CN116554797B - Composite adhesive tape for lithium battery and preparation method thereof - Google Patents
Composite adhesive tape for lithium battery and preparation method thereof Download PDFInfo
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- CN116554797B CN116554797B CN202310704887.1A CN202310704887A CN116554797B CN 116554797 B CN116554797 B CN 116554797B CN 202310704887 A CN202310704887 A CN 202310704887A CN 116554797 B CN116554797 B CN 116554797B
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- stirring
- adhesive
- adhesive tape
- composite
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- 239000002390 adhesive tape Substances 0.000 title claims abstract description 58
- 239000002131 composite material Substances 0.000 title claims abstract description 50
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000003431 cross linking reagent Substances 0.000 claims description 56
- 238000003756 stirring Methods 0.000 claims description 54
- 230000001070 adhesive effect Effects 0.000 claims description 48
- 229920000058 polyacrylate Polymers 0.000 claims description 43
- 239000000853 adhesive Substances 0.000 claims description 40
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 28
- 239000000758 substrate Substances 0.000 claims description 28
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 27
- 239000011230 binding agent Substances 0.000 claims description 22
- 238000007599 discharging Methods 0.000 claims description 21
- 239000012790 adhesive layer Substances 0.000 claims description 20
- 239000010410 layer Substances 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 18
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 17
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 17
- 229920002545 silicone oil Polymers 0.000 claims description 17
- 229920002554 vinyl polymer Polymers 0.000 claims description 17
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 16
- 239000011248 coating agent Substances 0.000 claims description 16
- 238000000576 coating method Methods 0.000 claims description 16
- 239000001257 hydrogen Substances 0.000 claims description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims description 16
- 229920001721 polyimide Polymers 0.000 claims description 16
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 13
- -1 vinyl hydrogen Chemical compound 0.000 claims description 13
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 10
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 10
- 239000005062 Polybutadiene Substances 0.000 claims description 10
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 10
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 229920002857 polybutadiene Polymers 0.000 claims description 10
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims description 10
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 claims description 9
- 229940119545 isobornyl methacrylate Drugs 0.000 claims description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 8
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical group OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 8
- 238000005096 rolling process Methods 0.000 claims description 8
- 229910052710 silicon Inorganic materials 0.000 claims description 8
- 239000010703 silicon Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical group CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 7
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 239000011347 resin Substances 0.000 claims description 6
- 229920005989 resin Polymers 0.000 claims description 6
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 claims description 5
- VLSRKCIBHNJFHA-UHFFFAOYSA-N 2-(trifluoromethyl)prop-2-enoic acid Chemical compound OC(=O)C(=C)C(F)(F)F VLSRKCIBHNJFHA-UHFFFAOYSA-N 0.000 claims description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 4
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical group C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 239000001089 [(2R)-oxolan-2-yl]methanol Substances 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 2
- 239000003792 electrolyte Substances 0.000 description 19
- 239000000243 solution Substances 0.000 description 11
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 10
- 229910001416 lithium ion Inorganic materials 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 7
- 238000004132 cross linking Methods 0.000 description 5
- 238000002791 soaking Methods 0.000 description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 4
- 235000019345 sodium thiosulphate Nutrition 0.000 description 4
- 239000012086 standard solution Substances 0.000 description 4
- 125000003342 alkenyl group Chemical group 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000004448 titration Methods 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 229910002808 Si–O–Si Inorganic materials 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 239000003522 acrylic cement Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000005661 hydrophobic surface Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 230000002633 protecting effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- 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
- C09J7/22—Plastics; Metallised plastics
- C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
- C08F283/124—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes on to polysiloxanes having carbon-to-carbon double bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/04—Polymers provided for in subclasses C08C or C08F
- C08F290/048—Polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
-
- 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
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/062—Copolymers with monomers not covered by C09J133/06
- C09J133/068—Copolymers with monomers not covered by C09J133/06 containing glycidyl groups
-
- 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
-
- 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
- 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
-
- 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
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
- C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
- C09J2301/122—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present only on one side of the carrier, e.g. single-sided adhesive tape
-
- 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
- C09J2479/00—Presence of polyamine or polyimide
- C09J2479/08—Presence of polyamine or polyimide polyimide
- C09J2479/086—Presence of polyamine or polyimide polyimide in the substrate
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Adhesive Tapes (AREA)
Abstract
The invention relates to the technical field of adhesive tapes and discloses a composite adhesive tape for a lithium battery and a preparation method thereof.
