CN116779264A - Zinc oxide-based varistor and manufacturing method thereof - Google Patents
Zinc oxide-based varistor and manufacturing method thereof Download PDFInfo
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- CN116779264A CN116779264A CN202310861666.5A CN202310861666A CN116779264A CN 116779264 A CN116779264 A CN 116779264A CN 202310861666 A CN202310861666 A CN 202310861666A CN 116779264 A CN116779264 A CN 116779264A
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 314
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 153
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 88
- 238000000034 method Methods 0.000 claims abstract description 40
- 239000002245 particle Substances 0.000 claims abstract description 35
- 230000008569 process Effects 0.000 claims abstract description 29
- 238000005245 sintering Methods 0.000 claims abstract description 23
- 238000004381 surface treatment Methods 0.000 claims abstract description 19
- 238000010438 heat treatment Methods 0.000 claims description 19
- 238000002156 mixing Methods 0.000 claims description 18
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 13
- 239000006255 coating slurry Substances 0.000 claims description 13
- 239000011701 zinc Substances 0.000 claims description 12
- 238000000498 ball milling Methods 0.000 claims description 11
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000011230 binding agent Substances 0.000 claims description 9
- 239000002270 dispersing agent Substances 0.000 claims description 9
- 229910020599 Co 3 O 4 Inorganic materials 0.000 claims description 8
- 238000009766 low-temperature sintering Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 239000002002 slurry Substances 0.000 claims description 8
- 238000005507 spraying Methods 0.000 claims description 8
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 claims description 8
- 230000001680 brushing effect Effects 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 7
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 claims description 6
- 229910052691 Erbium Inorganic materials 0.000 claims description 6
- 229910052804 chromium Inorganic materials 0.000 claims description 6
- 239000008213 purified water Substances 0.000 claims description 6
- 239000007858 starting material Substances 0.000 claims description 6
- 229910052787 antimony Inorganic materials 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 239000002518 antifoaming agent Substances 0.000 claims description 3
- 239000011247 coating layer Substances 0.000 claims description 3
- 238000005498 polishing Methods 0.000 claims description 3
- -1 polytetrafluoroethylene Polymers 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 229920006215 polyvinyl ketone Polymers 0.000 claims description 3
- 238000003825 pressing Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims description 3
- 235000019982 sodium hexametaphosphate Nutrition 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 3
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 2
- 239000013530 defoamer Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 9
- 238000009413 insulation Methods 0.000 abstract description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 4
- 239000002086 nanomaterial Substances 0.000 abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052799 carbon Inorganic materials 0.000 abstract description 2
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 2
- 238000002474 experimental method Methods 0.000 description 20
- 238000012360 testing method Methods 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 18
- 239000000843 powder Substances 0.000 description 15
- 238000002360 preparation method Methods 0.000 description 12
- 239000011248 coating agent Substances 0.000 description 9
- 238000000576 coating method Methods 0.000 description 9
- 239000000919 ceramic Substances 0.000 description 6
- 239000010410 layer Substances 0.000 description 4
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 230000000630 rising effect Effects 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 2
- 238000005056 compaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000012720 thermal barrier coating Substances 0.000 description 2
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000007805 chemical reaction reactant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000000713 high-energy ball milling Methods 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000002096 quantum dot Substances 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01C—RESISTORS
- H01C7/00—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material
- H01C7/10—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material voltage responsive, i.e. varistors
- H01C7/105—Varistor cores
- H01C7/108—Metal oxide
- H01C7/112—ZnO type
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01C—RESISTORS
- H01C1/00—Details
- H01C1/02—Housing; Enclosing; Embedding; Filling the housing or enclosure
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01C—RESISTORS
- H01C17/00—Apparatus or processes specially adapted for manufacturing resistors
- H01C17/006—Apparatus or processes specially adapted for manufacturing resistors adapted for manufacturing resistor chips
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01C—RESISTORS
- H01C17/00—Apparatus or processes specially adapted for manufacturing resistors
- H01C17/30—Apparatus or processes specially adapted for manufacturing resistors adapted for baking
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01C—RESISTORS
- H01C7/00—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material
- H01C7/10—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material voltage responsive, i.e. varistors
- H01C7/12—Overvoltage protection resistors
Landscapes
- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Manufacturing & Machinery (AREA)
- Thermistors And Varistors (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
The application relates to a zinc oxide-based varistor and a manufacturing method thereof, which comprises a raw material mainly comprising zinc oxide, other oxides and auxiliary raw materials. The application adopts the proportion and the components among specific raw materials, adopts a double-layer structure comprising a core part of the zinc oxide-based varistor and a shell part of the zinc oxide-based varistor surrounding the core part, utilizes a good heat insulation outer layer to limit the growth of grains inside the resistor in the sintering process, and improves the sintering tightness degree of ZnO main materials. And simultaneously, the ZnO nano material with the surface treatment is combined, and the electrical characteristics of the ZnO series piezoresistor sheet are further improved by utilizing the covalent bond combination of ZnO particles and carbon and nitrogen of sites on the surface of atoms. Thus, the ZnO resistor disc formula, the raw material treatment and the selective combination sintering process improve the nonlinear characteristics of the resistor disc, and realize low residual voltage ratio and higher energy density.
