CN116516389B - Ultra-high performance anode catalyst for alkaline water electrolysis tank and preparation method thereof - Google Patents
Ultra-high performance anode catalyst for alkaline water electrolysis tank and preparation method thereof Download PDFInfo
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- CN116516389B CN116516389B CN202210932695.1A CN202210932695A CN116516389B CN 116516389 B CN116516389 B CN 116516389B CN 202210932695 A CN202210932695 A CN 202210932695A CN 116516389 B CN116516389 B CN 116516389B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 101
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 65
- 229910002640 NiOOH Inorganic materials 0.000 claims abstract description 55
- 239000011259 mixed solution Substances 0.000 claims abstract description 28
- 239000002243 precursor Substances 0.000 claims abstract description 26
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 19
- -1 transition metal salt Chemical class 0.000 claims abstract description 16
- 239000000758 substrate Substances 0.000 claims abstract description 14
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 13
- 239000003792 electrolyte Substances 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 239000006260 foam Substances 0.000 claims abstract description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims description 24
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 10
- 230000007704 transition Effects 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 9
- 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
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- NLPVCCRZRNXTLT-UHFFFAOYSA-N dioxido(dioxo)molybdenum;nickel(2+) Chemical group [Ni+2].[O-][Mo]([O-])(=O)=O NLPVCCRZRNXTLT-UHFFFAOYSA-N 0.000 claims description 5
- 150000001768 cations Chemical class 0.000 claims description 3
- RPZHFKHTXCZXQV-UHFFFAOYSA-N mercury(i) oxide Chemical compound O1[Hg][Hg]1 RPZHFKHTXCZXQV-UHFFFAOYSA-N 0.000 claims description 3
- 229910021518 metal oxyhydroxide Inorganic materials 0.000 claims description 3
- 238000011056 performance test Methods 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 238000013112 stability test Methods 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 abstract description 9
- 238000007254 oxidation reaction Methods 0.000 abstract description 9
- 230000007246 mechanism Effects 0.000 abstract description 7
- 238000006555 catalytic reaction Methods 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 3
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 7
- 238000004502 linear sweep voltammetry Methods 0.000 description 6
- 229910052750 molybdenum Inorganic materials 0.000 description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000011733 molybdenum Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 238000001237 Raman spectrum Methods 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 235000015393 sodium molybdate Nutrition 0.000 description 3
- 239000011684 sodium molybdate Substances 0.000 description 3
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 3
- 229910018553 Ni—O Inorganic materials 0.000 description 2
- 230000010718 Oxidation Activity Effects 0.000 description 2
- OSOVKCSKTAIGGF-UHFFFAOYSA-N [Ni].OOO Chemical compound [Ni].OOO OSOVKCSKTAIGGF-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000013507 mapping Methods 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 229910000483 nickel oxide hydroxide Inorganic materials 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000004832 voltammetry Methods 0.000 description 2
- 229910006279 γ-NiOOH Inorganic materials 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910003296 Ni-Mo Inorganic materials 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- ZMXPKUWNBXIACW-UHFFFAOYSA-N [Fe].[Co].[Mo] Chemical compound [Fe].[Co].[Mo] ZMXPKUWNBXIACW-UHFFFAOYSA-N 0.000 description 1
- QXFFFIVQNZXVHM-UHFFFAOYSA-N [Fe].[Ni].[Mo].[W] Chemical compound [Fe].[Ni].[Mo].[W] QXFFFIVQNZXVHM-UHFFFAOYSA-N 0.000 description 1
- OWUGOENUEKACGV-UHFFFAOYSA-N [Fe].[Ni].[W] Chemical compound [Fe].[Ni].[W] OWUGOENUEKACGV-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- ANHCSPFMUODTLU-UHFFFAOYSA-N cobalt iron molybdenum tungsten Chemical compound [Fe][Co][Mo][W] ANHCSPFMUODTLU-UHFFFAOYSA-N 0.000 description 1
- DIUDTORAKXIZFQ-UHFFFAOYSA-N cobalt iron tungsten Chemical compound [Fe][Co][W] DIUDTORAKXIZFQ-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- VAWNDNOTGRTLLU-UHFFFAOYSA-N iron molybdenum nickel Chemical compound [Fe].[Ni].[Mo] VAWNDNOTGRTLLU-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 1
- 229910021508 nickel(II) hydroxide Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000004098 selected area electron diffraction Methods 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- JSPLKZUTYZBBKA-UHFFFAOYSA-N trioxidane Chemical compound OOO JSPLKZUTYZBBKA-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
- C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
