Manufacturing Method of Modified Nickel Paste for MLCC

Abstract

This application relates to the field of electronic materials for multilayer ceramic chip capacitors, and specifically to a method for manufacturing a modified nickel paste for MLCCs. The method for manufacturing a modified nickel paste for MLCCs includes a nano-BaTiO3 preliminary dispersion step of uniformly mixing and dispersing nano-BaTiO3 powder, a diluent, and a dispersant in a specific mass ratio to obtain a nano-BaTiO3 preliminary dispersion, and a step of mixing, dispersing, and filtering a BaTiO3 preliminary dispersion, an adhesive, a dispersant, a diluent, and nickel powder in a specific mass ratio to obtain a modified nickel paste for MLCCs. In this application, first, the nano-BaTiO3 powder is preliminarily dispersed with a dispersant to obtain a uniformly dispersed nano-BaTiO3 preliminary dispersion, and then the nano-BaTiO3 preliminary dispersion is mixed with nickel powder and other raw materials in the above ratio and dispersed with a three-roll mill to obtain a uniformly dispersed nickel paste, thereby solving the problem that the nano-BaTiO3 powder is not uniformly dispersed in the nickel paste for MLCCs.

Description

Technical Field

[0001] This application relates to the field of electronic materials for multilayer ceramic chip capacitors, and specifically to a method for manufacturing a modified nickel paste for MLCCs.

Background Art

[0002] MLCC (Multi-layer Ceramic Capacitor) is the English abbreviation for multilayer ceramic chip capacitor. An MLCC forms a structure similar to a monolith by shifting and overlapping ceramic dielectric diaphragms printed with electrodes (internal electrodes), sintering them at a high temperature at once to form a ceramic chip, and further sealing metal layers (external electrodes) at both ends of the chip, so it is also called a monolithic ceramic capacitor.

[0003] Currently, the paste used for the internal electrodes of MLCCs is usually nickel paste. In related technologies, nickel powder, nano BaTiO3, an adhesive, a dispersant, and an organic solvent are mixed and uniformly stirred, and the above raw materials are dispersed by utilizing the pressure, gap, and frictional shear force of a triple-roll mill to manufacture nickel paste. However, since the particle size of nano BaTiO3 powder is smaller than that of nickel powder, considering the dispersion effect of nano BaTiO3, it is necessary to adjust the gap of the three-roll mill to be smaller. In this way, nickel powder with a large particle size is destroyed. Considering the dispersion effect of nickel powder, it is necessary to adjust the gap of the three-roll mill to be larger. In this way, nano BaTiO3 with a small particle size aggregates and a good dispersion effect cannot be achieved. For nickel paste for MLCCs, the dispersibility of nickel powder is extremely important. Therefore, nano BaTiO3 usually cannot achieve a good dispersion effect. In this way, there are holes in the internal electrodes of MLCCs, which are discontinuous and further affect the performance of MLCC finished products.

[0004] Therefore, in order to improve the performance of MLCC finished products, it is necessary to quickly improve the dispersion performance of nano BaTiO3 powder in nickel paste.

Summary of the Invention

Problems to be Solved by the Invention

[0005] In order to solve the problem that nano BaTiO3 powder is not uniformly dispersed in the nickel paste for MLCC, the present application provides a method for manufacturing a modified nickel paste for MLCC.

Means for Solving the Problems

[0006] In a first aspect, the present application provides a method for manufacturing a modified nickel paste for MLCC, and uses the following technical means.

[0007] The method for manufacturing a modified nickel paste for MLCC is as follows: A nano BaTiO3 preliminary dispersion step of uniformly mixing and dispersing nano BaTiO3 powder, a diluent, and a dispersant at a mass ratio of (60-90):(20-30):1 to obtain a nano BaTiO3 preliminary dispersion; A nickel paste manufacturing step of mixing, dispersing, and filtering a BaTiO3 preliminary dispersion, an adhesive, a dispersant, a diluent, and nickel powder at a mass ratio of 10:(10-15):(0.1-1):(10-15):(25-60) to obtain a modified nickel paste for MLCC.

[0008] According to the above technical means, first, the nano BaTiO3 powder is preliminarily dispersed with a dispersant to obtain a uniformly dispersed nano BaTiO3 preliminary dispersion, and then the nano BaTiO3 preliminary dispersion is mixed with nickel powder and other raw materials at the above ratio and dispersed with a three-roll mill to obtain a uniformly dispersed nickel paste, thereby solving the problem that the nano BaTiO3 powder is not uniformly dispersed in the nickel paste for MLCC and improving the use performance of the MLCC finished product.

[0009] Preferably, the mass ratio of the BaTiO3 preliminary dispersion to the nickel powder is 10:(50-60).

[0010] Preferably, the particle size of the nano BaTiO3 powder is 10 to 200 nm.

[0011] According to the above technical means, when the particle size of the nano BaTiO3 powder is within the above range, the dispersion performance of the nano BaTiO3 powder in the nickel paste is excellent.

[0012] Preferably, the manufacturing method of the adhesive is as follows: A step of manufacturing a terminal epoxy group hyperbranched polyester by reacting a terminal hydroxyl group hyperbranched polyester and epichlorohydrin at a mass ratio of (10 to 20):1 to obtain a terminal epoxy group hyperbranched polyester, A step of manufacturing a modified polyvinyl butyral by reacting the terminal epoxy group hyperbranched polyester and polyvinyl butyral at a mass ratio of (10 to 25):1 to obtain a modified polyvinyl butyral, And a step of manufacturing an adhesive by reacting the modified polyvinyl butyral and ethyl cellulose at a mass ratio of (2 to 10):1 to obtain an adhesive.

[0013] According to the above technical means, the terminal hydroxyl group hyperbranched polyester and epichlorohydrin are reacted at the above mass ratio to obtain a terminal epoxy group hyperbranched polyester, and then the excessive terminal epoxy group hyperbranched polyester and polyvinyl butyral are reacted. In this process, the epoxy group on the terminal epoxy group hyperbranched polyester reacts with the hydroxyl group on the polyvinyl butyral to form a hydroxyl group and an ether bond, obtaining a modified polyvinyl butyral, which contains unreacted epoxy groups on the modified polyvinyl butyral. Further, the modified polyvinyl butyral and ethyl cellulose are reacted, and the epoxy group on the modified polyvinyl butyral reacts with the hydroxyl group on the ethyl cellulose to form a hydroxyl group and an ether bond.

