CN117038200A - Aqueous conductive paste containing one-dimensional carbon nanomaterial and preparation method and application thereof - Google Patents
Aqueous conductive paste containing one-dimensional carbon nanomaterial and preparation method and application thereof Download PDFInfo
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- CN117038200A CN117038200A CN202311030184.1A CN202311030184A CN117038200A CN 117038200 A CN117038200 A CN 117038200A CN 202311030184 A CN202311030184 A CN 202311030184A CN 117038200 A CN117038200 A CN 117038200A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 59
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 238000010494 dissociation reaction Methods 0.000 claims abstract description 45
- 230000005593 dissociations Effects 0.000 claims abstract description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 41
- 238000000227 grinding Methods 0.000 claims abstract description 38
- 238000002156 mixing Methods 0.000 claims abstract description 28
- 239000003381 stabilizer Substances 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000002270 dispersing agent Substances 0.000 claims abstract description 19
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 7
- 239000002041 carbon nanotube Substances 0.000 claims description 25
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 25
- 238000003756 stirring Methods 0.000 claims description 24
- 239000011259 mixed solution Substances 0.000 claims description 23
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 16
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 16
- 239000002002 slurry Substances 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 13
- 239000007773 negative electrode material Substances 0.000 claims description 7
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 7
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 7
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 239000011889 copper foil Substances 0.000 claims description 5
- 239000011267 electrode slurry Substances 0.000 claims description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 4
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- 239000004793 Polystyrene Substances 0.000 claims description 2
- 235000021355 Stearic acid Nutrition 0.000 claims description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 2
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 2
- 239000011230 binding agent Substances 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 2
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 2
- YRIUSKIDOIARQF-UHFFFAOYSA-N dodecyl benzenesulfonate Chemical compound CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 YRIUSKIDOIARQF-UHFFFAOYSA-N 0.000 claims description 2
- MOTZDAYCYVMXPC-UHFFFAOYSA-N dodecyl hydrogen sulfate Chemical compound CCCCCCCCCCCCOS(O)(=O)=O MOTZDAYCYVMXPC-UHFFFAOYSA-N 0.000 claims description 2
- 229940043264 dodecyl sulfate Drugs 0.000 claims description 2
- 229940071161 dodecylbenzenesulfonate Drugs 0.000 claims description 2
- 239000000194 fatty acid Substances 0.000 claims description 2
- 229930195729 fatty acid Natural products 0.000 claims description 2
- 150000002191 fatty alcohols Chemical class 0.000 claims description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 2
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 2
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 2
- 229920002223 polystyrene Polymers 0.000 claims description 2
- 150000003856 quaternary ammonium compounds Chemical class 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 2
- 239000008117 stearic acid Substances 0.000 claims description 2
- 229960004274 stearic acid Drugs 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 8
- 230000008901 benefit Effects 0.000 abstract description 7
- 238000010907 mechanical stirring Methods 0.000 abstract description 5
- 238000003860 storage Methods 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 13
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 9
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 9
- 239000004576 sand Substances 0.000 description 8
- 239000006185 dispersion Substances 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 6
- 239000006258 conductive agent Substances 0.000 description 5
- 239000000499 gel Substances 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 5
- 238000005507 spraying Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000010405 anode material Substances 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000006183 anode active material Substances 0.000 description 1
- 239000006256 anode slurry Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000002003 electrode paste Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- -1 i.e. Substances 0.000 description 1
- 235000015110 jellies Nutrition 0.000 description 1
- 239000008274 jelly Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
-
- 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
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention provides a water-based conductive paste containing one-dimensional carbon nano materials, and a preparation method and application thereof, wherein the preparation method comprises the steps of firstly mixing a dispersing agent, a stabilizing agent and water, and then adding the one-dimensional carbon nano materials for mixing to obtain a premixed solution; sequentially performing first dissociation, first grinding, second dissociation and second grinding on the obtained premixed solution to obtain the water-based conductive paste; according to the preparation method, the two times of alternate dissociation and grinding are utilized, so that the obtained aqueous conductive paste is not easy to generate gel, small in viscosity rebound, good in fluidity and dispersibility in the storage process, mechanical stirring is not needed before the aqueous conductive paste is used, meanwhile, the length of the one-dimensional carbon nano material in the obtained aqueous conductive paste is high, the advantage of long-range conductivity is ensured, and the aqueous conductive paste has excellent conductivity, so that the lithium ion battery prepared by the aqueous conductive paste has excellent electrical property.
