CN115074056A - Aluminum-plastic film inner layer adhesive for lithium battery packaging and preparation method thereof - Google Patents
Aluminum-plastic film inner layer adhesive for lithium battery packaging and preparation method thereof Download PDFInfo
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- CN115074056A CN115074056A CN202210752686.4A CN202210752686A CN115074056A CN 115074056 A CN115074056 A CN 115074056A CN 202210752686 A CN202210752686 A CN 202210752686A CN 115074056 A CN115074056 A CN 115074056A
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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
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/26—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers modified by chemical after-treatment
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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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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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
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
- C09J123/04—Homopolymers or copolymers of ethene
- C09J123/08—Copolymers of ethene
- C09J123/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C09J123/0853—Vinylacetate
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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
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
- C09J123/04—Homopolymers or copolymers of ethene
- C09J123/08—Copolymers of ethene
- C09J123/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C09J123/0869—Acids or derivatives thereof
- C09J123/0876—Neutralised polymers, i.e. ionomers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts
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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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- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Sealing Battery Cases Or Jackets (AREA)
Abstract
The invention provides an aluminum plastic film inner layer adhesive for lithium battery packaging and a preparation method thereof, wherein the adhesive comprises a component A and a component B; the component A comprises: polyolefin with low melting point, anhydride monomer, initiator, auxiliary agent and organic solvent I; the component B comprises: bisphenol A epoxy resin, modified bisphenol A epoxy resin and organic solvent II; the auxiliary agent is a multifunctional organic micromolecule containing a triazine ring. The invention takes the polyolefin with low melting point as the main resin, matches with a small amount of bisphenol A epoxy resin, and adds a small amount of multifunctional organic micromolecules containing triazine ring, thereby obviously improving the bonding strength and the electrolyte resistance.
Description
Technical Field
The invention relates to the technical field of lithium battery soft packages, in particular to an aluminum plastic film inner layer adhesive for lithium battery packaging and a preparation method thereof.
Background
With the development of technology in recent years, lithium ion batteries have been rapidly developed in the fields of digital electronics, new energy vehicles, energy storage and the like gradually due to the advantages of large capacity, long cycle life, no memory effect, environmental friendliness and the like. The traditional lithium battery is packaged by rigid materials such as a steel shell, and the pressure can not be timely relieved when the pressure of the battery is too high, so that safety accidents are easy to occur. Therefore, aiming at the problem of packaging the lithium ion battery, an aluminum-plastic composite film packaging material is developed.
The aluminum-plastic composite film mainly comprises nylon, aluminum foil and a polypropylene film, and the interlayer bonding force is increased by adhesives among layers. The polypropylene film is in direct contact with the battery electrolyte, and factors such as heat and gas generated in the using process can generate chemical corrosion or thermal aging effects on the composite film, so that the adhesive is required to have better electrolyte resistance and heat resistance. However, due to the defects of the preparation method of the common adhesive, the common adhesive is difficult to have good long-term electrolyte resistance and good heat-sealing strength at high temperature, so that the common adhesive is difficult to meet the requirements of the current aluminum plastic film packaging.
At present, polyolefin is generally used as main resin of the inner layer adhesive in the market, polar groups are introduced on the main resin to increase the adhesive force with the aluminum foil, and meanwhile, the adhesive force of the adhesive and a polypropylene film is ensured. However, in this method, the number of introduced polar groups is limited due to the few active sites on the polyolefin, and it is difficult to make the adhesive have good adhesive strength, high temperature resistance and electrolyte resistance.
Therefore, at present, modified resin or resin with high unsaturation degree is used as main resin for further modification, but the cost is increased, the unsaturated resin is easy to crack in the reaction process, the consistency of each experiment is difficult to control, and great interference is brought to practical application.
The patent CN202010268184.5 discloses a lithium battery aluminum plastic film inner layer adhesive and a preparation method thereof, wherein the method comprises the following steps of preparing a modified polyolefin component A containing carboxyl or anhydride groups, a modified polyolefin component B-1 containing glycidyl ether groups, and a modified polyolefin component B-2 containing glycidyl amine groups; a modified polyolefin component C containing isocyanate groups; and an organic solvent D. The adhesive can achieve an ideal curing effect after being cured at 70-90 ℃ for three days after being coated, and has excellent bonding strength and electrolyte resistance. However, the method has complex components, leads to complex curing reaction, and therefore has low controllability, and electrolyte resistance is still to be improved.
