CN111732456A - Ceramic conductive material and preparation method and application thereof - Google Patents
Ceramic conductive material and preparation method and application thereof Download PDFInfo
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- CN111732456A CN111732456A CN202010613269.2A CN202010613269A CN111732456A CN 111732456 A CN111732456 A CN 111732456A CN 202010613269 A CN202010613269 A CN 202010613269A CN 111732456 A CN111732456 A CN 111732456A
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/89—Coating or impregnation for obtaining at least two superposed coatings having different compositions
- C04B41/90—Coating or impregnation for obtaining at least two superposed coatings having different compositions at least one coating being a metal
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/52—Multiple coating or impregnating multiple coating or impregnating with the same composition or with compositions only differing in the concentration of the constituents, is classified as single coating or impregnation
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01P—WAVEGUIDES; RESONATORS, LINES, OR OTHER DEVICES OF THE WAVEGUIDE TYPE
- H01P1/00—Auxiliary devices
- H01P1/20—Frequency-selective devices, e.g. filters
Abstract
The invention provides a ceramic conductive material and a preparation method and application thereof. The ceramic conductive material comprises a ceramic matrix and a functional coating on the surface of the ceramic matrix, and sequentially comprises the following components: the conductive film comprises a ceramic substrate, a polymer conductive film, a copper layer, a silver layer and a silver protective layer; wherein, the polymer conductive film is one or a combination of a plurality of polypyrrole derivatives, polythiophene derivatives and polystyrene sulfonic acid derivatives; the thickness of the copper layer is 5-10 μm; the thickness of the silver layer is 1-3 μm. The invention also provides a preparation method and application of the ceramic conductive material. The ceramic conductive material has the characteristics of strong bonding force and high conductivity.
Description
Technical Field
The invention relates to a conductive material, in particular to a ceramic conductive material, and belongs to the technical field of conductive material preparation.
Background
With the development of 5G networks, 5G base stations develop towards miniaturization, light weight and high integration, MassiveMIMO technology multiplies the number of antennas, and thus the demand for filters will increase greatly. The 5G ceramic filter selects ceramic as a transmission medium material, has the advantages of high Q value, low insertion loss, high dielectric constant, low loss, small volume, light weight, low cost and the like, and is bound to become the mainstream of the 5G base station filter.
The conventional treatment method for metallizing ceramic surfaces (the current industrial method) is mainly characterized in that metal powder coating is brushed or sprayed on the ceramic surfaces, and then fillers and solvents are removed by a sintering method to obtain metallized layers which play a role in electric conduction. 201310392098.5, 201480007836.2, 201510794320.3, 201710118096.5; 201810259217.2, respectively; 201910787991.5, respectively; 202010008271.7, all of which use different metal powders, or slurries thereof, to achieve a metallized coating. In actual mass production, silver paste (solid content is 65-85%) is used, imported superfine silver powder is selected as a main conductive material, pre-sintering is carried out after brushing is finished, and then high-temperature sintering is carried out, so that a material of metal silver on the surface of ceramic is obtained and used as a core component of the ceramic filter.
This method has the following problems:
(1) in order to achieve a certain conductive effect, a metal layer with the thickness of about 10 micrometers is generally required to be sprayed and brushed, the uniformity of the process is difficult to control, and particularly in holes, multiple times of circulating operation is often required;
(2) in order to realize the conductive effect, the thickness of silver needs to be about 10 micrometers, in the specific production, due to the uniformity problem, in order to realize that the place difficult to attach can meet the requirement, the thickness of other places often exceeds 3-10 times, the thickness needs to be reduced through a subsequent grinding process, a large amount of silver is consumed, and the cost is very expensive;
(3) the superfine silver powder used in the existing silver paste process is mainly obtained through import, and the technology of the aspect is much laggard in China;
(4) when the ceramic filter produced by using the silver paste process is welded, the ceramic and the metal layer are easily separated due to the fact that the difference between the thermal expansion coefficient of the metal and the thermal expansion coefficient of the ceramic is large, and the yield of the product is reduced.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a ceramic conductive material which has good bonding force, excellent conductive performance and low cost and is easy for industrial production.
The invention also aims to provide a preparation method and application of the ceramic conductive material with excellent performance.
