CN114792810B - 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
- Publication number
- CN114792810B CN114792810B CN202210367432.0A CN202210367432A CN114792810B CN 114792810 B CN114792810 B CN 114792810B CN 202210367432 A CN202210367432 A CN 202210367432A CN 114792810 B CN114792810 B CN 114792810B
- Authority
- CN
- China
- Prior art keywords
- ldh
- ncnts
- nife
- feni
- water bath
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 90
- 229920001690 polydopamine Polymers 0.000 claims abstract description 38
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 32
- 239000004744 fabric Substances 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 28
- 239000002243 precursor Substances 0.000 claims abstract description 26
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims description 70
- 239000000243 solution Substances 0.000 claims description 59
- 238000010438 heat treatment Methods 0.000 claims description 44
- 235000019850 ferrous citrate Nutrition 0.000 claims description 37
- 239000011640 ferrous citrate Substances 0.000 claims description 37
- 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 37
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 35
- 239000004202 carbamide Substances 0.000 claims description 35
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 28
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 28
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 28
- 239000011259 mixed solution Substances 0.000 claims description 21
- 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 15
- 239000007983 Tris buffer Substances 0.000 claims description 14
- 239000012300 argon atmosphere Substances 0.000 claims description 14
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 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
- 238000004519 manufacturing process Methods 0.000 claims 3
- 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
- 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 39
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 15
- 239000007787 solid Substances 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 6
- 239000002064 nanoplatelet 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
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000009977 dual effect Effects 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
- 238000010998 test method Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- 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
- H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
-
- 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
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Inert Electrodes (AREA)
Abstract
The invention provides a preparation method of an Fe (Ni) -NCNTs@NiFe-LDH in-situ electrode. Preparing a double-layer hydroxide (Fe (Ni) -LDH) precursor on Carbon Cloth (CC) by using a water bath method, attaching Polydopamine (PDA) on the precursor, preparing Fe (Ni) -NCNTs by Chemical Vapor Deposition (CVD) annealing, and finally growing nickel-iron double-layer hydroxide on the Fe (Ni) -NCNTs by using the water bath method again to prepare the final sample Fe (Ni) -NCNTs@NiFe-LDH. The technical scheme of the invention has the advantages of low cost of 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 performances, excellent stability and rich active sites, and can provide excellent electrode materials for subsequent research of zinc-air batteries.
Description
Technical Field
The invention relates to preparation of a multi-component multifunctional material, and belongs to the field of electrocatalytic and energy conversion materials and devices.
Background
In view of global energy shortage and climate change problems, it is becoming vital to develop advanced technologies for producing sustainable energy. The reversible zinc-air battery has stable performance, no pollution and high theoretical energy density (1084 Wh.kg), and is a promising substitute for solving the current global energy crisis and serious environmental problems. However, the inherent decrease in Oxygen Evolution Reaction (OER) kinetics during charging and insufficient Oxygen Reduction Reaction (ORR) activity during discharging severely hamper commercialization. Thus, the search for efficient bifunctional catalysts remains a great challenge.
NiFe double hydroxide (NiFe-LDH) nanoplatelets are well known as low cost non-noble metal catalysts for their excellent OER catalytic activity. However, its inherent low conductivity and self-agglomeration, as well as the only single OER activity without ORR performance, severely hamper its use in reversible zinc air cells. To overcome these drawbacks of NiFe-LDHs, researchers have tried to combine NiFe-LDHs with various carbon matrices to increase their conductivity (Angew.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 environment. Sci.2016,9, 2020-2024). M (Fe, ni) -N-C based catalysts have proven to be potential ORR catalysts, which perform even better than Pt/C, but have poor stability themselves.
In order to improve the stability and OER performance of the M (Fe, ni) -N-C-based catalyst, a NiFe-LDH catalyst, namely an in-situ electrode of Fe (Ni) -NCNTs@NiFe-LDH, is introduced to the surface of the M-N-C. The prepared Fe (Ni) -NCNTs@NiFe-LDH in-situ electrode is expected to have excellent ORR and OER double performances, excellent stability and rich active sites, and can provide excellent electrode materials for subsequent research of zinc-air batteries.
Disclosure of Invention
In view of this, the present invention provides a method for preparing an in situ electrode of Fe (Ni) -NCNTs@NiFe-LDH, comprising the steps of:
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, and completely immersing carbon cloth in the solution to obtain a Fe (Ni) -LDH precursor through reaction at a certain temperature for a certain time;
s2, wrapping polydopamine: dissolving a certain amount of dopamine hydrochloride in a Tris solution, suspending the carbon cloth loaded with Fe (Ni) -LDH precursor in the mixed solution, and standing for a period of time to attach PDA;
s3, preparing Fe (Ni) -NCNTs: under argon atmosphere, dicyandiamide is used as a nitrogen fixation source, a CVD method is utilized to place Fe (Ni) -LDH precursors attached with PDA in a tube furnace, and Fe (Ni) -NCNTs are prepared by sintering;
s4, preparing an 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 pipe, fe (Ni) -NCNTs are completely immersed in the solution, and the final sample Fe (Ni) -NCNTs@NiFe-LDH is prepared through reaction at a certain time and a certain temperature.
In S1, the mass ratio of ferrous citrate to urea is 1:3-1:4, the temperature of the water bath is maintained to 95-100 ℃ for 3-4 hours, preferably the temperature of the water bath is maintained to 95 ℃ for 3 hours.
And (2) nickel chloride is also added into the mixed solution in the step (S1), and the concentration ratio of the nickel chloride to the ferrous citrate is 1:1-1:3.
