An electronic component oxidation-resistant metal electrode material and a method for preparing the same

Abstract

This invention discloses an antioxidant metal electrode material for electronic components and its preparation method in the field of electronic materials technology. The antioxidant metal electrode material comprises conductive metal powder, a reduced vanadium oxide-sulfide core-shell composite modifier, a yttrium-doped manganese-cobalt composite oxide interface stabilizer, an inorganic binder, and an organic carrier. This invention is prepared by mixing and dispersing the conductive metal powder with two inorganic modifying compounds and an inorganic binder in an organic carrier, followed by grinding and degassing. The reduced vanadium oxide-sulfide core-shell composite modifier can efficiently scavenge oxygen free radicals and form a strong coordination relationship with the metal matrix. The yttrium-doped manganese-cobalt composite oxide interface stabilizer can form a dense conductive protective layer on the surface of the metal particles. The synergistic effect of these two modifiers significantly improves the antioxidant performance and conductive stability of the electrode material.

Description

Technical Field

[0001] This invention relates to the field of electronic materials technology, specifically to an antioxidant metal electrode material for electronic components and its preparation method. Background Technology

[0002] With the rapid development of electronic components towards miniaturization, integration, and high performance, higher requirements are being placed on the conductivity, stability, and reliability of electrode materials. Base metal electrode materials, such as nickel and copper electrodes, have become an important development direction to replace traditional precious metal electrodes due to their excellent conductivity and significant cost advantages, and are widely used in electronic components such as multilayer ceramic capacitors, chip inductors, and piezoelectric ceramic devices. However, base metal electrode materials are prone to oxidation reactions during high-temperature sintering or long-term use, forming an insulating oxide layer on the surface of the metal particles. This leads to a significant decrease in the conductivity of the electrode and a sharp increase in contact resistance, seriously affecting the electrical performance and long-term reliability of electronic components. Therefore, how to effectively inhibit the oxidation and corrosion of metal electrodes and improve the oxidation resistance of electrode materials during high-temperature processing has become a key technical problem that urgently needs to be solved in this field.

[0003] To address the aforementioned issues, various technical solutions have been proposed in the existing technology to improve the oxidation resistance of metal electrodes. One common method is to coat the surface of base metal particles with an antioxidant metal layer, such as using silver or silver alloys to coat nickel powder, where the physical isolation of the noble metal layer inhibits oxygen diffusion. Another method is to add antioxidants to the electrode material, such as adding boron, chromium, yttrium, and other metal powders. These elements preferentially react with oxygen at high temperatures to form dense oxides, thereby protecting the base metal matrix. Another approach involves using inorganic glass binders, introducing glass powder into the electrode material to form a continuous glass phase during sintering, which encapsulates and protects the metal particles. Furthermore, passivating the electrode surface with a metal oxide coating is also an effective way to improve oxidation resistance. The above technical solutions have improved the oxidation resistance of metal electrodes to a certain extent, but they still have their own limitations: the bonding strength between the surface noble metal coating layer and the metal substrate is limited, and diffusion and interface separation are prone to occur at high temperatures; the oxidation resistance efficiency of traditional antioxidant additives is low, and excessive addition will reduce the conductivity of the electrode; a single inorganic glass binder is difficult to achieve good interface bonding with the metal substrate while ensuring densification sintering.

[0004] Therefore, existing technologies still require the development of a metal electrode material that combines highly efficient antioxidant properties with excellent electrical conductivity. This material should be able to form a stable and dense antioxidant protective layer during high-temperature sintering while maintaining good electrical contact between metal particles. This invention designs two synergistic inorganic modifying compounds: a reduced vanadium oxide-sulfide core-shell composite modifier and a yttrium-doped manganese-cobalt composite oxide interface stabilizer. These compounds achieve antioxidant functions from two levels: free radical scavenging and interface passivation, effectively overcoming the technical challenge of simultaneously achieving antioxidant efficiency and electrical conductivity in existing technologies, representing a significant technological advancement. Summary of the Invention

[0005] The purpose of this invention is to provide an antioxidant metal electrode material for electronic components and its preparation method, which solves the technical problems of existing metal electrode materials being prone to oxidation during high-temperature sintering and the difficulty in balancing antioxidant and conductivity performance.

