Exploring dopant-enhanced ionic conductivity of AgCl-doped Li_(7)P_(3)S_(11) solid electrolytes: Integrating synchrotron Rietveld analysis, DFT, and ANN-based molecular dynamics approaches  

作　　者：Yong‐Seok Choi Youngin Lee Hyuna Ahn Jiwon Jeong Kyung YoonChung David OScanlon Jae‐Chul Lee 

机构地区：[1]Department of Materials Science andEngineering,Dankook University,Cheonan,Republic of Korea [2]Department of Materials Science andEngineering,Korea University,Seoul,Republic of Korea [3]Center for Energy Storage Research,Korea Institute of Science and Technology,Seoul,Republic of Korea [4]The School of Chemistry,Universityof Birmingham,Edgbaston,Birmingham,UK [5]Institute of Green ManufacturingResearch,Korea University,Seoul,Republic of Korea

出　　处：《Carbon Energy》2024年第11期113-125,共13页碳能源(英文)

基　　金：National Research Foundation of Korea,Grant/A ward Numbers:MEST,NRF-2021R1A2C2009596;Engineeringand Physical Sciences Research Council,Grant/A ward Numbers:EP/R029431,EP/P020194,EP/T022213;Korea government(Ministry of Science and ICT,MSIT),Grant/Award Number:RS-2023-00236572;European Research Council,ERC,Grant/Award Numbers:EP/R029431,EP/P020194,EP/T022213。

摘　　要：The effectiveness of dual-doping as a method of improving the conductivity of sulfide solid electrolytes(SEs)is not in doubt;however,the atomic-level mechanisms underpinning these enhancements remain elusive.In this study,we investigate the atomic mechanisms associated with the high ionic conductivity of the Li_(7)P_(3)S_(11)(LPS)SE and its response to Ag/Cl dual dopants.Synthesis and electrochemical characterizations show that the 0.2 M AgCl-doped LPS(Li_(6.8)P_(3)Ag_(0.1)S_(10.9)Cl_(0.1))exhibited an over 80%improvement in ionic conductivity compared with the undoped LPS.The atomic-level structures responsible for the enhanced conductivity were generated by a set of experiment and simulation techniques:synchrotron X-ray diffractometry,Rietveld refinement,density functional theory,and artificial neural network-based molecular dynamics simulations.This thorough characterization highlights the role of dual dopants in altering the structure and ionic conductivity.We found that the PS_(4) and P_(2)S_(7) structural motifs of LPS undergo transformation into various PS_(x) substructures.These changes in the substructures,in conjunction with the paddle-wheel effect,enable rapid Li migration.The dopant atoms serve to enhance the flexibility of PS_(4)–P_(2)S_(7) polyhedral frameworks,consequently enhancing the ionic conductivity.Our study elucidates a clear structure–conductivity relationship for the dual-doped LPS,providing a fundamental guideline for the development of sulfide SEs with superior conductivity.

关 键 词：density functional theory molecular dynamnics paddle-wheel dynamics sulfide solid electrolytes synchrotron Rietveld analysis 

分 类 号：TG1[金属学及工艺—金属学]