Mechanism of Bilayer Polymer-Based Electrolyte with Functional Molecules in Enhancing the Capacity and Cycling Stability of High-Voltage Lithium Batteries

Poly(ethylene oxide) (PEO)-based solid polymer electrolytes (SPEs) are favorable for all-solid-state lithium metal batteries (ASSLBs) to ensure safety and enhance energy density. However, their narrow work windows and unstable electrode/electrolyte interfaces hinder their practical application in high-voltage ASSLBs. Although introducing additives in SPEs has been proven to be effective to address the above issues, it could hardly optimize both cathode and anode interfaces by an individual additive. Herein, heterogeneously double-layer SPEs are constructed with two typical additives (LiPO₂F₂ and LiFSI), which are used to modify the LiNi_0.6Co_0.2Mn_0.2O₂ (NCM)-cathode/electrolyte interface (CEI) and lithium-anode/solid electrolyte interface (SEI), and further understand their respective mechanism in enhancing the capacity and cycling stability of ASSLBs. Specifically, LiPO₂F₂ not only leads to a uniform CEI layer to prevent the oxidation decomposition of PEO and LiTFSI but also ensures fast Li⁺ diffusion at high voltage (>3.9 V), improving the rate performances and life spans of the cells. The LiFSI contributes to a stable SEI layer with rich LiF, suppressing the growth of lithium dendrites and maximizing the specific capacity for ASSLBs. Integrating the advantages of the two functional molecules, the optimized ASSLB displays an excellent capacity of 141.4 mAh g^-1 at 1C and an outstanding capacity retention of 81.6% after 400 cycles when using the NCM cathode, even reaching 154.2 mAh g^-1 at 0.1 mA cm^-2 with a high mass loading (6.4 mg cm^-2). Additionally, the bilayer SPEs also match well with a LiFePO₄ electrode with a high mass loading of 11.0 mg cm^-2, displaying a high capacity of 155.7 mAh g^-1 at 0.1 mA cm^-2 © 2023 American Chemical Society