CN1210153A - One-step process of nickle hydroxide electrolysing - Google Patents
One-step process of nickle hydroxide electrolysing Download PDFInfo
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- CN1210153A CN1210153A CN98107135A CN98107135A CN1210153A CN 1210153 A CN1210153 A CN 1210153A CN 98107135 A CN98107135 A CN 98107135A CN 98107135 A CN98107135 A CN 98107135A CN 1210153 A CN1210153 A CN 1210153A
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Abstract
A process for preparing nickel hydroxide based on electrochemical deposition principle includes such technological steps as electrolyzing the electrolyte containing chloride of alkali-metal with constant direct current under the condition of stirring to convert metal nickel nickel hydroxide, separating the nickel hydroxide from electrolyte, washing in water, and drying to spherical or ball-like particles of nickel hydroxide. The obtained nickel hydroxide is suitable to make positive electrode of alkaline accumulator.
Description
The invention belongs to the non-sintered type nickel oxyhydroxide active substance manufacturing technology field of nickel series Edison battery.
The core component of nickel series Edison battery nickel oxyhydroxide pole plate is a nickel hydroxide.Nickel oxyhydroxide has sintered type and non-sintered type two big classes.The sintered type nickel oxyhydroxide is that the nickel hydroxide of sintered porous Ni substrate through chemical impregnation or the generation of electrochemical impregnation process is deposited in the micropore of porous sintered nickel, so the sintered type nickel oxyhydroxide need not to prepare separately nickel hydroxide, but the non-sintered type nickel oxyhydroxide needs to prepare separately nickel hydroxide.The present invention be directed to non-sintered type nickel oxyhydroxide ball-shape nickel hydroxide, a kind of preparation method who is proposed.
The preparation method of ball-shape nickel hydroxide can be divided into two classes basically.One class is to be raw material with soluble nickel salt and caustic alkali, is having or is not having under the complexing agent existence condition, the chemical precipitation method of nickel salt and the reaction of caustic alkali generation double decomposition precipitation.Another kind of is to be raw material with the elemental nickel, or through the electrolytic oxidation hydrolysis, or through the precipitator method non-chemically of chemical oxidation hydrolysis.
Chinese patent application 94101458.4, the clear 61-104565 of Japanese JP, the flat 1-187765 of JP, the flat 2-6340 of JP once addressed the chemical precipitation method of ball-shape nickel hydroxide among the flat 7-211318 of JP.Its basic skills is: with the single nickel salt or the mixed Ni salts solution of solubility or contain nickel salt solution, the caustic solution of ammonia/ammonium compound, or ammonia/ammonium compound solution and flowing in the input reactor.Under the concentration of controlling each solution, flow, pH value in reaction, temperature of reaction, reaction times, stirring intensity, ammonia/conditions such as nickel mol ratio, allow nickel salt and caustic alkali generation double decomposition precipitation react, preparing particle shape through separation, washing, drying is the spheric nickel hydroxide powder.
Chemical precipitation method is the ball-shape nickel hydroxide preparation method who generally uses at present, the subject matter of its existence is: (1) has the by product of contaminate environment to generate, these by products are different according to used nickel salt and caustic alkali kind, may be sodium sulfate, vitriolate of tartar, SODIUMNITRATE, saltpetre, sodium-chlor, Repone K.These by products or because of no recovery value or because of reclaiming directly discharging causes the soil salinization.(2) need the technological factor controlled many and difficultly realize stable control in the production process, cause the difficult control of homogeneity of different batches product performance.(3) can not closed cycle production, have the nickel of a great deal of in the reaction mother liquor with the complexing solubilised state, this part nickel needs can reclaim through special processing, causes the production cost of unit product higher.If reaction mother liquor is directly discharged, cause environmental pollution on the one hand, also can strengthen production cost on the other hand because of the nickel loss.(4) needing with cell-grade nickel salt and caustic alkali is raw material, is the unit cost height of raw material with the higher electrolytic metal nickel of purity more directly.
