CN1282114A - Preparation method of nickel positive active material spherical alpha-nickel hydroxide - Google Patents
Preparation method of nickel positive active material spherical alpha-nickel hydroxide Download PDFInfo
- Publication number
- CN1282114A CN1282114A CN00123599A CN00123599A CN1282114A CN 1282114 A CN1282114 A CN 1282114A CN 00123599 A CN00123599 A CN 00123599A CN 00123599 A CN00123599 A CN 00123599A CN 1282114 A CN1282114 A CN 1282114A
- Authority
- CN
- China
- Prior art keywords
- nickel
- solution
- mol
- preparation
- concentration
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 16
- 239000007774 positive electrode material Substances 0.000 title claims description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 239000007788 liquid Substances 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 9
- 230000032683 aging Effects 0.000 claims abstract description 7
- 239000007787 solid Substances 0.000 claims abstract description 7
- 239000007864 aqueous solution Substances 0.000 claims abstract description 6
- 239000008367 deionised water Substances 0.000 claims abstract description 6
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000000926 separation method Methods 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 30
- 239000000126 substance Substances 0.000 claims description 11
- 239000008139 complexing agent Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 8
- 239000012452 mother liquor Substances 0.000 claims description 8
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 8
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- PXEDJBXQKAGXNJ-QTNFYWBSSA-L disodium L-glutamate Chemical compound [Na+].[Na+].[O-]C(=O)[C@@H](N)CCC([O-])=O PXEDJBXQKAGXNJ-QTNFYWBSSA-L 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 229910021645 metal ion Inorganic materials 0.000 claims description 4
- 235000013923 monosodium glutamate Nutrition 0.000 claims description 4
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 4
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 4
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 3
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 239000001509 sodium citrate Substances 0.000 claims description 3
- 229940073490 sodium glutamate Drugs 0.000 claims description 3
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims description 3
- 229940038773 trisodium citrate Drugs 0.000 claims description 3
- VZOPRCCTKLAGPN-ZFJVMAEJSA-L potassium;sodium;(2r,3r)-2,3-dihydroxybutanedioate;tetrahydrate Chemical compound O.O.O.O.[Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O VZOPRCCTKLAGPN-ZFJVMAEJSA-L 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229940074446 sodium potassium tartrate tetrahydrate Drugs 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical group [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- 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 1
- 238000007599 discharging Methods 0.000 abstract description 8
- 239000000203 mixture Substances 0.000 abstract description 6
- 239000011149 active material Substances 0.000 abstract description 3
- 150000002815 nickel Chemical class 0.000 abstract description 2
- -1 nickel anion Chemical class 0.000 abstract description 2
- 238000005406 washing Methods 0.000 abstract description 2
- 239000003153 chemical reaction reagent Substances 0.000 abstract 1
- 238000005086 pumping Methods 0.000 abstract 1
- 230000029219 regulation of pH Effects 0.000 abstract 1
- 229910006527 α-Ni(OH)2 Inorganic materials 0.000 abstract 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 150000003863 ammonium salts Chemical class 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- 230000005611 electricity Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000012266 salt solution Substances 0.000 description 4
- 229910006279 γ-NiOOH Inorganic materials 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- 229940024606 amino acid Drugs 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 230000027756 respiratory electron transport chain Effects 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- OVBJJZOQPCKUOR-UHFFFAOYSA-L EDTA disodium salt dihydrate Chemical compound O.O.[Na+].[Na+].[O-]C(=O)C[NH+](CC([O-])=O)CC[NH+](CC([O-])=O)CC([O-])=O OVBJJZOQPCKUOR-UHFFFAOYSA-L 0.000 description 2
- 150000001413 amino acids Chemical class 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229940071106 ethylenediaminetetraacetate Drugs 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910001453 nickel ion Inorganic materials 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 241000080590 Niso Species 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 239000001996 bearing alloy Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 229940001468 citrate Drugs 0.000 description 1
- 229960004106 citric acid Drugs 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 229940012017 ethylenediamine Drugs 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000010808 liquid waste Substances 0.000 description 1
- AIBQNUOBCRIENU-UHFFFAOYSA-N nickel;dihydrate Chemical compound O.O.[Ni] AIBQNUOBCRIENU-UHFFFAOYSA-N 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 229960001367 tartaric acid Drugs 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 229910003160 β-NiOOH 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 preparation method of nickel anion active material spherical alpha-nickel hydroxide includes the following steps: pumping the nickel salt aqueous solution and sodium hydroxide alkaline aqueous solution with a certain quantity and concentration and auxiliary reaction reagent into reactor containing deionized water by means of metering pump; under the conditions of constant temp. system, solid content retaining system and pH regulation system to proceed reaction, after reation is complete, ageing and implementing crystalline conversion. The solid-liquid mixture system in reactor is undergone the processes of solid-liquid separation, washing and drying to obtain the invented product alpha-Ni(OH)2. Said product possesses excellent performance of high charging efficiency, large discharging depth and charging-discharging with heavy current.
