Pressure-Tolerant 3D Anodes Enable Short-Circuit Prevention and Low Heat Generation in Argyrodite Solid-State Batteries

Abstract

Solid-state batteries (SSBs) offer a safer, higher-energy-density alternative to lithium-ion batteries, yet commercialization is hindered by incompatibility with lithium metal. To overcome these challenges, we developed a cost-effective, commercially available prelithiated micro carbon fiber framework (Li–Cf) anode featuring a high-pressure-tolerance, for use with argyrodite solid-state electrolytes (SSEs). This 3D structure accommodates uniform lithium deposition, simplifies cell assembly under elevated pressure, inhibits dendrite growth toward SSEs, reduces heat generation, and enhances overall compatibility. Notably, our architecture enables the cell to tolerate pressures up to 400 MPa without short-circuiting during assembly. Meanwhile, the 3D framework serves as a preferential pathway for lithium deposition, thereby reducing lithium growth toward the SSEs and mitigating the risk of dendrite formation in SSEs. Operando calorimetry and distribution of relaxation times analysis reveal that lithium morphology degradation at the interface with the SSEs is a key failure mechanism in lithium metal argyrodite SSBs, leading to increased diffusion resistance and heat generation. In contrast, the Li–Cf anode mitigates these issues by reducing both heat flux and charge transfer resistance. Full cells with LiNi_0.8Co_0.1Mn_0.1O₂/Li₆PS₅Cl/Li–Cf retain ∼79% capacity after 600 cycles, demonstrating significantly improved cycling stability and strong potential for practical energy storage applications.