CN105033241A - Ultrathin metallic nickel nanosheet, manufacturing method thereof and application of nanosheets as electrode materials - Google Patents
Ultrathin metallic nickel nanosheet, manufacturing method thereof and application of nanosheets as electrode materials Download PDFInfo
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- CN105033241A CN105033241A CN201510303542.0A CN201510303542A CN105033241A CN 105033241 A CN105033241 A CN 105033241A CN 201510303542 A CN201510303542 A CN 201510303542A CN 105033241 A CN105033241 A CN 105033241A
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 205
- 239000002135 nanosheet Substances 0.000 title claims abstract description 34
- 239000007772 electrode material Substances 0.000 title claims abstract description 32
- 238000004519 manufacturing process Methods 0.000 title 1
- 239000000758 substrate Substances 0.000 claims abstract description 56
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 26
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000001257 hydrogen Substances 0.000 claims abstract description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 16
- 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 14
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000010406 cathode material Substances 0.000 claims abstract description 6
- 239000000446 fuel Substances 0.000 claims abstract description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 98
- 239000002120 nanofilm Substances 0.000 claims description 55
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 51
- 229910052751 metal Inorganic materials 0.000 claims description 45
- 239000002184 metal Substances 0.000 claims description 45
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 claims description 38
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 28
- 239000000243 solution Substances 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 239000006260 foam Substances 0.000 claims description 20
- 238000002360 preparation method Methods 0.000 claims description 17
- 238000005406 washing Methods 0.000 claims description 17
- 239000007864 aqueous solution Substances 0.000 claims description 14
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 14
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 14
- 150000002815 nickel Chemical class 0.000 claims description 14
- 238000003491 array Methods 0.000 claims description 13
- 239000012267 brine Substances 0.000 claims description 12
- 238000005868 electrolysis reaction Methods 0.000 claims description 12
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims description 12
- 239000002057 nanoflower Substances 0.000 claims description 10
- 230000035484 reaction time Effects 0.000 claims description 10
- 238000006722 reduction reaction Methods 0.000 claims description 9
- 239000012279 sodium borohydride Substances 0.000 claims description 8
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 7
- 239000004202 carbamide Substances 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- 235000003642 hunger Nutrition 0.000 claims description 6
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical group [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 6
- 230000037351 starvation Effects 0.000 claims description 6
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 5
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 5
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 5
- 229910000363 nickel(II) sulfate Inorganic materials 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
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 229920005862 polyol Polymers 0.000 claims description 4
- 150000003077 polyols Chemical class 0.000 claims description 4
- 238000010306 acid treatment Methods 0.000 claims description 3
- 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
- 238000010438 heat treatment Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 36
- 238000000034 method Methods 0.000 abstract description 7
- 239000010405 anode material Substances 0.000 abstract description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 10
- 230000010287 polarization Effects 0.000 description 10
- 238000001035 drying Methods 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 5
- 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
- 230000002441 reversible effect Effects 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000004506 ultrasonic cleaning Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000002086 nanomaterial Substances 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
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000002003 electron diffraction Methods 0.000 description 2
- WJLFHDKAOYPRJZ-UHFFFAOYSA-N hydrazine;dihydrate Chemical compound O.O.NN.NN WJLFHDKAOYPRJZ-UHFFFAOYSA-N 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 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
- 230000005611 electricity Effects 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
- 239000012535 impurity Substances 0.000 description 1
- 238000011065 in-situ storage Methods 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
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000007704 transition Effects 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
Abstract
The invention discloses an ultrathin metallic nickel nanosheet. The size of the ultrathin metallic nickel nanosheet is that the thickness ranges from 2 nanometers to 5 nanometers, the length ranges from 100 nanometers to 300 nanometers, and the width ranges from 50 nanometers to 300 nanometers. The invention further discloses an electrode material with the surface provided with an ultrathin metallic nickel nanosheet array. The electrode material comprises a porous conductive substrate and the ultrathin metallic nickel nanosheet array which grows on the substrate and is perpendicular to the porous conductive substrate. The invention further discloses an electrode material with the surface provided with a metallic nickel nanosheet assembling body. The three materials mentioned above can be manufactured through two steps of a hydrothermal synthesis method. The materials are large in specific surface area, high in stability, excellent in electro-catalytic property and capable of being used as an anode material of a hydrazine hydrate oxygenated fuel battery and a cathode material of electrolyzed elutriation hydrogen.
