CN114530333B - 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 73
- 239000010941 cobalt Substances 0.000 title claims abstract description 72
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 71
- 239000007772 electrode material Substances 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 32
- 239000002184 metal Substances 0.000 claims abstract description 27
- 239000011148 porous material Substances 0.000 claims abstract description 21
- 210000003041 ligament Anatomy 0.000 claims abstract description 14
- 238000009826 distribution Methods 0.000 claims abstract description 8
- 229910000808 amorphous metal alloy Inorganic materials 0.000 claims description 49
- 229910045601 alloy Inorganic materials 0.000 claims description 31
- 239000000956 alloy Substances 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 31
- 230000010287 polarization Effects 0.000 claims description 28
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 18
- 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
- 238000002074 melt spinning Methods 0.000 claims description 14
- 229910017855 NH 4 F Inorganic materials 0.000 claims description 10
- 238000010791 quenching Methods 0.000 claims description 10
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 9
- 229910052697 platinum Inorganic materials 0.000 claims description 9
- 230000000171 quenching effect Effects 0.000 claims description 9
- 238000003723 Smelting Methods 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 238000012360 testing method Methods 0.000 abstract description 6
- 239000008367 deionised water Substances 0.000 description 18
- 229910021641 deionized water Inorganic materials 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
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- 230000008018 melting Effects 0.000 description 12
- 238000002844 melting Methods 0.000 description 12
- 239000010453 quartz Substances 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 238000004506 ultrasonic cleaning Methods 0.000 description 12
- 229910052726 zirconium Inorganic materials 0.000 description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 11
- 239000000463 material Substances 0.000 description 9
- 230000007797 corrosion Effects 0.000 description 8
- 238000005260 corrosion Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 238000006731 degradation reaction Methods 0.000 description 7
- 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
- 229940012189 methyl orange Drugs 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 6
- 238000005520 cutting process Methods 0.000 description 6
- 238000004070 electrodeposition Methods 0.000 description 6
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
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- 230000003197 catalytic effect Effects 0.000 description 3
- 238000000840 electrochemical analysis Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000007769 metal material Substances 0.000 description 3
- 239000007783 nanoporous material Substances 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 241001391944 Commicarpus scandens Species 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
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- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 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
- 229910000531 Co alloy Inorganic materials 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- -1 ammonium ions Chemical class 0.000 description 1
- 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
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
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- 239000004744 fabric Substances 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
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- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
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- 238000006722 reduction reaction Methods 0.000 description 1
- 235000009566 rice Nutrition 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
- 238000001228 spectrum Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- 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
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- 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
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- C22C1/11—Making amorphous alloys
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- C22C—ALLOYS
- C22C45/00—Amorphous alloys
- C22C45/10—Amorphous alloys with molybdenum, tungsten, niobium, tantalum, titanium, or zirconium or Hf as the major constituent
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Abstract
The invention discloses a nano porous cobalt electrode material which is a self-supporting nano porous strip and has a structure formed by mutually nested three-dimensional continuous holes and metal ligaments, wherein the metal ligaments are uniformly distributed; cobalt in the nano porous cobalt electrode material is elemental cobalt. The nano porous cobalt electrode material has uniform pore distribution, large specific surface area and stable testing performance, realizes self-support of the electrode material, and can be directly used as the electrode material to be applied to the electrochemical field.
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
Electrode materials are a major factor limiting development of electrochemical applications, and therefore, development of working electrode materials excellent in properties is one of important ways to improve electrochemical performance.
The nano porous metal is taken as a novel functional structural material, has the metal property of the metal material and the porous property of the porous material, and the structural characteristics endow the nano porous metal material with a plurality of unique physical and chemical properties, so that the application of the nano porous metal material in the aspect of electrochemistry is particularly attractive.
Early researches on nano porous metals mainly focused on the preparation and application of noble metal nano porous materials such as nano porous gold, nano porous silver and the like, but the high cost of noble metals restricts the application development of the noble metals, so researchers start to direct the eyes to transition metal nano porous materials.
The transition metal-based nanomaterial has the advantages of large abundance, easy acquisition, simple synthesis and the like, and many researches in recent years prove that cobalt and oxides and hydroxides thereof have excellent electrochemical properties, 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 nanomaterial is further increased due to the lower cost of the cobalt-based nanomaterial.
However, the research of applying the nano porous cobalt material as an electrode to the electrochemical field is not very common at present, because the nano porous cobalt is generally a powder material, and the nano porous cobalt is required to be adhered to a carrier such as a glassy carbon electrode, carbon paper, carbon cloth and the like through a medium such as polyvinyl alcohol and the like for use, the method is easy to have the problem of poor electrode material performance caused by low load capacity, uneven load and aggregation of nano structures, and the method has complex process, long time consumption and is unfavorable for large-scale use; by using the traditional chemical dealloying method, huge corrosion stress is generated between the porous layer and the amorphous alloy strip due to strong corrosion of strong acid, so that the porous cobalt material is easy to break, and therefore, the strip material cannot be obtained, and the development of the application of the nano porous cobalt as an electrode material in the electrochemical field is limited.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a nano porous cobalt electrode material which has a structure consisting of three-dimensional continuous holes and metal ligaments, has uniform pore distribution and stable testing performance, realizes self-support of the electrode material, and can be directly used as the electrode material to be applied to the electrochemical field.
Another object of the present invention is to provide a method for preparing a nanoporous cobalt electrode material.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
The preparation method of the nano porous cobalt electrode material comprises the following steps:
S1: proportioning metal elements according to a target alloy Zr aAlbCocMd, and smelting to obtain a master alloy; wherein, a is more than or equal to 50 percent and less than or equal to 60 percent and at percent, b is more than or equal to 13 percent and less than or equal to at percent, c is more than or equal to 23 percent and less than or equal to at percent and less than or equal to 28at percent, d is more than or equal to 0 percent and less than or equal to 5 percent and at percent, and M is any one of metal elements such as Au, ag, ni, nb and the like;
s2: treating the master alloy obtained in the step S1 by a single-roller spin quenching method to obtain Zr aAlbCocMd amorphous alloy strips;
s3: in a standard three-electrode system, taking a Zr aAlbCocMd amorphous alloy strip obtained in the step S2 as a working electrode, taking a platinum sheet as a counter electrode, taking a saturated calomel electrode as a reference electrode, taking a mixed aqueous solution of NH 4 F and (NH 4)2SO4) as an electrolyte, carrying out constant potential polarization under a certain polarization potential, carrying out electrochemical dealloying treatment on the Zr aAlbCocMd amorphous alloy strip by a constant potential polarization method, and directly obtaining a nano-porous cobalt electrode material on the Zr aAlbCocMd amorphous alloy strip electrode;
Wherein the nano porous cobalt electrode material is a self-supporting nano porous strip and has mutually nested three-dimensional continuous structure
The structure comprises holes and metal ligaments, and the metal ligaments are uniformly distributed; the cobalt in the nano porous cobalt electrode material is elemental cobalt, and the atomic percentage content of the elemental cobalt is 26.85-84.01%.
Further, the pore diameters of the holes are uniformly distributed and normally distributed.
Further, the specific surface area of the nano porous cobalt electrode material is 13.9 times of that of the original amorphous alloy strip.
Further, the concentration of NH 4 F is 0.1-0.15M, (NH 4)2SO4 concentration is 0.1-1M).
Further, the polarization potential is 1.5-2.5V, and the polarization time is 1-4h.
Further, the number of copper roller revolutions during the melt-spinning by the single roller spin-quenching method is 2200rpm.
The invention has the beneficial effects that:
1. The self-supporting nano porous cobalt electrode material is a self-supporting nano porous strip, ammonium ions in ammonium fluoride are weak acid through electrochemical dealloying, the acidity of an acid solution is reduced, and a certain amount of ammonium sulfate is added to adjust the pH value, so that the whole solution is weak acid, the corrosion capacity is reduced, the generation of corrosion stress is reduced, the sufficient diffusion time of cobalt atoms is given, the corrosion can be started only under the condition of external voltage, the corrosion process is milder and controllable, the effect of reducing the corrosion stress is achieved, the finally prepared nano porous cobalt strip cannot be broken, the problem that nano porous cobalt is easy to break when the strip material is prepared is solved, the special self-supporting structure can be directly applied to the electrochemical field as the electrode material, no further treatment is needed, the problems of low load capacity, uneven load and complex procedure and long consumption time caused by a load treatment structure are avoided, the problem of reducing 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 of the invention takes amorphous alloy Zr aAlbCocMd as a precursor for electrochemical dealloying,
The Zr aAlbCocMd amorphous alloy has the advantages that metal elements are distributed in a disordered way on an atomic scale, orientation is not generated, component distribution is uniform enough, crystal defects such as grain boundaries and the like are avoided, active metal atoms are corroded in the dealloying process, and stable metal atoms form ligaments through diffusion, so that the rice porous cobalt electrode material with a uniform nano porous structure is obtained, the pore diameters are uniformly distributed, electrons are transferred more uniformly when current passes through a strip, and accordingly the current is corresponding in the electrochemical test process, and the test 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 the advantages of large response current, better performance and larger specific surface area which is 13.9 times of the specific surface area of the original amorphous alloy strip, the larger specific surface area improves the contact efficiency of the electrode material and an electrochemical solution, provides diffusion and transmission channels required by reaction molecules for the test of electrochemical performance, provides more attachment points for the reaction and more redox sites, thereby having more active sites, accelerating the reaction, and the degradation rate of methyl orange can reach 98.20 percent.
4. The invention prepares the nano porous cobalt electrode material through electrochemical dealloying, has simple preparation process, low cost, further mass production and better practicability, does not need strong acid solution in the whole process, is environment-friendly and is beneficial to environmental protection.
Drawings
FIGS. 1-6 are SEM images of the surfaces of the nanoporous cobalt electrode materials obtained in examples 1-6, 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 pore size distribution of the nanoporous cobalt electrode material obtained in example 5.
FIG. 9 is a plot of capacitance current versus scan rate fit for the nanoporous cobalt electrode material and ZrAlCo amorphous strips obtained in example 5 at a voltage of 0.05V.
FIG. 10 is a graph of ultraviolet and visible light spectrum of methyl orange degradation using ZrAlCo amorphous alloy strips, pure Co simple substance, and the nano-porous cobalt electrode material obtained in example 5 as working electrodes.
Detailed Description
For a better understanding of the technical content of the present invention, specific examples are set forth below, along with the accompanying drawings.
Unless otherwise indicated, the starting materials in the examples below were all purchased commercially.
Example 1
S1: taking Zr, al, co, au pure metal (purity is 99.99%) of 40g according to atomic ratio of 56:13:28:3 of Zr to Al to Co to Au, and respectively carrying out ultrasonic cleaning by using acetone and deionized water to remove surface pollutants. The cleaned Zr, al, co, au pure metal is mixed in a crucible in an arc melting furnace and is melted under the argon atmosphere, and the melting current is about 180A. During smelting, the two side surfaces of the alloy ingot are respectively smelted twice, and about 3 min parts of the alloy ingot are smelted each time.
S2: about 10 percent of melted Zr 56Al13Co28Au3 master alloy g is taken and placed at the bottom of a specially made quartz tube (the diameter of the quartz tube is 16 mm, the bottom opening is 5 mm), the Zr 56Al13Co28Au3 amorphous alloy strip is obtained through a single copper roller melt-spinning quenching method under the argon atmosphere, the copper roller revolution is 2200 rpm during melt-spinning, and the injection is carried out when the alloy is melted to a molten state through induction heating, so that the Zr 56Al13Co28Au3 amorphous alloy strip with the width of 5 mm and the thickness of 20-80 mu m is finally obtained.
S3: and cutting off a sample with the length of about 1.5cm from the obtained Zr 56Al13Co28Au3 amorphous alloy strip, and respectively carrying out ultrasonic cleaning by absolute ethyl alcohol and deionized water to remove surface pollutants. It was then spot welded to nickel wire, and coated with insulation at the weld for electrochemical experiments. Electrochemical deposition is carried out in a standard three-electrode system, a treated Zr 65Al13Co23Au3 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 cm by 1.1 cm), a Saturated Calomel Electrode (SCE) is used as a reference electrode for carrying out constant potential polarization experiment, electrolyte is 60 mL of 0.1M NH 4 F and 0.1M (NH 4)2SO4 mixed aqueous solution, the polarization potential is 1.9V vs. SCE, and the polarization time is 3h. After electrochemical dealloying, a sample is washed by deionized water for multiple times to remove surface residual electrolyte, and the nano-porous cobalt electrode material is obtained.
Example 2
S1: taking Zr, al, co, au pure metal (purity is 99.99%) of 40g according to atomic ratio of 56:13:28:3 of Zr to Al to Co to Au, and respectively carrying out ultrasonic cleaning by using acetone and deionized water to remove surface pollutants. The cleaned Zr, al, co, au pure metal is mixed in a crucible in an arc melting furnace and is melted under the argon atmosphere, and the melting current is about 180A. During smelting, the two side surfaces of the alloy ingot are respectively smelted twice, and about 3 min parts of the alloy ingot are smelted each time.
S2: about 10 percent of melted Zr 56Al13Co28Au3 master alloy g is taken and placed at the bottom of a specially made quartz tube (the diameter of the quartz tube is 16 mm, the bottom opening is 5 mm), the Zr 56Al13Co28Au3 amorphous alloy strip is obtained through a single copper roller melt-spinning quenching method under the argon atmosphere, the copper roller revolution is 2200 rpm during melt-spinning, and the injection is carried out when the alloy is melted to a molten state through induction heating, so that the Zr 56Al13Co28Au3 amorphous alloy strip with the width of 5 mm and the thickness of 20-80 mu m is finally obtained.
S3: and cutting off a sample with the length of about 1.5cm from the obtained Zr 56Al13Co28Au3 amorphous alloy strip, and respectively carrying out ultrasonic cleaning by absolute ethyl alcohol and deionized water to remove surface pollutants. It was then spot welded to nickel wire, and coated with insulation at the weld for electrochemical experiments. Electrochemical deposition is carried out in a standard three-electrode system, a treated Zr 56Al13Co28Au3 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 cm by 1.1 cm), a Saturated Calomel Electrode (SCE) is used as a reference electrode for carrying out constant potential polarization experiment, electrolyte is 60 mL of 0.15M NH 4 F and 0.1M (NH 4)2SO4 mixed aqueous solution, the polarization potential is 2.5V vs. SCE, and the polarization time is 3h. After electrochemical dealloying, a sample is washed by deionized water for multiple times to remove surface residual electrolyte, so that the nano-porous cobalt electrode material is obtained.
Example 3
S1: taking Zr, al, co, ni pure metal (purity is 99.99%) with atomic ratio of Zr to Al to Co to Ni of 60 to 14 to 23 to 40g, and respectively carrying out ultrasonic cleaning with acetone and deionized water to remove surface pollutants. The cleaned Zr, al, co, ni pure metal is mixed in a crucible in an arc melting furnace and is melted under the argon atmosphere, and the melting current is about 180A. During smelting, the two side surfaces of the alloy ingot are respectively smelted twice, and about 3 min parts of the alloy ingot are smelted each time.
S2: about 10 percent of melted Zr 60Al14Co23Ni3 master alloy g is taken and placed at the bottom of a specially made quartz tube (the diameter of the quartz tube is 16 mm, the bottom opening is 5 mm), the Zr 60Al14Co23Ni3 amorphous alloy strip is obtained through a single copper roller melt-spinning quenching method under the argon atmosphere, the copper roller revolution is 2200 rpm during melt-spinning, and the injection is carried out when the alloy is melted to a molten state through induction heating, so that the Zr 50Al18Co27Ag5 amorphous alloy strip with the width of 5 mm and the thickness of 20-80 mu m is finally obtained.
S3: and cutting off a sample with the length of about 1.5cm from the obtained Zr 60Al14Co23Ni3 amorphous alloy strip, and respectively carrying out ultrasonic cleaning by absolute ethyl alcohol and deionized water to remove surface pollutants. It was then spot welded to nickel wire, and coated with insulation at the weld for electrochemical experiments. Electrochemical deposition is carried out in a standard three-electrode system, a treated Zr 60Al14Co23Ni3 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 cm by 1.1 cm), a Saturated Calomel Electrode (SCE) is used as a reference electrode for carrying out constant potential polarization experiment, the electrolyte is 60 mL of a mixed aqueous solution of 0.135M NH 4 F and 0.5M (NH 4)2SO4, the polarization potential is 1.9V vs. SCE, and the polarization time is 1h. After electrochemical dealloying, a sample is washed by deionized water for a plurality of times to remove surface residual electrolyte, so that the nano-porous cobalt electrode material is obtained.
Example 4
S1: taking Zr, al, co, nb pure metals (the purity is 99.99%) of which total 40g according to the atomic ratio of Zr to Al to Co to Nb is 56:13:28:3, and respectively carrying out ultrasonic cleaning by using acetone and deionized water to remove surface pollutants. The cleaned Zr, al, co, nb pure metal is mixed in a crucible in an arc melting furnace and is melted under the argon atmosphere, and the melting current is about 180A. During smelting, the two side surfaces of the alloy ingot are respectively smelted twice, and about 3 min parts of the alloy ingot are smelted each time.
S2: about 10 percent of melted Zr 56Al13Co28Nb3 master alloy g is taken and placed at the bottom of a specially made quartz tube (the diameter of the quartz tube is 16 mm, the bottom opening is 5 mm), the Zr 56Al13Co28Nb3 amorphous alloy strip is obtained through a single copper roller melt-spinning quenching method under the argon atmosphere, the copper roller revolution is 2200 rpm during melt-spinning, and the injection is carried out when the alloy is melted to a molten state through induction heating, so that the Zr 56Al13Co28Nb3 amorphous alloy strip with the width of 5 mm and the thickness of 20-80 mu m is finally obtained.
S3: and cutting off a sample with the length of about 1.5cm from the obtained Zr 56Al13Co28Nb3 amorphous alloy strip, and respectively carrying out ultrasonic cleaning by absolute ethyl alcohol and deionized water to remove surface pollutants. It was then spot welded to nickel wire, and coated with insulation at the weld for electrochemical experiments. Electrochemical deposition is carried out in a standard three-electrode system, a treated Zr 56Al13Co28Nb3 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 cm by 1.1 cm), a Saturated Calomel Electrode (SCE) is used as a reference electrode for carrying out constant potential polarization experiment, the electrolyte is 60 mL of a mixed aqueous solution of 0.135M NH 4 F and 1M (NH 4)2SO4), the polarization potential is 1.5V vs. SCE, the polarization time is 3h, and after electrochemical dealloying, a sample is washed by deionized water for multiple times to remove surface residual electrolyte, so that the nano-porous cobalt electrode material is obtained.
Example 5
S1: taking 40g of pure metals (with purity of 99.99%) of Zr, al and Co according to the atomic ratio of 56:16:28, and respectively carrying out ultrasonic cleaning by using acetone and deionized water to remove surface pollutants. The cleaned Zr, al and Co pure metals are mixed in a crucible in an arc melting furnace and are melted in an argon atmosphere, and the melting current is about 180A. During smelting, the two side surfaces of the alloy ingot are respectively smelted twice, and about 3 min parts of the alloy ingot are smelted each time.
S2: about 10 percent of melted Zr 56Al16Co28 master alloy g is taken and placed at the bottom of a specially made quartz tube (the diameter of the quartz tube is 16 mm, the bottom opening is 5 mm), the Zr 56Al16Co28 amorphous alloy strip is obtained through a single copper roller melt-spinning quenching method under the argon atmosphere, the copper roller revolution is 2200 rpm during melt-spinning, and the injection is carried out when the alloy is melted to a molten state through induction heating, so that the Zr 56Al16Co28 amorphous alloy strip with the width of 5 mm and the thickness of 20-80 mu m is finally obtained.
S3: and cutting off a sample with the length of about 1.5cm from the obtained Zr 56Al16Co28 amorphous alloy strip, and respectively carrying out ultrasonic cleaning by absolute ethyl alcohol and deionized water to remove surface pollutants. It was then spot welded to nickel wire, and coated with insulation at the weld for electrochemical experiments. Electrochemical deposition is carried out in a standard three-electrode system, a treated Zr 56Al16Co28 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 cm by 1.1 cm), a Saturated Calomel Electrode (SCE) is used as a reference electrode for carrying out constant potential polarization experiment, the electrolyte is 60 mL of 0.135M NH 4 F and 1M (NH 4)2SO4 mixed aqueous solution, the polarization potential is 1.9V vs. SCE, the polarization time is 3h, and after electrochemical dealloying, the sample is washed by deionized water for multiple times to remove the surface residual electrolyte, so that the nano-porous cobalt electrode material is obtained.
Example 6
S1: taking Zr, al, co, ag pure metal (purity is 99.99%) of 40g according to atomic ratio of Zr to Al to Co to Ag of 50 to 18 to 27, respectively carrying out ultrasonic cleaning by using acetone and deionized water to remove surface pollutants. The cleaned Zr, al and Co pure metals are mixed in a crucible in an arc melting furnace and are melted in an argon atmosphere, and the melting current is about 180A. During smelting, the two side surfaces of the alloy ingot are respectively smelted twice, and about 3 min parts of the alloy ingot are smelted each time.
S2: about 10 percent of melted Zr 50Al18Co27Ag5 master alloy g is taken and placed at the bottom of a specially made quartz tube (the diameter of the quartz tube is 16 mm, the bottom opening is 5 mm), the Zr 50Al18Co27Ag5 amorphous alloy strip is obtained through a single copper roller melt-spinning quenching method under the argon atmosphere, the copper roller revolution is 2200 rpm during melt-spinning, and the injection is carried out when the alloy is melted to a molten state through induction heating, so that the Zr 50Al18Co27Ag5 amorphous alloy strip with the width of 5 mm and the thickness of 20-80 mu m is finally obtained.
S3: and cutting off a sample with the length of about 1.5cm from the obtained Zr 50Al18Co27Ag5 amorphous alloy strip, and respectively carrying out ultrasonic cleaning by absolute ethyl alcohol and deionized water to remove surface pollutants. It was then spot welded to nickel wire, and coated with insulation at the weld for electrochemical experiments. Electrochemical deposition is carried out in a standard three-electrode system, a treated Zr 50Al18Co27Ag5 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 cm by 1.1 cm), a Saturated Calomel Electrode (SCE) is used as a reference electrode for carrying out constant potential polarization experiment, the electrolyte is 60mL of 0.135M NH 4 F and 1M (NH 4)2SO4, the polarization potential is 1.9V vs. SCE, and the polarization time is 4 h. After electrochemical dealloying, a sample is washed with deionized water for a plurality of times to remove surface residual electrolyte, and the nano-porous cobalt electrode material is obtained.
[ PREPARATION METHOD ]
1. SEM and EDS
Fig. 1 to 6 are SEM images of the surfaces of the nano-porous cobalt electrode materials obtained in examples 1 to 6, respectively, from which it can be seen that the surfaces of the amorphous alloy strips after dealloying form a nano-porous structure with uniform pore diameters, and the nano-porous cobalt and amorphous alloy strips are connected together without adhesive composition and can be directly used as electrode materials.
Table 1 shows EDS data for corresponding regions of the nanoporous cobalt electrode materials obtained in examples 1-6
TABLE 1
As can be seen from the EDS data of each embodiment combined with the SEM image, the nano-porous cobalt electrode material obtained by each embodiment is a nano-porous material of simple substance cobalt, and the atomic percentage content of the simple substance cobalt is 26.85-84.01%; as can be seen from comparison of the data in examples 1 and 2, the corrosion depth is insufficient when the concentration of the electrolyte is low, so that the content of elements in the amorphous alloy strip matrix is too high; from the comparison of the data in examples 5 and 6, it is shown that adding a small amount of silver element into ZrAlCo alloy system reduces the average pore size from 44.7nm to 24.6nm, which indicates that the addition of silver element can effectively refine the ligament and pore size of the nano-porous cobalt.
2、 TEM
Fig. 7 (a) is a TEM image of the nano-porous cobalt electrode material obtained in example 5, and a black shadow zone and a white bright spot zone are clearly observed from the matrix in fig. 7 (a), wherein the black shadow zone represents the porous structure ligament, the white bright spot zone represents the porous pore, and the uniformly distributed white bright spot zone and black shadow zone simultaneously indicate that the pore size and ligament are uniformly distributed, which is consistent with the result observed by SEM image. In order to better determine the components of the nano-porous structure formed after dealloying, TEM selective diffraction spectrum analysis is carried out on the nano-porous structure, and the three main diffraction rings are (312), (204) and (513) crystal faces of Co, as shown in fig. 7 (b), so that the nano-porous structure of the amorphous alloy after dealloying, which is mainly simple substance Co, is further proved.
3. Pore size distribution statistical graph
FIG. 8 is a statistical graph of pore size distribution of the nanoporous cobalt electrode material obtained in example 5, from which it can be seen that pore size fractions
The amorphous alloy is distributed normally and mainly distributed at about 40nm, and the pore size distribution is uniform, which further proves the theory that the amorphous alloy generates a uniform nano porous structure in the dealloying process.
4. Specific surface area
FIG. 9 is a capacitive electricity at a voltage of 0.05V of the nanoporous cobalt electrode material and ZrAlCo amorphous strips obtained in example 5
And (3) carrying out cyclic voltammetry on the two materials under the potential condition of 0.05V to obtain a response current difference value of oxidation reaction and reduction reaction of the materials under the potential condition, selecting a scanning rate of 10-50mV/s to obtain the current difference value under the scanning rates, then carrying out linear fitting, wherein the larger the slope of the linear fitting result is, the better the performance in the electrochemical test is, the ratio of the slope of the obtained fitting straight line is the ratio of electrochemical active areas, and the obtained result is that the slope of the nano porous cobalt is 13.9 times that of the amorphous alloy strip, namely the electrochemical active specific surface area is 13.9 times that of the amorphous alloy strip, and the electrode material has larger electrochemical active specific surface area, so that more active sites are provided and the reaction is accelerated.