In S2, the concentration of the dopamine hydrochloride is 0.4-0.6mg/mL, and the time for attaching the PDA is 24-30h at normal temperature.
Further, the concentration of the dopamine hydrochloride is preferably 0.4mg/mL, and the time for attaching the PDA is preferably 24 hours.
Further, in S3, the mass ratio of dicyandiamide to Fe (Ni) -LDH precursor after PDA is attached is 10-30:1. The CVD sintering condition is that the temperature is raised to 350-420 ℃ from the room temperature at the temperature raising rate of 5-10 ℃/min, the temperature is kept for 1-2h, the temperature is raised to 800-900 ℃ at the temperature raising rate of 3-5 ℃/min, and the temperature is kept for 2-5h.
Further, 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 hexadecyl trimethyl ammonium bromide is 0.1-2mmol, the temperature of the water bath is maintained to 95-100 ℃, and the time is 3-4h.
The invention has the following beneficial effects:
the Fe (Ni) -NCNTs@NiFe-LDH in-situ electrode has excellent ORR and OER dual performance in a 1M KOH and 0.1M KOH test system.
2. Excellent stability and rich active sites.
3. Can provide excellent electrode materials for subsequent research of zinc-air batteries.
Drawings
FIG. 1, 1M KOH test conditions OER-ORR linear voltammetric scan curves for examples 1, 2, 3, 4, inset is a partial enlargement.
FIG. 2, 1M KOH test conditions, OER-ORR linear voltammetric scan curves for examples 5, 6, 7, 8, inset is a partial enlargement.
FIG. 3, 0.1M KOH test conditions of the OER-ORR linear voltammetric scan of examples 1, 2, 3, 4, inset is a partial enlargement.
FIG. 4, 0.1M KOH test conditions of OER-ORR linear voltammetric scan curve, inset, partial enlargement of examples 5, 6, 7, 8.
FIG. 5, 0.1M KOH test conditions of OER-ORR linear voltammetric scan curve, inset, partial enlargement of examples 9, 10, 11, 12.
Fig. 6, sample SEM (a) of example 1, 5000 x (b) 20000 x.
Fig. 7, example 4 sample SEM (a) 5000 x (b) 22000 x.
Fig. 8, example 5 sample SEM (a) 5000 x (b) 20000 x.
Fig. 9, example 8 sample SEM (a) 5000 x (b) 20000 x.
Detailed Description
Characterization conditions
The OER-ORR test method in the embodiment of the invention comprises the following steps: the example samples are used as working electrodes, carbon rods are used as counter electrodes, saturated Hg/HgO electrodes are used as reference electrodes, and the electrolytes are as follows: 1M aqueous KOH solution and 0.1M aqueous KOH solution, the scanning speed is 5 to 10mV/s. Oxygen was introduced during the ORR-OER test. Oxygen was naturally saturated in 1M aqueous KOH and 0.1M aqueous KOH and stirred with 150 revolutions per minute during the test. The saturated Hg/HgO electrode was corrected with a reversible hydrogen electrode, and the potentials described below were all potentials relative to the reversible hydrogen electrode. Potential (IR) compensation was automatically performed with the Shanghai 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 the carbon cloth is completely immersed in the solution for water bath reaction at 95 ℃ for 3 hours to prepare the Fe-LDH/CC. A Tris solution with ph=8.5 was prepared, and 0.4mg/mL of dopamine hydrochloride was dissolved therein, and the carbon cloth loaded with the precursor was suspended in the mixed solution and left for 24 hours to attach PDA. Under argon atmosphere, taking Dicyandiamide (DCA) as a solid source, placing the Fe-LDH/CC attached with PDA into a tube furnace by using a CVD method, heating to 350 ℃ at a heating rate of 10 ℃/min from room temperature, preserving heat for 1h, heating to 900 ℃ at a heating rate of 3 ℃/min, and preserving heat for 2h to prepare the 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 to a water bath tube, and Fe-NCNTs are subjected to water bath reaction at 95 ℃ for 3 hours to prepare Fe-NCNTs@NiFe-LDH.
As can be seen from the OER-ORR linear voltammetric scan curve of the sample prepared in example 1 under the 1M KOH test condition in FIG. 1, the current density passing through the electrode during OER is 10mA/cm 2 When the oxygen is generated by OER reaction in the alkaline aqueous solution, the corresponding overpotential is 180mV; when the current density passing through the electrode is 100mA/cm 2 When the oxygen is generated by OER reaction in the alkaline aqueous solution, the corresponding overpotential is 230mV. Half wave E of example 1 sample in ORR procedure 1/2 ΔΣ of example 1 sample (ΔΣ=e at 0.885V j＝10 -E 1/2 ) Is 0.53V.
As can be seen from the OER-ORR linear voltammetric scan curve of the sample prepared in example 1 under the 0.1M KOH test condition in FIG. 3, the current density passing through the electrode during OER is 10mA/cm 2 When the oxygen is generated by OER reaction in the alkaline aqueous solution, the corresponding overpotential is 251mV; when the current density passing through the electrode is 100mA/cm 2 When the oxygen is generated by OER reaction in the alkaline aqueous solution, the corresponding overpotential is 315mV. Half wave E of example 1 sample in ORR procedure 1/2 ΔΣ of example 1 sample at 0.851V (ΔΣ=e j＝10 -E 1/2 ) 0.63V.