Description
Technical field
The invention belongs to inorganic advanced technical field of nano material
Background technology
Metal nano material, owing to having small-size effect and special Electronic Structure, thus has the excellent character such as optics, electricity, catalysis, thus has a wide range of applications.Compared to conventional metals nano material, two-dimensional ultrathin nano-sheet metal material has very excellent thermal conductivity, the specific area of super large and the electron mobility of superelevation and electric conductivity etc., thus at physics, chemistry and material science, there is high using value [Nat.Commun.2014,5,3093].But metallic atom tends to form three-dimensional close-packed structure, the ultrathin nanometer laminated structure making liquid phase synthesis have a large amount of unsaturated coordination atom becomes great challenge.Existing synthetic method can only prepare noble metal nano sheet structure under extreme harsh conditions, for the preparation of transition non-noble metal nano sheet only having several atomic layer level thickness, never has report.So, how to adopt simple preparation method to synthesize and there is the key issue that ultra-thin non-noble metal nano Pian Shi scientific circles need solution badly.
For solving the problem, the present invention is proposed.
Summary of the invention
The present invention adopts simple unique synthetic method, prepares the metal nickel nano sheet and assembly thereof with superthin structure.During as electrode material, super thin metal nickel nano film and assembly thereof show extremely excellent electrocatalysis characteristic.
A first aspect of the present invention relates to a kind of super thin metal nickel nano film, and it is of a size of: thickness 2-5 nanometer, length 100-300 nanometer, width 50-300 nanometer.
A second aspect of the present invention relates to a kind of preparation method of super thin metal nickel nano film, described super thin metal nickel nano film thickness 2-5 nanometer, length 100-300 nanometer, width 50-300 nanometer, and described preparation method comprises:
A. by nickel salt solution and precipitating reagent, the hydro-thermal reaction in closed container generates ultra-thin nickel hydroxide nano sheet, and it is of a size of thickness 5-10 nanometer, length 1.0-5.0 micron, width 0.5-3.0 micron;
B. by the original appearance reduction in alkaline polyol solution of described ultra-thin nickel hydroxide nano sheet.
In above-mentioned preparation method, described hydrothermal reaction condition is heated up and carry out hydro-thermal reaction at autogenous pressures by the aqueous solution comprising soluble nickel salt and hexamethylenetetramine or urea, wherein said original appearance reduction reaction conditions heats up for nickel hydroxide nano sheet being placed in alkaline polyol solution and carrying out alcohothermal reaction at autogenous pressures, wherein said polyalcohol is selected from ethylene glycol, propane diols, BDO, hexylene glycol.Described 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 comprises:
Porous, electrically conductive substrate;
Perpendicular to the super thin metal nickel nano film array of this substrate grown in described porous, electrically conductive substrate;
Wherein said super thin metal nickel nano film is of a size of: thickness 2-5 nanometer, length 100-300 nanometer, width 50-300 nanometer.
Fourth aspect, the present invention relates to the electrode material that a kind of surface has nickel metal nickel nano sheet assembly, it comprises:
Porous, electrically conductive substrate;
Perpendicular to the metal nickel nano sheet assembly of this substrate grown in described porous, electrically conductive substrate, described assembly intersects by metal nickel nano sheet the spherical nickel nano flower array assembled; The diameter of wherein said metal nickel nano sheet assembly is 30-70 nanometer.Preferably, the diameter of described metal nickel nano sheet assembly is 40-60 nanometer, is more preferably 45-55 nanometer, such as 50 ran.
In the present invention, described porous, electrically conductive substrate is nickel foam or foam copper.Wherein, described porous, electrically conductive substrate refers to the conductive substrates with loose structure, and this substrate is metal in material, can be called foam metal.Wherein metal can be selected from any applicable metal, such as, when metal is copper, is then called foam copper, when metal is nickel, is then called nickel foam.About how detailed introduction and the preparation method of foam metal, can see existing patented technology document.Such foam metal be also can be commercially available or can make by oneself according to pertinent literature content.
