CN102863032A - Preparation method of porous nano-nickel oxide material - Google Patents
Preparation method of porous nano-nickel oxide material Download PDFInfo
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- CN102863032A CN102863032A CN201210332729XA CN201210332729A CN102863032A CN 102863032 A CN102863032 A CN 102863032A CN 201210332729X A CN201210332729X A CN 201210332729XA CN 201210332729 A CN201210332729 A CN 201210332729A CN 102863032 A CN102863032 A CN 102863032A
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- nickel oxide
- water
- nitrate hexahydrate
- oxide material
- bicarbonate
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Abstract
The invention relates to a preparation method of a porous nano-nickel oxide material. The method comprises the following steps: a) respectively dissolving ammonium bicarbonate and nickel nitrate hexahydrate in water, stirring and mixing, wherein mole ratio of the materials is ammonium bicarbonate: nickel nitrate hexahydrate = 2: 1; b) adding ammonia water into the above mixed liquid to adjust pH of the solution, stirring at room temperature, transferring to a reactor, and putting into a constant temperature drying oven of 120-180 DEG C to age for 2 hours so as to obtain a solid-liquid mixture; and c) taking out the solid-liquid mixture, filtering, washing, drying and roasting to obtain a black nickel oxide powder. The whole process is environmentally friendly and has no pollution. A surfactant and the like needn't to be added. The particle size distribution of the nano-nickel oxide material prepared by the method is uniform and controllable. The nano-nickel oxide material has good dispersion and very high specific capacitance which can reach up to 630 F/g.
Description
Technical field
The present invention relates to a kind of preparation method of porous nano nickel oxide material, belong to inorganic porous material and field of nanometer material technology.
Background technology
Nickel oxide is widely used in catalysis, electrochomeric films, and fuel cell electrode, gas sensor, etc., nickel oxide is widely used in ultracapacitor as a kind of energy storage material especially in recent years.About the preparation of nano-nickel oxide, a lot of relevant reports have been arranged both at home and abroad, the methods such as sol-gel method, chemical precipitation method, electrochemical deposition method are wherein arranged.All there is such-and-such problem in these methods, such as, complex process, reaction process are difficult to control, and energy consumption is large, heavily contaminated, preparation cost is higher, and the gained nano particle diameter is difficult to control etc.(patent No.: CN 1686831A) adopt the method for solid state reaction and microwave heating, synthesized purity take basic nickel carbonate and oxalic acid as raw material higher, the uniform nano oxidized nickel material of particle diameter for Chinese invention patent " microwave synthetizing nano nickel oxide ".But above-mentioned reaction need add the nano-nickel oxide crystal seed in advance, and two-step reaction all need to carry out under microwave condition, so synthetic cost increases, is unfavorable for scale operation.CN 101143734A is with nickel acetate or nickelous nitrate, citric acid, and ethylene glycol or ethylene glycol monomethyl ether are raw material, it is even to adopt sol-gel method to obtain particle size distribution, the nickel oxide nano-crystal material that the chemical property that purity is high is good.But the method cost is higher, and reaction process is difficult to control, and technique is complicated.
The present invention relates to a kind of synthetic method of hydrothermal deposition, prepare nano level nickel oxide material, take Nickelous nitrate hexahydrate and bicarbonate of ammonia as raw material, finally obtain the product of Nanoparticulate.Reaction mechanism is as follows:
A) bicarbonate of ammonia hydrolysis produce OH-:
HCO
3 -+H
2O→OH
-+H
2CO
3;
B) light green Ni (OH)
2Generation:
|Ni
2++2OH
-→Ni(OH)
2↓;
C) 400 ℃ of lower roastings obtain black nano nickel oxide powder:
The material that obtains is used for ultracapacitor as positive electrode material, has good chemical property.
Summary of the invention
The object of the invention is to for the high energy consumption that exists in the current techniques, heavily contaminated, complex process, and the uneven first-class deficiency of grain-size provide a kind of synthetic method of simple hydrothermal deposition to prepare the nano level nickel oxide material.Cost of material of the present invention is cheap, and cost is low, and building-up process is simple, easy handling, and condition is loose, environmentally safe.The product that obtains simultaneously is pure nickel oxide particle, and particle diameter is controlled at 10～20nm, and size is homogeneous relatively.
The present invention adopts the synthetic method of hydrothermal deposition, and take Nickelous nitrate hexahydrate as the nickel source, bicarbonate of ammonia is precipitation agent, by the pH value of ammoniacal liquor regulator solution.By changing hydrothermal temperature, obtain the nano oxidized nickel material of different-grain diameter.
