CN113462353A - Conductive adhesive for laminated photovoltaic module and preparation method and application thereof - Google Patents

Conductive adhesive for laminated photovoltaic module and preparation method and application thereof Download PDF

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CN113462353A
CN113462353A CN202110814942.3A CN202110814942A CN113462353A CN 113462353 A CN113462353 A CN 113462353A CN 202110814942 A CN202110814942 A CN 202110814942A CN 113462353 A CN113462353 A CN 113462353A
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resin
conductive adhesive
photovoltaic module
oxazine
hydrogen
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CN113462353B (en
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刘展
张保坦
邹余凤
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Shenzhen Mingyue Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
    • C09J183/04—Polysiloxanes
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/042—PV modules or arrays of single PV cells
    • H01L31/05—Electrical interconnection means between PV cells inside the PV module, e.g. series connection of PV cells
    • H01L31/0504—Electrical interconnection means between PV cells inside the PV module, e.g. series connection of PV cells specially adapted for series or parallel connection of solar cells in a module
    • H01L31/0512—Electrical interconnection means between PV cells inside the PV module, e.g. series connection of PV cells specially adapted for series or parallel connection of solar cells in a module made of a particular material or composition of materials
    • 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
    • C08K2003/0806—Silver
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/001—Conductive additives
    • 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
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    • C08K2201/005—Additives being defined by their particle size in general
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • 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
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    • Y02E10/50—Photovoltaic [PV] energy

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Abstract

The invention discloses a conductive adhesive for a laminated photovoltaic module and a preparation method and application thereof. The invention discloses a conductive adhesive for a laminated photovoltaic module, which comprises the following raw materials: vinyl silicone resin, oxazine resin and crosslinking agent. According to the invention, a triazine heterocyclic structure is introduced into the structure of the organic silicon conductive adhesive through molecular structure design, and organic silicon resin containing unsaturated bonds is combined with the triazine resin, so that the crosslinking density of the resin and the bonding strength and tensile strength of the colloid are improved, and the conductive adhesive for the tiled photovoltaic module, which is high in strength, good in bonding property and ageing-resistant, is obtained; meanwhile, the moisture and heat resistance of the organic silicon can be improved, and the problems of poor toughness, cracking, hardening, brittleness and the like of the existing organic silicon conductive adhesive after aging are effectively solved.

Description

Conductive adhesive for laminated photovoltaic module and preparation method and application thereof
Technical Field
The invention relates to the technical field of adhesives, in particular to a conductive adhesive for a laminated photovoltaic module and a preparation method and application thereof.
Background
Solar photovoltaic modules are developed very rapidly, the relative concept of high-efficiency modules is also changing constantly, and the laminated module is a novel photovoltaic packaging technology. The tiling technology redesigns the grid lines of the battery pieces into patterns which can be reasonably cut into small pieces, so that the positive and negative poles of each small piece after cutting are designed according to the tiling technology. And each small piece is welded into a string, the traditional technology that a battery structure is connected in series by welding tapes is abandoned, and the battery structure is welded into the string by using a conductive adhesive material, so that gaps in the assembly are fully utilized, more than 13% of battery pieces than the conventional assembly can be placed in the same area, and due to the optimization of the assembly structure, the non-welding-tape design is adopted, the line loss of the assembly is reduced, and the output power of the assembly is greatly improved. From the above, it can be seen that the conductive adhesive is one of the key materials for determining the reliability of the laminated assembly.
The conductive adhesive is an adhesive with certain electric and thermal conductivity after being cured, and generally comprises matrix resin, conductive filler, an auxiliary agent and the like, and can be divided into an acrylic system, an epoxy system, an organic silicon system and the like according to the structure of basic resin. The organic silicon system is fast in curing and good in aging resistance, and is widely applied to the photovoltaic solar industry. Because the overlapped parts of the cell sheets in the laminated assembly need to be connected in series by using the conductive adhesive, the conductive adhesive is required to have good flexibility and excellent bonding property, however, the conductive adhesive of the current organic silicon system has poor bonding property due to the addition of the conductive filler, and the application in the laminated photovoltaic assembly is limited.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art. Therefore, the conductive adhesive for the laminated photovoltaic module has the characteristics of good cohesiveness and high tensile strength.
The invention further provides a preparation method of the conductive adhesive for the laminated photovoltaic module.
The invention further provides an application of the conductive adhesive for the laminated photovoltaic module.