In a preferred embodiment of the present invention, described super thin metal nickel nano film sheet is with the superficial growth of the form of array perpendicular to this porous, electrically conductive substrate, and be 100nm-300nm with the length of conductive substrates contact surface, the width of described nickel nano film is 50nm-300nm, and the thickness of described nickel nano film is 2nm-5nm.Wherein said array refers to the expansion of single nanometer sheet in two dimension or three-dimensional, and this expansion can be orderly orientating type expansion, also can be unordered non-orientation type expansion.
The assembly diameter assembled by nickel nano film in the present invention is at about 50nm, overall appearance is like spheric granules, surface is long multilevel hierarchy, and characterized by transmission electron microscope and can find out that this assembly is intersected mutually by multi-disc nanometer sheet and form, the present inventor is by its called after " nickel nano flower ".Such super thin metal nickel nano film array and be mutually closely cross-linked to form three-dimensional porous nickel nano flower.Multiple ball shaped nano is spent can also be orderly or to be unorderedly stacked each other, forms more complicated three-dimensional structure.
5th aspect, the present invention relates to the preparation method that a kind of surface as described in third aspect present invention has the electrode material of ultra-thin nickel nano film array, it comprises the following steps:
A. the aqueous solution of soluble nickel salt and hexamethylenetetramine or urea will be comprised, join in reactor, again reactor is put in the porous, electrically conductive substrate of surface after acid treatment, then this reactor airtight, heat up and carry out hydro-thermal reaction at autogenous pressures, with this substrate grown nickel hydroxide nano chip arrays vertical on this porous, electrically conductive substrate surface;
B. the porous, electrically conductive substrate of nickel hydroxide nano chip arrays is had to take out by long for surface, dry after washing;
C. in the second reactor, add the ethylene glycol solution of NaOH, again this reactor is put in the porous, electrically conductive substrate obtained through step b, sealed reactor, heat up and carry out alcohothermal reaction at autogenous pressures, making nickel hydroxide nano sheet original appearance described in each be reduced into ultra-thin nickel nano film array; Washing also, after vacuum drying, obtains the electrode material that described surface has ultra-thin nickel nano film array, and saves backup under the condition of starvation.
In preferred version in the 5th, wherein said soluble nickel salt is selected from nickel nitrate, nickelous sulfate or nickel chloride; In wherein said hydro-thermal reaction, in the described aqueous solution, soluble nickel salinity is 0.1-0.5 mol/L, and hexamethylenetetramine concentration is 0.2-1.0 mol/L, and the condition of described first hydro-thermal reaction is: temperature is 90-120 DEG C, and the reaction time is 8-20 hour; In alcohothermal reaction, the concentration of NaOH in ethylene glycol is 0.3-1.0 mol/L, and the condition of described alcohothermal reaction is: temperature is 140-180 DEG C, and the reaction time is 8-24 hour.
6th aspect, the invention discloses the preparation method that a kind of surface as described in fourth aspect present invention has the electrode material of ultra-thin nickel nano film assembly, it comprises the following steps:
A. the aqueous solution comprising soluble nickel salt and hexamethylenetetramine or urea is joined in reactor, again reactor is put in the porous, electrically conductive substrate of surface after acid treatment, then this reactor airtight, heat up and carry out hydro-thermal reaction at autogenous pressures, with this substrate grown nickel hydroxide nano chip arrays vertical on this porous, electrically conductive substrate surface;
B. the porous, electrically conductive substrate of nickel hydroxide nano chip arrays is had to take out by long for surface, dry after washing;
C. in the second reactor, add the ethylene glycol solution of NaOH and sodium borohydride, again this reactor is put in the porous, electrically conductive substrate obtained through step b, sealed reactor, heat up and carry out alcohothermal reaction at autogenous pressures, make nickel hydroxide nano sheet original appearance described in each be reduced into ultra-thin nickel nano film and form described ultrathin nanometer sheet assembly; Washing also, after vacuum drying, obtains the electrode material that described surface has ultra-thin nickel nano film assembly, and saves backup under the condition of starvation.