Chinese patent application 95114810.9, european patent application 90104985.8 disclose a kind of method for preparing nickel hydroxide with the metallic carbonyls nickel powder.Its method is at first metal nickel powder to be suspended in the aqueous solution that contains ammonia/ammonium compound, to the suspension aerating oxygen, makes metal nickel powder be converted into nickel hydroxide.The problem of this method is: (1) requires to reach 0.2m with specific surface
2The metal nickel powder of/g, and the price of this metal nickel powder itself is just higher, causes the cost of made nickel hydroxide higher.The simultaneous out-phase reaction of gas, liquid, solid three-phase takes place in (2) the preparation system, and it is limited that metal nickel powder is converted into the transformation efficiency of nickel hydroxide, needs through the magnetic separating treatment, isolate do not transform, residue in the metal nickel powder in the nickel hydroxide product.
U.S. Pat 5391265 and Chinese patent application 94119619.4 also disclose a kind of by metallic nickel through electrolytic anodization, prepare the method for ball-shape nickel hydroxide.Its method divides two step four-stages to carry out: (1) electrolysis in the electrolytic solution of sulfur-bearing acid group and chlorine root, anodized metallization nickel prepares gluey nickel hydroxide.(2) handle gluey nickel hydroxide with sodium hydroxide solution and become the reactive hydrogen nickel oxide.(3), the reactive hydrogen nickel oxide is converted into the hexaammine nickel chloride precipitation with the strong aqua processing reaction nickel hydroxide that contains sodium-chlor.(4) with the muriate of hot sodium hydroxide solution processing hexamine nickel, hexaammine nickel chloride is changed into ball-shape nickel hydroxide.The deficiency of this method is: (1) needs just to prepare the ball-shape nickel hydroxide that tap density is 2.1g/ml through four-stage, and preparation workshop section is many and make the cost of nickel hydroxide product higher.(2) electrolytic metal nickel prepares in the electrolytic process of gluey nickel hydroxide workshop section, still needs to add in electrolytic solution continuously nickel sulfate solution.Cause the cumulative bad of sulfate radical content in the electrolytic solution to increase, make electrolytic solution can not realize the closed cycle use fully, still certain discharging will be arranged.(3) the prepared nickel hydroxide of electrolysis workshop section is a jelly, and this jelly residues in the washing water in washing, pressure-filtering process inevitably.Because the amount of washing water is quite big, it is impossible recycling fully, but if this washing water that contain the gluey nickel hydroxide of a great deal of of discharging can cause environmental pollution on the one hand, can cause the loss of nickel on the other hand and strengthens production cost.(4) the prepared nickel hydroxide of electrolysis workshop section is a jelly, no matter this jelly is to stir or not under the agitation condition, the phenomenon of anode and negative electrode all may occur adhering to.If adhere to anode, the anodic oxidation of inferior nickel can take place, and anodic current efficiency is descended.If adhere to negative electrode, can increase the overpotential of hydrogen evolution of negative electrode, and bath voltage is raise.(5) only in low temperature, strong aqua, could exist because of hexaammine nickel chloride with insoluble attitude precipitation forms.So in colloidal state hydroxide production hexaammine nickel chloride process, need to use strong aqua just can make nickel hydroxide comparatively complete to the sedimentary conversion of hexaammine nickel chloride.Make consumption increase, the ammonia content possibility in the Working environment atmosphere of ammonia higher like this.
The objective of the invention is to provide a kind of is gone on foot, need not again through any chemical treatment or conversion through electrolysis one by elemental nickel, prepare the method that granule-morphology is sphere or class ball-shape nickel hydroxide, this method also will be a kind of method for preparing ball-shape nickel hydroxide under the mode that the complete closed cycle of by product, electrolytic solution that does not produce any possibility contaminate environment is used continuously.
