CN1137851C - Nanometer alpha-nickel hydroxide and its preparation - Google Patents
Nanometer alpha-nickel hydroxide and its preparation Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 62
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 239000008139 complexing agent Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 230000032683 aging Effects 0.000 claims abstract description 8
- 239000000654 additive Substances 0.000 claims abstract description 5
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims abstract description 3
- 229940044175 cobalt sulfate Drugs 0.000 claims abstract description 3
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims abstract description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims abstract description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims abstract description 3
- 150000003839 salts Chemical class 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 239000012452 mother liquor Substances 0.000 claims description 8
- 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 7
- 235000013923 monosodium glutamate Nutrition 0.000 claims description 7
- 241000220317 Rosa Species 0.000 claims description 6
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 claims description 5
- 150000002500 ions Chemical class 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 claims description 5
- 239000001509 sodium citrate Substances 0.000 claims description 5
- 229940073490 sodium glutamate Drugs 0.000 claims description 5
- 235000011006 sodium potassium tartrate Nutrition 0.000 claims description 5
- 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 5
- 229940038773 trisodium citrate Drugs 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 235000019263 trisodium citrate Nutrition 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 238000005469 granulation Methods 0.000 claims description 3
- 230000003179 granulation Effects 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 229910021645 metal ion Inorganic materials 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 150000002815 nickel Chemical class 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 2
- 229910052759 nickel Inorganic materials 0.000 abstract description 14
- 239000000203 mixture Substances 0.000 abstract description 5
- 230000002349 favourable effect Effects 0.000 abstract 1
- 229910006527 α-Ni(OH)2 Inorganic materials 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 21
- 229910052751 metal Inorganic materials 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 229910006279 γ-NiOOH Inorganic materials 0.000 description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 239000006258 conductive agent Substances 0.000 description 4
- 230000005611 electricity Effects 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- 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 3
- 239000011149 active material Substances 0.000 description 3
- 238000003483 aging Methods 0.000 description 3
- 229940024606 amino acid Drugs 0.000 description 3
- 150000003863 ammonium salts Chemical class 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
- 238000007599 discharging Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- -1 nickel (cobalt) ion Chemical class 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
- 239000012266 salt solution Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 229910003160 β-NiOOH Inorganic materials 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
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000001413 amino acids Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229940071106 ethylenediaminetetraacetate Drugs 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 229910001453 nickel ion Inorganic materials 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 238000009818 secondary granulation Methods 0.000 description 2
- 229940095064 tartrate Drugs 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910002640 NiOOH Inorganic materials 0.000 description 1
- 241000080590 Niso Species 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-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
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 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
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 1
- AIBQNUOBCRIENU-UHFFFAOYSA-N nickel;dihydrate Chemical compound O.O.[Ni] AIBQNUOBCRIENU-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 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 nano-grade alpha-nickel hydroxide and a preparation method thereof. In the method, a nickel sulfate water solution and a sodium hydroxide water solution containing complexing agents and additives are prepared, in which salt of doped elements is dissolved; then a cobalt sulfate water solution and a sodium hydroxide water solution containing complexing agents are prepared; the solutions are added in a reactor for chemical reaction; finally, the solution mixture is moved to an aging tank to obtain the nano-grade spherical alpha-Ni(OH)2 product. The method of the present invention has the advantages of simple technological process and easy realization of technological parameter control, and the prepared nickel anode has the advantages of little expansion, high specific capacity, favorable performance of large multiplying power charge and discharge and high practicability.
Description
The present invention relates to a kind of nanometer alpha-nickel hydroxide and preparation method thereof, belong to chemical engineering and field of new.
Nickel hydroxide (Ni (OH)
2) be multiple alkaline rechargeable battery (as Ni/Cd, Ni/Zn, Ni/MH, Ni/H
2Deng) positive electrode active materials, capacity, life-span and the chemical property of battery played key effect.There is different crystal formations in nickel hydroxide with oxidation state going back ortho states, and present nickel electrode all adopts β-Ni (OH)
2 β-NiOOH electricity is to circulation, and the variation of the oxidation state of nickle atom in electrochemical reaction process 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.β-Ni (OH)
2But β-NiOOH electricity can not satisfy modern electrical equipment to performance demands such as rechargeable battery small volume, light weight, heavy body, long lifetime high current charge-discharges well to circulation.
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 at α-Ni (OH)
2 γ-NiOOH 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 storage also will reach 380mAh/g.
