CN115926040B - Preparation method of lithium ion battery negative electrode slurry - Google Patents
Preparation method of lithium ion battery negative electrode slurry Download PDFInfo
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- CN115926040B CN115926040B CN202211519622.6A CN202211519622A CN115926040B CN 115926040 B CN115926040 B CN 115926040B CN 202211519622 A CN202211519622 A CN 202211519622A CN 115926040 B CN115926040 B CN 115926040B
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- lithium ion
- ion battery
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- 239000011267 electrode slurry Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 26
- 239000000178 monomer Substances 0.000 claims abstract description 161
- 239000003999 initiator Substances 0.000 claims abstract description 46
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 37
- 239000000853 adhesive Substances 0.000 claims abstract description 31
- 230000001070 adhesive effect Effects 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 19
- 238000003756 stirring Methods 0.000 claims abstract description 17
- 239000007773 negative electrode material Substances 0.000 claims abstract description 10
- 239000006258 conductive agent Substances 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 24
- 229910002804 graphite Inorganic materials 0.000 claims description 21
- 239000010439 graphite Substances 0.000 claims description 21
- 239000011230 binding agent Substances 0.000 claims description 15
- 239000006229 carbon black Substances 0.000 claims description 11
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 6
- 239000006256 anode slurry Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 239000006257 cathode slurry Substances 0.000 claims description 4
- 150000002978 peroxides Chemical class 0.000 claims description 4
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 4
- 239000012966 redox initiator Substances 0.000 claims description 4
- 125000000524 functional group Chemical group 0.000 claims description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 19
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 14
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 14
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 14
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 13
- 239000006185 dispersion Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 235000019241 carbon black Nutrition 0.000 description 10
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 7
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 7
- 238000001228 spectrum Methods 0.000 description 7
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 5
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 5
- 239000004289 sodium hydrogen sulphite Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000006245 Carbon black Super-P Substances 0.000 description 2
- 102100026735 Coagulation factor VIII Human genes 0.000 description 2
- 101000911390 Homo sapiens Coagulation factor VIII Proteins 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 1
- NQSLZEHVGKWKAY-UHFFFAOYSA-N 6-methylheptyl 2-methylprop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C(C)=C NQSLZEHVGKWKAY-UHFFFAOYSA-N 0.000 description 1
- SCDXDAWFADXGLT-UHFFFAOYSA-N C(C=C)(=O)OCC(=O)O.[Na] Chemical compound C(C=C)(=O)OCC(=O)O.[Na] SCDXDAWFADXGLT-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 241000872198 Serjania polyphylla Species 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- -1 ammonium peroxide Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000002003 electrode paste Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 101150016402 fsn-1 gene Proteins 0.000 description 1
- 125000003827 glycol group Chemical group 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- NZIDBRBFGPQCRY-UHFFFAOYSA-N octyl 2-methylprop-2-enoate Chemical compound CCCCCCCCOC(=O)C(C)=C NZIDBRBFGPQCRY-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 description 1
- 229910000342 sodium bisulfate Inorganic materials 0.000 description 1
- PFUVRDFDKPNGAV-UHFFFAOYSA-N sodium peroxide Chemical compound [Na+].[Na+].[O-][O-] PFUVRDFDKPNGAV-UHFFFAOYSA-N 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
-
- 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
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The application relates to the technical field of lithium ion battery negative electrode slurry, and particularly provides a preparation method of lithium ion battery negative electrode slurry, which comprises the steps of adding a conductive agent into a water-based adhesive, stirring and dispersing, adding a negative electrode material, and stirring and dispersing to obtain the lithium ion battery negative electrode slurry; the aqueous adhesive is prepared according to the following method: adding the first monomer combination into water, adding a first initiator at a certain temperature for reaction, continuing the reaction for 0-8 hours after the addition, adding a second monomer combination within 30 minutes-8 hours, and then or synchronously adding a second initiator within 5 minutes-4 hours, and cooling to obtain the water-based adhesive; the first monomer combination consists of a first hydrophilic monomer and a first hydrophobic monomer, wherein the first hydrophobic monomer accounts for 0-40% of the weight of the first monomer combination; the second monomer combination consists of a second hydrophilic monomer and a second hydrophobic monomer, wherein the second hydrophobic monomer accounts for 40-100% of the weight of the second monomer combination. The lithium ion battery negative electrode slurry has good stability.
