CN114975962A - Method for preparing silicon-carbon cathode material by using photovoltaic waste silicon powder and graphene oxide - Google Patents
Method for preparing silicon-carbon cathode material by using photovoltaic waste silicon powder and graphene oxide Download PDFInfo
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- CN114975962A CN114975962A CN202210729550.1A CN202210729550A CN114975962A CN 114975962 A CN114975962 A CN 114975962A CN 202210729550 A CN202210729550 A CN 202210729550A CN 114975962 A CN114975962 A CN 114975962A
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- graphene oxide
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Images
Classifications
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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
- H01M4/364—Composites as mixtures
-
- 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
- H01M4/58—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
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- 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 discloses a method for preparing a silicon-carbon cathode material by utilizing photovoltaic waste silicon powder and graphene oxide, wherein the photovoltaic waste silicon powder is subjected to acid washing, ethanol washing and drying, then ball-milled and refined in the presence of a dispersing agent and a grinding aid, and then the graphene oxide, a linking agent and a coating agent are added for ball-milling reaction to form composite slurry; then the composite slurry is sequentially subjected to spray drying, carbonization, hydrofluoric acid soaking, cleaning and drying to obtain the eggshell structure silicon-carbon composite particles; and finally, mixing the shell-structured silicon-carbon composite particles with asphalt and graphite, and then carbonizing to obtain the multi-carbon-coated silicon-carbon negative electrode material. The silicon-carbon cathode material prepared by the method has higher reversible capacity and more stable cycle performance, and is beneficial to practical production and application.
Description
Technical Field
The invention relates to the technical field of silicon-carbon cathode materials. In particular to a method for preparing a silicon-carbon cathode material by utilizing photovoltaic waste silicon powder and graphene oxide.
Background
Along with the continuous consumption of non-renewable energy sources such as coal, petroleum and the like in the world, the problems of energy crisis and environmental pollution are increasingly aggravated; with the continuous and deep research on the storage and utilization technology of clean, renewable and sustainable energy sources and the continuous expansion of the industrial application scale, the development trend in the field of photovoltaic solar energy industry is more rapid in recent years. At present, the productivity of silicon materials and crystalline silicon rises year by year to reach 60 ten thousand tons, the productivity is likely to break through 100 ten thousand tons in the future, crystalline silicon is about 40 percent lost in the production of crushing, single crystal pulling preparation, linear cutting and the like, the waste silicon powder can not be directly recycled, larger particles are recycled and reused in the metallurgical industry after acid washing and purification, and the recycling value of fine silicon powder is not high.
In the field of energy storage, lithium ion batteries have been widely used due to their advantages of high capacity, long cycle life, good safety performance, etc. With the continuous progress of science and technology, the performance of the lithium ion battery has higher requirements, and particularly in the application aspect of hybrid electric vehicles and pure electric vehicles, the battery is required to have the characteristics of high energy density, small weight and volume, long service life, low cost, wide working temperature range and short charging time. The current commercialized lithium ion battery cathode material is mainly graphite material, the theoretical capacity of which is 372mAh/g, and the requirement of high capacity cannot be met. The theoretical capacity of silicon is 4200mAh/g, and the lithium insertion voltage is lower than 0.5V, the silicon material is the preferable negative electrode material of the power battery, and a large amount of waste silicon powder in the photovoltaic industry is one of the potential silicon sources of the silicon-carbon negative electrode material; however, silicon itself has poor conductivity, and when lithium is inserted and removed during battery cycling, large volume expansion (the volume is increased by 300% after lithium insertion) is generated to cause material fragmentation, a stable SEI film cannot be formed, and finally, the conductive material and a current collector fall off, so that the cycling performance of the electrode is rapidly reduced. Chinese patent CN 110474032B utilizes photovoltaic waste silicon powder as a silicon source, although an organic carbon source is introduced in the sanding process, and a carbon coating layer is formed on the surface of the silicon particle by high-temperature pyrolysis, the problem of volume expansion of the silicon particle during lithium intercalation cannot be solved fundamentally, and the stability of long-time circulation of the silicon-carbon negative electrode material cannot be realized, which is limited in practical application.
Disclosure of Invention
Therefore, the technical problem to be solved by the present invention is to provide a method for preparing a silicon-carbon negative electrode material by using photovoltaic waste silicon powder and graphene oxide, so as to solve the problem that when the photovoltaic waste silicon powder is used for preparing the silicon-carbon negative electrode material, the silicon-carbon negative electrode material has poor long-time cycle stability due to the fact that volume expansion is likely to occur when lithium is embedded in silicon particles.
In order to solve the technical problems, the invention provides the following technical scheme:
the method for preparing the silicon-carbon cathode material by utilizing the photovoltaic waste silicon powder and the graphene oxide comprises the following steps:
(1) pretreatment: carrying out acid washing and alcohol washing on the photovoltaic waste silicon powder in sequence to remove impurities in the photovoltaic waste silicon powder and obtain purified photovoltaic waste silicon powder;
(2) ball milling and refining: adding a dispersing agent and a grinding aid into the purified photovoltaic waste silicon powder, then carrying out ball milling to refine photovoltaic waste silicon powder particles and convert the refined photovoltaic waste silicon powder particles into nano silicon particles, and obtaining nano silicon dispersion liquid after the ball milling is finished;
(3) ball-milling reaction: adding graphene oxide, a linking agent and a coating agent into the nano-silicon dispersion liquid, supplementing a grinding aid, and then carrying out a ball milling reaction to obtain a composite slurry after the ball milling reaction is finished;
(4) spray drying: adding a solvent into the composite slurry for dilution, stirring, and uniformly stirring to obtain diluted composite slurry liquid; spray drying the diluted composite slurry liquid to obtain precursor composite particles after the spray drying is finished;
(5) sintering and carbonizing: putting the precursor composite particles into a high-temperature furnace, and sintering and carbonizing under the protection of inert atmosphere to obtain silicon-carbon composite particles after sintering and carbonizing;
(6) acid leaching reaction: placing the silicon-carbon composite particles in acid liquor for acid leaching reaction, washing the silicon-carbon composite particles with deionized water after the acid leaching reaction is finished until the supernatant is neutral, and then drying the silicon-carbon composite particles to obtain the silicon-carbon composite particles with the eggshell structure;
(7) and (3) post-treatment: and mixing the shell-structured silicon-carbon composite particles, asphalt and graphite, and then carrying out carbonization treatment to obtain the multi-carbon-coated silicon-carbon negative electrode material after carbonization.
In the method for preparing the silicon-carbon negative electrode material by using the photovoltaic waste silicon powder and the graphene oxide, in the step (1), the acid solution used in the acid washing is an aqueous solution of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, citric acid or acetic acid; the mass fraction of the hyaluronic acid in the acid solution is 5-30 wt%; the alcohol solution used in the alcohol washing is absolute ethyl alcohol; during pretreatment, the photovoltaic waste silicon powder is placed in an acid solution and stirred to react for 2-8 hours at the temperature of 25-80 ℃ for acid washing, the acid washing is finished, then the filtration is carried out, deionized water is used for washing the product to be neutral, and then absolute ethyl alcohol is used for washing the product for 1-3 times and then the product is dried;
in the step (1), the photovoltaic waste silicon powder is polycrystalline and/or monocrystalline waste silicon powder generated by crushing and cutting in the production process of the photovoltaic industry; the mass fraction of silicon in the photovoltaic waste silicon powder is greater than or equal to 96 wt%; the median particle size D50 of the photovoltaic waste silicon powder is less than or equal to 100 microns, if the median particle size of the photovoltaic waste silicon powder is greater than 100 microns, a pulverizer is required to crush and screen the photovoltaic waste silicon powder, otherwise, the follow-up ball milling is not facilitated.
In the method for preparing the silicon-carbon cathode material by using the photovoltaic waste silicon powder and the graphene oxide, in the step (2), the dispersing agent is one or a mixture of two or more of cetyl trimethyl ammonium bromide, sodium lignosulfonate, sodium dodecyl benzene sulfonate, fatty alcohol-polyoxyethylene ether, dodecyl trimethyl ammonium bromide and ethyl phenyl polyethylene glycol;
in the step (2), the grinding aid is one or a mixture of two or more of deionized water, ethanol, methanol, propanol, N-methylpyrrolidone and isopropanol;
in the step (2), the mass ratio of the photovoltaic waste silicon powder to the dispersing agent to the grinding aid is 20-25: 0.1-0.5: 70-100 parts; the ball milling speed is 200-1000 rpm during ball milling refinement, and the ball milling time is 8-30 h; the particle size of the photovoltaic waste silicon powder in the nano silicon dispersion liquid is 10-1000 nm, and preferably, the particle size of the photovoltaic waste silicon powder in the nano silicon dispersion liquid is 10-200 nm; if the particle size of the photovoltaic waste silicon powder in the nano silicon dispersion liquid is too large, the prepared carbon silicon negative electrode material has poor battery cycle stability and low capacity retention rate when used for manufacturing a battery.
