CN1299370C - Method for coating and mixing metal M alpha-Co(OH)2 on ball shape nickel hydroxide surface - Google Patents
Method for coating and mixing metal M alpha-Co(OH)2 on ball shape nickel hydroxide surface Download PDFInfo
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- CN1299370C CN1299370C CNB2004100779498A CN200410077949A CN1299370C CN 1299370 C CN1299370 C CN 1299370C CN B2004100779498 A CNB2004100779498 A CN B2004100779498A CN 200410077949 A CN200410077949 A CN 200410077949A CN 1299370 C CN1299370 C CN 1299370C
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- nickel hydroxide
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- shape nickel
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Links
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 title claims abstract description 45
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 40
- 239000002184 metal Substances 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims description 23
- 238000002156 mixing Methods 0.000 title claims description 7
- 238000000576 coating method Methods 0.000 title abstract description 26
- 239000011248 coating agent Substances 0.000 title abstract description 25
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 title abstract 3
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 32
- 239000010941 cobalt Substances 0.000 claims abstract description 32
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 32
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 7
- 229910052706 scandium Inorganic materials 0.000 claims abstract description 6
- 229910052769 Ytterbium Inorganic materials 0.000 claims abstract description 5
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 5
- 229910052738 indium Inorganic materials 0.000 claims abstract description 5
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 4
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 4
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 75
- 239000007864 aqueous solution Substances 0.000 claims description 61
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 54
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 34
- 235000006408 oxalic acid Nutrition 0.000 claims description 25
- 239000008139 complexing agent Substances 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 21
- 239000003513 alkali Substances 0.000 claims description 19
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 18
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000000047 product Substances 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 10
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 150000002739 metals Chemical class 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 238000005303 weighing Methods 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 239000012265 solid product Substances 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 239000012295 chemical reaction liquid Substances 0.000 claims description 3
- 150000001868 cobalt Chemical class 0.000 claims description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 3
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical group [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 239000011593 sulfur Substances 0.000 claims description 3
- 238000005516 engineering process Methods 0.000 abstract description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052760 oxygen Inorganic materials 0.000 abstract description 2
- 239000001301 oxygen Substances 0.000 abstract description 2
- 229910021508 nickel(II) hydroxide Inorganic materials 0.000 abstract 1
- 229910052725 zinc Inorganic materials 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 description 29
- 230000000052 comparative effect Effects 0.000 description 9
- 239000000376 reactant Substances 0.000 description 9
- 229910018916 CoOOH Inorganic materials 0.000 description 5
- 239000011651 chromium Substances 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000006258 conductive agent Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910018502 Ni—H Inorganic materials 0.000 description 3
- 239000011149 active material Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 3
- 229910021617 Indium monochloride Inorganic materials 0.000 description 2
- 239000001996 bearing alloy Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- APHGZSBLRQFRCA-UHFFFAOYSA-M indium(1+);chloride Chemical compound [In]Cl APHGZSBLRQFRCA-UHFFFAOYSA-M 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- SSZYQIIHUYTBFX-UHFFFAOYSA-L [OH-].[OH-].[Co++].[Y] Chemical compound [OH-].[OH-].[Co++].[Y] SSZYQIIHUYTBFX-UHFFFAOYSA-L 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001869 cobalt compounds Chemical class 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000320 mechanical mixture Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- NASFKTWZWDYFER-UHFFFAOYSA-N sodium;hydrate Chemical compound O.[Na] NASFKTWZWDYFER-UHFFFAOYSA-N 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
Landscapes
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention relates to a technology for coating the spherical nickel hydroxide surface with alpha-Co(OH)2. The tap density of the prepared the spherical nickel hydroxide coated with cobalt can reach about 2.2 g/cm<3>. The technology mainly comprises the steps that the spherical nickel hydroxide surface coated with a layer of alpha-Co(OH)2 doped with one or more metal M such as Y, Al, Cr, Mn, Yb, Sc, La, In, Ti and Zn. When a molar ratio of (Co+M) to Ni is from 0.03 to 0.1, the coated-type spherical nickel hydroxide can obviously improve the electrical conductivity of the spherical nickel hydroxide products, improves the Ni(OH)2 electrode property, and thereby, obviously improves the property of batteries, such as specific capacity, output power, charge/discharge cycle life, quick charge capability, over-charge/over-discharge resistant capability, shelf life, overpotential for oxygen evolution, etc.
