Performance of 3D Network-Structured LiFePO@LiV(PO)/Carbon Nanofibers via Coaxial Electrospinning as Self-Supporting Cathode for Lithium-Ion Batteries.

Lithium-ion batteries (LIBs) with high power, high capacity, and support for fast charging are increasingly favored by consumers. As a commercial electrode material for power batteries, LiFePO was limited from further wide application due to its low conductivity and lithium-ion diffusion rate. The development of advanced architectures integrating rational conductive networks with optimized ion transport pathways represents a critical frontier in optimizing the performance of cathode materials. In this paper, a novel self-supporting cathode material (designated as LFP@LVP-CES) was synthesized through an integrated coaxial electrospinning and controlled pyrolysis strategy. This methodology directly converts LiFePO, LiV(PO), and polyacrylonitrile (PAN)) into flexible, binder-free cathodes with a hierarchical structural organization. The 3D carbon nanofiber (CNF) matrix synergistically integrates LiFePO (Li/Fe/PO) and LiV(PO) (Li/V/PO) nanoparticles, where CNFs act as a conductive scaffold to enhance electron transport, while the PO polyanionic frameworks stabilize Li diffusion pathways. Morphological characterizations (SEM and TEM) revealed a 3D cross-connected carbon nanofiber matrix (diameter: 250 ± 50 nm) uniformly embedded with active material particles. Electrochemical evaluations demonstrated that the LFP@LVP-CES cathode delivers an initial specific capacity of 165 mAh·g at 0.1 C, maintaining 80 mAh·g at 5 C. Notably, the material exhibited exceptional rate capability and cycling stability, demonstrating a 96% capacity recovery after high-rate cycling upon returning to 0.1 C, along with 97% capacity retention over 200 cycles at 1 C. Detailed kinetic analysis through EIS revealed significantly reduced R and increased Li diffusion. This superior electrochemical performance can be attributed to the synergistic effects between the 3D conductive network architecture and dual active materials. Compared with traditional coating processes and high-temperature calcination, the preparation of controllable electrospinning and low-temperature pyrolysis to some extent avoid the introduction of harmful substances and reduce raw material consumption and carbon emissions. This original integration strategy establishes a paradigm for designing freestanding electrode architectures through 3D structural design combined with a bimodal active material, providing critical insights for next-generation energy storage systems.