CN117198595A - Oil-based single-walled carbon nanotube conductive paste and preparation method and application thereof - Google Patents
Oil-based single-walled carbon nanotube conductive paste and preparation method and application thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 52
- 239000002033 PVDF binder Substances 0.000 claims abstract description 84
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims abstract description 84
- 239000000203 mixture Substances 0.000 claims abstract description 73
- 239000002270 dispersing agent Substances 0.000 claims abstract description 69
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims abstract description 49
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 claims abstract description 39
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 6
- JDFDHBSESGTDAL-UHFFFAOYSA-N 3-methoxypropan-1-ol Chemical compound COCCCO JDFDHBSESGTDAL-UHFFFAOYSA-N 0.000 claims description 66
- 239000001913 cellulose Substances 0.000 claims description 66
- 229920002678 cellulose Polymers 0.000 claims description 66
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 46
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 46
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 46
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 43
- 239000004576 sand Substances 0.000 claims description 23
- 238000002156 mixing Methods 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 17
- 238000000227 grinding Methods 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 10
- 239000006185 dispersion Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
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- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000012752 auxiliary agent Substances 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- 239000006258 conductive agent Substances 0.000 description 9
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- 230000000052 comparative effect Effects 0.000 description 8
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- 230000002195 synergetic effect Effects 0.000 description 6
- 239000002041 carbon nanotube Substances 0.000 description 5
- 229910021393 carbon nanotube Inorganic materials 0.000 description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000002048 multi walled nanotube Substances 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
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- 238000001878 scanning electron micrograph Methods 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
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- 230000008676 import Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000011268 mixed slurry Substances 0.000 description 1
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- 229920000642 polymer Polymers 0.000 description 1
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- 239000011885 synergistic combination Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
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Abstract
The application relates to an oil-based single-walled carbon nanotube conductive paste, and a preparation method and application thereof. The conductive paste comprises the following components in parts by weight: 0.1 to 1.0 part of single-walled carbon nanotube mixture, 0.1 to 1.0 part of dispersing agent, 0.1 to 1.0 part of polyvinylidene fluoride and 97.0 to 100 parts of N-methyl pyrrolidone; wherein the single-walled carbon nanotube mixture comprises unmodified single-walled carbon nanotubes and octadecylamine modified single-walled carbon nanotubes. The oil-based single-walled carbon nanotube conductive paste provided by the application has the advantages of good dispersibility of the single-walled carbon nanotubes, excellent conductive performance and small usage amount of auxiliary agents, and can enhance the conductive performance of a battery, increase the battery capacity and have good application prospects when applied to a lithium ion battery.
Description
Technical Field
The application relates to the field of conductive materials, in particular to an oil-based single-walled carbon nanotube conductive paste, and a preparation method and application thereof.
Background
Carbon nanotubes are excellent conductive agents, and generally have a size of 2 to 100 nanometers and a length of 10 to 50 micrometers. Carbon nanotubes are widely used in the lithium battery industry as conductive agents with excellent electrical conductivity, thermal conductivity, and good mechanical strength among various carbon nanomaterials. For carbon nanotubes, single-walled carbon nanotubes (SWCNTs), double-walled carbon nanotubes, and multi-walled carbon nanotubes are classified according to the number of coaxial carbon nanotube walls. Compared with the multi-wall carbon nano tube, the defects on the wall of the single-wall carbon nano tube are fewer, the diameter distribution range is smaller, the tube length can reach hundreds of nanometers to tens of micrometers, and the uniformity and the stability are extremely high. In addition, SWCNTs have more excellent electrical and thermal conductivity, optical properties, thermal stability, high strength and toughness than multi-walled carbon nanotubes.
Since battery customers need to further provide battery energy density, cycle life, etc., it is necessary to increase the proportion of the positive electrode active material and decrease the proportion of the conductive agent, which puts higher demands on the conductivity of the conductive agent. The single-wall carbon nanotube conductive agent has more excellent conductivity and less additive amount, so that the proportion of the positive electrode active material can be increased when a battery manufacturer uses the single-wall carbon nanotube conductive agent. The single-wall carbon nanotubes in the current market mainly depend on import, the imported products are high in price on one hand, the addition proportion of the dispersing auxiliary is large on the other hand, the SWCNTs are poor in dispersibility and limited in conductivity.
In view of the above-mentioned related art, the inventors considered that there is a need for a conductive paste of SWCNTs that has better conductivity and less auxiliary agent usage
Disclosure of Invention
In order to solve the defects in the prior art, the application provides the oil-based single-walled carbon nanotube conductive paste, which has good dispersibility of single-walled carbon nanotubes, excellent conductive performance and small using amount of auxiliary agent, and can enhance the conductive performance of a battery, increase the battery capacity and have good application prospect when being applied to a lithium ion battery.
Therefore, the application provides an oil-based single-walled carbon nanotube conductive paste, which comprises the following components in parts by weight: 0.1 to 1.0 part of single-walled carbon nanotube mixture, 0.1 to 1.0 part of dispersing agent, 0.1 to 1.0 part of polyvinylidene fluoride and 97.0 to 100 parts of N-methyl pyrrolidone;
wherein the single-walled carbon nanotube mixture comprises unmodified single-walled carbon nanotubes and octadecylamine modified single-walled carbon nanotubes.
