CN115895549A - UV (ultraviolet) delayed curing adhesive and preparation method and application thereof - Google Patents
UV (ultraviolet) delayed curing adhesive and preparation method and application thereof Download PDFInfo
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- CN115895549A CN115895549A CN202310015552.9A CN202310015552A CN115895549A CN 115895549 A CN115895549 A CN 115895549A CN 202310015552 A CN202310015552 A CN 202310015552A CN 115895549 A CN115895549 A CN 115895549A
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- 239000000853 adhesive Substances 0.000 title claims abstract description 110
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 110
- 230000003111 delayed effect Effects 0.000 title abstract description 14
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 239000003822 epoxy resin Substances 0.000 claims abstract description 66
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 66
- 238000000034 method Methods 0.000 claims abstract description 50
- 238000007789 sealing Methods 0.000 claims abstract description 46
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000012745 toughening agent Substances 0.000 claims abstract description 10
- 239000003085 diluting agent Substances 0.000 claims abstract description 9
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002318 adhesion promoter Substances 0.000 claims abstract description 8
- 239000003623 enhancer Substances 0.000 claims abstract description 5
- 238000001723 curing Methods 0.000 claims description 65
- 238000004826 seaming Methods 0.000 claims description 37
- 238000003756 stirring Methods 0.000 claims description 27
- 239000003292 glue Substances 0.000 claims description 26
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 12
- -1 hexafluoroantimonate Chemical compound 0.000 claims description 12
- 239000010410 layer Substances 0.000 claims description 12
- 238000011417 postcuring Methods 0.000 claims description 10
- 239000012790 adhesive layer Substances 0.000 claims description 9
- 229920001971 elastomer Polymers 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
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- 239000011258 core-shell material Substances 0.000 claims description 7
- AHHWIHXENZJRFG-UHFFFAOYSA-N oxetane Chemical compound C1COC1 AHHWIHXENZJRFG-UHFFFAOYSA-N 0.000 claims description 7
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- 125000005409 triarylsulfonium group Chemical group 0.000 claims description 4
- OLPZCIDHOZATMA-UHFFFAOYSA-N 2,2-dioxooxathiiran-3-one Chemical class O=C1OS1(=O)=O OLPZCIDHOZATMA-UHFFFAOYSA-N 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 239000003795 chemical substances by application Substances 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
- 150000002170 ethers Chemical class 0.000 claims description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 3
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- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 3
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- 150000003839 salts Chemical class 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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- 238000004026 adhesive bonding Methods 0.000 abstract description 12
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- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 7
- 239000002390 adhesive tape Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
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- FVCSARBUZVPSQF-UHFFFAOYSA-N 5-(2,4-dioxooxolan-3-yl)-7-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C(C(OC2=O)=O)C2C(C)=CC1C1C(=O)COC1=O FVCSARBUZVPSQF-UHFFFAOYSA-N 0.000 description 2
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- BXGYYDRIMBPOMN-UHFFFAOYSA-N 2-(hydroxymethoxy)ethoxymethanol Chemical compound OCOCCOCO BXGYYDRIMBPOMN-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- MEVBAGCIOOTPLF-UHFFFAOYSA-N 2-[[5-(oxiran-2-ylmethoxy)naphthalen-2-yl]oxymethyl]oxirane Chemical compound C1OC1COC(C=C1C=CC=2)=CC=C1C=2OCC1CO1 MEVBAGCIOOTPLF-UHFFFAOYSA-N 0.000 description 1
- JFWJMICCQJMARP-UHFFFAOYSA-N 2-propoxynaphtho[2,3-b]oxirene Chemical compound C1=CC=C2C(OCCC)=C(O3)C3=CC2=C1 JFWJMICCQJMARP-UHFFFAOYSA-N 0.000 description 1
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- 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
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000002313 adhesive film Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012952 cationic photoinitiator Substances 0.000 description 1
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Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Adhesives Or Adhesive Processes (AREA)
- Sealing Battery Cases Or Jackets (AREA)
Abstract
The invention relates to a UV (ultraviolet) delayed curing adhesive for sealing a cylindrical battery, and a preparation method and application thereof. The adhesive is prepared from 15 to 45 parts by weight of one or more naphthalene type epoxy resins, 5 to 15 parts by weight of one or more bridge ring type epoxy resins, 10 to 40 parts by weight of a toughening agent, 10 to 40 parts by weight of a reactive diluent, 0 to 5 parts by weight of a contact enhancer, 0.1 to 0.5 parts by weight of a photoinitiator and 0 to 5 parts by weight of an adhesion promoter. The obtained adhesive has excellent mechanical property, good bonding effect on aluminum materials, good sealing property, delayed curing, solvent corrosion resistance, low shrinkage, aging resistance and good impact shock resistance, is matched with a corresponding gluing and curing process, is applied to top cover sealing of a new energy cylindrical battery, can play a good sealing effect, and prevents electrolyte leakage.
Description
Technical Field
The invention relates to a new energy power battery, in particular to a UV (ultraviolet) delayed curing adhesive for sealing a cylindrical battery and a preparation method and application thereof.
Background
At present new forms of energy power battery mainly divide into square battery, cylinder battery and laminate polymer battery three major types, and wherein the structure of cylinder battery is inside electric core of aluminium system shell parcel and electrolyte, and according to current battery manufacturing process, top cap and middle cylinder casing about cylinder battery case divide into need seal and seal top cap and casing through the seaming technology. However, this process has certain quality implications: due to mechanical occlusion between metals, small gaps exist between occlusion positions, so that the whole battery is poor in sealing, the defects are not easy to detect in the production process, electrolyte leakage occurs in the use process, or defective products are increased, and the yield is reduced.