The object of the present invention is achieved like this:
With elemental metals nickel plate or the elemental metals nickel that places titanium indigo plant as anode, with the steel plate of elemental nickel plate or nickel plating or nickel plating molybdenum alloy as negative electrode, place electrolytic solution, under agitation condition, use the direct current constant-current electrolysis, and in electrolytic process in electrolytic solution, to add ammonia with the suitable flow of used electric current; The nickel hydroxide that electrolytic process generates is separated from electrolytic solution, and through washing, drying, being prepared into particle shape is sphere or class spheric nickel hydroxide.
The electrolytic solution here is the aqueous solution that contains ammonia or ammonium compound, alkali metal chloride, base metal nitrate, and it consists of: the concentration of ammonia or ammonium is 0.05-0.8M, and optimum concn is 0.15-0.4M; The concentration of chlorine root is 0.5-4.5M, and optimum concn is 1.5-2.5M; The concentration of nitre root is 0-0.3M, and optimum concn is 0.02-0.06M.Described basic metal is at least a kind of in lithium, sodium, the potassium.
The current density of constant-current electrolysis is 1-6Adm among the present invention
-2The temperature of electrolytic solution is 10-60 ℃.
The process of ammonification is to add ammonia continuously or be interrupted interpolation ammonia in electrolytic solution after electrolysis is carried out 0-2 hour.The ammonia that it replenished can be ammoniacal liquor, also can be ammonia.Add the amount of ammonia and the ratio of the selected electric current of actual electrolyzer is: 1-5molNH
3/ h (52.6A) promptly calculates by 100% current efficiency, makes NH
3With Ni
2+Mol ratio be 1-5, optimum value is 2-4.
By the solid-state nickel hydroxide that electrolysis generated, continuing under the electrolytic condition, the mean residence time in electrolytic solution is 10-150 hour, most optimal retention time is 30-120 hour.Its with can be separating of electrolytic solution step static, decant mode, also can be continuous discharge, filter type.
Isolate the electrolytic solution behind the solid-state nickel hydroxide among the present invention, need not to handle the soluble state nickel that residues in the electrolytic solution, after only needing to adjust the concentration of chlorine root, nitrate radical and alkalimetal ion, can return electrolyzer and recycle.
Compared with prior art, the present invention has outstanding feature: (1) ball-shape nickel hydroxide only needs one step of electrolysis to generate, and production process is few, and spatiotemporal efficiency is higher; (2) can realize closed cycle zero release production, not produce the by product of any possibility contaminate environment; (3) processing parameter is realized stable control easily, an even property that helps improving the quality of products.
Accompanying drawing is a schematic flow sheet of the present invention.
With reference to the accompanying drawings the present invention is further described below below.
In the accompanying drawings, 1 is anode, and 2 is negative electrode, and 3 is electrolytic cell, and 4 is electrolyte, and 5 for ammoniacal liquor adds pipe, and 6 are The constant flow pump of control ammoniacal liquor flow, 7 is dc constant flowing power, and 8 is agitator, and 9 is filtering settling pond.