In the application, the single-walled carbon nanotube in the conductive paste comprises an unmodified single-walled carbon nanotube and an octadecylamine modified single-walled carbon nanotube, and the octadecylamine modified single-walled carbon nanotube forms an organic layer on the surface of the tube wall, so that the aggregation phenomenon of the single-walled carbon nanotube can be weakened, the compatibility between the single-walled carbon nanotube and an organic solvent can be improved, the uniform dispersion of the carbon nanotube in the organic solvent is promoted, but the self structure of the modified single-walled carbon nanotube is damaged to a certain extent in the modification process, and the conductive performance of the modified single-walled carbon nanotube is reduced. The inventor of the application creatively discovers through research that when the octadecylamine modified single-walled carbon nanotube and the unmodified single-walled carbon nanotube are added together as a conductive agent, not only is the dispersibility of the octadecylamine modified single-walled carbon nanotube in a solvent better, but also the dispersion of the unmodified single-walled carbon nanotube in the solvent can be promoted, and through the synergistic combination of the octadecylamine modified single-walled carbon nanotube and the unmodified single-walled carbon nanotube, the single-walled carbon nanotube mixture in the conductive paste has better dispersibility, the using amount of an auxiliary agent is reduced, meanwhile, the conductive paste has better conductivity, and the finally prepared conductive paste has excellent conductive performance.
Further, the application can make the resistivity of the conductive paste lower and the conductivity better by controlling the amount of each component in the conductive paste within the above range.
In some preferred embodiments, the conductive paste comprises the following components in parts by weight: 0.3 to 0.5 part of single-walled carbon nanotube mixture, 0.3 to 0.7 part of dispersing agent, 0.3 to 0.7 part of polyvinylidene fluoride and 98.0 to 99.0 parts of N-methyl pyrrolidone.
In some most preferred embodiments, the conductive paste comprises the following components in parts by weight: 0.4 part
Single-walled carbon nanotube mixture, 0.5 part of dispersant, 0.5 part of polyvinylidene fluoride and 98.3 parts of N-methylpyrrolidone.
In some embodiments, the mass ratio of unmodified single-walled carbon nanotubes to octadecylamine-modified single-walled carbon nanotubes in the single-walled carbon nanotube mixture is (3-7): 1.
In some embodiments, the mass ratio of unmodified single-walled carbon nanotubes to octadecylamine-modified single-walled carbon nanotubes in the single-walled carbon nanotube mixture may be, for example, 3:1, 4:1, 5:1, 6:1, 7:1, or the like. In some preferred embodiments, the mass ratio of unmodified single-walled carbon nanotubes to octadecylamine-modified single-walled carbon nanotubes in the single-walled carbon nanotube mixture is (4-5): 1.
According to the application, the mass ratio of the unmodified single-walled carbon nanotubes to the octadecylamine modified single-walled carbon nanotubes in the single-walled carbon nanotube mixture is controlled within the range, and particularly, the synergistic effect between the unmodified single-walled carbon nanotubes and the octadecylamine modified single-walled carbon nanotubes can be better exerted when the mass ratio is controlled to be (4-5): 1, so that the conductivity of the conductive paste is further improved.
In the application, the diameter of the unmodified single-walled carbon nanotube in the single-walled carbon nanotube mixture can be 1-2 nm, the length can be 5-30 mu m, the length-diameter ratio is larger, and the conductivity is excellent.
The octadecylamine modified single-walled carbon nanotube can be directly obtained from a commercial product or can be used after self-made. The method of preparing the octadecylamine modified single-walled carbon nanotubes is conventional in the art and can be routinely selected by those skilled in the art. In some embodiments, the octadecylamine modified single-walled carbon nanotubes can be prepared by: (1) Mixing the single-walled carbon nanotube with concentrated nitric acid solution, and performing ultrasonic reflux treatment at 70-90 ℃ for 15-20 hours to obtain an acidified single-walled carbon nanotube;
(2) Mixing the acidified single-walled carbon nanotubes, thionyl chloride and dimethylformamide, then carrying out heating reflux reaction at 70-80 ℃ for 15-20 h, carrying out solid-liquid separation on the mixed liquid after the reaction is finished, collecting solid precipitate, and washing with tetrahydrofuran to obtain the acyl-chlorinated single-walled carbon nanotubes;
(3) Mixing the acyl-chlorinated single-walled carbon nanotube with octadecylamine, stirring and reacting in water bath at 85-95 ℃, and removing unreacted octadecylamine after the reaction is finished to obtain the octadecylamine modified single-walled carbon nanotube.
In some embodiments, the dispersant is a mixture of polyvinylpyrrolidone, cetyltrimethylammonium bromide, and hydroxypropyl methyl ether of cellulose.
In the application, the dispersing agent in the conductive paste comprises polyvinylpyrrolidone, cetyltrimethylammonium bromide and cellulose hydroxypropyl methyl ether, and the single-walled carbon nanotube mixture can be better dispersed in the solvent through the synergistic cooperation of the polyvinylpyrrolidone, the cetyltrimethylammonium bromide and the cellulose hydroxypropyl methyl ether, and the dispersed system is more stable, so that the use amount of the dispersing agent can be reduced, and the prepared conductive paste has better conductivity and more stable system.
In some embodiments, the mass ratio of polyvinylpyrrolidone, cetyltrimethylammonium bromide and hydroxypropyl methyl ether of cellulose in the mixture is (2-5): (1-3): 1.
In some embodiments, the mass ratio of polyvinylpyrrolidone, cetyltrimethylammonium bromide, and hydroxypropyl methyl ether of cellulose in the mixture may be, for example, 2:1:1, 3:1:1, 4:1:1, 5:1:1, 3:2:1, 4:2:1, 5:2:1, 3:3:1, 4:3:1, or 5:3:1, etc. In some preferred embodiments, the mass ratio of polyvinylpyrrolidone, cetyltrimethylammonium bromide and hydroxypropyl methyl ether of cellulose in the mixture is (3-4): 2:1. In some most preferred embodiments, the mass ratio of polyvinylpyrrolidone, cetyltrimethylammonium bromide and cellulose hydroxypropyl methyl ether in the mixture is 4:2:1.
