CN114277401B - Vanadium-doped nickel-cobalt layered double hydroxide full-hydrolysis electrode material, preparation method and application - Google Patents
Vanadium-doped nickel-cobalt layered double hydroxide full-hydrolysis electrode material, preparation method and application Download PDFInfo
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- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 title claims abstract description 62
- 238000006460 hydrolysis reaction Methods 0.000 title claims abstract description 55
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 239000007772 electrode material Substances 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 57
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000001257 hydrogen Substances 0.000 claims abstract description 34
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 34
- 238000009713 electroplating Methods 0.000 claims abstract description 33
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 28
- 238000007747 plating Methods 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 15
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 9
- 229910052751 metal Inorganic materials 0.000 claims description 47
- 239000002184 metal Substances 0.000 claims description 38
- 239000000243 solution Substances 0.000 claims description 36
- 239000012266 salt solution Substances 0.000 claims description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 239000002135 nanosheet Substances 0.000 claims description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- 239000008367 deionised water Substances 0.000 claims description 19
- 229910021641 deionized water Inorganic materials 0.000 claims description 19
- 229910003266 NiCo Inorganic materials 0.000 claims description 16
- 239000002243 precursor Substances 0.000 claims description 16
- 239000000956 alloy Substances 0.000 claims description 15
- 229910045601 alloy Inorganic materials 0.000 claims description 15
- 239000006260 foam Substances 0.000 claims description 14
- 239000011248 coating agent Substances 0.000 claims description 12
- 238000000576 coating method Methods 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 11
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 9
- 239000004202 carbamide Substances 0.000 claims description 9
- 238000005868 electrolysis reaction Methods 0.000 claims description 9
- 239000000758 substrate Substances 0.000 claims description 9
- 238000001291 vacuum drying Methods 0.000 claims description 9
- 229910021550 Vanadium Chloride Inorganic materials 0.000 claims description 8
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 8
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 238000011010 flushing procedure Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 8
- RPESBQCJGHJMTK-UHFFFAOYSA-I pentachlorovanadium Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[V+5] RPESBQCJGHJMTK-UHFFFAOYSA-I 0.000 claims description 8
- -1 polytetrafluoroethylene Polymers 0.000 claims description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 8
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 3
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 230000004913 activation Effects 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- 230000007547 defect Effects 0.000 abstract description 2
- 229910017052 cobalt Inorganic materials 0.000 abstract 1
- 239000010941 cobalt Substances 0.000 abstract 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 21
- 239000001301 oxygen Substances 0.000 description 21
- 229910052760 oxygen Inorganic materials 0.000 description 21
- 230000007062 hydrolysis Effects 0.000 description 15
- 230000000694 effects Effects 0.000 description 9
- 238000005265 energy consumption Methods 0.000 description 8
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 230000018109 developmental process Effects 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 5
- 238000010586 diagram Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000004832 voltammetry Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- 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
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a vanadium-doped nickel-cobalt layered double hydroxide full-hydrolysis electrode material, a preparation method and application thereof. On one hand, the material has the advantages of unique double-plate layer structure, large specific surface area, wide ion passage and easy structure adjustment, can provide stable and more active area for reaction, and enables the reaction to be easier to carry out, meanwhile, the doping of vanadium element enables strong synergistic effect to exist between nickel, cobalt and vanadium three elements, so that the reaction activation energy is reduced, and the catalytic activity is improved; on the other hand, the plating layer is further modified on the hydrothermal plating layer by an electroplating method, so that a unique double-nano-sheet-layer cross structure is formed, the specific surface area of the material is further increased, and meanwhile, the defect of the original material in hydrogen evolution performance is improved, so that the material can be applied to full hydrolysis reaction.
Description
Technical Field
The invention belongs to the technical field of preparation of fully hydrolyzed electrode materials for hydrogen production by water electrolysis, and particularly relates to a vanadium-doped nickel-cobalt layered double hydroxide fully hydrolyzed electrode material, a preparation method and application thereof.
