CN103030171A - Method for preparing modified zinc oxide - Google Patents
Method for preparing modified zinc oxide Download PDFInfo
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- CN103030171A CN103030171A CN2012105486549A CN201210548654A CN103030171A CN 103030171 A CN103030171 A CN 103030171A CN 2012105486549 A CN2012105486549 A CN 2012105486549A CN 201210548654 A CN201210548654 A CN 201210548654A CN 103030171 A CN103030171 A CN 103030171A
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- zinc oxide
- bismuth
- oxide
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- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical class [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 title claims abstract description 11
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 70
- 239000011787 zinc oxide Substances 0.000 claims abstract description 37
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 34
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 30
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000000203 mixture Substances 0.000 claims abstract description 13
- 229910000416 bismuth oxide Inorganic materials 0.000 claims abstract description 12
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000011248 coating agent Substances 0.000 claims abstract description 6
- 238000000576 coating method Methods 0.000 claims abstract description 6
- PPNKDDZCLDMRHS-UHFFFAOYSA-N dinitrooxybismuthanyl nitrate Chemical compound [Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PPNKDDZCLDMRHS-UHFFFAOYSA-N 0.000 claims description 29
- 238000002360 preparation method Methods 0.000 claims description 27
- 239000000463 material Substances 0.000 claims description 17
- 239000000843 powder Substances 0.000 claims description 17
- 238000000498 ball milling Methods 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 5
- 238000007669 thermal treatment Methods 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 229940049676 bismuth hydroxide Drugs 0.000 claims description 2
- TZSXPYWRDWEXHG-UHFFFAOYSA-K bismuth;trihydroxide Chemical compound [OH-].[OH-].[OH-].[Bi+3] TZSXPYWRDWEXHG-UHFFFAOYSA-K 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 238000001149 thermolysis Methods 0.000 claims description 2
- 239000011701 zinc Substances 0.000 abstract description 21
- 229910052725 zinc Inorganic materials 0.000 abstract description 21
- 230000007613 environmental effect Effects 0.000 abstract description 6
- 239000002243 precursor Substances 0.000 abstract 2
- 239000010405 anode material Substances 0.000 abstract 1
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 abstract 1
- 238000005979 thermal decomposition reaction Methods 0.000 abstract 1
- 235000014692 zinc oxide Nutrition 0.000 description 27
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 210000004027 cell Anatomy 0.000 description 4
- 229910052797 bismuth Inorganic materials 0.000 description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 3
- 210000001787 dendrite Anatomy 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 229940105847 calamine Drugs 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 239000006071 cream Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 229910052864 hemimorphite Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- -1 polypropylene Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000002912 waste gas Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- CPYIZQLXMGRKSW-UHFFFAOYSA-N zinc;iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Fe+3].[Fe+3].[Zn+2] CPYIZQLXMGRKSW-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000022131 cell cycle Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000006353 environmental stress Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a method for preparing modified zinc oxide. The modified zinc oxide is prepared by coating bismuth oxide on zinc oxide; according to the weight percentage, the contents of the bismuth oxide is 5-25 percent and the zinc oxide is 75-95 percent; and one of sodium hydroxide or potassium hydroxide is mixed with zinc oxide and bismuth nitrate, the mixture is ball-milled to prepare a precursor of a Bi(OH)3-coated ZnO, and then the thermal decomposition is carried out to the precursor in the high temperature environment to obtain the bismuth oxide coated modified zinc oxide. The prepared modified zinc oxide as the anode material of a secondary zinc electrode has the advantages of low price, environmental protection, less investment, good electric conductivity, high charge acceptance, high specific capacity, long cycle life and the like.
Description
Technical field
The present invention relates to technical field of chemical power, especially a kind of preparation method of modified zinc oxide.
Background technology
Along with the fast development of society, environmental pollution and traditional energy shortage, people need more efficient, and more the energy of environmental protection substitutes or additional traditional energy, and this causes the demand of mixed power electric car, power truck more and more.