The invention provides a conductive adhesive for a laminated photovoltaic module, which comprises the following raw materials: vinyl silicone resin, oxazine resin and crosslinking agent.
The conductive adhesive for the laminated photovoltaic module provided by the embodiment of the invention at least has the following beneficial effects: according to the invention, the organic silicon resin (vinyl organic silicon resin) containing unsaturated bonds is independently designed and selected and combined with the oxazine resin, so that the crosslinking density of the resin and the adhesive strength and tensile strength of colloid are improved; meanwhile, the moisture and heat resistance of the organic silicon can be improved, the problems of poor toughness, cracking, hardening, embrittlement and the like of the existing organic silicon conductive adhesive after aging are effectively solved, and the conductive adhesive for the laminated photovoltaic module, which has high strength, good cohesiveness and ageing resistance, is obtained, so that the reliability of the laminated photovoltaic module is improved, and the conductive and ageing resistance requirements of the laminated photovoltaic module can be met. In addition, the conductive adhesive prepared by the invention has better conductivity, lower contact resistance and good toughness, can be widely used for conductive bonding of the photovoltaic laminated assembly cell, simplifies the connection process of the existing laminating technology, and improves the production efficiency and yield of the laminated assembly.
In some embodiments of the present invention, the triazine-based resin comprises a triazine-based resin.
Through the implementation mode, a triazine heterocyclic structure is introduced into the structure of the organic silicon conductive adhesive through molecular structure design, organic silicon resin (vinyl organic silicon resin) containing unsaturated bonds is combined with hybrid resin of a six-membered heterocyclic triazine structure, the cross-linking density of the resin and the adhesive strength and tensile strength of the adhesive are improved, and the conductive adhesive for the laminated photovoltaic module, which is high in strength, good in adhesive property and ageing-resistant, is obtained; meanwhile, the moisture and heat resistance of the organic silicon can be improved, and the problems of poor toughness, cracking, hardening, brittleness and the like of the existing organic silicon conductive adhesive after aging are effectively solved. The volume resistivity of the cured conductive adhesive is 4.9 multiplied by 10-4The laminated photovoltaic module has the advantages that the tensile shear strength (namely the bonding strength) is more than 5.6Mpa and the tensile strength is more than 26.9Mpa, so that the problems of low strength and poor caking property of the conventional organic silicon conductive adhesive for the laminated photovoltaic module are effectively solved, the reliability of the laminated photovoltaic module is improved, and the conductive and anti-aging requirements of the laminated photovoltaic module can be met. The conductive adhesive prepared by the invention has better conductivity, lower contact resistance and good toughness, can be widely used for conductive bonding of the photovoltaic laminated assembly cell, simplifies the connection process of the existing laminating technology, and improves the production efficiency and yield of the laminated assembly。
In some preferred embodiments of the present invention, the triazine resin is an s-triazine resin having the formula:
Figure BDA0003169690190000021
in some more preferred embodiments of the present invention, the substituent E of the s-triazine resin1Comprises at least one of an epoxy group, an alicyclic epoxy group or an allyl group.
In some more preferred embodiments of the present invention, the substituent E of the s-triazine resin2Comprises at least one of an epoxy group, an alicyclic epoxy group or an allyl group.
In some more preferred embodiments of the present invention, the substituent E of the s-triazine resin3Comprises at least one of an epoxy group, an alicyclic epoxy group or an allyl group.
In some more preferred embodiments of the present invention, the substituent R of the s-triazine resin1Includes at least one of linear or branched substituents.
In some more preferred embodiments of the present invention, the substituent R of the s-triazine resin2Includes at least one of linear or branched substituents.
In some more preferred embodiments of the present invention, the substituent R of the s-triazine resin3Includes at least one of linear or branched substituents.
In some more preferred embodiments of the present invention, the substituent R of the s-triazine resin1Includes at least one of alkylene, oxyalkylene, or oxyalkylene carbonyl groups.
In some more preferred embodiments of the present invention, the substituent R of the s-triazine resin2Includes at least one of alkylene, oxyalkylene, or oxyalkylene carbonyl groups.
In some more preferred embodiments of the invention, both of saidSubstituent R of triazine resin3Includes at least one of alkylene, oxyalkylene, or oxyalkylene carbonyl groups.
