CN114388801B - Carbon nanotube conductive dispersion liquid and preparation method and application thereof - Google Patents
Carbon nanotube conductive dispersion liquid and preparation method and application thereof Download PDFInfo
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- 239000006185 dispersion Substances 0.000 title claims abstract description 114
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 84
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 84
- 239000007788 liquid Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000002270 dispersing agent Substances 0.000 claims abstract description 55
- 239000002002 slurry Substances 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 27
- 229920000642 polymer Polymers 0.000 claims abstract description 17
- 239000007787 solid Substances 0.000 claims abstract description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 16
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 16
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 16
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 13
- 125000003277 amino group Chemical group 0.000 claims description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 239000004349 Polyvinylpyrrolidone-vinyl acetate copolymer Substances 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000002612 dispersion medium Substances 0.000 claims description 6
- 235000019448 polyvinylpyrrolidone-vinyl acetate copolymer Nutrition 0.000 claims description 6
- 239000007970 homogeneous dispersion Substances 0.000 claims description 5
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 4
- 229930002875 chlorophyll Natural products 0.000 claims description 4
- 235000019804 chlorophyll Nutrition 0.000 claims description 4
- ATNHDLDRLWWWCB-AENOIHSZSA-M chlorophyll a Chemical group C1([C@@H](C(=O)OC)C(=O)C2=C3C)=C2N2C3=CC(C(CC)=C3C)=[N+]4C3=CC3=C(C=C)C(C)=C5N3[Mg-2]42[N+]2=C1[C@@H](CCC(=O)OC\C=C(/C)CCC[C@H](C)CCC[C@H](C)CCCC(C)C)[C@H](C)C2=C5 ATNHDLDRLWWWCB-AENOIHSZSA-M 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000002609 medium Substances 0.000 claims description 3
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 3
- 239000004793 Polystyrene Substances 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- 229920002223 polystyrene Polymers 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 9
- 238000003860 storage Methods 0.000 abstract description 7
- 239000002904 solvent Substances 0.000 abstract description 6
- 229910052799 carbon Inorganic materials 0.000 abstract description 5
- 238000000265 homogenisation Methods 0.000 abstract description 4
- 239000012535 impurity Substances 0.000 abstract description 4
- 239000002086 nanomaterial Substances 0.000 abstract description 3
- 238000011010 flushing procedure Methods 0.000 abstract description 2
- 239000002048 multi walled nanotube Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 238000004090 dissolution Methods 0.000 description 10
- 238000012360 testing method Methods 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 4
- 239000011267 electrode slurry Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- MSWZFWKMSRAUBD-IVMDWMLBSA-N 2-amino-2-deoxy-D-glucopyranose Chemical compound N[C@H]1C(O)O[C@H](CO)[C@@H](O)[C@@H]1O MSWZFWKMSRAUBD-IVMDWMLBSA-N 0.000 description 3
- PFRYFZZSECNQOL-UHFFFAOYSA-N 2-methyl-4-[(2-methylphenyl)diazenyl]aniline Chemical compound C1=C(N)C(C)=CC(N=NC=2C(=CC=CC=2)C)=C1 PFRYFZZSECNQOL-UHFFFAOYSA-N 0.000 description 3
- MSWZFWKMSRAUBD-UHFFFAOYSA-N beta-D-galactosamine Natural products NC1C(O)OC(CO)C(O)C1O MSWZFWKMSRAUBD-UHFFFAOYSA-N 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 229960002442 glucosamine Drugs 0.000 description 3
- 239000001397 quillaja saponaria molina bark Substances 0.000 description 3
- 229930182490 saponin Natural products 0.000 description 3
- 150000007949 saponins Chemical class 0.000 description 3
- 238000001132 ultrasonic dispersion Methods 0.000 description 3
- JCBPETKZIGVZRE-UHFFFAOYSA-N 2-aminobutan-1-ol Chemical compound CCC(N)CO JCBPETKZIGVZRE-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- WUGQZFFCHPXWKQ-UHFFFAOYSA-N Propanolamine Chemical compound NCCCO WUGQZFFCHPXWKQ-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 239000000987 azo dye Substances 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 150000003141 primary amines Chemical class 0.000 description 2
- 150000003335 secondary amines Chemical class 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- CWKVFRNCODQPDB-UHFFFAOYSA-N 1-(2-aminoethylamino)propan-2-ol Chemical compound CC(O)CNCCN CWKVFRNCODQPDB-UHFFFAOYSA-N 0.000 description 1
