CN116936207A - Zinc oxide piezoresistor medium with high potential gradient and high nonlinear coefficient and preparation method thereof - Google Patents
Zinc oxide piezoresistor medium with high potential gradient and high nonlinear coefficient and preparation method thereof Download PDFInfo
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Abstract
The zinc oxide piezoresistor medium with high potential gradient and high nonlinear coefficient is characterized by comprising the following components in parts by mole: znO 100 parts, sb 2 O 3 0.01-1.8 parts of Co 2 O 3 0.01-1.8 parts of Bi 2 O 3 0.01-1.8 parts of Ni 2 O 3 0.01-1.8 parts of Cr 2 O 3 0.01-1.8 parts of Ag 2 CaV 4 O 12 0.01-1.8 parts of Al 2 O 3 0.01-1.0 part, zinc borate 0.01-1.0 part, liNO 3 0.01-1.0 part of ZnTeO 4 0.01-1.0 parts. The invention also provides the zinc oxide voltage-sensitive electricity with high potential gradient and high nonlinear coefficientA method for preparing a resistor medium. The zinc oxide piezoresistor medium has high potential gradient and high nonlinear coefficient, has strong pulse impact resistance, and can be applied to lightning protection overvoltage protection of a power arrester or other power electronic circuits.
Description
Technical Field
The invention relates to a dielectric material of a piezoresistor, in particular to a zinc oxide piezoresistor dielectric with high potential gradient and high nonlinear coefficient and a preparation method thereof.
Background
The zinc oxide varistor material can be used to make high energy zinc oxide varistor sheets, which can be used to make lightning arresters or varistors, for use in power electronics to absorb abnormal overvoltage to protect the circuit system. The abnormal overvoltage of the circuit is often caused by lightning strike load in the power electronic circuit, and the zinc oxide ceramic dielectric material is widely used in the power electronic circuit to absorb or inhibit the abnormal overvoltage and protect the power electronic equipment from being damaged.
However, the voltage gradient (voltage sensitive voltage per unit thickness) of the zinc oxide varistor dielectric materials which are currently used is generally lower than 250V/mm, and for power electronic circuits with higher working voltages, the thickness of the varistor sheets used is larger or the number of series connection is larger. If the potential gradient of the pressure sensitive material can be improved, the thickness of the piezoresistor sheets in the same application occasion can be reduced or the number of series connection can be reduced, the height of the lightning arrester made of the piezoresistor sheets can be greatly reduced, the cost of the lightning arrester can be reduced, the gravity load of the application occasion of the lightning arrester can be reduced, and the reliability of a power transmission and distribution system can be improved.
While patent application No. 97103063.4 (titled: voltage nonlinear resistor, voltage-sensitive nonlinear resistor manufacturing method and arrester) discloses that a varistor with a potential gradient of 400-450V/mm can be manufactured, the process requires a cooling rate of 0-5 ℃/hour between 700-400 ℃, which is difficult to realize in production, and the invention requires cooling or annealing in an atmosphere with an oxygen partial pressure of more than 50% to improve the voltage nonlinearity, which greatly increases the manufacturing of the varistorThe cost is high. The patent application with the application number of 200510025398.5 (named as preparation and application of high-potential gradient zinc oxide varistor material) discloses that the varistor material with high-potential gradient can be obtained, but the preparation process of the varistor material requires multiple ball milling and sintering, and the pulse impact resistance of the varistor material is not disclosed. Patent application No. 200610042720.X (named: rare earth oxide doped ZnO-Bi 2 O 3 A pressure sensitive ceramic medium) discloses a pressure sensitive material with the voltage gradient reaching 500V/mm, but the nonlinear coefficient is smaller and the leakage current is larger.
Disclosure of Invention
The invention aims to provide a zinc oxide varistor medium with high potential gradient, high nonlinear coefficient and high pulse impact resistance and a preparation method thereof. The technical scheme adopted is as follows:
the zinc oxide piezoresistor medium with high potential gradient and high nonlinear coefficient is characterized by comprising the following components in parts by mole: znO 100 parts, sb 2 O 3 0.01-1.8 parts of Co 2 O 3 0.01-1.8 parts of Bi 2 O 3 0.01-1.8 parts of Ni 2 O 3 0.01-1.8 parts of Cr 2 O 3 0.01-1.8 parts of Ag 2 CaV 4 O 12 0.01-1.8 parts of Al 2 O 3 0.01-1.0 part, zinc borate 0.01-1.0 part, liNO 3 0.01-1.0 part of ZnTeO 4 0.01-1.0 parts.
