CN113979740A - Pressure-sensitive ceramic additive, pressure-sensitive ceramic material, pressure-sensitive ceramic and preparation method thereof, pressure-sensitive resistor and preparation method thereof, and resistor element - Google Patents

Pressure-sensitive ceramic additive, pressure-sensitive ceramic material, pressure-sensitive ceramic and preparation method thereof, pressure-sensitive resistor and preparation method thereof, and resistor element Download PDF

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CN113979740A
CN113979740A CN202111183825.8A CN202111183825A CN113979740A CN 113979740 A CN113979740 A CN 113979740A CN 202111183825 A CN202111183825 A CN 202111183825A CN 113979740 A CN113979740 A CN 113979740A
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voltage
sensitive
sintering
additive
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CN113979740B (en
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郝留成
宋继光
陈蕊
徐仲勋
李凯
姜珊盼
赵新科
张琳
刘威
徐晨博
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State Grid Zhejiang Electric Power Co Ltd
Pinggao Group Co Ltd
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State Grid Zhejiang Electric Power Co Ltd
Pinggao Group Co Ltd
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Abstract

The invention relates to a voltage-sensitive ceramic additive, a voltage-sensitive ceramic material, a voltage-sensitive ceramic and a preparation method thereof, a voltage-sensitive resistor and a preparation method thereof, and a resistor element, and belongs to the technical field of voltage-sensitive resistor materials. The additive for ZnO voltage-sensitive ceramic is prepared by sintering the following raw materials: gd (Gd)2O3、Bi2O3And Sb2O3. The invention can optimize the microstructure and uniformity of the ZnO voltage-sensitive ceramic material by an additive sintering process. The grain distribution effect of the ZnO varistor plays a leading role in energy absorption capacity, and uneven grain distribution and high porosity can cause uneven leakage current and concentrated heat, thereby reducing the energy absorption capacity. The additive is sintered to reduce the surface energy of the raw materials, so that the particle size distribution is more uniform, the density is higher, and the energy absorption capacity of the ZnO varistor is improved, and the energy absorption capacity of the ZnO varistor prepared by the additive for ZnO varistor ceramic can reach 290J/cm3。

Description

Pressure-sensitive ceramic additive, pressure-sensitive ceramic material, pressure-sensitive ceramic and preparation method thereof, pressure-sensitive resistor and preparation method thereof, and resistor element
Technical Field
The invention relates to a voltage-sensitive ceramic additive, a voltage-sensitive ceramic material, a voltage-sensitive ceramic and a preparation method thereof, a voltage-sensitive resistor and a preparation method thereof, and a resistor element, and belongs to the technical field of voltage-sensitive resistor materials.
Background
The nonlinear ohmic characteristic of the zinc oxide piezoresistor valve plate is a crystal boundary effect, and the formation mechanism of the pressure-sensitive performance of the zinc oxide piezoresistor valve plate is closely related to a crystal boundary structure, such as the number of crystal boundaries, donor concentration, interface state density, Schottky barrier height and the like, of electricity to the piezoceramicParameters (non-linear coefficient alpha, voltage-dependent voltage gradient E)1mAAnd leakage current ILEtc.) to produce a direct effect. The grain boundary characteristics of the ZnO varistor depend on the formula components and the preparation process of the sample. The zinc oxide pressure-sensitive ceramic is prepared by using ZnO as main material and adding various oxides (Bi)2O3、Sb2O3、Co2O3、MnO2Etc.), the novel multifunctional semiconductor ceramic element is formed by sintering through the traditional ceramic process, and the change of the types of the additives and the optimization of process parameters become main means for regulating and controlling the microstructure and the grain boundary property of the ZnO voltage-sensitive ceramic and improving the electrical property of the ZnO voltage-sensitive ceramic.
The zinc oxide voltage-sensitive valve plate has the advantages of excellent nonlinear ohmic characteristic, large energy absorption capacity, short response time and the like, so that the zinc oxide voltage-sensitive valve plate is applied to a surge absorber for protecting a valve core of a lightning arrester of a power line from being influenced by voltage surge, wherein the voltage-sensitive voltage gradient and the energy absorption capacity are main characteristic parameters of the ZnO voltage-sensitive resistor valve plate. At present, the ZnO varistor valve plate has low voltage-dependent voltage gradient, and the miniaturization of the arrester product prepared by the ZnO varistor valve plate is limited.
Disclosure of Invention
The invention aims to provide an additive for ZnO voltage-sensitive ceramics, and the ZnO voltage-sensitive ceramics prepared by using the additive has high voltage gradient.
The second purpose of the invention is to provide a ZnO voltage-sensitive ceramic material.
The third purpose of the invention is to provide a ZnO voltage-sensitive ceramic.
The fourth purpose of the invention is to provide a preparation method of the ZnO voltage-sensitive ceramic.
A fifth object of the present invention is to provide a ZnO varistor.
The sixth purpose of the invention is to provide a preparation method of the ZnO varistor.
A seventh object of the present invention is to provide a varistor element.