Description
Technical Field
The invention relates to the technical field of adhesive tapes, in particular to a composite adhesive tape for a lithium battery and a preparation method thereof.
Background
The ion battery has the characteristics of light weight, high power, small pollution, high energy density and the like, so the ion battery is widely applied to a plurality of fields such as mobile phones, notebook computers and the like, and along with the development of technology, the lithium ion battery is used as a power energy source in the automobile field in recent years to replace the traditional fossil energy source, thereby becoming a research hot spot. In the assembly process of the lithium ion battery, the positions of the battery core, the electrode lug and the like of the battery are fixed by using the adhesive tape to play a role in protection, and the adhesive tape used by the lithium ion battery is generally required to have good adhesive property, so that the lithium ion battery is not easy to deglue and loses the protection. Meanwhile, the lithium ion battery can generate heat in the charge and discharge process, so that the adhesive tape can always work continuously at a higher temperature, and the adhesive tape special for the lithium ion battery is required to have excellent heat resistance. In addition, the special adhesive tape for the lithium ion battery can be contacted with electrolyte in the battery assembly and subsequent use processes, and the adhesive tape can not be reduced in adhesive property and finally degummed under the long-term soaking of the electrolyte.
The present market mostly adopts acrylic acid pressure-sensitive adhesive as a special adhesive tape for lithium ion batteries, while the acrylic acid pressure-sensitive adhesive has the advantages of good viscosity, weather resistance, transparency and the like, the polarity of acrylic acid polymers is larger, swelling occurs after long-term soaking in electrolyte, so that the viscosity is lost, the Chinese patent application with the application number of CN202110963216.8 discloses an electrolyte solvent-resistant acrylic acid pressure-sensitive adhesive and a preparation method, acrylic acid, hydroxyethyl acrylate, isobornyl acrylate, glycidyl methacrylate, methyl acrylate and the like are used as monomers, dibenzoyl peroxide is used as an initiator, and the electrolyte solvent-resistant acrylic acid pressure-sensitive adhesive is prepared, but the patent does not improve the heat resistance of the acrylic acid pressure-sensitive adhesive, and can not ensure that the pressure-sensitive adhesive does not lose adhesion at a higher temperature.
Based on the above, the invention provides a composite adhesive tape which can be directly applied to lithium ion batteries.
Disclosure of Invention
The invention aims to provide a composite adhesive tape for a lithium battery and a preparation method thereof, which solve the problem that the heat resistance and electrolyte resistance of an acrylic adhesive tape are poor.
The aim of the invention can be achieved by the following technical scheme:
the composite adhesive tape for the lithium battery comprises a release layer, a film substrate layer and an adhesive layer from outside to inside in sequence; the adhesive comprises the following raw materials in parts by weight: 60-80 parts of polyacrylate binder, 5-15 parts of tackifying resin and 2-8 parts of curing agent; the preparation method of the polyacrylate adhesive comprises the following steps:
the first step: pouring 200-350 parts of ethyl acetate, 50-60 parts of methyl methacrylate, 20-30 parts of isobornyl methacrylate, 5-10 parts of acrylic acid, 4-8 parts of hydroxyethyl acrylate, 2-6 parts of glycidyl methacrylate and 1-3 parts of a first cross-linking agent into a reactor, stirring and mixing uniformly, adding 0.5-1 part of benzoyl peroxide, introducing nitrogen for protection, raising the temperature of the system to 50-60 ℃, and stirring for 1-2 hours to obtain a premix;
and a second step of: adding 2-5 parts of a second cross-linking agent and 0.1-0.2 part of benzoyl peroxide into the premix, stirring uniformly, raising the temperature of the system to 70-80 ℃, stirring for 4-12h, cooling, filtering and discharging to obtain a polyacrylate adhesive;
the first crosslinking agent is prepared by introducing fluorine-containing unsaturated alkenyl functional groups at the tail ends of rubber molecular chains;
the second cross-linking agent is prepared by introducing a furan structure into a silicone oil structure.
According to the technical scheme, ethyl acetate is used as a solvent, methyl methacrylate, isobornyl methacrylate, acrylic acid, hydroxyethyl acrylate and glycidyl methacrylate are used as comonomers, benzoyl peroxide is used as an initiator, and the polyacrylate adhesive with high crosslinking degree is formed through the crosslinking action of the first crosslinking agent and the second crosslinking agent.
