CN111193013A - Preparation method of silicon-carbon negative electrode material for lithium ion battery - Google Patents
Preparation method of silicon-carbon negative electrode material for lithium ion battery Download PDFInfo
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- CN111193013A CN111193013A CN202010019604.6A CN202010019604A CN111193013A CN 111193013 A CN111193013 A CN 111193013A CN 202010019604 A CN202010019604 A CN 202010019604A CN 111193013 A CN111193013 A CN 111193013A
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- 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
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- H—ELECTRICITY
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- 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
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- H—ELECTRICITY
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- 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
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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Abstract
A preparation method of a silicon-carbon negative electrode material for a lithium ion battery comprises the following steps: mixing a reducing agent and graphite powder in proportion, introducing argon to replace air, heating to 400-1100 ℃, and mixing to obtain a cathode material precursor A; and adding the precursor A into a high-temperature rotary furnace, introducing argon to remove air, setting a heating curve, heating to 900-1200 ℃ in the furnace, introducing silicon tetrachloride gas, and washing a product after the reaction by acid washing to obtain a cathode material precursor B. Mixing the precursor B with a binder, adding a conductive agent, performing secondary granulation, and obtaining a precursor C after the granulation is finished; and mixing the precursor C and an organic carbon source in a mixer in proportion, carbonizing under the protection of nitrogen, and finally performing demagnetizing, grading and screening to obtain the silicon-carbon anode material. The invention has the following advantages: the method has the advantages of simple raw materials, stable process, uniform silicon source distribution, high capacity of the obtained battery, long cycle and easy commercial application.
Description
Technical Field
The invention relates to a material for a lithium ion battery, in particular to a preparation method of a silicon-carbon cathode material for the lithium ion battery, and belongs to the technical field of lithium ion batteries.
Background
Under the background of global energy shortage and continuous deterioration of the environment, energy storage batteries are advocated to be adopted as new energy greatly in our country, and lithium ion batteries have the advantages of high energy density, long cycle life, no pollution and the like, become the most important energy storage batteries in the market and are widely applied to the fields of 3C products, energy storage power stations, electric vehicles and the like. The negative electrode material is one of the main components of the lithium ion battery, while the graphite negative electrode material is the mainstream negative electrode material in the market in these years, but the capacity of the graphite negative electrode material in the market at present is close to the upper limit of the theoretical capacity, and the demand of the lithium ion battery for high-speed development cannot be met.
Silicon itself has very high theoretical capacity (theoretical value 4200mAH/g), and is the most potential material for improving capacity of negative electrode material. However, silicon as a negative electrode material of a lithium battery has large volume expansion during charging and discharging, thereby causing the reduction of battery performance. At present, the silicon-carbon cathode composite material is prepared by compounding silicon nanocrystallization and graphite, which is the most industrialized means at present, and the volume expansion of silicon is reduced by means of the special size effect of nanoparticles. However, the dispersion of the nano-silicon is a difficult point, the dispersibility of the nano-silicon among graphite particles is poor, the nano-silicon agglomeration can cause overlarge expansion, an SEI film is repeatedly broken, and the cycle performance is reduced, so that the problem of poor dispersibility of the nano-silicon is solved by finding a technical means, and a key goal is achieved.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of a silicon-carbon cathode material for a lithium ion battery, which utilizes gas phase reaction to uniformly disperse nano silicon particles among graphite particles and overcomes the defect of poor dispersibility of nano silicon. The silicon-carbon cathode composite material prepared by the preparation method has the advantages of high capacity, small volume expansion and good cycle stability.
In order to solve the technical problems, the technical scheme provided by the invention is as follows: a preparation method of a silicon-carbon negative electrode material for a lithium ion battery comprises the following steps:
(1) reducing agent and graphite powder are mixed according to the ratio of (0.1-50): 100, placing the mixture in a high-temperature mixer for mixing, introducing argon to replace air, heating to 400-1100 ℃, mixing for 2 hours, and obtaining a precursor A of the cathode material;
(2) adding the precursor A obtained in the step (1) into a high-temperature rotary furnace, introducing argon to remove air, setting a heating curve, introducing silicon tetrachloride gas when the temperature in the furnace is increased to 900-1200 ℃, reacting with the precursor A, and washing a product after the reaction by pickling water to obtain a cathode material precursor B;
(3) mixing the precursor B in the step (2) with an organic binder, adding a conductive agent, adding into a high-temperature roller furnace for secondary granulation, and obtaining a precursor C after the granulation is finished;
(4) mixing the precursor C obtained in the step (3) with an organic carbon source solution according to the ratio of 100: and (5-20) mixing in a mixer, then feeding into a pushed slab kiln, carrying out carbonization treatment under the protection of nitrogen, and finally carrying out the processes of demagnetization, classification and screening to obtain the silicon-carbon negative electrode material.
Preferably, the reducing agent in the step (1) is one or more of zinc powder, zinc oxide, zinc hydroxide, zinc carbonate, zinc acetate, zinc oxalate and zinc sulfate powder.