Description
Technical field
The invention belongs to the new chemical materials preparation field.Be particularly related to a kind of α-Co (OH) in ball shape nickel hydroxide surface coating-doping metal M
2Method
Background technology
Ball-shape nickel hydroxide is the positive electrode active materials of alkaline rechargeable batteries such as Ni-H cell.At present, Ni-H cell has been widely used in fields such as electronics, communication, and has also demonstrated good prospects for application in electric automobiles.But because Ni (OH)
2Be low electric conductivity p N-type semiconductor N, charge/discharge efficient is lower, and electrode performance is relatively poor, and the capacity of battery reduces, for the utilance that improves active material and and collector between conductivity, when generally making electrode at Ni (OH)
2An amount of Ni powder, Co powder, CoO powder or the Co (OH) of middle adding
2Powder is as conductive agent, and these materials will be oxidized to the CoOOH of high conductivity in charging process, is Ni (OH)
2Provide conductivity preferably between the particle and between particle and the collector.Currently used technology is hybrid additive process.
The cobalt of hybrid interpolation or the compound of cobalt, in electrochemical process or alkali treatment process, through dissolving-deposition process again, part is redeposited on the surface or collector of ball nickel again, forms conductive network.Yet, the restriction of process conditions of being mixed and material self character, active material can not be very even with mixing of conductive agent, the sedimentary deposit that this technology forms, its uniformity and deposition are undesirable, can not reduce Ni (OH) effectively
2Reach the contact resistance between particle and the collector between the particle, thereby can not improve electrode performance largely; In addition, the left cavity in cobalt compound dissolving back also fails to be fully utilized, thereby has limited the loadings of active material, has reduced the specific capacity of battery.
Can plate the porous membrane of layer of metal nickel or metallic cobalt in addition at ball shape nickel hydroxide surface by the method for chemical plating.Yet the nickel film that plates can be oxidized to Ni (OH) gradually in charge and discharge process
2And participate in the charge and discharge process of battery, by the formed conductive network of conductive nickel film thereby be damaged, cause battery performance sharply to descend; The cobalt film that plates then can generate Co (OH)
2And finally be converted to CoOOH with high conductivity.Yet from the technological angle of chemical plating, its operating condition is very harsh, and needs to use precious metal as catalyst, cause the cost of product to increase the pollution that reaches environment, thereby this technology is restricted on industrial production.
Can also be with chemical method at ball shape nickel hydroxide surface coating beta-Co (OH)
2, but the β-Co that is coated (OH)
2Activating velocity is slower, must before use it be oxidized to the CoOOH of high conductivity, but oxidation technology is comparatively complicated.The present invention has developed a kind of highdensity coating alpha-Co (OH)
2Spherical Ni (OH)
2, the tap density of product can reach 2.2gcm
-3, and the α-Co that is coated (OH)
2Can be than the CoOOH that is easier to be oxidized to high conductivity.
Summary of the invention
The purpose of this invention is to provide a kind of α-Co (OH) in ball shape nickel hydroxide surface coating-doping metal M
2Method, it is characterized in that this method comprises following each step successively:
One. compound concentration is the cobalt saline solution of 0.5～3 mol;
Two. compound concentration is the aqueous solution of the doped metal salt of wanting of 0.1～0.5 mol;
Three. compound concentration is the aqueous alkali of 3～8 mol;
Four. prepare certain density complexing agent aqueous solution;
Five. take by weighing the ball-shape nickel hydroxide of constant weight and the deionized water of 1～5 times of weight and place reactor, with above-mentioned cobalt saline solution, the saline solution of metallic element M, aqueous alkali and complexing agent aqueous solution are input in the reactor of band stirring respectively continuously with pump, the flow of control cobalt saline solution and complexing agent aqueous solution, promptly control the mol ratio of complexing agent and Co, it is 8～11 that the flow of adjusting aqueous alkali makes the pH value of reactor internal reaction liquid, control reaction temperature is 30～60 ℃, the mol ratio of the Ni of the nickel hydroxide that metal M that coats and Co and quilt are coated is: (Co+M): Ni=0.03～0.1, the mol ratio of metal M and Co is 0.01～0.25, and this reaction is intermittent reaction;
Six. the step 5 products therefrom changed over to carries out Separation of Solid and Liquid in the solid-liquid separator, with the solid product of deionized water washing Separation of Solid and Liquid gained to the pH value of washings less than till 8; Product after the washing is dry under 60～100 ℃ in drier, obtains the α-Co (OH) of coating-doping metal
2The ball-shape nickel hydroxide product.
