CN104752689A - Composite Co(OH)2+ alkali metal ion spherical nickel hydroxide coated anode material and preparation method thereof - Google Patents
Composite Co(OH)2+ alkali metal ion spherical nickel hydroxide coated anode material and preparation method thereof Download PDFInfo
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- CN104752689A CN104752689A CN201310752098.1A CN201310752098A CN104752689A CN 104752689 A CN104752689 A CN 104752689A CN 201310752098 A CN201310752098 A CN 201310752098A CN 104752689 A CN104752689 A CN 104752689A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/24—Electrodes for alkaline accumulators
- H01M4/32—Nickel oxide or hydroxide electrodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/24—Electrodes for alkaline accumulators
- H01M4/26—Processes of manufacture
- H01M4/28—Precipitating active material on the carrier
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/10—Energy storage using batteries
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Abstract
The invention discloses a composite Co(OH)2+alkali metal ion coated spherical nickel hydroxide anode material and a preparation method of the composite Co(OH)2+alkali metal ion coated spherical nickel hydroxide anode material. The method comprises the following steps: adding a cobalt sulfate solution to a base solution containing spherical nickel hydroxide and alkali metal soluble salt at gradually increasing speed, adding a complexing agent solution and alkali liquor simultaneously, controlling the reaction temperature to be 40-80 DEG C and the stirring speed to be 100-250 r/min, keeping the PH value of a reaction system to be 9-13.5, and controlling the reaction time to be 2-5 hours, so as to form 'gradient coating'. The Co(OH)2 coated spherical nickel hydroxide electrode material prepared by adopting the method disclosed by the invention has a firm and compact coating layer, has excellent large current charging and discharging performance and high-temperature property, and can effectively improve the dynamic property of a nickel-based secondary battery.
Description
Technical field
The present invention relates to a kind of Ni-based secondary battery positive electrode material, be compound coating Co (OH)
2+ alkali metal ion ball-shape nickel hydroxide, belongs to field of functional materials.
Background technology
Ni-based secondary cell especially metal hydride nickel-hydrogen secondary cell (Ni/MH), with its high-energy-density, high-specific-power, long-life, the fail safe excellent combination property such as good, is still the best power source power supply of hybrid vehicle (HEV).At present, the bottleneck of its development is mainly the shortcoming of high rate during charging-discharging, fast charging and discharging performance and high-temperature behavior.Ball-shape nickel hydroxide, as the positive electrode of Ni-based secondary cell, plays vital effect to the quality of battery performance, and the combination property improving nickel hydroxide anode material is still current problem demanding prompt solution.
Research shows Ni (OH)
2the coated Co compound of bulk phase-doped, particle surface, effectively can promote the combination property of nickel hydroxide.Especially the coated Co compound of particle surface, has become the major industrialized means promoting nickel hydroxide electrical property.But still there are some problems in current industrialization coated Co compound method, main manifestations is:
The first, coating technology is too simple.The normal coated mode adopting general chemistry deposition in production, coating layer simple " accumulations " is at particle surface, and in course of reaction, easy and matrix departs from, and affects the performance of electrode material; Although there is the coated cobalt patent (Chinese patent 99107434.3) adopting integration feeding manner, because of some complexity of its technique, apply not yet in the industry;
The second, the amount of coated cobalt is too high.Generally reach more than 5% (wt), increase the cost of nickel hydroxide on the one hand, also cause coating layer " blocked up " on the other hand, so density is poor, in charge and discharge cycles process, also easily cause coming off of coating layer, affect performance;
Three, coating layer composition is single.At present, main coated Co (OH) in production
2or CoOOH, have at most and ooze Li process, coating layer composition is too single, and thus electrode performance room for improvement is little.
Summary of the invention
The present invention is directed to above Problems existing, a kind of compound coating Co (OH) is provided
2+ alkali metal ion ball-shape nickel hydroxide positive electrode and preparation method thereof, adopts the Gradient Coated technology being easy to operate and control, controls below 3% by coated cobalt content, simultaneously in coating layer compound coating alkali metal ion as Na
+, K
+deng, the problems such as coated composition is single, coated defective tightness can be solved well, significantly improve high current charge-discharge and the hot properties of ball-shape nickel hydroxide positive electrode, be conducive to the development bottleneck problem solving Ni-MH power cell.
