CN108305702A - A kind of preparation and its application of medium temperature graphene/silver composite conducting slurry - Google Patents
A kind of preparation and its application of medium temperature graphene/silver composite conducting slurry Download PDFInfo
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Abstract
Graphene has good chemical stability, excellent electric conductivity and mechanical flexibility.But due to graphene dispersion in electrocondution slurry after, it is difficult to form the contact of " bridging " formula between graphene sheet layer and lamella, it is difficult to form perfect conductive path, and in lamella junction, there are larger contact resistances so that the sheet resistance of its conductive coating formed is difficult to further decrease.The graphene that the present invention is prepared using liquid phase ultrasound stripping method, collectively as conductive filler, uses cryogenic glass powder for binder with nano-silver powder, and the graphene/silver composite conducting slurry for providing elevated temperature cohesiveness energy is mixed with other organic solvents and additive.And be coated onto potsherd surface, by high temperature sintering for a period of time after, potsherd surface obtain one layer with certain binding force and superior electrical conductivity can graphene/silver conductive composite coating.
Description
Technical field
The present invention relates to conductive coating more particularly to a kind of medium temperature graphene/silver composite conducting slurries and ceramic matrix
The preparation method of surface graphene/silver conductive composite coating.
Background technology
Electrocondution slurry (electricallyconductivepaste) is to collect material, metallurgy, chemical industry, electronic technology in one
The electronic functional material of body is hydrid integrated circuit, sensing element, surface mounting technology, resistor network, display, and each
The basic material of kind electronic discrete device etc..With the high speed development of information industry so that device is to micromation, precise treatment and soft
The directions such as property are developed, and lot of domestic and international scientific research institution produces great interest to the development and application of electrocondution slurry.
Electrocondution slurry generally includes 3 kinds of function phase, organic carrier, Binder Phase components.I.e. conductive phase (gold, silver, copper, silver and
Tin-bismuth alloy electroplating etc.), organic carrier (organic resin and solvent) and/or permanent adhesive agent (silicate glass etc.).According to conductive paste
Expect that the property of composition, electrocondution slurry are broadly divided into organic type electrocondution slurry, inorganic type electrocondution slurry and compound-type conducting slurry.Its
In, for compound-type conducting slurry using conductive metal particles as conductive phase, high molecular polymer is Binder Phase, has excellent electric conductivity
And mechanical performance, process is relatively easy, and repeatability and conductive stability are stronger, and the stable storing phase is longer, has higher
Practicability, have a wide range of applications, at present on the market most of electrocondution slurry be it is such.
Carbon conductive filler (including carbon black, graphite, carbon fiber and its mixture) is usually used in electrically conductive ink.In recent ten years
The research of carbon series conductive ink is concentrated mainly on influence of the factors such as the pattern by conductive filler, proportioning to electrically conductive ink performance
Rule.Using carbon black, graphite and silver powder as conductive filler, Xiao Shuan etc. is filled out using the carbon dust of different-shape and proportioning as conduction Ma Xiaoxu etc.
Material, has obtained the influence of the type, pattern of conductive phase to performances such as carbon slurry viscosity, resistance.Novel carbon conductive filler includes
Carbon nanotube (CNTs) and graphene have excellent electric conductivity due to big pi bond, but in the application exist stablize separation and
Scattering problem.Grandson waits quietly using sun/nonionic surfactant compounding dispersing Nano carbon tubes under the conditions of sand milling, with mica or two
Titanium oxide is compound, hence it is evident that improves the dispersibility of CNTs, more traditional carbon nano tube surface absorption charged ion or organic matter etc. side
Method dispersibility is more preferable.
As a kind of new carbon, graphene itself has high conductivity and high-termal conductivity, theoretically its electron transfer
Rate can reach 2 × 105cm2/ Vs, 140 times of electron mobility about in silicon, 20 times of GaAs, temperature stability is high, reason
By upper, conductivity is up to 108S/m, it is lower than copper, silver, it is conductive best material at room temperature, with graphene as conductive paste
Conductive phase (conductive filler) in material, can reduce the cost of electrocondution slurry.