Wherein: anode 1 is made of the metallic nickel behind electrorefining, its form or metal nickel plate or put Metal nickel block in titanium basket, its effect provide the required nickel of preparation nickel hydroxide. Requirement to its purity Higher, both can not contain and can under electrolytic condition, dissolve, may produce the alkaline storage battery nickel oxyhydroxide again The impurity element of adverse effect is such as copper, thallium, chromium etc. Certainly anode can be equipped with the useful unit of proper proportion Plain such as cobalt, cadmium, zinc etc., since prepare the nickel hydroxide that contains corresponding interpolation element;
The water that electrolyte 4 forms for containing ammonia or ammonium compounds, alkali metal chloride, alkali nitrates Solution, wherein ammonia or ammonium root concentration are 0.05-0.8M, optium concentration is 0.15-0.4M; Chlorine root concentration is 0. 5-4.5M optium concentration is 1.5-2.5M; The concentration of nitrate anion is 0-0.3M, and optium concentration is 0.02-0. 06M; Corresponding cation is at least a kind of in alkali metal lithium, sodium, the potassium. Wherein the effect of ammonia or ammonium root is, With Ni2+Form [Ni (NH3)
n]
2+To slow down the nucleation rate of nickel hydroxide precipitate; The effect of chlorion is Guarantee on the one hand the anionic electroconductive of electrolyte, be the normal dissolving that guarantees nickel anode on the other hand, prevent The passivation of nickel anode; The effect of nitrate anion is to prevent nickel ion form deposition, guarantor with metallic nickel on negative electrode The cathode efficiency of card take the preparation nickel hydroxide as standard; Used alkali metal ion is lithium, sodium, potassium ion, Its effect is the cationic conductivity that guarantees electrolyte.
Anode 1 and negative electrode 2 are placed electrolyte 4, open agitator 8, electrolyte 4 is stirred; Under the stirring, connect dc constant flowing power 7, directly carry out the direct current electrolysis; Used galvanic electric current is close Degree is controlled at 1-6A/dm2, corresponding tank voltage is 2.4-12V, current density is not so large as to make anode 1 electricity The position reaches the degree of analysing chlorine; And adding pipe 5 by ammoniacal liquor in electrolytic process adds in electrolyte 4 continuously Ammonification, the flow and the used electric current that add ammonia are complementary, and are controlled by the constant flow pump 6 of control ammoniacal liquor flow, add The time of ammonification, difference is generally advanced in electrolysis according to the difference that contains ammonia or ammonium compounds amount in the liquid at the bottom of the electrolysis 4 Row began to electrolyte 4 discontinuous or continuous adding ammonia after 0-2 hour. Add ammonia amount should be controlled at Making ammonia/nickel mol ratio is 1-5, and best ammonia/nickel mol ratio is 2.0-4.0. The meaning of ammonia/nickel mol ratio herein By in the unit interval the molal quantity of adding ammonia pressed 100% current efficiency calculating gained unit with using electric current Produce the ratio of the molal quantity of nickel ion in time. According to the requirement to prepared nickel hydroxide density, control The time that electrolysis processed continues, prepare the above at least electrolysis 40 of ball-shape nickel hydroxide of tapped density 2.0g/ml More than individual hour. The prolongation electrolysis duration can be improved density and the degree of crystallinity of nickel hydroxide. Whole electrolysis Process must be carried out under stirring condition, and the purpose of stirring is the uniformity that guarantees whole electrolyte property, and is anti-Cathodic region and anode region electrolyte only appear in the difference of the aspects such as composition and pH. Because electrolytic process generates Nickel hydroxide be the ball-shape nickel hydroxide with certain degree of crystallinity, so in whole electrolytic process, can not send out Give birth to the adhesion of nickel hydroxide on negative electrode or anode.
In electrolytic process, the nickel hydroxide that needs constantly to generate is separated. Because this method institute hydrogen manufacturing Nickel oxide just generates with sphere or spherical particle form in electrolytic cell 3, and density is higher, so hydrogen-oxygen Changing nickel realizes with taking the static natural subsidence of batch (-type) and decant mode separating of electrolyte 4; But for carrying High score preferably adopts continuous discharge, filter type from speed, is about to nickel hydroxide and electrolyte 4 mixed liquors certainly The bottom of electrolytic cell 3 enters sedimentation and filtration in the filtering settling pond 9 continuously, separates. Isolated electrolysis Liquid recycles through online detection with after adjusting each component concentration. Isolated electrolyte is except containing original electricity Separate outside chlorine root, nitrate anion, alkali metal ion, free ammonia or the ammonium root contained in the liquid, also have solubility ammonia nickel network Ion, but the existence of solubility ammonia nickel complex ion does not affect recycling of electrolyte.
