CN115895549B - UV delay curing adhesive, preparation method and application thereof - Google Patents
UV delay curing adhesive, preparation method and application thereof Download PDFInfo
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- CN115895549B CN115895549B CN202310015552.9A CN202310015552A CN115895549B CN 115895549 B CN115895549 B CN 115895549B CN 202310015552 A CN202310015552 A CN 202310015552A CN 115895549 B CN115895549 B CN 115895549B
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- 230000001070 adhesive effect Effects 0.000 title claims abstract description 110
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 239000003822 epoxy resin Substances 0.000 claims abstract description 62
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 62
- 238000007789 sealing Methods 0.000 claims abstract description 60
- 238000000034 method Methods 0.000 claims abstract description 52
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- 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 10
- 239000012745 toughening agent Substances 0.000 claims abstract description 10
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- 239000002318 adhesion promoter Substances 0.000 claims abstract description 8
- 238000001723 curing Methods 0.000 claims description 67
- 238000005096 rolling process Methods 0.000 claims description 38
- 239000003292 glue Substances 0.000 claims description 19
- 239000010410 layer Substances 0.000 claims description 14
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- 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
- 125000005520 diaryliodonium group Chemical group 0.000 claims description 3
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- 238000000016 photochemical curing Methods 0.000 claims description 3
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- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
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- 229910052782 aluminium Inorganic materials 0.000 abstract description 14
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 14
- 239000000463 material Substances 0.000 abstract description 9
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-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
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- 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
- 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 1
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- 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 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 delay curing adhesive for sealing a cylindrical battery, and a preparation method and application thereof. The adhesive of the invention is made 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 bridged 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 touch-up agent, 0.1 to 0.5 parts by weight of a photoinitiator, and 0 to 5 parts by weight of an adhesion promoter. The adhesive obtained by the method has excellent mechanical properties, good bonding effect on aluminum materials, good sealing performance, delayed curing, solvent erosion resistance, low shrinkage, aging resistance, good impact shock resistance and corresponding sizing and curing processes, is applied to top cover sealing of new energy cylindrical batteries, and can play a good sealing role in preventing electrolyte leakage.
Description
Technical Field
The invention relates to a new energy power battery, in particular to a UV delay curing adhesive for sealing a cylindrical battery, and a preparation method and application thereof.
Background
At present, the new energy power battery is mainly divided into three major categories of square batteries, cylindrical batteries and soft package batteries, wherein the cylindrical batteries are structurally formed by wrapping an internal electric core and electrolyte with an aluminum shell, and the cylindrical batteries are divided into an upper top cover, a lower top cover and a middle cylindrical shell according to the existing battery manufacturing process, and the top cover and the shell are required to be sealed and sealed through a rolling and sealing process. However, this process has certain quality hazards: due to the mechanical occlusion between metals, small gaps exist between occlusion positions, so that poor sealing of the whole battery is caused, and the defects are difficult to detect in the production process, so that 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 glue or the adhesive tape is used for gluing and sealing the rolling sealing position, which is a method for effectively compensating hidden leakage trouble and improving yield, but because the manufacturing process, the service environment and the service life of the power battery have higher requirements, the glue or the adhesive tape is required to have the following requirements:
1) The wettability is good, the bonding surface can be fully infiltrated, and the filling of the tiny gaps can be made up;
2) The adhesive force is good, and the adhesive strength to the aluminum shell is good;
3) Vibration resistance, the battery service environment relates to jolt vibration, so that the adhesive needs to be ensured not to fall off and crack under the vibration condition;
4) The adhesive material contacts the electrolyte at the sealing position, and good sealing performance is still required to be maintained under the condition of long-term contact with the electrolyte;
5) The room temperature is quickly cured, and the curing is required to be completed in a short time in consideration of the production efficiency and the production line construction, so that the process can be carried out;
6) The high-low temperature stability is good, the external environment of the battery can be alternated in winter and summer, and the battery is heated and cooled in the use process, so that the rubber material is required to ensure good performance in the environment temperature and the use temperature range.
