CN102610329B - Quaternary composite carbon conductive agent and preparation method thereof - Google Patents
Quaternary composite carbon conductive agent and preparation method thereof Download PDFInfo
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- CN102610329B CN102610329B CN201210065281XA CN201210065281A CN102610329B CN 102610329 B CN102610329 B CN 102610329B CN 201210065281X A CN201210065281X A CN 201210065281XA CN 201210065281 A CN201210065281 A CN 201210065281A CN 102610329 B CN102610329 B CN 102610329B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a quaternary composite carbon conductive agent, which mainly comprises carbon black, carbon nanofiber, graphite and quasi-two-dimensional nano carbon, and a preparation method of the quaternary composite carbon conductive agent mainly comprises the following steps: taking a mixture of carbon black and graphite as a carbon-containing mixture, firstly carrying out microwave discharge under the protection of nitrogen to generate a conductive agent primary product with partial carbon nanofibers; then adding a dispersing agent, a binder and a solvent to carry out wet stirring and ball milling; the quaternary composite carbon conductive agent is prepared. The quaternary composite carbon conductive agent has the characteristics of high conductivity, high specific surface area, high purity, high dispersibility, low addition proportion and the like, the conductivity is more than 10S/cm, the specific surface area can reach 40 (m) 2 /g), ash content less than 0.02%, the proportion of addition generally being less than 2%. The product of the invention has excellent conductivity, can be fully dispersed in an electrode, and can be used as a conductive agent of a high-performance battery.
Description
Technical Field
The invention relates to an electrode material of a battery and a preparation method thereof, in particular to the technical field of a conductive agent material of an electrode and a preparation method thereof.
Background
Energy crisis and petrochemical resource exhaustion, alternative energy is searched, and development and utilization of renewable energy are greatly enhanced, and a high-performance energy storage battery is one of key components of renewable energy power generation systems such as a solar photovoltaic power generation system and a wind power generation system, so that the quality of electric energy generated by solar energy and wind energy is related, the cost of generated power is decisively influenced, and whether the solar energy and wind energy power generation technology can really enter thousands of households is further influenced; the aggravation of environmental protection pressure and the advocation of low-carbon economy put forward more and more urgent requirements on the development of few pollution-free electric vehicles, and the power battery is the key of the electric vehicles, and the high price and limited performance of the power battery are the bottleneck encountered in the popularization and application process of the electric vehicles at present; in the aspect of national safety, novel weapons represented by laser weapons and microwave weapons are 'killing maces' which are winning in future wars, the weapons need pulse power supplies with extra high power above MW level to be excited, and the high-power pulse technology is a key technology which needs to be mastered when the novel weapons are equipped; with the informatization and automation of the society, the application of notebook computers, video cameras, mobile phones, electric tools and the like is more and more popularized, and higher requirements on the performance of power storage devices are provided. In the background described above, the development of high-performance power storage devices has shown its great importance and urgency.
The electrode material of most high-performance batteries has low conductivity, so that the internal resistance of the whole electrode is increased, the utilization rate of active substances is low, and the overall performance is reduced.
Disclosure of Invention
The invention aims to provide a quaternary composite carbon conductive agent which has the characteristics of high conductivity, high specific surface area, high dispersibility, low addition proportion and the like and can be used as a conductive agent of a high-performance battery.
The second purpose of the invention is to provide a preparation method of the quaternary composite carbon conductive agent.
In order to achieve the first object, the technical scheme of the invention is as follows:
a quaternary composite carbon conductive agent mainly comprises carbon black, carbon nanofiber, graphite and quasi two-dimensional nano carbon, wherein the weight ratio of the components is as follows: 2-6: 0.5-1.5: 2-6;
preferably, the carbon black composite material comprises a dispersing agent, a binder and a solvent, wherein the weight ratio of the four-element carbon mixture to the dispersing agent to the binder to the solvent is as follows: 40-49: 2-20: 40-49: 30-300.
