Manganese Local Environment Modulation via SiO4 Substitution to Boost Sodium Storage Performance of Na4MnCr(PO4)3

Manganese-based Na superionic conductors (NASICONs) Na4 MnCr(PO4 )3 with three-electron reaction are attractive cathode materials for sodium-ion batteries. However, the irreversible distortion of Mn local structure leads to sluggish electrode kinetics, voltage hysteresis, and poor cycling stability. Here, SiO4 is introduced to substitute PO4 to modulate the local environment of Mn to activate the redox activity and stabilize the reversibility of Na4 MnCr(PO4 )2.9 (SiO4 )0.1 (NMCP-Si). A combined experimental and theoretical investigation have been undertaken to reveal the evolution of electronic structures and Na storage properties associated with SiO4 substitution. The NMCP-Si exhibits much-enhanced rate capability and cycling stability, being attributed to the unique Jahn-Teller distortion (Mn3+ ) that facilitates sodium de/insertion kinetics by optimizing the Na ion diffusion channels. This work addresses the challenge of stabilizing the structure of Mn-based NASICONs and represents a breakthrough in understanding how to improve the Na+ conductivity by regulating local structure.