In the nickel electrode electrochemical process, proton shifting speed is its controlled step, how to improve the rate of migration of proton, is the key that improves the nickel electrode high rate during charging-discharging.Shorten the migration path of proton, can improve the ability of the high current charge-discharge of material.Nanometer Ni (OH)
2But from theory and practice all is a method that improves performance of nickel electrodes.Nano level Ni (OH)
2Crystalline size little, in charge and discharge process, proton is shorter at intracrystalline migration path; The specific surface area that it is huge can increase contacting of active substance and electrolyte solution; In addition, nanometer Ni (OH)
2Also have quantum size effect, surface effects and macroscopical tunnel effect, crystalline structure is stable, has bigger diffusion of protons coefficient, is expected the electrode materials that becomes a kind of high-energy-density, long lifetime, is suitable for high current charge-discharge.
Prepare nano level α-Ni (OH)
2, will be effectively in conjunction with α-Ni (OH)
2With nanometer Ni (OH)
2Advantage.With nanometer alpha-Ni (OH)
2Nickel positive pole for the active material preparation, it reacts good reversibility, electrochemical reaction resistance is little, the electrochemistry capacitance height, the expansion of electrode will be avoided effectively, and greatly improve the specific discharge capacity of battery, satisfy well modern electrical equipment to rechargeable battery small volume, light weight, heavy body, long lifetime and electromobile to performance demands such as power cell high current charge-discharges.
Yet, because the nano-scale particle particle diameter is less, has bigger surface energy, agglomeration takes place easily, and washing, filtration, drying are all very difficult, cause the tap density of sample lower, use properties 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 α-Ni (OH) effectively
2 γ-right the usefulness of NiOOH electricity.
The objective of the invention is to propose a kind of nanometer alpha-nickel hydroxide and preparation method thereof, that uses two or more has the mixed twine mixture of different complex abilitys to nickel (cobalt) ion and dopant ion, doped metallic elements behind the spraying drying secondary granulation, makes the nickel positive electrode material.
The nanometer alpha-nickel hydroxide of the present invention's preparation, its structural formula is:
(Ni
1-2xM
2x(OH)
2(CO
3)
xNH
2O)
1-y(Co (OH)
2)
y, 5%＜x＜15%, 2%＜y＜10% wherein
The preparation method of the nanometer alpha-nickel hydroxide that the present invention proposes comprises following each step:
(1) stock liquid preparation: preparation contains the nickel sulfate solution A of complexing agent and additive, the concentration that makes single nickel salt wherein is 0.1～2.5 mol, complexing agent wherein is at least a material in trisodium citrate, Seignette salt, Sodium Glutamate and the disodium ethylene diamine tetraacetate, its concentration is 0.01～0.5 mol, additive wherein is zinc sulfate or rose vitriol, and concentration is 0.001～0.5 mol; Prepare ammoniated aqueous sodium hydroxide solution B, making concentration sodium hydroxide wherein is 2～8 mol, and the concentration of ammonia is 0.1～2.0 mol; The salt of doped element is dissolved in solution A or the solution B, doped element is existed with the form of metal ion or acid ion, doped element is Al, Co, Fe, Mn, or any among the In, and doping is: M (OH)
3/ Ni (OH)
2=(0.10～0.30)/1.0 (mol ratio); Preparation contains the cobalt sulfate solution C of complexing agent, wherein the concentration of rose vitriol is 0.05～1.5 mol, complexing agent is at least a material in trisodium citrate, Seignette salt, Sodium Glutamate and the disodium ethylene diamine tetraacetate, and its concentration is 0.005～0.2 mol; Preparation aqueous sodium hydroxide solution D, its concentration is 2～8 mol;
(2) reaction: add 1 liter of solution A in special reactor E in advance, the temperature in the controlling reactor is 30～80 ℃; Under stirring condition, solution B pumped into 250～350 milliliters/hour flow carry out chemical reaction in the reactor, in reaction process, the pH value of control reaction system terminal point is 11～13, the reaction times is 2～4 hours;
In reactor F, add 400 ml soln C in advance, temperature in the controlling reactor is 20～60 ℃: under stirring condition, solution D pumped into 150～250 milliliters/hour flow carry out chemical reaction in the reactor, in reaction process, the pH value of control reaction system is 10～11, and the reaction times is 0.5～1.5 hour;
(3) ageing: will contain α-Ni (OH) among the reactor E
2Mother liquor and reactor F in contain Co (OH)
2Mother liquor transfer in the aging tank, continue down to stir 2.5 hours at 50 ℃;
(4) product and mother liquor enter washer and wash with deionized water, utilize spray-dryer to carry out drying and granulation then, obtain nano-level sphere α-Ni (OH)
2Product.
What one of characteristics of the inventive method were to use two or more has the mixed twine mixture of different complex abilitys to nickel (cobalt) ion and dopant ion;
Selectable complexing agent comprises: ammoniacal liquor or ammonium salt (ammonium sulfate, ammonium nitrate or ammonium chloride), citric acid or Citrate trianion, amino acid or amino acid salts (single amino acid or kilnitamin all can), tartrate or tartrate, quadrol, 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.
