CN117712393A - Preparation method of self-supporting oxygen diffusion electrode of carbon nano tube - Google Patents
Preparation method of self-supporting oxygen diffusion electrode of carbon nano tube Download PDFInfo
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- CN117712393A CN117712393A CN202410025257.6A CN202410025257A CN117712393A CN 117712393 A CN117712393 A CN 117712393A CN 202410025257 A CN202410025257 A CN 202410025257A CN 117712393 A CN117712393 A CN 117712393A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 51
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 51
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 239000001301 oxygen Substances 0.000 title claims abstract description 37
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 37
- 238000009792 diffusion process Methods 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 claims abstract description 31
- 239000002184 metal Substances 0.000 claims abstract description 31
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 15
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 10
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- 238000000576 coating method Methods 0.000 claims abstract description 9
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- 238000000137 annealing Methods 0.000 claims abstract description 7
- 239000002344 surface layer Substances 0.000 claims abstract description 6
- 238000004140 cleaning Methods 0.000 claims abstract description 5
- 229910052573 porcelain Inorganic materials 0.000 claims abstract description 4
- 239000012153 distilled water Substances 0.000 claims abstract description 3
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- 238000000034 method Methods 0.000 claims description 27
- 239000003054 catalyst Substances 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 22
- 238000004321 preservation Methods 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 238000011065 in-situ storage Methods 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000010935 stainless steel Substances 0.000 claims description 14
- 229910001220 stainless steel Inorganic materials 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 238000000151 deposition Methods 0.000 claims description 11
- 230000008021 deposition Effects 0.000 claims description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- 229920000642 polymer Polymers 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 238000004070 electrodeposition Methods 0.000 claims description 7
- 229910044991 metal oxide Inorganic materials 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 229920000877 Melamine resin Polymers 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 239000003792 electrolyte Substances 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 230000000630 rising effect Effects 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 229910052723 transition metal Inorganic materials 0.000 claims description 2
- 150000003624 transition metals Chemical class 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- XEUFSQHGFWJHAP-UHFFFAOYSA-N cobalt(2+) manganese(2+) oxygen(2-) Chemical compound [O--].[O--].[Mn++].[Co++] XEUFSQHGFWJHAP-UHFFFAOYSA-N 0.000 description 10
- MZZUATUOLXMCEY-UHFFFAOYSA-N cobalt manganese Chemical compound [Mn].[Co] MZZUATUOLXMCEY-UHFFFAOYSA-N 0.000 description 9
- 239000007772 electrode material Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 5
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 5
- 229940071125 manganese acetate Drugs 0.000 description 5
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000002905 metal composite material Substances 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
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- -1 carbon nanotube metal oxide Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000022131 cell cycle Effects 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
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- 239000002071 nanotube Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000005121 nitriding Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
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- Inert Electrodes (AREA)
Abstract
The invention provides a preparation method of a self-supporting oxygen diffusion electrode of a carbon nano tube. The preparation method of the self-supporting oxygen diffusion electrode of the carbon nano tube comprises the following steps: firstly, ultrasonically treating a metal net with a certain size in an organic solution to remove an organic coating on the surface layer, ultrasonically removing oxide impurities on the surface layer in an acid solution, and then cleaning by using distilled water and drying; and step two, uniformly coating a certain amount of nitrogen-containing high molecular organic compounds on the surface of the cleaned metal net, then placing the treated metal net in a porcelain boat, and carrying out annealing treatment in a tubular furnace at a certain atmosphere and temperature. The preparation method of the self-supporting oxygen diffusion electrode of the carbon nano tube has excellent ORR/OER catalytic activity, and can be directly used as an air positive electrode of a zinc-air battery to ensure high output voltage and cycle stability of the battery.
Description
Technical Field
The invention relates to the technical field of electrode materials, in particular to a preparation method of a self-supporting oxygen diffusion electrode of a carbon nano tube.
