CN114530333A - Nano porous cobalt electrode material and preparation method thereof - Google Patents
Nano porous cobalt electrode material and preparation method thereof Download PDFInfo
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- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 74
- 239000010941 cobalt Substances 0.000 title claims abstract description 74
- 239000007772 electrode material Substances 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims description 9
- 229910052751 metal Inorganic materials 0.000 claims abstract description 32
- 239000002184 metal Substances 0.000 claims abstract description 29
- 239000011148 porous material Substances 0.000 claims abstract description 20
- 210000003041 ligament Anatomy 0.000 claims abstract description 14
- 239000000126 substance Substances 0.000 claims abstract description 12
- 238000009826 distribution Methods 0.000 claims abstract description 11
- 229910000808 amorphous metal alloy Inorganic materials 0.000 claims description 49
- 229910045601 alloy Inorganic materials 0.000 claims description 32
- 239000000956 alloy Substances 0.000 claims description 32
- 230000010287 polarization Effects 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 26
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 22
- 239000003792 electrolyte Substances 0.000 claims description 15
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 14
- 229910052802 copper Inorganic materials 0.000 claims description 14
- 239000010949 copper Substances 0.000 claims description 14
- 229910052697 platinum Inorganic materials 0.000 claims description 11
- 238000010791 quenching Methods 0.000 claims description 10
- 230000000171 quenching effect Effects 0.000 claims description 10
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 9
- 238000003723 Smelting Methods 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
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- 230000007797 corrosion Effects 0.000 description 8
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- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 7
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- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 6
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
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- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
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- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
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- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
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- 239000008204 material by function Substances 0.000 description 1
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- 239000010944 silver (metal) Substances 0.000 description 1
- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/03—Making non-ferrous alloys by melting using master alloys
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/11—Making amorphous alloys
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C45/00—Amorphous alloys
- C22C45/10—Amorphous alloys with molybdenum, tungsten, niobium, tantalum, titanium, or zirconium or Hf as the major constituent
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
- C25F3/00—Electrolytic etching or polishing
- C25F3/02—Etching
- C25F3/08—Etching of refractory metals
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention discloses a nano porous cobalt electrode material which is a self-supporting nano porous strip and has a structure formed by three-dimensional continuous holes and metal ligaments which are mutually nested, wherein the metal ligaments are uniformly distributed; the cobalt in the nano-porous cobalt electrode material is simple substance cobalt. The nano porous cobalt electrode material disclosed by the invention is uniform in pore distribution, large in specific surface area and stable in test performance, realizes self-support of the electrode material, and can be directly applied to the electrochemical field as the electrode material.
Description
Technical Field
The invention relates to the technical field of nano metal functional materials, in particular to a nano porous cobalt electrode material and a preparation method thereof.
Background
The electrode material is a main factor for restricting the development of electrochemical application, so that the development of a working electrode material with excellent properties is one of important ways for improving the electrochemical performance.
As a novel functional structural material, the nano-porous metal not only has the metal property of a metal material, but also has the porous characteristic of a porous material, and the structural characteristics endow the nano-porous metal material with a plurality of unique physical and chemical properties, so that the nano-porous metal material is particularly attractive in application in electrochemistry.
Early research on nano-porous metals mainly focuses on preparation and application of noble metal nano-porous materials such as nano-porous gold and nano-porous silver, but the high cost of noble metals restricts the application development of noble metals, so researchers begin to aim at transition metal nano-porous materials.
The transition metal-based nano material has the advantages of large abundance, easiness in obtaining, simplicity in synthesis and the like, and a plurality of researches in recent years prove that the cobalt and the oxide and hydroxide nano material thereof have excellent electrochemical performance and are widely researched in the fields of supercapacitors, sensors, electrocatalysis, photocatalysis, battery energy sources and the like, and the potential of large-scale production and application of the cobalt-based material is further increased due to the lower cost of the cobalt-based material.
