WO2018081941A1 - 结构胶纸及其制备方法、在电极片预留极耳空位的方法 - Google Patents

结构胶纸及其制备方法、在电极片预留极耳空位的方法 Download PDF

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Publication number
WO2018081941A1
WO2018081941A1 PCT/CN2016/104319 CN2016104319W WO2018081941A1 WO 2018081941 A1 WO2018081941 A1 WO 2018081941A1 CN 2016104319 W CN2016104319 W CN 2016104319W WO 2018081941 A1 WO2018081941 A1 WO 2018081941A1
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WIPO (PCT)
Prior art keywords
structural adhesive
acrylate
meth
group
methacrylate
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Ceased
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PCT/CN2016/104319
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English (en)
French (fr)
Inventor
戴志芳
龙海
陶兴华
张盛武
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Ningde Amperex Technology Ltd
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Ningde Amperex Technology Ltd
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Priority to PCT/CN2016/104319 priority Critical patent/WO2018081941A1/zh
Publication of WO2018081941A1 publication Critical patent/WO2018081941A1/zh
Anticipated expiration legal-status Critical
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/50—Current conducting connections for cells or batteries
    • H01M50/531—Electrode connections inside a battery casing
    • 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
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • 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
    • 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

Definitions

  • the invention relates to the field of adhesive tape, in particular to a structural adhesive tape and a preparation method thereof, and a method for leaving a ferrule in an electrode sheet.
  • the prior art adhesive tape generally uses a PET substrate and an acrylate-based pressure-sensitive adhesive plus a foaming agent particle to effect foaming to peel off from the current collector to reserve a crater on the current collector.
  • the blowing agent particles 21' are completely coated in the adhesive in the adhesive layer 2'. Even if the foaming agent particles 21' expand after foaming, the contact area between the adhesive and the current collector cannot be effectively reduced, and the adhesive paper is difficult to be peeled off, and the polar ear vacancies cannot be reserved on the current collector. Referring to FIGS.
  • the foaming agent particles generally have a wide particle size distribution (5 ⁇ m to 30 ⁇ m), they are mixed and coated in an adhesive for drying and drying, and two failure modes are apt to occur.
  • the adhesive layer is too thick, and the foaming expansion of the foaming agent particles cannot effectively reduce the contact area between the adhesive and the current collector, resulting in excessive viscosity after foaming, and cannot be peeled off from the empty foil region of the current collector. Causes a broken belt.
  • the adhesive layer is too thin, and the foaming agent particles are exposed outside the adhesive, which hinders the contact between the adhesive and the empty foil area of the current collector, resulting in weak viscosity after foaming, due to the foaming agent particles.
  • the foaming agent When the foaming agent is not completely dried during foaming, when the foaming agent particles are weakly viscous, the adhesive tape is easily taken up by the hot air and sticks to the wet film area. After the wet film is dried, the foaming agent particles are intensively increased and cannot be normalized. Peeling can also cause broken belts.
  • the thickness of the adhesive layer is usually required to be small, the precision of the conventional coating process cannot meet the requirements, and the thickness fluctuation causes a large amount of products to be scrapped.
  • an object of the present invention is to provide a structural adhesive tape and a method for preparing the same, and a method for preserving a vacancy of a tab on an electrode sheet, wherein the structural adhesive sheet is in conformity with the object to be pasted.
  • High and easy to carry out Batch production has solved the problem of serious viscosity fluctuation after foaming agent particles in conventional adhesive tape.
  • Another object of the present invention is to provide a structural adhesive tape and a preparation method thereof, and a method for preserving a vacancy of a tab on an electrode sheet, which can improve the utilization rate of the active material of the battery and avoid waste of the active material, and at the same time Improve battery energy density, fast-shooting performance and heat dissipation.
  • the present invention provides a structural adhesive tape comprising: an adhesive layer for attaching to an object to be pasted; and a substrate located at a distance from the structural adhesive tape Paste one side of the object.
  • the adhesive layer includes a first adhesive, a first curing agent, a second adhesive, a second curing agent, and blowing agent particles distributed therein.
  • the curing temperature of the first adhesive and the first curing agent is 20 ° C to 80 ° C; the curing temperature of the second adhesive and the second curing agent is greater than 80 ° C and less than or equal to 180 ° C.
  • the present invention provides a method for preparing a structural adhesive tape for preparing the structural adhesive tape according to one aspect of the present invention, comprising the steps of: first adhesive, first curing agent, The second adhesive and the second curing agent are dissolved in the solvent, and after being uniformly stirred, the foaming agent particles are added to form a slurry; the slurry is coated on one surface of the substrate, and then dried in an oven. The solvent is removed; the structural adhesive tape is taken out from the oven and then matured to complete the preparation of the structural adhesive tape.
  • the present invention provides a method of preserving a tab vacancy in an electrode sheet, comprising the steps of: pasting a structure according to an aspect of the invention on a reserved area on a current collector of the electrode sheet Adhesive paper, the adhesive layer of the structural adhesive paper is pasted on the current collector, and the electrode slurry is coated on the surface of the structural adhesive paper substrate to obtain a wet film; the wet film is sent to the low temperature zone of the oven for baking.
  • the structural adhesive paper still remains bonded to the current collector, wherein the baking temperature in the low temperature zone is less than the initial foaming temperature of the foaming agent particles; the wet film is continuously sent to the high temperature zone of the oven for baking, so that the structural adhesive tape is The foaming agent particles are foamed, the structural adhesive paper is curled, and the bonding force between the structural adhesive paper and the current collector is not more than 4 N/cm 2 , wherein the baking temperature in the high temperature region is greater than or equal to the blowing agent particles.
  • the structural adhesive paper of the invention has extremely high viscosity consistency with the object to be pasted, and is easy to be mass-produced, and solves the problem that the viscosity of the foaming agent particles in the conventional adhesive paper is severe after foaming.
  • the structural adhesive tape of the invention can improve the utilization rate of the active material of the battery, avoid the waste of the active material, and at the same time improve the energy density, fast-release performance and heat dissipation performance of the battery.
  • FIG. 1 is a perspective view of a current collector of a bonded object to which a structural adhesive tape according to the present invention is applied;
  • Figure 2 is a perspective view of a structural adhesive tape adhered to a current collector of a bonded object according to the present invention
  • Figure 3 is a perspective view of a structural adhesive coated electrode slurry according to the present invention.
  • Figure 4 is a perspective view of the structural adhesive tape after peeling according to the present invention.
  • Figure 5 is a perspective view of a structural adhesive tape according to the present invention.
  • Figure 6 is a front view of Figure 5;
  • FIG. 7A to 7B are respectively schematic views of an embodiment of a prior art adhesive tape, wherein FIG. 7A shows a schematic view of the foaming agent particles before foaming, and FIG. 7B shows a schematic view of the foaming agent particles after foaming;
  • FIG. 8A to 8B are respectively schematic views of another embodiment of the prior art adhesive tape, wherein FIG. 8A shows a schematic view of the foaming agent particles before foaming, and FIG. 8B shows a schematic view of the foaming agent particles after foaming;
  • FIGS. 9A to 9B are respectively schematic views of still another embodiment of the prior art adhesive tape, wherein Fig. 9A shows a schematic view of the foaming agent particles before foaming, and Fig. 9B shows a schematic view of the foaming agent particles after foaming.
  • the structural adhesive tape 1 according to the first aspect of the present invention comprises: an adhesive layer 11 for sticking on an object to be pasted; and a substrate 12 which is located away from the structural adhesive tape 1.
  • the adhesive layer 11 includes a first adhesive, a first curing agent, a second adhesive, a second curing agent, and blowing agent particles 111 distributed therein.
