CN100448074C - Making method of nickel hydroxide with coated gamma hydroxy cobalt oxide - Google Patents
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Abstract
The invention relates to a preparation method for nickel hydroxide, which is used as a Ni-H storage battery positive material, coated with gamma hydroxy cobalt oxide. The preparation includes that the sphere surface of nickel hydroxide is coated with a layer of cobalt hydroxide firstly; then, under the conditions of high-density sodium hydroxide and oxygen, the cobalt hydroxide layer coated on the surface is oxidized the gamma hydroxy cobalt oxide, or the treatment of embedding doped metals is exerted on the gamma hydroxy cobalt oxide layer. By controlling the coating layer to be the cobalt hydroxide presenting a shape of flake, the method makes the resulted conducting network coated with the coating layer of gamma hydroxy cobalt oxide more uniform, more integrated and better conductive, and thus attributes the nickel hydroxide positive active material coated with gamma hydroxy cobalt oxide with some characteristics of high recovering rate of over-discharging capacity, good performance of big current discharging, low self-discharging, long lifetime of cycling use and so on.
Description
Technical field:
The present invention relates to be applied to the preparation method of the positive electrode active materials in the nickel-hydrogen accumulator.
Background technology:
Nickel-hydrogen accumulator is applied in various fields such as communication, information already on a large scale as a kind of good green secondary cell.As use therein positive electrode active materials, the properties of product of nickel hydroxide directly affect the performance of nickel-hydrogen secondary cell.Along with the development of modern electric elements and be subjected to the restriction of world petroleum resource and environmental pollution factors influences and the electric automobile field of researching and developing out, all higher performance requirement has been proposed nickel-hydrogen secondary cell.Ni-MH battery market to high conductivity, height ratio capacity, big multiplying power discharging property is good, self discharge is low, cross that to put back restorability demand good, that recycle long high-quality nickel hydroxide anode material of life-span increasing.
What the nickel hydroxide positive plate active material used at first is conventional ball-shape nickel hydroxide, also need add CoO or Co (OH) in being applied to the electrode preparation of nickel-hydrogen accumulator
2Additive, this additive is oxidized to β-CoOOH by oxidation with conductivity at the battery charge initial stage, play the function of conductive network, thereby make discharging and recharging of active material nickel hydroxide react smooth, still CoO or the Co (OH) that adds with this form
2Additive can not be completely oxidized to β-CoOOH in charge and discharge process, make the utilance of nickel hydroxide active material not high; Afterwards, people had studied on the surface of ball-shape nickel hydroxide and had coated one deck β-Co (OH)
2Research, developed the nickel hydroxide positive plate active material that coats cobalt, this β-Co (OH) that evenly is coated on the surface
2β-CoOOH that oxidation generates in charge and discharge process can improve the uniformity of conductive network, thereby can improve the utilance of nickel hydroxide active material.But, the nickel-hydrogen secondary cell that uses this positive active material is in state such as heavy-current discharge, deep discharge, short circuit following time, the irrecoverable problem that positive electrode capacity is often arranged, main cause wherein mainly is when carrying out the deep discharge of nickel hydroxide, the conductive network material β-CoOOH of nickel hydroxide surface also can carry out the reduction reaction of part, divalent cobalt after its reduction can form cobalt in the electrolyte of battery complex ion causes the problems of dissolution of cobalt, thereby causes the imperfect of β-CoOOH conductive network.
