CN115895548B - Positive electrode plate UV delay type glue, preparation method and protection method thereof - Google Patents
Positive electrode plate UV delay type glue, preparation method and protection method thereof Download PDFInfo
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- CN115895548B CN115895548B CN202310012639.0A CN202310012639A CN115895548B CN 115895548 B CN115895548 B CN 115895548B CN 202310012639 A CN202310012639 A CN 202310012639A CN 115895548 B CN115895548 B CN 115895548B
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- 239000003292 glue Substances 0.000 title claims abstract description 82
- 238000000034 method Methods 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title abstract description 19
- 229920005989 resin Polymers 0.000 claims abstract description 69
- 239000011347 resin Substances 0.000 claims abstract description 69
- 239000000945 filler Substances 0.000 claims abstract description 39
- 239000003822 epoxy resin Substances 0.000 claims abstract description 35
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 35
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 32
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 32
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000001816 cooling Methods 0.000 claims abstract description 24
- 239000012948 isocyanate Substances 0.000 claims abstract description 19
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 239000003085 diluting agent Substances 0.000 claims abstract description 18
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002318 adhesion promoter Substances 0.000 claims abstract description 11
- VPASWAQPISSKJP-UHFFFAOYSA-N ethyl prop-2-enoate;isocyanic acid Chemical compound N=C=O.CCOC(=O)C=C VPASWAQPISSKJP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 10
- 150000005846 sugar alcohols Polymers 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 238000001723 curing Methods 0.000 claims description 72
- 239000012952 cationic photoinitiator Substances 0.000 claims description 22
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 20
- 229910052744 lithium Inorganic materials 0.000 claims description 20
- 239000012949 free radical photoinitiator Substances 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 19
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical group CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 claims description 18
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 15
- 229920005862 polyol Polymers 0.000 claims description 15
- 150000003077 polyols Chemical class 0.000 claims description 15
- -1 acrylic ester Chemical class 0.000 claims description 14
- 239000011248 coating agent Substances 0.000 claims description 13
- 238000000576 coating method Methods 0.000 claims description 13
- 238000009413 insulation Methods 0.000 claims description 12
- 238000004381 surface treatment Methods 0.000 claims description 12
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 11
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims description 11
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 11
- 239000004842 bisphenol F epoxy resin Substances 0.000 claims description 10
- 238000002844 melting Methods 0.000 claims description 10
- 230000008018 melting Effects 0.000 claims description 10
- 238000004804 winding Methods 0.000 claims description 10
- 238000005520 cutting process Methods 0.000 claims description 9
- 238000007599 discharging Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000003698 laser cutting Methods 0.000 claims description 9
- WDHYRUBXLGOLKR-UHFFFAOYSA-N phosphoric acid;prop-2-enoic acid Chemical group OC(=O)C=C.OP(O)(O)=O WDHYRUBXLGOLKR-UHFFFAOYSA-N 0.000 claims description 9
- 229920001451 polypropylene glycol Polymers 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims description 6
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 5
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 5
- 238000010008 shearing Methods 0.000 claims description 5
- 238000004090 dissolution Methods 0.000 claims description 4
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- 238000005406 washing Methods 0.000 claims description 4
- 229910052582 BN Inorganic materials 0.000 claims description 3
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 3
- 229910001593 boehmite Inorganic materials 0.000 claims description 3
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 3
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 3
- AHHWIHXENZJRFG-UHFFFAOYSA-N oxetane Chemical compound C1COC1 AHHWIHXENZJRFG-UHFFFAOYSA-N 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 2
- 239000011353 cycloaliphatic epoxy resin Substances 0.000 claims description 2
- 230000001070 adhesive effect Effects 0.000 abstract description 18
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract 1
- 239000003792 electrolyte Substances 0.000 description 19
- 239000000853 adhesive Substances 0.000 description 16
- 238000012360 testing method Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 11
- 239000000463 material Substances 0.000 description 10
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- 239000002390 adhesive tape Substances 0.000 description 9
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- 229910052782 aluminium Inorganic materials 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 238000005286 illumination Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
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- 230000000694 effects Effects 0.000 description 6
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- 239000010410 layer Substances 0.000 description 4
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- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- 239000004416 thermosoftening plastic Substances 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 238000003848 UV Light-Curing Methods 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- 239000000084 colloidal system Substances 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 239000010954 inorganic particle Substances 0.000 description 3
- 230000001678 irradiating effect Effects 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 238000011417 postcuring Methods 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- 238000004513 sizing Methods 0.000 description 3
- 229920001169 thermoplastic Polymers 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
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- 238000004519 manufacturing process Methods 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
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- 238000007711 solidification Methods 0.000 description 2
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- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- HBGPNLPABVUVKZ-POTXQNELSA-N (1r,3as,4s,5ar,5br,7r,7ar,11ar,11br,13as,13br)-4,7-dihydroxy-3a,5a,5b,8,8,11a-hexamethyl-1-prop-1-en-2-yl-2,3,4,5,6,7,7a,10,11,11b,12,13,13a,13b-tetradecahydro-1h-cyclopenta[a]chrysen-9-one Chemical compound C([C@@]12C)CC(=O)C(C)(C)[C@@H]1[C@H](O)C[C@]([C@]1(C)C[C@@H]3O)(C)[C@@H]2CC[C@H]1[C@@H]1[C@]3(C)CC[C@H]1C(=C)C HBGPNLPABVUVKZ-POTXQNELSA-N 0.000 description 1
- PFRGGOIBYLYVKM-UHFFFAOYSA-N 15alpha-hydroxylup-20(29)-en-3-one Natural products CC(=C)C1CCC2(C)CC(O)C3(C)C(CCC4C5(C)CCC(=O)C(C)(C)C5CCC34C)C12 PFRGGOIBYLYVKM-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- MPIZVHPMGFWKMJ-AKGZTFGVSA-N L-alpha-(methylidenecyclopropyl)glycine Chemical compound OC(=O)[C@@H](N)C1CC1=C MPIZVHPMGFWKMJ-AKGZTFGVSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 229930182555 Penicillin Natural products 0.000 description 1
- JGSARLDLIJGVTE-MBNYWOFBSA-N Penicillin G Chemical compound N([C@H]1[C@H]2SC([C@@H](N2C1=O)C(O)=O)(C)C)C(=O)CC1=CC=CC=C1 JGSARLDLIJGVTE-MBNYWOFBSA-N 0.000 description 1
- 229920003006 Polybutadiene acrylonitrile Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- SOKRNBGSNZXYIO-UHFFFAOYSA-N Resinone Natural products CC(=C)C1CCC2(C)C(O)CC3(C)C(CCC4C5(C)CCC(=O)C(C)(C)C5CCC34C)C12 SOKRNBGSNZXYIO-UHFFFAOYSA-N 0.000 description 1
- 229920006397 acrylic thermoplastic Polymers 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
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- 230000000593 degrading effect Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- VJIDDJAKLVOBSE-UHFFFAOYSA-N ethylhydroquinone Natural products CCC1=CC(O)=CC=C1O VJIDDJAKLVOBSE-UHFFFAOYSA-N 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000000051 modifying effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229940049954 penicillin Drugs 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000005381 potential energy Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000012745 toughening agent Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Adhesives Or Adhesive Processes (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The positive plate UV delay type glue comprises the following components in parts by weight: 20-50 parts of epoxy resin, 10-15 parts of flexible acrylic resin, 40-60 parts of filler, 20-30 parts of toughening resin, 10-20 parts of reactive diluent, 1-3 parts of adhesion promoter and 1-5 parts of photoinitiator. The flexible acrylic resin is prepared by the following method: s1: melt mixing hydrogenated bisphenol A and polyalcohol, removing water and cooling; s2: dropping isocyanate to react to form hydroxyl end-capped resin, and cooling; s3: adding isocyanate ethyl acrylate into the hydroxyl end-capped resin for reaction; s4: and adding hydroquinone to obtain the flexible acrylic resin. The glue disclosed by the invention has excellent comprehensive properties such as adhesive property, insulativity, electrochemical stability and mechanical property, the preparation method and raw materials are environment-friendly, the application is simple and convenient, and the curing degree and speed can be regulated and controlled.
