CN114447292B - Lithium ion battery negative electrode material and preparation method thereof - Google Patents
Lithium ion battery negative electrode material and preparation method thereof Download PDFInfo
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 48
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 9
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000004005 microsphere Substances 0.000 claims abstract description 90
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 81
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 62
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 39
- 239000004917 carbon fiber Substances 0.000 claims abstract description 39
- 239000010405 anode material Substances 0.000 claims abstract description 30
- 239000002131 composite material Substances 0.000 claims abstract description 23
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 17
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 17
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 9
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 156
- 229920005989 resin Polymers 0.000 claims description 105
- 239000011347 resin Substances 0.000 claims description 105
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 78
- RGSCXUOGQGNWFC-UHFFFAOYSA-N [Hf].[C] Chemical compound [Hf].[C] RGSCXUOGQGNWFC-UHFFFAOYSA-N 0.000 claims description 58
- 239000000243 solution Substances 0.000 claims description 58
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 57
- 239000005011 phenolic resin Substances 0.000 claims description 57
- 229920001568 phenolic resin Polymers 0.000 claims description 57
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 35
- 239000011259 mixed solution Substances 0.000 claims description 32
- 238000002156 mixing Methods 0.000 claims description 29
- 239000002296 pyrolytic carbon Substances 0.000 claims description 22
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 21
- 239000011812 mixed powder Substances 0.000 claims description 20
- 238000002791 soaking Methods 0.000 claims description 19
- 239000002904 solvent Substances 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 10
- 238000012545 processing Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 238000013329 compounding Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 24
- 239000003575 carbonaceous material Substances 0.000 description 15
- 239000000203 mixture Substances 0.000 description 15
- 239000012300 argon atmosphere Substances 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000006183 anode active material Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 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
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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
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
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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
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Abstract
The application relates to a lithium ion battery negative electrode material and a preparation method thereof, wherein the lithium ion battery negative electrode material comprises a carrier and an inlay; the inlay is inlaid on the carrier to form a composite material with an inlaid interlocking structure; the carrier comprises carbon fibers and/or carbon nanotubes; the inlay includes hafnium and carbon microspheres. According to the lithium ion battery anode material, hafnium and carbon microspheres are introduced to serve as inlays to be inlaid on a carrier formed by carbon fibers and/or carbon nanotubes, and the inlay interlocking structure composite material is formed by compounding, so that the energy density and the conductivity can be improved.
Description
Technical Field
The application relates to the field of lithium ion batteries, in particular to a lithium ion battery negative electrode material and a preparation method thereof.
Background
Lithium ion batteries have been widely used in notebook computers, smart phones, and other fields. The lithium ion battery mainly comprises a positive electrode, a negative electrode, electrolyte and a diaphragm, and mainly works by means of lithium ions moving between the positive electrode and the negative electrode. In the charge and discharge process, lithium ions are inserted and extracted back and forth between the two electrodes, and when the lithium ions are charged, the lithium ions are extracted from the positive electrode and inserted into the negative electrode through the electrolyte, and the negative electrode is in a lithium-rich state; the opposite is true when discharging. Wherein the traditional negative electrode material is graphite, and the theoretical specific capacity of the graphite can not fully meet the increasing requirement of high energy density of the power battery. Therefore, the development of the novel lithium ion battery cathode material with high capacity has important practical significance.
Disclosure of Invention
The application aims to solve the technical problem of providing an improved lithium ion battery anode material and further providing an improved lithium ion battery.
The technical scheme adopted for solving the technical problems is as follows: constructing a lithium ion battery anode material, which comprises a carrier and an inlay; the inlay is inlaid on the carrier to form a composite material with an inlaid interlocking structure; the carrier comprises carbon fibers and/or carbon nanotubes; the inlay includes hafnium and carbon microspheres.
Preferably, the inlay further comprises resin carbon and/or pyrolytic carbon.
Preferably, the carbon nanotubes have a diameter of 200-400 nm and a length of 1-3 μm.
Preferably, the carbon fibers have a diameter of 5-8 microns and a length of 10-15 microns.
Preferably, the carbon microsphere has a particle size of 600-900 nanometers.
The application also constructs a preparation method of the lithium ion battery anode material, which is used for preparing the lithium ion battery anode material and comprises the following steps:
s1, mixing hafnium-carbon resin and phenolic resin to form mixed resin, and dissolving the mixed resin in a first solvent to form a first mixed solution;
s2, adding carbon fibers and/or carbon nanotubes into the mixed solution, soaking for a set time to form carbon fibers coated with the mixed resin, and processing under a first temperature condition to form a first complex;
s3, treating the first composite material at a second temperature, and introducing a second solvent to obtain a second composite body;
s4, mixing the carbon microspheres and the phenolic microspheres to obtain mixed powder, dissolving the mixed powder in a third solvent, and uniformly stirring to form a second mixed solution;
s5, soaking the second composite body in the second mixed solution, and processing under the condition of a third temperature under the condition of surrounding of inert gas to form the composite material with the embedded interlocking structure.
Preferably, in the step S1, the mass ratio of the hafnium-carbon resin to the phenolic resin is 1:5-1:10;
the first solvent comprises an ethanol solution with a concentration of 5g/ml to 30 g/ml.
Preferably, in the step S2, the first temperature condition is 1200 to 1400 degrees.
Preferably, in the step S3, the first temperature condition is 1000-1100 degrees;
the second solvent is a mixed solution formed by mixing methanol and ethanol according to the volume ratio of 3:1-6:1.
Preferably, in the step S4, the mass ratio of the carbon microsphere to the phenolic microsphere is 1:1-1:3;
the third solvent is a solution prepared by dissolving phenolic resin in ethanol to form 10-20% by mass;
in the step S5, the third temperature condition is 800 to 1000 ℃.
The lithium ion battery anode material and the preparation method thereof have the following beneficial effects: according to the lithium ion battery anode material, hafnium and carbon microspheres are introduced to serve as inlays to be inlaid on a carrier formed by carbon fibers and/or carbon nanotubes, and the inlay interlocking structure composite material is formed by compounding, so that the energy density and the conductivity can be improved.
Drawings
The application will be further described with reference to the accompanying drawings and examples, in which:
FIG. 1 is an SEM of a lithium ion battery anode material according to some embodiments of the application;
fig. 2 is a process flow diagram of the negative electrode material of the lithium ion battery shown in fig. 1.
Detailed Description
For a clearer understanding of technical features, objects and effects of the present application, a detailed description of embodiments of the present application will be made with reference to the accompanying drawings.
Fig. 1 shows some preferred embodiments of the lithium ion battery anode material of the application. The lithium ion battery anode material can be used as an anode active material without adding an additional conductive agent, and has the advantages of high energy density, good conductivity and strong stability. The energy density of the lithium ion battery cathode material can be as high as 210W h/kg, and is improved by 1.45 times compared with that of the traditional lithium ion battery.
Further, in some embodiments, the lithium ion battery anode material includes a carrier and an inlay that can be inlaid on the carrier to form a composite material having an inlaid interlock structure, and stability of the lithium ion battery anode material can be improved by forming the composite material of the inlaid interlock structure. In some embodiments, the support may comprise carbon fibers, although it will be appreciated that in other embodiments, the support may also comprise carbon nanotubes; or comprise only carbon nanotubes. In some embodiments, the inlay may include hafnium, carbon microspheres, resin carbon, and pyrolytic carbon. Of course, it will be appreciated that in other embodiments, the resin carbon and pyrolytic carbon may be omitted. In some embodiments, the energy density and conductivity of the lithium ion battery anode material can be greatly improved by introducing hafnium and carbon microspheres.
Further, in some embodiments, the carbon nanotubes may have diameters of 200-400 nanometers and lengths of 1-3 microns. In some embodiments, the carbon nanotubes may be selected to have a diameter of 300 nanometers and a length of 2 microns.
Further, in some embodiments, the carbon fibers may have a diameter of 5-8 microns and a length of 1-3 microns; in some embodiments, the carbon fiber may alternatively have a diameter of 6.5 microns and a length of 2 microns.
Further, in some embodiments, the carbon microsphere may be 600-900 nanometers in particle size, alternatively, in some embodiments, the carbon microsphere may be 750 nanometers in particle size.
Fig. 2 shows a method for preparing a lithium ion battery anode material according to the present application, which can be used to prepare a lithium ion battery anode material according to the present application.
As shown in fig. 2, in some embodiments, the lithium ion battery anode material may include the steps of:
s1, mixing hafnium-carbon resin and phenolic resin to form mixed resin, and dissolving the mixed resin in a first solvent to form a first mixed solution. Wherein, the mass ratio of the hafnium-carbon resin to the phenolic resin can be 1:5-1:10; the first solvent may be an ethanol solution having a concentration of 5g/ml to 30 g/ml; the first mixed solution is a mixed resin of hafnium-carbon resin and phenolic resin.
Specifically, the mixed resin of hafnium-carbon resin and phenolic resin can be mixed according to the mass ratio of 1:5-1:10 to obtain the mixed resin of hafnium-carbon resin and phenolic resin, and then the mixed resin of hafnium-carbon resin and phenolic resin is dissolved in ethanol solution with the concentration of 5g/ml-30g/ml to obtain the ethanol solution of the mixed resin.
S2, adding the carbon fibers and/or the carbon nanotubes into the mixed solution, soaking for a set time to form the carbon fibers coated with the mixed resin, and processing under a first temperature condition to form a first composite. Wherein the set time may be 24-48 hours; the first temperature condition may be 1200 to 1400 degrees; the first composite is a hafnium-carbon fiber-pyrolytic carbon material.
Specifically, carbon fibers and/or carbon nanotubes can be added into an ethanol solution of the mixed resin, soaked for 24-48 hours to obtain carbon fibers coated with the mixed resin, and then placed in a high-temperature furnace to be treated for 1-3 hours at the temperature of 1200-1400 ℃ to obtain the hafnium-carbon fiber-pyrolytic carbon material.
S3, treating the first composite material at a second temperature, and introducing a second solvent to obtain a second composite body. Wherein the second temperature condition may be 1000-1100 degrees; the second solvent can be mixed liquid formed by mixing methanol and ethanol according to the volume ratio of 3:1-6:1; the second composite may be a hafnium-carbon fiber-pyrolytic carbon-resin carbon material.
Specifically, methanol and ethanol can be mixed according to a volume ratio of 3:1-6:1 to form a mixed solution of the methanol and the ethanol, then the hafnium-carbon fiber-pyrolytic carbon material is placed in a high-temperature furnace for treatment at a temperature of 1000-1100 ℃, and meanwhile, the mixed solution of the methanol and the ethanol is introduced at a rate of 5-10 mL/h for 10-30 minutes, so that the hafnium-carbon fiber-pyrolytic carbon-resin carbon material is obtained.
S4, mixing the carbon microspheres and the phenolic microspheres to obtain mixed powder, dissolving the mixed powder in a third solvent, and uniformly stirring to form a second mixed solution. Wherein the mass ratio of the carbon microsphere to the phenolic microsphere is 1:1-1:3; the third solvent is a solution prepared by dissolving phenolic resin in ethanol to prepare a mass fraction of 10-20%; the second mixed solution is an ethanol solution containing carbon microspheres and a mixture of phenolic microspheres and phenolic resin.
Specifically, mixing carbon microspheres and phenolic microspheres according to a mass ratio of 1:1-1:3 to form mixed powder of the carbon microspheres and the phenolic microspheres, and dissolving phenolic resin in ethanol to prepare a solution with a mass fraction of 10-20%; and then placing the mixed powder of the carbon microspheres and the phenolic microspheres in the solution, and uniformly stirring to obtain an ethanol solution containing the mixture of the carbon microspheres and the phenolic resin.
S5, soaking the second composite body in the second mixed solution, and processing the second composite body under the condition of a third temperature under the condition of surrounding inert gas to form the composite material with the embedded interlocking structure. Wherein the inert gas may be argon; the third temperature condition may be 800 to 1000 degrees.
Specifically, the hafnium-carbon fiber-pyrolytic carbon-resin carbon material is soaked in an ethanol solution containing carbon microspheres and a mixture of phenolic microspheres and phenolic resin for 24-48 hours, then placed in a high-temperature furnace, and subjected to high-temperature heat treatment for 1-4 hours at 800-1000 ℃ in an argon atmosphere, so that the anode material of the embedded interlocking structure lithium ion battery can be obtained.
The present application will be described in detail with reference to specific examples.
Example 1
Mixing the mixed resin of the hafnium-carbon resin and the phenolic resin according to the mass ratio of 1:5 to obtain the mixed resin of the hafnium-carbon resin and the phenolic resin, and dissolving the mixed resin of the hafnium-carbon resin and the phenolic resin in an ethanol solution with the concentration of 5g/ml to obtain an ethanol solution of the mixed resin.
Adding carbon fiber into ethanol solution of mixed resin, soaking for 24 hours to obtain carbon fiber coated with the mixed resin, and then placing the carbon fiber coated with the mixed resin into a high-temperature furnace for treatment for 1 hour at the temperature of 1200 ℃ to obtain the hafnium-carbon fiber-pyrolytic carbon material.
Mixing methanol and ethanol according to a volume ratio of 3:1 to form a mixed solution of methanol and ethanol, then placing the hafnium-carbon fiber-pyrolytic carbon material in a high-temperature furnace, treating at a temperature of 1000 ℃, and simultaneously introducing the mixed solution of methanol and ethanol at a rate of 5mL/h for 10 minutes to obtain the hafnium-carbon fiber-pyrolytic carbon-resin carbon material.
Mixing carbon microspheres and phenolic microspheres according to a mass ratio of 1:1 to form mixed powder of the carbon microspheres and the phenolic microspheres, and dissolving phenolic resin in ethanol to prepare a solution with a mass fraction of 10%; and then placing the mixed powder of the carbon microspheres and the phenolic microspheres in the solution, and uniformly stirring to obtain an ethanol solution containing the mixture of the carbon microspheres and the phenolic resin.
Soaking the hafnium-carbon fiber-pyrolytic carbon-resin carbon material in an ethanol solution containing carbon microspheres and a mixture of phenolic microspheres and phenolic resin for 24 hours, then placing the material in a high-temperature furnace, and carrying out high-temperature heat treatment for 1 hour under the condition of 800 ℃ in an argon atmosphere to obtain the anode material of the embedded interlocking structure lithium ion battery.
Example 2
Mixing the mixed resin of the hafnium-carbon resin and the phenolic resin according to the mass ratio of 1:10 to obtain the mixed resin of the hafnium-carbon resin and the phenolic resin, and dissolving the mixed resin of the hafnium-carbon resin and the phenolic resin in an ethanol solution with the concentration of 30g/ml to obtain an ethanol solution of the mixed resin.
Adding carbon fiber into ethanol solution of mixed resin, soaking for 48 hours to obtain carbon fiber coated with the mixed resin, and then placing the carbon fiber coated with the mixed resin in a high-temperature furnace for 3 hours at the temperature of 1400 ℃ to obtain the hafnium-carbon fiber-pyrolytic carbon material.
Mixing methanol and ethanol according to a volume ratio of 6:1 to form a mixed solution of methanol and ethanol, then placing the hafnium-carbon fiber-pyrolytic carbon material in a high-temperature furnace, treating at 1100 ℃, and simultaneously introducing the mixed solution of methanol and ethanol at a rate of 10mL/h for 30 minutes to obtain the hafnium-carbon fiber-pyrolytic carbon-resin carbon material.
Mixing carbon microspheres and phenolic microspheres according to a mass ratio of 1:3 to form mixed powder of the carbon microspheres and the phenolic microspheres, and dissolving phenolic resin in ethanol to prepare a solution with a mass fraction of 20%; and then placing the mixed powder of the carbon microspheres and the phenolic microspheres in the solution, and uniformly stirring to obtain an ethanol solution containing the mixture of the carbon microspheres and the phenolic resin.
Soaking the hafnium-carbon fiber-pyrolytic carbon-resin carbon material in an ethanol solution containing carbon microspheres and a mixture of phenolic microspheres and phenolic resin for 48 hours, then placing the material in a high-temperature furnace, and carrying out high-temperature heat treatment for 4 hours under the condition of 1000 ℃ in an argon atmosphere to obtain the anode material of the embedded interlocking structure lithium ion battery.
Example 3
Mixing the mixed resin of the hafnium-carbon resin and the phenolic resin according to the mass ratio of 1:7 to obtain the mixed resin of the hafnium-carbon resin and the phenolic resin, and dissolving the mixed resin of the hafnium-carbon resin and the phenolic resin in an ethanol solution with the concentration of 10g/ml to obtain an ethanol solution of the mixed resin.
Adding carbon fiber into ethanol solution of mixed resin, soaking for 36 hours to obtain carbon fiber coated with the mixed resin, and then placing the carbon fiber coated with the mixed resin in a high-temperature furnace for 2 hours at the temperature of 1300 ℃ to obtain the hafnium-carbon fiber-pyrolytic carbon material.
Mixing methanol and ethanol according to a volume ratio of 4:1 to form a mixed solution of methanol and ethanol, then placing the hafnium-carbon fiber-pyrolytic carbon material in a high-temperature furnace, treating at 1050 ℃, and simultaneously introducing the mixed solution of methanol and ethanol at a rate of 8mL/h for 20 minutes to obtain the hafnium-carbon fiber-pyrolytic carbon-resin carbon material.
Mixing carbon microspheres and phenolic microspheres according to a mass ratio of 1:2 to form mixed powder of the carbon microspheres and the phenolic microspheres, and dissolving phenolic resin in ethanol to prepare a solution with a mass fraction of 15%; and then placing the mixed powder of the carbon microspheres and the phenolic microspheres in the solution, and uniformly stirring to obtain an ethanol solution containing the mixture of the carbon microspheres and the phenolic resin.
Soaking the hafnium-carbon fiber-pyrolytic carbon-resin carbon material in an ethanol solution containing carbon microspheres and a mixture of phenolic microspheres and phenolic resin for 36 hours, then placing the material in a high-temperature furnace, and carrying out high-temperature heat treatment for 2 hours under the condition of 900 ℃ in an argon atmosphere to obtain the anode material of the embedded interlocking structure lithium ion battery.
Example 4
Mixing the mixed resin of the hafnium-carbon resin and the phenolic resin according to the mass ratio of 1:8 to obtain the mixed resin of the hafnium-carbon resin and the phenolic resin, and dissolving the mixed resin of the hafnium-carbon resin and the phenolic resin in an ethanol solution with the concentration of 20g/ml to obtain an ethanol solution of the mixed resin.
Adding carbon fiber into ethanol solution of mixed resin, soaking for 38 hours to obtain carbon fiber coated with the mixed resin, and then placing the carbon fiber coated with the mixed resin in a high-temperature furnace for 3 hours at the temperature of 1400 ℃ to obtain the hafnium-carbon fiber-pyrolytic carbon material.
Mixing methanol and ethanol according to a volume ratio of 5:1 to form a mixed solution of methanol and ethanol, then placing the hafnium-carbon fiber-pyrolytic carbon material in a high-temperature furnace, treating at a temperature of 1000 ℃, and simultaneously introducing the mixed solution of methanol and ethanol at a rate of 8mL/h for 20 minutes to obtain the hafnium-carbon fiber-pyrolytic carbon-resin carbon material.
Mixing carbon microspheres and phenolic microspheres according to a mass ratio of 1:3 to form mixed powder of the carbon microspheres and the phenolic microspheres, and dissolving phenolic resin in ethanol to prepare a solution with a mass fraction of 20%; and then placing the mixed powder of the carbon microspheres and the phenolic microspheres in the solution, and uniformly stirring to obtain an ethanol solution containing the mixture of the carbon microspheres and the phenolic resin.
Soaking the hafnium-carbon fiber-pyrolytic carbon-resin carbon material in an ethanol solution containing carbon microspheres and a mixture of phenolic microspheres and phenolic resin for 24 hours, then placing the material in a high-temperature furnace, and carrying out high-temperature heat treatment for 3 hours under the condition of 800 ℃ in an argon atmosphere to obtain the anode material of the embedded interlocking structure lithium ion battery.
Example 5
Mixing the mixed resin of the hafnium-carbon resin and the phenolic resin according to the mass ratio of 1:9 to obtain the mixed resin of the hafnium-carbon resin and the phenolic resin, and dissolving the mixed resin of the hafnium-carbon resin and the phenolic resin in an ethanol solution with the concentration of 25g/ml to obtain an ethanol solution of the mixed resin.
Adding carbon fiber into ethanol solution of mixed resin, soaking for 40 hours to obtain carbon fiber coated with the mixed resin, and then placing the carbon fiber coated with the mixed resin into a high-temperature furnace for 3 hours at the temperature of 1250 ℃ to obtain the hafnium-carbon fiber-pyrolytic carbon material.
Mixing methanol and ethanol according to a volume ratio of 5:1 to form a mixed solution of methanol and ethanol, then placing the hafnium-carbon fiber-pyrolytic carbon material in a high-temperature furnace, treating at a temperature of 1000 ℃, and simultaneously introducing the mixed solution of methanol and ethanol at a rate of 8mL/h for 25 minutes to obtain the hafnium-carbon fiber-pyrolytic carbon-resin carbon material.
Mixing carbon microspheres and phenolic microspheres according to a mass ratio of 1:2 to form mixed powder of the carbon microspheres and the phenolic microspheres, and dissolving phenolic resin in ethanol to prepare a solution with a mass fraction of 20%; and then placing the mixed powder of the carbon microspheres and the phenolic microspheres in the solution, and uniformly stirring to obtain an ethanol solution containing the mixture of the carbon microspheres and the phenolic resin.
Soaking the hafnium-carbon fiber-pyrolytic carbon-resin carbon material in an ethanol solution containing carbon microspheres and a mixture of phenolic microspheres and phenolic resin for 40 hours, then placing the material in a high-temperature furnace, and carrying out high-temperature heat treatment for 4 hours under the condition of 800 ℃ in an argon atmosphere to obtain the anode material of the embedded interlocking structure lithium ion battery.
Example 6
Mixing the mixed resin of the hafnium-carbon resin and the phenolic resin according to the mass ratio of 1:6 to obtain the mixed resin of the hafnium-carbon resin and the phenolic resin, and dissolving the mixed resin of the hafnium-carbon resin and the phenolic resin in an ethanol solution with the concentration of 25g/ml to obtain an ethanol solution of the mixed resin.
Adding carbon fiber into ethanol solution of mixed resin, soaking for 30 hours to obtain carbon fiber coated with the mixed resin, and then placing the carbon fiber coated with the mixed resin in a high-temperature furnace for 3 hours at the temperature of 1200 ℃ to obtain the hafnium-carbon fiber-pyrolytic carbon material.
Mixing methanol and ethanol according to a volume ratio of 4:1 to form a mixed solution of methanol and ethanol, then placing the hafnium-carbon fiber-pyrolytic carbon material in a high-temperature furnace, treating at 1100 ℃, and simultaneously introducing the mixed solution of methanol and ethanol at a rate of 10mL/h for 25 minutes to obtain the hafnium-carbon fiber-pyrolytic carbon-resin carbon material.
Mixing carbon microspheres and phenolic microspheres according to a mass ratio of 1:3 to form mixed powder of the carbon microspheres and the phenolic microspheres, and dissolving phenolic resin in ethanol to prepare a solution with a mass fraction of 10%; and then placing the mixed powder of the carbon microspheres and the phenolic microspheres in the solution, and uniformly stirring to obtain an ethanol solution containing the mixture of the carbon microspheres and the phenolic resin.
Soaking the hafnium-carbon fiber-pyrolytic carbon-resin carbon material in an ethanol solution containing carbon microspheres and a mixture of phenolic microspheres and phenolic resin for 28 hours, then placing the material in a high-temperature furnace, and carrying out high-temperature heat treatment for 3.5 hours under the condition of 950 ℃ in an argon atmosphere to obtain the anode material of the embedded interlocking structure lithium ion battery.
