Sodium iron phosphate-pyrophosphate, Na₄Fe₃(PO₄)₂P₂O₇ (NFPP) emerges as an excellent cathode material for sodium-ion batteries. Because of lower electronic conductivity, its electrochemical performance depends drastically on the synthesis method. Herein, we provide a simple and unified method for synthesis of composites between NFPP and reduced graphene oxide (rGO) and standard carbon black, designed as electrode materials for both sodium- and lithium-ion batteries. The carbon additives affect only the morphology and textural properties of the composites. The performance of composites in sodium and lithium cells is evaluated at elevated temperatures. It is found that NFPP/rGO outperforms NFPP/C in both Na and Li storage due to its hybrid mechanism of energy storage. In sodium half-cells, NFPP/rGO delivers a reversible capacity of 95 mAh/g at 20 °C and 115 mAh/g at 40 °C with a cycling stability of 95% and 88% at a rate of C/2. In lithium half-cells, the capacity reaches a value of 120 mAh/g at 20 and 40 °C, but the cycling stability becomes worse, especially at 40 °C. The electrochemical performance is discussed on the basis of ex situ XRD and microscopic studies. The good Na storage performance of NFPP/rGO at an elevated temperature represents a first step towards its commercialization.

Recently, there has been increased interest in NASICON-type electrodes for sodium-ion batteries due to their unique combination of intercalation properties, low cost, and safety. However, their commercialization is hindered by the low electrical conductivity. One strategy to overcome this issue is to integrate NASICON materials with carbon additives. This study shows that carbon additives improve the sodium storage performance of a NASICON-type electrode in various ways, depending on the additives’ functional groups, texture, and conductivity properties. The proof-of-concept is based on a multi-electron phospho-sulphate electrode, NaFeVPO₄(SO₄)₂ (NFVPS) mixed with carbon black (C) and reduced graphene oxide (rGO). Carbon-coated samples are obtained via a simple ball milling procedure followed by thermal treatment in an argon flow. Sodium storage in the composites occurs through capacitive and Faradaic reactions. The Faradaic reaction is facilitated at the carbon black composite, while the capacitive reaction dominates for the rGO composite. NFVPS operates through two-electron reactions at 20 °C, while the increased temperatures favor the three-electron reaction. The rGO composite outperforms the carbon black composite in terms of cycling stability and rate capability at 20 and 40 °C. The role of the rGO and carbon black in electrochemical performance is discussed based on the different reactivity of hydroxyl/epoxide and carbonyl functional groups with the electrolyte salt, NaPF₆, and the solvent, polypropylene carbonate.