  • the curing temperature of the first adhesive and the first curing agent is 20 ° C to 80 ° C; the curing temperature of the second adhesive and the second curing agent is greater than 80 ° C and less than or equal to 180 ° C.
  • the first adhesive and the second curing agent do not Cross-linking curing occurs; the second adhesive does not crosslink and cure with the first curing agent.
  • a curing accelerator may be further included in the adhesive layer 11, and the first adhesive is adjusted by adjusting the composition and the content ratio of the curing accelerator.
  • the first adhesive may be selected from a hydroxyl group-containing (meth) acrylate copolymer.
  • the hydroxyl group-containing (meth) acrylate copolymer may be selected from a solvent type hydroxy group-containing (meth) acrylate copolymer.
  • the monomer component of the hydroxyl group-containing (meth) acrylate copolymer may include a hydroxyl group-containing (meth) acrylate functional monomer.
  • the hydroxyl group-containing (meth) acrylate functional monomer may be selected from one or more selected from the group consisting of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, and hydroxypropyl methacrylate.
  • the monomer component of the hydroxyl group-containing (meth) acrylate copolymer may further include: a (meth)acrylic monomer.
  • the (meth)acrylic monomer may be selected from the group consisting of acrylic acid, methacrylic acid, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, and tert-butyl methacrylate.
  • the monomer component of the hydroxyl group-containing (meth) acrylate copolymer may further include a vinyl-based monomer.
  • the vinylic monomer may be selected from vinyl acetate.
  • the first curing agent may be selected from one or more of a polythiol, a polyisocyanate.
  • the polythiol may be selected from one or more of n-dodecyl mercaptan, secondary dodecyl mercaptan, t-dodecyl mercaptan, mercaptoethanol, thioglycolic acid.
  • the polyisocyanate may be selected from the group consisting of toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), benzene dimethylene diisocyanate ( XDI), one or more of methylcyclohexyl diisocyanate (HTDI), dicyclohexylmethane diisocyanate (HMDI), p-phenylene diisocyanate (PPDI), dimethylbiphenyl diisocyanate (TODI).
  • TDI toluene diisocyanate
  • MDI diphenylmethane diisocyanate
  • HDI hexamethylene diisocyanate
  • IPDI isophorone diisocyanate
  • XDI benzene dimethylene diisocyanate
  • HMDI dicyclohexylme
  • the second adhesive may be selected from an amine group-containing (meth) acrylate copolymer.
  • the amine group-containing (meth) acrylate copolymer may be selected from a solvent type amine group-containing (meth) acrylate copolymer.
  • the monomer component of the amine group-containing (meth) acrylate copolymer may include: an amine group-containing (meth) acrylate functional sheet body.
  • the amine group-containing (meth) acrylate functional monomer may be selected from dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, and tert-butyl methacrylate.
  • the monomer component of the amine group-containing (meth) acrylate copolymer may further include: a (meth)acrylic monomer.
  • the (meth)acrylic monomer may be selected from the group consisting of acrylic acid, methacrylic acid, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, and tert-butyl methacrylate.
  • the monomer component of the amine group-containing (meth) acrylate copolymer may further include a vinyl-based monomer.
  • the vinylic monomer may be selected from vinyl acetate.
  • the second curing agent may be selected from epoxy resins.
  • the specific kind of the epoxy resin is not limited.
  • the epoxy resin may be selected from one or more of E42, E44, E51, E54, Ex40, Ex48, F44, F48, F51, JF43, JF45.
  • the curing temperature of the first adhesive and the first curing agent when the curing temperature of the first adhesive and the first curing agent is less than 20 ° C, it is easy to cause curing at room temperature, resulting in an adhesive layer.
  • the slurry gel of 11 can not be coated on the substrate 12, so that the structural adhesive paper 1 is scrapped; when the curing temperature of the first adhesive and the first curing agent is greater than 80 ° C, the curing temperature is lower than the structural adhesive.
  • the adhesive layer 11 is incompletely cured during the curing process, and the residual glue appears on the current collector 2, and the residual glue cannot be peeled off, that is, the ear can not be reserved on the current collector 2. Vacancies for soldering the ears.
  • the curing temperature of the first adhesive and the first curing agent is from 40 ° C to 50 ° C.
  • the structural adhesive paper 1 when the curing temperature of the second adhesive and the second curing agent is less than 80 ° C, the structural adhesive paper 1 is liable to cause early loss of adhesion during use. Referring to Figures 3 and 4, the structural adhesive tape 1 is easily carried by the hot air, adhered to the wet film area (wet electrode paste 3), contaminating the finally formed film; when the second adhesive and the second curing agent are When the curing temperature is higher than 180 ° C, the surface adhesive sheet 3 is excessively dried during the use of the structural adhesive paper 1 , and a series of problems such as cracking of the film, streaking, and denaturation of the active material occur.
  • the curing temperature of the second adhesive and the second curing agent is from 105 ° C to 115 ° C.
  • the structural adhesive sheet 1 may have a total thickness of from 20 ⁇ m to 120 ⁇ m.
  • the structural adhesive paper 1 may have a total thickness of 40 ⁇ m to 70 ⁇ m.
  • the total thickness of the structural adhesive tape 1 means the sum of the thickness of the substrate 12 and the thickness of the adhesive layer 11.
  • the area of the structural adhesive sheet 1 may be from 1 mm 2 to 600 mm 2 .
  • the area of the structural adhesive tape 1 may be from 80 mm 2 to 480 mm 2 .
  • the substrate 12 may be selected from polyethylene terephthalate.
  • the particle size of the blowing agent particles 111 may be from 5 ⁇ m to 30 ⁇ m.
  • the foaming agent particles 111 may have a foaming temperature of from 105 ° C to 150 ° C.
  • the foaming agent particles 111 may have a foaming temperature of from 110 ° C to 140 ° C.
  • the foaming agent particles 111 may have a foaming temperature of from 120 ° C to 130 ° C.
  • the blowing agent particles 111 may be a physical foaming agent and/or a chemical foaming agent.
  • the physical foaming agent is an alkane long-chain series foaming agent.
  • the physical blowing agent may be selected from one or more of an isopentane blowing agent, an isobutane blowing agent, and a cyclopentane blowing agent.
  • the chemical blowing agent may be selected from the group consisting of azodicarbonamide (AC), azobisisobutyronitrile (AIBN), N,N-dinitrosopentamethylenetetramine (DPT), 4,4' One or more of oxobisbenzenesulfonylhydrazide (OBSH) and p-toluenesulfonylhydrazide (TSH).
  • AC azodicarbonamide
  • AIBN azobisisobutyronitrile
  • DPT N,N-dinitrosopentamethylenetetramine
  • OBSH oxobisbenzenesulfonylhydrazide
  • TSH p-toluenesulfonylhydrazide
  • a method for preparing the structural adhesive paper 1 according to the second aspect of the present invention for preparing the structural adhesive paper 1 according to the first aspect of the present invention includes the steps of: first adhesive, first curing agent, and The second adhesive and the second curing agent are dissolved in the solvent, and after being uniformly stirred, the foaming agent particles 111 are added to form a slurry; the slurry is coated on one surface of the substrate 12, and then dried in an oven. To remove the solvent; the structural adhesive paper 1 was taken out from the oven and then matured to complete the preparation of the structural adhesive paper 1.
  • a curing accelerator may be added during the preparation of the slurry, and the first adhesive is adjusted by adjusting the composition and the content ratio of the curing accelerator.
  • the curing temperature of the adhesive and the first curing agent and the curing temperature of the second adhesive and the second curing agent may be adjusted by adjusting the composition and the content ratio of the curing accelerator.
  • the oven temperature may be set to be not lower than the curing temperature of the first adhesive and the first curing agent, and lower than the second adhesive.
