CN112467112A - Preparation method of lithium ion battery negative electrode material - Google Patents

Preparation method of lithium ion battery negative electrode material Download PDF

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Publication number
CN112467112A
CN112467112A CN202011381418.3A CN202011381418A CN112467112A CN 112467112 A CN112467112 A CN 112467112A CN 202011381418 A CN202011381418 A CN 202011381418A CN 112467112 A CN112467112 A CN 112467112A
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China
Prior art keywords
graphite
silicon
lithium ion
ion battery
composite material
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CN202011381418.3A
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Chinese (zh)
Inventor
崔大祥
李天昊
李梦飞
刘鹏飞
周霖
葛美英
张芳
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Shanghai National Engineering Research Center for Nanotechnology Co Ltd
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Shanghai National Engineering Research Center for Nanotechnology Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention provides a preparation method of a silicon/graphite/carbon lithium ion battery cathode material, which takes commercial micron-sized silicon powder and graphite as raw materials, utilizes a ball milling method to crush and mix the silicon and the graphite, prepares a silicon/graphite/pyrolytic carbon composite material after mass ratio through a pyrolysis method, and can effectively improve the conductivity of the electrode material. The preparation process is simple and easy to operate.

Description

Preparation method of lithium ion battery negative electrode material
Technical Field
The invention designs a preparation method of a lithium ion battery cathode material.
Background
Lithium ion batteries are widely used in various fields due to their outstanding advantages of high energy density, excellent cycle life, high operating voltage, low self-discharge rate, environmental friendliness, etc. Graphite cathode materials are the main cathode materials used by commercial lithium ion batteries at present, and can not meet the requirements of next generation high specific energy lithium ion batteries. Therefore, it is a hot spot to find a negative electrode material with an ultra-high lithium storage capacity to replace graphite-based materials.
At present, most reports use the center of gravity for researching nano silicon-carbon composite materials with good cycle performance, but the nano materials have low stacking density, and the huge specific surface area causes more irreversible side reactions, thereby causing low first efficiency and limiting the practical application of the nano silicon-carbon composite materials.
Compared with the nanometer material, the micron material has higher tap density, and the silicon-carbon composite material with micron level high performance is an urgent need for the recent industrialization of the silicon-based material.
According to the invention, micron-sized commercial silicon powder is used as a silicon source, a preparation method of the silicon-carbon composite material capable of meeting the industrial requirement is developed, and the micron-sized silicon-carbon composite material with excellent electrochemical performance is obtained.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a preparation method of a lithium ion battery cathode material, namely a Si/G/C composite material with a specific mass ratio.
The purpose of the invention is realized by the following scheme: a preparation method of a lithium ion battery cathode material is a composite material of a sintered Si/graphite/carbon mixture and silicon monoxide, wherein the weight ratio of silicon/graphite/carbon: the mass ratio of the silicon monoxide is 17:83, and the method comprises the following steps:
(1) according to the mass ratio of 1: (2-3.5) commercially using 200-mesh silicon powder and graphite materials as raw materials, and ball-milling for 80h at the rotating speed of 275 r/min;
(2) adding the obtained silicon/graphite composite material to 1, 4-butylene oxide (C) dissolved with a certain amount of asphalt4H8O) solution, continuously stirring to uniformly mix;
(3) obtaining a solid mixture after the 1, 4-epoxybutane is completely volatilized, and pyrolyzing the material in a tube furnace at 900 ℃ for 3 hours in an argon atmosphere;
(4) and (3) after the tubular furnace is cooled to room temperature, crushing and sieving the material to obtain a silicon/graphite/pyrolytic carbon composite material (Si/G/C), and mechanically mixing the silicon/graphite/pyrolytic carbon composite material with the silicon monoxide to the ratio to obtain the final product, namely the lithium ion battery cathode material.
The used silicon powder is 200-mesh micron-sized silicon powder, and the particle size distribution is about 80 mu m.
The solvent used was a solution of 1, 4-butylene oxide containing bitumen.
The silicon/graphite/pyrolytic carbon composite material with a proper mass ratio is prepared by a pyrolysis method, and the conductivity of the electrode material can be effectively improved. The preparation process is simple and easy to operate.
Drawings
FIG. 1 is an SEM image of a negative electrode plate made of a Si/G/C composite material.
Detailed Description
Example 1:
a lithium ion battery cathode material is a composite material obtained by sintering a Si/graphite/carbon mixture and silicon monoxide, wherein the weight ratio of silicon/graphite/carbon: the mass ratio of the silicon monoxide is 17:83, and the preparation method comprises the following steps:
(1) 5g of commercial 200-mesh silicon powder and 15g of graphite are used as raw materials, and ball milling is carried out for 80 hours at the rotating speed of 275 r/min;
(2) adding the obtained silicon/graphite composite material to 1, 4-butylene oxide (C) dissolved with a certain amount of asphalt4H8O) solution, continuously stirring to uniformly mix;
(3) obtaining a solid mixture after the 1, 4-epoxybutane is completely volatilized, and pyrolyzing the material in a tube furnace at 900 ℃ for 3 hours in an argon atmosphere;
(4) and (3) cooling the material to room temperature by using a tube furnace, crushing the material, sieving the crushed material by using a 100-mesh sieve to obtain a silicon/graphite/pyrolytic carbon composite material (Si/G/C), and mechanically mixing 17G of Si/G/C and 83G of silicon monoxide in the material to obtain the final product, namely the lithium ion battery cathode material. FIG. 1 is an SEM image of a negative pole piece made of a Si/G/C composite material, and it can be seen from the SEM image that the obtained sample has good dispersibility, and the prepared negative pole piece film has good compactness, and can prevent the performance reduction or failure of the battery caused by the cracking of the pole piece.
The beneficial effects of the material obtained by the embodiment are as follows: 17% silicon/graphite/pyrolytic carbon: 83% silica exhibits a first coulombic efficiency of 84.9% and 458.1 mAh g-1The capacity and 300-cycle capacity retention rate is 95.2%, and good industrial application prospects are shown.
Example 2:
a lithium ion battery cathode material is similar to that in example 1, except that the mixing ratio of silicon powder and graphite is different, and the lithium ion battery cathode material is prepared by the following steps:
(1) taking 0.3g of commercial 200-mesh silicon powder and 0.75g of graphite as raw materials, and carrying out ball milling for 80h at the rotating speed of 275 r/min;
(2) adding the obtained silicon/graphite composite material to 1, 4-butylene oxide (C) dissolved with a certain amount of asphalt4H8O) solution, continuously stirring to uniformly mix;
(3) obtaining a solid mixture after the 1, 4-epoxybutane is completely volatilized, and pyrolyzing the material in a tube furnace at 900 ℃ for 3 hours in an argon atmosphere;
(4) and (3) after the tubular furnace is cooled to room temperature, crushing and sieving the material to obtain a silicon/graphite/pyrolytic carbon composite material (Si/G/C), and mechanically mixing 1.7G of Si/G/C and 8.3G of silicon monoxide to the ratio to obtain the final product, namely the lithium ion battery cathode material.
The beneficial effects of the material obtained by the embodiment are as follows: 83% of silica exhibits a first coulombic efficiency of 84.9% and 458.1 mAh g-1The capacity and 300-cycle capacity retention rate is 95.2%, and good industrial application prospects are shown.
The embodiments described above are described to facilitate an understanding and appreciation of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the embodiments described herein, and those skilled in the art should make improvements and modifications to the present invention based on the disclosure of the present invention within the protection scope of the present invention.

Claims (4)

1. A preparation method of a lithium ion battery cathode material is characterized in that the lithium ion battery cathode material is a composite material obtained by sintering a Si/graphite/carbon mixture and silicon monoxide, and the preparation method is characterized in that the Si/graphite/carbon: the mass ratio of the silicon monoxide is 17:83, and the method comprises the following steps:
(1) according to the mass ratio of 1: (2-3.5) commercially using 200-mesh silicon powder and graphite materials as raw materials, and ball-milling for 80h at the rotating speed of 275 r/min;
(2) adding the obtained silicon/graphite composite material to 1, 4-butylene oxide (C) dissolved with a certain amount of asphalt4H8O) solution, continuously stirring to uniformly mix;
(3) obtaining a solid mixture after the 1, 4-epoxybutane is completely volatilized, and pyrolyzing the material in a tube furnace at 900 ℃ for 3 hours in an argon atmosphere;
(4) and (3) after the tubular furnace is cooled to room temperature, crushing and sieving the material to obtain a silicon/graphite/pyrolytic carbon composite material (Si/G/C), and mechanically mixing the silicon/graphite/pyrolytic carbon composite material with the silicon monoxide to the ratio to obtain the final product, namely the lithium ion battery cathode material.
2. The preparation method of the lithium ion battery anode material according to claim 1, characterized by comprising the following steps: the particle size distribution of 200-mesh silicon powder is 80 μm.
3. The method for preparing the negative electrode material of the lithium ion battery according to claim 1 or 2, wherein: the preparation method comprises the following steps:
(1) 5g of commercial 200-mesh silicon powder and 15g of graphite are used as raw materials, and ball milling is carried out for 80 hours at the rotating speed of 275 r/min;
(2) adding the obtained silicon/graphite composite material to 1, 4-butylene oxide (C) dissolved with a certain amount of asphalt4H8O) solution, continuously stirring to uniformly mix;
(3) obtaining a solid mixture after the 1, 4-epoxybutane is completely volatilized, and pyrolyzing the material in a tube furnace at 900 ℃ for 3 hours in an argon atmosphere;
(4) and (3) cooling the material to room temperature by using a tube furnace, crushing the material, sieving the crushed material by using a 100-mesh sieve to obtain a silicon/graphite/pyrolytic carbon composite material (Si/G/C), and mechanically mixing 17G of Si/G/C and 83G of silicon monoxide in the material to obtain the final product, namely the lithium ion battery cathode material.
4. The method for preparing the negative electrode material of the lithium ion battery according to claim 1 or 2, wherein: the preparation method comprises the following steps:
(1) taking 0.3g of commercial 200-mesh silicon powder and 0.75g of graphite as raw materials, and carrying out ball milling for 80h at the rotating speed of 275 r/min;
(2) adding the obtained silicon/graphite composite material to 1, 4-butylene oxide (C) dissolved with a certain amount of asphalt4H8O) solution, continuously stirring to uniformly mix;
(3) obtaining a solid mixture after the 1, 4-epoxybutane is completely volatilized, and pyrolyzing the material in a tube furnace at 900 ℃ for 3 hours in an argon atmosphere;
(4) and (3) after the tubular furnace is cooled to room temperature, crushing and sieving the material to obtain a silicon/graphite/pyrolytic carbon composite material (Si/G/C), and mechanically mixing 1.7G of Si/G/C and 8.3G of silicon monoxide to the ratio to obtain the final product, namely the lithium ion battery cathode material.
CN202011381418.3A 2020-12-01 2020-12-01 Preparation method of lithium ion battery negative electrode material Pending CN112467112A (en)

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