CN114792810A - Preparation method of Fe (Ni) -NCNTs @ NiFe-LDH in-situ electrode - Google Patents
Preparation method of Fe (Ni) -NCNTs @ NiFe-LDH in-situ electrode Download PDFInfo
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- 238000011065 in-situ storage Methods 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 88
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 41
- 229920001690 polydopamine Polymers 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 33
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 31
- 239000004744 fabric Substances 0.000 claims abstract description 29
- 239000002243 precursor Substances 0.000 claims abstract description 24
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 17
- 239000000243 solution Substances 0.000 claims description 68
- 238000010438 heat treatment Methods 0.000 claims description 52
- 235000019850 ferrous citrate Nutrition 0.000 claims description 36
- 239000011640 ferrous citrate Substances 0.000 claims description 36
- APVZWAOKZPNDNR-UHFFFAOYSA-L iron(ii) citrate Chemical compound [Fe+2].OC(=O)CC(O)(C([O-])=O)CC([O-])=O APVZWAOKZPNDNR-UHFFFAOYSA-L 0.000 claims description 36
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 33
- 239000004202 carbamide Substances 0.000 claims description 33
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 29
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 29
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 28
- 239000007983 Tris buffer Substances 0.000 claims description 26
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims description 26
- 239000011259 mixed solution Substances 0.000 claims description 20
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims description 17
- 229960001149 dopamine hydrochloride Drugs 0.000 claims description 17
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 14
- 239000012300 argon atmosphere Substances 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 238000005245 sintering Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000007772 electrode material Substances 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract 6
- 238000000137 annealing Methods 0.000 abstract 1
- 238000003912 environmental pollution Methods 0.000 abstract 1
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 87
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 43
- 239000001301 oxygen Substances 0.000 description 43
- 229910052760 oxygen Inorganic materials 0.000 description 43
- 239000007864 aqueous solution Substances 0.000 description 40
- 238000004519 manufacturing process Methods 0.000 description 36
- 238000004832 voltammetry Methods 0.000 description 16
- 238000001075 voltammogram Methods 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 6
- 239000002135 nanosheet Substances 0.000 description 6
- 239000002071 nanotube Substances 0.000 description 4
- 230000002441 reversible effect Effects 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000007777 multifunctional material Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
- H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
The invention provides a preparation method of an Fe (Ni) -NCNTs @ NiFe-LDH in-situ electrode. Firstly, preparing a double-layer hydroxide (Fe (Ni) — LDH) precursor on a Carbon Cloth (CC) by using a water bath method, then attaching Polydopamine (PDA) on the precursor, annealing by using a chemical vapor deposition method (CVD) to prepare Fe (Ni) — NCNTs, and finally growing a nickel iron double-layer hydroxide on the Fe (Ni) — NCNTs by using the water bath method again to prepare a final sample Fe (Ni) — NCNTs @ NiFe-LDH. The technical scheme of the invention has the advantages of low cost of the required raw materials, simple operation, short time consumption, less environmental pollution and the like; the prepared Fe (Ni) -NCNTs @ NiFe-LDH in-situ electrode has excellent ORR and OER double performance, excellent stability and rich active sites, and can provide an excellent electrode material for the subsequent research of a zinc-air battery.
Description
Technical Field
The invention relates to preparation of multi-component multifunctional materials, and belongs to the field of electrocatalysis and energy conversion materials and devices.
Background
In view of global energy shortages and climate change issues, the development of advanced technologies for the production of sustainable energy becomes of paramount importance. The reversible zinc-air battery has stable performance, no pollution and high theoretical energy density (1084Wh kg), and is a promising substitute for solving the current global energy crisis and serious environmental problems. However, the commercialization thereof is severely hampered by the reduced kinetics of Oxygen Evolution Reaction (OER) inherent in the charging process and by the insufficient activity of Oxygen Reduction Reaction (ORR) during discharging. Therefore, the search for highly efficient bifunctional catalysts remains a great challenge.
NiFe double hydroxide (NiFe-LDH) nanosheets are well known as low cost non-noble metal catalysts for their excellent OER catalytic activity. However, its inherently low conductivity and self-agglomeration, and only single OER activity without ORR properties, severely hampers its application in reversible zinc-air batteries. To overcome these deficiencies of NiFe-LDH, researchers have attempted to combine NiFe-LDH with various carbon substrates to increase their conductivity (angelw.chem., int.ed.2014,53,7584-7588. adv.mater.2015,27, 7051-7057.) or to physically mix them with ORR active materials to obtain bifunctional properties (Energy environ.sci.2016,9, 2020-2024). M (Fe, Ni) -N-C based catalysts proved to be potential ORR catalysts with performance even better than Pt/C but with poor stability on their own.
In order to improve the stability and OER performance of an M (Fe, Ni) -N-C based catalyst, a NiFe-LDH catalyst, namely Fe (Ni) -NCNTs @ NiFe-LDH in-situ electrode, is introduced to the surface of M-N-C. The prepared Fe (Ni) -NCNTs @ NiFe-LDH in-situ electrode has excellent ORR and OER double performance, excellent stability and rich active sites, and can provide an excellent electrode material for the subsequent research of a zinc-air battery.
Disclosure of Invention
In view of this, the invention provides a method for preparing an in situ electrode of Fe (Ni) -NCNTs @ NiFe-LDH, which comprises the following steps:
s1, preparing Fe (Ni) -LDH precursor: dissolving ferrous citrate and urea in UP water to obtain a mixed solution, transferring the mixed solution into a water bath tube, completely immersing carbon cloth in the solution, and reacting at a certain time and a certain temperature to obtain a Fe (Ni) -LDH precursor;
s2, wrapping polydopamine: dissolving a certain amount of dopamine hydrochloride in a Tris solution, suspending carbon cloth loaded with a Fe (Ni) -LDH precursor in the mixed solution, and standing for a period of time to attach PDA;
s3, preparation of Fe (Ni) -NCNTs: placing the Fe (Ni) -LDH precursor attached with PDA in a tube furnace by using a CVD method under the argon atmosphere and using dicyandiamide as a solid nitrogen source, and sintering to prepare Fe (Ni) -NCNTs;
s4, preparation of Fe (Ni) -NCNTs @ NiFe-LDH in situ electrode: ferrous citrate, nickel chloride, urea and hexadecyl trimethyl ammonium bromide are dissolved in UP water, then the solution is transferred into a water bath tube, and Fe (Ni) -NCNTs are completely immersed in the solution for reaction at a certain time and a certain temperature to prepare a final sample Fe (Ni) -NCNTs @ NiFe-LDH.