Technical scheme of the present invention is:
A kind of preparation method of porous nano nickel oxide material may further comprise the steps:
A) bicarbonate of ammonia and Nickelous nitrate hexahydrate is water-soluble respectively, after stirring at normal temperature made it form uniform solution respectively, then with its mixing, its material proportion mol ratio was bicarbonate of ammonia: Nickelous nitrate hexahydrate=2: 1;
B) adding ammoniacal liquor regulator solution pH value in the above-mentioned mixed solution is 9～10, continues under the room temperature to stir 30～60min, changes in the reactor, and the thermostatic drying chamber of putting into 120 ℃～180 ℃ wore out 2 hours, obtained solidliquid mixture;
C) solidliquid mixture is taken out rear the filtration, water and ethanol wash respectively, 70 ℃ of thermostatic drying chamber inner dryings 12 hours, obtain the light green nickel hydroxide powder afterwards, 400 ℃ of roastings 2 hours in retort furnace obtain the black nickel oxide powder under the last air conditions.
In the described step a), the water-soluble proportioning of bicarbonate of ammonia is: every 2.4g bicarbonate of ammonia is dissolved in 30ml water; The water-soluble proportioning of Nickelous nitrate hexahydrate is: every 4.4g Nickelous nitrate hexahydrate is dissolved in the 30ml water.
The concentration of regulating the ammoniacal liquor of pH value in the described step b) is mass concentration 25%.
The synthetic sample that obtains is black powder, can obtain the porous nano nickel oxide material of different-grain diameter and different pore size size under different experimental conditions.
The present invention has following characteristics:
1. to adopt Nickelous nitrate hexahydrate be the nickel source in the present invention, and take bicarbonate of ammonia as precipitation agent, ammoniacal liquor is pH value buffer reagent, and water is the synthetic nickel oxide precursor of solvent, and experimental raw all is the common inorganic materials that is easy to get, and has reduced experimental cost.Roasting for presoma is in common tube furnace, and need not to pass into rare gas element.Whole process environment is friendly, and is pollution-free.
2. the present invention need not to add tensio-active agent etc., and just by regulating the temperature of hydro-thermal reaction, can obtain particle diameter is that 10～20nm, specific surface area are about 77.937～118.092m
2/ g and aperture are the nickel oxide material of 5.5nm.The nano-nickel oxide material particle size that the method prepares is evenly distributed and is controlled, favorable dispersity.
3. preparation technology of the present invention and equipment are simple, and is easy and simple to handle, easy control of reaction conditions.The nano oxidized nickel material that the method prepares has very high ratio electric capacity, reaches as high as 630F/g, is a kind of good super capacitor material, can be widely used in electrochemistry.
Description of drawings
Fig. 1 is sample XRD figure sheet, and (a) embodiment 1, and (b) embodiment 2, and (c) embodiment 3, and (d) embodiment 4.
Fig. 2 is the graph of pore diameter distribution that nitrogen adsorption-desorption isotherm and DFT method are calculated, and (a) embodiment 1, and (b) embodiment 2.
Fig. 3 is Sample Scan Electronic Speculum figure, (a) and (b) embodiment 1, and (c) and (d) embodiment 2, (e) embodiment 3, and (f) embodiment 4.
Specific embodiments
Embodiment 1:
4.4g Nickelous nitrate hexahydrate and 2.4g bicarbonate of ammonia are dissolved in respectively in the 30ml water, its material proportion mol ratio is Nickelous nitrate hexahydrate: bicarbonate of ammonia=1:2, stir respectively under the room temperature and form all with transparent solution, both are mixed, adding ammoniacal liquor (quality solubility is 25%) adjusting pH value is 9, continue to stir 30～60min under the room temperature, mixture is transferred to in the teflon-lined reactor, put into 180 ℃ of thermostatic drying chambers and wore out 2 hours, cool off under the room temperature, after solidliquid mixture is taken out, filter, and water and washing with alcohol are for several times, and 70 ℃ of thermostatic drying chamber inner dryings 12 hours obtain the light green nickel hydroxide powder.Then with 400 ℃ of roastings 2 hours in retort furnace under its air conditions, finally obtain the nickel oxide powder of black.Can obtain 2 θ by X-ray diffracting spectrum is 37.2 °, 43.2 °, 62.7 °, locate to occur apparent in view diffraction peak (among Fig. 1 a) for 76.5 ° and 79.9 °, respectively corresponding (110), (200), (220), (311) and (222) crystalline phase, and there are not other magazine peaks, show that product is single isometric system nickel oxide (JCPDS 65-2901, Fm-3m(225), a=b=c=0.4177nm).According to maximum diffraction peak (200) crystalline phase, by the Scherrer formula (
) count particles particle diameter 11.7nm.Nitrogen adsorption and graph of pore diameter distribution (among Fig. 2 a) the show sample specific surface area be 118.092 m
2/ g, the aperture is 5.53 nm.A and b Scanning Electron Microscope photos reveal sample dispersion are good among Fig. 3, and sample crystal grain is approximately 10～15nm, conform to XRD calculation result.The nano oxidized nickel material that is obtained by this method is as working electrode, and under three-electrode system, it is 520 F/g than electric capacity.