According to the application, the mass ratio of polyvinylpyrrolidone, cetyltrimethylammonium bromide and cellulose hydroxypropyl methyl ether in the dispersing agent mixture is controlled within the above range, especially controlled to be 4:2:1, so that the dispersing agent can better exert the dispersing performance, and the dispersing effect of the single-walled carbon nanotube mixture is better.
The polyvinylpyrrolidone, the cetyl trimethyl ammonium bromide and the cellulose hydroxypropyl methyl ether are conventional commercial products, the molecular weight of the polyvinylpyrrolidone can be 4 ten thousand to 10 ten thousand, and the molecular weight of the cellulose hydroxypropyl methyl ether can be 6 ten thousand to 10 ten thousand.
In some embodiments, the polyvinylidene fluoride (PVDF) has a molecular weight of 20 to 70 tens of thousands. In some preferred embodiments, the polyvinylidene fluoride has a molecular weight of 50 ten thousand.
If the molecular weight of the binder PVDF adopted in the application is too high, such as more than 70 ten thousand, the viscosity of the electrode slurry is too high when the prepared conductive slurry is used for preparing a lithium ion battery, the dispersion of electrode active substances is not facilitated, and the coating processability is also reduced. However, the bonding force provided by the PVDF with low molecular weight is limited, and the required bonding performance cannot be exerted, so that the cellulose hydroxypropyl methyl ether is added in the dispersing agent disclosed by the application, the cellulose hydroxypropyl methyl ether is not only beneficial to the dispersion of the single-wall carbon nano tube, but also can be matched with the PVDF to provide a certain bonding force, so that the prepared conductive paste has better service performance.
In some embodiments, the mass ratio of polyvinylidene fluoride to hydroxypropyl methyl ether of cellulose is (5-10): 1. In some preferred embodiments, the mass ratio of polyvinylidene fluoride to hydroxypropyl methyl ether of cellulose is 7:1.
The application can further improve the performance of the prepared conductive slurry by controlling the dosage relation of the polyvinylidene fluoride and the cellulose hydroxypropyl methyl ether in the range.
A second aspect of the present application provides a method for preparing the conductive paste according to the first aspect of the present application, the method comprising the steps of:
s1, mixing a first amount of N-methyl pyrrolidone with the dispersant to obtain a dispersant solution;
s2, mixing a second dosage of N-methyl pyrrolidone with the polyvinylidene fluoride to obtain a polyvinylidene fluoride solution;
s3, mixing the rest amount of N-methyl pyrrolidone with the single-walled carbon nanotube mixture, and then grinding and dispersing to obtain a single-walled carbon nanotube mixed solution;
and S4, mixing the single-walled carbon nanotube mixed solution with the dispersing agent solution, then carrying out grinding dispersion, and stirring and mixing the obtained mixed solution with the polyvinylidene fluoride solution, and then carrying out grinding dispersion to obtain the conductive slurry.
Because the dispersing agent and the binder in the conductive paste both contain polymers, in the preparation process of the conductive paste, the dispersing agent and the binder are respectively dissolved by adopting the solvent, and then the dissolved dispersing agent solution and binder solution are mixed with the mixed solution containing the single-walled carbon nanotube mixture, so that the dispersion of the single-walled carbon nanotube mixture powder is facilitated.
In some embodiments, the first amount of N-methylpyrrolidone is 8 to 12 weight percent of the total amount of N-methylpyrrolidone and the second amount of N-methylpyrrolidone is 25 to 30 weight percent of the total amount of N-methylpyrrolidone.
In the application, the sum of the first dosage of N-methyl pyrrolidone, the second dosage of N-methyl pyrrolidone and the rest amount of N-methyl pyrrolidone is the total dosage of N-methyl pyrrolidone in the application.
In the present application, "mixing" in the method may be performed under stirring conditions, for example, stirring may be performed using a stirring tank or a stirring disperser, and the stirring time may be 60 to 240 minutes.
In some embodiments, the grinding and dispersing are performed using a sand mill, the sand medium of the sand mill is zirconia balls, the zirconia balls have a diameter of 0.5-2 mm, the sand time is 2-5 hours, and the sand speed is 1000-1500 r/min.
In the application, the single-walled carbon nanotube mixture can be better dispersed in the solvent N-methylpyrrolidone by grinding and dispersing by a sand mill under the above parameter conditions.
In a third aspect, the application provides an electroconductive paste according to the first aspect of the application, or an electroconductive paste prepared by the method according to the second aspect, for use in the preparation of a lithium ion battery.
The oil-based single-walled carbon nanotube conductive paste provided by the application has the advantages of good dispersibility, low resistivity, excellent conductivity and small usage amount of auxiliary agent, so that the oil-based single-walled carbon nanotube conductive paste can be better applied to the preparation of lithium ion batteries.
