CN110408947A - A kind of nickel cobalt oxide electrode material and the preparation method and application thereof of combined oxidation silver - Google Patents
A kind of nickel cobalt oxide electrode material and the preparation method and application thereof of combined oxidation silver Download PDFInfo
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- CN110408947A CN110408947A CN201910655151.3A CN201910655151A CN110408947A CN 110408947 A CN110408947 A CN 110408947A CN 201910655151 A CN201910655151 A CN 201910655151A CN 110408947 A CN110408947 A CN 110408947A
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- nickel
- electrode material
- silver
- cobalt oxide
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- 239000007772 electrode material Substances 0.000 title claims abstract description 52
- YTBWYQYUOZHUKJ-UHFFFAOYSA-N oxocobalt;oxonickel Chemical compound [Co]=O.[Ni]=O YTBWYQYUOZHUKJ-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 230000003647 oxidation Effects 0.000 title claims abstract description 26
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 26
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 25
- 239000004332 silver Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 106
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 53
- 239000006260 foam Substances 0.000 claims abstract description 48
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 18
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 claims abstract description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002070 nanowire Substances 0.000 claims abstract description 12
- 239000001301 oxygen Substances 0.000 claims abstract description 12
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 12
- 239000002243 precursor Substances 0.000 claims abstract description 9
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002057 nanoflower Substances 0.000 claims abstract description 6
- 239000012266 salt solution Substances 0.000 claims abstract description 6
- 239000000758 substrate Substances 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 16
- 239000003054 catalyst Substances 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 150000002815 nickel Chemical class 0.000 claims description 8
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 6
- 238000000137 annealing Methods 0.000 claims description 6
- 239000004202 carbamide Substances 0.000 claims description 6
- 150000001868 cobalt Chemical class 0.000 claims description 6
- 238000005868 electrolysis reaction Methods 0.000 claims description 6
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 claims description 6
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical group [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 4
- 229910001923 silver oxide Inorganic materials 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [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
- 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 2
- 239000002994 raw material Substances 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 229910000480 nickel oxide Inorganic materials 0.000 claims 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 13
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 238000004458 analytical method Methods 0.000 abstract description 4
- 241000446313 Lamella Species 0.000 abstract description 3
- 230000007797 corrosion Effects 0.000 abstract description 3
- 238000005260 corrosion Methods 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 238000004134 energy conservation Methods 0.000 abstract 1
- 230000007613 environmental effect Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 14
- 229910003266 NiCo Inorganic materials 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000000034 method Methods 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000012876 topography Methods 0.000 description 6
- 238000011161 development Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000000356 contaminant Substances 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 238000004502 linear sweep voltammetry Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- CZAYMIVAIKGLOR-UHFFFAOYSA-N [Ni].[Co]=O Chemical class [Ni].[Co]=O CZAYMIVAIKGLOR-UHFFFAOYSA-N 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229960004756 ethanol Drugs 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 235000012149 noodles Nutrition 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- -1 therefore Substances 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/892—Nickel and noble metals
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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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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- 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
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
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- 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
- C25B11/093—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 at least one noble metal or noble metal oxide and at least one non-noble metal oxide
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Abstract
The invention discloses a kind of nickel cobalt oxide electrode materials and the preparation method and application thereof of combined oxidation silver.The electrode material grows stratiform nickel hydroxide using nickel foam as substrate, in substrate surface, attachment oxidation Nano silver grain on layered nickel hydroxide, grows nano wire again on lamella, the nano flower of nickel cobalt oxide is grown on nano wire.The preparation method of the material includes: first to prepare first step precursor salt solution, is put into pretreated nickel foam, and the stratiform nickel hydroxide of silver-doped is generated using hydro-thermal method；Second step precursor salt solution is prepared again, is put into the nickel foam that the first step obtains, and the nickel cobalt double-hydroxide of silver-doped is generated using hydro-thermal method；It finally anneals in air, obtains the nickel cobalt oxide of combined oxidation silver.The present invention realizes that surface reactive material is combined with foam nickel base, and preparation process is simple, time saving, low energy consumption, energy conservation and environmental protection；Have biggish active area and excellent analysis oxygen catalytic activity, it is corrosion-resistant under alkaline condition.