Embodiment 1:
275 gram KCl are mixed with 1200 ml solns and put into electrolyzer as electrolytic solution, and respectively as negative electrode and anode, the degree of depth of this two electrodes immersion electrolytic solution is 10cm with two areas electrolytic metal nickel plate that is 6.5 * 13.5cm.Adding weight percent concentration in electrolysis forward direction electrolytic solution is the strong aqua 20ml of 25-28% (about 14M), and after stirring, the direct current with 2A under whipped state carries out electrolysis.After electrolysis is carried out 1 hour, with the ammoniacal liquor of the flow of 2.0ml/5min constant current in electrolytic solution interpolation 4.9M.The temperature that electrolytic solution in the process is carried out in electrolysis rises to 33 ℃ gradually by 31 ℃.After electrolysis is carried out 40 hours, stop electrolysis and stirring, electrolytic solution is separated out in nickel hydroxide natural subsidence hypsokinesis to be generated.After isolated nickel hydroxide washing, oven dry is 10 hours under 50 ℃ of temperature of what, crosses 300 mesh sieves, and obtaining 109.2 gram particle shapes is the nickel hydroxide of 2.1g/ml for spherical, tapped density.The current efficiency of this electrolytic process is 78.7%.
Embodiment 2:
With 195 gram KCl and 2 gram NH
4NO
3Be mixed with 1200 ml solns and put into electrolyzer as electrolytic solution, respectively as negative electrode and anode, the degree of depth that this two electrode immerses electrolytic solution is 10cm with two areas electrolytic metal nickel plate that is 6.5 * 13.5cm.Adding weight percent concentration in electrolysis forward direction electrolytic solution is the strong aqua 10ml of 25-28% (about 14M), and after stirring, the direct current with 2A under whipped state carries out electrolysis.After electrolysis is carried out 1 hour, with the ammoniacal liquor of the flow of 2.0ml/5min constant current in electrolytic solution interpolation 4.9M.The temperature that electrolytic solution in the process is carried out in electrolysis rises to 33 ℃ gradually by 31 ℃.Electrolysis time is 130 hours, stops electrolysis and stirring then, and electrolytic solution is separated out in nickel hydroxide natural subsidence hypsokinesis to be generated.After isolated nickel hydroxide washing, oven dry is 10 hours under 50 ℃ of temperature of what, crosses 300 mesh sieves, and obtaining 385 gram particle shapes is the nickel hydroxide of 2.04g/ml for spherical, tapped density.The current efficiency of this electrolytic process is 85.4%.
Embodiment 3:
183 gram KCl and 64 gram LiCl are mixed with 1200 ml solns and put into electrolyzer as electrolytic solution, and respectively as negative electrode and anode, the degree of depth of this two electrodes immersion electrolytic solution is 10cm with two areas electrolytic metal nickel plate that is 6.5 * 13.5cm.Adding weight percent concentration in electrolysis forward direction electrolytic solution is the strong aqua 20ml of 25-28% (about 14M), and after stirring, the direct current with 2A under whipped state carries out electrolysis.After electrolysis is carried out 1 hour, with the ammoniacal liquor of the flow of 2.0ml/5min constant current in electrolytic solution interpolation 4.9M.The temperature that electrolytic solution in the process is carried out in electrolysis rises to 33 ℃ gradually by 31 ℃.Electrolysis time is 55 hours, stops electrolysis and stirring then, and electrolytic solution is separated out in nickel hydroxide natural subsidence hypsokinesis to be generated.After isolated nickel hydroxide washing, oven dry is 10 hours under 50 ℃ of temperature of what, crosses 300 mesh sieves, and obtaining 102.5 gram particle shapes is the nickel hydroxide of 1.88g/ml for spherical, tapped density.The current efficiency of this electrolytic process is 53.7%.
