CN102070208B - Preparation method of nickel-cobalt hydroxide with controllable appearance - Google Patents
Preparation method of nickel-cobalt hydroxide with controllable appearance Download PDFInfo
- Publication number
- CN102070208B CN102070208B CN2010105737389A CN201010573738A CN102070208B CN 102070208 B CN102070208 B CN 102070208B CN 2010105737389 A CN2010105737389 A CN 2010105737389A CN 201010573738 A CN201010573738 A CN 201010573738A CN 102070208 B CN102070208 B CN 102070208B
- Authority
- CN
- China
- Prior art keywords
- nickel
- hydroxide
- cobalt
- preparation
- cobalt hydroxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
- Battery Electrode And Active Subsutance (AREA)
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 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 new material of nano science; The hydroxide of nickel and cobalt and oxide-based nanomaterial in transition metal hydroxide and the oxide 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 storages.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.Cobalt hydroxide is a kind of additives for battery of excellent performance, at gas sensor, and catalyst, magnetic material, 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 hydroxide 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 hydroxide, and with the synthetic nickel cobalt manganese hydroxide of the method for cocrystallization, the particle that obtains product is a sheet, strip and closely spherical under ammonia property environment.The mixing of The addition of C o in the nickel hydroxide electrode can have been reduced the electrode internal resistance, improved the invertibity of electrode reaction, and made its discharge capacity and cycle life obtain obvious improvement.CN101062792A utilizes the cushioning liquid 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 uniformity 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 to prepare nickel cobalt complex hydroxide; At first in nickel salt and cobalt saline solution, add the ethyleneamines chelating agent and make the metal amine chelate solution; Make metal ion and the abundant chelating of chelating agent through stirring; In reaction system, add alkali hydroxide soln then, obtain precipitation of hydroxide through the 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 ions, 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, realizes the control to nickel cobalt hydroxide pattern through regulating these parameters.As the mol ratio of controlling nickel ion and cobalt ions is 2:1, and selecting ethylenediamine for use is chelating agent, the nickel cobalt hydroxide of the sphere that can obtain being dressed up by the two-wheel structural group; The mol ratio of control nickel ion and cobalt ions is 1:3, and selecting triethylene tetramine for use is chelating agent, the nickel cobalt hydroxide of the three-dimensional sisal hemp shape that can obtain being 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 mixed solution of cobalt salt under the normal temperature, and magnetic agitation 1-2h adds the ethyleneamines chelating agent under stirring condition; 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 ions is 1 ~ 5:1 ~ 5, and chelating agent 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, sulfate, halide, phosphate, the organic carboxylate, wherein preferably nitrate.
Described ethyleneamines chelating agent comprises: one or more in ethylenediamine, diethylenetriamine, triethylene tetramine, TEPA, the five ethene hexamines, wherein preferred ethylenediamine and triethylene tetramine.
Described alkali metal hydroxide comprises: NaOH, potassium hydroxide, one or more in the lithium hydroxide, wherein preferred NaOH.
The basic structural unit of said spherical structure 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 jackshaft 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 said three-dimensional sisal hemp shape structure mainly contains smooth club shaped structure and step club shaped structure, and wherein the length of rod 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 preparation provided by the invention, can realize control in proper order through the mol ratio and the dropping thereof of the mol ratio of nickel ion in the regulation system and cobalt ions, the kind of ethyleneamines, different amine to nickel cobalt hydroxide pattern; (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 case study on implementation 1 of the present invention.
The X-ray diffractogram of the nickel cobalt hydroxide that Fig. 2 obtains for case study on implementation 1 of the present invention.
The stereoscan photograph of the nickel cobalt hydroxide that Fig. 3 obtains for case study on implementation 2 of the present invention.
The stereoscan photograph of the nickel cobalt hydroxide that Fig. 4 obtains for case study on implementation 3 of the present invention.
The stereoscan photograph of the nickel cobalt hydroxide that Fig. 5 obtains for case study on implementation 4 of the present invention.
The specific embodiment
Below in conjunction with concrete embodiment technical scheme of the present invention is further specified.
