CN109023412A - A kind of nanoporous ambrose alloy/amorphous combination electrode material and preparation method thereof - Google Patents
A kind of nanoporous ambrose alloy/amorphous combination electrode material and preparation method thereof Download PDFInfo
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Abstract
A kind of nanoporous ambrose alloy/amorphous combination electrode material and preparation method thereof, belongs to electro-catalysis technical field.The preparation method of the nanometer combined electrode material specifically includes that Cu-Ni-Zr-Ti amorphous alloy, which is prepared, using melt spun method makees presoma, selective corrosion is carried out to amorphous precursor body using the de- alloyage process of chemistry and removes Zr and Ti, finally obtains surface with nanometer through-hole ambrose alloy structure and inner base keeps amorphous " sandwich " composite construction.The nanometer combined electrode material that the present invention is prepared has the structure of similar " sandwich ", and nanoporous ambrose alloy is evenly distributed in amorphous substrate, has good mechanical flexibility, and pattern is uniform, large specific surface area, electro catalytic activity with higher.The nanocomposite of the invention can be directly used as the electrode material of electrolysis water liberation of hydrogen, be 10mA/cm in current density2When hydrogen-evolution overpotential be about 120mV, Tafel slope is 38mV/dec, is a kind of cheap high-performance electric catalysis material, can be used for electro-catalysis and produce the new energy fields such as hydrogen.
Description
Technical field
The invention belongs to electro-catalysis field, in particular to a kind of nanoporous ambrose alloy that can be used for electrolysis water hydrogen making/
Amorphous combination electrode material and preparation method thereof.
Background technique
With the aggravation of world energy sources crisis, tap a new source of energy extremely urgent, in numerous new energy, Hydrogen Energy conduct
A kind of energy of high-efficiency cleaning got the attention and applies in 21 century.Hydrogen Energy has huge in hydrogen fuel cell field
Application potential, at present Toyota Motor factory volume production hydrogen cell automobile.Its working principle is exactly to pass through electrolysis water system
It takes hydrogen to be then injected into automobile and provides power with oxygen mix burning driving motor for vehicle.The method of hydrogen making has very much,
Wherein electrolysis water evolving hydrogen reaction (Hydrogen evolution reaction, HER) has that technique and operating process be simple, ring
The advantages that border is friendly, product purity is high and industrialization is mature is to realize that industrialization inexpensively prepares the important means of hydrogen.
Electrolysis water evolving hydrogen reaction is exactly a process for converting electric energy to Hydrogen Energy.Electrode material catalytic activity is not high to be led
The waste of electric energy during solving elutriation hydrogen is sent a telegraph, therefore the catalytic activity for improving electrode material is to reduce water electrolysis hydrogen production energy consumption
It is crucial.Electrode used at present has the sulfide of transition group, phosphide, nano porous metal etc..Although magnesium-yttrium-transition metal is cheap
But catalytic activity is bad, obtained product catalyst activity is bad and cannot be directly as electrode using needing to be supported on glass
On carbon electrode, complex process is inconvenient, is unfavorable for industrialization.Nano porous metal is shown preferably in terms of electrolysis water liberation of hydrogen
Catalytic performance, but block nanometer porous metals brittleness is larger, need to be modified, support processing, cannot be used directly for function
Device.Also there is document report Pd at present40Ni10Cu30P20Amorphous alloy shows good catalysis in terms of electrolysis water liberation of hydrogen
Performance, but noble metal higher cost, amorphous block, band specific surface area are smaller, and HER catalytic activity needs further to be mentioned
It rises.The current electrode material in HER all includes noble metal, and there are expensive, specific surface area is low, electro catalytic activity is not high scarce
Point causes electrolysis electrode hydrogen-evolution overpotential excessively high, and energy consumption is excessive, at high cost, seriously constrains the development of water electrolysis method hydrogen producing technology.
Therefore, it develops with high HER catalytic activity and cheap hydrogen evolution electrode material has the meaning and practical application valence of important science
Value.