In some embodiments of the present invention, the oxazine resin structure contains unsaturated bonds or epoxy groups or contains both unsaturated bonds and epoxy groups, and due to the unsaturated bonds or epoxy groups, the bonding of the silicone resin containing unsaturated bonds (vinyl silicone resin) and the oxazine resin is facilitated, the cross-linking density of the resin and the adhesive strength and tensile strength of the colloid are improved, and the adhesiveness and aging resistance of the conductive adhesive are improved.
In some embodiments of the invention, the ratio of parts by mass of the vinyl silicone resin to the oxazine resin is (15-90) to (15-60).
In some preferred embodiments of the present invention, the ratio of the parts by mass of the vinyl silicone resin to the oxazine resin is (15-80) to (15-30).
In some preferred embodiments of the present invention, the ratio of the parts by mass of the vinyl silicone resin to the oxazine resin is (15-75) to (15-30).
In some preferred embodiments of the present invention, the ratio of the parts by mass of the vinyl silicone resin to the oxazine resin is (65-80) to (15-30).
In some embodiments of the invention, the oxazine resin includes at least one of triallyl isocyanurate, 1, 3-diallyl isocyanurate, 1-allyl isocyanurate, tris-epoxypropyl isocyanurate, 1, 3-diepoxy propyl isocyanurate, 1-allyl, 3-epoxypropyl isocyanurate, and prepolymers thereof.
In some preferred embodiments of the present invention, the oxazine resin includes at least one of Japanese daily chemical TEPIC-G, Japanese daily chemical TEPIC-P, Japanese daily chemical TEPIC-S, Japanese daily chemical TEPIC-SP, or Japanese daily chemical MT 239.
In some embodiments of the invention, the vinyl silicone resin comprises at least one of MT silicone, MQ silicone, MDT silicone, MTQ silicone, MDQ silicone, or MDTQ silicone.
In some preferred embodiments of the present invention, the vinyl silicone resin comprises at least one of resins of Kjeldahl P-100, Kjeldahl KR-255, Kjeldahl KR-282, Wake SILRES IC368, Wake SILRES IC678, Wake SILRES IC836, Wake SILRES SY300, Dayi chemical VMQ101, Dayi chemical VMQ102, or Dayi chemical VMQ 103.
In some preferred embodiments of the present invention, the crosslinking agent is a hydrogen-containing crosslinking agent.
In some preferred embodiments of the present invention, the hydrogen-containing crosslinking agent is at least one of a linear hydrogen-containing silicone oil or a branched crosslinked hydrogen-containing silicone resin.
In some more preferred embodiments of the present invention, the hydrogen-containing crosslinking agent has a molecular structure containing at least two or more silicon-hydrogen bonds.
In some more preferred embodiments of the present invention, the molecular structure of the hydrogen-containing crosslinking agent is Ha(R4)bSiO(4-a-b)/2Wherein R is4Is a hydrocarbon radical a>0，b>0，a+b≤3。
In some more preferred embodiments of the invention, R4Comprising CH3、C2H5、C6H5At least one of (1).
In some more preferred embodiments of the present invention, 0.001. ltoreq. a.ltoreq.2, 0.7. ltoreq. b.ltoreq.2, 0.8. ltoreq. a + b.ltoreq.3.
In some more preferred embodiments of the present invention, the hydrogen-containing cross-linking agent has silicon hydrogen bonds distributed at both ends or in the middle of the molecular chain.
In some more preferred embodiments of the present invention, the hydrogen-containing crosslinking agent has a hydrogen-containing mass fraction of 0.1% to 1.5%.
In some more preferred embodiments of the present invention, the hydrogen-containing crosslinking agent has a viscosity of 30 to 10000 mPas.
In some more preferred embodiments of the invention, the hydrogen-containing crosslinking agent comprises at least one of Nippon KF-99, Nippon KR-2046, or Dow Corning MHX-1107.
In some preferred embodiments of the present invention, the ratio of the mass parts of the oxazine resin to the crosslinking agent is (15-90) to (3-30).
In some more preferred embodiments of the present invention, the ratio of the mass parts of the oxazine resin to the crosslinking agent is (15-75) to (3-15).
In some more preferred embodiments of the present invention, the ratio of the mass parts of the oxazine resin to the crosslinking agent is (15-30) to (3-8).
In some embodiments of the present invention, the method further comprises the following steps: an accelerator.
In some preferred embodiments of the invention, the promoter comprises at least one of a group VIII metal compound or complex, a group VII metal compound or complex, or a rare earth metal compound.