Background
With the increasing global energy crisis and environmental problems, the demand for renewable, clean and sustainable energy has been unprecedented. Zinc-air batteries, particularly in rechargeable form, represent one of the most promising renewable energy storage technologies due to their extremely high theoretical energy density. However, when a complex multi-electron redox process is performed, the critical Oxygen Reduction Reaction (ORR) and Oxygen Evolution Reaction (OER) occurring in the air positive electrode have problems of slow kinetics and large overpotential, resulting in limited energy density, low efficiency and short cycle life of the battery. Pt and its alloys are currently recognized as the best ORR electrocatalyst, but are not highly effective for OER catalysis, ir and RuO2 have excellent OER activity, but are poorly active, and the high cost and scarcity of these precious metals have prevented their widespread commercialization. Therefore, there is an urgent need to develop a bi-functional catalyst electrode with abundant reserves, durability and high efficiency to accelerate oxygen reduction and kinetic processes, thereby achieving efficient conversion of energy.
In addition, the air positive electrode is generally prepared by fixing a catalyst to a conductive substrate using a binder, which increases the internal resistance of the electrode and is very likely to block reactive active sites. More importantly, the subsequent adhesion method is difficult to ensure that the catalyst cannot fall off in the long-term circulation process, so that the performance of the battery is reduced. One of the most effective methods for solving the above problems is to construct a self-supporting electrode, and construct a material with bifunctional oxygen catalytic activity on a conductive substrate in situ, which is beneficial to material transmission, reducing ohmic polarization and diffusion polarization, and stabilizing a gas, solid and liquid three-phase reaction interface.
Disclosure of Invention
In order to solve the technical problem, the invention provides a preparation method of a self-supporting oxygen diffusion electrode of a carbon nano tube.
The preparation method of the self-supporting oxygen diffusion electrode of the carbon nano tube provided by the invention comprises the following steps:
firstly, ultrasonically treating a metal net with a certain size in an organic solution to remove an organic coating on the surface layer, ultrasonically removing oxide impurities on the surface layer in an acid solution, and then cleaning by using distilled water and drying;
uniformly coating a certain amount of nitrogen-containing high molecular organic compound on the surface of the cleaned metal net, then placing the treated metal net in a porcelain boat, and carrying out annealing treatment in a tubular furnace at a certain atmosphere and temperature;
step three, placing the metal mesh pretreated in the step two in a three-electrode electrolytic cell, using a mixed solution of a plurality of metal salts with certain concentration as electrolyte, performing step-by-step electrodeposition reaction, and then cleaning the metal mesh and drying;
and step four, oxidizing the metal mesh obtained in the step three in an air atmosphere to obtain the in-situ carbon nanotube self-supporting oxygen catalyst with the metal oxide array growing.
The metal mesh material in the first step is a copper mesh, a nickel mesh, a titanium mesh, a platinum mesh, a stainless steel mesh or an iron mesh; more preferably stainless steel mesh and iron mesh.
Further defined, the organic solution in step one is a ketone, such as acetone, butanone, and the like.
Further defined, the acid solution in the first step is dilute hydrochloric acid or dilute nitric acid, and the concentration of the acid solution is 0.5M-1M.
Further limiting the ultrasonic treatment time in the first step to be 5-20 min; preferably 10min.
Further defined, the metal mesh material in step two is a stainless steel mesh of 200-700 mesh, more preferably 300-500 mesh.
Further defined, the organic compounds in step two are dicyandiamide, polyacrylonitrile, melamine and urea.
The second step is to put the metal mesh material on the downstream of the nitrogen-containing polymer organic compound powder, and the nitrogen-containing polymer organic compound paste or the nitrogen-containing polymer organic compound powder; preferably, the nitrogen-containing polymer organic compound paste is covered, and the solvent is deionized water, ethanol or DMF (N, N-dimethylformamide), more preferably an ethanol solution; the mass ratio of the nitrogen-containing high molecular organic compound to the solvent is 1 (10-25), preferably 1 (10-20), more preferably 1 (15-20); and then vacuum drying is carried out for 10 to 12 hours at the temperature of 40 to 70 ℃.
