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CN-121983372-A - Copper-nickel alloy inner electrode slurry and preparation method and application thereof

CN121983372ACN 121983372 ACN121983372 ACN 121983372ACN-121983372-A

Abstract

The invention discloses a preparation method of copper-nickel alloy inner electrode slurry, which specifically comprises the following steps of preparing copper-nickel nano alloy powder, preparing copper-nickel micro alloy powder, synthesizing a copper complex, and preparing copper-nickel alloy inner electrode slurry according to products obtained in the steps 1-3. The invention also discloses copper-nickel alloy inner electrode slurry and application thereof. The electrode paste prepared by the invention has better oxidation resistance, and the capacitance solute prepared by the electrode paste has higher performance.

Inventors

  • Yin Danning
  • FENG YAN

Assignees

  • 阿梓萨科技(深圳)有限公司

Dates

Publication Date
20260505
Application Date
20260316

Claims (8)

  1. 1. The preparation method of the copper-nickel alloy inner electrode slurry is characterized by comprising the following steps: Step 1, preparing copper-nickel nano alloy powder; Step 2, preparing copper-nickel micron alloy powder; Step 3, synthesizing a copper complex; and 4, preparing copper-nickel alloy inner electrode slurry according to the product obtained in the step 1-3.
  2. 2. The method for preparing the copper-nickel alloy inner electrode slurry according to claim 1, wherein the specific process of the step 1 is as follows: step 1.1, taking 13.4-26.8 g copper chloride and 12.9-25.8 g nickel chloride, dissolving in 300-600 mL water, adding 50-100mL ethylenediamine and 50-100g polyvinylpyrrolidone, and stirring at room temperature for 60-120min to obtain a blue-green copper-nickel mixed solution; Step 1.2, weighing 18.9-37.8 gNaBH 4 , putting into a beaker, adding into 300-600 mL ice water mixed solution, stirring and dissolving to obtain NaBH 4 solution; Step 1.3, slowly dripping NaBH 4 solution into the copper-nickel mixed solution under the protection of nitrogen at 80-90 ℃ by using a constant pressure dropping funnel for 45-65min, changing the color of the solution from blue-green to black, continuously stirring and reacting for 1-2h after the NaBH 4 solution is added, obtaining a copper-nickel-containing colloidal solution, adding 500-1000mL of ethanol for dilution, centrifuging at 8000-10000rpm for 20-30min, removing supernatant, repeating for three times, centrifuging and collecting a solid product, and drying at 50-60 ℃ for 6-12h to obtain black copper-nickel nano alloy powder.
  3. 3. The method for preparing the copper-nickel alloy inner electrode slurry according to claim 2, wherein the specific process of the step 2 is as follows: Step 2.1, dissolving 46.6-93.2g of copper sulfate and 31.4-62.8g of nickel sulfate in 300-600 mL g of water, adding 100-200mL of ethylenediamine, and stirring at room temperature for 20-30min to obtain a blue-green copper-nickel mixed solution; Step 2.2, dropwise adding the copper-nickel mixed solution prepared in the step 2.1 into 500-1000mL of acetone solution, stirring while dropwise adding for 20-40min, collecting solid precipitate, and drying at 50-60 ℃ for 6-12h to obtain blue and uniformly mixed copper-nickel powder; Step 2.3, spreading the copper-nickel powder obtained in the step 2.2 into a reaction boat, transferring the reaction boat into a tube furnace, introducing H 2 /N 2 mixed gas, ventilating for 30-60min at room temperature, removing air, heating at 4-8 o C/min, keeping the temperature for 1-2H when the temperature reaches 500-600 o C, cooling at 6-10 o C/min, taking out the reaction boat, putting the sintered copper-nickel alloy powder into a mortar, and grinding for 1-2H to obtain the copper-nickel micron alloy powder.
  4. 4. The method for preparing the copper-nickel alloy inner electrode slurry according to claim 3, wherein in the step 2.3, H 2 /N 2 mixed gas is introduced to obtain a flow rate of 20-30mL/min.
  5. 5. A preparation method of the copper-nickel alloy inner electrode slurry according to claim 3 is characterized in that the specific process of the step 3 comprises the steps of dispersing 10-20g of 2, 4-pentanedione in 50-60mL of ethanol solution, adding 6.8-13.6g of sodium ethoxide, stirring at room temperature for 30-40min, adding 3.5-7g of copper chloride, continuing stirring at room temperature for 30-40min, dropwise adding the reaction solution into 200-400mL of ice water with the temperature of 0 o C after the reaction is finished, precipitating precipitates, collecting a filter cake, washing the filter cake with 200-400mL of ice water with the temperature of 0 o C, repeating the washing process for three times, removing unreacted copper chloride and sodium ethoxide, and drying the collected solid product in a reaction oven for 12-18h at the temperature of 40-60 o C to obtain a copper complex.
  6. 6. A preparation method of the copper-nickel alloy inner electrode slurry according to claim 5 is characterized in that the specific process of the step 4 comprises the steps of weighing 5-10g of copper complex, dissolving in a mixed solution of 22-44g of terpineol and 8-16g of diethylene glycol butyl ether acetate, stirring for 30-40min at room temperature, adding 1.5-3g of ethylcellulose powder, continuously mechanically stirring for 2-4h in a water bath at 70-80 ℃ until ethylcellulose is completely dissolved to obtain a viscous uniform solution, cooling to room temperature for standby, adding 1-2g of aliphatic alcohol polyether phosphate, 1.5-3g of hydrogenated castor oil and 0.1-0.2g of benzotriazole auxiliary agent, stirring uniformly, adding 10.9-21.8g of copper-nickel nano alloy and 50-100g of copper-nickel micro alloy while stirring and mixing, grinding for 5-10 times by a three-roller grinder to obtain uniform copper-nickel alloy slurry, finally adopting diethylene glycol butyl ether acetate to prepare the nickel slurry viscosity, controlling the viscosity to 20000-cP, and then preparing the copper-nickel alloy inner stress slurry, and standing for 18-24h to obtain the final electrode slurry.
  7. 7. The copper-nickel alloy inner electrode slurry prepared by the preparation method of the copper-nickel alloy inner electrode slurry according to any one of claims 1-6.
  8. 8. Use of the copper-nickel alloy inner electrode paste according to claim 7 in a multilayer ceramic capacitor.