In order to achieve the second object, the technical scheme of the invention is as follows:
the preparation method of the quaternary composite carbon conductive agent mainly comprises the following steps:
a, taking a mixture of carbon black and graphite as a carbon-containing mixture, firstly, carrying out microwave discharge under the protection of nitrogen to generate a conductive agent primary product with partial carbon nanofibers;
b, then adding a dispersing agent, a binder and a solvent to carry out wet stirring and ball milling; the weight ratio of the components is that the mixture containing carbon, the dispersant, the binder and the solvent is as follows: 40-49: 2-20: 40-49: 40-400.
And c, finally preparing the quaternary composite carbon conductive agent consisting of carbon black, carbon nano-fibers, graphite and quasi-two-dimensional nano-carbon.
According to the further setting of the technical scheme:
in the mixture of the carbon black and the graphite, the weight ratio of the carbon black to the graphite is 5: 1-1: 5; wherein the carbon black is one or more of conductive carbon black, acetylene black and carbon black, the graphite is one or more of crystalline flake graphite, expanded graphite and conductive graphite, and the granularity of the graphite is smaller than 200 meshes.
The microwave discharge power is 500W-5000W, and the microwave discharge time is 2 minutes-60 minutes.
The dispersing agent in the step b comprises one or more of polyvinylpyrrolidone, alkylphenol polyoxyethylene alcohol, benzoic acid polyoxyethylene ester, naphthol polyoxyethylene ether, polyoxyethylene sorbitan fatty acid ester, alkylphenol polyoxyethylene and sodium dodecyl benzene sulfonate.
The binder in the step b comprises one or more of polyvinylidene fluoride, polytetrafluoroethylene, sodium carboxymethyl cellulose, carboxyethyl cellulose, carboxypropyl cellulose and styrene butadiene rubber.
The solvent in the step b comprises one or more of N-methyl pyrrolidone, N-dimethylformamide, N-dimethylacetamide, absolute ethyl alcohol, isopropanol and deionized water;
the ratio of the grinding materials is 10: 1-1: 1 during stirring and ball milling in the step b, the ball milling speed is 100-1000 r/min, and the ball milling time is 0.5-5 hours;
the invention has the following technical advantages:
the invention is a quaternary composite carbon conductive agent consisting of carbon black, carbon nano-fiber, graphite and quasi-two-dimensional nano-carbon, has the characteristics of high conductivity, high specific surface area, high purity, high dispersibility, low addition proportion and the like, the conductivity is more than 10S/cm, and the specific surface area can exceed 400 (m is m/cm) 2 /g), ash content less than 0.02%, the proportion of addition generally being less than 2%. The product of the invention has excellent performanceThe conductive material has conductivity, can be fully dispersed in an electrode, and can be used as a conductive agent of a high-performance battery.
The product of the invention can be applied to high-performance batteries such as zinc-manganese batteries, lithium ion batteries, nickel-hydrogen batteries and the like. The high-performance battery has wide application prospects in the aspects of electric vehicles, wind-solar power generation, national defense weapons and the like. In addition, with the informatization and automation of society, the applications of notebook computers, camcorders, mobile phones, electric tools and the like are more and more popularized, and the demands of high-performance batteries and conductive agents thereof are more and more extensive.
Detailed Description
Example 1
This example illustrates a quaternary composite carbon conductive agent and a method for preparing the same according to the present invention:
uniformly mixing 23 g of conductive carbon black and 23 g of crystalline flake graphite with the screened granularity of less than 200 meshes, putting the mixture into a microwave oven with the power of 2500W, carrying out microwave discharge heating for 18 minutes in nitrogen atmosphere, cooling, taking out microwave discharge products, adding 8 g of polyvinylpyrrolidone, 46 g of polyvinylidene fluoride and 200 g of N-methylpyrrolidone, putting the mixture into a stirring ball mill, and carrying out stirring ball milling under the process conditions that: the grinding material ratio is 5:1, the ball milling speed is 550 r/min, and the ball milling time is 2.5 hours, finally the quaternary composite carbon conductive agent consisting of carbon black, carbon nanofiber, graphite and quasi-two-dimensional nano carbon is prepared.
The technical performance indexes of the project product are as follows:
conductivity (S/cm) 15
Specific surface area (m) 2 /g) 450
Ash (%) 0.02
The conductive performance of the material can be greatly enhanced by adding the conductive material into the positive electrode material of the lithium ion battery according to the proportion of 1.5%.
