CN110423573B - Conductive silver adhesive and preparation method and application thereof - Google Patents
Conductive silver adhesive and preparation method and application thereof Download PDFInfo
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- CN110423573B CN110423573B CN201910760519.2A CN201910760519A CN110423573B CN 110423573 B CN110423573 B CN 110423573B CN 201910760519 A CN201910760519 A CN 201910760519A CN 110423573 B CN110423573 B CN 110423573B
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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
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
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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
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- 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
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- 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
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- 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
- C08K2201/011—Nanostructured additives
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Abstract
The invention provides a conductive silver adhesive and a preparation method and application thereof. The conductive silver adhesive comprises silver nano sheets and a low-modulus high-molecular polymer carrier, wherein the low-modulus high-molecular polymer carrier comprises a low-modulus high-molecular polymer and an organic solvent, the elastic modulus of the low-modulus high-molecular polymer is less than 100MPa, the organic solvent accounts for 60-80% of the total weight of the high-molecular polymer carrier, the silver nano sheets account for 70-90% of the total weight of the silver nano sheets and the low-modulus high-molecular polymer, and the low-modulus high-molecular polymer accounts for 10-30%. The invention uses low modulus high molecular polymer as the adhesive of the conductive silver adhesive, which is adapted to the modulus of the flexible circuit, and different modulus polymers can meet the requirements of flexible circuits with different moduli. Under larger strain, the two-dimensional material silver nanosheet in the conductive silver adhesive can still maintain a good conductive path, so that the conductive silver adhesive has high tensile property and conductive performance.
Description
Technical Field
The invention relates to the field of conductive adhesives, and particularly relates to a conductive silver adhesive and a preparation method and application thereof.
Background
In recent years, flexible, stretchable, bendable electronic devices have become more and more appreciated, such as bending displays and touch screens, radio frequency identification tags, wearable sensors, implantable medical devices, bracelets, watches, and even cell phones, and the like. Flexibility and bendability are the future development trend of electronic devices. The traditional method for constructing the conductive path is mainly realized by lead-tin soldering or conductive silver adhesive of an epoxy resin system with higher modulus. However, lead-tin soldering is very polluted, and the soldering temperature is high, so that the flexible substrate is not suitable for being used on a flexible substrate. The conductive silver paste of the epoxy resin system is not used for flexible electronic components because of its non-adapted modulus. Although the conductive rigid material can be used for constructing the interconnection line in the flexible electronic device in a thin film form (tens of nanometers or tens of micrometers) or through a special structural design, such as a snake shape, an island bridge shape, a spiral shape or a fractal shape, the thin film manufacturing process is complex, and the special structural design is at a cost in space. The conductive silver paste invented in patent CN201510648113 is added with one or more of flexible conductive materials graphene, carbon nanotube, graphite, etc. to achieve flexibility, but only to achieve flexibility, and cannot be stretched.
Disclosure of Invention
In view of the above-mentioned shortcomings of the prior art, the present invention aims to provide a conductive silver paste, a preparation method and an application thereof, which solve the problem that the current conductive silver paste cannot be stretched. According to the invention, the high-conductivity filler silver nanosheet is filled into the low-modulus high-molecular polymer, so that the problem of connection of flexible electronic components is solved, and meanwhile, the conductive silver adhesive has the characteristics of simple preparation process, adjustable viscosity, long-term storage at room temperature and high curing speed.
In order to achieve the above objects and other related objects, the present invention is achieved by the following technical solutions:
the invention provides a conductive silver adhesive, which comprises silver nano-sheets and a low-modulus high-molecular polymer carrier, wherein the low-modulus high-molecular polymer carrier comprises a low-modulus high-molecular polymer and an organic solvent, the elastic modulus of the low-modulus high-molecular polymer is less than 100MPa, the organic solvent accounts for 60-80% of the total weight of the high-molecular polymer carrier, such as 60-70% or 70-80%, the silver nano-sheets account for 70-90%, such as 70-80% or 80-90%, and the low-modulus high-molecular polymer accounts for 10-30%, based on the total weight of the silver nano-sheets and the low-modulus high-molecular polymer.
The viscosity of the conductive silver adhesive can be adjusted by an organic solvent so as to meet the requirements of the device manufacturing process.
The silver nano-sheet has better conductive property than silver nano-wire and silver nano-particle, and can still maintain a conductive path under large strain. Preferably, the silver nanosheet has a plate diameter of 2 μm and a thickness of 5-10 nm.
Preferably, the low modulus high molecular weight polymer comprises a polyurethane-based elastomer. The low modulus, high molecular weight polymer excludes polymers that have failed to cure due to silver nanoplates, such as polydimethylsiloxane-type elastomers and polyimide-type elastomers, which have failed to cure due to silver nanoplates. The polyurethane elastomer is a low-modulus high-molecular polymer, namely the elastic modulus is less than 100 MPa.
Preferably, the organic solvent is selected from one or more of dimethylformamide, toluene and ethyl acetate.
The second aspect of the present invention provides a method for preparing the conductive silver paste, comprising the following steps: and mixing the low-modulus high-molecular polymer carrier with the silver nanosheets according to the weight percentage of the conductive silver adhesive to obtain the conductive silver adhesive.
Preferably, the method comprises the following steps:
1) mixing the low-modulus high-molecular polymer and an organic solvent according to the weight percentage of the conductive silver adhesive to obtain a low-modulus high-molecular polymer carrier;
2) mixing the low-modulus high-molecular polymer carrier obtained in the step 1) with silver nanosheets according to the weight percentage of the conductive silver adhesive to obtain the conductive silver adhesive.
The third aspect of the invention provides the application of the conductive silver adhesive for connecting flexible electronic components.
Preferably, the flexible electronic component is a flexible stretchable electronic component.
Compared with the prior art, the invention has at least one of the following advantages:
(1) according to the invention, the high-conductivity filler silver nanosheet is filled into the low-modulus high-molecular polymer, so that the problem of connection of flexible electronic components is solved.
(2) The invention uses low modulus high molecular polymer as the adhesive of conductive silver adhesive, which is matched with the modulus of flexible circuit.
(3) Different modulus high molecular polymers can meet different modulus flexible circuits.
(4) The conductive silver adhesive with adjustable viscosity is suitable for different processing technologies, such as 3D printing, spraying, spin coating, screen printing and the like.
(5) The low modulus, high molecular weight polymer allows the conductive silver paste to be used to construct flexible circuits that maintain high performance under high elongation (e.g., 100% elongation).
(6) Under larger strain, the two-dimensional material silver nanosheet in the conductive silver adhesive can still maintain a good conductive path, so that the conductive silver adhesive has high tensile property and conductive performance.
(7) The conductive silver adhesive has low curing temperature and short curing time, the curing time is less than 15 minutes at the temperature of 80 ℃, and the curing time is less than half an hour at normal temperature.
(8) The conductive silver adhesive has the advantages of simple formula and preparation process, adjustable viscosity, long-term storage at room temperature and high curing speed.
Drawings
Fig. 1 is an SEM of the conductive silver paste of example 1 after curing.
Fig. 2 is a graph of the relationship between the content of the silver nanosheet in the conductive silver adhesive and the resistance.
Fig. 3 is a strain-stress relationship diagram of conductive silver paste and TPU.
Fig. 4 is a graph of the strain-resistance relationship of conductive silver paste.
Detailed Description
The technical solution of the present invention is illustrated by specific examples below. It is to be understood that one or more method steps recited herein do not preclude the presence of additional method steps before or after the recited combining step, or that additional method steps may be intervening between the explicitly recited steps; it should also be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Moreover, unless otherwise indicated, the numbering of the various method steps is merely a convenient tool for identifying the various method steps, and is not intended to limit the order in which the method steps are arranged or the scope of the invention in which the invention may be practiced, nor is it intended to limit the scope of the invention in which changes or modifications in the relative relationship thereto may be made without materially changing the technical disclosure.
Example 1 silver nanoplates comprise 70 wt% based on the total weight of the silver nanoplates and low modulus high molecular weight polymer
Selecting a silver nanosheet with the sheet diameter of about 2 mu m and the thickness of 5-10 nm as a conductive filler, using a thermoplastic polyurethane elastomer TPU as an elastomer polymer (German Pasv 35A polyurethane), using dimethylformamide DMF as an organic solvent, and mixing the TPU and the DMF according to the weight ratio of 1: 4, and mixing the silver nanosheet and the TPU according to a weight ratio of 7: 3, and fully and uniformly stirring to obtain the conductive silver paste for connecting the PMDS elastomer-based flexible sensor and the lead. The SEM of the cured conductive silver paste is shown in figure 1. The conductive silver paste is dotted between the lead and the flexible sensor electrode, DMF is volatilized at room temperature, the DMF can be completely volatilized within half an hour, the lead is firmly connected with the electrode, the contact resistance is below 1 omega (figure 2), the maximum tensile resistance can reach 330 percent (figure 3), the resistance is almost unchanged at 70 percent of the tensile resistance (figure 4), and good conductive performance is kept.
Comparative example 1 silver nanoplates accounted for 60 wt% based on the total weight of the silver nanoplates and low modulus high molecular weight polymer
Selecting a silver nanosheet with the sheet diameter of about 2 mu m and the thickness of 5-10 nm as a conductive filler, using a thermoplastic polyurethane elastomer TPU as an elastomer polymer (German Pasv 35A polyurethane), using dimethylformamide DMF as an organic solvent, and mixing the TPU and the DMF according to the weight ratio of 1: 4, and mixing the silver nanosheet and the TPU according to a weight ratio of 1.5: 1, and fully and uniformly stirring to obtain the conductive silver paste for connecting the PMDS elastomer-based flexible sensor and the lead. The conductive silver paste is dotted between the lead and the flexible sensor electrode, and is solidified, the lead is connected with the electrode, as shown in fig. 2, when the silver nano-chip component is 60%, the resistance is too large, and the conductive silver paste is not suitable for being used as conductive silver glue; although the conductive silver paste having a silver nanoparticle component of 60% has a maximum elongation of 350% in fig. 3, the resistance sharply increases when the conductive silver paste is elongated to about 10% as shown in fig. 4. Conductive silver paste for flexible electronics needs to maintain stable resistance throughout its applicable tensile range.
Example 2 silver nanoplates comprise 80 wt% based on the total weight of the silver nanoplates and low modulus high molecular weight polymer
Selecting a silver nanosheet with the sheet diameter of about 2 mu m and the thickness of 5-10 nm as a conductive filler, using a thermoplastic polyurethane elastomer (TPU) as an elastomer polymer (German Pasv 35A polyurethane), using Dimethylformamide (DMF) as an organic solvent, and mixing the TPU and the DMF according to the weight ratio of 1: 1.5, and mixing the silver nanosheet and TPU according to a weight ratio of 8: 2, and after fully and uniformly stirring, the mixture is used for 3D printing of pattern electrodes on a flexible substrate. Weight ratio of TPU to DMF 1: the conductive silver paste prepared by the high molecular polymer carrier of 1.5 has increased viscosity, can be smoothly extruded from the 3D printing nozzle, and cannot flow on a printed substrate, so that the completeness and accuracy of patterns are ensured. Meanwhile, as the specific gravity of DMF is reduced, the curing time of the conductive silver paste is shortened, and the conductive silver paste is cured within a few seconds after being printed on the flexible substrate. The contact resistance is below 1 omega, the maximum can be stretched to 210 percent (figure 3), the resistance is hardly changed in 100 percent stretching (figure 4), and good conductive performance is kept.
Example 3 silver nanoplates comprise 90 wt% based on the total weight of the silver nanoplates and low modulus high molecular weight polymer
Selecting a silver nanosheet with the sheet diameter of about 2 mu m and the thickness of 5-10 nm as a conductive filler, selecting a thermoplastic polyurethane elastomer TPU as an elastomer polymer (German Pasv 35A polyurethane) and selecting dimethylformamide DMF as an organic solvent, and fully and uniformly stirring to obtain the conductive silver paste, wherein the comprehensive conductivity and modulus are 1: the conductive silver paste of 9 can be used for PCB wiring (wherein the weight ratio of TPU to DMF is 1: 4) to replace the traditional soldering tin wiring. The implementation method comprises the following steps: preparing conductive silver paste according to a proportion, dotting a thin wire at an original welding point, simultaneously dotting the silver paste, and successfully connecting the wire after DMF is volatilized. Because the modulus of the cured conductive silver paste is less than that of soldering tin, the wiring firmness is not as good as that of the traditional soldering tin wiring, but the safety is high. Although the proportion of silver is increased and the maximum elongation of the conductive silver paste is reduced to 36%, the conductivity thereof is improved (fig. 3 and 2), so that it is more suitable for wiring of rigid circuits.
While the invention has been described with respect to a preferred embodiment, it will be understood by those skilled in the art that the foregoing and other changes, omissions and deviations in the form and detail thereof may be made without departing from the scope of this invention. Those skilled in the art can make various changes, modifications and equivalent arrangements, which are equivalent to the embodiments of the present invention, without departing from the spirit and scope of the present invention, and which may be made by utilizing the techniques disclosed above; meanwhile, any changes, modifications and variations of the above-described embodiments, which are equivalent to those of the technical spirit of the present invention, are within the scope of the technical solution of the present invention.
Claims (7)
1. The conductive silver adhesive is characterized by comprising silver nanosheets and a low-modulus high-molecular polymer carrier, wherein the low-modulus high-molecular polymer carrier comprises a low-modulus high-molecular polymer and an organic solvent, the elastic modulus of the low-modulus high-molecular polymer is less than 100MPa, the organic solvent accounts for 60-80% of the total weight of the high-molecular polymer carrier, the silver nanosheets account for 70-90% of the total weight of the silver nanosheets and the low-modulus high-molecular polymer, and the low-modulus high-molecular polymer accounts for 10-30%; the silver nanosheet is 2 microns in sheet diameter and 5-10 nm in thickness.
2. The conductive silver paste of claim 1, wherein said low modulus high molecular weight polymer comprises a polyurethane-based elastomer.
3. The conductive silver paste of claim 1, wherein the organic solvent is selected from one or more of dimethylformamide, toluene and ethyl acetate.
4. A method for preparing conductive silver paste according to any one of claims 1 to 3, comprising the steps of: and mixing the low-modulus high-molecular polymer carrier with the silver nanosheets according to the weight percentage of the conductive silver adhesive to obtain the conductive silver adhesive.
5. The method for preparing conductive silver paste according to claim 4, comprising the steps of:
1) mixing the low-modulus high-molecular polymer and an organic solvent according to the weight percentage of the conductive silver adhesive to obtain a low-modulus high-molecular polymer carrier;
2) mixing the low-modulus high-molecular polymer carrier obtained in the step 1) with silver nanosheets according to the weight percentage of the conductive silver adhesive to obtain the conductive silver adhesive.
6. The conductive silver paste as claimed in any one of claims 1 to 3, which is used for connection of flexible electronic components.
7. Use of the conductive silver paste of claim 6, wherein the flexible electronic component is a flexible stretchable electronic component.
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