Invention content
In view of the deficiencies of the prior art, a kind of medium temperature graphene/silver composite conducting slurry of present invention offer and ceramic base
The preparation method of body surface face graphene/silver conductive composite coating, obtain it is a kind of with good combination power and superior electrical conductivity can
Graphene/silver conductive composite coating.
In order to achieve the above objectives, the technical solution adopted in the present invention is as follows：
A kind of preparation method of medium temperature graphene/silver composite conducting slurry, includes the following steps：
(1) under the conditions of 50-100 DEG C, by magnetic agitation respectively by the antifoaming agent of 0.5-9wt.% and 0.5-9wt.%
Thickener be dissolved in terpinol；
(2) under the conditions of 50-100 DEG C, by magnetic agitation, proportionally successively addition 0.5-4wt.% dispersant,
0.5-6wt.% levelling agents, 0.5-4wt.% plasticizer, mixing time 10-30h obtain the organic carrier of the electrocondution slurry
Phase；
(3) it weighs organic carrier to be mutually placed in vacuum stirring kettle, under the stirring condition of 100-800r/min, add in batches
Enter uniformly mixed nano-silver powder and glass powder with low melting point, obtains nano silver mixed slurry；Add nano-silver powder, organic carrier phase
Ratio with glass powder is 30-80: 20-75: 2-15；
(4) it under the stirring condition of 120-800r/min, weighs dry, activation graphene powder and is placed in above-mentioned steps
(3) in obtained nano silver mixed slurry, graphene/silver paste material precursor is obtained；Wherein graphene powder and nano-silver powder
Ratio be：1∶15-2∶10；
(5) it is 120-160 DEG C the graphene obtained in above-mentioned steps (4)/silver paste material precursor to be placed in temperature, vacuum degree
In the constant-temperature vacuum baking oven of -0.1Mpa, to heat 1-2h, maturation process is carried out to precursor；
(6) presoma after above-mentioned curing is placed in the de-airing mixer that vacuum degree is -0.1Mpa with 500-
The rotating speed of 1500r/min persistently stirs 24-72h, obtains graphene/silver composite conducting slurry of stable dispersion；
(7) graphene obtained in above-mentioned steps (6)/silver composite conducting slurry is uniformly coated to the surface of potsherd,
Coated area is 2.5 × 2.5cm2；
(8) it is 300- the potsherd that graphene/silver composite conducting slurry has been coated in above-mentioned steps (7) to be placed in temperature
In 500 DEG C of Muffle furnace, it is sintered 0.5-4h, obtains the potsherd for covering graphene/silver conductive composite coating.
Preferably, in step (1), the antifoaming agent is tributyl phosphate, additive amount 1-5wt.%；The thickener
For ethyl cellulose, additive amount 1-5wt.%.
Preferably, in step (2), the dispersant is silane coupling agent, additive amount 1-2wt.%；The levelling agent
For dimethicone or butyl cellosolve, additive amount 1-3wt.%；The plasticizer is dibutyl phthalate, addition
Amount is 1-2wt.%；Mixing time in step (2) is 12-24h.
Preferably, the ratio of the nano-silver powder in the step (3), organic carrier and glass powder is 35-65: 25-55: 5-
10；Mixing speed in the step (4) is 200-500r/min, the ratio of graphene and nano-silver powder is：1∶9-3∶7.
Preferably, by the way of drop coating that the graphene prepared/silver composite conducting slurry is uniform in the step (7)
It is coated to potsherd surface.
Preferably, the step (8) is to set the potsherd that graphene/silver composite conducting slurry has been coated in step (7)
In the Muffle furnace that temperature is 350-450 DEG C, it is sintered 0.5-2h.
The present invention also provides a kind of conductive coating, which adopts is prepared with the aforedescribed process.