By further discovering, γ-the CoOOH of another kind of crystal formation has the conductivity higher than β-CoOOH, and this γ-CoOOH can form the state that is higher than 3.0 valencys, compare its reduction potential in alkaline electrolyte with β-CoOOH lower, be not easy to be reduced characteristics such as 2.0 valency states, thereby can avoid the dissolving of cobalt in the conductive network in discharge process preferably, cause the decline problem of positive electrode capacity.On this theoretical foundation, people have worked out the preparation method of the nickel hydroxide of coated gamma-CoOOH.U.S. Pat P5629111 reported under the coexistence of alkaline aqueous solution and air, to the nickel hydroxide particle that is coated with cobalt hydroxide heat, oxidation processes, obtained the cobalt/cobalt oxide of surperficial coating 2.9 valencys.Patent CN1186352A proposed under alkali lye and air conditions, by microwave heating equipment the nickel hydroxide particle with cobalt hydroxide coating layer is carried out the method for oxidation processes, and obtaining the coating layer conductive network is to be the high order cobalt/cobalt oxide of main composition with gamma hydroxy cobalt oxide.
The inventor thinks: the nickel hydroxide material of the coated gamma hydroxy cobalt oxide that obtains in the above-mentioned patent report all also has the space of improving aspect the electrical performance indexes such as life-span, heavy-current discharge performance recycling of revealing of conductivity, integrality and material list such as conductive network.
Because in above-mentioned patent report, just unilaterally detailed oxidation reaction process to the cobalt hydroxide coating layer has carried out trickle Control Study, and not to its another relevant critical process---the technology of coating reaction is controlled to carry out simultaneously and is studied in great detail.
The inventor thinks by research: the surface of nickel hydroxide coats the oxidation reaction of cobaltous hydroxide layer, not only is subjected to the control influence of oxidizing process; Simultaneously, the technology control in the time of formed by cobalt hydroxide influences, particularly can be with closely related with the surface crystallization state (crystallite pattern) of coating layer.That is to say: the uniformity of surface gamma-CoOOH coating layer that the crystallite pattern of cobalt hydroxide generates final oxidation, integrality and have a direct impact, these improvement with the bonding tightness of matrix will directly improve nickel hydroxide heavy-current discharge performance, overdischarge restorability and recycle the life-span etc.
This be because, cover in the oxidizing process of cobaltous hydroxide layer at his-and-hers watches bread, exist the complex ion (HCoO that dissolves and form cobalt again of a part divalent cobalt
2 -), crystal aggregation becomes the process of γ-CoOOH again again.As following reaction equation:
Co (OH)
2+ OH
-→ HCoO
2 -+ H
2O (solubilizing reaction)
HCoO
2 -+ 1/2H
2O+1/4O
2→ CoOOH+OH
-(oxidation evolution reaction)
What can estimate is, coat the difference of the crystallite form of cobaltous hydroxide layer, with directly can to its dissolving and again accumulation process, the oxidation efficiency after the crystallization exert an influence, because if γ-CoOOH that above oxidation is assembled does not occur in the surface of nickel hydroxide particle, and be free in separately beyond the ball-shape nickel hydroxide particle, then can directly influence the cobalt covering amount of nickel hydroxide particle surface, and then influence the electrical conductance of uniformity, integrality and the particle of conductive network; Simultaneously, the surface coats the crystallite pattern that cobaltous hydroxide layer presents control, can make that oxidizing process is more easy to control, oxidation rate is faster, oxidation is more thorough, make the cobalt hydroxide after the oxidation present complete γ-CoOOH crystal formation, thereby help coating the raising of electrical property of the nickel hydroxide product of γ-CoOOH.
At present, influence research and the relevant preparation method thereof to this property relationship also do not see relevant report.
Summary of the invention:
The preparation method who the purpose of this invention is to provide the nickel hydroxide of more even, the more complete coated gamma hydroxy cobalt oxide of a kind of conductive network that makes nickel hydroxide surface.
The present invention mainly studies surperficial coating beta-Co (OH) in the preparation method
2The oxidation technology of technology and coating layer thereof is by control β-Co (OH)
2The surface topography of coating layer, the uniformity of the conductive network of the coated gamma hydroxy cobalt oxide that raising obtains after oxidation, integrality and electrical conductance, make the nickel hydroxide of the coated gamma hydroxy cobalt oxide of preparation have that high conductivity, conductive network are even and complete, active material utilizes characteristics such as height, show good comprehensive electrochemical properties.
