US-12620580-B2 - Silicon-oxygen composite anode material, preparation method thereof and lithium-ion battery

US12620580B2US 12620580 B2US12620580 B2US 12620580B2US-12620580-B2

Abstract

The present application relates to a silicon-oxygen composite anode material and the preparation method thereof, and a lithium-ion battery. Wherein the silicon-oxygen composite anode material comprises a silicon-oxygen material and a composite coating layer coating the surface of the silicon-oxygen material. The composite coating layer comprises a carbon material and a lithium-containing compound, the carbon material has pores, and the lithium-containing compound is filled in the pores. The silicon-oxygen composite anode material and the preparation method thereof are simple and low cost, which is also easy to conduct industrial production, moreover, the prepared silicon-oxygen composite anode material has excellent electrochemical cycle and expansion inhibition performance, which can prolong the life-span of a lithium ion battery.

Inventors

Wei Xie
Chunlei Pang
Zhiqiang DENG
JIANGUO REN
Xueqin HE

Assignees

BTR NEW MATERIAL GROUP CO., LTD.
DINGYUAN NEW ENERGY TECHNOLOGY CO., LTD.

Dates

Publication Date: 20260505
Application Date: 20220310
Priority Date: 20210324

Claims (13)

1 . A silicon-oxygen composite anode material, wherein the silicon-oxygen composite anode material comprises a silicon-oxygen material and a composite coating layer coating the surface of the silicon-oxygen material, and the composite coating layer comprises a carbon material and a lithium-containing compound, the carbon material has pores, and the lithium-containing compound is filled in the pores, wherein the lithium-containing compound comprises at least one of multi-lithium phosphate, multi-lithium silicate, and multi-lithium-containing metal oxide, wherein the multi-lithium phosphate comprises Li x R y M 2 PO 4 , wherein R is at least one selected from the group consisting of Mg, V and Cr, and M is at least one selected from the group consisting of Al, Sc, Ti, Cu, Zn, Y, Mo, Nb, La and Zr, 0.3≤x≤1.2, 0.5≤y≤1.0, 0≤z≤0.2; the multi-lithium silicate comprises Li x R y M 2 SiO 4 , wherein R is at least one selected from the group consisting of Mg, V and Cr, and M is at least one selected from the group consisting of Al, Sc, Ti, Cu, Zn, Y, Mo, Nb, La and Zr, 0.8≤x≤2.2, 0.8≤y≤1.2, 0≤z≤0.2; and the multi-lithium-containing metal oxide comprises Li x R y M 2 O 2 , wherein R is at least one selected from the group consisting of Al, V and Cr, and M is at least one selected from the group consisting of Mg, Sc, Ti, Cu, Zn, Y, Mo, Nb, La and Zr, 0.3≤x≤0.7, 0.2≤y≤5, 0≤z≤0.2.
2 . The silicon-oxygen composite anode material according to claim 1 , wherein the silicon-oxygen composite anode material satisfies at least one of the following conditions a to f: a. the chemical formula of the silicon-oxygen material is SiOn, wherein 0.5≤n≤1.5; b. the average particle size of the silicon-oxygen material is 3.5 μm to 8.0 μm; c. the thickness of the composite coating layer is 1 nm to 150 nm; d. based on 100% of the mass of silicon-oxygen composite anode material, the mass amount of the lithium-containing compound accounts for 0.1% to 10.0%; e. the morphology of the lithium-containing compound comprises at least one of granular, flocculent and fibrous; and f. the average particle size of the lithium-containing compound is 1 nm to 80 nm.
3 . The silicon-oxygen composite anode material according to claim 1 , wherein the silicon-oxygen composite anode material satisfies at least one of the following conditions a to g: a. the tap density of the silicon-oxygen composite anode material is 0.7 g/cm 3 to 1.2 g/cm 3 ; b. the specific surface area of the silicon-oxygen composite anode material is 1.50 m 2 /g to 5.00 m 2 /g; c. the porosity of the silicon-oxygen composite anode material is 0.5% to 15.0%; d. the porosity of the composite coating layer is 0.5% to 15%; e. the average particle size of the silicon-oxygen composite anode material is 1.0 μm to 12.0 μm; f. the mass percentage content of carbon in the silicon-oxygen composite anode material is 3.0% to 6.0%; g. the pH of the silicon-oxygen composite anode material is 10.0 to 12.0.
