CN111063872A - Silicon-carbon negative electrode material and preparation method thereof - Google Patents
Silicon-carbon negative electrode material and preparation method thereof Download PDFInfo
- Publication number
- CN111063872A CN111063872A CN201911259751.4A CN201911259751A CN111063872A CN 111063872 A CN111063872 A CN 111063872A CN 201911259751 A CN201911259751 A CN 201911259751A CN 111063872 A CN111063872 A CN 111063872A
- Authority
- CN
- China
- Prior art keywords
- silicon
- negative electrode
- graphene
- carbon
- electrode material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- 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
- H01M4/366—Composites as layered products
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- 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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- 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
- 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
A silicon carbon negative electrode material and a preparation method thereof belong to the technical field of lithium ion batteries and comprise the following contents: (1) adding silicon-based nanoparticles into aqueous dispersion of graphene oxide, stirring and mixing, performing spray drying on the mixed solution, and then carbonizing at high temperature in an inert atmosphere to obtain a graphene-coated nano-silicon composite material; (2) and kneading and stirring the graphene-coated silicon nano material, the graphite and the adhesive with high solid content, then carrying out spray drying on the mixture of the graphene-coated silicon nano material, the graphite and the adhesive, and further carrying out carbonization treatment under high-temperature inert atmosphere to obtain graphite and graphene-coated silicon carbon secondary particles. According to the invention, the surface of the nanometer silicon-based material is coated with a layer of graphene, so that the conductivity of the silicon-based material is improved, and the volume expansion of a silicon cathode in the charging and discharging processes is inhibited; and then, in-situ compounding the graphene coated silicon-carbon negative electrode, graphite and the adhesive to form silicon-carbon graphite secondary particles, so that the dynamic property of the battery is improved, and the volume expansion is further reduced.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a silicon-carbon composite negative electrode material for a lithium ion battery and a preparation method thereof.
Background
The lithium ion battery has wide application prospect in the fields of portable consumer electronics, electric tools, energy storage and the like due to excellent performance. Currently, commercial lithium ion batteries mainly use graphite as a negative electrode material. However, due to the rapid increase in the demand for energy density of batteries in the above-mentioned fields, development of lithium ion batteries with higher energy density is urgently required.
The specific capacity of the silicon negative electrode material can reach 4200mAh/g at most, which is much higher than 372mAh/g of the carbon material, and the silicon negative electrode material is a material which is known to be used for negative electrode materials and has the highest theoretical specific capacity at present. However, the silicon negative electrode material has the problems of poor conductivity, large volume change, continuous generation of SEI film and low cycle life, and is usually required to be used in combination with a carbon material to form a novel silicon-carbon negative electrode material to solve the problems.
Graphene is a novel carbon nanomaterial, and has a large specific surface area and excellent electrical and mechanical properties, the excellent conductivity of graphene can improve the rate capability of a lithium ion battery to a great extent, but the large specific surface area of graphene increases the side reaction of an interface, resulting in lower coulombic efficiency, and meanwhile, the sparse two-dimensional structure of graphene results in lower electrode compaction density, which brings more challenges for practical application. However, the compounding of graphene and silicon cathode materials is expected to solve the problems existing in respective independent application, the large surface area of graphene can be used as an effective carrier in the nano-silicon dispersion process, the graphene-coated silicon cathode material can be formed through sintering and in-situ compounding treatment, the problems of poor conductivity, large volume expansion and the like existing in the silicon cathode use process can be powerfully solved through the excellent conductivity and strong mechanical property of graphene, the specific surface area of the graphene coated with silicon is reduced, and the tap density is improved.
The patent with publication number of CN105470459B provides a preparation method of a silicon carbon negative electrode material, wherein the coating material used is a high polymer material, but the high polymer has poor conductivity, the strength of the expanded beam of the silicon carbon negative electrode is not enough, the whole process is relatively complex, more impurities are introduced, and the preparation cost is relatively high.
The patent with publication number of CN106159215A also discloses a preparation method of a silicon carbon negative electrode material, which forms a silicon carbon negative electrode material coated with a carbon material by in-situ coating on a silicon surface through multi-step polymerization, but the whole process involves more polymerization reactions, is difficult to control, has high cost, and is not convenient for industrial preparation.
Disclosure of Invention
The invention of the invention is: in order to overcome the defects of the silicon-carbon cathode in the prior art, the invention provides a simple silicon-carbon cathode material convenient for industrialization and a preparation method thereof.
The invention is realized by the following technical scheme.