Description
Technical Field
The present application relates to a power component and a method of manufacturing the same, and more particularly, to a zinc oxide-based varistor and a method of manufacturing the same.
Background
Currently, in an electric power system, overvoltage needs to be effectively limited to protect insulation of high-voltage equipment from being damaged, and a Metal Oxide Arrester (MOA) is a key device for limiting overvoltage in the electric power system, and the overvoltage protection level determines the insulation level of various devices of the electric power system to a large extent. The ZnO varistor valve plate is a core device in the lightning arrester, has excellent nonlinear characteristics and higher energy absorption capacity, and can effectively limit overvoltage.
Compared with the foreign high-performance valve plates, the ZnO varistor valve plates produced by domestic manufacturers have the problems of low voltage-sensitive voltage gradient, large voltage limiting ratio, small through-current capacity, mechanical aging and the like.
The zinc oxide-based resistor sheet has a plurality of domestic scientific researches and engineering workers develop experiments and production researches. For example, chinese patent publication CN 103021608A relates to a high-gradient high-capacity zinc oxide varistor and a preparation method thereof, wherein the varistor is composed of zinc oxide, bismuth trioxide, cobaltosic oxide, antimonous oxide and the like, and the preparation method thereof adopts the steps of ball milling, granulating, discharging glue, presintering coating, sintering, grinding, heat treatment, electrode spraying, glazing and the like. The patent technology records that the potential gradient of the prepared zinc oxide varistor greatly improves the 2ms square wave current capacity and keeps unchanged compared with the common varistor under the same specification; the preparation method not only reduces the working procedures, but also saves energy, and simultaneously avoids secondary pollution of auxiliary material additives. However, this type of technique does not refine the formulation and raw material selection of the ZnO series nonlinear resistor sheet, nor optimize, for example, the nonlinear resistance characteristics (high potential gradient) and the residual voltage ratio.
Disclosure of Invention
The present application ameliorates one or more of the above needs and disadvantages. In a first aspect of the present application, there is provided a zinc oxide based varistor sheet comprising the following raw material components in mole percent:
ZnO：80-85％，Sb 2 O 3 ：3-7％，Bi 2 O 3 ：3-5％，Co 2 O 3 ：0.5-2％，Co 3 O 4 ：0.5-1.0％，SiO 2 ：1.5-3％，MnO 2 ：1-3％，Cr 2 O 3 ：.0.5-1.5％，NiO：0.2-0.8％，B 2 O 3 ：0.5-1.0％，Al(NO 3 ) 3 ：0.1-0.5％，Er 2 O 3 :0.1-0.5%; and optionally further auxiliary components including one or more of a binder, a dispersant and a defoamer;
wherein the ZnO raw material of the zinc oxide based varistor has a particle size of about 50-100nm and,
the zinc oxide-based varistor sheet includes a core portion of the zinc oxide-based varistor sheet, and a shell portion of the zinc oxide-based varistor sheet surrounding the core portion of the zinc oxide-based varistor sheet.
Wherein preferably the mole percentage content of Zn component in the shell portion is lower than the mole percentage content of Zn component in the core portion.
Further, according to an alternative embodiment, the average particle diameter of the core portion of the zinc oxide-based varistor sheet is about 150nm to 200nm, and the average particle diameter of the shell portion of the zinc oxide-based varistor sheet is about 500nm to 5 μm.
According to an alternative technical scheme, the shell part of the zinc oxide-based piezoresistor sheet is made of ZnO and SiO 2 And Al 2 O 3 Composition is prepared.
According to an alternative embodiment, the ZnO component is present in the shell portion of the zinc oxide-based varistor sheet in an amount of 10% to 40% by mole based on the total content of the shell portion.
According to an alternative embodiment, the zinc oxide-based varistor has a shell portion made of ZnO, siO 2 And Al 2 O 3 The composition is according to the mol ratio of 1:1:1.
