CN115717046A - 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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- CN115717046A CN115717046A CN202310022296.6A CN202310022296A CN115717046A CN 115717046 A CN115717046 A CN 115717046A CN 202310022296 A CN202310022296 A CN 202310022296A CN 115717046 A CN115717046 A CN 115717046A
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- new energy
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- 238000007789 sealing Methods 0.000 title claims abstract description 127
- 239000000853 adhesive Substances 0.000 title claims abstract description 67
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 67
- 238000000034 method Methods 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims description 15
- 229920005989 resin Polymers 0.000 claims abstract description 58
- 239000011347 resin Substances 0.000 claims abstract description 58
- 239000003822 epoxy resin Substances 0.000 claims abstract description 28
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 28
- 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 21
- 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
- 238000010438 heat treatment Methods 0.000 claims abstract description 14
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims abstract description 13
- 238000011417 postcuring Methods 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
- 239000004842 bisphenol F epoxy resin Substances 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 125000002723 alicyclic group Chemical group 0.000 claims abstract description 4
- 239000003292 glue Substances 0.000 claims description 34
- 239000011248 coating agent Substances 0.000 claims description 21
- 238000000576 coating method Methods 0.000 claims description 21
- 239000003792 electrolyte Substances 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 21
- -1 alkyl sulfonium salts Chemical class 0.000 claims description 12
- 230000001678 irradiating effect Effects 0.000 claims description 12
- 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
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 10
- 238000003825 pressing Methods 0.000 claims description 9
- 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
- 239000012974 tin catalyst 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
- AHHWIHXENZJRFG-UHFFFAOYSA-N oxetane Chemical compound C1COC1 AHHWIHXENZJRFG-UHFFFAOYSA-N 0.000 claims description 3
- 239000000565 sealant Substances 0.000 claims description 3
- 125000005409 triarylsulfonium group Chemical group 0.000 claims description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 2
- 229910052753 mercury Inorganic materials 0.000 claims description 2
- 229910052724 xenon Inorganic materials 0.000 claims description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 1
- 239000002904 solvent Substances 0.000 abstract description 7
- 230000007797 corrosion Effects 0.000 abstract description 2
- 238000005260 corrosion Methods 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 2
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- 230000008901 benefit Effects 0.000 description 7
- 238000005286 illumination Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 6
- 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
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 238000007599 discharging Methods 0.000 description 5
- 239000003999 initiator Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000004806 packaging method and process Methods 0.000 description 5
- 238000010008 shearing Methods 0.000 description 5
- 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
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000002835 absorbance Methods 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
- 229910052744 lithium Inorganic materials 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 239000012790 adhesive layer Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
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- 230000008018 melting Effects 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
- 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
- 229920002334 Spandex Polymers 0.000 description 2
- 238000004026 adhesive bonding Methods 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
- 238000004132 cross linking Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 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
- 238000002329 infrared spectrum Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 239000004759 spandex Substances 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
- 206010011469 Crying Diseases 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 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
- 239000004743 Polypropylene Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
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- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
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- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 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 UV adhesive for sealing the new energy battery 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 selected from at least one of bisphenol A epoxy resin, bisphenol F epoxy resin and alicyclic epoxy resin; the toughened resin is prepared by the following method: s1: melt mixing hydrogenated bisphenol A and polyether polyol; s2: removing water and cooling; s3: dripping isocyanate to react; s4: and heating to obtain the hydroxyl-terminated toughened resin. The UV adhesive disclosed by the invention can be used for effectively realizing the bonding and sealing of a new energy battery through UV light pre-curing and heating post-curing, has good comprehensive properties such as solvent corrosion resistance and impact vibration resistance, and the like, is adjustable in curing speed and degree, and improves the safety and reliability of a product.
Description
Technical Field
The invention belongs to the technical field of adhesives for batteries, in particular relates to a UV (ultraviolet) light pre-curing and heating post-curing adhesive, and particularly relates to a new energy battery sealing UV adhesive, and a preparation method and a sealing method thereof.
Background
Present new forms of energy power battery divides mainly to be square battery, cylinder battery and laminate polymer battery three major types, and wherein square battery includes that top cap, shell, positive plate, negative plate, diaphragm are constituteed or coiling piece, insulating part, safety subassembly etc. and top cap and shell are assembled through welding mode and are wrapped up other electric core interior materials together, and welding mode's advantage lies in that intensity is high, fast, process manufacturing is simpler, still has some problems: firstly, welding slag is easily generated in the preparation process, and the welding slag enters the battery core and can pierce a diaphragm to cause short circuit, so that the battery can be spontaneously combusted; secondly, due to insufficient soldering, part of positions cannot be effectively bonded, and the risk of internal electrolyte leakage exists; thirdly, dust or impurities on the shell or the top cover easily cause explosion points during welding, fine holes exist at the positions, and the risk of leakage of the internal electrolyte exists; in addition, partial position welding is excessive, leads to welding to wear, has inside electrolyte weeping risk, has the welding slag to fall into the inside risk of electricity core simultaneously.
