CN107910557A - The preparation method of graphene-supported cobaltosic oxide nano crystal composite material and its application in zinc-air battery air cathode - Google Patents
The preparation method of graphene-supported cobaltosic oxide nano crystal composite material and its application in zinc-air battery air cathode Download PDFInfo
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- CN107910557A CN107910557A CN201710986217.8A CN201710986217A CN107910557A CN 107910557 A CN107910557 A CN 107910557A CN 201710986217 A CN201710986217 A CN 201710986217A CN 107910557 A CN107910557 A CN 107910557A
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Abstract
A kind of preparation method the present invention relates to graphene-supported cobaltosic oxide nano crystal composite material and its application in zinc-air battery air cathode.By graphene oxide ultrasonic disperse in deionized water, graphene oxide suspension is obtained；Take cobalt salt solution and sodium salt solution to add in graphene oxide suspension, above-mentioned mixed liquor is stirred evenly；Ammonium hydroxide is added into mixed solution, obtains cobalt amine complex solution；Then obtained mixed solution is subjected to hydro-thermal process under sealing, obtains black precipitate；The black precipitate is washed through deionized water, absolute ethyl alcohol successively, it is dry under air atmosphere, finally obtain graphene-supported cobaltosic oxide nano crystal.Above-mentioned material is mixed with organic solvent and binding agent, slurry is obtained after ultrasonic disperse；Slurry is uniformly dripped and is invested on pretreated carbon paper, up to the air cathode piece after drying.The method of the present invention is simple, easy to operate, economic and environment-friendly, and cost is low, has preferable industrial application value.
Description
Technical field
The invention belongs to metal-air battery electro-catalysis field, and in particular to a kind of high efficiency low cost rechargeable type zinc-air electricity
The preparation method of pond air cathode material.
Background technology
At present, increasingly serious the problems such as fossil energy crisis, climate warming, finding fungible energy source becomes the task of top priority.
Zinc-air battery is obtained more next with the features such as its higher theoretical energy density and power density, cheap and easy to get, safety and environmental protection
More concerns.Zinc and air cell is mainly made of three parts：Zinc metal anode, air cathode and separation layer.Wherein, rechargeable type zinc
The empty commercialized main problem of battery is to find pair of oxygen reduction reaction and oxygen evolution reaction that efficient catalytic occurs in air cathode
Function catalyst.
Spinelle cobaltosic oxide has extensively in fields such as electrode material for super capacitor, solid state sensor and optics
General application.Due to have significant impact of the avtive spot for the electrocatalysis characteristic of material of nano material difference crystal face exposure, institute
Become the research emphasis of nano material scholar to prepare the nanocrystal with particular crystal plane exposure.So far, Ren Menyi
Through having prepared the cobaltosic oxide nano crystal of different-shape, such as nanotube, nanometer rods, nanometer sheet, nano cubic in succession
Deng.But as a kind of transition metal oxide, cobaltosic oxide nano crystal electric conductivity is poor, is easy to limit the features such as reunion
The further lifting of its electrocatalysis characteristic is made.Graphene has superior electronic conduction speed, great specific surface area and good
The advantages that mechanical performance got well, be a kind of fabulous catalyst carrier material.Therefore, load has particular crystal plane on graphene
The advantages of exposed cobaltosic oxide nano crystal composite material can integrate two kinds of materials, greatly lifts electrocatalysis characteristic,
And then prepare a kind of zinc-air battery device of high efficiency low cost.
The content of the invention
It is an object of the invention to provide a kind of the simple and environmentally-friendly, efficiently honest and clean of graphene-supported cobaltosic oxide nano crystal
The preparation method of valency.Four oxidations with particular crystal plane exposure of the uniform load on graphene are prepared using one step hydro thermal method
The superior performance of three cobalt nanocrystal bodies, its electro-catalysis oxygen evolution reaction and oxygen reduction reaction.