The silicon-carbon negative electrode material comprises the following raw materials in percentage by mass: graphene silicon carbon negative electrode nano composite material: graphite: adhesive = (5% -80%): (90% -10%): (5% -30%), the sum of the mass percentages of the graphene silicon carbon negative electrode nano composite material, the graphite and the adhesive is 100%; the graphene silicon carbon cathode nano composite material comprises the following raw materials in percentage by weight: and (3) graphene oxide: the silicon-based negative electrode material (5-90%) is (95-10%), and the sum of the mass percentages of the graphene oxide and the silicon-based negative electrode material in the graphene silicon carbon negative electrode nano composite material is 100%.
A preparation method of a silicon-carbon negative electrode material comprises the following steps:
s1, adding a silicon-based negative electrode material into the graphene oxide solution, mixing to obtain a dispersion liquid, wherein the mass percentage of the graphene oxide to the silicon-based negative electrode material in the dispersion liquid is (5% -90%) to (95% -10%), the sum of the mass percentages of the silicon-based negative electrode material and the graphene oxide is 100%, and uniformly stirring the dispersion liquid;
s2, sequentially carrying out primary spray drying and primary carbonization on the dispersion liquid stirred and mixed in the step S1 to obtain the graphene silicon carbon negative electrode nano composite material of the graphene-coated silicon-based negative electrode material;
s3, kneading and stirring the graphene silicon carbon cathode nano composite material prepared in the step S2, graphite and an adhesive fully at a high solid content for 60-600 min, wherein the kneading and stirring speed is 10-50 rpm, the solid content of the kneading and stirring is 40-80%; wherein the graphene silicon carbon negative electrode nano composite material comprises the following components in percentage by weight: graphite: the adhesive comprises the following components in percentage by mass (5-80%): (90% -10%): (5% -30%), the sum of the mass percentages of the graphene silicon carbon negative electrode nano composite material, the graphite and the adhesive is 100%;
and S4, carrying out secondary spray drying and secondary carbonization on the mixture prepared by kneading and stirring the high solid content in the step S3 in sequence to obtain the silicon-carbon negative electrode material.
Further, in the step S1, graphene oxide in the dispersion liquid is carbonized for the first time in the step S2 to prepare graphene coated outside the silicon-based negative electrode material, and the mass percentage of the graphene and the silicon-based negative electrode material in the graphene silicon carbon negative electrode nanocomposite is (1.5% -85%): (98.5% -15%), wherein the sum of the mass percentages of the graphene and the silicon-based negative electrode material is 100%; in the step S3, the adhesive is carbonized for the second time in the step S4 to prepare amorphous carbon, and the graphene silicon carbon negative electrode nano composite material in the silicon carbon negative electrode material: graphite: the amorphous carbon comprises (6-80%) by mass: (92-15%): (2% -25%), and the sum of the mass percentages of the graphene silicon carbon negative electrode nano composite material, the graphite and the amorphous carbon is 100%.
Further, in the step S1, the solvent of the dispersion liquid is one or a mixture of several of water, ethanol and nitrogen methyl pyrrolidone, the dispersion speed of the mixed liquid is 2000-5000 rpm, the solid content of the dispersion liquid is 20-80%, and the dispersion time is 3-72 h.
Further, in the step S1, the particle size of the silicon-based negative electrode material is 10 to 200nm, and the silicon-based negative electrode material is silicon-basedThe silicon-based nano particles in the cathode material are silicon or silicon oxide SiOXWherein x is>0。
Further, the silicon-based nanoparticles are silicon oxide SiOXWherein x is 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1 or 2.
Further, in the step S1, the mass percentage of the graphene oxide solution is 10% to 50%.
Further, in the step S2, the first spray drying process is performed in an inert atmosphere, and the drying temperature is 80 to 300 ℃, wherein the particle size of the obtained graphene oxide/silicon-based nanoparticles is 300nm to 1.5 um; the primary carbonization temperature is 300-1000 ℃, and the particle size of the carbonized graphene/silicon-based nanoparticles is 30-500 nm.
Further, in the step S3, the graphite is one or a mixture of several of artificial graphite, natural graphite, and mesocarbon microbeads, wherein the particle size D50 of the graphite is 8-20 um, and the graphitization degree is greater than 90%.
Further, in step S3, the adhesive is one or more of polyvinylidene fluoride, polytetrafluoroethylene, styrene butadiene rubber, sodium carboxymethylcellulose, or sodium alginate.
Further, in the step S4, the second spray drying process is performed in an inert atmosphere, the drying temperature is 80 to 300 ℃, and the particle size of the silicon-carbon composite material obtained after drying is 10 to 25 um; the carbonization temperature of the second carbonization is 300-1000 ℃, the particle size D50 of the obtained graphene-coated silicon carbon/graphite particles is 10-20 um, and the specific surface area is 1-5 m2/g。
Further, the dry inert atmosphere is helium, argon, nitrogen or a mixed gas of three gases.
