CN111318688A - Preparation method and application of aluminum-based conductive powder - Google Patents
Preparation method and application of aluminum-based conductive powder Download PDFInfo
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- CN111318688A CN111318688A CN202010214483.0A CN202010214483A CN111318688A CN 111318688 A CN111318688 A CN 111318688A CN 202010214483 A CN202010214483 A CN 202010214483A CN 111318688 A CN111318688 A CN 111318688A
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 97
- 239000000843 powder Substances 0.000 title claims abstract description 67
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000002131 composite material Substances 0.000 claims abstract description 32
- 238000007747 plating Methods 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 23
- 229910052802 copper Inorganic materials 0.000 claims abstract description 16
- 239000000126 substance Substances 0.000 claims abstract description 12
- 229910052709 silver Inorganic materials 0.000 claims abstract description 10
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 9
- 229910052718 tin Inorganic materials 0.000 claims abstract description 9
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 9
- 239000000725 suspension Substances 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 21
- 239000010949 copper Substances 0.000 claims description 19
- 238000005406 washing Methods 0.000 claims description 19
- 230000007935 neutral effect Effects 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 12
- 239000006228 supernatant Substances 0.000 claims description 12
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 11
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 11
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 11
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 239000006185 dispersion Substances 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 229910017767 Cu—Al Inorganic materials 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 229910001868 water Inorganic materials 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 3
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000000276 potassium ferrocyanide Substances 0.000 claims description 3
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 claims description 3
- 229940074439 potassium sodium tartrate Drugs 0.000 claims description 3
- 235000011006 sodium potassium tartrate Nutrition 0.000 claims description 3
- XOGGUFAVLNCTRS-UHFFFAOYSA-N tetrapotassium;iron(2+);hexacyanide Chemical compound [K+].[K+].[K+].[K+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] XOGGUFAVLNCTRS-UHFFFAOYSA-N 0.000 claims description 3
- ILJSQTXMGCGYMG-UHFFFAOYSA-N triacetic acid Chemical compound CC(=O)CC(=O)CC(O)=O ILJSQTXMGCGYMG-UHFFFAOYSA-N 0.000 claims description 3
- 238000011549 displacement method Methods 0.000 claims description 2
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 abstract description 8
- 230000003647 oxidation Effects 0.000 abstract description 8
- 238000007254 oxidation reaction Methods 0.000 abstract description 8
- 239000004332 silver Substances 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 3
- 239000011159 matrix material Substances 0.000 abstract description 2
- 230000005012 migration Effects 0.000 abstract description 2
- 238000013508 migration Methods 0.000 abstract description 2
- 238000005245 sintering Methods 0.000 description 10
- 239000000523 sample Substances 0.000 description 8
- 229910000510 noble metal Inorganic materials 0.000 description 6
- 229910018725 Sn—Al Inorganic materials 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000000635 electron micrograph Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 4
- 238000000576 coating method Methods 0.000 description 3
- 239000011267 electrode slurry Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- 238000007650 screen-printing Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 230000004584 weight gain Effects 0.000 description 3
- 235000019786 weight gain Nutrition 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007772 electroless plating Methods 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- KSSJBGNOJJETTC-UHFFFAOYSA-N COC1=C(C=CC=C1)N(C1=CC=2C3(C4=CC(=CC=C4C=2C=C1)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)C1=CC(=CC=C1C=1C=CC(=CC=13)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)C1=CC=C(C=C1)OC Chemical compound COC1=C(C=CC=C1)N(C1=CC=2C3(C4=CC(=CC=C4C=2C=C1)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)C1=CC(=CC=C1C=1C=CC(=CC=13)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)C1=CC=C(C=C1)OC KSSJBGNOJJETTC-UHFFFAOYSA-N 0.000 description 1
- 229910021205 NaH2PO2 Inorganic materials 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229940116411 terpineol Drugs 0.000 description 1
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/17—Metallic particles coated with metal
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
- C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
- C23C18/36—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents using hypophosphites
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/42—Coating with noble metals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
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- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Conductive Materials (AREA)
Abstract
The invention discloses a preparation method of aluminum-based conductive powder, which takes pre-treated aluminum powder as a basic unit and prepares mixed or coated X-Al composite conductive powder by a chemical plating reduction method or a chemical plating replacement method, wherein X is Sn, Ni, Ag, Cu or Zn, and the mass ratio of X in the X-Al composite conductive powder is 10-20%; the X-Al composite conductive powder prepared by the method has stable use effect and high oxidation resistance; the aluminum electrode prepared by adopting the aluminum-based conductive powder has smooth and complete surface, compact and uniform tissue and good binding force with a matrix, and does not have ion migration phenomenon compared with a pure silver electrode; is suitable for industrial production and market popularization and application.