Compared with prior art, beneficial effects of the present invention are：
Graphene has good chemical stability, excellent electric conductivity and mechanical flexibility.But due to graphene dispersion
It is difficult to form the contact of " bridging " formula after in electrocondution slurry, between graphene sheet layer and lamella, that is, is difficult to be formed perfect
Conductive path, and in lamella junction, there are larger contact resistances so that the sheet resistance of its conductive coating formed is difficult to
It further decreases.Patent of the present invention is filled out with nano-silver powder collectively as conduction using graphene prepared by liquid phase ultrasound stripping method
Material, uses cryogenic glass powder for binder, is mixed with other organic solvents and additive and provides elevated temperature cohesiveness energy
Graphene/silver composite conducting slurry.And be coated onto potsherd surface, by high temperature sintering for a period of time after, in potsherd
Surface obtains one layer of graphene/silver conductive composite coating with certain binding force and superior electrical conductivity energy.
Graphene/silver conductive composite coating can be sintered in 350~450 DEG C of temperature range in patent of the present invention,
The sintering temperature of the more conventional electrocondution slurry of sintering temperature is low, more energy conservation and environmental protection.
The present invention using high conductivity graphene and nano-silver powder be conductive bodies, wherein graphene can be with nanometer
Silver powder mixes, and preferably forms conductive path (i.e.：Nano silver is filled to the junction of graphene sheet layer), and can greatly drop
The dosage of low nano silver, compared to conventional conductive silver slurry, cost is more cheap.
Patent of the present invention is using glass powder with low melting point as Binder Phase so that the conductive components such as graphene/silver can be more preferable
Combination on ceramic matrix surface, solve adhesion problem of the conductive phases such as graphene/silver in matrix surface.
Description of the drawings
Fig. 1 a are the SEM spectrum of graphene；
Fig. 1 b are graphene powder Raman collection of illustrative plates；
Fig. 1 c are the blank ceramics sheet matrix used in the present invention；
Fig. 1 d are the ceramic matrix for the graphene/silver conductive coating being prepared in the embodiment of the present invention 5；
Fig. 1 e are the ceramic matrix for the graphene/silver conductive coating being prepared in comparative example 2 of the present invention.
Specific implementation mode
The present invention is expanded on further below by specific implementation example with reference, but is not limited to the present invention.I.e.
These examples are only for illustrating the present invention and are not intended to limit the scope of the present invention.In addition, having read of the invention lecture
After content, those skilled in the art can make various modifications or changes to the present invention, and such equivalent forms equally fall within this Shen
It please the appended claims limited range.
Embodiment 1
A kind of preparation method of medium temperature graphene/silver composite conducting slurry, includes the following steps：
(1) under the conditions of 50 DEG C, by magnetic agitation respectively by the second of the tributyl phosphate of 0.5wt.% and 0.5wt.%
Base cellulose is dissolved in terpinol；
(2) under the conditions of 50 DEG C, by magnetic agitation, proportionally successively addition 0.5wt.% silane coupling agent,
0.5wt.% dimethicones, 0.5wt.% dibutyl phthalates, mixing time 10h, obtain the electrocondution slurry has
Airborne body phase；
(3) it weighs organic carrier to be mutually placed in vacuum stirring kettle, under the stirring condition of 100r/min, be added in batches mixed
Uniform nano-silver powder and glass powder with low melting point are closed, nano silver mixed slurry is obtained；Add nano-silver powder, organic carrier phase and glass
The ratio of glass powder is 30: 20: 2；
(4) it under the stirring condition of 120r/min, weighs dry, activation graphene powder and is placed in above-mentioned steps (3) institute
In obtained nano silver mixed slurry, graphene/silver paste material precursor is obtained；The wherein ratio of graphene powder and nano-silver powder
For：1∶15；
(5) by the graphene obtained in above-mentioned steps (4)/silver paste material precursor be placed in temperature be 120 DEG C, vacuum degree be-
In the constant-temperature vacuum baking oven of 0.1Mpa, 1h is heated, maturation process is carried out to precursor；
(6) presoma after above-mentioned curing is placed in the de-airing mixer that vacuum degree is -0.1Mpa with 500r/min
Rotating speed persistently stir for 24 hours, obtain graphene/silver composite conducting slurry of stable dispersion；
(7) graphene obtained in above-mentioned steps (6)/silver composite conducting slurry is uniformly coated to the surface of potsherd,
Coated area is 2.5 × 2.5cm2；
(8) it is 300 DEG C the potsherd that graphene/silver composite conducting slurry has been coated in above-mentioned steps (7) to be placed in temperature
Muffle furnace in, be sintered 0.5h, obtain the potsherd for covering graphene/silver conductive composite coating.