[0006] The present invention achieves the above objectives through the following technical solutions: A method for preparing an antioxidant metal electrode material for electronic components, comprising the following steps: S1. By weight, mix 50-70 parts of conductive metal powder, 3-8 parts of reduced vanadium oxide-sulfide core-shell composite modifier, 2-6 parts of yttrium-doped manganese-cobalt composite oxide interface stabilizer, and 8-15 parts of inorganic binder to obtain a solid mixed powder; mix the organic solvent, organic binder, and organic additive, and stir at 80-100℃ to obtain an organic carrier; add the solid mixed powder to the organic carrier and stir to obtain a slurry; transfer the slurry to a grinding mill and grind it to obtain a ground slurry. S2. Place the ground slurry in a vacuum degassing machine for degassing treatment.

[0007] In this invention, the preparation of the antioxidant metal electrode material for electronic components is achieved through the uniform composite of multiphase components. Conductive metal powder, modifier, interface stabilizer, and inorganic binder are thoroughly mixed in an organic carrier, which consists of an organic solvent, binder, and additives. After heating and dissolving, a homogeneous solution is formed. The solid components are then added and ground to ensure uniform dispersion of particles within the carrier, forming a stable slurry. The slurry undergoes vacuum degassing to completely remove air bubbles and prevent porosity defects during sintering. In the final electrode material, the core-shell structure modifier blocks oxidation, the interface stabilizer strengthens interfacial bonding, and the inorganic binder promotes densification. The synergistic effect of these three components significantly enhances the electrode's antioxidant capacity and conductivity stability, meeting the long-term reliable operation requirements of electronic components in harsh environments.

[0008] According to a preferred embodiment of the present invention, in step S1, the conductive metal powder is selected from at least one of nickel powder, copper powder, and silver powder; the inorganic binder is lead-free glass powder and / or borosilicate glass powder; the organic solvent is selected from at least one of terpineol, diethylene glycol butyl ether, and turpentine; the organic binder is selected from at least one of ethyl cellulose, polyvinyl butyral, and polyvinyl acetate; and the organic additive is dibutyl phthalate and / or tetraethyl silicate.

[0009] According to a preferred embodiment of the present invention, in step S2, the degassing treatment time is 15-30 min.

[0010] According to a preferred embodiment of the present invention, the preparation method of the reduced vanadium oxide-sulfide core-shell composite modifier includes: A1. By weight, 50-70 parts of vanadium pentoxide are dispersed in deionized water and ultrasonically dispersed to obtain a suspension; 15-20 parts of thiourea and 5-8 parts of sodium hydroxide are added to the suspension and stirred at 78-82℃; after the reaction is completed, the mixture is centrifuged to obtain a precipitate; the precipitate is washed with deionized water and then with anhydrous ethanol to obtain a washed precipitate; the washed precipitate is dried in a vacuum drying oven at 78-82℃ to obtain a dried product. A2. Redisperse the dried product in anhydrous ethanol, add 8-10 parts of thioacetamide and 3-4 parts of polyvinylpyrrolidone, and stir the reaction at 58-62℃. After the reaction is complete, centrifuge, wash with anhydrous ethanol, and vacuum dry at 58-62℃.

[0011] In the preparation of a reduced vanadium oxide-sulfide core-shell composite modifier, vanadium pentoxide first undergoes a reduction reaction with thiourea under alkaline conditions. Sodium hydroxide provides the alkaline environment, and thiourea acts as a reducing agent to gradually reduce pentavalent vanadium to tetravalent vanadium. The reduced low-valent vanadium oxide is then centrifuged, washed with water and ethanol to obtain a pure precipitate. Subsequently, this precipitate is redispersed in anhydrous ethanol, and thioacetamide and polyvinylpyrrolidone are added. Thioacetamide hydrolyzes in the ethanol solvent to generate sulfur ions, which coordinate with the surface of the vanadium oxide to form an inorganic sulfide layer. Polyvinylpyrrolidone acts as a surfactant, effectively stabilizing the growth process of the sulfide layer, ultimately forming a core-shell structured composite modifier. This structure, through the dense coverage of the sulfide layer, significantly blocks the contact between oxygen and the metal substrate, providing excellent antioxidant properties for the electrode. According to a preferred embodiment of the present invention, in step A1, the stirring reaction is carried out at 78-82°C for 4-6 hours.

