CN101096767A - Method for electrolytic preparing hydroxy cobalt nickel oxide - Google Patents
Method for electrolytic preparing hydroxy cobalt nickel oxide Download PDFInfo
- Publication number
- CN101096767A CN101096767A CNA200710054762XA CN200710054762A CN101096767A CN 101096767 A CN101096767 A CN 101096767A CN A200710054762X A CNA200710054762X A CN A200710054762XA CN 200710054762 A CN200710054762 A CN 200710054762A CN 101096767 A CN101096767 A CN 101096767A
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- nickel oxide
- electrolytic
- cobalt nickel
- hydroxy cobalt
- chloride solution
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Abstract
The invention discloses an electrolytic hydroxyl cobalt nickel oxide process, which is provided with the high oxidation efficiency, the short oxidation time and the friendly environment. The general formula of hydroxyl cobalt nickel oxide is NixCo1-xOOH, wherein x isn't less than 0 and isn't more than 0.85; the alkali chloride solution is in the anode chamber and cathode chamber which are divided by the barrier diaphragm, Ni(OH)2 is putted in he alkali chloride solution of the anode chamber, pH is adjusted to alkalinity with NaOH, cobalt hydroxide is electrolytic generated in the ambient temperature, 1.5-10 V constant pressure and mixing condition, wherein the concentration of the alkali chloride solution is 1-7M, the hydroxyl cobalt nickel oxide is produced by filtering, washing and drying. The invention is used for preparing the anode material of the lithium battery.
Description
Technical field:
The present invention relates to the method for a kind of method of hydroxy cobalt nickel oxide, particularly a kind of electrolytic preparing hydroxy cobalt nickel oxide.
Background technology:
Lithium nickel cobalt dioxide LiNixCo
1-xO
2Be a kind of novel anode material for lithium-ion batteries, have LiCoO
2And LiNiO
2Advantage, be that many being expected to of research at present substitutes LiCoO
2One of positive electrode material.Find after deliberation with hydroxy cobalt nickel oxide Ni
xCo
1-xOOH (0≤x≤0.85) is when being presoma, by himself existing laminate structure and niccolic condition, can be under air conditions and lower temperature synthetic positive electrode material LiNi
xCo
1-xO
2, it is low and controlled to have the reaction conditions temperature, and laminate structure is good, the capacity advantages of higher.When X=0, compound is hydroxy cobalt oxide CoOOH, and it is a kind of high price cobalt/cobalt oxide of high conductivity, can be used as conductive agent directly adds in the nickel hydroxide positive plate active substance, improve the electroconductibility between the electrode active material, and technology is simple, for most of battery producer adopts.CoOOH also is the good presoma of preparation LiCoO2 simultaneously, adopts CoOOH replaced C o
3O
4With Li
2CO
3Or LiOH mixing back high temperature solid state reaction, can significantly reduce calcining temperature, shorten calcination time, energy-saving and cost-reducing (battery, 2005,35 (2): 133-134)
Hydroxy cobalt nickel oxide Ni
xCo
1-xThe method of OOH (0≤x≤0.85) preparation mainly is: first chemosynthesis nickel hydroxide cobalt Ni
xCo
1-x(OH) 2 (0≤x≤0.85) are carried out chemical oxidation or electrolytic oxidation with it then, thereby are prepared into product.Generally can use excessive chemical oxidizing agents such as hypochlorite, permanganate when adopting chemical oxidization method, environmental pollution is big, and oxidation efficiency is low.Can be recycled and existing electrolytic oxidation has electrolytic solution, do not use chemical oxidizing agent, environmentally friendly.But its electrolytic oxidation time is long, and efficient is lower.Therefore studying the environmental protection electrolysis process with high electrolytic oxidation efficient has great practical value.
Summary of the invention:
The method that the purpose of this invention is to provide a kind of electrolytic preparing hydroxy cobalt nickel oxide, this method have the oxidation efficiency height, and oxidization time is short, friendly environment.Technical scheme of the present invention is that a kind of method of electrolytic preparing hydroxy cobalt nickel oxide is characterized in that: the general formula of hydroxy cobalt nickel oxide is Ni
xCo
1-xIn the OOH formula: there is alkali metal chloride solution 0≤x≤0.85 in anolyte compartment that is separated by barrier film and the cathode compartment, with Ni (OH)
2Put into the alkali metal chloride solution of anolyte compartment, transfer pH to alkalescence with NaOH, electrolysis generates the hydroxyl hydrogen cobalt oxide under 1.5-10 volt constant voltage, room temperature and stirring, and the concentration of described alkali metal chloride solution is 1-7M.Hydroxy cobalt oxide to preparation filters, washs, dries and make hydroxyl hydrogen cobalt nickel oxide finished product.It is short that the present invention has oxidization time compared with the prior art, the remarkable advantage of oxidation efficiency height and friendly environment.
Description of drawings:
Accompanying drawing is the electrolyzer longitudinal diagram that preparation hydroxy nickel oxide, cobalt method are used.
Embodiment:
Existing electrolytic oxidation time length, inefficient reason mainly are that cell construction has deficiency, and its anodic material is metal nickel plate or foaming nickel plate, and electrolytic solution is the alkaline solution of anaerobic chlorion.
Cell construction of the present invention is, barrier film of using with known lithium ion battery in groove 1 or alkaline cell are separated into anolyte compartment 3 and cathode compartment 4 with barrier film with electrolyzer, and anode 2 and negative electrode 5 place anolyte compartment and cathode compartment respectively.Be provided with agitator 6 in the anolyte compartment, cathode material is an inert material, and anode is a ti-supported lead dioxide electric pole, and its structure has layer: titanium net base layer, SnO
2And SbO
3Middle layer, β-PbO
2Coating, its making method are that (1) carries out substrate pretreated: 10 * 5cm titanium net is boiled with 10%HCL solution boiled in 10% oxalic acid solution 2 hours in 1 hour again, with acetone ultrasonic cleaning 10min, dry standby; (2) coat the middle layer: prepare a certain proportion of SnCl
4And SbCl
3Hydrochloric acid-butanol solution, with hairbrush it is coated on the matrix equably, then the electricity consumption hot blast drying, under 120-140 ℃ of condition dry 15 minutes again, be coated with again drier, repeat 5-7 time after, under 450-500 ℃ of condition, cure pyrolysis and use distilled water flushing after 1 hour, dry standby; (3) electroplate preparation β-PbO
2Upper layer: above-mentioned electrode immersed be added with a certain amount of NaF and HNO
3The lead nitrate aqueous solution in, be negative electrode with the copper coin, under 65 ℃ of temperature with 3.5A/m
2Current density under electroplated 4 hours, plate and has then used distilled water flushing, dry standby.
Electrolytic solution in the electrolyzer is alkali-metal muriatic basic solution, and nickel hydroxide is placed the anolyte compartment of electrolyzer, and the control electrolysis voltage at room temperature carries out electrolysis, following reaction takes place: the Ni of anolyte compartment
xCo
1-x(OH)
2(0≤x≤0.85)-e
-=Ni
xCo
1-xOOH (0≤x≤0.85)+H
+
2Cl
--e
-＝Cl
2
Cl
2+OH
-→ClO
-+H
2O
4Ni
xCo
1-x(OH)
2(0≤x≤0.85)+2ClO
-→4 Ni
xCo
1-xOOH(0≤x≤0.85)+2Cl
-+2H
2O。
Cathode compartment 2H
2O+e
-→ H
2+ 2OH
-
Advantage of the present invention is, titanium-matrix electrode oxygen overpotential height, oxidation capacity is strong, good conductivity is corrosion-resistant, in the anolyte compartment except with nickel hydroxide cobalt Ni
xCo
1-x(OH)
2(0≤x≤0.85) is direct oxidation into Ni
xCo
1-xOutside the OOH (0≤x≤0.85), also can be with the Cl in the electrolytic solution
-Be oxidized to Cl
2, and Cl
2With the OH in the electrolytic solution
-Be combined into ClO
-, the ClO of generation
-Can be with Ni
xCo
1-x(OH)
2(0≤x≤0.85) is oxidized to Ni
xCo
1-xOOH (0≤x≤0.85), the Cl in the electrolytic solution
-In fact played the effect of catalyzer, electrolytic oxidation organically combines with chemical oxidation and makes oxidation efficiency improve greatly; With barrier film anolyte compartment and cathode compartment are separated, avoided the reductive action of the hydrogen of cathode compartment generation, make oxidation efficiency farthest improve hydroxy cobalt nickel oxide.The present invention can control Cl by electrolytic condition
2The amount of separating out, make Cl
2With OH in the solution
-Reaction generates ClO
-Speed and ClO
-Oxidation Ni
xCo
1-x(OH)
2The speed that (0≤x≤0.85) is consumed equates, can avoid Cl
2Effusion, reacted the mother liquor of after-filtration as long as replenish a certain amount of KCl and adjust pH value and then just can continue to recycle, this can be avoided the discharging of waste liquid.Therefore the present invention is not only efficient but also environmentally friendly.
