CN1228867C - Prepn of Y-containing spherical nickel hydroxide - Google Patents
Prepn of Y-containing spherical nickel hydroxide Download PDFInfo
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- CN1228867C CN1228867C CNB021595089A CN02159508A CN1228867C CN 1228867 C CN1228867 C CN 1228867C CN B021595089 A CNB021595089 A CN B021595089A CN 02159508 A CN02159508 A CN 02159508A CN 1228867 C CN1228867 C CN 1228867C
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- yttrium
- nickel hydroxide
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- hydroxide
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- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 title claims abstract description 72
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 62
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims abstract description 62
- 238000002360 preparation method Methods 0.000 claims abstract description 48
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 47
- 238000002156 mixing Methods 0.000 claims abstract description 24
- DEXZEPDUSNRVTN-UHFFFAOYSA-K yttrium(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[Y+3] DEXZEPDUSNRVTN-UHFFFAOYSA-K 0.000 claims abstract description 18
- 239000011248 coating agent Substances 0.000 claims abstract description 14
- 238000000576 coating method Methods 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 13
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 59
- 239000007864 aqueous solution Substances 0.000 claims description 58
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 25
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 22
- 239000000047 product Substances 0.000 claims description 22
- 239000011701 zinc Substances 0.000 claims description 22
- 239000007788 liquid Substances 0.000 claims description 21
- 238000005406 washing Methods 0.000 claims description 20
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 claims description 19
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims description 19
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 claims description 19
- 238000000926 separation method Methods 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- 229910021529 ammonia Inorganic materials 0.000 claims description 11
- 238000005516 engineering process Methods 0.000 claims description 10
- 239000012265 solid product Substances 0.000 claims description 10
- 238000005303 weighing Methods 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000000376 reactant Substances 0.000 claims description 8
- 229910017052 cobalt Inorganic materials 0.000 claims description 7
- 239000010941 cobalt Substances 0.000 claims description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 5
- 230000001105 regulatory effect Effects 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000006104 solid solution Substances 0.000 abstract description 5
- 238000000034 method Methods 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 2
- 238000005234 chemical deposition Methods 0.000 abstract 1
- 238000000975 co-precipitation Methods 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 241000080590 Niso Species 0.000 description 10
- 229910018502 Ni—H Inorganic materials 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000003643 water by type Substances 0.000 description 4
- 239000000320 mechanical mixture Substances 0.000 description 3
- 239000001996 bearing alloy Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000001035 drying Methods 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
- 238000011056 performance test Methods 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- UZLYXNNZYFBAQO-UHFFFAOYSA-N oxygen(2-);ytterbium(3+) Chemical compound [O-2].[O-2].[O-2].[Yb+3].[Yb+3] UZLYXNNZYFBAQO-UHFFFAOYSA-N 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 229940075624 ytterbium oxide Drugs 0.000 description 1
- 229910003454 ytterbium oxide Inorganic materials 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)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The present invention discloses a process for preparing yttric spherical nickel hydroxide, which belongs to the field of chemical material preparation. In the process, the coprecipitation method is mainly used for forming hydroxide solid solutions of yttrium and nickel to prepare yttric spherical nickel hydroxide; the chemical deposition method is used for coating a layer of yttrium hydroxide on the grain surface of yttric or yttrium-free spherical nickel hydroxide. When the molar ratio of yttrium to nickel is 1 to 3%, the charge and discharge performance of the solid solution type and coating type yttric spherical nickel hydroxide products at the temperature of 60DEGC can be obviously improved, and the discharge specific capacity of batteries in which Y2O3 is added in a mechanical mixing mode at the temperature of 60DEGC is increased from about 60% that at a normal temperature to more than 80%; thus, the yttric spherical nickel hydroxide has important application value.
Description
Technical field
The invention belongs to the chemical materials preparation field, particularly a kind of preparation method who contains the yttrium ball-shape nickel hydroxide who is used for alkaline rechargeable battery.