- HTTJABKRGRZYRN-UHFFFAOYSA-N Heparin Chemical compound OC1C(NC(=O)C)C(O)OC(COS(O)(=O)=O)C1OC1C(OS(O)(=O)=O)C(O)C(OC2C(C(OS(O)(=O)=O)C(OC3C(C(O)C(O)C(O3)C(O)=O)OS(O)(=O)=O)C(CO)O2)NS(O)(=O)=O)C(C(O)=O)O1 HTTJABKRGRZYRN-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 description 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229960002897 heparin Drugs 0.000 description 1
- 229920000669 heparin Polymers 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- -1 polyethylene terephthalate Polymers 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000002109 single walled nanotube Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Carbon And Carbon Compounds (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention belongs to the technical field of carbon nano materials, and discloses a carbon nano tube conductive dispersion liquid, a preparation method and application thereof. The carbon nanotube conductive dispersion liquid comprises carbon nanotubes, amphiphilic block polymer dispersing agent, second dispersing agent, auxiliary dispersing agent and dispersing medium, wherein the preparation method adopts a micro-jet and high-pressure homogenization mode, and the dispersion of the carbon nanotubes is realized by opposite flushing of slurry, so that the dispersion effect is good, and impurities are not easy to introduce in the dispersion process; meanwhile, the amphiphilic block polymer dispersing agent is added to be matched with a second dispersing agent, and the auxiliary dispersing agent is used, so that the carbon nano tube is not easy to absorb the solvent when dispersing under higher solid content. Therefore, the dispersion liquid can keep the viscosity change to be less than 400% in a long-time storage process, has good conductivity and stability, and has good application prospect in batteries.
Description
Technical Field
The invention belongs to the technical field of carbon nano materials, and particularly relates to a carbon nano tube conductive dispersion liquid, a preparation method and application thereof.
Background
The carbon nano tube is used as a one-dimensional nano material with high length-diameter ratio, high conductivity and high flexibility, is widely applied in the field of lithium batteries, and can be added into an electrode material of the lithium ion battery to form an effective conductive network, so that the capacity and the cycle performance of the battery are greatly improved. However, since the high specific surface area and high aspect ratio of the carbon nanotubes make it extremely difficult to disperse, only the carbon nanotubes can be prepared into a paste to sufficiently exert their effects, and it is required in industrial applications that the mass content of the carbon nanotubes in the carbon nanotube conductive paste is 1% or more and that the carbon nanotubes have a storage life of at least several months.
In the prior art, the carbon nanotube conductive paste generally uses N-methyl pyrrolidone (NMP) as a dispersion medium, uses an amphiphilic polymer and a block polymer as a dispersing agent, and adopts ultrasonic dispersion or sand grinding dispersion in a dispersion mode. Although the ultrasonic dispersion can obtain a better dispersion effect, the ultrasonic dispersion can damage the carbon nano tube and influence the conductivity; the common sanding dispersion in industrial production can realize batch production, the sanding medium generally uses zirconium beads, the zirconium beads are large in filling volume in the sanding process, the carbon nano tubes can be damaged, and impurities are easy to introduce.
The carbon nanotubes are dispersed in a slurry opposite-impact mode by the aid of micro-jet and high-pressure homogenization, so that good dispersing effect can be achieved, damage to the carbon nanotubes is small, impurities are not easy to introduce in the dispersing process, and the original performance of the carbon nanotubes is kept. However, in the dispersing process, the carbon nano tube is opened to absorb the solvent, so that the viscosity of the slurry is increased sharply, and the phenomenon of blocking and even overload occurs during micro-jet and high-pressure homogeneous dispersion.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems in the prior art described above. Therefore, the invention provides a carbon nano tube conductive dispersion liquid which has excellent conductive performance and long storage life.
The invention also provides a preparation method of the carbon nanotube conductive dispersion liquid.