  • the curing temperature with the second curing agent may be set to be not lower than the curing temperature of the first adhesive and the first curing agent, and lower than the second adhesive.
  • the oven temperature can be set to 70 ° C to 80 ° C.
  • the baking time may be from 1 min to 2 min.
  • the curing temperature is not excessively high, otherwise the outer wall of the blowing agent particles 111 is easily hardened, so that the foaming force is reduced.
  • the curing temperature may be from 20 ° C to 60 ° C.
  • the curing temperature may be from 40 ° C to 60 ° C.
  • the aging temperature is from 40 ° C to 45 ° C.
  • the aging time may be 60 h or more.
  • a method of preserving a pole vacancy in an electrode sheet according to a third aspect of the present invention includes the steps of: pasting a reserved area 21 on a current collector 2 of an electrode sheet according to the first aspect of the present invention
  • the adhesive tape 1 is adhered to the current collector 2 of the adhesive tape 1 of the structural adhesive paper 1, and the electrode paste 3 is coated on the surface of the substrate 12 of the structural adhesive paper 1 to obtain a wet film;
  • the structural adhesive paper 1 After being sent to the low temperature zone of the oven for baking, the structural adhesive paper 1 remains bonded to the current collector 2, wherein the baking temperature in the low temperature zone is lower than the initial foaming temperature of the foaming agent particles 111; the wet film is continuously fed into the oven
  • the high temperature zone is baked to foam the foaming agent particles 111 in the structural adhesive paper 1, the structural adhesive paper 1 is curled, and the bonding force between the structural adhesive paper 1 and the current collector 2 is not more than 4 N/cm 2 Wherein, the baking temperature in the high temperature zone is greater than or equal
  • the oven temperature should be set to a low temperature zone and a high temperature zone, and the baking temperature of the low temperature zone is used for preheating drying of the electrode paste 3, The fluidity of the electrode paste 3 is reduced, and the baking temperature of the high temperature region is used to cure the second adhesive and the second curing agent, and to foam the blowing agent particles 111.
  • the baking temperature in the low temperature region is too low, which easily causes the electrode paste 3 to be effectively dried during the baking process, resulting in poor drying;
  • the baking temperature in the low temperature zone is too high, and the foaming agent particles 111 are easily foamed in advance, and the structural adhesive tape 1 is prone to early premature sticking during use.
  • the structural adhesive tape 1 is easily taken up by the hot air. , adhered to the wet film area (wet electrode paste 3), contaminating the electrode film that is finally formed.
  • the baking temperature in the low temperature region may be 40 ° C to 105 ° C.
  • the baking temperature in the low temperature zone may be from 80 ° C to 100 ° C.
  • the baking temperature in the high temperature region is too low, and the foaming agent particles 111 cannot be effectively foamed, resulting in poor foaming of the structural adhesive paper 1.
  • the structural adhesive paper 1 cannot be peeled off from the current collector 2, and thus the pole vacancies cannot be reserved on the current collector 2; the baking temperature in the high temperature region is too high, which easily leads to structural adhesive
  • the electrode paste 3 on the surface of the paper 1 is excessively dried, and a series of problems such as cracking of the film, streaking, and denaturation of the active material occur.
  • the baking temperature in the high temperature region may be from 105 ° C to 180 ° C.
  • the baking temperature in the high temperature zone may be from 125 ° C to 145 ° C.
  • the baking temperature in the high temperature region may be from 130 ° C to 135 ° C.
  • the baking time in the low temperature region may be 30 s to 300 s.
  • the baking time in the low temperature zone may be 30 s to 60 s.
  • the baking time in the high temperature region may be 30 s to 300 s.
  • the baking time in the high temperature zone may be from 30 s to 120 s.
  • the adhesion between the structural adhesive tape 1 and the current collector 2 after the end of the low temperature region is not more than 50 N/cm 2 , After the end of the baking in the low temperature zone, the structural adhesive paper 1 remains bonded to the current collector 2.
  • the bonding force between the structural adhesive tape 1 and the current collector 2 after the end of the low temperature region baking may be 1 N/ Cm 2 to 23 N/cm 2 .
  • the coating thickness of the electrode paste 3 is thick.
  • the degree may be from 40 ⁇ m to 300 ⁇ m.
  • the electrode paste 3 may have a coating thickness of 60 ⁇ m to 180 ⁇ m.
  • the first adhesive (2-ethylhexyl acrylate + vinyl acetate + hydroxyethyl acrylate copolymer), the first curing agent (toluene diisocyanate, TDI), the second adhesive (acrylic acid - 2-ethylhexyl ester + vinyl acetate + dimethylaminoethyl methacrylate copolymer), second curing agent (epoxy resin E51) and curing accelerator dissolved in solvent toluene and ethyl acetate 1:1 (V / The mixture of V) was stirred at a number of revolutions of 40 rpm to 60 rpm for 30 minutes; then, foaming agent particles AC (foaming temperature of 115 ° C to 125 ° C) were added, and stirring was continued for 30 minutes at a number of revolutions of 40 rpm to 60 rpm to obtain a slurry.
  • V The mixture of V
  • the slurry was coated on a substrate PET (thickness: 15 ⁇ m) using a conventional doctor blade to form a roll I (total thickness of 60 ⁇ m), and then the solvent was removed by baking in an oven, and the running speed of the roll I was 15 m/min.
  • the structural adhesive tape is matured and cut and shipped.
  • the curing temperature of the first adhesive and the first curing agent, the curing temperature of the second adhesive and the second curing agent, the baking process parameters, and the curing process parameters are shown in Table 1.
  • the film is sent to the low temperature zone of the oven for baking; then the wet film is sent to the high temperature zone of the oven for baking, so that the structural adhesive tape is foamed and curled; after the baking is finished, the structural adhesive tape is peeled off, and the film can be reserved in the positive electrode sheet.
  • the ear is empty. Among them, the low temperature zone baking temperature and time, the high temperature zone baking temperature and time are shown in Table 2.
  • the curing temperature of the first adhesive and the first curing agent is too low, resulting in opening at room temperature.
  • the curing begins, causing the slurry gel of the adhesive layer to be coated on the substrate, and the structural adhesive paper is scrapped.
  • the curing temperature of the second adhesive and the second curing agent was 70 ° C, and the curing temperature was low.
  • the second adhesive was cured by crosslinking with the epoxy resin E51. Too fast, the cohesive force inside the adhesive layer rises rapidly, so that the adhesiveness of the adhesive layer of the structural adhesive paper drops too fast, resulting in early loss of adhesion of the structural adhesive tape and contamination of the film.
  • the curing temperature of the first adhesive and the first curing agent is 80 ° C, which is greater than the curing temperature of the structural adhesive paper, resulting in incomplete curing of the first adhesive and the first curing agent.
  • the surface of the current collector is pasted, residual glue appears, which causes the structural adhesive paper to be scrapped.
  • the baking temperature in the high temperature region is lower than the curing temperature of the second adhesive and the epoxy resin E51, and the second adhesive and the epoxy resin E51 cannot be cured in the high temperature region.
  • the structural adhesive tape and the current collector still maintain a strong bond, which causes the structural adhesive tape to be peeled off, and thus the pole vacancies cannot be reserved on the current collector.
