CN108329023A - A kind of preparation method of zinc oxide base nano composite granule resistor disc - Google Patents

A kind of preparation method of zinc oxide base nano composite granule resistor disc Download PDF

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Publication number
CN108329023A
CN108329023A CN201810180412.6A CN201810180412A CN108329023A CN 108329023 A CN108329023 A CN 108329023A CN 201810180412 A CN201810180412 A CN 201810180412A CN 108329023 A CN108329023 A CN 108329023A
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zinc oxide
nano composite
composite granule
base nano
oxide base
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CN108329023B (en
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陆佳政
潘碧宸
陈宝辉
李波
吴传平
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State Grid Corp of China SGCC
State Grid Hunan Electric Power Co Ltd
Disaster Prevention and Mitigation Center of State Grid Hunan Electric Power Co Ltd
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State Grid Corp of China SGCC
State Grid Hunan Electric Power Co Ltd
Disaster Prevention and Mitigation Center of State Grid Hunan Electric Power Co Ltd
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    • C04B35/453—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zinc, tin, or bismuth oxides or solid solutions thereof with other oxides, e.g. zincates, stannates or bismuthates
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Abstract

The invention discloses a kind of preparation methods of zinc oxide base nano composite granule resistor disc, the process that preparation, aqueous, tabletting, sintering, grinding cleaning including zinc oxide base nano composite granule, aluminium-plated, side apply insulation glaze, finally obtains zinc oxide base nano composite granule resistor disc.The present invention is Nano grade powder by the Multimetal oxide including zinc oxide prepared by chemical sol-gel processes, each component is uniformly mixed, the particle diameter distribution of particle is small, to improve the electric potential gradient, through-current capability and tolerance high current impulse withstanding capability of zinc oxide resistance sheet；The preparation of zinc oxide resistance sheet of the present invention needs not move through ball milling, prilling, not only can be cost-effective, but also improves production efficiency, is conducive to mass production；The present invention does not have to that adhesive polyethylene alcohol is added, and crude green body can also keep good intensity made from tabletting, slight crack will not occurs in calcining, reduce production cost, and environmentally friendly.

Description

A kind of preparation method of zinc oxide base nano composite granule resistor disc
Technical field
The invention belongs to high pressure electrician's ceramic material sensitive to heat-humidity technical fields, are related to a kind of zinc oxide base nano composite granule electricity Hinder the preparation method of piece.
Background technology
Zinc oxide resistance sheet is a kind of multi-component metal oxide poly semiconductor ceramics, is main with zinc oxide (ZnO) Raw material, addition Multimetal oxide ingredient (Bi2O3、MnO2、Co2O3、Cr2O3、Sb2O3、SiO2、TiO2Deng), using typical Ceramic material processes are prepared.Core component of the zinc oxide resistance sheet as arrester, performance directly affect zinc oxide and keep away The performance of thunder device product.Extra-high voltage grade, since technical sophistication, cost are higher, is only lacked at present with Zinc-Oxide Arrester resistor disc Number country possesses, and foreign countries have production ZnO Arrester for UHV and the company of pressure-sensitive voltage gradient valve block ability includes： The TMT＆D (being combined by Mitsubishi, Toshiba for 2002) of Japan and Hitachi, Russia's electroceramics union, the U.S. GE, OB, Sweden ABB, Britain EMP.In order to accelerate the development of China's power industry, the dependence to foreign technology is broken away from, high negotiability, high voltage are developed The zinc oxide resistance sheet of gradient has realistic meaning.
Cause the study found that the main reason for influencing resistor disc through-current capability is microcosmic unevenness structure inside resistor disc The unevenness of current distribution, resulting heat cause built-in thermal stress to be formed, to make resistor disc puncture or burst.Separately Outside, the voltage gradient of resistor disc is related with the composition particle size of resistor disc particle, and the grain size of particle is smaller, the voltage of resistor disc Gradient is bigger.
The technological process of production of existing zinc oxide resistance sheet is：Dispensing, grinding, granulation, aqueous, tabletting, sintering, grinding are clear It washes, aluminium-plated upper side insulating layer, finally obtains zinc oxide resistance sheet, technique is cumbersome, and the production cycle is long, and production efficiency is relatively low；It is general All over ball-milling technology is used, the grain size of particle is larger after ball milling, mixing it is ineffective, it is difficult to obtain nano level raw material powder； And it needs to add binder polyvinyl alcohol into slurry when being granulated, the CO that can be decomposed in sintering2、H2O and charcoal It is black, the porosity of zinc oxide resistance sheet is increased, the homogeneity of resistor disc internal structure is reduced；Production cost is increased simultaneously, Since polyvinyl alcohol has chemical toxicity, it is unfavorable for the safety in production of operating personnel, pollution is also will produce to environment.
