CN108660474A - (FeaCobNic)xMyRzSystem's analysis oxygen catalysis material and the application on Oxygen anodic evolution electrode - Google Patents
(FeaCobNic)xMyRzSystem's analysis oxygen catalysis material and the application on Oxygen anodic evolution electrode Download PDFInfo
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- CN108660474A CN108660474A CN201810559308.8A CN201810559308A CN108660474A CN 108660474 A CN108660474 A CN 108660474A CN 201810559308 A CN201810559308 A CN 201810559308A CN 108660474 A CN108660474 A CN 108660474A
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- C25B1/00—Electrolytic production of inorganic compounds or non-metals
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- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C1/11—Making amorphous alloys
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C30/02—Alloys containing less than 50% by weight of each constituent containing copper
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- C22C45/008—Amorphous alloys with Fe, Co or Ni as the major constituent
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
The invention discloses one kind (FeaCobNic)xMyRzSystem's analysis oxygen catalysis material and the application on Oxygen anodic evolution electrode, (FeaCobNic)xMyRzThe atomic percent dosage of system's analysis oxygen catalysis material is a+b+c=1,0.5≤a≤0.94,0.01≤b≤0.9,0.5≤c≤0.94,50≤x≤95,5≤y≤35,0.5≤z≤15；Wherein M is the one or more in B, Si, C, P, the one or more in R Nb, Cr, Mn, Ru, Mo, Zr, Cu, Y, La.(FeaCobNic)xMyRzSystem's analysis oxygen catalysis material uses electric arc melting and induction melting band and obtains thickness as 0.05~500 μm of alloy thin band.By (FeaCobNic)xMyRzIt is applied in electrolysis water directly as working electrode, is reaching 10mAcm‑2In the case of current density, overpotential is 220mV~360mV.
Description
Technical field
The present invention relates to the electrode catalytic materials in a kind of water electrolysis hydrogen production, refer to one kind more particularly
(FeaCobNic)xMyRzIt is the preparation method of non-crystaline amorphous metal or amorphous and nanocrystalline composite material and is applied in electrolysis elutriation
On oxygen catalysis electrode, to obtain high catalytic activity.
Background technology
Water electrolysis hydrogen producing is a kind of method of conveniently hydrogen making.It is passed through in the electrolytic cell full of electrolyte straight
Electrochemical reaction occurs on the electrode for galvanic electricity, hydrone, resolves into hydrogen and oxygen.
In the today's society of energy shortage, Hydrogen Energy is a kind of green energy resource for great potential that the mankind generally acknowledge, is that can solve
The certainly ideal secondary energy sources of shortage of resources and environmental pollution.Nowadays, the preparation of hydrogen is essentially from fossil fuel, water and life
Object.In numerous hydrogen production process, water electrolysis hydrogen production is considered as the hydrogen producing technology of the following most possible large-scale application, has and prepares
Simple for process, high degree of automation, product purity is higher, the remarkable advantages such as safety and environmental protection.Electrolysis water is to provide power by electric energy,
By the chemical process that water decomposition is hydrogen and oxygen.Currently, practical and research and development water electrolysis hydrogen production methods have：Alkaline electrolysis is consolidated
The hydrolysis of body polymer electrolyte, high temperature electrolysis of steam etc..But during electrolysis water, electrode surface, especially Oxygen anodic evolution electricity
Polarization can occur for pole surface electrode reaction is caused to deviate equilibrium electrod potential so as to cause overpotential to be to cause electrolysis water
The main reason for energy consumption is big, efficiency is low.Its fancy price of traditional precious metal catalytic material limits the industry hair of electrolysis water
Exhibition, thus non-noble metallic materials are of increased attention, transition metal oxide, hydroxide, phosphide, sulfide
Etc. having obtained extensive research, however the catalytic activity of these materials is still up for improving.Therefore, research is urged with high oxygen separated
Change active anode material, solve the problems, such as that overpotential for oxygen evolution is excessively high, for improving the energy efficiency of water electrolysis hydrogen production, reduces system
Hydrogen cost, and then extensive transformation of the fossil fuel to clean energy resource is promoted to have important practical significance.
Invention content
An object of the present invention is to provide a kind of novel analysis oxygen catalytically-active materials.
The second object of the present invention is to propose a kind of method preparing novel analysis oxygen catalytically-active materials.
The third object of the present invention is to provide a kind of anode applied in water electrolysis hydrogen production.
One kind (Fe of the present inventionaCobNic)xMyRzSystem's analysis oxygen catalysis material, (FeaCobNic)xMyRzSystem's analysis oxygen is catalyzed material
Atomic percent dosage in material is a+b+c=1,0.5≤a≤0.94,0.01≤b≤0.9,0.5≤c≤0.94,50≤x≤
95,5≤y≤35,0.5≤z≤15；Wherein M be B, Si, C, P in one or more kinds of elements, R Nb, Cr, Mn, Ru,
One or more kinds of elements in Mo, Zr, Cu, Y, La.
(FeaCobNic)xMyRzSystem's analysis oxygen catalyticing anode electrode material is reaching 10mAcm-2In the case of current density,
Overpotential is 220mV~360mV.
In the present invention, one kind (Fe is preparedaCobNic)xMyRzThe method of system's analysis oxygen catalysis material, it is characterised in that including
There are the following steps：
Step 1：According to target ingredient composition；
According to (FeaCobNic)xMyRzTarget component weighs Fe, Co, Ni, M, R each element, when wherein M is B, C, P element,
FeM alloy replacings, the mass percent purity of each element can be used to be not less than 99.0%；
Step 2：Master alloy melting；
Load weighted Fe, Co, Ni, M, R each element in step 1 is uniformly mixed, and is carried out in vacuum arc melting furnace
Melting obtains (FeaCobNic)xMyRzSubject alloy ingot；
Smelting parameter：Melting protective atmosphere is the argon gas that mass percent is 99.999%；
Vacuum degree is 1 × 10-4~8 × 10-3Pa；
Melting electric current is 30~200A；
Smelting time：Every time 1~20min of melting, melting 1~10 time；
Step 3：Melt spinning method method prepares subject alloy band；
By the master alloy Mechanical Crushing obtained in step 2 at being preset in quartz ampoule after fritter, and integrally it is put into fast rapid hardening
It is fixedly mounted in the vacuum induction melting furnace set, is ejected on high-speed rotating copper wheel after it is melted completely, to which thickness be prepared
(the Fe that degree is 0.05~500 μmaCobNic)xMyRzAlloy thin band；
Parameter setting：Melting protective atmosphere is the argon gas that mass percent is 99.0%；
Vacuum degree is：6×10-2~2 × 10-1Pa；
Coil-induced electric current is 2~20A；
Smelting time：10~180s；
Injection pressure：0.01~0.1MPa；
Copper wheel velocity of rotation：1000~4000m/s.
