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Mechanism of Capacity Fading Caused by Mn(Ⅱ)deposition on Anodes for Spinel Lithium manganese Oxide Cell

Journal of Wuhan University of Technology(Materials Science) 2017年第1期32卷 1-10页

作者：陈海辉 MA Tianyi ZENG Yingying GUO Xiuyan 邱新平 College of Chemistry&Chemical Engineering Jinggangshan UniversityJi'An 343009China Department of Chemistry Tsinghua UniversityBeijing 100008China School of Mechanical&Electrical Engineering Jinggangshan UniversityJi'an 343009China

The capacity fade of spinel lithium manganese oxide in lithium-ion batteries is a bottleneck challenge for the large-scale *** traditional opinion is that Mn（Ⅱ） ions in the anode are reduced to the metallic manganese that helps for catalyzing electrolyte *** could poison and damage the solid electrolyte interface（SEI） film,leading to the the capacity fade in Li-ion *** propose a new mechanism that Mn（Ⅱ） deposites at the anode hinders and/or blocks the intercalation/de-intercalation of lithium ions,which leads to the capacity fade in Li-ion *** on the new mechanism assumption,a kind of new structure with core-shell characteristic is designed to inhabit manganese ion dissolution,thus improving electrochemical cycle performance of the *** the way,this mechanism hypothesis is also supported by the results of these *** LiMn2-xTixO4 shell layer enhances cathode resistance to corrosion attack and effectively suppresses dissolution of Mn,then improves battery cycle performance with LiMn_2O_4 cathode,even at high rate and elevated temperature.

关键词： capacity fade manganese deposition lithium manganese oxide core-shell structure

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Mechanism of high-concentration electrolyte inhibiting the destructive effect of Mn(Ⅱ)on the performance of lithium-ion batteries

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Journal of Energy Chemistry 2023年第3期78卷 381-392,I0011页

作者： Xiaoling Cui Jinlong Sun Dongni Zhao Jingjing Zhang Jie Wang Hong Dong Peng Wang Junwei Zhang Shumin Wu Linhu Song Ningshuang Zhang Chunlei Li Shiyou Li School of Petrochemical Technology Lanzhou University of TechnologyLanzhou 730050GansuChina Key Laboratory of Low Carbon Energy and Chemical Engineering of Gansu Province Lanzhou 730050GansuChina Gansu Engineering Laboratory of Electrolyte Material for Lithium-ion Battery Baiyin 730900GansuChina

By optimizing electrolyte formulation to inhibit the deposition of transition metal ions(TMIs) on the surface of the graphite anode is an effective way to improve the electrochemical performance of lithium-ion *** present,it is generally believed the formation of an effective interfacial film on the surface of the anode electrode is the leading factor in reducing the dissolution of TMIs and prevent TMIs from being embedded in the *** ignores the influence of the solvation structures in the electrolyte system with different composition,and is not conducive to the design of the electrolyte formulation from the perspective of changing the concentration and the preferred solvent to inhibit the degradation of battery performance caused by TMIs *** this work,by analyzing the special solvation structures of the high-concentra tion electrolyte,we study the main reason why high-concentration electrolyte inhibits the destructive effect of Mn(Ⅱ) on the electrochemical performance of *** combining the potentialresolved in-situ electrochemical impedance spectroscopy technology(PRIs-EIS) and density functional theory(DFT) calculation,we find that Mn(Ⅱ) mainly exists in the form of contact ions pairs(CIPs) and aggregates(AGGs) in high-concentration *** solvation structures can reduce the destructive effect of Mn(Ⅱ) on battery performance from two aspects:on the one hand,it can rise the lowest unoccupied orbital(LUMO) value of the solvation structures of Mn(Ⅱ),thereby reducing the chance of its reduction;on the other hand,the decrease of Mn2+ions reduction can reduce the deposition of metallic manganese in the solid electrolyte interphase(SEI),thereby avoiding the continuous growth of the *** study can be provided inspiration for the design of electrolytes to inhibit the destructive effect of TMls on LIBs.

关键词： Lithium-ion battery High-concentration electrolyte manganese deposition Solvation structures

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