Further defined, the atmosphere in step two is an inert gas such as argon, nitrogen or a mixture of nitrogen and argon, more preferably nitrogen.
Further limiting, wherein the heating speed in the annealing treatment in the second step is 2-5 ℃/min, the heat preservation temperature is 600-1000 ℃, the heat preservation treatment time is 1-4 h, the atmosphere is nitrogen, and the air flow rate is controlled to be 5-25 mL/min; more preferably, the heating rate is 5 ℃/min, the heat preservation temperature is 700-900 ℃, the heat preservation treatment time is 2-3 h, and the air flow rate is controlled to be 10-25 mL/min.
Further defined, in step three, the metal salt solution is an acetate solution or a nitrate solution of a (Fe, co, ni, mn etc.) transition metal; the solvent is deionized water or a mixed solution of deionized water and ethanol, and the concentration of the solution is 0.05M-0.25M; more preferably, the solvent is deionized water at a concentration of 0.1M to 0.15M.
Further defined, the multi-step electrodeposition in the third step is potentiostatic deposition, the deposition potential is-0.5V to-1.5V, the deposition time is 60s to 600s, preferably 120s to 420s, more preferably the deposition potential is-0.5V to-1V, and the deposition time is 240s to 420s.
Further limited, the drying treatment in the third step is carried out for 9 to 12 hours at the temperature of 40 to 50 ℃.
Further limiting the temperature rising speed in the oxidation treatment in the step four to be 2-5 ℃/min, the heat preservation temperature to be 300-600 ℃ and the heat preservation time to be 1-4 h; more preferably, the heating speed is 2 ℃/min, the heat preservation temperature is 300 ℃ to 400 ℃, and the heat preservation time is 2 hours to 4 hours.
The in-situ carbon nanotube self-supported oxygen catalyst of the multi-metal oxide array prepared by the preparation method is applied to an air positive electrode material of a zinc-air battery.
Compared with the related art, the preparation method of the self-supporting oxygen diffusion electrode of the carbon nano tube has the following beneficial effects:
the invention provides a preparation method of a self-supporting oxygen diffusion electrode of a carbon nano tube, which comprises the following steps:
the invention provides a method for in-situ growth of a carbon nanotube metal oxide catalyst array by taking a metal mesh as a substrate, which comprises the steps of firstly uniformly coating the metal mesh with melamine to provide a nitrogen source and a carbon source required by nanotube growth, catalyzing nitrogen-doped carbon nanotubes to germinate from the metal mesh substrate under a high temperature condition, interweaving and coating the prepared carbon nanotubes with uniform pipe diameters on a substrate fiber, and then constructing an in-situ carbon nanotube self-supporting oxygen diffusion electrode with a bimetallic oxide array by electrodeposition and annealing technology, wherein the electrode combines the high conductivity of the metal mesh and the in-situ growth of the nitrogen-doped carbon nanotubes, and has a three-dimensional hierarchical structure and rich multi-scale holes, so that rich catalytic active sites can be provided;
the multi-metal oxide array/carbon nano tube self-supporting oxygen diffusion electrode prepared by the invention not only has excellent ORR/OER catalytic activity, but also can be directly used as an air positive electrode of a zinc-air battery to ensure high output voltage and cycle stability of the battery, and has great potential for replacing the commercialized noble metal composite catalyst.
