High interfacial-energy heterostructure facilitates large-sized lithium nucleation and rapid Li desolvation process.

High interfacial energy Li-electrolyte interface contributes to larger Li nucleation embryos and a more stable interface, so the interfacial energy is essential for highly reversible Li deposition/stripping. Herein, a high interfacial-energy artificial solid electrolyte interphase (SEI) with rich LiF embedded in lithiated poly-2-acrylamido-2-methylpropane sulfonic acid (PAMPS-Li) network is designed to realize favorable Li nucleation and rapid desolvation of Li simultaneously. The Li-F bonds in LiF (001) exhibit stronger ion-dipole interactions with Li atoms, offering higher interfacial energies. When the growth surface energy and total interfacial energy of Li are balanced, the high interfacial energy SEI with abundant LiF can promote the formation of larger Li nucleation embryos. In addition, the PAMPS-Li with immobilized anions presents weaker interaction with Li and possesses higher polymer-Li interfacial energy, and its amide and sulfonic acid groups exhibit higher binding energies with Li. Therefore, PAMPS-Li can easily promote the Li to escape from the solvent sheath and weaken the desolvation energy barrier. The highly reversible Li deposition behavior with restricted side reactions is achieved based on the synergistic modification of high interfacial energy SEI with heterostructure. Most importantly, lifespan of multi-layered Li pouch cell (330 Wh kg) with a low N/P ratio (1.67) is over 100 cycles, verifying its potential practical application.