- C25B11/031—Porous electrodes
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/054—Electrodes comprising electrocatalysts supported on a carrier
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Catalysts (AREA)
Abstract
The invention relates to an ultra-high performance anode catalyst for an alkaline water electrolysis tank and a preparation method thereof, and the scheme comprises the following steps: s00, preparing a transition metal salt mixed solution and treating foam nickel, taking the treated foam nickel as a growth substrate, and placing the growth substrate and the transition metal salt mixed solution into a reaction kettle for hydrothermal reaction to generate a required precursor catalyst; and S10, applying a set voltage to the precursor catalyst in the electrolyte until the current is stabilized to finish the electrochemical reconstruction to form the A-NiOOH catalyst. The catalyst prepared by the invention has the advantages of ultra-low overpotential, ultra-high current density and ultra-stability, and meanwhile, the electrocatalytic water oxidation performance is far superior to that of the pure Ni-based catalyst reported at present. Can be directly used in commercial alkaline electrolytic tanks, and provides important material support for further researching the water oxidation catalysis mechanism of the Ni-based catalyst.
Description
Technical Field
The invention relates to the field of alkaline electrolyzed water catalysis, in particular to an ultra-high performance anode catalyst for an alkaline water electrolysis tank and a preparation method thereof.
Background
The water electrolysis technology has become an effective way for producing hydrogen in a large scale, the main bottleneck limiting the water electrolysis efficiency is Oxygen Evolution Reaction (OER) occurring on an anode, and the development of an efficient water oxidation catalyst is a key for reducing the OER potential of the anode and improving the hydrogen production efficiency of water electrolysis.
Commercial noble metal catalysts, while effective and stable, are not only costly but also impractical for large scale use. Transition group oxides represented by iron, cobalt, nickel and the like developed at present are excellent in alkaline water oxidation catalysis, and are effective ways for replacing noble metal catalysts to reduce hydrogen production cost, but the ambiguity of a catalytic mechanism caused by multi-metal components cannot provide clear guiding significance for designing the catalysts.
Ni is considered as a transition metalThe most potential OER catalytic metal element of the catalyst is developed to various doped nonmetallic elements surrounding Ni groups or synergistic metal elements show excellent water oxidation activity, and the catalyst mechanism tends to maintain more Ni 4+ Exist to obtain better OER performance. In addition, factors such as catalyst structure and morphology can affect the active site chemistry and the number of active site exposures. Although the water oxidation activity of Ni has been demonstrated to be greater than metals such as Fe, co, mn, pure nickel-based catalysts have not been developed with OER performance comparable to commercial catalysts.
Therefore, the development of the single-metal nickel-based catalyst not only can simplify the synthesis steps, but also has a relatively clear catalyst mechanism, and has important significance for analyzing the catalysis mechanism of the Ni-based catalyst and determining the active center. There is a need to develop an anode catalyst for alkaline water baths having ultra-low overpotential, ultra-high current density and ultra-stable nickel oxyhydroxide (NiOOH).
Disclosure of Invention
The invention aims at solving the problems in the prior art and provides an ultra-high performance anode catalyst for an alkaline water electrolysis tank and a preparation method thereof.
In order to achieve the above object, the present invention adopts the following technical scheme: the preparation method of the ultra-high performance anode catalyst of the alkaline water electrolysis tank comprises the following steps:
s00, preparing a transition metal salt mixed solution and treating foam nickel, taking the treated foam nickel as a growth substrate, and placing the growth substrate and the transition metal salt mixed solution into a reaction kettle for hydrothermal reaction to generate a required precursor catalyst;
s10, applying a set voltage to the precursor catalyst in electrolyte until current is stabilized, and forming an A-NiOOH catalyst by electrochemical reconstruction, wherein the A-NiOOH catalyst is used as an anode to be prepared;
wherein the transition group metal salt mixed solution at least comprises a molybdenum source and a nickel source, and the pH value of the transition group metal salt mixed solution is controlled between 4 and 5;
wherein the precursor catalyst is a nickel molybdenum oxide catalyst.
