CN114388801A - Carbon nano tube conductive dispersion liquid and preparation method and application thereof - Google Patents
Carbon nano tube conductive dispersion liquid and preparation method and application thereof Download PDFInfo
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- CN114388801A CN114388801A CN202111578607.4A CN202111578607A CN114388801A CN 114388801 A CN114388801 A CN 114388801A CN 202111578607 A CN202111578607 A CN 202111578607A CN 114388801 A CN114388801 A CN 114388801A
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- 239000006185 dispersion Substances 0.000 title claims abstract description 130
- 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 52
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 239000002270 dispersing agent Substances 0.000 claims abstract description 53
- 239000002002 slurry Substances 0.000 claims abstract description 32
- 229920000642 polymer Polymers 0.000 claims abstract description 16
- 239000002612 dispersion medium Substances 0.000 claims abstract description 9
- 239000007787 solid Substances 0.000 claims abstract description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 17
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 16
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 16
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 16
- 125000003277 amino group Chemical group 0.000 claims description 13
- 239000007970 homogeneous dispersion Substances 0.000 claims description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 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
- 235000019448 polyvinylpyrrolidone-vinyl acetate copolymer Nutrition 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 4
- 239000000987 azo dye Substances 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 compound 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
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 239000001397 quillaja saponaria molina bark Substances 0.000 claims description 4
- 229930182490 saponin Natural products 0.000 claims description 4
- 150000007949 saponins Chemical class 0.000 claims description 4
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 3
- 125000002924 primary amino group Chemical class [H]N([H])* 0.000 claims description 3
- 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 claims description 2
- 229920000459 Nitrile rubber Polymers 0.000 claims description 2
- 239000004793 Polystyrene Substances 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- 229960002897 heparin Drugs 0.000 claims description 2
- 229920000669 heparin Polymers 0.000 claims description 2
- 229920002223 polystyrene Polymers 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 22
- 230000000694 effects Effects 0.000 abstract description 7
- 238000003860 storage Methods 0.000 abstract description 7
- 239000002904 solvent Substances 0.000 abstract description 6
- 239000012535 impurity Substances 0.000 abstract description 4
- 229910052799 carbon Inorganic materials 0.000 abstract description 3
- 238000000265 homogenisation Methods 0.000 abstract description 3
- 239000002086 nanomaterial Substances 0.000 abstract description 3
- 239000002048 multi walled nanotube Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 238000004090 dissolution Methods 0.000 description 10
- 239000000463 material Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- 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
- 239000011230 binding agent Substances 0.000 description 3
- 239000006258 conductive agent Substances 0.000 description 3
- 230000006378 damage Effects 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 229960002442 glucosamine Drugs 0.000 description 3
- 238000010998 test method 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
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003792 electrolyte Substances 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
- 238000001132 ultrasonic dispersion 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
- 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
- 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
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000006256 anode slurry Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000011267 electrode slurry Substances 0.000 description 1
- 238000000227 grinding Methods 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
- 230000007774 longterm Effects 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 238000002156 mixing 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
Abstract
The invention belongs to the technical field of carbon nano materials, and discloses a carbon nano tube conductive dispersion liquid, and a preparation method and application thereof. The carbon nanotube conductive dispersion liquid comprises a carbon nanotube, an amphiphilic block polymer dispersant, a second dispersant, an auxiliary dispersant and a dispersion medium, wherein the preparation method adopts a mode of micro-jet flow and high-pressure homogenization, the carbon nanotube is dispersed by making slurry impact, the dispersion effect is good, and impurities are not easy to introduce in the dispersion process; meanwhile, the amphiphilic block polymer dispersant is added to match with the second dispersant and the use of the auxiliary dispersant, so that the carbon nano tube is not easy to absorb the solvent when the dispersion is carried out at a higher solid content. Therefore, the dispersion liquid can keep the viscosity change less than 400 percent 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 and 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 more and more widely applied in the field of lithium batteries, and can form an effective conductive network by adding the carbon nano tube into an electrode material of a lithium ion battery, so that the capacity and the cycle performance of the battery are greatly improved. However, since the high specific surface area and the high aspect ratio of the carbon nanotube make the dispersion extremely difficult, the carbon nanotube can be made into a slurry only to sufficiently exert the function of the carbon nanotube, and the carbon nanotube conductive slurry is required to have a mass content of the carbon nanotube of 1% or more and a storage life of at least several months in industrial use.