Description
Technical Field
The application relates to the technical field of lithium ion battery negative electrode slurry, in particular to a preparation method of lithium ion battery negative electrode slurry.
Background
The negative electrode of the lithium ion battery generally adopts graphite and carbon black as active substances, and the surface hydrophobicity of the graphite and the carbon black is strong and is difficult to disperse stably, so that the negative electrode slurry with good stability is difficult to obtain. The aqueous acrylic acid adhesive has good adhesion performance, and the aqueous acrylic acid adhesive is matched with graphite and carbon black to prepare lithium ion battery cathode slurry in the prior art, but the aqueous acrylic acid adhesive has poor dispersion stability on the graphite and the carbon black, and the aqueous acrylic acid adhesive needs to be compounded with sodium carboxymethyl acrylate (CMC) for use.
Disclosure of Invention
The application provides a preparation method of lithium ion battery negative electrode slurry, which aims to solve the technical problem that the dispersion stability of graphite and carbon black is poor when a water-based acrylic acid adhesive is adopted for preparing the lithium ion battery negative electrode slurry in the prior art.
The application adopts the following technical scheme:
The preparation method of the lithium ion battery negative electrode slurry comprises the steps of adding a conductive agent into a water-based adhesive, stirring and dispersing, adding a negative electrode material, and stirring and dispersing to obtain the lithium ion battery negative electrode slurry;
The aqueous adhesive is prepared according to the following method: adding the first monomer combination into water, adding a first initiator at a certain temperature for reaction, continuing the reaction for 0-8 hours after the addition, adding a second monomer combination within 30 minutes-8 hours, and then or synchronously adding a second initiator within 5 minutes-4 hours, and cooling to obtain the water-based adhesive;
The first monomer combination consists of a first hydrophilic monomer and a first hydrophobic monomer, wherein the first hydrophobic monomer accounts for 0-40% of the weight of the first monomer combination;
The second monomer combination consists of a second hydrophilic monomer and a second hydrophobic monomer, wherein the second hydrophobic monomer accounts for 40-100% of the weight of the second monomer combination.
Preferably, the concentration of the aqueous binder is 5 to 40wt%.
Preferably, the negative electrode material is selected from one or both of graphite and carbon black.
Preferably, the first initiator and the second initiator are independently selected from one or more of a water-soluble azo initiator, a water-soluble peroxide initiator, a water-soluble persulfate initiator and a water-soluble redox initiator.
Preferably, the first hydrophilic monomer and the second hydrophilic monomer are independently selected from monomers with a chemical formula of CH 2=CR1R2, wherein R 1 is selected from H or C1-C4 alkyl, R 2 is selected from -CONH2、-CONHCH3、-CONHCH2CH3、-CON(CH3)2、-CON(CH2CH3)2、-CONHCH2OH、-CONHCH2CH2OH、-COOCH2CH2OH、-COOCH2CH2CH2OH、-COOCH2CHCH3OH、-COOCH2CH2CH2CH2OH、-COO(CH2CH2O)aH and-COO (one or more of CH 2)bPO3 H, and/or one or more of organic structures containing-COOH, -COOM, - (C 6H5)COOM、-SO3 M and- (C 6H5)SO3 M) functional groups, a=1-40, b=1-12, and M is selected from one or more of Li +、Na+ and K +.
Preferably, the first hydrophobic monomer and the second hydrophobic monomer are independently selected from monomers with a chemical formula of CH 2=CR3R4, wherein R 3 is selected from H or C1-C4 alkyl, R 4 is selected from one or more of-COOC nH2n+1 and-C mH2m CN, n=1-40, and m=0-6.