  • the baking temperature in the high temperature zone is lower than the initial foaming temperature of the foaming agent particles, and the foaming agent particles cannot be effectively foamed, resulting in poor foaming of the structural adhesive paper, so that after the current collector is removed from the oven, the structure The adhesive tape cannot be peeled off from the current collector, and it is impossible to reserve a tab space on the current collector.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)

Abstract

本发明提供一种结构胶纸及其制备方法、在电极片预留极耳空位的方法。所述结构胶纸包括：胶黏剂层，用于粘贴在被粘贴对象上；以及基材，位于结构胶纸的远离被粘贴对象的一侧。胶黏剂层包括分布在其内的第一胶黏剂、第一固化剂、第二胶黏剂、第二固化剂以及发泡剂颗粒。第一胶黏剂与第一固化剂的固化温度为20℃～80℃；第二胶黏剂与第二固化剂的固化温度大于80℃且小于等于180℃。本发明的结构胶纸与被粘贴对象的粘性一致性极高，易于进行批量化生产，解决了常规胶纸中发泡剂颗粒发泡后粘性波动严重的问题。本发明的结构胶纸能提升电池活性物质的利用率、避免活性物质的浪费，同时提升电池的能量密度、快冲快放性能以及散热性能。

Description

结构胶纸及其制备方法、在电极片预留极耳空位的方法 技术领域
本发明涉及胶纸领域，尤其涉及一种结构胶纸及其制备方法、在电极片预留极耳空位的方法。
背景技术
现有技术的胶纸一般采用PET基材和丙烯酸酯系压敏型胶黏剂加发泡剂颗粒实现发泡从而与集流体产生剥离，以在集流体上预留出极耳空位。参照图7A和图7B，当胶黏剂层2＇的残余溶剂量过大时(>10％)，发泡剂颗粒21＇被完全包覆在胶黏剂层2＇中的胶黏剂中，即使发泡剂颗粒21＇发泡后膨胀，也无法有效减小胶黏剂与集流体的接触面积，导致胶纸难以剥离，无法在集流体上预留出极耳空位。参照图8A和图8B，当胶黏剂层2＇的残余溶剂量相对合适时(5％～10％)，部分发泡剂颗粒21＇挨着胶黏剂与集流体之间的界面，发泡剂颗粒21＇发泡后可以有效减小胶黏剂与集流体的接触面积，胶纸可以正常剥离，但是该工艺要求苛刻，合格率较低，无法满足批量化生产的需求。参照图9A和图9B，当胶黏剂层2＇的残余溶剂量过低时(<5％)，大多数发泡剂颗粒21＇已经裸露在胶黏剂之外，发泡剂颗粒21＇发泡后，胶黏剂几乎与集流体失去粘结，导致胶纸失粘，污染膜片。
由于通常发泡剂颗粒本身粒径分布较宽(5μm～30μm)，混合在胶黏剂中进行涂布烘干，容易出现两种失效模式。第一种，胶黏剂层过厚，发泡剂颗粒发泡膨胀不能有效减小胶黏剂与集流体的接触面积，导致发泡后粘性过大，无法从集流体的空箔区剥离，造成断带。第二种，胶黏剂层过薄，发泡剂颗粒裸露在胶黏剂外，阻碍了胶黏剂与集流体的空箔区的接触，造成发泡后粘性过弱，由于发泡剂颗粒发泡时电极浆料未完全干燥，因此发泡剂颗粒粘性偏弱时，胶纸容易被热风带起，粘在湿膜区，湿膜干燥后，发泡剂颗粒嵌入力度增大，无法正常剥离，也会造成断带。
另外，由于胶黏剂层的厚度通常要求范围较小，常规的涂布工艺精度无法满足要求，厚度波动导致大量产品报废。
发明内容
鉴于背景技术中存在的问题，本发明的一目的在于提供一种结构胶纸及其制备方法、在电极片预留极耳空位的方法，所述结构胶纸与被粘贴对象的粘性一致性极高，易于进行 批量化生产，解决了常规胶纸中发泡剂颗粒发泡后粘性波动严重的问题。
本发明的又一目的在于提供一种结构胶纸及其制备方法、在电极片预留极耳空位的方法，所述结构胶纸能提升电池活性物质的利用率、避免活性物质的浪费，同时提升电池的能量密度、快冲快放性能以及散热性能。
为了达到上述目的，在本发明的一方面，本发明提供了一种结构胶纸，其包括：胶黏剂层，用于粘贴在被粘贴对象上；以及基材，位于结构胶纸的远离被粘贴对象的一侧。胶黏剂层包括分布在其内的第一胶黏剂、第一固化剂、第二胶黏剂、第二固化剂以及发泡剂颗粒。第一胶黏剂与第一固化剂的固化温度为20℃～80℃；第二胶黏剂与第二固化剂的固化温度大于80℃且小于等于180℃。
在本发明的另一方面，本发明提供了一种结构胶纸的制备方法，用于制备本发明一方面所述的结构胶纸，包括步骤：将第一胶黏剂、第一固化剂、第二胶黏剂、第二固化剂溶于溶剂中，搅拌均匀后加入发泡剂颗粒制成浆料；将浆料涂布在基材的其中一个表面上，之后置于烘箱中烘干以除去溶剂；将结构胶纸从烘箱取出后进行熟化，完成结构胶纸的制备。
在本发明的又一方面，本发明提供了一种在电极片预留极耳空位的方法，其包括步骤：在电极片的集流体上的预留区域粘贴根据本发明一方面所述的结构胶纸，使结构胶纸的胶黏剂层粘贴在集流体上，将电极浆料涂布在结构胶纸的基材的表面上，得到湿膜；将湿膜送入烘箱的低温区烘烤，结构胶纸仍保持与集流体粘结，其中，低温区的烘烤温度小于发泡剂颗粒的起始发泡温度；继续将湿膜送入烘箱的高温区烘烤，使结构胶纸中的发泡剂颗粒发泡，结构胶纸产生卷曲，且使结构胶纸与集流体之间的粘结力不大于4N/cm2，其中，高温区的烘烤温度大于等于发泡剂颗粒的起始发泡温度；烘烤结束后将结构胶纸剥离，即可在电极片预留极耳空位。
相对于现有技术，本发明的有益效果为：
本发明的结构胶纸与被粘贴对象的粘性一致性极高，易于进行批量化生产，解决了常规胶纸中发泡剂颗粒发泡后粘性波动严重的问题。
本发明的结构胶纸能提升电池活性物质的利用率、避免活性物质的浪费，同时提升电池的能量密度、快冲快放性能以及散热性能。
附图说明
图1为根据本发明的结构胶纸所应用的被粘结对象集流体的立体图；
图2为根据本发明的结构胶纸粘贴于被粘结对象集流体的立体图；
图3为根据本发明的结构胶纸涂布电极浆料的立体图；
图4为根据本发明的结构胶纸剥离后的立体图；
图5为根据本发明的结构胶纸的一立体图；
图6为图5的一前视图；
图7A至图7B分别为现有技术的胶纸的一实施例的一示意图，其中，图7A示出发泡剂颗粒发泡前的示意图，图7B示出发泡剂颗粒发泡后的示意图；
图8A至图8B分别为现有技术的胶纸的另一实施例的一示意图，其中，图8A示出发泡剂颗粒发泡前的示意图，图8B示出发泡剂颗粒发泡后的示意图；