A second aspect of the present application provides a method of manufacturing the zinc oxide-based varistor as described above, the method comprising the steps of:
step 1): preparing raw materials of the zinc oxide-based varistor, wherein the raw materials comprise ZnO in mole percent: 80-85%, sb 2 O 3 ：3-7％，Bi 2 O 3 ：3-5％，Co 2 O 3 ：0.5-2％，Co 3 O 4 ：0.5-1.0％，SiO 2 ：1.5-3％，MnO 2 ：1-3％，Cr 2 O 3 ：.0.5-1.5％，NiO：0.2-0.8％，B 2 O 3 ：0.5-1.0％，Al(NO 3 ) 3 ：0.1-0.5％，Er 2 O 3 :0.1-0.5%; and an auxiliary component, and wherein the particle size of the ZnO starting material is between about 50-100 nm;
step 2): mixing the above raw materials except for the ZnO in a ball milling device for ball milling, calcining at a temperature below 600 ℃ for 0.5-2 hours, and then crushing in the ball milling device again;
step 3), carrying out a surface treatment process on the ZnO raw material;
step 4), adding ZnO subjected to the surface treatment process into mixing equipment, adding other raw material components crushed in a ball mill, adding auxiliary components accounting for not more than 5% of the total mass of the raw materials, and mixing in the mixing equipment;
step 5): pressing the mixture into a resistor disc blank, and performing preliminary low-temperature sintering on the blank, wherein in the preliminary low-temperature sintering, the temperature is increased to 200 ℃ from room temperature at a heating rate of 50-60 ℃/h; heating to 400 ℃ at a heating rate of 65-75 ℃/h, heating to 600 ℃ at a heating rate of 75-85 ℃/h, and preserving heat for 20 minutes at 600 ℃;
step 6): is prepared from nano ZnO as raw material and SiO as raw material 2 、Al 2 O 3 Ball milling the shell raw materials in a ball mill, and adding a binder accounting for 0.5-1.5% of the total mass of the shell raw materials, a dispersing agent accounting for 0.5-2% of the total mass of the shell raw materials and deionized water to mix to prepare a heat-insulating coating slurry;
step 7): spraying or brushing the heat-insulating coating slurry on the side surface, the top surface and the bottom surface of the resistance sheet blank subjected to the preliminary low-temperature sintering in the step 5) to form a shell structure and a core structure of the resistance sheet blank covered by the heat-insulating coating slurry;
step 8): carrying out secondary sintering on the resistance sheet blank sheet with the shell structure and the core structure, wherein the temperature is raised to 400 ℃ under the condition of the temperature raising rate of 70-90 ℃/h, the temperature is raised to the sintering temperature of 850 ℃ under the temperature raising rate of 40-50 ℃/h, the resistance sheet blank sheet is kept at the temperature of 850 ℃ for 3 hours, and then the resistance sheet blank sheet is raised to 950 ℃ under the slow temperature raising rate of 40-50 ℃/h and is kept for 1 hour; subsequently, the sintered sheet is cooled with a furnace to obtain a zinc oxide-based varistor sheet including a shell portion and a core portion.
According to an alternative technical scheme, the surface treatment process of the ZnO raw material in the step 3) is implemented according to the following method:
adding ammonium citrate and purified water into a sealed reaction tank of polytetrafluoroethylene according to the molar ratio of the ammonium citrate to the purified water of 1:20 for hydrothermal reaction, and controlling the reaction temperature to be 100-150 ℃ and the reaction time to be 2-5 hours; and (3) filtering by using a microporous filter after the hydrothermal reaction is finished, drying and grinding the filtered substance, and mixing the obtained product with the nano ZnO raw material in the step (1) to obtain the ZnO raw material subjected to the surface treatment process.
Preferably, according to an alternative technical solution, wherein in the step 6), the nano ZnO, siO 2 、Al 2 O 3 The molar ratio of the slurry is 1:1:1; and
the thickness of the heat-insulating coating layer formed in the step 7) is about 300 μm to 500 μm.
Preferably, wherein the step 4) further comprises the step of adding an auxiliary component accounting for not more than 5% of the total mass of the raw material components:
adding a binder polyvinyl ketone (PVP) accounting for 3% of the total mass of the raw material components, a dispersing agent sodium hexametaphosphate accounting for 0.5% of the total mass of the raw material components and a defoaming agent tributyl phosphate accounting for 0.2% of the total mass of the raw material components, and fully mixing the components; and
the step 8) further comprises polishing the shallow surface of the zinc oxide-based varistor and attaching electrodes to the upper and lower surfaces of the zinc oxide-based varistor.
The oxide-based varistor device obtained according to the raw material proportioning, the treatment process and the manufacturing steps adopts the proportioning and the components among specific raw materials, adopts a double-layer structure comprising a core part of the zinc oxide-based varistor and a shell part of the zinc oxide-based varistor surrounding the core part of the zinc oxide-based varistor, utilizes a good heat insulation outer layer (shell part) to limit the growth of internal grains of the resistor, and improves the sintering compactness of ZnO main materials. And simultaneously, the ZnO nano material with the surface treatment is combined, and the electrical characteristics of the ZnO series piezoresistor sheet are further improved by utilizing the covalent bond combination of ZnO particles and carbon and nitrogen of sites on the surface of atoms. Thus, the ZnO resistor disc formula, the raw material treatment and the selective combination sintering process improve the nonlinear characteristics of the resistor disc, and realize low residual voltage ratio and higher energy density.
Drawings
The accompanying drawings are included to provide a further understanding of the disclosed embodiments and are incorporated in and constitute a part of this specification, illustrate embodiments of the disclosure and together with the description serve to explain the principles of the disclosure.
Fig. 1 is a schematic diagram of an oxide-based varistor device prepared in accordance with the present application and SEM pictures of a central region (core portion), a transition region, and an edge region (shell portion).
Detailed Description
The present application is described in more detail below to facilitate an understanding of the application.
Before the description of the specific embodiments, it is to be noted that those skilled in the art, based on the teachings and teachings of the present disclosure, are able to select appropriate raw materials, and perform the relevant tests using the relevant test equipment and obtain the corresponding results, and that those skilled in the art, for raw materials not specifying a particular manufacturer or route, are able to select raw materials meeting the corresponding needs as reaction starting materials based on the disclosure and needs of the present specification. It is also understood in light of this disclosure that the starting materials for the reaction between the process portion compounds or components are derived from the primary product synthesized in the preamble of this application.
