CN117012459A - Carbon nanomaterial conductive paste and preparation method thereof - Google Patents
Carbon nanomaterial conductive paste and preparation method thereof Download PDFInfo
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- CN117012459A CN117012459A CN202311279065.XA CN202311279065A CN117012459A CN 117012459 A CN117012459 A CN 117012459A CN 202311279065 A CN202311279065 A CN 202311279065A CN 117012459 A CN117012459 A CN 117012459A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 122
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 74
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000002002 slurry Substances 0.000 claims abstract description 30
- 239000003292 glue Substances 0.000 claims abstract description 28
- 238000000227 grinding Methods 0.000 claims abstract description 25
- 239000000853 adhesive Substances 0.000 claims abstract description 20
- 230000001070 adhesive effect Effects 0.000 claims abstract description 20
- 238000007599 discharging Methods 0.000 claims abstract description 12
- 239000002041 carbon nanotube Substances 0.000 claims description 37
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 36
- 239000011230 binding agent Substances 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 19
- 239000002904 solvent Substances 0.000 claims description 18
- 239000002033 PVDF binder Substances 0.000 claims description 14
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 14
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 13
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 229910002804 graphite Inorganic materials 0.000 claims description 7
- 239000010439 graphite Substances 0.000 claims description 7
- 239000006230 acetylene black Substances 0.000 claims description 4
- 239000002134 carbon nanofiber Substances 0.000 claims description 4
- 239000003273 ketjen black Substances 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- 229920003063 hydroxymethyl cellulose Polymers 0.000 claims description 2
- 229940031574 hydroxymethyl cellulose Drugs 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 abstract description 13
- 238000007790 scraping Methods 0.000 abstract description 9
- 239000000843 powder Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 8
- 230000001276 controlling effect Effects 0.000 description 7
- 238000000265 homogenisation Methods 0.000 description 7
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 5
- 239000011324 bead Substances 0.000 description 5
- 229910052726 zirconium Inorganic materials 0.000 description 5
- 239000011149 active material Substances 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 239000006258 conductive agent Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- 239000011163 secondary particle Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000005347 demagnetization Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000001502 supplementing effect Effects 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/24—Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon
-
- 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
- H01M4/62—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)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Nanotechnology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Composite Materials (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a carbon nanomaterial conductive paste and a preparation method thereof, wherein the preparation method comprises the following steps: delivering the adhesive glue solution to IMS online dispersing equipment, adding carbon nano materials, carrying out dispersing treatment at a rotating speed of 1500-1800rpm/min, controlling the discharging temperature to be less than or equal to 60 ℃, and obtaining first conductive slurry with the scraper fineness of less than or equal to 20 mu m; performing high-pressure homogenizing dispersion on the first conductive slurry to obtain second conductive slurry with the scraper fineness less than or equal to 15 mu m; grinding is carried out in a second conductive paste conveying grinder at a rotating speed of 1200-1300rpm, the temperature of the grinding paste is controlled to be less than or equal to 50 ℃, and third conductive paste with the scraper fineness of less than or equal to 8 mu m is obtained; and obtaining the carbon nano material conductive paste through post-treatment. The carbon nano material in the conductive paste is uniformly dispersed, the fineness of the scraping plate is lower than that of the conventional conductive paste, and the conductive paste is used for a battery, so that the stability and the conductivity of the battery are improved.
Description
Technical Field
The invention relates to the field of battery materials, in particular to a carbon nanomaterial conductive slurry and a preparation method thereof.
Background
The lithium ion battery has the advantages of stable discharge, high specific energy, long service life, environmental friendliness and the like, but as the active materials of most lithium ion batteries are low in conductivity, the problems of large internal resistance, poor rate performance, poor cycle performance and the like easily occur in the manufacturing process of solid batteries, therefore, the conductivity of the active materials is usually improved by adding a conductive agent, and the comprehensive performance is further improved.