According to the method for preparing the silicon-carbon negative electrode material by using the photovoltaic waste silicon powder and the graphene oxide, the mass ratio of the adding amount of the grinding aid in the step (3) to the adding amount of the grinding aid in the step (2) is 2-4: 1;
in the step (3), the mass ratio of the graphene oxide to the nano silicon in the dispersion liquid is 1: 1-1: 20; the mass ratio of the linking agent to the nano-silicon in the dispersion liquid is 1:10 to 1: 50; the mass ratio of the coating agent to the nano-silicon in the dispersion liquid is 3:10 to 1: 1; the cost is high and the compacted density is low due to excessive addition of the graphene oxide, but if the addition of the graphene oxide is too low, the battery prepared from the carbon-silicon negative electrode material has poor cycle performance; while too much addition of the linking agent results in formation of more hard carbon and reduction of battery capacity, if too little addition of the linking agent affects coating stability, so that the silicon-carbon negative electrode material is loose and is not favorable for battery cycling stability. Therefore, the addition amounts of the graphene oxide, the linking agent and the coating agent are reasonably controlled, so that the prepared silicon-carbon negative electrode material is good in coating property, the compacted density and the hard carbon content are moderate, and the prepared battery not only has good circulation stability, but also is high in capacity.
In the step (3), the graphene oxide is a single-layer or multi-layer graphene oxide prepared from natural crystalline flake graphite by a Hummers process (the performance of a silicon-carbon negative electrode material prepared from the single-layer graphene oxide is superior to that of the multi-layer graphene oxide, but the cost of the silicon-carbon negative electrode material is higher), and the median diameter D50 of the graphene oxide is less than or equal to 10 μm; if the sheet diameter of the graphene oxide is too large, the graphene oxide is not beneficial to spray balling, and if the sheet diameter is small, the graphene oxide is beneficial to dispersion and coating;
in the step (3), the linking agent is one or a mixture of two or more of lithium hydroxide, lithium carbonate, citric acid, phthalic anhydride, phosphorus pentoxide, boron oxide, gamma-aminopropyltriethoxysilane and tetraethoxysilane;
in the step (3), the coating agent is one or a mixture of two or more of glucose, sucrose, chitosan, phenolic resin, epoxy resin, coumarone resin, polyvinylpyrrolidone, sodium carboxymethylcellulose and polyacrylic acid; during the ball milling reaction, the ball milling speed is 200-600 rpm, and the ball milling reaction time is 6-10 h;
in the step (4), the solvent for dilution is absolute ethyl alcohol and/or deionized water; the stirring speed is 500-1000 rpm, and the stirring time is 1-2 h; the solid content of the diluted composite slurry liquid is 1-20 wt%, and the optimal solid content is 5-10 wt%; the air inlet temperature of spray drying is 115-135 ℃, and the air outlet temperature is 90-100 ℃; when the solid content in the diluted composite slurry liquid is within the range of 5-10 wt%, the spraying effect is best under the spraying condition.
According to the method for preparing the silicon-carbon cathode material by using the photovoltaic waste silicon powder and the graphene oxide, in the step (5), the inert atmosphere protective gas is one or more than two of nitrogen, argon or hydrogen in the non-oxidizing gas; part of hydrogen is used as inert atmosphere protective gas to mainly reduce carboxyl, hydroxyl and aldehyde groups on the graphene oxide, and simultaneously, the content of oxygen in materials is reduced to improve the first coulombic efficiency of the battery; the high-temperature furnace is a roller furnace, a rotary furnace or a tubular furnace; the sintering carbonization temperature is 200-1000 ℃, the preferred temperature range is 850-950 ℃, and the time is 3-12 h. If the sintering carbonization temperature is too low or the carbonization time is not enough, the carbonization of organic matters is incomplete, the oxygen content is high, the conductivity and the first coulombic efficiency of the battery are influenced, and if the sintering carbonization temperature exceeds 1000 ℃ or the carbonization time is too long, silicon carbide without battery activity is generated, so that the performance of the silicon-carbon negative electrode material is influenced.
According to the method for preparing the silicon-carbon cathode material by using the photovoltaic waste silicon powder and the graphene oxide, during sintering carbonization, the temperature is firstly increased from room temperature to 300 ℃ at a speed of 2 ℃/min and is kept for 2h, then the temperature is increased to 950 ℃ at a speed of 3 ℃/min and is kept for 4h, then the heating and cooling are stopped to the room temperature, and the sintering carbonization is finished. The sintering mode of gradual temperature rise carbonization is easy to form a regular and stable carbon coating layer in the silicon-carbon composite particles, and is beneficial to improving the stability of the cycle performance of the battery.
According to the method for preparing the silicon-carbon cathode material by using the photovoltaic waste silicon powder and the graphene oxide, in the step (6), an acid solution used in an acid leaching reaction is a hydrofluoric acid solution, and the mass fraction of hydrofluoric acid in the hydrofluoric acid solution is 2-30 wt%, preferably 5-10 wt%; if the concentration of the hydrofluoric acid solution is too low, the generated silicon dioxide cannot be completely removed, so that the conductivity and the first coulombic efficiency of the battery are affected; if the concentration of the hydrofluoric acid is higher than 30 wt%, the hydrofluoric acid has strong volatility and has safety risk when being used; the time of the acid leaching reaction is 5-20 h, and the temperature is 20-80 ℃; under the acid leaching reaction condition, the generation of silicon carbide can be effectively avoided, and silicon dioxide can be thoroughly removed; during acid leaching, the mass-volume ratio of the silicon-carbon composite particles to the acid liquor is 0.03-0.25 g/mL; under the condition of the feed liquid ratio, the complete removal of silicon dioxide is most facilitated in the process of acid leaching reaction; the drying temperature is 50-110 ℃, and the drying time is 30-240 min; too short a drying time may result in incomplete drying, which may increase the risk of contamination of the battery material if the drying time course is carried out;
in the step (7), 5-50 parts by weight of the shell-structured silicon-carbon composite particles, 2-30 parts by weight of asphalt and 20-90 parts by weight of graphite are mixed, and during mixing, tetrahydrofuran is used as a solvent for stirring and ball milling mixing, and a fusion machine or a VC mixer is used for mixing; the excessive addition of asphalt can affect the capacity of the battery and reduce the first coulombic efficiency, and the insufficient addition of asphalt is not beneficial to the cycling stability of the battery; if the addition amount of the graphite is too small, the cycling stability of the battery is influenced, and if the addition amount of the graphite is too large, the capacity of the battery is influenced; the addition amount of the shell-structured silicon-carbon composite particles is too much, so that the cycling stability of the battery is affected, and the increase range of the battery capacity is not obvious if the addition amount of the shell-structured silicon-carbon composite particles is too little, so that the proportion of the shell-structured silicon-carbon composite particles, the shell-structured silicon-carbon composite particles and the battery capacity is reasonably controlled, the prepared silicon-carbon negative electrode material has higher battery capacity and first coulombic efficiency, and good battery cycling stability is achieved.
In the step (7), the graphite is one or a mixture of two or more of artificial graphite, microcrystalline graphite, spherical graphite, expanded graphite and mesocarbon microbeads.
The method for preparing the silicon-carbon cathode material by using the photovoltaic waste silicon powder and the graphene oxide comprises the specific operation method in the step (7) as follows:
step (7-1): adding tetrahydrofuran into a mixture of the eggshell structure silicon-carbon composite particles, the asphalt and the graphite to obtain a mixed feed liquid;
step (7-2): placing the mixed material liquid on a planetary ball mill for ball milling, and drying after the ball milling is finished to obtain a mixed raw material;
step (7-3): and (3) placing the mixed raw materials in a tubular furnace, carrying out carbonization treatment under the protection of argon, and grinding, crushing and sieving the carbonized product to obtain the multi-carbon coated silicon-carbon negative electrode material.
According to the method for preparing the silicon-carbon cathode material by using the photovoltaic waste silicon powder and the graphene oxide, in the step (7-1), the mass fraction of tetrahydrofuran in the mixed material liquid is 15-50 wt%;
in the step (7-2), the ball milling speed of the planetary ball mill is 200-400 rpm, and the ball milling time is 1-4 h; the drying temperature is 60-105 ℃, and the drying time is 60-300 min;
in the step (7-3), during carbonization treatment, firstly heating to 200-500 ℃ at 3 ℃/min for 1-4 h, then heating to 700-1000 ℃ at 5 ℃/min for 2-8 h, and finally stopping heating and cooling to room temperature; and finally grinding and crushing the carbonized product and sieving the crushed product by a 325-mesh sieve.