The main oxide raw material of the application is obtained from commercial procurement, wherein the main raw material zinc oxide is obtained from nano zinc oxide powder with the purity of more than 99.8wt% and the average particle size of 60-80nm provided by Jiangsu Xianfeng nano material technology Co., ltd, or zinc oxide fine powder with the particle size of 100-150 nm (used as a comparative experiment).
Other submicron oxide powders and other raw materials are also commercially available with purities of over 99.5 wt%. The person skilled in the art can also refine the raw material powder further to the desired particle size range (e.g. high energy ball milling etc.) using methods known in the art and can purify or remove impurities depending on the purity requirements of the raw material.
In the electron microscope test of the present application, an SEM scanning electron microscope JSM-IT200 of JEOL corporation of Japan was used for the test;
and adopting a western An Hongduo KG-5kA/500A zinc oxide resistor sheet impact current tester to carry out 8/20 mu s lightning impact current simulation test on the resistor sheet, and measuring the residual voltage value U5kA of the resistor sheet after passing through 5kA impact current, thereby calculating the residual voltage ratio.
U-I testing was performed on the resistor disc using a KEITHLEY 2410 digital source meter to obtain a potential gradient (E1 mA).
Example 1 (E1)
The present embodiment provides an oxide-based varistor device that is a zinc oxide-based varistor. The preparation method involves the following steps.
Step 1): preparing a raw material of the oxide-based varistor device. The raw materials used relate to the following components in mole percent:
ZnO：81％，Sb 2 O 3 ：5.5％，Bi 2 O 3 ：5％，Co 2 O 3 ：0.5％，Co 3 O 4 ：1.0％，SiO 2 ：3％，MnO 2 ：1％，Cr 2 O 3 ：0.5％，NiO：0.5％，B 2 O 3 ：1.0％，Al(NO 3 ) 3 ：0.5％，Er 2 O 3 :0.5%. The zinc oxide-based varistor may also contain additional auxiliary components.
In this example, the zinc oxide raw material was selected from zinc oxide fine powder having an average particle diameter of 60 to 80 nm. The zinc oxide fine powder is ready for use after a surface treatment process which will be described in detail below.
In this embodiment, the particle size of the above raw material components other than ZnO is selected to be 0.2 μm or less, for example, 0.1 to 0.2 μm, so as to match the particle size of the ZnO raw material with each other.
Step 2): the above raw materials except for the above ZnO were mixed and ball-milled in a ball mill of 100 rpm for 5 hours, calcined at 500 ℃ for 1 hour, and pulverized again in a ball mill.
Step 3): the ZnO starting material is subjected to a surface treatment process, which will be described in detail below.
Step 4): znO after the surface treatment process and other raw material components after being crushed in a ball mill are added into mixing equipment, and then binder polyvinyl ketone (PVP) accounting for 3 percent of the total mass of the raw material components, dispersing agent sodium hexametaphosphate accounting for 0.5 percent of the total mass of the raw material components and defoaming agent tributyl phosphate accounting for 0.2 percent of the total mass of the raw material components are added into the mixing equipment to carry out the full mixing of the components.
Step 5): and pressing the mixture into a resistor disc blank, and performing preliminary low-temperature sintering on the blank. In the preliminary low-temperature sintering step, the temperature is increased to 200 ℃ from room temperature at a heating rate of 50-60 ℃/h; heating to 400 ℃ at a heating rate of 65-75 ℃/h, heating to 600 ℃ at a heating rate of 75-85 ℃/h, and preserving heat for 20 minutes at 600 ℃.
The resistor blank sheet obtained by the above steps can be used as the core part of the final zinc oxide-based varistor sheet.
Step 6): next, a nano ZnO material and SiO material are prepared 2 、Al 2 O 3 And (3) forming slurry. Adding powder raw materials according to the molar ratio of 1:1:1, ball milling in a ball mill, adding binder accounting for 1% of the total mass of the mixed powder raw materials, dispersing agent accounting for 1% and excessive amountAnd mixing deionized water to prepare the heat-insulating coating slurry.
Step 7): and spraying or brushing the coating slurry on the side surface, the top surface and the bottom surface of the resistor disc blank sheet to form a resistor disc blank sheet shell and core structure covered by the thermal insulation coating slurry. The thermal barrier coating slurry was formed to a thickness of about 500 μm.
Step 8): and (3) performing secondary sintering on the resistor disc blank sheet with the shell and core structure. Heating to 400 ℃ at the temperature rising rate of 70-90 ℃/h, heating to the sintering temperature of 850 ℃ at the slow temperature rising rate of 40-50 ℃/h, maintaining at the temperature of 850 ℃ for 3 hours, heating to 950 ℃ at the slow temperature rising rate of 40-50 ℃/h, and maintaining for 1 hour. Subsequently, the sintered sheet is cooled with a furnace to obtain a zinc oxide-based varistor sheet including a shell portion and a core portion.
Polishing the shallow surface of the zinc oxide-based varistor. Then, optionally, electrode attachment (coating of an electrode layer) or glazing treatment is performed according to the subsequent use requirement.
And performing related electrical property tests on the obtained zinc oxide-based varistor product, and performing cross-section SEM scanning electron microscope tests on the varistor. This will be described in detail in the performance testing and analysis section below.
The inventors have found that the gradient performance, residual voltage ratio and energy density of an oxide-based varistor device can be further improved by subjecting untreated nano zinc oxide powder to particle surface modification.
Thus, the inventors performed the following surface treatment process for the raw material nano zinc oxide fine powder in example 1: ammonium citrate and purified water are selected, added into a sealed reaction tank of polytetrafluoroethylene according to the molar ratio of the ammonium citrate to the purified water of 1:20 for hydrothermal reaction, and the reaction temperature is controlled to be 120 ℃ and the reaction time is controlled to be 3 hours. And (3) filtering by using a microporous filter after the hydrothermal reaction is finished, drying and grinding the filtered substance, and mixing the obtained product with the nano ZnO raw material in the step (1) to obtain the ZnO raw material subjected to the surface treatment process.
More specifically, zinc oxide fine powder with the average particle diameter of 60-80nm is added into an excessive ethanol solvent, the product after the hydrothermal treatment is added according to the molar ratio of the zinc oxide fine powder to the ammonium citrate of 10:1, stirring is continued for 15 minutes, and the ZnO raw material after the surface treatment process is formed after filtration and drying.
Example 2 (E2)
The inventors performed example 2 of preparing a zinc oxide based varistor. In example 2, exactly the same experimental procedure as in example 1 was carried out, except that the raw materials used involved the following components in mole percent:
ZnO：85％，Sb 2 O 3 ：3％，Bi 2 O 3 ：3％，Co 2 O 3 ：2％，Co 3 O 4 ：0.5％，SiO 2 ：3％，MnO 2 ：1.5％，Cr 2 O 3 ：0.5％，NiO：0.5％，B 2 O 3 ：0.5％，Al(NO 3 ) 3 ：0.3％，Er 2 O 3 ：0.3％。
the zinc oxide based varistor of example 2 was also subjected to related electrical performance tests.
Comparative example 1 (C1)
In this experiment, the same preparation procedure as in example 1 was still employed, except that the starting materials used involved the following components in mole percent, see table 2:
table 2: comparative example 1 molar ratio of raw materials of Zinc oxide-based varistor
In table 2 of comparative example 1, the marked portion with the horizontal line in the raw material component was not subjected to the selection and proportioning of the raw materials according to the components of the examples of the present application.
Comparative example 2 (C2)
The present experiments relate to the preparation and comparison of the shell portion of zinc oxide based varistor sheets.
In the experiment of comparative example 2-1 (C2-1), the coating paste preparation of example 1 was not included, as compared to the experimental step of example 1, and it was sprayed or brushed onto the side, top and bottom surfaces of the resistor sheet blank to form an experimental step of thermally insulating coating paste-coated resistor sheet. That is, the zinc oxide-based varistor sheet does not include a shell structure for heat insulation.
In the experiment of comparative example 2-2 (C2-2), compared to the experimental procedure in example 1, the experimental procedure including the above-mentioned coating paste spraying or brushing on the side surfaces, top surfaces and bottom surfaces of the green sheet of the resistor sheet, the green sheet shell of the resistor sheet covered with the thermal insulation coating paste, the core structure, was formed. In contrast, sb in the raw materials is used 2 O 3 And Bi (Bi) 2 O 3 Adding the powder raw materials according to the mol ratio of 1:1, ball milling in a ball mill, adding the binder accounting for 1% of the total mass of the mixed powder raw materials, and mixing the dispersant accounting for 1% with excessive deionized water to prepare the coating slurry. Thereafter, the same spraying or brushing process as in example 1 was performed to form a resistance sheet covered with the coating paste.
In the experiment of comparative examples 2 to 3 (C2 to 3), the experimental procedure of the thermal barrier coating slurry-coated green sheet shell, core structure was also included by spraying or brushing the above-mentioned coating slurry on the side surfaces, top surfaces and bottom surfaces of the green sheet, as compared with the experimental procedure of example 1. In contrast, will contain ZnO, sb 2 O 3 And Bi (Bi) 2 O 3 The coating slurry is prepared according to the raw material mol ratio of 2:1:1. Thereafter, the same spraying or brushing process as in example 1 was performed to form a resistance sheet covered with the coating paste.
Comparative example 3 (C3)
The present experiments relate to the preparation and comparison of the shell portion of zinc oxide based varistor sheets.
In the experiment of comparative example 3-1 (C3-1), a similar preparation process to example 1 was carried out. Except that zinc oxide fine powder having an average particle diameter of 60 to 80nm was selected as the zinc oxide raw material, but the zinc oxide fine powder was not subjected to the surface treatment process of example 1, but was directly mixed with the above raw material other than ZnO and subjected to the rest of the process of example 1.