Because the adhesive has the advantages of good wettability, good cohesive force, high mechanical strength, good sealing performance and the like, the method for gluing and sealing the seaming position by using the glue or the adhesive tape is a method for effectively making up the hidden trouble of leakage and improving the yield, but the manufacturing process, the service environment and the service life of the power battery have higher requirements, and the glue or the adhesive tape is required to have the following requirements:
1) The wetting property is good, the bonding surface can be fully wetted, and small gaps can be filled;
2) The adhesive force is good, and the adhesive strength to the aluminum shell is good;
3) The adhesive is vibration-resistant, and the battery use environment relates to bumping vibration, so that the adhesive is required to be prevented from falling off and cracking under the vibration condition;
4) The sealing gasket is resistant to solvent erosion, and a rubber material can contact with an electrolyte at a seaming position, so that good sealing performance is required to be kept under the condition of long-term contact with the electrolyte;
5) The curing is rapidly carried out at room temperature, the curing is required to be finished in a short time in consideration of production efficiency and production line construction, so that the subsequent working procedures can be carried out;
6) High low temperature stability is good, and battery external environment can have winter and summer alternation, also has the intensification and cools down in the battery use, consequently needs to glue the material and all guarantee the functional quality in ambient temperature and service temperature scope.
In view of the above requirements, some existing products on the market at present have certain problems, and cannot completely meet the requirements of the process and the use. For example, the adhesive tape is simple in use process, strength is quickly built in a short time after the adhesive tape is attached, and the adhesive tape can resist vibration and impact, but due to the fact that unevenness possibly exists on the surface of an attaching surface, the adhesive tape is difficult to completely attach, and the sealing effect cannot be guaranteed. The thermoplastic adhesive has simple sizing process, high curing speed, good bonding force to aluminum and vibration impact resistance, but poor interface wettability of the thermoplastic adhesive and large attenuation of high-temperature and low-temperature performances. The thermosetting adhesive can meet the application requirements, but the thermosetting adhesive needs to be heated or placed at room temperature for a long time during curing, and cannot meet the requirement on production efficiency. For the UV curing adhesive, the general acrylic acid type UV curing adhesive has simple sizing process and high curing speed, but has the problems of poor solvent resistance, large shrinkage rate, oxygen inhibition, large bonding interface stress and the like. The cationic UV delayed curing adhesive can realize delayed curing, but has large bonding interface stress and poor bonding force on aluminum materials.
Therefore, there remains a need in the art for an adhesive that can be used for sealing cylindrical batteries and that meets the process and performance requirements of use.
Disclosure of Invention
In view of the foregoing, there remains a need in the art for an adhesive that can be used for sealing cylindrical cells and that meets the process and performance requirements of use. The inventor of the invention finds that by compounding epoxy resins with different photocuring reaction speeds, the pre-cured adhesive can be cured to be in a gel or visco-elastic state, so that the adhesive has certain body strength, but the adhesive which is not completely cured on the surface of the adhesive layer still has wettability and adhesiveness to an adhered interface, and is convenient for seaming and post-curing. The obtained adhesive product has good mechanical property, good bonding effect on aluminum materials, good sealing property, shadow curing and delayed curing, solvent corrosion resistance, low shrinkage, aging resistance and good impact shock resistance, is matched with corresponding sizing and curing processes, is applied to sealing of cylindrical batteries, shows good sealing effect and prevents electrolyte leakage. Thus, the present invention has been completed.
Accordingly, in a first aspect, there is provided an adhesive made from the following components:
15 to 45 parts by weight of one or more naphthalene type epoxy resins;
5 to 15 parts by weight of one or more bridge ring type epoxy resins;
10 to 40 parts by weight of a toughening agent selected from an epoxidized polyolefin resin or a core shell rubber;
10 to 40 parts by weight of a reactive diluent selected from at least one of polyether polyol, glycidyl ether, oxetane;
0 to 5 parts by weight of a contact enhancer selected from nano alumina or organobentonite;
0.1 to 0.5 parts by weight of a photoinitiator selected from at least one of diazonium salts, hexafluoroantimonate salts, diaryliodonium salts, triarylsulfonium salts, alkylsulfonium salts, iron arene salts, sulfonyloxy ketones, and triarylsiloxy ethers;
0 to 5 parts by weight of an adhesion promoter which is a silane coupling agent.
In a second aspect, there is provided a method of preparing the adhesive of the first aspect, comprising the steps of:
(1) Mixing naphthalene epoxy resin, bridged ring epoxy resin, reactive diluent and optional adhesion promoter to be uniform;
(2) Adding the toughening agent and the contact agent, and mixing uniformly again;
(3) Adding the photoinitiator, and stirring in vacuum until no bubbles exist.
In a third aspect, there is provided a method of sealing a cylindrical battery comprising the step of using the adhesive of the first aspect.