Background
With the development and progress of human society, the demand for energy is increasing, and a great deal of use of traditional chemical energy brings about a great environmental problem, so that the active development of new energy sources with sustainable clean regeneration, such as wind energy, solar energy, etc., has become a focus of attention, and these renewable resources are being developed and utilized to a considerable extent, but are affected by natural factors and geographical locations, and these resources cannot guarantee a stable supply. The hydrogen energy is also used as clean renewable resources, has the advantages of high efficiency, storability and transportation and no pollution of combustion products, and therefore becomes a novel energy source which is expected.
Water electrolysis hydrogen production is a technology for obtaining high-purity hydrogen by electrolyzing water, but the current cost of water electrolysis hydrogen production is too high, wherein the electricity cost accounts for more than 75% of the total cost, so the hydrogen production energy consumption must be reduced, and the electricity consumption is reduced to improve the possibility of large-scale use of water electrolysis hydrogen production. The theoretical decomposition voltage of water is 1.23V, but in actual production, the average bath pressure of an industrial electrolytic bath can reach 1.8V, and the higher overpotential leads to the improvement of energy consumption, so that the development of an electrode material with low overpotential is a key for reducing the energy consumption of the electrolytic bath.
The electrode materials used earlier are usually noble metal electrodes, e.g. Pt, pd, irO 2 And the like, such noble metal materials are expensive and unfavorable for large-scale use, and therefore, development of non-noble metal electrodes having excellent catalytic performance is required.
At present, a plurality of non-noble metal water electrolysis electrode materials are researched as porous foam nickel-based materials, and the catalytic performance of the electrode materials can be improved by modifying foam nickel through methods such as surface structure modification, metal element doping and the like. The advantages of the unique double-plate layer structure of the Layered Double Hydroxide (LDH) are utilized, such as large specific surface area, wide ion passage, easy structure adjustment and the like, so that the excellent water electrolysis electrode can be prepared, meanwhile, the same catalyst material is used at the anode and cathode, the production flow can be simplified, the production cost can be reduced, the device installation flow can be simplified, the full hydrolysis electrode has hydrogen evolution and oxygen evolution activities, the overpotential is lower, and the stability is longer.
However, the currently used foam nickel-based LDH electrode generally only has one of hydrogen evolution and oxygen evolution, and cannot be used for both anode and cathode, so that the preparation of the foam nickel-based LDH full-hydrolysis electrode with noble metal and hydrogen evolution and oxygen evolution activities is a very promising development direction.
Disclosure of Invention
In view of the above, the invention aims to provide a two-step preparation method for preparing a foam nickel-based LDH full-hydrolysis electrode with hydrogen evolution and oxygen evolution activities, and the full-hydrolysis electrode material prepared by the method has the advantages of low cost, easy control of reaction conditions, good catalytic performance and strong stability, and has great significance for preparing novel full-hydrolysis electrodes.
The technical scheme of the invention is as follows:
a vanadium-doped nickel-cobalt layered double hydroxide full-hydrolysis electrode material is characterized in that: the NiCoV-LDH/NF nano sheet material is prepared by hydrothermal synthesis, and the NiCoV-LDH/NF material is plated with a NiCo hydroxide alloy plating layer by an electroplating method.
A preparation method of a vanadium-doped nickel-cobalt layered double hydroxide fully hydrolyzed electrode material comprises the following steps:
firstly, nickel nitrate, cobalt nitrate and vanadium chloride are mixed according to the atomic molar ratio of metal elements of 1-2: 1-2: 0.3 to 0.6 of the metal salt is dissolved in deionized water to obtain a metal salt solution;
step two, weighing the metal salt solution elements with the total molar ratio of 1:3, adding urea into the metal salt solution, and mixing to obtain a precursor solution;
step three, placing the precursor solution and the foam nickel substrate into a polytetrafluoroethylene reaction kettle, heating to 110-130 ℃ and keeping for 12-16h, and then cooling along with a furnace;
taking out the cooled material, repeatedly flushing with deionized water and ethanol solution, and vacuum drying at 60 ℃ for 12 hours to obtain the NiCoV-LDH/NF nano sheet material;
step five, plating a NiCo hydroxide alloy coating on the surface of the NiCoV-LDH/NF nano sheet material by adopting an electroplating method by taking the NiCoV-LDH/NF nano sheet material as a cathode, taking a Pt electrode as an anode and taking an Ag/AgCl electrode as a reference electrode, wherein the electroplating solution is 300mL and contains 10mmol/L NiCl 2 ·6H 2 O and 10mmol/LCoCl 2 ·6H 2 O, the electroplating voltage is-1.3V vs RHE, the electroplating time is 5-30 min, the electroplating temperature is 25-40 ℃, the electrode after plating is repeatedly washed by deionized water and ethanol, and the electrode is dried in vacuum for 12h at 60 ℃ to obtain the vanadium-doped nickel-cobalt layered double hydroxide full-hydrolysis electrode.
