfei; Nie, Anmin; Zheng, Jianming; Zhou, Yungang; Lu, Dongping; Zhang, Xiaofeng; Xu, Rui; Belharouak, Ilias; Zu, Xiaotao; Xiao, Jie; Amine, Khalil; Liu, Jun; Gao, Fei; Shahbazian-Yassar, Reza; Zhang, Jiguang; Wang, Chong M.

2015-01-14

Voltage and capacity fading of layer structured lithium and manganese rich (LMR) transition metal oxide is directly related to the structural and composition evolution of the material during the cycling of the battery. However, understanding such evolution at atomic level remains elusive. Based on atomic level structural imaging, elemental mapping of the pristine and cycled samples and density functional theory calculations, it is found that accompanying the hoping of Li ions is the simultaneous migration of Ni ions towards the surface from the bulk lattice, leading to the gradual depletion of Ni in the bulk lattice and thickening of a Ni enriched surface reconstruction layer (SRL). Furthermore, Ni and Mn also exhibit concentration partitions within the thin layer of SRL in the cycled samples where Ni is almost depleted at the very surface of the SRL, indicating the preferential dissolution of Ni ions in the electrolyte. Accompanying the elemental composition evolution, significant structural evolution is also observed and identified as a sequential phase transition of C2/m →I41→Spinel. For the first time, it is found that the surface facet terminated with pure cation is more stable than that with a mixture of cation and anion. These findings firmly established how the elemental species in the lattice of LMR cathode transfer from the bulk lattice to surface layer and further into the electrolyte, clarifying the long standing confusion and debate on the structure and chemistry of the surface layer and their correlation with the voltage fading and capacity decaying of LMR cathode. Therefore, this work provides critical insights for designing of cathode materials with both high capacity and voltage stability during cycling.

Underlying mechanisms leading to El Niño-to-La Niña transition are unchanged under global warming

Science.gov (United States)

Yun, Kyung-Sook; Yeh, Sang-Wook; Ha, Kyung-Ja

2018-05-01

El Niño's transitions play critical roles in modulating severe weather and climate events. Therefore, understanding the dynamic factors leading to El Niño's transitions and its future projection is a great challenge in predicting the diverse socioeconomic influences of El Niño over the globe. This study focuses on two dynamic factors controlling the El Niño-to-La Niña transition from the present climate and to future climate, using the observation, the historical and the RCP8.5 simulations of Coupled Model Intercomparison phase 5 climate models. The first is the inter-basin coupling between the Indian Ocean and the western North Pacific through the subtropical high variability. The second is the enhanced sensitivity between sea surface temperature and a deep tropical convection in the central tropical Pacific during the El Niño's developing phase. We show that the dynamic factors leading to El Niño-to-La Niña transition in the present climate are unchanged in spite of the increase of greenhouse gas concentrations. We argue that the two dynamic factors are strongly constrained by the climatological precipitation distribution over the central tropical Pacific and western North Pacific as little changed from the present climate to future climate. This implies that two dynamical processes leading to El Niño-to-La Niña transitions in the present climate will also play a robust role in global warming.

Intermartensitic transitions in Ni-Mn-Fe-Cu-Ga Heusler alloys

International Nuclear Information System (INIS)

Khan, Mahmud; Gautam, Bhoj; Pathak, Arjun; Dubenko, Igor; Stadler, Shane; Ali, Naushad

2008-01-01

A series of Fe doped Ni 2 Mn 0.75-x Fe x Cu 0.25 Ga Heusler alloys have been investigated by means of x-ray diffraction, magnetizations, thermal expansion, and electrical resistivity measurements. In Ni 2 Mn 0.75 Cu 0.25 Ga, martensitic and ferromagnetic transitions occur at the same temperature. Partial substitution of Mn by Fe results in a decrease of the martensitic transition temperature, T M , and an increase of the ferromagnetic transition temperature, T C , resulting in separation of the two transitions. In addition to the martensitic transition, complete thermoelastic intermartensitic transformations have been observed in the Fe doped Ni 2 Mn 0.75-x Fe x Cu 0.25 Ga samples with x>0.04. An unusual transition is observed in the alloy with x = 0.04. The magnetization curve as a function of increasing temperature shows only one first-order transition in the temperature range 5-400 K, which is identified as a typical coupled magnetostructural martensitic transformation. The magnetization curve as a function of decreasing temperature shows three different transitions, which are characterized as the ferromagnetic transition, the martensitic transition and the intermartensitic transition.

Novel Approach for in Situ Recovery of Lithium Carbonate from Spent Lithium Ion Batteries Using Vacuum Metallurgy.

Science.gov (United States)

Xiao, Jiefeng; Li, Jia; Xu, Zhenming

2017-10-17

Lithium is a rare metal because of geographical scarcity and technical barrier. Recycling lithium resource from spent lithium ion batteries (LIBs) is significant for lithium deficiency and environmental protection. A novel approach for recycling lithium element as Li 2 CO 3 from spent LIBs is proposed. First, the electrode materials preobtained by mechanical separation are pyrolyzed under enclosed vacuum condition. During this process the Li is released as Li 2 CO 3 from the crystal structure of lithium transition metal oxides due to the collapse of the oxygen framework. An optimal Li recovery rate of 81.90% is achieved at 973 K for 30 min with a solid-to-liquid ratio of 25 g L -1 , and the purity rate of Li 2 CO 3 is 99.7%. The collapsed mechanism is then presented to explain the release of lithium element during the vacuum pyrolysis. Three types of spent LIBs including LiMn 2 O 4 , LiCoO 2 , and LiCo x Mn y Ni z O 2 are processed to prove the validity of in situ recycling Li 2 CO 3 from spent LIBs under enclosed vacuum condition. Finally, an economic assessment is taken to prove that this recycling process is positive.

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

International Nuclear Information System (INIS)

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

2015-01-01

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

Superconcentrated electrolytes for a high-voltage lithium-ion battery

Science.gov (United States)

Wang, Jianhui; Yamada, Yuki; Sodeyama, Keitaro; Chiang, Ching Hua; Tateyama, Yoshitaka; Yamada, Atsuo

2016-01-01

Finding a viable electrolyte for next-generation 5 V-class lithium-ion batteries is of primary importance. A long-standing obstacle has been metal-ion dissolution at high voltages. The LiPF6 salt in conventional electrolytes is chemically unstable, which accelerates transition metal dissolution of the electrode material, yet beneficially suppresses oxidative dissolution of the aluminium current collector; replacing LiPF6 with more stable lithium salts may diminish transition metal dissolution but unfortunately encounters severe aluminium oxidation. Here we report an electrolyte design that can solve this dilemma. By mixing a stable lithium salt LiN(SO2F)2 with dimethyl carbonate solvent at extremely high concentrations, we obtain an unusual liquid showing a three-dimensional network of anions and solvent molecules that coordinate strongly to Li+ ions. This simple formulation of superconcentrated LiN(SO2F)2/dimethyl carbonate electrolyte inhibits the dissolution of both aluminium and transition metal at around 5 V, and realizes a high-voltage LiNi0.5Mn1.5O4/graphite battery that exhibits excellent cycling durability, high rate capability and enhanced safety. PMID:27354162

Facile synthesis of single-crystal mesoporous CoNiO2 nanosheets assembled flowers as anode materials for lithium-ion batteries

International Nuclear Information System (INIS)

Liu, Yanguo; Zhao, Yanyan; Yu, Yanlong; Ahmad, Mashkoor; Sun, Hongyu

2014-01-01

Highlights: • Mesoporous CoNiO 2 microflowers have been synthesized. • Li-ion batteries performance of CoNiO 2 has been investigated. • CoNiO 2 structure delivers high capacity, good cycling stability and high rate capability. • The electrochemical performance is attributed to the mesoporous nature and the 3D structure. • CoNiO 2 can be considered to be an attractive candidate as an electrode material for LIBs. - Abstract: Mesoporous CoNiO 2 microflowers assembled with single-crystal nanosheets were successfully synthesized by a hydrothermal method and subsequent annealing process and their lithium storage capacity were investigated. The structural and compositional analysis of the mesoporous CoNiO 2 microflowers has been studied by X-ray diffraction, field emission scanning electron microscopy and high-resolution transmission electron microscopy. The Bruauer–Emmett–Teller specific surface area of CoNiO 2 microflowers has been calculated by the nitrogen isotherm curve and pore size distribution has been determined by the Barret–Joyner–Halenda method. It has been found that the as-prepared CoNiO 2 electrodes delivered satisfied capacity, good cycling stability and rate capability. The improved electrochemical performance is attributed to the mesoporous nature and the 3D assembled structure. Therefore, such a structure can be considered to be an attractive candidate as an electrode material for lithium-ion batteries

Formation of NiCo{sub 2}V{sub 2}O{sub 8} yolk-double shell spheres with enhanced lithium storage properties

Energy Technology Data Exchange (ETDEWEB)

Lu, Yan; Nai, Jianwei; Lou, Xiong Wen David [School of Chemical and Biomedical Engineering, Nanyang Technological University, Singapore (Singapore)

2018-03-05

Complex nanostructures with multi-components and intricate architectures hold great potential in developing high-performance electrode materials for lithium-ion batteries (LIBs). Herein, we demonstrate a facile self-templating strategy for the synthesis of metal vanadate nanomaterials with complex chemical composition of NiCo{sub 2}V{sub 2}O{sub 8} and a unique yolk-double shell structure. Starting with the Ni-Co glycerate spheres, NiCo{sub 2}V{sub 2}O{sub 8} yolk-double shell spheres are synthesized through an anion-exchange reaction of Ni-Co glycerate templates with VO{sub 3}{sup -} ions, followed by an annealing treatment. By virtue of compositional and structural advantages, these NiCo{sub 2}V{sub 2}O{sub 8} yolk-double shell spheres manifest outstanding lithium storage properties when evaluated as anodes for LIBs. Impressively, an extra-high reversible capacity of 1228 mAh g{sup -1} can be retained after 500 cycles at a high current density of 1.0 Ag{sup -1}. (copyright 2018 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

One-Pot Synthesis of Lithium-Rich Cathode Material with Hierarchical Morphology.

Science.gov (United States)

Luo, Kun; Roberts, Matthew R; Hao, Rong; Guerrini, Niccoló; Liberti, Emanuela; Allen, Christopher S; Kirkland, Angus I; Bruce, Peter G

2016-12-14

Lithium-rich transition metal oxides, Li 1+x TM 1-x O 2 (TM, transition metal), have attracted much attention as potential candidate cathode materials for next generation lithium ion batteries because their high theoretical capacity. Here we present the synthesis of Li[Li 0.2 Ni 0.2 Mn 0.6 ]O 2 using a facile one-pot resorcinol-formaldehyde method. Structural characterization indicates that the material adopts a hierarchical porous morphology consisting of uniformly distributed small pores and disordered large pore structures. The material exhibits excellent electrochemical cycling stability and a good retention of capacity at high rates. The material has been shown to be both advantageous in terms of gravimetric and volumetric capacities over state of the art commercial cathode materials.

Layered oxides-LiNi1/3Co1/3Mn1/3O2 as anode electrode for symmetric rechargeable lithium-ion batteries

Science.gov (United States)

Wang, Yuesheng; Feng, Zimin; Yang, Shi-Ze; Gagnon, Catherine; Gariépy, Vincent; Laul, Dharminder; Zhu, Wen; Veillette, René; Trudeau, Michel L.; Guerfi, Abdelbast; Zaghib, Karim

2018-02-01

High-performance and long-cycling rechargeable lithium-ion batteries have been in steadily increasing demand for the past decades. Nevertheless, the two dominant anodes at the moment, graphite and L4T5O12, suffer from a safety issue of lithium plating (operating voltage at ∼ 0.1 V vs. Li+/Li) and low capacity (175 mAh/g), respectively. Here, we report LiNi1/3Co1/3Mn1/3O2 as an alternative anode material which has a working voltage of ∼1.1 V and a capacity as high as 330 mAh/g at the current rate of C/15. Symmetric cells with both electrodes containing LiNi1/3Co1/3Mn1/3O2 can deliver average discharge voltage of 2.2 V. In-situ XRD, HRTEM and first principles calculations indicate that the reaction mechanism of a LiNi1/3Co1/3Mn1/3O2 anode is comprised mainly of conversion. Both the fundamental understanding and practical demonstrations suggest that LiNi1/3Co1/3Mn1/3O2 is a promising negative electrode material for lithium-ion batteries.

Orbital-Specific observation of O2p and Ni3d electrons in LiNi0.5Mn0.5O2, a cathode material for lithium-ion batteries

Science.gov (United States)

Satou, Yoshinori; Komine, Shigeki; Shimizu, Sumera

2017-09-01

Cathode materials for lithium-ion batteries containing Ni2+ have attracted much interest because of their high theoretical capacity. However, the precise electronic structures of these cathode materials have not yet been clearly observed, especially the energy positions of the O2p and Ni3d orbitals and the shape of the density of states. The aim of this study was to investigate the relative energy positions and shape of the density of states of O2p and Ni3d for LiNi0.5Mn0.5O2 experimentally. We cleaved a LiNi0.5Mn0.5O2 pellet in an Ar-filled glove box and performed synchrotron ultraviolet photoelectron spectroscopy for different photon energies, which enabled us to investigate the relative cross-section intensity of O2p and Ni3d. As a result, the valence-band structure was determined. We found that O2p electrons are itinerant and exist in the vicinity of the Fermi energy more than Ni3d electrons. Ni3d electrons are more localized and spread mainly from 1.2-1.5 eV below the Fermi energy. To validate the electronic structure, we measured the synchrotron O K-edge X-ray absorption fine structure of electrochemically lithium-extracted LiNi0.5Mn0.5O2. The electronic structure demonstrated that ligand holes in the oxygen atoms form below the Fermi level during the initial stage of Li extraction and that the formation rate of the holes decreases with Li extraction.

Electrochemical performances of LiNi1−xMnxPO4 (x = 0.05–0.2) olivine cathode materials for high voltage rechargeable lithium ion batteries

DEFF Research Database (Denmark)

Karthikprabhu, S.; Karuppasamy, K.; Vikraman, Dhanasekaran

2018-01-01

This study demonstrated to synthesis of carbon-free lithium nickel phosphate (LiNiPO4) and its analogue of manganese doped LiNi1−xMnxPO4 (x = 0.05–0.2) cathode materials by a facile polyol method and their suitability for use in high voltage lithium ion batteries (LIBs). The physicochemical...

Pb3O4 type antimony oxides MSb2O4 (M = Co, Ni) as anode for Li-ion batteries

International Nuclear Information System (INIS)

Jibin, A.K.; Reddy, M.V.; Subba Rao, G.V.; Varadaraju, U.V.; Chowdari, B.V.R.

2012-01-01

Graphical abstract: Isostructural Pb 3 O 4 type MSb 2 O 4 (M = Co, Ni) compounds were investigated as possible anodes for lithium ion batteries. The reversible capacity is due to electrochemically active Sb and the transition metal and Li 2 O form an inactive matrix which buffers volume variations associated with alloying-de-alloying of antimony. Highlights: ► Isostructural MSb 2 O 4 (M = Co, Ni) were studied as anode for LIBs for first time. ► Li/MSb 2 O 4 (M = Co, Ni) cells displayed reversibility due to electrochemically active Sb. ► CoSb 2 O 4 showed good reversibility compared to NiSb 2 O 4 . - Abstract: Polycrystalline samples of isostructural MSb 2 O 4 (M = Co, Ni) have been prepared by solid state synthesis and lithium-storage is investigated as possible anode materials for lithium-ion batteries. The reaction mechanism of lithium with MSb 2 O 4 (M = Co, Ni) is explored by galvanostatic cycling, cyclic voltammogram and ex situ studies. Both CoSb 2 O 4 and NiSb 2 O 4 exhibit similar electrochemical behavior and show reversible capacity of 490 and 412 mAh g −1 respectively in the first cycle. Reversible alloying de-alloying of Li x Sb takes place in an amorphous matrix of M (Co, Ni) and Li 2 O during electrochemical cycling.

Various aspects of LiNiO2 chemistry: A review

Directory of Open Access Journals (Sweden)

P. Kalyani and N. Kalaiselvi

2005-01-01

Full Text Available Despite the appearance of ever first report on the synthesis of LiNiO2 in 1954, active research to identify and evaluate its suitability as an electrode material in rechargeable lithium batteries started only in late 80's. Following this, numerous articles discussed the synthesis, electrochemical behavior and the problems associated with the compound. In this connection, the present communication reviews certain important experimental results obtained by different research groups on various aspects of LiNiO2, in order to understand the significance of LiNiO2 as a potential cathode material for rechargeable lithium batteries. Also selected type of methodologies adopted to synthesize the title compound have also been discussed to substantiate the dependence of electrochemical behavior of LiNiO2 on the method of synthesis and reaction conditions. The subject has been discussed at length and may provide useful information on the properties of LiNiO2 and may enable the fabrication of tailor made nickel-based electrode materials for 'next generation' lithium or lithium-ion batteries along with the highlights of doped and coated derivatives of LiNiO2.

Mesoporous NiCo2O4 nanoneedles grown on three dimensional graphene networks as binder-free electrode for high-performance lithium-ion batteries and supercapacitors

International Nuclear Information System (INIS)

Liu, Sainan; Wu, Jun; Zhou, Jiang; Fang, Guozhao; Liang, Shuquan

2015-01-01

Graphical abstract: Mesoporous NiCo 2 O 4 nanoneedles grown on three dimensional graphene networks have been successfully prepared by a facile solvothermal reaction with subsequent annealing treatment. Significantly, as a binder-free electrode for high-performance lithium-ion batteries and supercapacitors, the hybrid exhibits high specific capacity/capacitance and excellent cycling stability over long-term cycling. - Highlights: • Mesoporous NiCo 2 O 4 nanoneedles grown on 3D graphene networks are successfully prepared. • The NiCo 2 O 4 /3DGN hybrid is directly used as binder-free electrode for LIBs and SCs. • The hybrid exhibits superior long-term cycling stability up to 2000 cycles for LIBs application. • The hybrid delivers a high specific capacitance of 970 F g −1 at 20 A g −1 . • The hybrid demonstrates excellent capacitance retention of ∼96.5% after 3000 cycles for SCs application. - Abstract: Mesoporous nickel cobaltite (NiCo 2 O 4 ) nanoneedles grown on three dimensional graphene networks have been successfully prepared by a facile solvothermal reaction with subsequent annealing treatment. The NiCo 2 O 4 /3DGN hybrid is then used as binder-free electrode for high-performance lithium-ion batteries and supercapacitors. The three dimensional graphene based binder-free electrode is considered more desirable than powder nanostructures in terms of shorter Li + ion diffusion and electron transportation paths, good strain accommodation, better interfacial/chemical distributions and high electrical conductivity. As a result, when used as an anode material for lithium-ion batteries (LIBs), it exhibits high specific discharge capacity as well as superior cycling stability up to 2000 cycles. When it is used for supercapacitor application, this hybrid delivers a high specific capacitance of 970 F g −1 at a high current density of 20 A g −1 with excellent capacitance retention of ∼96.5% after 3000 cycles. Moreover, this synthesis strategy is simple

Monodispersed Carbon-Coated Cubic NiP2 Nanoparticles Anchored on Carbon Nanotubes as Ultra-Long-Life Anodes for Reversible Lithium Storage.

Science.gov (United States)

Lou, Peili; Cui, Zhonghui; Jia, Zhiqing; Sun, Jiyang; Tan, Yingbin; Guo, Xiangxin

2017-04-25

In search of new electrode materials for lithium-ion batteries, metal phosphides that exhibit desirable properties such as high theoretical capacity, moderate discharge plateau, and relatively low polarization recently have attracted a great deal of attention as anode materials. However, the large volume changes and thus resulting collapse of electrode structure during long-term cycling are still challenges for metal-phosphide-based anodes. Here we report an electrode design strategy to solve these problems. The key to this strategy is to confine the electroactive nanoparticles into flexible conductive hosts (like carbon materials) and meanwhile maintain a monodispersed nature of the electroactive particles within the hosts. Monodispersed carbon-coated cubic NiP 2 nanoparticles anchored on carbon nanotubes (NiP 2 @C-CNTs) as a proof-of-concept were designed and synthesized. Excellent cyclability (more than 1000 cycles) and capacity retention (high capacities of 816 mAh g -1 after 1200 cycles at 1300 mA g -1 and 654.5 mAh g -1 after 1500 cycles at 5000 mA g -1 ) are characterized, which is among the best performance of the NiP 2 anodes and even most of the phosphide-based anodes reported so far. The impressive performance is attributed to the superior structure stability and the enhanced reaction kinetics incurred by our design. Furthermore, a full cell consisting of a NiP 2 @C-CNTs anode and a LiFePO 4 cathode is investigated. It delivers an average discharge capacity of 827 mAh g -1 based on the mass of the NiP 2 anode and exhibits a capacity retention of 80.7% over 200 cycles, with an average output of ∼2.32 V. As a proof-of-concept, these results demonstrate the effectiveness of our strategy on improving the electrode performance. We believe that this strategy for construction of high-performance anodes can be extended to other phase-transformation-type materials, which suffer a large volume change upon lithium insertion/extraction.

Orbital-Specific observation of O2p and Ni3d electrons in LiNi0.5Mn0.5O2, a cathode material for lithium-ion batteries

Directory of Open Access Journals (Sweden)

Yoshinori Satou

2017-09-01

Full Text Available Cathode materials for lithium-ion batteries containing Ni2+ have attracted much interest because of their high theoretical capacity. However, the precise electronic structures of these cathode materials have not yet been clearly observed, especially the energy positions of the O2p and Ni3d orbitals and the shape of the density of states. The aim of this study was to investigate the relative energy positions and shape of the density of states of O2p and Ni3d for LiNi0.5Mn0.5O2 experimentally. We cleaved a LiNi0.5Mn0.5O2 pellet in an Ar-filled glove box and performed synchrotron ultraviolet photoelectron spectroscopy for different photon energies, which enabled us to investigate the relative cross-section intensity of O2p and Ni3d. As a result, the valence-band structure was determined. We found that O2p electrons are itinerant and exist in the vicinity of the Fermi energy more than Ni3d electrons. Ni3d electrons are more localized and spread mainly from 1.2–1.5 eV below the Fermi energy. To validate the electronic structure, we measured the synchrotron O K-edge X-ray absorption fine structure of electrochemically lithium-extracted LiNi0.5Mn0.5O2. The electronic structure demonstrated that ligand holes in the oxygen atoms form below the Fermi level during the initial stage of Li extraction and that the formation rate of the holes decreases with Li extraction.

Synthetic Control of Kinetic Reaction Pathway and Cationic Ordering in High-Ni Layered Oxide Cathodes

Energy Technology Data Exchange (ETDEWEB)

Wang, Dawei [Sustainable Energy Technologies Department, Brookhaven National Laboratory, Upton NY 11973 USA; Collaborative Innovation Center of Chemistry for Energy Materials, State Key Laboratory Physical Chemistry Solid Surfaces, Department of Chemistry, Xiamen University, Xiamen Fujian 361005 China; Kou, Ronghui [X-Ray Science Division, Advanced Photon Source, Argonne National Laboratory, Argonne IL 60439 USA; Ren, Yang [X-Ray Science Division, Advanced Photon Source, Argonne National Laboratory, Argonne IL 60439 USA; Sun, Cheng-Jun [X-Ray Science Division, Advanced Photon Source, Argonne National Laboratory, Argonne IL 60439 USA; Zhao, Hu [Sustainable Energy Technologies Department, Brookhaven National Laboratory, Upton NY 11973 USA; Zhang, Ming-Jian [Sustainable Energy Technologies Department, Brookhaven National Laboratory, Upton NY 11973 USA; School of Advanced Materials, Peking University Shenzhen Graduate School, Shenzhen Guangdong 518055 P. R. China; Li, Yan [Chemical Sciences and Engineering Division, Argonne National Laboratory, Argonne IL 60439 USA; Huq, Ashifia [Chemical and Engineering Materials Division, Oak Ridge National Laboratory, Oak Ridge TN 37831 USA; Ko, J. Y. Peter [The Cornell High Energy Synchrotron Source, Cornell University, Ithaca NY 14853 USA; Pan, Feng [School of Advanced Materials, Peking University Shenzhen Graduate School, Shenzhen Guangdong 518055 P. R. China; Sun, Yang-Kook [Department of Energy Engineering, Hanyang University, Seoul 133-791 South Korea; Yang, Yong [Collaborative Innovation Center of Chemistry for Energy Materials, State Key Laboratory Physical Chemistry Solid Surfaces, Department of Chemistry, Xiamen University, Xiamen Fujian 361005 China; Amine, Khalil [Chemical Sciences and Engineering Division, Argonne National Laboratory, Argonne IL 60439 USA; Bai, Jianming [National Synchrotron Light Source II, Brookhaven National Laboratory, Upton NY 11973 USA; Chen, Zonghai [Chemical Sciences and Engineering Division, Argonne National Laboratory, Argonne IL 60439 USA; Wang, Feng [Sustainable Energy Technologies Department, Brookhaven National Laboratory, Upton NY 11973 USA

2017-08-25

Nickel-rich layered transition metal oxides, LiNi1-x(MnCo)(x)O-2 (1-x >= 0.5), are appealing candidates for cathodes in next-generation lithium-ion batteries (LIBs) for electric vehicles and other large-scale applications, due to their high capacity and low cost. However, synthetic control of the structural ordering in such a complex quaternary system has been a great challenge, especially in the presence of high Ni content. Herein, synthesis reactions for preparing layered LiNi0.7Mn0.15Co0.15O2 (NMC71515) by solid-state methods are investigated through a combination of time-resolved in situ high-energy X-ray diffraction and absorption spectroscopy measurements. The real-time observation reveals a strong temperature dependence of the kinetics of cationic ordering in NMC71515 as a result of thermal-driven oxidation of transition metals and lithium/oxygen loss that concomitantly occur during heat treatment. Through synthetic control of the kinetic reaction pathway, a layered NMC71515 with low cationic disordering and a high reversible capacity is prepared in air. The findings may help to pave the way for designing high-Ni layered oxide cathodes for LIBs.

Cathode material for lithium batteries

Science.gov (United States)

Park, Sang-Ho; Amine, Khalil

2013-07-23

A method of manufacture an article of a cathode (positive electrode) material for lithium batteries. The cathode material is a lithium molybdenum composite transition metal oxide material and is prepared by mixing in a solid state an intermediate molybdenum composite transition metal oxide and a lithium source. The mixture is thermally treated to obtain the lithium molybdenum composite transition metal oxide cathode material.

Carbonized polydopamine coated single-crystalline NiFe2O4 nanooctahedrons with enhanced electrochemical performance as anode materials in a lithium ion battery

International Nuclear Information System (INIS)

Liu, Xinxin; Zhang, Tong; Qu, Yue; Tian, Ge; Yue, Huijuan; Zhang, Dong; Feng, Shouhua

2017-01-01

Graphical abstract: NiFe 2 O 4 @ NCweresuccessfullyfabricatedviaasubsequentcarbonizationofpolydopamine.(*) A nanocomposite containing 20% mass fraction of dopamine exhibited enhanced lithium ion battery performance with high reversible cycle capacity and good rate retention performance. - Highlights: • NiFe 2 O 4 nanooctahedrons were synthesized by a facile hydrothermal process. • A phase formation mechanism was studied by time-dependent experiments. • NiFe 2 O 4 with N-doped carbon shell was fabricated via carbonization of polydopamine. • NiFe 2 O 4 @NC 20 showed the best rate capability and cycle stability. - Abstract: Combining nanostructure engineering with conductive carbonaceous material is a promising strategy to obtain high-performance lithium ion batteries (LIBs). In this work, spinel NiFe 2 O 4 nanooctahedrons were initially synthesized at a low temperature without further annealing. We investigated the phase formation mechanism by time-dependent experiments. Next, octahedral NiFe 2 O 4 with a nitrogen-doped carbon shell (NiFe 2 O 4 @NC) were successfully fabricated via a subsequent carbonization of polydopamine (PDA). We systematically varied the dopamine content in the NiFe 2 O 4 /carbon nanocomposites and found that a nanocomposite containing 20% mass fraction of dopamine exhibited enhanced lithium ion battery performance with high reversible cycle capacity and good rate retention performance compared with the pure material. Remarkably, the hybrid nanocomposite delivered a high reversible capacity of 1297 mAh g −1 even after 50 cycles at a current density of 100 mA g −1 . Additionally, a high capacity of 1204 mAh g −1 was retained at a high current density of 500 mA g −1 after 300 cycles. This improvement in electrochemical performance is attributed to the enhanced structural stability and electrical conductivity caused by the carbon layer, and is supported by TEM and EIS measurements.

Nanotubes within transition metal silicate hollow spheres: Facile preparation and superior lithium storage performances

Energy Technology Data Exchange (ETDEWEB)

Zhang, Fan; An, Yongling; Zhai, Wei; Gao, Xueping [Key Laboratory for Liquid–Solid Structural Evolution & Processing of Materials (Ministry of Education), Jinan 250100 (China); Feng, Jinkui, E-mail: jinkui@sdu.edu.cn [Key Laboratory for Liquid–Solid Structural Evolution & Processing of Materials (Ministry of Education), Jinan 250100 (China); Ci, Lijie [Key Laboratory for Liquid–Solid Structural Evolution & Processing of Materials (Ministry of Education), Jinan 250100 (China); Xiong, Shenglin [School of Materials Science and Engineering, School of Chemistry and Chemical Engineering, Shandong University, Jinan 250100 (China)

2015-10-15

Highlights: • The hollow Co{sub 2}SiO{sub 4}, MnSiO{sub 3} and CuSiO{sub 3} were successfully prepared by a facile hydrothermal method using SiO{sub 2} nanosphere. • The hollow Co{sub 2}SiO{sub 4}, MnSiO{sub 3} and CuSiO{sub 3} were tested as anode materials for lithium batteries. • The hollow Co{sub 2}SiO{sub 4}, MnSiO{sub 3} and CuSiO{sub 3} delivered superior electrochemical performance. • The lithium storage mechanism is probe via cyclic voltammetry and XPS. - Abstract: A series of transition metal silicate hollow spheres, including cobalt silicate (Co{sub 2}SiO{sub 4}), manganese silicate (MnSiO{sub 3}) and copper silicate (CuSiO{sub 3}.2H{sub 2}O, CuSiO{sub 3} as abbreviation in the text) were prepared via a simple and economic hydrothermal method by using silica spheres as chemical template. Time-dependent experiments confirmed that the resultants formed a novel type of hierarchical structure, hollow spheres assembled by numerous one-dimensional (1D) nanotubes building blocks. For the first time, the transition metal silicate hollow spheres were characterized as novel anode materials of Li-ion battery, which presented superior lithium storage capacities, cycle performance and rate performance. The 1D nanotubes assembly and hollow interior endow this kind of material facilitate fast lithium ion and electron transport and accommodate the big volume change during the conversion reactions. Our study shows that low-cost transition metal silicate with rationally designed nanostructures can be promising anode materials for high capacity lithium-ion battery.

Positive electrode for a lithium battery

Science.gov (United States)

Park, Sang-Ho; Amine, Khalil

2015-04-07

A method for producing a lithium alkali transition metal oxide for use as a positive electrode material for lithium secondary batteries by a precipitation method. The positive electrode material is a lithium alkali transition metal composite oxide and is prepared by mixing a solid state mixed with alkali and transition metal carbonate and a lithium source. The mixture is thermally treated to obtain a small amount of alkali metal residual in the lithium transition metal composite oxide cathode material.

Investigation of positive electrode materials based on MnO2 for lithium batteries

International Nuclear Information System (INIS)

Le, My Loan Phung; Lam, Thi Xuan Binh; Pham, Quoc Trung; Nguyen, Thi Phuong Thoa

2011-01-01

Various composite materials of MnO 2 /C have been synthesized by electrochemical deposition and then used for the synthesis of lithium manganese oxide (LiMn 2 O 4 ) spinel as a cathode material for lithium ion batteries. The structure and electrochemical properties of electrode materials based on MnO 2 /C, spinel LiMn 2 O 4 and doped spinel LiNi 0.5 Mn 1.5 O 4 have been studied. The influence of synthesis conditions on the structural and electrochemical properties of synthesized materials was investigated by x-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electronic microscopy (TEM) and charge–discharge experiments. Some of the studied materials exhibit good performance of cycling and discharge capacity

Micro-stress dominant displacive reconstructive transition in lithium aluminate

Energy Technology Data Exchange (ETDEWEB)

Hu, Qiwei; Yan, Xiaozhi; Zhang, Leilei; Peng, Fang [Institute of Atomic and Molecular Physics, Sichuan University, 610065 Chengdu (China); Lei, Li, E-mail: lei@scu.edu.cn; He, Duanwei [Institute of Atomic and Molecular Physics, Sichuan University, 610065 Chengdu (China); Key Laboratory of High Energy Density Physics and Technology of Ministry of Education, Sichuan University, 610065 Chengdu (China); Li, Xiaodong [Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049 (China)

2016-08-15

It is supposed that diffusive reconstructive transitions usually take place under hydrostatic pressure or low stresses, and displacive reconstructive phase transitions easily occur at nonhydrostatic pressure. Here, by in-situ high pressure synchrotron X-ray diffraction and single-crystal Raman scattering studies on lithium aluminate at room temperature, we show that the reconstructive transition mechanism is dependent on the internal microscopic stresses rather than the macroscopic stresses. In this case, even hydrostatic pressure can favor the displacive transition if the compressibility of crystal is anisotropic. During hydrostatic compression, γ-LiAlO{sub 2} transforms to δ-LiAlO{sub 2} at about 4 GPa, which is much lower than that in previous nonhydrostatic experiments (above 9 GPa). In the region where both phases coexist, there are enormous microscopic stresses stemming from the lattice mismatch, suggesting that this transition is displacive. Furthermore, the atomic picture is drawn with the help of the shear Raman modes.

Solid NMR study of lithium ions accommodated in various transition metal oxides

International Nuclear Information System (INIS)

Kanzaki, Yasushi; Suzuki, Noriko

2008-01-01

Solid NMR was used to elucidate the lithium accommodation/extraction reaction in various transition metal oxides. The first study was the lithium ion exchange reaction of titanium antimonic acid (TiSbA). The effect of hydration on the selectivity of lithium ion in the solid phase was examined using 7 Li NMR. The second study was the irreversible ion exchange behavior of HNbO 3 . The selectivity for the lithium ion and the irreversible behavior were examined using 1 H and 7 Li NMR. The third study was the isotope separation between 6 Li and 7 Li in various inorganic ion exchangers. The high isotope separation coefficient was ascribed to the degree of dehydration during the ion exchange reaction. The degree of dehydration was examined by 1 H and 7 Li NMR studies. The last study was determining the mechanism of the lithium accommodation/extraction reaction of λ-MnO 2 in an aqueous solution. The different paths between the accommodation and extraction and the formation of MnO 4- during the accommodation were determined by chemical analysis. The Knight shift in the 7 Li MAS-NMR spectra of Li 0.5 MnO 2 suggested the localization of the electron density on the lithium nuclei. An XPS study also suggested the presence of an electron density on the lithium nuclei. A pH-independent redox couple was assumed to account for the accommodation/extraction reaction of lithium ions, such as Li(I)/Li(0). (author)

An Insight into the Convenience and Efficiency of the Freeze-Drying Route to Construct 3D Graphene-Based Hybrids for Lithium-Ion Batteries

International Nuclear Information System (INIS)

Ding, Caihua; Zhao, Yongjie; Yan, Dong; Zhao, Yuzhen; Zhou, Heping; Li, Jingbo; Jin, Haibo

2016-01-01

Constructing hybrids of transition metal oxides with different kinds of carbon based materials has attracted a lot of attention recently. However, scalable synthesis of homogeneous hybrids with active controllable of microstructure remains great challenge. Here, we proposed a convenient and efficient strategy named freeze-drying process for scalable production of 3D NiO/graphene hybrids. With a controllable procedure, NiO microflowers and graphene layers could preserve uniform configuration from fully mixed solvent to final hybrids materials. The mechanical stability and electrical conductivity of NiO microflowers was increased by graphene. NiO microflowers as spacers intercalated into graphene layers and effectively prevented it from aggregation or restacking, leading to a high specific surface area in hybrids. The NiO/graphene exhibited enhanced cycle stability and rate performance when evaluated as an anode for lithium ion batteries. It rendered high specific capacities about 1000 mA h g −1 after 70 cycles, and 770 mA h g −1 after 100 cycles at 300 mA g −1 . Excellent electrochemical properties were probably ascribed to the synergistic effect of NiO microflowers and graphene layers, as a result of smart structure design by a freeze-drying route. This strategy with merits of rational construction and scalable production could establish new aspects for diverse hybrid towards industrialization.

Synthesis and properties of Li{sub 2}MnO{sub 3}-based cathode materials for lithium-ion batteries

Energy Technology Data Exchange (ETDEWEB)

Xue, Leigang; Zhang, Shu; Li, Shuli; Lu, Yao; Toprakci, Ozan [Fiber and Polymer Science Program, Department of Textile Engineering, Chemistry and Science, North Carolina State University, Raleigh, NC 27695-8301 (United States); Xia, Xin [Fiber and Polymer Science Program, Department of Textile Engineering, Chemistry and Science, North Carolina State University, Raleigh, NC 27695-8301 (United States); College of Textile and Clothing, Xinjiang University, Xinjiang, Urumchi 830046 (China); Chen, Chen [College of Textile and Clothing, Xinjiang University, Xinjiang, Urumchi 830046 (China); Hu, Yi [Fiber and Polymer Science Program, Department of Textile Engineering, Chemistry and Science, North Carolina State University, Raleigh, NC 27695-8301 (United States); Engineering Research Center for Eco-Dyeing and Finishing of Textiles, Zhejiang Sci-Tech University, Hangzhou, Zhejiang 310018 (China); Zhang, Xiangwu, E-mail: xiangwu_zhang@ncsu.edu [Fiber and Polymer Science Program, Department of Textile Engineering, Chemistry and Science, North Carolina State University, Raleigh, NC 27695-8301 (United States)

2013-11-15

Highlights: •0.3Li{sub 2}MnO{sub 3}·0.5LiMn{sub 0.5}Ni{sub 0.5}O{sub 2}·0.2LiCoO{sub 2} was synthesized by a co-precipitation method. •The preparation method is simple and this material is inexpensive due to the high contents of Mn and Ni. •The material could be charged to a high potential to extract more lithium without structural damage. •A relatively high capacity of 178 mAh g{sup −1} is delivered between 2.0 and 4.6 V with excellent cycling performance. -- Abstract: Lithium-ion batteries have been wildly used in various portable electronic devices and the application targets are currently moving from small-sized mobile devices to large-scale electric vehicles and grid energy storage. Therefore, lithium-ion batteries with higher energy densities are in urgent need. For high-energy cathodes, Li{sub 2}MnO{sub 3}–LiMO{sub 2} layered–layered (M = Mn, Co, Ni) materials are of significant interest due to their high specific capacities over wide operating potential windows. Here, three Li{sub 2}MnO{sub 3}-based cathode materials with α-NaFeO{sub 2} structure were prepared by a facile co-precipitation method and subsequent heat treatment. Among these three materials, 0.3Li{sub 2}MnO{sub 3}·0.5LiMn{sub 0.5}Ni{sub 0.5}O{sub 2}·0.2LiCoO{sub 2} shows the best lithium storage capability. This cathode material is composed of uniform nanosized particles with diameters ranging from 100 to 200 nm, and it could be charged to a high cutoff potential to extract more lithium, resulting in a high capacity of 178 mAh g{sup −1} between 2.0 and 4.6 V with almost no capacity loss over 100 cycles.

Vanadium based amorphous mixed oxides used as negative electrodes of lithium batteries; Oxydes mixtes amorphes a base de vanadium comme electrodes negatives de batteries au lithium

Energy Technology Data Exchange (ETDEWEB)

Guyomard, D.; Leroux, F.; Sigala, C.; Le Gal La Salle, A.; Piffard, Y. [Institut des Materiaux de Nantes, 44 (France). Laboratoire de Chimie des Solides

1996-12-31

This paper presents recent results concerning the chemical and electrochemical synthesis, the electrochemical properties and the characterization of two new families of amorphous oxides of formula Li{sub x}MVO{sub 4} (1Ni, Co, Zn, Cd) and M`V{sub 2}O{sub 6+{delta}} (0.5<{delta}<1; M` = Mn, Co). These oxides allows the low potential reversible insertion of lithium and can be used as negative electrodes in high performance lithium-ion batteries. (J.S.) 19 refs.

Vanadium based amorphous mixed oxides used as negative electrodes of lithium batteries; Oxydes mixtes amorphes a base de vanadium comme electrodes negatives de batteries au lithium

Energy Technology Data Exchange (ETDEWEB)

Guyomard, D; Leroux, F; Sigala, C; Le Gal La Salle, A.; Piffard, Y [Institut des Materiaux de Nantes, 44 (France). Laboratoire de Chimie des Solides

1997-12-31

This paper presents recent results concerning the chemical and electrochemical synthesis, the electrochemical properties and the characterization of two new families of amorphous oxides of formula Li{sub x}MVO{sub 4} (1Ni, Co, Zn, Cd) and M`V{sub 2}O{sub 6+{delta}} (0.5<{delta}<1; M` = Mn, Co). These oxides allows the low potential reversible insertion of lithium and can be used as negative electrodes in high performance lithium-ion batteries. (J.S.) 19 refs.

The effect of lithium adsorption on the formation of 1T-MoS2 phase based on first-principles calculation

International Nuclear Information System (INIS)

Zheng, Yuanliao; Huang, Yan; Shu, Haibo; Zhou, Xiaohao; Ding, Jiayi; Chen, Xiaoshuang; Lu, Wei

2016-01-01

The effect of lithium adsorption on the phase transition from 1H-MoS 2 to 1T-MoS 2 is studied by first-principles computations. The results indicate the possibilities of the phase transition for the lithium adsorption. Based on the results of charge density difference and charge-transfer of molybdenum disulfide with lithium adsorption, we elucidated that the mechanism of the changes of electronic property accompanying the phase transition is attributed to the electron transfer of different atoms. According to the result of transition state, it can be found that the phase-transition barrier is related to the coverage of lithium atoms on MoS 2 surface. It may be helpful to obtaining experimentally the stable 1T-MoS 2 structure. - Highlights: • The transformation of MoS 2 from semiconducting to metallic phases is elucidated on the essence of the electron transfer. • The relationship between Li coverage and phase transition barrier is obtained. • The decomposing of Lithiated 1T-MoS 2 at a high concentration of Li adsorption is explained. • The results can be helpful to obtaining experimentally the stable 1T-MoS 2 structure.

A FeNiMnC alloy with strain glass transition

Directory of Open Access Journals (Sweden)

Hui Ma

2018-02-01

Full Text Available Recent experimental and theoretical investigations suggested that doping sufficient point defects into a normal ferroelastic/martensitic alloy systems could lead to a frozen disordered state of local lattice strains (nanomartensite domains, thereby suppressing the long-range strain-ordering martensitic transition. In this study, we attempt to explore the possibility of developing novel ferrous Elinvar alloys by replacing nickel with carbon and manganese as dopant species. A nominal Fe89Ni5Mn4.6C1.4 alloy was prepared by argon arc melting, and XRD, DSC, DMA and TEM techniques were employed to characterize the strain glass transition signatures, such as invariance in average structure, frequency dispersion in dynamic mechanical properties (storage modulus and internal friction and the formation of nanosized strain domains. It is indicated that doping of Ni, Mn and C suppresses γ→α long-range strain-ordering martensitic transformation in Fe89Ni5Mn4.6C1.4 alloy, generating randomly distributed nanosized domains by strain glass transition. Keywords: Strain glass transition, Elinvar alloys, Point defects, Nanosized domains

Anion Redox Chemistry in the Cobalt Free 3d Transition Metal Oxide Intercalation Electrode Li[Li0.2Ni0.2Mn0.6]O2.

Science.gov (United States)

Luo, Kun; Roberts, Matthew R; Guerrini, Niccoló; Tapia-Ruiz, Nuria; Hao, Rong; Massel, Felix; Pickup, David M; Ramos, Silvia; Liu, Yi-Sheng; Guo, Jinghua; Chadwick, Alan V; Duda, Laurent C; Bruce, Peter G

2016-09-07

Conventional intercalation cathodes for lithium batteries store charge in redox reactions associated with the transition metal cations, e.g., Mn(3+/4+) in LiMn2O4, and this limits the energy storage of Li-ion batteries. Compounds such as Li[Li0.2Ni0.2Mn0.6]O2 exhibit a capacity to store charge in excess of the transition metal redox reactions. The additional capacity occurs at and above 4.5 V versus Li(+)/Li. The capacity at 4.5 V is dominated by oxidation of the O(2-) anions accounting for ∼0.43 e(-)/formula unit, with an additional 0.06 e(-)/formula unit being associated with O loss from the lattice. In contrast, the capacity above 4.5 V is mainly O loss, ∼0.08 e(-)/formula. The O redox reaction involves the formation of localized hole states on O during charge, which are located on O coordinated by (Mn(4+)/Li(+)). The results have been obtained by combining operando electrochemical mass spec on (18)O labeled Li[Li0.2Ni0.2Mn0.6]O2 with XANES, soft X-ray spectroscopy, resonant inelastic X-ray spectroscopy, and Raman spectroscopy. Finally the general features of O redox are described with discussion about the role of comparatively ionic (less covalent) 3d metal-oxygen interaction on anion redox in lithium rich cathode materials.

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

Science.gov (United States)

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

2018-06-19

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

Effect of mixed transition metal ions on DC conductivity in lithium bismuth borate glasses

Energy Technology Data Exchange (ETDEWEB)

Khasa, S.; Yadav, Arti, E-mail: artidabhur@gmail.com; Dahiya, M. S.; Seema,; Ashima [Physics Department, Deenbandhu Chhotu Ram University of Science & Technology, Murthal-131039 (India); Agarwal, A. [Physics Department, G.J. University of science and technology, Hisar-125001 (India)

2015-06-24

The DC conductivities of glasses having composition x(2NiO·V{sub 2}O{sub 5})·(30-x)Li{sub 2}O·20Bi{sub 2}O{sub 3}·50B{sub 2}O{sub 3} (with x=0, 2, 5, 7 and 10, i.e. NVLBB glasses) and glass samples having composition 7NiO·23 Li{sub 2}O·20Bi{sub 2}O{sub 3}·50B{sub 2}O{sub 3} and 7V{sub 2}O{sub 5}·23Li{sub 2}O·20Bi{sub 2}O{sub 3}·50B{sub 2}O{sub 3} (NLBB and VLBB respectively) are investigated as a function of temperature. Conductivity for glasses containing higher percentage of lithium ions is predominantly ionic and in glasses containing higher percentage of transition metal (TM) ions is predominantly electronic. The observed increase in conductivity with x and peak-like behavior at x=7 in NVLBB glasses due to competitive transport of small polaron contributing to a significant structural change in NVLBB glasses. Variation of molar volume and density was also observed with x. In NVLBB glasses, as x increases density increases except a slight decrease at x=7. Also density increases in NLBB whereas in case of VLBB it decreases in comparison to NVLBB1 glass composition. Mott’s small polaron hopping (SPH) model has been applied to analyze the high temperature conductivity data and activation energy.

Lithium-Based High Energy Density Flow Batteries

Science.gov (United States)

Bugga, Ratnakumar V. (Inventor); West, William C. (Inventor); Kindler, Andrew (Inventor); Smart, Marshall C. (Inventor)

2014-01-01

Systems and methods in accordance with embodiments of the invention implement a lithium-based high energy density flow battery. In one embodiment, a lithium-based high energy density flow battery includes a first anodic conductive solution that includes a lithium polyaromatic hydrocarbon complex dissolved in a solvent, a second cathodic conductive solution that includes a cathodic complex dissolved in a solvent, a solid lithium ion conductor disposed so as to separate the first solution from the second solution, such that the first conductive solution, the second conductive solution, and the solid lithium ionic conductor define a circuit, where when the circuit is closed, lithium from the lithium polyaromatic hydrocarbon complex in the first conductive solution dissociates from the lithium polyaromatic hydrocarbon complex, migrates through the solid lithium ionic conductor, and associates with the cathodic complex of the second conductive solution, and a current is generated.

One-pot synthesis of NiO/C composite nanoparticles as anode materials for lithium-ion batteries

Energy Technology Data Exchange (ETDEWEB)

Zhang, Lipeng, E-mail: lipeng.zhang@jcu.edu.au [School of Chemical Engineering, Shandong University of Technology, Zibo 255049 (China); College of Science, Technology and Engineering, James Cook University, Douglas, Queensland 4811 (Australia); Mu, Jiechen; Wang, Zhao; Li, Guomin; Zhang, Yanling [School of Chemical Engineering, Shandong University of Technology, Zibo 255049 (China); He, Yinghe, E-mail: yinghe.he@jcu.edu.au [College of Science, Technology and Engineering, James Cook University, Douglas, Queensland 4811 (Australia)

2016-06-25

Nanostructured NiO/C composite particles with controlled carbon content for lithium-ion battery anode were prepared via a one-pot hydrothermal approach and subsequent calcination in a high purity nitrogen atmosphere. The composites were composed of amorphous carbon and nanocrystalline NiO. The structure of the NiO crystals was determined with X-ray diffraction (XRD) analysis and the content of carbon was calculated from the energy dispersive spectroscopy (EDS) results. Scanning electron microscopy (SEM) images showed a relatively narrow distribution of particle size for both the neat NiO and NiO/C nanoparticles. Electrochemical performance measurements demonstrated that, after 50 cycles, NiO/C nanocomposites maintained a high reversible capacity of 585.9 mAh g{sup −1}, much higher than that of 356.1 mAh g{sup −1} of the neat NiO nanoparticles without carbon. The NiO/C nanoparticles also exhibited a remarkable discharge capacity, a high charge/discharge rate and an excellent cycle stability. The improvements can be attributed to the even carbon coating on the NiO particles, which significantly enhances the conductivity and improves the structural stability of the electrode. - Highlights: • NiO/C nanocomposite material is prepared via a one-pot hydrothermal approach. • Both NiO and NiO/C composite have a narrow particle size distribution. • Carbon in the NiO/C enhanced the conductivity and suppressed particle aggregation. • NiO/C composites maintained a reversible capacity of 585.9 mAh g{sup −1} after 50 cycles.

Oxide Fiber Cathode Materials for Rechargeable Lithium Cells

Science.gov (United States)

Rice, Catherine E.; Welker, Mark F.

2008-01-01

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

Characterization and electrochemical performance of lithium-active titanium dioxide inlaid LiNi{sub 0.5}Co{sub 0.2}Mn{sub 0.3}O{sub 2} material prepared by lithium residue-assisted method

Energy Technology Data Exchange (ETDEWEB)

Li, Lingjun [School of Physics and Electronic Science, Changsha University of Science and Technology, Changsha 410114 (China); Department of Mechanical and Biomedical Engineering, City University of Hong Kong, 83 Tat Chee Avenue, Kowloon (Hong Kong); Chen, Zhaoyong, E-mail: csullj@hotmail.com [School of Physics and Electronic Science, Changsha University of Science and Technology, Changsha 410114 (China); Song, Liubin [Hunan Provincial Key Laboratory of Materials Protection for Electric Power and Transportation, School of Chemistry and Biological Engineering, Changsha University of Science and Technology, Changsha 410004, Hunan (China); Xu, Ming; Zhu, Huali; Gong, Li [School of Physics and Electronic Science, Changsha University of Science and Technology, Changsha 410114 (China); Zhang, Kaili, E-mail: kaizhang@cityu.edu.hk [Department of Mechanical and Biomedical Engineering, City University of Hong Kong, 83 Tat Chee Avenue, Kowloon (Hong Kong)

2015-07-25

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

Porous Hollow Superlattice NiMn2O4/NiCo2O4 Mesocrystals as a Highly Reversible Anode Material for Lithium-Ion Batteries

Directory of Open Access Journals (Sweden)

Lingjun Li

2018-05-01

Full Text Available As a promising high-capacity anode material for Li-ion batteries, NiMn2O4 always suffers from the poor intrinsic conductivity and the architectural collapse originating from the volume expansion during cycle. Herein, a combined structure and architecture modulation is proposed to tackle concurrently the two handicaps, via a facile and well-controlled solvothermal approach to synthesize NiMn2O4/NiCo2O4 mesocrystals with superlattice structure and hollow multi-porous architecture. It is demonstrated that the obtained NiCo1.5Mn0.5O4 sample is made up of a new mixed-phase NiMn2O4/NiCo2O4 compound system, with a high charge capacity of 532.2 mAh g−1 with 90.4% capacity retention after 100 cycles at a current density of 1 A g−1. The enhanced electrochemical performance can be attributed to the synergistic effects of the superlattice structure and the hollow multi-porous architecture of the NiMn2O4/NiCo2O4 compound. The superlattice structure can improve ionic conductivity to enhance charge transport kinetics of the bulk material, while the hollow multi-porous architecture can provide enough void spaces to alleviate the architectural change during cycling, and shorten the lithium ions diffusion and electron-transportation distances.

PC based electrolytes with LiDFOB as an alternative salt for lithium-ion batteries

Science.gov (United States)

Knight, Brandon M.