In some more preferred embodiments of the present invention, the promoter comprises at least one of a platinum-based catalyst, a rhodium-based catalyst, or a palladium-based catalyst.
In some more preferred embodiments of the invention, the promoter comprises at least one of a Speier catalyst, a Karstedt catalyst, or a Wilkinson catalyst.
In some more preferred embodiments of the invention, the promoter comprises a chloroplatinic acid complex catalyst.
In some more preferred embodiments of the present invention, the chloroplatinic acid complex catalyst has a Pt content of 1000-5000 ppm.
In some preferred embodiments of the present invention, the ratio of the mass parts of the oxazine resin to the accelerator is (15-90) to (0.3-3).
In some more preferred embodiments of the present invention, the ratio of the mass parts of the oxazine resin to the accelerator is (15-30) to (0.3-3).
In some more preferred embodiments of the present invention, the ratio of the mass parts of the oxazine resin to the accelerator is (15-30) to (0.3-0.8).
In some embodiments of the present invention, the method further comprises the following steps: and (3) conductive filler.
In some preferred embodiments of the present invention, the conductive filler includes at least one of gold, silver, copper, nickel, or aluminum.
In some more preferred embodiments of the present invention, the conductive filler comprises at least one of gold powder, silver powder, copper powder, nickel powder, silver-coated copper powder, silver-coated glass beads, silver-coated nickel powder, or silver-coated aluminum powder.
In some preferred embodiments of the present invention, the conductive filler is in the shape of at least one of a plate, a sphere-like, a dendrite, or a rod.
In some more preferred embodiments of the present invention, the conductive filler shape includes at least one of a plate shape or a dendritic shape.
In some preferred embodiments of the present invention, the conductive filler has an average particle size ranging from 0.1 to 50 μm.
In some more preferred embodiments of the present invention, the conductive filler has an average particle diameter ranging from 0.5 to 20 μm.
In some more preferred embodiments of the present invention, the conductive filler has an average particle diameter ranging from 5 to 10 μm.
In some preferred embodiments of the present invention, the ratio of the mass fraction of the oxazine resin to the conductive filler is (15-90): 195-800.
In some more preferred embodiments of the present invention, the ratio of the mass fraction of the oxazine resin to the conductive filler is (15-30): (300-800).
The invention provides a preparation method of the conductive adhesive for the laminated photovoltaic module, which comprises the following steps:
s1, mixing and stirring vinyl organic silicon resin, oxazine resin and a cross-linking agent to obtain a mixture I;
s2, adding the conductive filler into the mixture I obtained in the step S1, dispersing and grinding, adding the accelerator, mixing and defoaming.
According to the laminated photovoltaic module conductive adhesive disclosed by the invention, a triazine heterocyclic structure is introduced into the structure of an organic silicon conductive adhesive through molecular structure design, so that the crosslinking density of resin and the tensile strength of the adhesive are improved; meanwhile, the bonding strength and the humidity resistance of the organic silicon can be improved, and the problems of poor toughness, cracking, hardening, brittleness and the like of the conventional organic silicon conductive adhesive after aging are effectively solved. In addition, the conductive adhesive prepared by the invention has better conductivity, lower contact resistance and good toughness, can be widely used for conductive bonding of the photovoltaic laminated assembly cell, simplifies the connection process of the existing laminating technology, and improves the production efficiency and yield of the laminated assembly.
In a third aspect of the invention, the application of the conductive adhesive for the laminated photovoltaic module in a photovoltaic cell packaging material, a laminated photovoltaic module, an electronic component or an integrated circuit is provided.
The triazine heterocyclic structure is introduced into the structure of the organic silicon conductive adhesive through molecular structure design, organic silicon resin (vinyl organic silicon resin) containing unsaturated bonds is combined with hybrid resin of a six-membered heterocyclic triazine structure, the cross-linking density of the resin and the adhesive strength and tensile strength of colloid are improved, and the conductive adhesive for the shingled photovoltaic module, which is high in strength, good in adhesive property and ageing-resistant, is obtained; meanwhile, the moisture and heat resistance of the organic silicon can be improved, and the problems of poor toughness, cracking, hardening, brittleness and the like of the existing organic silicon conductive adhesive after aging are effectively solved.