Description
Technical field
The present invention relates to a kind of nickel cobalt oxide electrode materials and the preparation method and application thereof of combined oxidation silver, belong to electricity
Xie Shui catalysis analysis oxygen technical field.
Background technique
The energy is the most important motive force of human productivity development as the various movable foundation stones of production of human society.
From ancient times to the present, the energy that fossil energy is mainly utilized as the mankind, depletion rate become to be getting faster with the development of the mankind,
Since especially into industrialization society, existing storage will be depleted within several centuries.The consumption of fossil energy
Problem of environmental pollution is brought, therefore, developing sustainable clean alternative energy source is the task of top priority.Due to combustion of hydrogen process energy
It discharges huge energy and product is water, therefore, hydrogen is considered a kind of sustainable clean energy resource.Come from environmental-friendly angle
It says, electrochemical catalysis hydrogen production by water decomposition is to prepare one of desirable route of hydrogen.Electrolysis water includes the production oxygen reaction (OER) of anode
With the evolving hydrogen reaction (HER) of cathode, wherein OER reaction is the slow process of dynamics of four electronics transfers, generally requires to disappear
Consume higher energy.Currently, noble metal-based catalysts (RuO2/IrO2) it is a kind of efficient production VPO catalysts, however these your gold
Belong to the expensive of base catalyst, reserves are limited, limit its heavy industrialization application.Therefore, it can be held to meet development
The oxygen-separating catalyst of the requirement of the continuous energy, development and application high efficiency low cost seems very heavy to substitute expensive noble metal catalyst
It wants.
In recent years, have some base metals and be used as oxygen-separating catalyst, but catalytic stability and catalytic performance
Industrialization production requirements can not be reached.Therefore, develop a kind of cheap, easily prepared and high performance non-precious metal catalyst pair
Promote oxygen evolution reaction industrialization development important in inhibiting.Research finds that the oxygen evolution reaction under alkaline condition has pollution-free, behaviour
Make convenience, technology maturation, be easy to the advantages that large-scale production, becomes one of research hotspot.But oxygen evolution reaction under alkaline condition
Catalyst it is poor there are catalytic activity and stability the problems such as, it is also necessary to further research.
Summary of the invention
In view of the above-mentioned deficiencies in the prior art, the object of the present invention is to provide a kind of nickel cobalt oxides of silver-doped
Electrode material and the preparation method and application thereof, corrosion resistance is strong under alkaline condition for the electrode material, has biggish work
Property area and excellent analysis oxygen ability, preparation method passes through the knot that hydro-thermal method realizes surface reactive material and foam nickel base
It closes, preparation process is simple, equipment requirement is low, low energy consumption, it can be achieved that industrialization large-scale production.
To achieve the above object, The technical solution adopted by the invention is as follows: a kind of nickel cobalt oxide electricity of combined oxidation silver
Pole material, which is characterized in that it grows stratiform nickel hydroxide using nickel foam as substrate, on the surface of the nickel foam, in institute
Attachment oxidation Nano silver grain on stratiform nickel hydroxide is stated, nickel cobalt oxide nanometer is also grown on layered nickel hydroxide
Line grows the nano flower of nickel cobalt oxide on the nano wire.
The present invention also provides the preparation methods of the nickel cobalt oxide electrode material of above-mentioned combined oxidation silver, which is characterized in that
The following steps are included:
1) nickel foam is put into silver nitrate solution, carries out hydro-thermal reaction, product is washed into drying, obtains the layer of silver-doped
Shape nickel hydroxide electrode material；
2) precursor salt solution is configured to by raw material of nickel salt, cobalt salt, urea and deionized water；
3) that the stratiform nickel hydroxide electrode material of the resulting silver-doped of step 1) is put into the resulting presoma of step 2) is molten
In liquid, hydro-thermal reaction is carried out, product is washed into drying, obtains the nickel cobalt double-hydroxide electrode material of silver-doped；
4) the nickel cobalt double-hydroxide electrode material of the resulting silver-doped of step 3) is made annealing treatment in air, is obtained
To the nickel cobalt oxide electrode material of combined oxidation silver.
According to the above scheme, it is preferable that the concentration of silver nitrate solution described in step 1) is 0.001~0.002mol/L.
According to the above scheme, it is preferable that nickel foam purity described in step 1) is 99.8% or more, surface density 300-
450g/cm2。
According to the above scheme, it is preferable that nickel foam described in step 1) is by removal surface and oil contaminant and oxide contaminant layer
Pretreatment, ultrasonic method removal after specially being impregnated using organic solvent and acid solution.It is highly preferred that the organic solvent is
Methanol, ethyl alcohol, tetrahydrofuran or chloroform it is one or more, the acid is dilute hydrochloric acid, and the time of the ultrasound is 10-50min.
According to the above scheme, it is preferable that the temperature of hydro-thermal reaction described in step 1) is 160 DEG C, and the time is 6~8h.
According to the above scheme, it is preferable that nickel salt described in step 2) is nickel nitrate, nickel sulfate or nickel chloride；The cobalt salt is
Cobalt nitrate, cobaltous sulfate or cobalt chloride.It is highly preferred that the molar ratio of the nickel salt and cobalt salt, urea is 1:2:3.It is highly preferred that described
Nickel salt and the amount ratio of deionized water used are 0.05~0.1mol:1L.
According to the above scheme, it is preferable that the temperature of hydro-thermal reaction described in step 3) is 120 DEG C, and the time is 6~8h.
According to the above scheme, it is preferable that annealing temperature described in step 4) is 250 DEG C~350 DEG C, soaking time 2
~3h.
The present invention also provides the applications of the nickel cobalt oxide electrode material of above-mentioned combined oxidation silver, which is characterized in that described
Electrode material can be used as the electrode or catalyst of electrolysis water oxygen.
Compared with prior art, technical solution of the present invention has the following beneficial effects:
(1) present invention is prepared, prepared electrode material good corrosion resistance, shape using nickel foam as substrate using hydro-thermal method
Looks are controllable；And nickel based metal is cheap, stable in catalytic performance under alkaline condition.
(2) preparation method of the nickel cobalt oxide electrode material of combined oxidation silver provided by the invention, simple process, preparation
Low energy consumption for process, is easy to implement industrialized production.
(3) the nickel cobalt oxide electrode material pattern of the combined oxidation silver prepared by the present invention is unique, by the oxidation of zero dimension
Nano silver grain, one-dimensional nano wire, two-dimensional nano piece, three-dimensional manometer flower constitute, can expose more active sites, with compared with
Big active area.
(4) the nickel cobalt oxide electrode material catalytic activity with higher of the combined oxidation silver prepared by the present invention.With
Simple nickel cobalt oxide material is compared, and electrode material provided by the invention is 10mA/cm in current density2When, analysis oxygen performance mentions
High 57mv.It can be widely used as electrolyzed alkaline water hydrogen evolution electrode material, there is broad prospect of application.
Detailed description of the invention
Fig. 1 is NiCoO/AgO/ nickel foam combination electrode material surface topography scanning figure prepared by the embodiment of the present invention 1.
Fig. 2 is NiCo LDH/ foamed nickel electrode material surface topography scanning figure prepared by comparative example 1 of the present invention.
Fig. 3 is NiCoO/ nickel foam combination electrode material surface topography scanning figure prepared by comparative example 2 of the present invention.
Fig. 4 is that the present invention tests combination electrode prepared by obtained pure foam nickel, comparative example 1~2 and embodiment 1
The linear sweep voltammetry curve graph of material.
Specific embodiment
To further understand the present invention, it elaborates below with reference to specific example to the present invention.
Embodiment 1
A kind of preparation of NiCoO/AgO/ nickel foam combination electrode material, comprising the following steps:
I, the pretreatment of foam nickel base: the 1 × 3cm cut is chosen2Nickel foam (purity 99.8%, surface density
For 400g/cm2) be immersed in dehydrated alcohol, it is ultrasonically treated 15min, the hydrochloric acid for then using 2mol/L instead continues to be ultrasonically treated
15min removes the greasy dirt and oxide contaminant layer on surface, finally rinses foam nickel base with deionized water well.
II, NiCo LDH/Ag (the double hydrogen of the nickel cobalt of silver-doped are being formed by two step hydro-thermal reactions in pretreated nickel foam
Oxide):
1) silver nitrate solution after prepared and diluted: taking 0.5mL concentration is the silver nitrate solution of 0.15mol/L, is added
Silver nitrate solution in 39.5mL deionized water, after being diluted.