Preferably, the graphite powder in the step (1) is one or a mixture of more of natural spherical graphite, natural flaky graphite, artificial graphite, microcrystalline graphite and mesocarbon microbeads.
Preferably, the graphite powder in the step (1) has a particle size range D50 of 3 μm to 10 μm.
Preferably, the acid in the step (2) is one or more of hydrochloric acid, sulfuric acid and nitric acid.
Preferably, the conductive agent in the step (3) is one or more of conductive carbon black and graphene.
Preferably, the organic binder in step (3) is one or a mixture of several of glucose, sucrose, fructose, maltose, hydroxymethyl cellulose and polyethylene glycol.
Preferably, the organic carbon source in the step (4) is one or more of asphalt, hydroxymethyl cellulose, polyethylene, polybutadiene, phenolic resin, polyacrylonitrile and the like.
Preferably, the temperature of the carbonization treatment in the step (4) is 900-.
The invention has the following advantages: the method has the advantages of simple raw materials, stable process, uniform silicon source distribution, high capacity of the obtained battery, long cycle and easy commercial application; the method comprises the steps of carrying out reduction reaction on zinc or a zinc compound after thermal decomposition under a high-temperature condition to generate a zinc simple substance, then carrying out gasification under the high temperature condition, carrying out gas phase reaction on the zinc simple substance and carbon under the constant-temperature and constant-pressure condition in an argon protective atmosphere, generating high-purity silicon which can be uniformly distributed in graphite powder, solving the defects of difficult dispersion and nonuniform dispersion of nano silicon, and relieving the expansion of the silicon through gaps among powder particles by secondary granulation.
Drawings
Fig. 1 is an electron micrograph of a silicon carbon negative electrode material for a lithium ion battery according to the present invention.
Detailed Description
Example one
A preparation method of a silicon-carbon negative electrode material for a lithium ion battery comprises the following steps:
(1) mixing zinc powder and natural spherical graphite with the particle size D50 being 6 mu m according to the proportion of 15: 100, placing the mixture in a high-temperature mixer for mixing, introducing argon to replace air, rotating at 500rpm, mixing for 2 hours, and obtaining a precursor A of the cathode material;
(2) adding the precursor A into a high-temperature rotary furnace, introducing argon to replace air, setting a temperature rise curve, introducing silicon tetrachloride gas when the temperature in the furnace rises to 1000 ℃, reacting with the precursor A, and washing a product after the reaction by hydrochloric acid pickling water to obtain a cathode material precursor B;
(3) the precursor B and glucose are mixed according to the proportion of 100: 5, mixing in a conical mixer, adding conductive carbon black, adding into a high-temperature roller furnace for secondary granulation, and obtaining a precursor C after the granulation is finished;
(4) mixing the precursor C with pitch according to the proportion of 100:10, mixing in a mixer, then sending into a pushed slab kiln, carrying out carbonization treatment at the carbonization temperature of 900-1300 ℃ under the protection of nitrogen, and finally carrying out the procedures of demagnetization, classification and screening to obtain the silicon-carbon cathode material.
Example two
A preparation method of a silicon-carbon negative electrode material for a lithium ion battery comprises the following steps:
mixing zinc carbonate powder with artificial graphite with the particle size D50 being 6 μm according to the proportion of 45: 100, placing the mixture in a high-temperature mixer for mixing, introducing argon for protection, heating to 950 ℃, rotating at 500rpm, mixing for 2 hours, and obtaining a precursor A of the cathode material;
(2) adding the precursor A into a high-temperature rotary furnace, introducing argon to remove air, setting a temperature rise curve, introducing silicon tetrachloride gas when the temperature in the furnace rises to 1000 ℃, reacting with the precursor A, and washing a product after the reaction by hydrochloric acid pickling water to obtain a cathode material precursor B;
(3) the precursor B and glucose are mixed according to the proportion of 100: 5, mixing in a conical mixer, adding conductive carbon black, adding into a high-temperature roller furnace for secondary granulation, and obtaining a precursor C after the granulation is finished;
(4) mixing the precursor C with pitch according to the proportion of 100:10, mixing in a mixer, then sending into a pushed slab kiln, carrying out carbonization treatment at the carbonization temperature of 900-1300 ℃ under the protection of nitrogen, and finally carrying out the procedures of demagnetization, classification and screening to obtain the silicon-carbon cathode material.
Comparative examples
(1) Mixing nano silanol solution with solid content of 15 wt% and particle size D50 ═ 80nm with natural spherical graphite with particle size D50 ═ 3 μm in proportion of 47: 100, adding the dispersing agent into purified water, and dispersing at a high speed in a high-speed stirrer for 2 hours to obtain a precursor A of the negative electrode material.
(2) And adding the precursor A into a spray dryer, and carrying out spray drying to obtain a precursor B.
(3) And mixing the precursor B and an organic carbon source in a mixer according to the ratio of 100:10, then feeding the mixture into a pushed slab kiln, carrying out carbonization treatment at the carbonization temperature of 900-1300 ℃ under the protection of nitrogen, and finally carrying out a demagnetizing and screening process to obtain the silicon-carbon cathode material.
