CN1516301A - Preparation method of spherical nickel hydroxide containing nano-grade spherical nickel - Google Patents
Preparation method of spherical nickel hydroxide containing nano-grade spherical nickel Download PDFInfo
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- CN1516301A CN1516301A CNA031341691A CN03134169A CN1516301A CN 1516301 A CN1516301 A CN 1516301A CN A031341691 A CNA031341691 A CN A031341691A CN 03134169 A CN03134169 A CN 03134169A CN 1516301 A CN1516301 A CN 1516301A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
The invention provides a nano ball Ni-containing ball-shaped nickel hydrate making method, its character; firstly preparing mixed sulphate solution, thick ammonia and caustic alkali; then continuously pouring them into a 40-60 deg. C special reactor E and another 60-100 deg. C one F at the same time, making them continuously react and overflow in the ageing kettle, filtering, washing by water, and drying to obtain its high-density power. Its loose and tap densities can reach above 1.60g/Ml and above 2.35g/ML, respectively. Its discharge capacity is high; it is beneficial to making high-capacity cell.
Description
Technical field
The present invention relates to chemical engineering and field of new, particularly a kind of preparation method who contains the ball-shape nickel hydroxide of nanoscale ball nickel.
Background technology
Nickel hydroxide [Ni (OH)
2] be various alkaline secondary cells (Cd-Ni, MH-Ni, H
2-Ni etc.) positive electrode active materials.Capacity and life-span to battery are played crucial effects.Along with science and technology development, modernized electrical equipment is also had higher requirement to battery, and high power capacity, long-life, small size, the demand that can carry out the secondary cell of high current charge-discharge are sharply increased.
Yet, the ball-shape nickel hydroxide of manufacturing at present is micron order ball nickel, have bigger apparent density and tap density, but when making the process of anode, even ball nickel has good granularity gradient, also there is bigger gap between ball and the ball, the existence in this gap directly has influence on the proton motion in the battery charge and discharge process, thereby cause the discharge performance of battery to descend, especially heavy-current discharge performance.
In the electrochemical process of nickel electrode, protolysis speed is directly controlled the charge-discharge performance of battery.How improving protolysis speed is the key that improves battery performance.The migration path that shortens proton can improve the high rate during charging-discharging of material.Nano-sized nickel hydroxide all is the feasible method that improves electrode performance from theory and practice.The crystalline size of nano-sized nickel hydroxide is little, and proton is short at intracrystalline migration path in the charge and discharge process.In addition, nano-sized nickel hydroxide also has quantum size effect, skin effect and macroscopical tunnel effect, and crystal structure is stable, has bigger diffusion of protons coefficient.Yet it has very big surface energy again, and agglomeration very easily takes place, and brings great difficulty for filtration, washing, drying, causes the tap density of product low, and the loading when making battery is little, thereby reduces the capacity of battery.
Summary of the invention
The purpose of this invention is to provide a kind of preparation method who contains the ball-shape nickel hydroxide of nanoscale ball nickel, the advantage of comprehensive nanoscale and micron order ball nickel, abandon both defectives, to guarantee that product has good filtration, washing, drying property and high apparent density, tap density, has high charge-discharge performance simultaneously.
Technical scheme feature provided by the invention is:
Prepare following three kinds of materials earlier:
Material A: get nickelous sulfate, cobaltous sulfate, zinc sulfate and be mixed with mixed sulfate solution, its concentration ratio (mol ratio) is 0.5-2.0mol/L:0-0.1mol/L:0-0.2mol/L.
Optimum concentration range is: concentration of nickel sulfate is that 1.5～2.0mol/l, cobalt sulfate concentration are that 0.01-0.05mol/L and zinc sulfate concentration are the mixed sulfate of 0.05-0.15mol/L;
Material B density is the concentrated ammonia liquor of 0.88-0.92g/ml;
Material C concentration is the caustic solution of 6-10mol/L;
Then with above-mentioned three kinds of material A, B, C simultaneously continuously implantation temperature be 40-60 ℃ special reactor E and temperature be 60-100 ℃ another special reactor F in, react continuously simultaneously in two reactors and continuous overflow in aging tank, after filtration, obtain containing the high-density ball-shape nickel hydroxide powder of nanoscale ball nickel after the washing, oven dry.
The volumetric ratio of special reactor E and special reactor F is 10-100 in the course of reaction: 1, and the mixing speed ratio is 1: 1-10, the material A additional proportion of special reactor E and special reactor F is 10-100: 1.The additional proportion of material B also is 10-100: 1.By adjusting the addition of material C, with pH value in the control reactor between 10-12.
A special reflecting device F is a reactor of producing the nano-level sphere nickel hydroxide, and its product apparent density is 0.5-1.0g/ml; Another special reactor E is a reactor of producing high-density ball-shape nickel hydroxide, and its product apparent density is 1.7-1.85g/ml.