Description
Technical Field
The invention belongs to the technical field of adhesives for electrode plate protection, and particularly relates to a positive electrode plate UV delay type glue, a preparation method and a protection method thereof.
Background
After the die cutting of the positive plate of the lithium battery, metal burrs are easy to occur at the edge of the positive plate, and the metal burrs have the risk of piercing through the diaphragm, so that the positive plate and the negative plate are directly conducted, and fire, explosion and the like of the lithium battery are caused. Therefore, the edge of the positive pole piece is coated with the insulating layer, so that the width of the positive pole piece exceeds that of the negative pole piece, and the edge of the negative pole is opposite to the insulating layer of the positive pole after winding or lamination, thereby avoiding the safety risk that the positive pole and the negative pole are conducted through die cutting burrs.
In view of the above requirements, some existing products on the market at present have a certain problem, and cannot fully meet the process and use requirements, and the main product types on the market at present include the following products:
1. and (3) adhesive tape. The die cutting cost of the adhesive tape is high, and a step structure is arranged at the edge of the positive electrode material, so that the adhesive tape is difficult to completely attach, and electrolyte is permeated; in addition, the adhesive tape has lower adhesive force and is easy to fall off after long-term soaking.
2. A thermoplastic adhesive. The thermoplastic adhesive has the advantages of simple sizing process, high curing speed, good adhesion to aluminum, and capability of resisting vibration impact, but the thermoplastic adhesive has poor interface wettability and large high-temperature and low-temperature performance attenuation.
3. A thermosetting adhesive. Each performance of the thermosetting adhesive can meet the application requirement, but the thermosetting adhesive needs to be heated or placed at room temperature for a long time during curing, and cannot meet the requirement of production efficiency.
4. A solvent type adhesive. Has the environmental protection problem of solvent volatilization, and has weak adhesive force and electrolyte corrosion resistance.
5. And (3) UV curing the adhesive. The general acrylic acid UV curing adhesive has the advantages of simple sizing process, high curing speed, poor solvent resistance, large shrinkage, oxygen polymerization inhibition, large bonding interface stress and the like. The general cationic UV delay curing adhesive can realize delay curing, but has large bonding interface stress and poor adhesive force to aluminum materials.
In addition, polyvinylidene fluoride is dissolved in N-methyl pyrrolidone solvent, filler such as ceramic is added, then edges of two sides of the positive pole piece are coated, the positive pole piece is dried and rolled after being coated, then laser cutting is carried out with the next process, and the rolling is carried out after the superfluous part is cut off. However, the solvent type polyvinylidene fluoride protective material used at present has the following problems: the solvent is not environment-friendly in volatilization, the flash point of N-methyl pyrrolidone is high, the drying speed is low, the dispersibility of the filler is poor, and the filler is easy to settle.
Patent CN115172751a discloses a positive plate with a polymer edge insulating layer and its application in lithium battery, the polymer is a polymer coating or adhesive tape, and the polymer coating is polyimide polymer, acrylic polymer or thermoplastic fluorine-containing polymer; the adhesive tape is polyimide adhesive tape or PET adhesive tape which can resist the high temperature of more than 250 ℃, and the solvent is methanol, ethanol, diethyl ether, chloroform, pyridine, N-methylpyrrolidone or acetone. The invention adopts polymer coating or adhesive tape, and has the characteristics of low hardness, low surface roughness and high bonding strength. However, the insulating layer of the invention has higher preparation cost, is easy to peel from the positive electrode plate, has common liquid resistance, can drop after being soaked in electrolyte for a long time, is easy to fuse glue, causes aluminum exposure, and has short circuit risk.
Therefore, how to obtain UV-delay curing glue with good insulating property, bonding property and mechanical property, and stable electrochemical property, which can resist solvent erosion, and low shrinkage, is a technical problem to be solved in the field.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide the UV delay curing glue with good comprehensive properties such as bonding property, insulating property, electrochemical stability, mechanical property and the like, and the preparation method of the glue is simple, low in cost and environment-friendly, and the glue is applied to the edge insulation protection of the positive electrode plate of the battery, is simple and convenient to glue, and has adjustable curing degree and speed.