Description
Technical Field
The invention belongs to the field of electrode material preparation, and particularly relates to a preparation method of aluminum-based conductive powder and application of the aluminum-based conductive powder to a metal electrode.
Background
The traditional electrode slurry mostly relates to noble metals, in particular to silver electrode slurry, and has wide application range and high use frequency. However, in recent years, noble metal pastes typified by pure silver electrodes have been greatly limited due to the increase in the price of noble metals and the demand for low-cost production. The use of base metals in place of noble metals in electronic pastes has been greatly developed, particularly copper and aluminum electrode pastes. The copper electrode slurry can meet the requirement of sintering non-oxidation environment when in use, has certain limitation in use, and the aluminum electrode can be sintered in air, so that the use is more convenient. However, aluminum electrodes have a higher resistance than silver electrodes and are prone to oxidation when left for a long time. Therefore, the development of the anti-oxidation aluminum-based composite material for preparing the metal electrode has better development prospect. The aluminum-based conductive powder and the aluminum metal electrode are prepared by different coating methods, and the electrode has good performance and strong oxidation resistance.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a preparation method of aluminum-based conductive powder, which takes pre-treated aluminum powder as a basic unit and prepares mixed or coated X-Al composite conductive powder by a chemical plating reduction method or a chemical plating replacement method, wherein X is Sn, Ni, Ag, Cu or Zn, and the mass ratio of X in the X-Al composite conductive powder is 10-20%; the aluminum-based conductive powder prepared by the product can meet the requirement of preparing low-resistivity and high-oxidation-resistance aluminum electrodes in industrial production, so that noble metal electrodes such as pure silver electrodes and the like are replaced, and the cost is reduced.
The aluminum powder is pretreated in the method, aluminum powder with the particle size of 2-3 mu m is placed in 0.002-0.0025 mol/L alkali solution to be treated for 1-2 min, then the aluminum powder is taken out and washed to be neutral by deionized water, then the aluminum powder is placed in dilute hydrochloric acid with the volume concentration of 5-7% and the volume of 2-3 times of the powder volume, the aluminum powder is heated to 40-50 ℃ to be treated for 10-15 min, the precipitate is taken out and washed by water until the washing liquid is neutral, and the aluminum powder is dried for later use.
The alkali in the alkali solution is NaOH or KOH.
When X is Ag, coating Ag on the surface of Al by adopting a chemical plating displacement method, and specifically comprising the following steps:
(1) preparing the pretreated aluminum powder into an aluminum powder suspension with the mass concentration of 40-60%, dropwise adding the aluminum powder suspension into a Cu plating solution at the speed of 25-35 drops/min under the conditions of ultrasonic stirring and the temperature of 40-50 ℃, and dropwise adding a PVP dispersion with the mass concentration of 10-15%;
(2) after the aluminum powder suspension is dripped, continuing to perform ultrasonic stirring for 25-35 min, standing after the ultrasonic stirring is completed, pouring out supernatant, washing the powder with deionized water until the pH of the supernatant is neutral, and drying to obtain Cu-Al composite conductive powder;
(3) preparing a suspension with the mass concentration of 40-50% from Cu-Al composite conductive powder, dropwise adding the suspension into an Ag plating solution at a speed of 15-25 drops/min under the conditions of ultrasonic stirring and 45-55 ℃, and dropwise adding a PVP dispersion liquid with the mass concentration of 10-15%;
(4) and (4) continuing ultrasonic stirring for 25-35 min after the suspension liquid in the step (3) is dripped, taking out the solid, standing and washing until the pH of the supernatant liquid is neutral, and drying to obtain the Ag-Al composite conductive powder.