Embodiment 2
A kind of preparation method of medium temperature graphene/silver composite conducting slurry, includes the following steps：
(1) under the conditions of 100 DEG C, by magnetic agitation respectively by the ethyl of the tributyl phosphate of 9wt.% and 9wt.% fibre
Dimension element is dissolved in terpinol；
(2) under the conditions of 100 DEG C, by magnetic agitation, proportionally successively addition 4wt.% silane coupling agent,
It is airborne to obtain having for the electrocondution slurry by 6wt.% butyl cellosolves, 4wt.% dibutyl phthalates, mixing time 0h
Body phase；
(3) it weighs organic carrier to be mutually placed in vacuum stirring kettle, under the stirring condition of 800r/min, be added in batches mixed
Uniform nano-silver powder and glass powder with low melting point are closed, nano silver mixed slurry is obtained；Add nano-silver powder, organic carrier phase and glass
The ratio of glass powder is 80: 75: 15；
(4) it under the stirring condition of 800r/min, weighs dry, activation graphene powder and is placed in above-mentioned steps (3) institute
In obtained nano silver mixed slurry, graphene/silver paste material precursor is obtained；The wherein ratio of graphene powder and nano-silver powder
For：2∶10；
(5) by the graphene obtained in above-mentioned steps (4)/silver paste material precursor be placed in temperature be 160 DEG C, vacuum degree be-
In the constant-temperature vacuum baking oven of 0.1Mpa, 2h is heated, maturation process is carried out to precursor；
(6) presoma after above-mentioned curing is placed in the de-airing mixer that vacuum degree is -0.1Mpa with 1500r/min
Rotating speed persistently stir 72h, obtain graphene/silver composite conducting slurry of stable dispersion；
(7) graphene obtained in above-mentioned steps (6)/silver composite conducting slurry is uniformly coated to the surface of potsherd,
Coated area is 2.5 × 2.5cm2；
(8) it is 500 DEG C the potsherd that graphene/silver composite conducting slurry has been coated in above-mentioned steps (7) to be placed in temperature
Muffle furnace in, be sintered 4h, obtain the potsherd for covering graphene/silver conductive composite coating.
Embodiment 3
A kind of preparation method of medium temperature graphene/silver composite conducting slurry, includes the following steps：
(1) under the conditions of 60 DEG C, by magnetic agitation respectively by the ethyl of the tributyl phosphate of 1wt.% and 1wt.% fibre
Dimension element is dissolved in terpinol；
(2) under the conditions of 60 DEG C, by magnetic agitation, 1wt.% silane coupling agents, 1wt.% are proportionally added successively
Dimethicone, 1wt.% dibutyl phthalates, mixing time 12h obtain the organic carrier phase of the electrocondution slurry；
(3) organic carrier for weighing certain mass is mutually placed in vacuum stirring kettle, in the condition of 200r/min stirring at low speed
Under, then uniformly mixed nano-silver powder (being provided by Aladdin reagent Co., Ltd) and glass powder with low melting point are provided in batches,
The ratio for adding nano-silver powder, organic carrier and glass powder is 35: 25: 5；
(4) under conditions of 200r/min stirring at low speed, the drying of certain mass is weighed, activated graphene powder is set
In above-mentioned nano silver mixed slurry, the ratio of wherein graphene and nano-silver powder is：1∶9；
(5) it is 120 DEG C above-mentioned tentatively uniformly mixed graphene/silver paste material precursor to be placed in temperature, vacuum degree is-
In the constant-temperature vacuum baking oven of 0.1Mpa, 1h is heated, maturation process is carried out to precursor；
(6) presoma after above-mentioned curing is placed in the de-airing mixer that vacuum degree is -0.1Mpa with 500r/min
Rotating speed persistently stir for 24 hours, you can obtain graphene/silver composite conducting slurry of stable dispersion；
(7) by the graphene prepared/silver composite conducting slurry uniform coated ceramic piece surface in a manner of drop coating, control applies
Clad can product is 2.5 × 2.5cm2；
(8) potsherd for having coated graphene/silver composite conducting slurry is placed in the Muffle furnace that temperature is 350 DEG C, is burnt
Tie 0.5h, you can obtain covering the potsherd of graphene/silver conductive composite coating；
