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Mn-based cathode materials for rechargeable batteries

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Science China Chemistry 2024年第1期67卷 87-105页

作者： Xu Zhang Shiqi Liu Boya Wang Guoqing Wang Haozhe Du Xuanyu Wang Haidong Zhang Shu Zhao Lin Wang Haijun Yu Institute of Advanced Battery materials and Devices Faculty of Materials and ManufacturingBeijing University of TechnologyBeijing 100124China Key Laboratory of Advanced Functional materials Ministry of EducationBeijing University of TechnologyBeijing 100124China Create Energy&Benefit Future Co.Ltd. Beijing 100176China

The rapid expansion of renewable energies asks for great progress of energy-storage technologies for sustainable energy supplies,which raises the compelling demand of high-performance rechargeable batteries.To satisfy the huge demand from the coming energy-storage market,the resource and cost-effectiveness of rechargeable batteries become more and more important.Manganese(Mn)as a key transition element with advantages including high abundance,low cost,and low toxicity derives various kinds(spinels,layered oxides,polyanions,Prussian blue analogs,etc.)of high-performance Mn-based electrode materials,especially cathodes,for rechargeable batteries ranging from Li-ion batteries,Na-ion batteries,aqueous batteries,to multivalent metal-ion batteries.It is anticipated that Mn-based materials with Mn as the major transition-metal element will constitute a flourishing family of Mn-based rechargeable batteries(Mn RBs)for large-scale and differentiated energy-storage applications.On the other hand,several critical issues including Jahn-Teller effect,Mn dissolution,and O release greatly hinder the pace of Mn RBs,which require extensive material optimizations and battery/system improvements.This review aims to provide an investigation about Mn-based materials and batteries for the coming energy-storage demands,with compelling issues and challenges that must be overcome.

关键词： manganese cathode materials Mn-based rechargeable batteries energy storage

Advances of high-performance LiNi_(1-x-y)Co_(x)M_(y)O_(2) cathode materials and their precursor particles via co-precipitation process

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Particuology 2024年第3期86卷 67-85页

作者： Wenbiao Liang Yin Zhao Liyi Shi Zhuyi Wang Yi Wang Meihong Zhang Shuai Yuan School of materials Science and Engineering Shanghai UniversityShanghai200444China Research Center of Nanoscience and Nanotechnology Shanghai UniversityShanghai200444China Emerging Industries Institute Shanghai UniversityJiaxingZhejiang314006China

Layered LiNi_(1-x-y)Co_(x)M_(y)O_(2)(M=Mn or Al)is a promising cathode material for lithium-ion batteries due to its high specific capacity and acceptable manufacturing cost.However,the polycrystalline LiNi_(1-x-y)Co_(x)M_(y)O_(2) cathode material suffers from disordered orientation of primary particles and poor geometric symmetry of secondary particles,which severely hampers the migration of Lit ions.Furthermore,the resulting anisotropy accelerates the disintegration of the secondary particle structure,significantly affecting the electrochemical performance of the polycrystalline cathode.In spite of less grain boundary,the single-crystal LiNi_(1-x-y)Co_(x)M_(y)O_(2) cathodes still suffer from severe microcracks generated by repeated planar gliding during cycling,which poses a great challenge to the cycling stability of single-crystal materials.It's worth noting that the microstructure of the cathode material is mainly inherited from its precursor.Therefore,it is necessary to deeply understand the influence of the microstructure of Ni_(1-x-y)Co_(x)M_(y)(OH)2 on the electrochemical properties of LiNi_(1-x-y)Co_(x)M_(y)O_(2) cathode materials,so as to optimize the production process of preparing high-performance cathode precursors.In this review,we summarize recent advances in the research and development of Ni-rich cathode precursor materials.Firstly,the challenges faced by the Ni-rich hydroxide precursor materials are presented,including the effect of primary particle morphology and arrangement on the electrochemical performance of cathode materials,the influence of secondary particle morphology on lithium insertion reactions in cathode,and the effect of particle size on the microcracking of single-crystal particles.Secondly,the presentation of the conventional co-precipitation reactor,the mechanism of precursor particle growth,and the influence of coprecipitation parameters are described in detail.Finally,the strategies are systematically discussed to solve the challenges of hydroxide precursors,such as the inno

关键词： Lithium-ion batteries cathode materials Co-precipitation Ni-rich layered oxides Single crystal Precursor particles

Building Better Full Manganese‑Based cathode materialsfor Next‑Generation Lithium‑Ion Batteries

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Electrochemical Energy Reviews 2023年第1期6卷 148-185页

