CN110400938A - A kind of Co of porous surface club shaped structure3S4The preparation method of zinc and air cell catalyst - Google Patents
A kind of Co of porous surface club shaped structure3S4The preparation method of zinc and air cell catalyst Download PDFInfo
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- CN110400938A CN110400938A CN201910692230.1A CN201910692230A CN110400938A CN 110400938 A CN110400938 A CN 110400938A CN 201910692230 A CN201910692230 A CN 201910692230A CN 110400938 A CN110400938 A CN 110400938A
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- zinc
- air cell
- cell catalyst
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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
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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
- H01M4/8605—Porous electrodes
- H01M4/861—Porous electrodes with a gradient in the porosity
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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
- H01M4/88—Processes of manufacture
- H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
- H01M4/8882—Heat treatment, e.g. drying, baking
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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
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Abstract
The invention discloses a kind of Co of porous surface club shaped structure3S4The preparation method of zinc and air cell catalyst, cobalt acetate and diamine are dissolved in distilled water, and sulphur source is added after being uniformly mixed, and obtain uniform and stable solution sodium in 25 DEG C of stirring 10min；Obtained uniform and stable solution is transferred in the stainless steel autoclave of polytetrafluoroethyllining lining in 100-140 DEG C of holding 10-14h, to reaction kettle cooled to room temperature, by product, with secondary water washing, vacuum drying obtains the Co of porous surface club shaped structure afterwards for several times3S4Zinc and air cell catalyst.The zinc and air cell catalyst of porous surface club shaped structure produced by the present invention has biggish specific surface area, and 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 Co of porous surface club shaped structure3S4Zinc
The preparation method of empty cell 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
With experimental application, become the hot spot of Recent study.Catalyst is core component in zinc and air cell, and certainly
Determine the critical material of battery cost and performance.In recent years, the research about zinc and air cell catalyst emerges one after another, however synthesizes
ORR and OER bifunctional electrocatalyst is still challenging.Therefore, developing a kind of bifunctional electrocatalyst becomes zinc and air cell
There is one of major issue to be solved in catalyst synthesis technology field.
Recently, the synthesis of many transition metal base elctro-catalysts, such as transient metal sulfide, due to its height are had been realized in
Latent active, perfect stability and brilliance electric conductivity be applied to OER/ORR reaction, and then caused the extensive of people
Concern.Wherein transient metal sulfide specific surface area is larger, and active site exposure is more, and can preferably contact with electrolyte,
With good ORR performance, however it is unstable, is easy to happen reunion, these deficiencies restrict transient metal sulfide into
One step promotes and applies.
However, the catalytic performance of transient metal sulfide can be controlled by form, the surface of engineering defect is modified, facet,
Strain optimizes with interface and the electric structure of modulation.Specifically, adjustment form to generate 2D nanostructure, this usually along with
The deformation of surface texture and the variation of electrical structure, because without size and intrinsic Large ratio surface, it may be possible to it is advantageous in order to
Catalytic efficiency is improved, interface is the important area for improving catalytic activity.Exposed boundary defect is conducive to reactant in interface
Absorption and activation, this is conducive to catalytic performance.In addition, being recently proposed the common deficiency in the vacancy S in transient metal sulfide material
Significant impact can be generated.The catalytic activity for improving OER/ORR is measured by additional exposure activity edge site.Therefore, it develops
Defect interface nanometer sheet (NS) with abundant active site is of great significance for exploring efficient and stable elctro-catalyst.
Summary of the invention
That the technical problem to be solved by the present invention is to provide a kind of easy to operate, reaction conditions is mild, reaction efficiency is higher and
The Co of the lower porous surface club shaped structure of energy consumption3S4The preparation method of zinc and air cell catalyst.
The present invention adopts the following technical scheme that solve above-mentioned technical problem, a kind of Co of porous surface club shaped structure3S4Zinc
The preparation method of empty cell catalyst, it is characterised in that specific steps are as follows:
Step S1: cobalt acetate and diamine are dissolved in distilled water, and sulphur source is added after being uniformly mixed, in 25 DEG C of stirring 10min
Uniform and stable solution is obtained, the sulphur source is thioacetamide, thiocarbamide, vulcanized sodium, sulphur powder, ammonium sulfide or sodium thiosulfate；
Step S2: the uniform and stable solution that step S1 is obtained is transferred in the stainless steel autoclave of polytetrafluoroethyllining lining
In 100-140 DEG C of holding 10-14h, to reaction kettle cooled to room temperature, product is dried in vacuo afterwards for several times with secondary water washing
Obtain the Co of porous surface club shaped structure3S4Zinc and air cell catalyst；
The Co of the porous surface club shaped structure3S4To show higher OER, ORR bis- for zinc and air cell for zinc and air cell catalyst
Function electro catalytic activity, the Co with porous surface club shaped structure3S4Zinc and air cell catalyst can provide ideal for electrode reaction
Solid-liquid-gas threephase region, provide more multichannel for the transmission of electrolyte, and then improve the specific surface area of zinc and air cell catalyst,
Increase the catalytic activity of elctro-catalyst, while playing good synergistic effect between two component of Co and S, and in non-calcinated condition
Under obtain target product, avoid because calcining causes duct to collapse, and avoid because calcining causes Co3S4Structure variation, containment
The tendency of electrical property decaying.
Further preferably, the mass ratio that feeds intake of the cobalt acetate, diamine and sulphur source is 0.025-0.249:0.125:
0.076。
Compared with the prior art, the invention has the following beneficial effects:
1, the bifunctional electrocatalyst for the porous surface club shaped structure that the present invention synthesizes, synthetic method is easy to operate, reacts item
Part is mild, reaction efficiency is high and low energy consumption；
2, Co in the present invention3S4Zinc and air cell catalyst have biggish specific surface area, active site cruelly can with dew it is more, and
It can preferably be contacted with electrolyte, can effectively improve the electro catalytic activity of catalyst；
3, the Co for the porous surface club shaped structure that the present invention synthesizes3S4Metal sulfide not only can be improved in zinc and air cell catalyst
Stability, prevent it from reuniting, and the synergistic effect between nano particle also achieves material under the conditions of non-calcinated
The difunctional electro catalytic activity of OER, ORR is had both, is had broad application prospects on zinc and air cell.
Detailed description of the invention
Fig. 1 is Co made from the embodiment of the present invention 13S4The SEFEM of zinc and air cell catalyst schemes；
Fig. 2 is Co made from the embodiment of the present invention 13S4The SEFEM of zinc and air cell catalyst schemes；
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
It takes 0.025g cobalt acetate and 0.125g diamine to be dissolved in 30mL distilled water, 0.076g is added after being uniformly mixed thereto
Thiocarbamide is finally transferred in the stainless steel autoclave of polytetrafluoroethyllining lining keep in 120 DEG C in 25 DEG C of stirring 10min
12h is placed in oven and dried 12h after for several times through secondary water washing and obtains Co to reaction kettle cooled to room temperature3S4The empty electricity of zinc
Pond catalyst.
Take Co made from 2mg the present embodiment3S4Zinc and air cell catalyst is dispersed in alcohol dispersant, adds carbon black, will
It is coated in glassy carbon electrode surface after mixed liquor ultrasound is uniform, using three-electrode system, which is measured by electrochemical workstation
Performance, electric performance test result is as shown in Figure 3.
Embodiment 2
It takes 0.249g cobalt acetate and 0.125g diamine to be dissolved in 30mL distilled water, 0.076g is added after being uniformly mixed thereto
Thioacetamide is finally transferred in the stainless steel autoclave of polytetrafluoroethyllining lining in 25 DEG C of stirring 10min in 120
DEG C keep 12h be placed in oven and dried 12h to reaction kettle cooled to room temperature after for several times through secondary water washing and obtain Co3S4
Zinc and air cell catalyst.
Embodiment 3
It takes 0.249g cobalt acetate and 0.125g diamine to be dissolved in 30mL distilled water, 0.076g is added after being uniformly mixed thereto
Ammonium sulfide is finally transferred in the stainless steel autoclave of polytetrafluoroethyllining lining protect in 120 DEG C in 25 DEG C of stirring 10min
12h is held, to reaction kettle cooled to room temperature, 12h is placed in oven and dried after for several times through secondary water washing and obtains Co3S4Zinc is empty
Cell catalyst.
Comparative example 1
It takes 0.025g cobalt acetate and 0.250g diamine to be dissolved in 30mL distilled water, in 25 DEG C of stirring 10min, is finally transferred to poly- four
In 120 DEG C of holding 6h in the stainless steel autoclave of vinyl fluoride liner, to reaction kettle cooled to room temperature, through secondary washing
It washs and is placed in oven and dried 12h afterwards for several times and obtains Co (OH)2Zinc and air cell catalyst.
Take Co made from this comparative example of 2mg (OH)2Zinc and air cell catalyst is dispersed in alcohol dispersant, 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.
Comparative example 2
It takes 0.025g cobalt acetate to be dissolved in distilled water, 0.076g thiocarbamide is added after being uniformly mixed thereto, stirred in 25 DEG C
10min is finally transferred in the stainless steel autoclave of polytetrafluoroethyllining lining in 120 DEG C of holding 6h, to reaction kettle nature
It is cooled to room temperature, is placed in oven and dried 12h after for several times through secondary water washing and obtains CoS zinc and air cell catalyst.
It takes CoS zinc and air cell catalyst made from this comparative example of 2mg 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, which is measured by electrochemical workstation
Performance, electric performance test result is as shown in Figure 3.
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 (2)
1. a kind of Co of porous surface club shaped structure3S4The preparation method of zinc and air cell catalyst, it is characterised in that specific steps
Are as follows:
Step S1: cobalt acetate and diamine are dissolved in distilled water, and sulphur source is added after being uniformly mixed, in 25 DEG C of stirring 10min
Uniform and stable solution is obtained, the sulphur source is thioacetamide, thiocarbamide, vulcanized sodium, sulphur powder, ammonium sulfide or sodium thiosulfate；
Step S2: the uniform and stable solution that step S1 is obtained is transferred in the stainless steel autoclave of polytetrafluoroethyllining lining
In 100-140 DEG C of holding 10-14h, to reaction kettle cooled to room temperature, product is dried in vacuo afterwards for several times with secondary water washing
Obtain the Co of porous surface club shaped structure3S4Zinc and air cell catalyst；
The Co of the porous surface club shaped structure3S4Zinc and air cell catalyst shows the bis- function of higher OER, ORR for zinc and air cell
Energy electro catalytic activity, the Co with porous surface club shaped structure3S4Zinc and air cell catalyst can provide preferably for electrode reaction
Solid-liquid-gas threephase region provides more multichannel for the transmission of electrolyte, and then improves the specific surface area of zinc and air cell catalyst, increases
The catalytic activity of electrocatalyst, while good synergistic effect has been played between two component of Co and S, and under the conditions of non-calcinated
Target product is obtained, is avoided because calcining causes duct to collapse, and is avoided because calcining causes Co3S4Structure variation, containment
The tendency of electrical property decaying.
2. the Co of porous surface club shaped structure according to claim 13S4The preparation method of zinc and air cell catalyst, it is special
Sign is: the mass ratio that feeds intake of the cobalt acetate, diamine and sulphur source is 0.025-0.249:0.125:0.076.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114622220A (en) * | 2022-04-01 | 2022-06-14 | 南京晓庄学院 | Co3S4Doping SnSxPreparation method and application of heterogeneous nanosheet |
Citations (4)
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| CN101786671A (en) * | 2009-10-30 | 2010-07-28 | 陕西科技大学 | Method for preparing bar-shaped cobalt sulfide nanocrystalline |
| CN106824228A (en) * | 2017-03-21 | 2017-06-13 | 合肥工业大学 | A kind of flower-shaped cobalt sulfide photochemical catalyst and preparation method thereof |
| CN108630947A (en) * | 2017-03-15 | 2018-10-09 | 中国科学院福建物质结构研究所 | A kind of preparation method of the cobalt sulfide of rechargeable type zinc-air battery/carbon nanocatalyst |
| CN109309235A (en) * | 2017-07-27 | 2019-02-05 | 北京大学深圳研究生院 | A kind of bifunctional electrocatalyst and its application and preparation method |
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2019
- 2019-07-30 CN CN201910692230.1A patent/CN110400938A/en active Pending
Patent Citations (4)
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| CN101786671A (en) * | 2009-10-30 | 2010-07-28 | 陕西科技大学 | Method for preparing bar-shaped cobalt sulfide nanocrystalline |
| CN108630947A (en) * | 2017-03-15 | 2018-10-09 | 中国科学院福建物质结构研究所 | A kind of preparation method of the cobalt sulfide of rechargeable type zinc-air battery/carbon nanocatalyst |
| CN106824228A (en) * | 2017-03-21 | 2017-06-13 | 合肥工业大学 | A kind of flower-shaped cobalt sulfide photochemical catalyst and preparation method thereof |
| CN109309235A (en) * | 2017-07-27 | 2019-02-05 | 北京大学深圳研究生院 | A kind of bifunctional electrocatalyst and its application and preparation method |
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| J.H.ZHAN，ET AL.: "Hydrazine-Assisted Low-Temperature Hydrothermal Preparation of Nanocrystalline Jaipurite", 《JOURNAL OF SOLID STATE CHEMISTRY》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114622220A (en) * | 2022-04-01 | 2022-06-14 | 南京晓庄学院 | Co3S4Doping SnSxPreparation method and application of heterogeneous nanosheet |
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