In the prior art, N-methyl pyrrolidone (NMP) is generally used as a dispersion medium, an amphiphilic polymer and a block polymer are generally used as a dispersing agent, and the dispersion mode generally adopts ultrasonic dispersion or sand grinding dispersion. Although the ultrasonic dispersion can achieve a good dispersion effect, the carbon nano tube can be damaged, and the conductivity is influenced; the dispersion of the ordinary sanding of industrial production can the mass production, and the sanding medium generally uses the zirconium pearl, and sanding in-process zirconium pearl filled volume is great, can produce the destruction to carbon nanotube, and introduces impurity easily.
The microfluid and high-pressure homogenization disperse the carbon nanotubes by adopting a slurry hedging mode, so that a good dispersing effect can be achieved, the damage to the carbon nanotubes is small, impurities are not easily introduced in the dispersing process, and the original performance of the carbon nanotubes is favorably maintained. However, in the dispersing process, the carbon nanotubes can absorb the solvent when opened, so that the viscosity of the slurry is increased rapidly, and the phenomena of cavity blockage and even overload can be caused when the microfluid and high-pressure homogeneous dispersion is carried out.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art described above. Therefore, the invention provides a carbon nano tube conductive dispersion liquid which has excellent conductive performance and longer storage life.
The invention also provides a preparation method of the carbon nano tube conductive dispersion liquid.
The invention also provides application of the carbon nano tube conductive dispersion liquid.
According to one aspect of the invention, a carbon nanotube conductive dispersion liquid is provided, which comprises 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 comprises a compound containing amine groups and hydroxyl groups; 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 an aliphatic chain of the compound is less than or equal to 6, and the number of carbon atoms not connected with the hydroxyl groups is less than or equal to 4.
According to a preferred embodiment of the present invention, at least the following advantages are provided:
the amphiphilic block polymer dispersant is selected to match with the second dispersant, and the auxiliary dispersant is added, so that the carbon nanotube 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 comprises a benzene ring and an amino group, wherein the number of benzene rings is ≧ 2 and the number of amino groups is ≧ 1.
In some embodiments of the present invention, the co-dispersant accounts for less than or equal to 0.4% by mass of the carbon nanotube conductive dispersion liquid.
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 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 polymeric 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 present invention, the ratio of the two dispersants to the total solid content of the carbon nanotube conductive dispersion liquid 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 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 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 present invention, the dispersion medium is selected from 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 the amphiphilic block polymer dispersant, the second dispersant, the auxiliary dispersant and the dispersion medium, and then adding the carbon nano tube for continuous dispersion to obtain slurry;
s2: homogenizing and dispersing the slurry in the step S1 to obtain a carbon nanotube conductive dispersion liquid; preferably, the homogeneous dispersion comprises one of a microfluidics dispersion or a high pressure homogeneous dispersion.
The preparation method according to a preferred embodiment of the present invention has at least the following advantageous effects:
the invention adopts the mode of micro-jet flow and high-pressure homogenization, realizes the dispersion of the carbon nano tube by the opposite impact 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 dispersant is added to match with the second dispersant and the use of the auxiliary dispersant, so that the carbon nano tube is not easy to absorb the solvent when the dispersion is carried out at a 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 percent in a long-term storage process, and the carbon nano tube conductive dispersion liquid has good conductivity and stability.
In some embodiments of the present invention, the pre-dispersing and the dispersing in step S1 are performed by using a disperser, and the rotation speed of the disperser is 1500rpm to 2000 rpm.
In some embodiments of the present invention, in step S1, the pre-dispersion time is 30min to 45min, and the dispersion time is 30min to 60 min.
In some preferred embodiments of the present invention, in step S1, the pre-dispersion time is 30min, and the dispersion time is 30 min.
In some preferred embodiments of the present invention, in step S2, the homogeneous dispersion is high-pressure homogeneous dispersion.
In some embodiments of the present invention, in step S2, the homogeneous dispersion is sequentially dispersed using a low pressure to a 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 by 10MPa each time; the number of times of dispersion is less than or equal to 3 under each dispersion pressure.
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 anode slurry composition comprises a carbon nano tube 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 above battery positive electrode slurry composition was coated on a positive electrode current collector, dried and rolled to form a positive electrode of a battery.
The battery comprises a positive electrode, a negative electrode, a diaphragm 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 diaphragm 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 concept and technical effects of the present invention will be clearly and completely described below in conjunction with the embodiments to fully understand the objects, features and effects of the present invention. It is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and those skilled in the art can obtain other embodiments without inventive effort based on the embodiments of the present invention, and all embodiments are within the protection scope of the present invention. The test methods used in the examples are all conventional methods unless otherwise specified; the materials, reagents and the like used are commercially available reagents and materials unless otherwise specified.
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
In this embodiment, a carbon nanotube conductive dispersion liquid 1 is prepared, 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 dispersion machine, dispersing for 30min at 1500-2000 rpm, after complete dissolution, adding 9g of multi-walled carbon nanotubes, and continuing to disperse for 30min to obtain slurry; and adding the slurry into a microfluidizer, 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 nano tube conductive dispersion liquid 1.
Example 2
In this embodiment, a carbon nanotube conductive dispersion liquid 2 is prepared, 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 dispersion machine, dispersing for 30min at 1500-2000 rpm, after complete dissolution, adding 9g of multi-walled carbon nanotubes, and continuing to disperse for 30min to obtain slurry; and adding the slurry into a microfluidizer, 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 nano tube conductive dispersion liquid 2.
Example 3
In this embodiment, a carbon nanotube conductive dispersion liquid 3 is prepared, 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 dispersion machine, dispersing for 30min at 1500-2000 rpm, after complete dissolution, adding 9g of multi-walled carbon nanotubes, and continuing to disperse for 30min to obtain slurry; and adding the slurry into a microfluidizer, 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 nano tube conductive dispersion liquid 3.
Example 4
In this embodiment, a carbon nanotube conductive dispersion liquid 4 is prepared, 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 dispersion machine, dispersing for 30min at 1500-2000 rpm, after complete dissolution, adding 9g of multi-walled carbon nanotubes, and continuing to disperse for 30min to obtain slurry; and adding the slurry into a microfluidizer, 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 nano tube conductive dispersion liquid 4.
Example 5
In this embodiment, a carbon nanotube conductive dispersion liquid 5 is prepared, and the specific process is as follows:
adding 487.5g of NMP, 2g of PVP, 0.5g of solvent yellow 3 and 1g of 3-aminopropanol into a high-speed dispersion machine, dispersing for 30min at 1500-2000 rpm, after complete dissolution, adding 9g of multi-walled carbon nanotubes, and continuing to disperse for 30min to obtain slurry; and adding the slurry into a microfluidizer, 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 nano tube conductive dispersion liquid 5.
Example 6
In this embodiment, a carbon nanotube conductive dispersion liquid 6 is prepared, and the specific process is as follows:
adding 487.5g of NMP, 2g of PVP, 0.5g of solvent black 32 and 1g of glucosamine into a high-speed dispersion machine, dispersing for 30min at 1500-2000 rpm, after complete dissolution, adding 9g of multi-walled carbon nanotubes, and continuing to disperse for 30min to obtain slurry; and adding the slurry into a microfluidizer, 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 nano tube conductive dispersion liquid 6.
Comparative example 1
The present comparative example prepared the carbon nanotube conductive dispersion a, which is different from example 1 in that the second dispersant and the co-dispersant were not added to the carbon nanotube conductive dispersion prepared by the present comparative example. The specific process is as follows:
adding 489g of NMP and 2g of PVP into a high-speed dispersion machine, dispersing for 30min at 1500-2000 rpm, after complete dissolution, adding 9g of multi-walled carbon nanotubes, and continuing to disperse for 30min to obtain slurry; and adding the slurry into a microfluidizer, 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 nano tube conductive dispersion liquid a.
Comparative example 2
This example prepared a carbon nanotube conductive dispersion b, which was different from example 3 in that a second dispersant was not added to the carbon nanotube conductive dispersion prepared in this comparative example. The specific process is as follows:
adding 487.5g of NMP, 2g of PVP and 1g of glucosamine into a high-speed dispersion machine, dispersing for 30min at 1500-2000 rpm, after complete dissolution, adding 9g of multi-walled carbon nanotubes, and continuing to disperse for 30min to obtain slurry; and (3) adding the slurry into a microfluidizer, dispersing for 3 times under the pressure of 20MPa, adjusting the pressure to 30MPa, dispersing for 3 times, and adjusting the pressure to 40MPa, and dispersing for 3 times to obtain the carbon nano tube conductive dispersion liquid b.
Comparative example 3
This example prepared a carbon nanotube conductive dispersion c, which was different from example 5 in that the co-dispersant added to the carbon nanotube conductive dispersion prepared in this comparative example had a carbon number of > 6. The specific process is as follows:
adding 487.5g of NMP, 2g of PVP, 0.5g of solvent yellow 3 and 1g of triisopropanolamine into a high-speed dispersion machine, dispersing for 30min at 1500-2000 rpm, after complete dissolution, adding 9g of multi-walled carbon nanotubes, and continuing to disperse for 30min to obtain slurry; and adding the slurry into a microfluidizer, 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 nano tube conductive dispersion liquid c.
Comparative example 4
This example prepared a carbon nanotube conductive dispersion d, which is different from example 5 in that the number of amine groups of the dispersion aid additive added to the carbon nanotube conductive dispersion prepared in this comparative example was 2. The specific process is as follows:
adding 487.5g of NMP, 2g of PVP, 0.5g of solvent yellow 3 and 1g of N- (2-hydroxypropyl) ethylenediamine into a high-speed dispersion machine, dispersing for 30min at 1500-2000 rpm, after complete dissolution, adding 9g of multi-walled carbon nanotubes, and continuing to disperse for 30min to obtain slurry; and adding the slurry into a microfluidizer, 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 nano tube conductive dispersion liquid d.
Test examples
The experimental example tested the dispersion, viscosity and resistivity of the carbon nanotube conductive dispersions prepared in the examples and comparative examples. Wherein:
the dispersion was observed during the microfluidization process.
Viscosity test method: immediately testing the viscosity of the dispersion liquid by using a rotational viscometer after the preparation of the carbon nano tube conductive dispersion liquid is finished, and taking the viscosity as initial viscosity; the dispersion was then placed in a standard condition environment and the viscosity change was monitored over a 90d period, with the viscosity being measured every 30 d.
The resistivity test method comprises the following steps: preparing battery slurry by using a ternary nickel-cobalt-manganese active material (NCM523) as a main material and polyvinylidene fluoride (PVDF) as a binder, wherein the specific mass ratio is that of the ternary material: adhesive: conductive agent (carbon nanotube) ═ 100: 1.5: 0.2 (the conductive agent is the conductive agent placed for 90 days), adding appropriate NMP to adjust the viscosity, carrying out positive pole slurry mixing, coating on a polyethylene terephthalate (PET) film, drying, and testing the resistivity by adopting a four-probe volume resistivity testing instrument.
The test results are shown in tables 2, 3 and 4.
TABLE 2
TABLE 3
TABLE 4
In table 2, compared with the conductive dispersions 1, 2 and 4, the conductive dispersion a is not added with the second dispersant and the auxiliary dispersant, so that the conductive dispersion a is easy to block or overload in the dispersion process, the initial viscosity is high, the viscosity gradually rises along with the extension of the storage time, the viscosity is obviously greater than that of the conductive dispersions 1, 2 and 4, the viscosity change is greater than 400%, and the resistivity is also higher. The second dispersing agent and the auxiliary dispersing agent are beneficial to reducing the viscosity and the resistivity of the carbon nano tube conductive dispersion liquid, so that the dispersion liquid keeps good stability and conductivity.
In table 3, compared with the conductive dispersions 3 and 6, the conductive dispersion b has no second dispersant added, and has a slight cavity blocking phenomenon in the dispersion process, and the initial viscosity is almost the same as that of the conductive dispersions 3 and 6, but the viscosity gradually increases with the increase of the storage time, and is obviously greater than that of the conductive dispersions 3 and 6, and the viscosity change is greater than 400%, and the resistivity is also higher. The second dispersing agent can reduce the viscosity and the resistivity of the carbon nano tube conductive dispersing liquid to a certain extent, so that the dispersing liquid keeps good stability and conductivity.