The invention has the advantages that: the invention provides a UV delayed curing adhesive compounded by fast curing epoxy resin and slow curing epoxy resin, which can be used for sealing a cylindrical battery, solves the problems of large bonding interface stress and poor bonding force on aluminum materials of a cationic UV delayed curing adhesive, and can meet the process and performance requirements of battery sealing. By using the UV delayed curing adhesive, the inner layer seaming position of the top cover of the cylindrical battery is coated with glue in advance and is pre-cured, the pre-cured adhesive has certain body strength and can keep gel or visco-elastic state, the surface of the adhesive layer is ensured to be still wetted, the subsequent seaming is convenient, and then the post-curing is carried out, so that the fine leak and gap can be effectively compensated, the electrolyte is prevented from leaking outwards in the using process of the battery, the good sealing performance of the battery is ensured, the yield and the reliability of the product are improved, the process is simple, and the glue spraying process can be used for realizing automatic gluing.
Drawings
In order to more clearly illustrate the detailed description of the invention or the technical solutions in the prior art, the drawings used in the detailed description or the prior art description will be briefly described below.
FIG. 1 shows a shear strength comparison of an adhesive prepared according to an embodiment of the present invention and a control adhesive.
Fig. 2 shows a shore hardness comparison of an adhesive prepared according to an embodiment of the present disclosure and a control adhesive.
FIG. 3 shows a comparison of swelling ratios of an adhesive prepared according to an embodiment of the present invention and a control adhesive.
Figure 4 shows a comparison of the dissolution rates of an adhesive prepared according to an embodiment of the present invention and a control adhesive.
Figure 5 shows a comparison of impact times for an adhesive prepared according to an embodiment of the present invention and a control adhesive.
FIG. 6 shows a comparison of tack free times for adhesives prepared according to embodiments of the invention and a control adhesive.
Detailed Description
Hereinafter, the present invention will be described in detail with reference to the accompanying drawings. It is to be understood that the following description is intended to illustrate the present invention by way of example only and is not intended to limit the scope of the invention, which is defined by the appended claims. Also, it is understood by those skilled in the art that modifications may be made to the technical aspects of the present invention without departing from the spirit and gist of the present invention. Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art.
Where numerical ranges are provided, such as concentration ranges, percentage ranges, or ratio ranges, it is understood that each intervening value, to the tenth of the unit of the lower limit unless the context clearly dictates otherwise, between the upper and lower limit of that range and any other stated or intervening value in that stated range is encompassed within the subject matter. The upper and lower limits of these smaller ranges may independently be included in the smaller ranges, and such embodiments are also encompassed within the subject matter, subject to any specifically excluded limit in the stated range. Where the stated range includes one or both of the limits, ranges excluding either or both of those included limits are also included in the subject matter.
In the context of the present invention, many embodiments use the expression "comprising", "including" or "consisting essentially of … …". The expressions "comprising", "including" or "consisting essentially of … …" are generally to be understood as open-ended expressions that include not only the elements, components, assemblies, method steps, etc., specifically listed after the expression, but also other elements, components, assemblies, method steps. In addition, the expressions "comprising", "including" or "consisting essentially of … …" may in some cases also be understood as a closed expression, meaning that only the elements, components, assemblies, method steps specifically listed after the expression are included, but not any other elements, components, assemblies, method steps. At this time, the expression is equivalent to the expression "consisting of … …".
For a better understanding of the present teachings and not to limit the scope of the present teachings, unless otherwise indicated, all numbers expressing quantities, percentages or proportions used in the specification and claims, as well as other numerical values, are to be understood as being modified in all instances by the term "about". Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that may vary depending upon the desired properties sought to be obtained. At the very least, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.
Accordingly, in a first aspect, there is provided an adhesive made from the following components:
15 to 45 parts by weight of one or more naphthalene-type epoxy resins;
5 to 15 parts by weight of one or more bridge ring type epoxy resins;
10 to 40 parts by weight of a toughening agent selected from an epoxidized polyolefin resin or a core shell rubber;
10 to 40 parts by weight of a reactive diluent selected from at least one of polyether polyol, glycidyl ether, oxetane;
0 to 5 parts by weight of a contact enhancer selected from nano alumina or organobentonite;
0.1 to 0.5 parts by weight of a photoinitiator selected from at least one of diazonium salts, diaryliodonium salts, triarylsulfonium salts, alkylsulfonium salts, iron arene salts, sulfonyloxy ketones, and triarylsiloxy ethers;
0 to 5 parts by weight of an adhesion promoter, which is a silane coupling agent.
In the context of the present invention, the term "naphthalene-type epoxy resin" refers to an epoxy resin containing a naphthalene ring structure.
In a particular embodiment, the naphthalene type epoxy resin has a structure selected from the group consisting of formulas I-IV below:
formula I
Formula II
Formula III
Formula IV.
The naphthalene type epoxy resin may be obtained commercially, for example, a naphthalene type epoxy resin obtained from a monomer of formula II (1,6-bis (2,3-epoxypropan-1-yloxy) naphthalene) may be obtained from Epiclon HP-4032D (epoxy equivalent of 136-148) of DIC, and for example, a naphthalene type epoxy resin prepared from a monomer of formula I may be obtained from EXA-4710 (molecular weight of 556) of DIC, but is not limited thereto.
In the context of the present invention, the term "bridged ring type epoxy resin" refers to an epoxy resin containing a bridged ring structure.
In a specific embodiment, the bridge ring type epoxy resin has a structure selected from the following formulas V or VI:
formula V
Formula VI.
