Extending the solid solution range of sodium ferric pyrophosphate:Off‐stoichiometric Na_(3)Fe(2.5)(P_(2)O_(7))_(2)as a novel cathode for sodium‐ion batteries

Iron‐based pyrophosphates are attractive cathodes for sodium‐ion batteries due to their large framework,cost‐effectiveness,and high energy density.However,the understanding of the crystal structure is scarce and only a limited candidates have been reported so far.In this work,we found for the first time that a continuous solid solution,Na_(4−α)Fe_(2+α)_(2)(P_(2)O_(7))_(2)(0≤α≤1,could be obtained by mutual substitution of cations at center‐symmetric Na3 and Na4 sites while keeping the crystal building blocks of anionic P_(2)O_(7) unchanged.In particular,a novel off‐stoichiometric Na_(3)Fe(2.5)(P_(2)O_(7))_(2)is thus proposed,and its structure,energy storage mechanism,and electrochemical performance are extensively investigated to unveil the structure–function relationship.The as‐prepared off‐stoichiometric electrode delivers appealing performance with a reversible discharge capacity of 83 mAh g^(−1),a working voltage of 2.9 V(vs.Na^(+)/Na),the retention of 89.2%of the initial capacity after 500 cycles,and enhanced rate capability of 51 mAh g^(−1)at a current density of 1600 mA g^(−1).This research shows that sodium ferric pyrophosphate could form extended solid solution composition and promising phase is concealed in the range of Na_(4−α)Fe_(2+α)_(2)(P_(2)O_(7))_(2),offering more chances for exploration of new cathode materials for the construction of high‐performance SIBs.

Boosting rate and cycling performance of K-doped Na_(3)V_(2)(PO_(4))_(2)F_(3) cathode for high-energy-density sodium-ion batteries

As a promising cathode material,Na_(3)V_(2)(PO_(4))_(2)F_(3)(NVPF)has attracted wide attention for sodium-ion batteries(SIBs)because of its high operating voltage and high structural stability.However,the low intrinsic electronic conductivity and insufficient Na ion mobility of NVPF limit its development.Herein,K-doping NVPF is prepared through a facile ball-milling combined calcination method.The effects of K-doping on the crystal structure,kinetic properties and electrochemical performance are investigated.The results demonstrate that the Na_(2.90)K_(0.10)V_(2)(PO_(4))_(3)F_(3)(K0.10-NVPF)exhibits a high capacity(120.8 mAh g^(-1) at 0.1 C),high rate capability(66 mAh g^(-1) at 30 C)and excellent cycling performance(a capacity retention of 97.5%at 1 C over 500 cycles).Also,the occupation site of K ions in the lattice,electronic band structure and Na-ion transport kinetic property in K-doped NVPF are investigated by density functional theory(DFT)calculations,which reveals that the K-doped NVPF exhibits improved electronic and ionic conductivities,and located K^(+) ions in the lattice to contribute to high reversible capacity,rate capability and cycling stability.Therefore,the K-doped NVPF serves as a promising cathode material for high-energy and high-power SIBs.