[ Performance test ]
The method comprises the steps of respectively taking ZrAlCo amorphous alloy strips, pure Co simple substance and the nano porous cobalt electrode material obtained in the embodiment 5 as working electrodes, taking a platinum sheet as a counter electrode and a saturated calomel electrode as a reference electrode, simulating a Methyl Orange (MO) solution with 20mg/L pollutant, applying a square wave potential of 1.5V by using an electrochemical square wave method, carrying out degradation experiments on the methyl orange, and testing the absorbance of the methyl orange solution before and after degradation, wherein the results are shown in figure 10.
As can be seen from FIG. 10, the degradation rates of pure Co simple substance and 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 the high specific surface area, and the ligaments formed by the nano porous structure formed by the nested pore channels and the metal ligaments are uniformly distributed, so that the dispersibility and the specific surface area are increased, and the contact efficiency with pollutants is improved; the porous structure can enable liquid to flow rapidly, provide diffusion and transmission channels for guest reaction molecules, provide more attachment points for degradation reaction, provide more redox reaction places and accelerate reaction speed; on the other hand, the porous Co catalytic matrix material does not need to carry out load treatment, so that the self-supporting of the material can be realized, the problem of reduction of specific surface area caused by agglomeration is avoided, the stability of the electrode material is maintained, and the catalytic activity of the electrode material is ensured.
While the invention has been described with reference to preferred embodiments, it is not intended to be limiting. Those skilled in the art will appreciate that various modifications and adaptations can be made without departing from the spirit and scope of the present invention. Accordingly, the scope of the invention is defined by the appended claims.
Claims (6)
1. The preparation method of the nano porous cobalt electrode material is characterized by comprising the following steps:
S1: proportioning metal elements according to a target alloy Zr aAlbCocMd, and smelting to obtain a master alloy; wherein, 50. 50 at.ltoreq.a.ltoreq.60 60 at.ltoreq.13 13 at.ltoreq.b.ltoreq.18 18 at.ltoreq.23 23 at.ltoreq.c.ltoreq.28at.0. 0 at.ltoreq.d.ltoreq.5. 5 at.m is any one of the Au, ag, ni, nb metal elements;
s2: treating the master alloy obtained in the step S1 by a single-roller spin quenching method to obtain Zr aAlbCocMd amorphous alloy strips;
s3: in a standard three-electrode system, taking a Zr aAlbCocMd amorphous alloy strip obtained in the step S2 as a working electrode, taking a platinum sheet as a counter electrode, taking a saturated calomel electrode as a reference electrode, taking a mixed aqueous solution of NH 4 F and (NH 4)2SO4) as an electrolyte, carrying out constant potential polarization under a certain polarization potential, carrying out electrochemical dealloying treatment on the Zr aAlbCocMd amorphous alloy strip by a constant potential polarization method, and directly obtaining a nano-porous cobalt electrode material on the Zr aAlbCocMd amorphous alloy strip electrode;
Wherein the nano porous cobalt electrode material is a self-supporting nano porous strip and has mutually nested three-dimensional continuous structure
The structure comprises holes and metal ligaments, and the metal ligaments are uniformly distributed; the cobalt in the nano porous cobalt electrode material is elemental cobalt, and the atomic percentage content of the elemental cobalt is 26.85-84.01%.
2. The method for preparing a nano-porous cobalt electrode material according to claim 1, wherein the pore size distribution of the pores is uniform and normal.
3. The method of preparing a nanoporous cobalt electrode material according to claim 1, wherein the nanoporous cobalt electrode material has a specific surface area of 13.9 times that of the original amorphous alloy strip.
4. The method for preparing a nano-porous cobalt electrode material according to claim 1, wherein the concentration of NH 4 F is 0.1-0.15M, (NH 4)2SO4 concentration is 0.1-1M).
5. The method for preparing a nano-porous cobalt electrode material according to claim 1, wherein the polarization potential is 1.5-2.5V and the polarization time is 1-4h.
6. The method for preparing a nano-porous cobalt electrode material according to claim 1, wherein the number of copper roller revolutions is 2200rpm when the single roller spin quenching method is melt spinning.
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