The bridge ring type epoxy resin may be obtained commercially, for example, a bridge ring type epoxy resin obtained by polymerizing a monomer of formula V (dicyclopentadiene dimethanol diglycidyl ether) may be obtained from EP-4088L (epoxy equivalent weight 165) of ADEKA; also for example, a bridged epoxy resin obtained by polymerization of a monomer of formula VI (phenyl glycidyl ether-co-dicyclopentadiene), commercially available from DIC as Epiclon HP-7200H (epoxy equivalent weight 280), is a mixture comprising the compounds of the following exemplary structural formulae VI-1 to VI-3.
Formula VI-1
Formula VI-2
Formula VI-3
In yet another specific embodiment, the naphthalene type epoxy resin has a faster photocuring speed than the bridge ring type epoxy resin. Alternatively, the naphthalene type epoxy resin is a fast curing epoxy resin, and the bridge type epoxy resin is a slow curing epoxy resin, relatively speaking. The naphthalene epoxy resin is quickly photocured in the pre-curing step, so that the adhesive has certain body strength, and the bridge ring type epoxy resin in the adhesive is low in curing speed and is not completely cured, so that the adhesive can still keep gel or viscoelasticity and has wettability and adhesion to an adhered interface.
In the context of the present invention, the terms "fast curing epoxy resin" and "slow curing epoxy resin" are relative terms, and when formulated in the same formulation, the fast curing epoxy resin requires relatively less energy of light to achieve the final degree of cure, such as bisphenol a epoxy resin and bisphenol F epoxy resin, and also such as naphthalene type epoxy resin used in the present invention, can be cured rapidly in the system, serving to increase the adhesive strength of the adhesive and improve the toughness of the adhesive, while the slow curing epoxy resin requires relatively more energy of light to achieve the final degree of cure, such as bridge ring type epoxy resin used in the present invention, serves to regulate the curing speed in the adhesive, reduce interfacial shrinkage stress, and improve aging resistance.
In a particular embodiment, the toughening agent can be an epoxidized polyolefin resin, such as a polybutadiene epoxy resin, such as Poly bd 605E (molecular weight 1450) available from gram Lei Weili, but is not so limited. The lower polarity of the polyolefin epoxy resin and the rigidity of an epoxy adhesive system can ensure the solvent corrosion resistance of an adhesive layer formed after the adhesive is cured, so that the reliability of the cylindrical battery in the use process is ensured.
In yet another specific embodiment, the toughening agent can be a core shell rubber, such as, but not limited to, a core shell rubber available from Carnica under the trade designation MX-135 (viscosity 13000cps at 50 ℃).
The inventor finds that the toughening agent used in the adhesive disclosed by the invention can effectively reduce the hardness of a glue layer formed after the adhesive is cured, improve the vibration and impact resistance, ensure the solvent corrosion resistance of the glue layer formed after the adhesive is cured, and further ensure the reliability of the cylindrical battery in the using process.
In yet another specific embodiment, the reactive diluent is an oxetane, but is not limited thereto. Without wishing to be bound by theory, the inventor finds that the oxetane serving as the reactive diluent greatly improves the bonding strength of the adhesive to the aluminum material, realizes good bonding to the aluminum material, and further ensures good sealing performance of the cylindrical battery in the using process.
In yet another specific embodiment, the contact enhancer is an organobentonite clay. Without wishing to be bound by theory, the organobentonite as a thixotrope may modify the rheological properties of the adhesive.
In yet another specific embodiment, the photoinitiator is a triarylsulfonium salt. It will be appreciated by those skilled in the art that the individual components of the adhesives described above are present independently in the adhesive in an unreacted state prior to exposure to light. Once irradiated by UV light, the cationic photoinitiator can release Lewis acid under the irradiation of the UV light, so that the crosslinking reaction between epoxy groups is catalyzed, and the precuring of the glue is realized.
In yet another specific embodiment, the adhesion promoter is an epoxy-terminated silane coupling agent.
In a second aspect, there is provided a method of preparing the adhesive of the first aspect, comprising the steps of:
(1) Mixing naphthalene epoxy resin, bridged ring epoxy resin, reactive diluent and optional adhesion promoter to be uniform;
(2) Adding the toughening agent and the contact agent, and mixing uniformly again;
(3) Adding the photoinitiator, and stirring in vacuum until no bubbles exist.
The preparation can be carried out in equipment customary in the art, for example in a double planetary mixer. Step (1) may be carried out at room temperature for 30 to 60 minutes until homogeneous. Step (2) may also be carried out at room temperature for 30 to 60 minutes until homogeneous. Step (3) can also be carried out at room temperature for at least 30 minutes until no bubbles exist.
The UV delayed curing adhesive prepared by the method can be rapidly subjected to initial curing through UV illumination, the initial body strength is established, and the phenomenon that the liquid adhesive is extruded or thrown away when in seaming is avoided. Meanwhile, the adhesive after initial curing can maintain the wettability and the adhesiveness to the bonded interface due to the incompletely cured bridge ring type epoxy resin, so that the adhesive can be post-cured at room temperature or under a heating condition after being curled, the final strength is achieved, and the production efficiency is further met. The initial curing degree and the post-curing speed can be adjusted as required, and the diversification of the battery production process is further matched.
In a third aspect, there is provided a method of sealing a cylindrical battery comprising the step of using the adhesive of the first aspect.