In view of the above, there is a need for an improved aluminum plastic film inner layer adhesive for lithium battery encapsulation and a preparation method thereof, so as to solve the above problems.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide an inner layer adhesive of an aluminum plastic film for lithium battery packaging and a preparation method thereof.
In order to achieve the purpose, the invention provides an aluminum plastic film inner layer adhesive for lithium battery packaging, which comprises a component A and a component B; the component A comprises: polyolefin with low melting point, anhydride monomer, initiator, auxiliary agent and organic solvent I; the component B comprises: bisphenol A epoxy resin, modified bisphenol A epoxy resin and organic solvent II; the auxiliary agent is a multifunctional organic small molecule containing a triazine ring.
As a further improvement of the invention, the component A comprises the following components in parts by mass: 20-30 parts of low-melting-point modified polyolefin, 5-20 parts of anhydride monomer, 0.2-1 part of initiator, 0.1-0.5 part of auxiliary agent and 80-120 parts of organic solvent I; the component B comprises the following components in parts by mass: 13-20 parts of bisphenol A epoxy resin, 1-3 parts of modified bisphenol A epoxy resin and 75-100 parts of organic solvent II; the mass ratio of the component A to the component B is 100: (0.5-1).
As a further improvement of the invention, the functionality of the adjuvant is 2-4, and the active functional group is an alkylene group, a hydroxyl group or a carboxyl group.
As a further improvement of the invention, the auxiliary agent is 1,3, 5-triacryloylhexahydro-1, 3, 5-triazine or 1,3, 5-triglycidyl-S-triazinetrione.
As a further improvement of the invention, the low-melting polyolefin is maleic anhydride modified polyolefin, ethylene-vinyl acetate copolymer or ethylene acrylic acid copolymer; the modified bisphenol A epoxy resin is tetrafunctional epoxy resin.
As a further improvement of the invention, the low melting point polyolefin has a melt index of 5-200g/10min at 190 ℃ under a load of 2.16kg, a melting point of 70-130 ℃ and an acid value of 1-20 mg KOH/g.
As a further improvement of the invention, the anhydride monomer is one or more of maleic anhydride, 1,2,3,6 tetrahydrophthalic anhydride and nadic anhydride; preferably maleic anhydride;
the initiator is one or more of dibenzoyl peroxide, methyl ethyl ketone peroxide and azodiisobutyronitrile; the organic solvent I is one or more of toluene, xylene, cyclohexane and n-butyl ester;
the organic solvent II is one or more of toluene, xylene, ethyl ester, n-butyl ester, acetone and butanone.
The preparation method of any one of the above aluminum-plastic film inner layer adhesives for lithium battery packaging comprises the following steps:
(1) preparing a component A;
(2) preparing a component B;
(3) and uniformly mixing the component A with the solid content of 5-15% and the component B to obtain the aluminum plastic film inner layer adhesive for lithium battery packaging.
As a further improvement of the invention, the preparation method of the component A comprises the following steps:
s1, adding the low-melting-point polyolefin into a large reaction kettle, adding an organic solvent, heating to 100 ℃ and 130 ℃, and completely dissolving;
s2, dropwise adding a part of dissolved initiator into the mixed solution, and adding an anhydride monomer and an auxiliary agent into the mixed solution after dropwise adding; after the initiator is completely dissolved, dissolving the rest initiator and dropwise adding the initiator into the mixed solution, and preserving heat for 1-5 hours to carry out reaction after the initiator is completely dissolved;
s3, adding butanone while the reaction is hot after the reaction is finished, filtering to obtain white powder, and washing the obtained white powder with butanone for multiple times to obtain the component A.
As a further improvement of the invention, the preparation method of the component B comprises the following steps: and diluting the bisphenol A epoxy resin and the modified bisphenol A epoxy resin with an organic solvent.