Mixing the negative electrode materials (92.5 wt.%) prepared in the above examples and comparative examples with PVDF (7.5 wt.%), adding a certain amount of NMP, wherein the electrolyte is 1mol/LLIPF6/EC + DMC + EMC (mass ratio is 1: 1: 1), the diaphragm adopts Celgard2300, the soft-package battery is prepared by processes of pulping, smearing, tabletting, drying, packaging and the like, and the performance indexes such as capacity, coulomb efficiency, pole piece rebound and the like are tested by 1C charging and discharging.
The results of the examples and comparative examples are given in the table below:
| performance index | Example 1 | Example 2 | Comparative example |
| First week discharge capacity mAh/g | 654.3 | 661.9 | 617.3 |
| First week coulombic efficiency% | 90.79％ | 89.21.％ | 80.12％ |
| 48h pole piece rebound% | 1.71 | 1.79 | 4.21 |
The invention is characterized in that Zn gas and SiCl are mixed in a special device under the conditions of high temperature and inert gas4The gas reacts to generate simple substance silicon, the simple substance silicon is evenly compounded with graphite, and then secondary granulation is carried out, so that expansion space is reserved among graphite particles for silicon, the expansion of the silicon-carbon negative electrode material in a battery is reduced, and the capacity, the coulombic efficiency and the grade rebound of the silicon-carbon negative electrode material are obviously improved through the results of the embodiment and the comparative example.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention shall fall within the protection scope of the present invention.
Claims (9)
1. A preparation method of a silicon-carbon negative electrode material for a lithium ion battery is characterized by comprising the following steps:
(1) reducing agent and graphite powder are mixed according to the ratio of (0.1-50): 100, placing the mixture in a high-temperature mixer for mixing, introducing argon to replace air, heating to 400-1100 ℃, mixing for 2 hours, and obtaining a precursor A of the cathode material;
(2) adding the precursor A obtained in the step (1) into a high-temperature rotary furnace, introducing argon to remove air, setting a heating curve, introducing silicon tetrachloride gas when the temperature in the furnace is increased to 900-1200 ℃, reacting with the precursor A, and washing a product after the reaction by pickling water to obtain a cathode material precursor B;
(3) mixing the precursor B in the step (2) with an organic binder, adding a conductive agent, adding into a high-temperature roller furnace for secondary granulation, and obtaining a precursor C after the granulation is finished;
(4) mixing the precursor C obtained in the step (3) with an organic carbon source solution according to the ratio of 100: and (5-20) mixing in a mixer, then feeding into a pushed slab kiln, carrying out carbonization treatment under the protection of nitrogen, and finally carrying out the processes of demagnetization, classification and screening to obtain the silicon-carbon negative electrode material.
2. The preparation method of the silicon-carbon anode material for the lithium ion battery according to claim 1, wherein the preparation method comprises the following steps: the reducing agent in the step (1) is one or more of zinc powder, zinc oxide, zinc hydroxide, zinc carbonate, zinc acetate, zinc oxalate and zinc sulfate powder.
3. The preparation method of the silicon-carbon anode material for the lithium ion battery according to claim 1, wherein the preparation method comprises the following steps: the graphite powder in the step (1) is one or a mixture of more of natural spherical graphite, natural flaky graphite, artificial graphite, microcrystalline graphite and mesocarbon microbeads.
4. The preparation method of the silicon-carbon anode material for the lithium ion battery according to claim 1, wherein the preparation method comprises the following steps: the particle size range D50 of the graphite powder in the step (1) is 3-10 μm.
5. The preparation method of the silicon-carbon anode material for the lithium ion battery according to claim 1, wherein the preparation method comprises the following steps: the acid in the step (2) is one or more of hydrochloric acid, sulfuric acid and nitric acid.
6. The preparation method of the silicon-carbon anode material for the lithium ion battery according to claim 1, wherein the preparation method comprises the following steps: the conductive agent in the step (3) is one or more of conductive carbon black and graphene.
7. The preparation method of the silicon-carbon anode material for the lithium ion battery according to claim 1, wherein the preparation method comprises the following steps: the organic binder in the step (3) is one or a mixture of more of glucose, sucrose, fructose, maltose, hydroxymethyl cellulose and polyethylene glycol.
8. The preparation method of the silicon-carbon anode material for the lithium ion battery according to claim 1, wherein the preparation method comprises the following steps: the organic carbon source in the step (4) is one or more of asphalt, hydroxymethyl cellulose, polyethylene, polybutadiene, phenolic resin, polyacrylonitrile and the like.
9. The preparation method of the silicon-carbon anode material for the lithium ion battery according to claim 1, wherein the preparation method comprises the following steps: the temperature of the carbonization treatment in the step (4) is 900-1300 ℃.
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Cited By (2)
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| CN114050251A (en) * | 2021-11-18 | 2022-02-15 | 兰州城市学院 | Preparation and application of silicon-carbon composite micro-nano structure material |
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