However, at present, research on the application of the nano-porous cobalt material as an electrode to the electrochemical field is rare, because the nano-porous cobalt is generally a powder material and needs to be adhered to carriers such as a glassy carbon electrode, carbon paper, carbon cloth and the like through media such as polyvinyl alcohol and the like for use, the method is easy to have the problem of poor performance of the electrode material due to low load capacity, uneven load and agglomeration of a nano structure, and the method has complicated working procedures and long time consumption and is not beneficial to large-scale use; however, by using the traditional chemical dealloying method, because of the severe corrosion of strong acid, huge corrosion stress is generated between the porous layer and the amorphous alloy strip, so that the porous cobalt material is easy to break, and thus, a strip-shaped material cannot be obtained, and the development of applying the nano porous cobalt as an electrode material to the electrochemical field is limited.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a nano porous cobalt electrode material which has a structure consisting of three-dimensional continuous holes and metal ligaments, is uniform in pore distribution and stable in test performance, realizes self-support of the electrode material, and can be directly applied to the electrochemical field as the electrode material.
The invention also aims to provide a preparation method of the nano-porous cobalt electrode material.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a nano-porous cobalt electrode material is a self-supporting nano-porous strip, has a structure formed by three-dimensional continuous holes and metal ligaments which are mutually nested, and the metal ligaments are uniformly distributed; the cobalt in the nano-porous cobalt electrode material is simple substance cobalt.
Furthermore, the pore diameter distribution of the holes is uniform and is in normal distribution.
Further, the specific surface area of the nano-porous cobalt electrode material is 13.9 times that of the original amorphous alloy strip.
Further, the elemental cobalt is 26.85-84.01% by atomic percentage.
A preparation method of a nano-porous cobalt electrode material comprises the following steps:
s1: according to the target alloy ZraAlbCocMdProportioning all metal simple substances, and smelting to obtain a master alloy; wherein a is more than or equal to 50at percent and less than or equal to 60at percent, b is more than or equal to 13at percent and less than or equal to 18at percent, c is more than or equal to 23at percent and less than or equal to 28at percent, d is more than or equal to 0at percent and less than or equal to 5at percent, and M is any one of metal elements such as Au, Ag, Ni, Nb and the like;
s2: the master alloy obtained in S1 was treated by single roll rotary quenching to obtain ZraAlbCocMdAn amorphous alloy strip;
s3: in a standard three-electrode system, Zr obtained in S2aAlbCocMdThe amorphous alloy strip is taken as a working electrode, a platinum sheet is taken as a counter electrode, and Zr is treated by a constant potential polarization methodaAlbCocMdThe amorphous alloy strip is subjected to electrochemical dealloying treatment and is directly added with ZraAlbCocMdAnd (4) obtaining the nano porous cobalt electrode material on the amorphous alloy strip electrode.
Further, the standard three-electrode system specifically comprises: with ZraAlbCocMdThe amorphous alloy strip is used as a working electrode, a platinum electrode is used as a counter electrode, a saturated calomel electrode is used as a reference electrode, and NH is used4F and (NH)4)2SO4The mixed aqueous solution is used as electrolyte and is subjected to constant potential polarization under a certain polarization potential.
Further, the NH4The concentration of F is 0.1-0.15M, (NH)4)2SO4The concentration is 0.1-1M.
Further, the polarization potential is 1.5-2.5V, and the polarization time is 1-4 h.
Further, the number of revolutions of the copper roller during the strip throwing by the single-roller rotary quenching method is 2200 rpm.
The invention has the beneficial effects that:
1. the nano porous cobalt electrode material is a self-supporting nano porous strip, ammonium ions in ammonium fluoride are weakly acidic through electrochemical dealloying, the acidity of an acid solution is reduced, a certain amount of ammonium sulfate is added to adjust the pH value of the solution, so that the whole solution is also weakly acidic, the corrosion capability of the solution is reduced, the generation of corrosion stress is reduced, the cobalt atoms are sufficiently diffused for time, the corrosion can be started only under the condition of external voltage, the corrosion process is milder and more controllable, the effect of reducing the corrosion stress is achieved, the finally prepared nano porous cobalt strip cannot be broken, the problem that the nano porous cobalt is easy to break when the strip material is prepared is solved, the specific self-supporting structure can be directly applied to the electrochemical field as the electrode material, further treatment is not needed, and the low load caused by a load treatment structure is avoided, the problems of uneven load, complex process and long consumed time are solved, the problem of reduction of the specific surface area caused by agglomeration in the electrochemical test process is also avoided, and the test efficiency and stability are ensured.
