CN113036255A - Method for preparing silicon-carbon composite material by using waste lithium ion battery cathode and application - Google Patents
Method for preparing silicon-carbon composite material by using waste lithium ion battery cathode and application Download PDFInfo
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- CN113036255A CN113036255A CN202110217443.6A CN202110217443A CN113036255A CN 113036255 A CN113036255 A CN 113036255A CN 202110217443 A CN202110217443 A CN 202110217443A CN 113036255 A CN113036255 A CN 113036255A
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- 239000002153 silicon-carbon composite material Substances 0.000 title claims abstract description 38
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 30
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 50
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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
- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
-
- 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
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0416—Methods of deposition of the material involving impregnation with a solution, dispersion, paste or dry powder
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
-
- 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
-
- 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
- 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
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Abstract
The invention discloses a method for preparing a silicon-carbon composite material by utilizing a waste lithium ion battery cathode and application thereof. The method takes the cathode material of the waste lithium ion battery as the raw material, synthesizes the silicon-carbon composite material by recycling, has lower cost and simple operation, obtains excellent product performance, further utilizes waste resources, and plays a great role in environmental protection and resource recycling.
Description
Technical Field
The invention belongs to the field of recycling of lithium ion batteries, and particularly relates to a method for preparing a silicon-carbon composite material by using a waste lithium ion battery cathode and application of the silicon-carbon composite material.
Background
Since commercialization, lithium ion batteries have become an integral part of modern society, greatly affecting our lives. However, as the lithium ion battery is charged and discharged, the capacity of the lithium ion battery is attenuated, and finally the lithium ion battery cannot meet the use requirement and needs to be degraded for use or discarded. At present, the problem of environmental pollution caused by waste batteries is more and more emphasized by people, and the battery recycling technology is continuously developed.
Currently, the focus of attention is mainly on the economically high metals in the waste batteries, such as nickel, cobalt, manganese, lithium, aluminum, copper, and the like, and the waste materials remained after the recovery of metal ions are not subjected to recovery treatment. The main components of the waste materials after the recovered lithium ion battery is subjected to overdischarge, crushing, heat treatment and wet leaching are graphite, and the waste materials also contain unreacted diaphragms, adhesives, residual metal ions and the like. Generally, the way of disposing of these wastes is a high-temperature incineration disposal, which exacerbates waste of resources and greenhouse effect. Related technologies report how to efficiently recover metal ions such as nickel, cobalt, manganese, lithium, aluminum, copper and the like, and waste materials remaining after the recovery of the metal ions are not treated.
The preparation process of natural graphite, artificial graphite, modified graphite and the like usually requires high temperature of 2500-. However, the graphite structure in the waste lithium ion battery is ordered, the secondary treatment is not needed, and the carbon content of the graphite in the recovered graphite is higher than 85 percent and far higher than the grade of graphite ore (usually about 10 percent). If the graphite in the recovered negative electrode can be reused, the manufacturing cost can be reduced, and the environment can be protected. There is a related art that only a little mention is made of the recovery of graphite in the waste lithium ion battery, but the recovery method thereof is not described. Even though the related technology reports the recovery method of waste battery graphite, the cost is high, and the method has no practical application value.
The theoretical specific capacity (4200mAh/g) of silicon is about 11 times of that of graphite (372mAh/g), and the silicon serving as a new-generation lithium ion battery negative electrode material has more remarkable effect on improving the energy density of a battery than the graphite. However, the silicon material has disadvantages that it may generate a volume expansion of up to 300% during charging and discharging, resulting in pulverization of the active material, continuous generation of SEI film, continuous decrease in capacity, and poor cycle stability. In addition, silicon has low self-conductivity, which results in slower charge transport and poor rate capability. The existing method mainly relieves the volume expansion of silicon through nanocrystallization, and improves the conductivity by coating amorphous carbon and compounding the amorphous carbon with a carbon material. The principle is that carbon is used as a dispersing matrix to buffer the volume change of the silicon negative electrode during lithium extraction, the stability of the structure is kept, and meanwhile, the high conductivity of the carbon can improve the conductivity in the battery. In the related art, carbon nanotubes and carbon nanofibers are deposited on the surface of nano silicon powder or embedded between nano silicon powder particles to form a core, and the surface of the core is coated with a carbon layer. The first specific capacity is more than 500mAh/g, and the capacity retention rate is more than 92% after 60-cycle circulation. However, the preparation process is complicated and requires special equipment for its implementation. And a preparation method of the silicon-carbon negative electrode is also reported in the related technology, and the silicon-carbon negative electrode material is prepared by preparing a porous silicon material through secondary acid washing and then performing carbon coating. However, the preparation method is high in cost and cannot be applied in a large scale. At present, after the waste lithium ion battery is recycled, if the residual waste is not recycled, the environment is polluted; the graphite materials used for producing the silicon-carbon negative electrode are generally commercial graphite materials, and the cost is high.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art described above. Therefore, the invention provides a method for preparing a silicon-carbon composite material by utilizing a waste lithium ion battery cathode and application thereof, which have the advantages of convenience in operation, low production cost, low energy consumption and the like and are suitable for industrial production.
