CN1872703A - Method for preparing Nano material of hydrate through hydrolyzing acetate - Google Patents
Method for preparing Nano material of hydrate through hydrolyzing acetate Download PDFInfo
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- CN1872703A CN1872703A CN 200610027699 CN200610027699A CN1872703A CN 1872703 A CN1872703 A CN 1872703A CN 200610027699 CN200610027699 CN 200610027699 CN 200610027699 A CN200610027699 A CN 200610027699A CN 1872703 A CN1872703 A CN 1872703A
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Abstract
This invention provides a method for preparing cobalt or nickel hydroxide nanopowder by hydrolysis of corresponding acetate. The method comprises: (1) dissolving cobalt or nickel acetate in deionized water or a mixture of deionized water and glycerine at room temperature to obtain a uniform acetate solution; (2) transferring the solution to a reaction kettle, and performing hydrothermal reaction at 120-200 deg.C; (3) separating the product from the solution, washing and drying to obtain cobalt or nickel hydroxide nanopowder. The morphology of the nanopowder can be controlled by changing the temperature and time of the hydrothermal reaction, the concentration of the acetate solution, and the volume ratio of glycerin to deionized water. The method has such advantages as low raw material cost, simple process, easy operation and controllable product morphology.
Description
Technical field
The present invention relates to a kind of preparation method of oxyhydroxide, more precisely relate to by nickelous acetate or cobaltous acetate and being dissolved in the mixing solutions of deionized water or deionized water and glycerol, belong to field of nano material preparation by the method for Hydrothermal Preparation nickel hydroxide and cobaltous hydroxide nanostructured powders.
Background technology
In recent years, owing to developing rapidly of global information industry, various small portable electronic device such as mobile communication, notebook computer were to the demand surge of battery, and secondary cell occupies more and more important position in our life.As widely used nickel/cadmium (Ni/Cd), nickel/iron (Ni/Fe), nickel/zinc (Ni/Zn), nickle/metal hydrides nickel series secondary batteries such as (Ni/MH), because the positive pole in this series battery all is a nickel electrode, therefore to high reactivity, heavy body, high comprehensive performance nickel positive active material---the research of nickel hydroxide has important practical significance.
In order to improve the performance of anodal nickel hydroxide electrode, obtained very big progress for the research work of ball-shape nickel hydroxide and related compound material thereof.On the one hand, ball-shape nickel hydroxide has high relatively density and good filling flowability, can improve the unit volume loading level of electrode, thereby also with regard to the corresponding electrode capacity that improved.From another point of view, because diffusional resistance, the core of ball-shape nickel hydroxide still presents inertia under higher charge-discharge magnification and higher temperature.
In recent years, the nickel hydroxide nano material as a kind of novel, battery material has caused many investigators' concern efficiently.The nickel hydroxide nano particle diameter is little, and specific surface area is big, has increased and the contacting of electrolyte solution, and has reduced the diffusion length of proton in solid phase, thereby improves the diffusion of proton.Therefore, study the preparation technology of nickel hydroxide, produce the nickel hydroxide of heavy body, not only can improve the capacity of MH-Ni battery, the capacity of Cd-Ni battery is improved greatly.
Cobaltous hydroxide can improve the electrochemical activity of nickel secondary batteries as a kind of additive of nickel secondary batteries; Aspect the ultra-capacitor of energy density development potentiality is being arranged with the matrix material of Y zeolite, it also shows certain catalysis, emission and magnetic performance in addition.
