High‐Energy Sodium Ion Batteries Enabled by Switching Sodiophobic Graphite into Sodiophilic and High‐Capacity Anodes

Owing to the crustal abundance of sodium element, sodium ion batteries (SIBs) are considered a promising complementary to lithium-ion battery for stationary energy storage applications. The cointercalation chemistry enables the use of cost-effective graphite as anodes, whereas the low capacity (<130 mAh g^-1) and high redox potential (>0.6 V vs. Na/Na⁺) of graphite significantly limit the energy density of SIBs. Herein, we induce the high-capacity Na metal into sodiophilic ternary graphite intercalation compounds (t-GICs) via co-intercalation and deposition reactions, thereby achieving Na/t-GIC anodes with high capacities and low working voltage (0.18 V). The new anodes exhibit high coulombic efficiencies of above 99.7 % over 550 cycles and a high-rate capacity of 588.4 mAh g^-1 at 6 C (10 min per charge). When it is paired with Na₃V₂(PO₄)₂F₃ (NVPF) cathodes, the SIBs demonstrate a high energy density of 259 Wh kg^-1 _{both electrodes} surpassing that of commercial LiFePO₄//graphite batteries. The outstanding anode performance is attributed to the tailored sodiophilicity of graphite through manipulating the ether solvents and the in situ generated space among t-GIC flakes to stably accommodate Na metal. Our findings for stable Na plating/striping on sodiophilic graphite materials provide an effective approach for developing advanced SIBs.