In a specific embodiment, the method comprises:
(1) Coating the adhesive at the inner layer seaming position of the top cover of the cylindrical battery to form an adhesive layer;
(2) Pre-curing the glue layer by irradiating the glue layer with UV light;
(3) Rolling and sealing the top cover to a middle cylindrical shell of the cylindrical battery;
(4) And post-curing the pre-cured adhesive layer.
Before step (1), the top cover or the seaming position of the top cover may be cleaned, for example, by laser, but not limited thereto.
In step (1), the adhesive may be applied by means well known to those skilled in the art, such as, but not limited to, spraying, to obtain a film layer of adhesive that is uniformly distributed at the location of the inner seam of the overcap.
In a particular embodiment, the bondline may have a thickness of 0.2 mm to 0.5 mm.
In a preferred embodiment, the bondline may have a thickness of 0.3 mm to 0.4 mm.
In the step (2), the UV delayed curing adhesive is initially cured by utilizing the principle that the UV light enables the photoinitiator to release Lewis acid to catalyze the epoxy crosslinking reaction, the adhesive layer pre-cured by the UV light is in a gel or visco-elastic state and has certain body strength, but the surface of the adhesive layer still has wettability and adhesiveness, so that the seaming in the step (3) can be carried out, and the process requirement of rapid shaping can be met.
In yet another specific embodiment, a mercury lamp light source, an LED light source, or a xenon lamp light source may be used to provide UV light with a curing energy of 2000 mJ/cm2 to 12000 mJ/cm 2.
In a preferred embodiment, a mercury lamp light source, an LED light source, or a xenon lamp light source may be used to provide UV light having a curing energy of 3000 mJ/cm2 to 6000 mJ/cm 2.
It will thus be appreciated that the adhesives of the invention can be cured by a curing energy of 2000 mJ/cm2 to 12000 mJ/cm 2. In a preferred embodiment, the adhesive of the present invention can be cured by a curing energy of 3000 mJ/cm2 to 6000 mJ/cm 2. One skilled in the art will appreciate that cure energy = cure time x light intensity, a low cure energy indicating a short light time required for the same light intensity, and vice versa. The adhesive disclosed by the invention simultaneously comprises the fast curing epoxy resin such as naphthalene epoxy resin and the slow curing epoxy resin such as bridge epoxy resin, so that the adhesive not only can be suitable for low curing energy such as 2000 mJ/cm < 2 >, but also can be suitable for high curing energy such as 12000 mJ/cm < 2 >, and the situations that the adhesive loses adhesiveness prematurely due to overhigh curing energy or is not cured fully due to overlow curing energy and the like do not occur, so that the adhesive has a wider assembly process window while the process efficiency is ensured.
In the step (4), the post-curing process is a shadow-curable process, that is, part of the adhesive can be cured without being irradiated by UV light, because lewis acid released by the photoinitiator of the cationic system in the pre-curing step can continuously catalyze the epoxy crosslinking reaction in the post-curing step, thereby realizing the post-curing of the adhesive.
In yet another specific embodiment, the post-curing may be performed at normal temperature for 12 to 72 hours.
The liquid adhesive can realize the complete bonding of various special-shaped curved surfaces of the cylindrical battery, has good wettability on the surface of the top cover or the shell, and can effectively fill gaps and holes on the top cover or the shell; the adhesive force is good, and the adhesive can be effectively adhered to the top cover or the shell and cannot fall off. The adhesive layer of the adhesive has good toughness after being cured, and can resist vibration or impact; the solvent resistance is good, and the electrolyte is not easy to corrode; the high-low temperature performance is stable, and the requirements on sealing performance and reliability can be met in the use temperature environment.
Examples
In the following examples, the preparation method of the insulating adhesive film of the present invention and the characterization of the relevant properties are shown. Unless otherwise specified, the test methods employed therein were all conventional methods, and the test materials used in the following examples were all purchased from a conventional reagent store. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It should be noted that the terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The foregoing summary, as well as the following detailed description, is intended merely to be illustrative of the invention and is not intended to be in any way limiting. The scope of the invention is to be determined by the appended claims without departing from the spirit and scope of the invention.
Example 1: preparation of the Adhesives
Control adhesives and exemplary UV delayed cure adhesives of the present invention were prepared according to the control formulations one and two and formulations one through six given in table 1 below, respectively, in the following steps.
The first reference formula: adding 45 parts of bisphenol A epoxy resin, 15 parts of bisphenol F epoxy resin, 20 parts of polyether polyol and 1 part of silane coupling agent into a double-planet stirrer, stirring at room temperature for 30-60min until the mixture is uniform, adding 2 parts of fumed silica, stirring at room temperature for 30-60min until the mixture is uniform, finally adding 0.2 part of hexafluoroantimonate as a photoinitiator, and stirring at room temperature in vacuum for 30min until no bubbles exist.
And a second comparison formula: adding 45 parts of bisphenol A epoxy resin, 15 parts of bisphenol F epoxy resin, 20 parts of polyether polyol and 1 part of silane coupling agent into a double-planet stirrer, stirring at room temperature for 30-60min until the mixture is uniform, adding 2 parts of organic bentonite, stirring at room temperature for 30-60min until the mixture is uniform, finally adding 0.2 part of hexafluoroantimonate as a photoinitiator, and stirring at room temperature under vacuum for 30min until no bubbles exist.