The copper plating solution comprises 5g/200mL of copper sulfate pentahydrate, 6g/200mL of ethylenediamine tetraacetic acid, 2g/200mL of potassium sodium tartrate, 0.0004g/200mL of potassium ferrocyanide, 1.27mL/200mL of methanol, 1.66mL/200mL of formaldehyde and 8g/200mL of sodium hydroxide; the pH value of the copper plating solution is 9-10.
The composition of the Ag plating solution is AgNO39.85g/300mL, 32-35 mL/300mL of triacetic acid tetramine, C6H12O625～30g/300mL。
When X is Sn, Ni, Cu or Zn, preparing X-Al composite powder by adopting a chemical plating reduction method, and comprising the following steps:
(1) preparing the pretreated aluminum powder into an aluminum powder suspension with the mass concentration of 40-60%, dropwise adding the aluminum powder suspension into an X plating solution at the speed of 25-35 drops/min under the condition of ultrasonic stirring and at the temperature of 45-55 ℃, and dropwise adding a PVP (polyvinyl pyrrolidone) dispersion with the mass concentration of 10-15%, wherein X is Sn, Ni, Cu or Zn; the plating X solution is prepared by adopting a conventional formula;
(2) after the aluminum powder suspension is dripped, continuing to ultrasonically stir for 25-35 min, taking out the solid, standing and washing until the pH value of the supernatant is neutral, and drying to obtain X-Al composite conductive powder; x is Sn, Ni, Cu or Zn.
The invention also aims to apply the aluminum-based conductive powder prepared by the preparation method of the aluminum-based conductive powder to the preparation of the metal electrode.
The X-Al composite conductive powder prepared by the method has stable use effect and high oxidation resistance; the aluminum electrode prepared by adopting the aluminum-based conductive powder has smooth and complete surface, compact and uniform tissue and good binding force with a matrix, and does not have ion migration phenomenon compared with a pure silver electrode; is suitable for industrial production and market popularization and application.
Drawings
FIG. 1 is an SEM electron micrograph (at different magnifications) of Ag-Al composite conductive powder prepared by reduction-replacement of electroless plating in example 1;
FIG. 2 is an SEM (magnification difference) electron micrograph of an aluminum film on the surface of the aluminum electrode prepared in example 1;
FIG. 3 is an SEM electron micrograph (at different magnifications) of the Sn-Al composite conductive powder prepared by the electroless plating reduction method in example 2;
FIG. 4 is an SEM (scanning Electron microscope) image (under different magnifications) of the surface aluminum film of the aluminum electrode prepared in example 2;
FIG. 5 is an SEM photograph (under different magnifications) of a conventional aluminum electrode in a comparative example.
Detailed Description
The present invention is further illustrated by the following examples, but the scope of the invention is not limited to the above-described examples.