The use of glue to encapsulate the battery is a more common alternative at present. Patent CN113512366A discloses a curing adhesive, a battery, an electronic device and a battery packaging method, wherein the curing adhesive comprises 15 to 24 parts by mass of low-melting-point resin, 7 to 19 parts by mass of epoxy resin, 1.8 to 3.0 parts by mass of radical initiator and 0.5 to 1.0 part by mass of cationic initiator; the melting point of the low-melting-point resin is 90-160 ℃. The battery can be packaged under the conditions of low temperature and low pressure, 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 viscosity, high curing speed and the like. However, as a battery packaging adhesive, the invention does not pay attention to the solvent resistance of the curing adhesive, so that 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, low-melting-point resin is heated to a molten state, and potential safety and environmental protection hazards exist.
Patent CN115074056A discloses an inner layer adhesive of an aluminum plastic film for lithium battery packaging and a preparation method thereof, wherein the adhesive comprises a component A and a component B; the component A comprises: polyolefin with low melting point, anhydride monomer, initiator, auxiliary agent and organic solvent I; the component B comprises: bisphenol A epoxy resin, modified bisphenol A epoxy resin and organic solvent II; the auxiliary agent is a multifunctional organic micromolecule containing triazine ring. The invention takes polyolefin with low melting point as main resin, matches with a small amount of bisphenol A epoxy resin, and adds a small amount of multifunctional 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 to 5 days at 60 to 100 ℃ to achieve a good curing effect, and the curing efficiency is not favorable for large-scale industrial production.
Therefore, how to obtain an adhesive for sealing a battery, which has excellent comprehensive performance and high packaging safety and reliability, has controllable curing process and simple and convenient operation, and becomes a technical problem to be solved in the field.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides the new energy battery sealing UV adhesive (ultraviolet curing adhesive and shadowless adhesive) and the preparation method and the sealing method thereof, wherein the UV adhesive is especially used for new energy square batteries, has excellent comprehensive properties such as bonding effect, sealing property, electrolyte resistance, mechanical property and the like, and is flexible and controllable in the curing process. The UV glue is used for sealing the battery, can effectively prevent electrolyte from seeping, can use glue spraying or glue dispensing technology, is convenient to operate, and realizes automatic glue coating efficiently.
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 toughened resin
10-20 parts of reactive diluent
0.1 to 0.5 portion of photoinitiator
The epoxy resin is selected from at least one of bisphenol A epoxy resin, bisphenol F epoxy resin and alicyclic epoxy resin;
the toughened resin is prepared by the following method:
s1: melt mixing hydrogenated bisphenol A and polyether polyol with the molecular weight of 1600-2200 in a molar ratio of 1 (0.8-1.2);
s2: dewatering for 45-75min, and cooling to 100-130 deg.C;
s3: dropwise adding isocyanate accounting for 40-60% of the total molar amount of the hydrogenated bisphenol A and the polyether polyol to react;
s4: heating to 160-175 ℃ to obtain the hydroxyl-terminated toughened resin.
Epoxy resin is a commonly used light-cured resin and has the advantages of low curing shrinkage, strong adhesive force and the like, but the epoxy resin curing system has high crosslinking density and high brittleness, so that the application of the epoxy resin curing system is limited. 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 sealing batteries.
In the preparation of the toughening resin, polyether polyol with the molecular weight of 1600-2200 is selected, so that the excessive melt viscosity is not easy to cause, better melt mixing can be realized, and in addition, the polyether polyol has weaker molecular polarity and better flexibility of a molecular chain, the initial viscosity and the strength of a product can be reduced, and the adherend can be conveniently soaked.
The amount of reactive diluent used has a large effect on the curing 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 epoxy groups and initiators 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, although the reactive diluent has certain reactivity, the reactivity of the reactive diluent is lower than that of the epoxy resin, and the addition of a large amount of the reactive diluent causes the proportion of the epoxy resin in a resin system to be reduced, so that the reactivity of the whole resin system is reduced, and the curing reaction rate of the resin system is reduced. 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.
In view of the degree and speed of UV light precuring, the content of the photoinitiator is selected to be 0.1-0.5 part, so that the precuring efficiency can be ensured, and the precuring degree can be conveniently adjusted. Within this range, as the content of the photoinitiator increases, the precuring speed increases, and the precuring degree of the resin system shows an increasing tendency under the same curing conditions. When the content is less than 0.1 part, the UV light pre-curing takes a long time, which is not favorable for improving the production efficiency. However, when the content is more than 0.5 part, active sites 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 post-curing and the regulation and control of the bonding performance are not facilitated.