Method one of the present invention is: at first coating one deck crystallite pattern on the surface of ball-shape nickel hydroxide equably is the cobalt hydroxide of sheet, nickel hydroxide to the coating cobalt hydroxide that obtains carries out oxidation processes again, and surface coating layer is oxidized to gamma hydroxy cobalt oxide.This method may further comprise the steps:
(1) preparation 0.5～2M cobalt sulfate solution A; Weight ratio is respectively 10%～30% sodium hydroxide solution B; 5%～30% ammonia spirit C; 20%～60% sodium hydroxide solution D;
(2) adding the ball-shape nickel hydroxide and the pure water of 100～300 grams per liters in reactor, with solution B conditioned reaction liquid pH to 8.0～12.0, is 3～10 grams per liters with ammonia concentration in the solution C conditioned reaction liquid, and controlling temperature is 30～75 ℃;
(3) simultaneously and join continuously and carry out coating reaction in the reactor, reaction condition: the control mixing speed with solution A, solution B, solution C: 180～300 rev/mins, 30～75 ℃ of temperature, pH value 8.0～14.0; Ammonia concentration 3～10 grams per liters, 2～7 hours reaction time;
(4) product that step (3) reaction is obtained carries out Separation of Solid and Liquid, washs to pH7～10 with pure water, dries under 40～70 ℃ of temperature, obtains coating the nickel hydroxide of cobalt hydroxide;
(5) will coat in the nickel hydroxide adding oxidation reactor of cobalt hydroxide, add the nickel hydroxide weight 2～10% that coats cobalt hydroxide, temperature is 80～120 ℃ a solution D, aerating oxygen carries out oxidation, oxidation reaction condition: under the stirring condition, 60～150 ℃ of temperature, 0.1～1 liter/kg of oxygen flow nickel hydroxide minute, 0.1～2.5 hour reaction time;
(6) material after the oxidation is washed to pH7～10 with pure water, under 100～150 ℃ of temperature, dry, promptly obtain the nickel hydroxide product of coated gamma hydroxy cobalt oxide.
The inventive method two: its step is at first carried out with method one described (1)～(5) step, material is put into the reprocessing reactor after the oxidation that step (5) is obtained again, adding concentration is the lithium hydroxide solution of 5～20 grams per liters, make that the solid concentration of material in solution is 100～300 grams per liters after the oxidation, 30～100 ℃ of control reaction temperature, reaction time are 0.25～2 hour, after reaction finishes, material is through Separation of Solid and Liquid, wash to pH7～10 with pure water, under 100～150 ℃ of temperature, dry, promptly obtain the nickel hydroxide of coated gamma hydroxy cobalt oxide.
The surface coating layer crystallite pattern that method one and method two coat the nickel hydroxide of cobalt hydroxide is a laminated structure, and the amount that coats cobalt hydroxide is 3.0～12.0% of a nickel hydroxide matrix weight.
The amount of the hydroxy cobalt oxide that coats in method one and the method two is 3.0～12.0% of a nickel hydroxide matrix weight; The nickel hydroxide of the coated gamma hydroxy cobalt oxide that obtains, the average grain diameter of particle are 6～20 μ m, and BET is 5～25m
2/ g, the powder impedance of the particle of measuring with the mechanical ramming method is 1～5 Ω cm.
Method two contains 0.1～0.4%Li in the nickel hydroxide particle of coated gamma hydroxy cobalt oxide.
Description of drawings:
The crystallite shape appearance figure of the coating layer (sheet) of the nickel hydroxide of the coating cobalt hydroxide that Fig. 1 obtains for the present invention.
The XRD figure of the gamma hydroxy cobalt oxide that Fig. 2 the present invention obtains.
Embodiment:
Embodiment 1:
Main material: the ball-shape nickel hydroxide matrix is commercially available (Jintian Energy Material Co., Ltd.'s production).