Embodiment 2:
4.4g Nickelous nitrate hexahydrate and 2.4g bicarbonate of ammonia are dissolved in respectively in the 30ml water, its material proportion mol ratio is Nickelous nitrate hexahydrate: bicarbonate of ammonia=1:2, stir respectively under the room temperature and form all with transparent solution, both are mixed, adding ammoniacal liquor (quality solubility is 25%) adjusting pH value is 9, continue to stir 30～60min under the room temperature, mixture is transferred to in the teflon-lined reactor, put into 160 ℃ of thermostatic drying chambers and wore out 2 hours, cool off under the room temperature, after solidliquid mixture is taken out, filter, and water and washing with alcohol are for several times, and 70 ℃ of thermostatic drying chamber inner dryings 12 hours obtain the light green nickel hydroxide powder.Then with 400 ℃ of roastings 2 hours in retort furnace under its air conditions, finally obtain the nickel oxide powder of black.Can obtain 2 θ by X-ray diffracting spectrum is 37.2 °, 43.2 °, 62.7 °, locate to occur apparent in view diffraction peak (b among Fig. 1) for 76.5 ° and 79.9 °, respectively corresponding (110), (200), (220), (311) and (222) crystalline phase, and there are not other magazine peaks, show that product is single isometric system nickel oxide (JCPDS 65-2901, Fm-3m(225), a=b=c=0.4177nm).According to maximum diffraction peak (200) crystalline phase, by the Scherrer formula (
) count particles particle diameter 12.6nm.Nitrogen adsorption and graph of pore diameter distribution (b among Fig. 2) show sample specific surface area is 77.937m
2/ g, the aperture is 5.42 nm.C and d Scanning Electron Microscope photos reveal sample are sheet among Fig. 3, and good dispersity, and lamellar spacing is approximately 10～20nm, conform to XRD calculation result.
Embodiment 3:
4.4g Nickelous nitrate hexahydrate and 2.4g bicarbonate of ammonia are dissolved in respectively in the 30ml water, its material proportion mol ratio is Nickelous nitrate hexahydrate: bicarbonate of ammonia=1:2, stir respectively under the room temperature and form all with transparent solution, both are mixed, adding ammoniacal liquor (quality solubility is 25%) adjusting pH value is 9, continue to stir 30～60min under the room temperature, mixture is transferred to in the teflon-lined reactor, put into 140 ℃ of thermostatic drying chambers and wore out 2 hours, cool off under the room temperature, after solidliquid mixture is taken out, filter, and water and washing with alcohol are for several times, and 70 ℃ of thermostatic drying chamber inner dryings 12 hours obtain the light green nickel hydroxide powder.Then with 400 ℃ of roastings 2 hours in retort furnace under its air conditions, finally obtain the nickel oxide powder of black.Can obtain 2 θ by X-ray diffracting spectrum is 37.2 °, 43.2 °, 62.7 °, locate to occur apparent in view diffraction peak (c among Fig. 1) for 76.5 ° and 79.9 °, respectively corresponding (110), (200), (220), (311) and (222) crystalline phase, and there are not other magazine peaks, show that product is single isometric system nickel oxide (JCPDS 65-2901, Fm-3m(225), a=b=c=0.4177nm).According to maximum diffraction peak (200) crystalline phase, by the Scherrer formula (
) count particles particle diameter 14.3nm.E Scanning Electron Microscope photos reveal sample is particulate state among Fig. 3, and better dispersed.
Embodiment 4:
4.4g Nickelous nitrate hexahydrate and 2.4g bicarbonate of ammonia are dissolved in respectively in the 30ml water, its material proportion mol ratio is Nickelous nitrate hexahydrate: bicarbonate of ammonia=1:2, stir respectively under the room temperature and form all with transparent solution, both are mixed, adding ammoniacal liquor (quality solubility is 25%) adjusting pH value is 9, continue to stir 30～60min under the room temperature, mixture is transferred to in the teflon-lined reactor, put into 120 ℃ of thermostatic drying chambers and wore out 2 hours, cool off under the room temperature, after solidliquid mixture is taken out, filter, and water and washing with alcohol are for several times, and 70 ℃ of thermostatic drying chamber inner dryings 12 hours obtain the light green nickel hydroxide powder.Then with 400 ℃ of roastings 2 hours in retort furnace under its air conditions, finally obtain the nickel oxide powder of black.Can obtain 2 θ by X-ray diffracting spectrum is 37.2 °, 43.2 °, 62.7 °, locate to occur apparent in view diffraction peak (d among Fig. 1) for 76.5 ° and 79.9 °, respectively corresponding (110), (200), (220), (311) and (222) crystalline phase, and there are not other magazine peaks, show that product is single isometric system nickel oxide (JCPDS 65-2901, Fm-3m(225), a=b=c=0.4177nm).According to maximum diffraction peak (200) crystalline phase, by the Scherrer formula (
) count particles particle diameter 10.8nm.F Scanning Electron Microscope photos reveal sample is particulate state among Fig. 3, and favorable dispersity.The nano oxidized nickel material that is obtained by this method is as working electrode, and under three-electrode system, it is 630 F/g than electric capacity.