[0012] According to a preferred embodiment of the present invention, in step A2, the stirring reaction time at 58-62°C is 2-4 hours.

[0013] According to a preferred embodiment of the present invention, the preparation method of the yttrium-doped manganese-cobalt composite oxide interface stabilizer includes: B1. By weight, dissolve 35-40 parts of manganese acetate tetrahydrate, 24-25 parts of cobalt acetate tetrahydrate, and 4-5 parts of yttrium nitrate hexahydrate in anhydrous ethanol and stir to obtain a mixed solution; add 9-10 parts of citric acid ethanol solution dropwise to the mixed solution and continue stirring to obtain a sol; transfer the sol to a water bath at 78-82℃ and evaporate to obtain a wet gel; B2. Dry the wet gel in an oven at 115-125℃ to obtain a dry gel. Grind the dry gel and transfer it to an alumina crucible. Place it in a muffle furnace and heat it to 445-455℃ for pre-calcination. Then heat it to 795-805℃ for calcination. After calcination, cool it to room temperature with the furnace to obtain the product. Grind and sieve the product.

[0014] In this invention, the preparation of the yttrium-doped manganese-cobalt composite oxide interface stabilizer is based on the citric acid sol-gel method. Manganese, cobalt, and yttrium metal salts are dissolved in ethanol. Citric acid acts as a chelating agent, forming homogeneous complexes with the metal ions, inhibiting rapid precipitation and gradually transforming the solution into a transparent sol. The sol is then evaporated in a constant-temperature water bath to form a wet gel. After drying, the wet gel is pre-calcined to remove organic components and then calcined at high temperature. During calcination, the metal ions diffuse and combine fully, forming a spinel-structured yttrium-doped manganese-cobalt oxide. The doping of yttrium ions optimizes the crystal lattice, enhances interfacial stability, and makes the material less prone to structural collapse in high-temperature or oxidizing environments, thereby effectively protecting the electrode interface and reducing corrosion loss.

[0015] According to a preferred embodiment of the present invention, in step B1, the sol is transferred to a water bath at 78-82°C for evaporation for 5-10 hours.

[0016] According to a preferred embodiment of the present invention, in step B2, the calcination time at 795-805°C is 4-6 hours.

[0017] The present invention also provides an antioxidant metal electrode material for electronic components prepared according to the preparation method of the antioxidant metal electrode material for electronic components.

[0018] The beneficial effects of this invention are as follows: This invention presents the first design and synthesis of a reduced vanadium oxide-sulfide core-shell composite modifier. This modifier utilizes thiourea to reduce vanadium pentoxide under alkaline conditions, constructing a low-valence vanadium oxide shell rich in tetravalent vanadium ions on the vanadium pentoxide surface. Surface modification is then achieved by hydrolyzing thioacetamide to form a sulfide layer. The low-valence vanadium ions in this modifier possess excellent free radical scavenging capabilities, efficiently capturing and neutralizing reactive oxygen free radicals generated during metal oxidation, thus inhibiting the chain propagation of oxidation reactions at their source. Simultaneously, the sulfur atoms in the sulfide layer contain lone pairs of electrons, which can form strong coordination bonds with empty orbitals on the metal matrix surface, firmly anchoring the modifier to the metal particle surface and forming a stable chemical protective interface. Compared to traditional physical coating or simple mixing antioxidant additives, this modifier achieves a synergistic effect of chemical passivation and free radical scavenging, significantly improving antioxidant efficiency without negatively impacting the conductive pathways between metal particles.

