CN102557610B - High-potential-gradient zinc oxide varistor, and making method and application thereof - Google Patents
High-potential-gradient zinc oxide varistor, and making method and application thereof Download PDFInfo
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- CN102557610B CN102557610B CN2011104517691A CN201110451769A CN102557610B CN 102557610 B CN102557610 B CN 102557610B CN 2011104517691 A CN2011104517691 A CN 2011104517691A CN 201110451769 A CN201110451769 A CN 201110451769A CN 102557610 B CN102557610 B CN 102557610B
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Abstract
The invention discloses a high-potential-gradient zinc oxide varistor, and a making method and application thereof. The high-potential-gradient zinc oxide varistor is prepared from the following raw materials in part by weight: 86.0 to 90.0 parts of ZnO, 4.0 to 5.0 parts of nano-Bi2O3, 3.5 to 4.0 parts of nano-Sb2O3, 1.5 to 1.8 parts of Co3O4, 0.5 to 1.0 part of NiO, 0.5 to 1.0 part of MnO2, 0.5 to 1.0 part of Cr2O3, 0.01 to 0.05 part of Al(NO3)3.9H2O, 1.0 to 2.0 parts of Y2O3, 0.5 to 1.0 part of SiO2 and 0.3 to 0.5 part of MgO. The uniformity and compactness of microstructure distribution of the made ZnO varistor are improved, so that the potential gradient and high-current discharge current capacity of the ZnO varistor are also improved; and the ZnO varistor can be widely applied to arresters in the fields of electric power systems, high-speed railways and the like, and the weight, volume and production cost of the arresters can be remarkably reduced.
Description
Technical field
The present invention relates to a kind of zinc oxide varistor and method for making thereof and application, high-potential gradient zinc oxide piezoresistive sheet and method for making and application especially for fields such as electric power system, high-speed railways, belong to the electronic functional material technical field.
Background technology
Zinc oxide arrester have protective feature good, absorb that the overvoltage energy is large, the dirty characteristic of resistant is good, advantages of simple structure and simple, be widely used in electric power system as surge absoption and overvoltage protection.At present, the electric potential gradient of the ZnO varistor sheet of traditional mode of production is only the 200V/mm left and right, along with the development of China's superhigh pressure, extra-high voltage electric transmission and transformation technology and high-speed railway, more and more higher requirement has been proposed for fail safe, reliability and the miniaturization of the ZnO varistor sheet as the lightning arrester core parts.Therefore, the ZnO varistor sheet of research and development high-potential gracient, miniaturization and large discharge capacity becomes the key issue that needs to be resolved hurrily both at home and abroad.
Summary of the invention
The object of the invention is to: a kind of high-potential gradient zinc oxide piezoresistive sheet and method for making and application are provided.The electric potential gradient of ZnO varistor sheet provided by the present invention and large electric current discharge capacity are all higher, can be used for the lightning arrester in the fields such as electric power system, high-speed railway, and can obviously reduce weight, volume and the production cost of lightning arrester.
Technical scheme of the present invention: a kind of high-potential gradient zinc oxide piezoresistive sheet, according to listed as parts by weight, it is made by following material powder: 86.0～90.0 parts of ZnO, nanometer Bi
2O
34.0～5.0 parts, nanometer Sb
2O
33.5～4.0 parts, Co
3O
41.5～1.8 parts, 0.5～1.0 part of NiO, MnO
20.5～1.0 parts, Cr
2O
30.5～1.0 parts, Al (NO
3)
39H
20.01～0.05 part of O, Y
2O
31.0～2.0 parts, SiO
20.5 0.3～0.5 part of～1.0 parts and MgO.
According to listed as parts by weight, aforementioned zinc oxide varistor is preferably made by following material powder: 500 parts of ZnO, nanometer Bi
2O
324.17 part, nanometer Sb
2O
321.87 part, Co
3O
48.63 part, 5.18 parts of NiO, MnO
22.88 part, Cr
2O
33.45 part, Al (NO
3)
39H
20.17 part of O, Y
2O
35.76 part, SiO
23.45 1.96 parts of part and MgO.
Co
3O
4With Co
2O
3Can reduce the leakage current of zinc oxide varistor, improve the stability of resistor disc, but through contrast test, find, adopt Co in technical solution of the present invention
3O
4Effect to obviously be better than Co
2O
3Therefore, select Co
3O
4.