The beneficial technical effects of the application are as follows: the single-walled carbon nanotube mixture in the oil-based single-walled carbon nanotube conductive paste provided by the application contains the unmodified single-walled carbon nanotubes and the octadecylamine modified single-walled carbon nanotubes, and through the synergistic cooperation of the single-walled carbon nanotubes and the octadecylamine modified single-walled carbon nanotubes, the single-walled carbon nanotube mixture in the conductive paste has better dispersibility, the using amount of an auxiliary agent is reduced, and meanwhile, the conductive paste has better conductivity, so that the conductive paste prepared by the oil-based single-walled carbon nanotube conductive paste has excellent conductive performance. Meanwhile, the dispersing agent in the conductive paste contains polyvinylpyrrolidone, cetyltrimethylammonium bromide and cellulose hydroxypropyl methyl ether, so that the dispersing performance of the dispersing agent is excellent, the single-wall carbon nanotube mixture is better dispersed in a solvent, and the cellulose hydroxypropyl methyl ether in the dispersing agent can also provide binding force with PVDF with low molecular weight, so that the service performance and conductivity of the conductive paste are improved.
Drawings
Fig. 1 is an SEM image of single-walled carbon nanotubes in the conductive paste of oil-based single-walled carbon nanotubes prepared in example 1 of the present application.
Detailed Description
In order that the application may be more readily understood, the application will be further described in detail with reference to the following examples, which are given by way of illustration only and are not limiting in scope of application. The starting materials or components used in the present application may be prepared by commercial or conventional methods unless specifically indicated.
The unmodified single-walled carbon nanotubes used in the examples below had a tube diameter of 1.58nm and a length of 20. Mu.m; the molecular weight of polyvinylpyrrolidone is 4 ten thousand, and the molecular weight of cellulose hydroxypropyl methyl ether is 8.6 ten thousand.
Example 1: the preparation raw materials of the oil-based single-walled carbon nanotube conductive paste comprise the following components: 0.7 parts by weight of a single-walled carbon nanotube mixture, 0.5 parts by weight of a dispersant, 0.5 parts by weight of polyvinylidene fluoride, 98.3 parts by weight of N-methylpyrrolidone; wherein the mass ratio of the unmodified single-walled carbon nanotube to the octadecylamine modified single-walled carbon nanotube in the single-walled carbon nanotube mixture is 4:1, the dispersing agent contains polyvinylpyrrolidone, cetyltrimethylammonium bromide and cellulose hydroxypropyl methyl ether, the mass ratio of the polyvinylpyrrolidone, the cetyltrimethylammonium bromide and the cellulose hydroxypropyl methyl ether is 4:2:1, the mass ratio of polyvinylidene fluoride to the cellulose hydroxypropyl methyl ether is 7:1, and the molecular weight of the polyvinylidene fluoride is 50 ten thousand.
The preparation process comprises the following steps: mixing N-methyl pyrrolidone accounting for 10.5wt% of the total dosage of N-methyl pyrrolidone with a dispersing agent, stirring and dissolving for 60min to prepare a dispersing agent solution. And mixing 28.0wt% of N-methyl pyrrolidone and polyvinylidene fluoride, and stirring and dissolving for 240min to obtain PVDF solution. Mixing the rest N-methyl pyrrolidone with the single-walled carbon nanotube mixture, stirring and dispersing for 60min, starting a sand mill to grind for 2h, adding the dispersing agent solution, stirring and dispersing for 60min, grinding for 5h by the sand mill, adding the PVDF solution, stirring and dispersing for 60min, and grinding and dispersing by the sand mill for 2h to obtain the oil-based single-walled carbon nanotube conductive slurry. Wherein the sand grinding medium of the sand grinder is zirconium dioxide balls, the diameter of the zirconium dioxide balls is 0.9mm, and the sand grinding speed of the sand grinder is 1300r/min. An SEM image of the single-walled carbon nanotubes in the prepared oil-based single-walled carbon nanotube conductive paste is shown in fig. 1. As can be seen from fig. 1, the single-walled carbon nanotubes are uniformly dispersed in a solvent, and the dispersibility is excellent.
Example 2: the preparation raw materials of the oil-based single-walled carbon nanotube conductive paste comprise the following components: 0.4 parts by weight of a single-walled carbon nanotube mixture, 0.5 parts by weight of a dispersant, 0.5 parts by weight of polyvinylidene fluoride, 98.6 parts by weight of N-methylpyrrolidone; wherein the mass ratio of the unmodified single-walled carbon nanotube to the octadecylamine modified single-walled carbon nanotube in the single-walled carbon nanotube mixture is 4:1, the dispersing agent contains polyvinylpyrrolidone, cetyltrimethylammonium bromide and cellulose hydroxypropyl methyl ether, the mass ratio of the polyvinylpyrrolidone, the cetyltrimethylammonium bromide and the cellulose hydroxypropyl methyl ether is 4:2:1, the mass ratio of polyvinylidene fluoride to the cellulose hydroxypropyl methyl ether is 7:1, and the molecular weight of the polyvinylidene fluoride is 50 ten thousand.
The preparation process comprises the following steps: as in example 1.
Example 3: the preparation raw materials of the oil-based single-walled carbon nanotube conductive paste comprise the following components: 0.1 part by weight of a single-walled carbon nanotube mixture, 0.5 part by weight of a dispersant, 0.5 part by weight of polyvinylidene fluoride, 98.9 parts by weight of N-methylpyrrolidone; wherein the mass ratio of the unmodified single-walled carbon nanotube to the octadecylamine modified single-walled carbon nanotube in the single-walled carbon nanotube mixture is 4:1, the dispersing agent contains polyvinylpyrrolidone, cetyltrimethylammonium bromide and cellulose hydroxypropyl methyl ether, the mass ratio of the polyvinylpyrrolidone, the cetyltrimethylammonium bromide and the cellulose hydroxypropyl methyl ether is 4:2:1, the mass ratio of polyvinylidene fluoride to the cellulose hydroxypropyl methyl ether is 7:1, and the molecular weight of the polyvinylidene fluoride is 50 ten thousand.