In preferred version in the 6th, wherein said soluble nickel salt is selected from nickel nitrate, nickelous sulfate or nickel chloride; In wherein said hydro-thermal reaction, in the described aqueous solution, soluble nickel salinity is 0.1-0.5 mol/L, and hexamethylenetetramine concentration is 0.2-1.0 mol/L, and the condition of described first hydro-thermal reaction is: temperature is 90-120 DEG C, and the reaction time is 8-20 hour; In alcohothermal reaction, the concentration of NaOH in ethylene glycol is 0.3-1.0 mol/L, and the concentration of sodium borohydride in ethylene glycol is 0.1-0.5 mol/L, and the condition of described alcohothermal reaction is: temperature is 140-180 DEG C, and the reaction time is 8-24 hour.
Specifically, in the step a of above-mentioned 5th aspect and the 6th aspect, the first reactor is put into by tilting for porous, electrically conductive substrate, first aqueous solution comprising soluble nickel salt and hexamethylenetetramine is added again in this reactor, then this reactor airtight, heat up and carry out hydro-thermal reaction at autogenous pressures, being prepared in the nickel hydroxide nano chip arrays of this substrate grown vertical on this porous, electrically conductive substrate surface.Preferably, this porous, electrically conductive substrate will in advance through cleaning, to remove dirt on surface and impurity.Such cleaning can be ultrasonic cleaning in concentrated hydrochloric acid, is then transferred in such as deionized water and ethanol equal solvent, ultrasonic cleaning again.In this first aqueous solution, the concentration of various material can adjust as required, and such as, in a kind of preferred embodiment, described soluble nickel salinity is 0.1-0.5 mol/L, and hexamethylenetetramine concentration is 0.2-1.0 mol/L.Certainly, also other concentration range can be used.The condition of described first hydro-thermal reaction also can adjust as required, and such as a kind of optimum condition is: temperature is 90-120 DEG C, and the reaction time is 8-20 hour.Through the first hydro-thermal reaction, what porous, electrically conductive substrate obtained is nickel hydroxide nano chip arrays.Change the concentration of each material or change the condition of the first hydro-thermal reaction, can adjust nickel hydroxide nano chip arrays arranging density on this substrate, growing height etc., these can be tested by limited number of time and specifically grope its growth rhythm.Wherein said soluble nickel salt is selected from nickel nitrate, nickelous sulfate or nickel chloride, or their any hydrate with the crystallization water.After this first hydro-thermal reaction terminates, open after this first reactor is cooled to room temperature.
Specifically, in the step b of above-mentioned 5th aspect and the 6th aspect, take out this porous, electrically conductive substrate, washing is also dry.Do not limit concrete washing and drying mode, such as, washing can be carried out rinsing or ultrasonic cleaning with any suitable solvent such as water, ethanol etc., and drying can adopt the mode of drying in an oven.
Specifically, in the step c of above-mentioned 5th aspect, the second reactor is put into by tilting for the porous, electrically conductive substrate after step b process, the reducing solution comprising NaOH and ethylene glycol is added again in this reactor, seal this reactor, heat up and carry out alcohothermal reaction at autogenous pressures, making nickel hydroxide nano sheet described in each by the nickel nano film of in-situ reducing slabbing structure.In described second aqueous solution, various amount of substance can adjust as required, and such as, in a kind of preferred embodiment, the concentration of NaOH in ethylene glycol is 0.3-1.0 mol/L; The condition of described alcohothermal reaction also can adjust as required, and such as a kind of optimum condition is: temperature is 140-180 DEG C, and the reaction time is 8-24 hour.This porous, electrically conductive substrate is again taken out, washing also vacuum drying after reduction reaction terminates.Will carry out starvation to concrete washing and drying mode, such as, washing can be carried out rinsing or ultrasonic cleaning with the solvent of deoxygenation such as water, ethanol etc., and drying can adopt the mode of drying in vacuum drying oven.
Specifically, in the step c of above-mentioned 6th aspect, also add sodium borohydride to above-mentioned comprising in the reducing solution of NaOH and ethylene glycol, and other condition is constant, can prepare nickel nano flower.The concentration of sodium borohydride also can adjust as required, and such as, in a kind of preferred embodiment, the concentration of sodium borohydride in ethylene glycol is 0.1-0.5 mol/L.After the reaction of this alcohothermal terminates, open after this second reactor is cooled to room temperature.Follow-up washing drying steps is with described in fifth aspect present invention.
