CN102515743A - Method for preparing zinc oxide varistors while increasing potential gradient and nonlinear coefficient - Google Patents
Method for preparing zinc oxide varistors while increasing potential gradient and nonlinear coefficient Download PDFInfo
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Abstract
A method for preparing zinc oxide varistors includes: firstly, preparing sufficiently semiconducted crystal grains doped with zinc oxide; secondly, mixing the crystal grains with prepared inter-crystal phase components; and finally, forming the zinc oxide varistors by the sintering process. The difference between the method for preparing zinc oxide varistors and the known method for preparing zinc oxide varistors includes that the process of preparing the sufficiently semiconducted crystal grains doped with zinc oxide and the process of preparing high-impedance sintered powder are separated from each other. The method for preparing zinc oxide varistors has the advantages of increasing the potential gradient and the nonlinear coefficient of the zinc oxide varistors simultaneously and is applicable to manufacturing the zinc oxide varistors with the potential gradient ranging from 1200-9000V/mm and the nonlinear coefficient alpha ranging from 21.5 to 55.
Description
Technical field
The present invention relates to a kind of method for making of zinc oxide varistor, refer to a kind of method for making that makes zinc oxide varistor improve potential gradient and nonlinear factor simultaneously especially.
Background technology
Zinc oxide varistor has excellent Fei Aomu characteristic, is best overvoltage protection, is applied to that the Transient Voltage Suppressor as the protection assembly uses in electric power or the Circuits System, can bring into play to prevent moment surging and the effect of protection assembly.
Yet, along with countries in the world to the march toward planning of extra-high voltage transmission of power system, zinc oxide varistor must possess high potential gradient (potential gradient) and high-energy absorption characteristic, has become important development trend.
As everyone knows, the potential gradient of zinc oxide varistor is relevant with the zinc oxide grain boundaries quantity in the unit thickness, that is zinc oxide grain is more little in the unit thickness, and then the crystal boundary number is many more, and its potential gradient is also big more.Classical theory thinks that the voltage breakdown of zinc oxide grain boundaries is about the 3V/1 crystal boundary.And the Fei Aomu characteristic of zinc oxide varistor is because of formed pair of Schottky barrier between two zinc oxide grains, improves the height of potential barrier, can improve the nonlinear factor of zinc oxide varistor and the voltage breakdown of zinc oxide grain boundaries.
But; Use conventional formulation and the prepared zinc oxide varistor of technology, its potential gradient is merely
energy tolerance density and is not suitable for being applied on the circuit of extra-high voltage transmission for
.
Therefore, in order to develop the zinc oxide varistor of tool high potential gradient, the employed method of prior art, can conclude following two aspects:
One, in the dopant ion of zincite crystal, add the rare-earth oxide composition, the potential gradient of the prepared zinc oxide varistor of result is increased to 400V/mm;
Two, improve the preparation technology or the introducing novel process of zinc oxide ceramics powder, for example, introduce high-energy ball milling technology or nanometer flouring technology, the potential gradient of the prepared zinc oxide varistor of result is increased to 2,000V/mm.
But above-mentioned prior art to zinc oxide varistor raising potential gradient the rheostatic potential gradient of zinc oxide but occurs in case improve, and the shortcoming that its nonlinear factor descends.This is to the performance of zinc oxide varistor, and especially the pressure limiting influential effect to zinc oxide varistor is very big.
Summary of the invention
In view of this; Main purpose of the present invention is to provide a kind of method for making of zinc oxide varistor; Comprise: the doping zinc-oxide crystal grain of prefabricated abundant semiconductor earlier; And then mix with ready-formed intergranular phase component, through the prepared zinc oxide varistor of sintering process, have the advantages that to improve zinc oxide varistor potential gradient and nonlinear factor simultaneously at last.
Method for making of the present invention; With the difference of the known method for making of zinc oxide varistor, mainly be doping zinc-oxide crystal grain, with the agglomerated powder or the glass powder (claiming the intergranular phase component again) of preparation high resistance with the abundant semiconductor of preparation; Being divided into two independent process prepares; And obtain following beyond thought advantage, and broken through the restriction of the known method for making of zinc oxide varistor, so prepared zinc oxide varistor has high potential gradient and high nonlinear coefficient concurrently:
1. the schottky barrier height between the raising zinc oxide grain;
2. the crystal boundary number between the zinc oxide grain in the increase unit thickness;
3. improve the homogeneity of component and structure.
