CN117343642A - Composite chemical auxiliary agent and preparation method thereof - Google Patents
Composite chemical auxiliary agent and preparation method thereof Download PDFInfo
- Publication number
- CN117343642A CN117343642A CN202311509488.6A CN202311509488A CN117343642A CN 117343642 A CN117343642 A CN 117343642A CN 202311509488 A CN202311509488 A CN 202311509488A CN 117343642 A CN117343642 A CN 117343642A
- Authority
- CN
- China
- Prior art keywords
- pole piece
- parts
- composite chemical
- chemical auxiliary
- auxiliary agent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000126 substance Substances 0.000 title claims abstract description 93
- 239000012752 auxiliary agent Substances 0.000 title claims abstract description 69
- 239000002131 composite material Substances 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000005096 rolling process Methods 0.000 claims abstract description 81
- 239000000463 material Substances 0.000 claims abstract description 53
- 239000002270 dispersing agent Substances 0.000 claims abstract description 50
- 229920002545 silicone oil Polymers 0.000 claims abstract description 44
- 239000003755 preservative agent Substances 0.000 claims abstract description 35
- 230000002335 preservative effect Effects 0.000 claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000005336 cracking Methods 0.000 claims abstract description 21
- 239000008367 deionised water Substances 0.000 claims abstract description 19
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 19
- 230000001681 protective effect Effects 0.000 claims abstract description 19
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 16
- 238000000576 coating method Methods 0.000 claims description 78
- 239000011248 coating agent Substances 0.000 claims description 73
- 239000003094 microcapsule Substances 0.000 claims description 30
- 230000000694 effects Effects 0.000 claims description 27
- 239000007789 gas Substances 0.000 claims description 20
- 239000002808 molecular sieve Substances 0.000 claims description 19
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 19
- 230000007774 longterm Effects 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 18
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 17
- 239000003054 catalyst Substances 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 239000006260 foam Substances 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 13
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 12
- 239000002518 antifoaming agent Substances 0.000 claims description 12
- 229920000570 polyether Polymers 0.000 claims description 12
- 239000006185 dispersion Substances 0.000 claims description 10
- 229920001296 polysiloxane Polymers 0.000 claims description 10
- -1 polydimethylsiloxane Polymers 0.000 claims description 9
- 238000012545 processing Methods 0.000 claims description 8
- 229920002988 biodegradable polymer Polymers 0.000 claims description 6
- 239000004621 biodegradable polymer Substances 0.000 claims description 6
- 238000010382 chemical cross-linking Methods 0.000 claims description 6
- 230000032798 delamination Effects 0.000 claims description 6
- 238000009826 distribution Methods 0.000 claims description 6
- QCDWFXQBSFUVSP-UHFFFAOYSA-N 2-phenoxyethanol Chemical compound OCCOC1=CC=CC=C1 QCDWFXQBSFUVSP-UHFFFAOYSA-N 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical group [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 5
- 239000002736 nonionic surfactant Substances 0.000 claims description 5
- 229960005323 phenoxyethanol Drugs 0.000 claims description 5
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 5
- 239000011257 shell material Substances 0.000 claims description 5
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- CBTVGIZVANVGBH-UHFFFAOYSA-N aminomethyl propanol Chemical compound CC(C)(N)CO CBTVGIZVANVGBH-UHFFFAOYSA-N 0.000 claims description 4
- 229910052755 nonmetal Inorganic materials 0.000 claims description 4
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical group OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 4
- 239000010457 zeolite Substances 0.000 claims description 4
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 3
- 229910021536 Zeolite Inorganic materials 0.000 claims description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 230000001502 supplementing effect Effects 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 14
- 230000002829 reductive effect Effects 0.000 abstract description 12
- 238000005299 abrasion Methods 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 230000006378 damage Effects 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 53
- 238000011056 performance test Methods 0.000 description 22
- 239000002245 particle Substances 0.000 description 17
- 239000002671 adjuvant Substances 0.000 description 16
- 230000008859 change Effects 0.000 description 13
- 230000032683 aging Effects 0.000 description 12
- 238000013461 design Methods 0.000 description 12
- 230000014759 maintenance of location Effects 0.000 description 12
- 239000000047 product Substances 0.000 description 10
- 238000004132 cross linking Methods 0.000 description 9
- 230000007613 environmental effect Effects 0.000 description 8
- 238000009472 formulation Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 238000003860 storage Methods 0.000 description 8
- 238000006386 neutralization reaction Methods 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 239000004480 active ingredient Substances 0.000 description 6
- 238000005260 corrosion Methods 0.000 description 6
- 239000013530 defoamer Substances 0.000 description 6
- 239000004615 ingredient Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 5
- 230000001351 cycling effect Effects 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 230000006870 function Effects 0.000 description 5
- 239000011149 active material Substances 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000006065 biodegradation reaction Methods 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000013270 controlled release Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 230000002708 enhancing effect Effects 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 238000005461 lubrication Methods 0.000 description 3
- 230000003472 neutralizing effect Effects 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 235000021317 phosphate Nutrition 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 230000001737 promoting effect Effects 0.000 description 3
- 238000004626 scanning electron microscopy Methods 0.000 description 3
- 229920000331 Polyhydroxybutyrate Polymers 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000002609 medium Substances 0.000 description 2
- 230000000813 microbial effect Effects 0.000 description 2
- 239000005015 poly(hydroxybutyrate) Substances 0.000 description 2
- 229920000747 poly(lactic acid) Polymers 0.000 description 2
- 239000004626 polylactic acid Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000011002 quantification Methods 0.000 description 2
- 238000013139 quantization Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- 238000005211 surface analysis Methods 0.000 description 2
- 238000009827 uniform distribution Methods 0.000 description 2
- 238000011077 uniformity evaluation Methods 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- 239000012855 volatile organic compound Substances 0.000 description 2
- 208000002430 Multiple chemical sensitivity Diseases 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- WFGBXPXOFAFPTO-UHFFFAOYSA-N [P].[Fe].[Li] Chemical compound [P].[Fe].[Li] WFGBXPXOFAFPTO-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- 239000002482 conductive additive Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000012844 infrared spectroscopy analysis Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 229910021450 lithium metal oxide Inorganic materials 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 238000013031 physical testing Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000001303 quality assessment method Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
- H01M4/04—Processes of manufacture in general
- H01M4/043—Processes of manufacture in general involving compressing or compaction
- H01M4/0435—Rolling or calendering
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/20—Diluents or solvents
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
-
- 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
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing & Machinery (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a composite chemical auxiliary agent used in the preparation process of a lithium ion battery, in particular to an auxiliary agent used for preventing sticking and cracking in the pole piece rolling process. The composite chemical auxiliary agent consists of preparation raw materials, and comprises, by weight, 2-10 parts of modified silicone oil, 1-2 parts of preservative, 0.5-1 part of PH value regulator, 2-4 parts of dispersing agent and 85-95 parts of deionized water. According to the composite chemical auxiliary agent provided by the invention, the protective film is formed in the rolling process, so that the friction and adhesion between the metal roller and the battery pole piece material are effectively reduced, the damage and abrasion of the pole piece are reduced, and the production efficiency and the consistency of the battery performance are improved.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a composite chemical auxiliary agent for preventing sticking and cracking in a rolling process of a lithium ion battery pole piece and a preparation method thereof.
