CN109306501A - A kind of preparation method of cobalt sulfide-carbon original position electrode - Google Patents
A kind of preparation method of cobalt sulfide-carbon original position electrode Download PDFInfo
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
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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
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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
- H01M4/8825—Methods for deposition of the catalytic active composition
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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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- 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
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The present invention provides a kind of drop coating preparation method of multi-functional cobalt sulfide-carbon original position electrode, and cobalt salt and the carbonaceous organic materials such as Tx-100 or sucrose or aniline are dissolved in volatilization nonaqueous solvents, and thiocarbamide is added as sulphur source, obtains body liquid before Co-C-S；Above-mentioned preceding body liquid is applied in substrate, is put after dry in an ar atmosphere or N2In atmosphere, annealing vulcanization.The product that technical solution of the present invention obtains has that low equipment requirement, required low raw-material cost, reaction condition is easily controllable, simple production process, is formed by good product consistency, the advantages that environmental pollution is small can be used for the multi-functional elctro-catalyst of HER, OER and ORR.
Description
Technical field
The present invention relates to electrode in situ and its preparations, belong to energy stores and transition material and devices field.
Background technique
Efficient electrocatalysis material energy stores and switching device (such as: electrolysis water, metal-air battery, fuel cell
Deng) in play very important effect, environmental protection and the development of new energy will be pushed.Currently, platinum, palladium have excellent electro-catalysis
Liberation of hydrogen and hydrogen reduction function, i.e. catalysis Hydrogen evolving reaction (Hydrogen Evolution Reaction, HER) and hydrogen reduction are anti-
Answer (oxygen reduction reaction, ORR)；Yttrium oxide, ruthenium-oxide have excellent analysis oxygen (Oxygen
Evolution Reaction, OER) catalysis.However, these noble metals and its oxide reserves are limited, at high price,
Middle platinum is also easily gradually failed by methanol poisoning in catalysis ORR reaction process.Therefore a large amount of researcher is devoted to
Develop their alternative materials.The study found that transient metal sulfide can be used as HER elctro-catalyst, transition metal oxide or
Hydroxide has the function of good OER electro-catalysis, and carbon material can also be used as the alternative materials catalysis ORR of platinum, palladium, however few
There is material while having the function of difunctional or three (catalysis HER, OER and ORR reactions).Thus, the present invention is directed to prepare one kind
Inexpensively, efficiently three function elctro-catalysts --- the compound (cobalt sulfide-carbon) of cobalt sulfide and carbon, wherein cobalt sulfide plays catalysis
The cobalt oxide of Surface Creation plays the function of catalysis OER reaction in OER reaction, carbon is wherein catalyzed for the function of HER, cobalt sulfide
The function of ORR reaction, furthermore the appearance structure of this compound, conductive capability, surface component defect also can mutually cooperate with promotion
Catalysis reaction.
Summary of the invention
In view of this, cobalt sulfide-carbon electrode method is prepared in situ the object of the present invention is to provide a kind of, this method has
Equipment requirement is low, required low raw-material cost, reaction condition is easily controllable, simple production process, is formed by homogeneity of product
Well, the advantages that environmental pollution is small, can be used for the multi-functional elctro-catalyst of HER, OER and ORR, the batch production for electrode in situ
It is of great importance.
For this purpose, being coated on after forming a film in substrate, then prepare original position the present invention provides one kind with Co-C-S for forerunner's night
Cobalt sulfide-carbon electrode method, includes the following steps:
The first step, under the conditions of being stirred at room temperature, by cobalt salt and carbonaceous organic material (including Tx-100, glucose, sucrose, benzene
Any one in amine, preferably Tx-100) it is dissolved in n,N-Dimethylformamide isopolarity easy volatile solvent, thiocarbamide conduct is added
Sulphur source obtains body liquid before Co-C-S, and wherein the concentration of Co atom is 200~900mM, carbonaceous organic material (including Tx-100, grape
Sugar, sucrose, any one in aniline, preferably Tx-100) it with the volume ratio of nonaqueous solvents is 0.03~2.The meaning of the step
Justice is: carbonaceous organic material is (including any one in Tx-100, glucose, sucrose, aniline, preferably Tx- in precursor liquid
100) carbon can be not only provided, but also there is certain viscosity, be easy to be coated with and load capacity can be increased；Reaction reagent is uniform
Dispersion, obtain uniformly Co, C, S element without precipitating the mixed uniformly preceding body liquid of atomic scale be prepare uniform cobalt sulfide-
Carbon array lays good basis；Air pollution can be effectively reduced using thiocarbamide as sulphur source, it is safely controllable easy to operate.
