This work systematically reviewed recent progress of MOF-based solid electrolytes in all solid-state metal batteries which has rarely been summarized.

Recently, three-dimensional (3D) conductive frameworks have been chosen as the host for composite lithium (Li) metal anode because of their exceptional electrical conductivity and remarkable thermal and electrochemical stability. However, Li tends to accumulate on the top of the 3D frameworks with homogenous lithiophilicity and Li dendrite still growth. This work firstly designed a bimetallic metal-organic framework (MOF) (CuMn-MOF) derived Cu₂O and Mn₃O₄ nanoparticles decorated carbon cloth (CC) substrates (CC@Cu₂O/Mn₃O₄) to fabricate a composite Li anode. Thanks to the synergistic effects of lithiophilic Cu₂O and Mn₃O₄, the CC@Cu₂O/Mn₃O₄@Li symmetrical cell can afford a prolonged cycling lifespan (1400 h) under an ultrahigh current density and areal capacity (6 mA·cm⁻²/6 mAh·cm⁻²). When coupled with the LiFePO₄ (LFP) cathode, the LFP∥CC@Cu₂O/Mn₃O₄@Li full cell demonstrated a superior performance of 89.7 mAh·g⁻¹ even at an extremely high current density (10 C). Furthermore, it can also be matched well with LiNi_0.5Co_0.2Mn_0.3O₂ (NCM523) cathode. Importantly, to explain the excellent performances of the CC@Cu₂O/Mn₃O₄@Li composite anode, an intermittent model was also proposed. This study offers a novel model that can enhance our comprehension of the Li deposition behavior and pave the way to attain stable and safe Li metal anodes by employing bimetallic MOF-derived materials to construct 3D frameworks.