图9A至图9B分别为现有技术的胶纸的又一实施例的一示意图，其中，图9A示出发泡剂颗粒发泡前的示意图，图9B示出发泡剂颗粒发泡后的示意图。
其中，附图标记说明如下：
1结构胶纸
11胶黏剂层
111发泡剂颗粒
12基材
2集流体
21预留区域
3电极浆料
W宽度方向
L长度方向
T厚度方向
1＇基材
2＇胶黏剂层
21＇发泡剂颗粒
具体实施方式
下面详细说明根据本发明的结构胶纸及其制备方法、在电极片预留极耳空位的方法。
首先说明根据本发明第一方面的结构胶纸。
参照图3、图5至图6，根据本发明第一方面的结构胶纸1包括：胶黏剂层11，用于粘贴在被粘贴对象上；以及基材12，位于结构胶纸1的远离被粘贴对象的一侧。胶黏剂层11包括分布在其内的第一胶黏剂、第一固化剂、第二胶黏剂、第二固化剂以及发泡剂颗粒111。第一胶黏剂与第一固化剂的固化温度为20℃～80℃；第二胶黏剂与第二固化剂的固化温度大于80℃且小于等于180℃。
在根据本发明第一方面所述的结构胶纸1中，优选地，第一胶黏剂与第二固化剂不会 发生交联固化；第二胶黏剂与第一固化剂不会发生交联固化。
在根据本发明第一方面所述的结构胶纸1中，胶黏剂层11内还可包括固化促进剂，通过调节固化促进剂的组成以及含量配比，以调节第一胶黏剂与第一固化剂的固化温度以及第二胶黏剂与第二固化剂的固化温度。
在根据本发明第一方面所述的结构胶纸1中，第一胶黏剂可选自含有羟基的(甲基)丙烯酸酯共聚物。优选地，所述含有羟基的(甲基)丙烯酸酯共聚物可选自溶剂型含有羟基的(甲基)丙烯酸酯共聚物。
在根据本发明第一方面所述的结构胶纸1中，所述含有羟基的(甲基)丙烯酸酯共聚物的单体组分可包括：含有羟基的(甲基)丙烯酸酯功能单体。所述含有羟基的(甲基)丙烯酸酯功能单体可选自丙烯酸羟乙酯、丙烯酸羟丙酯、甲基丙烯酸羟乙酯、甲基丙烯酸羟丙酯中的一种或几种。
在根据本发明第一方面所述的结构胶纸1中，所述含有羟基的(甲基)丙烯酸酯共聚物的单体组分还可包括：(甲基)丙烯酸类单体。所述(甲基)丙烯酸类单体可选自丙烯酸、甲基丙烯酸、甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸正丁酯、甲基丙烯酸异丁酯、甲基丙烯酸叔丁酯、甲基丙烯酸己酯、甲基丙烯酸-2-乙基己酯、甲基丙烯酸异冰片酯、甲基丙烯酸月桂酯、丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丙酯、丙烯酸异丙酯、丙烯酸正丁酯、丙烯酸异丁酯、丙烯酸仲丁酯、丙烯酸叔丁酯、丙烯酸环己酯、2-乙基丙烯酸乙酯、丙烯酸-2-乙基己酯中的一种或几种。
在根据本发明第一方面所述的结构胶纸1中，所述含有羟基的(甲基)丙烯酸酯共聚物的单体组分还可包括：乙烯基类单体。所述乙烯基类单体可选自乙酸乙烯。
在根据本发明第一方面所述的结构胶纸1中，第一固化剂可选自聚硫醇、多异氰酸酯中的一种或几种。其中，聚硫醇可选自正十二烷基硫醇、仲十二烷基硫醇、叔十二烷基硫醇、巯基乙醇、巯基乙酸中的一种或几种。多异氰酸酯可选自甲苯二异氰酸酯(TDI)、二苯基甲烷二异氰酸酯(MDI)、六亚甲基二异氰酸酯(HDI)、异佛尔酮二异氰酸酯(IPDI)、苯二亚甲基二异氰酸酯(XDI)、甲基环己基二异氰酸酯(HTDI)、二环己基甲烷二异氰酸酯(HMDI)、对苯二异氰酸酯(PPDI)、二甲基联苯二异氰酸酯(TODI)中的一种或几种。
在根据本发明第一方面所述的结构胶纸1中，第二胶黏剂可选自含有胺基的(甲基)丙烯酸酯共聚物。优选地，所述含有胺基的(甲基)丙烯酸酯共聚物可选自溶剂型含有胺基的(甲基)丙烯酸酯共聚物。
在根据本发明第一方面所述的结构胶纸1中，所述含有胺基的(甲基)丙烯酸酯共聚物的单体组分可包括：含有胺基的(甲基)丙烯酸酯功能单体。所述含有胺基的(甲基)丙烯酸酯功能单体可选自丙烯酸二甲胺基乙酯、甲基丙烯酸二甲胺乙酯、甲基丙烯酸叔丁 基氨基乙酯、甲基丙烯酸二乙氨基乙酯、丙烯酸N,N-二乙基氨基乙酯中的一种或几种。
在根据本发明第一方面所述的结构胶纸1中，所述含有胺基的(甲基)丙烯酸酯共聚物的单体组分还可包括：(甲基)丙烯酸类单体。所述(甲基)丙烯酸类单体可选自丙烯酸、甲基丙烯酸、甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸正丁酯、甲基丙烯酸异丁酯、甲基丙烯酸叔丁酯、甲基丙烯酸己酯、甲基丙烯酸-2-乙基己酯、甲基丙烯酸异冰片酯、甲基丙烯酸月桂酯、丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丙酯、丙烯酸异丙酯、丙烯酸正丁酯、丙烯酸异丁酯、丙烯酸仲丁酯、丙烯酸叔丁酯、丙烯酸环己酯、2-乙基丙烯酸乙酯、丙烯酸-2-乙基己酯中的一种或几种。
在根据本发明第一方面所述的结构胶纸1中，所述含有胺基的(甲基)丙烯酸酯共聚物的单体组分还可包括：乙烯基类单体。所述乙烯基类单体可选自乙酸乙烯。
在根据本发明第一方面所述的结构胶纸1中，所述第二固化剂可选自环氧树脂。所述环氧树脂的具体种类不受限制。优选地，所述环氧树脂可选自E42、E44、E51、E54、Ex40、Ex48、F44、F48、F51、JF43、JF45中的一种或几种。
在根据本发明第一方面所述的结构胶纸1中，当第一胶黏剂与第一固化剂的固化温度小于20℃时，容易导致室温配胶时就开始固化，造成胶黏剂层11的浆料凝胶，无法涂布在基材12上，使结构胶纸1报废；当第一胶黏剂与第一固化剂的固化温度大于80℃时，容易使得固化温度低于结构胶纸1的熟化温度，胶黏剂层11在熟化过程中出现固化不完全，粘贴在集流体2上时出现残胶，该部分残胶无法剥离，即无法在集流体2上预留出极耳空位以供焊接极耳。
在根据本发明第一方面所述的结构胶纸1中，优选地，第一胶黏剂与第一固化剂的固化温度为40℃～50℃。
在根据本发明第一方面所述的结构胶纸1中，当第二胶黏剂与第二固化剂的固化温度小于80℃时，容易导致结构胶纸1在使用过程中出现提早失粘，参照图3和图4，结构胶纸1容易被热风带起，粘在湿膜区(湿的电极浆料3)，污染最终形成的膜片；当第二胶黏剂与第二固化剂的固化温度大于180℃时，容易导致结构胶纸1在使用过程中，表面的电极浆料3被过度干燥，出现膜片开裂、条纹以及活性材料变性等一系列问题。
在根据本发明第一方面所述的结构胶纸1中，优选地，第二胶黏剂与第二固化剂的固化温度为105℃～115℃。
在根据本发明第一方面所述的结构胶纸1中，结构胶纸1的总厚度可为20μm～120μm。优选地，结构胶纸1的总厚度可为40μm～70μm。结构胶纸1的总厚度是指基材12的厚度与胶黏剂层11的厚度之和。
在根据本发明第一方面所述的结构胶纸1中，结构胶纸1的面积可为1mm2～600mm2。优选地，结构胶纸1的面积可为80mm2～480mm2。
在根据本发明第一方面所述的结构胶纸1中，基材12可选自聚对苯二甲酸乙二醇酯。
