Metal negative electrodes that alloy with lithium have high theoretical charge storage capacity and are ideal candidates for developing high-energy rechargeable batteries. However, such electrode materials show limited reversibility in Li-ion batteries with standard non-aqueous liquid electrolyte solutions. To circumvent this issue, here we report the use of non-pre-lithiated aluminum-foil-based negative electrodes with engineered microstructures in an all-solid-state Li-ion cell configuration. When a 30-μm-thick Al_94.5In_5.5 negative electrode is combined with a Li₆PS₅Cl solid-state electrolyte and a LiNi_0.6Mn_0.2Co_0.2O₂-based positive electrode, lab-scale cells deliver hundreds of stable cycles with practically relevant areal capacities at high current densities (6.5 mA cm⁻²). We also demonstrate that the multiphase Al-In microstructure enables improved rate behavior and enhanced reversibility due to the distributed LiIn network within the aluminum matrix. These results demonstrate the possibility of improved all-solid-state batteries via metallurgical design of negative electrodes while simplifying manufacturing processes.

与锂合金的金属负极具有较高的理论电荷存储容量，是开发高能可充电电池的理想选择。然而，这种电极材料在使用标准非水液体电解质溶液的锂离子电池中表现出有限的可逆性。为了解决这个问题，我们在这里报告了在全固态锂离子电池配置中使用具有工程微结构的非预锂化铝箔负极。当 30 μm 厚的 Al _94.5 In _{5.5负极与 Li 6} PS ₅ Cl 固态电解质和 LiNi _0.6 Mn _0.2 Co _0.2 O ₂基正极组合时，实验室规模的电池可实现数百次稳定循环在高电流密度（6.5 mA cm ^-2）下具有实际相关的面积容量。我们还证明，由于铝基体中分布有 LiIn 网络，多相 Al-In 微观结构能够改善倍率行为并增强可逆性。这些结果证明了通过负极的冶金设计同时简化制造工艺来改进全固态电池的可能性。