Further, the reactive diluent is selected from at least one of glycidyl ether and oxetane; the photoinitiator is at least one selected from diazonium salts, diaryl iodonium salts, triaryl sulfonium salts, alkyl sulfonium salts, iron arene salts, sulfonyloxy ketones, triaryl siloxy ethers and hexafluoroantimonate.
Further, the polyether polyol is selected from at least one of Polytetrahydrofuran (PTMEG), tetrahydrofuran copolyether glycol (3 MCPG), polypropylene glycol (PPG) and polyethylene glycol (PEG); the isocyanate is selected from at least one of Hexamethylene Diisocyanate (HDI), dicyclohexylmethane diisocyanate (HMDI) and isophorone diisocyanate (IPDI). Compared with other toughening agents, the toughening resin disclosed by the invention is added into an epoxy system in a proper proportion, so that the obtained adhesive has the performances of obviously excellent shear strength, adhesive force and the like, and lower hardness, and is particularly suitable for bonding and sealing new energy batteries.
Through various formulation experiments, the invention preferably provides two toughened resins:
toughening resin I: the polyether polyol is PTMEG, and the molecular weight is 1800-2200; the isocyanate is dicyclohexylmethane diisocyanate; and before dripping the isocyanate, dripping an organic tin catalyst with the isocyanate molar content of 2-3%. The toughened resin prepared by Polytetrahydrofuran (PTMEG) has the advantages of low viscosity, high functionality, excellent mechanical property of the product and the like.
The toughened resin I is obtained by the method, and has the following structural formula:
and II, toughening resin: the polyether polyol is 3MCPG, and the molecular weight is 1600-2100; the isocyanate is isophorone diisocyanate; and before dripping the isocyanate, dripping an organic tin catalyst with the isocyanate molar content of 2-3%. The toughened resin prepared from tetrahydrofuran copolyether glycol (3 MCPG) has the advantages of low viscosity, high functionality, excellent mechanical properties of products and the like.
The toughened resin II is obtained by the method, and has the following structural formula:
furthermore, the new energy battery sealing UV adhesive is cured through UV light pre-curing and heating, and the cured adhesive at least has the following properties:
the shear strength is more than 20Mpa (the cementing area is 3mm multiplied by 3mm, and the test is carried out by a pusher at 6 mm/min);
the swelling rate is less than 5 percent (the mixture is placed in a lithium-containing electrolyte for 24 hours in an oven at 85 ℃);
the dissolution rate is less than 1 percent (the mixture is placed in lithium-free electrolyte for 24 hours in an oven at 85 ℃).
The excellent bonding performance, sealing performance and solvent resistance are important characteristics of the UV adhesive and are also the key of the UV adhesive which can be safely and stably used in the field of battery sealing. The UV adhesive is related to a plurality of factors such as the variety and the content ratio of each component of the UV adhesive.
In a second aspect, aiming at the new energy battery sealing UV glue, the invention also provides a preparation method of the new energy battery sealing UV glue, which comprises the following steps:
the method comprises the following steps: uniformly stirring the epoxy resin and the toughening resin at the temperature of 50 +/-3 ℃ for 30-60 min;
step two: adding active diluent, stirring at 50 + -3 deg.C for 30-60min, and cooling to room temperature;
step three: adding photoinitiator, and stirring at room temperature under vacuum for 20-40min until no bubbles exist.
In a third aspect, a sealing method for sealing the UV glue by using the new energy battery is provided, which includes the following steps:
s1: respectively coating the sealing surface of the battery shell and the sealing surface of the top cover with the new energy battery sealing UV glue, wherein the coating thickness is 1.0-2.0mm;
s2: irradiating with UV light to pre-cure at 20-40%;
s3: and (3) 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 viscoelastic, 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 the press bonding and the curing degree of the precuring have a certain positive phase relation, the pressure is also adjusted correspondingly according to the bonding area, usually 0.2-0.3MPa, and the pressure is small, so that the damage to the battery shell and the internal electronic components is avoided.
The degree of pre-cure is selected according to the bonding requirements. The curing process can be tracked through real-time infrared spectroscopy by accurately regulating and controlling the pre-curing degree, so that the pre-curing degree can be grasped through the pre-curing time. When infrared light passes through the sample, different groups in the colloid can selectively absorb infrared light with different wavelengths, and an epoxy group (about 913 cm) is measured in an infrared spectrogram -1 ) And benzene rings (about 1610 cm) -1 ) Absorbance before and after light irradiation:
wherein A is absorbance; i is 0 And I is the intensity of the incident light and the transmitted light, respectively;
degree of cure G of resin system:
wherein A is 0 And A 0 ' initial absorbances of epoxy group and benzene ring, respectively; a. The t And A t ' is the absorbance of the epoxy group and the benzene ring, respectively, after the illumination time t.