The preparation process comprises the following steps: as in example 1.
Example 4: the preparation raw materials of the oil-based single-walled carbon nanotube conductive paste comprise the following components: 0.7 parts by weight of a single-walled carbon nanotube mixture, 1.0 parts by weight of a dispersant, 1.0 parts by weight of polyvinylidene fluoride, 97.3 parts by weight of N-methylpyrrolidone; wherein the mass ratio of the unmodified single-walled carbon nanotube to the octadecylamine modified single-walled carbon nanotube in the single-walled carbon nanotube mixture is 4:1, the dispersing agent contains polyvinylpyrrolidone, cetyltrimethylammonium bromide and cellulose hydroxypropyl methyl ether, the mass ratio of the polyvinylpyrrolidone, the cetyltrimethylammonium bromide and the cellulose hydroxypropyl methyl ether is 4:2:1, the mass ratio of polyvinylidene fluoride to the cellulose hydroxypropyl methyl ether is 7:1, and the molecular weight of the polyvinylidene fluoride is 50 ten thousand.
The preparation process comprises the following steps: as in example 1.
Example 5: the preparation raw materials of the oil-based single-walled carbon nanotube conductive paste comprise the following components: 0.7 parts by weight of a single-walled carbon nanotube mixture, 0.5 parts by weight of a dispersant, 0.5 parts by weight of polyvinylidene fluoride, 98.3 parts by weight of N-methylpyrrolidone; wherein the mass ratio of the unmodified single-walled carbon nanotube to the octadecylamine modified single-walled carbon nanotube in the single-walled carbon nanotube mixture is 7:1, the dispersing agent contains polyvinylpyrrolidone, cetyltrimethylammonium bromide and cellulose hydroxypropyl methyl ether, the mass ratio of the polyvinylpyrrolidone, the cetyltrimethylammonium bromide and the cellulose hydroxypropyl methyl ether is 4:2:1, the mass ratio of polyvinylidene fluoride to the cellulose hydroxypropyl methyl ether is 7:1, and the molecular weight of the polyvinylidene fluoride is 50 ten thousand.
The preparation process comprises the following steps: as in example 1.
Example 6: the preparation raw materials of the oil-based single-walled carbon nanotube conductive paste comprise the following components: 0.7 parts by weight of a single-walled carbon nanotube mixture, 0.5 parts by weight of a dispersant, 0.5 parts by weight of polyvinylidene fluoride, 98.3 parts by weight of N-methylpyrrolidone; wherein the mass ratio of the unmodified single-walled carbon nanotube to the octadecylamine modified single-walled carbon nanotube in the single-walled carbon nanotube mixture is 3:1, the dispersing agent contains polyvinylpyrrolidone, cetyltrimethylammonium bromide and cellulose hydroxypropyl methyl ether, the mass ratio of the polyvinylpyrrolidone, the cetyltrimethylammonium bromide and the cellulose hydroxypropyl methyl ether is 4:2:1, the mass ratio of polyvinylidene fluoride to the cellulose hydroxypropyl methyl ether is 7:1, and the molecular weight of the polyvinylidene fluoride is 50 ten thousand.
The preparation process comprises the following steps: as in example 1.
Example 7: the preparation raw materials of the oil-based single-walled carbon nanotube conductive paste comprise the following components: 0.7 parts by weight of a single-walled carbon nanotube mixture, 0.5 parts by weight of a dispersant, 0.5 parts by weight of polyvinylidene fluoride, 98.3 parts by weight of N-methylpyrrolidone; wherein the mass ratio of the unmodified single-walled carbon nanotube to the octadecylamine modified single-walled carbon nanotube in the single-walled carbon nanotube mixture is 4:1, the dispersing agent contains polyvinylpyrrolidone, cetyltrimethylammonium bromide and cellulose hydroxypropyl methyl ether, the mass ratio of the polyvinylpyrrolidone, the cetyltrimethylammonium bromide and the cellulose hydroxypropyl methyl ether is 3:3:1, the mass ratio of polyvinylidene fluoride to the cellulose hydroxypropyl methyl ether is 7:1, and the molecular weight of the polyvinylidene fluoride is 50 ten thousand.
The preparation process comprises the following steps: as in example 1.
Example 8: the preparation raw materials of the oil-based single-walled carbon nanotube conductive paste comprise the following components: 0.7 parts by weight of a single-walled carbon nanotube mixture, 0.5 parts by weight of a dispersant, 0.5 parts by weight of polyvinylidene fluoride, 98.3 parts by weight of N-methylpyrrolidone; wherein the mass ratio of the unmodified single-walled carbon nanotube to the octadecylamine modified single-walled carbon nanotube in the single-walled carbon nanotube mixture is 4:1, the dispersing agent contains polyvinylpyrrolidone, cetyltrimethylammonium bromide and cellulose hydroxypropyl methyl ether, the mass ratio of the polyvinylpyrrolidone, the cetyltrimethylammonium bromide and the cellulose hydroxypropyl methyl ether is 5:1:1, the mass ratio of polyvinylidene fluoride to the cellulose hydroxypropyl methyl ether is 7:1, and the molecular weight of the polyvinylidene fluoride is 50 ten thousand.
The preparation process comprises the following steps: as in example 1.