Description
Technical Field
The invention belongs to the technical field of conductive paste, and particularly relates to an aqueous conductive paste containing one-dimensional carbon nanomaterial and a preparation method and application thereof.
Background
With the increasing environmental impact of petrochemical energy, clean energy is being widely used as a substitute, and new energy batteries, which are the main components of clean energy, are becoming the first choice for storing electric energy in the fields of passenger cars, buses and energy storage. The conductive agent is used as an important component in the new energy battery, and the performance of the conductive agent can directly influence the electrical performance of the new energy battery.
The dispersion degree and the length of the one-dimensional carbon nanomaterial serving as one of the most commonly used conductive agents at present are often opposite, and the uniformly dispersed carbon nanomaterial conductive paste can provide a uniform conductive network, so that the conductive performance is improved, and the carbon nanomaterial conductive paste with a high length-diameter ratio can better exert the long-range conductive advantage. However, in the aqueous conductive paste, the longer the one-dimensional carbon nanomaterial is, the more easily the one-dimensional carbon nanomaterial is entangled with each other and is difficult to disperse, and the problems of gel, i.e., jelly shape, poor fluidity, and the like are more easily generated in the long-term storage of the conductive paste prepared by the conventional process.
CN106046982a discloses a high dispersion type aqueous carbon nanotube conductive paste, which comprises the following components in parts by weight: 10-60 parts by mass of water-soluble resin, 5-40 parts by mass of activated carbon nano tube and 20-70 parts by mass of water-based solvent B; the activated carbon nanotube is obtained by stirring carbon nanotube at high speed, dissolving dispersant in liquid, spraying the dispersant into the stirred carbon nanotube powder in a spraying manner, and activating the surface of the carbon nanotube. CN106189577a discloses a method for preparing a high-dispersion type aqueous carbon nanotube conductive paste, which comprises the steps of stirring carbon nanotubes at a high speed, dissolving a dispersing agent in a liquid, spraying the dispersing agent into the stirred carbon nanotube powder in a spraying manner, so that the surface of the carbon nanotubes is activated, and obtaining activated carbon nanotubes; the active carbon nano tube is mixed with water-soluble resin, water-based solvent B, anti-sedimentation agent and defoamer, and is uniformly mixed by ultrasonic or sanding process, thus preparing the high-dispersion water-based carbon nano tube conductive slurry. The aqueous carbon nanotube slurry obtained in the two inventions has good dispersibility, but the length of the carbon nanotubes in the final slurry is low, so that the long-range conductive advantage of the carbon nanotubes is lost, and meanwhile, the slurry is easy to gel, has quick viscosity rebound and no fluidity, needs mechanical stirring before being used, and is not beneficial to industrial batch use.
Therefore, the development of a preparation method for preparing the aqueous conductive paste which has the advantages of higher length, difficult gel generation, good fluidity and good dispersibility and can be directly used is a technical problem which needs to be solved in the field.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide the water-based conductive paste containing the one-dimensional carbon nano material, and the preparation method and application thereof, wherein the preparation method utilizes two times of alternately-performed dissociation and grinding, so that the obtained water-based conductive paste is not easy to generate gel, has small viscosity rebound, good fluidity and better dispersibility in the storage process, can be directly used without mechanical stirring before use, and is easy to store and simple in process; meanwhile, the one-dimensional carbon nanomaterial is high in length, the advantage of long-range conduction is guaranteed, and the one-dimensional carbon nanomaterial has the characteristic of excellent conductivity, so that the lithium ion battery prepared by the one-dimensional carbon nanomaterial is excellent in electrical property.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for preparing an aqueous conductive paste containing one-dimensional carbon nanomaterial, the method comprising the steps of:
(1) Mixing a dispersing agent, a stabilizing agent and water, and then adding a one-dimensional carbon nano material for mixing to obtain a premixed solution;
(2) And (3) sequentially carrying out first dissociation, first grinding, second dissociation and second grinding on the pre-mixed solution obtained in the step (1) to obtain the water-based conductive paste.