Example 2
This example illustrates a quaternary composite carbon conductive agent and a method for preparing the same according to the present invention:
75 g of conductive carbon black with the granularity smaller than 200 meshes and 15 g of flake graphite are uniformly mixed, the mixture is placed into a microwave oven with the power of 5000W, microwave discharge heating is carried out for 2 minutes in the nitrogen atmosphere, the microwave discharge product is taken out after cooling, 4 g of alkylphenol polyoxyethylene alcohol, 90 g of polytetrafluoroethylene and 400 g of absolute ethyl alcohol are added, the mixture is placed into a stirring ball mill for stirring and ball milling, and the technological conditions during stirring and ball milling are as follows: the grinding material ratio is 10:1, the ball milling speed is 1000 r/min, and the ball milling time is 5 hours, so that the quaternary composite carbon conductive agent consisting of carbon black, carbon nanofibers, graphite and quasi-two-dimensional nanocarbon is finally prepared.
The technical performance indexes of the project product are as follows:
conductivity (S/cm) 12
Specific surface area (m) 2 /g) 490
Ash (%) 0.01
The conductive performance of the cathode material is obviously enhanced when the cathode material is added into the cathode material of the nickel-metal hydride battery according to the proportion of 0.5 percent.
Example 3
This example illustrates a quaternary composite carbon conductive agent and a method for preparing the same according to the present invention:
3 g of conductive carbon black and 15 g of crystalline flake graphite which are screened and screened to have granularity smaller than 200 meshes are uniformly mixed, the mixture is put into a microwave oven with power of 500W, microwave discharge heating is carried out for 60 minutes in nitrogen atmosphere, microwave discharge products are taken out after cooling, 9 g of polyvinylpyrrolidone, 9 g of polytetrafluoroethylene, 9 g of sodium carboxymethylcellulose, 15 g of N-methyl pyrrolidone and 15 g of isopropanol are added, the mixture is put into a stirring ball mill for stirring and ball milling, the stirring ball milling is carried out for 30 minutes, and the process conditions are as follows: the grinding material ratio is 1:1, the ball milling speed is 100 r/min, and the ball milling time is as follows, finally the quaternary composite carbon conductive agent consisting of carbon black, carbon nano-fiber, graphite and quasi-two-dimensional nano-carbon is prepared.
The technical performance indexes of the project product are as follows:
conductivity (S/cm) 18
Specific surface area (m) 2 /g) 410
Ash (%) 0.01
The additive is added into the positive electrode material of the alkaline zinc-manganese dioxide battery according to the proportion of 1.9%, and experiments prove that the conductivity of the positive electrode material is remarkably increased.
Claims (6)
1. The preparation method of the quaternary composite carbon conductive agent is characterized by mainly comprising the following steps:
a, taking a mixture of carbon black and graphite as a carbon-containing mixture, firstly carrying out microwave discharge under the protection of nitrogen to generate a conductive agent primary product with partial carbon nanofibers, wherein the microwave discharge power is 500W-5000W, and the microwave discharge time is 2 minutes-60 minutes;
b, then adding a dispersing agent, a binder and a solvent to perform wet stirring ball milling, and performing wet stirring ball milling on the conductive agent primary product obtained in the step a: dispersing agent: adhesive: the weight ratio of the solvent is as follows: 40 to 49:2 to 20:40 to 49:40 to 400; the milling material ratio during stirring and ball milling is 10-1:1, the ball milling speed is 100-1000 r/min, and the ball milling time is 0.5-5 hours;
and c, finally preparing the quaternary composite carbon conductive agent comprising carbon black, carbon nano-fibers, graphite and quasi-two-dimensional nano-carbon.
2. The method for preparing the quaternary composite carbon conductive agent according to claim 1, wherein the method comprises the following steps: the weight ratio of the carbon black to the graphite in the mixture is 5:1-1:5; wherein the carbon black is one or more of conductive carbon black and acetylene black, the graphite comprises one or more of crystalline flake graphite and expanded graphite, and the granularity of the graphite is smaller than 200 meshes.