The volume resistivity of the cured conductive adhesive is 4.9 multiplied by 10-4The laminated photovoltaic module has the advantages that the tensile shear strength (namely the bonding strength) is more than 5.6Mpa and the tensile strength is more than 26.9Mpa, so that the problems of low strength and poor caking property of the conventional organic silicon conductive adhesive for the laminated photovoltaic module are effectively solved, the reliability of the laminated photovoltaic module is improved, and the conductive and anti-aging requirements of the laminated photovoltaic module can be met. The conductive adhesive prepared by the invention has better conductivity, lower contact resistance and good toughness, can be widely used for conductive bonding of the photovoltaic laminated assembly cell, simplifies the connection process of the existing laminating technology, and improves the production efficiency and yield of the laminated assembly.
Detailed Description
The concept and technical effects of the present invention will be clearly and completely described below in conjunction with the embodiments to fully understand the objects, features and effects of the present invention. It is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and those skilled in the art can obtain other embodiments without inventive effort based on the embodiments of the present invention, and all embodiments are within the protection scope of the present invention.
Example 1
The embodiment prepares the conductive adhesive for the laminated photovoltaic module, and the specific process is as follows: adding 50 parts of SILRES IC836, 30 parts of VMQ102, 15 parts of TEPIC-G and 5 parts of KR-2046 into a planetary dispersion stirrer, dispersing and stirring at a high speed, wherein the stirring speed is 1000rpm, adding 300 parts of flake silver powder with the average particle size of 5 mu m in batches after mixing for 30min, and stirring at 80rpm after continuing stirring for 2h under a vacuum state (less than-0.08 MPa); then grinding the slurry for 3 times by using a three-roller grinding machine; after the grinding is finished, transferring the mixture to a stirrer, adding 0.5 part of Karstedt catalyst, and stirring at 20 ℃ and-0.095 MPa in vacuum (rotating speed of 300rpm) for 30min to remove bubbles to obtain the conductive adhesive.
Example 2
The embodiment prepares the conductive adhesive for the laminated photovoltaic module, and the specific process is as follows: adding 50 parts of SILRES IC836, 30 parts of VMQ102, 15 parts of TEPIC-G and 5 parts of KR-2046 into a planetary dispersion stirrer, dispersing and stirring at a high speed, wherein the stirring speed is 1000rpm, adding 400 parts of flake silver powder with the average particle size of 5 mu m in batches after mixing for 30min, and stirring at 80rpm after continuing stirring for 2h under a vacuum state (less than-0.08 MPa); then grinding the slurry for 3 times by using a three-roller grinding machine; after the grinding is finished, transferring the mixture to a stirrer, adding 0.5 part of Karstedt catalyst, and stirring at 20 ℃ and-0.095 MPa in vacuum (rotating speed of 300rpm) for 30min to remove bubbles to obtain the conductive adhesive.
Example 3
The embodiment prepares the conductive adhesive for the laminated photovoltaic module, and the specific process is as follows: adding 40 parts of SILRES IC678, 37 parts of VMQ101, 20 parts of TEPIC-SP and 3 parts of KF-99 into a planetary dispersion stirrer, dispersing and stirring at a high speed, wherein the stirring speed is 1000rpm, mixing for 30min, adding 300 parts of flake silver powder with the average particle size of 5 mu m and 100 parts of dendritic silver powder with the average particle size of 10 mu m in batches, and stirring for 2h under a vacuum state (less than-0.08 Mpa) at a stirring speed of 80 rpm; then grinding the slurry for 3 times by using a three-roller grinding machine; and transferring to a stirrer after grinding is finished, adding 0.3 part of Speier catalyst, and stirring at 20 ℃ and under vacuum of-0.095 MPa (rotating speed of 300rpm) for 30min to remove bubbles to obtain the conductive adhesive.
Example 4
The embodiment prepares the conductive adhesive for the laminated photovoltaic module, and the specific process is as follows: adding 55 parts of KR-255, 10 parts of VMQ103, 30 parts of MT239 and 5 parts of KR-2046 into a planetary dispersion stirrer, carrying out high-speed dispersion stirring at the stirring speed of 1000rpm, mixing for 30min, adding 250 parts of flake silver powder with the average particle size of 5 microns and 150 parts of dendritic silver powder with the average particle size of 10 microns in batches, and stirring for 2h under a vacuum state (less than-0.08 MPa) at the stirring speed of 80 rpm; then grinding the slurry for 3 times by using a three-roller grinding machine; after the grinding is finished, transferring the mixture to a stirrer, adding 0.8 part of Karstedt catalyst, stirring at 20 ℃ and-0.095 MPa in vacuum (rotating speed of 300rpm) for 30min, and removing bubbles to obtain the conductive adhesive.
