CN102092797A - Sol-gel preparation method of porous nickel cobaltate material - Google Patents
Sol-gel preparation method of porous nickel cobaltate material Download PDFInfo
- Publication number
- CN102092797A CN102092797A CN 201110033497 CN201110033497A CN102092797A CN 102092797 A CN102092797 A CN 102092797A CN 201110033497 CN201110033497 CN 201110033497 CN 201110033497 A CN201110033497 A CN 201110033497A CN 102092797 A CN102092797 A CN 102092797A
- Authority
- CN
- China
- Prior art keywords
- acetate
- sol
- cobaltous diacetate
- nickel
- porous
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a sol-gel preparation method of a porous nickel cobaltate material. The method comprises the following steps of: dissolving cobalt acetate and nickel acetate in distilled water to obtain acetate aqueous solution, adding citric acid aqueous solution, uniformly mixing, adding distilled water for diluting until the concentration of the cobalt acetate is between 0.016 and 0.05 mol/L to obtain diluted solution, and drying to obtain a precursor; and grinding and calcining the precursor to obtain the porous nickel cobaltate material. The method has a simple preparation process and is environmentally-friendly; and the obtained nickel cobaltate has a spinel cubic phase, high purity, high degree of crystallinity, uniform pore diameter distribution and the pore diameter size of less than 200 nanometers, and is porous.
Description
One, technical field
The present invention relates to a kind of preparation method of inorganic porous material, specifically a kind of sol-gel process for preparing of porous cobalt acid nickel material.
Two, background technology
NiCo
2O
4Be a kind of composite oxides of spinel type, the cobalt acid nickel of discovering in recent years has good application in many aspects, is a kind of important inorganic functional material.For example, cobalt acid nickel is good electrode materials in alkaline electrolyte, can be used as the active electrode of electrochemical capacitor, and some material is shown good catalytic activity.Someone finds NiCo
2O
4To H
2O
2Electrochemical reduction has high catalytic activity and stability, in petroleum industry to the advantages of high catalytic activity of having separated out of oxygen.Cobalt acid nickel also shows good magnetic performance after deliberation.
At present for preparation method's research of cobalt acid nickel also seldom, do not appear in the newspapers less than the sour nickel material of porous cobalt of 200nm in the aperture of preparing even structure.The method that forefathers prepare cobalt acid nickel material mainly contains high temperature solid-state method, hydrothermal method, sol-gel method etc.The temperature that high temperature solid state reaction is had relatively high expectations can cause size distribution inhomogeneous usually, and is dispersed bad.For hydrothermal method, reaction needs to carry out under comparatively high temps and pressure, has relatively high expectations for reaction conditions and equipment material, is difficult to industrialization and enlarges production.And sol-gel method has overcome the shortcoming and defect of above-mentioned several method to a certain extent, can realize a large amount of synthetic of material under comparatively gentle condition, has become one of important means of current preparation material.Prepare in the sol-gel method of cobalt acid nickel forefathers, most methods are with the part of macromolecule organic as metal ion, with organism as solvent, but macromolecule organic costs an arm and a leg, not environmental protection and a lot of organism are harmful.Therefore the method that we wish to find that a kind of technology is simple, cost of material cheap, environmental protection and harmless collosol and gel prepare cobalt acid nickel.
Three, summary of the invention
The present invention is for fear of above-mentioned the deficiencies in the prior art part, provides that a kind of controllability is good, the sol-gel process for preparing of the porous cobalt acid nickel material of phase purity height, even structure.
Technical solution problem of the present invention adopts following technical scheme:
The characteristics of the sol-gel process for preparing of porous cobalt acid nickel material of the present invention are to operate according to the following steps:
A, Cobaltous diacetate and nickel acetate are dissolved in distilled water, are made into acetate aqueous solution, make that the concentration of Cobaltous diacetate is 0.16-0.5mol/L in the described acetate aqueous solution, the mol ratio of described Cobaltous diacetate and described nickel acetate addition is 2: 1;
B, citric acid is dissolved in the distilled water, be made into aqueous citric acid solution, to get mixing solutions in the described aqueous citric acid solution adding step a gained acetate aqueous solution then, the mole number sum of described Cobaltous diacetate and nickel acetate is 1-2 with the ratio of the mole number of described citric acid: 1;
C, adding distil water dilution in described mixing solutions make that the concentration of Cobaltous diacetate is 0.016-0.05mol/L in the described mixing solutions, diluting soln; Described diluting soln was got precursor in 120-130 ℃ of dry 12-16 hour;
D, 200 mesh sieves are pulverized and crossed to described precursor, promptly get the sour nickel material of porous cobalt in 2-3 hour 350-400 ℃ of calcining then.