Lithium-ion batteries (LIBs) have been greatly sought after as a source of renewable energy storage. LIBs have a wide range of applications including but not limited portable electronic devices, electric vehicles, and power tools. As a direct result of their commercial viability an insatiable hunger for knowledge, advancement within the field of LIBs has been omnipresent for the last two decades. However, there are set backs evident within the LIB field; most notably the limitations of standard electrolyte formulations and LiPF6 lithium salt. The standard primary carbonate of ethylene carbonate (EC) has a very limited operating range due to its innate physical properties, and the LiPF6 salt is known to readily decompose to form HF which can further degrade LIB longevity. The goal of our research is to explore the use of a new primary salt LiDFOB in conjunction with a propylene carbonate based electrolyte to establish a more flexible electrolyte formulation by constructing coin cells and cycling them under various conditions to give a clear understanding of each formulation inherent performance capabilities. Our studies show that 1.2M LiDFOB in 3:7 PC/EMC + 1.5% VC is capable of performing comparably to the standard 1.2M LiPF6 in 3:7 EC/EMC at 25°C and the PC electrolyte also illustrates performance superior to the standard at 55°C. The degradation of lithium manganese spinel electrodes, including LiNi 0.5Mn1.5O4, is an area of great concern within the field of lithium ion batteries (LIBs). Manganese containing cathode materials frequently have problems associated with Mn dissolution which significantly reduces the cycle life of LIB. Thus the stability of the cathode material is paramount to the performance of Mn spinel cathode materials in LIBs. In an effort to gain a better understanding of the stability of LiNi0.5 Mn1.5O4 in common LiPF6/carbonate electrolytes, samples were stored at elevated temperature in the presence of electrolyte. Then after storage both

High voltage cathode compositions for lithium-ion batteries

Science.gov (United States)

Lu, Zhonghua; Eberman, Kevin W

2017-03-21

A lithium transition metal oxide composition. The composition has the formula Li.sub.a[Li.sub.bNi.sub.cMn.sub.dCo.sub.e]O.sub.2, where a.gtoreq.0.9, b.gtoreq.0, c>0, d>0, e>0, b+c+d+e=1, 1.05.ltoreq.c/d.ltoreq.1.4, 0.05.ltoreq.e.ltoreq.0.30, 0.9.ltoreq.(a+b)/M.ltoreq.1.06, and M=c+d+e. The composition has an O3 type structure.

Corrosion behavior of Ni-based structural materials for electrolytic reduction in lithium molten salt

International Nuclear Information System (INIS)

Cho, Soo Haeng; Park, Sung Bin; Lee, Jong Hyeon; Hur, Jin Mok; Lee, Han Soo

2011-01-01

In this study, the corrosion behavior of new Ni-based structural materials was studied for electrolytic reduction after exposure to LiCl-Li 2 O molten salt at 650 deg. C for 24-216 h under an oxidizing atmosphere. The new alloys with Ni, Cr, Al, Si, and Nb as the major components were melted at 1700 deg. C under an inert atmosphere. The melt was poured into a preheated metallic mold to prepare an as-cast alloy. The corrosion products and fine structures of the corroded specimens were characterized by scanning electron microscope (SEM), Energy Dispersive X-ray Spectroscope (EDS), and X-ray diffraction (XRD). The corrosion products of as cast and heat treated low Si/high Ti alloys were Cr 2 O 3 , NiCr 2 O 4 , Ni, NiO, and (Al,Nb,Ti)O 2 ; those of as cast and heat treated high Si/low Ti alloys were Cr 2 O 3 , NiCr 2 O 4 , Ni, and NiO. The corrosion layers of as cast and heat treated low Si/high Ti alloys were continuous and dense. However, those of as cast and heat treated high Si/low Ti alloys were discontinuous and cracked. Heat treated low Si/high Ti alloy showed the highest corrosion resistance among the examined alloys. The superior corrosion resistance of the heat treated low Si/high Ti alloy was attributed to the addition of an appropriate amount of Si, and the metallurgical evaluations were performed systematically.

Low temperature phase transition of the stoichiometric Ln2NiO4 oxides

International Nuclear Information System (INIS)

Fernandez, F.; Saez-Puche, R.; Botto, I.L.; Baran, E.J.

1991-01-01

In this paper we will present a comparative study of the structural phase transition in Ln 2 NiO 4 oxides, by means of neutron diffraction and infrared(IR) spectroscopy. In the Ln 2 NiO 4 oxides (Ln=La, Pr and Nd), there is a low temperature structural phase transition from the orthorhombic symmetry to a tetragonal phase, of first order character. The IR spectra show, at low temperature, a splitting of the bands related with the stretching Ni-O, strongly correlated with the phase transformation. From the neutron data, the phase transition can be visualized as a sudden tilt of the nickel octahedra

In situ57Fe Moessbauer Investigation of Solid-State Redox Reactions of Lithium Insertion Electrodes for Advanced Batteries

International Nuclear Information System (INIS)

Sakai, Yoichi; Ariyoshi, Kingo; Ohzuku, Tsutomu

2002-01-01

A novel in situ electrochemical cell for 57 Fe Moessbauer measurements was developed in order to clarify the mechanisms of solid-state redox reactions in lithium insertion materials containing iron. Our in situ Moessbauer technique was successfully applied to the determination as to which transition metal ion was a redox center in the insertion electrodes, such as LiFe 0.5 Mn 1.5 O 4 , LiFeTiO 4 , or LiFe 0.25 Ni 0.75 O 2 , for the 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

Lithium Carbonate Recovery from Cathode Scrap of Spent Lithium-Ion Battery: A Closed-Loop Process.

Science.gov (United States)

Gao, Wenfang; Zhang, Xihua; Zheng, Xiaohong; Lin, Xiao; Cao, Hongbin; Zhang, Yi; Sun, Zhi

2017-02-07

A closed-loop process to recover lithium carbonate from cathode scrap of lithium-ion battery (LIB) is developed. Lithium could be selectively leached into solution using formic acid while aluminum remained as the metallic form, and most of the other metals from the cathode scrap could be precipitated out. This phenomenon clearly demonstrates that formic acid can be used for lithium recovery from cathode scrap, as both leaching and separation reagent. By investigating the effects of different parameters including temperature, formic acid concentration, H 2 O 2 amount, and solid to liquid ratio, the leaching rate of Li can reach 99.93% with minor Al loss into the solution. Subsequently, the leaching kinetics was evaluated and the controlling step as well as the apparent activation energy could be determined. After further separation of the remaining Ni, Co, and Mn from the leachate, Li 2 CO 3 with the purity of 99.90% could be obtained. The final solution after lithium carbonate extraction can be further processed for sodium formate preparation, and Ni, Co, and Mn precipitates are ready for precursor preparation for cathode materials. As a result, the global recovery rates of Al, Li, Ni, Co, and Mn in this process were found to be 95.46%, 98.22%, 99.96%, 99.96%, and 99.95% respectively, achieving effective resources recycling from cathode scrap of spent LIB.

High-energy cathode material for long-life and safe lithium batteries

Science.gov (United States)

Sun, Yang-Kook; Myung, Seung-Taek; Park, Byung-Chun; Prakash, Jai; Belharouak, Ilias; Amine, Khalil

2009-04-01

Layered lithium nickel-rich oxides, Li[Ni1-xMx]O2 (M=metal), have attracted significant interest as the cathode material for rechargeable lithium batteries owing to their high capacity, excellent rate capability and low cost. However, their low thermal-abuse tolerance and poor cycle life, especially at elevated temperature, prohibit their use in practical batteries. Here, we report on a concentration-gradient cathode material for rechargeable lithium batteries based on a layered lithium nickel cobalt manganese oxide. In this material, each particle has a central bulk that is rich in Ni and a Mn-rich outer layer with decreasing Ni concentration and increasing Mn and Co concentrations as the surface is approached. The former provides high capacity, whereas the latter improves the thermal stability. A half cell using our concentration-gradient cathode material achieved a high capacity of 209mAhg-1 and retained 96% of this capacity after 50 charge-discharge cycles under an aggressive test profile (55∘C between 3.0 and 4.4V). Our concentration-gradient material also showed superior performance in thermal-abuse tests compared with the bulk composition Li[Ni0.8Co0.1Mn0.1]O2 used as reference. These results suggest that our cathode material could enable production of batteries that meet the demanding performance and safety requirements of plug-in hybrid electric vehicles.

Particle size effect of Ni-rich cathode materials on lithium ion battery performance

International Nuclear Information System (INIS)

Hwang, Ilkyu; Lee, Chul Wee; Kim, Jae Chang; Yoon, Songhun

2012-01-01

Graphical abstract: The preparation condition of Ni-rich cathode materials was investigated. When the retention time was short, a poor cathode performance was observed. For long retention time condition, cathode performance displayed a best result at pH 12. Highlights: ► Ni-rich cathode materials (LiNi 0.8 Co 0.15 Al 0.05 O 2 ) were prepared by co-precipitation method using separate addition of Al salt. ► Particle size of Ni-rich cathode materials became larger with increase of retention time and solution pH. ► Cathode performance was poor for low retention time. ► Optimal pH for co-precipitation was 12. -- Abstract: Herein, Ni-rich cathode materials (LiNi 0.8 Co 0.15 Al 0.05 O 2 ) in lithium ion batteries are prepared by a separate addition of Ni/Co salt and Al sol solution using a continuously stirred tank reactor. Retention time and solution pH were controlled in order to obtain high performance cathode material. Particle size increase was observed with a higher retention time of the reactants. Also, primary and secondary particles became smaller according to an increase of solution pH, which was probably due to a decrease of growth rate. From the cathode application, a high discharge capacity (175 mAh g −1 ), a high initial efficiency (90%) and a good cycleability were observed in the cathode material prepared under pH 12 condition, which was attributed to its well-developed layered property and the optimal particle size. However, rate capability was inversely proportional to the particle size, which was clarified by a decrease of charge-transfer resistance measured in the electrochemical impedance spectroscopy.

Corrosion behavior of Ni-based structural materials for electrolytic reduction in lithium molten salt

Energy Technology Data Exchange (ETDEWEB)

Cho, Soo Haeng, E-mail: nshcho1@kaeri.re.kr [Korea Atomic Energy Research Institute, 1045 Daedeokdaero Yuseong-gu, Daejeon 305-353 (Korea, Republic of); Park, Sung Bin [Korea Atomic Energy Research Institute, 1045 Daedeokdaero Yuseong-gu, Daejeon 305-353 (Korea, Republic of); Lee, Jong Hyeon, E-mail: jonglee@cnu.ac.kr [Graduate School of Green Energy Technology, Chungnam National University, 79 Daehak-ro, Yuseong-gu, Daejeon 305-764 (Korea, Republic of); Hur, Jin Mok; Lee, Han Soo [Korea Atomic Energy Research Institute, 1045 Daedeokdaero Yuseong-gu, Daejeon 305-353 (Korea, Republic of)

2011-05-01

In this study, the corrosion behavior of new Ni-based structural materials was studied for electrolytic reduction after exposure to LiCl-Li{sub 2}O molten salt at 650 deg. C for 24-216 h under an oxidizing atmosphere. The new alloys with Ni, Cr, Al, Si, and Nb as the major components were melted at 1700 deg. C under an inert atmosphere. The melt was poured into a preheated metallic mold to prepare an as-cast alloy. The corrosion products and fine structures of the corroded specimens were characterized by scanning electron microscope (SEM), Energy Dispersive X-ray Spectroscope (EDS), and X-ray diffraction (XRD). The corrosion products of as cast and heat treated low Si/high Ti alloys were Cr{sub 2}O{sub 3}, NiCr{sub 2}O{sub 4}, Ni, NiO, and (Al,Nb,Ti)O{sub 2}; those of as cast and heat treated high Si/low Ti alloys were Cr{sub 2}O{sub 3}, NiCr{sub 2}O{sub 4}, Ni, and NiO. The corrosion layers of as cast and heat treated low Si/high Ti alloys were continuous and dense. However, those of as cast and heat treated high Si/low Ti alloys were discontinuous and cracked. Heat treated low Si/high Ti alloy showed the highest corrosion resistance among the examined alloys. The superior corrosion resistance of the heat treated low Si/high Ti alloy was attributed to the addition of an appropriate amount of Si, and the metallurgical evaluations were performed systematically.

Impact of medium-range order on the glass transition in liquid Ni-Si alloys

Science.gov (United States)

Lü, Y. J.; Entel, P.

2011-09-01

We study the thermophysical properties and structure of liquid Ni-Si alloys using molecular dynamics simulations. The liquid Ni-5% and 10%Si alloys crystallize to form the face-centered cubic (Ni) at 900 and 850 K, respectively, and the glass transitions take place in Ni-20% and 25%Si alloys at about 700 K. The temperature-dependent self-diffusion coefficients and viscosities exhibit more pronounced non-Arrhenius behavior with the increase of Si content before phase transitions, indicating the enhanced glass-forming ability. These appearances of thermodynamic properties and phase transitions are found to closely relate to the medium-range order clusters with the defective face-centered cubic structure characterized by both local translational and orientational order. This locally ordered structure tends to be destroyed by the addition of more Si atoms, resulting in a delay of nucleation and even glass transition instead.

Magnetocaloric effect and multifunctional properties of Ni-Mn-based Heusler alloys

Energy Technology Data Exchange (ETDEWEB)

Dubenko, Igor, E-mail: igor_doubenko@yahoo.com [Department of Physics, Southern Illinois University, Carbondale, IL 62901 (United States); Samanta, Tapas; Kumar Pathak, Arjun [Department of Physics, Southern Illinois University, Carbondale, IL 62901 (United States); Kazakov, Alexandr; Prudnikov, Valerii [Faculty of Physics, Moscow State University, Vorob' evy Gory, 11999I Moscow (Russian Federation); Stadler, Shane [Department of Physics and Astronomy, Louisiana State University, Baton Rouge, LA 70803 (United States); Granovsky, Alexander [Faculty of Physics, Moscow State University, Vorob' evy Gory, 11999I Moscow (Russian Federation); IKERBASQUE, The Basque Foundation for Science, 48011 Bilbao (Spain); Departamento de Fisica de Materiales, Facultad de Quimica, Universidad del Pais Vasco, Paseo M. de Lardizabal 3, 20018 Donostia - San Sebastian (Spain); Zhukov, Arcady [IKERBASQUE, The Basque Foundation for Science, 48011 Bilbao (Spain); Departamento de Fisica de Materiales, Facultad de Quimica, Universidad del Pais Vasco, Paseo M. de Lardizabal 3, 20018 Donostia - San Sebastian (Spain); Ali, Naushad [Department of Physics, Southern Illinois University, Carbondale, IL 62901 (United States)

2012-10-15

The studies of magnetocaloric properties, phase transitions, and phenomena related to magnetic heterogeneity in the vicinity of the martensitic transition (MT) in Ni-Mn-In and Ni-Mn-Ga off-stoichiometric Heusler alloys are summarized. The crystal structure, magnetocaloric effect (MCE), and magnetotransport properties were studied for the following alloys: Ni{sub 50}Mn{sub 50-x}In{sub x}, Ni{sub 50-x}Co{sub x}Mn{sub 35}In{sub 15}, Ni{sub 50}Mn{sub 35-x}Co{sub x}In{sub 15}, Ni{sub 50}Mn{sub 35}In{sub 14}Z (Z=Al, Ge), Ni{sub 50}Mn{sub 35}In{sub 15-x}Si{sub x}, Ni{sub 50-x}Co{sub x}Mn{sub 25+y}Ga{sub 25-y}, and Ni{sub 50-x}Co{sub x}Mn{sub 32-y}FeyGa{sub 18}. It was found that the magnetic entropy change, {Delta}S, associated with the inverse MCE in the vicinity of the temperature of the magneto-structural transition, TM, persists in a range of (125-5) J/(kg K) for a magnetic field change {Delta}H=5 T. The corresponding temperature varies with composition from 143 to 400 K. The MT in Ni{sub 50}Mn{sub 50-x}In{sub x} (x=13.5) results in a transition between two paramagnetic states. Associated with the paramagnetic austenite-paramagnetic martensite transition {Delta}S=24 J/(kg K) was detected for {Delta}H=5 T at T=350 K. The variation in composition of Ni{sub 2}MnGa can drastically change the magnetic state of the martensitic phase below and in the vicinity of TM. The presence of the martensitic phase with magnetic moment much smaller than that in the austenitic phase above TM leads to the large inverse MCE in the Ni{sub 42}Co{sub 8}Mn{sub 32-y}FeyGa{sub 18} system. The adiabatic change of temperature ({Delta}T{sub ad}) in the vicinity of TC and TM of Ni{sub 50}Mn{sub 35}In{sub 15} and Ni{sub 50}Mn{sub 35}In{sub 14}Z (Z=Al, Ge) was found to be {Delta}T{sub ad}=-2 K and 2 K for {Delta}H=1.8 T, respectively. It was observed that |{Delta}T{sub ad}| Almost-Equal-To 1 K for {Delta}H=1 T for both types of transitions. The results on resistivity, magnetoresistance, Hall

Intra- and inter-atomic optical transitions of Fe, Co, and Ni ferrocyanides studied using first-principles many-electron calculations

Energy Technology Data Exchange (ETDEWEB)

Watanabe, Shinta, E-mail: s-watanabe@nucl.nagoya-u.ac.jp, E-mail: j-onoe@nucl.nagoya-u.ac.jp; Sawada, Yuki; Nakaya, Masato; Yoshino, Masahito; Nagasaki, Takanori; Onoe, Jun, E-mail: s-watanabe@nucl.nagoya-u.ac.jp, E-mail: j-onoe@nucl.nagoya-u.ac.jp [Department of Materials, Physics and Energy Engineering, Graduated School of Engineering, Nagoya University, Furo-cho, Chikusa-ku, Nagoya, Aichi 464-8603 (Japan); Kameyama, Tatsuya; Torimoto, Tsukasa [Department of Crystalline Materials Science, Graduated School of Engineering, Nagoya University, Furo-cho, Chikusa-ku, Nagoya, Aichi 464-8603 (Japan); Inaba, Yusuke; Takahashi, Hideharu; Takeshita, Kenji [Research Laboratory for Nuclear Reactors, Tokyo Institute of Technology, 2-12-1-N1-16 O-okayama, Meguro-ku, Tokyo 152-8550 (Japan)

2016-06-21

We have investigated the electronic structures and optical properties of Fe, Co, and Ni ferrocyanide nanoparticles using first-principles relativistic many-electron calculations. The overall features of the theoretical absorption spectra for Fe, Ni, and Co ferrocyanides calculated using a first-principles many-electron method well reproduced the experimental one. The origins of the experimental absorption spectra were clarified by performing a configuration analysis based on the many-electron wave functions. For Fe ferrocyanide, the experimental absorption peaks originated from not only the charge-transfer transitions from Fe{sup 2+} to Fe{sup 3+} but also the 3d-3d intra-transitions of Fe{sup 3+} ions. In addition, the spin crossover transition of Fe{sup 3+} predicted by the many-electron calculations was about 0.24 eV. For Co ferrocyanide, the experimental absorption peaks were mainly attributed to the 3d-3d intra-transitions of Fe{sup 2+} ions. In contrast to the Fe and Co ferrocyanides, Ni ferrocyanide showed that the absorption peaks originated from the 3d-3d intra-transitions of Ni{sup 3+} ions in a low-energy region, while from both the 3d-3d intra-transitions of Fe{sup 2+} ions and the charge-transfer transitions from Fe{sup 2+} to Ni{sup 3+} in a high-energy region. These results were quite different from those of density-functional theory (DFT) calculations. The discrepancy between the results of DFT calculations and those of many-electron calculations suggested that the intra- and inter-atomic transitions of transition metal ions are significantly affected by the many-body effects of strongly correlated 3d electrons.

The LiyNi0.2Mn0.2Co0.6O2 electrode materials: A structural and magnetic study

International Nuclear Information System (INIS)

Labrini, Mohamed; Saadoune, Ismael; Almaggoussi, Abdelmajid; Elhaskouri, Jamal; Amoros, Pedro

2012-01-01

Graphical abstract: EPR signal of the Li 0.6 Co 0.6 Ni 0.2 Mn 0.2 O 2 composition showing that Mn 4+ ions are the solely paramagnetic ions in the structure. Highlights: ► LiCo 0.6 Ni 0.2 Mn 0.2 O 2 was prepared by the combustion method with sucrose as a fuel. ► Chemical delithiaition was performed by using NO 2 BF 4 oxidizing agent. ► The rhombohedral symmetry was preserved upon lithium removal. ► Lithium extraction leads to Ni 2+ oxidation to Ni 4+ followed by Co 3+ oxidation. ► The EPR narrow signal of Li 0.6 Co 0.6 Ni 0.2 Mn 0.2 O 2 is due to the only active Mn 4+ ions. -- Abstract: Layered LiNi 0.2 Mn 0.2 Co 0.6 O 2 phase, belonging to a solid solution between LiNi 1/2 Mn 1/2 O 2 and LiCoO 2 most commercialized cathodes, was prepared via the combustion method at 900 °C for a short time (1 h). Structural and magnetic properties of this material during chemical extraction were investigated. The powders adopted the α-NaFeO 2 structure with almost none of the well-known Li/Ni cation disorder. The analysis of the magnetic properties in the paramagnetic domain agrees with the combination of Ni 2+ (S = 1), Co 3+ (S = 0) and Mn 4+ (S = 3/2) spin-only values. X-ray analysis of the chemically delithiated Li y Ni 0.2 Mn 0.2 Co 0.6 O 2 reveals no structural transition. The process of lithium extraction from and insertion into LiNi 0.2 Mn 0.2 Co 0.6 O 2 was discussed on the basis of ex situ EPR experiments and magnetic susceptibility. Oxidation of Ni 2+ (S = 1) to Ni 3+ (S = 1/2) and to Ni 4+ (S = 0) was observed upon lithium removal.

Electrochemical oxidation of organic carbonate based electrolyte solutions at lithium metal oxide electrodes

Energy Technology Data Exchange (ETDEWEB)

Imhof, R; Novak, P [Paul Scherrer Inst. (PSI), Villigen (Switzerland)

1999-08-01

The oxidative decomposition of carbonate based electrolyte solutions at practical lithium metal oxide composite electrodes was studied by differential electrochemical mass spectrometry. For propylene carbonate (PC), CO{sub 2} evolution was detected at LiNiO{sub 2}, LiCoO{sub 2}, and LiMn{sub 2}O{sub 4} composite electrodes. The starting point of gas evolution was 4.2 V vs. Li/Li{sup +} at LiNiO{sub 2}, whereas at LiCoO{sub 2} and LiMn{sub 2}O{sub 4}, CO{sub 2} evolution was only observed above 4.8 V vs. Li/Li{sup +}. In addition, various other volatile electrolyte decomposition products of PC were detected when using LiCoO{sub 2}, LiMn{sub 2}O4, and carbon black electrodes. In ethylene carbonate / dimethyl carbonate, CO{sub 2} evolution was only detected at LiNiO{sub 2} electrodes, again starting at about 4.2 V vs. Li/Li{sup +}. (author) 3 figs., 2 refs.

Nitrogen-doped carbon decorated Cu2NiSnS4 microflowers as superior anode materials for long-life lithium-ion batteries

Science.gov (United States)

Pan, Pei; Chen, Lihui; Ding, Yu; Du, Jun; Feng, Chuanqi; Fu, Zhengbin; Qin, Caiqin; Wang, Feng

2018-05-01

Nitrogen-doped carbon (NC) decorated Cu2NiSnS4 (CNTS) microflower composites (NC@CNTS) were fabricated through a facile solvothermal and pyrrole polymerization with further annealing treatment. The NC@CNTS composites possessed a three-dimension (3D) microflower-like hierarchical structure. The unique microflower structure of NC@CNTS composites exhibited remarkable electrochemical performance as electrode materials for long life lithium ion batteries. The as-prepared composites had a stable and reversible capacity that reached 943 mA h g-1 after 160 cycles at a current rate of 0.1 A g-1. It showed satisfactory cycle stability and rate capability even at 2 A g-1, and specific capacity stabilized at 288 mA g-1 after 1000 cycles. The present facile and cost-effective strategy can be applied for the synthesis of other transition metal sulfide nanomaterials for energy storage and conversion applications.

Structural and dielectric studies of LiNiPO4 and LiNi0.5Co0.5PO4 cathode materials for lithium-ion batteries

Directory of Open Access Journals (Sweden)

K. Vijaya Babu

2016-09-01

Full Text Available Olivine-type LiNiPO4 has been considered as a most competitive positive electrode active material for lithium-ion batteries. In the present paper, the LiNiPO4 and Co-doped LiNi0.5Co0.5PO4 are synthesized by solid-state reaction method under air atmosphere. All the X-ray diffraction peaks of both the compounds are indexed and it is found that the samples are well crystallized in orthorhombic olivine structure belonging to the space group Pnma. The crystallite size is calculated from the Scherrer formula and it is found to be 6.918 and 4.818 nm for pure and doped samples, respectively. The surface morphology and grain sizes of the materials are investigated through scanning electron microscope. Presence of preferred local cation environment is understood from Fourier transform infrared spectroscopy (FTIR studies. The conductivity and dielectric analysis of the samples are carried out at different temperatures and frequencies using the complex impedance spectroscopy technique. The electrical conductivity of LiNi0.5Co0.5PO4 is higher than that of pure LiNiPO4.

Zn substitution NiFe_2O_4 nanoparticles with enhanced conductivity as high-performances electrodes for lithium ion batteries

International Nuclear Information System (INIS)

Mao, Junwei; Hou, Xianhua; Huang, Fengsi; Shen, Kaixiang; Lam, Kwok-ho; Ru, Qiang; Hu, Shejun

2016-01-01

Zn"2"+ ion substituted nickel ferrite nanomaterials with the chemical formula Ni_1_−_xZn_xFe_2O_4 for x = 0, 0.3, 0.5, 0.7 and 1 have been synthesized by a facile green-chemical hydrothermal method as anode materials in lithium ion battery. The morphology and structure of the samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The physical and electrochemical properties were tested by electrochemical system. Furthermore, the energetic and electronic properties of the samples were investigated by density functional calculations. The results suggest that Zn substitution can affect the conduction performance of the zinc - nickel ferrite. Meanwhile, electrochemical results show that an enhancement in the capacity with increasing Zn concentration is observed especially for x = 0.3 which exhibit high discharge capacity of 1416 mAh g"−"1at the end of 100th cycle. Moreover, the theoretical research method with high yield synthesis strategy described in the present work holds promise for the general fabrication of other metallic elements substitution in complex transition metal oxides for high power LIBs. - Highlights: • Ni_1_−_xZn_xFe_2O_4 anodes have been synthesized by hydrothermal method. • First principles calculation was used to investigate the conduction performance. • Electrochemical performance was enhanced with Zn substitution.

Raman spectroscopy and dielectric Studies of multiple phase transitions in ZnO:Ni

Science.gov (United States)

Yadav, Harish Kumar; Sreenivas, K.; Gupta, Vinay; Scott, J. F.; Katiyar, R. S.

2008-03-01

We present Raman and dielectric data on Ni-doped ZnO (Zn1-xNixO) ceramics as a function of Ni concentration (x =0.03, 0.06, and 0.10) and temperature. A mode (around 130cm-1) is identified as TA(M) [J. M. Calleja and M. Cardona, Phys. Rev. B 16, 3753 (1977)] and appears due to an antiferromagnetic phase transition at low temperatures (100K) via the spin-orbit mechanism [P. Moch and C. Dugautier, Phys. Lett. A 43, 169 (1973)]. A strong dielectric anomaly occurs at around 430-460K, depending on Ni concentration, and is due to extrinsic electret effects (Ni ionic conduction) and not to a ferroelectric phase transition.

Morphology-controlled synthesis and electrochemical performance of NiCo{sub 2}O{sub 4} as anode material in lithium-ion battery application

Energy Technology Data Exchange (ETDEWEB)

Xu, Shan; Lu, Lin; Zhang, Qing; Zheng, Hao; Liu, Lian; Yin, Shengyu; Wang, Shiquan, E-mail: wsqhao@126.com; Li, Guohua; Feng, Chuanqi [Hubei University, Hubei Collaborative Innovation Center for Advanced Organic Chemical Materials, Ministry-of-Education Key Laboratory for Synthesis and Applications of Organic Functional Molecules (China)

2015-09-15

Mixed-valence oxide precursors were synthesized by a solvothermal method using NiSO{sub 4}, CoSO{sub 4}, and NH{sub 4}HCO{sub 3} as raw materials. The precursors were heat-treated in a muffle furnace at 500 °C to obtain the products (NiCo{sub 2}O{sub 4}). The samples were characterized by X-ray diffractometer, thermogravimetric, energy-dispersive spectroscopy, scanning electron microscopy, and transmission electron microscopy. The results show that dumbbells, microspheres, and particle-like NiCo{sub 2}O{sub 4} were successfully synthesized by changing the volume of solvent and solvothermal temperature. The NiCo{sub 2}O{sub 4} microspheres (prepared at 180 °C with 30 ml solvent) as anode material for lithium-ion battery, exhibit a reversible discharge capacity of 1160 mAh g{sup −1} and good cycling stability (729 mAh g{sup −1} after 50 cycles) at a constant current of 100 mA g{sup −1} in the voltage range of 0.01–3.0 V due to its high crystallinity and uniform porous morphology. Hence, the synthetic method could be extended to other high-capacity ternary metal oxide materials for lithium-ion battery application.

Ab initio study of adsorption and diffusion of lithium on transition metal dichalcogenide monolayers

OpenAIRE

Sun, Xiaoli; Wang, Zhiguo

2017-01-01

Using first principles calculations, we studied the stability and electronic properties of transition metal dichalcogenide monolayers of the type MX2 (M = Ti, Zr, Hf, V, Nb, Ta, Mo, Cr, W; X= S, Se, Te). The adsorption and diffusion of lithium on the stable MX2 phase was also investigated for potential application as an anode for lithium ion batteries. Some of these compounds were found to be stable in the 2H phase and some are in the 1T or 1T' phase, but only a few of them were stable in bot...

Magnetic properties of fcc Ni-based transition metal alloy

Czech Academy of Sciences Publication Activity Database

Kudrnovský, Josef; Drchal, Václav; Bruno, P.

2008-01-01

Roč. 77, č. 22 (2008), 224422/1-224422/8 ISSN 1098-0121 R&D Projects: GA MŠk OC 150; GA AV ČR IAA100100616; GA ČR GA202/07/0456 Institutional research plan: CEZ:AV0Z10100520 Keywords : Ni-based alloys * magnetic properties * Curie temperatures Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 3.322, year: 2008

Manufacturing of Protected Lithium Electrodes for Advanced Lithium-Air, Lithium-Water & Lithium-Sulfur Batteries

Energy Technology Data Exchange (ETDEWEB)

Visco, Steven J

2015-11-30

The global demand for rechargeable batteries is large and growing rapidly. Assuming the adoption of electric vehicles continues to increase, the need for smaller, lighter, and less expensive batteries will become even more pressing. In this vein, PolyPlus Battery Company has developed ultra-light high performance batteries based on its proprietary protected lithium electrode (PLE) technology. The Company’s Lithium-Air and Lithium-Seawater batteries have already demonstrated world record performance (verified by third party testing), and we are developing advanced lithium-sulfur batteries which have the potential deliver high performance at low cost. In this program PolyPlus Battery Company teamed with Corning Incorporated to transition the PLE technology from bench top fabrication using manual tooling to a pre- commercial semi-automated pilot line. At the inception of this program PolyPlus worked with a Tier 1 battery manufacturing engineering firm to design and build the first-of-its-kind pilot line for PLE production. The pilot line was shipped and installed in Berkeley, California several months after the start of the program. PolyPlus spent the next two years working with and optimizing the pilot line and now produces all of its PLEs on this line. The optimization process successfully increased the yield, throughput, and quality of PLEs produced on the pilot line. The Corning team focused on fabrication and scale-up of the ceramic membranes that are key to the PLE technology. PolyPlus next demonstrated that it could take Corning membranes through the pilot line process to produce state-of-the-art protected lithium electrodes. In the latter part of the program the Corning team developed alternative membranes targeted for the large rechargeable battery market. PolyPlus is now in discussions with several potential customers for its advanced PLE-enabled batteries, and is building relationships and infrastructure for the transition into manufacturing. It is likely

Phase transition in a rechargeable lithium battery

NARCIS (Netherlands)

Dreyer, W.; Gaberscek, M.; Guhlke, C.; Huth, R.; Jamnik, J.

We discuss the lithium storage process within a single-particle cathode of a lithium-ion battery. The single storage particle consists of a crystal lattice whose interstitial lattice sites may be empty or reversibly filled with lithium atoms. The resulting evolution equations describe diffusion with

Electrochemical Characteristics of Layered Transition Metal Oxide Cathode Materials for Lithium Ion Batteries: Surface, Bulk Behavior, and Thermal Properties.

Science.gov (United States)

Tian, Chixia; Lin, Feng; Doeff, Marca M

2018-01-16

Layered lithium transition metal oxides, in particular, NMCs (LiNi x Co y Mn z O 2 ) represent a family of prominent lithium ion battery cathode materials with the potential to increase energy densities and lifetime, reduce costs, and improve safety for electric vehicles and grid storage. Our work has focused on various strategies to improve performance and to understand the limitations to these strategies, which include altering compositions, utilizing cation substitutions, and charging to higher than usual potentials in cells. Understanding the effects of these strategies on surface and bulk behavior and correlating structure-performance relationships advance our understanding of NMC materials. This also provides information relevant to the efficacy of various approaches toward ensuring reliable operation of these materials in batteries intended for demanding traction and grid storage applications. In this Account, we start by comparing NMCs to the isostructural LiCoO 2 cathode, which is widely used in consumer batteries. Effects of changing the metal content (Ni, Mn, Co) upon structure and performance of NMCs are briefly discussed. Our early work on the effects of partial substitution of Al, Fe, and Ti for Co on the electrochemical and bulk structural properties is then covered. The original aim of this work was to reduce the Co content (and thus the raw materials cost) and to determine the effect of the substitutions on the electrochemical and bulk structural properties. More recently, we have turned to the application of synchrotron and advanced microscopy techniques to understand both bulk and surface characteristics of the NMCs. Via nanoscale-to-macroscale spectroscopy and atomically resolved imaging techniques, we were able to determine that the surfaces of NMC undergo heterogeneous reconstruction from a layered structure to rock salt under a variety of conditions. Interestingly, formation of rock salt also occurs under abuse conditions. The surface

Microwave hydrothermal synthesis of urchin-like NiO nanospheres as electrode materials for lithium-ion batteries and supercapacitors with enhanced electrochemical performances

Energy Technology Data Exchange (ETDEWEB)

Mondal, Anjon Kumar, E-mail: Anjon.K.Mondal@student.uts.edu.au [Centre for Clean Energy Technology, School of Chemistry and Forensic Science, University of Technology Sydney, Broadway, Sydney, NSW 2007 (Australia); Su, Dawei; Wang, Ying; Chen, Shuangqiang [Centre for Clean Energy Technology, School of Chemistry and Forensic Science, University of Technology Sydney, Broadway, Sydney, NSW 2007 (Australia); Liu, Qi [School of Petrochemical Engineering, Changzhou University, Changzhou 213164 (China); Wang, Guoxiu, E-mail: Guoxiu.wang@uts.edu.au [Centre for Clean Energy Technology, School of Chemistry and Forensic Science, University of Technology Sydney, Broadway, Sydney, NSW 2007 (Australia)

2014-01-05

Highlights: • Urchin-like NiO nanospheres were synthesised by a microwave hydrothermal method. • The NiO nanospheres consist of nanocrystals and porous structure. • NiO nanospheres exhibited a high reversible specific capacity of 1027 mA h g{sup −1}. • The NiO nanospheres also delivered a high supercapacitance of 736 F g{sup −1}. -- Abstract: Urchin-like NiO nanospheres were synthesised by a microwave hydrothermal method. The as-synthesised NiO nanospheres were characterised by X-ray diffraction, field emission scanning electron microscopy and transmission electron microscopy. It was found that NiO nanosphere consists of a nanoporous structure and nanosize crystals. When applied as anode materials in lithium-ion batteries, NiO nanospheres exhibited a high reversible specific capacity of 1027 mA h g{sup −1}, an excellent cycling performance and a good high rate capability. NiO nanospheres also showed a high specific capacitance as electrode materials for supercapacitors.

Enthalpies of formation of layered LiNi{sub x}Mn{sub x}Co{sub 1-2x}O{sub 2} (0 ≤ x ≤ 0.5) compounds as lithium ion battery cathode materials

Energy Technology Data Exchange (ETDEWEB)

Masoumi, Maryam; Cupid, Damian M.; Reichmann, Thomas L.; Seifert, Hans J. [Karlsruhe Institute of Technology, Eggenstein-Leopoldshafen (Germany). Inst. for Applied Materials - Applied Materials Physics; Chang, Keke; Music, Denis; Schneider, Jochen M. [RWTH Aachen Univ. (Germany). Materials Chemistry

2017-11-15

Layer-structured mixed transition metal oxides with the formula LiNi{sub x}Mn{sub x}Co{sub 1-2x}O{sub 2} (0 ≤ x ≤ 0.5) are considered as important cathode materials for lithium-ion batteries. In an effort to evaluate the relative thermodynamic stabilities of individual compositions in this series, the enthalpies of formation of selected stoichiometries are determined by high temperature oxide melt drop solution calorimetry and verified by ab-initio calculations. The measured and calculated data are in good agreement with each other, and the results show that LiCoO{sub 2}-LiNi{sub 0.5}Mn{sub 0.5}O{sub 2} solid solution approaches ideal behavior. By increasing x, i.e. by equimolar substitution of Mn{sup 4+} and Ni{sup 2+} for Co{sup 3+}, the enthalpy of formation of LiNi{sub x}Mn{sub x}Co{sub 1-2x}O{sub 2} from the elements becomes more exothermic, implying increased energetic stability. This conclusion is in agreement with the literature results showing improved structural stability and cycling performance of Ni/Mn-rich LiNi{sub x}Mn{sub x}Co{sub 1-2x}O{sub 2} compounds cycled to higher cut-off voltages.

Search for positron localization near transition-metal solutes of negative effective charge in Ni and Cu

International Nuclear Information System (INIS)

Hunter, D.M.; Grynszpan, R.I.; Arrott, A.S.

1993-01-01

Results of an early (1973) angular correlation (ACAR) study of dilute (0.5 at.%) Cu based alloys by a Japanese group were interpreted in terms of an attraction of e + by transition metal solutes of effective negative charge. Doppler Broadening (DB) measurements reveal no such an effect for Cu(Mn) and Cu(Ni) solid solutions as well as for Ni alloys with 3d, 4d and 5d transition metal solutes (0.1 to 1.5 at.%) i.e. no evidence of e + localization near these impurities is seen. Our results strongly suggest that the ACAR results are due to the metallurgical state of the samples. In contrast, significant DB lineshape parameter variations, observed for our Ni(Zr) alloys, are attributed to positron trapping in and near Ni 5 Zr precipitates. Our DB results for a series of Ni(Au) alloys are understood in terms of a combination of the effect of an overall lattice expansion and a positron preference for clusters of Au atoms. The above comparison between DB and ACAR results is supported by our 'spin polarized' DB results for a (001) Ni single crystal which resemble those obtained by other groups using a 'spin polarized' 2D-ACAR technique. (orig.)

Effect of transition metal composition on electrochemical performance of nickel-manganese-based lithium-rich layer-structured cathode materials in lithium-ion batteries

Energy Technology Data Exchange (ETDEWEB)

Konishi, Hiroaki, E-mail: hiroaki.konishi.yj@hitachi.com; Gunji, Akira; Feng, Xiaoliang; Furutsuki, Sho

2017-05-15

To evaluate the effect of transition metal composition on the electrochemical properties of Li-rich layer-structured cathode materials, Li{sub 1.2}Ni{sub x}Mn{sub 0.8−x}O{sub 2} (x=0.2, 0.25, 0.3, and 0.4) were synthesized, and their electrochemical properties were investigated. As nickel content x increased in Li{sub 1.2}Ni{sub x}Mn{sub 0.8−x}O{sub 2} (x=0.2, 0.25, 0.3, and 0.4), charge-discharge capacities at a low C-rate (0.05 C) decreased. The results obtained by dQ/dV curves indicate that, as the nickel content increased, the discharge capacity below 3.6 V greatly decreased, but that above 3.6 V increased. As the C-rate of the discharge process increased, the discharge reaction of Li{sub 1.2}Ni{sub x}Mn{sub 0.8−x}O{sub 2} (x=0.2) below 3.6 V greatly decreased. In contrast, that above 3.6 V slightly decreased. This indicates that the discharge reaction above 3.6 V exhibits higher rate performance than that below 3.6 V. For the high-nickel-content cathodes, the ratio of the discharge capacity above 3.6 V to the total discharge capacity was high. Therefore, they exhibited high rate performance. - Graphical abstract: Figure shows the discharge curves of Li{sub 1.2}Ni{sub x}Mn{sub 0.8−x}O{sub 2} (x=0.2 and 0.3) within potential range of 2.5−4.6 V (vs. Li/Li{sup +}) at 0.05 and 3 C. At low C-rate (0.05 C), the discharge capacity of high-nickel-content cathode (Li{sub 1.2}Ni{sub 0.3}Mn{sub 0.5}O{sub 2}) was less than that of low-nickel-content cathode (Li{sub 1.2}Ni{sub 0.2}Mn{sub 0.6}O{sub 2}); however, the discharge potential and capacity of Li{sub 1.2}Ni{sub 0.3}Mn{sub 0.5}O{sub 2} was higher than those of Li{sub 1.2}Ni{sub 0.2}Mn{sub 0.6}O{sub 2} at high C-rate (3 C). This means that the increase in Ni/Mn ratio was effective in improving rate-performance.

Microstructure of the Transitional Area of the Connection of a High-temperature Ni-based Brazing Alloy and Stainless Steel AISI 321 (X6CrNiTi 18–10

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R. Augustin

2010-01-01

Full Text Available This paper presents a detailed examination of the structure of the transitional area between a brazing alloy and the parent material, the dimensions of the diffusion zones that are created, and the influence on them of a change in the brazing parameters. Connections between Ni-based brazing alloys (NI 102 with a small content of B and AISI 321 stainless steel (X6CrNiTi 18–10 were created in a vacuum (10−2 Pa at various brazing temperatures and for various holding times at the brazing temperature. Various specimens were tested. First, the brazing alloys were wetted and the dependence of the wetting on the brazing parameters was assessed. Then a chemical microanalysis was made of the interface between the brazing alloy and the parent material. The individual diffusion zones were identified on pictures from a light microscope and REM, and their dimensions, together with their dependence on the brazing parameters, were determined.

Chemical, structural, and electrochemical characterization of 5 V spinel and complex layered oxide cathodes of lithium ion batteries

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Tiruvannamalai Annamalai, Arun Kumar

2007-12-01

proton insertion and oxygen loss at deep lithium extraction due to the chemical instability arising from a overlap of the Co3+/4+:3d band on the top of the O2-:2p band. The irreversible oxygen loss during the first charge and the consequent reversible capacities of the solid solutions between Li[Li1/3Mn 2/3]O2 and Li[Co1-yNiy]O2 has been found to be determined by the amount of lithium in the transition metal layer of the O3 type layered structure. The lithium content in the transition metal layer is, however, sensitively influenced by the tendency of Ni 3+ to get reduced to Ni2+ and the consequent volatilization of lithium during synthesis. Moreover, high Mn4+ content causes a decrease in oxygen mobility and loss. In addition, the chemically delithiated samples were found to adopt either the parent O3 type structure or the new P3 or O1 type structures depending upon the composition and synthesis temperature of the parent samples and the proton content inserted into the delithiated sample. In essence, the chemical and structural stabilities and the electrochemical performance factors of the layered (1-z) Li[Li1/3 Mn2/3]O2 · (z) Li[Co1-yNi y]O2 solid solution cathodes are found to be maximized by optimizing the contents of the various ions.

Ab initio study of adsorption and diffusion of lithium on transition metal dichalcogenide monolayers

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Xiaoli Sun

2017-12-01

Full Text Available Using first principles calculations, we studied the stability and electronic properties of transition metal dichalcogenide monolayers of the type MX2 (M = Ti, Zr, Hf, V, Nb, Ta, Mo, Cr, W; X= S, Se, Te. The adsorption and diffusion of lithium on the stable MX2 phase was also investigated for potential application as an anode for lithium ion batteries. Some of these compounds were found to be stable in the 2H phase and some are in the 1T or 1T' phase, but only a few of them were stable in both 2H/1T or 2H/1T' phases. The results show that lithium is energetically favourable for adsorption on MX2 monolayers, which can be semiconductors with a narrow bandgap and metallic materials. Lithium cannot be adsorbed onto 2H-WS2 and 2H-WSe2, which have large bandgaps of 1.66 and 1.96 eV, respectively. The diffusion energy barrier is in the range between 0.17 and 0.64 eV for lithium on MX2 monolayers, while for most of the materials it was found to be around 0.25 eV. Therefore, this work illustrated that most of the MX2 monolayers explored in this work can be used as promising anode materials for lithium ion batteries.

Ab initio study of adsorption and diffusion of lithium on transition metal dichalcogenide monolayers.

Science.gov (United States)

Sun, Xiaoli; Wang, Zhiguo

2017-01-01

Using first principles calculations, we studied the stability and electronic properties of transition metal dichalcogenide monolayers of the type MX 2 (M = Ti, Zr, Hf, V, Nb, Ta, Mo, Cr, W; X= S, Se, Te). The adsorption and diffusion of lithium on the stable MX 2 phase was also investigated for potential application as an anode for lithium ion batteries. Some of these compounds were found to be stable in the 2H phase and some are in the 1T or 1T' phase, but only a few of them were stable in both 2H/1T or 2H/1T' phases. The results show that lithium is energetically favourable for adsorption on MX 2 monolayers, which can be semiconductors with a narrow bandgap and metallic materials. Lithium cannot be adsorbed onto 2H-WS 2 and 2H-WSe 2 , which have large bandgaps of 1.66 and 1.96 eV, respectively. The diffusion energy barrier is in the range between 0.17 and 0.64 eV for lithium on MX 2 monolayers, while for most of the materials it was found to be around 0.25 eV. Therefore, this work illustrated that most of the MX 2 monolayers explored in this work can be used as promising anode materials for lithium ion batteries.

Hydrogen determination in chemically delithiated lithium ion battery cathodes by prompt gamma activation analysis

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Alvarez, Emilio, II

2007-12-01

Lithium ion batteries, due to their relatively high energy density, are now widely used as the power source for portable electronics. Commercial lithium ion cells currently employ layered LiCoO2 as a cathode but only 50% of its theoretical capacity can be utilized. The factors that cause the limitation are not fully established in the literature. With this perspective, prompt gamma-ray activation analysis (PGAA) has been employed to determine the hydrogen content in various oxide cathodes that have undergone chemical extraction of lithium (delithiation). The PGAA data is complemented by data obtained from atomic absorption spectroscopy (AAS), redox titration, thermogravimetric analysis (TGA), and mass spectroscopy to better understand the capacity limitations and failure mechanisms of lithium ion battery cathodes. As part of this work, the PGAA facility has been redesigned and reconstructed. The neutron and gamma-ray backgrounds have been reduced by more than an order of magnitude. Detection limits for elements have also been improved. Special attention was given to the experimental setup including potential sources of error and system calibration for the detection of hydrogen. Spectral interference with hydrogen arising from cobalt was identified and corrected for. Limits of detection as a function of cobalt mass present in a given sample are also discussed. The data indicates that while delithiated layered Li1- xCoO2, Li1-xNi 1/3Mn1/3Co1/3O2, and Li1- xNi0.5Mn0.5O2 take significant amounts of hydrogen into the lattice during deep extraction, orthorhombic Li 1-xMnO2, spinel Li1- xMn2O4, and olivine Li1- xFePO4 do not. Layered LiCoO2, LiNi 0.5Mn0.5O2, and LiNi1/3Mn1/3Co 1/3O2 have been further analyzed to assess their relative chemical instabilities while undergoing stepped chemical delithiation. Each system takes increasing amounts of protons at lower lithium contents. The differences are attributed to the relative chemical instabilities of the various cathodes

Phase-pure β-NiMoO4 yolk-shell spheres for high-performance anode materials in lithium-ion batteries

International Nuclear Information System (INIS)

Ahn, Jee Hyun; Park, Gi Dae; Kang, Yun Chan; Lee, Jong-Heun

2015-01-01

Phase-pure β-NiMoO 4 yolk-shell spheres for lithium-ion battery anodes were prepared for the first time by one-pot spray pyrolysis, and their electrochemical properties were investigated. The yolk-shell-structured β-NiMoO 4 powders exhibited high initial discharge/charge capacities (1634/1253 mA h g −1 ) at a current density of 1000 mA g −1 . After 200 cycles, these powders exhibited a high discharge capacity of 1292 mA h g −1 , whereas the initial discharge capacity (1341 mA h g −1 ) of the filled structured NiMoO 4 powders was dramatically decreased to 479 mA h g −1 . The significant enhancement of the cycling performance of the β-NiMoO 4 powders with ultrafine crystallite size was attributed to the structural stability of the yolk-shell structure

Local structural distortion and electronic modifications in PrNiO3 across the metal-insulator transition

International Nuclear Information System (INIS)

Piamonteze, C.; Tolentino, H.C.N.; Ramos, A.Y.; Massa, N. E.; Alonso, J.A.; Martinez-Lope, M.J.; Casais, M.T.

2003-01-01

Local electronic and structural properties of PrNiO3 perovskite were studied by means of X-ray Absorption Spectroscopy at Ni K and L edges. The EXAFS results at Ni K edge show a structural transition from three different Ni-O bond-lengths at the insulating phase to two Ni-O bond-lengths above TMI. These results were interpreted as being due to a transition from a structure with two different Ni sites at the insulating phase to one distorted Ni site at the metallic phase. The Ni L edge spectra show a remarkable difference between the spectra measured at the insulating and metallic phases that indicates a decreasing degree of hybridization between Ni3d and O2p bands from the metallic to the insulating phase

Electrode nanomaterials for lithium-ion batteries

International Nuclear Information System (INIS)

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

2015-01-01

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

Hydrometallurgical process for the recovery of high value metals from spent lithium nickel cobalt aluminum oxide based lithium-ion batteries

Science.gov (United States)

Joulié, M.; Laucournet, R.; Billy, E.

2014-02-01

A hydrometallurgical process is developed to recover valuable metals of the lithium nickel cobalt aluminum oxide (NCA) cathodes from spent lithium-ion batteries (LIBs). Effect of parameters such as type of acid (H2SO4, HNO3 and HCl), acid concentration (1-4 mol L-1), leaching time (3-18 h) and leaching temperature (25-90 °C) with a solid to liquid ratio fixed at 5% (w/v) are investigated to determine the most efficient conditions of dissolution. The preliminary results indicate that HCl provides higher leaching efficiency. In optimum conditions, a complete dissolution is performed for Li, Ni, Co and Al. In the nickel and cobalt recovery process, at first the Co(II) in the leaching liquor is selectively oxidized in Co(III) with NaClO reagent to recover Co2O3, 3H2O by a selective precipitation at pH = 3. Then, the nickel hydroxide is precipitated by a base addition at pH = 11. The recovery efficiency of cobalt and nickel are respectively 100% and 99.99%.

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

Energy Technology Data Exchange (ETDEWEB)

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

1996-12-31

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

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

Energy Technology Data Exchange (ETDEWEB)

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

1997-12-31

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

Mesoporous Tin-Based Oxide Nanospheres/Reduced Graphene Composites as Advanced Anodes for Lithium-Ion Half/Full Cells and Sodium-Ion Batteries.

Science.gov (United States)

He, Yanyan; Li, Aihua; Dong, Caifu; Li, Chuanchuan; Xu, Liqiang

2017-10-04

The large volume variations of tin-based oxides hinder their extensive application in the field of lithium-ion batteries (LIBs). In this study, structure design, hybrid fabrication, and carbon-coating approaches have been simultaneously adopted to address these shortcomings. To this end, uniform mesoporous NiO/SnO 2 @rGO, Ni-Sn oxide@rGO, and SnO 2 @rGO nanosphere composites have been selectively fabricated. Among them, the obtained NiO/SnO 2 @rGO composite exhibited a high capacity of 800 mAh g -1 at 1000 mA g -1 after 400 cycles. The electrochemical mechanism of NiO/SnO 2 as an anode for LIBs has been preliminarily investigated by ex situ XRD pattern analysis. Furthermore, an NiO/SnO 2 @rGO-LiCoO 2 lithium-ion full cell showed a high capacity of 467.8 mAh g -1 at 500 mA g -1 after 100 cycles. Notably, the NiO/SnO 2 @rGO composite also showed good performance when investigated as an anode for sodium-ion batteries (SIBs). It is believed that the unique mesoporous nanospherical framework, synergistic effects between the various components, and uniform rGO wrapping of NiO/SnO 2 shorten the Li + ion diffusion pathways, maintain sufficient contact between the active material and the electrolyte, mitigate volume changes, and finally improve the electrical conductivity of the electrode. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Phase transitions in alloys of the Ni-Mo system

International Nuclear Information System (INIS)

Ustinovshikov, Y.; Shabanova, I.

2011-01-01

Graphical abstract: The structure of Ni-20 at.% Mo and Ni-25 at.% Mo alloys was studied by methods of TEM and XPS. It is shown that at high temperatures the tendency toward phase separation takes place in the alloys and crystalline bcc Mo particles precipitate in the liquid solution. At 900 deg. C and below, the tendency toward ordering leads to the dissolution of Mo particles and precipitation of the particles of Ni 3 Mo, Ni 2 Mo or Ni 4 Mo chemical compounds. Highlights: → 'Chemical' phase transition 'ordering-phase separation' is first discovered in alloys of the Ni-Mo system. → It is first shown that the phase separation in the alloys studied begins at temperatures above the liquidus one. → The formation of Ni 3 Mo from A1 has gone through the intervening stage of the Ni 4 Mo and Ni 2 Mo coexistence. - Abstract: The structure of Ni-20 at.% Mo and Ni-25 at.% Mo alloys heat treated at different temperatures was studied by the method of transmission electron microscopy. X-ray photoelectron spectroscopy was used to detect the sign of the chemical interaction between Ni and Mo atoms at different temperatures. It is shown that at high temperatures the tendency toward phase separation takes place. The system of additional reflections at positions {1 1/2 0} on the electron diffraction patterns testifies that the precipitation of crystalline bcc Mo particles begins in the liquid solution. At 900 deg. C and below, the tendency toward ordering leads to the precipitation of the particles of the chemical compounds. A body-centered tetragonal phase Ni 4 Mo (D1 a ) is formed in the Ni-20 at.% Mo alloy. In the Ni-25 at.% Mo alloy, the formation of the Ni 3 Mo (D0 22 ) chemical compound from the A1 solid solution has gone through the intervening stage of the Ni 4 Mo (D1 a ) and Ni 2 Mo (Pt 2 Mo) formation.