Through the calculation formula, the pre-curing illumination time under various UV light source conditions can be accurately obtained, and insufficient or excessive pre-curing is avoided. The real-time infrared spectrum tracking curing process can be used for monitoring the pre-curing degree on line, 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 UV adhesive for sealing the new energy battery is 1.0-2.0mm, the curing energy is input to 2000-12000mJ/cm 2 Preferably 3000-6000mJ/cm 2 When the distance between the UV light source and the UV light source is 40-60mm, the pre-curing speed/time can be adjusted by adjusting the size of UV light irradiation curing energy, and the pre-curing degree can be adjusted by adjusting the input range of the pre-curing energy according to the curing energy = the light intensity. In the invention, the crosslinking degree of the pre-cured glue is controlled by controlling the curing energy, so that the pre-cured glue has certain initial strength, can be post-cured to achieve the aim of final bonding force, and 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 more than 60 days under the conditions of 85 ℃ and 85% humidity; and after the free falling body falls at the height of 1.5m, the sealing time is more than 60 days under the conditions of 85 ℃ and 85% humidity. The UV adhesive has excellent bonding performance and sealing performance in the application of battery top cover sealing, and fully meets the requirements of various scenes such as battery transportation, battery use and the like.
The invention has the advantages that:
1. according to the invention, the initial curing is rapidly carried out through UV illumination, the initial strength is established, the initial curing degree and the curing speed are adjustable, and the production process of the battery can be variously matched; meanwhile, the post-curing (or room temperature curing for a prolonged period of time) can be carried out 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 the complete bonding of various special-shaped curved surfaces, has good wettability to the surface of a shell, and cannot generate leak holes and pinholes; meanwhile, the glue is a high-molecular substance, is not easy to crack and cannot pierce through a diaphragm.
3. The new energy battery sealing UV adhesive prepared by the invention has good bonding force, and can be effectively adhered to a shell without falling off; the material has good toughness and can resist vibration or impact; the solvent resistance is good, and the electrolyte is not easy to corrode.
4. The new energy battery sealing UV adhesive prepared by the invention has stable high and low temperature performance, can meet the requirements of sealing performance and reliability under the use temperature environment, can effectively bond and seal by using the UV delayed curing type sealant and performing seaming after gluing the bonding position of the new energy square battery top cover and the shell in advance, prevents electrolyte from leaking in the use process of the battery, improves the safety and reliability of the product, and can realize automatic gluing by using a glue spraying or dispensing process.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be further described in detail with reference to the following examples.
In a 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 toughened resin
10-20 parts of reactive diluent
0.1 to 0.5 portion of photoinitiator
The epoxy resin is at least one of bisphenol A epoxy resin, bisphenol F epoxy resin and alicyclic epoxy resin; the reactive diluent is selected from at least one of glycidyl ether and oxetane; the photoinitiator is at least one selected from diazonium salts, diaryliodonium salts, triarylsulfonium salts, alkylsulfonium salts, iron arene salts, sulfonyloxy ketones, triarylsiloxy ethers, and hexafluoroantimonate salts.
The toughening resin is prepared by the following method:
s1: melt mixing hydrogenated bisphenol A and polyether polyol with the molecular weight of 1600-2200 in a molar ratio of 1 (0.8-1.2);
s2: dewatering for 45-75min, and cooling to 100-130 deg.C;
s3: dropwise adding isocyanate accounting for 40-60% of the total molar amount of the hydrogenated bisphenol A and the polyether polyol to react;
s4: heating to 160-175 ℃, discharging to obtain the hydroxyl-terminated toughened resin.
The polyether polyol is at least one selected from PTMEG, 3MCPG, PPG and PEG.
The isocyanate is at least one of hexamethylene diisocyanate, dicyclohexylmethane diisocyanate and isophorone diisocyanate.
A first tackifying resin: the polyether polyol is PTMEG, and the molecular weight is 1800-2200; the isocyanate is dicyclohexylmethane diisocyanate; and before dripping the isocyanate, dripping an organic tin catalyst with the isocyanate molar content of 2-3%.
And a second tackifying resin: the polyether polyol is 3MCPG and has the molecular weight of 1600-2100; the isocyanate is isophorone diisocyanate; and before dripping the isocyanate, dripping an organic tin catalyst with the isocyanate molar content of 2-3%.