In the invention, the formation process of the NiCoV-LDH/NF nano sheet material obtained in the first to fourth steps is as follows: ammonia generated by urea decomposition in the solution at high temperature and high pressure is dissolved to provide an alkaline environment, and metal ions generate double hydroxide in the alkaline environment.
In the invention, the formation mechanism of the NiCo hydroxide alloy coating obtained in the step five is as follows:
Ni 2+ +Co 2+ +H 2 O→NiCo(OH) 4 +4H +
the application of vanadium doped nickel cobalt layered double hydroxide fully hydrolyzed electrode as fully hydrolyzed electrode material for water electrolysis hydrogen production.
The invention has the advantages and positive effects that:
as shown in the attached figure 1, the vanadium-doped nickel-cobalt layered double hydroxide full-hydrolysis electrode has the unique nano sheet-shaped structure with large specific surface area and large ion passage, can provide stable and more active area for reaction, so that the reaction is easier to carry out, and meanwhile, as shown in the attached figure 3, after being doped with vanadium element, the combination energy of Ni 2p and Co 2p is increased, so that a strong synergistic effect exists between metal ions, the reaction activation energy is reduced, and the catalytic activity is improved; on the other hand, in order to improve the deficiency of the electrode material in hydrogen evolution performance, the plating layer is further modified on the hydrothermal plating layer by an electroplating method, so that a unique double-nano-sheet-layer cross structure is formed, the specific surface area of the material is further increased, and the material can be applied to full hydrolysis reaction.
Drawings
A in FIG. 1 is an SEM image of the NiCoV-LDH/NF material of the invention, and b-f are SEM images of vanadium-doped nickel cobalt layered double hydroxide fully hydrolyzed electrodes of various embodiments;
FIG. 2 is an XRD pattern of a vanadium doped nickel cobalt layered double hydroxide fully hydrolyzed electrode (NiCo-LDH@NiCoV-LDH/NF) of example 1 of the present invention, wherein the abscissa represents 2X incident angle and the ordinate represents diffraction intensity;
FIG. 3 is an XPS chart of a vanadium doped nickel cobalt layered double hydroxide fully hydrolyzed electrode (NiCo-LDH@NiCoV-LDH/NF) of example 1 of the present invention, wherein the abscissa indicates binding energy and the ordinate indicates measured intensity of photoelectrons;
FIG. 4 is a graph of linear voltammetry scans of hydrogen evolution, oxygen evolution and total hydrolysis of a vanadium doped nickel cobalt layered double hydroxide fully hydrolyzed electrode (NiCo-LDH@NiCoV-LDH/NF) of the present invention in a 1M KOH solution, where a is the hydrogen evolution curve; b is an oxygen evolution curve; c is the full hydrolysis curve (examples 1, 2, 3, 4, 5 in fig. 4a-c represent examples 1, 2, 3, 4, and 5, respectively), wherein the abscissa represents voltage and the ordinate represents current density.
Detailed Description
Embodiments of the invention are described in further detail below with reference to the attached drawing figures:
example 1:
step 1, nickel nitrate, cobalt nitrate and vanadium chloride are mixed according to the atomic molar ratio of metal elements of 1:1:0.4, dissolving in deionized water to obtain a metal salt solution;
step 2, weighing the metal salt solution, wherein the molar ratio of the metal salt solution to the total atomic number of the metal salt solution is 1:3, adding urea into the metal salt solution, and mixing to obtain a precursor solution;
step 3, placing the precursor solution and the foam nickel substrate into a polytetrafluoroethylene reaction kettle, heating to 110-130 ℃ and keeping for 12h, and then cooling along with a furnace;
step 4, taking out the cooled material, repeatedly flushing with deionized water and ethanol solution, and then vacuum drying at 60 ℃ for 12 hours to obtain the NiCoV-LDH/NF nano sheet material;
and 5, plating a NiCo hydroxide alloy coating on the surface of the NiCoV-LDH/NF material by adopting an electroplating method by taking the obtained NiCoV-LDH/NF as a cathode, wherein the electroplating temperature is 25 ℃ and the time is 15min, and finally obtaining the vanadium-doped nickel-cobalt layered double hydroxide full-hydrolysis electrode.
A in FIG. 1 is an SEM diagram of NiCoV-LDH/NF material, b is an SEM diagram of NiCo-LDH/@ NiCoV-LDH/NF electrode, FIG. 2 and FIG. 3 are XRD and XPS diagrams of a vanadium-doped nickel-cobalt layered double hydroxide fully hydrolyzed electrode and NiCo-LDH/NF material, respectively, and FIG. 4 is a hydrogen evolution, oxygen evolution and fully hydrolyzed linear voltammetry scan curve of the vanadium-doped nickel-cobalt layered double hydroxide fully hydrolyzed electrode in a 1M KOH solution. As can be seen from FIG. 4, the vanadium-doped nickel-cobalt layered double hydroxide full-hydrolysis electrode has a current density of 10mA/cm 2 The hydrogen evolution overpotential is 85mV, and the current density is 100mA/cm 2 The oxygen evolution overpotential is 260mV at a current density of 10mA/cm 2 The total hydrolysis potential was 1.55V, indicatingThe prepared vanadium-doped nickel-cobalt layered double hydroxide full-hydrolysis electrode has hydrogen evolution activity and oxygen evolution activity, has low overpotential, is low in tank pressure when being used for full-hydrolysis reaction, and can effectively reduce energy consumption when in use.
Example 2:
step 1, nickel nitrate, cobalt nitrate and vanadium chloride are mixed according to the atomic molar ratio of metal elements of 1:1:0.4, dissolving in deionized water to obtain a metal salt solution;
step 2, weighing the metal salt solution, wherein the molar ratio of the metal salt solution to the total atomic number of the metal salt solution is 1:3, adding urea into the metal salt solution, and mixing to obtain a precursor solution;
step 3, placing the precursor solution and the foam nickel substrate into a polytetrafluoroethylene reaction kettle, heating to 110 ℃ and keeping for 12 hours, and then cooling along with a furnace;
step 4, taking out the cooled sheet material, repeatedly flushing with deionized water and ethanol solution, and then vacuum drying at 60 ℃ for 12 hours to obtain the NiCoV-LDH/NF nano sheet material;
and 5, plating a NiCo hydroxide alloy coating on the surface of the NiCoV-LDH/NF material by adopting an electroplating method by taking the obtained NiCoV-LDH/NF nano sheet material as a cathode, wherein the electroplating temperature is 25 ℃ and the time is 30min, and finally obtaining the vanadium-doped nickel-cobalt layered double hydroxide full-hydrolysis electrode.
Fig. 1C is an SEM image of a vanadium-doped nickel cobalt layered double hydroxide full-hydrolysis electrode, and fig. 4 is a linear voltammetric sweep curve of the vanadium-doped nickel cobalt layered double hydroxide full-hydrolysis electrode for hydrogen evolution, oxygen evolution, and full hydrolysis in 1M KOH solution. As can be seen from FIG. 4, the vanadium-doped nickel-cobalt layered double hydroxide full-hydrolysis electrode has a current density of 10mA/cm 2 The hydrogen evolution overpotential is 100mV, and the current density is 100mA/cm 2 The oxygen evolution overpotential was 282mV at a current density of 10mA/cm 2 The full hydrolysis potential is 1.57V, which shows that the prepared vanadium-doped nickel-cobalt layered double hydroxide full hydrolysis electrode has hydrogen evolution and oxygen evolution activities at the same time, has low overpotential, has low tank pressure when being used for full hydrolysis reaction, and can effectively reduce the energy consumption when in use.
