WO2018013342A1 - Adhésifs électroconducteurs - Google Patents

Adhésifs électroconducteurs Download PDF

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Publication number
WO2018013342A1
WO2018013342A1 PCT/US2017/039475 US2017039475W WO2018013342A1 WO 2018013342 A1 WO2018013342 A1 WO 2018013342A1 US 2017039475 W US2017039475 W US 2017039475W WO 2018013342 A1 WO2018013342 A1 WO 2018013342A1
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WO
WIPO (PCT)
Prior art keywords
solar cell
electrically conductive
conductive adhesive
peroxide
acid
Prior art date
Application number
PCT/US2017/039475
Other languages
English (en)
Inventor
Fei Xiang
Jose Manuel Rodriguez-Parada
Lida QIU
Original Assignee
E. I. Du Pont De Nemours And Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from CN201611070470.0A external-priority patent/CN107629734B/zh
Application filed by E. I. Du Pont De Nemours And Company filed Critical E. I. Du Pont De Nemours And Company
Priority to US16/317,608 priority Critical patent/US20190292418A1/en
Publication of WO2018013342A1 publication Critical patent/WO2018013342A1/fr

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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
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • C09J9/02—Electrically-conducting adhesives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/14—Peroxides
    • 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
    • C09J109/00—Adhesives based on homopolymers or copolymers of conjugated diene hydrocarbons
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys

Definitions

  • the disclosure is related to electrically conductive adhesives (ECA) comprising olefinic carboxylic acid or derivatives thereof.
  • the solar cells have surface electrodes, to which the wiring members (also called electro-conductive interconnect members or ribbons) are connected for extracting power from the cells.
  • the wiring members are usually in the form of metal strips (such as Cu strips) and they are often
  • Such polymer-based electrically conductive adhesives typically are comprised of insulating polymers (such as, epoxy resins, acrylic polymers, phenoxy resins, polyimides, or silicone rubbers) and electro-conductive particles (such as Ag particles), see, for example, U.S. Patent Publication Nos. 2010/0147355 and 2012/0012153.
  • insulating polymers such as, epoxy resins, acrylic polymers, phenoxy resins, polyimides, or silicone rubbers
  • electro-conductive particles such as Ag particles
  • the purpose of the present disclosure is to provide an electrically
  • conductive adhesive composition comprising: a) a binder formed of or comprising at least one peroxide curable elastomer and at least one peroxide-based curing agent; b) 40-93 wt% of conductive particles dispersed in the binder; and c) 0.1 - 1.5 wt% of olefinic carboxylic acid or derivative thereof dispersed in the binder, with the wt% of all components comprised in the composition totaling to 100 wt%, and wherein, the olefinic carboxylic acid has a formula R 1 C02R 2 , R 1 being hydrocarbyl or substituted hydrocarbyl having 4 or more carbon atoms, and containing one a-olefinic double bond, provided that the double bond is not part of a ring; and R 2 being hydrogen, hydrocarbyl, or substituted hydrocarbyl.
  • the at least one peroxide-based curing agent is present in the binder at a level of 0.1 -20 wt%, or 0.5-10 wt%, or 1 -5 wt% and the at least one peroxide-based curing agent is selected from the group consisting of 1 ,1 -bis(tert-buty peroxy)- 3,3,5-trimethylcyclohexane; 1 , 1 -di(tert-butylperoxy)cyclohexane; 2,5-di(tert- butylperoxy)-2,5-dimethyl-3-hexyne; 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane; tert-Butylperoxy 2-ethylhexyl carbonate; dicumyl peroxide; benzoyl peroxide;
  • acetylacetone peroxide methyl isobutyl ketone peroxide; dibenzoyl peroxide; cyclohexanone peroxide; di(4-tert-butylcyclohexyl) peroxydicarbonate; and combinations of two or more thereof.
  • the at least one peroxide curable elastomer is a selected from the group consisting of fluoroelastomers, ethylene/alkyl (meth)acrylate copolymer elastomers, and combinations of two or more thereof.
  • the binder is present at a level of 7-60 wt%, or 15-60 wt%, or 17-55 wt%, based on the total weight of the electrically conductive adhesive
  • the conductive particles are present at a level of 40-85 wt% or 45- 83 wt%, based on the total weight of the electrically conductive adhesive composition, and wherein, the conductive particles are selected from the group consisting of Au, Ag, Ni, Cu, Al, Sn, Zn, Ti, Sn, Bi, W, Pb, and alloys of two or more thereof, or, the conductive particles are Ag flakes.
