Cobalt phosphide (CoP) has been emerging as alternative lithium-ion batteries (LIBs) anode in view of the outstanding thermodynamic stability and high theoretical capacity. However, the lithium storage behaviors were impeded by poor cycling and rate performance induced by huge volumetric changes of CoP anodes during Li⁺ intercalation/deintercalation and the poor reaction kinetics caused by low electronic conductivity. Herein, the uniquely designed hemoglobin-like composites consisting of CoP nanoparticles coated by N, P-doped carbon shell (CoP@PNC) were prepared via a supramolecular self-assembly method, followed by the facile heat treatment process, which presented the amorphous phase. Based on the synergistic effects of rational nano/microstructure, double heterogeneous elements doped carbon substrate and amorphous phase, the transport paths of Li⁺ and e⁻ were shortened, the electronic conductivity was enhanced, the volumetric changes were effectively alleviated, resulting in outstanding electrochemical performance when applied as anode electrodes. The CoP@PNC electrodes deliver a capacity of 806.8 mAh g⁻¹ after 100 cycles at 0.1 A g⁻¹ and 523.9 mAh g⁻¹ after 3000 cycles at 2.0 A g⁻¹. Furthermore, pseudo-capacitance behavior dominates the storage mechanism of CoP@PNC electrodes based on the quantitative kinetic analysis result that a high ratio of 66% in total capacity at 0.5 mV⁻¹. This work illuminates the route to effectively relieve the huge volumetric changes to improve the electrochemical performance of transition metal phosphide and promote their practical application steps as electrodes for high energy density batteries.

鉴于出色的热力学稳定性和高理论容量，磷化钴 (CoP) 已成为替代锂离子电池 (LIB) 的负极。^{然而，Li +}过程中CoP负极的巨大体积变化导致循环性能和倍率性能差，阻碍了锂的存储行为。嵌入/脱嵌和低电子电导率导致的不良反应动力学。在此，通过超分子自组装方法制备了由 N、P 掺杂碳壳包覆的 CoP 纳米粒子 (CoP@PNC) 组成的独特设计的类血红蛋白复合材料，随后采用简单的热处理工艺，呈现非晶相. 基于合理的纳米/微观结构、双异质元素掺杂碳基底和非晶相的协同作用，Li ⁺和 e ^{-的传输路径}缩短，电子电导率增强，体积变化得到有效缓解，用作阳极电极时具有出色的电化学性能。^{CoP@PNC 电极在 0.1 A g -1}下循环 100 次后的容量为 806.8 mAh g -1 ^，在 2.0 A g -1 下循环 3000 次^{后容量为 523.9 mAh g -1}。此外，基于定量动力学分析结果，赝电容行为主导了 CoP@PNC 电极的存储机制，即在 0.5 mV ^{-1时总容量的比例高达 66%}. 这项工作阐明了有效缓解巨大体积变化以提高过渡金属磷化物电化学性能并促进其作为高能量密度电池电极的实际应用步骤的途径。