The invention has the beneficial effects that:
1. the invention provides an aluminum plastic film inner layer adhesive for lithium battery packaging, which mainly comprises modified polyolefin containing carboxyl or anhydride groups and epoxy resin, and the performance of the aluminum plastic film inner layer adhesive is improved by adding a small amount of multifunctional organic micromolecules containing triazine rings. After the adhesive is coated, the adhesive can be cured for 2-5 days at 60-100 ℃ to achieve a good curing effect, and has good bonding strength, electrolyte resistance, high temperature resistance and water resistance.
2. The invention takes polyolefin with low melting point as the main resin component, adds proper amount of bisphenol A epoxy resin and modified polyfunctional bisphenol A epoxy resin, and can play a good role in regulating and controlling the curing crosslinking structure by matching proper amount of anhydride monomer and polyfunctional organic micromolecule auxiliary agent containing triazine ring, so that the adhesive curing network can play a good role in bonding between aluminum foil and polypropylene film, and the curing structure is not easy to be dissociated and destroyed after being soaked in electrolyte, thus the electrolyte resistance is excellent.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in detail below with reference to specific embodiments.
It should be noted that, in order to avoid obscuring the present invention with unnecessary details, only the structures and/or processing steps closely related to the scheme of the present invention are shown in the specific embodiments, and other details not closely related to the present invention are omitted.
In addition, it is also to be noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
The invention provides an aluminum plastic film inner layer adhesive for lithium battery packaging, which comprises a component A and a component B; the component A comprises: polyolefin with low melting point, anhydride monomer, initiator, auxiliary agent and organic solvent I; the component B comprises: bisphenol A epoxy resin, modified bisphenol A epoxy resin and organic solvent II; the auxiliary agent is a multifunctional organic small molecule containing a triazine ring. The experimental result shows that the small molecular auxiliary agent can play a remarkable enhancing role by adding a small amount of the small molecular auxiliary agent.
The functionality of the auxiliary agent is 2-4, and the active functional group is alkylene, hydroxyl or carboxyl, preferably alkylene. The auxiliary agent is preferably 1,3, 5-triacryloylhexahydro-1, 3, 5-triazine or 1,3, 5-triglycidyl-S-triazinetrione.
Specifically, the component A comprises the following components in parts by mass: 20-30 parts of low-melting-point modified polyolefin, 5-20 parts of anhydride monomer, 0.2-1 part of initiator, 0.1-0.5 part of auxiliary agent and 80-120 parts of organic solvent I; the component B comprises the following components in parts by mass: 13-20 parts of bisphenol A epoxy resin, 1-3 parts of modified bisphenol A epoxy resin and 75-100 parts of organic solvent II; the mass ratio of the component A to the component B is 100: (0.5-1).
The low-melting-point polyolefin is maleic anhydride modified polyolefin, ethylene-vinyl acetate copolymer or ethylene acrylic acid copolymer; the modified bisphenol A epoxy resin is tetrafunctional epoxy resin.
Example 1
An aluminum-plastic film inner layer adhesive for lithium battery packaging is prepared by the following steps:
the preparation method of the component A comprises the following steps:
(1) weighing 50 parts by mass of low-melting-point polyolefin elastomer into a reaction kettle, adding 200 parts by mass of dimethylbenzene, heating to 130 ℃, and dissolving for 30 min;
(2) weighing 0.5 part by mass of dibenzoyl peroxide, dissolving in 10 parts by mass of dimethylbenzene, uniformly stirring, and then dropwise adding into the solution at a constant speed at 130 ℃ for 30 min;
(3) weighing 10 parts by mass of maleic anhydride and 0.5 part of 1,3, 5-triacryloylhexahydro-1, 3, 5-triazine, adding into the solution, and dissolving for 10 min;
(4) weighing 0.5 part by mass of dibenzoyl peroxide, dissolving the dibenzoyl peroxide in 10 parts by mass of dimethylbenzene, uniformly stirring, then dripping the dibenzoyl peroxide into the solution at a constant speed at the temperature of 130 ℃ for 30min, and preserving heat for 2h for reaction after dripping.
The preparation method of the component B comprises the following steps:
weighing 18 parts by mass of bisphenol A type epoxy resin and 2 parts by mass of tetrafunctional epoxy resin, and diluting with 20 parts by mass of ethyl ester and 60 parts by mass of butanone.