According to the preparation method of the water-based conductive paste, the dispersing agent, the stabilizing agent and the water are mixed firstly, then the one-dimensional carbon nano material is added for mixing to obtain the premixed solution, then the obtained premixed solution is sequentially subjected to first dissociation, first grinding, second dissociation and second grinding, and the dissociation and the grinding are alternately carried out, so that the length and the length-diameter ratio of the one-dimensional carbon nano material are not damaged, the one-dimensional carbon nano material can be uniformly dispersed and cannot be intertwined into clusters, and finally the water-based conductive paste which is high in dispersion uniformity, not easy to generate gel, small in viscosity rebound, easy to store and free from mechanical stirring in use can be directly obtained; meanwhile, the length of the one-dimensional carbon nano material in the aqueous conductive paste is high, so that the conductivity of the aqueous conductive paste is very excellent, and further the long-range conductivity advantage of the carbon tube can be exerted when the aqueous conductive paste is applied to a lithium ion battery, and the electrical property of the lithium ion battery is greatly improved.
Preferably, the content of the dispersant in the pre-mixed solution is 1 to 10 parts by weight, for example, 2 parts by weight, 3 parts by weight, 4 parts by weight, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight, or the like.
Preferably, the dispersant comprises any one or a combination of at least two of polyvinylpyrrolidone, carboxymethyl cellulose salt or polystyrene butadiene.
Preferably, the content of the stabilizer in the pre-mixed solution is 1 to 10 parts by weight, for example, 2 parts by weight, 3 parts by weight, 4 parts by weight, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight, or the like.
Preferably, the stabilizer comprises a combination of polyvinyl alcohol and other stabilizers including any one or a combination of at least two of stearic acid, dodecylbenzene sulfonate, dodecylsulfate, fatty alcohol polyoxyethylene ether ammonium sulfate, quaternary ammonium compounds, or fatty acid glycerides.
As a preferred technical scheme of the invention, the combination of polyvinyl alcohol and other stabilizers is selected as the stabilizer, and has the advantages that the polyvinyl alcohol can change the surface activity of the one-dimensional carbon nanomaterial to increase the dispersion effect of the one-dimensional carbon nanomaterial, and the other stabilizers can change the viscosity of the slurry and interact with the polyvinyl alcohol to avoid re-agglomeration of the dispersed one-dimensional carbon nanomaterial.
Preferably, the mass ratio of the polyvinyl alcohol and other stabilizers is 2 (0.5-10), such as 2:0.6, 2:0.7, 2:0.8, 2:0.9, 2:1, 2:3, 2:5, 2:7 or 2:8, etc.
Preferably, the water content of the pre-mixed solution is 60 to 98 parts by weight, for example, 62 parts by weight, 64 parts by weight, 66 parts by weight, 68 parts by weight, 70 parts by weight, 72 parts by weight, 74 parts by weight, 76 parts by weight, 78 parts by weight, 80 parts by weight, 82 parts by weight, 84 parts by weight, 86 parts by weight, 88 parts by weight, 90 parts by weight, 92 parts by weight, 94 parts by weight, 96 parts by weight, or the like.
Preferably, the mixing of the dispersant, the stabilizer and the water is performed under stirring, and more preferably under stirring at a rotation speed of 1800 to 2200rpm (for example 1850rpm, 1900rpm, 1950rpm, 2000rpm, 2050rpm, 2100rpm, 2150rpm, or the like).
Preferably, the mixing time for mixing the dispersant, the stabilizer and the water is 0.5 to 12 hours, for example, 2 hours, 4 hours, 6 hours, 8 hours, 10 hours, 11 hours, or the like.
Preferably, the content of the one-dimensional carbon nanomaterial in the pre-mixed solution is 1 to 20 parts by weight, for example, 2 parts by weight, 4 parts by weight, 6 parts by weight, 8 parts by weight, 10 parts by weight, 12 parts by weight, 14 parts by weight, 16 parts by weight, 18 parts by weight, or the like.
Preferably, the one-dimensional carbon nanomaterial comprises carbon nanotubes and/or carbon fibers.
Preferably, the one-dimensional carbon nanomaterial is not less than 100 μm in length, for example, 110 μm, 120 μm, 130 μm, 140 μm, 150 μm, 160 μm, 170 μm, 180 μm, 190 μm, or the like, and more preferably 100 to 200 μm.