According to the method for preparing the lithium ion silicon carbon cathode material by using the photovoltaic waste silicon powder and the graphene oxide, the photovoltaic waste silicon powder is subjected to acid washing and ethanol impurity removal, and then is subjected to ball milling under the auxiliary action of a dispersing agent and a grinding agent, so that the photovoltaic waste silicon powder reaches a certain particle size, and meanwhile, the surface of silicon particles contains a large amount of hydroxyl groups under the particle size; then adding a linking agent, graphene oxide, a coating agent and the like to perform a high-energy ball-milling composite reaction; carrying out spray drying on the composite slurry after the ball milling reaction to obtain precursor composite particles; the precursor composite particles are subjected to high-temperature curing bonding reaction under the protection of inert gas, silicon dioxide on the surfaces of the silicon particles is removed by washing with hydrofluoric acid to obtain core silicon particles, silicon-carbon composite particles with gaps in the middle and an amorphous hard carbon eggshell structure coated with graphene and outer layers are obtained, the silicon-carbon composite particles, asphalt and graphite are subjected to secondary mixing coating and high-temperature carbonization to obtain a silicon-carbon negative electrode material, and the silicon-carbon negative electrode material has high reversible capacity and stable cycle performance and is beneficial to practical production and application.
The technical scheme of the invention achieves the following beneficial technical effects:
1. the photovoltaic waste silicon powder produced in the photovoltaic industry is used as a raw material, is subjected to acid cleaning purification and ball milling refinement and then is used as a silicon source, is used for preparing the silicon-carbon cathode material, improves the recycling value of the photovoltaic waste silicon powder, and has great cost advantage compared with the manufacturing cost of other silicon sources.
2. According to the invention, the silicon particles and the graphene oxide are firmly connected together through chemical bonds or electrostatic adsorption by using a linking agent through a high-energy ball milling method and a spray drying method, so that the silicon particles are uniformly dispersed in a lamellar coating structure of the graphene oxide. And then the silicon dioxide layer on the surface of the silicon particles is removed through hydrofluoric acid after the silicon particles are carbonized, a gap is formed between carbon and silicon, the problem that the silicon carbon cathode material is poor in long-time circulation stability due to the fact that the silicon particles are prone to volume expansion when lithium is embedded is solved, the reversible capacity and the circulation stability of the silicon carbon cathode are improved, and practical production is facilitated.
3. According to the invention, the graphene oxide is introduced during ball-milling coating of the silicon particles, and the graphene oxide is reduced into graphene during high-temperature carbonization, so that the conductivity of the silicon-carbon negative electrode material is improved. The high molecular polymer or the saccharides are used as the coating agent, so that the defect of insufficient graphene coating performance is overcome, silicon particles are prevented from being directly exposed in the electrolyte, a stable SEI (solid electrolyte interphase) film is favorably formed, and the reversible capacity and the cycling stability of the silicon-carbon negative electrode material are favorably improved.
4. According to the invention, the silicon-carbon composite particles are further compounded with asphalt and graphite to form a multi-carbon coating structure, so that the specific surface area of the silicon-carbon composite material is reduced, the density is improved, and the silicon-carbon composite material is more beneficial to the practical production and application of the material in lithium ion batteries.
5. According to the invention, photovoltaic waste silicon powder is used as a raw material, and the photovoltaic waste silicon powder is refined and purified, so that the utilization value of the waste silicon powder can be improved, and the production cost of the silicon-carbon cathode material is reduced; linking silicon particles in the graphene oxide sheet layer by using a linking agent, further coating by using a coating agent, then calcining at high temperature and cleaning by using hydrofluoric acid to obtain an amorphous carbon/graphene-coated silicon-carbon composite material with an egg shell structure, and then compounding the amorphous carbon/graphene-coated silicon-carbon composite material with asphalt and graphite to obtain a silicon-carbon cathode material, so that the cycling stability of the silicon-carbon cathode material is effectively improved, and the production and application are facilitated.
6. The silicon-carbon cathode material prepared by the method is structurally composed of silicon particles, a coating inner layer and a coating outer layer from inside to outside in sequence, gaps generated by hydrofluoric acid corrosion of silicon dioxide are formed between the silicon particles and the coating inner layer, the coating inner layer is composed of graphene obtained after high-temperature reduction of graphene oxide and amorphous carbon obtained after pyrolysis of organic matters, and the coating outer layer is a carbon coating layer generated by pyrolysis of graphite and asphalt. The silicon particles are products of photovoltaic waste silicon powder which is purified through acid washing and alcohol washing and refined in particle size, the particle size range is 10-1000 nm, the content of silicon in the silicon-carbon negative electrode material is 2-20 wt%, the content of organic pyrolytic carbon is 10-50 wt%, the content of graphene is 1-10 wt%, and the content of graphite is 20-90 wt%.
Drawings
FIG. 1 is a scanning electron microscope photograph of a silicon-carbon negative electrode material prepared in example 1 of the present invention;
FIG. 2 shows the capacity change of 100 charge/discharge cycles under the current density of 100mA/g for the Si-C negative electrode material prepared in example 1 of the present invention;
FIG. 3 is a scanning electron micrograph of a silicon carbon negative electrode material prepared according to comparative example 1 of the present invention;
FIG. 4 shows the capacity change of the Si-C negative electrode material prepared in comparative example 1 of the present invention after 100 charge/discharge cycles at a current density of 100 mA/g.
Detailed Description
Example 1
In this embodiment, the method for preparing the silicon-carbon negative electrode material by using the photovoltaic waste silicon powder and the graphene oxide includes the following steps:
(1) pretreatment: the photovoltaic waste silicon powder with the particle size D50 being 50 mu m and the silicon content being 98.5 wt% is sequentially subjected to acid washing and alcohol washing to remove impurities in the photovoltaic waste silicon powder; the acid solution used in the acid washing is 10 wt% HCl and 3 wt% HNO 3 According to the volume ratio of 1:1 in a certain proportion; during acid washing, the photovoltaic waste silicon powder is placed in an acid solution and stirred and reacts for 8 hours at the temperature of 60 ℃; filtering after acid washing is finished, washing the waste silicon powder to be neutral by using deionized water, washing the waste silicon powder for 2 times by using absolute ethyl alcohol, and drying the washed waste silicon powder to obtain purified photovoltaic waste silicon powder with the silicon content of 99.5 wt% and an oxide layer on the surface;
(2) ball milling and refining: putting 20g of purified photovoltaic waste silicon powder into a zirconia ball-milling tank, adding 0.1g of hexadecyl trimethyl ammonium bromide serving as a dispersing agent and 100mL of absolute ethyl alcohol serving as a grinding aid, then adding zirconia grinding balls according to a ball-to-material ratio of 8:1, carrying out ball milling at 600rpm for 10 hours to convert the refined photovoltaic waste silicon powder particles into nano silicon particles, and obtaining nano silicon dispersion after the ball milling is finished; the median particle diameter D50 of the photovoltaic waste silicon powder in the nano silicon dispersion liquid is 185 nm;
(3) ball-milling reaction: adding 2g of graphene oxide with the sheet diameter D50 of less than 5 mu m, 2g of citric acid serving as a linking agent and 10g of phenolic resin serving as a coating agent into the nano-silicon dispersion liquid, supplementing 300mL of absolute ethyl alcohol serving as a grinding aid, continuing to perform ball milling at the speed of 600rpm for 8 hours, performing ball milling reaction, and obtaining composite slurry after the ball milling reaction is finished;
(4) spray drying: adding absolute ethyl alcohol into the composite slurry to be used as a solvent for dilution, stirring for 2 hours on a high-speed stirrer at a stirring speed of 1000rpm, uniformly stirring to obtain diluted composite slurry liquid, and controlling the addition of the absolute ethyl alcohol to enable the solid content of the diluted composite slurry liquid to be 5 wt%; transferring the diluted composite slurry liquid to a spray dryer for spray drying, wherein the air inlet temperature is 130 ℃, the air outlet temperature is 95 ℃, and precursor composite particles are obtained after the spray drying is finished, wherein the precursor composite particles are graphene oxide/phenolic resin coated silicon composite particles;
(5) sintering and carbonizing: placing the precursor composite particles in a tubular furnace, sintering and carbonizing under the protection of a mixed atmosphere with the volume ratio of argon to hydrogen being 10:1, heating from room temperature to 300 ℃ at the speed of 2 ℃/min, keeping for 2h, heating to 950 ℃ at the speed of 3 ℃/min, keeping for 4h, stopping heating and cooling to room temperature to obtain silicon-carbon composite particles, wherein the silicon-carbon composite particles are graphene/amorphous hard carbon coated silicon particles;
(6) acid leaching reaction: placing 20g of silicon-carbon composite particles in 500mL of hydrofluoric acid solution with the concentration of 10 wt% for carrying out acid leaching reaction at 60 ℃ for 8 hours; filtering after the acid leaching reaction is finished, washing the product with deionized water until the supernatant is neutral, and then drying the product for 60min at the temperature of 85 ℃; the operation can effectively remove silicon dioxide on the surface of the nano silicon particles to obtain the shell-structured silicon-carbon composite particles;
(7) and (3) post-treatment: mixing the shell-structured silicon-carbon composite particles, the asphalt and the microcrystalline graphite according to the mass ratio of 7:20:73, and adding tetrahydrofuran into the mixture of the shell-structured silicon-carbon composite particles, the asphalt and the microcrystalline graphite to obtain a mixed feed liquid, wherein the mass fraction of the tetrahydrofuran in the mixed feed liquid is 15 wt%; placing the mixed material liquid on a planetary ball mill, ball-milling for 2h at the ball-milling speed of 200rpm, and then drying for 60min at the temperature of 95 ℃ to obtain a mixed raw material; placing the mixed raw materials in a tube furnace, and carrying out carbonization treatment under the protection of argon: heating from room temperature to 300 deg.C at 3 deg.C/min for 2h, heating to 950 deg.C at 5 deg.C/min for 4h, and cooling to room temperature; and grinding and crushing the carbonized product and sieving the crushed product with a 325-mesh sieve to obtain the silicon-carbon negative electrode material.