Background
In the manufacturing process of lithium ion batteries, pole piece rolling is a key step, which involves uniformly coating active materials on the surface of a current collector. The quality of this step directly affects the performance and lifetime of the battery. However, in the conventional rolling process, problems of sticking of the rolls and cracking of the pole pieces often occur, which not only deteriorate the quality of the pole pieces, but also reduce the production efficiency and the overall performance of the battery. The sticking phenomenon is mainly due to high friction between the pole piece material and the roll surface of the roll squeezer, and the pole piece cracking is usually caused by stress concentration and poor elastic recovery of the material.
In view of these problems, there is an urgent need in the industry for a composite chemical auxiliary agent that can effectively improve the interaction between the pole piece and the roll surface during the rolling process in the manufacturing process of lithium ion batteries.
Disclosure of Invention
The application provides a composite chemical auxiliary agent for preventing sticking and cracking in the rolling process of a lithium ion battery pole piece and a preparation method thereof, so that a protective film is formed in the rolling process, friction and adhesion between a metal roller and a battery pole piece material are reduced, and damage and abrasion of the battery pole piece are reduced.
The application provides a composite chemical auxiliary agent for preventing sticking and cracking in the rolling process of a lithium ion battery pole piece, which comprises, by weight, 2-10 parts of modified silicone oil, 1-2 parts of preservative, 0.5-1 part of PH value regulator, 2-4 parts of dispersing agent and 85-95 parts of deionized water.
Further, the modified silicone oil is hydroxyl-terminated polydimethylsiloxane or polysiloxane containing alkyl groups; the preservative is selected from hydroxybenzoates, phenoxyethanol or a mixture thereof; the PH value regulator is ammonia water, monoethanolamine or AMP-95; the dispersing agent is at least one of nonionic surfactant, polyether or polyether modified silicone oil.
Furthermore, the preservative has silane functional groups and is used for carrying out covalent bond reaction with the battery pole piece material on the surface of the battery pole piece, so that a long-term protection effect is provided.
Further, the dispersing agent is an amphiphilic molecule with directional lipophilic and hydrophilic areas, and is used for effectively reducing the surface tension of the battery pole piece material in the rolling process, thereby improving the dispersing performance and preventing the reagglomeration phenomenon.
Still further, the weight ratio of the modified silicone oil to the dispersant is from 4:1 to 6:1.
Still further, the composite chemical auxiliary further includes a molecular sieve material for absorbing and neutralizing harmful gases that may be released during the rolling process.
Still further, the composite chemical auxiliary agent further comprises 0.05-0.5 parts by weight of an inorganic non-metal catalyst, wherein the inorganic non-metal catalyst is selected from materials consisting of silicate, zeolite or phosphate, and is used for promoting chemical crosslinking reaction on the surface of the battery pole piece, enhancing the bonding strength of the coating and the pole piece, and simultaneously reducing the risk of delamination of the materials in the rolling process.
Furthermore, the composite chemical auxiliary agent also comprises 2-3 parts by weight of environment-sensitive microcapsule, wherein the environment-sensitive microcapsule is internally packaged with the modified organic silicone oil and the dispersing agent, and the shell material of the environment-sensitive microcapsule is a biodegradable polymer and is designed to be dissociated when reaching the specific humidity or pH value condition of battery pole piece processing, so that the timed release of the auxiliary agent is ensured, and the distribution and the attaching effect on the surface of the battery pole piece are optimized.
Still further, the composite chemical auxiliary agent further comprises 0.1 to 1.0 parts by weight of an antifoaming agent selected from silicone or polyether antifoaming agents for effectively suppressing the generation of foam during rolling, ensuring the uniformity and surface quality of the coating, and simultaneously improving rolling efficiency and reducing material loss during rolling.
The application provides a preparation method of a composite chemical auxiliary agent for preventing sticking and cracking in a rolling process of a lithium ion battery pole piece, which comprises the following steps:
s1, adding 50 parts of deionized water according to a weight ratio;
s2, respectively adding 2-10 parts of modified organic silicone oil and 2-4 parts of dispersing agent according to the weight ratio at the stirring speed of 30-50 r/min, and stirring for 20-30 min;
s3, after the modified organic silicone oil is fully dissolved, supplementing 35-45 parts of deionized water according to the weight ratio, adding 1-2 parts of preservative, and stirring for 5-10 minutes;
s4, adding 0.5-1 part of PH value regulator according to the weight ratio, and stirring for 5-10 minutes.
The beneficial technical effects of the invention are as follows:
(1) By forming a layer of lubricating film in the rolling process, the auxiliary agent disclosed by the invention obviously reduces the adhesion phenomenon between the pole piece material and the roller surface, reduces the stress concentration of the pole piece, and effectively prevents the problem of pole piece cracking.
(2) The addition of the modified organic silicone oil improves the affinity of the auxiliary agent and the pole piece material, and enhances the wettability, thereby ensuring the uniformity and consistency of the pole piece surface coating.
(3) The deionized water is mainly used as a solvent and is matched with the ecological-friendly preservative, so that the auxiliary agent is more environment-friendly and has no irritation to operators.
(4) The auxiliary agent can reduce the replacement frequency of the scraper blade and the use of consumable products, thereby reducing the production cost.
(5) The synergistic effect of the PH value regulator and the dispersing agent ensures the uniform distribution of active substances in the coating, and avoids the defect of the pole piece caused by particle aggregation, thereby improving the overall quality of the battery pole piece.
Detailed Description
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present application. This application is, however, susceptible of embodiment in many other ways than those herein described and similar generalizations can be made by those skilled in the art without departing from the spirit of the application and the application is therefore not limited to the specific embodiments disclosed below.
The first embodiment of the application provides a composite chemical auxiliary agent for preventing sticking and cracking in the rolling process of a lithium ion battery pole piece, which comprises, by weight, 2-10 parts of modified silicone oil, 1-2 parts of preservative, 0.5-1 part of PH value regulator, 2-4 parts of dispersing agent and 85-95 parts of deionized water. The modified organic silicone oil is hydroxyl-terminated polydimethylsiloxane or polysiloxane containing alkyl groups; the preservative is selected from hydroxybenzoates, phenoxyethanol or a mixture thereof; the PH value regulator is ammonia water, monoethanolamine or AMP-95; the dispersing agent is at least one of nonionic surfactant, polyether or polyether modified silicone oil.
The composite chemical auxiliary agent in the embodiment is specially designed for the rolling process of the lithium ion battery pole piece. It comprises the following components:
modified organic silicone oil: the auxiliary agent is a main active ingredient of the auxiliary agent and is used for forming a protective layer on the surface of the battery pole piece so as to reduce adhesion with rolling equipment and prevent the generation of pole piece cracks. The modified silicone oil is used in an amount of 2 to 10 parts in this example, the specific amount depending on the desired viscosity and thickness of the protective film. The modified silicone oil is hydroxyl-terminated polydimethylsiloxane or polysiloxane containing alkyl groups, and the materials are selected for excellent lubricity and chemical resistance.