  • the olefinic carboxylic acid or derivative thereof is present at a level of 0.2-1 .5 wt% or 0.5-1 wt%, based on the total weight of the electrically
  • the olefinic carboxylic acid or derivative thereof is selected from the group consisting of 4-pentenoic acid; 2-methyl-4-pentenoic acid methyl ester;
  • 2,2-dimethyl-4-pentenoic acid 5-hexenoic acid; 6-heptenoic acid; 6-heptenoic acid methyl ester; 7-octenoic acid; 8-nonenoic acid; 9-decenoic acid; 10- undecenoic acid; mono-2-(methacryloyloxy)ethyl succinate; methyl 10- undecenoate; 1 1 -dodecenoic acid; 7-oxo-1 1 -dodecenoic acid; 12-tridecanoic acid; and combinations of two or more thereof.
  • an electrically conductive adhesive prepared from the electrically conductive adhesive composition as described above, wherein, the at least one peroxide curable elastomer is cured by the at least one peroxide-based curing agent.
  • a solar cell module comprising at least one solar cell and at least one wiring member, wherein, the at least one solar cell has at least one surface electrode and the at least one wiring member is connected to the at least one surface electrode via the electrically conductive adhesive described above.
  • the at least one solar cell has a front surface electrode and a back surface electrode, and wherein there are one or more front wiring members connected to the front surface electrode via the electrically conductive adhesive and one or more back wiring members connected to the back surface electrode via the electrically conductive adhesive.
  • the at least one solar cell is a wafer-based solar cell.
  • the at least one solar cell is a thin film solar cell.
  • a solar cell module comprising one or more strings of solar cells, wherein each string of solar cells comprise at least a first solar cell and a second solar cell, with i) each of the first and second solar cells comprising a front surface electrode and a back surface electrode; ii) the first and second solar cells being positioned with an edge of the back surface of the second solar cell overlapping an edge of the front surface of the first solar cell; and iii) a portion of the front surface electrode of the first solar cell being hidden by the second solar cell and bonded to a portion of the back surface electrode of the second solar cell with the electrically conductive adhesive described above to electrically connect the first and second solar cells in series.
  • the range includes any value that is within the two particular end points and any value that is equal to or about equal to any of the two end points.
  • ECA electrically conductive adhesive compositions that comprise: a) a binder formed of or comprising at least one peroxide curable elastomer and at least one peroxide-based curing agent, b) conductive particles, and c) at least one olefinic carboxylic acid or derivative thereof.
  • Peroxide curable elastomers include both saturated and unsaturated elastomers and the basic chemistry of peroxide decomposition and subsequent crosslink-forming reactions is well established. In general, at the beginning of the curing process, the organic peroxide splits into 2 free radicals, according to the equation:
  • Suitable peroxide curable elastomers include, without limitation,
  • fluroelastomers ethylene/alkyl (meth)acrylate copolymer elastomers (AEM rubbers), ethylene vinyl acetate (EVA), silicones (including fluorosilicones), cyanoacrylates, nitrile butadiene rubbers (NBR), hydrogenated nitrile butadiene rubbers (HNBR), neoprene rubbers, ethylene propylene diene monomer (M-class) rubbers (EPDM rubbers), etc.
  • AEM rubbers ethylene/alkyl (meth)acrylate copolymer elastomers
  • EVA ethylene vinyl acetate
  • silicones including fluorosilicones
  • cyanoacrylates cyanoacrylates
  • NBR nitrile butadiene rubbers
  • HNBR hydrogenated nitrile butadiene rubbers
  • neoprene rubbers ethylene propylene diene monomer (M-class) rubbers (EPDM rubbers)
  • the peroxide curable elastomers used herein are fluoroelastomers containing the following cure site monomers, i) bromine- containing olefins; ii) iodine-containing olefins; iii) bromine-containing vinyl ethers; iv) iodine-containing vinyl ethers; v) 1 , 1 ,3,3,3-pentafluoropropene (2-HPFP); and vi) non-conjugated dienes.
  • bromine-containing olefins examples include
  • CF 2 CFOCF2CF2CF 2 OCF2CF2Br; bromotrifluoroethylene; 4-bromo-3,3,4,4- tetrafluorobutene-1 (BTFB); etc.
  • exemplary bromine-containing olefins also include other vinyl bromide, such as, 1 -bromo-2,2-difluoroethylene; perfluoroallyl bromide; 4-bromo-1 , 1 ,2-trifluorobutene-1 ; 4-bromo-1 , 1 ,3,3,4,4,-hexafluorobutene;
  • Z-CH2CHR-I wherein R is -H or -CH3 and Z is a C1-C18 (per)fluoroalkylene radical, linear or branched, optionally containing one or more ether oxygen atoms, or a (per)fluoropolyoxyalkylene radical as disclosed in U.S. Patent 5,674,959.
