CN112290021A - Preparation method of carbon nano tube conductive agent for lithium ion battery - Google Patents
Preparation method of carbon nano tube conductive agent for lithium ion battery Download PDFInfo
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- CN112290021A CN112290021A CN202011039698.XA CN202011039698A CN112290021A CN 112290021 A CN112290021 A CN 112290021A CN 202011039698 A CN202011039698 A CN 202011039698A CN 112290021 A CN112290021 A CN 112290021A
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- 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
- 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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- 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 preparation method of a carbon nano tube conductive agent for a lithium ion battery, which relates to the technical field of lithium ion batteries and comprises the following steps: dissolving ferric nitrate nonahydrate, cobalt acetate tetrahydrate, magnesium nitrate hexahydrate, aluminum nitrate nonahydrate and citric acid in deionized water, stirring and evaporating to be viscous, roasting, and crushing to obtain a metal catalyst; growing carbon nanotubes on the surface of the metal catalyst by adopting a vapor deposition method; acid washing the carbon nano tube with hydrochloric acid and nitric acid to remove impurities; and crushing the carbon nano tube after acid washing, and dispersing the crushed carbon nano tube and a dispersing agent into a solvent to obtain the carbon nano tube conductive agent. The invention adopts citric acid complexation method to prepare the metal catalyst for growing the carbon nano tube, and controls the tube diameter size of the carbon nano tube by controlling the type and proportion of active metal in the metal catalyst. The carbon nanotube conductive agent is added into the lithium ion battery anode material, so that the conductivity of a pole piece can be improved, the internal resistance of the pole piece is reduced, the cycle life of the battery is prolonged, and the energy density of the battery is improved.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a preparation method of a carbon nano tube conductive agent for a lithium ion battery.
Background
The carbon nano tube has a unique nano structure and excellent physical and chemical properties, so that the carbon nano tube has lithium storage capacity far larger than that of traditional carbon materials such as natural graphite, artificial graphite, amorphous carbon and the like, and is used as a positive electrode conductive material of a lithium ion battery. In order to fully utilize the properties of single carbon nanotubes, it is necessary to uniformly disperse carbon nanotube powder in a solvent by a physical method to prepare a carbon nanotube conductive slurry as an electrode material of a lithium battery.
The conductivity and the dispersibility of the carbon nano tube are related to the tube diameter length of the carbon nano tube, the longer the carbon nano tube is, the smaller the tube diameter is, the better the conductivity of the carbon nano tube is, the better the performance of the prepared conductive agent is, but the less easy the dispersion is. At present, the diameter of the commercialized small-diameter carbon nano tube is about 8-15 nm, and the small-diameter carbon nano tube has a larger length-diameter ratio and is difficult to disperse, so that the viscosity of the prepared conductive agent is higher than 10000mPa & s, the viscosity of the conductive agent is too high, and the processability is poor, thereby limiting the application of the small-diameter carbon nano tube conductive agent.
The conductive agent with low viscosity in the market is basically prepared from carbon nanotubes with larger tube diameter, but the conductivity of the conductive agent is far lower than that of the conductive agent of the carbon nanotubes with small tube diameter. Therefore, it is an urgent need to solve the problem in the art to provide a new conductive agent for a lithium ion battery with small diameter and easy dispersion.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides a preparation method of a carbon nano tube conductive agent for a lithium ion battery, and the prepared carbon nano tube has small tube diameter, easy dispersion and good conductivity.
The invention provides a preparation method of a carbon nano tube conductive agent for a lithium ion battery, which comprises the following steps:
s1, dissolving ferric nitrate nonahydrate, cobalt acetate tetrahydrate, magnesium nitrate hexahydrate, aluminum nitrate nonahydrate and citric acid in deionized water to obtain a mixed solution;
s2, stirring and evaporating the mixed solution to be viscous, roasting and crushing to obtain a metal catalyst;
s3, growing carbon nanotubes on the surface of the metal catalyst by adopting a vapor deposition method;
s4, carrying out acid washing and impurity removal on the carbon nano tube by using hydrochloric acid and nitric acid;
and S5, crushing the carbon nano tube after acid washing, dispersing the crushed carbon nano tube and a dispersing agent into a solvent, and grinding and dispersing the mixture in a sand mill to obtain the carbon nano tube conductive agent.
