Preparation method of zinc oxide resistor with high gradient, large through-flow and stable impact

Abstract

The invention belongs to the technical field of resistor electrical elements, and particularly relates to a preparation method of a zinc oxide resistor with high gradient, large through-flow and stable impact. The zinc oxide resistor comprises zinc oxide, bismuth trioxide, antimony trioxide, nickel sesquioxide, manganous-manganic oxide, cobaltosic oxide, tin dioxide, diboron trioxide, nano silver powder, aluminum nitrate nonahydrate, barium acetate, a binder, a dispersing agent and deionized water. The zinc oxide varistor designed by the invention has the advantage of good stability under high gradient and large flux, overcomes the degeneration behavior of the zinc oxide varistor caused by the influence of the existing large-current surge impact on the zinc oxide crystal boundary potential barrier, and is suitable for industrial popularization.

Description

Technical Field

[0001] The present invention belongs to the technical field of resistive electrical components, and particularly relates to a preparation method of a zinc oxide resistor with high gradient, large current-carrying capacity and impact stability. Background Art

[0002] A metal oxide arrester is a protector used to limit overvoltage. It is usually connected in parallel with the protected equipment between the system and the ground. Under normal operating voltage, it exhibits a very high resistance, equivalent to an insulator. When the system experiences overvoltage, its excellent non-linear volt-ampere characteristics cause its high resistance to become low resistance, and the residual voltage across its two ends is limited to an acceptable level, and the overvoltage energy is absorbed, thereby protecting the circuit. Zinc oxide varistors have become the core components of metal oxide arresters due to their excellent non-linear volt-ampere characteristics and energy absorption capabilities, and are widely used in surge protection of power systems and electronic devices.

[0003] With the rapid development of ultra-high voltage power systems and the demand for device miniaturization, there is an urgent need for zinc oxide varistors with enhanced performance. The non-linear coefficient of pure zinc oxide is very small, and different types and contents of additives often need to be doped to improve the electrical properties of zinc oxide varistors. The reason why zinc oxide varistors have good non-linearity is that there is a grain boundary barrier at their grain boundaries, and the formation of the grain boundary barrier stems from the microscopic defect structure inside zinc oxide. As is well known, there are intrinsic zinc interstitials, oxygen vacancies, zinc vacancies and atomic or ionic defects formed by additives in zinc oxide varistors. The use of different additives and dosages has different effects on the defect structure, and the macroscopic electrical properties of the prepared resistor chips also vary.

[0004] At present, many studies only focus on the research of three parameters, while ignoring the influence of current-carrying capacity and stability on zinc oxide varistors. Therefore, a suitable raw material formula and additive content are one of the keys to preparing resistor chips with high gradient, low resistivity and high stability.

[0005] Therefore, based on the improvement of materials and preparation processes, the present method proposes a preparation method of a zinc oxide resistor with high gradient, large current-carrying capacity and impact stability, which has the advantage of good stability under high gradient and large current, overcomes the degradation behavior of zinc oxide varistors caused by the influence of large current surge on the grain boundary barrier of zinc oxide, and is suitable for industrial promotion. Summary of the Invention

[0006] The present invention aims to provide a preparation method of a zinc oxide resistor with high gradient, large current-carrying capacity and impact stability, which has a good improvement effect on the degradation behavior of zinc oxide varistors caused by the influence of the grain boundary barrier under large current surge through the improvement of related processes and raw materials.

[0007] Highlights of this method: 1. During the preparation of zinc oxide-silver composite, it is necessary to ensure that silver nanoparticles can effectively coat the surface of zinc oxide. Since silver is relatively soft and has good deformability and toughness, planetary ball milling is used for preliminary coating. Subsequent heat treatment is conducive to the mutual solid solution diffusion of silver, improving the coating effect. 2. During the preparation of the cold-pressed powder, it is necessary to ensure the uniformity of raw material mixing during the mixing process and avoid the agglomeration of large particle raw materials. Therefore, the proportions of the dispersant and binder should be appropriate. In addition, dissolving the dispersant and binder first to prepare glue is also to avoid the agglomeration of raw materials caused by adding them together. 3. During the green compact pressing process, the generation of defects should be avoided, especially cracks, which may cause cracking failure during the subsequent sintering process.