Example 3:
step 1, nickel nitrate, cobalt nitrate and vanadium chloride are mixed according to the atomic molar ratio of metal elements of 1:1:0.6, dissolving in deionized water to obtain a metal salt solution;
step 2, weighing the metal salt solution, wherein the molar ratio of the metal salt solution to the total atomic number of the metal salt solution is 1:3, adding urea into the metal salt solution, and mixing to obtain a precursor solution;
step 3, placing the precursor solution and the foam nickel substrate into a polytetrafluoroethylene reaction kettle, heating to 110 ℃ and keeping for 16 hours, and then cooling along with a furnace;
step 4, taking out the cooled sheet material, repeatedly flushing with deionized water and ethanol solution, and then vacuum drying at 60 ℃ for 12 hours to obtain the NiCoV-LDH/NF nano sheet material;
and 5, plating a NiCo hydroxide alloy coating on the surface of the NiCoV-LDH/NF material by adopting an electroplating method by taking the obtained NiCoV-LDH/NF nano sheet material as a cathode, wherein the electroplating temperature is 25 ℃ and the time is 15min, and finally obtaining the vanadium-doped nickel-cobalt layered double hydroxide full-hydrolysis electrode.
D in fig. 3 is an SEM image of the vanadium-doped nickel cobalt layered double hydroxide full-hydrolysis electrode, and fig. 4 is a linear voltammetric sweep curve of the vanadium-doped nickel cobalt layered double hydroxide full-hydrolysis electrode for hydrogen evolution, oxygen evolution and full hydrolysis in 1M KOH solution. As can be seen from FIG. 4, the vanadium-doped nickel-cobalt layered double hydroxide full-hydrolysis electrode has a current density of 10mA/cm 2 The hydrogen evolution overpotential is 95mV, and the current density is 100mA/cm 2 The oxygen evolution overpotential is 273mV at a current density of 10mA/cm 2 The full hydrolysis potential is 1.56V, which shows that the prepared vanadium-doped nickel-cobalt layered double hydroxide full hydrolysis electrode has hydrogen evolution and oxygen evolution activities at the same time, has low overpotential, has low tank pressure when being used for full hydrolysis reaction, and can effectively reduce the energy consumption when in use.
Example 4:
step 1, nickel nitrate, cobalt nitrate and vanadium chloride are mixed according to the atomic molar ratio of metal elements of 1:1:0.4, dissolving in deionized water to obtain a metal salt solution;
step 2, weighing the metal salt solution, wherein the molar ratio of the metal salt solution to the total atomic number of the metal salt solution is 1:3, adding urea into the metal salt solution, and mixing to obtain a precursor solution;
step 3, placing the precursor solution and the foam nickel substrate into a polytetrafluoroethylene reaction kettle, heating to 130 ℃ and keeping for 12 hours, and then cooling along with a furnace;
step 4, taking out the cooled sheet material, repeatedly flushing with deionized water and ethanol solution, and then vacuum drying at 60 ℃ for 12 hours to obtain the NiCoV-LDH/NF nano sheet material;
and 5, plating a NiCo hydroxide alloy coating on the surface of the NiCoV-LDH/NF material by adopting an electroplating method by taking the obtained NiCoV-LDH/NF material as a cathode, wherein the electroplating temperature is 40 ℃ and the time is 30min, and finally obtaining the vanadium-doped nickel-cobalt layered double hydroxide full-hydrolysis electrode.
Fig. 1 e is an SEM image of a vanadium-doped nickel cobalt layered double hydroxide full-hydrolysis electrode, and fig. 4 is a linear voltammetric sweep curve of the vanadium-doped nickel cobalt layered double hydroxide full-hydrolysis electrode for hydrogen evolution, oxygen evolution and full hydrolysis in 1M KOH solution. As can be seen from FIG. 4, the vanadium-doped nickel-cobalt layered double hydroxide full-hydrolysis electrode has a current density of 10mA/cm 2 The hydrogen evolution overpotential is 140mV, and the current density is 100mA/cm 2 The oxygen evolution overpotential was 300mV at a current density of 10mA/cm 2 The full hydrolysis potential is 1.62V, which shows that the prepared vanadium-doped nickel-cobalt layered double hydroxide full hydrolysis electrode has hydrogen evolution and oxygen evolution activities at the same time, has low overpotential, has low tank pressure when being used for full hydrolysis reaction, and can effectively reduce the energy consumption when in use.