In order to achieve the technical purpose, the invention provides a ceramic conductive material, which comprises a ceramic substrate and a functional coating formed on the surface of the ceramic substrate, wherein the functional coating comprises a polymer conductive film, a copper layer, a silver layer and a silver protective layer which are sequentially arranged from inside to outside; the polymer conducting film is one or a combination of a plurality of polypyrrole derivatives, polythiophene derivatives and polystyrene sulfonic acid derivatives; the thickness of the copper layer is 5-10 μm; the thickness of the silver layer is 1-3 μm. According to the ceramic conductive material, the polymer conductive film is used as the transition layer, so that firm bonding force can be formed between the ceramic conductive material and a ceramic substrate; the copper layer is used as the main conductive layer, so that the conductive film has better conductivity and lower preparation cost; the silver layer is used as outer metal, so that the copper layer can be protected, the copper layer is prevented from being oxidized, and meanwhile, the effect of improving welding bonding force can be achieved.
The invention also provides a preparation method of the ceramic conductive material, which adopts an in-situ polymerization method, a layer of polymer conductive film is synthesized on the ceramic substrate as a seed layer, then a copper layer with the thickness of 5-10 mu m is prepared on the conductive layer by a copper electroplating method, then a silver layer (1-3 mu m) is prepared by a silver electroplating method, and finally a silver protective layer is coated to play a role in protecting the copper, so that a metalized coating is obtained, and the welding requirement is met. The preparation method comprises the following steps:
in-situ generation of a polymer conductive film on a ceramic substrate: sequentially carrying out surface adjustment, oxidation and catalytic treatment on the ceramic substrate to obtain a ceramic substrate for in-situ generation of the polymer conducting film;
preparing a copper layer: carrying out electro-coppering treatment on the ceramic substrate with the in-situ generated polymer conductive film to form a copper layer;
pre-plating a silver layer on the copper layer: immersing the copper-plated ceramic substrate into a pre-silver plating solution to obtain a pre-silver-plated substrate;
preparing a silver layer: carrying out electrosilvering treatment on the ceramic substrate subjected to the preliminary silvering to form a silver layer;
annealing: carrying out high-temperature annealing treatment on the ceramic substrate subjected to silver electroplating in an inert gas atmosphere;
preparing a silver protective layer: and immersing the annealed ceramic matrix into a silver discoloration inhibitor, and washing and drying.
The preparation method of the ceramic conductive material also comprises the step of pretreating the ceramic matrix. In one embodiment of the present invention, the pre-treatment comprises: coarsening, cleaning and drying;
wherein, the coarsening is to put the ceramic substrate into coarsening liquid (containing 5-10 wt% of 85% nitric acid, 1-2 wt% of 25% HF and the balance of water) to coarsen for 15-30min, and ultrasonic cleaning is carried out after the coarsening is finished.
Wherein, the cleaning is to put the ceramic substrate after coarsening into ultrasonic cleaning for ultrasonic cleaning (10min), and air-dry after cleaning; then putting into ethanol for ultrasonic cleaning (10 min); after cleaning, vacuum drying is carried out (50-80 ℃ C.; 5-10 min).
The preparation method of the ceramic conductive material comprises the step of preparing a polymer conductive film. A layer of polymer conductive film with high binding force, good stability and excellent conductivity is prepared on a ceramic matrix by an in-situ growth method. Among them, the ceramic substrate of the present invention may be a ceramic substrate that is conventional in the art.
In one embodiment of the present invention, the surface conditioning, oxidation and catalytic treatment are sequentially performed on the ceramic substrate during the in-situ growth of the polymer conductive film.
Wherein the surface conditioning is carried out by immersing the substrate in an aqueous solution containing 0.2 to 0.8 wt% of a vinylimidazolium ion polycondensate and 0.05 to 0.2 wt% of polyvinylpyrrolidone at 45 to 55 ℃ for 30 to 60 seconds.
Wherein, the oxidation treatment is carried out in an aqueous solution containing 5-15 wt% of sodium permanganate and 0.5-2 wt% of sodium borate at 85-90 ℃ for 1-2 min.
Wherein, when the catalytic treatment is carried out, the catalyst is treated for 1 to 3min at normal temperature in an aqueous solution containing 1 to 3wt percent of thiophene or pyrrole polymer monomer (such as 3, 4-ethylenedioxythiophene, 3-butyrylpyrrole and the like which are conventional), 1 to 3wt percent of polyoxyethylene ether phosphate dispersant (such as tristyrylphenol polyoxyethylene ether phosphate potassium salt) and 2 to 5wt percent of phosphoric acid;
the method for preparing the ceramic conductive material comprises the step of preparing a copper layer.