[0008] The specific implementation scheme of a preparation method of a zinc oxide resistor with high gradient, large current-carrying capacity and impact stability involved in the present invention is as follows: The raw materials of a zinc oxide resistor with high gradient, large current-carrying capacity and impact stability include zinc oxide, bismuth trioxide, antimony trioxide, nickel trioxide, manganese tetroxide, cobalt tetroxide, tin dioxide, boron trioxide, silver nanopowder, aluminum nitrate nonahydrate, barium acetate, binder, dispersant, deionized water; Measured by mass parts, wherein: 80-100 parts of zinc oxide, 2-4 parts of bismuth trioxide, 2-5 parts of antimony trioxide, 0.5-2 parts of nickel trioxide, 0.2-2 parts of manganese tetroxide, 0.5-3 parts of cobalt tetroxide, 0.1-0.4 parts of tin dioxide, 0.3-1 part of boron trioxide, 0.5-1.5 parts of silver nanopowder, 0.01-0.05 parts of aluminum nitrate nonahydrate, 0.5-1.5 parts of barium acetate, 1-3 parts of binder, 0.5-1.5 parts of dispersant, 320-450 parts of deionized water; The zinc oxide has a spherical powder with a particle size of 60-100 nm; The silver nanopowder is a spherical powder with a particle size of 20-50 nm; The binder is at least one of polyvinyl alcohol and polyvinylpyrrolidone; The dispersant is polyacrylic acid; A preparation method of a zinc oxide resistor with high gradient, large current-carrying capacity and impact stability includes steps such as the preparation of zinc oxide-silver composite, the preparation of cold-pressed powder, the preparation of green compact, sintering and post-treatment, and the specific implementation process is as follows: The preparation process of the zinc oxide-silver composite is as follows: The first step: Vacuum mix zinc oxide and silver nanopowder to obtain a zinc oxide-silver mixture. The mixing method is dry planetary ball milling, with a rotation speed of 200-300 rpm, a time of 1-3 h, and a vacuum degree of 1-10 Pa; Step 2: Perform vacuum heat treatment on the zinc oxide-silver mixture at a heat treatment temperature of 900 - 1000 °C, a heat treatment time of 30 - 60 min, and a vacuum degree of 0.1 - 1 Pa; Step 3: Disperse and screen the zinc oxide-silver mixture after vacuum heat treatment to obtain a zinc oxide-silver composite. The dispersion method is a jet mill, and the particle size of the powder is 100 - 200 nm; The preparation process of the cold-pressed powder is as follows: Step 1: Mix bismuth trioxide, antimony trioxide, nickel trioxide, manganese tetroxide, cobalt tetroxide, tin dioxide, boron trioxide and 20 - 50 parts of deionized water to obtain a wet slurry 1. The mixing method is wet planetary ball milling, with a rotation speed of 100 - 300 rpm and a ball milling time of 24 - 48 h; Step 2: Screen, dry and crush the wet slurry 1 to obtain a mixed powder 1. The aperture of the sieve for screening is 100 - 200 mesh, the drying temperature is 100 - 120 °C, and the crushing method is a jet mill; Step 3: Dissolve the binder, dispersant, aluminum nitrate nonahydrate, and barium acetate in 300 - 400 parts of deionized water, and stir well to obtain a glue solution. The stirring method is mechanical stirring, with a rotation speed of 200 - 400 rpm and a time of 30 - 60 min; Step 4: Perform wet ball milling and screening on the zinc oxide-silver composite, the mixed powder 1, and the glue solution to obtain a granulating slurry. The ball milling time is 20 - 30 h, the rotation speed is 100 - 300 rpm, and the sieve mesh number is 120 - 200 mesh; Step 5: Use a spray dryer to perform spray granulation on the granulating slurry to obtain granulated material. The spray granulation temperature is 150 - 180 °C; The preparation process of the green compact is as follows: Press the granulated material with a dry press to obtain a green compact. The dry pressing pressure is 100 - 200 Mpa, and the density of the obtained green compact is 3.2 - 3.3 g / cm 3 ; The preparation process of the sintering is as follows: Step 1: Perform debinding on the green compact at a debinding temperature of 400 - 430 °C, in an air atmosphere, and a debinding time of 60 - 90 min; Step 2: Perform sintering on the debound green compact to obtain a resistor chip blank. The sintering temperature is 1000 - 1100 °C, and the sintering time is 1 - 3 h; The preparation process of the post-treatment is as follows: Step 1: Grind, clean, dry, and perform heat treatment on the resistor chip blank, where the drying temperature is 150 - 170 °C, the heat treatment temperature is 500 - 550 °C, and the heat treatment time is 13 - 17 h; Step 2: Spray aluminum on the heat-treated resistor chips, coat the sides with insulating paint, and wrap with double-layer tape to obtain the finished zinc oxide resistor. Beneficial effects

[0009] (1) In the method designed by the present invention, by adjusting the ratio of each raw material in the resistor chip material and doping with boron trioxide glass powder, the preparation of resistor chips with high gradient, large current-carrying capacity and good stability is realized, overcoming the degradation behavior of zinc oxide varistors caused by the influence of existing large current surge impacts on the grain boundary barrier of zinc oxide. (2) In the method designed by the present invention, zinc oxide and nano silver powder are ball-milled and heat-treated to obtain a composite powder, enabling silver ions to penetrate into zinc oxide grains and reducing the influence of large current surge impacts on the grain boundary barrier of zinc oxide. (3) The zinc oxide resistor prepared by the method designed by the present invention has a diameter of 42.60 - 44.30 mm, a thickness of 11.05 - 12.50 mm, a varistor potential gradient range of 227 - 264 V / mm, a non-linear coefficient of 26 - 35, and a residual voltage ratio of 1.68 - 1.74 for a 5 kA 8 / 20 us lightning wave. Description of the drawings

[0010] Figure 1 It is a process flow chart for the preparation method of a zinc oxide resistor with high gradient, large current-carrying capacity and impact stability. Detailed implementation manners

[0011] In order to make the objectives, technical solutions and advantages of the present invention clearer, the present invention will be further described in detail below with reference to the drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention. Embodiment

