CN108305703A - A kind of preparation and its application of medium temperature graphene/nickel composite conducting slurry - Google Patents
A kind of preparation and its application of medium temperature graphene/nickel composite conducting slurry Download PDFInfo
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- CN108305703A CN108305703A CN201810054914.4A CN201810054914A CN108305703A CN 108305703 A CN108305703 A CN 108305703A CN 201810054914 A CN201810054914 A CN 201810054914A CN 108305703 A CN108305703 A CN 108305703A
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- 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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- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/14—Conductive material dispersed in non-conductive inorganic material
- H01B1/16—Conductive material dispersed in non-conductive inorganic material the conductive material comprising metals or alloys
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- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/14—Conductive material dispersed in non-conductive inorganic material
- H01B1/18—Conductive material dispersed in non-conductive inorganic material the conductive material comprising carbon-silicon compounds, carbon or silicon
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- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/24—Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon
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- H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
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-nickel powder, and the graphene/nickel 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/nickel conductive composite coating.
Description
Technical field
The present invention relates to conductive coating more particularly to a kind of medium temperature graphene/nickel composite conducting slurries and ceramic matrix
The preparation method of surface graphene/nickel 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, nickel, copper, nickel 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 nickel 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 large Π bond, but exist stablize separation in the application
And scattering problem.Grandson waits quietly under the conditions of sand milling using sun/nonionic surfactant compounding dispersing Nano carbon tubes, with mica or
Titanium dioxide is compound, hence it is evident that improves the dispersibility of CNTs, more traditional carbon nano tube surface adsorbs charged ion or organic matter etc.
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, nickel, 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/nickel composite conducting slurry of present invention offer and ceramic base
The preparation method of body surface face graphene/nickel conductive composite coating, obtain it is a kind of with good combination power and superior electrical conductivity can
Graphene/nickel 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/nickel 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 uses dilute hydrochloric acid to carry out pickling to nano-nickel powder particle, obtains the nano-nickel powder in grey black；
(4) 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 and by above-mentioned steps (3) treated nano-nickel powder and glass powder with low melting point, obtains nano nickel mixing slurry
Material；The ratio for adding nano-nickel powder, organic carrier phase and glass powder is 30-80: 20-75: 2-15；
(5) it under the stirring condition of 120-800r/min, weighs dry, activation graphene powder and is placed in above-mentioned steps
(4) in obtained nano nickel mixed slurry, graphene/nickel slurry presoma is obtained；Wherein graphene powder and nano-nickel powder
Ratio be：1∶15-2∶10；
(6) it is 120-160 DEG C the graphene/nickel slurry presoma obtained in above-mentioned steps (5) 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；
(7) presoma after above-mentioned curing is placed in the de-airing mixer that vacuum degree is a 0.1Mpa with 500-
The rotating speed of 1500r/min persistently stirs 24-72h, obtains the graphene/nickel composite conducting slurry of stable dispersion；
(8) the graphene/nickel composite conducting slurry obtained in above-mentioned steps (7) is uniformly coated to the surface of potsherd,
Coated area is 2.5 × 2.5cm2；
(9) it is 300- the potsherd that graphene/nickel composite conducting slurry has been coated in above-mentioned steps (8) to be placed in temperature
500 DEG C and have in the tube-type atmosphere furnace of inert gas shielding, is sintered 0.5-4h, obtains covering graphene/nickel composite guide electropaining
The potsherd of layer.
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 dilute hydrochloric acid in the step (3) be use 36wt.% concentrated hydrochloric acid dilute made of mass fraction for
6-15wt.% dilute hydrochloric acid；Further include distilled water washing, absolute ethyl alcohol dispersion, drying and processing after the pickling.
Preferably, the ratio of the nano-nickel powder in the step (4), organic carrier and glass powder is 35-70: 25-55: 5-
10；Mixing speed in the step (5) is 200-500r/min, the ratio of graphene and nano-nickel powder is：1∶9-3∶7.
Preferably, by the way of drop coating that the graphene/nickel composite conducting slurry prepared is uniform in the step (8)
It is coated to potsherd surface.
Preferably, the step (9) is to set the potsherd that graphene/nickel composite conducting slurry has been coated in step (8)
It is 350-450 DEG C in temperature and has in the tube-type atmosphere furnace of nitrogen protection, 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-nickel 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/nickel 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/nickel conductive composite coating with certain binding force and superior electrical conductivity energy.
