阅读说明：本技术 金属氧化物压电变阻片关键材料修饰改性提高其电性能的方法 (Method for improving electrical property of metal oxide piezoelectric varistor piece by modifying key material ) 是由 黄海 靳国青 涂远生 赵旭 李明双 涂宗洋 于 2019-11-22 设计创作，主要内容包括：本发明涉及氧化锌避雷器制造技术领域，且公开了一种金属氧化物压电变阻片关键材料修饰改性提高其电性能的方法，包括以下步骤：氧化物单质选取、纳米粉体合成、关键材料修饰、金属氧化物粉体细化、混合煅烧和电性能测试。本发明通过在关键材料中加入一定比例的重金属Ag进行修饰改性后更加适应现有生产工艺和设备，提高了生产效率，减少了金属氧化物原料的用量，降低了生产成本，节约了一定量的化工原料，以修饰后的氧化锌、氧化铋、氧化钴为原料生产出的电阻片压比U<Sub>10kA</Sub>/U<Sub>1mA</Sub>在1.68?1.75之间，较之前有显著降低，电阻片的4/10μs大电流两次耐受能力可以达到100kA，达到了国际标准。(The invention relates to the technical field of manufacturing of zinc oxide arresters, and discloses a method for improving the electrical property of a metal oxide piezoelectric varistor sheet by modifying key materials, which comprises the following steps: selecting simple substances of oxides, synthesizing nano powder, modifying key materials, refining metal oxide powder, mixing and calcining and testing electrical property. The invention is more suitable for the prior production after adding a certain proportion of heavy metal Ag into the key material for modificationThe process and the equipment improve the production efficiency, reduce the consumption of metal oxide raw materials, reduce the production cost, save a certain amount of chemical raw materials, and produce the resistance card pressure ratio U by using the modified zinc oxide, bismuth oxide and cobalt oxide as raw materials 10kA /U 1mA Between 1.68 and 1.75, the resistance card is obviously reduced compared with the prior resistance card, and the twice endurance capacity of 4/10 mu s large current of the resistance card can reach 100kA, thereby reaching the international standard.)

1. The method for improving the electrical property of the metal oxide piezoelectric varistor sheet by modifying key materials is characterized by comprising the following steps of:

1) selecting simple substances of oxides: selecting simple substances of oxides such as zinc oxide, bismuth oxide, cobalt oxide, lead oxide, nickel oxide, chromium oxide, antimony oxide, silicon dioxide and the like, weighing and selecting the simple substances, and respectively adding the simple substances into a nitric acid solution with a certain concentration;

2) synthesizing nano powder: synthesizing nano oxide metal oxide powder by a hydrothermal synthesis method;

3) key material modification: doping a certain proportion of noble metal Ag in the above synthetic key materials such as zinc oxide, bismuth oxide, cobalt oxide and silicon dioxide to modify the key materials;

4) refining metal oxide powder: ball-milling the metal oxide by using cleaned agate balls, and drying and sieving after the ball-milling is finished;

5) mixing and calcining: mixing and calcining the sieved powder, and controlling the calcining temperature;

6) and (3) testing electrical properties: and after the calcination is finished, sequentially carrying out spray granulation, molding, plastic discharging, glazing, secondary sintering, grinding and heat treatment until a finished piezoelectric varistor sheet product is prepared, and then carrying out electrical property test.

2. The method for improving the electrical property of the metal oxide piezoelectric varistor as claimed in claim 1, wherein the molar mass ratio of zinc oxide, bismuth oxide, cobalt oxide, lead oxide, nickel oxide, chromium oxide, antimony oxide and silicon dioxide is 93-95: 0.7-0.9: 1.1-1.3: 0.1-0.3: 0.6-0.7: 1.0-1.2: 1.3 to 1.5.

3. The method for improving the electrical property of the metal oxide piezoelectric varistor as claimed in claim 1, wherein the temperature in the hydrothermal synthesis method is controlled to be 100-1000 ℃.

4. The method for improving the electrical property of the metal oxide piezoelectric varistor piece through modifying key materials of the metal oxide piezoelectric varistor piece, according to claim 1, is characterized in that after drying and sieving, the obtained oxide powder is not more than 2 microns.

5. The method for improving the electrical property of the metal oxide piezoelectric varistor sheet through key material modification according to claim 1, wherein the temperature of the mixed calcination stage is 100-1250 ℃, and the mixed calcination stage is kept for 3-4 hours after the highest temperature is reached.

Technical Field

The invention relates to the technical field of manufacturing of zinc oxide arresters, in particular to a method for improving the electrical property of a metal oxide piezoelectric varistor by modifying key materials.

Background

The zinc oxide, bismuth oxide, cobalt oxide and other metal oxides are used as important additives in the zinc oxide resistance card and play an important role in the performance of the resistance card. In recent years, with the continuous development of the technology of the resistive sheet, the performance requirements of the resistive sheet in the international standard are higher and higher, which is mainly expressed as: the potential gradient, the energy absorption density and the allowable charge rate of the zinc oxide resistance card are continuously increased, and the leakage current and the residual voltage ratio are continuously reduced. In order to meet the requirement, key materials used in the production of the zinc oxide resistance chip, such as zinc oxide, bismuth oxide, cobalt oxide and other metal oxides, are modified, so that the piezoelectric performance of the metal oxide piezoelectric resistance chip is improved

Disclosure of Invention

Technical problem to be solved

Aiming at the defects of the prior art, the invention provides a method for improving the electrical property of a metal oxide piezoelectric varistor by modifying key materials, which has the advantages of higher production efficiency, lower production cost, lower voltage ratio, stronger large current impact resistance and the like, and solves the problems of low production efficiency, high production cost, higher voltage ratio and weaker large current impact resistance of the conventional varistor.

(II) technical scheme

In order to achieve the purposes of higher production efficiency, lower production cost, lower voltage ratio and stronger large current impact resistance, the invention provides the following technical scheme: the method for improving the electrical property of the metal oxide piezoelectric varistor by modifying key materials comprises the following steps:

1) selecting simple substances of oxides: selecting simple substances of oxides such as zinc oxide, bismuth oxide, cobalt oxide, lead oxide, nickel oxide, chromium oxide, antimony oxide, silicon dioxide and the like, weighing and selecting the simple substances, and respectively adding the simple substances into a nitric acid solution with a certain concentration;

2) synthesizing nano powder: synthesizing nano oxide metal oxide powder by a hydrothermal synthesis method;

3) key material modification: doping a certain proportion of noble metal Ag in the above synthetic key materials such as zinc oxide, bismuth oxide, cobalt oxide and silicon dioxide to modify the key materials;

4) refining metal oxide powder: ball-milling the metal oxide by using cleaned agate balls, and drying and sieving after the ball-milling is finished;

5) mixing and calcining: mixing and calcining the sieved powder, and controlling the calcining temperature;

6) and (3) testing electrical properties: and after the calcination is finished, sequentially carrying out spray granulation, molding, plastic discharging, glazing, secondary sintering, grinding and heat treatment until a finished piezoelectric varistor sheet product is prepared, and then carrying out electrical property test.

Preferably, the molar mass ratio of zinc oxide, bismuth oxide, cobalt oxide, lead oxide, nickel oxide, chromium oxide, antimony oxide and silicon dioxide is 93-95: 0.7-0.9: 1.1-1.3: 0.1-0.3: 0.6-0.7: 1.0-1.2: 1.3 to 1.5.

Preferably, the temperature in the hydrothermal synthesis method is controlled to be 100 to 1000 ℃.

Preferably, the oxide powder obtained after drying and sieving does not exceed 2 microns.

Preferably, the temperature of the mixed calcination stage is 100-1250 ℃, and the mixed calcination stage is kept for 3-4 hours after the highest temperature is reached.

(III) advantageous effects

Compared with the prior art, the invention provides a method for improving the electrical property of a metal oxide piezoelectric varistor sheet by modifying key materials, which has the following beneficial effects:

1. the zinc oxide resistance card is more suitable for the existing production process and equipment after the key materials of the zinc oxide resistance card, such as zinc oxide, bismuth oxide, cobalt oxide and other metal oxide powders, are modified, and the production efficiency is improved.

2. Through experiments, the consumption of metal oxide raw materials is reduced, the production cost is reduced, and a certain amount of chemical raw materials are saved.

3. Resistance card pressure ratio U produced by using modified zinc oxide, bismuth oxide and cobalt oxide as raw materials_10kA/U_1mABetween 1.68 and 1.75, a significant reduction compared to the previous.

4. The 4/10 mus large current twice-enduring capacity of the resistance card can reach 100kA, and the international standard is reached.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.