硫化锂：全固态电池时代的“基石”材料

doi:10.19799/j.cnki.2095-4239.2025.0030

摘要/Abstract

摘要：

硫化锂(Li₂S)作为合成高性能硫化物固态电解质的关键前体原料，是硫化物全固态电池实现产业化应用的“基石”材料。系统认知硫化锂材料的关键物性参数，开发高质量、低成本的规模化制备技术，对推动硫化物全固态电池产业发展具有重要战略意义。本文从论述硫化锂在全固态电池技术体系中的核心地位出发，重点解析硫化锂的基础理化参数、关键性能指标及其对产业化应用的关键影响。基于产业化可行性视角，系统归纳了五类具有产业化前景的制备工艺：锂硫化合法、碳热还原法、水合肼还原法、液相复分解法及硫化氢中和法。通过构建多维评价体系，从工艺特性、产品性能、安全风险及经济性等维度对各制备技术进行了对比分析，进而阐明制约当前硫化锂产业化进程的关键瓶颈，提出了针对性优化策略，并展望未来规模化制备技术的发展方向。为硫化锂的工业化生产及其在硫化物全固态电池中的高效应用提供参考，助力硫化物固态电解质体系的技术升级与成本优化。

关键词: 硫化物全固态电池, 硫化锂, 产品指标, 量产技术, 成本

Abstract:

Lithium sulfide (Li₂S), as a critical precursor for synthesizing high-performance sulfide solid electrolytes, forming the foundation of the industrial development of sulfide-based all-solid-state batteries (ASSBs). Achieving a deep understanding of Li₂S's key physicochemical properties, alongside advancing high-quality, cost-effective, and scalable fabrication techniques, is strategically significant for the sulfide ASSB industry. This study elucidates the central role of Li₂S within the technological framework of ASSBs, emphasizing its core physicochemical parameters, key performance metrics, and their critical impact on industrial applications. Five promising synthesis methos are systematically reviewed from an industrial feasibility perspective, including direct sulfurization of metallic lithium, carbothermal reduction, hydrazine hydrate reduction, liquid-phase metathesis, and hydrogen sulfide neutralization. A multidimensional evaluation framework is constructed to compare these techniques across several dimensions, such as process characteristics, product performance, safety risks, and economic viability. This analysis identifies the key bottlenecks restricting the industrialization of Li₂S and proposes targeted strategies for optimization. Potential future directions in large-scale production technologies are also outlined. This study aims to serve as a valuable reference for the industrial production of Li₂S and its efficient integration into sulfide-based all-solid-state batteries, thereby facilitating technological advancements and cost reductions in sulfide solid electrolyte systems.

Key words: sulfide solid-state battery, lithium sulfide, product specification, mass production technology, cost

中图分类号:

TK 02

何特特, 卢洋, 刘洋, 徐斌, 陈永乐, 刘芳洋. 硫化锂：全固态电池时代的“基石”材料[J]. 储能科学与技术, 2025, 14(3): 898-912.

Tete HE, Yang LU, Yang LIU, Bin XU, Yongle CHEN, Fangyang LIU. Lithium sulfide: the "cornerstone" material in the era of all-solid-state batteries[J]. Energy Storage Science and Technology, 2025, 14(3): 898-912.

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材料化学式	制备工艺	电导率测试关键参数	室温电导率/(mS/cm)
Li_9.54Si_1.74P_1.44S_11.7Cl_0.3	固相球磨-压片-密封烧结	制片压强：未提及阻塞电池：金阻塞电池频率：0.1 Hz~3 MHz	25
Li_5.5PS_4.5Cl_1.5	固相球磨-压片-密封烧结	制片压强：370 MPa 阻塞电池：不锈钢阻塞电池频率：1 Hz~7 MHz	9.5
Li₇P₃S₁₁	固相球磨-烧结	制片压强：未提及阻塞电池：气相沉积Au阻塞电池频率：0.1 Hz~7 MHz	2
Li₃PS₄	液相反应-密封烧结	制片压强：未提及阻塞电池：涂炭铝箔阻塞电池频率：1 Hz~1 MHz	0.16
Li₇P₃S_7.5O_3.5	固相球磨-烧结	制片压强：380 MPa 阻塞电池：不锈钢阻塞电池频率：1 Hz~35 MHz	0.46
Li_6.8Si_0.8As_0.2S₅I	固相球磨-压片-密封烧结	制片压强：870 MPa 阻塞电池：Swagelok模型电池频率：1 Hz~8 MHz	10.4
Li₁₀GeP₂S₁₂	固相球磨-压片-密封烧结	制片压强：未提及阻塞电池：涂覆金浆，500 ℃烧结频率范围：0.1 Hz~1 MHz	12
Li_9.54[Si_0.6Ge_0.4]_1.74P_1.44 S_11.1Br_0.3O_0.6	固相球磨-压片-密封烧结	制片压强：370MPa 阻塞电池：涂覆金浆，500 ℃烧结频率范围：0.1 Hz~1 MHz	32

指标	测试方法	测量目标	意义
粉体颜色(白度)	目视(白度仪)	碳、多硫等显色杂质	杂质对电解质制备及性能产生显著影响
物相	XRD	无机盐杂质	氢氧化锂、氧化锂之类的杂质相在电解质制备中造成杂质相生成，降低电导率
水含量	卡尔-费休水分测试仪	硫化锂含水量	水分对硫化锂的储存、使用影响较大
碳含量	红外碳硫分析仪测试电子电导	硫化锂含碳量	碳含量会造成电解质的电子电导率升高，并可能诱导电解质分解
溶剂含量	GC-MS/TGA-DSC	硫化锂的有机溶剂残留	溶剂影响计量比，在后续电解质烧结时碳化会提高电子电导率
水溶颜色	溶于水后的水溶液颜色	金属离子、多硫等杂质	金属离子或多硫杂质超标会对电解质化学计量比以及晶体结构产生不利影响

反应类型	反应方程式	锂源量/t	硫源量/t	助剂量/t	单吨硫化锂的原料成本/(万元/t)
碳热还原工艺	2C+Li₂SO₄·H₂O=Li₂S+2CO₂+H₂O	2.78		0.52	13.61
硫化氢中和工艺	H₂S+2LiOH·H₂O=Li₂S+4H₂O	1.83	0.92	—	14.61
水合肼还原工艺	2S+4LiOH·H₂O+N₂H₄·H₂O =2Li₂S+N₂(g)+9H₂O	1.83	0.70	0.68	14.75
复分解工艺	Na₂S·nH₂O+2LiCl=Li₂S+2NaCl+nH₂O	1.85	2.83	—	15.01
锂硫化合工艺	2Li+S=Li₂S	0.30	0.70	—	21.26

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