Description
The present invention relates to a kind of preparation method of nickel positive active material spherical alpha-nickel hydroxide, belong to Chemical Engineering and field of new.
Nickel hydroxide (Ni (OH)
2) be various alkaline rechargeable batteries (as Ni/Cd, Ni/Zn, Ni/MH, Ni/H
2Deng) positive electrode active materials.Capacity and life-span to battery are played key effect.There is different crystal formations in nickel hydroxide with oxidation state going back ortho states, and present nickel electrode all adopts
Electricity is to circulation, and in the right electrochemical reaction process of this electricity, the variation of the oxidation state of nickle atom is about 1, thereby its electron transfer number has only 1, and its theoretical specific capacity only is 289mAh/g; In addition, when electrode when overcharging, β-NiOOH is converted into γ-NiOOH, changes α-Ni (OH) in discharge overcharges into
2, α-Ni (OH)
2Unstable in alkali lye, become β-Ni (OH) during placement again
2Because α-Ni (OH)
2And the crystalline density of γ-NiOOH is all less than β-Ni (OH)
2, thereby there is swelling in electrode in charge and discharge process.The expansion of electrode has caused redistributing of battery electrolyte inside, has increased the internal resistance and the polarization of electrode, causes the interior voltage rise height of battery and climbs the alkali phenomenon, has accelerated the inefficacy speed of battery.
But circulation can not have been satisfied modern electrical equipment well to performance demands such as rechargeable battery small size, light weight, high power capacity, long-life high current charge-discharges.
α-Ni (OH)
2Close with the crystalline density of γ-NiOOH, also there is the electrochemistry circulation between the two.Because the oxidation state of nickle atom can reach 3.67 among γ-NiOOH, thereby
Electricity is in the circulation, and the electron transfer number of each nickle atom can surpass 1 in theory, and its theoretical specific capacity will reach 480mAh/g, consider the influence of doping, and its electric specific capacity also will reach 380 mAh/g.With α-Ni (OH)
2For the nickel positive pole of active material preparation, will avoid the expansion of electrode effectively, and greatly improve the specific discharge capacity of battery, satisfy modern electrical equipment well to the above-mentioned performance demands of rechargeable battery.
The 3 a large amount of valence metal ions that mix in the nickel hydroxide crystal can improve α-Ni (OH)
2Stability in alkali lye, thus guarantee to discharge and recharge
Between carry out.Prepare β-Ni (OH) at present
2Technology adopt the liquid phase reactor method more, contain in the nickel salt solution and sodium hydroxide solution adding system simultaneously of doped chemical (cobalt, zinc), having under the condition of stirring, generate nickel hydroxide.Yet, adopt this prepared α-Ni (OH)
2, when the amount of doped chemical is big, there is serious segregation phenomena, the doped chemical major part can not be evenly distributed in the nickel hydroxide lattice, but separates out separately in the system mother liquor.α-the Ni (OH) of preparation
2Form is amorphous or sheet, and washing, filtration, drying are all very difficult, causes the tap density of sample lower, and serviceability is relatively poor, be difficult for being filled in nickel foam or the nickel fiber, thereby the fill volume of the battery that reduces can not be brought into play effectively
The usefulness that electricity is right.
The objective of the invention is to propose a kind of preparation method of nickel positive active material spherical alpha-nickel hydroxide, that uses two or more has the mixed twine mixture of different complexing powers to nickel ion and dopant ion; Doping elements is with the form of metal ion or acid ion, and with nickel ion doping deposition, crystallization forms substitutional solid solution Ni under the trend that different pH changes
1-2xM
2x(OH)
2(CO
3)
xNH
2O (5%＜x＜15%).
