CN114551885A - Black adhesive for lithium battery aluminum plastic film and use method thereof - Google Patents
Black adhesive for lithium battery aluminum plastic film and use method thereof Download PDFInfo
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- CN114551885A CN114551885A CN202210155972.2A CN202210155972A CN114551885A CN 114551885 A CN114551885 A CN 114551885A CN 202210155972 A CN202210155972 A CN 202210155972A CN 114551885 A CN114551885 A CN 114551885A
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- black
- isocyanate
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- plastic film
- black adhesive
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- 239000000853 adhesive Substances 0.000 title claims abstract description 75
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 75
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 67
- 239000002985 plastic film Substances 0.000 title claims abstract description 52
- 229920006255 plastic film Polymers 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 23
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 18
- 239000006229 carbon black Substances 0.000 claims abstract description 49
- 239000004677 Nylon Substances 0.000 claims abstract description 46
- 229920001778 nylon Polymers 0.000 claims abstract description 46
- 239000011888 foil Substances 0.000 claims abstract description 31
- 239000003795 chemical substances by application Substances 0.000 claims description 50
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 42
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 39
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 33
- 239000003085 diluting agent Substances 0.000 claims description 24
- 239000003960 organic solvent Substances 0.000 claims description 23
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 18
- 239000004743 Polypropylene Substances 0.000 claims description 16
- 229920001155 polypropylene Polymers 0.000 claims description 16
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 15
- 239000011265 semifinished product Substances 0.000 claims description 15
- 239000011248 coating agent Substances 0.000 claims description 14
- 238000000576 coating method Methods 0.000 claims description 14
- 239000012948 isocyanate Substances 0.000 claims description 14
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 13
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 13
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- 239000004359 castor oil Substances 0.000 claims description 12
- 235000019438 castor oil Nutrition 0.000 claims description 12
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 150000002513 isocyanates Chemical class 0.000 claims description 11
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 238000007865 diluting Methods 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- 239000012535 impurity Substances 0.000 claims description 8
- 238000000967 suction filtration Methods 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- ULQISTXYYBZJSJ-UHFFFAOYSA-N 12-hydroxyoctadecanoic acid Chemical compound CCCCCCC(O)CCCCCCCCCCC(O)=O ULQISTXYYBZJSJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 238000003825 pressing Methods 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- 229920005862 polyol Polymers 0.000 claims description 5
- 150000003077 polyols Chemical group 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 4
- 241000872198 Serjania polyphylla Species 0.000 claims description 4
- 238000000944 Soxhlet extraction Methods 0.000 claims description 4
- -1 aromatic isocyanate Chemical class 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000000605 extraction Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 229920005906 polyester polyol Polymers 0.000 claims description 4
- HHIRBXHEYVDUAM-UHFFFAOYSA-N 1-chloro-3-isocyanatobenzene Chemical compound ClC1=CC=CC(N=C=O)=C1 HHIRBXHEYVDUAM-UHFFFAOYSA-N 0.000 claims description 3
- ADAKRBAJFHTIEW-UHFFFAOYSA-N 1-chloro-4-isocyanatobenzene Chemical compound ClC1=CC=C(N=C=O)C=C1 ADAKRBAJFHTIEW-UHFFFAOYSA-N 0.000 claims description 3
- PJVRNNRZWASOIT-UHFFFAOYSA-N 1-isocyanato-4-propan-2-ylbenzene Chemical compound CC(C)C1=CC=C(N=C=O)C=C1 PJVRNNRZWASOIT-UHFFFAOYSA-N 0.000 claims description 3
- YIDSTEJLDQMWBR-UHFFFAOYSA-N 1-isocyanatododecane Chemical compound CCCCCCCCCCCCN=C=O YIDSTEJLDQMWBR-UHFFFAOYSA-N 0.000 claims description 3
- QWDQYHPOSSHSAW-UHFFFAOYSA-N 1-isocyanatooctadecane Chemical compound CCCCCCCCCCCCCCCCCCN=C=O QWDQYHPOSSHSAW-UHFFFAOYSA-N 0.000 claims description 3
- 229940114072 12-hydroxystearic acid Drugs 0.000 claims description 3
- GSLTVFIVJMCNBH-UHFFFAOYSA-N 2-isocyanatopropane Chemical compound CC(C)N=C=O GSLTVFIVJMCNBH-UHFFFAOYSA-N 0.000 claims description 3
