CN114388205A - Varistor material, method for producing same, and method for producing varistor - Google Patents
Varistor material, method for producing same, and method for producing varistor Download PDFInfo
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- CN114388205A CN114388205A CN202111627413.9A CN202111627413A CN114388205A CN 114388205 A CN114388205 A CN 114388205A CN 202111627413 A CN202111627413 A CN 202111627413A CN 114388205 A CN114388205 A CN 114388205A
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- 239000000463 material Substances 0.000 title claims abstract description 37
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 25
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000000654 additive Substances 0.000 claims abstract description 34
- 230000000996 additive effect Effects 0.000 claims abstract description 31
- 238000000498 ball milling Methods 0.000 claims abstract description 27
- 239000011787 zinc oxide Substances 0.000 claims abstract description 26
- 150000002500 ions Chemical class 0.000 claims abstract description 24
- 239000002002 slurry Substances 0.000 claims abstract description 23
- 238000005245 sintering Methods 0.000 claims abstract description 22
- 239000002019 doping agent Substances 0.000 claims abstract description 16
- 239000000843 powder Substances 0.000 claims abstract description 15
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 11
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- UPWOEMHINGJHOB-UHFFFAOYSA-N cobalt(III) oxide Inorganic materials O=[Co]O[Co]=O UPWOEMHINGJHOB-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000004014 plasticizer Substances 0.000 claims abstract description 7
- 239000011230 binding agent Substances 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 25
- 229910052709 silver Inorganic materials 0.000 claims description 10
- 239000004332 silver Substances 0.000 claims description 10
- 239000002003 electrode paste Substances 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 238000000605 extraction Methods 0.000 claims description 6
- 239000011265 semifinished product Substances 0.000 claims description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- 238000005266 casting Methods 0.000 claims description 3
- 229910010293 ceramic material Inorganic materials 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 14
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 9
- 230000007423 decrease Effects 0.000 description 6
- 239000002270 dispersing agent Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 230000001419 dependent effect Effects 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 3
- GNMQOUGYKPVJRR-UHFFFAOYSA-N nickel(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Ni+3].[Ni+3] GNMQOUGYKPVJRR-UHFFFAOYSA-N 0.000 description 3
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 2
- SWELZOZIOHGSPA-UHFFFAOYSA-N palladium silver Chemical compound [Pd].[Ag] SWELZOZIOHGSPA-UHFFFAOYSA-N 0.000 description 2
- 238000005036 potential barrier Methods 0.000 description 2
- 229940090181 propyl acetate Drugs 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01C—RESISTORS
- H01C7/00—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material
- H01C7/10—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material voltage responsive, i.e. varistors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01C—RESISTORS
- H01C17/00—Apparatus or processes specially adapted for manufacturing resistors
- H01C17/06—Apparatus or processes specially adapted for manufacturing resistors adapted for coating resistive material on a base
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01C—RESISTORS
- H01C17/00—Apparatus or processes specially adapted for manufacturing resistors
- H01C17/28—Apparatus or processes specially adapted for manufacturing resistors adapted for applying terminals
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- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Thermistors And Varistors (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
The application discloses a piezoresistor material, a manufacturing method thereof and a manufacturing method of a piezoresistor. The manufacturing method comprises the following steps: providing a raw powder comprising a grain boundary additive and dopant ions, the grain boundary additive comprising Bi2O3、Sb2O3And Co2O3The dopant ions include Al3+、In3+、Ga3+、Nb5+、Ni3+、Mn4+At least one of; adding the raw powder into a solvent for carrying out first ball milling treatment to obtain first slurry; adding zinc oxide into the first slurry, and performing second ball milling treatment to obtain second slurry; and adding a binder and a plasticizer into the second slurry, and carrying out third ball milling treatment to obtain the piezoresistor material. The varistor material of the present application may be inThe ceramic material is matched with the inner electrode for sintering at a lower temperature, and can still maintain better pressure-sensitive characteristic and lower leakage current at a high temperature.
Description
Technical Field
The application relates to the field of piezoresistors and manufacturing thereof, in particular to a piezoresistor material, a manufacturing method thereof and a manufacturing method of a piezoresistor.