2) again by the silver nitrate solution after the pretreated foam nickel base of step I is put into the dilution, in high pressure
In reaction kettle, product is washed drying by hydro-thermal reaction 6h at 160 DEG C, is obtained to surface and be grown the stratiform nickel hydroxide of attachment silver
Foam nickel material.
3) 2.5mmol Lvization Nie ﹑ 5mmol cobalt nitrate and 7.5mmol urea are dissolved in 30ml deionized water, it is molten obtains precursor salt
Liquid.
4) foam nickel material that the surface after step 2) hydro-thermal grown to the stratiform nickel hydroxide of attachment silver is put into institute
It states in precursor salt solution, in autoclave, hydro-thermal reaction 6h, washs drying for product after reaction at 120 DEG C, obtains
It grown the foam nickel material of NiCo LDH/Ag to surface.
III, annealing: it step II must be arrived into surface grown the foam nickel material of NiCo LDH/Ag and be put into tube furnace
In, 300 DEG C are heated to the heating rate of 5 DEG C/min under air atmosphere, keeps the temperature 2h, then drop with the rate of temperature fall of 5 DEG C/min
To room temperature, NiCoO/AgO/ nickel foam combination electrode material is obtained.
Fig. 1 is the stratiform nickel hydroxide of growth attachment silver oxide in the nickel foam that is prepared of the present embodiment, on lamella again
Nano wire is grown, the surface topography scanning electron microscope (SEM) photograph of the electrode material of the nano flower of nickel cobalt oxide is grown on nano wire.
Comparative example 1
A kind of preparation of NiCo LDH/ foamed nickel electrode material, comprising the following steps:
I, the pretreatment of foam nickel base: specifically with 1 step I of embodiment.
II, NiCo LDH is being formed by hydro-thermal reaction in pretreated nickel foam:
2.5mmol Lvization Nie ﹑ 5mmol cobalt nitrate and 7.5mmo urea are dissolved in 30ml deionized water, it is molten to obtain precursor salt
Liquid.It will be put into through the pretreated foam nickel base of step I in the precursor salt solution, in autoclave, at 120 DEG C
Hydro-thermal reaction 6h, washs drying for product after reaction, obtains to surface and grown the foam nickel material of linear NiCo LDH.
Fig. 2 is the surface topography scanning for the NiCo LDH/ nickel foam composite nano materials that this comparative example 1 is prepared
Electron microscope.
Comparative example 2
A kind of preparation of NiCoO/ nickel foam combination electrode material, comprising the following steps:
I, the pretreatment of foam nickel base: specifically with 1 step I of comparative example.
II, NiCo LDH is being formed by hydro-thermal reaction in pretreated nickel foam: specifically with 1 step of comparative example
II。
III, annealing form NiCoO: the NiCo LDH/ nickel foam obtained through step II hydro-thermal is put into tube furnace
In, 300 DEG C are heated to the heating rate of 5 DEG C/min under air atmosphere, keeps the temperature 2h, then drop with the rate of temperature fall of 5 DEG C/min
To room temperature.
Fig. 3 is the surface topography scanning electron microscope (SEM) photograph for the NiCoO/ foamed nickel electrode material that this comparative example 2 is prepared.
Interpretation of result:
By in Fig. 1-3 stereoscan photograph it will be clear that nickel cobalt double-hydroxide is received in comparative example 1
Rice noodles homoepitaxial is in nickel foam；Nano wire homoepitaxial grows nickel in nickel foam in comparative example 2 on nano wire
The nano flower of cobalt/cobalt oxide；The stratiform nickel hydroxide of silver oxide is adhered in growth in nickel foam in embodiment 1, grows again on lamella
Nano wire grows the nano flower of nickel cobalt oxide on nano wire, can greatly increase the active area and catalytic activity of material.
Measure of merit:
It is applied to electricity for electrode material prepared in above-mentioned comparative example 1~2 and embodiment 1 as electrolysis water electrode
Xie Shui is catalyzed oxygen processed, and using pure foam nickel as blank control.
The survey of linear sweep voltammetry curve is carried out to the combination electrode material that pure foam nickel, above three embodiments are prepared respectively
Examination:
Three-electrode system being used in test process, using 1mol/L KOH as electrolyte, wherein carbon-point is used as to electrode,
Saturated calomel electrode successively makees the combination electrode material that nickel foam, three embodiments are prepared respectively as reference electrode respectively
It is tested for working electrode, wherein guaranteeing that combination electrode material prepared by nickel foam, three kinds of embodiments is having the same several
What area, test results are shown in figure 4.
As shown in Figure 4, when current density is 10mA/cm2When, the performance of the nickel cobalt oxide electrode material of Ag doping is compared
It has a distinct increment for pure foam nickel.By above-mentioned comparison it can be concluded that, prepared silver-doped in the embodiment of the present invention 1
When nickel cobalt oxide electrode material is as electrolysis water catalyst, with nickel cobalt double-hydroxide prepared in comparative example 1 and
The foam nickel material of prepared nickel cobalt oxide is compared in comparative example 2, and active area is big, and catalytic performance is excellent, has uncommon
Prestige can substitute noble metal catalyst in electrolysis water oxygen field.
The above is a preferred embodiment of the present invention, cannot limit the right model of the present invention with this certainly
It encloses, it is noted that for those skilled in the art, without departing from the principle of the present invention, may be used also
To make several improvement and variation, these, which improve and change, is also considered as protection scope of the present invention.
Claims (10)
1. a kind of nickel cobalt oxide electrode material of combined oxidation silver, which is characterized in that it is using nickel foam as substrate, in the bubble
The surface of foam nickel grows stratiform nickel hydroxide, the attachment oxidation Nano silver grain on layered nickel hydroxide, in the layer
Nickel cobalt oxide nano wire is also grown on shape nickel hydroxide, and the nano flower of nickel cobalt oxide is grown on the nano wire.
2. the preparation method of the nickel cobalt oxide electrode material of combined oxidation silver described in claim 1, which is characterized in that including
Following steps:
1) nickel foam is put into silver nitrate solution, carries out hydro-thermal reaction, product is washed into drying, obtains the stratiform hydrogen of silver-doped
Nickel oxide electrode material；
2) precursor salt solution is configured to by raw material of nickel salt, cobalt salt, urea and deionized water；
3) the stratiform nickel hydroxide electrode material of the resulting silver-doped of step 1) is put into the resulting precursor solution of step 2),
Hydro-thermal reaction is carried out, product is washed into drying, obtains the nickel cobalt double-hydroxide electrode material of silver-doped；
4) the nickel cobalt double-hydroxide electrode material of the resulting silver-doped of step 3) is made annealing treatment in air, is answered
Close the nickel cobalt oxide electrode material of silver oxide.
3. the preparation method of the nickel cobalt oxide electrode material of combined oxidation silver according to claim 2, which is characterized in that
The concentration of silver nitrate solution described in step 1) is 0.001~0.002mol/L.
4. the preparation method of the nickel cobalt oxide electrode material of combined oxidation silver according to claim 2, which is characterized in that
Nickel foam purity described in step 1) is 99.8% or more, surface density 300-450g/cm2。
5. the preparation method of the nickel cobalt oxide electrode material of combined oxidation silver according to claim 2, which is characterized in that
The temperature of hydro-thermal reaction described in step 1) is 160 DEG C, and the time is 6~8h.
6. the preparation method of the nickel cobalt oxide electrode material of combined oxidation silver according to claim 2, which is characterized in that
Nickel salt described in step 2) is nickel nitrate, nickel sulfate or nickel chloride；The cobalt salt is cobalt nitrate, cobaltous sulfate or cobalt chloride.
7. the preparation method of the nickel cobalt oxide electrode material of combined oxidation silver according to claim 6, which is characterized in that
It is highly preferred that the molar ratio of the nickel salt and cobalt salt, urea is 1:2:3；The nickel salt and the amount ratio of deionized water used are
0.05~0.1mol:1L.
8. the preparation method of the nickel cobalt oxide electrode material of combined oxidation silver according to claim 2, which is characterized in that
The temperature of hydro-thermal reaction described in step 3) is 120 DEG C, and the time is 6~8h.
9. the preparation method of the nickel cobalt oxide electrode material of combined oxidation silver according to claim 2, which is characterized in that
Annealing temperature described in step 4) is 250 DEG C~350 DEG C, and soaking time is 2~3h.
10. the application of the nickel cobalt oxide electrode material of the silver of combined oxidation described in claim 1, which is characterized in that the electrode
Material can be used as the electrode or catalyst of electrolysis water oxygen.
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