CN105033241B - A kind of super thin metal nickel nano film, its preparation method and the application as electrode material - Google Patents
A kind of super thin metal nickel nano film, its preparation method and the application as electrode material Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 170
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 83
- 239000002120 nanofilm Substances 0.000 title claims abstract description 45
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 42
- 239000002184 metal Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims description 15
- 239000007772 electrode material Substances 0.000 title abstract description 22
- 239000001257 hydrogen Substances 0.000 claims abstract description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims abstract description 17
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 12
- 239000000446 fuel Substances 0.000 claims abstract description 5
- 239000010406 cathode material Substances 0.000 claims abstract description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 36
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 claims description 31
- 239000000243 solution Substances 0.000 claims description 22
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 150000002815 nickel Chemical class 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000006722 reduction reaction Methods 0.000 claims description 7
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- 239000004202 carbamide Substances 0.000 claims description 5
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 claims description 4
- 229920005862 polyol Polymers 0.000 claims description 4
- 150000003077 polyols Chemical class 0.000 claims description 4
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
- 230000001376 precipitating effect Effects 0.000 claims description 3
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 2
- 229940051250 hexylene glycol Drugs 0.000 claims description 2
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical class CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 150000005846 sugar alcohols Polymers 0.000 claims description 2
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 claims 1
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 39
- 239000000758 substrate Substances 0.000 abstract description 38
- 238000000034 method Methods 0.000 abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- 239000006260 foam Substances 0.000 description 18
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 18
- 239000003054 catalyst Substances 0.000 description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 10
- 230000010287 polarization Effects 0.000 description 10
- 238000005406 washing Methods 0.000 description 10
- 238000003491 array Methods 0.000 description 9
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 9
- 239000004312 hexamethylene tetramine Substances 0.000 description 9
- 239000002057 nanoflower Substances 0.000 description 8
- 230000035484 reaction time Effects 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 239000012279 sodium borohydride Substances 0.000 description 5
- 229910000033 sodium borohydride Inorganic materials 0.000 description 5
- 241000209094 Oryza Species 0.000 description 4
- 235000007164 Oryza sativa Nutrition 0.000 description 4
- 239000012670 alkaline solution Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 4
- 235000003642 hunger Nutrition 0.000 description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical group [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 4
- 230000002441 reversible effect Effects 0.000 description 4
- 235000009566 rice Nutrition 0.000 description 4
- 230000037351 starvation Effects 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 3
- 239000010405 anode material Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000010189 synthetic method Methods 0.000 description 3
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000002135 nanosheet Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 241000549556 Nanos Species 0.000 description 1
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000006392 deoxygenation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002003 electron diffraction Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000009605 growth rhythm Effects 0.000 description 1
- -1 hydrogen Nickel oxide Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- 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
Landscapes
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Powder Metallurgy (AREA)
Abstract
The invention discloses a kind of super thin metal nickel nano film, its size is：25 nanometers of thickness, 100 300 nanometers of length, 50 300 nanometers of width.The invention also discloses surface to have super thin metal nickel nano film array electrode material, and it includes：Porous, electrically conductive substrate；Perpendicular to the super thin metal nickel nano film array of the substrate grown in the porous, electrically conductive substrate.The invention also discloses the electrode material that surface has metal nickel nano piece assembly.Above-mentioned three kinds of materials can be prepared with two-step hydrothermal route method.Above-mentioned material specific surface area is high, stability is strong, electrocatalysis characteristic is superior, can be used as the positive electrode of hydrazine hydrate oxidized fuel cell and the cathode material of electrolysis water liberation of hydrogen.
Description
Technical field
The invention belongs to inorganic advanced technical field of nano material
Background technology
Metal nano material has excellent light due to small-size effect and special Electronic Structure
The properties such as, electricity, catalysis, so as to have a wide range of applications.Compared to conventional metals nano material, two-dimensional ultrathin nano-sheet
Metal material has a very excellent thermal conductivity, the specific surface area of super large and the electron mobility of superelevation and electric conductivity etc., because
And there is high application value [Nat.Commun.2014,5,3093] in physics, chemistry and materials science field.But
Metallic atom tends to form three-dimensional close-packed structure so that liquid phase synthesis has the ultrathin nanometer of a large amount of unsaturated coordination atoms
Laminated structure turns into greatly challenge.Existing synthetic method can only prepare noble metal nano sheet knot under extreme harsh conditions
Structure, for only having the preparation of the transition non-noble metal nano piece of several atomic layer level thickness, never have been reported that.So how to use
Simple preparation method synthesize with ultra-thin non-noble metal nano piece be scientific circles' urgent need to resolve a key issue.