Aiming at the requirements, some existing products on the market at present have certain problems, and the process and use requirements cannot be completely met. For example, the adhesive tape has simple application process, can quickly establish strength in a short time after bonding, can resist vibration impact, but can not ensure sealing effect because the surface of the bonding surface is possibly uneven, and the adhesive tape is difficult to completely bond. The thermoplastic adhesive has the advantages of simple sizing process, high curing speed, good binding force to aluminum and capability of resisting vibration impact, but poor interface wettability of the thermoplastic adhesive and large high-temperature and low-temperature performance attenuation. Each performance of the thermosetting adhesive can meet the application requirement, but the thermosetting adhesive needs to be heated or placed at room temperature for a long time during curing, and cannot meet the requirement of production efficiency. For the UV curing adhesive, the general acrylic acid type UV curing adhesive has the advantages of simple sizing process, high curing speed, but the problems of poor solvent resistance, large shrinkage, oxygen inhibition, large bonding interface stress and the like. The cationic UV delay curing adhesive can realize delay curing, but has large bonding interface stress and poor bonding force for aluminum materials.
Thus, there remains a need in the art for an adhesive that can be used in cylindrical battery seals and meets the handling and performance requirements.
Disclosure of Invention
As previously mentioned, there remains a need in the art for an adhesive that can be used in cylindrical battery seals and meets the handling and performance requirements. The inventor of the present invention found that by compounding epoxy resins having different photo-curing reaction rates, the pre-cured adhesive can be cured to a gel or viscoelastic shape, thereby having a certain body strength, but the adhesive which is not completely cured on the surface of the adhesive layer still has wettability and adhesiveness to the bonded interface, thereby facilitating the rolling and post-curing. The adhesive product obtained by the method has good mechanical properties, good bonding effect on aluminum materials, good sealing performance, shadow curing and delayed curing, and is resistant to solvent erosion, low in shrinkage, ageing-resistant, good in impact shock resistance, and suitable for sealing of cylindrical batteries in cooperation with corresponding sizing and curing processes, and shows good sealing effect to prevent electrolyte leakage. Thus, the present invention has been completed.
Thus, 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 bridged 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 touch-enhancing agent selected from nano alumina or organic bentonite;
0.1 to 0.5 parts by weight of a photoinitiator selected from at least one of diazonium salts, hexafluoroantimonates, diaryliodonium salts, triarylsulfonium salts, alkylsulfinium salts, iron arene salts, sulfonyloxy ketones, and triarylsiloxane 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 type epoxy resin, bridged ring type epoxy resin, reactive diluent and optional adhesion promoter until uniform;
(2) Adding a toughening agent and a touch agent, and mixing again until uniform;
(3) The photoinitiator was added and stirred in vacuo until no bubbles were present.
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 delay curing adhesive for compounding fast curing epoxy resin and slow curing epoxy resin, which can be used for sealing cylindrical batteries, solves the problems of high bonding interface stress and poor bonding force on aluminum materials of cationic UV delay curing adhesives, and can meet the process and performance requirements of battery sealing. The UV delay curing adhesive is used for gluing and pre-curing in advance at the inner layer rolling position of the top cover of the cylindrical battery, the pre-cured adhesive can keep gel or viscoelastic shape while having certain body strength, the surface of the adhesive layer is ensured to have wettability, the subsequent rolling is convenient, and then post-curing is performed, so that tiny holes and gaps existing in the battery can be effectively compensated, electrolyte infiltration in the use process of the battery is prevented, good tightness of the battery is ensured, the yield and reliability of the product are improved, the process is simple, and the automatic gluing can be realized by using a glue spraying process.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below.
FIG. 1 shows the shear strength comparison of an adhesive made according to an embodiment of the invention and a control adhesive.
Fig. 2 shows a shore hardness comparison of an adhesive prepared according to an embodiment of the invention and a control adhesive.
Fig. 3 shows the swell ratio comparison of an adhesive prepared according to an embodiment of the invention and a control adhesive.
Fig. 4 shows the dissolution rate comparison of an adhesive prepared according to an embodiment of the invention and a control adhesive.
Fig. 5 shows the impact number comparison of an adhesive prepared according to an embodiment of the invention and a control adhesive.
Figure 6 shows a tack-free time comparison of an adhesive prepared in accordance with an embodiment 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 invention by way of example only, and is not intended to limit the scope of the invention as defined by the appended claims. And, it is understood by those skilled in the art that modifications may be made to the technical scheme of the present invention without departing from the spirit and gist of the present invention. The technical means used in the examples are conventional means well known to those skilled in the art unless otherwise indicated.
Where a range of values is provided, such as a range of concentrations, a range of percentages, or a range of ratios, it is to be understood that each intervening value, to the tenth of the unit of the lower limit, between the upper and lower limit of the range, and any other stated or intervening value in that stated range, is encompassed within the subject matter unless the context clearly dictates otherwise. The upper and lower limits of these smaller ranges may independently be included in the smaller ranges, and such embodiments are also included in 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/mainly of … …". The expression "comprising," "including," or "consisting essentially of … …" is generally understood to mean an open-ended expression that includes not only the individual elements, components, assemblies, method steps, etc., specifically listed thereafter, but also other elements, components, assemblies, method steps. In addition, the expression "comprising," "including," or "consisting essentially of … …" is also to be understood in some instances as a closed-form expression, meaning that only the elements, components, assemblies, and method steps specifically listed thereafter are included, and no other elements, components, assemblies, and method steps are included. At this time, the expression is equivalent to the expression "consisting of … …".