7th aspect, the invention still further relates to according to a first aspect of the present invention described super thin metal nickel nano film, electrode material that electrode material that surface described in the third aspect has ultra-thin nickel nano film array or surface described according to a fourth aspect of the present invention have ultra-thin nickel nano film assembly is used as the purposes of the positive electrode of hydrazine hydrate oxidized fuel cell or is used as the purposes of brine electrolysis cathode material for hydrogen evolution.
In the present invention, no matter be that surface has ultra-thin nickel nano film or has nickel nano flower, considerably increase the surface area of material of the present invention undoubtedly, and enhance its electrical contact efficiency.Material of the present invention is very suitable for the cathode material of positive electrode as hydrazine hydrate fuel cell and brine electrolysis evolving hydrogen reaction, and the performance shown all is superior to current commercial best platinum C catalyst.But do not get rid of material of the present invention yet and find to there is other purposes in the future.
Beneficial effect of the present invention is as follows:
1, preparation method of the present invention synthesizes under simple hydrothermal reaction condition, and method is easy, with low cost, reproducible, very friendly to environment; Synthetic method uniqueness set forth in the present invention is ingenious, for synthesis ultrathin nanometer sheet metal provides new approaches.The thickness of synthesized super thin metal nickel nano film is only several nanoscale, has electric conductivity and the quantum effect of superelevation.
2, homogeneous, the ordered arrangement of material structure of the present invention, what is more important its be monoblock type material, directly be connected with the conductive substrates as collector as the nickel nano film of electrode active material and assembly thereof in material, without the need to adding adhesive during making, and novel structure, there is good conduction property; Such structure avoids the problem that the little and interfacial gases product of general powder body material and collector loose contact, electric transmission weak effect, specific area adheres to, and then improves the integrated electronic performance of electrode and the fuel cell comprising this material.
Accompanying drawing explanation
Fig. 1 is the high resolution transmission electron microscopy figure (HRTEM) that ultra-thin nickel nano film two panels of the present invention overlaps.
Fig. 2 is the lattice diffraction pattern of the nickel nano film of monolithic shown in Fig. 1, (111) crystal face of the corresponding metallic nickel of spacing of lattice 0.203nm.The provable nickel hydroxide of Fig. 2 is reduced completely, and nanometer sheet is pure metallic nickel nanometer sheet.
Fig. 3 is the X-ray diffractogram (XRD) of material change in material synthesis processes shown in Fig. 1, after foam nickel base grows nickel hydroxide, there will be nickel hydroxide characteristic peak.And after reduction reaction, the characteristic peak of nickel hydroxide disappears, only there is the characteristic peak of standard nickel, prove that nickel hydroxide is all reduced.
Fig. 4 a and Fig. 4 b is the thickness phenogram of the monolithic nickel nano film of material shown in Fig. 1, can find out that the thickness of every sheet nickel nano film is within the scope of 2nm-5nm.
Fig. 5 is the stereoscan photograph figure (SEM) of material of the present invention, wherein clearly shows, and ultra-thin nickel nano film array grows perpendicular to substrate surface, and forms the three-dimensional porous structure that aperture is less than 100nm between ultra-thin nickel nano film; Wherein substrate is nickel foam.
Fig. 6 be material shown in Fig. 5, foam nickel base, nickel hydroxide array and 20% commercial Pt/C catalyst as anode material, oxidation polarization curve respective in 0.5mol/l hydrazine hydrate alkaline solution take reversible hydrogen electrode as reference electrode.As seen from the figure, electrode material of the present invention has minimum overpotential and the fastest electric current growth rate, function admirable when proving the anode material that material of the present invention is oxidized as hydrazine hydrate.
Fig. 7 a is the oxidation polarization curve of material shown in Fig. 5 in variable concentrations hydrazine hydrate solution, and Fig. 7 b is corresponding current versus time curve figure, can find out that material of the present invention can have good stability in the oxidation test at variable concentrations hydrazine hydrate solution.