But the existing method for preparing materials such as nickel hydroxide and cobaltous hydroxide all will be introduced alkali source usually, as sodium hydroxide (Y.Wang, Q.S.Zhu, H.G.Zhang, Chem.Commun.2006,5231; D.N.Yang, R.M.Wang, M.S.He, J.Zhang, Z.F.Liu, J.Phys.Chem.B 2005,109, and 7654; D.L.Chen, L.Gao, Chem.Phys.Lett.2005,405,159; Y.L.Hou, H.Kondoh, M.Shimojo, T.Kogure, T.ohta, J.Phys.Chem.B 2005,109,19094), ammoniacal liquor (X.M.Ni, Q.B.Zhao, B.B.Li, J.Cheng, H.G.Zheng, Solid StateCommun.2006,137,585; C.Coudun, J.F.Hochepied, J.Phys.Chem.B 2005,109,6069.), urea (M.Jayalakshmi, N.Venugopal, B.Ramachandra Reddy, M.Mohan Rao, J.Power Sources, 2005,150,272.), vulkacit H (Z.P.Liu, R.Z.Ma, M.Osada, T.Sasaki, J.Am.Chem.Soc.2005,127,13869.) etc., sometimes also to introduce tensio-active agent or other inorganic salt or organic solvent (Y.Wang, Q.S.Zhu, H.G.Zhang, Chem.Commun.2006,5231; C.Coudun, J.F.Hochepied, J.Phys.Chem.B2005,109,6069; D.B.Wang, C.X.Song, Z.S.hu, X.Fu, J.Phys.Chem.B2005,109,1125; J.T.Sampanthar, H.C.Zeng, J.Am.Chem.Soc.2002,124,6668.) nano material of preparation different-shape.The present invention attempts the mixing solutions with deionized water or deionized water and glycerol, need not add other alkali source and tensio-active agent etc., can simplify preparation technology.Simultaneously, water and glycerol can reduce cost greatly as reaction solvent, have important practical significance in suitability for industrialized production.
Summary of the invention
The object of the present invention is to provide a kind of method of preparing Nano material of hydrate through hydrolyzing acetate, is the low cost simple preparation method of a kind of oxyhydroxide (nickel and cobalt) nanostructured powders.The present invention is a raw material by the acetate with the oxyhydroxide of desire preparation, is solvent with the mixed solution of deionized water or deionized water and glycerol, at room temperature mixes forming the homogeneous liquid-phase reaction solution; The concentration of described acetate is 0.01 mol～0.2 mol, and the volume ratio of glycerol and water is 0～2; Again uniform solution is changed in the reactor, carry out hydro-thermal reaction after, processing can obtain nickel hydroxide and cobaltous hydroxide nanometer powder.The method that is provided is simple, and is easy to operate, and used raw material is cheap and easy to get, is a kind of preparation method who is suitable for suitability for industrialized production.
Concrete technology as shown in Figure 1.Concrete steps are:
1, the preparation of liquid-phase reaction system: the corresponding acetate with the oxyhydroxide of desire preparation is a raw material, mixed solution with deionized water or deionized water and glycerol is a solvent, oxyhydroxide kind according to preparation is prepared reaction system, obtains uniform solution by stirring;
2, uniform solution is transferred in the reactor and carries out hydrothermal treatment consists at 120～200 ℃, the hydrothermal treatment consists time is 1～48 hour.Concrete temperature and time is determined according to the oxyhydroxide kind of preparation.
3, the product in the liquid-phase reaction system after the hydrothermal treatment consists is separated, separated products is washed and drying treatment, drying temperature is a room temperature to 100 ℃, promptly gets the nanometer powder of oxyhydroxide.
Described acetate as reactant comprises that nickelous acetate and acetate bore.
The preparation method of oxyhydroxide provided by the invention (nickel and cobalt) nano structural material has the following advantages:
(1) Zhi Bei oxyhydroxide (nickel and cobalt) powder crystallization is good.
(2) by the suitable preparation condition of control, can make oxyhydroxide (nickel and the cobalt) powder of different-shape and size, comprise 1. nano-sheet, 2. nanometer sheet is adorned the similar carnation pattern of formation from the ancestral, 3. mixing of nanometer sheet and nanometer carnation, 4. or the floriform appearance that forms of the 5. flower-shaped or nanometer sheet self-assembly that forms of nanometer sheet self-assembly and the mixing of single nanometer sheet.