Drawings
FIG. 1 is a scanning electron microscope of a carbon nanotube self-supporting oxygen catalyst (CNT/SS) prepared in example 1, 1a magnification 500 times, 1b magnification 10000 times;
FIG. 2 is a scanning electron microscope, 2a magnification 2000 times, 2b magnification 10000 times, of a cobalt manganese oxide array/carbon nanotube self-supporting oxygen catalyst prepared by the method described in example 1;
FIG. 3 is a scanning electron microscope, 3a magnification 2000 times, 3b magnification 10000 times, of the cobalt manganese oxide array/carbon nanotube self-supporting oxygen catalyst prepared by the method described in example 2;
FIG. 4 is an XRD spectrum of a CoMn-CNT/SS sample and a blank SS in example 1;
FIG. 5 is an open circuit voltage plot of a zinc air cell assembled from CoMn-CNT/SS samples of example 1;
fig. 6 is a zinc air cell cycle stability test of cobalt manganese oxide array in situ carbon nanotube self-supported catalyst of example 1.
Description of the embodiments
The invention will be further described with reference to the drawings and embodiments.
Description of the embodiments
Example 1: in this embodiment, the preparation method of the in-situ carbon nanotube self-supported catalyst with the cobalt-manganese bimetallic oxide array is performed according to the following steps:
step one, immersing a 300-mesh stainless steel mesh (1 cm multiplied by 3 cm) into an acetone solution for ultrasonic treatment for 10min, then removing surface oxides by ultrasonic treatment in a 0.5M dilute hydrochloric acid solution for 10min, finally washing by ultrasonic treatment in deionized water until the pH is neutral, and drying at 50 ℃ for 12h for standby.
Pouring 1g of melamine into 20mL of ethanol solution, stirring for 1h at 60 ℃ to obtain melamine covered on a stainless steel mesh, drying for 12h at 60 ℃ in a vacuum oven, placing the treated stainless steel mesh in a porcelain boat at the central position of a tube furnace, annealing for 2h under high-purity nitrogen, wherein the heating rate is 5 ℃/min, and the heat preservation temperature is 900 ℃; the air flow rate was controlled at 20mL/min.
Step three, dissolving 7.27g of cobalt nitrate and 6.23g of manganese acetate in 100mL of deionized water, stirring until the cobalt nitrate and the manganese acetate are completely dissolved, and performing constant potential deposition at room temperature in a solution containing cobalt nitrate and manganese acetate for 240s; and then washing for 2-3 times by deionized water and ethanol in turn, and drying at 50 ℃.
Step four, oxidizing the stainless steel mesh obtained in the step three in an air atmosphere, wherein the heating rate is 2 ℃/min, and the heat preservation temperature is 300 ℃; and (3) lasting for 2 hours to obtain the in-situ carbon nanotube self-supporting catalyst with the cobalt-manganese bimetallic oxide array.
Fig. 1 shows that: an array of uniformly distributed carbon nanotubes can be obtained on the surface of stainless steel by the method described in example 1.
Fig. 2 shows that: an in-situ carbon nanotube self-supporting oxygen diffusion electrode grown with a cobalt manganese bi-metal oxide array can be obtained by the method described in example 1.
The in-situ carbon nanotube self-supported catalyst (MnCo-CNT/SS) grown with cobalt-manganese bimetallic oxide array prepared in this example was compared with single metal catalysts (Co-CNT/SS and Mn-CNT/SS) obtained by electrodeposition of cobalt nitrate and manganese acetate alone, and the average value was measured three times under each condition. The test was performed using an electrochemical workstation (CHI 660E), using a three electrode system with 1MKOH as the electrolyte, mnCo-CNT/SS, co-CNT/SS and Mn-CNT/SS as the working electrodes, saturated calomel as the reference electrode, silver chloride as the counter electrode, and a LSV test was performed at a scan rate of 5 mV/s. The test results are shown in Table 1.