In S1, the mass ratio of the ferrous citrate to the urea is 1:3-1:4, the temperature of the water bath is maintained to 95-100 ℃ for 3-4h, and preferably the temperature of the water bath is maintained to 95 ℃ for 3 h.
The mixed solution in the S1 is also added with nickel chloride, and the concentration ratio of the nickel chloride to the ferrous citrate is 1:1-1: 3.
In S2, the concentration of dopamine hydrochloride is 0.4-0.6mg/mL, and the time for attaching PDA is 24-30h at normal temperature.
Further, preferably, the concentration of the dopamine hydrochloride is 0.4mg/mL, and the time for attaching PDA is 24 h.
Further, in S3, the mass ratio of dicyandiamide to the PDA-attached Fe (Ni) -LDH precursor is 10-30: 1. The CVD sintering condition is that the temperature is raised to 350-420 ℃ from room temperature at the temperature raising rate of 5-10 ℃/min, the temperature is kept for 1-2h, then the temperature is raised to 800-900 ℃ at the temperature raising rate of 3-5 ℃/min, and the temperature is kept for 2-5 h.
Further, the mass ratio of the nickel chloride to the ferrous citrate is 1:1-1:3, the mass ratio of the ferrous citrate to the urea is 1:3-1:4, the dosage of the hexadecyl trimethyl ammonium bromide is 0.1-2mmol, the temperature of the water bath is maintained to 95-100 ℃, and the time is 3-4 hours.
The invention has the following beneficial effects:
the Fe (Ni) -NCNTs @ NiFe-LDH in-situ electrode has excellent ORR and OER double performance in both 1M KOH and 0.1M KOH test systems.
2. Has excellent stability and abundant active sites.
3. Can provide excellent electrode materials for the follow-up research of zinc-air batteries.
Drawings
FIG. 1, 1M KOH test conditions OER-ORR linear voltammetry sweep curves for examples 1, 2, 3, 4 with partial magnification inset.
FIG. 2, OER-ORR linear voltammogram curves for examples 5, 6, 7, 8 under 1M KOH test conditions, with the inset being a partial magnified view.
FIG. 3, OER-ORR linear voltammogram curves for examples 1, 2, 3, 4 under 0.1M KOH test conditions, with a partial magnified inset.
FIG. 4, OER-ORR linear voltammogram curves for examples 5, 6, 7, 8 under 0.1M KOH test conditions, with the inset showing a partial magnified view.
FIG. 5, OER-ORR linear voltammogram curves for examples 9, 10, 11, 12 under 0.1M KOH test conditions, with the inset showing a partial magnified view.
FIG. 6 SEM (a)5000 times (b)20000 times for the sample of example 1.
FIG. 7, SEM (a)5000 times (b)22000 times of the sample of example 4.
Fig. 8, sample sem (a)5000 times (b)20000 times of example 5.
FIG. 9 SEM (a)5000 times (b)20000 times for example 8.
Detailed Description
Characterizing conditions
The OER-ORR test method in the embodiment of the invention comprises the following steps: the working electrode, the carbon rod and the saturated Hg/HgO electrode were used as reference electrodes, and the following electrolytes were used: 1M KOH aqueous solution and 0.1M KOH aqueous solution, and the scanning speed is 5-10 mV/s. Oxygen was bubbled into the ORR-OER test. Oxygen was naturally saturated in 1M aqueous KOH and 0.1M aqueous KOH and was stirred at 150 rpm during the test. The saturated Hg/HgO electrodes were corrected with a reversible hydrogen electrode, and the potentials described hereinafter are all relative to the reversible hydrogen electrode. The potential (IR) compensation is automatically carried out by using the Shanghai chemical workstation in the LSV test. Scanning electron microscope images were acquired using an aspect F50 scanning electron microscope (FEI America).
Example 1
0.7378g of ferrous citrate and 2.667g of urea are dissolved in 40mL of UP water, then the solution is transferred into a water bath tube, and a carbon cloth is completely immersed in the solution to be subjected to water bath reaction at the temperature of 95 ℃ for 3 hours to prepare Fe-LDH/CC. And preparing a Tris solution with the pH value of 8.5, dissolving 0.4mg/mL dopamine hydrochloride in the Tris solution, suspending the carbon cloth loaded with the precursor in the mixed solution, and standing for 24 hours to attach the PDA. Placing Fe-LDH/CC attached with PDA in a tube furnace by using Dicyandiamide (DCA) as a solid source under argon atmosphere and a CVD method, heating to 350 ℃ from room temperature at a heating rate of 10 ℃/min, preserving heat for 1h, heating to 900 ℃ at a heating rate of 3 ℃/min, preserving heat for 2h, and preparing Fe-NCNTs. 0.71307g of ferrous citrate, 0.2459g of nickel chloride, 2.667g of urea and 0.7289g of CTAB are dissolved in 40mL of UP water, then the solution is transferred into a water bath tube, and Fe-NCNTs are subjected to water bath reaction for 3 hours at the temperature of 95 ℃ to prepare Fe-NCNTs @ NiFe-LDH.
