CN114447292A - Lithium ion battery cathode material and preparation method thereof - Google Patents
Lithium ion battery cathode material and preparation method thereof Download PDFInfo
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- CN114447292A CN114447292A CN202111595042.0A CN202111595042A CN114447292A CN 114447292 A CN114447292 A CN 114447292A CN 202111595042 A CN202111595042 A CN 202111595042A CN 114447292 A CN114447292 A CN 114447292A
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 51
- 239000010406 cathode material Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000004005 microsphere Substances 0.000 claims abstract description 91
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 78
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 61
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 39
- 239000004917 carbon fiber Substances 0.000 claims abstract description 39
- 239000002131 composite material Substances 0.000 claims abstract description 28
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 15
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 15
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 8
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 156
- 229920005989 resin Polymers 0.000 claims description 104
- 239000011347 resin Substances 0.000 claims description 104
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 78
- 239000000243 solution Substances 0.000 claims description 61
- RGSCXUOGQGNWFC-UHFFFAOYSA-N [Hf].[C] Chemical compound [Hf].[C] RGSCXUOGQGNWFC-UHFFFAOYSA-N 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 50
- 239000005011 phenolic resin Substances 0.000 claims description 50
- 229920001568 phenolic resin Polymers 0.000 claims description 50
- 239000011259 mixed solution Substances 0.000 claims description 33
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 27
- 238000002156 mixing Methods 0.000 claims description 23
- 239000002296 pyrolytic carbon Substances 0.000 claims description 22
- 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
- -1 phenolic aldehyde Chemical class 0.000 claims description 17
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 13
- 239000007773 negative electrode material Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 10
- 239000010405 anode material Substances 0.000 claims description 8
- 238000012545 processing Methods 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 description 20
- 239000000463 material Substances 0.000 description 18
- 239000003575 carbonaceous material Substances 0.000 description 16
- 239000012300 argon atmosphere Substances 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- RCHKEJKUUXXBSM-UHFFFAOYSA-N n-benzyl-2-(3-formylindol-1-yl)acetamide Chemical compound C12=CC=CC=C2C(C=O)=CN1CC(=O)NCC1=CC=CC=C1 RCHKEJKUUXXBSM-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 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
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006182 cathode active material Substances 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
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000012360 testing method Methods 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
-
- 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
- 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
The invention relates to a lithium ion battery cathode material and a preparation method thereof, wherein the lithium ion battery cathode material comprises a carrier and an inlay; the inlay is inlaid on the carrier to form a composite material having a mosaic interlocking structure; the carrier comprises carbon fibers and/or carbon nanotubes; the inlay includes hafnium and carbon microspheres. The lithium ion battery cathode material is embedded on a carrier formed by carbon fibers and/or carbon nano tubes by introducing hafnium and carbon microspheres as inlays and compounded to form a composite material with an embedded interlocking structure, so that the energy density and the conductivity can be improved.
Description
Technical Field
The invention relates to the field of lithium ion batteries, in particular to a lithium ion battery cathode material and a preparation method thereof.
Background
Lithium ion batteries have been widely used in the fields of notebook computers, smart phones, and the like. The lithium ion battery mainly comprises a positive electrode, a negative electrode, an electrolyte and a diaphragm, and mainly depends on lithium ions to move between the positive electrode and the negative electrode to work. During charging and discharging, lithium ions are inserted and extracted back and forth between the two electrodes, during charging, 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 during discharge. The traditional negative electrode material is graphite, and the theoretical specific capacity of the graphite cannot completely meet the increasing requirement of high energy density of the power battery. Therefore, the development of a novel high-capacity lithium ion battery cathode material has important practical significance.
Disclosure of Invention
The invention aims to provide an improved lithium ion battery cathode material, and further provides an improved lithium ion battery.
The technical scheme adopted by the invention for solving the technical problems is as follows: constructing a lithium ion battery cathode material, which comprises a carrier and an inlay; the inlay is inlaid on the carrier to form a composite material having a mosaic interlocking structure; the carrier comprises carbon fibers and/or carbon nanotubes; the inlay includes hafnium and carbon microspheres.