Embodiment 4:
275 gram NaCl are mixed with 1200 ml solns and put into electrolyzer as electrolytic solution, and respectively as negative electrode and anode, the degree of depth of this two electrodes immersion electrolytic solution is 10cm with two areas electrolytic metal nickel plate that is 6.5 * 13.5cm.Adding weight percent concentration in electrolysis forward direction electrolytic solution is the strong aqua 20ml of 25-28% (about 14M), and after stirring, the direct current with 2A under whipped state carries out electrolysis.After electrolysis is carried out 1 hour, with the ammoniacal liquor of the flow of 2.0ml/5min constant current in electrolytic solution interpolation 4.9M.The temperature that electrolytic solution in the process is carried out in electrolysis rises to 33 ℃ gradually by 31 ℃.Electrolysis time is 40 hours, stops electrolysis and stirring then, and electrolytic solution is separated out in nickel hydroxide natural subsidence hypsokinesis to be generated.After isolated nickel hydroxide washing, oven dry is 10 hours under 50 ℃ of temperature of what, crosses 300 mesh sieves, and obtaining 121 gram particle shapes is the nickel hydroxide of 1.9g/ml for spherical, tapped density.The current efficiency of this electrolytic process is 87.2%.
Embodiment 5:
With 195 gram NaCl and 3 gram NH
4NO
3Be mixed with 1200 ml solns and put into electrolyzer as electrolytic solution, respectively as negative electrode and anode, the degree of depth that this two electrode immerses electrolytic solution is 10cm with two areas electrolytic metal nickel plate that is 6.5 * 13.5cm.No longer add ammoniacal liquor to electrolytic solution before electrolysis is carried out, directly the direct current with 2A carries out electrolysis under whipped state.After electrolysis is carried out 1 hour, with the ammoniacal liquor of the flow of 2.0ml/5min constant current in electrolytic solution interpolation 4.9M.The temperature that electrolytic solution in the process is carried out in electrolysis rises to 33 ℃ gradually by 31 ℃.After electrolysis is carried out 110 hours, stop electrolysis and stirring then, electrolytic solution is separated out in nickel hydroxide natural subsidence hypsokinesis to be generated.After isolated nickel hydroxide washing, oven dry is 10 hours under 50 ℃ of temperature of what, crosses 300 mesh sieves, and obtaining 305 gram particle shapes is the nickel hydroxide of 2.17g/ml for spherical, tapped density.The current efficiency of this electrolytic process is 80%.
Claims (9)
1, a kind of one-step process of nickle hydroxide electrolysing, it is characterized in that elemental metals nickel plate or the elemental metals nickel that places titanium indigo plant as anode, with the steel plate of elemental nickel plate or nickel plating or nickel plating molybdenum alloy as negative electrode, place electrolytic solution, under agitation condition, use the direct current constant-current electrolysis, and in electrolytic process in electrolytic solution, to add ammonia with the suitable flow of used electric current; The nickel hydroxide that electrolytic process generates is separated from electrolytic solution, and through washing, drying, being prepared into particle shape is sphere or class spheric nickel hydroxide.
2, method according to claim 1 is characterized in that described electrolytic solution is the aqueous solution that contains ammonia or ammonium compound, alkali metal chloride, base metal nitrate, and it consists of: the concentration of ammonia or ammonium is 0.05-0.8M, and optimum concn is 0.15-0.4M; The concentration of chlorine root is 0.5-4.5M, and optimum concn is 1.5-2.5M; The concentration of nitre root is 0-0.3M, and optimum concn is 0.02-0.06M.Described basic metal is at least a kind of in lithium, sodium, the potassium.
3, method according to claim 1, the current density that it is characterized in that constant-current electrolysis is 1-6Adm
-2
4, method according to claim 1, the temperature that it is characterized in that electrolytic solution is 10-60 ℃.