The present invention has following examples:
Embodiment 1,
(10cm * 5cm) is an anode, and stainless steel is a negative electrode, places the anolyte compartment and the cathode compartment that separate with alkaline battery separator respectively, with 20g nickel hydroxide cobalt Ni with ti-supported lead dioxide electric pole
0.8Co
0.2(OH)
2Add and fill in the electrolyzer anode chamber of 400ml 3MKCL solution, regulating its pH value with NaOH is 13, under agitation adopt the constant voltage mode to carry out electrolysis then, voltage control is at 5V, electrolysis 20h under the room temperature, the product that will reach required oxidisability filters, washing, 60 ℃ of dryings 6 hours, sample of the present invention.
The oxidisability of the different electrolysis times of table 1.
| Electrolysis time (h) | 4 | 6 | 8 | 10 | 12 | 14 | 16 | 18 | 2 |
| Oxidisability (%) | 40.2 | 53.5 | 65.9 | 73.3 | 83.6 | 90.2 | 98.1 | 100.1 | 110.5 |
(10cm * 5cm) is an anode, and the titanium sheet is a negative electrode, places the anolyte compartment and the cathode compartment that separate with alkaline battery separator respectively, with 20g nickel hydroxide cobalt Ni with titanium base ruthenium dioxide electrode
0.8Co
0.2(OH)
2Add and fill in the electrolyzer anode chamber of 400ml 5MKCL solution, regulating its pH value with NaOH is 11, under agitation adopt the constant voltage mode to carry out electrolysis then, voltage control is at 7V, electrolysis 20h under the room temperature, the product that will reach required oxidisability filters, washing, 80 ℃ of dryings 5 hours, sample of the present invention.
The oxidisability of the different electrolysis times of table 2.
| Electrolysis time (h) | 4 | 6 | 8 | 10 | 12 | 14 | 16 | 18 | 20 |
| Oxidisability (%) | 48.2 | 63.6. | 76.4 | 93.7 | 96.5 | 98.2 | 99.7 | 107.2 | 112.4 |
Embodiment 3,
(10cm * 5cm) is an anode, and the nickel sheet is a negative electrode, places the anolyte compartment and the cathode compartment that separate with alkaline battery separator respectively, with 20g nickel hydroxide cobalt Ni with titanium base iridium dioxide electrode
0.8Co
0.2(OH)
2Add and fill in the electrolyzer anode chamber of 400ml 3M NaCL solution, regulating its pH value with KOH is 13, under agitation adopt the constant voltage mode to carry out electrolysis then, voltage control is at 6V, electrolysis 20h under the room temperature, the product that will reach required oxidisability filters, washing, 100 ℃ of dryings 4 hours, sample of the present invention.
The oxidisability of the different electrolysis times of table 3.
| Electrolysis time (h) | 4 | 6 | 8 | 10 | 12 | 14 | 16 | 18 | 20 |
| Oxidisability (%) | 37.4 | 51.9 | 66.7 | 86.3 | 92.2 | 96.6 | 99.7 | 100.5 | 101.7 |
(10cm * 5cm) is an anode, and graphite is negative electrode, places the anolyte compartment and the cathode compartment that separate with lithium ion battery separator respectively, with 40g nickel hydroxide cobalt Ni with titanium base ruthenium dioxide iridium electrode
0.5Co
0.5(OH)
2Add and fill in the electrolyzer anode chamber of 400ml 1MKCL solution, regulating its pH value with NaOH is 10, under agitation adopt the constant voltage mode to carry out electrolysis then, voltage control is at 3V, electrolysis 20h under the room temperature, the product that will reach required oxidisability filters, washing, 80 ℃ of dryings 6 hours, sample of the present invention.
The oxidisability of the different electrolysis times of table 4.
| Electrolysis time (h) | 4 | 6 | 8 | 10 | 12 | 14 | 16 | 18 | 20 |
| Oxidisability (%) | 30.4 | 42.2 | 51.9 | 60.4 | 71.2 | 78.2 | 87.4 | 95.3 | 100.1 |
So that ti-supported lead dioxide electric pole 2 * (10cm * 5cm) is an anode, and nickel foam is a negative electrode, places the anolyte compartment and the cathode compartment that separate with lithium ion battery separator respectively, with 100g Co (OH)
2Add and fill in the electrolyzer anode chamber of 400ml 3MKCL solution, regulating its pH value with NaOH is 13, under agitation adopt the constant voltage mode to carry out electrolysis then, voltage control is at 5V, electrolysis 4h under the room temperature, the product that will reach required oxidisability filters, washing, 60 ℃ of dryings 6 hours, sample of the present invention.
The oxidisability of the different electrolysis times of table 5.
| Electrolysis time (min) | 40 | 80 | 120 | 160 | 200 | 240 |
| Oxidisability (%) | 23.8 | 45.7 | 58.9 | 74.7 | 90.3 | 100.5 |
Embodiment 6,
So that ti-supported lead dioxide electric pole 2 * (10cm * 5cm) is an anode, and nickel foam is a negative electrode, places the anolyte compartment and the cathode compartment that separate with lithium ion battery separator respectively, with 20g nickel hydroxide cobalt Ni
0.8Co
0.2(OH)
2Add and fill in the electrolyzer anode chamber of 400ml 4MKCL solution, regulating its pH value with NaOH is 14, under agitation adopt the constant voltage mode to carry out electrolysis then, voltage control is at 7V, electrolysis 20h under the room temperature, the hydroxy nickel oxide product that will reach required oxidisability filters, washing, 60 ℃ of dryings 6 hours, sample of the present invention.
The oxidisability of the different electrolysis times of table 6.
| Electrolysis time (h) | 4 | 6 | 8 | 10 | 12 | 14 | 16 | 18 | 20 |
| Oxidisability (%) | 27.1 | 36.7 | 45.7 | 53.7 | 67.3 | 79.8 | 88.2 | 97.8 | 100.7 |
Claims (2)
1, a kind of method of electrolytic preparing hydroxy cobalt nickel oxide is characterized in that: the general formula of hydroxy cobalt nickel oxide is Ni
xCo
1-xIn the OOH formula: there is alkali metal chloride solution 0≤x≤0.85 in anolyte compartment that is separated by barrier film and the cathode compartment, with Ni (OH)
2Put into the alkali metal chloride solution of anolyte compartment, transfer pH to alkalescence with NaOH, electrolysis generates hydroxy cobalt nickel oxide under 1.5-10 volt constant voltage, room temperature and stirring, and the concentration of described alkali metal chloride solution is 1-7M.
2, the method for a kind of electrolytic preparing hydroxy cobalt nickel oxide as claimed in claim 1 is characterized in that: the hydroxy cobalt oxide to preparation filters, washs, dries and make the hydroxy cobalt nickel oxide finished product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA200710054762XA CN101096767A (en) | 2007-06-28 | 2007-06-28 | Method for electrolytic preparing hydroxy cobalt nickel oxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA200710054762XA CN101096767A (en) | 2007-06-28 | 2007-06-28 | Method for electrolytic preparing hydroxy cobalt nickel oxide |
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| Publication Number | Publication Date |
|---|---|
| CN101096767A true CN101096767A (en) | 2008-01-02 |
Family
ID=39010839
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|---|---|---|---|
| CNA200710054762XA Pending CN101096767A (en) | 2007-06-28 | 2007-06-28 | Method for electrolytic preparing hydroxy cobalt nickel oxide |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103715422A (en) * | 2013-12-24 | 2014-04-09 | 天津巴莫科技股份有限公司 | Method for preparing high nickel-based anode material for lithium ion battery through electrolytic process |
| CN103872314A (en) * | 2014-03-21 | 2014-06-18 | 个旧圣比和实业有限公司 | Pre-oxidization method of high-nickel ternary positive electrode active substance precursor of lithium ion battery |
| CN112151900A (en) * | 2019-06-26 | 2020-12-29 | 西南科技大学 | Method for directly regenerating lithium cobaltate from lithium cobaltate-containing material |
-
2007
- 2007-06-28 CN CNA200710054762XA patent/CN101096767A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103715422A (en) * | 2013-12-24 | 2014-04-09 | 天津巴莫科技股份有限公司 | Method for preparing high nickel-based anode material for lithium ion battery through electrolytic process |
| CN103715422B (en) * | 2013-12-24 | 2015-10-28 | 天津巴莫科技股份有限公司 | Electrolysis prepares the method for the nickelic system positive electrode of lithium ion battery |
| CN103872314A (en) * | 2014-03-21 | 2014-06-18 | 个旧圣比和实业有限公司 | Pre-oxidization method of high-nickel ternary positive electrode active substance precursor of lithium ion battery |
| CN112151900A (en) * | 2019-06-26 | 2020-12-29 | 西南科技大学 | Method for directly regenerating lithium cobaltate from lithium cobaltate-containing material |
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Open date: 20080102 |