Further, the ratio of Ni to Mo in the precursor catalyst is 1:2.5, but is not limited thereto.
Further, in step S00, the specific steps of the hydrothermal reaction are:
s01, placing the mixed solution of the transition metal salt and the growth substrate in a reaction kettle with a polytetrafluoroethylene lining;
s02, placing the reaction kettle in an oven with a set temperature until a precursor catalyst is formed.
Further, in step S00, the mixed solution of the transition metal salt should at least include any one of molybdate and scheelite for cation precipitation for structural recombination, and at least include any one of ferric nitrate, nickel nitrate and cobalt nitrate for forming metal oxyhydroxide.
Further, in step S10, the electrolyte is 1.0M KOH solution.
Further, in step S10, electrochemical reconstitution is such that electrolysis occurs at least half an hour at a set voltage.
Further, the method also comprises a step S20, which comprises the following specific steps:
s20, performing electrochemical reconstruction performance test on the catalyst subjected to electrochemical reconstruction through an electrochemical workstation three-electrode system, wherein a working electrode of the electrochemical workstation three-electrode system is an A-NiOOH catalyst, a counter electrode is a platinum mesh, a reference electrode is a mercury-mercury oxide electrode, and an electrolyte is 1.0M KOH solution.
Further, in step S20, the a-NiOOH catalyst is stably tested for at least 1000 hours, but is not limited thereto.
Further, the mixed solution of the transition metal salt is the mixed solution of nickel nitrate and molybdate or the mixed solution of nickel nitrate and sodium molybdate.
The ultra-high performance anode of the alkaline water electrolyzer is prepared by the preparation method of the ultra-high performance anode catalyst of the alkaline water electrolyzer.
The beneficial effects are that: 1. compared with the prior art, the A-NiOOH catalyst provided by the invention has the advantages that a large amount of Mo ion sources with specific proportions and specific types are introduced in the precursor synthesis process, the pH value of the mixed solution is controlled to be 4-5 by regulating and controlling the Mo ion sources, and then a large amount of catalytic active sites are constructed by dissolving out the Mo ions through electrochemical treatment, so that the ultra-high performance Ni-based oxyhydroxide catalyst is obtained. This Ni-based oxyhydroxide catalyst has a greatly increased gamma-NiOOH loading compared to other Mo sources, thus exposing the a-NiOOH catalyst to more expensive Ni active species and having excellent OER performance. Therefore, the catalyst is very suitable for being used as an ultra-high performance anode catalyst of an alkaline water electrolysis tank.
2. Compared with the prior art, the performance of the A-NiOOH catalyst disclosed by the invention is almost superior to that of all pure nickel-based catalysts reported at home and abroad at present, and the number of catalytic sites of the A-NiOOH catalyst obtained through oxidation-reduction peak integration of active sites is 150-200 times that of the conventional NiFe catalyst. In addition, the rough micro-morphology of the folds formed after the electrochemical reconstruction of the A-NiOOH also improves the electrochemical active area of the material body and promotes the mass transfer process.
3. Compared with the prior art, the A-NiOOH has high OER stability, and can be used for 500 mA cm in alkaline electrolyte -2 And 1000 mA cm -2 The electrolysis is performed for more than 1000 hours under the current density, the potential change is almost unchanged, and the method can be directly applied to the alkaline water electrolysis process.
4. Compared with the prior art, the A-NiOOH catalyst is simple and easy to prepare, the reconstruction process from the precursor to the high-activity catalyst can be realized in an electrolytic tank, and the method has application value in practical commercial alkaline electrolytic tanks. In addition, the method and mechanism for preparing the catalyst can be applied to the reconstruction process of chromium, molybdenum, tungsten, vanadium, niobium, tantalum and the like.