Summary of the invention
The purpose of the present invention is overcoming the shortcomings of existing hydrogen evolution electrode material, a kind of nanometer for water electrolysis hydrogen production is provided
Porous ambrose alloy/amorphous combination electrode material and preparation method thereof reduces cost while keeping good catalytic, and has
There is good mechanical flexibility, can be used directly as electrode.Using with good mechanical it is flexible and have it is good amorphous at
Then the Cu-Ni-Zr-Ti amorphous alloy of ability freely corrodes to obtain nanoporous, passes through control as presoma by chemistry
Surface is prepared with nanoporous ambrose alloy in de- alloying time, and matrix still keeps amorphous " sandwich " structure electrode material
Material.The disadvantage that nanoporous ambrose alloy/amorphous combination electrode material not only can overcome bulk metal brittleness larger, but also can fill
Divide using electrode material the characteristics of its nanostructure directly as electrolysis water liberation of hydrogen, improves the specific surface area of electrode, make activity
The uniform sequential distribution of substance improves the catalytic performance of electrolysis water liberation of hydrogen.
Nanoporous ambrose alloy/amorphous combination electrode material, it is characterised in that there is three-dimensional uniform " sandwich " layering knot
Structure, it may be assumed that surface is nanoporous ambrose alloy, and centre is noncrystal substrate, forms the compound of nanoporous ambrose alloy and amorphous；Nanometer it is more
Hole ambrose alloy is evenly distributed in amorphous substrate, and surface layer is porous to show as continuous through-hole, and the diameter in hole is about the left side 10nm~30nm
It is right.
Nanoporous ambrose alloy/amorphous the combination electrode material, it is characterised in that shown while without precious metal
Good electro-chemical activity: Tafel slope is down to 38mV/dec, 10mA/cm2Overpotential under current density is about 120mV.
The present invention provides a kind of nanoporous ambrose alloy/amorphous combination electrode material preparation side for water electrolysis hydrogen production
Method, the material preparation method are main including the following steps:
(1) preparation of amorphous alloy strips: Cu-Ni-Zr-Ti alloy is selected to be prepared by melt-quenching method flexible non-
Crystal zone material；
(2) nanoporous ambrose alloy/amorphous combination electrode material preparation: use Cu-Ni-Zr-Ti amorphous alloy strips as
Amorphous thin ribbon is placed in various concentration HF corrosive liquid under condition of different temperatures and carries out as corrosive liquid by presoma, HF solution
Surface takes off Alloying Treatment, and strip is taken out from HF solution, is cleaned multiple times through ultrapure water and absolute alcohol, removes residual in hole
Stay chemical substance.Finally obtain nanoporous ambrose alloy/amorphous combination electrode material.
Nanoporous ambrose alloy/amorphous combination electrode material preparation method, which is characterized in that in the step 1)
The nominal composition of the Cu-Ni-Zr-Ti amorphous alloy presoma used is CuaNibZrcTid, wherein 10≤a≤45,10≤b≤
45,10≤c≤45,10≤d≤35, a+b+c+d=100, marked ingredient are atomic percent.
Nanoporous ambrose alloy/amorphous combination electrode material preparation method, which is characterized in that in the step 1)
The Cu-Ni-Zr-Ti amorphous alloy ribbon prepared by melt-quenching method with a thickness of 20~30 μm, width is 1~2mm；It is described
Amorphous alloy ribbon have good mechanical bend flexible.
Nanoporous ambrose alloy/amorphous combination electrode material preparation method, which is characterized in that in the step 2)
Surface takes off the corrosive liquid that uses of alloying for the HF solution of 0.01~0.2mol/L, etching time for 0.5~for 24 hours, de- alloy
Changing temperature is 25~70 DEG C.
Nanoporous ambrose alloy/amorphous combination electrode material preparation method, which is characterized in that in the step 2)
The aperture of the porous ambrose alloy of flexible nano is 5~30nm, and porous layer thickness is 500nm~2 μm.
Compared with existing electrolysis water cathode material for hydrogen evolution, beneficial effects of the present invention are as follows:
(1) nanoporous ambrose alloy/amorphous combination electrode material prepared by the present invention is without precious metal and has excellent electricity
Catalytic activity and good mechanical flexibility, can be directly as the electrode material of electrolysis water liberation of hydrogen, without using glass-carbon electrode
Etc. being modified.Therefore, electrode material of the invention is easy to device, cost performance height, is suitble to produce in enormous quantities.