The alloy thin band that thickness is 0.05~500 μm can be made.
In the present invention, (Fe is preparedaCobNic)xMyRzThe method of the Oxygen anodic evolution electrode of system's analysis oxygen catalysis material, it is special
Sign is：First use conducting resinl by copper conductor and (FeaCobNic)xMyRzAlloy strip is fixedly connected, by non-test part with not
Electroconductive resin seals, and exposes (FeaCobNic)xMyRzThe scope of freedom of alloy strip, obtains (FeaCobNic)xMyRzAnalyse oxygen catalysis
Anode electrode；Then by (FeaCobNic)xMyRzAnalyse 3~10 cycles that oxygen catalyticing anode electrode carries out lye and aerobic environment
Processing, obtains directly available Oxygen anodic evolution electrode.Anode electrode obtained is applied in electrolysis water.
The lye is sodium hydroxide, potassium hydroxide, calcium hydroxide, lithium hydroxide, a hydration ammonia, sodium carbonate, bicarbonate
It is one or more in sodium, a concentration of 0.1~3mol/L；
The temperature impregnated in lye in the surface treatment is 280~310K；
The time impregnated in lye in the surface treatment is 2min~for 24 hours；
The temperature placed under aerobic environment in the surface treatment is 280~310K；
The oxygen content placed under aerobic environment in the surface treatment is 21~40%；
The time placed under aerobic environment in the surface treatment be 2~for 24 hours.
(the Fe being prepared in the present inventionaCobNic)xMyRzThe Oxygen anodic evolution electrode of system's analysis oxygen catalysis material, is reaching
10mA·cm-2In the case of current density, overpotential is 220mV~360mV.
Advantage is the present invention compared with prior art：
1. (Fe prepared by the present inventionaCobNic)xMyRzThe composition range of system's analysis oxygen catalysis material is wide, in a certain range may be used
It adjusts, element group becomes：(FeaCobNic)xMyRz, wherein M be B, Si, C, P in one or more, R Nb, Cr, Mn,
One or more kinds of combinations in Ru, Mo, Zr, Cu, Y, La, atomic percent dosage are a+b+c=1,0.5≤a≤
0.94,0.01≤b≤0.9,0.5≤c≤0.94,50≤x≤95,5≤y≤35,0.5≤z≤15.
2. (Fe prepared by the present inventionaCobNic)xMyRzSystem's analysis oxygen catalysis material is continuous, toughness and excellent surface quality
The alloy thin band that thickness is 0.05~500 μm.
3. (Fe prepared by the present inventionaCobNic)xMyRzSystem's analysis oxygen material is non-crystaline amorphous metal or amorphous and nanocomposite material
Material, wherein the contact area and then exposure when nanocrystalline presence can increase material as anode between electrolyte are more urged
Change active site, promotes electrolysis water liberation of hydrogen efficiency.
4. (Fe prepared by the present inventionaCobNic)xMyRzSystem's analysis oxygen catalysis material analyses oxygen due to have passed through surface treatment
Overpotential has significant reduction, catalytic activity to get a promotion.
5. (Fe prepared by the present inventionaCobNic)xMyRzSystem's analysis oxygen catalysis material be non-crystaline amorphous metal or amorphous with it is nanocrystalline multiple
Condensation material belongs to a kind of novel analysis oxygen catalytically-active materials, and oxygen mistake is analysed applied to can effectively be reduced in electrolysis elutriation oxygen electrode
Current potential shows excellent catalytic activity, significantly improves the energy efficiency of water electrolysis hydrogen production.
6. (the Fe being prepared through the method for the present inventionaCobNic)xMyRzThe alloy strip of system's analysis oxygen catalysis material, Neng Gouzhi
It connects as in application of electrode to electrolysis water, and then shortens technological process, convenience is provided for large-scale production.
7. the preparation method that the present invention uses is simple, operability is strong, and universality is strong, is suitable for large-scale production, is being permitted
More Industrial Catalysis or other scientific domains have huge application value.
Description of the drawings
Fig. 1 is through (Fe made from the method for the present inventionaCobNic)xMyRzAnalyse the X ray diffracting spectrum of oxygen electrode.
Fig. 2 is that Fe is made in embodiment 140Co8Ni40B10Ru2It is bent that analysis oxygen catalysis electrode carries out the polarization that electro-chemical test obtains
Line.
Fig. 3 is that Fe is made in embodiment 140Co8Ni40B10Ru2Analysis oxygen catalysis electrode carries out electro-chemical test and obtains constant current survey
Try curve.
Fig. 4 is for Fe in example 235Co12Ni35Si14Nb4Analysis oxygen electrode carries out electro-chemical test and obtains constant current test song
Line.
Fig. 5 is Fe in example 332Co14Ni32Si8P8Nb4Mo2Analysis oxygen electrode carries out electro-chemical test and obtains constant current test
Curve.
Specific implementation mode
Below in conjunction with drawings and examples, the present invention is described in further detail.
One kind (Fe of the present inventionaCobNic)xMyRzSystem's analysis oxygen catalytic electrode material, atomic percent dosage are a+b+c=
1,0.5≤a≤0.94,0.01≤b≤0.9,0.5≤c≤0.94,50≤x≤95,5≤y≤35,0.5≤z≤15；Wherein M
For one or more kinds of elements in B, Si, C, P, one kind in R Nb, Cr, Mn, Ru, Mo, Zr, Cu, Y, La or it is a kind of with
Upper element.