TABLE 1 results of OER test of cobalt manganese oxide array in situ carbon nanotube self-supported catalyst
(electrolyte 1 MKOH)
| Sample name | 10mAcm -2 Potential (Vvs. RHE) | 100mAcm -2 Potential (Vvs. RHE) | Overpotential (mV) |
| MnCo-CNT/SS | 1.45 | 1.55 | 220 |
| Co-CNT/SS | 1.50 | 1.58 | 270 |
| Mn-CNT/SS | 1.51 | 1.58 | 280 |
From Table 1, it can be seen that the MnCo-CNT/SS catalyst has an overpotential of 220mV, which is a catalyst having more excellent electrocatalytic performance than a single metal sample.
As shown in FIG. 4, in comparison with a blank stainless steel mesh (SS) sample, the XRD spectrum of CoMn-CNT/SS prepared in example 1 has MnO in addition to the characteristic peaks of the stainless steel mesh itself 2 And Co (OH) 2 The presence of the above components in the CoMn-CNT/SS sample was demonstrated by the characteristic peaks of the corresponding graphitized carbon of the carbon nanotubes.
It can be seen from fig. 5 that the CoMn-CNT/SS sample assembled zinc-air cell prepared in example 1 has an open circuit voltage of 1.45V and is higher than the single metal composite samples Co-CNT/SS and Mn-CNT/SS prepared in a similar manner.
The in-situ carbon nanotube self-supported catalyst of the cobalt-manganese bimetallic oxide array obtained in the embodiment is directly used as an air anode to assemble a zinc-air battery, and a charge-discharge curve of the zinc-air battery is obtained through testing under constant current density.
Under the condition that the loading capacity of the in-situ carbon nanotube self-supporting catalyst of the cobalt-manganese bimetallic oxide array is the same in the electrode material, testing the battery performance of the electrode material under different current densities; the average was measured three times under each condition. The test results are shown in Table 2.
TABLE 2 charge and discharge Performance of cobalt manganese oxide array/carbon nanotube electrode materials under different Current Density conditions
| Different current densities (mA.cm) -2 ) | Discharge voltage (V) | Charging voltage (V) | E (discharge voltage-charge voltage) (V) | Cycle time (h) |
| 5 | 1.96 | 1.14 | 0.82 | 300 |
| 10 | 2.07 | 1.10 | 0.97 | 150 |
| 20 | 2.11 | 1.05 | 1.06 | 150 |
As shown in fig. 6, the CoMn-CNT/SS sample assembled zinc-air cell prepared in case 1 has excellent cycling stability, can be charge-discharge cycled for 330 hours, and has no significant potential decay.
Commercial electrode materials (Pt/C (20%) + RuO were used 2 ) The cobalt manganese oxide array/carbon nanotube electrode material in the alternative example was used to prepare an air positive electrode assembly zinc-air battery, and the performance thereof was tested, and the test results are shown in table 3.
TABLE 3 commercial Pt/C+RuO 2 Charge and discharge performance of electrode material under different current density conditions
| Different current densities (mA.cm) -2 ) | Discharge voltage (V) | Charging voltage (V) | E (discharge voltage-charge voltage) (V) | Cycle time (h) |
| 5 | 1.96 | 1.16 | 0.80 | 120 |
| 10 | 2.08 | 1.11 | 0.97 | 83 |
| 20 | 2.16 | 1.07 | 1.09 | 52 |
As can be seen from a comparison between tables 2 and 3, the zinc-air battery assembled by using the in-situ carbon nanotubes of the cobalt-manganese bi-metal oxide array prepared by the method of the present invention as an air positive electrode shows excellent charge and discharge performance, particularly in that the battery has a smaller charge and discharge voltage difference and longer cycleTime. In addition, with commercial Pt/C (20%) +RuO 2 Compared with a zinc-air battery prepared from the electrode material, the zinc-air battery prepared from the electrode material has greater advantages, which shows that the in-situ carbon nanotube self-supported catalyst of the cobalt-manganese bimetallic oxide array prepared by the invention has wide market application prospect.
