The development of low-cost and long-lasting all-climate cathode materials for the sodium ion battery has been one of the key issues for the success of large-scale energy storage. One option is the utilization of earth-abundant elements such as iron. Here, we synthesize a NASICON-type tuneable Na 4 Fe 3 (PO 4 ) 2 (P 2 O 7 )/C nanocomposite which shows both excellent rate performance and outstanding cycling stability over more than 4400 cycles. Its air stability and all-climate properties are investigated, and its potential as the sodium host in full cells has been studied. A remarkably low volume change of 4.0% is observed. Its high sodium diffusion coefficient has been measured and analysed via first-principles calculations, and its three-dimensional sodium ion diffusion pathways are identified. Our results indicate that this low-cost and environmentally friendly Na 4 Fe 3 (PO 4 ) 2 (P 2 O 7 )/C nanocomposite could be a competitive candidate material for sodium ion batteries.

Recently, room-temperature stationary sodium-ion batteries (SIBs) have received extensive investigations for large-scale energy storage systems (EESs) and smart grids due to the huge natural abundance and low cost of sodium. The SIBs share a similar "rocking-chair" sodium storage mechanism with lithium-ion batteries; thus, selecting appropriate electrodes with a low cost, satisfactory electrochemical performance, and high reliability is the key point for the development for SIBs. On the other hand, the carefully chosen elements in the electrodes also largely determine the cost of SIBs. Therefore, earth-abundantmetal-based compounds are ideal candidates for reducing the cost of electrodes. Among all the high-abundance and low-cost metal elements, cathodes containing iron and/or manganese are the most representative ones that have attracted numerous studies up till now. Herein, recent advances on both ironand manganese-based cathodes of various types, such as polyanionic, layered oxide, MXene, and spinel, are highlighted. The structure-function property for the iron-and manganese-based compounds is summarized and analyzed in detail. With the participation of iron and manganese in sodium-based cathode materials, real applications of room-temperature SIBs in large-scale EESs will be greatly promoted and accelerated in the near future.

The peak-loading shift function of sodium-ion batteries in large-grid energy store station poses a giant challenge on the account of poor rate performance of cathodes. NASICON type Na3V2(PO4)3 with a stable three-dimensional framework and fast ion diffusion channels has been regarded as one of the potential candidates and extensively studied. Nevertheless, a multilevel integrated tactic to boost the performance of Na3V2(PO4)3 in terms of crystal structure modulation, coated carbon graphitization regulation, and particle morphology design is rarely reported and deserves much attention. In this study, organic ferric was used to prepare Fe-doped Na3V2(PO4)3@C cathode on the account of low cost, environmental friendliness, and catalytic function of Fe on carbon graphitization. The density functional theory calculation depicts that the most stable site for Fe atom is the V site and moderate replacement of Fe at V position would reduce the band gap energy from 2.19 by 0.43 eV and improve the electron transfer, which is crucial for the intrinsic poor conductivity of Na3V2(PO4)3. The experimental results show that Fe element can be introduced into the bulk structure successfully, modulating relevant structural parameters. In addition, the coated carbon layer graphitization degree is also regulated due to the catalysis function of Fe. And, the decomposition of organic ferric would infuse the formation of porous structure, which can promote electrolyte permeation and shorten the electron/ion diffusion. Finally, the optimized Na3V1.85Fe0.15(PO4)3@C could possess a high capacity of 103.69 mA h g–1 and retain 91.45% after 1200 cycles at 1.0C as well as 94.45 mA h g–1 at 20C. In addition, the excellent performance is comprehensively elucidated via ex situ X-ray diffraction and pseudocapacitance characterization. The multifunction contribution of Fe-doping may provide new clue for designing porous electrode materials and a new sight into Fe-doped carbon-coated material.