CN102267729A - Preparation method of spherical nickel hydroxide used as battery cathode material - Google Patents
Preparation method of spherical nickel hydroxide used as battery cathode material Download PDFInfo
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- CN102267729A CN102267729A CN2011101804694A CN201110180469A CN102267729A CN 102267729 A CN102267729 A CN 102267729A CN 2011101804694 A CN2011101804694 A CN 2011101804694A CN 201110180469 A CN201110180469 A CN 201110180469A CN 102267729 A CN102267729 A CN 102267729A
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Abstract
The invention discloses a preparation method of spherical nickel hydroxide used as a battery cathode material, and the preparation method comprises the following steps: adding a nickel source into a cyclamine ionic liquid to obtain a nickel source solution, adding an additive into the nickel source solution and mixing evenly; and then adding a crystallizing agent aqueous solution, reacting while stirring at the temperature of 50-220 DEG C for 1.5-36 hours, cooling to room temperature, separating, washing and drying to obtain spherical nickel hydroxide. In the invention, an ionothermal preparation technology of spherical nickel hydroxide used as a cathode material at low temperature and normal pressure is provided, thereby avoiding the requirements of a hydrothermal method on high pressure; and the ionic liquid not only is used as a reaction medium but also is a structure adjusting and controlling agent for crystal growth, thus spherical nickel hydroxide used as the cathode material with uniform particle size and morphology structure is easily obtained.
Description
One, technical field
The present invention relates to a kind of preparation method of cell positive material, exactly is the preparation method of a kind of cell positive material with ball-shape nickel hydroxide.
Two, background technology
Ni (OH)
2Be the main positive electrode active materials of multiple Edison battery (as Ni/Cd, Ni/Zn, Ni/MH), the capacity and life-span of battery played critical effect.Along with as the widespread use of the green nickel metal hydride battery of high specific energy of new generation at aspects such as mobile communication, power tool and electromobiles, the research of nickel hydroxide material and technology of preparing thereof is also more and more paid attention to.
At present, ball-shape nickel hydroxide generally uses is the chemical precipitation crystal growth in preparation in the suitability for industrialized production, that is: with nickel salt (as NiSO
4, or NiCl
2, or Ni (NO
3)
2Deng) solution, coordination compound (as ammonia or ammonium salt or citric acid or sodium tartrate or disodium ethylene diamine tetraacetate etc.) solution and alkali lye (NaOH or KOH), at a certain temperature, the pH and the stirring velocity of control solution system, the successive reaction certain hour obtains ball-shape nickel hydroxide.
Above-mentioned chemical precipitation crystal growth is reaction medium with the aqueous solution, and the subject matter of existence is for obtaining the ball-shape nickel hydroxide that median size and size-grade distribution meet the requirements, and is very strict to reaction conditions control.And ionic liquid provides new chance as novel solvent and reaction medium for material synthetic, and ion thermal synthesis technology provides new approach for the preparation of ball-shape nickel hydroxide.
Three, summary of the invention
The present invention aims to provide the preparation method of a kind of cell positive material with ball-shape nickel hydroxide.Technical problem to be solved be with ionic liquid as reaction solvent, obtain uniform particles, the regular ball-shape nickel hydroxide particle of pattern by ion process for thermosynthesizing and conditioned reaction condition.
The present invention is to be reaction medium and structure regulating agent with cyclammonium class ionic liquid, under the effect of additive, the crystallization agent is added in the liquid medium of nickel source and the formation of cyclammonium class ionic liquid, the heated and stirred reaction synthesizes the ball-shape nickel hydroxide that size distribution is even, consistence is good.
Technical solution problem of the present invention adopts following technical scheme:
To obtain the nickel source solution that concentration is 50-500g/L in the nickel source adding cyclammonium class ionic liquid, in the solution of nickel source, add additive and mix, add the crystallization agent aqueous solution then, in 50-220 ℃ of stirring reaction 1.5-36 hour, be cooled to room temperature and after separation, washing and drying, obtain ball-shape nickel hydroxide;
The addition of described additive is the 0.2%-10% of described nickel source quality;
The concentration of the described crystallization agent aqueous solution is 150-1000g/L;
The mol ratio of described nickel source and described crystallization agent is 1: 1-6.
Described nickel source is one or more in single nickel salt, nickelous nitrate, nickelous acetate, the nickelous chloride.
Described cyclammonium class ionic liquid is to have in the ionic liquid of following general structure one or more:
[CAH]
+[RCOO]
-
R is H or C in the formula
1-C
2Alkyl; CA is hexamethylenetetramine, imidazoles, 5-pyrazolone, 1H-1,2, and 4-triazole, piperazine, melamine (acyl) amine, 2-imidazolyl ethamine, cyanuric chloride, sym-trinitrobenzene or 2,4-two chloro-6-(adjacent chloro amido) sym-trinitrobenzene.
Described additive is one or more in sodium laurylsulfonate, Sodium dodecylbenzene sulfonate, cetyl trimethylammonium bromide, the polyoxyethylene glycol.
Described crystallization agent is one or more in sodium hydroxide, potassium hydroxide, urea, thiocarbamide, yellow soda ash, volatile salt, the bicarbonate of ammonia.
Compared with the prior art, beneficial effect of the present invention is embodied in:
1, the present invention as reaction medium, meets the growing environment of ball-shape nickel hydroxide with cyclammonium class ionic liquid, is easy to reach the final control that realizes last crystalline nucleation and coarsening rate of adjusting by controlled temperature, obtains ball-shape nickel hydroxide.
2, the invention provides a kind of hot method technology of preparing of ion of ball-shape nickel hydroxide positive electrode material of atmospheric low-temperature, can keep away the system hydrothermal method the highly compressed requirement; Ionic liquid is not only made reaction medium but also be the structure regulating agent of crystal growth, is easy to obtain particle size, appearance structure uniform spherical nickel hydroxide anode material.
3, to be used for the ionic liquid of reaction medium and structure regulating agent in the hot method of ion is synthetic be cyclammonium class ionic liquid in the present invention, and such ionic liquid has and is easy to synthesize, and cost is lower, the characteristics of Heat stability is good, and can be by separating the realization recycling.
4, preparation cycle of the present invention is short, energy consumption is little, and the product size distribution is even, consistence is good, and chemical property has satisfactory stability.And the ionic liquid of use can reuse through separating after the use owing to have good thermostability.
Four, description of drawings
Fig. 1 is the XRD figure of the ball-shape nickel hydroxide positive electrode material of embodiment 1 preparation.
Fig. 2 is the SEM figure of the ball-shape nickel hydroxide positive electrode material of embodiment 2 preparations.
Fig. 3 is the discharge curve first of the ball-shape nickel hydroxide positive electrode material of embodiment 2 preparations.
Five, embodiment
Embodiment 1:
Take by weighing the adding of 4.71g nickelous chloride 50mL 1H-1 is housed, 2, in the round-bottomed flask of 4-triazole acetato-liquid, add the 0.4g sodium laurylsulfonate simultaneously, stir and make its all dissolving in ionic liquid; Under stirring condition, drip the solution that 0.8g sodium hydroxide and 4mL water form, be heated to 100 ℃ of reaction 12h; To precipitate successively after the cooling and after separation, washing and drying, obtain ball-shape nickel hydroxide.
Ball-shape nickel hydroxide sample according to embodiment 1 preparation is tested through XRD, shows other dephasign diffraction peaks not occur, and the sample of this explanation preparation is that degree of crystallinity is good, the beta crystal Ni (OH) of the complete method of crystalline structure
2
Embodiment 2:
Take by weighing the adding of 4.71g nickelous chloride 50mL 11H-1 is housed, 2, in the round-bottomed flask of 4-triazole acetato-liquid, add the 0.4g sodium laurylsulfonate simultaneously, stir and make its all dissolving in ionic liquid; Under stirring condition, drip the solution that 1.12g potassium hydroxide and 4mL water form, be heated to 50 ℃ of reaction 20h; To precipitate successively after the cooling and after separation, washing and drying, obtain ball-shape nickel hydroxide.
Ball-shape nickel hydroxide sample according to embodiment 2 preparations is sphere and uniform particles through the SEM test shows; Through electrochemical property test, its first loading capacity reach 262.4mAh/g, and more smooth discharge platform is arranged, sample of this explanation preparation has good electrochemical.
Embodiment 3:
Take by weighing the adding of 2.5g nickelous acetate 50mL 1H-1 is housed, 2, in the round-bottomed flask of 4-triazole acetato-liquid, add the 0.25g Sodium dodecylbenzene sulfonate simultaneously, stirring is uniformly dispersed it in ionic liquid; Under stirring condition, drip the solution that 3.4g sodium hydroxide and 3.4mL water form, be heated to 220 ℃ of reaction 1.5h; To precipitate successively after the cooling and after separation, washing and drying, obtain ball-shape nickel hydroxide.
Embodiment 4:
Take by weighing the adding of 25g nickelous nitrate and be equipped with in the ion liquid round-bottomed flask of 50mL 2-imidazolyl ethamine propionic acid, add the 2.5g cetyl trimethylammonium bromide simultaneously, stir and make its all dissolving in ionic liquid; Under stirring condition, drip the solution that 13.2g urea and 88mL water form, be heated to 50 ℃ of reaction 36h; To precipitate successively after the cooling and after separation, washing and drying, obtain ball-shape nickel hydroxide.
Embodiment 5:
Take by weighing the adding of 5.26g single nickel salt and be equipped with in the ion liquid round-bottomed flask of 50mL piperazinecarboxylic acid, add the 0.3g cetyl trimethylammonium bromide simultaneously, stirring is uniformly dispersed it in ionic liquid; Under stirring condition, drip the solution that 4.8g urea and 40mL water form, be heated to 80 ℃ of reaction 16h; To precipitate successively after the cooling and after separation, washing and drying, obtain ball-shape nickel hydroxide.
Embodiment 6:
Take by weighing the adding of 4.71g nickelous chloride and be equipped with in the ion liquid round-bottomed flask of 50mL piperazinecarboxylic acid, add the 0.4g cetyl trimethylammonium bromide simultaneously, stirring is uniformly dispersed it in ionic liquid; Under stirring condition, the solution that Dropwise 5 g urea and 9mL water form is heated to 120 ℃ of reaction 10h; To precipitate successively after the cooling and after separation, washing and drying, obtain ball-shape nickel hydroxide.
Embodiment 7:
Take by weighing the adding of 5.26g single nickel salt 50mL2 is housed, in the round-bottomed flask of 4-two chloro-6-(adjacent chloro amido) sym-trinitrobenzene formate ion liquid, add the 0.4g cetyl trimethylammonium bromide simultaneously, stirring is uniformly dispersed it in ionic liquid; Under stirring condition, drip the solution that 4.8g urea and 10mL water form, be heated to 150 ℃ of reaction 7h; To precipitate successively after the cooling and after separation, washing and drying, obtain ball-shape nickel hydroxide.
Embodiment 8:
Take by weighing the adding of 5.82g nickelous nitrate and be equipped with in the ion liquid round-bottomed flask of 50mL imidazoleacetic acid, add the 0.5g cetyl trimethylammonium bromide simultaneously, stirring is uniformly dispersed it in ionic liquid; Under stirring condition, drip the solution that 4.8g urea and 8mL water form, be heated to 180 ℃ of reaction 3h; To precipitate successively after the cooling and after separation, washing and drying, obtain ball-shape nickel hydroxide.
Claims (5)
1. a cell positive material is with the preparation method of ball-shape nickel hydroxide, it is characterized in that: will obtain the nickel source solution that concentration is 50-500g/L in the nickel source adding cyclammonium class ionic liquid, in the solution of nickel source, add additive and mix, add the crystallization agent aqueous solution then, in 50-220 ℃ of stirring reaction 1.5-36 hour, be cooled to room temperature and after separation, washing and drying, obtain ball-shape nickel hydroxide;
The addition of described additive is the 0.2%-10% of described nickel source quality;
The concentration of the described crystallization agent aqueous solution is 150-1000g/L;
The mol ratio of described nickel source and described crystallization agent is 1: 1-6.
2. preparation method according to claim 1 is characterized in that: described nickel source is one or more in single nickel salt, nickelous nitrate, nickelous acetate, the nickelous chloride.
3. preparation method according to claim 1 is characterized in that: described cyclammonium class ionic liquid is to have in the ionic liquid of following general structure one or more:
[CAH]
+[RCOO]
-
R is H or C in the formula
1-C
2Alkyl; CA is hexamethylenetetramine, imidazoles, 5-pyrazolone, 1H-1,2, and 4-triazole, piperazine, melamine (acyl) amine, 2-imidazolyl ethamine, cyanuric chloride, sym-trinitrobenzene or 2,4-two chloro-6-(adjacent chloro amido) sym-trinitrobenzene.
4. preparation method according to claim 1 is characterized in that: described additive is one or more in sodium laurylsulfonate, Sodium dodecylbenzene sulfonate, cetyl trimethylammonium bromide, the polyoxyethylene glycol.
5. preparation method according to claim 1 is characterized in that: described crystallization agent is one or more in sodium hydroxide, potassium hydroxide, urea, thiocarbamide, yellow soda ash, volatile salt, the bicarbonate of ammonia.
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| CN2011101804694A CN102267729B (en) | 2011-06-30 | 2011-06-30 | Preparation method of spherical nickel hydroxide used as battery cathode material |
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| CN102267729B CN102267729B (en) | 2013-06-12 |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| CN103387268A (en) * | 2013-07-30 | 2013-11-13 | 浙江大学 | Preparation method of nano-nickel oxide for electrode material of supercapacitor, and nano-nickel oxide prepared by method |
| CN106018507A (en) * | 2016-05-16 | 2016-10-12 | 天津理工大学 | Preparation method of mesoporous nickel oxide having excellent ammonia gas sensitive properties |
| CN106745133A (en) * | 2017-01-24 | 2017-05-31 | 武汉工程大学 | A kind of preparation method of water insoluble hydroxide |
| CN112362713A (en) * | 2020-11-24 | 2021-02-12 | 吉林大学 | Sensitive electrode material for direct electrochemical detection of ammonia nitrogen in water and preparation method thereof |
| CN115259246A (en) * | 2022-07-08 | 2022-11-01 | 深圳市豪鹏科技股份有限公司 | Spherical alpha-nickel hydroxide, synthesis method, positive plate and battery |
Citations (3)
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|---|---|---|---|---|
| CN1221707A (en) * | 1998-12-11 | 1999-07-07 | 清华大学 | Tech. for preparing high density spherical nickel hydroxide by controlled crystallizing process |
| US6432580B1 (en) * | 1998-08-17 | 2002-08-13 | Ovonic Battery Company, Inc. | Method of making a nickel hydroxide material |
| CN102054987A (en) * | 2010-11-24 | 2011-05-11 | 安徽亚兰德新能源材料有限公司 | Spherical nickel hydroxide for high-temperature battery anode and preparation method thereof |
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2011
- 2011-06-30 CN CN2011101804694A patent/CN102267729B/en not_active Expired - Fee Related
Patent Citations (3)
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| US6432580B1 (en) * | 1998-08-17 | 2002-08-13 | Ovonic Battery Company, Inc. | Method of making a nickel hydroxide material |
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Non-Patent Citations (1)
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| CN103387268A (en) * | 2013-07-30 | 2013-11-13 | 浙江大学 | Preparation method of nano-nickel oxide for electrode material of supercapacitor, and nano-nickel oxide prepared by method |
| CN106018507A (en) * | 2016-05-16 | 2016-10-12 | 天津理工大学 | Preparation method of mesoporous nickel oxide having excellent ammonia gas sensitive properties |
| CN106018507B (en) * | 2016-05-16 | 2018-05-15 | 天津理工大学 | A kind of preparation method of the mesoporous nickel oxide with ammonia air-sensitive performance |
| CN106745133A (en) * | 2017-01-24 | 2017-05-31 | 武汉工程大学 | A kind of preparation method of water insoluble hydroxide |
| CN106745133B (en) * | 2017-01-24 | 2018-03-20 | 武汉工程大学 | A kind of preparation method of hydroxide not soluble in water |
| CN112362713A (en) * | 2020-11-24 | 2021-02-12 | 吉林大学 | Sensitive electrode material for direct electrochemical detection of ammonia nitrogen in water and preparation method thereof |
| CN112362713B (en) * | 2020-11-24 | 2021-12-07 | 吉林大学 | Sensitive electrode material for direct electrochemical detection of ammonia nitrogen in water and preparation method thereof |
| CN115259246A (en) * | 2022-07-08 | 2022-11-01 | 深圳市豪鹏科技股份有限公司 | Spherical alpha-nickel hydroxide, synthesis method, positive plate and battery |
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