In order to achieve the purpose, the technical scheme of the additive for the ZnO voltage sensitive ceramic is as follows:
an additive for ZnO pressure-sensitive ceramics is prepared by sintering the following raw materials: gd (Gd)2O3、Bi2O3And Sb2O3。
When the additive for ZnO voltage-sensitive ceramic is used for preparing ZnO voltage-sensitive ceramic, ZnO and Sb2O3Reaction to form Zn7Sb2O12Spinel phase, rare earth oxide Gd2O3And Bi2O3、Sb2O3Reaction to produce Bi6Gd2O12、Gd3Sb5O12The phase, these second phases gather at the grain boundary to play the role of "pinning", inhibiting the growth of ZnO main crystal grains. The voltage-dependent voltage gradient is primarily influenced by the grain size and breakdown voltage per grain boundary, and can be given by equation E1mA＝VgbAnd d is calculated. Wherein E is1mAIs the voltage-dependent voltage gradient, d is the number of grain boundaries, VgbIs the breakdown voltage of each grain boundary. Smaller ZnO grains and higher VgbResulting in a higher breakdown voltage. Taking into account V of the samplegbThe variation is relatively small, so that the grain size is adjusted and controlled1mAPlays a major role. The second phase generated in the sintering process reduces the average grain size of ZnO through the pinning effect, thereby obviously improving the voltage-sensitive potential gradient of the ZnO voltage-sensitive resistor. The voltage-sensitive voltage gradient of the ZnO voltage-sensitive resistor prepared by the invention can reach 480-600V/mm.
Preferably, the Gd is2O3、Bi2O3And Sb2O3The molar ratio of (A) to (B) is 0.25-1.00: 0.50-0.80: 0.80-1.20.
Preferably, the feedstock also includes Co2O3、MnO2、NiO、SiO2And Cr2O3。
Preferably, the Gd is2O3、Bi2O3、Sb2O3、Co2O3、MnO2、NiO、SiO2And Cr2O3The molar ratio of (A) to (B) is 0.25-1.00: 0.50-0.80: 0.80-1.20: 0.60-0.90:0.50～0.90:0.30～0.80:1.30～1.60:0.10～0.50。
Preferably, the sintering temperature is 700-900 ℃.
Preferably, the sintering time is 2-4 h.
Preferably, the heating rate of heating to the sintering temperature is 3 ℃/min to 5 ℃/min.
Preferably, the raw materials are mixed and ground prior to sintering.
Preferably, the milling is ball milling.
Preferably, the ball milling medium is absolute ethanol.
Preferably, the addition amount of the absolute ethyl alcohol is 1.0 mL-1.5 mL per g of the powder.
More preferably, the addition amount of the absolute ethyl alcohol is 1.2mL per g of the powder.
Preferably, the ball milling rate is 400r/min to 600 r/min.
More preferably, the ball milling rate is 400 r/min.
Preferably, the ball milling time is 5h to 12 h.
More preferably, the ball milling time is 5 h.
The technical scheme of the ZnO voltage-sensitive ceramic material comprises the following steps:
a ZnO varistor ceramic material comprises ZnO and the additive for ZnO varistor ceramic.
By adding the sintering additive, the ZnO voltage-sensitive ceramic material can increase the mixing uniformity of the additives on one hand and can effectively reduce the sintering activity of the additives on the other hand. The two functions can improve the microscopic uniformity of the ZnO voltage-sensitive ceramic material, thereby improving the energy absorption capacity of the ZnO voltage-sensitive resistor.
Preferably, the ZnO varistor ceramic material consists of ZnO and additives for ZnO varistor ceramics. Preferably, the additive for the ZnO voltage sensitive ceramic is prepared by sintering the following raw materials: gd (Gd)2O3、Bi2O3、Sb2O3、Co2O3、MnO2、NiO、SiO2And Cr2O3。
Preferably, the additive for the ZnO voltage sensitive ceramic is prepared by sintering the following raw materials in mole percentage based on the total mole number of the ZnO and the additive for the ZnO voltage sensitive ceramic as 100 parts:
Gd2O3 0.25～1.00，Sb2O3 0.80～1.20，Co2O3 0.60～0.90，MnO2 0.50～0.90，Bi2O30.50～0.80，NiO 0.30～0.80，SiO2 1.30～1.60，Cr2O3 0.10～0.50。
preferably, the ZnO voltage-sensitive ceramic material is obtained by a preparation method comprising the following steps: ZnO and the above-mentioned additive for ZnO pressure sensitive ceramics were mixed.
Preferably, the mixing comprises a ball milling process.
Preferably, the ball milling medium is absolute ethanol.
Preferably, the ball milling rate is 400 r/min.
Preferably, the ball milling time is 5 h.
Preferably, the preparation method further comprises the following steps: and mixing and sieving.
Preferably, the mesh number of the sieve is 100.
The technical scheme of the ZnO voltage-sensitive ceramic is as follows:
the ZnO varistor ceramic material is obtained by sintering treatment.