FIG. 6 is an SEM photograph of example 1, showing that ultrathin NiFe-LDH nanoplatelets are uniformly grown vertically 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 the carbon cloth is completely immersed in the solution for water bath reaction at 95 ℃ for 3 hours to prepare the Fe-LDH/CC. A Tris solution with ph=8.5 was prepared, and 0.4mg/mL of dopamine hydrochloride was dissolved therein, and the carbon cloth loaded with the precursor was suspended in the mixed solution and left for 24 hours to attach PDA. Under argon atmosphere, taking Dicyandiamide (DCA) as a solid source, placing the Fe-LDH/CC attached with PDA into a tube furnace by using a CVD method, heating to 350 ℃ at a heating rate of 10 ℃/min from room temperature, preserving heat for 1h, heating to 900 ℃ at a heating rate of 3 ℃/min, and preserving heat for 2h to prepare the 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 to a water bath tube, and Fe-NCNTs are subjected to water bath reaction at 95 ℃ for 3 hours to prepare Fe-NCNTs@NiFe-LDH.
As can be seen from the OER-ORR linear voltammetric scan curve of the sample prepared in example 2 under the 1M KOH test condition in FIG. 1, the current density passing through the electrode during OER is 10mA/cm 2 When the oxygen is generated by OER reaction in the alkaline aqueous solution, the corresponding overpotential is 210mV; when the current density passing through the electrode is 100mA/cm 2 When the oxygen is generated by OER reaction in the alkaline aqueous solution, the corresponding overpotential is 260mV. Half wave E of example 2 sample in ORR procedure 1/2 ΔΣ of example 2 sample at 0.86V (ΔΣ=e j＝10 -E 1/2 ) Is 0.58V.
As can be seen from the OER-ORR linear voltammetric scan curve of the sample prepared in example 2 under the 0.1M KOH test condition in FIG. 3, the current density passing through the electrode during OER is 10mA/cm 2 When the oxygen is generated by OER reaction in the alkaline aqueous solution, the corresponding overpotential is 272mV; when the current density passing through the electrode is 100mA/cm 2 When the oxygen is generated by OER reaction in the alkaline aqueous solution, the corresponding overpotential is 345mV. Half wave E of example 2 sample in ORR procedure 1/2 ΔΣ of example 2 sample at 0.866V (ΔΣ=e j＝10 -E 1/2 ) Is 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 the carbon cloth is completely immersed in the solution for water bath reaction at 95 ℃ for 3 hours to prepare the Fe-LDH/CC. A Tris solution with ph=8.5 was prepared, and 0.4mg/mL of dopamine hydrochloride was dissolved therein, and the carbon cloth loaded with the precursor was suspended in the mixed solution and left for 24 hours to attach PDA. Under argon atmosphere, taking Dicyandiamide (DCA) as a solid source, placing the Fe-LDH/CC attached with PDA into a tube furnace by using a CVD method, heating to 350 ℃ at a heating rate of 10 ℃/min from room temperature, preserving heat for 1h, heating to 900 ℃ at a heating rate of 3 ℃/min, and preserving heat for 2h to prepare the 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 to a water bath tube, and Fe-NCNTs are subjected to water bath reaction at 95 ℃ for 3 hours to prepare Fe-NCNTs@NiFe-LDH.
As can be seen from the OER-ORR linear voltammetric scan curve of the sample prepared in example 3 under the 1M KOH test condition in FIG. 1, the current density passing through the electrode during OER is 10mA/cm 2 When the oxygen is generated by OER reaction in the alkaline aqueous solution, the corresponding overpotential is 190mV; when the current density passing through the electrode is 100mA/cm 2 When the oxygen is generated by OER reaction in the alkaline aqueous solution, the corresponding overpotential is 240mV. Half wave E of example 3 sample in ORR procedure 1/2 ΔΣ of example 3 sample at 0.86V (ΔΣ=e j＝10 -E 1/2 ) Is 0.58V.
As can be seen from the OER-ORR linear voltammetric scan curve of the sample prepared in example 3 under the 0.1M KOH test condition in FIG. 3, the current density passing through the electrode during OER is 10mA/cm 2 When the oxygen is generated by OER reaction in the alkaline aqueous solution, the corresponding overpotential is 260mV; when the current density passing through the electrode is 100mA/cm 2 When the oxygen is generated by OER reaction in the alkaline aqueous solution, the corresponding overpotential is 325mV. Half wave E of example 3 sample in ORR procedure 1/2 ΔΣ of example 3 sample (ΔΣ=e) was 0.851V j＝10 -E 1/2 ) 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 the carbon cloth is completely immersed in the solution for water bath reaction at 95 ℃ for 3 hours to prepare the Fe-LDH/CC. A Tris solution with ph=8.5 was prepared, and 0.4mg/mL of dopamine hydrochloride was dissolved therein, and the carbon cloth loaded with the precursor was suspended in the mixed solution and left for 24 hours to attach PDA. Under argon atmosphere, taking Dicyandiamide (DCA) as a solid source, placing the Fe-LDH/CC attached with PDA into a tube furnace by using a CVD method, heating to 350 ℃ at a heating rate of 10 ℃/min from room temperature, preserving heat for 1h, heating to 900 ℃ at a heating rate of 3 ℃/min, and preserving heat for 2h to prepare the 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 to a water bath tube, and Fe-NCNTs are subjected to water bath reaction at 95 ℃ for 3 hours to prepare Fe-NCNTs@NiFe-LDH.