Second step by above-mentioned preceding body drop-coated or is spun in substrate, such as carbon cloth, graphite paper, copper or nickel foil, in dry empty
It is dry in gas, or in 70~100 DEG C of rapid draing in thermal station, the meaning of the step is: n,N-Dimethylformamide is quickly waved
It is left after hair by Co salt, carbonaceous organic material (including any one in Tx-100, glucose, sucrose, aniline, preferably Tx-
100) with the mixed uniformly forerunner's film layer of thiocarbamide, uniform cobalt sulfide-carbon film is still obtained after guaranteeing subsequent high temperature annealing reaction.
Third step, by precursor film in step 2 in Ar atmosphere or N2In atmosphere, through 500~900 DEG C of sintering 30min~
Cobalt sulfide-carbon composite in-situ electrode can be obtained in 4h, furnace cooling taking-up.
Cobalt sulfide-carbon original position electrode preparation principle is exactly: 1. utilizing the uniform of Co, C in Co-C-S precursor liquid and S atom
Combination and cobalt salt, Tx-100 and the easy homogeneous film formation of thiocarbamide precursor liquid；2. it is reacted using 500~900 DEG C of high annealings, wherein
The sulfur-containing compound (such as: hydrogen sulfide) and Co salt reaction in-situ that thiocarbamide pyrolytic generates generate cobalt sulfide, and Tx-100 is as carbon
Under the high temperature of source gradually dehydrogenation deoxidation (hydrone of formation and a small amount of carbon oxygen, hydrocarbon oxygen small molecule by argon gas with) form carbon, this
Outer thiocarbamide decomposes the hydrogen sulfide generated, ammonia can also mix carbon skeleton in carbon material forming process or surface forms S, N doping
Carbon material is to improve ORR catalytic performance.
Detailed description of the invention
Cobalt sulfide prepared by Fig. 1 embodiment 1-carbon original position electrode SEM.
Cobalt sulfide prepared by Fig. 2 embodiment 1,2-carbon original position electrode (a) HER, (b) OER, the linear volt-ampere of (c) ORR are swept
Retouch (LSV).
Stability test figure of cobalt sulfide prepared by Fig. 3 embodiment 1-carbon original position electrode under 200mA constant current.
Cobalt sulfide prepared by Fig. 4 (a) embodiment 4-carbon original position electrode linear voltammetric scan of HER (LSV)；(b) implement
Cobalt sulfide prepared by example 3,4-carbon original position electrode linear voltammetric scan of OER (LSV)；(c) embodiment 3, vulcanization prepared by 4
Cobalt-carbon original position electrode linear voltammetric scan of ORR (LSV).
Cobalt sulfide prepared by Fig. 5 embodiment 4-carbon original position electrode SEM.
Cobalt sulfide prepared by Fig. 6 embodiment 4-carbon original position electrode XRD.
Cobalt sulfide prepared by Fig. 7 (a) embodiment 5-carbon original position electrode linear voltammetric scan of HER (LSV)；(b) implement
Cobalt sulfide prepared by example 5-carbon original position electrode linear voltammetric scan of OER (LSV)；(c) embodiment 5, vulcanization prepared by 6,7
Cobalt-carbon original position electrode linear voltammetric scan of ORR (LSV).
Cobalt sulfide prepared by Fig. 8 embodiment 8,9-carbon original position electrode linear voltammetric scan of ORR (LSV).