Compared with the prior art, the invention has the beneficial effects that:
1. the silicon-based nanoparticles are dispersed into the dispersion liquid of the graphene oxide, so that the silicon-based nanoparticles and the graphene oxide can be uniformly mixed, and then uniform particles of the graphene-coated silicon-based nanoparticles are prepared by spray drying. Meanwhile, the surface of the silicon-based nanoparticles is coated with graphene, so that a silicon-carbon composite material similar to a core-shell structure can be formed, wherein the graphene is positioned on the surface of the silicon-based nanoparticles, the electrical conductivity of the silicon-carbon composite material can be enhanced, and the strong mechanical property of the graphene can effectively restrict the volume expansion of silicon in the circulation process.
2. After the surface of the silicon-based nano particle is coated with graphene, the silicon-based nano particle has better affinity with graphite, and the graphene-coated silicon-based nano particle, the graphite and the adhesive are kneaded and stirred, so that the graphene-coated silicon-based nano material and the graphite can be fully and uniformly mixed on the one hand, and on the other hand, the adhesive can be uniformly distributed on the surfaces of the graphene-coated silicon-based nano particle and the graphite in the kneading process, so that after further carbonization, the existence of the adhesive further enhances the combination degree of the silicon-carbon composite material and the graphite, secondary particles of silicon carbon and graphite are formed, the dynamic performance of the composite material can be further improved, and the cyclic expansion is reduced.
Drawings
FIG. 1 is an SEM image of a silicon carbon negative electrode material prepared in example 1.
FIG. 2 is a charge-discharge curve diagram of the silicon-carbon negative electrode material prepared in example 1.
Detailed Description
The present invention is further illustrated by the following specific examples, which are merely representative examples to clearly and completely explain the present invention, but the scope of the present invention is not limited by these examples.
Example 1
S1, adding silicon nanoparticles with the D50 of 30nm into the graphene oxide aqueous dispersion, and then obtaining the silicon-based material-graphene oxide dispersion under the high-speed shearing force, wherein the weight ratio of silicon: graphene oxide mass = 50%: 50%, the initial concentration of the graphene oxide solution is 0.1g/ml, the solid content of the mixed solution is 20%, and then the mixed solution is dispersed for 24 hours at the speed of 2000rpm to obtain a uniform graphene oxide-silicon nanoparticle dispersion solution;
s2, carrying out first spray drying on the mixed solution obtained in the step S1 at 120 ℃, wherein the diameter of the graphene oxide coated silicon nano particle obtained after drying is 1um, carrying out first carbonization at 600 ℃ in an argon atmosphere, and obtaining graphene coated nano silicon particles with the particle size of about 800nm, wherein the graphene in the composite material: the weight percentage of silicon is 40%: 60 percent;
s3, adding a proper amount of water into the graphene-coated silicon-carbon nano particles obtained in the step S2, the artificial graphite and the SBR adhesive, kneading and stirring in a stirring tank, wherein the graphene-silicon-carbon composite material is prepared by the following steps: graphite: adhesive = 5%: 85%: 10 percent, the kneading stirring speed is 20rpm, the kneading stirring solid content is 60 percent, the kneading time is 120min, and the particle size D50 of the graphite is 13 um;
s4, carrying out secondary spray drying on the kneaded mixture obtained in the step S3, wherein the drying temperature is 120 ℃, and the particle size of the silicon-carbon composite material obtained after spray drying is 14 um; and then further carbonizing at 800 ℃ in an argon atmosphere for a second time to obtain graphene-coated silicon carbon-graphite secondary particles, wherein the graphene silicon carbon: graphite: the mass percent of the amorphous carbon is 6%: 88%: the 6% secondary particle diameter D50 is 13um, the specific surface area is 3m2/g。
Example 2
S1, adding silicon nanoparticles with the D50 of 150nm into the graphene oxide aqueous dispersion, and then obtaining the silicon-based material-graphene oxide dispersion under the high-speed shearing force, wherein the weight ratio of silicon: graphene oxide mass = 50%: 50%, the initial concentration of the graphene oxide solution is 0.1g/ml, the solid content of the mixed solution is 20%, and then the mixed solution is dispersed for 24 hours at the speed of 2000rpm to obtain a uniform graphene oxide-silicon nanoparticle dispersion solution;
s2, carrying out first spray drying on the mixed solution obtained in the step S1 at 120 ℃, wherein the diameter of the graphene oxide coated silicon nano particle obtained after drying is 1um; carrying out primary carbonization at 600 ℃ in an argon atmosphere to obtain graphene-coated nano silicon particles with the particle size of about 800nm, wherein the graphene in the composite material is as follows: the weight percentage of silicon is 40%: 60 percent;
s3, adding a proper amount of water into the graphene-coated silicon-carbon nano particles obtained in the step S2, the artificial graphite and the SBR adhesive, kneading and stirring in a stirring tank, wherein the graphene-silicon-carbon composite material is prepared by the following steps: graphite: adhesive = 5%: 85%: 10 percent, the kneading stirring speed is 20rpm, the kneading stirring solid content is 60 percent, the kneading time is 120min, and the particle size D50 of the graphite is 13 um;
s4, carrying out secondary spray drying on the kneaded mixture obtained in the step S3, wherein the drying temperature is 120 ℃, and the particle size of the silicon-carbon composite material obtained after spray drying is 18 um; further carbonizing for the second time at 800 ℃ in argon atmosphere to obtain the graphene-coated silicon carbon-graphite secondary particles, wherein the particle size D50 of the secondary particles is 17um, and the specific surface area is 1.3m2(iv) per gram, wherein the graphene silicon carbon in the secondary particles: graphite: the mass percent of the amorphous carbon is 6%: 88%: 6 percent.