The purpose of the present invention is what is be achieved through the following technical solutions：
A kind of preparation method of graphene-supported cobaltosic oxide nano crystal composite material, includes the following steps：
1) graphene oxide ultrasonic disperse in deionized water, is weighed, obtains graphene oxide suspension；
2) cobalt salt solution, sodium salt solution, are weighed, is uniformly mixed at room temperature, is then added in graphene oxide suspension
Obtain mixed solution；
3) ammonium hydroxide, is added into mixed solution, is stirred evenly, obtains cobalt amine complex solution；
4), the mixed solution for obtaining step 3) carries out hydro-thermal process under sealed conditions, obtains black precipitate；
5), black precipitate obtained by step 4) is washed through deionized water, absolute ethyl alcohol successively, it is dry under air atmosphere, obtain
To graphene-supported cobaltosic oxide nano crystal composite material.
Step 1) the graphene oxide suspension concentration is 0.5-3.0mg/mL, and reaction volume is 10~30mL.
Step 2) the cobalt salt is cobalt nitrate or cobalt acetate, and concentration is 0.5~2mol/L, and dosage is 0.5~2mL；Institute
It is sodium nitrate or sodium acetate to state sodium salt, and concentration is 0.1~2mol/L, and dosage is 0.5~2mL.
The volume that the step 3) adds ammonium hydroxide is 0.5~15mL.The mixing time is 0.5~4h.
The temperature of the step 4) hydro-thermal reaction is 155~185 DEG C, and the time of hydro-thermal process is 12h.
The temperature of the step 5) drying temperature is 40~80 DEG C, and drying time is 6~15h.
The graphene-supported cobaltosic oxide nano crystal composite material of the present invention is applied to zinc and air cell air cathode, will
Graphene-supported cobaltosic oxide compound is mixed with organic solvent and binding agent, and slurry is obtained after ultrasonic disperse；Slurry is equal
Even drop is invested on pretreated carbon paper, up to the electrode slice after drying.
In the application, the additive amount of composite material is 1~5mg；The volume ratio of the organic solvent and binding agent is
1000:10~1000:50；The organic solvent is isopropanol, and the binding agent is Nafion solution.
Optimum condition is as follows：
The dosage of cobalt salt (cobalt acetate, cobalt nitrate) solution is 0.5~1mL, and concentration is 0.5~1mol/L；
The dosage of sodium nitrate solution is 0.5~1mL, and concentration is 0.5~1mol/L；
The dosage of graphene oxide dispersion is 17~23mL, and concentration is 0.5~1.5mol/L；
The volume of the step 3) ammonium hydroxide is 1~8mL, and mixing time is 0.5~4h；
The temperature of the step 4) hydro-thermal reaction is 155~185 DEG C, and the time of hydro-thermal process is 12h；
The temperature of the step 5) drying temperature is 50~70 DEG C, and drying time is 6~12h；
The additive amount of composite material is 2~4mg in the application；The volume ratio of the organic solvent and binding agent is
1000:20~1000:40；The organic solvent is isopropanol, and the binding agent is Nafion solution.
Using X-ray diffraction (XRD) and transmission electron microscope (TEM) to its thing phase morphology with knowable to being characterized, party's legal system
Equably loaded for the cobaltosic oxide nano crystal for going out size uniformity on graphene, basic soilless sticking phenomenon；Pass through at the same time
Raman spectrum (Raman) understands that graphene is more fully hereinafter reduced by hydro-thermal reaction.
Compared with prior art, the present invention has following beneficial effect：
(1) present invention is under conditions of hydro-thermal reaction, while realizes the reduction of graphene oxide and cobaltosic oxide is received
The preparation of meter Jing Ti.Experimental procedure is simplified, improves the preparation speed of reactant.
(2) present invention reduces the quality of electrode slice, improves by the use of by the use of the carbon paper of industrialized production as collector
Electrode performance, suitable for commercial applications.