According to one aspect of the invention, the method for preparing the silicon-carbon composite material by using the cathode of the waste lithium ion battery comprises the following steps:
s1, splitting a waste lithium ion battery to obtain a positive electrode sheet and a negative electrode sheet, and carrying out heat treatment, crushing and sieving on the negative electrode sheet to obtain minus sieve graphite negative electrode powder;
s2, dissolving the graphite negative electrode powder in an acid solution, stirring, carrying out solid-liquid separation, taking and washing a precipitate, and drying to obtain a graphite material;
s3, dissolving asphalt in kerosene to obtain a mixed solution, adding the graphite material and a silicon source, and stirring until the kerosene is completely volatilized to obtain a mixed material;
and S4, carbonizing the mixed material to obtain the carbon-silicon composite material.
In some embodiments of the present invention, the temperature of the heat treatment in step S1 is 200-500 ℃; the heat treatment time is 2-48 h.
In some preferred embodiments of the present invention, in step S1, the temperature of the heat treatment is 220-350 ℃; the heat treatment time is 5-20 h.
In some embodiments of the present invention, in step S1, the rotation speed used for crushing is 20000-.
In some embodiments of the present invention, in step S1, the screening mesh number is 100-400 mesh.
In some preferred embodiments of the present invention, in step S1, the mesh number of the screen is 200-300 meshes.
In some embodiments of the invention, in step S2, the acid solution is at least one of hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, hydrofluoric acid, or acetic acid; the concentration of the acid solution is 1-5 mol/L.
In some preferred embodiments of the present invention, the concentration of the acid solution is 2 to 5 mol/L.
In some embodiments of the invention, in step S2, the stirring time is 2-15 h.
In some preferred embodiments of the present invention, in step S2, the stirring time is 4-12 h.
In some embodiments of the present invention, in step S2, the solid-liquid separation is performed by one of centrifugation, vacuum filtration or filter press.
In some preferred embodiments of the present invention, the rotational speed of the centrifugation is 3000-10000 r/min; the vacuum degree of the vacuum filtration is 0.85-0.95 MPa.
In some embodiments of the present invention, in step S2, the washing process is: the solid precipitate was repeatedly washed with deionized water and anhydrous ethanol until the filtrate was neutral (pH 7).
In some embodiments of the invention, the temperature of the drying is 60-100 ℃ in step S2; the drying time is 5-15 h.
In some embodiments of the invention, in step S3, the mass ratio of asphalt to kerosene is 1: (10-200).
In some preferred embodiments of the present invention, in step S3, the mass ratio of asphalt to kerosene is 1: (10-100).
In some embodiments of the present invention, in step S2 and/or step S3, the stirring manner is magnetic stirring or electric stirring.
In some embodiments of the present invention, in step S3, the mass ratio of the graphite material, the silicon source and the pitch is 1: (0.05-0.2): (0.1-1).
In some preferred embodiments of the present invention, in step S3, the mass ratio of the graphite material, the silicon source and the pitch is 1: (0.08-0.15): (0.1-0.4).
In some embodiments of the present invention, in step S3, the silicon source is one or both of elemental silicon or nano silicon.
In some embodiments of the present invention, in step S3, the volatilized kerosene gas is introduced into a condenser for collection, and then the kerosene and water are separated by an oil-water separator, so as to recycle the kerosene.