2. The nano porous cobalt electrode material is amorphous alloy ZraAlbCocMdPerforming electrochemical dealloying for precursor ZraAlbCocMdThe metal elements in the amorphous alloy are disordered in atomic scale, orientation is avoided, the component distribution is uniform enough, crystal defects such as crystal boundaries are avoided, in the process of dealloying, active metal atoms are corroded, and stable metal atoms form ligaments through diffusion, so that the nano-porous cobalt electrode material with a uniform nano-porous structure is obtained, the pore diameters are uniformly distributed, when current passes through strips, electron transfer is more uniform, the current corresponds in the process of electrochemical testing, and the testing is more stable; the analysis of the pore diameter shows that the pore diameter is normally distributed, and further proves that the pores and the metal ligaments are uniformly distributed.
3. The nano porous cobalt electrode material has large response current, good performance and larger specific surface area which is 13.9 times of the specific surface area of the original amorphous alloy strip, improves the contact efficiency of the electrode material and an electrochemical solution, provides a diffusion and transmission channel required by reaction molecules for the test of electrochemical performance, provides more attachment points for reaction, provides more redox places, has more active sites and accelerates the reaction, and has the degradation rate of methyl orange up to 98.20%.
4. The preparation method of the nano porous cobalt electrode material through electrochemical dealloying has the advantages of simple preparation process, low cost, capability of further large-scale production, better practicability, no need of strong acid solution in the whole process, environmental friendliness and contribution to environmental protection.
Drawings
Fig. 1 to 6 are SEM images of the surfaces of the nanoporous cobalt electrode materials obtained in examples 1 to 6, respectively.
Fig. 7(a) is a TEM image of the nanoporous cobalt electrode material obtained in example 5.
FIG. 7(b) is a TEM selected area diffraction spectrum analysis chart of the nano-porous cobalt electrode material obtained in example 5.
Fig. 8 is a statistical graph of the pore size distribution of the nanoporous cobalt electrode material obtained in example 5.
FIG. 9 is a plot of capacitance current versus scan rate for the nanoporous cobalt electrode material and ZrAlCo amorphous strips obtained from example 5at a voltage of 0.05V.
FIG. 10 is a diagram of an ultraviolet-visible spectrum of a ZrAlCo amorphous alloy ribbon, a pure Co simple substance, and a nano-porous cobalt electrode material obtained in example 5 as a working electrode for degrading methyl orange.
Detailed Description
In order to better understand the technical content of the present invention, specific embodiments are described below with reference to the accompanying drawings.
The raw materials in the following examples were all purchased from commercial sources unless otherwise specified.
Example 1
S1: taking 40g of pure metals of Zr, Al, Co and Au (the purity is 99.99%) according to the atomic ratio of Zr to Al to Co to Au of 56:13:28:3, and respectively carrying out ultrasonic cleaning by using acetone and deionized water to remove surface pollutants. And mixing the cleaned pure metals of Zr, Al, Co and Au in a crucible in an electric arc melting furnace, and melting under the argon atmosphere, wherein the melting current is about 180A. And two side surfaces of the alloy ingot are respectively smelted twice during smelting, and each time lasts for about 3 min.
S2: taking the smelted Zr56Al13Co28Au3About 10g of mother alloy is placed at the bottom of a specially-made quartz tube (the diameter of the quartz tube is 16mm, the bottom opening is 5mm), and the mother alloy is treated by a single copper roller melt-spinning quenching method under the argon atmosphere to obtain Zr56Al13Co28Au3An amorphous alloy strip, the revolution of a copper roller during strip throwing is 2200 revolutions per minute, the alloy is melted to be in a molten state through induction heating and then is sprayed, and finally Zr with the width of 5mm and the thickness of 20-80 mu m is obtained56Al13Co28Au3Amorphous alloy ribbon.