Example 9: the preparation raw materials of the oil-based single-walled carbon nanotube conductive paste comprise the following components: 0.7 parts by weight of a single-walled carbon nanotube mixture, 0.5 parts by weight of a dispersant, 0.5 parts by weight of polyvinylidene fluoride, 98.3 parts by weight of N-methylpyrrolidone; wherein the mass ratio of the unmodified single-walled carbon nanotube to the octadecylamine modified single-walled carbon nanotube in the single-walled carbon nanotube mixture is 4:1, the dispersing agent contains polyvinylpyrrolidone, cetyltrimethylammonium bromide and cellulose hydroxypropyl methyl ether, the mass ratio of the polyvinylpyrrolidone, the cetyltrimethylammonium bromide and the cellulose hydroxypropyl methyl ether is 2:2:1, the mass ratio of polyvinylidene fluoride to the cellulose hydroxypropyl methyl ether is 5:1, and the molecular weight of the polyvinylidene fluoride is 50 ten thousand.
The preparation process comprises the following steps: as in example 1.
Example 10: the preparation raw materials of the oil-based single-walled carbon nanotube conductive paste comprise the following components: 0.7 parts by weight of a single-walled carbon nanotube mixture, 0.5 parts by weight of a dispersant, 0.7 parts by weight of polyvinylidene fluoride, 98.1 parts by weight of N-methylpyrrolidone; wherein the mass ratio of the unmodified single-walled carbon nanotube to the octadecylamine modified single-walled carbon nanotube in the single-walled carbon nanotube mixture is 4:1, the dispersing agent contains polyvinylpyrrolidone, cetyltrimethylammonium bromide and cellulose hydroxypropyl methyl ether, the mass ratio of the polyvinylpyrrolidone, the cetyltrimethylammonium bromide and the cellulose hydroxypropyl methyl ether is 2:2:1, the mass ratio of polyvinylidene fluoride to the cellulose hydroxypropyl methyl ether is 7:1, and the molecular weight of the polyvinylidene fluoride is 50 ten thousand.
The preparation process comprises the following steps: as in example 1.
Example 11: the preparation raw materials of the oil-based single-walled carbon nanotube conductive paste comprise the following components: 0.7 parts by weight of a single-walled carbon nanotube mixture, 0.5 parts by weight of a dispersant, 1.0 part by weight of polyvinylidene fluoride, 97.8 parts by weight of N-methylpyrrolidone; wherein the mass ratio of the unmodified single-walled carbon nanotube to the octadecylamine modified single-walled carbon nanotube in the single-walled carbon nanotube mixture is 4:1, the dispersing agent contains polyvinylpyrrolidone, cetyltrimethylammonium bromide and cellulose hydroxypropyl methyl ether, the mass ratio of the polyvinylpyrrolidone, the cetyltrimethylammonium bromide and the cellulose hydroxypropyl methyl ether is 2:2:1, the mass ratio of polyvinylidene fluoride to the cellulose hydroxypropyl methyl ether is 10:1, and the molecular weight of the polyvinylidene fluoride is 50 ten thousand.
The preparation process comprises the following steps: as in example 1.
Example 12: the preparation raw materials of the oil-based single-walled carbon nanotube conductive paste comprise the following components: 0.7 parts by weight of a single-walled carbon nanotube mixture, 0.5 parts by weight of a dispersant, 0.5 parts by weight of polyvinylidene fluoride, 98.3 parts by weight of N-methylpyrrolidone; wherein the mass ratio of the unmodified single-walled carbon nanotube to the octadecylamine modified single-walled carbon nanotube in the single-walled carbon nanotube mixture is 4:1, the dispersing agent contains polyvinylpyrrolidone and cetyltrimethylammonium bromide, the polyvinylpyrrolidone and the cetyltrimethylammonium bromide are 2:1, and the molecular weight of polyvinylidene fluoride is 50 ten thousand.
The preparation process comprises the following steps: as in example 1.
Example 13: the preparation raw materials of the oil-based single-walled carbon nanotube conductive paste comprise the following components: 0.7 parts by weight of a single-walled carbon nanotube mixture, 0.5 parts by weight of a dispersant, 0.5 parts by weight of polyvinylidene fluoride, 98.3 parts by weight of N-methylpyrrolidone; wherein the mass ratio of the unmodified single-walled carbon nanotube to the octadecylamine modified single-walled carbon nanotube in the single-walled carbon nanotube mixture is 4:1, the dispersing agent contains polyvinylpyrrolidone and cellulose hydroxypropyl methyl ether, the mass ratio of polyvinylpyrrolidone to cetyltrimethylammonium bromide is 6:1, the mass ratio of polyvinylidene fluoride to cellulose hydroxypropyl methyl ether is 7:1, and the molecular weight of polyvinylidene fluoride is 50 ten thousand.
The preparation process comprises the following steps: as in example 1.
Example 14: the preparation raw materials of the oil-based single-walled carbon nanotube conductive paste comprise the following components: 0.7 parts by weight of a single-walled carbon nanotube mixture, 0.5 parts by weight of a dispersant, 0.5 parts by weight of polyvinylidene fluoride, 98.3 parts by weight of N-methylpyrrolidone; wherein the mass ratio of the unmodified single-walled carbon nanotube to the octadecylamine modified single-walled carbon nanotube in the single-walled carbon nanotube mixture is 4:1, the dispersing agent only contains polyvinylpyrrolidone, and the molecular weight of polyvinylidene fluoride is 50 ten thousand.
The preparation process comprises the following steps: as in example 1.
Example 15: the preparation raw materials of the oil-based single-walled carbon nanotube conductive paste comprise the following components: 0.7 parts by weight of a single-walled carbon nanotube mixture, 0.5 parts by weight of a dispersant, 0.5 parts by weight of polyvinylidene fluoride, 98.3 parts by weight of N-methylpyrrolidone; wherein the mass ratio of the unmodified single-walled carbon nanotube to the octadecylamine modified single-walled carbon nanotube in the single-walled carbon nanotube mixture is 4:1, the dispersing agent only contains hexadecyl trimethyl ammonium bromide, and the molecular weight of polyvinylidene fluoride is 50 ten thousand.