Specifically, the invention provides UV delay curing type glue for protecting the edge insulation of a positive electrode plate, which comprises the following components in parts by weight:
20-50 parts of epoxy resin
10-15 parts of flexible acrylic resin
40-60 parts of filler
10-30 parts of toughening resin
10-20 parts of reactive diluent
1-3 parts of adhesion promoter
1-5 parts of photoinitiator
The flexible acrylic resin is prepared by the following method:
s1: mixing hydrogenated bisphenol A and polyalcohol in a molar ratio of 1 (0.8-1.2), removing water for 45-75min, and cooling to 100-130deg.C;
s2: dripping isocyanate accounting for 40-60% of the total mole of hydrogenated bisphenol A and polyol, reacting for 50-70min to form hydroxyl end-capped resin, and cooling to 50-70 ℃;
s3: adding isocyanate ethyl acrylate which is 0.9-1.10 times of the total mole of hydrogenated bisphenol A and polyalcohol into the hydroxyl end-capped resin, and reacting for 100-150min;
s4: adding hydroquinone with the mol content of 0.05-0.10% of isocyanate ethyl acrylate, and reacting to obtain the acrylic ester end-capped flexible acrylic resin.
The epoxy resin has the advantages of low curing shrinkage, strong adhesive force and the like, but the epoxy resin curing system has higher crosslinking density and large brittleness, and limits the application of the epoxy resin. The invention uses the epoxy resin to compound with the synthetic flexible acrylic resin, then adds the synthetic toughening resin, and then is assisted with the components such as filler, reactive diluent, photoinitiator, and the like, so that the obtained product has good mechanical property, good bonding effect on aluminum materials, good mechanical strength and toughness, delayed curing, solvent erosion resistance, low shrinkage, stable electrochemical performance, good impact shock resistance, and good insulation and protection performance, can be applied to pole piece edge insulation protection by matching with the corresponding sizing and curing process, and can replace the existing process for coating polyvinylidene fluoride (PVDF).
The flexible acrylic resin is a hydroxyl-terminated resin formed by reacting hydrogenated bisphenol A, polyalcohol and isocyanate according to a certain proportion, and then adding isocyanate ethyl acrylate and hydroquinone to react to form the acrylic ester-terminated resin. Compared with other acrylic resins, the synthesized flexible acrylic resin has the effects of small shrinkage, good toughness and tolerance to electrolyte soaking. The specific structural formula is as follows:
further, the epoxy resin is selected from at least one, preferably a combination of two, of bisphenol a epoxy resin, bisphenol F epoxy resin, and cycloaliphatic epoxy resin; the reactive diluent is at least one selected from glycidyl ether and oxetane; the adhesion promoter is a phosphate acrylate.
The amount of reactive diluent used has a large effect on the cure speed. When the weight part of the reactive diluent is less than 10 parts, the viscosity of the system is high, the movement difficulty of materials such as various reactive groups, initiator and the like is high, and the curing speed is limited and difficult to regulate and control; when the content of the reactive diluent is more than 20 parts, the curing reaction is also easily inhibited, but the reactive diluent itself has a certain reactivity, but the reactivity is lower than that of the epoxy resin, and the addition of a large amount of the reactive diluent causes a decrease in the ratio of the epoxy resin in the resin system, so that the reactivity of the whole resin system is decreased, and the curing reaction rate of the resin system is decreased. Therefore, the content of the reactive diluent is selected to be 10-20 parts, so that the viscosity of the system is moderate, and the regulation and control of the curing speed are not excessively hindered.
Considering the degree and the speed of UV light pre-curing, the content of the photoinitiator is selected to be 1-5 parts, so that the pre-curing efficiency can be ensured, and the pre-curing degree can be conveniently adjusted. Within this range, as the content of the photoinitiator increases, the pre-curing speed increases, and the pre-curing degree of the resin system under the same curing conditions tends to increase. When the content is less than 1 part, the UV light pre-curing takes longer time, which is unfavorable for the improvement of the production efficiency. However, when the content is more than 5 parts, the active points generated after illumination are obviously increased, which easily causes uncontrollable pre-curing rate and excessively high curing degree, and is not beneficial to the regulation and control of subsequent winding and post curing. Furthermore, too high a photoinitiator content leads to excessive residues in the resin with the risk of degrading the glue properties.
Further, the photoinitiator is compounded by adopting a free radical photoinitiator and a cationic photoinitiator according to the mass ratio of 1 (0.8-1.5); the free radical photoinitiator is an acetophenone photoinitiator; the cationic photoinitiator is hexafluoroantimonate. For photo-pre-curing, the present invention uses in particular a combination of free radical photoinitiators and cationic photoinitiator formulations. Because the initiation speed of free radical polymerization is high, but the reaction light is stopped, the invention uses short-time light to pre-cure the free radical to carry out the quick viscoelastization of the surface. The cationic photoinitiation speed is lower than that of the free radical initiator, but the photoinitiation dependency is lower, the photoinitiation can be continued even though the ultraviolet irradiation is lacking later, the overall curing speed and degree can be effectively improved by matching with the curing after rolling, and the energy consumption is saved. In the invention, the advantages of UV light pre-curing are utilized, but the defects that the curing speed of a single free radical initiator is too high and the single free radical initiator is influenced by illumination, the initiation speed of a single cation initiator is slower and the like are avoided, the pre-curing speed and degree can be effectively regulated, the winding process is not influenced, the peripheral parts are not easy to pollute, and the impurity mixing can be avoided to reduce the protection performance.
Further, the toughening resin is prepared by the following method:
s1: melting hydrogenated bisphenol A at 160-175 ℃ for dewatering, and cooling to 100-130 ℃;
s2: dripping isocyanate with the molar content of 1.80-2.2 times of hydrogenated bisphenol A for reaction;
s3: adding polyol with the same molar content as isocyanate for reaction, wherein the molecular weight of the polyol is 1300-2100;
s4: heating to 160-175 ℃, discharging to obtain the hydroxyl-terminated toughened resin.
Further, the polyol is at least one selected from Polytetrahydrofuran (PTMEG), tetrahydrofuran copolyether glycol (3 MCPG), polypropylene glycol (PPG) and polyethylene glycol (PEG); the isocyanate is at least one selected from Hexamethylene Diisocyanate (HDI), dicyclohexylmethane diisocyanate (HMDI) and isophorone diisocyanate (IPDI).
Specifically, the invention mainly synthesizes two toughening resins.