In one embodiment of the present invention, the copper layer is prepared by:
electroplating the ceramic substrate with polymer conducting film in-situ formed as cathode, phosphor-copper plate as anode and current density of 2-5A/dm2(ii) a Electroplating at 20-30 deg.C for 15-30min to form copper layer.
The electroplating solution is conventional, such as: 150g/L of copper sulfate, 150g/L of sulfuric acid, 50ppm of hydrochloric acid, 1g/L of brightener, 10g/L of carrier and 15g/L of leveling agent;
the preparation method of the ceramic conductive material comprises the step of pre-plating a silver layer.
In one embodiment of the invention, during the pre-silver plating, the copper-plated ceramic substrate is immersed into the pre-silver plating tank after being washed by water, and is treated for 0.5-2min at normal temperature.
The preparation method of the ceramic conductive material comprises the step of preparing the silver layer.
In one embodiment of the present invention, the silver layer is prepared by:
the ceramic substrate after pre-silvering is washed by water and hung on a cathode, the ceramic substrate is put into an electro-silvering tank after being powered on, a pure silver plate is taken as an anode, and the current density is controlled to be 0.1-0.5A/dm2Electroplating at 20-30 deg.C for 2-6 min.
The preparation method of the ceramic conductive material comprises the step of high-temperature annealing. The bonding force between the ceramic substrate and the metal layer is firmer through high-temperature annealing.
In one embodiment of the present invention, the high temperature annealing is performed under vacuum at 850-.
The preparation method of the ceramic conductive material comprises the step of preparing the silver protective layer.
In a specific embodiment of the invention, when preparing the silver protective layer, the ceramic substrate after high-temperature annealing is put into a silver protective agent to be soaked for 3-5min, and then is washed and dried.
The raw material for the silver protective layer may be an organic film protecting agent that is conventional in the art.
The present invention also provides a device comprising a part made of the ceramic conductive film of the present invention. The device includes, but is not limited to, a filter.
According to the preparation method of the ceramic conductive film, the polymer conductive film is generated in situ and firmly combined with the ceramic substrate, so that the binding force between the coating and the ceramic is increased; meanwhile, the conductive treatment of the ceramic surface can be realized; by using the method of copper electroplating, the uniformity of the plating layer can reach more than 95 percent; the electroplated copper layer is used as the main conductive layer, so that the use of silver is greatly reduced, and the material cost is reduced.
The preparation method of the ceramic conductive film can solve the problems of binding force, uniformity and the like in the brushing process, so that the prepared ceramic conductive film has the characteristics of good binding force, uniform coating, high conductivity, low price and the like.
Drawings
Fig. 1 is a schematic structural view of a ceramic conductive material in embodiment 1 of the present invention.
Detailed Description
Example 1
The embodiment provides a ceramic conductive material, which has a structure shown in fig. 1, and comprises a ceramic substrate and a functional coating formed on the surface of the ceramic substrate, wherein the functional coating comprises a polymer conductive film, a copper layer, a silver layer and a silver protective layer which are sequentially arranged from inside to outside; the polymer conductive film is one or a combination of more of polypyrrole and its derivatives, polythiophene and its derivatives, and polystyrenesulfonic acid and its derivatives (in this embodiment, the polymer conductive film is a mixture of polythiophene and polystyrenesulfonic acid); the thickness of the copper layer is 7.5 mu m; the thickness of the silver layer is 1.8 μm.
The ceramic conductive material is prepared by the following steps: coarsening, cleaning, drying, surface conditioning, oxidizing, catalyzing, washing, drying, copper electroplating, pre-silver plating, annealing and silver protection.
The method specifically comprises the following steps:
step S1: coarsening: putting the ceramic substrate into a mixture of 85% nitric acid: 5% (mass percentage, the same below), 25% HF: 2 percent; and (4) roughening for 15-30min in the roughening liquid with the balance of water, and carrying out ultrasonic cleaning after roughening is finished (the roughening liquid in other ranges has little influence on the properties of the ceramic substrate).