(2) present invention proposes first to prepare flexible Cu-Ni-Zr-Ti amorphous band, then again using the side of the de- alloying of chemistry
Surface is prepared with nanoporous ambrose alloy in method and matrix keeps amorphous composite construction.The nanoporous that this method obtains
The aperture of ambrose alloy film and film thickness are controllable, and the shape of regulation nanoporous ambrose alloy is realized by controlling de- alloying time
Looks.Preparation method is simple, easily operated, and environmental-friendly.
(3) the preparation-obtained nanoporous ambrose alloy film of the present invention has the through-hole structure of three-dimensional uniformly co-continuous, micro-
Structure-controllable is seen, bent toughness is good, and internal large specific surface area improves electrode material activity relative to traditional electrode material
The contact area of substance and electrolyte improves electro-catalysis efficiency.
(4) nanoporous ambrose alloy/amorphous combination electrode material prepared by the present invention is 10mA/cm in current density2Shi Xi
Hydrogen potential is about 120mV, and it is a kind of ideal high performance catalyst material that Tafel slope, which is 38mV/dec, has very big city
Field application potential.
Detailed description of the invention
Fig. 1 is with Cu20Ni10Zr45Ti25The surface shape for the nanoporous ambrose alloy that amorphous alloy is obtained as precursor preparation
Looks scanning electron microscope diagram piece.
Fig. 2 is with Cu20Ni10Zr45Ti25Amorphous alloy ribbon is prepared as presoma using the de- alloyage of chemistry
Nanoporous ambrose alloy film sections scanning electron microscope diagram piece.
Fig. 3 is Cu40Ni10Zr35Ti15、Cu25Ni25Zr35Ti15And Cu10Ni40Zr35Ti15The X-ray of amorphous alloy ribbon is spread out
Penetrate map.
Fig. 4 is Cu40Ni10Zr35Ti15Nanoporous ambrose alloy/amorphous combination electrode that amorphous alloy obtains after de- alloying
The linear volt-ampere curve that material measures in 1M KOH.
Fig. 5 is Cu25Ni25Zr35Ti15Amorphous alloy ribbon takes off the nanoporous nickel obtained after alloying at different conditions
The linear volt-ampere curve that copper/amorphous combination electrode material measures in 1M KOH.
Fig. 6 is Cu25Ni25Zr35Ti15Amorphous alloy at different conditions take off alloying after obtain nanoporous ambrose alloy/it is non-
The Tafel slope that brilliant combination electrode material measures in 1M KOH.
Fig. 7 is Cu10Ni40Zr35Ti15Amorphous alloy ribbon takes off the nanoporous ambrose alloy/amorphous compound electric obtained after alloying
The linear volt-ampere curve that pole material measures in 1M KOH.
Fig. 8 is Cu10Ni40Zr35Ti15Nanoporous ambrose alloy/amorphous that amorphous alloy ribbon obtains after de- alloying is compound
The Tafel slope that electrode material measures in 1M KOH.
Specific embodiment
With reference to the accompanying drawings and examples, technical scheme of the present invention will be described in further detail.
Embodiment 1: with Cu20Ni10Zr45Ti25As presoma alloy nominal composition, pure element needed for body alloy being driven
(Cu99.99wt%, Zr 99.99wt%, Ti 99.99wt%, Ni99.99wt%), by weight of the atomic percent of alloy
It is weighed up at quality, the method for then using the vacuum arc melting of high-purity argon atmosphere, melting obtains Cu20Ni10Zr45Ti25Master alloy knob
Ingot is detained, melting is multiple, to guarantee that master alloy ingot ingredient is uniform.By master alloy ingot, induction heating melts again in quartz ampoule respectively
Change, and is continuously quickly ejected into water cooling rotary copper roller (copper roller diameter under the high-purity argon gas effect that pressure is 0.2MPa or so
220mm, 2700~3000r/min of revolving speed), form Cu20Ni10Zr45Ti25Fast quenching amorphous alloy ribbon.
With Cu20Ni10Zr45Ti25Fast quenching amorphous alloy ribbon as precursor 0.1mol/L HF aqueous solution as corrosion
Liquid carries out the de- alloying of chemistry, Cu20Ni10Zr45Ti25Amorphous alloy ribbon is successively anti-with ultrapure water and absolute alcohol before treatment
Multiple ultrasonic cleaning.By treated, amorphous alloy ribbon is placed in HF corrosive liquid, and Alloying Treatment 1.5h is taken off under the conditions of 25 DEG C.