Preferably, the one-dimensional carbon nanomaterial is added and mixed under stirring, and more preferably under stirring at a rotation speed of 1800 to 2200rpm (e.g., 1850rpm, 1900rpm, 1950rpm, 2000rpm, 2050rpm, 2100rpm, 2150rpm, or the like).
Preferably, the mixing time of adding the one-dimensional carbon nanomaterial for mixing in the step (1) is 20-80 min, for example, 25min, 30min, 35min, 40min, 50min, 60min or 70min, and more preferably 40-60 min.
Preferably, the time of the first dissociation is 30 to 50min, for example, 32min, 34min, 36min, 38min, 40min, 42min, 44min, 46min or 48min, etc.
Preferably, the pressure of the first dissociation is 1000-1500 bar, for example 1050bar, 1100bar, 1150bar, 1200bar, 1250bar, 1300bar, 1350bar, 1400bar or 1450bar, etc., further preferably 1000-1200 bar.
Preferably, the rotation speed of the first grinding is 800-1200 r/min, such as 820r/min, 840r/min, 860r/min, 880r/min, 1000r/min, 1020r/min, 1040r/min, 1060r/min, 1080r/min, 1100r/min, 1120r/min, 1140r/min, 1160r/min, 1180r/min, etc.
Preferably, the time of the first grinding is 20 to 60 minutes, for example, 25 minutes, 30 minutes, 35 minutes, 40 minutes, 45 minutes, 50 minutes, 55 minutes, or the like.
Preferably, the time of the second dissociation is 30-50 min, for example, 32min, 34min, 36min, 38min, 40min, 42min, 44min, 46min or 48min, etc.
Preferably, the pressure of the second dissociation is 1000 to 1500bar, more preferably 1000 to 1200bar, for example 1020bar, 1040bar, 1060bar, 1080bar, 1100bar, 1120bar, 1140bar, 1160bar or 1180bar, etc.
Preferably, the rotation speed of the second grinding is 800-1200 r/min, for example 850r/min, 900r/min, 950r/min, 1000r/min, 1050r/min, 1100r/min or 1150r/min, etc.
Preferably, the second grinding is performed for 20 to 60 minutes, for example, 25 minutes, 30 minutes, 35 minutes, 40 minutes, 45 minutes, 50 minutes, 55 minutes, or the like, and more preferably 40 to 50 minutes.
As a preferred technical scheme of the invention, the preparation method of the aqueous conductive paste containing the one-dimensional carbon nanomaterial comprises the following steps:
(1) Mixing a dispersing agent, a stabilizing agent and water for 0.5-12 h under the stirring condition of the rotating speed of 1800-2200 rpm, adding a one-dimensional carbon nano material, and mixing for 20-80 min under the stirring condition of the rotating speed of 1800-2200 rpm to obtain a premixed solution;
(2) And (3) performing primary high-energy dissociation for 30-50 min under the condition of the pressure of 1000-1500 bar, performing primary grinding for 20-60 min under the condition of the rotating speed of 800-1200 r/min, performing secondary high-energy dissociation for 30-50 min under the condition of the pressure of 1000-1500 bar, and performing secondary grinding for 20-60 min under the condition of the rotating speed of 800-1200 r/min to obtain the water-based conductive paste.
In a second aspect, the present invention provides an aqueous conductive paste containing one-dimensional carbon nanomaterial, the aqueous conductive paste being prepared by the preparation method according to the first aspect.
In a third aspect, the present invention provides a negative electrode slurry comprising the aqueous electroconductive slurry according to the second aspect, a negative electrode active material, and a binder.
Preferably, the negative electrode active material includes silicon carbide.
In a fourth aspect, the present invention provides a negative electrode tab comprising a copper foil and a negative electrode material coated on the copper foil;
the raw materials for preparing the anode material comprise the anode slurry according to the third aspect.
In a fifth aspect, the present invention provides a lithium ion battery comprising a negative electrode tab as described in the fourth aspect.