Embodiment 4
A kind of preparation method of medium temperature graphene/silver composite conducting slurry, includes the following steps：
(1) under the conditions of 80 DEG C, by magnetic agitation respectively by the ethyl of the tributyl phosphate of 5wt.% and 5wt.% fibre
Dimension element is dissolved in terpinol；
(2) under the conditions of 80 DEG C, by magnetic agitation, 2wt.% silane coupling agents, 3wt.% are proportionally added successively
Butyl cellosolve, 2wt.% dibutyl phthalates, mixing time are for 24 hours, to obtain the organic carrier phase of the electrocondution slurry；
(3) organic carrier for weighing certain mass is mutually placed in vacuum stirring kettle, in the condition of 500r/min stirring at low speed
Under, then uniformly mixed nano-silver powder (being provided by Aladdin reagent Co., Ltd) and glass powder with low melting point are provided in batches,
The ratio for adding nano-silver powder, organic carrier and glass powder is 65: 55: 10；
(4) under conditions of 500r/min stirring at low speed, the drying of certain mass is weighed, activated graphene powder is set
In above-mentioned nano silver mixed slurry, the ratio of wherein graphene and nano-silver powder is：3∶7；
(5) it is 60 DEG C above-mentioned tentatively uniformly mixed graphene/silver paste material precursor to be placed in temperature, vacuum degree is-
In the constant-temperature vacuum baking oven of 0.1Mpa, 2h is heated, maturation process is carried out to precursor；
(6) presoma after above-mentioned curing is placed in the de-airing mixer that vacuum degree is -0.1Mpa with 1500r/min
Rotating speed persistently stir 272h, you can obtain graphene/silver composite conducting slurry of stable dispersion；
(7) by the graphene prepared/silver composite conducting slurry uniform coated ceramic piece surface in a manner of drop coating, control applies
Clad can product is 2.5 × 2.5cm2；
(8) potsherd for having coated graphene/silver composite conducting slurry is placed in the Muffle furnace that temperature is 450 DEG C, is burnt
Tie 2h, you can obtain covering the potsherd of graphene/silver conductive composite coating.
Embodiment 5
A kind of preparation method of medium temperature graphene/silver composite conducting slurry, includes the following steps：
(1) under the conditions of 80 DEG C, by magnetic agitation respectively by the ethyl of the tributyl phosphate of 2wt.% and 5wt.% fibre
Dimension element is dissolved in terpinol；
(2) under the conditions of 80 DEG C, by magnetic agitation, 2wt.% silane coupling agents, 3wt.% are proportionally added successively
Dimethicone, 1wt.% dibutyl phthalates, mixing time 12h obtain the organic carrier phase of the electrocondution slurry；
(3) organic carrier for weighing certain mass is mutually placed in vacuum stirring kettle, in the condition of 500r/min stirring at low speed
Under, then uniformly mixed nano-silver powder (being provided by Aladdin reagent Co., Ltd) and glass powder with low melting point are provided in batches,
The ratio for adding nano-silver powder, organic carrier and glass powder is 35: 55: 5-10；
(4) under conditions of 500r/min stirring at low speed, the drying of certain mass is weighed, activated graphene powder is set
In above-mentioned nano silver mixed slurry, the ratio of wherein graphene and nano-silver powder is：1∶9；
(5) it is 150 DEG C above-mentioned tentatively uniformly mixed graphene/silver paste material precursor to be placed in temperature, vacuum degree is-
In the constant-temperature vacuum baking oven of 0.1Mpa, 1h is heated, maturation process is carried out to precursor；
(6) presoma after above-mentioned curing is placed in the de-airing mixer that vacuum degree is -0.1Mpa with 1000r/min
Rotating speed persistently stir 48h, you can obtain graphene/silver composite conducting slurry of stable dispersion；
(7) by the graphene prepared/silver composite conducting slurry uniform coated ceramic piece surface in a manner of drop coating, control applies
Clad can product is 2.5 × 2.5cm2；
(8) potsherd for having coated graphene/silver composite conducting slurry is placed in the Muffle furnace that temperature is 450 DEG C, is burnt
Tie 0.5h, you can obtain covering the potsherd of graphene/silver conductive composite coating.
