CN110797541A - Cathode dual-function electrocatalyst for molten salt iron air battery and application of cathode dual-function electrocatalyst - Google Patents
Cathode dual-function electrocatalyst for molten salt iron air battery and application of cathode dual-function electrocatalyst Download PDFInfo
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- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 63
- 150000003839 salts Chemical class 0.000 title claims abstract description 63
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 23
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 60
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 28
- 239000000243 solution Substances 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000003756 stirring Methods 0.000 claims abstract description 22
- 239000012153 distilled water Substances 0.000 claims abstract description 21
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 21
- 230000001588 bifunctional effect Effects 0.000 claims abstract description 20
- 239000002243 precursor Substances 0.000 claims abstract description 17
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 11
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000011259 mixed solution Substances 0.000 claims abstract description 11
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims abstract description 9
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims abstract 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 abstract description 9
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000004202 carbamide Substances 0.000 claims abstract description 8
- 238000001354 calcination Methods 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 239000003054 catalyst Substances 0.000 claims description 19
- 238000005406 washing Methods 0.000 claims description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000003792 electrolyte Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 238000011065 in-situ storage Methods 0.000 claims description 5
- -1 polytetrafluoroethylene Polymers 0.000 claims description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- MIDXCONKKJTLDX-UHFFFAOYSA-N 3,5-dimethylcyclopentane-1,2-dione Chemical compound CC1CC(C)C(=O)C1=O MIDXCONKKJTLDX-UHFFFAOYSA-N 0.000 claims description 4
- 235000013736 caramel Nutrition 0.000 claims description 4
- 230000000694 effects Effects 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
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- 238000011068 loading method Methods 0.000 claims description 2
- 239000003973 paint Substances 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims 1
- 239000006260 foam Substances 0.000 abstract description 9
- 238000007599 discharging Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000002484 cyclic voltammetry Methods 0.000 description 5
- 229910005798 NiMnO3 Inorganic materials 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000002159 nanocrystal Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
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- 239000007789 gas Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000693 micelle Substances 0.000 description 2
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- 238000006722 reduction reaction Methods 0.000 description 2
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910014103 Na-S Inorganic materials 0.000 description 1
- 229910014138 Na—NiCl2 Inorganic materials 0.000 description 1
- 229910014147 Na—S Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
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- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
-
- 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
- H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
-
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M2004/8678—Inert electrodes with catalytic activity, e.g. for fuel cells characterised by the polarity
- H01M2004/8684—Negative electrodes
-
- 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
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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- General Chemical & Material Sciences (AREA)
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- Materials Engineering (AREA)
- Inert Electrodes (AREA)
- Hybrid Cells (AREA)
Abstract
The invention relates to a cathode bifunctional electrocatalyst of a molten salt iron-air battery and application thereof, wherein the cathode bifunctional electrocatalyst of the molten salt iron-air battery is prepared by the following steps of dissolving manganese nitrate, nickel nitrate and lanthanum nitrate in distilled water, and uniformly stirring and mixing to obtain a nitrate precursor solution; dissolving cetyl trimethyl ammonium bromide in distilled water, stirring to prepare micellar solution, adding the micellar solution into a nitrate precursor solution under stirring, and finally adding urea to obtain a mixed solution; secondly, carrying out hydrothermal reaction on the mixed solution and the cut nickel foam to obtain nickel foam loaded with an electrocatalyst precursor; step three: calcining the foamed nickel loaded with the electrocatalyst precursor for 6 hours at 700 ℃ to finally prepare NiMnO3‑La2O3Fused salt iron air battery cathodeA very bifunctional electrocatalyst. The bifunctional electrocatalyst synthesized by the invention has stable OER/ORR bifunctional activity under the condition of high-temperature molten salt environment.
Description
The technical field is as follows:
the invention relates to the technical field of iron-air battery catalysts, in particular to a cathode dual-function electrocatalyst of a molten salt iron-air battery and application thereof.
Secondly, background art:
the molten salt iron air battery is a battery technology for realizing energy storage by using high-temperature molten salt as electrolyte, is used as clean energy and has high specific energy; in addition, the iron resource is rich, cheap and nontoxic, and is different from metal electrodes such as lithium, zinc and the like, the iron electrode has no dendritic crystal generation in the charging and discharging process, has long service life and is safer than metal lithium and sodium; the iron has high storage capacity (transferring 3 electrons) of multiple electrons, is far greater than that of a lithium ion battery with single electron storage, and is also far higher than that of a lithium ion battery with Na-S and Na-NiCl2A high-temperature molten salt battery as a representative; the molten salt iron air battery can directly work in an air environment, water molecules in the air have little influence on the performance of the battery, no battery diaphragm is used, the battery construction technology is simplified, the charge-discharge current intensity of the molten salt iron air battery is far higher than that of a normal-temperature battery energy storage technology, and the molten salt iron air battery is particularly suitable for large-scale power grid energy storage and is used as a power supply of an electric automobile.
In the molten salt iron air battery, a cathode electrocatalyst is a core component and is also a key material for determining the cost and the performance of the battery. In recent years, research shows that NiO nanocrystals, lithiated NiO nanocrystals, PdO modified NiO nanocrystals and amorphous MnO2The fused salt iron air battery cathode electro-catalyst such as the lithiated NiO nano-sheet has good charge and discharge performance, however, the stable catalytic oxygen evolution reaction/oxygen reduction reaction (ORR/OER) bifunctional electro-catalyst is still challenging to synthesize due to the corrosive environment of the fused salt electrolyte at high temperature. Therefore, the development of the bifunctional electrocatalyst with stable structure and performance becomes the technical field of the synthesis of the catalyst of the molten salt iron-air batteryOne of the important problems to be solved.
