CN115458747A - Positive current collector with solid electrolyte surface treatment and preparation method and application thereof - Google Patents

Positive current collector with solid electrolyte surface treatment and preparation method and application thereof Download PDF

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CN115458747A
CN115458747A CN202211329892.0A CN202211329892A CN115458747A CN 115458747 A CN115458747 A CN 115458747A CN 202211329892 A CN202211329892 A CN 202211329892A CN 115458747 A CN115458747 A CN 115458747A
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solid electrolyte
parts
dispersing
current collector
slurry
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施雅玲
谭军豪
闫昭
沈德赟
李婷
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Huzhou Nanmu Nano Technology Co ltd
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Huzhou Nanmu Nano Technology Co ltd
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    • 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
    • H01M4/64—Carriers or collectors
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/661—Metal or alloys, e.g. alloy coatings
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/665—Composites
    • H01M4/667—Composites in the form of layers, e.g. coatings
    • 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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  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • Composite Materials (AREA)
  • Manufacturing & Machinery (AREA)
  • Cell Electrode Carriers And Collectors (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The embodiment of the invention relates to a positive current collector with solid electrolyte surface treatment, a preparation method and application. The preparation method comprises the following steps: mixing 40-75 parts of water and 0.1-0.5 part of thickening agent according to parts by weight, dispersing at a high speed for 20-60 minutes, then adding 20-40 parts of solid electrolyte, dispersing at a high speed for 30-90 minutes, and then adding 0.1-0.5 part of wetting agent, dispersing at a high speed for 20-60 minutes to obtain a first slurry; mixing 1-3 parts of dispersing agent, 50-90 parts of water and 0-20 parts of solvent according to parts by weight, dispersing at high speed until the mixture is uniform, adding 5-20 parts of nano carbon material, and dispersing at high speed for 2-5 hours to obtain second slurry; according to the weight portion, 3-10 portions of the first slurry and 75-90 portions of the second slurry are mixed at a high speed, 0.5-1.5 portions of pH regulator and 0.1-0.5 portions of flatting agent are added and mixed evenly at a low speed, and finally 4-10 portions of binder are added to obtain the conductive slurry of the positive current collector with solid electrolyte surface treatment; and uniformly coating the conductive slurry on the surface of the aluminum foil to obtain the positive electrode current collector with solid electrolyte surface treatment for the power battery.

Description

Positive current collector with solid electrolyte surface treatment and preparation method and application thereof
Technical Field
The invention relates to the technical field of new energy materials, in particular to a positive current collector with solid electrolyte surface treatment, a preparation method and application thereof.
Background
Lithium ion batteries have evolved from the 20 th century, the 60 th era, and have now become mature and commercially viable, almost completely replacing conventional secondary batteries because they have advantages over conventional batteries: the output voltage is higher than that of the traditional secondary battery, the energy density is higher than that of the traditional battery, the service life is longer than that of the traditional battery, the environment is protected, the pollution is less, the memory effect is small, and the storage performance is better than that of other batteries. The lithium ion battery is developed to the present, is rapidly updated, has a very wide prospect, and still has some problems to be solved urgently. The safety of the power type lithium ion battery is not high, the power type lithium ion battery is easy to ignite and explode, and the safety performance is not firm; the increasing demand of people and the continuous innovation of science and technology, the higher requirement of people on lithium ions, the breakthrough of cycle performance and the improvement of rate capability are all the directions in which lithium ion batteries need to be developed. The main materials of the lithium battery comprise a positive electrode material, a negative electrode material, electrolyte and a diaphragm. However, in addition to the four main parts, the current collectors used for storing the positive and negative electrode materials are also important components of the lithium battery. For lithium ion batteries, the positive current collector typically used is aluminum foil and the negative current collector is copper foil.
In the field of lithium batteries, aluminum foils are used as current collectors of lithium ion batteries, generally, rolled aluminum foils are used as positive current collectors in the lithium ion battery industry, and the current collectors play an important role in improving the charging and discharging efficiency of the lithium batteries. And the surface of the aluminum foil is coated with the conductive slurry, so that the polarization of the battery can be inhibited, the heat effect can be reduced, the multiplying power performance of the battery can be improved, the adhesion of an active substance and the aluminum foil can be improved, and the using amount of a binder can be reduced.