[0012] The raw materials of a zinc oxide resistor with high gradient, large current-carrying capacity and impact stability include zinc oxide, bismuth trioxide, antimony trioxide, nickel trioxide, manganese tetroxide, cobalt tetroxide, tin dioxide, boron trioxide, nano silver powder, aluminum nitrate nonahydrate, barium acetate, binder, dispersant, deionized water; Measured by mass parts, where: 80 parts of zinc oxide, 2 parts of bismuth trioxide, 2 parts of antimony trioxide, 0.5 part of nickel trioxide, 0.2 part of manganese tetroxide, 0.5 part of cobalt tetroxide, 0.1 part of tin dioxide, 0.3 part of boron trioxide, 0.5 part of nano silver powder, 0.01 part of aluminum nitrate nonahydrate, 0.5 part of barium acetate, 1 part of binder, 0.5 part of dispersant, 320 parts of deionized water; The zinc oxide is a spherical powder with a particle size of 60 nm; The nano silver powder is a spherical powder with a particle size of 20 nm; The binder is polyvinyl alcohol; The dispersant is polyacrylic acid; A preparation method of a zinc oxide resistor with high-gradient large current-carrying impact stability includes steps such as preparation of a zinc oxide-silver composite, preparation of cold-pressed powder, preparation of green compact, sintering, and post-treatment. The specific implementation process is as follows: The preparation process of the zinc oxide-silver composite is as follows: First step: Vacuum mix zinc oxide and nano silver powder to obtain a zinc oxide-silver mixture. The mixing method is dry planetary ball milling, with a rotation speed of 200 rpm, a time of 1 h, and a vacuum degree of 1 Pa; Second step: Vacuum heat-treat the zinc oxide-silver mixture. The heat-treatment temperature is 900 °C, the heat-treatment time is 30 min, and the vacuum degree is 0.1 Pa; Third step: Disperse and screen the zinc oxide-silver mixture after vacuum heat-treatment to obtain a zinc oxide-silver composite. The dispersion method is jet milling, and the powder particle size is 100 nm; The preparation process of the cold-pressed powder is as follows: First step: Mix bismuth trioxide, antimony trioxide, nickel trioxide, manganese tetroxide, cobalt tetroxide, tin dioxide, boron trioxide and 20 parts of deionized water to obtain wet slurry one. The mixing method is wet planetary ball milling, with a rotation speed of 100 rpm and a ball milling time of 24 h; Second step: Screen, dry and crush wet slurry one to obtain mixed powder one. The screen aperture for screening is 100 mesh, the drying temperature is 100 °C, and the crushing method is jet milling; Third step: Dissolve the binder, dispersant, aluminum nitrate nonahydrate, and barium acetate in 300 parts of deionized water, and fully stir to obtain a glue solution. The stirring method is mechanical stirring, with a rotation speed of 200 rpm and a time of 30 min; Fourth step: Wet ball mill and screen the zinc oxide-silver composite, mixed powder one, and the glue solution to obtain granulating slurry. The ball milling time is 20 h, the rotation speed is 100 rpm, and the screen mesh number is 120 mesh; Fifth step: Use a spray dryer to perform spray granulation on the granulating slurry to obtain granulated material. The spray granulation temperature is 150 °C; The preparation process of the green compact is as follows: Press the granulated material with a dry press to obtain a green compact. The dry pressing pressure is 100 Mpa, and the density of the obtained green compact is 3.2 g / cm 3 ; The preparation process of the sintering is as follows: First step: Debind the green compact. The debinding temperature is 400 °C, the atmosphere is air, and the debinding time is 60 min; Step 2: Sinter the debinded green compact to obtain a resistor blank body, with a sintering temperature of 1000 - 1100 °C and a sintering time of 1 h; The preparation process of the post-treatment is as follows: Step 1: Grind, clean, dry, and heat-treat the resistor blank body, where the drying temperature is 150 °C, the heat-treatment temperature is 500 °C, and the heat-treatment time is 13 h; Step 2: Spray aluminum on the heat-treated resistor, coat the side with insulating paint, and wrap it with double-layer tape to obtain a finished zinc oxide resistor. Example

[0013] A raw material for a zinc oxide resistor with high gradient and large current-carrying capacity and impact stability includes zinc monoxide, bismuth trioxide, antimony trioxide, nickel trioxide, manganese tetroxide, cobalt tetroxide, tin dioxide, boron trioxide, nano silver powder, aluminum nitrate nonahydrate, barium acetate, binder, dispersant, deionized water; Measured by mass parts, where: 100 parts of zinc monoxide, 4 parts of bismuth trioxide, 5 parts of antimony trioxide, 2 parts of nickel trioxide, 2 parts of manganese tetroxide, 3 parts of cobalt tetroxide, 0.4 parts of tin dioxide, 1 part of boron trioxide, 1.5 parts of nano silver powder, 0.05 parts of aluminum nitrate nonahydrate, 1.5 parts of barium acetate, 3 parts of binder, 1.5 parts of dispersant, 450 parts of deionized water; The zinc monoxide has a spherical powder with a particle size of 100 nm; The nano silver powder is a spherical powder with a particle size of 50 nm; The binder is polyvinyl alcohol; The dispersant is polyacrylic acid; A preparation method of a zinc oxide resistor with high gradient and large current-carrying capacity and impact stability includes steps such as the preparation of zinc monoxide-silver composite, the preparation of cold-pressed powder, the preparation of green compact, sintering, and post-treatment, and the specific implementation process is as follows: The preparation process of the zinc monoxide-silver composite is as follows: Step 1: Vacuum mix zinc monoxide and nano silver powder to obtain a zinc monoxide-silver mixture. The mixing method is dry planetary ball milling, with a rotation speed of 300 rpm, a time of 3 h, and a vacuum degree of 10 Pa; Step 2: Vacuum heat-treat the zinc monoxide-silver mixture, with a heat-treatment temperature of 1000 °C, a heat-treatment time of 60 min, and a vacuum degree of 1 Pa; Step 3: Disperse and screen the zinc monoxide-silver mixture after vacuum heat-treatment to obtain a zinc monoxide-silver composite. The dispersion method is jet mill, and the powder particle size is 200 nm; The preparation process of the cold-pressed powder is as follows: Step 1: Mix bismuth trioxide, antimony trioxide, nickel trioxide, manganese tetroxide, cobalt tetroxide, tin dioxide, boron trioxide and 50 parts of deionized water to obtain Wet Slurry 1. The mixing method is wet planetary ball milling, with a rotation speed of 300 rpm and a ball milling time of 48 h; Step 2: Screen, dry and crush Wet Slurry 1 to obtain Mixed Powder 1. The screen aperture for screening is 200 mesh, the drying temperature is 120 °C, and the crushing method is jet mill; Step 3: Dissolve the binder, dispersant, aluminum nitrate nonahydrate, and barium acetate in 400 parts of deionized water, and stir well to obtain a glue solution. The stirring method is mechanical stirring, with a rotation speed of 400 rpm and a time of 60 min; Step 4: Perform wet ball milling and screening on the zinc oxide-silver composite, Mixed Powder 1, and the glue solution to obtain Granulation Slurry. The ball milling time is 30 h, the rotation speed is 300 rpm, and the screen mesh is 200 mesh; Step 5: Use a spray dryer to perform spray granulation on the Granulation Slurry to obtain Granulated Material. The spray granulation temperature is 180 °C; The preparation process of the green compact is as follows: Press the Granulated Material using a dry press to obtain a green compact. The dry pressing pressure is 200 Mpa, and the density of the obtained green compact is 3.3 g / cm 3 ; The preparation process of the sintering is as follows: Step 1: Debind the green compact. The debinding temperature is 430 °C, the atmosphere is air, and the debinding time is 90 min; Step 2: Sinter the debound green compact to obtain a resistor chip blank. The sintering temperature is 1100 °C, and the sintering time is 3 h; The preparation process of the post-treatment is as follows: Step 1: Grind, clean, dry, and heat-treat the resistor chip blank. Among them, the drying temperature is 170 °C, the heat treatment temperature is 550 °C, and the heat treatment time is 17 h; Step 2: Spray aluminum on the heat-treated resistor chip, coat the side with insulating paint, and wrap it with double-layer tape to obtain a finished zinc oxide resistor. Example