For a better understanding of the present teachings and without limiting the scope of the present teachings, all numbers expressing quantities, percentages or proportions used in the specification and claims, and other numerical values, are to be understood as being modified in all instances by the term "about" unless otherwise indicated. 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.
Thus, 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 bridged 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 touch-enhancing agent selected from nano alumina or organic bentonite;
0.1 to 0.5 parts by weight of a photoinitiator selected from at least one of diazonium salts, diaryliodonium salts, triarylsulfonium salts, alkyl sulfonium salts, iron arene salts, sulfonyloxy ketones, and triarylsiloxane 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 specific embodiment, the naphthalene type epoxy resin has a structure selected from the following formulas I-IV:
i is a kind of
II (II)
Formula III
Formula IV.
The naphthalene type epoxy resin may be commercially available, for example, naphthalene type epoxy resin obtained from the monomer of formula II (1, 6-bis (2, 3-epoxypropane-1-yloxy) naphthalene) may be purchased from Epiclon HP-4032D (having an epoxy equivalent of 136-148) of DIC, and for example, naphthalene type epoxy resin prepared from the monomer of formula I may be purchased from EXA-4710 (having a 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 bridged ring epoxy resin has a structure selected from formulas V or VI below:
v (V)
Formula VI.
The bridged ring type epoxy resin may be commercially available, for example, a bridged ring type epoxy resin obtained by polymerizing a monomer of formula V (dicyclopentadiene dimethanol diglycidyl ether) may be available from EP-4088L (epoxy equivalent 165) of ADEKA; also for example, bridged ring epoxy resins obtained from the polymerization of monomers of formula VI (phenyl glycidyl ether-co-dicyclopentadiene), epicolin HP-7200H (epoxy equivalent 280) available from DIC, are mixtures of compounds comprising the following exemplary structural formulas VI-1 through VI-3.
Formula VI-1
VI-2
VI-3
In yet another specific embodiment, the naphthalene type epoxy resin has a faster photo-curing speed than the bridged ring type epoxy resin. Alternatively, the naphthalene type epoxy is a fast curing epoxy and the bridged ring type epoxy is a slow curing epoxy. The naphthalene type epoxy resin is quickly photo-cured in the pre-curing step, so that the adhesive has certain body strength, and the bridge ring type epoxy resin in the adhesive is slower in curing speed and not fully cured, so that the adhesive can still keep gel or viscoelastic shape, and has wettability and adhesiveness 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 illumination energy to reach the final cure level, 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 fast cured in the system, which serves to increase the adhesion of the adhesive, improve the toughness of the adhesive, while the slow curing epoxy resin requires relatively more illumination energy to reach the final cure level, such as the bridged ring type epoxy resin used in the present invention, which serves to adjust the cure rate, reduce interfacial shrinkage stress, and improve the aging resistance in the adhesive.
In a particular embodiment, the toughening agent may be an epoxidized polyolefin resin, such as a polybutadiene epoxy resin, for example, poly bd 605E (molecular weight 1450) available from gram Lei Weili, but is not limited thereto. The lower polarity of the polyolefin epoxy resin and the rigidity of the epoxy adhesive system can ensure the solvent erosion resistance of the adhesive layer formed after the adhesive is cured, thereby ensuring the reliability of the cylindrical battery in the use process.
In yet another specific embodiment, the toughening agent may be a core shell rubber, such as, but not limited to, a core shell rubber available from Carnican under the trade designation MX-135 (viscosity 13000cps at 50 ℃).
The inventor discovers that the toughening agent used in the adhesive can not only effectively reduce the hardness of the adhesive layer formed after the adhesive is cured and improve the vibration resistance and impact resistance, but also ensure the solvent erosion resistance of the adhesive layer formed after the adhesive is cured, thereby ensuring the reliability of the cylindrical battery in the use process.
In yet another specific embodiment, the reactive diluent is oxetane, but is not limited thereto. Without wishing to be bound by theory, the inventors have found that oxetane as a reactive diluent allows the bond strength of the adhesive to aluminum material to be greatly improved, good bonding to aluminum material is achieved, and good sealability of the cylindrical battery in use is further ensured.