- GIIBAUDXEXFBHL-UHFFFAOYSA-N 3-(3-methylphenoxy)propane-1,2-diol Chemical compound CC1=CC=CC(OCC(O)CO)=C1 GIIBAUDXEXFBHL-UHFFFAOYSA-N 0.000 claims description 3
- VLJQDHDVZJXNQL-UHFFFAOYSA-N 4-methyl-n-(oxomethylidene)benzenesulfonamide Chemical compound CC1=CC=C(S(=O)(=O)N=C=O)C=C1 VLJQDHDVZJXNQL-UHFFFAOYSA-N 0.000 claims description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 3
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 3
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- KQWGXHWJMSMDJJ-UHFFFAOYSA-N cyclohexyl isocyanate Chemical compound O=C=NC1CCCCC1 KQWGXHWJMSMDJJ-UHFFFAOYSA-N 0.000 claims description 3
- WUDNUHPRLBTKOJ-UHFFFAOYSA-N ethyl isocyanate Chemical compound CCN=C=O WUDNUHPRLBTKOJ-UHFFFAOYSA-N 0.000 claims description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 3
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 229920000570 polyether Polymers 0.000 claims description 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 2
- 238000009835 boiling Methods 0.000 abstract description 11
- 150000001721 carbon Chemical class 0.000 abstract description 11
- 238000002360 preparation method Methods 0.000 abstract description 5
- 239000012752 auxiliary agent Substances 0.000 abstract description 2
- 238000004040 coloring Methods 0.000 abstract description 2
- 239000012790 adhesive layer Substances 0.000 abstract 1
- 230000007547 defect Effects 0.000 abstract 1
- 239000010410 layer Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 15
- 238000004080 punching Methods 0.000 description 8
- 239000002994 raw material Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 241001330498 Corsia Species 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 238000010030 laminating Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- MGYGFNQQGAQEON-UHFFFAOYSA-N 4-tolyl isocyanate Chemical group CC1=CC=C(N=C=O)C=C1 MGYGFNQQGAQEON-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910021392 nanocarbon Inorganic materials 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Cell Electrode Carriers And Collectors (AREA)
Abstract
The invention discloses a black adhesive for a lithium battery aluminum plastic film and a use method thereof. The modified carbon black has affinity with an adhesive system, presents excellent dispersing capacity, solves the problem that common nano-scale carbon black is easy to agglomerate and settle, and does not need to add a dispersing auxiliary agent in the adhesive preparation process. And then, the black adhesive is used as an adhesive layer of nylon and aluminum foil to realize aluminum-plastic film coloring, and the defects of low adhesive strength, no high temperature and humidity resistance, no boiling resistance and the like of the traditional ink printing type black aluminum-plastic film nylon layer and the aluminum foil are overcome.
Description
Technical Field
The invention relates to the field of aluminum plastic films for lithium ion batteries, in particular to a black adhesive for an aluminum plastic film for a lithium battery and a using method thereof.
Background
At present, the black aluminum plastic film for the lithium ion battery is mainly colored by adopting printing ink on a nylon layer, the printing ink coating is difficult to realize stronger mutual bonding with a polymer coating, the bonding strength of the nylon layer and an aluminum foil is reduced, the high-temperature high-humidity resistance and boiling resistance of the finished aluminum plastic film are poor, and the high-end product requirement is difficult to meet.
Therefore, how to achieve the improvement of the high temperature, high humidity and boiling resistance of the finished product and reduce the production cost is one of the directions that the skilled person is constantly working on.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provide a black adhesive for a lithium battery aluminum plastic film, which improves the high-temperature high-humidity resistance and boiling resistance of a finished black aluminum plastic film, reduces the production cost and improves the product performance and economic benefit.
The invention also provides a use method of the black adhesive for the lithium battery aluminum plastic film.
The purpose of the invention is realized as follows:
the invention provides a black adhesive for a lithium battery aluminum plastic film, which comprises the following components in parts by weight:
the black adhesive is prepared by dispersing the nano-scale carbon black with the average particle size of 100-200nm in the second organic solvent, wherein the weight ratio of the nano-scale carbon black to the second organic solvent is 2: 3.