Example 2
Compared with the example 1, the difference of the aluminum plastic film inner layer adhesive for lithium battery packaging is that the auxiliary agent is 1,3, 5-triglycidyl-S-triazinetrione. The rest is substantially the same as that of embodiment 1, and will not be described herein.
Examples 3 to 4
Compared with the example 1, the difference of the aluminum-plastic film inner layer adhesive for lithium battery packaging is that anhydride monomers are 1,2,3,6 tetrahydrophthalic anhydride and nadic anhydride respectively. The rest is substantially the same as embodiment 1, and will not be described herein.
Comparative example 1
Compared with the embodiment 1, the aluminum plastic film inner layer adhesive for lithium battery packaging is characterized in that the auxiliary agent is 1, 3-butadiene. The rest is substantially the same as that of embodiment 1, and will not be described herein.
Comparative example 2
Compared with the example 1, the difference of the aluminum plastic film inner layer adhesive for lithium battery packaging is that the auxiliary agent is 1,3, 5-tris (2, 3-dibromopropyl) -1,3, 5-triazinane-2, 4, 6-triketone. The rest is substantially the same as that of embodiment 1, and will not be described herein.
Comparative example 3
Compared with the embodiment 1, the difference of the aluminum-plastic film inner layer adhesive for lithium battery packaging is that the preparation method of the component B comprises the following steps:
weighing 16 parts by mass of bisphenol A type epoxy resin and 4 parts by mass of tetrafunctional epoxy resin, and diluting with 20 parts by mass of ethyl ester and 60 parts by mass of butanone. The rest is substantially the same as that of embodiment 1, and will not be described herein.
Comparative example 4
Compared with the embodiment 1, the difference of the aluminum-plastic film inner layer adhesive for lithium battery packaging is that the preparation method of the component B comprises the following steps: 20 parts by mass of bisphenol A epoxy resin was weighed and diluted with 20 parts by mass of ethyl ester and 60 parts by mass of methyl ethyl ketone. The rest is substantially the same as that of embodiment 1, and will not be described herein.
Preparation and evaluation of the adhesive:
(1) weighing 100 parts by mass of 9% (w/w) content component A solution and 0.8 part by mass of prepared component B solution, and uniformly mixing to obtain a final 9% (w/w) content adhesive solution;
(2) coating the adhesive on the smooth surface of an aluminum foil treated by a trivalent chromium agent, drying and then attaching the aluminum foil to a CPP film at 100 ℃, and controlling the gluing amount of the adhesive to be 20-30g/m 2 (amount of wet glue). Placing the attached aluminum-plastic film into an oven at 85 ℃ for curing for 4 days;
(3) cutting the cured aluminum-plastic film into sample strips of 100mm multiplied by 15mm, testing the change of T-shaped peeling force to represent the peeling strength of the inner layer adhesive, then additionally preparing sample strips of 100mm multiplied by 15mm, soaking the sample strips in a mixed solution of 1: 1 of ethylene carbonate/dimethyl carbonate/diethyl carbonate containing 1mol/L lithium hexafluorophosphate, setting the temperature of an oven at 85 ℃, and testing the change of T-shaped peeling force after soaking for 7 days to represent the electrolyte resistance of the sample strips.
(4) Cutting the cured aluminum-plastic film into sample strips of 150mm multiplied by 100mm, folding the CPPs face to face, carrying out heat sealing under the conditions that the sealing temperature is 175 +/-5 ℃, the time is 3.5 +/-5 s and the pressure is 0.3-0.4MPa, and then carrying out heat sealing again in the vertical direction to obtain transverse heat sealing strips and longitudinal heat sealing strips. Each of the sheets was cut into 15mm wide strips, and the heat-seal surfaces were tested for T-peel force variation to characterize the heat-seal strength.
(5) The cured aluminum-plastic film was packaged into a 60 mm × 80 mm sample bag, and 3 mL of electrolyte was injected and heat-sealed. And (3) keeping the sample bag in an environment with the temperature of (85 +/-2) DEG C and the relative humidity of 85% for 24 hours, taking out the sample bag, and naturally cooling to the normal temperature. Cutting one hot edge sealing, pouring out the electrolyte, cutting off the residual heat edge sealing, wiping the electrolyte remained on the membrane surface, and carrying out heat sealing again within 5 minutes. The strips were then cut to 15mm width and tested for T-peel force variation to characterize their heat seal strength after immersion in electrolyte.