The invention also provides application of the carbon nanotube conductive dispersion liquid.
According to one aspect of the present invention, a carbon nanotube conductive dispersion is provided, comprising carbon nanotubes, an amphiphilic block polymer dispersant, a second dispersant, a co-dispersant, and a dispersion medium;
the second dispersant comprises at least one of saponin, heparin, chlorophyll or azo dye;
The dispersion aid agent comprises a compound containing amino and hydroxyl; the amine group comprises one of a primary amine or a secondary amine; the number of amine groups is 1, the number of hydroxyl groups is more than or equal to 1, the number of carbon atoms in the fatty chain of the compound is less than or equal to 6, and the number of carbon atoms which are not connected with the hydroxyl groups is less than or equal to 4.
According to a preferred embodiment of the invention, there is at least the following advantageous effect:
According to the carbon nanotube conductive dispersion liquid, the amphiphilic block polymer dispersing agent is matched with the second dispersing agent, and the auxiliary dispersing agent is added, so that the carbon nanotubes can be well dispersed, and the carbon nanotube conductive dispersion liquid has good stability and conductivity.
In some embodiments of the present invention, the azo dye includes a benzene ring and an amino group, wherein the benzene ring number is greater than or equal to 2 and the amino group number is greater than or equal to 1.
In some embodiments of the invention, the dispersion aid agent accounts for less than or equal to 0.4% of the carbon nanotube conductive dispersion by mass.
In some embodiments of the invention, the carbon nanotubes comprise at least one of single-walled carbon nanotubes, multi-walled carbon nanotubes, or arrayed carbon nanotubes.
In some preferred embodiments of the present invention, the carbon nanotubes are selected from multi-walled carbon nanotubes.
In some embodiments of the invention, the amphiphilic block polymer dispersant comprises at least one of polyvinylpyrrolidone (PVP), hydrogenated Nitrile Butadiene Rubber (HNBR), polyvinyl butyral (PVB), polyvinylpyrrolidone-vinyl acetate copolymer (PVP-VA), polystyrene acrylonitrile copolymer (SAN).
In some preferred embodiments of the present invention, the amphiphilic block polymer dispersant comprises at least one of polyvinylpyrrolidone (PVP) or polyvinylpyrrolidone-vinyl acetate copolymer (PVP-VA).
In some more preferred embodiments of the invention, the amphiphilic block polymer dispersant is selected from polyvinylpyrrolidone (PVP).
In some embodiments of the invention, the ratio of the two dispersants to the total solid content of the carbon nanotube conductive dispersion is 30% by mass or less.
In some embodiments of the invention, the mass ratio of the amphiphilic block polymer dispersant to the second dispersant is from 2:1 to 8:1.
In some preferred embodiments of the present invention, the mass ratio of the amphiphilic block polymer dispersant to the second dispersant is from 2:1 to 5:1.
In some embodiments of the invention, the dispersion medium comprises at least one of N-methylpyrrolidone (NMP), acetamide, or N, N-dimethylformamide.
In some preferred embodiments of the invention, the dispersion medium is selected from the group consisting of N-methylpyrrolidone.
According to still another aspect of the present invention, there is provided a method for preparing the carbon nanotube conductive dispersion, comprising the steps of:
S1: pre-dispersing an amphiphilic block polymer dispersing agent, a second dispersing agent, an auxiliary dispersing agent and a dispersing medium, and then adding carbon nano tubes to continue dispersing to obtain slurry;
s2: the slurry in the step S1 is subjected to homogenization and dispersion to obtain carbon nanotube conductive dispersion liquid; preferably, the homogenous dispersion comprises one of a microfluidic dispersion or a high pressure homogenous dispersion.
The preparation method according to a preferred embodiment of the present invention has at least the following advantageous effects:
The invention adopts a mode of micro-jet and high-pressure homogenization, realizes the dispersion of the carbon nano tube by opposite flushing of the slurry, has good dispersion effect, has less damage to the carbon nano tube, and is not easy to introduce impurities in the dispersion process; meanwhile, the amphiphilic block polymer dispersing agent is added to be matched with a second dispersing agent, and the auxiliary dispersing agent is used, so that the carbon nano tube is not easy to absorb the solvent when dispersing under higher solid content. Therefore, the viscosity of the carbon nano tube conductive dispersion liquid prepared by the method is not increased sharply, the viscosity change can be kept to be less than 400% in a long-time storage process, and the carbon nano tube conductive dispersion liquid has good conductivity and stability.