Example 3
S1, adding silicon nanoparticles with the D50 of 100nm into the graphene oxide aqueous dispersion, and then obtaining the silicon-graphene oxide dispersion under high-speed shearing force, wherein the weight ratio of silicon: graphene oxide mass = 50%: 50%, the initial concentration of the graphene oxide solution is 0.1g/ml, the solid content of the mixed solution is 50%, and then the mixed solution is dispersed for 24 hours at the speed of 2000rpm to obtain a uniform graphene oxide-silicon nanoparticle dispersion solution;
s2, carrying out first spray drying on the mixed solution obtained in the step S1 at 120 ℃, wherein the diameter of the graphene oxide coated silicon nano particle obtained after drying is 1.5 um; carbonizing for the first time at the temperature of 800 ℃ in an argon atmosphere to obtain graphene-coated nano silicon particles with the particle size of about 1.2um, wherein the graphene in the composite material is as follows: the weight percentage of silicon is 40%: 60 percent;
s3, adding a proper amount of water into the graphene-coated silicon-carbon nano particles obtained in the step S2, the artificial graphite and the SBR adhesive, kneading and stirring in a stirring tank, wherein the graphene-silicon-carbon composite material is prepared by the following steps: graphite: adhesive = 5%: 85%: 10 percent, the kneading and stirring speed is 20rpm, the kneading and stirring solid content is 60 percent, the kneading time is 120min, and the particle size D50 of the graphite is 13 um;
s4, carrying out secondary spray drying on the kneaded mixture obtained in the step S3, wherein the drying temperature is 120 ℃, and the particle size of the silicon-carbon composite material obtained after spray drying is 16 um; further treated at 800 deg.C under argon atmosphere for a second timeCarbonizing to obtain graphene-coated silicon carbon-graphite secondary particles, wherein the average particle size D50 of the secondary particles is 15um, and the specific surface area is 2m2(iv) per gram, wherein the graphene silicon carbon in the secondary particles: graphite: the mass percent of the amorphous carbon is 6%: 88%: 6 percent.
Example 4
S1, adding silicon nanoparticles with the D50 of 100nm into the graphene oxide aqueous dispersion, and then obtaining the silicon-based material-graphene oxide dispersion under the high-speed shearing force, wherein the weight ratio of silicon: graphene oxide mass = 80%: 20%, the initial concentration of the graphene oxide solution is 0.1g/ml, the solid content of the mixed solution is 50%, and then the mixed solution is dispersed for 24 hours at the speed of 2000rpm to obtain a uniform graphene-silicon nanoparticle dispersion solution;
s2, carrying out first spray drying on the mixed solution obtained in the step S1 at 120 ℃, wherein the diameter of the graphene oxide coated silicon nano particles obtained after drying is 1.5 um; carbonizing for the first time at 800 ℃ in an argon atmosphere to obtain graphene-coated nano silicon particles with the particle size of about 1.2um;
s3, adding a proper amount of water into the graphene-coated silicon carbon nano particles obtained in the step S2, the artificial graphite and the SBR adhesive, and kneading and stirring in a stirring tank, wherein the ratio of graphene silicon carbon: graphite: adhesive = 5%: 80%: 15 percent, the kneading stirring speed is 20rpm, the kneading stirring solid content is 60 percent, the kneading time is 120min, and the particle size D50 of the graphite is 13 um;
s4, carrying out secondary spray drying on the kneaded mixture obtained in the step S3, wherein the drying temperature is 120 ℃, and the particle size of the silicon-carbon composite material obtained after spray drying is 16 um; further carbonizing for the second time at 800 ℃ in argon atmosphere to obtain the graphene-coated silicon carbon-graphite secondary particles, wherein the particle size D50 of the secondary particles is 15um, and the specific surface area is 3m2/g。
Example 5
S1, SiO nano-particles with the D50 of 50nm are added into the graphene oxide water dispersion liquid, and then the SiO-graphene oxide dispersion liquid is obtained under the high-speed shearing force, wherein the SiO: graphene oxide mass = 80%: 20%, the initial concentration of the graphene oxide solution is 0.1g/ml, the solid content of the mixed solution is 50%, and then the mixed solution is dispersed for 24 hours at the speed of 2000rpm to obtain uniform SiO-graphene oxide nanoparticle dispersion liquid;
s2, carrying out first spray drying on the mixed solution obtained in the step S1 at 120 ℃, wherein the diameter of the graphene oxide coated silicon oxide nano particles obtained after drying is 1.2um, carrying out first carbonization at 600 ℃ in an argon atmosphere to obtain graphene coated SiO particles with the particle size of about 1um, wherein the graphene in the composite material: the weight percentage of the silica is 40%: 60 percent;