Assembling the silicon-carbon negative electrode material prepared by the embodiment into a half cell and testing the electrochemical performance; silicon-carbon negative electrode material: super P: CMC: homogenizing and smearing SBR according to the mass ratio of 93:2.5:2.5:2, wherein the electrolyte is conventional LiPF6 electrolyte; the lithium plate is used as a counter electrode and assembled into a CR2025 button cell. Under the condition of normal temperature, a charge-discharge test is carried out by utilizing an LANHE CT2001A blue test system under the current density of 100mA/g, and the voltage range is 0.005-2.0V; the test results are shown in Table 1.
Example 2
In this embodiment, the method for preparing the silicon-carbon negative electrode material by using the photovoltaic waste silicon powder and the graphene oxide includes the following steps:
(1) pretreatment: the photovoltaic waste silicon powder with the particle size D50 being 50 mu m and the silicon content being 98.5 wt% is sequentially subjected to acid washing and alcohol washing to remove impurities in the photovoltaic waste silicon powder; the acid solution used in the acid washing is 15 wt% HCl and 3 wt% HNO 3 According to the volume ratio of 1:1 in a certain proportion; during acid washing, the photovoltaic waste silicon powder is placed in an acid solution and stirred and reacts for 8 hours at the temperature of 60 ℃; filtering after acid washing is finished, washing the waste silicon powder to be neutral by using deionized water, washing the waste silicon powder for 2 times by using absolute ethyl alcohol, and drying the washed waste silicon powder to obtain purified photovoltaic waste silicon powder with the silicon content of 99.3 wt% and an oxide layer on the surface;
(2) ball milling and refining: putting 20g of purified photovoltaic waste silicon powder into a zirconia ball milling tank, adding 0.1g of hexadecyl trimethyl ammonium bromide serving as a dispersing agent and 100mL of absolute ethyl alcohol serving as a grinding aid, then adding zirconia grinding balls according to a ball-to-material ratio of 8:1, carrying out ball milling at 600rpm for 12h to convert the refined photovoltaic waste silicon powder particles into nano silicon particles, and obtaining nano silicon dispersion after the ball milling is finished; the median particle diameter D50 of the photovoltaic waste silicon powder in the nano silicon dispersion liquid is 145 nm;
(3) ball-milling reaction: adding 2g of graphene oxide with the sheet diameter D50 of less than 5 mu m, 2g of gamma-aminopropyltriethoxysilane KH550 serving as a linking agent and 15g of phenolic resin serving as a coating agent into the nano-silicon dispersion liquid, supplementing 300mL of absolute ethyl alcohol serving as a grinding aid, continuing performing ball milling at the speed of 600rpm for 8 hours, performing ball milling reaction, and obtaining composite slurry after the ball milling reaction is finished;
(4) spray drying: adding absolute ethyl alcohol into the composite slurry to be used as a solvent for dilution, stirring the mixture for 1 hour on a high-speed stirrer at a stirring speed of 1000rpm, uniformly stirring the mixture to obtain diluted composite slurry liquid, and controlling the addition of the absolute ethyl alcohol to enable the solid content of the diluted composite slurry liquid to be 5 wt%; transferring the diluted composite slurry liquid to a spray dryer for spray drying, wherein the air inlet temperature is 130 ℃, the air outlet temperature is 95 ℃, and precursor composite particles are obtained after the spray drying is finished, wherein the precursor composite particles are graphene oxide/phenolic resin coated silicon composite particles;
(5) sintering and carbonizing: placing the precursor composite particles in a tubular furnace to perform sintering carbonization under the protection of a mixed atmosphere with the volume ratio of argon to hydrogen being 10:1, heating from room temperature to 300 ℃ at the speed of 2 ℃/min, keeping for 2h, heating to 950 ℃ at the speed of 3 ℃/min, keeping for 4h, stopping heating and cooling to room temperature to obtain silicon-carbon composite particles, wherein the silicon-carbon composite particles are graphene/amorphous hard carbon coated silicon particles;
(6) acid leaching reaction: placing 23g of silicon-carbon composite particles in 500mL of hydrofluoric acid solution with the concentration of 15 wt% for carrying out acid leaching reaction at 70 ℃ for 6 hours; filtering after the acid leaching reaction is finished, washing the product with deionized water until the supernatant is neutral, and then drying the product for 100min at the temperature of 90 ℃; the operation can effectively remove silicon dioxide on the surface of the nano silicon particles to obtain the shell-structured silicon-carbon composite particles;
(7) and (3) post-treatment: mixing the shell-structured silicon-carbon composite particles, the asphalt and the expanded graphite according to the mass ratio of 8:20:72, and adding tetrahydrofuran into a mixture obtained by mixing the shell-structured silicon-carbon composite particles, the asphalt and the expanded graphite to obtain a mixed feed liquid, wherein the mass fraction of the tetrahydrofuran in the mixed feed liquid is 20 wt%; placing the mixed material liquid on a planetary ball mill, ball-milling for 2h at the ball-milling speed of 200rpm, and then drying for 120min at the temperature of 80 ℃ to obtain a mixed raw material; placing the mixed raw materials in a tube furnace, and carrying out carbonization treatment under the protection of argon: heating from room temperature to 300 deg.C at 3 deg.C/min for 2h, heating to 950 deg.C at 5 deg.C/min for 4h, and cooling to room temperature; and grinding and crushing the carbonized product and sieving the crushed product with a 325-mesh sieve to obtain the silicon-carbon negative electrode material.
The silicon-carbon negative electrode material prepared in this example was assembled into a half cell by the method in example 1 and subjected to electrochemical performance test in the same manner as in example 1, and the test results are shown in table 1.