Described α-Co (OH)
2Doping metals M be among Y, Al, Cr, Mn, Yb, Sc, La, In, Ti or the Zn one or more.
Described cobalt salt is cobaltous sulfate or cobalt nitrate.
The salt of described doping metals is one or more in chloride, nitrate or the sulfur dissolving hydrochlorate, and adding proportion is M: Co=0.01～0.25 (mol ratio); Institute's doping metals is obtain solution separately, and charging separately also can be mixed with the mixed solution charging with cobalt saline solution or aqueous alkali.
Described aqueous alkali is sodium hydrate aqueous solution or potassium hydroxide aqueous solution.
Described complexing agent is one or two or more kinds the mixing in ammonia, ethylenediamine, oxalic acid or the citric acid.Complexing agent is obtain solution separately, and charging separately also can be mixed with the mixed solution charging with cobalt saline solution or aqueous alkali.
The mol ratio of described complexing agent and Co is respectively: NH
3: Co=0.1～0.5, ethylenediamine: Co=0.1～0.3, oxalic acid: Co=0.05～0.2, citric acid: Co=0.01～0.1.
The invention has the beneficial effects as follows α-Co (OH) of the coating-doping metallic element M that is proposed
2The technology of ball-shape nickel hydroxide compare this α-Co (OH) with the technology that traditional usefulness mechanical mixture formula is added metal Co and/or its compound
2Coating can change the CoOOH of high conductivity rapidly into during through peroxidating or at initial charge, thereby obviously improves the electric conductivity of ball-shape nickel hydroxide, has improved Ni (OH)
2Electrode performance, and then obviously improve the performance of battery, as: lower charging voltage and higher discharge potential, height ratio capacity and power output, longer charge/discharge cycle life and quick charge capability, overcharging resisting/discharge capability with shelve for a long time after capacity restoration, improve overpotential for oxygen evolution etc., have great application value.
Embodiment
The invention provides a kind of α-Co (OH) in ball shape nickel hydroxide surface coating-doping metal M
2Method.This method comprises following each step successively:
One. compound concentration is the cobalt saline solution of 0.5～3 mol;
Two. compound concentration is the aqueous solution of the doped metal salt of wanting of 0.1～0.5 mol;
Three. compound concentration is the aqueous alkali of 3～8 mol;
Four. prepare certain density complexing agent aqueous solution;
Five. take by weighing the ball-shape nickel hydroxide of constant weight and the deionized water of 1～5 times of weight and place reactor, with above-mentioned cobalt saline solution, the saline solution of metallic element M, aqueous alkali and complexing agent aqueous solution are input in the reactor of band stirring respectively continuously with pump, the flow of control cobalt saline solution and complexing agent aqueous solution, promptly control the mol ratio of complexing agent and Co, it is 8～11 that the flow of adjusting aqueous alkali makes the pH value of reactor internal reaction liquid, control reaction temperature is 30～60 ℃, the mol ratio of the Ni of the nickel hydroxide that metal M that coats and Co and quilt are coated is: (Co+M): Ni=0.03～0.1, the mol ratio of metal M and Co is 0.01～0.25, and this reaction is intermittent reaction;
Six. the step 5 products therefrom changed over to carries out Separation of Solid and Liquid in the solid-liquid separator, with the solid product of deionized water washing Separation of Solid and Liquid gained to the pH value of washings less than till 8; Product after the washing is dry under 60～100 ℃ in drier, obtains the α-Co (OH) of coating-doping metal
2The ball-shape nickel hydroxide product.
Described α-Co (OH)
2Doping metals M be among Y, Al, Cr, Mn, Yb, Sc, La, In, Ti or the Zn one or more.
Described cobalt salt is cobaltous sulfate or cobalt nitrate.
The salt of described doping metals is one or more in chloride, nitrate or the sulfur dissolving hydrochlorate, and adding proportion is M: Co=0.01～0.25 (mol ratio); Institute's doping metals is obtain solution separately, and charging separately also can be mixed with the mixed solution charging with cobalt saline solution or aqueous alkali.