The preparation method of the black adhesive comprises the following steps:
the method comprises the following steps: dispersing 5 parts by weight of carbon black in 40 parts by weight of toluene, extracting impurities in the carbon black by Soxhlet extraction for 24 hours, and drying for later use after extraction is finished;
step two: dispersing the carbon black subjected to impurity removal in the step one in 20 parts by weight of hydrogen peroxide, reacting for 1h at 100 ℃, cooling to room temperature, performing suction filtration and collection, washing with deionized water until a washing liquid is neutral, and performing vacuum drying at 65 ℃ to constant weight;
step three: dispersing the carbon black subjected to the oxidation treatment in the step and 20 parts by weight of isocyanate in 100 parts by weight of anhydrous N, N-dimethylformamide, heating to 80 ℃ with stirring and vacuumizing, injecting a dibutyltin dilaurate solution serving as a catalyst, continuously reacting for 5 hours, cooling to room temperature, introducing air, performing suction filtration and collection, washing for 3 times by using the anhydrous N, N-dimethylformamide, and performing vacuum drying at 85 ℃ to constant weight; wherein the dibutyltin dilaurate is prepared by dissolving 0.1 weight part of dibutyltin dilaurate in 0.4 weight part of anhydrous N, N-dimethylformamide.
The black adhesive is characterized in that the second organic solvent is at least one selected from ethyl acetate, toluene, tetrahydrofuran, acetone and butanone.
The black adhesive is characterized in that the isocyanate is monofunctional isocyanate and is at least one selected from ethyl isocyanate, isopropyl isocyanate, dodecyl isocyanate, octadecyl isocyanate, cyclohexyl isocyanate, m-chlorophenyl isocyanate, p-chlorophenyl isocyanate, m-toluene isocyanate, p-isopropylphenyl isocyanate, and p-toluenesulfonyl isocyanate.
The black adhesive is prepared from a main agent, a secondary agent and a solvent, wherein the main agent is polyol selected from polyether polyol, polyester polyol, castor oil, hydrogenated castor oil, oxidized castor oil, dehydrated castor oil or 12-hydroxystearic acid.
The black adhesive is prepared from a curing agent, a curing agent and a curing agent, wherein the curing agent is an aliphatic or aromatic isocyanate prepolymer and is selected from hexamethylene diisocyanate prepolymer, isophorone diisocyanate prepolymer, diphenylmethane diisocyanate prepolymer or toluene diisocyanate prepolymer.
In the black adhesive, the initial solid contents of the main agent, the curing agent and the color paste are respectively 30%, 75% and 40%.
The black adhesive may further comprise a second organic solvent, wherein the second organic solvent is at least one selected from ethyl acetate, toluene, tetrahydrofuran, acetone, and methyl ethyl ketone.
The invention also provides a use method of the black adhesive for the lithium battery aluminum plastic film, wherein the lithium battery aluminum plastic film comprises a nylon layer and an aluminum foil/polypropylene semi-finished product, and the use method comprises the following steps:
step 1: weighing color paste, a main agent, a curing agent and a first organic solvent according to a certain mass part, diluting the color paste and the main agent to preset concentrations by using the first organic solvent to respectively obtain a color paste diluent and a host diluent, sequentially adding the color paste diluent and the curing agent into the main agent diluent along with stirring, and passing the mixed solution through a filter to obtain the black adhesive; wherein the filter cut-off particle size is 0.8 μm;
step 2: coating the black adhesive prepared in the step 1 on the lower surface of the aluminum plastic film nylon layer of the lithium battery, wherein the coating weight is 4-8g/m2And then arranging the nylon layer on the upper surface of the aluminum foil/polypropylene semi-finished product and pressing the aluminum foil/polypropylene semi-finished product and the nylon layer together, volatilizing the solvent and curing to obtain a black aluminum-plastic film, wherein the curing temperature is 60-90 ℃ and the curing time is 3-10 days.