The preparation method of the nickel positive active material spherical alpha-nickel hydroxide that the present invention proposes may further comprise the steps:
1, material liquid preparation: preparation contains the nickel sulfate solution A of complexing agent and additive, wherein the concentration of nickelous sulfate is 0.5～3 mol, complexing agent is at least a material in trisodium citrate, sodium potassium tartrate tetrahydrate, sodium glutamate and the disodium ethylene diamine tetraacetate, its concentration is 0.01～0.5 mol, additive is zinc sulfate or cobaltous sulfate, and concentration is 0.001～0.5 mol; Preparation contains the sodium hydrate aqueous solution B of ammonia, and wherein concentration sodium hydroxide is 5～8 mol, and the concentration of ammonia is 0.1～2.0 mol; With a certain amount of doped chemical (Al, Co, Fe, Mn, salt In) is dissolved in solution A or the solution B, and doped chemical is existed with the form of metal ion or acid ion, its doping is: M (OH)
3/ Ni (OH)
2=10～30% (mol ratio).
2, reaction: add a certain amount of deionized water in special reactor in advance, the temperature in the control reactor is 30～80 ℃; Under stirring condition, solution A and solution B be continuously pumped into respectively according to certain flow-rate ratio carry out chemical reaction in the reactor, the nickel hydroxide of generation is discharged reactor continuously.In course of reaction, the pH value of control reaction system is 8～13, and the reaction time is 2～6 hours.
3, ageing: that will discharge contains α-Ni (OH)
2Mother liquor transfer in the aging tank, at room temperature be exposed in the air, continue to stir 1 hour.
4, product and mother liquor carry out Separation of Solid and Liquid through solid-liquid separator, wherein solid spherical α-Ni (OH)
2Particle enters washer and washs with deionized water, enter then drier 60 ℃ dry 2 hours down, dry back obtains spherical alpha-Ni (OH)
2Product.After mother liquor is discharged by solid-liquid separator, discharging after the liquid waste processing device is handled.
Selectable complexing agent comprises: ammoniacal liquor or ammonium salt (ammonium sulfate, ammonium nitrate or ammonium chloride), citric acid or citrate, amino acid or amino-acid salt (single amino acid or kilnitamin all can), tartaric acid or tartrate, ethylenediamine, EDTA.As mentioned above, the complexing agent that mix to use, wherein a kind of is ammoniacal liquor or ammonium salt, in addition, selects for use at least aly from above-mentioned optionally other complexing agent, mixes use with ammoniacal liquor or ammonium salt then.The 3 valency metallic elements that mix can be from selecting one or more the column element down, and these elements comprise: Al, Co, Fe, Mn, In and Ga.Doped chemical shared ratio in crystal is about 10～30%.
The crystallization control and the two-way engagement technology of the use mixed twine mixture that the present invention proposes are compared the α-Ni that makes (OH) as the technology of complexing agent with using single ammoniacal liquor or ammonium salt
2Mode of appearance is sphere or class sphere, and the electron transfer number of each nickle atom in charge and discharge process can reach 1.4～1.5, and electro-chemical activity is higher, and serviceability is better.
The preparation spherical alpha-Ni (OH) that the present invention set up
2Technology have the following advantages: technological process is simple, and technological parameter control realizes easily.The anodal expansion of the nickel that adopts this kind active material to make is little, the specific capacity height, and the high rate charge-discharge performance is good, has bigger practical value.
Introduce embodiments of the invention below:
Embodiment one, takes by weighing 78 gram ZnSO
47H
2O, 370 gram doped chemical salt, CoSO
47H
2O, 1970 gram NiSO
46H
2O, 20 gram sodium glutamates are dissolved in the deionized water, are mixed with 3000 ml water solution A; Take by weighing 600 gram NaOH, measure 115 milliliters of the ammoniacal liquor of 13 mol, be mixed with 3000 ml water solution B; In effective volume is 7 liters reactor, add 6 liters of deionized waters.Having under the condition of stirring, reacting according to above-mentioned technology the 2nd step, wherein the flow of water solution A is 700 milliliters/hour, and the flow of aqueous solution B is～650 milliliters/hour.The pH value of controlling reaction system by the flow of adjusting aqueous solution B is 12.0+0.05.Reaction temperature is 50 ± 0.5 ℃.The mother liquor of discharging at room temperature is exposed in the air, continues to stir 1 hour.After stopping to stir, mother liquor carries out Separation of Solid and Liquid through solid-liquid separator, and wherein solid spherical alpha-nickel hydroxide particle enters washer and washs, and enters 60 ℃ of dryings of drier 2 hours then, obtains the spherical alpha-nickel hydroxide sample.The tap density that records this sample is 1.52g/cm
3Take by weighing 0.5 this sample of gram, 25 milligrams of nickel powders, 20 milligram 60% poly-tetrafluoro emulsion and suitable quantity of water are that collector is made positive pole with the nickel foam, are negative pole with the hydrogen bearing alloy, 25 ℃ record the specific discharge capacity of this sample when 0.2C discharges and recharges is 335mAh/g.