Compared with the prior art, the invention has the following beneficial effects:
(1) The preparation method of the water-based conductive paste containing the one-dimensional carbon nano material comprises the steps of mixing a dispersing agent, a stabilizing agent and water, adding the one-dimensional carbon nano material, mixing to obtain a pre-mixed solution, and sequentially carrying out first dissociation, first grinding, second dissociation and second grinding on the obtained pre-mixed solution; the aqueous conductive paste obtained by the preparation method can be stored for a long time for 180 days, has no hydrogel phenomenon, small viscosity rebound and good fluidity, and does not need to be dispersed by adding a mechanical stirring process before use, so that the cost of an application process is not required to be increased additionally;
(2) The water-based conductive slurry obtained by the preparation method provided by the invention can ensure that the one-dimensional carbon nano material has higher length while ensuring that the one-dimensional carbon nano material is uniformly dispersed, and can improve the performance of the anode material when being used as an anode conductive agent, so that the cycle life of a lithium ion battery can be effectively prolonged, the surface of anode active material particles can be completely and uniformly covered in the charging and discharging processes of the lithium battery, and the anode material can always maintain excellent conductivity;
(3) Specifically, the capacity retention rate of the button cell prepared by using the aqueous conductive paste as the conductive agent can reach 95%, and the initial charge specific capacity can reach 458mAhg -1 The specific capacity of the first discharge can reach 418mAhg -1 。
Drawings
FIG. 1 is a scanning electron microscope image of the carbon nanotubes used in example 1;
FIG. 2 is a scanning electron microscope image of the aqueous electroconductive paste provided in example 1;
FIG. 3 is a graph showing the viscosity rebound at various times of the aqueous slurries obtained in examples 1 to 9 and comparative examples 1 to 3.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
The preparation method of the aqueous conductive paste containing the one-dimensional carbon nanomaterial specifically comprises the following steps:
(1) Mixing 8 parts by weight of polyvinylpyrrolidone (commercially available conventional product K30), 2 parts by weight of sodium dodecylbenzenesulfonate, 4 parts by weight of polyvinyl alcohol (commercially available conventional product 2488) and 80 parts by weight of distilled water under stirring at a rotation speed of 2000rpm for 40min, adding 10 parts by weight of carbon nanotubes (length of about 200 μm) under stirring at a rotation speed of 2000rpm for 40min to obtain a premixed solution;
(2) Transferring the pre-mixed solution obtained in the step (1) into high-energy dissociation equipment through a screw pump, performing first high-energy dissociation for 40min under the condition of the pressure of 1000bar, transferring the pre-mixed solution after high-energy dissociation into sand mill equipment through the screw pump, performing first grinding for 30min under the condition of the rotating speed of 1000r/min, transferring the pre-mixed solution after grinding into the high-energy dissociation equipment through the screw pump again, performing second high-energy dissociation for 40min under the condition of the pressure of 1000bar, and finally transferring the pre-mixed solution after high-energy dissociation into the sand mill equipment again, and performing second grinding for 30min under the condition of the rotating speed of 1000r/min to obtain the water-based conductive slurry.
Example 2
A method for preparing aqueous conductive paste containing one-dimensional carbon nanomaterial, comprising the following steps:
(1) Mixing 5 parts by weight of polyvinylpyrrolidone (commercially available conventional product K30), 3 parts by weight of sodium dodecylbenzenesulfonate, 6 parts by weight of polyvinyl alcohol (commercially available conventional product 2488) and 70 parts by weight of distilled water under stirring at a rotation speed of 1800rpm for 40min, adding 5 parts by weight of carbon nanotubes (length of about 100 μm) under stirring at a rotation speed of 1800rpm for 60min to obtain a premixed solution;
(2) Transferring the pre-mixed solution obtained in the step (1) into high-energy dissociation equipment through a screw pump, performing first high-energy dissociation for 30min under the condition of 1200bar pressure, transferring the pre-mixed solution after high-energy dissociation into sand mill equipment through the screw pump, performing first grinding for 20min under the condition of 1200r/min rotation speed, transferring the pre-mixed solution after sand grinding into the high-energy dissociation equipment through the screw pump again, performing second high-energy dissociation for 30min under the condition of 1200bar pressure, and finally transferring the pre-mixed solution after high-energy dissociation into the sand mill equipment again, and performing second grinding for 20min under the condition of 1200r/min rotation speed to obtain the water-based conductive slurry.
Example 3
The preparation method of the aqueous conductive paste containing the one-dimensional carbon nanomaterial is different from example 1 only in that the addition amount of sodium dodecyl benzene sulfonate is 4 parts by weight, the addition amount of polyvinyl alcohol is 2 parts by weight, and other components, amounts and steps are the same as those of example 1.
Example 4
The preparation method of the aqueous conductive paste containing the one-dimensional carbon nanomaterial is different from example 1 only in that the addition amount of sodium dodecyl benzene sulfonate is 1 part by weight, the addition amount of polyvinyl alcohol is 5 parts by weight, and other components, amounts and steps are the same as those of example 1.
Example 5
The preparation method of the aqueous conductive paste containing the one-dimensional carbon nanomaterial is different from example 1 only in that sodium dodecyl benzene sulfonate is not added, the addition amount of polyvinyl alcohol is 6 parts by weight, and other components, amounts and steps are the same as those of example 1.
Example 6
The preparation method of the aqueous conductive paste containing the one-dimensional carbon nanomaterial is different from example 1 only in that no polyvinyl alcohol is added, the addition amount of sodium dodecyl benzene sulfonate is 6 parts by weight, and other components, amounts and steps are the same as those of example 1.
Example 7
The aqueous conductive paste containing one-dimensional carbon nanomaterial and the preparation method thereof are different from example 1 only in that the time of the first grinding and the second grinding in the step (2) is 40min, and other components, amounts and steps are the same as those in example 1.
Example 8
The preparation method of the aqueous conductive paste containing the one-dimensional carbon nanomaterial is different from example 1 only in that the time of the first grinding and the second grinding in the step (2) is 60min, and other components, amounts and steps are the same as those in example 1.
Example 9
The preparation method of the aqueous conductive paste containing the one-dimensional carbon nanomaterial is different from example 1 only in that the pressure of the first high-energy dissociation and the second high-energy dissociation in the step (2) is 1500bar, and other components, amounts and steps are the same as those in example 1.
Comparative example 1
A method for preparing aqueous conductive paste containing one-dimensional carbon nanomaterial, comprising the following steps:
(1) Mixing 8 parts by weight of polyvinylpyrrolidone (commercially available conventional product K30), 2 parts by weight of sodium dodecylbenzenesulfonate, 4 parts by weight of polyvinyl alcohol (commercially available conventional product 2488) and 80 parts by weight of distilled water under stirring at a rotation speed of 2000rpm for 40min, adding 10 parts by weight of carbon nanotubes (length of about 200 μm) under stirring at a rotation speed of 2000rpm for 40min to obtain a premixed solution;
(2) Transferring the pre-mixed solution obtained in the step (1) into high-energy dissociation equipment through a screw pump, performing high-energy dissociation for 80min under the condition of the pressure of 1000bar, transferring the pre-mixed solution after high-energy dissociation into sand mill equipment through the screw pump, and grinding for 60min under the condition of the rotating speed of 1000r/min to obtain the water-based conductive paste.
Comparative example 2
A method for preparing aqueous conductive paste containing one-dimensional carbon nanomaterial, comprising the following steps:
(1) Mixing 8 parts by weight of polyvinylpyrrolidone (commercially available conventional product K30), 2 parts by weight of sodium dodecylbenzenesulfonate, 4 parts by weight of polyvinyl alcohol (commercially available conventional product 2488) and 80 parts by weight of distilled water under stirring at a rotation speed of 2000rpm for 40min, adding 10 parts by weight of carbon nanotubes (length of about 200 μm) under stirring at a rotation speed of 2000rpm for 40min to obtain a premixed solution;
(2) Transferring the pre-mixed solution obtained in the step (1) into high-energy dissociation equipment through a screw pump, performing high-energy dissociation for 40min under the condition of the pressure of 1000bar, transferring the pre-mixed solution after high-energy dissociation into sand mill equipment through the screw pump, and grinding for 30min under the condition of the rotating speed of 1000r/min to obtain the water-based conductive paste.
Comparative example 3
A method for preparing aqueous conductive paste containing one-dimensional carbon nanomaterial, comprising the following steps:
(1) Mixing 8 parts by weight of polyvinylpyrrolidone (commercially available conventional product K30), 2 parts by weight of sodium dodecylbenzenesulfonate, 4 parts by weight of polyvinyl alcohol (commercially available conventional product 2488) and 80 parts by weight of distilled water under stirring at a rotation speed of 2000rpm for 40min, adding 10 parts by weight of carbon nanotubes (length of about 200 μm) under stirring at a rotation speed of 2000rpm for 40min to obtain a premixed solution;
(2) Transferring the pre-mixed solution obtained in the step (1) into sand mill equipment through a screw pump, and grinding for 30min under the condition of 1000r/min of rotating speed to obtain the water-based conductive paste.