Preferably, the first hydrophobic monomer comprises 10-30% by weight of the first monomer combination.
Preferably, the second hydrophobic monomer comprises 50-90% by weight of the second monomer combination.
Preferably, the weight ratio of the first monomer combination to the second monomer combination is 1:9-9:1.
More preferably, the weight ratio of the first monomer combination to the second monomer combination is 4:6-8:2.
In summary, the application has the following beneficial effects:
1. The application adopts a two-step polymerization process to realize that hydrophilic monomers and hydrophobic monomers form similar 'block' distribution on the polymer chain of the water-based adhesive according to a proportion, the hydrophilic difference between blocks is obvious, and the hydrophilic monomers and the hydrophobic monomers are randomly copolymerized in the blocks. The inventor finds that the structure has better dispersibility for graphite and carbon black with stronger hydrophobicity, can obtain cathode slurry with good stability, can ensure that the slurry can keep active particles from gathering or less from gathering for a longer time without adding CMC for auxiliary dispersion, and has no problems of layering, sedimentation and the like.
2. According to the application, a two-step polymerization process is adopted, the feeding ratio and feeding sequence of the hydrophilic monomer and the hydrophobic monomer are simply adjusted, so that the hydrophilic and hydrophobic aqueous adhesive with a specific structure can be obtained, wherein the hydrophobic chain segment can be effectively infiltrated and adsorbed on the surface of the negative electrode active particles to play a role in dispersing particles, the hydrophilic chain segment is free in a water phase, and the thickening of the water phase and the prevention of agglomeration, sedimentation and the like of the dispersed negative electrode active particles can be realized through the winding action and the steric hindrance action between the chain segments, so that the overall stability of the slurry can be improved.
3. The application can adjust the polymer structure in the aqueous adhesive to be similar to a two-block or three-block structure by controlling the reaction time of the first monomer, and different dispersing effects can be realized due to different hydrophile and hydrophobicity among the blocks. When the polymer is "triblock-like", the monomer combination ratio of the intermediate block is between the first monomer combination and the second monomer combination, and the hydrophilicity and hydrophobicity between the triblock changes in order.
Drawings
FIG. 1 is a reference spectrum of the back-scattered light of example 1;
FIG. 2 is a reference spectrum of the back-scattered light of example 4;
FIG. 3 is a reference spectrum of the back-scattered light of example 6;
FIG. 4 is a reference spectrum of the back-scattered light of example 7;
FIG. 5 is a reference spectrum of the back-scattered light of comparative example 1;
FIG. 6 is a reference spectrum of the back-scattered light of comparative example 2;
FIG. 7 is a graph of a reference back-scattered light spectrum of comparative example 3;
FIG. 8 is a graph comparing the overall kinetic instability test of examples 1, 4, 6, 7 and comparative examples 1, 2, 3.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below.
Throughout the specification, unless specifically indicated otherwise, the terms used herein should be understood as meaning as commonly used in the art. Accordingly, unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification will control.
The application provides a preparation method of lithium ion battery negative electrode slurry, which comprises the steps of adding a conductive agent into a water-based adhesive, stirring and dispersing, adding a negative electrode material, and stirring and dispersing to obtain the lithium ion battery negative electrode slurry;
In the present application, the conductive agent is not particularly limited, and may be selected from conductive carbon blacks such as acetylene black, carbon fibers, carbon nanotubes, ketjen black, etc., or a combination of the above several conductive carbon blacks.
The aqueous adhesive is prepared according to the following method: adding the first monomer combination into water, adding a first initiator at a certain temperature for reaction, continuing the reaction for 0-8 hours after the addition, adding a second monomer combination within 30 minutes-8 hours, and then or synchronously adding a second initiator within 5 minutes-4 hours, and cooling to obtain the water-based adhesive;
The first monomer combination consists of a first hydrophilic monomer and a first hydrophobic monomer, wherein the first hydrophobic monomer accounts for 0-40% of the weight of the first monomer combination;
the second monomer combination consists of a second hydrophilic monomer and a second hydrophobic monomer, wherein the second hydrophobic monomer accounts for 40-100% of the weight of the second monomer combination.