As can be seen from the OER-ORR linear voltammetric scan curve of the sample prepared in example 4 under the 1M KOH test condition in FIG. 1, the current density passing through the electrode during OER is 10mA/cm 2 When the oxygen is generated by OER reaction in the alkaline aqueous solution, the corresponding overpotential is 190mV; when the current density passing through the electrode is 100mA/cm 2 When the oxygen is generated by OER reaction in the alkaline aqueous solution, the corresponding overpotential is 240mV. Half wave E of example 4 sample in ORR procedure 1/2 ΔΣ of example 4 sample at 0.84V (ΔΣ=e j＝10 -E 1/2 ) 0.57V.
As can be seen from the OER-ORR linear voltammetric scan curve of the sample prepared in example 4 under the 0.1M KOH test condition in FIG. 3, the current density passing through the electrode during OER is 10mA/cm 2 When the oxygen is generated by OER reaction in the alkaline aqueous solution, the corresponding overpotential is 252mV; when the current density passing through the electrode is 100mA/cm 2 When the oxygen is generated by OER reaction in the alkaline aqueous solution, the corresponding overpotential is 325mV. Half wave E of example 4 sample in ORR procedure 1/2 ΔΣ of example 4 sample at 0.861V (ΔΣ=e j＝10 -E 1/2 ) Is 0.62V.
FIG. 7 is an SEM photograph of a sample of example 4 showing that NiFe-LDH grows vertically on Fe-NCNTs nanotubes, but a portion of the region exhibits agglomeration.
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 the carbon cloth is completely immersed in the solution and subjected to water bath reaction at 95 ℃ for 3 hours to prepare the NiFe-LDH/CC. A Tris solution with ph=8.5 was prepared, and 0.4mg/mL of dopamine hydrochloride was dissolved therein, and the carbon cloth loaded with the precursor was suspended in the mixed solution and left for 24 hours to attach PDA. And placing the NiFe-LDH/CC attached with the PDA into a tube furnace by using a CVD method under the argon atmosphere and taking Dicyandiamide (DCA) as a solid source, heating to 350 ℃ at a heating rate of 10 ℃/min from the room temperature, preserving heat for 1h, heating to 800 ℃ at a heating rate of 3 ℃/min, and preserving heat 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 were dissolved in 40mL of UP water, then the solution was transferred to a water bath tube, and the Fe-NCNTs were subjected to a water bath reaction at 95℃for 3 hours to prepare NiFe-NCNTs@NiFe-LDH.
As can be seen from the OER-ORR linear voltammetric scan curve of the sample prepared in example 5 under the 1M KOH test condition in FIG. 2, the current density passing through the electrode during OER is 10mA/cm 2 When the oxygen is generated by OER reaction in the alkaline aqueous solution, the corresponding overpotential is 200mV; when the current density passing through the electrode is 100mA/cm 2 When the oxygen is generated by OER reaction in the alkaline aqueous solution, the corresponding overpotential is 270mV. Half wave E of example 5 sample in ORR procedure 1/2 ΔΣ of example 5 sample at 0.81V (ΔΣ=e j＝10 -E 1/2 ) Is 0.62V.
As can be seen from the OER-ORR linear voltammetric scan curve of the sample prepared in example 5 under the 0.1M KOH test condition in FIG. 4, the current density passing through the electrode during OER is 10mA/cm 2 When the oxygen is generated by OER reaction in the alkaline aqueous solution, the corresponding overpotential is 290mV; when the current density passing through the electrode is 100mA/cm 2 When the oxygen is generated by OER reaction in the alkaline aqueous solution, the corresponding overpotential is 300mV. Half wave E of example 5 sample in ORR procedure 1/2 ΔΣ of example 5 sample at 0.82V (ΔΣ=e j＝10 -E 1/2 ) Is 0.70V.
FIG. 8 is a photograph of an SEM of the sample of example 5, showing that NiFe-LDH nanoplatelets grow on Fe-NCNTs nanotubes, but that the NiFe-LDH nanoplatelets grow too thick and agglomerate 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 the carbon cloth is completely immersed in the solution and subjected to water bath reaction at 95 ℃ for 3 hours to prepare the NiFe-LDH/CC. A Tris solution with ph=8.5 was prepared, and 0.4mg/mL of dopamine hydrochloride was dissolved therein, and the carbon cloth loaded with the precursor was suspended in the mixed solution and left for 24 hours to attach PDA. And placing the NiFe-LDH/CC attached with the PDA into a tube furnace by using a CVD method under the argon atmosphere and taking Dicyandiamide (DCA) as a solid source, heating to 350 ℃ at a heating rate of 10 ℃/min from the room temperature, preserving heat for 1h, heating to 800 ℃ at a heating rate of 3 ℃/min, and preserving heat for 2h to prepare the NiFe-NCNTs. 0.71307g of ferrous citrate, 0.2459g of nickel chloride, 2.667g of urea and 0.3645g of CTAB were dissolved in 40mL of UP water, then the solution was transferred to a water bath tube, and the Fe-NCNTs were subjected to a water bath reaction at 95℃for 3 hours to prepare NiFe-NCNTs@NiFe-LDH.
As can be seen from the OER-ORR linear voltammetric scan curve of the sample prepared in example 6 under the 1M KOH test condition in FIG. 2, the current density passing through the electrode during OER is 10mA/cm 2 When the oxygen is generated by OER reaction in the alkaline aqueous solution, the corresponding overpotential is 200mV; when the current density passing through the electrode is 100mA/cm 2 When the oxygen is generated by OER reaction in the alkaline aqueous solution, the corresponding overpotential is 230mV. Half wave E of example 6 sample in ORR procedure 1/2 ΔΣ of example 6 sample at 0.82V (ΔΣ=e j＝10 -E 1/2 ) Is 0.61V.
