Sulfonate-grafted graphene separators enabling electrostatic regulation of Li ⁺ desolvation and transport in lithium metal batteries

In lithium metal batteries, sluggish Li+ desolvation and anion-dominated ion transport at the separator–electrolyte interface fundamentally limits interfacial kinetics and trigger unstable lithium deposition. Lithium metal batteries suffer from slow interfacial kinetics and unstable lithium deposition, due to poor Li+ desolvation and uncontrolled anion transmittance at the separator–electrolyte interface. Here, a sulfonate-functionalized graphene was coated onto a polypropylene (PP) separators to construct an intrinsic anionic electrostatic field layer, which simultaneously regulates ion transport and promotes interfacial desolvation. This negatively charged field not only repels anions but also reshapes the local solvation environment, thereby facilitating Li+ desolvation and transport, leading to a high lithium-ion transference number of 0.79. Meanwhile, the negatively charged interface repels polarized solvent molecules and redistributes local electric field lines, weakening Li+-solvent charge–dipole interactions and lowering the Li+ desolvation energy barrier, thereby accelerating Li+ transport kinetics. Benefiting from homogenized Li+ flux and facilitated desolvation, the modified separator enables uniform lithium deposition and effectively suppresses dendrite growth, allowing Li symmetric cells to cycle stably for over 1000 h with low polarization. In full cells, LiNCM622 batteries exhibit excellent high-voltage cycling stability, achieving 82% capacity retention after 1000 cycles, more than doubling that of cells using conventional PP separators. Moreover, Si–CNCM811 pouch cells retain over 80% capacity after 700 cycles at 1C, demonstrating promising scalability and practical applicability.