At present, the common conductive agent for the lithium battery is a carbon nano material, such as a carbon nano tube, graphite, carbon black, acetylene black, ketjen black, graphene, vapor grown carbon fiber and the like, and the carbon nano material and a binder and the like are subjected to dispersion treatment to prepare conductive slurry containing the carbon nano material, so that a high-efficiency three-dimensional conductive network can be formed in a battery system, and Li in the charging and discharging processes of the battery is quickened + And the transmission speed of electrons, has important significance for improving the multiplying power performance, the cycle performance and the safety performance of the lithium ion battery.
The carbon nano tube has a one-dimensional tubular structure and generally shows better mechanical and electrochemical properties than other carbon nano materials, however, the carbon nano tube also has the characteristics of small specific surface area and easier agglomeration, so that the carbon nano material containing the carbon nano tube has lower dispersity in the process of preparing conductive slurry, the fineness of a slurry scraping plate can only reach 10-15 microns, and even a small part of the slurry scraping plate exceeds 25 microns of large particles, which is unfavorable for the performance exertion of the carbon nano material.
Disclosure of Invention
The invention provides a preparation method of carbon nano material conductive slurry, which can uniformly disperse carbon nano material containing carbon nano tubes in the slurry and remarkably reduce the scraping fineness of the slurry.
The invention also provides the carbon nano material conductive paste prepared by the preparation method, and the uniformity of the carbon nano material conductive paste is good, and the scraping plate fineness is low, so that the conductive paste is used for a battery, and the stability and the conductivity of the battery can be improved.
In a first aspect, the present invention provides a method for preparing a conductive paste of a carbon nanomaterial, comprising the steps of:
s1: dissolving a binder in a solvent to prepare a binder glue solution;
s2: delivering the adhesive glue solution to IMS online dispersing equipment, then beginning to input carbon nano materials comprising carbon nano tubes, carrying out dispersing treatment at a rotating speed of 1500-1800rpm/min, controlling the discharging temperature to be less than or equal to 60 ℃ and obtaining first conductive slurry with the viscosity of 60000-70000cps and the scraper fineness to be less than or equal to 20 mu m;
s3: carrying out homogenizing and dispersing treatment on the first conductive paste with the pressure of 0.11-0.13Mpa and the frequency of 30-35HZ to obtain second conductive paste with the viscosity of 70000-7500cps and the scraper fineness of less than or equal to 15 mu m;
s4: conveying the second conductive paste into a grinder containing medium balls with the diameter of 0.8-1mm, grinding at the rotating speed of 1200-1300rpm, controlling the temperature of the grinding paste to be less than or equal to 50 ℃ and obtaining third conductive paste with the viscosity of 80000-85000cps and the scraper fineness of less than or equal to 80 mu m;
s5: the third conductive paste is demagnetized and screened through a 100-mesh sieve to obtain the carbon nano material conductive paste;
wherein the radial dimension of the carbon nano tube is 1-20nm, and the axial dimension is 0.1-2 mu m.
Further, step S1 includes: adding the binder and the solvent into a material stirring tank, and dispersing for 10-15min at a rotating speed of 300-350rpm/min by using IMS online dispersing equipment to obtain the binder glue solution.
Further, step S2 includes: and conveying the adhesive glue solution to IMS online dispersing equipment, starting to input the carbon nano material comprising the carbon nano tube, performing primary dispersing treatment at the rotating speed of 500-550rpm/min until the carbon nano material is fed, performing secondary dispersing treatment at the rotating speed of 1500-1800rpm/min, controlling the discharging temperature to be less than or equal to 50 ℃, and obtaining the first conductive paste with the viscosity of 60000-61000cps and the scraper fineness of less than or equal to 15 mu m.
Further, in the carbon nano material conductive paste, the mass ratio of the carbon nano tube is 3% -5%.
Further, the mass ratio of the binder to the solvent to the carbon nanomaterial is 1:90-95:4-6.