Preferably, in S1, the mass percentages of the solutes in the mixed solution are: 8.1-18.5% of ferric nitrate nonahydrate, 2.5-7.5% of cobalt acetate tetrahydrate, 20.8-31.6% of magnesium nitrate hexahydrate, 2.5-5.5% of aluminum nitrate nonahydrate and 40.0-61.6% of citric acid.
Preferably, in S2, the roasting temperature is 500-600 ℃, and the roasting time is 4-5 h.
Preferably, in S2, the general structural formula of the metal catalyst is FeCoa(MgAlb)cOdWherein a is not more than 1, b is 0.1-0.2, and c is 2-4.
The metal catalyst has a perovskite structure or a perovskite-like structure, the catalytic active components of the metal catalyst are Fe and Co, and the carrier is an oxide of Mg and Al.
Preferably, in S2, the crushing is carried out by vibration sieving, and the mesh size is 100-150 meshes.
Preferably, in S3, the vapor deposition method uses natural gas and acetylene as carbon sources and hydrogen as a reducing gas.
Preferably, in S3, the vapor deposition is specifically performed as follows: putting the catalyst in a tubular furnace, introducing hydrogen, heating the tubular furnace to 720-820 ℃, introducing a mixed gas of natural gas and acetylene as a carbon source, and growing the carbon nano tube on the surface of the metal catalyst by chemical vapor deposition, wherein the deposition time is 1.5-3 h.
Preferably, in S3, the volume ratio of the input volume of the natural gas, the input volume of the ethylene and the input volume of the hydrogen is 35-135: 0.1-1: 1 to 6.
Preferably, in S4, the pickling temperature of hydrochloric acid is 85-95 ℃, and the pickling time is 20-30 h; preferably, the pickling temperature of the nitric acid is 90-100 ℃, and the pickling time is 18-28 h.
In the invention, in order to ensure that the structure of the carbon nano tube is not damaged by acid washing and maintain the excellent conductivity of the carbon nano tube, the method adopts the two acid washing processes.
Preferably, in S4, the addition amount of the dispersant accounts for 0.1-0.5% of the total mass of the carbon nanotube conductive agent.
Has the advantages that: the invention provides a preparation method of a carbon nano tube conductive agent for a lithium ion battery, which comprises the steps of preparing a catalyst for growing a carbon nano tube by adopting a citric acid complexing method, controlling the type and the proportion of each metal compound in a catalyst preparation raw material, thereby controlling the type and the proportion of active metal in the catalyst, and further regulating and controlling the pipe diameter size of the carbon nano tube growing on the surface of the catalyst by a vapor deposition method. The method adopts two pickling processes of hydrochloric acid and nitric acid, and removes impurities and purifies the carbon nano tube while maintaining the excellent conductive performance of the carbon nano tube. The carbon nano tube prepared by the invention has small tube diameter, is easy to disperse and has excellent conductivity. The prepared carbon nanotube conductive agent is added into the lithium ion battery anode material, so that the conductivity of a pole piece can be improved, the internal resistance of the pole piece is reduced, the problems of battery cycle deterioration and the like caused by the increase of the internal resistance of the battery in the cycle process are solved, and the cycle life of the battery and the energy density of the battery are improved.
Drawings
FIG. 1 is an SEM image of carbon nanotubes prepared in example 1 of the present invention;
FIG. 2 is an SEM image of carbon nanotubes prepared in example 2 of the present invention;
FIG. 3 is an SEM image of carbon nanotubes prepared in example 3 of the present invention;
FIG. 4 is an SEM image of carbon nanotubes prepared in example 4 of the present invention;
FIG. 5 is an SEM image of carbon nanotubes prepared in example 5 of the present invention;
FIG. 6 is an SEM image of carbon nanotubes in a comparative example of the present invention;
FIG. 7 is a DCR plot at different SOCs for the cells prepared in examples 1-5 of the present invention and comparative example;
fig. 8 is a graph showing the normal temperature cycle of the batteries fabricated in examples 1 to 5 of the present invention and the comparative example.
Detailed Description
The technical solution of the present invention will be described in detail below with reference to specific examples.