s3, adding a proper amount of water into the graphene-coated SiO nanoparticles, the artificial graphite and the SBR adhesive obtained in the step S2, kneading and stirring in a stirring tank, and mixing the graphene-coated SiO composite material: graphite: adhesive = 10%: 80%: 10 percent, the kneading and stirring speed is 20rpm, the kneading and stirring solid content is 60 percent, the kneading time is 120min, and the particle size D50 of the graphite is 13 um;
s4, carrying out secondary spray drying on the kneaded mixture obtained in the step S3, wherein the drying temperature is 120 ℃, and the particle size of the silicon-carbon composite material obtained after spray drying is 17 um; further carbonizing for the second time at 800 ℃ in argon atmosphere to obtain the graphene-coated SiO-graphite secondary particles, wherein the particle size D50 of the secondary particles is 16 mu m, and the specific surface area is 1.5m2/g。
Comparative example 1
A graphene-coated silicon-graphite negative electrode material was prepared in substantially the same manner as in example 1, except that the graphene and silicon were directly physically mixed and then dispersed at a high speed in step 1, and the processes such as spray drying and carbonization were not performed.
Comparative example 2
A graphene-coated silicon-graphite negative electrode material was prepared in substantially the same manner as in example 1, except that spray drying and carbonization steps were not performed after completion of step 3. The mixture was directly dried to a material.
The obtained material is mixed with adhesive and conductive agent in the same proportion, then coated on a copper current collector, rolled and punched to form an electrode plate, and then a button half cell is assembled by taking a lithium plate as a negative electrode to carry out charge-discharge capacity test. Table 1 shows physical parameters and electrochemical properties of the graphene-coated nano silicon-graphite composite material obtained in each example and comparative example.
Table 1 different examples and comparative example data
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (12)
1. A silicon-carbon negative electrode material is characterized in that: the silicon-carbon negative electrode material comprises the following raw materials in percentage by mass: graphene silicon carbon negative electrode nano composite material: graphite: adhesive = (5% -80%): (90% -10%): (5% -30%), the sum of the mass percentages of the graphene silicon carbon negative electrode nano composite material, the graphite and the adhesive is 100%; the graphene silicon carbon cathode nano composite material comprises the following raw materials in percentage by weight: and (3) graphene oxide: the silicon-based negative electrode material (5-90%) is (95-10%), and the sum of the mass percentages of the graphene oxide and the silicon-based negative electrode material in the graphene silicon carbon negative electrode nano composite material is 100%.
2. The preparation method of the silicon-carbon negative electrode material according to claim 1, characterized by comprising the following steps:
s1, adding a silicon-based negative electrode material into the graphene oxide solution, mixing to obtain a dispersion liquid, wherein the mass percentage of the graphene oxide to the silicon-based negative electrode material in the dispersion liquid is (5% -90%) to (95% -10%), the sum of the mass percentages of the silicon-based negative electrode material and the graphene oxide is 100%, and uniformly stirring the dispersion liquid;
s2, sequentially carrying out primary spray drying and primary carbonization on the dispersion liquid stirred and mixed in the step S1 to obtain the graphene silicon carbon negative electrode nano composite material of the graphene-coated silicon-based negative electrode material;
s3, kneading and stirring the graphene silicon carbon cathode nano composite material prepared in the step S2, graphite and an adhesive fully at a high solid content for 60-600 min, wherein the kneading and stirring speed is 10-50 rpm, the solid content of the kneading and stirring is 40-80%; wherein the graphene silicon carbon negative electrode nano composite material comprises the following components in percentage by weight: graphite: the adhesive comprises the following components in percentage by mass (5-80%): (90% -10%): (5% -30%), the sum of the mass percentages of the graphene silicon carbon negative electrode nano composite material, the graphite and the adhesive is 100%;
and S4, carrying out secondary spray drying and secondary carbonization on the mixture prepared by kneading and stirring the high solid content in the step S3 in sequence to obtain the silicon-carbon negative electrode material.
3. The preparation method of the silicon-carbon negative electrode material according to claim 2, characterized in that: in the step S1, the graphene oxide in the dispersion liquid is carbonized for the first time in the step S2 to prepare graphene coated outside the silicon-based negative electrode material, and the mass percentage of the graphene and the silicon-based negative electrode material in the graphene silicon carbon negative electrode nanocomposite is (1.5% -85%): (98.5% -15%), wherein the sum of the mass percentages of the graphene and the silicon-based negative electrode material is 100%; in the step S3, the adhesive is carbonized for the second time in the step S4 to prepare amorphous carbon, and the graphene silicon carbon negative electrode nano composite material in the silicon carbon negative electrode material: graphite: the amorphous carbon comprises (6-80%) by mass: (92-15%): (2% -25%), and the sum of the mass percentages of the graphene silicon carbon negative electrode nano composite material, the graphite and the amorphous carbon is 100%.
4. The preparation method of the silicon-carbon negative electrode material according to claim 2, characterized in that: in the step S1, the solvent of the dispersion liquid is one or a mixture of several of water, ethanol and azomethyl pyrrolidone, the dispersion speed of the mixed liquid is 2000-5000 rpm, the solid content of the dispersion liquid is 20-80%, and the dispersion time is 3-72 h.
5. The method for preparing silicon-carbon negative electrode material according to claim 2, wherein the method is characterized in thatIn the following steps: in the step S1, the particle size of the silicon-based negative electrode material is 10 to 200nm, and the silicon-based nanoparticles in the silicon-based negative electrode material are silicon or silicon oxide SiOXWherein x is>0。
6. The preparation method of the silicon-carbon negative electrode material as claimed in claim 5, wherein the preparation method comprises the following steps: the silicon-based nano particles are oxide SiO of siliconXWherein x is 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1 or 2.
7. The preparation method of the silicon-carbon negative electrode material according to claim 2, characterized in that: in the step S1, the graphene oxide solution is 10% to 50% by mass.
8. The preparation method of the silicon-carbon negative electrode material according to claim 2, characterized in that: in the step S2, the first spray drying process is performed in an inert atmosphere, the drying temperature is 80 to 300 ℃, wherein the particle size of the obtained graphene oxide/silicon-based nanoparticles is 300nm to 1.5 um; the primary carbonization temperature is 300-1000 ℃, and the particle size of the carbonized graphene/silicon-based nanoparticles is 30-500 nm.
9. The preparation method of the silicon-carbon negative electrode material according to claim 2, characterized in that: in the step S3, the graphite is one or a mixture of several of artificial graphite, natural graphite, and mesocarbon microbeads, wherein the particle size D50 of the graphite is 8-20 um, and the graphitization degree is greater than 90%.
10. The preparation method of the silicon-carbon negative electrode material according to claim 2, characterized in that: in the step S3, the adhesive is one or more of polyvinylidene fluoride, polytetrafluoroethylene, styrene butadiene rubber, sodium carboxymethylcellulose, or sodium alginate.
11. The silicon-carbon anode material of claim 2The preparation method is characterized by comprising the following steps: in the step S4, the second spray drying process is performed in an inert atmosphere, the drying temperature is 80-300 ℃, and the particle size of the silicon-carbon composite material obtained after drying is 10-25 um; the carbonization temperature of the second carbonization is 300-1000 ℃, the particle size D50 of the obtained graphene-coated silicon carbon/graphite particles is 10-20 um, and the specific surface area is 1-5 m2/g。
12. The method for preparing the silicon-carbon negative electrode material according to claim 8 or 11, wherein the method comprises the following steps: the dry inert atmosphere is helium, argon, nitrogen or a mixed gas of three gases.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911259751.4A CN111063872A (en) | 2019-12-10 | 2019-12-10 | Silicon-carbon negative electrode material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911259751.4A CN111063872A (en) | 2019-12-10 | 2019-12-10 | Silicon-carbon negative electrode material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111063872A true CN111063872A (en) | 2020-04-24 |
Family
ID=70300461
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911259751.4A Pending CN111063872A (en) | 2019-12-10 | 2019-12-10 | Silicon-carbon negative electrode material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111063872A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112736231A (en) * | 2021-01-12 | 2021-04-30 | 杭州新川新材料有限公司 | Preparation method of silicon monoxide negative electrode material of lithium ion battery |
| CN113839034A (en) * | 2021-09-23 | 2021-12-24 | 深圳华算科技有限公司 | Sodium ion battery negative electrode material, preparation method thereof and sodium ion battery |
| CN114094034A (en) * | 2020-08-24 | 2022-02-25 | 芯量科技股份有限公司 | Method for manufacturing multilayer long-cycle silicon-carbon negative electrode material |
| CN114613971A (en) * | 2022-03-31 | 2022-06-10 | 南京工业大学 | Preparation method and application of compact and stable pomegranate-shaped silicon-graphene composite electrode material |
| CN114914418A (en) * | 2022-05-16 | 2022-08-16 | 合肥国轩高科动力能源有限公司 | Silicon-based nano composite negative electrode material and preparation method thereof |
| CN114975962A (en) * | 2022-06-24 | 2022-08-30 | 内蒙古瑞盛天然石墨应用技术研究院 | Method for preparing silicon-carbon cathode material by using photovoltaic waste silicon powder and graphene oxide |
| CN117276523A (en) * | 2023-06-20 | 2023-12-22 | 湖北斯诺新材料科技有限公司 | Preparation method and application of silicon-carbon composite material |
| CN114094034B (en) * | 2020-08-24 | 2024-04-12 | 芯量科技股份有限公司 | Method for manufacturing multi-layer long-cycle silicon-carbon anode material |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102244240A (en) * | 2011-06-15 | 2011-11-16 | 中南大学 | Lithium ion battery composite anode material and preparation method thereof |
| CN102306757A (en) * | 2011-08-26 | 2012-01-04 | 上海交通大学 | Silicon graphene composite anode material of lithium ion battery and preparation method of silicon graphene composite anode material |
| CN103050666A (en) * | 2012-12-12 | 2013-04-17 | 中南大学 | Preparation method of silicon and carbon-coated graphene composite cathode material |
| CN103346305A (en) * | 2013-07-01 | 2013-10-09 | 华南师范大学 | Preparation and application of lithium battery silicon-carbon composite material taking synthetic graphite as carrier |
| CN105489866A (en) * | 2016-01-19 | 2016-04-13 | 陕西煤业化工技术研究院有限责任公司 | Lithium ion battery, anode composite thereof and preparation method |
| CN107611394A (en) * | 2017-09-08 | 2018-01-19 | 成都硅宝科技股份有限公司 | A kind of nuclear shell structure nano silicon/graphene composite negative pole of carbon coating and preparation method thereof |
| CN108172834A (en) * | 2018-01-26 | 2018-06-15 | 山东星火科学技术研究院 | A kind of low cost graphene is modified the preparation method of negative material |
-
2019
- 2019-12-10 CN CN201911259751.4A patent/CN111063872A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102244240A (en) * | 2011-06-15 | 2011-11-16 | 中南大学 | Lithium ion battery composite anode material and preparation method thereof |
| CN102306757A (en) * | 2011-08-26 | 2012-01-04 | 上海交通大学 | Silicon graphene composite anode material of lithium ion battery and preparation method of silicon graphene composite anode material |
| CN103050666A (en) * | 2012-12-12 | 2013-04-17 | 中南大学 | Preparation method of silicon and carbon-coated graphene composite cathode material |
| CN103346305A (en) * | 2013-07-01 | 2013-10-09 | 华南师范大学 | Preparation and application of lithium battery silicon-carbon composite material taking synthetic graphite as carrier |
| CN105489866A (en) * | 2016-01-19 | 2016-04-13 | 陕西煤业化工技术研究院有限责任公司 | Lithium ion battery, anode composite thereof and preparation method |
| CN107611394A (en) * | 2017-09-08 | 2018-01-19 | 成都硅宝科技股份有限公司 | A kind of nuclear shell structure nano silicon/graphene composite negative pole of carbon coating and preparation method thereof |
| CN108172834A (en) * | 2018-01-26 | 2018-06-15 | 山东星火科学技术研究院 | A kind of low cost graphene is modified the preparation method of negative material |
Non-Patent Citations (2)
| Title |
|---|
| ZHOULU WANG等: "Sub-micron silicon/pyrolyzed carbon@natural graphite self-assembly composite anode material for lithium-ion batteries", 《CHEMICAL ENGINEERING JOURNAL》 * |
| 李肖 等: "NaF-Si-C-RGO杂化材料的制备及电化学性能", 《新型炭材料》 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114094034A (en) * | 2020-08-24 | 2022-02-25 | 芯量科技股份有限公司 | Method for manufacturing multilayer long-cycle silicon-carbon negative electrode material |
| CN114094034B (en) * | 2020-08-24 | 2024-04-12 | 芯量科技股份有限公司 | Method for manufacturing multi-layer long-cycle silicon-carbon anode material |
| CN112736231A (en) * | 2021-01-12 | 2021-04-30 | 杭州新川新材料有限公司 | Preparation method of silicon monoxide negative electrode material of lithium ion battery |
| CN113839034A (en) * | 2021-09-23 | 2021-12-24 | 深圳华算科技有限公司 | Sodium ion battery negative electrode material, preparation method thereof and sodium ion battery |
| CN114613971A (en) * | 2022-03-31 | 2022-06-10 | 南京工业大学 | Preparation method and application of compact and stable pomegranate-shaped silicon-graphene composite electrode material |
| CN114613971B (en) * | 2022-03-31 | 2023-04-07 | 南京工业大学 | Preparation method and application of compact and stable pomegranate-shaped silicon-graphene composite electrode material |
| CN114914418A (en) * | 2022-05-16 | 2022-08-16 | 合肥国轩高科动力能源有限公司 | Silicon-based nano composite negative electrode material and preparation method thereof |
| CN114914418B (en) * | 2022-05-16 | 2023-06-02 | 合肥国轩高科动力能源有限公司 | Silicon-based nano composite anode material and preparation method thereof |
| CN114975962A (en) * | 2022-06-24 | 2022-08-30 | 内蒙古瑞盛天然石墨应用技术研究院 | Method for preparing silicon-carbon cathode material by using photovoltaic waste silicon powder and graphene oxide |
| CN117276523A (en) * | 2023-06-20 | 2023-12-22 | 湖北斯诺新材料科技有限公司 | Preparation method and application of silicon-carbon composite material |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5509458B2 (en) | Negative electrode material and manufacturing method thereof | |
| CN111063872A (en) | Silicon-carbon negative electrode material and preparation method thereof | |
| CN106356519B (en) | Preparation method of expanded graphite/silicon @ carbon negative electrode material for lithium ion battery | |
| Zhang et al. | Preparation of a porous Sn@ C nanocomposite as a high-performance anode material for lithium-ion batteries | |
| CN107221654B (en) | Three-dimensional porous nest-shaped silicon-carbon composite negative electrode material and preparation method thereof | |
| CN104966824A (en) | Nitrogen-doped porous carbon sphere and cobaltous oxide nano-composite anode material based on chitosan and derivatives thereof and preparation method thereof | |
| CN107959027B (en) | Silicon-based negative electrode binder of lithium ion battery and preparation method of negative plate containing binder | |
| CN102299306A (en) | Nano-silicon composite lithium ion battery cathode material with poly (3,4-ethylenedioxythiophene) as coating and carbon source and preparation method thereof | |
| CN104868112A (en) | Carbon-coated titanium dioxide nanosheet array and graphene composite electrode material and preparation method thereof | |
| CN105702958B (en) | Preparation method and application of tin dioxide quantum dot solution and composite material thereof | |
| Fan et al. | One‐pot hydrothermal synthesis of ZnS nanospheres anchored on 3D conductive MWCNTs networks as high‐rate and cold‐resistant anode materials for sodium‐ion batteries | |
| Jun et al. | Preparing a composite including SnS2, carbon nanotubes and S and using as cathode material of lithium-sulfur battery | |
| Chen et al. | Membrane and electrode engineering of high-performance lithium-sulfur batteries modified by stereotaxically-constructed graphene | |
| CN111697218A (en) | Silicon-carbon negative electrode material and preparation method thereof | |
| CN105118966A (en) | Sn-C composite material with high N content of lithium battery cathode and preparation method of Sn-C composite material | |
| CN104282894B (en) | A kind of preparation method of porous Si/C complex microsphere | |
| Xie et al. | Nitrogen-doped carbon caging silicon nanoparticles for high performance lithium-ion battery anodes | |
| CN105810918B (en) | A kind of fabricated in situ TiO2The method and its application of mesomorphic carbon graphite alkene nano composite material | |
| Li et al. | Construction of a novel three-dimensional porous lead-carbon network for improving the reversibility of deep discharge lead-carbon batteries | |
| CN108963237B (en) | Preparation method of sodium ion battery negative electrode material | |
| CN112510187A (en) | Electrostatic self-assembly spherical molybdenum trioxide/MXene composite material and preparation method and application thereof | |
| CN112694080A (en) | Carbon microsphere with embedded conductive network structure, preparation method and energy storage application thereof | |
| CN110970599B (en) | Graphene-based composite negative electrode material, preparation method thereof and lithium ion battery | |
| CN110970611A (en) | Hierarchical silicon-carbon composite material and preparation method and application thereof | |
| CN112421002B (en) | High-capacity silicon-carbon material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200424 |
|
| RJ01 | Rejection of invention patent application after publication |