Invention content
The purpose of the present invention is to provide a kind of preparation methods of zinc oxide base nano composite granule resistor disc, are prepared Zinc oxide resistance sheet have that ingredient is uniform, grain diameter is small, at low cost, environmentally friendly, voltage gradient is high and circulation energy The advantages that power is strong.
A kind of preparation method of zinc oxide base nano composite granule resistor disc of the present invention, includes the following steps：
(1) the various metals salt mixture including zinc salt is made into aqueous solution, instills surface modifier thereto, stirs It mixes and uniformly obtains metal mixed salt solution；
(2) complexing agent is dissolved in the ethanol solution for being made into complexing agent in absolute ethyl alcohol, metal mixed salt solution is dripped It is added in the ethanol solution of complexing agent, stirring at a set temperature makes it fully dissolve, and then keeps the temperature, and it is solidifying that white is obtained after filtering Glue；
(3) it by white gels washes clean, is put into tube furnace, calcines at a set temperature, by products therefrom after dry Washes clean obtains zinc oxide base nano composite granule after dry；
(4) aqueous：The distilled water of predetermined amount is added into zinc oxide base nano composite granule, stirs；
(5) tabletting：Powder after will be aqueous, which is put into tablet press machine, is compressed into tablet form crude green body；
(6) it is sintered：By crude green body in Muffle furnace calcination processing；
(7) it is ground, cleans：By resistor disc grinding two end surfaces, cleaned up using distilled water；
(8) aluminium-plated, side applies insulation glaze：Resistor disc both ends of the surface are sprayed into aluminium electrode, insulation glaze is applied in side, is aoxidized Zinc-base composite nano-powder resistor disc.
Preferably, the component molar percentage of the various metals salt mixture is：Zinc salt：80%~90%, bismuth salt： 4%~5%, antimonic salt：4%~5%, magnesium salts：1%~2%, aluminium salt：1%~2%, cobalt salt：1%~2%, chromic salts：0%~ 1%, manganese salt：0%~1%, titanium salt：0%~1%, yttrium salt：0%~0.1%.
Preferably, the metal salt is one kind in nitrate, acetate.
Preferably, a concentration of 0.6~0.8mol/L of the metal salt solution.
Preferably, the surface modifier is one kind or one in dodecyl sodium sulfate, Triammonium citrate and Tween 80 Kind or more, the dosage of surface modifier is the 2%~3% of metal salt weight.
Preferably, the complexing agent is the one or more in oxalic acid, citric acid and Triammonium citrate.
Preferably, a concentration of 0.6~0.8mol/L of the ethanol solution of the complexing agent.
Preferably, in the step (2), whipping temp is 80~90 DEG C, and mixing time is 1~2h；Holding temperature is 80 ~90 DEG C, soaking time is 0.5~1h.
Preferably, in the step (3), white gels drying temperature is 80~90 DEG C, and drying time is 1~2h.
Preferably, in the step (3), the calcination temperature of gel is 300~400 DEG C, and soaking time is 2~3h.
Preferably, in the step (4), 1%~1.5% mass fraction is added into zinc oxide base nano composite granule Distilled water.
Preferably, in the step (6), calcination temperature is 1100~1200 DEG C, and soaking time is 90~100h.
The present invention also provides what is be prepared according to the preparation method of the zinc oxide base nano composite granule resistor disc Zinc oxide base nano composite granule resistor disc.
The principle of the present invention：The present invention prepares nanometer grade composit powder material using chemical sol-gel processes, makes from molecular level Each component uniformly mixes, because without ball milling, gel in calcining using not exclusively calcining (300~400 DEG C, soaking time 2 ~3h), make member-retaining portion hydroxyl in composite granule obtained that can enhance powder since there are hydrogen bonds between hydroxyl and hydroxyl Between interaction, therefore without be added adhesive polyethylene alcohol, and without be granulated, directly by zinc oxide base nano composite granule Crude green body made from aqueous, tabletting can also keep good intensity, be not in slight crack in calcining, due to being not required to addition polyethylene Alcohol, when sintering, not will produce CO2、H2O and carbon black, reduce the porosity of zinc oxide resistance sheet, and resistor disc each component is evenly distributed Property, to improve the electric potential gradient, through-current capability and tolerance high current impulse withstanding capability of zinc oxide resistance sheet.
