Enhancing Orbital Interaction in Spinel LiNi0.5Mn1.5O4 Cathode for High‐Voltage and High‐Rate Li‐Ion Batteries

High voltage cobalt‐free spinel LiNi0.5Mn1.5O4 (LNMO) is well organized as a high‐power cathode material for lithium (Li)‐ion batteries, however, the weak interaction between the 3d orbital of the transition metal (TM) ions and the 2p orbital of oxygen (O) leads to the instability of crystal structural, hindering the long‐term stable cycling of LNMO cathode especially at high temperatures. Here, a design strategy of orbital interaction is initiated to strengthen TM 3d‐O 2p framework in P‐doped LNMO (P‐LNMO) by choosing phytic acid as P dopant, which can realize more uniform doping compared to regular phosphate. The results show that the enhancement of TM 3d‐O 2p orbital interaction in P‐LNMO can suppress the Jahn–Teller effect and subsequent dissolution of Mn, as well as lowers the energy barrier for Li ion insertion/extraction kinetics. As a result, superior electrochemical performances including high discharge capacity, stable cycling behavior and enhanced rate capability of P‐LNMO are obtained. Significantly, the P‐LNMO pouch cell shows great cycling stability with 97.4% capacity retention after 100 cycles. In this work, P‐LNMO is ingeniously designed by inspiration of orbital interaction theory and the band structures of Mn 3d, Ni 3d, and O 2p are regulated by the introduction of P dopant. The P‐LNMO//Li metal full cell retain 97.4% of its initial capacity after 100 cycles.