The preparation process comprises the following steps: as in example 1.
Example 16: the preparation raw materials of the oil-based single-walled carbon nanotube conductive paste comprise the following components: 0.7 parts by weight of a single-walled carbon nanotube mixture, 0.5 parts by weight of a dispersant, 0.5 parts by weight of polyvinylidene fluoride, 98.3 parts by weight of N-methylpyrrolidone; wherein the mass ratio of the unmodified single-walled carbon nanotube to the octadecylamine modified single-walled carbon nanotube in the single-walled carbon nanotube mixture is 4:1, the dispersing agent only contains cellulose hydroxypropyl methyl ether, the mass ratio of polyvinylidene fluoride to the cellulose hydroxypropyl methyl ether is 1:1, and the molecular weight of polyvinylidene fluoride is 50 ten thousand.
The preparation process comprises the following steps: as in example 1.
Example 17: the preparation raw materials of the oil-based single-walled carbon nanotube conductive paste comprise the following components: substantially the same as in example 1, except that the molecular weight of polyvinylidene fluoride in the electroconductive paste was 20 ten thousand.
The preparation process comprises the following steps: as in example 1.
Example 18: the preparation raw materials of the oil-based single-walled carbon nanotube conductive paste comprise the following components: substantially the same as in example 1, except that the molecular weight of polyvinylidene fluoride in the electroconductive paste was 100 ten thousand.
The preparation process comprises the following steps: as in example 1.
Comparative example 1: the preparation raw materials of the oil-based single-walled carbon nanotube conductive paste comprise the following components: substantially the same as in example 1, except that the single-walled carbon nanotubes in the conductive paste were russian imported single-walled carbon nanotubes.
The preparation process comprises the following steps: as in example 1.
Comparative example 2: the preparation raw materials of the oil-based single-walled carbon nanotube conductive paste comprise the following components: 0.7 parts by weight of unmodified single-walled carbon nanotubes, 0.5 parts by weight of a dispersant, 0.5 parts by weight of polyvinylidene fluoride, 98.3 parts by weight of N-methylpyrrolidone; wherein the dispersing agent contains polyvinylpyrrolidone, cetyltrimethylammonium bromide and cellulose hydroxypropyl methyl ether, the mass ratio of the polyvinylpyrrolidone to the cetyltrimethylammonium bromide to the cellulose hydroxypropyl methyl ether is 4:2:1, the mass ratio of the polyvinylidene fluoride to the cellulose hydroxypropyl methyl ether is 7:1, and the molecular weight of the polyvinylidene fluoride is 50 ten thousand.
The preparation process comprises the following steps: as in example 1.
Comparative example 3: the preparation raw materials of the oil-based single-walled carbon nanotube conductive paste comprise the following components: 0.7 parts by weight of octadecylamine modified single-walled carbon nanotube, 0.5 parts by weight of dispersant, 0.5 parts by weight of polyvinylidene fluoride, 98.3 parts by weight of N-methylpyrrolidone; wherein the dispersing agent contains polyvinylpyrrolidone, cetyltrimethylammonium bromide and cellulose hydroxypropyl methyl ether, the mass ratio of the polyvinylpyrrolidone to the cetyltrimethylammonium bromide to the cellulose hydroxypropyl methyl ether is 4:2:1, the mass ratio of the polyvinylidene fluoride to the cellulose hydroxypropyl methyl ether is 7:1, and the molecular weight of the polyvinylidene fluoride is 50 ten thousand.
Comparative example 4: preparation of oil-based single-walled carbon nanotube conductive paste
The raw materials comprise: as in example 1.
The preparation process comprises the following steps: mixing the dispersant, polyvinylidene fluoride and single-walled carbon nanotube mixture with the total amount of N-methyl pyrrolidone, stirring and dissolving for 300min, and grinding and dispersing for 7h by a sand mill to obtain the oil-based single-walled carbon nanotube conductive slurry. Wherein the sand grinding medium of the sand grinder is zirconium dioxide balls, the diameter of the zirconium dioxide balls is 0.9mm, and the sand grinding speed of the sand grinder is 1300r/min.
Test case
The conductive properties of the oil-based single-walled carbon nanotube conductive pastes prepared in examples 1 to 18 and comparative examples 1 to 4 were examined, and the conductive properties were characterized by volume resistivity, with lower volume resistivity leading to better conductivity. The volume resistivity detection steps are as follows: (1) Weighing N-methyl pyrrolidone, polyvinylidene fluoride and oil system single-walled carbon nanotube conductive paste with corresponding weights, mixing and stirring for 1h, adding positive electrode active materials with corresponding weights, and stirring and dispersing for 4h to obtain mixed paste;
(2) And preparing the mixed slurry into a pole piece, detecting the pole piece by using a four-probe resistance meter, and measuring the volume resistivity of the pole piece.
The test results are shown in Table 1.