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.Battery as the electric motor car power source often will stand powerful charging and discharge in use, and at this moment, battery will generate heat and cause that temperature raises.At present, commercial Ni-H cell at high temperature (50～60 ℃) charge-discharge performance obviously descends, and the charge efficiency under 60 ℃ has only about 50% of normal temperature.Be difficult to satisfy the requirement of electric motor car to the electrokinetic cell high-temperature behavior.Nickel hydroxide as the Ni-H cell positive electrode active materials is the key factor that influences battery high-temperature behavior.In order to improve the high-temperature behavior of Ni-H cell, existing way is when making positive pole, add some material (as: rare earth oxides such as calcium oxide, yittrium oxide or ytterbium oxide) with the mechanical mixture method and mix use with ball-shape nickel hydroxide, but battery high-temperature behavior improves undesirablely.
Summary of the invention
The purpose of this invention is to provide a kind of yttrium ball-shape nickel hydroxide preparation method that contains that can improve the Ni-H cell high-temperature behavior, is to add YCl in the sulfuric acid solution of nickel, cobalt, zinc in molar ratio
3The aqueous solution mixes with NaOH, ammonia spirit again, fully reacts in reactor, is settled out and contains yttrium ball-shape nickel hydroxide material.Yttrium can be mixed in the nickel hydroxide with the form of solid solution and make the ball-shape nickel hydroxide material that contains yttrium in the method that ball shape nickel hydroxide surface coats yttrium hydroxide.Preparation contains the technology of yttrium ball-shape nickel hydroxide, may further comprise the steps:
1. contain the preparation of yttrium ball-shape nickel hydroxide:
1. in the sulfate solution of nickel, cobalt, zinc, add YCl
3The aqueous solution is mixed with mixed-salt aqueous solution, wherein: Ni
2+Concentration be 1.5～2.0 mol, the mol ratio of Ni: Co: Zn: Y is 100: 1.5～4: 3～8: 1～4;
2. prepare sodium hydrate aqueous solution, concentration sodium hydroxide is 4～6 mol; The preparation ammonia spirit, the concentration of ammonia is 10～14 mol;
3. respectively continuously be input in reactor with pump above-mentioned mixed-salt aqueous solution, sodium hydrate aqueous solution and ammonia spirit, mixed material nature overflow in the reactor is discharged, it is 9～12 hours that the flow of regulating each solution makes the mean residence time of material in reactor, NH
3/ Ni=0.5～1, the pH value of reactant liquor is 11～12, control reaction temperature is 40～60 ℃;
4. with step 3. products therefrom change over to and carry 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 in 80～100 ℃ times dry 2～4 hours, obtains mixing yttrium ball-shape nickel hydroxide product in drier.
2. ball shape nickel hydroxide surface coats yttrium hydroxide:
(1) prepares the ball-shape nickel hydroxide of mixing yttrium and not mixing yttrium by step in the technology 1, wherein: the component ratio of mixing the yttrium ball-shape nickel hydroxide is that the mol ratio of Ni: Co: Zn: Y is 100: 1.5～4: 3～8: 1～2, and the component ratio of not mixing the yttrium ball-shape nickel hydroxide is Ni: Co: Zn=100: 1.5～4: 3～8;
(2) preparation YCl
3With the mixed aqueous solution of disodium ethylene diamine tetraacetate, YCl
3Concentration is 1～2 mol, and the concentration of disodium ethylene diamine tetraacetate is 0.01～0.02 mol; The sodium hydrate aqueous solution of preparation 4～6 mol;
(3) take by weighing constant weight set by step (1) preparation mix yttrium or do not mix the ball-shape nickel hydroxide of yttrium and the deionized water of 4 times of weight places reactor, with pump YCl of continuous input step (2) preparation respectively in reactor
3, disodium ethylene diamine tetraacetate mixed aqueous solution and sodium hydrate aqueous solution, the pH value of control reactant liquor is 8～10, reaction temperature is 40～60 ℃, and the reaction time is 3～4 hours, and the yttrium hydroxide of coating with the mol ratio of the nickel hydroxide that is coated is: Y: Ni=0.5～2: 100;
(4) step (3) products therefrom changed over to carry 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 in 80～100 ℃ times dry 2～4 hours, obtains coating mixing yttrium or not mixing yttrium ball-shape nickel hydroxide product of yttrium hydroxide in drier.
The invention has the beneficial effects as follows that preparation contains the technology of yttrium ball-shape nickel hydroxide and traditional usefulness mechanical mixture formula is added Y
2O
3Technology compare, the Ni-H cell of making has better high temperature charge-discharge performance, the specific discharge capacity under 60 ℃ is more than 80% of normal temperature specific discharge capacity, and the mechanical mixture formula is added Y
2O
360 ℃ on battery under specific discharge capacity only be about 60% of normal temperature specific discharge capacity, have great application value.
