CN103400998B - A kind of electrochemistry assisting sol gel method prepares the method for γ-cobalt acid sodium electrode material - Google Patents
A kind of electrochemistry assisting sol gel method prepares the method for γ-cobalt acid sodium electrode material Download PDFInfo
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- CN103400998B CN103400998B CN201310325550.6A CN201310325550A CN103400998B CN 103400998 B CN103400998 B CN 103400998B CN 201310325550 A CN201310325550 A CN 201310325550A CN 103400998 B CN103400998 B CN 103400998B
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Abstract
The invention belongs to the metal oxide electrode material in functional material and preparing technical field thereof, particularly a kind of cobalt acid sodium electrode material and preparation method thereof, is characterized in that the collosol and gel synthetic technology that make use of electrochemistry and ultrasonic wave added.The method adopted is: utilize absolute ethyl alcohol and alkoxide preparation electrolyte, wherein acetylacetone,2,4-pentanedione is as complexing agent, and TBAB is as conductive agent.Adopt electrochemical method, using high-purity cobalt sheet as anode, stainless steel substrates, as negative electrode, under argon shield and ultrasonic wave added, adopts electrolysis mode to obtain precursor liquid.Precursor liquid forms colloidal sol, gel under 60 DEG C of magnetic agitation conditions, gel through washing with centrifugal after under 60 DEG C of conditions vacuumize obtain xerogel, finally sintering obtain dusty material.γ prepared by the present invention-cobalt acid sodium electrode material powder purity is higher, complete crystallization, even particle size distribution, and its layer structure is obvious, produces in whole preparation process without toxic gas.
Description
Technical field
The invention belongs to the metal oxide electrode material in functional material and preparing technical field thereof, particularly a kind of cobalt acid sodium electrode material and preparation method thereof.
Background technology
In recent years, ultracapacitor is with its excellent charge-discharge performance and be better than the high-specific-power of traditional capacitor, the feature of high power capacity, shows unprecedented application prospect in fields such as telecommunications, Aero-Space, military and national defense and new-energy automobiles.Electrode material is one of key factor determining ultracapacitor performance, and metal oxide becomes the focus of research because of its fake capacitance characteristic.Early stage research concentrates on the noble metals such as ruthenic oxide, and the oxide of the magnesium-yttrium-transition metals such as cobalt has multivalent state, therefore has the fake capacitance characteristic approximate with ruthenic oxide, can be used as the substitute of its cheapness.The cobalt base oxide cobalt acid sodium of layer structure, due to its good conductivity and stability, have catalytic performance, and this material non-toxic is harmless, environmentally safe simultaneously, therefore can be used as a kind of electrode material and use in alkaline fuel cell.
At present, the preparation method of cobalt acid sodium has solid phase method, solution combustion method, polymeric composite method, electrical spinning method and sol-gal process.It is uneven to there is raw material mixing in solid phase method, solution combustion method, polymeric composite fado, often pernicious gas is produced in follow-up sintering process, product purity not high (oxide remains more), the problem that grain size is thick and uneven, and Electrospun rule cost is higher.
Sol-gal process a kind ofly adopts suitable organic or inorganic salt to be mixed with solution, then the solution that can make it nucleation, gelation is added, control the gelinite that its gelation process obtains having spheric granules, obtain the method for required thing phase through uniform temperature calcining and decomposing.Like this, raw material achieves the uniformity of molecular level, and the temperature of synthesis is lower.Electrochemistry assisting sol gel method make use of electrochemical method and sol-gel method simultaneously, by means of the cavitation of ultrasonic technique, by the control to reaction condition (temperature, current density, pH, reaction time), achieve the control of the grain size to product, productive rate.
At present, there is not yet the relevant report that electrochemistry assisting sol gel method prepares γ-cobalt acid sodium electrode material both at home and abroad.
Summary of the invention
The object of the invention is to provide a kind of electrochemistry assisting sol gel method to prepare the method for γ-cobalt acid sodium electrode material.