Compared with the prior art, the invention has the following beneficial effects:
1) the modified nano-scale carbon black is selected for coloring, so that the problems of easy agglomeration and sedimentation of the common nano-scale carbon black are solved, and no dispersing auxiliary agent is required to be additionally added in the adhesive preparation process;
2) the surface modification is carried out on the carbon black to increase the compatibility of the carbon black with an adhesive system, so that the problems of agglomeration, deposition, precipitation and the like in the use process are avoided;
3) the black adhesive is used for replacing a black printing film, so that the high-temperature and high-humidity resistance and boiling resistance of a finished black aluminum plastic film can be improved, the production cost can be reduced, and the product performance and the economic benefit can be improved.
Drawings
FIG. 1 is a reaction scheme for the preparation of nanoscale carbon black by surface modification of carbon black in accordance with the present invention;
FIG. 2 is a schematic structural diagram of a black aluminum-plastic film prepared by using the black adhesive of the present invention.
Detailed Description
The present invention will be further described with reference to the following examples. It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
The invention provides a black adhesive for a lithium battery aluminum plastic film, which comprises the following components in parts by weight:
the color paste is prepared by dispersing the nano-scale carbon black with the average particle size of 100-200nm in a second organic solvent, wherein the weight ratio of the nano-scale carbon black to the second organic solvent is 2: 3.
The preparation method of the nano-scale carbon black comprises the following steps:
the method comprises the following steps: dispersing 5 parts by weight of carbon black in 40 parts by weight of toluene, extracting impurities in the carbon black by Soxhlet extraction for 24 hours, and drying for later use after extraction is finished;
step two: dispersing the carbon black subjected to impurity removal in the step one in 20 parts by weight of hydrogen peroxide, reacting for 1h at 100 ℃, cooling to room temperature, performing suction filtration and collection, washing with deionized water until a washing liquid is neutral, and performing vacuum drying at 65 ℃ to constant weight;
step three: dispersing the carbon black subjected to the oxidation treatment in the step and 20 parts by weight of isocyanate in 100 parts by weight of anhydrous N, N-dimethylformamide, heating to 80 ℃ with stirring and vacuumizing, injecting a dibutyltin dilaurate solution serving as a catalyst, continuously reacting for 5 hours, cooling to room temperature, introducing air, performing suction filtration and collection, washing for 3 times by using the anhydrous N, N-dimethylformamide, and performing vacuum drying at 85 ℃ to constant weight; wherein the dibutyltin dilaurate is prepared by dissolving 0.1 weight part of dibutyltin dilaurate in 0.4 weight part of anhydrous N, N-dimethylformamide.
The second organic solvent is at least one selected from the group consisting of ethyl acetate, toluene, tetrahydrofuran, acetone, and butanone.
The isocyanate is monofunctional isocyanate and is at least one selected from ethyl isocyanate, isopropyl isocyanate, dodecyl isocyanate, octadecyl isocyanate, cyclohexyl isocyanate, m-chlorophenyl isocyanate, p-chlorophenyl isocyanate, m-toluene isocyanate, p-isopropylphenyl isocyanate and p-toluenesulfonyl isocyanate.
The main agent is polyalcohol selected from polyether polyol, polyester polyol, castor oil, hydrogenated castor oil, oxidized castor oil, dehydrated castor oil or 12-hydroxystearic acid.
The curing agent is aliphatic or aromatic isocyanate prepolymer and is selected from hexamethylene diisocyanate prepolymer, isophorone diisocyanate prepolymer, diphenylmethane diisocyanate prepolymer or toluene diisocyanate prepolymer.
The initial solid contents of the main agent, the curing agent and the color paste are respectively 30%, 75% and 40%.
The first organic solvent is at least one selected from the group consisting of ethyl acetate, toluene, tetrahydrofuran, acetone, and butanone.
The invention also provides a use method of the black adhesive for the lithium battery aluminum plastic film, wherein the lithium battery aluminum plastic film comprises a nylon layer and an aluminum foil/polypropylene semi-finished product, and the use method comprises the following steps:
step 1: weighing color paste, a main agent, a curing agent and a first organic solvent according to a certain mass part, diluting the color paste and the main agent to preset concentrations by using the first organic solvent to respectively obtain a color paste diluent and a host diluent, sequentially adding the color paste diluent and the curing agent into the main agent diluent along with stirring, and passing the mixed solution through a filter to obtain the black adhesive; wherein the filter cut-off particle size is 0.8 μm;
step 2: coating the black adhesive prepared in the step 1 on the lower surface of the nylon layer of the aluminum plastic film of the lithium battery, wherein the coating weight is 4-8g/m2And then arranging the nylon layer on the upper surface of the aluminum foil/polypropylene semi-finished product and pressing the aluminum foil/polypropylene semi-finished product and the nylon layer together, volatilizing the solvent and curing to obtain a black aluminum-plastic film, wherein the curing temperature is 60-90 ℃ and the curing time is 3-10 days.