Described aqueous alkali is sodium hydrate aqueous solution or potassium hydroxide aqueous solution.
Described complexing agent is one or two or more kinds the mixing in ammonia, ethylenediamine, oxalic acid or the citric acid.Complexing agent is obtain solution separately, and charging separately also can be mixed with the mixed solution charging with cobalt saline solution or aqueous alkali.
The mol ratio of described complexing agent and Co is respectively: NH
3: Co=0.1～0.5, ethylenediamine: Co=0.1～0.3, oxalic acid: Co=0.05～0.2, citric acid: Co=0.01～0.1.
Introduce embodiments of the invention below:
Embodiment one, preparation contain CoSO
47H
2O 1.8 mol, YCl
30.02 350 milliliters of the mixed aqueous solutions of mol are prepared 0.2 mol oxalic acid solution 400mL, contain NH
3Concentration is 400 milliliters of the sodium hydrate aqueous solutions of 4 mol of 0.9 mol.Take by weighing ball-shape nickel hydroxide 600 gram, placing dischargeable capacity is 5 liters reactor, adds 0.6 liter of deionized water simultaneously.Temperature in the control reactor is 45 ℃, and mixing speed is 1200 rev/mins.With CoSO
4, YCl
3Mixed aqueous solution, oxalic acid solution and contain NH
3Sodium hydrate aqueous solution be input in the reactor CoSO respectively continuously with measuring pump
4, YCl
3The flow of mixed aqueous solution is 1.5 ml/min, and the flow of oxalic acid solution is pressed oxalic acid: Co (mol ratio)=0.12 charging, and be 10.00 ± 0.02 by the pH value that the flow of regulating the NaOH aqueous solution is controlled reactant liquor.Work as CoSO
4, YCl
3Stop reaction after mixed aqueous solution uses up, from reactor, discharge feed liquid and carry out Separation of Solid and Liquid.Wash solid products till the pH of cleaning solution value is less than 8 with 60 ℃ deionized waters.Solid product after the washing is put into drying box descended dry 4 hours, obtain coating the ball-shape nickel hydroxide product of mixing the yttrium cobalt hydroxide at 80 ℃.
Embodiment two, the used Co (NO of coating
3)
26H
2O 1.8 mol, YCl
30.02 totally 245 milliliters of the mixed aqueous solutions of mol, the flow of oxalic acid solution is pressed oxalic acid: Co (mol ratio)=0.2 charging, and the temperature in the control reactor is 60 ℃, other condition is identical with embodiment one.
Embodiment three, the used CoSO of coating
47H
2O1.8 mol, Y (NO
3)
30.02 totally 105 milliliters of the mixed aqueous solutions of mol, the flow of oxalic acid solution is pressed oxalic acid: Co (mol ratio)=0.05 charging, and the temperature in the control reactor is 30 ℃, other condition is identical with embodiment one.
Embodiment four, the used CoSO of coating
47H
2O 1.8 mol, Y (SO
4)
30.02 totally 245 milliliters of the mixed aqueous solutions of mol are prepared 0.2 mol citric acid solution 400mL, the flow of citric acid solution is pressed citric acid: Co (mol ratio)=0.05 charging, other condition is identical with embodiment one.
Embodiment five, preparation contain CoSO
47H
2O 1.8 mol, YCl
30.27 216 milliliters of the mixed aqueous solutions of mol, other condition is identical with embodiment four.
Embodiment six, preparation contain CoSO
47H
2O 1.8 mol, YCl
30.45 199 milliliters of the mixed aqueous solutions of mol, other condition is identical with embodiment four.
Embodiment seven, preparation contain CoSO
47H
2O 1.8 mol, ScCl
30.02 245 milliliters of the mixed aqueous solutions of mol, other condition is identical with embodiment one.
Embodiment eight, preparation contain CoSO
47H
2O 0.5 mol, Sc (NO
3)
30.08 770 milliliters of the mixed aqueous solutions of mol, preparation contains NH
3Concentration is 800 milliliters of the sodium hydrate aqueous solutions of 2 mol of 0.1 mol.Take by weighing ball-shape nickel hydroxide 600 gram, placing dischargeable capacity is 10 liters reactor, adds 3 liters of deionized waters simultaneously.Wherein the flow of oxalic acid solution is pressed oxalic acid: Co (mol ratio)=0.2 charging, other condition with
Embodiment one is identical.
