CN113122161A - Composite hot-melt double-sided adhesive tape for lithium ion battery and preparation method thereof - Google Patents
Composite hot-melt double-sided adhesive tape for lithium ion battery and preparation method thereof Download PDFInfo
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- CN113122161A CN113122161A CN202110511442.2A CN202110511442A CN113122161A CN 113122161 A CN113122161 A CN 113122161A CN 202110511442 A CN202110511442 A CN 202110511442A CN 113122161 A CN113122161 A CN 113122161A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/29—Laminated material
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
- C09J151/006—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to block copolymers containing at least one sequence of polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/35—Heat-activated
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/33—Applications of adhesives in processes or use of adhesives in the form of films or foils for batteries or fuel cells
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2451/00—Presence of graft polymer
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2467/00—Presence of polyester
- C09J2467/006—Presence of polyester in the substrate
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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
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- 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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Abstract
The invention discloses a composite hot-melt double-sided adhesive tape for a lithium ion battery and a preparation method thereof, wherein the composite hot-melt double-sided adhesive tape for the lithium ion battery sequentially comprises the following components from bottom to top: the composite hot-melt double-sided adhesive tape for the lithium ion battery is characterized by comprising a first hot-melt adhesive layer, a first base film layer, an acrylic adhesive layer, a second base film layer, a second hot-melt adhesive layer and a release film layer, wherein the two base film layers are arranged, the inner surfaces of the two base film layers are connected through the acrylic adhesive layer, the lithium ion battery is soaked in battery electrolyte at 85 ℃ for 24 hours by using the composite hot-melt double-sided adhesive tape, the acrylic adhesive layer in the composite hot-melt double-sided adhesive tape is softened, the acrylic adhesive layer is swelled flocculent gel after being soaked for 48 hours, and the state of the acrylic adhesive layer in the electrolyte and the structure of the adhesive tape.
Description
Technical Field
The invention belongs to the technical field of adhesive tapes, and particularly relates to a composite hot-melt double-sided adhesive tape for a lithium ion battery and a preparation method thereof.
Background
At present, with the continuous development and promotion of the state in the aspects of new energy, energy conservation and emission reduction, products such as pure electric vehicles and smart phones are rapidly developed, and the market demand of high-performance lithium batteries corresponding to the products is rapidly increased. Meanwhile, the requirements on the safety performance of the lithium battery are more and more strict. The current battery core adopts adhesive tape to fix, insulate and protect the electrode ear, the battery core stopping edge, the battery core and the aluminum plastic film when designing.
But the fixed protection hot melt double-sided tape of usefulness of current electric core termination limit, electric core and plastic-aluminum membrane, though have higher adhesion to the thing of being pasted, but lack good shock-absorbing capacity, lead to electric core when receiving the impact easily, electric core inner structure is destroyed and is leaded to electric core short circuit to take place to fire the detonation.
The existing composite hot-melt double-sided adhesive tape for the lithium ion battery is mainly characterized in that a plurality of adhesive layers are coated on the upper surface and the lower surface of a base film, when the adhesive tape is impacted, all forces are concentrated on the adhesive layers, and the internal structure of a battery cell is easily damaged to cause the short circuit of the battery cell.
Disclosure of Invention
In order to solve the technical problems, the invention provides a composite hot-melt double-sided adhesive tape for a lithium ion battery and a preparation method thereof.
The technical scheme adopted by the invention is as follows:
the utility model provides a compound hot melt double sticky tape for lithium ion battery, compound hot melt double sticky tape for lithium ion battery includes by lower supreme in proper order: the adhesive comprises a first hot melt adhesive layer, a first base film layer, an acrylic adhesive layer, a second base film layer, a second hot melt adhesive layer and a release film layer.
The first base film layer and the second base film layer are both transparent PET films; the thickness of the first base film layer and the second base film layer is 6-12 mu m
Testing in an environment with 23 +/-1 ℃ and 50 +/-5% humidity, wherein the peeling force of the first hot melt adhesive layer is larger than that of the second hot melt adhesive layer; the peeling force of the first hot melt adhesive layer is 0.1-0.45N/mm; the stripping force of the second hot melt adhesive layer is less than or equal to 0.03N/mm, and the second hot melt adhesive layer does not have viscosity below 15 ℃.
The thickness of the first hot melt adhesive layer is 5-8 mu m.
The thickness of the acrylic adhesive layer is 4-7 mu m.
The thickness of the second hot melt adhesive layer is 5-8 mu m.
