Gas generation induced by parasitic reactions in lithium-metal batteries (LMB) has been regarded as one of the fundamental barriers to the reversibility of this battery chemistry, which occurs via the complex interplays among electrolytes, cathode, anode, and the decomposition species that travel across the cell. In this work, a novel in situ differential electrochemical mass spectrometry is constructed to differentiate the speciation and source of each gas product generated either during cycling or during storage in the presence of cathode chemistries of varying structure and nickel contents. It unambiguously excludes the trace moisture in electrolyte as the major source of hydrogen and convincingly identifies the layer-structured NCM cathode material as the source of instability that releases active oxygen from the lattice at high voltages when NCM experiences H2 → H3 phase transition, which in turn reacts with carbonate solvents, producing both CO₂ and proton at the cathode side. Such proton in solvated state travels across the cell and becomes the main source for hydrogen generated at the anode side. Mechanisms are proposed to account for these irreversible reactions, and two electrolyte additives based on phosphate structure are adopted to mitigate the gas generation based on the understanding of the above decomposition chemistries.

The incorporation of inorganic fillers into poly(ethyleneoxide)(PEO)-based solid polymer electrolytes (SPEs) is well known as a low-cost and effective method to improve their mechanical and electrochemical properties. Porous zeolitic imidazolate framework-8 (ZIF-8) is firstly used as the filler for PEO-based SPEs in this work. Due to the introduction of ZIF-8, an ionic conductivity of 2.2 × 10^-5 S/cm (30 °C) is achieved for the composite SPE, which is one order of magnitude higher than that of the pure PEO. ZIF-8 also accounts for the broader electrochemical stability window and lithium ion transference number (0.36 at 60 °C) of the composite SPE. Moreover, the improved mechanism of ZIF-8 to the composite SPE is investigated by zeta potential and Fourier transform infrared spectrograph characterizations. The stability at the composite SPE/lithium interface is greatly enhanced. The LiFePO₄||Li cells using the composite SPE exhibit high capacity and excellent cycling performance at 60 °C, i.e., 85% capacity retention with 111 mA·h/g capacity retained after 350 cycles at 0.5 C. In comparison, the cells using the pure PEO show fast capacity decay to 74 mA·h/g maintaining only 68% capacity. These results indicate that the PEO-based SPEs with ZIF-8 are of great promise for the application in solid-state lithium metal batteries.