Object of the present invention realizes in the following manner: a kind of electrochemistry assisting sol gel method prepares the method for γ-cobalt acid sodium electrode material, comprises the following steps:
(1) pre-treatment of cobalt sheet: after the mechanical polishing of cobalt sheet, soak in watery hydrochloric acid and acetone soln respectively, except degrease;
(2) preparation of electrolyte: with analytically pure ethylate for solute, with analytically pure absolute ethyl alcohol for solvent, the ethanolic solution of preparation ethylate, after abundant stirring, carry out filtration and obtain clear liquid, add TBAB and acetylacetone,2,4-pentanedione, obtain electrolyte;
(3) preparation of precursor liquid: using high-purity cobalt sheet as anode, stainless steel substrates, as negative electrode, carries out electrolysis 2 ~ 6 hours with the electrolyte of step (2) in two electrode systems, simultaneously auxiliary with ultrasonic technique and with inert gas shielding;
(4) formation of colloidal sol and gel: precursor liquid stirs at constant temperature lower magnetic force and regulates pH to alkalescence, continues to be stirred to formation colloidal sol, gel;
(5) cleaning of gel is with dry: centrifugal after gel washes of absolute alcohol, then carries out vacuumize at 40 DEG C ~ 80 DEG C;
(6) sintering of gel: dried gel sinters at 700 DEG C ~ 950 DEG C, finally obtains γ-cobalt acid sodium electrode material powder.
In described step (2), ethylate is caustic alcohol.
Described step (3) make use of electrochemical method, and the parameter of employing is constant current 0.016A/cm
2with permanent electromotive force 0.8V.
The ultrasonic power adopted in described step (3) is 60W, and temperature is 60 DEG C.
The invention has the advantages that:
1. utilize electrochemical method and ultrasonic technique to shorten the reaction time, reactant fully mixes, and reaction is easy to control.
2. the γ using this method obtained-cobalt acid sodium electrode material powder purity is high, better crystallinity degree, epigranular, reproducibility are good.
Accompanying drawing explanation
Fig. 1 is the XRD collection of illustrative plates of γ-cobalt acid sodium electrode material product prepared in embodiment 1.
Fig. 2 is the SEM photo of γ-cobalt acid sodium electrode material product prepared in embodiment 1.
Fig. 3 is the SEM photo of γ-cobalt acid sodium electrode material product prepared in embodiment 1.
Fig. 4 is the battery charging and discharging picture of γ-cobalt acid sodium electrode material product prepared in embodiment 1.
Embodiment
Below in conjunction with instantiation, the present invention is further described.
Embodiment 1
Cobalt sheet, after mechanical polishing, soaks 15 minutes, respectively except degrease in watery hydrochloric acid and acetone soln.With analytically pure caustic alcohol 2g for solute, with analytically pure absolute ethyl alcohol 150ml for solvent, the ethanolic solution of preparation caustic alcohol, after fully stirring, carries out filtration and obtains clear liquid, add TBAB 1.0g and acetylacetone,2,4-pentanedione solution 10ml, obtain electrolyte.Using high-purity cobalt sheet (30mm × 40mm) as anode; stainless steel substrates (40mm × 40mm) is as negative electrode; carry out with constant current 0.2A electrolysis 2 hours in two electrode systems with above-mentioned electrolyte; simultaneously auxiliary with ultrasonic technique (for 60W, temperature is 60 DEG C to regulating power) and with argon shield.Precursor liquid stirs at constant temperature 60 DEG C of condition lower magnetic forces and dropwise adds ammoniacal liquor and regulates pH to 10, continues to be stirred to form colloidal sol, gel.With the centrifugation twice of 6000r/min after gel washes of absolute alcohol, then at 60 DEG C, in the vacuum drying chamber of 0.1MPa, carry out vacuumize.Dried gel, at 800 DEG C of sintering 5h, finally obtains γ-cobalt acid sodium electrode material powder.
Embodiment 2
Cobalt sheet, after mechanical polishing, soaks 15 minutes, respectively except degrease in watery hydrochloric acid and acetone soln.With analytically pure caustic alcohol 2g for solute, with analytically pure absolute ethyl alcohol 150ml for solvent, the ethanolic solution of preparation caustic alcohol, after fully stirring, carries out filtration and obtains clear liquid, add TBAB 1.0g and acetylacetone,2,4-pentanedione solution 10ml, obtain electrolyte.Using high-purity cobalt sheet (30mm × 40mm) as anode; stainless steel substrates (40mm × 40mm) is as negative electrode; in two electrode systems, electrolysis is carried out 2 hours with constant potential 0.8V with above-mentioned electrolyte; simultaneously auxiliary with ultrasonic technique (for 60W, temperature is 60 DEG C to regulating power) and with argon shield.Precursor liquid stirs at constant temperature 60 DEG C of condition lower magnetic forces and dropwise adds ammoniacal liquor and regulates pH to 10, continues to be stirred to form colloidal sol, gel.With the centrifugation twice of 6000r/min after gel washes of absolute alcohol, then at 60 DEG C, in the vacuum drying chamber of 0.1MPa, carry out vacuumize.Dried gel, at 800 DEG C of sintering 5h, finally obtains γ-cobalt acid sodium electrode material powder.