Example 1: the preparation method of the aluminum-based conductive powder takes the pre-treated aluminum powder as a basic unit, and prepares the Ag-Al composite conductive powder by chemical plating displacement, wherein the mass ratio of Ag in the Ag-Al composite conductive powder is 10 percent, and the method comprises the following steps:
(1) placing aluminum powder with the particle size of 2-3 microns in 0.002mol/L aqueous alkali for treatment for 1.5min, taking out, washing with deionized water to be neutral, placing in dilute hydrochloric acid with the volume concentration of 5% and the volume of 2 times of that of the powder, heating to 40 ℃, treating for 15min, taking out a precipitate, washing with water until the washing liquid is neutral, and drying to obtain pre-treated aluminum powder;
(2) preparing the pretreated aluminum powder into an aluminum powder suspension with the mass concentration of 50%, dropwise adding 40mL of the aluminum powder suspension into 200mL of Cu plating solution at the speed of 30 drops/min under the conditions of ultrasonic stirring and 45 ℃, and dropwise adding PVP dispersion liquid (0.6 g of prepared solution) with the mass concentration of 10%; wherein the composition of the Cu plating solution is 5g/200mL of copper sulfate pentahydrate, 6g/200mL of ethylenediamine tetraacetic acid, 2g/200mL of potassium sodium tartrate, 0.0004g/200mL of potassium ferrocyanide, 1.27mL/200mL of methanol, 1.66mL/200mL of formaldehyde and 8g/200mL of sodium hydroxide; the pH value of the copper plating solution is 9-10;
(3) after the aluminum powder suspension is dripped, continuing to perform ultrasonic stirring for 30min, standing after the ultrasonic stirring is completed, pouring out supernatant, washing the powder with deionized water until the pH of the supernatant is neutral, and drying to obtain Cu-Al composite conductive powder;
(4) preparing 50mL of suspension with the mass concentration of 40% from Cu-Al composite conductive powder, dropwise adding the suspension into 300mL of Ag plating solution at 20 drops/min under the conditions of ultrasonic stirring and 50 ℃, and dropwise adding PVP dispersion with the mass concentration of 10%; wherein the composition of the Ag plating solution is AgNO39.85g/300mL, 32mL/300mL of triacetic acid tetraamine, C6H12O625g/300mL；
(5) After the suspension liquid in the step (4) is dripped, continuing to stir ultrasonically for 30min, taking out the solid, standing and washing until the pH value of the supernatant liquid is neutral, and drying to obtain Ag-Al composite conductive powder; the Ag-Al composite conductive powder has high silver powder coverage rate and good combination with aluminum powder. The results are shown in FIG. 1, from which it can be seen that the coating effect is better;
(6) uniformly mixing 70% of Ag-Al composite conductive powder, 15% of glass powder and 15% of organic carrier (ethyl cellulose-terpineol series), and rolling on a three-roll mill until the fineness is less than or equal to 10 mu m;
(7) printing the aluminum paste obtained in the step (6) on a substrate by adopting a screen printing mode, wherein the mesh number of a screen is 250 meshes, then leveling for 5min, and drying for later use by infrared irradiation at 150 ℃;
(8) sintering the sample by using a tubular furnace, wherein the sintering temperature is 620 ℃, the heat preservation time is 10min, the temperature rise time is 25min, the temperature reduction time is 25min, the temperature is reduced to 200 ℃, taking out the sample from the air for cooling, the duration time of the whole sintering process is 1h, and cooling to obtain an aluminum electrode; the aluminum film electron microscope image of the aluminum electrode is shown in fig. 2, and the better melting effect of the conductive powder in the electrode can be seen from the image.
The electrode prepared by the embodiment is flat and smooth in appearance, the resistance of the electrode is measured by a four-probe resistance meter, the resistance of the electrode is 0.15 omega, the oxidation weight gain/30 days is 2.81%, and the resistance change rate/30 d is 2.7%.