Adulterated metallic element can be from element al, Co, and Fe selects one or more among Mn and the In, and doped element shared ratio in crystal is about 10～30%.These elements (except that Al) are with the form of metal ion, with nickel ion codeposition under identical pH variation tendency; Adulterated Al element is with the form of acid ion, and with the nickel ion deposition (two-way engagement) of mixing under different pH variation tendencies, crystallization forms substitutional solid solution Ni
1-2XM
2x(OH)
2(CO
3)
xNH
2O (5%＜x＜15%).
Another one characteristics of the present invention are α-Ni (OH) of preparing
2With conductive agent Co (OH)
2Be nano level, α-Ni (OH)
2With Co (OH)
2Mix the distributing very evenly of conductive agent at nano level; Behind the spraying drying secondary granulation, the product that makes is a micron order, and the tap density of product and use properties are significantly improved.α-Ni (OH) with this prepared
2, it consists of (Ni
1-2xM
2x(OH)
2(CO
3)
xNH
2O)
1-y(Co (OH)
2)
y(5%＜x＜15%, 2%＜y＜10%), its exterior appearance are spherical, and the electron transfer number of sample can reach 1.4～1.5.With the nickel positive pole of this specimen preparation, its charging efficiency height, depth of discharge is big, the excellent property of high current charge-discharge.
The present invention prepares nano-level sphere α-Ni (OH)
2Method have the following advantages: technical process is simple, and processing parameter control realizes that easily conductive agent mixes at nano level with active material, and the conductive agent distribution is very even.The anodal expansion of the nickel that adopts this kind active material to make is little, the specific storage 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 22 gram ZnSO
47H
2O, 145 gram CoSO
47H
2O, 650 gram NiSO
46H
2O, 5 gram Sodium Glutamates are dissolved in the deionized water, are mixed with 1000 ml water solution A, add effective volume and are among 3 liters the reactor E.Take by weighing 250 gram NaOH, measure 40 milliliters of the ammoniacal liquor of 13 mol, be mixed with 1000 ml water solution B.Having under the condition of stirring, reacting according to above-mentioned technology the 2nd step, wherein the flow of aqueous solution B is～300 milliliters/hour.Temperature of reaction is 40 ± 0.5 ℃.
Take by weighing 50 gram CoSO
47H
2O, 2 gram Sodium Glutamates are dissolved in the deionized water, are mixed with 400 ml water solution C, add effective volume and are among 1.5 liters the reactor F.Take by weighing 15 gram NaOH, be mixed with 500 ml water solution D.Having under the condition of stirring, reacting according to above-mentioned technology the 2nd step, wherein the flow of aqueous solution D is～200 milliliters/hour.Temperature of reaction is 60 ± 0.5 ℃.
Mother liquor among reactor E and the reactor D is transferred to effective volume and is in 5 liters the aging tank, is exposed in the air under 60 ± 0.5 ℃, continues to stir 2.5 hours.
Product and mother liquor enter washer and simply wash with deionized water, utilize spray-dryer to carry out drying and granulation then, obtain spherical alpha-Ni (OH)
2Product.X=0.11 in the sample, y=0.07.The tap density that records this sample is 1.52g/cm
3Take by weighing 1.0 these samples of gram, 100 milligrams of graphite, 50 milligrams of acetylene blacks, 20 milligram 60% poly-tetrafluoro emulsion and suitable quantity of water, with the nickel foam is that collector is made positive pole, is negative pole with the hydrogen storage alloy, and 25 ℃ record the specific discharge capacity of this sample when 2 ampere electric currents discharge and recharge is 332mAh/g.
Embodiment two, add trisodium citrate 15 grams when obtain solution A, do not add Sodium Glutamate and rose vitriol: add Al in solution liquid B
2(SO
4)
33H
2O 100 grams, other forms feed liquid with embodiment one, finishes preparation process according to the operational condition among the embodiment.X=0.055 in the sample, y=0.07.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 these sample 2 ampere electric currents and discharging and recharging is 329mAh/g.
Embodiment three, add MnSO when obtain solution A
4H
2The O50 gram, disodium ethylene diamine tetraacetate (EDTA) 3 grams no longer add rose vitriol and other complexing agents; No longer add other metal salt solutions in the solution B, other is formed with embodiment one, finishes preparation process according to the operational condition among the embodiment one.X=0.06 in the sample, y=0.07.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 these sample 2 ampere electric currents and discharging and recharging is 322mAh/g.
