Optimizing Depth-of-Discharge in Li-Rich Halide All-Solid-State Batteries for Enhanced Capacity and Cycling Stability

Although halide solid electrolytes (HSEs) demonstrate a higher voltage window and superior interfacial stability toward Li-rich layered oxides (LLOs) compared to sulfide systems, HSE-based all-solid-state lithium batteries (HSE-ASSLBs) still face a fundamental trade-off between achieving high capacity and maintaining cycling stability. To resolve this issue, a rational adjustment of the depth-of-discharge (DOD) via discharge cut-off voltage control is proposed. Analysis of dQ/dV profiles and post-cycled electrodes indicates that excessive DOD (lower cut-off voltages) aggravates structural degradation and interfacial side reactions, whereas insufficient DOD (higher cut-off voltage) fails to fully utilize the compensatory capacity from low-voltage redox couples. Notably, an optimized cut-off voltage of 2.6 V activates a stable low-voltage redox reaction centered around 2.85 V, which effectively offsets high-voltage capacity loss while suppressing unfavorable interfacial evolution. As a result, the ASSLB configured with a Li1.2Ni0.13Mn0.54Co0.13O2 cathode and a Li2.75In0.75Zr0.25Cl6 HSE delivers an initial discharge capacity of 281.6 mAh g−1 at 1C and achieves significantly improved capacity retention from 71.8% to 86.1% over 300 cycles. This study confirms that DOD regulation offers a simple and effective electrochemical protocol for enabling durable high-capacity output in LLO-based ASSLBs.