Can find out that from top embodiment the present invention can obtain the nano-nickel oxide powder in different-grain diameter and different specific surface area and aperture by regulating different temperature of reaction.
Claims (3)
1. the preparation method of a porous nano nickel oxide material is characterized by and may further comprise the steps:
A) bicarbonate of ammonia and Nickelous nitrate hexahydrate is water-soluble respectively, after stirring at normal temperature made it form uniform solution respectively, then with its mixing, its material proportion mol ratio was bicarbonate of ammonia: Nickelous nitrate hexahydrate=2: 1;
B) adding ammoniacal liquor regulator solution pH value in the above-mentioned mixed solution is 9～10, continues under the room temperature to stir 30～60min, changes in the reactor, and the thermostatic drying chamber of putting into 120 ℃～180 ℃ wore out 2 hours, obtained solidliquid mixture;
C) solidliquid mixture is taken out rear the filtration, water and ethanol wash respectively, 70 ℃ of thermostatic drying chamber inner dryings 12 hours, obtain the light green nickel hydroxide powder afterwards, 400 ℃ of roastings 2 hours in retort furnace obtain the black nickel oxide powder under the last air conditions.
2. the preparation method of porous nano nickel oxide material as claimed in claim 1 is characterized by in the described step a), and the water-soluble proportioning of bicarbonate of ammonia is: every 2.4g bicarbonate of ammonia is dissolved in 30ml water; The water-soluble proportioning of Nickelous nitrate hexahydrate is: every 4.4g Nickelous nitrate hexahydrate is dissolved in the 30ml water.
3. the preparation method of porous nano nickel oxide material as claimed in claim 1, it is characterized by the concentration of regulating the ammoniacal liquor of pH value in the described step b) is mass concentration 25%.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103936083A (en) * | 2013-01-23 | 2014-07-23 | 中国石油化工股份有限公司 | Nickel magnesium composite oxide and preparation method thereof |
| CN108373176A (en) * | 2018-04-16 | 2018-08-07 | 沈阳建筑大学 | A kind of nano-nickel oxide raw powder's production technology for ultracapacitor |
| CN110102457A (en) * | 2019-04-19 | 2019-08-09 | 东北大学秦皇岛分校 | A method of preparing nickel oxide nano-crystal electrochomeric films at low temperature |
| CN114308041A (en) * | 2020-09-30 | 2022-04-12 | 天津理工大学 | Preparation method of black nickel oxide and application of black nickel oxide in catalyzing oxidation reaction of 1, 2-diol for breaking C-C bond |
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| CN101269850A (en) * | 2008-05-06 | 2008-09-24 | 华东理工大学 | Method for preparing flower form nickelous oxide |
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| CN101269850A (en) * | 2008-05-06 | 2008-09-24 | 华东理工大学 | Method for preparing flower form nickelous oxide |
| CN102139931A (en) * | 2010-01-29 | 2011-08-03 | 中国石油化工股份有限公司 | Preparation method of nano nickel oxide |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103936083A (en) * | 2013-01-23 | 2014-07-23 | 中国石油化工股份有限公司 | Nickel magnesium composite oxide and preparation method thereof |
| CN103936083B (en) * | 2013-01-23 | 2016-04-13 | 中国石油化工股份有限公司 | Nickel-magnesia mixed oxide and preparation method thereof |
| CN108373176A (en) * | 2018-04-16 | 2018-08-07 | 沈阳建筑大学 | A kind of nano-nickel oxide raw powder's production technology for ultracapacitor |
| CN110102457A (en) * | 2019-04-19 | 2019-08-09 | 东北大学秦皇岛分校 | A method of preparing nickel oxide nano-crystal electrochomeric films at low temperature |
| CN114308041A (en) * | 2020-09-30 | 2022-04-12 | 天津理工大学 | Preparation method of black nickel oxide and application of black nickel oxide in catalyzing oxidation reaction of 1, 2-diol for breaking C-C bond |
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