Zinc-nickel cell is a kind of alkaline secondary cell that has development potentiality of environmental protection, and it has, and specific energy height, specific power are large, the cheap advantage such as abundant and pollution-free of stable operating voltage, raw material.Yet the short problem of Zinc-nickel battery negative cycle life has limited its commercial applications.The deformation of zinc negative pole and dendrite are the major causes that causes zinc-nickel cell cycle life short.Zinc dendrite growth and zinc electrode distortion all are that the zinc oxide dissolving enters into electrolytic solution, and the special growth characteristics of zinc crystal and inhomogeneous galvanic deposit cause during charging.
For dendrite and the problem on deformation of zinc oxide, the researchist has proposed many methods both at home and abroad, and wherein relatively effective means is the coating technology of zinc negative material.
Publication number is the Chinese invention patent document (number of patent application: 200510060941.5) disclose " negative material of a kind of alkaline secondary zinc electrode and preparation method thereof " of CN 1744355A, the technical scheme of this invention is: take the Zinc oxide-base conductive oxide as kernel, described kernel evenly is enclosed with nano granular of zinc oxide outward, wherein the chemical constitution of Zinc oxide-base conductive oxide is: the ZnO of 90～98 weight parts, the Co of 2～5 weight parts
2O
3, also can be with ZnO, Co
2O
3Be main component, add again other conductive oxide component.
This invents described material preparation method: the employing zinc nitrate is raw material, ammoniacal liquor, urea is as precipitation agent, be dissolved in respectively zinc nitrate and urea in the distilled water, fully the dissolving after with the two mixing, then in solution, add described Zinc oxide-base conductive oxide, ultrasonic stirring is heated to 90～100 ℃, be incubated 2～3 hours, cooled and filtered, washing, drying obtains take the Zinc oxide-base conductive oxide as kernel, and kernel evenly is enclosed with the particle of zinc nitrate outward, then make zinc nitrate be converted into nano zine oxide in 1～2 hour 400～500 ℃ of lower calcinings, obtain the negative material of alkaline secondary zinc electrode.
This invents described preparation method, can sketch to be following process: at first must prepare first the Zinc oxide-base conductive oxide as kernel 1.; 2. then prepare zinc nitrate coating zinc oxide base conductive oxide as presoma, equipment used relates to ultrasonic wave and heating system etc.; 3. again to pass through filtration washing, 4. at high temperature zinc nitrate is decomposed into nano zine oxide at last.
We can draw to draw a conclusion by analysis:
1. this preparation method is too loaded down with trivial details, and the equipment that relates to is more, so facility investment is larger.
2. this not environmental protection of preparation method's production technique, washing produces a large amount of waste water, waste gas with calcination process, has therefore increased environmental stress, is not suitable for suitability for industrialized production.
3. this preparation method's cost is higher, and used material is such as Co
2O
3It is a kind of valuable raw material, its price is equivalent to more than 20 times of zinc oxide material price, if the adding proportion by this invention is calculated, the cost of the zinc oxide negative material of this invention preparation is equivalent to 3～5 times of common zinc oxide material, and this cost is disadvantageous to suitability for industrialized production.
Summary of the invention
For solving above-mentioned drawback, technical problem to be solved by this invention is, a kind of preparation method of modified zinc oxide is provided, by the modified zinc oxide of the present invention preparation, as the secondary zinc electrode negative material have cheapness, environmental protection, less investment, good conductivity, the advantage such as charge acceptance is strong, specific storage is high, have extended cycle life.In order to solve the problems of the technologies described above, the technical solution used in the present invention is that a kind of preparation method of modified zinc oxide adopts the preparation of bismuth oxide coating zinc oxide; By weight, wherein bismuth oxide content is 5～25%, and zinc oxide content is 75%～95%; A kind of, zinc oxide in sodium hydroxide or the potassium hydroxide, Bismuth trinitrate are mixed, mixture is carried out ball milling prepare Bi (OH)
3Then the presoma of clading ZnO carries out thermolysis under hot environment, obtain the modified zinc oxide that bismuth oxide coats; In the said process, Bismuth trinitrate and sodium hydroxide or potassium hydroxide reaction obtain the bismuth hydroxide presoma, then process obtaining bismuth oxide under hot environment.
Described zinc oxide is commercially available zinc oxide material, need to satisfy following technological standard:
Preferably, the preparation method of described modified zinc oxide comprises the steps:
The first step: take by weighing quantitative zinc oxide, Bismuth trinitrate is put into ball grinder, the control ratio of grinding media to material is 10:1～50:1, and the weight of Bismuth trinitrate is 10.9%～67% of zinc oxide weight, with the said mixture ball milling, raw material is smashed; Wherein the quality of Bismuth trinitrate is precalculated, according to the cubage of bismuth oxide in modified zinc oxide.
Second step: get a certain amount of sodium hydroxide or potassium hydroxide and add in the described ball grinder of the first step, wherein the mole number of sodium hydroxide or potassium hydroxide is equivalent to the first step and takes by weighing 3.1～3.3 times of Bismuth trinitrate mole number, and add a little deionized water, the weight of water is 1%～5% of Bismuth trinitrate weight, with said mixture ball milling 20min～30min, obtain white powder;
The 3rd step: second step gained powder put into place in the retort furnace, at the uniform velocity heat up and heat-treat, thermal treatment temp is 400～650 ℃, and is incubated 1～2h, obtains a kind of pale yellow powder, i.e. the modified oxidized zinc powder of the present invention preparation.
Beneficial effect of the present invention is:
1, preparation technology of the present invention is simple, and is with short production cycle, is easy to suitability for industrialized production, and facility investment is less, is a kind of low input, the new technology project of high production.
2, not producing waste gas, waste water, waste residue in the preparation process of the present invention, is a kind of production technology of environmental protection, without any byproduct, does not need to carry out water treatment and gas processing.
3, the prepared modified oxidized zinc powder of the present invention is a kind of high oxide powder and zinc that presses down hydrogen overpotential, and operating voltage is higher, can reduce the certainly corrosion of zinc negative pole, and suppresses the generation of hydrogen in process of charging, so can reduce the decomposition of water, is conducive to the sealing of battery.
4, the sedimentation potential of bismuth is lower than zinc, so bismuth also is the conductive agent of zinc active material simultaneously, can improve the power that discharges and recharges of negative pole.
5, the bismuth coating zinc oxide can obviously improve cycle performance and the loading capacity of electrode, reduces charging platform, has improved the electrochemical activity of zinc oxide.
The present invention will be further described below in conjunction with the drawings and specific embodiments.
Description of drawings
Accompanying drawing is the modified zinc oxide that adopts each example preparation of the present invention and the common zinc oxide cycle life graphic representation as the negative electrode active material material.
Embodiment
Embodiment 1: the first step: take by weighing 1000 gram zinc oxide, 200 gram Bismuth trinitrates are put into ball grinder, and the control ratio of grinding media to material is 25:1, with said mixture ball milling 20min, raw material is smashed.
Second step: get potassium hydroxide 72 grams and put into the described ball grinder of the first step, and add 2 gram deionized waters, with said mixture ball milling 20min, obtain white powder.
The 3rd step: second step gained powder put into place in the retort furnace, heat up with the speed of 5 ℃/min and heat-treat, thermal treatment temp is 450 ℃, and insulation 1h, obtains a kind of pale yellow powder, i.e. the modified oxidized zinc powder of the present invention preparation.
Embodiment 2: the first step: take by weighing 500 gram zinc oxide, 250 gram Bismuth trinitrates are put into ball grinder, and the control ratio of grinding media to material is 30:1, with said mixture ball milling 25min, raw material is smashed.
Second step: get potassium hydroxide 90 grams and put into the described ball grinder of the first step, and add 5 gram deionized waters, with said mixture ball milling 30min, obtain white powder.
The 3rd step: second step gained powder put into place in the retort furnace, heat up with the speed of 5 ℃/min and heat-treat, thermal treatment temp is 500 ℃, and insulation 1.5h, obtains a kind of pale yellow powder, i.e. the modified oxidized zinc powder of the present invention preparation.
Embodiment 3: the first step: take by weighing 2000 gram zinc oxide, 800 gram Bismuth trinitrates are put into ball grinder, and the control ratio of grinding media to material is 20:1, with said mixture ball milling 30min, raw material is smashed.
Second step: get sodium hydroxide 205 grams and put into the described ball grinder of the first step, and add 24 gram deionized waters, with said mixture ball milling 28min, obtain white powder.
The 3rd step: second step gained powder put into place in the retort furnace, heat up with the speed of 5 ℃/min and heat-treat, thermal treatment temp is, 400 ℃, and insulation 2h, obtain a kind of pale yellow powder, i.e. the modified oxidized zinc powder of the present invention preparation.
Get modified zinc oxide and commercially available zinc oxide that an amount of example 1-3 makes, add respectively an amount of PTFE emulsion and CMC as binding agent, add simultaneously a small amount of deionized water, modulation oxidation calamine cream, then it is online the oxidation calamine cream to be coated in tin-coated copper, scrape off floating powder on surface after the vacuum-drying, then be pressed into pole plate at twin rollers, the zinc negative pole.Nickel electrode adopts the slurry legal system standby as anode.With nickel electrode external parcel one deck polypropylene non-woven fabric, the polypropylene grafted film of pocket type is as battery diaphragm, zinc electrode is packed in the pocket type barrier film, positive and negative electrode is stacked in the battery jar of packing into, pour into the potassium hydroxide solution of 7mol as electrolytic solution, be test cell, adopt 20mA/cm after test cell is left standstill 6h
2Constant current voltage limiting discharges and recharges, charging voltage restriction 1.9V, discharge cut-off voltage restriction 1.4V, the chemical property of repeatedly surveying modified oxidized zinc active material like this.Adopt modified zinc oxide and the common zinc oxide of each example preparation of the present invention to see accompanying drawing as the cycle life curve of negative electrode active material material.
Claims (2)
1. the preparation method of a modified zinc oxide is characterized in that, adopts the preparation of bismuth oxide coating zinc oxide; By weight, wherein bismuth oxide content is 5～25%, and zinc oxide content is 75%～95%; A kind of, zinc oxide in sodium hydroxide or the potassium hydroxide, Bismuth trinitrate are mixed, mixture is carried out ball milling prepare Bi (OH)
3Then the presoma of clading ZnO carries out thermolysis under hot environment, obtain the modified zinc oxide that bismuth oxide coats; In the said process, Bismuth trinitrate and sodium hydroxide or potassium hydroxide reaction obtain the bismuth hydroxide presoma, then process obtaining bismuth oxide under hot environment.
2. the preparation method of a kind of modified zinc oxide as claimed in claim 1 is characterized in that, the preparation method of described modified zinc oxide comprises the steps:
The first step: take by weighing quantitative zinc oxide, Bismuth trinitrate is put into ball grinder, the control ratio of grinding media to material is 10:1～50:1, and the weight of Bismuth trinitrate is 10.9%～67% of zinc oxide weight, with the said mixture ball milling, raw material is smashed;
Second step: get a certain amount of sodium hydroxide or potassium hydroxide and add in the described ball grinder of the first step, wherein the mole number of sodium hydroxide or potassium hydroxide is equivalent to the first step and takes by weighing 3.1～3.3 times of Bismuth trinitrate mole number, and add a little deionized water, the weight of water is 1%～5% of Bismuth trinitrate weight, with said mixture ball milling 20min～30min, obtain white powder;
The 3rd step: second step gained powder put into place in the retort furnace, at the uniform velocity heat up and heat-treat, thermal treatment temp is 400～650 ℃, and is incubated 1～2h, obtains a kind of pale yellow powder, i.e. the modified oxidized zinc powder of the present invention preparation.
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| CN201210548654.9A CN103030171B (en) | 2012-12-17 | 2012-12-17 | Method for preparing modified zinc oxide |
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| CN107130147A (en) * | 2017-06-22 | 2017-09-05 | 合肥市闵葵电力工程有限公司 | The aluminium alloy conductor material and preparation method of a kind of high conductivity |
| CN107265494A (en) * | 2017-06-06 | 2017-10-20 | 安徽锦华氧化锌有限公司 | A kind of modified nano zinc oxide |
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| CN116835973A (en) * | 2023-06-16 | 2023-10-03 | 华中科技大学 | Bismuth oxide coated zinc oxide powder and preparation method and application thereof |
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