In order to solve the problems, patent CN 104538638B discloses a lithium ion battery anode aluminum foil conductive agent and a preparation method thereof, which are prepared from the following raw materials, by weight, 15.0% -22.0% of graphite, 3.0% -6.0% of conductive carbon black, 5.0% -10.0% of modified waterborne epoxy resin, 11.0% -25.0% of butadiene styrene polymer, 0.1% -1.5% of sodium carboxymethylcellulose, 0.05% -0.5% of sodium polyacrylate, 2.0% -6.5% of peach gum, 0.3% -0.8% of 2-amino-2-methyl-1-propanol, 0.05% -0.5% of polyoxyethylene sorbitan monolaurate, 0.2% -0.7% of polyvinylpyrrolidone, 0.3% -1.0% of sodium methylene dinaphthalene sulfonate, 2.0% -6.0% of ammonia water, and the balance of deionized water. The invention provides the lithium ion battery anode aluminum foil conductive agent with good conductivity, good adhesive force and good solvent tolerance. However, the carbon-coated aluminum foil has high impedance, high temperature rise effect after the battery is manufactured, no obvious increase in cycle performance is caused, and the performance of the power battery is not obviously improved.
In conclusion, the conductive paste with low impedance, good long-cycle performance and weak temperature rise effect has wide market application value and prospect, and can effectively promote the further development of the lithium battery industry.
Disclosure of Invention
The invention aims to provide a positive current collector with solid electrolyte surface treatment, a preparation method and application thereof, which can reduce battery impedance, promote long cycle of a battery and improve temperature rise effect of the battery.
To this end, in a first aspect, embodiments of the present invention provide a method for preparing a positive electrode current collector having a solid electrolyte surface treatment, the method comprising:
mixing 40-75 parts of water and 0.1-0.5 part of thickening agent according to parts by weight, dispersing at high speed for 20-60 minutes, adding 20-40 parts of solid electrolyte, dispersing at high speed for 30-90 minutes, then adding 0.1-0.5 part of wetting agent, and dispersing at high speed for 20-60 minutes to obtain first slurry;
mixing 1-3 parts of dispersing agent, 50-90 parts of water and 0-20 parts of solvent according to parts by weight, dispersing at high speed until the mixture is uniform, adding 5-20 parts of nano carbon material, and dispersing at high speed for 2-5 hours to obtain second slurry;
according to the weight portion, 3-10 portions of first slurry and 75-90 portions of second slurry are mixed at high speed, then 0.5-1.5 portions of pH regulator and 0.1-0.5 portions of flatting agent are added and mixed evenly at low speed, and finally 4-10 portions of binder are added, so as to obtain the conductive slurry of the positive current collector with solid electrolyte surface treatment;
and uniformly coating the conductive slurry on the surface of the aluminum foil to obtain the positive electrode current collector with solid electrolyte surface treatment for the power battery.
Preferably, the apparatus for high-speed dispersion comprises: one or more of a high-speed dispersion machine, a high-speed shearing emulsifying machine, a vacuum defoaming dispersion machine and a sand mill; the dispersion speed of the high-speed dispersion is 2000r/min-12000r/min; the dispersing speed of the low-speed dispersion is 200r/min-500r/min.
Preferably, the thickener comprises: one or more of methylcellulose, hydroxyethyl cellulose, modified starch, polyvinyl alcohol, polyethylene wax and polymethacrylate;
the wetting agent comprises: one or more of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, polyethylene glycol and alkylphenol polyoxyethylene;
the solid electrolyte includes: one or more of garnet type solid electrolyte material, NASICON type solid electrolyte material, LISICON solid electrolyte material and perovskite type solid electrolyte material are mixed;
the nanoscale carbon material comprises: one or more of carbon black, graphene and carbon nanotubes; the primary particle size D50 of the carbon black is 30-60 nm, the graphene is single-layer graphene or multi-layer graphene, and the carbon nanotube is a single-walled carbon nanotube or a multi-walled carbon nanotube;
the solvent comprises: one or more of ethylene glycol, propylene glycol, hexylene glycol, ethylene glycol butyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, tripropylene glycol n-butyl ether, propylene glycol phenyl ether, hexylene glycol butyl ether acetate and 3-ethoxy ethyl propionate;
the dispersing agent is a hydrophilic acrylic hyperbranched block copolymer;
the pH regulator comprises: one or more of ammonia, 2-amino-2-methyl-1-propanol, dimethylethanolamine, N-methylethanolamine, diethanolamine, butylethanolamine, 2-amino-2 ethyl-1, 3-propanediol, sodium hydroxide and potassium hydroxide;
the leveling agent comprises: one or more of waterborne modified polyacrylate, anionic acrylic copolymer, nonionic polyamine-ethylene oxide condensate, nonionic polyethylene glycol ester and alkylphenol polyoxyethylene are mixed;
the binder comprises one or more of polyacrylate type binder, styrene butadiene rubber SBR type binder, polyacrylonitrile type binder or other resin type binder.