In some embodiments of the present invention, in step S4, the carbonization treatment is performed under an inert atmosphere, which is one of nitrogen, helium, argon, or neon.
In some preferred embodiments of the present invention, in step S4, the inert atmosphere is nitrogen or argon.
In some embodiments of the present invention, the carbonization temperature is 600-1500 ℃ in step S4; the carbonization time is 5-36 h.
In some preferred embodiments of the present invention, the carbonization temperature is 700-1000 ℃ in step S4; the carbonization time is 5-15 h.
The invention also provides application of the method in preparation of batteries.
According to a preferred embodiment of the present invention, at least the following advantages are provided:
1. the method takes the cathode material of the waste lithium ion battery as the raw material, synthesizes the silicon-carbon composite material by recycling, has lower cost and simple operation, and obtains the product with excellent performance, thereby further utilizing waste resources and playing a great role in environmental protection and resource recycling;
2. the method has the advantages that the variety of the usable graphite raw materials is multiple, the dependence on the graphite raw material source is low, one or more types of recovered graphite can be mixed for use, the manufacturing cost of the silicon-carbon composite material is further reduced, and the application value of the waste graphite is improved;
3. in the method, the kerosene is used as a solvent in the stirring of the silicon source, the asphalt and the graphite material, and the mixture can be carbonized without being dried after being fully mixed, so that the energy consumption in the production process is greatly reduced;
4. the carbon-silicon composite material prepared by the method has the advantages that under the conditions that the voltage is 0.01-2V and the current density is 100mA/g, the first lithium intercalation specific capacity is 670-760mAh/g, the first lithium deintercalation specific capacity is 530-610mAh/g, the first efficiency is 80-81%, and the capacity retention ratio is 95-97% after 50 times of circulation. The performance of the material is equivalent to that of a silicon-carbon composite material prepared from commercial graphite, and the material can meet the requirement of a lithium ion battery on high energy density.
Drawings
The invention is further described with reference to the following figures and examples, in which:
FIG. 1 is an XRD pattern of a silicon carbon composite material prepared in example 1 of the present invention;
FIG. 2 is an SEM image of a silicon-carbon composite material prepared in example 1 of the present invention;
FIG. 3 is a graph showing the cycle performance of the silicon-carbon composites prepared in examples 1 and 2 and comparative examples 1 and 3 at a current density of 100 mA/g.
Detailed Description
The concept and technical effects of the present invention will be clearly and completely described below in conjunction with the embodiments to fully understand the objects, features and effects of the present invention. It is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and those skilled in the art can obtain other embodiments without inventive effort based on the embodiments of the present invention, and all embodiments are within the protection scope of the present invention.
Example 1
The embodiment prepares the silicon-carbon composite material, and the specific process comprises the following steps:
s1, removing a shell of a waste lithium ion single battery, separating positive and negative plates, collecting the negative plates of a plurality of batteries, keeping the temperature of the recovered negative plates at 300 ℃ for 12 hours, performing heat treatment, removing surface organic matters, polyvinylidene fluoride (PVDF), carboxymethyl cellulose (CMC) and the like, crushing the heat-treated negative plates at 34000r/min for 15min, sieving the crushed negative plates with a 300-mesh sieve, and separating copper foil and graphite negative powder to obtain graphite negative powder undersize, wherein the weight of the undersize is about 750 g;
s2, dissolving the undersize product of the graphite negative electrode powder in a 5mol/L sulfuric acid solution, stirring for 6 hours, removing residual metal ions, carrying out solid-liquid separation on the obtained solution, collecting solid precipitates, repeatedly washing the solid precipitates with deionized water and absolute ethyl alcohol until the filtrate is neutral (pH is 7), and drying at 60 ℃ for 12 hours to obtain about 700g of graphite material;
s3, dissolving 70g of asphalt in 700g of kerosene, uniformly stirring to obtain a mixed solution, adding 700g of the graphite material obtained in the step S2 and 70g of nano silicon into the mixed solution, continuously stirring until the kerosene is completely volatilized to obtain a mixed material, introducing volatilized kerosene gas into a condenser for collection, separating the kerosene and water through an oil-water separator, and recycling the kerosene;
and S4, heating the mixed material obtained in the step S3 to 700 ℃ in a nitrogen atmosphere, preserving the heat for 8 hours, and taking out to obtain the silicon-carbon composite material.