As can be seen from the OER-ORR linear voltammetric scan curve of the sample prepared in example 6 under the 0.1M KOH test condition in FIG. 4, the current density passing through the electrode during OER is 10mA/cm 2 When the oxygen is generated by OER reaction in the alkaline aqueous solution, the corresponding overpotential is 270mV; when the current density passing through the electrode is 100mA/cm 2 When the oxygen is generated by OER reaction in the alkaline aqueous solution, the corresponding overpotential is 290mV. Half wave E of example 6 sample in ORR procedure 1/2 ΔΣ of example 6 sample at 0.81V (ΔΣ=e j＝10 -E 1/2 ) 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 the carbon cloth is completely immersed in the solution and subjected to water bath reaction at 95 ℃ for 3 hours to prepare the NiFe-LDH/CC. A Tris solution with ph=8.5 was prepared, and 0.4mg/mL of dopamine hydrochloride was dissolved therein, and the carbon cloth loaded with the precursor was suspended in the mixed solution and left for 24 hours to attach PDA. And placing the NiFe-LDH/CC attached with the PDA into a tube furnace by using a CVD method under the argon atmosphere and taking Dicyandiamide (DCA) as a solid source, heating to 350 ℃ at a heating rate of 10 ℃/min from the room temperature, preserving heat for 1h, heating to 800 ℃ at a heating rate of 3 ℃/min, and preserving heat for 2h to prepare the NiFe-NCNTs. 0.71307g of ferrous citrate, 0.2459g of nickel chloride, 2.667g of urea and 0.1822g of CTAB were dissolved in 40mL of UP water, then the solution was transferred to a water bath tube, and the Fe-NCNTs were subjected to a water bath reaction at 95℃for 3 hours to prepare NiFe-NCNTs@NiFe-LDH.
As can be seen from the OER-ORR linear voltammetric scan curve of the sample prepared in example 7 under the 1M KOH test condition in FIG. 2, the current density passing through the electrode during OER is 10mA/cm 2 When the oxygen is generated by OER reaction in the alkaline aqueous solution, the corresponding overpotential is 190mV; when the current density passing through the electrode is 100mA/cm 2 When the oxygen is generated by OER reaction in the alkaline aqueous solution, the corresponding overpotential is 250mV. Half wave E of example 7 sample in ORR procedure 1/2 ΔΣ of example 7 sample at 0.83V (ΔΣ=e j＝10 -E 1/2 ) 0.59V.
As can be seen from the OER-ORR linear voltammetric scan curve of the sample prepared in example 7 under the 0.1M KOH test condition in FIG. 4, the current density passing through the electrode during OER is 10mA/cm 2 When the oxygen is generated by OER reaction in the alkaline aqueous solution, the corresponding overpotential is 270mV; when the current density passing through the electrode is 100mA/cm 2 When the oxygen is generated by OER reaction in the alkaline aqueous solution, the corresponding overpotential is 300mV. Half wave E of example 7 sample in ORR procedure 1/2 ΔΣ of example 7 sample at 0.80V (ΔΣ=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 the carbon cloth is completely immersed in the solution and subjected to water bath reaction at 95 ℃ for 3 hours to prepare the NiFe-LDH/CC. A Tris solution with ph=8.5 was prepared, and 0.4mg/mL of dopamine hydrochloride was dissolved therein, and the carbon cloth loaded with the precursor was suspended in the mixed solution and left for 24 hours to attach PDA. And placing the NiFe-LDH/CC attached with the PDA into a tube furnace by using a CVD method under the argon atmosphere and taking Dicyandiamide (DCA) as a solid source, heating to 350 ℃ at a heating rate of 10 ℃/min from the room temperature, preserving heat for 1h, heating to 800 ℃ at a heating rate of 3 ℃/min, and preserving heat for 2h to prepare the NiFe-NCNTs. 0.71307g of ferrous citrate, 0.2459g of nickel chloride and 2.667g of urea were dissolved in 40mL of UP water, then the solution was transferred to a water bath tube, and the Fe-NCNTs were subjected to a water bath reaction at 95℃for 3 hours to prepare NiFe-NCNTs@NiFe-LDH.
As can be seen from the OER-ORR linear voltammetric scan curve of the sample prepared in example 8 under the 1M KOH test condition in FIG. 2, the current density passing through the electrode during OER is 10mA/cm 2 When the oxygen is generated by OER reaction in the alkaline aqueous solution, the corresponding overpotential is 180mV; when the current density passing through the electrode is 100mA/cm 2 When the oxygen is generated by OER reaction in the alkaline aqueous solution, the corresponding overpotential is 230mV. Half wave E of example 8 sample in ORR procedure 1/2 ΔΣ of example 8 sample at 0.84V (ΔΣ=e j＝10 -E 1/2 ) 0.57V.
As can be seen from the OER-ORR linear voltammetric scan curve of the sample prepared in example 8 under the 0.1M KOH test condition in FIG. 4, the current density passing through the electrode during OER is 10mA/cm 2 When the oxygen is generated by OER reaction in the alkaline aqueous solution, the corresponding overpotential is 246mV; when the current density passing through the electrode is 100mA/cm 2 When the oxygen is generated by OER reaction in the alkaline aqueous solution, the corresponding overpotential is 290mV. Half wave E of example 8 sample in ORR procedure 1/2 ΔΣ of example 8 sample at 0.86V (ΔΣ=e j＝10 -E 1/2 ) Is 0.62V.