Background
The piezoresistor is an electronic component with the resistance value changing along with the voltage nonlinearity, and the piezoresistor sold in the market at present mainly takes zinc oxide as a main component, and is formed by adding other metal oxide components and sintering the mixture into a ceramic body at high temperature. The piezoresistor has higher nonlinear coefficient and higher large current absorption capacity, so the piezoresistor is widely applied to the protection field of electronic circuits.
The upper limit of the use temperature of the voltage dependent resistor products sold in the market at present is about 85-125 ℃, when the temperature is further increased, the leakage current of the products is rapidly increased, the power consumption of the circuit operation is increased, meanwhile, the temperature of the products is continuously increased due to the increase of the heat productivity of the products, and the products face the risk of burning. In addition, the increase of the temperature can also reduce the voltage-sensitive voltage and the nonlinear coefficient of the piezoresistor, so that the product loses the voltage-sensitive characteristic and loses the protection effect on the circuit. With the rapid development of the electronic industry, the usage scenarios of electronic devices are continuously widened, and the varistor serving as a circuit protection device needs to be adapted to a higher-temperature working environment (such as a part of the usage scenarios of vehicle-mounted electronics), so that a varistor capable of maintaining high stability at a high temperature needs to be developed.
On the other hand, the sintering temperature of the piezoresistor is about 1000 ℃ at present, the piezoresistor needs to be matched with high-temperature-resistant sintered silver palladium slurry when a patch product is manufactured, and the cost of the piezoresistor is in a higher level due to overhigh price of palladium. In order to reduce the manufacturing cost, pure silver inner paste is used for replacing silver palladium paste, the melting point of silver is about 950 ℃, and the sintering temperature of the ceramic material for preparing the piezoresistor is required to be reduced to be lower than the temperature so as to be matched with the silver layer of the inner electrode for sintering. There is thus a need for a varistor material that can be co-fired at low temperature to match the pure silver material.
Disclosure of Invention
The embodiment of the application provides a piezoresistor material, a manufacturing method thereof and a manufacturing method of a piezoresistor, so that the piezoresistor material can be matched and sintered with an inner electrode at a lower temperature, and a better piezoresistor characteristic and a lower leakage current can be still maintained at a high temperature.
In a first aspect, an embodiment of the present application provides a method for manufacturing a varistor material, including:
s1: providing a raw powder comprising a grain boundary additive and dopant ions, the grain boundary additive comprising Bi2O3、Sb2O3And Co2O3The dopant ions include Al3+、In3+、Ga3+、Nb5+、Ni3+、Mn4+At least one of; adding the raw powder into a solvent for carrying out first ball milling treatment to obtain first slurry;
s2: adding zinc oxide into the first slurry, and performing second ball milling treatment to obtain second slurry;
s3: and adding a binder and a plasticizer into the second slurry, and carrying out third ball milling treatment to obtain the piezoresistor material.
Alternatively, the particle size of the zinc oxide satisfies: d95 is 0.5-1.0 μm.
Optionally, in the grain boundary additive, Bi2O3And Sb2O3In a molar ratio of 3:1 to 4.5:1, Bi2O3And Co2O3The molar ratio of (a) to (b) is 1:1 to 1.2: 1.
Optionally, the molar ratio of the grain boundary additive to the zinc oxide is 1:100 to 1.4: 100.
Alternatively, in the raw powder of the S1 step, the dopant ions are represented by at least one of an oxide, a carbonate, and a nitrate containing the dopant ions.
Optionally, the mass ratio of the doped ions to the zinc oxide is 2% to 5%.
In a second aspect, an embodiment of the present application provides a method for manufacturing a varistor, including the method according to any one of the preceding claims, after step S3, further including:
s4: casting to form a piezoresistor diaphragm with a preset size;
s5: forming inner electrode paste on the piezoresistor film, forming a structure in which a plurality of layers of piezoresistor films and a plurality of layers of inner electrode paste are sequentially laminated, and sintering to obtain a semi-finished product;
s6: and forming extraction electrodes at two opposite ends of the semi-finished product, and connecting the extraction electrodes with the sintered inner electrodes to form the piezoresistor.
Alternatively, in the S5 step, the sintering treatment temperature is A, and 870 ℃. ltoreq. A.ltoreq.910 ℃.
Optionally, the internal electrode paste includes silver.
In a third aspect, embodiments of the present application provide a varistor material produced by using the method of any one of the preceding claims.
