An Effective Catholyte for Sulfide‐Based All‐Solid‐State Batteries Utilizing Gas Absorbents

• Published in: Small (Weinheim an der Bergstrasse, Germany) Germany), 2024-11, Vol.20 (44), p.e2403147-n/a
• Main Authors: Choi, Hyunbeen, Cho, Sungjin, Kim, Yoon‐Seong, Cho, Jun Sic, Kim, Haesol, Lee, Hyungjin, Ko, Sumin, Kim, Kyungjun, Lee, Sang‐Min, Hong, Seung‐Tae, Choi, Chang Hyuck, Seo, Dong‐Hwa, Park, Soojin
• Format: Article
• Language: English
• Subjects: all‐solid‐state batteries; Cathodes; Cathodic protection; Composite materials; Density functional theory; Electrolytes; gas absorbent; Ion currents; Lithium ions; Molten salt electrolytes; Oxidation resistance; Solid electrolytes; sufide‐based solid electrolytes; sulfur‐based gas; Zinc oxide; Zinc oxides; ZnO catholyte
• ISSN: 1613-6810; 1613-6829; 1613-6829
• DOI: 10.1002/smll.202403147

All‐solid‐state batteries (ASSBs) possess the advantage of ensuring safety while simultaneously maximizing energy density, making them suitable for next‐generation battery models. In particular, sulfide solid electrolytes (SSEs) are viewed as promising candidates for ASSB electrolytes due to their excellent ionic conductivity. However, a limitation exists in the form of interfacial side reactions occurring between the SSEs and cathode active materials (CAMs), as well as the generation of sulfide‐based gases within the SSE. These issues lead to a reduction in the capacity of CAMs and an increase in internal resistance within the cell. To address these challenges, cathode composite materials incorporating zinc oxide (ZnO) are fabricated, effectively reducing various side reactions occurring in CAMs. Acting as a semiconductor, ZnO helps mitigate the rapid oxidation of the solid electrolyte facilitated by an electronic pathway, thereby minimizing side reactions, while maintaining electron pathways to the active material. Additionally, it absorbs sulfide‐based gases, thus protecting the lithium ions within CAMs. In this study, the mass spectrometer is employed to observe gas generation phenomena within the ASSB cell. Furthermore, a clear elucidation of the side reactions occurring at the cathode and the causes of capacity reduction in ASSB are provided through density functional theory calculations. With a ZnO additive in LPSCl catholyte that can modulate electron‐conductivity at cathode composite and has affinity for sulfur gas, both solid‐state oxidative degradation and gaseous sulfur byproducts are successfully diminished. This strategy also microscopically safeguards NCM, particularly against the capacity loss due to gas infusion. The approach led to impressive performance in an all‐solid‐state full cell (ASSFC), maintaining 80% capacity over 100 cycles at 0.1C current density.