Embodiment
The present invention is a kind of yttrium ball-shape nickel hydroxide preparation method that contains, and is to add YCl in molar ratio in the sulfuric acid solution of nickel, Cobalt, zinc
3The aqueous solution mixes with NaOH, ammonia spirit again, fully reacts in reactor, is settled out and contains yttrium ball-shape nickel hydroxide material, and available yttrium mixes in the nickel hydroxide, coats yttrium hydroxide at ball shape nickel hydroxide surface with the form of solid solution.Preparation contains the technology of yttrium ball-shape nickel hydroxide, may further comprise the steps:
1. contain the preparation of yttrium ball-shape nickel hydroxide:
1. in the sulfate solution of nickel, cobalt, zinc, add YCl
3The aqueous solution is mixed with mixed-salt aqueous solution, wherein: Ni
2+Concentration be 1.5～2.0 mol, the mol ratio of Ni: Co: Zn: Y is 100: 1.5～4: 3～8: 1～4;
2. prepare sodium hydrate aqueous solution, concentration sodium hydroxide is 4～6 mol; The preparation ammonia spirit, the concentration of ammonia is 10～14 mol;
3. respectively continuously be input in reactor with pump above-mentioned mixed-salt aqueous solution, sodium hydrate aqueous solution and ammonia spirit, mixed material nature overflow in the reactor is discharged, it is 9～12 hours that the flow of regulating each solution makes the mean residence time of material in reactor, NH
3/ Ni=0.5～1, the pH value of reactant liquor is 11～12, control reaction temperature is 40～60 ℃;
4. with step 3. products therefrom change over to and carry 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 in 80～100 ℃ times dry 2～4 hours, obtains mixing yttrium ball-shape nickel hydroxide product in drier.
2. ball shape nickel hydroxide surface coats yttrium hydroxide:
(1) prepares the ball-shape nickel hydroxide of mixing yttrium and not mixing yttrium by step in the technology 1, wherein: the component ratio of mixing the yttrium ball-shape nickel hydroxide is that the mol ratio of Ni: Co: Zn: Y is 100: 1.5～4: 3～8: 1～2, and the component ratio of not mixing the yttrium ball-shape nickel hydroxide is Ni: Co: Zn=100: 1.5～4: 3～8;
(2) preparation YCl
3With the mixed aqueous solution of disodium ethylene diamine tetraacetate, YCl
3Concentration is 1～2 mol, and the concentration of disodium ethylene diamine tetraacetate is 0.01～0.02 mol; The sodium hydrate aqueous solution of preparation 4～6 mol;
(3) take by weighing constant weight set by step (1) preparation mix yttrium or do not mix the ball-shape nickel hydroxide of yttrium and the deionized water of 4 times of weight places reactor, with pump YCl of continuous input step (2) preparation respectively in reactor
3, disodium ethylene diamine tetraacetate mixed aqueous solution and sodium hydrate aqueous solution, the pH value of control reactant liquor is 8～10, reaction temperature is 40～60 ℃, and the reaction time is 3～4 hours, and the yttrium hydroxide of coating with the mol ratio of the nickel hydroxide that is coated is: Y: Ni=0.5～2: 100;
(4) step (3) products therefrom changed over to carry 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 in 80～100 ℃ times dry 2～4 hours, obtains coating mixing yttrium or not mixing yttrium ball-shape nickel hydroxide product of yttrium hydroxide in drier.