[0014] As can be seen from the above, ethyl cellulose is grafted onto polyvinyl butyral molecules using the terminal epoxy group hyperbranched polyester as a bridge to obtain an adhesive containing a plurality of active groups. The adhesive is added to the nickel paste, and some of the active groups of the adhesive crosslink with each other to firmly adhere the components, while some of the other active groups bind to the hydroxyl groups of the ceramic coating layer, thereby imparting good adhesion between the nickel paste and the ceramic coating layer, improving the performance of the MLCC finished product.

[0015] Preferably, the mass ratio of the terminal epoxy group hyperbranched polyester to polyvinyl butyral is (10 - 15):1.

[0016] Preferably, the diluent is one or more of terpineol, isobornyl acetate, isophorone, and butyl acetate.

[0017] Preferably, the diluent is prepared by blending terpineol, isobornyl acetate, and butyl acetate in a mass ratio of (0.2 - 1):(0.5 - 1.5):1.

[0018] According to the above technical means, by adding a diluent prepared by blending terpineol, isobornyl acetate, and butyl acetate in the above specific mass ratio to the nickel paste, the influence on the ceramic coating layer is small, and the possibility of the diluent damaging the ceramic coating layer is reduced.

[0019] Preferably, the nickel powder is synthesized by a chemical method, and the raw material of the nickel powder contains nickel sulfate and other metal salts. The other metal salts are one or more of chromium sulfate, copper sulfate, and silver sulfate.

[0020] According to the above technical means, doping the nickel powder with other metals and sulfur imparts good pressure resistance and high temperature resistance to the nickel powder. Using this nickel powder as a raw material to manufacture a nickel paste, and further using the nickel paste in the manufacture of MLCC, a MLCC finished product with good breakdown voltage performance and high temperature resistance can be manufactured.

[0021] Preferably, the nickel powder is synthesized by physical vapor deposition method, and the raw materials of the nickel powder include a nickel target, sulfur powder and other metal targets, and the other metal targets are one or more of a chromium target, a copper target and a silver target.

[0022] According to the above technical means, other metals and sulfur are doped into the nickel powder to endow the nickel powder with good pressure resistance and high temperature resistance. Using this nickel powder as a raw material, nickel paste is manufactured, and further the nickel paste is used in the manufacture of MLCC, and an MLCC finished product with good breakdown voltage performance and high temperature resistance can be manufactured.

Advantages of the Invention

[0023] As described above, the present application has the following beneficial effects.

[0024] 1. In the present application, the nano BaTiO3 powder is preliminarily dispersed with a dispersant to obtain a uniformly dispersed nano BaTiO3 preliminary dispersion. Next, the nano BaTiO3 preliminary dispersion is mixed with nickel powder and other raw materials at a specific ratio and dispersed to obtain a uniformly dispersed nickel paste, thereby solving the problem that the nano BaTiO3 powder is not uniformly dispersed in the nickel paste for MLCC and improving the use performance of the MLCC finished product.

[0025] 2. In the present application, ethyl cellulose is grafted onto polyvinyl butyral molecules using terminal epoxy group hyperbranched polyester as a bridge to obtain an adhesive containing a plurality of active groups. The adhesive is added to the nickel paste, and some of the active groups of the adhesive crosslink with each other to firmly adhere each component, and the other part of the active groups bind to the hydroxyl groups of the ceramic coating layer, thereby giving a good adhesion between the nickel paste and the ceramic coating layer, so as to improve the performance of the MLCC finished product.

[0026] 3. In this application, nickel powder is modified by adding sulfur and other metals to the nickel powder. The modified nickel powder is used as a raw material to manufacture nickel paste, and further the nickel paste is used in the manufacture of MLCCs, enabling the production of MLCC finished products with good withstand voltage performance and high temperature resistance performance.

Brief Description of the Drawings

[0027]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Figure 6

Modes for Carrying Out the Invention

[0028] Hereinafter, this application will be described in more detail with reference to the examples.

[0029] Unless otherwise specified, refer to Table 1 (Raw Material Specification Information) for the specifications of the raw materials used in the following examples and comparative examples.

[0030]

Table 1

[0031] Manufacturing Example of Adhesive Manufacturing Example 1 The adhesive was manufactured according to the following steps.

[0032] In the production step of the terminal epoxy group hyperbranched polyester, 10 kg of the terminal hydroxyl group hyperbranched polyester and 20 kg of DMF were uniformly mixed, heated to 60 °C, nitrogen gas was introduced, 1 kg of epichlorohydrin was added, and the mixture was kept warm for 3 h for reaction, then cooled to 30 °C, 550 g of sodium hydroxide saturated solution was added, kept at a constant temperature for 3 h, 500 g of dichloromethane was added, followed by washing with water three times and drying to obtain the terminal epoxy group hyperbranched polyester. In the production step of the modified polyvinyl butyral, 5 kg of the above terminal epoxy group hyperbranched polyester and 10 kg of DMF were mixed, heated to 50 °C, 0.5 kg of polyvinyl butyral was added, kept warm for 5 h, and dried to obtain the modified polyvinyl butyral. In the production step of the adhesive, 2 kg of the modified polyvinyl butyral produced above and 5 kg of DMF were mixed, heated to 65 °C, 1 kg of ethyl cellulose was further added, kept warm for 8 h, and dried to obtain the adhesive.

[0033] Production Examples 2 - 3 Regarding the adhesive, the difference from Production Example 1 is that the usage amounts of some materials are different in the production process of the adhesive. The specific usage amounts are shown in Table 2 (the masses of some materials in the production process of the adhesive).

[0034]

Table 2

[0035] Production Example of Nickel Powder Production Example a The nickel powder was produced according to the following steps S1 - S3.

[0036] In S1, for the preparation of the mixed solution, 10 kg of nickel nitrate and 2 kg of sodium citrate dihydrate were weighed and dissolved in 40 L of deionized water. In S2, for the preparation of the reducing solution, 6.5 kg of 80% hydrazine hydrate was weighed, 8 kg of sodium hydroxide, 1 kg of triethanolamine and 120 L of deionized water were added, and the mixture was stirred and dissolved. In S3, the mixed solution was placed in a water bath at 80 °C, the reducing solution was dropped into the mixed solution, and after reacting for 10 min, the solution began to turn gray, gradually generating bubbles. Then, 1.2 kg of triethanolamine and 0.1 kg of dimethylpolysiloxane antifoaming agent were added. Subsequently, after reacting for 30 min, the reaction was stopped and cooled, and left standing overnight. The supernatant was taken out, washed, and then dried in a vacuum oven at 70 °C to obtain nickel powder.