Further, the solvent comprises deionized water,Methyl pyrrolidone, N,>dimethylformamide, N,>any one or a combination of at least two of dimethylacetamide and absolute ethanol.
Further, the binder includes any one or a combination of at least two of polyvinylidene fluoride, polyvinylpyrrolidone, sodium hydroxymethyl cellulose and styrene butadiene rubber.
Further, the carbon nanomaterial further includes any one or a combination of at least two of conductive graphite, conductive carbon black, acetylene black, ketjen black, vapor grown carbon fiber, and expanded graphite.
Further, the carbon nanomaterial comprises conductive carbon black and carbon nanotubes in a mass ratio of 1:4-5.
In a second aspect, the present invention provides a carbon nanomaterial conductive paste prepared by the preparation method provided in the first aspect.
The carbon nanomaterial conductive slurry prepared by the invention contains carbon nanotubes, wherein the carbon nanomaterial is uniformly dispersed in the carbon nanomaterial, and the scraping fineness is lower than 10 mu m, so that the conductive slurry is used for a battery, and the stability and the conductivity of the battery can be improved.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the invention and together with the description, serve to explain the principles of the invention.
FIG. 1 is a process flow diagram of the preparation method of the present invention.
Detailed Description
The present invention will be described in further detail below for the purpose of better understanding of the aspects of the present invention by those skilled in the art. The following detailed description is merely illustrative of the principles and features of the present invention, and examples are set forth for the purpose of illustration only and are not intended to limit the scope of the invention. All other embodiments, which can be made by those skilled in the art based on the examples of the invention without making any inventive effort, are intended to be within the scope of the invention.
In one aspect, the present invention provides a method for preparing a conductive paste of a carbon nanomaterial, which is described in detail with reference to fig. 1, and includes the following steps:
s1: dissolving a binder in a solvent to prepare a binder glue solution;
s2: delivering the adhesive glue solution to IMS online dispersing equipment, then beginning to input carbon nano materials comprising carbon nano tubes, carrying out dispersing treatment at a rotating speed of 1500-1800rpm/min, controlling the discharging temperature to be less than or equal to 60 ℃ and obtaining first conductive slurry with the viscosity of 60000-70000cps and the scraper fineness to be less than or equal to 20 mu m;
s3: carrying out homogenizing and dispersing treatment on the first conductive paste with the pressure of 0.11-0.13Mpa and the frequency of 30-35HZ to obtain second conductive paste with the viscosity of 70000-7500cps and the scraper fineness of less than or equal to 15 mu m;
s4: conveying the second conductive paste into a grinder containing medium balls with the diameter of 0.8-1mm, grinding at the rotating speed of 1200-1300rpm, controlling the temperature of the grinding paste to be less than or equal to 50 ℃ and obtaining third conductive paste with the viscosity of 80000-85000cps and the scraper fineness of less than or equal to 8 mu m;
s5: the third conductive paste is demagnetized and screened through a 100-mesh sieve to obtain the carbon nano material conductive paste;
wherein the radial dimension of the carbon nano tube is 1-20nm, and the axial dimension is 0.1-2 mu m.
The carbon nano tube has a one-dimensional tubular structure, can play a role of a wire in a conductive network of the conductive paste, but is too fine to be mutually wound in the paste to cause agglomeration and influence the scraping fineness of the paste, and in the invention, by combining the preparation method, the small-size carbon nano tube can be uniformly dispersed in the conductive paste, and the reason is that: on one hand, the invention adopts IMS on-line dispersing equipment to carry out main dispersing treatment, and the on-line speed of the equipment can obtain high shearing force exceeding 30m/s, so that the carbon nano material containing carbon nano tubes is dispersed in the conductive slurry faster and more uniformly; on the other hand, the second conductive paste with proper uniformity is obtained by controlling parameters such as the discharging temperature, the scraping fineness, the viscosity, the high-pressure homogenization and the like of each step, and the conductive paste is combined with a specific grinding process, so that the conductive paste of the carbon nano material, which is more uniform in carbon nano tube dispersion and has the scraping fineness (less than or equal to 8 mu m) which is obviously lower than that of the existing product, can be obtained.