Comparative example
Dissolving phenolic resin in ethanol with the concentration of 25g/ml to obtain phenolic resin ethanol solution, arranging carbon fibers in the phenolic resin ethanol solution, and soaking for 30 hours to obtain carbon fibers coated with the phenolic resin; placing the carbon fiber-pyrolytic carbon material in a high-temperature furnace, and treating for 3 hours at the temperature of 1200 ℃ to obtain a sample carbon fiber-pyrolytic carbon material; mixing methanol and ethanol according to a volume ratio of 4:1 to obtain a mixed solution, placing the carbon fiber-pyrolytic carbon material in a high-temperature furnace, and introducing the mixed solution of methanol and ethanol at a rate of 10mL/h for 25 minutes at a temperature of 1100 ℃ to obtain the anode material.
The energy density of this comparative example was 100W h/kg by experiment; while examples 1 to 6 of the present application incorporated hafnium and carbon microspheres with energy densities significantly higher than those of the comparative examples, the highest values of energy densities in examples 1 to 6 could reach 210W h/kg, which is 52.4% higher than that of the comparative examples.
It is to be understood that the above examples only represent preferred embodiments of the present application, which are described in more detail and are not to be construed as limiting the scope of the application; it should be noted that, for a person skilled in the art, the above technical features can be freely combined, and several variations and modifications can be made without departing from the scope of the application; therefore, all changes and modifications that come within the meaning and range of equivalency of the claims are to be embraced within their scope.
Claims (8)
1. The preparation method of the lithium ion battery anode material is characterized by comprising the following steps of:
s1, mixing hafnium-carbon resin and phenolic resin to form mixed resin, and dissolving the mixed resin in a first solvent to form a first mixed solution; the first solvent comprises an ethanol solution with the concentration of 5g/ml to 30 g/ml;
s2, adding carbon fibers and/or carbon nanotubes into the first mixed solution, soaking for a set time to form carbon fibers and/or carbon nanotubes coated with the mixed resin, and processing under a first temperature condition to form a first complex; the first temperature condition is 1200-1400 ℃;
s3, treating the first complex under a second temperature condition, and introducing a second solvent to obtain a second complex; the second temperature condition is 1000-1100 ℃; the second solvent is a mixed solution formed by mixing methanol and ethanol according to the volume ratio of 3:1-6:1;
s4, mixing the carbon microspheres and the phenolic microspheres to obtain mixed powder, dissolving the mixed powder in a third solvent, and uniformly stirring to form a second mixed solution; the third solvent is a solution prepared by dissolving phenolic resin in ethanol to form 10-20% by mass;
s5, soaking the second composite body in the second mixed solution, and processing the second composite body under the condition of a third temperature under the condition of surrounding inert gas to form a composite material with an embedded interlocking structure; the third temperature condition is 800-1000 ℃; the composite material includes a carrier and an inlay; the inlay is inlaid on the carrier, and the carrier comprises the carbon fiber and/or the carbon nano tube; the inlay includes hafnium and the carbon microsphere.
2. The method according to claim 1, wherein in the step S1, the mass ratio of the hafnium-carbon resin to the phenolic resin is 1:5-1:10.
3. The method for preparing a negative electrode material for a lithium ion battery according to claim 1, wherein in the step S4, the mass ratio of the carbon microspheres to the phenolic microspheres is 1:1-1:3.
4. A lithium ion battery anode material, characterized by being prepared by the preparation method of the lithium ion battery anode material according to any one of claims 1 to 3, comprising a carrier and an inlay; the inlay is inlaid on the carrier to form a composite material with an inlaid interlocking structure; the carrier comprises carbon fibers and/or carbon nanotubes; the inlay includes hafnium and carbon microspheres.
5. The lithium ion battery anode material of claim 4, wherein the inlay further comprises resin carbon and/or pyrolytic carbon.
6. The negative electrode material for lithium ion battery according to claim 4, wherein the carbon nanotubes have a diameter of 200-400 nm and a length of 1-3 μm.
7. The lithium ion battery anode material of claim 4, wherein the carbon fiber has a diameter of 5-8 microns and a length of 10-15 microns.
8. The lithium ion battery anode material of claim 4, wherein the carbon microsphere has a particle size of 600-900 nanometers.
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