CN109913894A - A kind of corrosion resistance hydrogen-precipitating electrode and preparation method thereof - Google Patents
A kind of corrosion resistance hydrogen-precipitating electrode and preparation method thereof Download PDFInfo
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- 238000005260 corrosion Methods 0.000 title claims abstract description 47
- 230000007797 corrosion Effects 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 239000001257 hydrogen Substances 0.000 claims abstract description 57
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 57
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 33
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000011777 magnesium Substances 0.000 claims abstract description 26
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 24
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 21
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 21
- 239000004411 aluminium Substances 0.000 claims abstract description 20
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000007772 electrode material Substances 0.000 claims abstract description 19
- 239000003792 electrolyte Substances 0.000 claims abstract description 15
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims description 36
- 239000000843 powder Substances 0.000 claims description 14
- 238000005245 sintering Methods 0.000 claims description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 238000001125 extrusion Methods 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 9
- 238000004502 linear sweep voltammetry Methods 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims description 2
- 238000009704 powder extrusion Methods 0.000 claims description 2
- 230000008878 coupling Effects 0.000 abstract description 2
- 238000010168 coupling process Methods 0.000 abstract description 2
- 238000005859 coupling reaction Methods 0.000 abstract description 2
- 238000009826 distribution Methods 0.000 abstract description 2
- 230000037427 ion transport Effects 0.000 abstract description 2
- 229910045601 alloy Inorganic materials 0.000 description 9
- 239000000956 alloy Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 5
- 230000005611 electricity Effects 0.000 description 5
- 238000005868 electrolysis reaction Methods 0.000 description 5
- 229910000861 Mg alloy Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical class [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 235000012254 magnesium hydroxide Nutrition 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910001051 Magnalium Inorganic materials 0.000 description 1
- 229910003271 Ni-Fe Inorganic materials 0.000 description 1
- 229910003296 Ni-Mo Inorganic materials 0.000 description 1
- 229910018605 Ni—Zn Inorganic materials 0.000 description 1
- 229910018503 SF6 Inorganic materials 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000004210 cathodic protection Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000006260 foam Substances 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
- 238000007327 hydrogenolysis reaction Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- -1 oxonium ion Chemical class 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- SFZCNBIFKDRMGX-UHFFFAOYSA-N sulfur hexafluoride Chemical compound FS(F)(F)(F)(F)F SFZCNBIFKDRMGX-UHFFFAOYSA-N 0.000 description 1
- 229960000909 sulfur hexafluoride Drugs 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 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
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Landscapes
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a kind of corrosion resistance hydrogen-precipitating electrode and preparation method thereof, which uses corrosion resistance hydrogen evolution electrode material, which includes following element: magnesium and aluminium；Wherein, the weight ratio of magnesium and aluminium is (1~9): (9~1).Electrode of the invention can be avoided to be corroded during liberation of hydrogen, improve the service life of electrode, using the electrode liberation of hydrogen, apply ultrasonic wave and the magnetic field NS simultaneously, the average liberation of hydrogen rate of electrode can be effectively improved, magnetic field can be such that nickel electrode magnetizes, and nickel electrode is promoted to discharge electronics, ultrasound-magnetic coupling can promote ion transport, and the electrolyte in electrolytic cell can be promoted to recycle, make electrolyte intermediate ion uniform concentration distribution.
Description
Technical field
The present invention relates to a kind of hydrogen-precipitating electrodes, and in particular to a kind of corrosion resistance hydrogen-precipitating electrode and preparation method thereof.
Background technique
Hydrogen Energy is a kind of new energy of current universally acknowledged most worth exploitation, and combustion heat value is high, every 1000 grams of hydrogen burnings
Heat afterwards is about three times of gasoline, and 3.9 times of alcohol, 4.5 times of coke.Hydrogen can be obtained by water, and water is then the earth
Resource abundant is gone up, the product after hydrogen burning only has water, will not pollute to environment.And hydrogen energy source has safety, unit
The characteristic of weight energy height and no pollution is that current various countries make great efforts to develop as one of following most important alternative energy source.