In yet another specific embodiment, the touch-up agent is an organobentonite. Without wishing to be bound by theory, organobentonite as a touch-up agent may alter the rheological properties of the adhesive.
In yet another specific embodiment, the photoinitiator is a triarylsulfonium salt. Those skilled in the art will appreciate that the individual components of the adhesive described above are independently present in the adhesive and are not reacted prior to exposure to light. Once irradiated by UV light, the cationic photoinitiating agent releases Lewis acid under the UV light, so as to catalyze the crosslinking reaction between epoxy groups, and realize the pre-curing of the glue.
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 type epoxy resin, bridged ring type epoxy resin, reactive diluent and optional adhesion promoter until uniform;
(2) Adding a toughening agent and a touch agent, and mixing again until uniform;
(3) The photoinitiator was added and stirred in vacuo until no bubbles were present.
The preparation process may be carried out in equipment commonly used in the art, for example in a double planetary mixer. Step (1) may be performed at room temperature for 30 to 60 minutes until uniform. Step (2) may also be carried out at room temperature for 30 to 60 minutes until uniform. The step (3) may be carried out at room temperature for at least 30 minutes until no bubbles are present.
The prepared UV delay curing adhesive can be used for rapidly carrying out initial curing of the adhesive through UV illumination, so that the initial body strength is established, and the liquid adhesive is prevented from being extruded or thrown away during the roll-sealing process. Meanwhile, the adhesive after initial curing can keep wettability and adhesiveness to an adhered interface due to the bridge ring type epoxy resin which is not cured completely, so that after the adhesive is rolled and sealed, post curing of the adhesive can be carried out at room temperature or under heating conditions, the final strength is achieved, and the production efficiency is further met. The initial curing degree and the post curing speed can be adjusted according to the requirement, so as to match the diversification of the battery production process.
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 on the inner layer rolling and sealing 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 rolled and sealed on a middle cylindrical shell of the cylindrical battery;
(4) Post-curing the pre-cured glue layer.
The top cover or the sealing position of the top cover may be cleaned, for example, but not limited to, by laser cleaning, before step (1).
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 of adhesive uniformly distributed at the inner layer seaming location of the top cover.
In a specific embodiment, the glue layer may have a thickness of 0.2 to mm to 0.5 to mm.
In a preferred embodiment, the glue layer may have a thickness of 0.3 to mm a to 0.4 to mm a.
In the step (2), the principle that the photoinitiator releases Lewis acid to catalyze epoxy crosslinking reaction is utilized to perform initial curing on the UV delay curing adhesive, the adhesive layer pre-cured by the UV light is in a gel state or a viscoelastic state and has certain body strength, but the adhesive layer surface still has wettability and adhesiveness, so that the winding and sealing of the step (3) can be performed, and the process requirement of rapid setting can be met.
In yet another specific embodiment, a mercury lamp source, an LED source, or a xenon lamp source may be employed to provide UV light having a curing energy of 2000 mJ/cm2 to 12000 mJ/cm 2.
In a preferred embodiment, a mercury lamp source, an LED source, or a xenon lamp source may be used to provide UV light having a curing energy of 3000 mJ/cm2 to 6000 mJ/cm 2.
It will be appreciated that the adhesive of the present invention may 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. Those skilled in the art will appreciate that curing energy = curing time x light intensity, a low curing energy indicates a short light time required for the same light intensity conditions, and vice versa. The adhesive disclosed by the invention comprises the quick-curing epoxy resin such as naphthalene-type epoxy resin and the slow-curing epoxy resin such as bridged-ring epoxy resin, so that the adhesive can be suitable for low curing energy such as 2000 mJ/cm < 2 >, high curing energy such as 12000 mJ/cm < 2 >, and the situation that the adhesive is lost in early time due to too high curing energy or is insufficiently cured due to too low curing energy can not occur, so that the process efficiency is ensured, and meanwhile, the wider assembly process window is provided.
In the step (4), the post-curing process is a shadow-curable process, i.e. the adhesive can be cured locally without UV light irradiation, because the lewis acid released by the photoinitiator of the cationic system in the pre-curing step can continue to catalyze the epoxy crosslinking reaction in the post-curing step, thereby realizing the post-curing of the glue.
In yet another specific embodiment, the post-curing may be performed at an ordinary temperature for 12 to 72 hours.
The liquid adhesive can realize complete fit between various special-shaped curved surfaces of the cylindrical battery, has good wettability to 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 without falling 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 erode; the high-low temperature performance is stable, and the requirements of tightness and reliability can be met in the use temperature environment.