FIG. 9 is a photograph of an SEM of the sample of example 8, showing that NiFe-LDH nanoplatelets grow on Fe-NCNTs nanotubes, but that NiFe-LDH nanoplatelets grow too thick and agglomerate 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 the carbon cloth is completely immersed in the solution and subjected to water bath reaction at 95 ℃ for 3 hours to prepare the NiFe-LDH/CC. A Tris solution with ph=8.5 was prepared, and 0.4mg/mL of dopamine hydrochloride was dissolved therein, and the carbon cloth loaded with the precursor was suspended in the mixed solution and left for 24 hours to attach PDA. Under argon atmosphere, dicyandiamide (DCA) is used as a solid source, a CVD method is used for placing the NiFe-LDH/CC attached with the PDA into a tube furnace, the temperature is raised to 350 ℃ at a heating rate of 10 ℃/min from the room temperature, the heat is preserved for 1h, the temperature is raised to 900 ℃ at a heating rate of 3 ℃/min, and the heat is preserved for 2h, so that the NiFe-NCNTs is prepared. 0.71307g of ferrous citrate, 0.2459g of nickel chloride, 2.667g of urea and 0.7289g of CTAB were dissolved in 40mL of UP water, then the solution was transferred to a water bath tube, and the Fe-NCNTs were subjected to a water bath reaction at 95℃for 3 hours to prepare NiFe-NCNTs@NiFe-LDH.
As can be seen from the OER-ORR linear voltammetric scan curve of the sample prepared in example 9 under the 0.1M KOH test condition in FIG. 5, the current density passing through the electrode during OER is 10mA/cm 2 When the oxygen is generated by OER reaction in the alkaline aqueous solution, the corresponding overpotential is 165mV; when the current density passing through the electrode is 100mA/cm 2 When the oxygen is generated by OER reaction in the alkaline aqueous solution, the corresponding overpotential is 190mV. Half wave E of example 9 sample in ORR procedure 1/2 ΔΣ of example 9 sample at 0.78V (ΔΣ=e j＝10 -E 1/2 ) Is 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 the carbon cloth is completely immersed in the solution and subjected to water bath reaction at 95 ℃ for 3 hours to prepare the NiFe-LDH/CC. A Tris solution with ph=8.5 was prepared, and 0.4mg/mL of dopamine hydrochloride was dissolved therein, and the carbon cloth loaded with the precursor was suspended in the mixed solution and left for 24 hours to attach PDA. Under argon atmosphere, dicyandiamide (DCA) is used as a solid source, a CVD method is used for placing the NiFe-LDH/CC attached with the PDA into a tube furnace, the temperature is raised to 350 ℃ at a heating rate of 10 ℃/min from the room temperature, the heat is preserved for 1h, the temperature is raised to 900 ℃ at a heating rate of 3 ℃/min, and the heat is preserved for 2h, so that the NiFe-NCNTs is prepared. 0.71307g of ferrous citrate, 0.2459g of nickel chloride, 2.667g of CTAB urea and 0.3645g of CTAB urea were dissolved in 40mL of UP water, then the solution was transferred to a water bath tube, and the Fe-NCNTs were subjected to a water bath reaction at 95℃for 3 hours to prepare NiFe-NCNTs@NiFe-LDH.
From the OER-ORR linear voltammetric scan curve measured for the sample prepared in example 10 under the 0.1M KOH test condition in FIG. 5, it can be seen that the electrode is on during OERThe density of the passing current is 10mA/cm 2 When the oxygen is generated by OER reaction in the alkaline aqueous solution, the corresponding overpotential is 148mV; when the current density passing through the electrode is 100mA/cm 2 When the oxygen is generated by OER reaction in the alkaline aqueous solution, the corresponding overpotential is 210mV. Half wave E of example 10 sample in ORR procedure 1/2 ΔΣ of example 10 sample at 0.78V (ΔΣ=e j＝10 -E 1/2 ) Is 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 the carbon cloth is completely immersed in the solution and subjected to water bath reaction at 95 ℃ for 3 hours to prepare the NiFe-LDH/CC. A Tris solution with ph=8.5 was prepared, and 0.4mg/mL of dopamine hydrochloride was dissolved therein, and the carbon cloth loaded with the precursor was suspended in the mixed solution and left for 24 hours to attach PDA. Under argon atmosphere, dicyandiamide (DCA) is used as a solid source, a CVD method is used for placing the NiFe-LDH/CC attached with the PDA into a tube furnace, the temperature is raised to 350 ℃ at a heating rate of 10 ℃/min from the room temperature, the heat is preserved for 1h, the temperature is raised to 900 ℃ at a heating rate of 3 ℃/min, and the heat is preserved for 2h, so that the NiFe-NCNTs is prepared. 0.71307g of ferrous citrate, 0.2459g of nickel chloride, 2.667g of CTAB urea and 0.1822g of CTAB urea were dissolved in 40mL of UP water, then the solution was transferred to a water bath tube, and the Fe-NCNTs were subjected to a water bath reaction at 95℃for 3 hours to prepare NiFe-NCNTs@NiFe-LDH.