  • Iodine-containing vinyl ethers include iodoethylene; 4-iodo-3, 3,4,4- tetrafluorobutene-1 (ITFB); 3-chloro-4-iodo-3,4,4-trifluorobutene; 2-iodo-1 , 1 ,2,2- tetrafluoro-1 -(vinyloxy)ethane; 2-iodo-1 -(perfluorovinyloxy)-l, 1 ,-2,2- tetrafluoroethylene; 1 , 1 ,2,3,3,3-hexafluoro-2-iodo-1 -(perfluorovinyloxy)propane; 2-iodoethyl vinyl ether; 3,3,4,5,5,5-hexafluoro-4-iodopentene; and
  • Non-conjugated diene cure site monomers include, but are not limited to
  • a suitable triene is 8-methyl-4-ethylidene-1 ,7-octadiene.
  • BTFB 4-bromo- 3,3,4,4-tetrafluorobutene-1
  • ITFB 4-iodo-3,3,4,4- tetrafluorobutene-1
  • allyl iodide 4-iodo-3,3,4,4- tetrafluorobutene-1
  • bromotrifluoroethylene 4-bromo- 3,3,4,4-tetrafluorobutene-1 (BTFB); 4-iodo-3,3,4,4- tetrafluorobutene-1 (ITFB); allyl iodide; and bromotrifluoroethylene.
  • iodine-containing end groups, bromine-containing end groups or mixtures thereof may optionally be present at one or both of the
  • fluoroelastomer polymer chain ends as a result of the use of chain transfer or molecular weight regulating agents during preparation of the fluoroelastomers.
  • the amount of chain transfer agent, when employed, is calculated to result in an iodine or bromine level in the fluoroelastomer in the range of about 0.005-5 wt%, or about 0.05-3 wt%.
  • chain transfer agents include iodine-containing compounds that result in incorporation of bound iodine at one or both ends of the polymer molecules.
  • 3,3,4,4,tetrafluorohexane are representative of such chain transfer agents.
  • Other iodinated chain transfer agents include 1 ,3-diiodoperfluoropropane; 1 ,6- diiodoperfluorohexane; 1 ,3-diiodo-2- chloroperfluoropropane; 1 ,2- di(iododifluoromethyl)-perfluorocyclobutane; monoiodoperfluoroethane;
  • brominated chain transfer agents examples include 1 -bromo-2- iodoperfluoroethane; 1 -bromo-3-iodoperfluoropropane; 1 -iodo-2-bromo-1 , 1 - difluoroethane and others such as disclosed in U.S. Patent 5, 151 ,492.
  • chain transfer agents suitable for use in the fluoroelastomers used herein include those disclosed in U.S. Patent 3,707,529.
  • chain transfer agents include isopropanol, diethylmalonate, ethyl acetate, carbon tetrachloride, acetone, and dodecyl mercaptan.
  • Units of cure site monomer are typically present at a level of about 0.05-10 wt%, or about 0.05-5 wt%, or about 0.05-3 wt%, based on the total weight of fluoroelastomer used herein.
  • fluoroelastomers which may be used herein include, without limitation, those fluoroelastomers having at least about 53 wt% fluorine and comprising copolymerized units of i) vinylidene fluoride and hexafluoropropylene; ii) vinylidene fluoride, hexafluoropropylene, and tetrafluoroethylene; iii) vinylidene fluoride, hexafluoropropylene, tetrafluoroethylene, and 4-bromo-3, 3,4,4- tetrafluorobutene-1 ; iv) vinylidene fluoride, hexafluoropropylene,
  • the fluoroelastomers used herein are typically prepared in an emulsion polymerization process, which may be a continuous, semi-batch, or batch process.
  • fluoroelastomers useful herein are also commercially available from various vendors.
  • suitable fluoroelastomers may be obtained from E. I. du Pont de Nemours and Company (U.S.A.) (hereafter'OuPonf) under the trade names Viton®GF-S; Viton®GAL-S; Viton®GBL-S; Viton®GBL; Viton®GLT- S; Viton®GBLT-S; Viton®GFLT-S; Viton®ETP-S; or from 3M (U.S.A.) under the trade names 3MTMDyneonTMFLS 2650; DyneonTM2260; DyneonTMFPO3740;
  • DyneonTMFP03741 or from Daikin Industries, Ltd. (Japan) under the trade names DAI-ELTM 801 ; DAI-ELTM 802; DAI-ELTM 8002; DAI-ELTM 901 ; DAI-ELTM 952; DAI-ELTM LT252; DAI-ELTM LT303L; or from Tetralene Elastomer, Inc.
  • the peroxide curable elastomers are
  • ethylene/alkyl (meth)acrylate copolymer elastomers also known as AEM rubbers.
  • AEM rubbers are derived from copolymerization of polymerized units of ethylene and about 45-90 wt%, or about 50-80 wt%, or about 50-75 wt% of polymerized units of at least one alkyl (meth)acrylate.