Drawings
FIG. 1 is a flow chart of a preparation method of the present invention;
FIG. 2 is a Scanning Electron Microscope (SEM) of an A-NiOOH field emission synthesized after chemical reconstitution of the precursor Ni: mo ratio (1:2.5) according to a preferred embodiment of the present invention;
FIG. 3 is a Transmission Electron Microscope (TEM) image (detail images of a drawing a and b) and a selected area electron diffraction (insert image of b) and an element distribution mapping image (images c, d, e) of an A-NiOOH synthesized after chemical reconstruction of the precursor Ni: mo ratio (1:2.5) according to a preferred embodiment of the present invention;
FIG. 4 shows a Raman spectrum (a) and an infrared spectrum (b) of the A-NiOOH synthesized by the invention.
FIG. 5 is a graph showing the results of three-electrode OER cyclic sweep voltammetry (CV) measurements in 1.0M KOH solution after electrochemical treatment, screening precursors of different Ni/Mo ratios in accordance with a preferred embodiment of the present invention;
FIG. 6 is a graph showing CV curves of two different NiOOH formed after other Mo source and other Mo synthesis treatment in other embodiments of the invention;
FIG. 7 is a graph of A-NiOOH synthesized in accordance with the present invention with a popular NiFe LDH catalyst, commercially RuO 2 Linear Sweep Voltammetry (LSV) patterns of the substrate NF in 1.0M KOH solution;
FIG. 8 is a graph comparing the Tafel slope of the synthesized A-NiOOH of the present invention with that of a commercially popular catalyst;
FIG. 9 is a chart of the invention of A-NiOOH at 500 mA cm for 1M KOH -2 And 1000 mA cm -2 Maintaining the test result graph for more than 1000 hours under the current density;
FIG. 10 is NiFeWO of the present invention x LSV profile before and after electrochemical reconstruction of the formed NiFe oxyhydroxide.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which are derived by a person skilled in the art based on the embodiments of the invention, fall within the scope of protection of the invention.
The invention aims to provide an ultra-low overpotential and ultra-high current density and ultra-stable nickel oxyhydroxide (NiOOH) oxygen evolution electrocatalyst through research and development of a hydrothermal synthesis method and a formula. By controlling the molybdenum source of hydrothermal synthesis, uniform rod-shaped nickel-molybdenum oxide grows on the foam nickel electrode, and after special electrochemical reconstruction treatment, the electrode material is converted into high-load, defect-filled and amorphous loose rod-shaped hydroxyl oxygenNickel oxide (a-NiOOH) has electrocatalytic water oxidation properties that exceed those of the pure Ni-based catalysts currently reported. Up to 10 mA/cm in 1.0M KOH electrolyte 2 And 500 mA/cm 2 The current density only needs 180 mV and 245 mV overpotential, at 500 and 1000 mA/cm 2 Can stably operate for more than 1000 hours at a high current density. The catalyst prepared by the invention can be used as a standard pole of the OER performance of the Ni-based catalyst, can be directly used in commercial alkaline electrolytic cells, and provides important material support for further researching the water oxidation catalysis mechanism of the Ni-based catalyst.
Example 1
As shown in fig. 1, the preparation method of the ultra-high performance anode catalyst of the alkaline water electrolysis tank comprises the following steps:
s00, preparing a transition group metal salt mixed solution and treating foam nickel, taking the treated foam nickel as a growth substrate, and placing the growth substrate and the transition group metal salt mixed solution into a reaction kettle for hydrothermal reaction to generate a required precursor catalyst;
in this example, the specific steps of the hydrothermal reaction are:
s01, placing the mixed solution of the transition metal salt and the growth substrate in a reaction kettle with a 30 ml polytetrafluoroethylene lining;
s02, placing the reaction kettle in an oven with a set temperature (such as 150 ℃) until a precursor catalyst is formed (6 hours in the embodiment);
the mixed solution of the transition group metal salt at least comprises any one of molybdate and scheelite for separating out cations for structural recombination, and at least comprises any one of ferric nitrate, nickel nitrate and cobalt nitrate for forming metal oxyhydroxide.
