“双碳”背景下固态锂电池用硫化物固态电解质的发展趋势

doi:10.16085/j.issn.1000-6613.2023-1903

摘要/Abstract

摘要：

随着我国实施碳达峰、碳中和战略，电动汽车和储能成为实施该战略的重要抓手。锂离子电池作为电动汽车和储能的核心技术，近年来取得极大发展。目前的锂离子电池主要采用液态电解质，其安全性及能量密度面临瓶颈，难以满足电动汽车和储能的应用需求。硫化物全固态锂电池采用无机硫化物固态电解质取代目前广泛应用的液态电解质，有望回避液态电解质易燃易爆的安全问题。同时，基于硫化物电解质的高离子电导率，使硫化物全固态锂电池表现出优异的倍率性能。本文从硫化物电解质的分类与结构入手，首先介绍了硫化物电解质的发展历史，然后讨论了玻璃态、晶体硫化物电解质的结构特点、离子传输机制与电化学性能，接着介绍了硫化物电解质的三种不同合成方法以及其获得的硫化物电解质的电化学性能，最后总结了硫化物电解质的空气稳定性、界面稳定性等决定其产业化应用的关键性能。本文拟为硫化物电解质下一步的研究方向提供建议，有利于促进全固态锂电池产业化应用及我国“双碳”战略目标实现。

关键词: 全固态锂电池, 硫化物电解质, 产业化应用

Abstract:

China's carbon peaking and carbon neutrality strategy has made electric vehicles and energy storage crucial tools for its implementation. Lithium-ion batteries have emerged as a core technology for electric vehicles and energy storage, exhibiting significant progress in recent years. Current lithium-ion batteries (LIBs) predominantly use liquid electrolytes, which encounter safety and energy density bottlenecks, posing challenges to meet the application demand for electric vehicles and energy storage. Sulfide all-solid-state lithium batteries (ASSLBs) incorporate an inorganic sulfide solid-state electrolyte in place of the commonly used liquid electrolyte, presenting a solution to the flammable and explosive safety concerns associated with the latter. Meanwhile, based on the high ionic conductivity of the sulfide electrolyte, the sulfide electrolyte based ASSLB has exhibited excellent rate performance. In this review, the history of their development was introduced before the classification and structure of sulfide electrolytes. Then, it was followed by a discussion of the structural features, ion transport mechanisms and electrochemical properties of both glassy and crystalline sulfide electrolytes. Three different synthesis methods and the corresponding electrochemical properties of the resulting sulfide electrolytes were then presented. Finally, key properties such as air stability and interfacial stability that determined their industrial applications were summarized. It was suggested in conclusion to offer recommendations for the future research path of sulfide electrolyte, which could boost the industrial usage of ASSLBs and contribute to the fulfilment of China's "dual carbon goals".

Key words: all-solid-state lithium battery (ASSLB), sulfide electrolyte, industrial application

中图分类号:

TQ152

郭沛, 崔灿灿, 孔德洁, 黄晟. “双碳”背景下固态锂电池用硫化物固态电解质的发展趋势[J]. 化工进展, 2024, 43(9): 5193-5206.

GUO Pei, CUI Cancan, KONG Dejie, HUANG Sheng. Development trend of sulfide solid electrolytes for solid-state lithium batteries in the context of “dual carbon goals”[J]. Chemical Industry and Engineering Progress, 2024, 43(9): 5193-5206.

图/表 6

图1 硫化物电解质发展历史

表1 不同结构硫化物电解质优、缺点和离子电导率的比较

电解质	优点	缺点	离子电导率/S·cm^-1
玻璃态电解质	在全固态电池中利用率很高，合成简单	离子电导率相对较低	<10^-3
玻璃-陶瓷态电解质	离子电导率较高	合成步骤复杂	>10^-3
Thio-LISICON型电解质	合成简单，热稳定性好，电子电导率小	离子电导率相对较低	<10^-3
Li_11-_x M_2-_x P₁₊_x S₁₂（M=Ge, Sn, Si）结构	离子电导率高	成本较高，空气稳定性差	>10^-3
硫银锗矿型电解质	电化学稳定性好	空气稳定性较差	>10^-3

图2 不同Li2S含量的xLi2S-(100倍)P2S5的拉曼和31P轨道自旋核磁共振(MAS-NMR)谱(a)；在Li2S-P2S5二元体系中产生的不同晶体相(b)；Li6PS5X (X=Ⅰ‍)的晶体结构，锂的三种不同跃迁机制(c)；(1-x) Li4GeS4-x -xLi3PS4固溶体的三个区域（1Å=0.1nm）(d)；Li4SiS4的晶体结构（e）；Li10GeP2S12的晶体结构（f）

图3 硫化物电解质合成方法

表2 不同硫化物电解质合成方法的优缺点

合成方法	操作步骤	离子电导率 /S·cm^-1	操作环境	生产规模
机械球磨	复杂	<10^-3	友好	较小
机械球磨后退火	复杂	>10^-3	友好	较小
高温固相合成	简单	>10^-3	友好	较大
液相合成	复杂	<10^-4	苛刻	较大

图4 Li10Ge(P0.925Sb0.075)2S12样品暴露空气前后的离子电导率（a）；O掺杂电解质和全固态电池的优越性（b）；计算多种固体电解质的电化学稳定性窗口（c）；LGPS在锂化和析出过程中电压分布和相平衡的第一性原理计算结果（d）

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