Air-stable Li_3.12P_0.94Bi_0.06S_3.91I_0.18 solid-state electrolyte with high ionic conductivity and lithium anode compatibility toward high-performance all-solid-state lithium metal batteries

Abstract

Sulfide solid-state electrolytes (SSEs) with superior ionic conductivity and processability are highly promising candidates for constructing all-solid-state lithium metal batteries (ASSLMBs). However, their practical applications are limited by their intrinsic air instability and serious interfacial incompatibility. Herein, a novel glass-ceramic electrolyte Li_3.12P_0.94Bi_0.06S_3.91I_0.18 was synthesized by co-doping Li₃PS₄ with Bi and I for high-performance ASSLMBs. Owing to the strong Bi–S bonds that are thermodynamically stable to water, increased unit cell volume and Li⁺ concentration caused by P⁵⁺ substitution with Bi³⁺, and the in situ formed robust solid electrolyte interphase layer LiI at lithium surface, the as-prepared Li_3.12P_0.94Bi_0.06S_3.91I_0.18 SSE achieved excellent air stability with a H₂S concentration of only 0.205 cm³ g^–1 (after 300 min of air exposure), outperforming Li₃PS₄ (0.632 cm³ g^–1) and the most reported sulfide SSEs, together with high ionic conductivity of 4.05 mS cm^–1. Furthermore, the Li_3.12P_0.94Bi_0.06S_3.91I_0.18 effectively improved lithium metal stability. With this SSE, an ultralong cyclability of 700 h at 0.1 mA cm^–2 was realized in a lithium symmetrical cell. Moreover, the Li_3.12P_0.94Bi_0.06S_3.91I_0.18-based ASSLMBs with LiNi_0.8Mn_0.1Co_0.1O₂ cathode achieved ultrastable capacity retention rate of 95.8% after 300 cycles at 0.1 C. This work provides reliable strategy for designing advanced sulfide SSEs for commercial applications in ASSLMBs.

Keywords

air stability / all-solid-state lithium metal battery / glass-ceramic / lithium metal compatibility / sulfide solid-state electrolyte

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RIGHTS & PERMISSIONS

2024 The Author(s). SusMat published by Sichuan University and John Wiley & Sons Australia, Ltd.