The raw materials and their sources used in the following examples are specifically as follows:
1. the main agent is polyester polyol which is purchased from Corsia polymer (China) Limited and has the product brand of
AD 2047；
2. The curing agent is diphenylmethane diisocyanate prepolymer which is purchased from Corsia Polymer (China) Co., Ltd and has the product brand of
E 1660；
3. The first organic solvent and the second organic solvent are both ethyl acetate and are purchased from chemical reagents of national drug group, Inc.;
4. the carbon Black is purchased from Shanghai Special chemistry (Shanghai) Co., Ltd, and the product brand is Lamp Black 101;
5. toluene was purchased from national pharmaceutical group chemical agents, ltd;
6. hydrogen peroxide is purchased from national medicine group chemical reagents limited;
7. the isocyanate is p-toluene isocyanate which is purchased from Corsia polymer (China) Co.Ltd;
8. anhydrous N, N-dimethylformamide was purchased from national pharmaceutical group chemicals ltd;
9. dibutyl tin dilaurate was purchased from Shanghai Allantin Biotech Co., Ltd;
10. the reaction route of the nano-scale carbon black is shown in figure 1, and the specific steps are as follows:
the method comprises the following steps: dispersing 5 parts by weight of carbon black in 40 parts by weight of toluene, extracting impurities in the carbon black by Soxhlet extraction for 24 hours, and drying for later use after extraction is finished;
step two: dispersing the carbon black subjected to impurity removal in the step one in 20 parts by weight of hydrogen peroxide, reacting for 1 hour at 100 ℃, cooling to room temperature, performing suction filtration and collection, washing with deionized water until washing liquor is neutral, and performing vacuum drying at 65 ℃ to constant weight;
step three: dispersing the carbon black subjected to the oxidation treatment in the step and 20 parts by weight of isocyanate in 100 parts by weight of anhydrous N, N-dimethylformamide, heating to 80 ℃ with stirring and vacuumizing, injecting a dibutyltin dilaurate solution serving as a catalyst, continuously reacting for 5 hours, cooling to room temperature, introducing air, performing suction filtration and collection, washing for 3 times by using the anhydrous N, N-dimethylformamide, and performing vacuum drying at 85 ℃ to constant weight; wherein the dibutyltin dilaurate is prepared by dissolving 0.1 weight part of dibutyltin dilaurate in 0.4 weight part of anhydrous N, N-dimethylformamide.
11. The color paste is prepared by dispersing nano-scale carbon black in a second organic solvent, and the mass ratio of the nano-scale carbon black to the second organic solvent is 2: 3.
The features and properties of the present invention are further described in detail below with reference to the examples.
Example 1
The black adhesive comprises the following raw materials in parts by weight:
wherein the initial solid contents of the main agent, the curing agent and the color paste are respectively 30%, 75% and 40%.
The black aluminum-plastic film is prepared by coating a black adhesive on the surface of nylon and then compounding the nylon surface with an aluminum foil/polypropylene semi-finished product, and the method comprises the following specific steps:
the method comprises the following steps: weighing the raw materials in parts by mass, diluting 18.75 parts by weight of color paste by using 20.25 parts by weight of ethyl acetate, diluting 250 parts by weight of main agent by using 140 parts by weight of ethyl acetate to respectively obtain color paste diluent and main agent diluent, sequentially adding the color paste diluent and 29 parts by weight of curing agent into the main agent diluent along with stirring, and passing the mixed solution through a filter (the particle size is intercepted by the filter to be 0.8 mu m) to obtain the black adhesive;
step two: the black adhesive is coated on the nylon surface (coating weight is 6 g/m)2) Then pressing and laminating the nylon and the aluminum foil/polypropylene semi-finished product together, volatilizing the solvent and curing to obtain a black aluminum-plastic film, wherein the curing temperature is 70 ℃, and the curing time is 7 days.
