C. Dong, Z.H. Bi, R. Li, Y.X. Ma, B. Li, H.D. Shi, Z.Z. Zhang and Z.-S. Wu *

National Science Review, 2025, accepted.

Sulfide solid-state electrolytes (SSEs) are promising candidates for next-generation high-safety all-solid-state lithium batteries (ASSLBs). However, they still face challenges such as low anodic stability limits and poor interfacial compatibility with high-voltage cathode active materials. Here, we present a series of fluorine doped argyrodite sulfide SSEs, Li5.5PS4.5Cl1.5–xFx (LPSCl1.5–xFx) (0 < x ≤ 1.5), toward high-voltage LiCoO2 (LCO)-based ASSLBs, via the in-situ formation of a stable fluorine-containing passivating interphase on the cathode active materials surface. Notably, fluorine incorporation significantly raises the practical oxidation limit of LPSCl1.5 from 2.4 V to 3.5 V for LPSClF0.5, while maintaining a high room-temperature ionic conductivity of 3.3 mS cm–1. This enhancement is attributed to increased lithium-ion disorder and fluorine’s high electronegativity. The ASSLBs, fabricated by directly assembling LPSClF0.5 SSE with uncoated commercial LCO cathode, demonstrate stable cycling with low polarization voltage at 4.3 V (vs. Li+/Li), achieving 92.1% capacity retention after 700 cycles at 0.2 C. Remarkably, even under 4.6 V high-voltage condition, our battery maintains 96.2% capacity retention over 300 cycles, attributed to the in-situ formation of a stable fluorine-containing cathode-electrolyte interphase on the LCO surface. When coupled with a lithium metal anode, Li|LPSClF0.5|LCO ASSLB achieves stable cycling at 4.6 V and delivered 137 mAh g-1 after 100 cycles at 0.5 C. Significantly, the Si|LPSCl1.5|LPSClF0.5|LCO ASSLB, cycled at an ultra-high mass loading LCO of 203.8 mg cm–2, exhibits an exceptional areal capacity of 25.7 mAh cm–2, demonstrating immense potential of LPSClF0.5 SSE for practical high-energy ASSLBs.