CN1067659C - Tech. for preparing high density spherical nickel hydroxide by controlled crystallizing process - Google Patents
Tech. for preparing high density spherical nickel hydroxide by controlled crystallizing process Download PDFInfo
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- CN1067659C CN1067659C CN98123187A CN98123187A CN1067659C CN 1067659 C CN1067659 C CN 1067659C CN 98123187 A CN98123187 A CN 98123187A CN 98123187 A CN98123187 A CN 98123187A CN 1067659 C CN1067659 C CN 1067659C
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- complexing agent
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Abstract
The present invention relates to a technology for preparing high-density spherical nickel hydroxide by the crystallization control process. In the technology, a nickel salt water solution with certain concentration reacts with an alkali solution in the presence of a complexing agent to generate spherical nickel hydroxide polycrystal grains, and through solid-liquid separation, washing and drying, the nickel hydroxide product is obtained. The present invention is characterized in that the used complexing agent is two or more than two mixed complexing agents with different nickel ion complexing power; compared with the use of a single complexing agent, the use of the mixed complexing agent has the advantages that the crystallization rate and the crystallization degree of nickel hydroxide can be effectively controlled, and the final product has higher electrochemistry activity.
Description
The present invention relates to a kind ofly be equipped with the technology of high-density ball-shape nickel hydroxide, belong to chemical engineering and field of new with the crystallization control legal system.
High-density ball-shape nickel hydroxide (Ni (OH)
2) mainly as the positive electrode active materials of alkaline rechargeable battery.At present the direction of rechargeable battery forward height ratio capacity develops, and this just requires positive electrode active materials will have high-density and advantage of high activity, and the degree of crystallinity that to influence its active principal element be nickel hydroxide.The fundamental point of the crystallization control technology of preparation ball-shape nickel hydroxide is to regulate and control the speed of response of nickel salt and alkali and the crystallization velocity of reaction product nickel hydroxide by adding certain complexing agent, thereby controls its degree of crystallinity.At present, all be to adopt ammoniacal liquor or this single complexing agent of ammonium salt both at home and abroad usually in this technology.Adopting ammonia or a kind of complexing agent of ammonium salt to prepare in the technology of ball-shape nickel hydroxide, have higher density in order to guarantee product, the degree of crystallinity of nickel hydroxide must be higher, therefore influenced its activity.
The objective of the invention is to propose a kind of technology that is equipped with high-density ball-shape nickel hydroxide with the crystallization control legal system, select at least two kinds of complexing agent mixing uses that nickel ion had different complex abilitys, guaranteeing that nickel hydroxide has under the prerequisite of higher density, suitably reduce its degree of crystallinity, thereby improve its activity.
The present invention design be equipped with the technology of high-density ball-shape nickel hydroxide with the crystallization control legal system, comprise following each step:
(1) nickel concentration be add additive in the nickel sulfate solution of 1～2.2 mol and complexing agent standby, additive wherein is the vitriol of cobalt, zinc or cadmium, the mol ratio of add-on is Co: Ni=0.005～0.1: 1, Zn: Ni=0.02～0.06: 1, Cd: Ni=0.02～0.06: 1, complexing agent wherein is any in Trisodium Citrate, Sodium Glutamate, Seignette salt, the disodium ethylene diamine tetraacetate or two kinds, and the mol ratio of add-on is: complexing agent: nickel=0.001～0.5: 1;
(2) standby with sodium hydroxide and complexing agent ammonia preparation alkali aqueous solution, wherein concentration sodium hydroxide is 4～6 mol, and the mol ratio of ammonia and sodium hydroxide is: ammonia: sodium hydroxide=0.1～0.5: 1;
(3) with volume pump above-mentioned two kinds of solution being continuously pumped in the crystallization reactor, is 10～13 by the flow control reaction pH value of regulating alkali aqueous solution, and temperature of reaction is 40～60 ℃, and the reaction times is: 4～10 hours;
(4) above-mentioned three-step reaction product carries out solid-liquid separation through solid-liquid separator, and the nickel hydroxide that separation obtains is after the washer washing, and drying is 2～4 hours under 60～100 ℃, is the high-density ball-shape nickel hydroxide product.
The crystallization control technology of the use mixed twine mixture that the present invention proposes is compared as the technology of complexing agent with using single ammoniacal liquor or ammonium salt, and the ball-shape nickel hydroxide of gained has same high density, but its specific surface area is bigger, and crystal grain is thinner, and electrochemical activity is higher.
Introduce embodiments of the invention below:
The composition of embodiment one, nickel salt aqueous solution is a single nickel salt, additive and complexing agent, and wherein additive is rose vitriol and zinc sulfate, the concentration of single nickel salt is 1.9 mol, Co: Zn: Ni=2.5: 5.0: 100 (mol ratio), complexing agent are trisodium citrate, and concentration is 0.07 mol.The composition of alkali aqueous solution is sodium hydroxide and complexing agent ammonia, and concentration sodium hydroxide is 5.0 mol, and the concentration of ammonia is 1.0 mol.5 liters of the effective volumes of crystallization reactor, with volume pump with above-mentioned nickel salt aqueous solution and alkali aqueous solution respectively continuous and quantitative be input in the crystallization reactor, stirring velocity is 700 rev/mins.Control reaction pH value by the flow of regulating alkali aqueous solution, the pH value is 11.00 ± 0.05.50 ± 0.5 ℃ of temperature of reaction, the reaction times is 7 hours.The nickel hydroxide that generates is washed through solid-liquid separation, and 80 ℃ of dryings obtained sample in two hours.Recording this sample is β-Ni (OH)
2, sphere, tap density 2.10g/cm
3, median size 10-15 μ m, BET specific surface area 23m
2/ g, (101) crystal face X-ray diffraction peak halfwidth is 1.01 °, the specific discharge capacity when 0.2C discharges and recharges is 284mAh/g.
Adding complexing agent in embodiment two, the nickel salt aqueous solution is Sodium Glutamate, and concentration is 0.038 mol, and the ammonia concentration in the alkali aqueous solution is 0.5 mol, and other conditions are with embodiment one.The nickel hydroxide sample of present embodiment is β-Ni (OH) after tested
2, sphere, tap density 2.12g/cm
3, median size 10-15 μ m, BET specific surface area 25m
2/ g, (101) crystal face X-ray diffraction peak halfwidth is 1.05 °, the specific discharge capacity when 0.2C discharges and recharges is 287mAh/g.
Complexing agent is a Seignette salt in embodiment three, the nickel salt aqueous solution, and concentration is 0.10 mol, and reaction pH value is 10.90 ± 0.05, and other conditions are with embodiment one.The nickel hydroxide sample of present embodiment is β-Ni (OH) after tested
2, sphere, tap density 2.10g/cm
3, median size 10-15 μ m, BET specific surface area 22m
2/ g, (101) crystal face X-ray diffraction peak halfwidth is 0.96 °, the specific discharge capacity when 0.2C discharges and recharges is 281mAh/g.
Complexing agent is a disodium ethylene diamine tetraacetate in embodiment four, the nickel salt aqueous solution, and concentration is 0.02 mol, and the concentration that adds complexing agent ammonia in the alkali aqueous solution is 1.2 mol, and reaction pH value is 11.10 ± 0.05, and other conditions are with embodiment one.The nickel hydroxide sample of present embodiment is β-Ni (OH) after tested
2, sphere, tap density 2.15g/cm
3, median size 10-15 μ m, BET specific surface area 21m
2/ g, (101) crystal face X-ray diffraction peak halfwidth is 0.99 °, the specific discharge capacity when 0.2C discharges and recharges is 286mAh/g.
Adding complexing agent in embodiment five, the nickel salt aqueous solution is Sodium Glutamate and disodium ethylene diamine tetraacetate.Concentration 0.017 mol of Sodium Glutamate, the concentration of disodium ethylene diamine tetraacetate is 0.01 mol, other conditions are with embodiment one.The nickel hydroxide sample of present embodiment is β-Ni (OH) after tested
2, sphere, tap density 2.15g/cm
3, median size 10-15 μ m, BET specific surface area 21m
2/ g, (101) crystal face X-ray diffraction peak halfwidth is 1.03 °, the specific discharge capacity when 0.2C discharges and recharges is 285mAh/g.
Additive therefor is rose vitriol and Cadmium Sulphate in embodiment six, the nickel salt aqueous solution, Co: Cd: Ni=2.5: 5.0: 100 (mol ratio), other conditions are with embodiment five.The nickel hydroxide sample of present embodiment is β-Ni (OH) after tested
2, sphere, tap density 2.17g/cm
3, median size 10-15 μ m, BET specific surface area 24m
2/ g, (101) crystal face X-ray diffraction peak halfwidth is 1.05 °, the specific discharge capacity when 0.2C discharges and recharges is 288mAh/g.
The effective volume of embodiment seven, crystallization reactor is 5 cubic metres, and 400 liters/hour of nickel salt aqueous solution flows, alkali aqueous solution flow are 300 liters/hour, 200 rev/mins of stirring velocitys, and other conditions are with embodiment five.The nickel hydroxide sample of present embodiment is β-Ni (OH) after tested
2, sphere, tap density 2.19g/cm
3, median size 10-15 μ m, BET specific surface area 22m2/g, (101) crystal face X-ray diffraction peak halfwidth is 1.03 °, the specific discharge capacity when 0.2C discharges and recharges is 287mAh/g.
The composition of comparing embodiment one, nickel salt aqueous solution is single nickel salt and additive sulfuric acid cobalt and zinc sulfate, the concentration of single nickel salt is 1.9 mol, Co: Zn: Ni=2.5: 5.0: 100 (mol ratio), the composition of alkali aqueous solution is sodium hydroxide and complexing agent ammonia, concentration sodium hydroxide is 5.0 mol, the concentration of ammonia is 1.2 mol, and other conditions are with embodiment one.The nickel hydroxide sample of comparing embodiment is β-Ni (OH) after tested
2, sphere, tap density 2.12g/cm
3, median size 10-15 μ m, BET specific surface area 15m
2/ g, (101) crystal face X-ray diffraction peak halfwidth is 0.87 °, the specific discharge capacity when 0.2C discharges and recharges is 273mAh/g.
Claims (1)
1, a kind ofly be equipped with the technology of high-density ball-shape nickel hydroxide, it is characterized in that this technology comprises following each step with the crystallization control legal system:
(1) nickel concentration be add additive in the nickel sulfate solution of 1～2.2 mol and complexing agent standby, additive wherein is the vitriol of cobalt, zinc or cadmium, the mol ratio of add-on is Co: Ni=0.005～0.1: 1, Zn: Ni=0.02～0.06: 1, Cd: Ni=0.02～0.06: 1, complexing agent wherein is any in Trisodium Citrate, Sodium Glutamate, Seignette salt, the disodium ethylene diamine tetraacetate or two kinds, and the add-on mol ratio is: complexing agent: nickel=0.001～0.5: 1;
(2) standby with sodium hydroxide and complexing agent ammonia preparation alkali aqueous solution, wherein concentration sodium hydroxide is 4～6 mol, and the mol ratio of ammonia and sodium hydroxide is: ammonia: sodium hydroxide=0.1～0.5: 1;
(3) with volume pump above-mentioned two kinds of solution being continuously pumped in the crystallization reactor, is 10～13 by the flow control reaction pH value of regulating alkali aqueous solution, and temperature of reaction is 40～60 ℃, and the reaction times is: 4～10 hours;
(4) above-mentioned three-step reaction product carries out solid-liquid separation through solid-liquid separator, and the nickel hydroxide that separation obtains is after the washer washing, and drying is 2～4 hours under 60～100 ℃, is the high-density ball-shape nickel hydroxide product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98123187A CN1067659C (en) | 1998-12-11 | 1998-12-11 | Tech. for preparing high density spherical nickel hydroxide by controlled crystallizing process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98123187A CN1067659C (en) | 1998-12-11 | 1998-12-11 | Tech. for preparing high density spherical nickel hydroxide by controlled crystallizing process |
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| CN1221707A CN1221707A (en) | 1999-07-07 |
| CN1067659C true CN1067659C (en) | 2001-06-27 |
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| CN98123187A Expired - Fee Related CN1067659C (en) | 1998-12-11 | 1998-12-11 | Tech. for preparing high density spherical nickel hydroxide by controlled crystallizing process |
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW520575B (en) * | 2000-04-21 | 2003-02-11 | Sony Corp | Positive electrode material and nickel-zinc battery |
| CN100406392C (en) * | 2006-12-29 | 2008-07-30 | 北京工业大学 | Preparing process of nickel hydroxide film in nano structure |
| CN101577333B (en) * | 2009-06-10 | 2011-09-28 | 江门市长优实业有限公司 | High specific capacity discharge platform spherical nickel hydroxide |
| CN101635356B (en) * | 2009-06-10 | 2011-06-22 | 江门市长优实业有限公司 | Spherical nickel hydroxide for high-temperature nickel batteries and preparation method thereof |
| CN102267729B (en) * | 2011-06-30 | 2013-06-12 | 合肥工业大学 | Preparation method of spherical nickel hydroxide used as battery cathode material |
| CN103259010B (en) * | 2013-04-23 | 2015-06-17 | 宁夏东方钽业股份有限公司 | Preparation method of amphoteric metal element doped lithium-ion cathode material precursor |
| CN106186088A (en) * | 2016-07-11 | 2016-12-07 | 潮州三环（集团）股份有限公司 | A kind of nickel oxide powder body and preparation method thereof |
| CN106025265B (en) * | 2016-07-12 | 2019-07-02 | 广东工业大学 | A method of preparing α nickel hydroxide |
| CN111675247A (en) * | 2020-06-12 | 2020-09-18 | 福建常青新能源科技有限公司 | Method for preparing precursor of NCM high-nickel ternary cathode material |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5684323A (en) * | 1979-12-06 | 1981-07-09 | Sumitomo Metal Mining Co Ltd | Removing method for cobalt from aqueous nickel sulfate solution |
| CN1075697A (en) * | 1993-04-09 | 1993-09-01 | 河南师范大学 | Preparation method of corpuscle ball type nickel hydroxide |
| JPH0848506A (en) * | 1994-08-05 | 1996-02-20 | Nikko Metal Pureeteingu Kk | Production of metal hydroxide powder |
| US5498403A (en) * | 1994-05-20 | 1996-03-12 | Hyundai Motor Company | Method for preparing high density nickel hydroxide used for alkali rechargeable batteries |
-
1998
- 1998-12-11 CN CN98123187A patent/CN1067659C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5684323A (en) * | 1979-12-06 | 1981-07-09 | Sumitomo Metal Mining Co Ltd | Removing method for cobalt from aqueous nickel sulfate solution |
| CN1075697A (en) * | 1993-04-09 | 1993-09-01 | 河南师范大学 | Preparation method of corpuscle ball type nickel hydroxide |
| US5498403A (en) * | 1994-05-20 | 1996-03-12 | Hyundai Motor Company | Method for preparing high density nickel hydroxide used for alkali rechargeable batteries |
| JPH0848506A (en) * | 1994-08-05 | 1996-02-20 | Nikko Metal Pureeteingu Kk | Production of metal hydroxide powder |
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