Embodiment nine, preparation contain CoSO
47H
2O 3 mol (feed temperature keeps 45 ℃), ScCl
30.45 130 milliliters of the mixed aqueous solutions of mol, the flow of oxalic acid solution is pressed oxalic acid: Co (mol ratio)=0.05 charging, other condition is identical with embodiment one.
Embodiment ten, preparation contain CoSO
47H
2O 1.8 mol, YbCl
30.18 225 milliliters of the mixed aqueous solutions of mol are prepared 0.2 mol oxalic acid solution 300mL, press oxalic acid: the charging of Co (mol ratio)=0.12 control oxalic acid flow, the pH value of control reactant liquor is 8.00 ± 0.02, other condition is identical with embodiment one.
The pH value of embodiment 11, control reactant liquor is 9.00 ± 0.02, and other condition is identical with embodiment ten.
The pH value of embodiment 12, control reactant liquor is 10.00 ± 0.02, and other condition is identical with embodiment ten.
The pH value of embodiment 13, control reactant liquor is 11.00 ± 0.02, and other condition is identical with embodiment ten.
Embodiment 14, preparation contain CoSO
47H
2O 1.8 mol, InCl
30.18 225 milliliters of the mixed aqueous solutions of mol, prepare 0.2 mol citric acid solution 300mL, press citric acid: the charging of Co (mol ratio)=0.1 control citric acid flow, the pH value of control reactant liquor is 9.00 ± 0.02, control reaction temperature is 60 ℃, and other condition is identical with embodiment one.
Embodiment 15, preparation 0.2 mol citric acid solution 300mL, press the charging of citric acid/Co (mol ratio)=0.05 control citric acid flow, the pH value of control reactant liquor is 10.00 ± 0.02, and control reaction temperature is 45 ℃, and other condition is identical with embodiment 14.
Embodiment 16, preparation 0.2 mol citric acid solution 300mL, press citric acid: the charging of Co (mol ratio)=0.01 control citric acid flow, the pH value of control reactant liquor is 11.00 ± 0.02, and control reaction temperature is 30 ℃, and other condition is identical with embodiment 14.
Embodiment 17, preparation contain CoSO
47H
2O 1.8 mol, LaCl
30.18 225 milliliters of the mixed aqueous solutions of mol, prepare 0.2 mol oxalic acid solution 300mL, press oxalic acid: the charging of Co (mol ratio)=0.01 control oxalic acid flow, preparation contain 600 milliliters of the sodium hydrate aqueous solutions that ethylenediamine concentration is 3 mol of 0.2 mol.The pH value of control reactant liquor is 11.00 ± 0.02, and other condition is identical with embodiment one.
Embodiment 18, preparation contain 400 milliliters of the sodium hydrate aqueous solutions that ethylenediamine concentration is 6 mol of 0.4 mol.Other condition is identical with embodiment 17.
Embodiment 19, preparation contain 400 milliliters of the sodium hydrate aqueous solutions that ethylenediamine concentration is 8 mol of 0.54 mol.Other condition is identical with embodiment 17.
Embodiment 20, the used CoSO of coating
41.8 mol, CrCl
30.02 totally 245 milliliters of mol mixed aqueous solutions contain NH
3Concentration is 400 milliliters of the sodium hydrate aqueous solutions of 4 mol of 0.2 mol.Other condition is identical with embodiment one.
Embodiment 21, the used CoSO of coating
41.8 mol, Cr (NO
3)
30.27 totally 216 milliliters of mol mixed aqueous solutions.Other condition is identical with embodiment 20.
Embodiment 22, the used CoSO of coating
41.8 mol, Cr (SO
4)
30.45 totally 199 milliliters of mol mixed aqueous solutions.Other condition is identical with embodiment 20.
Embodiment 23, the used CoSO of coating
41.8 mol, YCl
30.02 mol, MnSO
40.02 totally 245 milliliters of mol mixed aqueous solutions.Other condition is identical with embodiment one.
Embodiment 24, the used CoSO of coating
41.8 mol, Yb (NO
3)
30.02 mol, MnCl
20.16 totally 225 milliliters of mol mixed aqueous solutions.Other condition is identical with embodiment one.
Embodiment 25, the used CoSO of coating
41.8 mol, La (NO
3)
30.02 mol, Mn (NO
3)
30.4 totally 200 milliliters of mol mixed aqueous solutions.Other condition is identical with embodiment one.
Embodiment 26, the used CoSO of coating
41.8 mol, ScCl
30.02 mol, TiCl
40.02 totally 245 milliliters of mol mixed aqueous solutions.Other condition is identical with embodiment one.
Embodiment 27, the used CoSO of coating
41.8 mol, CrCl
30.02 mol, Ti (SO
4)
20.16 totally 225 milliliters of mol mixed aqueous solutions.Other condition is identical with embodiment one.
Embodiment 28, the used CoSO of coating
41.8 mol, In (NO
3)
30.02 mol, Ti (NO
3)
40.4 totally 200 milliliters of mol mixed aqueous solutions.Other condition is identical with embodiment one.
Embodiment 29, preparation contain CoSO
47H
2O 1.8 mol, 350 milliliters of the mixed aqueous solutions of oxalic acid 0.3 mol contain Al
2(SO
4)
30.02 400 milliliters of the sodium hydrate aqueous solutions of 3.6 mol of mol.Other condition is identical with embodiment one.
Embodiment 30, preparation contain NaAlO
20.18 400 milliliters of the sodium hydrate aqueous solutions of 3.6 mol of mol.Other condition is identical with embodiment 29.
Embodiment 31, preparation contain Al (NO
3)
30.45 400 milliliters of the sodium hydrate aqueous solutions of 3.6 mol of mol.Other condition is identical with embodiment 29.
Embodiment 32, preparation contain ZnSO
40.02 400 milliliters of the sodium hydrate aqueous solutions of 3.6 mol of mol.Other condition is identical with embodiment 29.
Embodiment 33, preparation contain Na
2ZnO
20.18 400 milliliters of the sodium hydrate aqueous solutions of 3.6 mol of mol.Other condition is identical with embodiment 29.
Embodiment 34, preparation contain Zn (NO
3)
20.45 400 milliliters of the sodium hydrate aqueous solutions of 3.6 mol of mol.Other condition is identical with embodiment 29.
Comparing embodiment one, preparation CoSO
47H
2350 milliliters of the aqueous solution of O 1.8 mol.Other condition is identical with embodiment one, and what any other metal ion was not mixed in preparation covers the cobalt ball-shape nickel hydroxide.
Comparing embodiment two, do not add any complexing agent in the coating process, other condition is identical with embodiment one, and what yttrium was mixed in preparation covers the cobalt ball-shape nickel hydroxide.
Comparing embodiment three, the temperature when coating are 20 ℃, and other condition is identical with embodiment one, prepare mix yttrium cover the cobalt ball-shape nickel hydroxide.
Comparing embodiment three, the temperature when coating are 70 ℃, and other condition is identical with embodiment one, prepare mix yttrium cover the cobalt ball-shape nickel hydroxide.
Comparing embodiment four, when coating pH value is controlled at 7.00 ± 0.02, other condition is identical with embodiment seven, prepare mix scandium cover the cobalt ball-shape nickel hydroxide.
When comparing embodiment five, coating the pH value is controlled at 12.00 ± 0.02.Other condition is identical with embodiment ten, and what ytterbium was mixed in preparation covers the cobalt ball-shape nickel hydroxide.
Comparing embodiment six, the used CoSO of coating
41.8 mol, InCl
30.27 totally 30 milliliters of mol mixed aqueous solutions.Other condition is identical with embodiment 15, and what indium was mixed in preparation covers the cobalt ball-shape nickel hydroxide.
Comparing embodiment seven, the used CoSO of coating
41.8 mol, CrCl
30.6 totally 400 milliliters of mol mixed aqueous solutions.Other condition is identical with embodiment 20, and what chromium was mixed in preparation covers the cobalt ball-shape nickel hydroxide.
Comparing embodiment eight, the used CoSO of coating
41.8 mol, CrCl
30.54 totally 190 milliliters of mol mixed aqueous solutions.Other condition is identical with embodiment 20, and what scandium was mixed in preparation covers the cobalt ball-shape nickel hydroxide.
