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Interfacial engineering of the layered oxide cathode materials for sodium-ion battery

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Nano Research 2024年第3期17卷 1441-1464页

作者： Quanqing Zhao Ruru Wang Ming Gao Faheem KButt Jianfeng Jia Haishun Wu Youqi Zhu Key Laboratory of Magnetic Molecules and Magnetic Information Materials of Ministry of Education School of Chemistry and Materials ScienceShanxi Normal UniversityTaiyuan 030032China Metals and Chemistry Research Institute China Academy of Railway Sciences Corporation LimitedBeijing 100081China Department of Physics Division of Science and TechnologyUniversity of EducationLahore 54770Pakistan Research Center of Materials Science Beijing Key Laboratory of Construction Tailorable Advanced Functional Materials and Green ApplicationsBeijing Institute of TechnologyBeijing 100081China

The layered metal oxides are reviewed as the hopeful cathode materials for high-performance sodium-ion batteries(SIBs)due to their large theoretical capacity,favorable two-dimensional(2D)ion diffusion channel,and simple manipuility.However,their cycling stability,rate capability,and thermal stability are still significantly concerned and highlighted before further practical application.The chemical,mechanical and electrochemical stability of the cathode–electrolyte interfaces upon cycling is of great significance.Herein,the unique structural and electrochemical properties of the layered oxide cathode materials for SIB are reviewed.The mechanism of bulk/surface degradation induced by oxygen evolution,phase transition,microcrack,and electrolyte decomposition is thoroughly understood.Furthermore,the interfacial engineering to construct stable interface through various effective methods is fully discussed.The future outlook and challenges for interfacial engineering in this filed are also summarized.This review should shed light on the rational design and construct of robust interface for applications of superior layered oxide cathodes in SIB and may suggest future research directions.

关键词： interfacial engineering sodium-ion battery layered oxide electrolyte interface

Mg/Fe site-specific dual-doping to boost the performance of cobalt-free nickle-rich layered oxide cathode for high-energy lithium-ion batteries

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Journal of Energy Chemistry 2024年第4期91卷 670-679页

作者： Yunting Wang Gaohui Du Di Han Wenhao Shi Jiahao Deng Huayu Li Wenqi Zhao Shukai Ding Qingmei Su Bingshe Xu Materials Institute of Atomic and Molecular Science Shaanxi University of Science and TechnologyXi'an 710021ShanxiChina Shanxi-Zheda Institute of Advanced Materials and Chemical Engineering Taiyuan 030024ShanxiChina Key Laboratory of Interface Science and Engineering in Advanced Materials Taiyuan University of TechnologyTaiyuan 030024ShanxiChina

Layer-type LiNi0.9Mn0.1O2is promising to be the primary cathode material for lithium-ion batteries(LIBs)due to its excellent electrochemical performance.Unfortunately,the cathode with high nickel content suffers from severely detrimental structural transformation that causes rapid capacity attenuation.Herein,site-specific dual-doping with Fe and Mg ions is proposed to enhance the structural stability of LiNi0.9Mn0.1O2.The Fe3+dopants are inserted into transition metal sites(3b)and can favorably provide additional redox potential to compensate for charge and enhance the reversibility of anionic redox.The Mg ions are doped into the Li sites(3a)and serve as O_(2)^(-)-Mg^(2+)-O_(2)^(-)pillar to reinforce the electrostatic cohesion between the two adjacent transition-metal layers,which further suppress the cracking and the generation of harmful phase transitions,ultimately improving the cyclability.The theoretical calculations,including Bader charge and crystal orbital Hamilton populations(COHP)analyses,confirm that the doped Fe and Mg can form stable bonds with oxygen and the electrostatic repulsion of O_(2)^(-)-O_(2)^(-)can be effectively suppressed,which effectively mitigates oxygen anion loss at the high delithiation state.This dual-site doping strategy offers new avenues for understanding and regulating the crystalline oxygen redox and demonstrates significant potential for designing high-performance cobalt-free nickel-rich cathodes.

关键词： Cobalt-free layered oxide Cathode Dual dopants Density functional theory calculation

P2-type Na_(0.6)[Mg(Ⅱ)_(0.3)Mn(Ⅳ)_(0.7)]O_2 as a new model material for anionic redox reaction

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Chinese Chemical Letters 2018年第12期29卷 1791-1794页

作者： Xiaohui Rong Fei Gao Yaxiang Lu Kai Yang Yongsheng Hu State Key Laboratory of Operation and Control of Renewable Energy and Storage Systems China Electric Power Research Institute Key Laboratory for Renewable Energy Beijing Key Laboratory for New Energy Materials and Devices Beijing National Laboratory for Condensed Matter Physics Institute of Physics Chinese Academy of Sciences Center of Materials Science and Optoelectronics Engineering University of Chinese Academy of Sciences

A new model material of Na[Mg(Ⅱ)Mn(Ⅳ)]O, with only Mgand Mnin the transition metal layers, is synthesized for the research of anionic redox reaction. The material delivers a capacity of ～130 mAh/g with a long plateau at ～4.2 V in the initial charge profile, indicating anionic redox reaction(ARR) involved during the initial desodiation process. In the following cycles, the reversible capacity can reach a high value of ～210 mAh/g, which is probably derived from the participation of both ARR and Mn/Mnredox couples, further proving the charge compensation from ARR during the initial charge and following cycles. The designed cathode material without Mnhelps avoid the influence of oxygen activity from transition metals, enabling the investigation of ARR without other distractions.

关键词： Na-ion batteries layered oxide Cathode Anionic redox reaction Na_(0.6)[Mg_(0.3)Mn_(0.7)]O_2

Dual-strategy modification on P2-Na_(0.67)Ni_(0.33)Mn_(0.67)O_(2)realizes stable high-voltage cathode and high energy density full cell for sodium-ion batteries

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SusMat 2023年第1期3卷 58-71页

作者： Guanglin Wan Bo Peng Liping Zhao Feng Wang Lai Yu Rong Liu Genqiang Zhang Hefei National Research Center for Physical Sciences at the Microscale CAS Key Laboratory of Materials for Energy ConversionDepartment of Materials Science and EngineeringUniversity of Science and Technology of ChinaHefeiAnhuiP.R.China Department of Chemistry University of Science and Technology of ChinaHefeiAnhuiP.R.China

P2-type Na_(0.67)Ni_(0.33)Mn_(0.67)O_(2)is considered as a potential cathode material for sodium-ion batteries due to the merits of high voltage,low cost,and air stability.However,the unsatisfied cycling stability and rate performance caused by the destructive phase transition and side reactions hinder its practical application.Herein,we present a feasible dual strategy of Mg^(2+)doping integrated with ZrO_(2)surface modification for P2-Na_(0.67)Ni_(0.33)Mn_(0.67)O_(2),which can well address the issues of phase transition and side reactions benefitting from the enhanced structural and interfacial stabilities.Specifically,it exhibits a decent cycling stability with a capacity retention of 81.5%at 1 C and promising rate performance with a discharge capacity of 76.6 mA h g^(−1)at 5 C.The in situ X-ray diffraction measurement confirms that the damaged P2-O2 phase transition is suppressed with better reversibility in high-voltage region,whereas the side reactions are inhibited due to the protective ZrO_(2)surfacemodification.Commendably,the full cell achieves an outstanding operating voltage of 3.57 V and a fabulous energy density of 238.91 W h kg^(−1)at 36.73 W kg^(−1),demonstrating great practicability.This work is expected to provide a new insight for designing stable high-voltage cathode materials and high energy density full cells for sodium ion batteries.

关键词： cathode full cell high voltage layered oxide sodium-ion battery

Oxygen vacancy promising highly reversible phase transition in layered cathodes for sodium-ion batteries

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Nano Research 2021年第11期14卷 4100-4106页

作者： Kezhu Jiang Shaohua Guo Wei Kong Pang Xueping Zhang Tiancheng Fang Shao-fei Wang Fangwei Wang Xiaoyu Zhang Ping He Haoshen Zhou Center of Energy Storage Materials&Technology College of Engineering and Applied SciencesNational Laboratory of Solid State MicrostructuresCollaborative Innovation Center of Advanced MicrostructuresJiangsu Key Laboratory of Artificial Functional MaterialsNanjing UniversityNanjing210093China Institute for Superconducting&Electronic Materials School of MechanicalMaterials and Mechatronics EngineeringUniversity of WollongongWollongongNSW2522Australia China Spallatoin Neutron Source Institute of High Energy PhysicsChinese Academy of SciencesDongguan523808China School of Nuclear Science and Technology University of Chinese Academy of SciencesBeijing101408China Beijing National Laboratory for Condensed Matter Physics Institute of Physics Chinese Academy of SciencesBeijing100190China School of Physical Sciences University of Chinese Academy of SciencesBeijing101408China Songshan Lake Materials Laboratory Dongguan523808China School of materials science and engineering Jiangsu UniversityZhenjiang212013China Energy Technology Research Institute National Institute of Advanced Industrial Science and Technology(AIST)Umezono 1-1-1Tsukuba305-8568Japan