Preservative: to maintain the stability of the composite chemical auxiliary agent and prolong the shelf life of the composite chemical auxiliary agent, 1-2 parts of preservative is added. The preservative is selected from the group consisting of hydroxybenzoates, phenoxyethanol or mixtures thereof. These substances inhibit microbial growth and prevent deterioration and spoilage of the product.
pH regulator: the auxiliary agent uses 0.5-1 part of PH value regulator to maintain the product in a proper pH range, thereby ensuring the best performance. Ammonia water, monoethanolamine or AMP-95 as a PH adjustor can adjust the PH of the solution, thereby affecting the solubility and dispersion state of the silicone oil in water.
Dispersing agent: the addition of the dispersing agent (2-4 parts) aims at improving the dispersibility of the modified organic silicone oil in deionized water and ensuring the uniform coating of the auxiliary agent on the surface of the pole piece. In this embodiment, at least one of nonionic surfactant, polyether or polyether-modified silicone oil and the like is selected as the dispersant.
Deionized water: the solvent and the carrier of the auxiliary agent are added with deionized water in an amount of 85-95 parts. Deionized water is a preferred solvent because it does not contain any mineral salts, thereby avoiding ion contamination that may negatively impact cell performance.
The modified organic silicone oil plays a role of a protective agent in the composite chemical auxiliary agent, and can form a layer of protective film on the surface of the battery pole piece, and the layer of protective film can effectively reduce direct physical contact between the battery pole piece and the rolling mechanical component and reduce friction, so that the abrasion and tearing possibility of the pole piece are reduced. Meanwhile, the protective film can also prevent the adhesion phenomenon of pole piece materials in the rolling process.
The preservative ensures that the composite chemical auxiliary agent is not polluted by microorganisms in the storage and use processes, and maintains the long-term stability and reliability of the product. The pH value regulator keeps the pH value of the composite chemical auxiliary agent in an optimal range, which is beneficial to improving the stability and the dispersibility of the modified organic silicone oil and simultaneously preventing any instability possibly caused by the fluctuation of the pH value.
The dispersing agent is used for ensuring stable dispersion of the auxiliary agent in a water-based environment and ensuring uniformity in the coating process. Finally, deionized water is used as a solvent to provide an ion-free pure medium, which is helpful for keeping the pole piece clean and pure in the coating process, and is also a diluting and carrying medium for other components.
In the embodiment, the composite chemical auxiliary agent which can prevent the adhesive roller and the pole piece from cracking and can maintain long-term stability and reliability is prepared by carefully selecting components and adjusting the formula, and is particularly suitable for being used in the rolling process of the pole piece of the lithium ion battery. Each component is selected and proportioned to maximize the performance of the additive during the battery manufacturing process and to ensure its effectiveness in practical applications.
Table 1 comparison of properties of various composite chemical adjuvants prepared by various combinations
Table 1 is intended to show a comparison of the performance of the composite chemical adjuvants of different formulations during rolling of lithium ion battery pole pieces. Each formula is formed by mixing five main components according to a specific proportion, and the overall performance of the auxiliary agent is influenced by different formula proportions. The formulation numbers a to D in the table represent four different test samples, each of which has different amounts of ingredients, in order to test the performance differences at various amounts. The performance test results are rated according to a quantization standard set in advance for comparison. In this example and other examples below, hydroxyl-terminated polydimethylsiloxane was used as the modified silicone oil, phenoxyethanol was used as the preservative, aqueous ammonia was used as the pH adjustor, and a nonionic surfactant was used as the dispersant, unless otherwise specified.
In Table 1, it can be seen that the amount of modified silicone oil increases from 2 to 10, which generally affects the viscosity of the adjuvant and the resulting protective film thickness. The amount of preservative is kept between 1 and 2 parts to ensure that the prepared adjuvant inhibits microbial growth during storage and use. The amounts of pH adjustor and dispersant vary from 0.5 to 1 part and 2 to 4 parts, respectively, which affects the pH stability of the adjuvant and the dispersibility in deionized water. Deionized water is used as a base solvent and a carrier, and the dosage of the deionized water is correspondingly adjusted according to the dosage of other components.
The performance evaluations fall into three categories:
(1) The rolling effect is as follows: the ability of the adjuvants to prevent sticking to the rolls during rolling was examined. Excellent rolling effect means that the pole piece sticks very little during rolling, good means that there is some sticking, but still in a controllable range, and generally indicates that the sticking is more frequent.
The following are the quantization criteria for the roll effect scale:
excellent: in standard roll testing, the pole piece coated with the composite chemical auxiliary agent shows extremely low roll sticking phenomenon, and the incidence rate is lower than 5%.
Good: the occurrence of pole piece sticking is between 5% and 15%, indicating that in most cases the adjuvant is effective in preventing sticking, but in some cases there is still the possibility of occurrence.
Generally: the occurrence rate of the pole piece sticking phenomenon exceeds 15%, which means that the preventive effect of the auxiliary agent on the sticking phenomenon is not particularly ideal.
(2) Pole piece cracking resistance: the pole pieces were tested for their ability to resist crack formation after rolling. The excellent cracking resistance indicates that the pole piece has almost no cracks, good cracking resistance indicates that a certain crack occurs, but the number is small, and the common cracking resistance indicates that the cracks are relatively more.
The following are quantification criteria for pole piece cracking resistance performance ratings:
excellent: the pole piece shows extremely high crack resistance after rolling, and the crack occurrence rate is lower than 1%.
Good: the crack occurrence rate is between 1% and 5%, which indicates that the pole piece has better cracking resistance, but cracks can occur under high pressure or adverse conditions.
Generally: the crack occurrence rate exceeds 5%, which indicates that the pole piece is easy to crack after rolling, and the auxiliary agent formula or the processing condition needs to be improved.
(3) Long-term stability: the stability of the adjuvant after storage for a certain period of time was evaluated. Excellent long-term stability means that the auxiliaries hardly undergo a change in chemical and physical properties during storage, good long-term stability means that the change is within an acceptable range, whereas general long-term stability means that the auxiliaries have a relatively large change in properties.
The following are quantification criteria for long-term stability performance levels:
excellent: after at least 6 months of storage, the chemical and physical properties of the composite chemical auxiliary agent are not obviously changed, which indicates that the auxiliary agent has excellent stability.
Good: after 6 months of storage, the chemical and physical properties of the adjuvant changed by no more than 5%, indicating that the adjuvant has good stability, but may change slightly under extreme conditions.
Generally: after 6 months of storage, the chemical and physical properties of the adjuvant change by more than 5%, which may affect its performance and safety, requiring improvements in formulation or storage conditions.
In Table 1, the specific amounts and test results for formulations A to D are as follows:
formulation a uses the lowest end of ingredient usage and therefore may have a thinner protective film and lower viscosity, which may result in rolling effects and pole piece cracking resistance reaching only "good" and "normal" levels, but long term stability is shown to be "excellent".
The component dosage of the formula B and the formula C is moderate, so that better balance can be realized, the rolling effect and the pole piece cracking resistance are improved to the excellent level and the good level, and the excellent long-term stability is maintained.
Formulation D uses a high level of ingredients, which may lead to reduced rolling effectiveness and long-term stability (rated "good" and "normal"), which may be due to reduced performance caused by too high amounts of ingredients.
These performance evaluation results provide the practitioner with important information about the impact of different formulations on the performance of the composite chemical adjuvant and can guide further optimization of the formulation.
In a second embodiment of the present application, based on the first embodiment, the preservative has a silane functional group for covalent bond reaction with a battery pole piece material on a surface of the battery pole piece, thereby providing a long-term protection effect.