In the embodiment, the pH value of the mixed solution is controlled between 4 and 5 by regulating and controlling the Mo ion source.
S10, applying a set voltage to a precursor catalyst in 1.0M KOH electrolyte until current is stabilized and electrochemical reconstruction is completed to form an A-NiOOH catalyst, wherein the A-NiOOH catalyst is used as an anode to be prepared;
among these, the set voltage is preferably 1.3V (mass transfer resistance between 0.3 and 0.4 ohm with respect to mercury-oxidized mercury reference electrode), i.e. electrochemical reconstruction is about 30 minutes electrolysis occurring at 1.3V.
S20, performing electrochemical reconstruction performance test on the catalyst subjected to electrochemical reconstruction through an electrochemical workstation three-electrode system, and performing stable test for more than 1000 hours, wherein the working electrode of the electrochemical workstation three-electrode system is an A-NiOOH catalyst, the counter electrode is a platinum mesh, the reference electrode is a mercury-mercury oxide electrode, and the electrolyte is 1.0M KOH solution.
Wherein the mixed solution of the transition metal salt at least comprises a molybdenum source and a nickel source; in this embodiment, the mixed solution of the transition metal salt is a mixed solution of nickel nitrate and molybdate or a mixed solution of nickel nitrate and sodium molybdate. The ratio of the amounts of substances such as nickel nitrate and molybdate is increased from 1:0 to 1:2.5, and the two metal salts are jointly dissolved in deionized water to form a mixed solution. The proportion of sodium molybdate as Mo source and the synthesis procedure were the same as above, except that the molybdenum source was replaced.
Wherein the precursor catalyst is nickel molybdenum oxide (NiMoO) 4 . 0.7H 2 O) catalysts.
Preferably, other multi-metal catalysts used in such electrochemical treatment methods include, but are not limited to, nickel iron molybdenum, nickel iron tungsten, nickel iron molybdenum tungsten, cobalt iron molybdenum, cobalt iron tungsten, cobalt iron molybdenum tungsten, and the like.
In the embodiment, the electrochemical workstation is model CHI1140 of Shanghai, and the three-electrode working electrode is 1 cm 2 A-NiOOH catalyst of (2), counter electrode 1 cm 2 The reference electrode is a mercury-oxidized mercury electrode and the electrolyte is a 1M KOH solution.
As shown in FIG. 2, FIG. 2 is an A-NiOOH field emission Scanning Electron Microscope (SEM) diagram which is synthesized by chemically reconstructing the precursor Ni to Mo ratio (1:2.5) prepared by the method of the present embodiment, and is divided into a diagram under a low power electron microscope and a diagram under a high power electron microscope. From the graph b, the average size of the section of the micron rod with loose surface is about 1 micron, and the rod-shaped structures are uniformly and densely distributed on the substrate, so that the load capacity is greatly increased.
As shown in FIG. 3, FIG. 3 is a Transmission Electron Microscope (TEM) image (detail images a and b) of the Ni-Mo ratio (1:2.5) of the precursor prepared by the method of the present example, and a diffraction pattern (b image inset) and an element distribution mapping image (images c, d, e) of the selected area, wherein the overall loose structure can be seen in the image a, the b image can be seen without obvious crystal lattice stripes, the selected area diffraction has no obvious diffraction rings, and the even distribution of Ni and O elements can be seen in the images d and e, which prove that the structure is a loose porous amorphous NiOOH.
It is the Ni to Mo ratio of 1:2.5 in the precursor that forms the special amorphous NiOOH with the special Mo source. The loading of the NiOOH is also greatly increased relative to other ratios, and the gamma-NiOOH loading formed relative to other Mo sources is greatly increased, so that the A-NiOOH catalyst exposes more high-valence Ni active species and has excellent OER performance.
As shown in FIG. 4, FIG. 4 shows the Raman spectrum (a graph) and the infrared spectrum (b graph) of the A-NiOOH synthesized by the method. Wherein the raman spectra 472, 554 cm -1 Exhibit pronounced Ni-O bending and stretching vibrations and Ni 4+ Is abundant in 1050 cm -1 Left and right O-O - The presence of intermediate substances, 650-850 cm in the IR spectrum -1 A series of infrared absorption peaks of Ni-O are shown.