  • (meth)acrylate is used herein to refer to esters of methacrylic acids and/or esters of acrylic acids, and the term “meth” is used herein to refer to -H or branched or non-branched groups C1-C10 alkyl, and the term “alkyl” is used herein to refer to -H or branched or non- branched groups of C1-C12 alkyl, C1-C20 alkoxyalkyl, C1 -C12 cyanoalkyl, or C1 -C12 fluoroalkyl.
  • the alkyl (meth)acrylate groups used herein include, without limitation, alkyl acrylate, alkyl methacrylates, alkyl ethacrylates, alkyl
  • alkyl hexacrylates alkoxyalkyl methacrylates, alkoxyalkyl ethacryates, alkoxyalkyl propacrylates and alkoxyalkyl hexacrylates.
  • the alkyl groups may be substituted with cyano groups or one or more fluorine atoms.
  • the alkyl group may be a C1 -C12 cyanoalkyl group or a C1-C12 fluoroalkyl group.
  • the AEM rubbers may also comprise copolymerized units of more than one species of the alkyl (meth)acrylates, for example two different alkyl acrylate monomers.
  • the ethylene/alkyl (meth)acrylate copolymers used herein include, without limitation, ethylene/methyl acrylate copolymers (EMA), ethylene/ethyl acrylate copolymers (EEA), and ethylene/butyl acrylate
  • the AEM rubbers used herein may optionally further comprise up to about 5 wt% of a functionalized comonomer, based on the total weight of the AEM rubbers.
  • the optional functionalized comonomers used herein include, without limitation, (meth)acrylate glycidyl esters (such as glycidyl methacrylate), chlorovinyl ether, maleic acids, and other comonomers having one or more reactive groups including acid, hydroxyl, anhydride, epoxy, isocyanates, amine, oxazoline, chloroacetate, carboxylic ester moieties, or diene functionality.
  • the AEM rubbers used herein are made by copolymerizing ethylene and more than one (e.g., two) alkyl (meth)acrylate monomers.
  • Examples are AEM rubbers made by polymerizing ethylene, methyl acrylate, and a second acrylate (such as butyl acrylate).
  • the AEM rubbers may be prepared by various processes well known in the polymer art.
  • the copolymerization can be run as a continuous process in an autoclave reactor.
  • the AEM rubbers used herein may be produced at high pressure and elevated temperature in a tubular reactor or the like. They can be separated from the product mixture with the un-reacted monomers and solvent (if used) by conventional means, e.g., vaporizing the non- polymerized materials and solvent under reduced pressure and at an elevated temperature.
  • the AEM rubbers used herein are also available commercially.
  • Exemplary AEM rubbers may include those available from DuPont under the trade name Vamac®DP.
  • the peroxide curable elastomers used herein are ethylene/vinyl copolymers (EVA), derived from copolymerization of polymerized units of ethylene and about 5-50 wt%, or about 15-45 wt%, or about 20-45 wt% of copolymerized units of vinyl acetates, based on the total weight of the EVA.
  • EVA ethylene/vinyl copolymers
  • the EVA used herein may also comprise up to about 35 wt%, or up to about 25 wt%, or up to about 20 wt% of copolymerized units of one or more additional monomers.
  • Such one or more additional comonomers may include, without limitation, (meth)acrylic acid, maleic anhydride, butyl acrylate, carbon monoxide, and combinations of two or more thereof.
  • Suitable EVA also may be obtained commercially.
  • Elvax® EVA resins available from DuPont; EvataneTM EVA copolymers available from Arkerma, Inc. (France); EscoreneTM EVA resins available from ExxonMobil Chemical (U.S.A.); Evaflex® EVA resins available from DuPont-Mitsui
  • the peroxide curable elastomers used herein are silicones having a general forming unit R x SiO[(4-x)/2], wherein R is identical or different and is an unsubstituted or substituted hydrocarbon radical and x is a number that is >0 and less or equal to 3 or preferably from 1 .9 to 2.1.
  • Suitable silicones include, without limitation, those commercially available from Dow Chemicals (U.S.A.) under the trade names, Dow CorningTMC6-235; Dow CorningTMC6-250; Dow CorningTMC6-265; SilasticTMHCM 60-1225 GRAY; SilasticTMQ7-4535; SilasticTMQ7-4565; and Toray DY 32-315 U, or from Wacker Chemical AG (Germany) under the trade names, CenusilTMR 340; CenusilTMR 350; ElastosilTM B 242; ElastosilTM B 227M; ElastosilTM C 713; ElastosilTM C 1451 ; ElastosilTM R 770/50; ElastosilTM R 752/70; ElastosilTM R Plus4806/20; ElastosilTM R Plus41 10/70; PowersilTM 460; PowersilTM 3100 MH; SilpuranTM 8060/40;
  • the silicones used herein also may include fluorosilicones, which contain a silicone polymer chain with fluorinated side-chains.