The prepared black aluminum-plastic film structure is shown in fig. 2 and comprises a nylon layer 1, a black adhesive 2, an aluminum foil layer 3, an adhesive 4 and a polypropylene film layer 5 from top to bottom.
Example 2
The black adhesive comprises the following raw materials in parts by weight:
wherein the initial solid contents of the main agent, the curing agent and the color paste are respectively 30%, 75% and 40%.
The black aluminum-plastic film is prepared by coating a black adhesive on the surface of nylon and then compounding the nylon surface with an aluminum foil/polypropylene semi-finished product, and the method comprises the following specific steps:
the method comprises the following steps: weighing the raw materials in parts by mass, diluting 9.375 parts by weight of color paste by using 10.125 parts by weight of ethyl acetate, diluting 250 parts by weight of main agent by using 140 parts by weight of ethyl acetate to respectively obtain color paste diluent and main agent diluent, sequentially adding the color paste diluent and 29 parts by weight of curing agent into the main agent diluent along with stirring, and passing the mixed solution through a filter (the particle size is intercepted by the filter to be 0.8 mu m) to obtain the black adhesive;
step two: the black adhesive is coated on the nylon surface (coating weight is 6 g/m)2)，Then pressing and laminating the nylon and the aluminum foil/polypropylene semi-finished product together, volatilizing the solvent, and curing to obtain the black aluminum-plastic film, wherein the curing temperature is 70 ℃, and the curing time is 7 days.
Example 3
The black adhesive comprises the following raw materials in parts by weight:
wherein the initial solid contents of the main agent, the curing agent and the color paste are respectively 30%, 75% and 40%.
The black aluminum-plastic film is prepared by coating a black adhesive on the surface of nylon and then compounding the nylon surface with an aluminum foil/polypropylene semi-finished product, and the method comprises the following specific steps:
the method comprises the following steps: weighing the raw materials in parts by mass, diluting 3.75 parts by weight of color paste by using 4.05 parts by weight of ethyl acetate, diluting 250 parts by weight of main agent by using 140 parts by weight of ethyl acetate to respectively obtain color paste diluent and main agent diluent, sequentially adding the color paste diluent and 29 parts by weight of curing agent into the main agent diluent along with stirring, and passing the mixed solution through a filter (the particle size is intercepted by the filter to be 0.8 mu m) to obtain the black adhesive;
step two: the black adhesive is coated on the nylon surface (coating weight is 6 g/m)2) Then pressing and laminating the nylon and the aluminum foil/polypropylene semi-finished product together, volatilizing the solvent and curing to obtain a black aluminum-plastic film, wherein the curing temperature is 70 ℃, and the curing time is 7 days.
Comparative example 1
The difference between the comparative example and the example 1 is that the color paste comprises common nano carbon black, a dispersing aid and ethyl acetate, wherein the initial solid content of the color paste is 40 percent, and the color paste is purchased from three liter company Limited and has the brand number of 9007-U.
Comparative example 2
This comparative example differs from the examples in that it is a conventional printed nylon-based black aluminum plastic film.
For examples 1-3 and comparative examples 1 and 2, the bonding fastness of the aluminum foil and nylon is characterized by the initial peel strength of the aluminum foil/nylon, and the high-temperature and high-humidity resistance of the aluminum foil/nylon is reflected by the peel strength of the aluminum foil/nylon after high-temperature and high-humidity treatment.
Characterization of high temperature and high humidity resistance stripping performance of black aluminum plastic film
Strips 15mm wide are scribed from examples 1-3 and comparative examples 1 and 2, placed in a constant temperature and humidity box with the environmental parameters of 70 ℃ and 90% RH, two strips are taken out after 0h, 1h, 4h and 8h in sequence, the nylon and the aluminum foil are peeled off, the peel strength is tested on a universal tensile machine, the distance between an upper clamp and a lower clamp is 50mm, and the tensile speed is 200 mm/min.