The silane functional group has the function of forming a firm protective film through covalent bond reaction with the surface of the battery pole piece material in the chemical auxiliary agent. This reaction is typically accomplished by one or more silane coupling agents that can react with the active material of the battery pole piece (e.g., graphite or lithium metal oxide) and the surface of the current collector. The chemical bond has high bonding strength and is not easy to be stripped by water or other solvents, thereby providing long-acting protection for the battery pole piece and preventing moisture, oxygen and other substances possibly causing performance degradation from invading.
In addition, the addition of the silane functional group not only improves the corrosion resistance of the auxiliary agent, but also possibly improves the overall chemical stability of the battery pole piece, because the covalent bond protective film can resist the corrosion of environmental factors to pole piece materials, such as the electrochemical reaction stability in the charging and discharging processes of the battery.
And (3) performance test design:
to demonstrate that preservatives with added silane functional groups can effectively provide long-term protection, the following performance tests can be designed:
test purpose:
and verifying the capability and durability of the preservative containing silane functional groups to form a protective film on the surface of the battery pole piece.
Test material:
battery pole piece material (such as graphite or lithium iron phosphorus)
Preservative composite chemical auxiliary agent containing silane functional group
Standard preservative without silane functional group as control group
The testing method comprises the following steps:
(1) Surface treatment:
the battery pole pieces are divided into two groups: the test group was coated with a preservative containing silane functional groups and the control group was coated with a standard preservative containing no silane functional groups.
The preservative is coated on the surface of the pole piece by using a spin coating or dipping mode, and is allowed to dry at room temperature to form a protective film.
(2) Accelerated aging test:
the treated pole pieces are placed in an accelerated aging oven, subjected to suitable temperature and humidity conditions (e.g., 60 c, 90% relative humidity), and maintained for a period (e.g., 500 hours).
Performance evaluation:
the anti-corrosion effect of the pole piece is evaluated before and after the aging test, and the change of the electrochemical performance of the pole piece can be evaluated through electrochemical tests (such as cyclic voltammetry and battery charge-discharge test).
Surface analysis techniques such as Scanning Electron Microscopy (SEM), X-ray photoelectron spectroscopy (XPS) are used to observe the chemical changes of the pole piece surface and the integrity of the protective film.
Comparison of results:
and comparing the results of the experimental group and the control group, and evaluating the effect of the preservative containing the silane functional group on improving the corrosion resistance and the electrochemical stability of the battery pole piece.
And judging the protective effect of the preservative with the silane functional group according to the electrochemical performance and the stability of the surface protective film.
TABLE 2 comparison of performance of silane functional group preservatives test results
In table 2, the data before aging shows that the battery capacities and internal resistances of the experimental group and the control group are identical, being baseline data. The data after accelerated aging show that the capacity retention rate and the internal resistance increase rate of the experimental group battery are both superior to those of the control group, which shows that the preservative containing silane functional groups more effectively protects the battery pole piece.
The capacity retention is the ratio of the battery capacity after aging to the battery capacity before aging. The capacity retention of the experimental group was high, indicating its excellent anti-aging ability. The internal resistance increase rate is the ratio of the internal resistance of the battery after aging to the internal resistance of the battery before aging. The small increase of the internal resistance of the experimental group indicates that the conductivity of the battery pole piece is less affected by aging.
SEM analysis showed that the surface protective film of the experimental group did not crack or peel significantly after aging, whereas the control group showed these phenomena, indicating that the silane functional group-containing preservative performed better in maintaining the integrity of the surface protective film.
XPS analysis results show that no obvious chemical component change exists after the ageing of the experimental group, and oxide and other corrosion products are detected by the control group, which shows that the preservative containing silane functional groups can better maintain the chemical stability of the surface of the pole piece.
From the above data, it can be concluded that the silane functional group-containing preservative has a superior protective effect than the conventional preservative in terms of improving the corrosion resistance and electrochemical stability of the battery pole piece.
In a third embodiment of the present application, based on the first embodiment, the dispersing agent is an amphiphilic molecule having a directional lipophilic and hydrophilic region, and is used to effectively reduce the surface tension of the battery pole piece material during the rolling process, thereby improving the dispersing performance and preventing the re-aggregation phenomenon.
The structure of an amphiphilic molecule typically comprises a long hydrophobic carbon chain (lipophilic moiety) and a polar hydrophilic head group, such as a carboxylate, sulfonate or polyol. The structure can enable the dispersing agent to self-assemble into microcapsules or micelles in the aqueous medium, and wrap particles of the pole piece material, thereby reducing the surface tension of the particles, increasing the repulsive force among the particles and preventing the particles from re-gathering in the rolling process.
In lithium ion battery production, roll pressing is a process of uniformly coating a mixture of an active material, a binder, and the like onto a metal foil. The function of the dispersing agent is to ensure that the components can form a uniform slurry, thereby obtaining battery pole pieces with consistent performance. If the particles are re-polymerized, the battery performance may be uneven, affecting the life and reliability thereof.
And (3) performance test design:
to demonstrate the effect of amphiphilic dispersants containing oriented lipophilic and hydrophilic regions, the following was the design of the performance test:
test purpose:
the effectiveness of the amphiphilic dispersant in reducing the surface tension of the battery pole piece material, improving the dispersion performance and preventing the refolding phenomenon was evaluated.
Test material:
battery pole piece coating using standard dispersant (control group)
Battery pole piece coating using amphiphilic dispersant (experimental group)
The test method is as follows:
(1) Surface tension test:
the surface tension of the coating was measured using a tensiometer.
And comparing the measurement results of the experimental group and the control group to determine the influence of the amphiphilic dispersing agent on the surface tension.
(2) Dispersion performance test:
the particle size and distribution of the coating mixture over time were observed and recorded.
An optical microscope or a particle size analyzer was used to evaluate whether the particles were uniformly dispersed.
(3) Refocusing phenomenon test:
after a period of time by standing, it was evaluated whether the particles were subjected to a reagglomeration phenomenon.
SEM (scanning electron microscope) analysis was performed on particles of the refocusing phenomenon.
(4) Evaluation of the rolling process:
the coating is actually applied to the battery pole piece and a roll process is performed.
And evaluating the surface evenness and uniformity of the rolled pole piece.
(5) Cell performance test:
and manufacturing a battery, and performing charge-discharge cycle test.
The capacity, internal resistance and cycling stability of the battery were recorded to evaluate the impact of the pole piece quality on the battery performance.
Analysis of results:
all test results were analyzed comprehensively, comparing the performance of the experimental and control groups.
The effect of the amphiphilic dispersing agent in improving the dispersing performance of the paint, reducing the phenomenon of refolding and optimizing the rolling process is verified.
And evaluating the quality of the final battery pole piece according to the battery charge and discharge performance test result.
TABLE 3 comparison of Performance of amphiphilic dispersants
In table 3, it can be seen that for surface tension, the experimental group was significantly lower than the control group, indicating that the amphiphilic dispersant reduced the surface tension of the coating more effectively.
Average particle size: the experimental group had smaller particle size and more uniform distribution, indicating better dispersion.
Uniformity of particle distribution: the particle size distribution of the experimental group was more uniform and the standard deviation was lower.