For achieving the above object, the present invention is by the following technical solutions:
Compound coating Co (OH)
2the preparation method of+alkali metal ion ball-shape nickel hydroxide positive electrode, comprises the steps:
E. preparation raw material liquid
Preparation cobalt sulfate solution, cobalt concentration is at 0.01-1.5mol/L;
Preparation alkali hydroxide soln, wherein alkali metal is Na or K, alkali concn 0.2-8mol/L;
Preparation enveloping agent solution, complexing agent is citric acid, NH
3h
2o or EDTA, complexing agent concentration 0.01-2mol/L;
F. end liquid in reactor is prepared
By spherical Ni (OH) to be covered
2join in reactor, add deionized water, the mass ratio of ball-shape nickel hydroxide and deionized water is between 1:2-12; Alkali-metal soluble-salt is joined in reactor, is mixed to form feed liquid with nickel hydroxide, with alkali metal ion/Ni (OH)
20.1 ~ 2.0wt% determines addition; Add alkali lye, adjust end liquid pH value between 9-13.5; Add part complexing agent again, the concentration of complexing agent in end liquid is in the scope of > 0-0.02mol/L;
G. coated cobalt reaction
After end liquid prepares, open and stir, end liquid stirs more than 2h, temperature 20-30 DEG C in a kettle. continuously; Warming while stirring after end liquid stirs, reaction temperature controls at 40-80 DEG C, and maintenance speed of agitator is 100 ~ 250r/min; Open cobalt sulfate solution measuring pump, complexing agent measuring pump and alkali lye measuring pump, each material liquid is inputted in end liquid respectively and reacts; Wherein, it is 5 ~ 10mL/min that cobalt sulfate solution initially adds speed, reacts after 30 ~ 60 minutes, and adjustment cobalt sulfate solution liquid inlet volume, increases progressively with the flow of 0.05 ~ 0.5mL/min, reach 10 ~ 30mL/min to cobalt sulfate solution flow; Enveloping agent solution continues charging with the speed that adds of 5 ~ 10mL/min, is formed " Gradient Coated "; Intermittently pump into alkali lye, reacting system PH value controls between 9-13.5; Reaction time controls at 2-5 hour; The sample size of cobaltous sulfate is according to Co/Ni (OH)
2be 1 ~ 3wt%;
H. reprocessing
The compound coating ball-shape nickel hydroxide prepared by step C and mother liquor more than ageing 2h, carry out Separation of Solid and Liquid subsequently, and spend deionized water to neutral, 70 ~ 90 DEG C of drying 3 ~ 5h in drying box, sieve to obtain compound coating Co (OH)
2+ alkali metal ion nickel hydroxide product.
Preparation method as above, preferably, described alkali-metal soluble-salt is the sulfate of Na or K, nitrate or hydrochloride.
A kind of compound coating Co (OH)
2+ alkali metal ion ball-shape nickel hydroxide positive electrode, it adopts method as above to prepare.
Ball-shape nickel hydroxide of the present invention can be commercially available ball-shape nickel hydroxide.
" gradient eutectic is coated " of the present invention mechanism is theoretical according to nonhomogen-ous nucleation, in the crystal nucleation and growth course of heterogeneous system, cenotype is formed or grows in existing solid phase, the recruitment of its system surface Gibbs free energy is less than the recruitment of self nucleation (homogeneous nucleation) system surface Gibbs free energy, so heterogeneous nucleation has precedence over the homogeneous nucleation in system.Can realize heterogeneous coated by the pH value of the hierarchy of control, degree of supersaturation and stirring etc.Initial long response time, to ensure coated interface close and firm, after forming tight coating layer, increases inlet amount gradually, continues gradient growth in tight cover surface.Due to coating layer Co (OH)
2for layer structure, a small amount of alkali metal ion can be inserted as Na
+deng, these ions as the carrier of charge transfer, can be conducive to ionic conduction and the diffusion of protons of intra-die, thus the charge-discharge performance of active material under improve high temperature.
