CN112961625A - Conductive silver adhesive and preparation method and application thereof - Google Patents

Conductive silver adhesive and preparation method and application thereof Download PDF

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Publication number
CN112961625A
CN112961625A CN202110152330.2A CN202110152330A CN112961625A CN 112961625 A CN112961625 A CN 112961625A CN 202110152330 A CN202110152330 A CN 202110152330A CN 112961625 A CN112961625 A CN 112961625A
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silver
silver powder
modified
resin
conductive
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CN112961625B (en
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王传博
邸江涛
王晓娜
李清文
包健
敖毅伟
岡本珍範
刘海东
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Changzhou Fusion New Material 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
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • C09J9/02—Electrically-conducting adhesives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • 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
    • C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
    • C09J161/04—Condensation polymers of aldehydes or ketones with phenols only
    • C09J161/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • 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
    • C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
    • C09J161/04—Condensation polymers of aldehydes or ketones with phenols only
    • C09J161/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • C09J161/14—Modified phenol-aldehyde condensates
    • 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
    • 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

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Conductive Materials (AREA)

Abstract

The invention discloses a conductive silver adhesive and a preparation method and application thereof. The preparation method comprises the following steps: fully contacting the silver powder with a modifier for reaction, and then carrying out illumination treatment, so as to generate silver nano particles on the surface of the silver powder and obtain modified silver powder; wherein the modifier comprises any one of a potassium iodide solution, an iodine solution and oxalic acid; and mixing the modified silver powder, the resin matrix and the solvent for dispersion treatment to obtain the conductive silver adhesive. The modification treatment of the silver powder has strong controllability, and the preparation method of the conductive silver adhesive is simple and can be used for industrial production; the preparation process is all nontoxic reagents, and meets the requirements of environmental protection and low energy consumption; meanwhile, the conductive silver adhesive prepared by the invention and the preparation method thereof are combined with actual production, so that the conductive silver adhesive not only has strong academic significance, but also has good economic benefit.