In a second aspect, the preparation method of the new energy battery sealing UV adhesive comprises the following steps:
the method comprises the following steps: uniformly stirring the epoxy resin and the toughening resin at the temperature of 50 +/-3 ℃ for 30-60 min;
step two: adding active diluent, stirring at 50 + -3 deg.C for 30-60min, and cooling to room temperature;
step three: adding photoinitiator, and stirring at room temperature under vacuum for 20-40min until no bubbles exist.
In a third aspect, the sealing method for sealing the UV adhesive by using the new energy battery comprises the following steps:
s1: respectively coating the sealing surface of the battery shell and the sealing surface of the top cover with the new energy battery sealing UV glue, wherein the coating thickness is 1.0-2.0mm;
s2: irradiating with UV light to pre-cure, 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 Precuring to be viscoelastic;
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 for bonding is preferably 0.2-0.3MPa.
The new energy battery sealing UV adhesive is cured through UV light precuring and heating, and at least has the following properties after curing:
the shear strength is more than 20Mpa (the bonding area is 3mm multiplied by 3mm, the adhesive layer thickness is 0.1 to 0.2mm,365mm, the irradiation energy is 3000mJ/cm under the illumination of an LED light source 2 Curing at 105 ℃ for 1h, and testing by using a Dage chip pusher at 6 mm/min);
the swelling rate is less than 5 percent (the mixture is placed in a lithium-containing electrolyte for 24 hours in an oven at 85 ℃);
the dissolution rate is less than 1 percent (the mixture is placed in 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 more than 60 days under the conditions of 85 ℃ and 85% humidity; and after the free falling body falls at the height of 1.5m, the sealing time is more than 60 days under the conditions of 85 ℃ and 85% humidity. Therefore, the new energy battery sealing UV adhesive has good comprehensive performances such as solvent corrosion resistance and impact and vibration resistance, can effectively realize the bonding 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 and use.
Example 1
The new energy battery sealing UV adhesive comprises the following components in parts by weight:
bisphenol A epoxy resin 45 parts
Bisphenol F epoxy resin 15 parts
10 portions of toughened resin
10 parts of glycidyl ether
0.2 portion of photoinitiator
The first toughening resin is prepared by the following method:
s1: melt-mixing 1mol of hydrogenated bisphenol A with 1mol of PTMEG (molecular weight 2000, mitsubishi, PTMG 2000) at 170 ℃;
s2: dewatering for 1 hour, and cooling to 120 ℃;
s3: adding 0.02mol of DBTDL (dibutyltin dilaurate), dropwise adding 1mol of dicyclohexylmethane diisocyanate, and reacting for 60min;
s4: and heating to 170 ℃, and discharging to obtain the hydroxyl-terminated toughened resin I.
The preparation method of the new energy battery sealing UV adhesive comprises the following steps:
the method comprises the following steps: uniformly stirring the epoxy resin and the toughening resin I at 50 ℃ for 45 min;
step two: adding active diluent, stirring at 50 deg.C for 45min, and cooling to room temperature;
step three: the photoinitiator was added and stirred at room temperature under vacuum for 30min until no bubbles were present.
The application of the new energy battery sealing UV adhesive in the new energy battery top cover sealing comprises the following steps:
s1: respectively coating the sealing surface of the battery shell and the sealing surface of the top cover with the new energy battery sealing UV glue, wherein the coating thickness is 1.5mm;
s2: irradiating with UV light selected from 365nm LED light source to pre-cure to viscoelastic state, wherein the curing degree of the light pre-curing is 30%, and the curing energy is 3000mJ/cm 2 ；
S3: and (3) 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:
bisphenol A epoxy resin 45 parts
15 parts of bisphenol F epoxy resin
Second 10 parts of toughened resin
10 parts of glycidyl ether
0.2 part of photoinitiator
The toughened resin II is prepared by the following method:
s1: 1mol of hydrogenated bisphenol A and 1mol of 3MCPG (molecular weight 2000, lyca of LYCRA Company, trade name 3MCPG 2010) were melt mixed 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: and (3) heating to 170 ℃, and discharging to obtain the hydroxyl-terminated toughened resin II.
The preparation method of the new energy battery sealing UV adhesive comprises the following steps:
the method comprises the following steps: uniformly stirring the epoxy resin and the second toughening resin at 50 ℃ for 45 min;
step two: adding active diluent, stirring at 50 deg.C for 45min, and cooling to room temperature;
step three: adding the photoinitiator, and stirring in vacuum for 30min at room temperature until no bubbles exist.
