Decoding Internal Stress‐Induced Micro‐Short Circuit Events in Sulfide‐Based All‐Solid‐State Li‐Metal Batteries via Operando Pressure Measurements

Abstract

Despite the relatively low stiffness of sulfide solid‐state electrolytes (SSEs), which makes them capable of better formability and accommodation for volume changes of active materials, the low fracture toughness (KIC) indicates a high susceptibility to fracture caused by electrochemo‐mechanical stresses. This susceptibility to mechanical damages and the subsequent lithium filament penetration, manifesting as micro‐short circuit events, seriously hinders the practical application of lithium metal in high‐energy‐density sulfide‐based all‐solid‐state lithium metal batteries (ASSLMBs). A full understanding of the stress evolution of Li metal anodes during cycling is key to decoding the mechanical damage‐induced micro‐short circuit behavior. Here, an operando and quantitative measurement of the stress evolution of an LTO/SSE/Li configuration all‐solid‐state battery (ASSB) operating with various parameters, including cell capacity and current density, is shown. Two micro‐short circuit modes and their corresponding mechanisms are revealed based on the electrochemo‐mechanical response of the Li metal anode. Furthermore, a finite element model (FEM) is used to explain this mechanical failure and a ′safety zone″ for the Li metal anode related to the ′internal stress″ is given. These findings provide new insight into the micro‐short circuit events induced by electrochemo‐mechanical damage in sulfide‐based ASSLMBs.

Enhanced Ionic Conductivity toward Air-Stable Li4SnS4 Solid Electrolytes Achieved by Soft Acid Bi3+ Doping

“…As shown in Figure 5c,d, the gc-LSB 0.025 S pellets have a denser surface, indicating that the Bi 3+ doping is effective in reducing interfacial and grain boundary impedance, benefiting the Li + transportation. 60,61 In addition, the comparison of EDS elemental mapping between gc-LSB 0.025 S and gc-LSS (Figures S5 and S6) also confirms the successful doping of Bi 3+ and the uniform distribution of Sn, S, and Bi in the electrolyte.…”

“…Based on the analysis of electrolyte powders in Figure a,c, it can be observed that gc-LSS and gc-LSB 0.025 S, which are both submicrometer materials with agglomerates, exhibit no significant difference from one another. As shown in Figure c,d, the gc-LSB 0.025 S pellets have a denser surface, indicating that the Bi 3+ doping is effective in reducing interfacial and grain boundary impedance, benefiting the Li + transportation. , In addition, the comparison of EDS elemental mapping between gc-LSB 0.025 S and gc-LSS (Figures S5 and S6) also confirms the successful doping of Bi 3+ and the uniform distribution of Sn, S, and Bi in the electrolyte.…”

Exploring Lithium-Ion Battery Degradation: A Concise Review of Critical Factors, Impacts, Data-Driven Degradation Estimation Techniques, and Sustainable Directions for Energy Storage Systems

“…Lithium plating results in LLI and may make the cell less safe since it can induce internal short circuits by allowing lithium dendrites to form [17]. Various modeling techniques of lithium plating have been presented in [50][51][52][53]. Lithium plating can be estimated using the Butler-Volmer equation [47].…”

“…Furthermore, mechanical stress could permit the electrolyte to penetrate the anode material and start chemical reactions that eventually weaken the anode and reduce battery capacity [50]. Moreover, internal short circuits brought on by stress-induced dendritic formation-a process in which microscopic lithium metal fibers protrude from the anode surface-can enter the separator and result in safety hazards like thermal runaway, overheating, or even explosions [51][52][53]59]. As the particles go through a phase transition, the intercalation of lithium ions into the anode may cause sudden variations in volume [60,61].…”