[0014] A raw material for a zinc oxide resistor with high gradient and large current-carrying capacity and stable impact includes zinc oxide, bismuth trioxide, antimony trioxide, nickel trioxide, manganese tetroxide, cobalt tetroxide, tin dioxide, boron trioxide, nano silver powder, aluminum nitrate nonahydrate, barium acetate, binder, dispersant, and deionized water; Measured by parts by mass, where: 90 parts of zinc monoxide, 3 parts of bismuth trioxide, 4 parts of antimony trioxide, 1 part of nickel trioxide, 1.2 parts of manganese tetroxide, 1.5 parts of cobalt tetroxide, 0.3 parts of tin dioxide, 0.7 parts of boron trioxide, 1 part of nano silver powder, 0.03 parts of aluminum nitrate nonahydrate, 1 part of barium acetate, 2 parts of binder, 1 part of dispersant, 380 parts of deionized water; The zinc monoxide has a spherical powder with a particle size of 80 nm; The nano silver powder is a spherical powder with a size of 30 nm; The binder is polyvinylpyrrolidone; The dispersant is polyacrylic acid; A preparation method of a zinc oxide resistor with high-gradient large current-carrying impact stability includes steps such as preparation of zinc monoxide-silver composite, preparation of cold-pressed powder, preparation of green compact, sintering, and post-treatment. The specific implementation process is as follows: The preparation process of the zinc monoxide-silver composite is as follows: First step: Vacuum mix zinc monoxide and nano silver powder to obtain a zinc monoxide-silver mixture. The mixing method is dry planetary ball milling, with a rotation speed of 250 rpm, a time of 2 h, and a vacuum degree of 5 Pa; Second step: Vacuum heat-treat the zinc monoxide-silver mixture. The heat-treatment temperature is 950 °C, the heat-treatment time is 40 min, and the vacuum degree is 0.5 Pa; Third step: Disperse and screen the zinc monoxide-silver mixture after vacuum heat-treatment to obtain a zinc monoxide-silver composite. The dispersion method is jet milling, and the particle size of the powder is 150 nm; The preparation process of the cold-pressed powder is as follows: First step: Mix bismuth trioxide, antimony trioxide, nickel trioxide, manganese tetroxide, cobalt tetroxide, tin dioxide, boron trioxide and 30 parts of deionized water to obtain wet slurry one. The mixing method is wet planetary ball milling, with a rotation speed of 200 rpm and a ball milling time of 30 h; Second step: Screen, dry, and crush wet slurry one to obtain mixed powder one. The aperture of the sieve for screening is 150 mesh, the drying temperature is 110 °C, and the crushing method is jet milling; Third step: Dissolve the binder, dispersant, aluminum nitrate nonahydrate, and barium acetate in 350 parts of deionized water, and stir well to obtain a glue solution. The stirring method is mechanical stirring, with a rotation speed of 300 rpm and a time of 40 min; Fourth step: Wet ball mill and screen the zinc monoxide-silver composite, mixed powder one, and glue solution to obtain granulation slurry. The ball milling time is 25 h, the rotation speed is 200 rpm, and the sieve mesh number is 180 mesh; Step 5: Use a spray dryer to perform spray granulation on the granulation slurry to obtain granulated material, and the spray granulation temperature is 160 °C; The preparation process of the green compact is as follows: Press the granulated material using a dry press to obtain a green compact. The dry pressing pressure is 150 Mpa, and the density of the obtained green compact is 3.2 g / cm 3 ; The preparation process of the sintering is as follows: Step 1: Perform debinding on the green compact. The debinding temperature is 420 °C, the atmosphere is air, and the debinding time is 80 min; Step 2: Perform sintering on the debound green compact to obtain a resistor chip blank. The sintering temperature is 1050 °C, and the sintering time is 2 h; The preparation process of the post-treatment is as follows: Step 1: Grind, clean, dry, and perform heat treatment on the resistor chip blank. Among them, the drying temperature is 160 °C, the heat treatment temperature is 520 °C, and the heat treatment time is 15 h; Step 2: Spray aluminum, coat insulating paint on the side, and wrap double-layer tape on the heat-treated resistor chip to obtain a finished zinc oxide resistor.