Application example 1
A button cell, its preparation process includes: mixing silicon carbon, the aqueous conductive paste obtained in example 1, CMC and SBR in a mass ratio of 92:3:2:3 in deionized water to obtain a negative electrode paste with a solid content of 60%; and then coating the obtained negative electrode slurry on a copper foil, wherein the coating thickness is 200 mu m, drying and rolling to obtain a negative electrode plate, and preparing the button cell by adopting a metal lithium plate as a counter electrode.
Application examples 2 to 9
A button cell is different from application example 1 only in that aqueous electroconductive pastes obtained in examples 2 to 9 are used in place of aqueous electroconductive paste obtained in example 1, respectively, and other components, amounts and manufacturing processes are the same as those of application example 1.
Comparative application examples 1 to 3
A button cell is different from application example 1 only in that aqueous electroconductive pastes obtained in comparative examples 1 to 3 are used in place of aqueous electroconductive paste obtained in example 1, respectively, and other components, amounts and manufacturing processes are the same as those of application example 1.
Performance testing
(1) Morphology observation: diluting the carbon nano tube used in the embodiment 1 and the finally obtained water-based conductive paste by using distilled water, depositing the diluted and dispersed paste on a substrate, and drying at 120 ℃ for 5 hours to obtain a sample to be tested; testing the diluted carbon nanotubes and the aqueous conductive paste by using a scanning electron microscope, wherein scanning electron microscope images of the carbon nanotubes and the aqueous conductive paste provided in the example 1 are respectively shown in fig. 1 and fig. 2;
as can be seen from fig. 1 to 2: the carbon nanotubes used in example 1 had a length of about 200nm, and the aqueous electroconductive paste prepared was very uniformly dispersed without agglomeration.
(2) Viscosity counterelasticity: the aqueous slurries obtained in examples 1 to 9 and comparative examples 1 to 3 were tested for viscosity after 180 days by using a viscometer, and viscosity rebound diagrams at different times of the aqueous slurries obtained in examples 1 to 9 and comparative examples 1 to 3 were obtained as shown in fig. 3;
as can be seen from fig. 3: the aqueous electroconductive pastes provided in examples 1 to 9 were excellent in stability, and the viscosity after 180 days of standing was hardly changed, whereas the aqueous electroconductive pastes provided in comparative examples 1 to 3 were inferior in stability, and the viscosity after 180 days of standing was remarkably increased.
(3) Cyclic capacity retention rate: capacity retention after 100 weeks of 0.2C cycling was tested at 25 ℃;
(4) First charge specific capacity and first discharge specific capacity: the test was performed at a current of 0.2C, a normal temperature of 25℃ and a voltage range of 2.0 to 4.5V.
Button cells provided in application examples 1 to 9 and comparative application examples 1 to 3 were tested according to the above test methods, and the test results are shown in table 1:
TABLE 1
From the data in table 1, it can be seen that:
first, the retention rate of the cycling capacity of the button cell obtained in application examples 1 to 9 was 83 to 95%, and the specific capacity of the first charge was 416 to 458mAhg -1 Specific volume of first discharge is 388-418 mAhg -1 。
Secondly, as is clear from the data of comparative application examples 1 and comparative application examples 1 to 3, the cyclic capacity retention rate of the button cell provided in comparative application examples 1 to 3 is low, and the specific capacity for first charge and specific capacity for first discharge are low, both due to poor dispersibility and poor conductivity of the aqueous conductive paste used.
The applicant states that the present invention is described by the above examples as an aqueous conductive paste containing one-dimensional carbon nanomaterial and a method for preparing the same and application thereof, but the present invention is not limited to the above process steps, i.e., it does not mean that the present invention must be carried out by relying on the above process steps. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of selected raw materials, addition of auxiliary components, selection of specific modes, etc. fall within the scope of the present invention and the scope of disclosure.
