CN1724390A - Process for preparing alpha-phase nickel hydroxide by microwave water heating method - Google Patents
Process for preparing alpha-phase nickel hydroxide by microwave water heating method Download PDFInfo
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- CN1724390A CN1724390A CN 200510027346 CN200510027346A CN1724390A CN 1724390 A CN1724390 A CN 1724390A CN 200510027346 CN200510027346 CN 200510027346 CN 200510027346 A CN200510027346 A CN 200510027346A CN 1724390 A CN1724390 A CN 1724390A
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- microwave
- nickel hydroxide
- salt
- class alpha
- phase nickel
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Abstract
A process for preparing alpha-nickel hydroxide by microwave hydrothermal method features that the Ni ions are replaced by Al ions under the action of microwave reflux to generate Al substituted alpha-nickel hydroxide and it is possible to dope one or more kinds of metallic ions. Its advantage is excellent electrochemical performance.
Description
Technical field
The present invention relates to the method that a kind of preparation method of mineral compound, particularly microwave-hydrothermal method prepare class alpha-phase nickel hydroxide.
Background technology
As nickel-hydrogen battery positive pole material, class alpha-phase nickel hydroxide is compared with beta phase nickel hydroxide has lot of advantages, for example has higher discharge platform, high specific discharge capacity and long lifetime, but because class alpha-phase nickel hydroxide can not stable existence in highly basic, so the commercialization of still being unrealized.Main at present by introducing a large amount of trivalents or divalent metal element ion and negatively charged ion in the lattice of class alpha-phase nickel hydroxide, to improve its stability in the highly basic medium.Can replace Ni
2+The doping metals positively charged ion of synthetic class alpha-phase nickel hydroxide mainly contains Co
3+, Mn
3+, Fe
3+, Al
3+, Zn
2+, In
2+Deng, wherein use Co
3+The specific discharge capacity that replaces the synthetic class alpha-phase nickel hydroxide is bigger, but discharge platform is lower; Use Fe
3+The discharge platform that replaces the synthetic class alpha-phase nickel hydroxide is higher, but specific discharge capacity is low, and Fe
3+Existence to O
2Formation also have katalysis, be unsuitable for doing battery electrode.What study morely at present is to adopt Al
3+The research that replaces, Al
3+The class alpha-phase nickel hydroxide Stability Analysis of Structures that replaces, discharge platform is also higher, and specific discharge capacity is bigger.The multiple metal ion that mixes simultaneously can improve the stability and the chemical property of class alpha-phase nickel hydroxide.The synthetic main direct precipitation method that adopts of class alpha-phase nickel hydroxide prepares class alpha-phase nickel hydroxide, and a small amount of report about complex-precipitation method and the preparation of urea homogeneous precipitation method is also arranged in recent years.(Chinese patent CN1287693A) adopts the complex-precipitation method to prepare the class alpha-phase nickel hydroxide of high specific discharge capacity to people such as the Martin of the U.S. and Cha Kai.Concrete preparation method is: the nickel nitrate solution that at first will contain doped element is to disperse fully or the mode of droplet slowly adds in ammoniacal liquor or ammonium salt (ammonium nitrate, ammonium sulfate and the ammonium acetate etc.) solution, heat up then and stir 24h, so that class alpha-phase nickel hydroxide nucleation and slowly growth, then through the ammonia of catching up with of 36h, final pH value is 9, throw out is placed 12h again in mother liquor, then after filtration, the washing, the oven dry, the specific storage of the class alpha-phase nickel hydroxide product of preparation reaches 390mAh/g.Ammoniacal liquor or ammonium salt are not only made complexing agent but also do precipitation agent in the method, metal ion at first formed the ammonium title complex when mixed nitrate solution was added drop-wise in ammoniacal liquor or the ammonium salt solution, experience ammonium title complex is decomposed to form the nucleus of oxyhydroxide, the process of nuclei growth in heat-processed subsequently.But this method need add a large amount of ammoniacal liquor, and production environment is abominable, and need handle ammonia-containing water.People such as Dixit (Dixit M, Subbanna G N, and Kamath P V.J.Mater.Chem.1996,6:1429～1432) make precipitation agent with urea, with urea soln and nickel salt solution mixing post-heating, adopt homogeneous precipitation method to prepare non-substituted type class alpha-phase nickel hydroxide, but do not report its chemical property.People such as Achary (Acharya R, Subbaiah T, Anand S, et al.Mat.Chem.Phy.2003,81:45～49) adopt similar methods to prepare non-substituted type class alpha-phase nickel hydroxide, but degree of crystallinity is very poor.Microwave is combined with hydrothermal technique, is that the R ROY of U.S. University of Pennsylvania proposed in 1992.Compare with traditional hydrothermal method, the microwave hydrothermal synthesis method has fast, the characteristics such as system is even that are quick on the draw, are heated of rate of heating, and concentration that can be by changing starting raw material, the pH value and the conditions such as temperature, reaction times and the various additives of adding of reaction system prepare homogeneous fast, have the superfine powder of certain pattern.
