CN110993863B - High-cohesiveness water-based PVDF slurry, preparation method and application thereof - Google Patents
High-cohesiveness water-based PVDF slurry, preparation method and application thereof Download PDFInfo
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- 239000002033 PVDF binder Substances 0.000 title claims abstract description 123
- 229920002981 polyvinylidene fluoride Polymers 0.000 title claims abstract description 119
- 239000002002 slurry Substances 0.000 title claims abstract description 65
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims abstract description 70
- 229910010271 silicon carbide Inorganic materials 0.000 claims abstract description 69
- 239000011230 binding agent Substances 0.000 claims abstract description 19
- 239000000080 wetting agent Substances 0.000 claims abstract description 17
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 239000002270 dispersing agent Substances 0.000 claims abstract description 12
- -1 alcohol fatty acid ester Chemical class 0.000 claims description 30
- 239000002518 antifoaming agent Substances 0.000 claims description 16
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 14
- RBNPOMFGQQGHHO-UHFFFAOYSA-N glyceric acid Chemical compound OCC(O)C(O)=O RBNPOMFGQQGHHO-UHFFFAOYSA-N 0.000 claims description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 9
- 229910052744 lithium Inorganic materials 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 8
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 8
- 229910000318 alkali metal phosphate Inorganic materials 0.000 claims description 7
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 6
- 239000003945 anionic surfactant Substances 0.000 claims description 5
- 239000002736 nonionic surfactant Substances 0.000 claims description 5
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 claims description 5
- 229940048086 sodium pyrophosphate Drugs 0.000 claims description 5
- 235000019818 tetrasodium diphosphate Nutrition 0.000 claims description 5
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 4
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 4
- 239000000194 fatty acid Substances 0.000 claims description 4
- 229930195729 fatty acid Natural products 0.000 claims description 4
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 4
- 229920001451 polypropylene glycol Polymers 0.000 claims description 4
- 235000019982 sodium hexametaphosphate Nutrition 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 3
- 230000001464 adherent effect Effects 0.000 claims 1
- 125000000129 anionic group Chemical group 0.000 claims 1
- 229940005740 hexametaphosphate Drugs 0.000 claims 1
- 239000011248 coating agent Substances 0.000 abstract description 16
- 238000000576 coating method Methods 0.000 abstract description 16
- 239000003990 capacitor Substances 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 4
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000003763 carbonization Methods 0.000 abstract 1
- 239000013530 defoamer Substances 0.000 abstract 1
- 229910052710 silicon Inorganic materials 0.000 abstract 1
- 239000010703 silicon Substances 0.000 abstract 1
- 239000000919 ceramic Substances 0.000 description 23
- 239000002245 particle Substances 0.000 description 23
- 239000004952 Polyamide Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- 229920002647 polyamide Polymers 0.000 description 12
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 8
- 239000004202 carbamide Substances 0.000 description 8
- 239000012528 membrane Substances 0.000 description 8
- 229940051841 polyoxyethylene ether Drugs 0.000 description 8
- 229920000056 polyoxyethylene ether Polymers 0.000 description 8
- 239000002585 base Substances 0.000 description 7
- 229920005822 acrylic binder Polymers 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 6
- 230000001070 adhesive effect Effects 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- 238000005524 ceramic coating Methods 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 239000003292 glue Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 4
- 238000007731 hot pressing Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- UDHMTPILEWBIQI-UHFFFAOYSA-N butyl naphthalene-1-sulfonate;sodium Chemical compound [Na].C1=CC=C2C(S(=O)(=O)OCCCC)=CC=CC2=C1 UDHMTPILEWBIQI-UHFFFAOYSA-N 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- LADXKQRVAFSPTR-UHFFFAOYSA-M sodium;2-hydroxyethanesulfonate Chemical compound [Na+].OCCS([O-])(=O)=O LADXKQRVAFSPTR-UHFFFAOYSA-M 0.000 description 2
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
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- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000007719 peel strength test Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
Classifications
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
- C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
- C08J5/2218—Synthetic macromolecular compounds
- C08J5/2231—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds
- C08J5/2237—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds containing fluorine
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/10—Metal compounds
- C08K3/14—Carbides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08L27/16—Homopolymers or copolymers or vinylidene fluoride
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/431—Inorganic material
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
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- 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
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- 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
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Abstract
本发明属于锂离子电池隔膜生产技术领域，具体涉及一种高粘结性的水性PVDF浆料和制备方法及其应用，具体包括以下重量百分比的原料：3～7％分散剂、1～5％润湿剂、5～10％助粘结剂、0.5～3％消泡剂、0.1～3％防沉剂、15～25％PVDF和0.05～2.5％碳化硅，余量为水，所述碳化硅的添加量与PVDF的添加量按质量比计为1：10～300。通过将SiC均匀分散在PVDF长链中，形成大量的微电容结构，借助SiC高的热传导能力和桥联作用，可以将外界热量快速传递至PVDF浆料内部中，加快PVDF浆料的粘结，进而提高水性PVDF浆料的粘结性能，得到一种涂层较薄、又有较好粘接力的水性PVDF浆料。The invention belongs to the technical field of lithium ion battery separator production, and in particular relates to a highly cohesive water-based PVDF slurry, a preparation method and application thereof, and specifically includes the following raw materials by weight: 3-7% dispersant, 1-5% Wetting agent, 5-10% co-binder, 0.5-3% defoamer, 0.1-3% anti-settling agent, 15-25% PVDF and 0.05-2.5% silicon carbide, the balance is water, the carbonization The added amount of silicon and the added amount of PVDF are 1:10-300 in terms of mass ratio. By dispersing SiC evenly in the PVDF long chain, a large number of micro-capacitor structures are formed. With the help of the high thermal conductivity and bridging effect of SiC, the external heat can be quickly transferred to the interior of the PVDF slurry to speed up the bonding of the PVDF slurry. Further, the bonding performance of the water-based PVDF slurry is improved, and a water-based PVDF slurry with a thinner coating and better bonding force is obtained.
Description
Technical Field
The invention relates to the technical field of lithium ion battery diaphragm production, in particular to high-cohesiveness water-based PVDF slurry, a preparation method and application thereof.
Background
The diaphragm is an indispensable key material of the electrode, although the diaphragm does not participate in the electrochemical reaction in the battery, the key performances of the battery, such as capacity, cycle performance, charge-discharge current density and the like, have a direct relation with the diaphragm, and the improvement of the diaphragm performance plays an important role in improving the comprehensive performance of the lithium battery. The separator mainly plays a role in connecting an electrode active material, a conductive agent and an electrode current collector, and maintains the structural integrity of an electrode. The diaphragm also has high temperature self-closing properties to block current conduction from explosion during overcharge or elevated temperatures.
Currently, the most common binder used in the lithium ion battery industry is polyvinylidene fluoride (PVDF), which has the advantages of strong oxidation and reduction resistance, good thermal stability, easy dispersion, and the like. However, the adhesive capacity of the glued membrane to the electrode current collector has a great relationship with the coating amount of the PVDF, the higher the coating amount is, the better the adhesive performance is, but with the increase of the coating amount of the PVDF, the increment of the air permeability value of the membrane is larger, the risk of pore blocking of the membrane is increased, the internal resistance of the lithium battery is increased, the multiplying power is reduced, and the cycle performance is reduced, so that the PVDF slurry with a thinner coating and better adhesive force is needed.
Chinese patent No. CN201811140887.9 discloses a preparation method of a ceramic coating diaphragm for a lithium ion battery, wherein the ceramic coating diaphragm comprises a polymer porous base film, polymer glue solution coated on one side or two sides of the surface of the base film, a ceramic coating coated on the surface of the polymer glue solution, and PVDF and copolymer glue solution coated on the surface of the ceramic coating and the other side of the surface of the base film. The adhesion of the ceramic coating to the polymer porous base membrane is increased by a multilayer design. In addition, Chinese patent No. CN201810623817.2 discloses a diaphragm and a preparation method thereof and a lithium-sulfur battery, wherein the diaphragm comprises a base material diaphragm, and water system glue layers are formed on the two side surfaces of the base material diaphragm; an aqueous heat conductive material layer is formed on the aqueous adhesive layer on the surface of the base separator. The negative electrode of the lithium-sulfur battery is opposite to the water-based heat conduction material layer, and the positive electrode is opposite to the water-based glue layer. The slurry is water-based slurry, which is beneficial to generating cohesive force between the anode and the diaphragm, better forming the battery cell and relieving the dissolution and diffusion of polysulfide ions. However, in the process of coating the multilayer structure, the thickness of the diaphragm coating is increased virtually, and the porosity of the coating is inconsistent, so that the aperture tortuosity of the composite diaphragm is increased, the internal resistance of the lithium battery is increased, the electrochemical performance is reduced, the bonding performance between the composite diaphragm and the positive plate and the negative plate of the battery is poor, and the battery performance cannot achieve the ideal effect.
Disclosure of Invention
In view of the above-mentioned disadvantages of the prior art, the present invention aims to provide a highly adhesive aqueous PVDF slurry, a preparation method and applications thereof.
The high-cohesiveness aqueous PVDF slurry comprises the following raw materials in percentage by weight: 3-7% of a dispersing agent, 1-5% of a wetting agent, 5-10% of a co-binder, 0.5-3% of a defoaming agent, 0.1-3% of an anti-settling agent, 15-25% of PVDF (polyvinylidene fluoride), 0.05-2.5% of silicon carbide and the balance of water, wherein the addition amount of the silicon carbide and the addition amount of the PVDF are 1:10 to 300.
Adopt above-mentioned technical scheme: the silicon carbide (SiC) ceramic has stable chemical property, high heat conductivity coefficient up to 490W/mK, small thermal expansion coefficient and high dielectric constant. SiC is dispersed in the aqueous PVDF slurry, a large number of heat conduction paths are generated inside PVDF, and a large number of micro-capacitor structures are formed, so that in the hot-pressing polymerization bonding process of the diaphragm coated with the aqueous PVDF slurry, due to the high heat conduction capacity of SiC, external heat can be quickly transferred into the PVDF slurry, the bonding of the PVDF slurry is accelerated, the bonding performance of the aqueous PVDF slurry is improved, and abnormal phenomena such as powder falling, stripping and falling of the aqueous PVDF slurry are reduced. Secondly, fluorine atoms in PVDF are strong electron-withdrawing groups, and on the surface of SiC, the surface of silicon atoms hybridized by sp3 has a large amount of positive charges, and the fluorine atoms can adsorb the silicon atoms through electrostatic action, so that SiC ceramic particles are uniformly dispersed in a PVDF long chain structure to form more micro capacitive structures.
Further, the adding amount of the silicon carbide and the adding amount of the PVDF are 1:20 to 100. The proper addition amount can ensure good bonding performance and electrochemical performance; if the addition amount of the silicon carbide is too low, an effective number of micro-capacitor structures cannot be formed, and the improvement effect on the bonding performance is limited; however, if the amount of silicon carbide added is too high, part of the silicon carbide ceramic particles can be uniformly dispersed in PVDF, but the bonding between the silicon carbide ceramic particles and PVDF is poor, part of the silicon carbide ceramic particles are almost completely exposed to PVDF, and the number of agglomerated particles increases, so that many pores exist in the separator, and electrochemical performance is reduced.
Further, the material comprises the following raw materials in percentage by weight: 5% of dispersing agent, 3% of wetting agent, 7% of binder aid, 1.5% of defoaming agent, 1% of anti-settling agent, 20% of PVDF (polyvinylidene fluoride), 0.5% of silicon carbide and the balance of water, wherein the addition amount of the silicon carbide and the addition amount of the PVDF are 1: 40.
further, the dispersant is alkali metal phosphate.
Further, the alkali metal phosphate is one or more of sodium tripolyphosphate, sodium hexametaphosphate and sodium pyrophosphate. The SiC ceramic particles are directly added into the aqueous PVDF slurry, and because the specific surface area of the SiC ceramic particles is large and the incompatibility of multiple phases is easy to cause the SiC ceramic particles to agglomerate and introduce air holes into the slurry, the loss of the diaphragm is increased, and the compressive strength is reduced; alkali metal phosphates are dissociated in water to generate ions with positive charges, and the ions are dispersed around silicon carbide, so that the surface of the SiC ceramic particles is provided with strong positive charges, and strong charge repulsion is generated among the ions to limit agglomeration and promote dispersion, therefore, the SiC ceramic particles can be stably dispersed in the aqueous PVDF slurry to form a more compact network in a limited volume, and the enhancement of the positive charges is also beneficial to the uniform dispersion of the SiC ceramic particles in a PVDF long-chain structure, so that the overlapping among the sheet layers is more obvious, more heat conduction paths beneficial to heat transfer are formed, and the hot-pressing bonding performance is enhanced.
Further, the wetting agent is a mixture of one or more of an anionic surfactant and a nonionic surfactant. The anionic surfactant is sodium alkylaryl sulfonate, sodium butylnaphthalene sulfonate, sodium hydroxyethyl sulfonate or sodium dodecyl sulfonate; the nonionic surfactant is long-chain fatty alcohol-polyoxyethylene ether, alkylphenol polyoxyethylene, polyoxyethylene alkylolamide or fatty alcohol-polyoxyethylene ether. The wetting agent is added, so that the interfacial tension of SiC ceramic particles can be increased, the hydrophilicity of the aqueous PVDF slurry and the wettability between the aqueous PVDF slurry and a PVDF diaphragm are improved, the aqueous PVDF slurry is more easily coated on the diaphragm, and the thickness uniformity of a coating layer is improved.
Further, the auxiliary binder is an acrylic type binder.
Further, the defoaming agent is one of a higher alcohol fatty acid ester complex, polyoxyethylene polyoxypropylene pentaerythritol ether, polyoxyethylene polyoxypropylene amine ether, polyoxypropylene glycerol ether, polyoxypropylene polyoxyethylene glycerol ether and polydimethylsiloxane.
Adopt above-mentioned technical scheme: the defoaming agent is added to reduce the quantity of foams in the slurry and improve the coating quality of the coated diaphragm, the defoaming agent is utilized to reduce the wetting effect of the wetting agent, so that the water-based PVDF slurry in partial areas cannot be wetted with the surface of the diaphragm, and a non-full-coverage coating is formed after drying, so that the air permeability of the diaphragm is improved, and the battery performance is improved.
Further, the anti-settling agent is one of urea modified polyamide and polyamide wax. The addition of the anti-settling agent can prevent the SiC ceramic particles from settling too quickly when the SiC ceramic particles are kept stand and stored.
The preparation method of the aqueous PVDF slurry comprises the following steps:
s1, adding silicon carbide and a dispersing agent into water, and performing ultrasonic dispersion to obtain a suspension A;
s2, adding PVDF, an anti-settling agent and a defoaming agent into the suspension A, and stirring at normal temperature at the stirring speed of 100-200r/min for 30-40min to obtain a mixed solution B;
and S3, adding the auxiliary binder and the wetting agent into the mixed solution B, and stirring at normal temperature to obtain the high-cohesiveness water-based PVDF slurry.
The application of the aqueous PVDF slurry in the preparation of the lithium battery diaphragm comprises the PVDF diaphragm and the aqueous PVDF slurry coated on one side or two sides of the PVDF diaphragm.
Further, the aqueous PVDF slurry is coated on the lithium battery diaphragm in a rolling, spraying or spot coating mode.
Further, drying the diaphragm coating at 50-80 ℃.
By adopting the technical scheme provided by the invention, the method has the following beneficial effects:
1. by uniformly dispersing SiC in the PVDF long chain, a large number of micro-capacitor structures are formed, and external heat can be quickly transferred into the PVDF slurry by virtue of the high heat conduction capacity and the bridging action of SiC, so that the bonding of the PVDF slurry is accelerated, the bonding performance of the aqueous PVDF slurry is further improved, and the aqueous PVDF slurry with a thin coating and good bonding force is obtained.
2. The SiC ceramic particles are provided with strong positive charges through the dissociation of alkali metal phosphates, so that strong charge repulsion is generated among the SiC ceramic particles, the stable dispersion of the SiC ceramic particles in the water-based PVDF slurry is promoted, a more compact network is formed in a limited volume, the enhancement of the positive charges is also beneficial to the uniform dispersion of the SiC ceramic particles in a PVDF long chain structure, the overlapping among the sheet layers is more obvious, more heat conduction paths which are beneficial to heat transfer are formed, and the hot-pressing bonding performance is enhanced.
3. The defoaming agent is utilized to reduce the wetting effect of the wetting agent, so that the water-based PVDF slurry in a partial area cannot be wetted with the surface of the diaphragm, and a non-full-coverage coating is formed after drying, thereby improving the air permeability of the diaphragm and improving the battery performance.
4. According to the invention, through the interaction among the dispersing agent, the wetting agent, the binder aid, the defoaming agent, the anti-settling agent and the silicon carbide, N-methylpyrrolidone (NMP) is not required to be used as a solvent, so that the liquid absorption rate of the battery diaphragm is reduced, and the battery performance is improved.
Detailed Description
The technical solutions of the present invention are described clearly and completely below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The high-cohesiveness aqueous PVDF slurry comprises the following raw materials in percentage by weight: 3-7% of a dispersing agent, 1-5% of a wetting agent, 5-10% of a co-binder, 0.5-3% of a defoaming agent, 0.1-3% of an anti-settling agent, 15-25% of PVDF (polyvinylidene fluoride), 0.05-2.5% of silicon carbide and the balance of water, wherein the addition amount of the silicon carbide and the addition amount of the PVDF are 1:10 to 300.
The alkali metal phosphate is one or more of sodium tripolyphosphate, sodium hexametaphosphate and sodium pyrophosphate; the wetting agent is one or a mixture of anionic surfactant and nonionic surfactant. The anionic surfactant is sodium alkylaryl sulfonate, sodium butylnaphthalene sulfonate, sodium hydroxyethyl sulfonate or sodium dodecyl sulfonate; the nonionic surfactant is long-chain fatty alcohol-polyoxyethylene ether, alkylphenol ethoxylate, polyoxyethylene alkylolamide or fatty alcohol-polyoxyethylene ether; the auxiliary binder is an acrylic acid type binder; the defoaming agent is one of a high-alcohol fatty acid ester compound, polyoxyethylene polyoxypropylene pentaerythritol ether, polyoxyethylene polyoxypropylene amine ether, polyoxypropylene glycerol ether, polyoxypropylene polyoxyethylene glycerol ether and polydimethylsiloxane; the anti-settling agent is one of urea modified polyamide and polyamide wax. The inventors have conducted extensive studies to find that the kind of the wetting agent, the defoaming agent and the anti-settling agent does not greatly affect the binding properties of the aqueous PVDF slurry when one or more kinds thereof are selected within the scope of the claims of the present invention.
The preparation method of the aqueous PVDF slurry comprises the following steps:
s1, adding silicon carbide and a dispersing agent into water, and performing ultrasonic dispersion to obtain a suspension A; s2, adding PVDF, an anti-settling agent and a defoaming agent into the suspension A, and stirring at normal temperature at the stirring speed of 100-200r/min for 30-40min to obtain a mixed solution B; and S3, adding the auxiliary binder and the wetting agent into the mixed solution B, and stirring at normal temperature to obtain the high-cohesiveness water-based PVDF slurry. The following examples and comparative examples were prepared using this method to obtain aqueous PVDF slurries.
Example 1
The high-cohesiveness aqueous PVDF slurry comprises the following raw materials in percentage by weight: 7% of sodium tripolyphosphate, 5% of sodium alkylaryl sulfonate, 5% of an acrylic acid type binder, 3% of a higher alcohol fatty acid ester composite, 0.1% of polyamide wax, 15% of PVDF and 0.05% of silicon carbide, and the balance of water, wherein the addition amount of the silicon carbide and the addition amount of the PVDF are 1: 300.
example 2
The high-cohesiveness aqueous PVDF slurry comprises the following raw materials in percentage by weight: 6% of sodium hexametaphosphate, 4% of sodium butylnaphthalene sulfonate, 6% of an acrylic binder, 2% of polyoxyethylene polyoxypropylene pentaerythritol ether, 0.5% of polyamide wax, 20% of PVDF and 0.2% of silicon carbide, wherein the balance is water, and the addition amount of the silicon carbide and the addition amount of the PVDF are 1: 100.
example 3
The high-cohesiveness aqueous PVDF slurry comprises the following raw materials in percentage by weight: 5% of sodium tripolyphosphate, 3% of long-chain fatty alcohol-polyoxyethylene ether, 7% of an acrylic binder, 1.5% of polyoxypropylene glycerol ether, 1% of urea modified polyamide, 20% of PVDF and 0.5% of silicon carbide, and the balance of water, wherein the addition amount of the silicon carbide and the addition amount of the PVDF are 1: 40.
example 4
The high-cohesiveness aqueous PVDF slurry comprises the following raw materials in percentage by weight: 4% of sodium pyrophosphate, 2% of alkylphenol polyoxyethylene, 10% of acrylic binder, 1% of polyoxypropylene polyoxyethylene glycerol ether, 2% of urea modified polyamide, 20% of PVDF and 1% of silicon carbide, and the balance being water, wherein the addition amount of the silicon carbide and the addition amount of the PVDF are in a mass ratio of 1: 20.
example 5
The high-cohesiveness aqueous PVDF slurry comprises the following raw materials in percentage by weight: 3% of sodium pyrophosphate, 1% of polyoxyethylene alkylolamide, 10% of an acrylic acid type binder, 0.5% of polydimethylsiloxane, 3% of urea modified polyamide, 25% of PVDF and 2.5% of silicon carbide, wherein the balance is water, and the addition amount of the silicon carbide and the addition amount of the PVDF are 1: 10.
comparative example 1
Comparative example 1 is essentially the same as example 3, except that: the raw materials of the aqueous PVDF slurry do not comprise silicon carbide, namely the aqueous PVDF slurry comprises the following raw materials in percentage by weight: 5% of sodium tripolyphosphate, 3% of long-chain fatty alcohol-polyoxyethylene ether, 7% of an acrylic binder, 1.5% of polyoxypropylene glycerol ether, 1% of urea modified polyamide, 20% of PVDF and the balance of water.
Comparative example 2
Comparative example 2 is essentially the same as example 3, except that: the water-based PVDF slurry comprises 5% of sodium tripolyphosphate, 3% of long-chain fatty alcohol-polyoxyethylene ether, 7% of an acrylic binder, 1.5% of polyoxypropylene glycerol ether, 1% of urea modified polyamide, 20% of PVDF and 0.05% of silicon carbide, and the balance of water, wherein the addition amount of the silicon carbide and the addition amount of the PVDF are 1: 400.
comparative example 3
Comparative example 3 is substantially the same as example 3 except that: the water-based PVDF slurry comprises 5% of sodium tripolyphosphate, 3% of long-chain fatty alcohol-polyoxyethylene ether, 7% of an acrylic binder, 1.5% of polyoxypropylene glycerol ether, 1% of urea modified polyamide, 20% of PVDF and 4% of silicon carbide, and the balance of water, wherein the addition amount of the silicon carbide and the addition amount of the PVDF are 1: 5.
comparative example 4
Comparative example 4 is essentially the same as example 3, except that: replacing the raw material silicon carbide of the aqueous PVDF slurry with equal mass of silicon dioxide, namely, the addition amount of the silicon dioxide and the addition amount of the PVDF are 1: 40.
application example Performance detection
Coating the aqueous PVDF slurry obtained in the examples 1-5 and the comparative examples 1-4 on a PVDF diaphragm of a lithium battery in a roller coating, spraying or spot coating mode, and then drying the diaphragm at the temperature of 50-80 ℃, wherein the thickness of the dried diaphragm is about 3 mu m; then the adhesive force of the diaphragm is measured by an adhesive force tester, and the measuring method refers to a GB/T2792-1998 pressure-sensitive adhesive tape 180-degree peel strength test method; the specific method comprises the following steps: the pole pieces were cut into 12mm wide and 20mm long sample strips and mounted on an aluminum plate. The 3M scotch tape was adhered to the sample strip, the tape was pulled down 180 ° using a universal tensile machine, and the peel strength was recorded. The peeling speed was 5 mm/min. The specific measurement results are shown in Table 1.
TABLE 1 Performance data for aqueous PVDF slurries
As can be seen from Table 1, after the SiC ceramic particles are added (examples 1-5), the cohesive force of the diaphragm is greatly improved and is obviously stronger than that of a common PVDF diaphragm without silicon carbide. With the increase of the adding proportion of the silicon carbide, the bonding performance is gradually improved, because the SiC ceramic particles have good thermal conductivity, the hot-pressing bonding of the PVDF membrane can be promoted, so that the peeling force required for destroying a bonding system is greatly increased, the bonding strength of the PVDF membrane is obviously improved, but the dispersity of the PVDF membrane is gradually reduced as the content of the SiC ceramic particles is further improved, the electrochemical performance is reduced in spite of higher bonding strength, especially when the content of the SiC ceramic particles is too high, if the content is increased to the content of comparative example 3, part of the silicon carbide ceramic particles are almost completely exposed out of the PVDF, a conglomerate structure is formed, more air holes exist in the membrane, and the electrochemical performance is obviously reduced. Comparative example 4 in comparison with example 3, SiC was replaced by SiO with similar properties2Due to SiO2The thermal conductivity coefficient is extremely low, only 7.6W/mK, a micro-capacitor structure cannot be formed in PVDF, and the bonding performance is not basically improved. Therefore, only the good proportion of the silicon carbide and the PVDF can ensure the bonding performance and the electrochemical performance of the lithium battery.
Claims (9)
1. The high-cohesiveness aqueous PVDF slurry is characterized by comprising the following raw materials in percentage by weight: 3-7% of a dispersing agent, 1-5% of a wetting agent, 5-10% of a co-binder, 0.5-3% of a defoaming agent, 0.1-3% of an anti-settling agent, 15-25% of PVDF (polyvinylidene fluoride), 0.05-2.5% of silicon carbide and the balance of water, wherein the mass ratio of the addition amount of the silicon carbide to the addition amount of the PVDF is 1: 10-300; the dispersant is alkali metal phosphate.
2. The highly-binding aqueous PVDF slurry according to claim 1, wherein the ratio of the amount of silicon carbide added to the amount of PVDF added is 1:20 to 100 by mass.
3. The high-cohesiveness aqueous PVDF paste as described in claim 1, comprising the following raw materials in weight percent: 5% of dispersing agent, 3% of wetting agent, 7% of binder aid, 1.5% of defoaming agent, 1% of anti-settling agent, 20% of PVDF, 0.5% of silicon carbide and the balance of water, wherein the mass ratio of the addition amount of the silicon carbide to the addition amount of the PVDF is 1: 40.
4. The highly cementitious aqueous PVDF slurry of claim 1 in which the alkali metal phosphate is one or more of sodium tripolyphosphate, hexametaphosphate, and sodium pyrophosphate.
5. The highly cohesive aqueous PVDF slurry of claim 1, wherein the wetting agent is a mixture of one or more of anionic and non-ionic surfactants.
6. The high-adhesion aqueous PVDF slurry of claim 1, wherein the co-binder is an acrylic-type binder.
7. The highly adherent aqueous PVDF slurry according to claim 1, wherein the defoaming agent is one of a higher alcohol fatty acid ester complex, polyoxyethylene polyoxypropylene pentaerythritol ether, polyoxyethylene polyoxypropylene amine ether, polyoxypropylene glycerol ether, polyoxypropylene polyoxyethylene glycerol ether and polydimethylsiloxane.
8. The method for preparing the aqueous PVDF slurry as claimed in any one of claims 1 to 7, comprising the steps of:
s1, adding silicon carbide and a dispersing agent into water, and performing ultrasonic dispersion to obtain a suspension A;
s2, adding PVDF, an anti-settling agent and a defoaming agent into the suspension A, and stirring at normal temperature at the stirring speed of 100-200r/min for 30-40min to obtain a mixed solution B;
and S3, adding the auxiliary binder and the wetting agent into the mixed solution B, and stirring at normal temperature to obtain the high-cohesiveness water-based PVDF slurry.
9. Use of the aqueous PVDF slurry of any one of claims 1 to 7 in the preparation of a lithium battery separator, wherein the lithium battery separator comprises a PVDF separator and the aqueous PVDF slurry coated on one or both sides of the PVDF separator.
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| KR1020217037937A KR102421795B1 (en) | 2019-11-11 | 2020-10-27 | Aqueous PVDF slurry with high tackiness, manufacturing method and its application |
| PCT/CN2020/123945 WO2021093572A1 (en) | 2019-11-11 | 2020-10-27 | Aqueous pvdf paste having strong binding property, preparation method therefor, and application thereof |
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| CN114464893A (en) * | 2021-12-14 | 2022-05-10 | 湖北钛时代新能源有限公司 | A kind of manufacturing method of square cylindrical composite titanium battery |
| CN117783893B (en) * | 2023-12-28 | 2024-07-16 | 江苏万锂达智能科技有限公司 | Lithium battery energy storage monitoring system and method |
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