Engineering of Cerium Modified TiNb2O7 Nanoparticles For Low-Temperature Lithium-Ion Battery.

Although TiNb2O7 (TNO) with comparable operating potential and ideal theoretical capacity is considered to be the most ideal replacement for negative Li4Ti5O12 (LTO), the low ionic and electronic conductivity still limit its practical application as satisfactory anode for lithium-ion batteries (LIBs) with high-power density. Herein, TNO nanoparticles modified by Cerium (Ce) with outstanding electrochemical performance are synthesized. The successful introduction of Ce3+ in the lattice leads to increased interplanar spacing, refined grain size, more oxygen vacancy, and a smaller lithium diffusion barrier, which are conducive to improve conductivity of both Li+ and electrons. As a result, the modified TNO reaches high reversible capacity of 256.0 mA h g-1 at 100 mA g-1 after 100 cycles, and 183.0 mA h g-1 even under 3200 mA g-1. In particular, when the temperature drops to -20 °C, the cell undergoing 1500 cycles at a high current density of 500 mA g-1 can still reach 89.7 mA h g-1, corresponding to a capacity decay rate per cycle of only 0.033%. This work provides a new way to improve the electrochemical properties of alternative anodes for LIBs at extreme temperature.

Bulk Modification of Porous TiNb2 O7 Microsphere to Achieve Superior Lithium-Storage Properties at Low Temperature.

TiNb2 O7 , as a promising alternative of Li4 Ti5 O12 , exhibits giant potential as low-temperature anode due to its higher theoretical capacity and comparable structural stability. However, the sluggish electronic conductivity still remains a challenge. Herein, bulk modification of Cu+ doping in porous TiNb2 O7 microsphere is proposed via a simple one-step solvothermal method with subsequent calcination treatment. The results show that the electronic conductivity is improved effectively due to the reduced band gap after doping, while enhanced lithium-ion diffusion is achieved benefiting from the increased interplanar spacing. Therefore, the optimal sample of Cu0.06 Ti0.94 Nb2 O7 exhibits a high reversible capacity of 244.4 mA h g-1 at 100 mA g-1 after 100 cycles, superior rate capability, and long-term cycling stability at 1000 mA g-1 at room temperature. Particularly, it can also display good performance in a wide temperature range from 25 to -30 °C, including a reversible capacity of 76.6 mA h g-1 at -20 °C after 200 cycles at 200 mA g-1 . Moreover, Cu0.06 Ti0.94 Nb2 O7 //LiFePO4 full cell can deliver a high reversible capacity of 177.5 mA h g-1 at 100 mA g-1 . The excellent electrochemical properties at both ambient and low-temperatures demonstrate the great potential of Cu+ -doped TiNb2 O7 in energy-storage applications.