α‑TiPO4 as a Negative Electrode Material for Lithium-Ion Batteries

To realize high-power performance, lithium-ion batteries require stable, environmentally benign, and economically viable noncarbonaceous anode materials capable of operating at high rates with low strain during charge–discharge. In this paper, we report the synthesis, crystal structure, and electrochemical properties of a new titanium-based member of the MPO4 phosphate series adopting the α-CrPO4 structure type. α-TiPO4 has been obtained by thermal decomposition of a novel hydrothermally prepared fluoride phosphate, NH4TiPO4F, at 600 °C under a hydrogen atmosphere. The crystal structure of α-TiPO4 is refined from powder X-ray diffraction data using a Rietveld method and verified by electron diffraction and high-resolution scanning transmission electron microscopy, whereas the chemical composition is confirmed by IR, energy-dispersive X-ray, electron paramagnetic resonance, and electron energy loss spectroscopies. Carbon-coated α-TiPO4/C demonstrates reversible electrochemical activity ascribed to the Ti3+/Ti2+ redox transition delivering 125 mAh g–1 specific capacity at C/10 in the 1.0–3.1 V versus Li+/Li potential range with an average potential of ∼1.5 V, exhibiting good rate capability and stable cycling with volume variation not exceeding 0.5%. Below 0.8 V, the material undergoes a conversion reaction, further revealing capacitive reversible electrochemical behavior with an average specific capacity of 270 mAh g–1 at 1C in the 0.7–2.9 V versus Li+/Li potential range. This work suggests a new synthesis route to metastable titanium-containing phosphates holding prospective to be used as negative electrode materials for metal-ion batteries.