Example 1
(1) Preparation of the catalyst
According to the mass percentage, the ferric nitrate nonahydrate: cobalt acetate tetrahydrate: magnesium nitrate hexahydrate: aluminum nitrate nonahydrate: citric acid 9.2%: 5.62%: 21.78%: 2.54%: 60.86 percent of the mixture is added into deionized water to prepareThe mixed solution with 35 percent of solid content is obtained. Adding the mixed solution into a 500L reaction kettle, stirring and mixing, wherein the temperature of the reaction kettle is set to 90 ℃, the rotating speed is set to 50r/min, stirring is carried out until the solution is viscous, and the solution density is 1.40g/cm3And pouring the viscous solution into the crucible in equal amount, and placing the crucible into a roasting furnace for roasting, wherein the roasting temperature is set to 550 ℃, and the roasting time is 4.5 hours. And (3) crushing the solid catalyst obtained after roasting by a 120-mesh vibrating screen to obtain the metal catalyst.
(2) Preparation of carbon nanotubes
Putting the metal catalyst prepared in the step (1) into a tubular furnace, and introducing natural gas, ethylene and hydrogen; wherein the weight of the metal catalyst powder in the tubular furnace is 12g, the natural gas introduction amount is 100L/min, the ethylene introduction amount is 0.8L/min, and the hydrogen introduction amount is 2L/min; the temperature of the tubular furnace is 780 ℃ and the reaction time is 2 h.
Acid washing and purifying the prepared carbon nano tube: the 1 st time is hydrochloric acid pickling, the concentration of hydrochloric acid is 37%, and the pickling proportion is that of the carbon nano tube: hydrochloric acid: deionized water 1: 3: 15, pickling at the temperature of 90 ℃ for 24 hours, and washing with deionized water to be neutral after pickling; the 2 nd time is nitric acid pickling, the concentration of the nitric acid is 68 percent, and the pickling proportion is that of the carbon nano tube: nitric acid: deionized water 3: 8: and (20) pickling at the temperature of 95 ℃ for 20h, washing with deionized water to be neutral after pickling, putting into an oven, and drying to obtain the pickled and purified carbon nano tube.
(3) Preparation of carbon nanotube conductive agent
And (3) preparing the carbon nano tube obtained in the step (2), a dispersant PVP and a solvent NMP into suspension with solid content of 5.35%, adding the suspension into a sand mill for dispersing, wherein the addition of the dispersant is 0.35%, and dispersing for 1 hour to obtain the carbon nano tube conductive agent.
(4) Preparation of prismatic cell
And (4) adding the carbon nano tube conductive agent prepared in the step (3) into a positive electrode material, and processing the positive electrode material into a battery for performance test. As per NCM 622: carbon nanotube conductive agent: PVDF 98: 1: 1 in NMP solvent, coating the mixed slurry on an aluminum foil, and then carrying out vacuum drying and rolling to prepare the positive plate. And matching with a graphite negative plate to assemble the square battery with 50 Ah. The electrolyte adopts standard test electrolyte 1molLiPF6+ EC + EMC + DEC, and the diaphragm is a gluing diaphragm. Detecting the DCR value of the battery under different SOC, and adopting a 1C/1C charge-discharge normal temperature cycle performance test, wherein the charge-discharge voltage range is 2.8-4.2V.
Example 2
(1) Preparation of metal catalysts
According to the mass percentage, the ferric nitrate nonahydrate: cobalt acetate tetrahydrate: magnesium nitrate hexahydrate: aluminum nitrate nonahydrate: citric acid 9.2%: 5.72%: 24.48%: 2.64%: 57.96% was added to deionized water to make a 35% solids mixed solution. Adding the mixed solution into a 500L reaction kettle, stirring and mixing, wherein the temperature of the reaction kettle is set to 90 ℃, the rotating speed is set to 50r/min, stirring is carried out until the solution is viscous, and the solution density is 1.40g/cm3And pouring the viscous solution into the crucible in equal amount, and placing the crucible in a roasting furnace for roasting at the temperature of 550 ℃ for 4.5 hours. And (3) crushing the solid catalyst obtained after roasting by a 120-mesh vibrating screen to obtain the metal catalyst.