[0019] This invention presents the first synthesis of a yttrium-doped manganese-cobalt composite oxide interface stabilizer. This stabilizer is prepared using a citric acid sol-gel method, by uniformly incorporating yttrium ions into the manganese-cobalt spinel lattice to form the yttrium-doped manganese-cobalt composite oxide. The introduction of yttrium effectively stabilizes the spinel crystal structure, inhibiting the migration of lattice defects and the formation of oxygen vacancies at high temperatures, significantly improving the high-temperature stability of the protective layer. Manganese provides abundant catalytic active sites, capable of catalytically decomposing infiltrated trace oxygen molecules. Cobalt imparts good electronic conductivity to the material, ensuring that the protective layer itself does not hinder electrode conductivity. This interface stabilizer can form a dense, continuous protective layer in situ on the surface of metal particles, effectively blocking the diffusion of oxygen into the metal matrix through physical isolation, while simultaneously forming a strong chemical bond with the metal matrix. This solves the technical problem of traditional inorganic protective layers being prone to cracking and peeling at high temperatures.

[0020] This invention achieves a three-dimensional structure of antioxidant function by synergistically compounding a reduced vanadium oxide-sulfide core-shell composite modifier with a yttrium-doped manganese-cobalt composite oxide interface stabilizer. The two modifiers function at two levels: free radical scavenging and interface passivation. The former focuses on blocking the initiation and propagation of oxidation reactions, while the latter focuses on constructing a dual physicochemical barrier. Their synergistic effect significantly enhances the antioxidant performance of the electrode material. Detailed Implementation

[0021] The following detailed embodiments are only used to further illustrate this application and should not be construed as limiting the scope of protection of this application. Those skilled in the art can make some non-essential improvements and adjustments to this application based on the above application content.

[0022] Example 1 This embodiment provides a method for preparing an antioxidant metal electrode material for electronic components, the steps of which include: S1. Place 60g of nickel powder, 5g of reduced vanadium oxide-sulfide core-shell composite modifier, 4g of yttrium-doped manganese cobalt composite oxide interface stabilizer, and 12g of lead-free glass powder in a three-dimensional mixer and premix at 250r / min for 45min to obtain a solid mixed powder. Mix terpineol, ethyl cellulose, and dibutyl phthalate at 75%, 18%, and 7% by weight, respectively, and stir under 90℃ water bath heating until the organic binder is completely dissolved to form a transparent and uniform organic carrier, wherein the total mass of the organic carrier is 20g. Slowly add the solid mixed powder to the organic carrier while stirring. After the addition is complete, stir at 800r / min for 30min. Then transfer the resulting slurry to a three-roll mill and grind it 4 times. Control the fineness of the slurry after grinding to ≤10μm to obtain the ground slurry.

[0023] S2. Place the ground slurry in a vacuum degassing machine and degas it for 20 minutes at a vacuum of -0.095MPa to obtain the anti-oxidation metal electrode material for electronic components.

[0024] Preparation of reduced vanadium oxide-sulfide core-shell composite modifier: A1. Disperse 60g of vanadium pentoxide in 1200mL of deionized water and sonicate for 30min to obtain a suspension. Add 18g of thiourea and 6g of sodium hydroxide to the suspension and stir at 80℃ for 5h. During the reaction, the solution color gradually changes from pale yellow to dark blue. After the reaction is complete, centrifuge to obtain a precipitate. Wash the precipitate three times with deionized water and then twice with anhydrous ethanol to obtain a washed precipitate. Place the washed precipitate in a vacuum drying oven at 80℃ for 12h to obtain a dried product.

[0025] A2. The dried product was redispersed in 550 mL of anhydrous ethanol, and 9 g of thioacetamide and 3.5 g of polyvinylpyrrolidone were added. The mixture was stirred at 60 °C for 3 h. After the reaction was completed, the product was centrifuged, washed three times with anhydrous ethanol, and dried under vacuum at 60 °C for 8 h to obtain the reduced vanadium oxide-sulfide core-shell composite modifier.

[0026] Preparation of yttrium-doped manganese-cobalt composite oxide interface stabilizer: B1. Dissolve 38g of manganese acetate tetrahydrate, 24.5g of cobalt acetate tetrahydrate, and 4.5g of yttrium nitrate hexahydrate in 550mL of anhydrous ethanol and stir magnetically for 30min to obtain a mixed solution. Add 9.5g of citric acid in ethanol at a concentration of 1mol / L at a dropping rate of 2mL / min to the mixed solution and continue stirring for 2h to obtain a sol. Transfer the sol to an 80℃ water bath and evaporate for 8h to obtain a wet gel.