Example 2
The embodiment prepares the silicon-carbon composite material, and the specific process comprises the following steps:
s1, removing a shell of a waste lithium ion single battery, separating positive and negative plates, collecting the negative plates of a plurality of batteries, keeping the temperature of the recovered negative plates at 320 ℃ for 10 hours, performing heat treatment, removing surface organic matters, PVDF (polyvinylidene fluoride), CMC (carboxy methyl cellulose) and the like, crushing the heat-treated negative plates at 34000r/min for 15min, sieving the crushed negative plates with a 300-mesh sieve, and separating copper foil from graphite negative powder to obtain graphite negative powder undersize, wherein the weight of the undersize is about 750 g;
s2, dissolving the undersize product of the graphite negative electrode powder in a 5mol/L sulfuric acid solution, stirring for 4 hours, removing residual metal ions, carrying out solid-liquid separation on the obtained solution, collecting solid precipitates, repeatedly washing the solid precipitates with deionized water and absolute ethyl alcohol until the filtrate is neutral (pH is 7), and drying at 70 ℃ for 10 hours to obtain about 700g of graphite material;
s3, dissolving 80g of asphalt in 700g of kerosene, uniformly stirring to obtain a mixed solution, adding 700g of the graphite material obtained in the step S2 and 60g of nano silicon into the mixed solution, continuously stirring until the kerosene is completely volatilized to obtain a mixed material, introducing volatilized kerosene gas into a condenser for collection, separating the kerosene and water through an oil-water separator, and recycling the kerosene;
and S4, heating the mixed material obtained in the step S3 to 800 ℃ in a nitrogen atmosphere, preserving the heat for 5 hours, and taking out to obtain the silicon-carbon composite material.
Example 3
The embodiment prepares the silicon-carbon composite material, and the specific process comprises the following steps:
s1, removing a shell of a waste lithium ion single battery, separating positive and negative plates, collecting the negative plates of a plurality of batteries, keeping the temperature of the recovered negative plates at 350 ℃ for 6 hours, carrying out heat treatment, removing surface organic matters, PVDF (polyvinylidene fluoride), CMC (carboxy methyl cellulose) and the like, crushing the negative plates after the heat treatment, wherein the crushing rotation speed is 34000r/min, the crushing time is 15min, sieving the crushed negative plates with a 300-mesh sieve, and separating copper foil from graphite negative powder to obtain graphite negative powder undersize, which is about 750 g;
s2, dissolving the undersize product of the graphite negative electrode powder in a 4mol/L hydrochloric acid solution, stirring for 6 hours, removing residual metal ions, carrying out solid-liquid separation on the obtained solution, collecting solid precipitates, repeatedly washing the solid precipitates with deionized water and absolute ethyl alcohol until the filtrate is neutral (pH is 7), and drying at 80 ℃ for 6 hours to obtain about 700g of graphite material;
s3, dissolving 70g of asphalt in 800g of kerosene, uniformly stirring to obtain a mixed solution, adding 700g of the graphite material obtained in the step S2 and 80g of nano silicon into the mixed solution, continuously stirring until the kerosene is completely volatilized to obtain a mixed material, simultaneously introducing volatilized kerosene gas into a condenser for collection, separating the kerosene from water through an oil-water separator, and recycling the kerosene;
and S4, heating the mixed material obtained in the step S3 to 800 ℃ in a nitrogen atmosphere, preserving the heat for 5 hours, and taking out to obtain the silicon-carbon composite material.
Example 4
The embodiment prepares the silicon-carbon composite material, and the specific process comprises the following steps:
s1, removing a shell of a waste lithium ion single battery, separating positive and negative plates, collecting the negative plates of a plurality of batteries, keeping the temperature of the recovered negative plates at 350 ℃ for 6 hours, carrying out heat treatment, removing surface organic matters, PVDF (polyvinylidene fluoride), CMC (carboxy methyl cellulose) and the like, crushing the negative plates after the heat treatment, wherein the crushing rotation speed is 34000r/min, the crushing time is 15min, sieving the crushed negative plates with a 300-mesh sieve, and separating copper foil from graphite negative powder to obtain graphite negative powder undersize, which is about 750 g;
s2, dissolving the undersize product of the graphite negative electrode powder in a 3mol/L hydrochloric acid solution, stirring for 6 hours, removing residual metal ions, carrying out solid-liquid separation on the obtained solution, collecting solid precipitates, repeatedly washing the solid precipitates with deionized water and absolute ethyl alcohol until the filtrate is neutral (pH is 7), and drying at 80 ℃ for 6 hours to obtain about 700g of graphite material;
s3, dissolving 100g of asphalt in 1200g of kerosene, uniformly stirring to obtain a mixed solution, adding 700g of the graphite material and 100g of nano silicon obtained in the step S2 into the mixed solution, continuously stirring until the kerosene is completely volatilized to obtain a mixed material, introducing volatilized kerosene gas into a condenser for collection, separating the kerosene and water through an oil-water separator, and recycling the kerosene;
and S4, heating the mixed material obtained in the step S3 to 1000 ℃ in a nitrogen atmosphere, preserving heat for 3 hours, and taking out to obtain the silicon-carbon composite material.
Comparative example 1
The comparative example prepares a silicon-carbon composite material, and the difference with the example 4 is mainly that the pickling step is lacked, and the specific process is as follows:
s1, removing a shell of a waste lithium ion single battery, separating positive and negative plates, collecting the negative plates of a plurality of batteries, keeping the temperature of the recovered negative plates at 350 ℃ for 6 hours, carrying out heat treatment, removing surface organic matters, PVDF (polyvinylidene fluoride), CMC (carboxy methyl cellulose) and the like, crushing the negative plates after the heat treatment, wherein the crushing rotation speed is 34000r/min, the crushing time is 15min, sieving the crushed negative plates with a 300-mesh sieve, and separating copper foil from graphite negative powder to obtain graphite negative powder undersize, which is about 750 g;
s2, dissolving 90g of asphalt in 900g of kerosene, uniformly stirring to obtain a mixed solution, adding 750g of the graphite material and 90g of nano silicon obtained in the step S1 into the mixed solution, continuously stirring until the kerosene is completely volatilized to obtain a mixed material, simultaneously introducing volatilized kerosene gas into a condenser for collection, separating the kerosene from water through an oil-water separator, and recycling the kerosene;
and S3, heating the mixed material obtained in the step S2 to 1000 ℃ in a nitrogen atmosphere, preserving heat for 3 hours, and taking out to obtain the silicon-carbon composite material.
Comparative example 2
The comparative example prepares a silicon-carbon composite material, and the difference with the example 4 is mainly that the carbonization temperature is very low, and the specific process is as follows:
s1, removing a shell of a waste lithium ion single battery, separating positive and negative plates, collecting the negative plates of a plurality of batteries, keeping the temperature of the recovered negative plates at 350 ℃ for 6 hours, carrying out heat treatment, removing surface organic matters, PVDF (polyvinylidene fluoride), CMC (carboxy methyl cellulose) and the like, crushing the negative plates after the heat treatment, wherein the crushing rotation speed is 34000r/min, the crushing time is 15min, sieving the crushed negative plates with a 300-mesh sieve, and separating copper foil from graphite negative powder to obtain graphite negative powder undersize, which is about 800 g;
s2, dissolving the undersize product of the graphite negative electrode powder in a 3mol/L hydrochloric acid solution, stirring for 6 hours, removing residual metal ions, carrying out solid-liquid separation on the obtained solution, collecting solid precipitates, repeatedly washing the solid precipitates with deionized water and absolute ethyl alcohol until the filtrate is neutral (pH is 7), and drying at 80 ℃ for 6 hours to obtain about 700g of graphite material;
s3, dissolving 80g of asphalt in 800g of kerosene, uniformly stirring to obtain a mixed solution, adding 700g of the graphite material obtained in the step S2 and 100g of nano silicon into the mixed solution, continuously stirring until the kerosene is completely volatilized to obtain a mixed material, introducing volatilized kerosene gas into a condenser for collection, separating the kerosene and water through an oil-water separator, and recycling the kerosene;
and S4, heating the mixed material obtained in the step S3 to 400 ℃ in a nitrogen atmosphere, preserving the heat for 20 hours, and taking out to obtain the silicon-carbon composite material.
Comparative example 3
The comparative example prepares a silicon-carbon composite material, and the difference with the example 3 is mainly that commercial graphite is used for replacing recycled graphite material, and the specific process is as follows:
s1, dissolving 50g of asphalt in 500g of kerosene, uniformly stirring to obtain a mixed solution, adding 500g of commercial graphite and 50g of nano-silicon into the mixed solution, continuously stirring until the kerosene is completely volatilized to obtain a mixed material, introducing volatilized kerosene gas into a condenser for collection, separating the kerosene and water through an oil-water separator, and recycling the kerosene.
S2, heating the mixed material obtained in the step S1 to 800 ℃ in a nitrogen atmosphere, preserving heat for 5 hours, and taking out to obtain the silicon-carbon composite material.
Comparative example 4
This comparative example prepared a silicon carbon material according to the method of the patent (publication No. CN101153358A), and the specific procedure was:
ball-milling silicon powder with D50 of 2 mu m for 10h, adding the silicon powder into an NMP (N-methylpyrrolidone) solution of polypyrrole, stirring for 2h, and drying at low temperature; 1.5g of the silicon powder is added into carbon disulfide solution of adhesive asphalt (0.5g of the adhesive asphalt is dissolved in 15ml of the carbon disulfide solution) and stirred for 1 hour; slowly adding 8.5g D50 spherical graphite with the particle size of 19 μm into the system, stirring for 1h, and drying; the material is put into a tube furnace with argon protection for carbonization, the carbonization temperature is 1000 ℃, and the carbonization time is 5 hours; adding the prepared material into a toluene solution of impregnant asphalt (0.3g of impregnant asphalt is dissolved in 25ml of toluene solution), stirring for 2 hours, and volatilizing the solvent; the material is put into a tube furnace with argon protection for carbonization at the temperature of 1000 ℃ for 5h to obtain the silicon-carbon material.
Test examples
The silicon-carbon composite negative electrode materials obtained in the examples and the comparative examples are subjected to button cell manufacturing and electrical property tests, which specifically comprise the following steps:
adding a proper amount of N-methyl pyrrolidone into the silicon-carbon composite material prepared in the examples 1-4 and the comparative examples 1-3, the conductive carbon black and the polyvinylidene fluoride according to the mass ratio of 92:2:6, stirring for a certain time to prepare negative electrode slurry, and uniformly coating the negative electrode slurry on a copper foil; drying the plate for a plurality of times at 85 ℃, and punching the plate; placing the punched pole piece in a vacuum drying oven to be dried for 12 hours in vacuum at 100 ℃; assembling the pole piece, the diaphragm, the lithium piece, the electrolyte and the positive and negative electrode shells in a glove box according to a certain sequence to complete the assembly of the CR2430 button cell; the assembled cell was left to stand for 3h and tested.
The battery test conditions are as follows: at room temperature of 25 ℃, the charging and discharging voltage is 0.01-2.0V, and the current density is 100 mA/g. The test results are shown in table 1.
TABLE 1 comparison of electrochemical Properties of examples and comparative examples
As can be seen from Table 1, the composite material prepared in the examples has a first lithium intercalation specific capacity of 670-760mAh/g, a first lithium deintercalation specific capacity of 530-610mAh/g, a first efficiency of 80-81%, and a capacity retention rate of 95-97% after 50 cycles. The comparison ratio has better performance, and the synthesis method is simpler. Compared with the method disclosed by the invention, the comparative example 1 is lack of an acid washing step, and the prepared silicon-carbon negative electrode is high in impurity content and low in capacity. The carbonization temperature in comparative example 2 is too low and is not in the preferred range of the method, and the finally prepared silicon-carbon negative electrode material has low capacity. Comparative example 3 a silicon carbon composite anode material was prepared using commercial graphite, and the capacity and cycle performance thereof were similar to those of the silicon carbon composite anode material prepared using the recycled graphite according to the present invention. Compared with the methods of other patents in the comparative example 4, the method for preparing the silicon-carbon cathode by recycling the waste lithium ion battery cathode has better performance of the synthesized silicon-carbon cathode material. The method has higher feasibility for preparing the silicon-carbon composite negative electrode material by recycling the waste lithium ion battery negative electrode.
Fig. 1 is an XRD pattern of the silicon-carbon composite material prepared in example 1 of the present invention, and it can be seen from the XRD pattern that the composite material is a silicon-carbon composite material. Fig. 2 is an SEM image of the silicon-carbon composite material prepared in example 1, and it can be seen that the nano-silicon particles are uniformly coated on the graphite surface and uniformly dispersed. Fig. 3 is a graph showing the cycle performance of the silicon-carbon composite materials prepared in examples 1 and 2 and comparative examples 1 and 3 at a current density of 100mA/g, and it can be seen that the silicon-carbon composite material prepared in example 1 has good cycle stability, and the capacity retention rate after 50 cycles is 95.3%, which is equivalent to the performance of comparative example 3 using commercial graphite as a raw material.
The embodiments of the present invention have been described in detail with reference to the accompanying drawings, but the present invention is not limited to the above embodiments, and various changes can be made within the knowledge of those skilled in the art without departing from the gist of the present invention. Furthermore, the embodiments of the present invention and features of the embodiments may be combined with each other without conflict.
Claims (10)
1. A method for preparing a silicon-carbon composite material by utilizing a waste lithium ion battery cathode is characterized by comprising the following steps:
s1, splitting a waste lithium ion battery to obtain a positive electrode sheet and a negative electrode sheet, and carrying out heat treatment, crushing and sieving on the negative electrode sheet to obtain undersize graphite negative electrode powder;
s2, dissolving the graphite negative electrode powder in an acid solution, stirring, carrying out solid-liquid separation, taking and washing a precipitate, and drying to obtain a graphite material;
s3, dissolving asphalt in kerosene to obtain a mixed solution, adding the graphite material and a silicon source, and stirring until the kerosene is completely volatilized to obtain a mixed material;
and S4, carbonizing the mixed material to obtain the carbon-silicon composite material.
2. The method as claimed in claim 1, wherein the temperature of the heat treatment in step S1 is 200-500 ℃; the heat treatment time is 2-48 h.
3. The method as claimed in claim 1, wherein in step S1, the sieving mesh number is 100-400 meshes.
4. The method according to claim 1, wherein in step S2, the acid solution is at least one of hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, hydrofluoric acid, or acetic acid; the concentration of the acid solution is 1-5 mol/L.
5. The method according to claim 1, wherein in step S2, the drying temperature is 60-100 ℃; the drying time is 5-15 h.
6. The method according to claim 1, wherein in step S3, the mass ratio of asphalt to kerosene is 1: (10-200).
7. The method according to claim 1, wherein in step S3, the mass ratio of the graphite material, the silicon source and the pitch is 1: (0.05-0.2): (0.1-1).
8. The method of claim 1, wherein in step S3, the silicon source is one or both of elemental silicon or nano-silicon.
9. The method according to claim 1, wherein in step S4, the carbonization treatment is performed under an inert atmosphere; the carbonization temperature is 600-1500 ℃; the carbonization time is 5-36 h.
10. Use of the method of any one of claims 1 to 9 in the manufacture of a battery.
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| CN202110217443.6A CN113036255A (en) | 2021-02-26 | 2021-02-26 | Method for preparing silicon-carbon composite material by using waste lithium ion battery cathode and application |
| PCT/CN2021/142487 WO2022179292A1 (en) | 2021-02-26 | 2021-12-29 | Method for preparing silicon-carbon composite material using negative electrodes of waste lithium-ion batteries and application |
| HU2200269A HUP2200269A1 (en) | 2021-02-26 | 2021-12-29 | Method for preparing silicon-carbon composite material using negative electrodes of waste lithium-ion batteries and application |
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| WO2022179292A1 (en) * | 2021-02-26 | 2022-09-01 | 广东邦普循环科技有限公司 | Method for preparing silicon-carbon composite material using negative electrodes of waste lithium-ion batteries and application |
| CN115332662A (en) * | 2022-08-09 | 2022-11-11 | 东莞理工学院 | Recovery method and application of waste lithium battery graphite negative electrode material |
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