To solve the above problems, propose the present invention.
The content of the invention
The present invention prepares metal nickel nano piece and its assembling with superthin structure using simple unique synthetic method
Body.During as electrode material, super thin metal nickel nano film and its assembly show extremely excellent electrocatalysis characteristic.
The first aspect of the present invention is related to a kind of super thin metal nickel nano film, and its size is：Thickness 2-5 nanometers, length
100-300 nanometers, width 50-300 nanometers.
The second aspect of the present invention is related to a kind of preparation method of super thin metal nickel nano film, the super thin metal nickel nanometer
Piece thickness 2-5 nanometers, length 100-300 nanometers, width 50-300 nanometers, the preparation method include：
A. ultra-thin nickel hydroxide nano piece is generated by the hydro-thermal reaction of nickel salt solution and precipitating reagent in closed container, its
Size is thickness 5-10 nanometers, length 1.0-5.0 microns, width 0.5-3.0 microns；
B. by the ultra-thin nickel hydroxide nano piece, original appearance reduces in alkaline polyol solution.
In above-mentioned preparation method, the hydrothermal reaction condition is that will include soluble nickel salt and hexamethylenetetramine or urea
The aqueous solution heat up and carry out hydro-thermal reaction at autogenous pressures, wherein the original appearance reduction reaction conditionses are to receive nickel hydroxide
Rice piece, which is placed in alkaline polyol solution, to heat up and carries out alcohothermal reaction at autogenous pressures, wherein the polyalcohol is selected from
Ethylene glycol, propane diols, BDO, hexylene glycol.The precipitating reagent is selected from hexamethylenetetramine or urea.
The third aspect, the present invention relates to the electrode material that a kind of surface has super thin metal nickel nano film array, it includes：
Porous, electrically conductive substrate；
Perpendicular to the super thin metal nickel nano film array of the substrate grown in the porous, electrically conductive substrate；
The size of wherein described super thin metal nickel nano film is：Thickness 2-5 nanometers, length 100-300 nanometers, width 50-
300 nanometers.
Fourth aspect, the present invention relates to the electrode material that a kind of surface has nickel metal nickel nano piece assembly, it includes：
Porous, electrically conductive substrate；
It is perpendicular to the metal nickel nano piece assembly of the substrate grown, the assembly in the porous, electrically conductive substrate
The spherical nickel nano flower array assembled is intersected by metal nickel nano piece；Wherein described metal nickel nano piece assembly it is straight
Footpath is 30-70 nanometers.Preferably, a diameter of 40-60 nanometers of the metal nickel nano piece assembly, more preferably 45-55 receive
Rice, such as 50 rans.
In the present invention, the porous, electrically conductive substrate is nickel foam or foam copper.Wherein, described porous, electrically conductive substrate refers to
Conductive substrates with loose structure, the substrate are metal in material, are properly termed as foam metal.Wherein metal can be selected from
Any suitable metal, such as when metal is copper, then referred to as foam copper, when metal is nickel, then referred to as nickel foam.On bubble
The more of foam metal are discussed in detail and preparation method, may refer to existing patented technology document.Such foam metal is also
It is being commercially available or can be made by oneself according to pertinent literature content.
In a preferred embodiment of the present invention, described super thin metal nickel nano film piece in an array manner perpendicular to
The superficial growth of the porous, electrically conductive substrate, and be 100nm-300nm with the length of conductive substrates contact surface, the nickel nano film
Width is 50nm-300nm, and the thickness of the nickel nano film is 2nm-5nm.Wherein described array refers to single nanometer sheet in two dimension
Or the extension on three-dimensional, the orientating type extension or the extension of unordered non-orientation type that the extension can be ordered into.