在根据本发明第一方面所述的结构胶纸1中，发泡剂颗粒111的粒径可为5μm～30μm。
在根据本发明第一方面所述的结构胶纸1中，发泡剂颗粒111的发泡温度可为105℃～150℃。优选地，发泡剂颗粒111的发泡温度可为110℃～140℃。进一步优选地，发泡剂颗粒111的发泡温度可为120℃～130℃。
在根据本发明第一方面所述的结构胶纸1中，发泡剂颗粒111可为物理发泡剂和/或化学发泡剂。其中，所述物理发泡剂为烷烃类长链系列发泡剂。优选地，所述物理发泡剂可选自异戊烷发泡剂、异丁烷发泡剂、环戊烷发泡剂中的一种或几种。所述化学发泡剂可选自偶氮二甲酰胺(AC)、偶氮二异丁腈(AIBN)、N,N-二亚硝基五次甲基四胺(DPT)、4,4'-氧代双苯磺酰肼(OBSH)、对甲苯磺酰肼(TSH)中的一种或几种。
其次说明根据本发明第二方面的结构胶纸1的制备方法，其用于制备本发明第一方面所述的结构胶纸1，包括步骤：将第一胶黏剂、第一固化剂、第二胶黏剂、第二固化剂溶于溶剂中，搅拌均匀后加入发泡剂颗粒111制成浆料；将浆料涂布在基材12的其中一个表面上，之后置于烘箱中烘干以除去溶剂；将结构胶纸1从烘箱取出后进行熟化，完成结构胶纸1的制备。
在根据本发明第二方面所述的结构胶纸1的制备方法中，在制备浆料的过程中还可加入固化促进剂，通过调节固化促进剂的组成以及含量配比，以调节第一胶黏剂与第一固化剂的固化温度以及第二胶黏剂与第二固化剂的固化温度。
在根据本发明第二方面所述的结构胶纸1的制备方法中，烘箱温度可设定为不低于第一胶黏剂与第一固化剂的固化温度，且低于第二胶黏剂与第二固化剂的固化温度。
在根据本发明第二方面所述的结构胶纸1的制备方法中，烘箱温度可设定为70℃～80℃。
在根据本发明第二方面所述的结构胶纸1的制备方法中，烘烤时间可为1min～2min。
在根据本发明第二方面所述的结构胶纸1的制备方法中，熟化温度不能过高，否则容易造成发泡剂颗粒111的外壁硬化，使得发泡力减小。具体地，熟化温度可为20℃～60℃。优选地，熟化温度可为40℃～60℃。进一步优选地，熟化温度为40℃～45℃。
在根据本发明第二方面所述的结构胶纸1的制备方法中，熟化时间可大于等于60h。
再次说明根据本发明第三方面的在电极片预留极耳空位的方法。
参照图1至图6，根据本发明第三方面的在电极片预留极耳空位的方法包括步骤：在电极片的集流体2上的预留区域21粘贴根据本发明第一方面所述的结构胶纸1，使结构胶纸1的胶黏剂层11粘贴在集流体2上，将电极浆料3涂布在结构胶纸1的基材12的表 面上，得到湿膜；将湿膜送入烘箱的低温区烘烤，结构胶纸1仍保持与集流体2粘结，其中，低温区的烘烤温度小于发泡剂颗粒111的起始发泡温度；继续将湿膜送入烘箱的高温区烘烤，使结构胶纸1中的发泡剂颗粒111发泡，结构胶纸1产生卷曲，且使结构胶纸1与集流体2之间的粘结力不大于4N/cm2，其中，高温区的烘烤温度大于等于发泡剂颗粒111的起始发泡温度；烘烤结束后将结构胶纸1剥离，即可在电极片预留极耳空位。
在根据本发明第三方面所述的在电极片预留极耳空位的方法中，烘箱温度应设定低温区与高温区，低温区的烘烤温度用于电极浆料3的预热干燥，减小电极浆料3的流动性，高温区的烘烤温度用于使第二胶黏剂和第二固化剂固化、以及使发泡剂颗粒111发泡。
在根据本发明第三方面所述的在电极片预留极耳空位的方法中，低温区的烘烤温度太低，容易导致电极浆料3在烘烤过程中无法有效干燥，出现干燥不良；低温区的烘烤温度太高，容易使得发泡剂颗粒111提前发泡，结构胶纸1在使用过程中容易出现提早失粘，参照图3和图4，结构胶纸1容易被热风带起，粘在湿膜区(湿的电极浆料3)，污染最终形成的电极膜片。
在根据本发明第三方面所述的在电极片预留极耳空位的方法中，具体地，低温区的烘烤温度可为40℃～105℃。优选地，低温区的烘烤温度可为80℃～100℃。
在根据本发明第三方面所述的在电极片预留极耳空位的方法中，高温区的烘烤温度太低，发泡剂颗粒111无法有效发泡，导致结构胶纸1出现发泡不良，使得将集流体2从烘箱移出后，结构胶纸1无法从集流体2上剥离，进而无法在集流体2上预留出极耳空位；高温区的烘烤温度太高，容易导致结构胶纸1表面的电极浆料3被过度干燥，出现膜片开裂、条纹以及活性材料变性等一系列问题。
在根据本发明第三方面所述的在电极片预留极耳空位的方法中，具体地，高温区的烘烤温度可为105℃～180℃。优选地，高温区的烘烤温度可为125℃～145℃。进一步优选地，高温区的烘烤温度可为130℃～135℃。
在根据本发明第三方面所述的在电极片预留极耳空位的方法中，低温区的烘烤时间可为30s～300s。优选地，低温区的烘烤时间可为30s～60s。
在根据本发明第三方面所述的在电极片预留极耳空位的方法中，高温区的烘烤时间可为30s～300s。优选地，高温区的烘烤时间可为30s～120s。
在根据本发明第三方面所述的在电极片预留极耳空位的方法中，低温区烘烤结束后使结构胶纸1与集流体2之间的粘结力可不大于50N/cm2，以保证低温区烘烤结束后，结构胶纸1仍保持与集流体2粘结。
在根据本发明第三方面所述的在电极片预留极耳空位的方法中，优选地，低温区烘烤结束后使结构胶纸1与集流体2之间的粘结力可为1N/cm2～23N/cm2。
在根据本发明第三方面所述的在电极片预留极耳空位的方法中，电极浆料3的涂覆厚 度可为40μm～300μm。优选地，电极浆料3的涂覆厚度可为60μm～180μm。
下面结合实施例，进一步阐述本申请。应理解，这些实施例仅用于说明本申请而不用于限制本申请的范围。
实施例1-5与对比例1-20的结构胶纸制备如下：
室温下，将第一胶黏剂(丙烯酸-2-乙基己酯+乙酸乙烯+丙烯酸羟乙酯共聚物)、第一固化剂(甲苯二异氰酸酯，TDI)、第二胶黏剂(丙烯酸-2-乙基己酯+乙酸乙烯+甲基丙烯酸二甲胺乙酯共聚物)、第二固化剂(环氧树脂E51)以及固化促进剂溶于溶剂甲苯和乙酸乙酯1:1(V/V)的混合物中，在转速为40rpm～60rpm下搅拌30min；之后加入发泡剂颗粒AC(发泡温度为115℃～125℃)，在转速为40rpm～60rpm下继续搅拌30min，得到浆料。
将浆料采用普通刮刀涂布在基材PET(厚度为15μm)上，生成料卷I(总厚度为60μm)，之后在烘箱烘烤除去溶剂，料卷I的走速为15m/min。
将结构胶纸熟化、分切出货。
其中，第一胶黏剂与第一固化剂的固化温度、第二胶黏剂与第二固化剂的固化温度、烘烤工艺参数、熟化工艺参数示出在表1中。
表1实施例1-5和对比例1-20的结构胶纸的制备参数
Figure PCTCN2016104319-appb-000001
Figure PCTCN2016104319-appb-000002
Figure PCTCN2016104319-appb-000003