Step S2: placing the roughened ceramic substrate into ultrasonic cleaning for ultrasonic cleaning (10min), and drying in the air after cleaning; then putting into ethanol for ultrasonic cleaning (10 min); after cleaning, vacuum drying is carried out (80 ℃ C.; 10min)
Step S3: surface conditioning: immersing the ceramic substrate subjected to roughening cleaning into a surface adjusting tank, wherein the adjusting tank contains an adjusting liquid: imidazolium ionomer (N-vinyl imidazolium chloride polymer) 0.5%, polyvinylpyrrolidone 0.1%, and the balance of deionized water; soaking at 50 deg.C for 45 s;
step S4: and (3) oxidation: immersing the ceramic substrate with the surface adjusted in an oxidation tank for treatment, wherein the oxidation tank contains: 10% of sodium permanganate and 1% of sodium borate; the balance of deionized water; ultrasonic treating at 85-90 deg.C for 2 min.
Step S5: catalyzing: immersing the ceramic substrate subjected to oxidation treatment into a catalytic tank for treatment; the catalytic tank contains: 1% of 3, 4-ethylenedioxythiophene, 1% of triphenylvinyl phenol polyoxyethylene ether phosphate potassium salt and 2% of phosphoric acid; the balance of deionized water. Carrying out ultrasonic treatment for 1-3min at normal temperature; and washing and drying after treatment.
Step S6: copper plating: putting the ceramic matrix material subjected to in-situ synthesis of the conductive film into an electroplating bath as a cathode and a copper plate as an anode, wherein the electroplating bath contains 150g/L of copper sulfate, 150g/L of sulfuric acid, 50ppm of hydrochloric acid, 1g/L of brightener (commercially available SH110), 10g/L of carrier (commercially available PE6400) and 15g/L of leveling agent (commercially available PN, octadecyl quaternary ammonium salt); current density 2A/dm2Electroplating at 20-30 deg.C for 22 min.
Step S7: washing the copper-plated ceramic substrate with water, and then immersing the copper-plated ceramic substrate into a pre-silver plating tank, wherein the silver nitrate is 0.5g/L, the sodium sulfite is 100g/L, and the balance is deionized water; and treating for 0.5-2min at normal temperature.
Step S8: washing the pre-silvered ceramic substrate with water, and putting the ceramic substrate into an electro-silvering tank as soon as possible in an electrified manner, wherein 30g/L of silver nitrate, 500g/L of cylinder opening agent (sold in the market under the CT-361 trademark), 80g/L of ammonia water, 20g/L of brightener A, 20g/L of brightener B and the balance of deionized water are added; the current density is controlled at 0.5A/dm2(ii) a Electroplating at 25 deg.C for 4 min.
Step S9: and (3) putting the plated ceramic substrate into an annealing furnace, and annealing for 0.5h at 950 ℃ under the argon condition.
Step S10: and (3) soaking the annealed ceramic substrate in a silver antitarnish agent (commercially available Lesi WS) for 3-5min, and then washing and drying.
The ceramic substrate treated in example 1, wherein the copper layer thickness is 7.5 μm; the thickness of the silver layer is 1.8 mu m; conductivity 2.36 x 10-8Omega, m; the tensile force of a copper wire with the diameter of 1mm is 20.1N in a welding test.
Example 2
This example first provides a ceramic conductive material, which is substantially identical to that of example 1, except that:
in step S3, soaking at 45 ℃ for 60S;
in step S6, the current density is 5A/dm2Electroplating for 15 min;
in step S8, the current density was 0.2A/dm2Electroplating for 5 min.
The ceramic substrate treated in example 2, wherein the copper layer has a thickness of 10 μm; the thickness of the silver layer is 1 mu m; conductivity 2.21 x 10-8Omega, m; the tensile force of the copper wire with the diameter of 1mm is 19.9N in a welding test.
Example 3
This example first provides a ceramic conductive material, which is substantially identical to that of example 1, except that:
in step S3, soaking at 55 deg.C for 30S;
in step S6, the current density is 3A/dm2Electroplating for 12 min;
in step S8, the current density is 0.5A/dm2Electroplating for 6 min;
the ceramic substrate treated in example 3, wherein the copper layer has a thickness of 5 μm; the thickness of the silver layer is 3 mu m; conductivity 2.43 x 10-8Omega, m; the tensile force of a copper wire with the diameter of 1mm is 20.3N in a welding test.