In the experiment of comparative example 3-2 (C3-2), a preparation process similar to that of example 1 was carried out. The difference is that the zinc oxide raw material is selected from zinc oxide fine powder with average particle diameter of 150-200 nm. The zinc oxide fine powder was not subjected to the surface treatment process of example 1, but was directly mixed with the above raw materials other than ZnO and subjected to the rest of the process of example 1.
In the experiment of comparative example 3-2 (C3-3), a preparation process similar to that of example 1 was carried out. The difference is that the zinc oxide raw material is selected from zinc oxide fine powder with average particle diameter of 150-200 nm. The rest of the processes, including the surface treatment process of the zinc oxide powder, were the same as those of example 1.
Test experiment
In the test of the present application, the potential gradient (E1 mA, V/mm), the residual voltage ratio (K) and the energy density (J/cm) of the zinc oxide-based varistor sheets obtained in each of the examples and comparative examples were tested 3 ). The test process accords with the test flow and the test standard of the alternating-current metal oxide arrester of the GB/T11032-2020 standard.
In the test process, firstly, the voltage (U1 mA) at two ends of the prepared zinc oxide-based varistor when passing through direct current of 1mA is measured, and the voltage (U5 kA) at two ends of the varistor when passing through lightning of 8/20s is measured, and the ratio of the voltage to the residual voltage is the residual voltage ratio (K), so that the nonlinear characteristic of the prepared varistor is reflected. In addition, the ratio of the voltage corresponding to the 1mA current to the thickness of the resistor sheet is used for obtaining the potential gradient (E1 mA, V/mm) of the resistor sheet, and the resistor sheet of the embodiment can realize the potential gradient of 600V/mm or even higher. Residual pressure ratio (K), potential gradient (E1 mA), and energy density (J/cm) 3 ) The test results of (2) are shown in Table 3.
Table 3: performance test of each example and comparative example
From the test data of examples and comparative examples, the samples of examples 1 and 2 of the present application obtained the highest potential gradient nonlinear characteristics, better energy density and lower residual voltage ratio.
In this regard, the inventors do not wish to be bound by any theory. However, according to the test and experimental results of the inventors, in combination with corresponding test means, some corresponding explanation and possible theoretical analysis can be obtained. The inventors conducted SEM scanning electron microscope tests on longitudinal sections (profiles) of various locations of the zinc oxide-based varistor sheet prepared in example 1, as shown in fig. 1. In fig. 1, a zinc oxide-based varistor sheet 1 includes a core portion (i.e., a portion from region a to region b), and a sheath portion 3 is sprayed or brushed onto the side, top and bottom surfaces of the varistor sheet blank to form a thermally insulating coating slurry-coated varistor sheet blank case. The sprayed or brushed material of the shell portion 3 (forming region a) of the present embodiment is composed of ZnO, and SiO 2 、Al 2 O 3 The slurry is composed, and the coating composed of Zn, al and Si oxides has good heat insulation performance, so that the growth of ceramic particles in the region a of the central region of the zinc oxide-based varistor is effectively inhibited. As can be seen from SEM pictures, in the central region a of the zinc oxide-based varistor sheet obtained after sintering, the average particle size of the sintered particles is about 150-200nm, and the growth of the ceramic particles in the central region is effectively limited by combining the short-time sintering process of the application. Here, the region 2 is shown as a region bordered and transited by the central region and the peripheral shell portions. Whereas SEM pictures of the corresponding longitudinal cross-section of the b region nearer the edge (shell portion) show that the ceramic particles grow significantly during the high temperature sintering step, to the order of hundreds of nanometers to microns. And to the edge c (region including the shell portion), particles including the shell portion grow rapidly under high temperature sintering, and the outermost periphery includes ZnO, and SiO 2 、Al 2 O 3 The particle size of the sintered particles of the slurry is more than 2 mu m. Thus, znO, and SiO in the design concept of the inventors 2 、Al 2 O 3 The slurry formed serves as a heat insulating protective layer, protects the ceramic particles of the core portion from growing up, compacts the particle density of the zinc oxide-based varistor of examples (1 and 2), and has better nonlinear characteristics to obtain the optimal energy density (J/cm) 3 ) And a potential gradient (E1 mA). In contrast, therefore, in the series of experiments of comparative example C2, the resistor sheet not including the shell structure did not realize the optimized potential gradient and energy density. It is worth mentioning that the inventors have surprisingly found that the use of Zn and Zn oxides plays a role in further optimizing the sintering effect and the resistance properties in the shell structure. However, when using other raw material components not containing Zn element as the coating layer of the shell portion (C2-2), the potential gradient and the energy density are deteriorated as compared with the examples, and the inventors speculate that ceramic grains at the boundary of the Zn-free shell portion and the core portion joining portion containing a large amount of Zn are not staggered with each other, so that the sintering density and the degree of compaction of the ceramic sheet as a whole are deteriorated, affecting further improvement of the nonlinear characteristics. Further, the insulating properties of the other components (such as Sb and Bi oxides) in the comparative example were good, but the insulating properties were not good, and thus the other types of oxides could not function as good insulating layers. On the other hand, when the content of Zn element in the shell portion is high (equal to or more than 50% by mole), or when the shell element is free of Si oxide element (e.g., C2-3), the heat insulating property of the shell portion cannot be optimally ensured, and thus the nonlinear resistance characteristics and the potential gradient cannot be optimally improved. Thus in an embodiment of the application, it is preferred that the mole percent content of the Zn component in the shell portion of the resistor sheet is 10% to 40% of the total component of the shell portion. More preferably, the shell portion of the zinc oxide based varistor is made of ZnO, siO 2 And Al 2 O 3 The raw materials of (2) are composed according to the mol ratio of 1:1:1.