From the OER-ORR linear voltammogram measured on the sample prepared in example 1 under the 1M KOH test condition in FIG. 1, it can be seen that the current density when the electrode passes during the OER process is 10mA/cm 2 When the reaction is carried out, the overpotential corresponding to the oxygen production by the OER reaction in the alkaline aqueous solution is 180 mV; when the current density of the electrode passing through is 100mA/cm 2 When the reaction is carried out, the overpotential corresponding to the production of oxygen by OER in the alkaline aqueous solution is 230 mV. Half-wave E of the sample of example 1 during ORR 1/2 At 0.885V, Δ Ε of example 1 samples (Δ Ε ═ E ∑ E) j＝10 -E 1/2 ) It was 0.53V.
As can be seen from the OER-ORR linear voltammogram scan measured on the sample prepared in example 1 under the 0.1M KOH test condition in FIG. 3, the current density when the electrode passes during the OER process is 10mA/cm 2 When the reaction is carried out, the overpotential corresponding to the oxygen production of the OER in the alkaline aqueous solution is 251 mV; when the current density of the electrode passing through is 100mA/cm 2 When the reaction is carried out, the overpotential corresponding to the oxygen production by the OER reaction in the alkaline aqueous solution is 315 mV. Half-wave E of the sample of example 1 during ORR 1/2 At 0.851V, Δ Ε of the example 1 samples (Δ Ε ═ E) j＝10 -E 1/2 ) It was 0.63V.
FIG. 6 is a SEM picture of example 1 showing that ultrathin NiFe-LDH nanosheets were grown uniformly and perpendicularly on Fe-NCNTs nanotubes.
Example 2
0.7378g of ferrous citrate and 2.667g of urea are dissolved in 40mL of UP water, then the solution is transferred into a water bath tube, and a carbon cloth is completely immersed in the solution to be subjected to water bath reaction at the temperature of 95 ℃ for 3 hours to prepare Fe-LDH/CC. And preparing a Tris solution with the pH value of 8.5, dissolving 0.4mg/mL dopamine hydrochloride in the Tris solution, suspending the carbon cloth loaded with the precursor in the mixed solution, and standing for 24 hours to attach the PDA. Placing the Fe-LDH/CC with the PDA attached in a tube furnace by a CVD method with Dicyandiamide (DCA) as a solid source in an argon atmosphere, heating to 350 ℃ from room temperature at a heating rate of 10 ℃/min, keeping the temperature for 1h, heating to 900 ℃ at a heating rate of 3 ℃/min, and keeping the temperature for 2h to prepare Fe-NCNTs. 0.71307g of ferrous citrate, 0.2459g of nickel chloride, 2.667g of urea and 0.3645g of CTAB are dissolved in 40mL of UP water, then the solution is transferred into a water bath tube, and Fe-NCNTs are subjected to water bath reaction for 3 hours at the temperature of 95 ℃ to prepare Fe-NCNTs @ NiFe-LDH.
From the OER-ORR linear voltammogram measured on the sample prepared in example 2 under the 1M KOH test condition in FIG. 1, it can be seen that the current density when the electrode passes during the OER process is 10mA/cm 2 When the reaction is carried out, the overpotential corresponding to the oxygen production of the OER in the alkaline aqueous solution is 210 mV; when the current density of the electrode passing through is 100mA/cm 2 When the reaction is carried out, the overpotential corresponding to the oxygen generation of the OER reaction in the alkaline aqueous solution is 260 mV. Half-wave E of the sample of example 2 during ORR 1/2 At 0.86V, Δ Ε of example 2 samples (Δ Ε ═ E ∑ E) j＝10 -E 1/2 ) It was 0.58V.
As can be seen from the OER-ORR linear voltammetry scan curve measured on the sample prepared in example 2 under the 0.1M KOH test condition in FIG. 3, the current density when the electrode passes during the OER process is 10mA/cm 2 When the reaction is carried out, the overpotential corresponding to the oxygen production of the OER in the alkaline aqueous solution is 272 mV; when the current density of the electrode passing through is 100mA/cm 2 When the reaction is carried out, the overpotential corresponding to the production of oxygen by OER in the alkaline aqueous solution is 345 mV. Half-wave E of the sample of example 2 during ORR 1/2 At 0.866V, Δ Ε of example 2 sample (Δ Ε ═ E) j＝10 -E 1/2 ) And was 0.64V.
Example 3
0.7378g of ferrous citrate and 2.667g of urea are dissolved in 40mL of UP water, then the solution is transferred into a water bath tube, and a carbon cloth is completely immersed in the solution to be subjected to water bath reaction at the temperature of 95 ℃ for 3 hours to prepare Fe-LDH/CC. And preparing a Tris solution with the pH value of 8.5, dissolving 0.4mg/mL dopamine hydrochloride in the Tris solution, suspending the carbon cloth loaded with the precursor in the mixed solution, and standing for 24 hours to attach the PDA. Placing the Fe-LDH/CC with the PDA attached in a tube furnace by a CVD method with Dicyandiamide (DCA) as a solid source in an argon atmosphere, heating to 350 ℃ from room temperature at a heating rate of 10 ℃/min, keeping the temperature for 1h, heating to 900 ℃ at a heating rate of 3 ℃/min, and keeping the temperature for 2h to prepare Fe-NCNTs. 0.71307g of ferrous citrate, 0.2459g of nickel chloride, 2.667g of urea and 0.1822g of CTAB are dissolved in 40mL of UP water, then the solution is transferred into a water bath tube, and Fe-NCNTs are subjected to water bath reaction for 3 hours at the temperature of 95 ℃ to prepare Fe-NCNTs @ NiFe-LDH.