  • fluorosilicones include, without limitation, those commercially available from Dow Chemicals under the trade names, SilasticTMLS5-8740; Dow Corning TorayTM DY 37-016U; Dow Corning TorayTM DY 37-029U; Dow Corning TorayTM LS 63U;
  • the monomer is selected from methyl cyanoacrylate, ethyl-2-cyanoacrylate, propyl cyanoacrylates, butyl
  • cyanoacrylates such as n-butyi-2 -cyanoacrylate
  • octyi cyanoacrylates ally! cyanoacrylate
  • 3-methoxyethyl cyanoacrylate 3-methoxyethyl cyanoacrylate and combinations thereof.
  • a particularly desirable one is ethyl-2-cyanoacrylate.
  • Suitable cyanoacrylates may be obtained commercially from Henkel (Germany) under the trade names
  • Nitrile butadiene rubber is a family of unsaturated copolymers of 2- propenenitrile and one or both of 1 ,2-butadiene and 1 ,3-butadiene,.
  • Suitable NBR may be obtained from Nantex Industry Co., Ltd. (Taiwan) under the trade name, NANCARTMNBR, from JSR Corporation (Japan) under the product names, JSR N220S; JSR 240S; etc., from Synthos S.A. (Poland) under the product name KER, from LG Chem (Korea) under the product names, NBR7150; NBR3250; etc., or from Kumho Petrochemical (Korea) under the product names, KNB35L; KNB40M; etc.
  • HNBR Hydrogenated nitrile butadiene rubber
  • HNBR also are commercially available from Zeon Company (Japan) under the trade names, Zetpol®ZP-0020; Zetpol®ZP-2010; Zetpol®ZP4300; etc., or from LANXESS under the trade names, Therban®3406; Therban®4367;
  • neoprene rubbers may be obtained from Denka Company Limited (Japan) under product name, Denka Chloroprene, or from Tosoh Corporation (Japan) under the trade names, SkypreneTM G-70; SkypreneTM B-30S; SkypreneTM Y-30S; etc., or from Shanna Synthetic Rubber Co., Ltd. (China) under the product name, SN 322, or from Lanxess Corporation (U.S.A.) under the trade name, BayprenTM.
  • the peroxide curable elastomers used herein are EPDM rubbers (ethylene propylene diene monomer (M-class) rubber), a type of synthetic rubber. Suitable EPDM rubbers may be obtained from China
  • Suitable peroxide-based curing agents include, without limitation, 1 , 1 -bis(tert-buty peroxy)-3,3,5- trimethylcyclohexane; 1 , 1 -di(tert-butylperoxy)cyclohexane; 2,5-di(tert- butylperoxy)-2,5-dimethyl-3-hexyne; 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane; fe/f-Butylperoxy 2-ethylhexyl carbonate; dicumyl peroxide; benzoyl peroxide;
  • acetylacetone peroxide methyl isobutyl ketone peroxide; dibenzoyl peroxide; cyclohexanone peroxide; di(4-tert-butylcyclohexyl) peroxydicarbonate; and etc.
  • the at least one peroxide-based curing agent may be present in the binder material at a level of about 0.1 -20 wt%, or about 0.5-10 wt%, or about 1 -5 wt%.
  • the binder material may be present at a level of about 7-60 wt%, or about 15-60 wt%, or about 17-55 wt%.
  • the conductive particles used herein provide electrical conductivity in the adhesive composition upon circuit connection.
  • the conductive particles may include metal particles, non-metal particles, metal coated particles, and
  • Suitable metal particles include, without limitation, particles of Au, Ag, Ni, Cu, Al, Sn, Zn, Ti, Sn, Bi, W, Pb, and alloys of two or more thereof.
  • Suitable non-metal particles include, without limitation, carbon nanotube, graphene, polyaniline, polyacetylene, and polypyrrole, and combinations of two or more thereof.
  • the metal coating material used in the metal coated particles may include, without limitation, Au, Ag, Ni, and combinations of two or more thereof.
  • Suitable metal coated particles include, without limitation, Ag-coated glass beads, Ag-coated polystyrene particles, Ag-coated Cu particles, Ni-coated Cu particles, and combinations of two or more thereof. The size of the
  • conductive particles may be determined depending on the pitch of circuits and may be, e.g., about 0.1 to about 50 pm, depending on the intended application.
  • the conductive particles may be present at a level of about 40-93 wt%, or about 40-85 wt%, or about 45- 83 wt%.
  • the olefinic carboxylic acids used herein have a formula R 1 C02R 2 , wherein R 1 is hydrocarbyl or substituted hydrocarbyl having 4 or more carbon atoms, and containing one a-olefinic double bond, provided that the double bond is not part of a ring; and R 2 is hydrogen, hydrocarbyl or substituted hydrocarbyl.
  • Exemplary suitable olefinic carboxylic acids include, without limitation, 4- pentenoic acid; 2-methyl-4-pentenoic acid methyl ester; 2,2-dimethyl-4-pentenoic acid; 5-hexenoic acid; 6-heptenoic acid; 6-heptenoic acid methyl ester; 7- octenoic acid; 8-nonenoic acid; 9-decenoic acid; 10-undecenoic acid; mono-2- (methacryloyloxy)ethyl succinate; methyl 10-undecenoate; 1 1 -dodecenoic acid; 7-OXO-1 1 -dodecenoic acid; 12-tridecanoic acid; and etc.
  • the olefinic carboxylic acids may be present at a level of about 0.1 - 1.5 wt%, or about 0.2-1.5 wt%, or about 0.5-1 wt%.
  • ECA sheets or tapes formed of the electrically conductive adhesive compositions disclosed. Further, the ECA compositions or ECA sheets or tapes, as disclosed above may be cured under heat and optional pressure. During the curing process, the peroxide-curable elastomers are crosslinked by the peroxide-based curing agents. Therefore, further disclosed herein are ECA comprising a binder matrix formed of peroxide cured elastomer(s), and conductive particles dispersed in the binder matrix, and olefinic carboxylic acids or derivatives thereof dispersed in the binder matrix.
  • articles comprising the ECA described above.
  • the articles include, without limitation, solar cell modules, light emitting diode (LED) bulb, hand-held devices (such as smart phone), tablet PC, digital camera, laptop, portable wifi server, wearable devices like smart band, wireless telecom infrastructure (WTI), display, and etc.
  • LED light emitting diode
  • WTI wireless telecom infrastructure
  • solar cell modules that comprise one or more solar cells and the ECA.
  • the ECA are included to electrically connect the surface electrodes of the solar cells with the wiring members (also called ribbons).
  • the wiring members are included to electrically connect the solar cells in series and/or in parallel and to form conductive paths for extracting the electric power out from the modules.
  • the solar cells used herein may be any article or material that can convert light into electrical energy.
  • the solar cells used herein include, without limitation, wafer-based solar cells (e.g., c-Si or mc-Si based solar cells) and thin film solar cells (e.g., a-Si, pc-Si, CdTe, copper indium selenide (CIS), copper-indium-gallium selenide (CIGS), light absorbing dyes, or organic
  • the surface electrodes of the solar cells may be made of any suitable materials that can provide electrical conduction.
  • the surface electrodes may be formed by printing (e.g., screen printing or ink-jet printing) conductive paste over the solar cell surfaces.
  • suitable paste materials include, without limitation, silver paste, silver-containing glass paste, gold paste, carbon paste, nickel paste, aluminum paste, transparent conducting oxide (TCO) (such as indium tin oxide (ITO) or aluminum zinc oxide (AZO).
  • the wiring members may be formed of any high conductive materials, such as copper, silver, aluminum, gold, nickel, cadmium, and alloys thereof.
  • the surface electrodes of the solar cells may be in any suitable patterns and the connection between the surface electrodes and the wiring member may be in any suitable forms.
  • each solar cell may comprise a front surface electrode and a back surface electrode, wherein the front surface electrode may be comprised of a plurality of parallel conductive fingers and two or more conductive bus bars perpendicular to and connecting the conductive fingers, and wherein the back surface electrode may be comprised of a layer of conductive paste and two or more conductive bus bars.
  • the conductive fingers and the conductive bus bars may be formed of silver paste and the layer of conductive paste comprised in the back surface electrode may be formed of aluminum paste.
  • the wiring members are connected to the front and back surface electrodes by adhering to the bus bars of the front and back surface electrodes via the ECA disclosed herein.
  • the front and/or back surface electrodes comprised in the solar cells may be free of bus bars. That is to say, for example, each of the solar cells comprises a front surface electrode that is formed of the plurality of conductive fingers only without bus bars and a back surface electrode that is formed of a layer of conductive paste and two or more conductive bus bars.
  • the wiring members are connected to the front surface electrode by adhering to the conductive fingers via the electrically conductive adhesives and to the back surface electrode by adhering to the bus bars via the ECA.
  • each of the solar cells comprises a front surface electrode that is formed of the plurality of conductive finger and two or more bus bars and a back surface electrode that is formed of the conductive paste only without the bus bars.
  • the wiring members are connected to the front surface electrode by adhering to the bus bars via the electrically conductive adhesives and to the back surface electrode by adhering to the conductive paste via the ECA.
  • each of the solar cells comprises a front surface electrode that is formed of the plurality of conductive fingers only without bus bars and a back surface electrode that is formed of the conductive paste only without the bus bars.
  • the wiring members are connected to the front surface electrode by adhering to the conductive fingers via the ECA and to the back surface electrode by adhering to the conductive paste via the ECA.
  • the opposite surface electrodes are typically formed of transparent TCO layers or metal grids.
  • the back surface electrodes may also be formed of metal films, (such as Al, TiN, Zn, Mo, stainless steel).
  • the wiring members may be connected to the electrodes by adhering to the electrodes via the ECA. In certain embodiments, however, bus bars may be used and
  • each of the electrodes and the wiring members may be connected to the electrodes by adhering to the bus bars via the ECA.
  • the solar cell modules comprise one or more strings of series-connected solar cells arranged in an over-lapping shingle pattern. It is also termed shingled cell modules or dense cell interconnects.
  • the series-connected solar cells comprise at least a first solar cell and a second solar cell.
  • Each of the first and second solar cells comprises a front surface electrode and a back surface electrode.
  • the first and second solar cells are positioned with an edge of the back surface of the second solar cell overlapping an edge of the front surface of the first solar cell and a portion of the front surface electrode of the first solar cell is hidden by the second solar cell and bonded to a portion of the back surface electrode of the second solar cell with the ECA disclosed herein to electrically connect the first and second solar cells in series.
  • each of the series-connected solar cells may have a rectangular or substantially rectangular shape.
  • the front surface electrode may be comprised of a plurality of parallel conductive fingers and a bus bar perpendicular to and connecting the conductive fingers and positioned adjacent to the edge of one side of the solar cell.
  • the back surface electrode may be comprised of a layer of conductive paste and a bus bar also positioned to the edge of one side of the solar cell and the front and back bus bars are positioned along opposite sides of the solar cells.
  • two adjacent solar cells of the series-connected solar cells are positioned in an overlapping geometry with their sides bearing the bus bars parallel to each other and with the back bus bar of one of the solar cells overlapping and physically and electrically connected to the front bus bar of the other solar cell via the ECA disclosed above.
  • either one of both of the front and back bus bars are replaced by a contact pad.
  • either one of both of the front and back bus bars are replaced by two or more discrete contact pads that are arranged along the edge of one side of the solar cells.
  • either one or both of the front and back bus bars are omitted.
  • the current- collecting functions would be performed, or partially performed, by the ECAs used to bond the adjacent and overlapping solar cells.
  • any suitable process may be used to adhere the wiring member(s) to the surface electrode(s) via the electrically conductive adhesives disclosed herein.
  • the process may include: mixing and dissolving the peroxide curable elastomer(s), the peroxide-based curing agent(s), the conductive particles, the olefinic carboxylic acid or derivative thereof, and other additives in a solvent (such as methyl isobutyl ketone, methyl ethyl ketone, diisobutyl ketone, C-1 1 ketone, or mixtures thereof); casting the solution over one or both sides of the wiring member(s) followed by drying; and laminating the coated wiring members over the surface electrode(s) of the solar cells.
  • a solvent such as methyl isobutyl ketone, methyl ethyl ketone, diisobutyl ketone, C-1 1 ketone, or mixtures thereof
  • the process may include: mixing and dissolving the peroxide curable elastomer, the peroxide- based curing agent, the conductive particles, the olefinic carboxylic acid or derivative thereof, and other additives in a suitable solvent; casting the solution over the surface electrode(s) of the solar cells followed by drying; and laminating the wiring members over the coated surface of the surface electrode(s).
  • the process may include first preparing a pre-formed film or sheet of the ECA composition and then laminating the wiring member(s) over the surface electrode(s) with the pre-formed electrically conductive film or sheet inbetween.
  • the pre-formed ECA film or sheet may be prepared by any suitable methods, such as casting (over a release film), extrusion, calendering, etc.
  • FE-1 a vinylidene fluoride/hexafluoropropylene/tetrafluoroethylene
  • FE-2 a vinylidene fluoride/hexafluoropropylene/tetrafluoroethylene
  • AEM an ethylene acrylate dipolymer elastomer obtained from DuPont under the trade name Vamac® DP;
  • TAIC triallyl isocyanurate obtained from DuPont under the trade name of DiakTM7;
  • Antioxidant 4,4'-bis(a,a-dimenthylbenzyl) diphenylamince obtained from Chemtura Corporation (U.S.A.) under the trade name NaugurdTM 445; MgO: magnesium oxide, obtained from Kyowa Chemical Industry Co., Ltd. (Japan);
  • Adhesion promoter-1 a bonding agent obtained from Dow Chemical
  • Adhesion promoter-2 ⁇ -glycidylpropyltrimethoxysilane obtained from
  • Oleic acid obtained from Sigma-Aldrich
  • an ECA composition was prepared by first dissolving the elastomer(s), the processing aids, and the curing agent in a
  • MIBK/DIBK solvent methyl isobutyl ketone/diisobutyl ketone (1 :3 by weight)
  • other constituent materials e.g., the Ag flakes, adhesion promoters, and optionally acid(s)
  • the ECA solution as prepared above was blade-casted on an insulating glass slide to form a 30x2 mm strip; dried at 80°C for 10 min; and cured in a vacuum laminator at about 0.1 MPa and about 155°C for about 15 min.