The IMS online dispersing device (Intelligence Mixing System) adopts an online dispersing system of powder and liquid, can generate high-speed flow by pumping the liquid, forms strong vacuum in a dispersing area, can directly suck the powder from a powder tank car, a storage bin, a small bag and a ton bag without loss by vacuum suction, and fully disperses and mixes the powder with the liquid.
In the present invention, the radial dimension of the carbon nanotubes is 1-20nm, the axial dimension is 0.1-2 μm, the radial dimension is understood as the tube outer diameter of the carbon nanotubes, the axial dimension is understood as the tube length, and preferably, the radial dimension of the carbon nanotubes is 5-10nm, and more preferably, 6-7nm.
The step S1 comprises the following steps: adding the binder and the solvent into a material stirring tank, and dispersing for 10-15min at a rotating speed of 300-350rpm/min by using IMS online dispersing equipment to obtain the binder glue solution. The embodiment can obtain the adhesive glue solution with certain initial viscosity, and the adhesive glue solution is more beneficial to the subsequent dispersion of the carbon nano material.
In a preferred embodiment, step S2 includes: and conveying the adhesive glue solution to IMS online dispersing equipment, starting to input the carbon nano material comprising the carbon nano tube, performing primary dispersing treatment at the rotating speed of 500-550rpm/min until the carbon nano material is fed, performing secondary dispersing treatment at the rotating speed of 1500-1800rpm/min, controlling the discharging temperature to be less than or equal to 50 ℃, and obtaining the first conductive paste with the viscosity of 60000-61000cps and the scraper fineness of less than or equal to 15 mu m.
In the above embodiment, the lower dispersion speed (500-550 rpm/min) is maintained, the carbon nanomaterial is added into the adhesive glue solution, the feeding is completed, and then the rotating speed (1500-1800 rpm/min) is increased, so that compared with the stirring after the feeding of the carbon nanomaterial, or the stirring is directly carried out at a high speed, the agglomeration phenomenon is not easy to occur, the scraper fineness of the slurry can be improved, and meanwhile, the scraper fineness of the slurry can be further reduced to 5-6 mu m by limiting the discharging temperature to be less than or equal to 50 ℃.
In a preferred embodiment, the mass ratio of the carbon nano material conductive paste to the carbon nano tube is 3% -5%. The carbon nano tube in the range can be more uniformly dispersed in the conductive paste, so that the excellent physical properties of the carbon nano tube are better exerted, and the electrochemical properties of the active material are improved.
In a preferred embodiment, the mass ratio of the binder, the solvent and the carbon nanomaterial is 1:90-95:4-6. The carbon nanomaterial conductive paste can further improve the electrical property of the electrode plates, and can also improve the dispersion uniformity of the carbon nanomaterial in the conductive paste.
The binder and the solvent are not particularly limited in principle, and for example, the binder may include any one or a combination of at least two of polyvinylidene fluoride, polyvinylpyrrolidone, sodium carboxymethylcellulose, and styrene-butadiene rubber; the solvent comprises deionized water,Methyl pyrrolidone, N,>dimethylformamide, N,>any one or a combination of at least two of dimethylacetamide and absolute ethanol. However, since the viscosity of the slurry obtained in each step is important for the present invention, the following is an example in order to improve the rate and controllability of the slurry uniformity in each stepThe binder is preferably polyvinylidene fluoride and the solvent is preferably +.>Methyl pyrrolidone.
In a preferred embodiment, the carbon nanomaterial further comprises any one or a combination of at least two of conductive graphite, conductive carbon black, acetylene black, ketjen black, vapor grown carbon fiber, and expanded graphite. It is understood that the carbon nanomaterial of the present invention is nano-sized, for example, having a particle size in any of 1 to 1000nm, 20 to 800nm, 50 to 700nm, 80 to 600nm, 100 to 500nm, 200 to 400nm, etc.