In addition, the inventors have surprisingly found that non-linear modification of, for example, commercially available ZnO nanopowders or nanoparticles can further improve the energy density and potential gradient of the resistive sheetSex characteristics. When ammonium citrate is used for hydrothermal reaction, the quantum dots containing C material are formed, and the surface of the carbon quantum dots may have oxygen-containing coordination groups, such as carbonyl (-C=O-) and amino (-NH) 2 ) When the nano zinc oxide powder is further mixed with nano zinc oxide particles, the nano zinc oxide powder can be fully coordinated with metal cation dangling bonds on the surface of the nano zinc oxide before and after sintering, so that adsorbed oxygen molecules are reduced, easily polymerized hydroxyl groups combined on the surface of the nano zinc oxide are reduced, the sintering density of the ZnO material is improved, and the energy density and the nonlinear characteristics are improved.
Therefore, when the ZnO nanoparticles, which were not surface-treated, were subjected to the preparation experiment in comparison with comparative example C3 of the present application, the energy density could not be optimally exhibited. Notably, if the particle size of the starting ZnO raw material is larger (e.g., C3-3), the nonlinear characteristics are slightly deteriorated while achieving a better energy density, which may be related to excessive growth of the main component particles upon sintering, affecting optimization of the nonlinear characteristics of the ZnO resistor sheet.
Finally, in terms of raw material selection of the nonlinear resistor, the inventor finds that the selection and proportion of Si, multivalent Co and rare earth element types and ZnO as a main material have an influence on the electrical performance of the nonlinear resistor through experiments. Wherein when SiO 2 If the ratio is too high, the degree of sintering compaction is reduced, and nonlinear conduction between Zn components may be affected, so that, in a preferred embodiment, siO 2 The molar ratio of (2) is not more than 3%; in addition, co 2 O 3 With Co 3 O 4 Mixing in proper proportions is the preferred solution for optimizing the nonlinear resistor, when Co 3 O 4 If the ratio (C1-2) is too low, the optimization of the nonlinear characteristics is not favored. In a preferred embodiment of the present application, co in the feedstock 3 O 4 The molar ratio of (2) should be greater than or equal to 0.5%. This may be related to the self-sintered atomic architecture of the Co oxide. Finally, the inventors found Er 2 O 3 Is a better rare earth trace element, and the synergistic effect is better than Y reported in the related technology 2 O 3 This may be in combination with the more optimal electron transport properties of ErRelated to the following. When Al (NO) 3 ) 3 Nitrate can also act as a site for binding to the ZnO surface when used as one of the raw materials, so the sintering density and the degree of particle binding are better in the example using nitrate of Al.
Although the present disclosure includes specific embodiments, it will be obvious to those skilled in the art that various substitutions and modifications may be made in form and detail without departing from the spirit and scope of the present claims and their equivalents. The embodiments described herein should be considered in an illustrative sense only and not for the purpose of limitation. The description of features and aspects in each embodiment is considered to apply to similar features and aspects in other embodiments. Therefore, the scope of the present disclosure should not be limited by the specific description, but by the claims, and all changes within the scope of the claims and the equivalents thereof are to be construed as being included in the technical solutions of the present disclosure.
Claims (10)
1. The zinc oxide-based varistor is characterized by comprising the following raw material components in percentage by mole:
ZnO：80-85％，Sb 2 O 3 ：3-7％，Bi 2 O 3 ：3-5％，Co 2 O 3 ：0.5-2％，Co 3 O 4 ：0.5-1.0％，SiO 2 ：1.5-3％，MnO 2 ：1-3％，Cr 2 O 3 ：.0.5-1.5％，NiO：0.2-0.8％，B 2 O 3 ：0.5-1.0％，Al(NO 3 ) 3 ：0.1-0.5％，Er 2 O 3 :0.1-0.5%; and optionally further auxiliary components including one or more of a binder, a dispersant and a defoamer;
wherein the ZnO raw material of the zinc oxide based varistor has a particle size of about 50-100nm and,
the zinc oxide-based varistor sheet includes a core portion of the zinc oxide-based varistor sheet, and a shell portion of the zinc oxide-based varistor sheet surrounding the core portion of the zinc oxide-based varistor sheet.
2. The zinc oxide-based varistor of claim 1, wherein the mole percent content of Zn component in the shell portion is lower than the mole percent content of Zn component in the core portion.
3. The zinc oxide-based varistor as in claim 1, wherein the average particle size of the core portion of the zinc oxide-based varistor is about 150nm to 200nm and the average particle size of the shell portion of the zinc oxide-based varistor is about 500nm to 5 μm.
4. A zinc oxide-based varistor as claimed in claim 1 or 2, wherein the shell portion of the zinc oxide-based varistor is made of ZnO, siO 2 And Al 2 O 3 Composition is prepared.