Preferably, the coating method is one of gravure coating, micro-gravure coating and slot extrusion coating.
In a second aspect, the embodiment of the present invention provides a positive electrode current collector with a solid electrolyte surface treatment for a power battery, which is prepared by the preparation method of the first aspect.
Preferably, the positive electrode current collector includes: a solid electrolyte doped conductive coating and an aluminum foil;
the conductive paste forming the solid electrolyte doped conductive coating comprises: the electrolyte comprises a solid electrolyte, a dispersing agent, a thickening agent, a wetting agent, water, a second solvent, a nano-scale carbon material, a leveling agent, a pH regulator and a binder.
In a third aspect, embodiments of the present invention provide a lithium battery positive electrode comprising the positive electrode current collector for a power battery with a solid electrolyte surface treatment as described in the second aspect above.
In a fourth aspect, an embodiment of the present invention provides a lithium battery including the lithium battery positive electrode in the third aspect.
According to the preparation method of the positive current collector with the solid electrolyte surface treatment, provided by the embodiment of the invention, the conductivity of the aluminum foil carbon-coated layer is increased through the nano-scale carbon material, the interface of the positive current collector and the electrolyte is effectively regulated and controlled through the addition of the solid electrolyte, and meanwhile, the solid electrolyte has relatively high ionic conductivity and electronic insulation performance, so that the preparation method has positive significance for reducing the interface impedance. After the solid electrolyte is doped, a stable interface is formed on the surface of the positive current collector, and continuous reaction between the positive current collector and the electrolyte is inhibited. Therefore, the impedance of the battery is stabilized over a long cycle. Therefore, the solid electrolyte doped aluminum foil conductive paste for the positive electrode current collector can effectively improve the performance of the whole lithium battery, including but not limited to reducing impedance, improving long cycle stability of the battery and weakening the temperature rise effect of the power battery. . A lithium battery made of the surface-treated positive current collector aluminum foil is low in impedance, good in long-term cycle performance, weak in temperature rise effect and excellent in overall electrical performance.
Drawings
Fig. 1 is a flow chart of a method for preparing a positive electrode current collector with a surface treatment of a solid electrolyte according to an embodiment of the present invention.
Detailed Description
The technical solution of the present invention is further described in detail by the accompanying drawings and embodiments.
The embodiment of the invention provides a preparation method of a positive current collector with solid electrolyte surface treatment, as shown in fig. 1, the preparation method mainly comprises the following steps:
step 110, mixing 40-75 parts of water and 0.1-0.5 part of thickening agent according to parts by weight, dispersing for 20-60 minutes at a high speed, adding 20-40 parts of solid electrolyte, dispersing for 30-90 minutes at a high speed, then adding 0.1-0.5 part of wetting agent, and dispersing for 20-60 minutes at a high speed to obtain first slurry;
wherein, the equipment used for high-speed dispersion comprises: one or more of a high-speed dispersion machine, a high-speed shearing emulsification machine, a vacuum defoaming dispersion machine and a sand mill; the dispersion speed of the high-speed dispersion is 2000r/min-12000r/min.
The thickening agent comprises: one or more of methylcellulose, hydroxyethyl cellulose, modified starch, polyvinyl alcohol, polyethylene wax and polymethacrylate;
the wetting agents include: one or more of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, polyethylene glycol and alkylphenol polyoxyethylene;
the solid electrolyte includes: one or more of garnet type solid electrolyte material, NASICON type solid electrolyte material, LISICON solid electrolyte material and perovskite type solid electrolyte material.