Example 5
The embodiment prepares the conductive adhesive for the laminated photovoltaic module, and the specific process is as follows: adding 50 parts of SILRES IC836, 30 parts of KR-255, 15 parts of MT239, 3 parts of KR-2046 and 1 part of MHX-1107 into a planetary dispersion stirrer, performing high-speed dispersion stirring at the stirring speed of 1000rpm, mixing for 30min, adding 600 parts of flake silver powder with the average particle size of 5 mu m and 200 parts of dendritic silver powder with the average particle size of 10 mu m in batches, and stirring for 2h under vacuum (less than-0.08 MPa) at the stirring speed of 80 rpm; then grinding the slurry for 3 times by using a three-roller grinding machine; after the grinding is finished, transferring the mixture to a stirrer, adding 0.8 part of Karstedt catalyst, stirring at 20 ℃ and-0.095 MPa in vacuum (rotating speed of 300rpm) for 30min, and removing bubbles to obtain the conductive adhesive.
Example 6
The embodiment prepares the conductive adhesive for the laminated photovoltaic module, and the specific process is as follows: adding 17 parts of SILRES SY300, 30 parts of KR-255, 20 parts of VMQ101, 25 parts of TEPIC-SP and 8 parts of KR-2046 into a planetary dispersing mixer, dispersing and stirring at a high speed of 1000rpm, mixing for 30min, adding 550 parts of flake silver powder with an average particle size of 5 microns and 150 parts of dendritic silver powder with an average particle size of 10 microns in batches, and stirring for 2h under vacuum (less than-0.08 MPa) at a stirring speed of 80 rpm; then grinding the slurry for 3 times by using a three-roller grinding machine; after the grinding is finished, transferring the mixture to a stirrer, adding 0.5 part of Karstedt catalyst, and stirring at 20 ℃ and-0.095 MPa in vacuum (rotating speed of 300rpm) for 30min to remove bubbles to obtain the conductive adhesive.
Test examples
The performance of the conductive adhesive for the laminated photovoltaic module prepared in the embodiment is tested in the test example. Wherein:
determination of tensile shear strength (test of bond strength):
the tensile shear strength was tested according to the requirements specified in GB7124-86 adhesive tensile shear Strength determination method, Metal to Metal, and loaded at a steady speed of (100 + -10) mm/min.
Testing of volume resistivity:
the slide glass is cleaned by absolute ethyl alcohol, an insulating adhesive tape is pasted, the middle part is cut into a standard rectangle by a steel knife, and then the conductive adhesive is smeared. And placing the coated slide glass into an oven for curing. After curing, after the conductive adhesive is cooled, the thickness of the conductive adhesive sheet is measured by a micrometer, the width of the conductive adhesive is measured by a vernier caliper, and the resistance is directly measured by a direct current digital resistance tester.
The volume resistivity was calculated according to the following formula (1).
Figure BDA0003169690190000091
In the formula: ρ -resistivity, Ω · cm;
r-measured resistance, Ω;
w is the width of the glue layer, cm;
t is the thickness of the adhesive layer, cm;
l is the length of the glue layer, cm.
Measuring the thickness of five places on each slide glass, and taking the average value; 5 samples were made for each formulation and the 5 resistivities were averaged.
Testing of tensile Strength:
the tensile strength was tested according to the requirements specified in GB/T6329-1996 determination of the tensile strength of the adhesive butt joint.
The results of testing the adhesive strength, volume resistivity, and tensile strength of the conductive paste for a laminated photovoltaic module prepared in examples 1 to 6 are shown in table 1 below:
table 1 performance test results of conductive adhesive for shingled photovoltaic modules
Figure BDA0003169690190000092
According to the conductive adhesive for the laminated photovoltaic module, a triazine heterocyclic structure is introduced into the structure of the organic silicon conductive adhesive through molecular structure design, so that the crosslinking density of resin and the adhesive strength and tensile strength of colloid are improved, and the conductive adhesive for the laminated photovoltaic module is high in strength, good in adhesive property and ageing-resistant; meanwhile, the moisture and heat resistance of the organic silicon can be improved, and the problems of poor toughness, cracking, hardening, brittleness and the like of the existing organic silicon conductive adhesive after aging are effectively solved.