Examples
In the following examples, the preparation method of the insulating film of the present invention and characterization of the relevant properties are shown. Unless otherwise indicated, all test procedures used herein were conventional, and all test materials used in the examples described below were purchased from a conventional reagent store, unless otherwise indicated. 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 is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The foregoing summary of the invention and the following detailed description are only for the purpose of illustrating the invention and are not intended to limit the invention in any way. The scope of the invention is determined by the appended claims without departing from the spirit and scope of the invention.
Example 1: preparation of adhesive
The control adhesive and the exemplary UV-delay cured adhesive of the present invention were prepared according to the control formulations one and two and formulations one to six, respectively, given in table 1 below, in the following steps.
Control formula one: 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 are added into a double planetary mixer, the mixture is stirred at room temperature for 30-60 min to be uniform, 2 parts of fumed silica is added, the mixture is stirred at room temperature for 30-60 min to be uniform, and finally 0.2 part of hexafluoroantimonate is added as a photoinitiator, and the mixture is stirred at room temperature for 30min under vacuum to be bubble-free.
And a second control formula: 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 are added into a double planetary mixer, the mixture is stirred at room temperature for 30-60 min to be uniform, 2 parts of organic bentonite is added, the mixture is stirred at room temperature for 30-60 min to be uniform, and finally 0.2 part of hexafluoroantimonate is added as a photoinitiator, and the mixture is stirred at room temperature for 30min under vacuum to be bubble-free.
Formula I: 45 parts of naphthalene-type epoxy resin, 15 parts of bridged ring-type epoxy resin and 1 part of silane coupling agent are added into a double-planetary stirrer, stirred at room temperature for 30-60 min until uniform, then 20 parts of epoxy polyolefin resin and 2 parts of organic bentonite are added, stirred at room temperature for 30-60 min until uniform, finally 0.2 part of hexafluoroantimonate is added as a photoinitiator, and stirred at room temperature for 30min until no bubbles are generated.
And the formula II: 45 parts of naphthalene-type epoxy resin, 15 parts of bridged ring-type epoxy resin and 1 part of silane coupling agent are added into a double-planetary stirrer, stirred at room temperature for 30-60 min until uniform, then 40 parts of epoxy polyolefin resin and 2 parts of organic bentonite are added, stirred at room temperature for 30-60 min until uniform, finally 0.2 part of hexafluoroantimonate is added as a photoinitiator, and stirred at room temperature for 30min until no bubbles are generated.
And the formula III: adding 35 parts of naphthalene-type epoxy resin, 5 parts of bridged ring-type epoxy resin and 1 part of silane coupling agent into a double-planetary stirrer, stirring for 30-60 min at room temperature until uniform, adding 40 parts of epoxy polyolefin resin and 2 parts of organic bentonite, stirring for 30-60 min at room temperature until uniform, and finally adding 0.2 part of hexafluoroantimonate as a photoinitiator, and stirring for 30min at room temperature under vacuum until no bubbles.
Table 1: parts by weight of each component in the adhesive
And a formula IV: adding 40 parts of naphthalene-type epoxy resin, 10 parts of bridged ring-type epoxy resin, 10 parts of oxetane and 1 part of silane coupling agent into a double planetary mixer, stirring at room temperature for 30-60 min to be uniform, adding 20 parts of epoxy polyolefin resin and 2 parts of organic bentonite, stirring at room temperature for 30-60 min to be uniform, and finally adding 0.2 part of hexafluoroantimonate serving as a photoinitiator, and stirring at room temperature in vacuum for 30min to be bubble-free.
Formula five: adding 35 parts of naphthalene-type epoxy resin, 5 parts of bridged ring-type epoxy resin, 20 parts of oxetane and 1 part of silane coupling agent into a double planetary mixer, stirring at room temperature for 30-60 min to be uniform, adding 20 parts of core-shell rubber and 2 parts of organic bentonite, stirring at room temperature for 30-60 min to be uniform, adding 0.2 part of photoinitiator, and stirring at room temperature for 30min to be bubble-free.
Formula six: adding 40 parts of naphthalene-type epoxy resin, 10 parts of bridged ring-type epoxy resin, 10 parts of oxetane and 1 part of silane coupling agent into a double planetary mixer, stirring at room temperature for 30-60 min to be uniform, adding 20 parts of core-shell rubber and 2 parts of organic bentonite, stirring at room temperature for 30-60 min to be uniform, adding 0.2 part of photoinitiator, and stirring at room temperature for 30min to be bubble-free.