As shown in FIG. 5, FIG. 5 is a graph showing the results of three-electrode OER cyclic scanning voltammetry (CV) in 1.0M KOH solution after electrochemical treatment for screening precursors with different Ni and Mo ratios according to the present invention. From the CV comparison curve, it can be seen that the Ni group is 1:2.5: the OER performance of the A-NiOOH formed after the Mo precursor proportion treatment is the best, and the size of an oxidation peak is obviously a key factor of good performance. Wherein each ratio has two distinct oxidation peaks, which can be considered as Ni 2+ To Ni 3+ To Ni 4+ A large amount of Ni in a ratio of 1:2.5 4+ The production results in the best OER activity. Wherein the overpotential (overpotential) is referenced to the Reversible Hydrogen Electrode (RHE): e (E) RHE ＝E Ag/AgCl +0.098+0.059×pH-1.23, pH of 1.0M KOH 13.65. All CV tests were at 2 mV/sUnder scanning, ohmic compensation is 90%.
As shown in fig. 6, fig. 6 is a CV graph of two different NiOOH formed after other Mo source and other Mo synthesis treatment, and it can be seen from the graph that the a-NiOOH performance is significantly better than γ -NiOOH, and the oxidation and reduction processes of Ni with significant oxidation-reduction peaks and the significant increase of active substances. The number of catalytic sites of the A-NiOOH obtained was found to be 150-200 times that of the conventional NiFe catalyst by integration of the redox peaks at the active sites.
As shown in FIG. 7, FIG. 7 shows the A-NiOOH synthesized according to the present invention with a popular NiFe LDH catalyst, commercial IrO 2 And Linear Sweep Voltammetry (LSV) patterns of the substrate NF were measured in 1.0M KOH solution. From the LSV comparison curve, the A-NiOOH synthesized by the method is far superior to the OER performance of the comparison catalyst, and the A-NiOOH catalyst can provide higher current density at lower overpotential.
As shown in FIG. 8, FIG. 8 shows the A-NiOOH synthesized by the present invention and commercially popular catalysts (NF, irO) 2 And NiFe LDH) can reflect the dynamics of OER. Wherein Tafel is selected from 8-40 mA cm in LSV -2 The current density interval, the Tafel slope of the A-NiOOH catalyst of the invention is the lowest, reflecting faster kinetics.
As shown in FIG. 9, FIG. 9 shows that the A-NiOOH synthesized by the method of the present invention is a single crystal at 1.0M KOH at 500 mA cm -2 (a graph) and 1000 mA cm -2 (b) graph of test results maintained at current density for more than 1000 hours. After 1000 hours of constant current testing, the voltage remained essentially unchanged, reflecting that the catalyst can operate stably for a long period of time under high current.
As shown in FIG. 10, FIG. 10 is NiFeWO x The LSV curve of the NiFe oxyhydroxide formed by electrochemical reconstruction can obviously improve the performance after electrochemical treatment, which reflects the universality of the electrochemical treatment method.
As shown in table 1 below:
| catalyst | Load on foam Nickel (mg cm-2) | Overpotential (mV) @ 10 mA cm-2 | Overpotential (mV) @ 500 mA cm-2 | Durability of |
| DR-NiOOH | 3.5 | 300 | / | 260 h @ 10 mA cm-2 |
| Ni(OH)2 | 1 | 292 | / | / |
| NiOOH | 1 | 308 | / | / |
| NiOOH/ Ni3O2(OH)4 | / | 260 | / | / |
| Ni (oxy) hydroxide | / | 288 | 377 | 240 h @ 100 mA cm-2 |
| Activated NF | / | 382 | / | 20 h @ 100 mA cm-2 |
| CR-NiOOH | 1.2 | 278.2 | / | 1350 h @ 10 mA cm-2 |
| Porous NiO | / | 310 | / | 24 h @ 10 mA cm-2 |
| NiOOH | 1.1 | 333 | / | / |
| A-NiOOH | 13.5 | 180 | 245 | >1000 h @ 500 mA cm-2 1000 mA cm-2 |
TABLE 1
The comparison of the OER performance of the catalyst A-NiOOH of the invention and the pure nickel-based catalyst developed in recent years at home and abroad shows that the catalyst A-NiOOH of the invention has obvious advantages in both overpotential and long-time stability test under the same current density.