Embodiment two, add trisodium citrate 70 grams when obtain solution A, do not add sodium glutamate and cobaltous sulfate; In solution B, add Al
2(SO
4)
33H
2O 238 grams, other forms feed liquid with embodiment one, finishes preparation process according to the operating condition among the embodiment one.The tap density that records the gained sample is 1.51g/cm
3, identical with anode formula among the embodiment one, the specific discharge capacity when recording this sample 0.2C and discharging and recharging is 329mAh/g.
Embodiment three, add MnSO when obtain solution A
4H
2The O102 gram, disodium ethylene diamine tetraacetate (EDTA) 5 grams no longer add other complexing agents; No longer add other metal salt solutions among the solution liquid B, other is formed with embodiment one, finishes preparation process according to the operating condition among the embodiment one.The tap density that records the gained sample is 1.65g/cm
3, identical with anode formula among the embodiment one, the specific discharge capacity when recording this sample 0.2C and discharging and recharging is 322mAh/g.
Embodiment four, add FeSO when obtain solution A
4H
2The O140 gram no longer adds other metal salt solutions, and other is formed with embodiment one, finishes preparation process according to the operating condition among the embodiment one.The tap density that records the gained sample is 1.47g/cm
3, identical with anode formula among the embodiment one, the specific discharge capacity when recording this sample 0.2C and discharging and recharging is 306mAh/g.
Embodiment five, add InSO when obtain solution A
4The 18O gram no longer adds other metal salt solutions, and other is formed with embodiment one, finishes preparation process according to the operating condition among the embodiment one.The tap density that records the gained sample is 1.49g/cm
3, identical with anode formula among the embodiment one, the specific discharge capacity when recording this sample 0.2C and discharging and recharging is 312mAh/g.
Comparative example one: blending process and parameter are with embodiment two, but Al
2(SO
4)
33H
2O is formulated in the solution A.Other forms feed liquid with embodiment two.Having under the condition of stirring, solution A and solution B are added in the reactor simultaneously, the flow of solution A is 700 milliliters/hour, and the pH value of controlling reaction system by the flow of adjusting solution B is 8.5+0.05.Other parameter is with embodiment one.Obtain sample through reaction, ageing with after separating drying.The tap density that records this sample is 1.2g/cm
3Anode formula is with embodiment one, and recording the specific discharge capacity of this sample when the 0.2C rate charge-discharge is 293mAh/g.
Comparative example two: blending process and parameter be with embodiment one, but do not contain other complexing agents in the solution A; Other is formed with embodiment one.Having under the condition of stirring, solution A and solution B are added in the reactor simultaneously, the flow of water solution A is 700 milliliters/hour, and the pH value of controlling reaction system by the flow of adjusting solution B is 12.0 ± 0.05.Other parameter is with embodiment one.Obtain product through reaction, ageing with after separating drying.The tap density that records this sample is 1.1g/cm
3Anode formula is with embodiment one, and recording the specific discharge capacity of this sample when the 0.2C rate charge-discharge is 296mAh/g.