Description

Conductive silver adhesive and preparation method and application thereof
Technical Field
The invention belongs to the technical field of conductive silver adhesive, and particularly relates to conductive silver adhesive and a preparation method and application thereof.
Background
The conductive adhesive is an adhesive which has connection performance and conductive performance after being cured, is a composite material and generally consists of conductive filler and a resin matrix. The resin matrix (typically including epoxy, polyimide, silicone, and polyurethane, etc.) provides physical and mechanical properties, and the metal filler (gold, silver, copper, and nickel, etc.) provides electrical conductivity. The main components of the conductive adhesive are a resin matrix, a curing agent and a conductive filler. Compared with the traditional lead-containing solder, the solder has low use temperature, and can be used even at room temperature; lead element is not contained, and the environment is not polluted; the viscosity is controllable, the linear resolution is high, and a fine structure can be welded; the sample has the advantages of wide application range and the like, so that the lead-containing solder can be replaced in the electronic packaging material.
Common conductive fillers are gold, silver, copper, nickel, gold (resistivity: 2.404X 10)-6Ω. cm) has good conductivity and resistance stability, but it is very expensive, mostly for precision instruments or aerospaceThe field of the technology. Silver (resistivity: 1.62X 10)-6Omega cm) has good electrical conductivity and thermal conductivity, and the silver oxide has certain electrical conductivity and the price is far lower than that of gold, so the silver is widely used as the conductive filler of the conductive adhesive. Copper (resistivity: 5.92X 10)-6Omega cm) also has better conductivity and low price, but has poor resistance stability, and is easier to generate oxidation reaction with oxygen in the air to generate a non-conductive oxide layer, so that the conductivity of the conductive adhesive is discontinuous. The silver-coated copper powder integrates the advantages of silver and copper, has low price, good conductivity and certain resistance stability, but the oxidation resistance of the silver-coated copper powder needs to be further improved. Nickel (resistivity: 7.234X 10)-6Ω · cm), aluminum (resistivity: 2.624X 10-6Omega cm), iron, etc. are generally used as conductive fillers in the form of alloys with metals such as gold, silver, etc. in conductive adhesives because they have higher intrinsic conductivity than those of gold, silver, etc. and are easily affected by moisture and oxygen in the air, easily oxidized, and unstable in resistivity. As described above, since the silver filler has good electrical conductivity, thermal conductivity and its oxide formed also have electrical conductivity, the price is relatively low.
The relatively common silver fillers are generally prepared by ball milling, and some fatty acid is added as a lubricant during ball milling, and the lubricant makes the ball milling process easier. Therefore, the prepared silver powder has a lubricant adsorbed on the surface, and although the lubricant can enhance the interaction between the conductive silver filler and the resin and improve the dispersion of the silver powder in the resin, the lubricant is insulating and can adversely affect the conductivity of the conductive paste. Therefore, in order to improve the conductive performance of the conductive silver paste, it is generally required to reduce the content of the surface-moistening agent of the conductive silver filler as much as possible without affecting the dispersibility of the conductive silver filler in the resin. The proportion content of silver powder in the conductive silver adhesive on the market is about 70 wt% -80 wt%, and the resistivity of the prepared conductive silver adhesive is 10-4On the order of Ω. However, there are few reports on high-content and low-resistivity conductive silver adhesive.
Disclosure of Invention
The invention mainly aims to provide conductive silver adhesive, a preparation method and application thereof, so as to overcome the defects of the prior art.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a preparation method of conductive silver adhesive, which comprises the following steps:
fully contacting the silver powder with a modifier for reaction, and then carrying out illumination treatment, so as to generate silver nanoparticles on the surface of the silver powder and obtain modified silver powder, wherein the modifier comprises any one of a potassium iodide solution, an iodine solution and oxalic acid;
and mixing the modified silver powder, the resin matrix and the solvent for dispersion treatment to obtain the conductive silver adhesive.
The embodiment of the invention also provides the conductive silver adhesive prepared by the method.
The embodiment of the invention also provides application of the conductive silver adhesive in preparation of photoelectric devices.
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the invention, high-content modified silver powder is used as a conductive filler, and the surface of the conductive filler is modified and irradiated to generate silver nano particles, so that the contact between adjacent silver powder and silver powder is increased, the conductivity of the conductive filler is further improved, and the conductive filler has an obvious effect when applied to conductive silver adhesive;
