Homeostatic Solid Solution Reaction in Phosphate Cathode: Breaking High‐Voltage Barrier to Achieve High Energy Density and Long Life of Sodium‐Ion Batteries

Abstract The stable phase transformation during electrochemical progress drives extensive research on vanadium‐based polyanions in sodium‐ion batteries (SIBs), especially Na₃V₂(PO₄)₃ (NVP). And the electron transfer between V^3+/4+ redox couple in NVP could be generally achieved, owing to the confined crystal variation during battery service. However, the more favorable V^4+/5+ redox couple is still in hard‐to‐access situation due to the high barrier and further brings about the corresponding inefficiency in energy densities. In this work, the multilevel redox in NVP frame (MLNP) alters reaction pathway to undergo homeostatic solid solution process and breaks the high barrier of V^4+/5+ at high voltage, taking by progressive transition metal (V, Fe, Ti, and Cr) redox couple. The diversified reaction paths across diffusion barriers could be realized by distinctive release/uptake of inactive Na1 site, confirmed by the calculations of density functional theory. Thereby its volume change is merely 1.73% during the multielectron‐transfer process (≈2.77 electrons). MLNP cathode could achieve an impressive energy density of 440 Wh kg⁻¹, driving the leading development of MLNP among other NASICON structure SIBs. The integration of multiple redox couples with low strain modulates the reaction pathway effectively and will open a new avenue for fabricating high‐performance cathodes in SIBs.