Example 3
In this embodiment, the method for preparing the silicon-carbon negative electrode material by using the photovoltaic waste silicon powder and the graphene oxide includes the following steps:
(1) pretreatment: the photovoltaic waste silicon powder with the particle size D50 being 10 mu m and the silicon content being 96.5 wt% is sequentially subjected to acid washing and alcohol washing to remove impurities in the photovoltaic waste silicon powderQuality; the acid solution used in the acid washing is 10 wt% H 2 SO 4 And HNO at a concentration of 3 wt% 3 According to the volume ratio of 1.5: 1 in a certain proportion; during acid washing, the photovoltaic waste silicon powder is placed in an acid solution and stirred and reacts for 8 hours at the temperature of 60 ℃; filtering after acid washing is finished, washing the waste silicon powder to be neutral by using deionized water, washing the waste silicon powder for 2 times by using absolute ethyl alcohol, and drying the washed waste silicon powder to obtain purified photovoltaic waste silicon powder with 98.5 wt% of silicon content and an oxide layer on the surface;
(2) ball milling and refining: putting 25g of purified photovoltaic waste silicon powder into a zirconia ball-milling tank, adding 0.1g of sodium lignosulfonate as a dispersing agent and 100mL of absolute ethyl alcohol as a grinding aid, then adding zirconia grinding balls according to a ball-to-material ratio of 8:1, carrying out ball milling at 600rpm for 10 hours to convert the refined photovoltaic waste silicon powder particles into nano silicon particles, and obtaining nano silicon dispersion liquid after the ball milling is finished; the median particle diameter D50 of the photovoltaic waste silicon powder in the nano silicon dispersion liquid is 200 nm;
(3) ball-milling reaction: adding 2g of graphene oxide with the sheet diameter D50 of less than 5 mu m, 2g of phthalic anhydride as a linking agent and 20g of polyacrylic acid as a coating agent into the nano-silicon dispersion liquid, supplementing 300mL of absolute ethyl alcohol as a grinding aid, continuing to perform ball milling at the speed of 600rpm for 8 hours, performing ball milling reaction, and obtaining composite slurry after the ball milling reaction is finished;
(4) spray drying: adding absolute ethyl alcohol as a solvent into the composite slurry for dilution, stirring for 2 hours on a high-speed stirrer at a stirring speed of 500rpm, uniformly stirring to obtain diluted composite slurry liquid, and controlling the addition of the absolute ethyl alcohol so that the solid content of the diluted composite slurry liquid is 6 wt%; transferring the diluted composite slurry liquid to a spray dryer for spray drying, wherein the air inlet temperature is 130 ℃, the air outlet temperature is 100 ℃, and precursor composite particles are obtained after the spray drying is finished, wherein the precursor composite particles are graphene oxide/polyacrylic acid-coated silicon composite particles;
(5) sintering and carbonizing: placing the precursor composite particles in a tubular furnace, sintering and carbonizing under the protection of a mixed atmosphere with the volume ratio of argon to hydrogen being 8:1, heating from room temperature to 300 ℃ at the speed of 2 ℃/min, keeping for 2h, heating to 950 ℃ at the speed of 3 ℃/min, keeping for 4h, stopping heating and cooling to room temperature to obtain silicon-carbon composite particles, wherein the silicon-carbon composite particles are graphene/amorphous hard carbon coated silicon particles;
(6) acid leaching reaction: placing 18g of silicon-carbon composite particles in 500mL of hydrofluoric acid solution with the concentration of 10 wt% for carrying out acid leaching reaction at 60 ℃ for 10 h; filtering after the acid leaching reaction is finished, washing the product with deionized water until the supernatant is neutral, and then drying the product for 120min at 85 ℃; the operation can effectively remove silicon dioxide on the surface of the nano silicon particles to obtain the shell-structured silicon-carbon composite particles;
(7) and (3) post-treatment: mixing the eggshell structure silicon-carbon composite particles, the asphalt and the spherical graphite according to the mass ratio of 8:15:77, and adding tetrahydrofuran into a mixture obtained by mixing the three components to obtain a mixed feed liquid, wherein the mass fraction of the tetrahydrofuran in the mixed feed liquid is 20 wt%; placing the mixed material liquid on a planetary ball mill, ball-milling for 2h at the ball-milling speed of 200rpm, and then drying for 100min at the temperature of 80 ℃ to obtain a mixed raw material; placing the mixed raw materials in a tube furnace, and carrying out carbonization treatment under the protection of argon: heating from room temperature to 300 deg.C at 3 deg.C/min for 2h, heating to 950 deg.C at 5 deg.C/min for 4h, and cooling to room temperature; and grinding and crushing the carbonized product and sieving the crushed product with a 325-mesh sieve to obtain the silicon-carbon negative electrode material.
The silicon-carbon negative electrode material prepared in this example was assembled into a half cell by the method in example 1 and subjected to electrochemical performance test in the same manner as in example 1, and the test results are shown in table 1.
Example 4
In this embodiment, the method for preparing the silicon-carbon negative electrode material by using the photovoltaic waste silicon powder and the graphene oxide includes the following steps:
(1) pretreatment: sequentially carrying out acid washing and alcohol washing on the photovoltaic waste silicon powder with the particle size D50 being 60 mu m and the silicon content being 96.5 wt% to remove impurities in the photovoltaic waste silicon powder; the acid solution used in the acid washing is 10 wt% H 2 SO 4 And HNO at a concentration of 3 wt% 3 According to the volume ratio of 1.5: 1 in a certain proportion; during acid washing, the photovoltaic waste silicon powder is placed in an acid solution and stirred and reacts for 8 hours at the temperature of 60 ℃; filtering after acid washing, washing with deionized water to neutrality, washing with anhydrous ethanol for 2 timesDrying to obtain purified photovoltaic waste silicon powder with an oxide layer on the surface, wherein the silicon content of the purified photovoltaic waste silicon powder is 98.5 wt%;
(2) ball milling and refining: putting 25g of purified photovoltaic waste silicon powder into a zirconia ball-milling tank, adding 0.1g of sodium lignosulfonate as a dispersing agent and 100mL of absolute ethyl alcohol as a grinding aid, then adding zirconia grinding balls according to a ball-to-material ratio of 8:1, carrying out ball milling for 12 hours at 600rpm to convert the refined photovoltaic waste silicon powder particles into nano silicon particles, and obtaining a nano silicon dispersion liquid after the ball milling is finished; the median particle diameter D50 of the photovoltaic waste silicon powder in the nano silicon dispersion liquid is 155 nm;
(3) ball-milling reaction: adding 2g of graphene oxide with the sheet diameter D50 of 3 mu m and 1g of lithium carbonate serving as a linking agent and 22g of polyvinylpyrrolidone serving as a coating agent into the nano-silicon dispersion liquid, supplementing 300mL of absolute ethyl alcohol serving as a grinding aid, continuing ball milling at the speed of 600rpm for 8 hours, carrying out ball milling reaction, and obtaining composite slurry after the ball milling reaction is finished;
(4) and (3) spray drying: adding absolute ethyl alcohol into the composite slurry to be used as a solvent for dilution, stirring the mixture for 1.5 hours on a high-speed stirrer at a stirring speed of 500rpm, uniformly stirring the mixture to obtain diluted composite slurry liquid, and controlling the addition of the absolute ethyl alcohol to enable the solid content of the diluted composite slurry liquid to be 6 wt%; transferring the diluted composite slurry liquid to a spray dryer for spray drying, wherein the air inlet temperature is 130 ℃, the air outlet temperature is 100 ℃, and precursor composite particles are obtained after the spray drying is finished, wherein the precursor composite particles are graphene oxide/polyvinylpyrrolidone coated silicon composite particles;
(5) sintering and carbonizing: placing the precursor composite particles in a tubular furnace, sintering and carbonizing under the protection of a mixed atmosphere with the volume ratio of argon to hydrogen being 10:1, heating from room temperature to 300 ℃ at the speed of 2 ℃/min, keeping for 2h, heating to 950 ℃ at the speed of 3 ℃/min, keeping for 4h, stopping heating and cooling to room temperature to obtain silicon-carbon composite particles, wherein the silicon-carbon composite particles are graphene/amorphous hard carbon coated silicon particles;
(6) acid leaching reaction: placing 19g of silicon-carbon composite particles in 500mL of hydrofluoric acid solution with the concentration of 10 wt% for carrying out acid leaching reaction at 70 ℃ for 8 hours; filtering after the acid leaching reaction is finished, washing the product with deionized water until the supernatant is neutral, and then drying the product; the operation can effectively remove silicon dioxide on the surface of the nano silicon particles to obtain the shell-structured silicon-carbon composite particles;
(7) and (3) post-treatment: mixing the shell-structured silicon-carbon composite particles, asphalt and artificial graphite according to the mass ratio of 7:2:71, and adding tetrahydrofuran into the mixture of the shell-structured silicon-carbon composite particles, the asphalt and the artificial graphite to obtain a mixed feed liquid, wherein the mass fraction of the tetrahydrofuran in the mixed feed liquid is 25 wt%; placing the mixed material liquid on a planetary ball mill, ball-milling for 2h at the ball-milling speed of 200rpm, and then drying for 90min at the temperature of 80 ℃ to obtain a mixed raw material; placing the mixed raw materials in a tube furnace, and carrying out carbonization treatment under the protection of argon: heating from room temperature to 300 deg.C at 3 deg.C/min for 2h, heating to 950 deg.C at 5 deg.C/min for 4h, and cooling to room temperature; and grinding and crushing the carbonized product and sieving the crushed product with a 325-mesh sieve to obtain the silicon-carbon negative electrode material.