Battery is made and the performance test condition: take by weighing embodiment one～34 respectively, the cobalt ball-shape nickel hydroxide sample that covers that the gold doping of comparing embodiment one～eight belongs to element M respectively 15 restrains, do not add other conductive agent, add an amount of carboxymethyl cellulose (CMC), polytetrafluoroethylene (PETF) emulsion as binder, with the nickel foam is collector, per 15 gram samples are made three positive plates respectively, are negative pole (every contains 7.5 gram hydrogen bearing alloys) with the hydrogen bearing alloy pole piece, make three AA type Ni-H cells.After battery discharges and recharges activation through 3 0.2C, carry out the charge-discharge test (charge-discharge magnification is 1C) of normal temperature (25 ℃) and high temperature (60 ℃) again, test result (three batteries of each sample making are averaged) is listed in the table 1.
Comparing embodiment nine, take by weighing ball-shape nickel hydroxide sample 15 gram that does not cover cobalt, add 0.5 gram nickel powder, 1.05 gram cobalt oxyhydrogen powders as conductive agent, other operating condition is identical with above-mentioned battery making and performance test condition with step.Test result is listed in the table 1.
Table 1
| Sample number | Tap density (g/cm 3) | Specific discharge capacity (mAh/g) |
| Embodiment one | 2.23 | 271 |
| Embodiment two | 2.19 | 269 |
| Embodiment three | 2.20 | 273 |
| Embodiment four | 2.18 | 265 |
| Embodiment five | 2.20 | 268 |
| Embodiment six | 2.26 | 268 |
| Embodiment seven | 2.17 | 269 |
| Embodiment eight | 2.15 | 272 |
| Embodiment nine | 2.20 | 270 |
| Embodiment ten | 2.16 | 265 |
| Embodiment 11 | 2.10 | 269 |
| Embodiment 12 | 2.17 | 265 |
| Embodiment 13 | 2.21 | 271 |
| Embodiment 14 | 2.22 | 269 |
| Embodiment 15 | 2.17 | 275 |
| Embodiment 16 | 2.20 | 274 |
| Embodiment 17 | 2.16 | 269 |
| Embodiment 18 | 2.19 | 274 |
| Embodiment 19 | 2.19 | 278 |
| Embodiment 20 | 2.16 | 266 |
| Embodiment 21 | 2.23 | 270 |
| Embodiment 22 | 2.22 | 270 |
| Embodiment 23 | 2.19 | 272 |
| Embodiment 24 | 2.18 | 271 |
| Embodiment 25 | 2.16 | 268 |
| Embodiment 26 | 2.22 | 271 |
| Embodiment 27 | 2.25 | 272 |
| Embodiment 28 | 2.19 | 268 |
| Embodiment 29 | 2.12 | 269 |
| Embodiment 30 | 2.17 | 265 |
| Embodiment 31 | 2.23 | 273 |
| Embodiment 32 | 2.18 | 271 |
| Embodiment 33 | 2.20 | 271 |
| Embodiment 34 | 2.14 | 269 |
| Comparative example one | 2.12 | 248 |
| Comparative example two | 1.79 | 260 |
| Comparative example three | 1.92 | 235 |
| Comparative example four | 1.85 | 246 |
| Comparative example five | 1.78 | 239 |
| Comparative example six | 2.20 | 230 |
| Comparative example seven | 1.56 | 219 |
| Comparative example eight | 1.89 | 228 |
| Comparative example nine | 2.28 | 239 |
Claims (7)
1. α-the Co in ball shape nickel hydroxide surface coating-doping metal M (OH)
2Method, it is characterized in that: this method comprises following each step successively:
One. compound concentration is the cobalt saline solution of 0.5～3 mol;
Two. compound concentration is the aqueous solution of the doped metal salt of wanting of 0.1～0.5 mol;
Three. compound concentration is the aqueous alkali of 3～8 mol;
Four. prepare certain density complexing agent aqueous solution;
Five. take by weighing the ball-shape nickel hydroxide of constant weight and the deionized water of 1～5 times of weight and place reactor, with above-mentioned cobalt saline solution, the saline solution of metallic element M, aqueous alkali and complexing agent aqueous solution are input in the reactor of band stirring respectively continuously with pump, the flow of control cobalt saline solution and complexing agent aqueous solution, promptly control the mol ratio of complexing agent and Co, it is 8～11 that the flow of adjusting aqueous alkali makes the pH value of reactor internal reaction liquid, control reaction temperature is 30～60 ℃, the mol ratio of the Ni of the nickel hydroxide that metal M that coats and Co and quilt are coated is: (Co+M): Ni=0.03～0.1, the mol ratio of metal M and Co is 0.01～0.25, and this reaction is intermittent reaction;
Six. the step 5 products therefrom changed over to carries out Separation of Solid and Liquid in the solid-liquid separator, with the solid product of deionized water washing Separation of Solid and Liquid gained to the pH value of washings less than till 8; Product after the washing is dry under 60～100 ℃ in drier, obtains the α-Co (OH) of coating-doping metal
2The ball-shape nickel hydroxide product.