Preparing carbon nanotube powder according to the same process as in step (2) of example 1;
preparing a carbon nanotube conductive agent according to the same process as in the step (3) in the example 1;
a50 Ah square battery was prepared and tested for performance by the same procedure as in step (4) of example 1.
Example 3
Preparing a metal catalyst by the same process as in the step (1) in example 1;
(2) preparation of carbon nanotubes
Putting the metal catalyst prepared in the step (1) into a tubular furnace, and introducing natural gas, ethylene and hydrogen; wherein the weight of the catalyst powder put into the tubular furnace is 12g, the natural gas introduction amount is 90L/min, the ethylene introduction amount is 1L/min, and the hydrogen introduction amount is 2L/min; the temperature of the tubular furnace is 800 ℃, and the reaction time is 2 h.
Acid washing and purifying the prepared carbon nano tube: the 1 st time is hydrochloric acid pickling, the concentration of hydrochloric acid is 37%, and the pickling proportion is that of the carbon nano tube: hydrochloric acid: deionized water 1: 4: 15, pickling at the temperature of 90 ℃ for 24 hours, and washing with deionized water to be neutral after pickling; the 2 nd time is nitric acid pickling, the concentration of the nitric acid is 68 percent, and the pickling proportion is that of the carbon nano tube: nitric acid: deionized water 2: 8: and (20) pickling at the temperature of 95 ℃ for 20h, washing with deionized water to be neutral after pickling, putting into an oven, and drying the carbon nano tube.
Preparing a carbon nanotube conductive agent according to the same process as in the step (3) in the example 1;
a50 Ah square battery was prepared and tested for performance by the same procedure as in step (4) of example 1.
Example 4
The metal catalyst was prepared by the same procedure as in step (1) in example 1 except that: ferric nitrate nonahydrate: cobalt acetate tetrahydrate: magnesium nitrate hexahydrate: aluminum nitrate nonahydrate: citric acid 8.5%: 7.5%: 27%: 5%: 52 percent; stirring until the solution is viscous, and the solution density is 1.3g/cm3(ii) a The roasting temperature is set to be 500 ℃, and the roasting time is 5 hours; sieving with 120 mesh vibrating screen, and pulverizing.
Carbon nanotube powder was prepared by the same procedure as in step (2) of example 1, except that: (1) the weight of the metal catalyst powder in the tubular furnace is 12g, the introduction amount of natural gas is 35L/min, the introduction amount of ethylene is 0.1L/min, and the introduction amount of hydrogen is 1L/min; the temperature of the tubular furnace is 720 ℃, and the reaction time is 3 h. (2) The pickling temperature of hydrochloric acid is 85 ℃, the pickling time is 20 hours, the pickling temperature of nitric acid is 90 ℃, and the pickling time is 18 hours.
The same procedure as in step (3) of example 1 was followed to prepare a carbon nanotube conductive agent, except that: the amount of the dispersant added was 0.1%.
A50 Ah square battery was prepared and tested for performance by the same procedure as in step (4) of example 1.
Example 5
The metal catalyst was prepared by the same procedure as in step (1) in example 1 except that: ferric nitrate nonahydrate: cobalt acetate tetrahydrate: magnesium nitrate hexahydrate: aluminum nitrate nonahydrate: 18.5% of citric acid: 2.5%: 31.5%: 3.5%: 44%; stirring until the solution is viscousThe solution density was 1.5g/cm3(ii) a The roasting temperature is set as 600 ℃, and the roasting time is 4 hours; sieving with 120 mesh vibrating screen, and pulverizing.
Carbon nanotube powder was prepared by the same procedure as in step (2) of example 1, except that: (1) the weight of the metal catalyst powder in the tubular furnace is 12g, the introduction amount of natural gas is 135L/min, the introduction amount of ethylene is 0.8L/min, and the introduction amount of hydrogen is 6L/min; the temperature of the tubular furnace is 820 ℃, and the reaction time is 1.5 h. (2) The pickling temperature of hydrochloric acid is 95 ℃, the pickling time is 30 hours, the pickling temperature of nitric acid is 100 ℃, and the pickling time is 20 hours.
