Build a High-Performance All-Solid-State Lithium Battery through Introducing Competitive Coordination Induction Effect in Polymer-Based Electrolyte.

Polymer-inorganic composite electrolytes (PICE) have attracted tremendous attention in all-solid-state lithium batteries (ASSLBs) due to facile processability. However, the poor Li + conductivity at room temperature (RT) and interfacial instability severely hamper the practical application. Herein, we propose a concept of competitive coordination induction effects (CCIE) and reveal the essential correlation between the local coordination structure and the interfacial chemistry in PEO-based PICE. CCIE introduction greatly enhances the ionic conductivity and electrochemical performances of ASSLBs at 30 °C. Owing to the competitive coordination (Cs +… TFSI -… Li + , Cs +… C-O-C … Li + and 2,4,6-TFA … Li … TFSI - ) from the competitive cation (Cs + from CsPF 6 ) and molecule (2,4,6-TFA: 2,4,6-trifluoroaniline), a multimodal weak coordination environment of Li + is constructed enabling a high efficient Li + migration at 30 °C (Li + conductivity: 6.25×10 -4  S cm -1 ; t Li + =0.61). Since Cs + tends to be enriched at the interface, TFSI - and PF 6 - in situ form LiF-Li 3 N-Li 2 O-Li 2 S enriched solid electrolyte interface with electrostatic shielding effects. The assembled ASSLBs without adding interfacial wetting agent exhibit outstanding rate capability (LiFePO 4: 147.44 mAh g -1 @1 C and 107.41mAhg -1 @2 C) and cycling stability at 30 °C (LiFePO 4 :94.65 %@200cycles@0.5 C; LiNi 0.5 Co 0.2 Mn 0.3 O 2 : 94.31 %@200 cycles@0.3 C). This work proposes a concept of CCIE and reveals its mechanism in designing PICE with high ionic conductivity as well as high interfacial compatibility at near RT for high-performance ASSLBs.