Illustration of the fabrication process of 77S/Mo_xC@NC.

Solid polymer electrolytes have attracted considerable attention, owing to their flexibility and safety. At present, poly(ethylene oxide) is the most widely studied polymer electrolyte matrix. It exhibits higher safety than the polyolefin diaphragm used in traditional lithium-ion batteries. However, it readily crystallizes at room temperature, resulting in low ionic conductivity, and the preparation process involves organic solvents. In this study, from the perspective of molecular design, solvent-free polyaspartate polyurea (PAEPU) and the cheap and easily available polypropylene (PP) nonwoven fabric were used as support materials for the PAEPU/PP composite solid polymer electrolyte (PAEPU/PPm-CPE). This CPE has good thermal stability, dimensional stability, flexibility, and mechanical properties. Among the different CPEs that were analyzed, PAEPU/PP10-CPE@20 had the highest ionic conductivity, which was reinforced with 10 g/m(2) PP nonwoven fabric and the content of lithium salt was 20 wt %. Furthermore, PAEPU/PP10-CPE@20 exhibited the highest electrochemical stability with an electrochemical window value of 5.53 V. Moreover, the capacity retention rate of the Li//PAEPU/PP10-CPE@20//LiFePO4 half-cell was 96.82% after 150 cycles at 0.05 C and 60 degrees C, and the capacity recovery rate in the rate test reached 98.81%.

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@D₁₅ 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|LiFePO₄ battery based on PAEPU-SPE@D₁₅ had a wide electrochemical stability window of 5.18 V, demonstrating a superior interface compatibility toward LiFePO₄ 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@D₁₅ 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.