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 sample was prepared by a die shear method (die shear test), the glass substrate was bonded to the aluminum substrate with a bonding area of 3 mm x 3 mm, the aluminum substrate was irradiated with 365 nm LED light source, the irradiation energy was 3000 mJ/cm2, and after 24 hours of room temperature curing, the aluminum substrate was tested by a Dage chip pusher at a speed of 6 mm/min, and the test results are shown in fig. 1.
As can be seen from fig. 1, the shear strength of formulations one to six of the present invention is higher than that of the control formulations one and two, and in particular formulations three to six, which have significantly higher shear strengths than those of the control formulations one and two.
Hardness: the adhesive was prepared to a thickness of 6. 6 mm, irradiated with 365 nm LED light source, and subjected to irradiation energy 9000 mJ/cm2, and cured at room temperature for 24 hours, and then tested by using a Shore durometer, and the test results are shown in FIG. 2.
As can be seen from FIG. 2, the formulations one to six of the present invention have slightly lower hardness than the comparative formulations one and two, and exhibit 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/cm < 2 >, after the adhesive is cured for 24 hours at room temperature, the adhesive is put into a PP cup for sealing, 50+/-0.5 g of lithium-containing electrolyte is added, the adhesive is placed in an oven at the temperature of 85 ℃ for 24 hours, the adhesive is taken out and then is dried and weighed, the weight difference before and after the experiment and the percentage of the initial weight are measured, and the test result is shown in figure 3.
As can be seen from fig. 3, the swelling ratios of the formulations one to six of the present invention were significantly lower than those of the control formulations one and two.
In addition, the control formula has small bubbles on the surface of the gel block in the process of soaking the electrolyte, but the formula of the invention does not have the phenomenon, which indicates that the fumed silica can react with components in the electrolyte to generate gas, and is not suitable for being used in the application.
Dissolution rate: extruding the adhesive to 1.4+/-0.05 g, irradiating with 365 nm LED light source, irradiating with energy 6000 mJ/cm2, solidifying at room temperature for 24 hr, sealing in a penicillin bottle, adding 7+/-0.1 g of lithium-free electrolyte, standing in an oven at 85deg.C for 24 hr, taking out, extracting the solution while hot with a syringe, testing the mass fraction of solute in the solution with TGA, calculating the solute mass in the whole solution, and looking at the percentage of solute mass to initial weight, and 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 were significantly lower than those of the control formulations one and two.
Dupont impact strength: the cross bonding method comprises the steps of preparing samples, dispensing the samples into circles on aluminum sheets, bonding the circles with the inner diameter of the circles being 25.4 mm and the width of a glue line being 1.0+/-0.1 mm, aligning the circle center of another perforated glass round hole with the circle center of the circle surrounded by the glue line, controlling the thickness of the glue layer to be 0.25 mm, irradiating with light from a 365 nm LED light source, irradiating with energy being 6000 mJ/cm < 2 >, curing at room temperature for 24 hours, testing with a DuPont impact tester, and testing impact hammer 200 g and height 50 cm, wherein the impact times during the test and the test results are shown in figure 5.
As can be seen from fig. 5, the dupont impact strengths of formulations one through six of the present invention are significantly better than the control formulations one and two, and particularly formulations three and five, showing the most excellent impact resistance.
Open time: the aluminum sheet was irradiated with 0.1ml of glue, each of which was irradiated with an illumination intensity of 3000 mJ/cm2 and 6000 mJ/cm2, and the surface tackiness was measured by finger touch after irradiation and the time was counted until the surface tackiness was lost, which was regarded as the tack-free time.
As can be seen from fig. 6, the formulations one to six of the present invention had significantly longer tack-free times than the control formulation, with a broader assembly process window.
Example 3: rolling seal
In this example, the adhesive prepared in example 1 was used to seal the battery. The rolling and sealing process is as follows:
roll-sealing control 1: and placing the battery top cover on a battery shell for rolling and sealing, and placing the battery top cover for 24 hours at room temperature after rolling and sealing.
Roll-sealing control 2: placing the battery top cover on a clamp, gluing the control formula at a rolling position by using an automatic gluing machine, irradiating and pre-solidifying the battery top cover by using a light source with the thickness of 0.3 mm,365 nm LED, wherein the solidifying energy is 3000 mJ/cm < 2 >, then placing the battery top cover on a battery shell for rolling and sealing, and solidifying the battery top cover for 24 hours at room temperature after rolling and sealing.