The formula I is as follows: adding 45 parts of naphthalene epoxy resin, 15 parts of bridge ring epoxy resin and 1 part of silane coupling agent into a double-planet stirrer, stirring at room temperature for 30-60min to be uniform, then adding 20 parts of epoxidized polyolefin resin and 2 parts of organic bentonite, stirring at room temperature for 30-60min to be uniform, finally adding 0.2 part of hexafluoroantimonate as a photoinitiator, and stirring at room temperature in vacuum for 30min to be bubble-free.
And a second formula: adding 45 parts of naphthalene epoxy resin, 15 parts of bridge ring epoxy resin and 1 part of silane coupling agent into a double-planet stirrer, stirring at room temperature for 30-60min to be uniform, then adding 40 parts of epoxidized polyolefin resin and 2 parts of organic bentonite, stirring at room temperature for 30-60min to be uniform, finally adding 0.2 part of hexafluoroantimonate as a photoinitiator, and stirring at room temperature in vacuum for 30min to be bubble-free.
And the formula III: adding 35 parts of naphthalene epoxy resin, 5 parts of bridge ring epoxy resin and 1 part of silane coupling agent into a double-planet stirrer, stirring at room temperature for 30 to 60min to be uniform, adding 40 parts of epoxidized polyolefin resin and 2 parts of organic bentonite, stirring at room temperature for 30 to 60min to be uniform, adding 0.2 part of hexafluoroantimonate serving as a photoinitiator, and stirring at room temperature in vacuum for 30min to be bubble-free.
Table 1: the weight portions of each component in the adhesive
The formula four: adding 40 parts of naphthalene epoxy resin, 10 parts of bridge ring epoxy resin, 10 parts of oxetane and 1 part of silane coupling agent into a double-planet stirrer, stirring at room temperature for 30 to 60min till the mixture is uniform, then adding 20 parts of epoxidized polyolefin resin and 2 parts of organic bentonite, stirring at room temperature for 30 to 60min till the mixture is uniform, finally adding 0.2 part of hexafluoroantimonate as a photoinitiator, and stirring at room temperature for 30min till no bubbles exist.
And a fifth formula: adding 35 parts of naphthalene epoxy resin, 5 parts of bridge ring epoxy resin, 20 parts of oxetane and 1 part of silane coupling agent into a double-planet stirrer, stirring at room temperature for 30 to 60min till the mixture is uniform, then adding 20 parts of core-shell rubber and 2 parts of organic bentonite, stirring at room temperature for 30 to 60min till the mixture is uniform, finally adding 0.2 part of photoinitiator, and stirring at room temperature under vacuum for 30min till no bubbles exist.
And the formula six: adding 40 parts of naphthalene epoxy resin, 10 parts of bridged epoxy resin, 10 parts of oxetane and 1 part of silane coupling agent into a double-planet stirrer, stirring at room temperature for 30 to 60min till the mixture is uniform, then adding 20 parts of core-shell rubber and 2 parts of organic bentonite, stirring at room temperature for 30 to 60min till the mixture is uniform, finally adding 0.2 part of photoinitiator, and stirring at room temperature under vacuum for 30min till no bubbles exist.
Example 2: characterization of the Adhesives
In this example, the adhesives prepared in example 1 (control formulations one and two and formulations one to six) were each tested as follows:
shear strength: the samples were prepared by die shear test (die shear test) in which a glass substrate was bonded to an aluminum substrate with a bonding area of 3 mm by 3 mm, irradiated with light from a 365 nm LED light source at an irradiation energy of 3000 mJ/cm2, cured at room temperature for 24 hours, and then tested by a Dage diethrust press at a speed of 6 mm/min, and the results are shown in FIG. 1.
As can be seen from fig. 1, the shear strengths of the formulations one to six of the present invention are higher than those of the control formulations one and two, especially the formulations three to six, which are significantly higher than those of the control formulations one and two.
Hardness: the adhesive is prepared into the thickness of 6 mm, a 365 nm LED light source is used for illumination, the irradiation energy is 9000 mJ/cm < 2 >, the adhesive is cured for 24 hours at room temperature, and then a Shore hardness tester is used for testing, and the test result is shown in figure 2.
As can be seen from fig. 2, the formulations one through six of the present invention have a slightly lower hardness than the comparative formulations one and two, and show good impact shock resistance.
Swelling ratio: 2.0 +/-0.05 g of adhesive is irradiated by a 365 nm LED light source, the irradiation energy is 6000 mJ/cm2, the adhesive is placed in a PP cup for sealing after being cured for 24 hours at room temperature, 50 +/-0.5 g of lithium-containing electrolyte is added, the PP cup is placed in an oven at 85 ℃ for 24 hours, the PP cup is taken out and wiped and weighed, the weight difference before and after the experiment and the initial weight are in percentage, and the test result is shown in figure 3.
As can be seen from fig. 3, the swelling ratios of the inventive formulations one to six were significantly lower than the comparative formulations one and two.
In addition, in the process of soaking the electrolyte in the contrast formula, small bubbles appear on the surface of the rubber block, but the phenomenon does not appear in the formula of the invention, which indicates that the gas-phase silicon dioxide can react with the components in the electrolyte to generate gas, so the gas-phase silicon dioxide is not suitable for being used in the application.
Dissolution rate: extruding the adhesive to form 1.4 +/-0.05 g, irradiating by using a 365 nm LED light source, irradiating with energy of 6000 mJ/cm2, curing at room temperature for 24 hours, then placing into a penicillin bottle for sealing, adding 7 +/-0.1 g of lithium-free electrolyte, placing in an oven at 85 ℃ for 24 hours, taking out, extracting the solution while hot by using an injector, testing the mass fraction of the solute in the solution by using TGA, calculating the mass of the solute in the whole solution, and considering the percentage of the mass of the solute to the initial weight, wherein the test result is shown in figure 4.