Example 4
This example first provides a ceramic conductive material, which is substantially identical to that of example 1, except that: in step S3, the adjustment solution is: imidazolium ionomer (N-vinyl imidazolium chloride polymer) 0.2%, polyvinylpyrrolidone (PVP) 0.2%, the balance being deionized water; the ceramic substrate treated in example 4, wherein the copper layer thickness is 7.5 μm; the thickness of the silver layer is 1.8 mu m; the conductivity is 2.39 omega.m; the tensile force of a copper wire with the diameter of 1mm is 20.2N in a welding test.
Example 5
This example first provides a ceramic conductive material, which is substantially identical to that of example 1, except that: in step S3, the adjustment solution is: imidazolium ionic polymer (N-vinyl imidazolium chloride polymer) 0.8%, polyvinylpyrrolidone 0.05%, and the balance of deionized water; the ceramic substrate treated in example 5, wherein the copper layer thickness is 7.5 μm; the thickness of the silver layer is 1.8 mu m; the conductivity is 2.32 omega.m; the tensile force of a copper wire with the diameter of 1mm is 20.0N in a welding test.
Example 6
This example first provides a ceramic conductive material, which is substantially identical to that of example 1, except that: in step S5, the catalyst tank includes: 3% of 3, 4-ethylenedioxythiophene, 3% of triphenylvinyl phenol polyoxyethylene ether phosphate potassium salt and 5% of phosphoric acid; the balance of deionized water; the ceramic substrate treated in example 6, wherein the copper layer thickness is 7.5 μm; the thickness of the silver layer is 1.8 mu m; the conductivity is 2.32 omega.m; the tensile force of a copper wire with the diameter of 1mm is 20.0N in a welding test.
Example 7
This example first provides a ceramic conductive material, which is substantially identical to that of example 1, except that: in step S5, the catalyst tank includes: 2% of 3, 4-ethylenedioxythiophene, 2% of triphenylvinyl phenol polyoxyethylene ether phosphate potassium salt and 3% of phosphoric acid; the balance of deionized water; the ceramic substrate treated in example 7, wherein the copper layer thickness was 7.5 μm; the thickness of the silver layer is 1.8 mu m; the conductivity is 2.34 omega.m; the tensile force of a copper wire with the diameter of 1mm is 20.0N in a welding test.
Example 8
This example first provides a ceramic conductive material, which is substantially identical to that of example 1, except that: in step S9, the annealing temperature is 850 ℃; the ceramic substrate treated in example 8, wherein the copper layer thickness was 7.5 μm; the thickness of the silver layer is 1.8 mu m; the conductivity is 2.36 omega.m; the tensile force of a copper wire with the diameter of 1mm is 19.8N in a welding test.
Example 9
This example first provides a ceramic conductive material, which is substantially identical to that of example 1, except that: in step S9, the annealing temperature is 1000 ℃; the ceramic substrate treated in example 9, wherein the copper layer thickness is 7.5 μm; the thickness of the silver layer is 1.8 mu m; the conductivity is 2.36 omega.m; the tensile force of a copper wire with the diameter of 1mm is 20.2N in a welding test.
Comparative example 1
This comparative example provides a ceramic conductive material, which is substantially the same as that in example 1 except that: the absence of step S3 prevents the conductive film from being adsorbed alone, and thus prevents the formation of a polymer conductive film on the surface of the substrate.
Comparative example 2
This comparative example provides a ceramic conductive material, which is substantially the same as that in example 1 except that: the step S4 is not performed, so that the in-situ formed polymer conductive film is particularly easily detached from the substrate surface.
Comparative example 3
This comparative example provides a ceramic conductive material, which is substantially the same as that in example 1 except that: step S5 is not performed, and thus a polymer conductive film cannot be formed on the surface of the substrate.
Comparative example 4
This comparative example provides a ceramic conductive material, which is substantially the same as that in example 1 except that: the step S7 is not performed, which results in the formed electroplated copper layer undergoing a displacement reaction with the silver layer, consuming a portion of the copper layer, and also causing the copper layer to migrate toward the silver layer, thereby affecting subsequent use.