In a preferred embodiment of the application, the concentration of the aqueous binder is 5-40wt%. Further preferably, the aqueous binder of the present application has a concentration of 5 to 30 wt% and a viscosity (25 ℃) of 500 to 50000 mPa.s.
In a preferred embodiment of the present application, the negative electrode material is selected from one or both of graphite and carbon black. In a further preferred embodiment, the negative electrode material may be selected from natural graphite, artificial graphite, mesophase carbon microspheres, soft carbon, hard carbon, and the like.
In a preferred embodiment of the present application, the first initiator and the second initiator are independently selected from one or more of a water-soluble azo initiator, a water-soluble peroxide initiator, a water-soluble persulfate initiator, and a water-soluble redox initiator. The water-soluble azo initiator is not particularly limited, and may be azobisisobutyrimidine hydrochloride (AIBA), azobisiso Ding Mi (AIBI) hydrochloride, or the like; the water-soluble peroxide initiator is not particularly limited, and may be hydrogen peroxide, sodium peroxide, ammonium peroxide, or the like; the water-soluble persulfate initiator is not particularly limited, and may be ammonium persulfate, potassium persulfate, sodium persulfate, or the like; the water-soluble redox initiator is not particularly limited, and may be/,/sodium bisulphite, hydrogen peroxide/tartaric acid, hydrogen peroxide/sodium bisulfate, ammonium persulfate/, hydrogen peroxide/ferrous sulfate, or the like. Different water-soluble initiators have different corresponding reaction temperatures, for example, when AIBA is selected as the water-soluble initiator, a certain temperature can be 50-60 ℃, when ammonium persulfate is selected as the water-soluble initiator, a certain temperature can be 60-80 ℃, and when ammonium persulfate/is selected as the water-soluble initiator, a certain temperature can be 40-45 ℃. The first initiator and the second initiator may be added in portions directly or may be added dropwise after being formulated into an aqueous solution. For example, the first initiator may be added dropwise to the reaction system in the form of a solution for a period of 0.5 to 8 hours. The second initiator is added dropwise to the reaction system in the form of a solution for a period of time of 0.5 to 8 hours.
The first initiator and the second initiator may comprise 0.1 to 1% of the sum of the weights of the first monomer combination and the second monomer combination, respectively. Further, for better polymerization, the weight ratio of the first initiator to the second initiator may be 7:3 to 8:2. In the present application, the first initiator and the second initiator may be the same or different. Preferably, the first initiator and the second initiator are the same, or the first initiator and the second initiator are different, but their initiation temperatures are close (e.g., the initiator temperature difference does not exceed 5 ℃), which is more advantageous for controlling the reaction temperature.
In the present application, the hydrophilic monomer means a compound having at least one carbon-carbon unsaturated double bond in a molecule capable of undergoing radical polymerization, and the compound has at least one hydrophilic group such as hydroxyl group, carboxyl group, carboxylate, phosphate, sulfonate, amino group, substituted amino group, amide, substituted amide, etc., or polyethylene glycol group having at least two ethylene glycol units in its molecular structure. In a preferred embodiment of the present application, the first hydrophilic monomer and the second hydrophilic monomer are independently selected from monomers having a chemical formula of CH 2=CR1R2, wherein R 1 is selected from H or C1-C4 alkyl, R 2 is selected from one or more of -CONH2、-CONHCH3、-CONHCH2CH3、-CON(CH3)2、-CON(CH2CH3)2、-CONHCH2OH、-CONHCH2CH2OH、-COOCH2CH2OH、-COOCH2CH2CH2OH、-COOCH2CHCH3OH、-COOCH2CH2CH2CH2OH、-COO(CH2CH2O)aH and-COO (CH 2)bPO3 H), and/or one or more of organic structures containing-COOH, -COOM, - (C 6H5)COOM、-SO3 M, and- (C 6H5)SO3 M) functional groups, a=1-40, b=1-12, and M is selected from one or more of Li +、Na+ and K +.