(3) preparation method of the present invention realizes the controllable preparation of the cobaltosic oxide nano crystal with particular crystal plane, right
There is great directive significance in practical application.
Brief description of the drawings
Fig. 1 is the graphene-supported cobaltosic oxide nano crystal with the exposure of { 112 } crystal face that this method is prepared
The XRD spectrum of compound.
Fig. 2 is the graphene-supported cobaltosic oxide nano crystal with the exposure of { 112 } crystal face that this method is prepared
The transmission electron microscope picture of compound.
Fig. 3 is the graphene-supported cobaltosic oxide nano crystal with the exposure of { 112 } crystal face that this method is prepared
The Raman collection of illustrative plates of compound.
Embodiment
With reference to specific embodiment, the present invention is described in detail.Following embodiments will be helpful to the technology of this area
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the ordinary skill to this area
For personnel, without departing from the inventive concept of the premise, various modifications and improvements can be made.These belong to the present invention
Protection domain.
Embodiment 1
By a certain amount of graphene oxide, ultrasonic disperse obtains the graphene oxide point of 1mg/mL in 17mL deionized waters
Dispersion liquid, graphene oxide dispersion is added by the sodium nitrate solution of the cobalt nitrate solution of 1mL 1mol/L and 1mL 0.5mol/L
In, it is uniformly mixed at room temperature；8mL ammonium hydroxide is added drop-wise in above-mentioned mixed liquor, mechanical agitation 4h, above-mentioned mixed liquor is transferred to instead
Answer in kettle, react 12h at 185 DEG C, when gained black precipitate deionized water, washes of absolute alcohol to be dried to one section afterwards three times
Between, that is, the graphene-supported cobaltosic oxide nano crystal composite material with the exposure of { 112 } crystal face is obtained, its XRD spectrum is such as
Shown in Fig. 1.
3mg products are added in 0.03mL Nafion solutions and 1mL isopropanols, ultrasonic disperse is uniform, by gained slurry
Drop is attached on pretreated carbon paper, and zinc-air battery air cathode electrode slice is obtained after dry.
Embodiment 2
By a certain amount of graphene oxide, ultrasonic disperse obtains the graphene oxide of 0.5mg/mL in 22mL deionized waters
Dispersion liquid, the sodium nitrate solution of the cobalt nitrate solution of 0.5mL 1mol/L and 1mL 0.5mol/L addition graphene oxide are disperseed
In liquid, it is uniformly mixed at room temperature；2mL ammonium hydroxide is added drop-wise in above-mentioned mixed liquor, mechanical agitation 4h, above-mentioned mixed liquor is transferred to
In reaction kettle, 12h is reacted at 185 DEG C, when gained black precipitate deionized water, washes of absolute alcohol to be dried to one section afterwards three times
Between, that is, obtain the graphene-supported cobaltosic oxide nano crystal composite material with the exposure of { 100 } crystal face.
2mg products are added in 0.02mL Nafion solutions and 1mL isopropanols, ultrasonic disperse is uniform, by gained slurry
Drop is attached on pretreated carbon paper, and zinc-air battery air cathode electrode slice is obtained after dry.
Embodiment 3
By a certain amount of graphene oxide, ultrasonic disperse obtains the graphene oxide of 1.5mg/mL in 23mL deionized waters
Dispersion liquid, the sodium nitrate solution of the cobalt nitrate solution of 1mL 0.5mol/L and 0.5mL 1mol/L addition graphene oxide are disperseed
In liquid, it is uniformly mixed at room temperature；2mL ammonium hydroxide is added drop-wise in above-mentioned mixed liquor, mechanical agitation 4h, above-mentioned mixed liquor is transferred to
In reaction kettle, 12h is reacted at 185 DEG C, when gained black precipitate deionized water, washes of absolute alcohol to be dried to one section afterwards three times
Between, that is, obtain the graphene-supported cobaltosic oxide nano crystal composite material with the exposure of { 111 } crystal face.
4mg products are added in 0.04mL Nafion solutions and 1mL isopropanols, ultrasonic disperse is uniform, by gained slurry
Drop is attached on pretreated carbon paper, and zinc-air battery air cathode electrode slice is obtained after dry.
Embodiment 4
By a certain amount of graphene oxide, ultrasonic disperse obtains the graphene oxide point of 1mg/mL in 17mL deionized waters
Dispersion liquid, graphite oxide is added by the sodium nitrate solution of the cobalt nitrate solution of 0.75mL 0.75mol/L and 0.75mL 0.75mol/L
In alkene dispersion liquid, it is uniformly mixed at room temperature；8mL ammonium hydroxide is added drop-wise in above-mentioned mixed liquor, mechanical agitation 4h, by above-mentioned mixed liquor
It is transferred in reaction kettle, reacts 12h at 155 DEG C, gained black precipitate is dried afterwards three times with deionized water, washes of absolute alcohol
For a period of time, that is, the poor cobaltosic oxide nano crystal of the graphene-supported crystallinity with the exposure of { 112 } crystal face is obtained to answer
Condensation material, its transmission electron microscope picture are as shown in Figure 2.
3mg products are added in 0.03mL Nafion solutions and 1mL isopropanols, ultrasonic disperse is uniform, by gained slurry
Drop is attached on pretreated carbon paper, and zinc-air battery air cathode electrode slice is obtained after dry.
Embodiment 5
By a certain amount of graphene oxide, ultrasonic disperse obtains the graphene oxide point of 1mg/mL in 17mL deionized waters
Dispersion liquid, graphene oxide dispersion is added by the sodium nitrate solution of the cobalt nitrate solution of 1mL 1mol/L and 1mL 0.5mol/L
In, it is uniformly mixed at room temperature；8mL ammonium hydroxide is added drop-wise in above-mentioned mixed liquor, mechanical agitation 4h, above-mentioned mixed liquor is transferred to instead
Answer in kettle, react 12h at 165 DEG C, when gained black precipitate deionized water, washes of absolute alcohol to be dried to one section afterwards three times
Between, that is, the general cobaltosic oxide nano crystal composite material of the graphene-supported crystallinity with the exposure of { 112 } crystal face is obtained,
Its Raman collection of illustrative plates is as shown in Figure 3.
3mg products are added in 0.03mL Nafion solutions and 1mL isopropanols, ultrasonic disperse is uniform, by gained slurry
Drop is attached on pretreated carbon paper, and zinc-air battery air cathode electrode slice is obtained after dry.
Embodiment 6
By a certain amount of graphene oxide, ultrasonic disperse obtains the graphene oxide point of 1mg/mL in 17mL deionized waters
Dispersion liquid, graphene oxide dispersion is added by the sodium nitrate solution of the cobalt nitrate solution of 1mL 1mol/L and 1mL 0.5mol/L
In, it is uniformly mixed at room temperature；8mL ammonium hydroxide is added drop-wise in above-mentioned mixed liquor, mechanical agitation 0.5h, above-mentioned mixed liquor is transferred to
In reaction kettle, 12h is reacted at 185 DEG C, when gained black precipitate deionized water, washes of absolute alcohol to be dried to one section afterwards three times
Between, that is, obtain the graphene-supported larger-size cobaltosic oxide nano crystal composite material with the exposure of { 112 } crystal face.
3mg products are added in 0.03mL Nafion solutions and 1mL isopropanols, ultrasonic disperse is uniform, by gained slurry
Drop is attached on pretreated carbon paper, and zinc-air battery air cathode electrode slice is obtained after dry.