Refocusing phenomenon scoring: the lower scores in the experimental group indicate that the amphiphilic dispersant is more effective in preventing particle reagglomeration.
Surface flatness score after rolling: the higher score obtained by the experimental group reflects that the surface of the pole piece is smoother after rolling.
Initial battery capacity: both groups were initially identical to ensure the accuracy of the comparison.
Capacity retention rate: after the cyclic test, the capacity retention rate of the experimental group is higher than that of the control group, which indicates that the quality of the battery pole piece is better.
Internal resistance change rate: the increase of the internal resistance of the experimental group is less, which indicates that the electrochemical performance of the battery is more stable.
Charge-discharge cycle stability score: the experimental group number is higher, which shows that the battery performance is less changed after a plurality of charge and discharge cycles.
From the above data, it can be concluded that the composite chemical auxiliary agent containing the amphiphilic dispersant has significant advantages in improving the dispersion performance of the battery pole piece coating, reducing the refolding phenomenon, and optimizing the pole piece surface quality in the rolling process. In addition, the battery performance test result shows that the battery pole piece using the dispersing agent can maintain higher capacity and more stable electrochemical performance in the long-term use process.
In a fourth embodiment of the present application, based on the first embodiment, the weight ratio of the modified silicone oil to the dispersant is 4:1 to 6:1.
This particular ratio is calculated based on experimental results and theory, with the aim of achieving optimal lubrication and dispersion effects, while ensuring uniformity of the coating and stability of the pole piece material.
In complex chemical aids, modified silicone oils are typically used to provide lubricity, reduce friction and blocking of the pole pieces, and dispersants are used to promote uniform dispersion of powders (e.g., active materials and conductive additives) in a solvent. The weight ratio of the modified silicone oil to the dispersant has an important influence on the final properties of the auxiliary. A higher proportion of silicone oil is advantageous for lubricity, but if excessive, it may affect the conductivity and adhesion strength of the coating. Conversely, too high a proportion of dispersant may result in an unnecessary increase in cost, and excessive dispersion may affect the structural stability of the coating. Therefore, it is important to determine the optimal weight ratio.
And (3) performance test design:
the performance test aims to verify that the performance of the composite chemical auxiliary agent in the production of the battery pole piece can be improved by optimizing the proportion of the modified organic silicone oil to the dispersing agent. The following is a design scheme for performance test:
Test purpose:
ensuring that the composite chemical auxiliary provides excellent coating uniformity, lubricity and battery performance at a given ratio of modified silicone oil to dispersant.
Test material:
experimental group: composite chemical auxiliary agent of modified organic silicone oil and dispersing agent are mixed according to the proportion of 4:1 to 6:1
Control group: using non-optimised proportions of complex chemical auxiliary agents
The testing method comprises the following steps:
(1) Coating uniformity test:
the auxiliary ingredients were weighed using a precision balance and mixed to a ratio of 4:1 to 6:1.
The auxiliary agent was coated on the battery pole piece, and after drying, the uniformity of the coating was evaluated using a microscope.
(2) Lubricity test:
and measuring the friction coefficient of the surface of the pole piece coated with the auxiliary agent by using a friction coefficient tester.
The difference in friction coefficients of the experimental group and the control group was compared.
(3) Cell performance test:
and preparing a battery sample, and performing charge-discharge cycle test.
The initial capacity, capacity retention and internal resistance were measured and recorded.
TABLE 4 comparison of Performance of composite chemical assistants comprising modified organic Silicone oil and dispersant in different proportions
/>
As can be seen from table 4, the experimental groups of 4:1 and 5:1 ratios showed excellent coating uniformity, with the 5:1 ratio being slightly better than 4:1. The 6:1 ratio also shows better uniformity but is reduced compared to the other two ratios.
The 5:1 ratio achieves the lowest surface coefficient of friction, indicating that this ratio may provide the best lubrication without sacrificing the structural integrity of the coating.
All groups, including the control group, were identical in initial capacity to ensure consistency of the comparison.
Capacity retention after 100 cycles: the 5:1 ratio has the highest capacity retention, indicating that this ratio may provide the best balance between lubrication and coating integrity, beneficial for long term battery performance.
Internal resistance increase rate: the 5:1 ratio of the internal resistance increase rate was the lowest, suggesting that the cell maintained better electrochemical stability during cycling, with advantages over other ratios and control groups.
From Table 4, it can be concluded that a 5:1 ratio of modified silicone oil to dispersant provides the best overall performance, although experimental groups within all tested ratio ranges show performance improvements over non-optimized ratio control groups.
A fifth embodiment of the present application is the composite chemical assistant of the first embodiment, further comprising a molecular sieve material for absorbing and neutralizing harmful gases that may be released during the rolling process.
Molecular sieves are porous materials that can selectively adsorb molecules of a specific size through their pore structure, and are commonly used in adsorption and separation applications. During the rolling process of the battery pole piece, the molecular sieve can effectively absorb harmful gases such as Volatile Organic Compounds (VOCs) or other decomposition products which are possibly released, thereby improving the safety of the working environment and the consistency of the battery performance.
The addition of molecular sieve material can realize the following functions:
adsorbing harmful gas: during rolling, certain chemicals may decompose and release harmful gases due to mechanical pressure and heat. Molecular sieves can trap these gases and prevent them from diffusing into the environment.
Neutralization: certain molecular sieve materials can also chemically neutralize these deleterious substances, for example, by acid-base neutralization reactions, or by catalytic decomposition into harmless substances.
The quality of the pole piece is improved: molecular sieves help to maintain the quality of the pole piece material and the final battery product by reducing contamination in the production environment.
The type of molecular sieve includes, but is not limited to, 3A, 4A, 5A, 13X, etc., which is selected depending on the size and chemistry of the target gas. In practice, the amount and form of molecular sieve addition (e.g., powder, particle, or coating) will need to be determined based on the particular application and the adsorption capacity desired.
And (3) performance test design:
in order to prove that the added molecular sieve material can effectively absorb and neutralize harmful gas, improve the safety of the production process and maintain the quality of the pole piece, the following is a performance test design scheme:
test purpose:
The ability of the composite chemical auxiliary added with the molecular sieve material to absorb harmful gases in the rolling process and the influence on the battery performance are verified.
Test material:
experimental group: adding a composite chemical auxiliary agent of a molecular sieve material.
Control group: no composite chemical auxiliary agent of molecular sieve material is added.
The testing method comprises the following steps:
(1) Harmful gas absorption test:
the rolling process was simulated in a closed vessel and the change in concentration of the harmful gases was monitored.
The gas concentration in the container was measured using a gas analyzer, and the experimental group and the control group were compared.
(2) And (3) neutralization effect test:
if the molecular sieve has chemical neutralization ability, the neutralization effect can be evaluated by detecting the product.
And analyzing the chemical composition change of the gas in the container to confirm the neutralization of harmful substances.
(3) And (3) pole piece quality assessment:
and preparing the rolled battery pole piece, and performing visual and physical inspection.
The surface quality, thickness uniformity and mechanical strength of the pole pieces were evaluated.
(4) Cell performance test:
and manufacturing a battery cell, and performing standard charge and discharge tests.
The capacity, internal resistance and cycling stability of the cells were compared.
TABLE 5 comparison of the Properties of composite chemical auxiliary with molecular sieves added
As can be seen from table 5, the experimental group showed almost complete absorption of the harmful gas in the container for the harmful gas absorption efficiency, whereas the control group did not.
Harmful gas neutralization efficiency: the experimental group also significantly neutralized these gases, reducing the presence of harmful substances.
Pole piece surface quality scoring: the surface quality score of the pole piece of the experimental group is higher, which indicates that fewer defects exist in the rolling process.
Pole piece thickness consistency scoring: the experimental set of pole pieces were more uniform in thickness, which may be due to better production conditions.
Battery capacity retention rate: the capacity retention rate of the experimental group after charge and discharge cycles is higher than that of the control group, which shows that the stability of the battery performance can be improved by adding the auxiliary agent of the molecular sieve.
Rate of change of internal resistance of battery: the lower internal resistance change of the experimental group indicates that the battery keeps better performance in the use process.
From these data, it is evident that the composite chemical additives added to the molecular sieve material have positive effects in improving the working environment, absorbing and neutralizing harmful gases, and enhancing the performance of the final battery product.
According to a sixth embodiment of the application, based on the first embodiment, the composite chemical auxiliary agent further comprises 0.05-0.5 part by weight of an inorganic nonmetallic catalyst, wherein the inorganic nonmetallic catalyst is selected from materials consisting of silicate, zeolite or phosphate, and is used for promoting chemical crosslinking reaction on the surface of the battery pole piece, enhancing the bonding strength of a coating and the pole piece, and simultaneously reducing the risk of delamination of the materials in the rolling process.
In this embodiment, the inorganic nonmetallic catalyst functions to promote chemical crosslinking reaction during the coating process of the battery pole piece. The chemical crosslinking reaction can improve the structural stability of the coating, increase the bonding strength between the coating and the pole piece, and reduce the delamination or the shedding of the coating in the rolling process, which is important for improving the performance and the reliability of the battery.
The inorganic nonmetallic catalysts are selected based on their ability to activate or accelerate the crosslinking reaction at room temperature or lower heat treatment temperatures. Silicates, zeolites, and phosphates are materials widely used in the catalytic field, which materials are used as catalysts due to their pore structure and surface active sites. In this application, they promote cross-linking between the polymer chains that make up the coating, forming a network structure that is more compact and better in mechanical properties.
The amount of catalyst added during the preparation should be strictly controlled to 0.05 to 0.5 parts by weight to ensure a sufficient catalytic effect without excessively affecting the functions of the other components. This ratio is experimentally optimized to balance catalytic efficiency and cost effectiveness.
And (3) performance test design:
to demonstrate the effect of composite chemical adjuvants comprising inorganic nonmetallic catalysts in improving the coating bond strength and reducing the risk of delamination, the following is a performance test design scheme:
Test purpose:
the efficacy of the inorganic nonmetallic catalyst in promoting the crosslinking reaction of the battery pole piece coating and improving the structural stability of the coating is verified.
Test material:
experimental group: adding composite chemical assistant of inorganic nonmetallic catalyst.
Control group: no composite chemical assistant of inorganic nonmetallic catalyst is added.
The testing method comprises the following steps:
(1) Coating bond strength test:
and preparing the battery pole piece with various auxiliary agents.
The bond strength of the coating to the pole piece was evaluated by peel testing or shear strength testing.
(2) Evaluation of chemical crosslinking degree:
the degree of completion of the crosslinking reaction is evaluated by infrared spectroscopic analysis or thermogravimetric analysis.
The degree of crosslinking was compared between the experimental and control groups.
(3) Stability test in rolling process:
after the simulated rolling process, the integrity of the coating and whether delamination occurred were checked.
The stability of the coating was evaluated by visual inspection and physical testing.
(4) Cell performance test:
and manufacturing a battery and performing charge and discharge tests.
The battery capacity, internal resistance and cycling stability were measured.
TABLE 6 comparison of performance of catalyst-loaded composite chemical assistants
As can be seen from table 6, for the bonding strength: the bonding strength of the experimental group is obviously higher than that of the control group, which proves that the catalyst effectively promotes the crosslinking reaction and enhances the adhesion between the coating and the pole piece.
Degree of crosslinking: the degree of crosslinking in the experimental group was higher than that in the control group, indicating that the coating crosslinking reaction was more complete.
Coating integrity score: the experimental group has high score, reflects that the integrity of the coating after rolling is better, and has no obvious defect.
Layering occurrence rate: the layering incidence of the experimental group is lower, which indicates that the coating is more stable in the rolling process and is not easy to be layered.
Initial battery capacity: the initial capacities of the two groups are the same to ensure the fairness of the test.
Capacity retention after cycling: the experimental group showed higher capacity retention after battery charge and discharge cycles, indicating that the catalyst helps to maintain battery performance.
Internal resistance change rate: the internal resistance of the experimental group is less changed, which indicates that the internal structure of the battery is more stable.
From these data, it can be concluded that the composite chemical auxiliary added with the inorganic non-metal catalyst has a significant effect in improving the bonding strength and structural stability of the battery pole piece coating, and helps to improve the performance of the final battery product.
According to the seventh embodiment, based on the first embodiment, the composite chemical auxiliary agent further comprises 2-3 parts by weight of an environment-sensitive microcapsule, the microcapsule contains a mixture of modified organic silicone oil and a dispersing agent, the shell material of the microcapsule is a biodegradable polymer, and the microcapsule is designed to be dissociated when reaching the specific humidity or pH value condition of battery pole piece processing, so that the timed release of the auxiliary agent is ensured, and the distribution and the attaching effect on the surface of the battery pole piece are optimized.
In this embodiment, a composite chemical adjuvant comprising environmentally sensitive microcapsules is provided. These microcapsules contain a mixture of modified silicone oil and a dispersing agent inside, while the shell is made of a biodegradable polymer. This design allows the microcapsules to release the internal active ingredient at the appropriate time during the processing of the battery pole pieces in response to specific environmental conditions (e.g., changes in humidity or pH). Such a controlled release mechanism can improve the uniformity and adhesion of the coating while reducing waste and environmental impact.
The core design of the environmentally sensitive microcapsules is that they are able to respond to environmental changes that may occur during the pole piece processing. For example, if the ambient humidity is increased or the pH is changed during the coating process, the microcapsules dissociate, releasing the modified silicone oil and dispersant contained therein, thereby forming a more uniform coating on the surface of the pole piece. The biodegradable polymer is selected from PLA (polylactic acid), PHB (polyhydroxybutyrate) and the like, and the biodegradable polymer can be degraded after meeting specific conditions, so that the problem of long-term environmental accumulation is reduced.
In practice, the preparation of the microcapsules involves selecting an appropriate biodegradable polymeric material, encapsulating the modified silicone oil and dispersant mixture within the microcapsules, and adjusting the preparation process to ensure that the microcapsules are sensitive to a particular humidity or pH. The size, shell thickness and content (2-3 parts by weight) of the microcapsules need to be optimized experimentally to achieve optimal release.
And (3) performance test design:
the purpose of the performance test is to verify whether the controlled release mechanism of the environmentally sensitive microcapsules can improve the effect of the coating during the pole piece processing.
Test material:
experimental group: adding the composite chemical auxiliary agent of the environment-sensitive microcapsule.
Control group: no microcapsule composite chemical auxiliary agent is added.
The testing method comprises the following steps:
(1) And (3) testing the control release effect:
and simulating the processing environment of the battery pole piece, and artificially regulating the humidity and the pH value.
The dissociation behaviour of the microcapsules and the release of the active ingredient under different environmental conditions were observed and recorded.
(2) Coating uniformity evaluation:
the two auxiliary agents are coated on the pole piece and dried under the condition of specific humidity or pH value respectively.
The uniformity of the coating is assessed using an optical microscope or other surface analysis technique.
(3) Coating adhesion effect test:
the adhesion strength of the coating to the pole piece was evaluated by a peel test.
The coating adhesion strength of the experimental and control groups was compared.
(4) Environmental impact assessment:
degradation of the microcapsule material was evaluated by a biodegradation test.
Degradation products were measured and their potential impact on the environment was assessed.
TABLE 7 comparison of the Performance of microencapsulated Complex chemical Advances
As can be seen from table 7, the microcapsules in the experimental group dissociated within 10 minutes, releasing the active ingredient, whereas the control group was unsuitable for this test since there were no microcapsules.
Coating uniformity scoring: the coating uniformity score was higher for the experimental group, indicating that the controlled release of microcapsules helped to form a more uniform coating.
Coating adhesion strength: the adhesion strength of the coating of the experimental group is higher than that of the control group, which indicates that the active ingredients released in the microcapsule can effectively enhance the combination of the coating and the pole piece.
Biodegradation rate: the microcapsule materials in the experimental group have high biodegradation rate, and the long-term influence on the environment is reduced.
The test results can be used for concluding that the composite chemical auxiliary agent added with the environment-sensitive microcapsule can effectively control the release of active ingredients under specific environmental conditions, improve the uniformity and the adhesion effect of the coating and provide a degradable environment-friendly solution.
According to the eighth embodiment, based on the first embodiment, the composite chemical auxiliary agent further comprises 0.1-1.0 parts by weight of an antifoaming agent, wherein the antifoaming agent is selected from silicone or polyether antifoaming agents and is used for effectively inhibiting foam generation in a rolling process, ensuring uniformity and surface quality of a coating, improving rolling efficiency and reducing material loss in the rolling process.
During the rolling process, air bubbles in the coating may cause non-uniformity of the coating, affecting the quality of the pole piece and the performance of the battery. The silicone or polyether defoamer can effectively destroy the stability of the foam and accelerate the dissipation of the foam. Silicone-based defoamers generally have excellent thermal stability and chemical inertness, while polyether-based defoamers are known for their low surface tension and good dispersibility.
When preparing the composite chemical auxiliary agent, the addition amount of the defoaming agent needs to be precisely controlled within the range of 0.1-1.0 parts by weight so as to ensure an effective defoaming effect and avoid affecting other properties of the coating. In addition, it is also important to choose an appropriate type of defoamer to ensure that it is compatible with the other ingredients in the adjuvant.
To verify the effect of the defoamer-added composite chemical auxiliary in improving the coating uniformity and rolling efficiency, the following performance test scheme is adopted in the embodiment:
test purpose:
and verifying the effect of the composite chemical auxiliary agent added with the defoaming agent on inhibiting foam generation in the rolling process and the influence of the composite chemical auxiliary agent on the coating quality and the rolling efficiency.
Test material:
experimental group: a complex chemical auxiliary agent of an antifoaming agent (silicone type) is added.
Control group: no complex chemical auxiliary agent of defoamer is added.
The testing method comprises the following steps:
(1) Foam generation test:
under simulated rolling conditions, the formation of foam in the coatings of the experimental and control groups was compared.
The degree of foam generation was evaluated by visual observation and foam amount measurement.
(2) Coating uniformity evaluation:
the pole pieces were coated with two adjuvants and after drying the uniformity of the coating was evaluated using an optical microscope.
The coating quality was evaluated by uniformity of coating thickness and surface finish.
(3) And (3) rolling efficiency test:
the time and energy consumption during the rolling process were measured.
The rolling efficiency of the experimental group and the control group were compared.
Table 8 comparison of Properties of composite chemical auxiliary with defoamer added
Data interpretation of table 8:
foam amount: the experimental group showed significantly less foam generation than the control group, indicating that the defoamer effectively reduced foam generation.
Coating uniformity scoring: the coating uniformity score was higher for the experimental group, indicating that the addition of defoamer improved the uniformity and surface quality of the coating.
Rolling time: the time required for the rolling process of the experimental group was shorter than that of the control group, indicating that the addition of the antifoaming agent can improve the rolling efficiency.
Roller pressure energy consumption: the energy consumption of the rolling process of the experimental group is lower than that of the control group, and the improvement of the rolling efficiency is further confirmed.
According to the test results, the conclusion can be drawn that the composite chemical auxiliary agent added with the defoaming agent effectively inhibits foam generation in the rolling process, improves the uniformity of the coating and the rolling efficiency, and reduces the material loss and the energy consumption in the rolling process.
The ninth embodiment of the application provides a preparation method of a composite chemical auxiliary agent for preventing sticking and cracking in a rolling process of a lithium ion battery pole piece, which comprises the following steps:
s1, adding 50 parts of deionized water according to a weight ratio;
s2, respectively adding 2-10 parts of modified organic silicone oil and 2-4 parts of dispersing agent according to the weight ratio at the stirring speed of 30-50 r/min, and stirring for 20-30 min;
s3, after the modified organic silicone oil is fully dissolved, supplementing 35-45 parts of deionized water according to the weight ratio, adding 1-2 parts of preservative, and stirring for 5-10 minutes;
s4, adding 0.5-1 part of PH value regulator according to the weight ratio, and stirring for 5-10 minutes. And turning off the stirrer after stirring, and filling according to the packaging specification.
While the preferred embodiment has been described, it is not intended to limit the invention thereto, and any person skilled in the art may make variations and modifications without departing from the spirit and scope of the present invention, so that the scope of the present invention shall be defined by the claims of the present application.
Claims (10)
1. The composite chemical auxiliary agent for preventing sticking and cracking in the rolling process of the lithium ion battery pole piece is characterized by comprising, by weight, 2-10 parts of modified silicone oil, 1-2 parts of preservative, 0.5-1 part of pH value regulator, 2-4 parts of dispersing agent and 85-95 parts of deionized water.
2. The composite chemical auxiliary according to claim 1, wherein the modified silicone oil is hydroxyl-terminated polydimethylsiloxane or polysiloxane containing alkyl groups; the preservative is selected from hydroxybenzoates, phenoxyethanol or a mixture thereof; the PH value regulator is ammonia water, monoethanolamine or AMP-95; the dispersing agent is at least one of nonionic surfactant, polyether or polyether modified silicone oil.
3. The composite chemical auxiliary according to claim 1, wherein the preservative has silane functional groups for covalent bond reaction with the battery pole piece material at the surface of the battery pole piece, thereby providing a long term protective effect.
4. The composite chemical auxiliary according to claim 1, wherein the dispersing agent is an amphiphilic molecule having directional lipophilic and hydrophilic regions for effectively reducing surface tension of the battery pole piece material during rolling, thereby improving dispersion properties and preventing a re-polymerization phenomenon.
5. The composite chemical auxiliary according to claim 1, wherein the weight ratio of the modified silicone oil to the dispersant is 4:1 to 6:1.
