Zwitterionic Polyurethane Solid Polymer Electrolytes: A Pathway to High-Performance All-Solid-State Lithium-Ion Batteries
Authors: Kim Sangil , Wang Kun , Gao Yuechen , Seol Hyang , Lyu Xingyi , Koverga Volodymyr , Guo Hanzeng , Li Tao , Ngo Anh , Cheng Gang 
Published: February 2024

Lithium-ion batteries (LIBs) currently dominate the energy storage market for electronic devices, thanks to their high energy density, high operating voltage, and good cycling performance. However, commercial LIBs employing organic liquid electrolyte and lithium (Li) salts pose significant safety concerns, including flammability and the risk of thermal runaway. Consequently, the development of solid electrolytes is of paramount importance. Among several solid ion conductors, solid polymer electrolytes (SPEs) can offer numerous advantages, including excellent flexibility and interfacial compatibility with electrodes, good processibility, low cost, and light weight characteristics. However, current SPEs face challenges such as poor thermal stability, inferior electrochemical stability, and low Li-ion conductivity at room temperature (~ 10-5 S cm-1 at 25 ℃).
In this study, we introduce a multifunctional zwitterionic polyurethane-based solid polymer electrolyte (zPU-SPE) for all-solid-state LIBs (SLBs) that addresses the limitations of conventional SPE materials. We synthesized zPU [i.e., poly((diethanolamine ethyl acetate)-co-poly(tetrahydrofuran)-co-(1,6-diisocyanatohexane))] and demonstrated its capability to host high amounts of LiTFSI without phase separation (up to 90 wt% LiTFSI loading). The Li-ion conductivity of zPU-SPE at 25° C is 7.4 × 10-4 S/cm, nearly 14 times greater than that of poly(ethylene oxide) (PEO) SPE (EO/Li+ = 16). Moreover, the high surface energy of zPU-SPE (487.5 J/m2 vs. 1.39 J/m2 of PEO) minimizes interfacial resistance. The zPU-SPE also exhibits outstanding elasticity, with a tensile break of 1700%, attributable to its dense inter- and intra-molecular hydrogen bonding.
We evaluated the SLB battery performance of PEO and zPU-SPEs using a solid-state Li/SPE/LiFePO4 cell, which we cycled at a constant current rate of 1 C at 25 °C. The SLB cell with zPU-SPE demonstrates remarkable cycle stability, retaining 86% capacity after 1,000 cycles and 76% capacity after 2,000 cycles at a 1C rate and room temperature, while maintaining nearly 100% coulombic efficiency. In contrast, the capacity of the SLB cell with PEO rapidly decreases to 30% of its initial capacity and fails after 100 cycles. Given that significant capacity loss in LIBs under cold weather conditions poses a challenge for electric vehicles, we also assessed the temperature-dependent battery performance. The SLB with zPU-SPE retains 93.8% capacity at 0 °C, a substantial improvement over state-of-the-art LIBs (< 80% capacity retention). We attribute the high-capacity retention of zPU-SPE at low temperatures to the excellent chain mobility of the soft segment in the zPU matrix, which has a low glass transition temperature (-45 °C) and a high ion transport rate due to the zwitterionic group. We also conducted atomistic molecular modeling to investigate the dissolution and dissociation of Li salts and the Li-ion transport mechanism within the zPU polymer matrix. Furthermore, we employed small-angle X-ray scattering to examine the structural organization of the zPU-SPE matrix and its correlation with ion conductivity. Our work aims to guide the design of novel polymer electrolytes capable of overcoming the trade-offs associated with ion-conducting polymers (i.e., stability and ion conductivity).

Figure 1