Preferably, the inlay further comprises resinous 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 to 8 micrometers and a length of 10 to 15 micrometers.
Preferably, the particle size of the carbon microsphere is 600-900 nm.
The invention also discloses a preparation method of the lithium ion battery cathode material, which is used for preparing the lithium ion battery cathode 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 at a first temperature to form a first composite body;
s3, treating the first composite material at a second temperature, and introducing a second solvent to obtain a second composite;
s4, mixing the carbon microspheres and the phenolic aldehyde microspheres to obtain mixed powder, dissolving the mixed powder in a third solvent, and uniformly stirring to form a second mixed solution;
and S5, soaking the second composite body in the second mixed solution, and processing the second composite body under the inert gas surrounding and under the third temperature condition to form the composite material with the mosaic interlocking structure.
Preferably, in the step S1, the mass ratio of the hafnium-carbon resin to the phenolic resin is 1:5 to 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-;
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 microspheres to the phenolic microspheres is 1:1-1: 3;
the third solvent is a solution prepared by dissolving phenolic resin in ethanol and the mass fraction of the solution is 10-20%;
in the step S5, the third temperature condition is 800 to 1000 ℃.
The lithium ion battery cathode material and the preparation method thereof have the following beneficial effects: according to the lithium ion battery cathode material, hafnium and carbon microspheres are introduced to serve as inlays and are inlaid on a carrier formed by carbon fibers and/or carbon nano tubes and compounded to form a composite material with an inlaid interlocking structure, so that the energy density can be improved and the conductivity can be improved.
Drawings
The invention will be further described with reference to the accompanying drawings and examples, in which:
fig. 1 is an SEM image of a lithium ion battery anode material in some embodiments of the invention;
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 more clear understanding of the technical features, objects and effects of the present invention, embodiments of the present invention will now be described in detail with reference to the accompanying drawings.
Fig. 1 shows some preferred embodiments of the negative electrode material of a lithium ion battery of the present invention. The lithium ion battery cathode material can be used as a cathode active material, and a conductive agent is not required to be additionally added, so that the lithium ion battery cathode material 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, which is improved by 1.45 times compared with the energy density of the traditional lithium ion battery.
Further, in some embodiments, the lithium ion battery negative electrode material comprises a carrier and an inlay, wherein the inlay can be inlaid on the carrier to form a composite material, the composite material has a mosaic interlocking structure, and the stability of the lithium ion battery negative electrode material can be improved by forming the composite material with the mosaic interlocking structure. In some embodiments, the carrier may comprise carbon fibers, although it will be appreciated that in other embodiments, the carrier may also comprise carbon nanotubes; or only carbon nanotubes. In some embodiments, the inlay may include hafnium, carbon microspheres, resin carbon, and pyrolytic carbon. Of course, it is understood that in other embodiments, the resin carbon and the pyrolytic carbon may be omitted. In some embodiments, the energy density and the conductivity of the lithium ion battery negative electrode material can be greatly improved by introducing hafnium and carbon microspheres.
Further, in some embodiments, the carbon nanotubes may have a diameter of 200-400 nm and a length of 1-3 μm. 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 fibers may alternatively have a diameter of 6.5 microns and a length of 2 microns.
Further, in some embodiments, the carbon microsphere may have a particle size of 600 nm and 900 nm, and optionally, in some embodiments, the carbon microsphere may have a particle size of 750 nm.
Fig. 2 illustrates a method for preparing a lithium ion battery anode material according to the present invention, which can be used to prepare a lithium ion battery anode material according to the present invention.
As shown in fig. 2, in some embodiments, the lithium ion battery negative electrode material may include the steps of:
s1, mixing the hafnium-carbon resin and the phenolic resin to form a 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 can be ethanol solution with the concentration of 5g/ml-30 g/ml; the first mixed solution is a mixed resin of a hafnium-carbon resin and a phenolic resin.
Specifically, the mixed resin of the hafnium-carbon resin and the phenolic resin is mixed in a mass ratio of 1:5 to 1:10 to obtain a mixed resin of the hafnium-carbon resin and the phenolic resin, and the mixed resin of the hafnium-carbon resin and the phenolic resin is dissolved in an ethanol solution having a concentration of 5g/ml to 30g/ml to obtain an ethanol solution of the mixed resin.
And S2, adding carbon fibers and/or carbon nanotubes into the mixed solution, soaking for a set time to form the carbon fibers coated with the mixed resin, and treating under a first temperature condition to form a first composite body. Wherein, the set time can be 24-48 hours; the first temperature condition can be 1200-1400 ℃; the first composite is a hafnium-carbon fiber-pyrolytic carbon material.
Specifically, the carbon fibers and/or the carbon nanotubes can be added into an ethanol solution of the mixed resin, and soaked for 24-48 hours to obtain the carbon fibers coated with the mixed resin, and then the carbon fibers coated with the mixed resin are placed in a high-temperature furnace and processed at 1200-1400 ℃ for 1-3 hours to obtain the hafnium-carbon fiber-pyrolytic carbon material.
And S3, treating the first composite material at a second temperature, and introducing a second solvent to obtain a second composite. Wherein the second temperature condition may be 1000-; the second solvent can be a mixed solution 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, the methanol and the ethanol are mixed according to the 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 and treated under the condition that the temperature is 1000-1100 ℃, and simultaneously the mixed solution of the methanol and the ethanol is introduced at the rate of 5mL/h-10mL/h for 10-30 minutes, so as to obtain the hafnium-carbon fiber-pyrolytic carbon-resin carbon material.
And S4, mixing the carbon microspheres and the phenolic aldehyde 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 microspheres to the phenolic microspheres is 1:1-1: 3; the third solvent is a solution prepared by dissolving phenolic resin in ethanol and the mass fraction of the solution is 10-20%; the second mixed solution is ethanol solution containing carbon microspheres and a mixture of phenolic microspheres and phenolic resin.
Specifically, mixing carbon microspheres and phenolic aldehyde microspheres according to the mass ratio of 1:1-1:3 to form mixed powder of the carbon microspheres and the phenolic aldehyde microspheres, and dissolving phenolic aldehyde resin in ethanol to prepare a solution with the 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, the phenolic microspheres and the phenolic resin.
And S5, soaking the second composite body in the second mixed solution, and processing the second composite body under the inert gas surrounding and under the third temperature condition to form the composite material with the mosaic interlocking structure. Wherein the inert gas may be argon; the third temperature condition may be 800-1000 ℃.
Specifically, the hafnium-carbon fiber-pyrolytic carbon-resin carbon material can be soaked in an ethanol solution containing a mixture of carbon microspheres, phenolic microspheres and phenolic resin for 24-48 hours, and then placed in a high-temperature furnace to be subjected to high-temperature heat treatment for 1-4 hours at 800-1000 ℃ in an argon atmosphere, so that the lithium ion battery cathode material with the mosaic interlocking structure can be obtained.
The present invention will be described in detail with reference to specific examples.
Example 1
The mixed resin of the hafnium-carbon resin and the phenolic resin is mixed according to the mass ratio of 1:5 to obtain the mixed resin of the hafnium-carbon resin and the phenolic resin, and then the mixed resin of the hafnium-carbon resin and the phenolic resin is dissolved in an ethanol solution with the concentration of 5g/ml to obtain the ethanol solution of the mixed resin.
Adding carbon fibers into an ethanol solution of the mixed resin, soaking for 24 hours to obtain carbon fibers coated with the mixed resin, placing the carbon fibers coated with the mixed resin into a high-temperature furnace, and treating for 1 hour at the temperature of 1200 ℃ to obtain the hafnium-carbon fiber-pyrolytic carbon material.
Mixing methanol and ethanol according to the 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 the temperature of 1000 ℃, simultaneously introducing the mixed solution of methanol and ethanol at the rate of 5mL/h for 10 minutes, thereby obtaining the hafnium-carbon fiber-pyrolytic carbon-resin carbon material.
