Solvation-Tailored PVDF-Based Solid-State Electrolyte for High-Voltage Lithium Metal Batteries

Poly(vinylidene fluoride) (PVDF)-based polymer electro-lytes are attracting increasing attention for high-voltage solid-state lithium metal batteries because of their high room temperature ionic conductivity, adequate mechanical strength and good thermal stability. However, the presence of highly reactive residual solvents, such as N, N-dimethylformamide (DMF), severely jeopardizes the long-term cycling stability. Herein, we propose a solvation-tailoring strategy to confine residual solvent molecules by introducing low-cost 3 angstrom zeolite molecular sieves as fillers. The strong interaction between DMF and the molecular sieve weakens the ability of DMF to participate in the solvation of Li+, leading to more anions being involved in solvation. Benefiting from the tailored anion-rich coordination environment, the interfacial side reactions with the lithium anode and high-voltage NCM811 cathode are effectively suppressed. As a result, the solid-state Li||Li symmetrical cells demonstrates ultra-stable cycling over 5100 h at 0.1 mA cm-2, and the Li||NCM811 full cells achieve excellent cycling stability for more than 1130 and 250 cycles under the charging cut-off voltages of 4.3 V and 4.5 V, respectively. Our work is an innovative exploration to address the negative effects of residual DMF in PVDF-based solid-state electrolytes and highlights the importance of modulating the solvation structures in solid-state polymer electrolytes. Residual DMF solvents in PVDF-based solid-state electrolytes suffered from inevitably serious side reactions with high-voltage NCM811 cathode and lithium metal anode which restrict the cycling performance of solid-state Li||NCM811 cells. We proposed a novel strategy of anchoring DMF solvents by incorporating low-cost 3 angstrom zeolite molecular sieves as fillers to modulate the solvation structures in PVDF-based solid state electrolyte. Inorganic-rich SEI and CEI derived from the tailored anion-rich solvated structure guarantee long-term cycling stability of the solid-state Li||NCM811 cell at high cut-off voltages of 4.3 V and 4.5 V. image