The characteristics of the sol-gel process for preparing of porous cobalt of the present invention acid nickel material also are: adding distil water dilution in described mixing solutions among the described step c makes that the volumetric molar concentration of Cobaltous diacetate is 0.016-0.03mol/L in the described mixing solutions.
The characteristics of the sol-gel process for preparing of porous cobalt acid nickel material of the present invention also are: the mole number sum that Cobaltous diacetate and nickel acetate described in the described step b add is 1: 1 with the ratio of the mole number that described citric acid adds.
The characteristics of the sol-gel process for preparing of porous cobalt acid nickel material of the present invention also are: calcining temperature is 380-400 ℃ in the described steps d, and calcination time is 2.5-3 hour.
What the present invention adopted is the metal-chelating gel method, and gained cobalt acid nickel is spinel type, and be characterized in: the vesicular of even structure, the aperture is less than 200nm.
Compared with the prior art beneficial effect of the present invention is embodied in:
1, the present invention adopts the synthesizing porous cobalt of sol-gel method acid nickel material, compare with other chemical synthesis process have environmental protection, advantages such as technology is simple, no waste water and dregs, low-temp low-pressure.
2, gained cobalt acid nickel material of the present invention is that spinel type cube phase, purity height, degree of crystallinity height, porous, even aperture distribution and aperture size are less than 200nm.Because the pattern of material is uniform vesicular, have that volume density is little, specific surface area big, than characteristics such as mechanics performance height, be a kind of novel structure function material, can be used for catalytic reaction engineering, electrochemistry and field of petrochemical industry.
Four, description of drawings
Fig. 1 is the XRD figure of the porous cobalt acid nickel material of embodiment of the invention 1-5 preparation.Wherein curve 1 is the XRD curve of the porous cobalt acid nickel material of embodiment 1 preparation; Curve 2 is the XRD curve of the porous cobalt acid nickel material of embodiment 2 preparations; Curve 3 is the XRD curve of the porous cobalt acid nickel material of embodiment 3 preparations; Curve 4 is the XRD curve of the porous cobalt acid nickel material of embodiment 4 preparations; Curve 5 is the XRD curve of the porous cobalt acid nickel material of embodiment 5 preparations.
Fig. 2 is the stereoscan photograph of the porous cobalt acid nickel material of the embodiment of the invention 1 preparation.
Five, embodiment
For better understanding the present invention, the present invention will be further described below in conjunction with accompanying drawing and example, but the scope of protection of present invention is not limited to the scope that embodiment represents.
Embodiment 1:
The sol-gel process for preparing of the porous cobalt acid nickel material of present embodiment is operated according to the following steps:
With 50mL concentration is that the cobalt acetate solution of 0.32mol/L and nickel acetate solution that 50mL concentration is 0.16mol/L mix, be made into acetate aqueous solution, adding 50mL concentration then in acetate aqueous solution is the aqueous citric acid solution of 0.48mol/L, to make Cobaltous diacetate volumetric molar concentration in the solution after mixing be 0.016mol/L for adding distil water dilution again, mix and be placed in the loft drier, got presoma down in dry 16 hours at 120 ℃, the gained precursor is ground and crosses 200 mesh sieves, be placed in the tube furnace in 400 ℃ of calcining 2h, promptly get the sour nickel material of porous cobalt.
Embodiment 2:
The sol-gel process for preparing of the porous cobalt acid nickel material of present embodiment is operated according to the following steps:
With 50mL concentration is that the cobalt acetate solution of 0.32mol/L and nickel acetate solution that 50mL concentration is 0.16mol/L mix, be made into acetate aqueous solution, adding 50mL concentration then in acetate aqueous solution is the aqueous citric acid solution of 0.48mol/L, to make Cobaltous diacetate volumetric molar concentration in the solution after mixing be 0.016mol/L for adding distil water dilution again, mix and be placed in the loft drier, got presoma down in dry 12 hours at 130 ℃, the gained precursor is ground and crosses 200 mesh sieves, be placed in the tube furnace in 350 ℃ of calcining 3h, promptly get the sour nickel material of porous cobalt.
