包覆与掺杂对富锂锰基材料的改性研究及产业化进展
收稿日期: 2023-01-06
网络出版日期: 2023-09-19
基金资助
青海省高原绿色建筑与生态社区重点实验室开放基金项目(KLKF-2021-009)
Research and industrialization progress on coating and doping modification of lithium-rich manganese-based materials
Received date: 2023-01-06
Online published: 2023-09-19
随着碳酸锂价格一路飙升及镍、钴价格的高居不下，层状富锂锰基材料以高比容量（≥250 mA·h/g）、高电压、低成本、高安全等多重优势引起新能源行业的关注。然而该材料存在不可逆的氧化还原、过渡金属迁移及结构转变等一系列问题，导致电压和容量衰减严重、首次库伦效率低等问题，因此能稳定、量产富锂锰基动力电池的企业较少，阻碍了其商业化进程。掺杂、包覆是提高富锂锰基材料电化学性能的常见有效策略，通过阐述富锂锰基材料的改性策略以及改性机理的同时分析富锂锰基材料的产业发展现状，提出了富锂锰基材料未来的发展方向主要包括：1）全面探究富锂锰基材料的失效机制；2）借助先进设备探究富锂锰基材料的失效机制；3）新材料、新技术的开发与应用。
陈天东 , 赵光钊 , 海春喜 , 董生德 , 贺欣 , 许琪 , 冯航 , 袁少雄 , 马路祥 , 周园 . 包覆与掺杂对富锂锰基材料的改性研究及产业化进展[J]. 无机盐工业, 2023 , 55(9) : 1 -8 . DOI: 10.19964/j.issn.1006-4990.2023-0012
With the prices of Li2CO3，nickel and cobalt rising，layered lithium-rich manganese-based materials have attracted the attention of the new energy industry with multiple advantages such as high specific capacity（≥250 mA·h/g），high voltage，low cost and high safety.Nevertheless，the material has a series of problems such as irreversible oxygen redox，transition metal migration and structural transformation，resulting in serious voltage and capacity decay and low initial coulombic efficiency.Therefore，there are few enterprises that can stably produce lithium-rich manganese based power batteries，which hinders its commercialization process.Doping and coating are common and effective strategies to improve the electrochemical performance of lithium-rich manganese-based materials.The current industrial development of lithium-rich manganese-based materials was analyzed while the modification strategies and modification mechanisms of lithium-rich manganese-based materials were described，and the future development direction of lithium-rich manganese-based materials was proposed，which mainly included the following points：1）comprehensively exploring the failure mechanism of lithium-rich manganese-based materials；2）exploring the failure mechanism of lithium-rich manganese-based materials with the help of advanced equipment；3）development and application of new materials and technologies.
| 1 | 李学田.高温球磨法合成磷酸铁锂正极材料及其改性研究［D］.沈阳：东北大学，2019. |
| LI Xuetian.Synthesis and modification of ferrous lithium phosphate cathode materials by high temperature ball milling［D］.Shenyang：Northeastern University，2019. | |
| 2 | 袁东.锰酸锂正极材料的合成制备及改性研究［D］.贵阳：贵州大学，2019. |
| YUAN Dong.Synthesis，preparation and modification of lithium manganate cathode material［D］.Guiyang：Guizhou University， 2019. | |
| 3 | 程续.层状结构高镍三元正极材料的改性及电化学性能的研究［D］.北京：北京科技大学，2022. |
| CHENG Xu.Study on modification and electrochemical properties of layered high nickel ternary cathode materials［D］.Beijing：University of Science and Technology Beijing，2022. | |
| 4 | ZHU Yulong， ZHANG Nan， ZHAO Li，et al.Improving electrochemical performance of lithium-rich cathode material Li1.2Mn0.52Ni0.13Co0.13W0.02O2 coated with Li2WO4 for lithiumion batteries［J］.Journal of Alloys and Compounds，2019，811：152023. |
| 5 | WANG Lei， YU Xin， LI Guoxin，et al.Oxidative degradation of phenol by corona dielectric barrier discharge at gas-liquid interphase［J］.Asian Journal of Chemistry，2014，26（3）：853-859. |
| 6 | MA Luxiang， CHEN Tiandong， Chunxi HAI，et al.Surface engineering of Li-and Mn-rich layered oxides for superior Li-ion battery［J］.Tungsten，2022：1-10. |
| 7 | REN Xuqiang， LI Donglin， ZHAO Zhenzhen，et al.Dual effect of aluminum doping and lithium tungstate coating on the surface improves the cycling stability of lithium-rich Manganese-based cathode materials［J］.Acta Chimica Sinica，2020，78（11）：1268. |
| 8 | TENG Rui， YU Haitao， GUO Chenfeng，et al.Effect of cation doping on the electrochemical properties of Li2MoO3 as a promising cathode material for lithium-ion battery［J］.Ionics，2020，26（9）：4413-4422. |
