CN115717046B - New energy battery sealing UV adhesive and preparation method and sealing method thereof - Google Patents
New energy battery sealing UV adhesive and preparation method and sealing method thereof Download PDFInfo
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- CN115717046B CN115717046B CN202310022296.6A CN202310022296A CN115717046B CN 115717046 B CN115717046 B CN 115717046B CN 202310022296 A CN202310022296 A CN 202310022296A CN 115717046 B CN115717046 B CN 115717046B
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- 238000007789 sealing Methods 0.000 title claims abstract description 125
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 66
- 239000000853 adhesive Substances 0.000 title claims abstract description 65
- 238000000034 method Methods 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title description 15
- 229920005989 resin Polymers 0.000 claims abstract description 55
- 239000011347 resin Substances 0.000 claims abstract description 55
- 239000003822 epoxy resin Substances 0.000 claims abstract description 28
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 28
- 239000003292 glue Substances 0.000 claims abstract description 26
- 239000012948 isocyanate Substances 0.000 claims abstract description 25
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 25
- 239000003085 diluting agent Substances 0.000 claims abstract description 20
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 18
- 229920000570 polyether Polymers 0.000 claims abstract description 18
- 229920005862 polyol Polymers 0.000 claims abstract description 18
- 150000003077 polyols Chemical class 0.000 claims abstract description 18
- 238000001816 cooling Methods 0.000 claims abstract description 16
- 238000011417 postcuring Methods 0.000 claims abstract description 15
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims abstract description 13
- 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 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- 239000004842 bisphenol F epoxy resin Substances 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 125000002723 alicyclic group Chemical group 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 238000001723 curing Methods 0.000 claims description 89
- 238000003756 stirring Methods 0.000 claims description 23
- 239000003792 electrolyte Substances 0.000 claims description 20
- 239000011248 coating agent Substances 0.000 claims description 13
- 238000000576 coating method Methods 0.000 claims description 13
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 11
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims description 10
- -1 alkyl sulfonium salt Chemical class 0.000 claims description 10
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 10
- 238000003825 pressing Methods 0.000 claims description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 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 6
- 239000000565 sealant Substances 0.000 claims description 6
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 5
- 238000004090 dissolution Methods 0.000 claims description 5
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 5
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 4
- 229920001451 polypropylene glycol Polymers 0.000 claims description 4
- 230000008961 swelling Effects 0.000 claims description 4
- OLPZCIDHOZATMA-UHFFFAOYSA-N 2,2-dioxooxathiiran-3-one Chemical compound O=C1OS1(=O)=O OLPZCIDHOZATMA-UHFFFAOYSA-N 0.000 claims description 3
- 125000005520 diaryliodonium group Chemical group 0.000 claims description 3
- 239000012954 diazonium Substances 0.000 claims description 3
- 150000001989 diazonium salts Chemical class 0.000 claims description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 3
- 229910052753 mercury Inorganic materials 0.000 claims description 3
- AHHWIHXENZJRFG-UHFFFAOYSA-N oxetane Chemical compound C1COC1 AHHWIHXENZJRFG-UHFFFAOYSA-N 0.000 claims description 3
- 125000005409 triarylsulfonium group Chemical group 0.000 claims description 3
- 229910052724 xenon Inorganic materials 0.000 claims description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 3
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- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 5
- 239000012975 dibutyltin dilaurate Substances 0.000 description 5
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- 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 4
- 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 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 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 4
- 229920002334 Spandex Polymers 0.000 description 4
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- 238000002835 absorbance Methods 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 125000003700 epoxy group Chemical group 0.000 description 4
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
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- 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
- 230000009257 reactivity Effects 0.000 description 3
- 239000002893 slag Substances 0.000 description 3
- BJZYYSAMLOBSDY-QMMMGPOBSA-N (2s)-2-butoxybutan-1-ol Chemical compound CCCCO[C@@H](CC)CO BJZYYSAMLOBSDY-QMMMGPOBSA-N 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- MPIZVHPMGFWKMJ-AKGZTFGVSA-N L-alpha-(methylidenecyclopropyl)glycine Chemical compound OC(=O)[C@@H](N)C1CC1=C MPIZVHPMGFWKMJ-AKGZTFGVSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- 239000012790 adhesive layer Substances 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 229910000278 bentonite Inorganic materials 0.000 description 2
- 239000000440 bentonite Substances 0.000 description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
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- 238000009472 formulation Methods 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
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- 238000003475 lamination Methods 0.000 description 2
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- 229920000098 polyolefin Polymers 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 239000012745 toughening agent Substances 0.000 description 2
- 229910013870 LiPF 6 Inorganic materials 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
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- 229910045601 alloy Inorganic materials 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
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- 229940049954 penicillin Drugs 0.000 description 1
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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
- Sealing Battery Cases Or Jackets (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The new energy battery sealing UV glue comprises the following components in parts by weight: 47-70 parts of epoxy resin, 10-40 parts of toughening resin, 10-20 parts of reactive diluent and 0.1-0.5 part of photoinitiator, wherein the epoxy resin is at least one selected from bisphenol A epoxy resin, bisphenol F epoxy resin and alicyclic epoxy resin; the toughening resin is prepared by the following method: s1: melt mixing hydrogenated bisphenol A with polyether polyol; s2: dewatering and cooling; s3: dropping isocyanate for reaction; s4: and heating to obtain the hydroxyl-terminated toughened resin. The UV adhesive provided by the invention effectively realizes the adhesion and sealing of a new energy battery through UV light pre-curing and heating post-curing, has good comprehensive performances such as solvent corrosion resistance, impact shock resistance and the like, is adjustable in curing speed and degree, and improves the safety and reliability of products.