TABLE 1
From the test results of examples 1, 5 to 6 and comparative example 1 in table 1, it is understood that the conductive properties of the conductive paste using the single-walled carbon nanotube mixture containing the unmodified single-walled carbon nanotubes and the octadecylamine-modified single-walled carbon nanotubes of the present application as the conductive agent are more excellent than those of the imported single-walled carbon nanotubes. Meanwhile, as shown by the detection results of examples 1, 5-6 and comparative examples 2-3, when the conductive agent in the conductive paste is only an unmodified single-walled carbon nanotube or only an octadecylamine modified single-walled carbon nanotube, the conductive performance of the conductive paste is obviously reduced, which indicates that the unmodified single-walled carbon nanotube and the octadecylamine modified single-walled carbon nanotube in the single-walled carbon nanotube mixture can play a synergistic effect, and the conductive performance of the prepared conductive paste is more excellent under the synergistic effect of the unmodified single-walled carbon nanotube and the octadecylamine modified single-walled carbon nanotube.
From the test results of examples 1 to 4 in Table 1, it is understood that when the electroconductive paste comprises the following components in parts by weight: 0.7 part of single-walled carbon nanotube mixture, 0.5 part of dispersing agent, 0.5 part of polyvinylidene fluoride and 98.3 parts of N-methyl pyrrolidone, thereby being more beneficial to improving the conductivity of the conductive slurry.
From the test results of examples 1, 7-9 and 12-16 in table 1, it is known that when the dispersing agent in the conductive paste includes polyvinylpyrrolidone, cetyltrimethylammonium bromide and cellulose hydroxypropyl methyl ether, the three components in the dispersing agent can perform synergistic effect, so that the dispersibility of the single-walled carbon nanotube mixture in the solvent is better, and the conductive performance of the conductive paste is obviously improved.
From the test results of examples 9 to 11 in Table 1, it is found that the conductive properties of the conductive paste are improved more advantageously when the mass ratio of polyvinylidene fluoride to hydroxypropyl methyl ether of cellulose in the conductive paste is 7:1. And from the test results of examples 1 and 17-18 in table 1, it is found that the conductive properties of the conductive paste are improved more advantageously when the molecular weight of polyvinylidene fluoride in the conductive paste is 50 ten thousand.
As can be seen from the test results of example 1 and comparative example 4 in table 1, in the preparation process of the conductive paste, the dispersant and the binder are dissolved by using the solvent, and then the dissolved dispersant solution and binder solution are mixed with the mixed solution containing the single-walled carbon nanotube mixture, so that the dispersion of the single-walled carbon nanotube mixture powder is facilitated.
It should be noted that the above-described embodiments are only for explaining the present application and do not constitute any limitation of the present application. The application has been described with reference to exemplary embodiments, but it is understood that the words which have been used are words of description and illustration, rather than words of limitation. Modifications may be made to the application as defined in the appended claims, and the application may be modified without departing from the scope and spirit of the application. Although the application is described herein with reference to particular means, materials and embodiments, the application is not intended to be limited to the particulars disclosed herein, as the application extends to all other means and applications which perform the same function.
Claims (10)
1. The oil-based single-walled carbon nanotube conductive paste is characterized by comprising the following components in parts by weight: 0.1 to 1.0 part of single-walled carbon nanotube mixture, 0.1 to 1.0 part of dispersing agent, 0.1 to 1.0 part of polyvinylidene fluoride and 97.0 to 100 parts of N-methyl pyrrolidone;
wherein the single-walled carbon nanotube mixture comprises unmodified single-walled carbon nanotubes and octadecylamine modified single-walled carbon nanotubes.
2. The conductive paste according to claim 1, wherein the mass ratio of the unmodified single-walled carbon nanotubes to the octadecylamine modified single-walled carbon nanotubes in the single-walled carbon nanotube mixture is (3-7): 1.
3. The conductive paste according to claim 1 or 2, wherein the dispersant is a mixture of polyvinylpyrrolidone, cetyltrimethylammonium bromide and cellulose hydroxypropyl methyl ether.
4. The conductive paste according to claim 3, wherein the mass ratio of polyvinylpyrrolidone, cetyltrimethylammonium bromide and cellulose hydroxypropyl methyl ether in the mixture is (2-5): (1-3): 1.
5. The conductive paste according to claim 1 or 2, wherein the polyvinylidene fluoride has a molecular weight of 20 to 70 ten thousand.
6. The conductive paste according to claim 5, wherein the mass ratio of the polyvinylidene fluoride to the cellulose hydroxypropyl methyl ether is (5-10): 1.
7. A method for producing the electroconductive paste according to any one of claims 1 to 6, comprising the steps of:
s1, mixing a first amount of N-methyl pyrrolidone with the dispersant to obtain a dispersant solution;
s2, mixing a second dosage of N-methyl pyrrolidone with the polyvinylidene fluoride to obtain a polyvinylidene fluoride solution;
s3, mixing the rest amount of N-methyl pyrrolidone with the single-walled carbon nanotube mixture, and then grinding and dispersing to obtain a single-walled carbon nanotube mixed solution;
and S4, mixing the single-walled carbon nanotube mixed solution with the dispersing agent solution, then carrying out grinding dispersion, and stirring and mixing the obtained mixed solution with the polyvinylidene fluoride solution, and then carrying out grinding dispersion to obtain the conductive slurry.
8. The method of claim 7, wherein the first amount of N-methylpyrrolidone is 8 to 12wt% of the total amount of N-methylpyrrolidone and the second amount of N-methylpyrrolidone is 25 to 30wt% of the total amount of N-methylpyrrolidone.
9. The method according to claim 7 or 8, wherein the grinding and dispersing are performed by a sand mill, a sand medium of the sand mill is zirconium dioxide balls, the diameter of the zirconium dioxide balls is 0.5-2 mm, the sand time is 2-5 hours, and the sand speed is 1000-1500 r/min.
10. Use of the conductive paste according to any one of claims 1 to 6 or the conductive paste prepared by the method according to any one of claims 7 to 9 in the preparation of lithium ion batteries.
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