In some embodiments of the invention, the pre-dispersing and the dispersing of step S1 are accomplished using a disperser with a speed of 1500rpm to 2000rpm.
In some embodiments of the present invention, in step S1, the pre-dispersing time is 30min to 45min, and the dispersing time is 30min to 60min.
In some preferred embodiments of the present invention, in step S1, the pre-dispersion time is 30min, and the dispersion time is 30min.
In some preferred embodiments of the present invention, in step S2, the homogeneous dispersion is a high-pressure homogeneous dispersion.
In some embodiments of the invention, in step S2, the homogeneously dispersing is sequentially dispersing using low to high pressure.
In some embodiments of the present invention, in step S2, the dispersion pressure of the homogeneous dispersion is 20MPa to 40MPa, and the dispersion pressure is gradually increased, and each time the dispersion pressure is adjusted by 10MPa; at each dispersing pressure, the dispersing times are less than or equal to 3.
According to a third aspect of the present invention, there is provided the use of the carbon nanotube conductive dispersion in a battery paste composition.
A battery positive electrode slurry composition comprises a carbon nanotube conductive dispersion liquid, an electrode active material, a binder and a solvent. The carbon nanotube conductive dispersion liquid is selected from the carbon nanotube conductive dispersion liquid, and the electrode active material, the binder and the solvent are selected from materials commonly used in the field of batteries.
According to a fourth aspect of the present invention, there is provided the use of the carbon nanotube conductive dispersion in a battery.
The battery positive electrode slurry composition is coated on a positive electrode current collector, dried and calendered to form the positive electrode of the battery.
A battery comprises a positive electrode, a negative electrode, a separator arranged between the positive electrode and the negative electrode and an electrolyte, wherein the positive electrode is the positive electrode of the battery, and the negative electrode, the separator arranged between the positive electrode and the negative electrode and the electrolyte are selected from materials commonly used in the field of batteries.
Detailed Description
The conception and the technical effects produced by the present invention will be clearly and completely described in conjunction with the embodiments below to fully understand the objects, features and effects of the present invention. It is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments, and that other embodiments obtained by those skilled in the art without inventive effort are within the scope of the present invention based on the embodiments of the present invention. The test methods used in the examples are conventional methods unless otherwise specified; the materials, reagents and the like used, unless otherwise specified, are those commercially available.
The components of the carbon nanotube conductive dispersions prepared in examples 1 to 6 and comparative examples 1 to 4 are shown in Table 1.
TABLE 1
Example 1
The embodiment prepares the carbon nanotube conductive dispersion liquid 1, and the specific process is as follows:
Adding 487.5g of NMP, 2g of PVP, 0.5g of chlorophyll and 1g of 2-amino-1-butanol into a high-speed dispersing machine, dispersing at 1500 rpm-2000 rpm for 30min, and adding 9g of multi-wall carbon nano tubes to continue dispersing for 30min after complete dissolution to obtain slurry; adding the slurry into a micro-jet homogenizer, dispersing for 3 times under the pressure of 20MPa, adjusting the pressure to 30MPa for 3 times, and adjusting the pressure to 40MPa for 3 times to obtain the carbon nanotube conductive dispersion liquid 1.
Example 2
The embodiment prepares the carbon nanotube conductive dispersion liquid 2, and the specific process is as follows:
Adding 487.5g of NMP, 2g of PVP, 0.5g of saponin and 1g of 2-amino-1-butanol into a high-speed dispersing machine, dispersing for 30min at 1500 rpm-2000 rpm, and adding 9g of multi-wall carbon nano tubes for continuous dispersion for 30min after complete dissolution to obtain slurry; adding the slurry into a micro-jet homogenizer, dispersing for 3 times under the pressure of 20MPa, adjusting the pressure to 30MPa for 3 times, and adjusting the pressure to 40MPa for 3 times to obtain the carbon nanotube conductive dispersion liquid 2.