In the present application, the hydrophobic monomer means a compound having at least one carbon-carbon unsaturated double bond in a molecule capable of undergoing radical polymerization, and the compound does not have a hydrophilic group in a molecular structure. In a preferred embodiment of the present application, the first hydrophobic monomer and the second hydrophobic monomer are independently selected from monomers having a chemical formula of CH 2=CR3R4, wherein R 3 is selected from H or C1-C4 alkyl, R 4 is selected from one or more of-COOC nH2n+1 and-C mH2m CN, n=1 to 40, and m=0 to 6. For example, the first and second hydrophobic monomers may be methyl Methacrylate (MAA), butyl Methacrylate (BMA), butyl Acrylate (BA), ethyl Methacrylate (EMA), ethyl Acrylate (EA), isobutyl methacrylate, isooctyl methacrylate, n-octyl methacrylate, lauryl methacrylate, stearic methacrylate, acrylonitrile (AN), methacrylonitrile (MAN), methacrylonitrile, and the like, respectively.
In a preferred embodiment of the present application, the first hydrophobic monomer comprises 10-30% by weight of the first monomer combination. The inventors found that when the first hydrophobic monomer is in the above range based on the combined weight of the first monomer, the obtained negative electrode slurry has better dispersion stability.
In a preferred embodiment of the present application, the second hydrophobic monomer comprises 50-90% by weight of the second monomer combination. The inventors found that when the second hydrophobic monomer is in the above range based on the combined weight of the second monomer, the obtained negative electrode slurry has better dispersion stability.
In the preferred technical scheme of the application, the weight ratio of the first monomer combination to the second monomer combination is 1:9-9:1.
In a more preferred embodiment of the present application, the weight ratio of the first monomer combination to the second monomer combination is 4:6-8:2. Still more preferably, the weight ratio of the first monomer combination to the second monomer combination is from 5:5 to 8:2.
In the preparation of the aqueous adhesive, the time for continuing the reaction after the first initiator is added can be further 30min-6 hours. The longer the reaction time is continued, the more fully the first monomer combination reacts, and when the second monomer combination is added, the weight ratio of hydrophilic monomer to hydrophobic monomer in the unreacted monomer in the reaction system approaches the weight ratio of hydrophilic monomer to hydrophobic monomer in the second monomer combination. The addition time of the second monomer combination is more preferably 1 to 4 hours.
The preparation method of the lithium ion battery cathode slurry provided by the application can be more specifically carried out according to the following method: when the viscosity of the aqueous adhesive is high, a proper amount of water can be added to adjust the viscosity to 500-2000mPa.s (25 ℃), the aqueous adhesive is wetted by adding the conductive agent, 30-80% of the negative electrode material by weight is added after stirring and dispersing, and the rest of the negative electrode material is added after stirring and dispersing. Finally, the viscosity of the final negative electrode slurry (25 ℃) is 2000-4000 Pa.s, and the viscosity can be adjusted according to the viscosity of the negative electrode slurry with or without adding water. In the above preparation method of the lithium ion battery anode slurry, the stirring and dispersing rotational speed is not particularly limited and may be 200 to 600rpm.
The method for preparing the lithium ion battery anode slurry according to the present application will be described in detail with reference to examples, comparative examples and experimental data. Unless otherwise indicated, the parts in the following preparations, examples and comparative examples are parts by weight.
Preparation example 1
50 Parts of AA monomer, 40 parts of AM monomer, 10 parts of AN monomer and 400 parts of water are added into a reaction bottle, stirring is carried out at a speed of 350rpm, the temperature is raised to 45 ℃, 0.7 part of sodium bisulphite is added, and then 30 parts of ammonium persulfate aqueous solution with the concentration of 1wt% is added dropwise for 6 hours. After the dropwise addition, 0.3 part of sodium bisulphite was continuously added, and 10 parts of AN aqueous ammonium persulfate solution with a concentration of 1wt% was added dropwise, and a mixed monomer consisting of 50 parts of AA monomer and 50 parts of AN monomer was simultaneously added dropwise, the dropwise addition time of the aqueous ammonium persulfate solution was 7 hours, and the dropwise addition time of the mixed monomer was 3 hours. After all the water-based adhesive is dripped, the temperature is kept for 30 minutes, the temperature is reduced to below 40 ℃, the pH of the reaction system is regulated to 6-8, the solid content is regulated to 20%, and the water-based adhesive is obtained, and the viscosity (25 ℃) is 5300 Pa.s.