Compared with the existing technology, the present invention has following advantageous effects：
(1) Multimetal oxide including zinc oxide that the present invention is prepared by chemical sol-gel processes is to receive The other powder of meter level, each component be uniformly mixed, the particle diameter distribution of particle is small, to improve zinc oxide resistance sheet electric potential gradient, Through-current capability and tolerance high current impulse withstanding capability.
(2) preparation of zinc oxide resistance sheet of the present invention needs not move through ball milling, prilling, not only can be cost-effective, but also Production efficiency is improved, mass production is conducive to.
(3) present invention does not have to that adhesive polyethylene alcohol is added, and crude green body can also keep good intensity made from tabletting, will not There is slight crack in calcining, reduces production cost, and environmentally friendly.
Description of the drawings
Fig. 1 is the microstructure SEM figures of 1 gained zinc oxide resistance sheet of the embodiment of the present invention.
Fig. 2 is the microstructure SEM figures of 2 gained zinc oxide resistance sheet of the embodiment of the present invention.
Fig. 3 is the microstructure SEM figures of 3 gained zinc oxide resistance sheet of the embodiment of the present invention.
Fig. 4 is the microstructure SEM figures for the zinc oxide resistance sheet that comparative example 1 is prepared.
Specific implementation mode
The technical scheme in the embodiments of the invention will be clearly and completely described below, it is clear that described implementation Example is only a part of the embodiment of the present invention, rather than whole embodiments, based on the embodiments of the present invention, the common skill in this field The every other embodiment that art personnel are obtained without making creative work belongs to the model that the present invention protects It encloses.
Experimental method described in following embodiments is unless otherwise specified conventional method, the reagent and material, such as Without specified otherwise, commercially obtain.
Embodiment 1
The raw material of the present embodiment is prepared by following molar percentage, and specific formula is as follows：
Zinc salt：85%, bismuth salt：4%, antimonic salt：4%, magnesium salts：2%, aluminium salt：2%, cobalt salt：1.5%, chromic salts：0.5%, Manganese salt：0.5%, titanium salt：0.4%, yttrium salt：0.1%.
A kind of preparation method of zinc oxide base nano composite granule resistor disc of the present invention, includes the following steps：
(1) it is accurate weigh 101.108g zinc acetates, 10.036g bismuth acetates, 7.774g antimony acetates, 1.846g magnesium acetates, 2.652g aluminum acetates, 1.726g cobalt acetates, 0.744g chromic acetates, 0.562g manganese acetates, 0.738g acetic acid titanium and 0.173g acetic acid Yttrium is dissolved in 1L distilled water, forms aqueous metal salt, and 2.547g dodecyl sodium sulfates are added, being vigorously stirred makes it fill Divide dissolving, obtains metal mixed salt solution；
(2) it is accurate weigh 162g oxalic acid and be dissolved in 3L absolute ethyl alcohols be made into oxalic acid ethanol solution, the metal that will be prepared Mixed salt solution is slowly dropped in oxalic acid ethanol solution, is placed in 85 DEG C of stirred in water bath 1h, so that it is fully dissolved, then Insulation reaction 0.5h, is obtained by filtration white gels；
(3) white gels are respectively washed twice with distilled water and absolute ethyl alcohol respectively, is placed in 80 DEG C of vacuum drying chambers and does Gel after drying is put into 300 DEG C of tube furnaces and calcines 3h by dry 2h, then uses distilled water and absolute ethyl alcohol each respectively products therefrom It washes twice, can be prepared by zinc oxide base nano composite granule after dry；
(4) aqueous：The distilled water of 1% mass fraction is added into zinc oxide base nano composite granule, stirs；
(5) tabletting：Powder after will be aqueous, which is put into tablet press machine, is compressed into tablet form crude green body；
(6) it is sintered：Crude green body is calcined into 100h at 1100 DEG C；
(7) it is ground, cleans：Resistor disc both ends are polished, are cleaned up using distilled water；
(8) aluminium-plated, side applies insulation glaze：Resistor disc both ends are sprayed into aluminium electrode, insulation glaze is applied in side, obtains zinc oxide Based nanometer composite powder resistor disc.