[0015] Comparative Example 1: A raw material for a zinc oxide resistor with high-gradient large current-carrying capacity and impact stability includes zinc monoxide, bismuth trioxide, antimony trioxide, nickel trioxide, manganese tetraoxide, cobalt tetraoxide, tin dioxide, boron trioxide, aluminum nitrate nonahydrate, barium acetate, binder, dispersant, deionized water; Measured by mass portion dosage, among them: 90 parts of zinc monoxide, 3 parts of bismuth trioxide, 4 parts of antimony trioxide, 1 part of nickel trioxide, 1.2 parts of manganese tetraoxide, 1.5 parts of cobalt tetraoxide, 0.3 part of tin dioxide, 0.7 part of boron trioxide, 0.03 part of aluminum nitrate nonahydrate, 1 part of barium acetate, 2 parts of binder, 1 part of dispersant, 380 parts of deionized water; The zinc monoxide is a spherical powder with a particle size of 80 nm; The binder is polyvinyl alcohol; The dispersant is polyacrylic acid; A preparation method of a zinc oxide resistor with high-gradient large current-carrying capacity and impact stability respectively includes steps such as preparation of cold-pressed powder, preparation of green compact, sintering, and post-treatment. The specific implementation process is as follows: The preparation process of the cold-pressed powder is as follows: Step 1: Mix bismuth trioxide, antimony trioxide, nickel trioxide, manganese tetraoxide, cobalt tetraoxide, tin dioxide, boron trioxide and 30 parts of deionized water to obtain wet slurry one. The mixing method is wet planetary ball milling, the rotation speed is 200 rpm, and the ball milling time is 30 h; Step 2: Screen, dry, and crush the wet slurry 1 to obtain mixed powder 1. The aperture of the screening mesh is 150 meshes, the drying temperature is 110 °C, and the crushing method is jet mill; Step 3: Dissolve the binder, dispersant, aluminum nitrate nonahydrate, and barium acetate in 350 parts of deionized water, and stir well to obtain a glue solution. The stirring method is mechanical stirring, the rotation speed is 300 rpm, and the time is 40 min; Step 4: Perform wet ball milling and screening on zinc oxide, mixed powder 1, and the glue solution to obtain granulating slurry. The ball milling time is 25 h, the rotation speed is 200 rpm, and the mesh number of the screening mesh is 180 meshes; Step 5: Use a spray dryer to perform spray granulation on the granulating slurry to obtain granulated material. The spray granulation temperature is 160 °C; The preparation process of the green compact is as follows: Press the granulated material with a dry press to obtain a green compact. The dry pressing pressure is 150 Mpa, and the density of the obtained green compact is 3.2 g / cm 3 ; The preparation process of the sintering is as follows: Step 1: Perform debinding on the green compact. The debinding temperature is 420 °C, the atmosphere is air, and the debinding time is 80 min; Step 2: Sinter the debound green compact to obtain a resistor chip blank. The sintering temperature is 1050 °C, and the sintering time is 2 h; The preparation process of the post-treatment is as follows: Step 1: Grind, clean, dry, and heat-treat the resistor chip blank. Among them, the drying temperature is 160 °C, the heat treatment temperature is 520 °C, and the heat treatment time is 15 h; Step 2: Spray aluminum on the heat-treated resistor chip, coat insulating paint on the side, and wrap double-layer tape to obtain a finished zinc oxide resistor.

[0016] Comparative Example 2: A raw material for a zinc oxide resistor with high-gradient large current-carrying impact stability includes zinc oxide, bismuth trioxide, antimony trioxide, nickel trioxide, manganese tetroxide, cobalt tetroxide, boron trioxide, nano silver powder, aluminum nitrate nonahydrate, barium acetate, binder, dispersant, and deionized water; Measured by mass parts dosage, among them: 90 parts of zinc oxide, 3 parts of bismuth trioxide, 4 parts of antimony trioxide, 1 part of nickel trioxide, 1.2 parts of manganese tetroxide, 1.5 parts of cobalt tetroxide, 0.7 part of boron trioxide, 1 part of nano silver powder, 0.03 part of aluminum nitrate nonahydrate, 1 part of barium acetate, 2 parts of binder, 1 part of dispersant, and 380 parts of deionized water; The zinc oxide has a spherical powder with a particle size of 80 nm; The nano silver powder is a spherical powder with a diameter of 30 nm; The binder is polyvinyl alcohol; The dispersant is polyacrylic acid; A method for preparing a high-gradient, large-current impact-stable zinc oxide resistor comprises the steps of preparing a zinc oxide-silver composite, preparing a cold-pressed powder, preparing a green body, sintering and post-processing. The specific implementation process is as follows: The preparation process of the cold pressed powder is as follows: The first step: bismuth trioxide, antimony trioxide, nickel trioxide, manganese tetraoxide, cobalt tetraoxide, boron trioxide and 30 parts of deionized water are mixed to obtain a wet slurry 1, and the mixing method is wet planetary ball milling, the rotation speed is 200 rpm, and the ball milling time is 30 hours; Step 2: Screening, drying and crushing the wet slurry 1 to obtain a mixed powder 1, the sieve mesh size is 150 mesh, the drying temperature is 110°C, and the crushing method is air jet mill; Step 3: Dissolve the binder, dispersant, aluminum nitrate nonahydrate and barium acetate in 350 parts of deionized water, stir thoroughly to obtain a glue solution, stir mechanically at a speed of 300 rpm for 40 minutes; Step 4: Wet ball milling the zinc oxide, nano silver powder, mixed powder 1 and glue solution, and sieving to obtain granulation slurry, the ball milling time is 25h, the rotation speed is 200rpm, and the mesh number of the sieve is 180 mesh; Step 5: Use a spray dryer to spray granulate the granulation slurry to obtain granulated material, and the spray granulation temperature is 160°C; The preparation process of the green block is as follows: The granulated material was pressed into a green block using a dry press. The dry pressing pressure was 150 MPa. The density of the green block obtained by pressing was 3.2 g / cm 3 ; The sintering preparation process is as follows: Step 1: Debinding the green block at a temperature of 420°C, in an air atmosphere, for 80 minutes; Step 2: Sinter the green block after debinding to obtain the resistor chip body, the sintering temperature is 1050°C, and the sintering time is 2h; The preparation process of the post-treatment is as follows: Step 1: Grind, clean, dry and heat treat the resistor chip blank, where the drying temperature is 160°C, the heat treatment temperature is 520°C and the heat treatment time is 15h; Step 2: Spray aluminum on the heat-treated resistor, apply insulating paint on the side and wrap it with double-layer tape to obtain a finished zinc oxide resistor.

