CN102070208A - Preparation method of nickel-cobalt hydroxide with controllable appearance - Google Patents
Preparation method of nickel-cobalt hydroxide with controllable appearance Download PDFInfo
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- CN102070208A CN102070208A CN 201010573738 CN201010573738A CN102070208A CN 102070208 A CN102070208 A CN 102070208A CN 201010573738 CN201010573738 CN 201010573738 CN 201010573738 A CN201010573738 A CN 201010573738A CN 102070208 A CN102070208 A CN 102070208A
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Abstract
The invention discloses a preparation method of nickel-cobalt hydroxide with controllable appearance, belonging to the technical field of chemical engineering and new materials. The preparation method comprises the following steps of: firstly adding an ethylene amine chelating agent into mixed solution of soluble nickel salt and cobalt salt to form metal amine chelating agent solution, fully chelating metal ions and the chelating agent by stirring, then adding alkali metal hydroxide solution into a reaction system, and obtaining hydroxide precipitate by controlling the reaction temperature; and filtering, cleaning and drying the obtained hydroxide precipitate and obtaining the nickel-cobalt hydroxide with a spherical structure or a three-dimensional sisal-shaped structure. The preparation method has the advantages that 1, a new appearance of the nickel-cobalt hydroxide is provided; 2, for the nickel-cobalt hydroxide prepared by using the method provided by the invention, the control for the appearance of the nickel-cobalt hydroxide can be realized by adjusting the molar ratio of nickel ions and cobalt ions in the system, the variety of ethylene amine, the molar ratio of different amines and the dropping sequence; and 3, in the method provided by the invention, the reaction technology is simple, the condition is mild, and the process is short, so that the preparation method is suitable for industrial production.
Description
Technical field
The invention belongs to chemical engineering and field of new, the preparation method of the nickel cobalt hydroxide that particularly a kind of pattern is controlled.
Background technology
Transition metal hydroxide and oxide compound are because its special redox property and phase structure characteristic all have important use in a lot of fields.New field has been opened up in the research that develops into novel material of nano science, the oxyhydroxide of nickel and cobalt and oxide-based nanomaterial in transition metal hydroxide and the oxide compound have wide application prospect owing to have interesting magnetic, light, transmission, catalysis, electrochemistry and an emission characteristic in fields such as magnetic, catalysis, sensing, energy storage.Pattern has material impact to performance, and the variation of material pattern can cause changes of properties.That therefore, carries out that the material morphology control shows is particularly important.
Nickel hydroxide is the positive electrode active materials of nickel series battery, also is widely used in catalysis and electrochromism field simultaneously.Cobaltous hydroxide is a kind of additives for battery of excellent performance, at gas sensor, and catalyzer, magneticsubstance, the electrochromism field also has a wide range of applications.Pattern, particle diameter and crystallinity have material impact to the electrical property and the catalytic performance of nickel hydroxide and nickel hydroxide.
Because single oxyhydroxide has certain limitation on pattern and performance, people begin to pay close attention to the research of complex hydroxide, realize the variation of pattern and the improvement of performance.CN1884089A provides a kind of method of making nickel cobalt manganese oxyhydroxide, and with the synthetic nickel cobalt manganese oxyhydroxide of the method for cocrystallization, the particle that obtains product is a sheet, strip and closely spherical under the ammonia environment.The mixing of The addition of C o in the nickel hydroxide electrode can have been reduced the electrode internal resistance, improved the reversibility of electrode reaction, and made its loading capacity and cycle life obtain obvious improvement.CN101062792A utilizes the buffered soln method to prepare the ball-shape nickel hydroxide of doping Co.
At present, the pattern of preparation nickel cobalt hydroxide is comparatively single, and most of pattern all is spherical, and the general cycle of preparation method is longer, is realizing that the product crystallinity is good, and also there is bigger difficulty in the controlled aspect of uniform particle diameter and pattern.
Summary of the invention
In order to address the above problem, the pattern of the object of the present invention is to provide that a kind of technology is simple, mild condition, flow process are short is controlled, and guarantees the product good crystallinity that obtains, the preparation method of the nickel cobalt complex hydroxide that uniform particle diameter and consistence are good.