4 . A silicon-oxygen composite anode material, wherein the silicon-oxygen composite anode material comprises a silicon-oxygen material and a composite coating layer coating the surface of the silicon-oxygen material, and the composite coating layer comprises a carbon material and a lithium-containing compound, the lithium-containing compound is distributed inside of the carbon material, wherein the lithium-containing compound comprises at least one of multi-lithium phosphate, multi-lithium silicate, and multi-lithium-containing metal oxide, wherein the multi-lithium phosphate comprises Li x R y M 2 PO 4 , wherein R is at least one selected from the group consisting of Mg, V and Cr, and M is at least one selected from the group consisting of Al, Sc, Ti, Cu, Zn, Y, Mo, Nb, La and Zr, 0.3≤x≤1.2, 0.5≤y≤1.0, 0≤z≤0.2; the multi-lithium silicate comprises Li x R y M 2 SiO 4 , wherein R is at least one selected from the group consisting of Mg, V and Cr, and M is at least one selected from the group consisting of Al, Sc, Ti, Cu, Zn, Y, Mo, Nb, La and Zr, 0.8≤x≤2.2, 0.8≤y≤1.2, 0≤z≤0.2; and the multi-lithium-containing metal oxide comprises Li x R y M 2 O 2 , wherein R is at least one selected from the group consisting of Al, V and Cr, and M is at least one selected from the group consisting of Mo, Sc, Ti, Cu, Zn, Y, Mo, Nb, La and Zr, 0.3≤x≤0.7, 0.2≤y≤5, 0≤z≤0.2.
5 . The silicon-oxygen composite anode material according to claim 2 , wherein the silicon-oxygen composite anode material satisfies at least one of the following conditions l to q: l. The chemical formula of the silicon-oxygen material is SiO n , wherein 0.5≤n≤1.5; m. the average particle size of the silicon-oxygen material is 3.5 μm to 8.0 μm; n. the thickness of the composite coating layer is 1 nm to 150 nm; o. based on 100% of the mass of silicon-oxygen composite anode material, the mass amount of the lithium-containing compound accounts for 0.1% to 10.0%; p. the morphology of the lithium-containing compound comprises at least one of granular, flocculent and fibrous; and q. the average particle size of the lithium-containing compound is 1 nm to 80 nm.
6 . The silicon-oxygen composite anode material according to claim 4 , wherein the silicon-oxygen composite anode material satisfies at least one of the following conditions h to n: h. the tap density of the silicon-oxygen composite anode material is 0.7 g/cm 3 to 1.2 g/cm 3 ; i. the specific surface area of the silicon-oxygen composite anode material is 1.50 m 2 /g to 5.00 m 2 /g; j. the porosity of the silicon-oxygen composite anode material is 0.5% to 15.0%; k. the porosity of the composite coating layer is 0.5% to 15%; l. the average particle size of the silicon-oxygen composite anode material is 1.0 μm to 12.0 μm; m. the mass percentage content of carbon in the silicon-oxygen composite anode material is 3.0% to 6.0%; n. the pH of the silicon-oxygen composite anode material is 10.0 to 12.0.
7 . A method for preparing a silicon-oxygen composite anode material, comprising: mixing a precursor with a pre-lithiated carbon-coated silicon-oxygen material, and carrying out a solid-phase thermal reaction in a protective atmosphere to obtain the silicon-oxygen composite anode material; wherein the precursor comprises at least one of a mixture of a phosphate containing ionic compound and a metal compound, a metal phosphates, a mixture of a silicate containing ionic compound and a metal compound, and a metal silicate; the silicon-oxygen composite anode material comprises a silicon-oxygen material and a composite coating layer formed on the surface of the silicon-oxygen material; the composite coating layer comprises a carbon material and a lithium-containing compound, the carbon material has pores, and the lithium-containing compound is filled in the pores, wherein the lithium-containing compound comprises at least one of multi-lithium phosphate, multi-lithium silicate, and multi-lithium-containing metal oxide, wherein the multi-lithium phosphate comprises Li x R y M 2 PO 4 , wherein R is at least one selected from the group consisting of Mg, V and Cr, and M is at least one selected from the group consisting of Al, Sc, Ti, Cu, Zn, Y, Mo, Nb, La and Zr, 0.3≤x≤1.2, 0.5≤y≤1.0, 0≤z≤0.2; the multi-lithium silicate comprises Li x R y M 2 SiO 4 , wherein R is at least one selected from the group consisting of Mg, V and Cr, and M is at least one selected from the group consisting of Al, Sc, Ti, Cu, Zn, Y, Mo, Nb, La and Zr, 0.8<x≤2.2, 0.8≤y≤1.2, 0≤z≤0.2; and the multi-lithium-containing metal oxide comprises Li x R y M 2 O 2 , wherein R is at least one selected from the group consisting of Al, V and Cr, and M is at least one selected from the group consisting of Mg, Sc, Ti, Cu, Zn, Y, Mo, Nb, La and Zr, 0.3≤x≤0.7, 0.2≤y≤5, 0≤z≤0.2.
8 . The method according to claim 7 , wherein the pre-lithiated carbon-coated silicon-oxygen material is obtained by the reaction of a carbon-coated silicon-oxygen material with a lithium source.
9 . The method according to claim 8 , wherein the method satisfies at least one of the following conditions a to e: a. the lithium source comprises at least one of lithium hydride, alkyl lithium, metal lithium, lithium aluminum hydride, lithium amide, and lithium borohydride; b. the reaction temperature between the carbon-coated silicon-oxygen material and the lithium source is 150° C. to 300° C.; c. the reaction time between the carbon-coated silicon-oxygen material and the lithium source is 2.0 h to 6.0 h; d. the mass ratio of the carbon-coated silicon-oxygen material to the lithium source is 1:(0.01-0.20); e. the mass percentage content of lithium in the pre-lithiated carbon-coated silicon-oxygen material is 1.0% to 20.0%.