Example 2
The ultra-high performance anode of the alkaline water electrolysis cell is prepared by the preparation method of the ultra-high performance anode catalyst of the alkaline water electrolysis cell in the embodiment 1.
The invention is not described in detail in the prior art, and therefore, the invention is not described in detail.
It will be understood that the terms "a" and "an" should be interpreted as referring to "at least one" or "one or more," i.e., in one embodiment, the number of elements may be one, while in another embodiment, the number of elements may be plural, and the term "a" should not be interpreted as limiting the number.
Although specific terms are used more herein, the use of other terms is not precluded. These terms are used merely for convenience in describing and explaining the nature of the invention; they are to be interpreted as any additional limitation that is not inconsistent with the spirit of the present invention.
The present invention is not limited to the above-mentioned preferred embodiments, and any person can obtain various other products without departing from the scope of the present invention, but any changes in shape or structure of the present invention are within the scope of the present invention.
Claims (8)
1. The preparation method of the ultra-high performance anode catalyst of the alkaline water electrolysis tank is characterized by comprising the following steps:
s00, preparing a transition metal salt mixed solution and treating foam nickel, taking the treated foam nickel as a growth substrate, and placing the growth substrate and the transition metal salt mixed solution into a reaction kettle for hydrothermal reaction to generate a required precursor catalyst;
s10, applying a set voltage to the precursor catalyst in electrolyte until current is stabilized to finish electrochemical reconstruction to form an A-NiOOH catalyst, wherein the A-NiOOH catalyst is used as an anode catalyst to be prepared;
wherein the molybdate of the transition group metal salt mixed solution is used for separating out cations with restructured structures, the nickel nitrate of the transition group metal salt mixed solution is used for forming metal oxyhydroxide, and the pH value of the transition group metal salt mixed solution is controlled between 4 and 5;
wherein the precursor catalyst is a nickel molybdenum oxide catalyst.
2. The method for preparing the ultra-high performance anode catalyst of the alkaline water electrolysis bath according to claim 1, wherein the ratio of Ni to Mo in the precursor catalyst is 1:2.5.
3. The method for preparing the ultra-high performance anode catalyst of the alkaline water electrolysis bath according to claim 1, wherein in the step S00, the specific steps of the hydrothermal reaction are as follows:
s01, placing the mixed solution of the transition metal salt and the growth substrate in a reaction kettle with a polytetrafluoroethylene lining;
and S02, placing the reaction kettle in an oven with a set temperature until the precursor catalyst is formed.
4. The method for preparing an ultra-high performance anode catalyst for an alkaline water electrolysis cell according to claim 1, wherein in step S10, the electrolyte is 1.0M KOH solution.
5. The method for preparing an ultra-high performance anode catalyst for an alkaline water electrolysis cell according to claim 1, wherein in step S10, electrochemical reconstitution is such that electrolysis occurs at least half an hour at a set voltage.
6. The method for preparing an ultra-high performance anode catalyst for an alkaline water electrolyzer according to any one of claims 1 to 5, further comprising the step of S20, specifically:
s20, performing electrochemical reconstruction performance test on the catalyst subjected to electrochemical reconstruction through an electrochemical workstation three-electrode system, wherein a working electrode of the electrochemical workstation three-electrode system is an A-NiOOH catalyst, a counter electrode is a platinum mesh, a reference electrode is a mercury-mercury oxide electrode, and an electrolyte is 1.0M KOH solution.
7. The method for preparing an ultra-high performance anode catalyst for an alkaline water electrolysis cell according to claim 6, wherein the stability test of the a-NiOOH catalyst is performed for at least 1000 hours in step S20.
8. The ultra-high performance anode for the alkaline water electrolysis tank is characterized by being prepared by the preparation method of the ultra-high performance anode catalyst for the alkaline water electrolysis tank according to any one of claims 1 to 7.
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