作者： Jin Song Hangchao Wang Yuxuan Zuo Kun Zhang Tonghuan Yang Yali Yang Chuan Gao Tao Chen Guang Feng Zewen Jiang Wukun Xiao Tie Luo Dingguo Xia Beijing Key Laboratory of Theory and Technology for Advanced Battery materials School of Materials Science and EngineeringPeking UniversityBeijing 100871China College of Chemistry and Molecular Science Wuhan UniversityWuhan 430072HubeiChina College of Engineering Peking UniversityBeijing 100871China

Lithium-manganese-oxides have been exploited as promising cathode materials for many years due to their environmental friendliness,resource abundance and low biotoxicity.Nevertheless,inevitable problems,such as Jahn-Teller distortion,manganese dissolution and phase transition,still frustrate researchers;thus,progress in full manganese-based cathode materials(FMCMs)has been relatively slow and limited in recent decades.Recently,with the fast growth of vehicle electrification and large-scale energy-storage grids,there has been an urgent demand to develop novel FMCMs again;actually,new waves of research based on FMCMs are being created.Herein,we systematically review the history of FMCMs,correctly describe their structures,evaluate the advantages and challenges,and discuss the resolution strategies and latest developments.Additionally,beyond FMCMs,a profound discussion of current controversial issues,such as oxygen redox reaction,voltage decay and voltage hysteresis in Li_(2)MnO_(3)-based cathode materials,is also presented.This review summarizes the effectively optimized approaches and offers a few new possible enhancement methods from the perspective of the electronic-coordination-crystal structure for building better FMCMs for next-generation lithium-ion batteries.

关键词： Energy storage Lithium-ion batteries cathode materials Manganese oxides

Enhanced stability and electrochemical properties of lanthanum and cerium co-modified LiVOPO_(4) cathode materials for Li-ion batteries

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Journal of Rare Earths 2023年第10期41卷 1590-1596,I0005页

作者： Zishan Ahsan Zhenfei Cai Shuai Wang Haichuan Wang Yangzhou Ma Guangsheng Song Shihong Zhang Weidong Yang Muhammad Imran Cuie Wen Key Laboratory of Green Fabrication and Surface Technology of Advanced Metal materials Ministry of EducationSchool of Materials Science and EngineeringAnhui University of TechnologyMaanshan243000China School of Metallurgical Engineering Anhui University of TechnologyMaanshan243002China Future Manufacturing Flagship Commonwealth Scientific and Industry Research OrganizationMelbourneVictoria3168Australia Department of Chemistry Faculty of ScienceKing Khalid UniversityAbha61413Saudi Arabia School of Engineering RMIT UniversityBundooraVictoria3083Australia

A facile and efficient ball-milling assisted sol-gel synthesis route was developed to prepare triclinic e-LiVOPO_(4)(LVOP)material with lanthanum(La)and cerium(Ce)modification individually as well as simultaneously.An LVOP/LaPO_(4)/CePO_(4)composite cathode material was successfully synthesized and results show that La and Ce co-modification noticeably improves the electrochemical performance by enhancing the high voltage capacity upon cycling,which indicates contributions from the good ionic conductors LaPO_(4)and CePO_(4).The simultaneous La and Ce modification improves the high voltage performance significantly with an increase of 50%in high voltage capacity after 20 cycles compared to pure LVOP.It also shows stabilized cycling perfo rmance with 91%capacity rete ntion after 50 cycles at 0.1 C rate,along with high-rate capability with a capacity of 83.1 mAh/g compared to the pristine sample showing the capacity of 51.6 mAh/g at a high rate of 5C.This can be attributed to the good conductivity of LaPO_(4)and CePO_(4).In addition,the LVOP/LaPO_(4)/CePO_(4)composite and the pristine LVOP give a charge transfer resistance of-105 and-212Ω,respectively,showing much lower impedance due to a combination of La and Ce addition.

关键词： Li-ion bateries ε-LiVOP04 cathode materials La Ce co-modification Enhanced stability Rare earths

Organopolysulfides as high-performance cathode materials for rechargeable aluminum-ion batteries

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Journal of materials Science & Technology 2023年第23期154卷 159-165页

作者： Weiqin Chu Xu Zhang Fulong Zhu Shuaixia Li Yongzhu Fu Haijun Yu Institute of Advanced Battery materials and Devices Faculty of Materials and Manufacturing Beijing University of Technology Beijing 100124 China Key Laboratory of Advanced Functional materials Ministry of Education Beijing University of Technology Beijing 100124 China College of Chemistry Zhengzhou University Zhengzhou 450001 China

The development of aluminum-ion batteries(AIBs)is significantly confined by the limited high-performance cathode materials.Herein,organopolysulfides are investigated as active cathode materials to fabricate AIBs.A liquid-phase phenyl tetrasulfide(PTS)can deliver a capacity above 600 mAh g−1 after activation,with the maintenance of 253 mAh g−1 after 100 cycles.Owing to the different S locations,PTS shows several voltage plateaus and an average voltage of∼0.7 V vs.Al3+/Al with no decay upon cycling.More importantly,the liquid PTS can serve as a high-Coulombic-efficiency cathode(∼99.88%±0.57%after stabilization),enlighting the design of high-efficiency and low-resistance conversion-type cathode materials for AIBs.By experimental characterizations accompanied by theoretical calculations,it is found that PTS undergoes stepwise reaction procedures during discharge with final products of Al2S3 and AlCl2-coordinated phenyl sulfide,and partially reforms with elemental S and other organopolysulfides during charge.This study demonstrates new opportunities for the design of high-efficiency conversion-type cathode materials for advanced AIBs.

关键词： Aluminum-ion batteries cathode materials Organopolysulfides High coulombic efficiency

Unlocking the multi-electron transfer reaction in NASICON-type cathode materials

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materials Futures 2023年第2期2卷 109-122页

作者： Yuan Liu Xiaohui Rong Fei Xie Yaxiang Lu Junmei Zhao Liquan Chen Yong-Sheng Hu Beijing National Laboratory for Condensed Matter Physics Institute of PhysicsChinese Academy of SciencesBeijing 100190People’s Republic of China College of materials Science and Optoelectronic Technology University of Chinese Academy of SciencesBeijing 100049People’s Republic of China Yangtze River Delta Physics Research Center Co.Ltd Liyang 213300People’s Republic of China Huairou Division Institute of PhysicsChinese Academy of SciencesBeijing 101400People’s Republic of China CAS Key Laboratory of Green Process and Engineering State Key Laboratory of Biochemical EngineeringInstitute of Process EngineeringChinese Academy of SciencesBeijingPeople’s Republic of China

The growing concern about scarcity and large-scale applications of lithium resources has attracted efforts to realize cost-effective phosphate-based cathode materials for next-generation Na-ion batteries(NIBs).In previous work,a series of materials(such as Na_(4)Fe_(3)(PO_(4))_(2)(P_(2)O_(7)),Na_(3)VCr(PO_(4))_(3),Na_(4)VMn(PO_(4))3,Na_(3)MnTi(PO_(4))_(3),Na_(3)MnZr(PO_(4))3,etc)with∼120 mAh g^(-1) specific capacity and high operating potential has been proposed.However,the mass ratio of the total transition metal in the above compounds is only∼22 wt%,which means that one-electron transfer for each transition metal shows a limited capacity(the mass ratio of Fe is 35.4 wt%in LiFePO_(4)).Therefore,a multi-electron transfer reaction is necessary to catch up to or go beyond the electrochemical performance of LiFePO_(4).This review summarizes the reported NASICON-type and other phosphate-based cathode materials.On the basis of the aforementioned experimental results,we pinpoint the multi-electron behavior of transition metals and shed light on designing rules for developing high-capacity cathodes in NIBs.

关键词： NASICON Na-ion batteries cathode materials multi-electron transfer reactions

Surface Doping vs.Bulk Doping of cathode materials for Lithium-Ion Batteries:A Review

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Electrochemical Energy Reviews 2022年第4期5卷 254-285页

作者： Huaming Qian Haoqi Ren Ying Zhang Xianfeng He Wenbin Li Jingjing Wang Junhua Hu Hong Yang Hirbod Maleki Kheimeh Sari Yu Chen Xifei Li Xi’an Key Laboratory of New Energy materials and Devices Institute of Advanced Electrochemical Energy and School of Materials Science and EngineeringXi’an University of TechnologyXi’an 710048ShaanxiChina Shaanxi International Joint Research Center of Surface Technology for Energy Storage materials Xi’an 710048ShaanxiChina Department of Mechanical and materials Engineering University of Western OntarioLondonOntario N6A 5B9Canada State Center for International Cooperation On Designer Low‑Carbon and Environmental materials(CDLCEM) Zhengzhou University100 Kexue AvenueZhengzhou 450001China Xi’an Safty Energy Technology Co. LtdXi’an 710005ShaanxiChina

To address the capacity degradation,voltage fading,structural instability and adverse interface reactions in cathode materi-als of lithium-ion batteries(LIBs),numerous modification strategies have been developed,mainly including coating and doping.In particular,the important strategy of doping(surface doping and bulk doping)has been considered an effective strategy to modulate the crystal lattice structure of cathode materials.However,special insights into the mechanisms and effectiveness of the doping strategy,especially comparisons between surface doping and bulk doping in cathode materials,are still lacking.In this review,recent significant progress in surface doping and bulk doping strategies is demonstrated in detail by focusing on their inherent differences as well as effects on the structural stability,lithium-ion(Li-ion)diffusion and electrochemical properties of cathode materials from the following mechanistic insights:preventing the exposure of reactive Ni on the surface,stabilizing the Li slabs,mitigating the migration of transition metal(TM)ions,alleviating unde-sired structural transformations and adverse interface issues,enlarging the Li interslab spacing,forming three-dimensional(3D)Li-ion diffusion channels,and providing more active sites for the charge-transfer process.Moreover,insights into the correlation between the mechanisms of hybrid surface engineering strategies(doping and coating)and their influences on the electrochemical performance of cathode materials are provided by emphasizing the stabilization of the Li slabs,the enhancement of the surface chemical stability,and the alleviation of TM ion migration.Furthermore,the existing challenges and future perspectives in this promising field are indicated.

关键词： Lithium-ion batteries cathode materials Surface doping Bulk doping Hybrid surface engineering Structural stability Lithium-ion diffusion

3D anchoring structured for LiFe_(0.5)Mn_(0.5)PO_(4)@cornstalk-C cathode materials

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中国化学快报:英文版 2023年第8期34卷 302-305页

作者： Guangliang Zhang Riran Zang Man Mo Zhijie Fang Yangxian Huang Kunsong Hu Jiali Huang Xinxiang Liu Lingyun Huang Guohui Kang Weijian Li Haiqing Zhan Xianquan Ming Guanhan Huang Guiliang Li Feng Zhan School of Resources Environment and materials Guangxi UniversityNanning 530004China School of Electronics Engineering Guangxi University of Science and TechnologyLiuzhou 545006China State Key Laboratory of Featured Metal materials and Life-cycle Safety for Composite Structures Guangxi UniversityNanning 530004China Guangxi Higher Education Key Laboratory of High Performance Structural materials and Heat Treatment&Surface Processing Guangxi UniversityNanning 53004China South Manganese Group Limited Nanning 530029China

The organic carbon source coating LiFe_(x)Mn_(1-x)PO_(4)suffers from the problem of non-uniform carbon cladding.Too thick carbon cladding layer instead hinders the de-embedding of lithium ions.In this paper,we choose cornstalk as the carbon source,then LiFe_(0.5)Mn_(0.5)PO_(4)@cornstalk-C(LFMP@C-C)with 3D anchoring structure is prepared by the solvothermal method.The results show that the LFMP with cornstalk as the carbon source has better performance compared to the sucrose-coated LFMP material(LFMP@C).The discharge capacity of LFMP@C-C is 116 mAh/g for the first cycle at 1 C and the capacity retention rate is 94.0%after 500 cycles,and the discharge capacity of LFMP@C-C is more than 17.17%higher than that of LFMP@C.

关键词： LiFe_(0.5)Mn_(0.5)PO_(4) Cornstalk Solvothermal method 3D anchoring structure cathode materials

Methods of improving the initial Coulombic efficiency and rate performance of both anode and cathode materials for sodium-ion batteries

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Chinese Chemical Letters 2022年第2期33卷 730-742页

作者： Nkongolo Tshamala Aristote Kangyu Zou Andi Di Wentao Deng Baowei Wang Xinglan Deng Hongshuai Hou Guoqiang Zou Xiaobo Ji College of Chemistry and Chemical Engineering Central South UniversityChangsha 410083China Department of materials and Environmental Chemistry Stockholm UniversityStockholm 10691Sweden

Sodium-ion batteries(SIBs) have gained more scientists’ interest, owing to some facts such as the natural abundance of Na, the similarities of physicochemical characteristics between Li and Na. The irreversible Na+ions consumption during the first cycle of charge/discharge process(due to the formation of the solid electrolyte interface(SEI) on the electrode surface and other irreversible reactions) is the factor that determines high performance SIBs and largely reduces the capacity of the full cell SIBs. Thus, the initial coulombic efficiency(ICE) of SIBs for both anode and cathode materials, is a key parameter for high performance SIBs, and the point is to increase the transport rate of the Na+ions. Therefore, developing SIBs with high ICE and rate performance becomes vital to boost the commercialization of SIBs. Here we provide a review on the methods to improve the ICE and the rate performance, by summarizing some methods of improving the ICE and rate performance of the anode and cathode materials for SIBs, and end by a conclusion with some perspectives and recommendations.

关键词： Initial coulombic efficiency Rate performance Sodium-ion batteries Anode materials cathode materials