Example 5:
step 1, nickel nitrate, cobalt nitrate and vanadium chloride are mixed according to the atomic molar ratio of metal elements of 1:2:0.5, dissolving in deionized water to obtain a metal salt solution;
step 2, weighing the metal salt solution, wherein the molar ratio of the metal salt solution to the total atomic number of the metal salt solution is 1:3, adding urea into the metal salt solution, and mixing to obtain a precursor solution;
step 3, placing the precursor solution and the foam nickel substrate into a polytetrafluoroethylene reaction kettle, heating to 110 ℃ and keeping for 12 hours, and then cooling along with a furnace;
step 4, taking out the cooled sheet material, repeatedly flushing with deionized water and ethanol solution, and then vacuum drying at 60 ℃ for 12 hours to obtain the NiCoV-LDH/NF nano sheet material;
and 5, plating a NiCo hydroxide alloy coating on the surface of the NiCoV-LDH/NF material by adopting an electroplating method by taking the obtained NiCoV-LDH/NF material as a cathode, wherein the electroplating temperature is 25 ℃ and the time is 30min, and finally obtaining the vanadium-doped nickel-cobalt layered double hydroxide full-hydrolysis electrode.
In FIG. 1, f is an SEM image of a vanadium-doped nickel-cobalt layered double hydroxide full-hydrolysis electrode, and FIG. 4 is a linear voltammetric sweep curve of hydrogen evolution, oxygen evolution and full-hydrolysis of a NiCo-LDH@NiCoV-LD/NF electrode in a 1M KOH solution. As can be seen from FIG. 4, the vanadium-doped nickel-cobalt layered double hydroxide full-hydrolysis electrode has a current density of 10mA/cm 2 The hydrogen evolution overpotential is 93mV at a current density of 100mA/cm 2 The oxygen evolution overpotential was 291mV at a current density of 10mA/cm 2 The full hydrolysis potential is 1.58V, which shows that the prepared vanadium-doped nickel-cobalt layered double hydroxide full hydrolysis electrode has hydrogen evolution and oxygen evolution activities at the same time, has low overpotential, has lower tank pressure when being used for full hydrolysis reaction, and can effectively reduce the energy consumption when in use.
The invention takes porous foam nickel NF as a substrate, prepares a vanadium-doped nickel-cobalt layered double hydroxide matrix (noted as NiCoV-LDH/NF) by a hydrothermal synthesis method, and then plates a plating layer by an electroplating method to form a water electrolysis hydrogen production material (noted as NiCo-LDH@NiCoV-LDH/NF) which has a double-layer structure and can be simultaneously applied to the anode and cathode.
The invention has the advantages that: on one hand, the unique double-plate layer structure of the layered double hydroxide has large specific surface area, wide ion passage and easy structure adjustment, can provide stable and more active area for the reaction, so that the reaction is easier to carry out, and meanwhile, the doping of the vanadium element enables strong synergistic effect between metal elements, so that the reaction activation energy is reduced, and the catalytic activity is improved; on the other hand, the plating layer is further modified on the hydrothermal plating layer by an electroplating method, so that a unique double-nano-sheet-layer cross structure is formed, the specific surface area of the material is further increased, and meanwhile, the defect of the original material in hydrogen evolution performance is improved, so that the material can be applied to full hydrolysis reaction.
Although the embodiments of the present invention and the accompanying drawings have been disclosed for illustrative purposes, those skilled in the art will appreciate that: various substitutions, changes and modifications are possible without departing from the spirit and scope of the invention and the appended claims, and therefore the scope of the invention is not limited to the embodiments and the disclosure of the drawings.