(2) the silver powder is modified, the technical controllability is strong, the preparation method of the conductive silver adhesive is simple, and the conductive silver adhesive can be used for industrial production; the preparation process is all nontoxic reagents, and meets the requirements of environmental protection and low energy consumption;
(3) the conductive silver adhesive and the preparation method thereof are combined with actual production, so that the conductive silver adhesive not only has strong academic significance, but also has good economic benefit.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments described in the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIGS. 1a to 1b are respective pictures of printed samples prepared in example 1 of the present invention;
FIG. 2 is an infrared spectrum of a surface-treated silver powder obtained by modifying a silver powder with potassium iodide solutions of different concentrations in example 1 of the present invention;
FIG. 3 is a line resistance diagram of conductive silver pastes prepared in example 1 and comparative example 1 of the present invention;
FIG. 4 is a graph showing the volume resistance of the conductive silver paste prepared in example 1 of the present invention and comparative example 1;
FIG. 5 is a graph showing the viscosity of conductive silver paste prepared in example 1 of the present invention and comparative example 1;
FIG. 6 is a graph showing the tensile strength of conductive silver paste prepared in example 1 of the present invention and comparative example 1;
FIG. 7 is a 3D micrograph of a conductive silver paste prepared by modifying silver powder with 0.025mol/L potassium iodide solution according to this example;
FIGS. 8a to 8b are pictures of silver powder before and after the solar light irradiation treatment in example 1.
Detailed Description
In view of the defects of the prior art, the inventor of the present invention has long studied and largely practiced to propose the technical solution of the present invention, which will be clearly and completely described below, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
One aspect of the embodiments of the present invention provides a method for preparing conductive silver paste, which includes:
fully contacting the silver powder with a modifier for reaction, and then carrying out illumination treatment, so as to generate silver nanoparticles on the surface of the silver powder and obtain modified silver powder, wherein the modifier comprises any one of a potassium iodide solution, an iodine solution and oxalic acid;
and mixing the modified silver powder, the resin matrix and the solvent for dispersion treatment to obtain the conductive silver adhesive.
Furthermore, the resin matrix has better adhesive property with the TCO film.
Further, the molecular weight of the resin matrix is 300-60000 Da.
Further, the solvent includes any one or a combination of two or more of terpineol, diethylene glycol butyl ether acetate, and decaglycol ester, and is not limited thereto.
Further, the resin matrix includes any one or a combination of two or more of epoxy resin, acrylic resin, phenol resin, bisphenol a resin, bisphenol F resin, modified epoxy resin, modified acrylic resin, modified phenol resin, modified bisphenol a resin, and modified bisphenol F resin, and is not limited thereto.
In some more specific embodiments, the silver powder comprises silver nanoplatelets and/or silver microspheres.
Further, the silver powder has a particle size of 3-15 μm and a volume resistivity of 4.0 × 10-6～7.0×10-6Ω·em。
In some more specific embodiments, the preparation method comprises: mixing the silver powder and the modifier, and reacting for 30-60 min under the conditions that the rotating speed is 800-1000 rpm and the temperature is 25-30 ℃.
Further, the preparation method further comprises the following steps: after the reaction is completed, the obtained mixture is washed and dried.
In some more specific embodiments, the preparation method comprises: reacting silver powder with a modifier to obtain a mixture, wherein the illumination intensity of the mixture is 1000-1200W/m2The modified silver powder is obtained after 1-2 h of illumination treatment under the condition of (1).
In the invention, the silver nanoparticles can be generated on the surface of the silver powder by illumination.
In the invention, the silver powder after being treated is subjected to solar irradiation treatment,the silver nanoparticles are generated on the surface of the silver-based composite material, the small-size silver particles can be sintered in the curing process, the contact between the adjacent silver powder and the silver powder is increased, the conductivity of the silver-based composite material is further improved, the silver-based composite material is applied to production, the effect is obvious, and the principle is as follows: 2I-+Ag2O+H 20→2OH-+2 AgI; and the silver iodide is subjected to light treatment, silver particles and iodine vapor are generated by the decomposition of the silver iodide after the light treatment, only the silver particles are remained, and the contact area between adjacent silver powders is increased by the silver particles in the sintering process, so that the conductivity of the silver powder is improved.
In the invention, the used oxalic acid in situ replaces long-chain lubricant molecules on the surface of the conductive filler, partial long-chain lubricant molecules are removed, and the contact between the conductive filler and the conductive filler is increased, so that the conductivity can be improved.
In some more specific embodiments, the preparation method comprises: and mixing the modified silver powder, the resin matrix and a solvent, and then carrying out defoaming, dispersing and centrifuging to obtain the conductive silver adhesive.