Beneficial effect of the present invention is: the first, Gradient Coated preparation method is easy to control, and gained coating layer is tight; The second, compound coating Co (OH)
2+ alkali metal ion ball-shape nickel hydroxide effectively can reduce coated cobalt amount, thus reduces the cost covering cobalt nickel hydroxide; Three, compound coating Co (OH)
2+ alkali metal ion ball-shape nickel hydroxide, has excellent high rate during charging-discharging and hot properties, effectively can promote the dynamic characteristics of Ni-based secondary cell.
Accompanying drawing explanation
Fig. 1 is sample 1C charging and discharging curve at 25 DEG C prepared by embodiment 1-3;
Fig. 2 is sample 2C charging and discharging curve at 25 DEG C prepared by embodiment 1-3;
Fig. 3 is sample 3C charging and discharging curve at 25 DEG C prepared by embodiment 1-3;
Fig. 4 is sample 0.2C charging and discharging curve at 65 DEG C prepared by embodiment 1-3;
Fig. 5 is sample 2C charging and discharging curve at 65 DEG C prepared by embodiment 1-3;
Fig. 6 is sample compound alkali metal containing ion coated Co (OH) prepared by embodiment 3
2ball-shape nickel hydroxide SEM schemes.
Embodiment
Below in conjunction with embodiment, the present invention is further described.
In following examples, ball-shape nickel hydroxide is for containing the commercially available spherical Ni of Zn3wt%, Co1.2wt% (OH)
2.
Embodiment 1:
Preparation cobalt concentration 0.2mol/L cobalt sulfate solution, the NaOH solution of 0.8mol/L, 1.2mol/L ammonia spirit; Get 3kg ball-shape nickel hydroxide powder, add deionized water and be made into liquid at the bottom of 30L, according to K
+the ratio of/nickel hydroxide 0.5wt% adds potassium sulfate, adds NH
3h
2o and alkali lye adjust end liquid pH value to be 11, at 25 DEG C, stir 2h; Liquid at the bottom of Keep agitation is also warming up to 50 DEG C of maintenances, according to Co/Ni (OH)
2(wt.%) quantitative cobalt sulfate solution and ammonia spirit inputted in reactor by the ratio of 2% in 5 hours, wherein cobalt sulfate solution initial charge speed is 6mL/min, 60min rear feeding speed is gone forward one by one with the speed of 0.25mL/min, until reach 21mL/min; Ammonia spirit continues charging with 5mL/min flow, and the charging of NaOH solution adjusts for benchmark 12 at any time to keep the pH value of system, and stirring frequency is 200r/min.Charging terminates rear ageing 2h, after carry out Separation of Solid and Liquid, washing, oven dry, sieve to obtain sample 1.
Embodiment 2:
Preparation cobalt concentration 0.5mol/L cobalt sulfate solution, the NaOH solution of 1.2mol/L, 0.2mol/LEDTA solution; Get 3kg ball-shape nickel hydroxide powder, add deionized water and be made into liquid at the bottom of 20L, then with Na
+/ nickel hydroxide ratio 1.0wt% adds sodium sulphate, adds EDTA solution in end liquid, makes EDTA concentration in end liquid be 0.01mol/L, adds alkali lye and adjusts end liquid pH value to be stir end liquid 2h at 13,30 DEG C; Liquid at the bottom of Keep agitation is also warming up to 50 DEG C of maintenances, according to Co/Ni (OH)
2(wt.%) quantitative cobalt sulfate solution and EDTA solution inputted in reactor by the ratio of 2% in 3.5 hours, wherein cobalt sulfate solution initial charge speed is 5mL/min, 60min rear feeding speed is gone forward one by one with the speed of 0.25mL/min, until reach 15mL/min; EDTA solution continues charging with 10mL/min flow, and the charging of NaOH solution adjusts for benchmark 13.5 at any time to keep the pH value of system, and stirring frequency is 220r/min.Charging terminates rear ageing 2h, after carry out Separation of Solid and Liquid, washing, oven dry, sieve to obtain sample 2.
Embodiment 3:
Preparation cobalt concentration 0.8mol/L cobalt sulfate solution, the NaOH solution of 1.8mol/L, 0.4mol/LEDTA solution; Get 3kg ball-shape nickel hydroxide powder, add deionized water and be made into liquid at the bottom of 24L, with Na
+/ nickel hydroxide ratio 1.4wt% adds sodium sulphate, adds EDTA solution in end liquid, makes EDTA concentration in end liquid be 0.01mol/L, adds alkali lye and adjusts end liquid pH value to be 12,30 DEG C of stirring 3h; Liquid at the bottom of Keep agitation is also warming up to 55 DEG C of maintenances, according to Co/Ni (OH)
2(wt.%) quantitative cobalt sulfate solution and ammonia spirit inputted in reactor by the ratio of 2% in 3 hours, wherein cobalt sulfate solution initial charge speed is 5mL/min, 60min rear feeding speed is gone forward one by one with the speed of 0.1mL/min, until reach 11mL/min; EDTA solution continues charging with 5mL/min flow, and the charging of NaOH solution adjusts for benchmark 13 at any time to keep the pH value of system, and stirring frequency is 200r/min.Charging terminates rear ageing 3h, after carry out Separation of Solid and Liquid, washing, oven dry, sieve to obtain sample 3.
Embodiment 4: analytical test
(1) EDS analyzes
Carry out EDS analysis to the sample that embodiment 2 and 3 obtains, analysis result is as shown in table 1.As can be seen from the table, along with Na
2sO
4increase, the content of grain surface layer Na increases.By present invention process, the compound coating to nickel hydroxide can be realized, for raising nickel hydroxide high temperature and high rate during charging-discharging provide an approach.
Table 1 compound coating Na+ and Co (OH)
2nickel hydroxide EDS data analysis
(2) electric performance test
Gained sample carries out different discharge and recharge system at normal temperature 25 DEG C and high temperature 65 DEG C electrochemical property test with three electrode forms prepared by embodiment 1-3.
Fig. 1-5 prepares the cycle performance test result of gained sample for embodiment 1-3.
From electric performance test result, prepared by embodiment 1-3, cover Co (OH)
2+ Na
+ball-shape nickel hydroxide has good high rate during charging-discharging and high-temperature behavior.
(3) SEM photo
Fig. 6 is that compound prepared by embodiment 3 contains Na
+coated Co (OH)
2ball-shape nickel hydroxide SEM schemes.Schemed from SEM, compound coating Co (OH)
2+ Na
+nickel hydroxide particle outward appearance is still spherical or class is spherical, and coating layer is firmly fine and close, and after compound coating, sample does not occur peeling off obscission, and spheric granules surface is without floccule.Co (OH) in compound coating process is described
2+ Na
+not separate out separately with tablet form, but evenly firmly at spherical Ni (OH)
2particle surface crystalline growth, forms tight coating layer.
Claims (3)
1. compound coating Co (OH)
2the preparation method of+alkali metal ion ball-shape nickel hydroxide positive electrode, it is characterized in that, the method comprises the steps:
A. preparation raw material liquid
Preparation cobalt sulfate solution, cobalt concentration is at 0.01-1.5mol/L;
Preparation alkali hydroxide soln, wherein alkali metal is Na or K, alkali concn 0.2-8mol/L;
Preparation enveloping agent solution, complexing agent is citric acid, NH
3h
2o or EDTA, complexing agent concentration 0.01-2mol/L;
B. end liquid in reactor is prepared
By spherical Ni (OH) to be covered
2join in reactor, add deionized water, the mass ratio of ball-shape nickel hydroxide and deionized water is between 1:2-12; Alkali-metal soluble-salt is joined in reactor, is mixed to form feed liquid with nickel hydroxide, with alkali metal ion/Ni (OH)
20.1 ~ 2.0wt% determines addition; Add alkali lye, adjust end liquid pH value between 9-13.5; Add part complexing agent again, the concentration of complexing agent in end liquid is in the scope of > 0-0.02mol/L;
C. coated cobalt reaction
After end liquid prepares, open and stir, end liquid stirs more than 2h, temperature 20-30 DEG C in a kettle. continuously; Warming while stirring after end liquid stirs, reaction temperature controls at 40-80 DEG C, and maintenance speed of agitator is 100 ~ 250r/min; Open cobalt sulfate solution measuring pump, complexing agent measuring pump and alkali lye measuring pump, each material liquid is inputted in end liquid respectively and reacts; Wherein, it is 5 ~ 10mL/min that cobalt sulfate solution initially adds speed, reacts after 30 ~ 60 minutes, and adjustment cobalt sulfate solution liquid inlet volume, increases progressively with the flow of 0.05 ~ 0.5mL/min, reach 10 ~ 30mL/min to cobalt sulfate solution flow; Enveloping agent solution continues charging with the speed that adds of 5 ~ 10mL/min, is formed " Gradient Coated "; Intermittently pump into alkali lye, reacting system PH value controls between 9-13.5; Reaction time controls at 2-5 hour; The sample size of cobaltous sulfate is according to Co/Ni (OH)
2be 1 ~ 3wt%;
D. reprocessing
The compound coating ball-shape nickel hydroxide prepared by step C and mother liquor more than ageing 2h, carry out Separation of Solid and Liquid subsequently, and spend deionized water to neutral, 70 ~ 90 DEG C of drying 3 ~ 5h in drying box, sieve to obtain compound coating Co (OH)
2+ alkali metal ion nickel hydroxide product.
2. preparation method as claimed in claim 1, is characterized in that, described alkali-metal soluble-salt is the sulfate of Na or K, nitrate or hydrochloride.
3. a compound coating Co (OH)
2+ alkali metal ion ball-shape nickel hydroxide positive electrode, is characterized in that, it adopts method as claimed in claim 1 or 2 to prepare.
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|---|---|---|---|
| CN201310752098.1A CN104752689A (en) | 2013-12-31 | 2013-12-31 | Composite Co(OH)2+ alkali metal ion spherical nickel hydroxide coated anode material and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108370021A (en) * | 2015-10-21 | 2018-08-03 | 尼拉国际股份公司 | Metal hydride battery added with hydrogen, oxygen or hydrogen peroxide |
| CN110828791A (en) * | 2019-10-23 | 2020-02-21 | 金川集团股份有限公司 | Anti-oxidation method in coating reaction process of cobalt-coated positive electrode material |
| CN113023788A (en) * | 2019-12-25 | 2021-06-25 | 洛阳尖端技术研究院 | Nickel-cobalt hollow composite particle, preparation method and application thereof |
-
2013
- 2013-12-31 CN CN201310752098.1A patent/CN104752689A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| 赫文秀等: "覆钴型氢氧化镍的电化学性能研究", 《人工晶体学报》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108370021A (en) * | 2015-10-21 | 2018-08-03 | 尼拉国际股份公司 | Metal hydride battery added with hydrogen, oxygen or hydrogen peroxide |
| CN108370021B (en) * | 2015-10-21 | 2022-04-26 | 尼拉国际股份公司 | Metal hydride battery with added hydrogen, oxygen or hydrogen peroxide |
| CN110828791A (en) * | 2019-10-23 | 2020-02-21 | 金川集团股份有限公司 | Anti-oxidation method in coating reaction process of cobalt-coated positive electrode material |
| CN113023788A (en) * | 2019-12-25 | 2021-06-25 | 洛阳尖端技术研究院 | Nickel-cobalt hollow composite particle, preparation method and application thereof |
| CN113023788B (en) * | 2019-12-25 | 2023-06-30 | 洛阳尖端技术研究院 | Nickel-cobalt hollow composite particle, preparation method and application thereof |
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