Preferably Ag as described above 2 CaV 4 O 12 、ZnTeO 4 The method adopts the conventional chemical raw materials to synthesize the compound by a solid phase method.
Above Ag 2 CaV 4 O 12 The preparation method can be adopted as follows: ag is prepared according to the mol ratio of 1:1:2 2 CO 3 、CaCO 3 And V 2 O 5 Then to Ag 2 CO 3 、CaCO 3 And V 2 O 5 Grinding and uniformly mixing; then Ag is added 2 CO 3 、CaCO 3 And V 2 O 5 Placing the mixture in an alumina crucible, and maintaining the temperature at 450-500 ℃ for 120 minutes to obtain Ag 2 CaV 4 O 12 . The Ag obtained 2 CaV 4 O 12 After cooling, grinding and sieving with a 200 mesh sieve for standby.
The ZnTeO mentioned above 4 The preparation method can be adopted as follows: according to the following steps of 1:1 molar ratio of ZnO and TeO 3 Then for ZnO and TeO 3 Grinding and uniformly mixing; znO and TeO are then added 3 Placing the mixture in an alumina crucible, and preserving heat at 550-600 ℃ for 120 minutes to obtain ZnTeO 4 . The obtained ZnTeO 4 Grinding after cooling, and sieving with a 200-mesh sieve for standby.
Above Ag 2 CaV 4 O 12 Can improve potential gradient, reduce leakage current and lower sintering temperature. The ZnTeO mentioned above 4 The potential gradient can be improved, the nonlinear coefficient can be improved, and the sintering temperature can be reduced.
The invention also provides a preparation method of the zinc oxide piezoresistor medium with high potential gradient and high nonlinear coefficient, which is characterized by comprising the following steps:
(1) Preparing ZnO and Sb according to a certain proportion 2 O 3 、Co 2 O 3 、Bi 2 O 3 、Ni 2 O 3 、Cr 2 O 3 、Ag 2 CaV 4 O 12 、Al 2 O 3 Zinc borate, liNO 3 And ZnTeO 4 ；
(2) Preparation of additive slurries
Sb prepared in the step (1) 2 O 3 、Co 2 O 3 、Bi 2 O 3 、Ni 2 O 3 、Cr 2 O 3 、Ag 2 CaV 4 O 12 、Al 2 O 3 Zinc borate, liNO 3 And ZnTeO 4 Mixing to obtain a mixture; adding pure water and an ammonium salt dispersing agent into the mixture for ball milling, so that the components are uniformly mixed, and an additive slurry is obtained;
(3) Preparation of spray slurry
Adding ZnO prepared in the step (1) into the additive slurry, and adding a polyvinyl alcohol aqueous solution to obtain mixed slurry; then ball milling is carried out on the mixed slurry until the specific gravity of the mixed slurry is 1.5-2.0 and the viscosity is 40-200cps (the ball milling time is about 3 hours), so as to obtain spray slurry;
(4) Spraying and granulating the spraying slurry obtained in the step (3) by using a spray drying tower to obtain powder;
(5) Dry-pressing to form the powder obtained in the step (4) into a green sheet;
(6) And (3) removing polyvinyl alcohol from the green sheet obtained in the step (5), and then preserving heat for 2-4 hours in an environment with the temperature of 950-980 ℃ to sinter the green sheet, thereby obtaining the zinc oxide varistor medium with high potential gradient and high nonlinear coefficient.
Preferably, in the step (2), during ball milling, the adding amount of the ammonium salt dispersing agent is 0.8-1.3% of the total weight of the mixture, and the weight ratio of the ball-milled mixture, the ball and the water is as follows: mixture, ball, water=1:3 (0.6-1.0).