Advantage of the present invention is:
1, product apparent density and tap density height can reach 1.60g/mL respectively and more than the 2.35g/mL;
2, product discharge capacity height, its 0.2C seal discharge capacity can on average reach 280-285mAh/g near theoretical limit;
3, after product was made battery, loading was big, helped making high-capacity battery.
Embodiment
Embodiment 1:
A special reactor E volume 2m
3, another special reactor F volume 0.2m
3
Material A: the molar concentration of mixed sulfate solution nickelous sulfate is that the concentration of 1.5mol/L, cobaltous sulfate is that 0.05mol/L, sulfuric acid zinc concentration are 0.05mol/L, and technology is mixed with mixed sulfate solution routinely.
Material B density is 0.90g/ml, and material C molar concentration is 8.0mom/l.
In the course of reaction among the special reactor E addition of material A be 120L/h, the reinforced mol ratio of material B and material A is M
NH3H2O: M
Ni2+=1.8: 1, mixing speed is 280 rev/mins, and temperature is 60 ℃, and the addition by control material C reaches in the control reactor pH value 11.0 ± 0.1; The addition of material A is 12L/h among the special reactor F, and the reinforced mol ratio of material B and material A is M
NH3H2O: M
Ni2+=1.8: 1, mixing speed is 780 rev/mins, and temperature is 80 ℃, and the addition by control material C reaches in the control reactor pH value 11.5 ± 0.1.
The product apparent density of reaction post-reactor E is 1.84g/ml, and the product apparent density of reactor F is 0.78g/ml, and the product apparent density is 1.74g/ml after aging tank mixes, and tap density is 2.42g/ml.Making behind the AA battery 0.2C of product, on average to seal discharge capacity be 283.7mAh/g, and battery total capacity is 2058mAh.
Embodiment 2:
Special reactor E volume 2m
3, special reactor F volume 0.02m
3
Material A: the concentration of mixed sulfate solution nickelous sulfate is that the concentration of 2.0mol/L, cobaltous sulfate is that 0.01mol/L, sulfuric acid zinc concentration are 0.15mol/L, and technology is mixed with mixed sulfate solution routinely.
Material B density is 0.91g/ml, and material C molar concentration is 6.0mom/l.
In the course of reaction among the special reactor E addition of material A be 120L/h, the reinforced mol ratio of ammonia nickel is M
NH3H2O: M
Ni2+=1.8: 1, mixing speed is 280 rev/mins, and temperature is 40 ℃, and the addition by control material C reaches in the control reactor pH value 11.4 ± 0.1; The addition of material A is 1.2L/h among the special reactor F, and the reinforced mol ratio of ammonia nickel is M
NH3H2O: M
Ni2+=1.8: 1, mixing speed is 780 rev/mins, and temperature is 90 ℃, and the addition by control material C reaches in the control reactor pH value 11.6 ± 0.1.The product apparent density of reaction post-reactor E is 1.80g/ml, and the product apparent density of reactor E is 0.53g/ml, and the product apparent density is 1.79g/ml after aging tank mixes, and tap density is 2.45g/ml.Making behind the AA battery 0.2C of product, on average to seal discharge capacity be 284.6mAh/g, and battery total capacity is 2079mAh.
Embodiment 3:
A special reactor E volume 2m
3, another special reactor F volume 0.2m
3
Material A: the concentration of mixed sulfate solution nickelous sulfate is that the concentration of 1.5mol/L, cobaltous sulfate is that 0.05mol/L, sulfuric acid zinc concentration are 0.05mol/L, and technology is mixed with mixed sulfate solution routinely.
Material B density is 0.90g/ml, and material C molar concentration is 8.0mol/l.
In the course of reaction among the special reactor E addition of material A be 120L/h, the reinforced mol ratio of material B and material A is M
NH3H2O: M
Ni2-=1.8: 1, mixing speed is 280 rev/mins, and temperature is 60 ℃, and the addition by control material C reaches in the control reactor pH value 11.0 ± 0.1; The addition of material A is 6L/h among the special reactor F, and the reinforced mol ratio of material B and material A is M
NH3H2O: M
Ni2+=1.8: 1, mixing speed is 780 rev/mins, and temperature is 100 ℃, and the addition by control material C reaches in the control reactor pH value 11.5 ± 0.1.
The product apparent density of reaction post-reactor E is 1.84g/ml, and the product apparent density of reactor F is 0.58g/ml, and the product apparent density is 1.74g/ml after aging tank mixes, and tap density is 2.42g/ml.Making behind the AA battery 0.2C of product, on average to seal discharge capacity be 283.7mAh/g, and battery total capacity is 2088mAh.