Embodiment four, add FeSO when obtain solution A
4H
2The O45 gram, Seignette salt 6 grams no longer add other metal salt solutions, and other is formed with embodiment one, finishes preparation process according to the operational condition among the embodiment one.X=0.06 in the sample, y=0.07.The tap density that records the gained sample is 1.47g/cm
3, identical with anode formula among the embodiment one, recording the specific discharge capacity of this sample when 2 ampere electric currents discharge and recharge is 306mAh/g.
Embodiment five, add InSO when obtain solution A
4100 grams, quadrol 3.5 grams no longer add other metal salt solutions, and other is formed with embodiment one, finishes preparation process according to the operational condition among the embodiment one.X=0.095 in the sample, y=0.07.The tap density that records the gained sample is 1.49g/cm
3, identical with anode formula among the embodiment one, recording the specific discharge capacity of this sample when 2 ampere electric currents discharge and recharge 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, and other processing parameter is with embodiment one.After reaction, ageing and spraying drying, obtain sample.X=0.055 in the sample, y=0.07.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 2 ampere electric currents discharge and recharge is 298mAh/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.Other processing parameter is with embodiment one.After reaction, ageing and spraying drying, obtain product.X=0.11 in the sample, y=0.07.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 (2)
1, a kind of nanometer alpha-nickel hydroxide is characterized in that its structural formula is:
(Ni
1-2xM
2x(OH)
2(CO
3)
xNH
2O)
1-y(Co (OH)
2)
y, wherein M is a doped element, is respectively any among Al, Co, Fe, Mn or the In, wherein 5%＜x＜15%, 2%＜y＜10%
2, a kind of preparation method of nanometer alpha-nickel hydroxide is characterized in that this method may further comprise the steps:
(1) stock liquid preparation: preparation contains the nickel sulfate solution A of complexing agent and additive, wherein the concentration of single nickel salt is 0.1～2.5 mol, complexing agent is at least a material in trisodium citrate, Seignette salt, Sodium Glutamate and the disodium ethylene diamine tetraacetate, its concentration is 0.01～0.5 mol, additive is zinc sulfate or rose vitriol, and concentration is 0.001～0.5 mol; Prepare ammoniated aqueous sodium hydroxide solution B, making concentration sodium hydroxide wherein is 2～8 mol, and the concentration of ammonia is 0.1～2.0 mol; The salt of doped element is dissolved in solution A or the solution B, doped element is existed with the form of metal ion or acid ion, doped element is any among Al, Co, Fe, Mn and the In, and doping is: M (OH)
3/ Ni (OH)
2=(0.10～0.30)/1.0 mol ratio; Preparation contains the cobalt sulfate solution C of complexing agent, wherein the concentration of rose vitriol is 0.05～1.5 mol, complexing agent is at least a material in trisodium citrate, Seignette salt, Sodium Glutamate and the disodium ethylene diamine tetraacetate, and its concentration is 0.005～0.2 mol; Preparation aqueous sodium hydroxide solution D, its concentration is 2～8 mol;
(2) reaction: add 1 liter of solution A in reactor E in advance, the temperature in the controlling reactor is 30～80 ℃; Under stirring condition, solution B pumped into 250～350 milliliters/hour flow carry out chemical reaction in the reactor, in reaction process, the pH value of control reaction system terminal point is 11～13, the reaction times is 2～4 hours;
Add 400 ml soln C in reactor F in advance, the temperature in the controlling reactor is 20～60 ℃; Under stirring condition, solution D pumped into 150～250 milliliters/hour flow carry out chemical reaction in the reactor, in reaction process, the pH value of control reaction system is 10～11, the reaction times is 0.5～1.5 hour;
(3) ageing: will contain α-Ni (OH) among the reactor E
2Mother liquor and reactor F in contain Co (OH)
2Mother liquor transfer in the aging tank, continue down to stir 2.5 hours at 50 ℃;
(4) product and mother liquor enter washer and wash with deionized water, utilize spray-dryer to carry out drying and granulation then, obtain nano-level sphere α-Ni (OH)
2Product.
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| CNB011296151A CN1137851C (en) | 2001-06-22 | 2001-06-22 | Nanometer alpha-nickel hydroxide and its preparation |
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| CN1137851C true CN1137851C (en) | 2004-02-11 |
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| CN1303706C (en) * | 2003-07-25 | 2007-03-07 | 桂林工学院 | Microemulsion synthesizing method for doping nanometer multiphase alpha-Ni(OH)2 |
| 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 |
| CN111994965B (en) * | 2019-05-27 | 2022-08-19 | 湖北万润新能源科技股份有限公司 | Preparation method of precursor of LTH-structure ternary cathode material |
| CN110217756B (en) * | 2019-06-28 | 2022-09-20 | 桂林电子科技大学 | Preparation method and application of carbon-supported bismuth aluminum-based composite hydrogen production material |
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