The same procedure as in step (3) of example 1 was followed to prepare a carbon nanotube conductive agent, except that: the amount of the dispersant added was 0.5%.
A50 Ah square battery was prepared and tested for performance by the same procedure as in step (4) of example 1.
Comparative example
A carbon nanotube conductive agent was prepared by using commercially available carbon nanotubes according to the step (3) in example 1. And a 50Ah square battery was prepared according to the same process as that for the square battery preparation of example 1, and the performance was tested.
The carbon nanotubes and assembled batteries of examples 1 to 5 according to the present invention and comparative example were tested for their performance, in which the powder squares were carbon nanotube powder pressed into squares of a certain thickness by a tablet press, and the results of the tests are shown in tables 1 to 2 and fig. 1 to 8.
TABLE 1 comparison table of basic properties of carbon nanotubes
TABLE 2 comparison of carbon nanotube conductor Properties
As can be seen from tables 1-2 and FIGS. 1-6, the carbon nanotubes prepared in examples 1-5 of the present invention have similar parameters of tube diameter, specific surface area, etc. to those of the comparative example, but the dispersion time of the carbon nanotubes in examples 1-5 is significantly shorter than that of the comparative example, and the viscosity of the conductive agent is much smaller. Therefore, the carbon nano tube prepared by the method has larger length-diameter ratio and is easy to disperse, and the prepared conductive agent has lower viscosity.
As can be seen from fig. 7 and 8, the electrochemical performance of the batteries prepared in examples 1 to 5 of the present invention was also superior to that of the comparative example.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (10)
1. A preparation method of a carbon nano tube conductive agent for a lithium ion battery is characterized by comprising the following steps:
s1, dissolving ferric nitrate nonahydrate, cobalt acetate tetrahydrate, magnesium nitrate hexahydrate, aluminum nitrate nonahydrate and citric acid in deionized water to obtain a mixed solution;
s2, stirring and evaporating the mixed solution to be viscous, roasting and crushing to obtain a metal catalyst;
s3, growing carbon nanotubes on the surface of the metal catalyst by adopting a vapor deposition method;
s4, carrying out acid washing and impurity removal on the carbon nano tube by using hydrochloric acid and nitric acid;
and S5, crushing the carbon nano tube after acid washing, dispersing the crushed carbon nano tube and a dispersing agent into a solvent, and grinding and dispersing the mixture in a sand mill to obtain the carbon nano tube conductive agent.
2. The method for preparing the carbon nanotube conductive agent for a lithium ion battery according to claim 1, wherein in S1, the mass percentages of the solutes in the mixed solution are: 8.1-18.5% of ferric nitrate nonahydrate, 2.5-7.5% of cobalt acetate tetrahydrate, 20.8-31.6% of magnesium nitrate hexahydrate, 2.5-5.5% of aluminum nitrate nonahydrate and 40.0-61.6% of citric acid.
3. The method for preparing a carbon nanotube conductive agent for a lithium ion battery according to claim 1, wherein the baking temperature is 500 to 600 ℃ and the baking time is 4 to 5 hours in S2.
4. The method of claim 1, wherein the general structural formula of the metal catalyst in S2 is FeCoa(MgAlb)cOdWherein a is not more than 1, b is 0.1-0.2, and c is 2-4.
5. The method for preparing a carbon nanotube conductive agent for a lithium ion battery according to claim 1, wherein in S2, the pulverization is carried out by vibration sieving, and the mesh size is 100-150 meshes.
6. The method of claim 1, wherein in step S3, the vapor deposition method uses natural gas and acetylene as carbon sources and hydrogen as a reducing gas.
7. The method for preparing a carbon nanotube conductive agent for a lithium ion battery according to claim 6, wherein the vapor deposition is performed in S3 as follows: putting the catalyst in a tubular furnace, introducing hydrogen, heating the tubular furnace to 720-820 ℃, introducing a mixed gas of natural gas and acetylene as a carbon source, and growing the carbon nano tube on the surface of the metal catalyst by chemical vapor deposition, wherein the deposition time is 1.5-3 h.
8. The method for preparing the carbon nanotube conductive agent for the lithium ion battery according to claim 6 or 7, wherein in S3, the volume ratio of the input volume of natural gas, ethylene and hydrogen is 35-135: 0.1-1: 1 to 6.
9. The method for preparing the carbon nanotube conductive agent for a lithium ion battery according to claim 1, wherein in S4, the pickling temperature of hydrochloric acid is 85 to 95 ℃, and the pickling time is 20 to 30 hours; preferably, the pickling temperature of the nitric acid is 90-100 ℃, and the pickling time is 18-28 h.
10. The method for preparing a carbon nanotube conductive agent for a lithium ion battery according to claim 1, wherein the amount of the dispersant added in S4 is 0.1 to 0.5% of the total mass of the carbon nanotube conductive agent.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114887626A (en) * | 2022-05-05 | 2022-08-12 | 湖北冠毓新材料科技有限公司 | Preparation method of carbon nanotube catalyst with high specific surface area and high length-diameter ratio |
| CN115353102A (en) * | 2022-07-11 | 2022-11-18 | 安徽南都华铂新材料科技有限公司 | Preparation method of low-cost negative electrode graphite |
Citations (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20040082950A (en) * | 2003-03-20 | 2004-09-30 | 이철진 | Massive synthesis method of double-walled carbon nanotubes using the vapor phase growth |
| CN1696052A (en) * | 2004-05-10 | 2005-11-16 | 华东理工大学 | Method for preparing Nano carbon tubes |
| CN101804355A (en) * | 2009-02-13 | 2010-08-18 | 锦湖石油化学株式会社 | Catalyst composition for the synthesis of thin multi-walled carbon nanotube and its manufacturing method |
| DE102009038464A1 (en) * | 2009-08-21 | 2011-02-24 | Bayer Materialscience Ag | Carbon nanotubes agglomerate |
| CN102962087A (en) * | 2011-08-31 | 2013-03-13 | 中国科学院金属研究所 | Carbon nanotube/silicon carbide foam catalytic composite material and preparation method thereof |
| US20130207026A1 (en) * | 2012-02-13 | 2013-08-15 | Korea Kumho Petrochemical Co., Ltd. | Highly Conductive Carbon Nanotube Having Bundle Moieties With Ultra-Low Bulk Density and Its Manufacturing Method |
| CN103721750A (en) * | 2014-01-09 | 2014-04-16 | 深圳市三顺中科新材料有限公司 | Catalyst for preparing long-pipe-diameter carbon nano tubes and preparation method of catalyst |
| CN104084214A (en) * | 2014-07-21 | 2014-10-08 | 深圳市三顺中科新材料有限公司 | Catalyst for preparing carbon nanotube, preparation method of catalyst, carbon nanotube, preparation method of carbon nanotube and lithium ion battery |
| JP2014208328A (en) * | 2013-03-29 | 2014-11-06 | 東洋インキＳｃホールディングス株式会社 | Carbon nanotube synthesis catalyst, carbon nanotube aggregate and method for producing thereof |
| CN105174244A (en) * | 2015-08-31 | 2015-12-23 | 无锡东恒新能源科技有限公司 | Carbon nano-tube preparation method |
| CN107074546A (en) * | 2014-11-14 | 2017-08-18 | 户田工业株式会社 | CNT and its manufacture method and the lithium rechargeable battery using CNT |
| CN107500268A (en) * | 2017-10-19 | 2017-12-22 | 焦作集越纳米材料技术有限公司 | A kind of preparation method of CNT |
| CN108079999A (en) * | 2017-12-06 | 2018-05-29 | 山东大展纳米材料有限公司 | A kind of method of continuous producing carbon nano-tube poly-metal deoxide pore space structure catalyst |
| CN110545914A (en) * | 2017-03-03 | 2019-12-06 | 锦湖石油化学株式会社 | Catalyst for mass production of multi-walled carbon nanotubes |
| CN110586115A (en) * | 2019-09-29 | 2019-12-20 | 内蒙古骏成新能源科技有限公司 | High-rate carbon nanotube catalyst, carbon nanotube and preparation method thereof |
| CN110801843A (en) * | 2019-11-11 | 2020-02-18 | 内蒙古骏成新能源科技有限公司 | Two-stage method for preparing high-magnification carbon nano tube with superfine tube diameter, catalyst and preparation method thereof |