[0037] Production Example b Regarding the nickel powder, the difference from Production Example a is that 10 kg of nickel nitrate was changed to 9.5 kg of nickel sulfate hexahydrate + 0.2 kg of copper sulfate + 0.3 kg of silver sulfate.

[0038] Production Example c Nickel powder was produced according to the following steps S1 to S4.

[0039] In S1, 10 kg of nickel targets were selected and placed into the reactor. In S2, the reactor was filled with nitrogen gas, and the pressure per unit area in the reactor was controlled to 100 kPa. In S3, ignition was carried out to generate an arc, and the arc was burned between the plasma gun and nickel until the nickel particles were completely melted, and the magnitude of the current of the plasma gun was controlled. In S4, as the nickel particles gradually evaporated into particulate nickel and entered the condenser, the magnitude of the current of the plasma gun was increased and controlled until nickel powder was formed in the collector connected to the condenser.

[0040] Production Example d Nickel powder was produced according to the following steps S1 to S4.

[0041] In S1, 9.8 kg of nickel targets, 0.1 kg of sulfur powder, and 0.1 kg of chromium targets were selected, filled, and placed into the reactor. In S2, the reactor was filled with nitrogen gas, and the pressure per unit area in the reactor was controlled to 100 kPa. In S3, ignition is carried out to generate an arc, and the arc is burned between the plasma gun and nickel until the nickel particles are completely melted, and the magnitude of the current of the plasma gun is controlled. In S4, the magnitude of the current of the plasma gun is increased and controlled until the nickel particles gradually evaporate to become particulate nickel, enter the condenser, and nickel powder is formed in the collector connected to the condenser.

[0042] Manufacturing examples of diluents Manufacturing example A The diluent was manufactured according to the following steps.

[0043] 2 kg of terpineol for electronics, 5 kg of isobornyl acetate for electronics, and 10 kg of butyl acetate for electronics were uniformly mixed to obtain a diluent.

[0044] Manufacturing example B The diluent was manufactured according to the following steps.

[0045] 4.85 kg of terpineol for electronics, 7.3 kg of isobornyl acetate for electronics, and 4.85 kg of butyl acetate for electronics were uniformly mixed to obtain a diluent.

[0046] Manufacturing example C The diluent was manufactured according to the following steps.

[0047] 1.1 kg of terpineol for electronics, 5.3 kg of isobornyl acetate for electronics, and 10.6 kg of butyl acetate for electronics were uniformly mixed to obtain a diluent.

[0048] Manufacturing example D The diluent was manufactured according to the following steps.

[0049] 2.4 kg of terpineol for electronics, 2.4 kg of isobornyl acetate for electronics, and 12.2 kg of butyl acetate for electronics were uniformly mixed to produce a diluent.

[0050] Production Example E The diluent was produced according to the following steps.

[0051] 7.6 kg of terpineol for electronics, 3.1 kg of isobornyl acetate for electronics, and 6.3 kg of butyl acetate for electronics were uniformly mixed to produce a diluent.

[0052] Production Example F The diluent was produced according to the following steps.

[0053] 1.1 kg of terpineol for electronics, 10.6 kg of isobornyl acetate for electronics, and 5.3 kg of butyl acetate for electronics were uniformly mixed to produce a diluent.

[0054] Production Example G It is a diluent, and the difference from Production Example A is that the diluent in this production example is 17 kg of terpineol for electronics.

[0055] Production Example H It is a diluent, and the difference from Production Example A is that the diluent in this production example is 17 kg of isobornyl acetate for electronics.

[0056] Production Example I It is a diluent, and the difference from Production Example A is that the diluent in this production example is 17 kg of butyl acetate for electronics.

[0057] Examples Example 1 The modified nickel paste for MLCC was produced according to the following steps.

[0058] In the nano BaTiO3 preliminary dispersion step, 6 kg of nano BaTiO3 powder with a particle size of 10 nm, 2 kg of diluent produced in Production Example A, and 0.1 kg of dispersant were mixed, stirred in a mixer for 30 min, and uniformly mixed. Then, it was pulverized and dispersed with a three-roll mill to obtain a nano BaTiO3 preliminary dispersion. Regarding the process parameters of the three-roll mill, (1) the rotation speed ratio of the three rolls was set to 1:3:9, and the rotation speeds of the three rolls were 50 r / min, 150 r / min, and 450 r / min, respectively; (2) the roll warp was designed so that the warp was 50 μm; (3) the temperature of the three rolls was set to 25 °C; (4) the hydraulic pressure of the three rolls was set to 3 bar, and the pressure between the scraper and the roll was set to 1 bar; (5) the number of pulverization times was set to 5 times. In the nickel paste production step, 1 kg of the BaTiO3 preliminary dispersion, 1 kg of adhesive produced in Production Example 1, 0.01 kg of dispersant, 1 kg of diluent produced in Production Example A, and 3 kg of nickel powder produced in Production Example a were mixed to obtain a mixture. The mixture was put into a planetary mixer for preliminary mixing, and the mixed nickel paste was put into a three-roll mill for pulverization and dispersion. The dispersed nickel paste was filtered under pressure, the pore size of the filter element was set to 15 μm, and the pressure was set to 10 kPa. Finally, a modified nickel paste for MLCC was obtained. The rotation speed of the dispersion disk in the planetary mixer was set to 100 r / min, the rotation speed of the central axis disk was set to 200 r / min, the vacuum pressure was set to 10 kPa, and the mixing time was set to 60 min. When dispersing the nickel paste, regarding the process parameters of the three-roll mill, (1) the rotation speed ratio of the three rolls was set to 1:3:9, and the rotation speeds of the three rolls were 50 r / min, 150 r / min, and 450 r / min, respectively; (2) the roll warp was designed so that the warp was 100 μm; (3) the temperature of the three rolls was set to 25 °C; (4) the hydraulic pressure of the three rolls was set to 3 bar, and the pressure between the scraper and the roll was set to 2 bar; (5) the number of pulverization times was set to 5 times.

[0059] Example 2 It is a modified nickel paste for MLCC. The difference from Example 1 is that a different adhesive is selected. In this example, the adhesive manufactured in Production Example 2 was selected.

[0060] Example 3 It is a modified nickel paste for MLCC. The difference from Example 1 is that a different adhesive is selected. In this example, the adhesive manufactured in Production Example 3 was selected.