120, mixing 1-3 parts of dispersing agent, 50-90 parts of water and 0-20 parts of solvent in parts by weight, dispersing at a high speed until the mixture is uniform, adding 5-20 parts of nano carbon material, and dispersing at a high speed for 2-5 hours to obtain second slurry;
wherein the dispersion speed of the high-speed dispersion is 2000r/min-12000r/min;
the nanoscale carbon material includes: one or more of carbon black, graphene and carbon nanotubes; wherein the primary particle size D50 of the carbon black is 30-60 nm, the graphene is single-layer graphene or multi-layer graphene, and the carbon nano tube is a single-wall carbon nano tube or a multi-wall carbon nano tube;
the solvent comprises: one or more of ethylene glycol, propylene glycol, hexanediol, ethylene glycol butyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, tripropylene glycol n-butyl ether, propylene glycol phenyl ether, hexanediol butyl ether acetate and 3-ethoxyethyl propionate;
the dispersant is hydrophilic acrylic hyperbranched block copolymer. The block copolymer dispersant can concentrate the anchoring sections during dispersion, enhance the anchoring effect and perform complexation with the nano carbon material, thereby obtaining excellent dispersion effect. In addition, the acrylic copolymer provides good adhesion of the sizing agent on the surface of the aluminum foil, and the stability of the coating is improved.
Step 130, mixing 3-10 parts of first slurry and 75-90 parts of second slurry at a high speed, then adding 0.5-1.5 parts of pH regulator and 0.1-0.5 part of flatting agent, uniformly mixing at a low speed, and finally adding 4-10 parts of binder to obtain conductive slurry of the positive current collector with solid electrolyte surface treatment;
wherein the dispersion speed of the low-speed dispersion is 200r/min-500r/min.
The pH regulator comprises: one or more of ammonia water, 2-amino-2-methyl-1-propanol, dimethylethanolamine, N-methylethanolamine, diethanolamine, butylethanolamine, 2-amino-2 ethyl-1, 3-propanediol, sodium hydroxide and potassium hydroxide;
the leveling agent comprises: one or more of waterborne modified polyacrylate, anionic acrylic copolymer, nonionic polyamine-ethylene oxide condensate, nonionic polyethylene glycol ester and alkylphenol polyoxyethylene are mixed;
the binder comprises one or more of polyacrylate binder, styrene Butadiene Rubber (SBR) binder, polyacrylonitrile binder or other resin binder.
And step 140, uniformly coating the conductive slurry on the surface of the aluminum foil to obtain the positive electrode current collector with solid electrolyte surface treatment for the power battery.
Wherein, the coating method is one of gravure coating, micro-concave coating and slit extrusion coating.
The positive electrode current collector with solid electrolyte surface treatment for the power battery prepared by the invention comprises the following components in percentage by weight: a solid electrolyte doped conductive coating and an aluminum foil;
the conductive paste for forming a solid electrolyte doped conductive coating includes: the electrolyte comprises a solid electrolyte, a dispersing agent, a thickening agent, a wetting agent, water, a second solvent, a nanoscale carbon material, a leveling agent, a pH regulator and a binder. The specific usable substances of the materials of the various parts are already described above and are not described in detail.
The positive electrode current collector can be used as a positive electrode of a lithium battery to be applied to the lithium battery.
The positive electrode current collector with surface treatment of solid electrolyte and the method for preparing the same proposed by the present invention have been described above, and will be further described in detail by some specific examples, but the scope of the present invention is not limited thereto.
Example 1
The embodiment provides a preparation method of a surface-treated positive electrode current collector aluminum foil containing solid electrolyte for a power battery, which comprises the following steps:
s1, mixing 60 parts of water and 0.5 part of hydroxyethyl cellulose thickener according to parts by weight, dispersing at a high speed of 8000r/min for 40 minutes, and then adding 39 parts of solid electrolyte Li 7 La 3 Zr 2 O 12 Dispersing at the same speed for 45 minutes at a high speed, then adding 0.5 part of wetting agent surfactant alkylphenol polyoxyethylene ether, and dispersing at the same speed for 60 minutes to obtain first slurry;
s2, mixing 2 parts of dispersant hydrophilic acrylic hyperbranched segmented copolymer, 75 parts of water and 8 parts of ethylene glycol butyl ether at a high speed and dispersing the mixture uniformly, adding 15 parts of nano carbon black, and dispersing the mixture at a high speed of 6000r/min for 4 hours to obtain a second slurry;
s3, mixing 8 parts of first slurry and 83 parts of second slurry at a high speed, then adding 1 part of pH regulator dimethylethanolamine to uniformly mix at 500r/min, and finally adding 8 parts of binder to obtain the conductive slurry of the positive current collector with the solid electrolyte surface treatment for the power battery;
and S4, extruding and coating the conductive slurry by a slit, controlling the thickness of a dry film to be 1um, and uniformly coating the conductive slurry on the surface of an aluminum foil to finally obtain the positive current collector with solid electrolyte surface treatment for the power battery.