Fig. 8 be material shown in Fig. 5, foam nickel base, nickel hydroxide array and 20% commercial Pt/C catalyst as cathode material, the polarization curve in 0.1mol/lKOH solution during brine electrolysis liberation of hydrogen take reversible hydrogen electrode as reference electrode.Electrode material of the present invention has overpotential close to Pt/C catalyst and the fastest electric current growth rate, proves that material of the present invention is as function admirable during brine electrolysis hydrogen-precipitating electrode.
Fig. 9 is current versus time curve figure during brine electrolysis liberation of hydrogen in 0.1mol/lKOH solution of material shown in Fig. 5, after wherein using 10 hours, the current density value of commercial Pt/C catalyst reduces to 86.7% of initial current density values, and surface of the present invention has the electrode material of ultra-thin nickel nano film, use after 10 hours, its current density value is 94.9% of initial current density values.As can be seen from Figure, compared to current commercial best Pt/C catalyst, material of the present invention has higher stability.
Figure 10 is the high resolution transmission electron microscopy figure (HRTEM) of super thin metal nickel nano film assembly.Wherein clearly show, mutually intersected by multi-disc nickel nano film, be assembled into outward appearance spheroidal " nickel nano flower ".
Figure 11 a is the Electronic Speculum figure of multiple metal nickel nano sheet assembly shown in Figure 10, Figure 11 b is corresponding electron diffraction diagram, the different crystal faces of corresponding pure nickel.Be reduced completely from the provable nickel hydroxide of Figure 15 b, nano flower is pure metallic nickel nano flower.
Figure 12 is the X-ray diffractogram (XRD) of material change in material synthesis processes shown in Figure 10.Nickel hydroxide array is after reduction reaction, and the characteristic peak of nickel hydroxide disappears, and proves that nickel hydroxide is all reduced.
Figure 13 be material shown in Figure 10, foam nickel base, nickel hydroxide array and 20% commercial Pt/C catalyst as anode material, oxidation polarization curve respective in 0.5mol/l hydrazine hydrate alkaline solution take reversible hydrogen electrode as reference electrode.As seen from the figure, electrode material of the present invention has minimum overpotential and the fastest electric current growth rate, function admirable when proving the anode material that material of the present invention is oxidized as hydrazine hydrate.
Figure 14 is the current versus time curve figure of material shown in Figure 10 in variable concentrations hydrazine hydrate solution, can find out that material of the present invention can have good stability in the oxidation test at variable concentrations hydrazine hydrate solution.
Figure 15 be material shown in Figure 10, foam nickel base, nickel hydroxide array and 20% commercial Pt/C catalyst as cathode material, the polarization curve in 0.1mol/lKOH solution during brine electrolysis liberation of hydrogen take reversible hydrogen electrode as reference electrode.
Figure 16 is material shown in Figure 10 and 20% commercial Pt/C catalyst current versus time curve figure during brine electrolysis liberation of hydrogen in 0.1mol/lKOH solution, and as can be seen from Figure, compared to current commercial best Pt/C catalyst, material of the present invention has higher stability.
Detailed description of the invention
The present invention is further illustrated by following examples.Embodiment is only illustrative, and not restrictive.
Embodiment 1
A. the first reactor is put into by tilting for foam nickel base, the nickel nitrate comprising 0.125 mol/L is added again in this reactor, the aqueous solution of the hexamethylenetetramine of 0.25 mol/L, then this reactor airtight, be warming up to 100 DEG C and keep at autogenous pressures carrying out hydro-thermal reaction in 10 hours, with at this foam nickel base this substrate grown nickel hydroxide nano chip arrays vertical on the surface;
B. take out this foam nickel base, washing is also dry;
C. the second reactor is put into by tilting for the nickel hydroxide nano chip arrays substrate after step b process, add in this reactor again and comprise the solution that the concentration of NaOH in ethylene glycol is 0.625 mol/L, seal this reactor, be warming up to 160 DEG C and keep at autogenous pressures carrying out alcohothermal reaction in 12 hours, making nickel hydroxide nano sheet original appearance described in each be reduced into nickel nano film.After the reaction of this alcohothermal terminates, open after this second reactor is cooled to room temperature; And the foam nickel base of again taking out after this reduction, washing also, after vacuum drying, saves backup under the condition of starvation.
The high magnification transmission electron microscope figure of the super thin metal nickel nano film obtained is see accompanying drawing 1, its lattice diffraction pattern is see accompanying drawing 2, its XRD spectra is see accompanying drawing 3, its single-sheet thickness is see accompanying drawing Fig. 4 a and Fig. 4 b, its SEM figure being grown on nickel foam is see accompanying drawing 5, its in the alkaline solution of hydrazine hydrate hydrazine hydrate oxidation polarization curve see accompanying drawing 6, its polarization curve in the hydrazine hydrate solution of variable concentrations and stability test figure are see accompanying drawing 7a and Fig. 7 b, the cathodic polarization curve figure of its brine electrolysis liberation of hydrogen in 0.1mol/LKOH solution is see accompanying drawing 8, the current versus time curve figure of its brine electrolysis liberation of hydrogen in 0.1mol/LKOH solution is see accompanying drawing 9.
Embodiment 2
See the method in embodiment 1, the sodium borohydride of 0.33mol/L will be added in the reduction system in embodiment 1 step c, and when other condition is constant, the assembly of nickel nano film can be prepared, i.e. nickel nano flower.
The high magnification transmission electron microscope figure of the ultra-thin nickel nano film assembly materials obtained is see accompanying drawing 10, its high magnification transmission electron microscope figure and electron diffraction diagram are see accompanying drawing 11a and Figure 11 b, its XRD spectra is see accompanying drawing 12, its in the alkaline solution of hydrazine hydrate hydrazine hydrate oxidation polarization curve see accompanying drawing 13, its stability test figure in the hydrazine hydrate solution of variable concentrations is see accompanying drawing 14, the cathodic polarization curve figure of its brine electrolysis liberation of hydrogen in 0.1mol/LKOH solution is see accompanying drawing 15, the current versus time curve figure of its brine electrolysis liberation of hydrogen in 0.1mol/LKOH solution is see accompanying drawing 16.
Each experimental data shown in the drawings, sufficient proof surface of the present invention has the excellent properties that the electrode material of super thin metal nickel nano film array and surface have the electrode material of metal nickel nano sheet assembly, its a lot of physicochemical property has surmounted the Pt/C electrode material of current commercialization greatly, is an important breakthrough in electrode material field.
Claims (11)
1. a super thin metal nickel nano film, it is of a size of: thickness 2-5 nanometer, length 100-300 nanometer, width 50-300 nanometer.
2. a preparation method for super thin metal nickel nano film, described super thin metal nickel nano film thickness 2-5 nanometer, length 100-300 nanometer, width 50-300 nanometer, described preparation method comprises:
A. by nickel salt solution and precipitating reagent, the hydro-thermal reaction in closed container generates ultra-thin nickel hydroxide nano sheet, and it is of a size of thickness 5-10 nanometer, length 1.0-5.0 micron, width 0.5-3.0 micron;
B. by the original appearance reduction in alkaline polyol solution of described ultra-thin nickel hydroxide nano sheet.
3. preparation method according to claim 2, wherein said hydrothermal reaction condition is heated up in closed container by the aqueous solution comprising soluble nickel salt and hexamethylenetetramine or urea and carry out hydro-thermal reaction at autogenous pressures, wherein said original appearance reduction reaction conditions for heating up nickel hydroxide nano sheet and alkaline polyol solution and carrying out alcohothermal reaction at autogenous pressures in closed container, wherein said polyalcohol is selected from ethylene glycol, propane diols, BDO, hexylene glycol.
4. surface has an electrode material for super thin metal nickel nano film array, and it comprises:
Porous, electrically conductive substrate;
Perpendicular to the super thin metal nickel nano film array of this substrate grown in described porous, electrically conductive substrate;
Wherein said super thin metal nickel nano film is of a size of: thickness 2-5 nanometer, length 100-300 nanometer, width 50-300 nanometer.
5. surface has an electrode material for metal nickel nano sheet assembly, and it comprises:
Porous, electrically conductive substrate;
Perpendicular to the metal nickel nano sheet assembly of this substrate grown in described porous, electrically conductive substrate, described assembly intersects by metal nickel nano sheet the spherical nickel nano flower array assembled; The diameter of wherein said metal nickel nano sheet assembly is 30-70 nanometer.
6. the electrode material according to claim 4 or 5, wherein said porous, electrically conductive substrate is nickel foam or foam copper.
7. surface as claimed in claim 4 has a preparation method for the electrode material of ultra-thin nickel nano film array, and it comprises the following steps:
A. the aqueous solution of soluble nickel salt and hexamethylenetetramine or urea will be comprised, join in reactor, again reactor is put in the porous, electrically conductive substrate of surface after acid treatment, then this reactor airtight, heat up and carry out hydro-thermal reaction at autogenous pressures, with this substrate grown nickel hydroxide nano chip arrays vertical on this porous, electrically conductive substrate surface;
B. the porous, electrically conductive substrate of nickel hydroxide nano chip arrays is had to take out by long for surface, dry after washing;
C. in the second reactor, add the ethylene glycol solution of NaOH, again this reactor is put in the porous, electrically conductive substrate obtained through step b, sealed reactor, heat up and carry out alcohothermal reaction at autogenous pressures, making nickel hydroxide nano sheet original appearance described in each be reduced into ultra-thin nickel nano film array; Washing also, after vacuum drying, obtains the electrode material that described surface has ultra-thin nickel nano film array, and saves backup under the condition of starvation.
8. preparation method according to claim 7, wherein said soluble nickel salt is selected from nickel nitrate, nickelous sulfate or nickel chloride; In wherein said hydro-thermal reaction, in the described aqueous solution, soluble nickel salinity is 0.1-0.5 mol/L, and hexamethylenetetramine concentration is 0.2-1.0 mol/L, and the condition of described first hydro-thermal reaction is: temperature is 90-120 DEG C, and the reaction time is 8-20 hour; In alcohothermal reaction, the concentration of NaOH in ethylene glycol is 0.3-1.0 mol/L, and the condition of described alcohothermal reaction is: temperature is 140-180 DEG C, and the reaction time is 8-24 hour.
9. surface as claimed in claim 5 has a preparation method for the electrode material of ultra-thin nickel nano film assembly, and it comprises the following steps:
A. the aqueous solution comprising soluble nickel salt and hexamethylenetetramine or urea is joined in reactor, again reactor is put in porous, electrically conductive substrate, then this reactor airtight, heat up and carry out hydro-thermal reaction at autogenous pressures, with this substrate grown nickel hydroxide nano chip arrays vertical on this porous, electrically conductive substrate surface;
B. the porous, electrically conductive substrate of nickel hydroxide nano chip arrays is had to take out by long for surface, dry after washing;
C. in the second reactor, add the ethylene glycol solution of NaOH and sodium borohydride, again this reactor is put in the porous, electrically conductive substrate obtained through step b, sealed reactor, heat up and carry out alcohothermal reaction at autogenous pressures, make nickel hydroxide nano sheet original appearance described in each be reduced into ultra-thin nickel nano film and form described ultrathin nanometer sheet assembly; Washing also, after vacuum drying, obtains the electrode material that described surface has ultra-thin nickel nano film assembly, and saves backup under the condition of starvation.
10. preparation method according to claim 9, wherein said soluble nickel salt is selected from nickel nitrate, nickelous sulfate or nickel chloride; In wherein said hydro-thermal reaction, in the described aqueous solution, soluble nickel salinity is 0.1-0.5 mol/L, and hexamethylenetetramine concentration is 0.2-1.0 mol/L, and the condition of described first hydro-thermal reaction is: temperature is 90-120 DEG C, and the reaction time is 8-20 hour; In alcohothermal reaction, the concentration of NaOH in ethylene glycol is 0.3-1 mol/L, and the concentration of sodium borohydride in ethylene glycol is 0.1-0.5 mol/L, and the condition of described alcohothermal reaction is: temperature is 140-180 DEG C, and the reaction time is 8-24 hour.
11. super thin metal nickel nano films according to claim 1, surface according to claim 4 have the electrode material that the electrode material of ultra-thin nickel nano film array or surface according to claim 5 have a ultra-thin nickel nano film assembly and are used as the positive electrode of hydrazine hydrate oxidized fuel cell or are used as the purposes of brine electrolysis cathode material for hydrogen evolution.
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