| 9 | 杨陈，向延鸿，章顺坤，等.Co掺杂对富锂锰基正极材料Li1.2Ni0.2Mn0.6O2电化学性能的影响［J］.人工晶体学报，2018，47（3）：629-634. |
| YANG Chen， XIANG Yanhong， ZHANG Shunkun，et al.Effect of Co doping on the electrochemical properties of Li1.2Ni0.2Mn0.6O2 rich lithium manganese based cathode materials［J］.Journal of Synthetic Crystals，2018，47（3）：629-634. | |
| 10 | LIM S N， SEO J Y， JUNG D S，et al.The crystal structure and electrochemical performance of Li1.167Mn0.548Ni0.18Co0.105O2 composite cathodes doped and co-doped with Mg and F［J］.Journal of Electroanalytical Chemistry，2015，740：88-94. |
| 11 | ZHANG Chunxiao， WEI Bo， WANG Meiyu，et al.Regulating oxygen covalent electron localization to enhance anionic redox reversibility of lithium-rich layered oxide cathodes［J］.Energy Storage Materials，2022，46：512-522. |
| 12 | YU Ruizhi， BANIS M N， WANG Changhong，et al.Tailoring bulk Li+ ion diffusion kinetics and surface lattice oxygen activity for high-performance lithium-rich Manganese-based layered oxid-es［J］.Energy Storage Materials，2021，37：509-520. |
| 13 | CHEN Jun， ZOU Guoqiang， DENG Wentao，et al.Pseudo-bonding and electric-field harmony for Li-rich Mn-based oxide cathode［J］.Advanced Functional Materials，2020，30（46）：2004302. |
| 14 | CHEN Song， CHEN Zhuo， XIA Min，et al.Toward alleviating voltage decay by sodium substitution in lithium-rich Manganese-based oxide cathodes［J］.ACS Applied Energy Materials，2018，1（8）：4065-4074. |
| 15 | CHENG Yaxin， WU Zhen， DAI Xin，et al.Enhanced electrochemical properties of potassium-doped lithium-rich（email protected）as cathode material for lithium-ion batteries［J］.Journal of Colloid and Interface Science，2022，605：718-726. |
| 16 | ZHANG Chunxiao， WEI Bo， JIANG Wenjun，et al.Insights into the enhanced structural and thermal stabilities of Nb-substituted lithium-rich layered oxide cathodes［J］.ACS Applied Materials & Interfaces，2021，13（38）：45619-45629. |
| 17 | DONG Shengde， ZHOU Yuan， Chunxi HAI，et al.Understanding electrochemical performance improvement with Nb doping in lithium-rich Manganese-based cathode materials［J］.Journal of Power Sources，2020，462：228185. |
| 18 | ZHANG Kai， SHENG Hang， WU Xiongwei，et al.Improving electrochemical properties by sodium doping for lithium-rich layered oxides［J］.ACS Applied Energy Materials，2020，3（9）：8953-8959. |
| 19 | YANG Jiachao， CHEN Yongxiang， LI Yunjiao，et al.Encouraging voltage stability upon long cycling of Li-rich Mn-based cathode materials by Ta-Mo dual doping［J］.ACS Applied Materials & Interfaces，2021，13（22）：25981-25992. |
| 20 | WANG Daqiang， WU Yuqing， WU Chen，et al.Highly oriented｛010｝crystal plane induced by boron in cobalt-free Li-and Mn-rich layered oxide［J］.ACS Applied Materials & Interfaces，2022， 14（2）：2711-2719. |
| 21 | CAO Fei， ZENG Weihao， ZHU Jiawei，et al.Inhibiting Mn migration by Sb-pinning transition metal layers in lithium-rich cathode material for stable high-capacity properties［J］.Small，2022，18（24）：2200713. |
| 22 | ZHANG Kun， QI Jizhen， SONG Jin，et al.Sulfuration of Li-rich Mn-based cathode materials for multianionic redox and stabilized coordination environment［J］.Advanced Materials，2022，34（11）：2109564. |
| 23 | GAO Xianggang， LI Shihao， ZHANG Haiyan，et al.Constructing a robust integrated surface structure for enhancing the performance of Li-rich Mn-based oxides cathodes［J］.Materials Today Energy，2022，30：101152. |
| 24 | ZHENG Hongfei， ZHANG Chenying， ZHANG Yinggan，et al.Manipulating the local electronic structure in Li-rich layered cathode towards superior electrochemical performance［J］.Advanced Functional Materials，2021，31（30）：2100783. |
