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 s...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.展开更多
基金National Research Foundation of Korea,Grant/A ward Numbers:MEST,NRF-2021R1A2C2009596Engineeringand Physical Sciences Research Council,Grant/A ward Numbers:EP/R029431,EP/P020194,EP/T022213+1 种基金Korea government(Ministry of Science and ICT,MSIT),Grant/Award Number:RS-2023-00236572European Research Council,ERC,Grant/Award Numbers:EP/R029431,EP/P020194,EP/T022213。
文摘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.