In table 4, compared with conductive dispersion liquid 5, the number of carbon atoms of the dispersion aid in conductive dispersion liquid c is greater than 6, the number of amine groups of the dispersion aid in conductive dispersion liquid d is 2, and different from the dispersion aid in dispersion liquid 5 (the number of carbon atoms is less than or equal to 6, and the number of amine groups is 1), the dispersion aid is easy to block/overload during dispersion, the initial viscosity is high, the viscosity gradually increases with the increase of storage time and is significantly greater than that of conductive dispersion liquid 5, the viscosity change is greater than 400%, and the resistivity is also high. The selection of the auxiliary dispersing agent is shown to have certain limitation, and the requirement that the auxiliary dispersing agent comprises amino and hydroxyl, wherein the amino is one of primary amine or secondary amine, the number of the amine is 1, the number of the hydroxyl is more than or equal to 1, the number of the carbon atoms is less than or equal to 6, and the number of the carbon atoms of the unconnected hydroxyl is less than or equal to 4 is met, the viscosity and the resistivity of the carbon nano tube conductive dispersing liquid are increased, and the dispersing liquid cannot maintain good stability and conductivity.
The embodiments of the present invention have been described in detail, but the present invention is not limited to the embodiments, and various changes can be made without departing from the gist of the present invention within the knowledge of those skilled in the art. Furthermore, the embodiments of the present invention and the features of the embodiments may be combined with each other without conflict.
Claims (10)
1. A carbon nanotube conductive dispersion, comprising: the carbon nano tube dispersion agent comprises a carbon nano tube, 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 comprises a compound containing amine groups and hydroxyl groups; 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 an aliphatic chain of the compound is less than or equal to 6, and the number of carbon atoms not connected with the hydroxyl groups is less than or equal to 4.
2. The dispersion as claimed in claim 1, wherein the azo dye comprises benzene rings and amino groups, wherein the number of benzene rings is 2 or more and the number of amino groups is 1 or more.
3. The dispersion of claim 1, wherein the co-dispersant is present in the carbon nanotube conductive dispersion at a mass fraction of 0.4% or less.
4. The dispersion of claim 1, wherein said amphiphilic block polymer dispersant comprises at least one of polyvinylpyrrolidone, hydrogenated nitrile rubber, polyvinyl butyral, polyvinylpyrrolidone-vinyl acetate copolymer, polystyrene acrylonitrile copolymer.
5. The dispersion liquid according to claim 1, wherein the ratio of the two dispersing agents to the total solid content of the carbon nanotube conductive dispersion liquid is 30% by mass or less; preferably, the mass ratio of the amphiphilic block polymer dispersant to the second dispersant is 2: 1-8: 1.
6. The dispersion of claim 1, wherein the dispersion medium comprises at least one of N-methylpyrrolidone, acetamide, or N, N-dimethylformamide.
7. A method for producing the dispersion liquid as claimed in any one of claims 1 to 6, characterized by comprising the steps of:
s1: pre-dispersing the amphiphilic block polymer dispersant, the second dispersant, the auxiliary dispersant and the dispersion medium, and then adding the carbon nano tube for continuous dispersion to obtain slurry;
s2: homogenizing and dispersing the slurry in the step S1 to obtain a carbon nanotube conductive dispersion liquid; preferably, the homogeneous dispersion comprises one of a microfluidics dispersion or a high pressure homogeneous dispersion.
8. The production method according to claim 7, wherein the dispersion pressure of the homogeneous dispersion is 20 to 40 MPa; preferably, the dispersing pressure is increased gradually, and 10MPa is adjusted each time; preferably, the number of dispersions is < 3 at each of said dispersion pressures.
9. Use of the dispersion according to any one of claims 1 to 6 or the dispersion produced by the production method according to any one of claims 7 to 8 in a battery paste composition.
10. Use of the dispersion according to any one of claims 1 to 6 or the dispersion produced by the production method according to any one of claims 7 to 8 in a battery.
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