Technical scheme of the present invention is: the preparation method of the nickel cobalt hydroxide that a kind of pattern is controlled:
The present invention adopts coprecipitation method to prepare nickel cobalt complex hydroxide, at first in nickel salt and cobalt saline solution, add the ethyleneamines sequestrant and make the metal amine chelate solution, make metal ion and the abundant chelating of sequestrant by stirring, in reaction system, add alkali hydroxide soln then, obtain precipitation of hydroxide by control reaction temperature.Through filtering, to wash, drying makes nickel cobalt complex hydroxide.The mol ratio of the mol ratio of nickel ion and cobalt ion, the kind of ethyleneamines, different amine and dropping thereof order has determined the pattern of coprecipitated product jointly in the reaction system of the present invention, by regulating the control of these parameters realizations to nickel cobalt hydroxide pattern.As the mol ratio of controlling nickel ion and cobalt ion is 2:1, and selecting quadrol for use is sequestrant, can obtain the spheric nickel cobalt hydroxide of being dressed up by the two-wheel structural group; The mol ratio of control nickel ion and cobalt ion is 1:3, and selecting triethylene tetramine for use is sequestrant, can obtain the nickel cobalt hydroxide of the three-dimensional sisal hemp shape that is assembled into by smooth club shaped structure.
Concrete preparation process is:
Compound concentration is the soluble nickel salt of 0.5-1mol/L and the mixing solutions of cobalt salt under the normal temperature, magnetic agitation 1-2h, under agitation condition, add the ethyleneamines sequestrant, continue to stir 1-2h, add alkali hydroxide soln again, the pH value that makes reaction system is greater than 13, stopping behind the 1-2h stirring, is 80 ~ 120 ℃ in temperature, insulation 3h, filtration washing, the spherical or three-dimensional sisal hemp shape nickel cobalt hydroxide that behind dry 12h under 40 ℃, obtains then; Wherein, the mol ratio of nickel ion and cobalt ion is 1 ~ 5:1 ~ 5, and sequestrant is 1 ~ 5:1 with the mol ratio of total metal ion, and alkali hydroxide soln concentration is 6-10mol/L.
Described soluble nickel salt, cobalt salt comprise: one or more in the nitrate of nickel, cobalt, vitriol, halogenide, phosphoric acid salt, the organic carboxylate, wherein preferably nitrate.
Described ethyleneamines sequestrant comprises: one or more in quadrol, diethylenetriamine, triethylene tetramine, tetraethylene pentamine, the five ethene hexamines, wherein preferred quadrol and triethylene tetramine.
Described alkali metal hydroxide comprises: sodium hydroxide, potassium hydroxide, one or more in the lithium hydroxide, wherein preferred sodium hydroxide.
The basic structural unit of described globosity mainly contains two-wheel shape structure and hexagon dish, the diameter of two-wheel shape structure two side wheels is 1-2 μ m, and thickness is 70-120nm, and tunnel shaft length is 50-70nm, the thickness of hexagon dish is 100-300nm, and the length of side is 600-900nm; The basic structural unit of described three-dimensional sisal hemp shape structure mainly contains smooth club shaped structure and step club shaped structure, and wherein Bang length is 1-2 μ m, and diameter is 300-600nm.
The invention has the advantages that: (1) provides the new pattern of nickel cobalt hydroxide; (2) with the nickel cobalt hydroxide of method provided by the invention preparation, mol ratio that can be by the mol ratio of nickel ion in the regulation system and cobalt ion, the kind of ethyleneamines, different amine and dropping thereof realize the control to nickel cobalt hydroxide pattern in proper order; (3), mild condition simple with method reaction process provided by the invention, flow process are short, are fit to suitability for industrialized production.
Description of drawings
The stereoscan photograph of the nickel cobalt hydroxide that Fig. 1 obtains for the invention process case 1.
The X-ray diffractogram of the nickel cobalt hydroxide that Fig. 2 obtains for the invention process case 1.
The stereoscan photograph of the nickel cobalt hydroxide that Fig. 3 obtains for the invention process case 2.
The stereoscan photograph of the nickel cobalt hydroxide that Fig. 4 obtains for the invention process case 3.
The stereoscan photograph of the nickel cobalt hydroxide that Fig. 5 obtains for the invention process case 4.
Embodiment
Below in conjunction with concrete embodiment technical scheme of the present invention is described further.