The test results are shown in table 1 below:
TABLE 1 results of the test for peeling resistance to high temperature and high humidity of examples 1 to 3 and comparative examples 1 and 2
The above experimental data show that the aluminum foil/nylon bonding strength and high temperature and high humidity resistance of the black adhesive-based aluminum plastic film (examples 1-3 and comparative example 1) are higher than those of the printed nylon-based aluminum plastic film (comparative example 2). The reason is that the black adhesive of the former is directly contacted with the surfaces of the aluminum foil and the nylon to realize adhesion, the existence of the printing layer prevents the adhesive from being directly contacted with the nylon layer, and the adhesive force of the printing layer on the nylon is lower than that of the adhesive, so that the adhesion fastness and the high temperature and high humidity resistance of the aluminum foil and the nylon of the former are superior to those of the latter.
The aluminum plastic film using the modified carbon black (example 1) has slightly better aluminum foil/nylon bonding strength and high temperature and high humidity resistance than the film using the dispersion aid (comparative example 1). This is probably because the relatively high viscosity of the adhesive system is not favorable for the dispersion aid to exert the dispersion-assisting effect, and the dispersion of the unmodified carbon black is limited, so that the dispersion is not uniform, and the mechanical properties and the bonding ability of the adhesive are adversely affected.
As the content of the modified carbon black was increased from 2% (example 1) to 5% (example 2) and 10% (example 3), the aluminum foil/nylon bond strength and the high temperature and high humidity resistance of the black adhesive-based aluminum plastic film increased and then decreased. The reason is that a small amount of carbon black is uniformly dispersed in the adhesive, plays a role of crystallization nuclei, and can promote the local crystallization of polyurethane (a cured adhesive main body), so that the mechanical property of the adhesive is improved, and the bonding strength is enhanced; however, when the carbon black is excessive, the local agglomeration can occur, the compatibility with polyurethane is reduced, and phase separation occurs, so that the mechanical property of the adhesive is poor, and the bonding strength is weakened.
Characterization of boiling resistance of black aluminum plastic film
According to the examples 1-3 and the comparative examples 1 and 2, the shell punching depth of 5.5mm is obtained by punching through a deep punching machine, then the shell punching depth is placed in a water bath environment at 60 ℃ for several hours, the shell punching depth is taken out, the layering conditions of nylon and aluminum foil on the outer side of the shell punching are observed (10 samples are taken as a group), and the boiling resistance of the black aluminum-plastic film is judged according to the time for layering of the shell punching of each sample and the number of the shell punching with layering.
The test results are shown in table 2 below:
TABLE 2 results of the boil resistance test of examples 1 to 3 and comparative examples 1 and 2
The above experimental data show that the boiling resistance of the black adhesive aluminum plastic film (examples 1-3 and comparative example 1) is better than that of the printed nylon aluminum plastic film (comparative example 2); the boiling resistance of the aluminum plastic film (example 1) adopting the modified carbon black is slightly better than that of the aluminum plastic film (comparative example 1) added with the dispersing aid; as the content of the modified carbon black was increased from 2% (example 1) to 5% (example 2) and 10% (example 3), the boiling resistance of the black adhesive-based aluminum plastic film increased and then decreased, and the black adhesive-based aluminum plastic film was consistent with the adhesive strength and the high-temperature and high-humidity resistance.
The analysis and comparison of test results show that the direct use of the black adhesive obviously improves the aluminum foil/nylon bonding strength of the black aluminum-plastic film and the high temperature, high humidity and boiling resistance of the material, and has obvious advantages compared with the conventional printing black aluminum-plastic film. In addition, the excellent dispersibility of the modified carbon black enables the modified carbon black to be fed in a higher proportion, the upper limit of the addition of the modified carbon black in the adhesive is higher than that of the unmodified carbon black, so that the degree of dyeing of a black film is higher, and the time and the money cost are saved more when the modified carbon black is selected than when the highly-dispersed compound carbon color paste is screened.
The above embodiments are provided only for illustrating the present invention and not for limiting the present invention, and those skilled in the art can make various changes and modifications without departing from the spirit and scope of the present invention, and therefore all equivalent technical solutions should also fall within the scope of the present invention, and should be defined by the claims.
Claims (10)
1. The black adhesive for the lithium battery aluminum plastic film is characterized by comprising the following components in parts by weight: the black adhesive comprises the following components in parts by weight:
2. the black adhesive according to claim 1, wherein the color paste is prepared by dispersing nano-scale carbon black with an average particle size of 100-200nm in a second organic solvent, wherein the weight ratio of the nano-scale carbon black to the second organic solvent is 2: 3.