5. A zinc oxide-based varistor as claimed in any one of claims 1 to 4, wherein the ZnO component is present in the shell portion of the zinc oxide-based varistor in a molar percentage of 10 to 40 percent of the total content of the shell portion.
6. The zinc oxide-based varistor as in any one of claims 1-5, wherein in a shell portion of the zinc oxide-based varistor, the shell portion is composed of ZnO, siO 2 And Al 2 O 3 The composition is according to the mol ratio of 1:1:1.
7. A method of manufacturing a zinc oxide based varistor as claimed in any one of claims 1 to 6, the method comprising the steps of:
step 1): preparing raw materials of the zinc oxide-based varistor, wherein the raw materials comprise ZnO in mole percent: 80-85%, sb 2 O 3 ：3-7％，Bi 2 O 3 ：3-5％，Co 2 O 3 ：0.5-2％，Co 3 O 4 ：0.5-1.0％，SiO 2 ：1.5-3％，MnO 2 ：1-3％，Cr 2 O 3 ：.0.5-1.5％，NiO：0.2-0.8％，B 2 O 3 ：0.5-1.0％，Al(NO 3 ) 3 ：0.1-0.5％，Er 2 O 3 :0.1-0.5%; and an auxiliary component, and wherein the particle size of the ZnO starting material is between about 50-100 nm;
step 2): mixing the above raw materials except for the ZnO in a ball milling device for ball milling, calcining at a temperature below 600 ℃ for 0.5-2 hours, and then crushing in the ball milling device again;
step 3), carrying out a surface treatment process on the ZnO raw material;
step 4), adding ZnO subjected to the surface treatment process into mixing equipment, adding other raw material components crushed in a ball mill, adding auxiliary components accounting for not more than 5% of the total mass of the raw materials, and mixing in the mixing equipment;
step 5): pressing the mixture into a resistor disc blank, and performing preliminary low-temperature sintering on the blank, wherein in the preliminary low-temperature sintering, the temperature is increased to 200 ℃ from room temperature at a heating rate of 50-60 ℃/h; heating to 400 ℃ at a heating rate of 65-75 ℃/h, heating to 600 ℃ at a heating rate of 75-85 ℃/h, and preserving heat for 20 minutes at 600 ℃;
step 6): is prepared from nano ZnO as raw material and SiO as raw material 2 、Al 2 O 3 Ball milling the shell raw materials in a ball mill, and adding a binder accounting for 0.5-1.5% of the total mass of the shell raw materials, a dispersing agent accounting for 0.5-2% of the total mass of the shell raw materials and deionized water to mix to prepare a heat-insulating coating slurry;
step 7): spraying or brushing the heat-insulating coating slurry on the side surface, the top surface and the bottom surface of the resistance sheet blank subjected to the preliminary low-temperature sintering in the step 5) to form a shell structure and a core structure of the resistance sheet blank covered by the heat-insulating coating slurry;
step 8): carrying out secondary sintering on the resistance sheet blank sheet with the shell structure and the core structure, wherein the temperature is raised to 400 ℃ under the condition of the temperature raising rate of 70-90 ℃/h, the temperature is raised to the sintering temperature of 850 ℃ under the temperature raising rate of 40-50 ℃/h, the resistance sheet blank sheet is kept at the temperature of 850 ℃ for 3 hours, and then the resistance sheet blank sheet is raised to 950 ℃ under the slow temperature raising rate of 40-50 ℃/h and is kept for 1 hour; subsequently, the sintered sheet is cooled with a furnace to obtain a zinc oxide-based varistor sheet including a shell portion and a core portion.
8. The method according to claim 7, wherein the surface treatment of the ZnO starting material in step 3) is performed according to the following method:
adding ammonium citrate and purified water into a sealed reaction tank of polytetrafluoroethylene according to the molar ratio of the ammonium citrate to the purified water of 1:20 for hydrothermal reaction, and controlling the reaction temperature to be 100-150 ℃ and the reaction time to be 2-5 hours; and after the hydrothermal reaction is finished, filtering by using a microporous filter, and drying and grinding the filtered substance to obtain the ZnO raw material subjected to the surface treatment process.
9. The method according to claim 7 or 8, wherein in the step 6), the nano ZnO, siO 2 、Al 2 O 3 The molar ratio of the slurry is 1:1:1; and
the thickness of the heat-insulating coating layer formed in the step 7) is about 300 μm to 500 μm.
10. The method according to any one of claims 7 to 9, wherein the further addition of an auxiliary component in the step 4) in an amount of not more than 5% by mass based on the total mass of the raw material components means that:
adding a binder polyvinyl ketone (PVP) accounting for 3% of the total mass of the raw material components, a dispersing agent sodium hexametaphosphate accounting for 0.5% of the total mass of the raw material components and a defoaming agent tributyl phosphate accounting for 0.2% of the total mass of the raw material components, and fully mixing the components; and
the step 8) further comprises polishing the shallow surface of the zinc oxide-based varistor and attaching electrodes to the upper and lower surfaces of the zinc oxide-based varistor.
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