Dual-doping for enhancing chemical stability of functional anionic units in sulfide for high-performance all-solid-state lithium batteries  

作　　者：Peiwen Yu Niaz Ahmad Jie Yang Chaoyuan Zeng Xiaoxiao Liang Weiming Huang Mei Ni Pengcheng Mao Wen Yang 

机构地区：[1]Key Laboratory of Cluster Science of Ministry of Education,Beijing Key Laboratory of Photoelectronic/Electrophotonic Conversion Materials,School of Chemistry and Chemical Engineering,Beijing Institute of Technology,Beijing 100081,China [2]Analysis&Testing Center,Beijing Institute of Technology,Beijing 100081,China [3]Key Laboratory of Ministry of Education for Advanced Materials in Tropical Island Resources,Hainan Provincial Key Lab of Fine Chemistry,School of Chemical Engineering and Technology,Hainan University,Haikou 570228,Hainan,China [4]Department of Basic Courses,China Fire and Rescue Institute,Beijing 102202,China [5]College of Chemistry,Jilin University,Changchun 130012,Jilin,China [6]Key Laboratory of Physics and Technology for Advanced Batteries of Ministry of Education,Jilin University,Changchun 130012,Jilin,China [7]Southern Marine Science and Engineering Guangdong Lab(Zhanjiang),Zhanjiang 524002,Guangdong,China

出　　处：《Journal of Energy Chemistry》2023年第11期382-390,I0009,共10页能源化学（英文版）

基　　金：supported by the National Natural Science Foundation of China(Nos.21203008,21975025,12274025);the Hainan Province Science and Technology Special Fund(Nos.ZDYF2021SHFZ232,ZDYF2023GXJS022);the Hainan Province Postdoctoral Science Foundation(No.300333)。

摘　　要：The sulfide-based solid-state electrolytes(SEs)reactivity toward moisture and Li-metal are huge barriers that impede their large-scale manufactu ring and applications in all-solid-state lithium batteries(ASSLBs).Herein,we proposed an Al and O dual-doped strategy for Li_(3)PS_(4)SE to regulate the chemical/electrochemical stability of anionic PS_(4)^(3-)tetrahedra to mitigate structural hydrolysis and parasitic reactions at the SE/Li interface.The optimized Li_(3.08)A_(10.04)P_(0.96)S_(3.92)O_(0.08)SE presents the highestσLi+of 3.27 mS cm^(-1),which is~6.8 times higher than the pristine Li_(3)PS_(4)and excellently inhibits the structural hydrolysis for~25 min@25%humidity at RT.DFT calculations confirmed that the enhanced chemical stability was revealed to the intrinsically stable entities,e.g.,POS33-units.Moreover,Li_(3.08)Al_(0.04)P_(0.96)S_(3.92)O_(0.08)SE cycled stably in Li//Li symmetric cell over 1000 h@0.1 mA cm^(-2)/0.1 mA h cm^(-2),could be revealed to Li-Al alloy and Li_(2)Oat SE/Li interface impeding the growth of Li-dendrites during cycling.Resultantly,LNO@LCO/Li_(3.08)Al_(0.04)P_(0.96)S_(3.92)O_(0.08)/Li-In cell delivered initial discharge capacities of 129.8 mA h g^(-1)and 83.74%capacity retention over 300 cycles@0.2 C at RT.Moreover,the Li_(3.08)Al_(0.04)P_(0.96)S_(3.92)O_(0.08)SE presented>90%capacity retention over 200 and 300 cycles when the cell was tested with LiNi_(0.8)Co_(0.15)Al_(0.05)O_(2)(NCA)cathode material vs.5 and 10 mg cm^(-2)@RT.

关 键 词：Dual doping High Li^(+) conductivity Air-stability Pos_(3)^(3-) functional units Stable SE/electrode interface 

分 类 号：TB34[一般工业技术—材料科学与工程] TM912[电气工程—电力电子与电力传动]