Embodiment 3:
The sol-gel process for preparing of the porous cobalt acid nickel material of present embodiment is operated according to the following steps:
With 50mL concentration is that the cobalt acetate solution of 0.32mol/L and nickel acetate solution that 50mL concentration is 0.16mol/L mix, be made into acetate aqueous solution, adding 50mL concentration then in acetate aqueous solution is the aqueous citric acid solution of 0.48mol/L, to make Cobaltous diacetate volumetric molar concentration in the solution after mixing be 0.03mol/L for adding distil water dilution again, mix and be placed in the loft drier, got presoma down in dry 14 hours at 125 ℃, the gained precursor is ground and crosses 200 mesh sieves, be placed in the tube furnace in 380 ℃ of calcining 2h, promptly get the sour nickel material of porous cobalt.
Embodiment 4:
The sol-gel process for preparing of the porous cobalt acid nickel material of present embodiment is operated according to the following steps:
With 50mL concentration is that the cobalt acetate solution of 1.0mol/L and nickel acetate solution that 50mL concentration is 0.5mol/L mix, be made into acetate aqueous solution, adding 50mL concentration then in acetate aqueous solution is the aqueous citric acid solution of 1.5mol/L, to make Cobaltous diacetate volumetric molar concentration in the solution after mixing be 0.05mol/L for adding distil water dilution again, mix and be placed in the loft drier, got presoma down in dry 16 hours at 120 ℃, the gained precursor is ground and crosses 200 mesh sieves, be placed in the tube furnace in 400 ℃ of calcining 2h, promptly get the sour nickel material of porous cobalt.
Embodiment 5:
The sol-gel process for preparing of the porous cobalt acid nickel material of present embodiment is operated according to the following steps:
With 50mL concentration is that the cobalt acetate solution of 1.0mol/L and nickel acetate solution that 50mL concentration is 0.5mol/L mix, be made into acetate aqueous solution, adding 50mL concentration then in acetate aqueous solution is the aqueous citric acid solution of 0.75mol/L, to make Cobaltous diacetate volumetric molar concentration in the solution after mixing be 0.04mol/L for adding distil water dilution again, mix and be placed in the loft drier, got presoma down in dry 12 hours at 130 ℃, the gained precursor is ground and crosses 200 mesh sieves, be placed in the tube furnace in 400 ℃ of calcining 2h, promptly get the sour nickel material of porous cobalt.
The XRD test result of the porous cobalt acid nickel material of embodiment 1-5 preparation is seen curve 1-5 among Fig. 1, and all diffraction peaks can both be corresponding with the base peak of the spinel type of bottom as can be seen from Figure 1, and hence one can see that, and gained cobalt acid nickel is a cube phase spinel structure.
The SEM test result of the porous cobalt acid nickel material of embodiment 1-5 preparation is seen Fig. 2, and material is amplified 10000 times, and we can see the surface tissue of material clearly.It is characterized in that: even structure, porous, the aperture is less than 200nm.Because the pattern of material is uniform vesicular, have that volume density is little, specific surface area big, than characteristics such as mechanics performance height, be a kind of novel structure function material, can be used for catalytic reaction engineering, electrochemistry and field of petrochemical industry.
Claims (4)
1. the sol-gel process for preparing of porous cobalt acid nickel material is characterized in that operating according to the following steps:
A, Cobaltous diacetate and nickel acetate are dissolved in distilled water, are made into acetate aqueous solution, make that the concentration of Cobaltous diacetate is 0.16-0.5mol/L in the described acetate aqueous solution, the mol ratio of described Cobaltous diacetate and described nickel acetate addition is 2: 1;
B, citric acid is dissolved in the distilled water, be made into aqueous citric acid solution, to get mixing solutions in the described aqueous citric acid solution adding step a gained acetate aqueous solution then, the mole number sum of described Cobaltous diacetate and nickel acetate is 1-2 with the ratio of the mole number of described citric acid: 1;
C, adding distil water dilution in described mixing solutions make that the concentration of Cobaltous diacetate is 0.016-0.05mol/L in the described mixing solutions, diluting soln; Described diluting soln was got precursor in 120-130 ℃ of dry 12-16 hour;
D, 200 mesh sieves are pulverized and crossed to described precursor, promptly get the sour nickel material of porous cobalt in 2-3 hour 350-400 ℃ of calcining then.