The volume resistivity of the cured conductive adhesive is 4.9 multiplied by 10-4The stretching shear strength is below 5.6Mpa, the stretching strength is above 26.9Mpa, the problems of low strength and poor caking property of the current organic silicon conductive adhesive for the laminated photovoltaic module are effectively solved, the reliability of the laminated photovoltaic module is improved, and the conductive and anti-aging requirements of the laminated photovoltaic module can be met. The conductive adhesive prepared by the invention has better conductivity, lower contact resistance and good toughness, can be widely used for conductive bonding of the photovoltaic laminated assembly cell, simplifies the connection process of the existing laminating technology, and improves the production efficiency and yield of the laminated assembly.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention.

Claims (10)

1. The utility model provides a shingled photovoltaic module is with conducting resin which characterized in that, including following raw materials: vinyl silicone resin, oxazine resin and crosslinking agent.
2. The conductive adhesive for the laminated photovoltaic module according to claim 1, wherein the triazine resin comprises a triazine resin; preferably, the triazine resin is an s-triazine resin, and the structural formula is as follows:
Figure FDA0003169690180000011
preferably, the substituent E of the s-triazine resin1Comprises at least one of epoxy group, alicyclic epoxy group or allyl group, and a substituent E of the s-triazine resin2Comprises at least one of epoxy group, alicyclic epoxy group or allyl group, and a substituent E of the s-triazine resin3Comprises at least one of epoxy group, alicyclic epoxy group or allyl group;
preferably, the substituent R of the s-triazine resin1Comprises at least one of linear or branched substituents, and a substituent R of the s-triazine resin2Comprises at least one of linear or branched substituents, and a substituent R of the s-triazine resin3Includes at least one of linear or branched substituents;
preferably, the substituent R of the s-triazine resin1Including at least one of alkylene, oxyalkylene or oxyalkylene carbonyl, and the substituent R of the s-triazine resin2Including at least one of alkylene, oxyalkylene or oxyalkylene carbonyl groups, the s-triazine resinSubstituent R3Includes at least one of alkylene, oxyalkylene, or oxyalkylene carbonyl groups.
3. The conductive adhesive for the laminated photovoltaic module as claimed in claim 1, wherein the ratio of the mass parts of the vinyl silicone resin to the mass parts of the oxazine resin is (15-90) to (15-60); preferably, the mass part ratio of the vinyl organic silicon resin to the oxazine resin is (15-80) to (15-30); preferably, the mass part ratio of the vinyl organic silicon resin to the oxazine resin is (15-75) to (15-30); preferably, the mass part ratio of the vinyl organic silicon resin to the oxazine resin is (65-80) to (15-30).
4. The conductive adhesive for a photovoltaic module, according to claim 1, wherein the oxazine resin comprises at least one of triallyl isocyanurate, 1, 3-diallyl isocyanurate, 1-allyl isocyanurate, tris-epoxypropyl isocyanurate, 1, 3-diepoxy propyl isocyanurate, 1-allyl, 3-epoxypropyl isocyanurate, and prepolymers thereof; preferably, the oxazine resin includes at least one of daily chemical TEPIC-G, daily chemical TEPIC-P, daily chemical TEPIC-S, daily chemical TEPIC-SP, or daily chemical MT 239.
5. The conductive adhesive for a laminated photovoltaic module according to claim 1, wherein the vinyl silicone resin comprises at least one of MT silicone resin, MQ silicone resin, MDT silicone resin, MTQ silicone resin, MDQ silicone resin, or MDTQ silicone resin; preferably, the vinyl silicone resin comprises at least one of resins of Xinyue KSP-100, Xinyue KR-255, Xinyue KR-282, Wake SILRES IC368, Wake SILRES IC678, Wake SILRES IC836, Wake SILRESSY300, Dayi chemical VMQ101, Dayi chemical VMQ102 or Dayi chemical VMQ 103.
