Activating Stable Multielectron Transfer via High‐Frequency Na ⁺ Jumping for a Sc‐doped Na _3.97 VMn _0.97 Sc _0.03 (PO ₄ ) ₃

Abstract The Na ₄ VMn(PO ₄ ) ₃ (NVMP) cathode is considered one of the most promising candidates for sodium‐ion batteries (SIBs), but it suffers from a low capacity due to the limited kinetics of V ³⁺ /V ⁴⁺ and Mn ²⁺ /Mn ³⁺ in the electrochemical reaction. A higher capacity can be achieved by activating a redox pair with high valence states like V ⁴⁺ /V ⁵⁺ . However, activation of those redox pairs in conventional NVMP cathode requires a redox potential beyond 4.0 V (vs Na ⁺ /Na) and induces serious structural degradation. Herein, a scandium (Sc)‐doped Na _3.97 VMn _0.97 Sc _0.03 (PO ₄ ) ₃ is designed, which activates multielectron transfer while effectively mitigating reversibility compromises by configuring a rational voltage range. The capacity can be improved by 16.7% to 113.8 mAh g ⁻¹ based on more electron transfer from 1.75e ⁻ to 2.05 e ⁻ , which is mainly attributed to the accelerated redox reactions of V ³⁺ /V ⁴⁺ and Mn ²⁺ /Mn ³⁺ within 2.0–3.8 V (vs Na ⁺ /Na). The enhanced kinetics are achieved by faster Na ⁺ diffusion kinetics via high‐frequency Na ⁺ jumping, which originates from enriched V _Na ′ vacancy by Sc doping. The improved kinetics also ameliorate grain uniformity during repeatable charge‐discharge cycling, leading to an excellent capacity retention of 80.2% after 1400 cycles at 5C. These findings offer a promising pathway toward facile and controllable multi‐electron transfer cathodes.