Comparative example 1
The sintering temperature of 5 step of embodiment (8) is adjusted to 250 DEG C, remaining parameter constant.
Comparative example 2
The sintering temperature of 5 step of embodiment (8) is adjusted to 850 DEG C, remaining parameter constant.
Comparative example 3
The ratio of the addition nano-silver powder, organic carrier and glass powder of 5 step of embodiment (3) is adjusted to 20: 15: 1,
Remaining parameter constant.
Comparative example 4
The ratio of the addition nano-silver powder, organic carrier and glass powder of 5 step of embodiment (3) is adjusted to 90: 80: 20,
Remaining parameter constant.
Test method：
(1) the surface electricity after the test sintering of DIGITAL MULTIMETER VC480C+ type digital display resistance meters is used
Resistance rate, each embodiment test 3 samples.
(2) according to the face coat knot of sample after the method test sintering of ASTMD 3359-2002 coating surfaces scribing line
With joint efforts, each embodiment tests 3 samples.
Test result is as shown in table 1-2：
Table 1：Embodiment 1-5 sample tests
Table 2：Comparative example 1-4 sample tests
Graphene made from the embodiment of the present invention 5/silver conductive composite coating photo is as shown in Figure 1 d, can from Fig. 1 d
Go out graphene and nano silver particles and be coated in potsherd matrix surface well so that whole surface is in black, and surfacing
Property is preferable.The electric conductivity and caking property of graphene made from embodiment 5/silver conductive composite coating are as shown in table 1.From table 1
It can be seen that the surface resistivity of the graphene/silver conductive composite coating is 2.97 × 10-2-3.45×10-2Ohm, i.e., it is conductive
Property is preferable.Force test method is combined using the surfaces ASTMD 3359-2002, it is found that the intersection in scribing line has the paint of small pieces
It falls off, but the gross area that falls off is less than 5%, i.e. coating adhesion can reach 4B grades.
According to the test data of comparative example 1-4 it is found that the excessively high or too low and nano-silver powder of sintering temperature, have it is airborne
The excessively high or too low of the ratio of body and glass powder can have an adverse effect to the electric conductivity and adhesive force of final products, this
Sintering temperature and nano-silver powder, the ratio of organic carrier and glass powder of invention have reached balance appropriate.
Graphene/silver conductive composite coating can be 350~450 under inert gas atmosphere protective condition in patent of the present invention
DEG C temperature range be sintered, the sintering temperature of the more conventional electrocondution slurry of sintering temperature is low, more energy conservation and environmental protection.
The present invention using high conductivity graphene and nano-silver powder be conductive bodies, wherein graphene can be with nanometer
Silver powder mixes, and preferably forms conductive path (i.e.：Nano silver is filled to the junction of graphene sheet layer), and can greatly drop
The dosage of low nano silver, compared to conventional conductive silver slurry, cost is more cheap.
Patent of the present invention is using glass powder with low melting point as Binder Phase so that the conductive components such as graphene/silver can be more preferable
Combination on ceramic matrix surface, solve adhesion problem of the conductive phases such as graphene/silver in matrix surface.