From the OER-ORR linear voltammetry scan curves measured on the sample prepared in example 3 under the 1M KOH test condition in FIG. 1, the current density when the electrode passes during the OER process is 10mA/cm 2 When the reaction is carried out, the overpotential corresponding to the oxygen production by the OER reaction in the alkaline aqueous solution is 190 mV; when the current density of the electrode passing through is 100mA/cm 2 When the reaction is carried out, the overpotential corresponding to the oxygen production by the OER reaction in the alkaline aqueous solution is 240 mV. Half-wave E of the sample of example 3 during ORR 1/2 At 0.86V, Δ Ε of the example 3 samples (Δ Ε ═ E) j＝10 -E 1/2 ) It was 0.58V.
As can be seen from the OER-ORR linear voltammetry scan curves measured on the samples prepared in example 3 under the 0.1M KOH test condition in FIG. 3, the current density when the electrode passes during the OER process is 10mA/cm 2 When the reaction is carried out, the overpotential corresponding to the oxygen production by the OER reaction in the alkaline aqueous solution is 260 mV; when the current density of the electrode passing through is 100mA/cm 2 In this case, the overpotential corresponding to the oxygen generation by the OER reaction in the alkaline aqueous solution was 325 mV. Half-wave E of the sample of example 3 during ORR 1/2 At 0.851V, Δ Ε of the example 3 samples (Δ Ε ═ E) j＝10 -E 1/2 ) It was 0.63V.
Example 4
0.7378g of ferrous citrate and 2.667g of urea are dissolved in 40mL of UP water, then the solution is transferred into a water bath tube, and a carbon cloth is completely immersed in the solution to be subjected to water bath reaction at the temperature of 95 ℃ for 3 hours to prepare Fe-LDH/CC. And preparing a Tris solution with the pH value of 8.5, dissolving 0.4mg/mL dopamine hydrochloride in the Tris solution, suspending the carbon cloth loaded with the precursor in the mixed solution, and standing for 24 hours to attach the PDA. Placing Fe-LDH/CC attached with PDA in a tube furnace by using Dicyandiamide (DCA) as a solid source under argon atmosphere and a CVD method, heating to 350 ℃ from room temperature at a heating rate of 10 ℃/min, preserving heat for 1h, heating to 900 ℃ at a heating rate of 3 ℃/min, preserving heat for 2h, and preparing Fe-NCNTs. 0.71307g of ferrous citrate, 0.2459g of nickel chloride and 2.667g of urea are dissolved in 40mL of UP water, then the solution is transferred into a water bath tube, and Fe-NCNTs are subjected to water bath reaction at the temperature of 95 ℃ for 3 hours to prepare Fe-NCNTs @ NiFe-LDH.
From the OER-ORR linear voltammetry scan curves measured on the sample prepared in example 4 under the 1M KOH test condition in FIG. 1, the current density when the electrode passes during the OER process is 10mA/cm 2 When the reaction is carried out, the overpotential corresponding to the oxygen production by the OER reaction in the alkaline aqueous solution is 190 mV; when the current density of the electrode passing through is 100mA/cm 2 When the reaction is carried out, the overpotential corresponding to the oxygen production by the OER reaction in the alkaline aqueous solution is 240 mV. Half-wave E of the sample of example 4 during ORR 1/2 At 0.84V, Δ Ε of example 4 samples (Δ Ε ═ E) j＝10 -E 1/2 ) It was 0.57V.
As can be seen from the OER-ORR linear voltammetry scan curves measured on the samples prepared in example 4 under the 0.1M KOH test condition in FIG. 3, the current density when the electrode passes during the OER process is 10mA/cm 2 When the reaction is carried out, the overpotential corresponding to the oxygen production by the OER reaction in the alkaline aqueous solution is 252 mV; when the current density of the electrode passing through is 100mA/cm 2 In this case, the overpotential corresponding to the oxygen generation by the OER reaction in the alkaline aqueous solution was 325 mV. Half-wave E of the sample of example 4 during ORR 1/2 At 0.861V, Δ Ε of the example 4 samples (Δ Ε ═ E) j＝10 -E 1/2 ) And was 0.62V.
FIG. 7 is an SEM picture of a sample of example 4, which shows that NiFe-LDH grows perpendicularly on Fe-NCNTs nanotubes, but a part of the region shows an agglomeration phenomenon.
Example 5
0.7378g of ferrous citrate, 0.3565g of nickel chloride and 2.667g of urea are dissolved in 40mL of UP water, then the solution is transferred into a water bath tube, and a carbon cloth is completely immersed in the solution to be subjected to water bath reaction at the temperature of 95 ℃ for 3 hours to prepare NiFe-LDH/CC. And preparing a Tris solution with the pH value of 8.5, dissolving 0.4mg/mL dopamine hydrochloride in the Tris solution, suspending the carbon cloth loaded with the precursor in the mixed solution, and standing for 24 hours to attach the PDA. Placing NiFe-LDH/CC attached with PDA in a tube furnace by using Dicyandiamide (DCA) as a solid source under argon atmosphere and a CVD method, heating to 350 ℃ from room temperature at a heating rate of 10 ℃/min, preserving heat for 1h, heating to 800 ℃ at a heating rate of 3 ℃/min, preserving heat for 2h, and preparing the NiFe-NCNTs. 0.71307g of ferrous citrate, 0.2459g of nickel chloride, 2.667g of urea and 0.7289g of CTAB are dissolved in 40mL of UP water, then the solution is transferred into a water bath tube, and Fe-NCNTs are subjected to water bath reaction at the temperature of 95 ℃ for 3 hours to prepare NiFe-NCNTs @ NiFe-LDH.
From the OER-ORR linear voltammetry scan curve measured on the sample prepared in example 5 under the 1M KOH test condition in FIG. 2, the current density when the electrode passes during the OER process is 10mA/cm 2 When the reaction is carried out, the overpotential corresponding to the oxygen production of the OER in the alkaline aqueous solution is 200 mV; when the current density of the electrode passing through is 100mA/cm 2 When the reaction is carried out, the overpotential corresponding to the oxygen production by the OER reaction in the alkaline aqueous solution is 270 mV. Half-wave E of the sample of example 5 during ORR 1/2 At 0.81V, Δ Ε of example 5 samples (Δ Ε ═ E) j＝10 -E 1/2 ) And was 0.62V.