| CN111333055A (en) * | 2020-03-30 | 2020-06-26 | 江西远东电池有限公司 | Preparation method of carbon nanotube doped lithium ion battery cathode material |
-
2020
- 2020-09-28 CN CN202011039698.XA patent/CN112290021B/en active Active
Patent Citations (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20040082950A (en) * | 2003-03-20 | 2004-09-30 | 이철진 | Massive synthesis method of double-walled carbon nanotubes using the vapor phase growth |
| CN1696052A (en) * | 2004-05-10 | 2005-11-16 | 华东理工大学 | Method for preparing Nano carbon tubes |
| CN101804355A (en) * | 2009-02-13 | 2010-08-18 | 锦湖石油化学株式会社 | Catalyst composition for the synthesis of thin multi-walled carbon nanotube and its manufacturing method |
| DE102009038464A1 (en) * | 2009-08-21 | 2011-02-24 | Bayer Materialscience Ag | Carbon nanotubes agglomerate |
| CN102962087A (en) * | 2011-08-31 | 2013-03-13 | 中国科学院金属研究所 | Carbon nanotube/silicon carbide foam catalytic composite material and preparation method thereof |
| US20130207026A1 (en) * | 2012-02-13 | 2013-08-15 | Korea Kumho Petrochemical Co., Ltd. | Highly Conductive Carbon Nanotube Having Bundle Moieties With Ultra-Low Bulk Density and Its Manufacturing Method |
| JP2014208328A (en) * | 2013-03-29 | 2014-11-06 | 東洋インキＳｃホールディングス株式会社 | Carbon nanotube synthesis catalyst, carbon nanotube aggregate and method for producing thereof |
| CN103721750A (en) * | 2014-01-09 | 2014-04-16 | 深圳市三顺中科新材料有限公司 | Catalyst for preparing long-pipe-diameter carbon nano tubes and preparation method of catalyst |
| CN104084214A (en) * | 2014-07-21 | 2014-10-08 | 深圳市三顺中科新材料有限公司 | Catalyst for preparing carbon nanotube, preparation method of catalyst, carbon nanotube, preparation method of carbon nanotube and lithium ion battery |
| CN107074546A (en) * | 2014-11-14 | 2017-08-18 | 户田工业株式会社 | CNT and its manufacture method and the lithium rechargeable battery using CNT |
| CN105174244A (en) * | 2015-08-31 | 2015-12-23 | 无锡东恒新能源科技有限公司 | Carbon nano-tube preparation method |
| CN110545914A (en) * | 2017-03-03 | 2019-12-06 | 锦湖石油化学株式会社 | Catalyst for mass production of multi-walled carbon nanotubes |
| CN107500268A (en) * | 2017-10-19 | 2017-12-22 | 焦作集越纳米材料技术有限公司 | A kind of preparation method of CNT |
| CN108079999A (en) * | 2017-12-06 | 2018-05-29 | 山东大展纳米材料有限公司 | A kind of method of continuous producing carbon nano-tube poly-metal deoxide pore space structure catalyst |
| CN110586115A (en) * | 2019-09-29 | 2019-12-20 | 内蒙古骏成新能源科技有限公司 | High-rate carbon nanotube catalyst, carbon nanotube and preparation method thereof |
| CN110801843A (en) * | 2019-11-11 | 2020-02-18 | 内蒙古骏成新能源科技有限公司 | Two-stage method for preparing high-magnification carbon nano tube with superfine tube diameter, catalyst and preparation method thereof |
| CN111333055A (en) * | 2020-03-30 | 2020-06-26 | 江西远东电池有限公司 | Preparation method of carbon nanotube doped lithium ion battery cathode material |
Non-Patent Citations (1)
| Title |
|---|
| 张亚昆等: "三元金属催化剂Fe/Co/Ni/MgO催化热解法制备碳纳米管", 《新乡学院学报》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114887626A (en) * | 2022-05-05 | 2022-08-12 | 湖北冠毓新材料科技有限公司 | Preparation method of carbon nanotube catalyst with high specific surface area and high length-diameter ratio |
| CN115353102A (en) * | 2022-07-11 | 2022-11-18 | 安徽南都华铂新材料科技有限公司 | Preparation method of low-cost negative electrode graphite |
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