接下来将实施例1-5与对比例1-20的结构胶纸粘贴在集流体铝箔上的预留区域，使结构胶纸的胶黏剂层粘贴在集流体上，使用重量为2Kg的压辊来回辊压6次，之后撕去结构胶纸，观察集流体的表面是否有残胶出现。如无残胶出现，则重新取一份结构胶纸并粘贴在集流体铝箔上的预留区域，将正极浆料涂布在结构胶纸的基材PET的表面上，得到湿膜；将湿膜送入烘箱的低温区烘烤；之后将湿膜送入烘箱的高温区烘烤，使结构胶纸发泡，产生卷曲；烘烤结束后将结构胶纸剥离，即可在正极片预留极耳空位。其中，低温区烘烤温度以及时间、高温区烘烤温度以及时间示出在表2中。
表2实施例1-5和对比例1-20的结构胶纸的烘烤参数及测试结果
Figure PCTCN2016104319-appb-000004
Figure PCTCN2016104319-appb-000005
从表2中可以看出，在实施例1-5中，当结构胶纸在低温区进行烘烤时，结构胶纸仍保持与集流体粘结，此时发泡剂颗粒尚未发泡；当结构胶纸在高温区进行烘烤时，发泡剂颗粒发泡使结构胶纸卷曲，同时第二胶黏剂与环氧树脂E51快速交联固化，胶黏剂层内部的内聚力迅速上升，胶黏剂层的粘性急速下降，很容易将结构胶纸从集流体剥离(例如通过机械毛刷)，且不会产生残胶。
在对比例1-5中，第一胶黏剂与第一固化剂的固化温度过低，导致在室温配胶时就开 始固化，造成胶黏剂层的浆料凝胶，无法涂布在基材上，使结构胶纸报废。
在对比例6-7中，第二胶黏剂与第二固化剂的固化温度为70℃，固化温度较低，在高温区烘烤时，第二胶黏剂与环氧树脂E51交联固化过快，胶黏剂层内部的内聚力迅速上升，使得结构胶纸的胶黏剂层的粘性下降过快，导致结构胶纸提早失粘，污染膜片。
在对比例9-12、19中，第一胶黏剂与第一固化剂的固化温度为80℃，大于结构胶纸的熟化温度，导致第一胶黏剂与第一固化剂固化不完全，粘贴在集流体的表面时出现残胶，使结构胶纸报废。
在对比例13-15中，高温区的烘烤温度低于第二胶黏剂与环氧树脂E51的固化温度，第二胶黏剂与环氧树脂E51在高温区烘烤时无法进行固化，结构胶纸与集流体仍保持较强的粘结，导致结构胶纸无法剥离，进而无法在集流体上预留出极耳空位。此外，高温区的烘烤温度还低于发泡剂颗粒的起始发泡温度，发泡剂颗粒无法有效发泡，导致结构胶纸出现发泡不良，使得将集流体从烘箱移出后，结构胶纸无法从集流体上剥离，进而无法在集流体上预留出极耳空位。
同样，在对比例8、16-17中，尽管高温区的烘烤温度高于第二胶黏剂与环氧树脂E51的固化温度，第二胶黏剂与环氧树脂E51能够正常固化，但是由于高温区的烘烤温度仍低于发泡剂颗粒的起始发泡温度，发泡剂颗粒无法有效发泡，导致结构胶纸出现发泡不良，使得将集流体从烘箱移出后，结构胶纸无法从集流体上剥离，进而无法在集流体上预留出极耳空位。
在对比例14、18、20中，由于低温区的烘烤温度太低，导致正极浆料在烘烤过程中无法有效干燥，出现干燥不良。

Claims (39)

  1. 一种结构胶纸(1)，包括：
    胶黏剂层(11)，用于粘贴在被粘贴对象上；以及
    基材(12)，位于结构胶纸(1)的远离被粘贴对象的一侧；
    其特征在于，
    胶黏剂层(11)包括分布在其内的第一胶黏剂、第一固化剂、第二胶黏剂、第二固化剂以及发泡剂颗粒(111)；
    第一胶黏剂与第一固化剂的固化温度为20℃～80℃；
    第二胶黏剂与第二固化剂的固化温度大于80℃且小于等于180℃。
  2. 根据权利要求1所述的结构胶纸(1)，其特征在于，第一胶黏剂选自含有羟基的(甲基)丙烯酸酯共聚物，所述含有羟基的(甲基)丙烯酸酯共聚物的单体组分包括：含有羟基的(甲基)丙烯酸酯功能单体。
  3. 根据权利要求2所述的结构胶纸(1)，其特征在于，所述含有羟基的(甲基)丙烯酸酯共聚物选自溶剂型含有羟基的(甲基)丙烯酸酯共聚物。
  4. 根据权利要求2所述的结构胶纸(1)，其特征在于，所述含有羟基的(甲基)丙烯酸酯功能单体选自丙烯酸羟乙酯、丙烯酸羟丙酯、甲基丙烯酸羟乙酯、甲基丙烯酸羟丙酯中的一种或几种。
  5. 根据权利要求2所述的结构胶纸(1)，其特征在于，所述含有羟基的(甲基)丙烯酸酯共聚物的单体组分还包括：(甲基)丙烯酸类单体。
  6. 根据权利要求5所述的结构胶纸(1)，其特征在于，所述(甲基)丙烯酸类单体选自丙烯酸、甲基丙烯酸、甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸正丁酯、甲基丙烯酸异丁酯、甲基丙烯酸叔丁酯、甲基丙烯酸己酯、甲基丙烯酸-2-乙基己酯、甲基丙烯酸异冰片酯、甲基丙烯酸月桂酯、丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丙酯、丙烯酸异丙酯、丙烯酸正丁酯、丙烯酸异丁酯、丙烯酸仲丁酯、丙烯酸叔丁酯、丙烯酸环己酯、2-乙基丙烯酸乙酯、丙烯酸-2-乙基己酯中的一种或几种。
  7. 根据权利要求5所述的结构胶纸(1)，其特征在于，所述含有羟基的(甲基)丙 烯酸酯共聚物的单体组分还包括：乙烯基类单体。
  8. 根据权利要求7所述的结构胶纸(1)，其特征在于，所述乙烯基类单体选自乙酸乙烯。
  9. 根据权利要求1所述的结构胶纸(1)，其特征在于，第一固化剂选自聚硫醇、多异氰酸酯中的一种或几种。
  10. 根据权利要求9所述的结构胶纸(1)，其特征在于，
    聚硫醇选自正十二烷基硫醇、仲十二烷基硫醇、叔十二烷基硫醇、巯基乙醇、巯基乙酸中的一种或几种；
    多异氰酸酯选自甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯、苯二亚甲基二异氰酸酯、甲基环己基二异氰酸酯、二环己基甲烷二异氰酸酯、对苯二异氰酸酯、二甲基联苯二异氰酸酯中的一种或几种。
  11. 根据权利要求1所述的结构胶纸(1)，其特征在于，第二胶黏剂选自含有胺基的(甲基)丙烯酸酯共聚物，所述含有胺基的(甲基)丙烯酸酯共聚物的单体组分包括：含有胺基的(甲基)丙烯酸酯功能单体。
  12. 根据权利要求11所述的结构胶纸(1)，其特征在于，所述含有胺基的(甲基)丙烯酸酯共聚物选自溶剂型含有胺基的(甲基)丙烯酸酯共聚物。
  13. 根据权利要求11所述的结构胶纸(1)，其特征在于，所述含有胺基的(甲基)丙烯酸酯功能单体选自丙烯酸二甲胺基乙酯、甲基丙烯酸二甲胺乙酯、甲基丙烯酸叔丁基氨基乙酯、甲基丙烯酸二乙氨基乙酯、丙烯酸N，N-二乙基氨基乙酯中的一种或几种。
  14. 根据权利要求11所述的结构胶纸(1)，其特征在于，所述含有胺基的(甲基)丙烯酸酯共聚物的单体组分还包括：(甲基)丙烯酸类单体。