Example 3
The embodiment prepares the carbon nanotube conductive dispersion 3, and the specific process is as follows:
adding 487.5g of NMP, 2g of PVP, 0.5g of chlorophyll and 1g of glucosamine into a high-speed dispersing machine, dispersing for 30min at 1500-2000 rpm, and adding 9g of multi-wall carbon nano tube to continue dispersing for 30min after complete dissolution to obtain slurry; adding the slurry into a micro-jet homogenizer, dispersing for 3 times under the pressure of 20MPa, adjusting the pressure to 30MPa for 3 times, and adjusting the pressure to 40MPa for 3 times to obtain the carbon nanotube conductive dispersion liquid 3.
Example 4
The embodiment prepares the carbon nanotube conductive dispersion liquid 4, and the specific process is as follows:
Adding 487.5g of NMP, 2g of PVP-VA, 0.5g of saponin and 1g of 3-aminopropanol into a high-speed dispersing machine, dispersing for 30min at 1500 rpm-2000 rpm, and adding 9g of multi-wall carbon nano tubes to continue dispersing for 30min after complete dissolution to obtain slurry; adding the slurry into a micro-jet homogenizer, dispersing for 3 times under the pressure of 20MPa, adjusting the pressure to 30MPa for 3 times, and adjusting the pressure to 40MPa for 3 times to obtain the carbon nanotube conductive dispersion liquid 4.
Example 5
The embodiment prepares the carbon nanotube conductive dispersion 5 by the following specific processes:
Adding NMP 487.5g,PVP 2g,0.5g solvent yellow 3 and 3-aminopropanol 1g into a high-speed dispersing machine, dispersing for 30min at 1500 rpm-2000 rpm, and adding multi-wall carbon nano tube 9g for continuous dispersing for 30min after complete dissolution to obtain slurry; adding the slurry into a micro-jet homogenizer, dispersing for 3 times under the pressure of 20MPa, adjusting the pressure to 30MPa for 3 times, and adjusting the pressure to 40MPa for 3 times to obtain the carbon nanotube conductive dispersion liquid 5.
Example 6
The embodiment prepares the carbon nanotube conductive dispersion 6, and the specific process is as follows:
Adding NMP 487.5g,PVP 2g,0.5g solvent black 32 and glucosamine 1g into a high-speed dispersing machine, dispersing for 30min at 1500 rpm-2000 rpm, and adding multi-wall carbon nano tube 9g for continuous dispersing for 30min after complete dissolution to obtain slurry; adding the slurry into a micro-jet homogenizer, dispersing for 3 times under the pressure of 20MPa, adjusting the pressure to 30MPa for 3 times, and adjusting the pressure to 40MPa for 3 times to obtain the carbon nanotube conductive dispersion liquid 6.
Comparative example 1
The carbon nanotube conductive dispersion liquid a was prepared in this comparative example, which is different from example 1 in that the second dispersant and the auxiliary dispersant were not added to the carbon nanotube conductive dispersion liquid prepared in this comparative example. The specific process is as follows:
adding NMP 489g,PVP 2g,1500rpm-2000 rpm into a high-speed dispersing machine for dispersing for 30min, and adding 9g of multi-wall carbon nano tubes for continuing dispersing for 30min after complete dissolution to obtain slurry; adding the slurry into a micro-jet homogenizer, dispersing for 3 times under the pressure of 20MPa, adjusting the pressure to 30MPa for 3 times, and adjusting the pressure to 40MPa for 3 times to obtain the carbon nanotube conductive dispersion liquid a.
Comparative example 2
The present example prepared a carbon nanotube conductive dispersion b, which was different from example 3 in that the carbon nanotube conductive dispersion prepared in the present comparative example was not added with a second dispersant. The specific process is as follows:
Adding 487.5g of NMP, 2g of PVP and 1g of glucosamine into a high-speed dispersing machine, dispersing for 30min at 1500-2000 rpm, and adding 9g of multi-wall carbon nano tube to continue dispersing for 30min after complete dissolution to obtain slurry; adding the slurry into a micro-jet homogenizer, dispersing for 3 times under the pressure of 20MPa, adjusting the pressure to 30MPa for 3 times, and adjusting the pressure to 40MPa for 3 times to obtain the carbon nanotube conductive dispersion liquid b.