The preparation method of aforementioned high-potential gradient zinc oxide piezoresistive sheet is: in formula and ratio, take various material powders, then add deionized water to make it abundant mixing in grinding in ball grinder, after drying is crossed 80 mesh sieves, adding concentration is that 5% polyvinyl alcohol water solution (PVA) is made binding agent, it is the green compact of 25mm that dry-pressing becomes Φ 34mm, thickness, after slowly being warming up to 400 ℃ of binder removals, be warming up to again 1100～1200 ℃, cool to room temperature with the furnace after heat preservation sintering 2h, in 650 ℃ of annealing, the burning infiltration silver electrode, obtain product.
Of the present invention is the traditional ceramics sintering process, why its sintering temperature selects 1100～1200 ℃, because the inventor finds in the experimental study process, if further reduce sintering temperature, the electric potential gradient of resistor disc can increase, but the through-current capability of 2ms square wave is reduced greatly, and leakage current increases, the overall performance of resistor disc descends, therefore the present invention finally selectes sintering temperature, is 1100～1200 ℃.Although in prior art, disclosed ZnO varistor sheet sintering temperature has a little less than this temperature, but the ZnO varistor sheet Tissue distribution that makes under sintering temperature of the present invention is even, more than electric potential gradient all reaches 400V/mm, and to 2ms square wave absorption energy, can reach 350J/cm
2.
In aforementioned preparation method, the milling time of material powder in ball mill is 20～24 hours.If the long production cost of Ball-milling Time increases, reduces benefit, but the too short material powder of Ball-milling Time can not mix fully, do not reach best result of use.The inventor is through experiment sieving, and finally definite 20～24 hours is suitable Ball-milling Time.
Can be used for surge absoption and overvoltage protection in electric power system, high-speed railway, electric equipment with the lightning arrester that above-described high-potential gradient zinc oxide piezoresistive sheet makes.Specifically, the zinc oxide varistor that makes is placed in the lightning arrester of electric power system, high-speed railway or electric equipment, electric current is very little when rated voltage is passed through the zinc oxide arrester valve block, is equivalent to insulator.When the voltage on zinc oxide arrester surpasses rated voltage, valve block will be in " conducting " state, and large electric current is leaked in the earth by valve block, and its residual voltage can not surpass the withstand voltage of protected equipment.Be used as when following to rated voltage with voltage drop, valve block, with automatic stop " conducting " state, returns to insulator state.Because zinc oxide varistor of the present invention, as the core parts of lightning arrester, has very excellent nonlinear characteristic, under the higher state of magnitude of voltage, its resistance is very little, and a large amount of lightning currents of can releasing, play the effect of conducting; Otherwise when the normal voltage value, the resistance of resistor disc is very large, is in state of insulation.
The electric potential gradient of the ZnO varistor sheet that the present invention makes is 400～600V/mm; Although in prior art there be higher than of the present invention the electric potential gradient of disclosed ZnO varistor sheet, the prepared ZnO varistor sheet of the present invention energy through-current capability is greatly improved than traditional Z nO piezoresistive wafer, and the 2ms square wave absorbs energy and reaches 350J/cm
2, can be used for actual production.
In addition, with zinc oxide arrester used on market, compare, the large electric current discharge capacity of ZnO varistor sheet of the present invention has improved approximately 30%; The length of the lightning arrester after encapsulation shortens to 0.9m by original 1.5m, the lightning arrester weight reducing nearly 45%, volume reduces approximately 40%; Thereby the production cost of lightning arrester also obviously reduces naturally.
Compared with prior art, the present invention Bi used
2O
3And Sb
2O
3Be nano material, nanometer Bi
2O
3With nanometer Sb
2O
3Can reduce sintering temperature in sintering process, make Tissue distribution even; Therefore, material powder material of the present invention is after sintering, and the uniformity of prepared ZnO varistor sheet Tissue distribution and density improve, thereby has improved simultaneously electric potential gradient and the large electric current discharge capacity of ZnO varistor sheet; This resistor disc can be widely used in the lightning arrester in the fields such as electric power system, high-speed railway, electric equipment, and can obviously reduce weight, volume and the production cost of lightning arrester.
Embodiment
Embodiments of the invention 1: the preparation of high-potential gradient zinc oxide piezoresistive sheet: take following material powder: ZnO500g, nanometer Bi
2O
324.17g, nanometer Sb
2O
321.87g, Co
3O
48.63g, NiO 5.18g, MnO
22.88g, Cr
2O
33.45g, Al (NO
3)
39H
2O 0.17g, Y
2O
35.76g, SiO
23.45g and MgO 1.96g, then add appropriate amount of deionized water to make it abundant mixing at grinding in ball grinder 22h, after drying was crossed 80 mesh sieves, adding appropriate concentration was that 5% polyvinyl alcohol water solution (PVA) is made binding agent, and it is the green compact of 25mm that dry-pressing becomes Φ 34mm, thickness, after slowly being warming up to 400 ℃ of binder removals, be warming up to again 1150 ℃, cool to room temperature with the furnace after heat preservation sintering 2h, in 650 ℃ of annealing, the burning infiltration silver electrode, obtain product.The electric potential gradient of gained ZnO varistor sheet is 600V/mm.
Embodiments of the invention 2: the preparation of high-potential gradient zinc oxide piezoresistive sheet: take following material powder: ZnO86g, nanometer Bi
2O
34g, nanometer Sb
2O
33.5g, Co
3O
41.5g, NiO 0.5g, MnO
20.5g, Cr
2O
30.5g, Al (NO
3)
39H
2O 0.01g, Y
2O
31.0g, SiO
20.5g and MgO 0.3g, then add appropriate amount of deionized water to make it abundant mixing at grinding in ball grinder 24h, after drying was crossed 80 mesh sieves, adding appropriate concentration was that 5% polyvinyl alcohol water solution (PVA) is made binding agent, and it is the green compact of 25mm that dry-pressing becomes Φ 34mm, thickness, after slowly being warming up to 400 ℃ of binder removals, be warming up to again 1100 ℃, cool to room temperature with the furnace after heat preservation sintering 2h, in 650 ℃ of annealing, the burning infiltration silver electrode, obtain product.The electric potential gradient of gained ZnO varistor sheet is 500V/mm.
Embodiments of the invention 3: the preparation of high-potential gradient zinc oxide piezoresistive sheet: take following material powder: ZnO90g, nanometer Bi
2O
35g, nanometer Sb
2O
34g, Co
3O
41.8g, NiO 1g, MnO
21g, Cr
2O
31g, Al (NO
3)
39H
2O 0.05g, Y
2O
32g, SiO
21g and MgO 0.5g, then add appropriate amount of deionized water to make it abundant mixing at grinding in ball grinder 20h, after drying was crossed 80 mesh sieves, adding appropriate concentration was that 5% polyvinyl alcohol water solution (PVA) is made binding agent, and it is the green compact of 25mm that dry-pressing becomes Φ 34mm, thickness, after slowly being warming up to 400 ℃ of binder removals, be warming up to again 1200 ℃, cool to room temperature with the furnace after heat preservation sintering 2h, in 650 ℃ of annealing, the burning infiltration silver electrode, obtain product.The electric potential gradient of gained ZnO varistor sheet is 400V/mm.
Embodiments of the invention 4: the preparation of high-potential gradient zinc oxide piezoresistive sheet: take following material powder: ZnO880g, nanometer Bi
2O
345g, nanometer Sb
2O
338g, Co
3O
417g, NiO 8g, MnO
27g, Cr
2O
38g, Al (NO
3)
39H
2O 0.3g, Y
2O
315g, SiO
28g and MgO 4g, then add appropriate amount of deionized water to make it abundant mixing at grinding in ball grinder 22h, after drying was crossed 80 mesh sieves, adding appropriate concentration was that 5% polyvinyl alcohol water solution (PVA) is made binding agent, and it is the green compact of 25mm that dry-pressing becomes Φ 34mm, thickness, after slowly being warming up to 400 ℃ of binder removals, be warming up to again 1180 ℃, cool to room temperature with the furnace after heat preservation sintering 2h, in 650 ℃ of annealing, the burning infiltration silver electrode, obtain product.The electric potential gradient of gained ZnO varistor sheet is 540V/mm.
Embodiments of the invention 5: the application of high-potential gradient zinc oxide piezoresistive sheet: the lightning arrester that the prepared zinc oxide varistor of embodiment 1-4 is placed in electric power system, high-speed railway or electric equipment, electric current is very little when rated voltage is passed through the zinc oxide arrester valve block, is equivalent to insulator.When the voltage on zinc oxide arrester surpasses rated voltage, valve block will be in " conducting " state, and large electric current is leaked in the earth by valve block, and its residual voltage can not surpass the withstand voltage of protected equipment.Be used as when following to rated voltage with voltage drop, valve block, with automatic stop " conducting " state, returns to insulator state.
Claims (5)
1. high-potential gradient zinc oxide piezoresistive sheet, it is characterized in that: according to listed as parts by weight, it is made by following material powder: 86.0～90.0 parts of ZnO, nanometer Bi
2O
34.0～5.0 parts, nanometer Sb
2O
33.5～4.0 parts, Co
3O
41.5～1.8 parts, 0.5～1.0 part of NiO, MnO
20.5～1.0 parts, Cr
2O
30.5～1.0 parts, Al (NO
3)
39H
20.01～0.05 part of O, Y
2O
31.0～2.0 parts, SiO
20.5 0.3～0.5 part of～1.0 parts and MgO; Preparation process is: in formula and ratio, take various material powders, then add deionized water grinding in ball grinder 20～24 hours, make it abundant mixing, after drying is crossed 80 mesh sieves, adding concentration is that 5% polyvinyl alcohol water solution is made binding agent, it is the green compact of 25mm that dry-pressing becomes Φ 34mm, thickness, after slowly being warming up to 400 ℃ of binder removals, then is warming up to 1100～1200 ℃, cool to room temperature with the furnace after heat preservation sintering 2h, in 650 ℃ of annealing, the burning infiltration silver electrode, obtain.
2. high-potential gradient zinc oxide piezoresistive sheet, it is characterized in that: it is made by following material powder: ZnO 500g, nanometer Bi
2O
324.17g, nanometer Sb
2O
321.87g, Co
3O
48.63g, NiO 5.18g, MnO
22.88g, Cr
2O
33.45g, Al (NO
3)
39H
2O 0.17g, Y
2O
35.76g, SiO
23.45g and MgO 1.96g; Preparation process is: take various material powders, then add deionized water grinding in ball grinder 22 hours, make it abundant mixing, after drying is crossed 80 mesh sieves, adding concentration is that 5% polyvinyl alcohol water solution is made binding agent, it is the green compact of 25mm that dry-pressing becomes Φ 34mm, thickness, after slowly being warming up to 400 ℃ of binder removals, then is warming up to 1150 ℃, cool to room temperature with the furnace after heat preservation sintering 2h, in 650 ℃ of annealing, the burning infiltration silver electrode, obtain.
3. the preparation method of high-potential gradient zinc oxide piezoresistive sheet as claimed in claim 1, it is characterized in that: in formula and ratio, take various material powders, then add deionized water grinding in ball grinder 20～24 hours, make it abundant mixing, after drying is crossed 80 mesh sieves, adding concentration is that 5% polyvinyl alcohol water solution is made binding agent, dry-pressing becomes Φ 34mm, thickness is the green compact of 25mm, after slowly being warming up to 400 ℃ of binder removals, be warming up to again 1100～1200 ℃, cool to room temperature with the furnace after heat preservation sintering 2h, in 650 ℃ of annealing, the burning infiltration silver electrode, obtain product.
4. the lightning arrester that makes with the described high-potential gradient zinc oxide piezoresistive sheet of claim 1 or 2.
5. lightning arrester as claimed in claim 4 is in the surge absoption of electric power system, high-speed railway, electric equipment and the application in overvoltage protection.
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| CN102557610B true CN102557610B (en) | 2013-11-13 |
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| CN103021608B (en) * | 2012-12-23 | 2015-11-18 | 南阳中祥电力电子有限公司 | A kind of high gradient Large Copacity zinc oxide varistor and preparation method thereof |
| CN103086710B (en) * | 2013-01-18 | 2014-08-27 | 西安恒翔电子新材料有限公司 | Wide-gradient range special porcelain powder for zinc oxide piezoresistor and preparation method thereof |
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| CN105118591A (en) * | 2015-09-17 | 2015-12-02 | 合肥海畅电气技术有限公司 | Resistance valve plate of lightning arrester |
| CN105957666A (en) * | 2016-06-30 | 2016-09-21 | 全球能源互联网研究院 | Varistor valve plate for lightning arrester and preparation method thereof |
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| CN109485405A (en) * | 2017-09-13 | 2019-03-19 | 东莞碧克电子有限公司 | High-performance varistor of durable type and preparation method thereof |
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| CN108358625A (en) * | 2018-02-05 | 2018-08-03 | 合肥市大卓电力有限责任公司 | A kind of resistor disc for manufacturing high pass current capacity varistor |
| CN113651610A (en) * | 2021-08-18 | 2021-11-16 | 西安神电(泾阳)电器有限公司 | Preparation method of high-performance ZnO varistor without chromium oxide and silicon oxide and ZnO varistor |
| CN115346743B (en) * | 2022-08-08 | 2023-12-01 | 安徽锦华氧化锌有限公司 | Preparation method of metal oxide arrester resistor disc |
| CN116143511A (en) * | 2022-12-30 | 2023-05-23 | 南阳金牛电气有限公司 | Preparation method of zinc oxide resistor disc with low voltage ratio and high current capacity |
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