Example 2: the preparation method of the aluminum-based conductive powder takes the pre-treated aluminum powder as a basic unit, and prepares the Sn-Al composite conductive powder by a chemical plating reduction method, wherein the mass ratio of Sn in the Sn-Al composite conductive powder is 15 percent, and the method comprises the following steps:
(1) placing aluminum powder with the particle size of 2-3 mu m in 0.0025mol/L aqueous alkali for treatment for 1min, taking out, washing with deionized water to be neutral, then placing in dilute hydrochloric acid with the volume concentration of 6% which is 3 times of the volume of the powder, heating to 50 ℃, treating for 10min, taking out a precipitate, washing with water until the washing liquid is neutral, and drying to obtain pre-treated aluminum powder;
(2) the Sn plating solution is prepared by mixing SnCl2·2H2O 11.4g、(NH2)Cs 30.5g、NaH2PO2·H2O 24.8g、C6H5Na2O7·2H2Dissolving 6.8g of O in water respectively, and diluting to 250mL of constant volume to obtain the product, wherein the pH value is 5.8-6.2;
(3) preparing the pretreated aluminum powder into an aluminum powder suspension with the mass concentration of 50%, dropwise adding 50mL of the aluminum powder suspension into 250mL of Sn plating solution at the speed of 30 drops/min under the conditions of ultrasonic stirring and 50 ℃, and dropwise adding PVP dispersion (0.6 g for preparation) with the mass concentration of 10%;
(4) after the aluminum powder suspension is dripped, continuing to ultrasonically stir for 30min, taking out the solid, standing and washing until the pH value of the supernatant is neutral, and drying to obtain Sn-Al composite conductive powder; the electron micrograph of the powder is shown in FIG. 3;
(5) uniformly mixing 70% of Sn-Al composite conductive powder, 15% of glass powder and 15% of organic carrier, and rolling on a three-roll mill until the fineness is less than or equal to 10 mu m;
(6) printing the aluminum paste obtained in the step (5) on a substrate by adopting a screen printing mode, wherein the mesh number of a screen is 250 meshes, then leveling for 5min, and drying for later use by infrared irradiation at 150 ℃;
(7) sintering the sample by using a tubular furnace, wherein the sintering temperature is 620 ℃, the heat preservation time is 10min, the temperature rise time is 25min, the temperature reduction time is 25min, the temperature is reduced to 200 ℃, taking out the sample from the air for cooling, the duration time of the whole sintering process is 1h, and cooling to obtain an aluminum electrode; the aluminum film electron microscope image of the aluminum electrode is shown in FIG. 4, and it is seen that the surface of the aluminum electrode has partial holes;
the electrode prepared by the embodiment is flat and smooth in appearance, and the resistance of the electrode is measured by a four-probe resistance meter method, wherein the resistance of the electrode is 0.56 omega, the oxidation weight gain is 3.2% per 30 days, and the resistance change rate is 8.9% per 30 days.
Comparative example:
1. uniformly mixing 70% of aluminum powder conductor without any treatment, 10% of glass powder and 20% of organic carrier, and rolling on a three-roll mill until the fineness is less than or equal to 10 mu m;
2. printing the aluminum paste in the step 1 on a substrate by adopting a screen printing mode, wherein the mesh number of a screen is 250 meshes, then leveling for 5min, and drying in a drying oven at 150 ℃ for later use;
3. sintering a sample by using a tubular furnace, wherein the sintering temperature is 620 ℃, the high-temperature heat preservation time is 10min, the temperature rise time is 25min, the temperature reduction time is 25min, the temperature is reduced to 200 ℃, the sample is taken out of the air and cooled, the duration of the whole sintering process is 1h, and a common aluminum electrode is obtained after cooling is finished; the surface electron micrograph of the aluminum electrode is shown in FIG. 5; the electrode resistance of the common aluminum electrode is 1.23 omega, the oxidation weight gain is 6.7% per 30 days, and the resistance change rate is 11.2% per 30 days;
from the results, the aluminum-based conductive powder prepared by the method can be used for preparing ohmic electrodes, replaces noble metal slurry such as pure silver electrodes and the like, and reduces the cost.
Claims (8)
1. A preparation method of aluminum-based conductive powder is characterized by comprising the following steps: the method comprises the steps of taking pre-treated aluminum powder as a basic unit, and preparing mixed or coated X-Al composite conductive powder by a chemical plating reduction method or a chemical plating replacement method, wherein X is Sn, Ni, Ag, Cu or Zn, and the mass ratio of X in the X-Al composite conductive powder is 10-20%.