By the assembly diameter that nickel nano film assembles in 50nm or so in the present invention, overall appearance like spheric granules,
Surface is characterized by transmission electron microscope and can be seen that the assembly is intersected by multi-disc nanometer sheet and form with multilevel hierarchy,
The present inventor is named as " nickel nano flower ".Such super thin metal nickel nano film array and mutually closely it is cross-linked to form three-dimensional
Porous nickel nano flower.Multiple ball shaped nanos spend can also each other it is orderly or it is unordered be stacked, form more complicated three-dimensional
Structure.
5th aspect, the present invention relates to a kind of surface as described in third aspect present invention to have ultra-thin nickel nano film array
Electrode material preparation method, it comprises the following steps：
A. by the aqueous solution comprising soluble nickel salt and hexamethylenetetramine or urea, it is added in reactor, then by table
The acid treated porous, electrically conductive substrate in face is put into reactor, then the closed reactor, is heated up and is entered at autogenous pressures
Water-filling thermal response, with vertical substrate grown nickel hydroxide nano chip arrays on the porous, electrically conductive substrate surface；
B. porous, electrically conductive substrate of the surface with nickel hydroxide nano chip arrays is taken out, dried after washing；
C. the ethylene glycol solution of sodium hydroxide, then the porous, electrically conductive base that will be obtained through step b are added into the second reactor
Bottom is put into the reactor, seals reactor, and heating simultaneously carries out alcohothermal reaction at autogenous pressures so that each hydrogen
Nickel oxide nano piece original appearance is reduced into ultra-thin nickel nano film array；After washing and being dried in vacuo, produce the surface have it is ultra-thin
The electrode material of nickel nano film array, and saved backup under conditions of starvation.
In the preferred scheme of the 5th aspect, wherein the soluble nickel salt is selected from nickel nitrate, nickel sulfate or nickel chloride；Its
Described in hydro-thermal reaction, soluble nickel salinity is 0.1-0.5 mol/Ls in the aqueous solution, hexamethylenetetramine concentration
For 0.2-1.0 mol/Ls, the condition of first hydro-thermal reaction is：Temperature is 90-120 DEG C, and the reaction time is 8-20 hours；
In alcohothermal reaction, concentration of the sodium hydroxide in ethylene glycol is 0.3-1.0 mol/Ls, the bar of the alcohothermal reaction
Part is：Temperature is 140-180 DEG C, and the reaction time is 8-24 hours.
6th aspect, the invention discloses a kind of surface as described in fourth aspect present invention to have ultra-thin nickel nano film group
The preparation method of the electrode material of body is filled, it comprises the following steps：
A. the aqueous solution comprising soluble nickel salt and hexamethylenetetramine or urea is added in reactor, then by surface
Acid treated porous, electrically conductive substrate is put into reactor, then the closed reactor, is heated up and is carried out at autogenous pressures
Hydro-thermal reaction, with vertical substrate grown nickel hydroxide nano chip arrays on the porous, electrically conductive substrate surface；
B. porous, electrically conductive substrate of the surface with nickel hydroxide nano chip arrays is taken out, dried after washing；
C. add the ethylene glycol solution of sodium hydroxide and sodium borohydride into the second reactor, then will be obtained through step b
Porous, electrically conductive substrate is put into the reactor, seals reactor, and heating simultaneously carries out alcohothermal reaction at autogenous pressures so that
Each nickel hydroxide nano piece original appearance is reduced into ultra-thin nickel nano film and forms the ultrathin nanometer piece assembly；Washing is simultaneously
After vacuum drying, producing the surface has the electrode material of ultra-thin nickel nano film assembly, and under conditions of starvation
Save backup.
In the preferred scheme of the 6th aspect, wherein the soluble nickel salt is selected from nickel nitrate, nickel sulfate or nickel chloride；Its
Described in hydro-thermal reaction, soluble nickel salinity is 0.1-0.5 mol/Ls in the aqueous solution, hexamethylenetetramine concentration
For 0.2-1.0 mol/Ls, the condition of first hydro-thermal reaction is：Temperature is 90-120 DEG C, and the reaction time is 8-20 hours；
In alcohothermal reaction, concentration of the sodium hydroxide in ethylene glycol is 0.3-1.0 mol/Ls, and sodium borohydride is in ethylene glycol
Concentration is 0.1-0.5 mol/Ls, and the condition of the alcohothermal reaction is：Temperature is 140-180 DEG C, reaction time 8-24
Hour.