Summary of the invention
The purpose of this invention is to provide the method that a kind of reaction conditions gentleness, the reaction times is short, simple and easy to do, production cost is low microwave-hydrothermal method prepare class alpha-phase nickel hydroxide.Employing replaces nickel ion with aluminum ion under microwave backflow effect, generate aluminium for class alpha-phase nickel hydroxide, and one or more other metal ions that can mix therein.
The concrete steps of method that microwave-hydrothermal method of the present invention prepares class alpha-phase nickel hydroxide are as follows:
1) preparing metal ionic concentration is 0.1～2 mol nickel salt aqueous solution nickel salt aqueous solution by nickel salt, aluminium salt and tensio-active agent is formed or be made up of metal-salt and the tensio-active agent of nickel salt, aluminium salt, doping metals M; Wherein aluminium salt interpolation molar ratio is Al/ (M+Ni+Al)=0.05～0.3, and it is M/ (M+Ni+Al)=0～0.25 that the metal-salt of doping metals M adds molar ratio, and the tensio-active agent addition is 0.1g/l～1.5g/l;
2) compound concentration is 0.1～10 mol aqueous solution of urea;
3) above-mentioned nickel salt aqueous solution and aqueous solution of urea are mixed after, ultra-sonic dispersion 5 minutes, join in the microwave reactor that has reflux, reaction is 10 minutes～8 hours under microwave action, microwave frequency 2.45GHz, microwave power is 100W～650W, 50～130 ℃ of Heating temperatures, after reaction finished, ageing was 1～12 hour under the normal temperature, filters subsequently, wash successively with distilled water and ethanol, methyl alcohol or acetone again, filter, and placed 60～120 ℃ of following dryings of baking oven 3～24 hours, promptly get class alpha-phase nickel hydroxide.
Nickel salt used in the present invention is selected from a kind of in hydrochloride, vitriol or the nitrate.
Aluminium salt used in the present invention is selected from a kind of in hydrochloride, vitriol or the nitrate.
The metal-salt of doping metals M used in the present invention is selected from one or more in hydrochloride, nitrate or the solvable vitriol, and wherein doping metals M is selected from one or more among Y, Ti, Cr, Sc, La, Co, Fe, In or the Zn.
Tensio-active agent used in the present invention is selected from one or more in polyoxyethylene alkylphenol ether, tween, Si Pan, polyvinyl alcohol or the polyoxyethylene glycol.
The method that microwave-hydrothermal method of the present invention prepares class alpha-phase nickel hydroxide is the precipitation from homogeneous solution (PFHS) agent with urea, utilizes the microwave hydrothermal effect to make its decomposes constantly generate NH
4OH is along with the pH value rising of solution, metal ion and OH
-Ionic bond produces precipitation, because OH
-Produce in the urea decomposition process, environment pH value changes less, makes precipitin reaction evenly to carry out.Mix in the time of multiple in addition metal ion and can further improve the stability and the chemical property of class alpha-phase nickel hydroxide.The method raw material that the present invention prepares class alpha-phase nickel hydroxide be simple and easy to, weak point consuming time, mild condition, simple and easy to do.The gained class alpha-phase nickel hydroxide has excellent electrochemical properties, and specific discharge capacity can reach 358mAh/g, and can be in highly basic stable existence.
Description of drawings
Fig. 1. with the not doped with Al of microwave-hydrothermal method preparation for the class alpha-phase nickel hydroxide X-ray diffractogram.
Fig. 2 with the not doped with Al of microwave-hydrothermal method preparation for the charging and discharging curve figure of class alpha-phase nickel hydroxide under 25 ℃.
Embodiment
Below by several concrete embodiment technical scheme of the present invention is further described, but do not limit this
Invention scope.
Embodiment 1
(1) preparation of nickel salt aqueous solution
With 19.31 gram NiSO
46H
2O, 3.03 gram Al (NO
3)
39H
2O, 0.03 gram alkyl phenol polyoxyethylene is dissolved in 100 ml distilled waters, and is standby.
(2) preparation of aqueous solution of urea
4.85g urea is dissolved in 100 ml distilled waters, standby.