Claims (4)
1. A vanadium-doped nickel-cobalt layered double hydroxide full-hydrolysis electrode material is characterized in that: the preparation method comprises a NiCoV-LDH/NF nano sheet material and a NiCo hydroxide alloy coating, wherein the NiCoV-LDH/NF nano sheet material is prepared by hydrothermal synthesis, and the NiCoV-LDH/NF nano sheet material is plated with the NiCo hydroxide alloy coating by an electroplating method;
the preparation method of the NiCoV-LDH/NF nano sheet material comprises the following steps:
nickel nitrate, cobalt nitrate and vanadium chloride are mixed according to the atomic mole ratio of metal elements of 1-2: 1-2: 0.3-0.6 of the metal salt is dissolved in deionized water to obtain a metal salt solution;
the total mole ratio of the weighed metal salt solution atoms is 1:3, adding urea into the metal salt solution, and mixing to obtain a precursor solution;
placing the precursor solution and the foam nickel substrate into a polytetrafluoroethylene reaction kettle, heating to 110-130 ℃ and keeping for 12-16h, and then cooling along with a furnace;
taking out the cooled material, repeatedly flushing with deionized water and ethanol solution, and vacuum drying at 60 ℃ for 12 hours to obtain a NiCoV-LDH/NF nano sheet material;
the plating method of the NiCo hydroxide alloy plating layer comprises the following steps:
the method comprises the steps of using a NiCoV-LDH/NF nano sheet material as a cathode, using a Pt electrode as an anode, using a reference electrode as an Ag/AgCl electrode, plating a NiCo hydroxide alloy coating on the surface of the NiCoV-LDH/NF nano sheet material by adopting an electroplating method, wherein an electroplating solution is 300mL, and the electroplating solution comprises 10mmol/L NiCl 2 ·6H 2 O and 10mmol/L CoCl 2 ·6H 2 O, the electroplating voltage is-1.3V vsRHE, the electroplating time is 5 min-30 min, and the electroplating temperature isAnd (3) washing the electrode subjected to plating by using deionized water and ethanol repeatedly at 25-40 ℃, and vacuum drying at 60 ℃ for 12 hours to obtain the vanadium-doped nickel-cobalt layered double hydroxide full-hydrolysis electrode.
2. A method for preparing the vanadium-doped nickel cobalt layered double hydroxide fully hydrolyzed electrode material according to claim 1, wherein the method comprises the following steps: comprises a preparation method of NiCoV-LDH/NF nano sheet material and a method for plating a NiCo hydroxide alloy coating on the NiCoV-LDH/NF nano sheet material;
the preparation method of the NiCoV-LDH/NF nano sheet material comprises the following steps:
nickel nitrate, cobalt nitrate and vanadium chloride are mixed according to the atomic mole ratio of metal elements of 1-2: 1-2: 0.3-0.6 of the metal salt is dissolved in deionized water to obtain a metal salt solution;
the total mole ratio of the weighed metal salt solution atoms is 1:3, adding urea into the metal salt solution, and mixing to obtain a precursor solution;
placing the precursor solution and the foam nickel substrate into a polytetrafluoroethylene reaction kettle, heating to 110-130 ℃ and keeping for 12-16h, and then cooling along with a furnace;
taking out the cooled material, repeatedly flushing with deionized water and ethanol solution, and vacuum drying at 60 ℃ for 12 hours to obtain a NiCoV-LDH/NF nano sheet material;
the plating method of the NiCo hydroxide alloy plating layer comprises the following steps:
the method comprises the steps of using a NiCoV-LDH/NF nano sheet material as a cathode, using a Pt electrode as an anode, using a reference electrode as an Ag/AgCl electrode, plating a NiCo hydroxide alloy coating on the surface of the NiCoV-LDH/NF nano sheet material by adopting an electroplating method, wherein an electroplating solution is 300mL, and the electroplating solution comprises 10mmol/L NiCl 2 ·6H 2 O and 10mmol/L CoCl 2 ·6H 2 O, the electroplating voltage is-1.3V vsRHE, the electroplating time is 5 min-30 min, the electroplating temperature is 25-40 ℃, the electrode after plating is repeatedly washed by deionized water and ethanol, and the electrode is dried in vacuum at 60 ℃ for 12h to obtain the vanadium-doped nickel-cobalt layered double hydroxide full-hydrolysis electrode.
3. The method for preparing the vanadium-doped nickel-cobalt layered double hydroxide fully hydrolyzed electrode material according to claim 2, wherein the method comprises the following steps: the nano-sheet structure size of the prepared NiCoV-LDH/NF nano-sheet material is 10-20 nm.
4. Use of a vanadium doped nickel cobalt layered double hydroxide fully hydrolyzed electrode prepared by the method of claim 2 or 3 in the production of hydrogen fully hydrolyzed electrode material by water electrolysis.
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