Adopt the sealing of new forms of energy battery sealed UV to glue, include the following step:
s1: respectively coating the sealing surface of the battery shell and the sealing surface of the top cover with the new energy battery sealing UV glue, wherein the coating thickness is 1.5mm;
s2: irradiating with UV light selected from 365nm LED light source, pre-curing to visco-elastic state, wherein the curing degree of the light pre-curing is 30%, and the curing energy is 3000mJ/cm 2 ；
S3: and (3) 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:
bisphenol A epoxy resin 45 parts
Bisphenol F epoxy resin 15 parts
20 portions of toughened resin
10 parts of glycidyl ether
0.2 part of photoinitiator
The toughened resin I is prepared by the following method:
s1: melt-mixing 1mol of hydrogenated bisphenol A with 1mol of PTMEG (molecular weight 2000, mitsubishi, PTMG 2000) at 170 ℃;
s2: dewatering for 1 hour, and cooling to 120 ℃;
s3: adding 0.02mol of DBTDL, dropwise adding 1mol of dicyclohexylmethane diisocyanate, and reacting for 60min;
s4: and (3) heating to 170 ℃, and discharging to obtain the hydroxyl-terminated toughened resin I.
The preparation method of the new energy battery sealing UV adhesive comprises the following steps:
the method comprises the following steps: uniformly stirring the epoxy resin and the toughening resin I at 50 ℃ for 45 min;
step two: adding active diluent, stirring at 50 deg.C for 45min, and cooling to room temperature;
step three: initiator is added and stirred for 30min under vacuum at room temperature until no bubbles exist.
The sealing method for sealing the UV adhesive by adopting the new energy battery comprises the following steps:
s1: respectively coating the sealing surface of the battery shell and the sealing surface of the top cover with the new energy battery sealing UV glue, wherein the coating thickness is 1.5mm;
s2: irradiating with UV light selected from 365nm LED light source, pre-curing to visco-elastic state, wherein the curing degree of the light pre-curing is 30%, and the curing energy is 3000mJ/cm 2 ；
S3: and (3) 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
20 portions of toughened resin
10 parts of glycidyl ether
0.2 portion of photoinitiator
The toughened resin II is prepared by the following method:
s1: 1mol of hydrogenated bisphenol A and 1mol of 3MCPG (molecular weight 2000, lyca of LYCRA Company, trade name 3MCPG 2010) were melt mixed 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: and (3) heating to 170 ℃, and discharging to obtain the hydroxyl-terminated toughened resin II.
The preparation method of the new energy battery sealing UV adhesive comprises the following steps:
the method comprises the following steps: uniformly stirring the epoxy resin and the second toughening resin at 50 ℃ for 45 min;
step two: adding active diluent, stirring at 50 deg.C for 45min, and cooling to room temperature;
step three: the photoinitiator was added and stirred at room temperature under vacuum 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: respectively coating the sealing surface of the battery shell and the sealing surface of the top cover with the new energy battery sealing UV glue, wherein the coating thickness is 1.5mm;
s2: irradiating with UV light selected from LED light source, pre-curing to visco-elastic state, wherein the curing degree of the light pre-curing is 30%, and the curing energy is 3000mJ/cm 2 ；
S3: and (3) 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 the new energy battery sealing UV glue and the embodiment 1 is that the first toughening resin is 30 parts in the components of the new energy battery sealing UV glue.
Example 6
The difference between the embodiment and the embodiment 1 is that the first toughening resin in the components of the new energy battery sealing UV adhesive is 40 parts.
Comparative example 1
The main difference between comparative example 1 and example 1 is that the components of the sealing UV glue are different, the toughened resin prepared according to the invention is replaced by a CTBN (carboxyl terminated polybutadiene acrylonitrile) toughening agent commonly used in the prior art, and organobentonite is used, specifically as follows:
the sealing UV adhesive comprises the following components in parts by weight:
45 parts of bisphenol A epoxy resin
15 parts of bisphenol F epoxy resin
CTBN 10 parts
10 parts of glycidyl ether
1 part of silane coupling agent
2 portions of organic bentonite
0.2 part of photoinitiator.
The preparation method of the UV adhesive comprises the following steps:
the method comprises the following steps: stirring epoxy resin, CTBN, glycidyl ether and a silane coupling agent at room temperature for 45min to be uniform;
step two: adding organic bentonite, and stirring at room temperature for 45min to obtain a uniform mixture;
step three: adding the photoinitiator, and stirring in vacuum for 30min at room temperature until no bubbles exist.
The sealing method adopting the sealing UV adhesive comprises the following steps:
s1: coating the battery sealing UV glue on the sealing surface of the battery shell and the sealing surface of the top cover respectively, wherein the coating thickness is 1.5mm;
s2: irradiating with UV light selected from LED light source, pre-curing to visco-elastic state, wherein the light pre-curing has a curing degree of about 30% and curing energy of 3000mJ/cm 2 ；
S3: and (3) 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
The difference between the comparative example 2 and the example 1 is that the content of the first toughening resin of the sealing UV adhesive is different, and the specific content is as follows:
the 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 5 parts
10 parts of glycidyl ether
0.2 part of photoinitiator.