[0061] Example 4 It is a modified nickel paste for MLCC. The difference from Example 1 is that a different adhesive is selected. In this example, the adhesive manufactured in Production Example 1 was changed to polyvinyl butyral in equal mass.

[0062] Example 5 It is a modified nickel paste for MLCC. The difference from Example 1 is that a different adhesive is selected. In this example, the adhesive manufactured in Production Example 1 was changed to ethyl cellulose in equal mass.

[0063] Example 6 A modified nickel paste for MLCC was manufactured according to the following steps.

[0064] In the nano BaTiO3 preliminary dispersion step, 6.02 kg of nano BaTiO3 powder with a particle size of 10 nm, 2.01 kg of diluent manufactured in Production Example A, and 0.07 kg of dispersant were mixed. After uniformly mixing, they were dispersed with a three-roll mill to obtain a nano BaTiO3 preliminary dispersion. The process parameters of the three-roll mill were the same as those in Example 1. In the nickel paste manufacturing step, 0.85 kg of BaTiO3 pre-dispersion, 1.27 kg of the adhesive manufactured in Production Example 1, 0.08 kg of the dispersant, 1.27 kg of the diluent manufactured in Production Example A, and 2.54 kg of nickel powder manufactured in Production Example a were mixed to obtain a mixture. The mixture was put into a planetary mixer for preliminary mixing, and the mixed nickel paste was put into a three-roll mill for dispersion. The dispersed nickel paste was filtered under pressure to obtain a modified nickel paste for MLCC. The specifications of the filter element, the process parameters of the planetary mixer, and the process parameters of the three-roll mill were all the same as those in Example 1.

[0065] Example 7 A modified nickel paste for MLCC was manufactured according to the following steps.

[0066] In the nano BaTiO3 pre-dispersion step, 6.08 kg of nano BaTiO3 powder with a particle size of 10 nm, 1.94 kg of the diluent manufactured in Production Example A, and 0.08 kg of the dispersant were mixed. After uniform mixing, they were dispersed by a three-roll mill to obtain a nano BaTiO3 pre-dispersion. The process parameters of the three-roll mill were the same as those in Example 1. In the nickel paste manufacturing step, 0.94 kg of BaTiO3 pre-dispersion, 1.25 kg of the adhesive manufactured in Production Example 1, 0.06 kg of the dispersant, 1.25 kg of the diluent manufactured in Production Example A, and 2.51 kg of nickel powder manufactured in Production Example a were mixed to obtain a mixture. The mixture was put into a planetary mixer for preliminary mixing, and the mixed nickel paste was put into a three-roll mill for dispersion. The dispersed nickel paste was filtered under pressure to obtain a modified nickel paste for MLCC. The specifications of the filter element, the process parameters of the planetary mixer, and the process parameters of the three-roll mill were all the same as those in Example 1.

[0067] Example 8 It is a modified nickel paste for MLCC. The difference from Example 1 is that in the nickel paste manufacturing step, the masses of the BaTiO3 preliminary dispersion, adhesive, dispersant, diluent, and nickel powder are different. In this example, the masses of the above materials are 0.75 kg, 0.75 kg, 0.01 kg, 0.75 kg, and 3.75 kg respectively.

[0068] Example 9 It is a modified nickel paste for MLCC. The difference from Example 1 is that in the nickel paste manufacturing step, the masses of the BaTiO3 preliminary dispersion, adhesive, dispersant, diluent, and nickel powder are different. In this example, the masses of the above materials are 0.667 kg, 0.667 kg, 0.007 kg, 0.667 kg, and 4.002 kg respectively.

[0069] Example 10 It is a modified nickel paste for MLCC. The difference from Example 1 is that the particle size of the nano BaTiO3 powder is different. In this example, the particle size of the nano BaTiO3 powder is 200 nm.

[0070] Examples 11 - 18 It is a modified nickel paste for MLCC. The difference from Example 1 is that the source of the diluent is different. The specific sources are shown in Table 3 (Source of Diluent) below.

[0071]

Table 3

[0072] Example 19 It is a modified nickel paste for MLCC. The difference from Example 1 is that the source of the nickel powder is different. In this example, the nickel powder manufactured in Production Example a was changed to an equal mass of the nickel powder manufactured in Production Example b.

[0073] Example 20 It is a modified nickel paste for MLCC. The difference from Example 1 is that the source of the nickel powder is different. In this example, the nickel powder produced in Production Example a was changed to an equal mass of the nickel powder produced in Production Example c.

[0074] Example 21 It is a modified nickel paste for MLCC. The difference from Example 1 is that the source of the nickel powder is different. In this example, the nickel powder produced in Production Example a was changed to an equal mass of the nickel powder produced in Production Example d.

[0075] Example 22 It is a modified nickel paste for MLCC. The difference from Example 1 is that a different adhesive was selected. In this example, the adhesive was a mixture of 0.5 kg of polyvinyl butyral and 0.5 kg of ethyl cellulose.

[0076] Example 23 A modified nickel paste for MLCC was manufactured according to the following steps.

[0077] In the nano BaTiO3 preliminary dispersion step, 750 g of nano BaTiO3 powder with a particle size of 150 nm, 240 g of diluent produced in Production Example A, and 10 g of dispersant were mixed and stirred in a mixer for 30 min. After uniform mixing, it was pulverized and dispersed with a three-roll mill to obtain a nano BaTiO3 preliminary dispersion. Regarding the process parameters of the three-roll mill, (1) the rotation speed ratio of the three rolls was 1:3:9, the rotation speeds of the three rolls were 50 r / min, 150 r / min, and 450 r / min respectively, (2) the roll warp was designed to be 50 μm, (3) the temperature of the three rolls was 25 °C, (4) the hydraulic pressure of the three rolls was 3 bar, the pressure between the scraper and the roll was 1 bar, and (5) the number of pulverization times was 5 times. In the nickel paste manufacturing step, the above-mentioned BaTiO3 preliminary dispersion, the adhesive manufactured in Production Example 1, the dispersant DISPERBYK-108, the diluent manufactured in Production Example A, and the nickel powder with a particle size of 600 nm manufactured in Production Example b were mixed at a mass ratio of 20:20:1:20:50 (assuming the mass of the BaTiO3 preliminary dispersion is 600 g) to obtain a mixture. The mixture was put into a planetary mixer for preliminary mixing, and the mixed nickel paste was put into a three-roll mill for grinding and dispersion. The dispersed nickel paste was filtered under pressure, with the pore size of the filter element being 15 μm and the pressure being 10 kPa. Finally, a modified nickel paste for MLCC was obtained. The rotation speed of the dispersion disk in the planetary mixer was set at 100 r / min, the rotation speed of the central axis disk was set at 200 r / min, the vacuum pressure was set at 10 kPa, and the mixing time was set at 60 min. When dispersing the nickel paste, regarding the process parameters of the three-roll mill: (1) The rotation speed ratio of the three rolls was set at 1:3:9, and the rotation speeds of the three rolls were 50 r / min, 150 r / min, and 450 r / min respectively; (2) The roll warp was designed to be 100 μm; (3) The temperatures of the three rolls were set at 25 °C; (4) The hydraulic pressure of the three rolls was set at 3 bar, and the pressure between the scraper and the roll was set at 2 bar; (5) The number of grinding times was set at 5 times.