2. the sol-gel process for preparing of porous cobalt according to claim 1 acid nickel material is characterized in that: adding distil water dilution in described mixing solutions among the described step c makes that the volumetric molar concentration of Cobaltous diacetate is 0.016-0.03mol/L in the described mixing solutions.
3. the sol-gel process for preparing of porous cobalt acid nickel material according to claim 1 is characterized in that: the mole number sum that Cobaltous diacetate and nickel acetate described in the described step b add is 1: 1 with the ratio of the mole number that described citric acid adds.
4. the sol-gel process for preparing of porous cobalt acid nickel material according to claim 1, it is characterized in that: calcining temperature is 380-400 ℃ in the described steps d, calcination time is 2.5-3 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100334973A CN102092797B (en) | 2011-01-30 | 2011-01-30 | Sol-gel preparation method of porous nickel cobaltate material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100334973A CN102092797B (en) | 2011-01-30 | 2011-01-30 | Sol-gel preparation method of porous nickel cobaltate material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102092797A true CN102092797A (en) | 2011-06-15 |
| CN102092797B CN102092797B (en) | 2012-05-23 |
Family
ID=44126088
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011100334973A Expired - Fee Related CN102092797B (en) | 2011-01-30 | 2011-01-30 | Sol-gel preparation method of porous nickel cobaltate material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102092797B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102350504A (en) * | 2011-10-27 | 2012-02-15 | 哈尔滨工业大学 | Preparation method of Fe2Ni alloy powder in nitric acid system |
| CN103400998A (en) * | 2013-07-22 | 2013-11-20 | 烟台大学 | Method for preparing gamma-sodium cobaltate electrode material by electrochemistry-assisted sol-gel process |
| CN104022261A (en) * | 2014-05-28 | 2014-09-03 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of composite oxide AB2O4 for lithium ion secondary battery cathode material |
| CN104870087A (en) * | 2012-11-09 | 2015-08-26 | 巴斯夫欧洲公司 | Process for producing a carbon-supported nickel-cobalt-oxide catalyst and its use in rechargeable electrochemical metal-oxygen cells |
| CN105399149A (en) * | 2015-11-24 | 2016-03-16 | 青岛能迅新能源科技有限公司 | Preparation method of supercapacitor electrode material |
| CN107324407A (en) * | 2017-08-15 | 2017-11-07 | 陕西科技大学 | A kind of NiCo2O4Hexagonal prism crystal and preparation method thereof |
| CN107473273A (en) * | 2017-08-02 | 2017-12-15 | 东北大学秦皇岛分校 | Three-dimensional structure micron order cobalt acid Ni cluster, preparation method and the usage |
Citations (2)
| 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 |
| CN101549890A (en) * | 2009-04-30 | 2009-10-07 | 中山大学 | Solvothermal synthesis method of nickel cobaltate nano particles |
-
2011
- 2011-01-30 CN CN2011100334973A patent/CN102092797B/en not_active Expired - Fee Related
Patent Citations (2)
| 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 |
| CN101549890A (en) * | 2009-04-30 | 2009-10-07 | 中山大学 | Solvothermal synthesis method of nickel cobaltate nano particles |
Non-Patent Citations (2)
| Title |
|---|
| 《React.Kinet.Catal.Lett.》 20061231 Jian Liu et al. STUDY OF THE CATALYTIC COMBUSTION OF DIESEL SOOT OVER NANOMETRIC LANTHANUM-COBALT MIXED OXIDE CATALYSTS 107-114 第87卷, 第1期 2 * |
| 《电源技术》 20010630 韩景立等 新柠檬酸溶胶凝胶法研究 第25卷, 第3期 2 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102350504A (en) * | 2011-10-27 | 2012-02-15 | 哈尔滨工业大学 | Preparation method of Fe2Ni alloy powder in nitric acid system |
| CN104870087A (en) * | 2012-11-09 | 2015-08-26 | 巴斯夫欧洲公司 | Process for producing a carbon-supported nickel-cobalt-oxide catalyst and its use in rechargeable electrochemical metal-oxygen cells |
| CN103400998A (en) * | 2013-07-22 | 2013-11-20 | 烟台大学 | Method for preparing gamma-sodium cobaltate electrode material by electrochemistry-assisted sol-gel process |
| CN103400998B (en) * | 2013-07-22 | 2015-11-18 | 烟台大学 | A kind of electrochemistry assisting sol gel method prepares the method for γ-cobalt acid sodium electrode material |