In a preferred embodiment, the carbon nanomaterial comprises conductive carbon black and carbon nanotubes in a mass ratio of 1:4-5. In the embodiment, the carbon nanotubes can be uniformly dispersed in the conductive paste, so that a relatively clear conductive wire is formed, and the conductive carbon black is further dispersed near the conductive wire to play a role in supplementing, so that the excellent physical properties of the carbon nanotubes are better exerted, and the electrochemical properties of the active material are improved.
In a preferred embodiment, the step S2 of adding the carbon nanomaterial includes the following steps: and opening a vacuum powder suction valve on the IMS equipment, and adding the carbon nano material into the IMS online dispersing equipment in a vacuum powder suction mode.
The material of the medium ball is not particularly limited in principle, but in order to achieve the polishing effect more preferably, the medium ball is a zirconium bead.
In a preferred embodiment, the demagnetization comprises the following processes: and the third conductive paste is conveyed into a demagnetizing cavity of the demagnetizer and is contacted with a high-magnetism magnetic rod for demagnetizing.
In yet another aspect, the present invention provides a carbon nanomaterial conductive paste prepared by the preparation method provided in the first aspect.
The carbon nano material conductive paste can be directly mixed with an anode active substance and the like, and a stable high-speed three-dimensional conductive network system can be formed by coating the carbon nano material conductive paste on the surface of a current collector.
The invention is further illustrated by the following examples:
the Carbon Nanotubes (CNTs) used in the following examples or comparative examples had a radial dimension of 5 to 10nm and an axial dimension of 0.8 to 1.5. Mu.m; IMS on-line dispersion equipment was produced from the Oryza sativa, inc., of the sciences group; the polyvinylidene fluoride was model 25618 and had a weight average molecular weight (Mw) of 160 ten thousand.
Example 1
The example provides a carbon nanomaterial conductive paste, the preparation method of which comprises the following steps:
s1: 94wt% of N-methylpyrrolidone (NMP) and 1wt% of polyvinylidene fluoride (PVDF) are added into a material stirring tank, an IMS online dispersing device is used, the device is circulated for 10 minutes at the speed of 300rpm/min, so that the PVDF is completely dissolved in an NMP solvent, and a binder glue solution is prepared;
s2: the adhesive glue solution is conveyed to IMS online dispersing equipment by using a double screw pump, the rotating speed of the equipment is regulated to 500rpm/min, a vacuum powder suction valve on the IMS equipment is opened, and 4wt% of CNT and 1wt% of super conductive carbon black SP are added into the adhesive glue solution in a vacuum powder suction mode; after the powder feeding process is finished, the rotating speed of the equipment is adjusted to 1500-1800rpm/min, the dispersion is carried out for 30 minutes, the discharging temperature is 48-50 ℃, and the first conductive paste with the viscosity of 61000cps and the scraper fineness of 13-15 mu m is prepared;
s3: carrying out high-pressure homogenization dispersion on the first conductive paste, wherein the pressure is 0.11-0.13Mpa, the homogenization frequency is 35HZ, the viscosity of the homogenized conductive paste is 70000-7500cps, and the scraper fineness is 12 mu m, so as to obtain second conductive paste;
s4: conveying the second conductive paste to a grinder through a double screw pump for grinding, wherein the diameter of zirconium beads is 0.8-1mm, grinding one batch, the grinding rotating speed is 1300rpm, the temperature of the grinding paste is 50 ℃, and preparing third conductive paste with the viscosity of 81000cps and the scraper fineness of 5 mu m;
s5: and the third conductive paste passes through a demagnetizer, the paste is in contact with a high-magnetism magnetic rod in a demagnetizing cavity to perform demagnetizing, the content of magnetic components in the paste is reduced, and the paste is filtered through a 100-mesh screen after the demagnetizing is finished to prepare a carbon nanotube conductive paste finished product.
