Thermodynamics-directed bulk/grain-boundary engineering for superior electrochemical durability of Ni-rich cathode  

作　　者：Kangyu Zou Mingzhu jiang Tianxiang Ning Lei Tan Junchao Zheng Jiexi Wang Xiaobo Ji Lingjun Li 

机构地区：[1]School of Materials Science and Engineering,Changsha University of Science and Technology,Changsha 410114,Hunan,China [2]Cllege of Chemistry and Chemical Engineering,Central South University,Changsha 410083,Hunan,China [3]School of Metallurgy and Environment,Central South University,Changsha 410083,Hunan,China [4]National Engineering Research Centre of Advanced Energy Storage Materials,Changsha 410205,Hunan,China

出　　处：《Journal of Energy Chemistry》2024年第10期321-331,I0006,共12页能源化学（英文版）

基　　金：supported by the National Natural Science Foundation of China (52374299,52304320 and 52204306);the Outstanding Youth Foundation of Hunan Province (2023JJ10044);the Key Project of Hunan Provincial Department of Education (22A0211);the Natural Science Foundation of Hunan Province (2023JJ40014)。

摘　　要：Introducing high-valence Ta element is an essential strategy for addressing the structu ral deterioration of the Ni-rich LiNi_(1-x-y)Co_(x)Mn_(y)O_(2)(NCM)cathode,but the enlarged Li/Ni cation mixing leads to the inferior rate capability originating from the hindered Li~+migration.Note that the non-magnetic Ti~(4+)ion can suppress Li/Ni disorder by removing the magnetic frustration in the transition metal layer.However,it is still challenging to directionally design expected Ta/Ti dual-modification,resulting from the complexity of the elemental distribution and the uncertainty of in-situ formed coating compounds by introducing foreign elements.Herein,a LiTaO_3 grain boundary(GB)coating and bulk Ti-doping have been successfully achieved in LiNi_(0.834)Co_(0.11)Mn_(0.056)O_(2) cathode by thermodynamic guidance,in which the structural formation energy and interfacial binding energy are employed to predict the elemental diffusion discrepancy and thermodynamically stable coating compounds.Thanks to the coupling effect of strengthened structural/interfacial stability and improved Li~+diffusion kinetics by simultaneous bulk/GB engineering,the Ta/Ti-NCM cathode exhibits outstanding capacity retention,reaching 91.1%after 400 cycles at 1 C.This elaborate work contributes valuable insights into rational dual-modification engineering from a thermodynamic perspective for maximizing the electrochemical performances of NCM cathodes.

关 键 词：Ni-rich layered cathode Dual-modification Grain boundary coating Bulk doping Thermodynamic perspective 

分 类 号：TM912[电气工程—电力电子与电力传动] TQ131.11[化学工程—无机化工]