Preparation example 2
In preparation example 1, the mixed monomer composition was adjusted to be composed of 50 parts of AA monomer and 50 parts of AN monomer, and 20 parts of AA monomer and 80 parts of AN monomer, and the remaining steps were kept unchanged, to obtain AN aqueous adhesive, the solid content was adjusted to 19.9%, and the viscosity (25 ℃) was 5000mpa.s.
Preparation example 3
Into a reaction flask, 80 parts of MAA monomer, 20 parts of EA monomer and 400 parts of water were added, stirred at 300rpm, heated to 45℃and 0.7 part of sodium bisulphite was added, and 30 parts of an aqueous solution of 1wt% ammonium persulfate was added dropwise over 6 hours. After the completion of the dropwise addition, 0.3 part of sodium bisulphite and 10 parts of AN aqueous solution of ammonium persulfate with the concentration of 1wt% are continuously added, a mixed monomer consisting of 40 parts of MAA monomer and 60 parts of AN monomer is synchronously added dropwise, the dropwise addition time of the aqueous solution of ammonium persulfate is 6 hours, the dropwise addition time of the mixed monomer is 3 hours, 300 parts of water is started after 2 hours of dropwise addition of the mixed monomer, and the dropwise addition is completed for 2 hours. And (3) after the ammonium persulfate aqueous solution is completely dripped, carrying out heat preservation reaction for 30 minutes, cooling to below 40 ℃, adjusting the pH of a reaction system to 6-8, adjusting the solid content to 15.2%, and adjusting the viscosity (25 ℃) to 3800 Pa.s.
Preparation example 4
In preparation example 3, 80 parts of MAA monomer and 20 parts of EA monomer were adjusted to 112 parts of MAA monomer and 28 parts of EA monomer, the mixed monomer was adjusted from a combination of 40 parts of MAA monomer and 60 parts of AN monomer to a combination of 24 parts of MAA monomer and 36 parts of AN monomer, and the remaining steps were kept unchanged to obtain AN aqueous adhesive having a solid content of 15% and a viscosity (25 ℃) of 3700mpa.s.
Preparation example 5
Into a reaction flask, 80 parts of MAA monomer, 16 parts of HEMA monomer, 4 parts of BMA monomer, 20 parts of AN monomer and 400 parts of water were added, and stirred at 400rpm, heated to 70℃and 70 parts of AN aqueous solution of ammonium persulfate having a concentration of 1wt% was added dropwise for 6 hours. After the dropwise addition, the reaction was continued for 4 hours, 30 parts of AN aqueous ammonium persulfate solution having a concentration of 1wt% and a mixed monomer composed of 18 parts of AA monomer, 6 parts of HEMA monomer, 16 parts of BMA monomer and 40 parts of AN monomer were simultaneously added dropwise, the time for adding the aqueous ammonium persulfate solution was 6 hours, and the time for adding the mixed monomer dropwise was 3 hours. After all the water-based adhesive is dripped, the temperature is kept for 2 minutes, the temperature is reduced to below 40 ℃, the pH of the reaction system is regulated to 6-8, the solid content is regulated to 15%, and the water-based adhesive is obtained, and the viscosity (25 ℃) is 3700 Pa.s.
Example 1
18 Parts of the aqueous binder of preparation example 1 and 400 parts of water were dispersed with stirring at 300rpm for 12 minutes, 10 parts of the conductive agent Super-P was added to wet for 15 minutes, and then stirred at 500rpm for 120 minutes; the rotation speed was adjusted to 300rpm, 500 parts of KD-1 graphite was added and stirred for dispersion for 20 minutes, 472 parts of KD-1 graphite and 400 parts of water were added and stirring was continued for dispersion for 30 minutes, and then stirring was continued for 120 minutes at 500 rpm. After the completion of the dispersion, water was added to adjust the viscosity (25 ℃) to 3200mPa.s, and the mixture was filtered through a 150-mesh filter screen to obtain a negative electrode slurry.
Example 2
In example 1, the aqueous binder of preparation example 1 was replaced with an equal weight of the aqueous binder of preparation example 2, the remaining steps were kept unchanged, and the viscosity (25 ℃) of the final negative electrode slurry was at 3500mpa.s.
Example 3
In example 1, the aqueous binder of preparation example 1 was replaced with an equal weight of the aqueous binder of preparation example 3, the remaining steps were kept unchanged, and the viscosity (25 ℃) of the final negative electrode slurry was 3300mpa.s.
Example 4
In example 1, the aqueous binder of preparation example 1 was replaced with an equal weight of the aqueous binder of preparation example 4, the remaining steps were kept unchanged, and the viscosity (25 ℃) of the final negative electrode slurry was 3600mpa.s.
Example 5
In example 1, the aqueous binder of preparation example 1 was replaced with an equal weight of the aqueous binder of preparation example 5, the remaining steps were kept unchanged, and the viscosity (25 ℃) of the final negative electrode slurry was 2800mpa.s.
Example 6
In example 4, KD-1 graphite was replaced with equal weight of FSN-1 graphite, the rest of the procedure was kept unchanged, and the final negative electrode slurry viscosity (25 ℃) was 3700 Pa.s.
Example 7
In example 4, KD-1 graphite was replaced with equal weight of AGP-2L-P graphite, the rest of the procedure was kept unchanged, and the final negative electrode paste viscosity (25 ℃) was at 3500mPa.s.
Example 8
In example 4, KD-1 graphite was replaced with an equal weight of G58 graphite, the rest of the procedure was kept unchanged, and the final negative electrode slurry viscosity (25 ℃) was 3800 Pa.s.
Example 9
In example 4, KD-1 graphite was replaced with an equal weight of NT-3S graphite, the rest of the procedure was kept unchanged, and the final negative electrode slurry viscosity (25 ℃) was at 3500 Pa.s.
Comparative example 1
18 Parts of CMC and 12 parts of Japanese sialon SBR emulsion AL-3001A are stirred and dispersed in 400 parts of water, 10 parts of conductive agent Super-P is added for wetting for 15 minutes, and then stirring is carried out for 120 minutes at 500 rpm; the rotation speed was adjusted to 300rpm, 488 parts of KD-1 graphite was added and stirred for dispersion for 20 minutes, 472 parts of KD-1 graphite and 400 parts of water were added and stirred for dispersion for 30 minutes, and then stirring was continued for 120 minutes at 500 rpm. After the completion of the dispersion, water was added to adjust the viscosity (25 ℃) to be at 3500mPa.s, and the mixture was filtered through a 150-mesh filter to obtain a negative electrode slurry having a viscosity (25 ℃) of 4100mPa.s.
Comparative example 2
In preparation 4, 112 parts of MAA monomer and 28 parts of EA monomer were adjusted to 70 parts of MAA monomer and 70 parts of EA monomer, and the remaining steps were kept unchanged.
In example 4, the aqueous binder of preparation example 4 was replaced with the same weight of the above aqueous binder, and the remaining steps were kept unchanged, and the viscosity (25 ℃) of the final negative electrode slurry was 3700mpa.s.
Comparative example 3
In preparation example 3, the mixed monomer was adjusted from a combination of 24 parts of MAA and 36 parts of AN monomer to a combination of 42 parts of MAA and 18 parts of AN monomer, and the remaining steps were kept unchanged, and the viscosity (25 ℃) of the final negative electrode slurry was at 3500mpa.s.
In example 4, the aqueous adhesive of preparation 4 was replaced with an equal weight of the above aqueous adhesive, and the rest of the procedure was kept unchanged.
Performance testing
Instrument testing: the stability of the negative electrode slurry to be measured was analyzed using a turbo LAB stability analyzer (multiple light scattering instrument) from formula company. FIGS. 1-7 are the test results of examples 1, 4, 6 and 7 and comparative examples 1-3, respectively, and FIG. 8 is a comparison of the overall kinetic instability test of examples 1, 4, 6 and 7 and comparative examples 1,2 and 3. As can be seen from the results of figures 1-8, the lithium ion battery negative electrode slurry has better stability, and has better stability compared with the existing dispersion combination of CMC and SBR emulsion.
The present embodiment is only for explanation of the present application and is not to be construed as limiting the present application, and modifications to the present embodiment, which may not creatively contribute to the present application as required by those skilled in the art after reading the present specification, are all protected by patent laws within the scope of claims of the present application.
Claims (5)
1. A preparation method of lithium ion battery cathode slurry is characterized by comprising the following steps: adding a conductive agent into the aqueous adhesive, stirring and dispersing, adding a negative electrode material, and stirring and dispersing to obtain the negative electrode slurry of the lithium ion battery;
The aqueous adhesive is prepared according to the following method: adding the first monomer combination into water, adding a first initiator at a certain temperature for reaction, continuing the reaction for 0-8 hours after the addition, adding a second monomer combination within 30 minutes-8 hours, and then or synchronously adding a second initiator within 5 minutes-4 hours, and cooling to obtain the water-based adhesive;
the first monomer combination consists of a first hydrophilic monomer and a first hydrophobic monomer, wherein the first hydrophobic monomer accounts for 10-30% of the weight of the first monomer combination;
The second monomer combination consists of a second hydrophilic monomer and a second hydrophobic monomer, wherein the second hydrophobic monomer accounts for 50-90% of the weight of the second monomer combination;
The weight ratio of the first monomer combination to the second monomer combination is 1:9-9:1;
the first hydrophobic monomer and the second hydrophobic monomer are independently selected from monomers with a chemical formula of CH 2=CR3R4, wherein R 3 is selected from H or C1-C4 alkyl, R 4 is selected from one or more of-COOC nH2n+1 and-C mH2m CN, n=1-40, m=0-6
The first initiator and the second initiator are independently selected from one or more of water-soluble azo initiators, water-soluble peroxide initiators, water-soluble persulfate initiators or water-soluble redox initiators.
2. The method for preparing the lithium ion battery anode slurry according to claim 1, wherein the method comprises the following steps: the concentration of the aqueous binder is 5-40wt%.
3. The method for preparing the lithium ion battery anode slurry according to claim 1, wherein the method comprises the following steps: the negative electrode material is selected from one or two of graphite and carbon black.
4. The method for preparing the lithium ion battery anode slurry according to claim 1, wherein the method comprises the following steps: the first hydrophilic monomer and the second hydrophilic monomer are independently selected from monomers with a chemical formula of CH 2=CR1R2, wherein R 1 is selected from H or C1-C4 alkyl, R 2 is selected from -CONH2、-CONHCH3、-CONHCH2CH3、-CON(CH3)2、-CON(CH2CH3)2、-CONHCH2OH、-CONHCH2CH2OH、-COOCH2CH2OH、-COOCH2CH2CH2OH、-COOCH2CHCH3OH、-COOCH2CH2CH2CH2OH、-COO(CH2CH2O)aH and-COO (one or more of CH 2)bPO3 H), and/or one or more of organic structures containing-COOH, -COOM, - (C 6H5)COOM、-SO3 M and- (C 6H5)SO3 M functional groups), a=1-40, b=1-12, and M is selected from one or more of Li +、Na+ and K +.
5. The method for preparing the lithium ion battery anode slurry according to claim 1, wherein the method comprises the following steps: the weight ratio of the first monomer combination to the second monomer combination is 4:6-8:2.
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