Further, the tackifying resin is any one of rosin or hydrogenated rosin; the curing agent is toluene-2, 4-diisocyanate.
Further, the preparation method of the first cross-linking agent specifically comprises the following steps:
mixing hydroxyl-terminated liquid polybutadiene with tetrahydrofuran, stirring uniformly, adding 2- (trifluoromethyl) acrylic acid and a composite catalyst, stirring uniformly, introducing nitrogen for protection, stirring at room temperature for 12-24h, distilling under reduced pressure to remove low-boiling substances, cooling and discharging to obtain the first cross-linking agent.
Further, the hydroxyl-terminated liquid polybutadiene has a hydroxyl number of 0.8 to 1.0mmol/g and a number average molecular weight of 2800 to 3500.
Further, the composite catalyst is dicyclohexylcarbodiimide and 4-dimethylaminopyridine in a mass ratio of 6-8:1.
Through the technical scheme, under the action of a composite catalyst, hydroxyl at the molecular chain end of hydroxyl-terminated liquid polybutadiene can be dehydrated and condensed with carboxyl in a 2- (trifluoromethyl) acrylic acid structure to generate esterification reaction, and a fluorine-containing unsaturated alkenyl functional group is introduced into the molecular chain end of the hydroxyl-terminated liquid polybutadiene to obtain the first cross-linking agent.
Further, the preparation method of the second crosslinking agent specifically comprises the following steps:
mixing vinyl hydrogen-containing silicone oil, tetrahydrofurfuryl alcohol and toluene, stirring to form a uniform solution, adding a catalyst, introducing nitrogen for protection, raising the temperature of the system to 90-100 ℃, stirring for 4-12h, evaporating the solvent after the reaction is finished, cooling, discharging and purifying to obtain the second cross-linking agent.
Further, the vinyl hydrogen silicone oil has a hydrogen content of 0.1% -1% and a vinyl content of 0.1% -10%.
Further, the catalyst is trifluoroacetic acid.
Through the technical scheme, the vinyl hydrogen-containing silicone oil structure contains terminal alkenyl and Si-H bond, and under the action of trifluoroacetic acid catalyst, the Si-H bond in the vinyl hydrogen-containing silicone oil structure can react with hydroxyl in the tetrahydrofurfuryl alcohol structure, so that furan side groups are introduced into the molecular chain of the vinyl hydrogen-containing silicone oil to obtain the second cross-linking agent.
The preparation method of the composite adhesive tape for the lithium battery comprises the following steps:
step one: uniformly coating a non-silicon release agent on the surface of a polyimide film substrate with the thickness of 10-50um, transferring the substrate into an oven with the temperature of 100-120 ℃, curing for 5-10min, taking out to form a release layer, and controlling the thickness of the release layer to be 0.1-1um;
step two: pouring polyacrylate binder and tackifying resin in parts by weight into a stirrer, stirring and mixing for 30-60min, adding curing agent in parts by weight, continuously stirring for 20-40min, and discharging to obtain an adhesive;
step three: uniformly coating the adhesive on the other surface of the polyimide film substrate, placing in an oven at 110-130 ℃, curing for 40-60min, taking out to form an adhesive layer, controlling the thickness of the adhesive layer to be 10-50um, and rolling to obtain the composite adhesive tape for the lithium battery.
The invention has the beneficial effects that:
(1) According to the invention, the first cross-linking agent is prepared and introduced into the polyacrylate binder matrix in a copolymerization mode, and the interface performance between the polybutadiene liquid rubber and the polyacrylate matrix is effectively improved in a copolymerization connection mode. The polybutadiene shows non-polarity, so that the polarity of a polyacrylate adhesive matrix can be reduced, swelling caused by soaking of an adhesive layer in electrolyte in the adhesive tape can be avoided to a certain extent, the electrolyte resistance of the adhesive tape is improved, the first cross-linking agent structure contains fluorine element with strong hydrophobic property, and the fluorine element can be dissociated to the surface of the polyacrylate adhesive because of low surface energy, so that a special orderly-arranged structure is formed, and the adhesive layer of the adhesive tape has strong solvent resistance, further has shielding and protecting effects, and can effectively resist the corrosion of the electrolyte, so that the electrolyte resistance of the adhesive tape is further enhanced.