[0027] B2. The wet gel was dried in an oven at 120°C for 12 hours to obtain a dry gel. The dry gel was ground and transferred to an alumina crucible, and placed in a muffle furnace and heated to 450°C for 2 hours at a heating rate of 5°C / min. Then, it was heated to 800°C for 5 hours at a heating rate of 5°C / min. After calcination, it was cooled to room temperature with the furnace to obtain the product. The product was ground and passed through a 200-mesh sieve to obtain the yttrium-doped manganese-cobalt composite oxide interface stabilizer.

[0028] Example 2 The specific implementation method is the same as in Example 1, except that this example provides a method for preparing an antioxidant metal electrode material for electronic components, the steps of which include: S1. Place 50g of copper powder, 3g of reduced vanadium oxide-sulfide core-shell composite modifier, 2g of yttrium-doped manganese cobalt composite oxide interface stabilizer, and 8g of borosilicate glass powder in a three-dimensional mixer and premix at 200r / min for 30min to obtain a solid mixed powder. Mix diethylene glycol butyl ether, polyvinyl butyral, and tetraethyl silicate at 65%, 25%, and 10% by weight, respectively, and stir under 80℃ water bath heating until the organic binder is completely dissolved to form a transparent and uniform organic carrier, wherein the total mass of the organic carrier is 15g. Slowly add the solid mixed powder to the organic carrier while stirring. After the addition is complete, stir at 500r / min for 30min. Then transfer the resulting slurry to a three-roll mill and grind it 3 times. Control the fineness of the slurry after grinding to ≤10μm to obtain the ground slurry.

[0029] S2. Place the ground slurry in a vacuum degassing machine and degas it for 15 minutes under a vacuum of -0.09MPa to obtain the anti-oxidation metal electrode material for electronic components.

[0030] Preparation of reduced vanadium oxide-sulfide core-shell composite modifier: A1. Disperse 50g of vanadium pentoxide in 1000mL of deionized water and sonicate for 30min to obtain a suspension. Add 15g of thiourea and 5g of sodium hydroxide to the suspension and stir at 78℃ for 4h. During the reaction, the solution color gradually changes from pale yellow to dark blue. After the reaction, centrifuge to obtain a precipitate. Wash the precipitate three times with deionized water and then twice with anhydrous ethanol to obtain a washed precipitate. Place the washed precipitate in a vacuum drying oven at 78℃ for 12h to obtain a dried product.

[0031] A2. The dried product was redispersed in 500 mL of anhydrous ethanol, 8 g of thioacetamide and 3 g of polyvinylpyrrolidone were added, and the mixture was stirred at 58 °C for 2 h. After the reaction was completed, the product was centrifuged, washed three times with anhydrous ethanol, and vacuum dried at 58 °C for 8 h to obtain the reduced vanadium oxide-sulfide core-shell composite modifier.

[0032] Preparation of yttrium-doped manganese-cobalt composite oxide interface stabilizer: B1. Dissolve 35g of manganese acetate tetrahydrate, 24g of cobalt acetate tetrahydrate, and 4g of yttrium nitrate hexahydrate in 500mL of anhydrous ethanol and stir magnetically for 30min to obtain a mixed solution. Add 9g of ethanol solution of citric acid (1mol / L) dropwise to the mixed solution at a rate of 2mL / min and continue stirring for 2h to obtain a sol. Transfer the sol to a 78℃ water bath and evaporate for 5h to obtain a wet gel.

[0033] B2. The wet gel was dried in an oven at 115℃ for 12 hours to obtain a dry gel. The dry gel was ground and transferred to an alumina crucible, and placed in a muffle furnace and heated to 445℃ for 2 hours at a heating rate of 5℃ / min. Then, it was heated to 795℃ for 4 hours at a heating rate of 5℃ / min. After calcination, it was cooled to room temperature in the furnace to obtain the product. The product was ground and passed through a 200-mesh sieve to obtain the yttrium-doped manganese-cobalt composite oxide interface stabilizer.

