DataSheet1_Temperature-dependent compatibility study on halide solid-state electrolytes in solid-state batteries.docx

All-solid-state lithium batteries (ASSLBs) have attracted much attention owing to their high safety and energy density compared to conventional organic electrolytes. However, the interfaces between solid-state electrolytes and electrodes retain some knotty problems regarding compatibility. Among the various SSEs investigated in recent years, halide SSEs exhibit relatively good interfacial compatibility. The temperature-dependent interfacial compatibility of halide SSEs in solid-state batteries is investigated by thermal analysis using simultaneous thermogravimetry and differential scanning calorimetry (TG–DSC) and X-ray diffraction (XRD). Halide SSEs, including rock-salt-type Li3InCl6 and anti-perovskite-type Li2OHCl, show good thermal stability with oxides LiCoO2, LiMn2O4, and Li4Ti5O12 up to 320 °C. Moreover, anti-perovskite-type Li2OHCl shows a chemical reactivity with other battery materials (eg., LiFePO4, LiNi0.8Co0.1Mn0.1O2, Si-C, and Li1.3Al0.3Ti1.7(PO4)3) at 320°C, which reaches the melting point of Li2OHCl. It indicated that Li2OHCl has relatively high chemical reactivity after melting. In contrast, rock-salt-type Li3InCl6 shows higher stability and interfacial compatibility. This work delivers insights into the selection of suitable battery materials with good compatibility for ASSLBs.</p

Bilayer Halide Electrolytes for All-Inorganic Solid-State Lithium-Metal Batteries with Excellent Interfacial Compatibility

Inorganic solid-state electrolytes (ISSEs) have been extensively researched as the critical component in all-solid-state lithium-metal batteries (ASSLMBs). Many ISSEs exhibit high ionic conductivities up to 10–3 S cm–1. However, most of them suffer from poor interfacial compatibility with electrodes, especially lithium-metal anodes, limiting their application in high-performance ASSLMBs. To achieve good interfacial compatibility with a high-voltage cathode and a lithium-metal anode simultaneously, we propose Li3InCl6/Li2OHCl bilayer halide ISSEs with complementary advantages. In addition to the improved interfacial compatibility, the Li3InCl6/Li2OHCl bilayer halide ISSEs exhibit good thermal stability up to 160 °C. The Li-symmetric cells with sandwich electrolytes Li2OHCl/Li3InCl6/Li2OHCl exhibit long cycling life of over 300 h and a high critical current density of over 0.6 mA cm–2 at 80 °C. Moreover, the all-inorganic solid-state lithium-metal batteries (AISSLMBs) LiFePO4–Li3InCl6/Li3InCl6/Li2OHCl/Li fabricated by a facile cold-press method exhibit good rate performance and long-term cycling stability that stably cycle for about 3000 h at 80 °C. This work presents a facile and cost-effective method to construct bilayer halide ISSEs, enabling the development of high-performance AISSLMBs with good interfacial compatibility and thermal stability