Claims (4)
1. electrochemistry assisting sol gel method prepares a method for γ-cobalt acid sodium electrode material, it is characterized in that: comprise the following steps:
(1) pre-treatment of cobalt sheet: cobalt sheet, after mechanical polishing, soaks, respectively except degrease in watery hydrochloric acid and acetone soln;
(2) preparation of electrolyte: with analytically pure ethylate for solute, with analytically pure absolute ethyl alcohol for solvent, the ethanolic solution of preparation ethylate, after abundant stirring, carry out filtration and obtain clear liquid, add TBAB and acetylacetone,2,4-pentanedione, obtain electrolyte;
(3) preparation of precursor liquid: using high-purity cobalt sheet as anode, stainless steel substrates, as negative electrode, carries out electrolysis 2 ~ 6 hours with the electrolyte of step (2) in two electrode systems, simultaneously auxiliary with ultrasonic technique and with inert gas shielding;
(4) formation of colloidal sol and gel: precursor liquid stirs at constant temperature lower magnetic force and regulates pH to alkalescence, continues to be stirred to formation colloidal sol, gel;
(5) cleaning of gel is with dry: centrifugal after gel washes of absolute alcohol, then carries out vacuumize at 60 DEG C ~ 80 DEG C;
(6) sintering of gel: dried gel sinters at 700 DEG C ~ 950 DEG C, finally obtains γ-cobalt acid sodium powder.
2. electrochemistry assisting sol gel method according to claim 1 prepares the method for γ-cobalt acid sodium electrode material, and it is characterized in that, in described step (2), ethylate is caustic alcohol.
3. electrochemistry assisting sol gel method according to claim 1 prepares the method for γ-cobalt acid sodium electrode material, and it is characterized in that, in described step (3), the preparation of precursor liquid have employed electrochemical method, and the parameter of employing is constant current 0.016A/cm
2with permanent electromotive force 0.8V.
4. electrochemistry assisting sol gel method according to claim 1 prepares the method for γ-cobalt acid sodium electrode material, and it is characterized in that, the ultrasonic power adopted in described step (3) is 60W, and temperature is 60 DEG C.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101254952A (en) * | 2008-04-02 | 2008-09-03 | 钢铁研究总院 | Acetate doping natrium cobaltite thermoelectric materials and preparation method thereof |
| CN101717125A (en) * | 2009-12-04 | 2010-06-02 | 华东师范大学 | Method for preparing cobalt oxide nano-sheet sol |
| CN102092797A (en) * | 2011-01-30 | 2011-06-15 | 合肥工业大学 | Sol-gel preparation method of porous nickel cobaltate material |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101254952A (en) * | 2008-04-02 | 2008-09-03 | 钢铁研究总院 | Acetate doping natrium cobaltite thermoelectric materials and preparation method thereof |
| CN101717125A (en) * | 2009-12-04 | 2010-06-02 | 华东师范大学 | Method for preparing cobalt oxide nano-sheet sol |
| CN102092797A (en) * | 2011-01-30 | 2011-06-15 | 合肥工业大学 | Sol-gel preparation method of porous nickel cobaltate material |
Non-Patent Citations (3)
| Title |
|---|
| NaxCo2O4热电材料的研究进展;厉英,等;《东北大学学报(自然科学版)》;20050331;第26卷(第3期);第236-239页 * |
| NaxCo2O4陶瓷的力学弛豫和阻抗弛豫研究;刘文峰，等;《中山大学学报(自然科学版)》;20090531;第48卷(第3期);第33-36页 * |
| 溶胶-凝胶法制备γ-NaxCo2O4热电材料及其电性能;张莉，等;《武汉理工大学学报》;20090331;第31卷(第5期);第24-26页 * |
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Effective date of registration: 20170221 Address after: Shandong city of Qingdao province Hongkong city 266000 A Road No. 6 Building 24 layer C Patentee after: Qingdao Amos Resources Technology Co., Ltd. Address before: 264005 Shandong Province, Yantai city Laishan District Road No. 32 spring Patentee before: Yantai University |
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Denomination of invention: Method for preparing gamma-sodium cobaltate electrode material by electrochemistry-assisted sol-gel process Effective date of registration: 20180816 Granted publication date: 20151118 Pledgee: Qingdao Huitong Chinese financing Company limited by guarantee Pledgor: Qingdao Amos Resources Technology Co., Ltd. Registration number: 2018370010085 |