5, method according to claim 1 is characterized in that the ammonification process is for adding ammonia continuously or be interrupted interpolation ammonia in electrolytic solution after 0-2h is carried out in electrolysis.
6, according to claim 1 and 5 described methods, it is characterized in that the ammonia that is replenished can be ammoniacal liquor, also can be ammonia.Add the amount of ammonia and the ratio of the selected electric current of actual electrolyzer is: 1-5molNH
3/ h: 52.6A.
7, method according to claim 1 is characterized in that the solid-state nickel hydroxide that electrolysis generates, and is continuing under the electrolytic condition, and the mean residence time in electrolytic solution is 10-150 hour, and most optimal retention time is 30-120 hour.
8, according to claim 1 and 7 described methods, it is characterized in that nickel hydroxide and separating of electrolytic solution can be step static, decant modes, also can be continuous discharge, filter type.
9, according to claim 1 and 8 described methods, it is characterized in that isolating the electrolytic solution behind the solid-state nickel hydroxide, need not to handle the soluble state nickel that residues in the electrolytic solution, after only needing to adjust the concentration of chlorine root, nitrate radical and alkalimetal ion, can return electrolyzer and recycle.
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|---|---|---|---|
| CN98107135A CN1062612C (en) | 1998-02-27 | 1998-02-27 | One-step process of nickle hydroxide electrolysing |
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|---|---|---|---|
| CN98107135A CN1062612C (en) | 1998-02-27 | 1998-02-27 | One-step process of nickle hydroxide electrolysing |
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| CN1062612C CN1062612C (en) | 2001-02-28 |
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Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000068462A1 (en) * | 1999-05-07 | 2000-11-16 | H.C. Starck Gmbh | Method for producing nickel hydroxides |
| CN1311104C (en) * | 2003-09-28 | 2007-04-18 | 北京航空航天大学 | Process for preparing nickel hydroxide material using electric deposition method |
| CN102249349A (en) * | 2011-04-26 | 2011-11-23 | 北京化工大学 | Multi-component doped spherical nano nickel hydroxide synthesized by chemical-electrochemical combined method |
| CN102603016A (en) * | 2012-03-08 | 2012-07-25 | 中国科学院苏州纳米技术与纳米仿生研究所 | Method for preparing nanometer nickel oxide and application of method |
| CN107190274A (en) * | 2017-05-10 | 2017-09-22 | 东北大学 | A kind of method that nickel chloride electricity conversion directly prepares nickel hydroxide |
| CN107236964A (en) * | 2017-05-10 | 2017-10-10 | 东北大学 | A kind of method that cobalt chloride electricity conversion directly prepares cobalt hydroxide |
| CN107236963A (en) * | 2017-05-10 | 2017-10-10 | 东北大学 | A kind of method that chlorination ferroelectricity conversion directly prepares iron hydroxide or iron oxide |
| CN107254687A (en) * | 2017-05-10 | 2017-10-17 | 东北大学 | A kind of method that electrolytic chlorination rare earth prepares rare earth oxide |
| CN109755029A (en) * | 2019-01-31 | 2019-05-14 | 燕山大学 | A kind of preparation method of flower piece shape nano-nickel oxide |
| CN110129825A (en) * | 2019-05-23 | 2019-08-16 | 天津市大陆制氢设备有限公司 | A kind of efficient Ni/Ni (OH)2Hydrogen-precipitating electrode and preparation method thereof |
| CN111118521A (en) * | 2020-01-17 | 2020-05-08 | 西北师范大学 | Method for preparing nano nickel hydroxide by electrolytic process |
| CN113120978A (en) * | 2021-04-19 | 2021-07-16 | 贵州源驰新能源科技有限公司 | A kind of Ni (OH)2And method for preparing the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57138775A (en) * | 1981-02-20 | 1982-08-27 | Matsushita Electric Ind Co Ltd | Production of electrode for alkaline storage battery |
| JPH08315850A (en) * | 1995-05-18 | 1996-11-29 | Toshiba Battery Co Ltd | Alkaline secondary battery and its manufacture |
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1998
- 1998-02-27 CN CN98107135A patent/CN1062612C/en not_active Expired - Fee Related
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|---|---|---|---|---|
| WO2000068462A1 (en) * | 1999-05-07 | 2000-11-16 | H.C. Starck Gmbh | Method for producing nickel hydroxides |
| US6752918B1 (en) | 1999-05-07 | 2004-06-22 | H. C. Starck Gmbh | Method for producing nickel hydroxides |
| CN1311104C (en) * | 2003-09-28 | 2007-04-18 | 北京航空航天大学 | Process for preparing nickel hydroxide material using electric deposition method |
| CN102249349A (en) * | 2011-04-26 | 2011-11-23 | 北京化工大学 | Multi-component doped spherical nano nickel hydroxide synthesized by chemical-electrochemical combined method |
| CN102249349B (en) * | 2011-04-26 | 2013-06-05 | 北京化工大学 | Multi-component doped spherical nano nickel hydroxide synthesized by chemical-electrochemical combined method |
| CN102603016A (en) * | 2012-03-08 | 2012-07-25 | 中国科学院苏州纳米技术与纳米仿生研究所 | Method for preparing nanometer nickel oxide and application of method |
| CN107190274A (en) * | 2017-05-10 | 2017-09-22 | 东北大学 | A kind of method that nickel chloride electricity conversion directly prepares nickel hydroxide |
| CN107236964A (en) * | 2017-05-10 | 2017-10-10 | 东北大学 | A kind of method that cobalt chloride electricity conversion directly prepares cobalt hydroxide |
| CN107236963A (en) * | 2017-05-10 | 2017-10-10 | 东北大学 | A kind of method that chlorination ferroelectricity conversion directly prepares iron hydroxide or iron oxide |
| CN107254687A (en) * | 2017-05-10 | 2017-10-17 | 东北大学 | A kind of method that electrolytic chlorination rare earth prepares rare earth oxide |
| CN113302168A (en) * | 2019-01-16 | 2021-08-24 | 麻省理工学院 | Reaction schemes involving acids and bases; a reactor comprising a spatially varying chemical composition gradient; and related systems and methods |
| CN109755029B (en) * | 2019-01-31 | 2020-04-03 | 燕山大学 | Preparation method of flower-like nano nickel oxide |
| CN109755029A (en) * | 2019-01-31 | 2019-05-14 | 燕山大学 | A kind of preparation method of flower piece shape nano-nickel oxide |
| CN110129825A (en) * | 2019-05-23 | 2019-08-16 | 天津市大陆制氢设备有限公司 | A kind of efficient Ni/Ni (OH)2Hydrogen-precipitating electrode and preparation method thereof |
| CN110129825B (en) * | 2019-05-23 | 2022-02-01 | 天津市大陆制氢设备有限公司 | High-efficiency Ni/Ni (OH)2Hydrogen evolution electrode and preparation method thereof |
| CN111118521A (en) * | 2020-01-17 | 2020-05-08 | 西北师范大学 | Method for preparing nano nickel hydroxide by electrolytic process |
| CN114959754A (en) * | 2021-02-24 | 2022-08-30 | 中国科学院上海硅酸盐研究所 | Device and method for efficiently preparing hydrogen and nickel compound |
| CN113120978A (en) * | 2021-04-19 | 2021-07-16 | 贵州源驰新能源科技有限公司 | A kind of Ni (OH)2And method for preparing the same |
| CN113120978B (en) * | 2021-04-19 | 2022-07-01 | 贵州源驰新能源科技有限公司 | A kind of Ni (OH)2And method for preparing the same |
| CN114774960A (en) * | 2022-04-28 | 2022-07-22 | 江西八六三实业有限公司 | Efficient OER electrochemical active catalyst |
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