6. The conductive adhesive for the laminated photovoltaic module according to claim 1, wherein the conductive adhesive is prepared by mixing a conductive resin and a binderWherein the crosslinking agent is a hydrogen-containing crosslinking agent; preferably, the hydrogen-containing crosslinking agent is at least one of linear hydrogen-containing silicone oil or branched crosslinked hydrogen-containing silicone resin; preferably, the molecular structure of the hydrogen-containing cross-linking agent at least contains two or more silicon-hydrogen bonds; preferably, the molecular structural formula of the hydrogen-containing cross-linking agent is Ha(R4)bSiO(4-a-b)/2Wherein R is4Is a hydrocarbon radical a>0，b>0, a + b is less than or equal to 3; preferably, R4Comprising CH3、C2H5、C6H5At least one of; preferably, 0.001. ltoreq. a.ltoreq.2, 0.7. ltoreq. b.ltoreq.2, 0.8. ltoreq. a + b.ltoreq.3; preferably, the silicon-hydrogen bonds in the hydrogen-containing cross-linking agent are distributed at two ends or in the middle of a molecular chain; preferably, the hydrogen-containing cross-linking agent has a hydrogen-containing mass fraction of 0.1% to 1.5%; preferably, the hydrogen-containing cross-linking agent has a viscosity of 30 to 10000mPa · s; preferably, the hydrogen-containing cross-linking agent comprises at least one of Xinyue KF-99, Xinyue KR-2046 or Dow Corning MHX-1107; preferably, the mass part ratio of the oxazine resin to the cross-linking agent is (15-90) to (3-30); preferably, the mass part ratio of the oxazine resin to the cross-linking agent is (15-75) to (3-15); preferably, the mass part ratio of the oxazine resin to the cross-linking agent is (15-30) to (3-8).
7. The conductive adhesive for the laminated photovoltaic module according to claim 1, further comprising the following raw materials: an accelerator; preferably, the promoter comprises at least one of a group VIII metal compound or complex, a group VII metal compound or complex or a rare earth metal compound; preferably, the promoter comprises at least one of a platinum-series catalyst, a rhodium-series catalyst or a palladium-series catalyst; preferably, the promoter comprises at least one of a Speier catalyst, a Karstedt catalyst, or a Wilkinson catalyst; preferably, the promoter comprises a chloroplatinic acid complex catalyst; preferably, the chloroplatinic acid complex catalyst has a Pt content of 1000-5000 ppm; preferably, the mass part ratio of the oxazine resin to the accelerator is (15-90) to (0.3-3); preferably, the mass part ratio of the oxazine resin to the accelerator is (15-30) to (0.3-3); preferably, the mass part ratio of the oxazine resin to the accelerator is (15-30) to (0.3-0.8).
8. The conductive adhesive for the laminated photovoltaic module according to claim 1, further comprising the following raw materials: a conductive filler; the conductive filler comprises at least one of gold, silver, copper, nickel or aluminum; preferably, the conductive filler comprises at least one of gold powder, silver powder, copper powder, nickel powder, silver-coated copper powder, silver-coated glass beads, silver-coated nickel powder or silver-coated aluminum powder; preferably, the conductive filler is at least one of flaky, spherical, spheroidal, dendritic or rod-like in shape; preferably, the conductive filler shape includes at least one of a plate shape or a dendritic shape; preferably, the conductive filler has an average particle diameter ranging from 0.1 to 50 μm; preferably, the conductive filler has an average particle diameter ranging from 0.5 to 20 μm; preferably, the conductive filler has an average particle diameter ranging from 5 to 10 μm; preferably, the mass part ratio of the oxazine resin to the conductive filler is (15-90): 195-800); preferably, the ratio of the mass parts of the oxazine resin to the conductive filler is (15-30): (300-800).
9. A preparation method of a conductive adhesive for a laminated photovoltaic module is characterized by comprising the following steps:
s1, mixing and stirring vinyl organic silicon resin, oxazine resin and a cross-linking agent to obtain a mixture I;
s2, adding the conductive filler into the mixture I obtained in the step S1, dispersing and grinding, adding the accelerator, mixing and defoaming.
10. Use of the conductive adhesive for a tiled photovoltaic module according to any one of claims 1 to 8 or the conductive adhesive for a tiled photovoltaic module prepared by the preparation method of claim 9 in photovoltaic cell packaging materials, tiled photovoltaic modules, electronic components or integrated circuits.
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CN109749702A (en) * 2018-12-28 2019-05-14 广州市儒兴科技开发有限公司 A kind of conducting resinl and preparation method thereof for imbrication photovoltaic module
CN109762167A (en) * 2018-12-14 2019-05-17 中国科学院深圳先进技术研究院 A kind of LED small-size chips heat conductive insulating die bond material and preparation method thereof
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Publication number Priority date Publication date Assignee Title
JP2021004362A (en) * 2016-02-15 2021-01-14 三洋化成工業株式会社 Antistatic silicone resin composition
CN109762167A (en) * 2018-12-14 2019-05-17 中国科学院深圳先进技术研究院 A kind of LED small-size chips heat conductive insulating die bond material and preparation method thereof
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