A state-space-based prognostics model for lithium-ion battery degradation

International Nuclear Information System (INIS)

Xu, Xin; Chen, Nan

2017-01-01

This paper proposes to analyze the degradation of lithium-ion batteries with the sequentially observed discharging profiles. A general state-space model is developed in which the observation model is used to approximate the discharging profile of each cycle, the corresponding parameter vector is treated as the hidden state, and the state-transition model is used to track the evolution of the parameter vector as the battery ages. The EM and EKF algorithms are adopted to estimate and update the model parameters and states jointly. Based on this model, we construct prediction on the end of discharge times for unobserved cycles and the remaining useful cycles before the battery failure. The effectiveness of the proposed model is demonstrated using a real lithium-ion battery degradation data set. - Highlights: • Unifying model for Li-Ion battery SOC and SOH estimation. • Extended Kalman filter based efficient inference algorithm. • Using voltage curves in discharging to have wide validity.

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

International Nuclear Information System (INIS)

Zhu, Youqi; Cao, Chuanbao

2015-01-01

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

First-principles assessment of potential ultrafast laser-induced structural transition in Ni

Energy Technology Data Exchange (ETDEWEB)

Bévillon, E.; Colombier, J.P., E-mail: jean.philippe.colombier@univ-st-etienne.fr; Stoian, R.

2016-06-30

Highlights: • First-principles theory calculations in nonequilibrium conditions. • Electronic temperatures fully and consistently taken into account. • Evaluation of an ultrafast laser-induced solid-to-solid transition in Ni. • Relative energies, phonon spectra and energy path are evaluated. • Discussion on the generation of non-thermal forces in metals. - Abstract: The possibility to trigger ultrafast solid-to-solid transitions in transition metals under femtosecond laser irradiation is investigated by means of first-principles calculations. Electronic heating can drastically modify screening, charge distribution and atomic binding features, potentially determining new structural relaxation paths in the solid phase, before thermodynamic solid-to-liquid transformations set in. Consequently, we evaluate here the effect of electronic excitation on structural stability and conditions for structural transitions. Ni is chosen as a case study for the probability of a solid transition, and the stability of its FCC phase is compared to the non-standard HCP structure while accounting for the heating of the electronic subsystem. From a phonon spectra analysis, we show that the thermodynamic stability order reverses at an electronic temperature of around 10{sup 4} K. Both structures exhibit a dynamic stability, indicating they present a metastability depending on the heating. However, the general hardening of phonon modes with the increase of the electronic temperature points out that no transformation will occur, as confirmed by the study of a typical FCC to HCP diffusionless transformation path, showing an increasing energy barrier. Finally, based on electronic density of states interpretation, the tendency of different metal categories to undergo or not an ultrafast laser-induced structural transition is discussed.

Origin of the strain glass transition in Ti_5_0(Ni_5_0_−_x D_x) alloys

International Nuclear Information System (INIS)

Wang, Xu; Shang, Jia-Xiang; Wang, Fu-He; Chen, Yue

2016-01-01

Direct evidence was recently discovered for the unique strain glass (STG) transition, which breaks the local symmetries (PRL 112, 025701 (2014)). To understand the origin of the STG transition, the effects of doping point defects on Ti_5_0(Ni_5_0_−_x D_x) are investigated using first-principle calculations. The experimental observation that STG only exists in a limited range of chemical composition x is successfully rationalized. The mechanisms that correspond to the division of a system into domains with distinctly different compositions are found to be directly related to a dip in the defect formation energy. - Highlights: • The strain glass transition phenomenon in Ti−Ni-based alloys is rationalized. • The electronic-structure origins of the strain glass transition are uncovered. • The separation of domains with different compositions is explained.

Recent Developments in Synthesis of xLi2MnO3 · (1 − x)LiMO2 (M = Ni, Co, Mn) Cathode Powders for High-Energy Lithium Rechargeable Batteries

International Nuclear Information System (INIS)

Doan, The Nam Long; Yoo, Kimoon; Hoang, Tuan K. A.; Chen, P.

2014-01-01

Lithium-rich layered powders, Li 2 MnO 3 -stabilized LiMO 2 (M = Ni, Co, Mn), are attractive cathode candidates for the next generations of high-energy lithium-ion batteries. However, most of the state-of-the-art preparation procedures are complicated and require multiple energy-intensive reaction steps. Thus, elucidating a low-cost synthetic protocol is important for the application of these materials in future lithium-ion batteries. Recent developments in the synthesis procedures of lithium-rich layered powders are discussed and future directions are pointed out in this review.

Phase transformations in the reaction cell of TiNi-based sintered systems

Science.gov (United States)

Artyukhova, Nadezhda; Anikeev, Sergey; Yasenchuk, Yuriy; Chekalkin, Timofey; Gunther, Victor; Kaftaranova, Maria; Kang, Ji-Hoon; Kim, Ji-Soon

2018-05-01

The present work addresses the structural-phase state changes of porous TiNi-based compounds fabricated by reaction sintering (RS) of Ti and Ni powders with Co, Mo, and no additives introduced. The study also emphasizes the features of a reaction cell (RC) during the transition from the solid- to liquid-phase sintering. Mechanisms of phase transformations occurring in the solid phase, involving the low-melting Ti2Ni phase within the RC, have been highlighted. Also, the intermediate Ti2Ni phase had a crucial role to provide both the required RS behavior and modified phase composition of RS samples, and besides, it is found to be responsible for the near-equiatomic TiNi saturation of the melt. Both cobalt and molybdenum additives are shown to cause additional structuring of the transition zone (TZ) at the Ti2Ni‑TiNi interface and broadening of this zone. The impact of Co and Mo on the Ti2Ni phase is evident through fissuring of this phase layer, which is referred to solidified stresses increased in the layer due to post-alloying defects in the structure.

Three-dimensional TiO2 nanowire@NiMoO4 ultrathin nanosheet core-shell arrays for lithium ion batteries

Science.gov (United States)

Cao, Minglei; Bu, Yi; Lv, Xiaowei; Jiang, Xingxing; Wang, Lichuan; Dai, Sirui; Wang, Mingkui; Shen, Yan

2018-03-01

This study reports a general and rational two-step hydrothermal strategy to fabricate three-dimensional (3D) TiO2 nanowire@NiMoO4 ultrathin nanosheet core-shell arrays (TNAs-NMO) as additives-free anodes for lithium-ion batteries (LIBs). The TNAs-NMO electrode delivers a reversible capacity of up to 446.6 mA h g-1 over 120 cycles at the current density of 0.2 A g-1 and a high rate capacity of 234.2 mA h g-1 at 2.0 A g-1. Impressively, the capacity retention efficiency is 74.7% after 2500 cycles at the high rate of 2.0 A g-1. In addition, the full cell consisting of TNAs-NMO anode and LCO cathode can afford a specific energy of up to 220.3 W h kg-1 (based on the entire mass of both electrodes). The high electrochemical performance of the TNAs-NMO electrode is ascribed to its 3D core-shell nanowire array architecture, in which the TiO2 nanowire arrays (TNAs) and the ultrathin NiMoO4 nanosheets exhibit strong synergistic effects. The TNAs maintain mechanical integrity of the electrode and the ultrathin NiMoO4 nanosheets contribute to high capacity and favorable electronic conductivity.

Investigation of route to martensitic transition in Ni-Mn-In shape memory alloys

Science.gov (United States)

Nevgi, R.; Priolkar, K. R.; Righi, L.

2018-04-01

The temperature dependent x-ray diffraction and magnetization measurements on the off stoichiometric Ni2Mn1+xIn1-x alloys have confirmed the appearance of martensite at critical Mn concentration of x=0.35. The high temperature phase of all the alloys have cubic L21 structure with the lattice constant steadily decreasing with increase in Mn concentration. Martensitic transition begins to appear in Ni2Mn1.35In0.65 at about 197K and the structure seems to adopt two phases including the major cubic along with the modulated monoclinic phase. This has been explained on the basis of number of Mn-Ni-Mn hybridized pairs that are responsible for inducing martensitic transition.

Maximum Recommended Dosage of Lithium for Pregnant Women Based on a PBPK Model for Lithium Absorption

Directory of Open Access Journals (Sweden)

Scott Horton

2012-01-01

Full Text Available Treatment of bipolar disorder with lithium therapy during pregnancy is a medical challenge. Bipolar disorder is more prevalent in women and its onset is often concurrent with peak reproductive age. Treatment typically involves administration of the element lithium, which has been classified as a class D drug (legal to use during pregnancy, but may cause birth defects and is one of only thirty known teratogenic drugs. There is no clear recommendation in the literature on the maximum acceptable dosage regimen for pregnant, bipolar women. We recommend a maximum dosage regimen based on a physiologically based pharmacokinetic (PBPK model. The model simulates the concentration of lithium in the organs and tissues of a pregnant woman and her fetus. First, we modeled time-dependent lithium concentration profiles resulting from lithium therapy known to have caused birth defects. Next, we identified maximum and average fetal lithium concentrations during treatment. Then, we developed a lithium therapy regimen to maximize the concentration of lithium in the mother’s brain, while maintaining the fetal concentration low enough to reduce the risk of birth defects. This maximum dosage regimen suggested by the model was 400 mg lithium three times per day.

Study of the phase transition in lithium potassium rubidium sulfate system

Science.gov (United States)

Hamed, A. E.; Abd. El-Aziz, Y. M.; Madi, N. K.; Kassem, M. E.

1998-10-01

Specific heat, Cp, measurements have been performed in lithium potassium rubidium sulfate, (Li 0.5- x/2 K 0.5- x/2 Rb x) 2SO 4, system in a wide range of Rb 2SO 4 content ( x) ( x=0 up to x=10%). Measurements were made between 300 and 800 K with special attention paid to the phase transition at 708 K. It is shown that for small contents, ( x), ( x=0.2 up to x=2%) quantitative changes in the temperature dependence of specific heat Cp( T) around the transition point, T1, are observed. A larger content, x, results in essential changes in the critical behavior of Cp( T) and a considerable change in the phase transition accompanied by a progressive decrease in the thermodynamic parameters. The ratios of the Landau expansion coefficients change as the content of Rb 2SO 4 increases.

Measurements of 2s-2p transition energies in helium-like and lithium-like nickel

International Nuclear Information System (INIS)

Zacarias, A.S.; Livingston, A.E.; Lu, Y.N.; Ward, R.F.; Berry, H.G.; Dunford, R.W.

1987-01-01

The wavelength of the fine structure transition 1s2s 3 S 1 - 1s2p 3 P 2 in Ni XXVII has been measured using fast-ion spectroscopy. The transition energy is sensitive to relativistic and Lamb shift corrections in this high-Z two-electron system. Comparison is made with measurements in other high-Z ions and with recent theoretical calculations. A preliminary measurement of the 1s 2 2s 2 S/sub 1/2/ - 1s 2 2p 2 P/sub 1/2/ find structure transition in Ni XXVI is also reported. 18 refs., 1 fig., 2 tabs

Lithium-based neutron detectors

International Nuclear Information System (INIS)

Yursova, L.

1977-01-01

The problems of using scintillation lithium-based detectors (LiJ(Eu) and 6 LiJ(Eu)), as well as lithium glasses for neutron detection are described. As compared with the glasses the LiJ(Eu) monocrystal possesses substantially higher energy resolution, its luminescence yield is considerably higher (in some cases ten fold), its application makes possible gamma radiation discrimination with the energy approximately four times higher and its higher specific mass ensures better efficiency of gamma radiation counting. The only 6 LiJ(Eu) drawback is its high hydroscopicity as well as its possibility to be used only in a limited temperature range (maximum temperature +35 deg C). The lithium glass can be used (with the exception of spectrometric measurements and radiation mixed regions measurement) with more than 1 MeV gamma radiation energy in a wide temperature range, in agressive, corroding and acid media

Improving the Electrochemical Performance of LiNi0.80Co0.15Al0.05O2 in Lithium Ion Batteries by LiAlO2 Surface Modification

OpenAIRE

Chunhua Song; Wenge Wang; Huili Peng; Ying Wang; Chenglong Zhao; Huibin Zhang; Qiwei Tang; Jinzhao Lv; Xianjun Du; Yanmeng Dou

2018-01-01

LiNi0.80Co0.15Al0.05O2 (NCA) as a lithium ion battery cathode material has received attention for its highly specific capacity and excellent low temperature performance. However, the disadvantages of its high surface lithium compound residues and high pH value have influenced its processing performance and limited its application. This paper uses a facile method to modify NCA through LiAlO2 coating. The results showed that when the molar ratio of Al(NO3)3·9H2O and lithium compound residues at...

Hierarchical flower-like carbon nanosheet assembly with embedded hollow NiCo{sub 2}O{sub 4} nanoparticles for high- performance lithium ion batteries

Energy Technology Data Exchange (ETDEWEB)

Fang, Ling; Qiu, Huajun; Luo, Pan; Li, Wenxiang; Zhang, Huijuan; Wang, Yu, E-mail: wangy@cqu.edu.cn

2017-05-01

Highlights: • Flower-like NiCo{sub 2}O{sub 4}@carbon nanosphere is firstly synthesized for Li-ion batteries. • The nanostructure exhibits the unique feature of hollow NiCo{sub 2}O{sub 4} nanoparticles embedded inside and graphitized carbon layers coating outside. • The sample reveals stable structure, large specific surface area and good electrical conductivity. • The composite exhibits superior rate capability, cycling capacity and excellent Coulombic efficiency. - Abstract: The fabrication of closely bounded metal oxides/carbon hybrid nano-structures is significant for its use in energy-related areas especially lithium ion batteries (LIBs). In this research, a flower-like carbon sphere with hollow NiCo{sub 2}O{sub 4} nanoparticles encapsulated inside the carbon thin nanopetal is fabricated by using a mixed basic carbonate nickel and cobalt sphere as the precursor and templates followed by the outer carbon membrane covering and two-step calcination process. When tested as anode material for LIBs, this flower-like carbon-based hybrid sphere demonstrates a significantly enhanced reversible capacity and cycling stability at various current densities.

Influence of martensitic transformation on the magnetic transition in Ni-Mn-Ga

Energy Technology Data Exchange (ETDEWEB)

Kokorin, V.V. [Institute of Magnetism of NASU and MESU, Vernadsky blvd., 03680 Kyiv (Ukraine); Konoplyuk, S.M., E-mail: ksm@imag.kiev.ua [Institute of Magnetism of NASU and MESU, Vernadsky blvd., 03680 Kyiv (Ukraine); Dalinger, A.; Maier, H.J. [Institut für Werkstoffkunde (Materials Science), Leibnitz Universität Hannover, An der Universität 2, D-30823 Garbsen (Germany)

2017-06-15

Highlights: • The magnetic transition with temperature hysteresis occurs in Ni{sub 51.9}Mn{sub 27}Ga{sub 211}. • Its second-order character is confirmed by magnetic measurements. • The reason for this phenomenon lies in temperature dependence of lattice constant. - Abstract: The magnetic transition with a temperature hysteresis of about 7 K was observed in the martensitic phase of Ni{sub 51.9}Mn{sub 27}Ga{sub 211}. The measurements of AC magnetic susceptibility in constant magnetic fields up to 570 kA/m have proved its magnetic origin. The transport and caloric measurements were used to gain better understanding of the nature of this phenomenon. The variation of the martensite lattice parameters with temperature is suggested to account for the hysteresis of the magnetic transition.

Nickel Hexacyanoferrate Nanoparticles as a Low Cost Cathode Material for Lithium-Ion Batteries

International Nuclear Information System (INIS)

Omarova, Marzhana; Koishybay, Aibolat; Yesibolati, Nulati; Mentbayeva, Almagul; Umirov, Nurzhan; Ismailov, Kairat; Adair, Desmond; Babaa, Moulay-Rachid; Kurmanbayeva, Indira; Bakenov, Zhumabay

2015-01-01

Potassium nickel hexacyanoferrate KNi[Fe(CN) 6 ] (NiHCF) was synthesized by a simple co-precipitation method and investigated as a cathode material for lithium-ion batteries. The X-ray diffraction and transmission electron microscopy studies revealed the formation of pure phase of agglomerated NiHCF nanoparticles of about 20–50 nm in size. The material exhibited stable cycling performance as a cathode in a lithium half-cell within a wide range of current densities, and a working potential around 3.3 V vs. Li + /Li. The lithium ion diffusion coefficient in this system was determined to be in a range of 10 −9 to 10 −8 cm 2 s −1 , which is within the values for the cathode materials for lithium-ion batteries with high rate capability. Considering promising electrochemical performance and attractive lithium-ion diffusion properties of this material along with its economical benefits and simplified preparation, NiHCF could be considered as a very promising cathode for large scale lithium-ion batteries.

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

International Nuclear Information System (INIS)

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

2006-01-01

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

Phase transition of Ni-Mn-Ga alloy powders prepared by vibration ball milling

International Nuclear Information System (INIS)

Tian, B.; Chen, F.; Tong, Y.X.; Li, L.; Zheng, Y.F.; Liu, Y.; Li, Q.Z.

2011-01-01

Research highlights: → The vibration ball milling with a high milling energy introduces the atomic disorder and large lattice distortion in the alloy during milling and makes the formation of disordered fcc structure phase in the alloy. → The transition temperature and activation energy for disordered fcc → disordered bcc are ∼320 o C and 209 ± 8 kJ/mol, respectively. → The alloy powders annealed at 800 o C for 1 h show a one-stage martensitic transformation with quite lower latent heat compared to the bulk alloy. - Abstract: This study investigated the phase transformation of the flaky shaped Ni-Mn-Ga powder particles with thickness around 1 μm prepared by vibration ball milling and post-annealing. The SEM, XRD, DSC and ac magnetic susceptibility measurement techniques were used to characterize the Ni-Mn-Ga powders. The structural transition of Heusler → disordered fcc occurred in the powders prepared by vibration ball milling (high milling energy) for 4 h, which was different from the structural transition of Heusler → disordered fct of the powders fabricated by planetary ball milling (low milling energy) for 4 h. The two different structures after ball milling should be due to the larger lattice distortion occurred in the vibration ball milling process than in the planetary ball milling process. The structural transition of disordered fcc → disordered bcc took place at ∼320 o C during heating the as-milled Ni-Mn-Ga powders, which was attributed to the elimination of lattice distortion caused by ball milling. The activation energy for this transition was 209 ± 8 kJ/mol. The Ni-Mn-Ga powder annealed at 800 o C mainly contained Heusler austenite phase at room temperature and showed a low volume of martensitic transformation upon cooling. The inhibition of martensitic transformation might be attributed to the reduction of grain size in the annealed Ni-Mn-Ga particles.

Effects of Ni vacancy, Ni antisite, Cr and Pt on the third-order elastic constants and mechanical properties of NiAl

KAUST Repository

Wu, Shaohua; Wu, Xiaozhi; Wang, Rui; Liu, Qing; Gan, Liyong

2014-01-01

Effects of Ni vacancy, Ni antisite in Al sublattice, Cr in Al sublattice, Pt in Ni sublattice on the second-order elastic constants (SOECs) and third-order elastic constants (TOECs) of the B2 NiAl have been investigated using the first-principles methods. Lattice constant and the SOECs of NiAl are in good agreement with the previous results. The brittle/ductile transition map based on Pugh ratio G/B and Cauchy pressure Pc shows that Ni antisite, Cr, Pt and pressure can improve the ductility of NiAl, respectively. Ni vacancy and lower pressure can enhance the Vickers hardness Hv of NiAl. The density of states (DOS) and the charge density difference are also used to analysis the effects of vacancy, Ni antisite, Cr and Pt on the mechanical properties of NiAl, and the results are in consistent with the transition map. © 2014 Elsevier Ltd. All rights reserved.

Effects of Ni vacancy, Ni antisite, Cr and Pt on the third-order elastic constants and mechanical properties of NiAl

KAUST Repository

Wu, Shaohua

2014-12-01

Effects of Ni vacancy, Ni antisite in Al sublattice, Cr in Al sublattice, Pt in Ni sublattice on the second-order elastic constants (SOECs) and third-order elastic constants (TOECs) of the B2 NiAl have been investigated using the first-principles methods. Lattice constant and the SOECs of NiAl are in good agreement with the previous results. The brittle/ductile transition map based on Pugh ratio G/B and Cauchy pressure Pc shows that Ni antisite, Cr, Pt and pressure can improve the ductility of NiAl, respectively. Ni vacancy and lower pressure can enhance the Vickers hardness Hv of NiAl. The density of states (DOS) and the charge density difference are also used to analysis the effects of vacancy, Ni antisite, Cr and Pt on the mechanical properties of NiAl, and the results are in consistent with the transition map. © 2014 Elsevier Ltd. All rights reserved.

Preparation and application of PVDF-HFP composite polymer electrolytes in LiNi0.5Co0.2Mn0.3O2 lithium-polymer batteries

International Nuclear Information System (INIS)

Yang, Chun-Chen; Lian, Zuo-Yu; Lin, S.J.; Shih, Jeng-Ywan; Chen, Wei-Houng

2014-01-01

Graphical abstract: - Highlights: • PVDF-HFP/SBA15 membrane and NCM cathode material were prepared for Li ion battery. • SBA15 fillers can trap more liquid electrolytes to enhance the ionic conductivity. • Modified fillers with functional groups play a key role in reducing impedance. • LiNi 0.5 Co 0.2 Mn 0.3 O 2 polymer battery showed excellent electrochemical performance. - Abstract: This study reports the preparation of a composite polymer electrolyte for application in LiNi 0.5 Co 0.2 Mn 0.3 O 2 lithium-polymer batteries. Poly(vinylidiene fluoride-hexafluoropropylene) (denoted as PVDF-HFP) was used as the polymer host and mesoporous modified-silica fillers (denoted as m-SBA15) used as the solid plasticizer were added into the polymer matrix. The characteristic properties of the composite polymer membranes were examined using Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM), X-ray diffraction (XRD), and an AC impedance method. The discharge capacities of LiNi 0.5 Co 0.2 Mn 0.3 O 2 polymer batteries with a PE separator, pure PVDF-HFP polymer membrane, or a PVDF-HFP/10 wt.%m-SBA15 composite at 0.1 C were determined to be 155.5, 159.5, and 198.6 mAh g −1 , respectively. The LiNi 0.5 Co 0.2 Mn 0.3 O 2 polymer battery containing the PVDF-HFP/10 wt.%m-SBA15 composite achieved discharge capacities of 194, 170, 161, 150, 129, 115, and 87 mAh g −1 at 0.1, 0.2, 0.5, 1, 3, 5, and 10 C, respectively. The lithium-polymer battery demonstrated a high coulomb efficiency of ca. 99%. The PVDF-HFP/m-SBA15 composite membrane is a strong candidate for application in LiNi 0.5 Co 0.2 Mn 0.3 O 2 lithium-polymer batteries

Lithium Diffusion and Magnetism in Battery Cathode Material LixNi1/3Co1/3Mn1/3O2

International Nuclear Information System (INIS)

Månsson, M; Prša, K; Nozaki, H; Sugiyama, J; Wikberg, J M; Sassa, Y; Dahbi, M; Kamazawa, K; Sedlak, K; Watanabe, I

2014-01-01

We have studied low-temperature magnetic properties as well as high-temperature lithium ion diffusion in the battery cathode materials Li x Ni 1/3 Co 1/3 Mn 1/3 O 2 by the use of muon spin rotation/relaxation. Our data reveal that the samples enter into a 2D spin-glass state below T SG ≈ 12 K. We further show that lithium diffusion channels become active for T ≥ T diff ∼ 125 K where the Li-ion hopping-rate [v(T)] starts to increase exponentially. Further, v(T) is found to fit very well to an Arrhenius type equation and the activation energy for the diffusion process is extracted as E a ≈ 100 meV

Preparation of 3D flower-like NiO hierarchical architectures and their electrochemical properties in lithium-ion batteries

International Nuclear Information System (INIS)

Li, Qing; Chen, Yuejiao; Yang, Ting; Lei, Danni; Zhang, Guanhua; Mei, Lin; Chen, Libao; Li, Qiuhong; Wang, Taihong

2013-01-01

3D flower-like NiO hierarchical architectures have been synthesized by a simple ethanolamine (EA)-mediated self-assembly route and subsequent calcination process. The synthesized β-Ni(OH) 2 precursors annealed at 300, 400 and 500 °C exhibit similar morphology by scanning electron microscopy and different crystallinity, surface area, and pore distribution via X-ray diffraction, Fourier transform infrared spectroscopy and nitrogen adsorption/desorption isotherms. The electrochemical properties indicate that the synthesized NiO hierarchical architectures annealed at 300 °C show the best electrochemical performance, which presents a reversible specific capacity of 713 mAh g −1 at a current density of 100 mA g −1 after 40 cycles. With varying the rate from 100 to 1000 mA g −1 , the capacity still remains 580 mAh g −1 at 500 mA g −1 after 18 cycles and resumes to 470 mAh g −1 at the same rate after 30 cycles. The above results indicate that the 3D flower-like NiO hierarchical architectures are promising anode materials for lithium ion batteries

A novel process for recycling and resynthesizing LiNi1/3Co1/3Mn1/3O2 from the cathode scraps intended for lithium-ion batteries

International Nuclear Information System (INIS)

Zhang, Xihua; Xie, Yongbing; Cao, Hongbin; Nawaz, Faheem; Zhang, Yi

2014-01-01

Highlights: • A simple process to recycle cathode scraps intended for lithium-ion batteries. • Complete separation of the cathode material from the aluminum foil is achieved. • The recovered aluminum foil is highly pure. • LiNi 1/3 Co 1/3 Mn 1/3 O 2 is directly resynthesized from the separated cathode material. - Abstract: To solve the recycling challenge for aqueous binder based lithium-ion batteries (LIBs), a novel process for recycling and resynthesizing LiNi 1/3 Co 1/3 Mn 1/3 O 2 from the cathode scraps generated during manufacturing process is proposed in this study. Trifluoroacetic acid (TFA) is employed to separate the cathode material from the aluminum foil. The effects of TFA concentration, liquid/solid (L/S) ratio, reaction temperature and time on the separation efficiencies of the cathode material and aluminum foil are investigated systematically. The cathode material can be separated completely under the optimal experimental condition of 15 vol.% TFA solution, L/S ratio of 8.0 mL g −1 , reacting at 40 °C for 180 min along with appropriate agitation. LiNi 1/3 Co 1/3 Mn 1/3 O 2 is successfully resynthesized from the separated cathode material by solid state reaction method. Several kinds of characterizations are performed to verify the typical properties of the resynthesized LiNi 1/3 Co 1/3 Mn 1/3 O 2 powder. Electrochemical tests show that the initial charge and discharge capacities of the resynthesized LiNi 1/3 Co 1/3 Mn 1/3 O 2 are 201 mAh g −1 and 155.4 mAh g −1 (2.8–4.5 V, 0.1 C), respectively. The discharge capacity remains at 129 mAh g −1 even after 30 cycles with a capacity retention ratio of 83.01%

Simulations of Lithium-Based Neutron Coincidence Counter for Gd-Loaded Fuel

Energy Technology Data Exchange (ETDEWEB)

Cowles, Christian C. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Kouzes, Richard T. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Siciliano, Edward R. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

2014-10-01

The Department of Energy Office of Nuclear Safeguards and Security (NA-241) is supporting the project Lithium-Based Alternative Neutron Detection Technology Coincidence Counting for Gd-loaded Fuels at Pacific Northwest National Laboratory for the development of a lithium-based neutron coincidence counter for nondestructively assaying Gd loaded nuclear fuel. This report provides results from MCNP simulations of a lithium-based coincidence counter for the possible measurement of Gd-loaded nuclear fuel. A comparison of lithium-based simulations and UNCL-II simulations with and without Gd loaded fuel is provided. A lithium-based model, referred to as PLNS3A-R1, showed strong promise for assaying Gd loaded fuel.

Prospects for designing structural cast eutectic alloys on Al-Ce-Ni system base

International Nuclear Information System (INIS)

Belov, N.A.; Naumova, E.S.

1996-01-01

The phase diagram of Al-Ce-Ni system is built for an aluminium corner at component concentration up to 16 mass %Ce and 8 mass%Ni. A ternary eutectic reaction is established at 12%Ce, 5%Ni and 626 deg C. The ternary eutectic alloy is similar in structure to rapidly cooled Al base alloys with transition metals. The possibility to design new cast alloys based on three-phase (Al)+NiAl 3 +CeAl 4 eutectics is under consideration. Al-Zn-Mg-Cu, Al-Sc and Al-Zr base alloys can be used as (Al) constituent of the eutectics. The new alloys may be considered as heat resistant ones due to the fact that no structural changes are observed in castings on heating up to 350 deg C. 18 refs.; 4 figs.; 2 tabs

A lithium-oxygen battery based on lithium superoxide.

Science.gov (United States)

Lu, Jun; Lee, Yun Jung; Luo, Xiangyi; Lau, Kah Chun; Asadi, Mohammad; Wang, Hsien-Hau; Brombosz, Scott; Wen, Jianguo; Zhai, Dengyun; Chen, Zonghai; Miller, Dean J; Jeong, Yo Sub; Park, Jin-Bum; Fang, Zhigang Zak; Kumar, Bijandra; Salehi-Khojin, Amin; Sun, Yang-Kook; Curtiss, Larry A; Amine, Khalil

2016-01-21

Batteries based on sodium superoxide and on potassium superoxide have recently been reported. However, there have been no reports of a battery based on lithium superoxide (LiO2), despite much research into the lithium-oxygen (Li-O2) battery because of its potential high energy density. Several studies of Li-O2 batteries have found evidence of LiO2 being formed as one component of the discharge product along with lithium peroxide (Li2O2). In addition, theoretical calculations have indicated that some forms of LiO2 may have a long lifetime. These studies also suggest that it might be possible to form LiO2 alone for use in a battery. However, solid LiO2 has been difficult to synthesize in pure form because it is thermodynamically unstable with respect to disproportionation, giving Li2O2 (refs 19, 20). Here we show that crystalline LiO2 can be stabilized in a Li-O2 battery by using a suitable graphene-based cathode. Various characterization techniques reveal no evidence for the presence of Li2O2. A novel templating growth mechanism involving the use of iridium nanoparticles on the cathode surface may be responsible for the growth of crystalline LiO2. Our results demonstrate that the LiO2 formed in the Li-O2 battery is stable enough for the battery to be repeatedly charged and discharged with a very low charge potential (about 3.2 volts). We anticipate that this discovery will lead to methods of synthesizing and stabilizing LiO2, which could open the way to high-energy-density batteries based on LiO2 as well as to other possible uses of this compound, such as oxygen storage.

Synthesis and Characterization of Network Single Ion Conductors(NSIC) Based On Comb-Branched Polyepoxide Ethers and Lithium Bis(allylmalonato)borate

International Nuclear Information System (INIS)

Sun, Xiao-Guang; Kerr, John B.

2004-01-01

Network single ion conductors (NSICs) based on comb-branch polyepoxide ethers and lithium bis(allylmalonato) borate have been synthesized and thoroughly characterized by means of ionic conductivity measurements, electrochemical impedance and by dynamic mechanical analysis (DMA). The materials have been tested as battery electrolytes by cycling in symmetrical Li/Li half cells and in Li/V 6 O 13 full cells in which the NSIC was used as both binder and electrolyte in the cathode electrode and as the electrolyte separator membrane,. The substitution of the trimethylene oxide (TMO) unit into the side chains in place of ethylene oxide (EO) units increased the polymerion mobility (lower glass transition temperature). However, the ionic conductivity was nearly one and half orders of magnitude lower than the corresponding pure EO based single ion conductor at the same salt concentration. This effect may be ascribed to the lower dielectric constant of the TMO side chains that result in a lower concentration of free conducting lithium cations. For a highly cross-linked system (EO/Li=20), only 47 wt% plasticizing solvent (ethylene carbonate (EC)/ethyl methyl carbonate (EMC), 1/1 by wt) could be taken up and the ionic conductivity was only increased by one order of magnitude over the dry polyelectrolyte while for a less densely crosslinked system (EO/Li=80), up to 75 wt% plasticizer could be taken up and the ionic conductivity was increased by nearly two orders of magnitude. A Li/Li symmetric cell that was cycled at 85 C at a current density of 25(micro)Acm -2 showed no concentration polarization or diffusional relaxation, consistent with a lithium ion transference number of one. However, both the bulk and interfacial impedances increased after 20 cycles, apparently due to continued cross-linking reactions within the membrane and on the surface of the lithium electrodes. A Li/V 6 O 13 full cell constructed using a single ion conductor gel (propylene carbonate (PC)/EMC, 1/1 in

Spin-driven pyroelectricity in Ni{sub 3}TeO{sub 6} without ferroelectric signatures of the transition at Neel temperature

Energy Technology Data Exchange (ETDEWEB)

Zhao, L.; Komarek, A.C. [Max-Planck-Institute for Chemical Physics of Solids, Dresden (Germany); Du, C.H. [Department of Physics, Tamkang University, Tamsui, Taiwan (China)

2017-07-15

Here we report on dielectric studies on Ni{sub 3}TeO{sub 6}. We confirm the spin-driven pyroelectric transition at the Neel temperature (T{sub N}) of ∝52.5 K. The measurement of single crystalline and polycrystalline samples excludes a ferroelectric nature of the transition at T{sub N} in this compound. The excellent pyroelectric properties without any intrinsic ferroelectric hysteresis make Ni{sub 3}TeO{sub 6} appropriate for applications in future devices. Pyroelectric measurements on our Ni{sub 3}TeO{sub 6} single crystals. The polarization that appears on cooling through T{sub N} can not be inverted by opposite poling fields (applied when cooling from above T{sub N} to base temperature). (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Synthesis of nickel oxide nanospheres by a facile spray drying method and their application as anode materials for lithium ion batteries

Energy Technology Data Exchange (ETDEWEB)

Xiao, Anguo, E-mail: hixiaoanguo@126.com; Zhou, Shibiao; Zuo, Chenggang; Zhuan, Yongbing; Ding, Xiang

2015-10-15

Graphical abstract: NiO nanospheres prepared by a facile spray drying method show high lithium ion storage performance as anode of lithium ion battery. - Highlights: • NiO nanospheres are prepared by a spray drying method. • NiO nanospheres are composed of interconnected nanoparticles. • NiO nanospheres show good lithium ion storage properties. - Abstract: Fabrication of advanced anode materials is indispensable for construction of high-performance lithium ion batteries. In this work, nickel oxide (NiO) nanospheres are fabricated by a facial one-step spray drying method. The as-prepared NiO nanospheres show diameters ranging from 100 to 600 nm and are composed of nanoparticles of 30–50 nm. As an anode for lithium ion batteries, the electrochemical properties of the NiO nanospheres are investigated by cyclic voltammetry (CV) and galvanostatic charge/discharge tests. The specific reversible capacity of NiO nanospheres is 656 mA h g{sup −1} at 0.1 C, and 476 mA h g{sup −1} at 1 C. The improvement of electrochemical properties is attributed to nanosphere structure with large surface area and short ion/electron transfer path.

Synthesis of nickel oxide nanospheres by a facile spray drying method and their application as anode materials for lithium ion batteries

International Nuclear Information System (INIS)

Xiao, Anguo; Zhou, Shibiao; Zuo, Chenggang; Zhuan, Yongbing; Ding, Xiang

2015-01-01

Graphical abstract: NiO nanospheres prepared by a facile spray drying method show high lithium ion storage performance as anode of lithium ion battery. - Highlights: • NiO nanospheres are prepared by a spray drying method. • NiO nanospheres are composed of interconnected nanoparticles. • NiO nanospheres show good lithium ion storage properties. - Abstract: Fabrication of advanced anode materials is indispensable for construction of high-performance lithium ion batteries. In this work, nickel oxide (NiO) nanospheres are fabricated by a facial one-step spray drying method. The as-prepared NiO nanospheres show diameters ranging from 100 to 600 nm and are composed of nanoparticles of 30–50 nm. As an anode for lithium ion batteries, the electrochemical properties of the NiO nanospheres are investigated by cyclic voltammetry (CV) and galvanostatic charge/discharge tests. The specific reversible capacity of NiO nanospheres is 656 mA h g −1 at 0.1 C, and 476 mA h g −1 at 1 C. The improvement of electrochemical properties is attributed to nanosphere structure with large surface area and short ion/electron transfer path

Zn substitution NiFe{sub 2}O{sub 4} nanoparticles with enhanced conductivity as high-performances electrodes for lithium ion batteries

Energy Technology Data Exchange (ETDEWEB)

Mao, Junwei [Guang dong Engineering Technology Research Center of Efficient Green Energy and Environmental Protection Materials, Guangzhou 510006 (China); Guang dong Provincial Key Laboratory of Quantum Engineering and Quantum Materials, School of Physics and Telecommunication Engineering, South China Normal University, Guangzhou 510006 (China); Hou, Xianhua, E-mail: houxh@scnu.edu.cn [Guang dong Engineering Technology Research Center of Efficient Green Energy and Environmental Protection Materials, Guangzhou 510006 (China); Guang dong Provincial Key Laboratory of Quantum Engineering and Quantum Materials, School of Physics and Telecommunication Engineering, South China Normal University, Guangzhou 510006 (China); Huang, Fengsi; Shen, Kaixiang [Guang dong Engineering Technology Research Center of Efficient Green Energy and Environmental Protection Materials, Guangzhou 510006 (China); Guang dong Provincial Key Laboratory of Quantum Engineering and Quantum Materials, School of Physics and Telecommunication Engineering, South China Normal University, Guangzhou 510006 (China); Lam, Kwok-ho [Department of Electrical Engineering, The Hong Kong Polytechnic University, Hunghom, Kowloon 999077 (Hong Kong); Ru, Qiang [Guang dong Engineering Technology Research Center of Efficient Green Energy and Environmental Protection Materials, Guangzhou 510006 (China); Guang dong Provincial Key Laboratory of Quantum Engineering and Quantum Materials, School of Physics and Telecommunication Engineering, South China Normal University, Guangzhou 510006 (China); Hu, Shejun, E-mail: husj@scnu.edu.cn [Guang dong Engineering Technology Research Center of Efficient Green Energy and Environmental Protection Materials, Guangzhou 510006 (China); Guang dong Provincial Key Laboratory of Quantum Engineering and Quantum Materials, School of Physics and Telecommunication Engineering, South China Normal University, Guangzhou 510006 (China)

2016-08-15

Zn{sup 2+} ion substituted nickel ferrite nanomaterials with the chemical formula Ni{sub 1−x}Zn{sub x}Fe{sub 2}O{sub 4} for x = 0, 0.3, 0.5, 0.7 and 1 have been synthesized by a facile green-chemical hydrothermal method as anode materials in lithium ion battery. The morphology and structure of the samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The physical and electrochemical properties were tested by electrochemical system. Furthermore, the energetic and electronic properties of the samples were investigated by density functional calculations. The results suggest that Zn substitution can affect the conduction performance of the zinc - nickel ferrite. Meanwhile, electrochemical results show that an enhancement in the capacity with increasing Zn concentration is observed especially for x = 0.3 which exhibit high discharge capacity of 1416 mAh g{sup −1}at the end of 100th cycle. Moreover, the theoretical research method with high yield synthesis strategy described in the present work holds promise for the general fabrication of other metallic elements substitution in complex transition metal oxides for high power LIBs. - Highlights: • Ni{sub 1−x}Zn{sub x}Fe{sub 2}O{sub 4} anodes have been synthesized by hydrothermal method. • First principles calculation was used to investigate the conduction performance. • Electrochemical performance was enhanced with Zn substitution.

Comparative Investigation of 0.5Li2MnO3·0.5LiNi0.5Co0.2Mn0.3O2 Cathode Materials Synthesized by Using Different Lithium Sources

Directory of Open Access Journals (Sweden)

Peng-Bo Wang

2018-05-01

Full Text Available Lithium-rich manganese-based cathode materials has been attracted enormous interests as one of the most promising candidates of cathode materials for next-generation lithium ion batteries because of its high theoretic capacity and low cost. In this study, 0.5Li2MnO3·0.5LiNi0.5Co0.2Mn0.3O2 materials are synthesized through a solid-state reaction by using different lithium sources, and the synthesis process and the reaction mechanism are investigated in detail. The morphology, structure, and electrochemical performances of the material synthesized by using LiOH·H2O, Li2CO3, and CH3COOLi·2H2O have been analyzed by using Thermo gravimetric analysis (TGA, X-ray diffraction (XRD, Scanning electron microscope (SEM, Transmission electron microscope (TEM, X-ray photoelectron spectroscopy (XPS, and electrochemical measurements. The 0.5Li2MnO3·0.5LiNi0.5Co0.2Mn0.3O2 material prepared by using LiOH·H2O displays uniform morphology with nano particle and stable layer structure so that it suppresses the first cycle irreversible reaction and structure transfer, and it delivers the best electrochemical performance. The results indicate that LiOH·H2O is the best choice for the synthesis of the 0.5Li2MnO3·0.5LiNi0.5Co0.2Mn0.3O2 material.

A facile synthesis of Li_2Fe_1_/_3Mn_1_/_3Ni_1_/_3SiO_4/C composites as cathode materials for lithium-ion batteries

International Nuclear Information System (INIS)

Yang, Rong; Wang, Liqing; Deng, Kunfa; Lv, Mengni; Xu, Yunhua

2016-01-01

The novel Li_2Fe_1_/_3Mn_1_/_3Ni_1_/_3SiO_4/C has been successfully synthesized by a feasible solution process in ternary system. The spherical carbon-coated composites are obtained using a heat treatment in the presence of sucrose. X-ray diffraction (XRD) diffractogram displays that the Li_2Fe_1_/_3Mn_1_/_3Ni_1_/_3SiO_4/C crystallized in an orthorhombic structure with a space group of Pmn21. The energy-dispersive X-ray spectroscopy mappings indicate that Fe, Mn and Ni elements are distributed homogenously in Li_2Fe_1_/_3Mn_1_/_3Ni_1_/_3SiO_4/C nano-spherical particle with size less than 50 nm. The lithium storage capacity and cycling performance of the Li_2Fe_1_/_3Mn_1_/_3Ni_1_/_3SiO_4/C presents good results when tested as cathode materials in lithium cells at room temperature. It delivers an initial discharge capacity of 181.4 mAh g"−"1 and a discharge capacity of 172.9 mAh g"−"1 after 20 cycles at 0.1C in the voltage range of 1.5–4.6V. Furthermore, it also exhibits an excellent rate capability with a capacity under different current densities of about 144.0 mAh g"−"1 (0.2 C), 117.9 mAh g"−"1 (0.5 C), 106.1 mAh g"−"1 (1 C), respectively and a good capacity cycling maintenance of 153.7 mAh g"−"1 after 60 cycles. Above results indicate that the spherical Li_2Fe_1_/_3Mn_1_/_3Ni_1_/_3SiO_4/C becomes a very promising candidate for cathode material in lithium-ion batteries. - Highlights: • Li_2Fe_1_/_3Mn_1_/_3Ni_1_/_3SiO_4/C was obtained by solution process in a ternary system. • The material was pure phase ternary solid solution with tetrahedral morphology. • The spherical particle size was less than 50 nm with graphitized carbon coating. • The nanocomposite revealed high discharge capacity and excellent rate capability.

Transparent plastic scintillators for neutron detection based on lithium salicylate

International Nuclear Information System (INIS)

Mabe, Andrew N.; Glenn, Andrew M.; Carman, M. Leslie; Zaitseva, Natalia P.; Payne, Stephen A.

2016-01-01

Transparent plastic scintillators with pulse shape discrimination containing "6Li salicylate have been synthesized by bulk polymerization with a maximum "6Li loading of 0.40 wt%. Photoluminescence and scintillation responses to gamma-rays and neutrons are reported herein. Plastics containing "6Li salicylate exhibit higher light yields and permit a higher loading of "6Li as compared to previously reported plastics based on lithium 3-phenylsalicylate. However, pulse shape discrimination performance is reduced in lithium salicylate plastics due to the requirement of adding more nonaromatic monomers to the polymer matrix as compared to those based on lithium 3-phenylsalicylate. Reduction in light yield and pulse shape discrimination performance in lithium-loaded plastics as compared to pulse shape discrimination plastics without lithium is interpreted in terms of energy transfer interference by the aromatic lithium salts. - Highlights: • Plastic scintillator with 0.4% "6Li loading is reported using lithium salicylate. • Influence of lithium salts on the scintillation mechanism is explored. • New lithium-loaded scintillator provides improved light yield and reduced cost.

Wetting - Dewetting Transitions of Au/Ni Bilayer Films

Science.gov (United States)

Cen, Xi

the initial deposition sequence of the as-deposited Au/Ni/SiO2/Si interface structure, the majority of the metal/SiO2 interface is Au/SiO2 after annealing at 675°C for 1 hour. Cross-Sectional TEM revealed that void nucleation is predominantly observed at Au/Ni/SiO 2 triple junctions, rather than grain boundary grooving at free surface of the metal film. The formation of Au/SiO2 interface sections is found to be energetically preferred over Ni/SiO2 due to compressive stress in the as-deposited Ni layer. In-situ cross-sectional TEM heating studies demonstrate that the dewetting transition initiates at 400°C. Au diffuses through Ni grain boundaries towards the underlying Ni layer and forms more energetically favorable Au/SiO2 interface. The adsorption of Au along Ni grain boundaries, NiOx/Ni and SiO2/Ni phase boundaries is observed to lower the interfacial energy. The experimental observations suggest that alloying, unequal self-diffusion coefficient and metal/metal interface strongly affect the bilayer dewetting process.

Electronic Topological Transitions in CuNiMnAl and CuNiMnSn under pressure from first principles study

Science.gov (United States)

Rambabu, P.; Kanchana, V.

2018-06-01

A detailed study on quaternary ordered full Heusler alloys CuNiMnAl and CuNiMnSn at ambient and under different compressions is presented using first principles electronic structure calculations. Both the compounds are found to possess ferromagnetic nature at ambient with magnetic moment of Mn being 3.14 μB and 3.35 μB respectively in CuNiMnAl and CuNiMnSn. The total magnetic moment for both the compounds is found to decrease under compression. Fermi surface (FS) topology change is observed in both compounds under pressure at V/V0 = 0.90, further leading to Electronic Topological Transitions (ETTs) and is evidenced by the anomalies visualized in density of states and elastic constants under compression.

Enhanced Prognostic Model for Lithium Ion Batteries Based on Particle Filter State Transition Model Modification

Directory of Open Access Journals (Sweden)

Buddhi Arachchige

2017-11-01

Full Text Available This paper focuses on predicting the End of Life and End of Discharge of Lithium ion batteries using a battery capacity fade model and a battery discharge model. The proposed framework will be able to estimate the Remaining Useful Life (RUL and the Remaining charge through capacity fade and discharge models. A particle filter is implemented that estimates the battery’s State of Charge (SOC and State of Life (SOL by utilizing the battery’s physical data such as voltage, temperature, and current measurements. The accuracy of the prognostic framework has been improved by enhancing the particle filter state transition model to incorporate different environmental and loading conditions without retuning the model parameters. The effect of capacity fade in the reduction of the EOD (End of Discharge time with cycling has also been included, integrating both EOL (End of Life and EOD prediction models in order to get more accuracy in the estimations.

Ni And Co Segregations On Selective Surface Facets And Rational Design Of Layered Lithium Transition-metal Oxide Cathodes

Energy Technology Data Exchange (ETDEWEB)

Yan, Pengfei; Zheng, Jianming; Zheng, Jiaxin; Wang, Zhiguo; Teng, Gaofeng; Kuppan, Saravanan; Xiao, Jie; Chen, Guoying; Zhang, Jiguang; Wang, Chong M.; Pan, Feng

2016-05-05

The chemical processes occurring on the surface of cathode materials during battery cycling play a crucial role in determining battery’s performance. However, our understanding on such surface chemistry is far from clear due to the complexity of redox chemistry during battery charge/discharge. In this work, through intensive aberration corrected STEM investigation on eight layered oxide cathode materials, we report two important findings on the pristine oxides. First, Ni and Co show strong plane selectivity when building up their respective surface segregation layers (SSL). Specifically, Ni-SSL is exclusively developed on (200)m facet in Li-Mn-rich oxides (monoclinic C2/m symmetry) and (012)h facet in Mn-Ni equally rich oxides (hexagonal R-3m symmetry), while Co-SSL has a strong preference to (20-2)m plane with minimal Co-SSL also developed on some other planes in LMR cathodes. Structurally, Ni-SSLs tend to form spinel-like lattice while Co-SSLs are in a rock-salt-like structure. Secondly, by increasing Ni concentration in these layered oxides, Ni and Co SSLs can be suppressed and even eliminated. Our findings indicate that Ni and Co SSLs are tunable through controlling particle morphology and oxide composition, which opens up a new way for future rational design and synthesis of cathode materials.

Effect of Nb and F Co-doping on Li1.2Mn0.54Ni0.13Co0.13O2 Cathode Material for High-Performance Lithium-Ion Batteries

Directory of Open Access Journals (Sweden)

Lei Ming

2018-04-01

Full Text Available The Li1.2Mn0.54−xNbxCo0.13Ni0.13O2−6xF6x (x = 0, 0.01, 0.03, 0.05 is prepared by traditional solid-phase method, and the Nb and F ions are successfully doped into Mn and O sites of layered materials Li1.2Mn0.54Co0.13Ni0.13O2, respectively. The incorporating Nb ion in Mn site can effectively restrain the migration of transition metal ions during long-term cycling, and keep the stability of the crystal structure. The Li1.2Mn0.54−xNbxCo0.13Ni0.13O2−6xF6x shows suppressed voltage fade and higher capacity retention of 98.1% after 200 cycles at rate of 1 C. The replacement of O2− by the strongly electronegative F− is beneficial for suppressed the structure change of Li2MnO3 from the eliminating of oxygen in initial charge process. Therefore, the initial coulombic efficiency of doped Li1.2Mn0.54−xNbxCo0.13Ni0.13O2−6xF6x gets improved, which is higher than that of pure Li1.2Mn0.54Co0.13Ni0.13O2. In addition, the Nb and F co-doping can effectively enhance the transfer of lithium-ion and electrons, and thus improving rate performance.

Graphene-Based Composites as Cathode Materials for Lithium Ion Batteries

Directory of Open Access Journals (Sweden)

Libao Chen

2013-01-01

Full Text Available Owing to the superior mechanical, thermal, and electrical properties, graphene was a perfect candidate to improve the performance of lithium ion batteries. Herein, we review the recent advances in graphene-based composites and their application as cathode materials for lithium ion batteries. We focus on the synthesis methods of graphene-based composites and the superior electrochemical performance of graphene-based composites as cathode materials for lithium ion batteries.

High-pressure structural and dielectric studies of the phase transitions in lithium thallium tartrate monohydrate

Czech Academy of Sciences Publication Activity Database

Kamba, Stanislav; Kulda, J.; Petříček, Václav; McIntyre, G.; Kiat, J. P.

2002-01-01

Roč. 14, č. 15 (2002), s. 4045-4054 ISSN 0953-8984 R&D Projects: GA ČR GA202/01/0612; GA AV ČR IAA1010213 Institutional research plan: CEZ:AV0Z1010914 Keywords : lithium thalim tartarate monohzdrate * phase transitions * neutrom diffraction Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 1.775, year: 2002

Leaching process for recovering valuable metals from the LiNi1/3Co1/3Mn1/3O2 cathode of lithium-ion batteries.

Science.gov (United States)

He, Li-Po; Sun, Shu-Ying; Song, Xing-Fu; Yu, Jian-Guo

2017-06-01

In view of the importance of environmental protection and resource recovery, recycling of spent lithium-ion batteries (LIBs) and electrode scraps generated during manufacturing processes is quite necessary. An environmentally sound leaching process for the recovery of Li, Ni, Co, and Mn from spent LiNi 1/3 Co 1/3 Mn 1/3 O 2 -based LIBs and cathode scraps was investigated in this study. Eh-pH diagrams were used to determine suitable leaching conditions. Operating variables affecting the leaching efficiencies for Li, Ni, Co, and Mn from LiNi 1/3 Co 1/3 Mn 1/3 O 2 , such as the H 2 SO 4 concentration, temperature, H 2 O 2 concentration, stirring speed, and pulp density, were investigated to determine the most efficient conditions for leaching. The leaching efficiencies for Li, Ni, Co, and Mn reached 99.7% under the optimized conditions of 1M H 2 SO 4 , 1vol% H 2 O 2 , 400rpm stirring speed, 40g/L pulp density, and 60min leaching time at 40°C. The leaching kinetics of LiNi 1/3 Co 1/3 Mn 1/3 O 2 were found to be significantly faster than those of LiCoO 2 . Based on the variation in the weight fraction of the metal in the residue, the "cubic rate law" was revised as follows: θ(1-f) 1/3 =(1-kt/r 0 ρ), which could characterize the leaching kinetics optimally. The activation energies were determined to be 64.98, 65.16, 66.12, and 66.04kJ/mol for Li, Ni, Co, and Mn, respectively, indicating that the leaching process was controlled by the rate of surface chemical reactions. Finally, a simple process was proposed for the recovery of valuable metals from spent LiNi 1/3 Co 1/3 Mn 1/3 O 2 -based LIBs and cathode scraps. Copyright © 2017 Elsevier Ltd. All rights reserved.

Corrosion susceptibility study of candidate pin materials for ALTC (active lithium/thionyl chloride) batteries. [Active lithium/thionyl chloride

Energy Technology Data Exchange (ETDEWEB)

Bovard, F.S.; Cieslak, W.R.

1987-09-01

(ALTC = active lithium/thionyl chloride.) We have investigated the corrosion susceptibilities of eight alternate battery pin materials in 1.5M LiAlCl/sub 4//SOCl/sub 2/ electrolyte using ampule exposure and electrochemical tests. The thermal expansion coefficients of these candidate materials are expected to match Sandia-developed Li-corrosion resistant glasses. The corrosion resistances of the candidate materials, which included three stainless steels (15-5 PH, 17-4 PH, and 446), three Fe-Ni glass sealing alloys (Kovar, Alloy 52, and Niromet 426), a Ni-based alloy (Hastelloy B-2) and a zirconium-based alloy (Zircaloy), were compared to the reference materials Ni and 316L SS. All of the candidate materials showed some evidence of corrosion and, therefore, did not perform as well as the reference materials. The Hastelloy B-2 and Zircaloy are clearly unacceptable materials for this application. Of the remaining alternate materials, the 446 SS and Alloy 52 are the most promising candidates.

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

Science.gov (United States)

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

2017-04-01

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

Advanced and safer lithium-ion battery based on sustainable electrodes

KAUST Repository

Ding, Xiang

2018-02-17

Seeking advanced and safer lithium-ion battery with sustainable characteristic is significant for the development of electronic devices and electric vehicles. Herein, a new porous TiO nanobundles (PTNBs) is synthesized though a scalable and green hydrothermal strategy from the TiO powders without using any high-cost and harmful organic titanium-based compounds. The PTNBs exhibits an extremely high lithium storage capacity of 296 mAh g at 100 mA g, where the capacity can maintain over 146 mAh g even after 500 cycles at 1000 mA g. To pursue more reliable Li-ion batteries, full batteries of PTNBs/LiNiMnO (x = 0, 0.5) using spinel structured cathode are constructed. The batteries have the features of sustainability and deliver high capacities of 112 mAh g and 102 mAh g with stable capacity retentions of 99% and 90% over 140 cycles. Note that the energy densities can achieve as high as 267 and 270 Wh kg (535 and 540 Wh kg ) respectively, which is feasible to satisfy diverse requirements for energy storage products. We believe that the universal synthetic strategy, appealing structure and intriguing properties of PTNBs is applicable for wider applications, while the concept of sustainable strategy seeking reliable and safer Li-ion battery can attract broad interest.

Atomic Resolution Structural and Chemical Imaging Revealing the Sequential Migration of Ni, Co, and Mn upon the Battery Cycling of Layered Cathode

Energy Technology Data Exchange (ETDEWEB)

Yan, Pengfei; Zheng, Jianming; Zhang, Ji-Guang; Wang, Chongmin

2017-05-11

Layered lithium transition metal oxides (LTMO) are promising candidate cathode materials for next generation high energy density lithium ion battery. The challenge for using this category of cathode is the capacity and voltage fading, which is believed to be associated with the layered structure disordering, a process that is initiated from the surface or solid-electrolyte interface and facilitated by transition metal (TM) reduction and oxygen vacancy formation. However, the atomic level dynamic mechanism of such a layered structure disordering is still not fully clear. In this work, utilizing atomic resolution electron energy loss spectroscopy (EELS), we map, for the first time at atomic scale, the spatial evolution of Ni, Co and Mn in a cycled LiNi1/3M1/3Co1/3O2 layered cathode. In combination with atomic level structural imaging, we discovered the direct correlation of TM ions migration behavior with lattice disordering, featuring the residing of TM ions in the tetrahedral site and a sequential migration of Ni, Co, and Mn upon the increased lattice disordering of the layered structure. This work highlights that Ni ions, though acting as the dominant redox species in many LTMO, are labile to migrate to cause lattice disordering upon battery cycling; while the Mn ions are more stable as compared with Ni and Co and can act as pillar to stabilize layered structure. Direct visualization of the behavior of TM ions during the battery cycling provides insight for designing of cathode with structural stability and correspondingly a superior performance.

In Situ X-ray Diffraction Studies of Cathode Materials in Lithium Batteries

International Nuclear Information System (INIS)

Yang, X. Q.; Sun, X.; McBreen, J.; Mukerjee, S.; Gao, Yuan; Yakovleva, M. V.; Xing, X. K.; Daroux, M. L.

1998-01-01

There is an increasing interest in lithiated transition metal oxides because of their use as cathodes in lithium batteries. LiCoO 2 , LiNiO 2 and LiMn 2 O 4 are the three most widely used and studied materials, At present, although it is relative expensive and toxic, LiCoO 2 is the material of choice in commercial lithium ion batteries because of its ease of manufacture, better thermal stability and cycle life. However, the potential use of lithium ion batteries with larger capacity for power tools and electric vehicles in the future will demand new cathode materials with higher energy density, lower cost and better thermal stability. LiNiO 2 is isostructural with LiCoO 2 . It offers lower cost and high energy density than LiCoO 2 . However, it has much poorer thermal stability than LiCoO 2 , in the charged (delithiated) state. Co, Al, and other elements have been used to partially replace Ni in LiNiO 2 system in order to increase the thermal stability. LiMn 2 O 4 has the highest thermal stability and lowest cost and toxicity. However, the low energy density and poor cycle life at elevated temperature are the major obstacles for this material. In order to develop safer, cheaper, and better performance cathode materials, the in-depth understanding of the relationships between the thermal stability and structure, performance and structure are very important. The performance here includes energy density and cycle life of the cathode materials. X-ray diffraction (XRD) is one of the most powerful tools to study these relationships. The pioneer ex situ XRD work on cathode materials for lithium batteries was done by Ohzuku. His XRD studies on LiMn 2 O 4 , LiCoO 2 , LiNiO 2 , LiNi 0.5 Co 0.5 O 2 , and LiAl x Ni 1-x O 2 cathodes at different states of charge have provided important guidelines for the development of these new materials. However, the kinetic nature of the battery system definitely requires an in situ XRD technique to study the detail structural changes of the

Capacity fade of LiNi(1-x-y)CoxAlyO2 cathode for lithium-ion batteries during accelerated calendar and cycle life test. I. Comparison analysis between LiNi(1-x-y)CoxAlyO2 and LiCoO2 cathodes in cylindrical lithium-ion cells during long term storage test

Science.gov (United States)

Watanabe, Shoichiro; Kinoshita, Masahiro; Nakura, Kensuke

2014-02-01

Ni-based LiNi(1-x-y)CoxAlyO2 (NCA) and LiCoO2 (LCO) cathode materials taken out of lithium-ion cells after storage for 2 years at 45 °C were analyzed by various spectroscopic techniques. X-ray photoelectron spectroscopy exhibited that there was no difference between NCA and LCO. On the other hand, scanning transmission electron microscopy-electron energy-loss spectroscopy demonstrated there was a remarkably large difference between the two cathode materials. Ni-L2,3 energy-loss near-edge structure (ELNES) spectra of the NCA showed a peak at about 856.5 eV, which was assigned to trivalent nickel, was maintained even after storage, indicating that the NCA had no significant change in its surface structure during storage. On the other hand, in the Co-L2,3 ELNES spectra of the LCO a peak at about 782.5 eV, which was assigned to trivalent cobalt, significantly shifted to the lower energies after storage. These results suggest that crystal structure change of the active material surface is a predominant reason of deterioration during the storage test.

Metal–insulator transition in Ni-doped Na0.75CoO2: Insights from ...

Indian Academy of Sciences (India)

resistivity on lowering the temperature, with the metal-to-insulator transition temperature. (TMIT) increasing with the Ni ... The Ni-doped sample is seen to change over from a metallic to insulating behaviour at ~175 K. The ..... neutron diffraction to look for structural changes, viz., changes in bond lengths and site occupancies ...

Post mortem analysis of fatigue mechanisms in LiNi0.8Co0.15Al0.05O2 - LiNi0.5Co0.2Mn0.3O2 - LiMn2O4/graphite lithium ion batteries

Science.gov (United States)

Lang, Michael; Darma, Mariyam Susana Dewi; Kleiner, Karin; Riekehr, Lars; Mereacre, Liuda; Ávila Pérez, Marta; Liebau, Verena; Ehrenberg, Helmut

2016-09-01

The fatigue of commercial lithium ion batteries after long-term cycling at two different temperatures and cycling rates is investigated. The cells are opened after cycling and post-mortem analysis are conducted. Two main contributions to the capacity loss of the batteries are revealed. The loss of active lithium leads to a relative shift between anodes and cathodes potentials. A growth of the solid electrolyte interface (SEI) on the anode is determined as well as the formation of lithium fluoride species as an electrolyte decomposition product. Those effects are reinforced by increasing cycling rates from 1C/2C (charge/discharge) to 2C/3C as well as by increasing cycling temperatures from 25 °C to 40 °C. The other contribution to the capacity loss originates from a fatigue of the blended cathodes consisting of LiNi0.5Co0.2Mn0.3O2 (NCM), LiNi0.8Co0.15Al0.05O2 (NCA) and LiMn2O4 (LMO). Phase-specific capacity losses and fatigue mechanisms are identified. The layered oxides tend to form microcracks and reveal changes of the surface structure leading to a worsening of the lithium kinetics. The cathode exhibits a loss of manganese at 40 °C cycling temperature. Cycling at 40 °C instead of 25 °C has the major impact on cathodes capacity loss, while cycling at 2C/3C rates barely influences it.

Wide-Temperature Electrolytes for Lithium-Ion Batteries

Energy Technology Data Exchange (ETDEWEB)

Li, Qiuyan; Jiao, Shuhong; Luo, Langli; Ding, Michael S.; Zheng, Jianming; Cartmell, Samuel S.; Wang, Chong-Min; Xu, Kang; Zhang, Ji-Guang; Xu, Wu

2017-05-26

Formulating electrolytes with solvents of low freezing points and high dielectric constants is a direct approach to extend the service temperature range of lithium (Li)-ion batteries (LIBs), for which propylene carbonate (PC), ethyl methyl carbonate (EMC), diethyl carbonate (DEC), methyl butyrate (MB) are excellent candidates. In this work, we report such low temperature electrolyte formulations by optimizing the content of ethylene carbonate (EC) in the EC-PC-EMC ternary solvent system with LiPF6 salt and CsPF6 additive. An extended service temperature range from 40°C to 60°C was obtained in LIBs with lithium nickel cobalt aluminum mixed oxide (LiNi0.80Co0.15Al0.05O2, NCA) as cathode and graphite as anode. The discharge capacities at low temperatures and the cycle life at room and elevated temperatures were systematically investigated in association with the ionic conductivity and phase transition behaviors. The most promising electrolyte formulation was identified as 1.0 M LiPF6 in EC-PC-EMC (1:1:8 by wt.) with 0.05 M CsPF6, which was demonstrated in both coin cells of graphite||NCA and 1 Ah pouch cells of graphite||LiNi1/3Mn1/3Co1/3O2. This optimized electrolyte enables excellent wide-temperature performances, as evidenced by the 68% capacity retention at 40C and C/5 rate, and nearly identical stable cycle life at room and elevated temperatures up to 60C.

Wide-Temperature Electrolytes for Lithium-Ion Batteries.

Science.gov (United States)

Li, Qiuyan; Jiao, Shuhong; Luo, Langli; Ding, Michael S; Zheng, Jianming; Cartmell, Samuel S; Wang, Chong-Min; Xu, Kang; Zhang, Ji-Guang; Xu, Wu

2017-06-07

Formulating electrolytes with solvents of low freezing points and high dielectric constants is a direct approach to extend the service-temperature range of lithium (Li)-ion batteries (LIBs). In this study, we report such wide-temperature electrolyte formulations by optimizing the ethylene carbonate (EC) content in the ternary solvent system of EC, propylene carbonate (PC), and ethyl methyl carbonate (EMC) with LiPF 6 salt and CsPF 6 additive. An extended service-temperature range from -40 to 60 °C was obtained in LIBs with lithium nickel cobalt aluminum oxide (LiNi 0.80 Co 0.15 Al 0.05 O 2 , NCA) as cathode and graphite as anode. The discharge capacities at low temperatures and the cycle life at room temperature and elevated temperatures were systematically investigated together with the ionic conductivity and phase-transition behaviors. The most promising electrolyte formulation was identified as 1.0 M LiPF 6 in EC-PC-EMC (1:1:8 by wt) with 0.05 M CsPF 6 , which was demonstrated in both coin cells of graphite∥NCA and 1 Ah pouch cells of graphite∥LiNi 1/3 Mn 1/3 Co 1/3 O 2 . This optimized electrolyte enables excellent wide-temperature performances, as evidenced by the high capacity retention (68%) at -40 °C and C/5 rate, significantly higher than that (20%) of the conventional LIB electrolyte, and the nearly identical stable cycle life as the conventional LIB electrolyte at room temperature and elevated temperatures up to 60 °C.

An advanced lithium-ion battery based on a graphene anode and a lithium iron phosphate cathode.

Science.gov (United States)

Hassoun, Jusef; Bonaccorso, Francesco; Agostini, Marco; Angelucci, Marco; Betti, Maria Grazia; Cingolani, Roberto; Gemmi, Mauro; Mariani, Carlo; Panero, Stefania; Pellegrini, Vittorio; Scrosati, Bruno

2014-08-13

We report an advanced lithium-ion battery based on a graphene ink anode and a lithium iron phosphate cathode. By carefully balancing the cell composition and suppressing the initial irreversible capacity of the anode in the round of few cycles, we demonstrate an optimal battery performance in terms of specific capacity, that is, 165 mAhg(-1), of an estimated energy density of about 190 Wh kg(-1) and a stable operation for over 80 charge-discharge cycles. The components of the battery are low cost and potentially scalable. To the best of our knowledge, complete, graphene-based, lithium ion batteries having performances comparable with those offered by the present technology are rarely reported; hence, we believe that the results disclosed in this work may open up new opportunities for exploiting graphene in the lithium-ion battery science and development.

Ascorbic Acid-Assisted Eco-friendly Synthesis of NiCo2O4 Nanoparticles as an Anode Material for High-Performance Lithium-Ion Batteries

Science.gov (United States)

Karunakaran, Gopalu; Maduraiveeran, Govindhan; Kolesnikov, Evgeny; Balasingam, Suresh Kannan; Viktorovich, Lysov Dmitry; Ilinyh, Igor; Gorshenkov, Mikhail V.; Sasidharan, Manickam; Kuznetsov, Denis; Kundu, Manab

2018-05-01

We have synthesized NiCo2O4 nanoparticles (NCO NPs) using an ascorbic acid-assisted co-precipitation method for the first time. When NCO NPs are used as an anode material for lithium-ion batteries, the cell exhibits superior lithium storage properties, such as high capacity (700 mA h g-1 after 300 cycles at 200 mA g-1), excellent rate capabilities (applied current density range 100-1200 mA g-1), and impressive cycling stability (at 1200 mA g-1 up to 650 cycles). The enhanced electrochemical properties of NCO NPs are due to the nanometer dimensions which not only offers a smooth charge-transport pathway and short diffusion paths of the lithium ions but also adequate spaces for volume expansion during Li storage. Hence, this eco-friendly synthesis approach will provide a new strategy for the synthesis of various nanostructured metal oxide compounds, for energy conversion and storage systems applications.

Soft mode and magnetic phase transition in PrNi

International Nuclear Information System (INIS)

Alekseev, P.A.; Lazukov, V.N.; Sadikov, I.P.; Klement'ev, E.S.; Allenspach, P.; Chumlyakov, Yu.I.

2002-01-01

The spectrum of the magnetic excitation of the PrNi intermetallic compound monocrystal is studied through the neutrons inelastic scattering. Essential softening of certain collective modes of the magnetic excitation near the temperature of the ferromagnetic ordering T c ∼ 20 K is identified. The above result is analyzed from the viewpoint of the model, describing the magnetic phase transition in the systems with the directed magnetic moment [ru

Martensitic phase transition in Cu–14%Al–4%Ni shape memory alloys studied by Brillouin light scattering

International Nuclear Information System (INIS)

Graczykowski, B; Mielcarek, S; Mroz, B; Breczewski, T; No, M L; San-Juan, J

2013-01-01

The paper presents the influence of the martensitic phase transition on hypersonic thermally excited surface acoustic waves propagating in Cu–14%Al–4%Ni (wt%) shape memory alloy. Non-destructive and non-contact testing using Brillouin light scattering spectroscopy permitted determination of the elastic constants of austenite versus temperature. Experimental results obtained for martensite were interpreted using the proposed model of the cubic to orthorhombic martensitic phase transition based on the Landau model of a first-order phase transition. Additionally we adopted the approximation of the domain structure of martensite by a polycrystalline sample using the Voigt–Reuss–Hill procedure of averaging the elastic constants. (paper)

Lithium carbon batteries with solid polymer electrolyte; Accumulateur lithium carbone a electrolyte solide polymere

Energy Technology Data Exchange (ETDEWEB)

Andrieu, X.; Boudin, F. [Alcatel Alsthom Recherche, 91 - Marcoussis (France)

1996-12-31

The lithium carbon batteries studied in this paper use plasticized polymer electrolytes made with passive polymer matrix swollen by a liquid electrolyte with a high ionic conductivity (> 10{sup -3} S/cm at 25 deg. C). The polymers used to prepare the gels are polyacrylonitrile (PAN) and vinylidene poly-fluoride (PVdF). The electrochemical and physical properties of these materials are analyzed according to their composition. The behaviour of solid electrolytes with different materials of lithium ion insertion (graphite and LiNiO{sub 2}) are studied and compared to liquid electrolytes. The parameters taken into account are the reversible and irreversible capacities, the cycling performance and the admissible current densities. Finally, complete lithium ion batteries with gelled electrolytes were manufactured and tested. (J.S.) 2 refs.

Lithium carbon batteries with solid polymer electrolyte; Accumulateur lithium carbone a electrolyte solide polymere

Energy Technology Data Exchange (ETDEWEB)

Andrieu, X; Boudin, F [Alcatel Alsthom Recherche, 91 - Marcoussis (France)

1997-12-31

The lithium carbon batteries studied in this paper use plasticized polymer electrolytes made with passive polymer matrix swollen by a liquid electrolyte with a high ionic conductivity (> 10{sup -3} S/cm at 25 deg. C). The polymers used to prepare the gels are polyacrylonitrile (PAN) and vinylidene poly-fluoride (PVdF). The electrochemical and physical properties of these materials are analyzed according to their composition. The behaviour of solid electrolytes with different materials of lithium ion insertion (graphite and LiNiO{sub 2}) are studied and compared to liquid electrolytes. The parameters taken into account are the reversible and irreversible capacities, the cycling performance and the admissible current densities. Finally, complete lithium ion batteries with gelled electrolytes were manufactured and tested. (J.S.) 2 refs.

Formation and Applications of Bulk Glassy Alloys in Late Transition Metal Base System

International Nuclear Information System (INIS)

Inoue, Akihisa; Shen Baolong

2006-01-01

This paper reviews our recent results of the formation, fundamental properties, workability and applications of late transition metal (LTM) base bulk glassy alloys (BGAs) developed since 1995. The BGAs were obtained in Fe-(Al,Ga)-(P,C,B,Si), Fe-(Cr,Mo)-(C,B), Fe-(Zr,Hf,Nb,Ta)-B, Fe-Ln-B(Ln=lanthanide metal), Fe-B-Si-Nb and Fe-Nd-Al for Fe-based alloys, Co-(Ta,Mo)-B and Co-B-Si-Nb for Co-based alloys, Ni-Nb-(Ti,Zr)-(Co,Ni) for Ni-based alloys, and Cu-Ti-(Zr,Hf), Cu-Al-(Zr,Hf), Cu-Ti-(Zr,Hf)-(Ni,Co) and Cu-Al-(Zr,Hf)-(Ag,Pd) for Cu-based alloys. These BGAs exhibit useful properties of high mechanical strength, large elastic elongation and high corrosion resistance. In addition, Fe- and Co-based glassy alloys have good soft magnetic properties which cannot be obtained for amorphous and crystalline type magnetic alloys. The Fe- and Ni-based BGAs have already been used in some application fields. These LTM base BGAs are promising as new metallic engineering materials

Transition between periodic and quasiperiodic structures in Al-Ni-Co

International Nuclear Information System (INIS)

Grushko, B.; Wittmann, R.

1998-01-01

A series of Al-Ni-Co alloys forming stable decagonal (D-ANC) quasicrystals was studied in as-cast and annealed states. It was shown that under certain conditions periodic structures with pseudodecagonal (PD) symmetry can be produced at the same compositions as stable decagonal quasicrystals. Different variants of D-ANC and PD were observed in a compositional range of 70-72.5 at.% Al and 13-18 at.% Co. As-cast D-ANC can be transformed to single-phase PD of the same local composition. Single-phase PDs can be transformed to D-ANC of the same composition by heating to a temperature higher than the formation temperature of these PDs. The transition between PD and D-ANC was studied in more detail in Al 71 Ni 14.5 Co 14.5 and Al 70 Ni 15 Co 15 by electron microscopy, powder X-ray diffractometry and differential thermal analysis. The results of this study do not confirm the thermodynamic stability of this PD structure. (orig.)

A rocking chair type all-solid-state lithium ion battery adopting Li2O-ZrO2 coated LiNi0.8Co0.15Al0.05O2 and a sulfide based electrolyte

Science.gov (United States)

Ito, Seitaro; Fujiki, Satoshi; Yamada, Takanobu; Aihara, Yuichi; Park, Youngsin; Kim, Tae Young; Baek, Seung-Wook; Lee, Jae-Myung; Doo, Seokgwang; Machida, Nobuya

2014-02-01

An all-solid-state lithium-ion battery (ASSB) using non-flammable solid electrolytes is a candidate for a next-generation battery. Although the excellent cycle performance and its high energy density are suggested in the literature, a practical size battery has not been appeared yet. In this paper, we have adopted a sulfide based electrolyte, Li2S-P2S5 (80:20 mol%) to a rocking chair type lithium ion battery. The electrochemical cell consists of a Li2O-ZrO2 coated LiNi0.8Co0.15Al0.05O2 (NCA) cathode, an artificial graphite anode and the sulfide based electrolyte without any organic and inorganic liquids. The cathode charge transfer resistance is significantly reduced by the Li2O-ZrO2 coating. The total cell resistance of the Li2O-ZrO2 (LZO) coated NCA adopted cell is approximately one quarter of non-treated one. A standard type single cell with the nominal capacity of 100 mAh at 25 °C is fabricated by wet printing process, and its capacity retention is approximately 80% at 100 cycles. Also, a 1 Ah class battery was constructed by stacking the single cells, and demonstrated.

Phase transition in lithium ammonium sulphate doped with cesium metal ions

Science.gov (United States)

Gaafar, M.; Kassem, M. E.; Kandil, S. H.

2000-07-01

Effects of doped cesium (C s+) metal ions (with different molar ratios n) on the phase transition of lithium ammonium sulphate LiNH 4SO 4 system have been studied by measuring the specific heat Cp( T) of the doped systems in the temperature range from 400 to 480 K. The study shows a peculiar phase transition of the pure system ( n=0) characterized by double distinct peaks, changed to a single sharp and narrow one as a result of the doping process. The measurements exhibit different effects of enhanced molar ratios of dopants on the phase transition behaviour of this system. At low dopant content ( n≤3%), the excess specific heat (Δ Cp) max at the transition temperature T1 decreases till a minimum value at n=0.8%, then it increases gradually. In this case, Δ Cp( T) behaviour is varied quantitatively and not modified. Enhanced dopant content ( n>3%) has a pronounced effect on the critical behaviour, which is significantly changed and considerably modified relative to the pure system. In addition, broadening of the critical temperature region, and decrease of (Δ Cp) max associated with changes of the Landau expansion coefficients are obtained and discussed. The study deals with the contribution of the thermally excited dipoles to the specific heat in the ferroelectric region and shows that their energy depends on doping.

Crosslinkable fumed silica-based nanocomposite electrolytes for rechargeable lithium batteries

Energy Technology Data Exchange (ETDEWEB)

Li, Yangxing; Yerian, Jeffrey A.; Khan, Saad A.; Fedkiw, Peter S. [Department of Chemical & amp; Biomolecular Engineering, North Carolina State University, Raleigh, NC 27695-7905 (United States)

2006-10-27

Electrochemical and rheological properties are reported of composite polymer electrolytes (CPEs) consisting of dual-functionalized fumed silica with methacrylate and octyl groups+low-molecular weight poly(ethylene glycol) dimethyl ether (PEGdm)+lithium bis(trifluoromethanesulfonyl)imide (LiTFSI, lithium imide)+butyl methacrylate (BMA). The role of butyl methacrylate, which aids in formation of a crosslinked network by tethering adjacent fumed silica particles, on rheology and electrochemistry is examined together with the effects of fumed silica surface group, fumed silica weight percent, salt concentration, and solvent molecular weight. Chemical crosslinking of the fumed silica with 20% BMA shows a substantial increase in the elastic modulus of the system and a transition from a liquid-like/flocculated state to an elastic network. In contrast, no change in lithium transference number and only a modest decrease (factor of 2) on conductivity of the CPE are observed, indicating that a crosslinked silica network has minimal effect on the mechanism of ionic transport. These trends suggest that the chemical crosslinks occur on a microscopic scale, as opposed to a molecular scale, between adjacent silica particles and therefore do not impede the segmental mobility of the PEGdm. The relative proportion of the methacrylate and octyl groups on the silica surface displays a nominal effect on both rheology and conductivity following crosslinking although the pre-cure rheology is a function of the surface groups. Chemical crosslinked nanocomposite polymer electrolytes offer significant higher elastic modulus and yield stress than the physical nanocomposite counterpart with a small/negligible penalty of transport properties. The crosslinked CPEs exhibit good interfacial stability with lithium metal at open circuit, however, they perform poorly in cycling of lithium-lithium cells. (author)

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.

Nitriding behavior of Ni and Ni-based binary alloys

Energy Technology Data Exchange (ETDEWEB)

Fonovic, Matej

2015-01-15

Gaseous nitriding is a prominent thermochemical surface treatment process which can improve various properties of metallic materials such as mechanical, tribological and/or corrosion properties. This process is predominantly performed by applying NH{sub 3}+H{sub 2} containing gas atmospheres serving as the nitrogen donating medium at temperatures between 673 K and 873 K (400 C and 600 C). NH{sub 3} decomposes at the surface of the metallic specimen and nitrogen diffuses into the surface adjacent region of the specimen whereas hydrogen remains in the gas atmosphere. One of the most important parameters characterizing a gaseous nitriding process is the so-called nitriding potential (r{sub N}) which determines the chemical potential of nitrogen provided by the gas phase. The nitriding potential is defined as r{sub N} = p{sub NH{sub 3}}/p{sub H{sub 2}{sup 3/2}} where p{sub NH{sub 3}} and p{sub H{sub 2}} are the partial pressures of the NH{sub 3} and H{sub 2} in the nitriding atmosphere. In contrast with nitriding of α-Fe where the nitriding potential is usually in the range between 0.01 and 1 atm{sup -1/2}, nitriding of Ni and Ni-based alloys requires employing nitriding potentials higher than 100 atm{sup -1/2} and even up to ∞ (nitriding in pure NH{sub 3} atmosphere). This behavior is compatible with decreased thermodynamic stability of the 3d-metal nitrides with increasing atomic number. Depending on the nitriding conditions (temperature, nitriding potential and treatment time), different phases are formed at the surface of the Ni-based alloys. By applying very high nitriding potential, formation of hexagonal Ni{sub 3}N at the surface of the specimen (known as external nitriding) leads to the development of a compound layer, which may improve tribological properties. Underneath the Ni{sub 3}N compound layer, two possibilities exist: (i) alloying element precipitation within the nitrided zone (known as internal nitriding) and/or (ii) development of metastable and

Glass-forming ability and crystallization behavior of some binary and ternary Ni-based glassy alloys

International Nuclear Information System (INIS)

Louzguine-Luzgin, Dmitri V.; Louzguina-Luzgina, Larissa V.; Xie Guoqiang; Li Song; Zhang Wei; Inoue, Akihisa

2008-01-01

The purpose of the current paper is to study the influence of Ti, V, Nb, Al, Sn and Pd additions on the glass-forming ability, formation of a supercooled liquid region and a devitrification process of some Ni-Zr glassy alloys as well as to compare the results with those obtained for similar Cu-based alloys studied earlier. The Ni-based glassy alloys were investigated by using X-ray diffraction, differential scanning and isothermal calorimetries. Although the studied Ni-based alloys showed high values of the reduced glass-transition temperature of about 0.6, their glass-forming ability is quite low. This fact may be explained by low stability of the supercooled liquid against crystallization and formation of the equilibrium intermetallic compounds with a high growth rate compared to those observed in similar Cu-based alloys studied earlier. Relatively low thermal conductivity of Ni-based alloys is also found to be another factor limiting their glass-forming ability

Comparing magnetostructural transitions in Ni{sub 50}Mn{sub 18.75}Cu{sub 6.25}Ga{sub 25} and Ni{sub 49.80}Mn{sub 34.66}In{sub 15.54} Heusler alloys

Energy Technology Data Exchange (ETDEWEB)

Dubenko, Igor [Department of Physics, Southern Illinois University, Carbondale, IL 62901 (United States); Granovsky, Alexander [Faculty of Physics, Lomonosov Moscow State University, Moscow 119991 (Russian Federation); Lahderanta, Erkki [Lappeenranta University of Technology, 53851 (Finland); Kashirin, Maxim; Makagonov, Vladimir [Voronezh State Technical University, Voronezh 394026 (Russian Federation); Aryal, Anil; Quetz, Abdiel; Pandey, Sudip [Department of Physics, Southern Illinois University, Carbondale, IL 62901 (United States); Rodionov, Igor [Faculty of Physics, Lomonosov Moscow State University, Moscow 119991 (Russian Federation); Samanta, Tapas; Stadler, Shane [Department of Physics & Astronomy, Louisiana State University, Baton Rouge, LA 70803 (United States); Mazumdar, Dipanjan, E-mail: dmazumdar@siu.edu [Department of Physics, Southern Illinois University, Carbondale, IL 62901 (United States); Ali, Naushad [Department of Physics, Southern Illinois University, Carbondale, IL 62901 (United States)

2016-03-01

The crystal structure, magnetic and transport properties, including resistivity and thermopower, of Ni{sub 50}Mn{sub 18.75}Cu{sub 6.25}Ga{sub 25} and Ni{sub 49.80}Mn{sub 34.66}In{sub 15.54} Heusler alloys were studied in the (10–400) K temperature interval. We show that their physical properties are remarkably different, thereby pointing to different origin of their magnetostructural transition (MST). A Seebeck coefficient (S) was found to pass minimum of about −20 µV/K in respect of temperature for both compounds. It was shown that MST observed for both compounds results in jump-like changes in S for Ga-based compound and jump in resistivity of about 20 and 200 µΩ cm for Ga and In –based compounds, respectively. The combined analyzes of the present results with that from literature show that the density of states at the Fermi level does not change strongly at the MST in the case of Ni–Mn–In alloys as compared to that of Ni–Mn–Ga. - Graphical abstract: Temperature dependencies of resistivity for Ni{sub 50}Mn{sub 18.75}Cu{sub 6.25}Ga{sub 25} and Ni{sub 49.80}Mn{sub 34.66}In{sub 15.54} obtained on heating (open symbols) and cooling (closed symbols). Arrows indicate the temperature of direct (T{sub M}) and inverse (T{sub A}) martensitic transitions and ferromagnetic ordering of the austenitic (T{sub C}) and martensitic (T{sub CM}) phases. The T{sub CM}=T{sub A}/T{sub M} in the case of Ga-based alloy. - Highlights: • Magnetostructural transitions (MST) in two compounds with same parent material. • The figure exemplifies how sensitive MST properties are to the density of states. • Proper understanding is required for utilizing these multifunctional materials.

Heteroaromatic-based electrolytes for lithium and lithium-ion batteries

Science.gov (United States)

Cheng, Gang; Abraham, Daniel P.

2017-04-18

The present invention provides an electrolyte for lithium and/or lithium-ion batteries comprising a lithium salt in a liquid carrier comprising heteroaromatic compound including a five-membered or six-membered heteroaromatic ring moiety selected from the group consisting of a furan, a pyrazine, a triazine, a pyrrole, and a thiophene, the heteroaromatic ring moiety bearing least one carboxylic ester or carboxylic anhydride substituent bound to at least one carbon atom of the heteroaromatic ring. Preferred heteroaromatic ring moieties include pyridine compounds, pyrazine compounds, pyrrole compounds, furan compounds, and thiophene compounds.

Interaction of steel elements with products of lithium-water reactions

International Nuclear Information System (INIS)

Starkov, O.V.; Orlov, A.V.; Orlova, E.A.

1980-01-01

Isobar and isothermal potentials of reactions of products of lithium interaction with water (Li 2 O, LiOH) with components of structural steels (Fe, Cr, Ni, Cr 4 C, Ni, Ti, Si, Al) are calculated at the general pressure of P=1 at in the absence of mutual solubility of components. The chemical resistance of steel components to lithium oxide and hydroxide effect in the temperature range of 300-1500 K is estimated comparatively. Lithium oxide and hydroxide have different corrosion properties relatively to chromium-nickel steels (simple and complex compounds form with LiOH, which do not form with Li 2 O). Titanium, niobium, silicon, aluminium form stable compounds when interacting with LiOH. In reactions with Li 2 O only complex titanium compounds are stable at the temperature >1150 K; aluminium compounds are stable in the whole range of temperatures investigated

Pseudomorphic-to-bulk fcc phase transition of thin Ni films on Pd(100)

International Nuclear Information System (INIS)

Rizzi, G.A.; Petukhov, M.; Sedona, F.; Granozzi, G.; Cossaro, A.; Bruno, F.; Cvetko, D.; Morgante, A.; Floreano, L.

2004-01-01

We have measured the transformation of pseudomorphic Ni films on Pd(100) into their bulk fcc phase as a function of the film thickness. We made use of x-ray diffraction and x-ray induced photoemission to study the evolution of the Ni film and its interface with the substrate. The growth of a film with tetragonally strained face centered symmetry (fct) has been observed by out-of-plane x-ray diffraction up to a limit thickness of 10 Ni pseudomorphic layers (some of them partially filled and intermixed with the substrate), where a new fcc bulklike phase is formed. After the formation of the bulklike Ni domains, we observed the pseudomorphic fct domains to disappear preserving the number of layers and their spacing. The phase transition thus proceeds via lateral growth of the bulklike phase within the pseudomorphic one, i.e., the bulklike fcc domains penetrate down to the substrate when formed. This large depth of the walls separating the domains of different phases is also indicated by the increase of the intermixing at the substrate-film interface, which starts at the onset of the transition and continues at even larger thickness. The bulklike fcc phase is also slightly strained; its relaxation towards the orthomorphic lattice structure proceeds slowly with the film thickness, being not yet completed at the maximum thickness presently studied of 30 A (∼17 layers)

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

NARCIS (Netherlands)

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

2004-01-01

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

Analysis of the October 5, 1979 lithium spill and fire in the Lithium Processing Test Loop

International Nuclear Information System (INIS)

Maroni, V.A.; Beatty, R.A.; Brown, H.L.; Coleman, L.F.; Foose, R.M.; McPheeters, C.C.; Slawecki, M.; Smith, D.L.; Van Deventer, E.H.; Weston, J.R.

1981-12-01

On October 5, 1979, the Lithium Processing Test Loop (LPTL) developed a lithium leak in the electromagnetic (EM) pump channel, which damaged the pump, its surrounding support structure, and the underlying floor pan. A thorough analysis of the causes and consequences of the pump failure was conducted by personnel from CEN and several other ANL divisions. Metallurgical analyses of the elliptical pump channel and adjacent piping revealed that there was a significant buildup of iron-rich crystallites and other solid material in the region of the current-carrying bus bars (region of high magnetic field), which may have resulted in a flow restriction that contributed to the deterioration of the channel walls. The location of the failure was in a region of high residual stress (due to cold work produced during channel fabrication); this failure is typical of other cold work/stress-related failures encountered in components operated in forced-circulation lithium loops. Another important result was the isolation of crystals of a compound characterized as Li/sub x/CrN/sub y/. Compounds of this type are believed to be responsible for much of the Fe, Cr, and Ni mass transfer encountered in lithium loops constructed of stainless steel. The importance of nitrogen in the mass-transfer mechanism has long been suspected, but the existence of stable ternary Li-M-N compounds (M = Fe, Cr, Ni) had not previously been verified

Effect of Molecular Guest Binding on the d-d Transitions of Ni2+ of CPO-27-Ni: A Combined UV-Vis, Resonant-Valence-to-Core X-ray Emission Spectroscopy, and Theoretical Study.

Science.gov (United States)

Gallo, Erik; Gorelov, Evgeny; Guda, Alexander A; Bugaev, Aram L; Bonino, Francesca; Borfecchia, Elisa; Ricchiardi, Gabriele; Gianolio, Diego; Chavan, Sachin; Lamberti, Carlo

2017-12-04

We used Ni K-edge resonant-valence-to-core X-ray emission spectroscopy (RVtC-XES, also referred to as direct RIXS), an element-selective bulk-sensitive synchrotron-based technique, to investigate the electronic structure of the CPO-27-Ni metal-organic framework (MOF) upon molecular adsorption of significant molecular probes: H 2 O, CO, H 2 S, and NO. We compare RVtC-XES with UV-vis spectroscopy, and we show that the element selectivity of RVtC-XES is of strategic significance to observe the full set of d-d excitations in Ni 2+ , which are partially overshadowed by the low-energy π-π* transitions of the Ni ligands in standard diffuse-reflectance UV-vis experiments. Our combined RVtC-XES/UV-vis approach provides access to the whole set of d-d excitations, allowing us a complete discussion of the changes undergone by the electronic configuration of the Ni 2+ sites hosted within the MOF upon molecular adsorption. The experimental data have been interpreted by multiplet ligand-field theory calculations based on Wannier orbitals. This study represents a step further in understanding the ability of the CPO-27-Ni MOFs in molecular sorption and separation applications.

Enhanced electrochemical properties of LiNiO{sub 2}-based cathode materials by nanoscale manganese carbonate treatment

Energy Technology Data Exchange (ETDEWEB)

Zhao, Junkai; Wang, Zhixing, E-mail: zxwang.csu@hotmail.com; Guo, Huajun; Li, Xinhai

2017-05-01

Highlights: • Li residuals are consumed during the process of modification. • MnO{sub 2} coating layer can protect bulk material from the erosion of electrolyte. • The electrochemical performance is enhanced by the nanosacle MnCO{sub 3} treatment. • The enhancement of coating can be strengthened by the removal of lithium impurities. - Abstract: LiNiO{sub 2}-based layered oxides are of great importance as cathode materials for rechargeable batteries. In this paper, illustrating LiNi{sub 0.8}Co{sub 0.15}Al{sub 0.05}O{sub 2} as an example, the effect of nanoscale MnCO{sub 3} treatment on LiNiO{sub 2}-based materials is investigated for the first time. The structures of materials and the properties about the object surface are characterized by XRD, SEM, TEM, EDAX and XPS. The results demonstrate that a part of MnCO{sub 3} is able to react with lithium impurities to form nonstoichiometric Li{sub x}Mn{sub y}O{sub 4} and the rest of MnCO{sub 3} is converted to MnO{sub 2} coating on the surface of the material in situ. After 100 repeated cycles at 1C, the modified material exhibits a capacity retention rate of 91.2%, while the bare material only remains 84.8%. And the modified material exhibits more significantly improved cycling stability when cycling at 60 °C, maintaining 85.7% of its initial capacity at 1C after 100th cycles. The consumption of Li impurities can decelerate the decomposition of electrolyte during cycling, thus result in less resistive byproducts. Moreover, the obtained MnO{sub 2} coating layer acts as an isolating layer to suppress the drastic reaction between active material and electrolyte. This synergistic effect is responsible for the excellent properties of MnCO{sub 3}-modified material.

Deposition and characterization of thin films of materials with application in cathodes for lithium rechargeable micro batteries

International Nuclear Information System (INIS)

Lopez I, J.

2007-01-01

In this thesis work is reported the deposition and characterization of thin films of materials of the type LiMO 2 , with M=Co and Ni, which have application in cathodes for micro-batteries of lithium ions. In the last years some investigators have reported that the electrochemical operation of the lithium ions batteries it can improve recovering the cathode, in bundle form, with some metal oxides as the Al 2 O 3 ; for that the study of the formation of thin films in bilayer form LiMO 2 /AI 2 O 3 is of interest in the development of lithium ions micro batteries. The thin films were deposited using the laser ablation technique studying the effect of some deposit parameters in the properties of the one formed material, as: laser fluence, substrate temperature and working atmosphere, with the purpose of optimizing it. In the case of the LiCoO 2 it was found that to use an inert atmosphere of argon allows to obtain the material with the correct composition. Additionally, with the use of a temperature in the substrate of 150 C is possible to obtain to the material with certain crystallinity grade that to the subjected being to a post-deposit thermal treatment at 300 C for three hours, it gives as result a totally crystalline material. In the case of the thin films of LiNiO 2 , it was necessary to synthesize the oxide starting from a reaction of solid state among nickel oxide (NiO) and lithium oxide (Li 2 O) obtaining stoichiometric LiNiO 2 . For the formation of the thin films of LiNiO 2 it was used an argon atmosphere and the laser fluence was varied, the deposits were carried out to two different substrates temperatures, atmosphere and 160 C. In both cases the material it was recovered with an alumina layer, found that this layer didn't modify the structural properties of the base oxide (LiCoO 2 and LiNiO 2 ). (Author)

Exclusive study of Ni+Ni and Ni+Au central collisions: phase coexistence and spinodal decomposition; Etude exclusive des collisions centrales Ni+Ni et Ni+Au: coexistence de phase et decomposition spinodale

Energy Technology Data Exchange (ETDEWEB)

Guiot, B

2002-12-01

The INDRA multidetector allowed us to study the Ni+Ni collisions at 32A MeV and the Ni+Au collisions at 52,4 MeV. Central collisions leading to 'quasi-fused' systems were isolated using multidimensional analysis techniques: the Discriminant Analysis and the Principal Component Analysis. Comparison with a statistical model shows that the selected events are compatible with thermodynamical equilibrium. The average thermal excitation energy is 5A MeV for both systems. Calculations of heat capacities show that the deexcitation of the hot sources are akin to a liquid-gas phase transition of nuclear matter. Indeed heat capacities exhibit a negative branch as expected for a phase transition of a finite system. The dynamics of this phase transition has been investigated by applying the charge correlation method. An enhanced production of events with equal-sized fragments has been evidenced for Ni+Au at 52A MeV. No signal was found for Ni+Ni at 32A MeV. Finally this method was improved by taking into account the total charge conservation. The signal is seen more clearly for Ni+Au at 52A MeV, but is ambiguous for Ni+Ni at 32A MeV. The path followed in the state diagram, or the involved time scales, seem to be different for these systems. (authors)

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

Science.gov (United States)

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

2015-02-18

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

Quantum anomalous Hall effect and topological phase transition in two-dimensional antiferromagnetic Chern insulator NiOsCl6

Science.gov (United States)

Yang, Wei-Wei; Li, Lei; Zhao, Jing-Sheng; Liu, Xiao-Xiong; Deng, Jian-Bo; Tao, Xiao-Ma; Hu, Xian-Ru

2018-05-01

By doing calculations based on density functional theory, we predict that the two-dimensional anti-ferromagnetic (AFM) NiOsCl6 as a Chern insulator can realize the quantum anomalous Hall (QAH) effect. We investigate the magnetocrystalline anisotropy energies in different magnetic configurations and the Néel AFM configuration is proved to be ground state. When considering spin–orbit coupling (SOC), this layered material with spins perpendicular to the plane shows properties as a Chern insulator characterized by an inversion band structure and a nonzero Chern number. The nontrivial band gap is 37 meV and the Chern number C  =  ‑1, which are induced by a strong SOC and AFM order. With strong SOC, the NiOsCl6 system performs a continuous topological phase transition from the Chern insulator to the trivial insulator upon the increasing Coulomb repulsion U. The critical U c is indicated as 0.23 eV, at which the system is in a metallic phase with . Upon increasing U, the E g reduces linearly with C  =  ‑1 for 0    U c . At last we analysis the QAH properties and this continuous topological phase transition theoretically in a two-band model. This AFM Chern insulator NiOsCl6 proposes not only a promising way to realize the QAH effect, but also a new material to study the continuous topological phase transition.

Atomic Layer Deposition of Stable LiAlF4 Lithium Ion Conductive Interfacial Layer for Stable Cathode Cycling.

Science.gov (United States)

Xie, Jin; Sendek, Austin D; Cubuk, Ekin D; Zhang, Xiaokun; Lu, Zhiyi; Gong, Yongji; Wu, Tong; Shi, Feifei; Liu, Wei; Reed, Evan J; Cui, Yi

2017-07-25

Modern lithium ion batteries are often desired to operate at a wide electrochemical window to maximize energy densities. While pushing the limit of cutoff potentials allows batteries to provide greater energy densities with enhanced specific capacities and higher voltage outputs, it raises key challenges with thermodynamic and kinetic stability in the battery. This is especially true for layered lithium transition-metal oxides, where capacities can improve but stabilities are compromised as wider electrochemical windows are applied. To overcome the above-mentioned challenges, we used atomic layer deposition to develop a LiAlF 4 solid thin film with robust stability and satisfactory ion conductivity, which is superior to commonly used LiF and AlF 3 . With a predicted stable electrochemical window of approximately 2.0 ± 0.9 to 5.7 ± 0.7 V vs Li + /Li for LiAlF 4 , excellent stability was achieved for high Ni content LiNi 0.8 Mn 0.1 Co 0.1 O 2 electrodes with LiAlF 4 interfacial layer at a wide electrochemical window of 2.75-4.50 V vs Li + /Li.

Electron paramagnetic resonance response and magnetic interactions in ordered solid solutions of lithium nickel oxides

Energy Technology Data Exchange (ETDEWEB)

Azzoni, C.B. [Istituto Nazionale di Fisica della Materia, Dipartimento di Fisica ' Alessandro Volta' , Universita di Pavia, Pavia (Italy); Paleari, A. [Istituto Nazionale di Fisica della Materia, Dipartimento di Fisica, Universita di Milano, Milan (Italy); Massarotti, V.; Capsoni, D. [Dipartimento di Chimica-Fisica, Universita di Pavia, Pavia (Italy)

1996-09-23

EPR data of ordered solid solutions of lithium nickel oxides are reported as a function of the lithium content. The features of the signal and the EPR centre density are analysed by a model of dynamical trapping of holes in [(Ni{sup 2+}-O-Ni{sup 2+})-h{sup +}] complexes. The possible origin of the interactions responsible for the magnetic ordering and some features of the transport properties are also discussed. (author)

A General and Mild Approach to Controllable Preparation of Manganese-Based Micro- and Nanostructured Bars for High Performance Lithium-Ion Batteries.

Science.gov (United States)

Ma, Guo; Li, Sheng; Zhang, Weixin; Yang, Zeheng; Liu, Shulin; Fan, Xiaoming; Chen, Fei; Tian, Yuan; Zhang, Weibo; Yang, Shihe; Li, Mei

2016-03-07

One-dimensional (1D) micro- and nanostructured electrode materials with controllable phase and composition are appealing materials for use in lithium-ion batteries with high energy and power densities, but they are challenging to prepare. Herein, a novel ethanol-water mediated co-precipitation method by a chimie douce route (synthesis conducted under mild conditions) has been exploited to selectively prepare an extensive series of manganese-based electrode materials, manifesting the considerable generalizability and efficacy of the method. Moreover, by simply tuning the mixed solvent and reagents, transition metal oxide bars with differing aspect ratios and compositions were prepared with an unprecedented uniformity. Application prospects are demonstrated by Li-rich 0.5 Li2 MnO3 ⋅0.5 LiNi1/3 Co1/3 Mn1/3 O2 bars, which demonstrate excellent reversible capacity and rate capability thanks to the steerable nature of the synthesis and material quality. This work opens a new route to 1D micro- and nanostructured materials by customizing the precipitating solvent to orchestrate the crystallization process. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Phase transitions and molecular motions in [Ni(ND3)6](ClO4)2

International Nuclear Information System (INIS)

Migdal-Mikuli, Anna; Mikuli, Edward; Gorska, Natalia; Kowalska, Aneta; Ulanski, Jacek

2004-01-01

[Ni(ND 3 ) 6 ](ClO 4 ) 2 has three solid phases between 100 and 300 K. The phase transitions temperatures at heating (T C1 h =164.1 K and T C2 h =145.1 K) are shifted, as compared to the non-deuterated compound, towards the lower temperature of ca. 8 and 5 K, respectively. The ClO 4 - anions perform fast, picosecond, isotropic reorientation with the activation energy of 6.6 kJ mol -1 , which abruptly slow down at T C1 c phase transition, during sample cooling. The ND 3 ligands perform fast uniaxial reorientation around the Ni-N bond in all three detected phases, with the effective activation energy of 2.9 kJ mol -1 . The reorientational motion of ND 3 is only slightly distorted at the T C1 phase transition due to the dynamical orientational order-disorder process of anions. The low value of the activation energy for the ND 3 reorientation suggests that this reorientation undergoes the translation-rotation coupling, which makes the barrier to the rotation of the ammonia ligands not constant but fluctuating. The phase polymorphism and the dynamics of the molecular reorientations of the title compound are similar but not quite identical with these of the [Ni(NH 3 ) 6 ](ClO 4 ) 2

Coating effect of LiFePO4 and Al2O3 on Li1.2Mn0.54Ni0.13Co0.13O2 cathode surface for lithium ion batteries

CSIR Research Space (South Africa)

Seteni, Bonani

2017-06-01

Full Text Available Lithium-manganese-rich cathode material Li1.2Mn0.54Ni0.13Co0.13O2 is prepared by combustion method, and then coated with nano-sized LiFePO4 and nano-sized Al2O3 particles via a wet chemical process. The as-prepared Li1.2Mn0.54Ni0.13Co0.13O2, LiFePO4...

Enhanced cycling performance of a Li metal anode in a dimethylsulfoxide-based electrolyte using highly concentrated lithium salt for a lithium-oxygen battery

Science.gov (United States)

Togasaki, Norihiro; Momma, Toshiyuki; Osaka, Tetsuya

2016-03-01

Stable charge-discharge cycling behavior for a lithium metal anode in a dimethylsulfoxide (DMSO)-based electrolyte is strongly desired of lithium-oxygen batteries, because the Li anode is rapidly exhausted as a result of side reactions during cycling in the DMSO solution. Herein, we report a novel electrolyte design for enhancing the cycling performance of Li anodes by using a highly concentrated DMSO-based electrolyte with a specific Li salt. Lithium nitrate (LiNO3), which forms an inorganic compound (Li2O) instead of a soluble product (Li2S) on a lithium surface, exhibits a >20% higher coulombic efficiency than lithium bis(trifluoromethanesulfonyl)imide, lithium bis(fluorosulfonyl)imide, and lithium perchlorate, regardless of the loading current density. Moreover, the stable cycling of Li anodes in DMSO-based electrolytes depends critically on the salt concentration. The highly concentrated electrolyte 4.0 M LiNO3/DMSO displays enhanced and stable cycling performance comparable to that of carbonate-based electrolytes, which had not previously been achieved. We suppose this enhancement is due to the absence of free DMSO solvent in the electrolyte and the promotion of the desolvation of Li ions on the solid electrolyte interphase surface, both being consequences of the unique structure of the electrolyte.

Facile and Reliable in Situ Polymerization of Poly(Ethyl Cyanoacrylate)-Based Polymer Electrolytes toward Flexible Lithium Batteries.

Science.gov (United States)

Cui, Yanyan; Chai, Jingchao; Du, Huiping; Duan, Yulong; Xie, Guangwen; Liu, Zhihong; Cui, Guanglei

2017-03-15

Polycyanoacrylate is a very promising matrix for polymer electrolyte, which possesses advantages of strong binding and high electrochemical stability owing to the functional nitrile groups. Herein, a facile and reliable in situ polymerization strategy of poly(ethyl cyanoacrylate) (PECA) based gel polymer electrolytes (GPE) via a high efficient anionic polymerization was introduced consisting of PECA and 4 M LiClO 4 in carbonate solvents. The in situ polymerized PECA gel polymer electrolyte achieved an excellent ionic conductivity (2.7 × 10 -3 S cm -1 ) at room temperature, and exhibited a considerable electrochemical stability window up to 4.8 V vs Li/Li + . The LiFePO 4 /PECA-GPE/Li and LiNi 1.5 Mn 0.5 O 4 /PECA-GPE/Li batteries using this in-situ-polymerized GPE delivered stable charge/discharge profiles, considerable rate capability, and excellent cycling performance. These results demonstrated this reliable in situ polymerization process is a very promising strategy to prepare high performance polymer electrolytes for flexible thin-film batteries, micropower lithium batteries, and deformable lithium batteries for special purpose.

Exclusive study of Ni+Ni and Ni+Au central collisions: phase coexistence and spinodal decomposition

International Nuclear Information System (INIS)

Guiot, B.

2002-12-01

The INDRA multidetector allowed us to study the Ni+Ni collisions at 32A MeV and the Ni+Au collisions at 52,4 MeV. Central collisions leading to 'quasi-fused' systems were isolated using multidimensional analysis techniques: the Discriminant Analysis and the Principal Component Analysis. Comparison with a statistical model shows that the selected events are compatible with thermodynamical equilibrium. The average thermal excitation energy is 5A MeV for both systems. Calculations of heat capacities show that the deexcitation of the hot sources are akin to a liquid-gas phase transition of nuclear matter. Indeed heat capacities exhibit a negative branch as expected for a phase transition of a finite system. The dynamics of this phase transition has been investigated by applying the charge correlation method. An enhanced production of events with equal-sized fragments has been evidenced for Ni+Au at 52A MeV. No signal was found for Ni+Ni at 32A MeV. Finally this method was improved by taking into account the total charge conservation. The signal is seen more clearly for Ni+Au at 52A MeV, but is ambiguous for Ni+Ni at 32A MeV. The path followed in the state diagram, or the involved time scales, seem to be different for these systems. (authors)

Magnetic Properties of Porous Metal-Organic Frameworks: Ni2(BODC)2(TED) and Ni2(BDC)2(TED)

Science.gov (United States)

Hamida, Youcef; Danilovic, Dusan; Lin, Chyan; Yuen, Tan; Li, Kunhao; Padmanabhan, Moothetty; Li, Jing

2010-03-01

Results of χ(T), M(H), and heat capacity C(T) measurements on two Ni dimer based porous materials Ni2(BODC)2(TED) and Ni2(BDC)2(TED) are reported. These materials form a tetragonal crystal structure of space group P4/ncc with a=b = 14.9 å and c = 19.4 å and Ni-Ni separation of 2.61å within the dimer. Magnetic data of Ni2(BODC)2(TED) revealed a ferromagnetic-like transition at about 17 K with θ = 8 K, and a coercivity field of 1700 G was observed in the hysteresis curve. Though isostructural to Ni2(BODC)2(TED), χ(T) and M(H) results of Ni2(BDC)2(TED) showed an antiferromagnetic transition at 10 K with θ = - 132 K, and no hysteresis was observed. Although specific heat data C(T) showed no clear transition in both compounds, nonlinear behavior is clearly seen in C/T vs. T plots, and a fit to the electron and phonon contributions to C(T) gives a large heavy-fermion-like γ in both cases. A model for the magnetic interactions is proposed and a comparison to the Cu and Co analogues is also made.