Claims (1)
1, a kind of preparation method of nickel positive active material spherical alpha-nickel hydroxide is characterized in that, this method may further comprise the steps:
(1) material liquid preparation: preparation contains the nickel sulfate solution A of complexing agent and additive, wherein the concentration of nickelous sulfate is 0.5～3 mol, complexing agent is at least a material in trisodium citrate, sodium potassium tartrate tetrahydrate, sodium glutamate and the disodium ethylene diamine tetraacetate, its concentration is 0.01～0.5 mol, additive is zinc sulfate or cobaltous sulfate, and concentration is 0.001～0.5 mol; Preparation contains the sodium hydrate aqueous solution B of ammonia, and wherein concentration sodium hydroxide is 5～8 mol, and the concentration of ammonia is 0.1～2.0 mol; The salt of doped chemical M is dissolved in solution A or the solution B, doped chemical is existed with the form of metal ion or acid ion, above-mentioned doped chemical M is any among Al, Co, Fe, Mn or the In, and the mol ratio of doping is: M (OH)
3/ Ni (OH)
2=10～30%;
(2) reaction: add deionized water in reactor in advance, the temperature in the control reactor is 30～80 ℃; Under stirring condition, is that the ratio of A: B=1: 0.6-0.9 is continuously pumped into respectively and carries out chemical reaction in the reactor with solution A and solution B according to flow-rate ratio, the nickel hydroxide that generates is discharged reactor continuously, in course of reaction, the pH value of control reaction system is 8～13, and the reaction time is 2～6 hours;
(3) ageing: that will discharge contains α-Ni (OH)
2Mother liquor transfer in the aging tank, at room temperature be exposed in the air, continue to stir 1 hour;
(4) product and mother liquor carry out Separation of Solid and Liquid through solid-liquid separator, wherein solid spherical α-Ni (OH)
2Particle enters washer and washs with deionized water, enters drier then and descends dry 2 hours at 60 ℃, promptly obtains spherical alpha-Ni of the present invention (OH) after the drying
2Product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN00123599A CN1111918C (en) | 2000-08-25 | 2000-08-25 | Preparation method of nickel positive active material spherical alpha-nickel hydroxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN00123599A CN1111918C (en) | 2000-08-25 | 2000-08-25 | Preparation method of nickel positive active material spherical alpha-nickel hydroxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1282114A true CN1282114A (en) | 2001-01-31 |
| CN1111918C CN1111918C (en) | 2003-06-18 |
Family
ID=4589991
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN00123599A Expired - Fee Related CN1111918C (en) | 2000-08-25 | 2000-08-25 | Preparation method of nickel positive active material spherical alpha-nickel hydroxide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1111918C (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102070208A (en) * | 2010-12-06 | 2011-05-25 | 北京科技大学 | Preparation method of nickel-cobalt hydroxide with controllable appearance |
| CN103288145A (en) * | 2013-05-30 | 2013-09-11 | 先进储能材料国家工程研究中心有限责任公司 | Method for preparing spherical alpha-nickel hydroxide |
| CN103400973A (en) * | 2013-08-08 | 2013-11-20 | 郭建 | Nickel-cobalt lithium aluminate and preparation method of precursor thereof |
| CN103553152A (en) * | 2013-10-22 | 2014-02-05 | 金天能源材料有限公司 | High-density spherical nickel-cobalt-aluminum precursor material and preparation method thereof |
| CN105070512A (en) * | 2015-08-06 | 2015-11-18 | 太原理工大学 | Mg-doped nano spherical flower-shaped alpha-Ni(OH)2 electrode material and preparation method thereof |
| CN109585815A (en) * | 2018-11-16 | 2019-04-05 | 大连理工大学 | A kind of nickel-zinc cell method for preparing anode material adulterating phosphomolybdic acid |
| CN110061221A (en) * | 2019-04-29 | 2019-07-26 | 江苏理工学院 | A kind of interphase alpha-beta-Ni1-xMnx(OH)2/ CNTs composite material and preparation method and application |
| CN112142126A (en) * | 2019-06-28 | 2020-12-29 | 丰田自动车株式会社 | Nickel hydroxide, positive electrode material, alkaline battery, and method for producing nickel hydroxide |
| CN112647092A (en) * | 2020-12-18 | 2021-04-13 | 江苏大学 | Supported nickel-based composite hydrogen evolution catalyst and preparation method and application thereof |
-
2000
- 2000-08-25 CN CN00123599A patent/CN1111918C/en not_active Expired - Fee Related
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102070208A (en) * | 2010-12-06 | 2011-05-25 | 北京科技大学 | Preparation method of nickel-cobalt hydroxide with controllable appearance |
| CN102070208B (en) * | 2010-12-06 | 2012-05-23 | 北京科技大学 | Preparation method of nickel-cobalt hydroxide with controllable appearance |
| CN103288145A (en) * | 2013-05-30 | 2013-09-11 | 先进储能材料国家工程研究中心有限责任公司 | Method for preparing spherical alpha-nickel hydroxide |