| 25 | WANG Shengxian， WANG Shimin， YI Wentao，et al.Simultaneously dual modification of a ternary cathode material by aluminum bis（oxalato）borate-based electrolyte［J］.ACS Applied Energy Materials，2021，4（2）：1601-1609. |
| 26 | DONG Shengde， ZHOU Yuan， Chunxi HAI，et al.Enhanced cathode performance：Mixed Al2O3 and LiAlO2 coating of Li1.2Ni0.13Co0.13Mn0.54O2 ［J］.ACS Applied Materials & Interfaces，2020，12（34）：38153-38162. |
| 27 | ZHANG Xiaofeng， BELHAROUAK I， LI Li，et al.Structural and electrochemical study of Al2O3 and TiO2 coated Li1.2Ni0.13Mn0.54Co0.13O2 Cathode material using ALD［J］.Advanc-ed Energy Materials，2013，3（10）：1299-1307. |
| 28 | WU Yihang， ZHANG Xiaomeng， HU Minghui，et al.Effect of Laggera alata on hepatocyte damage induced by carbon tetrachloride in vitro and in vivo［J］.Journal of Ethnopharmacology，2009，126（1）：50-56. |
| 29 | WANG Zhiyuan， LIU Enzuo， HE Chunnian，et al.Effect of amorphous FePO4 coating on structure and electrochemical performance of Li1.2Ni0.13Co0.13Mn0.54O2 as cathode material for Li-ion batteries［J］.Journal of Power Sources，2013，236：25-32. |
| 30 | ZHOU Miaomiao， ZHAO Jianjun， WANG Xiaodong，et al.Surface engineering for high stable lithium-rich Manganese-based cathode materials［J］.Chinese Chemical Letters，2023，34（6）：107793. |
| 31 | LI G R， FENG X， DING Y，et al.AlF3-coated Li（Li0.17Ni0.25Mn0.58）O2 as cathode material for Li-ion batteries［J］.Electrochimica Acta，2012，78：308-315. |
| 32 | LIU Xuefeng， CHOI B， GOZUBENLI N，et al.Periodic arrays of metal nanorings and nanocrescents fabricated by a scalable colloidal templating approach［J］.Journal of Colloid and Interface Science，2013，409：52-58. |
| 33 | ARMSTRONG A R， HOLZAPFEL M， NOVáK P，et al.Demonstrating oxygen loss and associated structural reorganization in the lithium battery cathode Li（Ni0.2Li0.2Mn0.6）O2 ［J］.Journal of the American Chemical Society，2006，128（26）：8694- 8698. |
| 34 | WEI Hanxin， HUANG Yingde， TANG Linbo，et al.Lithium-rich Manganese-based cathode materials with highly stable lattice and surface enabled by perovskite-type phase-compatible layer［J］.Nano Energy，2021，88：106288. |
| 35 | LI Yu， HUANG Hui， YU Jiage，et al.Improved high rate capability of Li［Li0.2Mn0.534Co0.133Ni0.133］O2 cathode material by surface modification with Co3O4 ［J］.Journal of Alloys and Compounds，2019，783：349-356. |
| 36 | WU Chao， CAO Shuang， LI Heng，et al.Enhancing performances of Co-free Li-rich Mn-based layered cathode materials via interface modification of multiple-functional Mn3O4 shell［J］.Chemical Engineering Journal，2022，431：134208. |
| 37 | YU Fuda， QUE Lanfang， XU Chengyan，et al.Dual conductive surface engineering of Li-Rich oxides cathode for superior high-energy-density Li-Ion batteries［J］.Nano Energy，2019，59：527-536. |
| 38 | LIN Tongen， SCHULLI T U， HU Yuxiang，et al.Faster activation and slower capacity/voltage fading：A bifunctional urea treatment on lithium-rich cathode materials［J］.Advanced Functional Materials，2020，30（13）：1909192. |
| 39 | LI Jili， JIA Tiekun， TANG Chunjuan，et al.Stabilizing voltage and prolonged cycling life of Li-rich Mn-based oxides through spinel “lithium ion pump” heteroepitaxial coating strategy［J］.Scripta Materialia，2021，204：114133. |
| 40 | ZHANG Mengke， QIU Lang， SUN Yan，et al.Microstructure-controlled Li-rich Mn-based cathodes by a gas-solid interface reaction for tackling the continuous activation of Li2MnO3 ［J］.ACS Applied Materials & Interfaces，2021，13（34）：40995-41003. |
| 41 | HE Weitao， ZHANG Chunxiao， WANG Meiyu，et al.Countering voltage decay，redox sluggishness，and calendering incompatibility by near-zero-strain interphase in lithium-rich，Manganese-based layered oxide electrodes［J］.Advanced Functional Materials，2022，32（29）：2200322. |
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