Example 2
The example provides a carbon nanomaterial conductive paste, the preparation method of which comprises the following steps:
s1: adding 94wt% of NMP and 1wt% of PVDF into a material stirring tank, and circulating for 10 minutes by using IMS online dispersing equipment at the rotating speed of 300rpm/min to completely dissolve the PVDF into NMP solvent to prepare adhesive glue solution;
s2: the adhesive glue solution is conveyed to IMS on-line dispersing equipment by using a double screw pump, the rotating speed of the equipment is adjusted to 1500-1800rpm/min, a vacuum powder suction valve on the IMS equipment is opened, and 4wt% of CNT and 1wt% of super conductive carbon black SP are added into the adhesive glue solution in a vacuum powder suction mode; after the powder feeding process is finished, maintaining the rotation speed of equipment at 1500-1800rpm/min, and dispersing for 30 minutes at the discharge temperature of 55 ℃ to prepare first conductive slurry with the viscosity of 70000cps and the scraper fineness of 18 mu m;
s3: carrying out high-pressure homogenizing dispersion on the first conductive paste, wherein the pressure is 0.11-0.13Mpa, the homogenizing frequency is 35HZ, the viscosity of the homogenized conductive paste is 74000cps, and the scraper fineness is 15 mu m, so as to obtain second conductive paste;
s4: conveying the second conductive paste to a grinder through a double screw pump for grinding, wherein the diameter of zirconium beads is 0.8-1mm, grinding one batch, the grinding rotating speed is 1300rpm, the temperature of the grinding paste is 50 ℃, and preparing third conductive paste with the viscosity of 84000cps and the scraper fineness of 8 mu m;
s5: and the third conductive paste passes through a demagnetizer, the paste is in contact with a high-magnetism magnetic rod in a demagnetizing cavity to perform demagnetizing, the content of magnetic components in the paste is reduced, and the paste is filtered through a 100-mesh screen after the demagnetizing is finished to prepare a carbon nanotube conductive paste finished product.
Example 3
The example provides a carbon nanomaterial conductive paste, the preparation method of which comprises the following steps:
s1: adding 94wt% of NMP and 1wt% of PVDF into a material stirring tank, and circulating for 10 minutes by using IMS online dispersing equipment at the rotating speed of 300rpm/min to completely dissolve the PVDF into NMP solvent to prepare adhesive glue solution;
s2: the adhesive glue solution is conveyed to IMS online dispersing equipment by using a double screw pump, the rotating speed of the equipment is regulated to 500rpm/min, a vacuum powder suction valve on the IMS equipment is opened, and 4wt% of CNT and 1wt% of super conductive carbon black SP are added into the adhesive glue solution in a vacuum powder suction mode; after the powder feeding process is finished, maintaining the rotation speed of equipment at 1500-1800rpm/min, and dispersing at a discharge temperature of 60 ℃ for 30 minutes to prepare first conductive slurry with viscosity of 62000cps and scraper fineness of 17 mu m;
s3: carrying out high-pressure homogenization dispersion on the first conductive paste, wherein the pressure is 0.11-0.13Mpa, the homogenization frequency is 35HZ, the viscosity of the homogenized conductive paste is 70000cps, and the scraper fineness is 15 mu m, so as to obtain second conductive paste;
s4: conveying the second conductive paste to a grinder through a double screw pump for grinding, wherein the diameter of zirconium beads is 0.8-1mm, grinding one batch, the grinding rotating speed is 1300rpm, the temperature of the grinding paste is 50 ℃, and preparing third conductive paste with the viscosity of 83000cps and the scraper fineness of 7 mu m;
s5: and the third conductive paste passes through a demagnetizer, the paste is in contact with a high-magnetism magnetic rod in a demagnetizing cavity to perform demagnetizing, the content of magnetic components in the paste is reduced, and the paste is filtered through a 100-mesh screen after the demagnetizing is finished to prepare a carbon nanotube conductive paste finished product.
Comparative example 1
The example provides a carbon nanomaterial conductive paste, the preparation method of which comprises the following steps:
s1: adding 94wt% of NMP and 1wt% of PVDF into a material stirring tank, and circulating for 50 minutes by using a planetary stirrer at the equipment rotating speed of 1000rpm/min to completely dissolve the PVDF into NMP solvent to prepare binder glue solution;
s2: the adhesive glue solution is conveyed to a planetary mixer by using a double screw pump, the rotation speed of equipment is adjusted to 1000rpm/min, and 4wt% of CNT and 1wt% of super conductive carbon black SP are added into the adhesive glue solution; after the powder feeding process is finished, the rotating speed of the equipment is regulated to 1200rpm/min, dispersion treatment is carried out, the discharging temperature is controlled to be 50 ℃, and the first conductive paste with the viscosity of 53000cps and the scraper fineness of 20 mu m is prepared;
s3: carrying out high-pressure homogenization dispersion on the first conductive paste, wherein the pressure is 0.11-0.13Mpa, the homogenization frequency is 35HZ, the viscosity of the homogenized conductive paste is 65000cps, and the scraper fineness is less than or equal to 16 mu m, so as to obtain second conductive paste;
s4: conveying the second conductive paste to a grinder for grinding through a double screw pump, wherein the diameter of zirconium beads is 0.8-1mm, grinding a batch, the grinding rotating speed is 1300rpm, the temperature of the grinding paste is less than or equal to 50 ℃, and preparing the third conductive paste with the viscosity of 81000 cps;
s5: and the third conductive paste passes through a demagnetizer, the paste is in contact with a high-magnetism magnetic rod in a demagnetizing cavity to perform demagnetizing, the content of magnetic components in the paste is reduced, and the paste is filtered through a 100-mesh screen after the demagnetizing is finished to prepare a carbon nanotube conductive paste finished product.
Performance test:
primary particle diameter D of carbon nanomaterial conductive paste of example 1 and comparative example 1 was observed by scanning electron microscopy y 50 and a secondary particle diameter D50, the results are shown in table 1;
the carbon nanomaterial conductive slurries of examples 1-2 and comparative example 1 were tested for fineness by a fineness scraper and the results are shown in table 1;
the resistivity of the carbon nanomaterial conductive slurries of examples 1-3 and comparative example 1 was measured using a slurry resistance meter, and the results are shown in table 1;
the carbon nanomaterial conductive pastes of example 1 and comparative example 1 were respectively fabricated by the same process (the paste was coated on a copper foil, baked, compacted to fabricate a test discharge electrode sheet), and the performance of the electrode sheet was tested, and the results are shown in table 2.
Table 1:
note that: "-" indicates that table 1 did not record the test results.
Table 2:
as can be seen from table 1: the primary particles, secondary particles, blade fineness and resistivity of the carbon nanomaterial conductive slurry prepared by the preparation methods of examples 1-3 are lower than those of the carbon nanomaterial conductive slurry prepared by comparative example 1, and particularly the blade fineness and resistivity of the carbon nanomaterial conductive slurry of example 1 are the lowest.