As can be seen from the OER-ORR linear voltammetric scan curve of the sample prepared in example 11 under the 0.1M KOH test condition in FIG. 5, the current density passing through the electrode during OER is 10mA/cm 2 When the oxygen produced by the OER reaction in the alkaline aqueous solution corresponds to an overpotential of 174mV. Half wave E of example 11 sample in ORR procedure 1/2 ΔΣ of example 11 sample at 0.70V (ΔΣ=e j＝10 -E 1/2 ) Is 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 the carbon cloth is completely immersed in the solution and subjected to water bath reaction at 95 ℃ for 3 hours to prepare the NiFe-LDH/CC. A Tris solution with ph=8.5 was prepared, and 0.4mg/mL of dopamine hydrochloride was dissolved therein, and the carbon cloth loaded with the precursor was suspended in the mixed solution and left for 24 hours to attach PDA. Under argon atmosphere, dicyandiamide (DCA) is used as a solid source, a CVD method is used for placing the NiFe-LDH/CC attached with the PDA into a tube furnace, the temperature is raised to 350 ℃ at a heating rate of 10 ℃/min from the room temperature, the heat is preserved for 1h, the temperature is raised to 900 ℃ at a heating rate of 3 ℃/min, and the heat is preserved for 2h, so that the NiFe-NCNTs is prepared. 0.71307g of ferrous citrate, 0.2459g of nickel chloride and 2.667g of urea were dissolved in 40mL of UP water, then the solution was transferred to a water bath tube, and the Fe-NCNTs were subjected to a water bath reaction at 95℃for 3 hours to prepare NiFe-NCNTs@NiFe-LDH.
As can be seen from the OER-ORR linear voltammetric scan curve of the sample prepared in example 12 under the 0.1M KOH test condition in FIG. 5, the current density passing through the electrode during OER is 10mA/cm 2 When the oxygen is generated by OER reaction in the alkaline aqueous solution, the corresponding overpotential is 125mV; when the current density passing through the electrode is 100mA/cm 2 When the oxygen is generated by OER reaction in the alkaline aqueous solution, the corresponding overpotential is 185mV. Half wave E of example 12 sample in ORR procedure 1/2 ΔΣ of example 12 sample at 0.73V (ΔΣ=e j＝10 -E 1/2 ) 0.63V.
Claims (9)
1. A preparation method of an in-situ electrode of Fe-NCNTs@NiFe-LDH or FeNi-NCNTs@NiFe-LDH is characterized by comprising the following steps of:
s1, preparing Fe-LDH precursor: dissolving ferrous citrate and urea in UP water to obtain a mixed solution, transferring the mixed solution into a water bath pipe, and completely immersing carbon cloth in the solution to obtain a Fe-LDH precursor through reaction at a certain time and a certain temperature; or preparing FeNi-LDH precursor, namely dissolving ferrous citrate, nickel chloride and urea in UP water to obtain a mixed solution, transferring the mixed solution into a water bath pipe, and completely immersing carbon cloth in the solution to prepare the FeNi-LDH precursor through reaction at a certain temperature for a certain time;
s2, wrapping polydopamine: dissolving dopamine hydrochloride in Tris solution, suspending carbon cloth loaded with Fe-LDH or FeNi-LDH precursor in the mixed solution, and standing for a period of time to attach PDA;
s3, preparing Fe-NCNTs or FeNi-NCNTs: under argon atmosphere, dicyandiamide is used as a nitrogen fixation source, a CVD method is utilized to place Fe-LDH attached to PDA or FeNi-LDH precursor attached to PDA in a tube furnace, and Fe-NCNTs or FeNi-NCNTs are prepared after sintering;
s4, preparing an in-situ electrode of Fe-NCNTs@NiFe-LDH or FeNi-NCNTs@NiFe-LDH: 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-NCNTs or FeNi-NCNTs are completely immersed in the solution for reaction to prepare a final sample Fe-NCNTs@NiFe-LDH or FeNi-NCNTs@NiFe-LDH.
2. The method for preparing the Fe-NCNTs@NiFe-LDH or FeNi-NCNTs@NiFe-LDH in-situ electrode according to claim 1, wherein in S1, the mass ratio of ferrous citrate to urea is 1:3-1:4.
3. The method for preparing the in-situ electrode of Fe-NCNTs@NiFe-LDH or FeNi-NCNTs@NiFe-LDH according to claim 1, wherein the mass ratio of nickel chloride to ferrous citrate in S1 is 1:1-1:3.
4. The method for producing an in-situ electrode of Fe-NCNTs@NiFe-LDH or FeNi-NCNTs@NiFe-LDH according to claim 1, wherein in S1, the temperature of the water bath is maintained to 95-100 ℃ for 3-4h.
5. The method for preparing the in-situ electrode of Fe-NCNTs@NiFe-LDH or FeNi-NCNTs@NiFe-LDH according to claim 1, wherein 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.
6. The method for preparing the in-situ electrode of Fe-NCNTs@NiFe-LDH or FeNi-NCNTs@NiFe-LDH according to claim 1, wherein in S3, the mass ratio of dicyandiamide to the precursor of Fe-LDH after PDA is attached or FeNi-LDH after PDA is attached is 10-30:1.
7. The method for producing an in-situ electrode of Fe-NCNTs@NiFe-LDH or FeNi-NCNTs@NiFe-LDH as claimed in claim 1, wherein in S3, the CVD method is performed by heating up to 350-420 ℃ from room temperature at a heating rate of 5-10 ℃/min, keeping the temperature at 1-2h, heating up to 800-900 ℃ at a heating rate of 3-5 ℃/min, and keeping the temperature at 2-5h.
8. The method for preparing the in-situ electrode of Fe-NCNTs@NiFe-LDH or FeNi-NCNTs@NiFe-LDH according to 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 hexadecyl trimethyl ammonium bromide is 0.1-2mmol, and the temperature of the water bath is maintained to 95-100 ℃ for 3-4h.