Prepare (the Fe of the present inventionaCobNic)xMyRzSystem's analysis oxygen catalysis material comprises the steps of：
Step 1：According to target ingredient composition；
According to (FeaCobNic)xMyRzTarget component weigh Fe, Co, Ni, M, R each element (wherein M be B, C, P element when,
FeM alloy replacings can be used), the mass percent purity of each element is not less than 99.0%；
Step 2：Master alloy melting；
(when wherein M is B, C, P element, FeM alloys are can be used into load weighted Fe, Co, Ni, M, R each element in step 1
Substitute) it is uniformly mixed, and melting is carried out in vacuum arc melting furnace, obtain (FeaCobNic)xMyRzSubject alloy ingot；
Smelting parameter：Melting protective atmosphere is the argon gas that mass percent is 99.999%；
Vacuum degree is 1 × 10-4~8 × 10-3Pa；
Melting electric current is 30~200A；
Smelting time：Every time 1~20min of melting, melting 1~10 time；
Step 3：Melt spinning method method prepares subject alloy band；
By the master alloy Mechanical Crushing obtained in step 2 at being preset in quartz ampoule after fritter, quartz ampoule outlet at bottom is wide
Degree is 1~10mm, and is integrally put into the vacuum induction melting furnace of quick solidification apparatus, and high speed is ejected into after it is melted completely
On the copper wheel of rotation, to which (the Fe that thickness is 0.05~500 μm be preparedaCobNic)xMyRzAlloy thin band；
Parameter setting：Melting protective atmosphere is the argon gas that mass percent is 99.0%；
Vacuum degree is：6×10-2~2 × 10-1Pa；
Coil-induced electric current is 2~20A；
Smelting time：10~180s；
Injection pressure：0.01~0.1MPa；
Copper wheel velocity of rotation：1000~4000m/s.
In the present invention, it is able to demonstrate that through (Fe made from the method for the present invention by X diffractionaCobNic)xMyRzSystem's analysis oxygen is urged
Change material for amorphous or amorphous and nanocrystalline composite material, as shown in Figure 1.
The catalytic performance of anode electrode is verified
(the Fe for being obtained copper conductor and step 3 using conducting resinlaCobNic)xMyRzAlloy strip is fixedly connected, by non-survey
The non-conductive resin seal in examination part, exposes (FeaCobNic)xMyRzThe scope of freedom of alloy strip, obtains (FeaCobNic)xMyRzAnalyse oxygen catalyticing anode electrode；
The circular treatment of lye and aerobic environment：First by (FeaCobNic)xMyRzIt is raw in lye to analyse oxygen catalyticing anode electrode
At oxide on surface, then oxide on surface is set to stablize in an oxygen-containing environment；The circular treatment 3 of repetition lye and aerobic environment~
10 times, reach (FeaCobNic)xMyRzThe overpotential for oxygen evolution of analysis oxygen catalyticing anode electrode has significant reduction, catalytic activity to obtain
To promotion.Reaching 10mAcm-2In the case of current density, overpotential is 220mV~360mV.
The lye is sodium hydroxide, potassium hydroxide, calcium hydroxide, lithium hydroxide, a hydration ammonia, sodium carbonate, bicarbonate
It is one or more in sodium, a concentration of 0.1~3mol/L；The temperature impregnated in lye in the surface treatment be 280~
310K；The time impregnated in lye in the surface treatment is 2min~for 24 hours；It is transferred in aerobic environment in the surface treatment
The temperature set is 280~310K；The oxygen content placed under aerobic environment in the surface treatment is 21~40%；The surface
The time placed under aerobic environment in processing be 2~for 24 hours.
Embodiment 1
Prepare Fe40Co8Ni40B10Ru2It analyses oxygen and is catalyzed amorphous alloy electrode
Step 1：According to target ingredient composition；
According to atomic percent dosage Fe40Co8Ni40B10Ru2Target component weighs each simple substance element of Fe, Co, Ni, B, Ru,
Wherein B element can be replaced with FeB prealloys, and the mass percent purity of each element is not less than 99.0%；
Step 2：Master alloy melting；
Load weighted Fe, Co, Ni, FeB, Ru each element in step 1 is uniformly mixed, and in vacuum arc melting furnace
Melting is carried out, Fe is obtained40Co8Ni40B10Ru2Subject alloy ingot；
Smelting parameter：Melting protective atmosphere is the argon gas that mass percent is 99.999%；
Vacuum degree is 8.5 × 10-3Pa；
Melting electric current is 150A；
Smelting time：Every time melting 2min, melting 4 times；
Step 3：Melt spinning method method prepares subject alloy band；
By the master alloy Mechanical Crushing obtained in step 2 at being preset in quartz ampoule after fritter, quartz ampoule outlet at bottom is wide
Degree is 3mm, and is integrally put into the vacuum induction melting furnace of quick solidification apparatus, and high speed rotation is ejected into after it is melted completely
Copper wheel on, be 10 μm of Fe to which thickness be prepared40Co8Ni40B10Ru2Alloy thin band；
Parameter setting：Melting protective atmosphere is the argon gas that mass percent is 99.0%；
Vacuum degree is：8×10-2Pa；
Coil-induced electric current is 8A；
Smelting time：15s；
Injection pressure：0.02MPa；
Copper wheel velocity of rotation：3000m/s.
Through alloy thin band made from step 3 through X diffractometries, embodiment 1 is non crystalline structure material, as shown in Figure 1.By
XRD spectrum shown in FIG. 1 can be seen that the subject alloy band prepared using the above method and is shown as through X-ray diffraction detection
The diffusing scattering peak of one continuous widthization, and without apparent crystal diffraction peak, show that it is non crystalline structure.
Step 4：Make analysis oxygen catalysis electrode；
The Fe for being obtained step 3 using conducting resinl40Co8Ni40B10Ru2Alloy strip is fixedly connected with copper conductor, by non-survey
The non-conductive resin seal in examination part, exposes the scope of freedom of band；
Step 5：The processing of the electrode cycle of lye and aerobic environment；
The Fe that step 4 is prepared40Co8Ni40B10Ru2Electrode impregnates in the KOH solution liquid of a concentration of 0.1mol/L
30min is placed (environment temperature 298K, oxygen content 21%) for 24 hours in an oxygen-containing environment after taking-up.In this, as one cycle,
Carry out 6 cycles.