(2) According to the invention, the second cross-linking agent is introduced into the polyacrylic acid binder matrix in a copolymerization mode, and as the silicone oil structure contains a large number of silicon-oxygen bonds with higher bond energy, the heat resistance of the polyacrylate binder can be improved, and the polyacrylate binder can be further cooperated with the first cross-linking agent to generate a hydrophobic surface, so that the polyacrylate binder can resist the erosion of electrolyte together, and the electrolyte resistance of the adhesive tape is improved. In addition, the second cross-linking agent structure contains furan side groups, the furan side groups have good wettability with the substrate, the adhesion of the polyacrylate adhesive to the substrate can be improved, the adhesive property of the adhesive tape is further enhanced, and the furan is annular side groups, so that the rigidity and elasticity of the polyacrylate adhesive can be improved, the polyacrylate adhesive shows higher cohesive force and creep resistance, and the heat resistance and electrolyte resistance of the adhesive tape are further enhanced.
(3) According to the invention, the polyacrylate adhesive is synergistically modified by the first crosslinking agent and the second crosslinking agent, under the combined action of the first crosslinking agent and the second crosslinking agent, the polyacrylate adhesive forms a three-dimensional crosslinking network, higher cohesive strength is shown, and solvents are not easy to penetrate into the polyacrylate adhesive, so that the adhesive tape has excellent adhesive property, heat resistance and electrolyte resistance through the synergistic effect of the first crosslinking agent and the second crosslinking agent.
Of course, it is not necessary for any one product to practice the invention to achieve all of the advantages set forth above at the same time.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed for the description of the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is an infrared spectrum of vinyl hydrogen silicone oil and a second crosslinking agent in example 1 of the present invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
1. Preparation of the first crosslinking agent
10mL of hydroxyl-terminated liquid polybutadiene is mixed with tetrahydrofuran, after stirring evenly, 1.5g of 2- (trifluoromethyl) acrylic acid, 0.8g of dicyclohexylcarbodiimide and 0.1g of 4-dimethylaminopyridine are added, the mixture is evenly mixed, nitrogen protection is introduced, stirring is carried out at room temperature for 16 hours, low-boiling substances are removed by reduced pressure distillation, cooling and discharging are carried out, and the first cross-linking agent is obtained, wherein the hydroxyl value of the hydroxyl-terminated liquid polybutadiene is 1.0mmol/g, and the number average molecular weight is 3000.
Accurately weighing 0.4g of a first cross-linking agent sample, placing the first cross-linking agent sample in a reactor, adding 20mL of chloroform into the reactor, stirring to form a uniform solution, transferring 30mL of Welch solution into the solution, fully and uniformly mixing, placing the reactor in a dark place for 1h, adding 20mL of KI solution with the mass fraction of 15 percent into the solution, simultaneously adding 100mL of pure water, quickly titrating with 0.1M sodium thiosulfate standard solution after the addition, adding 1mL of starch indicator with the mass fraction of 1 percent into the solution when the color of the solution is about to fade, and continuing the titration until the solution is dissolved
The color of the liquid disappears, a blank experiment is carried out, and the unsaturated value of the sample is calculated by using a formula m, wherein W is the unsaturated value in 0.4g of the sample, and mmol/g; v0 is the volume and mL of the sodium thiosulfate standard solution used in the titration blank experiment; v is the volume of the sodium thiosulfate standard solution used for titrating the sample, and mL; m is the mass of the sample, g; c is the concentration of the sodium thiosulfate standard solution and mol/L; the unsaturation value of the sample was found to be 0.381mmol/g by titration experiments.
2. Preparation of the second crosslinker
Mixing 4mL of vinyl hydrogen silicone oil, 0.8mL of tetrahydrofurfuryl alcohol and toluene, stirring to form a uniform solution, adding 0.05mL of trifluoroacetic acid, introducing nitrogen for protection, raising the temperature of the system to 100 ℃, stirring for 8 hours, evaporating the solvent after the reaction is finished, cooling, discharging and purifying to obtain a second cross-linking agent, wherein the hydrogen content of the vinyl hydrogen silicone oil is 0.6%, and the vinyl content is 4%.