The ZnO voltage-sensitive ceramic material mainly comprises ZnO and Gd2O3，Sb2O3And Bi2O3As raw materials, ZnO and Sb in the sintering process2O3Reaction to form Zn7Sb2O12Spinel phase, rare earth oxide Gd2O3And Bi2O3、Sb2O3Reaction to produce Bi6Gd2O12、Gd3Sb5O12The phase, these second phases gather at the grain boundary to play the role of "pinning", inhibiting the growth of ZnO main crystal grains. Thus, by optimizingGd2O3And other additives can further improve the voltage-sensitive voltage gradient. The voltage-sensitive voltage gradient of the ZnO voltage-sensitive resistor prepared by the invention can reach 480-600V/mm. In addition, the invention can optimize the microstructure and uniformity of the ZnO voltage-sensitive ceramic material through an additive sintering process. The grain distribution effect of the ZnO varistor plays a leading role in energy absorption capacity, and uneven grain distribution and high porosity can cause uneven leakage current and concentrated heat, thereby reducing the energy absorption capacity. The additive is sintered to reduce the surface energy of the raw materials, so that the particle size distribution is more uniform, the density is higher, and the energy absorption capacity of the ZnO varistor is improved, and the energy absorption capacity of the ZnO varistor prepared by the additive for ZnO varistor ceramic can reach 290J/cm3。
The technical scheme of the preparation method of the ZnO voltage-sensitive ceramic comprises the following steps:
a preparation method of ZnO voltage-sensitive ceramic comprises the following steps: and sintering the ZnO voltage-sensitive ceramic material to obtain the ZnO voltage-sensitive ceramic material.
The preparation method of the ZnO voltage-sensitive ceramic is simple to operate, and the voltage-sensitive voltage gradient and the energy absorption capacity of the voltage-sensitive resistor can be improved by utilizing the ZnO voltage-sensitive ceramic prepared by the invention.
Preferably, the particle size of the ZnO voltage-sensitive ceramic material is not more than 0.15 mm.
Preferably, the sintering process comprises two stages, a first sintering and a second sintering.
Preferably, the temperature of the first sintering is 400-550 ℃.
More preferably, the temperature of the first sintering is 500 ℃.
Preferably, the time of the first sintering is 2-4 h.
More preferably, the time of the first sintering is 2 h.
Preferably, the heating rate of heating to the first sintering temperature is 1-3 ℃/min.
Preferably, the temperature of the second sintering is 1000-1200 ℃.
Preferably, the time of the second sintering is 2-4 h.
More preferably, the time of the second sintering is 2 h.
Preferably, the heating rate of the temperature rise from the first sintering temperature to the second sintering temperature is 3-5 ℃/min.
Preferably, the preparation method of the ZnO voltage-sensitive ceramic further comprises the following steps: and granulating and tabletting sequentially before sintering.
Preferably, the specific process of granulation is as follows: adding 6-10% of PVA (polyvinyl alcohol) by mass into the ZnO voltage-sensitive ceramic material, uniformly mixing, manually granulating, and then sieving to obtain powder of 60-100 meshes to obtain spherical powder with uniform size.
Preferably, the specific process of tabletting is as follows: and adding the granulated powder into a die, pressing by using a manual tablet press, slowly pressurizing to 8-15 Mpa, maintaining the pressure for 10min, and then demolding to obtain the green sheet.
The technical scheme of the ZnO varistor of the invention is as follows:
the ZnO varistor is prepared from the ZnO varistor ceramic.
The invention adds rare earth oxide Gd2O3The additive can inhibit the growth of crystal grains through a pinning effect, effectively improve the voltage-sensitive voltage gradient, optimize the microstructure and the uniformity of the ZnO voltage-sensitive ceramic through an additive sintering process, and further improve the energy absorption capacity of the ZnO voltage-sensitive ceramic, wherein the voltage-sensitive voltage gradient of the ZnO voltage-sensitive resistor can reach 480-600V/mm, and the energy absorption capacity can reach 290J/cm3And a certain application foundation is laid for the miniaturization of the valve core of the lightning arrester and the protected electronic component.
The technical scheme of the preparation method of the ZnO varistor comprises the following steps:
a preparation method of a ZnO piezoresistor comprises the following steps: and carrying out silver coating and silver firing treatment on the ZnO voltage-sensitive ceramic.
The ZnO varistor prepared by the invention has high-voltage sensitive voltage gradient and high energy absorption capacity, can effectively meet the requirements of low cost, high safety and reliability, small size and the like of a high-voltage arrester, and has great economic and social benefits.
Preferably, the temperature of the silver firing treatment is 600-820 ℃.
More preferably, the temperature of the silver firing treatment is 600 ℃.
Preferably, the time of the silver firing treatment is 1-3 h.
More preferably, the time of the silver firing treatment is 2 hours.
Preferably, the heating rate of heating to the silver burning treatment temperature is 2-4 ℃/min.
More preferably, the temperature increase rate of the temperature increase to the temperature of the silver firing treatment is 2 ℃/min.
The technical scheme of the piezoresistor element is as follows:
a varistor element produced from the above ZnO varistor or the above ZnO varistor.
When the ZnO voltage-sensitive ceramic or the ZnO voltage-sensitive resistor is used for preparing a voltage-sensitive resistor element, the requirements of a high-voltage arrester on low cost, high safety and reliability, small size and the like can be effectively met.
Drawings
FIG. 1 is an X-ray diffraction picture of the ZnO varistor prepared in example 17;
FIG. 2 is an electron microscope photograph of the ZnO varistor prepared in example 18;
FIG. 3 is an electron microscope photograph of the ZnO varistor prepared in example 19;
fig. 4 is an electron microscope picture of the ZnO varistor prepared in example 20.
Detailed Description
The technical solution of the present invention will be further explained with reference to the specific embodiments. It should be noted that the purpose of this embodiment is to further illustrate the present invention, and not to limit the protection scope of the present invention.
