Among the inorganic-organic hybrid complexes the zinc phenyl phosphinate (PhPZn) represent high char yield to the benefit of electron transfer of its derivatives. Herein, a γ/α-Zn2P2O7/C composite derived from PhPZn during pyrolysis exhibits surface porous framework supported by thin nanosheet shells and the internal mesoporous structure. Based on the conversion/alloy reaction mechanism, the γ/α-Zn2P2O7/C anode for sodium storage shows the impressive reversible capacity of 277 mA h g−1 at 0.1 A g−1, rate capability of 107 mA h g−1 at 5 A g−1 and cyclic stability of 115 mA h g−1 after 1000 cycles at 1 A g−1 with a capacity retention rate of 73.0%. This work is of great significance in broadening the anode material systems of sodium-ion batteries.