As can be seen from fig. 4, the dissolution rates of the formulations one to six of the present invention are significantly lower than those of the control formulations one and two.
Dupont impact strength: the cross bonding method is used for preparing samples, a circle is dispensed on an aluminum sheet, the inner diameter of the circle is 25.4 mm, the width of a glue line is 1.0 +/-0.1 mm, the circle center of another punched glass round hole is aligned to the circle center surrounded by the glue line for bonding, the thickness of a glue layer is controlled to be 0.25 mm, a 365 nm LED light source is used for illumination, the irradiation energy is 6000 mJ/cm < 2 >, after the glass round hole is solidified for 24 hours at room temperature, a DuPont impact tester is used for testing, an impact hammer 200 g and the height of 50 cm are used for testing the impact frequency during damage, and the test result is shown in figure 5.
As can be seen from fig. 5, the dupont impact strengths of the formulations one to six of the present invention are significantly better than those of the control formulations one and two, especially the formulations three and five, and exhibit the most excellent impact resistance.
Opening time: 0.1ml of glue is applied on an aluminum sheet, the aluminum sheet is irradiated by the illumination intensity of 3000 mJ/cm2 and 6000 mJ/cm2 respectively, the surface viscosity of the aluminum sheet is tested by a finger touch method after irradiation, timing is started until the time when the surface loses viscosity is regarded as surface drying time.
As can be seen from fig. 6, the open time for formulations one to six of the present invention is significantly longer than the control formulation, with a broader assembly process window.
Example 3: roll seal
In this example, the adhesive prepared in example 1 was used to crimp a battery. The seaming process is as follows:
roll seal control example 1: and (4) placing the battery top cover on the battery shell for seaming, and then placing for 24 hours at room temperature.
Crimp control example 2: the battery top cover is placed on a clamp, a dual-purpose automatic glue spreader for a reference formula is used for gluing at a sealing position, the thickness is 0.3 mm, the pre-curing is carried out by 365 nm LED light source irradiation, the curing energy is 3000 mJ/cm < 2 >, then the battery top cover is placed on a battery shell for sealing, and the battery top cover is cured for 24 hours at room temperature after sealing.
Comparative roll-sealing example 3: placing the top cover of the battery on a clamp, gluing the battery at a sealing position by using a dual-purpose automatic glue spreader for comparison formula, pre-curing by irradiating a 365 nm LED light source with the thickness of 0.3 mm and the curing energy of 6000 mJ/cm < 2 >, then placing the battery on a battery shell for sealing, and curing for 24 hours at room temperature after sealing.
Crimp example 1: the battery top cover is placed on a clamp, a formula three-purpose automatic glue spreader is used for spreading glue at a sealing position, the thickness is 0.3 mm, the curing is performed by irradiation of a 365 nm LED light source, the curing energy is 3000 mJ/cm < 2 >, then the battery top cover is placed on a battery shell for sealing, and the battery top cover is cured for 24 hours at room temperature after being sealed.
Crimp example 2: the battery top cover is placed on a clamp, a formula three-purpose automatic glue spreader is used for gluing at a seaming position, the thickness is 0.4 mm, the precuring is carried out by the radiation of a 365 nm LED light source, the curing energy is 3000 mJ/cm < 2 >, then the battery top cover is placed on a battery shell for seaming, and the battery top cover is cured for 72 hours at room temperature after seaming.
Crimp example 3: the battery top cover is placed on a clamp, a formula three-purpose automatic glue spreader is used for gluing at a seaming position, the thickness is 0.3 mm, the battery is pre-cured by irradiation of a 365 nm LED light source, the curing energy is 6000 mJ/cm < 2 >, then the battery top cover is placed on a battery shell for seaming, and the battery top cover is cured for 24 hours at room temperature after seaming.
Crimp example 4: the battery top cover is placed on a clamp, a formula three-purpose automatic glue spreader is used for gluing at a seaming position, the thickness is 0.4 mm, the battery is pre-cured by irradiation of a 365 nm LED light source, the curing energy is 6000 mJ/cm < 2 >, then the battery top cover is placed on a battery shell for seaming, and the battery top cover is cured for 24 hours at room temperature after seaming.
Crimp example 5: placing the top cover of the battery on a clamp, gluing the formula four at a seaming position by using an automatic gluing machine, estimating the thickness of the battery by using a 365 nm LED light source irradiation, and placing the battery on a battery shell for seaming, wherein the curing energy is 3000 mJ/cm < 2 >, and the battery is cured for 24 hours at room temperature after seaming.
Crimp example 6: the battery top cover is placed on a clamp, the formula five-purpose automatic glue spreader is used for spreading glue at a seaming position, the thickness is 0.3 mm, the estimation of 365 nm LED light source irradiation is carried out, the curing energy is 3000 mJ/cm < 2 >, then the battery top cover is placed on a battery shell for seaming, and the battery top cover is cured for 24 hours at room temperature after seaming.
Crimp example 7: placing the top cover of the battery on a clamp, gluing the formula VI at a seaming position by using an automatic gluing machine, estimating the thickness of the battery by using a 365 nm LED light source irradiation, and placing the battery on a battery shell for seaming, wherein the curing energy is 3000 mJ/cm < 2 >, and the battery is cured for 24 hours at room temperature after seaming.