Description
Technical Field
The invention belongs to the technical field of adhesives for batteries, in particular to a UV (ultraviolet) light pre-curing and heating post-curing adhesive, and particularly relates to a new energy battery sealing UV adhesive, a preparation method and a sealing method thereof.
Background
At present, the new energy power battery is mainly divided into three major categories of square batteries, cylindrical batteries and soft package batteries, wherein the square batteries comprise a top cover, a shell, a positive plate, a negative plate and a lamination or winding piece, an insulating piece, a safety component and the like which are formed by a diaphragm, the top cover and the shell are assembled together in a welding mode to wrap other internal materials of the battery cell, and the welding mode has the advantages of high strength, high speed and simpler process, but still has some problems: firstly, welding slag is easy to generate in the preparation process, and the welding slag enters the battery core to puncture the diaphragm, so that short circuit is caused, and spontaneous combustion of the battery is caused; secondly, the part of the positions cannot be effectively bonded due to the cold joint, and the risk of leakage of the internal electrolyte exists; thirdly, dust or impurities on the shell or the top cover easily cause explosion points during welding, tiny holes exist at the positions, and the risk of leakage of the electrolyte in the inner part exists; in addition, partial positions are excessively welded, so that the welding is penetrated, the risk of leakage of the internal electrolyte exists, and the risk that welding slag falls into the battery cell exists.
The use of glue to encapsulate the battery is currently a more common alternative. Patent CN113512366a discloses a curing glue, a battery, an electronic device and a packaging method of the battery, wherein the curing glue comprises, by mass, 15-24 parts of low-melting resin, 7-19 parts of epoxy resin, 1.8-3.0 parts of free radical initiator and 0.5-1.0 part of cationic initiator; the melting point of the low-melting point resin is 90-160 ℃. The invention can package the battery under the low temperature and low pressure condition, the pressure applied to the battery is small, and the damage to electronic components in the battery is small; the packaged battery has good weather resistance and small deformation rate; the curing adhesive has the advantages of low adhesiveness, high curing speed and the like. However, as the battery packaging adhesive, the invention does not pay attention to the solvent resistance of the curing adhesive, the risk of bonding and sealing failure caused by electrolyte leakage exists in the long-term use process, and the mechanical properties and the like of the battery packaging adhesive are still insufficient; in addition, the packaging process of the battery is complex, the controllability is poor, for example, the low-melting-point resin is heated to be in a molten state, and the safety and environmental protection risks exist.
Patent CN115074056a discloses an aluminum-plastic film inner layer adhesive for lithium battery packaging and a preparation method thereof, wherein the adhesive comprises a component a and a component B; the component A comprises: low-melting point polyolefin, anhydride monomer, initiator, auxiliary agent and organic solvent I; the component B comprises: bisphenol A epoxy resin, modified bisphenol A epoxy resin and an organic solvent II; the auxiliary agent is a multifunctional organic small molecule containing triazine ring. The invention uses low-melting point polyolefin as main resin, and adds a small amount of bisphenol A epoxy resin, and simultaneously adds a small amount of multi-functionality organic micromolecules containing triazine ring, thereby obviously improving the bonding strength and electrolyte resistance. However, after the adhesive is coated, the adhesive needs to be cured for 2-5 days at 60-100 ℃ to achieve good curing effect, and the curing efficiency is unfavorable for large-scale industrial production.
Therefore, how to obtain an adhesive for battery sealing with excellent comprehensive performance, high packaging safety and reliability, controllable curing process and simple and convenient operation becomes a technical problem to be solved in the field.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a new energy battery sealing UV adhesive (ultraviolet light curing adhesive and shadowless adhesive) and a preparation method and a sealing method thereof, wherein the UV adhesive is particularly used for new energy square batteries, has excellent comprehensive properties such as bonding effect, sealing property, electrolyte resistance, mechanical property and the like, and has flexible and controllable curing process. The UV adhesive is used for sealing a battery, can effectively prevent electrolyte from leaking, can use an adhesive spraying or dispensing process, is convenient to operate, and can efficiently realize automatic adhesive coating.