[0078] Example 24 A modified nickel paste for MLCC was manufactured according to the following steps.

[0079] In the nano BaTiO3 preliminary dispersion step, 750 g of nano BaTiO3 powder with a particle size of 100 nm, 240 g of diluent produced in Production Example A, and 10 g of dispersant are mixed, stirred in a mixer for 30 min, and uniformly mixed. Then, it is ground and dispersed with a three-roll mill to obtain a nano BaTiO3 preliminary dispersion. Regarding the process parameters of the three-roll mill, (1) the rotation speed ratio of the three rolls is 1:3:9, and the rotation speeds of the three rolls are 50 r / min, 150 r / min, and 450 r / min respectively; (2) the roll warp is designed to be 50 μm; (3) the temperature of the three rolls is 25 °C; (4) the hydraulic pressure of the three rolls is 3 bar, and the pressure between the scraper and the roll is 1 bar; (5) the number of grinding times is 5 times. In the nickel paste production step, the above-mentioned BaTiO3 preliminary dispersion, the adhesive produced in Production Example 1, dispersant DISPERBYK-108, the diluent produced in Production Example A, and nickel powder with a particle size of 400 nm produced in Production Example b are mixed at a mass ratio of 20:20:1:20:50 (assuming the mass of the BaTiO3 preliminary dispersion is 600 g) to obtain a mixture. The mixture is put into a planetary mixer for preliminary mixing, and the mixed nickel paste is put into a three-roll mill for grinding and dispersion. The dispersed nickel paste is filtered under pressure, with the pore size of the filter element being 15 μm and the pressure being 10 kPa. Finally, a modified nickel paste for MLCC is obtained. The rotation speed of the dispersion disk in the planetary mixer is 100 r / min, the rotation speed of the central axis disk is 200 r / min, the vacuum pressure is 10 kPa, and the mixing time is 60 min. When dispersing the nickel paste, regarding the process parameters of the three-roll mill, (1) the rotation speed ratio of the three rolls is 1:3:9, and the rotation speeds of the three rolls are 50 r / min, 150 r / min, and 450 r / min respectively; (2) the roll warp is designed to be 100 μm; (3) the temperature of the three rolls is 25 °C; (4) the hydraulic pressure of the three rolls is 3 bar, and the pressure between the scraper and the roll is 2 bar; (5) the number of grinding times is 5 times.

[0080] Example 25 A modified nickel paste for MLCC was manufactured according to the following steps.

[0081] In the nano BaTiO3 preliminary dispersion step, 750 g of nano BaTiO3 powder with a particle size of 80 nm, 240 g of diluent produced in Production Example A, and 10 g of dispersant were mixed, stirred in a mixer for 30 min, and uniformly mixed. Then, it was pulverized and dispersed with a three-roll mill to obtain a nano BaTiO3 preliminary dispersion. Regarding the process parameters of the three-roll mill, (1) the rotation speed ratio of the three rolls was 1:3:9, the rotation speeds of the three rolls were 50 r / min, 150 r / min, and 450 r / min respectively, (2) the roll warp was designed to be 50 μm, (3) the temperatures of the three rolls were 25 °C, (4) the hydraulic pressures of the three rolls were 3 bar, the pressure between the scraper and the roll was 1 bar, and (5) the number of pulverization times was 5 times. In the nickel paste production step, the above BaTiO3 preliminary dispersion, the adhesive produced in Production Example 1, dispersant DISPERBYK-108, the diluent produced in Production Example A, and nickel powder with a particle size of 400 nm produced in Production Example b were mixed at a mass ratio of 20:20:1:20:50 (assuming the mass of the BaTiO3 preliminary dispersion was 600 g) to obtain a mixture. The mixture was put into a planetary mixer for preliminary mixing, and the mixed nickel paste was put into a three-roll mill for pulverization and dispersion. The dispersed nickel paste was filtered under pressure, with the pore size of the filter element being 15 μm and the pressure being 10 kPa. Finally, a modified nickel paste for MLCC was obtained. The rotation speed of the dispersion disk in the planetary mixer was 100 r / min, the rotation speed of the central axis disk was 200 r / min, the vacuum pressure was 10 kPa, and the mixing time was 60 min. When dispersing nickel paste, regarding the process parameters of the three-roll mill: (1) Set the rotation speed ratio of the three rolls to 1:3:9, and set the rotation speeds of the three rolls to 50 r / min, 150 r / min, and 450 r / min respectively; (2) Design the roll warp so that the warp is 100 μm; (3) Set the temperature of the three rolls to 25 °C; (4) Set the hydraulic pressure of the three rolls to 3 bar, and set the pressure between the scraper and the roll to 2 bar; (5) Set the number of grinding times to 5 times.

[0082] Example 26 The modified nickel paste for MLCC was manufactured according to the following steps.