Comparative example 3
The carbon nanotube conductive dispersion c was prepared in this example, which is different from example 5 in that the carbon number of the auxiliary dispersant added to the carbon nanotube conductive dispersion prepared in this comparative example was > 6. The specific process is as follows:
Adding NMP 487.5g,PVP 2g,0.5g solvent yellow 3 and triisopropanolamine 1g into a high-speed dispersing machine, dispersing for 30min at 1500 rpm-2000 rpm, and adding 9g of multi-wall carbon nano tubes to continue dispersing for 30min after complete dissolution to obtain slurry; adding the slurry into a micro-jet homogenizer, dispersing for 3 times under the pressure of 20MPa, adjusting the pressure to 30MPa for 3 times, and adjusting the pressure to 40MPa for 3 times to obtain the carbon nanotube conductive dispersion liquid c.
Comparative example 4
The carbon nanotube conductive dispersion d was prepared in this example, which is different from example 5 in that the number of amine groups of the auxiliary dispersant added to the carbon nanotube conductive dispersion prepared in this comparative example was 2. The specific process is as follows:
Adding NMP 487.5g,PVP 2g,0.5g solvent yellow 3 and N- (2-hydroxypropyl) ethylenediamine 1g into a high-speed dispersing machine, dispersing for 30min at 1500 rpm-2000 rpm, adding multi-wall carbon nano tube 9g after complete dissolution, and continuing dispersing for 30min to obtain slurry; adding the slurry into a micro-jet homogenizer, dispersing for 3 times under the pressure of 20MPa, adjusting the pressure to 30MPa for 3 times, and adjusting the pressure to 40MPa for 3 times to obtain the carbon nanotube conductive dispersion d.
Test examples
The present test example tests the dispersion, viscosity and resistivity of the carbon nanotube conductive dispersion prepared in the examples and comparative examples. Wherein:
the dispersion was observed during the microfluidic process.
The viscosity test method comprises the following steps: immediately after the preparation of the carbon nanotube conductive dispersion, the viscosity of the dispersion was tested with a rotational viscometer as an initial viscosity; the dispersion was then placed in a standard condition environment and monitored for viscosity changes within 90d, with viscosity measurements taken every 30 d.
Resistivity testing method: the method comprises the steps of preparing battery slurry by using a ternary nickel cobalt manganese active material (NCM 523) as a main material and polyvinylidene fluoride (PVDF) as a binder, wherein the specific mass ratio is as follows: and (2) a binder: conductive agent (carbon nanotube) =100: 1.5:0.2 (the conductive agent is placed for 90 d), proper NMP is added to adjust viscosity, positive electrode slurry is carried out, the positive electrode slurry is coated on a polyethylene terephthalate (PET) film, the film is dried, and a four-probe volume resistivity tester is used for testing the resistivity.
The test results are shown in tables 2,3 and 4.
TABLE 2
TABLE 3 Table 3
TABLE 4 Table 4
In table 2, compared with the conductive dispersions 1, 2 and 4, the conductive dispersion a is free from adding the second dispersing agent and the auxiliary dispersing agent, is easy to block/overload in the dispersing process, has high initial viscosity, gradually increases the viscosity along with the extension of the storage time, is obviously larger than the viscosity of the conductive dispersions 1, 2 and 4, has a viscosity change of more than 400%, and has higher resistivity. The second dispersant and the auxiliary dispersant are shown to be beneficial to reducing the viscosity and resistivity of the carbon nanotube conductive dispersion, thereby maintaining good stability and conductivity of the dispersion.
In table 3, the second dispersant was not added to the conductive dispersion b, and there was a slight blocking phenomenon during dispersion, but the initial viscosity was almost the same as that of the conductive dispersions 3 and 6, but the viscosity was gradually increased with the storage time, significantly higher than that of the conductive dispersions 3 and 6, and the viscosity was changed by more than 400%, and the resistivity was also higher. The second dispersing agent can reduce the viscosity and the resistivity of the carbon nanotube conductive dispersion liquid to a certain extent, so that the dispersion liquid can keep good stability and conductivity.