Preferably, in the step (3), the solid content of the added aqueous polyvinyl alcohol solution is ZnO or Sb 2 O 3 、Co 2 O 3 、Bi 2 O 3 、Ni 2 O 3 、Cr 2 O 3 、Ag 2 CaV 4 O 12 、Al 2 O 3 Zinc borate, liNO 3 And ZnTeO 4 0.9-1.3% of the total weight of (C).
Preferably, in step (6), the green sheet is subjected to an atmosphere of 500-550 ℃ to exclude polyvinyl alcohol.
During the sintering process of step (6), moisture, ammonium salt dispersant and residual polyvinyl alcohol in the green sheet may be removed.
Compared with the prior art, the invention has the following advantages: (1) The potential gradient of the obtained zinc oxide piezoresistor medium is 816-863V/mm; (2) The nonlinear coefficient alpha of the obtained zinc oxide piezoresistor medium is 95-106; (3) The obtained zinc oxide piezoresistor medium has strong pulse impact resistance; and (4) the preparation process is simple and feasible.
The zinc oxide piezoresistor medium has high potential gradient and high nonlinear coefficient, has strong pulse impact resistance, and can be applied to lightning protection overvoltage protection of a power arrester or other power electronic circuits.
Detailed Description
Example 1
First, ag is synthesized by solid phase method 2 CaV 4 O 12 、ZnTeO 4 。
Ag 2 CaV 4 O 12 The preparation method comprises the following steps: ag is prepared according to the mol ratio of 1:1:2 2 CO 3 、CaCO 3 And V 2 O 5 Then to Ag 2 CO 3 、CaCO 3 And V 2 O 5 Grinding and uniformly mixing; then Ag is added 2 CO 3 、CaCO 3 And V 2 O 5 Placing the mixture in an alumina crucible, and preserving the temperature at 480 ℃ for 120 minutes to obtain Ag 2 CaV 4 O 12 . The Ag obtained 2 CaV 4 O 12 After cooling, grinding and sieving with a 200 mesh sieve for standby.
ZnTeO 4 The preparation method comprises the following steps: according to the following steps of 1:1 molar ratio of ZnO and TeO 3 Then for ZnO and TeO 3 Grinding and uniformly mixing; znO and TeO are then added 3 Placing the mixture in an alumina crucible, and preserving the temperature at 580 ℃ for 120 minutes to obtain ZnTeO 4 . The obtained ZnTeO 4 Grinding after cooling, and sieving with a 200-mesh sieve for standby.
Then, preparing a zinc oxide piezoresistor medium with high potential gradient and high nonlinear coefficient according to the following steps:
(1) Preparing ZnO and Sb according to a certain proportion 2 O 3 、Co 2 O 3 、Bi 2 O 3 、Ni 2 O 3 、Cr 2 O 3 、Ag 2 CaV 4 O 12 、Al 2 O 3 Zinc borate, liNO 3 And ZnTeO 4 ；
In this example, the ratio of the raw materials was calculated in terms of mole fractionThe method comprises the following steps: znO 100 parts, sb 2 O 3 0.3 part of Co 2 O 3 0.3 part of Bi 2 O 3 0.3 part of Ni 2 O 3 0.3 part of Cr 2 O 3 0.3 part of Ag 2 CaV 4 O 12 0.3 part of Al 2 O 3 0.4 part of zinc borate 0.4 part, liNO 3 0.4 part of ZnTeO 4 0.4 parts;
(2) Preparation of additive slurries
Sb prepared in the step (1) 2 O 3 、Co 2 O 3 、Bi 2 O 3 、Ni 2 O 3 、Cr 2 O 3 、Ag 2 CaV 4 O 12 、Al 2 O 3 Zinc borate, liNO 3 And ZnTeO 4 Mixing to obtain a mixture; adding pure water and an ammonium salt dispersing agent into the mixture for ball milling, so that the components are uniformly mixed, and an additive slurry is obtained;
in the step (2), during ball milling, the adding amount of the ammonium salt dispersing agent is 1 percent of the total weight of the mixture, and the weight ratio of the ball-milled mixture, the ball and the water is as follows: mixture ball water=1:3:0.7;
(3) Preparation of spray slurry
Adding ZnO prepared in the step (1) into the additive slurry, and adding a polyvinyl alcohol aqueous solution to obtain mixed slurry; then ball milling is carried out on the mixed slurry until the specific gravity of the mixed slurry is 1.8 and the viscosity is 100cps (the ball milling time is about 3 hours), so as to obtain spray slurry;
in the step (3), the solid content of the added aqueous solution of polyvinyl alcohol is ZnO or Sb 2 O 3 、Co 2 O 3 、Bi 2 O 3 、Ni 2 O 3 、Cr 2 O 3 、Ag 2 CaV 4 O 12 、Al 2 O 3 Zinc borate, liNO 3 And ZnTeO 4 1% of the total weight of (2);
(4) Spraying and granulating the spraying slurry obtained in the step (3) by using a spray drying tower to obtain powder;
(5) Dry-press molding (dry-press molding of powder at 100 MPa), and pressing the powder obtained in the step (4) into a green sheet (the green sheet is a disc with a diameter of 23mm and a thickness of 2 mm);
(6) And (3) removing polyvinyl alcohol from the green sheet obtained in the step (5) (the green sheet can be placed in an environment of 520 ℃ to remove the polyvinyl alcohol), and preserving the heat for 3 hours in the environment of 970 ℃ to sinter the green sheet, so as to obtain the zinc oxide varistor medium with high potential gradient and high nonlinear coefficient.
Manufacturing metal electrodes on two sides of the obtained high-potential gradient high-nonlinearity coefficient zinc oxide piezoresistor dielectric sheet (printing silver electrode slurry on two sides of the zinc oxide piezoresistor dielectric material sheet, and reducing at 600 ℃ to obtain a metal silver electrode layer, namely forming a metal electrode); and then welding tin-plated copper leads on the two sides of the metal electrode, dip-coating high-temperature epoxy insulating paint, curing, then thermally coating powder epoxy encapsulating material, and curing to obtain the electrical property test sample.
Example 2
First, ag is synthesized by solid phase method 2 CaV 4 O 12 、ZnTeO 4 。
Ag 2 CaV 4 O 12 The preparation method comprises the following steps: ag is prepared according to the mol ratio of 1:1:2 2 CO 3 、CaCO 3 And V 2 O 5 Then to Ag 2 CO 3 、CaCO 3 And V 2 O 5 Grinding and uniformly mixing; then Ag is added 2 CO 3 、CaCO 3 And V 2 O 5 Placing the mixture in an alumina crucible, and preserving heat at 460 ℃ for 120 minutes to obtain Ag 2 CaV 4 O 12 . The Ag obtained 2 CaV 4 O 12 After cooling, grinding and sieving with a 200 mesh sieve for standby.
ZnTeO 4 The preparation method comprises the following steps: according to the following steps of 1:1 molar ratio of ZnO and TeO 3 Then for ZnO and TeO 3 Grinding and uniformly mixing; znO and TeO are then added 3 Placing the mixture in an alumina crucible, and preserving the temperature at 600 ℃ for 120 minutes to obtain ZnTeO 4 . The obtained ZnTeO 4 Grinding after cooling, and sieving with a 200-mesh sieve for standby.
Then, preparing a zinc oxide piezoresistor medium with high potential gradient and high nonlinear coefficient according to the following steps:
(1) Preparing ZnO and Sb according to a certain proportion 2 O 3 、Co 2 O 3 、Bi 2 O 3 、Ni 2 O 3 、Cr 2 O 3 、Ag 2 CaV 4 O 12 、Al 2 O 3 Zinc borate, liNO 3 And ZnTeO 4 ；
In the embodiment, the prepared raw materials are in the following proportion by mol portion: znO 100 parts, sb 2 O 3 1.2 parts, co 2 O 3 1.2 parts of Bi 2 O 3 1.2 parts of Ni 2 O 3 1.2 parts of Cr 2 O 3 1.2 parts of Ag 2 CaV 4 O 12 1.2 parts of Al 2 O 3 0.55 part of zinc borate 0.55 part, liNO 3 0.55 part of ZnTeO 4 0.55 parts;
(2) Preparation of additive slurries
Sb prepared in the step (1) 2 O 3 、Co 2 O 3 、Bi 2 O 3 、Ni 2 O 3 、Cr 2 O 3 、Ag 2 CaV 4 O 12 、Al 2 O 3 Zinc borate, liNO 3 And ZnTeO 4 Mixing to obtain a mixture; adding pure water and an ammonium salt dispersing agent into the mixture for ball milling, so that the components are uniformly mixed, and an additive slurry is obtained;
in the step (2), during ball milling, the adding amount of the ammonium salt dispersing agent is 1.2 percent of the total weight of the mixture, and the weight ratio of the ball-milled mixture, the ball and the water is as follows: mixture ball water=1:3:0.6;
(3) Preparation of spray slurry
Adding ZnO prepared in the step (1) into the additive slurry, and adding a polyvinyl alcohol aqueous solution to obtain mixed slurry; then ball milling is carried out on the mixed slurry until the specific gravity of the mixed slurry is 2.0 and the viscosity is 180cps (the ball milling time is about 3 hours), so as to obtain spray slurry;
in the step (3), the solid content of the added aqueous solution of polyvinyl alcohol is ZnO or Sb 2 O 3 、Co 2 O 3 、Bi 2 O 3 、Ni 2 O 3 、Cr 2 O 3 、Ag 2 CaV 4 O 12 、Al 2 O 3 Zinc borate, liNO 3 And ZnTeO 4 1.2% of the total weight of (2);
(4) Spraying and granulating the spraying slurry obtained in the step (3) by using a spray drying tower to obtain powder;
(5) Dry-press molding (dry-press molding of powder at 100 MPa), and pressing the powder obtained in the step (4) into a green sheet (the green sheet is a disc with a diameter of 23mm and a thickness of 2 mm);
(6) And (3) removing polyvinyl alcohol from the green sheet obtained in the step (5) (the green sheet can be placed in an environment of 550 ℃ to remove the polyvinyl alcohol), and preserving the heat for 2.5 hours in the environment of 980 ℃ to sinter the green sheet, so as to obtain the zinc oxide varistor medium with high potential gradient and high nonlinear coefficient.
Manufacturing metal electrodes on two sides of the obtained high-potential gradient high-nonlinearity coefficient zinc oxide piezoresistor dielectric sheet (printing silver electrode slurry on two sides of the zinc oxide piezoresistor dielectric material sheet, and reducing at 600 ℃ to obtain a metal silver electrode layer, namely forming a metal electrode); and then welding tin-plated copper leads on the two sides of the metal electrode, dip-coating high-temperature epoxy insulating paint, curing, then thermally coating powder epoxy encapsulating material, and curing to obtain the electrical property test sample.
Example 3
First, ag is synthesized by solid phase method 2 CaV 4 O 12 、ZnTeO 4 。
Ag 2 CaV 4 O 12 The preparation method comprises the following steps: ag is prepared according to the mol ratio of 1:1:2 2 CO 3 、CaCO 3 And V 2 O 5 Then to Ag 2 CO 3 、CaCO 3 And V 2 O 5 Grinding and uniformly mixing; then Ag is added 2 CO 3 、CaCO 3 And V 2 O 5 Placing the mixture in an alumina crucible, and preserving the temperature for 120 minutes at 500 ℃ to obtain Ag 2 CaV 4 O 12 . The Ag obtained 2 CaV 4 O 12 After cooling, grinding and sieving with a 200 mesh sieve for standby.
ZnTeO 4 The preparation method comprises the following steps: according to the following steps of 1:1 molar ratio of ZnO and TeO 3 Then for ZnO and TeO 3 Grinding and uniformly mixing; znO and TeO are then added 3 Placing the mixture in an alumina crucible, and preserving the temperature at 550 ℃ for 120 minutes to obtain ZnTeO 4 . The obtained ZnTeO 4 Grinding after cooling, and sieving with a 200-mesh sieve for standby.
Then, preparing a zinc oxide piezoresistor medium with high potential gradient and high nonlinear coefficient according to the following steps:
(1) Preparing ZnO and Sb according to a certain proportion 2 O 3 、Co 2 O 3 、Bi 2 O 3 、Ni 2 O 3 、Cr 2 O 3 、Ag 2 CaV 4 O 12 、Al 2 O 3 Zinc borate, liNO 3 And ZnTeO 4 ；
In the embodiment, the prepared raw materials are in the following proportion by mol portion: znO 100 parts, sb 2 O 3 0.73 part, co 2 O 3 0.73 part of Bi 2 O 3 0.73 part of Ni 2 O 3 0.73 part of Cr 2 O 3 0.73 part of Ag 2 CaV 4 O 12 0.73 part of Al 2 O 3 0.35 part of zinc borate 0.35 part, liNO 3 0.35 part of ZnTeO 4 0.35 parts;
(2) Preparation of additive slurries
Sb prepared in the step (1) 2 O 3 、Co 2 O 3 、Bi 2 O 3 、Ni 2 O 3 、Cr 2 O 3 、Ag 2 CaV 4 O 12 、Al 2 O 3 Zinc borate, liNO 3 And ZnTeO 4 Mixing to obtain a mixture; adding pure water and an ammonium salt dispersing agent into the mixture for ball milling, so that the components are uniformly mixed, and an additive slurry is obtained;
in the step (2), during ball milling, the adding amount of the ammonium salt dispersing agent is 0.8 percent of the total weight of the mixture, and the weight ratio of the ball-milled mixture, the ball and the water is as follows: mixture ball water=1:3:1.0;
(3) Preparation of spray slurry
Adding ZnO prepared in the step (1) into the additive slurry, and adding a polyvinyl alcohol aqueous solution to obtain mixed slurry; then ball milling is carried out on the mixed slurry until the specific gravity of the mixed slurry is 1.6 and the viscosity is 80cps (the ball milling time is about 3 hours), so as to obtain spray slurry;
in the step (3), the solid content of the added aqueous solution of polyvinyl alcohol is ZnO or Sb 2 O 3 、Co 2 O 3 、Bi 2 O 3 、Ni 2 O 3 、Cr 2 O 3 、Ag 2 CaV 4 O 12 、Al 2 O 3 Zinc borate, liNO 3 And ZnTeO 4 0.9% of the total weight of (a);
(4) Spraying and granulating the spraying slurry obtained in the step (3) by using a spray drying tower to obtain powder;
(5) Dry-press molding (dry-press molding of powder at 100 MPa), and pressing the powder obtained in the step (4) into a green sheet (the green sheet is a disc with a diameter of 23mm and a thickness of 2 mm);
(6) And (3) removing polyvinyl alcohol from the green sheet obtained in the step (5) (the green sheet can be placed in an environment of 500 ℃ to remove the polyvinyl alcohol), and preserving the heat for 4 hours in the environment of 950 ℃ to sinter the green sheet, so as to obtain the zinc oxide varistor medium with high potential gradient and high nonlinear coefficient.
Manufacturing metal electrodes on two sides of the obtained high-potential gradient high-nonlinearity coefficient zinc oxide piezoresistor dielectric sheet (printing silver electrode slurry on two sides of the zinc oxide piezoresistor dielectric material sheet, and reducing at 600 ℃ to obtain a metal silver electrode layer, namely forming a metal electrode); and then welding tin-plated copper leads on the two sides of the metal electrode, dip-coating high-temperature epoxy insulating paint, curing, then thermally coating powder epoxy encapsulating material, and curing to obtain the electrical property test sample.
Example 4
In the case where the other portions are the same as in example 1, the present example differs from example 1 in that ZnO, sb 2 O 3 、Co 2 O 3 、Bi 2 O 3 、Ni 2 O 3 、Cr 2 O 3 、Ag 2 CaV 4 O 12 、Al 2 O 3 Zinc borate, liNO 3 And ZnTeO 4 The amounts of (3) vary. In the embodiment, the prepared raw materials are in the following proportion by mol portion: znO 100 parts, sb 2 O 3 0.2 part of Co 2 O 3 0.2 part of Bi 2 O 3 1.3 parts of Ni 2 O 3 1.3 parts of Cr 2 O 3 1.3 parts of Ag 2 CaV 4 O 12 1.3 parts of Al 2 O 3 0.3 part of zinc borate 0.65 part of LiNO 3 0.65 part of ZnTeO 4 0.65 parts.
Example 5
In the case where the other portions are the same as in example 1, the present example differs from example 2 in that ZnO, sb 2 O 3 、Co 2 O 3 、Bi 2 O 3 、Ni 2 O 3 、Cr 2 O 3 、Ag 2 CaV 4 O 12 、Al 2 O 3 Zinc borate, liNO 3 And ZnTeO 4 The amounts of (3) vary. In the embodiment, the prepared raw materials are in the following proportion by mol portion: znO 100 parts, sb 2 O 3 0.35 part, co 2 O 3 0.35 part of Bi 2 O 3 0.65 part of Ni 2 O 3 0.65 part of Cr 2 O 3 0.65 part of Ag 2 CaV 4 O 12 0.65 part of Al 2 O 3 0.25 part of zinc borate 0.73 part of LiNO 3 0.73 part of ZnTeO 4 0.73 parts.
Example 6
In the case where the other portions are the same as in example 1, the present example differs from example 3 in that ZnO, sb 2 O 3 、Co 2 O 3 、Bi 2 O 3 、Ni 2 O 3 、Cr 2 O 3 、Ag 2 CaV 4 O 12 、Al 2 O 3 Zinc borate, liNO 3 And ZnTeO 4 The amounts of (3) vary. In the embodiment, the prepared raw materials are in the following proportion by mol portion: znO 100 parts, sb 2 O 3 0.9 part of Co 2 O 3 0.9 part of Bi 2 O 3 0.35 part of Ni 2 O 3 0.35 part of Cr 2 O 3 0.35 part of Ag 2 CaV 4 O 12 0.35 part of Al 2 O 3 0.75 part of zinc borate 0.75 part, liNO 3 0.75 part of ZnTeO 4 0.75 parts.
The samples of examples 1-6 were tested for voltage dependent voltage (V 1mA ) V (V) 0.1mA Using a constant voltage source (voltage adjusted to 83% V 1mA ) The samples of examples 1-6 were tested for leakage current and the nonlinear coefficient alpha values of the samples of examples 1-6 were calculated using the relevant formulas. The capability of bearing impulse current is the key of the pressure sensitive element to be practically applied. The pulse impact test waveforms of the samples of examples 1 to 6 of the invention are 8/20 mu s simulated lightning waves, the peak current target value is 5000A, the voltage-sensitive voltages of the samples are tested before and after the pulse impact test, the change rate of the voltage-sensitive voltages is calculated, and the appearance structure of the samples after the pulse impact is observed and judged, if the voltage-sensitive voltage V 1mA The change rate is within +/-10%, and the appearance structure of the sample is not damaged after the sample is subjected to pulse impact, so that the sample is judged to be qualified in the performance of the sample subjected to the pulse impact, otherwise, the sample is judged to be invalid. The specific performance test results are shown in table 1.
TABLE 1 Performance test results of Zinc oxide varistor media prepared in accordance with various embodiments of the present invention
As can be seen from the table 1, the zinc oxide piezoresistor medium prepared by the invention has high potential gradient (the potential gradient is 816-863V/mm); low leakage current (leakage current is 0.10-0.18 mu A); the nonlinear coefficient is high (the nonlinear coefficient is more than 95, and particularly, 95-106); the pulse impact resistance is strong, and the pulse impact protection device can be used for lightning protection overvoltage protection of a power lightning arrester or other power electronic circuits.
Claims (7)
1. The zinc oxide piezoresistor medium with high potential gradient and high nonlinear coefficient is characterized by comprising the following components in parts by mole: znO 100 parts, sb 2 O 3 0.01-1.8 parts of Co 2 O 3 0.01-1.8 parts of Bi 2 O 3 0.01-1.8 parts of Ni 2 O 3 0.01-1.8 parts of Cr 2 O 3 0.01-1.8 parts of Ag 2 CaV 4 O 12 0.01-1.8 parts of Al 2 O 3 0.01-1.0 part, zinc borate 0.01-1.0 part, liNO 3 0.01-1.0 part of ZnTeO 4 0.01-1.0 parts.
2. The high potential gradient high nonlinear coefficient zinc oxide varistor medium of claim 1, characterized in that said Ag 2 CaV 4 O 12 The preparation method comprises the following steps: ag is prepared according to the mol ratio of 1:1:2 2 CO 3 、CaCO 3 And V 2 O 5 Then to Ag 2 CO 3 、CaCO 3 And V 2 O 5 Grinding and uniformly mixing; then Ag is added 2 CO 3 、CaCO 3 And V 2 O 5 Placing the mixture in an alumina crucible, and maintaining the temperature at 450-500 ℃ for 120 minutes to obtain Ag 2 CaV 4 O 12 。
3. The high potential gradient high nonlinear coefficient zinc oxide varistor medium of claim 1, characterized in that said ZnTeO 4 The preparation method comprises the following steps: according to the following steps of 1:1 molar ratio of ZnO and TeO 3 Then for ZnO and TeO 3 Grinding and uniformly mixing; then ZnO and Te are addedO 3 Placing the mixture in an alumina crucible, and preserving heat at 550-600 ℃ for 120 minutes to obtain ZnTeO 4 。
4. The method for preparing the high-potential-gradient high-nonlinear-coefficient zinc oxide varistor medium as claimed in claim 1, which is characterized by comprising the following steps:
(1) Preparing ZnO and Sb according to a certain proportion 2 O 3 、Co 2 O 3 、Bi 2 O 3 、Ni 2 O 3 、Cr 2 O 3 、Ag 2 CaV 4 O 12 、Al 2 O 3 Zinc borate, liNO 3 And ZnTeO 4 ；
(2) Preparation of additive slurries
Sb prepared in the step (1) 2 O 3 、Co 2 O 3 、Bi 2 O 3 、Ni 2 O 3 、Cr 2 O 3 、Ag 2 CaV 4 O 12 、Al 2 O 3 Zinc borate, liNO 3 And ZnTeO 4 Mixing to obtain a mixture; adding pure water and an ammonium salt dispersing agent into the mixture for ball milling, so that the components are uniformly mixed, and an additive slurry is obtained;
(3) Preparation of spray slurry
Adding ZnO prepared in the step (1) into the additive slurry, and adding a polyvinyl alcohol aqueous solution to obtain mixed slurry; ball milling is carried out on the mixed slurry until the specific gravity of the mixed slurry is 1.5-2.0 and the viscosity is 40-200cps, and spray slurry is obtained;
(4) Spraying and granulating the spraying slurry obtained in the step (3) by using a spray drying tower to obtain powder;
(5) Dry-pressing to form the powder obtained in the step (4) into a green sheet;
(6) And (3) removing polyvinyl alcohol from the green sheet obtained in the step (5), and then preserving heat for 2-4 hours in an environment with the temperature of 950-980 ℃ to sinter the green sheet, thereby obtaining the zinc oxide varistor medium with high potential gradient and high nonlinear coefficient.
5. The method for preparing the high-potential-gradient high-nonlinearity-coefficient zinc oxide varistor medium according to claim 4, wherein the method comprises the following steps: in the step (2), during ball milling, the adding amount of the ammonium salt dispersing agent is 0.8-1.3% of the total weight of the mixture, and the weight ratio of the ball-milled mixture, the ball and the water is as follows: mixture, ball, water=1:3 (0.6-1.0).
6. The method for preparing the high-potential-gradient high-nonlinearity-coefficient zinc oxide varistor medium according to claim 4, wherein the method comprises the following steps: in the step (3), the solid content of the added polyvinyl alcohol aqueous solution is ZnO and Sb 2 O 3 、Co 2 O 3 、Bi 2 O 3 、Ni 2 O 3 、Cr 2 O 3 、Ag 2 CaV 4 O 12 、Al 2 O 3 Zinc borate, liNO 3 And ZnTeO 4 0.9-1.3% of the total weight of (C).
7. The method for preparing the high-potential-gradient high-nonlinearity-coefficient zinc oxide varistor medium according to claim 4, wherein the method comprises the following steps: in step (6), the green sheet is placed in an environment of 500-550 ℃ to exclude polyvinyl alcohol.
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| CN117843346A (en) * | 2024-01-09 | 2024-04-09 | 汕头保税区松田电子科技有限公司 | A high-stability, low-resistivity NTC thermistor dielectric material and preparation method thereof |
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| CN117843346A (en) * | 2024-01-09 | 2024-04-09 | 汕头保税区松田电子科技有限公司 | A high-stability, low-resistivity NTC thermistor dielectric material and preparation method thereof |
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