Journal of the American Chemical Society

Georgina L. Gregory, Hui Gao Boyang Liu, Xiangwen Gao, Gregory J. Rees, Mauro Pasta, Peter G. Bruce & Charlotte K. Williams

Polymers designed with a specific combination of electrochemical, mechanical, and chemical properties could help overcome challenges limiting practical all-solid-state batteries for high-performance next-generation energy storage devices. In composite cathodes, comprising active cathode material, inorganic solid electrolyte, and carbon, battery longevity is limited by active particle volume changes occurring on charge/discharge. To overcome this, impractical high pressures are applied to maintain interfacial contact. Herein, block polymers designed to address these issues combine ionic conductivity, electrochemical stability, and suitable elastomeric mechanical properties, including adhesion. The block polymers have “hard-soft-hard”, ABA, block structures, where the soft “B” block is poly(ethylene oxide) (PEO), known to promote ionic conductivity, and the hard “A” block is a CO₂-derived polycarbonate, poly(4-vinyl cyclohexene oxide carbonate), which provides mechanical rigidity and enhances oxidative stability. ABA block polymers featuring controllable PEO and polycarbonate lengths are straightforwardly prepared using hydroxyl telechelic PEO as a macroinitiator for CO₂/epoxide ring-opening copolymerization and a well-controlled Mg(II)Co(II) catalyst. The influence of block polymer composition upon electrochemical and mechanical properties is investigated, with phosphonic acid functionalities being installed in the polycarbonate domains for adhesive properties. Three lead polymer materials are identified; these materials show an ambient ionic conductivity of 10 ^–4 S cm^–1, lithium-ion transport (t_Li+ 0.3–0.62), oxidative stability (>4 V vs Li^+/Li), and elastomeric or plastomer properties (G′ 0.1–67 MPa). The best block polymers are used in composite cathodes with LiNi_0.8Mn_0.1Co_0.1O₂ active material and Li₆PS₅Cl solid electrolyte–the resulting solid-state batteries demonstrate greater capacity retention than equivalent cells featuring no polymer or commercial polyelectrolytes.