[0034] Example 3 This embodiment provides a method for preparing an antioxidant metal electrode material for electronic components, the steps of which include: S1. Place 70g of silver powder, 8g of reduced vanadium oxide-sulfide core-shell composite modifier, 6g of yttrium-doped manganese cobalt composite oxide interface stabilizer, and 15g of borosilicate glass powder in a three-dimensional mixer and premix at 300r / min for 60min to obtain a solid mixed powder. Mix turpentine, polyvinyl acetate, and dibutyl phthalate at 85%, 10%, and 5% by weight, respectively, and stir under 100℃ water bath heating conditions until the organic binder is completely dissolved to form a transparent and uniform organic carrier, wherein the total mass of the organic carrier is 25g. Slowly add the solid mixed powder to the organic carrier while stirring. After the addition is complete, stir at 1000r / min for 30min. Then transfer the resulting slurry to a three-roll mill and grind it 5 times, controlling the fineness of the slurry after grinding to ≤10μm to obtain the ground slurry.

[0035] S2. Place the ground slurry in a vacuum degassing machine and degas it for 30 minutes under a vacuum of -0.1MPa to obtain the anti-oxidation metal electrode material for electronic components.

[0036] Preparation of reduced vanadium oxide-sulfide core-shell composite modifier: A1. Disperse 70g of vanadium pentoxide in 1500mL of deionized water and sonicate for 30min to obtain a suspension. Add 20g of thiourea and 8g of sodium hydroxide to the suspension and stir at 82℃ for 6h. During the reaction, the solution color gradually changes from pale yellow to dark blue. After the reaction is complete, centrifuge to obtain a precipitate. Wash the precipitate three times with deionized water and then twice with anhydrous ethanol to obtain a washed precipitate. Place the washed precipitate in a vacuum drying oven at 82℃ for 12h to obtain a dried product.

[0037] A2. The dried product was redispersed in 600 mL of anhydrous ethanol, 10 g of thioacetamide and 4 g of polyvinylpyrrolidone were added, and the mixture was stirred at 62 °C for 4 h. After the reaction was completed, the product was centrifuged, washed three times with anhydrous ethanol, and dried under vacuum at 62 °C for 8 h to obtain the reduced vanadium oxide-sulfide core-shell composite modifier.

[0038] Preparation of yttrium-doped manganese-cobalt composite oxide interface stabilizer: B1. Dissolve 40g of manganese acetate tetrahydrate, 25g of cobalt acetate tetrahydrate, and 5g of yttrium nitrate hexahydrate in 600mL of anhydrous ethanol and stir magnetically for 30min to obtain a mixed solution. Add 10g of ethanol solution of citric acid (1mol / L) dropwise to the mixed solution at a rate of 2mL / min and continue stirring for 2h to obtain a sol. Transfer the sol to an 82℃ water bath and evaporate for 10h to obtain a wet gel.

[0039] B2. The wet gel was dried in an oven at 125°C for 12 hours to obtain a dry gel. The dry gel was ground and transferred to an alumina crucible, and placed in a muffle furnace and heated to 455°C for 2 hours at a heating rate of 5°C / min. Then, it was heated to 805°C for 6 hours at a heating rate of 5°C / min. After calcination, it was cooled to room temperature in the furnace to obtain the product. The product was ground and passed through a 200-mesh sieve to obtain the yttrium-doped manganese-cobalt composite oxide interface stabilizer.

[0040] Comparative Example 1 The specific implementation method is the same as in Example 1, except that the reduced vanadium oxide-sulfide core-shell composite modifier and the yttrium-doped manganese-cobalt composite oxide interface stabilizer are not added. Otherwise, it is the same as in Example 1.

[0041] Comparative Example 2 The specific implementation method is the same as in Example 1, except that no reduced vanadium oxide-sulfide core-shell composite modifier is added, and only yttrium-doped manganese-cobalt composite oxide interface stabilizer is added. The rest is the same as in Example 1.

[0042] Comparative Example 3 The specific implementation method is the same as in Example 1, except that no yttrium-doped manganese-cobalt composite oxide interface stabilizer is added, and only a reduced vanadium oxide-sulfide core-shell composite modifier is added. The rest is the same as in Example 1.