| CN104022261A (en) * | 2014-05-28 | 2014-09-03 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of composite oxide AB2O4 for lithium ion secondary battery cathode material |
| CN105399149A (en) * | 2015-11-24 | 2016-03-16 | 青岛能迅新能源科技有限公司 | Preparation method of supercapacitor electrode material |
| CN107473273A (en) * | 2017-08-02 | 2017-12-15 | 东北大学秦皇岛分校 | Three-dimensional structure micron order cobalt acid Ni cluster, preparation method and the usage |
| CN107324407A (en) * | 2017-08-15 | 2017-11-07 | 陕西科技大学 | A kind of NiCo2O4Hexagonal prism crystal and preparation method thereof |
| CN107324407B (en) * | 2017-08-15 | 2019-12-10 | 陕西科技大学 | NiCo 2 O 4 hexagonal column crystal and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102092797B (en) | 2012-05-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102092797B (en) | Sol-gel preparation method of porous nickel cobaltate material | |
| CN108346522B (en) | Cobaltosic oxide hierarchical structure nano array material, preparation method and application thereof | |
| Yan et al. | Enhanced bifunctional catalytic activity of manganese oxide/perovskite hierarchical core–shell materials by adjusting the interface for metal–air batteries | |
| CN109759077B (en) | Perovskite oxide catalyst and preparation method and application thereof | |
| WO2015103920A1 (en) | Multi-stage micro-nano structural material and preparation method therefor, and battery containing same | |
| CN103318978B (en) | Preparation method of mesoporous nickel cobaltate fiber and application thereof | |
| Su et al. | A top-down strategy for the synthesis of mesoporous Ba0. 5Sr0. 5Co0. 8Fe0. 2O3− δ as a cathode precursor for buffer layer-free deposition on stabilized zirconia electrolyte with a superior electrochemical performance | |
| CN100532272C (en) | Method for preparing porous balls of strontium titanate | |
| CN103007946B (en) | Co3O4/three-dimensional ordered macroporous La0.6Sr0.4CoO3 catalyst, preparation method and application | |
| KR20200019540A (en) | Method for Preparing Metal Composite Oxides Using Deep Eutectic Solvent | |
| Jiang et al. | Rare earth oxide based electrocatalysts: synthesis, properties and applications | |
| CN109665525B (en) | Preparation method of dumbbell-shaped iron-nitrogen double-doped porous carbon | |
| CN110416560B (en) | Calcium manganese oxide material and preparation method and application thereof | |
| CN102867965A (en) | Porous microsphere perovskite type calcium manganese oxide compound and preparation method and application thereof | |
| US11788196B2 (en) | ABO3 type high-entropy perovskite Bax(FeCoNiZrY)0.2O3-delta electrocatalytic material and preparation method thereof | |
| CN107792884A (en) | A kind of air electrode catalyst material nano hexagon ZnMnO3Preparation method and application | |
| CN110526304A (en) | Nickel cobaltosic sulfate/cobalt hydroxide nanosheet array structure composite material and preparation and application thereof | |
| Wan et al. | Building block nanoparticles engineering induces multi-element perovskite hollow nanofibers structure evolution to trigger enhanced oxygen evolution | |
| CN108695521A (en) | A kind of bilayer grade porous Fe-N codope carbon materials and its preparation method and application | |
| CN102479958B (en) | Application of catalyst in medium-temperature solid oxide fuel cell cathode | |
| WO2024066179A1 (en) | Surface-modified perovskite oxide electrocatalyst as well as preparation method therefor and use thereof | |
| CN103831097B (en) | Nanocatalyst lanthanum strontium manganese oxygen material and its preparation method and application | |
| CN110890557A (en) | Perovskite type catalyst for oxygen reduction reaction, preparation method and application | |
| CN102942204A (en) | Method for preparing cerium dioxide nanometer powder | |
| CN102867966A (en) | Porous micro-sphere post-spinel nitride calcium manganese oxygen compound, and preparation of and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20120523 Termination date: 20150130 |
|
| EXPY | Termination of patent right or utility model |