Further, the preparation method comprises the following steps: and carrying out the dispersion treatment by adopting a three-roller machine.
In some more specific embodiments, the modifier includes any one or a combination of two or more of potassium iodide solution, iodine solution, oxalic acid, and is not limited thereto.
Further, the concentration of the potassium iodide solution is 0.006-0.1 mol/L.
In some more specific embodiments, the method for preparing the conductive silver paste specifically comprises:
(1) surface treatment of silver powder: preparing potassium iodide solutions with different concentrations, wherein the concentrations are 0.006mol/L, 0.0125mol/L, 0.025mol/L, 0.05mol/L and 0.1mol/L respectively, then adding a silver powder sample, sticking a preservative film to prevent liquid and the sample from splashing out during magneton stirring, controlling the rotating speed to be 800-;
(2) preparing conductive silver adhesive: mixing the modified silver powder, the organic carrier (resin matrix) and a solvent (wherein the mass ratio of the modified silver powder to the bisphenol A resin is 9: 1), putting the mixture into a centrifuge for mixing and defoaming, then dispersing the mixture in a three-roll machine to uniformly disperse the mixture, then performing centrifugal treatment after the treatment of the three-roll machine to further improve the dispersibility of the slurry, and finally performing printing treatment on the dispersed conductive silver adhesive to print the conductive silver adhesive on a photovoltaic panel.
Although the promotion of the conductive silver adhesive is not several orders of magnitude, in the actual industrial production of the conductive silver adhesive, the small promotion is a great progress on the cost and the performance of the industrial production.
In another aspect of the embodiment of the invention, the conductive silver adhesive prepared by the method is also provided.
Further, the conductive silver adhesive comprises 85-95 wt% of modified silver powder, 5-15 wt% of resin matrix, and the balance of solvent.
Further, the resin matrix includes any one or a combination of two or more of epoxy resin, acrylic resin, phenol resin, bisphenol a resin, bisphenol F resin, modified epoxy resin, modified acrylic resin, modified phenol resin, modified bisphenol a resin, and modified bisphenol F resin, and is not limited thereto.
Further, the solvent includes any one or a combination of two or more of terpineol, diethylene glycol butyl ether acetate, and decaglycol ester, and is not limited thereto.
Another aspect of the embodiments of the present invention also provides a use of the aforementioned conductive silver paste in the preparation of a photovoltaic device.
For example, the conductive silver paste is printed on the photovoltaic panel through a printing process.
The technical solutions of the present invention are further described in detail below with reference to several preferred embodiments and the accompanying drawings, which are implemented on the premise of the technical solutions of the present invention, and a detailed implementation manner and a specific operation process are provided, but the scope of the present invention is not limited to the following embodiments.
The experimental materials used in the examples used below were all available from conventional biochemical reagents companies, unless otherwise specified.
Example 1
(1) Preparing potassium iodide solutions with different concentrations (the concentrations are respectively 0.006mol/L, 0.0125mol/L, 0.025mol/L, 0.05mol/L and 0.1mol/L), mixing with silver powder, stirring at 900rpm to make the silver powder and the potassium iodide solution fully contact and react for 45min at 27 ℃, washing the reacted silver powder with absolute ethyl alcohol for 4-5 times to remove redundant potassium iodide solution, drying to obtain surface-treated silver powder, and illuminating at the illumination intensity of 1100W/m2Carrying out illumination treatment for 1.5h to obtain modified silver powder;
(2) mixing the modified silver powder, the bisphenol A resin and the terpineol (wherein the mass ratio of the modified silver powder to the bisphenol A resin is 9: 1), then putting the mixture into a centrifuge for mixing and defoaming, then carrying out dispersion treatment and centrifugation treatment on the mixture by a three-roll machine to obtain conductive silver colloid, and finally carrying out printing treatment on the dispersed conductive silver colloid to obtain a printing sample.
Comparative example 1
The preparation method was the same as example 1 except that the silver powder in this comparative example was not subjected to light treatment and the concentration of the potassium iodide solution was 0.025 mol/L.
And (3) performance characterization:
FIGS. 1 a-1 b are photographs of printed samples prepared according to example 1 of the present invention;
FIG. 2 is an infrared spectrum of the surface-treated silver powder obtained by modifying silver powder with potassium iodide solutions of different concentrations in this example 1, from which it can be seen that the lubricant is 1000-3700cm-1Infrared signals appear in the range of 3000cm-1There is an absorption peak of carboxylic acid nearby, that is, a characteristic peak of the dispersant, and it can be seen from the figure that the infrared signal intensity of the characteristic peak of the silver powder sample after treatment is lower as the KI concentration is increased, that is, the dispersant on the surface of the silver powder can be partially removed by using the KI reagent.