Claims (10)
1. The preparation method of the aqueous conductive paste containing the one-dimensional carbon nanomaterial is characterized by comprising the following steps of:
(1) Mixing a dispersing agent, a stabilizing agent and water, and then adding a one-dimensional carbon nano material for mixing to obtain a premixed solution;
(2) And (3) sequentially carrying out first dissociation, first grinding, second dissociation and second grinding on the pre-mixed solution obtained in the step (1) to obtain the water-based conductive paste.
2. The method according to claim 1, wherein the content of the dispersant in the pre-mixed solution is 1 to 10 parts by weight;
preferably, the dispersant comprises any one or a combination of at least two of polyvinylpyrrolidone, carboxymethyl cellulose salt or polystyrene butadiene.
3. The preparation method according to claim 1 or 2, wherein the content of the stabilizer in the premixed solution is 1 to 10 parts by weight;
preferably, the stabilizer comprises a combination of polyvinyl alcohol and other stabilizers including any one or a combination of at least two of stearic acid, dodecylbenzene sulfonate, dodecylsulfate, fatty alcohol polyoxyethylene ether ammonium sulfate, quaternary ammonium compounds, or fatty acid glycerides;
preferably, the mass ratio of the polyvinyl alcohol to other stabilizers is 2 (0.5-10);
preferably, the water content of the pre-mixed solution is 60 to 98 parts by weight;
preferably, the mixing of the dispersant, the stabilizer and the water is performed under stirring conditions, more preferably under stirring conditions at a rotation speed of 1800 to 2200 rpm;
preferably, the mixing time for mixing the dispersant, the stabilizer and the water is 0.5 to 12 hours.
4. The method according to any one of claims 1 to 3, wherein the content of the one-dimensional carbon nanomaterial in the premixed solution is 1 to 20 parts by weight;
preferably, the one-dimensional carbon nanomaterial comprises carbon nanotubes and/or carbon fibers;
preferably, the length of the one-dimensional carbon nanomaterial is not less than 100 μm, and more preferably 100 to 200 μm;
preferably, the one-dimensional carbon nanomaterial is added and mixed under stirring, and more preferably under stirring at a rotation speed of 1800-2200 rpm;
preferably, the mixing time for adding the one-dimensional carbon nanomaterial to mix is 20-80 min, and more preferably 40-60 min.
5. The method according to any one of claims 1 to 4, wherein the time for the first dissociation is 30 to 50min;
preferably, the pressure of the first dissociation is 1000 to 1500bar, more preferably 1000 to 1200bar;
preferably, the rotating speed of the first grinding is 800-1200 r/min;
preferably, the time of the first grinding is 20-60 min;
preferably, the time of the second dissociation is 30-50 min;
preferably, the pressure of the second dissociation is 1000-1500 bar, more preferably 1000-1200 bar;
preferably, the rotation speed of the second grinding is 800-1200 r/min;
preferably, the second grinding time is 20 to 60 minutes, more preferably 40 to 50 minutes.
6. The preparation method according to any one of claims 1 to 5, characterized in that the preparation method comprises the steps of:
(1) Mixing the dispersing agent, the stabilizing agent and the water for 0.5-12 h under the stirring condition of the rotating speed of 1800-2200 rpm, adding the one-dimensional carbon nano material, and continuously mixing for 20-80 min under the stirring condition of the rotating speed of 1800-2200 rpm to obtain a premixed solution;
(2) And (3) performing primary high-energy dissociation for 30-50 min under the condition of the pressure of 1000-1500 bar, performing primary grinding for 20-60 min under the condition of the rotating speed of 800-1200 r/min, performing secondary high-energy dissociation for 30-50 min under the condition of the pressure of 1000-1500 bar, and performing secondary grinding for 20-60 min under the condition of the rotating speed of 800-1200 r/min to obtain the water-based conductive paste.
7. An aqueous conductive paste containing one-dimensional carbon nanomaterial, wherein the aqueous conductive paste is prepared by the preparation method according to any one of claims 1 to 6.
8. A negative electrode slurry, characterized in that the negative electrode slurry comprises the aqueous electroconductive slurry according to claim 7, a negative electrode active material, and a binder;
preferably, the negative electrode active material includes silicon carbide.
9. The negative electrode plate is characterized by comprising a copper foil and a negative electrode material coated on the copper foil;
the raw materials for preparing the negative electrode material comprise the negative electrode slurry according to claim 8.
10. A lithium ion battery comprising the negative electrode tab of claim 9.
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