(3) microwave-hydrothermal method prepares class alpha-phase nickel hydroxide
After above-mentioned nickel salt aqueous solution and aqueous solution of urea mixed, ultra-sonic dispersion 5 minutes, join in the microwave reactor that has reflux, under microwave action, react, microwave frequency 2450MHZ, microwave power is 325W, be 4 hours heat-up time, Heating temperature is 103 ℃, and after reaction finished, ageing was 10 hours under the normal temperature, filter subsequently, wash successively with distilled water and ethanol again, filter, and place 90 ℃ in baking oven following dry 4 hours, promptly get Al for class alpha-phase nickel hydroxide, its X-ray diffractogram and charging and discharging curve are distinguished as depicted in figs. 1 and 2: by the prepared as can be seen material of X-ray diffractogram really is class alpha-phase nickel hydroxide, and the diffraction peak of X-ray diffractogram is all narrower and sharp-pointed, and degree of crystallinity of the class alpha-phase nickel hydroxide of this explanation employing the inventive method preparation is higher.As seen from Figure 2, prepared Al reaches 341mAh/g for the specific discharge capacity of class alpha-phase nickel hydroxide, discharges and recharges condition: density of charging current 120mA/g, discharge current density 60mA/g.
Embodiment 2
(1) preparation of nickel salt aqueous solution
With 18.99 gram Ni (NO
3)
26H
2O, 6.06 gram Al (NO
3)
39H
2O, 0.02 gram alkyl phenol polyoxyethylene is dissolved in 100 ml distilled waters, and is standby.
(2) preparation of aqueous solution of urea
4.85g urea is dissolved in 100 ml distilled waters, standby.
(3) microwave-hydrothermal method prepares class alpha-phase nickel hydroxide
After above-mentioned nickel salt aqueous solution and aqueous solution of urea mixed, ultra-sonic dispersion 5 minutes joined in the microwave reactor that has reflux, react under microwave action, microwave frequency 2450MHZ, microwave power are 260W, be 3 hours heat-up time, and Heating temperature is 90 ℃, after reaction finishes, ageing is 10 hours under the normal temperature, filter subsequently, wash successively with distilled water and ethanol again, filter, and placed 90 ℃ of following dryings of baking oven 4 hours, promptly get Al for class alpha-phase nickel hydroxide.Specific discharge capacity reaches 318mAh/g.The condition that discharges and recharges is with embodiment 1.
Embodiment 3
(1) preparation of nickel salt aqueous solution
With 20.77 gram Ni (NO
3)
26H
2O, 2.27 gram Al (NO
3)
39H
2O, 1.16 gram Co (NO
3)
26H
2O, 0.03 gram alkyl phenol polyoxyethylene is dissolved in 100 ml distilled waters, and is standby.
(2) preparation of aqueous solution of urea
4.85g urea is dissolved in 100 ml distilled waters, standby.
(3) microwave-hydrothermal method prepares class alpha-phase nickel hydroxide
After above-mentioned nickel salt aqueous solution and aqueous solution of urea mixed, ultra-sonic dispersion 5 minutes joined in the microwave reactor that has reflux, react under microwave action, microwave frequency 2450MHZ, microwave power are 325W, be 5 hours heat-up time, and Heating temperature is 103 ℃, after reaction finishes, ageing is 10 hours under the normal temperature, filter subsequently, wash successively with distilled water and ethanol again, filter, and placed 90 ℃ of following dryings of baking oven 6 hours, promptly get the Co doped with Al for class alpha-phase nickel hydroxide.Specific discharge capacity reaches 358mAh/g.The condition that discharges and recharges is with embodiment 1.
Claims (5)
1. microwave-hydrothermal method prepares the method for class alpha-phase nickel hydroxide, it is characterized in that the preparation method is as follows:
1) preparing metal ionic concentration is 0.1～2 mol nickel salt aqueous solution, and nickel salt aqueous solution is by nickel salt, aluminium salt and tensio-active agent is formed or be made up of metal-salt and the tensio-active agent of nickel salt, aluminium salt, doping metals M; Wherein aluminium salt interpolation molar ratio is Al/ (M+Ni+Al)=0.05～0.3, and it is M/ (M+Ni+Al)=0～0.25 that the metal-salt of doping metals M adds molar ratio, and the tensio-active agent addition is 0.1g/l～1.5g/l;
2) compound concentration is 0.1～10 mol aqueous solution of urea;
3) above-mentioned nickel salt aqueous solution and aqueous solution of urea are mixed after, ultra-sonic dispersion 5 minutes, join in the microwave reactor that has reflux, reaction is 10 minutes～8 hours under microwave action, microwave frequency 2.45GHz, microwave power is 100W～650W, 50～130 ℃ of Heating temperatures, after reaction finished, ageing was 1～12 hour under the normal temperature, filters subsequently, wash successively with distilled water and ethanol, methyl alcohol or acetone again, filter, and placed 60～120 ℃ of following dryings of baking oven 3～24 hours, promptly get class alpha-phase nickel hydroxide.
2. microwave-hydrothermal method according to claim 1 prepares the method for class alpha-phase nickel hydroxide, it is characterized in that nickel salt is selected from a kind of in hydrochloride, vitriol or the nitrate.