Introducing embodiment is below further specified the present invention:
Embodiment one, use NiSO
46H
2O, CoSO
47H
2O, ZnSO
47H
2The YCl of O and 1.5 mol
3Solution preparation mixed-salt aqueous solution, wherein: NiSO
4Concentration be 1.7 mol, Ni: Co: Zn: Y=100: 2.5: 5: 1 (mol ratio).Prepare the NaOH aqueous solution of 5 mol and the NH of 12 mol
3The aqueous solution.The dischargeable capacity of reactor is 5 liters, adds 5 liters of deionized waters in advance.With measuring pump with above-mentioned mixed-salt aqueous solution, the NaOH aqueous solution and NH
3The aqueous solution is input to respectively in the reactor continuously, and the mixing speed of control reactor is 1500 rev/mins, and the flow of mixed-salt aqueous solution is 5 ml/min, NH
3The flow of the aqueous solution is 1 ml/min, and the pH value of controlling reactant liquor by the flow of regulating the NaOH aqueous solution is 11.50 ± 0.02.Reaction temperature is 50 ± 0.05 ℃.Product and mother liquor enter in the pans from the overfall nature overflow of reactor.Continuously operation stopped charging after 48 hours, the material in the reactor is discharged and places centrifuge to 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 mixing yttrium ball-shape nickel hydroxide product at 80 ℃.
The proportion of composing of embodiment two, mixed-salt aqueous solution is: Ni: Co: Zn: Y=100: 1.5: 3: 2 (mol ratio), NiSO
4Concentration be 1.5 mol, other condition is identical with embodiment one.
The proportion of composing of embodiment three, mixed-salt aqueous solution is: Ni: Co: Zn: Y=100: 3: 7: 3 (mol ratio), NiSO
4Concentration be 2 mol, other condition is identical with embodiment one.
Embodiment four, preparation contain YCl
31.5 mol, contain 35 milliliters of the mixed aqueous solutions of disodium ethylene diamine tetraacetate 0.015 mol, 100 milliliters of the sodium hydrate aqueous solutions of 4.5 mol.Take by weighing by embodiment one condition preparation mix yttrium ball-shape nickel hydroxide 500 grams, placing dischargeable capacity is 5 liters reactor, adds 4 liters of deionized waters simultaneously.Temperature in the control reactor is 50 ℃, and mixing speed is 1000 rev/mins.With YCl
3, disodium ethylene diamine tetraacetate mixed aqueous solution and sodium hydrate aqueous solution be input in the reactor YCl respectively continuously with measuring pump
3, the disodium ethylene diamine tetraacetate mixed aqueous solution flow be 1 ml/min, the pH value of controlling reactant liquor by the flow of regulating the NaOH aqueous solution is 10.00 ± 0.02.Work as YCl
3, that the disodium ethylene diamine tetraacetate mixed aqueous solution uses up the back is out of service, 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 yttrium hydroxide at 80 ℃.
Embodiment five, the used YCl of coating
3, totally 70 milliliters of disodium ethylene diamine tetraacetate mixed aqueous solutions, 100 milliliters of the sodium hydrate aqueous solutions of 4.5 mol.Take by weighing by yttrium ball-shape nickel hydroxide 500 other conditions of gram of mixing of embodiment two conditions preparation identical with embodiment four.
Embodiment six, the used YCl of coating
3, totally 17.5 milliliters of disodium ethylene diamine tetraacetate mixed aqueous solutions, 100 milliliters of the sodium hydrate aqueous solutions of 4.5 mol.Take by weighing by yttrium ball-shape nickel hydroxide 500 other conditions of gram of mixing of embodiment three conditions preparation identical with embodiment four.
Embodiment seven, use NiSO
46H
2O, CoSO
47H
2O, ZnSO
47H
2O prepares mixed-salt aqueous solution, wherein: NiSO
4Concentration be 1.7 mol, Ni: Co: Zn=100: 2.5: 5 (mol ratio), other condition is identical with embodiment one, the ball-shape nickel hydroxide of yttrium is not mixed in preparation; Take by weighing 500 grams and do not mix the operation that ball-shape nickel hydroxide 500 grams of yttrium coat yttrium hydroxide, other condition is identical with embodiment four.
Embodiment eight, use NiSO
46H
2O, CoSO
47H
2O, ZnSO
47H
2O prepares mixed-salt aqueous solution, wherein: NiSO
4Concentration be 1.7 mol, Ni: Co: Zn=100: 4: 8 (mol ratio), other condition is identical with embodiment one, the ball-shape nickel hydroxide of yttrium is not mixed in preparation; Take by weighing 500 grams and do not mix the operation that ball-shape nickel hydroxide 500 grams of yttrium coat yttrium hydroxide, coat used YCl
3, totally 70 milliliters of disodium ethylene diamine tetraacetate mixed aqueous solutions, wherein contain YCl
31.5 mol, contain disodium ethylene diamine tetraacetate 0.015 mol, other condition is identical with embodiment four.