For the toughening resin I, dicyclohexylmethane diisocyanate (HMDI) is selected as isocyanate, and 3MCPG is selected as polyol. The preparation method of the toughening resin I preferably comprises the following steps:
melting hydrogenated bisphenol A at 170 ℃ for water removal for 1 hour, then cooling to 120 ℃, slowly dropwise adding HMDI with the molar content of 1.80-2.2 times of the hydrogenated bisphenol A, reacting for 60 minutes after finishing, adding 3MCPG (with the molecular weight of about 1400) with the same molar content as the HMDI, reacting for 60 minutes, and then heating to 170 ℃ for discharging to obtain toughened resin I, wherein the structural formula is as follows:
and the toughening resin II adopts Hexamethylene Diisocyanate (HDI) as isocyanate and adopts PPG as polyol. The preparation method of the toughening resin II preferably comprises the following steps:
melting hydrogenated bisphenol A at 170 ℃ for dewatering for 1 hour, then cooling to 120 ℃, slowly dropwise adding HDI with the molar content of 1.80-2.2 times of that of the hydrogenated bisphenol A, reacting for 60 minutes after finishing, adding PPG (with the molecular weight of about 2000) with the molar content of the HDI, reacting for 60 minutes, and then heating to 170 ℃ for discharging to obtain toughened resin II, wherein the structural formula is as follows:
the toughening resin synthesized by the invention is a hydroxyl-terminated polyol toughening agent formed by reacting hydrogenated bisphenol A, polyol and isocyanate in a certain content ratio. Compared with other toughening resins, the synthesized toughening resin has the effects of high adhesion, good toughness and electrolyte soaking resistance.
Further, the filler is at least one selected from boehmite, alumina and boron nitride; the filler is subjected to surface treatment, and comprises the following steps:
s1: carrying out plasma surface treatment on the filler, controlling the electron energy to be 1-10eV, and the gas flux to be 0.5-5L/min, wherein the treatment time is 1-5min;
s2: introducing the filler subjected to plasma surface treatment into a silane coupling agent solution with the weight percentage of 2-5%, and treating for 2-4 hours at 50-80 ℃;
s3: filtering, washing with absolute ethanol for 2-4 times, and vacuum drying for 1.5-2 h.
The UV delay type glue disclosed by the invention contains insulating filler with a large proportion and has excellent positive pole piece edge insulating protection performance. The surface of the filler is activated by adopting plasma, so that a large number of hydroxyl/carboxyl active groups and the like are generated on the surface of the filler, the surface polarity is enhanced, the surface wetting tension is improved, the potential energy of the surface of the filler can be improved by at least 1 order of magnitude, and the bonding energy barrier of the subsequent modified material or matrix resin and the surface of the filler is obviously reduced; and after the electron impact, the surface of the filler generates a miniature dense recess, thereby achieving the effect of roughening the surface to improve the surface activity. In addition, the cleanliness of the filler can be improved, and the combination firmness of the follow-up modified materials and the like and the filler can be improved.
The silane coupling agent has outstanding modifying effect on the surfaces of inorganic particles, can improve the dispersibility of the inorganic particles and the adhesive property of the inorganic particles and matrix resin, and greatly improves the comprehensive properties of the composite material, such as uniformity, mechanical property, heat resistance, weather resistance and the like. Through the above treatment, the filler has good matrix compatibility, shows excellent dispersion uniformity, and can fully exert the advantages of insulation and the like, although the filler is used in a large amount.
On the other hand, the preparation method of the anode plate UV delay type glue comprises the following steps:
step one: uniformly stirring epoxy resin, flexible acrylic resin and toughening resin at 50+/-3 ℃ for 30-60 min;
step two: adding active diluent, stirring at 50+ -3deg.C for 30-60min, and cooling to room temperature;
step three: adding filler, stirring for 30-60 min;
step four: adding adhesion promoter and photoinitiator, and vacuum stirring at room temperature for 20-40min until no bubbles.
The filler can be added in batches to be fully mixed and infiltrated with the resin, so that the high-performance glue with good uniformity and stability is formed.
In a third aspect, a protection method for applying the positive electrode piece UV delay glue to edge insulation protection of a positive electrode piece of a lithium battery is provided, including the following steps:
s1: coating glue with the thickness of 20-40 mu m on the edge of the positive electrode plate of the lithium battery;
s2: pre-curing the glue by UV light irradiation, wherein the curing degree is 40-60%;
s3: cutting and winding by laser; the glue is cured after being rolled by the heat released by laser cutting.
In the invention, the pre-curing degree is 40-60%, the colloid has certain body strength, the surface no longer presents pressure sensitivity, and the surfaces can not be adhered to each other or foreign objects, thereby being beneficial to later laser cutting and winding.
The invention can accurately control the pre-curing degree by tracking the curing process through real-time infrared spectrum, thereby grasping the pre-curing degree through the pre-curing time. When infrared light passes through the sample, different groups in the colloid selectively absorb infrared light with different wavelengths, and epoxy groups (about 913cm -1 ) And benzene ring (about 1610 cm) -1 ) Absorbance before and after illumination:
wherein A is absorbance; i 0 And I is the intensity of the incident light and the transmitted light, respectively;
degree of cure of resin system G:
wherein A is 0 And A 0 ' initial absorbance of epoxy group and benzene ring, respectively; a is that t And A t ' is the absorbance of the epoxy group and benzene ring after illumination time t, respectively.
Through the calculation formula, the pre-curing illumination time under the condition of various UV light sources can be accurately obtained, and the insufficient or excessive pre-curing is avoided. The real-time infrared spectrum tracking curing process can be used for on-line monitoring the pre-curing degree, and can also be combined with the calculation formula through a large number of experiments to find out more convenient and practical technical parameter combinations, for example, in particular, when the glue coating thickness is 20-40 mu m, the curing energy is input to 3000-12000mJ/cm 2 Preferably 3000-9000mJ/cm 2 When the distance between the UV light source and the UV light source is 40-60mm, the adjustment mode of the pre-curing speed/time can be the adjustment of the intensity of the curing energy of the UV light irradiation, and the pre-curing degree is adjusted by adjusting the input range of the curing energy of the pre-curing according to the time of the curing energy=the intensity of the light. In the invention, the crosslinking degree of the pre-cured glue is controlled by controlling the curing energy, so that the pre-cured glue meets the requirement of certain initial strength, and the post-curing can be performed to achieve the final protection purpose, thereby being a more convenient control means than real-time infrared spectrum tracking and monitoring.
Optionally, the UV light source is at least one selected from mercury lamp light source, LED light source, xenon lamp light source, preferably 365nm LED light source.
After the edge of the positive pole piece of the lithium battery is coated with the UV delay type glue, UV photo-curing is carried out, and then laser cutting is carried out. Can effectively bond, prevent that glue from coming off in the battery use, improve the security and the reliability of product, can use the coating technology simultaneously, realize automatic rubber coating.