Embodiment 7
By a certain amount of graphene oxide, ultrasonic disperse obtains the graphene oxide point of 1mg/mL in 17mL deionized waters
Dispersion liquid, graphene oxide dispersion is added by the sodium nitrate solution of the cobalt nitrate solution of 1mL 1mol/L and 1mL 0.5mol/L
In, it is uniformly mixed at room temperature；8mL ammonium hydroxide is added drop-wise in above-mentioned mixed liquor, mechanical agitation 2h, above-mentioned mixed liquor is transferred to instead
Answer in kettle, react 12h at 185 DEG C, when gained black precipitate deionized water, washes of absolute alcohol to be dried to one section afterwards three times
Between, that is, obtain the general cobaltosic oxide nano crystal composite material of the graphene-supported size with the exposure of { 112 } crystal face.
3mg products are added in 0.03mL Nafion solutions and 1mL isopropanols, ultrasonic disperse is uniform, by gained slurry
Drop is attached on pretreated carbon paper, and zinc-air battery air cathode electrode slice is obtained after dry.
The preparation method of graphene-supported cobaltosic oxide nano crystal composite material that the present invention is disclosed and proposed and its
In the application of zinc-air battery air cathode, those skilled in the art can be by using for reference present disclosure, appropriate feed change and work
The links such as skill route are realized, related although the method and technology of preparing of the present invention are described by preferred embodiment
Technical staff can substantially not depart from present invention, methods and techniques described herein route changed in spirit and scope
Move or reconfigure, to realize final technology of preparing.In particular, all similar replacements and change are to this
It is it will be apparent that they are considered as being included in spiritual, scope and content of the invention for field technology personnel.
Claims (9)
- A kind of 1. preparation method of graphene-supported cobaltosic oxide nano crystal composite material, it is characterized in that step is as follows：1) graphene oxide ultrasonic disperse in deionized water, is weighed, obtains graphene oxide suspension；2) cobalt salt solution, sodium salt solution, are weighed, is uniformly mixed at room temperature, is then added in graphene oxide suspension and obtains Mixed solution；3) ammonium hydroxide, is added into mixed solution, is stirred evenly, obtains cobalt amine complex solution；4), the mixed solution for obtaining step 3) carries out hydro-thermal process under sealed conditions, obtains black precipitate；5), black precipitate obtained by step 4) is washed through deionized water, absolute ethyl alcohol successively, it is dry under air atmosphere, obtain stone Black alkene supported cobaltosic oxide nano crystal composite material.
- 2. the method as described in claim 1, it is characterized in that the cobalt salt is cobalt nitrate or cobalt acetate, concentration for 0.5~ 2mol/L, dosage are 0.5~2mL；The sodium salt is sodium nitrate or sodium acetate, and concentration is 0.1~2mol/L, dosage 0.5 ~2mL.
- 3. the method as described in claim 1, it is characterized in that the graphene oxide suspension concentration is 0.5-3.0mg/mL, instead It is 10~30mL to answer volume.
- 4. the method as described in claim 1, it is characterized in that the volume for adding ammonium hydroxide is 0.5~15mL.
- 5. the method as described in claim 1, it is characterized in that the mixing time is 0.5~4h.
- 6. the method as described in claim 1, it is characterized in that the temperature of the hydro-thermal reaction is 155~185 DEG C, hydro-thermal process Time is 12h.
- 7. the method as described in claim 1, it is characterized in that the temperature of the drying temperature is 40~80 DEG C, drying time 6 ~15h.
- 8. the graphene-supported cobaltosic oxide nano crystal composite material of claim 1 is applied to zinc and air cell air cathode, Graphene-supported cobaltosic oxide compound is mixed with organic solvent and binding agent, slurry is obtained after ultrasonic disperse；By slurry Uniformly drop is invested on pretreated carbon paper, up to the electrode slice after drying.
- 9. application as claimed in claim 8, it is characterised in that the additive amount of the composite material is 1~5mg；It is described organic The volume ratio of solvent and binding agent is 1000:10~1000:50；The organic solvent is isopropanol, and the binding agent is Nafion solution.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109755600A (en) * | 2019-01-29 | 2019-05-14 | 天津大学 | The application of carbon cloth nickel-loaded cobalt oxide nano-sheet composite material and preparation method and electrode |
| CN109817993A (en) * | 2019-01-21 | 2019-05-28 | 天津大学 | The preparation method of nickel cobalt oxygen nano-sized membrane and its application in zinc-air battery |
| CN110098448A (en) * | 2019-05-28 | 2019-08-06 | 中国科学技术大学 | A kind of high-performance composite zinc air secondary battery |
| CN110299532A (en) * | 2019-06-21 | 2019-10-01 | 天津大学 | A kind of preparation method of water system aluminum-air battery device |
| CN110323080A (en) * | 2019-07-04 | 2019-10-11 | 西北工业大学 | The preparation method of aqueous super capacitor |
| CN111261883A (en) * | 2020-02-21 | 2020-06-09 | 河北工业大学 | Preparation method and application of ionic liquid functionalized graphene oxide loaded nano cobaltosic oxide composite material |
| CN111584254A (en) * | 2020-05-19 | 2020-08-25 | 佛山科学技术学院 | Nano porous electrode and preparation method thereof |
| CN113394028A (en) * | 2021-06-17 | 2021-09-14 | 辽宁工程技术大学 | Preparation of Co by gas phase diffusion3O4Method for compounding supercapacitor material with graphene |
| CN113717395A (en) * | 2021-09-01 | 2021-11-30 | 哈尔滨师范大学 | { P6Mo18O73Porous electrode material based on metal organic framework and preparation method and application thereof |
| CN115536011A (en) * | 2022-09-23 | 2022-12-30 | 河南农业大学 | Preparation method of mesoporous metal oxide-graphene composite nanosheet |
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| CN109817993A (en) * | 2019-01-21 | 2019-05-28 | 天津大学 | The preparation method of nickel cobalt oxygen nano-sized membrane and its application in zinc-air battery |
| CN109755600A (en) * | 2019-01-29 | 2019-05-14 | 天津大学 | The application of carbon cloth nickel-loaded cobalt oxide nano-sheet composite material and preparation method and electrode |
| CN110098448A (en) * | 2019-05-28 | 2019-08-06 | 中国科学技术大学 | A kind of high-performance composite zinc air secondary battery |
| CN110299532A (en) * | 2019-06-21 | 2019-10-01 | 天津大学 | A kind of preparation method of water system aluminum-air battery device |
| CN110323080B (en) * | 2019-07-04 | 2021-07-16 | 西北工业大学 | Preparation method of water system super capacitor |
| CN110323080A (en) * | 2019-07-04 | 2019-10-11 | 西北工业大学 | The preparation method of aqueous super capacitor |
| CN111261883A (en) * | 2020-02-21 | 2020-06-09 | 河北工业大学 | Preparation method and application of ionic liquid functionalized graphene oxide loaded nano cobaltosic oxide composite material |
| CN111584254A (en) * | 2020-05-19 | 2020-08-25 | 佛山科学技术学院 | Nano porous electrode and preparation method thereof |
| CN113394028A (en) * | 2021-06-17 | 2021-09-14 | 辽宁工程技术大学 | Preparation of Co by gas phase diffusion3O4Method for compounding supercapacitor material with graphene |
| CN113717395A (en) * | 2021-09-01 | 2021-11-30 | 哈尔滨师范大学 | { P6Mo18O73Porous electrode material based on metal organic framework and preparation method and application thereof |
| CN113717395B (en) * | 2021-09-01 | 2023-02-24 | 哈尔滨师范大学 | Porous electrode material with { P6Mo18O73} based metal organic framework and preparation method and application thereof |
| CN115536011A (en) * | 2022-09-23 | 2022-12-30 | 河南农业大学 | Preparation method of mesoporous metal oxide-graphene composite nanosheet |
| CN115536011B (en) * | 2022-09-23 | 2023-11-21 | 河南农业大学 | Preparation method of mesoporous metal oxide-graphene composite nano-sheet |
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Application publication date: 20180413 |