Comparing embodiment one, use NiSO
46H
2O, CoSO
47H
2O, ZnSO
47H
2O prepares mixed-salt aqueous solution, wherein: NiSO
4Concentration be 1.7 mol, Ni: Co: Zn=100: 2.5: 5 (mol ratio), other condition is identical with embodiment one, the ball-shape nickel hydroxide of yttrium is not mixed in preparation.
The proportion of composing of comparing embodiment two, mixed-salt aqueous solution is: Ni: Co: Zn: Y=100: 2.5: 5: 0.5 (mol ratio), other condition is identical with embodiment one, and the ball-shape nickel hydroxide of yttrium is mixed in preparation.
The proportion of composing of comparing embodiment three, mixed-salt aqueous solution is: Ni: Co: Zn: Y=100: 2.5: 5: 3.5 (mol ratio), other condition is identical with embodiment one, and the ball-shape nickel hydroxide of yttrium is mixed in preparation.
Comparing embodiment four, the used YCl of coating
3, totally 87.5 milliliters of disodium ethylene diamine tetraacetate mixed aqueous solutions, wherein contain YCl
31.5 mol, contain disodium ethylene diamine tetraacetate 0.015 mol, other condition is identical with embodiment four, preparation coats the ball-shape nickel hydroxide of yttrium hydroxide.
Comparing embodiment five, take by weighing the ball-shape nickel hydroxide sample of not mixing yttrium 15 gram of comparing embodiment one, add 0.5 gram nickel powder, 1.05 gram cobalt oxyhydrogen powders, add 0.2 gram Y again as conductive agent
2O
3, other operating condition and step and embodiment one to eight, the battery making and the performance test condition of comparing embodiment one to four are identical.Test result is listed in the table 1.
Battery is made and the performance test condition: take by weighing embodiment one to eight respectively, the yttrium ball-shape nickel hydroxide sample that contains of comparing embodiment one to four respectively 15 restrains, respectively add 0.5 gram nickel powder, 1.05 gram cobalt oxyhydrogen powders as 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, with the hydrogen bearing alloy pole piece is negative pole (every contains 7.5 gram hydrogen bearing alloys), makes 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.
Table 1
| Sample number | Solid solution yttrium content Y/Ni (mol ratio) % | Surface yttrium content Y/Ni (mol ratio) % | Specific discharge capacity (25 ℃) mAh/g | Specific discharge capacity (60 ℃) mAh/g | 60 ℃ of following capability retention % |
| Embodiment one | 1 | 0 | 1351 | 1081 | 80 |
| Embodiment two | 2 | 0 | 1274 | 1083 | 85 |
| Embodiment three | 3 | 0 | 1216 | 1058 | 87 |
| Embodiment four | 1 | 1 | 1245 | 1021 | 82 |
| Embodiment five | 1 | 2 | 1223 | 1027 | 84 |
| Embodiment six | 1 | 0.5 | 1322 | 1071 | 81 |
| Embodiment seven | 0 | 1 | 1359 | 1006 | 74 |
| Embodiment eight | 0 | 2 | 1267 | 1001 | 79 |
| Comparative example one | 0 | 0 | 1367 | 725 | 53 |
| Comparative example two | 0.5 | 0 | 1358 | 869 | 64 |
| Comparative example three | 3.5 | 0 | 1140 | 992 | 87 |
| Comparative example four | 0 | 3.5 | 1123 | 876 | 78 |
| Comparative example five | 0 | Mix and add: 1.2 | 1345 | 874 | 65 |
Claims (3)
1. one kind contains yttrium ball-shape nickel hydroxide preparation method, it is characterized in that: the technology that preparation contains the yttrium ball-shape nickel hydroxide may further comprise the steps:
1. in the sulfate solution of nickel, cobalt, zinc, add YCl
3The aqueous solution is mixed with mixed-salt aqueous solution, wherein: Ni
2+Concentration be 1.5～2 mol, the mol ratio of Ni: Co: Zn: Y is 100: 1.5～4: 3～8: 1～4;
2. prepare sodium hydrate aqueous solution, concentration sodium hydroxide is 4～6 mol; The preparation ammonia spirit, the concentration of ammonia is 10～14 mol;
3. respectively continuously be input in reactor with pump above-mentioned mixed-salt aqueous solution, sodium hydrate aqueous solution and ammonia spirit, mixed material nature overflow in the reactor is discharged, it is 9～12 hours that the flow of regulating each solution makes the mean residence time of material in reactor, NH
3/ Ni=0.5～1, the pH value of reactant liquor is 11～12, control reaction temperature is 40～60 ℃;
4. with step 3. products therefrom change over to and carry 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 in 80～100 ℃ times dry 2～4 hours, obtains mixing yttrium ball-shape nickel hydroxide product in drier.