  15. 根据权利要求14所述的结构胶纸(1)，其特征在于，所述(甲基)丙烯酸类单体选自丙烯酸、甲基丙烯酸、甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸正丁酯、甲基丙烯酸异丁酯、甲基丙烯酸叔丁酯、甲基丙烯酸己酯、甲基丙烯酸-2-乙基己酯、甲基丙烯酸异冰片酯、甲基丙烯酸月桂酯、丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丙酯、丙烯酸 异丙酯、丙烯酸正丁酯、丙烯酸异丁酯、丙烯酸仲丁酯、丙烯酸叔丁酯、丙烯酸环己酯、2-乙基丙烯酸乙酯、丙烯酸-2-乙基己酯中的一种或几种。
  16. 根据权利要求14所述的结构胶纸(1)，其特征在于，所述含有胺基的(甲基)丙烯酸酯共聚物的单体组分还包括：乙烯基类单体。
  17. 根据权利要求16所述的结构胶纸(1)，其特征在于，所述乙烯基类单体选自乙酸乙烯。
  18. 根据权利要求1所述的结构胶纸(1)，其特征在于，所述第二固化剂选自环氧树脂。
  19. 根据权利要求1所述的结构胶纸(1)，其特征在于，
    第一胶黏剂与第一固化剂的固化温度为40℃～50℃；
    第二胶黏剂与第二固化剂的固化温度为105℃～115℃。
  20. 根据权利要求1所述的结构胶纸(1)，其特征在于，结构胶纸(1)的总厚度为20μm～120μm，优选地，结构胶纸(1)的总厚度为40μm～70μm。
  21. 根据权利要求1所述的结构胶纸(1)，其特征在于，结构胶纸(1)的面积为1mm2～600mm2，优选地，结构胶纸(1)的面积为80mm2～480mm2。
  22. 根据权利要求1所述的结构胶纸(1)，其特征在于，基材(12)选自聚对苯二甲酸乙二醇酯。
  23. 根据权利要求1所述的结构胶纸(1)，其特征在于，发泡剂颗粒(111)的粒径为5μm～30μm。
  24. 根据权利要求1所述的结构胶纸(1)，其特征在于，发泡剂颗粒(111)的发泡温度为105℃～150℃，优选地，发泡剂颗粒(111)的发泡温度为110℃～140℃，进一步优选地，发泡剂颗粒(111)的发泡温度为120℃～130℃。
  25. 根据权利要求24所述的结构胶纸(1)，其特征在于，发泡剂颗粒(111)为物理 发泡剂和/或化学发泡剂。
  26. 根据权利要求25所述的结构胶纸(1)，其特征在于，
    所述物理发泡剂选自异戊烷发泡剂、异丁烷发泡剂、环戊烷发泡剂中的一种或几种；
    所述化学发泡剂选自偶氮二甲酰胺、偶氮二异丁腈、N，N-二亚硝基五次甲基四胺、4，4′-氧代双苯磺酰肼、对甲苯磺酰肼中的一种或几种。
  27. 一种结构胶纸(1)的制备方法，用于制备权利要求1-26中任一项所述的结构胶纸(1)，包括步骤：
    将第一胶黏剂、第一固化剂、第二胶黏剂、第二固化剂溶于溶剂中，搅拌均匀后加入发泡剂颗粒(111)制成浆料；
    将浆料涂布在基材(12)的其中一个表面上，之后置于烘箱中烘干以除去溶剂；
    将结构胶纸(1)从烘箱取出后进行熟化，完成结构胶纸(1)的制备。
  28. 根据权利要求27所述的结构胶纸(1)的制备方法，其特征在于，烘箱温度不低于第一胶黏剂与第一固化剂的固化温度，且低于第二胶黏剂与第二固化剂的固化温度。
  29. 根据权利要求27所述的结构胶纸(1)的制备方法，其特征在于，烘箱温度设定为70℃～80℃。
  30. 根据权利要求27所述的结构胶纸(1)的制备方法，其特征在于，烘烤时间为1min～2min。
  31. 根据权利要求27所述的结构胶纸(1)的制备方法，其特征在于，熟化温度为20℃～60℃，优选地，熟化温度为40℃～60℃，进一步优选地，熟化温度为40℃～45℃。
  32. 根据权利要求27所述的结构胶纸(1)的制备方法，其特征在于，熟化时间大于等于60h。
  33. 一种在电极片预留极耳空位的方法，其特征在于，包括步骤：
    在电极片的集流体(2)上的预留区域(21)粘贴根据权利要求1-26中任一项所述的结构胶纸(1)，使结构胶纸(1)的胶黏剂层(11)粘贴在集流体(2)上，将电极浆料(3)涂布在结构胶纸(1)的基材(12)的表面上，得到湿膜；
    将湿膜送入烘箱的低温区烘烤，结构胶纸(1)仍保持与集流体(2)粘结，其中，低温区的烘烤温度小于发泡剂颗粒(111)的起始发泡温度；
    继续将湿膜送入烘箱的高温区烘烤，使结构胶纸(1)中的发泡剂颗粒(111)发泡，结构胶纸(1)产生卷曲，且使结构胶纸(1)与集流体(2)之间的粘结力不大于4N/cm2，其中，高温区的烘烤温度大于等于发泡剂颗粒(111)的起始发泡温度；
    烘烤结束后将结构胶纸(1)剥离，即可在电极片预留极耳空位。
  34. 根据权利要求33所述的在电极片预留极耳空位的方法，其特征在于，低温区的烘烤温度为40℃～105℃，优选地，低温区的烘烤温度为80℃～100℃。
  35. 根据权利要求33所述的在电极片预留极耳空位的方法，其特征在于，高温区的烘烤温度为105℃～180℃，优选地，高温区的烘烤温度为125℃～145℃，进一步优选地，高温区的烘烤温度为130℃～135℃。
  36. 根据权利要求33所述的在电极片预留极耳空位的方法，其特征在于，低温区的烘烤时间为30s～300s，优选地，低温区的烘烤时间为30s～60s。
  37. 根据权利要求33所述的在电极片预留极耳空位的方法，其特征在于，高温区的烘烤时间为30s～300s，优选地，高温区的烘烤时间为30s～120s。
  38. 根据权利要求33所述的在电极片预留极耳空位的方法，其特征在于，低温区烘烤结束后使结构胶纸(1)与集流体(2)之间的粘结力不大于50N/cm2，优选地，低温区烘烤结束后使结构胶纸(1)与集流体(2)之间的粘结力为1N/cm2～23N/cm2。
  39. 根据权利要求33所述的在电极片预留极耳空位的方法，其特征在于，电极浆料(3)的涂覆厚度为40μm～300μm，优选地，电极浆料(3)的涂覆厚度为60μm～180μm。
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CN109360940A (zh) * 2018-09-26 2019-02-19 桑顿新能源科技有限公司 一种锂电池极片微孔箔材的涂布方法
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CN113707839A (zh) * 2021-08-02 2021-11-26 惠州锂威新能源科技有限公司 条纹极片及其辊压工艺与多极耳极片
WO2024179890A1 (de) * 2023-02-27 2024-09-06 Tesa Se Reaktivklebeband zum einfachen lösen

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