[0043] Performance testing The antioxidant metal electrode materials for electronic components prepared in Examples 1-3 and Comparative Examples 1-3 were subjected to performance testing according to the following method, which included the following steps: Volume resistivity test: The electrode material was screen-printed onto an alumina ceramic substrate with a thickness of 20 μm and a printing area of ​​10 mm × 10 mm. The substrate was sintered at 850 °C for 30 min under nitrogen atmosphere protection. The sheet resistance of the sintered electrode film was measured using a four-probe resistivity meter with a probe spacing of 1 mm and a test current of 10 mA. Five different locations were measured for each sample and the average value was taken. The volume resistivity was calculated based on the relationship between sheet resistance and thickness, with the unit being μΩ·cm.

[0044] High-temperature weight gain test: 2g of electrode material was placed in an alumina crucible, and the crucible was placed in a synchronous thermal analyzer. The temperature was increased from room temperature to 600℃ at a rate of 10℃ / min under air atmosphere and held at a constant temperature for 2h. The mass change of the sample before and after heating was recorded. The weight gain rate was calculated by subtracting the mass before heating from the mass after heating and dividing by the mass before heating and multiplying by 100%. The unit is .

[0045] Adhesion test: The electrode material was screen-printed onto an alumina ceramic substrate with a thickness of 20 μm. It was sintered at 850℃ for 30 min under nitrogen atmosphere protection. After cooling, a copper lead with a diameter of 0.8 mm was soldered to the center of the electrode film surface using lead-free solder at a soldering temperature of 280℃ and a soldering time of 3 s. The copper lead was then stretched vertically at a 90° angle using a universal tensile testing machine at a stretching speed of 10 mm / min. The maximum tensile force when the lead detached from the electrode film surface was recorded. Each sample was tested 3 times and the average value was taken. The unit is N.

[0046] Test results: Table 1: Test results of each embodiment and comparative example ; As shown in Table 1, Comparative Example 1, without any added modifying compound, exhibited a high volume resistivity of 12.5 μΩ·cm and a high-temperature weight gain of 2.45%, indicating that severe oxidation of the base metal electrode at high temperatures led to a sharp decline in conductivity. Simultaneously, the adhesion was only 8.3 N, suggesting that the oxide layer damaged the bond strength between the electrode and the substrate. Comparative Example 2, with the addition of only a yttrium-doped manganese-cobalt composite oxide interface stabilizer, saw its volume resistivity decrease to 7.6 μΩ·cm, its high-temperature weight gain significantly reduced to 0.98%, and its adhesion improved to 12.1 N. This indicates that the modifier effectively suppressed oxygen diffusion by forming a dense interface protective layer, but its use alone still resulted in some conductivity loss. Comparative Example 3, with the addition of only a reduced vanadium oxide-sulfide core-shell composite modifier, had a volume resistivity of 6.9 μΩ·cm, a high-temperature weight gain of 1.24%, and an adhesion of 11.6 N, indicating that the modifier... While it exerts an antioxidant effect by scavenging free radicals, its antioxidant efficiency is slightly low when used alone. However, in Examples 1-3, the addition of two modified compounds further reduced the volume resistivity to 2.9-3.8 μΩ·cm, decreased the high-temperature weight gain to 0.06-0.12%, and improved the adhesion to 17.2-19.8 N. This indicates that the reduced vanadium oxide-sulfide core-shell composite modifier and the yttrium-doped manganese-cobalt composite oxide interface stabilizer produced a significant synergistic effect. The former blocks the oxidation chain reaction at the source of free radical scavenging, while the latter constructs a dense conductive protective layer to form a dual physical and chemical barrier. The complementary synergy between the two enables the electrode material to obtain excellent antioxidant capacity while maintaining excellent conductivity, and the electrode adhesion is significantly enhanced. This effectively solves the technical problems of easy oxidation of existing base metal electrodes during high-temperature sintering and the difficulty in balancing antioxidant and conductivity performance.

[0047] The embodiments described above are merely examples of several implementations of the present invention, and while the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the present invention. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these modifications and improvements all fall within the scope of protection of the present invention.