Sealing control 3: placing the battery top cover on a clamp, gluing the control formula at a rolling position by using an automatic gluing machine, pre-solidifying by irradiating light source with thickness 0.3 mm,365 nm LED, solidifying energy of 6000 mJ/cm < 2 >, placing the battery top cover on a battery shell, rolling and sealing, and solidifying for 24 hours at room temperature after rolling and sealing.
Seal example 1: placing the battery top cover on a clamp, gluing the formula at a rolling position by using a three-purpose automatic gluing machine, irradiating a light source with the thickness of 0.3 mm,365 nm LED for pre-curing, and then placing the battery top cover on a battery shell for rolling and sealing, wherein the curing energy is 3000 mJ/cm < 2 >, and curing for 24 hours at room temperature after rolling and sealing.
Seaming example 2: placing the battery top cover on a clamp, gluing the formula at a rolling position by using a three-purpose automatic gluing machine, irradiating a light source with the thickness of 0.4 mm,365 nm LED for pre-curing, and then placing the battery top cover on a battery shell for rolling and sealing, wherein the curing energy is 3000 mJ/cm < 2 >, and curing for 72 hours at room temperature after rolling and sealing.
Sealing example 3: placing the battery top cover on a clamp, gluing the formula at a rolling position by using a three-purpose automatic gluing machine, irradiating a light source with the thickness of 0.3 mm,365 nm LED for pre-curing, placing the battery top cover on a battery shell for rolling, and curing at room temperature for 24 hours after rolling, wherein the curing energy is 6000 mJ/cm < 2 >.
Seaming example 4: placing the battery top cover on a clamp, gluing the formula at a rolling position by using a three-purpose automatic gluing machine, irradiating a light source with the thickness of 0.4 mm,365 nm LED for pre-curing, placing the battery top cover on a battery shell for rolling, and curing at room temperature for 24 hours after rolling, wherein the curing energy is 6000 mJ/cm < 2 >.
Roll-sealing example 5: placing the battery top cover on a fixture, gluing the formula four times by using an automatic gluing machine at a rolling sealing position, pre-estimating the thickness 0.3 mm,365 nm LED by light source irradiation, placing the battery top cover on a battery shell for rolling sealing, and solidifying at room temperature for 24 hours after rolling sealing, wherein the solidifying energy is 3000 mJ/cm < 2 >.
Sealing example 6: placing the battery top cover on a clamp, gluing the glue at a rolling position by a five-purpose automatic gluing machine for the formula, pre-estimating the thickness 0.3 mm,365 nm LED by light source irradiation, placing the battery top cover on a battery shell for rolling, and solidifying the battery top cover at room temperature for 24 hours after rolling, wherein the solidifying energy is 3000 mJ/cm < 2 >.
Seaming example 7: placing the battery top cover on a fixture, gluing the formula six at a rolling sealing position by using an automatic gluing machine, pre-estimating the thickness 0.3 mm,365 nm LED by irradiating a light source, placing the battery top cover on a battery shell for rolling sealing, and solidifying the battery top cover at room temperature for 24 hours after rolling sealing, wherein the solidifying energy is 3000 mJ/cm < 2 >.
Example 4: testing of rolled sealed batteries
Helium detection: for the battery prepared by the roll-sealing process in example 3, helium with the pressure of 0.1 Mpa was added from the liquid injection hole into the sealed housing, and the battery was kept for 30 minutes, and the air pressure decay was detected, and the test results are shown in table 2. The results show that examples 1-7 using the adhesive at the time of the seaming all had an air pressure decay amplitude of <0.3, compared to comparative example 1 using no adhesive at the time of the seaming, and comparative examples 2 and 3 using the comparative formula two, indicating that excellent sealing effect can be obtained using the adhesive of the present invention.
And (3) liquid resistance test: for the battery prepared by the roll-sealing process in example 3, after electrolyte was added from the liquid injection hole into the sealed case, the battery was left to stand at 85 ℃ and 85% rh for continuous aging, and it was confirmed whether or not the electrolyte oozed out from the sealed place. The test results are shown in Table 2. The results show that comparative examples 1 and 3 began to develop electrolyte leakage on the first day, comparative example 2 began to develop electrolyte leakage on the 7 th day, whereas examples 1 to 7 each exceeded 60 days without electrolyte leakage, indicating that excellent blocking was possible with the adhesive of the present invention, and that electrolyte was tolerated.