(3) glycerol has played the effect (one of solvent) of complexing in nickel hydroxide and cobaltous hydroxide nanostructure synthetic, and glycerol also plays the effect of reductive agent in the preparation process of cobaltous hydroxide in addition.Do not need to add in addition other tensio-active agent in the reaction process, this can simplify production process greatly, reduces cost.So the mixture of preferentially recommending deionized water and glycerol is as solvent.
(4) raw material is cheap and easy to get, easy to operate, and preparation technology is simple, does not need cost and complex equipment, is easy to realize suitability for industrialized production.
Description of drawings
Preparation technology's schema of Fig. 1 oxyhydroxide (nickel and cobalt) powder.
The X-ray powder diffraction spectrogram of Fig. 2 nickel hydroxide.
The nickel hydroxide nano sheet transmission electron microscope photo that Fig. 3 obtained 200 ℃ of hydro-thermals in 3.5 hours.
The nickel hydroxide nano carnation that Fig. 4 obtained 200 ℃ of hydro-thermals in 3.5 hours: (a) electron scanning micrograph; (b) transmission electron microscope photo; (c) electron diffraction photo and (d) high resolution photo.
Nickel hydroxide nano sheet and nanometer carnation transmission electron microscope photo that Fig. 5 obtained 200 ℃ of hydro-thermals in 3.5 hours.
The X-ray powder diffraction spectrogram of Fig. 6 cobaltous hydroxide.
The cobaltous hydroxide flower electron scanning micrograph that Fig. 7 obtained 200 ℃ of hydro-thermals in 10.5 hours.
Fig. 8 is at 200 ℃ of hydro-thermals different amplification cobaltous hydroxide nanometer sheet that obtained in 24.5 hours and the electron scanning micrograph of spending (a, b, c).
Embodiment
Further specify embodiment and effect with following indefiniteness embodiment.
Embodiment 1. nickel hydroxide nano sheets
At room temperature, 0.625g nickelous acetate (0.104mol/L) is dissolved in the 24mL deionized water, the stirring at room dissolving obtains homodisperse solution.Change this solution in the reactor (the reactor capacity is 40mL), sealing.Reactor is put into baking oven, 200 ℃ of insulations 3.5 hours.After reactor naturally cools to room temperature, take out product, use the centrifuging separated product, isolating product respectively washs 3 times with deionized water and dehydrated alcohol respectively, 60 ℃ of air dryings.Fig. 3 is its transmission electron microscope photo, clearly finds out sheet structure.
Embodiment 2. nickel hydroxide nano carnations
At room temperature, 0.208g nickelous acetate (0.035mol/L) is dissolved in the mixing solutions of 1mL glycerol and 23mL deionized water, the stirring at room dissolving obtains homodisperse solution.Change this solution in the reactor (the reactor capacity is 40mL), sealing.Reactor is put into baking oven, 200 ℃ of insulations 3.5 hours.After reactor naturally cools to room temperature, take out product, use the centrifuging separated product, isolating product respectively washs 3 times with deionized water and dehydrated alcohol respectively, 60 ℃ of air dryings.Fig. 2 is the X-ray powder diffraction spectrogram of the nickel hydroxide nano carnation of present embodiment preparation, does not find the diffraction peak of any impurity in the spectrogram, illustrates that products therefrom is single-phase nickel hydroxide.Fig. 4 is its transmission electron microscope photo and electron scanning micrograph, clearly finds out the similar carnation structure that it forms for the nanometer sheet self-assembly.The selected area electron diffraction of inserting among the figure shows that nanometer sheet has orientation, and the single nanometer sheet that constitutes the similar carnation of nanometer in conjunction with the explanation of high-resolution electron microscopy photo has single crystal structure.
Embodiment 3. nickel hydroxide nano carnations
At room temperature, 0.208g nickelous acetate (0.035mol/L) is dissolved in the mixing solutions of 1mL glycerol and 23mL deionized water, the stirring at room dissolving obtains homodisperse solution.Change this solution in the reactor (the reactor capacity is 40mL), sealing.Reactor is put into baking oven, 120 ℃ of insulations 36 hours.After reactor naturally cools to room temperature, take out product, use the centrifuging separated product, isolating product respectively washs 3 times with deionized water and dehydrated alcohol respectively, 60 ℃ of air dryings.Find out that from light micrograph its pattern still is the structure of similar carnation.
Embodiment 4. has the preparation of the nickel hydroxide of nanometer sheet and nanometer carnation mixing pattern
At room temperature, 0.625g nickelous acetate (0.104mol/L) is dissolved in the mixing solutions of 2mL glycerol and 22mL deionized water, the stirring at room dissolving obtains homodisperse solution.Change this solution in the reactor (the reactor capacity is 40mL), sealing.Reactor is put into baking oven, 200 ℃ of insulations 3.5 hours.After reactor naturally cools to room temperature, take out product, use the centrifuging separated product, isolating product respectively washs 3 times with deionized water and dehydrated alcohol respectively, 60 ℃ of air dryings.Fig. 5 is its transmission electron microscope photo, find out that clearly it is the similar carnation structure of nanometer sheet self-assembly formation and the mixing pattern of one nanometer sheet, but the size of nanometer carnation is smaller than embodiment 2.
The preparation of embodiment 5. flower-shaped cobaltous hydroxides
At room temperature, 0.250g cobaltous acetate (0.033mol/L) is dissolved in the mixing solutions of 7.5mL glycerol and 22.5mL deionized water, the stirring at room dissolving obtains homodisperse solution.Change this solution in the reactor (the reactor capacity is 40mL), sealing.Reactor is put into baking oven, 200 ℃ of insulations 10.5 hours.After reactor naturally cools to room temperature, take out product, use the centrifuging separated product, isolating product respectively washs 3 times with deionized water and dehydrated alcohol respectively, 60 ℃ of air dryings.Fig. 6 is the X-ray powder diffraction spectrogram of the cobaltous hydroxide of present embodiment preparation, does not find the diffraction peak of any impurity in the spectrogram, illustrates that products therefrom is single-phase cobaltous hydroxide.Fig. 7 is its electron scanning micrograph, clearly finds out the flower-like structure that it forms for the nanometer sheet self-assembly.
Embodiment 6. has the preparation of the hydroxide brill of nanometer sheet and flower-shaped mixing pattern
At room temperature, 0.250g cobaltous acetate (0.033mol/L) is dissolved in the mixing solutions of 4mL glycerol and 26mL deionized water, the stirring at room dissolving obtains homodisperse solution.Change this solution in the reactor (the reactor capacity is 40mL), sealing.Reactor is put into baking oven, 200 ℃ of insulations 24.5 hours.After reactor naturally cools to room temperature, take out product, use the centrifuging separated product, isolating product respectively washs 3 times with deionized water and dehydrated alcohol respectively, 60 ℃ of air dryings.Fig. 8 is its electron scanning micrograph, find out that clearly it is the flower-like structure of nanometer sheet self-assembly formation and the mixing pattern of one nanometer sheet, it is that the nanometer sheet that does not have to curl constitutes that flower-like structure has a kind of, another kind is the more open structure that curls into by nanometer sheet, flower-shaped similar among the embodiment 4.
Claims (5)
1, a kind of method with preparing Nano material of hydrate through hydrolyzing acetate comprises preparation, the hydrothermal treatment consists of reaction system, separation, washing and the drying process of product, it is characterized in that comprising following step:
(1) the corresponding acetate for preparing oxyhydroxide with desire is a raw material, is solvent with the mixed solution of deionized water or deionized water and glycerol, forms uniform solution under the room temperature; The concentration of described acetate is 0.01 mol～0.2 mol, and the volume ratio of glycerol and water is 0～2;
(2) uniform solution is transferred in the reactor and carries out hydrothermal treatment consists at 120～200 ℃, the hydrothermal treatment consists time is 1～48 hour.Concrete temperature and time is according to the oxyhydroxide kind and the temperature and determine that the loading level of reactor is 50%-80% of preparation;
(3) product in the liquid-phase reaction system after the hydrothermal treatment consists is separated, separated products is washed and drying treatment, drying temperature is a room temperature to 100 ℃, at air drying.
2,, it is characterized in that described acetate as reactant is a kind of in nickelous acetate or the cobaltous acetate by the described method with preparing Nano material of hydrate through hydrolyzing acetate of claim 1.
3, by the described method of claim 1, it is characterized in that described solvent is the mixed solution of deionized water and glycerol with preparing Nano material of hydrate through hydrolyzing acetate.
4, by the described method of claim 1, it is characterized in that by control reactant concn, the time of hydro-thermal reaction and nickel hydroxide and the cobaltous hydroxide that temperature of reaction makes different-shape with preparing Nano material of hydrate through hydrolyzing acetate.
5, by the described method of claim 1 with preparing Nano material of hydrate through hydrolyzing acetate, the pattern that it is characterized in that prepared Nano material of hydrate is a nanometer sheet, nanometer sheet is adorned the similar carnation of formation from the ancestral, nanometer sheet is mixed with the nanometer carnation, the mixing of the flower-shaped and single nanometer sheet that the flower-shaped or nanometer sheet self-assembly that the nanometer sheet self-assembly forms forms.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102807255A (en) * | 2011-05-31 | 2012-12-05 | 中国科学院大连化学物理研究所 | Flower-like nanometer cobalt hydroxide material and preparation method thereof |
| CN102849804A (en) * | 2012-09-21 | 2013-01-02 | 中国科学院过程工程研究所 | Cobaltosic oxide columnar structure material and preparation method thereof |
| CN102897852A (en) * | 2012-09-25 | 2013-01-30 | 江苏大学 | Method for hydrothermal synthesis of nickel hydroxide hierarchical structure microspheres assembled by nano-sheets |
| CN114014385A (en) * | 2021-10-12 | 2022-02-08 | 广东邦普循环科技有限公司 | Method for preparing nickel oxide by using water quenched nickel |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS5435197A (en) * | 1977-08-23 | 1979-03-15 | Matsushita Electric Ind Co Ltd | Preparation of zinc hydroxide platy crystals |
| JP2639916B2 (en) * | 1986-08-19 | 1997-08-13 | 三洋電機株式会社 | Method for producing sintered nickel electrode for alkaline storage battery |
| CN1206021A (en) * | 1997-07-17 | 1999-01-27 | 中国科学院化学研究所 | Tubular organosilicon polymer compound and its preparation |
| JP2000268820A (en) * | 1999-03-19 | 2000-09-29 | Tanaka Kagaku Kenkyusho:Kk | Manufacture of positive electrode active material for alkaline storage battery |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102807255A (en) * | 2011-05-31 | 2012-12-05 | 中国科学院大连化学物理研究所 | Flower-like nanometer cobalt hydroxide material and preparation method thereof |
| CN102807255B (en) * | 2011-05-31 | 2014-05-28 | 中国科学院大连化学物理研究所 | Flower-like nanometer cobalt hydroxide material and preparation method thereof |
| CN102849804A (en) * | 2012-09-21 | 2013-01-02 | 中国科学院过程工程研究所 | Cobaltosic oxide columnar structure material and preparation method thereof |
| CN102849804B (en) * | 2012-09-21 | 2014-11-05 | 中国科学院过程工程研究所 | Cobaltosic oxide columnar structure material and preparation method thereof |
| CN102897852A (en) * | 2012-09-25 | 2013-01-30 | 江苏大学 | Method for hydrothermal synthesis of nickel hydroxide hierarchical structure microspheres assembled by nano-sheets |
| CN102897852B (en) * | 2012-09-25 | 2014-10-29 | 江苏大学 | Method for hydrothermal synthesis of nickel hydroxide hierarchical structure microspheres assembled by nano-sheets |
| CN114014385A (en) * | 2021-10-12 | 2022-02-08 | 广东邦普循环科技有限公司 | Method for preparing nickel oxide by using water quenched nickel |
| CN114014385B (en) * | 2021-10-12 | 2023-10-17 | 广东邦普循环科技有限公司 | Method for preparing nickel oxide by utilizing water quenched nickel |
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