10 . The method according to claim 8 , wherein the method also comprises coating the silicon-oxygen material with carbon to obtain the carbon-coated silicon-oxygen material.
11 . The method according to claim 10 , wherein the method satisfies at least one of the following conditions a to e: a. the chemical formula of the silicon-oxygen material is SiO n , wherein 0.5≤n≤1.5; b. the average particle size of the silicon-oxygen material is 3.5 μm to 8.0 μm; c. the thickness of the carbon coating layer on the surface of the silicon-oxygen material is 1 nm to 150 nm; d. the carbon coating comprises gas-phase carbon coating, the conditions for gas-phase carbon coating are as follows: raising the temperature of the silicon-oxygen material to 600° C. to 1000° C. under protective atmosphere, feeding organic carbon source gas, keeping the temperature for 0.5 h to 10 h and then cooling down; wherein, the organic carbon source gas comprises hydrocarbons, and the hydrocarbons comprises at least one of methane, ethylene, ethyne, and benzene; e. the carbon coating comprises solid-phase carbon coating, the conditions for solid-phase carbon coating are as follows: after 0.5 h to 2 h of the fusion of the silicon-oxygen material with a carbon source, carbonizing the obtained carbon mixture under the temperature of 600° C. to 1000° C. for 2 h to 6 h and then cooling down; wherein, the carbon source comprises at least one of polymer, saccharides, organic acid and pitch.
12 . The method according to claim 7 , wherein the method satisfies at least one of the following conditions a to i: a. the phosphate containing ionic compound is at least one selected from the group consisting of phosphoric acid, phosphate and metaphosphate; b. the silicate containing ionic compound is at least one selected from the group consisting of silicic acid, silicate and silicon dioxide; c. the metal compound comprises metal oxides and/or soluble metal salts; d. the molar ratio of the phosphate containing ionic compound to the metal compound is 1:(0.05 to 1.20); e. the molar ratio of the silicate containing ionic compound to the metal compound is 1:(0.05 to 1.20); f. the conditions for obtaining the mixture of the phosphate containing ionic compound and the metal compound or the mixture of the silicate containing ionic compound and the metal compound are as follows: controlling the mixing temperature to be 20° C. to 80° C., and the mixing time to be 3 h to 6 h; g. the conditions for obtaining the mixture of the phosphate containing ionic compound and the metal compound or the mixture of the silicate containing ionic compound and the metal compound are as follows: dispersing the mixture by at least one of ultrasonic dispersion, stirring dispersion, and wet ball-milling dispersion; h. the average particle size of the precursor particles is 1 nm to 400 nm; i. the average particle size of the precursor particles is 1 nm to 50 nm.
13 . The method according to claim 7 , wherein the method satisfies at least one of the following conditions a to l: a. the steps of mixing a precursor with the pre-lithiated carbon-coated silicon-oxygen material comprises: disperse the precursor in a solvent to form a suspension, then add the pre-lithiated carbon-coated silicon-oxygen material to the suspension, disperse adequately and remove the solvent; b. the method of dispersing adequately is wet ball-milling dispersion; c. the mass ratio of the precursor to the pre-lithiated carbon-coated silicon-oxygen material is (0.005 to 0.1):1; d. the mass ratio of the added solvent to the sum of the precursor and the pre-lithiated carbon-coated silicon-oxygen material is 0.3 to 1.0; e. the solvent comprises at least one of ethyl alcohol, acetone, dioctyl ether, hexadecane, tetraethylene glycol dimethyl ether, and trioctylamine; f. the protective atmosphere comprises at least one of nitrogen, helium, neon, argon, krypton and xenon; g. the temperature of the solid-phase thermal reaction is 500° C. to 1300° C.; h. the temperature of the solid-phase thermal reaction is 700° C. to 1050° C.; i. the time for the solid-phase thermal reaction is 0.5 h to 12 h; j. the time for the solid-phase thermal reaction is 3 h to 10 h; k. the heating rate of the solid-phase thermal reaction is 1° C./min to 5° C./min; l. The method also comprises: screening the products of the solid-phase thermal reaction, to obtain the silicon-oxygen composite anode material, wherein the screening comprises at least one of crushing, ball milling, filtering, or pneumatic classification.