6. The composite chemical auxiliary according to claim 1, further comprising a molecular sieve material to absorb and neutralize harmful gases that may be released during rolling.
7. The composite chemical auxiliary according to claim 1, further comprising 0.05-0.5 parts by weight of an inorganic non-metal catalyst selected from materials consisting of silicate, zeolite or phosphate to promote chemical crosslinking reaction at the surface of the battery pole piece, enhance the bonding strength of the coating to the pole piece, and reduce the risk of delamination of the material during rolling.
8. The composite chemical auxiliary according to claim 1, further comprising 2-3 parts by weight of an environmentally sensitive microcapsule in which the modified silicone oil and the dispersing agent are encapsulated, wherein the shell material of the environmentally sensitive microcapsule is a biodegradable polymer designed to dissociate upon reaching a specific humidity or pH condition for battery pole piece processing, ensuring the timed release of the auxiliary, thereby optimizing the distribution and adhesion effect on the battery pole piece surface.
9. The composite chemical auxiliary according to claim 1, further comprising 0.1 to 1.0 parts by weight of an antifoaming agent selected from silicone-based or polyether-based antifoaming agents for effectively suppressing the generation of foam during rolling, ensuring uniformity and surface quality of a coating, and simultaneously improving rolling efficiency and reducing material loss during rolling.
10. The preparation method of the composite chemical auxiliary agent for preventing sticking and cracking in the rolling process of the lithium ion battery pole piece is characterized by comprising the following steps:
s1, adding 50 parts of deionized water according to a weight ratio;
s2, respectively adding 2-10 parts of modified organic silicone oil and 2-4 parts of dispersing agent according to the weight ratio at the stirring speed of 30-50 r/min, and stirring for 20-30 min;
s3, after the modified organic silicone oil is fully dissolved, supplementing 35-45 parts of deionized water according to the weight ratio, adding 1-2 parts of preservative, and stirring for 5-10 minutes;
s4, adding 0.5-1 part of PH value regulator according to the weight ratio, and stirring for 5-10 minutes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311509488.6A CN117343642A (en) | 2023-11-14 | 2023-11-14 | Composite chemical auxiliary agent and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311509488.6A CN117343642A (en) | 2023-11-14 | 2023-11-14 | Composite chemical auxiliary agent and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117343642A true CN117343642A (en) | 2024-01-05 |
Family
ID=89363266
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311509488.6A Pending CN117343642A (en) | 2023-11-14 | 2023-11-14 | Composite chemical auxiliary agent and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117343642A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017063218A1 (en) * | 2015-10-14 | 2017-04-20 | 中航锂电（洛阳）有限公司 | Composite separator for lithium ion battery and preparation method therefor, and lithium ion battery |
| CN108511691A (en) * | 2018-03-21 | 2018-09-07 | 深圳市皓飞实业有限公司 | A kind of anti-sticking roller mould release and preparation method thereof for electrodes of lithium-ion batteries |
| CN109326767A (en) * | 2017-07-31 | 2019-02-12 | 宁德时代新能源科技股份有限公司 | Positive plate, secondary battery and preparation method thereof |
| WO2019236371A2 (en) * | 2018-05-29 | 2019-12-12 | Nanotek Instruments, Inc. | Fire-resistant lithium battery containing an electrode-protecting layer |
| CN114864873A (en) * | 2022-04-20 | 2022-08-05 | 江苏正力新能电池技术有限公司 | Pre-lithiation method for negative plate, negative plate obtained by pre-lithiation method and secondary battery |
-
2023
- 2023-11-14 CN CN202311509488.6A patent/CN117343642A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017063218A1 (en) * | 2015-10-14 | 2017-04-20 | 中航锂电（洛阳）有限公司 | Composite separator for lithium ion battery and preparation method therefor, and lithium ion battery |
| CN109326767A (en) * | 2017-07-31 | 2019-02-12 | 宁德时代新能源科技股份有限公司 | Positive plate, secondary battery and preparation method thereof |
| CN108511691A (en) * | 2018-03-21 | 2018-09-07 | 深圳市皓飞实业有限公司 | A kind of anti-sticking roller mould release and preparation method thereof for electrodes of lithium-ion batteries |
| WO2019236371A2 (en) * | 2018-05-29 | 2019-12-12 | Nanotek Instruments, Inc. | Fire-resistant lithium battery containing an electrode-protecting layer |
| CN114864873A (en) * | 2022-04-20 | 2022-08-05 | 江苏正力新能电池技术有限公司 | Pre-lithiation method for negative plate, negative plate obtained by pre-lithiation method and secondary battery |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Jia et al. | Effects of filler loading and surface modification on electrical and thermal properties of epoxy/montmorillonite composite☆ | |
| CN107057014B (en) | Modified bentonite/polyurethane composite material and preparation method and application thereof | |
| EP3250537B1 (en) | Ceramic binder composition for ceramic coated separator for lithium ion batteries, methods of producing same, and uses thereof | |
| EP2678266A2 (en) | Self-aligned graphene polymer nanocomposites | |
| DE112007002375T5 (en) | Stabilized lithium metal powder for Li-ion application, composition and method | |
| WO2014149181A1 (en) | Gum-like electrolytes and methods of making the same | |
| CN110444793B (en) | Durable proton exchange membrane, preparation method and application thereof | |
| KR20130073891A (en) | Sealing material composition for secondary battery, method for producing same, and secondary battery using same | |
| Jamshidnejad et al. | Synthesis of self-healing smart epoxy and polyurethane coating by encapsulation of olive leaf extract as corrosion inhibitor | |
| Wang et al. | Environmentally friendly plant‐based waterborne polyurethane for hydrophobic and heat‐resistant films | |
| CN117343642A (en) | Composite chemical auxiliary agent and preparation method thereof | |
| Woo et al. | Investigating the effect of solvent composition on ink structure and crack formation in polymer electrolyte membrane fuel cell catalyst layers | |
| CN113416414B (en) | Preparation method and application of aramid nanofiber/porous graphene/polyaniline composition, hydrogel and film with high mechanical strength | |
| Kim et al. | Effects of ionic liquids and silica nanoparticles on the ionic conductivities, mechanical properties, and rheological properties of sodium-containing solid polymer electrolytes | |
| Liu et al. | Preparation of poly (N-isopropylacrylamide) brush bonded on silicon substrate and its water-based lubricating property | |
| Lawandy et al. | Penetration of oils into polychloroprene rubber | |
| Liu et al. | Inhibiting liquid permeation into silicone rubber by superhydrophobic coating for prolonged service life | |
| CN115322679B (en) | Waterproof material emulsion and application thereof | |
| JP2007131830A (en) | Urethane resin composition and electrical and electronic part subjected to insulation treatment using the resin composition | |
| CN113150640B (en) | Cerium ion-loaded two-dimensional nanomaterial-based self-healing barrier dual-function coating and preparation method and application thereof | |
| Yu et al. | Preparation and corrosion resistance of polyaniline and waterborne polyurethane composite coating film | |
| CN111808521B (en) | Self-repairing waterborne polyurethane coating composition and coating | |
| JP2009067816A (en) | Polyurethane resin electric insulation composition | |
| CN116848200A (en) | Thermally stable conductive polymer coating | |
| CN110628207A (en) | Rat-proof and ant-proof condensation-proof foam material, preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |