CN103030171B - Method for preparing modified zinc oxide - Google Patents
Method for preparing modified zinc oxide Download PDFInfo
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- CN103030171B CN103030171B CN201210548654.9A CN201210548654A CN103030171B CN 103030171 B CN103030171 B CN 103030171B CN 201210548654 A CN201210548654 A CN 201210548654A CN 103030171 B CN103030171 B CN 103030171B
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- zinc oxide
- bismuth
- oxide
- zinc
- modified
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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 19
- 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
- 239000000463 material Substances 0.000 claims description 17
- 239000000843 powder Substances 0.000 claims description 17
- 238000002360 preparation method Methods 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
- 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
- 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
- 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
- 239000004202 carbamide Substances 0.000 description 2
- 239000006071 cream Substances 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
- 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
- 238000001354 calcination Methods 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
- 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
- 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
- 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
Classifications
-
- 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 social fast development, environmental pollution and traditional energy shortage, people need more efficient, and more the energy of environmental protection substitutes or supplementary traditional energy, and this causes the demand of mixed power electric car, power truck more and more.
Zinc-nickel cell is a kind of extremely potential alkaline secondary cell of environmental protection, and it has, and specific energy is high, specific power is large, the cheap advantage such as abundant and pollution-free of stable operating voltage, raw material.But 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 are all that zinc oxide dissolving enters into electrolytic solution, and when charging, the special growth characteristics of zinc crystal and inhomogeneous galvanic deposit cause.
For dendrite and the problem on deformation of zinc oxide, 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 Zinc oxide-base conductive oxide as kernel, described kernel is evenly 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, can be also with ZnO, Co
2o
3for main component, then add other conductive oxide component.
The preparation method of the described material of this invention is: employing zinc nitrate is raw material, ammoniacal liquor, urea is as precipitation agent, zinc nitrate and urea are dissolved in respectively in distilled water, completely dissolve after by 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, dry, obtain take Zinc oxide-base conductive oxide as kernel, kernel is evenly enclosed with the particle of zinc nitrate outward, then at 400～500 ℃, calcine and make zinc nitrate be converted into nano zine oxide in 1～2 hour, obtain the negative material of alkaline secondary zinc electrode.
Preparation method described in this invention, can sketch as following process: 1. first must first prepare Zinc oxide-base conductive oxide as kernel; 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. finally at high temperature zinc nitrate is decomposed into nano zine oxide.
We can draw to draw a conclusion by analysis:
1. this preparation method is too loaded down with trivial details, and the equipment relating to is more, and therefore 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 material used is as Co
2o
3it is a kind of valuable raw material, its price is equivalent to the more than 20 times of zinc oxide material price, if calculated by the adding proportion of this invention, the cost of zinc oxide negative material prepared by this invention 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, the modified zinc oxide of being prepared by the present invention, as secondary zinc electrode negative material there is 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%; One in sodium hydroxide or potassium hydroxide, zinc oxide, Bismuth trinitrate are mixed, mixture is carried out to ball milling and prepare Bi (OH)
3the presoma of clading ZnO then carries out thermolysis under hot environment, obtains the coated modified zinc oxide of bismuth oxide; In said process, Bismuth trinitrate reacts and obtains bismuth hydroxide presoma with sodium hydroxide or potassium hydroxide, then under hot environment, processes and obtains bismuth oxide.
Described zinc oxide is commercially available zinc oxide material, need to meet following technological standard:
Preferably, the preparation method of described modified zinc oxide comprises the steps:
The first step: take quantitative zinc oxide, Bismuth trinitrate is put into ball grinder, controlling 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, by said mixture ball milling, raw material is smashed; Wherein the quality of Bismuth trinitrate is precalculated, the cubage according to bismuth oxide in modified zinc oxide.
Second step: get a certain amount of sodium hydroxide or potassium hydroxide and add in the ball grinder described in the first step, wherein the mole number of sodium hydroxide or potassium hydroxide is equivalent to the first step and takes 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, by said mixture ball milling 20min～30min, obtain white powder;
The 3rd step: second step gained powder is put into and is placed in 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. modified oxidized zinc powder prepared by the present invention.
Beneficial effect of the present invention is:
1, preparation technology of the present invention is simple, 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, in preparation process of the present invention, not producing waste gas, waste water, waste residue, 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 corrosion certainly of zinc negative pole, and suppresses the generation of hydrogen in process of charging, therefore can reduce the decomposition of water, is conducive to the sealing of battery.
4, the sedimentation potential of bismuth is lower than zinc, and therefore bismuth is also the conductive agent of zinc active material simultaneously, can improve the power that discharges and recharges of negative pole.
5, 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.
Below in conjunction with the drawings and specific embodiments, the present invention will be further described.
Accompanying drawing explanation
Accompanying drawing is to adopt modified zinc oxide prepared by the present invention each example and the common zinc oxide cycle life graphic representation as negative electrode active material material.
Embodiment
Embodiment 1: the first step: take 1000 grams of zinc oxide, 200 grams of Bismuth trinitrates are put into ball grinder, and control ratio of grinding media to material is 25:1, by said mixture ball milling 20min, raw material are smashed.
Second step: get 72 grams, potassium hydroxide and put into the ball grinder described in the first step, and add 2 grams of deionized waters, by said mixture ball milling 20min, obtain white powder.
The 3rd step: second step gained powder is put into and is placed in retort furnace, heat up and heat-treat with the speed of 5 ℃/min, thermal treatment temp is 450 ℃, and is incubated 1h, obtains a kind of pale yellow powder, i.e. modified oxidized zinc powder prepared by the present invention.
Embodiment 2: the first step: take 500 grams of zinc oxide, 250 grams of Bismuth trinitrates are put into ball grinder, and control ratio of grinding media to material is 30:1, by said mixture ball milling 25min, raw material are smashed.
Second step: get 90 grams, potassium hydroxide and put into the ball grinder described in the first step, and add 5 grams of deionized waters, by said mixture ball milling 30min, obtain white powder.
The 3rd step: second step gained powder is put into and is placed in retort furnace, heat up and heat-treat with the speed of 5 ℃/min, thermal treatment temp is 500 ℃, and is incubated 1.5h, obtains a kind of pale yellow powder, i.e. modified oxidized zinc powder prepared by the present invention.
Embodiment 3: the first step: take 2000 grams of zinc oxide, 800 grams of Bismuth trinitrates are put into ball grinder, and control ratio of grinding media to material is 20:1, by said mixture ball milling 30min, raw material are smashed.
Second step: get 205 grams, sodium hydroxide and put into the ball grinder described in the first step, and add 24 grams of deionized waters, by said mixture ball milling 28min, obtain white powder.
The 3rd step: second step gained powder is put into and is placed in retort furnace, heat up and heat-treat with the speed of 5 ℃/min, thermal treatment temp is, 400 ℃, and be incubated 2h, obtain a kind of pale yellow powder, i.e. modified oxidized zinc powder prepared by the present invention.
Get modified zinc oxide and commercially available zinc oxide that appropriate example 1-3 makes, add respectively appropriate PTFE emulsion and CMC as binding agent, add a small amount of deionized water simultaneously, modulation oxidation calamine cream, then oxidation calamine cream is coated in to tin-coated copper online, after vacuum-drying, scrape off floating powder on surface, then on twin rollers, be pressed into pole plate, zinc negative pole.Nickel electrode, as anode, adopts slurry legal system standby.By 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 pocket type barrier film, positive and negative electrode is stacked and packed in battery jar, pour into the potassium hydroxide solution of 7mol as electrolytic solution, be test cell, will after standing test cell 6h, adopt 20mA/cm
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.The modified zinc oxide and the common zinc oxide that adopt the each example of the present invention to prepare are shown in accompanying drawing as the cycle life curve of negative electrode active material material.
Claims (1)
1. a preparation method for 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%; One in sodium hydroxide or potassium hydroxide, zinc oxide, Bismuth trinitrate are mixed, mixture is carried out to ball milling and prepare Bi (OH)
3the presoma of clading ZnO then carries out thermolysis under hot environment, obtains the coated modified zinc oxide of bismuth oxide; In said process, Bismuth trinitrate reacts and obtains bismuth hydroxide presoma with sodium hydroxide or potassium hydroxide, then under hot environment, processes and obtains bismuth oxide;
The preparation method of described modified zinc oxide comprises the steps:
The first step: take quantitative zinc oxide, Bismuth trinitrate is put into ball grinder, controlling 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, by said mixture ball milling, raw material is smashed;
Second step: get a certain amount of sodium hydroxide or potassium hydroxide and add in the ball grinder described in the first step, wherein the mole number of sodium hydroxide or potassium hydroxide is equivalent to the first step and takes 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, by the mixture ball milling 20min～30min of second step gained, obtain white powder;
The 3rd step: second step gained powder is put into and is placed in 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. modified oxidized zinc powder prepared by the present invention.
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| CN201210548654.9A CN103030171B (en) | 2012-12-17 | 2012-12-17 | Method for preparing modified zinc oxide |
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| CN201210548654.9A CN103030171B (en) | 2012-12-17 | 2012-12-17 | Method for preparing modified zinc oxide |
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| CN103030171A CN103030171A (en) | 2013-04-10 |
| CN103030171B true CN103030171B (en) | 2014-05-28 |
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| EP3016199B1 (en) | 2013-06-28 | 2019-01-09 | Positec Power Tools (Suzhou) Co., Ltd | Electrolytic solution and battery |
| US11069891B2 (en) | 2014-09-26 | 2021-07-20 | Positec Power Tools (Suzhou) Co., Ltd. | Battery, battery pack and continuous power supply |
| CN107039645B (en) * | 2017-04-11 | 2020-01-31 | 宁波富邦电池有限公司 | Primary alkaline battery negative electrode material and preparation method thereof |
| CN107265494B (en) * | 2017-06-06 | 2019-04-02 | 安徽锦华氧化锌有限公司 | A kind of modified nano zinc oxide |
| CN107394117A (en) * | 2017-06-09 | 2017-11-24 | 安徽零度新能源科技有限公司 | A kind of electrode of lithium cell |
| 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 |
| CN107338672A (en) * | 2017-07-15 | 2017-11-10 | 合肥皖水信息科技有限公司 | A kind of electro-photographic paper with good humidity resistance |
| CN107474419A (en) * | 2017-09-26 | 2017-12-15 | 安徽斯威达建材科技有限公司 | A kind of polystyrene fire-retardant heat insulation plate |
| CN108767215B (en) * | 2018-05-15 | 2021-03-26 | 华中科技大学 | Material for inhibiting zinc dendrite and preparation method and application thereof |
| CN109112003B (en) * | 2018-09-28 | 2021-08-06 | 广州市加茜亚化妆品有限公司 | Washing gel bead for dish-washing machine and preparation method |
| CN109592705A (en) * | 2019-01-02 | 2019-04-09 | 东莞理工学院 | A kind of no-solvent synthesis process of zinc oxide and application |
| CN110066109B (en) * | 2019-05-28 | 2022-02-22 | 江西陶瓷工艺美术职业技术学院 | Flux for antique pigment and application method thereof |
| CN111387351A (en) * | 2020-03-25 | 2020-07-10 | 济源市鲁泰纳米材料有限公司 | Surface-coated nano zinc oxide powder and preparation method thereof |
| 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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| GB792644A (en) * | 1954-12-22 | 1958-04-02 | Exxon Research Engineering Co | Improvements in or relating to catalytic dehydrogenation of secondary alcohols to ketones |
| US3778743A (en) * | 1973-02-23 | 1973-12-11 | Matsushita Electric Ind Co Ltd | Voltage-nonlinear resistors |
| US5039452A (en) * | 1986-10-16 | 1991-08-13 | Raychem Corporation | Metal oxide varistors, precursor powder compositions and methods for preparing same |
| CN1011839B (en) * | 1988-02-02 | 1991-02-27 | 西安交通大学 | Production method of zinc oxide resistor chip |
| CN1569616A (en) * | 2003-07-22 | 2005-01-26 | 西南科技大学 | Hydrothermal fluid process for preparation of doped zinc oxide powder |
| CN101533908B (en) * | 2009-04-02 | 2011-07-20 | 浙江理工大学 | Alkaline zinc-based secondary battery cathode material and preparation method thereof |
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