Comparative example 3
Comparative example 3 differs from example 1 in the specific operation manner in the step of applying the sealing UV paste in the sealing of the top cap of the cell, and this comparative example specifically includes the following steps:
s1: coating the sealing UV glue on the sealing surface of the battery shell and the sealing surface of the top cover respectively, wherein 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 (3) 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 composition of materials for examples 1-6 and comparative examples 1-3
Performance testing
(1) Shear strength: preparing a sample by a chip shearing method, adhering a glass sheet with the area of 3mm to 3mm on an aluminum substrate with the area of 25.4mm to 101.6mm, coating all adhesive surfaces of the glass sheet with adhesive, irradiating an LED light source with the adhesive layer thickness of 0.1-0.2mm and 365mm under the irradiation of illumination energy of 3000mJ/cm 2 And after curing for 1h at 105 ℃, testing by a Dage chip pusher, pushing the edge of the glass sheet by the pusher until the edge is damaged at the speed of 6mm/min, wherein the stress mode is the same as that of stretching shearing and compression shearing.
(2) Hardness: the glue is prepared into an LED light source with the thickness of 6mm and 365mm for illumination, and the irradiation energy is 9000mJ/cm 2 And testing after curing for 1h at 105 ℃, and testing by using a Shore hardness tester.
(3) Swelling ratio: irradiating glue 2.0 + -0.05 g with 365mm LED light source at 6000mJ/cm 2 After curing at 105 ℃ for 1h, the resulting mixture was sealed in a PP cup, 50 ± 0.5g of a lithium-containing electrolyte (ethylene carbonate EC/propylene carbonate PC/diethyl carbonate DEC/ethyl propionate EP =3, and 1mol/L LiPF 6) was added, the mixture was left in an oven at 85 ℃ for 24h, taken out, wiped dry and weighed, and the weight difference between before and after the experiment was a percentage of the initial weight.
(4) Dissolution rate: glue is addedExtruding 1.4 + -0.05 g, illuminating with 365mm LED light source with irradiation energy of 6000mJ/cm 2 After curing at 105 ℃ for 1h, the solution is sealed in a penicillin bottle, 7 ± 0.1g of lithium-free electrolyte (pure solvent formulation ethylene carbonate EC/propylene carbonate PC/diethyl carbonate DEC/ethyl propionate EP = 3) is added, the solution is placed in an oven at 85 ℃ for 24h, the solution is extracted while hot by a syringe after being taken out, and the mass fraction of the solute in the solution is tested by TGA to calculate the mass of the solute in the whole solution, and the mass of the solute is then read as a percentage of the initial weight. Dissolution rate TGA measurement procedure: the temperature is raised to 320 ℃ at 30 ℃, the temperature raising speed is 10 ℃ per minute, the solvent is evaporated, and the residual weight percentage is seen after the procedure is finished.
(5) Dupont impact strength: preparing a sample by a cross bonding method, dispensing a circle with an inner diameter of 25.4mm and a width of 1.0 +/-0.1 mm on an aluminum sheet, bonding the circle center of another punched glass circular hole with the circle center surrounded by glue lines, controlling the thickness of a glue layer to be 0.25mm, illuminating by a 365mm LED light source, and irradiating with energy of 6000mJ/cm 2 Curing at 105 ℃ for 1h, and testing by using a DuPont impact tester, wherein the impact hammer is 200g, the height is 50cm, and the impact frequency is tested when the rubber is damaged.
(6) High-temperature high-humidity strength: preparing a sample by a chip shearing method, wherein the bonding area is 3mm to 3mm, the bonding area is 365mm, and the irradiation energy is 3000mJ/cm 2 Curing at 105 ℃ for 1h, putting into an environment with 85 ℃/85% humidity for 1000 hours, taking out, volatilizing water, cooling to room temperature for testing, testing by a Dage chip pusher at the speed of 6mm/min, and bonding glass with aluminum.
(7) High and low temperature cycle strength: preparing a sample by a chip shearing method, wherein the bonding area is 3mm to 3mm, the bonding area is 365mm, and the irradiation energy is 3000mJ/cm 2 Curing at 105 ℃ for 1h, putting the glass into an environment with high-low temperature circulation (the temperature is between 20 ℃ and 70 ℃, the temperature is 1h each time, and the temperature rise and fall time is 30 min) for 1000 h, taking out the glass, recovering the glass to room temperature, testing the glass by a Dage chip pusher, and bonding the glass with aluminum at the speed of 6 mm/min.