First, specific examples of the additive for ZnO pressure sensitive ceramics of the present invention are as follows:
example 1
The additive for ZnO voltage sensitive ceramic of the embodiment consists of Gd2O3、Sb2O3And Bi2O3Sintering to obtain the material; wherein, the molar ratio of each raw material in the additive is nGd2O3:nSb2O3:nBi2O30.75:1.10: 0.70; the sintering temperature is 700 ℃, the sintering time is 2h, and the heating rate of heating to the sintering temperature is 3 ℃/min. The preparation method of the additive for the ZnO voltage sensitive ceramic comprises the following steps: weighing Gd according to the formula amount2O3，Sb2O3And Bi2O3Mixing; and then putting the mixed raw materials into a planetary ball mill, adding 1.2mL of absolute ethyl alcohol into each g of raw materials, wet-milling the raw materials at the rotation speed of 400r/min for 5h by using the absolute ethyl alcohol as a medium, then putting the slurry into a drying box at the temperature of 80 ℃ for drying, putting the dried raw materials into a crucible and a muffle furnace, heating to 700 ℃ at the speed of 3 ℃/min, carrying out heat preservation sintering for 2h, and cooling to room temperature to obtain the additive for the ZnO voltage sensitive ceramic.
Example 2
The additive for ZnO voltage sensitive ceramic of the embodiment consists of Gd2O3、Sb2O3、Co2O3、MnO2、Bi2O3、NiO、SiO2And Cr2O3Sintering to obtain the material; wherein, the molar ratio of each raw material in the additive is nGd2O3:nSb2O3:nCo2O3:nMnO2:nBi2O3:nNiO:nSiO2:nCr2O30.75:1.10:0.80:0.70:0.70:0.50:1.50: 0.30; the sintering temperature is 700 ℃, the sintering time is 2h, and the heating rate of heating to the sintering temperature is 3 ℃/min. The preparation method of the additive for the ZnO voltage sensitive ceramic comprises the following steps: weighing Gd according to the formula amount2O3，Sb2O3，Co2O3，MnO2，Bi2O3，NiO，SiO2，Cr2O3Mixing; then thePutting the mixed raw materials into a planetary ball mill, adding 1.2mL of absolute ethyl alcohol into each g of raw materials, wet-milling the raw materials by taking the absolute ethyl alcohol as a medium at the rotating speed of 400r/min for 5h, then putting the slurry into a drying box at the temperature of 80 ℃ for drying, putting the dried raw materials into a crucible and a muffle furnace, heating to 700 ℃ at the speed of 3 ℃/min, carrying out heat preservation sintering for 2h, and cooling to room temperature to obtain the additive for the ZnO voltage sensitive ceramic.
Example 3
The additive for ZnO voltage sensitive ceramic of the embodiment consists of Gd2O3、Sb2O3、Co2O3、MnO2、Bi2O3、NiO、SiO2And Cr2O3Sintering to obtain the material; wherein, the molar ratio of each raw material in the additive is nGd2O3:nSb2O3:nCo2O3:nMnO2:nBi2O3:nNiO:nSiO2:nCr2O30.5:0.80:0.60:0.70:0.80:0.60:1.50: 0.40; the sintering temperature is 800 ℃, the sintering time is 4h, and the heating rate of heating to the sintering temperature is 3 ℃/min. The preparation method of the additive for the ZnO voltage sensitive ceramic comprises the following steps: weighing Gd according to the formula amount2O3，Sb2O3，Co2O3，MnO2，Bi2O3，NiO，SiO2，Cr2O3Mixing; and then putting the mixed raw materials into a planetary ball mill, adding 1.2mL of absolute ethyl alcohol into each g of raw materials, wet-milling the raw materials at the rotating speed of 400r/min for 5h by using the absolute ethyl alcohol as a medium, then putting the slurry into a drying box at the temperature of 80 ℃ for drying, putting the dried raw materials into a crucible and a muffle furnace, heating to 800 ℃ at the speed of 3 ℃/min, carrying out heat preservation sintering for 4h, and cooling to room temperature to obtain the additive for the ZnO voltage sensitive ceramic.
Example 4
The additive for ZnO voltage sensitive ceramic of the embodiment consists of Gd2O3、Sb2O3、Co2O3、MnO2、Bi2O3、NiO、SiO2And Cr2O3Mixing and sintering to obtain the material; wherein, the molar ratio of each raw material in the additive is nGd2O3:nSb2O3:nCo2O3:nMnO2:nBi2O3:nNiO:nSiO2:nCr2O30.25:0.90:0.70:0.90:0.60:0.80:1.30: 0.50; the sintering temperature is 900 ℃, the sintering time is 2h, and the heating rate of heating to the sintering temperature is 5 ℃/min; the preparation method of the additive for the ZnO voltage sensitive ceramic comprises the following steps: weighing Gd according to the formula amount2O3，Sb2O3，Co2O3，MnO2，Bi2O3，NiO，SiO2，Cr2O3Mixing; and then putting the mixed raw materials into a planetary ball mill, adding 1.2mL of absolute ethyl alcohol into each g of raw materials, wet-milling the raw materials at the rotating speed of 400r/min for 5h by using the absolute ethyl alcohol as a medium, then putting the slurry into a drying box at the temperature of 80 ℃ for drying, putting the dried raw materials into a crucible and a muffle furnace, heating to 900 ℃ at the speed of 5 ℃/min, carrying out heat preservation sintering for 2h, and cooling to room temperature to obtain the additive for the ZnO voltage sensitive ceramic.
Example 5
The additive for ZnO voltage sensitive ceramic of the embodiment consists of Gd2O3、Sb2O3、Co2O3、MnO2、Bi2O3、NiO、SiO2And Cr2O3Mixing and sintering to obtain the material; wherein, the molar ratio of each raw material in the additive is nGd2O3:nSb2O3:nCo2O3:nMnO2:nBi2O3:nNiO:nSiO2:nCr2O31.0:1.20:0.90:0.50:0.50:0.60:1.60: 0.10; the sintering temperature is 800 ℃, the sintering time is 3h, and the temperature rise rate of the temperature rise to the sintering temperature is 4 ℃min; the preparation method of the additive for the ZnO voltage sensitive ceramic comprises the following steps: weighing Gd according to the formula amount2O3，Sb2O3，Co2O3，MnO2，Bi2O3，NiO，SiO2，Cr2O3Mixing; and then putting the mixed raw materials into a planetary ball mill, adding 1.2mL of absolute ethyl alcohol into each g of raw materials, wet-milling the raw materials at the rotation speed of 400r/min for 5h by using the absolute ethyl alcohol as a medium, then putting the slurry into a drying box at the temperature of 80 ℃ for drying, putting the dried raw materials into a crucible and a muffle furnace, heating to 800 ℃ at the speed of 4 ℃/min, carrying out heat preservation sintering for 3h, and cooling to room temperature to obtain the additive for the ZnO voltage sensitive ceramic.
Secondly, the specific embodiment of the ZnO voltage-sensitive ceramic material of the invention is as follows:
example 6
The ZnO varistor ceramic material of this example consisted of the additive for ZnO varistor ceramic of example 1 and the main material ZnO, wherein the ratio of the total moles of the additive for ZnO varistor ceramic to the moles of the main material ZnO was 2.55: 97.45. The ZnO varistor ceramic material of the embodiment is obtained by a preparation method comprising the following steps: weighing the additive for the ZnO voltage sensitive ceramic and ZnO powder according to the formula ratio, mixing, then putting the mixed powder into a planetary ball mill, carrying out wet milling by taking absolute ethyl alcohol as a medium, wherein the rotating speed is 400r/min, the ball milling time is 5h, then putting the slurry into a drying oven at 80 ℃ for drying, and sieving by a 100-mesh sieve to obtain the ZnO voltage sensitive ceramic material.
Example 7
The ZnO varistor ceramic material of this example consisted of the additive for ZnO varistor ceramic of example 2 and the main material ZnO, wherein the ratio of the total moles of the additive for ZnO varistor ceramic to the moles of the main material ZnO was 6.35: 93.65. The ZnO varistor ceramic material of the embodiment is obtained by a preparation method comprising the following steps: weighing the additive for the ZnO voltage sensitive ceramic and ZnO powder according to the formula ratio, mixing, then putting the mixed powder into a planetary ball mill, carrying out wet milling by taking absolute ethyl alcohol as a medium, wherein the rotating speed is 400r/min, the ball milling time is 5h, then putting the slurry into a drying oven at 80 ℃ for drying, and sieving by a 100-mesh sieve to obtain the ZnO voltage sensitive ceramic material.
Example 8
The ZnO varistor ceramic material of the present example consists of the additive for ZnO varistor ceramic of example 3 and ZnO as the main material, wherein the ratio of the total moles of the additive for ZnO varistor ceramic to the moles of ZnO as the main material is 5.9: 94.1; the ZnO varistor ceramic material of the embodiment is obtained by a preparation method comprising the following steps: weighing an additive for ZnO voltage-sensitive ceramic and ZnO powder according to the formula ratio, mixing, then putting the mixed powder into a planetary ball mill, and carrying out wet milling by taking absolute ethyl alcohol as a medium, wherein the rotating speed is 400r/min, and the ball milling time is 5 h; and then placing the slurry in a drying oven at 80 ℃ for drying, and sieving by a 100-mesh sieve to obtain the ZnO voltage-sensitive ceramic material.
Example 9
The ZnO varistor ceramic material of the present example consists of the additive for ZnO varistor ceramic of example 4 and ZnO as the main material, wherein the ratio of the total moles of the additive for ZnO varistor ceramic to the moles of ZnO as the main material is 5.95: 94.05; the ZnO varistor ceramic material of the embodiment is obtained by a preparation method comprising the following steps: weighing an additive for ZnO voltage-sensitive ceramic and ZnO powder according to the formula ratio, mixing, then putting the mixed powder into a planetary ball mill, and carrying out wet milling by taking absolute ethyl alcohol as a medium, wherein the rotating speed is 400r/min, and the ball milling time is 5 h; and then placing the slurry in a drying oven at 80 ℃ for drying, and sieving by a 100-mesh sieve to obtain the ZnO voltage-sensitive ceramic material.
Example 10
The ZnO varistor ceramic material of the present example consists of the additive for ZnO varistor ceramic of example 5 and ZnO as the main material, wherein the ratio of the total moles of the additive for ZnO varistor ceramic to the moles of ZnO as the main material is 6.4: 93.6; the ZnO varistor ceramic material of the embodiment is obtained by a preparation method comprising the following steps: weighing an additive for ZnO voltage-sensitive ceramic and ZnO powder according to the formula ratio, mixing, then putting the mixed powder into a planetary ball mill, and carrying out wet milling by taking absolute ethyl alcohol as a medium, wherein the rotating speed is 400r/min, and the ball milling time is 5 h; and then placing the slurry in a drying oven at 80 ℃ for drying, and sieving by a 100-mesh sieve to obtain the ZnO voltage-sensitive ceramic material.
Thirdly, the specific embodiment of the ZnO voltage sensitive ceramic of the invention is as follows:
the ZnO varistor of this example was obtained by sintering the varistor ceramic material of example 6, example 7, example 8, example 9 or example 10.
Fourthly, the specific embodiment of the preparation method of the ZnO voltage-sensitive ceramic of the invention is as follows:
example 11
The preparation method of the ZnO voltage-sensitive ceramic comprises the following steps:
according to the preparation process of electronic ceramics, 89.074g of the ZnO voltage-sensitive ceramic material of embodiment 6 is added with 13.361g of PVA with the mass fraction of 8%, after being mixed uniformly, the mixture is granulated manually, then sieved, powder of 60-100 meshes is taken to obtain spherical powder with uniform size, then the spherical powder is added into a die, a manual tablet press is adopted for pressing, the pressure is slowly increased to 9Mpa, and the pressure is maintained for 10min, so that green sheets are prepared; and placing the green sheets in a sagger, placing the sagger with the green sheets in a muffle furnace for high-temperature calcination, firstly heating to 500 ℃ at the speed of 1 ℃/min, preserving the heat for 2h, then heating to 1000 ℃ at the speed of 3 ℃/min, preserving the heat for 2h, and then cooling to room temperature along with the furnace to obtain the ZnO pressure-sensitive ceramic.
Example 12
The preparation method of the ZnO voltage-sensitive ceramic comprises the following steps:
according to the preparation process of electronic ceramics, 89.074g of the ZnO voltage-sensitive ceramic material of embodiment 7 is added with 13.361g of PVA with the mass fraction of 8%, after being mixed uniformly, the mixture is granulated manually, then sieved, powder of 60-100 meshes is taken to obtain spherical powder with uniform size, then the spherical powder is added into a die, a manual tablet press is adopted for pressing, the pressure is slowly increased to 9Mpa, and the pressure is maintained for 10min, so that green sheets are prepared; and placing the green sheets in a sagger, placing the sagger with the green sheets in a muffle furnace for high-temperature calcination, firstly heating to 500 ℃ at the speed of 1 ℃/min, preserving the heat for 2h, then heating to 1000 ℃ at the speed of 3 ℃/min, preserving the heat for 2h, and then cooling to room temperature along with the furnace to obtain the ZnO pressure-sensitive ceramic.
Example 13
The preparation method of the ZnO voltage-sensitive ceramic comprises the following steps:
according to the preparation process of electronic ceramics, 88.372g of the ZnO voltage-sensitive ceramic material of embodiment 8 is added with 13.256g of PVA with the mass fraction of 8%, after being uniformly mixed, the mixture is granulated manually, then sieved, powder of 60-100 meshes is taken to obtain spherical powder with uniform size, then the spherical powder is added into a die, a manual tablet press is adopted for pressing, the pressure is slowly increased to 9MPa, and the pressure is maintained for 10min, so that green sheets are prepared; and placing the green sheets in a sagger, placing the sagger with the green sheets in a muffle furnace for high-temperature calcination, firstly heating to 500 ℃ at the speed of 3 ℃/min, preserving the heat for 3h, then heating to 1100 ℃ at the speed of 3 ℃/min, preserving the heat for 2h, and then cooling to room temperature along with the furnace to obtain the ZnO voltage-sensitive ceramic.
Example 14
The preparation method of the ZnO voltage-sensitive ceramic comprises the following steps:
according to the preparation process of electronic ceramics, 87.670g of the ZnO voltage-sensitive ceramic material of embodiment 9 is added with 13.150g of PVA with the mass fraction of 8%, after being mixed uniformly, the mixture is granulated manually, then sieved, powder of 60-100 meshes is taken to obtain spherical powder with uniform size, then the spherical powder is added into a die, a manual tablet press is adopted for pressing, the pressure is slowly increased to 9MPa, and the pressure is maintained for 10min, so that green sheets are prepared; and placing the green sheet into a sagger, placing the sagger with the green sheet into a muffle furnace for high-temperature calcination, firstly heating to 400 ℃ at the speed of 2 ℃/min, preserving the heat for 4h, then heating to 1200 ℃ at the speed of 5 ℃/min, preserving the heat for 2h, and then cooling to room temperature along with the furnace to obtain the ZnO voltage-sensitive ceramic.
Example 15
The preparation method of the ZnO voltage-sensitive ceramic comprises the following steps:
according to the preparation process of electronic ceramic, 89.778g of ZnO pressure-sensitive ceramic powder of embodiment 10 is added with 13.467g of PVA with the mass fraction of 8%, after being uniformly mixed, the mixture is manually granulated and then sieved, powder of 60-100 meshes is taken to obtain spherical powder with uniform size, then the spherical powder is added into a die, a manual tablet press is adopted for pressing, the pressure is slowly increased to 9Mpa, and the pressure is maintained for 10min, so that green sheets are prepared; and placing the green sheets in a sagger, placing the sagger with the green sheets in a muffle furnace for high-temperature calcination, firstly heating to 550 ℃ at the speed of 2 ℃/min, preserving the heat for 2h, then heating to 1100 ℃ at the speed of 4 ℃/min, preserving the heat for 2h, and then cooling to room temperature along with the furnace to obtain the ZnO voltage-sensitive ceramic.
Fifthly, the specific embodiment of the ZnO varistor of the invention is as follows:
the ZnO varistor of this example was prepared from the ZnO varistor ceramic prepared in example 11, example 12, example 13, example 14 or example 15.
Sixthly, the specific embodiment of the preparation method of the ZnO varistor of the invention is as follows:
example 16
The preparation method of the ZnO varistor of the embodiment comprises the following steps:
the ZnO varistor ceramic prepared in the example 11 was coated with silver on both sides, placed in a sagger, put in a muffle furnace to heat up to 600 ℃ at a rate of 2 ℃/min, and cooled to room temperature after heat preservation for 2 hours, to obtain a ZnO varistor.
Example 17
The preparation method of the ZnO varistor of the embodiment comprises the following steps:
the ZnO varistor ceramic prepared in example 12 was coated with silver on both sides, placed in a sagger, placed in a muffle furnace to heat to 600 ℃ at a rate of 2 ℃/min, and cooled to room temperature after 2 hours of heat preservation to obtain a ZnO varistor.
The ZnO varistor prepared in this example was subjected to X-ray diffraction analysis, and the result is shown in FIG. 1. As can be seen from FIG. 1, the varistor prepared was ZnO in the main crystal phase and contained a small amount of spinel Zn7Sb2O12、Bi6Gd2O12And Gd3Sb5O12And waiting for the second phase.
The ZnO piezoresistor prepared in the embodiment is used for testing the voltage-sensitive voltage gradient and the leakage current according to the testing method specified in GB/T16528-The flow and energy absorption capacity is tested according to the test method specified in GB/T10193-1997 for nonlinear coefficient, and the characteristic parameters of the ZnO varistor prepared in the embodiment are as follows: the voltage-dependent voltage gradient is 486V/mm, the nonlinear coefficient alpha is 52, and the leakage current IL1.47 muA, and an energy absorption capacity of 290J/cm3。
Example 18
The preparation method of the ZnO varistor of the embodiment comprises the following steps:
the ZnO varistor ceramic prepared in example 13 was covered with silver on both sides, placed in a sagger, and placed in a muffle furnace to heat up to 600 ℃ at a rate of 2 ℃/min, and after heat preservation for 2h, cooled to room temperature, to obtain a ZnO varistor.
The ZnO piezoresistor prepared in this example was analyzed by an electron microscope, and the result is shown in fig. 2, and it can be seen from fig. 2 that the ZnO piezoresistor prepared has good micro-uniformity, and the microstructure thereof is composed of a main crystal phase ZnO and Bi located at the grain boundary2O3And a second phase composition at the grain boundary/triple grain boundary.
The ZnO varistor prepared in the embodiment is used for testing the voltage-dependent voltage gradient, the leakage current and the energy absorption capacity according to the testing method specified in GB/T16528-: the voltage-sensitive voltage gradient is 543V/mm, the nonlinear coefficient alpha is 58, and the leakage current IL1.23 muA, and an energy absorption capacity of 257J/cm3。
Example 19
The preparation method of the ZnO varistor of the embodiment comprises the following steps:
the ZnO varistor ceramic prepared in example 14 was coated with silver on both sides, placed in a sagger, and placed in a muffle furnace to heat up to 600 ℃ at a rate of 2 ℃/min, and after heat preservation for 2 hours, cooled to room temperature, to obtain a ZnO varistor.
The result of analyzing the ZnO varistor prepared in this example by using an electron microscope is shown in fig. 3, and it can be seen from fig. 3 that the ZnO varistor prepared in this example has good micro-uniformity, and the microstructure thereof is composed of a main crystal phase ZnO and is located at the grain boundaryOf Bi2O3And a second phase composition at the grain boundary/triple grain boundary.
The ZnO varistor prepared in the embodiment is used for testing the voltage-dependent voltage gradient, the leakage current and the energy absorption capacity according to the testing method specified in GB/T16528-: the voltage-dependent voltage gradient is 578V/mm, the nonlinear coefficient alpha is 56, and the leakage current IL1.32 muA, and 243J/cm of energy absorption capacity3。
Example 20
The preparation method of the ZnO varistor of the embodiment comprises the following steps:
the ZnO varistor ceramic prepared in example 15 was covered with silver on both sides, placed in a sagger, and placed in a muffle furnace to heat up to 600 ℃ at a rate of 2 ℃/min, and after heat preservation for 2h, cooled to room temperature, to obtain a ZnO varistor.
The ZnO piezoresistor prepared in this example was analyzed by an electron microscope, and the result is shown in fig. 4, and it can be seen from fig. 4 that the ZnO piezoresistor prepared has good micro-uniformity, and the microstructure thereof is composed of a main crystal phase ZnO and Bi located at the grain boundary2O3And a second phase composition at the grain boundary/triple grain boundary.
The ZnO varistor prepared in the embodiment is used for testing the voltage-dependent voltage gradient, the leakage current and the energy absorption capacity according to the testing method specified in GB/T16528-: voltage-dependent voltage gradient 592V/mm, non-linear coefficient alpha 61, leakage current IL1.08 muA, and 243J/cm of energy absorption capacity3。
In other examples, the ZnO varistor ceramic prepared in examples 9 to 12 was coated with silver on both sides, placed in a sagger, and placed in a muffle furnace, heated to 600 ℃, 820 ℃ at rates of 2 ℃/min, 3 ℃/min, and 4 ℃/min, respectively, and cooled to room temperature after heat preservation for 1 hour, 2 hours, and 3 hours, and the characteristic parameters of the obtained ZnO varistor were equivalent to those obtained in examples 13 to 16.
Seventhly, the specific embodiment of the varistor element of the invention is as follows:
the varistor element of this example was prepared from the ZnO varistor of example 11, example 12, example 13, example 14 or example 15 or from the ZnO varistor of example 16, example 17, example 18, example 19 or example 20.

Claims (18)

1. An additive for ZnO pressure-sensitive ceramics is characterized by being prepared by sintering the following raw materials: gd (Gd)2O3、Bi2O3And Sb2O3。
2. The additive for ZnO varistor ceramic according to claim 1, wherein Gd is present2O3、Bi2O3And Sb2O3The molar ratio of (A) to (B) is 0.25-1.00: 0.50-0.80: 0.80-1.20.
3. The additive for ZnO pressure sensitive ceramics of claim 1, wherein the raw material further comprises Co2O3、MnO2、NiO、SiO2And Cr2O3。
4. The additive for ZnO varistor ceramic according to claim 3, wherein Gd is present2O3、Bi2O3、Sb2O3、Co2O3、MnO2、NiO、SiO2And Cr2O3The molar ratio of (A) to (B) is 0.25-1.00: 0.50-0.80: 0.80-1.20: 0.60-0.90: 0.50-0.90: 0.30-0.80: 1.30-1.60: 0.10-0.50.
5. The additive for ZnO pressure sensitive ceramics according to any of the claims 1 to 4, wherein the sintering temperature is 700 ℃ to 900 ℃; the sintering time is 2-4 h; the heating rate of heating to the sintering temperature is 3-5 ℃/min.
6. A ZnO varistor ceramic material, comprising ZnO and the additive for ZnO varistor ceramic according to any one of claims 1 to 5.
7. The ZnO voltage sensitive ceramic material according to claim 6, wherein the additive for ZnO voltage sensitive ceramic is prepared by sintering the following raw materials: gd (Gd)2O3、Bi2O3、Sb2O3、Co2O3、MnO2、NiO、SiO2And Cr2O3(ii) a The additive for the ZnO voltage-sensitive ceramic is prepared by sintering the following raw materials in mol percentage, wherein the total mole number of the ZnO and the additive for the ZnO voltage-sensitive ceramic is 100 parts:
Gd2O3 0.25～1.00，Sb2O3 0.80～1.20，Co2O3 0.60～0.90，MnO2 0.50～0.90，Bi2O30.50～0.80，NiO 0.30～0.80，SiO2 1.30～1.60，Cr2O3 0.10～0.50。
8. a ZnO varistor ceramic characterized by being obtained by subjecting the ZnO varistor ceramic material according to claim 6 or 7 to a sintering treatment.
9. The method for preparing the ZnO pressure sensitive ceramic of claim 8, comprising the steps of: and sintering the ZnO voltage-sensitive ceramic material to obtain the ZnO voltage-sensitive ceramic material.
10. The method for producing the ZnO varistor ceramic according to claim 9, wherein the ZnO varistor ceramic material has a particle size of not more than 0.15 mm.
11. The method for producing a ZnO pressure-sensitive ceramic according to claim 9 or 10, wherein the sintering process includes two stages of first sintering and second sintering; the temperature of the first sintering is 400-550 ℃; the first sintering time is 2-4 h; the temperature of the second sintering is 1000-1200 ℃; and the time of the second sintering is 2-4 h.
12. The method for preparing the ZnO voltage-sensitive ceramic according to claim 11, wherein the temperature rise rate of raising the temperature to the first sintering temperature is 1 to 3 ℃/min.
13. The method for preparing the ZnO voltage-sensitive ceramic according to claim 11, wherein the rate of temperature rise from the first sintering temperature to the second sintering temperature is 3 to 5 ℃/min.
14. A ZnO varistor prepared from the ZnO varistor of claim 8.
15. A preparation method of a ZnO piezoresistor is characterized by comprising the following steps: the ZnO varistor ceramic according to claim 8 is subjected to silver and silver firing treatment.
16. The preparation method of the ZnO varistor as claimed in claim 15, wherein the temperature of the silver firing treatment is 600-820 ℃; the silver firing treatment time is 1-3 h.
17. The method for preparing the ZnO varistor according to claim 15, wherein a temperature rise rate of raising the temperature to the temperature of the silver firing treatment is 2 to 4 ℃/min.
18. A varistor element produced from the ZnO varistor of claim 8 or from the ZnO varistor of claim 14.
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