Specifically, the invention provides a new energy battery sealing UV adhesive, which comprises the following components in parts by weight:
47-70 parts of epoxy resin
10-40 parts of toughening resin
10-20 parts of reactive diluent
0.1 to 0.5 part of photoinitiator
The epoxy resin is at least one selected from bisphenol A epoxy resin, bisphenol F epoxy resin and alicyclic epoxy resin;
the toughening resin is prepared by the following method:
s1: melt mixing hydrogenated bisphenol A with a polyether polyol having a molecular weight of 1600 to 2200 in a molar ratio of 1 (0.8 to 1.2);
s2: dewatering for 45-75min, and cooling to 100-130deg.C;
s3: dripping isocyanate accounting for 40-60% of the total mole of hydrogenated bisphenol A and polyether polyol for reaction;
s4: and heating to 160-175 ℃ to obtain the hydroxyl-terminated toughened resin.
The epoxy resin is a common photo-curing resin and 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, thereby limiting the application of the epoxy resin curing system. Therefore, the invention particularly adopts the toughening resin to optimize the epoxy system, so that the adhesive has better toughness, can effectively resist vibration or impact, and integrally improves the efficiency of the epoxy resin system in the field of adhesives for battery sealing.
In the preparation of the toughening resin, polyether polyol with molecular weight of 1600-2200 is selected, so that the melt viscosity is not easy to be too high, the high-performance toughening resin can be well melt-mixed, and the polyether polyol has weak molecular polarity and good flexibility of a molecular chain, so that the initial viscosity and strength of a product are reduced, and an adherend is conveniently infiltrated.
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 higher, the movement difficulty of materials such as epoxy groups, initiators 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 0.1-0.5 part, 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 0.1 part, the UV light pre-curing takes longer time, which is disadvantageous for the improvement of the production efficiency. However, when the content is more than 0.5 part, the active points generated after illumination are obviously increased, the reaction rate of the epoxy resin is accelerated, the pre-curing rate is easily uncontrollable, the curing degree is too high, and the regulation and control of post-curing and bonding performance are not facilitated.
Further, the reactive diluent is at least one selected from glycidyl ether and oxetane; the photoinitiator is at least one selected from diazonium salt, diaryl iodonium salt, triarylsulfonium salt, alkyl sulfonium salt, iron arene salt, sulfonyloxy ketone, triarylsiloxane ether and hexafluoroantimonate.
Further, the polyether 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). Compared with other toughening agents, the toughening resin disclosed by the invention is added with an epoxy system in a proper proportion, so that the obtained adhesive has obviously excellent performances such as shear strength and adhesion, has lower hardness, and is particularly suitable for adhesion sealing of new energy batteries.
Through various formulation experiments, the invention preferably provides two toughening resins:
toughening resin one: the polyether polyol is PTMEG and has a molecular weight of 1800-2200; the isocyanate is dicyclohexylmethane diisocyanate; and before dropping the isocyanate, dropping an organotin catalyst with the molar content of 2-3% of the isocyanate. The toughened resin prepared by Polytetrahydrofuran (PTMEG) has the advantages of low viscosity, high functionality, excellent mechanical properties of products and the like.
The structural formula of the toughened resin I obtained by the method is as follows:
toughening resin II: the polyether polyol is 3MCPG and has a molecular weight of 1600-2100; the isocyanate is isophorone diisocyanate; and before dropping the isocyanate, dropping an organotin catalyst with the molar content of 2-3% of the isocyanate. The toughened resin prepared from the tetrahydrofuran copolyether glycol (3 MCPG) has the advantages of low viscosity, high functionality, excellent mechanical properties of products and the like.
The structural formula of the toughened resin II obtained by the method is as follows:
further, the new energy battery sealing UV glue is cured after being pre-cured and heated by UV light, and the cured glue has at least the following properties:
the shear strength is above 20Mpa (the bonding area is 3mm multiplied by 3mm, and the test is carried out by a thrust machine at 6 mm/min);
the swelling rate is less than 5 percent (the lithium-containing electrolyte is placed in an oven at 85 ℃ for 24 hours);
the dissolution rate is less than 1 percent (the solution is placed in a lithium-free electrolyte for 24 hours in an oven at 85 ℃).
The excellent adhesive property, sealing property and solvent resistance are important characteristics of the UV adhesive, and are also key for safely and stably applying the UV adhesive to the field of battery sealing. This is related to various factors such as the content ratio of each component of the UV adhesive.
In a second aspect, the invention further provides a preparation method of the new energy battery sealing UV adhesive, which comprises the following steps:
step one: uniformly stirring the epoxy resin and the 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 the photoinitiator, and stirring at room temperature under vacuum for 20-40min until no bubbles exist.
In a third aspect, a sealing method for sealing UV glue by using the new energy battery is provided, which comprises the following steps:
s1: the sealing surface of the battery shell and the sealing surface of the top cover are respectively coated with the new energy battery sealing UV adhesive, and the coating thickness is 1.0-2.0mm;
s2: pre-curing by irradiation of UV light, wherein the pre-curing degree is 20-40%;
s3: and correspondingly pressing and bonding the sealing surface of the top cover and the sealing surface of the battery shell, and finishing post-curing at 90-115 ℃.
In the invention, the pre-curing degree is 20-40%, the colloid is in a viscoelastic shape, at the moment, the colloid has certain body strength, but the surface of the adhesive layer still has viscosity, the top cover is covered, and certain pressure is applied to ensure that the adhesive is bonded in place. The pressure of press bonding and the curing degree of pre-curing have a certain normal phase relation, the pressure is correspondingly adjusted according to the bonding area, and is generally 0.2-0.3MPa, and the pressure is smaller, so that the damage to the battery shell and the internal electronic components is avoided.
The pre-curing degree is selected according to the bonding requirement. The accurate regulation and control of the pre-curing degree can track the curing process through real-time infrared spectrum, so that the pre-curing degree can be mastered 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, specifically, when the coating thickness of the new energy battery sealing UV adhesive is 1.0-2.0mm, the curing energy is input to 2000-12000mJ/cm 2 Preferably 3000-6000mJ/cm 2 The pre-curing speed is controlled when the distance between the UV light source and the UV light source is 40-60mmThe adjustment mode of time/can be to adjust the adjustment of the curing energy of the UV light irradiation, and the pre-curing degree is adjusted by adjusting the curing energy input range of the pre-curing according to the curing energy = light intensity time. In the invention, the crosslinking degree of the pre-cured glue is controlled by controlling the curing energy, so that the purposes of not only having certain initial strength, but also realizing final adhesion by post-curing are met, and the method is a more convenient control means than real-time infrared spectrum tracking and monitoring.
Further, after the battery shell is sealed by the top cover, electrolyte is injected, and the sealing time is longer than 60 days under the condition of 85 ℃ and 85% humidity; and after the free falling body falls at the height of 1.5m, the sealing time is longer than 60 days under the condition of 85 ℃ and 85% humidity. In the application of sealing the battery top cover, the excellent bonding performance and sealing performance of the UV adhesive fully meet the requirements of various scenes such as battery transportation, use and the like, and the UV adhesive has wider application prospect along with the development and popularization of new energy technology.
The invention has the advantages that:
1. the invention rapidly performs initial fixation through UV illumination, establishes initial strength, has adjustable initial curing degree and curing speed, and can be used for diversifying and matching battery production processes; and meanwhile, the post-curing (or room temperature curing for a prolonged time) can be performed under the heating condition, so that the final strength is achieved, and the satisfactory production quality and efficiency are obtained.
2. The initial adhesive has good liquid fluidity, can realize complete lamination among various special-shaped curved surfaces, has good wettability to the surface of the shell, and does not generate loopholes and pinholes; meanwhile, the glue is a high polymer substance, is not easy to crack and cannot puncture a diaphragm.
3. The new energy battery sealing UV adhesive prepared by the invention has good adhesive force, and can be effectively adhered to a shell without falling off; the alloy has good toughness and can resist vibration or impact; the solvent resistance is good, and the electrolyte is not easy to erode.
4. The new energy battery sealing UV adhesive prepared by the invention has stable high and low temperature performance, can meet the requirements of tightness and reliability in a use temperature environment, and can be used for sealing after the bonding position of the top cover of the new energy square battery and the shell is glued in advance, so that the bonding and sealing can be effectively carried out, the electrolyte is prevented from leaking out in the use process of the battery, the safety and the reliability of the product are improved, and meanwhile, the glue spraying or dispensing process can be used, and the automatic glue coating is realized.
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 examples.
In the first aspect, the new energy battery sealing UV adhesive comprises the following components in parts by weight:
47-70 parts of epoxy resin
10-40 parts of toughening resin
10-20 parts of reactive diluent
0.1 to 0.5 part 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 photoinitiator is at least one selected from diazonium salt, diaryl iodonium salt, triarylsulfonium salt, alkyl sulfonium salt, iron arene salt, sulfonyloxy ketone, triarylsiloxane ether and hexafluoroantimonate.
Wherein the toughening resin is prepared by the following method:
s1: melt mixing hydrogenated bisphenol A with a polyether polyol having a molecular weight of 1600 to 2200 in a molar ratio of 1 (0.8 to 1.2);
s2: dewatering for 45-75min, and cooling to 100-130deg.C;
s3: dripping isocyanate accounting for 40-60% of the total mole of hydrogenated bisphenol A and polyether polyol for reaction;
s4: heating to 160-175 ℃, discharging to obtain the hydroxyl-terminated toughened resin.
The polyether polyol 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.
Tackifying resin one: the polyether polyol is PTMEG and has a molecular weight of 1800-2200; the isocyanate is dicyclohexylmethane diisocyanate; and before dropping the isocyanate, dropping an organotin catalyst with the molar content of 2-3% of the isocyanate.
Tackifying resin II: the polyether polyol is 3MCPG and has a molecular weight of 1600-2100; the isocyanate is isophorone diisocyanate; and before dropping the isocyanate, dropping an organotin catalyst with the molar content of 2-3% of the isocyanate.
In a second aspect, the preparation method of the new energy battery sealing UV adhesive comprises the following steps:
step one: uniformly stirring the epoxy resin and the 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 the photoinitiator, and stirring at room temperature under vacuum for 20-40min until no bubbles exist.
In a third aspect, a sealing method for sealing UV glue by using a new energy battery includes the following steps:
s1: the sealing surface of the battery shell and the sealing surface of the top cover are respectively coated with the new energy battery sealing UV adhesive, and the coating thickness is 1.0-2.0mm;
s2: pre-curing by irradiation of UV light, wherein the pre-curing degree is 20-40%; wherein the UV light source is at least one selected from mercury lamp light source, LED light source and xenon lamp light source, preferably 365nm LED light source, and the pre-curing energy is 2000-12000mJ/cm 2 Preferably 3000-6000mJ/cm 2 Pre-curing to a viscoelastic shape;
s3: correspondingly pressing and bonding the sealing surface of the top cover and the sealing surface of the battery shell, and finishing post-curing at 90-115 ℃; the pressure of the press bonding is preferably 0.2-0.3Mpa.
The new energy battery sealing UV glue is cured after being cured by UV light and heated, and at least has the following properties:
the shear strength is above 20Mpa (bonding area is 3mm multiplied by 3 m)m, glue layer thickness 0.1~0.2mm,365mm LED light source illumination, irradiation energy 3000mJ/cm 2 Curing at 105 ℃ for 1h, and testing with a Dage chip pusher at 6 mm/min);
the swelling rate is less than 5 percent (the lithium-containing electrolyte is placed in an oven at 85 ℃ for 24 hours);
the dissolution rate is less than 1 percent (the solution is placed in a lithium-free electrolyte for 24 hours in an oven at 85 ℃).
After the battery shell is sealed by the top cover, electrolyte is injected, and the sealing time is longer than 60 days under the condition of 85 ℃ and 85% humidity; and after the free falling body falls at the height of 1.5m, the sealing time is longer than 60 days under the condition of 85 ℃ and 85% humidity. Therefore, the new energy battery sealing UV adhesive has good comprehensive performances such as solvent corrosion resistance, impact vibration resistance and the like, can effectively realize the adhesion and sealing of the new energy battery top cover and the shell, and ensures the safety and the lasting stability of the battery in various environments such as production, transportation, use and the like.
Example 1
The new energy battery sealing UV adhesive comprises the following components in parts by weight:
45 parts of bisphenol A epoxy resin
Bisphenol F epoxy resin 15 parts
10 parts of toughening resin
Glycidyl ether 10 parts
0.2 part of photoinitiator
The toughened resin I is prepared by the following method:
s1: 1mol of hydrogenated bisphenol A was melt-mixed with 1mol of PTMEG (molecular weight 2000, mitsubishi, PTMG 2000) at 170 ℃;
s2: dewatering for 1 hour, and cooling to 120 ℃;
s3: 0.02mol of DBTDL (dibutyl tin dilaurate) is added, 1mol of dicyclohexylmethane diisocyanate is added dropwise, and the reaction is carried out for 60min;
s4: heating to 170 ℃, discharging to obtain the hydroxyl-terminated toughened resin I.
The preparation method of the new energy battery sealing UV adhesive comprises the following steps:
step one: uniformly stirring epoxy resin and toughening resin I at 50 ℃ for 45 min;
step two: adding active diluent, stirring at 50deg.C for 45min, and cooling to room temperature;
step three: adding the photoinitiator, and stirring at room temperature under vacuum for 30min until no bubbles exist.
The application of the new energy battery sealing UV adhesive in the new energy battery top cover sealing comprises the following steps:
s1: the sealing surface of the battery shell and the sealing surface of the top cover are respectively coated with the new energy battery sealing UV adhesive, and the coating thickness is 1.5mm;
s2: pre-curing with UV light, wherein the UV light source is 365nm LED light source, pre-curing to be viscoelastic, the light pre-curing has a curing degree of 30%, and the curing energy is 3000mJ/cm 2 ；
S3: and correspondingly pressing and bonding the sealing surface of the top cover and the sealing surface of the battery shell, and finishing post-curing for 1h at 105 ℃.
Example 2
The new energy battery sealing UV adhesive comprises the following components in parts by weight:
45 parts of bisphenol A epoxy resin
Bisphenol F epoxy resin 15 parts
Toughening resin II 10 parts
Glycidyl ether 10 parts
0.2 part of photoinitiator
The toughening resin is prepared by the following method:
s1: 1mol of hydrogenated bisphenol A was melt-mixed with 1mol of 3MCPG (molecular weight 2000, lycra The LYCRA Company, trade name 3MCPG 2010) at 170 ℃;
s2: dewatering for 1 hour, and cooling to 120 ℃;
s3: adding 0.03mol of DBTDL, dropwise adding 1mol of dicyclohexylmethane diisocyanate, and reacting for 60min;
s4: heating to 170 ℃, discharging to obtain the hydroxyl-terminated toughened resin II.
The preparation method of the new energy battery sealing UV adhesive comprises the following steps:
step one: uniformly stirring epoxy resin and toughened resin II at 50 ℃ for 45 min;
step two: adding active diluent, stirring at 50deg.C for 45min, and cooling to room temperature;
step three: adding the photoinitiator, and stirring at room temperature under vacuum for 30min until no bubbles exist.
The sealing of the new energy battery sealing UV glue comprises the following steps:
s1: the sealing surface of the battery shell and the sealing surface of the top cover are respectively coated with the new energy battery sealing UV adhesive, and the coating thickness is 1.5mm;
s2: irradiating with UV light, wherein the UV light source is 365nm LED light source, pre-curing to viscoelastic state, the light pre-curing degree is 30%, and the curing energy is 3000mJ/cm 2 ；
S3: and correspondingly pressing and bonding the sealing surface of the top cover and the sealing surface of the battery shell, and finishing post-curing for 1h at 105 ℃.
Example 3
The new energy battery sealing UV adhesive comprises the following components in parts by weight:
45 parts of bisphenol A epoxy resin
Bisphenol F epoxy resin 15 parts
20 parts of toughening resin
Glycidyl ether 10 parts
0.2 part of photoinitiator
The toughened resin I is prepared by the following method:
s1: 1mol of hydrogenated bisphenol A was melt-mixed with 1mol of PTMEG (molecular weight 2000, mitsubishi, PTMG 2000) at 170 ℃;
s2: dewatering for 1 hour, and cooling to 120 ℃;
s3: 0.02mol of DBTDL is added, 1mol of dicyclohexylmethane diisocyanate is added dropwise, and the reaction is carried out for 60min;
s4: heating to 170 ℃, discharging to obtain the hydroxyl-terminated toughened resin I.
The preparation method of the new energy battery sealing UV adhesive comprises the following steps:
step one: uniformly stirring epoxy resin and toughening resin I at 50 ℃ for 45 min;
step two: adding active diluent, stirring at 50deg.C for 45min, and cooling to room temperature;
step three: the initiator was added and stirred in vacuo at room temperature for 30min until no bubbles were present.
The sealing method for sealing the UV adhesive by adopting the new energy battery comprises the following steps:
s1: the sealing surface of the battery shell and the sealing surface of the top cover are respectively coated with the new energy battery sealing UV adhesive, and the coating thickness is 1.5mm;
s2: irradiating with UV light, wherein the UV light source is 365nm LED light source, pre-curing to viscoelastic state, the light pre-curing degree is 30%, and the curing energy is 3000mJ/cm 2 ；
S3: and correspondingly pressing and bonding the sealing surface of the top cover and the sealing surface of the battery shell, and finishing post-curing for 1h at 105 ℃.
Example 4
The new energy battery sealing UV adhesive comprises the following components in parts by weight:
45 parts of bisphenol A epoxy resin
Bisphenol F epoxy resin 15 parts
Toughened resin II 20 parts
Glycidyl ether 10 parts
0.2 part of photoinitiator
The toughening resin is prepared by the following method:
s1: 1mol of hydrogenated bisphenol A was melt-mixed with 1mol of 3MCPG (molecular weight 2000, lycra The LYCRA Company, trade name 3MCPG 2010) at 170 ℃;
s2: dewatering for 1 hour, and cooling to 120 ℃;
s3: adding 0.03mol of DBTDL, dropwise adding 1mol of dicyclohexylmethane diisocyanate, and reacting for 60min;
s4: heating to 170 ℃, discharging to obtain the hydroxyl-terminated toughened resin II.
The preparation method of the new energy battery sealing UV adhesive comprises the following steps:
step one: uniformly stirring epoxy resin and toughened resin II at 50 ℃ for 45 min;
step two: adding active diluent, stirring at 50deg.C for 45min, and cooling to room temperature;
step three: adding the photoinitiator, and stirring at room temperature under vacuum for 30min until no bubbles exist.
The sealing method for sealing the UV adhesive by adopting the new energy battery comprises the following steps:
s1: the sealing surface of the battery shell and the sealing surface of the top cover are respectively coated with the new energy battery sealing UV adhesive, and the coating thickness is 1.5mm;
s2: irradiating with UV light selected from LED light source, pre-curing to viscoelastic state, light pre-curing with a curing degree of 30% and a curing energy of 3000mJ/cm 2 ；
S3: and correspondingly pressing and bonding the sealing surface of the top cover and the sealing surface of the battery shell, and finishing post-curing for 1h at 105 ℃.
Example 5
The difference between this example and example 1 is that the toughening resin one of the components of the new energy battery sealing UV gel is 30 parts.
Example 6
The difference between this example and example 1 is that the toughening resin one of the components of the new energy battery sealing UV gel is 40 parts.
Comparative example 1
Comparative example 1 is mainly different from example 1 in that the components of the sealing UV glue are different, and CTBN (carboxyl terminated polybutadiene acrylonitrile) toughening agent commonly used in the prior art is used to replace the toughening resin prepared by the present invention, and organobentonite is used, specifically as follows:
the UV sealant comprises the following components in parts by weight:
45 parts of bisphenol A epoxy resin
Bisphenol F epoxy resin 15 parts
CTBN 10 parts
Glycidyl ether 10 parts
Silane coupling agent 1 part
2 parts of organic bentonite
0.2 parts of photoinitiator.
The preparation method of the UV adhesive comprises the following steps:
step one: stirring epoxy resin, CTBN, glycidyl ether and a silane coupling agent at room temperature for 45min until the mixture is uniform;
step two: adding organic bentonite, and stirring at room temperature for 45min until uniform;
step three: adding the photoinitiator, and stirring at room temperature under vacuum for 30min until no bubbles exist.
The sealing method adopting the sealing UV adhesive comprises the following steps:
s1: the battery sealing UV glue is respectively coated on the sealing surface of the battery shell and the sealing surface of the top cover, and the coating thickness is 1.5mm;
s2: irradiating with UV light selected from LED light sources, pre-curing to viscoelastic shape, and pre-curing with light of about 30% and curing energy of 3000mJ/cm 2 ；
S3: and correspondingly pressing and bonding the sealing surface of the top cover and the sealing surface of the battery shell, and finishing post-curing for 1h at 100 ℃.
Comparative example 2
Comparative example 2 differs from example 1 in that the toughening resin content of the UV sealer is different, specifically as follows:
the UV sealant comprises the following components in parts by weight:
45 parts of bisphenol A epoxy resin
Bisphenol F epoxy resin 15 parts
5 parts of toughening resin
Glycidyl ether 10 parts
0.2 parts of photoinitiator.
Comparative example 3
Comparative example 3 differs from example 1 in the specific manner of operation of the UV sealer in the application step of the battery top cover seal, and specifically includes the steps of:
s1: the sealing UV glue is respectively coated on the sealing surface of the battery shell and the sealing surface of the top cover, and the coating thickness is 0.5mm;
s2: irradiating with UV light selected from LED light source with pre-curing degree of 50% and curing energy of 2000mJ/cm 2 ；
S3: and correspondingly pressing and bonding the sealing surface of the top cover and the sealing surface of the battery shell, and finishing post-curing for 1h at 105 ℃.
The compositions of the materials of examples 1-6 and comparative examples 1-3 are shown in Table 1:
table 1 the material composition tables of examples 1-6 and comparative examples 1-3
Performance testing
(1) Shear strength: the chip shearing method is used for sample preparation, glass sheets with the area of 3mm and 3mm are adhered on an aluminum substrate with the area of 25.4mm and 101.6mm, all adhesive surfaces of the glass sheets are coated, the adhesive layer thickness 0.1~0.2mm,365mm LED is irradiated by a light source, and the irradiation energy is 3000mJ/cm 2 After curing for 1h at 105 ℃, the Dage chip pusher is used for testing, the edge of the glass sheet is pushed by the pusher until the edge is broken, the speed is 6mm/min, and the stress mode is the same as that of stretching shearing and compression shearing.
(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 was put into a PP cup for sealing, and then 50+ -0.5 g of lithium-containing electrolyte (ethylene carbonate EC/propylene carbonate PC/diethyl carbonate DEC/ethyl propionate EP=3:3:1:3, and 1mol/L LiPF 6) was added, and the mixture was placed in an oven at 85 ℃ for 24h, and after removal, the mixture was wiped dry and weighed, and the weight difference before and after the experiment was compared with 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 Curing at 105 ℃ for 1 hour, putting into a penicillin bottle for sealing, and adding 7+/-0.1 g of lithium-free electrolysisThe solution (pure solvent formulation ethylene carbonate EC/propylene carbonate PC/diethyl carbonate DEC/ethyl propionate ep=3:3:1:3) was placed in an oven at 85 ℃ for 24h, the solution was withdrawn hot by syringe, the mass fraction of solute in the solution was tested by TGA, the solute mass in the whole solution was calculated, and the percentage of solute mass to initial weight was seen. Dissolution rate TGA measurement procedure: the temperature was raised to 320℃at a rate of 10℃per minute, the solvent was evaporated, and the residual weight percentage was seen after the end of the procedure.
(5) Dupont impact strength: the cross bonding method comprises the steps of preparing samples, dispensing the samples on an aluminum sheet in a circular shape with the inner diameter of 25.4mm and the width of 1.0+/-0.1 mm, bonding the circle center of another perforated glass round hole with the circle center surrounded by the glue line, controlling the thickness of the glue layer to be 0.25mm, irradiating with 365mm LED light source, and irradiating with energy of 6000mJ/cm 2 After curing for 1h at 105 ℃, the test was carried out with a DuPont impact tester, with an impact hammer of 200g and a height of 50cm, and the number of impacts at the time of failure was tested.
(6) High temperature and high humidity 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 Solidifying at 105 deg.c for 1 hr, putting in 85 deg.c/85% humidity environment for 1000 hr, taking out, volatilizing to eliminate water, cooling to room temperature, test in Dage chip pusher, test at speed of 6mm/min and adhering glass to aluminum.
(7) High low temperature cycle 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) after curing for 1h at 105 ℃, placing the materials into a high-low temperature circulation (-20-70 ℃, each temperature is 1h, the temperature rise time is 30 min) environment for 1000 hours, taking out the materials, and then, restoring the materials to room temperature for testing, testing by a Dage chip pusher, wherein the speed is 6mm/min, and the glass is bonded with aluminum.
(8) Helium detection: the batteries prepared in the examples and comparative examples were prepared by adding helium gas at a pressure of 0.1Mpa from the liquid injection hole into the sealed housing, maintaining the mixture for 30 minutes, and detecting the air pressure decay;
(9) Liquid resistance: the batteries prepared in examples and comparative examples were continuously aged at 85℃under 85% humidity after electrolyte was added from the filling hole into the sealed case, and it was confirmed whether or not the electrolyte oozed out from the sealed portion.
(10) Drop test: the batteries prepared in examples and comparative examples were sealed after electrolyte was added from the liquid injection hole into the sealed case, and the batteries were dropped at a height of 1.5m and tested for sealability after dropping.
Comparing the above examples 1-6 with comparative examples 1-3, the specific test results are shown in Table 2:
table 2 comparison of the properties of 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 new energy battery sealing UV adhesive is characterized by comprising the following components in parts by weight:
47-70 parts of epoxy resin
10-40 parts of toughening resin
10-20 parts of reactive diluent
0.1 to 0.5 part of photoinitiator
The epoxy resin is at least one selected from bisphenol A epoxy resin, bisphenol F epoxy resin and alicyclic epoxy resin;
the toughening resin is prepared by the following method:
s1: melt mixing hydrogenated bisphenol A with a polyether polyol having a molecular weight of 1600 to 2200 in a molar ratio of 1 (0.8 to 1.2);
s2: dewatering for 45-75min, and cooling to 100-130deg.C;
s3: dripping isocyanate accounting for 40-60% of the total mole of hydrogenated bisphenol A and polyether polyol for reaction;
s4: heating to 160-175 ℃ to obtain hydroxyl-terminated toughened resin;
the sealing method of the new energy battery sealing UV glue comprises the following steps:
s1: the sealing surface of the battery shell and the sealing surface of the top cover are respectively coated with the new energy battery sealing UV adhesive, and the coating thickness is 1.0-2.0mm;
s2: pre-curing by irradiation of UV light, wherein the pre-curing degree is 20-40%;
s3: correspondingly pressing and bonding the sealing surface of the top cover and the sealing surface of the battery shell, and finishing post-curing at 90-115 ℃;
wherein the UV light source is at least one selected from mercury lamp light source, LED light source and xenon lamp light source, and the curing energy is 2000-12000mJ/cm 2 。
2. The new energy battery sealant UV gel of claim 1, wherein the reactive diluent is selected from at least one of glycidyl ether, oxetane; the photoinitiator is at least one selected from diazonium salt, diaryl iodonium salt, triarylsulfonium salt, alkyl sulfonium salt, iron arene salt, sulfonyloxy ketone, triarylsiloxane ether and hexafluoroantimonate.
3. The new energy battery sealant UV glue of claim 1 or 2, wherein the polyether 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.
4. The new energy battery sealant UV gel of claim 3 wherein the polyether polyol is PTMEG and has a molecular weight of 1800-2200; the isocyanate is dicyclohexylmethane diisocyanate; and before dropping the isocyanate, dropping an organotin catalyst with the molar content of 2-3% of the isocyanate.
5. The new energy battery sealant UV gel of claim 3, wherein the polyether polyol is 3MCPG and has a molecular weight of 1600-2100; the isocyanate is isophorone diisocyanate; and before dropping the isocyanate, dropping an organotin catalyst with the molar content of 2-3% of the isocyanate.
6. The new energy battery sealing UV gel of claim 4 or 5, wherein the new energy battery sealing UV gel is pre-cured by UV light, post-cured by heating; after solidification, the shear strength is above 20Mpa, the swelling rate is less than 5%, and the dissolution rate is less than 1%.
7. A method for preparing the new energy battery sealing UV glue as claimed in any one of claims 1-6, comprising the steps of:
step one: uniformly stirring the epoxy resin and the 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 the photoinitiator, and stirring at room temperature for 20-40min under vacuum.
8. A sealing method for sealing UV gel by using the new energy battery according to any one of claims 1 to 6, comprising the steps of:
s1: the sealing surface of the battery shell and the sealing surface of the top cover are respectively coated with the new energy battery sealing UV adhesive, and the coating thickness is 1.0-2.0mm;
s2: pre-curing by irradiation of UV light, wherein the pre-curing degree is 20-40%;
s3: correspondingly pressing and bonding the sealing surface of the top cover and the sealing surface of the battery shell, and finishing post-curing at 90-115 ℃;
wherein the UV light source is at least one selected from mercury lamp light source, LED light source and xenon lamp light source, and the curing energy is 2000-12000mJ/cm 2 。
9. The sealing method according to claim 8, wherein after the battery case is sealed by the top cover, an electrolyte is injected, and the sealing time is longer than 60 days at 85 ℃ and 85% humidity; and after the free falling body falls at the height of 1.5m, the sealing time is longer than 60 days under the condition of 85 ℃ and 85% humidity.
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| CN105001824B (en) * | 2015-08-03 | 2017-08-29 | 中国工程物理研究院化工材料研究所 | A kind of cold curing ultralow temperature epoxy sealing glue and preparation method thereof |
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