CN-116812969-B - Preparation method of hierarchical pore indium oxide nanotube for lithium ion battery cathode

CN116812969BCN 116812969 BCN116812969 BCN 116812969BCN-116812969-B

Abstract

The invention discloses a preparation method of a multistage hole indium oxide nanotube for a lithium ion battery cathode, which comprises the following steps of (1) placing indium salt and terephthalic acid In an organic solvent, uniformly stirring under an oil bath condition to obtain a homogeneous dispersion liquid, (2) continuously heating and continuously stirring the homogeneous dispersion liquid for reaction, naturally cooling to room temperature after the reaction is finished to obtain a mixed reaction system, (3) carrying out suction filtration on the mixed reaction system, washing a solid product obtained by suction filtration with absolute ethyl alcohol, drying, obtaining a precursor MIL-68 (In) after the drying is finished, and (4) placing the precursor MIL-68 (In) In a tubular furnace, carrying out pyrolysis treatment In an air atmosphere, and obtaining the multistage hole indium oxide nanotube after the pyrolysis treatment is finished. The invention can solve the problems of poor cycle performance, poor multiplying power performance and the like of the existing In 2 O 3 -based anode material.

Inventors

LI XUELEI
LIU SHI
LIU JUN
NAN DING
DONG JUNHUI

Assignees

内蒙古工业大学

Dates

Publication Date: 20260505
Application Date: 20230714

Claims (5)

1. The preparation method of the hierarchical pore indium oxide nanotube for the lithium ion battery cathode is characterized by comprising the following steps of: step (1), placing indium salt and terephthalic acid in an organic solvent, and uniformly stirring to obtain a homogeneous dispersion; Continuously heating and continuously stirring the homogeneous dispersion liquid to perform hydrothermal synthesis reaction, and naturally cooling to room temperature after the reaction is finished to obtain a mixed reaction system; Step (3), carrying out suction filtration on the mixed reaction system, washing a solid product obtained by suction filtration with absolute ethyl alcohol, and drying to obtain a precursor MIL-68 (In) after the drying is finished; Step (4), placing a precursor MIL-68 (In) In a tube furnace, and performing pyrolysis treatment In an air atmosphere to obtain a hierarchical pore indium oxide nanotube HPNT-In 2 O 3 for the negative electrode of the lithium ion battery after the pyrolysis treatment is finished; in the step (1), the indium salt is indium nitrate hydrate or indium chloride hydrate, the mass ratio of the indium salt to terephthalic acid is 1:2-5, and the volume mass ratio of the organic solvent to terephthalic acid is 100-150 mL/g; in the step (2), continuously heating the homogeneous dispersion liquid to 115-125 ℃ and continuously stirring for 45-75 min; In step (4), the pyrolysis treatment includes the following two stages: step (4-1), raising the temperature from room temperature to 120-130 ℃ at a temperature raising rate of 4-6 ℃ per minute, and preserving heat for 2-2.5 h; continuously heating to 400-410 ℃ at a heating rate of 4-6 ℃ per minute, and preserving heat for 2-2.5 h; In the step (1), the organic solvent is N, N-dimethylformamide, and the stirring time is 20min; The multi-level pore indium oxide nanotube has a macroporous structure of 50nm-100nm, a mesoporous structure of 2-50nm and a microporous structure smaller than 2 nm.
2. The method for preparing a hierarchical porous indium oxide nanotube for a negative electrode of a lithium ion battery according to claim 1, wherein in the step (1), the indium salt is indium nitrate pentahydrate, the mass ratio of the indium nitrate pentahydrate to terephthalic acid is 1:3, and the volume mass ratio of the organic solvent to terephthalic acid is 120mL/g.
3. The method for preparing a hierarchical pore indium oxide nanotube for a negative electrode of a lithium ion battery according to claim 1, wherein in the step (2), the homogeneous dispersion is continuously heated to 120 ℃ and stirred for 60 minutes.
4. The method for preparing a hierarchical pore indium oxide nanotube for a negative electrode of a lithium ion battery according to claim 1, wherein in the step (4), the pyrolysis treatment comprises the following two stages: step (4-1), raising the temperature from room temperature to 120 ℃ at a temperature raising rate of 5 ℃ per minute, and preserving the heat for 2 hours; And (4-2) continuously heating to 400 ℃ at a heating rate of 5 ℃ per minute, and preserving heat for 2 hours.
5. The method for preparing the multi-pore indium oxide nanotube for the lithium ion battery cathode according to claim 1, wherein in the step (3), an organic filter membrane with the pore diameter of 0.22 μm is adopted for suction filtration, the times of washing with absolute ethyl alcohol are at least 3 times, the drying temperature is 50-65 ℃, and the drying time is 4-5 hours.