Study on property-gradient polymer electrolyte for rechargeable lithium batteries; Lithium niji denchi no tame no keisha tokusei kobunshi denkaishitsu no sosei ni kansuru kenkyu

Energy Technology Data Exchange (ETDEWEB)

Kokumi, Z; Kanemura, S; Inaba, M; Takehara, Z; Yao, K; Uchimoto, Y [Kyoto University, Kyoto (Japan)

1997-02-01

This paper describes the fundamental experiments for creating property-gradient polymer electrolyte for rechargeable lithium batteries. The rechargeable lithium battery is composed of an anodic composite agent section with high ion conductivity, a separator equivalent section with high mechanical strength (high bridging degree), and a section surpressing the precipitation of metal lithium by contacting with it. The continuous property-gradient polymer electrolyte was tried to be synthesized by means of the plasma polymerization method. As a result, plasma polymerization electrolyte with high ion conductivity could be prepared from the liquid phase by using a monomer with low vapor pressure. Porous material simulating the anodic composite agent was impregnated by the monomer, which was plasma-polymerized. As a result, it was found that the bridging degree decreased from the surface towards the inside of the plasma-polymerized porous material. In addition, polymer was prepared using fluorine-base monomer. Thus, LiF thin film could be prepared through the reaction between the polymer and metal lithium. 3 figs.

Effect of excess Ni on martensitic transition, exchange bias and inverse magnetocaloric effect in Ni{sub 2+x}Mn{sub 1.4−x}Sn{sub 0.6} alloy

Energy Technology Data Exchange (ETDEWEB)

Ray, Mayukh K., E-mail: mayukh.ray@saha.ac.in; Bagani, K.; Banerjee, S., E-mail: sangam.banerjee@saha.ac.in

2014-07-05

Highlights: • Excess Ni causes an increase in the martensite transition temperature. • The system Ni{sub 2+x}Mn{sub 1.4−x}Sn{sub 0.6} exhibit multifunctional properties. • The RCP and EB increases continuously with excess Ni concentration in the system. • Antiferromagnetic interaction increases with excess Ni concentration. - Abstract: The martensitic transition, exchange bias (EB) and inverse magnetocaloric effect (IMCE) of bulk Ni{sub 2+x}Mn{sub 1.4−x}Sn{sub 0.6} (x = 0, 0.06, 0.12, 0.18) Heusler alloy is investigated in this paper. Substitution of Mn by Ni causes an increase in the martensite transition temperature (T{sub M}), decrease in Curie temperature of austenite phase (T{sub C}{sup A}) and also a decrease in the saturation magnetic moment (M{sub sat}). While the decrease in T{sub C}{sup A} and M{sub sat} is explained by the dilution of the magnetic subsystems and on the other hand the increase in T{sub M} is due to the increase of valence electron concentration per atom (e/a). All the alloys shows EB effect below a certain temperature (T{sup ∗}) and EB field (H{sub EB}) value is almost thrice in magnitude for x = 0.18 sample compared to x = 0 sample at 5 K. In these alloys, Ni/Mn atoms at regular site couples antiferromagnetically (AFM) with the excess Ni atoms at Mn or Sn sites and this AFM coupling plays the key role in the observation of EB. For the IMCE, the change in magnetic entropy (ΔS{sub M}) initially increased with excess Ni concentration upto x = 0.12 but then a drastic fall in ΔS{sub M} value is observed for the sample x = 0.18 but the relative cooling power (RCP) value is increased continuously with the excess Ni concentration.

First-principles calculations for the elastic properties of Ni-base model superalloys: Ni/Ni3Al multilayers

International Nuclear Information System (INIS)

Yun-Jiang, Wang; Chong-Yu, Wang

2009-01-01

A model system consisting of Ni[001](100)/Ni 3 Al[001](100) multi-layers are studied using the density functional theory in order to explore the elastic properties of single crystal Ni-based superalloys. Simulation results are consistent with the experimental observation that rafted Ni-base superalloys virtually possess a cubic symmetry. The convergence of the elastic properties with respect to the thickness of the multilayers are tested by a series of multilayers from 2γ'+2γ to 10γ'+10γ atomic layers. The elastic properties are found to vary little with the increase of the multilayer's thickness. A Ni/Ni 3 Al multilayer with 10γ'+10γ atomic layers (3.54 nm) can be used to simulate the mechanical properties of Ni-base model superalloys. Our calculated elastic constants, bulk modulus, orientation-dependent shear modulus and Young's modulus, as well as the Zener anisotropy factor are all compatible with the measured results of Ni-base model superalloys R1 and the advanced commercial superalloys TMS-26, CMSX-4 at a low temperature. The mechanical properties as a function of the γ' phase volume fraction are calculated by varying the proportion of the γ and γ' phase in the multilayers. Besides, the mechanical properties of two-phase Ni/Ni 3 Al multilayer can be well predicted by the Voigt–Reuss–Hill rule of mixtures. (classical areas of phenomenology)

Insights on the fundamental lithium storage behavior of all-solid-state lithium batteries containing the LiNi0.8Co0.15Al0.05O2 cathode and sulfide electrolyte

Science.gov (United States)

Peng, Gang; Yao, Xiayin; Wan, Hongli; Huang, Bingxin; Yin, Jingyun; Ding, Fei; Xu, Xiaoxiong

2016-03-01

An insightful study on the fundamental lithium storage behavior of all-solid-state lithium battery with a structure of LiNi0.8Co0.15Al0.05O2 (NCA)/Li10GeP2S12/Li-In is carried out in this work. The relationship between electrochemical performances and particle size, surface impurities and defects of the NCA positive material is systematically investigated. It is found that a ball-milling technique can decrease the particle size and remove surface impurities of the NCA cathode while also give rise to surface defects which could be recovered by a post-annealing process. The results indicate that the interfacial resistance between the NCA and Li10GeP2S12 is obviously decreased during the ball-milling followed by a post-annealing. Consequently, the discharge capacity of NCA in the NCA/Li10GeP2S12/Li-In solid-state battery is significantly enhanced, which exhibits a discharge capacity of 146 mAh g-1 at 25 °C.

Spin glass transition in a thin-film NiO/permalloy bilayer

Science.gov (United States)

Ma, Tianyu; Urazhdin, Sergei

2018-02-01

We experimentally study magnetization aging in a thin-film NiO/permalloy bilayer. Aging characteristics are nearly independent of temperature below the exchange bias blocking temperature TB, but rapidly vary above it. The dependence on the magnetic history qualitatively changes across TB. The observed behaviors are consistent with the spin glass transition at TB, with significant implications for magnetism and magnetoelectronic phenomena in antiferromagnet/ferromagnet bilayers.

The electronic structure and magnetic interactions in the mixed transition-metal oxide La(Co,Ni)O{sub 3} studied by X-ray absorption spectroscopies

Energy Technology Data Exchange (ETDEWEB)

Huang, Meng-Jie

2016-11-11

Transition-metal oxides have attracted a lot of attention because they exhibit a variety of intriguing physical properties. Among the transition-metal oxides, LaCoO{sub 3} is a very special compound which shows different spin states and spin-state transitions. Further, the physical properties can be controlled by changing temperature, replacement of rare-earth element, electron- or hole-doping, or by applying strain. The ground state of LaCoO{sub 3} is a non-magnetic insulator because the lowest energy configuration is t{sub 2g}{sup 6}e{sub g}{sup 0} (S = 0). However, the partial substitution of Co by Ni in La(Co,Ni)O{sub 3} (LCNO) will induce a ferromagnetic behavior. A number of models have been proposed for explaining the nature of the magnetic behavior in the past decades, but it is still a puzzle. In order to understand the origin of the ferromagnetism in La(Co,Ni)O{sub 3}, I have studied the electronic structure and magnetic interaction in this compound in a very direct way: by using X-ray absorption (XAS) and X-ray magnetic circular dichroism (XMCD) along with multiplet simulations. Samples were synthesized by the sol-gel method and structurally and magnetically characterized by XRD and SQUID. XAS clearly indicates a mixed-valence state for both Co and Ni, with both valences increasing monotonously with Ni content, x. While the gradual spin-state transition of Co{sup 3+} from low-spin (LS) to high-spin (HS) is preserved for low x it is suppressed in the high Ni-content samples. Regarding the spin configuration of Ni we find it stabilized in a ''mixed'' spin state, unlike the purely LS state of Ni in LaNiO{sub 3}. XMCD identifies the element-specific contributions to the magnetic moment and interactions. In particular, we find that it must be the coexistence of the HS state in both Co{sup 3+} and Ni{sup 3+} that induces t{sub 2g}-based ferromagnetic interaction via a ''double-exchange-like'' mechanism. Other species

Study of fatigue and fracture behavior of NbCr{sub 2}-based alloys: Phase stability in Nb-Cr-Ni ternary system

Energy Technology Data Exchange (ETDEWEB)

Zhu, J.H.; Liaw, P.K. [Univ. of Tennessee, Knoxville, TN (United States). Dept. of Materials Science and Engineering; Liu, C.T. [Oak Ridge National Lab., TN (United States). Metals and Ceramics Div.

1997-12-01

Phase stability in a ternary Nb-Cr-Ni Laves phase system was studied in this paper. Their previous study in NbCr{sub 2}-based transition-metal Laves phases has shown that the average electron concentration factor, e/a, is the dominating factor in controlling the phase stability of NbCr{sub 2}-based Laves phases when the atomic size ratios are kept identical. Since Ni has ten out-shell electrons, the substitution of Ni for Cr in NbCr{sub 2} will increase the average electron concentration of the alloy, thus leading to the change of the crystal structures from C15 to C14. In this paper, a number of pseudo-binary Nb(Cr,Ni){sub 2} alloys were prepared, and the crystal structures of the alloys after a long heat-treatment at 1000 C as a function of the Ni content were determined by the X-ray diffraction technique. The boundaries of the C15/C14 transition were determined and compared to their previous predictions. It was found that the electron concentration and phase stability correlation is obeyed in the Nb-Cr-Ni system. However, the e/a ratio corresponding to the C15/C14 phase transition was found to move to a higher value than the predicted one. The changes in the lattice constant, Vickers hardness and fracture toughness were also determined as a function of the Ni content, which were discussed in light of the phase stability difference of the alloys.

Mathematical modeling of the lithium deposition overcharge reaction in lithium-ion batteries using carbon-based negative electrodes

International Nuclear Information System (INIS)

Arora, P.; Doyle, M.; White, R.E.

1999-01-01

Two major issues facing lithium-ion battery technology are safety and capacity grade during cycling. A significant amount of work has been done to improve the cycle life and to reduce the safety problems associated with these cells. This includes newer and better electrode materials, lower-temperature shutdown separators, nonflammable or self-extinguishing electrolytes, and improved cell designs. The goal of this work is to predict the conditions for the lithium deposition overcharge reaction on the negative electrode (graphite and coke) and to investigate the effect of various operating conditions, cell designs and charging protocols on the lithium deposition side reaction. The processes that lead to capacity fading affect severely the cycle life and rate behavior of lithium-ion cells. One such process is the overcharge of the negative electrode causing lithium deposition, which can lead to capacity losses including a loss of active lithium and electrolyte and represents a potential safety hazard. A mathematical model is presented to predict lithium deposition on the negative electrode under a variety of operating conditions. The Li x C 6 vertical bar 1 M LiPF 6 , 2:1 ethylene carbonate/dimethyl carbonate, poly(vinylidene fluoride-hexafluoropropylene) vert b ar LiMn 2 O 4 cell is simulated to investigate the influence of lithium deposition on the charging behavior of intercalation electrodes. The model is used to study the effect of key design parameters (particle size, electrode thickness, and mass ratio) on the lithium deposition overcharge reaction. The model predictions are compared for coke and graphite-based negative electrodes. The cycling behavior of these cells is simulated before and after overcharge to understand the hazards and capacity fade problems, inherent in these cells, can be minimized

Nickel/carbon core/shell nanotubes: Lanthanum nickel alloy catalyzed synthesis, characterization and studies on their ferromagnetic and lithium-ion storage properties

International Nuclear Information System (INIS)

Anthuvan Rajesh, John; Pandurangan, Arumugam; Senthil, Chenrayan; Sasidharan, Manickam

2014-01-01

Highlights: • Ni/CNTs core/shell structure was synthesized using LaNi 5 alloy catalyst by CVD. • The magnetic and lithium-ion storage properties of Ni/CNTs structure were studied. • The specific Ni/CNTs structure shows strong ferromagnetic property with large coercivity value of 446.42 Oe. • Ni/CNTs structure shows enhanced electrochemical performance in terms of stable capacity and better rate capability. - Abstract: A method was developed to synthesize ferromagnetic nickel core/carbon shell nanotubes (Ni/CNTs) by chemical vapor deposition using Pauli paramagnetic lanthanum nickel (LaNi 5 ) alloy both as a catalyst and as a source for the Ni-core. The Ni-core was obtained through oxidative dissociation followed by hydrogen reduction during the catalytic growth of the CNTs. Transmission electron microscopy (TEM), selected area electron diffraction (SAED) and X-ray diffraction (XRD) analyses reveal that the Ni-core exists as a face centered cubic single crystal. The magnetic hysteresis loop of Ni/CNTs particle shows increased coercivity (446.42 Oe) than bulk Ni at room temperature. Furthermore, the Ni/CNTs core/shell particles were investigated as anode materials in lithium-ion batteries. The Ni/CNTs electrode delivered a high discharge capacity of 309 mA h g −1 at 0.2 C, and a stable cycle-life, which is attributed to high structural stability of Ni/CNTs electrode during electrochemical lithium-ion insertion and de-insertion redox reactions

A Lithium-Ion Battery with Enhanced Safety Prepared using an Environmentally Friendly Process.

Science.gov (United States)

Mueller, Franziska; Loeffler, Nicholas; Kim, Guk-Tae; Diemant, Thomas; Behm, R Jürgen; Passerini, Stefano

2016-06-08

A new lithium-ion battery chemistry is presented based on a conversion-alloying anode material, a carbon-coated Fe-doped ZnO (TMO-C), and a LiNi1/3 Mn1/3 Co1/3 O2 (NMC) cathode. Both electrodes were fabricated using an environmentally friendly cellulose-based binding agent. The performance of the new lithium-ion battery was evaluated with a conventional, carbonate-based electrolyte (ethylene carbonate:diethyl carbonate-1 m lithium hexafluorophosphate, EC:DEC 1 m LiPF6 ) and an ionic liquid (IL)-based electrolyte (N-butyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide-0.2 m lithium bis(trifluoromethanesulfonyl)imide, Pyr14 TFSI 0.2 m LiTFSI), respectively. Galvanostatic charge/discharge tests revealed a reduced rate capability of the TMO-C/Pyr14 TFSI 0.2 m LiTFSI/NMC full-cell compared to the organic electrolyte, but the coulombic efficiency was significantly enhanced. Moreover, the IL-based electrolyte substantially improves the safety of the system due to a higher thermal stability of the formed anodic solid electrolyte interphase and the IL electrolyte itself. While the carbonate-based electrolyte shows sudden degradation reactions, the IL exhibits a slowly increasing heat flow, which does not constitute a serious safety risk. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Monte Carlo simulation of ordering transformations in Ni-Mo-based alloys

International Nuclear Information System (INIS)

Kulkarni, U.D.

2004-01-01

The quenched in state of short range order (SRO) in binary Ni-Mo alloys is characterized by intensity maxima at {1 (1/2) 0} and equivalent positions in the reciprocal space. Ternary addition of a small amount of Al to the binary alloy, on the other hand, leads to a state of SRO that gives rise to intensity maxima at {1 0 0} and equivalent, in addition to {1 (1/2) 0} and equivalent, positions in the selected area electron diffraction patterns. Different geometric patterns of streaks of diffuse intensity, joining the SRO maxima with the superlattice positions of the emerging long range ordered (LRO) structures or in some cases between the superlattice positions of different LRO structures, are observed during the SRO-to-LRO transitions in the Ni-Mo-based and other 1 (1/2) 0 alloys. Monte Carlo simulations have been carried out here in order to shed some light on the atomic structures of the SRO and the SRO-to-LRO transition states in these alloys

Development of lithium target for accelerator based neutron capture therapy

International Nuclear Information System (INIS)

Taskaev, Sergey; Bayanov, Boris; Belov, Victor; Zhoorov, Eugene

2006-01-01

Pilot innovative accelerator based neutron source for neutron capture therapy of cancer is now of the threshold of its operation at the BINP, Russia. One of the main elements of the facility is lithium target producing neutrons via threshold 7 Li(p,n) 7 Be reaction at 25 kW proton beam with energies 1.915 MeV or 2.5 MeV. The main problems of lithium target were determined to be: 7 Be radioactive isotope activation keeping lithium layer solid, presence of photons due to proton inelastic scattering on lithium nuclei, and radiation blistering. The results of thermal test of target prototype were presented as previous NCT Congress. It becomes clear that water is preferable for cooling the target, and that lithium target 10 cm in diameter is able to run before melting. In the present report, the conception of optimal target is proposed: thin metal disk 10 cm in diameter easy for detaching, with evaporated thin layer of pure lithium from the side of proton beam exposure, its back being intensively cooled with turbulent water flow to maintain lithium layer solid. Design of the target for the neutron source constructed at BINP is shown. The results of investigation of radiation blistering and lithium layer are presented. Target unit of facility is under construction now, and obtaining neutrons is expected in nearest future. (author)

Lithium ion batteries with titania/graphene anodes

Science.gov (United States)

Liu, Jun; Choi, Daiwon; Yang, Zhenguo; Wang, Donghai; Graff, Gordon L; Nie, Zimin; Viswanathan, Vilayanur V; Zhang, Jason; Xu, Wu; Kim, Jin Yong

2013-05-28

Lithium ion batteries having an anode comprising at least one graphene layer in electrical communication with titania to form a nanocomposite material, a cathode comprising a lithium olivine structure, and an electrolyte. The graphene layer has a carbon to oxygen ratio of between 15 to 1 and 500 to 1 and a surface area of between 400 and 2630 m.sup.2/g. The nanocomposite material has a specific capacity at least twice that of a titania material without graphene material at a charge/discharge rate greater than about 10 C. The olivine structure of the cathode of the lithium ion battery of the present invention is LiMPO.sub.4 where M is selected from the group consisting of Fe, Mn, Co, Ni and combinations thereof.

77 FR 2437 - Special Conditions: Gulfstream Aerospace Corporation, Model GVI Airplane; Rechargeable Lithium...

Science.gov (United States)

2012-01-18

... delivery of the affected aircraft. In addition, the substance of these special conditions has been subject... Ni-Cd and lead-acid cells, some types of lithium-battery cells use flammable liquid electrolytes. The... lithium batteries. The flammable-fluid fire-protection requirements of Sec. 25.863. In the past, this rule...

First principles study of the diffusional phenomena across the clean and Re-doped γ -Ni/ γ ’-Ni3Al interface of Ni-based single crystal superalloy

International Nuclear Information System (INIS)

Sun Min; Wang Chong-Yu

2016-01-01

Density functional theory calculations in conjunction with the climbing images nudged elastic band method are conducted to study the diffusion phenomena of the Ni-based single crystal superalloys. We focus our attention on the diffusion processes of the Ni and Al atoms in the γ and γ ’ phases along the direction perpendicular to the interface. The diffusion mechanisms and the expressions of the diffusion coefficients are presented. The vacancy formation energies, the migration energies, and the activation energies for the diffusing Ni and Al atoms are estimated, and these quantities display the expected and clear transition zones in the vicinity of the interface of about 3–7 (002) layers. The local density-of-states profiles of atoms in each (002) layer in the γ and γ ’ phases and the partial density-of-states curves of Re and some of its nearest-neighbor atoms are also presented to explore the electronic effect of the diffusion behavior. (paper)

Crystal structures and magnetic properties of iron (III)-based phosphates: Na4NiFe(PO4)3 and Na2Ni2Fe(PO4)3

International Nuclear Information System (INIS)

Essehli, Rachid; Bali, Brahim El; Benmokhtar, Said; Bouziane, Khalid; Manoun, Bouchaib; Abdalslam, Mouner Ahmed; Ehrenberg, Helmut

2011-01-01

Graphical abstract: A perspective view of the Na 2 Ni 2 Fe(PO 4 ) 3 structure along the [0 0 1] direction. Both compounds seem to exibit antiferromagnetic interactions between magnetic entities at low temperature. Display Omitted Research highlights: → Nasicon and Alluaudite compounds, Iron(III)-based phosphates, Crystal structures of Na 4 NiFe(PO 4 ) 3 and Na 2 Ni 2 Fe(PO 4 ) 3 . → Magnetism behaviours of Na 4 NiFe(PO 4 ) 3 and Na 2 Ni 2 Fe(PO 4 ) 3 . → Antiferromagnetism interactions. → Mossbauer spectroscopy. - Abstract: Crystal structures from two new phosphates Na 4 NiFe(PO 4 ) 3 (I) and Na 2 Ni 2 Fe(PO 4 ) 3 (II) have been determined by single crystal X-ray diffraction analysis. Compound (I) crystallizes in a rhombohedral system (S. G: R-3c, Z = 6, a = 8.7350(9) A, c = 21.643(4) A, R 1 = 0.041, wR 2 =0.120). Compound (II) crystallizes in a monoclinic system (S. G: C2/c, Z = 4, a = 11.729(7) A, b = 12.433(5) A, c = 6.431(2) A, β = 113.66(4) o , R 1 = 0.043, wR 2 =0.111). The three-dimensional structure of (I) is closely related to the Nasicon structural type, consisting of corner sharing [(Ni/Fe)O 6 ] octahedra and [PO 4 ] tetrahedra forming [NiFe(PO 4 ) 3 ] 4+ units which align in chains along the c-axis. The Na + cations fill up trigonal antiprismatic sites within these chains. The crystal structure of (II) belongs to the alluaudite type. Its open framework results from [Ni 2 O 10 ] units of edge-sharing [NiO 6 ] octahedra, which alternate with [FeO 6 ] octahedra that form infinite chains. Coordination of these chains yields two distinct tunnels in which site Na + . The magnetization data of compound (I) reveal antiferromagnetic (AFM) interactions by the onset of deviations from a Curie-Weiss behaviour at low temperature as confirmed by Moessbauer measurements performed at 4.2 K. The corresponding temperature dependence of the reciprocal susceptibility χ -1 follows a typical Curie-Weiss behaviour for T > 105 K. A canted AFM state is proposed for

Pressure dependence of BaNi2As2

Energy Technology Data Exchange (ETDEWEB)

Ronning, Filip [Los Alamos National Laboratory; Park, Tuscon [Los Alamos National Laboratory; Bauer, Eric D [Los Alamos National Laboratory; Thompson, Joe D [Los Alamos National Laboratory

2009-01-01

We report results from resistivity measurements of BaNi{sub 2}As{sub 2} up to 27.4 kbar of pressure. We find the structural transition at 130 K is broadened slightly with increasing pressure. There is also minimal influence on the superconducting transition, where the resistive onset increases from 2 to 3 K, but the temperature at which zero resistance is obtained is unchanged up to 27.4 kbar. This behavior is in contrast to that observed in the Fe-based systems as well as in LaNiPO and LaNiAsO.

The Evaluation of Triphenyl Phosphate as a Flame Retardant Additive to Improve the Safety of Lithium-Ion Battery Electrolytes

Science.gov (United States)

Smart, M. C.; Krause, F. C.; Hwang, C.; West, W. C.; Soler, J.; Prakash, G. K. S.; Ratnakumar, B. V.

2011-01-01

With the intent of improving the safety characteristics of lithium ion cells, electrolytes containing flame retardant additives have been investigated. A number of triphenyl phosphate-containing electrolytes were evaluated in both coin cells and experimental three electrode lithium-ion cells (containing reference electrodes). A number of chemistries were investigated, including MCMB carbon/LiNi(0.8)Co(0.2)O2 (NCO), graphite/LiNi(0.8)Co(0.15)Al(0.05)O2 (NCA), Li/Li(Li(0.17)Ni(0.25)Mn(0.58))O2, Li/LiNiMnCoO2 (NMC) and graphite/LiNiMnCoO2 (NMC), to study the effect that different electrolyte compositions have upon performance. A wide range of TPP-containing electrolytes were demonstrated to have good compatibility with the C/NCO, C/NCA, and Li/NMC systems, however, poor performance was initially observed with the high voltage C/NMC system. This necessitated the development of improved electrolytes with stabilizing additives, leading to formulations containing lithium bis(oxalato)borate (LiBOB) that displayed substantially improved performance.

Effects of Residual Lithium in the precursors of Li[Ni1/3Co1/3Mn1/3]O2 on their lithium-ion battery performance

Science.gov (United States)

Jo, Minsang; Ku, Heesuk; Park, Sanghyuk; Song, Junho; Kwon, Kyungjung

2018-07-01

Li[Ni1/3Co1/3Mn1/3]O2 cathode active materials are synthesized from co-precipitated hydroxide precursors Lix[Ni1/3Co1/3Mn1/3]1-x(OH)2, and the effect of residual Li in the precursors on the lithium-ion battery (LIB) performance of their corresponding cathode active materials is investigated. Three kinds of precursors that contain different amounts of Li are selected depending on different conditions of the solution composition for the co-precipitation and washing process. It is confirmed that the introduction of Li to the precursors reduces the degree of structural perfection by X-ray diffraction analysis. Undesirable cation mixing occurs with the increasing Li content of the precursors, which is inferred from a decline in lattice parameters and the calculated intensity ratio of (003) and (104) peaks. In the voltage range of 3.0-4.3 V, the initial charge/discharge capacities and the rate capability of the cathode active materials are aggravated when Li exists in the precursors. Therefore, it could be concluded that the strict control of Li in a solution for co-precipitation of precursors is necessary in the resynthesis of cathode active materials from spent LIBs.

Electrochemical properties of rapidly solidified Si-Ti-Ni(-Cu) base anode for Li-ion rechargeable batteries

Science.gov (United States)

Kwon, Hye Jin; Sohn, Keun Yong; Park, Won-Wook

2013-11-01

In this study, rapidly solidified Si-Ti-Ni-Cu alloys have been investigated as high capacity anodes for Li-ion secondary batteries. To obtain nano-sized Si particles dispersed in the inactive matrix, the alloy ribbons were fabricated using the melt spinning process. The thin ribbons were pulverized using ball-milling to make a fine powder of ˜ 4 µm average size. Coin-cell assembly was carried out under an argon gas in a glove box, in which pure lithium was used as a counter-electrode. The cells were cycled using the galvanostatic method in the potential range of 0.01 V and 1.5 V vs. Li/Li+. The microstructure and morphology were examined using an x-ray diffractometer, Field-Emission Scanning Electron Microscopy and High Resolution Transmission Electron Microscopy. Among the anode alloys, the Si70Ti15Ni15 electrodes had the highest discharge capacity (974.1 mAh/g) after the 50th cycle, and the Si60Ti16Ni16Cu8 electrode showed the best coulombic efficiency of ˜95.9% in cyclic behavior. It was revealed that the Si7Ni4Ti4 crystal phase coexisting with an amorphous phase, could more efficiently act as a buffer layer than the fully crystallized Si7Ni4Ti4 phase. Consequently, the electrochemical properties of the anode materials pronouncedly improved when the nano-sized primary Si particle was dispersed in the inactive Si7Ni4Ti4-based matrix mixed with an amorphous structure.

Spin reorientation transitions of Fe/Ni/Cu(001) studied by using the depth-resolved X-ray magnetic circular dichroism technique

International Nuclear Information System (INIS)

Abe, Hitoshi; Amemiya, Kenta; Matsumura, Daiju; Kitagawa, Soichiro; Watanabe, Hirokazu; Yokoyama, Toshihiko; Ohta, Toshiaki

2006-01-01

The spin reorientation transition (SRT) of Ni/Cu(001) induced by Fe deposition was investigated using the X-ray magnetic circular dichroism (XMCD) method. In-plane magnetized Ni films (= =10ML) also exhibit a transition to in-plane by 1-2ML Fe deposition. A precise magnetic anisotropy phase diagram was obtained using a combination of wedge-shaped Ni samples and stepwise Fe deposition. Magnetic anisotropy energies in the bulk, surface and interface layers of Ni films were separately determined using the depth-resolved XMCD technique, while values in the 1ML and 2ML portions of the Fe films were obtained from the conventional XMCD measurements. The origin of the SRTs is successfully explained with a simple phenomenological layer model using the obtained magnetic anisotropy energies. es

Detailed studies of a high-capacity electrode material for rechargeable batteries, Li2MnO3-LiCo(1/3)Ni(1/3)Mn(1/3)O2.

Science.gov (United States)

Yabuuchi, Naoaki; Yoshii, Kazuhiro; Myung, Seung-Taek; Nakai, Izumi; Komaba, Shinichi

2011-03-30

Lithium-excess manganese layered oxides, which are commonly described by the chemical formula zLi(2)MnO(3)-(1-z)LiMeO(2) (Me = Co, Ni, Mn, etc.), are of great importance as positive electrode materials for rechargeable lithium batteries. In this Article, Li(x)Co(0.13)Ni(0.13)Mn(0.54)O(2-δ) samples are prepared from Li(1.2)Ni(0.13)Co(0.13)Mn(0.54)O(2) (or 0.5Li(2)MnO(3)-0.5LiCo(1/3)Ni(1/3)Mn(1/3)O(2)) by an electrochemical oxidation/reduction process in an electrochemical cell to study a reaction mechanism in detail before and after charging across a voltage plateau at 4.5 V vs Li/Li(+). Changes of the bulk and surface structures are examined by synchrotron X-ray diffraction (SXRD), X-ray absorption spectroscopy (XAS), X-ray photoelectron spectroscopy (XPS), and time-of-flight secondary ion mass spectroscopy (SIMS). SXRD data show that simultaneous oxygen and lithium removal at the voltage plateau upon initial charge causes the structural rearrangement, including a cation migration process from metal to lithium layers, which is also supported by XAS. This is consistent with the mechanism proposed in the literature related to the Li-excess manganese layered oxides. Oxygen removal associated with the initial charge on the high voltage plateau causes oxygen molecule generation in the electrochemical cells. The oxygen molecules in the cell are electrochemically reduced in the subsequent discharge below 3.0 V, leading to the extra capacity. Surface analysis confirms the formation of the oxygen containing species, such as lithium carbonate, which accumulates on the electrode surface. The oxygen containing species are electrochemically decomposed upon second charge above 4.0 V. The results suggest that, in addition to the conventional transition metal redox reactions, at least some of the reversible capacity for the Li-excess manganese layered oxides originates from the electrochemical redox reaction of the oxygen molecules at the electrode surface.

Effects of Nickel Particle Size and Graphene Support on the Electrochemical Performance of Lithium/Dissolved Polysulfide Batteries

International Nuclear Information System (INIS)

Mosavati, Negar; Chitturi, Venkateswara Rao; Arava, Leela Mohana Reddy; Salley, Steven O.; Ng, K.Y. Simon

2015-01-01

Highlights: • Electrodes with different nano size Ni particles are prepared. • The electrocatalytic effect of Ni nanoparticle sizes is investigated. • The graphene supported Ni nanoparticle is synthesized. • The effect of the graphene support to the anchor Ni nanoparticle is investigated. • Ni/graphene electrode exhibits remarkably enhanced discharge capacity. - Abstract: The electrocatalytic effect of nickel (Ni) nanoparticle sizes on the lithium polysulfide conversion reactions in dissolved lithium sulfur battery configuration is investigated. The Ni particles of 20 nm with the higher cathode surface area show a superior capacity of 1066 mAh g −1 sulfur compared to Ni particles of 40 and 100 nm for the first cycle. In addition, to further improve the capacity retention and discharge capacity of the cell, the effect of the graphene support on Ni nanoparticle dispersion and cycling performance is investigated. The results show a significant improvement in the discharge capacity compared to the other electrodes. This could be explained by the homogeneous distribution of Ni nanoparticle within the carbon matrix, which suppress the agglomeration and surface area loss of the Ni nanoparticle after cycling; as well as a synergetic effect of graphene structure and Ni nanoparticle.

KLL resonant Auger transitions in metallic Cu and Ni

International Nuclear Information System (INIS)

Koever, L.; Berenyi, Z.; Cserny, I.

2004-01-01

Complete text of publication follows. KLL Auger spectra of 3d transition metals contain important information on the effects of the solid environment on deep core Auger transitions. Following the changes in the spectra when fine tuning the exciting photon energy across the K-shell ionization threshold with high energy resolution is informative concerning the possible resonant processes, expected to indicate the single-step nature of threshold Auger emission. The satellite structures in these spectra are strongly related to the unoccupied local electronic states above the Fermi level, as well as to the excitation, relaxation and screening processes associated with core hole ionization. In spite of the fundamental significance of the phenomena mentioned above, even non resonant high energy resolution studies of KLL Auger spectra of 3d transition metals (using laboratory X-ray sources) are very scarce due to the demanding experimental conditions requested. A very efficient tool for studying these phenomena is the Tunable High Energy XPS developed at HASYLAB which provides unique conditions, photon x and energy resolution for deep core Auger spectroscopy. Using the THE-XPS instrument at the BW2 beamline the high energy resolution (ΔE = 0.2 eV) KL 2,3 L 2,3 Auger spectra of polycrystalline Cu and Ni foils were measured with the Scienta SES-200 hemispherical analyzer. In the high energy range Cu 2p photo-electron peaks appearing in the Cu KLL Auger spectra due to the excitation by internal Cu K X-rays and trusted value for the Cu 2p3/2 binding energy were used for energy calibration. The exciting photon energy range was tuned up to about 50 eV above the K absorption edge and for the resonant energy region to 5 eV (Cu KLL) and 4 eV (Ni KLL) below threshold ensuring a photon beam with an energy width of about 1.1 eV. The evolution of the satellite structure as a function of excitation energy above threshold indicates di rent behaviour for particular satellites, making

Homogeneous lithium electrodeposition with pyrrolidinium-based ionic liquid electrolytes.

Science.gov (United States)

Grande, Lorenzo; von Zamory, Jan; Koch, Stephan L; Kalhoff, Julian; Paillard, Elie; Passerini, Stefano

2015-03-18

In this study, we report on the electroplating and stripping of lithium in two ionic liquid (IL) based electrolytes, namely N-butyl-N-methylpyrrolidinium bis(fluorosulfonyl) imide (Pyr14FSI) and N-butyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (Pyr14TFSI), and mixtures thereof, both on nickel and lithium electrodes. An improved method to evaluate the Li cycling efficiency confirmed that homogeneous electroplating (and stripping) of Li is possible with TFSI-based ILs. Moreover, the presence of native surface features on lithium, directly observable via scanning electron microscope imaging, was used to demonstrate the enhanced electrolyte interphase (SEI)-forming ability, that is, fast cathodic reactivity of this class of electrolytes and the suppressed dendrite growth. Finally, the induced inhomogeneous deposition enabled us to witness the SEI cracking and revealed previously unreported bundled Li fibers below the pre-existing SEI and nonrod-shaped protuberances resulting from Li extrusion.

Thermal capture cross section for 58Ni (n,γ)59 Ni reaction

International Nuclear Information System (INIS)

Carbonari, A.W.; Pecequilo, B.R.S.

1989-01-01

The 58 Ni total thermal capture cross section was determined by suming the partial cross sections calculated for the primary transitions of the reaction 58 Ni (n,γ) 59 Ni. The primary transitions energies and intensities were determined from the 58 Ni thermal neutrons prompt gamma capture gamma rays spectrum in the 3.7 to 9.3 MeV region. The obtained value for the total cross section was 4.52 + 0.10b. (author) [pt

OCV Hysteresis in Li-Ion Batteries including Two-Phase Transition Materials

Directory of Open Access Journals (Sweden)

Michael A. Roscher

2011-01-01

Full Text Available The relation between batteries' state of charge (SOC and open-circuit voltage (OCV is a specific feature of electrochemical energy storage devices. Especially NiMH batteries are well known to exhibit OCV hysteresis, and also several kinds of lithium-ion batteries show OCV hysteresis, which can be critical for reliable state estimation issues. Electrode potential hysteresis is known to result from thermodynamical entropic effects, mechanical stress, and microscopic distortions within the active electrode materials which perform a two-phase transition during lithium insertion/extraction. Hence, some Li-ion cells including two-phase transition active materials show pronounced hysteresis referring to their open-circuit voltage. This work points out how macroscopic effects, that is, diffusion limitations, superimpose the latte- mentioned microscopic mechanisms and lead to a shrinkage of OCV hysteresis, if cells are loaded with high current rates. To validate the mentioned interaction, Li-ion cells' state of charge is adjusted to 50% with various current rates, beginning from the fully charged and the discharged state, respectively. As a pronounced difference remains between the OCV after charge and discharge adjustment, obviously the hysteresis vanishes as the target SOC is adjusted with very high current rate.

Ni/boride interfaces and environmental embrittlement in Ni-based superalloys: A first-principles study

International Nuclear Information System (INIS)

Sanyal, Suchismita; Waghmare, Umesh V.; Hanlon, Timothy; Hall, Ernest L.

2011-01-01

Highlights: ► Fracture strengths of Ni/boride interfaces through first-principles calculations. ► Fracture strengths of Ni/boride interfaces are higher than Ni/Ni 3 Al and NiΣ5 grain boundaries. ► Ni/boride interfaces have higher resistance to O-embrittlement than Ni/Ni 3 Al and NiΣ5 grain boundaries. ► CrMo-borides are more effective than Cr-borides in resisting O-embrittlement. ► Electronegativity differences between alloying elements correlate with fracture strengths. - Abstract: Motivated by the vital role played by boride precipitates in Ni-based superalloys in improving mechanical properties such as creep rupture strength, fatigue crack growth rates and improved resistance towards environmental embrittlement , we estimate fracture strength of Ni/boride interfaces through determination of their work of separation using first-principles simulations. We find that the fracture strength of Ni/boride interfaces is higher than that of other commonly occurring interfaces in Ni-alloys, such as Ni Σ-5 grain boundaries and coherent Ni/Ni 3 Al interfaces, and is less susceptible to oxygen-induced embrittlement. Our calculations show how the presence of Mo in Ni/M 5 B 3 (M = Cr, Mo) interfaces leads to additional reduction in oxygen-induced embrittlement. Through Electron-Localization-Function based analyses, we identify the electronic origins of effects of alloying elements on fracture strengths of these interfaces and observe that chemical interactions stemming from electronegativity differences between different atomic species are responsible for the trends in calculated strengths. Our findings should be useful towards designing Ni-based alloys with higher interfacial strengths and reduced oxygen-induced embrittlement.

Bridging exchange bias effect in NiO and Ni(core)@NiO(shell) nanoparticles

Energy Technology Data Exchange (ETDEWEB)

Rinaldi-Montes, Natalia, E-mail: nataliarin@gmail.com [Departamento de Física, Universidad de Oviedo, E-33007 Oviedo (Spain); Gorria, Pedro [Departamento de Física & IUTA, EPI, Universidad de Oviedo, E-33203 Gijón (Spain); Martínez-Blanco, David [Servicios Científico-Técnicos, Universidad de Oviedo, E-33006 Oviedo (Spain); Fuertes, Antonio B. [Instituto Nacional del Carbón, CSIC, E-33080 Oviedo (Spain); Fernández Barquín, Luis [CITIMAC, Facultad de Ciencias, Universidad de Cantabria, E-39005 Santander (Spain); Puente-Orench, Inés [Instituto de Ciencia de Materiales de Aragón, CSIC-Universidad de Zaragoza and Institut Laue-Langevin, BP 156, F-38042 Grenoble Cedex 9 (France); Blanco, Jesús A. [Departamento de Física, Universidad de Oviedo, E-33007 Oviedo (Spain)

2016-02-15

Among all bi-magnetic core(transition metal)@shell(transition metal oxide) nanoparticles (NPs), Ni@NiO ones show an onset temperature for the exchange bias (EB) effect far below the Néel temperature of bulk antiferromagnetic NiO. In this framework, the role played by the magnetism of NiO at the nanoscale is investigated by comparing the microstructure and magnetic properties of NiO and Ni@NiO NPs. With the aim of bridging the two systems, the diameter of the NiO NPs (~4 nm) is chosen to be comparable to the shell thickness of Ni@NiO ones (~2 nm). The EB effect in Ni@NiO NPs is attributed to the exchange coupling between the core and the shell, with an interfacial exchange energy of ΔE~0.06 erg cm{sup −2}, thus comparable to previous reports on Ni/NiO interfaces both in thin film and NP morphologies. In contrast, the EB detected in NiO NPs is explained in a picture where uncompensated spins located on a magnetically disordered surface shell are exchange coupled to the antiferromagnetic core. In all the studied NPs, the variation of the EB field as a function of temperature is described according to a negative exponential law with a similar decay constant, yielding a vanishing EB effect around T~40–50 K. In addition, the onset temperature for the EB effect in both NiO and Ni@NiO NPs seems to follow a universal dependence with the NiO crystallite size. - Highlights: • Comparison of the exchange bias effect in NiO and Ni(core)@NiO(shell) nanoparticles. • Universal temperature dependence of the exchange bias effect. • Suggested similar physical origin of the effect in both systems. • Size and crystallinity of the NiO shell hold the key for exchange bias properties.

Study of LiNiVO{sub 4} thin films used as anodes in lithium micro-batteries; Etude de couches minces de type LiNiVO{sub 4} utilisables en tant qu'electrode negative dans des microbatteries au lithium

Energy Technology Data Exchange (ETDEWEB)

Reddy, V.

2003-03-01

Since fifteen years, considerable effort has been invested in developing thin film solid state micro-batteries as possible integrated components in microelectronics. The recent technological improvement concerning miniaturized systems opens a large field of applications for the future use of micro-batteries. LiNiVO{sub 4} thin films are promising materials as anodes for lithium micro-batteries. All the thin films have been prepared by radio-frequency magnetron sputtering using a LiNiVO{sub 4} target. The discharge gas was either pure argon or a mixture of argon and oxygen. We have studied the influence of some experimental parameters such as the oxygen partial pressure, the sputtering power, the target-substrate distance, the total pressure and the substrate temperature on the composition, the microstructure and the electrochemical properties. The chemical composition of the thin films has been determined by Rutherford backscattering spectroscopy combined with nuclear reaction analysis. Among all experimental parameters investigated, only the partial pressure of oxygen has a considerable influence on the thin film composition. Auger spectroscopy has revealed a good homogeneity of the thin films. X-ray diffraction shows that the as-deposited thin films are amorphous. The near-stoichiometric composition Li{sub 1.12}NiV{sub 1.02}O{sub 4}.11 has highlighted good electrochemical properties in the potential range [3 V - 0.02 V]. This particular composition displays a high capacity of 1000 mAh/g which is enhanced when the film is annealed at 300 degrees C. (author)

Phase transitions and thermal expansion in Ni51- x Mn36 + x Sn13 alloys

Science.gov (United States)

Kaletina, Yu. V.; Gerasimov, E. G.; Kazantsev, V. A.; Kaletin, A. Yu.

2017-10-01

Thermal expansion and structural and magnetic phase transitions in alloys of the Ni-Mn-Sn system have been investigated. The spontaneous martensitic transformation in Ni51-xMn36 + xSn13 (0 ≤ x ≤ 3) alloys is found to be accompanied by high jumps in the temperature dependences of the linear thermal expansion. The relative change in the linear sizes of these alloys at the martensitic transformation is 1.5 × 10-3. There are no anomalies in the magnetic-ordering temperature range in the temperature dependences of the coefficient of linear thermal expansion. The differences in the behavior of linear thermal expansion at the martensitic transformation in Ni51-xMn36 + xSn13 (0 ≤ x ≤ 3) and Ni47Mn40Sn13( x = 4) alloys have been established.

Rapid Mapping of Lithiation Dynamics in Transition Metal Oxide Particles with Operando X-ray Absorption Spectroscopy

Science.gov (United States)

Nowack, Lea; Grolimund, Daniel; Samson, Vallerie; Marone, Federica; Wood, Vanessa

2016-02-01

Since the commercialization of lithium ion batteries (LIBs), layered transition metal oxides (LiMO2, where M = Co, Mn, Ni, or mixtures thereof) have been materials of choice for LIB cathodes. During cycling, the transition metals change their oxidation states, an effect that can be tracked by detecting energy shifts in the X-ray absorption near edge structure (XANES) spectrum. X-ray absorption spectroscopy (XAS) can therefore be used to visualize and quantify lithiation kinetics in transition metal oxide cathodes; however, in-situ measurements are often constrained by temporal resolution and X-ray dose, necessitating compromises in the electrochemistry cycling conditions used or the materials examined. We report a combined approach to reduce measurement time and X-ray exposure for operando XAS studies of lithium ion batteries. A highly discretized energy resolution coupled with advanced post-processing enables rapid yet reliable identification of the oxidation state. A full-field microscopy setup provides sub-particle resolution over a large area of battery electrode, enabling the oxidation state within many transition metal oxide particles to be tracked simultaneously. Here, we apply this approach to gain insights into the lithiation kinetics of a commercial, mixed-metal oxide cathode material, nickel cobalt aluminium oxide (NCA), during (dis)charge and its degradation during overcharge.

Magnetic properties of NiMn2O4−δ (nickel manganite): Multiple magnetic phase transitions and exchange bias effect

International Nuclear Information System (INIS)

Tadic, Marin; Savic, S.M.; Jaglicic, Z.; Vojisavljevic, K.; Radojkovic, A.; Prsic, S.; Nikolic, Dobrica

2014-01-01

Highlights: • We have successfully synthesized NiMn 2 O 4−δ sample by complex polymerization synthesis. • Magnetic measurements reveal complex properties and triple magnetic phase transitions. • Magnetic measurements of M(H) show hysteretic behavior below 120 K. • Hysteresis properties after cooling of the sample in magnetic field show exchange bias effect. -- Abstract: We present magnetic properties of NiMn 2 O 4−δ (nickel manganite) which was synthesized by complex polymerization synthesis method followed by successive heat treatment and final calcinations in air at 1200 °C. The sample was characterized by using X-ray powder diffractometer (XRPD), scanning electron microscopy (SEM), field-emission scanning electron microscopy (FE-SEM) and superconducting quantum interference device (SQUID) magnetometer. The XRPD and FE-SEM studies revealed NiMn 2 O 4−δ phase and good crystallinity of particles. No other impurities have been observed by XRPD. The magnetic properties of the sample have been studied by measuring the temperature and field dependence of magnetization. Magnetic measurements of M(T) reveal rather complex magnetic properties and multiple magnetic phase transitions. We show three magnetic phase transitions with transition temperatures at T M1 = 35 K (long-range antiferromagnetic transition), T M2 = 101 K (antiferromagnetic-type transition) and T M3 = 120 K (ferromagnetic-like transition). We found that the T M1 transition is strongly dependent on the strength of the applied magnetic field (T M1 decreases with increasing applied field) whereas the T M3 is field independent. Otherwise, the T M2 maximum almost disappears in higher applied magnetic fields (H = 1 kOe and 10 kOe). Magnetic measurements of M(H) show hysteretic behavior below T M3 . Moreover, hysteresis properties measured after cooling of the sample in magnetic field of 10 kOe show exchange bias effect with an exchange bias field |H EB |=196 Oe. In summary, the properties that

Martensitic transition near room temperature and the temperature- and magnetic-field-induced multifunctional properties of Ni49CuMn34In16 alloy

Science.gov (United States)

Sharma, V. K.; Chattopadhyay, M. K.; Khandelwal, A.; Roy, S. B.

2010-11-01

A near room-temperature martensitic transition is observed in the ferromagnetic austenite state of Ni50Mn34In16 alloy with 2% Cu substitution at the Ni site. Application of magnetic field in the martensite state induces a reverse martensitic transition in this alloy. dc magnetization, magnetoresistance and strain measurements in this alloy reveal that associated with this martensitic transition there exist a large magnetocaloric effect, a large magnetoresitance and a magnetic-field temperature-induced strain. This NiMnIn alloy system thus is an example of an emerging class of magnetic materials whose physical properties can be tuned by suitable chemical substitutions, to achieve magnetic-field and temperature-induced multifunctional properties at and around room temperature

Solution-combustion synthesized nickel-substituted spinel cathode materials (LiNixMn2-xO4; 0≤x≤0.2) for lithium ion battery: enhancing energy storage, capacity retention, and lithium ion transport

CSIR Research Space (South Africa)

Kebede, MA

2014-01-01

Full Text Available Spherically shaped Ni-substituted LiNi(subx)Mn(sub2-x)O(sub4) (x=0, 0.1, 0.2) spinel cathode materials for lithium ion battery with high first cycle discharge capacity and remarkable cycling performance were synthesized using the solution...

Lithium ion batteries based on nanoporous silicon

Science.gov (United States)

Tolbert, Sarah H.; Nemanick, Eric J.; Kang, Chris Byung-Hwa

2015-09-22

A lithium ion battery that incorporates an anode formed from a Group IV semiconductor material such as porous silicon is disclosed. The battery includes a cathode, and an anode comprising porous silicon. In some embodiments, the anode is present in the form of a nanowire, a film, or a powder, the porous silicon having a pore diameters within the range between 2 nm and 100 nm and an average wall thickness of within the range between 1 nm and 100 nm. The lithium ion battery further includes, in some embodiments, a non-aqueous lithium containing electrolyte. Lithium ion batteries incorporating a porous silicon anode demonstrate have high, stable lithium alloying capacity over many cycles.

Resonant Ni and Fe KLL Auger spectra photoexcited from NiFe alloys

International Nuclear Information System (INIS)

Koever, L.; Cserny, I.; Berenyi, Z.; Egri, S.; Novak, M.

2005-01-01

Complete text of publication follows. KLL Auger spectra of 3d transition metal atoms in solid environment, measured using high energy resolution, give an insight into the details of the local electronic structure surrounding the particular atoms emitting the signal Auger electrons. Fine tuning the energy of the exciting monochromatic photons across the K-absorption edge, features characteristic to resonant phenomena can be identified in the spectra. The shapes of the resonantly photoexcited KLL Auger spectra induced from 3d transition metals and alloys are well interpreted by the single step model of the Auger process, based on the resonant scattering theory. The peak shapes are strongly influenced by the 4p partial density of unoccupied electronic states around the excited atom. High energy resolution studies of KLL Auger spectra of 3d transition metals using laboratory X-ray sources, however, request very demanding experiments and yield spectra of limited statistical quality making the evaluation of the fine details in the spectra difficult. The Tunable High Energy XPS (THE- XPS) instrument at BW2 offers optimum photon x and energy resolution for spectroscopy of deep core Auger transitions. For the present measurements high purity polycrystalline Ni and Fe sheets as well as NiFe alloy samples of different compositions (Ni 80 Fe 20 , Ni 50 Fe 50 , Ni 20 Fe 80 ) were used. The surfaces of the samples were cleaned by in-situ argon ion sputtering. The measurements of the Ni and Fe KL 23 L 23 Auger spectra of the metal and alloy samples were performed with the THE-XPS instrument using high electron energy resolution (0.2 eV). In Fig.1, the measured Fe KL 23 L 23 spectrum, photoexcited at the Fe K absorption edge from Fe metal, is compared with the respective spectrum excited from a Ni 50 Fe 50 alloy. A significant broadening of the 1 D 2 peak and an enhancement of the spectral intensity at the low energy loss part of this peak observed in the alloy sample, while the

Quantitative analysis of Ni2+/Ni3+ in Li[NixMnyCoz]O2 cathode materials: Non-linear least-squares fitting of XPS spectra

Science.gov (United States)

Fu, Zewei; Hu, Juntao; Hu, Wenlong; Yang, Shiyu; Luo, Yunfeng

2018-05-01

Quantitative analysis of Ni2+/Ni3+ using X-ray photoelectron spectroscopy (XPS) is important for evaluating the crystal structure and electrochemical performance of Lithium-nickel-cobalt-manganese oxide (Li[NixMnyCoz]O2, NMC). However, quantitative analysis based on Gaussian/Lorentzian (G/L) peak fitting suffers from the challenges of reproducibility and effectiveness. In this study, the Ni2+ and Ni3+ standard samples and a series of NMC samples with different Ni doping levels were synthesized. The Ni2+/Ni3+ ratios in NMC were quantitatively analyzed by non-linear least-squares fitting (NLLSF). Two Ni 2p overall spectra of synthesized Li [Ni0.33Mn0.33Co0.33]O2(NMC111) and bulk LiNiO2 were used as the Ni2+ and Ni3+ reference standards. Compared to G/L peak fitting, the fitting parameters required no adjustment, meaning that the spectral fitting process was free from operator dependence and the reproducibility was improved. Comparison of residual standard deviation (STD) showed that the fitting quality of NLLSF was superior to that of G/L peaks fitting. Overall, these findings confirmed the reproducibility and effectiveness of the NLLSF method in XPS quantitative analysis of Ni2+/Ni3+ ratio in Li[NixMnyCoz]O2 cathode materials.

A holistic aging model for Li(NiMnCo)O2 based 18650 lithium-ion batteries

Science.gov (United States)

Schmalstieg, Johannes; Käbitz, Stefan; Ecker, Madeleine; Sauer, Dirk Uwe

2014-07-01

Knowledge on lithium-ion battery aging and lifetime estimation is a fundamental aspect for successful market introduction in high-priced goods like electric mobility. This paper illustrates the parameterization of a holistic aging model from accelerated aging tests. More than 60 cells of the same type are tested to analyze different impact factors. In calendar aging tests three temperatures and various SOC are applied to the batteries. For cycle aging tests especially different cycle depths and mean SOC are taken into account. Capacity loss and resistance increase are monitored as functions of time and charge throughput during the tests. From these data physical based functions are obtained, giving a mathematical description of aging. To calculate the stress factors like temperature or voltage, an impedance based electric-thermal model is coupled to the aging model. The model accepts power and current profiles as input, furthermore an ambient air temperature profile can be applied. Various drive cycles and battery management strategies can be tested and optimized using the lifetime prognosis of this tool. With the validation based on different realistic driving profiles and temperatures, a robust foundation is provided.