3. microwave-hydrothermal method according to claim 1 prepares the method for class alpha-phase nickel hydroxide, it is characterized in that aluminium salt is selected from a kind of in hydrochloride, vitriol or the nitrate.
4. microwave-hydrothermal method according to claim 1 prepares the method for class alpha-phase nickel hydroxide, the metal-salt that it is characterized in that doping metals M is selected from one or more in hydrochloride, nitrate or the solvable vitriol, and wherein doping metals M is selected from one or more among Y, Ti, Cr, Sc, La, Co, Fe, In or the Zn.
5. microwave-hydrothermal method according to claim 1 prepares the method for class alpha-phase nickel hydroxide, it is characterized in that tensio-active agent is selected from one or more in polyoxyethylene alkylphenol ether, tween, Si Pan, polyvinyl alcohol or the polyoxyethylene glycol.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103137962A (en) * | 2013-03-11 | 2013-06-05 | 佛山市邦普循环科技有限公司 | Method for preparing nickel-cobalt-manganese hydroxide |
| CN103342396A (en) * | 2013-06-21 | 2013-10-09 | 北京理工大学 | Method for microwave liquid-phase synthesis of graphene-like two-dimensional nickel hydroxide nano material |
| CN105591087A (en) * | 2016-03-21 | 2016-05-18 | 内蒙古科技大学 | Preparation method of nickel hydroxide/graphene composite material for nickel-metal hydride battery positive pole |
| CN109585805A (en) * | 2018-10-31 | 2019-04-05 | 新疆舰目摩托车有限公司 | A kind of Ni-H cell anode plate material |
| CN110342588A (en) * | 2019-07-23 | 2019-10-18 | 上海应用技术大学 | A kind of ternary cathode material of lithium ion battery and preparation method thereof |
| CN111041214A (en) * | 2019-12-23 | 2020-04-21 | 先进储能材料国家工程研究中心有限责任公司 | Method for recycling and preparing α spherical nickel by utilizing waste zinc-containing nickel-hydrogen battery |
| CN111508730A (en) * | 2020-04-26 | 2020-08-07 | 陈昌弟 | Nickel-aluminum double metal hydroxide supercapacitor electrode material and preparation method thereof |
| CN115557547A (en) * | 2022-10-27 | 2023-01-03 | 浙江师范大学 | High-energy-density nano-disk-shaped alpha nickel hydroxide, preparation method thereof, electrode and battery |
-
2005
- 2005-06-30 CN CN 200510027346 patent/CN1724390A/en active Pending
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103137962A (en) * | 2013-03-11 | 2013-06-05 | 佛山市邦普循环科技有限公司 | Method for preparing nickel-cobalt-manganese hydroxide |
| CN103342396A (en) * | 2013-06-21 | 2013-10-09 | 北京理工大学 | Method for microwave liquid-phase synthesis of graphene-like two-dimensional nickel hydroxide nano material |
| CN105591087A (en) * | 2016-03-21 | 2016-05-18 | 内蒙古科技大学 | Preparation method of nickel hydroxide/graphene composite material for nickel-metal hydride battery positive pole |
| CN105591087B (en) * | 2016-03-21 | 2017-12-12 | 内蒙古科技大学 | A kind of preparation method of anode of nickel-metal hydride battery nickel hydroxide/graphene composite material |
| CN109585805A (en) * | 2018-10-31 | 2019-04-05 | 新疆舰目摩托车有限公司 | A kind of Ni-H cell anode plate material |
| CN110342588A (en) * | 2019-07-23 | 2019-10-18 | 上海应用技术大学 | A kind of ternary cathode material of lithium ion battery and preparation method thereof |
| CN111041214A (en) * | 2019-12-23 | 2020-04-21 | 先进储能材料国家工程研究中心有限责任公司 | Method for recycling and preparing α spherical nickel by utilizing waste zinc-containing nickel-hydrogen battery |
| CN111041214B (en) * | 2019-12-23 | 2021-08-31 | 先进储能材料国家工程研究中心有限责任公司 | Method for preparing alpha spherical nickel by recycling waste zinc-containing nickel-hydrogen batteries |
| CN111508730A (en) * | 2020-04-26 | 2020-08-07 | 陈昌弟 | Nickel-aluminum double metal hydroxide supercapacitor electrode material and preparation method thereof |
| CN111508730B (en) * | 2020-04-26 | 2021-12-10 | 宋伟杰 | Nickel-aluminum double metal hydroxide supercapacitor electrode material and preparation method thereof |
| CN115557547A (en) * | 2022-10-27 | 2023-01-03 | 浙江师范大学 | High-energy-density nano-disk-shaped alpha nickel hydroxide, preparation method thereof, electrode and battery |
| CN115557547B (en) * | 2022-10-27 | 2023-12-08 | 浙江师范大学 | High-energy-density nano-wafer-shaped alpha nickel hydroxide, preparation method thereof, electrode and battery |
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