| CN103288145B (en) * | 2013-05-30 | 2015-02-25 | 先进储能材料国家工程研究中心有限责任公司 | Method for preparing spherical alpha-nickel hydroxide |
| CN103400973A (en) * | 2013-08-08 | 2013-11-20 | 郭建 | Nickel-cobalt lithium aluminate and preparation method of precursor thereof |
| CN103400973B (en) * | 2013-08-08 | 2015-11-11 | 郭建 | The preparation method of a kind of nickel cobalt lithium aluminate and presoma thereof |
| CN103553152B (en) * | 2013-10-22 | 2015-09-23 | 金天能源材料有限公司 | High-density spherical nickel-cobalt-aluminprecursor precursor material and preparation method thereof |
| CN103553152A (en) * | 2013-10-22 | 2014-02-05 | 金天能源材料有限公司 | High-density spherical nickel-cobalt-aluminum precursor material and preparation method thereof |
| CN105070512A (en) * | 2015-08-06 | 2015-11-18 | 太原理工大学 | Mg-doped nano spherical flower-shaped alpha-Ni(OH)2 electrode material and preparation method thereof |
| CN105070512B (en) * | 2015-08-06 | 2017-11-17 | 太原理工大学 | Mix the flower-shaped α Ni (OH) of Mg nanometer sphericals2Electrode material and preparation method thereof |
| CN109585815A (en) * | 2018-11-16 | 2019-04-05 | 大连理工大学 | A kind of nickel-zinc cell method for preparing anode material adulterating phosphomolybdic acid |
| CN110061221A (en) * | 2019-04-29 | 2019-07-26 | 江苏理工学院 | A kind of interphase alpha-beta-Ni1-xMnx(OH)2/ CNTs composite material and preparation method and application |
| CN112142126A (en) * | 2019-06-28 | 2020-12-29 | 丰田自动车株式会社 | Nickel hydroxide, positive electrode material, alkaline battery, and method for producing nickel hydroxide |
| CN112647092A (en) * | 2020-12-18 | 2021-04-13 | 江苏大学 | Supported nickel-based composite hydrogen evolution catalyst and preparation method and application thereof |
| CN112647092B (en) * | 2020-12-18 | 2022-02-15 | 江苏大学 | Supported nickel-based composite hydrogen evolution catalyst and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1111918C (en) | 2003-06-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109037644B (en) | Preparation method of coated lithium ion battery ternary cathode material | |
| CN115196691A (en) | Nickel-iron-manganese ternary precursor for sodium ion battery and preparation method and application thereof | |
| CN100533822C (en) | Anode active substance and its preparing method and anode and battery | |
| CN1956242A (en) | Preparation method of ternary compound potassium ion battery plus plate material | |
| CN114804232B (en) | Hollow ternary positive electrode material precursor and preparation method thereof | |
| CN101723473A (en) | Preparation method of multivariate doping spherical alpha-Ni(OH)2 with nanometer secondary structure | |
| CN1111918C (en) | Preparation method of nickel positive active material spherical alpha-nickel hydroxide | |
| JP4405547B2 (en) | Method for producing calcium zincate for cathode | |
| CN112960703A (en) | Preparation method of lithium ion battery anode core-shell material with concentration gradient | |
| CN113233519A (en) | Precursor of magnesium, antimony phosphate, aluminum and lithium phosphate co-modified high-nickel cobalt-free positive electrode material, preparation method of precursor and positive electrode material | |
| CN116199274A (en) | Porous hollow ternary precursor and preparation method thereof | |
| CN1089196C (en) | Process of surface cobalt-coating for high-density ball-shape nickel hydroxide | |
| CN102249349B (en) | Multi-component doped spherical nano nickel hydroxide synthesized by chemical-electrochemical combined method | |
| CN112194193A (en) | Preparation method of high-nickel quaternary lithium ion battery positive electrode precursor material | |
| CN100423329C (en) | Spherical nickel hydroxide surface modification method | |
| CN1137851C (en) | Nanometer alpha-nickel hydroxide and its preparation | |
| CN103288145A (en) | Method for preparing spherical alpha-nickel hydroxide | |
| CN100438153C (en) | Positive electrode material of alkaline battery and preparation method | |
| CN117263263A (en) | Small-particle monocrystalline-like cathode material of sodium ion battery, precursor thereof and preparation method | |
| CN114436343B (en) | Preparation method of nickel cobalt manganese hydroxide with particle size in single-peak wide distribution | |
| CN114956121A (en) | High-crystallization Prussian blue analogue material and preparation method and application thereof | |
| CN1075470C (en) | Process for coating cobalt oxide cobalt hydroxide on surface of spherical nickel hydroxide | |
| CN1794493A (en) | Method of improving high temperature performance of spherical nickel hydroxide | |
| CN1185045A (en) | Active material for cathode of nickel cell and prodn. method of cathod therefor | |
| CN101728531B (en) | Anode material of nickel-hydrogen power battery and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |