CN1053646C - Preparation of high density and activity spherical nickle hydroxide - Google Patents
Preparation of high density and activity spherical nickle hydroxide Download PDFInfo
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- CN1053646C CN1053646C CN97100691A CN97100691A CN1053646C CN 1053646 C CN1053646 C CN 1053646C CN 97100691 A CN97100691 A CN 97100691A CN 97100691 A CN97100691 A CN 97100691A CN 1053646 C CN1053646 C CN 1053646C
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- mother liquor
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Abstract
The present invention discloses a method for preparing high-density high-activity spherical nickel hydroxide, which relates to the preparation of high-density high-activity spherical nickel hydroxide for secondary anodal active materials for alkaline storage batteries. The present invention is characterized in that a nickel sulfate salt solution containing ammonia and ammonium and a sodium hydroxide water solution containing ammonia are continuously conveyed into a reactor, and nickel hydroxide particles and mother liquor generated in the reactor are respectively discharged from the reactor from two outlets; after the nickel hydroxide particles pass through a hydraulic particle separator, through aging, washing and drying, the product is obtained, and the mother liquor is treated and then returned to the reactor for repeated use. The nickel hydroxide produced by the present invention has the advantages of narrow distribution range of the particle size, low production cost and high industrial value.
Description
The invention relates to the positive electrode active materials of secondary Edison battery--the preparation method of nickel hydroxide.
Along with the develop rapidly and the electric vehicle engineering of portable communication equipment and portable computer progressively moves towards practicability, people are to ni-mh, and the specific energy of secondary cells such as NI-G constantly proposes higher requirement.Traditional sintered type technology for preparing electrode more and more can not satisfy this requirement.Exploitation in recent years be the specific energy that the non-sintered type technology for preparing electrode of collector has improved battery greatly with nickel foam and fiber nickel.Positive electrode active materials--nickel hydroxide has sphere for the ni-mh of non-sintered type high-energy-density and nickel-cadmium cell requirement, high-density and advantage of high activity.The more representational processing method of preparation high-density ball-shape nickel hydroxide is the scheme that JP2-6340 proposes.Its main points are: nickel salt aqueous solution, alkali aqueous solution and ammonia or ammonium salt aqueous solution import reactor respectively continuously, and reaction blended (nickel hydroxide particle and mother liquor) is discharged reactor continuously in the overflow mode, and the reaction solution pH value is 9-12, and temperature of reaction is 20-80 ℃.Reaction mixture is through solid-liquid separation, and washing and drying obtain product.The subject matter of this method is that product granularity is restive, be easy to generate two kinds of deflections: the one, more newborn nickel hydroxide fine particle is taken out of reactor by mother liquor, and the bigger particle of part may be stranded in and continues in the reactor to grow up the long period, to making Granularity Distribution wide; The 2nd, particle meeting sometimes " is grown up " synchronously, and to making product granularity excessive, density descends on the contrary.In order to overcome " growing up synchronously " problem, JP3-252318 has improved the technology that JP2-6340 proposes.Main improvement is: by periodically adjusting the method for pH value, obtain reasonably Granularity Distribution.But prepare in the processing condition of ball-shape nickel hydroxide at crystallization process, PH is one of the most responsive factor.It is not only influential to the granular size and the density of product, and its electrochemical activity is also had considerable influence.The frequent pH value of adjusting is difficult to guarantee the stable of product performance, in addition, does not all consider the multiplexing problem of mother liquor in the above-mentioned patent.
The purpose of this invention is to provide a kind of processing method for preparing high density and activity spherical nickle hydroxide, make that the particle size distribution of product is narrow, stable performance, the mother liquor reusable cuts down the consumption of energy, and reduces liquid waste disposal amount ratio.
The present invention is achieved like this: with single nickel salt, sodium hydroxide, ammoniacal liquor or ammonium salt and a small amount of active additive (rose vitriol and zinc sulfate) are initial feed, in dissolver, be mixed with the nickel sulfate solution that contains ammonia, ammonium and additive sulfuric acid cobalt, contain the aqueous sodium hydroxide solution of ammonia and additive sulfuric acid zinc.This feed liquid is transported in the reactor continuously, and the pH value of control reaction solution and temperature of reaction and continuous the stirring make it that chemical reaction take place in reactor, and wherein nickel salt and alkali generate nickel hydroxide, and ammonia is used for regulating the degree of saturation of crossing of nickel ion as a kind of complexing agent.Under in reactor, constantly stirring, nickel hydroxide crystal process nucleation that constantly generates and the sphere and the similar spheroidal particle of growing up and forming a certain size gradually, and generate the mother liquor that mainly contains sodium sulfate simultaneously.Above-mentioned said nickel hydroxide particle and mother liquor are discharged continuously from two outlets of reactor respectively, and wherein nickel hydroxide particle enters digestion tank after hydromechanics granular size separator separates, and mother liquor also is input in the digestion tank behind the mother liquor settler.Mother liquor and nickel hydroxide mix and ageing once more in digestion tank, mixture carries out solid-liquid separation through solid-liquid separator then, obtain product after the washing of nickel hydroxide particle process, the drying, and mother liquor is removed most of sodium sulfate through crystallization, wherein 90 percent return dissolver and prepare burden, 10 handle the back through the liquid waste disposal device again discharges.The PH of above-mentioned said reactor control reaction solution is 10.00-13.00, temperature of reaction 30-70 ℃, and reaction times 5-10 hour.
Fig. 1 is a process flow sheet of the present invention.Among Fig. 1: 1 is dissolver, and 2 is reactor, and 3 is the mother liquor settler, and 4 is hydromechanics granular size separator, and 5 is digestion tank, 6 is solid-liquid separator, and 7 is washer, and 8 is moisture eliminator, and 9 is the sulfate crystal device, 10 is the liquid waste disposal device, and C is an initial feed, and A is a product, and B is a waste liquid.
Below in conjunction with Fig. 1 technological process of the present invention is described. Give anti-by the material liquid continuous supplying of dissolvers 1 preparation Answer device 2, the mother liquor that generates in reactor 2 is transported in the digestion tank 5 after clarifier 3 clarifications, and generate Nickel hydroxide particle enters digestion tank 5 through hydraulics granular size separator 4. Mother liquor and nickel hydroxide advance respectively Again mix and ageing after entering digestion tank 5, mother liquor and nickel hydroxide mixture carry out through solid-liquid separator 6 then Separation of Solid and Liquid. Nickel hydroxide particle becomes product A again behind washer 7 and drier 8. Mother liquor is through crystallization After device 9 is removed most of sodium sulphate, wherein 90 percent return dissolvers 1 batching, ten Percent is again through useless Waste liquid B discharging after liquid processor 10 is processed.
Through the mother liquor contains sodium sulfate 30-40 grams per liter that crystallizer 9 is processed, ammonia 0.2-0.5 mol/L. Thus female The nickel sulfate solution nickel concentration of liquid preparation is the 1.0-2.0 mol/L, and ammonia concentration is the 0.1-0.4 mol/L; Thus mother liquor and ammoniacal liquor the preparation alkali lye, naoh concentration is the 2-6 mol/L, ammonia concentration 0.2-1.5 rubs You/liter.
Fig. 2 has provided reactor 2 in Fig. 1 flow process, mother liquor clarifier 3, and hydraulics granular size separator 4, The operating principle figure of digestion tank 5. Among Fig. 2,2. reactor, 3. mother liquor clarifier, 4. the hydraulics particle is big Little separator, 5. digestion tank, 11. nickel sulfate solutions, 12. sodium hydrate aqueous solutions, 13. measuring pumps, 14. overflow pipe.
Under steady operation conditions, enter the nickel sulfate solution 11 of reactor and sodium hydrate aqueous solution 12 Total flow should equal from the mother liquor of overflow pipe 14 outflows and the total flow of nickel hydroxide mixture. At this moment, when logical The mother liquid flow rate of crossing measuring pump 13 is during greater than the total flow of nickel sulfate solution 11 and sodium hydrate aqueous solution 12, Partial mother liquid will be from digestion tank 5 by hydraulics granular size separator Returning reactor 2. So just caused The mother liquor that returns and the adverse current of nickel hydroxide particle waterpower granular size separator of discharging from reactor 2 Effect, this backwash effect are exactly the hydraulic principle that granular size is separated, little particularly newly-generated of part The nickel hydroxide fine grained will be taken back reactor by the mother liquor of adverse current. If adjust measuring pump 13 control mother liquors With the flow proportional of nickel sulfate solution 11 and sodium hydrate aqueous solution 12, thereby control is by the hydraulics particle Size separation device 4 returns the flow velocity of mother liquor, just can to the size of the nickel hydroxide particle that enters digestion tank 5 and Distribution is controlled.
The invention has the advantages that:
(1) owing to adopted the size and the distribution of hydraulic method control product particle, not only make the product granularity size more suitable, narrow distribution range has avoided traditional technology to control the unsettled shortcoming of product performance that product granularity may cause by adjusting pH value merely simultaneously.
(2) the present invention has adopted the flow process that mother liquor is recycled, and can effectively save starting material, and for example: the multiplexing amount of ammonia accounts for 70 percent of total consumption.Liquid waste disposal amount (generally adopting evaporative crystallization to handle) has reduced 90 percent simultaneously, can cut down the consumption of energy greatly.Therefore, the present invention has big industrial value.
Embodiment one reactor useful volume is 200 liters.
Nickel sulfate solution (before mother liquor is multiplexing): concentration of nickel sulfate is 1.7 mol, rose vitriol 0.043 mol, do not contain ammonia or ammonium, PH=2-3. mother liquor is multiplexing back: concentration of nickel sulfate 1.7 mol, rose vitriol: 0.043 mol, ammonia and ammonium total concn 0.3 mol, sodium sulfate concentration 0.25 mol, PH=4-5,14.5 liters of flows/time.
Alkali aqueous solution (before mother liquor is multiplexing): naoh concentration 4.5 mol, zinc sulfate: 0.11 mol, ammonia concentration 1.2 mol.The multiplexing back of mother liquor: naoh concentration 4.5 mol, zinc sulfate 0.11 mol, ammonia concentration 0.8 mol, sodium sulfate concentration 0.2 mol, average discharge be about 10.5 liters/time, by regulating alkali aqueous solution flow control reaction solution PH=11.00 ± 0.02.Temperature of reaction is 50 ℃.
Mother liquor is through settler, and nickel hydroxide is discharged from reactor respectively through hydromechanics granular size separator.29 liters of mother liquid flow rates/time.
Embodiment two
Reactor effective volume: 2 meters
3The nickel sulfate solution flow: 145 liters/time, about 105 liters of flux of alkaline liquor/time, 290 liters of mother liquid flow rates/time, other conditions are with embodiment one.
Comparative example one
Mother liquor is not multiplexing.Single nickel salt and sodium hydroxide are prepared by deionized water.Composition and concentration are respectively with multiplexing each the preceding solution of mother liquor among the embodiment one.Other conditions are with embodiment one.
Comparative example two
Reaction mixture (mother liquor and nickel hydroxide) is discharged reactor from same overflow port, does not establish hydromechanics granular size tripping device.Other conditions are with embodiment two.
The size-grade distribution of above-mentioned four groups of laboratory samples and the measurement result of other performances are listed in the table 1.
Table 1
Size-grade distribution embodiment one embodiment two comparative examples one comparative example two
(differential rice) % % % %
More than 50 000 3.8
40-50 0 0.1 0 2.5
30-40 1.9 2.1 1.7 4.3
20-30 3.2 3.4 4.1 8.8
15-20 12.6 11.4 13.1 14.7
10-15 32.3 26.5 34.9 33.8
8-10 36.5 35.3 32.1 12.4
6-8 10.3 15.7 11.6 10.7
4-6 3.6 5.7 3.1 6.6
Below 4 0.6 0.8 0.4 2.4
Median size (micron) 11.52 11.04 11.73 12.46
Tap density (gram per centimeter
3) 2.17 2.15 2.18 2.14
Loading capacity
(MAH/gram)＞260＞260＞260＞260
Embodiment one, two and comparative example one contrast, mother liquor reclaims use and does not reclaim use, and product performance are basic identical, and the multiplexing product performance that do not influence of mother liquor are described.Embodiment one, two and comparative example two contrasts illustrate that the present invention adopts hydromechanics granular size lock out operation, and product particle degree distribution range obviously narrows down.
Claims (2)
1. preparation method who prepares high density and activity spherical nickle hydroxide, to contain ammonia, the nickel sulfate solution of ammonium and rose vitriol, the aqueous sodium hydroxide solution that contains ammonia and zinc sulfate is an original liquid, be transported to this feed liquid in the reactor continuously, the PH of conditioned reaction liquid and temperature of reaction in reactor, constantly stir, make it that chemical reaction take place, nickel hydroxide particle that generates and mother liquor are discharged reactor and are carried out solid-liquid separation, its nickel hydroxide particle washs, thereby the dry product that obtains, the nickel hydroxide particle and the mother liquor that it is characterized in that above-mentioned said generation are to discharge continuously from two outlets of reactor, wherein nickel hydroxide particle enters digestion tank through hydromechanics granular size separator, and mother liquor enters digestion tank through the mother liquor settler, above-mentioned nickel hydroxide and mother liquor mix and ageing in digestion tank once more, its mixture carries out solid-liquid separation, nickel hydroxide particle washing after the separation, obtain product after the drying, and mother liquor is after crystallization treatment, its mother liquor of 90 percent returns as feed liquid multiplexing, and 10 mother liquor discharges after treatment.
2. by aforesaid right requirement 1 described preparation method, it is characterized in that the PH of reaction solution in the described reactor is controlled at 10.00～13.00, temperature is controlled at 30～70 ℃
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97100691A CN1053646C (en) | 1997-03-14 | 1997-03-14 | Preparation of high density and activity spherical nickle hydroxide |
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| Application Number | Priority Date | Filing Date | Title |
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| CN97100691A CN1053646C (en) | 1997-03-14 | 1997-03-14 | Preparation of high density and activity spherical nickle hydroxide |
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| CN1193605A CN1193605A (en) | 1998-09-23 |
| CN1053646C true CN1053646C (en) | 2000-06-21 |
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| CN97100691A Expired - Fee Related CN1053646C (en) | 1997-03-14 | 1997-03-14 | Preparation of high density and activity spherical nickle hydroxide |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1091075C (en) * | 1998-10-21 | 2002-09-18 | 中国科学院金属腐蚀与防护研究所 | Method for producing spheroidal nickelous hydroxide series powder |
| CN1101341C (en) * | 1998-10-29 | 2003-02-12 | 中国科学院金属腐蚀与防护研究所 | Equipment for preparing spherical powder of nickelous hydroxide series |
| CN100385712C (en) * | 2004-10-26 | 2008-04-30 | 深圳市比克电池有限公司 | Multicomponent metal oxide, lithium ion battery anode material and its preparing method |
| CN109205685B (en) * | 2017-07-03 | 2022-04-26 | 东莞东阳光科研发有限公司 | Continuous preparation method of high-nickel ternary precursor for lithium ion battery |
| CN107623124B (en) * | 2017-09-30 | 2020-04-07 | 金驰能源材料有限公司 | Preparation method of spherical nickel-cobalt-manganese precursor material |
| CN109574094B (en) * | 2019-01-24 | 2022-03-08 | 广东迈纳科技有限公司 | Preparation method of nickel-cobalt-aluminum hydroxide with stable particle size and particle size distribution |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4244938A (en) * | 1978-11-20 | 1981-01-13 | Mooney Chemicals, Inc. | Preparation of transition metal hydrates by direct metal reaction |
| JPS6191855A (en) * | 1984-10-09 | 1986-05-09 | Matsushita Electric Ind Co Ltd | Sealed battery |
| JPS6340427A (en) * | 1986-08-06 | 1988-02-20 | Mitsubishi Electric Corp | Modulation system |
| CN1075697A (en) * | 1993-04-09 | 1993-09-01 | 河南师范大学 | Preparation method of corpuscle ball type nickel hydroxide |
| CN1107442A (en) * | 1994-02-26 | 1995-08-30 | 王维波 | Process for preparing nickel hydroxide |
| CN1112520A (en) * | 1994-05-24 | 1995-11-29 | 中国科学技术大学 | Preparation process for ultramicro particle nickel oxide |
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1997
- 1997-03-14 CN CN97100691A patent/CN1053646C/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4244938A (en) * | 1978-11-20 | 1981-01-13 | Mooney Chemicals, Inc. | Preparation of transition metal hydrates by direct metal reaction |
| JPS6191855A (en) * | 1984-10-09 | 1986-05-09 | Matsushita Electric Ind Co Ltd | Sealed battery |
| JPS6340427A (en) * | 1986-08-06 | 1988-02-20 | Mitsubishi Electric Corp | Modulation system |
| CN1075697A (en) * | 1993-04-09 | 1993-09-01 | 河南师范大学 | Preparation method of corpuscle ball type nickel hydroxide |
| CN1107442A (en) * | 1994-02-26 | 1995-08-30 | 王维波 | Process for preparing nickel hydroxide |
| CN1112520A (en) * | 1994-05-24 | 1995-11-29 | 中国科学技术大学 | Preparation process for ultramicro particle nickel oxide |
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