The silicon-carbon negative electrode material prepared in this example was assembled into a half cell by the method in example 1 and subjected to electrochemical performance test in the same manner as in example 1, and the test results are shown in table 1.
Example 5
In this embodiment, the method for preparing the silicon-carbon negative electrode material by using the photovoltaic waste silicon powder and the graphene oxide includes the following steps:
(1) pretreatment: the photovoltaic waste silicon powder with the particle size D50 being 50 mu m and the silicon content being 98.5 wt% is sequentially subjected to acid washing and alcohol washing to remove impurities in the photovoltaic waste silicon powder; the acid solution used in the acid washing is 15 wt% HCl and 3 wt% HNO 3 According to the volume ratio of 1:1 in a certain proportion; during acid washing, the photovoltaic waste silicon powder is placed in an acid solution and stirred and reacts for 8 hours at the temperature of 60 ℃; filtering after acid washing is finished, washing the waste silicon powder to be neutral by using deionized water, washing the waste silicon powder for 2 times by using absolute ethyl alcohol, and drying the washed waste silicon powder to obtain purified photovoltaic waste silicon powder with the silicon content of 99 wt% and an oxidation layer on the surface;
(2) ball milling and refining: putting 25g of purified photovoltaic waste silicon powder into a zirconia ball-milling tank, adding 0.5g of fatty alcohol-polyoxyethylene ether as a dispersing agent and 100mL of absolute ethyl alcohol as a grinding aid, adding zirconia grinding balls according to a ball-to-material ratio of 7:1, carrying out ball milling at 500rpm for 10 hours to convert the refined photovoltaic waste silicon powder particles into nano silicon particles, and obtaining nano silicon dispersion after the ball milling is finished; the median particle diameter D50 of the photovoltaic waste silicon powder in the nano silicon dispersion liquid is 185 nm;
(3) ball-milling reaction: adding 2g of graphene oxide with the sheet diameter D50 of 8 mu m, 1.5g of lithium hydroxide serving as a linking agent and 25g of epoxy resin serving as a coating agent into the nano-silicon dispersion liquid, supplementing 300mL of absolute ethyl alcohol serving as a grinding aid, continuing ball milling at the speed of 600rpm for 8 hours, carrying out ball milling reaction, and obtaining composite slurry after the ball milling reaction is finished;
(4) spray drying: adding absolute ethyl alcohol into the composite slurry to be used as a solvent for dilution, stirring the mixture for 1.5 hours on a high-speed stirrer at a stirring speed of 500rpm, uniformly stirring the mixture to obtain diluted composite slurry liquid, and controlling the addition of the absolute ethyl alcohol to enable the solid content of the diluted composite slurry liquid to be 6 wt%; transferring the diluted composite slurry liquid to a spray dryer for spray drying, wherein the air inlet temperature is 130 ℃, the air outlet temperature is 100 ℃, and precursor composite particles are obtained after the spray drying is finished, and are graphene oxide/epoxy resin coated silicon composite particles;
(5) sintering and carbonizing: placing the precursor composite particles in a tubular furnace, sintering and carbonizing under the protection of a mixed atmosphere with the volume ratio of argon to hydrogen being 10:1, heating from room temperature to 300 ℃ at the speed of 2 ℃/min, keeping for 2h, heating to 950 ℃ at the speed of 3 ℃/min, keeping for 4h, stopping heating and cooling to room temperature to obtain silicon-carbon composite particles, wherein the silicon-carbon composite particles are graphene/amorphous hard carbon coated silicon particles;
(6) acid leaching reaction: placing 21g of silicon-carbon composite particles in 500mL of hydrofluoric acid solution with the concentration of 10 wt% for carrying out acid leaching reaction at 60 ℃ for 10 h; filtering after the acid leaching reaction is finished, washing the product with deionized water until the supernatant is neutral, and then drying the product; the operation can effectively remove silicon dioxide on the surface of the nano silicon particles to obtain the shell-structured silicon-carbon composite particles;
(7) and (3) post-treatment: mixing the shell-structured silicon-carbon composite particles, the asphalt and the spherical graphite according to the mass ratio of 8:15:77, and adding tetrahydrofuran into the mixture of the shell-structured silicon-carbon composite particles, the asphalt and the spherical graphite to obtain a mixed feed liquid, wherein the mass fraction of the tetrahydrofuran in the mixed feed liquid is 20 wt%; placing the mixed material liquid on a planetary ball mill, ball-milling for 2h at the ball-milling speed of 200rpm, and then drying for 75min at the temperature of 80 ℃ to obtain a mixed raw material; placing the mixed raw materials in a tube furnace, and carrying out carbonization treatment under the protection of argon: heating from room temperature to 300 deg.C at 3 deg.C/min for 2h, heating to 950 deg.C at 5 deg.C/min for 4h, and cooling to room temperature; and grinding and crushing the carbonized product and sieving the crushed product with a 325-mesh sieve to obtain the silicon-carbon negative electrode material.
The silicon-carbon negative electrode material prepared in the embodiment is assembled into a half cell according to the method in embodiment 1, and electrochemical performance test is performed on the half cell, the test method is the same as that in embodiment 1, and the test results are shown in table 1.
Example 6
In this embodiment, the method for preparing the silicon-carbon negative electrode material by using the photovoltaic waste silicon powder and the graphene oxide includes the following steps:
(1) pretreatment: the photovoltaic waste silicon powder with the particle size D50 being 50 mu m and the silicon content being 98.5 wt% is sequentially subjected to acid washing and alcohol washing to remove impurities in the photovoltaic waste silicon powder; the acid solution used in the acid washing is 15 wt% HCl and 3 wt% HNO 3 According to the volume ratio of 1:1 in a certain proportion; during acid washing, the photovoltaic waste silicon powder is placed in an acid solution and stirred and reacts for 8 hours at the temperature of 60 ℃; filtering after acid washing is finished, washing the waste silicon powder to be neutral by using deionized water, washing the waste silicon powder for 2 times by using absolute ethyl alcohol, and drying the washed waste silicon powder to obtain purified photovoltaic waste silicon powder with 98.9 wt% of silicon content and an oxide layer on the surface;
(2) ball milling and refining: putting 25g of purified photovoltaic waste silicon powder into a zirconia ball-milling tank, adding 0.1g of dodecyl trimethyl ammonium bromide as a dispersing agent and 100mL of absolute ethyl alcohol as a grinding aid, then adding zirconia grinding balls according to a ball-to-material ratio of 8:1, carrying out ball milling at 600rpm for 8h to convert the refined photovoltaic waste silicon powder particles into nano silicon particles, and obtaining nano silicon dispersion after the ball milling is finished; the median particle diameter D50 of the photovoltaic waste silicon powder in the nano silicon dispersion liquid is 100 nm;
(3) ball-milling reaction: adding 2g of graphene oxide with the sheet diameter D50 of 8 mu m, 1g of phosphorus pentoxide as a linking agent and 20g of glucose as a coating agent into the nano-silicon dispersion liquid, supplementing 300mL of absolute ethyl alcohol as a grinding aid, continuing ball milling at 600rpm for 8h, carrying out ball milling reaction, and obtaining composite slurry after the ball milling reaction is finished;
(4) spray drying: adding absolute ethyl alcohol into the composite slurry to be used as a solvent for dilution, stirring the mixture for 1 hour on a high-speed stirrer at a stirring speed of 500rpm, uniformly stirring the mixture to obtain diluted composite slurry liquid, and controlling the addition of the absolute ethyl alcohol to enable the solid content of the diluted composite slurry liquid to be 6 wt%; transferring the diluted composite slurry liquid to a spray dryer for spray drying, wherein the air inlet temperature is 130 ℃, the air outlet temperature is 100 ℃, and precursor composite particles are obtained after the spray drying is finished, wherein the precursor composite particles are graphene oxide/glucose-coated silicon composite particles;
(5) sintering and carbonizing: placing the precursor composite particles in a tubular furnace, sintering and carbonizing under the protection of a mixed atmosphere with the volume ratio of argon to hydrogen being 10:1, heating from room temperature to 300 ℃ at the speed of 2 ℃/min, keeping for 2h, heating to 950 ℃ at the speed of 3 ℃/min, keeping for 4h, stopping heating and cooling to room temperature to obtain silicon-carbon composite particles, wherein the silicon-carbon composite particles are graphene/amorphous hard carbon coated silicon particles;
(6) acid leaching reaction: placing 20g of silicon-carbon composite particles in 500mL of hydrofluoric acid solution with the concentration of 10 wt% for carrying out acid leaching reaction at 60 ℃ for 10 h; filtering after the acid leaching reaction is finished, washing the product with deionized water until the supernatant is neutral, and then drying the product; the operation can effectively remove silicon dioxide on the surface of the nano silicon particles to obtain the shell-structured silicon-carbon composite particles;
(7) and (3) post-treatment: mixing the shell-structured silicon-carbon composite particles, the asphalt and the microcrystalline graphite according to a mass ratio of 8:20:72, and adding tetrahydrofuran into a mixture obtained by mixing the shell-structured silicon-carbon composite particles, the asphalt and the microcrystalline graphite to obtain a mixed feed liquid, wherein the mass fraction of the tetrahydrofuran in the mixed feed liquid is 20 wt%; placing the mixed material liquid on a planetary ball mill, ball-milling for 2h at the ball-milling speed of 200rpm, and then drying for 100min at the temperature of 80 ℃ to obtain a mixed raw material; placing the mixed raw materials in a tube furnace, and carrying out carbonization treatment under the protection of argon: heating from room temperature to 300 deg.C at 3 deg.C/min for 2h, heating to 950 deg.C at 5 deg.C/min for 4h, and cooling to room temperature; and grinding and crushing the carbonized product and sieving the crushed product with a 325-mesh sieve to obtain the silicon-carbon negative electrode material.