(8) Helium detection: in the batteries prepared in the embodiment and the comparative example, helium gas with the pressure of 0.1Mpa is added into the sealed shell from the liquid injection hole, the mixture is kept for 30min, and the air pressure attenuation condition is detected;
(9) Liquid resistance: in the batteries manufactured in the examples and comparative examples, after the electrolyte was applied to the sealed case from the liquid inlet, the case was left to stand at 85 ℃ under 85% humidity for continuous aging to see whether or not the electrolyte leaked from the sealed portion.
(10) And (3) drop test: in the batteries manufactured in the embodiment and the comparative example, electrolyte is added into the sealed shell from the liquid injection hole, the sealed shell is sealed well, and the batteries fall freely at the height of 1.5m, so that the sealing performance of the batteries after falling is tested.
The above examples 1-6 were compared with comparative examples 1-3, and the specific test results are shown in Table 2:
TABLE 2 comparison of the Properties of examples 1-6 with comparative examples 1-3
The foregoing describes preferred embodiments of the present invention, and is intended to provide a clear and concise description of the spirit and scope of the invention, and not to limit the same, but to include all modifications, substitutions, and alterations falling within the spirit and scope of the invention as defined by the appended claims.
Claims (10)
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 toughened resin
10-20 parts of reactive diluent
0.1 to 0.5 portion of photoinitiator
The epoxy resin is selected from at least one of bisphenol A epoxy resin, bisphenol F epoxy resin and alicyclic epoxy resin;
the toughened resin is prepared by the following method:
s1: melt mixing hydrogenated bisphenol A and polyether polyol with the molecular weight of 1600-2200 in a molar ratio of 1 (0.8-1.2);
s2: dewatering for 45-75min, and cooling to 100-130 deg.C;
s3: dropwise adding isocyanate accounting for 40-60% of the total molar amount of the hydrogenated bisphenol A and the polyether polyol to react;
s4: heating to 160-175 ℃ to obtain the hydroxyl-terminated toughened resin.
2. The new energy battery sealing UV glue 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 salts, diaryl iodonium salts, triaryl sulfonium salts, alkyl sulfonium salts, iron arene salts, sulfonyloxy ketone, triaryl siloxy ether and hexafluoroantimonate.
3. The new energy cell sealing 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 UV sealant for sealing new energy batteries according to claim 3, wherein the polyether polyol is PTMEG, and has a molecular weight of 1800-2200; the isocyanate is dicyclohexylmethane diisocyanate; and before dripping the isocyanate, dripping an organic tin catalyst with the isocyanate molar content of 2-3%.
5. The UV sealant for sealing the new energy battery of claim 3, wherein the polyether polyol is 3MCPG, and has a molecular weight of 1600-2100; the isocyanate is isophorone diisocyanate; and before dripping the isocyanate, dripping an organic tin catalyst with the isocyanate molar content of 2-3%.
6. The new energy battery sealing UV glue according to claim 4 or 5, wherein the new energy battery sealing UV glue is pre-cured by UV light and cured after heating; after curing, the shear strength is more than 20Mpa, the swelling ratio is less than 5 percent, and the dissolution rate is less than 1 percent.
7. The preparation method of the UV adhesive for sealing the new energy battery as claimed in any one of claims 1 to 6, characterized by comprising the following steps:
the method comprises the following steps: uniformly stirring the epoxy resin and the toughening resin at the temperature of 50 +/-3 ℃ for 30-60 min;
step two: adding active diluent, stirring at 50 + -3 deg.C for 30-60min, and cooling to room temperature;
step three: adding the photoinitiator, and stirring for 20-40min in vacuum at room temperature.
8. A sealing method for sealing UV adhesive by using the new energy battery as claimed in any one of claims 1 to 6, characterized by comprising the following steps:
s1: coating the new energy battery sealing UV glue on the sealing surface of the battery shell and the sealing surface of the top cover respectively, wherein the coating thickness is 1.0-2.0mm;
s2: irradiating with UV light to pre-cure, wherein the pre-curing degree is 20-40%;
s3: and (3) 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 ℃.
9. The sealing method according to claim 8, wherein the UV light source is at least one selected from a mercury lamp light source, an LED light source, and a xenon lamp light source, and the curing energy is 2000 to 12000mJ/cm 2 。
10. The sealing method according to claim 8 or 9, wherein after the battery case is sealed by the top cap, an electrolyte is injected for a sealing time of more 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 more than 60 days under the conditions of 85 ℃ and 85% humidity.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117907259A (en) * | 2024-03-20 | 2024-04-19 | 深圳市聚芯源新材料技术有限公司 | Epoxy structural adhesive curing detection device and detection method |
| CN117907259B (en) * | 2024-03-20 | 2024-05-14 | 深圳市聚芯源新材料技术有限公司 | Epoxy structural adhesive curing detection device and detection method |
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| CN115717046B (en) | 2023-05-12 |
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