Examples
The steps and the method are the same as those in the example 1, the melamine content is only increased to 2g, and the heat preservation temperature in the nitriding process is 800 ℃; the addition amount of cobalt nitrate is 10.9g, the addition amount of manganese acetate is 9.35g and the time is 150s in the electrodeposition process; the temperature rising speed in the oxidation process is 5 ℃/min, and the heat preservation temperature is 350 ℃; duration 2h.
Fig. 3 shows that: the in-situ carbon nanotube self-supporting oxygen diffusion electrode with the cobalt-manganese bimetallic oxide array can be obtained after the treatment of the method in the embodiment 2. As can be seen from the SEM image, the carbon nanotubes coated with cobalt manganese oxide nano-sheets uniformly grow on the surface of the stainless steel mesh. Using the cobalt manganese oxide array/carbon nanotube self-supporting oxygen diffusion electrode obtained in example 2, the catalyst also had good catalytic performance, confirming the versatility of the preparation method, under otherwise identical test conditions, as concluded from example 1. Compared with the preparation method of the cobalt manganese oxide array/carbon nano tube self-supporting oxygen diffusion electrode, the preparation method of the cobalt manganese oxide array/carbon nano tube self-supporting oxygen diffusion electrode has the advantages that the catalyst is more convenient and simpler to attach to the electrode, the cost is reduced, the performance is stable, and the preparation process of the electrode is simplified; the electrode obtained by the invention has excellent difunctional catalytic performance and stability and has the potential of large-scale production.
The foregoing description is only illustrative of the present invention and is not intended to limit the scope of the invention, and all equivalent structures or equivalent processes or direct or indirect application in other related technical fields are included in the scope of the present invention.
Claims (10)
1. The preparation method of the self-supporting oxygen diffusion electrode of the carbon nano tube is characterized by comprising the following steps of:
firstly, ultrasonically treating a metal net with a certain size in an organic solution to remove an organic coating on the surface layer, ultrasonically removing oxide impurities on the surface layer in an acid solution, and then cleaning by using distilled water and drying;
uniformly coating a certain amount of nitrogen-containing high molecular organic compound on the surface of the cleaned metal net, then placing the treated metal net in a porcelain boat, and carrying out annealing treatment in a tubular furnace at a certain atmosphere and temperature;
step three, placing the metal mesh pretreated in the step two in a three-electrode electrolytic cell, using a mixed solution of a plurality of metal salts with certain concentration as electrolyte, performing step-by-step electrodeposition reaction, and then cleaning the metal mesh and drying;
and step four, oxidizing the metal mesh obtained in the step three in an air atmosphere to obtain the in-situ carbon nanotube self-supporting oxygen catalyst with the metal oxide array growing.
2. The method for preparing a self-supporting oxygen diffusion electrode of carbon nanotubes according to claim 1, wherein the metal mesh material in the first step is copper mesh, nickel mesh, titanium mesh, platinum mesh, stainless steel mesh, or iron mesh; more preferably stainless steel mesh and iron mesh.
3. The method for preparing a self-supporting oxygen diffusion electrode for a carbon nanotube according to claim 1, wherein the organic solution in the first step is ketone, such as acetone, butanone, etc.
4. The method for preparing a self-supporting oxygen diffusion electrode for carbon nanotubes according to claim 1, wherein the acid solution in the step one is dilute hydrochloric acid or dilute nitric acid, and the concentration of the acid solution is 0.5-1M.
5. The method for preparing a self-supporting oxygen diffusion electrode for a carbon nanotube according to claim 1, wherein the ultrasonic treatment time in the first step is 5-20 min; preferably 10min.
6. The method for preparing a self-supporting oxygen diffusion electrode for carbon nanotubes according to claim 1, wherein the metal mesh material in the second step is a stainless steel mesh of 200-700 mesh, more preferably 300-500 mesh.
7. The method for preparing a self-supporting oxygen diffusion electrode for carbon nanotubes according to claim 1, wherein the organic compound in the second step is dicyandiamide, polyacrylonitrile, melamine and urea.
8. The method for preparing a self-supporting oxygen diffusion electrode of carbon nanotubes according to claim 1, wherein the coating treatment process in the second step is to place a metal mesh material downstream of the nitrogen-containing polymer organic compound powder, to cover the nitrogen-containing polymer organic compound paste or to cover the nitrogen-containing polymer organic compound powder; preferably, the nitrogen-containing polymer organic compound paste is covered, and the solvent is deionized water, ethanol or DMF (N, N-dimethylformamide), more preferably an ethanol solution; the mass ratio of the nitrogen-containing high molecular organic compound to the solvent is 1 (10-25), preferably 1 (10-20), more preferably 1 (15-20); and then vacuum drying is carried out for 10 to 12 hours at the temperature of 40 to 70 ℃.
9. The method for preparing a self-supporting oxygen diffusion electrode of a carbon nanotube according to claim 1, wherein the atmosphere in the second step is inert gas such as argon, nitrogen or a mixture of nitrogen and argon, more preferably nitrogen, the heating rate in the annealing treatment in the second step is 2-5 ℃/min, the heat preservation temperature is 600-1000 ℃, the heat preservation time is 1-4 h, the atmosphere is nitrogen, and the air flow rate is controlled to be 5-25 mL/min; more preferably, the heating rate is 5 ℃/min, the heat preservation temperature is 700-900 ℃, the heat preservation treatment time is 2-3 h, and the air flow rate is controlled to be 10-25 mL/min.
10. The method for preparing a self-supporting oxygen diffusion electrode for carbon nanotubes according to claim 1, wherein in the third step, the metal salt solution is an acetate solution or a nitrate solution of (Fe, co, ni, mn etc.) transition metal; the solvent is deionized water or a mixed solution of deionized water and ethanol, and the concentration of the solution is 0.05M-0.25M; more preferably, the solvent is deionized water with the concentration of 0.1M to 0.15M;
in the third step, multi-step electrodeposition is constant potential deposition, the deposition potential is-0.5V to-1.5V, the deposition time is 60s to 600s, preferably 120s to 420s, more preferably the deposition potential is-0.5V to-1V, and the deposition time is 240s to 420s;
the drying treatment in the third step is carried out for 9 to 12 hours at the temperature of 40 to 50 ℃;
the temperature rising speed in the oxidation treatment in the step four is 2-5 ℃/min, the heat preservation temperature is 300-600 ℃, and the heat preservation time is 1-4 h; more preferably, the heating speed is 2 ℃/min, the heat preservation temperature is 300 ℃ to 400 ℃, and the heat preservation time is 2 hours to 4 hours.
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| US20200286690A1 (en) * | 2017-07-07 | 2020-09-10 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | Method for preparing an electrode comprising a substrate, aligned carbon nanotubes and a metal oxide deposited by oxidative deposition, the electrode and uses thereof |
| CN114744224A (en) * | 2022-04-21 | 2022-07-12 | 浙江理工大学 | Preparation and application of nitrogen-doped carbon nanotube-loaded nickel-cobalt composite nanowire |
| US20230167569A1 (en) * | 2021-11-30 | 2023-06-01 | Xi'an University Of Architecture And Technology | Co3o4 nanosheet loaded stainless steel mesh, preparation method and application thereof |
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| US20200286690A1 (en) * | 2017-07-07 | 2020-09-10 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | Method for preparing an electrode comprising a substrate, aligned carbon nanotubes and a metal oxide deposited by oxidative deposition, the electrode and uses thereof |
| US20230167569A1 (en) * | 2021-11-30 | 2023-06-01 | Xi'an University Of Architecture And Technology | Co3o4 nanosheet loaded stainless steel mesh, preparation method and application thereof |
| CN114744224A (en) * | 2022-04-21 | 2022-07-12 | 浙江理工大学 | Preparation and application of nitrogen-doped carbon nanotube-loaded nickel-cobalt composite nanowire |
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