CN111276677B - Preparation method of carbon nano material/amorphous carbon/silicon monoxide composite material - Google Patents
Preparation method of carbon nano material/amorphous carbon/silicon monoxide composite material Download PDFInfo
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- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 title claims abstract description 108
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 102
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 78
- 229910003481 amorphous carbon Inorganic materials 0.000 title claims abstract description 64
- 239000002131 composite material Substances 0.000 title claims abstract description 61
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 65
- 239000002245 particle Substances 0.000 claims abstract description 38
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 23
- 239000002562 thickening agent Substances 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000011812 mixed powder Substances 0.000 claims description 19
- 239000000377 silicon dioxide Substances 0.000 claims description 19
- 239000002041 carbon nanotube Substances 0.000 claims description 16
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 16
- 238000000576 coating method Methods 0.000 claims description 16
- 238000003763 carbonization Methods 0.000 claims description 15
- 238000004898 kneading Methods 0.000 claims description 15
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 7
- 230000001681 protective effect Effects 0.000 claims description 7
- 238000011282 treatment Methods 0.000 claims description 6
- 239000002033 PVDF binder Substances 0.000 claims description 5
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 5
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 5
- 238000003541 multi-stage reaction Methods 0.000 claims description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 5
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- 229920002125 Sokalan® Polymers 0.000 claims description 3
- 239000001509 sodium citrate Substances 0.000 claims description 3
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 2
- 238000012216 screening Methods 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 14
- 239000011247 coating layer Substances 0.000 abstract description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 8
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 7
- 239000010406 cathode material Substances 0.000 abstract description 5
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
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- 230000001351 cycling effect Effects 0.000 description 3
- 238000005485 electric heating Methods 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- WDCKRYQAVLUEDJ-UHFFFAOYSA-N methyl(oxo)silicon Chemical compound C[Si]=O WDCKRYQAVLUEDJ-UHFFFAOYSA-N 0.000 description 3
- 239000007773 negative electrode material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000011149 active material Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 230000002779 inactivation Effects 0.000 description 1
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- 238000006138 lithiation reaction Methods 0.000 description 1
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- 238000000926 separation method Methods 0.000 description 1
- 229910021487 silica fume Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
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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
- H01M4/366—Composites as layered products
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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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
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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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
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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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- 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
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- 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 relates to the technical field of lithium ion battery cathode materials, and provides a carbon nano material/amorphous carbon/silicon monoxide composite material and a preparation method thereof, aiming at solving the problem that the existing silicon monoxide based composite material is easy to be separated from contact after being charged and discharged, so that silica particles lose electrochemical activity, wherein the carbon nano material/amorphous carbon/silicon monoxide composite material is prepared from the following components in parts by weight: 75-97 parts of silicon monoxide, 1-50 parts of a carbon source, 0.1-3 parts of a thickening agent and 0.1-5 parts of a carbon nano material. The composite material disclosed by the invention is based on the fact that the surface layer of the silicon oxide particles is coated with a layer of amorphous carbon, meanwhile, the carbon nano material is uniformly loaded on the surface of the silicon oxide particles, and the problem of structural pulverization failure in the charging and discharging processes of the material can be greatly improved due to the limiting effect of the amorphous carbon coating layer and the conductive effect of the carbon nano material, so that good electrochemical performance is shown.
Description
Technical Field
The invention relates to the technical field of lithium ion battery cathode materials, in particular to a preparation method of a carbon nano material/amorphous carbon/silicon monoxide composite material.
Background
In recent years, with the increasing demand for new energy automobiles and energy storage base stations, the energy field, in particular lithium ion batteries, attracts people's extensive attention. At present, the lithium ion battery cathode material widely applied in industry is a graphite carbon material, but the theoretical capacity of the lithium ion battery cathode material is low, and the search for a novel cathode material with excellent performance is a hotspot in the electrochemical field.
The silicon oxide has the advantages of high theoretical specific capacity, abundant raw material reserves, relatively low price, environmental friendliness and the like, so that the silicon oxide is a hotspot in research and industrialization of high-energy-density negative electrode materials. However, the problem to be solved is also existed in the use of the silicon monoxide as the negative electrode material of the lithium battery: large volume deformation (about 200%) occurs during charge and discharge, causing active materials to be pulverized and lose electrical contact, resulting in poor cycle performance. In addition, the problem of low conductivity of the silicon monoxide is also present, which limits the application of the silicon monoxide in the negative electrode of the lithium ion battery.
The carbon nano materials such as the carbon nano tube, the graphene, the carbon fiber and the like have excellent conductivity, good chemical stability and larger specific surface area, and provide a novel conductive agent for the active material of the lithium ion battery. However, in practical applications, the silicon oxide particles and the conductive agent on the electrode are easily separated from contact after charging and discharging, so that the silicon oxide particles lose electrochemical activity.
In the existing research on the silica-based composite material, the preparation method generally adopts a solid-phase, liquid-phase or gas-phase process to directly coat and carbonize on the surface of the silica, and a one-dimensional or two-dimensional carbon nano material structure is less introduced. In addition, it has been reported that the material structure is obtained by mixing a conductive agent into coated silica particles as a base material by physical means such as high-speed mixing and mechanical fusion. In the structure, the conductive agent is not combined on the particle surface in a chemical bond state, and is easy to separate from the particle surface to lose the conductive activity in the charge-discharge reaction process of the silicon monoxide, so that the advantages of the carbon nano material and the silicon monoxide composite material can not be exerted.
Disclosure of Invention
The invention provides a carbon nano material/amorphous carbon/silicon monoxide composite material with good electrochemical performance, aiming at overcoming the problem that the prior silicon monoxide composite material is easy to be separated from contact after charging and discharging and causes the electrochemical activity of silicon oxygen particles to be lost.
The invention also provides a preparation method of the carbon nano material/amorphous carbon/silicon monoxide composite material, the preparation process is simple to operate, no special requirements are required on equipment, the raw materials are easy to obtain and economic, and the preparation method is green, environment-friendly and easy to industrialize.
In order to achieve the purpose, the invention adopts the following technical scheme:
a carbon nano material/amorphous carbon/silicon monoxide composite material is prepared from the following components in parts by weight: 75-97 parts of silicon monoxide, 1-50 parts of a carbon source, 0.1-3 parts of a thickening agent and 0.1-5 parts of a carbon nano material.
According to the invention, the carbon nano material is loaded on the surface of the silicon monoxide particles through the thickening agent, and then the amorphous carbon is coated, so that the limitation buffer effect of the amorphous carbon coating and the electric conduction effect of the carbon nano material are combined, and the defect of the silicon monoxide can be well compensated. The carbon nano material is used as an effective conductive network to avoid the inactivation of the silicon monoxide. The limiting effect of the amorphous carbon is combined with the carbon nano material and the silicon monoxide particles, so that the pressure regulation and control capability of the silicon monoxide particles can be enhanced, and the pulverization of the silicon monoxide particles in the lithium ion insertion and separation processes can be effectively prevented.
Preferably, the median particle diameter of the silicon monoxide is controlled to be 1-10 μm; the carbon nano material is selected from one of carbon nano tube, graphene oxide and carbon fiber; the carbon nano material is in a tubular, fibrous or sheet structure.
Preferably, the carbon source is at least one of high-softening-point asphalt, medium-softening-point asphalt and low-softening-point asphalt; the softening point of the high-softening-point asphalt is 200-300 ℃; the medium softening point asphalt has a softening point of 120-200 ℃ and the low softening point asphalt has a softening point of 60-120 ℃.
Preferably, the carbon source has a median particle diameter of 0.1 to 20 μm. The carbon source has a median particle size too low to completely coat the surface of the silicon monoxide particles with the amorphous carbon layer. Too high a carbon source median particle size can cause the silica particles to adhere to each other, resulting in too large a composite particle size. Both of these conditions can negatively impact the final electrical properties of the composite.
Preferably, the thickener is one selected from sodium carboxymethylcellulose, sodium citrate, acrylic acid polymer and polyvinylidene fluoride.
Preferably, the preparation method of the carbon nano material/amorphous carbon/silicon monoxide composite material comprises the following steps: firstly, loading the carbon nano material on the surface of the silicon oxide particles, then adding a carbon source to carry out solid-phase coating carbonization to form an amorphous carbon coating layer, and obtaining the carbon nano material/amorphous carbon/silicon oxide composite material.
A preparation method of a carbon nano material/amorphous carbon/silicon monoxide composite material comprises the following steps:
(1) weighing the raw materials according to the proportion, adding the carbon nano material, the silica fume and the thickening agent into a double-planet stirrer, and starting revolution, autorotation, dispersion and mixing to obtain mixed powder; the time for dispersing and mixing is preferably 0.5-2 h;
(2) adding a solvent into the mixed powder obtained in the step (1), starting revolution and autorotation after the slurry state reaches a dough state, and carrying out high-viscosity shearing kneading; the time for high-viscosity shearing kneading is preferably 2-4 h; high-viscosity shearing kneading is realized by adding a thickening agent and controlling the solid content of the slurry, and the carbon nano material can be more uniformly loaded on the surface of the silicon oxide particles through the high-viscosity shearing kneading;
(3) drying the mixed powder treated in the step (2) at the temperature of 90-110 ℃, and then crushing and grading to obtain the carbon nano material/silicon monoxide composite material;
(4) adding the carbon nano material/silicon monoxide composite material obtained in the step (3) and a carbon source into low-temperature thermal composite reaction equipment, carrying out low-temperature solid-phase coating treatment, mixing and heating to 200-600 ℃ under a protective atmosphere, preserving heat for 2-6 h, and naturally cooling to obtain a precursor; the protective gas is one of nitrogen, argon and helium;
(5) and (4) transferring the precursor obtained in the step (4) into carbonization equipment, heating to 600-1200 ℃ in a protective atmosphere, preserving heat for 4-24 h, naturally cooling, and screening to obtain the carbon nanomaterial/amorphous carbon/silicon monoxide composite material. The protective gas is one of nitrogen, argon and helium; in the step, the thickening agent and a carbon source are converted into amorphous carbon through carbonization, and an amorphous carbon coating layer is formed on the surface of the carbon nano material/silicon monoxide composite material.
According to the invention, a solvent is added into a mixture of the silicon oxide, the carbon nano material and the thickening agent, high-viscosity kneading is carried out in a liquid phase state, the carbon nano material is loaded on the surface of silicon oxide particles, and then a carbon source is added for solid phase coating carbonization, so that the carbon nano material-amorphous carbon-silicon oxide composite material is prepared. Under the structural model, the carbon nano material is firmly combined with amorphous carbon and silicon oxide particles, the amorphous carbon coating layer has a limiting effect on the volume deformation of the silicon oxide, the stress generated in the lithiation process of the silicon oxide can be regulated and controlled, and the carbon nano tubes loaded on the surfaces of the particles can construct an excellent conductive network among the particles and between the particles and a current collector. According to the invention, the thickening agent is added to control the solid content to carry out high-viscosity kneading, then the solid-phase coating process is carried out, the carbon nano material-amorphous carbon-silicon oxide composite structure is designed, the surface layer of the silicon oxide particles is coated with a layer of amorphous carbon, and meanwhile, the carbon nano material is uniformly loaded on the surface of the silicon oxide particles. The restriction effect of the amorphous carbon coating layer and the conductive effect of the carbon nano material can greatly improve the problem of structural pulverization failure in the charge-discharge process of the material, and avoid the carbon nano material and the silicon monoxide particles from being separated to lose electrochemical activity.
Preferably, when the selected thickening agent is sodium carboxymethylcellulose, sodium citrate and an acrylic acid polymer, in the step (2), the solvent is water and is a water-soluble substance based on the thickening agent; when the used thickening agent is polyvinylidene fluoride, N-methyl pyrrolidone is required to be selected as a solvent, and the coating process of the amorphous carbon coating layer cannot be continuously realized because the polyvinylidene fluoride is insoluble in water and cannot provide a thickening effect.
Preferably, in the step (2), the mass ratio of the solvent to the mixed powder is (0.35-0.65): 1. the solid content of the mixed powder slurry is too high and the mixed powder slurry is not easy to agglomerate due to too small addition amount of the solvent; the excessive addition of the solvent can cause the solid content of the mixed powder slurry to be too low, the mixed powder slurry is in a liquid state and is not easy to form; the high-viscosity shearing kneading cannot be realized when the adding amount of the solvent is too much or too little, and the coating process of the amorphous carbon coating layer cannot be continuously realized.
Preferably, in the steps (1) and (2), the revolution speed is 20-40 rpm; the rotation speed of the rotation is 100-1000 rpm; the revolution and rotation speeds are too low, so that the shearing and kneading effect of the mixed powder slurry is poor, and the coating effect may not reach the expectation; the revolution and rotation speeds are too high, which can lead to the pulverization of the silicon oxide particles and influence the electrochemical performance of the composite material.
Preferably, in the step (4), the low-temperature thermal composite reaction equipment is selected from one of a roller furnace, a vertical kettle and a vertical small kettle.
Preferably, in the step (5), the carbonization device is one selected from a tubular carbonization furnace, a box-type carbonization furnace, a roller kiln and a pusher kiln.
Therefore, the invention has the following beneficial effects:
(1) the composite material is based on the fact that the surface layer of the silicon oxide particles is coated with a layer of amorphous carbon, meanwhile, the carbon nano material is uniformly loaded on the surface of the silicon oxide particles, the problem of structural pulverization failure in the charging and discharging processes of the material can be greatly improved due to the limiting effect of the amorphous carbon coating layer and the conductive effect of the carbon nano material, and good electrochemical performance is shown;
(2) the preparation process is simple and unique, liquid phase kneading and solid phase low-temperature coating are combined, high-viscosity shearing kneading is realized by adding the thickening agent and controlling the solid content of slurry, the carbon nano material can be more uniformly loaded on the surface of the silicon monoxide particles through kneading, then the carbon source is added to complete solid phase coating, and the thickening agent and the carbon source are converted into amorphous carbon through carbonization, so that the whole material preparation process is simple to operate, the equipment is common industrial equipment, the raw materials are economical, the pollution is small, and the industrialization is easy;
(3) the reversible capacity of the carbon nano material/amorphous carbon/silicon monoxide composite material reaches 1291.6mAh/g, the first efficiency is 79.1%, 1137.9mAh/g is still available after 50 weeks of circulation, and the carbon nano material/amorphous carbon/silicon monoxide composite material has good circulation performance. The amorphous carbon/silicon monoxide composite material prepared by pure solid phase coating also has the reversible capacity of 1411.0mAh/g, but only 409.8mAh/g is left after the circulation for 50 weeks.
Drawings
FIG. 1 is an XRD spectrum of the carbon nanotube/amorphous carbon/silica composite material prepared in example 1.
Fig. 2 is an SEM image of the carbon nanotube/amorphous carbon/silica composite material prepared in example 1 at different magnifications.
Fig. 3 is a charge-discharge curve of a button cell using the carbon nanotube/amorphous carbon/silicon oxide composite material prepared in example 1 as a negative electrode material.
FIG. 4 is a graph comparing the cycle curves of the carbon nanotube/amorphous carbon/silica composite obtained in example 1 and the amorphous carbon/silica composite obtained in comparative example 1.
Detailed Description
The technical solution of the present invention is further specifically described below by using specific embodiments and with reference to the accompanying drawings.
In the present invention, all the equipment and materials are commercially available or commonly used in the art, and the methods in the following examples are conventional in the art unless otherwise specified.
Example 1
(1) Adding 60g of carbon nanotube (length 2-20 μm, diameter 1-100 nm), 30g of sodium carboxymethylcellulose and 2.67kg of silicon monoxide powder (median diameter 4 μm) into a 5L double-planetary mixer, setting revolution at 30rpm and rotation at 300rpm, and stirring, dispersing and mixing for 30 minutes to obtain mixed powder;
(2) adding 1.4kg of deionized water into the mixed powder obtained in the step (1), setting revolution at 30rpm and rotation at 100rpm, kneading and stirring for 2 hours to obtain a dough-like uniform mixture;
(3) transferring the dough-like mixture into an electric heating constant-temperature drying oven for drying at 100 ℃, and then crushing and grading;
(4) transferring the powder obtained by crushing and 220g of pitch with medium softening point (the median particle size is 0.1 mu m) into VH thermal compound equipment, carrying out low-temperature solid-phase coating treatment, mixing and heating to 300 ℃ under the nitrogen atmosphere, preserving heat for 6h, and naturally cooling to obtain a precursor;
(5) transferring the precursor into a tubular carbonization furnace, heating to 900 ℃ in nitrogen atmosphere, and preserving heat for 10 hours. Naturally cooling, and sieving with 250 mesh sieve to obtain the composite material.
XRD and SEM characterization were performed on the carbon nanotube/amorphous carbon/silica composite material prepared in this example, and the results are shown in fig. 1 and 2. As can be seen from fig. 1, the carbon nanotube/amorphous carbon/silicon monoxide composite material successfully prepared by the method has no obvious impurity peak, and the (002) crystal plane peak of carbon can be observed at 26.8 ℃, which indicates that an amorphous carbon coating layer exists on the surface. Fig. 2 is an SEM image of the prepared carbon nanotube/amorphous carbon/silica composite material, and it can be seen that the carbon nanotubes are uniformly loaded on the surface of the silica particles and form an alternately linked conductive network structure.
The carbon nanotube/amorphous carbon/silica composite material prepared in the example, carbon black, CMC and SBR were homogenized, coated and rolled in a ratio of 96:1:1.5:1.5 to prepare a working electrode, a lithium sheet was used as a counter electrode to prepare a button cell, and charge and discharge tests were performed.
From the constant current charge-discharge diagram in fig. 3, it can be seen that the reversible discharge specific capacity of the carbon nanotube/amorphous carbon/silicon monoxide composite material prepared in the embodiment reaches 1291.6 mAh/g. As shown in fig. 4, after 50 weeks of cycling, the specific capacity of the carbon nanotube-amorphous carbon-silicon oxide was still 1137.9mAh/g, and the cycle capacity retention rate was still above 88%.
Example 2
(1) Under a dry environment (relative humidity is less than 10% RH), adding 120g of graphene (the number n of graphite layers is less than 10), 45g of polyvinylidene fluoride and 3.0kg of silicon oxide powder (the median particle size is 1 mu m) into a 5L double-planet stirrer, setting revolution at 20rpm and rotation at 100rpm, and stirring, dispersing and mixing for 2h to obtain mixed powder;
(2) adding 1.8kg of N-methyl pyrrolidone into the mixed powder obtained in the step (1), setting revolution at 25rpm and rotation at 200rpm, kneading and stirring for 4 hours to obtain a dough-like uniform mixture;
(3) transferring the dough-like mixture into an electric heating constant-temperature drying oven for drying at 110 ℃, and then crushing and grading;
(4) transferring the powder obtained by crushing and 191g of low-softening-point asphalt (the median particle size is 20 microns) into a roller furnace, carrying out low-temperature solid phase coating treatment, mixing and heating to 600 ℃ under the argon atmosphere, keeping the temperature for 2 hours, continuously heating to 550 ℃, keeping the temperature for 3 hours, and naturally cooling to obtain a precursor;
(5) and transferring the precursor into a tubular carbonization furnace, heating to 600 ℃ under the argon atmosphere, and preserving heat for 24 hours. Naturally cooling, and sieving with a 250-mesh sieve to obtain the graphene/amorphous carbon/silicon oxide composite material.
The graphene/amorphous carbon/silica composite material prepared in the embodiment, carbon black, CMC and SBR are homogenized, coated and rolled according to a ratio of 96:1:1.5:1.5 to prepare a working electrode, a lithium sheet is used as a counter electrode to prepare a button cell, and a charge and discharge test is performed.
Through tests, the reversible discharge specific capacity of the graphene/amorphous carbon/silicon monoxide composite material prepared by the embodiment reaches 1228.6mAh/g, and the first efficiency is 79.9%.
Example 3
(1) Adding 60g of carbon fiber VGCF (length is 2-20 μm, diameter is 1-100 nm), 40g of sodium carboxymethylcellulose and 2.5kg of silicon monoxide powder (median particle size is 10 μm) into a 5L double-planet stirrer, setting revolution at 40rpm and rotation at 1000rpm, and stirring, dispersing and mixing for 30 minutes to obtain mixed powder;
(2) adding 1.2kg of deionized water into the mixed powder obtained in the step (1), setting revolution at 30rpm and rotation at 100rpm, kneading and stirring for 3 hours to obtain a dough-like uniform mixture;
(3) transferring the dough-like mixture into an electric heating constant-temperature drying oven for drying at 90 ℃, and then crushing and grading;
(4) transferring the powder obtained by crushing and 340g of low-softening-point asphalt (the median particle size is 15 mu m) into a test roller furnace, carrying out low-temperature solid-phase coating treatment, mixing and heating to 200 ℃ under a protective atmosphere, preserving heat for 5h, and naturally cooling to obtain a precursor;
(5) transferring the precursor into a roller kiln, heating to 1050 ℃ under the nitrogen atmosphere, and carbonizing for 12 h. Naturally cooling, and sieving with a 250-mesh sieve to obtain the carbon fiber/amorphous carbon/silicon monoxide composite material.
The carbon fiber/amorphous carbon/silica composite material prepared in the embodiment, carbon black, CMC and SBR are homogenized, coated and rolled according to the ratio of 96:1:1.5:1.5 to prepare a working electrode, a lithium sheet is used as a counter electrode to prepare a button cell, and charging and discharging tests are carried out.
Through tests, the reversible discharge specific capacity of the carbon fiber/amorphous carbon/silicon monoxide composite material prepared by the embodiment reaches 1321.6mAh/g, and the first efficiency is 79.3%.
Comparative example 1
Adding 110g of pitch with a medium softening point and 1.35kg of silicon monoxide powder (the median particle size is 4 mu m) into a VH thermal composite reaction device, carrying out low-temperature solid phase coating treatment, mixing and heating to 300 ℃ under the nitrogen atmosphere, preserving heat for 6h, and naturally cooling to obtain a precursor. And then transferring the precursor into a tubular carbonization furnace, heating to 900 ℃ in nitrogen atmosphere, and preserving heat for 10 hours. Naturally cooling, and sieving with a 250-mesh sieve to obtain the amorphous carbon/silicon monoxide composite material.
The amorphous carbon/silica composite material prepared by the comparative example, carbon black, CMC and SBR are homogenized, coated and rolled according to the proportion of 96:1:1.5:1.5 to prepare a working electrode, a lithium sheet is used as a counter electrode to prepare a button cell, and a charge and discharge test is carried out.
The test results are shown in FIG. 4. the amorphous carbon/silica composite of this comparative example also had a reversible specific capacity of 1411.0mAh/g, but after 50 weeks of cycling, only 409.8mAh/g remained. After the carbon nanotube/amorphous carbon/silicon monoxide composite material prepared in the embodiment 1 is cycled for 50 weeks, the specific capacity is still 1137.9mAh/g, and the retention rate of the cycling capacity is still more than 88%.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and other variations and modifications may be made without departing from the spirit of the invention as set forth in the claims.
Claims (8)
1. A preparation method of a carbon nano material/amorphous carbon/silicon monoxide composite material is characterized by comprising the following steps:
(1) weighing the raw materials according to the proportion, adding the carbon nano material, the silica powder and the thickening agent into a double-planet stirrer, and starting revolution, autorotation, dispersion and mixing to obtain mixed powder;
(2) adding a solvent into the mixed powder obtained in the step (1), and after the slurry state reaches a dough state, starting revolution and autorotation to perform high-viscosity shearing kneading;
(3) drying the mixed powder treated in the step (2) at the temperature of 90-110 ℃, and then crushing and grading to obtain a carbon nano material/silicon monoxide composite material;
(4) adding the carbon nano material/silicon monoxide composite material obtained in the step (3) and a carbon source into low-temperature thermal composite reaction equipment, carrying out low-temperature solid-phase coating treatment, mixing and heating to 200-600 ℃ under a protective atmosphere, preserving heat for 2-6 h, and naturally cooling to obtain a precursor;
(5) transferring the precursor obtained in the step (4) into carbonization equipment, heating to 600-1200 ℃ under a protective atmosphere, preserving heat for 4-24 h, naturally cooling, and screening to obtain a carbon nano material/amorphous carbon/silicon monoxide composite material;
the carbon nano material/amorphous carbon/silicon monoxide composite material is prepared from the following components in parts by weight: 75-97 parts of silicon monoxide, 1-50 parts of a carbon source, 0.1-3 parts of a thickening agent and 0.1-5 parts of a carbon nano material.
2. The method for preparing a carbon nanomaterial/amorphous carbon/silica composite material according to claim 1, wherein the median particle size of the silica is controlled to be 1-10 μm; the carbon nano material is selected from one of carbon nano tube, graphene oxide and carbon fiber; the carbon nano material is in a tubular, fibrous or sheet structure.
3. The method for preparing a carbon nanomaterial/amorphous carbon/silica composite material according to claim 1, wherein the carbon source is at least one of high-softening-point pitch, medium-softening-point pitch, and low-softening-point pitch; the carbon source has a median particle size of 0.1-20 μm.
4. The method for preparing a carbon nanomaterial/amorphous carbon/silica composite material according to claim 1, wherein the thickener is one selected from sodium carboxymethylcellulose, sodium citrate, acrylic acid polymer and polyvinylidene fluoride.
5. The method for preparing a carbon nanomaterial/amorphous carbon/silica composite material according to claim 1, wherein in the step (2), the solvent is water or N-methylpyrrolidone; the mass ratio of the solvent to the mixed powder is (0.35-0.65): 1.
6. the method for preparing a carbon nanomaterial/amorphous carbon/silicon monoxide composite material according to claim 1, wherein in the steps (1) and (2), the revolution speed is 20-40 rpm; the rotation speed of the rotation is 100-1000 rpm.
7. The method for preparing a carbon nanomaterial/amorphous carbon/silicon monoxide composite material according to claim 1, wherein in the step (4), the low-temperature thermal composite reaction equipment is selected from one of a roller furnace, a vertical kettle and a small vertical kettle.
8. The method for preparing a carbon nanomaterial/amorphous carbon/siliconoxide composite material according to claim 1, wherein in the step (5), the carbonization device is selected from one of a tubular carbonization furnace, a box-type carbonization furnace, a roller kiln and a pushed slab kiln.