It is from type rete to adopt white double silicon from type rete, and it is by from type paper and be located from heavy type force layer, the light type force layer that leaves of type paper upper and lower surface and constitute, heavy type force layer with second hot melt adhesive layer contacts, light type force layer after the sticky tape lapping with first hot melt adhesive layer contacts.
The hot melt adhesive for forming the first hot melt adhesive layer comprises the following raw materials in parts by weight: 100 parts of maleic anhydride modified thermoplastic elastomer, 20-30 parts of epoxy modified saturated thermoplastic elastomer, 5-30 parts of low molecular weight high activity polyolefin, 10-50 parts of hydrogenated carbon penta petroleum resin, 40-90 parts of hydrogenated polydicyclopentadiene resin, 0.15-0.3 part of rubber vulcanizing agent and 400-700 parts of toluene.
In the formula of the hot melt adhesive for forming the first hot melt adhesive layer, the maleic anhydride modified thermoplastic elastomer is one or two of maleic anhydride modified SEBS and maleic anhydride modified SBS;
the epoxy modified saturated thermoplastic elastomer is one or two of an epoxy thermoplastic elastomer and epoxy modified SBS.
The low-molecular-weight high-activity polyolefin is high-activity polyisobutylene with the molecular weight of 1300-2800.
The softening point of the hydrogenated carbon penta petroleum resin is 100-130 ℃.
The softening point of the hydrogenated polydicyclopentadiene resin is 100-140 ℃.
The rubber vulcanizing agent is 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane.
The maleic anhydride grafting rate of the maleic anhydride modified SEBS is 1.2-2.0%. The maleic anhydride modified SEBS is preferably maleic anhydride grafted SEBS with the trade name of 9901.
The maleic anhydride grafting rate of the maleic anhydride modified SBS is 0.6-1.4%. The maleic anhydride modified SBS is preferably maleic anhydride grafted SBS with the trade name DY-307.
The glue for forming the acrylic glue layer comprises the following raw materials in parts by weight: 20-30 parts of butyl acrylate, 20-30 parts of 2-ethylhexyl acrylate, 10-18 parts of vinyl acetate, 20-30 parts of methyl acrylate, 16-28 parts of fluorine-containing monomer, 0.01-0.5 part of catalyst, 0.015-0.3 part of curing agent and 120-360 parts of organic solvent.
The viscosity of the glue for forming the acrylic glue layer is 1000-5000 CPs.
In the formula of the glue for forming the acrylic glue layer, the fluorine-containing monomer is any one or two of tridecyl methacrylate and dodecafluoro heptyl methacrylate.
The catalyst is benzoyl peroxide.
The curing agent is isocyanate or epoxy resin.
The organic solvent is a mixed solvent of toluene and ethyl acetate.
The hot melt adhesive for forming the second hot melt adhesive layer comprises the following raw materials in parts by weight: 100 parts of maleic anhydride modified thermoplastic elastomer, 50-70 parts of polyisoprene rubber, 10-40 parts of ethylene propylene diene monomer, 15-35 parts of carbon-nine petroleum resin, 5.0-15 parts of poly-alpha-methyl styrene resin, 20-60 parts of alicyclic saturated tackifying resin and 400-600 parts of toluene.
In the formula of the hot melt adhesive for forming the second hot melt adhesive layer, the maleic anhydride modified thermoplastic elastomer is maleic anhydride modified SEBS.
The maleic anhydride grafting rate of the maleic anhydride modified SEBS is 1.2-2.0%. The maleic anhydride modified SEBS is preferably a 7131 grade maleic anhydride grafted SEBS.
The isoprene content of the polyisoprene rubber is more than or equal to 96 percent. The polyisoprene rubber is preferably polyisoprene rubber with the brand number of SKI-3S.
The ethylene content of the ethylene propylene diene monomer is 59 +/-5%. The ethylene propylene diene monomer is preferably ethylene propylene diene monomer with the grade of 552E.
The softening point of the carbon-nine petroleum resin is 140-160 ℃.
The poly-alpha-methylstyrene resin has a softening point of 110 to 125 ℃.
The alicyclic saturated tackifying resin is hydrogenated carbon penta petroleum resin, and the softening point of the alicyclic saturated tackifying resin is 95-115 ℃.