As can be seen from the OER-ORR linear voltammetry scan curves measured on the samples prepared in example 5 under the 0.1M KOH test condition in FIG. 4, the current density when the electrode passes during the OER process is 10mA/cm 2 When the reaction is carried out, the overpotential corresponding to the oxygen production by the OER reaction in the alkaline aqueous solution is 290 mV; when the current density of the electrode passing through is 100mA/cm 2 When the reaction is carried out, the overpotential corresponding to the oxygen production of the OER reaction in the alkaline aqueous solution is 300 mV. Half-wave E of the sample of example 5 during ORR 1/2 At 0.82V, Δ Ε of example 5 samples (Δ Ε ═ E) j＝10 -E 1/2 ) It was 0.70V.
FIG. 8 is a SEM picture of the sample of example 5 showing that NiFe-LDH nanosheets were grown on Fe-NCNTs nanotubes, but the NiFe-LDH nanosheets were grown too thickly and agglomerated significantly.
Example 6
0.7378g of ferrous citrate, 0.3565g of nickel chloride and 2.667g of urea are dissolved in 40mL of UP water, then the solution is transferred into a water bath tube, and a carbon cloth is completely immersed in the solution to carry out water bath reaction at the temperature of 95 ℃ for 3 hours to prepare the NiFe-LDH/CC. And preparing a Tris solution with the pH value of 8.5, dissolving 0.4mg/mL dopamine hydrochloride in the Tris solution, suspending the carbon cloth loaded with the precursor in the mixed solution, and standing for 24 hours to attach the PDA. Placing NiFe-LDH/CC attached with PDA in a tube furnace by using Dicyandiamide (DCA) as a solid source under argon atmosphere and a CVD method, heating to 350 ℃ from room temperature at a heating rate of 10 ℃/min, preserving heat for 1h, heating to 800 ℃ at a heating rate of 3 ℃/min, preserving heat for 2h, and preparing the NiFe-NCNTs. 0.71307g of ferrous citrate, 0.2459g of nickel chloride, 2.667g of urea and 0.3645g of CTAB are dissolved in 40mL of UP water, then the solution is transferred into a water bath tube, and Fe-NCNTs are subjected to water bath reaction at the temperature of 95 ℃ for 3 hours to prepare NiFe-NCNTs @ NiFe-LDH.
From the OER-ORR linear voltammetry scan curve measured on the sample prepared in example 6 under the 1M KOH test condition in FIG. 2, the current density when the electrode passes during the OER process is 10mA/cm 2 When the reaction is carried out, the overpotential corresponding to the oxygen production of the OER in the alkaline aqueous solution is 200 mV; when the current density of the electrode passing through is 100mA/cm 2 When the reaction is carried out, the overpotential corresponding to the production of oxygen by OER in the alkaline aqueous solution is 230 mV. Half-wave E of the sample of example 6 during ORR 1/2 At 0.82V, Δ Ε of the example 6 sample (Δ Ε ═ E) j＝10 -E 1/2 ) And was 0.61V.
As can be seen from the OER-ORR linear voltammetry scan curves measured on the samples prepared in example 6 under the 0.1M KOH test condition in FIG. 4, the current density when the electrode passes during the OER process is 10mA/cm 2 When the reaction is carried out, the overpotential corresponding to the oxygen production by the OER reaction in the alkaline aqueous solution is 270 mV; when the current density of the electrode passing through is 100mA/cm 2 When the reaction is carried out, the overpotential corresponding to the oxygen production by the OER reaction in the alkaline aqueous solution is 290 mV. Half-wave E of the sample of example 6 during ORR 1/2 At 0.81V, Δ Ε of example 6 samples (Δ Ε ═ Δ Ε)E j＝10 -E 1/2 ) It was 0.69V.
Example 7
0.7378g of ferrous citrate, 0.3565g of nickel chloride and 2.667g of urea are dissolved in 40mL of UP water, then the solution is transferred into a water bath tube, and a carbon cloth is completely immersed in the solution to be subjected to water bath reaction at the temperature of 95 ℃ for 3 hours to prepare NiFe-LDH/CC. And preparing a Tris solution with the pH value of 8.5, dissolving 0.4mg/mL dopamine hydrochloride in the Tris solution, suspending the carbon cloth loaded with the precursor in the mixed solution, and standing for 24 hours to attach the PDA. Placing NiFe-LDH/CC attached with PDA in a tube furnace by using Dicyandiamide (DCA) as a solid source under argon atmosphere and a CVD method, heating to 350 ℃ from room temperature at a heating rate of 10 ℃/min, preserving heat for 1h, heating to 800 ℃ at a heating rate of 3 ℃/min, preserving heat for 2h, and preparing the NiFe-NCNTs. 0.71307g of ferrous citrate, 0.2459g of nickel chloride, 2.667g of urea and 0.1822g of CTAB are dissolved in 40mL of UP water, then the solution is transferred into a water bath tube, and Fe-NCNTs are subjected to water bath reaction at the temperature of 95 ℃ for 3 hours to prepare NiFe-NCNTs @ NiFe-LDH.
From the OER-ORR linear voltammetry scan curves measured on the sample prepared in example 7 under the 1M KOH test condition in FIG. 2, the current density when the electrode passes during the OER process is 10mA/cm 2 When the reaction is carried out, the overpotential corresponding to the oxygen production of the OER in the alkaline aqueous solution is 190 mV; when the current density of the electrode passing through is 100mA/cm 2 When the reaction is carried out, the overpotential corresponding to the production of oxygen by OER in the alkaline aqueous solution is 250 mV. Half-wave E of the sample of example 7 during ORR 1/2 At 0.83V, Δ Ε of the example 7 sample (Δ Ε ═ E) j＝10 -E 1/2 ) It was 0.59V.