Drop test: for the battery prepared by the roll-sealing process in example 3, electrolyte is added into the sealed shell from the liquid injection hole, the sealed shell is well sealed, the battery falls off in a 1.5m height free falling state, and the battery after falling off is placed at 85 ℃ and 85% RH for continuous aging, so as to see whether the electrolyte seeps out from the sealed part. The test results are shown in Table 2. The results show that the electrolyte leakage starts on the first day in each of comparative examples 1 to 3, and that the electrolyte leakage does not occur for more than 60 days in each of examples 1 to 7, and that the adhesive of the present invention can have excellent blocking effect, and that the adhesive can withstand the electrolyte and resist the influence of dropping.
Table 2: test results for rolled-up batteries
From the results of Table 2 above, it is clear that the adhesive of the present invention provides excellent sealing effect for a battery, not only exhibits extremely low air pressure decay amplitude, but also is resistant to electrolyte and can resist the influence of dropping, both at a lower curing energy of 3000 mJ/cm2 and at a higher curing energy of 6000 mJ/cm 2. While the adhesive using the mixture of bisphenol a epoxy resin and bisphenol F epoxy resin does not achieve a good seal at a higher curing energy of 6000 mJ/cm2, the sealing result is similar to that of the adhesive, and the sealing result at a lower curing energy of 3000 mJ/cm2 is far less than that of the adhesive of the invention, and also does not achieve an effective sealing effect, and cannot be used for a new energy power battery, although the sealing result is improved compared with that of the adhesive of the invention.
Claims (9)
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 bridged 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 touch-enhancing agent selected from nano alumina or organic bentonite;
0.1 to 0.5 parts by weight of a photoinitiator selected from at least one of diazonium salts, hexafluoroantimonates, diaryliodonium salts, triarylsulfonium salts, alkylsulfinium salts, iron arene salts, sulfonyloxy ketones, and triarylsiloxane ethers;
0 to 5 parts by weight of an adhesion promoter which is a silane coupling agent;
wherein the naphthalene type epoxy resin has a faster photo-curing speed than the bridged ring type epoxy resin.
2. The adhesive of claim 1 wherein the naphthalene type epoxy resin has a structure selected from the following formulas I or II:
i is a kind of
Formula II.
3. The adhesive of claim 1 or 2, wherein the bridged-ring epoxy resin has a structure selected from the following formulas V-VI:
v (V)
Formula VI.
4. A method of preparing the adhesive of any one of claims 1-3, comprising the steps of:
(1) Mixing naphthalene type epoxy resin, bridged ring type epoxy resin, reactive diluent and optional adhesion promoter until uniform;
(2) Adding a toughening agent and a touch agent, and mixing again until uniform;
(3) The photoinitiator was added and stirred in vacuo until no bubbles were present.
5. A method of sealing a cylindrical battery comprising the step of using the adhesive of any one of claims 1-3.
6. The method according to claim 5, wherein the method comprises:
(1) Coating the adhesive on the inner layer rolling and sealing 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 rolled and sealed on a middle cylindrical shell of the cylindrical battery;
(4) Post-curing the pre-cured glue layer.
7. The method of claim 6, wherein the glue layer has a thickness of 0.2-mm to 0.5-mm.
8. The method according to claim 6The method comprises providing a curing energy of 2000 mJ/cm by using a mercury lamp light source, an LED light source or a xenon lamp light source 2 To 12000 mJ/cm 2 UV light of (a) is provided.
9. The method of claim 6, wherein the post-curing is performed at ambient temperature for 12 to 72 hours.
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| CN115322655A (en) * | 2022-10-11 | 2022-11-11 | 拓迪新材料(苏州)有限公司 | Epoxy metal composite shell for accommodating lithium battery cell, lithium battery comprising composite shell and production method |
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| JP4639766B2 (en) * | 2004-11-16 | 2011-02-23 | 横浜ゴム株式会社 | Two-component room temperature curable epoxy resin composition and metal adhesive composition |
| WO2018174177A1 (en) * | 2017-03-22 | 2018-09-27 | パナソニックＩｐマネジメント株式会社 | Photocurable resin composition, adhesive, laminated body, method for producing laminated body, and display device |
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| CN115322655A (en) * | 2022-10-11 | 2022-11-11 | 拓迪新材料(苏州)有限公司 | Epoxy metal composite shell for accommodating lithium battery cell, lithium battery comprising composite shell and production method |
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Address after: 200120 1-2 / F, building 10, Shanghai Zhicheng, Lane 8666, Hunan highway, Pudong New Area, Shanghai Patentee after: Tuodi Chemical (Shanghai) Co.,Ltd. Address before: 200120 1-2 / F, building 10, Shanghai Zhicheng, Lane 8666, Hunan highway, Pudong New Area, Shanghai Patentee before: TUODI CHEMICAL (SHANGHAI) Co.,Ltd. |
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