Description of drawings
Fig. 1 is embodiment 4 specimen coding No 3-nm ZnO
*The X-ray diffraction collection of illustrative plates of crystal grain.
Fig. 2 is embodiment 4 specimen coding No 4-nm ZnO
*The X-ray diffraction collection of illustrative plates of crystal grain.
Fig. 3 is the I-V figure of embodiment 4 specimen coding No 3-nm disk type zinc oxide varistors.
Fig. 4 is the I-V figure of embodiment 4 specimen coding No 4-nm disk type zinc oxide varistors.
Fig. 5 processes the electronic scanning sectional view photo of disk type zinc oxide varistor with the ZnO crystal grain of dopant ion not for embodiment 8.
Fig. 6 is the ZnO of embodiment 8 with dopant ion
*Crystal grain is processed the electronic scanning sectional view photo of disk type zinc oxide varistor.
Embodiment
Zinc oxide varistor method for making of the present invention is applicable to and makes the zinc oxide varistor with superelevation potential gradient and nonlinear factor, preferable use be used to make potential gradient between
Nonlinear factor α between
And leakage current I
LBetween
Zinc oxide varistor; Best use is to be used to make the zinc oxide varistor that potential gradient surpasses 2000V/mm.
Zinc oxide varistor method for making of the present invention may further comprise the steps:
A) according to the potential gradient of zinc oxide varistor between
prefabricated doping non-equivalence ionic zinc oxide grain;
B) according to the potential gradient of zinc oxide varistor agglomerated powder (or glass powder) between
prefabricated high resistance;
C) be raw material with the zinc oxide grain of step a) and the agglomerated powder of step b), the ceramics powder that the preparation zinc oxide varistor is used; And
D) ceramics powder of use step c), the preparation potential gradient is between the zinc oxide varistor of
nonlinear factor α between
.
Step a) in method for making of the present invention is to make zinc oxide grain see through non-equivalence ionic doping (that is displacement Zn,
2+Ion or calking), but in the crystal growth of sintering process inhibited oxidation zinc, and reach abundant semiconductor.
According to the crystallography principle; The adulterated non-equivalence ion of zinc oxide grain, must be selected from by lithium (Li), copper (Cu), aluminium (Al), cerium (Ce), cobalt (Co), chromium (Cr), indium (In), gallium (Ga), molybdenum (Mo), manganese (Mn), niobium (Nb), lanthanum (La), yttrium (y), praseodymium (Pr), antimony (Sb), nickel (Ni), titanium (Ti), vanadium (v), the colony that formed of tungsten (W), zirconium (Zr), iron (Fe), boron (B), silicon (Si) and tin (Sn) wherein one or more; And non-equivalence ionic doping must be decided according to practical situation, and its doping is less than the 20mol% of zinc oxide.
Preparation zinc oxide grain doping non-equivalence ionic method comprises following two kinds:
1. method one:
Specified performance according to zinc oxide varistor; Select the soluble salt of intending dopant ion for use; Be mixed with the certain density aqueous solution; With Zinc oxide powder join in the above-mentioned solution through stir, after the oven dry; Again through
calcining, at last with sintered material through broken and levigate for use to required fineness.
2. method two:
According to the specified performance of zinc oxide varistor, adopt the physics method or the chemical method nanotechnology of preparation micro mist, preparation contains the zinc oxide grain of intending dopant ion.Wherein, said physics method comprises vapour deposition process, laser method, microwave method etc.; Said chemical method comprises the precipitator method, micro emulsion method, hydrothermal method, phase transfer method and sol-gel method etc.
Like the applied chemistry precipitator method, the solution that will contain zine ion mixes with the solution that contains dopant ion through stirring processes the homogeneous mixture solotion that contains zine ion and dopant ion; Under agitation condition, adopt forward or reverse addition method, precipitant solution is added above-mentioned mixing solutions, after controlling suitable pH value, obtain coprecipitate.Through repeatedly cleaning, after oven dry,, can obtain to contain the zinc oxide grain of dopant ion to coprecipitate at suitable temperature lower calcination.
Described precipitation agent can be selected from oxalic acid, urea, volatile salt, bicarbonate of ammonia, ammoniacal liquor, thanomin or other basic soln.Calcining temperature is looked the decomposition temperature of coprecipitate and is decided.
As use sol-gel method (Sol-Gel method); Be zine ion to be dispersed in contain in the inorganic salt or metal alkoxide colloidal sol of intending dopant ion; Through being hydrolyzed, after bunching reaction forms colloidal sol, again through solidifying and thermal treatment makes doping non-equivalence ionic zinc oxide grain.
Above-mentioned two kinds of nanometer technologies of preparing; Can obtain the dopant ion composition is scattered very uniform tiny particle diameter zinc oxide grain; And thermal treatment temp is lower, between
and be convenient to mass production.
Step a) in the method for making of the present invention is independently different operations with step b).Step b) in method for making of the present invention is an agglomerated powder (or claiming the intergranular phase component) of preparing different components according to the performance of zinc oxide varistor.
The method of the agglomerated powder of preparation high resistance comprises following two kinds:
1. method one:
Specified performance according to zinc oxide varistor; Wherein one or more oxide compound, oxyhydroxide, carbonate, nitrate salt or the oxalate that must be selected from bismuth-containing (Bi), antimony (Sb), manganese (Mn), cobalt (Co), chromium (Cr), nickel (Ni), titanium (Ti), silicon (Si), barium (Ba), boron (B), selenium (Se), lanthanum (La), praseodymium (Pr), yttrium (Y), indium (In), aluminium (Al) or tin (Sn) is raw material; The sintered material raw material of preparation different components behind thorough mixing; It is thin to required fineness to regrind through oversintering, promptly processes the agglomerated powder with high resistance performance; Or with after the raw materials mix, through high-temperature digestion, shrend, oven dry, regrinding is fine into agglomerated powder.
For example, said sintered material is an oxide raw material, must be selected from bismuth oxide (Bi
2O
3), boron oxide (B
2O
3), Antimony Trioxide: 99.5Min (Sb
2O
3), powder blue (Co
2O
3), Manganse Dioxide (MnO
2), chromic oxide (Cr
2O
3), Vanadium Pentoxide in FLAKES (V
2O
3), zinc oxide (ZnO), nickel oxide (NiO), silicon-dioxide (SiO
2) or wherein two or more mixture such as rare earth oxide.Wherein, said sintered material optionally adds the purpose of zinc oxide (ZnO) composition, is to promote the coking property of intergranular phase.
2. method two:
According to the specified performance of zinc oxide varistor, adopt the preparation of physics method or chemical method nanotechnology to have the nano particle of specified ingredients.The present invention preferably uses methods such as chemical precipitation method, micro emulsion method or sol-gel method to prepare the nano particle with high resistance performance.This method can obtain the tiny agglomerated powder of all even particle diameter of component.
Step c) in method for making of the present invention; Be the high resistance agglomerated powder that step b) prepares to be added water process slip; Under agitation condition, in the doping non-equivalence ionic zinc oxide grain adding slip with a certain proportion of step a) preparation, after stirring; Through oven dry, calcining, levigate again, promptly process the ceramics powder that zinc oxide varistor is used.
The zinc oxide grain of step a): the weight proportion of the agglomerated powder of step b) is
preferred
Step d) in method for making of the present invention; Be to process zinc oxide varistor by the processes well known method; Comprise that the ceramics powder of step c) is processed slurry to be spread to living embryo, print the interior electrode that interlocks more than 2 layers or 2 layers, the living embryonic crystal grain of calcining electrode in the tool; After the calcining, the two ends coating outer electrode of electrode in crystal grain exposed is to make disk type or multilayer sheet type zinc oxide varistor.
Zinc oxide varistor method for making of the present invention has following effect:
1. the schottky barrier height between the raising zinc oxide grain
Step a) in the method for making of the present invention is because be independent process; Overcome the shortcoming of the known method for making of zinc oxide varistor; In zinc oxide grain doping non-equivalence ionic process; The restriction of the high resistance intergranular phase component that needn't receive to be selected for use, and have the following advantages and improved the height of the Schottky barrier between the zinc oxide grain, the prepared zinc oxide varistor of result has superelevation potential gradient and non-linear character concurrently:
1) enlarges alternative dopant ion composition kind;
During the zinc oxide grain dopant ion, do not receive the restriction of high resistance intergranular phase component, having expanded zinc oxide grain greatly can adulterated non-equivalence ion component kind.
2) improved non-equivalence ionic doping;
Because zinc oxide grain can be created the best ion doping condition non-equivalence ion that mixes, the non-equivalence ions dosage of zinc oxide grain will greatly improve as a result.
2. the crystal boundary number between the zinc oxide grain in the increase unit thickness
In the method for making of the present invention; Come growing up of inhibited oxidation zinc crystal grain through adjustment intergranular phase component; Or the size of zinc oxide grain is reduced through ultra-fine grinding process; Or select nano level zinc oxide grain for use, and can improve the zinc oxide grain quantity of unit thickness and increase the crystal boundary number, make prepared zinc oxide varistor tool high potential gradient and non-linear character.
3. improve the homogeneity of intergranular phase component and structure thereof
Step b) in the method for making of the present invention is because be independent process, and the applying nano technology must be processed the intergranular phase component particle of nanometer particle size, and each made particle all contains and is close to identical component.The more important thing is Bi
2O
3With other intergranular phase component through levigate, calcining or (comprise Bi with selected
2O
3) each component applying nano technology is next synthetic mutually for intergranular, can make each nano particle have the Bi of containing
2O
3Similar component.In sintering process, be close to each component of intergranular phase of same structure, help to reduce Bi
2O
3Melt solubleness, the minimizing zinc oxide grain speed of growth and the inhibited oxidation zinc grain growth of zinc oxide in the body.So, because the zinc oxide grain quantity of unit thickness and the increase of crystal boundary number, prepared zinc oxide varistor tool high potential gradient and non-linear character.
Embodiment 1:
Prepare the sintered material of code name G1-10 with chemical precipitation method, its component is listed in table 1.
The mol ratio of each component of table 1. sintered material (ZnO of collocation 1mol)
| Component (mol%) | Bi 2O 3 | MnO 2 | Co 2O 3 | Sb 2O 3 | Y 2O 3 | Ce 2O 3 | SiO 2 | B 2O 3 |
| G1-10 | 1.50 | 1.00 | 1.00 | 1.00 | 0.003 | 0.003 | 0.50 | 0.005 |
Prepare doping ZnO with dopant ion solution soaking method
*Crystal grain, its doping ionic species and ratio are listed in table 2.
Table 2. doping ZnO
*Each doping ionic species and mol ratio in the crystal grain (ZnO is 1mol)
| Doping ionic species | Sn | Si | B | Al |
| Ratio (mol%) | 0.60 | 0.10 | 1.00 | 0.015 |
With doping ZnO
*After crystal grain and G1-10 sintered material powder mix, with 1000kg/cm
2Pressure is pressed into the disk of diameter 8.4mm, again with 920 ℃ of sintering of temperature 8 hours, then at 800 ℃ of sintering of accomplishing surperficial silver electrodes, processes the zinc oxide varistor of disk type, and calcining temperature was respectively 950 ℃ of sintering 2 hours; 1250 ℃ of sintering 2 hours; 1550 ℃ of sintering 2 hours.Its performance is listed in table 3.
Table 3. is with the doping ZnO of different calcining temperatures
*The performance of made zinc oxide varistor
Embodiment 2:
The zinc oxide grain sample for preparing listed doping 1mol% indium (In) the ion composition of table 5 with chemical coprecipitation.Prepare the sintered material of code name G1-00 with chemical coprecipitation, its composition and weight ratio are listed in table 4.
Each component of table 4. sintered material (wt%)
By the zinc oxide grain sample: the weight proportion of G1-00 sintered material is that the mixed of 100: 10 or 100: 15 or 100: 30 is even, then with 1000kg/cm
2Pressure be pressed into disk, again with 1065 ℃ of sintering of sintering temperature 2 hours, then accomplish the coated silver electrodes, and process disk type zinc oxide varistor at 800 ℃.Measure the performance of various zinc oxide varistors respectively, its result sees table 5 for details.
Can know by table 5, when zinc oxide grain mixes dopant ion composition of the same race, the pressure-sensitive character of zinc oxide varistor, will be along with the proportioning of zinc oxide grain and high resistance sintered material different and different.So,, can make the zinc oxide varistor that potential gradient surpasses 1700V/mm from the dopant ion composition kind of controlled oxidation zinc crystal grain or the proportioning of allotment zinc oxide grain and high resistance sintered material.
The same sintered material of table 5. is processed the voltage-dependent characteristic of zinc oxide varistor with different mixing match
Embodiment 3:
With embodiment 1, prepare G1-10 sintered material powder with chemical precipitation method, prepare doping ZnO with dopant ion solution soaking method
*Crystal grain, calcining temperature are 950 ℃ of sintering 2 hours, and its doping ionic species and ratio are listed in table 6.
Table 6. doping ZnO
*Each doping ionic species and mol ratio in the crystal grain (ZnO is 1mol)
With embodiment 1, be made into the zinc oxide varistor of disk type, its performance is listed in table 7.Wherein, the potential gradient of prepared specimen coding 1～4 zinc oxide varistor all surpasses 27.41 and leakage current I above 1200V/mm, non-linear character α
LBe lower than 16.5 μ A.The potential gradient of especially prepared specimen coding 4 zinc oxide varistors is up to 6023V/mm.
The adulterated ZnO of table 7. different ions
*The performance of the zinc oxide varistor that crystal grain is made
Embodiment 4:
With embodiment 1, prepare G1-10 sintered material powder with chemical precipitation method, prepare doping ZnO with sol-gel method
*Crystal grain, calcining temperature are 350 ℃ of sintering 3 hours, and its doping ionic species and ratio are same as the specimen coding 3 and 4 of embodiment 3 respectively, and specimen coding is compiled it respectively and is No 3-nm and No4-nm, and its X-ray diffraction collection of illustrative plates is listed in Fig. 1 and Fig. 2 respectively.From doping ZnO
*Crystal grain X-ray diffraction collection of illustrative plates and the comparison of ZnO standard diagram can be known, under this low calcination condition, have formed the crystal of zinc oxide.
Process disk type zinc oxide varistor with embodiment 1, its performance is listed in table 8.
Table 8. different ions doped n m-ZnO
*The rheostatic performance that crystal grain is made
Annotate: the sample of disruptive voltage more than 6500V/mm, its disruptive voltage has exceeded the measuring range of instrument.So, utilize and survey and draw out the I-V curve, use V then
1(I
1=0.1mA) and V
2(I
2=1.0mA) numerical value, by formula
Calculate nonlinear factor α value; Leakage current I
LElectric current when getting 80%BDV by regulation.
The I-V graphic representation of the disk sample of specimen coding No 3-nm and the disk sample of No 4-nm is respectively Fig. 3 and Fig. 4.
Wherein, the potential gradient of obtained specimen coding No 3-nm and No 4-nm zinc oxide varistor is all above 6800V/mm.The potential gradient of the zinc oxide varistor of especially prepared specimen coding No 4-nm surpasses 9000V/mm, non-linear character α and reaches 21.50 and leakage current I
LBe lower than 16 μ A.
Embodiment 5:
Get 1250 ℃ of incinerating doping ZnOs among the embodiment 1
*With G1-10 sintered material powder uniform mixing, through planetary mills equipment it is made three kinds of samples that median size is 2.1 μ m, 1.1 μ m and 0.56 μ m respectively, process the zinc oxide varistor of disk type by embodiment 1, its performance is listed in table 9
The rheostatic performance of the prepared disk type of the zinc oxide ceramics powder of table 9. different-grain diameter
Wherein, the particle diameter of zinc oxide ceramics powder is less than 1.1 μ m, and the potential gradient of prepared zinc oxide varistor is all above 1200V/mm.So present embodiment has confirmed to improve the fineness of zinc oxide ceramics powder, is the potential gradient that can improve zinc oxide varistor.
Embodiment 6:
With the 2 zinc oxide ceramics powder of the specimen coding among the embodiment 3, press the rheostatic routine fashion of multilayer chiop type, make 2220 and 1210 type multilayer chiop type varistors respectively, be that 900 ℃ of sintering burn till under 8 hours in calcining temperature, it electrically lists in table 10.
The multilayer chiop type varistor performance that table 10. specimen coding 2 zinc oxide ceramics powder are processed
Wherein, prepared 2220ML100 and the rheostatic potential gradient of 1210ML100 type multilayer chiop type all above 2000V/mm and non-linear character α all above 35.
Embodiment 7:
With the 3 zinc oxide ceramics powder of the No among the embodiment 3, press the rheostatic routine fashion of multilayer chiop type, make 2220 and 1210 type multilayer chiop type varistors respectively, be that 900 ℃ of sintering burn till under 8 hours in calcining temperature, it electrically lists in table 11.
The rheostatic performance of multilayer chiop type that table 11. specimen coding 3 zinc oxide ceramics powder are processed
Wherein, prepared 2220ML390 and the about 4000V/mm of the rheostatic potential gradient of 1210ML390 type multilayer chiop type and non-linear character α are all above 44.
Embodiment 8:
With embodiment 1; The zinc oxide grain of dopant ion and the zinc oxide grain of dopant ion are raw material respectively with not to use the G1-10 sintered material powder; Make disk type zinc oxide varistor, its performance is listed in table 12, and the electronic scanning sectional view photo of its disk test specimen is listed in Fig. 5 and Fig. 6 respectively.
The varistor performance that table 12. is processed with the zinc oxide grain of dopant ion and dopant ion not
Measure calculating according to electronic scanning sectional view photo, in the disk sample of dopant ion, the median size of its ZnO crystal grain is not 5.2 μ m, and in the disk sample of ion doping, its ZnO
*The median size of crystal grain is 2.2 μ m, and its particle diameter ratio is 2.4 times.Above-mentioned two samples burn till under similarity condition, but 2.4 times of zinc oxide grain difference in size, and the zinc oxide that promptly shows dopant ion gets effective inhibited oxidation zinc crystal grain and in sintering process, grows.
And, by the formula calculating of zinc oxide grain number in the unit thickness, should be 777.6V/mm (324V/mmx2.4) through the potential gradient of the zinc oxide disk of ion doping, but measured result be 1370V/mm with potential gradient.Therefore can think this additional 592.4V/mm (1370V/mm deducts 777.6V/mm) that improves, ion doping improves the Schottky barrier of zinc oxide grain boundaries due to, and is same, has bigger nonlinear factor through the zinc oxide varistor of ion doping.
Embodiment 9:
With embodiment 1, with the G1-10 sintered material powder respectively with the specimen coding 3 of embodiment 3 and 4 doping ZnO
*Process disk type zinc oxide varistor for raw material, the leakage current value of this varistor under differing temps listed in table 13.
The leakage current value of table 13. disk type zinc oxide varistor and the difference of temperature
Claims (8)
1. method for making that makes zinc oxide varistor improve potential gradient and nonlinear factor simultaneously, be used to make potential gradient between
Nonlinear factor α between
And leakage current I
LBetween
Zinc oxide varistor, it is characterized in that, comprise the following steps:
A) according to the potential gradient of zinc oxide varistor between one or more non-equivalence ionic zinc oxide grains of
prefabricated doping; And the adulterated non-equivalence ion of said confession zinc oxide grain, be selected from the colony that forms by lithium, copper, aluminium, cerium, cobalt, chromium, indium, gallium, molybdenum, manganese, niobium, lanthanum, yttrium, praseodymium, antimony, nickel, titanium, vanadium, tungsten, zirconium, iron, boron, silicon and tin wherein one or more;
B) according to the potential gradient of zinc oxide varistor agglomerated powder between
prefabricated high resistance; Wherein one or more oxide compound, oxyhydroxide, carbonate, nitrate salt or the oxalate that is selected from bismuth-containing, calcium halophosphate activated by antimony andmanganese, cobalt, chromium, nickel, titanium, silicon, barium, boron, selenium, lanthanum, praseodymium, yttrium, indium, aluminium or tin is raw material, through mix, sintering is levigate again to required fineness;
C) mixing step zinc oxide grain a) and the agglomerated powder of step b) by a certain percentage, the ceramics powder that the preparation zinc oxide varistor is used; And
D) use the ceramics powder of step c) to be raw material, prepare potential gradient between
and the disk type or the multilayer tablet type zinc oxide varistor of nonlinear factor α between
by ordinary method.
2. the method for making that makes zinc oxide varistor improve potential gradient and nonlinear factor simultaneously as claimed in claim 1; Wherein step a) is to Zinc oxide doped non-equivalence ionic method; Be that adulterated non-equivalence ion is processed solution; Soak zinc oxide; Levigate the making of calcining after oven dry, calcining temperature is between
3. the method for making that makes zinc oxide varistor improve potential gradient and nonlinear factor simultaneously as claimed in claim 1; Wherein step a) is to Zinc oxide doped non-equivalence ionic method; Be to adopt the zinc salt that contains that is prone to dissolve to obtain coprecipitate with coprecipitation method with plan dopant ion solution; After cleaning, drying, following calcining makes the dopant ion zinc oxide grain between
in calcining temperature.
4. the method for making that makes zinc oxide varistor improve potential gradient and nonlinear factor simultaneously as claimed in claim 1; Wherein step a) is to Zinc oxide doped non-equivalence ionic method; Be with sol-gel method zine ion to be dispersed in to contain in the inorganic salt or metal alkoxide colloidal sol of intending dopant ion; Through being hydrolyzed, after bunching reaction forms colloidal sol, again through solidify and calcining temperature between
down calcining make the dopant ion zinc oxide grain.
5. the method for making that makes zinc oxide varistor improve potential gradient and nonlinear factor simultaneously as claimed in claim 1, wherein the agglomerated powder of step b) is selected from by Bi
2O
3, Sb
2O
3, CoO, MnO, ZnO, Cr
2O
3, TiO
2, SiO
2, B
2O
3, Pr
2O
3, Y
2O
3And La
2O
3Wherein more than one the combination of the colony that is formed.
6. the method for making that makes zinc oxide varistor improve potential gradient and nonlinear factor simultaneously as claimed in claim 1; Wherein, The high resistance agglomerated powder of step b); Be that process is processed solution with raw material, chemical precipitation method, micro emulsion method or the sol-gel method of applying nano technology forms nanometer fine powder and makes.
7. the method for making that makes zinc oxide varistor improve potential gradient and nonlinear factor simultaneously as claimed in claim 1, wherein step c) is a) a zinc oxide grain set by step: the weight proportion of the agglomerated powder of step b) mixes for
.
8. the method for making that makes zinc oxide varistor improve potential gradient and nonlinear factor simultaneously as claimed in claim 1, wherein step a) and step b) are to set the agglomerated powder that carries out prefabricated dopant ion zinc oxide grain and prefabricated high resistance between
respectively according to the potential gradient of zinc oxide varistor.
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| CN109265161A (en) * | 2018-10-29 | 2019-01-25 | 惠州嘉科实业有限公司 | Middle pressure varistor and preparation method thereof |
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| CN104591726A (en) * | 2014-12-29 | 2015-05-06 | 广西新未来信息产业股份有限公司 | High-potential gradient zinc oxide voltage piezo-resistor material and preparation method thereof |
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| CN106946562A (en) * | 2017-04-13 | 2017-07-14 | 贵州大学 | In3+、Nb5+Compound donor doping ZnO voltage-sensitive ceramics and preparation method |
| CN106946560A (en) * | 2017-04-13 | 2017-07-14 | 贵州大学 | Y3+、Sn4+Compound donor doping ZnO voltage-sensitive ceramics and preparation method |
| CN106946561A (en) * | 2017-04-13 | 2017-07-14 | 贵阳高新益舸电子有限公司 | Y3+、Nb5+Compound donor doping ZnO voltage-sensitive ceramics and preparation method |
| CN106892657A (en) * | 2017-04-13 | 2017-06-27 | 贵州大学 | In3+、Sn4+Compound donor doping ZnO voltage-sensitive ceramics and preparation method |
| CN106946562B (en) * | 2017-04-13 | 2020-11-10 | 贵州大学 | In3+、Nb5+Composite donor doped ZnO pressure-sensitive ceramic and preparation method thereof |
| CN106946560B (en) * | 2017-04-13 | 2020-11-10 | 贵州大学 | Y3+、Sn4+Composite donor doped ZnO pressure-sensitive ceramic and preparation method thereof |
| CN106892657B (en) * | 2017-04-13 | 2020-11-20 | 贵州大学 | In3+、Sn4+Composite donor doped ZnO pressure-sensitive ceramic and preparation method thereof |
| CN106946561B (en) * | 2017-04-13 | 2020-12-04 | 贵阳高新益舸电子有限公司 | Y3+、Nb5+Composite donor doped ZnO pressure-sensitive ceramic and preparation method thereof |
| CN108675783A (en) * | 2018-05-24 | 2018-10-19 | 江苏时瑞电子科技有限公司 | A kind of material and preparation method thereof for zinc oxide varistor |
| CN109265161A (en) * | 2018-10-29 | 2019-01-25 | 惠州嘉科实业有限公司 | Middle pressure varistor and preparation method thereof |
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