2. according to the α-Co (OH) of the described ball shape nickel hydroxide surface coating-doping of claim 1 metal M
2Method, it is characterized in that: described α-Co (OH)
2Doping metals M be among Y, Al, Cr, Mn, Yb, Sc, La, In, Ti or the Zn one or more.
3. according to the α-Co (OH) of the described ball shape nickel hydroxide surface coating-doping of claim 1 metal M
2Method, it is characterized in that: described cobalt salt is cobaltous sulfate or cobalt nitrate.
4. according to the α-Co (OH) of the described ball shape nickel hydroxide surface coating-doping of claim 1 metal M
2Method, it is characterized in that: the salt of described doping metals is one or more in chloride, nitrate or the sulfur dissolving hydrochlorate, and the ratio of Tian Jiaing is M: Co=0.01～0.25 in molar ratio; Institute's doping metals is obtain solution separately, and charging separately also can be mixed with the mixed solution charging with cobalt saline solution or aqueous alkali.
5. according to the α-Co (OH) of the described ball shape nickel hydroxide surface coating-doping of claim 1 metal M
2Method, it is characterized in that: described aqueous alkali is sodium hydrate aqueous solution or potassium hydroxide aqueous solution.
6. according to the α-Co (OH) of the described ball shape nickel hydroxide surface coating-doping of claim 1 metal M
2Method, it is characterized in that: described complexing agent is one or two or more kinds the mixing in ammonia, ethylenediamine, oxalic acid or the citric acid, complexing agent is obtain solution separately, and charging separately also can be mixed with the mixed solution charging with cobalt saline solution or aqueous alkali.
7. according to the α-Co (OH) of the described ball shape nickel hydroxide surface coating-doping of claim 1 metal M
2Method, it is characterized in that: the mol ratio of described complexing agent and Co is respectively: NH
3: Co=0.1～0.5, ethylenediamine: Co=0.1～0.3, oxalic acid: Co=0.05～0.2, citric acid: Co=0.01～0.1.
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| US8883156B2 (en) | 2006-04-05 | 2014-11-11 | Abbvie Biotechnology Ltd. | Purified antibody composition |
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| CN100345770C (en) * | 2005-04-20 | 2007-10-31 | 河南新飞科隆电源有限公司 | Spherical nickel hydroxide with composite cobalt layer being coated and preparation method |
| CN1328804C (en) * | 2005-08-01 | 2007-07-25 | 桂林工学院 | Method for synthesizing molten salt package of spheric doping Li-Ni oxides |
| CN102054987A (en) * | 2010-11-24 | 2011-05-11 | 安徽亚兰德新能源材料有限公司 | Spherical nickel hydroxide for high-temperature battery anode and preparation method thereof |
| JP6461370B2 (en) * | 2015-11-06 | 2019-01-30 | トヨタ自動車株式会社 | Cathode active material and alkaline battery |
| CN105551818B (en) * | 2016-01-20 | 2018-07-06 | 复旦大学 | β-cobalt hydroxide nickel and nickel-plating carbon nanotube composite material and its preparation method and application |
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| CN110339838B (en) * | 2019-06-28 | 2022-02-11 | 华东师范大学 | Preparation method and application of transition metal doped nano alpha-cobalt hydroxide material |
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| US6620549B2 (en) * | 1998-06-16 | 2003-09-16 | Matsushita Electric Industrial Co., Ltd. | Alkaline storage battery |
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| US8883156B2 (en) | 2006-04-05 | 2014-11-11 | Abbvie Biotechnology Ltd. | Purified antibody composition |
| US8895009B2 (en) | 2006-04-05 | 2014-11-25 | Abbvie Biotechnology Ltd. | Purified antibody composition |
| US8906372B2 (en) | 2006-04-05 | 2014-12-09 | Abbvie Biotechnology Ltd. | Purified antibody composition |
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