Polyaspartate Polyurea-Based Solid Polymer Electrolyte with High Ionic Conductivity for the All-Solid-State Lithium-Ion Battery

[Image: see text] The existing in situ preparation methods of solid polymer electrolytes (SPEs) often require the use of a solvent, which would lead to a complicated process and potential safety hazards. Therefore, it is urgent to develop a solvent-free in situ method to produce SPEs with good processability and excellent compatibility. Herein, a series of polyaspartate polyurea-based SPEs (PAEPU-based SPEs) with abundant (PO)(x)(EO)(y)(PO)(z) segments and cross-linked structures were developed by systematically regulating the molar ratios of isophorone diisocyanate (IPDI) and isophorone diisocyanate trimer (tri-IPDI) in the polymer backbone and LiTFSI concentrations via an in situ polymerization method, which gave rise to good interfacial compatibility. Furthermore, the in situ-prepared PAEPU-SPE@D(15) based on the IPDI/tri-IPDI molar ratio of 2:1 and 15 wt % LiTFSI exhibits an improved ionic conductivity of 6.80 × 10(–5) S/cm at 30 °C and could reach 10(–4) orders of magnitude when the temperature was above 40 °C. The Li|LiFePO(4) battery based on PAEPU-SPE@D(15) had a wide electrochemical stability window of 5.18 V, demonstrating a superior interface compatibility toward LiFePO(4) and the lithium metal anode, exhibited a high discharge capacity of 145.7 mAh g(–1) at the 100th cycle and a capacity retention of 96.8%, and retained a coulombic efficiency of above 98.0%. These results showed that the PAEPU-SPE@D(15) system displayed a stable cycle performance, excellent rate performance, and high safety compared with PEO systems, indicating that the PAEPU-based SPE system may play a crucial role in the future.