The infrared test is carried out on vinyl hydrogen silicone oil and a second crosslinking agent, the test result is shown in figure 1, and the figure 1 shows that the vinyl containsHydrogen silicone oil 2800-3000 cm -1 The absorption peak of methyl appears at 2000-2200 cm -1 The absorption peak of Si-H bond appears at 1100-1200 cm -1 The absorption peak of Si-O-Si skeleton appears at the position, and the second cross-linking agent is 2800 cm to 3000cm -1 The absorption peaks of methyl and ethyl appear at 2000-2200 cm -1 The absorption peak area of Si-H bond is reduced at 1200-1300 cm -1 The absorption peak of ether bond appears at 1100-1200 cm -1 The absorption peak area of the Si-O-Si skeleton is increased because the Si-H bond in the vinyl hydrogen-containing silicone oil structure reacts with the hydroxyl group in the tetrahydrofurfuryl alcohol structure, part of the Si-H bond is consumed, and the furan group is introduced into the vinyl hydrogen-containing silicone oil structure.
3. Preparation of polyacrylate binders
The first step: pouring 200 parts of ethyl acetate, 50 parts of methyl methacrylate, 20 parts of isobornyl methacrylate, 5 parts of acrylic acid, 4 parts of hydroxyethyl acrylate, 2 parts of glycidyl methacrylate and 1 part of a first cross-linking agent into a reactor, stirring and uniformly mixing, adding 0.5 part of benzoyl peroxide, introducing nitrogen for protection, raising the temperature of the system to 50 ℃, and stirring for 1h to obtain a premix;
and a second step of: adding 2 parts of a second cross-linking agent and 0.1 part of benzoyl peroxide into the premix, stirring uniformly, raising the temperature of the system to 70 ℃, stirring for 4 hours, cooling, filtering and discharging to obtain the polyacrylate adhesive.
4. Preparation of composite adhesive tape for lithium battery
Step one: uniformly coating a non-silicon release agent on the surface of a polyimide film substrate with the thickness of 10um, transferring the substrate into a baking oven with the temperature of 100 ℃, curing for 5min, taking out to form a release layer, and controlling the thickness of the release layer to be 0.1um;
step two: pouring 60 parts of polyacrylate binder and 5 parts of rosin into a stirrer, stirring and mixing for 30min, adding 2 parts of toluene-2, 4-diisocyanate, continuously stirring for 20min, and discharging to obtain an adhesive;
step three: uniformly coating the adhesive on the other surface of the polyimide film substrate, placing in an oven at 110 ℃, curing for 40min, taking out to form an adhesive layer, controlling the thickness of the adhesive layer to be 10 mu m, and rolling to obtain the composite adhesive tape for the lithium battery.
Example 2
1. Preparation of polyacrylate binders
The first step: 300 parts of ethyl acetate, 55 parts of methyl methacrylate, 25 parts of isobornyl methacrylate, 8 parts of acrylic acid, 6 parts of hydroxyethyl acrylate, 5 parts of glycidyl methacrylate and 2 parts of a first cross-linking agent are poured into a reactor, after being stirred and mixed uniformly, 0.8 part of benzoyl peroxide is added, nitrogen is introduced for protection, the temperature of the system is raised to 60 ℃, and the mixture is stirred for 2 hours, so as to obtain a premix;
and a second step of: adding 4 parts of a second cross-linking agent and 0.2 part of benzoyl peroxide into the premix, stirring uniformly, increasing the system temperature to 80 ℃, stirring for 9 hours, cooling, filtering and discharging to obtain the polyacrylate adhesive.
Wherein the first crosslinking agent and the second crosslinking agent were prepared in the same manner as in example 1.
2. Preparation of composite adhesive tape for lithium battery
Step one: uniformly coating a non-silicon release agent on the surface of a polyimide film substrate with the thickness of 40um, transferring the substrate into a baking oven with the temperature of 110 ℃, curing for 8min, taking out to form a release layer, and controlling the thickness of the release layer to be 0.5um;
step two: pouring 70 parts of polyacrylate binder and 10 parts of hydrogenated rosin into a stirrer, stirring and mixing for 40min, adding 6 parts of toluene-2, 4-diisocyanate, continuously stirring for 30min, and discharging to obtain an adhesive;
step three: uniformly coating the adhesive on the other surface of the polyimide film substrate, placing in an oven at 120 ℃, curing for 50min, taking out to form an adhesive layer, controlling the thickness of the adhesive layer to be 30um, and rolling to obtain the composite adhesive tape for the lithium battery.
Example 3
1. Preparation of polyacrylate binders
The first step: 350 parts of ethyl acetate, 60 parts of methyl methacrylate, 30 parts of isobornyl methacrylate, 10 parts of acrylic acid, 8 parts of hydroxyethyl acrylate, 6 parts of glycidyl methacrylate and 3 parts of a first cross-linking agent are poured into a reactor, after being stirred and mixed uniformly, 1 part of benzoyl peroxide is added, nitrogen is introduced for protection, the temperature of the system is raised to 60 ℃, and stirring is carried out for 2 hours, so as to obtain a premix;
and a second step of: adding 5 parts of a second cross-linking agent and 0.2 part of benzoyl peroxide into the premix, stirring uniformly, increasing the system temperature to 80 ℃, stirring for 12 hours, cooling, filtering and discharging to obtain the polyacrylate adhesive.
Wherein the first crosslinking agent and the second crosslinking agent were prepared in the same manner as in example 1.
2. Preparation of composite adhesive tape for lithium battery
Step one: uniformly coating a non-silicon release agent on the surface of a polyimide film substrate with the thickness of 50um, transferring the substrate into a baking oven with the temperature of 120 ℃, curing for 10min, taking out to form a release layer, and controlling the thickness of the release layer to be 1um;
step two: pouring 80 parts of polyacrylate binder and 15 parts of rosin into a stirrer, stirring and mixing for 60min, adding 8 parts of toluene-2, 4-diisocyanate, continuously stirring for 40min, and discharging to obtain an adhesive;
step three: uniformly coating the adhesive on the other surface of the polyimide film substrate, placing in a baking oven at 130 ℃, curing for 60min, taking out to form an adhesive layer, controlling the thickness of the adhesive layer to be 50um, and rolling to obtain the composite adhesive tape for the lithium battery.
Comparative example 1
1. Preparation of polyacrylate binders
The first step: 300 parts of ethyl acetate, 55 parts of methyl methacrylate, 25 parts of isobornyl methacrylate, 8 parts of acrylic acid, 6 parts of hydroxyethyl acrylate, 5 parts of glycidyl methacrylate and 2 parts of a first cross-linking agent are poured into a reactor, after being stirred and mixed uniformly, 0.8 part of benzoyl peroxide is added, nitrogen is introduced for protection, the temperature of the system is raised to 60 ℃, and the mixture is stirred for 2 hours, so as to obtain a premix;
and a second step of: adding 0.2 part of benzoyl peroxide into the premix, stirring uniformly, increasing the temperature of the system to 80 ℃, stirring for 9 hours, cooling, filtering and discharging to obtain the polyacrylate adhesive.
Wherein the first crosslinking agent was prepared in the same manner as in example 1.
2. Preparation of composite adhesive tape for lithium battery
Step one: uniformly coating a non-silicon release agent on the surface of a polyimide film substrate with the thickness of 40um, transferring the substrate into a baking oven with the temperature of 110 ℃, curing for 8min, taking out to form a release layer, and controlling the thickness of the release layer to be 0.5um;
step two: pouring 70 parts of polyacrylate binder and 10 parts of hydrogenated rosin into a stirrer, stirring and mixing for 40min, adding 6 parts of toluene-2, 4-diisocyanate, continuously stirring for 30min, and discharging to obtain an adhesive;
step three: uniformly coating the adhesive on the other surface of the polyimide film substrate, placing in an oven at 120 ℃, curing for 50min, taking out to form an adhesive layer, controlling the thickness of the adhesive layer to be 30um, and rolling to obtain the composite adhesive tape for the lithium battery.
Comparative example 2
1. Preparation of polyacrylate binders
The first step: 300 parts of ethyl acetate, 55 parts of methyl methacrylate, 25 parts of isobornyl methacrylate, 8 parts of acrylic acid, 6 parts of hydroxyethyl acrylate and 5 parts of glycidyl methacrylate are poured into a reactor, and after being stirred and mixed uniformly, 0.8 part of benzoyl peroxide is added, nitrogen is introduced for protection, the temperature of the system is raised to 60 ℃, and the mixture is stirred for 2 hours, so as to obtain a premix;
and a second step of: adding 4 parts of a second cross-linking agent and 0.2 part of benzoyl peroxide into the premix, stirring uniformly, increasing the system temperature to 80 ℃, stirring for 9 hours, cooling, filtering and discharging to obtain the polyacrylate adhesive.
Wherein the second crosslinking agent was prepared in the same manner as in example 1.
2. Preparation of composite adhesive tape for lithium battery
Step one: uniformly coating a non-silicon release agent on the surface of a polyimide film substrate with the thickness of 40um, transferring the substrate into a baking oven with the temperature of 110 ℃, curing for 8min, taking out to form a release layer, and controlling the thickness of the release layer to be 0.5um;
step two: pouring 70 parts of polyacrylate binder and 10 parts of hydrogenated rosin into a stirrer, stirring and mixing for 40min, adding 6 parts of toluene-2, 4-diisocyanate, continuously stirring for 30min, and discharging to obtain an adhesive;
step three: uniformly coating the adhesive on the other surface of the polyimide film substrate, placing in an oven at 120 ℃, curing for 50min, taking out to form an adhesive layer, controlling the thickness of the adhesive layer to be 30um, and rolling to obtain the composite adhesive tape for the lithium battery.
Comparative example 3
1. Preparation of polyacrylate binders
The first step: 300 parts of ethyl acetate, 55 parts of methyl methacrylate, 25 parts of isobornyl methacrylate, 8 parts of acrylic acid, 6 parts of hydroxyethyl acrylate and 5 parts of glycidyl methacrylate are poured into a reactor, and after stirring and mixing uniformly, 1 part of benzoyl peroxide is added, nitrogen is introduced for protection, the temperature of the system is raised to 80 ℃, and stirring is carried out for 12 hours, so that the polyacrylate binder is obtained.
2. Preparation of composite adhesive tape for lithium battery
Step one: uniformly coating a non-silicon release agent on the surface of a polyimide film substrate with the thickness of 40um, transferring the substrate into a baking oven with the temperature of 110 ℃, curing for 8min, taking out to form a release layer, and controlling the thickness of the release layer to be 0.5um;
step two: pouring 70 parts of polyacrylate binder and 10 parts of hydrogenated rosin into a stirrer, stirring and mixing for 40min, adding 6 parts of toluene-2, 4-diisocyanate, continuously stirring for 30min, and discharging to obtain an adhesive;
step three: uniformly coating the adhesive on the other surface of the polyimide film substrate, placing in an oven at 120 ℃, curing for 50min, taking out to form an adhesive layer, controlling the thickness of the adhesive layer to be 30um, and rolling to obtain the composite adhesive tape for the lithium battery.
Performance detection
Referring to the national standard GB/T4852-2002 (method for testing the initial tackiness of pressure-sensitive adhesive tapes (ball method), a ball ramp stop test is adopted for testing, the measurement angle is set to be 20 degrees, and the initial tackiness performance of the composite adhesive tapes prepared in the invention examples 1-3 and the comparative examples 1-3 is tested; referring to national standard GB/T2792-2014, test 180 DEG peel force of the composite adhesive tape prepared in the embodiment 1-3 and the comparative example 1-3, after the test is finished, soaking the composite adhesive tape in lithium ion battery electrolyte, placing the composite adhesive tape in a temperature condition of 80 ℃ for 3 days, taking out the composite adhesive tape after soaking, testing 180 DEG peel force of the composite adhesive tape again, and evaluating electrolyte resistance of the composite adhesive tape; the composite tapes prepared in the invention examples 1-3 and comparative examples 1-3 were stuck on clean stainless steel plates, baked in a constant temperature oven at 150 ℃ for 4 hours, peeled off in the oven while hot, and the stainless steel plates were observed for residual adhesive marks, and the heat resistance of the composite tapes was evaluated, with the test results shown in the following table:
as can be seen from the above table, the composite adhesive tapes prepared in examples 1 to 3 of the present invention have good adhesive properties, electrolyte resistance and heat resistance.
The second cross-linking agent is not added in the composite adhesive tape prepared in the comparative example 1, so that the cross-linking density of the polyacrylate adhesive is low, the cohesive force is low, and the adhesive property and the heat resistance of the polyacrylate adhesive cannot be improved by utilizing the silicone oil and the furan group in the second cross-linking agent, so that the adhesive property, the heat resistance and the electrolyte resistance of the composite adhesive tape are poor.
The first crosslinking agent is not used in the composite adhesive tape prepared in comparative example 2, so that the crosslinking degree of the polyacrylate adhesive is low, the heat resistance and electrolyte resistance of the composite adhesive tape are affected to a certain extent, but the second crosslinking agent is added, so that the strong adhesive property is maintained.
The composite adhesive tape prepared in comparative example 3 was not added with the first and second crosslinking agents, so that the performance of the prepared composite adhesive tape was the worst.
The foregoing is merely illustrative and explanatory of the principles of the invention, as various modifications and additions may be made to the specific embodiments described, or similar thereto, by those skilled in the art, without departing from the principles of the invention or beyond the scope of the appended claims.
Claims (7)
1. The composite adhesive tape for the lithium battery is characterized by sequentially comprising a release layer, a film substrate layer and an adhesive layer from outside to inside; the adhesive comprises the following raw materials in parts by weight: 60-80 parts of polyacrylate binder, 5-15 parts of tackifying resin and 2-8 parts of curing agent; the preparation method of the polyacrylate adhesive comprises the following steps:
the first step: pouring 200-350 parts of ethyl acetate, 50-60 parts of methyl methacrylate, 20-30 parts of isobornyl methacrylate, 5-10 parts of acrylic acid, 4-8 parts of hydroxyethyl acrylate, 2-6 parts of glycidyl methacrylate and 1-3 parts of a first cross-linking agent into a reactor, stirring and mixing uniformly, adding 0.5-1 part of benzoyl peroxide, introducing nitrogen for protection, raising the temperature of the system to 50-60 ℃, and stirring for 1-2 hours to obtain a premix;
and a second step of: adding 2-5 parts of a second cross-linking agent and 0.1-0.2 part of benzoyl peroxide into the premix, stirring uniformly, raising the temperature of the system to 70-80 ℃, stirring for 4-12h, cooling, filtering and discharging to obtain a polyacrylate adhesive;
the preparation method of the first cross-linking agent specifically comprises the following steps:
mixing hydroxyl-terminated liquid polybutadiene with tetrahydrofuran, stirring uniformly, adding 2- (trifluoromethyl) acrylic acid and a composite catalyst, stirring uniformly, introducing nitrogen for protection, stirring at room temperature for 12-24 hours, distilling under reduced pressure to remove low-boiling substances, cooling and discharging to obtain a first cross-linking agent;
the preparation method of the second cross-linking agent specifically comprises the following steps:
mixing vinyl hydrogen-containing silicone oil, tetrahydrofurfuryl alcohol and toluene, stirring to form a uniform solution, adding a catalyst, introducing nitrogen for protection, raising the temperature of the system to 90-100 ℃, stirring for 4-12h, evaporating the solvent after the reaction is finished, cooling, discharging and purifying to obtain the second cross-linking agent.
2. The composite adhesive tape for lithium batteries according to claim 1, wherein said tackifying resin is any one of rosin and hydrogenated rosin; the curing agent is toluene-2, 4-diisocyanate.
3. The composite adhesive tape for lithium batteries according to claim 1, wherein said hydroxyl-terminated liquid polybutadiene has a hydroxyl value of 0.8 to 1.0mmol/g and a number average molecular weight of 2800 to 3500.
4. The composite adhesive tape for lithium batteries according to claim 1, wherein the composite catalyst is dicyclohexylcarbodiimide and 4-dimethylaminopyridine in a mass ratio of 6-8:1.
5. The composite adhesive tape for lithium batteries according to claim 1, wherein the vinyl hydrogen silicone oil has a hydrogen content of 0.1% -1% and a vinyl content of 0.1% -10%.
6. The composite tape for lithium batteries according to claim 1, wherein said catalyst is trifluoroacetic acid.
7. A method of preparing the composite tape for lithium batteries according to claim 1, comprising the steps of:
step one: uniformly coating a non-silicon release agent on the surface of a polyimide film substrate with the thickness of 10-50um, transferring the substrate into an oven with the temperature of 100-120 ℃, curing for 5-10min, taking out to form a release layer, and controlling the thickness of the release layer to be 0.1-1um;
step two: pouring polyacrylate binder and tackifying resin in parts by weight into a stirrer, stirring and mixing for 30-60min, adding curing agent in parts by weight, continuously stirring for 20-40min, and discharging to obtain an adhesive;
step three: uniformly coating the adhesive on the other surface of the polyimide film substrate, placing in an oven at 110-130 ℃, curing for 40-60min, taking out to form an adhesive layer, controlling the thickness of the adhesive layer to be 10-50um, and rolling to obtain the composite adhesive tape for the lithium battery.
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