In Table 4, the number of carbon atoms of the auxiliary dispersant in the conductive dispersion liquid c is > 6, the number of amine groups of the auxiliary dispersant in the conductive dispersion liquid d is 2, which is different from the auxiliary dispersant in the dispersion liquid 5 (the number of carbon atoms is not more than 6, the number of amine groups is 1), the auxiliary dispersant is easy to block/overload in the dispersion process, the initial viscosity is high, the viscosity is gradually increased along with the extension of the storage time, the viscosity is obviously higher than that of the conductive dispersion liquid 5, the viscosity change is higher than 400%, and the resistivity is also high. The selection of the dispersion aid agent is limited to a certain extent, and the dispersion aid agent is required to meet the requirements that the dispersion aid agent comprises an amino group and a hydroxyl group, wherein the amino group is one of primary amine or secondary amine, the amino group is 1, the hydroxyl group is more than or equal to 1, the carbon atom number is less than or equal to 6, and the carbon atom number of an unconnected hydroxyl group is less than or equal to 4, and if the conditions are not met, the viscosity and the resistivity of the carbon nano tube conductive dispersion liquid are increased, so that the dispersion liquid cannot maintain good stability and conductivity.
While the embodiments of the present invention have been described in detail, the present invention is not limited to the above embodiments, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art. Furthermore, embodiments of the invention and features of the embodiments may be combined with each other without conflict.
Claims (11)
1. A carbon nanotube conductive dispersion, comprising: carbon nanotubes, amphiphilic block polymer dispersant, second dispersant, auxiliary dispersant and dispersion medium; the second dispersant is chlorophyll;
The dispersion aid agent comprises a compound containing amino and hydroxyl; the amine group comprises one of a primary amine or a secondary amine; the number of amine groups is 1, the number of hydroxyl groups is more than or equal to 1, the number of carbon atoms in the fatty chain of the compound is less than or equal to 6, and the number of carbon atoms which are not connected with the hydroxyl groups is less than or equal to 4;
the amphiphilic block polymer dispersant comprises at least one of polyvinylpyrrolidone, polyvinyl butyral, polyvinylpyrrolidone-vinyl acetate copolymer and polystyrene acrylonitrile copolymer;
The mass ratio of the amphiphilic block polymer dispersing agent to the second dispersing agent is 2:1-5:1.
2. The dispersion of claim 1, wherein the co-dispersant comprises less than or equal to 0.4% by mass of the carbon nanotube conductive dispersion.
3. The dispersion liquid according to claim 1, wherein a ratio of two kinds of dispersing agents to a total solid content of the carbon nanotube conductive dispersion liquid is 30% by mass or less.
4. The dispersion of claim 1, wherein the dispersion medium comprises at least one of N-methylpyrrolidone, acetamide, or N, N-dimethylformamide.
5. The method for producing the dispersion liquid according to any one of claims 1 to 4, comprising the steps of:
S1: pre-dispersing an amphiphilic block polymer dispersing agent, a second dispersing agent, an auxiliary dispersing agent and a dispersing medium, and then adding carbon nano tubes to continue dispersing to obtain slurry;
s2: and (3) carrying out homogenizing dispersion on the slurry in the step (S1) to obtain the carbon nanotube conductive dispersion liquid.
6. The method of preparing according to claim 5, wherein the homogeneously dispersing comprises one of microfluidic dispersing or high pressure homogeneously dispersing.
7. The method according to claim 5, wherein the dispersion pressure of the homogeneous dispersion is 20MPa to 40MPa.
8. The method of claim 7, wherein the dispersion pressure is increased successively by 10MPa each time.
9. The method according to claim 8, wherein the number of dispersions is 3 or less at each of the dispersing pressures.
10. Use of the dispersion according to any one of claims 1 to 4 or the dispersion produced according to the production process of any one of claims 5 to 9 in a battery slurry composition.
11. Use of a dispersion according to any one of claims 1 to 4 or a dispersion prepared according to the preparation method of any one of claims 5 to 9 in a battery.
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