Example 2
The present example provides a method for preparing a surface-treated positive current collector aluminum foil containing a solid electrolyte for a power battery, which is substantially the same as in example 1, except that in step S3, 10 parts by weight of first slurry and 84.5 parts by weight of second slurry are mixed at a high speed by a conventional high-speed disperser, then 0.5 part by weight of a PH adjuster is added to mix uniformly, and finally 5 parts by weight of a binder is added to obtain a surface-treated positive current collector aluminum foil conductive slurry containing a solid electrolyte for a power battery.
Comparative example 1
This example provides a method of making a surface treated positive current collector aluminum foil containing solid state electrolyte for use in power cells that is essentially the same as example 1, except that the aluminum foil is coated with only the second slurry.
Comparative example 2
A blank aluminum foil was used as a comparative example.
The positive current collector aluminum foil of each of the above examples and comparative examples was coated with lithium iron phosphate positive electrode slurry, and a lithium plate was used as a negative electrode to prepare a CR2032 button cell, where the charging current was 1mA, the charging cut-off voltage was not less than 4.3V, and the discharging cut-off voltage was not more than 2.5V, and the impedance after different cycles at 0.2C rate was measured, and compared with a blank control aluminum foil to obtain table 1.
Figure BDA0003912327680000081
TABLE 1
Button cells were prepared from the positive current collector aluminum foils obtained in examples 1 and 2 and comparative example 1 and the blank aluminum foil, and tested according to the conventional standard, and the cycle retention after 1000 weeks of cycling at 1C rate was compared to obtain table 2.
Capacity retention rate
Example 1 87.81％
Example 2 91.35％
Comparative example 1 75.22％
Comparative example 2 65.53％
Table 2 the equivalent specific heat capacity of each button cell was measured and compared to a blank control aluminum foil to give table 3.
Equivalent specific heat capacity (J/(kg. Degree. C. Ah))
Example 1 57.21
Example 2 60.65
Comparative example 1 45.16
Comparative example 2 35.67
TABLE 3
As can be seen from table 1, the initial impedance of the collector surface coated with the conductive paste helps to lower the initial impedance of the button cell, as compared to example 1, 2 and comparative example 1, at the same rate and after different cycles. With the increase of cycle, the battery prepared by the positive electrode current collector prepared by the invention has better impedance performance, and with the increase of the addition amount of the solid electrolyte, the impedance stability is better, and the battery performance is better.
As can be seen from table 2, the coulombic efficiency of the battery made of the positive electrode current collector prepared by the preparation method provided by the embodiment of the present invention is significantly improved, and the cycle retention rate after 1000 weeks of cycling at 1C rate is significantly improved compared with that of the comparative example, especially compared with that of the battery without the solid electrolyte.
The higher the specific heat capacity, the better the temperature rise stability of the material, and as can be seen from table 3, the battery made by using the positive electrode current collector prepared by the invention has the better equivalent specific heat capacity, and the other side shows that the battery has the better temperature rise stability, and has important significance for the safety performance of the lithium battery.
In conclusion, the preparation method of the positive current collector with the solid electrolyte surface treatment, provided by the invention, has the advantages of simple preparation method, easiness in obtaining of used equipment and conditions, high preparation efficiency and suitability for mass production expansion. A lithium battery made of the surface-treated positive current collector aluminum foil is low in impedance, good in long-term cycle performance, weak in temperature rise effect and excellent in overall electrical performance. Has positive practical significance for the development of lithium batteries.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are merely exemplary embodiments of the present invention, and are not intended to limit the scope of the present invention, and any modifications, equivalent substitutions, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.