Description

Preparation method of hierarchical pore indium oxide nanotube for lithium ion battery cathode Technical Field The invention relates to the technical field of battery cathode materials. In particular to a preparation method of a hierarchical pore indium oxide nanotube for a lithium ion battery cathode. Background With the rapid development of electric vehicles and various electronic products, lithium ion batteries are urgently required to have higher energy density and power density. Currently commercial graphite anodes have reached theoretical limits in terms of energy density and power density. High energy density negative electrode materials have become the focus of research for next generation lithium ion batteries. Among the negative electrode materials, transition metal compounds based on a conversion reaction mechanism have attracted considerable attention from researchers because of their high theoretical specific capacity and relatively low production cost. In 2O3 In particular has received increasing attention due to its mature preparation technology, environmental protection, low operating voltage and higher theoretical specific lithium storage capacity. However, the transformation type negative electrode material can generate huge volume change in the process of lithium removal/intercalation, so that the pole piece is crushed. And the electrode material has poor rate capability due to poor conductivity of In 2O3. Therefore, the In 2O3 anode material has the problems of poor cycle performance, poor rate performance and the like, cannot meet the requirements In practical application, and is necessary to modify the structure to improve the electrochemical performance of the In 2O3 -based anode material. Disclosure of Invention Therefore, the technical problem to be solved by the invention is to provide a preparation method of the multistage hole indium oxide nanotube for the lithium ion battery cathode, so as to solve the problems of poor cycle performance, poor rate performance and the like of the existing In 2O3 -based cathode material. In order to solve the technical problems, the invention provides the following technical scheme: The preparation method of the hierarchical pore indium oxide nanotube for the lithium ion battery cathode comprises the following steps of (1) placing indium salt and terephthalic acid in an organic solvent, and uniformly stirring to obtain a homogeneous dispersion; Continuously heating and continuously stirring the homogeneous dispersion liquid to perform hydrothermal synthesis reaction, and naturally cooling to room temperature after the reaction is finished to obtain a mixed reaction system; Step (3), carrying out suction filtration on the mixed reaction system, washing a solid product obtained by suction filtration with absolute ethyl alcohol, and drying to obtain a precursor MIL-68 (In) after the drying is finished; And (4) placing a precursor MIL-68 (In) In a tube furnace, and performing pyrolysis treatment In an air atmosphere to obtain the multistage hole indium oxide nanotube HPNT-In 2O3 for the negative electrode of the lithium ion battery after the pyrolysis treatment is finished. According to the preparation method of the hierarchical pore indium oxide nanotube for the lithium ion battery cathode, in the step (1), indium salt is indium nitrate hydrate or indium chloride hydrate, the mass ratio of the indium salt to terephthalic acid is 1:2-5, and the volume mass ratio of an organic solvent to terephthalic acid is 100-150 mL/g. In the preparation method of the multi-level hole indium oxide nanotube for the lithium ion battery cathode, in the step (1), indium salt is indium nitrate pentahydrate, the mass ratio of the indium nitrate pentahydrate to terephthalic acid is 1:3, the volume mass ratio of an organic solvent to terephthalic acid is 120mL/g, and if the mass ratio of the indium nitrate pentahydrate to terephthalic acid is too small or too large, the nucleation rate of the reaction is slow, so that the rod-shaped MIL-68 (In) size is too small or too large, and the size is too small or too large, which is not beneficial to preparing the multi-level hole indium oxide nanotube HPNT-In 2O3 with ideal electrochemical properties. In the preparation method of the hierarchical pore indium oxide nanotube for the lithium ion battery cathode, in the step (2), the homogeneous dispersion liquid is continuously heated to 115-125 ℃ and continuously stirred for 45-75 min. In the preparation method of the hierarchical pore indium oxide nanotube for the lithium ion battery cathode, in the step (2), the homogeneous dispersion liquid is continuously heated to 120 ℃ and continuously stirred for 60min. The method has the advantages that the reaction temperature is low, the nucleation rate is low or even does not nucleate, the nucleation rate is too high to cause the rod-like size of MIL-68 (In) to become large when the temperature is too high, the rod-like size of MIL-68 (In)