Electrolysis water liberation of hydrogen is one of current generation common method of hydrogen, and electrolysis water liberation of hydrogen is with certain voltage or electricity
Stream is by soaking hydrogen and oxonium ion in a pair of electrodes electrolytic solution in the electrolytic solution, respectively in the extremely middle generation hydrogen of Yin and Yang and oxygen
Gas.
Traditional hydrogen-precipitating electrode has the precious metals such as platinum, palladium, with very high catalytic activity and stability, can effectively drop
Low overpotential of hydrogen evolution, but its reserves is rare, involves great expense, it is at high cost.Nickel foam as electrode, overpotential of hydrogen evolution also compared with
It is low, but its stability is not high, and the service life is short.The existing Ni-based bianry alloy as hydrogen-precipitating electrode has: Ni-Mo, Ni-Zn, Ni-
Co, Ni-W, Ni-Fe etc..
The chemical property of magnesium metal wave living, can be quickly oxidized in air, vigorous reaction be reached with water energy, in many Jie
Violent reaction can occur in matter causes it to be corroded.The intensity of pure magnesium is very low, is generally prepared into conjunction with other element combinations
Gold uses.
Currently, magnesium alloy is mainly used in Automobile Transportation, aerospace, medical instrument and some electronic equipments, tool
There are low-density, high-damping, good shock resistance and casting character.It is Mg-9Al-1Zn such as AZ91D magnesium alloy, due to addition
Al and Zn element has good mechanics and casting character.Magnesium also has application, such as magnesium cell in field of batteries, and AZ31 magnesium closes
Jin Yin has preferable deformability, by the negative electrode material as magnesium cell.
But magnesium alloy is more perishable, such as AZ31 magnesium alloy, corrosion rate is larger in water solution system, in battery
During electric discharge, electrode surface can adhere to a large amount of discharging product magnesium hydroxides, and the attachment of magnesium hydroxide and corrosion product causes
The internal resistance of cell increases.
Summary of the invention
The object of the present invention is to provide a kind of corrosion resistance hydrogen-precipitating electrodes and preparation method thereof, which solves existing analysis
The perishable problem of hydrogen electrode, can be avoided and be corroded during liberation of hydrogen, improve the service life of electrode.
In order to achieve the above object, it the present invention provides a kind of corrosion resistance hydrogen evolution electrode material, is wrapped in the electrode material
Containing following element: magnesium and aluminium；Wherein, the weight ratio of magnesium and aluminium is (1~9): (9~1).
Preferably, the electrode material by weight ratio be (1~9): the magnesium powder and aluminium powder extrusion molding of (9~1) and also
Sintering obtains under originality gaseous environment.
Preferably, the weight ratio of magnesium and aluminium is 1:3 in the electrode material.
The present invention also provides a kind of corrosion resistance hydrogen-precipitating electrode, which uses the corrosion resistance hydrogen-precipitating electrode material
Material preparation.
Preferably, the electrode is using the non-working surface in epoxy resin sealing corrosion resistance hydrogen evolution electrode material.
The present invention also provides a kind of liberation of hydrogen systems, which includes: electrolyte, and the anode and cathode of electrical connection；Its
In, the cathode uses the corrosion resistance hydrogen-precipitating electrode as described in claim 4 or 5.
Preferably, the electrolyte uses KOH aqueous solution；The anode uses pure nickel.
Preferably, the mass fraction of the KOH aqueous solution is 10~30%.
Preferably, several pairs of anode and cathodes in parallel in the system.
The present invention also provides a kind of preparation methods of corrosion resistance hydrogen evolution electrode material, and this method includes:
(1) be (1~9) by weight ratio: the magnesium powder and aluminium powder of (9~1) mix, at room temperature extrusion molding, forming pressure
For 200~300MPa, the too small alloy being sintered out of the forming pressure is not fine and close enough, influences intensity, and forming pressure increases to centainly
The intensity of alloy is improved less after degree, causes higher cost；
(2) sample of extrusion molding in step (1) is sintered under reducibility gas environment, sintering temperature is 500~600
DEG C, obtain electron pole material；The sintering temperature that the present invention selects is lower than smelting temperature no more than 600 DEG C, consolidate
Phase sintering, and have reducing gas protection in sintering process, therefore can effectively avoid burning and oxidative phenomena, while sintering temperature control
It makes at 600 DEG C hereinafter, avoiding the occurrence of the case where causing burning that alloy strength is caused to reduce, while the control of temperature sintering temperature exists
500 DEG C or more, avoid the occurrence of the case where too low caused voidage of temperature is excessively high and alloy strength reduces.
Preferably, in step (1), when extrusion molding, 25~35s of pressure maintaining, the dwell time is too short to be unfavorable in powder
Gas evolution, causes alloy void rate excessively high, due to the simple shape of forming, the dwell time is too long can reduce efficiency improve at
This.
Preferably, in step (1), the purity of the magnesium powder and aluminium powder is 99%.
Preferably, in step (2), the reducibility gas includes: hydrogen.
Preferably, in step (2), the sintered heat insulating 3 hours, the too short intensity and modeling that will affect alloy of soaking time
Property, soaking time is too long to be caused to recrystallize, and crystal grain is caused to be grown up, and reduce intensity.
The present invention also provides a kind of liberation of hydrogen methods, and this method includes:
It using the corrosion resistance hydrogen-precipitating electrode as cathode, is placed in electrolyte, using pure nickel as anode, keeps two electricity
Interpolar vertical range is 3~5cm, is forced into 3~5V using linear sweep voltammetry, is electrolysed under 3~5V voltage, had been electrolysed
Applying frequency to solution in journey is 24~30Hz, and power is the ultrasonic wave of 225~240W, while applying the magnetic field NS of 3~4T.
Liberation of hydrogen method of the invention, keeping vertical range between two electrodes is 3~5cm, and electrode spacing is too small to be easy to cause pole
Reaction product blocking between plate is unfavorable for the lasting progress of reaction, and electrode spacing is too small to will increase interelectrode resistance, is unfavorable for
The progress of reaction.
Liberation of hydrogen method of the invention, may advantageously facilitate the gas diffusion of electrode surface using ultrasonic wave, to be effectively reduced
Electrode electricity resistance, while applying the magnetic field NS of 3~4T, magnetic field may advantageously facilitate transmission speed of the electronics between pole plate, improve electricity
Solve efficiency.
Preferably, the linear sweep voltammetry is with 0.05V/s sweep speed.
Preferably, the linear sweep voltammetry is scanned by 1V to 3~5V.
Preferably, electrolysis time is 30min~8h under 3~5V voltage.
Preferably, the electrolyte uses KOH aqueous solution or NaOH aqueous solution.
Preferably, the mass fraction of the KOH aqueous solution or NaOH aqueous solution is 10~30%.
Preferably, in this method, several pairs of anode and cathodes in parallel such as can 3 pairs of anode and cathodes in parallel.
Preferably, in this method, the working face of the anode and cathode is 12mm × 12mm.
Corrosion resistance hydrogen-precipitating electrode of the invention and preparation method thereof solves the problems, such as that existing hydrogen-precipitating electrode is perishable,
It has the advantage that
(1) electrode of the invention is almag, and almag can play the role of good cathodic protection, therefore have
Preferable etch resistant properties can be avoided and be corroded during liberation of hydrogen, improve the service life of electrode；
(2) preparation method of electrode material of the invention has low-energy-consumption, high material using powder metallurgically manufacturing
Utilization rate, and the advantages that reduction manufacturing step；
(3) preparation method of electrode material of the invention uses metal magnesium powder, and magnesium is high active material, and tradition is molten
Have in sweetening process and protected using sulfur hexafluoride gas, but burning and the generation of oxidative phenomena can not be avoided completely, and
Method safety of the invention is reliable, and has preferable corrosion resistance in the electron pole electrolytic process prepared, uses the longevity
Life length；
(4) liberation of hydrogen method of the invention, while applying ultrasonic wave and the magnetic field NS, the average liberation of hydrogen speed of electrode can be effectively improved
Rate, magnetic field can be such that nickel electrode magnetizes, and nickel electrode is promoted to discharge electronics, and ultrasound-magnetic coupling can promote ion transport, can promote to be electrolysed
Electrolyte in pond recycles, makes electrolyte intermediate ion uniform concentration distribution.
Detailed description of the invention
The micro-organization chart of almag electrode prepared by Fig. 1 embodiment of the present invention 4.
Specific embodiment
The technical scheme in the embodiments of the invention will be clearly and completely described below, it is clear that described implementation
Example is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is common
Technical staff's every other embodiment obtained without making creative work belongs to the model that the present invention protects
It encloses.
Embodiment 1
A kind of preparation method of corrosion resistance hydrogen-precipitating electrode includes:
(1) commercial 99% pure magnesium and commercial 99% pure aluminium powder are mixed, two kinds of powder weight ratios are 9:1, agitated mixed
It closes uniform；
(2) mixed-powder for obtaining step (1) extrusion molding at room temperature, forming pressure 200MPa, pressure maintaining 25s；
(3) sample of extrusion molding in step (2) is sintered, is passed through hydrogen into quartzy tube furnace during the sintering process
Gas, to protect the bulk alloy after extrusion molding not oxidized, sintering temperature is 500 DEG C, and heat preservation was naturally cooling to room after 3 hours
Temperature obtains electron pole material, to alloy non-working surface using epoxy resin seal, reservations working face for 12mm ×
12mm, with 600~1000#Water-proof abrasive paper polish step by step after wash with distilled water, then after acetone oil removing again wash with distilled water,
Obtain electron pole.
A kind of liberation of hydrogen method, this method using the corrosion resistance hydrogen-precipitating electrode of above-mentioned preparation as cathode, it includes:
(S1) using KOH solution as electrolyte, KOH mass fraction is 30%, is stirred electrolyte using magnetite blender
It mixes uniformly, and cooled to room temperature；
(S2) corrosion resistance hydrogen-precipitating electrode is put into the KOH solution of step (S1) as cathode, using pure nickel as anode,
The electrode that a pair of of electrolysis area is 12mm × 12mm is selected, keeping vertical range between two electrodes is 3cm, using linear sweep voltammetry
Method pressurization, decomposition voltage are scanned to 5V by 1V with 0.05V/s sweep speed, retention time 8h are electrolysed under 5V voltage, is being electrolysed
Applying frequency to solution in the process is 24Hz, and power is the ultrasonic wave of 225W, while applying the magnetic field NS of 3T.
Electron pole prepared by the present embodiment 1, conductivity are 11%IACS (international
Annealing copper standard, International Annealed Copper Standard), rate of corrosion 0%, corresponding electric current is close under 5V voltage
Degree is 1.1A/cm2, and the corresponding 5V current density of pure Mg and pure Al is respectively 0.88A/cm2And 1.5A/cm2。
Embodiment 2
A kind of preparation method of corrosion resistance hydrogen-precipitating electrode, difference essentially identical with the preparation method of electrode in embodiment 1
Be: in step (1), 99% pure magnesium and 99% pure aluminium powder ratio are 3:1；In step (2), forming pressure is
300MPa, dwell time 35s.
Electron pole prepared by the present embodiment 2, conductivity 7%IACS, rate of corrosion 0%, under 5V voltage
Corresponding current density is 0.9A/cm2, and the corresponding 5V current density of pure Mg and pure Al is respectively 0.88A/cm2And 1.5A/
cm2。
Embodiment 3
A kind of preparation method of corrosion resistance hydrogen-precipitating electrode, difference essentially identical with the preparation method of electrode in embodiment 1
Be: in step (1), 99% pure magnesium and 99% pure aluminium powder ratio are 1:1；In step (3), sintering temperature is 600 DEG C.
Electron pole prepared by the present embodiment 3, conductivity 4%IACS, rate of corrosion 0%, under 5V voltage
Corresponding current density is 1.7A/cm2, and the corresponding 5V current density of pure Mg and pure Al is respectively 0.88A/cm2And 1.5A/
cm2。
Embodiment 4
A kind of preparation method of corrosion resistance hydrogen-precipitating electrode, difference essentially identical with the preparation method of electrode in embodiment 1
Be: in step (1), 99% pure magnesium and 99% pure aluminium powder ratio are 1:3.The almag electrode of the embodiment 4 preparation
Microscopic structure it is as shown in Figure 1.
A kind of liberation of hydrogen method, essentially identical with the liberation of hydrogen method of embodiment 1, difference is: in step (5), two electrodes
Spacing is 4cm.
Electron pole prepared by the present embodiment 4, conductivity 8%IACS, rate of corrosion 0%, under 5V voltage
Corresponding current density is 1.3A/cm2, and the corresponding 5V current density of pure Mg and pure Al is respectively 0.88A/cm2And 1.5A/
cm2。
Embodiment 5
A kind of preparation method of corrosion resistance hydrogen-precipitating electrode, difference essentially identical with the preparation method of electrode in embodiment 1
Be: in step (1), 99% pure magnesium and 99% pure aluminium powder ratio are 1:9.
A kind of liberation of hydrogen method, essentially identical with the liberation of hydrogen method of embodiment 1, difference is: in step (5), application
Ultrasonic frequency is 30Hz, power 240W.
Electron pole prepared by the present embodiment 5, conductivity 14%IACS, the damage of electrode material in electrolytic experiment
Consumption and the ratio of electrode weight before electrolytic experiment are rate of corrosion, rate of corrosion 45%, the corresponding current density under 5V voltage
For 1.35A/cm2, and the corresponding 5V current density of pure Mg and pure Al is respectively 0.88A/cm2And 1.5A/cm2。
Embodiment 6
A kind of preparation method of corrosion resistance hydrogen-precipitating electrode, difference essentially identical with the preparation method of electrode in embodiment 1
Be: in step (1), 99% pure magnesium and 99% pure aluminium powder ratio are 1:3.
The electrode corrosion rate of electron pole prepared by the present embodiment 6 is 0%.
A kind of liberation of hydrogen method, essentially identical with the liberation of hydrogen method of embodiment 1, difference is: in step (5), between electrode
Distance is 5cm, and it is 30min that the retention time is electrolysed under 5V voltage.
It is compared with existing platinum electrode as cathode, the average liberation of hydrogen rate of platinum electrode is only 1.696mL/ (min
cm2), and the liberation of hydrogen method of embodiment 6, average liberation of hydrogen rate are 1.71mL/ (mincm2)。
Embodiment 7
A kind of preparation method of corrosion resistance hydrogen-precipitating electrode, difference essentially identical with the preparation method of electrode in embodiment 1
Be: in step (1), 99% pure magnesium and 99% pure aluminium powder ratio are 3:1.
The electrode corrosion rate of electron pole prepared by the present embodiment 7 is 0%.
A kind of liberation of hydrogen method, essentially identical with the liberation of hydrogen method of embodiment 1, difference is: in step (4), KOH mass
Score is 10%；In step (5), apply the magnetic field NS of 4T.
Embodiment 8
A kind of preparation method of corrosion resistance hydrogen-precipitating electrode, difference essentially identical with the preparation method of electrode in embodiment 1
Be: in step (1), the mixed proportion of pure magnesium and pure aluminium powder is 1:3.
The electrode corrosion rate of electron pole prepared by the present embodiment 8 is 0%.
A kind of liberation of hydrogen method, essentially identical with the liberation of hydrogen method of embodiment 1, difference is: in step (5), between electrode
Away from for 5cm, KOH concentration of electrolyte is 20wt%, and decomposition voltage 3V, electrolysis time is 30 minutes, 3 pairs of anode and cathodes in parallel
The ultrasonic frequency of electrode slice, application is 30Hz, power 240W, applies the magnetic field NS of 4T.
The liberation of hydrogen method of the present embodiment 8, average liberation of hydrogen rate reach 2.65mL/ (mincm2), opposite embodiment 6 mentions
It is high by about 55%.
Decomposition voltage (liberation of hydrogen voltage) Ji Guo electricity of the electrode and common hydrogen-precipitating electrode that are prepared in the embodiment of the present invention 1~8
Pressure is referring to table 1, it is seen that decomposition voltage when embodiment 5 and 8 is electrolysed in the present invention is lower, illustrates electrolytic efficiency height, passes through corrosion resistant
Corrosion and decomposition voltage comprehensive analysis are it is found that magnalium ratio is most suitable for doing electrode for 1:3 is corresponding.
Table 1
It is discussed in detail although the contents of the present invention have passed through above preferred embodiment, but it should be appreciated that above-mentioned
Description is not considered as limitation of the present invention.After those skilled in the art have read above content, for of the invention
A variety of modifications and substitutions all will be apparent.Therefore, protection scope of the present invention should be limited to the appended claims.
Claims (10)
1. a kind of corrosion resistance hydrogen evolution electrode material, which is characterized in that include following element: magnesium and aluminium in the electrode material；Its
In, the weight ratio of magnesium and aluminium is (1~9): (9~1).
2. corrosion resistance hydrogen evolution electrode material according to claim 1, which is characterized in that the electrode material passes through weight ratio
For (1~9): the magnesium powder and aluminium powder extrusion molding of (9~1) and being sintered under reducibility gas environment obtains.
3. a kind of corrosion resistance hydrogen-precipitating electrode, which is characterized in that the electrode is used as described in any one of claims 1 to 3
Corrosion resistance hydrogen evolution electrode material preparation.
4. a kind of liberation of hydrogen system, which is characterized in that the system includes: electrolyte, and the anode and cathode of electrical connection；Wherein, institute
Cathode is stated using corrosion resistance hydrogen-precipitating electrode as claimed in claim 3.
5. liberation of hydrogen system according to claim 4, which is characterized in that the electrolyte uses KOH aqueous solution；The anode
Using pure nickel.
6. a kind of preparation method of corrosion resistance hydrogen evolution electrode material, which is characterized in that this method includes:
(1) be (1~9) by weight ratio: the magnesium powder and aluminium powder of (9~1) mix, at room temperature extrusion molding, forming pressure 200
~300MPa；
(2) sample of extrusion molding in step (1) being sintered under reducibility gas environment, sintering temperature is 500~600 DEG C,
Obtain electron pole material.
7. the preparation method of corrosion resistance hydrogen evolution electrode material according to claim 6, which is characterized in that in step (1)
In, when extrusion molding, 25~35s of pressure maintaining.
8. the preparation method of corrosion resistance hydrogen evolution electrode material according to claim 6, which is characterized in that in step (2)
In, the sintered heat insulating 3 hours.
9. a kind of liberation of hydrogen method, which is characterized in that this method includes:
Using corrosion resistance hydrogen-precipitating electrode as claimed in claim 3 as cathode, it is placed in electrolyte, using pure nickel as anode,
Keeping vertical range between two electrodes is 3~5cm, is forced into 3~5V using linear sweep voltammetry, is electrolysed under 3~5V voltage,
Applying frequency to solution in electrolytic process is 24~30Hz, and power is the ultrasonic wave of 225~240W, while applying 3~4T's
The magnetic field NS.
10. liberation of hydrogen method according to claim 9, which is characterized in that the linear sweep voltammetry is scanned with 0.05V/s
Rate；The electrolyte uses KOH aqueous solution or NaOH aqueous solution.
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