9. The method for producing an in-situ electrode of Fe-NCNTs@NiFe-LDH or FeNi-NCNTs@NiFe-LDH according to claim 1, wherein in S4, the temperature of the water bath is maintained to 95-100 ℃ for 3-4h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210367432.0A CN114792810B (en) | 2022-04-08 | 2022-04-08 | Preparation method of Fe (Ni) -NCNTs@NiFe-LDH in-situ electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210367432.0A CN114792810B (en) | 2022-04-08 | 2022-04-08 | Preparation method of Fe (Ni) -NCNTs@NiFe-LDH in-situ electrode |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114792810A CN114792810A (en) | 2022-07-26 |
| CN114792810B true CN114792810B (en) | 2024-01-30 |
Family
ID=82461406
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210367432.0A Active CN114792810B (en) | 2022-04-08 | 2022-04-08 | Preparation method of Fe (Ni) -NCNTs@NiFe-LDH in-situ electrode |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114792810B (en) |
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 |
|---|
| NiFe Nanoparticles Embedded N-doped Carbon Nanotubes as High-Efficient Electrocatalysts for Wearable Solid-State Zn-air Batteries;Hang Lei et al.;Nano Energy;第1-25页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114792810A (en) | 2022-07-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110148762B (en) | Carbon material with nitrogen, fluorine and transition metal co-doped graphene structure and one-step carbonization preparation method thereof | |
| CN109518216B (en) | Cobalt phosphide nano-framework and preparation and application thereof | |
| CN109852994B (en) | Co9S8Preparation method of nitrogen-doped carbon composite array electrode | |
| CN112481653B (en) | Defect-rich molybdenum-doped cobalt selenide/nano carbon electrocatalyst and preparation method and application thereof | |
| CN113363514A (en) | Carbon aerogel supported cobalt monoatomic catalyst for metal air battery, preparation method and application thereof | |
| CN108048868B (en) | Molybdenum nitride nanorod electrode material and preparation method and application thereof | |
| Gong et al. | Duckweed derived nitrogen self-doped porous carbon materials as cost-effective electrocatalysts for oxygen reduction reaction in microbial fuel cells | |
| CN113445072B (en) | Foamed nickel composite electrode and preparation method and application thereof | |
| Hu et al. | Boosting hydrogen generation by anodic oxidation of iodide over Ni–Co (OH) 2 nanosheet arrays | |
| CN112886029B (en) | Preparation and application of bifunctional oxygen electrocatalyst with hollow carbon nanotube as carrier | |
| CN113279005A (en) | Cobalt doped MoS2/NiS2Preparation method of porous heterostructure material and application of material in electrocatalytic hydrogen evolution | |
| CN112439459A (en) | Ultrathin nanosheet material with coexisting crystal and amorphous interface and application thereof in water electrolysis | |
| CN113694948A (en) | Fe-monoatomic-supported electrochemical catalyst and preparation method and application thereof | |
| CN111129522A (en) | Preparation and application of nickel-iron alloy/nitrogen-doped carbon fiber serving as zinc-air battery oxygen electrocatalyst | |
| CN110699702A (en) | Hillock-shaped in-situ nickel-vanadium double metal hydroxide catalyst and preparation method and application thereof | |
| CN111790416A (en) | High-efficiency oxygen evolution electrocatalyst and preparation method thereof | |
| CN110721749B (en) | NiCo coated with metal organic framework structure derived carbon composite2S4Nanowire array-shaped electrocatalyst and preparation method thereof | |
| CN115896848A (en) | Nitrogen/sulfur co-doped porous carbon loaded zinc monoatomic/metallic copper series catalyst and preparation method and application thereof | |
| CN112316965B (en) | Preparation method and application of composite material derived by loading molybdenum disulfide nanosheet based on laccase-copper phosphate nanoflowers as substrate | |
| CN114875442A (en) | Ruthenium-modified molybdenum-nickel nanorod composite catalyst and preparation method and application thereof | |
| CN114792810B (en) | Preparation method of Fe (Ni) -NCNTs@NiFe-LDH in-situ electrode | |
| CN116078413A (en) | Low-noble metal phosphide electrocatalyst based on microbial template derivatization and preparation method and application thereof | |
| CN113046720B (en) | Nd-graphene composite material and preparation method and application thereof | |
| CN115011997B (en) | Self-supporting hollow sugarcoated haws-end electrocatalyst and preparation method and application thereof | |
| CN114214662B (en) | MoS rich in metal vacancies 2 Base composite material and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20240103 Address after: Room 419, No. 500 Linyang Road, Qidong Economic Development Zone, Qidong City, Nantong City, Jiangsu Province, 226200 Applicant after: Qidong High Energy New Energy Co.,Ltd. Address before: 1003, Building A, Zhiyun Industrial Park, No. 13 Huaxing Road, Tongsheng Community, Dalang Street, Longhua District, Shenzhen City, Guangdong Province, 518000 Applicant before: Shenzhen Wanzhida Enterprise Management Co.,Ltd. Effective date of registration: 20240103 Address after: 1003, Building A, Zhiyun Industrial Park, No. 13 Huaxing Road, Tongsheng Community, Dalang Street, Longhua District, Shenzhen City, Guangdong Province, 518000 Applicant after: Shenzhen Wanzhida Enterprise Management Co.,Ltd. Address before: 443002 No. 8, University Road, Xiling District, Yichang, Hubei Applicant before: CHINA THREE GORGES University |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |