CN110571430B - Preparation method and application of Co3O 4/carbon nanotube - Google Patents
Preparation method and application of Co3O 4/carbon nanotube Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 51
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000011259 mixed solution Substances 0.000 claims abstract description 24
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 23
- 239000010941 cobalt Substances 0.000 claims abstract description 23
- 229910020599 Co 3 O 4 Inorganic materials 0.000 claims abstract description 21
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical compound [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229960003351 prussian blue Drugs 0.000 claims abstract description 18
- 239000013225 prussian blue Substances 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000843 powder Substances 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 12
- 239000007787 solid Substances 0.000 claims abstract description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims abstract description 9
- 238000010000 carbonizing Methods 0.000 claims abstract description 7
- 150000001868 cobalt Chemical class 0.000 claims abstract description 7
- IDUKLYIMDYXQQA-UHFFFAOYSA-N cobalt cyanide Chemical compound [Co].N#[C-] IDUKLYIMDYXQQA-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 239000004094 surface-active agent Substances 0.000 claims abstract description 7
- 239000006228 supernatant Substances 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 6
- 230000001590 oxidative effect Effects 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 6
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 6
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 6
- UCFIGPFUCRUDII-UHFFFAOYSA-N [Co](C#N)C#N.[K] Chemical group [Co](C#N)C#N.[K] UCFIGPFUCRUDII-UHFFFAOYSA-N 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 5
- 230000001681 protective effect Effects 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical group O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 4
- 230000000630 rising effect Effects 0.000 claims description 4
- ZBYYWKJVSFHYJL-UHFFFAOYSA-L cobalt(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Co+2].CC([O-])=O.CC([O-])=O ZBYYWKJVSFHYJL-UHFFFAOYSA-L 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000007772 electrode material Substances 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 19
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 19
- 239000000463 material Substances 0.000 abstract description 9
- 239000010406 cathode material Substances 0.000 abstract description 8
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 239000002114 nanocomposite Substances 0.000 abstract description 3
- 229910052799 carbon Inorganic materials 0.000 description 11
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 10
- 239000002131 composite material Substances 0.000 description 9
- 239000002243 precursor Substances 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 7
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 239000007773 negative electrode material Substances 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 3
- 238000003763 carbonization Methods 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000005087 graphitization Methods 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910002090 carbon oxide Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000002048 multi walled nanotube Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000002071 nanotube Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910000314 transition metal oxide 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
- 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
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/523—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron for non-aqueous cells
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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
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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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
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Abstract
The invention relates to the technical field of nano composite materials, in particular to Co 3 O 4 Preparation method and application of carbon nanotube. The preparation method comprises the following steps: (1) adding water into soluble cobalt salt and surfactant to prepare mixed solution A; (2) adding water into cobalt cyanide to prepare a mixed solution B; (3) uniformly mixing the mixed solution A and the mixed solution B, standing for layering, removing supernatant, washing the lower layer solution with water and alcohol for multiple times, and collecting solids; (4) drying the solid to obtain cobalt-based Prussian blue powder; (5) carbonizing the cobalt-based Prussian blue powder to obtain Co/carbon powder; (6) oxidizing the Co/carbon powder to obtain Co 3 O 4 A carbon nanotube. The method has the advantages of simple process, low cost, controllable morphology and structure, safe and reliable synthesis process, and obtained Co 3 O 4 The carbon nanotube material can be used as a lithium ion battery cathode material.
Description
Technical Field
The invention relates to the technical field of nano composite materials, in particular to Co 3 O 4 Preparation method and application of carbon nanotube.
Background
Along with the development of society, the demand of people on energy is increasing day by day, and the traditional energy such as petroleum \ coal and the like are all non-renewable resources, so that the problem of serious environmental pollution is also avoided. Therefore, the development of clean renewable energy sources such as solar energy, wind energy, etc. has become a trend of social development. However, solar energy and wind energy are limited by factors such as weather and regional natural conditions, and have the problems of unstable energy output and the like, and the problems need to be solved through energy storage.
The lithium ion battery is a good energy storage device and has the advantages of light weight, small volume, convenient carrying and the likeAnd a large number of commercial products are used in devices such as mobile phones and electric automobiles. The lithium ion battery commercially used at present mainly takes graphite as a negative electrode, but the theoretical specific capacity of the graphite as the negative electrode is too low and only 372mAh g -1 Greatly influencing the use efficiency of the lithium ion battery. In order to solve the problem, researchers are dedicated to developing novel high-specific-capacity lithium ion battery negative electrode materials, and mainly focus on several aspects such as transition metal oxides, nitrogen-doped carbides, and composite materials of carbon and metal oxides. The composite material of carbon and metal oxide not only has high specific capacity of the metal oxide, but also can alleviate the problem of instability of the metal oxide under the support and protection of the carbon, thereby improving the cycling stability.
At present, the cobaltosic oxide/carbon composite material shows greater potential in the application of lithium ion batteries, and has higher specific capacity and good stability. Wu et al (ACS Nano,2010,4,3187- 3 O 4 The nano particles are compounded with graphene to be used as a negative electrode material of a lithium ion battery, and the composite material shows larger specific capacity and excellent cycling stability, but the morphology of the prepared carbon is not in a nano tube shape, so that the composite material is not beneficial to material transmission in the application process of the lithium ion battery. Gu et al (Angew. chem., int. Ed.,2015,54,7060- 3 O 4 The composite material with the carbon nanotube array shows higher performance in the application of the lithium ion battery, but the adoption of a template method easily causes the complexity of a synthesis process and increases the difficulty of synthesis. Huang et al (ACS nano,2015,9,1592-1599) compound a multiwall carbon nanotube and a cobaltosic oxide composite material prepared by using ZIF-67 as a precursor of cobaltosic oxide and pyrolyzing the precursor and the multiwall carbon nanotube, and show high specific capacity and stability in lithium ion battery application.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide Co 3 O 4 Preparation method of carbon nano tubeMethods and uses. The method takes cobalt-based Prussian blue (Co-PBA) as a precursor, and in-situ synthesis of Co is carried out through two-step pyrolysis, including carbonization and oxidation 3 O 4 The carbon nano tube nano composite material has the advantages of simple process, low cost, controllable shape and structure and safe and reliable synthesis process. The obtained material can be used as a lithium ion battery cathode material.
The invention adopts the following technical scheme.
Co 3 O 4 The preparation method of the carbon nano tube comprises the following steps:
(1) adding water into soluble cobalt salt and surfactant to prepare mixed solution A;
(2) adding water into cobalt cyanide to prepare a mixed solution B;
(3) uniformly mixing the mixed solution A and the mixed solution B, standing for layering, removing supernatant, washing the lower layer solution with water and alcohol for multiple times, and collecting solids;
(4) drying the solid to obtain cobalt-based Prussian blue powder;
(5) carbonizing the cobalt-based Prussian blue powder to obtain Co/carbon powder;
(6) oxidizing the Co/carbon powder to obtain Co 3 O 4 A carbon nanotube.
Preferably, the ratio of the soluble cobalt salt to the surfactant is 1-3 mmol: 1-9 g.
Preferably, the soluble cobalt salt is cobalt nitrate hexahydrate or cobalt acetate tetrahydrate; the surfactant is polyvinylpyrrolidone.
The amount of polyvinylpyrrolidone has an influence on the particle size of the cobalt-based Prussian blue powder, too much addition can cause too small particles, and too little addition can cause too large particles, thereby influencing the subsequent Co 3 O 4 The shape and performance of the carbon nano tube.
Preferably, the cobalt cyanide is potassium cobalt cyanide.
Preferably, the concentration of the cobalt cyanide in the mixed liquid B is 0.00125-0.02 mol/L.
Preferably, the mixture is left to stand for 24 to 32 hours.
Preferably, the drying temperature is 60-80 ℃ and the drying time is 10-24 hours.