Case study on implementation 1
Normal temperature preparation 10ml concentration down is the mixing solutions of 0.75mol/L nickelous nitrate and Xiao Suangu, wherein the mol ratio of nickel ion and cobalt ion is 2:1, the quadrol that under agitation condition, adds 0.024mol, continue to stir 1h, add the sodium hydroxide solution that 48ml concentration is 7mol/L again, stop behind the 1h stirring, then temperature is controlled at 100 ℃ and keeps 1h, filtration washing, obtain final product nickel cobalt hydroxide behind the dry 12h down at 40 ℃ then, the scanned photograph of product and X-ray diffractogram are as depicted in figs. 1 and 2.Gained nickel cobalt hydroxide structure is a globosity, and basic structural unit is a two-wheel shape structure, and the diameter of two side wheels is 1.5 μ m, and thickness is 70nm, and tunnel shaft length is 50nm.
Case study on implementation 2
Normal temperature preparation 10ml concentration down is the mixing solutions of 0.75mol/L nickelous nitrate and Xiao Suangu, wherein the mol ratio of nickel ion and cobalt ion is 3:1, the triethylene tetramine that under agitation condition, adds 0.012mol, continue to stir 1h, add the sodium hydroxide solution that 48ml concentration is 8mol/L again, stop behind the 1.5h stirring, then temperature is controlled at 90 ℃ and keeps 1.5h, filtration washing obtains final product nickel cobalt hydroxide behind the dry 12h down at 40 ℃ then, and the scanned photograph of product as shown in Figure 3; Gained nickel cobalt hydroxide structure is a globosity, and basic structural unit is the hexagon dish, and the thickness of hexagon dish is 100nm, and the length of side is 600nm.
Case study on implementation 3
Normal temperature preparation 10ml concentration down is the mixing solutions of 0.8mol/L nickelous nitrate and Xiao Suangu, wherein the mol ratio of nickel ion and cobalt ion is 1:3, the triethylene tetramine that under agitation condition, adds 0.012mol, continue to stir 1h, add the sodium hydroxide solution that 48ml concentration is 7mol/L again, stop behind the 1.8h stirring, then temperature is controlled at 110 ℃ and keeps 2h, filtration washing obtains final product nickel cobalt hydroxide behind the dry 12h down at 40 ℃ then, and the scanned photograph of product as shown in Figure 4.Gained nickel cobalt hydroxide structure is three-dimensional sisal hemp shape structure, and basic structural unit is smooth club shaped structure, and wherein Bang length is 1,5 μ m, and diameter is 400nm.
Case study on implementation 4
Normal temperature preparation 10ml concentration down is the mixing solutions of 0.8mol/L nickelous chloride and cobalt chloride, wherein the mol ratio of nickel ion and cobalt ion is 1:1, the triethylene tetramine that under agitation condition, adds 0.006mol earlier, the quadrol that adds 0.012mol again, continue to stir 1.2h, add the potassium hydroxide solution that 48ml concentration is 9mol/L again, stop behind the 1h stirring, then temperature is controlled at 120 ℃ and keeps 2.5h, filtration washing, obtain final product nickel cobalt hydroxide behind the dry 12h down at 40 ℃ then, the scanned photograph of product as shown in Figure 5.Gained nickel cobalt hydroxide structure is three-dimensional sisal hemp shape structure, and basic structural unit is the step club shaped structure, and wherein Bang length is 2 μ m, and diameter is 600nm.
Case study on implementation 5
Normal temperature preparation 10ml concentration down is the mixing solutions of 0.75mol/L nickelous chloride and cobalt chloride, wherein the mol ratio of nickel ion and cobalt ion is 1:1, the quadrol that under agitation condition, adds 0.012mol earlier, the triethylene tetramine that adds 0.006mol again continues to stir 1h, adds the potassium hydroxide solution that 48ml concentration is 7mol/L again, stop behind the 1h stirring, then temperature is controlled at 100 ℃ and keeps 3h, filtration washing obtains final product nickel cobalt hydroxide behind the dry 12h down at 40 ℃ then.Gained nickel cobalt hydroxide structure is three-dimensional sisal hemp shape structure, and basic structural unit is the triangular prism structure, and wherein the length of triangular prism is 1 μ m, and the bottom surface length of side is 500nm.
Case study on implementation 6
Normal temperature preparation 10ml concentration down is the mixing solutions of 0.75mol/L single nickel salt and rose vitriol, wherein the mol ratio of nickel ion and cobalt ion is 3:1, the triethylene tetramine that under agitation condition, adds 0.006mol earlier, the quadrol that adds 0.012mol again continues to stir 2h, adds the sodium hydroxide solution that 48ml concentration is 7mol/L again, stop behind the 1h stirring, then temperature is controlled at 120 ℃ and keeps 3h, filtration washing obtains final product nickel cobalt hydroxide behind the dry 12h down at 40 ℃ then.Gained nickel cobalt hydroxide structure is a globosity, and basic structural unit is a single-wheel shape structure, and the diameter of wheel is 2 μ m, and thickness is 900nm.
Claims (5)
1. the preparation method of the controlled nickel cobalt hydroxide of a pattern is characterized in that, specifically may further comprise the steps:
Compound concentration is the soluble nickel salt of 0.5-1mol/L and the mixing solutions of cobalt salt under the normal temperature, magnetic agitation 1-2h, under agitation condition, add the ethyleneamines sequestrant, continue to stir 1-2h, add alkali hydroxide soln again, the pH value that makes reaction system is greater than 13, stop behind the 1-2h stirring, temperature is controlled at insulation 3 h between 80 ~ 120 ℃, and filtration washing is then at 40 ℃ of nickel cobalt hydroxides that obtain globosity or three-dimensional sisal hemp shape structure down behind the dry 12h; Wherein, the mol ratio of nickel ion and cobalt ion is 1 ~ 5:1 ~ 5, and sequestrant is 1 ~ 5:1 with the mol ratio of total metal ion, and alkali hydroxide soln concentration is 6-10mol/L.
2. the preparation method of the nickel cobalt hydroxide that pattern according to claim 1 is controlled is characterized in that, described soluble nickel salt, cobalt salt are: one or more in the nitrate of nickel, cobalt, vitriol, halogenide, phosphoric acid salt, the organic carboxylate.
3. the preparation method of the nickel cobalt hydroxide that pattern according to claim 1 is controlled is characterized in that, described ethyleneamines sequestrant is one or more in quadrol, diethylenetriamine, triethylene tetramine, tetraethylene pentamine, the five ethene hexamines.
4. the preparation method of the nickel cobalt hydroxide that pattern according to claim 1 is controlled is characterized in that, described alkali metal hydroxide is a sodium hydroxide, potassium hydroxide, one or more in the lithium hydroxide.
5. the preparation method of the nickel cobalt hydroxide that pattern according to claim 1 is controlled, it is characterized in that, the basic structural unit of described globosity mainly contains two-wheel shape structure and hexagon dish, the diameter of described two-wheel shape structure two side wheels is 1-2 μ m, thickness is 70-120nm, tunnel shaft length is 50-70nm, and the thickness of hexagon dish is 100-300nm, and the length of side is 600-900nm; The basic structural unit of described three-dimensional sisal hemp shape structure mainly contains smooth club shaped structure and step club shaped structure, and wherein Bang length is 1-2 μ m, and diameter is 300-600nm.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106841073A (en) * | 2017-04-20 | 2017-06-13 | 广州超邦化工有限公司 | The analysis method of nickel content in a kind of alkaline zinc-nickel alloy plating solution |
| CN108128785A (en) * | 2018-03-02 | 2018-06-08 | 浙江大学 | Using nickel amine complex as the method for template one-step synthesis ITE zeolite molecular sieves |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1282114A (en) * | 2000-08-25 | 2001-01-31 | 清华大学 | Preparation method of nickel positive active material spherical alpha-nickel hydroxide |
| CN101062792A (en) * | 2006-04-28 | 2007-10-31 | 长沙力元新材料股份有限公司 | Preparation method of spherical nickel hydroxid |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1282114A (en) * | 2000-08-25 | 2001-01-31 | 清华大学 | Preparation method of nickel positive active material spherical alpha-nickel hydroxide |
| CN101062792A (en) * | 2006-04-28 | 2007-10-31 | 长沙力元新材料股份有限公司 | Preparation method of spherical nickel hydroxid |
Non-Patent Citations (1)
| Title |
|---|
| 《中国优秀博硕士学位论文全文数据库（硕士） 工程科技I辑》 20030615 翟海军 掺杂alpha-Ni(OH)2的合成及其电化学性能研究 第8页第1.4节 1-5 , 第2 期 2 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106841073A (en) * | 2017-04-20 | 2017-06-13 | 广州超邦化工有限公司 | The analysis method of nickel content in a kind of alkaline zinc-nickel alloy plating solution |
| CN108128785A (en) * | 2018-03-02 | 2018-06-08 | 浙江大学 | Using nickel amine complex as the method for template one-step synthesis ITE zeolite molecular sieves |
| CN108128785B (en) * | 2018-03-02 | 2020-02-14 | 浙江大学 | Method for synthesizing ITE zeolite molecular sieve by using nickel-amine complex as template agent in one step |
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