Table 1 shows the results of the performance tests of examples 1 to 4 and comparative examples 1 to 4 and the market race
| Test specimen | Initial adhesion (N/15 mm) | After soaking in electrolyte for 7 days, the adhesion force (N/15 mm) | Heat sealing Strength (N/15 mm) | Heat seal Strength after immersion in electrolyte (N/15 mm) |
| Example 1 | 15.6 | 14.2 | 163 | 116 |
| Example 2 | 14.7 | 13.2 | 159 | 115 |
| Example 3 | 13.4 | 11.5 | 142 | 103 |
| Example 4 | 12.0 | 10.9 | 136 | 88 |
| Comparative example 1 | 14.3 | 12.7 | 156 | 109 |
| Comparative example 2 | 12.6 | 11.0 | 137 | 80 |
| Comparative example 3 | 13.4 | 11.0 | 145 | 96 |
| Comparative example 4 | 11.4 | 9.8 | 126 | 75 |
| Market contest 1 | 12.4 | 10.4 | 146 | 94 |
| Market contest 2 | 11.9 | 9.6 | 154 | 120 |
| Market contest 3 | 11.7 | 10.6 | 138 | 86 |
As can be seen from Table 1, example 1, a small amount of 1,3, 5-triacryloylhexahydro-1, 3, 5-triazine is added under the formula of the invention, so that the initial adhesive force of the cured adhesive and the adhesive force after soaking in electrolyte are both remarkably improved, and the adhesive strength and the electrolyte resistance after heat sealing are also excellent. Example 2 also has the superior performance when 1,3, 5-triglycidyl-S-triazinetrione is added. When the acid anhydride is changed, the cohesive force is reduced to different degrees, and the triazine organic auxiliary agent can generate more excellent effect by combining with the maleic anhydride. When the triazine organic auxiliary agent is replaced by the auxiliary agent without triazine ring, the bonding force is reduced to different degrees, for example, although the initial bonding force after curing is not obviously reduced compared with that of example 1 in comparative example 1, the bonding force is obviously reduced after soaking in the electrolyte, and the electrolyte resistance of the auxiliary agent is poor. Comparative example 2 addition of 1,3, 5-tris (2, 3-dibromopropyl) -1,3, 5-triazinane-2, 4, 6-trione, due to the change in active functionality, resulted in inferior adhesion to example 1. Comparative example 3 shows that, in the system of the present invention, when the content of the tetrafunctional epoxy resin is too high, the improvement of the adhesive force and the electrolyte resistance is not facilitated. Comparative example 4 shows that without the tetrafunctional epoxy resin, the adhesion and electrolyte resistance are significantly reduced with the system of the present invention.
In summary, the aluminum plastic film inner layer adhesive for lithium battery encapsulation provided by the invention can play a good role in regulating and controlling the curing crosslinking structure by matching with an appropriate amount of anhydride monomers and a multifunctional organic small molecular assistant containing a triazine ring under the condition that low-melting-point polyolefin is used as a main resin component and a proper amount of bisphenol A epoxy resin and modified multifunctional bisphenol A epoxy resin are added, so that the adhesive curing network can play a good bonding role between an aluminum foil and a polypropylene film, and the curing structure is not easily dissociated and damaged after being soaked in an electrolyte, thereby having excellent electrolyte resistance.
Although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the spirit and scope of the present invention.
Claims (10)
1. An aluminum plastic film inner layer adhesive for lithium battery packaging is characterized by comprising a component A and a component B; the component A comprises: polyolefin with low melting point, anhydride monomer, initiator, auxiliary agent and organic solvent I; the component B comprises: bisphenol A epoxy resin, modified bisphenol A epoxy resin and organic solvent II; the auxiliary agent is a multifunctional organic small molecule containing a triazine ring.
2. The aluminum-plastic film inner layer adhesive for lithium battery packaging as claimed in claim 1, wherein the component A comprises the following components in parts by mass: 20-30 parts of low-melting-point modified polyolefin, 5-20 parts of anhydride monomer, 0.2-1 part of initiator, 0.1-0.5 part of auxiliary agent and 80-120 parts of organic solvent I; the component B comprises the following components in parts by mass: 13-20 parts of bisphenol A epoxy resin, 1-3 parts of modified bisphenol A epoxy resin and 75-100 parts of organic solvent II; the mass ratio of the component A to the component B is 100: (0.5-1).
3. The aluminum plastic film inner layer adhesive for lithium battery packaging as claimed in claim 1, wherein the functionality of the auxiliary agent is 2-4, and the active functional group is alkylene, hydroxyl or carboxyl, preferably alkylene.
4. The aluminum plastic film inner layer adhesive for lithium battery encapsulation as claimed in claim 3, wherein the auxiliary agent is 1,3, 5-triacryloylhexahydro-1, 3, 5-triazine or 1,3, 5-triglycidyl-S-triazine trione.
5. The aluminum plastic film inner layer adhesive for lithium battery encapsulation as claimed in claim 1, wherein the low melting point polyolefin is maleic anhydride modified polyolefin, ethylene-vinyl acetate copolymer or ethylene acrylic acid copolymer; the modified bisphenol A epoxy resin is tetrafunctional epoxy resin.
6. The aluminum-plastic film inner layer adhesive for lithium battery packaging as claimed in claim 1, wherein the low-melting polyolefin has a melt index of 5-200g/10min at 190 ℃ under a load of 2.16kg, a melting point of 70-130 ℃ and an acid value of 1-20 mg KOH/g.
7. The aluminum plastic film inner layer adhesive for lithium battery packaging as claimed in claim 1, wherein the acid anhydride monomer is one or more of maleic anhydride, 1,2,3,6 tetrahydrophthalic anhydride and nadic anhydride; preferably maleic anhydride;
the initiator is one or more of dibenzoyl peroxide, methyl ethyl ketone peroxide and azodiisobutyronitrile; the organic solvent I is one or more of toluene, xylene, cyclohexane and n-butyl ester;
the organic solvent II is one or more of toluene, xylene, ethyl ester, n-butyl ester, acetone and butanone.
8. A preparation method of the aluminum plastic film inner layer adhesive for lithium battery packaging as claimed in any one of claims 1 to 7, characterized by comprising the following steps:
(1) preparing a component A;
(2) preparing a component B;
(3) and uniformly mixing the component A with the solid content of 5-15% and the component B to obtain the aluminum plastic film inner layer adhesive for lithium battery packaging.
9. The preparation method of the aluminum plastic film inner layer adhesive for lithium battery encapsulation as claimed in claim 8, wherein the preparation method of the component A comprises the following steps:
s1, adding the low-melting-point polyolefin into a large reaction kettle, adding an organic solvent, heating to 100 ℃ and 130 ℃, and completely dissolving;
s2, dropwise adding a part of dissolved initiator into the mixed solution, and adding an anhydride monomer and an auxiliary agent into the mixed solution after dropwise adding; after the initiator is completely dissolved, dissolving the rest initiator and dropwise adding the initiator into the mixed solution, and preserving heat for 1-5 hours to carry out reaction after the initiator is completely dissolved;
s3, adding butanone while the reaction is hot after the reaction is finished, filtering to obtain white powder, and washing the obtained white powder with butanone for multiple times to obtain the component A.
10. The preparation method of the aluminum plastic film inner layer adhesive for lithium battery encapsulation as claimed in claim 8, wherein the preparation method of the component B comprises the following steps: and diluting the bisphenol A epoxy resin and the modified bisphenol A epoxy resin with an organic solvent.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202210752686.4A CN115074056B (en) | 2022-06-29 | 2022-06-29 | Aluminum-plastic film inner layer adhesive for lithium battery packaging and preparation method thereof |
| PCT/CN2023/099085 WO2024001711A1 (en) | 2022-06-29 | 2023-06-08 | Aluminum-plastic film inner layer adhesive for lithium battery packaging and preparation method therefor |
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| CN202210752686.4A CN115074056B (en) | 2022-06-29 | 2022-06-29 | Aluminum-plastic film inner layer adhesive for lithium battery packaging and preparation method thereof |
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| Publication number | Publication date |
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| CN115074056B (en) | 2023-03-21 |
| WO2024001711A1 (en) | 2024-01-04 |
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