2. The method for producing an aluminum-based conductive powder according to claim 1, characterized in that: the aluminum powder is pretreated by placing aluminum powder with the particle size of 2-3 mu m into 0.002-0.0025 mol/L alkali solution for treatment for 1-2 min, taking out the aluminum powder and washing the aluminum powder to be neutral by using deionized water, then placing the aluminum powder into dilute hydrochloric acid with the volume concentration of 5-7% and the volume of 2-3 times of the volume of the powder, heating the aluminum powder to 40-50 ℃ for treatment for 10-15 min, taking out a precipitate, washing the precipitate by using water until the washing solution is neutral, and drying the precipitate for later use.
3. The method for producing an aluminum-based conductive powder according to claim 2, characterized in that: the alkali in the alkali solution is NaOH or KOH.
4. The method for preparing the aluminum-based conductive powder according to claim 1, wherein Ag is coated on the surface of Al by a chemical plating displacement method, comprising the following steps:
(1) preparing the pretreated aluminum powder into an aluminum powder suspension with the mass concentration of 40-60%, dropwise adding the aluminum powder suspension into a Cu plating solution at the speed of 25-35 drops/min under the conditions of ultrasonic stirring and the temperature of 40-50 ℃, and dropwise adding a PVP dispersion with the mass concentration of 10-15%;
(2) after the aluminum powder suspension is dripped, continuing to perform ultrasonic stirring for 25-35 min, standing after the ultrasonic stirring is completed, pouring out supernatant, washing the powder with deionized water until the pH of the supernatant is neutral, and drying to obtain Cu-Al composite conductive powder;
(3) preparing a suspension with the mass concentration of 40-50% from Cu-Al composite conductive powder, dropwise adding the suspension into an Ag plating solution at a speed of 15-25 drops/min under the conditions of ultrasonic stirring and 45-55 ℃, and dropwise adding a PVP dispersion liquid with the mass concentration of 10-15%;
(4) and (4) continuing ultrasonic stirring for 25-35 min after the suspension liquid in the step (3) is dripped, taking out the solid, standing and washing until the pH of the supernatant liquid is neutral, and drying to obtain the Ag-Al composite conductive powder.
5. The method for producing an aluminum-based conductive powder according to claim 4, characterized in that: the copper plating solution comprises 5g/200mL of copper sulfate pentahydrate, 6g/200mL of ethylenediamine tetraacetic acid, 2g/200mL of potassium sodium tartrate, 0.0004g/200mL of potassium ferrocyanide, 1.27mL/200mL of methanol, 1.66mL/200mL of formaldehyde and 8g/200mL of sodium hydroxide; the pH value of the copper plating solution is 9-10.
6. The method for producing an aluminum-based conductive powder according to claim 4, characterized in that: the composition of the Ag plating solution is AgNO39.85g/300mL, 32-35 mL/300mL of triacetic acid tetramine, C6H12O625～30g/300mL。
7. The method for preparing the aluminum-based conductive powder according to claim 1, wherein when X is Sn, Ni, Cu or Zn, the X-Al composite powder is prepared by a chemical plating reduction method, comprising the following steps:
(1) preparing the pretreated aluminum powder into an aluminum powder suspension with the mass concentration of 40-60%, dropwise adding the aluminum powder suspension into an X plating solution at the speed of 25-35 drops/min under the condition of ultrasonic stirring and at the temperature of 45-55 ℃, and dropwise adding a PVP (polyvinyl pyrrolidone) dispersion with the mass concentration of 10-15%, wherein X is Sn, Ni, Cu or Zn;
(2) after the aluminum powder suspension is dripped, continuing to ultrasonically stir for 25-35 min, taking out the solid, standing and washing until the pH value of the supernatant is neutral, and drying to obtain X-Al composite conductive powder; x is Sn, Ni, Cu or Zn.
8. The use of the aluminum-based conductive powder produced by the method for producing an aluminum-based conductive powder according to any one of claims 1 to 7 for producing a metal electrode.
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