Specifically, in the step a of above-mentioned 5th aspect and the 6th aspect, by porous, electrically conductive substrate, tilting to be put into first anti-
Answer in kettle, then first aqueous solution comprising soluble nickel salt and hexamethylenetetramine is added into the reactor, it is then closed to be somebody's turn to do
Reactor, heat up and carry out hydro-thermal reaction at autogenous pressures, prepare the vertical substrate life on the porous, electrically conductive substrate surface
Long nickel hydroxide nano chip arrays.Preferably, the porous, electrically conductive substrate important affair first passes through cleaning, to remove the dirt on surface
And impurity.Such cleaning can be cleaned by ultrasonic in concentrated hydrochloric acid, be then transferred to such as deionized water and ethanol equal solvent
In, it is cleaned by ultrasonic again.In first aqueous solution, the concentration of various materials can be adjusted as needed, for example, a kind of excellent
Select in embodiment, the soluble nickel salinity is 0.1-0.5 mol/Ls, and hexamethylenetetramine concentration is rubbed for 0.2-1.0
You/liter.It is of course also possible to use other concentration ranges.The condition of first hydro-thermal reaction can also be adjusted as needed
It is whole, such as a kind of optimum condition is：Temperature is 90-120 DEG C, and the reaction time is 8-20 hours.By the first hydro-thermal reaction, more
What is obtained in the conductive substrates of hole is nickel hydroxide nano chip arrays.Change the concentration of each material or change the bar of the first hydro-thermal reaction
Part, nickel hydroxide nano chip arrays arranging density on this substrate, growing height etc. can be adjusted, these can be by limited
It is secondary to test specifically to grope its growth rhythm.Wherein described soluble nickel salt is selected from nickel nitrate, nickel sulfate or nickel chloride, or it
Any hydrate with the crystallization water.After first hydro-thermal reaction terminates, beaten after first reactor is cooled into room temperature
Open.
Specifically, in the step b of above-mentioned 5th aspect and the 6th aspect, the porous, electrically conductive substrate is taken out, washs and does
It is dry.Specific washing and drying mode are not limited, for example, washing can be with any suitable solvent such as water, ethanol
It is rinsed or is cleaned by ultrasonic, drying can be by the way of dries in an oven.
Specifically, in the step c of above-mentioned 5th aspect, the is put into by the porous, electrically conductive substrate after step b processing is tilting
In two reactors, then the reducing solution comprising sodium hydroxide and ethylene glycol is added into the reactor, seal the reactor, heat up
And alcohothermal reaction is carried out at autogenous pressures so that each described nickel hydroxide nano piece is by in-situ reducing slabbing knot
The nickel nano film of structure.In second aqueous solution, the amount of various materials can be adjusted as needed, for example, a kind of preferred
In embodiment, concentration of the sodium hydroxide in ethylene glycol is 0.3-1.0 mol/Ls；The condition of the alcohothermal reaction
It can be adjusted as needed, such as a kind of optimum condition is：Temperature is 140-180 DEG C, and the reaction time is 8-24 hours.Also
Original reaction takes out the porous, electrically conductive substrate again after terminating, and washs and is dried in vacuo.Specific washing and drying mode will be entered
Row starvation, for example, washing can be rinsed or be cleaned by ultrasonic such as water, ethanol with the solvent of deoxygenation, drying can be with
By the way of being dried in vacuum drying oven.
Specifically, in the step c of above-mentioned 6th aspect, to the above-mentioned reducing solution comprising sodium hydroxide and ethylene glycol
In be additionally added sodium borohydride, and other conditions are constant, you can prepare nickel nano flower.The concentration of sodium borohydride can also be entered as needed
Row adjustment, for example, in a kind of preferred embodiment, concentration of the sodium borohydride in ethylene glycol is 0.1-0.5 mol/Ls.The alcohol
After thermal reduction reaction terminates, opened after second reactor is cooled into room temperature.Follow-up washing drying steps are the same as the present invention the
Described in five aspects.
7th aspect, the invention further relates to super thin metal nickel nano film described according to a first aspect of the present invention, third party
Surface described in face has the electrode material or surface described according to a fourth aspect of the present invention tool of ultra-thin nickel nano film array
The electrode material for having ultra-thin nickel nano film assembly is used as the purposes of the positive electrode of hydrazine hydrate oxidized fuel cell or as electricity
Solve the purposes of water cathode material for hydrogen evolution.
In the present invention, either surface undoubtedly considerably increases this with ultra-thin nickel nano film still with nickel nano flower
The surface area of the material of invention, and enhance it and make electrical contact with efficiency.The material of the present invention is very suitable for as hydrazine hydrate fuel
The positive electrode of battery and the cathode material of electrolysis water evolving hydrogen reaction, the performance shown are superior to currently commercially best
Platinum carbon catalyst.But the material for being also not excluded for the present invention finds other purposes be present in the future.
Beneficial effects of the present invention are as follows：
1st, preparation method of the invention synthesizes under simple hydrothermal reaction condition, and method is easy, and cost is cheap, repeatability
It is good, it is very friendly to environment；Synthetic method uniqueness set forth in the present invention is ingenious, is provided newly for synthesis ultrathin nanometer sheet metal
Thinking.The thickness of synthesized super thin metal nickel nano film is only several nanoscales, has the electric conductivity and quantum effect of superelevation.
2nd, material structure of the invention is homogeneous, ordered arrangement, and it is monoblock type material to what is more important, conduct in material
The nickel nano film and its assembly of electrode active material are directly connected with the conductive substrates as collector, without addition during making
Adhesive, and structure is novel, has good conduction property；Such structure avoids general powder body material and contacted with collector
Bad, the problem of electric transmission effect is poor, specific surface area is small and interfacial gases product adheres to, and then improve comprising the material
Electrode and fuel cell integrated electronic performance.
Brief description of the drawings
Fig. 1 is the high resolution transmission electron microscopy that the ultra-thin nickel nano film two panels of the present invention overlaps
(HRTEM)。
Fig. 2 is the lattice diffraction pattern of monolithic nickel nano film shown in Fig. 1, and spacing of lattice 0.203nm corresponds to (111) of metallic nickel
Crystal face.The provable nickel hydroxides of Fig. 2 are reduced completely, and nanometer sheet is pure metallic nickel nanometer sheet.
Fig. 3 is the X-ray diffractogram (XRD) that material changes in material synthesis processes shown in Fig. 1, raw in foam nickel base
After long nickel hydroxide, it may appear that nickel hydroxide characteristic peak.And after reduction reaction, the characteristic peak of nickel hydroxide disappears, and only deposits
In the characteristic peak of standard nickel, it was demonstrated that nickel hydroxide has been completely reduced.
Fig. 4 a and Fig. 4 b are the thickness phenograms of the monolithic nickel nano film of material shown in Fig. 1, it can be seen that every nickel nanometer
The thickness of piece is in the range of 2nm-5nm.
Fig. 5 is the stereoscan photograph figure (SEM) of the material of the present invention, wherein clearly showing, ultra-thin nickel nano film
Array is grown perpendicular to substrate surface, and the three-dimensional porous structure that aperture is less than 100nm is formed between ultra-thin nickel nano film；Wherein
Substrate is nickel foam.
Fig. 6 is material shown in Fig. 5, foam nickel base, nickel hydroxide array and 20% commercial Pt/C catalyst as anode
Material, the respective oxidation polarization curve in 0.5mol/l hydrazine hydrate alkaline solutions, using reversible hydrogen electrode as reference electrode.By
Figure is as can be seen that the electrode material of the present invention has minimum overpotential and most fast increase in current speed, it was demonstrated that of the invention
The function admirable during anode material that material aoxidizes as hydrazine hydrate.
Fig. 7 a are oxidation polarization curve of the material shown in Fig. 5 in various concentrations hydrazine hydrate solution, and Fig. 7 b are corresponding
Current versus time curve figure, it can be seen that material of the present invention has good in it can be tested in the oxidation of various concentrations hydrazine hydrate solution
Good stability.
Fig. 8 is material shown in Fig. 5, foam nickel base, nickel hydroxide array and 20% commercial Pt/C catalyst as negative electrode
Material, the polarization curve in 0.1mol/l KOH solutions during electrolysis water liberation of hydrogen, using reversible hydrogen electrode as reference electrode.This hair
Bright electrode material has the overpotential and most fast increase in current speed close to Pt/C catalyst, it was demonstrated that material of the invention is made
For electrolysis water hydrogen-precipitating electrode when function admirable.
Fig. 9 is current versus time curve figure during electrolysis water liberation of hydrogen in 0.1mol/l KOH solutions of material shown in Fig. 5, wherein
After 10 hours, the current density value of commercial Pt/C catalyst is reduced to the 86.7% of initial current density values, and the present invention
Surface has the electrode material of ultra-thin nickel nano film, and after 10 hours, its current density value is initial current density values
94.9%.It is seen that compared to currently commercially best Pt/C catalyst, material of the present invention has higher stabilization
Property.
Figure 10 is the high resolution transmission electron microscopy (HRTEM) of super thin metal nickel nano film assembly.It is wherein clear
Ground is shown, is intersected together by multi-disc nickel nano film, and it is spheroidal " nickel nano flower " to be assembled into outward appearance.
Figure 11 a are the electron microscopes of multiple metal nickel nano piece assemblies shown in Figure 10, and Figure 11 b are corresponding electronic diffractions
Figure, the different crystal faces of corresponding pure nickel.It has been reduced completely from the provable nickel hydroxides of Figure 15 b, nano flower is that pure metallic nickel is received
Popped rice.
Figure 12 is the X-ray diffractogram (XRD) that material changes in material synthesis processes shown in Figure 10.Nickel hydroxide array passes through
After crossing reduction reaction, the characteristic peak of nickel hydroxide is disappeared, it was demonstrated that nickel hydroxide has been completely reduced.
Figure 13 is material shown in Figure 10, foam nickel base, nickel hydroxide array and 20% commercial Pt/C catalyst as sun
Pole material, the respective oxidation polarization curve in 0.5mol/l hydrazine hydrate alkaline solutions, using reversible hydrogen electrode as reference electrode.
As seen from the figure, electrode material of the invention has minimum overpotential and most fast increase in current speed, it was demonstrated that the present invention
Material aoxidized as hydrazine hydrate anode material when function admirable.
Figure 14 is current versus time curve figure of the material shown in Figure 10 in various concentrations hydrazine hydrate solution, it can be seen that this
Invention material can have good stability in the oxidation test in various concentrations hydrazine hydrate solution.
Figure 15 is material shown in Figure 10, foam nickel base, nickel hydroxide array and 20% commercial Pt/C catalyst as cloudy
Pole material, the polarization curve in 0.1mol/l KOH solutions during electrolysis water liberation of hydrogen, using reversible hydrogen electrode as reference electrode.
Figure 16 is material shown in Figure 10 and 20% commercial Pt/C catalyst electrolysis water liberation of hydrogen in 0.1mol/l KOH solutions
When current versus time curve figure, it is seen that compared to currently commercially best Pt/C catalyst, material tool of the present invention
There is higher stability.
Embodiment
The present invention is further illustrated by following examples.What embodiment was merely exemplary, and it is nonrestrictive.
Embodiment 1
A. it is put into foam nickel base is tilting in the first reactor, then is added into the reactor and include 0.125 mol/L
Nickel nitrate, the aqueous solution of the hexamethylenetetramine of 0.25 mol/L, then closed reactor, be warming up to 100 DEG C and from
Keeps 10 hours progress hydro-thermal reactions under raw pressure, with the foam nickel base surface the vertical substrate grown nickel hydroxide receive
Rice chip arrays；
B. the foam nickel base is taken out, washs and dries；
C. it is put into the nickel hydroxide nano chip arrays substrate after step b processing is tilting in the second reactor, it is then anti-to this
Answer and the solution comprising concentration of the sodium hydroxide in ethylene glycol is 0.625 mol/L is added in kettle, seal the reactor, heat up
Keep to 160 DEG C and at autogenous pressures carrying out alcohothermal reaction in 12 hours, make each nickel hydroxide nano piece original appearance
It is reduced into nickel nano film.After alcohothermal reaction terminates, opened after second reactor is cooled into room temperature；And take again
The foam nickel base gone out after the reduction, after washing and being dried in vacuo, saved backup under conditions of starvation.
The high magnification transmission electron microscope figure of resulting super thin metal nickel nano film is referring to accompanying drawing 1, its lattice diffraction
Figure is referring to accompanying drawing 2, and its XRD spectra is referring to accompanying drawing 3, and for its single-sheet thickness referring to accompanying drawing Fig. 4 a and Fig. 4 b, it is grown on nickel foam
SEM figures aoxidize polarization curve referring to accompanying drawing 6 referring to accompanying drawing 5, its hydrazine hydrate in the alkaline solution of hydrazine hydrate, and it is in difference
For polarization curve and stability test figure in the hydrazine hydrate solution of concentration referring to accompanying drawing 7a and Fig. 7 b, it is molten in 0.1mol/L KOH
The cathodic polarization curve figure of electrolysis water liberation of hydrogen is referring to accompanying drawing 8, the electricity of its electrolysis water liberation of hydrogen in 0.1mol/L KOH solutions in liquid
Stream-time plot is referring to accompanying drawing 9.
Embodiment 2
Referring to the method in embodiment 1,0.33 mol/L boron hydrogen will be added in the reduction system in the step c of embodiment 1
Change sodium, and when other conditions are constant, you can prepare the assembly of nickel nano film, i.e. nickel nano flower.
For the high magnification transmission electron microscope figure of resulting ultra-thin nickel nano film assembly materials referring to accompanying drawing 10, it is high
Multiplying power transmission electron microscope figure and electron diffraction diagram are referring to accompanying drawing 11a and Figure 11 b, and its XRD spectra is referring to accompanying drawing 12, and it is in water
Close the hydrazine hydrate in the alkaline solution of hydrazine and aoxidize polarization curve referring to accompanying drawing 13, it is in the hydrazine hydrate solution of various concentrations
Stability test figure is referring to accompanying drawing 14, and the cathodic polarization curve figure of its electrolysis water liberation of hydrogen in 0.1mol/L KOH solutions is referring to attached
Figure 15, the current versus time curve figure of its electrolysis water liberation of hydrogen in 0.1mol/L KOH solutions is referring to accompanying drawing 16.
Each experimental data shown in the drawings, the surface for fully demonstrating the present invention have super thin metal nickel nano film array
Electrode material and surface have the excellent properties of the electrode material of metal nickel nano piece assembly, and its many physicochemical property is big
Current commercial Pt/C electrode materials are surmounted greatly, have been an important breakthrough in electrode material field.
Claims (3)
1. a kind of preparation method of super thin metal nickel nano film, the super thin metal nickel nano film thickness 2-5 nanometers, length 100-
300 nanometers, width 50-300 nanometers, the nanometer sheet is pure metallic nickel nanometer sheet, and the preparation method includes：
A. ultra-thin nickel hydroxide nano piece, its size are generated by the hydro-thermal reaction of nickel salt solution and precipitating reagent in closed container
For thickness 5-10 nanometers, length 1.0-5.0 microns, width 0.5-3.0 microns；
B. by ultra-thin nickel hydroxide nano piece alcohothermal in alkaline polyol solution.
2. preparation method according to claim 1, wherein the hydrothermal reaction condition is that will include soluble nickel salt and six
The aqueous solution of methine tetramine or urea heats up in closed container and carries out hydro-thermal reaction at autogenous pressures, wherein the alcohol
Thermal reduction reaction condition is that nickel hydroxide nano piece and alkaline polyol solution heat up and in self-generated pressure in closed container
Lower progress alcohothermal reaction, wherein the polyalcohol is selected from ethylene glycol, propane diols, BDO, hexylene glycol.
3. the application of super thin metal nickel nano film prepared by preparation method according to claim 1, it is characterised in that it can
Positive electrode as hydrazine hydrate oxidized fuel cell or as electrolysis water cathode material for hydrogen evolution.
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