Claims

1. A method for preparing an antioxidant metal electrode material for electronic components, characterized in that the steps include... include: S1. By weight, mix 50-70 parts of conductive metal powder, 3-8 parts of reduced vanadium oxide-sulfide core-shell composite modifier, 2-6 parts of yttrium-doped manganese-cobalt composite oxide interface stabilizer, and 8-15 parts of inorganic binder to obtain a solid mixed powder; mix the organic solvent, organic binder, and organic additive, and stir at 80-100℃ to obtain an organic carrier; add the solid mixed powder to the organic carrier and stir to obtain a slurry; transfer the slurry to a grinding mill and grind it to obtain a ground slurry. S2. Place the ground slurry in a vacuum degassing machine for degassing treatment.

2. The method for preparing the antioxidant metal electrode material for electronic components according to claim 1, characterized in that, In step S1, the conductive metal powder is selected from at least one of nickel powder, copper powder, and silver powder; the inorganic binder is lead-free glass powder and / or borosilicate glass powder; the organic solvent is selected from at least one of terpineol, diethylene glycol butyl ether, and turpentine; the organic binder is selected from at least one of ethyl cellulose, polyvinyl butyral, and polyvinyl acetate; and the organic additive is dibutyl phthalate and / or tetraethyl silicate.

3. The method for preparing the antioxidant metal electrode material for electronic components according to claim 1, characterized in that, In step S2, the degassing treatment time is 15-30 minutes.

4. The method for preparing the antioxidant metal electrode material for electronic components according to claim 1, characterized in that, The preparation method of the reduced vanadium oxide-sulfide core-shell composite modifier includes: A1. By weight, 50-70 parts of vanadium pentoxide are dispersed in deionized water and ultrasonically dispersed to obtain a suspension; 15-20 parts of thiourea and 5-8 parts of sodium hydroxide are added to the suspension and stirred at 78-82℃; after the reaction is completed, the mixture is centrifuged to obtain a precipitate; the precipitate is washed with deionized water and then with anhydrous ethanol to obtain a washed precipitate; the washed precipitate is dried in a vacuum drying oven at 78-82℃ to obtain a dried product. A2. Redisperse the dried product in anhydrous ethanol, add 8-10 parts of thioacetamide and 3-4 parts of polyvinylpyrrolidone, and stir the reaction at 58-62℃. After the reaction is complete, centrifuge, wash with anhydrous ethanol, and vacuum dry at 58-62℃.

5. The method for preparing the antioxidant metal electrode material for electronic components according to claim 4, characterized in that, In step A1, the reaction is stirred at 78-82℃ for 4-6 hours.

6. The method for preparing the antioxidant metal electrode material for electronic components according to claim 4, characterized in that, In step A2, the reaction is stirred at 58-62℃ for 2-4 hours.

7. The method for preparing the antioxidant metal electrode material for electronic components according to claim 1, characterized in that, The preparation method of the yttrium-doped manganese-cobalt composite oxide interface stabilizer includes: B1. By weight, dissolve 35-40 parts of manganese acetate tetrahydrate, 24-25 parts of cobalt acetate tetrahydrate, and 4-5 parts of yttrium nitrate hexahydrate in anhydrous ethanol and stir to obtain a mixed solution; add 9-10 parts of citric acid ethanol solution dropwise to the mixed solution and continue stirring to obtain a sol; transfer the sol to a water bath at 78-82℃ and evaporate to obtain a wet gel; B2. Dry the wet gel in an oven at 115-125℃ to obtain a dry gel. Grind the dry gel and transfer it to an alumina crucible. Place it in a muffle furnace and heat it to 445-455℃ for pre-calcination. Then heat it to 795-805℃ for calcination. After calcination, cool it to room temperature with the furnace to obtain the product. Grind and sieve the product.

8. The method for preparing the antioxidant metal electrode material for electronic components according to claim 7, characterized in that, In step B1, the sol is transferred to a water bath at 78-82℃ and evaporated for 5-10 hours.

9. The method for preparing the antioxidant metal electrode material for electronic components according to claim 7, characterized in that, In step B2, the calcination time at 795-805℃ is 4-6 hours.

10. An antioxidant metal electrode material for electronic components, characterized in that, The antioxidant metal electrode material for electronic components is prepared by the method described in any one of claims 1-9.