Phase transition is common during (de)-intercalating layered sodium oxides, which directly affects the structural stability and electrochemical performance. However, the artificial control of phase transition to achieve advanced sodium-ion batteries is lacking, since the remarkably little is known about the influencing factor relative to the sliding process of transition-metal slabs upon sodium release and uptake of layered oxides. Herein, we for the first time demonstrate the manipulation of oxygen vacancy concentrations in multinary metallic oxides has a significant impact on the reversibility of phase transition, thereby determining the sodium storage performance of cathode materials. Results show that abundant oxygen vacancies intrigue the return of the already slide transition-metal slabs between O_(3) and P_(3) phase transition, in contrast to the few oxygen vacancies and resulted irreversibility. Additionally, the abundant oxygen vacancies enhance the electronic and ionic conductivity of the Na0.9Ni0.3Co0.15Mn0.05Ti0.5O2 electrode, delivering the high initial Coulombic efficiency of 97.1%, large reversible capacity of 112.7 mAh·g−1, superior rate capability upon 100 C and splendid cycling performance over 1,000 cycles. Our findings open up new horizons for artificially manipulating the structural evolution and electrochemical process of layered cathodes, and pave a way in designing advanced sodium-ion batteries.

关键词： sodium-ion battery layered oxide O_(3)phase oxygen vacancy reversible phase transition

Ultralong Life Symmetric Potassium Ion Batteries Using a Bipolar Cr/Ti Based layered Material

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Chemical Research in Chinese Universities 2021年第3期37卷 739-744页

作者： WANG Ziyang ZHANG Xinyuan LIU Yuhan WANG Chunzhong DU Fei Key Laboratory of Physics and Technology for Advanced Batteries Ministry of EducationState Key Laboratory of Superhard MaterialsCollege of PhysicsJilin UniversityChangchun130012P.R.China

Based on low cost and earth abundance potassium resources,potassium-ion batteries have been regarded as the potential candidate for large-scale energy storage applications for renewable energy and smart grid.Although some earlier works have proposed reversible insertion/extraction of K^(+)ions in K cells,their cycle instability is insufficient for the further application of potassium-ion batteries.Herein,we report a symmetric potassium-ion battery with ultralong life employing a bipolar Cr/Ti based layered oxide,which contains two electrochemically active transition metals with the redox couples of Cr^(4+)/Cr^(3+)and Ti^(4+)/Ti^(3+)working on the cathode and anode side,respectively.Moreover,the(de)intercalation process in the structure and the in-situ electrochemical exchange process are investigated by ex-situ XRD.As a result,the symmetric cell based on the obtained K-based bipolar layered material exhibits a reversible capacity of 102 mA·h/g between 0.5 V and 3.5 V at 20 mA/g,an ultralong cycle life of 2000 cycles with a capacity retention of 80%and high rate capabilities.The outstanding cycling stability and rate performance endow this work with promising advantages for the future development of the novel energy storage system.

关键词： layered oxide Potassium-ion battery Symmetric electrode Ultralong life

Ferroelectricity in layered Perovskites as a Model of Ultra-Thin Films

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World Journal of Condensed Matter Physics 2016年第3期6卷 224-243页

作者： Masanori Fukunaga Masaki Takesada Akira Onodera Department of Physics Hokkaido University Sapporo Japan

The instability of thin ferroelectric films is discussed based on the close similarity of dielectric properties between bulk Bi-layered perovskites and thin BaTiO3 films. The dielectric properties of pseudo-two-dimensional layered perovskites suggest that the bulk layered ferroelectric is a good model of ultra-thin ferroelectric film with a few perovskite units, free from any misfit lattice strain. It seems plausible that the ferroelectric interaction is still prominent but shows a crossover from ferroelectric to antiferroelectric along the unique c-axis (perpendicular to the film plane);with decreasing thickness, the ferroelectricity appears within the plane, which results in so-called “canted ferroelectricity”. An extra relaxation mode induced by surface effect of thin films correlates with soft mode, which results in a new intermediate phase between the paraelectric and ferroelectric phases. These evidences may indicate no critical thickness even for ferroelectric ultra- thin films.

关键词： Ferroelectricity layered oxide Perovskite Thin Film Size Effect