Description

CROSS REFERENCE TO RELATED APPLICATIONS The present application is a U.S. National Phase of International Application No. PCT/CN2022/080087, entitled “SILICON-OXYGEN COMPOSITE NEGATIVE ELECTRODE MATERIAL, PREPARATION METHOD THEREFOR, AND LITHIUM ION BATTERY”, and filed on Mar. 10, 2022. International Application No. PCT/CN2022/080087 claims priority to Chinese Patent Application No. 202110311665.4 filed with on Mar. 24, 2021. The entire contents of each of the above-listed applications are hereby incorporated by reference for all purposes. TECHNICAL FIELD The present application relates to the field of lithium-ion battery, and to a silicon-oxygen composite anode material and the preparation method thereof, and lithium-ion battery. BACKGROUND Silicon monoxide material is an indispensable anode material in the new generation of ultra-large-capacity lithium-ion battery. The silicon monoxide industry has researched and deployed the silicon-based lithium-ion battery for more than ten years. However, silicon-based materials represented by silicon monoxide have not yet been used on a large scale. The main factor that limits the application of silicon monoxide materials is due to the natural disadvantages of silicon-based materials per se. High expansion, severe volume changes, and low initial coulombic efficiency are all problems that need to be solved urgently. The control of the interface reaction is one of the important directions to inhibit the expansion of the pole piece and extend the cyclic performance of the material. It can form a coating layer on the surface of the silicon-based material to inhibit the expansion of the pole piece. At present, there are many methods to choose and improve the coating layers. For example, a single carbon material coating is a relatively conventional coating option, since the conductive carbon can improve the conductivity of the material, and different carbon layer morphologies can also affect cyclic performance. It has been reported many times in academia that the carbon coating layer doped with some other elements, such as N, P, F, etc., can improve the conductivity of the carbon layer, and meanwhile reduce the Li ion migration energy barrier and improve the Li ion migration efficiency. Titanium dioxide is also one of the common coating materials, it improves the initial coulombic efficiency and capacity to some extent. However, the high coating cost and complex coating process limit its use, and at the same time, the performance improvement doesn't make a breakthrough. Therefore, it is still a technical problem in the field to develop a silicon-based material with excellent cyclic performance and low volumetric expansion effect, and the preparation method thereof. SUMMARY In view of the above-mentioned problems in the prior art, the purpose of the present application is to provide a silicon-oxygen composite anode material and the preparation method thereof, and a lithium-ion battery. The silicon-oxygen composite anode material of the present application has excellent electrochemical cycling and swelling inhibition performance, which can extend the life-span of lithium-ion batteries and reduce production costs. In order to achieve the above-mentioned purpose of the present application, in a first aspect, the present application provides a silicon-oxygen composite anode material. The silicon-oxygen composite anode material comprises a silicon-oxygen material and a composite coating layer coating the surface of the silicon-oxygen material. The composite coating layer comprises a carbon material and a lithium-containing compound. The carbon material has pores, and the lithium-containing compound is filled in the pores. In the above solution, the composite coating layer has a certain mechanical strength, which can ensure the integrity of the particles during lithium de-intercalation and intercalation of active silicon, inhibit particle pulverization, improve the stability of the silicon oxide material, and improve the overall cyclic performance of the finished battery. On the other hand, the lithium-containing compound in the composite coating layer isolates the silicon-oxygen material from direct contact with the electrolyte, so as to control the occurrence of additional side reactions between the electrolyte and the silicon-oxygen material. Finally, the composite coating layer ensures good electrical conductivity, which can greatly improve the ability of active silicon oxide to obtain electrons, improve the efficiency of lithium de-intercalation and intercalation of the silicon oxide material, and promote the capacity utilization and the deep lithium intercalation. The present application also provides a silicon-oxygen composite anode material. The silicon-oxygen composite anode material comprises a silicon-oxygen material and a composite coating layer coating the surface of the silicon-oxygen material. The composite coating layer comprises a carbon material and a lithium-co