The transition towards a new energy system has proliferated demand for lithium-ion batteries (LIBs) cathode materials with stable performance. To enhance the performance of the cathode materials, here-in, flexible LiMn0.8Fe0.2PO4/C (LMFP) dense microspheres with primary nanocrystalline are prepared by spray drying and solid state sintering. Coating the LiMn0.8Fe0.2PO4 primary nanocrystalline with a conformal carbon nanolayer (∼3 nm) significantly improves the electronic conductivity of the active cathode material. The prepared LMFP cathode exhibited excellent rate performance with a discharge capacity of 129.1 mAh g−1 at 10C. Furthermore, the LMFP cathode depicted excellent cyclic stability, maintained a capacity retention of 95% after 1000 cycles at 1C and only 0.0073 mAh g−1 loss per cycle. Thermodynamics, surface morphology, phase structure, and electrochemical performance were used to investigate the effect of blending flexible LMFP and Ni-rich LiNi0.85Co0.10Al0.05O2 (NCA) electrodes. The results depict that the thermal stability and cyclic reversibility of blending electrodes are significantly improved compared with the pristine NCA, and the blended electrodes display superior comprehensive properties.