S3: zr obtained56Al13Co28Au3Amorphous formThe alloy strip was cut to a length of about 1.5cm and ultrasonically cleaned with absolute ethanol and deionized water, respectively, to remove surface contaminants. It was then spot welded to a nickel wire and coated with insulation at the weld for use in electrochemical experiments. Electrochemical deposition was carried out in a standard three-electrode system to treat the Zr65Al13Co23Au3The amorphous alloy strip is used as a working electrode, a platinum sheet is used as a counter electrode (the area of the counter electrode is controlled to be 0.6 x 1.1cm), a Saturated Calomel Electrode (SCE) is used as a reference electrode to carry out a constant potential polarization experiment, and the electrolyte is 60mL of 0.1M NH4F and 0.1M (NH)4)2SO4The polarization potential of the mixed aqueous solution is 1.9V vs. SCE, and the polarization time is 3 h. And after electrochemical dealloying, washing the sample with deionized water for multiple times to remove residual electrolyte on the surface, thereby obtaining the nano porous cobalt electrode material.
Example 2
S1: taking 40g of pure metals of Zr, Al, Co and Au (the purity is 99.99%) according to the atomic ratio of Zr to Al to Co to Au of 56:13:28:3, and respectively carrying out ultrasonic cleaning by using acetone and deionized water to remove surface pollutants. And mixing the cleaned pure metals of Zr, Al, Co and Au in a crucible in an electric arc melting furnace, and melting under the argon atmosphere, wherein the melting current is about 180A. And two side surfaces of the alloy ingot are respectively smelted twice during smelting, and each time lasts for about 3 min.
S2: taking the smelted Zr56Al13Co28Au3About 10g of mother alloy is placed at the bottom of a specially-made quartz tube (the diameter of the quartz tube is 16mm, the bottom opening is 5mm), and the mother alloy is treated by a single copper roller melt-spinning quenching method under the argon atmosphere to obtain Zr56Al13Co28Au3An amorphous alloy strip, the revolution of a copper roller during strip throwing is 2200 revolutions per minute, the alloy is melted to be in a molten state through induction heating and then is sprayed, and finally Zr with the width of 5mm and the thickness of 20-80 mu m is obtained56Al13Co28Au3Amorphous alloy ribbon.
S3: zr obtained56Al13Co28Au3Cutting off a sample with the length of about 1.5cm from the amorphous alloy strip, and respectively carrying out ultrasonic cleaning by using absolute ethyl alcohol and deionized water to remove surface stainsAnd (5) dyeing the materials. It was then spot welded to a nickel wire and coated with insulation at the weld for use in electrochemical experiments. Electrochemical deposition was carried out in a standard three-electrode system to treat the Zr56Al13Co28Au3The amorphous alloy strip is used as a working electrode, a platinum sheet is used as a counter electrode (the area of the counter electrode is controlled to be 0.6 x 1.1cm), a Saturated Calomel Electrode (SCE) is used as a reference electrode to carry out a constant potential polarization experiment, and the electrolyte is 60mL of 0.15M NH4F and 0.1M (NH)4)2SO4The polarization potential of the mixed aqueous solution is 2.5V vs. SCE, and the polarization time is 3 h. And after electrochemical dealloying, washing the sample with deionized water for multiple times to remove residual electrolyte on the surface, thereby obtaining the nano porous cobalt electrode material.
Example 3
S1: taking 40g of pure metals (with the purity of 99.99%) of Zr, Al, Co and Ni according to the Zr-Al-Co-Ni atomic ratio of 60:14:23:3, and respectively carrying out ultrasonic cleaning by using acetone and deionized water to remove surface pollutants. And mixing the cleaned pure metals of Zr, Al, Co and Ni in a crucible in an electric arc melting furnace, and melting under the argon atmosphere, wherein the melting current is about 180A. And two side surfaces of the alloy ingot are respectively smelted twice during smelting, and each time lasts for about 3 min.