[0017] Comparative Example 3: A raw material for a zinc oxide resistor with high-gradient large current-carrying impact stability includes zinc monoxide, bismuth trioxide, antimony trioxide, nickel trioxide, manganese tetroxide, cobalt tetroxide, tin dioxide, nano silver powder, aluminum nitrate nonahydrate, barium acetate, binder, dispersant, deionized water; Measured by mass parts, wherein: 90 parts of zinc monoxide, 3 parts of bismuth trioxide, 4 parts of antimony trioxide, 1 part of nickel trioxide, 1.2 parts of manganese tetroxide, 1.5 parts of cobalt tetroxide, 0.3 parts of tin dioxide, 1 part of nano silver powder, 0.03 parts of aluminum nitrate nonahydrate, 1 part of barium acetate, 2 parts of binder, 1 part of dispersant, 380 parts of deionized water; The zinc monoxide has a spherical powder with a particle size of 80 nm; The nano silver powder is a spherical powder with a particle size of 30 nm; The binder is polyvinyl alcohol; The dispersant is polyacrylic acid; A preparation method of a zinc oxide resistor with high-gradient large current-carrying impact stability respectively includes steps such as preparation of zinc monoxide-silver composite, preparation of cold-pressed powder, preparation of green compact, sintering and post-treatment, and the specific implementation process is as follows: The preparation process of the zinc monoxide-silver composite is as follows: The first step: Vacuum mix zinc monoxide and nano silver powder to obtain a zinc monoxide-silver mixture. The mixing method is dry planetary ball milling, the rotation speed is 250 rpm, the time is 2 h, and the vacuum degree is 5 Pa; The second step: Vacuum heat-treat the zinc monoxide-silver mixture. The heat-treatment temperature is 950 °C, the heat-treatment time is 40 min, and the vacuum degree is 0.5 Pa; The third step: Disperse and screen the zinc monoxide-silver mixture after vacuum heat-treatment to obtain a zinc monoxide-silver composite. The dispersion method is jet mill, and the particle size of the powder is 150 nm; The preparation process of the cold-pressed powder is as follows: The first step: Mix bismuth trioxide, antimony trioxide, nickel trioxide, manganese tetroxide, cobalt tetroxide, tin dioxide and 30 parts of deionized water to obtain wet slurry one. The mixing method is wet planetary ball milling, the rotation speed is 200 rpm, and the ball milling time is 30 h; The second step: Screen, dry and crush wet slurry one to obtain mixed powder one. The screen aperture of screening is 150 mesh, the drying temperature is 110 °C, and the crushing method is jet mill; The third step: Dissolve the binder, dispersant, aluminum nitrate nonahydrate, and barium acetate in 350 parts of deionized water, and fully stir to obtain a glue solution. The stirring method is mechanical stirring, the rotation speed is 300 rpm, and the time is 40 min; Step 4: Wet ball-mill the zinc monoxide-silver composite, the first mixed powder, and the glue solution, and then screen them to obtain granulation slurry. The ball-milling time is 25 h, the rotation speed is 200 rpm, and the mesh number of the sieve is 180 meshes. Step 5: Use a spray dryer to perform spray granulation on the granulation slurry to obtain granulated material. The spray granulation temperature is 160 °C. The preparation process of the green compact is as follows: Press the granulated material with a dry press to obtain a green compact. The dry pressing pressure is 150 Mpa, and the density of the obtained green compact is 3.2 g / cm 3 ; The preparation process of the sintering is as follows: Step 1: Debind the green compact. The debinding temperature is 420 °C, the atmosphere is air, and the debinding time is 80 min. Step 2: Sinter the debound green compact to obtain a resistor chip blank. The sintering temperature is 1050 °C, and the sintering time is 2 h. The preparation process of the post-treatment is as follows: Step 1: Grind, clean, dry, and heat-treat the resistor chip blank. The drying temperature is 160 °C, the heat-treatment temperature is 520 °C, and the heat-treatment time is 15 h. Step 2: Spray aluminum on the heat-treated resistor chip, coat the side with insulating paint, and wrap it with double-layer tape to obtain a finished zinc oxide resistor.

[0018] Comparative Example 4: A raw material for a zinc oxide resistor with high gradient and large current-carrying capacity and impact stability includes zinc monoxide, bismuth trioxide, antimony trioxide, nickel trioxide, manganese tetroxide, tin dioxide, boron trioxide, nano silver powder, aluminum nitrate nonahydrate, barium acetate, binder, dispersant, and deionized water; Measured by mass parts, wherein: 90 parts of zinc monoxide, 3 parts of bismuth trioxide, 4 parts of antimony trioxide, 1 part of nickel trioxide, 1.2 parts of manganese tetroxide, 0.3 part of tin dioxide, 0.7 part of boron trioxide, 1 part of nano silver powder, 0.03 part of aluminum nitrate nonahydrate, 1 part of barium acetate, 2 parts of binder, 1 part of dispersant, and 380 parts of deionized water; The zinc monoxide is spherical powder with a particle size of 80 nm; The nano silver powder is spherical powder with a particle size of 30 nm; The binder is polyvinyl alcohol; The dispersant is polyacrylic acid; A preparation method of a zinc oxide resistor with high gradient and large current-carrying capacity and impact stability includes steps such as the preparation of zinc monoxide-silver composite, the preparation of cold-pressed powder, the preparation of green compact, sintering, and post-treatment. The specific implementation process is as follows: The preparation process of the zinc oxide-silver composite is as follows: The first step: Vacuum mix zinc oxide and nano silver powder to obtain a zinc oxide-silver mixture. The mixing method is dry planetary ball milling, with a rotation speed of 250 rpm, a time of 2 h, and a vacuum degree of 5 Pa; The second step: Vacuum heat-treat the zinc oxide-silver mixture. The heat-treatment temperature is 950 °C, the heat-treatment time is 40 min, and the vacuum degree is 0.5 Pa; The third step: Disperse and screen the zinc oxide-silver mixture after vacuum heat-treatment to obtain a zinc oxide-silver composite. The dispersion method is jet milling, and the powder particle size is 150 nm; The preparation process of the cold-pressed powder is as follows: The first step: Mix bismuth trioxide, antimony trioxide, nickel trioxide, manganese tetroxide, tin dioxide, boron trioxide and 30 parts of deionized water to obtain wet slurry one. The mixing method is wet planetary ball milling, with a rotation speed of 200 rpm and a ball milling time of 30 h; The second step: Screen, dry and crush wet slurry one to obtain mixed powder one. The screen aperture of screening is 150 mesh, the drying temperature is 110 °C, and the crushing method is jet milling; The third step: Wet ball mill the binder, dispersant, aluminum nitrate nonahydrate, barium acetate, zinc oxide-silver composite, mixed powder one and 350 parts of deionized water to obtain granulating slurry, with a ball milling time of 25 h and a rotation speed of 200 rpm; The fourth step: Use a spray dryer to perform spray granulation on the granulating slurry to obtain granulated material. The spray granulation temperature is 160 °C; The preparation process of the green compact is as follows: Press the granulated material with a dry press to obtain a green compact. The dry pressing pressure is 150 Mpa, and the density of the obtained green compact is 3.2 g / cm 3 ; The preparation process of the sintering is as follows: The first step: Debind the green compact. The debinding temperature is 420 °C, the atmosphere is air, and the debinding time is 80 min; The second step: Sinter the debound green compact to obtain a resistor chip blank. The sintering temperature is 1050 °C, and the sintering time is 2 h; The preparation process of the post-treatment is as follows: The first step: Grind, clean, dry and heat-treat the resistor chip blank, where the drying temperature is 160 °C, the heat-treatment temperature is 520 °C, and the heat-treatment time is 15 h; The second step: Spray aluminum, coat the side with insulating paint and wrap double-layer tape on the heat-treated resistor chip to obtain the finished zinc oxide resistor.