1. solution preparation: 1M cobalt sulfate solution, 20% sodium hydroxide solution, 20% ammonia spirit.
2. coat cobalt hydroxide:
Main material is put into reactor, adds pure water, sodium hydroxide solution and ammonia spirit, is made into nickel hydroxide solid concentration 200 grams per liters, ammonia concentration and is 5 grams per liters, pH and be 9.5, temperature is 60 ℃ reactant liquor; Again with the 1M cobalt sulfate solution, 20% sodium hydroxide solution, also continuous being added in the reactor simultaneously of 20% ammonia spirit that prepare, under 200 rev/mins stirring condition, keep that 60 ℃ of temperature of reaction system, pH are 9.5, ammonia concentration 5 grams per liters in the system, the reaction time continues 3 hours.The cobalt liquor amount that adds in the reaction accounts for 5% (WT) of nickel hydroxide matrix by the cobalt hydroxide amount that coats.With the material filtering after coating, wash to pH be 7.0, promptly obtain the nickel hydroxide that the surface coats cobalt hydroxide 60 ℃ of following oven dry again.
3. hydrogen oxide cobalt oxide: the nickel hydroxide that coats cobalt hydroxide by above-mentioned surface is put into oxidation reactor, under stirring condition, be warming up to 80 ℃, add simultaneously the temperature for preparing lentamente and be 80 ℃, 50% sodium hydroxide solution, the sodium hydroxide solution amount adds in the ratio of 4% (WT) of nickel hydroxide weight, simultaneously aerating oxygen (oxygen flow is: 0.6 liter/kg nickel hydroxide minute), temperature of reaction system are kept 80 ℃, and oxidization time is 10 minutes.Again the material after the oxidation is washed to pH with pure water after the oxidation reaction and be 8.0, promptly obtain the nickel hydroxide active material A of coated gamma hydroxy cobalt oxide again 110 ℃ of following oven dry.
The powder impedance of the nickel hydroxide active material A that embodiment 1 obtains is 2 Ω cm, and the cobalt average valence that goes out coating cobalt in surface by iodometric determination is 3.16, and the electrical property testing result sees Table 1.
Embodiment 2:
The nickel hydroxide active material A of the coated gamma hydroxy cobalt oxide that embodiment 1 is obtained mixes to modify and handles, and method is:
The nickel hydroxide active material A of coated gamma hydroxy cobalt oxide is joined in the lithium hydroxide solution of 10 grams per liters, making the solid concentration of nickel hydroxide active material A in solution is 200 grams per liters, keep 60 ℃ of temperature of reaction system under stirring condition, the reaction time is 30min; Again the material that will handle filter, with pure water wash to pH be 8.0, promptly obtain the nickel hydroxide active material B of coated gamma hydroxy cobalt oxide again 110 ℃ of following oven dry.
The powder impedance of the nickel hydroxide active material B that embodiment 2 obtains is 1 Ω cm, and the cobalt average valence that coats cobalt by the iodometric determination surface is 3.16, the results are shown in Table 1.