The silicon-carbon negative electrode material prepared in this example was assembled into a half cell by the method in example 1 and subjected to electrochemical performance test in the same manner as in example 1, and the test results are shown in table 1.
Example 7
In this embodiment, the method for preparing the silicon-carbon negative electrode material by using the photovoltaic waste silicon powder and the graphene oxide includes the following steps:
(1) pretreatment: sequentially carrying out acid washing and alcohol washing on the photovoltaic waste silicon powder with the particle size D50 being 100 mu m and the silicon content being 96 wt% to remove impurities in the photovoltaic waste silicon powder; the acid solution used in the acid washing is 10 wt% H 2 SO 2 And HNO at a concentration of 3 wt% 3 According to the volume ratio of 1.5: 1 in a certain proportion; during acid washing, the photovoltaic waste silicon powder is placed in an acid solution and stirred and reacts for 8 hours at the temperature of 60 ℃; filtering after acid washing is finished, washing the waste silicon powder to be neutral by using deionized water, washing the waste silicon powder for 2 times by using absolute ethyl alcohol, and drying the washed waste silicon powder to obtain purified photovoltaic waste silicon powder with 98.5 wt% of silicon content and an oxide layer on the surface;
(2) ball milling and refining: putting 25g of purified photovoltaic waste silicon powder into a zirconia ball-milling tank, adding 0.1g of sodium lignosulfonate as a dispersing agent and 100mL of absolute ethyl alcohol as a grinding aid, then adding zirconia grinding balls according to a ball-to-material ratio of 8:1, carrying out ball milling at 600rpm for 20h to convert the refined photovoltaic waste silicon powder particles into nano silicon particles, and obtaining nano silicon dispersion liquid after the ball milling is finished; the median particle diameter D50 of the photovoltaic waste silicon powder in the nano silicon dispersion liquid is 150 nm;
(3) ball-milling reaction: adding 2g of graphene oxide with the sheet diameter D50 of 10 mu m, 2g of citric acid serving as a linking agent and 20g of sodium carboxymethylcellulose serving as a coating agent into the nano-silicon dispersion liquid, supplementing 300mL of absolute ethyl alcohol serving as a grinding aid, continuing carrying out ball milling at the speed of 600rpm for 8h, carrying out ball milling reaction, and obtaining composite slurry after the ball milling reaction is finished;
(4) spray drying: adding absolute ethyl alcohol into the composite slurry to be used as a solvent for dilution, stirring for 2 hours on a high-speed stirrer at a stirring speed of 500rpm, uniformly stirring to obtain diluted composite slurry liquid, and controlling the addition of the absolute ethyl alcohol to enable the solid content of the diluted composite slurry liquid to be 5 wt%; transferring the diluted composite slurry liquid to a spray dryer for spray drying, wherein the air inlet temperature is 130 ℃, the air outlet temperature is 100 ℃, and precursor composite particles are obtained after the spray drying is finished, wherein the precursor composite particles are graphene oxide/sodium carboxymethylcellulose-coated silicon composite particles;
(5) sintering and carbonizing: placing the precursor composite particles in a tubular furnace, sintering and carbonizing under the protection of a mixed atmosphere with the volume ratio of argon to hydrogen being 10:1, heating from room temperature to 300 ℃ at the speed of 2 ℃/min, keeping for 2h, heating to 950 ℃ at the speed of 3 ℃/min, keeping for 4h, stopping heating and cooling to room temperature to obtain silicon-carbon composite particles, wherein the silicon-carbon composite particles are graphene/amorphous hard carbon coated silicon particles;
(6) acid leaching reaction: placing 20g of silicon-carbon composite particles in 500mL of hydrofluoric acid solution with the concentration of 10 wt% for carrying out acid leaching reaction at 60 ℃ for 10 h; filtering after the acid leaching reaction is finished, washing the product with deionized water until the supernatant is neutral, and then drying the product; the operation can effectively remove silicon dioxide on the surface of the nano silicon particles to obtain the shell-structured silicon-carbon composite particles;
(7) and (3) post-treatment: mixing the shell-structured silicon-carbon composite particles, the asphalt and the mesocarbon microbeads according to the mass ratio of 9:20:71, and adding tetrahydrofuran into the mixture of the shell-structured silicon-carbon composite particles, the asphalt and the mesocarbon microbeads to obtain a mixed feed liquid, wherein the mass fraction of the tetrahydrofuran in the mixed feed liquid is 20 wt%; placing the mixed material liquid on a planetary ball mill, ball-milling for 2h at the ball-milling speed of 200rpm, and then drying for 90min at the temperature of 80 ℃ to obtain a mixed raw material; placing the mixed raw materials in a tube furnace, and carrying out carbonization treatment under the protection of argon: heating from room temperature to 300 deg.C at 3 deg.C/min for 2h, heating to 950 deg.C at 5 deg.C/min for 4h, and cooling to room temperature; and grinding and crushing the carbonized product and sieving the crushed product with a 325-mesh sieve to obtain the silicon-carbon negative electrode material.
The silicon-carbon negative electrode material prepared in this example was assembled into a half cell by the method in example 1 and subjected to electrochemical performance test in the same manner as in example 1, and the test results are shown in table 1.
Comparative example 1
This comparative example differs from example 1 in that: during the ball milling reaction in the step (3), no graphene oxide is added; the other steps are the same as in example 1.
The silicon-carbon negative electrode material prepared by the comparative example is assembled into a half cell according to the method of example 1 and is subjected to electrochemical performance test, the test method is the same as example 1, and the test results are shown in table 1.
Comparative example 2
This comparative example differs from example 1 in that: and (4) the silicon-carbon composite particles-graphene amorphous hard carbon coated silicon particles prepared in the step (5) do not undergo acid leaching reaction in the step (6), but directly skip the step (6) and carry out post-treatment on the silicon-carbon composite particles by adopting the method in the step (7), so as to obtain the silicon-carbon negative electrode material.
The silicon-carbon negative electrode material prepared by the comparative example is assembled into a half cell according to the method of example 1 and is subjected to electrochemical performance test, the test method is the same as example 1, and the test results are shown in table 1.
TABLE 1
As can be seen from the above table, in comparative example 1, graphene oxide is not added, and the content of silicon in silicon carbon particles is higher than that in example 1, which results in a larger initial reversible capacity, and meanwhile, since nano-silicon is not coated by graphene, a stable SEI film cannot be formed during a battery cycle, and the capacity retention rate is only 65.59% after 100 cycles. Comparative example 2 silicon dioxide on the surface of the nano-silicon was not removed with hydrofluoric acid, and irreversible lithium silicate was formed during lithiation, resulting in a decrease in first coulombic efficiency and also having an influence on cycle performance.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications derived therefrom are intended to be within the scope of the claims of this patent.