[0019] Comparative Example 5: A raw material for zinc oxide resistor with high-gradient large current-carrying impact stability includes zinc monoxide, bismuth trioxide, antimony trioxide, nickel trioxide, cobalt tetroxide, tin dioxide, boron trioxide, nano silver powder, aluminum nitrate nonahydrate, barium acetate, binder, dispersant, and deionized water; Measured by mass parts, where: 90 parts of zinc monoxide, 3 parts of bismuth trioxide, 4 parts of antimony trioxide, 1 part of nickel trioxide, 1.5 parts of cobalt tetroxide, 0.3 part of tin dioxide, 0.7 part of boron trioxide, 1 part of nano silver powder, 0.03 part of aluminum nitrate nonahydrate, 1 part of barium acetate, 2 parts of binder, 1 part of dispersant, and 380 parts of deionized water; The zinc monoxide has a spherical powder with a particle size of 80 nm; The nano silver powder is a spherical powder with a particle size of 30 nm; The binder is polyvinyl alcohol; The dispersant is polyacrylic acid; A preparation method for a zinc oxide resistor with high-gradient large current-carrying impact stability includes steps such as the preparation of zinc monoxide-silver composite, the preparation of cold-pressed powder, the preparation of green compact, sintering, and post-treatment. The specific implementation process is as follows: The preparation process of the zinc monoxide-silver composite is as follows: First step: Vacuum mix zinc monoxide and nano silver powder to obtain a zinc monoxide-silver mixture. The mixing method is dry planetary ball milling, with a rotation speed of 250 rpm, a time of 2 h, and a vacuum degree of 5 Pa; Second step: Vacuum heat-treat the zinc monoxide-silver mixture. The heat-treatment temperature is 950 °C, the heat-treatment time is 40 min, and the vacuum degree is 0.5 Pa; Third step: Disperse and screen the zinc monoxide-silver mixture after vacuum heat-treatment to obtain a zinc monoxide-silver composite. The dispersion method is jet milling, and the powder particle size is 150 nm; The preparation process of the cold-pressed powder is as follows: First step: Mix bismuth trioxide, antimony trioxide, nickel trioxide, cobalt tetroxide, tin dioxide, boron trioxide, and 30 parts of deionized water to obtain wet slurry one. The mixing method is wet planetary ball milling, with a rotation speed of 200 rpm and a ball milling time of 30 h; Second step: Screen, dry, and crush wet slurry one to obtain mixed powder one. The screen aperture of the screen is 150 mesh, the drying temperature is 110 °C, and the crushing method is jet milling; Third step: Dissolve the binder, dispersant, aluminum nitrate nonahydrate, and barium acetate in 350 parts of deionized water, and fully stir to obtain a glue solution. The stirring method is mechanical stirring, with a rotation speed of 300 rpm and a time of 40 min; Step 4: Wet ball-mill the zinc oxide-silver composite, mixed powder I, and glue solution, and then sieve to obtain granulation slurry. The ball-milling time is 25 h, the rotation speed is 200 rpm, and the mesh number of the sieve is 180 meshes. Step 5: Use a spray dryer to perform spray granulation on the granulation slurry to obtain granulated material. The spray granulation temperature is 160 °C. The preparation process of the green compact is as follows: Press the granulated material with a dry press to obtain a green compact. The dry pressing pressure is 150 Mpa, and the density of the obtained green compact is 3.2 g / cm 3 ; The preparation process of the sintering is as follows: Step 1: Debind the green compact. The debinding temperature is 420 °C, the atmosphere is air, and the debinding time is 80 min. Step 2: Sinter the debound green compact to obtain a resistor chip blank. The sintering temperature is 1050 °C, and the sintering time is 2 h. The preparation process of the post-treatment is as follows: Step 1: Grind, clean, and dry the resistor chip blank, where the drying temperature is 160 °C. Step 2: Spray aluminum on the dried resistor chip, coat the side with insulating paint, and wrap it with double-layer tape to obtain the finished zinc oxide resistor.

