CN110400940A - A kind of preparation method and applications of the CoO bifunctional electrocatalyst with hollow out club shaped structure - Google Patents
A kind of preparation method and applications of the CoO bifunctional electrocatalyst with hollow out club shaped structure Download PDFInfo
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- CN110400940A CN110400940A CN201910678847.8A CN201910678847A CN110400940A CN 110400940 A CN110400940 A CN 110400940A CN 201910678847 A CN201910678847 A CN 201910678847A CN 110400940 A CN110400940 A CN 110400940A
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- Prior art keywords
- coo
- shaped structure
- hollow out
- club shaped
- bifunctional electrocatalyst
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
- H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
Abstract
The invention discloses a kind of preparation methods of CoO bifunctional electrocatalyst with hollow out club shaped structure, cobalt chloride and urea are dissolved in distilled water, it is uniformly mixed to be placed in reaction kettle and obtains purple powder precipitating in 80-200 DEG C of reaction, then vacuum drying obtains rodlike CoO presoma after secondary water and dehydrated alcohol washing for several times；It step S1 is obtained rodlike CoO presoma is placed in tube furnace to obtain the CoO bifunctional electrocatalyst with hollow out club shaped structure in 200-500 DEG C of calcining 2h.There are many holes on bifunctional electrocatalyst surface in the present invention, have biggish specific surface area, active site exposure is more, and can preferably contact with electrolyte, can effectively improve the electro catalytic activity of bifunctional electrocatalyst.
Description
Technical field
The invention belongs to zinc and air cell catalyst technical fields, and in particular to a kind of CoO with hollow out club shaped structure is bis-
The preparation method and applications of function elctro-catalyst.
Background technique
Zinc and air cell has the advantages such as high-energy-density, low cost, pollution-free, in many fields as a kind of clean energy resource
There is substantial application, becomes the hot spot of Recent study.In zinc and air cell, catalyst is core component, and certainly
Determine the critical material of battery cost and performance.In recent years, the research about zinc and air cell single function catalyst emerges one after another, so
And it is still challenging to synthesize ORR and OER bifunctional electrocatalyst.Therefore, developing a kind of bifunctional electrocatalyst becomes zinc
Empty cell catalyst synthesis technical field has one of major issue to be solved.
Recently, the synthesis of many transition metal base elctro-catalysts, such as transition metal oxide, due to its height are had been realized in
Latent active, perfect stability and brilliance electric conductivity be applied to OER/ORR reaction, caused the extensive pass of people
Note.Wherein transition metal oxide specific surface area is larger, and active site exposure is more, therefore has good OER performance, however
Its structure in catalytic process is more easily damaged, unstable, these deficiencies restrict the application of amorphous transition metal oxide.
The catalyst of engraved structure because it is with biggish specific surface area, thus can increase in catalytic process electrode and
The contact area of electrolyte exposes more catalytic sites, to improve its catalytic performance.However the material of this kind of structure by
In with slow dynamic characteristic, largely showing weaker OER performance, these problems need further to be solved.
Summary of the invention
That the technical problem to be solved by the present invention is to provide a kind of synthetic operations is simple, reaction condition is mild, reaction efficiency compared with
High and the CoO bifunctional electrocatalyst with hollow out club shaped structure that low energy consumption preparation method, the bis- function of CoO made from this method
Energy elctro-catalyst effectively increases the difunctional electro catalytic activity of OER, ORR of zinc and air cell elctro-catalyst for zinc and air cell.
The present invention adopts the following technical scheme that the CoO with hollow out club shaped structure is difunctional to solve above-mentioned technical problem
The preparation method of elctro-catalyst, it is characterised in that specific steps are as follows:
Step S1: cobalt chloride and urea are dissolved in distilled water, are uniformly mixed and are placed in reaction kettle in 80-200 DEG C instead
Purple powder precipitating should be obtained, then vacuum drying obtains rodlike CoO presoma after secondary water and dehydrated alcohol washing for several times；
Step S2: it step S1 is obtained rodlike CoO presoma is placed in tube furnace to obtain in 200-500 DEG C of calcining 2h with hollow out
The CoO bifunctional electrocatalyst of club shaped structure, the average diameter of club shaped structure are 500nm.
Preferably, the mass ratio that feeds intake of cobalt chloride described in step S1 and urea is 1:5-5:1.
CoO bifunctional electrocatalyst of the present invention with hollow out club shaped structure is applied in preparing zinc and air cell,
It is characterized in that detailed process are as follows: it disperses the CoO bifunctional electrocatalyst with hollow out club shaped structure in alcohol dispersant,
Add carbon black, by mixed liquor ultrasound uniformly after be coated in glassy carbon electrode surface, using three-electrode system, pass through electrochemical workstation
The performance of the catalyst is measured, which shows the difunctional electro catalytic activity of higher OER, ORR, has
The CoO bifunctional electrocatalyst of hollow out club shaped structure can provide big specific surface area for electrode reaction, increase difunctional electricity and urge
The catalytic activity of agent, while high porosity can promote the infiltration of electrolyte in electro-chemical test, promote diffuser efficiency.
Compared with the prior art, the invention has the following beneficial effects:
1, the bifunctional electrocatalyst of hollow out club shaped structure that the present invention synthesizes, synthetic method is easy to operate, reaction condition temperature
It is high with reaction efficiency and low energy consumption；
2, there are many holes on bifunctional electrocatalyst surface in the present invention, have biggish specific surface area, and active site exposure is more,
And can preferably be contacted with electrolyte, it can effectively improve the electro catalytic activity of bifunctional electrocatalyst；
3, the CoO zinc and air cell catalyst for the hollow out club shaped structure that the present invention synthesizes not only can make the material have both OER, ORR
Difunctional electro catalytic activity, and the stability of CoO can be improved in calcination process, prevents its structure in cyclic process from occurring broken
It is bad, have broad application prospects on zinc and air cell.
Detailed description of the invention
Fig. 1 is the SEM figure of rodlike CoO presoma made from the embodiment of the present invention 1；
Fig. 2 is the SEM figure of the CoO zinc and air cell catalyst obtained with hollow out club shaped structure of the embodiment of the present invention 1；
Fig. 3 is product electrochemical property test figure made from the embodiment of the present invention 1 and comparative example 1, comparative example 2.
Specific embodiment
Above content of the invention is described in further details by the following examples, but this should not be interpreted as to this
The range for inventing above-mentioned theme is only limitted to embodiment below, and all technologies realized based on above content of the present invention belong to this hair
Bright range.
Embodiment 1
1.2g cobalt chloride and 0.3g urea are dissolved in 60mL distilled water, are placed into after being uniformly mixed in 100mL reaction kettle,
By 140 DEG C, purple powder precipitating is obtained after 10h reaction, after secondary water and dehydrated alcohol washing for several times in a vacuum drying oven
It is dried to obtain rodlike CoO presoma；Obtained rodlike CoO presoma is finally obtained into tool in 400 DEG C of calcining 2h in tube furnace
There is the CoO zinc and air cell catalyst of engraved structure.The diameter of rodlike CoO presoma made from the present embodiment is about as shown in Figure 1
160nm；The diameter of the present embodiment CoO zinc and air cell catalyst obtained with hollow out club shaped structure is about as shown in Figure 2
500nm。
It takes CoO zinc and air cell catalyst made from 2mg the present embodiment to be dispersed in alcohol dispersant, adds carbon black, it will
It is coated in glassy carbon electrode surface after mixed liquor ultrasound is uniform, using three-electrode system, it is difunctional that this is measured by electrochemical workstation
The performance of elctro-catalyst, electric performance test result are as shown in Figure 3.
Embodiment 2
1.2g cobalt chloride and 0.3g urea are dissolved in 60mL distilled water, are placed into after being uniformly mixed in 100mL reaction kettle,
By 100 DEG C, purple powder precipitating is obtained after 10h reaction, after secondary water and dehydrated alcohol washing for several times in a vacuum drying oven
It is dried to obtain rodlike CoO presoma；Obtained rodlike CoO presoma is finally obtained into tool in 400 DEG C of calcining 2h in tube furnace
There is the CoO zinc and air cell catalyst of hollow out club shaped structure.
Embodiment 3
1.2g cobalt chloride and 0.3g urea are dissolved in 60mL distilled water, are placed into after being uniformly mixed in 100mL reaction kettle,
By 200 DEG C, purple powder precipitating is obtained after 10h reaction, after secondary water and dehydrated alcohol washing for several times in a vacuum drying oven
It is dried to obtain rodlike CoO presoma；Obtained rodlike CoO presoma is finally obtained into tool in 400 DEG C of calcining 2h in tube furnace
There is the CoO zinc and air cell catalyst of hollow out club shaped structure.
Comparative example 1
1.2g cobalt chloride and 0.3g urea are dissolved in 60mL distilled water, are placed into after being uniformly mixed in 100mL reaction kettle,
By 200 DEG C, purple powder precipitating is obtained after 10h reaction, after secondary water and dehydrated alcohol washing for several times in a vacuum drying oven
It is dried to obtain rodlike CoO presoma.
It takes rodlike CoO presoma made from this comparative example of 2mg to be dispersed in alcohol dispersant as catalyst, adds charcoal
It is black, by mixed liquor ultrasound uniformly after be coated in glassy carbon electrode surface, using three-electrode system, this is measured by electrochemical workstation and is urged
The performance of agent, electric performance test result are as shown in Figure 3.
Zinc and air cell catalyst produced by the present invention with hollow out club shaped structure has the difunctional electricity of good OER, ORR
Catalytic activity.In the electric performance test result of Fig. 3, (a) is that the ORR polarization of catalyst prepared by embodiment 1 and comparative example 1 is bent
Line, (b) the OER polarization curve of the catalyst prepared for embodiment 1 and comparative example 1, compared with comparative example 1, made from embodiment 1
Zinc and air cell catalyst with hollow out club shaped structure shows the difunctional electro catalytic activity of higher OER, ORR；We divide
Analysis thinks that the CoO zinc and air cell catalyst provided by the invention with hollow out club shaped structure can provide big for electrode reaction
Specific surface area increases the catalytic activity of bifunctional electrocatalyst, while high porosity can promote electricity in electro-chemical test
The infiltration of matter is solved, diffuser efficiency is promoted.The electricity of CoO zinc and air cell catalyst prepared by the present invention with hollow out club shaped structure is urged
It is excellent to change activity performance, is a kind of zinc and air cell catalyst with broad prospect of application.
Embodiment above describes basic principles and main features of the invention and advantage, the technical staff of the industry should
Understand, the present invention is not limited to the above embodiments, and the above embodiments and description only describe originals of the invention
Reason, under the range for not departing from the principle of the invention, various changes and improvements may be made to the invention, these changes and improvements are each fallen within
In the scope of protection of the invention.
Claims (3)
1. the preparation method of the CoO bifunctional electrocatalyst with hollow out club shaped structure, it is characterised in that specific steps are as follows:
Step S1: cobalt chloride and urea are dissolved in distilled water, are uniformly mixed and are placed in reaction kettle in 80-200 DEG C instead
Purple powder precipitating should be obtained, then vacuum drying obtains rodlike CoO presoma after secondary water and dehydrated alcohol washing for several times；
Step S2: it step S1 is obtained rodlike CoO presoma is placed in tube furnace to obtain in 200-500 DEG C of calcining 2h with hollow out
The CoO bifunctional electrocatalyst of club shaped structure, the average diameter of club shaped structure are 500nm.
2. the preparation method of the CoO bifunctional electrocatalyst according to claim 1 with hollow out club shaped structure, feature
Be: the mass ratio that feeds intake of cobalt chloride described in step S1 and urea is 1:5-5:1.
3. according to the method for claim 1 prepared by the CoO bifunctional electrocatalyst obtained with hollow out club shaped structure
It is applied in zinc and air cell, it is characterised in that detailed process are as follows: disperse the CoO bifunctional electrocatalyst with hollow out club shaped structure
In alcohol dispersant, add carbon black, by mixed liquor ultrasound uniformly after be coated in glassy carbon electrode surface, using three-electrode system,
The performance of the catalyst is measured by electrochemical workstation, which shows the bis- function of higher OER, ORR
Energy electro catalytic activity, the CoO bifunctional electrocatalyst with hollow out club shaped structure can provide big specific surface for electrode reaction
Product, increases the catalytic activity of bifunctional electrocatalyst, while high porosity can promote electrolyte in electro-chemical test
Infiltration promotes diffuser efficiency.
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| CN201910678847.8A CN110400940A (en) | 2019-07-25 | 2019-07-25 | A kind of preparation method and applications of the CoO bifunctional electrocatalyst with hollow out club shaped structure |
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| CN201910678847.8A CN110400940A (en) | 2019-07-25 | 2019-07-25 | A kind of preparation method and applications of the CoO bifunctional electrocatalyst with hollow out club shaped structure |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108390014A (en) * | 2018-01-08 | 2018-08-10 | 华南师范大学 | The preparation method of foamed nickel supported different-shape cobalt black nano material |
| CN108963274A (en) * | 2018-06-30 | 2018-12-07 | 河南师范大学 | A kind of preparation method of New-type bifunctional elctro-catalyst and its application in zinc and air cell |
| CN108963277A (en) * | 2018-07-02 | 2018-12-07 | 河南师范大学 | A kind of preparation method and applications of rechargeable type zinc and air cell bifunctional catalyst |
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- 2019-07-25 CN CN201910678847.8A patent/CN110400940A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108390014A (en) * | 2018-01-08 | 2018-08-10 | 华南师范大学 | The preparation method of foamed nickel supported different-shape cobalt black nano material |
| CN108963274A (en) * | 2018-06-30 | 2018-12-07 | 河南师范大学 | A kind of preparation method of New-type bifunctional elctro-catalyst and its application in zinc and air cell |
| CN108963277A (en) * | 2018-07-02 | 2018-12-07 | 河南师范大学 | A kind of preparation method and applications of rechargeable type zinc and air cell bifunctional catalyst |
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Application publication date: 20191101 |