2. according to the described yttrium ball-shape nickel hydroxide preparation method that contains of claim 1, it is characterized in that: the preparation technology at ball shape nickel hydroxide surface coating yttrium hydroxide may further comprise the steps:
(1) mix the yttrium ball-shape nickel hydroxide by the step of preparation process preparation of mixing the yttrium ball-shape nickel hydroxide in the claim 1, the component ratio of wherein mixing the yttrium ball-shape nickel hydroxide is that the mol ratio of Ni: Co: Zn: Y is 100: 1.5～4: 3～8: 1～2;
(2) preparation YCl
3With the mixed aqueous solution of disodium ethylene diamine tetraacetate, YCl
3Concentration is 1～2 mol, and the concentration of disodium ethylene diamine tetraacetate is 0.01～0.02 mol; The sodium hydrate aqueous solution of preparation 4～6 mol;
(3) take by weighing constant weight set by step (1) preparation mix the ball-shape nickel hydroxide of yttrium and the deionized water of 4 times of weight places reactor, with pump YCl of continuous input step (2) preparation respectively in reactor
3, disodium ethylene diamine tetraacetate mixed aqueous solution and sodium hydrate aqueous solution, the pH value of control reactant liquor is 8～10, reaction temperature is 40～60 ℃, and the reaction time is 3～4 hours, and the yttrium hydroxide of coating with the mol ratio of the nickel hydroxide that is coated is: Y: Ni=0.5～2: 100;
(4) step (3) products therefrom changed over to carry 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 in drier in 80～100 ℃ dry 2～4 hours down, what obtain coating yttrium hydroxide mixes yttrium ball-shape nickel hydroxide product.
3. described yttrium ball-shape nickel hydroxide preparation method that contains of claim 2 is characterized in that: the described preparation technology who coats yttrium hydroxide at ball shape nickel hydroxide surface is:
1) earlier the yttrium ball-shape nickel hydroxide is not mixed in preparation: by the mol ratio of Ni: Co: Zn is 100: 1.5～4: 3～8 to be mixed with sulfate solution, wherein: Ni
2+Concentration be 1.5～2 mol; Do not mixed the yttrium ball-shape nickel hydroxide by 2., the 3. and 4. step of claim 1 then;
2) by the step of preparation process (2) of claim 2, (3), (4) preparation, what obtain coating yttrium hydroxide does not mix yttrium ball-shape nickel hydroxide product.
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| CN100423329C (en) * | 2004-03-01 | 2008-10-01 | 长沙矿冶研究院 | Spherical nickel hydroxide surface modification method |
| 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 |
| CN102544469B (en) * | 2010-12-30 | 2015-03-11 | 河南科隆集团有限公司 | Nickel cobalt manganese hydroxide-coated doped spherical nickel oxyhydroxide and preparation method thereof |
| WO2012117989A1 (en) * | 2011-02-28 | 2012-09-07 | 三洋電機株式会社 | Alkaline storage battery |
| CN107293691A (en) * | 2017-07-03 | 2017-10-24 | 河南比得力高新能源科技有限公司 | A kind of positive plate and preparation method and the lithium ion battery including the positive plate |
| CN107492654A (en) * | 2017-07-03 | 2017-12-19 | 河南比得力高新能源科技有限公司 | A kind of column lithium ion battery and its preparation technology |
| CN107302090A (en) * | 2017-07-03 | 2017-10-27 | 河南比得力高新能源科技有限公司 | A kind of positive electrode and the positive plate including the positive electrode |
| CN108091845A (en) * | 2017-12-11 | 2018-05-29 | 宁波高新区锦众信息科技有限公司 | A kind of preparation method of alkaline secondary cell cobalt oxide cladding nickel hydroxide composite material |
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