Further, the glue at least has the following properties after curing:
the bonding area is 3mm multiplied by 3mm, the electrolyte is soaked in the environment at 85 ℃ for 500 hours, a thrust machine is used for testing at 6mm/min, and the shearing strength is more than 10Mpa;
soaking in the environment of lithium-containing electrolyte at 85 ℃ for 24 hours, wherein the swelling rate is less than 5%;
the dissolution rate is less than 2 percent after the electrolyte is soaked in the environment of lithium-free electrolyte at 85 ℃ for 24 hours.
The invention has the advantages that:
1) The invention utilizes the UV light curing principle of the UV colloid system to carry out primary curing, provides the initial adhesive force of the glue, meets the process requirement of quick setting, and utilizes the principle that the cationic system light curing agent releases Lewis acid to catalyze the epoxy crosslinking reaction to carry out the post curing of the glue, and has high curing speed and adjustability.
2) The invention utilizes the synthesized toughened epoxy resin and acrylic resin, can effectively reduce the hardness of the cured glue, improve the vibration resistance and impact resistance, greatly improve the bonding strength and ensure the electrolyte soaking resistance.
3) The glue prepared by the method has the advantages of good electrochemical stability, strong adhesion, good adhesion on aluminum foil, electrolyte soaking resistance, no falling off after long-term soaking, low cost, solid content up to 100 percent and environmental protection.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the following detailed description and examples. The types of materials used in the examples are not intended to be exhaustive, and only some materials are selected for illustrative purposes.
In the first aspect, the positive electrode plate UV delay type glue is used for insulating and protecting the edge of the positive electrode plate and comprises the following components:
20-50 parts of epoxy resin
10-15 parts of flexible acrylic resin
40-60 parts of filler
10-30 parts of toughening resin
10-20 parts of reactive diluent
1-3 parts of adhesion promoter
1-5 parts of photoinitiator
The epoxy resin is at least one selected from bisphenol A epoxy resin, bisphenol F epoxy resin and alicyclic epoxy resin; the reactive diluent is at least one selected from glycidyl ether and oxetane; the adhesion promoter is phosphate acrylate; the photoinitiator is compounded by adopting a free radical photoinitiator and a cationic photoinitiator according to the mass ratio of 1 (0.8-1.5), wherein the free radical photoinitiator is an acetophenone photoinitiator, and the cationic photoinitiator is hexafluoroantimonate.
In a second aspect, the preparation method of the positive electrode plate UV delay type glue comprises the following steps:
step 1: preparation of Flexible acrylic resins
S1.1: mixing hydrogenated bisphenol A and polyalcohol in a molar ratio of 1 (0.8-1.2), removing water for 45-75min, and cooling to 100-130deg.C;
s1.2: dripping isocyanate accounting for 40-60% of the total mole of hydrogenated bisphenol A and polyol, reacting for 50-70min to form hydroxyl end-capped resin, and cooling to 50-70 ℃;
s1.3: adding isocyanate ethyl acrylate which is 0.9-1.10 times of the total mole of hydrogenated bisphenol A and polyalcohol into the hydroxyl end-capped resin, and reacting for 100-150min;
s1.4: adding hydroquinone with the molar content of 0.05-0.10% of isocyanate ethyl acrylate, and reacting to obtain acrylic ester end-capped flexible acrylic resin;
step 2: preparation of toughening resin
S2.1: melting hydrogenated bisphenol A at 160-175 ℃ for dewatering, and cooling to 100-130 ℃;
s2.2: dripping isocyanate with the molar content of 1.8-2.2 times of hydrogenated bisphenol A for reaction;
s2.3: adding polyol with the same molar content as isocyanate for reaction, wherein the molecular weight of the polyol is 1300-2100;
s2.4: heating to 160-175 ℃, discharging to obtain hydroxyl-terminated toughened resin;
the polyalcohol is at least one selected from PTMEG and 3MCPG, PPG, PEG; the isocyanate is at least one selected from hexamethylene diisocyanate, dicyclohexylmethane diisocyanate and isophorone diisocyanate.
Specifically, the toughening resin can be selected from a first toughening resin and/or a second toughening resin, and the preparation method of the first toughening resin comprises the following steps:
s2.1-1: melting hydrogenated bisphenol A at 160-175 ℃ for dewatering, and cooling to 100-130 ℃;
s2.2-1: dripping dicyclohexylmethane diisocyanate with the molar content of hydrogenated bisphenol A of 1.8-2.2 times for reaction for 50-75min;
s2.3-1: adding 3MCPG (molecular weight of about 1400) with the same molar content as that of isocyanate for reaction for 50-75min;
s2.4-1: heating to 160-175 ℃, discharging to obtain hydroxyl-terminated toughened resin I;
the preparation method of the toughening resin II comprises the following steps:
s2.1-2: melting hydrogenated bisphenol A at 160-175 ℃ for dewatering, and cooling to 100-130 ℃;
s2.2-2: dripping hexamethylene diisocyanate with the molar content of 1.8-2.2 times of hydrogenated bisphenol A to react for 50-75min;
s2.3-2: adding PPG (molecular weight about 2000) with the same molar content as isocyanate for reaction for 50-75min;
s2.4-2: heating to 160-175 ℃, discharging to obtain hydroxyl-terminated toughened resin I;
step 3: and (3) carrying out surface treatment on a filler, wherein the filler is at least one selected from boehmite, alumina and boron nitride, and comprises the following steps:
s3.1: carrying out plasma surface treatment on the filler, controlling the electron energy to be 1-10eV, and the gas flux to be 0.5-5L/min, wherein the treatment time is 1-5min;
s3.2: introducing the filler subjected to plasma surface treatment into a silane coupling agent solution with the weight percentage of 2-5%, and treating for 2-4 hours at 50-80 ℃;
s3.3: filtering, washing with absolute ethanol for 2-4 times, and vacuum drying for 1.5-2 h;
step 4: uniformly stirring epoxy resin, flexible acrylic resin and toughening resin at 50+/-3 ℃ for 30-60 min;
step 5: adding active diluent, stirring at 50+ -3deg.C for 30-60min, and cooling to room temperature;
step 6: adding filler, stirring for 30-60 min; preferably, the filler is added in batches of 30%, 30% and 40% of the total amount of filler;
step 7: adding adhesion promoter and photoinitiator, and vacuum stirring at room temperature for 20-40min until no bubbles.