[0083] In the nano-BaTiO3 preliminary dispersion step, 750 g of nano-BaTiO3 powder with a particle size of 60 nm, 240 g of diluent manufactured in Production Example A, and 10 g of dispersant were mixed, stirred in a mixer for 30 min, and uniformly mixed. Then, it was ground and dispersed with a three-roll mill to obtain a nano-BaTiO3 preliminary dispersion. Regarding the process parameters of the three-roll mill: (1) Set the rotation speed ratio of the three rolls to 1:3:9, and set the rotation speeds of the three rolls to 50 r / min, 150 r / min, and 450 r / min respectively; (2) Design the roll warp so that the warp is 50 μm; (3) Set the temperature of the three rolls to 25 °C; (4) Set the hydraulic pressure of the three rolls to 3 bar, and set the pressure between the scraper and the roll to 1 bar; (5) Set the number of grinding times to 5 times. In the nickel paste manufacturing step, the above BaTiO3 preliminary dispersion, the adhesive manufactured in Production Example 1, dispersant DISPERBYK-108, the diluent manufactured in Production Example A, and nickel powder with a particle size of 300 nm manufactured in Production Example b were mixed at a mass ratio of 20:20:1:20:50 (assuming the mass of the BaTiO3 preliminary dispersion is 600 g) to obtain a mixture. The mixture was put into a planetary mixer for preliminary mixing, and the mixed nickel paste was put into a three-roll mill for grinding and dispersion. The dispersed nickel paste was filtered under pressure, with the pore size of the filter element set to 15 μm and the pressure set to 10 kPa. Finally, the modified nickel paste for MLCC was obtained. Set the rotational speed of the dispersion disk in the planetary mixer to 100 r / min, the rotational speed of the central axis disk to 200 r / min, the vacuum pressure to 10 kPa, and the mixing time to 60 min. When dispersing the nickel paste, for the process parameters of the three-roll mill: (1) Set the rotational speed ratio of the three rolls to 1:3:9, and the rotational speeds of the three rolls to 50 r / min, 150 r / min, and 450 r / min respectively; (2) Design the roll warp so that the warp is 100 μm; (3) Set the temperature of the three rolls to 25 °C; (4) Set the hydraulic pressure of the three rolls to 3 bar, and the pressure between the scraper and the roll to 2 bar; (5) Set the number of grinding times to 5 times.

[0084] Example 27 The modified nickel paste for MLCC was manufactured according to the following steps.

[0085] In the nano BaTiO3 preliminary dispersion step, 750 g of nano BaTiO3 powder with a particle size of 50 nm, 240 g of diluent manufactured in Production Example A, and 10 g of dispersant were mixed, stirred in a mixer for 30 min, uniformly mixed, and then ground and dispersed with a three-roll mill to obtain a nano BaTiO3 preliminary dispersion. For the process parameters of the three-roll mill: (1) Set the rotational speed ratio of the three rolls to 1:3:9, and the rotational speeds of the three rolls to 50 r / min, 150 r / min, and 450 r / min respectively; (2) Design the roll warp so that the warp is 50 μm; (3) Set the temperature of the three rolls to 25 °C; (4) Set the hydraulic pressure of the three rolls to 6 bar, and the pressure between the scraper and the roll to 5 bar; (5) Set the number of grinding times to 5 times. In the nickel paste manufacturing step, the above-mentioned BaTiO3 preliminary dispersion, the adhesive manufactured in Production Example 1, the dispersant DISPERBYK-108, the diluent manufactured in Production Example A, and the nickel powder with a particle size of 300 nm manufactured in Production Example b were mixed at a mass ratio of 20:20:1:20:50 (assuming the mass of the BaTiO3 preliminary dispersion is 600 g) to obtain a mixture. The mixture was put into a planetary mixer for preliminary mixing, and the mixed nickel paste was put into a three-roll mill for grinding and dispersion. The dispersed nickel paste was filtered under pressure, with the pore size of the filter element being 15 μm and the pressure being 10 kPa. Finally, a modified nickel paste for MLCC was obtained. The rotation speed of the dispersion disk in the planetary mixer was set at 100 r / min, the rotation speed of the central axis disk was set at 200 r / min, the vacuum pressure was set at 10 kPa, and the mixing time was set at 60 min. When dispersing the nickel paste, regarding the process parameters of the three-roll mill: (1) The rotation speed ratio of the three rolls was set at 1:3:9, and the rotation speeds of the three rolls were 50 r / min, 150 r / min, and 450 r / min respectively; (2) The roll warp was designed so that the warp was 100 μm; (3) The temperatures of the three rolls were set at 25 °C; (4) The hydraulic pressure of the three rolls was set at 3 bar, and the pressure between the scraper and the roll was set at 2 bar; (5) The number of grinding times was set at 5 times.

[0086] Example 28 A modified nickel paste for MLCC was manufactured according to the following steps.

[0087] In the nano BaTiO3 preliminary dispersion step, 750 g of nano BaTiO3 powder with a particle size of 40 nm, 240 g of diluent produced in Production Example A, and 10 g of dispersant were mixed and stirred in a mixer for 30 min. After uniform mixing, they were ground and dispersed with a three-roll mill to obtain a nano BaTiO3 preliminary dispersion. Regarding the process parameters of the three-roll mill, (1) the rotation speed ratio of the three rolls was 1:3:9, and the rotation speeds of the three rolls were 50 r / min, 150 r / min, and 450 r / min respectively; (2) the roll warp was designed to be 50 μm; (3) the temperature of the three rolls was 25 °C; (4) the hydraulic pressure of the three rolls was 3 bar, and the pressure between the scraper and the roll was 1 bar; (5) the number of grinding times was 5 times. In the nickel paste production step, the above-mentioned BaTiO3 preliminary dispersion, the adhesive produced in Production Example 1, dispersant DISPERBYK-108, the diluent produced in Production Example A, and nickel powder with a particle size of 200 nm produced in Production Example b were mixed at a mass ratio of 20:20:1:20:50 (assuming the mass of the BaTiO3 preliminary dispersion was 600 g) to obtain a mixture. The mixture was put into a planetary mixer for preliminary mixing, and the mixed nickel paste was put into a three-roll mill for grinding and dispersion. The dispersed nickel paste was filtered under pressure, with the pore size of the filter element being 15 μm and the pressure being 10 kPa. Finally, a modified nickel paste for MLCC was obtained. The rotation speed of the dispersion disk in the planetary mixer was 100 r / min, the rotation speed of the central axis disk was 200 r / min, the vacuum pressure was 10 kPa, and the mixing time was 60 min. When dispersing the nickel paste, regarding the process parameters of the three-roll mill, (1) the rotation speed ratio of the three rolls was 1:3:9, and the rotation speeds of the three rolls were 50 r / min, 150 r / min, and 450 r / min respectively; (2) the roll warp was designed to be 100 μm; (3) the temperature of the three rolls was 25 °C; (4) the hydraulic pressure of the three rolls was 3 bar, and the pressure between the scraper and the roll was 2 bar; (5) the number of grinding times was 5 times.

[0088] Comparative Example Comparative Example 1 A modified nickel paste for MLCC was manufactured according to the following steps.