As described above, in the embodiments of the present application, the grain boundary additive can greatly reduce the proportion of grain boundary phases (e.g., grain boundary Bi-rich phases) and the proportion of pinning phases in the varistor (material), so as to facilitate retention of only essential grain boundary components that promote zinc oxide grain growth and maintain the varistor characteristics, and facilitate sintering, thereby facilitating sintering at a lower temperature (e.g., 910 ℃ and below), and matching sintering with an internal electrode material such as silver paste; in addition, the grain boundary Bi-rich phase is a main channel of leakage current under low field intensity, so that the reduction of the leakage current is facilitated; on the other hand, by adjusting the proportion of Bi, Co and Sb ions in the crystal boundary phase, the crystal boundary potential barrier is improved, the nonlinear coefficient of the product is improved, and the leakage current of the product is further reduced; meanwhile, the grain resistance is reduced by doping high-valence ions, and the through-current density of the material is improved.
Drawings
FIG. 1 is a schematic flow chart of a method for manufacturing a varistor material according to an embodiment of the present application;
FIG. 2 is a schematic flow chart of a method for manufacturing a varistor according to an embodiment of the present application;
fig. 3 is a schematic diagram of electrical parameters of a varistor according to an embodiment of the present disclosure during a temperature characteristic test.
Detailed Description
In order to make the objects, technical solutions and advantages of the present application more apparent, the technical solutions of the present application will be described below in detail with reference to specific embodiments and accompanying drawings. It should be apparent that the embodiments described below are only some embodiments of the present application, and not all embodiments. In the following embodiments and features thereof, the present invention may be combined with each other and also belong to the technical solutions of the present application.
Fig. 1 is a schematic flow chart of a method for manufacturing a varistor material according to an embodiment of the present application. Referring to fig. 1, the method for manufacturing the varistor material includes the following steps S1-S3.
S1: providing a raw powder comprising a grain boundary additive and dopant ions, the grain boundary additive comprising Bi2O3、Sb2O3And Co2O3The dopant ions include Al3+、In3+、Ga3+、Nb5+、Ni3+、Mn4+At least one of; and adding the raw powder into a solvent for carrying out first ball milling treatment to obtain first slurry.
S2: and adding zinc oxide into the first slurry, and performing second ball milling treatment to obtain second slurry.
S3: and adding a binder and a plasticizer into the second slurry, and carrying out third ball milling treatment to obtain the piezoresistor material.
In step S1, in some scenarios, the additives including the grain boundary additive, the dopant ion, and the dispersant are mixed in the solvent according to a predetermined ratio to perform a first ball milling process, so that the additives and the solvent are sufficiently and uniformly mixed. Alternatively, the solvent may be propyl acetate and ethanol in a mass ratio of 7.5: 2.5; the mass ratio of the zirconia balls subjected to ball milling, the additive and the solvent can be 8:1: 3; the dispersing agent can be beneficial to crushing particles in the ball milling process, prevent the crushed particles from coagulating and keep the dispersion stable, and the addition amount of the dispersing agent is 0.8-1.5% of the total mass of the additive powder designed in the step S1; the first ball milling treatment can mill the additive to a particle size D95 of 1.5-2.0 μm.
In step S2, zinc oxide is added to the first slurry obtained in step S1, and ball milling treatment is continued, that is, secondary ball milling treatment is performed, so that the powder materials are uniformly mixed.
In the step S3, in some scenarios, a binder and a plasticizer are added to the second slurry obtained in the step S2, the ball milling is continued (i.e., a third ball milling treatment is performed), and the time can last for 20h to 30h, so as to prepare a uniform varistor material with a predetermined viscosity. Specific materials and types of the binder and the plasticizer can be found in the prior art, and the detailed description of the embodiments of the present application is omitted.
The varistor material manufactured through the foregoing steps of S1 to S3 has advantageous effects that the method of the corresponding embodiment has. Also, the varistor material prepared through the foregoing steps of S1 to S3 may be used to manufacture a varistor, the manufacturing method of which includes steps of S1 to S6, as shown in fig. 2.
S4: and casting to form the piezoresistor film with preset size.
S5: forming inner electrode paste on the piezoresistance film, forming a structure that the multilayer piezoresistance film and the multilayer inner electrode paste are sequentially laminated, and sintering to obtain a semi-finished product.
S6: and forming extraction electrodes at two opposite ends of the semi-finished product, and connecting the extraction electrodes with the sintered inner electrodes to form the piezoresistor.
In the manufacturing method of the embodiment of the application, the grain boundary additive can greatly reduce the proportion of a grain boundary phase (such as a grain boundary Bi-rich phase) and the proportion of a pinning phase in a piezoresistor (material), so that only necessary grain boundary components for promoting the growth of zinc oxide grains and maintaining the pressure-sensitive characteristic are reserved, the sintering can be promoted, and the sintering at a lower temperature (such as 910 ℃ and below) and the matched sintering with an internal electrode material such as silver paste are promoted; in addition, the grain boundary Bi-rich phase is a main channel of leakage current under low field intensity, so that the reduction of the leakage current is facilitated; on the other hand, by adjusting the proportion of Bi, Co and Sb ions in the crystal boundary phase, the crystal boundary potential barrier is improved, the nonlinear coefficient of the product is improved, and the leakage current of the product is further reduced; meanwhile, the grain resistance is reduced by doping high-valence ions, and the through-current density of the material is improved.
It should be understood that in an actual scenario, the specific processes of the respective steps may be adaptively determined; the ratio and particle size of the various materials are not limited in the examples of the present application.
For example, the particle size of zinc oxide satisfies: d95 is 0.5-1.0 μm, has small and uniform particle size, and is helpful for reducing sintering and for the grain boundary additive and doping ion to play corresponding roles in the sintering process.
For example, in the grain boundary additive, Bi2O3And Sb2O3In a molar ratio of 3:1 to 4.5:1, Bi2O3And Co2O3The molar ratio of (A) to (B) is 1: 1-1.2: 1; for another example, the molar ratio of the grain boundary additive to the zinc oxide is 1:100 to 1.4: 100; for example, the mass ratio of the dopant ion to the zinc oxide is 2 to 5%. By adjusting various materials within the corresponding proportion range, the varistor material can be matched and sintered with the inner electrode at a lower temperature, and can still maintain better varistor characteristics and lower leakage current at a high temperature.
For example, in the raw powder of step S1, the dopant ions are at least one of an oxide, a carbonate, and a nitrate containing the dopant ions, which facilitates rapid access of the dopant ions during sintering.
The foregoing manufacturing method is described below by way of example with specific embodiments, and in fig. 3, the stem sample can be regarded as the existing varistor described in the foregoing background.
Example 1
The main material (namely zinc oxide) and the additive have the following mole parts: 100 parts of zinc oxide; additive: bi2O30.55 part of Co2O30.54 part of Sb2O30.14 part of Mn3O40.06 part of Nb2O50.04 part of Ni2O30.02 part of Al (NO)3)3·9H2And O is 0.01 part.
Weighing an additive, a solvent and a dispersing agent according to the mass ratio, adding the additive and the solvent (the mass ratio of propyl acetate to ethanol is 7.5/2.5) into a ball milling tank, wherein the mass ratio of the additive to the solvent is 8:1:3, the addition amount of the dispersing agent is 1% of the total mass of the powder designed in the step S1, the rotation speed of the first ball milling is 200-400 rpm, and the time is 14-20h, so that the powder materials are uniformly mixed.
After the first ball milling treatment of the additive is finished, weighing zinc oxide powder, adding the zinc oxide powder, and continuing ball milling (namely, second ball milling) for 24 hours to uniformly mix the zinc oxide and the additive.
And then adding a proper amount of adhesive and plasticizer into the slurry, and continuously performing ball milling (namely, third ball milling) for 24 hours to obtain zinc oxide ceramic slurry which is uniformly dispersed and has certain viscosity, namely the piezoresistor material.
Further, in a scene of preparing the piezoresistor, the zinc oxide ceramic slurry is cast into a membrane with the thickness of 20-40 μm, a sheet type piezoresistor product with a preset size specification (such as 4532 size specification) is prepared according to a multilayer sheet type piezoresistor lamination process, pure silver slurry is used as an inner electrode material, the sintering is carried out for 2 hours in an air atmosphere at 910 ℃, the cooling is carried out to the room temperature, electrodes are adhered to two ends of the product, and the product preparation is completed after silver burning and electroplating, so that the finally required multilayer sheet type piezoresistor is obtained.
As shown in the attached table I and FIG. 3, the prepared piezoresistor has the test results that the potential gradient is 350V/mm, the average value of the nonlinear coefficients is 51, the leakage current (under 0.75V1 mA) is 0.01 muA, and the impact current density of 8/20 muS resistance is 59A/mm2。
| Temperature/. degree.C | Voltage-dependent voltage/V | Leakage current/. mu.A | Coefficient of |
| 25 | 37.55 | 0.01 | 45.6 |
| 50 | 37.55 | 0.04 | 47 |
| 75 | 37.6 | 0.08 | 46.4 |
| 100 | 37.65 | 0.29 | 43 |
| 125 | 37.65 | 0.93 | 40 |
| 150 | 37.59 | 2.56 | 35.9 |
| 175 | 37.49 | 6.90 | 31.1 |
Attached watch 1
The results shown in the attached table i and fig. 3 show that the varistor voltage of the embodiment of the present application does not decrease significantly when the ambient temperature increases to 150 ℃, and after the ambient temperature increases to 175 ℃, the varistor voltage decreases by only 0.16%, the leakage current is 6.9 μ Α, and the nonlinear coefficient is maintained above 30, which indicates that the varistor still maintains good varistor characteristics and low leakage current at 175 ℃.
Example 2
The main material (namely zinc oxide) and the additive have the following mole parts: 100 parts of zinc oxide; additive: bi2O30.5 part of Co2O30.44 part of Sb2O30.17 part of Mn3O40.05 part of Nb2O50.036 part of Ni2O30.015 part of Al (NO)3)3·9H2And O is 0.015 part.
The varistor was obtained by following the procedure of example 1 and completing the sintering at 890 ℃.
The electrical parameters of the piezoresistor subjected to temperature characteristic test are shown in the attached table II and figure 3, and the prepared piezoresistor is tested, the potential gradient is 405V/mm, the nonlinear coefficient average value is 53.6, the leakage current (under 0.75V1 mA) is 0.05 muA, and the impact current density of 8/20 mus impact resistance is 51A/mm2。
| Temperature/. degree.C | Voltage-dependent voltage/V | Leakage current/. mu.A | Coefficient of |
| 25 | 43.45 | 0.05 | 53.6 |
| 50 | 43.46 | 0.09 | 54 |
| 75 | 43.52 | 0.14 | 51.9 |
| 100 | 43.55 | 0.64 | 48.4 |
| 125 | 43.47 | 1.7 | 44.1 |
| 150 | 43.38 | 4.29 | 37.5 |
| 175 | 43.11 | 11.8 | 32.6 |
Attached watch 2
The results shown in the attached table ii and fig. 3 show that the varistor voltage of the embodiment of the present application does not decrease significantly when the ambient temperature increases to 150 ℃, and after the ambient temperature increases to 175 ℃, the varistor voltage decreases by only 0.7%, the leakage current is 11.8 μ Α, and the nonlinear coefficient is maintained above 32.6, which indicates that the varistor still maintains good varistor characteristics and leakage current within the required range at 175 ℃.
Example 3
The main material (namely zinc oxide) and the additive have the following mole parts: 100 parts of zinc oxide; additive: bi2O30.6 part of Co2O30.58 part of Sb2O30.14 part of Mn3O40.07 part of Nb2O5Is 0.045 parts of Ni2O30.025 parts of Al (NO)3)3·9H2And O is 0.01 part.
The varistor was obtained by following the procedure of example 1 and completing the sintering at 870 ℃.
The electrical parameters of the piezoresistor subjected to temperature characteristic test are shown in the third table and figure 3, and the prepared piezoresistor is tested to have the potential gradient of 550V/mm, the nonlinear coefficient average value of 54.4, the leakage current (under 0.75V1 mA) of 0.03 muA and the impact current density of 8/20 muS resistance of 45A/mm2。
| Temperature/. degree.C | Voltage-dependent voltage/V | Leakage current/. mu.A | Coefficient of |
| 25 | 62.03 | 0.03 | 54.4 |
| 50 | 62.83 | 0.05 | 53.4 |
| 75 | 62.79 | 0.13 | 53.3 |
| 100 | 62.2 | 0.58 | 49.6 |
| 125 | 62.15 | 1.4 | 46.2 |
| 150 | 61.98 | 3.7 | 40.9 |
| 175 | 61.68 | 11.5 | 33.9 |
Attached table III
The results shown in the attached table iii and fig. 3 show that the varistor voltage of the embodiment of the present application does not decrease significantly when the ambient temperature increases to 150 ℃, and after the ambient temperature increases to 175 ℃, the varistor voltage decreases by only 0.56%, the leakage current is 11.5 μ a, and the nonlinear coefficient is maintained above 30, which indicates that the varistor still maintains good varistor characteristics and leakage current within the required range at 175 ℃.
It should be understood that the above-mentioned embodiments are only some examples of the present application, and not intended to limit the scope of the present application, and all equivalent structural changes made by using the contents of the present specification and the drawings are included in the protection scope of the present application for those skilled in the art.
Claims (10)
1. A method of making a varistor material, comprising:
s1: providing a raw powder comprising a grain boundary additive and dopant ions, the grain boundary additive comprising Bi2O3、Sb2O3And Co2O3The doping ions comprise Al3+、In3+、Ga3+、Nb5+、Ni3+、Mn4+At least one of; adding the raw powder into a solvent for carrying out first ball milling treatment to obtain first slurry;
s2: adding zinc oxide into the first slurry, and performing second ball milling treatment to obtain second slurry;
s3: and adding a binder and a plasticizer into the second slurry, and carrying out third ball milling treatment to obtain the piezoresistor material.
2. The method according to claim 1, wherein the particle size of the zinc oxide satisfies: d95 is 0.5-1.0 μm.
3. The method of claim 1, wherein the Bi is in the grain boundary additive2O3And Sb2O3In a molar ratio of 3:1 to 4.5:1, Bi2O3And Co2O3In a molar ratio of 1:1 to 1.2:1。
4. The method of claim 1 or 3, wherein the molar ratio of the grain boundary additive to the zinc oxide is 1:100 to 1.4: 100.
5. The method according to claim 1, wherein the dopant ions represent at least one of an oxide, a carbonate, and a nitrate containing the dopant ions in the raw powder.
6. The method according to claim 1 or 5, wherein the mass ratio of the doping ions to the zinc oxide is 2 to 5% o.
7. A method of manufacturing a varistor, comprising the method of any one of claims 1 to 6, and further comprising, after the step of S3:
s4: casting to form a piezoresistor diaphragm with a preset size;
s5: forming inner electrode paste on the piezoresistor film, forming a structure in which a plurality of layers of piezoresistor films and a plurality of layers of inner electrode paste are sequentially stacked, and sintering to obtain a semi-finished product;
s6: and forming extraction electrodes at two opposite ends of the semi-finished product, wherein the extraction electrodes are connected with the sintered inner electrodes to form the piezoresistor.
8. The method of claim 7, wherein in the S5 step, the sintering treatment temperature is A, and 870 ℃ ≦ A ≦ 910 ℃.
9. The method of claim 7, wherein the internal electrode paste comprises silver.
10. A varistor material, characterized in that it is obtained by using the method according to any one of claims 1 to 6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111627413.9A CN114388205B (en) | 2021-12-28 | 2021-12-28 | Varistor material, method for producing same, and method for producing varistor |
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| CN115073163A (en) * | 2022-07-01 | 2022-09-20 | 深圳振华富电子有限公司 | Chip varistor and preparation method and application thereof |
| CN116023145A (en) * | 2022-12-29 | 2023-04-28 | 湖南福德电气有限公司 | Preparation method of silicon carbide series piezoresistor |
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| CN111499373A (en) * | 2020-04-28 | 2020-08-07 | 如东宝联电子科技有限公司 | Laminated zinc oxide composition suitable for low-temperature co-firing with silver inner electrode and manufacturing method thereof |
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| US20120135563A1 (en) * | 2010-11-26 | 2012-05-31 | Sfi Electronics Technology Inc. | Process for producing multilayer chip zinc oxide varistor containing pure silver internal electrodes and firing at ultralow temperature |
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| CN116023145A (en) * | 2022-12-29 | 2023-04-28 | 湖南福德电气有限公司 | Preparation method of silicon carbide series piezoresistor |
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