CN1156042C - Process for preparing nm-class alpha-phase nickel hydroxide used as electrode material - Google Patents
Process for preparing nm-class alpha-phase nickel hydroxide used as electrode material Download PDFInfo
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- CN1156042C CN1156042C CNB011096942A CN01109694A CN1156042C CN 1156042 C CN1156042 C CN 1156042C CN B011096942 A CNB011096942 A CN B011096942A CN 01109694 A CN01109694 A CN 01109694A CN 1156042 C CN1156042 C CN 1156042C
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- aqueous solution
- initial
- nickel salt
- surfactant
- nickel hydroxide
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- 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
Abstract
The present invention relates to a method for preparing nanometer alpha-phase nickel hydroxide as an electrode material, which is characterized in that one or many kinds of trivalent metal ions and another kind of divalent zinc ions are simultaneously used for replacing nickel ions; generated nanometer alpha-phase nickel hydroxide is treated by aging so that the nanometer alpha-phase nickel hydroxide can stably exist in strong alkali liquor. The nanometer alpha-phase nickel hydroxide electrode material prepared by the present invention with the electrochemistry capacity of 316 mAh/g and the 0.5C5 electric discharge platform no less than 1.25V has the advantages of little electrode expansion and long service life, and is a new generation of nanometer nickel electrode material which meets the requirement of practicality.
Description
Technical field the present invention relates to a kind of process for preparing nm-class alpha-phase nickel hydroxide used as electrode material.Belong to Chemical Engineering and field of new.
The anodal active component of multiple storage batterys such as the existing NI-G of background technology, Ni-MH battery is β phase ball-shape nickel hydroxide.At present, the quality electrochemistry capacitance of β phase ball-shape nickel hydroxide electrode material is near theoretical value, and utilance does not have substantially and exploits potentialities near 100%.In order further to improve the quality electrochemistry capacitance of nickel hydroxide electrode material, improve nickel electrode discharge platform characteristic, improve electrode density and fast charging and discharging performance, prolong battery useful life, people begin one's study nanometer beta phase nickel hydroxide electrode material and class alpha-phase nickel hydroxide used as electrode material.The theoretical capacity (quality capacity) that has now found that class alpha-phase nickel hydroxide used as electrode material exceeds more than 60% than beta phase nickel hydroxide electrode material.In addition, in the normal charge and discharge process of nickel electrode, the beta phase nickel hydroxide electrode expands seriously when overcharging, and nickel electrode is caused irreversible lesion, has a strong impact on the nickel electrode life-span.Class alpha-phase nickel hydroxide used as electrode material is in charge and discharge process, and nickel electrode expands less, and fast charging and discharging performance is good, has higher discharge platform, high quality electrochemistry capacitance and long-life.Therefore, class alpha-phase nickel hydroxide used as electrode material, especially nm-class alpha-phase nickel hydroxide used as electrode material might become the positive level of the nickel active material of desirable green battery such as ni-mh of new generation.
Yet class alpha-phase nickel hydroxide used as electrode material can not stable existence in highly basic.At present main by introducing a large amount of trivalents or divalent metal element ion and anion in the lattice of class alpha-phase nickel hydroxide, obtain a kind of two oxyhydroxides of stable hydrotalcite type.These compounds have the structure similar to class alpha-phase nickel hydroxide, and are stable in the highly basic medium, might be as the active material of high-performance nickel electrode.The trivalent metallic element of prior art mainly contains Co
3+, Mn
3+, Fe
3+, Al
3+Deng, divalent metal has Zn
2+Deng, but result of study so far proves that mix these metal ions respectively separately, its result is all undesirable.Co
3+Replace class alpha-phase nickel hydroxide and can obtain the better quality electrochemistry capacitance, but discharge platform is low; Fe
3+, Mn
3+Replace class alpha-phase nickel hydroxide and can obtain higher discharge platform, but the quality electrochemistry capacitance is low; Al
3+Replace class alpha-phase nickel hydroxide when higher alternative amount, nickel electrode activity function and heavy-current discharge performance are not good, when low replacement amount, are unfavorable for the cycle life of nickel electrode again.Reached 290mAh/g though aluminum current replaces the biggest quality electrochemistry capacitance of class alpha-phase nickel hydroxide used as electrode material, its cyclical stability is relatively poor, does not have practical value; Zn
2+The cycle life that replaces class alpha-phase nickel hydroxide used as electrode material is low, and cyclical stability is poor, does not have practical value equally.In a word, the class alpha-phase nickel hydroxide used as electrode material of prior art still is in the laboratory research stage, does not all reach practical requirement.