Embodiment 4:
Special reactor E volume 2m
3, special reactor F volume 0.02m
3
Material A: the concentration of mixed sulfate solution nickelous sulfate is that the concentration of 2.0mol/L, cobaltous sulfate is that 0.01mol/L, sulfuric acid zinc concentration are 0.15mol/L, and technology is mixed with mixed sulfate solution routinely.
Material B density is 0.91g/ml, and material C molar concentration is 6.0mom/l.
In the course of reaction among the special reactor E addition of material A be 120L/h, the reinforced mol ratio of ammonia nickel is M
NH3H2O: M
Ni2+=1.8: 1, mixing speed is 280 rev/mins, and temperature is 40 ℃, and the addition by control material C reaches in the control reactor pH value 11.4 ± 0.1; The addition of material A is 1.2L/h among the special reactor F, and the reinforced mol ratio of ammonia nickel is M
NH3H2O: M
Ni2+=2.0: 1, mixing speed is 780 rev/mins, and temperature is 90 ℃, and the addition by control material C reaches in the control reactor pH value 11.6 ± 0.1.The product apparent density of reaction post-reactor E is 1.80g/ml, and the product apparent density of reactor E is 0.53g/ml, and the product apparent density is 1.79g/ml after aging tank mixes, and tap density is 2.45g/ml.Making behind the AA battery 0.2C of product, on average to seal discharge capacity be 284.6mAh/g, and battery total capacity is 2109mAh.
Claims (4)
1, a kind of preparation method who contains the ball-shape nickel hydroxide of nanoscale ball nickel is characterized in that:
Prepare following three kinds of materials earlier:
Material A: get nickelous sulfate, cobaltous sulfate, zinc sulfate and be mixed with mixed sulfate solution, its molar concentration ratio is 0.5-2.0mol/L:0-0.1mol/L:0-0.2mol/L;
Material B density is the concentrated ammonia liquor of 0.88-0.92g/ml;
Material C concentration is the caustic solution of 6-10mol/L;
Then with above-mentioned three kinds of material A, B, C simultaneously continuously implantation temperature be 40-60 ℃ special reactor E and temperature be 60-100 ℃ another special reactor F in, react continuously simultaneously in two reactors and continuous overflow in aging tank, after filtration, obtain containing the high-density ball-shape nickel hydroxide powder of nanoscale ball nickel after the washing, oven dry.
2, method according to claim 1, its feature: the material A optimum molar concentration range of reactant is: nickelous sulfate is that 1.5～2.0mol/l, cobaltous sulfate are that 0.01-0.05mol/L, zinc sulfate are 0.05-0.15mol/L.
3, method according to claim 1, it is characterized in that: the volumetric ratio of a special reactor E and another special reactor F is 10-100 in the course of reaction: 1, the mixing speed ratio is 1: 1-10, the material additional proportion of two special reactors is 10-100: 1.
4, method according to claim 1 is characterized in that: a special reactor F is a reactor of producing the nano-level sphere nickel hydroxide, and its product apparent density is 0.5-1.0g/ml; Another special E reactor is a reactor of producing high-density ball-shape nickel hydroxide, and its product apparent density is 1.7-1.85g/ml.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA031341691A CN1516301A (en) | 2003-08-26 | 2003-08-26 | Preparation method of spherical nickel hydroxide containing nano-grade spherical nickel |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA031341691A CN1516301A (en) | 2003-08-26 | 2003-08-26 | Preparation method of spherical nickel hydroxide containing nano-grade spherical nickel |
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|---|---|
| CN1516301A true CN1516301A (en) | 2004-07-28 |
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| CNA031341691A Pending CN1516301A (en) | 2003-08-26 | 2003-08-26 | Preparation method of spherical nickel hydroxide containing nano-grade spherical nickel |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2463254C1 (en) * | 2011-03-09 | 2012-10-10 | Общество с ограниченной ответственностью "НИКОЛЬ" | Method of producing nickel (ii) hydroxide |
| CN111041214A (en) * | 2019-12-23 | 2020-04-21 | 先进储能材料国家工程研究中心有限责任公司 | Method for recycling and preparing α spherical nickel by utilizing waste zinc-containing nickel-hydrogen battery |
-
2003
- 2003-08-26 CN CNA031341691A patent/CN1516301A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2463254C1 (en) * | 2011-03-09 | 2012-10-10 | Общество с ограниченной ответственностью "НИКОЛЬ" | Method of producing nickel (ii) hydroxide |
| CN111041214A (en) * | 2019-12-23 | 2020-04-21 | 先进储能材料国家工程研究中心有限责任公司 | Method for recycling and preparing α spherical nickel by utilizing waste zinc-containing nickel-hydrogen battery |
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