The production method of the composite hot-melt double-sided adhesive tape for the lithium ion battery comprises the following steps:
(1) coating glue on one surface of the first base film layer, and drying at 110-120 ℃ to form an acrylic acid glue layer;
(2) coating a hot melt adhesive on one surface of the second base film layer, and drying at 120-130 ℃ to form a second hot melt adhesive layer;
(3) compounding the uncoated surface of the second base film layer with the acrylic adhesive layer on the first base film layer;
(4) coating hot melt adhesive on the uncoated surface of the first base film layer, and drying at 130-135 ℃ to form a first hot melt adhesive layer;
(5) and finally, attaching release paper to the surface of the second hot melt adhesive layer, and then rolling.
The composite hot-melt double-sided adhesive tape for the lithium ion battery is used for bonding the inner surface of an aluminum-plastic film of a battery shell by the second hot-melt adhesive layer, has good adhesion to a plastic film layer on the inner surface of the aluminum-plastic film, and is used for bonding the outer surface of a battery cell by the first hot-melt adhesive layer so as to effectively fix the battery cell and the aluminum-plastic film; the adhesive tape can also realize effective fixation of the cell terminating edge; the working environment of the composite hot-melt double-sided adhesive tape for the lithium ion battery is in electrolyte, an acrylic adhesive layer arranged between a first base film layer and a second base film layer in the adhesive tape is softened when soaked in battery electrolyte at 85 ℃ for 24 hours, and is swelled flocculent gel after soaked for 48 hours, so that the anti-buffering performance of the adhesive tape is greatly improved due to the state of the acrylic adhesive layer in the electrolyte.
The first hot melt adhesive layer and the second hot melt adhesive layer in the composite hot melt double-sided adhesive tape for the lithium ion battery provided by the invention are low in polarity, do not contain any free micromolecules, do not generate any chemical reaction with electrolyte, and after the composite hot melt double-sided adhesive tape is soaked in the electrolyte at 85 ℃ for 48 hours, the stripping force to an aluminum foil or an aluminum-plastic film is kept above 85%, the adhesive force to a base film layer is still kept above the initial 20%, and the electrolyte hardly changes color. The battery passing rate of the lithium ion battery using the adhesive tape is 100% in 1000 drop resistance tests, and the battery core has no internal structure and no damage phenomenon after disassembly. The composite hot-melt double-sided adhesive tape for the lithium ion battery is convenient for automatic bonding in use and can meet the repair requirement after later bonding.
Drawings
FIG. 1 is a schematic structural view of a composite hot-melt double-sided adhesive tape for a lithium ion battery in the present invention,
wherein, 1-a first hot melt adhesive layer, 2-a first base film layer, 3-an acrylic adhesive layer, 4-a second base film layer, 5-a second hot melt adhesive layer and 6-a release film layer.
Detailed Description
The utility model provides a compound hot melt double sticky tape for lithium ion battery, compound hot melt double sticky tape for lithium ion battery includes by lower supreme in proper order: the adhesive comprises a first hot melt adhesive layer 1, a first base film layer 2, an acrylic adhesive layer 3, a second base film layer 4, a second hot melt adhesive layer 5 and a release film layer 6.
First base rete, second base rete are transparent PET film to prevent this sticky tape when using because of using coloured PET film as the base rete and appear soaking the appearance that the decoloration leads to electrolyte to change color the problem, the PET film.
The thickness of the first base film layer and the second base film layer is 6-12 mu m; the thickness of the first hot melt adhesive layer is 5-8 mu m; the thickness of the acrylic adhesive layer is 4-7 mu m; the thickness of the second hot melt adhesive layer is 5-8 mu m, the adhesive tape formed by the layers with the thicknesses is stable in performance, the total thickness of the adhesive tape is smaller than 26-47 mu m, and the required space is smaller when the adhesive tape is used, so that a larger space can be reserved for an electric core, the electric core with a larger volume can be used, and the capacity of the battery is improved.
At normal temperature, the peeling force of the first hot melt adhesive layer is larger than that of the second hot melt adhesive layer; the peeling force of the first hot melt adhesive layer is 0.1-0.45N/mm; the stripping force of the second hot melt adhesive layer is less than or equal to 0.03N/mm, and the second hot melt adhesive layer does not have viscosity below 15 ℃. The first hot melt adhesive layer of the adhesive tape is used for bonding the inner surface of the aluminum plastic film of the battery shell, the adhesive tape has good adhesion to the plastic film layer on the inner surface of the aluminum plastic film, the second hot melt adhesive layer is used for bonding the outer surface of a battery cell, the adhesive tape does not have adhesion at the temperature below 15 ℃, in the heat setting stage (60 ℃ heat setting 4s) after the battery cell is attached to the adhesive tape, the adhesion of the second hot melt adhesive layer of the adhesive tape is not exerted, in addition, the battery cell has certain self weight, so the adhesion of the second hot melt adhesive layer under the heat setting is exerted very little, and the problem that the adhesive tape is adhered to an adsorption device can.
The hot melt adhesive for forming the first hot melt adhesive layer comprises the following raw materials in parts by weight: 100 parts of maleic anhydride modified thermoplastic elastomer, 20-30 parts of epoxy modified saturated thermoplastic elastomer, 5-30 parts of low molecular weight high activity polyolefin, 10-50 parts of hydrogenated carbon penta petroleum resin, 40-90 parts of hydrogenated polydicyclopentadiene resin, 0.15-0.3 part of rubber vulcanizing agent and 400-700 parts of toluene.
In the formula of the hot melt adhesive for forming the first hot melt adhesive layer, the maleic anhydride modified thermoplastic elastomer is one or two of maleic anhydride modified SEBS and maleic anhydride modified SBS.
The maleic anhydride grafting rate of the maleic anhydride modified SEBS is 1.2-2.0%; the maleic anhydride modified SEBS is preferably maleic anhydride grafted SEBS with the trade name of 9901. The maleic anhydride grafting rate of the maleic anhydride modified SBS is 0.6-1.4%; the maleic anhydride modified SBS is preferably maleic anhydride grafted SBS with the trade name DY-307. The maleic anhydride modified SEBS and the maleic anhydride modified SBS have moderate flexibility, good coordination with the whole hot melt adhesive formula system, and good flexibility after crosslinking and cohesion increase.
The epoxy modified saturated thermoplastic elastomer is one or two of an epoxy thermoplastic elastomer and epoxy modified SBS.
The low-molecular-weight high-activity polyolefin is high-activity polyisobutylene with the molecular weight of 1300-2800.
The softening point of the hydrogenated carbon penta petroleum resin is 100-130 ℃.
The softening point of the hydrogenated polydicyclopentadiene resin is 100-140 ℃.
The rubber vulcanizing agent is 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane.
According to the hot melt adhesive formula design of the first hot melt adhesive layer, a rubber vulcanizing agent can react with a maleic anhydride group, an epoxy group and a conjugated double bond at high temperature to perform a crosslinking curing reaction on a main elastomer, so that the cohesive force of the adhesive layer is improved, and the barrier property of the adhesive tape to electrolyte and the stability of the adhesive tape soaked in the electrolyte for a long time are enhanced; the low-molecular-weight high-activity polyisobutylene with the molecular weight has good flexibility and viscosity after being crosslinked, and can adjust the initial viscosity of an adhesive layer; in addition, hydrogenated carbon pentapetroleum resin with the softening point above is particularly preferred in order to make the glue line flexible properly with good reworking effect and good stability in the electrolyte (the electrolyte does not change color after soaking in the electrolyte at 85 ℃ for 48 hours).
The glue for forming the acrylic glue layer comprises the following raw materials in parts by weight: 20-30 parts of butyl acrylate, 20-30 parts of 2-ethylhexyl acrylate, 10-18 parts of vinyl acetate, 20-30 parts of methyl acrylate, 16-28 parts of fluorine-containing monomer, 0.01-0.5 part of catalyst, 0.015-0.3 part of curing agent and 120-360 parts of organic solvent.
The viscosity of the glue for forming the acrylic glue layer is 1000-5000 CPs.
In the formula of the glue for forming the acrylic glue layer, the fluorine-containing monomer is any one or two of tridecyl methacrylate and dodecafluoro heptyl methacrylate.
The catalyst is benzoyl peroxide.
The curing agent is isocyanate or epoxy resin.
The organic solvent is a mixed solvent of toluene and ethyl acetate.
The glue formula design of the acrylic acid glue layer ensures that the acrylic acid glue layer can be softened when being soaked in battery electrolyte at 85 ℃ for 24 hours and can be swelled to form flocculent gel after being soaked for 48 hours by designing and controlling the final number average molecular weight of the acrylic acid glue and adding a certain content of curing agent to adjust the final crosslinking degree of the glue layer at the later stage
The hot melt adhesive for forming the second hot melt adhesive layer comprises the following raw materials in parts by weight: 100 parts of maleic anhydride modified thermoplastic elastomer, 50-70 parts of polyisoprene rubber, 10-40 parts of ethylene propylene diene monomer, 15-35 parts of carbon-nine petroleum resin, 5.0-15 parts of poly-alpha-methyl styrene resin, 20-60 parts of alicyclic saturated tackifying resin and 400-600 parts of toluene.
In the formula of the hot melt adhesive for forming the second hot melt adhesive layer, the maleic anhydride modified thermoplastic elastomer is maleic anhydride modified SEBS; the maleic anhydride grafting rate of the maleic anhydride modified SEBS is 1.2-2.0%. The maleic anhydride modified SEBS is preferably a 7131 grade maleic anhydride grafted SEBS.
The isoprene content of the polyisoprene rubber is more than or equal to 96 percent. The polyisoprene rubber is preferably polyisoprene rubber with the brand number of SKI-3S.
The ethylene content of the ethylene propylene diene monomer is 59 +/-5%. The ethylene propylene diene monomer is preferably ethylene propylene diene monomer with the grade of 552E.
The softening point of the carbon-nine petroleum resin is 140-160 ℃.
The poly-alpha-methylstyrene resin has a softening point of 110 to 125 ℃.
The alicyclic saturated tackifying resin is hydrogenated carbon five resin, and the softening point of the alicyclic saturated tackifying resin is 95-115 ℃.
The hot melt adhesive formula of the second hot melt adhesive layer is designed, and the polarity of the adhesive layer is improved by using the SEBS modified by maleic anhydride, so that the adhesive force of the adhesive layer to the PET substrate is improved; polyisoprene rubber (SIS) is adopted to improve the flexibility of the adhesive layer and improve the attaching performance of the adhesive layer; the saturated elastomer ethylene propylene diene monomer rubber has excellent electrolyte resistance, and can enhance the electrolyte corrosion resistance of the adhesive tape; in addition, alicyclic saturated tackifying resins having softening points above are particularly preferred in order to achieve tack-free adhesive layers at room temperature in this system and to have good adhesive properties after hot-press soaking.
The production method of the composite hot-melt double-sided adhesive tape for the lithium ion battery comprises the following steps:
(1) coating glue on one surface of the first base film layer, and drying at 110-120 ℃ to form an acrylic acid glue layer;
(2) coating a hot melt adhesive on one surface of the second base film layer, and drying at 120-130 ℃ to form a second hot melt adhesive layer;
(3) compounding the uncoated surface of the second base film layer with the acrylic adhesive layer on the first base film layer;
(4) coating hot melt adhesive on the uncoated surface of the first base film layer, and drying at 130-140 ℃ to form a first hot melt adhesive layer;
(5) and finally, attaching release paper to the surface of the second hot melt adhesive layer, and then rolling.
The present invention will be described in detail with reference to examples.
Example 1
The utility model provides a lithium ion battery is with compound hot melt double-sided tape, it includes from top to bottom in proper order: the adhesive comprises a first hot melt adhesive layer, a transparent PET film, an acrylic adhesive layer, a transparent PET film, a second hot melt adhesive layer and a release film layer; the thickness of the transparent PET film was 6 μm. The formula of the glue of the first hot melt adhesive layer, the acrylic adhesive layer and the second hot melt adhesive layer is shown in table 1.
The production method of the composite hot-melt double-sided adhesive tape for the lithium ion battery comprises the following steps:
(1) adding all raw materials except a catalyst into a three-neck flask provided with a condenser pipe, a thermometer and a stirring device, stirring at a constant speed of 300-500 r/min until the temperature is slowly increased to 80 ℃, dripping 1/2 toluene solution of 10% by mass of benzoyl peroxide, reacting for 2 hours, adding the remaining toluene solution of benzoyl peroxide, reacting for 4 hours, finally heating to 85 ℃, preserving the temperature for 1 hour, cooling, filtering and discharging to obtain glue, coating the glue on one surface of a first base film layer, and drying at 120 ℃ to form an acrylic glue layer;
(2) coating a hot melt adhesive on one surface of the second base film layer, and drying at 130 ℃ to form a second hot melt adhesive layer;
(3) compounding the uncoated surface of the second base film layer with the acrylic adhesive layer on the first base film layer;
(4) coating hot melt adhesive on the uncoated surface of the first base film layer, and drying at 140 ℃ to form a first hot melt adhesive layer;
(5) and finally, attaching release paper to the surface of the second hot melt adhesive layer, and then rolling.
TABLE 1
Example 2
The utility model provides a lithium ion battery is with compound hot melt double-sided tape, it includes from top to bottom in proper order: the adhesive comprises a first hot melt adhesive layer, a transparent PET film, an acrylic adhesive layer, a transparent PET film, a second hot melt adhesive layer and a release film layer; the thickness of the transparent PET film was 6 μm. The formula of the glue of the first hot melt adhesive layer, the acrylic adhesive layer and the second hot melt adhesive layer is shown in table 2.
The production method of the composite hot-melt double-sided adhesive tape for the lithium ion battery is the same as that of the embodiment 1.
TABLE 2
Example 3
The utility model provides a lithium ion battery is with compound hot melt double-sided tape, it includes from top to bottom in proper order: the adhesive comprises a first hot melt adhesive layer, a transparent PET film, an acrylic adhesive layer, a transparent PET film, a second hot melt adhesive layer and a release film layer; the thickness of the transparent PET film was 6 μm. The formula of the glue of the first hot melt adhesive layer, the acrylic adhesive layer and the second hot melt adhesive layer is shown in table 3.
The production method of the composite hot-melt double-sided adhesive tape for the lithium ion battery is the same as that of the embodiment 1.
TABLE 3
Example 4
The utility model provides a lithium ion battery is with compound hot melt double-sided tape, it includes from top to bottom in proper order: the adhesive comprises a first hot melt adhesive layer, a transparent PET film, an acrylic adhesive layer, a transparent PET film, a second hot melt adhesive layer and a release film layer; the thickness of the transparent PET film was 6 μm. The formula of the glue of the first hot melt adhesive layer, the acrylic adhesive layer and the second hot melt adhesive layer is shown in table 4.
The production method of the composite hot-melt double-sided adhesive tape for the lithium ion battery is the same as that of the embodiment 1.
TABLE 4
Example 5
The utility model provides a lithium ion battery is with compound hot melt double-sided tape, it includes from top to bottom in proper order: the adhesive comprises a first hot melt adhesive layer, a transparent PET film, an acrylic adhesive layer, a transparent PET film, a second hot melt adhesive layer and a release film layer; the thickness of the transparent PET film was 6 μm. The formula of the glue of the first hot melt adhesive layer, the acrylic adhesive layer and the second hot melt adhesive layer is shown in table 5.
The production method of the composite hot-melt double-sided adhesive tape for the lithium ion battery is the same as that of the embodiment 1.
TABLE 5
Comparative example 1
The utility model provides a lithium ion battery is with compound hot melt double-sided tape, it includes from top to bottom in proper order: the adhesive comprises a first hot melt adhesive layer, a transparent PET film, an acrylic adhesive layer, a transparent PET film, a second hot melt adhesive layer and a release film layer; the thickness of the transparent PET film was 6 μm. The formula of the glue of the first hot melt adhesive layer, the acrylic adhesive layer and the second hot melt adhesive layer is shown in table 6.
The production method of the composite hot-melt double-sided adhesive tape for the lithium ion battery is the same as that of the embodiment 1.
TABLE 6
Comparative example 2
The utility model provides a lithium ion battery is with compound hot melt double-sided tape, it includes from top to bottom in proper order: the adhesive comprises a first hot melt adhesive layer, a transparent PET film, an acrylic adhesive layer, a transparent PET film, a second hot melt adhesive layer and a release film layer; the thickness of the transparent PET film was 6 μm. The formula of the glue of the first hot melt adhesive layer, the acrylic adhesive layer and the second hot melt adhesive layer is shown in table 7.
The production method of the composite hot-melt double-sided adhesive tape for the lithium ion battery is the same as that of the embodiment 1.
TABLE 7
The normal temperature peeling force of the composite hot melt double-sided adhesive tape for the lithium ion battery obtained in each embodiment and comparative example is tested by referring to the method in GB/T2792-2014, the adhered substrate is a stainless steel plate, the normal temperature peeling force of the first hot melt adhesive layer is required to be 0.1-0.3N/mm, the normal temperature peeling force of the second hot melt adhesive layer is required to be less than or equal to 0.03N/mm, and the results are shown in Table 8.
The composite hot-melt double-sided adhesive tapes for lithium ion batteries obtained in the examples and the comparative examples and the hot-press peeling force under 1MPa of immersing the tapes in an electrolyte (ethylene carbonate: methyl ethyl carbonate: dimethyl carbonate: 4:2:4) at 85 ℃ for 48h were tested by referring to the method in GB/T2792-2014, and the adhesion substrate of the first hot-melt adhesive layer was an aluminum foil; the adhesion substrate of the second hot melt adhesive layer is a PP material surface of an aluminum plastic film, the normal temperature peeling force of the first hot melt adhesive layer is required to be more than or equal to 0.15N/mm, and the normal temperature peeling force of the second hot melt adhesive layer is required to be more than 0.1N/mm, and the results are shown in Table 8.
The composite hot-melt double-sided adhesive tapes for lithium ion batteries obtained in the examples and the comparative examples were placed in an electrolyte (ethylene carbonate: methyl ethyl carbonate: dimethyl carbonate: 4:2:4) and soaked at 85 ℃ for 48 hours according to the method in GB/T2792-2014, and the results are shown in table 8.
The repair test method comprises the following steps: adhering the first hot melt adhesive layer surface of the adhesive tape to the aluminum foil, and rolling the adhesive tape by a 1Kg compression roller for two times; and standing for 24 hours, peeling the adhesive tape by using GB/T2792-2014, and if the adhesive layer is left on the aluminum foil, judging that the repair fails, and if the adhesive layer is not left on the aluminum foil, judging that the adhesive layer is qualified, wherein the results are shown in Table 8.
The testing method of the viscous hot-pressing device comprises the following steps: attaching the first hot melt adhesive layer surface of the adhesive tape to a plastic block of 300g, and contacting the second hot melt adhesive layer surface with a hot-pressing device under the pressure of 0.5 MPa; after pressing at 60 ℃ for 10 seconds, the plastic block was observed to be capable of adhering to the hot press apparatus, and the results are shown in Table 8.
Testing the electrochemical performance of the acrylic layer: adding a certain amount of conductive carbon black (the mass ratio of the dry glue to the conductive carbon black is 7: 3) into the glue for forming the acrylic acid layer in each example and each comparative example, uniformly mixing, and respectively and uniformly coating the glue on a copper foil and an aluminum foil with the coating thickness of 250 micrometers; drying at 120 ℃ for 12h for dewatering, taking the dried pole piece as a cathode, and preparing the button cell with a lithium piece and a lithium ion electrolyte. And respectively testing the anti-reduction performance of the copper foil buckle battery at 0-4V and the anti-oxidation performance of the aluminum foil buckle battery at 2-5V by using a cyclic voltammetry method. The results of the blank test using a 10% solids polyvinylidene fluoride solution are shown in Table 8.
The battery using the composite hot-melt double-sided adhesive tape for lithium ion batteries obtained in each example and comparative example was subjected to 1000 drop resistance tests with reference to the method of GB31241-2014, and the results are shown in table 8.
TABLE 8
According to the data, the composite hot-melt double-sided adhesive tape for the lithium ion battery disclosed by the invention has good electrolyte resistance and adhesion performance, and can be well matched with an automatic production process.
It was found from comparative example 1 that if the softening points of the respective hydrogenated tackifying resins were all lowered below the preferred softening point of the present invention, the peel strength of the first hot melt adhesive layer exceeded and the rework failed; the peeling force of the second hot melt adhesive layer exceeds the standard and is adhered with a hot pressing device; this comparative sample was not able to meet the design requirements and standards.
It was found from comparative example 2 that if the softening points of the hydrogenated resins are all increased to the softening points above the preferred softening point of the present invention, the peel force of the first hot-melt adhesive layer side of the adhesive tape is lower than the standard, and the second hot-melt adhesive layer side still does not exert good adhesiveness at 85 ℃/4h due to the excessively high softening point of the adhesive layer, resulting in the lifting of the adhesive tape.
As can be seen from a comparison of the above examples and comparative examples of the present invention, the present invention has the following advantages:
1. the first hot melt adhesive layer of the adhesive tape has good adhesive force to an aluminum foil and the second hot melt adhesive layer has good adhesive force to an aluminum plastic film, and the two hot melt adhesive layers of the adhesive tape have lower polarity, do not contain any free micromolecules and do not generate any chemical reaction with electrolyte. After the aluminum foil is soaked in the electrolyte at the temperature of 85 ℃ for 48 hours, the peeling force of the aluminum foil and the aluminum-plastic film is kept above 85%, and the electrolyte hardly changes color;
2. the acrylic adhesive layer in the adhesive tape disclosed by the invention is soaked in an electrolyte at 85 ℃ for 24 hours to cause the phenomenon of softening of the adhesive layer; the phenomenon of swelling flocculent gel appears after 48 hours, and the adhesive force to the PET layer is still kept above the initial 20 percent; the state of the middle acrylic adhesive layer of the adhesive tape in the electrolyte greatly improves the anti-buffering performance of the adhesive tape; the battery passing rate of the adhesive tape in 1000 times of drop resistance tests is 100%, and the electric core has no internal structure damage after being disassembled.
3. In the invention, the glue used for forming the acrylic glue layer has no obvious reduction reaction in the equilibrium potential of 0-4V; no obvious oxidation reaction is generated in the equilibrium potential of 2-5V; the adhesive tape has good electrochemical stability in a battery;
the above detailed description of the composite hot-melt double-sided tape for lithium ion battery and the preparation method thereof with reference to the embodiments is illustrative and not restrictive, and several embodiments can be enumerated according to the limited scope, so that changes and modifications without departing from the general concept of the present invention shall fall within the protection scope of the present invention.
Claims (10)
1. The utility model provides a lithium ion battery is with compound hot melt double sticky tape, its characterized in that, lithium ion battery includes from top to bottom in proper order with compound hot melt double sticky tape: the adhesive comprises a first hot melt adhesive layer, a first base film layer, an acrylic adhesive layer, a second base film layer, a second hot melt adhesive layer and a release film layer.
2. The composite hot-melt double-sided tape for the lithium ion battery according to claim 1, wherein the first base film layer and the second base film layer are both transparent PET films; the thickness of the first base film layer and the second base film layer is 6-12 mu m.
3. The composite hot-melt double-sided tape for the lithium ion battery according to claim 1, wherein the peel force of the first hot-melt adhesive layer is greater than that of the second hot-melt adhesive layer when tested in an environment of 23 ± 1 ℃ and 50 ± 5% humidity; the peeling force of the first hot melt adhesive layer is 0.1-0.45N/mm; the stripping force of the second hot melt adhesive layer is less than or equal to 0.03N/mm, and the second hot melt adhesive layer does not have viscosity below 15 ℃.
4. The composite hot-melt double-sided tape for the lithium ion battery according to claim 1, wherein the thickness of the first hot-melt adhesive layer and the thickness of the second hot-melt adhesive layer are both 5-8 μm.
5. The composite hot-melt double-sided tape for the lithium ion battery according to claim 1, wherein the thickness of the acrylic adhesive layer is 4-7 μm.
6. The composite hot-melt double-sided adhesive tape for the lithium ion battery according to claim 1, wherein the hot melt adhesive for forming the first hot-melt adhesive layer comprises the following raw materials in parts by weight: 100 parts of maleic anhydride modified thermoplastic elastomer, 20-30 parts of epoxy modified saturated thermoplastic elastomer, 5-30 parts of low molecular weight high activity polyolefin, 10-50 parts of hydrogenated carbon penta petroleum resin, 40-90 parts of hydrogenated polydicyclopentadiene resin, 0.15-0.3 part of rubber vulcanizing agent and 400-700 parts of toluene.
7. The composite hot-melt double-sided adhesive tape for the lithium ion battery according to claim 1, wherein the glue for forming the acrylic adhesive layer comprises the following raw materials in parts by weight: 20-30 parts of butyl acrylate, 20-30 parts of 2-ethylhexyl acrylate, 10-18 parts of vinyl acetate, 20-30 parts of methyl acrylate, 16-28 parts of fluorine-containing monomer, 0.01-0.5 part of catalyst, 0.015-0.3 part of curing agent and 120-360 parts of organic solvent.
8. The composite hot-melt double-sided adhesive tape for the lithium ion battery as claimed in claim 1 or 7, wherein the viscosity of the glue forming the acrylic glue layer is 1000 to 5000 CPs.
9. The composite hot-melt double-sided adhesive tape for the lithium ion battery according to claim 1, wherein the hot melt adhesive for forming the second hot-melt adhesive layer comprises the following raw materials in parts by weight: 100 parts of maleic anhydride modified thermoplastic elastomer, 50-70 parts of polyisoprene rubber, 10-40 parts of ethylene propylene diene monomer, 15-35 parts of carbon-nine petroleum resin, 5.0-15 parts of poly-alpha-methyl styrene resin, 20-60 parts of alicyclic saturated tackifying resin and 400-600 parts of toluene.
10. The production method of the composite hot-melt double-sided adhesive tape for the lithium ion battery according to any one of claims 1 to 9, characterized by comprising the steps of:
(1) coating glue on one surface of the first base film layer, and drying at 110-120 ℃ to form an acrylic acid glue layer;
(2) coating a hot melt adhesive on one surface of the second base film layer, and drying at 120-130 ℃ to form a second hot melt adhesive layer;
(3) compounding the uncoated surface of the second base film layer with the acrylic adhesive layer on the first base film layer;
(4) coating hot melt adhesive on the uncoated surface of the first base film layer, and drying at 130-140 ℃ to form a first hot melt adhesive layer;
(5) and finally, attaching release paper to the surface of the second hot melt adhesive layer, and then rolling.
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