[0020] The test results are shown in Table 1: Table 1: Performance Test Preparation method Piezoelectric potential gradient V / mm Nonlinear coefficient Ratio of residual voltage of 5kA 8 / 20us lightning wave Example 1 280.32 26.34 1.71 Example 2 267.41 28.77 1.73 Example 3 293.29 34.36 1.68 Comparative example 1 224.56 22.43 2.31 Comparative example 2 243.37 25.92 1.86 Comparative example 3 212.13 24.68 1.91 Comparative example 4 245.43 22.63 1.82 Comparative example 5 196.17 16.35 2.25 Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit them. Although the present invention has been described in detail with reference to the preferred embodiments, those of ordinary skill in the art should understand that the technical solutions of the present invention can be modified or equivalently replaced without departing from the spirit and scope of the technical solutions, and they should all be covered within the scope of the claims of the present invention.

Claims

1. A zinc oxide resistor with high-gradient large current flow and impact stability, characterized in that, The raw materials include zinc monoxide, bismuth trioxide, antimony trioxide, nickel trioxide, manganese tetroxide, cobalt tetroxide, tin dioxide, boron trioxide, nano silver powder, aluminum nitrate nonahydrate, barium acetate, binder, dispersant, and deionized water.

2. The zinc oxide resistor with high-gradient large current flow and impact stability according to claim 1, characterized in that The zinc oxide resistor is measured by mass parts, with 80 - 100 parts of zinc monoxide, 2 - 4 parts of bismuth trioxide, 2 - 5 parts of antimony trioxide, 0.5 - 2 parts of nickel trioxide, 0.2 - 2 parts of manganese tetroxide, 0.5 - 3 parts of cobalt tetroxide, 0.1 - 0.4 parts of tin dioxide, 0.3 - 1 part of boron trioxide, 0.5 - 1.5 parts of nano silver powder, 0.01 - 0.05 parts of aluminum nitrate nonahydrate, 0.5 - 1.5 parts of barium acetate, 1 - 3 parts of binder, 0.5 - 1.5 parts of dispersant, and 320 - 450 parts of deionized water.

3. A zinc oxide resistor with high - gradient large - current impact stability according to claim 1, characterized in that: The zinc monoxide has a spherical powder with a particle size of 60 - 100 nm; The nano silver powder is a spherical powder with a particle size of 20 - 50 nm; The binder is at least one of polyvinyl alcohol and polyvinylpyrrolidone; The dispersant is polyacrylic acid.

4. A preparation method of a zinc oxide resistor with high-gradient large current-carrying impact stability as described in claim 1, characterized in that, It respectively includes the preparation steps of zinc monoxide - silver composite, cold - pressed powder, green compact, sintering, and post - treatment.

5. The preparation method according to claim 4, wherein The preparation method of the zinc monoxide - silver composite includes: The first step: Vacuum - mix zinc monoxide and nano silver powder to obtain a zinc monoxide - silver mixture. The mixing method is dry planetary ball - milling, with a rotation speed of 200 - 300 rpm, a time of 1 - 3 h, and a vacuum degree of 1 - 10 Pa; The second step: Vacuum - heat - treat the zinc monoxide - silver mixture. The heat - treatment temperature is 900 - 1000 °C, the heat - treatment time is 30 - 60 min, and the vacuum degree is 0.1 - 1 Pa; The third step: Disperse and screen the zinc monoxide - silver mixture after vacuum heat - treatment to obtain a zinc monoxide - silver composite. The dispersion method is jet - milling, and the particle size of the powder is 100 - 200 nm.

6. The preparation method according to claim 4, characterized in that The preparation method of the cold - pressed powder includes: The first step: Mix bismuth trioxide, antimony trioxide, nickel trioxide, manganese tetroxide, cobalt tetroxide, tin dioxide, boron trioxide, and 20 - 50 parts of deionized water to obtain a wet slurry one. The mixing method is wet planetary ball - milling, with a rotation speed of 100 - 300 rpm and a ball - milling time of 24 - 48 h; The second step: Screen, dry, and crush the wet slurry one to obtain a mixed powder one. The screen aperture for screening is 100 - 200 mesh, the drying temperature is 100 - 120 °C, and the crushing method is jet - milling; The third step: Dissolve the binder, dispersant, aluminum nitrate nonahydrate, and barium acetate in 300 - 400 parts of deionized water, and fully stir to obtain a glue solution. The stirring method is mechanical stirring, with a rotation speed of 200 - 400 rpm and a time of 30 - 60 min; The fourth step: Wet - ball - mill and screen the zinc monoxide - silver composite, mixed powder one, and glue solution to obtain a granulating slurry. The ball - milling time is 20 - 30 h, the rotation speed is 100 - 300 rpm, and the screen mesh number is 120 - 200 mesh; Step 5: Use a spray dryer to perform spray granulation on the granulated slurry to obtain granulated material, and the spray granulation temperature is 150 - 180 °C.

7. The preparation method according to claim 6, characterized in that, The moisture content of the granulated material is 1 - 2%.

8. The preparation method according to claim 4, characterized in that The method for preparing the green compact includes: The granulated material is subjected to tabletting treatment using a dry press to obtain a green compact. The dry pressing pressure is 100 - 200 Mpa, and the density of the obtained green compact is 3.2 - 3.3 g / cm 3 .

9. The preparation method according to claim 4, characterized in that, The method for preparing the sintering includes: Step 1: Debind the green compact, the debinding temperature is 400 - 430 °C, the atmosphere is air, and the debinding time is 60 - 90 min; Step 2: Sinter the debound green compact to obtain a resistor chip blank, the sintering temperature is 1000 - 1100 °C, and the sintering time is 1 - 3 h.

10. The preparation method according to claim 4, characterized in that, The method for preparing the post-treatment includes: Step 1: Grind, clean, dry, and heat-treat the resistor chip blank, where the drying temperature is 150 - 170 °C, the heat treatment temperature is 500 - 550 °C, and the heat treatment time is 13 - 17 h; Step 2: Spray aluminum, coat the side with insulating paint, and wrap with double-layer tape on the heat-treated resistor chip to obtain a finished zinc oxide resistor.

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