Cobalt sulfide prepared by Fig. 9 embodiment 10,11-carbon original position electrode (a) OER, the linear voltammetric scan of (b) ORR
(LSV)。
Specific embodiment
To other explanations of above-mentioned attached drawing:
HER, OER, ORR performance LSV test method in inventive embodiments are as follows: cobalt sulfide-carbon original position electrode be working electrode,
Using carbon-point be to electrode, to be saturated Hg/HgO electrode as reference electrode, electrolyte used are as follows: 1MKOH aqueous solution, scanning speed are
5mVs-1.Wherein HER test is saturated with nitrogen, OER and ORR test is saturated with oxygen.
Embodiment 1:
At room temperature, six water of cobalt chloride, Tx-100 and thiocarbamide are dissolved in 2.7mL n,N-Dimethylformamide solution,
The concentration of six water of cobalt chloride is 400mM, and the amount of Tx-100 is 0.3mL, and the concentration of thiocarbamide is 1000mM.Before carbon paper is impregnated this
It is taken out after body liquid 30min, again by forerunner's night uniform drop coating on carbon paper after 80 DEG C in thermal station dry 10min, then proceedes to do
Dry 30min.Cated substrate is put into tube furnace, under an ar atmosphere 600 DEG C of reaction 1h, is taken out after natural cooling.
Fig. 1 is the figure of cobalt sulfide-carbon original position electrode SEM prepared by embodiment 1.As seen from the figure prepared by the embodiment
Cobalt sulfide-carbon is nano-sheet in electrode, and homoepitaxial is on the fiber stick of carbon paper.
Embodiment 2:
At room temperature, six water of cobalt chloride, Tx-100 and thiocarbamide are dissolved in 2.7mL n,N-Dimethylformamide solution,
Wherein the concentration of six water of cobalt chloride is 400mM, and the amount of Tx-100 is 0.3mL, and the concentration of thiocarbamide is 1000mM.Carbon paper is impregnated
Taken out after the preceding body liquid 30min, again by forerunner's night uniform drop coating on carbon paper after 80 DEG C in thermal station dry 10min, then after
Continuous dry 30min.Cated substrate is put into tube furnace, under an ar atmosphere 600 DEG C of reaction 1h, is taken after cooled to room temperature
Out.The carbon paper of taking-up is continued into 400 DEG C of reaction 30min in air, is taken out after cooled to room temperature.
Fig. 2 is (a) HER, (b) OER, the linear voltammetric scan of (c) ORR (LSV) of electrode in situ prepared by embodiment 1,2
Figure.When the current density that electrode passes through is 10mA/cm known to Fig. 2 (a)2When, embodiment 1 produces hydrogen and needs in alkaline aqueous solution
The overpotential of 0.21V；Embodiment 2 produces the overpotential that hydrogen needs 0.18V.Electricity prepared by the embodiment 1,2 as known to Fig. 2 (b)
Pole all has excellent analysis oxygen performance, when the current density that electrode passes through is 10mA/cm2When, current potential needed for embodiment 1 analyses oxygen is
1.40V, overpotential needed for analysing oxygen are 1.40-1.23=0.17V；The current potential that embodiment 2 analyses oxygen is 1.47V, analyses the overpotential of oxygen
For 1.47-1.23=0.24V.When the current density that electrode passes through is up to 300mA/cm2When, the made electrode of embodiment 1 produces oxygen only
The overpotential of 0.28V is needed, the made electrode of embodiment 2, which produces oxygen, also only needs the overpotential of 0.32V.By known to Fig. 2 (c) by embodiment 1,
Electrode prepared by 2 also has excellent hydrogen reduction performance, (is stirred in flask with magneton, n=in low speed rotation
230r.p.m.) 1 current density of embodiment can reach~6.0mA/cm2, 2 current density of embodiment can reach~4.0mA/cm2。
Fig. 3 is stability test of the original position electrode under 200mA constant current prepared by embodiment 1, as seen from the figure, embodiment 1
The electrode obtained has good stability.