The Fe that will be prepared in embodiment 140Co8Ni40B10Ru2Non-crystalline material carries out the electrochemistry of electrolysis water liberation of hydrogen anode electrode
Test comprises the following steps：
Electrochemistry experiment on 3 electrochemical workstations of Princeton Applied Research VersaSTAT in
It is carried out under 298K, using traditional three-electrode system, area 1cm2Pt pieces be auxiliary electrode, saturated calomel electrode as ginseng
Than electrode, Fe obtained in embodiment 140Co8Ni40B10Ru2Electrolysis water hydrogen-precipitating electrode is working electrode, electrolyte 1mol/L
KOH solution.According to formula ERHE=+ESCE+ 0.242V+0.059pH, potential value convert for the potential relative to reversible hydrogen electrode
Value.The sweep speed of dynamic potential polarization curve is 0.833mVs-1.The polarization curve of acquisition is as shown in Figure 2.Fig. 2 show up to
To 10mAcm-2In the case of current density, overpotential only has 266mV.What low overpotential illustrated to prepare in embodiment 1
Fe40Co8Ni40B10Ru2Electrolysis water hydrogen-precipitating electrode has excellent catalytic activity for hydrogen evolution.In addition, using constant-current electrolysis test side
Method (constant current density 20mAcm-2) measure Fe40Co8Ni40B10Ru2In 1molL-1The change of current potential at any time in KOH solution
Change curve.As shown in figure 3, Fe40Co8Ni40B10Ru2In the electrolysis test of 10h, current potential is held essentially constant.Explanation
Fe40Co8Ni40B10Ru2Not only there is excellent analysis oxygen catalytic activity, while also having both excellent analysis oxidative stability.
Embodiment 2
Prepare Fe35Co12Ni35Si14Nb4It analyses oxygen and is catalyzed amorphous alloy electrode
Step 1：Dispensing
According to Fe35Co12Ni35Si14Nb4Target component weighs each simple substance element of Fe, Co, Ni, Si, Nb, the quality of each element
Percent purity is not less than 99.0%；
Step 2：Master alloy melting
Load weighted Fe, Co, Ni, Si, Nb each element in step 1 is uniformly mixed, and in vacuum arc melting furnace into
Row melting, obtains Fe35Co12Ni35Si14Nb4Subject alloy ingot；
Smelting parameter：Melting protective atmosphere is the argon gas that mass percent is 99.999%；
Vacuum degree is 9 × 10-3Pa；
Melting electric current is 120A；
Smelting time：Every time melting 2min, melting 4 times；
Step 3：Melt spinning method method prepares subject alloy band
By the master alloy Mechanical Crushing obtained in step 2 at being preset in quartz ampoule after fritter, quartz ampoule outlet at bottom is wide
Degree is 3.2mm, and is integrally put into the vacuum induction melting furnace of quick solidification apparatus, and being ejected into high speed after it is melted completely revolves
On the copper wheel turned, to which the Fe that thickness is 15 μm be prepared35Co12Ni35Si14Nb4Band；
Parameter setting：Melting protective atmosphere is the argon gas that mass percent is 99.0%；
Vacuum degree is：8×10-2Pa；
Coil-induced electric current is 9.1A；
Smelting time：12s；
Injection pressure：0.02MPa；
Copper wheel velocity of rotation：3200m/s.
Through alloy thin band made from step 3 through X diffractometries, embodiment 2 is non crystalline structure material, as shown in Figure 1.By
XRD spectrum shown in FIG. 1 can be seen that the subject alloy band prepared using the above method and is shown as through X-ray diffraction detection
The diffusing scattering peak of one continuous widthization, and without apparent crystal diffraction peak, show that it is non crystalline structure.
Step 4：Make analysis oxygen catalysis electrode
The Fe for being obtained step 3 using conducting resinl35Co12Ni35Si14Nb4Alloy strip is fixedly connected with copper conductor, will be non-
The non-conductive resin seal of part of detecting, exposes the scope of freedom of band；
Step 5：The processing of the electrode cycle of lye and aerobic environment；
The Fe that step 4 is prepared35Co12Ni35Si14Nb4Electrode soaks in the KOH solution liquid of a concentration of 0.5mol/L
15min is steeped, is placed in an oxygen-containing environment after taking-up (environment temperature 303K, oxygen content 25%) for 24 hours.In this, as once following
Ring carries out 7 cycles.
The Fe that will be prepared in embodiment 235Co12Ni35Si14Nb4The electro-chemical test of electrolysis water liberation of hydrogen anode electrode includes such as
Lower step：
Electrochemistry experiment on 3 electrochemical workstations of Princeton Applied Research VersaSTAT in
It is carried out under 298K, using traditional three-electrode system, area 1cm2Pt pieces be auxiliary electrode, saturated calomel electrode as ginseng
Than electrode, Fe obtained in embodiment 235Co12Ni35Si14Nb4Electrolysis water hydrogen-precipitating electrode is working electrode, electrolyte 1mol/L
KOH solution.According to formula ERHE=+ESCE+ 0.242V+0.059pH, potential value convert for the potential relative to reversible hydrogen electrode
Value.The sweep speed of dynamic potential polarization curve is 0.833mVs-1.The polarization curve of acquisition is as shown in Figure 2.Fig. 2 show up to
To 10mAcm-2In the case of current density, overpotential only has 278mV.What low overpotential illustrated to prepare in embodiment 2
Fe35Co12Ni35Si14Nb4Electrolysis water hydrogen-precipitating electrode has excellent catalytic activity for hydrogen evolution.In addition, being tested using constant-current electrolysis
Method (constant current density 20mAcm-2) measure Fe35Co12Ni35Si14Nb4In 1molL-1Current potential is at any time in KOH solution
Change curve.As shown in figure 4, Fe35Co12Ni35Si14Nb4In the electrolysis test of 10h, current potential is held essentially constant.Explanation
Fe35Co12Ni35Si14Nb4Not only there is excellent analysis oxygen catalytic activity, while also having both excellent analysis oxidative stability.
Embodiment 3
Prepare Fe32Co14Ni32Si8P8Nb4Mo2It analyses oxygen and is catalyzed amorphous alloy electrode
Step 1：Dispensing
According to Fe32Co14Ni32Si8P8Nb4Mo2Target component weighs each simple substance element (its of Fe, Co, Ni, Si, P, Nb, Mo
Middle P can be replaced with FeP), the mass percent purity of each element is not less than 99.0%；
Step 2：Master alloy melting
Load weighted Fe, Co, Ni, Si, P (or FeP), Nb, Mo each element in step 1 are uniformly mixed, and in vacuum electric
Melting is carried out in arc smelting furnace, obtains Fe32Co14Ni32Si8P8Nb4Mo2Subject alloy ingot；
Smelting parameter：Melting protective atmosphere is the argon gas that mass percent is 99.999%；
Vacuum degree is 9 × 10-3Pa；
Melting electric current is 120A；
Smelting time：Every time melting 2.5min, melting 4 times；
Step 3：Melt spinning method method prepares subject alloy band
By the master alloy Mechanical Crushing obtained in step 2 at being preset in quartz ampoule after fritter, quartz ampoule outlet at bottom is wide
Degree is 3.4mm, and is integrally put into the vacuum induction melting furnace of quick solidification apparatus, and being ejected into high speed after it is melted completely revolves
On the copper wheel turned, to which the Fe that thickness is 18 μm be prepared32Co14Ni32Si8P8Nb4Mo2Band；
Parameter setting：Melting protective atmosphere is the argon gas that mass percent is 99.0%；
Vacuum degree is：8×10-2Pa；
Coil-induced electric current is 9.4A；
Smelting time：17s；
Injection pressure：0.02MPa；
Copper wheel velocity of rotation：3200m/s.
Through alloy thin band made from step 3 through X diffractometries, embodiment 3 is non crystalline structure material, as shown in Figure 1.By
XRD spectrum shown in FIG. 1 can be seen that the subject alloy band prepared using the above method and is shown as through X-ray diffraction detection
The diffusing scattering peak of one continuous widthization, and without apparent crystal diffraction peak, show that it is non crystalline structure.
Step 4：Make analysis oxygen catalysis electrode
The Fe for being obtained step 3 using conducting resinl32Co14Ni32Si8P8Nb4Mo2Alloy strip is fixedly connected with copper conductor,
By the non-conductive resin seal in non-test part, the scope of freedom of band is exposed；
Step 5：The processing of the electrode cycle of lye and aerobic environment；
The Fe that step 4 is prepared32Co14Ni32Si8P8Nb4Mo2NaOH solution of the electrode in a concentration of 0.5mol/L
18min is impregnated in liquid, places 20h (environment temperature 303K, oxygen content 25%) after taking-up in an oxygen-containing environment.In this, as one
Secondary cycle carries out 8 cycles.
The Fe that will be prepared in embodiment 332Co14Ni32Si8P8Nb4Mo2The electro-chemical test packet of electrolysis water liberation of hydrogen anode electrode
Containing following steps：
Electrochemistry experiment on 3 electrochemical workstations of Princeton Applied Research VersaSTAT in
It is carried out under 298K, using traditional three-electrode system, area 1cm2Pt pieces be auxiliary electrode, saturated calomel electrode as ginseng
Than electrode, Fe obtained in embodiment 332Co14Ni32Si8P8Nb4Mo2Electrolysis water hydrogen-precipitating electrode is working electrode, and electrolyte is
1mol/L KOH solutions.According to formula ERHE=+ESCE+ 0.242V+0.059pH, potential value conversion is in order to relative to reversible hydrogen electricity
The potential value of pole.The sweep speed of dynamic potential polarization curve is 0.833mVs-1.The polarization curve of acquisition is as shown in Figure 2.Fig. 2
Show reaching 10mAcm-2In the case of current density, overpotential only has 287mV.Low overpotential illustrates in embodiment 3
The Fe of preparation50Co8Ni20Si14Nb8Electrolysis water hydrogen-precipitating electrode has excellent catalytic activity for hydrogen evolution.In addition, using constant-current electrolysis
Test method (constant current density 20mAcm-2) measure Fe32Co14Ni32Si8P8Nb4Mo2In 1molL-1It is electric in KOH solution
Position versus time curve.As shown in figure 5, Fe32Co14Ni32Si8P8Nb4Mo2In the electrolysis test of 10h, current potential is protected substantially
It holds constant.Illustrate Fe32Co14Ni32Si8P8Nb4Mo2Not only there is excellent analysis oxygen catalytic activity, while also having both excellent analysis
Oxidative stability.
Embodiment 4
Prepare Fe27Co18Ni27B9Si9Cr5Ru4La1Analyse oxygen catalysis amorphous and crystalline state nanometer alloy electrode
Step 1：Dispensing
According to Fe27Co18Ni27B9Si9Cr5Ru4La1Target component weighs each simple substance member of Fe, Co, Ni, B, Si, Cr, Ru, La
Plain wherein B element can be replaced with FeB prealloys, and the mass percent purity of each element is not less than 99.0%；
Step 2：Master alloy melting
Load weighted Fe, Co, Ni, B (or FeB), Si, Cr, Ru, La each element in step 1 are uniformly mixed, and true
Melting is carried out in empty arc-melting furnace, obtains Fe27Co18Ni27B9Si9Cr5Ru4La1Subject alloy ingot；
Smelting parameter：Melting protective atmosphere is the argon gas that mass percent is 99.999%；
Vacuum degree is 9 × 10-3Pa；
Melting electric current is 105A；
Smelting time：Every time melting 3min, melting 3 times；
Step 3：Melt spinning method method prepares subject alloy band
By the master alloy Mechanical Crushing obtained in step 2 at being preset in quartz ampoule after fritter, quartz ampoule outlet at bottom is wide
Degree is 3.2mm, and is integrally put into the vacuum induction melting furnace of quick solidification apparatus, and being ejected into high speed after it is melted completely revolves
On the copper wheel turned, to which the Fe that thickness is 16 μm be prepared27Co18Ni27B9Si9Cr5Ru4La1Band；
Parameter setting：Melting protective atmosphere is the argon gas that mass percent is 99.0%；
Vacuum degree is：8×10-2Pa；
Coil-induced electric current is 8.3A；
Smelting time：9s；
Injection pressure：0.02MPa；
Copper wheel velocity of rotation：3400m/s.
Through alloy thin band made from step 3 through X diffractometries, embodiment 4 is amorphous and nanocomposite structural material,
As shown in Figure 1.XRD spectrum as shown in Figure 1 can be seen that the subject alloy band prepared using the above method and spread out through X-ray
Penetrate detection and show and be superimposed a faint and wideization crystal diffraction peak on diffusing scattering peak, show there is nanocrystalline precipitation, band at
Amorphous and nanocomposite structure.
Step 4：Make analysis oxygen catalysis electrode
The Fe for being obtained step 3 using conducting resinl27Co18Ni27B9Si9Cr5Ru4La1Alloy strip and copper conductor, which are fixed, to be connected
It connects, by the non-conductive resin seal in non-test part, exposes the scope of freedom of band；
Step 5：The processing of the electrode cycle of lye and aerobic environment；
The Fe that step 4 is prepared27Co18Ni27B9Si9Cr5Ru4La1Na of the electrode in a concentration of 0.5mol/L2CO3
30min is impregnated in solution liquid, is placed in an oxygen-containing environment after taking-up (environment temperature 303K, oxygen content 25%) for 24 hours.Made with this
For one cycle, 9 cycles are carried out.
The Fe that will be prepared in embodiment 427Co18Ni27B9Si9Cr5Ru4La1The electro-chemical test of electrolysis water liberation of hydrogen anode electrode
It comprises the following steps：
Electrochemistry experiment on 3 electrochemical workstations of Princeton Applied Research VersaSTAT in
It is carried out under 298K, using traditional three-electrode system, area 1cm2Pt pieces be auxiliary electrode, saturated calomel electrode as ginseng
Than electrode, Fe obtained in embodiment 427Co18Ni27B9Si9Cr5Ru4La1Electrolysis water hydrogen-precipitating electrode is working electrode, and electrolyte is
1mol/L KOH solutions.According to formula ERHE=+ESCE+ 0.242V+0.059pH, potential value conversion is in order to relative to reversible hydrogen electricity
The potential value of pole.The sweep speed of dynamic potential polarization curve is 0.833mVs-1.The polarization curve of acquisition is as shown in Figure 2.Fig. 2
Show reaching 10mAcm-2In the case of current density, overpotential only has 299mV.Low overpotential illustrates in embodiment 4
The Fe of preparation27Co18Ni27B9Si9Cr5Ru4La1Electrolysis water hydrogen-precipitating electrode has excellent catalytic activity for hydrogen evolution.
Embodiment 5
Prepare Fe25Co21Ni25Si7C7P5Nb5Cu3Y2Analyse oxygen catalysis amorphous and crystalline state nanometer alloy electrode
Step 1：Dispensing
According to Fe25Co21Ni25Si7C7P5Nb5Cu3Y2Target component weighs each simple substance of Fe, Co, Ni, Si, C, P, Nb, Cu, Y
Element, wherein C, P element can be replaced with FeC and FeP prealloys, and the mass percent purity of each element is not less than 99.0%；
Step 2：Master alloy melting
Load weighted Fe, Co, Ni, Si, C, P (or FeC, FeP), Nb, Cu, Y each element in step 1 are uniformly mixed, and
Melting is carried out in vacuum arc melting furnace, obtains Fe25Co21Ni25Si7C7P5Nb5Cu3Y2Subject alloy ingot；
Smelting parameter：Melting protective atmosphere is the argon gas that mass percent is 99.999%；
Vacuum degree is 9 × 10-3Pa；
Melting electric current is 125A；
Smelting time：Every time melting 2min, melting 6 times；
Step 3：Melt spinning method method prepares subject alloy band
By the master alloy Mechanical Crushing obtained in step 2 at being preset in quartz ampoule after fritter, quartz ampoule outlet at bottom is wide
Degree is 2.7mm, and is integrally put into the vacuum induction melting furnace of quick solidification apparatus, and being ejected into high speed after it is melted completely revolves
On the copper wheel turned, to which the Fe that thickness is 50 μm be prepared25Co21Ni25Si7C7P5Nb5Cu3Y2Band；
Parameter setting：Melting protective atmosphere is the argon gas that mass percent is 99.0%；
Vacuum degree is：9×10-2Pa；
Coil-induced electric current is 8.6A；
Smelting time：10s；
Injection pressure：0.03MPa；
Copper wheel velocity of rotation：3200m/s.
Through alloy thin band made from step 3 through X diffractometries, embodiment 5 is amorphous and nanocomposite structural material,
As shown in Figure 1.XRD spectrum as shown in Figure 1 can be seen that the subject alloy band prepared using the above method and spread out through X-ray
Penetrate detection and show and be superimposed two faint and wideization crystal diffraction peaks on diffusing scattering peak, show there is nanocrystalline precipitation, band at
Amorphous and nanocomposite structure.
Step 4：Make analysis oxygen catalysis electrode
The Fe for being obtained step 3 using conducting resinl25Co21Ni25Si7C7P5Nb5Cu3Y2Alloy strip and copper conductor, which are fixed, to be connected
It connects, by the non-conductive resin seal in non-test part, exposes the scope of freedom of band；
Step 5：The processing of the electrode cycle of lye and aerobic environment；
The Fe that step 4 is prepared25Co21Ni25Si7C7P5Nb5Cu3Y2KOH solution of the electrode in a concentration of 1mol/L
15min is impregnated in liquid, is placed in an oxygen-containing environment after taking-up (environment temperature 303K, oxygen content 25%) for 24 hours.In this, as one
Secondary cycle carries out 9 cycles.
The Fe that will be prepared in embodiment 525Co21Ni25Si7C7P5Nb5Cu3Y2The electrochemistry of electrolysis water liberation of hydrogen anode electrode is surveyed
Examination comprises the following steps：
Electrochemistry experiment on 3 electrochemical workstations of Princeton Applied Research VersaSTAT in
It is carried out under 298K, using traditional three-electrode system, area 1cm2Pt pieces be auxiliary electrode, saturated calomel electrode as ginseng
Than electrode, Fe obtained in embodiment 525Co21Ni25Si7C7P5Nb5Cu3Y2Electrolysis water hydrogen-precipitating electrode is working electrode, electrolyte
For 1mol/L KOH solutions.According to formula ERHE=+ESCE+ 0.242V+0.059pH, potential value convert in order to relative to reversible hydrogen
The potential value of electrode.The sweep speed of dynamic potential polarization curve is 0.833mVs-1.The polarization curve of acquisition is as shown in Figure 2.Figure
2 show reaching 10mAcm-2In the case of current density, overpotential only has 303mV.Low overpotential illustrates in embodiment 5
The Fe of preparation25Co21Ni25Si7C7P5Nb5Cu3Y2Electrolysis water hydrogen-precipitating electrode has excellent catalytic activity for hydrogen evolution.
Embodiment 6
Prepare Fe24Co15Ni24B9Si9C5P5Nb3Cr3Ru2La1Analyse oxygen catalysis amorphous and crystalline state nanometer alloy electrode
Step 1：Dispensing
According to Fe24Co15Ni24B9Si9C5P5Nb3Cr3Ru2La1Target component weigh Fe, Co, Ni, B, Si, C, P, Nb, Cr,
Each simple substance element of Ru, La, wherein B, P, C element can be replaced with FeB, FeP, FeC prealloy, the mass percent purity of each element
Not less than 99.0%；
Step 2：Master alloy melting
By load weighted Fe, Co, Ni, B, Si, C, P (or FeB, FeC, FeP), Nb, Cr, Ru, La each element in step 1
It is uniformly mixed, and carries out melting in vacuum arc melting furnace, obtain Fe24Co15Ni24B9Si9C5P5Nb3Cr3Ru2La1Target is closed
Ingot；
Smelting parameter：Melting protective atmosphere is the argon gas that mass percent is 99.999%；
Vacuum degree is 9 × 10-3Pa；
Melting electric current is 120A；
Smelting time：Every time melting 2min, melting 4 times；
Step 3：Melt spinning method method prepares subject alloy band
By the master alloy Mechanical Crushing obtained in step 2 at being preset in quartz ampoule after fritter, quartz ampoule outlet at bottom is wide
Degree is 2.6mm, and is integrally put into the vacuum induction melting furnace of quick solidification apparatus, and being ejected into high speed after it is melted completely revolves
On the copper wheel turned, to which the Fe that thickness is 90 μm be prepared24Co15Ni24B9Si9C5P5Nb3Cr3Ru2La1Band；
Parameter setting：Melting protective atmosphere is the argon gas that mass percent is 99.0%；
Vacuum degree is：8×10-2Pa；
Coil-induced electric current is 8.5A；
Smelting time：12s；
Injection pressure：0.03MPa；
Copper wheel velocity of rotation：2800m/s.
Through alloy thin band made from step 3 through X diffractometries, embodiment 6 is amorphous and nanocomposite structural material,
As shown in Figure 1.XRD spectrum as shown in Figure 1 can be seen that the subject alloy band prepared using the above method and spread out through X-ray
It penetrates on detection display diffusing scattering peak and has been superimposed two more sharp crystal diffraction peaks, show there is nanocrystalline precipitation, band is at amorphous
With nanocomposite structure.
Step 4：Make analysis oxygen catalysis electrode
The Fe for being obtained step 3 using conducting resinl24Co15Ni24B9Si9C5P5Nb3Cr3Ru2La1Alloy strip and copper conductor
It is fixedly connected, by the non-conductive resin seal in non-test part, exposes the scope of freedom of band；
Step 5：The processing of the electrode cycle of lye and aerobic environment；
The Fe that step 4 is prepared24Co15Ni24B9Si9C5P5Nb3Cr3Ru2La1Electrode is a concentration of 1.5mol/L's
10min is impregnated in NaOH solution liquid, is placed in an oxygen-containing environment after taking-up (environment temperature 303K, oxygen content 25%) for 24 hours.With
This carries out 7 cycles as one cycle.
The Fe that will be prepared in embodiment 624Co15Ni24B9Si9C5P5Nb3Cr3Ru2La1The electrification of electrolysis water liberation of hydrogen anode electrode
Test is learned to comprise the following steps：
Electrochemistry experiment on 3 electrochemical workstations of Princeton Applied Research VersaSTAT in
It is carried out under 298K, using traditional three-electrode system, area 1cm2Pt pieces be auxiliary electrode, saturated calomel electrode as ginseng
Than electrode, Fe obtained in embodiment 624Co15Ni24B9Si9C5P5Nb3Cr3Ru2La1Electrolysis water hydrogen-precipitating electrode is working electrode, electricity
Solution liquid is 1mol/L KOH solutions.According to formula ERHE=+ESCE+ 0.242V+0.059pH, potential value conversion is in order to relative to can
The potential value of inverse hydrogen electrode.The sweep speed of dynamic potential polarization curve is 0.833mVs-1.The polarization curve of acquisition such as Fig. 2 institutes
Show.Fig. 2 shows reaching 10mAcm-2In the case of current density, overpotential 358mV.Overpotential is excessively high to illustrate embodiment
The Fe prepared in 624Co15Ni24B9Si9C5P5Nb3Cr3Ru2La1Electrolysis water hydrogen-precipitating electrode is simultaneously lived without excellent liberation of hydrogen catalysis
Property.
Embodiment 7~21 (in addition to constituent content is different) is made using the preparation method of embodiment 1, other conditions with reality
It is identical to apply example 1.7~21 related content of embodiment see the table below：
It should be noted that according to the various embodiments described above of the present invention, those skilled in the art are that this hair may be implemented completely
Bright independent claims and the full scope of appurtenance, realize process and the same the various embodiments described above of method；And the present invention is not
It elaborates and partly belongs to techniques well known.
The above, part specific implementation mode only of the present invention, but scope of protection of the present invention is not limited thereto, appoints
In the technical scope disclosed by the present invention, the change or replacement that can be readily occurred in should all be covered what those skilled in the art
Within protection scope of the present invention.
Claims (10)
1. one kind (FeaCobNic)xMyRzSystem's analysis oxygen catalysis material, it is characterised in that：(FeaCobNic)xMyRzSystem's analysis oxygen is catalyzed material
Atomic percent dosage in material is a+b+c=1,0.5≤a≤0.94,0.01≤b≤0.9,0.5≤c≤0.94,50≤x≤
95,5≤y≤35,0.5≤z≤15；Wherein M be B, Si, C, P in one or more kinds of elements, R Nb, Cr, Mn, Ru,
One or more kinds of elements in Mo, Zr, Cu, Y, La.
2. (Fe according to claim 1aCobNic)xMyRzSystem's analysis oxygen catalysis material, it is characterised in that preferred non crystalline structure
Material composition has：Fe40Co8Ni40B10Ru2、Fe35Co12Ni35Si14Nb4Or Fe32Co14Ni32Si8P8Nb4Mo2、。
3. (Fe according to claim 1aCobNic)xMyRzSystem's analysis oxygen catalysis material, it is characterised in that preferred amorphous with receive
The brilliant sandwich ingredient of rice has：Fe27Co18Ni27B9Si9Cr5Ru4La1、Fe25Co21Ni25Si7C7P5Nb5Cu3Y2Or
Fe24Co15Ni24B9Si9C5P5Nb3Cr3Ru2La1。
4. (Fe according to claim 1 or 2 or 3aCobNic)xMyRzSystem's analysis oxygen catalysis material, it is characterised in that：Reaching
10mA·cm-2In the case of current density, overpotential is 220mV~360mV.
5. preparing (Fe described in claim 1aCobNic)xMyRzThe method of system's analysis oxygen catalysis material, it is characterised in that include
The following steps：
Step 1：According to target ingredient composition；
According to (FeaCobNic)xMyRzTarget component weighs Fe, Co, Ni, M, R each element can make when wherein M is B, C, P element
It is not less than 99.0% with the mass percent purity of FeM alloy replacings, each element；
Step 2：Master alloy melting；
Load weighted Fe, Co, Ni, M, R each element in step 1 is uniformly mixed, and is melted in vacuum arc melting furnace
Refining, obtains (FeaCobNic)xMyRzSubject alloy ingot；
Smelting parameter：Melting protective atmosphere is the argon gas that mass percent is 99.999%；
Vacuum degree is 1 × 10-4~8 × 10-3Pa；
Melting electric current is 30~200A；
Smelting time：Every time 1~20min of melting, melting 1~10 time；
Step 3：Melt spinning method method prepares subject alloy band；
By the master alloy Mechanical Crushing obtained in step 2 at being preset in quartz ampoule after fritter, and integrally it is put into quickly solidification dress
In the vacuum induction melting furnace set, it is ejected on high-speed rotating copper wheel after it is melted completely, is to which thickness be prepared
0.05~500 μm of (FeaCobNic)xMyRzAlloy thin band；
Parameter setting：Melting protective atmosphere is the argon gas that mass percent is 99.0%；
Vacuum degree is：6×10-2~2 × 10-1Pa；
Coil-induced electric current is 2~20A；
Smelting time：10~180s；
Injection pressure：0.01~0.1MPa；
Copper wheel velocity of rotation：1000~4000m/s.
6. preparation (Fe according to claim 5aCobNic)xMyRzThe method of system's analysis oxygen catalysis material, it is characterised in that：Energy
The alloy thin band that thickness is 0.05~500 μm is enough made.
7. preparing (FeaCobNic)xMyRzThe method of the Oxygen anodic evolution electrode of system's analysis oxygen catalysis material, it is characterised in that：First use
Conducting resinl is by copper conductor and (FeaCobNic)xMyRzAlloy strip is fixedly connected, by the non-conductive resin seal in non-test part,
Expose (FeaCobNic)xMyRzThe scope of freedom of alloy strip, obtains (FeaCobNic)xMyRzAnalyse oxygen catalyticing anode electrode；Then
By (FeaCobNic)xMyRz3~10 circular treatments that oxygen catalyticing anode electrode carries out lye and aerobic environment are analysed, are obtained directly
Available Oxygen anodic evolution electrode.
8. preparation (Fe according to claim 7aCobNic)xMyRzThe side of the Oxygen anodic evolution electrode of system's analysis oxygen catalysis material
Method, it is characterised in that：Anode electrode obtained is applied in electrolysis water.
9. preparation (Fe according to claim 7aCobNic)xMyRzThe side of the Oxygen anodic evolution electrode of system's analysis oxygen catalysis material
Method, it is characterised in that：The lye be sodium hydroxide, potassium hydroxide, calcium hydroxide, lithium hydroxide, one hydration ammonia, sodium carbonate,
It is one or more in sodium bicarbonate, a concentration of 0.1~3mol/L；
The temperature impregnated in lye in the surface treatment is 280~310K；
The time impregnated in lye in the surface treatment is 2min~for 24 hours；
The temperature placed under aerobic environment in the surface treatment is 280~310K；
The oxygen content placed under aerobic environment in the surface treatment is 21~40%；
The time placed under aerobic environment in the surface treatment be 2~for 24 hours.
10. preparation (Fe according to claim 7aCobNic)xMyRzThe side of the Oxygen anodic evolution electrode of system's analysis oxygen catalysis material
Method, it is characterised in that：Reaching 10mAcm-2In the case of current density, overpotential is 220mV~360mV.
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| CN113862722A (en) * | 2021-09-30 | 2021-12-31 | 东南大学 | High-entropy amorphous anode oxygen evolution electrode material and preparation method thereof |
| CN116180124A (en) * | 2023-03-22 | 2023-05-30 | 哈尔滨工业大学 | Preparation method and application of high-entropy alloy electrocatalytic electrode with core-shell structure |
| CN116288074A (en) * | 2023-03-22 | 2023-06-23 | 哈尔滨工业大学 | FeNi (Mo/Co) BP amorphous alloy oxygen evolution catalyst and preparation method thereof |
| CN116288076A (en) * | 2023-03-22 | 2023-06-23 | 哈尔滨工业大学 | Fe-based nanocrystalline/amorphous alloy for degrading aniline in organic wastewater and separating hydrogen and oxygen from electrolyzed water and application |
| CN116180124B (en) * | 2023-03-22 | 2023-12-12 | 哈尔滨工业大学 | Preparation method and application of high-entropy alloy electrocatalytic electrode with core-shell structure |
| CN116288076B (en) * | 2023-03-22 | 2024-04-05 | 哈尔滨工业大学 | Fe-based nanocrystalline/amorphous alloy for degrading aniline in organic wastewater and separating hydrogen and oxygen from electrolyzed water and application |
| CN116288074B (en) * | 2023-03-22 | 2024-04-05 | 哈尔滨工业大学 | FeNi (Mo/Co) BP amorphous alloy oxygen evolution catalyst and preparation method thereof |
| CN116334663A (en) * | 2023-05-29 | 2023-06-27 | 中石油深圳新能源研究院有限公司 | Method and device for preparing amorphous transition metal nitride electrocatalyst |
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