CN108660471B - A kind of preparation method for the nickel-ferric spinel water oxygen polarizing electrode being supported on azepine graphite foam - Google Patents
A kind of preparation method for the nickel-ferric spinel water oxygen polarizing electrode being supported on azepine graphite foam Download PDFInfo
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- CN108660471B CN108660471B CN201810141121.6A CN201810141121A CN108660471B CN 108660471 B CN108660471 B CN 108660471B CN 201810141121 A CN201810141121 A CN 201810141121A CN 108660471 B CN108660471 B CN 108660471B
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- ferric
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 239000010439 graphite Substances 0.000 title claims abstract description 79
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 79
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 239000006260 foam Substances 0.000 title claims abstract description 32
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 29
- XYOVOXDWRFGKEX-UHFFFAOYSA-N azepine Chemical compound N1C=CC=CC=C1 XYOVOXDWRFGKEX-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 239000001301 oxygen Substances 0.000 title claims abstract description 29
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 29
- 229910052596 spinel Inorganic materials 0.000 title claims abstract description 26
- 239000011029 spinel Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000011888 foil Substances 0.000 claims abstract description 52
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000004202 carbamide Substances 0.000 claims abstract description 12
- 239000008367 deionised water Substances 0.000 claims abstract description 12
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 12
- 238000000502 dialysis Methods 0.000 claims abstract description 11
- 150000002815 nickel Chemical class 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000011259 mixed solution Substances 0.000 claims abstract description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 8
- 239000002131 composite material Substances 0.000 claims abstract description 7
- 150000002505 iron Chemical class 0.000 claims abstract description 6
- 239000000463 material Substances 0.000 claims abstract description 5
- 230000002378 acidificating effect Effects 0.000 claims abstract description 4
- 150000003839 salts Chemical class 0.000 claims abstract description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 6
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 3
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 3
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical group [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical group [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical group [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 abstract description 5
- 230000001737 promoting effect Effects 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 6
- 229910000863 Ferronickel Inorganic materials 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000012266 salt solution Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000004575 stone Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910001701 hydrotalcite Inorganic materials 0.000 description 2
- 229960001545 hydrotalcite Drugs 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- -1 iron salt ferric sulfate Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- HKIQZBZCKQBMJT-UHFFFAOYSA-J nickel(2+) disulfate Chemical compound [Ni++].[Ni++].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O HKIQZBZCKQBMJT-UHFFFAOYSA-J 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- 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
-
- 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
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
- C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
- C25B11/031—Porous electrodes
-
- 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
- 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
-
- 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
- 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
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/069—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of at least one single element and at least one compound; consisting of two or more compounds
-
- 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
- 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
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
-
- 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
Abstract
The invention discloses a kind of preparation methods of nickel-ferric spinel water oxygen polarizing electrode being supported on azepine graphite foam, this method comprises the following steps: required graphite foil being placed in the concentrated sulfuric acid and concentrated nitric acid volume ratio is in the mixed solution of 3:1,2-12h is aoxidized at room temperature, take out obtained graphite oxide foil, it is placed in deionized water, dialysis removal remains in acidic materials and small organic molecule on graphite oxide foil；Then graphite oxide foil is placed in water heating kettle, the mixed solution of urea, solvable divalent nickel salt and trivalent iron salt is added, and hydro-thermal reaction 6-12h under the conditions of 120-180 DEG C, obtained composite material is washed with deionized, removal residual salt of dialysing is to get to the nickel-ferric spinel water oxygen polarizing electrode being supported on azepine graphite foam.Through the above scheme, invention achieves the purposes for obtaining the finely dispersed self-supporting electrode of hydrotalcite structure, have very high practical value and promotional value.
Description
Technical field
The invention belongs to nanocomposite technical fields, and in particular to a kind of ferronickel being supported on azepine graphite foam
The preparation method of hydrotalcite water oxygen polarizing electrode.
Background technique
Oxygen evolution reaction catalysis is the bottleneck for limiting electrolysis water and obtaining hydrogen energy source and its related energy resource system.Research shows that your gold
Metal catalyst such as IrO2 and RuO2 have an excellent catalytic activity, but its practical application is limited to expensive price and lower urges
Change stability.Transition-metal catalyst especially nickel-ferric spinel (NiFe LDH) is since high with catalytic activity, stability is high
And cheap feature and the extensive concern by researchers.As Chinese patent, application No. is 201610565736.2
A kind of FeOOH-nickel-ferric spinel integration analysis oxygen electrode and preparation and application, need outer biasing during the preparation process
Pressure, and use nickel foam as carrier, nickel foam is constant in itself in water-heat process, and nickel-ferric spinel structural load only occurs and exists
Behavior in nickel foam since nickel foam and hydrotalcite structure do not have stronger interaction force, thus cannot help neatly
Stone structure dispersion, so the ferronickel salinity in the patent is big, hydrotalcite structure piece being prepared is huge, reaches micron order
Other size, and nickel foam is all wrapped, it cannot act as large area working electrode.The carbon material (NC) of N doping loads
NiFe LDH can solve the problems, such as that pure NiFe LDH material conductivity is poor, easy to reunite, deposit to its oxygen evolution reaction catalytic activity is improved
It is acting synergistically, but NiFe LDH/NC oxygen evolution reaction catalysts preparation method is complicated at present, poor controllability, wherein using hydro-thermal
The compound that method is prepared is usually powder, and when use needs to be carried on the enterprising enforcement of glass-carbon electrode by binder
With cannot achieve the preparation of large area working electrode.
Summary of the invention
The purpose of the present invention is to provide a kind of nickel-ferric spinel water oxygen polarizing electrodes being supported on azepine graphite foam
Preparation method mainly solves oxygen evolution reaction poor controllability existing in the prior art, and the compound prepared is usually powder, only
The problem of capable of being supported on glass-carbon electrode, large area working electrode cannot be prepared.
To achieve the goals above, The technical solution adopted by the invention is as follows:
A kind of preparation method for the nickel-ferric spinel water oxygen polarizing electrode being supported on azepine graphite foam, including walk as follows
It is rapid:
(S1) required graphite foil is placed in the mixed solution that the concentrated sulfuric acid is 3:1 with concentrated nitric acid volume ratio, at room temperature oxygen
Change 2-12h, obtained loose porous graphite oxide foil；
(S2) obtained graphite oxide foil is placed in deionized water, dialysis removal remains in the acidity on graphite oxide foil
Substance and small organic molecule；
(S3) by (S2) clean graphite oxide foil be placed in water heating kettle, be added urea, solvable divalent nickel salt with it is solvable
The mixed solution of trivalent iron salt, and hydro-thermal reaction 6-12h under the conditions of 120-180 DEG C, obtain composite material；
(S4) obtained composite material is washed with deionized, dialyse removal residual salt to get to graphite foil it is big
Small consistent and nickel-ferric spinel water oxygen polarizing electrode of the uniform load on azepine graphite foam.
Further, urea concentration is 0.1-2mol/L in the step (S3).
Further, soluble divalent nickel salt is nickel sulfate, nickel nitrate or nickel chloride in the step (S3), and concentration
For 10-200mmol/L.
Specifically, soluble trivalent iron salt is ferric sulfate, ferric nitrate or iron chloride in the step (S3), and concentration is
2-100mmol/L。
Compared with prior art, the invention has the following advantages:
(1) present invention is aoxidized by the way that the graphite foil of required size to be put into the mixed solution of the concentrated sulfuric acid and concentrated nitric acid
Reaction obtains the graphite oxide foil of loose and porous structure, and graphite oxide foil is placed in water heating kettle, while urea, solvable is added
Property divalent nickel salt and trivalent iron salt, urea be only ferronickel ion hydrolysis provide alkaline environment, also to graphite oxide foil knot
Structure is doped, and the doping to carrier and ferronickel are completed while finally obtaining the structure, i.e. water-heat process of azepine graphite foil
The preparation of hydrotalcite, therefore and uniform load in the same size with graphite foil is obtained in azepine graphite after hydro-thermal reaction a few hours
Nickel-ferric spinel water oxygen polarizing electrode on foam.
(2) there are very strong interactions between nickel-ferric spinel and azepine graphite foil prepared by the present invention, so that neatly
Stone structure is evenly distributed, not easy to reunite or fall off, and can make the working electrode of large area, and with good stability and living
Property, difficulty in the prior art is overcome, great progress is achieved.
(3) graphite foil in the present invention can according to need and be cut into arbitrary dimension and shape, obtain after reaction and graphite foil
The consistent self-supporting electrode of size and shape, and graphite foil is flexible, can prepare larger electrode in smaller water heating kettle, reduce
Reactant needed for reaction, while preparing at normal temperatures and pressures, additional equipment is not needed, has saved reaction preparation cost, and grasp
Make simple, it can be achieved that producing in enormous quantities.
Detailed description of the invention
Fig. 1 is flowage structure schematic diagram of the invention.
Fig. 2 is that the scanning electron on the nickel-ferric spinel water oxygen polarizing electrode surface that the present invention is supported on azepine graphite foam is aobvious
Micro mirror photo.
Fig. 3 is the oxygen evolution reaction catalytic for the nickel-ferric spinel water oxygen polarizing electrode that the present invention is supported on azepine graphite foam
Energy and stability.
Specific embodiment
Present invention will be further explained below with reference to the attached drawings and examples, and embodiments of the present invention include but is not limited to
The following example.
A kind of preparation method for the nickel-ferric spinel water oxygen polarizing electrode being supported on azepine graphite foam, including walk as follows
It is rapid:
(S1) required graphite foil is placed in the mixed solution that the concentrated sulfuric acid is 3:1 with concentrated nitric acid volume ratio, at room temperature oxygen
Change 2-12h, obtained loose porous graphite oxide foil；
(S2) graphite oxide foil is placed in deionized water, dialysis removal remain in acidic materials on graphite oxide foil and
Small organic molecule；
(S3) the graphite oxide foil cleaned in (S2) is placed in water heating kettle, the urea that concentration is 0.1-2mol/L is added,
Concentration is solvable divalent nickel salt nickel sulfate, nickel nitrate or the nickel chloride of 10-200mmol/L, and concentration is the solvable of 2-100mmol/L
The mixed solution of trivalent iron salt ferric sulfate, ferric nitrate or iron chloride, and hydro-thermal reaction 6-12h under the conditions of 120-180 DEG C, obtain
Composite material；
(S4) obtained composite material is washed with deionized, dialyse removal residual salt to get to graphite foil it is big
Small consistent and nickel-ferric spinel water oxygen polarizing electrode of the uniform load on azepine graphite foam.
It is as follows that case is embodied:
Embodiment 1
200 μ m-thick graphite foils are cut into 4 × 2cm, in the concentrated sulfuric acid: Oxidation at room temperature 6h in concentrated nitric acid=3:1 mixed acid system
Graphite oxide foil is obtained, the graphite oxide foil being prepared is placed in deionized water dialysis and removes remaining acidic materials and small
Graphite oxide foil is placed in water heating kettle by molecular organic, and 0.2mol/L urea, the solvable nickel salt of 20mmol/L, 5mmol/L is added
Soluble iron mixed salt solution, hydro-thermal reaction 12h under the conditions of 180 DEG C are obtained and graphite foil size after deionized water cleaning dialysis
Consistent and nickel-ferric spinel water oxygen polarizing electrode of the uniform load on azepine graphite foam.
By (a, b) in Fig. 2 as it can be seen that azepine graphite foam surface still keeps the fold knot of graphite surface after hydro-thermal reaction
Structure, nickel-ferric spinel nanostructure size are evenly distributed, and intensively and are evenly distributed in azepine graphite foam surface；It can by Fig. 3
See, azepine graphite foam catalytic activity is extremely low, and nickel-ferric spinel/azepine graphite foam combination electrode activity is high, originates
Current potential is only 0.23V；Charge transfer resistance is small, only 0.25 Ω cm2, catalytic stability is high, after catalysis reaction 12h, catalysis electricity
Stream retains 93.5%.
Embodiment 2
500 μ m-thick graphite foils are cut into 2 × 1cm, in the concentrated sulfuric acid: Oxidation at room temperature 12h in concentrated nitric acid=3:1 mixed acid system
Graphite oxide foil is obtained, the graphite oxide foil being prepared is placed in dialysis in deionized water and removes remaining acid substance and small point
Obtained graphite oxide foil is placed in water heating kettle by sub- organic matter, be added 0.4mol/L urea, the solvable nickel salt of 40mmol/L,
10mmol/L soluble iron mixed salt solution, hydro-thermal reaction 12h under the conditions of 180 DEG C, deionized water cleaning obtains after dialysing and stone
The nickel-ferric spinel water oxygen polarizing electrode that black foil is in the same size and uniform load is on azepine graphite foam.
By Fig. 2 (c, d) as it can be seen that azepine graphite foam surface folding structure is constant after increasing nickel salt, iron salt concentration, ferronickel water
Talcum nanostructure size increases, still intensive and be evenly distributed in azepine graphite foam surface.
Embodiment 3
50 μ m-thick graphite foils are cut into 5 × 5cm, in the concentrated sulfuric acid: Oxidation at room temperature 6h is in concentrated nitric acid=3:1 mixed acid system
Graphite oxide foil is obtained, the graphite oxide foil being prepared is placed in dialysis in deionized water and removes remaining acid substance and small point
Obtained graphite oxide foil is placed in water heating kettle by sub- organic matter, be added 2mol/L urea, the solvable nickel salt of 200mmol/L,
50mmol/L soluble iron mixed salt solution, hydro-thermal reaction 12h under the conditions of 120 DEG C, deionized water cleaning dialysis after i.e. obtain with
The nickel-ferric spinel water oxygen polarizing electrode that graphite foil is in the same size and uniform load is on azepine graphite foam.
Embodiment 4
200 μ m-thick graphite foils are cut into 2 × 1cm, in the concentrated sulfuric acid: Oxidation at room temperature 8h in concentrated nitric acid=3:1 mixed acid system
Graphite oxide foil is obtained, the graphite oxide foil being prepared is placed in deionized water dialysis removal remaining acid substance and small
Obtained graphite oxide foil is placed in water heating kettle by molecular organic, be added 0.2mol/L urea, the solvable nickel salt of 80mmol/L,
20mmol/L soluble iron mixed salt solution, hydro-thermal reaction 12h under the conditions of 150 DEG C, deionized water cleaning dialysis after i.e. obtain with
The nickel-ferric spinel water oxygen polarizing electrode that graphite foil is in the same size and uniform load is on azepine graphite foam.
Above-described embodiment is merely a preferred embodiment of the present invention, and it is not intended to limit the protection scope of the present invention, as long as using
Design principle of the invention, and the non-creative variation worked and made is carried out on this basis, it should belong to of the invention
Within protection scope.
Claims (3)
1. a kind of preparation method for the nickel-ferric spinel water oxygen polarizing electrode being supported on azepine graphite foam, which is characterized in that packet
Include following steps:
(S1) required graphite foil is placed in the concentrated sulfuric acid and concentrated nitric acid volume ratio is to aoxidize 2- at room temperature in the mixed solution of 3:1
12h, obtained loose porous graphite oxide foil；
(S2) obtained graphite oxide foil is placed in deionized water, dialysis removal remains in the acidic materials on graphite oxide foil
And small organic molecule；
(S3) the graphite oxide foil cleaned in (S2) is placed in water heating kettle, urea, solvable divalent nickel salt and solvable trivalent is added
The mixed solution of molysite, and hydro-thermal reaction 6-12h under the conditions of 120-180 DEG C, obtain composite material；Wherein, urea concentration is
0.1-2mol/L。
(S4) obtained composite material is washed with deionized, dialyses removal residual salt to get arriving and graphite foil size one
Cause and nickel-ferric spinel water oxygen polarizing electrode of the uniform load on azepine graphite foam.
2. a kind of preparation of nickel-ferric spinel water oxygen polarizing electrode being supported on azepine graphite foam according to claim 1
Method, which is characterized in that soluble divalent nickel salt is nickel sulfate, nickel nitrate or nickel chloride in the step (S3), and concentration
For 10-200mmol/L.
3. a kind of preparation of nickel-ferric spinel water oxygen polarizing electrode being supported on azepine graphite foam according to claim 2
Method, which is characterized in that soluble trivalent iron salt is ferric sulfate, ferric nitrate or iron chloride in the step (S3), and concentration
For 2-100mmol/L.
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| CN201810141121.6A CN108660471B (en) | 2018-02-11 | 2018-02-11 | A kind of preparation method for the nickel-ferric spinel water oxygen polarizing electrode being supported on azepine graphite foam |
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| CN108660471A CN108660471A (en) | 2018-10-16 |
| CN108660471B true CN108660471B (en) | 2019-11-15 |
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| CN110528022B (en) * | 2019-08-13 | 2021-04-20 | 中国工程物理研究院材料研究所 | Preparation method of nitrogen-doped carbon nano array-nickel iron hydrotalcite oxygen evolution electrode |
| CN111952607B (en) * | 2020-07-16 | 2022-07-15 | 广东邦普循环科技有限公司 | Oxygen reduction catalyst prepared from waste graphite and preparation method thereof |
| CN112652779A (en) * | 2020-12-11 | 2021-04-13 | 广东邦普循环科技有限公司 | High-activity oxygen reduction catalyst and preparation method and application thereof |
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