In a third aspect, a protection method for protecting edge insulation of a positive electrode plate of a lithium battery by using positive electrode plate UV delay glue includes the following steps:
s1: coating glue with the thickness of 20-40 mu m on the edge of the positive electrode plate of the lithium battery;
s2: pre-curing the glue by UV light irradiation, wherein the curing degree is 40-60%; the UV light source is at least one selected from mercury lamp light source, LED light source, xenon lamp light source, preferably 365An nmLED light source; the curing energy is 3000-12000mJ/cm 2 Preferably 3000-9000mJ/cm 2 ；
S3: cutting and winding by laser; the glue is cured after being rolled by the heat released by laser cutting.
After the glue is solidified, the glue has at least the following properties:
the bonding area is 3mm multiplied by 3mm, the electrolyte is soaked in the environment at 85 ℃ for 500 hours, a thrust machine is used for testing at 6mm/min, and the shearing strength is more than 10Mpa;
soaking in the environment of lithium-containing electrolyte at 85 ℃ for 24 hours, wherein the swelling rate is less than 5%;
the dissolution rate is less than 2 percent after the electrolyte is soaked in the environment of lithium-free electrolyte at 85 ℃ for 24 hours.
Example 1
The anode plate UV delay type glue comprises the following components:
40 parts of epoxy resin
10 parts of flexible acrylic resin
Alumina 50 parts
10 parts of toughening resin
Glycidyl ether 10 parts
Phosphate acrylate 1 part
4 parts of photoinitiator
Wherein, in the epoxy resin, the mass ratio of bisphenol A epoxy resin to bisphenol F epoxy resin is 3:1; in the photoinitiator, the free radical photoinitiator and the cationic photoinitiator are compounded according to the mass ratio of 1:1, wherein the free radical photoinitiator is acetophenone photoinitiator, and the cationic photoinitiator is hexafluoroantimonate.
The preparation method of the anode plate UV delay type glue comprises the following steps:
step 1: preparation of Flexible acrylic resins
S1.1: melting and mixing 1mol of hydrogenated bisphenol A and 1mol of PTMEG, removing water for 60min, and cooling to 120 ℃;
s1.2: dropwise adding 1mol of hexamethylene diisocyanate, reacting for 60min to form hydroxyl-terminated resin, and cooling to 60 ℃;
s1.3: adding 2mol of isocyanate ethyl acrylate into the hydroxyl end-capped resin, and reacting for 120min;
s1.4: adding hydroquinone with the molar content of 0.08% of isocyanate ethyl acrylate, and reacting to obtain acrylic ester-terminated flexible acrylic resin;
step 2: preparation of toughened resin one
S2.1: melting 1mol of hydrogenated bisphenol A at 170 ℃ to remove water, and cooling to 120 ℃;
s2.2: 2mol dicyclohexylmethane diisocyanate is added dropwise for reaction for 60min;
s2.3: 2mol of 3MCPG (molecular weight about 1400) was added to carry out the reaction for 60min;
s2.4: heating to 170 ℃, discharging to obtain hydroxyl-terminated toughened resin I;
step 3: the surface treatment of alumina comprises the following steps:
s3.1: carrying out plasma surface treatment on aluminum oxide, controlling electron energy to be 5eV, and gas flux to be 3L/min, wherein the treatment time is 3min;
s3.2: introducing the filler subjected to plasma surface treatment into a silane coupling agent solution with the weight percentage of 2-5%, and treating for 3 hours at 70 ℃;
s3.3: filtering and washing with absolute ethyl alcohol for 3 times, and vacuumizing and drying 2 h;
step 4: uniformly stirring epoxy resin, flexible acrylic resin and toughening resin at 50 ℃ for 40 min;
step 5: adding active diluent, stirring at 50deg.C for 50min, and cooling to room temperature;
step 6: adding the filler in batches in a mode of 30%, 30% and 40% of the total amount of the filler, and uniformly stirring for 45 min;
step 7: adding the adhesion promoter and the photoinitiator, and stirring at room temperature under vacuum for 30min until no bubbles exist.
The protection method for the lithium battery positive electrode plate edge insulation protection by using the positive electrode plate UV delay type glue comprises the following steps:
s1: coating glue with the thickness of 25 mu m on the edge of the positive electrode plate of the lithium battery;
s2: solidifying the surface layer of the glue by using 365nm LED light sourceThe curing energy is 6000mJ/cm 2 And the overall solidification degree of the glue is 50%;
s3: cutting and winding by laser; the glue is cured after being rolled by the heat released by laser cutting.
Example 2
The main difference between this example and example 1 is that toughening resin two is used as the toughening resin.
Step 2: preparation of toughened resin II
S2.1: melting 1mol of hydrogenated bisphenol A at 170 ℃ to remove water, and cooling to 120 ℃;
s2.2: 2mol of hexamethylene diisocyanate is added dropwise for reaction for 60min;
s2.3: 2mol of PPG (molecular weight about 2000) was added to carry out the reaction for 60 minutes;
s2.4: heating to 170 ℃, discharging to obtain the hydroxyl-terminated toughened resin II.
Example 3
In this example, the parts of the flexible acrylic resin were different from those of example 1, specifically:
the anode plate UV delay type glue comprises the following components:
40 parts of epoxy resin
15 parts of flexible acrylic resin
Alumina 50 parts
10 parts of toughening resin
Glycidyl ether 10 parts
Phosphate acrylate 1 part
4 parts of photoinitiator
Wherein the mass ratio of bisphenol A epoxy resin to bisphenol F epoxy resin in the epoxy resin is 3:1; the free radical photoinitiator and the cationic photoinitiator in the photoinitiator are compounded according to the mass ratio of 1:1, wherein the free radical photoinitiator is acetophenone photoinitiator, and the cationic photoinitiator is hexafluoroantimonate.
Example 4
In this example, the parts of the flexible acrylic resin were different from those of example 2, specifically:
the anode plate UV delay type glue comprises the following components:
40 parts of epoxy resin
15 parts of flexible acrylic resin
Alumina 50 parts
Toughening resin II 10 parts
Glycidyl ether 10 parts
Phosphate acrylate 1 part
4 parts of photoinitiator
Wherein the mass ratio of bisphenol A epoxy resin to bisphenol F epoxy resin in the epoxy resin is 3:1; the free radical photoinitiator and the cationic photoinitiator in the photoinitiator are compounded according to the mass ratio of 1:1, wherein the free radical photoinitiator is acetophenone photoinitiator, and the cationic photoinitiator is hexafluoroantimonate.