Claims (9)
1. The method for preparing the silicon-carbon cathode material by using the photovoltaic waste silicon powder and the graphene oxide is characterized by comprising the following steps of:
(1) pretreatment: carrying out acid washing and alcohol washing on the photovoltaic waste silicon powder in sequence to remove impurities in the photovoltaic waste silicon powder and obtain purified photovoltaic waste silicon powder;
(2) ball milling and refining: adding a dispersing agent and a grinding aid into the purified photovoltaic waste silicon powder, then carrying out ball milling to refine photovoltaic waste silicon powder particles and convert the refined photovoltaic waste silicon powder particles into nano silicon particles, and obtaining nano silicon dispersion liquid after the ball milling is finished;
(3) ball-milling reaction: adding graphene oxide, a linking agent and a coating agent into the nano-silicon dispersion liquid, supplementing a grinding aid, and then carrying out a ball milling reaction to obtain a composite slurry after the ball milling reaction is finished;
(4) spray drying: adding a solvent into the composite slurry for dilution, stirring, and uniformly stirring to obtain diluted composite slurry liquid; spray drying the diluted composite slurry liquid to obtain precursor composite particles after the spray drying is finished;
(5) sintering and carbonizing: putting the precursor composite particles into a high-temperature furnace, and sintering and carbonizing under the protection of inert atmosphere to obtain silicon-carbon composite particles after sintering and carbonizing;
(6) acid leaching reaction: placing the silicon-carbon composite particles in acid liquor for acid leaching reaction, washing the silicon-carbon composite particles with deionized water after the acid leaching reaction is finished until the supernatant is neutral, and then drying the silicon-carbon composite particles to obtain the silicon-carbon composite particles with the eggshell structure;
(7) and (3) post-treatment: and mixing the shell-structured silicon-carbon composite particles, asphalt and graphite, and then carrying out carbonization treatment to obtain the multi-carbon-coated silicon-carbon negative electrode material after the carbonization is finished.
2. The method for preparing the silicon-carbon negative electrode material by using the photovoltaic waste silicon powder and the graphene oxide according to claim 1, wherein in the step (1), the acid solution used in the acid washing is an aqueous solution of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, citric acid or acetic acid; the mass fraction of the hyaluronic acid in the acid solution is 5-30 wt%; the alcohol solution used in the alcohol washing is absolute ethyl alcohol; during pretreatment, the photovoltaic waste silicon powder is placed in an acid solution and stirred to react for 2-8 hours at the temperature of 25-80 ℃ for acid washing, the acid washing is finished, then the filtration is carried out, deionized water is used for washing the product to be neutral, and then absolute ethyl alcohol is used for washing the product for 1-3 times and then the product is dried;
in the step (1), the photovoltaic waste silicon powder is polycrystalline and/or monocrystalline waste silicon powder generated by crushing and cutting in the generation process of the photovoltaic industry; the mass fraction of silicon in the photovoltaic waste silicon powder is greater than or equal to 96 wt%; the median particle diameter D50 of the photovoltaic waste silicon powder is less than or equal to 100 microns.
3. The method for preparing the silicon-carbon anode material by using the photovoltaic waste silicon powder and the graphene oxide according to claim 1, wherein in the step (2), the dispersing agent is one or a mixture of two or more of cetyl trimethyl ammonium bromide, sodium lignosulfonate, sodium dodecyl benzene sulfonate, fatty alcohol-polyoxyethylene ether, dodecyl trimethyl ammonium bromide and ethyl phenyl polyethylene glycol;
in the step (2), the grinding aid is one or a mixture of two or more of deionized water, ethanol, methanol, propanol, N-methylpyrrolidone and isopropanol;
in the step (2), the mass ratio of the photovoltaic waste silicon powder to the dispersing agent to the grinding aid is 20-25: 0.1-0.5: 70-100 parts; the ball milling speed is 200-1000 rpm during ball milling refinement, and the ball milling time is 8-30 h; the particle size of the photovoltaic waste silicon powder in the nano silicon dispersion liquid is 10-1000 nm, and the optimal particle size of the photovoltaic waste silicon powder in the nano silicon dispersion liquid is 10-200 nm.
4. The method for preparing the silicon-carbon negative electrode material by using the photovoltaic waste silicon powder and the graphene oxide according to claim 1, wherein the mass ratio of the addition amount of the grinding aid in the step (3) to the addition amount of the grinding aid in the step (2) is 2-4: 1;
in the step (3), the mass ratio of the graphene oxide to the nano silicon in the dispersion liquid is 1: 1-1: 20; the mass ratio of the linking agent to the nano-silicon in the dispersion liquid is 1:10 to 1: 50; the mass ratio of the coating agent to the nano-silicon in the dispersion liquid is 3:10 to 1: 1;
in the step (3), the graphene oxide is a single-layer or multi-layer graphene oxide prepared from natural crystalline flake graphite by a Hummers process, and the median diameter D50 of the graphene oxide is less than or equal to 10 μm;
in the step (3), the linking agent is one or a mixture of two or more of lithium hydroxide, lithium carbonate, citric acid, phthalic anhydride, phosphorus pentoxide, boron oxide, gamma-aminopropyltriethoxysilane and tetraethoxysilane;
in the step (3), the coating agent is one or a mixture of two or more of glucose, sucrose, chitosan, phenolic resin, epoxy resin, coumarone resin, polyvinylpyrrolidone, sodium carboxymethylcellulose and polyacrylic acid; during the ball milling reaction, the ball milling speed is 200-600 rpm, and the ball milling reaction time is 6-10 h;
in the step (4), the solvent for dilution is absolute ethyl alcohol and/or deionized water; the stirring speed is 500-1000 rpm, and the stirring time is 1-2 h; the solid content in the diluted composite slurry liquid is 1-20 wt%; the air inlet temperature of spray drying is 115-135 ℃, and the air outlet temperature is 90-100 ℃.
5. The method for preparing the silicon-carbon anode material by using the photovoltaic waste silicon powder and the graphene oxide according to claim 1, wherein in the step (5), the inert atmosphere protective gas is one or a mixture of two or more of nitrogen, argon and hydrogen in a non-oxidizing gas; the high-temperature furnace is a roller furnace, a rotary furnace or a tubular furnace; the sintering and carbonizing temperature is 200-1000 ℃, and the time is 3-12 h.
6. The method for preparing the silicon-carbon negative electrode material by using the photovoltaic waste silicon powder and the graphene oxide according to claim 5, wherein during sintering carbonization, the temperature is raised from room temperature to 200-500 ℃ at a rate of 2 ℃/min and is kept for 1-4 h, then the temperature is raised to 700-950 ℃ at a rate of 3 ℃/min and is kept for 2-8 h, then the heating and cooling are stopped, and the sintering carbonization is finished.
7. The method for preparing the silicon-carbon negative electrode material by using the photovoltaic waste silicon powder and the graphene oxide according to claim 1, wherein in the step (6), the acid solution used in the acid leaching reaction is a hydrofluoric acid solution, and the mass fraction of hydrofluoric acid in the hydrofluoric acid solution is 2-30 wt%; the time of the acid leaching reaction is 5-20 h, and the temperature is 20-80 ℃; during acid leaching, the mass-volume ratio of the silicon-carbon composite particles to the acid liquor is 0.03-0.25 g/mL; the drying temperature is 50-110 ℃, and the drying time is 30-240 min;
in the step (7), 5-50 parts by weight of the shell-structured silicon-carbon composite particles, 2-30 parts by weight of asphalt and 20-90 parts by weight of graphite are mixed, and during mixing, tetrahydrofuran is used as a solvent for stirring and ball milling mixing, and a fusion machine or a VC mixer is used for mixing;
in the step (7), the graphite is one or a mixture of two or more of artificial graphite, microcrystalline graphite, spherical graphite, expanded graphite and mesocarbon microbeads.
8. The method for preparing the silicon-carbon anode material by using the photovoltaic waste silicon powder and the graphene oxide according to claim 7, wherein the specific operation method in the step (7) is as follows:
step (7-1): adding tetrahydrofuran into a mixture obtained by mixing the shell-structured silicon-carbon composite particles, the asphalt and the graphite to obtain mixed feed liquid;
step (7-2): placing the mixed material liquid on a planetary ball mill for ball milling, and drying after the ball milling is finished to obtain a mixed raw material;
step (7-3): and (3) placing the mixed raw materials in a tubular furnace, carrying out carbonization treatment under the protection of argon, and grinding, crushing and sieving the carbonized product to obtain the multi-carbon coated silicon-carbon negative electrode material.
9. The method for preparing the silicon-carbon anode material by using the photovoltaic waste silicon powder and the graphene oxide according to claim 8, wherein in the step (7-1), the mass fraction of tetrahydrofuran in the mixed liquid is 15-50 wt%;
in the step (7-2), the ball milling speed of the planetary ball mill is 200-400 rpm, and the ball milling time is 1-4 h; the drying temperature is 60-105 ℃, and the drying time is 60-300 min;
in the step (7-3), during carbonization treatment, firstly heating to 200-500 ℃ at 3 ℃/min for 1-4 h, then heating to 700-1000 ℃ at 5 ℃/min for 2-8 h, and finally stopping heating and cooling to room temperature; and finally grinding and crushing the carbonized product and sieving the crushed product by a 325-mesh sieve.
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