Graphene/nickel 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-nickel powder be conductive bodies, wherein graphene can be with nanometer
Nickel powder mixes, and preferably forms conductive path (i.e.：Nano nickel is filled to the junction of graphene sheet layer), and can greatly drop
The dosage of low nano nickel, compared to conventional nickel base conductive pulp, 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/nickel can be more preferable
Combination on ceramic matrix surface, solve adhesion problem of the conductive phases such as graphene/nickel 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/nickel conductive coating being prepared in the embodiment of the present invention 5.
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/nickel 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) since there may be NiO, NiO for nano-nickel powder particle surface2And Ni2O3Equal oxides, influence its electric conductivity, need
It uses the concentrated hydrochloric acid of 36wt.% to be diluted to mass fraction and removes its oxide on surface for the progress pickling of 6~15wt.% dilute hydrochloric acid,
Using processing procedures such as distilled water washing, absolute ethyl alcohol dispersion, drying, the nano-nickel powder in grey black is obtained；
(4) it weighs organic carrier to be mutually placed in vacuum stirring kettle, under the stirring condition of 100r/min, be added in batches mixed
It closes uniformly and by above-mentioned steps (3) treated nano-nickel powder and glass powder with low melting point, obtains nano nickel mixed slurry；Add
The ratio of plus nano nickel powder, organic carrier phase and glass powder is 30: 20: 2；
(5) it under the stirring condition of 120r/min, weighs dry, activation graphene powder and is placed in above-mentioned steps (4) institute
In obtained nano nickel mixed slurry, graphene/nickel slurry presoma is obtained；The wherein ratio of graphene powder and nano-nickel powder
For：1∶15；
(6) by the graphene/nickel slurry presoma obtained in above-mentioned steps (5) 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；
(7) 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 the graphene/nickel composite conducting slurry for obtaining stable dispersion for 24 hours；
(8) the graphene/nickel composite conducting slurry obtained in above-mentioned steps (7) is uniformly coated to the surface of potsherd,
Coated area is 2.5 × 2.5cm2；
(9) it is 300 DEG C the potsherd that graphene/nickel composite conducting slurry has been coated in above-mentioned steps (8) to be placed in temperature
And have in the tube-type atmosphere furnace of inert gas shielding, it is sintered 0.5h, obtains the ceramics for covering graphene/nickel conductive composite coating
Piece.
Embodiment 2
A kind of preparation method of medium temperature graphene/nickel 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) since there may be NiO, NiO for nano-nickel powder particle surface2And Ni2O3Equal oxides, influence its electric conductivity, need
It uses the concentrated hydrochloric acid of 36wt.% to be diluted to mass fraction and removes its oxide on surface for the progress pickling of 6~15wt.% dilute hydrochloric acid,
Using processing procedures such as distilled water washing, absolute ethyl alcohol dispersion, drying, the nano-nickel powder in grey black is obtained；
(4) it weighs organic carrier to be mutually placed in vacuum stirring kettle, under the stirring condition of 800r/min, be added in batches mixed
It closes uniformly and by above-mentioned steps (3) treated nano-nickel powder and glass powder with low melting point, obtains nano nickel mixed slurry；Add
The ratio of plus nano nickel powder, organic carrier phase and glass powder is 80: 75: 15；
(5) it under the stirring condition of 800r/min, weighs dry, activation graphene powder and is placed in above-mentioned steps (4) institute
In obtained nano nickel mixed slurry, graphene/nickel slurry presoma is obtained；The wherein ratio of graphene powder and nano-nickel powder
For：2∶10；
(6) by the graphene/nickel slurry presoma obtained in above-mentioned steps (5) 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；
(7) 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 the graphene/nickel composite conducting slurry of stable dispersion；
(8) the graphene/nickel composite conducting slurry obtained in above-mentioned steps (7) is uniformly coated to the surface of potsherd,
Coated area is 2.5 × 2.5cm2；
(9) it is 500 DEG C the potsherd that graphene/nickel composite conducting slurry has been coated in above-mentioned steps (8) to be placed in temperature
And have in the tube-type atmosphere furnace that nitrogen is protected, it is sintered 4h, obtains the potsherd for covering graphene/nickel conductive composite coating.
Embodiment 3
A kind of preparation method of medium temperature graphene/nickel 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) since there may be NiO, NiO for nano-nickel powder particle surface2And Ni2O3Equal oxides, influence its electric conductivity, need
It uses the concentrated hydrochloric acid of 36wt.% to dilute into mass fraction and removes its surface oxidation for the progress pickling of the dilute hydrochloric acid of 6-15wt.%
Object obtains the nano-nickel powder in grey black using processing procedures such as distilled water washing, absolute ethyl alcohol dispersion, drying；
(4) 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 and pretreated nano-nickel powder (being provided by Aladdin reagent Co., Ltd) and eutectic are provided in batches
The ratio of point glass powder, addition nano-nickel powder, organic carrier and glass powder is 35: 25: 5；
(5) 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 nickel mixed slurry, the ratio of wherein graphene and nano-nickel powder is：1∶9；
(6) it is 120 DEG C above-mentioned tentatively uniformly mixed graphene/nickel slurry presoma 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；
(7) 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 the graphene/nickel composite conducting slurry of stable dispersion；
(8) by the graphene/nickel composite conducting slurry prepared, uniform coated ceramic piece surface, control apply in a manner of drop coating
Clad can product is 2.5 × 2.5cm2；
(9) potsherd for having coated graphene/nickel composite conducting slurry is placed in the pipe that temperature is 350 DEG C and nitrogen protection
In formula atmosphere furnace, it is sintered 0.5h, you can obtain covering the potsherd of graphene/nickel conductive composite coating；
Embodiment 4
A kind of preparation method of medium temperature graphene/nickel 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) since there may be NiO, NiO for nano-nickel powder particle surface2And Ni2O3Equal oxides, influence its electric conductivity, need
It uses the concentrated hydrochloric acid of 36wt.% to dilute into mass fraction and removes its surface oxidation for the progress pickling of the dilute hydrochloric acid of 6-15wt.%
Object obtains the nano-nickel powder in grey black using processing procedures such as distilled water washing, absolute ethyl alcohol dispersion, drying；
(4) 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 and pretreated nano-nickel powder (being provided by Aladdin reagent Co., Ltd) and eutectic are provided in batches
The ratio of point glass powder, addition nano-nickel powder, organic carrier and glass powder is 70: 55: 10；
(5) 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 nickel mixed slurry, the ratio of wherein graphene and nano-nickel powder is：3∶7；
(6) it is 60 DEG C above-mentioned tentatively uniformly mixed graphene/nickel slurry presoma 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；
(7) 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 the graphene/nickel composite conducting slurry of stable dispersion；
(8) by the graphene/nickel composite conducting slurry prepared, uniform coated ceramic piece surface, control apply in a manner of drop coating
Clad can product is 2.5 × 2.5cm2；
(9) potsherd for having coated graphene/nickel composite conducting slurry is placed in the pipe that temperature is 450 DEG C and nitrogen protection
In formula atmosphere furnace, it is sintered 2h, you can obtain covering the potsherd of graphene/nickel conductive composite coating.
Embodiment 5
A kind of preparation method of medium temperature graphene/nickel 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) since there may be NiO, NiO for nano-nickel powder particle surface2And Ni2O3Equal oxides, influence its electric conductivity, need
It uses the concentrated hydrochloric acid of 36wt.% to dilute into mass fraction and removes its oxide on surface for the progress pickling of the dilute hydrochloric acid of 10wt.%,
Using processing procedures such as distilled water washing, absolute ethyl alcohol dispersion, drying, the nano-nickel powder in grey black is obtained；
(4) 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 and pretreated nano-nickel powder (being provided by Aladdin reagent Co., Ltd) and eutectic are provided in batches
The ratio of point glass powder, addition nano-nickel powder, organic carrier and glass powder is 55: 35: 10；
(5) 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 nickel mixed slurry, the ratio of wherein graphene and nano-nickel powder is：2∶8；
(6) it is 150 DEG C above-mentioned tentatively uniformly mixed graphene/nickel slurry presoma 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；
(7) 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 the graphene/nickel composite conducting slurry of stable dispersion；
(8) by the graphene/nickel composite conducting slurry prepared, uniform coated ceramic piece surface, control apply in a manner of drop coating
Clad can product is 2.5 × 2.5cm2；
(9) potsherd for having coated graphene/nickel composite conducting slurry is placed in the pipe that temperature is 450 DEG C and nitrogen protection
In formula atmosphere furnace, it is sintered 0.5h, you can obtain covering the potsherd of graphene/nickel conductive composite coating.
Comparative example 1
The sintering temperature of 5 step of embodiment (9) is adjusted to 250 DEG C, remaining parameter constant.
Comparative example 2
The sintering temperature of 5 step of embodiment (9) is adjusted to 550 DEG C, remaining parameter constant.
Comparative example 3
The ratio of the addition nano-nickel powder, organic carrier and glass powder of 5 step of embodiment (4) is adjusted to 20: 15: 1,
Remaining parameter constant.
Comparative example 4
The ratio of the addition nano-nickel powder, organic carrier and glass powder of 5 step of embodiment (4) 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：
Table 1：Embodiment 1-5 sample tests
Table 2：Comparative example 1-4 sample tests
Graphene/nickel conductive composite coating photo made from the embodiment of the present invention 5 is as shown in Figure 1 d, can from Fig. 1 d
Go out graphene and nanometer nickel particles and be coated in potsherd matrix surface well so that whole surface is in black, and surfacing
Property is preferable.The electric conductivity of graphene/nickel conductive composite coating and caking property made from embodiment 5 are as shown in table 1.From table 1
It can be seen that the surface resistivity of the graphene/nickel conductive composite coating is 12.367-12.475 ohm, i.e., electric conductivity is preferable.
Force test method is combined using the surfaces ASTMD3359-2002, it is found that the intersection in scribing line has the peeling paint of small pieces, 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-nickel 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-nickel powder, the ratio of organic carrier and glass powder of invention have reached balance appropriate.
Graphene/nickel 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-nickel powder be conductive bodies, wherein graphene can be with nanometer
Nickel powder mixes, and preferably forms conductive path (i.e.：Nano nickel is filled to the junction of graphene sheet layer), and can greatly drop
The dosage of low nano nickel, compared to conventional nickel base conductive pulp, 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/nickel can be more preferable
Combination on ceramic matrix surface, solve adhesion problem of the conductive phases such as graphene/nickel in matrix surface.
Claims (8)
1. a kind of preparation method of medium temperature graphene/nickel 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）Pickling is carried out to nano-nickel powder particle using dilute hydrochloric acid, obtains the nano-nickel powder in grey black；
（4）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
It closes uniformly and passes through above-mentioned steps（3）Treated nano-nickel powder and glass powder with low melting point, obtains nano nickel mixed slurry；Add
The ratio of plus nano nickel powder, organic carrier phase and glass powder is 30-80:20-75:2-15；
（5）Under the stirring condition of 120-800r/min, weighs dry, activation graphene powder and be placed in above-mentioned steps（4）Institute
In obtained nano nickel mixed slurry, graphene/nickel slurry presoma is obtained；The wherein ratio of graphene powder and nano-nickel powder
It is 1:15-2:10；
（6）By above-mentioned steps（5）In obtained graphene/nickel slurry presoma 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；
（7）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 the graphene/nickel composite conducting slurry of stable dispersion；
（8）By above-mentioned steps（7）In obtained graphene/nickel composite conducting slurry be uniformly coated to the surface of potsherd, coating
Area is 2.5 × 2.5cm2；
（9）By above-mentioned steps（8）It is 300-500 DEG C that the middle potsherd for having coated graphene/nickel composite conducting slurry, which is placed in temperature,
And have in the tube-type atmosphere furnace of inert gas shielding, it is sintered 0.5-4h, obtains the pottery for covering graphene/nickel conductive composite coating
Tile.
2. the preparation method of medium temperature graphene/nickel composite conducting slurry according to claim 1, 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/nickel composite conducting slurry according to claim 2, 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/nickel composite conducting slurry according to claim 1, which is characterized in that described
Step（3）In dilute hydrochloric acid be use 36wt.% concentrated hydrochloric acid dilute made of mass fraction for 6-15wt.% dilute hydrochloric acid；It is described
Further include distilled water washing, absolute ethyl alcohol dispersion, drying and processing after pickling.
5. the preparation method of medium temperature graphene/nickel composite conducting slurry according to claim 1, which is characterized in that described
Step（4）In nano-nickel powder, organic carrier and glass powder ratio be 35-70:25-55:5-10；The step（5）In
Mixing speed is 200-500r/min, the ratio of graphene and nano-nickel powder is 1:9-3:7.
6. the preparation method of medium temperature graphene/nickel composite conducting slurry according to claim 1, which is characterized in that described
Step（8）It is middle that the graphene/nickel composite conducting slurry prepared is uniformly coated to potsherd surface by the way of drop coating.
7. the preparation method of medium temperature graphene/nickel composite conducting slurry according to claim 1, which is characterized in that described
Step（9）It is by step（8）The middle potsherd for having coated graphene/nickel composite conducting slurry be placed in temperature be 350-450 DEG C and
Have in the tube-type atmosphere furnace of nitrogen protection, is sintered 0.5-2h.
8. a kind of conductive coating, the conductive coating is used as what claim 1-7 any one of them methods were prepared leads
Plasma-based material is prepared.
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