Monolithic lithium-based aerogels via dispersed inorganic sol-gel method

International Nuclear Information System (INIS)

Xiao Shufang; Zhou Bin; Du Ai; Xu Xiang; Yang Xiaoyun; Shen Jun; Wu Guangming; Zhang Zhihua; Wan Huijun

2008-01-01

Monolithic lithium-based aerogels were prepared by poly acrylic acid (PAA) and propylene oxide (PO) via the dispersed inorganic sol-gel method and drying with CO 2 supercritical fluid dry process. The density of the prepared sample is about 150 g/m 3 . The microstructure of the lithium-based aerogels was characterized by TEM, IR, XPS and BET. The results show that the material mainly contains Li, C and O element s. BET surface area is up to 18.9 m 2 /g. (authors)

Effect of temperature and dissolved hydrogen on oxide films formed on Ni and Alloy 182 in simulated PWR water

International Nuclear Information System (INIS)

Mendonça, R.; Bosch, R.-W.; Van Renterghem, W.; Vankeerberghen, M.; Araújo Figueiredo, C. de

2016-01-01

Alloy 182 is a nickel-based weld metal, which is susceptible to stress corrosion cracking in PWR primary water. It shows a peak in SCC susceptibility at a certain temperature and hydrogen concentration. This peak is related to the electrochemical condition where the Ni to NiO transition takes place. One hypothesis is that the oxide layer at this condition is not properly developed and so the material is not optimally protected against SCC. Therefore the oxide layer formed on Alloy 182 is investigated as a function of the dissolved hydrogen concentration and temperature around this Ni/NiO transition. Exposure tests were performed with Alloy 182 and Ni coupons in a PWR environment at temperatures between 300 °C and 345 °C and dissolved hydrogen concentration between 5 and 35 cc (STP)H 2 /kg. Post-test analysis of the formed oxide layers were carried out by SEM, EDS and XPS. The exposure tests with Ni coupons showed that the Ni/NiO transition curve is at a higher temperature than the curve based on thermodynamic calculations. The exposure tests with Alloy 182 showed that oxide layers were present at all temperatures, but that the morphology changed from spinel crystals to needle like oxides when the Ni/NiO transition curve was approached. Oxide layers were present below the Ni/NiO transition curve i.e. when the Ni coupon was still free of oxides. In addition an evolved slip dissolution model was proposed that could explain the observed experimental results and the peak in SCC susceptibility for Ni-based alloys around the Ni/NiO transition. - Highlights: • Exposure tests with Ni-coupons showed that the Ni/NiO transition curve shifted to more oxidizing conditions. • The Ni specimens tested in PWR water were free of oxides at all temperatures. • The exposure tests with Alloy 182 showed that oxide layers were present at all temperatures. • The Alloy 182 surface morphology changed from spinel crystals to needle like oxides when the Ni/NiO curve was approached

Effect of temperature and dissolved hydrogen on oxide films formed on Ni and Alloy 182 in simulated PWR water

Energy Technology Data Exchange (ETDEWEB)

Mendonça, R. [CAPES Foundation, Ministry of Education, Brasilia (Brazil); Bosch, R.-W., E-mail: rbosch@sckcen.be [SCK-CEN, Boeretang 200, 2400 Mol (Belgium); Van Renterghem, W.; Vankeerberghen, M. [SCK-CEN, Boeretang 200, 2400 Mol (Belgium); Araújo Figueiredo, C. de [CDTN/CNEN, Av. Antônio Carlos 6627, 31270-901 Belo Horizonte, MG (Brazil)

2016-08-15

Alloy 182 is a nickel-based weld metal, which is susceptible to stress corrosion cracking in PWR primary water. It shows a peak in SCC susceptibility at a certain temperature and hydrogen concentration. This peak is related to the electrochemical condition where the Ni to NiO transition takes place. One hypothesis is that the oxide layer at this condition is not properly developed and so the material is not optimally protected against SCC. Therefore the oxide layer formed on Alloy 182 is investigated as a function of the dissolved hydrogen concentration and temperature around this Ni/NiO transition. Exposure tests were performed with Alloy 182 and Ni coupons in a PWR environment at temperatures between 300 °C and 345 °C and dissolved hydrogen concentration between 5 and 35 cc (STP)H{sub 2}/kg. Post-test analysis of the formed oxide layers were carried out by SEM, EDS and XPS. The exposure tests with Ni coupons showed that the Ni/NiO transition curve is at a higher temperature than the curve based on thermodynamic calculations. The exposure tests with Alloy 182 showed that oxide layers were present at all temperatures, but that the morphology changed from spinel crystals to needle like oxides when the Ni/NiO transition curve was approached. Oxide layers were present below the Ni/NiO transition curve i.e. when the Ni coupon was still free of oxides. In addition an evolved slip dissolution model was proposed that could explain the observed experimental results and the peak in SCC susceptibility for Ni-based alloys around the Ni/NiO transition. - Highlights: • Exposure tests with Ni-coupons showed that the Ni/NiO transition curve shifted to more oxidizing conditions. • The Ni specimens tested in PWR water were free of oxides at all temperatures. • The exposure tests with Alloy 182 showed that oxide layers were present at all temperatures. • The Alloy 182 surface morphology changed from spinel crystals to needle like oxides when the Ni/NiO curve was

Surfactant-assisted ultrasonic spray pyrolysis of nickel oxide and lithium-doped nickel oxide thin films, toward electrochromic applications

Energy Technology Data Exchange (ETDEWEB)

Denayer, Jessica [Group of Research in Energy and Environment for MATerials (GREENMAT), University of Liège, allée de la chimie 3, 4000 Liège (Belgium); Bister, Geoffroy [Environmental and Material Research Association (CRIBC-INISMa), avenue gouverneur cornez 4, 7000 Mons (Belgium); Simonis, Priscilla [Laboratory LPS, University of Namur, rue de bruxelles 61, 5000 Namur (Belgium); Colson, Pierre; Maho, Anthony [Group of Research in Energy and Environment for MATerials (GREENMAT), University of Liège, allée de la chimie 3, 4000 Liège (Belgium); Aubry, Philippe [Environmental and Material Research Association (CRIBC-INISMa), avenue gouverneur cornez 4, 7000 Mons (Belgium); Vertruyen, Bénédicte [Group of Research in Energy and Environment for MATerials (GREENMAT), University of Liège, allée de la chimie 3, 4000 Liège (Belgium); Henrist, Catherine, E-mail: catherine.henrist@ulg.ac.be [Group of Research in Energy and Environment for MATerials (GREENMAT), University of Liège, allée de la chimie 3, 4000 Liège (Belgium); Lardot, Véronique; Cambier, Francis [Environmental and Material Research Association (CRIBC-INISMa), avenue gouverneur cornez 4, 7000 Mons (Belgium); Cloots, Rudi [Group of Research in Energy and Environment for MATerials (GREENMAT), University of Liège, allée de la chimie 3, 4000 Liège (Belgium)

2014-12-01

Highlights: • Surfactant-assisted USP: a novel and low cost process to obtain high quality nickel oxide films, with or without lithium dopant. • Increased uniformity and reduced light scattering thanks to the addition of a surfactant. • Improved electrochromic performance (coloration efficiency and contrast) for lithium-doped films by comparison with the undoped NiO film. - Abstract: Lithium-doped nickel oxide and undoped nickel oxide thin films have been deposited on FTO/glass substrates by a surfactant-assisted ultrasonic spray pyrolysis. The addition of polyethylene glycol in the sprayed solution has led to improved uniformity and reduced light scattering compared to films made without surfactant. Furthermore, the presence of lithium ions in NiO films has resulted in improved electrochromic performances (coloration contrast and efficiency), but with a slight decrease of the electrochromic switching kinetics.

Dependence of the constitution, microstructure and electrochemical behaviour of magnetron sputtered Li-Ni-Mn-Co-O thin film cathodes for lithium-ion batteries on the working gas pressure and annealing conditions

International Nuclear Information System (INIS)

Strafela, Marc; Fischer, Julian; Leiste, Harald; Rinke, Monika; Bergfeldt, Thomas; Seifert, Hans Juergen; Ulrich, Sven; Music, Denis; Chang, Keke; Schneider, Jochen

2017-01-01

Li(Ni 1/3 Mn 1/3 Co 1/3 )O 2 as a cathode material for lithium ion batteries shows good thermal stability, high reversible capacity (290 mAh g -1 ), good rate capability and better results in terms of environmental friendliness. In this paper thin film cathodes in the material system Li-Ni-Mn-Co-O were deposited onto silicon and stainless steel substrates, by non-reactive r.f. magnetron sputtering from a ceramic Li 1.18 (Ni 0.39 Mn 0.19 Co 0.35 )O 1.97 target at various argon working gas pressures between 0.2 Pa and 20 Pa. A comprehensive study on the composition and microstructure was carried out. The results showed that the elemental composition varies depending on argon working gas pressure. The elemental composition was determined by inductively coupled plasma optical emission spectroscopy in combination with carrier gas hot extraction. The films showed different grain orientations depending argon working gas pressures. The degree of cation order in the lattice structure of the films deposited at 0.5 Pa and 7 Pa argon working gas pressure, was increased by annealing in an argon/oxygen atmosphere at different pressures for one hour. The microstructure of the films varies with annealing gas pressure and is characterized using X-ray diffraction and unpolarized micro-Raman spectroscopy at room temperature. Electrochemical characterization of as-deposited and annealed films was carried out by galvanostatic cycling in Li-Ni-Mn-Co-O half-cells against metallic lithium. Correlations between process parameters, constitution, microstructure and electrochemical behaviour are discussed in detail.

Charge-compensation in 3d-transition-metal-oxide intercalation cathodes through the generation of localized electron holes on oxygen.

Science.gov (United States)

Luo, Kun; Roberts, Matthew R; Hao, Rong; Guerrini, Niccoló; Pickup, David M; Liu, Yi-Sheng; Edström, Kristina; Guo, Jinghua; Chadwick, Alan V; Duda, Laurent C; Bruce, Peter G

2016-07-01

During the charging and discharging of lithium-ion-battery cathodes through the de- and reintercalation of lithium ions, electroneutrality is maintained by transition-metal redox chemistry, which limits the charge that can be stored. However, for some transition-metal oxides this limit can be broken and oxygen loss and/or oxygen redox reactions have been proposed to explain the phenomenon. We present operando mass spectrometry of (18)O-labelled Li1.2[Ni0.13(2+)Co0.13(3+)Mn0.54(4+)]O2, which demonstrates that oxygen is extracted from the lattice on charging a Li1.2[Ni0.13(2+)Co0.13(3+)Mn0.54(4+)]O2 cathode, although we detected no O2 evolution. Combined soft X-ray absorption spectroscopy, resonant inelastic X-ray scattering spectroscopy, X-ray absorption near edge structure spectroscopy and Raman spectroscopy demonstrates that, in addition to oxygen loss, Li(+) removal is charge compensated by the formation of localized electron holes on O atoms coordinated by Mn(4+) and Li(+) ions, which serve to promote the localization, and not the formation, of true O2(2-) (peroxide, O-O ~1.45 Å) species. The quantity of charge compensated by oxygen removal and by the formation of electron holes on the O atoms is estimated, and for the case described here the latter dominates.

Neutronics Evaluation of Lithium-Based Ternary Alloys in IFE Blankets

Energy Technology Data Exchange (ETDEWEB)

Jolodosky, A. [Univ. of California, Berkeley, CA (United States); Fratoni, M. [Univ. of California, Berkeley, CA (United States)

2015-09-22

, low electrical conductivity and therefore low MHD pressure drop, low chemical reactivity, and extremely low tritium inventory; the addition of sodium (FLiNaBe) has been considered because it retains the properties of FliBe but also lowers the melting point. Although many of these blanket concepts are promising, challenges still remain. The limited amount of beryllium available poses a problem for ceramic breeders such as the HCPB. FLiBe and FLiNaBe are highly viscous and have a low thermal conductivity. Lithium lead possesses a poor thermal conductivity which can cause problems in both DCLL and LiPb blankets. Additionally, the tritium permeation from these two blankets into plant components can be a problem and must be reduced. Consequently, Lawrence Livermore National Laboratory (LLNL) is attempting to develop a lithium-based alloy—most likely a ternary alloy—which maintains the beneficial properties of lithium (e.g. high tritium breeding and solubility) while reducing overall flammability concerns for use in the blanket of an inertial fusion energy (IFE) power plant. The LLNL concept employs inertial confinement fusion (ICF) through the use of lasers aimed at an indirect-driven target composed of deuterium-tritium fuel. The fusion driver/target design implements the same physics currently experimented at the National Ignition Facility (NIF). The plant uses lithium in both the primary coolant and blanket; therefore, lithium-related hazards are of primary concern. Although reducing chemical reactivity is the primary motivation for the development of new lithium alloys, the successful candidates will have to guarantee acceptable performance in all their functions. The scope of this study is to evaluate the neutronics performance of a large number of lithium-based alloys in the blanket of the IFE engine and assess their properties upon activation. This manuscript is organized as follows: Section 12 presents the models and methodologies used for the analysis; Section

Nitrile functionalized silyl ether with dissolved LiTFSI as new electrolyte solvent for lithium-ion batteries

International Nuclear Information System (INIS)

Pohl, Benjamin; Grünebaum, Mariano; Drews, Mathias; Passerini, Stefano; Winter, Martin; Wiemhöfer, Hans‑Dieter

2015-01-01

Highlights: • A new electrolyte based on a nitrile-silyl ether solvent and LiTFSI as lithium salt was successfully tested. • This electrolyte shows higher ionic conductivities as compared to earlier published silicon based solvents. • Due to the absence of ether groups, the electrochemical stability is extended to 5.4 V vs. Li/Li + . • With LiTFSI, the electrolyte can be cycled up to 4.15 V vs. Li/Li + without causing anodic aluminum dissolution. - Abstract: 3-((Trimethylsilyl) oxy) propionitrile is introduced as non-volatile solvent for lithium-ion battery electrolytes using LiTFSI as lithium salt. The thermal and chemical stability of the electrolytes offer an enhanced safety as compared to conventional volatile carbonate electrolytes. In cell tests, the investigated LiTFSI nitrile silyl ether electrolyte shows compatibility with LiFePO 4 , LiNi 0.33 Mn 0.33 Co 0.33 O 2 and graphite active materials.

Fine-structure energy levels, oscillator strengths and transition probabilities in Ni XVI

International Nuclear Information System (INIS)

Deb, N.C.; Msezane, A.Z.

2001-01-01

Fine-structure energy levels relative to the ground state, oscillator strengths and transition probabilities for transitions among the lowest 40 fine-structure levels belonging to the configurations 3s 2 3p, 3s3p 2 , 3s 2 3d, 3p 3 and 3s3p3d of Ni XVI are calculated using a large scale CI in program CIV3 of Hibbert. Relativistic effects are included through the Breit-Pauli approximation via spin-orbit, spin-other-orbit, spin-spin, Darwin and mass correction terms. The existing discrepancies between the calculated and measured values for many of the relative energy positions are resolved in the present calculation which yields excellent agreement with measurement. Also, many of our oscillator strengths for allowed and intercombination transitions are in very good agreement with the recommended data by the National Institute of Standard and Technology (NIST). (orig.)

High-flux neutron source based on a liquid-lithium target

Science.gov (United States)

Halfon, S.; Feinberg, G.; Paul, M.; Arenshtam, A.; Berkovits, D.; Kijel, D.; Nagler, A.; Eliyahu, I.; Silverman, I.

2013-04-01

A prototype compact Liquid Lithium Target (LiLiT), able to constitute an accelerator-based intense neutron source, was built. The neutron source is intended for nuclear astrophysical research, boron neutron capture therapy (BNCT) in hospitals and material studies for fusion reactors. The LiLiT setup is presently being commissioned at Soreq Nuclear research Center (SNRC). The lithium target will produce neutrons through the 7Li(p,n)7Be reaction and it will overcome the major problem of removing the thermal power generated by a high-intensity proton beam, necessary for intense neutron flux for the above applications. The liquid-lithium loop of LiLiT is designed to generate a stable lithium jet at high velocity on a concave supporting wall with free surface toward the incident proton beam (up to 10 kW). During off-line tests, liquid lithium was flown through the loop and generated a stable jet at velocity higher than 5 m/s on the concave supporting wall. The target is now under extensive test program using a high-power electron-gun. Up to 2 kW electron beam was applied on the lithium flow at velocity of 4 m/s without any flow instabilities or excessive evaporation. High-intensity proton beam irradiation will take place at SARAF (Soreq Applied Research Accelerator Facility) superconducting linear accelerator currently in commissioning at SNRC.

CLASSICAL AREAS OF PHENOMENOLOGY: First-principles calculations for the elastic properties of Ni-base model superalloys: Ni/Ni3Al multilayers

Science.gov (United States)

Wang, Yun-Jiang; Wang, Chong-Yu

2009-10-01

A model system consisting of Ni[001](100)/Ni3Al[001](100) multi-layers are studied using the density functional theory in order to explore the elastic properties of single crystal Ni-based superalloys. Simulation results are consistent with the experimental observation that rafted Ni-base superalloys virtually possess a cubic symmetry. The convergence of the elastic properties with respect to the thickness of the multilayers are tested by a series of multilayers from 2γ'+2γ to 10γ'+10γ atomic layers. The elastic properties are found to vary little with the increase of the multilayer's thickness. A Ni/Ni3Al multilayer with 10γ'+10γ atomic layers (3.54 nm) can be used to simulate the mechanical properties of Ni-base model superalloys. Our calculated elastic constants, bulk modulus, orientation-dependent shear modulus and Young's modulus, as well as the Zener anisotropy factor are all compatible with the measured results of Ni-base model superalloys R1 and the advanced commercial superalloys TMS-26, CMSX-4 at a low temperature. The mechanical properties as a function of the γ' phase volume fraction are calculated by varying the proportion of the γ and γ' phase in the multilayers. Besides, the mechanical properties of two-phase Ni/Ni3Al multilayer can be well predicted by the Voigt-Reuss-Hill rule of mixtures.

Bioleaching of valuable metals from spent lithium-ion mobile phone batteries using Aspergillus niger

Science.gov (United States)

Horeh, N. Bahaloo; Mousavi, S. M.; Shojaosadati, S. A.

2016-07-01

In this paper, a bio-hydrometallurgical route based on fungal activity of Aspergillus niger was evaluated for the detoxification and recovery of Cu, Li, Mn, Al, Co and Ni metals from spent lithium-ion phone mobile batteries under various conditions (one-step, two-step and spent medium bioleaching). The maximum recovery efficiency of 100% for Cu, 95% for Li, 70% for Mn, 65% for Al, 45% for Co, and 38% for Ni was obtained at a pulp density of 1% in spent medium bioleaching. The HPLC results indicated that citric acid in comparison with other detected organic acids (gluconic, oxalic and malic acid) had an important role in the effectiveness of bioleaching using A. niger. The results of FTIR, XRD and FE-SEM analysis of battery powder before and after bioleaching process confirmed that the fungal activities were quite effective. In addition, bioleaching achieved higher removal efficiency for heavy metals than the chemical leaching. This research demonstrated the great potential of bio-hydrometallurgical route to recover heavy metals from spent lithium-ion mobile phone batteries.

Site-specific transition metal occupation in multicomponent pyrophosphate for improved electrochemical and thermal properties in lithium battery cathodes: a combined experimental and theoretical study.

Science.gov (United States)

Shakoor, Rana A; Kim, Heejin; Cho, Woosuk; Lim, Soo Yeon; Song, Hannah; Lee, Jung Woo; Kang, Jeung Ku; Kim, Yong-Tae; Jung, Yousung; Choi, Jang Wook

2012-07-18

As an attempt to develop lithium ion batteries with excellent performance, which is desirable for a variety of applications including mobile electronics, electrical vehicles, and utility grids, the battery community has continuously pursued cathode materials that function at higher potentials with efficient kinetics for lithium insertion and extraction. By employing both experimental and theoretical tools, herein we report multicomponent pyrophosphate (Li(2)MP(2)O(7), M = Fe(1/3)Mn(1/3)Co(1/3)) cathode materials with novel and advantageous properties as compared to the single-component analogues and other multicomponent polyanions. Li(2)Fe(1/3)Mn(1/3)Co(1/3)P(2)O(7) is formed on the basis of a solid solution among the three individual transition-metal-based pyrophosphates. The unique crystal structure of pyrophosphate and the first principles calculations show that different transition metals have a tendency to preferentially occupy either octahedral or pyramidal sites, and this site-specific transition metal occupation leads to significant improvements in various battery properties: a single-phase mode for Li insertion/extraction, improved cell potentials for Fe(2+)/Fe(3+) (raised by 0.18 eV) and Co(2+)/Co(3+) (lowered by 0.26 eV), and increased activity for Mn(2+)/Mn(3+) with significantly reduced overpotential. We reveal that the favorable energy of transition metal mixing and the sequential redox reaction for each TM element with a sufficient redox gap is the underlying physical reason for the preferential single-phase mode of Li intercalation/deintercalation reaction in pyrophosphate, a general concept that can be applied to other multicomponent systems. Furthermore, an extremely small volume change of ~0.7% between the fully charged and discharged states and the significantly enhanced thermal stability are observed for the present material, the effects unseen in previous multicomponent battery materials.

Formulation, physicochemical characterization and stability study of lithium-loaded microemulsion system.

Science.gov (United States)

Mouri, Abdelkader; Legrand, Philippe; El Ghzaoui, Abdeslam; Dorandeu, Christophe; Maurel, Jean Claude; Devoisselle, Jean-Marie

2016-04-11

Lithium biocompatible microemulsion based on Peceol(®), lecithin, ethanol and water was studied in attempt to identify the optimal compositions in term of drug content, physicochemical properties and stability. Lithium solubilization in microemulsion was found to be compatible with a drug-surfactant binding model. Lithium ions were predominantly solubilized within lecithin head group altering significantly the interfacial properties of the system. Pseudo-ternary phase diagrams of drug free and drug loaded microemulsions were built at constant ethanol/lecithin weight ratio (40/60). Lithium loaded microemulsion has totally disappeared in the Peceol(®) rich part of phase diagram; critical fractions of lecithin and ethanol were required for the formation of stable microemulsion. The effect of lithium concentration on the properties and physical stability of microemulsions were studied using microscopy, Karl Fischer titrations, rheology analyses, conductivity measurements and centrifugation tests. The investigated microemulsions were found to be stable under accelerated storage conditions. The systems exhibited low viscosity and behaved as Newtonian fluid and no structural transition was shown. Copyright © 2016 Elsevier B.V. All rights reserved.

Synthesis of Li{sub 2}Si{sub 2}O{sub 5}-coated LiNi{sub 0.6}Co{sub 0.2}Mn{sub 0.2}O{sub 2} cathode materials with enhanced high-voltage electrochemical properties for lithium-ion batteries

Energy Technology Data Exchange (ETDEWEB)

Liu, Shengjie; Wu, Hao; Huang, Ling; Xiang, Mingwu; Liu, Heng; Zhang, Yun, E-mail: y_zhang@scu.edu.cn

2016-07-25

Ni-rich ternary layered oxides, (LiNi{sub x} [M]{sub 1−x}O{sub 2}, x ≥ 0.5, M = Co and Mn), have become one of the mainstream cathode materials for next-generation lithium-ion batteries due to their high capacity and cost efficiency compared with LiCoO{sub 2}. However, the high-voltage operation of the Ni-rich oxides (>4.3 V) required for high capacity is inevitably accompanied with a rapid capacity decay over numerous cycles. In this work, we reported a surface coating of LiNi{sub 0.6}Co{sub 0.2}Mn{sub 0.2}O{sub 2} with Li{sub 2}Si{sub 2}O{sub 5}via a facile and efficient synthetic approach, which involves the employment of silicic acid (H{sub 2}SiO{sub 3}) as remover to react with the surface residual lithium compounds (e.g. Li{sub 2}CO{sub 3} and LiOH) of LiNi{sub 0.6}Co{sub 0.2}Mn{sub 0.2}O{sub 2} and consequent formation of a robust and complete Li{sup +}-conductive Li{sub 2}Si{sub 2}O{sub 5} protective coating layer. The structure and morphology of the coated cathode materials are fully characterized by using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM) and scanning electron microscopy (SEM). Compared with the pristine LiNi{sub 0.6}Co{sub 0.2}Mn{sub 0.2}O{sub 2}, coating with the Li{sup +}-conductive Li{sub 2}Si{sub 2}O{sub 5} is found to be very effective for improving the rate capability of the LiNi{sub 0.6}Co{sub 0.2}Mn{sub 0.2}O{sub 2} when evaluated at a high cut-off voltage up to 4.5 V. Specifically, 1 wt. % H{sub 2}SiO{sub 3}-treated LiNi{sub 0.6}Co{sub 0.2}Mn{sub 0.2}O{sub 2} electrode exhibits high discharge specific capacities of 213.9 and 121.6 mAh g{sup −1} at 0.1 and 10 C, respectively, whereas the pristine electrode only shows 196.8 and 92.1 mAh g{sup −1}. Besides, the surface-modified LiNi{sub 0.6}Co{sub 0.2}Mn{sub 0.2}O{sub 2} electrode also manifests an enhanced long-term cycling stability (67% capacity retention after 200 cycles at 5 C), much better than the pristine

Features of Pd-Ni-Fe solder system for vacuum brazing of low alloy steels

International Nuclear Information System (INIS)

Radzievskij, V.N.; Kurochko, R.S.; Lotsmanov, S.N.; Rymar', V.I.

1975-01-01

The brazing solder of the Pd-Ni-Fe alloyed with copper and lithium, in order to decrease the melting point and provide for a better spreading, when soldered in vacuum ensures a uniform strength of soldered joints with the base metal of low-alloyed steels of 34KHNIM-type. The properties of low-alloyed steel joints brazed with the Pd-Ni-Fe-system solder little depend on the changes in the soldering parameters. The soldered joint keeps a homogeneous structure after all the stages of heat treatment (annealing, quenching and tempering)

Synthesis of LiNi0.65Co0.25Mn0.1O2 as cathode material for lithium-ion batteries by rheological phase method

International Nuclear Information System (INIS)

Cheng Cuixia; Tan Long; Hu Anzheng; Liu Haowen; Huang Xintang

2010-01-01

Research highlights: → In this paper, for the first time, rheological phase method, a simple and effective route, was applied to synthesis high capacity cathode material LiNi 0.65 Co 0.25 Mn 0.1 O 2 . → All of the results obtained by X-ray diffraction spectrometer, X-ray photoelectron spectrometer, charge-discharge tests and electrochemical impedance spectroscopy show that the rheological phase production have better properties than that of the report. - Abstract: Rheological phase (RP) method has been successfully applied to synthesize a promising cathode material LiNi 0.65 Co 0.25 Mn 0.1 O 2 . X-ray diffraction, X-ray photoelectron spectroscopy, inductively coupled plasma and transmission electron microscope are used to investigate the structure, composition and morphology, respectively. XRD result shows that the as-prepared powder has a layered α-NaFeO 2 structure. XPS pattern reveals that the Ni ions have valences of 2+ and 3+, and the Co and Mn are 3+, 4+, respectively. The electrode consisting of the obtained powder presents the better electrochemical properties, which is attributed to the fewer amounts of Ni 2+ ions and the smaller particles. All the results suggest that the rheological phase method is a promising technique for the preparation of LiNi 0.65 Co 0.25 Mn 0.1 O 2 cathode material of lithium-ion batteries.

Low temperature gaseous nitriding of Ni based superalloys

DEFF Research Database (Denmark)

Eliasen, K. M.; Christiansen, Thomas Lundin; Somers, Marcel A. J.

2010-01-01

In the present work the nitriding response of selected Ni based superalloys at low temperatures is addressed. The alloys investigated are nimonic series nos. 80, 90, 95 and 100 and nichrome (Ni/Cr......In the present work the nitriding response of selected Ni based superalloys at low temperatures is addressed. The alloys investigated are nimonic series nos. 80, 90, 95 and 100 and nichrome (Ni/Cr...

Improving the Electrochemical Performance of LiNi0.80Co0.15Al0.05O2 in Lithium Ion Batteries by LiAlO2 Surface Modification

Directory of Open Access Journals (Sweden)

Chunhua Song

2018-03-01

Full Text Available LiNi0.80Co0.15Al0.05O2 (NCA as a lithium ion battery cathode material has received attention for its highly specific capacity and excellent low temperature performance. However, the disadvantages of its high surface lithium compound residues and high pH value have influenced its processing performance and limited its application. This paper uses a facile method to modify NCA through LiAlO2 coating. The results showed that when the molar ratio of Al(NO33·9H2O and lithium compound residues at the surface of NCA cathode material was 0.25:1, the pH of the cathode material decreased from 12.70 to 11.80 and the surface lithium compound residues decreased from 3.99% to 1.48%. The NCA cell was charged and discharged for 100 cycles at 1 C in the voltage range of 3.0–4.3 V, to test the capacity retention of NCA. It was found to be as high as 94.67%, which was 5.36% higher than the control NCA cell. The discharge capacity of NCA-0.25-500 °C was 139.8 mAh/g even at 8 C rate, which was 15% higher than the raw NCA. Further research indicated that Al(NO33·9H2O reacted with the surface lithium compound residues of NCA and generated LiAlO2, which improved the NCA electrochemical performance.

Understanding Conversion-Type Electrodes for Lithium Rechargeable Batteries.

Science.gov (United States)

Yu, Seung-Ho; Feng, Xinran; Zhang, Na; Seok, Jeesoo; Abruña, Héctor D

2018-02-20

The need/desire to lower the consumption of fossil fuels and its environmental consequences has reached unprecedented levels in recent years. A global effort has been undertaken to develop advanced renewable energy generation and especially energy storage technologies, as they would enable a dramatic increase in the effective and efficient use of renewable (and often intermittent) energy sources. The development of electrical energy storage (EES) technologies with high energy and power densities, long life, low cost, and safe use represents a challenge from both the fundamental science and technological application points of view. While the advent and broad deployment of lithium-ion batteries (LIBs) has dramatically changed the EES landscape, their performance metrics need to be greatly enhanced to keep pace with the ever-increasing demands imposed by modern consumer electronics and especially the emerging automotive markets. Current battery technologies are mostly based on the use of a transition metal oxide cathode (e.g., LiCoO 2 , LiFePO 4 , or LiNiMnCoO 2 ) and a graphite anode, both of which depend on intercalation/insertion of lithium ions for operation. While the cathode material currently limits the battery capacity and overall energy density, there is a great deal of interest in the development of high-capacity cathode materials as well as anode materials. Conversion reaction materials have been identified/proposed as potentially high-energy-density alternatives to intercalation-based materials. However, conversion reaction materials react during lithiation to form entirely new products, often with dramatically changed structure and chemistry, by reaction mechanisms that are still not completely understood. This makes it difficult to clearly distinguish the limitations imposed by the mechanism and practical losses from initial particle morphology, synthetic approaches, and electrode preparations. Transition metal compounds such as transition metal oxides

Theoretical evaluation of high-energy lithium metal phosphate cathode materials in Li-ion batteries

Science.gov (United States)

Howard, Wilmont F.; Spotnitz, Robert M.

Lithium metal phosphates (olivines) are emerging as long-lived, safe cathode materials in Li-ion batteries. Nano-LiFePO 4 already appears in high-power applications, and LiMnPO 4 development is underway. Current and emerging Fe- and Mn-based intercalants, however, are low-energy producers compared to Ni and Co compounds. LiNiPO 4, a high voltage olivine, has the potential for superior energy output (>10.7 Wh in 18650 batteries), compared with commercial Li(Co,Ni)O 2 derivatives (up to 9.9 Wh). Speculative Co and Ni olivine cathode materials charged to above 4.5 V will require significant advances in electrolyte compositions and nanotechnology before commercialization. The major drivers toward 5 V battery chemistries are the inherent abuse tolerance of phosphates and the economic benefit of LiNiPO 4: it can produce 34% greater energy per dollar of cell material cost than LiAl 0.05Co 0.15Ni 0.8O 2, today's "standard" cathode intercalant in Li-ion batteries.

Electroplating lithium transition metal oxides

Science.gov (United States)

Zhang, Huigang; Ning, Hailong; Busbee, John; Shen, Zihan; Kiggins, Chadd; Hua, Yuyan; Eaves, Janna; Davis, Jerome; Shi, Tan; Shao, Yu-Tsun; Zuo, Jian-Min; Hong, Xuhao; Chan, Yanbin; Wang, Shuangbao; Wang, Peng; Sun, Pengcheng; Xu, Sheng; Liu, Jinyun; Braun, Paul V.

2017-01-01

Materials synthesis often provides opportunities for innovation. We demonstrate a general low-temperature (260°C) molten salt electrodeposition approach to directly electroplate the important lithium-ion (Li-ion) battery cathode materials LiCoO2, LiMn2O4, and Al-doped LiCoO2. The crystallinities and electrochemical capacities of the electroplated oxides are comparable to those of the powders synthesized at much higher temperatures (700° to 1000°C). This new growth method significantly broadens the scope of battery form factors and functionalities, enabling a variety of highly desirable battery properties, including high energy, high power, and unprecedented electrode flexibility. PMID:28508061

Effect of elevated lithium on the waterside corrosion of zircaloy-4: Experimental and predictive studies

International Nuclear Information System (INIS)

Pecheur, D.; Giordano, A.; Picard, E.; Billot, P.; Thomazet, J.

1997-01-01

Lithium and boron content in the coolant are known to influence the oxidation behaviour of the fuel cladding. Since new PWR operating conditions could consist in an increase of the lithium and the boron concentration in the coolant early in the cycle, a specific study has been conducted to analyze and to predict the effect of such new water chemistry conditions on the oxidation kinetics of the Zircaloy-4 material. Experimental studies have been performed in out-of-pile loop tests, under one and two phase flow heat transfer in various water chemistry conditions (0≤Li≤350 ppm, 0≤B≤1000 ppm, 0≤K≤56 ppm). A simulation of the effect of elevated lithium on the corrosion has been made using the semi-empirical COCHISE corrosion code. Under one phase flow heat transfer conditions, the addition of lithium hydroxide in the coolant increases the oxidation rate, essentially in the post-transition regime for low lithium levels (≤ 75 ppm) and immediately in the pre-transition phase for very high lithium level (350 ppm). Under two phase flow heat transfer, an enhancement of the corrosion is observed in the area of the rod submitted to boiling. Based on the out-of-pile loop test performed in presence of KOH instead of LiOH, such an enhancement of the corrosion appears to be due to a lithium enrichment in the oxide layer induced by boiling and not to a pH effect. The simulation of the increase of lithium content in the coolant from 2.2 to 3.5 ppm leads to an enhancement in corrosion rates which becomes only significant at high burn up. This predictive result of elevated lithium effect on corrosion is then compared with oxidation data derived from reactors operating under an elevated lithium regime. (author). 14 refs, 9 figs, 3 tabs

Effect of elevated lithium on the waterside corrosion of zircaloy-4: Experimental and predictive studies

Energy Technology Data Exchange (ETDEWEB)

Pecheur, D; Giordano, A; Picard, E; Billot, P [CEA Centre d` Etudes de Cadarache, 13 - Saint-Paul-lez-Durance (France); Thomazet, J [FRAMATOME, Nuclear Fuel Div., Lyon (France)

1997-02-01

Lithium and boron content in the coolant are known to influence the oxidation behaviour of the fuel cladding. Since new PWR operating conditions could consist in an increase of the lithium and the boron concentration in the coolant early in the cycle, a specific study has been conducted to analyze and to predict the effect of such new water chemistry conditions on the oxidation kinetics of the Zircaloy-4 material. Experimental studies have been performed in out-of-pile loop tests, under one and two phase flow heat transfer in various water chemistry conditions (0{<=}Li{<=}350 ppm, 0{<=}B{<=}1000 ppm, 0{<=}K{<=}56 ppm). A simulation of the effect of elevated lithium on the corrosion has been made using the semi-empirical COCHISE corrosion code. Under one phase flow heat transfer conditions, the addition of lithium hydroxide in the coolant increases the oxidation rate, essentially in the post-transition regime for low lithium levels ({<=} 75 ppm) and immediately in the pre-transition phase for very high lithium level (350 ppm). Under two phase flow heat transfer, an enhancement of the corrosion is observed in the area of the rod submitted to boiling. Based on the out-of-pile loop test performed in presence of KOH instead of LiOH, such an enhancement of the corrosion appears to be due to a lithium enrichment in the oxide layer induced by boiling and not to a pH effect. The simulation of the increase of lithium content in the coolant from 2.2 to 3.5 ppm leads to an enhancement in corrosion rates which becomes only significant at high burn up. This predictive result of elevated lithium effect on corrosion is then compared with oxidation data derived from reactors operating under an elevated lithium regime. (author). 14 refs, 9 figs, 3 tabs.

Oxygen, hydrogen, ethylene and CO 2 development in lithium-ion batteries

Science.gov (United States)

Holzapfel, M.; Würsig, A.; Scheifele, W.; Vetter, J.; Novák, P.

Gas evolution has been examined for different types of battery-related electrode materials via in situ differential electrochemical mass spectrometry (DEMS). Besides standard graphite also a novel silicon-based negative electrode was examined and it was shown that the evolution of hydrogen and ethylene is considerably reduced on this material compared to graphite. Oxygen evolution was proven to happen on the oxidative reaction of a Li 2O 2 electrode, besides a certain oxidation of the electrolyte. The 4.5 V plateau upon the oxidation of Li[Ni 0.2Li 0.2Mn 0.6]O 2 was likewise proven to be linked to oxygen evolution. Also in this case electrolyte oxidation was shown to be a side reaction. Layered positive electrode materials Li(Ni,Co,Al)O 2 and Li(Ni,Mn,Co)O 2 were also examined. The influence of different parameters on the CO 2 evolution in lithium-ion batteries was shown up. The amount of CO 2 formation is increased by high temperatures and cell voltages, while the addition of vinylene carbonate (VC) decreases it. Li(Ni,Mn,Co)O 2 shows much less CO 2 evolution than Li(Ni,Co,Al)O 2.

Magnetocaloric effect in Ni{sub 2}MnGa single crystal in the vicinity of the martensitic phase transition

Energy Technology Data Exchange (ETDEWEB)

Radelytskyi, I., E-mail: radel@ifpan.edu.pl [Institute of Physics, PAS, Al. Lotnikow 32/46, 02-668 Warsaw (Poland); Pękała, M. [Department of Chemistry, University of Warsaw, Al. Zwirki i Wigury 101, 02-089 Warsaw (Poland); Szymczak, R. [Institute of Physics, PAS, Al. Lotnikow 32/46, 02-668 Warsaw (Poland); Gawryluk, D.J. [Institute of Physics, PAS, Al. Lotnikow 32/46, 02-668 Warsaw (Poland); Laboratory for Scientific Developments and Novel Materials, Paul Scherrer Institut, 5232 Villigen PSI (Switzerland); Berkowski, M.; Fink-Finowicki, J. [Institute of Physics, PAS, Al. Lotnikow 32/46, 02-668 Warsaw (Poland); Diduszko, R. [Tele and Radio Research Institute, ul Ratuszowa 11, 03-450 Warsaw (Poland); Dyakonov, V.; Szymczak, H. [Institute of Physics, PAS, Al. Lotnikow 32/46, 02-668 Warsaw (Poland)

2017-05-15

The magnetocaloric effect in the vicinity of the martensitic transformation for a single crystalline alloy with a composition close to the stoichiometric Ni{sub 2}MnGa has been determined indirectly by M(T,H) magnetization measurements. It has an inverse character. The magnetocaloric parameters, i.e., the magnetic entropy change, refrigeration capacity and various hysteretic effects have been calculated from the M(T,H) dependences. Besides the martensitic transition a weak entirely separated intermartensitic transition was observed. These two successive magneto-structural transformations give contributions to the observed magnetocaloric effect. Unusual dependence of entropy change as a function of magnetic field has been explained as arising because of two different mechanisms. Additionally, to confirm that studied martensitic transformation is a first order phase transition electrical resistivity and thermoelectric power measurements have been performed. - Highlights: • Inverse magnetocaloric effect in Ni{sub 50.4}Mn{sub 24.9}Ga{sub 24.7} single crystal was measured. • The martensitic and separated intermartensitic transition were investigated. • Anisotropy of measured magnetocaloric effect was discussed.

Influence of electrode preparation on the electrochemical performance of LiNi0.8Co0.15Al0.05O2 composite electrodes for lithium-ion batteries

Science.gov (United States)

Tran, Hai Yen; Greco, Giorgia; Täubert, Corina; Wohlfahrt-Mehrens, Margret; Haselrieder, Wolfgang; Kwade, Arno

2012-07-01

The electrode manufacturing for lithium-ion batteries is based on a complex process chain with several influencing factors. A proper tailoring of the electrodes can greatly improve both the electrochemical performances and the energy density of the battery. In the present work, some significant parameters during the preparation of LiNi0.8Co0.15Al0.05O2-based cathodes were investigated. The active material was mixed with a PVDF-binder and two conductive additives in different ratios. The electrode thickness, the degree of compacting and the conductive agent type and mixing ratio have proven to have a strong impact on the electrochemical performances of the composite electrodes, especially on their behaviour at high C-rates. Further it has been shown that the compacting has an essential influence on the mechanical properties of NCA coatings, according to their total, ductile and elastic deformation behaviour.

Oxidation reaction of polyether-based material and its suppression in lithium rechargeable battery using 4 V class cathode, LiNi1/3Mn1/3Co1/3O2.

Science.gov (United States)

Kobayashi, Takeshi; Kobayashi, Yo; Tabuchi, Masato; Shono, Kumi; Ohno, Yasutaka; Mita, Yuichi; Miyashiro, Hajime

2013-12-11

The all solid-state lithium battery with polyether-based solid polymer electrolyte (SPE) is regarded as one of next-generation lithium batteries, and has potential for sufficient safety because of the flammable-electrolyte-free system. It has been believed that polyether-based SPE is oxidized at the polymer/electrode interface with 4 V class cathodes. Therefore, it has been used for electric devices such as organic transistor, and lithium battery under 3 V. We estimated decomposition reaction of polyether used as SPE of all solid-state lithium battery. We first identified the decomposed parts of polyether-based SPE and the conservation of most main chain framework, considering the results of SPE analysis after long cycle operations. The oxidation reaction was found to occur slightly at the ether bond in the main chain with the branched side chain. Moreover, we resolved the issue by introducing a self-sacrificing buffer layer at the interface. The introduction of sodium carboxymethyl cellulose (CMC) to the 4 V class cathode surface led to the suppression of SPE decomposition at the interface as a result of the preformation of a buffer layer from CMC, which was confirmed by the irreversible exothermic reaction during the first charge, using electrochemical calorimetry. The attained 1500 cycle operation is 1 order of magnitude longer than those of previously reported polymer systems, and compatible with those of reported commercial liquid systems. The above results indicate to proceed to an intensive research toward the realization of 4 V class "safe" lithium polymer batteries without flammable liquid electrolyte.

Energies of Electronic States of Ni (II) Ion in NiO-Al2O3 Catalyst Prepared by Impregnation

International Nuclear Information System (INIS)

Obadovic, D. Z.; Kiurski, J.; Marinkovic-Neducin, R. P.

2007-01-01

The behavior of NiO-Al2O3 catalysts is strongly dependent on the preparation method, as well as on pretreatment conditions. In the present work we investigated the influences of Ni(II) ion on NiO-Al2O3 catalysts properties due to the preparation by impregnation method. Based on experimental diffuse reflectance spectroscopy (DRS) data of electronic d-d transitions of Ni (II) promoter ion the energies of electronic states in spinel-like structure were calculated, and the most probable scheme of molecular orbital have been proposed

Shock-wave compression of lithium niobate from 2.4 to 44 GPa

International Nuclear Information System (INIS)

Stanton, P.L.; Graham, R.A.

1979-01-01

Shock compression of lithium niobate above the Hugoniot elastic limit (about 2.5 GPa) reveals a succession of unusual features. Just above the Hugoniot elastic limit, the shock velocity is observed to be well below the bulk sound speed, indicative of a drastic reduction of shear strength. The shock velocity is observed to increase with particle velocity at an unusually large rate due to the reduction of strength in a very stiff material and an anomalously large pressure derivative of the bulk modulus. This later behavior may be due to the effects of localized shock heating resulting from heterogeneous shear deformation in ferroelectrics like lithium niobate and lithium tantalate in which increases in temperature are shown to have a strong effect on bulk modulus. A shock-induced polymorphic phase transition occurs at 13.9 GPa. Above the transition point the slope of the Hugoniot curve relating shock velocity and particle velocity is unusually low, indicative of a broad mixed phase region of undetermined extent. Limited work is reported on the isomorphous crystal, lithium tantalate, which exhibits features similar to lithium niobate with a Hugoniot elastic limit of 4 GPa and a phase transition in the vicinity of 19 GPa

Microwave irradiation controls the manganese oxidation states of nanostructured (Li[Li0.2Mn0.52Ni0.13Co0.13Al0.02]O2) layered cathode materials for high-performance lithium ion batteries

CSIR Research Space (South Africa)

Jafta, CJ

2015-02-01

Full Text Available A hybrid synthesis procedure, combining microwave irradiation and conventional annealing process, is described for the preparation of lithium-rich manganese-rich cathode materials, Li[Li0.2Mn0.54Ni0.13Co0.13]O2 (LMNC) and its aluminum...

Silver effect of Co–Ni composite material on energy storage and structural behavior for Li-ion batteries

International Nuclear Information System (INIS)

Gnanamuthu, RM.; Prasanna, K.; Subburaj, T.; Jo, Yong Nam; Lee, Chang Woo

2013-01-01

Ag powder has been comparatively applied to the Co–Ni materials preparing by mixing method and the prepared electrodes were used as negative electrodes for Li-ion batteries applications. The prepared Co–Ni and Ag–Co–Ni with 10 wt.% of Ag composite electrodes are characterized by XRD, FE-SEM with EDX, impedance and electrochemical charge-discharge studies. These electrochemical studies are demonstrated at current rates of 0.1 C and 0.5 C between 0.01 and 2.0 V vs. Li/Li + . The porous Co–Ni and Ag–Co–Ni composite materials are electrochemically tested in lithium half cells. The porous Ag–Co–Ni composite material demonstrates that the initial and end of discharge capacity up to 20th cycles is, respectively, 860 and 715 mAh g −1 at 0.1 C rate maintaining at approximately 83%. The porous Ag–Co–Ni composite electrode may be a good candidate for high power lithium-ion batteries.

Performance of Lithium Polymer Cells with Polyacrylonitrile based Electrolyte

DEFF Research Database (Denmark)

Perera, Kumudu; Dissanayake, M.A.K.L.; Skaarup, Steen

2006-01-01

The performance of lithium polymer cells fabricated with Polyacrylonitrile (PAN) based electrolytes was studied using cycling voltammetry and continuous charge discharge cycling. The electrolytes consisted of PAN, ethylene carbonate (EC), propylene carbonate (PC) and lithium...... trifluoromethanesulfonate (LiCF3SO3 – LiTF). The polymer electrode material was polypyrrole (PPy) doped with dodecyl benzene sulfonate (DBS). The cells were of the form, Li / PAN : EC : PC : LiCF3SO3 / PPy : DBS. Polymer electrodes of three different thicknesses were studied using cycling at different scan rates. All cells...

Coupled Electronic and Magnetic Phase Transition in the Infinite-Layer Phase LaSrNiRuO4.

Science.gov (United States)

Patino, Midori Amano; Zeng, Dihao; Bower, Ryan; McGrady, John E; Hayward, Michael A

2016-09-06

Topochemical reduction of the ordered double perovskite LaSrNiRuO6 with CaH2 yields LaSrNiRuO4, an extended oxide phase containing infinite sheets of apex-linked, square-planar Ni(1+)O4 and Ru(2+)O4 units ordered in a checkerboard arrangement. At room temperature the localized Ni(1+) (d(9), S = (1)/2) and Ru(2+) (d(6), S = 1) centers behave paramagnetically. However, on cooling below 250 K the system undergoes a cooperative phase transition in which the nickel spins align ferromagnetically, while the ruthenium cations appear to undergo a change in spin configuration to a diamagnetic spin state. Features of the low-temperature crystal structure suggest a symmetry lowering Jahn-Teller distortion could be responsible for the observed diamagnetism of the ruthenium centers.

Controllable Fabrication of Amorphous Co-Ni Pyrophosphates for Tuning Electrochemical Performance in Supercapacitors.

Science.gov (United States)

Chen, Chen; Zhang, Ning; He, Yulu; Liang, Bo; Ma, Renzhi; Liu, Xiaohe

2016-09-07

Incorporation of two transition metals offers an effective method to enhance the electrochemical performance in supercapacitors for transition metal compound based electrodes. However, such a configuration is seldom concerned in pyrophosphates. Here, amorphous phase Co-Ni pyrophosphates are fabricated as electrodes in supercapacitors. Through controllably adjusting the ratios of Co and Ni as well as the calcination temperature, the electrochemical performance can be tuned. An optimized amorphous Ni-Co pyrophosphate exhibits much higher specific capacitance than monometallic Ni and Co pyrophosphates and shows excellent cycling ability. When employing Ni-Co pyrophosphates as positive electrode and activated carbon as a negative electrode, the fabricated asymmetric supercapacitor cell exhibits favorable capacitance and cycling ability. This study provides facile methods to improve the transition metal pyrophosphate electrodes for efficient electrodes in electrochemical energy storage devices.

Phase transition and magnetic properties of Mg-doped hexagonal close-packed Ni nanoparticles

International Nuclear Information System (INIS)

Yang Jinghai; Feng Bo; Liu Yang; Zhang Yongjun; Yang Lili; Wang Yaxin; Wei Maobin; Lang Jihui; Wang Dandan; Liu Xiaoyan

2008-01-01

Mg-doped Ni nanoparticles with the hexagonal close-packed (hcp) and face-centered cubic (fcc) structure have been synthesized by sol-gel method sintered at different temperatures in argon atmosphere. The sintering temperature played an important role in the control of the crystalline phase and the particle size. The pure hcp Mg-doped Ni nanoparticles with average particle size of 6.0 nm were obtained at 320 deg. C. The results indicated that the transition from the hcp to the fcc phase occurred in the temperature range between 320 deg. C and 450 deg. C. Moreover, the VSM results showed that the hcp Mg-doped Ni nanoparticles had unique ferromagnetic and superparamagnetic behavior. The unsaturation even at 5000 Oe is one of the superparamagnetic characteristics due to the small particle size. From the ZFC and FC curves, the blocking temperature T B of the hcp sample (6.0 nm) was estimated to be 10 K. The blocking temperature was related to the size of the magnetic particles and the magnetocrystalline anisotropy constant. By theoretical calculation, the deduced particle size was 6.59 nm for hcp Mg-doped Ni nanoparticles which was in agreement with the results of XRD and TEM

Effect of Fe substitution at the Ni and Mn sites on the magnetic properties of Ni50Mn35In15 Heusler alloys

International Nuclear Information System (INIS)

Halder, Madhumita; Suresh, K.G.

2015-01-01

The structural and magnetic properties of Ni 48 Fe 2 Mn 35 In 15 and Ni 50 Mn 34 FeIn 15 Heusler alloys have been investigated. At room temperature, Ni 48 Fe 2 Mn 35 In 15 has L2 1 cubic structure, whereas Ni 50 Mn 34 FeIn 15 shows a two-phase structure due to the martensitic transition. In the case of Ni 48 Fe 2 Mn 35 In 15 , there is only one magnetic transition at 316 K with no martensitic transition. However, in Ni 50 Mn 34 FeIn 15 , we observe the martensitic transition at about 280 K. The Curie temperatures for austenite and martensite phases are 314 and 200 K, respectively. The maximum magnetic entropy changes are found to be 5.5 and 4.5 J kg −1 K −1 for Ni 48 Fe 2 Mn 35 In 15 and Ni 50 Mn 34 FeIn 15 , respectively, for 50 kOe. Ni 50 Mn 34 FeIn 15 exhibits exchange bias behavior, with a bias field of 130 Oe at 5 K. Both the alloys satisfy the empirical relation between the martensitic transition and the valence electron concentration (e/a) ratio. - Highlights: • Structural and magnetic properties of Ni 48 Fe 2 Mn 35 In 15 and Ni 50 Mn 34 FeIn 15 Heusler alloys have been investigated. • Ni 48 Fe 2 Mn 35 In 15 does not undergo a martensitic transition, whereas Ni 50 Mn 34 FeIn 15 shows martensitic transition. • Ni 50 Mn 34 FeIn 15 alloy exhibits exchange bias behavior. • Both alloys satisfy the empirical relation between martensitic transition and valence electron concentration (e/a)

Ni2+-binding RNA motifs with an asymmetric purine-rich internal loop and a G-A base pair.