Case study on implementation 1
Normal temperature preparation 10ml concentration down is the mixed solution of 0.75mol/L nickel nitrate and cobalt nitrate; Wherein the mol ratio of nickel ion and cobalt ions is 2:1, under stirring condition, adds the ethylenediamine of 0.024mol, continues 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 end product nickel cobalt hydroxide behind the dry 12h down at 40 ℃ then, the scanned photograph and the X-ray diffractogram of product are as depicted in figs. 1 and 2.Gained nickel cobalt hydroxide structure is a spherical structure, 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 jackshaft length is 50nm.
Case study on implementation 2
Normal temperature preparation 10ml concentration down is the mixed solution of 0.75mol/L nickel nitrate and cobalt nitrate, and wherein the mol ratio of nickel ion and cobalt ions is 3:1, under stirring condition, adds the triethylene tetramine of 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 end product nickel cobalt hydroxide behind the dry 12h down at 40 ℃ then, and the scanned photograph of product is as shown in Figure 3; Gained nickel cobalt hydroxide structure is a spherical structure, 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 mixed solution of 0.8mol/L nickel nitrate and cobalt nitrate, and wherein the mol ratio of nickel ion and cobalt ions is 1:3, under stirring condition, adds the triethylene tetramine of 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 end product nickel cobalt hydroxide behind the dry 12h down at 40 ℃ then, and the scanned photograph of product is 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 the length of rod is 1,5 μ m, and diameter is 400nm.
Case study on implementation 4
Normal temperature preparation 10ml concentration down is the mixed solution of 0.8mol/L nickel chloride and cobalt chloride, and wherein the mol ratio of nickel ion and cobalt ions is 1:1, under stirring condition, adds the triethylene tetramine of 0.006mol earlier; The ethylenediamine 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 obtains end product nickel cobalt hydroxide behind the dry 12h down at 40 ℃ then, and the scanned photograph of product is 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 the length of rod is 2 μ m, and diameter is 600nm.
Case study on implementation 5
Normal temperature preparation 10ml concentration down is the mixed solution of 0.75mol/L nickel chloride and cobalt chloride, and wherein the mol ratio of nickel ion and cobalt ions is 1:1, under stirring condition, adds the ethylenediamine of 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 end 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 mixed solution of 0.75mol/L nickelous sulfate and cobaltous sulfate, and wherein the mol ratio of nickel ion and cobalt ions is 3:1, under stirring condition, adds the triethylene tetramine of 0.006mol earlier; The ethylenediamine 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 end product nickel cobalt hydroxide behind the dry 12h down at 40 ℃ then.Gained nickel cobalt hydroxide structure is a spherical structure, and basic structural unit is a single-wheel shape structure, and the diameter of wheel is 2 μ m, and thickness is 900nm.
Claims (3)
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 mixed solution of solubility cobalt salt under the normal temperature, and magnetic agitation 1-2h adds the ethyleneamines chelating agent under stirring condition; 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 between 80 ~ 120 ℃ insulation 3 h, and filtration washing is then at 40 ℃ of nickel cobalt hydroxides that obtain spherical structure or three-dimensional sisal hemp shape structure down behind the dry 12h; Wherein, the mol ratio of nickel ion and cobalt ions is 1 ~ 5:1 ~ 5, and chelating agent is 1 ~ 5:1 with the mol ratio of total metal ion, and alkali hydroxide soln concentration is 6-10mol/L; The basic structural unit of said spherical structure is two-wheel shape structure or hexagon dish; The diameter of said two-wheel shape structure two side wheels is 1-2 μ m, and thickness is 70-120nm, and jackshaft 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 said three-dimensional sisal hemp shape structure is smooth club shaped structure or step club shaped structure, and wherein the length of rod is 1-2 μ m, and diameter is 300-600nm; Described ethyleneamines chelating agent is one or more in ethylenediamine, diethylenetriamine, triethylene tetramine, TEPA, the five ethene hexamines.
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 is: one or more in the nitrate of nickel, sulfate, halide, the phosphate; The solubility cobalt salt is: one or more in the nitrate of cobalt, sulfate, halide, the phosphate.
3. 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 one or more in NaOH, potassium hydroxide, the lithium hydroxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105737389A CN102070208B (en) | 2010-12-06 | 2010-12-06 | Preparation method of nickel-cobalt hydroxide with controllable appearance |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105737389A CN102070208B (en) | 2010-12-06 | 2010-12-06 | Preparation method of nickel-cobalt hydroxide with controllable appearance |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102070208A CN102070208A (en) | 2011-05-25 |
| CN102070208B true CN102070208B (en) | 2012-05-23 |
Family
ID=44028995
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010105737389A Expired - Fee Related CN102070208B (en) | 2010-12-06 | 2010-12-06 | Preparation method of nickel-cobalt hydroxide with controllable appearance |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102070208B (en) |
Families Citing this family (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 |
| 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 |
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 |
-
2010
- 2010-12-06 CN CN2010105737389A patent/CN102070208B/en not_active Expired - Fee Related
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 |
|---|
| 翟海军.掺杂α-Ni(OH)2的合成及其电化学性能研究.《中国优秀博硕士学位论文全文数据库（硕士） 工程科技I辑》.2003,(第2 期),第8页第1.4节. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102070208A (en) | 2011-05-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106564967B (en) | Lithium-rich manganese-based anode material presoma, positive electrode and preparation method thereof | |
| CN100334003C (en) | Nanometer alpha-nickel hydroxide and its prepn | |
| CN102881891B (en) | Method for preparing trivalent ion-doped lithium-rich solid solution cathode material | |
| CN100554162C (en) | A kind of method for preparing high dispersity nano zinc oxide | |
| CN102916177B (en) | Nickel cobalt manganese hydroxide precursor and preparation method thereof | |
| CN111333126B (en) | Nickel cobalt lithium manganate material precursor, preparation method thereof and nickel cobalt lithium manganate positive electrode material | |
| CN101269849A (en) | High-density spherical lithium nickel cobalt manganese oxygen and method for preparing the same | |
| CN104934595A (en) | Methods for preparing nickel-cobalt-aluminum precursor material and nickel-cobalt-aluminum cathode material with gradient distribution of aluminum element | |
| CN109065847A (en) | A kind of white composite material and preparation method in Prussia and application | |
| CN101284684A (en) | Preparing method for nickel-cobalt-lithium manganate precursor of lithium ionic cell positive material | |
| CN103606654B (en) | The preparation method of the coated manganese oxide composite material of a kind of carbon | |
| CN103232069A (en) | Lithium ion battery lithium-rich manganese base positive electrode material preparation method | |
| CN109055976A (en) | A kind of multilevel structure transition metal nitride electrode material and preparation method thereof | |
| CN101304090A (en) | Method for synthesizing lithium ion battery anode material LiNixCoyMn(1-x-y)O2 | |
| CN107342418B (en) | A kind of ferrocyanogen positive electrode and its preparation method and application | |
| CN101269840A (en) | Spherical manganese carbonate and preparing method thereof | |
| CN102881894B (en) | Method for preparing lithium-enriched solid solution cathode material by doping iron, copper and tin ions | |
| CN103682311A (en) | Preparation method of ternary composite cathode material of lithium ion battery | |
| CN110323081A (en) | Nickel hydroxide/basic carbonate cobalt composite material method is prepared on a current collector | |
| CN105355910A (en) | A preparing method of a spherical nickel cobalt lithium aluminate cathode material for lithium ion batteries | |
| CN106904668B (en) | A kind of preparation method of cell positive material tetrakaidecahedron shape nanometer nickel-cobalt LiMn2O4 | |
| CN106115798B (en) | A kind of MnCo2O4Hexagonal nanometer rods and method for preparing Nano cube | |
| CN107742721A (en) | The preparation method of flower-shaped nickel cobalt manganese anode material for lithium-ion batteries | |
| CN107162066A (en) | A kind of nickel doped cobaltic-cobaltous oxide nano flower composite material and its preparation method and application | |
| CN102070208B (en) | Preparation method of nickel-cobalt hydroxide with controllable appearance |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20120523 Termination date: 20141206 |
|
| EXPY | Termination of patent right or utility model |