Summary of the invention method of the present invention is different with existing technology.The objective of the invention is to propose a kind of process for preparing nm-class alpha-phase nickel hydroxide used as electrode material.Utilize chemical coprecipitation, initial caustic-alkali aqueous solution at least by a kind of highly basic (NaOH or KOH) and a kind of sustained release agent (as Na
2C
2O
3, urea etc.) form; Initial nickel salt aqueous solution is by nickel salt (sulfate or nitrate, hydrochloride), trivalent metal salt (sulfate or nitrate or hydrochloride), divalent zinc salt (sulfate or nitrate, hydrochloride), at least a anion (Cl
-Or CO
3 2-, SO
4 2-, NO
3 -Deng) and mixing compositions such as at least a surfactant polysorbate (Tween), shrink sorbitol monooleate (Span) or Triton X-100 (OP-10).
The invention is characterized in simultaneously to replace class alpha-phase nickel hydroxide, and mix at least a anion with trivalent metal ion and two kinds of ions of divalent zinc ion; Feature of the present invention also is with the nucleation rate of sustained release agent control nickel hydroxide and with surfactant control small-particle stability, to obtain class alpha-phase nickel hydroxide used as electrode material nano-scale, perfect crystalline; Another feature of the present invention is the nm-class alpha-phase nickel hydroxide that generates to be done ageing handle, and makes it keep stable in strong base solution.
The present invention realizes like this.
At first prepare initial nickel salt aqueous solution and initial caustic-alkali aqueous solution.Nickel salt aqueous solution: wherein nickel salt concentration is 0.1mol/l～0.2mol/l, the trivalent metal salinity is 0.1mol/l～0.3mol/l, divalent zinc salt concentration is 0.005mol/l～0.015mol/l, surfactant concentration is 0.2g/l～1.5g/l, and anion concentration is 0.01mol/l～0.04mol/l.Through ultrasonic concussion 3～5 minutes, mix standby above-mentioned initial nickel salt aqueous solution; Initial caustic-alkali aqueous solution: the concentration of caustic alkali is 0.1mol/l～0.3mol/l, and the concentration of sustained release agent is 0.2mol/l～0.5mol/l, with above-mentioned initial caustic-alkali aqueous solution dissolving, through ultrasonic concussion 3 minutes～5 minutes, mixes standby.In the initial nickel salt aqueous solution and initial caustic-alkali aqueous solution while injecting reactor that prepare, 15 ℃～50 ℃ of reaction temperatures, reacting liquid pH value is 7～10, and mixing speed is 500 rev/mins～1500 rev/mins, and the reaction time is 1 hour～3 hours.Reaction product is through 60 ℃, and ageing more than 48 hours is cleaned, filtered, and through 60 ℃ of heat dryings, obtains nm-class alpha-phase nickel hydroxide used as electrode material, about average particle size 10 nanometers; Also can obtain nanostructure class alpha-phase nickel hydroxide electrode material through ultrasonic dispersion, cleaning and spray drying.The nanostructure class alpha-phase nickel hydroxide electrode material that obtains with spray drying is highdensity, and its tap density can reach 3.0g/cm
3Quality electrochemistry capacitance with the nm-class alpha-phase nickel hydroxide used as electrode material of manufacturing of the present invention can reach 316mAh/g, and the volume electrochemistry capacitance surpasses 700mAh/cm
3, 0.5C
5Discharge platform＞1.25V, nickel electrode has series of advantages such as expansion is little, good stability, long-life.
All with the deionized water preparation, initial caustic-alkali aqueous solution: 300ml contains 0.2mol/l NaOH, 0.4mol/lNa for initial nickel salt aqueous solution of embodiment and initial caustic-alkali aqueous solution
2C
2O
3Initial nickel salt aqueous solution: 300ml, the nitrate concentration of nickel, aluminium, zinc is respectively 0.17mol/l, 0.02mol/l, 0.01mol/l contains the OP-101 gram, HCl 1g.Initial nickel salt aqueous solution and the ultrasonic concussion of initial caustic-alkali aqueous solution difference 3～5 minutes with preparation, then in the while injecting reactor, the temperature of mixed reaction solution is 25 ℃, the pH value is 8, and in 1 hour 30 minutes reaction time, mixing speed is 1000 rev/mins, 60 ℃ of ageing temperature, 72 hours time is with washed with de-ionized water, filtration, through 60 ℃ of dryings.Nm-class alpha-phase nickel hydroxide average grain diameter 10 nanometers that obtain, spherical in shape.Its quality electrochemistry capacitance is 316mAh/g, 0.5C
5Discharge platform is 1.25V, and electrode does not have obvious expansion, do not find shedding.
Claims (8)
1 one kinds of process for preparing nm-class alpha-phase nickel hydroxide used as electrode material, comprise: the initial nickel salt aqueous solution and the initial caustic-alkali aqueous solution that contains at least a sustained release agent that contain at least a surfactant, surfactant is polysorbate, shrink sorbitol monooleate or Triton X-100 in the initial nickel salt aqueous solution, it is 0.2g/l-1.5g/l that initial nickel salt aqueous solution contains surfactant concentration, and sustained release agent is Na in the initial caustic-alkali aqueous solution
2C
2O
3, urea, it is 0.2mol/l-0.5mol/l that initial caustic-alkali aqueous solution contains sustained release agent concentration; Simultaneously in the injecting reactor, reaction product is through ageing, ultrasonic dispersion, cleaning and spray drying behind sonic oscillation for the initial nickel salt aqueous solution that will contain surfactant respectively and the initial caustic-alkali aqueous solution that contains sustained release agent.
2 manufacture methods as claimed in claim 1, the initial nickel salt aqueous solution that wherein contains surfactant is made up of nickel salt, trivalent metal salt, divalent zinc salt and at least a anion.
3 as claim 1,2 described manufacture methods, contain wherein that nickel salt, trivalent metal salt, divalent zinc salt are nitrate, sulfate or hydrochloride in the initial nickel salt aqueous solution of surfactant, and at least a anion is Cl
-, NO
3 -, SO
4 2-, CO
3 2-, anion is by HCl, HNO
3, H
2SO
4, Na
2CO
3Or NaHCO
3Provide.
4 manufacture methods as claimed in claim 3, contain wherein that nickel salt concentration is 0.1mol/l-0.2mol/l in the initial nickel salt aqueous solution of surfactant, the trivalent metal salinity is 0.01mol/l-0.03mol/l, divalent zinc salt concentration is 0.005mol/l-0.015mol/l, contains the anion that at least a concentration is 0.01mol/l-0.04mol/l.
5 manufacture methods as claimed in claim 1 contain wherein that caustic sodium concentration is 0.1mol/l-0.3mol/l in the initial caustic-alkali aqueous solution of sustained release agent.
6 manufacture methods as claimed in claim 1, the initial nickel salt aqueous solution that wherein contains surfactant uses preceding through sonic oscillation 3-5 minute with the initial caustic-alkali aqueous solution that contains sustained release agent.
7 as claim 1,5,6 described manufacture methods, the initial caustic-alkali aqueous solution that wherein contains the initial nickel salt aqueous solution of surfactant and contain sustained release agent is behind sonic oscillation simultaneously in the injecting reactor, in the reactor wherein blender is housed, mixing speed is 500-1500 rev/min.
8 manufacture methods as claimed in claim 7, wherein reactor internal reaction liquid temp is 15 ℃-50 ℃, and the reactant liquor pH value is 7-10, and the reaction time is 1 hour-3 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011096942A CN1156042C (en) | 2001-03-20 | 2001-03-20 | Process for preparing nm-class alpha-phase nickel hydroxide used as electrode material |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011096942A CN1156042C (en) | 2001-03-20 | 2001-03-20 | Process for preparing nm-class alpha-phase nickel hydroxide used as electrode material |
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| Publication Number | Publication Date |
|---|---|
| CN1313644A CN1313644A (en) | 2001-09-19 |
| CN1156042C true CN1156042C (en) | 2004-06-30 |
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ID=4658089
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|---|---|---|---|
| CNB011096942A Expired - Fee Related CN1156042C (en) | 2001-03-20 | 2001-03-20 | Process for preparing nm-class alpha-phase nickel hydroxide used as electrode material |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8017157B2 (en) | 2002-05-09 | 2011-09-13 | Osiris Therapeutics, Inc. | Method of treating a wound with acidified plasma or serum |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1303706C (en) * | 2003-07-25 | 2007-03-07 | 桂林工学院 | Microemulsion synthesizing method for doping nanometer multiphase alpha-Ni(OH)2 |
| CN100334003C (en) * | 2005-09-29 | 2007-08-29 | 华南理工大学 | Nanometer alpha-nickel hydroxide and its prepn |
| CN101908623B (en) * | 2010-07-30 | 2012-07-04 | 广州市云通磁电有限公司 | Method for preparing silver-doped nano nickel hydroxide anode material |
| CN106745133B (en) * | 2017-01-24 | 2018-03-20 | 武汉工程大学 | A kind of preparation method of hydroxide not soluble in water |
| CN107381663B (en) * | 2017-06-16 | 2019-05-14 | 上海交通大学 | A kind of nickel oxide nano flake gas sensor and preparation method based on aluminium doping |
| CN113265666A (en) * | 2021-04-12 | 2021-08-17 | 江苏九然新能源科技有限公司 | One-dimensional Fe-doped alpha-Ni (OH)2Nanobelt catalyst and preparation method and application thereof |
-
2001
- 2001-03-20 CN CNB011096942A patent/CN1156042C/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8017157B2 (en) | 2002-05-09 | 2011-09-13 | Osiris Therapeutics, Inc. | Method of treating a wound with acidified plasma or serum |
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| Publication number | Publication date |
|---|---|
| CN1313644A (en) | 2001-09-19 |
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