Claims (7)
1. a kind of preparation method of medium temperature graphene/silver composite conducting slurry, feature include the following steps：
（1）Under the conditions of 50-100 DEG C, by magnetic agitation respectively by the thickening of the antifoaming agent of 0.5-9wt.% and 0.5-9wt.%
Agent is dissolved in terpinol；
（2）Under the conditions of 50-100 DEG C, by magnetic agitation, dispersant, the 0.5- of 0.5-4wt.% are proportionally added successively
The levelling agent of 6wt.%, the plasticizer of 0.5-4wt.%, mixing time 10-30h obtain the organic carrier phase of the electrocondution slurry；
（3）It weighs organic carrier to be mutually placed in vacuum stirring kettle, under the stirring condition of 100-800r/min, be added in batches mixed
Uniform nano-silver powder and glass powder with low melting point are closed, nano silver mixed slurry is obtained；Add nano-silver powder, organic carrier phase and glass
The ratio of glass powder is 30-80:20-75:2-15；
（4）Under the stirring condition of 120-800r/min, weighs dry, activation graphene powder and be placed in above-mentioned steps（3）Institute
In obtained nano silver mixed slurry, graphene/silver paste material precursor is obtained；The wherein ratio of graphene powder and nano-silver powder
It is 1:15-2:10；
（5）By above-mentioned steps（4）In obtained graphene/silver paste material precursor to be placed in temperature be 120-160 DEG C, vacuum degree is-
In the constant-temperature vacuum baking oven of 0.1Mpa, 1-2h is heated, maturation process is carried out to precursor；
（6）Presoma after above-mentioned curing is placed in the de-airing mixer that vacuum degree is -0.1Mpa with 500-1500r/min
Rotating speed persistently stir 24-72h, obtain graphene/silver composite conducting slurry of stable dispersion；
（7）By above-mentioned steps（6）In obtained graphene/silver composite conducting slurry be uniformly coated to the surface of potsherd, coating
Area is 2.5 × 2.5cm2；
（8）By above-mentioned steps（7）It is 300-500 DEG C that the middle potsherd for having coated graphene/silver composite conducting slurry, which is placed in temperature,
Muffle furnace in, be sintered 0.5-4h, obtain the potsherd for covering graphene/silver conductive composite coating.
2. the preparation method of medium temperature graphene according to claim 1/silver composite conducting slurry, which is characterized in that in step
Suddenly（1）In, the antifoaming agent is tributyl phosphate, additive amount 1-5wt.%；The thickener is ethyl cellulose, additive amount
For 1-5wt.%.
3. the preparation method of medium temperature graphene according to claim 2/silver composite conducting slurry, which is characterized in that in step
Suddenly（2）In, the dispersant is silane coupling agent, additive amount 1-2wt.%；The levelling agent is dimethicone or ethylene glycol
Butyl oxide, additive amount 1-3wt.%；The plasticizer is dibutyl phthalate, additive amount 1-2wt.%；Step（2）In
Mixing time be 12-24h.
4. the preparation method of medium temperature graphene according to claim 1/silver composite conducting slurry, which is characterized in that described
Step（3）In nano-silver powder, organic carrier and glass powder ratio be 35-65:25-55:5-10；The step（4）In
Mixing speed is 200-500r/min, the ratio of graphene and nano-silver powder is 1:9-3:7.
5. the preparation method of medium temperature graphene according to claim 1/silver composite conducting slurry, which is characterized in that described
Step（7）It is middle that the graphene prepared/silver composite conducting slurry is uniformly coated to potsherd surface by the way of drop coating.
6. the preparation method of medium temperature graphene according to claim 1/silver composite conducting slurry, which is characterized in that described
Step（8）It is by step（8）It is 350-450 DEG C that the middle potsherd for having coated graphene/silver composite conducting slurry, which is placed in temperature,
In Muffle furnace, it is sintered 0.5-2h.
7. a kind of conductive coating, the conductive coating is led using what method as claimed in any one of claims 1 to 6 was prepared
Plasma-based material is prepared.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110942842A (en) * | 2019-12-17 | 2020-03-31 | 广东风华高新科技股份有限公司 | Conductor paste and conductor material |
| CN112242211A (en) * | 2019-07-18 | 2021-01-19 | 常州烯源纳米科技有限公司 | Polymer conductive and heat-conducting film slurry of graphene |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102254584A (en) * | 2011-05-12 | 2011-11-23 | 中国科学院宁波材料技术与工程研究所 | General electronic paste based on graphene filler |
| CN102664259A (en) * | 2012-05-02 | 2012-09-12 | 中国科学院宁波材料技术与工程研究所 | Method for preparing cathode material of lithium ion battery |
| CN104464883A (en) * | 2014-12-26 | 2015-03-25 | 苏州格瑞丰纳米科技有限公司 | Graphene electrocondution slurry with dispersants adsorbed on surface and manufacturing method and application thereof |
| CN105845198A (en) * | 2016-05-16 | 2016-08-10 | 南通天盛新能源股份有限公司 | Solar cell front side silver slurry doped with modified graphene and manufacture method therefor |
| CN105869770A (en) * | 2016-03-30 | 2016-08-17 | 成都新柯力化工科技有限公司 | Graphene conductive paste prepared by mechanical stripping and preparation method of graphene conductive paste |
| CN106469582A (en) * | 2015-08-18 | 2017-03-01 | 中国科学院上海微系统与信息技术研究所 | A kind of electrocondution slurry of graphene-containing and preparation method thereof |
-
2018
- 2018-01-19 CN CN201810054125.0A patent/CN108305702A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102254584A (en) * | 2011-05-12 | 2011-11-23 | 中国科学院宁波材料技术与工程研究所 | General electronic paste based on graphene filler |
| CN102664259A (en) * | 2012-05-02 | 2012-09-12 | 中国科学院宁波材料技术与工程研究所 | Method for preparing cathode material of lithium ion battery |
| CN104464883A (en) * | 2014-12-26 | 2015-03-25 | 苏州格瑞丰纳米科技有限公司 | Graphene electrocondution slurry with dispersants adsorbed on surface and manufacturing method and application thereof |
| CN106469582A (en) * | 2015-08-18 | 2017-03-01 | 中国科学院上海微系统与信息技术研究所 | A kind of electrocondution slurry of graphene-containing and preparation method thereof |
| CN105869770A (en) * | 2016-03-30 | 2016-08-17 | 成都新柯力化工科技有限公司 | Graphene conductive paste prepared by mechanical stripping and preparation method of graphene conductive paste |
| CN105845198A (en) * | 2016-05-16 | 2016-08-10 | 南通天盛新能源股份有限公司 | Solar cell front side silver slurry doped with modified graphene and manufacture method therefor |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112242211A (en) * | 2019-07-18 | 2021-01-19 | 常州烯源纳米科技有限公司 | Polymer conductive and heat-conducting film slurry of graphene |
| CN110942842A (en) * | 2019-12-17 | 2020-03-31 | 广东风华高新科技股份有限公司 | Conductor paste and conductor material |
| CN112992402A (en) * | 2021-04-16 | 2021-06-18 | 西安宏星电子浆料科技股份有限公司 | Silver and two-dimensional MXene mixed system conductor slurry for chip resistor and preparation method thereof |
| CN113764118A (en) * | 2021-09-09 | 2021-12-07 | 山西聚微天成科技有限公司 | Preparation method and application of stretchable high-conductivity material |
| CN113764118B (en) * | 2021-09-09 | 2023-11-28 | 北京星宇同辉科技有限公司 | Preparation method and application of stretchable high-conductivity material |
| CN113903494A (en) * | 2021-09-30 | 2022-01-07 | 兰州大学 | High-performance graphene composite silver paste and preparation method thereof |
| CN114038606A (en) * | 2021-11-05 | 2022-02-11 | 巨晶(广东)光电科技有限公司 | Liquid metal graphene composite conductive paste for transparent display screen |
| CN114155994A (en) * | 2021-12-21 | 2022-03-08 | 深圳市海德门电子有限公司 | Conductive material and preparation method thereof |
| CN115732117A (en) * | 2022-03-08 | 2023-03-03 | 重庆恩辰新材料科技有限责任公司 | Conductive silver paste for ceramic surface circuit printing and preparation method and application thereof |
| CN115732117B (en) * | 2022-03-08 | 2024-01-19 | 重庆恩辰新材料科技有限责任公司 | Conductive silver paste for ceramic surface circuit printing and preparation method and application thereof |
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