Claims (8)

1. A method for producing a positive electrode current collector having a solid electrolyte surface treatment, characterized by comprising:
mixing 40-75 parts of water and 0.1-0.5 part of thickening agent according to parts by weight, dispersing at high speed for 20-60 minutes, adding 20-40 parts of solid electrolyte, dispersing at high speed for 30-90 minutes, then adding 0.1-0.5 part of wetting agent, and dispersing at high speed for 20-60 minutes to obtain first slurry;
mixing 1-3 parts of dispersing agent, 50-90 parts of water and 0-20 parts of solvent according to parts by weight, dispersing at high speed until the mixture is uniform, adding 5-20 parts of nano carbon material, and dispersing at high speed for 2-5 hours to obtain second slurry;
according to the weight portion, 3-10 portions of first slurry and 75-90 portions of second slurry are mixed at high speed, then 0.5-1.5 portions of pH regulator and 0.1-0.5 portions of flatting agent are added and mixed evenly at low speed, and finally 4-10 portions of binder are added, so as to obtain the conductive slurry of the positive current collector with solid electrolyte surface treatment;
and uniformly coating the conductive slurry on the surface of the aluminum foil to obtain the positive electrode current collector with solid electrolyte surface treatment for the power battery.
2. The method of claim 1, wherein the equipment for high-speed dispersion comprises: one or more of a high-speed dispersion machine, a high-speed shearing emulsifying machine, a vacuum defoaming dispersion machine and a sand mill; the dispersion speed of the high-speed dispersion is 2000r/min-12000r/min; the dispersing speed of the low-speed dispersion is 200r/min-500r/min.
3. The production method according to claim 1,
the thickener comprises: one or more of methylcellulose, hydroxyethyl cellulose, modified starch, polyvinyl alcohol, polyethylene wax and polymethacrylate;
the wetting agent comprises: one or more of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, polyethylene glycol and alkylphenol polyoxyethylene;
the solid electrolyte includes: one or more of garnet type solid electrolyte material, NASICON type solid electrolyte material, LISICON solid electrolyte material and perovskite type solid electrolyte material are mixed;
the nanoscale carbon material includes: one or more of carbon black, graphene and carbon nanotubes; the primary particle size D50 of the carbon black is 30-60 nm, the graphene is single-layer graphene or multi-layer graphene, and the carbon nanotube is a single-walled carbon nanotube or a multi-walled carbon nanotube;
the solvent comprises: one or more of ethylene glycol, propylene glycol, hexanediol, ethylene glycol butyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, tripropylene glycol n-butyl ether, propylene glycol phenyl ether, hexanediol butyl ether acetate and 3-ethoxyethyl propionate;
the dispersing agent is a hydrophilic acrylic hyperbranched block copolymer;
the pH regulator comprises: one or more of ammonia, 2-amino-2-methyl-1-propanol, dimethylethanolamine, N-methylethanolamine, diethanolamine, butylethanolamine, 2-amino-2 ethyl-1, 3-propanediol, sodium hydroxide and potassium hydroxide;
the leveling agent comprises: one or more of waterborne modified polyacrylate, anionic acrylic copolymer, nonionic polyamine-ethylene oxide condensate, nonionic polyethylene glycol ester and alkylphenol polyoxyethylene are mixed;
the binder comprises one or more of polyacrylate type binder, styrene butadiene rubber SBR type binder, polyacrylonitrile type binder or other resin type binder.
4. The method of claim 1, wherein the coating is performed by one of gravure coating, and slot extrusion coating.
5. A positive electrode current collector for a power battery having a surface treatment of a solid electrolyte prepared by the preparation method as set forth in any one of claims 1 to 4.
6. The positive electrode current collector with solid electrolyte surface treatment for a power battery as claimed in claim 5, wherein the positive electrode current collector comprises: a solid electrolyte doped conductive coating and an aluminum foil;
the conductive paste forming the solid electrolyte doped conductive coating comprises: the electrolyte comprises a solid electrolyte, a dispersing agent, a thickening agent, a wetting agent, water, a second solvent, a nanoscale carbon material, a leveling agent, a pH regulator and a binder.
7. A lithium battery positive electrode comprising the positive electrode current collector for a power battery having a solid electrolyte surface treatment according to claim 5 or 6 above.
8. A lithium battery comprising the positive electrode for a lithium battery as claimed in claim 7.
CN202211329892.0A 2022-10-27 2022-10-27 Positive current collector with solid electrolyte surface treatment and preparation method and application thereof Pending CN115458747A (en)

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CN117275795A (en) * 2023-11-23 2023-12-22 琥崧科技集团股份有限公司 Graphene composite material conductive paste and preparation method thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117275795A (en) * 2023-11-23 2023-12-22 琥崧科技集团股份有限公司 Graphene composite material conductive paste and preparation method thereof
CN117275795B (en) * 2023-11-23 2024-01-26 琥崧科技集团股份有限公司 Graphene composite material conductive paste and preparation method thereof

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