Description

Copper-nickel alloy inner electrode slurry and preparation method and application thereof Technical Field The invention belongs to the technical field of manufacturing of multilayer ceramic capacitors, relates to copper-nickel alloy inner electrode slurry, and also relates to a preparation method and application of the copper-nickel alloy inner electrode slurry. Background The multilayer ceramic capacitor is a capacitor device formed by overlapping ceramics and metals in a staggered mode, and is widely applied to various electronic products and capacitor devices at present. The core component of the multilayer ceramic capacitor consists of an inner electrode, a terminal electrode and a ceramic body, wherein palladium-silver inner electrode slurry (a silver terminal electrode matched with the inner electrode) is developed in the early stage, and due to extremely high cost of palladium serving as a noble metal, silver inner electrode slurry (a silver terminal electrode matched with the silver inner electrode) is developed. In recent years, nickel internal electrode paste (copper terminal paste) and copper internal electrode paste (copper terminal paste) have been further developed for cost reduction. Obviously, the nickel inner electrode slurry has very high oxidation resistance, but the nickel conductivity is poor, the nickel is relatively expensive compared with copper, and the welding performance is poor due to heterogeneity between the nickel inner electrode and the copper end electrode, in contrast, the copper inner electrode material is low in cost, good in conductivity, and the inner electrode and the end electrode are easy to weld, but the copper inner electrode is easy to oxidize. How to combine the advantages of copper and nickel without circumventing their disadvantages. The construction of the copper-nickel alloy is one of the effective methods for preparing the slurry with high efficiency, low cost, conductivity and excellent bonding performance of the terminal electrode. It should be noted that, in the preparation process of the micro-scale and nano-scale copper-nickel alloys, the reduction potential of copper ions (+0.34V) and nickel ions (-0.25V) is positive or negative, so that the reduction of the copper ions and the nickel ions is asynchronous, the copper ions are easy to reduce, the nickel ions are difficult to reduce, copper and nickel phases are separated, alloy particles are easy to agglomerate, and the alloy effect is poor. In addition, when the copper-nickel alloy slurry is used for preparing the multilayer ceramic capacitor, the compactness of the inner electrode influences the performance of the capacitor, such as reliability, capacitance and the field of high-frequency application. Disclosure of Invention The invention aims to provide a preparation method of copper-nickel alloy inner electrode slurry, which has better oxidation resistance and higher capacitance solute performance. A second object of the present invention is to provide copper nickel alloy inner electrode paste. A third object of the present invention is to provide the use of copper nickel alloy inner electrode paste. The first technical scheme adopted by the invention is that the preparation method of the copper-nickel alloy inner electrode slurry specifically comprises the following steps: Step 1, preparing copper-nickel nano alloy powder; Step 2, preparing copper-nickel micron alloy powder; Step 3, synthesizing a copper complex; and 4, preparing copper-nickel alloy inner electrode slurry according to the product obtained in the step 1-3. The first technical scheme of the invention is characterized in that: The specific process of the step1 is as follows: step 1.1, taking 13.4-26.8 g copper chloride and 12.9-25.8 g nickel chloride, dissolving in 300-600 mL water, adding 50-100mL ethylenediamine and 50-100g polyvinylpyrrolidone, and stirring at room temperature for 60-120min to obtain a blue-green copper-nickel mixed solution; Step 1.2, weighing 18.9-37.8 gNaBH 4, putting into a beaker, adding into 300-600 mL ice water mixed solution, stirring and dissolving to obtain NaBH 4 solution; Step 1.3, slowly dripping NaBH 4 solution into the copper-nickel mixed solution under the protection of nitrogen at 80-90 ℃ by using a constant pressure dropping funnel for 45-65min, changing the color of the solution from blue-green to black, continuously stirring and reacting for 1-2h after the NaBH 4 solution is added, obtaining a copper-nickel-containing colloidal solution, adding 500-1000mL of ethanol for dilution, centrifuging at 8000-10000rpm for 20-30min, removing supernatant, repeating for three times, centrifuging and collecting a solid product, and drying at 50-60 ℃ for 6-12h to obtain black copper-nickel nano alloy powder. The specific process of the step 2 is as follows: Step 2.1, dissolving 46.6-93.2g of copper sulfate and 31.4-62.8g of nickel sulfate in 300-600 mL g of water, adding 100-200mL of ethylenediamine, and stir