Metal/non-metal co-doped lithium titanate spheres with hierarchical micro/nano architectures for high rate lithium ion batteries
View Patent ↗The present invention is to provide a lithium titanate (LTO) material for a lithium ion battery. The LTO material has hierarchical micro/nano architecture, and comprises a plurality of micron-sized secondary LTO spheres, and a plurality of pores incorporated with metal formed by a metal dopant. Each of the micron-sized secondary LTO spheres comprises a plurality of nano-sized primary LTO particles. A plurality of the nano-sized primary LTO particles is encapsulated by a non-metal layer formed by a non-metal dopant. The LTO material of the present invention has high electrical conductivity for increasing the capacity at high charging/discharging rates, and energy storage capacity.
1. A method for fabricating a metal and non-metal co-doped lithium titanate (LTO) material, comprising:
mixing at least one titanium (Ti) containing precursor, at least one lithium (Li) containing precursor, and at least one non-metal dopant precursor in at least one solvent to form a mixture;
hydrothermally heating the mixture under a pressure ranging from 1.5 to 5 atm, and a heating temperature ranging from 120 to 200° C. to form nano-sized primary LTO particles, wherein one or more of the nano-sized primary LTO particles are encapsulated by at least one layer of non-metal dopant;
calcining the nano-sized primary LTO particles at a first calcination temperature ranging from 450 to 750° C. to form micron-sized secondary LTO spheres;
immersing the micron-sized secondary LTO spheres into at least one metal dopant containing solution to incorporate at least one metal dopant into the micron-sized secondary LTO spheres;
drying the micron-sized secondary LTO spheres incorporated with the metal dopant in vacuum; and
calcining the micron-sized secondary LTO spheres incorporated with the metal dopant at a second calcination temperature ranging from 450 to 750° C. to form the LTO material.
2. The method of claim 1 , wherein the solution comprises 1-7 wt % of the Ti containing precursor, 4-10 wt % of the Li containing precursor, 80-92 wt % of the solvent, and 1-10 wt % of the non-metal dopant precursor.
3. The method of claim 1 , wherein the Ti containing precursor is tetrabutyl titanate, and the Li containing precursor is lithium acetate dehydrate.
4. The method of claim 1 , wherein the non-metal dopant precursor is a carbon source, or urea.
5. The method of claim 1 , wherein the non-metal dopant is carbon, nitrogen, or fluorine.
6. The method of claim 1 , wherein the metal dopant containing solution comprises one or more ions of copper, nickel, cobalt, manganese, gold, platinum, iron, and/or tin.
7. The method of claim 1 , wherein the step of calcinating the nano-sized LTO primary particles further comprises:
calcining the nano-sized primary LTO particles in a tube furnace under nitrogen atmosphere; and
heating the nano-sized LTO primary particles to the first calcination temperature at a first heating rate in a range of 0.5 to 5° C./min.
8. The method of claim 7 , wherein the step of calcining the micron-sized LTO secondary spheres further comprises:
calcining the micron-sized secondary LTO spheres in a tube furnace under nitrogen atmosphere; and
heating the micron-sized LTO secondary spheres to the second calcination temperature at a second heating rate in a range of 0.5 to 5° C./min.
9. The method of claim 1 , further comprising after the step of hydrothermally heating the mixture:
drying the nano-sized primary LTO particles; and
grinding the nano-sized primary LTO particles.