From the OER-ORR linear voltammogram measured on the sample prepared in example 7 under the 0.1M KOH test condition in FIG. 4, it can be seen that the current density when the electrode passes during the OER process is 10mA/cm 2 When the reaction is carried out, the overpotential corresponding to the oxygen production of the OER in the alkaline aqueous solution is 270 mV; when the current density of the electrode passing through is 100mA/cm 2 When the reaction is carried out, the overpotential corresponding to the oxygen production of the OER reaction in the alkaline aqueous solution is 300 mV. Half-wave E of the sample of example 7 during ORR 1/2 At 0.80V, Δ Ε of the example 7 sample (Δ Ε ═ E) j＝10 -E 1/2 ) Is 0.70V。
Example 8
0.7378g of ferrous citrate, 0.3565g of nickel chloride and 2.667g of urea are dissolved in 40mL of UP water, then the solution is transferred into a water bath tube, and a carbon cloth is completely immersed in the solution to be subjected to water bath reaction at the temperature of 95 ℃ for 3 hours to prepare NiFe-LDH/CC. And preparing a Tris solution with the pH value of 8.5, dissolving 0.4mg/mL dopamine hydrochloride in the Tris solution, suspending the carbon cloth loaded with the precursor in the mixed solution, and standing for 24 hours to attach the PDA. Placing NiFe-LDH/CC attached with PDA in a tube furnace by using Dicyandiamide (DCA) as a solid source under argon atmosphere and a CVD method, heating to 350 ℃ from room temperature at a heating rate of 10 ℃/min, preserving heat for 1h, heating to 800 ℃ at a heating rate of 3 ℃/min, preserving heat for 2h, and preparing the NiFe-NCNTs. 0.71307g of ferrous citrate, 0.2459g of nickel chloride and 2.667g of urea are dissolved in 40mL of UP water, then the solution is transferred into a water bath tube, and Fe-NCNTs are subjected to water bath reaction at the temperature of 95 ℃ for 3 hours to prepare NiFe-NCNTs @ NiFe-LDH.
From the OER-ORR linear voltammetry scan curve measured on the sample prepared in example 8 under the 1M KOH test condition in FIG. 2, the current density when the electrode passes during the OER process is 10mA/cm 2 When the reaction is carried out, the overpotential corresponding to the oxygen production by the OER reaction in the alkaline aqueous solution is 180 mV; when the current density of the electrode passing through is 100mA/cm 2 When the reaction is carried out, the overpotential corresponding to the oxygen production by the OER reaction in the alkaline aqueous solution is 230 mV. Half-wave E of the sample of example 8 during ORR 1/2 At 0.84V, Δ Ε of example 8 samples (Δ Ε ═ E) j＝10 -E 1/2 ) It was 0.57V.
As can be seen from the OER-ORR linear voltammetry scan curves measured on the sample prepared in example 8 under the 0.1M KOH test condition in FIG. 4, the current density when the electrode passes during the OER process is 10mA/cm 2 When the reaction is carried out, the overpotential corresponding to the oxygen production of the OER in the alkaline aqueous solution is 246 mV; when the current density of the electrode passing through is 100mA/cm 2 When the reaction is carried out, the overpotential corresponding to the production of oxygen by OER in the alkaline aqueous solution is 290 mV. Half-wave E of the sample of example 8 during ORR 1/2 At 0.86V, Δ Ε of example 8 samples (Δ Ε ═ E ∑ E) j＝10 -E 1/2 ) And was 0.62V.
FIG. 9 is a SEM picture of the sample of example 8 showing that NiFe-LDH nanosheets were grown on Fe-NCNTs nanotubes, but the NiFe-LDH nanosheets were grown too thickly and agglomerated significantly.
Example 9
0.7378g of ferrous citrate, 0.2377g of nickel chloride and 2.667g of urea are dissolved in 40mL of UP water, then the solution is transferred into a water bath tube, and a carbon cloth is completely immersed in the solution to be subjected to water bath reaction at the temperature of 95 ℃ for 3 hours to prepare NiFe-LDH/CC. And preparing a Tris solution with the pH value of 8.5, dissolving 0.4mg/mL dopamine hydrochloride in the Tris solution, suspending the carbon cloth loaded with the precursor in the mixed solution, and standing for 24 hours to attach the PDA. Placing the NiFe-LDH/CC with the PDA attached in a tube furnace by a CVD method with Dicyandiamide (DCA) as a solid source in an argon atmosphere, heating to 350 ℃ from room temperature at a heating rate of 10 ℃/min, keeping the temperature for 1h, heating to 900 ℃ at a heating rate of 3 ℃/min, and keeping the temperature for 2h to prepare the NiFe-NCNTs. 0.71307g of ferrous citrate, 0.2459g of nickel chloride, 2.667g of urea and 0.7289g of CTAB are dissolved in 40mL of UP water, then the solution is transferred into a water bath tube, and Fe-NCNTs are subjected to water bath reaction at the temperature of 95 ℃ for 3 hours to prepare NiFe-NCNTs @ NiFe-LDH.
From the OER-ORR linear voltammogram measured on the sample prepared in example 9 under the 0.1M KOH test condition in FIG. 5, it can be seen that the current density when the electrode passes during the OER process is 10mA/cm 2 When the reaction is carried out, the overpotential corresponding to the oxygen production by the OER reaction in the alkaline aqueous solution is 165 mV; when the current density of the electrode passing through is 100mA/cm 2 When the reaction is carried out, the overpotential corresponding to the oxygen production of the OER reaction in the alkaline aqueous solution is 190 mV. Half-wave E of the sample of example 9 during ORR 1/2 At 0.78V, Δ Ε of example 9 samples (Δ Ε ═ E ∑ E) j＝10 -E 1/2 ) And was 0.62V.