FIGS. 3 and 4 are graphs of the line resistance and the volume resistance of the conductive silver paste prepared by modifying silver powder with potassium iodide solutions of different concentrations in example 1 and the conductive silver paste prepared in comparative example 1, respectively; FIG. 5 is a graph showing the viscosity of conductive silver pastes prepared by modifying silver powder with potassium iodide solutions of different concentrations according to example 1 and the conductive silver paste prepared according to comparative example 1; FIG. 6 is a graph showing the tensile strength of the conductive silver paste prepared by modifying silver powder with potassium iodide solutions of different concentrations according to example 1 and the conductive silver paste prepared according to comparative example 1; FIG. 7 is a 3D micrograph of a conductive silver paste prepared by modifying silver powder with 0.025mol/L potassium iodide solution according to this example; FIGS. 8a to 8b are pictures of silver powder before and after the solar light irradiation treatment in example 1.
As can be seen from fig. 3 to fig. 6, the conductivity, viscosity and tensile strength of the conductive silver paste prepared by the light irradiation treatment are all improved obviously.
Example 2
(1) Mixing iodine solution (concentration of 0.0125mol/L) with silver powder, stirring at 800rpm to make the silver powder and iodine solution contact sufficiently, reacting at 25 deg.C for 60min, washing the reacted silver powder with anhydrous ethanol for 4 times to remove excessive iodine solution, drying to obtain surface-treated silver powder, and irradiating at illumination intensity of 1000W/m2The modified silver powder is obtained after 2 hours of illumination treatment under the condition of (1);
(2) mixing modified silver powder, modified phenolic resin and diethylene glycol monobutyl ether acetate (wherein the mass ratio of the modified silver powder to the modified phenolic resin is 9: 1), then placing the mixture into a centrifugal machine for mixing and defoaming, then performing dispersion treatment and centrifugal treatment on a three-roll machine to obtain conductive silver colloid, and finally performing printing treatment on the dispersed conductive silver colloid to obtain a printed sample, wherein the line resistance of the conductive silver colloid is 1.81 omega, and the volume resistance is 5.6 x 10-6Ω·cm。
Example 3
(1) Mixing oxalic acid (concentration is 0.0125mol/L) and silver powder, stirring at 1000rpm to make the silver powder and oxalic acid fully contact and react at 30 deg.C for 30min, washing the reacted silver powder with anhydrous ethanol for 4 times to remove excessive oxalic acid, drying to obtain surface-treated silver powder, and illuminating at 1200W/m2Is irradiated with light for 1h under the conditions of (1) to obtainObtaining modified silver powder;
(2) mixing modified silver powder, modified phenolic resin and dodecanol ester (wherein the mass ratio of the modified silver powder to the dodecanol ester is 9: 1), then putting the mixture into a centrifuge for mixing and defoaming, then carrying out dispersion treatment and centrifugation treatment on the mixture by a three-roll machine to obtain conductive silver colloid, and finally carrying out printing treatment on the dispersed conductive silver colloid to obtain a printed sample, wherein the line resistance of the conductive silver colloid is 1.85 omega, and the volume resistance is 5.73 x 10-6Ω·cm。
In addition, the inventors of the present invention have also made experiments with other materials, process operations, and process conditions described in the present specification with reference to the above examples, and have obtained preferable results.
The aspects, embodiments, features and examples of the present invention should be considered as illustrative in all respects and not intended to be limiting of the invention, the scope of which is defined only by the claims. Other embodiments, modifications, and uses will be apparent to those skilled in the art without departing from the spirit and scope of the claimed invention.
The use of headings and chapters in this disclosure is not meant to limit the disclosure; each section may apply to any aspect, embodiment, or feature of the disclosure.
Throughout this specification, where a composition is described as having, containing, or comprising specific components or where a process is described as having, containing, or comprising specific process steps, it is contemplated that the composition of the present teachings also consist essentially of, or consist of, the recited components, and the process of the present teachings also consist essentially of, or consist of, the recited process steps.
It should be understood that the order of steps or the order in which particular actions are performed is not critical, so long as the teachings of the invention remain operable. Further, two or more steps or actions may be performed simultaneously.
While the invention has been described with reference to illustrative embodiments, it will be understood by those skilled in the art that various other changes, omissions and/or additions may be made and substantial equivalents may be substituted for elements thereof without departing from the spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from its scope. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims. Moreover, unless specifically stated any use of the terms first, second, etc. do not denote any order or importance, but rather the terms first, second, etc. are used to distinguish one element from another.

Claims (10)

1. The preparation method of the conductive silver adhesive is characterized by comprising the following steps:
fully contacting the silver powder with a modifier for reaction, and then carrying out illumination treatment, so as to generate silver nanoparticles on the surface of the silver powder and obtain modified silver powder, wherein the modifier comprises any one of a potassium iodide solution, an iodine solution and oxalic acid;
and mixing the modified silver powder, the resin matrix and the solvent for dispersion treatment to obtain the conductive silver adhesive.
2. The production method according to claim 1, characterized by comprising: mixing the silver powder and the modifier, and reacting for 30-60 min under the conditions that the rotating speed is 800-1000 rpm and the temperature is 25-30 ℃.
3. The method of claim 2, further comprising: after the reaction is completed, the obtained mixture is washed and dried.
4. The production method according to claim 1, characterized by comprising: reacting silver powder with a modifier to obtain a mixture, wherein the illumination intensity of the mixture is 1000-1200W/m2The modified silver powder is obtained after illumination treatment for 1-2 hours under the condition of (1).
5. The production method according to claim 1, characterized by comprising: mixing the modified silver powder, the resin matrix and a solvent, and then carrying out defoaming, dispersing and centrifuging to obtain the conductive silver adhesive;
preferably, the preparation method comprises the following steps: and carrying out the dispersion treatment by adopting a three-roller machine.
6. The method of claim 1, wherein: the concentration of the potassium iodide solution is 0.006-0.1 mol/L;
and/or the molecular weight of the resin matrix is 300-;
and/or the solvent comprises one or the combination of more than two of terpineol, diethylene glycol butyl ether acetate and glycol decahydrate;
and/or the resin matrix comprises any one or the combination of more than two of epoxy resin, acrylic resin, phenolic resin, bisphenol A resin, bisphenol F resin, modified epoxy resin, modified acrylic resin, modified phenolic resin, modified bisphenol A resin and modified bisphenol F resin.
7. The method of claim 1, wherein: the silver powder comprises silver micron sheets and/or silver micron balls;
and/or the silver powder has the particle size of 3-15 mu m and the volume resistivity of 4.0 multiplied by 10-6～7.0×10-6Ω·cm。
8. Conductive silver paste produced by the method of any one of claims 1 to 7.
9. The conductive silver paste of claim 8, wherein: the conductive silver adhesive comprises 85-95 wt% of modified silver powder, 5-15 wt% of resin matrix and the balance of solvent.
10. Use of the conductive silver paste of claim 8 or 9 for the preparation of an optoelectronic device.
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KR101701317B1 (en) * 2016-04-01 2017-02-03 (주) 퓨리켐 Electro-conductive adhesive using graphene and preparation of electrode using the same
CN106753026A (en) * 2016-12-30 2017-05-31 中国科学院深圳先进技术研究院 The modified method in surface, modified silver powder and the conductive silver glue comprising it are carried out to silver powder

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Publication number Priority date Publication date Assignee Title
CN105733470A (en) * 2014-12-11 2016-07-06 中国科学院苏州纳米技术与纳米仿生研究所 Modified conductive filling material, preparation method thereof and application
KR101701317B1 (en) * 2016-04-01 2017-02-03 (주) 퓨리켐 Electro-conductive adhesive using graphene and preparation of electrode using the same
CN106753026A (en) * 2016-12-30 2017-05-31 中国科学院深圳先进技术研究院 The modified method in surface, modified silver powder and the conductive silver glue comprising it are carried out to silver powder

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