Strip is taken out, nanoporous ambrose alloy film is successively cleaned multiple times with ultrapure water and absolute alcohol, removes residualization in hole
Substance is learned, is obtained after dry using Cu20Ni10Zr45Ti25Nanoporous ambrose alloy/amorphous compound electric of amorphous alloy precursor preparation
Pole material.Fig. 1 is with Cu20Ni10Zr45Ti25The surface for the nanoporous ambrose alloy film that amorphous alloy is obtained as precursor preparation
Topography scan electron microscope picture.Fig. 2 is with Cu20Ni10Zr45Ti25Amorphous alloy ribbon is closed as presoma using chemistry is de-
The nanoporous ambrose alloy that golden method is prepared/amorphous combination electrode material cross sectional scanning electron microscope photograph.
Embodiment 2: with Cu40Ni10Zr35Ti15As presoma alloy nominal composition, pure element needed for body alloy being driven
(Cu99.99wt%, Zr 99.99wt%, Ti 99.99wt%, Ni99.99wt%), by weight of the atomic percent of alloy
It is weighed up at quality, the method for then using the vacuum arc melting of high-purity argon atmosphere, melting obtains Cu40Ni10Zr35Ti15Master alloy knob
Ingot is detained, melting is multiple, to guarantee that master alloy ingot ingredient is uniform.By master alloy ingot, induction heating melts again in quartz ampoule respectively
Change, and is continuously quickly ejected into water cooling rotary copper roller (copper roller diameter under the high-purity argon gas effect that pressure is 0.2MPa or so
220mm, 2700~3000r/min of revolving speed), form Cu40Ni10Zr35Ti15Fast quenching amorphous alloy ribbon.
With Cu40Ni10Zr35Ti15Fast quenching amorphous alloy ribbon as precursor 0.2mol/L HF aqueous solution as corrosion
Liquid carries out the de- alloying of chemistry, Cu respectively40Ni10Zr35Ti15Amorphous alloy ribbon is before treatment successively with ultrapure water and without watery wine
Smart ultrasonic cleaning repeatedly.By treated, amorphous alloy ribbon is placed in HF corrosive liquid, and Alloying Treatment is taken off under the conditions of 25 DEG C
1h.Strip is taken out, nanoporous ambrose alloy film is successively cleaned multiple times with ultrapure water and absolute alcohol, removes and is remained in hole
Chemical substance is obtained after dry using Cu40Ni10Zr35Ti15The nanoporous ambrose alloy amorphous of amorphous alloy precursor preparation is compound
Electrode material.Fig. 3 is Cu40Ni10Zr35Ti15The X ray diffracting spectrum of alloy thin band, it was demonstrated that the alloy thin band is amorphous state knot
Structure.Using nanoporous ambrose alloy/amorphous combination electrode material as working electrode, coated graphite rod electrrode is auxiliary electrode, Hg/HgO mark
Collimator electrode is that reference electrode constitutes three-electrode system, linear voltammetric scan is carried out in 1mol/L KOH solution, scanning speed is
50mV/s.Fig. 4 is Cu40Ni10Zr35Ti15Nanoporous ambrose alloy/amorphous combination electrode that amorphous alloy obtains after de- alloying
The linear volt-ampere curve that material measures in 1M KOH is 10mA/cm in current density2When hydrogen-evolution overpotential be about 130mV.
Embodiment 3:
With Cu25Ni25Zr35Ti15As presoma alloy nominal composition, pure element (Cu needed for body alloy being driven
99.99wt%, Zr 99.99wt%, Ti 99.99wt%, Ni 99.99wt%), it is converted into according to the atomic percent of alloy
Quality weighs up, and the method for then using the vacuum arc melting of high-purity argon atmosphere, melting obtains Cu25Ni25Zr35Ti15Master alloy button
Ingot, melting is multiple, to guarantee that master alloy ingot ingredient is uniform.The induction heating refuse in quartz ampoule respectively by master alloy ingot,
And (copper roller diameter is continuously quickly ejected into water cooling rotary copper roller under the high-purity argon gas effect that pressure is 0.2MPa or so
220mm, 2700~3000r/min of revolving speed), form Cu25Ni25Zr35Ti15Fast quenching amorphous alloy ribbon.
With Cu25Ni25Zr35Ti15Fast quenching amorphous alloy ribbon as precursor 0.1mol/L HF aqueous solution as corrosion
Liquid carries out the de- alloying of chemistry, Cu25Ni25Zr35Ti15Amorphous alloy ribbon is successively anti-with ultrapure water and absolute alcohol before treatment
Multiple ultrasonic cleaning.Will treated that amorphous alloy ribbon is placed in HF corrosive liquid, taken off under the conditions of 25 DEG C Alloying Treatment 1h and
3h.Strip is taken out, nanoporous ambrose alloy film is successively cleaned multiple times with ultrapure water and absolute alcohol, removes and is remained in hole
Chemical substance is obtained after dry using Cu25Ni25Zr35Ti15The nanoporous ambrose alloy amorphous of amorphous alloy precursor preparation is compound
Electrode material.Fig. 3 is Cu25Ni25Zr35Ti15The X ray diffracting spectrum of alloy thin band, it was demonstrated that the alloy thin band is amorphous.Fig. 5
For Cu25Ni25Zr35Ti15Amorphous alloy takes off the nanoporous ambrose alloy/amorphous combination electrode obtained after alloying at different conditions
The linear volt-ampere curve that material measures in 1M KOH, and Fig. 6 shows the Tafel slope of electrode material.Amorphous thin ribbon also table
Certain catalytic performance is now located, to the electrode material of amorphous thin ribbon removal alloying 3h in the HF corrosive liquid that concentration is 0.1mol/L
Material carries out the test of electrolysis water Hydrogen Evolution Performance, is 10mA/cm in current density2When hydrogen-evolution overpotential be only about 129mV, Tafel slope
For 39mV/dec.
Embodiment 4:
With Cu10Ni40Zr35Ti15As presoma alloy nominal composition, pure element (Cu needed for body alloy being driven
99.99wt%, Zr 99.99wt%, Ti 99.99wt%, Ni 99.99wt%), it is converted into according to the atomic percent of alloy
Quality weighs up, and the method for then using the vacuum arc melting of high-purity argon atmosphere, melting obtains Cu25Ni25Zr35Ti15Master alloy button
Ingot, melting is multiple, to guarantee that master alloy ingot ingredient is uniform.The induction heating refuse in quartz ampoule respectively by master alloy ingot,
And (copper roller diameter is continuously quickly ejected into water cooling rotary copper roller under the high-purity argon gas effect that pressure is 0.2MPa or so
220mm, 2700~3000r/min of revolving speed), form Cu10Ni40Zr35Ti15Fast quenching amorphous alloy ribbon.
With Cu10Ni40Zr35Ti15Fast quenching amorphous alloy ribbon as precursor 0.1mol/L HF aqueous solution as corrosion
Liquid carries out the de- alloying of chemistry, Cu respectively10Ni40Zr35Ti15Amorphous alloy ribbon is before treatment successively with ultrapure water and without watery wine
Smart ultrasonic cleaning repeatedly.By treated, amorphous alloy ribbon is placed in HF corrosive liquid, and Alloying Treatment is taken off under the conditions of 70 DEG C
1h.Strip is taken out, nanoporous ambrose alloy film is successively cleaned multiple times with ultrapure water and absolute alcohol, removes and is remained in hole
Chemical substance is obtained after dry using Cu10Ni40Zr35Ti15Nanoporous ambrose alloy/amorphous of amorphous alloy precursor preparation is compound
Electrode material.Fig. 3 is Cu10Ni40Zr35Ti15The X ray diffracting spectrum of alloy thin band, it was demonstrated that the alloy thin band is amorphous.Fig. 7
For Cu10Ni40Zr35Ti15Amorphous alloy takes off the nanoporous ambrose alloy/amorphous combination electrode material obtained after alloying in 1M KOH
In the linear volt-ampere curve that measures, and Fig. 8 shows the Tafel slope of electrode material.It is in concentration to amorphous thin ribbon
The electrode material of removal alloying 1h carries out the test of electrolysis water Hydrogen Evolution Performance in 0.1mol/L and 70 DEG C of HF corrosive liquid, close in electric current
Degree is 10mA/cm2When hydrogen-evolution overpotential be only about 120mV, Tafel slope is only 38mV/dec.
Claims (7)
1. a kind of nanoporous ambrose alloy/amorphous combination electrode material, it is characterised in that have three-dimensional uniform " sandwich " structure:
Surface is nanoporous ambrose alloy, and centre is noncrystal substrate, forms the compound of nanoporous ambrose alloy and amorphous；The porous ambrose alloy of nanometer
It is evenly distributed in amorphous substrate, surface layer is porous to show as continuous through-hole, and the diameter in hole is 5~30nm.
2. nanoporous ambrose alloy/amorphous combination electrode material as described in claim 1, it is characterised in that without precious metal, and
Show the catalytic activity of excellent electrolysis water liberation of hydrogen: Tafel slope is down to 38mV/dec, in 10mA/cm2Under current density
Overpotential is 120mV.
3. the preparation method of nanoporous ambrose alloy/amorphous combination electrode material as claimed in claim 1 or 2, which is characterized in that tool
Steps are as follows for body:
(1) preparation of amorphous alloy strips: select Cu-Ni-Zr-Ti alloy that flexible amorphous ribbon is prepared by melt-quenching method
Material；
(2) nanoporous ambrose alloy/amorphous combination electrode material preparation: use Cu-Ni-Zr-Ti amorphous alloy strips as forerunner
Amorphous thin ribbon is placed in various concentration HF corrosive liquid under condition of different temperatures as corrosive liquid and carries out surface by body, HF solution
De- Alloying Treatment, strip is taken out from HF solution, is cleaned multiple times through ultrapure water and absolute alcohol, removes residualization in hole
Substance is learned, nanoporous ambrose alloy/amorphous combination electrode material is finally obtained.
4. the preparation method of nanoporous ambrose alloy/amorphous combination electrode material as claimed in claim 3, which is characterized in that institute
The nominal composition of the Cu-Ni-Zr-Ti amorphous alloy presoma used in step 1) is stated as CuaNibZrcTid, wherein 10≤a≤
45,10≤b≤45,10≤c≤45,10≤d≤35, a+b+c+d=100, marked ingredient are atomic percent.
5. the preparation method of nanoporous ambrose alloy/amorphous combination electrode material as claimed in claim 3, which is characterized in that institute
State in step 1) copper roller diameter 220mm, 2700~3000r/min of revolving speed, the Cu-Ni-Zr-Ti amorphous of preparation in melt-quenching method
Alloy thin band with a thickness of 20~30 μm, width is 1~2mm；The amorphous alloy ribbon has good mechanical bend soft
Property.
6. the preparation method of nanoporous ambrose alloy/amorphous combination electrode material as claimed in claim 3, which is characterized in that institute
State surface in step 2) and take off corrosive liquid that alloying uses for the HF solution of 0.01~0.2mol/L, etching time for 0.5~
For 24 hours, taking off alloying temperature is 25~70 DEG C.
7. the preparation method of nanoporous ambrose alloy/amorphous combination electrode material as claimed in claim 3, which is characterized in that institute
The aperture for stating the porous ambrose alloy of flexible nano in step 2) is 5~30nm, and porous layer thickness is 500nm~2 μm.
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| CN110592614A (en) * | 2019-09-27 | 2019-12-20 | 西南石油大学 | Three-dimensional self-supporting electrocatalyst for preparing hydrogen by water decomposition and preparation method thereof |
| CN112877663A (en) * | 2021-01-13 | 2021-06-01 | 苏州涂冠镀膜科技有限公司 | Flexible anode material applied to fuel cell and preparation method thereof |
| CN113005460A (en) * | 2021-03-12 | 2021-06-22 | 沈阳大学 | Method for improving electrocatalytic oxidation performance of amorphous alloy |
| CN113416974A (en) * | 2021-03-22 | 2021-09-21 | 辽宁石油化工大学 | Method for rapidly preparing efficient porous silver electrocatalyst |
| CN114453587A (en) * | 2021-12-31 | 2022-05-10 | 西安理工大学 | Preparation method of nano porous copper-nickel alloy |
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| CN114453587B (en) * | 2021-12-31 | 2024-02-27 | 西安理工大学 | Preparation method of nano porous copper-nickel alloy |
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