Example 5
In this example, compared with example 4, the number of parts of the toughening resin two is different, specifically:
the anode plate UV delay type glue comprises the following components:
40 parts of epoxy resin
15 parts of flexible acrylic resin
Alumina 50 parts
Toughened resin II 20 parts
Glycidyl ether 10 parts
Phosphate acrylate 1 part
4 parts of photoinitiator
Wherein the mass ratio of bisphenol A epoxy resin to bisphenol F epoxy resin in the epoxy resin is 3:1; the free radical photoinitiator and the cationic photoinitiator in the photoinitiator are compounded according to the mass ratio of 1:1, wherein the free radical photoinitiator is acetophenone photoinitiator, and the cationic photoinitiator is hexafluoroantimonate.
Example 6
In this example, the epoxy resin composition was different from that of example 5, specifically:
the anode plate UV delay type glue comprises the following components:
40 parts of epoxy resin
15 parts of flexible acrylic resin
Alumina 50 parts
Toughened resin II 20 parts
Glycidyl ether 10 parts
Phosphate acrylate 1 part
4 parts of photoinitiator
Wherein the mass ratio of bisphenol A epoxy resin to alicyclic epoxy resin in the epoxy resin is 3:1; the free radical photoinitiator and the cationic photoinitiator in the photoinitiator are compounded according to the mass ratio of 1:1, wherein the free radical photoinitiator is acetophenone photoinitiator, and the cationic photoinitiator is hexafluoroantimonate.
Comparative example 1
The anode plate UV glue comprises the following components:
40 parts of epoxy resin
Alumina 50 parts
15 parts of CTBN toughening resin
Glycidyl ether 10 parts
Cationic photoinitiator 2 parts
Wherein the mass ratio of bisphenol A epoxy resin to bisphenol F epoxy resin in the epoxy resin is 3:1; the photoinitiator only comprises a cationic photoinitiator and is hexafluoroantimonate.
The preparation method of the glue comprises the following steps: adding 30 parts of bisphenol A epoxy resin, 10 parts of bisphenol F epoxy resin, 15 parts of CTBN toughening resin (carboxyl-terminated polybutadiene acrylonitrile toughening resin) and 10 parts of glycidyl ether into a double-planetary stirrer, stirring at room temperature for 30-60min till uniformity, adding 50 parts of aluminum oxide, stirring at room temperature for 30-60min till uniformity, finally adding 2 parts of cationic photoinitiator, and stirring at room temperature under vacuum for 30min till no bubbles.
Comparative example 2
Comparative example 2 differs from example 1 in that the content of the flexible acrylic resin and the toughening resin is low, and includes the following components:
40 parts of epoxy resin
Flexible acrylic resin 5 parts
Alumina 50 parts
5 parts of toughening resin
Glycidyl ether 10 parts
Phosphate acrylate 1 part
4 parts of photoinitiator
Wherein the mass ratio of bisphenol A epoxy resin to bisphenol F epoxy resin in the epoxy resin is 3:1; the free radical photoinitiator and the cationic photoinitiator in the photoinitiator are compounded according to the mass ratio of 1:1, wherein the free radical photoinitiator is acetophenone photoinitiator, and the cationic photoinitiator is hexafluoroantimonate.
Comparative example 3
Comparative example 3 is different from example 1 in that the protection method of the positive electrode sheet UV delay type glue for the edge insulation protection of the positive electrode sheet of the lithium battery is specifically as follows:
the protection method for the lithium battery positive electrode plate edge insulation protection by using the positive electrode plate UV delay type glue comprises the following steps:
s1: coating glue with the thickness of 10 mu m on the edge of the positive electrode plate of the lithium battery;
s2: irradiating with 365nm LED light source to pre-cure the glue with curing energy of 2000mJ/cm 2， And the overall solidification degree of the glue is 30%;
s3: cutting and winding by laser; the glue is cured after being rolled by the heat released by laser cutting.
Because the pre-curing degree is low, the surface of the glue sample of the comparative example 3 has certain pressure sensitivity, and the glue sample is mutually adhered during rolling, so that the problem that the glue sample cannot be unrolled again is caused.
The compositions of the materials of examples 1-6 and comparative examples 1-3 are shown in Table 1:
table 1 examples 1-6 and comparative examples 1-3 materials composition table
Performance testing
1) Shear strength: sample is prepared by a chip shearing method, the bonding area 3mm*3mm,365mm LED is illuminated by a light source, and the illumination energy is 3000mJ/cm 2 And (3) testing after curing at 105 ℃ for 1h, testing by a Dage chip pusher, and bonding glass with aluminum at a speed of 6 mm/min.
2) Hardness: the glue is prepared into a light source with the thickness of 6mm and 365mm, and the irradiation energy is 9000mJ/cm 2 And (5) curing at 105 ℃ for 1h, and testing by using a Shore durometer.
3) Swelling ratio: 2.0+ -0.05 g of glue is irradiated by 365mm LED light source with 6000mJ/cm energy 2 After curing for 1h at 105 ℃, the mixture is put into a PP cup for sealing, 50+/-0.5 g of lithium-containing electrolyte is added, the mixture is placed in an oven at 85 ℃ for 24h, and the mixture is taken out and is wiped dry for weighing, and the weight difference before and after the experiment is equal to the percentage of the initial weight.
4) Dissolution rate: extruding 1.4+ -0.05 g of the glue, irradiating with 365mm LED light source, and irradiating with energy of 6000mJ/cm 2 After curing for 1h at 105 ℃, placing the solution into a penicillin bottle for sealing, adding 7+/-0.1 g of lithium-free electrolyte, placing the solution in an oven at 85 ℃ for 24h, taking out the solution, extracting the solution while the solution is hot by using a syringe, testing the mass fraction of solute in the solution by using TGA, calculating the mass of solute in the whole solution, and looking at the percentage of the mass of solute to the initial weight.
5) Bending test: coating the glue into a glue film with the length of 8-10 cm and the thickness of 20-30 um, illuminating with 365mm LED light source, and illuminating with energy of 6000mJ/cm 2 After curing for 1h at 105 ℃, continuous folding test is carried out until the glue is broken.
6) And (3) soaking liquid test: sample is prepared by a chip shearing method, the bonding area 3mm*3mm,365mm LED is illuminated by a light source, and the illumination energy is 3000mJ/cm 2 Solidifying at 105 ℃ for 1h, then placing in an electrolyte environment at 85 ℃ for soaking for 500h, taking out, volatilizing water, cooling to room temperature, testing by a Dage chip pusher, testing at a speed of 6mm/min, and bonding glass with aluminum.
7) And (3) liquid resistance test: the batteries prepared in the above examples and comparative examples were continuously aged at 85 ℃ for 500H after electrolyte was added from the liquid inlet to the sealed case, and the battery was disassembled after aging to remove the glue.
The above examples 1-6 were compared with comparative examples 1-3, and the specific results are shown in Table 2:
TABLE 2 results of Performance test for examples 1-6 and comparative examples 1-3
The foregoing description of the preferred embodiments of the present invention has been presented for purposes of clarity and understanding, and is not intended to limit the invention to the particular embodiments disclosed, but is intended to cover all modifications, alternatives, and improvements within the spirit and scope of the invention as outlined by the appended claims.
Claims (9)
1. The anode plate UV delay type glue is used for insulating and protecting the edge of an anode plate and is characterized by comprising the following components in parts by weight:
20-50 parts of epoxy resin
10-15 parts of flexible acrylic resin
40-60 parts of filler
10-30 parts of toughening resin
10-20 parts of reactive diluent
1-3 parts of adhesion promoter
1-5 parts of photoinitiator
The flexible acrylic resin is prepared by the following method:
s1: mixing hydrogenated bisphenol A and polyalcohol in a molar ratio of 1 (0.8-1.2), removing water for 45-75min, and cooling to 100-130deg.C;
s2: dripping isocyanate accounting for 40-60% of the total mole of hydrogenated bisphenol A and polyol, reacting for 50-70min to form hydroxyl end-capped resin, and cooling to 50-70 ℃;
s3: adding isocyanate ethyl acrylate which is 0.9-1.10 times of the total mole of hydrogenated bisphenol A and polyalcohol into the hydroxyl end-capped resin, and reacting for 100-150min;
s4: adding hydroquinone with the molar content of 0.05-0.10% of isocyanate ethyl acrylate, and reacting to obtain acrylic ester end-capped flexible acrylic resin;
the toughening resin is prepared by the following method:
s1: melting hydrogenated bisphenol A at 160-175 ℃ for dewatering, and cooling to 100-130 ℃;
s2: dripping isocyanate with the molar content of 1.8-2.2 times of hydrogenated bisphenol A for reaction;
s3: adding polyol with the same molar content as isocyanate for reaction, wherein the molecular weight of the polyol is 1300-2100;
s4: heating to 160-175 ℃, discharging to obtain hydroxyl-terminated toughened resin;
the protection method for using the anode plate UV delay type glue for the edge insulation protection of the anode plate of the lithium battery comprises the following steps:
s1: coating glue with the thickness of 20-40 mu m on the edge of the positive electrode plate of the lithium battery;
s2: pre-curing the glue by UV light irradiation, wherein the curing degree is 40-60%;
s3: cutting and winding by laser; the glue is cured after being rolled by the heat released by laser cutting.
2. The glue of claim 1, wherein the epoxy resin is selected from at least one of bisphenol a epoxy resin, bisphenol F epoxy resin, and cycloaliphatic epoxy resin; the reactive diluent is at least one selected from glycidyl ether and oxetane; the adhesion promoter is a phosphate acrylate.
3. Glue according to claim 1 or 2, wherein the photoinitiator is formulated with a mass ratio of 1 (0.8-1.5) by means of a free radical photoinitiator and a cationic photoinitiator; the free radical photoinitiator is an acetophenone photoinitiator; the cationic photoinitiator is hexafluoroantimonate.
4. The glue of claim 3, wherein the polyol is selected from at least one of PTMEG, 3MCPG, PPG, PEG; the isocyanate is at least one selected from hexamethylene diisocyanate, dicyclohexylmethane diisocyanate and isophorone diisocyanate.
5. A glue according to claim 3, wherein the filler is selected from at least one of boehmite, alumina, boron nitride; the filler is subjected to surface treatment, and comprises the following steps:
s1: carrying out plasma surface treatment on the filler, controlling the electron energy to be 1-10eV, and the gas flux to be 0.5-5L/min, wherein the treatment time is 1-5min;
s2: introducing the filler subjected to plasma surface treatment into a silane coupling agent solution with the weight percentage of 2-5%, and treating for 2-4 hours at 50-80 ℃;
s3: filtering, washing with absolute ethanol for 2-4 times, and vacuum drying for 1.5-2 h.
6. A method for preparing the positive electrode sheet UV-delay glue as claimed in any one of claims 1 to 5, comprising the steps of:
step one: uniformly stirring epoxy resin, flexible acrylic resin and toughening resin at 50+/-3 ℃ for 30-60 min;
step two: adding active diluent, stirring at 50+ -3deg.C for 30-60min, and cooling to room temperature;
step three: adding filler, stirring for 30-60 min;
step four: adding the adhesion promoter and the photoinitiator, and stirring at room temperature under vacuum for 20-40min.
7. A protection method for using the positive electrode sheet UV delay glue of any one of claims 1 to 5 for edge insulation protection of a positive electrode sheet of a lithium battery, comprising the steps of:
s1: coating glue with the thickness of 20-40 mu m on the edge of the positive electrode plate of the lithium battery;
s2: pre-curing the glue by UV light irradiation, wherein the curing degree is 40-60%;
s3: cutting and winding by laser; the glue is cured after being rolled by the heat released by laser cutting.
8. The method of claim 7, wherein the pre-curing energy is in the range of 3000 to 12000mJ/cm 2 。
9. The protection method according to claim 7 or 8, wherein the glue has the following properties after curing: the shearing strength is more than 10Mpa, the swelling rate is less than 5%, and the dissolution rate is less than 2%.
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Address after: Room 209, Floor 2, Building 2, Shengchuang Science Park, No. 7, Weipu Road, Suzhou Industrial Park, Jiangsu 215127 Patentee after: Tuodi New Materials (Suzhou) Co.,Ltd. Patentee after: Tuodi Chemical (Shanghai) Co.,Ltd. Address before: Room 209, Floor 2, Building 2, Shengchuang Science Park, No. 7, Weipu Road, Suzhou Industrial Park, Jiangsu 215127 Patentee before: Tuodi New Materials (Suzhou) Co.,Ltd. Patentee before: TUODI CHEMICAL (SHANGHAI) Co.,Ltd. |
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