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A Novel Strategy to Suppress Capacity and Voltage Fading of Li‐ and Mn‐Rich Layered Oxide Cathode Material for Lithium‐Ion Batteries
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Shiming Zhang Haitao Gu Hongge Pan Suhui Yang Wubin Du Xiang Li Mingxia Gao Yongfeng Liu Min Zhu Liuzhang Ouyang Dechao Jian Feng Pan 《Liver Transplantation》2017,7(6)
Poor cycling stability is one of the key scientific issues needing to be solved for Li‐ and Mn‐rich layered oxide cathode. In this paper, sodium carboxymethyl cellulose (CMC) is first used as a novel binder in Li1.2Ni0.13Co0.13Mn0.54O2 cathode to enhance its cycling stability. Electrochemical performance is conducted by galvanostatic charge and discharge. Structure and morphology are characterized by X‐ray diffraction, scanning electronic microscopy, high‐resolution transmission electron microscopy, and X‐ray photoelectron spectroscopy. Results reveal that the CMC as binder can not only stabilize the electrode structure by preventing the electrode materials to detach from the current collector but also suppress the voltage fading of the Li1.2Ni0.13Co0.13Mn0.54O2 cathode due to Na+ ions doping. Most importantly, the dissolution of metal elements from the cathode materials into the electrolyte is also inhibited. 相似文献
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Sijiang Hu Yu Li Yuhua Chen Jiming Peng Tengfei Zhou Wei Kong Pang Christophe Didier Vanessa K. Peterson Hongqiang Wang Qingyu Li Zaiping Guo 《Liver Transplantation》2019,9(34)
Li‐rich layered oxides (LLOs) can deliver almost double the capacity of conventional electrode materials such as LiCoO2 and LiMn2O4; however, voltage fade and capacity degradation are major obstacles to the practical implementation of LLOs in high‐energy lithium‐ion batteries. Herein, hexagonal La0.8Sr0.2MnO3?y (LSM) is used as a protective and phase‐compatible surface layer to stabilize the Li‐rich layered Li1.2Ni0.13Co0.13Mn0.54O2 (LM) cathode material. The LSM is Mn? O? M bonded at the LSM/LM interface and functions by preventing the migration of metal ions in the LM associated with capacity degradation as well as enhancing the electrical transfer and ionic conductivity at the interface. The LSM‐coated LM delivers an enhanced reversible capacity of 202 mAh g?1 at 1 C (260 mA g?1) with excellent cycling stability and rate capability (94% capacity retention after 200 cycles and 144 mAh g?1 at 5 C). This work demonstrates that interfacial bonding between coating and bulk material is a successful strategy for the modification of LLO electrodes for the next‐generation of high‐energy Li‐ion batteries. 相似文献
4.
Ning Li Sooyeon Hwang Meiling Sun Yanbao Fu Vincent S. Battaglia Dong Su Wei Tong 《Liver Transplantation》2019,9(47)
Extensive efforts have been devoted to unraveling the true cause of voltage decay in Li, Mn‐rich layered oxides. An initial consensus was reached on structural rearrangement, then leaned toward the newly discovered lattice oxygen activity. It is challenging to differentiate their explicit roles because these events typically coexist during the electrochemical reaction of most Li‐rich layered oxides. Here, the voltage decay behavior is probed in Li1.2Ni0.2Ru0.6O2, a structurally and electrochemically relevant compound to Li, Mn‐rich layered oxide, but of no oxygen activity. Such intriguing characteristics allow the explicit decoupling of the contribution of transition metal migration and lattice oxygen activity to voltage decay in Li‐rich layered oxides. The results demonstrate that the microstructural evolution, mainly originating from transition metal migration, is a direct cause of voltage decay, and lattice oxygen activity likely accelerates the decay. 相似文献
5.
Site‐Selective In Situ Electrochemical Doping for Mn‐Rich Layered Oxide Cathode Materials in Lithium‐Ion Batteries
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Aram Choi Jungwoo Lim Hyung‐Jin Kim Sung Chul Jung Hyung‐Woo Lim Hanseul Kim Mi‐Sook Kwon Young Kyu Han Seung M. Oh Kyu Tae Lee 《Liver Transplantation》2018,8(11)
Various doped materials have been investigated to improve the structural stability of layered transition metal oxides for lithium‐ion batteries. Most doped materials are obtained through solid state methods, in which the doping of cations is not strictly site selective. This paper demonstrates, for the first time, an in situ electrochemical site‐selective doping process that selectively substitutes Li+ at Li sites in Mn‐rich layered oxides with Mg2+. Mg2+ cations are electrochemically intercalated into Li sites in delithiated Mn‐rich layered oxides, resulting in the formation of [Li1?xMgy][Mn1?zMz]O2 (M = Co and Ni). This Mg2+ intercalation is irreversible, leading to the favorable doping of Mg2+ at the Li sites. More interestingly, the amount of intercalated Mg2+ dopants increases with the increasing amount of Mn in Li1?x[Mn1?zMz]O2, which is attributed to the fact that the Mn‐to‐O electron transfer enhances the attractive interaction between Mg2+ dopants and electronegative Oδ? atoms. Moreover, Mg2+ at the Li sites in layered oxides suppresses cation mixing during cycling, resulting in markedly improved capacity retention over 200 cycles. The first‐principle calculations further clarify the role of Mg2+ in reduced cation mixing during cycling. The new concept of in situ electrochemical doping provides a new avenue for the development of various selectively doped materials. 相似文献
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Review on Challenges and Recent Advances in the Electrochemical Performance of High Capacity Li‐ and Mn‐Rich Cathode Materials for Li‐Ion Batteries
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Prasant Kumar Nayak Evan M. Erickson Florian Schipper Tirupathi Rao Penki Nookala Munichandraiah Philipp Adelhelm Hadar Sclar Francis Amalraj Boris Markovsky Doron Aurbach 《Liver Transplantation》2018,8(8)
Li and Mn‐rich layered oxides, xLi2MnO3·(1–x)LiMO2 (M=Ni, Mn, Co), are promising cathode materials for Li‐ion batteries because of their high specific capacity that can exceed 250 mA h g?1. However, these materials suffer from high 1st cycle irreversible capacity, gradual capacity fading, low rate capability, a substantial charge‐discharge voltage hysteresis, and a large average discharge voltage decay during cycling. The latter detrimental phenomenon is ascribed to irreversible structural transformations upon cycling of these cathodes related to potentials ≥4.5 V required for their charging. Transition metal inactivation along with impedance increase and partial layered‐to‐spinel transformation during cycling are possible reasons for the detrimental voltage fade. Doping of Li, Mn‐rich materials by Na, Mg, Al, Fe, Co, Ru, etc. is useful for stabilizing capacity and mitigating the discharge‐voltage decay of xLi2MnO3·(1–x)LiMO2 electrodes. Surface modifications by thin coatings of Al2O3, V2O5, AlF3, AlPO4, etc. or by gas treatment (for instance, by NH3) can also enhance voltage and capacity stability during cycling. This paper describes the recent literature results and ongoing efforts from our groups to improve the performance of Li, Mn‐rich materials. Focus is also on preparation of cobalt‐free cathodes, which are integrated layered‐spinel materials with high reversible capacity and stable performance. 相似文献
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Jianming Zheng Seungjun Myeong Woongrae Cho Pengfei Yan Jie Xiao Chongmin Wang Jaephil Cho Ji‐Guang Zhang 《Liver Transplantation》2017,7(6)
The lithium‐ and manganese‐rich (LMR) layered structure cathodes exhibit one of the highest specific energies (≈900 W h kg?1) among all the cathode materials. However, the practical applications of LMR cathodes are still hindered by several significant challenges, including voltage fade, large initial capacity loss, poor rate capability and limited cycle life. Herein, we review the recent progress and in depth understandings on the application of LMR cathode materials from a practical point of view. Several key parameters of LMR cathodes that affect the LMR/graphite full‐cell operation are systematically analyzed. These factors include the first‐cycle capacity loss, voltage fade, powder tap density, and electrode density. New approaches to minimize the detrimental effects of these factors are highlighted in this work. We also provide perspectives for the future research on LMR cathode materials, focusing on addressing the fundamental problems of LMR cathodes while keeping practical considerations in mind. 相似文献
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Defei Kong Jiangtao Hu Zhefeng Chen Kepeng Song Cheng Li Mouyi Weng Maofan Li Rui Wang Tongchao Liu Jiajie Liu Mingjian Zhang Yinguo Xiao Feng Pan 《Liver Transplantation》2019,9(41)
High‐Ni layered oxide cathodes are considered to be one of the most promising cathodes for high‐energy‐density lithium‐ion batteries due to their high capacity and low cost. However, surfice residues, such as NiO‐type rock‐salt phase and Li2CO3, are often formed at the particle surface due to the high reactivity of Ni3+, and inevitably result in an inferior electrochemical performance, hindering the practical application. Herein, unprecedentedly clean surfaces without any surfice residues are obtained in a representative LiNi0.8Co0.2O2 cathode by Ti‐gradient doping. High‐resolution transmission electron microscopy (TEM) reveals that the particle surface is composed of a disordered layered phase (≈6 nm in thickness) with the same rhombohedra structure as its interior. The formation of this disordered layered phase at the particle surface is electrochemically favored. It leads to the highest rate capacity ever reported and a superior cycling stability. First‐principles calculations further confirm that the excellent electrochemical performance has roots in the excellent chemical/structural stability of such a disordered layered structure, mainly arising from the improved robustness of the oxygen framework by Ti doping. This strategy of constructing the disordered layered phase at the particle surface could be extended to other high‐Ni layered transition metal oxides, which will contribute to the enhancement of their electrochemical performance. 相似文献
9.
Zhi Zhu Rui Gao Iradwikanari Waluyo Yanhao Dong Adrian Hunt Jinhyuk Lee Ju Li 《Liver Transplantation》2020,10(35)
Li‐rich metal oxide (LXMO) cathodes have attracted intense interest for rechargeable batteries because of their high capacity above 250 mAh g?1. However, the side effects of hybrid anion and cation redox (HACR) reactions, such as oxygen release and phase collapse that result from global oxygen migration (GOM), have prohibited the commercialization of LXMO. GOM not only destabilizes the oxygen sublattice in cycling, aggravating the well‐known voltage fading, but also intensifies electrolyte decomposition and Mn dissolution, causing severe full‐cell performance degradation. Herein, an artificial surface prereconstruction (ASR) for Li1.2Mn0.6Ni0.2O2 particles with a molten‐molybdate leaching is conducted, which creates a crystal‐dense anion‐redox‐free LiMn1.5Ni0.5O4 shell that completely encloses the LXMO lattice (ASR‐LXMO). Differential electrochemical mass spectroscopy and soft X‐ray absorption spectroscopy analyses demonstrate that GOM is shut down in cycling, which not only stabilizes HACR in ASR‐LXMO, but also mitigates the electrolyte decomposition and Mn dissolution. ASR‐LXMO displays greatly stabilized cycling performance as it retains 237.4 mAh g?1 with an average discharge voltage of 3.30 V after 200 cycles. More crucially, while the pristine LXMO cycling cannot survive 90 cycles in a pouch full‐cell matched with a commercial graphite anode and lean (2 g A?1 h?1) electrolyte, ASR‐LXMO shows high capacity retention of 76% after 125 cycles in full‐cell cycling. 相似文献
10.
A New Spinel‐Layered Li‐Rich Microsphere as a High‐Rate Cathode Material for Li‐Ion Batteries
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Dong Luo Guangshe Li Chaochao Fu Jing Zheng Jianming Fan Qi Li Liping Li 《Liver Transplantation》2014,4(11)
Li‐rich layered materials are considered to be the promising low‐cost cathodes for lithium‐ion batteries but they suffer from poor rate capability despite of efforts toward surface coating or foreign dopings. Here, spinel‐layered Li‐rich Li‐Mn‐Co‐O microspheres are reported as a new high‐rate cathode material for Li‐ion batteries. The synthetic procedure is relatively simple, involving the formation of uniform carbonate precursor under solvothermal conditions and its subsequent transformation to an assembled microsphere that integrates a spinel‐like component with a layered component by a heat treatment. When calcined at 700 °C, the amount of transition metal Mn and Co in the Li‐Mn‐Co‐O microspheres maintained is similar to at 800 °C, while the structures of constituent particles partially transform from 2D to 3D channels. As a consequence, when tested as a cathode for lithium‐ion batteries, the spinel‐layered Li‐rich Li‐Mn‐Co‐O microspheres obtained at 700 °C show a maximum discharge capacity of 185.1 mA h g?1 at a very high current density of 1200 mA g?1 between 2.0 and 4.6 V. Such a capacity is among the highest reported to date at high charge‐discharge rates. Therefore, the present spinel‐layered Li‐rich Li‐Mn‐Co‐O microspheres represent an attractive alternative to high‐rate electrode materials for lithium‐ion batteries. 相似文献
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Operando Lithium Dynamics in the Li‐Rich Layered Oxide Cathode Material via Neutron Diffraction
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Haodong Liu Yan Chen Sunny Hy Ke An Subramanian Venkatachalam Danna Qian Minghao Zhang Ying Shirley Meng 《Liver Transplantation》2016,6(7)
Neutron diffraction under operando battery cycling is used to study the lithium and oxygen dynamics of high Li‐rich Li(Lix/3Ni(3/8‐3x/8)Co(1/4‐x/4)Mn(3/8+7x/24)O2 (x = 0.6, HLR) and low Li‐rich Li(Lix/3Ni(1/3‐x/3)Co(1/3‐x/3)Mn(1/3+x/3)O2 (x = 0.24, LLR) compounds that exhibit different degrees of oxygen activation at high voltage. The measured lattice parameter changes and oxygen position show largely contrasting changes for the two cathodes where the LLR exhibits larger movement of oxygen and lattice contractions in comparison to the HLR that maintains relatively constant lattice parameters and oxygen position during the high voltage plateau until the end of charge. Density functional theory calculations show the presence of oxygen vacancy during the high voltage plateau; changes in the lattice parameters and oxygen position are consistent with experimental observations. Lithium migration kinetics for the Li‐rich material is observed under operando conditions for the first time to reveal the rate of lithium extraction from the lithium layer, and transition metal layer is related to the different charge and discharge characteristics. At the beginning of charging, the lithium extraction predominately occurs within the lithium layer. Once the high voltage plateau is reached, the lithium extraction from the lithium layer slows down and extraction from the transition metal layer evolves at a faster rate. 相似文献
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Understanding the Rate Capability of High‐Energy‐Density Li‐Rich Layered Li1.2Ni0.15Co0.1Mn0.55O2 Cathode Materials
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Xiqian Yu Yingchun Lyu Lin Gu Huiming Wu Seong‐Min Bak Yongning Zhou Khalil Amine Steven N. Ehrlich Hong Li Kyung‐Wan Nam Xiao‐Qing Yang 《Liver Transplantation》2014,4(5)
The high‐energy‐density, Li‐rich layered materials, i.e., xLiMO2(1‐x)Li2MnO3, are promising candidate cathode materials for electric energy storage in plug‐in hybrid electric vehicles (PHEVs) and electric vehicles (EVs). The relatively low rate capability is one of the major problems that need to be resolved for these materials. To gain insight into the key factors that limit the rate capability, in situ X‐ray absorption spectroscopy (XAS) and X‐ray diffraction (XRD) studies of the cathode material, Li1.2Ni0.15Co0.1Mn0.55O2 [0.5Li(Ni0.375Co0.25 Mn0.375)O2·0.5Li2MnO3], are carried out. The partial capacity contributed by different structural components and transition metal elements is elucidated and correlated with local structure changes. The characteristic reaction kinetics for each element are identified using a novel time‐resolved XAS technique. Direct experimental evidence is obtained showing that Mn sites have much poorer reaction kinetics both before and after the initial activation of Li2MnO3, compared to Ni and Co. These results indicate that Li2MnO3 may be the key component that limits the rate capability of Li‐rich layered materials and provide guidance for designing Li‐rich layered materials with the desired balance of energy density and rate capability for different applications. 相似文献
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Shuai Liu Zepeng Liu Xi Shen Xuelong Wang Sheng‐Chieh Liao Richeng Yu Zhaoxiang Wang Zhiwei Hu Chien‐Te Chen Xiqian Yu Xiaoqing Yang Liquan Chen 《Liver Transplantation》2019,9(32)
Li‐rich layered metal oxides are one type of the most promising cathode materials in lithium‐ion batteries but suffer from severe voltage decay during cycling because of the continuous transition metal (TM) migration into the Li layers. A Li‐rich layered metal oxide Li1.2Ti0.26Ni0.18Co0.18Mn0.18O2 (LTR) is hereby designed, in which some of the Ti4+ cations are intrinsically present in the Li layers. The native Li–Ti cation mixing structure enhances the tolerance for structural distortion and inhibits the migration of the TM ions in the TMO2 slabs during (de)lithiation. Consequently, LTR exhibits a remarkable cycling stability of 97% capacity retention after 182 cycles, and the average discharge potential drops only 90 mV in 100 cycles. In‐depth studies by electron energy loss spectroscopy and aberration‐corrected scanning transmission electron microscopy demonstrate the Li–Ti mixing structure. The charge compensation mechanism is uncovered with X‐ray absorption spectroscopy and explained with the density function theory calculations. These results show the superiority of introducing transition metal ions into the Li layers in reinforcing the structural stability of the Li‐rich layered metal oxides. These findings shed light on a possible path to the development of Li‐rich materials with better potential retention and a longer lifespan. 相似文献
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To pursue a higher energy density (>300 Wh kg?1 at the cell level) and a lower cost (<$125 kWh?1 expected at 2022) of Li‐ion batteries for making electric vehicles (EVs) long range and cost‐competitive with internal combustion engine vehicles, developing Ni‐rich/Co‐poor layered cathode (LiNi1?x?yCoxMnyO2, x+y ≤ 0.2) is currently one of the most promising strategies because high Ni content is beneficial to high capacity (>200 mAh g?1) while low Co content is favorable to minimize battery cost. Unfortunately, Ni‐rich cathodes suffer from limited structure stability and electrode/electrolyte interface stability in the charged state, leading to electrode degradation and poor cycling performance. To address these problems, various strategies have been employed such as doping, structural optimization design (e.g., core–shell structure, concentration‐gradient structure, etc.), and surface coating. In this review, five key aspects of Ni‐rich/Co‐poor layered cathode materials are explored: energy density, fast charge capability, service life including cycling life and calendar life, cost and element resources, and safety. This enables a comprehensive analysis of current research advances and challenges from the perspective of both academy and industry to help facilitate practical applications for EVs in the future. 相似文献
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Wontae Lee Shoaib Muhammad Taewhan Kim Hyunchul Kim Eunkang Lee Mihee Jeong Suhan Son Jae‐Hyun Ryou Won‐Sub Yoon 《Liver Transplantation》2018,8(4)
An increase in the amount of nickel in LiMO2 (M = Ni, Co, Mn) layered system is actively pursued in lithium‐ion batteries to achieve higher capacity. Nevertheless, fundamental effects of Ni element in the three‐component layered system are not systematically studied. Therefore, to unravel the role of Ni as a major contributor to the structural and electrochemical properties of Ni‐rich materials, Co‐fixed LiNi0.5+xCo0.2Mn0.3–xO2 (x = 0, 0.1, and 0.2) layered materials are investigated. The results, on the basis of synchrotron‐based characterization techniques, present a decreasing trend of Ni2+ content in Li layer with increasing total Ni contents. Moreover, it is discovered that the chex.‐lattice parameter of layered system is not in close connection with the interslab thickness related to actual Li ion pathway. The interslab thickness increases with increasing Ni concentration even though the chex.‐lattice parameter decreases. Furthermore, the lithium ion pathway is preserved in spite of the fact that the c‐axis is collapsed at highly deintercalated states. Also, a higher Ni content material shows better structural properties such as larger interslab thickness, lower cation disorder, and smoother phase transition, resulting in better electrochemical properties including higher Li diffusivity and lower overpotential when comparing materials with lower Ni content. 相似文献
18.
Ni and Co Segregations on Selective Surface Facets and Rational Design of Layered Lithium Transition‐Metal Oxide Cathodes
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Pengfei Yan Jianming Zheng Jiaxin Zheng Zhiguo Wang Gaofeng Teng Saravanan Kuppan Jie Xiao Guoying Chen Feng Pan Ji‐Guang Zhang Chong‐Min Wang 《Liver Transplantation》2016,6(9)
The chemical processes occurring on the surface of cathode materials during battery cycling play a crucial role in determining battery's performance. However, the understanding of such surface chemistry is far from clear due to the complexity of redox chemistry during battery charge/discharge. Through intensive aberration corrected STEM investigation on ten layered oxide cathode materials, two important findings on the pristine oxides are reported. First, Ni and Co show strong plane selectivity when building up their respective surface segregation layers (SSLs). Specifically, Ni‐SSL is exclusively developed on (200)m facet in Li–Mn‐rich oxides (monoclinic C2/m symmetry) and on (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 Li–Mn‐rich cathodes. Structurally, Ni‐SSLs tend to form spinel‐like lattice while Co‐SSLs are in a rock‐salt‐like structure. Second, by increasing Ni concentration in these layered oxides, Ni and Co SSLs can be suppressed and even eliminated. The 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. 相似文献
19.
Jun Wang Xin He Elie Paillard Nina Laszczynski Jie Li Stefano Passerini 《Liver Transplantation》2016,6(21)
Layered lithium‐ and manganese‐rich oxides (LMROs), described as xLi2MnO3·(1–x)LiMO2 or Li1+yM1–yO2 (M = Mn, Ni, Co, etc., 0 < x <1, 0 < y ≤ 0.33), have attracted much attention as cathode materials for lithium ion batteries in recent years. They exhibit very promising capacities, up to above 300 mA h g?1, due to transition metal redox reactions and unconventional oxygen anion redox reaction. However, they suffer from structural degradation and severe voltage fade (i.e., decreasing energy storage) upon cycling, which are plaguing their practical application. Thus, this review will aim to describe the pristine structure, high‐capacity mechanisms and structure evolutions of LMROs. Also, recent progress associated with understanding and mitigating the voltage decay of LMROs will be discussed. Several approaches to solve this problem, such as adjusting cycling voltage window and chemical composition, optimizing synthesis strategy, controlling morphology, doping, surface modification, constructing core‐shell and layered‐spinel hetero structures, are described in detail. 相似文献
20.
Arumugam Manthiram James C. Knight Seung‐Taek Myung Seung‐Min Oh Yang‐Kook Sun 《Liver Transplantation》2016,6(1)
Ni‐rich layered oxides and Li‐rich layered oxides are topics of much research interest as cathodes for Li‐ion batteries due to their low cost and higher discharge capacities compared to those of LiCoO2 and LiMn2O4. However, Ni‐rich layered oxides have several pitfalls, including difficulty in synthesizing a well‐ordered material with all Ni3+ ions, poor cyclability, moisture sensitivity, a thermal runaway reaction, and formation of a harmful surface layer caused by side reactions with the electrolyte. Recent efforts towards Ni‐rich layered oxides have centered on optimizing the composition and processing conditions to obtain controlled bulk and surface compositions to overcome the capacity fade. Li‐rich layered oxides also have negative aspects, including oxygen loss from the lattice during first charge, a large first cycle irreversible capacity loss, poor rate capability, side reactions with the electrolyte, low tap density, and voltage decay during extended cycling. Recent work on Li‐rich layered oxides has focused on understanding the surface and bulk structures and eliminating the undesirable properties. Followed by a brief introduction, an account of recent developments on the understanding and performance gains of Ni‐rich and Li‐rich layered oxide cathodes is provided, along with future research directions. 相似文献