As can be seen from table 2, the conductive paste of carbon nanomaterial prepared by the preparation method of example 1 can obtain higher specific capacity and cycle performance for a battery than that of comparative example 1.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (9)
1. The preparation method of the carbon nanomaterial conductive slurry is characterized by comprising the following steps of:
s1: dissolving a binder in a solvent to prepare a binder glue solution;
s2: delivering the adhesive glue solution to IMS online dispersing equipment, beginning to input carbon nano materials comprising carbon nano tubes, carrying out dispersing treatment at a rotating speed of 1500-1800rpm/min, controlling the discharging temperature to be less than or equal to 60 ℃, and obtaining first conductive slurry with the viscosity of 60000-70000cps and the scraper fineness to be less than or equal to 20 mu m;
s3: carrying out homogenizing and dispersing treatment on the first conductive paste with the pressure of 0.11-0.13Mpa and the frequency of 30-35HZ to obtain second conductive paste with the viscosity of 70000-7500cps and the scraper fineness of less than or equal to 15 mu m;
s4: conveying the second conductive paste into a grinder containing medium balls with the diameter of 0.8-1mm, grinding at the rotating speed of 1200-1300rpm, controlling the temperature of the grinding paste to be less than or equal to 50 ℃ and obtaining third conductive paste with the viscosity of 80000-85000cps and the scraper fineness of less than or equal to 8 mu m;
s5: the third conductive paste is demagnetized and screened through a 100-mesh sieve to obtain the carbon nano material conductive paste;
wherein the radial dimension of the carbon nano tube is 1-20nm, and the axial dimension is 0.1-2 mu m;
in the carbon nano material conductive paste, the mass ratio of the carbon nano tube is 3% -5%.
2. The method of claim 1, wherein step S1 comprises: adding the binder and the solvent into a material stirring tank, and dispersing for 10-15min at a rotating speed of 300-350rpm/min by using IMS online dispersing equipment to obtain the binder glue solution.
3. The method of claim 1, wherein step S2 comprises: and conveying the adhesive glue solution to IMS online dispersing equipment, starting to input the carbon nano material comprising the carbon nano tube, performing primary dispersing treatment at the rotating speed of 500-550rpm/min until the carbon nano material is fed, performing secondary dispersing treatment at the rotating speed of 1500-1800rpm/min, controlling the discharging temperature to be less than or equal to 50 ℃, and obtaining the first conductive paste with the viscosity of 60000-61000cps and the scraper fineness of less than or equal to 15 mu m.
4. A method according to any one of claims 1 to 3, wherein the mass ratio of the binder, the solvent and the carbon nanomaterial is 1:90-95:4-6.
5. A method of preparing according to any one of claims 1 to 3, wherein the binder comprises any one or a combination of at least two of polyvinylidene fluoride, polyvinylpyrrolidone, sodium hydroxymethyl cellulose and styrene butadiene rubber.
6. A method according to any one of claims 1 to 3, wherein the solvent comprises deionized water,Methyl pyrrolidone, N,>dimethylformamide, N,>any one or a combination of at least two of dimethylacetamide and absolute ethanol.
7. The method of any one of claims 1 to 3, wherein the carbon nanomaterial further comprises any one or a combination of at least two of conductive graphite, conductive carbon black, acetylene black, ketjen black, vapor grown carbon fiber, and expanded graphite.
8. The method of claim 7, wherein the carbon nanomaterial comprises conductive carbon black and carbon nanotubes in a mass ratio of 1:4-5.
9. A carbon nanomaterial electroconductive paste prepared by the preparation method of any one of claims 1 to 8.
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| CN110620237A (en) * | 2019-10-25 | 2019-12-27 | 新奥石墨烯技术有限公司 | Conductive paste, preparation method and application thereof, and battery |
| CN110634591A (en) * | 2019-09-29 | 2019-12-31 | 新奥石墨烯技术有限公司 | Conductive paste, preparation method and application thereof, and battery |
| CN113036142A (en) * | 2021-03-10 | 2021-06-25 | 哈尔滨万鑫石墨谷科技有限公司 | Carbon nano conductive slurry and preparation method and application thereof |
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| CN110634591A (en) * | 2019-09-29 | 2019-12-31 | 新奥石墨烯技术有限公司 | Conductive paste, preparation method and application thereof, and battery |
| CN110620237A (en) * | 2019-10-25 | 2019-12-27 | 新奥石墨烯技术有限公司 | Conductive paste, preparation method and application thereof, and battery |
| CN113036142A (en) * | 2021-03-10 | 2021-06-25 | 哈尔滨万鑫石墨谷科技有限公司 | Carbon nano conductive slurry and preparation method and application thereof |
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