Science.gov (United States)

Hofmann, H P; Limmer, S; Hornung, V; Sprinzl, M

1997-01-01

RNA molecules with high affinity for immobilized Ni2+ were isolated from an RNA pool with 50 randomized positions by in vitro selection-amplification. The selected RNAs preferentially bind Ni2+ and Co2+ over other cations from first series transition metals. Conserved structure motifs, comprising about 15 nt, were identified that are likely to represent the Ni2+ binding sites. Two conserved motifs contain an asymmetric purine-rich internal loop and probably a mismatch G-A base pair. The structure of one of these motifs was studied with proton NMR spectroscopy and formation of the G-A pair at the junction of helix and internal loop was demonstrated. Using Ni2+ as a paramagnetic probe, a divalent metal ion binding site near this G-A base pair was identified. Ni2+ ions bound to this motif exert a specific stabilization effect. We propose that small asymmetric purine-rich loops that contain a G-A interaction may represent a divalent metal ion binding site in RNA. PMID:9409620

Dependence of the constitution, microstructure and electrochemical behaviour of magnetron sputtered Li-Ni-Mn-Co-O thin film cathodes for lithium-ion batteries on the working gas pressure and annealing conditions

Energy Technology Data Exchange (ETDEWEB)

Strafela, Marc; Fischer, Julian; Leiste, Harald; Rinke, Monika; Bergfeldt, Thomas; Seifert, Hans Juergen; Ulrich, Sven [Karlsruhe Institute of Technology (KIT), Karlsruhe (Germany). Inst. for Applied Materials (IAM); Music, Denis; Chang, Keke; Schneider, Jochen [RWTH Aachen Univ. (Germany). Materials Chemistry

2017-11-15

Li(Ni{sub 1/3}Mn{sub 1/3}Co{sub 1/3})O{sub 2} as a cathode material for lithium ion batteries shows good thermal stability, high reversible capacity (290 mAh g{sup -1}), good rate capability and better results in terms of environmental friendliness. In this paper thin film cathodes in the material system Li-Ni-Mn-Co-O were deposited onto silicon and stainless steel substrates, by non-reactive r.f. magnetron sputtering from a ceramic Li{sub 1.18}(Ni{sub 0.39}Mn{sub 0.19}Co{sub 0.35})O{sub 1.97} target at various argon working gas pressures between 0.2 Pa and 20 Pa. A comprehensive study on the composition and microstructure was carried out. The results showed that the elemental composition varies depending on argon working gas pressure. The elemental composition was determined by inductively coupled plasma optical emission spectroscopy in combination with carrier gas hot extraction. The films showed different grain orientations depending argon working gas pressures. The degree of cation order in the lattice structure of the films deposited at 0.5 Pa and 7 Pa argon working gas pressure, was increased by annealing in an argon/oxygen atmosphere at different pressures for one hour. The microstructure of the films varies with annealing gas pressure and is characterized using X-ray diffraction and unpolarized micro-Raman spectroscopy at room temperature. Electrochemical characterization of as-deposited and annealed films was carried out by galvanostatic cycling in Li-Ni-Mn-Co-O half-cells against metallic lithium. Correlations between process parameters, constitution, microstructure and electrochemical behaviour are discussed in detail.

Corrosion susceptibility study of candidate pin materials for ALTC (Active Lithium/Thionyl Chloride) batteries

Science.gov (United States)

Bovard, Francine S.; Cieslak, Wendy R.

1987-09-01

The corrosion susceptibilities of eight alternate battery pin material candidates for ALTC (Active Lithium/Thionyl Chloride) batteries in 1.5M LiAlCl4/SOCl2 electrolyte have been investigated using ampule exposure and electrochemical tests. The thermal expansion coefficients of these candidate materials are expected to match Sandia-developed Li-corrosion resistant glasses. The corrosion resistances of the candidate materials, which included three stainless steels (15-5 PH, 17-4 PH, and 446), three Fe-Ni glass sealing alloys (Kovar, Alloy 52, and Niromet 426), a Ni-based alloy (Hastelloy B-2) and a zirconium-based alloy (Zircaloy), were compared to the reference materials Ni and 316L SS. All of the candidate materials showed some evidence of corrosion and, therefore, did not perform as well as the reference materials. The Hastelloy B-2 and Zircaloy are clearly unacceptable materials for this application. Of the remaining alternate materials, the 446 SS and Alloy 52 are the most promising candidates.

High pressure phase transition in Zr–Ni binary system: A first principle study

Energy Technology Data Exchange (ETDEWEB)

Mukherjee, Debojyoti, E-mail: debojyoti@barc.gov.in; Sahoo, B.D.; Joshi, K.D.; Gupta, Satish C.

2015-11-05

Total energy calculations have been performed on zirconium–nickel (with 50% nickel by atom) binary system to examine its structural stability under high pressure. The evolutionary structure search method in conjunction with density functional theory based projector augmented wave (PAW) method suggested that at zero pressure an orthorhombic phase with space group symmetry Cmcm is the lowest enthalpy structure, in agreement with the experiments. Further, it has been predicted that upon compression at ∼10 GPa, this structure will transform to a lower symmetry triclinic phase (space group P-1) which will remain stable up to ∼50 GPa, the maximum pressure of the present calculations. To support the results of our static lattice calculations, we performed lattice dynamic calculations also on Cmcm and P-1 structures. Lattice dynamic calculations correctly showed that at ambient condition the Cmcm phase is dynamically stable. Further, these calculations carried around the Cmcm to P-1 transition pressure predicted that the Cmcm phase will become unstable dynamically due to failure of acoustic zone boundary phonons, suggesting that the Cmcm to P-1 transition is phonon driven. For P-1 phase our calculations showed that this structure is dynamically stable not only at high pressures but also at ambient condition, indicating that at pressure lower than 10 GPa this phase could be a metastable structure. Further, we have calculated the elastic constants for both the phase at various pressures. - Highlights: • Pressure induced phonon driven orthorhombic to triclinic phase transformations in Zr–Ni binary system at ∼10 GPa. • Elastic and lattice dynamic stability of orthorhombic and triclinic phase. • Exploitation of evolutionary structure searching method to explore high pressure phase of Zr–Ni material.

Characterization of positive electrode/electrolyte interphase in lithium batteries

Energy Technology Data Exchange (ETDEWEB)

Dupre, N.; Martin, J.F.; Soudan, P.; Guyomard, D. [Inst.des Materiaux Jean Rouxel, Nantes (France)

2008-07-01

Lithium batteries appear to be the most viable energy source for portable electronic devices because of their energy density. The solid electrolyte interphase (SEI) between the negative electrode and the electrolyte of a Li-ion battery monitors the overall battery behaviour in terms of irreversible capacity loss, charge transfer kinetics and storage properties. This paper reported on a study that examined the influence of the storage atmosphere and the formation of a protective surface layer on the electrochemical performance. The objective was to better understand the interfacial problems controlling the long term life duration and cyclability. The positive/electrolyte interphase evolution was followed upon aging/cycling using 7Li MAS NMR, XPS and impedance spectroscopy. This very novel and uncommon technique was used to characterize the growth and evolution of the surface of some electrode materials for lithium batteries, due to contact with the ambient atmosphere or electrolyte or along electrochemical cycling. LiFePO4 and LiMn0.5Ni0.5O2 were chosen for the studies because they are among the most promising candidates for positive electrodes for future lithium batteries. The reaction of LiMn0.5Ni0.5O2 with the ambient atmosphere or LiPF6 electrolyte is extremely fast and leads to an important amount of lithium-containing diamagnetic species. The NMR spectra provided valuable structural information on the interaction between the interphase and the active material after contact with electrolyte or along electrochemical cycling. MAS NMR was shown to be a very promising tool to monitor phenomena taking place at the interface between electrode and electrolyte in lithium batteries. The study showed the affect of the potential on the strength of the interaction between the surface layer and the active material and the partial removal of this layer along the electrochemical cycling. 11 refs.

Compatibility between vandium-base alloys and flowing lithium: Partitioning of hydrogen at elevated temperatures

International Nuclear Information System (INIS)

Hull, A.B.; Chopra, O.K.; Loomis, B.; Smith, D.

1989-12-01

A major concern in fusion reactor design is possible hydrogen-isotope-induced embrittlement of structural alloys in the neutron environment expected in these reactors. Hydrogen fractionation occurs between lithium and various refractory metals according to a temperature-dependent distribution coefficient, K H , that is defined as the ration of the hydrogen concentration in the metallic specimen to that in the liquid lithium. In the present work, K H was determined for pure vanadium and several binary and ternary alloys, and the commercial Vanstar 7. Hydrogen distribution studies were performed in an austenitic steel forced-circulation lithium loop. Equilibrium concentrations of hydrogen in vanadium-base alloys exposed to flowing lithium at temperatures of 350 to 550 degree C were measured by inert gas fusion techniques and residual gas analysis. Thermodynamic calculations are consistent with the effect of chromium and titanium in the alloys on the resultant hydrogen fractionation. Experimental and calculated results indicate that K H values are very low; i.e., the hydrogen concentrations in the lithium-equilibrated vanadium-base alloy specimens are about two orders of magnitude lower than those in the lithium. Because of this low distribution coefficient, embrittlement of vanadium alloys by hydrogen in lithium would not be expected. 15 refs., 5 figs., 4 tabs

Magnetocaloric effect in Heusler alloys Ni50Mn34In16 and Ni50Mn34Sn16

Science.gov (United States)

Sharma, V. K.; Chattopadhyay, M. K.; Kumar, Ravi; Ganguli, Tapas; Tiwari, Pragya; Roy, S. B.

2007-12-01

We present results of detailed ac susceptibility, magnetization and specific heat measurements in Heusler alloys Ni50Mn34In16 and Ni50Mn34Sn16. These alloys undergo a paramagnetic to ferromagnetic transition around 305 K, which is followed by a martensitic transition in the temperature regime around 220 K. Inside the martensite phase both the alloys show signatures of field-induced transition from martensite to austenite phase. Both field- and temperature-induced martensite-austenite transitions are relatively sharp in Ni50Mn34In16. We estimate the isothermal magnetic entropy change and adiabatic temperature change across the various phase transitions in these alloys and investigate the possible influence of these transitions on the estimated magnetocaloric effect. The sharp martensitic transition in Ni50Mn34In16 gives rise to a comparatively large inverse magnetocaloric effect across this transition. On the other hand the magnitudes of the conventional magnetocaloric effect associated with the paramagnetic to ferromagnetic transition are quite comparable in these alloys.

Single-ion triblock copolymer electrolytes based on poly(ethylene oxide) and methacrylic sulfonamide blocks for lithium metal batteries

Science.gov (United States)

Porcarelli, Luca; Aboudzadeh, M. Ali; Rubatat, Laurent; Nair, Jijeesh R.; Shaplov, Alexander S.; Gerbaldi, Claudio; Mecerreyes, David

2017-10-01

Single-ion conducting polymer electrolytes represent the ideal solution to reduce concentration polarization in lithium metal batteries (LMBs). This paper reports on the synthesis and characterization of single-ion ABA triblock copolymer electrolytes comprising PEO and poly(lithium 1-[3-(methacryloyloxy)propylsulfonyl]-1-(trifluoromethylsulfonyl)imide) blocks, poly(LiMTFSI). Block copolymers are prepared by reversible addition-fragmentation chain transfer polymerization, showing low glass transition temperature (-55 to 7 °C) and degree of crystallinity (51-0%). Comparatively high values of ionic conductivity are obtained (up to ≈ 10-4 S cm-1 at 70 °C), combined with a lithium-ion transference number close to unity (tLi+ ≈ 0.91) and a 4 V electrochemical stability window. In addition to these promising features, solid polymer electrolytes are successfully tested in lithium metal cells at 70 °C providing long lifetime up to 300 cycles, and stable charge/discharge cycling at C/2 (≈100 mAh g-1).

Structural and compositional optimization of the LiNi0.8Co0.2O2 electrode by new synthesis conditions

International Nuclear Information System (INIS)

Mosqueda L, Y.; Milian P, C. R.; Pomares A, M.; Rodriguez H, J.; Perez C, E.

2012-01-01

The optimization of citrate precursor method to obtain the LiNi 0.8 Co 0.2 O 2 oxide from the thermal decomposition of the citrate precursor (NH 4 ) 3 LiNi 0.8 Co 0.2 (C 6 H 5 O 7 ) is presented. The optimization procedure consists of both the lithium atmosphere and the reaction time control during the decomposition of the citrate precursor. Were obtained and characterized two kind of the (Li l-x Ni x )(Ni 0.8 Co 0.2 )O 2 oxides, with and without optimized synthesis conditions, identified as A and B oxides, respectively. The A and B oxides are characterized by compositional, structural and electrochemical studies. The results showed that is possible to reach the ordered oxide phase at smaller reaction time if the lithium atmosphere is controlled. From the combination of the chemical analysis by Icp and the DRX Rietveld structural refinement it is possible to establish the Li, Ni(II), Ni(III) and Co(III) composition with great accuracy. The resulted structural and compositional transformations have a close relation with technological parameters of the rechargeable lithium battery using Li Ni 0.8 Co 0.2 O 2 oxide as cathode. (Author)

Enthalpies of formation of layered LiNixMnxCo1-2xO2 (0 ≤ x ≤ 0.5) compounds as lithium ion battery cathode materials

International Nuclear Information System (INIS)

Masoumi, Maryam; Cupid, Damian M.; Reichmann, Thomas L.; Seifert, Hans J.; Chang, Keke; Music, Denis; Schneider, Jochen M.

2017-01-01

Layer-structured mixed transition metal oxides with the formula LiNi x Mn x Co 1-2x O 2 (0 ≤ x ≤ 0.5) are considered as important cathode materials for lithium-ion batteries. In an effort to evaluate the relative thermodynamic stabilities of individual compositions in this series, the enthalpies of formation of selected stoichiometries are determined by high temperature oxide melt drop solution calorimetry and verified by ab-initio calculations. The measured and calculated data are in good agreement with each other, and the results show that LiCoO 2 -LiNi 0.5 Mn 0.5 O 2 solid solution approaches ideal behavior. By increasing x, i.e. by equimolar substitution of Mn 4+ and Ni 2+ for Co 3+ , the enthalpy of formation of LiNi x Mn x Co 1-2x O 2 from the elements becomes more exothermic, implying increased energetic stability. This conclusion is in agreement with the literature results showing improved structural stability and cycling performance of Ni/Mn-rich LiNi x Mn x Co 1-2x O 2 compounds cycled to higher cut-off voltages.

Neutronics and activation analysis of lithium-based ternary alloys in IFE blankets

Energy Technology Data Exchange (ETDEWEB)

Jolodosky, Alejandra, E-mail: aleja311@berkeley.edu [University of California Berkeley, Berkeley, CA 94706 (United States); Kramer, Kevin [Lawrence Livermore National Laboratory, P.O. Box 808, Livermore, CA (United States); Meier, Wayne; DeMuth, James; Reyes, Susana [TerraPower, Bellevue, WA 98005 (United States); Fratoni, Massimiliano [University of California Berkeley, Berkeley, CA 94706 (United States)

2016-06-15

Highlights: • Monte Carlo calculations were performed on numerous lithium ternary alloys. • Elements with high neutron multiplication performed well with low absorbers. • Enriching lithium decreases minimum lithium concentration of alloys by 60% or more. • Alloys that performed well neutronically were selected for activation calculations. • Alloys activated, except LiBaBi, do not pose major environmental or safety concerns. - Abstract: An attractive feature of using liquid lithium as the breeder and coolant in fusion blankets is that it has very high tritium solubility and results in very low levels of tritium permeation throughout the facility infrastructure. However, lithium metal vigorously reacts with air and water and presents plant safety concerns. The Lawrence Livermore National Laboratory is carrying an effort to develop a lithium-based ternary alloy that maintains the beneficial properties of lithium (e.g. high tritium breeding and solubility) and at the same time reduces overall flammability concerns. This study evaluates the neutronics performance of lithium-based alloys in the blanket of an inertial fusion energy chamber in order to inform such development. 3-D Monte Carlo calculations were performed to evaluate two main neutronics performance parameters for the blanket: tritium breeding ratio (TBR), and the fusion energy multiplication factor (EMF). It was found that elements that exhibit low absorption cross sections and higher q-values such as Pb, Sn, and Sr, perform well with those that have high neutron multiplication such as Pb and Bi. These elements meet TBR constrains ranging from 1.02 to 1.1. However, most alloys do not reach EMFs greater than 1.15. Additionally, it was found that enriching lithium with {sup 6}Li significantly increases the TBR and decreases the minimum lithium concentration by more than 60%. The amount of enrichment depends on how much total lithium is in the alloy to begin with. Alloys that performed well in the TBR

Solid-state lithium battery

Science.gov (United States)

Ihlefeld, Jon; Clem, Paul G; Edney, Cynthia; Ingersoll, David; Nagasubramanian, Ganesan; Fenton, Kyle Ross

2014-11-04

The present invention is directed to a higher power, thin film lithium-ion electrolyte on a metallic substrate, enabling mass-produced solid-state lithium batteries. High-temperature thermodynamic equilibrium processing enables co-firing of oxides and base metals, providing a means to integrate the crystalline, lithium-stable, fast lithium-ion conductor lanthanum lithium tantalate (La.sub.1/3-xLi.sub.3xTaO.sub.3) directly with a thin metal foil current collector appropriate for a lithium-free solid-state battery.

Characteristics of LiMO2 (M = Co, Ni, Ni0.2Co0.8, Ni0.8Co0.2) powders prepared from solution of their acetates

International Nuclear Information System (INIS)

Arof, A.K.

2008-01-01

Stoichiometric quantities of the acetates of lithium, cobalt and nickel were dissolved in distilled water and stirred with a magnetic stirrer. After complete dissolution was obtained, the solutions were heated at 120 deg. C under continuous stirring until some dark colored powder materials were formed. These precursor materials were divided into three batches and heated at 250 deg. C (for 24 h), 370 deg. C (for 24 h) and 800 deg. C for 10 h. The precursor and calcined samples were X-rayed. The X-ray diffractograms for the prepared samples were compared to that of commercialized samples and those published in the literature. The Bragg peak with Miller indices (0 0 3) in the diffractogram of the LiNi 0.8 Co 0.2 O 2 prepared sample showed a lower intensity compared to the (1 0 4) peak. The ratio of the (0 0 3) to (1 0 4) peaks for the LiNi 0.2 Co 0.8 O 2 sample is 1.56. Lattice parameters showed that the LiCoO 2 and LiNi 0.2 Co 0.8 O 2 samples produced by the method in the present investigation have potential to exhibit good electrochemical performance when used as electrodes in lithium ion batteries

Structural influence of mixed transition metal ions on lithium bismuth borate glasses

Science.gov (United States)

Yadav, Arti; Dahiya, Manjeet S.; Hooda, A.; Chand, Prem; Khasa, S.

2017-08-01

Lithium bismuth borate glasses containing mixed transition metals having composition 7CoO·23Li2O·20Bi2O3·50B2O3 (CLBB), 7V2O5·23Li2O·20Bi2O3·50B2O3 (VLBB) and x(2CoO·V2O5)·(30 - x)Li2O·20Bi2O3·50B2O3 (x = 0.0 (LBB) and x = 2.0, 5.0, 7.0, 10.0 mol% (CVLBB1-4)) are synthesized via melt quench route. The synthesized compositions are investigated for their physical properties using density (D) and molar volume (Vm), thermal properties by analyzing DSC/TG thermo-graphs, structural properties using IR absorption spectra in the mid-IR range and optical properties using UV-Vis-NIR spectroscopy. The Electron Paramagnetic Resonance (EPR) spectra of vanadyl and cobalt ion have been analyzed to study compositional effects on spin-Hamiltonian parameters. The non linear variations in physical properties depict a strong structural influence of Co/V- oxides on the glassy matrix. The compositional variations in characteristic temperatures (glass transition temperature Tg, glass crystallization temperature Tp and glass melting temperature Tm) reveals that Tg for glass samples CLBB is relatively less than that of pure lithium bismuth borate (LBB) glass sample wherein Tg for sample VLBB is higher than that of LBB. The increase in Tg (as compared with LBB) with an enhanced substitution of mixed transition metal oxides (2CoO·V2O5) shows a progressive structure modification of bismuth borate matrix. These predictions are very well corroborated by corresponding compositional trends of Tp and Tm. FTIR studies reveal that Co2+& VO2+ ions lead to structural rearrangements through the conversion of three-coordinated boron into four coordinated boron and thereby reducing number of non-bridging oxygen atoms. Bismuth is found to exist in [BiO6] octahedral units only, whereas boroxol rings are not present in the glass network. The theoretical values of optical basicity (Λth) and corresponding oxide ion polarizability (αo2-) have also been calculated to investigate oxygen covalency of

On anodic stability and decomposition mechanism of sulfolane in high-voltage lithium ion battery

International Nuclear Information System (INIS)

Xing, Lidan; Tu, Wenqiang; Vatamanu, Jenel; Liu, Qifeng; Huang, Wenna; Wang, Yating; Zhou, Hebing; Zeng, Ronghua; Li, Weishan

2014-01-01

Graphical abstract: - Highlights: • Influence of lithium salts on the anodic stability of sulfolane has been investigated. • Oxidation decomposition mechanisms of LiPF 6 /Sulfolane electrolyte have been well understood by theoretical and experimental methods. • Decomposition products of the electrolyte can be found on the electrode surface and in the interfacial electrolyte. - Abstract: In this work, we investigated the anodic stability and decomposition mechanism of sulfolane (SL). The anodic stability of SL-based electrolyte with different lithium salts on Pt and LiNi 0.5 Mn 1.5 O 4 electrodes was found to decrease as follows: LiPF 6 /SL > LiBF 4 /SL > LiClO 4 /SL. The oxidation potential of 1M LiPF 6 /SL electrolyte on both Pt and electrodes is about 5.0V vs Li/Li + . The presence of PF 6 - and another SL solvent dramatically alters the decomposition mechanism of SL. Oxidation decomposition of SL-SL cluster is the most favorable reaction in LiPF 6 /SL electrolyte. The dimer products with S-O-R group were detected by IR spectra on the charged LiNi 0.5 Mn 1.5 O 4 electrode surface and in the electrolyte near the electrode surface, and were found to increase the interfacial reaction resistance of the LiNi 0.5 Mn 1.5 O 4 electrode

Ultracold lithium-6 atoms in the BEC-BCS crossover: experiments and the construction of a new apparatus; Atomes de lithium-6 ultra froids dans la transition BEC-BCS: experiences et construction d'un montage experimental

Energy Technology Data Exchange (ETDEWEB)

Teichmann, M

2007-09-15

We use a fermionic gas of Lithium-6 as a model system to study superfluidity. The limiting cases of superfluidity are Bose-Einstein condensation (BEC) and superconductivity, described by the theory by Bardeen, Cooper and Schrieffer (BCS). In Lithium-6 gases, we can explore the whole range between the two cases, known as the BEC-BCS crossover, using a Feshbach resonance. We study the change of the momentum distribution of the gas in this cross-over and compare to theoretical models. We also investigate the hydrodynamic expansion, characteristic for a superfluid gas. We observe a sudden change of the ellipticity of the gas close to the transition to the superfluid phase. Moreover, we localized heteronuclear Feshbach resonances between {sup 6}Li and {sup 7}Li. We are currently constructing a second generation of the experimental setup. An new laser system, based on high power laser diodes, was developed. Changes in the vacuum chamber, including a complete reconstruction of the Zeeman slower, have increased the atomic flux, allowing us to increase the repetition rate of our experiment. Modifications of the geometry of the magnetic traps lead to a higher number of trapped atoms. (author)

Modeling of the lithium based neutralizer for ITER neutral beam injector

Energy Technology Data Exchange (ETDEWEB)

Dure, F., E-mail: franck.dure@u-psud.fr [LPGP, Laboratoire de Physique des Gaz et Plasmas, CNRS-Universite Paris Sud, Orsay (France); Lifschitz, A.; Bretagne, J.; Maynard, G. [LPGP, Laboratoire de Physique des Gaz et Plasmas, CNRS-Universite Paris Sud, Orsay (France); Simonin, A. [IRFM, Institut de Recherche sur la Fusion Magnetique, CEA Cadarache, 13108 Saint-Paul lez Durance (France); Minea, T. [LPGP, Laboratoire de Physique des Gaz et Plasmas, CNRS-Universite Paris Sud, Orsay (France)

2012-04-04

Highlights: Black-Right-Pointing-Pointer We compare different lithium based neutraliser configurations to the deuterium one. Black-Right-Pointing-Pointer We study characteristics of the secondary plasma and the propagation of the 1 MeV beam. Black-Right-Pointing-Pointer Using lithium increases the neutralisation effiency keeping correct beam focusing. Black-Right-Pointing-Pointer Using lithium also reduces the backstreaming effect in direction of the ion source. - Abstract: To achieve thermonuclear temperatures necessary to produce fusion reactions in the ITER Tokamak, additional heating systems are required. One of the main method to heat the plasma ions in ITER will be the injection of energetic neutrals (NBI). In the neutral beam injector, negative ions (D{sup -}) are electrostatically accelerated to 1 MeV, and then stripped of their extra electron via collisions with a target gas, in a structure known as neutralizer. In the current ITER specification, the target gas is deuterium. It has been recently proposed to use lithium vapor instead of deuterium as target gas in the neutralizer. This would allow to reduce the gas load in the NBI vessel and to improve the neutralization efficiency. A Particle-in-Cell Monte Carlo code has been developed to study the transport of the beams and the plasma formation in the neutralizer. A comparison between Li and D{sub 2} based neutralizers made with this code is presented here, as well as a parametric study on the geometry of the Li based neutralizer. Results demonstrate the feasibility of a Li based neutralizer, and its advantages with respect to the deuterium based one.

Direct evidence of Ni magnetic moment in TbNi{sub 2}Mn—X-ray magnetic circular dichroism

Energy Technology Data Exchange (ETDEWEB)

Yu, D.H., E-mail: dyu@ansto.gov.au [Bragg Institute, Australian Nuclear Science and Technology Organisation, Lucas Heights, Sydney, NSW 2234 (Australia); Huang, Meng-Jie [National Synchrotron Radiation Research Center, 101 Hsin-Ann Road, Hsinchu Science Park, Hsinchu 30076, Taiwan (China); Wang, J.L. [Bragg Institute, Australian Nuclear Science and Technology Organisation, Lucas Heights, Sydney, NSW 2234 (Australia); School of Physical, Environmental and Mathematical Sciences, University of New South Wales, Canberra at the Australian Defense Force Academy, Sydney, ACT 2600 (Australia); Institute for Superconductivity and Electronic Materials, University of Wollongong, Wollongong, NSW 2522 (Australia); Su, Hui-Chia; Lin, Hong-Ji; Chen, Chien-Te [National Synchrotron Radiation Research Center, 101 Hsin-Ann Road, Hsinchu Science Park, Hsinchu 30076, Taiwan (China); Campbell, S.J. [School of Physical, Environmental and Mathematical Sciences, University of New South Wales, Canberra at the Australian Defense Force Academy, Sydney, ACT 2600 (Australia)

2014-12-15

We have investigated the individual magnetic moments of Ni, Mn and Tb atoms in the intermetallic compound TbNi{sub 2}Mn in the Laves phase (magnetic phase transition temperature T{sub C} ∼131 K) by X-ray magnetic circular dichroism (XMCD) studies at 300 K, 80 K and 20 K. Analyses of the experimental results reveal that Ni atoms at 20 K in an applied magnetic field of 1 T carry an intrinsic magnetic moment of spin and orbital magnetic moment contributions 0.53±0.01 μ{sub B} and 0.05±0.01 μ{sub B}, respectively. These moment values are similar to those of the maximum saturated moment of Ni element. A very small magnetic moment of order <0.1 μ{sub B} has been measured for Mn. This suggests that Mn is antiferromagnetically ordered across the two nearly equally occupied sites of 16d and 8a. A magnetic moment of up to ∼0.3 μ{sub B} has been observed for the Tb atoms. Identification of a magnetic moment on the Ni atoms has provided further evidence for the mechanism of enhancement of the magnetic phase transition temperature in TbNi{sub 2}Mn compared with TbNi{sub 2} (T{sub C}∼37.5 K) and TbMn{sub 2} (T{sub C}∼54 K) due to rare earth–transition metal (R–T) and transition metal–transition metal (T–T) interactions. The behaviour of the X-ray magnetic circular dichroism spectra of TbNi{sub 2}Mn at 300 K, 80 K and 20 K – above and below the magnetic ordering temperature T{sub C} ∼131 K – is discussed. - Highlights: • We study the magnetic moment of TbNi{sub 2}Mn with XMCD. • We observe directly the Ni intrinsic magnetic moment in TbNi{sub 2}Mn. • We find that Mn ordered antiferromagnetically across the 16d and 8a sites. • We confirm the mechanism for increasing the magnetic phase transition temperature.

Renewable-Biomolecule-Based Full Lithium-Ion Batteries.

Science.gov (United States)

Hu, Pengfei; Wang, Hua; Yang, Yun; Yang, Jie; Lin, Jie; Guo, Lin

2016-05-01

A renewable-biomolecule-based full lithium-ion battery is successfully fabricated for the first time. Naturally derivable emodin and humic acid based electrodes are used as cathode and anode, respectively. The as-assembled batteries exhibit superb specific capacity and substantial operating voltage capable of powering a wearable electronic watch, suggesting the great potential for practical applications with the significant merits of sustainability and biocompatibility. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Two-dimensional Thermal Modeling of Lithium-ion Battery Cell Based on Electrothermal Impedance Spectroscopy

DEFF Research Database (Denmark)

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

2016-01-01

Thermal modeling of lithium-ion batteries is gaining its importance together with increasing power density and compact design of the modern battery systems in order to assure battery safety and long lifetime. Thermal models of lithium-ion batteries are usually either expensive to develop...... and accurate or equivalent thermal circuit based with moderate accuracy and without spatial temperature distribution. This work presents initial results that can be used as a fundament for the cost-efficient development of the two-dimensional thermal model of lithium-ion battery based on multipoint...

Engineering micro-supercapacitors of graphene nanowalls/Ni heterostructure based on microfabrication technology

Science.gov (United States)

Li, Jinhua; Zhu, Minjie; Wang, Zhuqing; Ono, Takahito

2016-10-01

Heterostructure of graphene nanowalls (GNW) supported Ni thin-layer was fabricated to form an on-chip pseudocapacitor via a standard microelectromechanical system process. Beyond a high-rate capability of the micro-supercapacitors, a large specific energy density of 2.1 mW h cm-3 and power density up to 5.91 W cm-3 have been achieved, which are two orders of magnitude higher than those commercial electrolytic capacitors and thin-film batteries, respectively. Rational analysis revealed a rapid GNW growth originated from the Pt current collector embedment by catalyzing hydrocarbon dissociating. The unique concept in our design includes that Ni was evaporated onto GNW to serve as both the shadow mask for microelectrode patterning and subsequently a precursor to be in-situ electrochemically converted into pseudo-capacitive Ni(OH)2 for capacitance enhancing. Addressing the challenge to uniformly coat in complex nanoporous structures, this strategy renders a conformal deposition of pseudo-capacitive material on individual graphene nanoflakes, leading to efficient merits harnessing of huge accessible surfaces from the conductive GNW networks and great capacitance of the Ni-based active materials for high performance delivery. The proof of concept can be potentially extended to other transition metals and paves the way to further apply GNW hybrids in diverse microsystems.

Structural behavior of Pd40Cu30Ni10P20 bulk metallic glass below and above the glass transition

DEFF Research Database (Denmark)

Mattern, N.; Hermann, H.; Roth, S.

2003-01-01

The thermal behavior of the structure of Pd40Cu30Ni10P20 bulk metallic glass has been investigated in situ through the glass transition by means of high-temperature x-ray synchrotron diffraction. The dependence of the x-ray structure factor S(q) of the Pd40Cu30Ni10P20 glass on temperature follows...... the Debye theory up to the glass transition with a Debye temperature theta=296 K. Above the glass transition temperature T-g, the temperature dependence of S(q) is altered, pointing to a continuous development of structural changes in the liquid with temperature. The atomic pair correlation functions g......(r) indicate changes in short-range-order parameters of the first and the second neighborhood with temperature. The temperature dependence of structural parameters is different in glass and in supercooled liquid, with a continuous behavior through the glass transition. The nearest-neighbor distance decreases...

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

Science.gov (United States)

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

2016-04-04

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

Determination of the mechanism and extent of surface degradation in Ni-based cathode materials after repeated electrochemical cycling

Directory of Open Access Journals (Sweden)

Sooyeon Hwang

2016-09-01

Full Text Available We take advantage of scanning transmission electron microscopy and electron energy loss spectroscopy to investigate the changes in near-surface electronic structure and quantify the degree of local degradation of Ni-based cathode materials with the layered structure (LiNi0.8Mn0.1Co0.1O2 and LiNi0.4Mn0.3Co0.3O2 after 20 cycles of delithiation and lithiation. Reduction of transition metals occurs in the near-surface region of cathode materials: Mn is the major element to be reduced in the case of relatively Mn-rich composition, while reduction of Ni ions is dominant in Ni-rich materials. The valences of Ni and Mn ions are complementary, i.e., when one is reduced, the other is oxidized in order to maintain charge neutrality. The depth of degradation zone is found to be much deeper in Ni-rich materials. This comparative analysis provides important insights needed for the devising of new cathode materials with high capacity as well as long lifetime.

Cycling of lithium/metal oxide cells using composite electrolytes containing fumed silicas

International Nuclear Information System (INIS)

Zhou Jian; Fedkiw, Peter S.

2003-01-01

The effect on cycle capacity is reported of cathode material (metal oxide, carbon, and current collector) in lithium/metal oxide cells cycled with fumed silica-based composite electrolytes. Three types of electrolytes are compared: filler-free electrolyte consisting of methyl-terminated poly(ethylene glycol) oligomer (PEGdm, M w =250)+lithium bis(trifluromethylsufonyl)imide (LiTFSI) (Li:O=1:20), and two composite systems of the above baseline liquid electrolyte containing 10-wt% A200 (hydrophilic fumed silica) or R805 (hydrophobic fumed silica with octyl surface group). The composite electrolytes are solid-like gels. Three cathode active materials (LiCoO 2 , V 6 O 13 , and Li x MnO 2 ), four conducting carbons (graphite Timrex [reg] SFG 15, SFG 44, carbon black Vulcan XC72R, and Ketjenblack EC-600JD), and three current collector materials (Al, Ni, and carbon fiber) were studied. Cells with composite electrolytes show higher capacity, reduced capacity fade, and less cell polarization than those with filler-free electrolyte. Among the three active materials studied, V 6 O 13 cathodes deliver the highest capacity and Li x MnO 2 cathodes render the best capacity retention. Discharge capacity of Li/LiCoO 2 cells is affected greatly by cathode carbon type, and the capacity decreases in the order of Ketjenblack>SFG 15>SFG 44>Vulcan. Current collector material also plays a significant role in cell cycling performance. Lithium/vanadium oxide (V 6 O 13 ) cells deliver increased capacity using Ni foil and carbon fiber current collectors in comparison to an Al foil current collector

Solid Lithium Ion Conductors (SLIC) for Lithium Solid State Batteries

Data.gov (United States)

National Aeronautics and Space Administration — To identify the most lithium-ion conducting solid electrolytes for lithium solid state batteries from the emerging types of solid electrolytes, based on a...

Degradation Behaviour of Lithium-Ion Batteries based on Field Measured Frequency Regulation Mission Profile

DEFF Research Database (Denmark)

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

2015-01-01

Energy storage systems based on Lithium-ion batteries have been proposed as an environmental friendly alternative to traditional conventional generating units for providing grid frequency regulation. One major challenge regarding the use of Lithium-ion batteries in such applications is their cost...... competitiveness in comparison to other storage technologies or with the traditional frequency regulation methods. In order to surpass this challenge and to allow for optimal sizing and proper use of the battery, accurate knowledge about the lifetime of the Lithium-ion battery and its degradation behaviour...... is required. This paper aims to investigate, based on a laboratory developed lifetime model, the degradation behaviour of the performance parameters (i.e., capacity and power capability) of a Lithium-ion battery cell when it is subjected to a field measured mission profile, which is characteristic...

Lithium in drinking water and suicide mortality: The interplay with lithium prescriptions

NARCIS (Netherlands)

Helbich, M; Leitner, M; Kapusta, N

Background Little is known about the effects of lithium intake through drinking water on suicide. This intake originates either from natural rock and soil elution and/or accumulation of lithium-based pharmaceuticals in ground water. Aims To examine the interplay between natural lithium in drinking

Electrochemical Properties of the LiNi0.6Co0.2Mn0.2O2 Cathode Material Modified by Lithium Tungstate under High Voltage.

Science.gov (United States)

Fu, Jiale; Mu, Daobin; Wu, Borong; Bi, Jiaying; Cui, Hui; Yang, Hao; Wu, Hanfeng; Wu, Feng

2018-05-31

An amount (5 wt %) of lithium tungstate (Li 2 WO 4 ) as an additive significantly improves the cycle and rate performances of the LiNi 0.6 Co 0.2 Mn 0.2 O 2 electrode at the cutoff voltage of 4.6 V. The 5 wt % Li 2 WO 4 -mixed LiNi 0.6 Co 0.2 Mn 0.2 O 2 electrode delivers a reversible capacity of 199.2 mA h g -1 and keeps 73.1% capacity for 200 cycles at 1 C. It retains 67.4% capacity after 200 cycles at 2 C and delivers a discharge capacity of 167.3 mA h g -1 at 10 C, while those of the pristine electrode are only 44.7% and 87.5 mA h g -1 , respectively. It is shown that the structure of the LiNi 0.6 Co 0.2 Mn 0.2 O 2 cathode material is not affected by mixing Li 2 WO 4 . The introduced Li 2 WO 4 effectively restrains the LiPF 6 and carbonate solvent decomposition by consuming PF 5 at high cutoff voltage, forming a stable cathode/electrolyte interface film with low resistance.

Ultracold lithium-6 atoms in the BEC-BCS crossover: experiments and the construction of a new apparatus; Atomes de lithium-6 ultra froids dans la transition BEC-BCS: experiences et construction d'un montage experimental

Energy Technology Data Exchange (ETDEWEB)

Teichmann, M

2007-09-15

We use a fermionic gas of Lithium-6 as a model system to study superfluidity. The limiting cases of superfluidity are Bose-Einstein condensation (BEC) and superconductivity, described by the theory by Bardeen, Cooper and Schrieffer (BCS). In Lithium-6 gases, we can explore the whole range between the two cases, known as the BEC-BCS crossover, using a Feshbach resonance. We study the change of the momentum distribution of the gas in this cross-over and compare to theoretical models. We also investigate the hydrodynamic expansion, characteristic for a superfluid gas. We observe a sudden change of the ellipticity of the gas close to the transition to the superfluid phase. Moreover, we localized heteronuclear Feshbach resonances between {sup 6}Li and {sup 7}Li. We are currently constructing a second generation of the experimental setup. An new laser system, based on high power laser diodes, was developed. Changes in the vacuum chamber, including a complete reconstruction of the Zeeman slower, have increased the atomic flux, allowing us to increase the repetition rate of our experiment. Modifications of the geometry of the magnetic traps lead to a higher number of trapped atoms. (author)

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

International Nuclear Information System (INIS)

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

2013-01-01

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

Characterization of silicon- and carbon-based composite anodes for lithium-ion batteries

International Nuclear Information System (INIS)

Khomenko, Volodymyr G.; Barsukov, Viacheslav Z.

2007-01-01

In recent years development of active materials for negative electrodes has been of great interest. Special attention has been focused on the active materials possessing higher reversible capacity than that of conventional graphite. In the present work the electrochemical performance of some carbon/silicon-based materials has been analyzed. For this purpose various silicon-based composites were prepared using such carbon materials as graphite, hard carbon and graphitized carbon black. An analysis of charging-discharging processes at electrodes based on different carbon materials has shown that graphite modified with silicon is the most promising anode material. It has also been revealed that the irreversible capacity mainly depends on the content of Si. An optimum content of Si has been determined with taking into account that high irreversible capacity is not suitable for practical application in lithium-ion batteries. This content falls within the range of 8-10 wt%. The reversible capacity of graphite modified with 8 wt% carbon-coated Si was as high as 604 mAh g -1 . The irreversible capacity loss with this material was as low as 8.1%. The small irreversible capacity of the material allowed developing full lithium-ion rechargeable cells in the 2016 coin cell configuration. Lithium-ion batteries based on graphite modified with silicon show gravimetric and volumetric specific energy densities which are higher by approximately 20% than those for a lithium-ion battery based on natural graphite

Hierarchically porous micro-rod lithium-rich cathode material Li1.2Ni0.13Mn0.54Co0.13O2 for high performance lithium-ion batteries

International Nuclear Information System (INIS)

Zhang, Linjing; Borong, Wu.; Ning, Li.; Feng, Wu.

2014-01-01

Graphical abstract: - Highlights: • The hierarchically porous micro-rod Li 1.2 Ni 0.13 Mn 0.54 Co 0.13 O 2 material is prepared by a facile hydrothermal method. • This material exhibits good cycling performance. • It delivers discharge capacities of 280.7, 254.8, 232.3, 225.6, 201.7 and 172.7 mAh g −1 at 0.1 C, 0.2 C, 0.5 C, 1 C, 2 C and 5 C rates, respectively. • Excellent rate capability and cycleability are obtained attributed to the hierarchically porous micro-rod structure. - Abstract: Lithium-rich cathode material Li 1.2 Ni 0.13 Mn 0.54 Co 0.13 O 2 with hierarchically porous micro-rod structures has been synthesized using a facile hydrothermal method. The morphology and XRD patterns explain the formation mechanism of the sample. Micro-rod oxalates precursor with rough surface is formed during the hydrothermal reaction, and then the product with hierarchically porous structures constructed of nanoparticles is synthesized during the sintering process at high temperatures. The electrochemical performance results show that the as-prepared sample exhibits high capacities, good cycleability and outstanding rate capability. It delivers discharge capacities of 280.7, 254.8, 232.3, 225.6, 201.7 and 172.7 mAh g −1 at 0.1 C, 0.2 C, 0.5 C, 1 C, 2 C and 5 C rates, respectively. The cycle voltammograms indicate the good reversibility of the as-prepared Li 1.2 Ni 0.13 Mn 0.54 Co 0.13 O 2 material. The high onset temperature of the exothermal peak in the differential scanning calorimetry curve implies its good thermal stability. The good performance of the as-prepared material is endowed by its hierarchically porous structures

Structural Transformations in High-Capacity Li ₂ Cu _0.5 Ni _0.5 O ₂ Cathodes

Energy Technology Data Exchange (ETDEWEB)

Ruther, Rose; Pandian, Amaresh S.; Yan, Pengfei; Weker, Johanna N.; Wang, Chongmin; Nanda, Jagjit

2017-03-21

Cathode materials that can cycle > 1 Li+ per transition metal are of substantial interest to increase the overall energy density of lithium-ion batteries. Li2Cu0.5Ni0.5O2 has a very high theoretical capacity of ~ 500 mAh/g assuming both Li+ are cycled reversibly. The Cu2+/3+ and Ni2+/3+/4+ redox couples are also at high voltage, which could further boost the energy density of this system. Despite such promise, Li2Cu0.5Ni0.5O2 undergoes irreversible phase changes during charge (delithiation) that result in large first-cycle irreversible loss and poor long-term cycling stability. Oxygen is evolved before the Cu2+/3+ or Ni3+/4+ transitions are accessed. In this contribution, XRD, TEM, and TXM-XANES are used to follow the chemical and structural changes that occur in Li2Cu0.5Ni0.5O2 during electrochemical cycling. Li2Cu0.5Ni0.5O2 is a solid solution of orthorhombic Li2CuO2 and Li2NiO2, but the structural changes more closely mimic the Li2NiO2 endmember. Li2Cu0.5Ni0.5O2 loses long-range order during charge, but TEM analysis provides clear evidence for particle exfoliation and the transformation from orthorhombic to a partially layered structure. Linear combination fitting and principal component analysis of TXM-XANES are used to map the different phases that emerge during cycling ex situ and in situ. Significant changes in the XANES at the Cu and Ni K-edges correlate with the onset of oxygen evolution.

A Universal Strategy for Hollow Metal Oxide Nanoparticles Encapsulated into B/N Co-Doped Graphitic Nanotubes as High-Performance Lithium-Ion Battery Anodes.

Science.gov (United States)

Tabassum, Hassina; Zou, Ruqiang; Mahmood, Asif; Liang, Zibin; Wang, Qingfei; Zhang, Hao; Gao, Song; Qu, Chong; Guo, Wenhan; Guo, Shaojun

2018-02-01

Yolk-shell nanostructures have received great attention for boosting the performance of lithium-ion batteries because of their obvious advantages in solving the problems associated with large volume change, low conductivity, and short diffusion path for Li + ion transport. A universal strategy for making hollow transition metal oxide (TMO) nanoparticles (NPs) encapsulated into B, N co-doped graphitic nanotubes (TMO@BNG (TMO = CoO, Ni 2 O 3 , Mn 3 O 4 ) through combining pyrolysis with an oxidation method is reported herein. The as-made TMO@BNG exhibits the TMO-dependent lithium-ion storage ability, in which CoO@BNG nanotubes exhibit highest lithium-ion storage capacity of 1554 mA h g -1 at the current density of 96 mA g -1 , good rate ability (410 mA h g -1 at 1.75 A g -1 ), and high stability (almost 96% storage capacity retention after 480 cycles). The present work highlights the importance of introducing hollow TMO NPs with thin wall into BNG with large surface area for boosting LIBs in the terms of storage capacity, rate capability, and cycling stability. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Pressure effect of glass transition temperature in Zr46.8Ti8.2Cu7.5Ni10Be27.5 bulk metallic glass

DEFF Research Database (Denmark)

Jiang, Jianzhong; Roseker, W.; Sikorski, M.

2004-01-01

Pressure effects on glass transition temperature and supercooled liquid region of a Zr46.8Ti8.2Cu7.5Ni10Be27.5 bulk glass have been investigated by performing in situ high-temperature and high-pressure x-ray powder diffraction measurements using synchrotron radiation. The glass transition was det...... range of 0-2.2 GPa. This method opens a possibility to study the pressure effect of glass transition process in glassy systems under high pressures (>1 GPa). (C) 2004 American Institute of Physics.......Pressure effects on glass transition temperature and supercooled liquid region of a Zr46.8Ti8.2Cu7.5Ni10Be27.5 bulk glass have been investigated by performing in situ high-temperature and high-pressure x-ray powder diffraction measurements using synchrotron radiation. The glass transition...... was detected from the change of the slope of peak position as a function of temperature. It is found that the glass transition temperature increases with pressure by 4.4 K/GPa for the Zr46.8Ti8.2Cu7.5Ni10Be27.5 bulk glass, and the supercooled liquid range decreases with pressure by 2.9 K/GPa in a pressure...

Reaction mechanism and thermal stability study on cathode materials for rechargeable lithium ion batteries

Science.gov (United States)

Fang, Jin

(0≤y≤0.4) is stable up to 600 °C with particle size above 100 nm particle. And in this work Mn rich olivine phase Fe1-yMnyPO4 is found to be thermally stable up to at least 450 °C with particle size down to below 50 nm, different delithiation methods result in different decomposition routes, electrochemical delithiation results in decreased thermal stability. Moisture exposure appears the most detrimental to the thermal stability of Mn-rich samples. LiNi0.5Mn1.5O4 has attracted a lot of attentions because the potential is even higher (˜ 4.7 V vs Li +/Li0). However, electrolyte decomposition is quite often observed during electrochemistry cycles due to the high voltage operation window. Spinel LiNi0.5Mn1.5O4 is known as ordered and disordered according to the distribution of cations which relates to the synthesis conditions. Mn and Ni ions distribute either randomly in 16d sites of an Fd3m-space group or ordered in 4a and 12d sites of P4332 space group. During discharge and charge processes, Li ions insert and extract from the structure with the oxidation state of Ni changing between +2 and +4 while Mn remains as Mn4+. So far the correlation between cation distribution and electrochemical performance is still unclear, mostly the disordered samples are observed to have better rate capabilities. In order to study the reaction mechanism, combined XRD and XAS are used to investigate the oxidation state of transition metals and structure change of LiNi0.5Mn1.5O4 during electrochemical cycling, disordered and ordered samples were compared and studied, and both samples show three phases transformation during charge and discharge. However, the samples suffer from severe electrolyte decomposition which has influence on the results. Good spinel samples with nice electrochemistry performance is required, pure spinel samples are obtained by using co-precipitation method, the distribution of transition metal ions can be controlled by controlling the synthesis temperature

Magnetic properties of NiMn{sub 2}O{sub 4−δ} (nickel manganite): Multiple magnetic phase transitions and exchange bias effect

Energy Technology Data Exchange (ETDEWEB)

Tadic, Marin, E-mail: marint@vinca.rs [Condensed Matter Physics Laboratory, Vinca Institute of Nuclear Sciences, University of Belgrade, POB 522, 11001 Belgrade (Serbia); Savic, S.M. [Institute for Multidisciplinary Research, University of Belgrade, Kneza Viseslava 1, 11000 Belgrade (Serbia); Jaglicic, Z. [University of Ljubljana, Faculty of Civil Engineering and Geodesy and Institute of Mathematics, Physics and Mechanics, Jadranska 19, 1000 Ljubljana (Slovenia); Vojisavljevic, K.; Radojkovic, A.; Prsic, S. [Institute for Multidisciplinary Research, University of Belgrade, Kneza Viseslava 1, 11000 Belgrade (Serbia); Nikolic, Dobrica [Department of Physics, University of Belgrade Faculty of Mining and Geology, Belgrade (Serbia)

2014-03-05

Highlights: • We have successfully synthesized NiMn{sub 2}O{sub 4−δ} sample by complex polymerization synthesis. • Magnetic measurements reveal complex properties and triple magnetic phase transitions. • Magnetic measurements of M(H) show hysteretic behavior below 120 K. • Hysteresis properties after cooling of the sample in magnetic field show exchange bias effect. -- Abstract: We present magnetic properties of NiMn{sub 2}O{sub 4−δ} (nickel manganite) which was synthesized by complex polymerization synthesis method followed by successive heat treatment and final calcinations in air at 1200 °C. The sample was characterized by using X-ray powder diffractometer (XRPD), scanning electron microscopy (SEM), field-emission scanning electron microscopy (FE-SEM) and superconducting quantum interference device (SQUID) magnetometer. The XRPD and FE-SEM studies revealed NiMn{sub 2}O{sub 4−δ} phase and good crystallinity of particles. No other impurities have been observed by XRPD. The magnetic properties of the sample have been studied by measuring the temperature and field dependence of magnetization. Magnetic measurements of M(T) reveal rather complex magnetic properties and multiple magnetic phase transitions. We show three magnetic phase transitions with transition temperatures at T{sub M1} = 35 K (long-range antiferromagnetic transition), T{sub M2} = 101 K (antiferromagnetic-type transition) and T{sub M3} = 120 K (ferromagnetic-like transition). We found that the T{sub M1} transition is strongly dependent on the strength of the applied magnetic field (T{sub M1} decreases with increasing applied field) whereas the T{sub M3} is field independent. Otherwise, the T{sub M2} maximum almost disappears in higher applied magnetic fields (H = 1 kOe and 10 kOe). Magnetic measurements of M(H) show hysteretic behavior below T{sub M3}. Moreover, hysteresis properties measured after cooling of the sample in magnetic field of 10 kOe show exchange bias effect with an

3-dimensional porous NiCo2O4 nanocomposite as a high-rate capacity anode for lithium-ion batteries

International Nuclear Information System (INIS)

Mo, Yudi; Ru, Qiang; Song, Xiong; Hu, Shejun; Guo, Lingyun; Chen, Xiaoqiu

2015-01-01

Highlights: • D-glucose molecules as organic carbon source, have a crucial effect on the morphology and pore distribution of the synthetic products. • Facile synthesis: solvothermal method. • High rate capacity: 625 mAh g −1 at 4.4 C. • Improved long-term cycling stability: 1389 mAh g −1 after 180 cycles at 0.55 C. - Abstract: In this work, organic carbon modified NiCo 2 O 4 (NCO@C) nanocomposite with porous 3-dimensional (3D) structure was successfully synthesized by a facile hydrothermal method in D-glucose-mediated processes. A detailed research reveals that D-glucose molecules play an important role in the formation of the porous 3D structure and also provide a conductive carbon network within the NCO@C nanocomposite materials. Such a porous 3D interconnected carbonaceous nanostructure applied as electrode material for lithium-ion batteries (LIBs) shows that its reversible capacity, cycling stability, and rate capability are significantly enhanced in comparison with those of pure NiCo 2 O 4 (NCO) electrode. The as-prepared NCO@C composite electrode with porous 3D nanostructure displays a higher discharge specific capacity of 1389 mAh g −1 even after 180 cycles at a current rate of 0.55 C. Furthermore, this composite material also presents a high rate capacity, when the current rate gradually increases to 0.55 C, 1.1 C, 2.2 C, and 4.4 C, the reversible capacity can still render about 1082, 1029, 850, and 625 mAh g −1 , respectively. The enhanced electrochemical performance indicated that the NCO@C nanocomposite might be a very promising candidate to replace conventional graphite-based anode materials for LIBs

Composition Optimization of Lithium-Based Ternary Alloy Blankets for Fusion Reactors

Science.gov (United States)

Jolodosky, Alejandra

The goal of this dissertation is to examine the neutronic properties of a novel type of fusion reactor blanket material in the form of lithium-based ternary alloys. Pure liquid lithium, first proposed as a blanket for fusion reactors, is utilized as both a tritium breeder and a coolant. It has many attractive features such as high heat transfer and low corrosion properties, but most importantly, it has a very high tritium solubility and results in very low levels of tritium permeation throughout the facility infrastructure. However, lithium metal vigorously reacts with air and water and presents plant safety concerns including degradation of the concrete containment structure. The work of this thesis began as a collaboration with Lawrence Livermore National Laboratory in an effort to develop a lithium-based ternary alloy that can maintain the beneficial properties of lithium while reducing the reactivity concerns. The first studies down-selected alloys based on the analysis and performance of both neutronic and activation characteristics. First, 3-D Monte Carlo calculations were performed to evaluate two main neutronics performance parameters for the blanket: tritium breeding ratio (TBR), and energy multiplication factor (EMF). Alloys with adequate results based on TBR and EMF calculations were considered for activation analysis. Activation simulations were executed with 50 years of irradiation and 300 years of cooling. It was discovered that bismuth is a poor choice due to achieving the highest decay heat, contact dose rates, and accident doses. In addition, it does not meet the waste disposal ratings (WDR). The straightforward approach to obtain Monte Carlo TBR and EMF results required 231 simulations per alloy and became computationally expensive, time consuming, and inefficient. Consequently, alternate methods were pursued. A collision history-based methodology recently developed for the Monte Carlo code Serpent, calculates perturbation effects on practically

Exaggerated natriuresis and lithium clearance in spontaneously hypertensive rats

DEFF Research Database (Denmark)

Holstein-Rathlou, N H; Kanters, J K; Leyssac, P P

1988-01-01

Since hypertension is associated with changes in the handling of various cations (including sodium and lithium) across the cell membrane, the present study investigated the validity of the lithium clearance method in hypertension by comparing two measures of proximal reabsorption. Thus, fractional...... lithium excretion and transit time (TT)-occlusion time (OT; e-TT/T) were determined successively in the same spontaneously hypertensive rat (SHR, Okamoto strain). The rats were examined both before and after an acute saline load. The results show that the lithium clearance method can be used...... for the determination of proximal reabsorption in SHR. Utilizing the lithium clearance method, the changes in renal sodium handling underlying the exaggerated natriuresis were investigated in unanaesthetized catheterized rats. It was found that the exaggerated natriuresis was associated with an increased output from...

Non-destructive fast charging algorithm of lithium-ion batteries based on the control-oriented electrochemical model

International Nuclear Information System (INIS)

Chu, Zhengyu; Feng, Xuning; Lu, Languang; Li, Jianqiu; Han, Xuebing; Ouyang, Minggao

2017-01-01

Highlights: •A novel non-destructive fast charging algorithm of lithium-ion batteries is proposed. •A close-loop observer of lithium deposition status is constructed based on the SP2D model. •The charging current is modified online using the feedback of the lithium deposition status. •The algorithm can shorten the charging time and can be used for charging from different initial SOCs. •The post-mortem observation and degradation tests show that no lithium deposition occurs during fast charging. -- Abstract: Fast charging is critical for the application of lithium-ion batteries in electric vehicles. Conventional fast charging algorithms may shorten the cycle life of lithium-ion batteries and induce safety problems, such as internal short circuit caused by lithium deposition at the negative electrode. In this paper, a novel, non-destructive model-based fast charging algorithm is proposed. The fast charging algorithm is composed of two closed loops. The first loop includes an anode over-potential observer that can observe the status of lithium deposition online, whereas the second loop includes a feedback structure that can modify the current based on the observed status of lithium deposition. The charging algorithm enhances the charging current to maintain the observed anode over-potential near the preset threshold potential. Therefore, the fast charging algorithm can decrease the charging time while protecting the health of the battery. The fast charging algorithm is validated on a commercial large-format nickel cobalt manganese/graphite cell. The results showed that 96.8% of the battery capacity can be charged within 52 min. The post-mortem observation of the surface of the negative electrode and degradation tests revealed that the fast charging algorithm proposed here protected the battery from lithium deposition.

Structural and physical properties of new uranium and transition element ternary stannides (Fe, Co, Ni, Ru, Rh, Pd, Ir, Pt); Proprietes structurales et physiques de nouveaux stannures ternaires a base d'uranium et d'element de transition (Fe, Co, Ni, Rh, Pd, Ir, Pt)

Energy Technology Data Exchange (ETDEWEB)

Mirambet, F

1993-12-15

This work is dedicated to the study of ternary stannides based on uranium. The author reviews the structural, magnetic and electric properties of different families of stannides. The study of the U{sub 2}M{sub 2}Sn family where M stands for Fe, Co, Ni, Ru, Rh, Pd, Ir and Pt shows that the magnetic behaviour of uranium in these compounds is strongly influenced by the transition element M, which is explained by the hybridization force 5f(U) - nd(M) that depends on the number of electrons on the d shell of the M element. For instance, for the elements whose d shell is low filled (Fe, Ru), the U{sub 2}M{sub 2}Sn stannides show no magnetic order. On the other hand, when the number of d-electrons increases, a magnetic order appears progressively.

Pulse Power Capability Estimation of Lithium Titanate Oxide-based Batteries

DEFF Research Database (Denmark)

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

2016-01-01

The pulse power capability (PPC) represents one of the parameters that describe the performance behavior of Lithium-ion batteries independent on the application. Consequently, extended information about the Li-ion battery PPC and its dependence on the operating conditions become necessary. Thus......, this paper analyzes the power capability characteristic of a 13Ah high power Lithium Titanate Oxide-based battery and its dependence on temperature, load current and state-of-charge. Furthermore, a model to predict the discharging PPC of the battery cell at different temperatures and load currents for three...

Kramers non-magnetic superconductivity in LnNiAsO superconductors.

Science.gov (United States)

Li, Yuke; Luo, Yongkang; Li, Lin; Chen, Bin; Xu, Xiaofeng; Dai, Jianhui; Yang, Xiaojun; Zhang, Li; Cao, Guanghan; Xu, Zhu-an

2014-10-22

We investigated a series of nickel-based oxyarsenides LnNiAsO (Ln=La, Ce, Pr, Nd, Sm) compounds. CeNiAsO undergoes two successive anti-ferromagnetic transitions at TN1=9.3 K and TN2=7.3 K; SmNiAsO becomes an anti-ferromagnet below TN≃3.5 K; NdNiAsO keeps paramagnetic down to 2 K but orders anti-ferromagnetically below TN≃1.3 K. Superconductivity was observed only in Kramers non-magnetic LaNiAsO and PrNiAsO with Tc=2.7 K and 0.93 K, respectively. The superconductivity of PrNiAsO is further studied by upper critical field and specific heat measurements, which reveal that PrNiAsO is a weakly coupled Kramers non-magnetic superconductor. Our work confirms that the nickel-based oxyarsenide superconductors are substantially different in mechanism to iron-based ones, and are likely to be described by the conventional superconductivity theory.

Graphene-based integrated electrodes for flexible lithium ion batteries

International Nuclear Information System (INIS)

Shi, Ying; Wen, Lei; Zhou, Guangmin; Chen, Jing; Pei, Songfeng; Huang, Kun; Cheng, Hui-Ming; Li, Feng

2015-01-01

We have prepared flexible free-standing electrodes with anode and cathode active materials deposited on a highly conductive graphene membrane by a two-step filtration method. Compared with conventional electrodes using metal as current collectors, these electrodes have displayed stronger adhesion, superior electrochemical performance, higher energy density, and better flexibility. A full lithium ion battery assembled by adopting these graphene-based electrodes has showed high rate capability and long cyclic life. We have also assembled a thin, lightweight, and flexible lithium ion battery with poly-(dimethyl siloxane) sheets as packaging material to light a red light-emitting diode. This flexible battery can be easily bent without structural failure or performance loss and operated well under a bent state. The fabrication process of these graphene-based integrated electrodes only has two filtration steps; thus it is easy to scale up. These results suggest great potential for these graphene-based flexible batteries in lightweight, bendable, and wearable electronic devices. (paper)

Life cycle environmental assessment of lithium-ion and nickel metal hydride batteries for plug-in hybrid and battery electric vehicles.

Science.gov (United States)

Majeau-Bettez, Guillaume; Hawkins, Troy R; Strømman, Anders Hammer

2011-05-15

This study presents the life cycle assessment (LCA) of three batteries for plug-in hybrid and full performance battery electric vehicles. A transparent life cycle inventory (LCI) was compiled in a component-wise manner for nickel metal hydride (NiMH), nickel cobalt manganese lithium-ion (NCM), and iron phosphate lithium-ion (LFP) batteries. The battery systems were investigated with a functional unit based on energy storage, and environmental impacts were analyzed using midpoint indicators. On a per-storage basis, the NiMH technology was found to have the highest environmental impact, followed by NCM and then LFP, for all categories considered except ozone depletion potential. We found higher life cycle global warming emissions than have been previously reported. Detailed contribution and structural path analyses allowed for the identification of the different processes and value-chains most directly responsible for these emissions. This article contributes a public and detailed inventory, which can be easily be adapted to any powertrain, along with readily usable environmental performance assessments.

Raman study of molecular motions in relation to phase transitions in [Ni(NH3)6](NO3)2

International Nuclear Information System (INIS)

Janik, J.M.; Pick, R.M.; Le Postollec, M.

1987-01-01

A Raman band at 710 cm -1 has been used for the study of the NO 3 - ions reorientation and of the phase transitions in [Ni(NH 3 ) 6 ](NO 3 ) 2 . The strong temperature dependence of the width of this band in phase 1 gives evidence for the NO 3 - reorientations in this phase. The reorientations stop in phase 2. The same band was used for studying the phase 2/phase 3 transition. The large thermal hysteresis of this transition has ben confirmed. 16 refs., 4 figs. (author)

High performance discharges in the Lithium Tokamak eXperiment with liquid lithium walls

Energy Technology Data Exchange (ETDEWEB)

Schmitt, J. C.; Bell, R. E.; Boyle, D. P.; Esposti, B.; Kaita, R.; Kozub, T.; LeBlanc, B. P.; Lucia, M.; Maingi, R.; Majeski, R.; Merino, E.; Punjabi-Vinoth, S.; Tchilingurian, G. [Princeton Plasma Physics Laboratory, Princeton, New Jersey 08543 (United States); Capece, A.; Koel, B.; Roszell, J. [Princeton University, Princeton, New Jersey 08544 (United States); Biewer, T. M.; Gray, T. K. [Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831 (United States); Kubota, S. [University of California at Los Angeles, Los Angeles, California 90095 (United States); Beiersdorfer, P. [Lawrence Livermore National Laboratory, Livermore, California 94550 (United States); and others

2015-05-15

The first-ever successful operation of a tokamak with a large area (40% of the total plasma surface area) liquid lithium wall has been achieved in the Lithium Tokamak eXperiment (LTX). These results were obtained with a new, electron beam-based lithium evaporation system, which can deposit a lithium coating on the limiting wall of LTX in a five-minute period. Preliminary analyses of diamagnetic and other data for discharges operated with a liquid lithium wall indicate that confinement times increased by 10× compared to discharges with helium-dispersed solid lithium coatings. Ohmic energy confinement times with fresh lithium walls, solid and liquid, exceed several relevant empirical scaling expressions. Spectroscopic analysis of the discharges indicates that oxygen levels in the discharges limited on liquid lithium walls were significantly reduced compared to discharges limited on solid lithium walls. Tokamak operations with a full liquid lithium wall (85% of the total plasma surface area) have recently started.

High performance discharges in the Lithium Tokamak eXperiment with liquid lithium walls

International Nuclear Information System (INIS)

Schmitt, J. C.; Bell, R. E.; Boyle, D. P.; Esposti, B.; Kaita, R.; Kozub, T.; LeBlanc, B. P.; Lucia, M.; Maingi, R.; Majeski, R.; Merino, E.; Punjabi-Vinoth, S.; Tchilingurian, G.; Capece, A.; Koel, B.; Roszell, J.; Biewer, T. M.; Gray, T. K.; Kubota, S.; Beiersdorfer, P.

2015-01-01

The first-ever successful operation of a tokamak with a large area (40% of the total plasma surface area) liquid lithium wall has been achieved in the Lithium Tokamak eXperiment (LTX). These results were obtained with a new, electron beam-based lithium evaporation system, which can deposit a lithium coating on the limiting wall of LTX in a five-minute period. Preliminary analyses of diamagnetic and other data for discharges operated with a liquid lithium wall indicate that confinement times increased by 10× compared to discharges with helium-dispersed solid lithium coatings. Ohmic energy confinement times with fresh lithium walls, solid and liquid, exceed several relevant empirical scaling expressions. Spectroscopic analysis of the discharges indicates that oxygen levels in the discharges limited on liquid lithium walls were significantly reduced compared to discharges limited on solid lithium walls. Tokamak operations with a full liquid lithium wall (85% of the total plasma surface area) have recently started

My Experience with Ti-Ni-Based and Ti-Based Shape Memory Alloys

Science.gov (United States)

Miyazaki, Shuichi

2017-12-01

The present author has been studying shape memory alloys including Cu-Al-Ni, Ti-Ni-based, and Ni-free Ti-based alloys since 1979. This paper reviews the present author's research results for the latter two materials since 1981. The topics on the Ti-Ni-based alloys include the achievement of superelasticity in Ti-Ni alloys through understanding of the role of microstructures consisting of dislocations and precipitates, followed by the contribution to the development of application market of shape memory effect and superelasticity, characterization of the R-phase and monoclinic martensitic transformations, clarification of the basic characteristics of fatigue properties, development of sputter-deposited shape memory thin films and fabrication of prototypes of microactuators utilizing thin films, development of high temperature shape memory alloys, and so on. The topics of Ni-free Ti-based shape memory alloys include the characterization of the orthorhombic phase martensitic transformation and related shape memory effect and superelasticity, the effects of texture, omega phase and adding elements on the martensitic transformation and shape memory properties, clarification of the unique effects of oxygen addition to induce non-linear large elasticity, Invar effect and heating-induced martensitic transformation, and so on.

Synthesis and electrochemical performance of long lifespan Li-rich Li1+x(Ni0.37Mn0.63)1−xO2 cathode materials for lithium-ion batteries

International Nuclear Information System (INIS)

Gao, Min; Lian, Fang; Liu, Hongquan; Tian, Cuijun; Ma, Leilei; Yang, Wangyue

2013-01-01

Highlights: ► Long lifespan Li 1+x (Ni 0.37 Mn 0.63 ) 1−x O 2 samples were obtained through adjusting the content of lithium. ► x = 0.123 and x = 0.111 can retain more than 80% of the initial discharge capacities at 0.5 C after 500 cycles. ► x = 0.086 shows high initial efficiency, high medium discharge voltage and good rate capability. ► The significant increase of charge-transfer resistance of the cells contributes to the capacity decay. -- Abstract: Li 1+x (Ni 0.37 Mn 0.63 ) 1−x O 2 (x = 0.123, 0.111, 0.086, 0.070, 0.031) cathode materials were synthesized via coprecipitation of carbonates and the samples with long lifespan for lithium ion batteries were obtained through adjusting the content of lithium. Their crystal structure and electrochemical performance were characterized by means of powder X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), inductive coupled plasma (ICP), galvanostatic charge/discharge test and electrochemical impedance spectrum (EIS). The XRD data show that the materials can be indexed as a single α-NaFeO 2 phase except the sample with x = 0.031. The FESEM results indicate that the primary particles size increase with an increase of x value and the secondary particles retain the spherical morphology. The as-prepared sample with x = 0.086 delivers the largest discharge capacity of 232.1 mAh g −1 and a high initial efficiency of 81.8% at 0.2 C in the potential range of 2.5–4.7 V. Moreover, the better cycle performances are obtained for samples with x = 0.123 and 0.111, and the capacity retentions are up to 89 and 81% of the first discharge capacity at 0.5 C after 500 cycles, respectively

Evidence of ion intercalation mediated band structure modification and opto-ionic coupling in lithium niobite

Science.gov (United States)

Shank, Joshua C.; Tellekamp, M. Brooks; Doolittle, W. Alan

2015-01-01

The theoretically suggested band structure of the novel p-type semiconductor lithium niobite (LiNbO2), the direct coupling of photons to ion motion, and optically induced band structure modifications are investigated by temperature dependent photoluminescence. LiNbO2 has previously been used as a memristor material but is shown here to be useful as a sensor owing to the electrical, optical, and chemical ease of lithium removal and insertion. Despite the high concentration of vacancies present in lithium niobite due to the intentional removal of lithium atoms, strong photoluminescence spectra are observed even at room temperature that experimentally confirm the suggested band structure implying transitions from a flat conduction band to a degenerate valence band. Removal of small amounts of lithium significantly modifies the photoluminescence spectra including additional larger than stoichiometric-band gap features. Sufficient removal of lithium results in the elimination of the photoluminescence response supporting the predicted transition from a direct to indirect band gap semiconductor. In addition, non-thermal coupling between the incident laser and lithium ions is observed and results in modulation of the electrical impedance.

Evidence of ion intercalation mediated band structure modification and opto-ionic coupling in lithium niobite

International Nuclear Information System (INIS)

Shank, Joshua C.; Tellekamp, M. Brooks; Doolittle, W. Alan

2015-01-01

The theoretically suggested band structure of the novel p-type semiconductor lithium niobite (LiNbO 2 ), the direct coupling of photons to ion motion, and optically induced band structure modifications are investigated by temperature dependent photoluminescence. LiNbO 2 has previously been used as a memristor material but is shown here to be useful as a sensor owing to the electrical, optical, and chemical ease of lithium removal and insertion. Despite the high concentration of vacancies present in lithium niobite due to the intentional removal of lithium atoms, strong photoluminescence spectra are observed even at room temperature that experimentally confirm the suggested band structure implying transitions from a flat conduction band to a degenerate valence band. Removal of small amounts of lithium significantly modifies the photoluminescence spectra including additional larger than stoichiometric-band gap features. Sufficient removal of lithium results in the elimination of the photoluminescence response supporting the predicted transition from a direct to indirect band gap semiconductor. In addition, non-thermal coupling between the incident laser and lithium ions is observed and results in modulation of the electrical impedance

Silicon oxide based high capacity anode materials for lithium ion batteries

Science.gov (United States)

Deng, Haixia; Han, Yongbong; Masarapu, Charan; Anguchamy, Yogesh Kumar; Lopez, Herman A.; Kumar, Sujeet

2017-03-21

Silicon oxide based materials, including composites with various electrical conductive compositions, are formulated into desirable anodes. The anodes can be effectively combined into lithium ion batteries with high capacity cathode materials. In some formulations, supplemental lithium can be used to stabilize cycling as well as to reduce effects of first cycle irreversible capacity loss. Batteries are described with surprisingly good cycling properties with good specific capacities with respect to both cathode active weights and anode active weights.

Hierarchical Mesoporous Lithium-Rich Li[Li0.2Ni0.2Mn0.6]O2 Cathode Material Synthesized via Ice Templating for Lithium-Ion Battery.

Science.gov (United States)

Li, Yu; Wu, Chuan; Bai, Ying; Liu, Lu; Wang, Hui; Wu, Feng; Zhang, Na; Zou, Yufeng

2016-07-27

Tuning hierarchical micro/nanostructure of electrode materials is a sought-after means to reinforce their electrochemical performance in the energy storage field. Herein, we introduce a type of hierarchical mesoporous Li[Li0.2Ni0.2Mn0.6]O2 microsphere composed of nanoparticles synthesized via an ice templating combined coprecipitation strategy. It is a low-cost, eco-friendly, and easily operated method using ice as a template to control material with homogeneous morphology and rich porous channels. The as-prepared material exhibits remarkably enhanced electrochemical performances with higher capacity, more excellent cycling stability and more superior rate property, compared with the sample prepared by conventional coprecipitation method. It has satisfactory initial discharge capacities of 280.1 mAh g(-1) at 0.1 C, 207.1 mAh g(-1) at 2 C, and 152.4 mAh g(-1) at 5 C, as well as good cycle performance. The enhanced electrochemical performance can be ascribed to the stable hierarchical microsized structure and the improved lithium-ion diffusion kinetics from the highly porous structure.

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

Science.gov (United States)

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

2018-02-01

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

Spherical NiO-C composite for anode material of lithium ion batteries

International Nuclear Information System (INIS)

Huang, X.H.; Tu, J.P.; Zhang, C.Q.; Chen, X.T.; Yuan, Y.F.; Wu, H.M.

2007-01-01

Spherical NiO-C composite was prepared by dispersing spherical NiO in glucose solution and subsequent carbonization under hydrothermal conditions at 180 o C. The microstructure and morphology of the NiO-C and NiO powders were characterized by means of X-ray diffraction (XRD) and scanning electron microscopy (SEM). The electrochemical properties of the electrodes were measured by galvanostatic charge-discharge tests, cyclic voltammetric analysis (CV), and electrochemical impedance spectroscopy (EIS). SEM images showed that the amorphous carbon not only coated on the surface but also filled the inner pores of the NiO spheres. Electrochemical tests showed that the NiO-C composite exhibited higher initial coulombic efficiency (66.6%) than NiO (56.4%), and better cycling performances. The improvement of these properties is attributed to the carbon, as it can reduce the specific surface area of porous sphere, and enhance the conductivity of porous NiO

Estimation of power lithium-ion battery SOC based on fuzzy optimal decision

Science.gov (United States)

He, Dongmei; Hou, Enguang; Qiao, Xin; Liu, Guangmin

2018-06-01

In order to improve vehicle performance and safety, need to accurately estimate the power lithium battery state of charge (SOC), analyzing the common SOC estimation methods, according to the characteristics open circuit voltage and Kalman filter algorithm, using T - S fuzzy model, established a lithium battery SOC estimation method based on the fuzzy optimal decision. Simulation results show that the battery model accuracy can be improved.

Five-dimensional visualization of phase transition in BiNiO3 under high pressure

International Nuclear Information System (INIS)

Liu, Yijin; Wang, Junyue; Yang, Wenge; Azuma, Masaki; Mao, Wendy L.

2014-01-01

Colossal negative thermal expansion was recently discovered in BiNiO 3 associated with a low density to high density phase transition under high pressure. The varying proportion of co-existing phases plays a key role in the macroscopic behavior of this material. Here, we utilize a recently developed X-ray Absorption Near Edge Spectroscopy Tomography method and resolve the mixture of high/low pressure phases as a function of pressure at tens of nanometer resolution taking advantage of the charge transfer during the transition. This five-dimensional (X, Y, Z, energy, and pressure) visualization of the phase boundary provides a high resolution method to study the interface dynamics of high/low pressure phase

General Approach to Prepare 0.33Li₂MnO₃ · 0.67LiNi1/3Co1/3Mn1/3O₂ Hollow Microspheres for High Performance Lithium Ion Batteries.

Science.gov (United States)

Li, Jingfa; Xu, Wenjin; Zhang, Lei; Li, Min

2018-06-01

Li-excess manganese-based oxide layered structures, have drawn increasing interests as the promising cathodes to succeed the conventional LiCoO2 in lithium ion batteries (LIBs). It could deliver a higher energy density and output potential, as well as the nature of environment benign and low cost. Pristine Li-excess manganese-based oxides however suffer from poor rate capacity and voltage fading after cycling, and their inherent capacity limits of bulk size in performance. Micro-/Nanostructured electrode materials are considered to hold the key to overcome these thresholds. This paper reports a general approach to prepare 0.33Li2MnO3 · 0.67LiNi1/3Co1/3Mn1/3O2 microspheres with pores and void space, which benefits improving both the capacity and cyclability. The electrode made of hollow 0.33Li2MnO3 · 0.67LiNi1/3Co1/3Mn1/3O2 microspheres exhibits a 224 mAh g-1 discharge capacity over 200 cycles at 0.25 C rate, and 195 mAh g-1 at 5.0 C rate. These results indicated good perspective of hollow microspheres for practical battery applications.

In situ visualization of Ni-Nb bulk metallic glasses phase transition

OpenAIRE

Oreshkin, A. I.; Mantsevich, V. N.; Savinov, S. V.; Oreshkin, S. I.; Panov, V. I.; Yavari, A. R.; Miracle, D. B.; Louzguine-Luzgin, D. V.

2013-01-01

We report the results of the Ni-based bulk metallic glass structural evolution and crystallization behavior in situ investigation. The X-ray diffraction (XRD), transmission electron microscopy (TEM), nano-beam diffraction (NBD), differential scanning calorimetry (DSC), radial distribution function (RDF) and scanning probe microscopy/spectroscopy (STM/STS) techniques were applied to analyze the structure and electronic properties of Ni63.5Nb36.5 glasses before and after crystallization. It was...

An Ultrastable and High-Performance Flexible Fiber-Shaped Ni-Zn Battery based on a Ni-NiO Heterostructured Nanosheet Cathode.

Science.gov (United States)

Zeng, Yinxiang; Meng, Yue; Lai, Zhengzhe; Zhang, Xiyue; Yu, Minghao; Fang, Pingping; Wu, Mingmei; Tong, Yexiang; Lu, Xihong

2017-11-01

Currently, the main bottleneck for the widespread application of Ni-Zn batteries is their poor cycling stability as a result of the irreversibility of the Ni-based cathode and dendrite formation of the Zn anode during the charging-discharging processes. Herein, a highly rechargeable, flexible, fiber-shaped Ni-Zn battery with impressive electrochemical performance is rationally demonstrated by employing Ni-NiO heterostructured nanosheets as the cathode. Benefiting from the improved conductivity and enhanced electroactivity of the Ni-NiO heterojunction nanosheet cathode, the as-fabricated fiber-shaped Ni-NiO//Zn battery displays high capacity and admirable rate capability. More importantly, this Ni-NiO//Zn battery shows unprecedented cyclic durability both in aqueous (96.6% capacity retention after 10 000 cycles) and polymer (almost no capacity attenuation after 10 000 cycles at 22.2 A g -1 ) electrolytes. Moreover, a peak energy density of 6.6 µWh cm -2 , together with a remarkable power density of 20.2 mW cm -2 , is achieved by the flexible quasi-solid-state fiber-shaped Ni-NiO//Zn battery, outperforming most reported fiber-shaped energy-storage devices. Such a novel concept of a fiber-shaped Ni-Zn battery with impressive stability will greatly enrich the flexible energy-storage technologies for future portable/wearable electronic applications. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

61Ni synchrotron radiation-based Mössbauer spectroscopy of nickel-based nanoparticles with hexagonal structure

Science.gov (United States)

Masuda, Ryo; Kobayashi, Yasuhiro; Kitao, Shinji; Kurokuzu, Masayuki; Saito, Makina; Yoda, Yoshitaka; Mitsui, Takaya; Hosoi, Kohei; Kobayashi, Hirokazu; Kitagawa, Hiroshi; Seto, Makoto

2016-01-01

We measured the synchrotron-radiation (SR)-based Mössbauer spectra of Ni-based nanoparticles with a hexagonal structure that were synthesised by chemical reduction. To obtain Mössbauer spectra of the nanoparticles without 61Ni enrichment, we developed a measurement system for 61Ni SR-based Mössbauer absorption spectroscopy without X-ray windows between the 61Ni84V16 standard energy alloy and detector. The counting rate of the 61Ni nuclear resonant scattering in the system was enhanced by the detection of internal conversion electrons and the close proximity between the energy standard and the detector. The spectrum measured at 4 K revealed the internal magnetic field of the nanoparticles was 3.4 ± 0.9 T, corresponding to a Ni atomic magnetic moment of 0.3 Bohr magneton. This differs from the value of Ni3C and the theoretically predicted value of hexagonal-close-packed (hcp)-Ni and suggested the nanoparticle possessed intermediate carbon content between hcp-Ni and Ni3C of approximately 10 atomic % of Ni. The improved 61Ni Mössbauer absorption measurement system is also applicable to various Ni materials without 61Ni enrichment, such as Ni hydride nanoparticles. PMID:26883185

Nanoconfined LiBH4 as a Fast Lithium Ion Conductor

DEFF Research Database (Denmark)

Blanchard, Didier; Nale, Angeloclaudio; Sveinbjörnsson, Dadi Þorsteinn

2015-01-01

is associated with a fraction of the confined borohydride that shows no phase transition, and most likely located close to the interface with the SiO2 pore walls. These results point to a new strategy to design low-temperature ion conducting solids for application in all solid-state lithium ion batteries, which......Designing new functional materials is crucial for the development of efficient energy storage and conversion devices such as all solid-state batteries. LiBH 4 is a promising solid electrolyte for Li-ion batteries. It displays high lithium mobility, although only above 110 °C at which a transition...

Empirical survey of the application of commercial-graded Lithium Polymer batteries in military systems in conjunction with solar panels and fuel cells

CSIR Research Space (South Africa)

Roux, A

2008-11-01

Full Text Available This paper presents the results of an empirical survey into the comparative characteristics of commercial NiCd, Lithium-ion and Lithium Polymer batteries when applied in a range of man portable military radios. The focus is on when the expected load...

Lithium ion conducting biopolymer electrolyte based on pectin doped with Lithium nitrate

Science.gov (United States)

Manjuladevi, R.; Selvin, P. Christopher; Selvasekarapandian, S.; Shilpa, R.; Moniha, V.

2018-04-01

The Biopolymer electrolyte based on pectin doped with lithium nitrate of different concentrations have been prepared by solution casting technique. The decrease in crystalline nature of the biopolymer has been identified by XRD analyses. The complex formation between the polymer and the salt has been revealed using FTIR analysis. The ionic conductivity has been explored using A.C. impedance spectroscopy which reveals that the biopolymer containing 30 wt% Pectin: 70wt%LiNO3 has highest ionic conductivity of 3.97 × 10-3 Scm-1.

Lithium current sources with an electrolyte based on aprotonic solvents

Energy Technology Data Exchange (ETDEWEB)

Shembel, Ye.M.; Ksenzhek, O.S.; Litvinova, V.I.; Martynenko, T.L.; Raykhelson, L.B.; Sokolov, L.A.; Strizhko, A.S.

1984-01-01

Lithium current sources with an electrolyte based on aprotonic solvents are examined. The effect of the composition of the electrolyte solution on the solubility of SO2 and the excess pressure of the gas above the electrolyte solution is established. The temperature characteristics of the electrolyte are studied from the standpoint of salt solubility, the association between the discharge conditions, the macrostructure of the porous inert cathode and the degree of usage of the active cathode substance of the SO2 as the necessary aspects for solving the problems of optimizing a lithium and SO2 system.

Composites Li2MnO3·LiMn1/3Ni1/3Co1/3O2: Optimized synthesis and applications as advanced high-voltage cathode for batteries working at elevated temperatures

International Nuclear Information System (INIS)

Yu Chuang; Li Guangshe; Guan Xiangfeng; Zheng Jing; Li Liping; Chen Tianwen

2012-01-01

Highlights: ► Composites xLi 2 MnO 3 ·(1 − x)LiMn 1/3 Ni 1/3 Co 1/3 O 2 (x = 0.1–0.4) were prepared by a novel two-step molten-salt route. ► Structure and chemical compositions of the composites were optimized to show an optimum electrochemical property. ► Composite electrode 0.3Li 2 MnO 3 ·0.7LiMn 1/3 Ni 1/3 Co 1/3 O 2 exhibited an excellent electrochemical performance at elevated temperature of 45.4 °C. ► Electrode kinetics of composites was uncovered for the excellent electrochemical performance at elevated temperature. - Abstract: This work reports on the optimized preparation of a series of composites xLi 2 MnO 3 ·(1 − x)LiMn 1/3 Ni 1/3 Co 1/3 O 2 (x = 0.1–0.4) with an aim to find an advanced high-voltage cathode for lithium-ion batteries that can work at elevated temperatures. Developing a two-step molten-salt method leads to composites with a layered-type structure, showing a particle size distribution ranging from 350 to 450 nm. The composites are featured by oxidation states stabilized as Mn 4+ , Ni 2+ , and Co 3+ , and by lattice occupation of Li + in both transition-metal layers and lithium layer of LiMn 1/3 Ni 1/3 Co 1/3 O 2 . When acting as a cathode of lithium-ion batteries, the composite at x = 0.3 shows an optimum electrochemical performance as characterized by a discharge capacity of 120 mAh g −1 at a high current density of 500 mA g −1 and a capacity retention of 64% after 20 cycles. Surprisingly, this electrochemical performance is significantly improved at elevated temperatures. Namely, discharge capacity is increased to 140.4 mAh g −1 at a high current density of 500 mA g −1 , while average capacity decay rate becomes very small to 0.76%. These excellent performance is explained in terms of the dramatically improved lithium-ion diffusions in both electrode and surface films at elevated temperatures.

Porous worm-like NiMoO4 coaxially decorated electrospun carbon nanofiber as binder-free electrodes for high performance supercapacitors and lithium-ion batteries

Science.gov (United States)

Tian, Xiaodong; Li, Xiao; Yang, Tao; Wang, Kai; Wang, Hongbao; Song, Yan; Liu, Zhanjun; Guo, Quangui

2018-03-01

The peculiar architectures consisting of electrospun carbon nanofibers coaxially decorated by porous worm-like NiMoO4 were successfully fabricated for the first time to address the poor cycling stability and inferior rate capability of the state-of-the-art NiMoO4-based electrodes caused by the insufficient structural stability, dense structure and low conductivity. The porous worm-like structure endows the electrode high capacitance/capacity due to large effective specific surface area and short electron/ion diffusion channels. Moreover, the robust integrated electrode with sufficient internal spaces can self-accommodate volume variation during charge/discharge processes, which is beneficial to the structural stability and integrity. By the virtue of rational design of the architecture, the hybrid electrode delivered high specific capacitance (1088.5 F g-1 at 1 A g-1), good rate capability (860.3 F g-1 at 20 A g-1) and long lifespan with a capacitance retention of 73.9% after 5000 cycles when used as supercapacitor electrode. For lithium-ion battery application, the electrode exhibited a high reversible capacity of 1132.1 mAh g-1 at 0.5 A g-1. Notably, 689.7 mAh g-1 can be achieved even after 150 continuous cycles at a current density of 1 A g-1. In the view of their outstanding electrochemical performance and the cost-effective fabrication process, the integrated nanostructure shows great promising applications in energy storage.

Graphene-Based Materials for Lithium-Ion Hybrid Supercapacitors.

Science.gov (United States)

Ma, Yanfeng; Chang, Huicong; Zhang, Miao; Chen, Yongsheng

2015-09-23

Lithium-ion hybrid supercapacitors (LIHSs), also called Li-ion capacitors, have attracted much attention due to the combination of the rapid charge-discharge and long cycle life of supercapacitors and the high energy-storage capacity of lithium-ion batteries. Thus, LIHSs are expected to become the ultimate power source for hybrid and all-electric vehicles in the near future. As an electrode material, graphene has many advantages, including high surface area and porous structure, high electric conductivity, and high chemical and thermal stability, etc. Compared with other electrode materials, such as activated carbon, graphite, and metal oxides, graphene-based materials with 3D open frameworks show higher effective specific surface area, better control of channels, and higher conductivity, which make them better candidates for LIHS applications. Here, the latest advances in electrode materials for LIHSs are briefly summarized, with an emphasis on graphene-based electrode materials (including 3D graphene networks) for LIHS applications. An outlook is also presented to highlight some future directions. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effect of chemical treatment on the electrochemical properties of Li1.2NixMn0.8-xO2 (x = 0.2 and 0.25) in lithium-ion batteries

Science.gov (United States)

Konishi, Hiroaki; Hirano, Tatsumi; Takamatsu, Daiko; Gunji, Akira; Feng, Xiaoliang; Furutsuki, Sho; Okumura, Takefumi; Terada, Shohei

2018-02-01

The effect of chemical treatment using (NH4)2SO4 on the electrochemical properties of Li1.2Ni0.2Mn0.6O2 and Li1.2Ni0.25Mn0.55O2 was investigated. The treatment was effective in improving the Coulombic efficiency and discharge capacity of a Li1.2Ni0.2Mn0.6O2 cathode, but treatment with too much (NH4)2SO4 degraded the cathode's electrochemical performance. The effect of (NH4)2SO4 treatment on the charge-discharge reaction mechanism of Li1.2Ni0.2Mn0.6O2 was investigated by evaluating reaction potential, particle configuration, and oxidation state of transition metal. The experimental results indicated that the changes in the electrochemical performance of the treated cathodes were attributed to the changes in the surface state and of the element contributing to the redox reaction. Treatment with an appropriate amount of (NH4)2SO4 also improved the electrochemical performance of the high-nickel-content lithium-rich layer-structured cathode material Li1.2Ni0.25Mn0.55O2.

Combined use of EPR and 23Na MAS NMR spectroscopy for assessing the properties of the mixed cobalt-nickel-manganese layers of P3-NayCo1-2xNixMnxO2.

Science.gov (United States)

Kalapsazova, M; Ivanova, S; Kukeva, R; Simova, S; Wegner, S; Zhecheva, E; Stoyanova, R

2017-10-11

Knowledge on the formation of mixed transition metal layers on lithium and sodium transition metal oxides, Li/Na(Co,Ni,Mn,)O 2 , determines the ability to control their electrochemical properties as electrode materials in alkaline ion batteries. Taking this into account, herein we combine the EPR and 23 Na MAS NMR spectroscopic techniques to gain insights into the structural peculiarities of the mixed cobalt-nickel-manganese layers of Na y Co 1-2x Ni x Mn x O 2 with a three-layer stacking (P3-type) structure. Two types of compositions are examined where diamagnetic Co 3+ and paramagnetic Ni 3+ and Mn 4+ are stabilized: Na 2/3 Co 1/3 Ni 1/3 Mn 1/3 O 2 and Na 1/2 Ni 1/2 Mn 1/2 O 2 . EPR spectroscopy operating in the X- and Q-band region is applied with an aim to improve the spectra resolution and, on the other hand, to provide straightforward information on the coordination of the transition metal ions inside the layers. The analysis of EPR spectra is based on the reference for the Mn 4+ and Ni 2+ ions occurring simultaneously in oxides with two layer stacking, P2-Na 2/3 Ni 1/3 Mn 2/3 O 2 . Complementary to EPR, 23 Na MAS NMR spectroscopy at high spinning rates is undertaken to assess the local structure of the Na nucleus in the layered P3-Na y Co 1-2x Ni x Mn x O 2 oxides. All results are discussed taking into account the EPR and NMR data for the well-known lithium analogues O3-LiCo 1/3 Ni 1/3 Mn 1/3 O 2 and O3-LiNi 1/2 Mn 1/2 O 2 . Finally, the structure peculiarities of the transition metal layers extracted from the EPR and NMR methods are demonstrated by electrochemical intercalation of Li + ions into P3-Na y Co 1-2x Ni x Mn x O 2 .

Unique edge-sharing sulfate-transition metal coordination in Na2M(SO4)2 (M=Ni and Co)

International Nuclear Information System (INIS)

Fry, Allyson M.; Sweeney, Owen T.; Adam Phelan, W.; Drichko, Natalia; Siegler, Maxime A.; McQueen, Tyrel M.

2015-01-01

Two compounds, Na 2 Ni(SO 4 ) 2 and Na 2 Co(SO 4 ) 2 , were synthesized and their structure and properties were characterized. They adopt a structure that contains a bidentate coordination of sulfate to the transition metal center, which was determined via single crystal X-ray diffraction combined with model refinements to both laboratory X-ray and time-of-flight neutron powder diffraction data. The compounds were both found to crystallize in the C2/c space group with Z=24 and a unit cell of a=23.3461(3) Å, b=10.3004(1) Å, c=17.4115(2) Å, β=98.8659(9)°, and V=4136.99(8) Å 3 for the cobalt analog and a=23.2253(1) Å, b=10.26155(6) Å, c=17.3353(1) Å, β=99.0376(5)°, and V=4080.20(5) Å 3 for the nickel analog. Magnetization measurements show that the transition metal centers have negligible interactions with neighboring sites. Infrared and Raman spectroscopies were used to further probe the unique sulfate-transition metal coordination, and confirm the bidentate binding motif. The resulting pseudo-trigonal bipyramidal coordination produces vivid violet, Na 2 Co(SO 4 ) 2 , and yellow, Na 2 Ni(SO 4 ) 2 , colors that were probed by diffuse reflectance. - Graphical abstract: Two blue distorted transition metal octahedra (oxygen in red) bridged by two sulfate tetrahedra are shown here. Each bridging sulfate tetrahedra shares an edge with one octahedron and a corner with the other. All of the remaining corners of the octahedra are corner sharing with four tetrahedra forming a polyhedral network. - Highlights: • Structure of Na2Ni(SO4)2 and Na2Co(SO4)2 is determined. • Unique sulfate-transition metal binding observed in the new structure. • Combined diffraction and spectroscopic techniques were used. • Magnetization measurements show negligible interactions between sites

Carbon-Based Materials for Lithium-Ion Batteries, Electrochemical Capacitors, and Their Hybrid Devices.

Science.gov (United States)

Yao, Fei; Pham, Duy Tho; Lee, Young Hee

2015-07-20

A rapidly developing market for portable electronic devices and hybrid electrical vehicles requires an urgent supply of mature energy-storage systems. As a result, lithium-ion batteries and electrochemical capacitors have lately attracted broad attention. Nevertheless, it is well known that both devices have their own drawbacks. With the fast development of nanoscience and nanotechnology, various structures and materials have been proposed to overcome the deficiencies of both devices to improve their electrochemical performance further. In this Review, electrochemical storage mechanisms based on carbon materials for both lithium-ion batteries and electrochemical capacitors are introduced. Non-faradic processes (electric double-layer capacitance) and faradic reactions (pseudocapacitance and intercalation) are generally explained. Electrochemical performance based on different types of electrolytes is briefly reviewed. Furthermore, impedance behavior based on Nyquist plots is discussed. We demonstrate the influence of cell conductivity, electrode/electrolyte interface, and ion diffusion on impedance performance. We illustrate that relaxation time, which is closely related to ion diffusion, can be extracted from Nyquist plots and compared between lithium-ion batteries and electrochemical capacitors. Finally, recent progress in the design of anodes for lithium-ion batteries, electrochemical capacitors, and their hybrid devices based on carbonaceous materials are reviewed. Challenges and future perspectives are further discussed. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hard x-ray photoemission study of the temperature-induced valence transition system EuNi2(Si1-xGex) 2

Science.gov (United States)

Ichiki, Katsuya; Mimura, Kojiro; Anzai, Hiroaki; Uozumi, Takayuki; Sato, Hitoshi; Utsumi, Yuki; Ueda, Shigenori; Mitsuda, Akihiro; Wada, Hirofumi; Taguchi, Yukihiro; Shimada, Kenya; Namatame, Hirofumi; Taniguchi, Masaki

2017-07-01

We investigated the bulk-derived electronic structure of the temperature-induced valence transition system EuNi2(Si1 -xGex )2 (x =0.70 , 0.79, and 0.82) by means of hard x-ray photoemission spectroscopy (HAXPES). The HAXPES spectra clearly show distinct temperature dependencies in the spectral intensities of the Eu2 + and Eu3 +3 d components. For x =0.70 , the changes in the Eu2 + and Eu3 +3 d spectral components with temperature reflect a continuous valence transition, whereas the sudden changes for x =0.79 and 0.82 reflect first-order valence transitions. The Eu 3 d spectral shapes for all x and particularly the drastic changes in the Eu3 +3 d feature with temperature are validated by a theoretical calculation based on the single-impurity Anderson model (SIAM). SIAM analysis reveals that the valence transition for each x is controlled by the c -f hybridization strength and the charge-transfer energy. Furthermore, the c -f hybridization strength governs the valence transition of this system, which is either first order or continuous, consistent with Kondo volume collapse.

Li3V2(PO4)3-coated Li1.17Ni0.2Co0.05Mn0.58O2 as the cathode materials with high rate capability for Lithium ion batteries

International Nuclear Information System (INIS)

Liu, Yi; Huang, Xiao; Qiao, Qiqi; Wang, Yonglong; Ye, Shihai; Gao, Xueping

2014-01-01

In this work, Lithium rich layered oxide Li 1.17 Ni 0.2 Co 0.05 Mn 0.58 O 2 (LNCMO) is prepared and coated with Li 3 V 2 (PO 4 ) 3 (LVP) by a chemical deposition method. The surface modification with LVP is introduced into Li-rich layered oxides LNCMO for the first time. After 100 cycles of charging and discharging at various rates, the Li 3 V 2 (PO 4 ) 3 -coated Li 1.17 Ni 0.2 Co 0.05 Mn 0.58 O 2 (LVP-coated LNCMO) (5 wt%) still provides a large capacity of 261.4 mAh g -1 , much higher than the pristine LNCMO (211.5 mAh g -1 ). At 5 C rate, the LVP-coated LNCMO exhibits a stable cyclic capacity of 153.4 mAh g -1 , higher than 114.1 mAh g -1 of the pristine LNCMO. The electrochemical impedance spectroscopy (EIS) analysis demonstrates the LVP coating layer can suppress interaction between the cathode surface and the electrolyte and enhance the kinetics of lithium-ion diffusion, contributing to the stable cyclic performance with more cyclic capacity as well as at the high current density

Experiments for liquid metal embrittlement of fusion reactor materials by liquid lithium

International Nuclear Information System (INIS)

Grundmann, M.; Borgstedt, H.U.

1984-10-01

The liquid metal embrittlement behaviour of two martensitic-ferritic steels [X22CrMoV121 (Nr. 1.4923) and X18CrMoVNb 121 (Nr. 1,4914)] and one austenite chromium-nickel-steel X5CrNi189 (Nr. 1.4301) was investigated. Tensile tests in liquid lithium at 200 and 250 0 C with two different strain rates on precorroded samples (1000 h at 550 0 C in lithium) were carried out. Reference values were gained from tensile tests in air (RT, 250 0 C). It is concluded that there is sufficient compatibility of the austenitic steel with liquid lithium. The use of the ferritic-martensitic steels in liquid lithium on the other hand, especially at temperatures of about 550 0 C, seems to be problematic. The experimental results led to a better understanding of LME, applying the theory of this material failure. (orig./IHOE) [de

Mesoporous Transition Metal Oxides for Supercapacitors.

Science.gov (United States)

Wang, Yan; Guo, Jin; Wang, Tingfeng; Shao, Junfeng; Wang, Dong; Yang, Ying-Wei

2015-10-14

Recently, transition metal oxides, such as ruthenium oxide (RuO₂), manganese dioxide (MnO₂), nickel oxides (NiO) and cobalt oxide (Co₃O₄), have been widely investigated as electrode materials for pseudo-capacitors. In particular, these metal oxides with mesoporous structures have become very hot nanomaterials in the field of supercapacitors owing to their large specific surface areas and suitable pore size distributions. The high specific capacities of these mesoporous metal oxides are resulted from the effective contacts between electrode materials and electrolytes as well as fast transportation of ions and electrons in the bulk of electrode and at the interface of electrode and electrolyte. During the past decade, many achievements on mesoporous transition metal oxides have been made. In this mini-review, we select several typical nanomaterials, such as RuO₂, MnO₂, NiO, Co₃O₄ and nickel cobaltite (NiCo₂O₄), and briefly summarize the recent research progress of these mesoporous transition metal oxides-based electrodes in the field of supercapacitors.

An in situ method of creating metal oxide–carbon composites and their application as anode materials for lithium-ion batteries

KAUST Repository

Yang, Zichao

2011-01-01

Transition metal oxides are actively investigated as anode materials for lithium-ion batteries (LIBs), and their nanocomposites with carbon frequently show better performance in galvanostatic cycling studies, compared to the pristine metal oxide. An in situ, scalable method for creating a variety of transition metal oxide-carbon nanocomposites has been developed based on free-radical polymerization and cross-linking of poly(acrylonitrile) in the presence of the metal oxide precursor containing vinyl groups. The approach yields a cross-linked polymer network, which uniformly incorporates nanometre-sized transition metal oxide particles. Thermal treatment of the organic-inorganic hybrid material produces nearly monodisperse metal oxide nanoparticles uniformly embedded in a porous carbon matrix. Cyclic voltammetry and galvanostatic cycling electrochemical measurements in a lithium half-cell are used to evaluate the electrochemical properties of a Fe3O 4-carbon composite created using this approach. These measurements reveal that when used as the anode in a lithium battery, the material exhibits stable cycling performance at both low and high current densities. We further show that the polymer/nanoparticle copolymerization approach can be readily adapted to synthesize metal oxide/carbon nanocomposites based on different particle chemistries for applications in both the anode and cathode of LIBs. © 2011 The Royal Society of Chemistry.

Study on the L–H transition power threshold with RF heating and lithium-wall coating on EAST

DEFF Research Database (Denmark)

Chen, Leifeng; Xu, G.S.; Nielsen, Anders Henry

2016-01-01

The power threshold for low (L) to high (H) confinement mode transition achieved by radio-frequency (RF) heating and lithium-wall coating is investigated experimentally on EAST for two sets of walls: an all carbon wall (C) and molybdenum chamber and a carbon divertor (Mo/C). For both sets of walls...... Ploss increases with neutral density near the lower X-point in EAST with the Mo/C wall, consistent with previous results in the C wall (Xu et al 2011 Nucl. Fusion 51 072001). These findings suggest that the edge neutral density, the ion ∇B drift as well as the divertor pumping capability play important...

Influence of intermartensitic transitions on transport properties of Ni$_{2.16}Mn_{0.84}$Ga alloy

CERN Document Server

Khovailo, V V; Wedel, C; Takagi, T; Abe, T; Sugiyama, K

2004-01-01

Magnetic, transport, and x-ray diffraction measurements of ferromagnetic shape memory alloy Ni$_{2.16}$Mn$_{0.84}$Ga revealed that this alloy undergoes an intermartensitic transition upon cooling, whereas no such a transition is observed upon subsequent heating. The difference in the modulation of the martensite forming upon cooling from the high-temperature austenitic state [5-layered (5M) martensite], and the martensite forming upon the intermartensitic transition [7-layered (7M) martensite] strongly affects the magnetic and transport properties of the alloy and results in a large thermal hysteresis of the resistivity $\\rho$ and magnetization $M$. The intermartensitic transition has an especially marked influence on the transport properties, as is evident from a large difference in the resistivity of the 5M and 7M martensite, $(\\rho_{\\mathrm{5M}} - \\rho_{\\mathrm{7M}})/\\rho _{\\mathrm{5M}} \\approx 15%$, which is larger than the jump of resistivity at the martensitic transition from the cubic austenitic phase ...

Magnetovolume effects and magnetic transitions in the invar systems Fe65Ni35 and Er2Fe14B at high hydrostatic pressure

International Nuclear Information System (INIS)

Sidorov, V.A.; Khvostantsev, L.G.

1994-01-01

The relative volume change and the initial ac-susceptibility have been measured for Fe 65 Ni 35 and Er 2 Fe 14 B under hydrostatic pressure up to 8.5 GPa at room temperature. The bulk modulus of Fe 65 Ni 35 begins to rise and the susceptibility begins to drop at 3.5-4 GPa, indicating the continuous disappearance of ferromagnetism at high pressure. The transition from ferromagnetic to paramagnetic state in Er 2 Fe 14 B at 5.7 GPa is more abrupt and the giant (order of magnitude) softening of the bulk modulus is observed before this transition. The spin reorientation (SR) transition in Er 2 Fe 14 B shifts under pressure to lower temperatures (dT SR /dP = -19 K/GPa). (orig.)

A facile cathode design combining Ni-rich layered oxides with Li-rich layered oxides for lithium-ion batteries

Energy Technology Data Exchange (ETDEWEB)

Song, Bohang; Li, Wangda; Yan, Pengfei; Oh, Seung-Min; Wang, Chong-Min; Manthiram, Arumugam

2016-09-01

A facile synthesis method was developed to prepare xLi₂MnO₃·(1-x)LiNi_0.7Co_0.15Mn_0.15O₂ (x = 0, 0.03, 0.07, 0.10, 0.20, and 0.30 as molar ratio) cathode materials, combining the advantages of high specific capacity from Ni-rich layered phase and surface chemical stability from Li-rich layered phase. X-ray diffraction (XRD), high resolution transmission electron microscope (HRTEM) and electrochemical charge/discharge performance confirm the formation of a Li-rich layered phase with C2/m symmetry. Most importantly, high-angle annular dark-field (HAADF) scanning transmission electron microscopy (STEM) reveals a spatial relationship that Li-rich nano-domain islands are integrated into a conventional Ni-rich layered matrix (R$\\bar{3}$m). This is the first time that Li-rich phase has been directly observed inside a particle at the nano-scale, when the overall composition of layered compounds (Li_1+δNi_xMn_yM_1-x-y-δO₂, M refers to transition metal elements) is Ni-rich (x > 0.5) rather than Mn-rich (y > 0.5). Remarkably, xLi₂MnO₃·(1-x)LiNi_0.7Co_0.15Mn_0.15O₂ cathode with optimized x value shows superior electrochemical performance at C/3, i.e., 170 mA h g^-1 with 90.3 % of capacity retention after 400 cycles at 25 °C and 164 mA h g^-1 with 81.3 % capacity retention after 200 cycles at 55 °C.

A revolution in electrodes: recent progress in rechargeable lithium-sulfur batteries.

Science.gov (United States)

Fang, Xin; Peng, Huisheng

2015-04-01

As a promising candidate for future batteries, the lithium-sulfur battery is gaining increasing interest due to its high capacity and energy density. However, over the years, lithium-sulfur batteries have been plagued by fading capacities and the low Coulombic efficiency derived from its unique electrochemical behavior, which involves solid-liquid transition reactions. Moreover, lithium-sulfur batteries employ metallic lithium as the anode, which engenders safety vulnerability of the battery. The electrodes play a pivotal role in the performance of lithium-sulfur batteries. A leap forward in progress of lithium-sulfur batteries is always accompanied by a revolution in the electrode technology. In this review, recent progress in rechargeable lithium-sulfur batteries is summarized in accordance with the evolution of the electrodes, including the diversified cathode design and burgeoning metallic-lithium-free anodes. Although the way toward application has still many challenges associated, recent progress in lithium-sulfur battery technology still paints an encouraging picture of a revolution in rechargeable batteries. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

International Space Station Lithium-Ion Battery

Science.gov (United States)

Dalton, Penni J.; Schwanbeck, Eugene; North, Tim; Balcer, Sonia

2016-01-01

The International Space Station (ISS) primary Electric Power System (EPS) currently uses Nickel-Hydrogen (Ni-H2) batteries to store electrical energy. The electricity for the space station is generated by its solar arrays, which charge batteries during insolation for subsequent discharge during eclipse. The Ni-H2 batteries are designed to operate at a 35 depth of discharge (DOD) maximum during normal operation in a Low Earth Orbit. Since the oldest of the 48 Ni-H2 battery Orbital Replacement Units (ORUs) has been cycling since September 2006, these batteries are now approaching their end of useful life. In 2010, the ISS Program began the development of Lithium-Ion (Li-Ion) batteries to replace the Ni-H2 batteries and concurrently funded a Li-Ion ORU and cell life testing project. When deployed, they will be the largest Li-Ion batteries ever utilized for a human-rated spacecraft. This paper will include an overview of the ISS Li-Ion battery system architecture, the Li-Ion battery design and development, controls to limit potential hazards from the batteries, and the status of the Li-Ion cell and ORU life cycle testing.

Polymer electrolytes based on aromatic lithium sulfonyl-imide compounds; Electrolytes polymeres a base de sulfonylimidures de lithium aromatiques

Energy Technology Data Exchange (ETDEWEB)

Reibel, L.; Bayoudh, S. [Centre National de la Recherche Scientifique (CNRS), 67 - Strasbourg (France). Institut Charles Sadron; Baudry, P. [Electricite de France, 77 - Moret sur Loing (France). Direction des Etudes et Recherches; Majastre, H. [Bollore Technologies, 29 - Quimper (France); Herlem, G. [UFR de Sciences et Techniques, L.E.S., 25 - Besancon (France)

1996-12-31

This paper presents ionic conductivity results obtained with polymer electrolytes and also with propylene carbonate solutions. The domain of electrochemical activity of this salt has been determined using cycle volt-amperometry in propylene carbonate. Preliminary experiments on the stability of the polymer electrolyte with respect to the lithium electrode have been carried out for a possible subsequent use in lithium batteries. (J.S.) 4 refs.

Polymer electrolytes based on aromatic lithium sulfonyl-imide compounds; Electrolytes polymeres a base de sulfonylimidures de lithium aromatiques