[0089] 0.74 kg of nano BaTiO3 powder with a particle size of 10 nm, 1 kg of the adhesive manufactured in Production Example 1, 0.02 kg of a dispersant, 1.25 kg of a diluent manufactured in Production Example A, and 3 kg of nickel powder manufactured in Production Example a were mixed to obtain a mixture. The mixture was put into a planetary mixer for preliminary mixing, and the nickel paste after mixing was put into a three-roll mill for dispersion. The nickel paste after dispersion was filtered under pressure to obtain a modified nickel paste for MLCC. The specifications of the filter element, the process parameters of the planetary mixer, and the process parameters of the three-roll mill were all the same as those in Example 1.

[0090] Comparative Example 2 A modified nickel paste for MLCC was manufactured according to the following steps.

[0091] In the nano BaTiO3 preliminary dispersion step, 6 kg of nano BaTiO3 powder with a particle size of 10 nm, 2 kg of a diluent manufactured in Production Example A, and 0.1 kg of a dispersant were mixed. After uniform mixing, they were dispersed with a three-roll mill to obtain a nano BaTiO3 preliminary dispersion. The process parameters of the three-roll mill were the same as those in Example 1. In the nickel paste manufacturing step, 0.55 kg of the BaTiO3 preliminary dispersion, 1.09 kg of the adhesive manufactured in Production Example 1, 0.01 kg of a dispersant, 1.09 kg of a diluent manufactured in Production Example A, and 3.27 kg of nickel powder manufactured in Production Example a were mixed to obtain a mixture. The mixture was put into a planetary mixer for preliminary mixing, and the nickel paste after mixing was put into a three-roll mill for dispersion. The nickel paste after dispersion was filtered under pressure to obtain a modified nickel paste for MLCC. The specifications of the filter element, the process parameters of the planetary mixer, and the process parameters of the three-roll mill were all the same as those in Example 1.

[0092] Comparative Example 3 The modified nickel paste for MLCC was manufactured according to the following steps.

[0093] In the nano BaTiO3 preliminary dispersion step, 6 kg of nano BaTiO3 powder with a particle size of 10 nm, 2 kg of diluent manufactured in Production Example A, and 0.1 kg of dispersant were mixed. After uniform mixing, they were dispersed by a three-roll mill to obtain a nano BaTiO3 preliminary dispersion. The process parameters of the three-roll mill were the same as those in Example 1. In the nickel paste manufacturing step, 2 kg of the BaTiO3 preliminary dispersion, 0.8 kg of adhesive manufactured in Production Example 1, 0.01 kg of dispersant, 0.8 kg of diluent manufactured in Production Example A, and 2.4 kg of nickel powder manufactured in Production Example a were mixed to obtain a mixture. The mixture was put into a planetary mixer for preliminary mixing, and the mixed nickel paste was put into a three-roll mill for dispersion. The dispersed nickel paste was filtered under pressure to obtain a modified nickel paste for MLCC. The specifications of the filter element, the process parameters of the planetary mixer, and the process parameters of the three-roll mill were all the same as those in Example 1.

[0094] Detection method In the dispersibility test, it was measured by a surface roughness tester. Using the modified nickel paste for MLCC manufactured in Examples 1 to 28 and Comparative Examples 1 to 3, a regular pattern of 10 mm × 10 mm (length × width) was printed on a glass substrate by screen printing. After drying in a bag-type drying furnace, the surface roughness Ra and Rt were measured to characterize the dispersion performance of the modified nickel paste. The lower the roughness, the better the dispersion performance. In the electrical performance test, using the modified nickel paste for MLCCs manufactured in Examples 1 to 28 and Comparative Examples 1 to 3, first, the thickness of the ceramic powder casting film was designed based on the dimensional specifications of the MLCCs and the K value of the selected ceramic powder. Then, the MLCCs were manufactured through the processes of ceramic powder casting film formation (manufacture of ceramic paste and casting of ceramic film) - manufacture of internal electrodes (screen printing of nickel paste and underlayer) - manufacture of capacitor chips (lamination and cutting separation) - formation of sintered ceramics (discharge of adhesive, sintering, and chamfering) - manufacture of external electrodes (terminal forming, baking, and electroplating). Using a four-parameter tester, performance tests were conducted on the above-manufactured MLCCs (each example / comparative example was regarded as a set, and 50 MLCCs were manufactured corresponding to each set). The capacitance value, loss, breakdown voltage, and TCC at 200°C of the MLCCs were tested. TCC = (C(200°C) - C(25°C)) / C(25°C) × 100%, and the smaller the absolute value of TCC, the better the high-temperature resistance performance of the MLCC (C(200°C) and C(25°C) represent the capacitance of the MLCC at different temperatures). The test voltage was set to 1V, and the frequency was set to 1kHz. The specific measurement results are shown in Table 4 below.

[0095] The capacitance value, loss, and TCC at 200°C are the average values of 50 MLCCs, and the breakdown voltage is a range value.

[0096] In the accelerated aging test, the above-manufactured MLCCs were placed in an aging tester (each example / comparative example was regarded as a set, and 100 MLCCs were manufactured corresponding to each set). Under the conditions of 8Ur, 150°C, and 8h, the capacitance (C), loss (DF), and insulation resistance (IR) of the MLCCs before and after being placed in the aging tester were tested. If |ΔC / C| ≦ 20%, DF ≦ 2 times the initial value, and IR ≧ 2000 mΩ, it was considered a good product. By testing the qualification rate of each set, the adhesion performance of the modified nickel paste and the ceramic coating layer and the influence of the diluent on the ceramic coating layer were characterized (qualification rate = number of good products / 100).

[0097]

Table 4

[0098] As can be seen from Table 4 (Performance Test), the nickel paste manufactured in the examples of the present application has Ra≤0.083 μm and Rt≤0.692 μm, which indicates that the dispersion performance of the nickel paste manufactured in the examples of the present application is excellent and the nano BaTiO3 powder is well dispersed in the nickel paste. The MLCC manufactured with the nickel paste manufactured in the examples of the present application has a capacitance value of ≥0.95 uF, a loss of ≤2.9%, a breakdown voltage of ≥345 V, an absolute value of TCC at 200 °C of ≤13.1, and a pass rate in the accelerated aging test of ≥85%, which indicates that the MLCC finished product has good use performance.

[0099] As can be seen by combining Example 1 and Comparative Example 1 and referring to Table 4, the roughness of the nickel paste in Example 1 is much smaller than that in Comparative Example 1, and the performance of each MLCC finished product manufactured from the nickel paste in Example 1 is also superior to that in Comparative Example 1. This is because in Example 1, the nano BaTiO3 powder was pre-dispersed with a dispersant to obtain a uniformly dispersed nano BaTiO3 pre-dispersion, and then the nano BaTiO3 pre-dispersion was mixed and dispersed with nickel powder and other raw materials at a specific ratio to obtain a uniformly dispersed nickel paste, thereby solving the problem that the nano BaTiO3 powder is not uniformly dispersed in the nickel paste for MLCC and improving the use performance of the MLCC finished product.

[0100] As can be seen by combining Example 1 and Comparative Examples 2 - 3 and referring to Table 4, the roughness of the nickel paste in Example 1 is much smaller than that in Comparative Examples 2 - 3, and the performance of each MLCC finished product manufactured from the nickel paste in Example 1 is also superior to that in Comparative Examples 2 - 3. This may be because the mass ratios of the BaTiO3 pre-dispersion, adhesive, dispersant, diluent, and nickel powder in Comparative Examples 2 - 3 are not within the scope of the present application. After multiple experiments by the inventor, by controlling the mass ratios of the above raw materials, the above raw materials are uniformly dispersed in the nickel paste, and the use performance of the MLCC finished product is improved.

[0101] As can be seen by combining Example 1 with Examples 11 to 18 and referring to Table 4, the pass rates of the MLCC finished products manufactured in Example 1 and Example 11 are much higher than those in Examples 12 to 18. This may be because the diluents selected in Example 1 and Example 11 are those obtained by blending terpineol, isobornyl acetate, and butyl acetate in a specific mass ratio. As discovered by the inventor through multiple experiments, by selecting the above diluent, the destruction of the ceramic coating layer can be reduced, so the anti-aging performance of the MLCC finished product can be improved.

[0102] As can be seen by combining Examples 1 to 5 with Example 22 and referring to Table 4, the pass rates of the MLCC finished products manufactured in Examples 1 to 3 are much higher than those in Examples 4 to 5 and Example 22. This may be because the adhesives selected in Examples 1 to 3 are different from those in Examples 4 to 5 and Example 22. In Examples 1 to 3, using terminal epoxy group hyperbranched polyester as a bridge, ethyl cellulose was grafted onto polyvinyl butyral molecules to obtain an adhesive containing multiple active groups. The adhesive was added to the nickel paste. Some of the active groups of the adhesive cross-linked with each other to firmly adhere each component, and some of the other active groups bonded to the hydroxyl groups of the ceramic coating layer, so as to have good adhesion between the nickel paste and the ceramic coating layer, thus improving the performance of the MLCC finished product.

[0103] The adhesive in Example 4 is pure polyvinyl butyral, the adhesive in Example 5 is pure ethyl cellulose, and the adhesive in Example 22 is obtained by simply blending polyvinyl butyral and ethyl cellulose. The adhesion of these three types of adhesives to the ceramic coating layer is smaller than that of the adhesive used in Examples 1 to 3.

[0104] As can be seen by combining Example 1 with Examples 19 to 21 and referring to Table 4, the breakdown voltage values of the MLCC finished products manufactured in Examples 19 and 21 are much higher than those in Examples 1 and 20, and the absolute value of TCC at 200 °C of the MLCC finished products manufactured in Examples 19 and 21 is lower than those in Examples 1 and 20. This is because the nickel powder selected in Examples 19 and 21 is doped with sulfur and other metals, and has better breakdown voltage performance and high-temperature resistance performance compared with the nickel powder selected in Examples 1 and 20. When this nickel powder is used in the manufacture of MLCCs, it may be possible to fundamentally improve the breakdown voltage performance and high-temperature resistance performance of MLCCs.

[0105] This specific embodiment is merely an illustration of the present application and does not limit the present application. After reading this specification, those skilled in the art can make modifications to this embodiment without creative contributions as needed, but as long as it is within the scope of the claims of the present application, it will be protected by the patent law.

Claims

1. A method for manufacturing a modified nickel paste for an MLCC (multilayer ceramic chip capacitor), wherein Nano BaTiO ３ The powder, diluent, and dispersant are uniformly mixed and dispersed at a mass ratio of (60 - 90):(20 - 30):1 to obtain a nano BaTiO ３ pre-dispersion body. The nano BaTiO ３ pre-dispersion step, and The nano BaTiO ３ A nickel paste manufacturing step of mixing a preliminary dispersion, an adhesive, a dispersant, a diluent, and nickel powder at a mass ratio of 10:(10-15):(0.1-1):(10-15):(25-60), dispersing them, and filtering to obtain a modified nickel paste for MLCC, is included, the adhesive is a step of manufacturing a terminal epoxy group hyperbranched polyester by reacting a terminal hydroxyl group hyperbranched polyester and epichlorohydrin at a mass ratio of (10 - 20):1 to obtain a terminal epoxy group hyperbranched polyester, a step of manufacturing a modified polyvinyl butyral by reacting the terminal epoxy group hyperbranched polyester and polyvinyl butyral at a mass ratio of (10 - 25):1 to obtain a modified polyvinyl butyral, and a step of manufacturing an adhesive by reacting the modified polyvinyl butyral and ethyl cellulose at a mass ratio of (2 - 10):1 to obtain an adhesive, and the manufacturing method is characterized by being manufactured by these steps.

2. The nano BaTiO ３ The manufacturing method according to claim 1, characterized in that the mass ratio of the preliminary dispersion to the nickel powder is 10:(50 to 60).

3. The nano BaTiO ３ The manufacturing method according to claim 1, characterized in that the particle size of the powder is 10 to 200 nm.

4. The manufacturing method according to Claim 1, wherein the diluent is one or more of terpineol, isobornyl acetate, isophorone, and butyl acetate.

5. The manufacturing method according to Claim 4, wherein the diluent is formulated by mixing terpineol, isobornyl acetate, and butyl acetate at a mass ratio of (0.2 - 1):(0.5 - 1.5):

1.

6. The manufacturing method according to Claim 1, wherein the nickel powder is synthesized by a chemical method, the raw material of the nickel powder contains nickel sulfate and other metal salts, and the other metal salts are one or more of chromium sulfate, copper sulfate, and silver sulfate.

7. The manufacturing method according to Claim 1, wherein the nickel powder is synthesized by a physical vapor deposition method, the raw material of the nickel powder contains a nickel target, sulfur powder, and other metal targets, and the other metal targets are one or more of a chromium target, a copper target, and a silver target.

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