In the invention, the obtained cobalt-based Prussian blue powder is used as a precursor, and Co can be synthesized in situ 3 O 4 The carbon nano tube has the advantages of simple required process conditions, low cost, controllable appearance and safe and reliable process.
Preferably, the carbonization is carried out in the protective atmosphere, the reaction is carried out for 1 to 1.5 hours at the temperature of 450-550 ℃, and then the reaction is carried out for 2 to 4 hours at the temperature of 450-1000 ℃, and the temperature rising speed is 1 to 10 ℃/min; the protective atmosphere is one of nitrogen, argon or hydrogen. The reaction at the temperature of 450-550 ℃ aims to completely decompose the structure of the precursor cobalt-based Prussian blue, and the reaction at the temperature of 450-1000 ℃ aims to promote the movement of cobalt atoms and the graphitization catalysis of cobalt elements on carbon materials, so that the hollow bamboo-like carbon nano tube is formed.
The cobalt-based Prussian blue powder is carbonized in the protective atmosphere, so that carbon elements in the precursor can be reserved to form the nanotube. The carbonization temperature, the temperature rise speed and the reaction time can affect the decomposition of the precursor, the catalysis of cobalt element on carbon graphitization and the formation of the carbon nano tube. The temperature is too low, the time is too short, the temperature rise speed is too high, the precursor can not be decomposed, or the cobalt element can not fully catalyze the graphitization of the carbon, so that the carbon nano tube can not be formed; if the temperature is too high, the time is too long, and the temperature rising speed is too slow, the carbon nanotubes will be cracked.
Preferably, the oxidation is carried out in air, and the reaction is carried out at 100-450 ℃ for 0.5-3 hours, and the temperature rising speed is 1-10 ℃/min. The cobalt in the Co/carbon powder can be oxidized into cobaltosic oxide by oxygen in the air by adopting air heating; the cobalt simple substance can not be completely changed into cobaltosic oxide at too low temperature and too short time; if the temperature is too high and the time is too long, the carbon nanotubes are oxidized into carbon dioxide and other gases, and the structure of the carbon nanotubes cannot be maintained.
Co prepared by the method 3 O 4 Carbon nanotubes having an average diameter of 50 to 100 nm.
Co as described above 3 O 4 The application of the carbon nano tube in the battery electrode material.
Preferably, Co as defined above 3 O 4 The application of the carbon nano tube in the negative electrode material of the lithium ion battery.
Further preferably, the Co is added 3 O 4 The carbon nanotube is used as the cathode material of the lithium ion battery. Specifically, a certain amount of Co is weighed 3 O 4 Adding certain amount of N-methyl pyrrolidone into carbon nanotube, super conductive carbon and polyvinylidene fluoride (PVDF), stirring and mixing for 4-10 hours, wherein Co is 3 O 4 Carbon nanotube Co 3 O 4 60-90% of the total mass of the carbon nanotube, the super conductive carbon and the PVDF, 5-20% of the super conductive carbon and 0.1-0.9g of N-methyl pyrrolidone; and coating the mixture on a copper foil by using a coater, drying for 3-12 hours at the temperature of 60-100 ℃, and cutting an electrode slice to obtain the lithium ion battery cathode material.
The excellent effects of the present invention: the method adopts cobalt-based Prussian blue powder as a precursor to synthesize Co in situ 3 O 4 The preparation method has the advantages of simple operation, low cost, easy control of reaction conditions and simple regulation and control of the shape and structure; prepared Co 3 O 4 The shape structure of the carbon nanotube is beneficial to the material transmission of the lithium ion battery in the application process, and the carbon nanotube is used as the negative electrode material of the lithium ion battery, so that the material has good performance.
Drawings
FIG. 1 shows the Co prepared by the present invention 3 O 4 SEM image of/carbon nanotube;
FIG. 2 shows the Co prepared by the present invention 3 O 4 XRD pattern of/carbon nanotube;
FIG. 3 shows the Co prepared by the present invention 3 O 4 The carbon nanotube is used as a constant current charge-discharge curve of the lithium ion battery cathode material, and the current density is 100 mA/g.
Detailed Description
The present invention will be described in detail below with reference to specific embodiments.
Example 1
Co 3 O 4 The preparation method of the carbon nano tube comprises the following steps:
(1) 0.5239g (1.8mmol) of cobalt nitrate hexahydrate and 6g of polyvinylpyrrolidone are added into 200mL of water to prepare a mixed solution A;
(2) 0.3323g (1mmol) of potassium cobalt cyanide is added into 200mL of water to prepare a mixed solution B;
(3) uniformly mixing the mixed solution A and the mixed solution B, standing for 24 hours until the solution is layered, removing supernatant, washing the lower-layer solution for 3 times by using water and ethanol, and centrifuging to collect solids;
(4) putting the solid into an oven, and drying at 60 ℃ for 12 hours to obtain cobalt-based Prussian blue powder;
(5) carbonizing cobalt-based Prussian blue powder in a nitrogen atmosphere, heating to 550 ℃ at the speed of 5 ℃/min, reacting for 1 hour, heating to 900 ℃ at the speed of 5 ℃/min, and reacting for 2 hours to obtain Co/carbon powder;
(6) co/carbon powder is put into air for oxidation, the temperature is raised to 300 ℃ at the rate of 5 ℃/minute, and the reaction is carried out for 1 hour to obtain Co 3 O 4 A carbon nanotube.
Example 2
Co 3 O 4 The preparation method of the carbon nano tube comprises the following steps:
(1) 0.8732g (3mmol) of cobalt nitrate hexahydrate and 9g of polyvinylpyrrolidone are added into 400mL of water to prepare a mixed solution A;
(2) adding 0.565g (1.7mmol) of potassium cobalt cyanide into 400mL of water to prepare a mixed solution B;
(3) uniformly mixing the mixed solution A and the mixed solution B, standing for 28 hours until the solution is layered, removing supernatant, washing the lower-layer solution for 3 times by using water and ethanol, and centrifuging to collect solids;
(4) putting the solid into an oven, and drying at 80 ℃ for 24 hours to obtain cobalt-based Prussian blue powder;
(5) carbonizing cobalt-based Prussian blue powder in a nitrogen atmosphere, heating to 450 ℃ at a speed of 2 ℃/min, reacting for 1 hour, heating to 1000 ℃ at a speed of 2 ℃/min, and reacting for 2 hours to obtain Co/carbon powder;
(6) co/carbon powder is put into air for oxidation, the temperature is raised to 450 ℃ at the rate of 2 ℃/minute, and the reaction is carried out for 1 hour, thus obtaining the productTo Co 3 O 4 A carbon nanotube.
Example 3
Co 3 O 4 The preparation method of the carbon nano tube comprises the following steps:
(1) 0.2491g (1mmol) of cobalt acetate tetrahydrate and 3g of polyvinylpyrrolidone are added into 100mL of water to prepare a mixed solution A;
(2) 0.1662g (0.5mmol) of potassium cobalt cyanide is added into 100mL of water to prepare a mixed solution B;
(3) uniformly mixing the mixed solution A and the mixed solution B, standing for 32 hours until the solution is layered, removing supernatant, washing the lower-layer solution for 3 times by using water and ethanol, and centrifuging to collect solids;
(4) putting the solid into an oven, and drying at 80 ℃ for 10 hours to obtain cobalt-based Prussian blue powder;
(5) carbonizing cobalt-based Prussian blue powder in a nitrogen atmosphere, heating to 450 ℃ at a rate of 3 ℃/min, reacting for 1 hour, heating to 800 ℃ at a rate of 3 ℃/min, and reacting for 3 hours to obtain Co/carbon powder;
(6) co/carbon powder is put into air for oxidation, the temperature is raised to 250 ℃ at the rate of 2 ℃/minute, and the reaction is carried out for 3 hours to obtain Co 3 O 4 A carbon nanotube.
Experimental example 1
For the Co prepared by the invention 3 O 4 The carbon nano tube is characterized.
Observation of Co in Scanning Electron Microscope (SEM) 3 O 4 The morphology of the carbon nanotubes is shown in FIG. 1, and hollow carbon nanotubes and Co are formed 3 O 4 Nanoparticle composite structures.
The X-ray diffraction of the material is shown in FIG. 2, which shows that Co is Co 3 O 4 Exist in the form of (1).
Experimental example 2
Co 3 O 4 The carbon nanotube is used as the lithium ion battery cathode material, and the constant current charge and discharge test is carried out on the battery cathode material.
Specifically, 8g of Co was weighed 3 O 4 Carbon nanotube, 1g of super conductive carbon and 1g ofPVDF, then 0.3g of N-methylpyrrolidone is added, stirred and mixed for 5 hours; and coating the mixture on a copper foil by using a coater, wherein the coating thickness is 100 mu m, drying at 80 ℃ for 8 hours, and cutting an electrode slice to obtain the lithium ion battery cathode material. And (4) placing the cut electrode slices into a glove box to be filled with batteries. And standing the assembled battery for 24 hours, and then carrying out constant-current charge and discharge test, wherein the current density is set to be 100mA/g and the voltage interval is set to be 0.01-3V during the test. The constant current charge and discharge curve is shown in fig. 3.
The test result shows that: under the current density of 100mA/g, the specific capacity can reach 950mAh/g, which is close to the theoretical specific capacity, and the composite material has excellent battery performance.
Claims (9)
1. Co 3 O 4 The preparation method of the carbon nano tube is characterized by comprising the following steps:
(1) adding water into soluble cobalt salt and surfactant to prepare mixed solution A;
(2) adding water into cobalt cyanide to prepare a mixed solution B;
(3) uniformly mixing the mixed solution A and the mixed solution B, standing for layering, removing supernatant, washing the lower layer solution with water and alcohol for multiple times, and collecting solids;
(4) drying the solid to obtain cobalt-based Prussian blue powder;
(5) carbonizing the cobalt-based Prussian blue powder to obtain Co/carbon powder;
(6) oxidizing the Co/carbon powder to obtain Co 3 O 4 A carbon nanotube;
carbonizing in protective atmosphere, reacting at 550 deg.C for 1-1.5 hr, and then at 1000 deg.C for 2-4 hr, with the temperature rise rate of 1-10 deg.C/min;
the oxidation is carried out in air, and the reaction is carried out for 0.5 to 3 hours at the temperature of 100 ℃ and 450 ℃, and the temperature rising speed is 1 to 10 ℃/min.
2. Co according to claim 1 3 O 4 The preparation method of the carbon nano tube is characterized in that the proportion of the soluble cobalt salt and the surfactant is1-3mmol：1-9g。
3. Co according to claim 1 3 O 4 The preparation method of the carbon nano tube is characterized in that the soluble cobalt salt is cobalt nitrate hexahydrate or cobalt acetate tetrahydrate; the surfactant is polyvinylpyrrolidone.
4. Co according to claim 1 3 O 4 The preparation method of the carbon nano tube is characterized in that the concentration of the cobalt cyanide in the mixed liquid B is 0.00125-0.02 mol/L.
5. Co according to claim 1 3 O 4 The preparation method of the carbon nano tube is characterized in that the cobalt cyanide is potassium cobalt cyanide.
6. Co according to claim 1 3 O 4 The preparation method of the carbon nano tube is characterized in that the drying temperature is 60-80 ℃, and the drying time is 10-24 hours.
7. Co according to claim 1 3 O 4 The preparation method of the carbon nano tube is characterized in that the protective atmosphere is one of nitrogen, argon or hydrogen.
8. Co prepared by the method of any one of claims 1 to 7 3 O 4 A carbon nanotube.
9. Co as recited in claim 8 3 O 4 The application of the carbon nano tube in the battery electrode material.
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