Mixing carbon microspheres and phenolic aldehyde microspheres according to the mass ratio of 1:1 to form mixed powder of the carbon microspheres and the phenolic aldehyde microspheres, and dissolving phenolic aldehyde resin in ethanol to prepare a solution with the 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, the phenolic microspheres and the phenolic resin.
Soaking the hafnium-carbon fiber-pyrolytic carbon-resin carbon material in the ethanol solution containing the mixture of the carbon microspheres and the phenolic resin for 24 hours, then placing the mixture in a high-temperature furnace, and carrying out high-temperature heat treatment for 1 hour at 800 ℃ in an argon atmosphere to obtain the lithium ion battery cathode material with the mosaic interlocking structure.
Example 2
The mixed resin of the hafnium-carbon resin and the phenolic resin is mixed according to the mass ratio of 1:10 to obtain the mixed resin of the hafnium-carbon resin and the phenolic resin, and then the mixed resin of the hafnium-carbon resin and the phenolic resin is dissolved in an ethanol solution with the concentration of 30g/ml to obtain the ethanol solution of the mixed resin.
Adding the carbon fiber into an ethanol solution of the mixed resin, soaking for 48 hours to obtain the carbon fiber coated with the mixed resin, placing the carbon fiber coated with the mixed resin into a high-temperature furnace, and treating for 3 hours at the temperature of 1400 ℃ to obtain the hafnium-carbon fiber-pyrolytic carbon material.
Mixing methanol and ethanol according to the 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 the temperature of 1100 ℃, simultaneously introducing the mixed solution of methanol and ethanol at the rate of 10mL/h for 30 minutes, thereby obtaining the hafnium-carbon fiber-pyrolytic carbon-resin carbon material.
Mixing carbon microspheres and phenolic aldehyde microspheres according to the mass ratio of 1:3 to form mixed powder of the carbon microspheres and the phenolic aldehyde microspheres, and dissolving phenolic aldehyde resin in ethanol to prepare a solution with the 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, the phenolic microspheres and the phenolic resin.
Soaking the hafnium-carbon fiber-pyrolytic carbon-resin carbon material in an ethanol solution containing a mixture of carbon microspheres, phenolic microspheres and phenolic resin for 48 hours, then placing the mixture in a high-temperature furnace, and carrying out high-temperature heat treatment for 4 hours at 1000 ℃ in an argon atmosphere to obtain the lithium ion battery cathode material with the mosaic interlocking structure.
Example 3
The mixed resin of the hafnium-carbon resin and the phenolic resin is mixed according to the mass ratio of 1:7 to obtain the mixed resin of the hafnium-carbon resin and the phenolic resin, and then the mixed resin of the hafnium-carbon resin and the phenolic resin is dissolved in an ethanol solution with the concentration of 10g/ml to obtain the ethanol solution of the mixed resin.
Adding the carbon fiber into an ethanol solution of the mixed resin, soaking for 36 hours to obtain the carbon fiber coated with the mixed resin, and then placing the carbon fiber coated with the mixed resin into a high-temperature furnace to be treated 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 ℃, simultaneously introducing the mixed solution of methanol and ethanol at a rate of 8mL/h for 20 minutes, thereby obtaining the hafnium-carbon fiber-pyrolytic carbon-resin carbon material.
Mixing carbon microspheres and phenolic aldehyde microspheres according to a mass ratio of 1:2 to form mixed powder of the carbon microspheres and the phenolic aldehyde microspheres, and dissolving phenolic aldehyde 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, the phenolic microspheres and the phenolic resin.
Soaking the hafnium-carbon fiber-pyrolytic carbon-resin carbon material in the ethanol solution containing the mixture of the carbon microspheres and the phenolic resin for 36 hours, then placing the mixture in a high-temperature furnace, and carrying out high-temperature heat treatment for 2 hours at 900 ℃ in an argon atmosphere to obtain the lithium ion battery cathode material with the mosaic interlocking structure.
Example 4
The mixed resin of the hafnium-carbon resin and the phenolic resin is mixed according to the mass ratio of 1:8 to obtain the mixed resin of the hafnium-carbon resin and the phenolic resin, and then the mixed resin of the hafnium-carbon resin and the phenolic resin is dissolved in an ethanol solution with the concentration of 20g/ml to obtain the ethanol solution of the mixed resin.
Adding the carbon fiber into an ethanol solution of the mixed resin, soaking for 38 hours to obtain the carbon fiber coated with the mixed resin, placing the carbon fiber coated with the mixed resin into a high-temperature furnace, and treating for 3 hours at the temperature of 1400 ℃ to obtain the hafnium-carbon fiber-pyrolytic carbon material.
Mixing methanol and ethanol according to the 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 the temperature of 1000 ℃, simultaneously introducing the mixed solution of methanol and ethanol at the rate of 8mL/h for 20 minutes, thereby obtaining the hafnium-carbon fiber-pyrolytic carbon-resin carbon material.
Mixing carbon microspheres and phenolic aldehyde microspheres according to the mass ratio of 1:3 to form mixed powder of the carbon microspheres and the phenolic aldehyde microspheres, and dissolving phenolic aldehyde resin in ethanol to prepare a solution with the 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, the phenolic microspheres and the phenolic resin.
Soaking the hafnium-carbon fiber-pyrolytic carbon-resin carbon material in the ethanol solution containing the mixture of the carbon microspheres and the phenolic resin for 24 hours, then placing the mixture in a high-temperature furnace, and carrying out high-temperature heat treatment for 3 hours at 800 ℃ in an argon atmosphere to obtain the lithium ion battery cathode material with the mosaic interlocking structure.
Example 5
The mixed resin of the hafnium-carbon resin and the phenolic resin is mixed according to the mass ratio of 1:9 to obtain the mixed resin of the hafnium-carbon resin and the phenolic resin, and then the mixed resin of the hafnium-carbon resin and the phenolic resin is dissolved in an ethanol solution with the concentration of 25g/ml to obtain the ethanol solution of the mixed resin.
Adding the carbon fiber into an ethanol solution of the mixed resin, soaking for 40 hours to obtain the carbon fiber coated with the mixed resin, and then placing the carbon fiber coated with the mixed resin into a high-temperature furnace to be treated for 3 hours at the temperature of 1250 ℃ to obtain the hafnium-carbon fiber-pyrolytic carbon material.
Mixing methanol and ethanol according to the 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 the temperature of 1000 ℃, simultaneously introducing the mixed solution of methanol and ethanol at the rate of 8mL/h for 25 minutes, thereby obtaining the hafnium-carbon fiber-pyrolytic carbon-resin carbon material.
Mixing carbon microspheres and phenolic aldehyde microspheres according to the mass ratio of 1:2 to form mixed powder of the carbon microspheres and the phenolic aldehyde microspheres, and dissolving phenolic aldehyde resin in ethanol to prepare a solution with the 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, the phenolic microspheres and the phenolic resin.
Soaking the hafnium-carbon fiber-pyrolytic carbon-resin carbon material in the ethanol solution containing the mixture of the carbon microspheres and the phenolic resin for 40 hours, and then placing the carbon material in a high-temperature furnace to perform high-temperature heat treatment for 4 hours at 800 ℃ in an argon atmosphere to obtain the lithium ion battery cathode material with the mosaic interlocking structure.
Example 6
The mixed resin of the hafnium-carbon resin and the phenolic resin is mixed according to the mass ratio of 1:6 to obtain the mixed resin of the hafnium-carbon resin and the phenolic resin, and then the mixed resin of the hafnium-carbon resin and the phenolic resin is dissolved in an ethanol solution with the concentration of 25g/ml to obtain the ethanol solution of the mixed resin.
Adding carbon fibers into an ethanol solution of the mixed resin, soaking for 30 hours to obtain carbon fibers coated with the mixed resin, placing the carbon fibers coated with the mixed resin into a high-temperature furnace, and treating 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 ℃, simultaneously introducing the mixed solution of methanol and ethanol at a rate of 10mL/h for 25 minutes, thereby obtaining the hafnium-carbon fiber-pyrolytic carbon-resin carbon material.
Mixing carbon microspheres and phenolic aldehyde microspheres according to the mass ratio of 1:3 to form mixed powder of the carbon microspheres and the phenolic aldehyde microspheres, and dissolving phenolic aldehyde resin in ethanol to prepare a solution with the 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, the phenolic microspheres and the phenolic resin.
Soaking the hafnium-carbon fiber-pyrolytic carbon-resin carbon material in the ethanol solution containing the mixture of the carbon microspheres and the phenolic resin for 28 hours, then placing the mixture in a high-temperature furnace, and carrying out high-temperature heat treatment for 3.5 hours at 950 ℃ in an argon atmosphere to obtain the lithium ion battery cathode material with the mosaic interlocking structure.
Comparative example
Dissolving phenolic resin in ethanol with the concentration of 25g/ml to obtain phenolic resin ethanol solution, and soaking carbon fibers in the phenolic resin ethanol solution 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, 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 cathode material.
Through the test, the energy density of the comparative example is 100W h/kg; while examples 1 to 6 of the present application introduce hafnium and carbon microspheres, the energy density is significantly higher than that of the comparative examples, the highest value of the energy density in examples 1 to 6 can reach 210W h/kg, and the ratio is increased by 52.4%.
It is to be understood that the foregoing examples, while indicating the preferred embodiments of the invention, are given by way of illustration and description, and are not to be construed as limiting the scope of the invention; it should be noted that, for those skilled in the art, the above technical features can be freely combined, and several changes and modifications can be made without departing from the concept of the present invention, which all belong to the protection scope of the present invention; therefore, all equivalent changes and modifications made within the scope of the claims of the present invention should be covered by the claims of the present invention.
Claims (10)
1. The lithium ion battery cathode material is characterized by comprising a carrier and an inlay; the inlay is inlaid on the carrier to form a composite material having a mosaic interlocking structure; the carrier comprises carbon fibers and/or carbon nanotubes; the inlay includes hafnium and carbon microspheres.
2. The lithium ion battery anode material of claim 1, wherein the inlay further comprises resinous carbon and/or pyrolytic carbon.
3. The lithium ion battery anode material as claimed in claim 1, wherein the diameter of the carbon nanotube is 200-400 nm, and the length thereof is 1-3 μm.
4. The lithium ion battery negative electrode material of claim 1, wherein the carbon fiber has a diameter of 5 to 8 micrometers and a length of 10 to 15 micrometers.
5. The lithium ion battery anode material as claimed in claim 1, wherein the particle size of the carbon microsphere is 600-900 nm.
6. A preparation method of the lithium ion battery negative electrode material is used for preparing the lithium ion battery negative electrode material of any one of claims 1 to 5, and is characterized by comprising 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 at a first temperature to form a first composite body;
s3, treating the first composite material at a second temperature, and introducing a second solvent to obtain a second composite;
s4, mixing the carbon microspheres and the phenolic aldehyde microspheres to obtain mixed powder, dissolving the mixed powder in a third solvent, and uniformly stirring to form a second mixed solution;
and S5, soaking the second composite body in the second mixed solution, and processing the second composite body under the inert gas surrounding and under the third temperature condition to form the composite material with the mosaic interlocking structure.
7. The preparation method of the negative electrode material for the lithium ion battery according to claim 6, wherein 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.
8. The method for preparing the negative electrode material of the lithium ion battery according to claim 6, wherein in the step S2, the first temperature condition is 1200-1400 ℃.
9. The method for preparing the anode material of the lithium ion battery as claimed in claim 6, wherein in the step S3, the first 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.
10. The preparation method of the lithium ion battery anode material according to claim 6, wherein in the step S4, the mass ratio of the carbon microspheres to the phenolic microspheres is 1:1-1: 3;
the third solvent is a solution prepared by dissolving phenolic resin in ethanol and the mass fraction of the solution is 10-20%;
in the step S5, the third temperature condition is 800 to 1000 ℃.
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