Embodiment 3:
At room temperature, six water of cobalt chloride, Tx-100 and thiocarbamide are dissolved in 2.7mL n,N-Dimethylformamide solution,
Wherein the concentration of six water of cobalt chloride is 400mM, and the amount of Tx-100 is 0.2mL, and the concentration of thiocarbamide is 1000mM.Carbon paper is impregnated
Taken out after the preceding body liquid 30min, again by forerunner's night uniform drop coating on carbon paper after 80 DEG C in thermal station dry 10min, then after
Continuous dry 30min.Cated substrate is put into tube furnace, under an ar atmosphere 600 DEG C of reaction 1h, is taken after cooled to room temperature
Out.
Embodiment 4:
At room temperature, six water of cobalt chloride, Tx-100 and thiocarbamide are dissolved in 2.0mL n,N-Dimethylformamide solution,
Wherein the concentration of six water of cobalt chloride is 400mM, and the amount of Tx-100 is 1.0mL, and the concentration of thiocarbamide is 1000mM.Carbon paper is impregnated
Taken out after the preceding body liquid 30min, again by forerunner's night uniform drop coating on carbon paper after 80 DEG C in thermal station dry 10min, then after
Continuous dry 30min.Cated substrate is put into tube furnace, under an ar atmosphere 600 DEG C of reaction 1h, is taken after cooled to room temperature
Out.
Fig. 4 is (a) HER, (b) OER, the linear voltammetric scan of (c) ORR (LSV) of electrode in situ prepared by embodiment 3,4
Figure.When the current density that electrode passes through is 10mA/cm known to Fig. 4 (a)2When, the made electrode of embodiment 4 produces in alkaline aqueous solution
Hydrogen needs the overpotential of 0.27V.Electrode prepared by the embodiment 3,4 as known to Fig. 4 (b) all has excellent analysis oxygen performance,
When the current density that electrode passes through is 10mA/cm2When, current potential needed for the made electrode of embodiment 3 analyses oxygen is 1.45V, is analysed needed for oxygen
Overpotential is 1.45-1.23=0.22V；Current potential needed for the made electrode of embodiment 4 analyses oxygen is 1.55V, and overpotential needed for analysing oxygen is
1.55-1.23=0.32V.When the current density that electrode passes through is 300mA/cm2When, the made electrode of embodiment 3 produces oxygen demand
The overpotential of 0.39V；The overpotential of the made electrode of embodiment 4 production oxygen demand 0.37V.By 3,4 institute of embodiment known to Fig. 4 (c)
The electrode of preparation also has excellent hydrogen reduction performance, and in low speed rotation, 3 current density of embodiment can reach~4.0mA/
cm2, 4 current density of embodiment can reach~5.4mA/cm2。
Fig. 5 is the figure of cobalt sulfide-carbon original position electrode SEM prepared by embodiment 4.As seen from the figure prepared by the embodiment
Cobalt sulfide-carbon is nanosphere homoepitaxial on the fiber stick of carbon paper in electrode.
Fig. 6 is cobalt sulfide-carbon original position electrode XRD prepared by embodiment 4, is used and embodiment to compare us
Six water of cobalt chloride and thiocarbamide is not added only in 4 identical sintering process, the carbon material after having obtained Tx-100 carbonization, XRD
It is also illustrated in Fig. 6 as a comparison.Pass through contrast standard card, it is known that the main component of the made sample of embodiment 4 is Co4S3With
Carbon.
Embodiment 5:
At room temperature, four water of cobalt acetate, Tx-100 and thiocarbamide are dissolved in 2.7mL n,N-Dimethylformamide solution,
Wherein the concentration of four water of cobalt acetate is 400mM, and the amount of Tx-100 is 0.3mL, and the concentration of thiocarbamide is 1000mM.Carbon paper is impregnated
Taken out after the preceding body liquid 30min, again by forerunner's night uniform drop coating on carbon paper after 80 DEG C in thermal station dry 10min, then after
Continuous dry 30min.Cated substrate is put into tube furnace, under an ar atmosphere 600 DEG C of reaction 1h, is taken after cooled to room temperature
Out.
Fig. 7 (a) is the linear voltammetric scan of HER (LSV) figure of electrode in situ prepared by embodiment 5, as seen from the figure the reality
Electrode prepared by example is applied with good HER performance.Fig. 7 (b) linearly lies prostrate for the OER of electrode in situ prepared by embodiment 5
Peace scanning (LSV) figure.As seen from the figure when the current density that electrode passes through is 10mA/cm2When, the made electrode of the embodiment analyses oxygen institute
Needing current potential is 1.42V, and overpotential needed for analysing oxygen is 1.42-1.23=0.19V.Fig. 7 (c) is electricity in situ prepared by embodiment 5
The linear voltammetric scan of the ORR of pole (LSV) figure, by figure know the electrode oxygen reduction current density it is reachable~5mA/cm2。
Embodiment 6:
At room temperature, seven water of cobaltous sulfate, Tx-100 and thiocarbamide are dissolved in 2.7mLN, dinethylformamide solution,
Wherein the concentration of seven water of cobaltous sulfate is 400mM, and the amount of Tx-100 is 0.3mL, and the concentration of thiocarbamide is 1000mM.Carbon paper is impregnated
It is taken out after the preceding body liquid, again by forerunner's night uniform drop coating on carbon paper after 80 DEG C in thermal station dry 10min, then proceedes to drying
30min.Cated substrate is put into tube furnace, under an ar atmosphere 600 DEG C of reaction 1h, is taken out after cooled to room temperature.
Fig. 7 (c) is the linear voltammetric scan of ORR (LSV) figure of electrode in situ prepared by embodiment 6.The reality as seen from the figure
Electrode prepared by example is applied with good ORR, current density is reachable~6.0mA/cm2。
Embodiment 7:
At room temperature, six water of cobalt nitrate, Tx-100 and thiocarbamide are dissolved in 2.7mLN, dinethylformamide solution,
Wherein the concentration of six water of cobalt nitrate is 400mM, and the amount of Tx-100 is 0.3mL, and the concentration of thiocarbamide is 1000mM.Carbon paper is impregnated
It is taken out after the preceding body liquid, again by forerunner's night uniform drop coating on carbon paper after 80 DEG C in thermal station dry 10min, then proceedes to drying
30min.Cated substrate is put into tube furnace, under an ar atmosphere 600 DEG C of reaction 1h, is taken out after cooled to room temperature.
Fig. 7 (c) is the linear voltammetric scan of ORR (LSV) figure of electrode in situ prepared by embodiment 7.The reality as seen from the figure
Apply current density during hydrogen reduction of electrode prepared by example it is reachable~5mA/cm2。
Embodiment 8:
At room temperature, six water of cobalt chloride, sucrose and thiocarbamide are dissolved in 3mLN, dinethylformamide solution, wherein
The concentration of six water of cobalt chloride is 400mM, and the amount of sucrose is 0.1g, and the concentration of thiocarbamide is 1000mM.Carbon paper is impregnated into the preceding body
It is taken out after liquid, again by forerunner's night uniform drop coating on carbon paper after 80 DEG C in thermal station dry 10min, then proceedes to dry 30min.
Cated substrate is put into tube furnace, it is further heated up to 900 DEG C of reaction 30min after 600 DEG C of reaction 1h under an ar atmosphere, certainly
It is taken out after being so cooled to room temperature.
Fig. 8 is the linear voltammetric scan of ORR (LSV) figure of electrode in situ prepared by embodiment 8.The embodiment as seen from the figure
Prepared electrode has good ORR performance.
Embodiment 9
At room temperature, six water of cobalt chloride, aniline and thiocarbamide are dissolved in 2.8mL n,N-Dimethylformamide solution,
The concentration of middle six water of cobalt chloride is 400mM, and the amount of aniline is 0.2mL, and the concentration of thiocarbamide is 1000mM.Before carbon paper is impregnated this
It is taken out after body liquid, again by forerunner's night uniform drop coating on carbon paper after 80 DEG C in thermal station dry 10min, then proceedes to drying
30min.Cated substrate is put into tube furnace, it is further heated up to 900 DEG C of reactions after 600 DEG C of reaction 1h under an ar atmosphere
30min takes out after cooled to room temperature.
Fig. 8 is the linear voltammetric scan of ORR (LSV) figure of electrode in situ prepared by embodiment 9.The embodiment as seen from the figure
Prepared electrode has good performance.
Embodiment 10:
At room temperature, six water of cobalt chloride, Tx-100 and thiocarbamide are dissolved in 2.7mL n,N-Dimethylformamide solution,
Wherein the concentration of six water of cobalt chloride is 400mM, and the amount of Tx-100 is 0.3mL, and the concentration of thiocarbamide is 1000mM.Carbon paper is impregnated
It is taken out after the preceding body liquid, again by forerunner's night uniform drop coating on carbon paper after 80 DEG C in thermal station dry 10min, then proceedes to drying
30min.Cated substrate is put into tube furnace, it is further heated up to 900 DEG C of reactions after 600 DEG C of reaction 1h under an ar atmosphere
30min takes out after cooled to room temperature.
Fig. 9 is (a) OER, the linear voltammetric scan of (b) ORR (LSV) figure of electrode in situ prepared by embodiment 10.By Fig. 9
(a) electrode prepared by the embodiment known to has excellent OER performance.It is 10mA/cm in current density2When, the electrode institute
Needing voltage is 1.50V, and required overpotential is 270mV.By electrode electric current in hydrogen reduction known to Fig. 9 (b) it is reachable~5.5mA/
cm2。
Embodiment 11:
At room temperature, six water of cobalt chloride, Tx-100 and thiocarbamide are dissolved in 2.7mL n,N-Dimethylformamide solution,
Wherein the concentration of six water of cobalt chloride is 400mM, and the amount of Tx-100 is 0.3mL, and the concentration of thiocarbamide is 1000mM.Carbon paper is impregnated
It is taken out after the preceding body liquid, again by forerunner's night uniform drop coating on carbon paper after 80 DEG C in thermal station dry 10min, then proceedes to drying
30min.Cated substrate is put into tube furnace, under an ar atmosphere 500 DEG C of reaction 1h, is taken out after cooled to room temperature.
Electrode prepared by the embodiment as known to Fig. 9 (a) has excellent OER performance.It is 10mA/ in current density
cm2When, voltage needed for the electrode is 1.56V, and required overpotential is 330mV.The electrode is electric in hydrogen reduction known to Fig. 9 (b)
Flow reachable~5.0mA/cm2。
Claims (7)
1. a kind of cobalt sulfide-carbon original position electrode preparation method, which is characterized in that it is specific the preparation method comprises the following steps:
(1) cobalt salt and carbonaceous organic material are dissolved in volatilization nonaqueous solvents, and sulphur source is added, obtain body before Co-C-S after mixing evenly
Liquid；
(2) body liquid is applied in substrate before above-mentioned Co-C-S, is put after dry in an ar atmosphere or N2The annealing vulcanization of atmosphere high temperature.
2. cobalt sulfide described in claim 1-carbon original position electrode preparation method, which is characterized in that volatilization nonaqueous solvents include
Ethyl alcohol or N,N-dimethylformamide.
3. cobalt sulfide described in claim 1-carbon original position electrode preparation method, which is characterized in that the carbonaceous organic material
Including any one in Tx-100, glucose, sucrose, aniline.
4. cobalt sulfide described in claim 1-carbon original position electrode preparation method, which is characterized in that cobalt salt, carbonaceous organic material
It is dissolved in the mixed solution of volatilization nonaqueous solvents, the concentration of Co atom is 200 ~ 900 mM, and carbonaceous organic material and volatilization are non-aqueous
The volume ratio of agent is 0.03 ~ 2.
5. cobalt sulfide described in claim 1-carbon original position electrode preparation method, which is characterized in that the substrate includes such as
Any one in carbon cloth, graphite paper, foam copper or nickel.
6. cobalt sulfide described in claim 1-carbon original position electrode preparation method, which is characterized in that the drying is in sky
It is spontaneously dried in gas, or in 70 ~ 100 DEG C of rapid draing in thermal station.
7. cobalt sulfide described in claim 1-carbon original position electrode preparation method, which is characterized in that annealing temperature be 500 ~
900 DEG C, the reaction time is 0.5 ~ 4 h.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109797405A (en) * | 2019-02-21 | 2019-05-24 | 三峡大学 | A kind of preparation method of cobalt sulfide and nitrogen-doped carbon composite array electrode |
| CN110010874A (en) * | 2019-04-11 | 2019-07-12 | 陕西科技大学 | A kind of preparation method of extra small spherical cobalt sulfide composite and flexible carbon cloth electrode material |
| CN110690469A (en) * | 2019-10-16 | 2020-01-14 | 三峡大学 | Preparation method of in-situ defect modified Co9S 8-porous nitrogen-doped carbon electrode |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104399494A (en) * | 2014-12-10 | 2015-03-11 | 吉林大学 | Carbon-coated cobalt sulfide material as well as preparing method thereof and application of carbon-coated cobalt sulfide material in aspect of water cracking hydrogen production |
| CN105289658A (en) * | 2015-10-23 | 2016-02-03 | 吉林大学 | Carbon fiber supported cobalt sulfide nanosheet catalyst and application thereof |
| CN105551810A (en) * | 2016-01-01 | 2016-05-04 | 三峡大学 | Solvothermal preparation method for in-situ electrode |
| CN105600745A (en) * | 2016-03-18 | 2016-05-25 | 复旦大学 | Cobalt disulfide/carbon nanofiber composite material and preparation method thereof |
| CN105719846A (en) * | 2016-04-13 | 2016-06-29 | 岭南师范学院 | Preparation method for cobalt sulfide/carbon composite material and product and application therefor |
| CN108046338A (en) * | 2017-12-14 | 2018-05-18 | 三峡大学 | A kind of cobalt doped molybdenum disulfide original position electrode and preparation method thereof |
| CN108385132A (en) * | 2018-03-09 | 2018-08-10 | 三峡大学 | A kind of Co doping MoS2The CVD preparation methods of array original position electrode |
-
2018
- 2018-09-11 CN CN201811057741.8A patent/CN109306501A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104399494A (en) * | 2014-12-10 | 2015-03-11 | 吉林大学 | Carbon-coated cobalt sulfide material as well as preparing method thereof and application of carbon-coated cobalt sulfide material in aspect of water cracking hydrogen production |
| CN105289658A (en) * | 2015-10-23 | 2016-02-03 | 吉林大学 | Carbon fiber supported cobalt sulfide nanosheet catalyst and application thereof |
| CN105551810A (en) * | 2016-01-01 | 2016-05-04 | 三峡大学 | Solvothermal preparation method for in-situ electrode |
| CN105600745A (en) * | 2016-03-18 | 2016-05-25 | 复旦大学 | Cobalt disulfide/carbon nanofiber composite material and preparation method thereof |
| CN105719846A (en) * | 2016-04-13 | 2016-06-29 | 岭南师范学院 | Preparation method for cobalt sulfide/carbon composite material and product and application therefor |
| CN108046338A (en) * | 2017-12-14 | 2018-05-18 | 三峡大学 | A kind of cobalt doped molybdenum disulfide original position electrode and preparation method thereof |
| CN108385132A (en) * | 2018-03-09 | 2018-08-10 | 三峡大学 | A kind of Co doping MoS2The CVD preparation methods of array original position electrode |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109797405A (en) * | 2019-02-21 | 2019-05-24 | 三峡大学 | A kind of preparation method of cobalt sulfide and nitrogen-doped carbon composite array electrode |
| CN110010874A (en) * | 2019-04-11 | 2019-07-12 | 陕西科技大学 | A kind of preparation method of extra small spherical cobalt sulfide composite and flexible carbon cloth electrode material |
| CN110690469A (en) * | 2019-10-16 | 2020-01-14 | 三峡大学 | Preparation method of in-situ defect modified Co9S 8-porous nitrogen-doped carbon electrode |
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