  • the sheet resistance of the cured ECA strips were measured by a four- probe method using a sheet resistivity meter (manufactured by Quatek Co. Ltd. (Taiwan) with the model name QT-70/5601Y) and the thickness of the cured ECA strip was measured using a Dektal XTTM stylus profiler (manufactured by Bruker Corp. (Germany)).
  • the volume resistivity of the cured ECA strips were
  • ECA solution as prepared above in each example was casted over the front bus bars of a c-Si solar cell followed by drying at 80°C for 15 min. Then a Tin coated Cu ribbon (1.2 mm wide) was manually soldered over the ECA strip at 220°C, followed by vacuum lamination at 155°C and 0.1 MPa for 15 min. The 180° peel strength between the Tin coated Cu ribbon and the front bus bars were determined in accordance with ASTM D903 and tabulated in Tables 1 and 2. Similarly, Tin coated Cu ribbons was bonded over the back bus bars of the back surface of the c-Si cell via the ECA prepared above, and the 180° peeling strength between the Tin coated Cu ribbon and the back bus bars was determined and tabulated in Tables 1 and 2.
  • the addition of the olefinic carboxylic acid disclosed herein could improve the adhesion property of the elastomer-based ECA.
  • the olefinic carboxylic acid disclosed herein e.g., 10-undecenoid acid or mono-2-(methacryloyloxy)ethyl succinate
  • CE6 in order to maintain low resistivity, it is preferred to keep the content level of the olefinic carboxylic acid not greater than 1 .5 wt%.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Physics & Mathematics (AREA)
  • Dispersion Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

L'invention concerne des compositions adhésives électroconductrices et leur utilisation dans des modules de cellules solaires, les adhésifs électroconducteurs comprenant un ou plusieurs acides carboxyliques oléfiniques ou leurs dérivés.
PCT/US2017/039475 2016-07-15 2017-06-27 Adhésifs électroconducteurs WO2018013342A1 (fr)

Priority Applications (1)

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US16/317,608 US20190292418A1 (en) 2016-07-15 2017-06-27 Electrically conductive adhesives

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CN201610555459 2016-07-15
CN201610555459.7 2016-07-15
CN201611070470.0A CN107629734B (zh) 2016-07-15 2016-11-29 导电粘合剂
CN201611070470.0 2016-11-29

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Cited By (2)

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CN111117498A (zh) * 2019-12-26 2020-05-08 江苏鹿山新材料有限公司 一种光伏用光热双重固化poe封装胶膜及其制备方法
IT201900002397A1 (it) 2019-02-19 2020-08-19 Fondazione St Italiano Tecnologia Adesivo elettricamente conduttivo.

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US20100063215A1 (en) * 2006-12-25 2010-03-11 Kaneka Corporation Curable composition
US20130340806A1 (en) * 2011-01-27 2013-12-26 Hitachi Chemical Company, Ltd. Electrically conductive adhesive composition, connector and solar cell module
US8709552B2 (en) * 2009-01-29 2014-04-29 Toray Industries, Inc. Resin composition and display device using the same
US20150357497A1 (en) * 2013-01-10 2015-12-10 E. I. Du Pont De Nemours And Company Electrically conductive adhesives comprising blend elastomers
US20170152410A1 (en) * 2014-08-29 2017-06-01 Furukawa Electric Co., Ltd. Conductive adhesive composition

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US20100063215A1 (en) * 2006-12-25 2010-03-11 Kaneka Corporation Curable composition
US8709552B2 (en) * 2009-01-29 2014-04-29 Toray Industries, Inc. Resin composition and display device using the same
US20130340806A1 (en) * 2011-01-27 2013-12-26 Hitachi Chemical Company, Ltd. Electrically conductive adhesive composition, connector and solar cell module
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IT201900002397A1 (it) 2019-02-19 2020-08-19 Fondazione St Italiano Tecnologia Adesivo elettricamente conduttivo.
US11859113B2 (en) 2019-02-19 2024-01-02 Fondazione Istituto Italiano Di Tecnologia Electrically conductive adhesive
CN111117498A (zh) * 2019-12-26 2020-05-08 江苏鹿山新材料有限公司 一种光伏用光热双重固化poe封装胶膜及其制备方法
CN111117498B (zh) * 2019-12-26 2022-04-29 江苏鹿山新材料有限公司 一种光伏用光热双重固化poe封装胶膜及其制备方法

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