Constructing the high-areal-capacity, solid-state Li polymer battery via the multiscale ion transport pathway design

The parasitic Li dendrite formation and retarded ion diffusion dynamics inhibit the deployment of solid-state batteries (SSBs) at high areal capacity loadings. Here, we present the modular design of the Li⁺ percolating network by grafting the ionic-conductive polyether amine (PEA) at the multiple scales: the PEA modified zinc hydroxystannate (PEA@ZHS) (flame retardant units) and polyamide 6 (mechanical rigid units) are coherently introduced to optimize the PEO-based solid electrolyte (PX-PEA@ZHS) with the Young's modulus (3.41 GPa), ionic conductivity (4.29 × 10⁻⁴ S cm⁻¹ at 55 °C) and flame retardancy (22% reduction of heat release rate); on the other hand, PEA molecules are grafted onto the acetylene black additive to establish the dual conductive network, endowing two orders of magnitude increase of ionic conductivity for the high-compaction cathodes. The as-integrated symmetric cell exhibits a critical current density up to 0.8 mA cm⁻² and cycling endurance for 1000 h at 0.2 mA cm⁻²; upon the SSBs assembly with the record high loading of LiFePO₄ (12.4 mg cm⁻²), the high-areal-capacity, cycling stability as well as the extreme temperature endurance till 110 °C are simultaneously realized, which inspire the rational design of commercially feasible, energy-dense, flame-resistance energy storage prototype.