3. A black adhesive according to claim 2, wherein the nanoscale carbon black is prepared by a process comprising the steps of:
the method comprises the following steps: dispersing 5 parts by weight of carbon black in 40 parts by weight of toluene, extracting impurities in the carbon black by Soxhlet extraction for 24 hours, and drying for later use after extraction is finished;
step two: dispersing the carbon black subjected to impurity removal in the step one in 20 parts by weight of hydrogen peroxide, reacting for 1h at 100 ℃, cooling to room temperature, performing suction filtration and collection, washing with deionized water until a washing liquid is neutral, and performing vacuum drying at 65 ℃ to constant weight;
step three: dispersing the carbon black subjected to the oxidation treatment in the step and 20 parts by weight of isocyanate in 100 parts by weight of anhydrous N, N-dimethylformamide, heating to 80 ℃ with stirring and vacuumizing, injecting a dibutyltin dilaurate solution serving as a catalyst, continuously reacting for 5 hours, cooling to room temperature, introducing air, performing suction filtration and collection, washing for 3 times by using the anhydrous N, N-dimethylformamide, and performing vacuum drying at 85 ℃ to constant weight; wherein the dibutyltin dilaurate is prepared by dissolving 0.1 weight part of dibutyltin dilaurate in 0.4 weight part of anhydrous N, N-dimethylformamide.
4. A black adhesive according to claim 2, wherein the second organic solvent is at least one selected from the group consisting of ethyl acetate, toluene, tetrahydrofuran, acetone and methyl ethyl ketone.
5. The black adhesive according to claim 3, wherein the isocyanate is a monofunctional isocyanate and is at least one selected from the group consisting of ethyl isocyanate, isopropyl isocyanate, dodecyl isocyanate, octadecyl isocyanate, cyclohexyl isocyanate, m-chlorophenyl isocyanate, p-chlorophenyl isocyanate, m-toluene isocyanate, p-isopropylphenyl isocyanate, and p-toluenesulfonyl isocyanate.
6. A black adhesive according to claim 1, wherein the primary agent is a polyol selected from the group consisting of polyether polyols, polyester polyols, castor oil, hydrogenated castor oil, oxidized castor oil, dehydrated castor oil and 12-hydroxystearic acid.
7. A black adhesive according to claim 1, wherein the curing agent is an aliphatic or aromatic isocyanate prepolymer selected from hexamethylene diisocyanate prepolymer, isophorone diisocyanate prepolymer, diphenylmethane diisocyanate prepolymer or toluene diisocyanate prepolymer.
8. A black adhesive according to claim 1, wherein the primary, curing and mill base have initial solids contents of 30%, 75% and 40%, respectively.
9. A black adhesive according to claim 1, wherein the first organic solvent is at least one selected from the group consisting of ethyl acetate, toluene, tetrahydrofuran, acetone and methyl ethyl ketone.
10. A method for using the black adhesive for the aluminum plastic film of the lithium battery as claimed in any one of claims 1 to 9, wherein the aluminum plastic film of the lithium battery comprises a nylon layer, an aluminum foil/polypropylene semi-finished product, and the method comprises the following steps:
step 1: weighing color paste, a main agent, a curing agent and a first organic solvent according to a certain mass part, diluting the color paste and the main agent to preset concentrations by using the first organic solvent to respectively obtain a color paste diluent and a host diluent, sequentially adding the color paste diluent and the curing agent into the main agent diluent along with stirring, and passing the mixed solution through a filter to obtain the black adhesive; wherein the filter cut-off particle size is 0.8 μm;
step 2: coating the black adhesive prepared in the step 1 on the lower surface of the aluminum plastic film nylon layer of the lithium battery, wherein the coating weight is 4-8g/m2And then arranging the nylon layer on the upper surface of the aluminum foil/polypropylene semi-finished product and pressing the aluminum foil/polypropylene semi-finished product and the nylon layer together, volatilizing the solvent and curing to obtain a black aluminum-plastic film, wherein the curing temperature is 60-90 ℃ and the curing time is 3-10 days.
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