S2: taking the smelted Zr60Al14Co23Ni3About 10g of mother alloy is placed at the bottom of a specially-made quartz tube (the diameter of the quartz tube is 16mm, the bottom opening is 5mm), and the mother alloy is treated by a single copper roller melt-spinning quenching method under the argon atmosphere to obtain Zr60Al14Co23Ni3An amorphous alloy strip, the revolution of a copper roller during strip throwing is 2200 revolutions per minute, the alloy is melted to be in a molten state through induction heating and then is sprayed, and finally Zr with the width of 5mm and the thickness of 20-80 mu m is obtained50Al18Co27Ag5Amorphous alloy ribbon.
S3: zr obtained60Al14Co23Ni3A sample with the length of about 1.5cm is cut off from the amorphous alloy strip, and the sample is respectively subjected to ultrasonic cleaning by absolute ethyl alcohol and deionized water to remove surface pollutants. It was then spot welded to a nickel wire and coated with insulation at the weld for use in electrochemical experiments. Electrochemical deviceChemical deposition was performed in a standard three-electrode system to treat the good Zr60Al14Co23Ni3The amorphous alloy strip is used as a working electrode, a platinum sheet is used as a counter electrode (the area of the counter electrode is controlled to be 0.6 x 1.1cm), a Saturated Calomel Electrode (SCE) is used as a reference electrode to carry out a constant potential polarization experiment, and the electrolyte is 60mL of 0.135M NH4F and 0.5M (NH)4)2SO4The polarization potential of the mixed aqueous solution is 1.9V vs. SCE, and the polarization time is 1 h. And after electrochemical dealloying, washing the sample with deionized water for multiple times to remove residual electrolyte on the surface, thereby obtaining the nano porous cobalt electrode material.
Example 4
S1: taking 40g of pure metals (with the purity of 99.99%) of Zr, Al, Co and Nb according to the atomic ratio of Zr to Al to Co to Nb of 56:13:28:3, and respectively carrying out ultrasonic cleaning by using acetone and deionized water to remove surface pollutants. And mixing the cleaned pure metals of Zr, Al, Co and Nb in a crucible in an electric arc melting furnace, and melting under the argon atmosphere, wherein the melting current is about 180A. And two side surfaces of the alloy ingot are respectively smelted twice during smelting, and each time lasts for about 3 min.
S2: taking the smelted Zr56Al13Co28Nb3About 10g of mother alloy is placed at the bottom of a specially-made quartz tube (the diameter of the quartz tube is 16mm, the bottom opening is 5mm), and the mother alloy is treated by a single copper roller melt-spinning quenching method under the argon atmosphere to obtain Zr56Al13Co28Nb3An amorphous alloy strip, the revolution of a copper roller during strip throwing is 2200 revolutions per minute, the alloy is melted to be in a molten state through induction heating and then is sprayed, and finally Zr with the width of 5mm and the thickness of 20-80 mu m is obtained56Al13Co28Nb3Amorphous alloy ribbon.
S3: zr obtained56Al13Co28Nb3A sample with the length of about 1.5cm is cut off from the amorphous alloy strip, and the sample is respectively subjected to ultrasonic cleaning by absolute ethyl alcohol and deionized water to remove surface pollutants. It was then spot welded to a nickel wire and coated with insulation at the weld for use in electrochemical experiments. Electrochemical deposition was carried out in a standard three-electrode system to treat the good Zr56Al13Co28Nb3The amorphous alloy strip is used as a working electrode, a platinum sheet is used as a counter electrode (the area of the counter electrode is controlled to be 0.6 x 1.1cm), a Saturated Calomel Electrode (SCE) is used as a reference electrode to carry out a constant potential polarization experiment, and the electrolyte is 60mL of 0.135M NH4F and 1M (NH)4)2SO4The polarization potential of the mixed aqueous solution is 1.5V vs. SCE, and the polarization time is 3 h. And after electrochemical dealloying, washing the sample with deionized water for multiple times to remove residual electrolyte on the surface, thereby obtaining the nano porous cobalt electrode material.
Example 5
S1: taking 40g of pure metals of Zr, Al and Co (the purity is 99.99%) according to the atomic ratio of Zr to Al to Co being 56:16:28, and respectively carrying out ultrasonic cleaning by using acetone and deionized water to remove surface pollutants. And mixing the cleaned pure metals of Zr, Al and Co in a crucible in an electric arc melting furnace, and melting under the argon atmosphere, wherein the melting current is about 180A. And two side surfaces of the alloy ingot are respectively smelted twice during smelting, and each time lasts for about 3 min.