3. The method for preparing the quaternary composite carbon conductive agent according to claim 1, wherein the method comprises the following steps: the dispersing agent comprises one or more of polyvinylpyrrolidone, alkylphenol polyoxyethylene alcohol, benzoic acid polyoxyethylene ester, naphthol polyoxyethylene ether, polyoxyethylene sorbitan fatty acid ester, alkylphenol polyoxyethylene ether and sodium dodecyl benzene sulfonate.
4. The method for preparing the quaternary composite carbon conductive agent according to claim 1, wherein the method comprises the following steps: the binder comprises one or more of polyvinylidene fluoride, polytetrafluoroethylene, sodium carboxymethylcellulose, carboxymethyl cellulose, carboxyethyl cellulose, carboxypropyl cellulose and styrene butadiene rubber.
5. The method for preparing the quaternary composite carbon conductive agent according to claim 1, wherein the method comprises the following steps: the solvent comprises one or more of N-methylpyrrolidone, N-dimethylformamide, N-dimethylacetamide, absolute ethyl alcohol, isopropanol and deionized water.
6. The quaternary composite carbon conductive agent prepared by the preparation method according to claim 1, wherein: the conductive agent comprises carbon black, carbon nanofiber, graphite and quasi-two-dimensional nano carbon, and the ratio of each component is carbon black: carbon nanofiber: graphite: the weight ratio of the quasi-two-dimensional nano carbon is as follows: 2 to 6: 0.5-1.5: 0.5-1.5: 2 to 6.
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| CN103474130B (en) * | 2013-09-30 | 2015-07-29 | 胡钧峰 | Preparation method of special nano grounding wire |
| CN103531814B (en) * | 2013-10-28 | 2015-03-25 | 深圳格林德能源有限公司 | Composite conductive agent and dispersion method thereof as well as positive plate and lithium ion battery |
| CN104505515B (en) * | 2014-12-26 | 2016-11-30 | 广东东莞市天润电子材料有限公司 | A kind of ferrous phosphate lithium battery nano-graphite conductive agent and preparation method thereof |
| CN104900883A (en) * | 2015-06-19 | 2015-09-09 | 中国第一汽车股份有限公司 | Preparation method of electroconductive agent for electrode |
| JP6988169B2 (en) * | 2017-05-26 | 2022-01-05 | トヨタ自動車株式会社 | A method for manufacturing a negative electrode for a non-aqueous electrolyte secondary battery, and a method for manufacturing a non-aqueous electrolyte secondary battery. |
| CN110252421A (en) * | 2019-07-10 | 2019-09-20 | 大英聚能科技发展有限公司 | A kind of conductive catalytic Netowrk tape and preparation method thereof |
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| CN1770515A (en) * | 2005-08-22 | 2006-05-10 | 中国科学院成都有机化学有限公司 | Anode, cathode material conductive agent for lithium-ion secondary battery and preparation method thereof |
| US7132062B1 (en) * | 2003-04-15 | 2006-11-07 | Plasticolors, Inc. | Electrically conductive additive system and method of making same |
| CN101355165A (en) * | 2007-07-23 | 2009-01-28 | 中国科学院成都有机化学有限公司 | Composite conductive agent for lithium ion battery anode material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US7132062B1 (en) * | 2003-04-15 | 2006-11-07 | Plasticolors, Inc. | Electrically conductive additive system and method of making same |
| CN1770515A (en) * | 2005-08-22 | 2006-05-10 | 中国科学院成都有机化学有限公司 | Anode, cathode material conductive agent for lithium-ion secondary battery and preparation method thereof |
| CN101355165A (en) * | 2007-07-23 | 2009-01-28 | 中国科学院成都有机化学有限公司 | Composite conductive agent for lithium ion battery anode material |
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Effective date of registration: 20221101 Address after: No. A172, Zhongchuang Card Tower, Entrepreneurship Building, University Science Park, No. 283, Middle Xiaoxiang Avenue, Juzizhou Street, Yuelushan University Science and Technology City, Changsha, 410000, Hunan Patentee after: Hunan Chuyoucai New Material Technology Co.,Ltd. Address before: 410082 School of materials science and engineering, Hunan University, Changsha, Hunan, Yuelu District Patentee before: CHANGSHA KAIBANG ENERGY TECHNOLOGY Co.,Ltd. |
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