Resistors that specification is Φ 70 are made in gained zinc oxide base nano composite granule, and (outer annular diameter is 72mm, annular diameters 26mm are highly 22.5mm), the microcosmic of zinc oxide resistance sheet of the present invention is analyzed using scanning electron microscope sem Structure, as shown in Figure 1, grain size is 7.6 μm, and the voltage gradient of test resistance piece, through-current capability and tolerance high current punching Ability is hit, as shown in table 1.
Embodiment 2
The raw material of the present embodiment is prepared by following molar percentage, and specific formula is as follows：
Zinc salt：85%, bismuth salt：4.5%, antimonic salt：4.5%, magnesium salts：1%, aluminium salt：2%, cobalt salt：1.8%, chromic salts： 0.6%, manganese salt：0.5%, yttrium salt：0.1%.
A kind of preparation method of zinc oxide base nano composite granule resistor disc of the present invention, includes the following steps：
(1) it is accurate weigh 108.885g zinc acetates, 12.159g bismuth acetates, 9.419g antimony acetates, 0.994g magnesium acetates, 2.856g aluminum acetates, 2.23g cobalt acetates, 0.962g chromic acetates, 0.606g manganese acetates and 0.186g acetic acid yttriums, are dissolved in 1L distilled water In, aqueous metal salt is formed, and 2.766g Tween 80s are added, being vigorously stirred makes it fully dissolve, and it is molten to obtain metal salt mixing Liquid；
(2) accurately weighing 346g citric acids is dissolved in the ethanol solution that citric acid is made into 3L absolute ethyl alcohols, will prepare Metal mixed salt solution be slowly dropped in the ethanol solution of citric acid, be placed in 80 DEG C of stirred in water bath 2h, it made to fill Divide dissolving, insulation reaction 1h that white gels are obtained by filtration；
(3) white gels are respectively washed twice with distilled water and absolute ethyl alcohol respectively, is placed in 90 DEG C of vacuum drying chambers and does Gel after drying is put into 400 DEG C of tube furnaces and calcines 3h by dry 1h, then uses distilled water and absolute ethyl alcohol each respectively products therefrom It washes twice, can be prepared by zinc oxide base nano composite granule after dry；
(4) aqueous：The distilled water of 1.5% mass fraction is added into zinc oxide base nano composite granule, is sufficiently stirred It is even；
(5) tabletting：Powder after will be aqueous, which is put into tablet press machine, is compressed into tablet form crude green body；
(6) it is sintered：Crude green body is calcined into 96h at 1150 DEG C；
(7) it is ground, cleans：Resistor disc both ends are polished, are cleaned up using distilled water；
(8) aluminium-plated, side applies insulation glaze：Resistor disc both ends are sprayed into aluminium electrode, insulation glaze is applied in side, obtains zinc oxide Based nanometer composite powder resistor disc.
Resistors that specification is Φ 70 are made in gained zinc oxide base nano composite granule, and (outer annular diameter is 72mm, annular diameters 26mm are highly 22.5mm), the microcosmic of zinc oxide resistance sheet of the present invention is analyzed using scanning electron microscope sem Structure, as shown in Fig. 2, grain size is 8.1 μm, and the voltage gradient of test resistance piece, through-current capability and tolerance high current punching Ability is hit, as shown in table 1.
Embodiment 3
The raw material of the present embodiment is prepared by following molar percentage, and specific formula is as follows：
Zinc salt：85%, bismuth salt：5%, antimonic salt：5%, magnesium salts：1%, aluminium salt：1%, cobalt salt：1.4%, chromic salts：0.5%, Manganese salt：0.5%, titanium salt：0.5%, yttrium salt：0.1%.
A kind of preparation method of zinc oxide base nano composite granule resistor disc of the present invention, includes the following steps：
(1) 128.52g zinc nitrates, 15.8g bismuth nitrates, 12.32g nitric acid antimony, 1.184g magnesium nitrates, 1.704g accurately are weighed Aluminum nitrate, 2.05g cobalt nitrates, 0.952g chromic nitrates, 0.716g manganese nitrates, 1.184g Titanium Nitrates and 0.22g yttrium nitrates, are dissolved in 1L In distilled water, aqueous metal salt is formed, and 3.293g Triammonium citrates are added, being vigorously stirred makes it fully dissolve, and obtains gold Belong to mixed salt solution；
(2) accurately weighing 162g oxalic acid is dissolved in the ethanol solution that oxalic acid is made into 3L absolute ethyl alcohols, the gold that will be prepared Belong to mixed salt solution to be slowly dropped in the ethanol solution of oxalic acid, be placed in 90 DEG C of stirred in water bath 1h, it is made fully to dissolve, 0.5h is kept the temperature, white gels are obtained by filtration；
(3) white gels are respectively washed twice with distilled water and absolute ethyl alcohol respectively, is placed in 85 DEG C of vacuum drying chambers and does Gel after drying is put into 350 DEG C of tube furnaces and calcines 2.5h by dry 2h, then products therefrom is used distilled water and absolute ethyl alcohol respectively It respectively washes twice, can be prepared by zinc oxide base nano composite granule after dry；
(4) aqueous：The distilled water of 1.2% mass fraction is added into zinc oxide base nano composite granule, is sufficiently stirred It is even；
(5) tabletting：Powder after will be aqueous, which is put into tablet press machine, is compressed into tablet form crude green body；
(6) it is sintered：Crude green body is calcined into 90h at 1200 DEG C；
(7) it is ground, cleans：Resistor disc both ends are polished, are cleaned up using distilled water；
(8) aluminium-plated, side applies insulation glaze：Resistor disc both ends are sprayed into aluminium electrode, insulation glaze is applied in side, obtains zinc oxide Based nanometer composite powder resistor disc.
Resistors that specification is Φ 70 are made in gained zinc oxide base nano composite granule, and (outer annular diameter is 72mm, annular diameters 26mm are highly 22.5mm), the microcosmic of zinc oxide resistance sheet of the present invention is analyzed using scanning electron microscope sem Structure, as shown in figure 3, grain size is 8.0 μm, and the voltage gradient of test resistance piece, through-current capability and tolerance high current punching Hit ability.
Comparative example 1
Using the preparation method for the Zinc oxide-base composite granule resistor disc that common ball grinding method obtains, including walk as follows Suddenly：
(1) raw material is prepared：
Weigh 44.007g zinc oxide, 3.471g bismuth oxides, 2.952g antimony oxides, 0.324g magnesia, 0.288g oxidations Aluminium, 0.486g cobalt oxides and 0.192g chromium oxide, are put into ball mill after mixing and grind 12h, obtain Zinc oxide-base composite granule；
(2) it grinds：The raw material weighed is added in the distilled water of 300% mass fraction and is stirred evenly, sand milling is then placed in 2h is ground in machine；
(3) it is granulated：The polyvinyl alcohol of 5% mass fraction is added into the slurry after grinding, is then placed in comminutor and sprays Mist is granulated；
(4) aqueous：The distilled water of 1.5% mass fraction is added into the powder after granulation, stirs；
(5) tabletting：Powder after will be aqueous, which is put into tablet press machine, is compressed into tablet form crude green body；
(6) it is sintered：Crude green body is calcined into 96h at 1150 DEG C；
(7) it is ground, cleans：Resistor disc both ends are polished, are cleaned up using distilled water；
(8) aluminium-plated, side applies insulation glaze：Resistor disc both ends are sprayed into aluminium electrode, insulation glaze is applied in side, obtains arrester Use zinc oxide resistance sheet.
Resistors that specification is Φ 70 are made in gained zinc oxide base nano composite granule, and (outer annular diameter is 72mm, annular diameters 26mm are highly 22.5mm), it is multiple using scanning electron microscope sem analysis Zinc oxide-base as obtained by ball-milling method The microstructure of powder resistance piece is closed, as shown in figure 4, grain size is 13.2 μm, and it is the voltage gradient of test resistance piece, through-flow Ability and tolerance high current impulse withstanding capability, as shown in table 1.
1 Zinc oxide-base composite granule resistor disc parameter comparison of table
The zinc oxide resistance sheet that the method provided through the invention synthesizes is can be seen that from embodiment 1-3 and comparative example 1, Its particle size is much smaller than the zinc oxide resistance sheet obtained using common ball grinding method, uses the method provided through the invention The electric potential gradient and through-current capability of zinc oxide resistance sheet made from the zinc oxide base nano composite granule of synthesis and conventional method system The electric potential gradient of the zinc oxide resistance sheet obtained has been compared with through-current capability to be obviously improved, and illustrates that the method provided through the invention is closed At zinc oxide base nano composite granule have evenly compared with the Zinc oxide-base composite granule that common ball-milling method obtains Ingredient and particle diameter distribution.Method provided by the invention needs not move through ball milling, is granulated during zinc oxide resistance sheet is made Technique, need not be added adhesive polyethylene alcohol, and the performance that manufactured zinc oxide resistance sheet has still had is reduced and is produced into This, improves production efficiency.
The above is only a preferred embodiment of the present invention, protection scope of the present invention is not limited merely to above-mentioned implementation Example.To those of ordinary skill in the art, obtained improvement and change in the case where not departing from the technology of the present invention concept thereof It changes and also should be regarded as protection scope of the present invention.

Claims (10)

1. a kind of preparation method of zinc oxide base nano composite granule resistor disc, includes the following steps：
(1) the various metals salt mixture including zinc salt is made into aqueous solution, instills surface modifier thereto, stirring is equal It is even to obtain metal mixed salt solution；
(2) complexing agent is dissolved in the ethanol solution for being made into complexing agent in absolute ethyl alcohol, metal mixed salt solution is added drop-wise to In the ethanol solution of complexing agent, stirring at a set temperature makes it fully dissolve, and then keeps the temperature, white gels are obtained after filtering；
(3) it by white gels washes clean, is put into tube furnace after dry, calcines at a set temperature, products therefrom is washed Totally, zinc oxide base nano composite granule is obtained after drying；
(4) aqueous：The distilled water of predetermined amount is added into zinc oxide base nano composite granule, stirs；
(5) tabletting：Powder after will be aqueous, which is put into tablet press machine, is compressed into tablet form crude green body；
(6) it is sintered：By crude green body in Muffle furnace calcination processing；
(7) it is ground, cleans；
(8) aluminium-plated, side applies insulation glaze.
2. the preparation method of zinc oxide base nano composite granule resistor disc according to claim 1, which is characterized in that described The component molar percentage of various metals salt mixture is：Zinc salt：80%~90%, bismuth salt：4%~5%, antimonic salt：4%~ 5%, magnesium salts：1%~2%, aluminium salt：1%~2%, cobalt salt：1%~2%, chromic salts：0%~1%, manganese salt：0%~1%, titanium Salt：0%~1%, yttrium salt：0%~0.1%.
3. the preparation method of zinc oxide base nano composite granule resistor disc according to claim 1 or 2, which is characterized in that The metal salt is one kind in acetate, nitrate；A concentration of 0.6~0.8mol/L of the metal salt solution.
4. the preparation method of zinc oxide base nano composite granule resistor disc according to claim 1 or 2, which is characterized in that The surface modifier is the one or more in dodecyl sodium sulfate, Triammonium citrate and Tween 80, and surface is modified The dosage of agent is the 2%~3% of metal salt weight.
5. the preparation method of zinc oxide base nano composite granule resistor disc according to claim 1 or 2, which is characterized in that The complexing agent is the one or more in oxalic acid, citric acid and Triammonium citrate；The absolute ethyl alcohol of the complexing agent is molten A concentration of 0.6~0.8mol/L of liquid.
6. the preparation method of zinc oxide base nano composite granule resistor disc according to claim 1 or 2, which is characterized in that In the step (2), whipping temp is 80~90 DEG C, and mixing time is 1~2h；Holding temperature is 80~90 DEG C, soaking time For 0.5~1h.
7. the preparation method of zinc oxide base nano composite granule resistor disc according to claim 1 or 2, which is characterized in that In the step (3), the calcination temperature of gel is 300~400 DEG C, and soaking time is 2~3h.
8. the preparation method of zinc oxide base nano composite granule resistor disc according to claim 1 or 2, which is characterized in that In the step (4), the distilled water of 1%~1.5% mass fraction is added into zinc oxide base nano composite granule.
9. the preparation method of zinc oxide base nano composite granule resistor disc according to claim 1 or 2, which is characterized in that In the step (6), calcination temperature is 1100~1200 DEG C, and soaking time is 90~100h.
10. a kind of preparation method system according to any one of the claim 1~10 zinc oxide base nano composite granule resistor disc Standby obtained zinc oxide base nano composite granule resistor disc.
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