S2: taking the smelted Zr56Al16Co28About 10g of mother alloy is placed at the bottom of a specially-made quartz tube (the diameter of the quartz tube is 16mm, the bottom opening is 5mm), and the mother alloy is treated by a single copper roller melt-spinning quenching method under the argon atmosphere to obtain Zr56Al16Co28An amorphous alloy strip, the revolution of a copper roller during strip throwing is 2200 revolutions per minute, the alloy is melted to be in a molten state through induction heating and then is sprayed, and finally Zr with the width of 5mm and the thickness of 20-80 mu m is obtained56Al16Co28Amorphous alloy ribbon.
S3: zr obtained56Al16Co28A sample with the length of about 1.5cm is cut off from the amorphous alloy strip, and the sample is respectively subjected to ultrasonic cleaning by absolute ethyl alcohol and deionized water to remove surface pollutants. It was then spot welded to a nickel wire and coated with insulation at the weld for use in electrochemical experiments. Electrochemical deposition was carried out in a standard three-electrode system to treat the Zr56Al16Co28The amorphous alloy strip is used as a working electrode, a platinum sheet is used as a counter electrode (the area of the counter electrode is controlled to be 0.6 x 1.1cm), a Saturated Calomel Electrode (SCE) is used as a reference electrode to carry out a constant potential polarization experiment, and the electrolyte is 60mL and 0.135M NH4F and 1M (NH)4)2SO4The polarization potential of the mixed aqueous solution is 1.9V vs. SCE, and the polarization time is 3 h. And after electrochemical dealloying, washing the sample with deionized water for multiple times to remove residual electrolyte on the surface, thereby obtaining the nano porous cobalt electrode material.
Example 6
S1: taking 40g of pure metals of Zr, Al, Co and Ag (the purity is 99.99%) according to the atomic ratio of Zr, Al, Co and Ag being 50:18:27:5, and respectively carrying out ultrasonic cleaning by using acetone and deionized water to remove surface pollutants. And mixing the cleaned pure metals of Zr, Al and Co in a crucible in an electric arc melting furnace, and melting under the argon atmosphere, wherein the melting current is about 180A. And two side surfaces of the alloy ingot are respectively smelted twice during smelting, and each time lasts for about 3 min.
S2: taking the smelted Zr50Al18Co27Ag5About 10g of mother alloy is placed at the bottom of a specially-made quartz tube (the diameter of the quartz tube is 16mm, the bottom opening is 5mm), and the mother alloy is treated by a single copper roller melt-spinning quenching method under the argon atmosphere to obtain Zr50Al18Co27Ag5An amorphous alloy strip, the revolution of a copper roller during strip throwing is 2200 revolutions per minute, the alloy is melted to be in a molten state through induction heating and then is sprayed, and finally Zr with the width of 5mm and the thickness of 20-80 mu m is obtained50Al18Co27Ag5Amorphous alloy ribbon.
S3: zr obtained50Al18Co27Ag5A sample with the length of about 1.5cm is cut off from the amorphous alloy strip, and the sample is respectively subjected to ultrasonic cleaning by absolute ethyl alcohol and deionized water to remove surface pollutants. It was then spot welded to a nickel wire and coated with insulation at the weld for use in electrochemical experiments. Electrochemical deposition was carried out in a standard three-electrode system to treat the Zr50Al18Co27Ag5The amorphous alloy strip is used as a working electrode, a platinum sheet is used as a counter electrode (the area of the counter electrode is controlled to be 0.6 x 1.1cm), a Saturated Calomel Electrode (SCE) is used as a reference electrode to carry out a constant potential polarization experiment, and the electrolyte is 60mL of 0.135M NH4F and 1M (NH)4)2SO4The polarization potential is 1.9V vs. SCE, and the polarization time is 4h. And after electrochemical dealloying, washing the sample with deionized water for multiple times to remove residual electrolyte on the surface, thereby obtaining the nano porous cobalt electrode material.