From the comparison between examples 1, 2 and 3, it can be seen that the thickness of the copper layer has an influence on both the resistivity and the tensile force, the thicker the copper layer is, the lower the resistivity is, but the thicker the plating layer is, the poorer the bonding force is;
through comparison among examples 1, 4 and 5, the concentration of the regulator has small influence on the thickness of the plating layer, but has certain influence on the binding force and the conductivity of the plating layer; the higher the concentration of the regulator is, the lower the resistivity of the formed plating layer is, and the higher the conductivity is, because when the concentration of the imidazolium ionic polymer in the regulator is high, the resistivity of the formed high-molecular conductive film layer is low, so that the resistivity of the plating layer is low; the binding force between the plating layer and the base material can be improved when the concentration of PVP is high;
through comparison among the embodiments 1, 6 and 7, it can be seen that the catalyst has a small influence on the thickness of the plating layer, but the higher the catalytic concentration is, the thicker the formed polymer conductive film is, and the conductivity can be improved to a certain extent; however, the higher the concentration is, the thicker the conductive film is, the certain influence on the binding force is also caused, and the binding force between the base material and the plating layer is reduced;
through comparison among examples 1, 8 and 9, it can be seen that the annealing temperature has little influence on the conductivity, but has a certain influence on the binding force, and the increase of the annealing temperature can increase the binding force between the plating layer and the substrate, but if the annealing temperature exceeds the recrystallization temperature of the copper plating layer, the plating layer can be peeled off.
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (9)
1. A ceramic conductive material comprising a ceramic base and a functional coating formed on a surface of the ceramic base, wherein: the functional coating comprises a polymer conductive film, a copper layer, a silver layer and a silver protective layer which are sequentially arranged from inside to outside; the polymer conducting film is one or a combination of a plurality of polypyrrole derivatives, polythiophene derivatives and polystyrene sulfonic acid derivatives; the thickness of the copper layer is 5-10 μm; the thickness of the silver layer is 1-3 μm.
2. A method for preparing a ceramic conductive material according to claim 1, comprising:
in-situ generation of a polymer conductive film on a ceramic substrate: sequentially carrying out surface adjustment, oxidation and catalytic treatment on the ceramic substrate to obtain a ceramic substrate for in-situ generation of the polymer conducting film;
preparing a copper layer: carrying out electro-coppering treatment on the ceramic substrate with the in-situ generated polymer conductive film to form a copper layer;
pre-plating a silver layer on the copper layer: immersing the copper-plated ceramic substrate into a pre-silver plating solution to obtain a pre-silver-plated substrate;
preparing a silver layer: carrying out electrosilvering treatment on the ceramic substrate subjected to the preliminary silvering to form a silver layer;
annealing: carrying out high-temperature annealing treatment on the ceramic substrate subjected to silver electroplating in an inert gas atmosphere;
preparing a silver protective layer: and immersing the annealed ceramic matrix into a silver discoloration inhibitor, and washing and drying.
3. The method for producing a ceramic conductive material according to claim 2, characterized in that: taking a ceramic substrate which generates a polymer conducting film in situ as a cathode and a phosphor copper plate as an anode to carry out electroplating in electroplating solution to form a copper layer, wherein the electroplating parameters are as follows: current density 2-5A/dm2Electroplating at 20-30 deg.C for 15-30 min.
4. The method for producing a ceramic conductive material according to claim 2, characterized in that: using ceramic substrate after pre-silver plating as cathode and pure silver plate asAs anode, at 20-30 deg.C and current density of 0.1-0.5A/dm2Electroplating for 2-6 min.
5. The method for producing a ceramic conductive material according to claim 2, characterized in that: the high-temperature annealing is carried out for 0.5 to 1 hour under the conditions of argon and the temperature of 850-1000 ℃.
6. The method for producing a ceramic conductive material according to claim 2, characterized in that: the surface conditioning is carried out by immersing the substrate in an aqueous solution containing 0.2 to 0.8 wt% of a vinylimidazolium ion polycondensate and 0.05 to 0.2 wt% of polyvinylpyrrolidone at 45 to 55 ℃ for 30 to 60 seconds.
7. The method for producing a ceramic conductive material according to claim 2, characterized in that: when the oxidation treatment is carried out, the treatment is carried out for 1-2min at 85-90 ℃ in an aqueous solution containing 5-15 wt% of sodium permanganate and 0.5-2 wt% of sodium borate.
8. The method for producing a ceramic conductive material according to claim 2, characterized in that: when the catalytic treatment is carried out, the catalyst is treated for 1 to 3min at normal temperature in aqueous solution containing 1 to 3 weight percent of thiophene or pyrrole polymerized monomer, 1 to 3 weight percent of polyoxyethylene ether phosphate dispersant and 2 to 5 weight percent of phosphoric acid.
9. A device comprising a part made of the ceramic conductive material according to any one of claims 1 to 9.
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