The low coulombic efficiency and poor cycle performance deriving from uncontrolled growth of dendrites have caused a serious obstacle to the practical application of lithium metal. Herein we propose a bifunctional regular-random dual cross-linking network solid polymer electrolyte (RRa-SPE) for dendrite-free all-solid-state lithium metal batteries. Under the synergistic effect of regular polymerization skeleton and random cross-linking network, the RRa-SPE effectively regulates the lithium deposition and facilitates the generation of a highly homogeneous and robust solid-electrolyte interphase (SEI) layer on lithium metal. Besides, this RRa-SPE shows benign ionic conductivity of 4.36 × 10⁻⁴ S cm⁻¹ (at 30 °C), high lithium ion transference number of 0.76 and enhanced mechanical strength. The Li/RRa-SPE/Li symmetric cell maintains low and stable voltage polarization (0.15 V) after circulating for 1200 h at 0.5 mA cm⁻². Improved LiFePO₄/RRa-SPE/Li cell exhibits excellent rate capability and prominent cycle performance with a capacity retention of 99.6% after 240 cycles at 0.5 C at 30 °C.

由于树枝状晶体不受控制的生长而导致的库仑效率低和循环性能差已经严重阻碍了锂金属的实际应用。在这里，我们提出了一种用于无枝晶的全固态锂金属电池的双功能规则随机双交联网络固体聚合物电解质（RRa-SPE）。在常规聚合骨架和无规交联网络的协同作用下，RRa-SPE有效调节锂的沉积并促进在锂金属上生成高度均一且坚固的固体电解质中间相（SEI）层。此外，该RRa-SPE的良性离子电导率为4.36×10 ^-4  S cm ^-1（在30°C下），高锂离子转移数为0.76，并提高了机械强度。Li / RRa-SPE / Li对称电池在0.5 mA cm ^-2下循环1200小时后，保持低且稳定的电压极化（0.15 V）。改进的LiFePO ₄ / RRa-SPE / Li电池具有出色的倍率性能和出色的循环性能，在30°C下于0.5 C进行240次循环后，容量保持率为99.6％。