[ characterizations ] of
1. SEM and EDS
Fig. 1 to 6 are SEM images of the surfaces of the nanoporous cobalt electrode materials obtained in examples 1 to 6, respectively, and it can be seen from the SEM images that a nanoporous structure with uniform pore diameter is formed on the surface of the amorphous alloy ribbon after dealloying, and the nanoporous cobalt is bonded with the amorphous alloy ribbon without an adhesive, and can be directly used as an electrode material.
Table 1 shows EDS data of corresponding regions of the nanoporous cobalt electrode materials obtained in examples 1-6
TABLE 1
As can be seen from EDS data of each example and an SEM image, the nano-porous cobalt electrode material obtained by each example is a nano-porous material of simple substance cobalt, and the atomic percent content of the simple substance cobalt is 26.85-84.01%; as can be seen from the comparison of the data of the embodiment 1 and the embodiment 2, when the concentration of the electrolyte is low, the corrosion depth is insufficient, so that the element content in the amorphous alloy strip matrix is too high; from the comparison of the data of examples 5 and 6, it can be seen that the average pore size is reduced from 44.7nm to 24.6nm by adding a small amount of silver element into the ZrAlCo alloy system, which indicates that the ligament and pore size of the nanoporous cobalt can be effectively refined by adding the silver element.
2、TEM
Fig. 7 is a TEM image of the nano-porous cobalt electrode material obtained in example 5, wherein black shaded areas and white bright areas are clearly observed from the matrix in fig. 7(a), wherein the black shaded areas represent porous structural ligaments, the white bright areas represent porous pores, and the uniformly distributed white bright areas and black shaded areas illustrate that the pore sizes and the ligaments are uniformly distributed, which is consistent with the result observed in the SEM image. In order to better determine the components of the nano-porous structure formed after dealloying, TEM selective diffraction spectrum analysis is performed on the nano-porous structure, and after calibration, as shown in fig. 7(b), three main diffraction rings are (312), (204) and (513) crystal planes of Co, which further proves that the dealloyed amorphous alloy is mainly a nano-porous structure of simple substance Co.
3. Pore size distribution statistical map
Fig. 8 is a statistical graph of the pore size distribution of the nanoporous cobalt electrode material obtained in example 5, and it can be seen from the graph that the pore size distribution is normally distributed, mainly around 40nm, and the pore size distribution is uniform, which further proves the theory that the amorphous alloy generates a uniform nanoporous structure in the dealloying process.
4. Specific surface area
FIG. 9 is a fitting graph of capacitance current and scanning rate of the nanoporous cobalt electrode material and the ZrAlCo amorphous strip obtained in example 5at a voltage of 0.05V, a cyclic voltammetry test is performed on the two materials under a potential condition of 0.05V, response current difference values of oxidation reaction and reduction reaction of the materials at the potential can be obtained, a scanning rate of 10-50mV/s is selected to obtain current difference values at the scanning rates, then linear fitting is performed, the larger the slope of the linear fitting result indicates that the performance in the electrochemical test is better, the ratio of the slope of the fitting straight line is the ratio of the electrochemical active area, and as can be seen from the graph, the obtained result indicates that the slope of the nanoporous cobalt is 13.9 times that of the amorphous alloy strip, that is, the electrochemical specific surface area is 13.9 times that of the amorphous alloy strip, and the electrode material has a larger electrochemical active specific surface area, thereby providing more active sites and accelerating the reaction.
[ Performance test ]
A ZrAlCo amorphous alloy strip, a pure Co simple substance and the nano-porous cobalt electrode material obtained in example 5 are used as working electrodes, a platinum sheet is used as a counter electrode, a saturated calomel electrode is used as a reference electrode, a Methyl Orange (MO) solution with a simulated pollutant of 20mg/L is applied with a square wave potential of 1.5V by using an electrochemical square wave method, a degradation experiment is carried out on methyl orange, and the absorbance of the methyl orange solution before and after degradation is tested, and the result is shown in FIG. 10.
As can be seen from fig. 10, the degradation rates of the pure Co simple substance and the ZrAlCo amorphous alloy strip on methyl orange can only reach 63.03% and 90.53%, respectively, while the degradation rate of the nano-porous cobalt electrode material obtained in example 5 on methyl orange can reach 98.20%. The high catalytic activity of the nano-porous cobalt electrode material benefits from high specific surface area, and ligaments formed by the mutually nested pore channels and the nano-porous structure formed by the metal ligaments are uniformly distributed, so that the dispersity and the specific surface area are increased, and the contact efficiency with pollutants is improved; the porous structure of the porous structure can enable liquid to flow rapidly, provide channels for diffusion and transmission of guest reaction molecules, provide more attachment points for degradation reaction, provide more redox reaction sites and accelerate reaction speed; on the other hand, the porous Co catalytic matrix material does not need to be subjected to load treatment, so that the material can be self-supported, the problem of reduction of the specific surface area caused by agglomeration is solved, the stability of the electrode material is maintained, and the catalytic activity of the electrode material is ensured.
Although the present invention has been described with reference to the preferred embodiments, it is not intended to be limited thereto. Those skilled in the art can make various changes and modifications without departing from the spirit and scope of the invention. Therefore, the protection scope of the present invention should be determined by the appended claims.
Claims (9)
1. A nanoporous cobalt electrode material, characterized in that: the nano-porous cobalt electrode material is a self-supporting nano-porous strip, has a structure consisting of three-dimensional continuous holes which are mutually nested and metal ligaments, and the metal ligaments are uniformly distributed; the cobalt in the nano-porous cobalt electrode material is simple substance cobalt.
2. The nanoporous cobalt electrode material of claim 1, wherein: the pore diameters of the holes are uniformly distributed and are in normal distribution.
3. The nanoporous cobalt electrode material of claim 1, wherein: the specific surface area of the nano-porous cobalt electrode material is 13.9 times of that of the original amorphous alloy strip.
4. The nanoporous cobalt electrode material of claim 1, wherein: the elemental cobalt has an atomic percent content of 26.85-84.01%.
5. A method of preparing a nanoporous cobalt electrode material according to any one of claims 1 to 4, comprising the steps of:
s1: according to the target alloy ZraAlbCocMdProportioning all metal simple substances, and smelting to obtain a master alloy; wherein a is more than or equal to 50at percent and less than or equal to 60at percent, b is more than or equal to 13at percent and less than or equal to 18at percent, c is more than or equal to 23at percent and less than or equal to 28at percent, d is more than or equal to 0at percent and less than or equal to 5at percent, and M is any one of metal elements such as Au, Ag, Ni, Nb and the like;
s2: the master alloy obtained in S1 was treated by single roll rotary quenching to obtain ZraAlbCocMdAn amorphous alloy strip;
s3: in a standard three-electrode system, Zr obtained in S2aAlbCocMdThe amorphous alloy strip is taken as a working electrode, a platinum sheet is taken as a counter electrode, and Zr is treated by a constant potential polarization methodaAlbCocMdElectrochemical dealloying treatment is carried out on the amorphous alloy strip, and Zr is directly added inaAlbCocMdAnd (4) obtaining the nano porous cobalt electrode material on the amorphous alloy strip electrode.
6. The preparation method of the nanoporous cobalt electrode material according to claim 5, wherein the standard three-electrode system is specifically: with ZraAlbCocMdThe amorphous alloy strip is used as a working electrode, a platinum electrode is used as a counter electrode, a saturated calomel electrode is used as a reference electrode, and NH is used4F and (NH)4)2SO4The mixed aqueous solution is used as electrolyte and is subjected to constant potential polarization under a certain polarization potential.
7. The method for preparing a nanoporous cobalt electrode material according to claim 6, wherein: the NH4The concentration of F is 0.1-0.15M, (NH)4)2SO4The concentration is 0.1-1M.
8. The method for preparing a nanoporous cobalt electrode material according to claim 6, wherein: the polarization potential is 1.5-2.5V, and the polarization time is 1-4 h.
9. The method for preparing a nanoporous cobalt electrode material according to claim 5, wherein: the revolution number of the copper roller is 2200rpm when the single-roller rotary quenching method is used for strip throwing.
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