Example 4: testing of crimped batteries
Helium detection: for the battery prepared by the roll sealing process in example 3, helium gas of 0.1 Mpa pressure was added into the sealed case from the liquid injection hole, the case was kept for 30min, and the air pressure decay condition was detected, and the test results are shown in table 2. The results show that examples 1-7, which used adhesive during roll sealing, both had an air pressure decay magnitude of <0.3 relative to control 1, which did not use adhesive during roll sealing, and to control 2 and control 3, which used control formulation two, indicating that excellent sealing results can be obtained with the adhesive of the present invention.
Liquid resistance test: in the battery manufactured by the roll sealing process in example 3, after the electrolyte was applied to the sealed case from the liquid inlet, the case was left to stand at 85 ℃ and 85% RH for aging, and it was checked whether or not the electrolyte was leaked from the sealed portion. The test results are shown in table 2. The results show that the electrolyte leakage started on day one in comparative examples 1 and 3, and the electrolyte leakage started on day 7 in comparative example 2, whereas the electrolyte leakage did not occur for more than 60 days in each of examples 1 to 7, which indicates that the sealing effect is excellent and the electrolyte can be tolerated.
And (3) drop test: for the battery prepared by the roll-sealing process in example 3, the electrolyte was applied from the filling hole into the sealed case, which was then sealed, and dropped freely at a height of 1.5m, and the battery after dropping was left to stand at 85 ℃ and 85% RH for continuous aging to see whether or not the electrolyte was oozed from the sealed portion. The test results are shown in table 2. The results show that the comparative examples 1-3 all start to leak the electrolyte in the first day, while the examples 1-7 do not leak the electrolyte in more than 60 days, which shows that the adhesive of the present invention has excellent sealing effect, and that the adhesive can resist the electrolyte and resist the influence of falling.
Table 2: test results for rolled and sealed batteries
From the results of table 2 above, it can be seen that the adhesive of the present invention can provide excellent seaming effect for the battery at a lower curing energy of 3000 mJ/cm2 or at a higher curing energy of 6000 mJ/cm2, and not only exhibits very low air pressure attenuation, but also can resist the electrolyte and resist the falling. The adhesive adopting the mixture of the bisphenol A epoxy resin and the bisphenol F epoxy resin cannot realize good sealing under the higher curing energy of 6000 mJ/cm < 2 >, the seaming result is similar to the seaming result without the adhesive, and the seaming result under the lower curing energy of 3000 mJ/cm < 2 > is much lower than the seaming result of the high curing energy, but the seaming result is not as good as the adhesive of the invention, the effective sealing effect is not realized at the same time, and the adhesive cannot be used for new energy power batteries.
Claims (10)
1. An adhesive, which is prepared from the following components:
15 to 45 parts by weight of one or more naphthalene-type epoxy resins;
5 to 15 parts by weight of one or more bridge ring type epoxy resins;
10 to 40 parts by weight of a toughening agent selected from an epoxidized polyolefin resin or a core shell rubber;
10 to 40 parts by weight of a reactive diluent selected from at least one of polyether polyol, glycidyl ether, oxetane;
0 to 5 parts by weight of a contact enhancer selected from nano alumina or organobentonite;
0.1 to 0.5 parts by weight of a photoinitiator selected from at least one of diazonium salts, hexafluoroantimonate, diaryliodonium salts, triarylsulfonium salts, alkylsulfonium salts, iron arene salts, sulfonyloxy ketones, and triarylsiloxy ethers;
0 to 5 parts by weight of an adhesion promoter which is a silane coupling agent.
2. The adhesive according to claim 1, wherein the naphthalene type epoxy resin has a faster light curing speed than the bridge ring type epoxy resin.
3. The adhesive of claim 1 or 2, wherein the naphthalene epoxy resin has a structure selected from the following formulas I-IV:
formula I
Formula II
Formula III
Formula IV.
4. The adhesive of claim 1 or 2, wherein the bridge ring type epoxy resin has a structure selected from the following formulas V-VI:
formula V
Formula VI.
5. A method of making the adhesive of any one of claims 1-4 comprising the steps of:
(1) Mixing naphthalene epoxy resin, bridged ring epoxy resin, reactive diluent and optional adhesion promoter to be uniform;
(2) Adding the toughening agent and the contact agent, and mixing uniformly again;
(3) Adding the photoinitiator, and stirring in vacuum until no bubbles exist.
6. A method of sealing a cylindrical battery comprising the step of using the adhesive of any one of claims 1-4.
7. The method of claim 6, wherein the method comprises:
(1) Coating the adhesive at the inner layer seaming position of the top cover of the cylindrical battery to form an adhesive layer;
(2) Pre-curing the glue layer by irradiating the glue layer with UV light;
(3) The top cover is sealed on the middle cylindrical shell of the cylindrical battery in a rolling mode;
(4) Post-curing the pre-cured glue layer.
8. The method of claim 7, wherein the bondline has a thickness of 0.2 mm to 0.5 mm.
9. The method of claim 7, wherein a mercury lamp light source, an LED light source, or a xenon lamp light source is used to provide UV light with a curing energy of 2000 mJ/cm2 to 12000 mJ/cm 2.
10. The method according to claim 7, wherein the post-curing is performed at normal temperature for 12 to 72 hours.
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