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| CN113206249B (en) * | 2021-04-19 | 2023-04-28 | 湖州金灿新能源科技有限公司 | Lithium battery silicon-oxygen composite anode material with good electrochemical performance and preparation method thereof |
| CN114122397B (en) * | 2021-10-12 | 2023-11-10 | 湖南金硅科技有限公司 | Carbon nanotube-connected double-carbon-layer-coated mesoporous silica composite material and preparation method and application thereof |
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005075720A (en) * | 2003-08-29 | 2005-03-24 | Yoshiaki Morisada | SiC-COATED CARBON NANOTUBE, MANUFACTURING METHOD THEREFOR AND COMPOSITE MATERIAL THEREOF |
| CN102983317A (en) * | 2012-12-05 | 2013-03-20 | 奇瑞汽车股份有限公司 | Silicon-based composite material and preparation method thereof, silicon-carbon composite material and lithium ion battery |
| CN103094533A (en) * | 2012-11-26 | 2013-05-08 | 中南大学 | Multi-core core-shell-structure silicon carbon composite negative pole material and preparation method thereof |
| EP2698848A1 (en) * | 2012-08-14 | 2014-02-19 | Samsung SDI Co., Ltd. | Negative active material for rechargeable lithium battery, and negative electrode and rechargeable lithium battery including same |
| CN103647056A (en) * | 2013-11-29 | 2014-03-19 | 深圳市贝特瑞新能源材料股份有限公司 | SiOx based composite negative electrode material, preparation method and battery |
| CN103855364A (en) * | 2014-03-12 | 2014-06-11 | 深圳市贝特瑞新能源材料股份有限公司 | SiOx-based composite material, preparation method and lithium ion battery |
| WO2017052278A1 (en) * | 2015-09-24 | 2017-03-30 | 주식회사 엘지화학 | Anode active material for lithium secondary battery and method for producing same |
| JP2017088437A (en) * | 2015-11-06 | 2017-05-25 | 国立大学法人 新潟大学 | Method for producing graphite-covered silicon composite body |
| CN109449385A (en) * | 2018-09-26 | 2019-03-08 | 桑顿新能源科技有限公司 | Carbon-coated unformed silicon/graphene composite negative pole and preparation method thereof and lithium ion battery |
| CN110600720A (en) * | 2019-09-20 | 2019-12-20 | 广东省稀有金属研究所 | Composite silicon-based material, negative electrode material, preparation methods of composite silicon-based material and negative electrode material, and lithium ion battery |
-
2020
- 2020-01-13 CN CN202010033890.1A patent/CN111276677B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005075720A (en) * | 2003-08-29 | 2005-03-24 | Yoshiaki Morisada | SiC-COATED CARBON NANOTUBE, MANUFACTURING METHOD THEREFOR AND COMPOSITE MATERIAL THEREOF |
| EP2698848A1 (en) * | 2012-08-14 | 2014-02-19 | Samsung SDI Co., Ltd. | Negative active material for rechargeable lithium battery, and negative electrode and rechargeable lithium battery including same |
| CN103594677A (en) * | 2012-08-14 | 2014-02-19 | 三星Sdi株式会社 | Negative active material for rechargeable lithium battery, negative electrode and rechargeable lithium battery |
| CN103094533A (en) * | 2012-11-26 | 2013-05-08 | 中南大学 | Multi-core core-shell-structure silicon carbon composite negative pole material and preparation method thereof |
| CN102983317A (en) * | 2012-12-05 | 2013-03-20 | 奇瑞汽车股份有限公司 | Silicon-based composite material and preparation method thereof, silicon-carbon composite material and lithium ion battery |
| CN103647056A (en) * | 2013-11-29 | 2014-03-19 | 深圳市贝特瑞新能源材料股份有限公司 | SiOx based composite negative electrode material, preparation method and battery |
| CN103855364A (en) * | 2014-03-12 | 2014-06-11 | 深圳市贝特瑞新能源材料股份有限公司 | SiOx-based composite material, preparation method and lithium ion battery |
| WO2017052278A1 (en) * | 2015-09-24 | 2017-03-30 | 주식회사 엘지화학 | Anode active material for lithium secondary battery and method for producing same |
| JP2017088437A (en) * | 2015-11-06 | 2017-05-25 | 国立大学法人 新潟大学 | Method for producing graphite-covered silicon composite body |
| CN109449385A (en) * | 2018-09-26 | 2019-03-08 | 桑顿新能源科技有限公司 | Carbon-coated unformed silicon/graphene composite negative pole and preparation method thereof and lithium ion battery |
| CN110600720A (en) * | 2019-09-20 | 2019-12-20 | 广东省稀有金属研究所 | Composite silicon-based material, negative electrode material, preparation methods of composite silicon-based material and negative electrode material, and lithium ion battery |
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