Table 1:
| Sample | 1.0C capacity (mAh/g) | 10C capacity (mAh/g) | 10C/1.0C ×100％ | Cross the capacity restoration rate (%) after putting | 1C cycle life (800 all capacity retention rates/%) |
| Active material A | 245.0 | 197.0 | 80.4 | 99.5 | 80.5 |
| Active material B | 246.8 | 200.4 | 81.2 | 100.3 | 82.9 |
Claims (6)
1. the preparation method of the nickel hydroxide of coated gamma hydroxy cobalt oxide, it is characterized in that: this method may further comprise the steps:
(1) preparation 0.5～2M cobalt sulfate solution A; Weight ratio is respectively 10%～30% sodium hydroxide solution B; 5%～30% ammonia spirit C; 20%～60% sodium hydroxide solution D;
(2) adding the ball-shape nickel hydroxide and the pure water of 100～300 grams per liters in reactor, with solution B conditioned reaction liquid pH to 8.0～12.0, is 3～10 grams per liters with ammonia concentration in the solution C conditioned reaction liquid, and controlling temperature is 30～75 ℃;
(3) solution A, solution B, solution C are also joined coating reaction in the reactor, reaction condition simultaneously continuously: 180～300 rev/mins of mixing speeds, 30～75 ℃ of temperature, pH value 8.0～14.0; Ammonia concentration 3～10 grams per liters, 2～7 hours reaction time;
(4) product that step (3) reaction is obtained carries out Separation of Solid and Liquid, washs to pH7～10 with pure water, dries under 40～70 ℃ of temperature, obtains coating the nickel hydroxide of cobalt hydroxide;
(5) will coat in the nickel hydroxide adding oxidation reactor of cobalt hydroxide, the adding temperature is 80～120 ℃ a solution D, solution D weight is for coating the nickel hydroxide weight 2～10% of cobalt hydroxide, aerating oxygen carries out oxidation, oxidation reaction condition: under the stirring condition, 60～150 ℃ of temperature, 0.1～1 liter/kg of oxygen flow nickel hydroxide minute, 0.1～2.5 hour reaction time;
(6) material after the oxidation is washed to pH7～10 with pure water, under 100～150 ℃ of temperature, dry, promptly obtain the nickel hydroxide product of coated gamma hydroxy cobalt oxide.
2. the preparation method of the nickel hydroxide of coated gamma hydroxy cobalt oxide, it is characterized in that: this method step is at first with claim 1 described (1)～(5), material is put into the reprocessing reactor after the oxidation that step (5) is obtained again, adding concentration is the lithium hydroxide solution of 5～20 grams per liters, make that the solid concentration of material in solution is 100～300 grams per liters after the oxidation, under stirring condition, 30～100 ℃ of control reaction temperature, reaction time is 0.25～2 hour, after reaction finishes, material is through Separation of Solid and Liquid, wash to pH7～10 with pure water, under 100～150 ℃ of temperature, dry, promptly obtain the nickel hydroxide of coated gamma hydroxy cobalt oxide.
3. according to the preparation method of the nickel hydroxide of claim 1 or 2 described coated gamma hydroxy cobalt oxides, it is characterized in that: the surface coating layer crystallite pattern that coats the nickel hydroxide of cobalt hydroxide is a laminated structure.
4. according to the preparation method of the nickel hydroxide of claim 1 or 2 described coated gamma hydroxy cobalt oxides, it is characterized in that: the amount that coats the amount of cobalt hydroxide and coat gamma hydroxy cobalt oxide is respectively 3.0～12.0% of a nickel hydroxide matrix weight.
5. according to the preparation method of the nickel hydroxide of the described coated gamma hydroxy cobalt oxide of claim 2, it is characterized in that: contain 0.1～0.4%Li in the nickel hydroxide particle of coated gamma hydroxy cobalt oxide.
6. according to the preparation method of the nickel hydroxide of claim 1 or 2 described coated gamma hydroxy cobalt oxides, it is characterized in that: the nickel hydroxide of the coated gamma hydroxy cobalt oxide that obtains, the average grain diameter of particle are 6～20 μ m, and BET is 5～25m
2/ g, the powder impedance of the particle of measuring with the mechanical ramming method is 1～5 Ω cm.
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| CN110331416B (en) * | 2019-08-09 | 2020-07-24 | 河南大学 | CoOOH nanosheet modified Fe2O3Preparation method and application of composite photo-anode |
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Effective date of registration: 20160206 Address after: 410000 Hunan province city industrial base Changsha Tongguanshan circular Wangcheng District Huaguo Road No. 955 Patentee after: JINCHI ENERGY MATERIAL CO., LTD. Address before: 411132 new material industrial park, Xiangtan port hi tech Zone, Hunan Patentee before: Jintian Energy Material Co., Ltd. |