复合卤化物电解质NaTaCl_(6)-Ta_(2)O_(5)的制备、结构及电化学性能研究  

Synthesis,Structure,and Electrochemical Performance of NaTaCl_(6)-Ta_(2)O_(5)Composite Halide Electrolyte

作　　者：陈馨 杨守猛 唐仪 杨洋 芮先宏 CHEN Xin;YANG Shoumeng;TANG Yi;YANG Yang;RUI Xianhong(School of Materials and Energy,Guangdong University of Technology,Guangzhou 510006,Chinese)

机构地区：[1]广东工业大学材料与能源学院,广州510006

出　　处：《西安工业大学学报》2025年第2期293-300,共8页Journal of Xi’an Technological University

基　　金：国家自然科学基金项目(52222210)。

摘　　要：针对传统钠离子卤化物电解质离子电导率低、界面兼容性差及电化学窗口受限等问题,本研究采用机械球磨法制备了复合卤化物电解质NaTaCl_(6)-Ta_(2)O_(5),并系统探究了其结构演变与电化学性能调控机制。研究结果表明,在NaTaCl_(6)-Ta_(2)O_(5)中Ta_(2)O_(5)诱导NaTaCl_(6)向非晶态转化,同时形成Cl-O键和O-3Ta/O-2Ta,从而优化了钠离子配位环境及Cl空位通道的连续性。电化学测试显示,NaTaCl_(6)-Ta_(2)O_(5)的室温离子电导率达3.4 mS·cm^(-1),较未复合Ta_(2)O_(5)的NaTaCl_(6)(1.2 mS·cm^(-1))提升了近3倍,活化能低至0.19 eV,电化学窗口拓宽至4.37 V(vs.Na/Na^(+))。此外,NaTaCl_(6)-Ta_(2)O_(5)的极限电流密度达到2.4 mA·cm^(-2),较NaTaCl_(6)(1.4 mA·cm^(-2))提升了71%。同时,组装的NaCrO_(2)||NaTaCl_(6)-Ta_(2)O_(5)||Na_(3)PS_(4)||Na_(3)Sn全电池在30℃、0.2 C的倍率下,显示出100 mAh·g^(-1)的高初始放电比容量,循环40圈后容量保持率为92.8%,表现出优异的钠离子传输动力学与界面稳定性。本研究为高安全性、高能量密度钠离子电池的电解质设计提供了新思路。This study aims to address the drawbacks of conventional sodium-ion halide electrolytes,including insufficient ionic conductivity,poor interfacial compatibility,and narrow electrochemical windows.To overcome these limitations,Ta_(2)O_(5)doped NaTaCl_(6)-Ta_(2)O_(5)electrolytes were prepared through high-energy mechanical milling and their structural evolution and the mechanism for the regulation of their electrochemical performance were systematically investigated.The results demonstrate that in NaTaCl_(6)-Ta_(2)O_(5)composites,Ta_(2)O_(5)induces the transformation of NaTaCl_(6)into an amorphous phase,forming Cl-O bonds and O-3Ta/O-2Ta configurations.This optimizes the sodium ion coordination environment and enhances the continuity of Cl vacancy channels.Electrochemical tests reveal that the room-temperature ionic conductivity of NaTaCl_(6)-Ta_(2)O_(5)reaches 3.4 mS·cm^(-1),nearly triple three times.that of pure NaTaCl_(6)(1.2 mS·cm^(-1)),with a low activation energy of 0.19 eV and an expanded electrochemical window of 4.37 V(vs.Na/Na^(+)).Additionally,the limiting current density of NaTaCl_(6)-Ta_(2)O_(5)reaches 2.4 mA·cm^(-2),71%higher than that of pristine NaTaCl_(6)(1.4 mA·cm^(-2)).The assembled NaCrO_(2)||NaTaCl_(6)-Ta_(2)O_(5)||Na_(3)PS_(4)||Na_(3)Sn full-cell delivers a high initial discharge capacity of 100 mAh·g^(-1)at 0.2 C and 30℃,with the capacity retention reaching 92.8%after 40 cycles,demonstrating excellent sodium-ion transport kinetics and interfacial stability.This study provides an innovative approach for the development of electrolytes in sodium-ion batteries with high safety and energy density.

关 键 词：钠离子电池 复合卤化物固态电解质 离子电导率 界面稳定性 

分 类 号：TH145.1[一般工业技术—材料科学与工程]