Example 10
0.7378g of ferrous citrate, 0.2377g of nickel chloride and 2.667g of urea are dissolved in 40mL of UP water, then the solution is transferred into a water bath tube, and a carbon cloth is completely immersed in the solution to carry out water bath reaction at the temperature of 95 ℃ for 3 hours to prepare the NiFe-LDH/CC. And preparing a Tris solution with the pH value of 8.5, dissolving 0.4mg/mL dopamine hydrochloride in the Tris solution, suspending the carbon cloth loaded with the precursor in the mixed solution, and standing for 24 hours to attach the PDA. Placing NiFe-LDH/CC attached with PDA in a tube furnace by using Dicyandiamide (DCA) as a solid source under argon atmosphere and a CVD method, heating to 350 ℃ from room temperature at a heating rate of 10 ℃/min, preserving heat for 1h, heating to 900 ℃ at a heating rate of 3 ℃/min, preserving heat for 2h, and preparing the NiFe-NCNTs. 0.71307g of ferrous citrate, 0.2459g of nickel chloride, 2.667g of urea CTAB and 0.3645g of urea CTAB are dissolved in 40mL of UP water, then the solution is transferred into a water bath tube, and Fe-NCNTs are subjected to water bath reaction for 3 hours at the temperature of 95 ℃ to prepare NiFe-NCNTs @ NiFe-LDH.
As can be seen from the OER-ORR linear voltammetry scan curves measured on the samples prepared in example 10 under the 0.1M KOH test condition in FIG. 5, the current density when the electrode passes during the OER process is 10mA/cm 2 When the reaction is carried out, the overpotential corresponding to the oxygen production by the OER reaction in the alkaline aqueous solution is 148 mV; when the current density of the electrode passing through is 100mA/cm 2 When the reaction is carried out, the overpotential corresponding to the oxygen generation of the OER reaction in the alkaline aqueous solution is 210 mV. Half-wave E of the sample of example 10 during ORR 1/2 At 0.78V, Δ Ε of example 10 samples (Δ Ε ═ E) j＝10 -E 1/2 ) It was 0.60V.
Example 11
0.7378g of ferrous citrate, 0.2377g of nickel chloride and 2.667g of urea are dissolved in 40mL of UP water, then the solution is transferred into a water bath tube, and a carbon cloth is completely immersed in the solution to be subjected to water bath reaction at the temperature of 95 ℃ for 3 hours to prepare NiFe-LDH/CC. And preparing a Tris solution with the pH value of 8.5, dissolving 0.4mg/mL dopamine hydrochloride in the Tris solution, suspending the carbon cloth loaded with the precursor in the mixed solution, and standing for 24 hours to attach the PDA. Placing the NiFe-LDH/CC with the PDA attached in a tube furnace by a CVD method with Dicyandiamide (DCA) as a solid source in an argon atmosphere, heating to 350 ℃ from room temperature at a heating rate of 10 ℃/min, keeping the temperature for 1h, heating to 900 ℃ at a heating rate of 3 ℃/min, and keeping the temperature for 2h to prepare the NiFe-NCNTs. 0.71307g of ferrous citrate, 0.2459g of nickel chloride, 2.667g of nickel chloride and 0.1822g of CTAB urea are dissolved in 40mL of UP water, then the solution is transferred into a water bath tube, and Fe-NCNTs are subjected to water bath reaction at the temperature of 95 ℃ for 3 hours to prepare NiFe-NCNTs @ NiFe-LDH.
OER-The ORR linear voltammetry scanning curve shows that the current density when the electrode passes in the OER process is 10mA/cm 2 In this case, the overpotential corresponding to the production of oxygen by the OER reaction in the aqueous alkaline solution was 174 mV. Half-wave E of the sample of example 11 during ORR 1/2 At 0.70V, Δ Ε of example 11 samples (Δ Ε ═ E ∑ E) j＝10 -E 1/2 ) It was 0.70V.
Example 12
0.7378g of ferrous citrate, 0.2377g of nickel chloride and 2.667g of urea are dissolved in 40mL of UP water, then the solution is transferred into a water bath tube, and a carbon cloth is completely immersed in the solution to be subjected to water bath reaction at the temperature of 95 ℃ for 3 hours to prepare NiFe-LDH/CC. And preparing a Tris solution with the pH value of 8.5, dissolving 0.4mg/mL dopamine hydrochloride in the Tris solution, suspending the carbon cloth loaded with the precursor in the mixed solution, and standing for 24 hours to attach the PDA. Placing NiFe-LDH/CC attached with PDA in a tube furnace by using Dicyandiamide (DCA) as a solid source under argon atmosphere and a CVD method, heating to 350 ℃ from room temperature at a heating rate of 10 ℃/min, preserving heat for 1h, heating to 900 ℃ at a heating rate of 3 ℃/min, preserving heat for 2h, and preparing the NiFe-NCNTs. 0.71307g of ferrous citrate, 0.2459g of nickel chloride and 2.667g of urea are dissolved in 40mL of UP water, then the solution is transferred into a water bath tube, and Fe-NCNTs react in the water bath at the temperature of 95 ℃ for 3 hours to prepare NiFe-NCNTs @ NiFe-LDH.
As can be seen from the OER-ORR linear voltammetry scan curves measured on the sample prepared in example 12 under the 0.1M KOH test condition in FIG. 5, the current density when the electrode passes during the OER process is 10mA/cm 2 When the reaction is carried out, the overpotential corresponding to the oxygen production of the OER in the alkaline aqueous solution is 125 mV; when the current density of the electrode passing through is 100mA/cm 2 When the reaction is carried out, the overpotential corresponding to the production of oxygen by the OER reaction in the alkaline aqueous solution is 185 mV. Half-wave E of the sample of example 12 during ORR 1/2 At 0.73V, Δ Ε of the example 12 samples (Δ Ε ═ E) j＝10 -E 1/2 ) It was 0.63V.
Claims (9)
1. A preparation method of a Fe (Ni) -NCNTs @ NiFe-LDH in-situ electrode is characterized by comprising the following steps:
s1, preparing Fe (Ni) -LDH precursor: dissolving ferrous citrate and urea in UP water to obtain a mixed solution, transferring the mixed solution into a water bath pipe, completely immersing carbon cloth in the solution, and reacting at a certain time and a certain temperature to obtain a Fe (Ni) -LDH precursor;
s2, wrapping polydopamine: dissolving dopamine hydrochloride in a Tris solution, suspending carbon cloth loaded with Fe (Ni) -LDH precursors in the mixed solution, and standing for a period of time to attach PDA;
s3, preparing Fe (Ni) -NCNTs: under the argon atmosphere, dicyandiamide is used as a solid nitrogen source, a CVD method is utilized to place the Fe (Ni) -LDH precursor attached with PDA into a tube furnace, and Fe (Ni) -NCNTs are prepared by sintering;
s4, preparation of Fe (Ni) -NCNTs @ NiFe-LDH in situ electrode: ferrous citrate, nickel chloride, urea and hexadecyl trimethyl ammonium bromide are dissolved in UP water, then the solution is transferred into a water bath tube, and Fe (Ni) -NCNTs are completely immersed into the solution to react to prepare a final sample Fe (Ni) -NCNTs @ NiFe-LDH.
2. The method for preparing an Fe (Ni) -NCNTs @ NiFe-LDH in-situ electrode according to claim 1, wherein the mass ratio of ferrous citrate to urea in S1 is 1:3-1: 4.
3. The method for preparing an Fe (Ni) -NCNTs @ NiFe-LDH in-situ electrode as claimed in claim 1, wherein the mixed solution of S1 is further added with nickel chloride, and the mass ratio of the nickel chloride to the ferrous citrate is 1:1-1: 3.
4. The method for preparing an in situ electrode of Fe (Ni) -NCNTs @ NiFe-LDH as claimed in claim 1, wherein the temperature of the water bath is maintained at 95-100 ℃ for 3-4h in S1.
5. The method for preparing an in-situ electrode of Fe (Ni) -NCNTs @ NiFe-LDH as claimed in claim 1, wherein the concentration of dopamine hydrochloride in S2 is 0.4-0.6mg/mL, and the time for attaching PDA is 24-30h at room temperature.
6. The method for preparing an Fe (Ni) -NCNTs @ NiFe-LDH in-situ electrode as claimed in claim 1, wherein the mass ratio of dicyandiamide to the Fe (Ni) -LDH precursor after PDA attachment in S3 is 10-30: 1.
7. The method for preparing an Fe (Ni) -NCNTs @ NiFe-LDH in-situ electrode as claimed in claim 1, wherein in S3, the CVD method comprises the steps of heating from room temperature to 350-420 ℃ at a heating rate of 5-10 ℃/min, maintaining the temperature for 1-2h, heating to 800-900 ℃ at a heating rate of 3-5 ℃/min, and maintaining the temperature for 2-5 h.
8. The method for preparing an Fe (Ni) -NCNTs @ NiFe-LDH in-situ electrode as claimed in claim 1, wherein in S4, the mass ratio of nickel chloride to ferrous citrate is 1:1-1:3, the mass ratio of ferrous citrate to urea is 1:3-1:4, the dosage of cetyl trimethyl ammonium bromide is 0.1-2mmol, the temperature of the water bath is maintained to 95-100 ℃, and the time is 3-4 h.
9. The method of claim 1 wherein the temperature of the water bath is maintained at 95-100 ℃ for 3-4h in S4.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105826574A (en) * | 2016-03-24 | 2016-08-03 | 青岛科技大学 | Nitrogen-doped graphene/ ferrocobalt hydrotalcite-like compound difunctional oxygen-reduction catalyst and preparing method and application thereof |
| CN109696463A (en) * | 2019-02-21 | 2019-04-30 | 三峡大学 | A kind of Co4S3With the preparation method of nitrogen-doped carbon composite array electrode |
| CN112886029A (en) * | 2021-01-12 | 2021-06-01 | 深圳清华大学研究院 | Bifunctional oxygen electrocatalyst with hollow carbon nanotube as carrier, preparation and application |
| CN113113615A (en) * | 2021-04-08 | 2021-07-13 | 浙江师范大学 | NiFe-LDH/Co-CNTs nano composite material and preparation method and application thereof |
| CN113258080A (en) * | 2021-05-13 | 2021-08-13 | 三峡大学 | Method for preparing nitrogen-doped carbon nanotube-coated cobalt metal electrocatalyst |
-
2022
- 2022-04-08 CN CN202210367432.0A patent/CN114792810B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105826574A (en) * | 2016-03-24 | 2016-08-03 | 青岛科技大学 | Nitrogen-doped graphene/ ferrocobalt hydrotalcite-like compound difunctional oxygen-reduction catalyst and preparing method and application thereof |
| CN109696463A (en) * | 2019-02-21 | 2019-04-30 | 三峡大学 | A kind of Co4S3With the preparation method of nitrogen-doped carbon composite array electrode |
| CN112886029A (en) * | 2021-01-12 | 2021-06-01 | 深圳清华大学研究院 | Bifunctional oxygen electrocatalyst with hollow carbon nanotube as carrier, preparation and application |
| CN113113615A (en) * | 2021-04-08 | 2021-07-13 | 浙江师范大学 | NiFe-LDH/Co-CNTs nano composite material and preparation method and application thereof |
| CN113258080A (en) * | 2021-05-13 | 2021-08-13 | 三峡大学 | Method for preparing nitrogen-doped carbon nanotube-coated cobalt metal electrocatalyst |
Non-Patent Citations (1)
| Title |
|---|
| HANG LEI ET AL.: "NiFe Nanoparticles Embedded N-doped Carbon Nanotubes as High-Efficient Electrocatalysts for Wearable Solid-State Zn-air Batteries", NANO ENERGY, pages 1 - 25 * |
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