Thirdly, the invention content:
the invention aims to provide a cathode bifunctional electrocatalyst of a molten salt iron-air battery, which is used for solving the problem that the structure and performance of the existing electrocatalyst of the molten salt iron-air battery are not stable enough in a high-temperature molten salt environment.
The technical scheme adopted by the invention for solving the technical problems is as follows: the cathode bifunctional electrocatalyst of the molten salt iron-air battery is NiMnO3-La2O3The cathode bifunctional electrocatalyst of the molten salt iron-air battery has the dual-functional activity of catalyzing OER/ORR, has a stable morphology structure similar to that of caramel treats in a high-temperature molten salt environment, and can provide a solid-liquid-gas three-phase region for electrode reaction due to NiMnO3-La2O3The catalyst is stable at high temperature, the appearance and the structure of the catalyst are basically consistent before and after the catalyst is used, and the electrocatalytic performance has no tendency of attenuation; the preparation method comprises the following steps:
the method comprises the following steps: dissolving manganese nitrate, nickel nitrate and lanthanum nitrate in distilled water, and stirring and mixing uniformly to form a nitrate precursor solution, wherein the molar ratio of the manganese nitrate to the nickel nitrate to the lanthanum nitrate is 1.5:1: 2.5; dissolving 0.005-0.03mmol of hexadecyl trimethyl ammonium bromide in distilled water, stirring to prepare micellar solution, then adding 10-30ml of prepared micellar solution into a nitrate precursor solution under stirring, and finally adding 20-80mmol of urea to obtain a mixed solution;
step two: adding the mixed solution obtained in the step one into a hydrothermal reaction kettle with a polytetrafluoroethylene lining, putting the cut nickel foam into the hydrothermal reaction kettle, sealing the hydrothermal reaction kettle and sealing the hydrothermal reaction kettle at 180 DEG CoC, carrying out hydrothermal reaction for 12h, naturally cooling to room temperature, taking out the foamed nickel, repeatedly washing with distilled water, washing with absolute ethyl alcohol, and then washing at 60 DEG CoVacuum drying for 12h under C to obtain foamed nickel loaded with the electrocatalyst precursor;
step three: putting the foamed nickel loaded with the electrocatalyst precursor obtained in the step two into an electric furnace, calcining for 6 hours at 700 ℃ in air atmosphere, and finally obtaining the NiMnO3-La2O3Cathode bifunctional electrocatalyst of molten salt iron-air battery loaded with in-situ growth NiMnO3-La2O3The nickel foam of (1).
Preferably, in the first scheme step: dissolving 7.5 mmol of manganese nitrate, 5 mmol of nickel nitrate and 12.5 mmol of lanthanum nitrate in 50 ml of distilled water, stirring for 30min, dissolving 0.015 mmol of hexadecyl trimethyl ammonium bromide in 20 ml of distilled water, stirring to prepare micellar solution, then adding the prepared micellar solution into a nitrate precursor solution under stirring, and finally adding 50 mmol of urea to obtain a mixed solution.
The cathode bifunctional electrocatalyst of the molten salt iron-air battery is applied to the molten salt iron-air battery, and specifically comprises the following components: loading with in-situ growth NiMnO3-La2O3The foamed nickel and the nickel wire are pressed together to be used as a cathode, and the molten salt iron air battery is assembled by adding molten salt electrolyte into an iron sheet anode current collector.
In the scheme, the molten salt electrolyte is added into 11.5mol percent KCl-45 mol percent Li0.87Na0.63K0.50CO343.5mol% LiOH Mixed salt to which 0.5mol of Fe was added2O3Mixed salt/kg and 3mol of NaOH/kg, and evenly mixed to form the water-based paint.
Has the advantages that:
1. the dual-function electrocatalyst synthesized by the invention has stable structure and performance in a high-temperature molten salt environment, compared with the existing fused salt iron-air battery electrocatalyst, the catalyst grains are not enlarged after 250 times of charge-discharge cycle use at 500 ℃, the space structure among the grains is basically not changed, the micro-morphology and the structure are basically consistent with those before use, the charge-discharge performance of the battery is not obviously attenuated, the stable OER/ORR dual-function activity under the high-temperature molten salt environment condition is realized, and the application prospect on the fused salt iron-air battery is wide.
2. The electrocatalyst provided by the invention is prepared by growing the catalyst precursor on the foamed nickel in situ by a hydrothermal method and then roasting, the preparation method is simple, easy to operate, low in cost and environment-friendly, no special equipment is required in the whole preparation process, and large-scale industrial production can be carried out.
Fourthly, explanation of the attached drawings:
FIG. 1 shows the electrocatalyst NiMnO obtained in the example3-La2O3Electrocatalyst NiMnO obtained in comparative examples 1 and 23And La2O3X-ray diffraction patterns of (a);
FIG. 2 shows an electrocatalyst, NiMnO, prepared in the examples3-La2O3SEM picture of (1);
FIG. 3 shows the electrocatalyst NiMnO obtained in the example3-La2O3Cyclic voltammetry performance curves;
FIG. 4 shows the electrocatalyst NiMnO obtained in the example3-La2O3A charge-discharge cycle performance curve;
FIG. 5 shows the electrocatalyst NiMnO obtained in the example3-La2O3Charge-discharge cycling charge medium voltage and discharge medium voltage curves;
FIG. 6 shows the electrocatalyst NiMnO obtained in the example3-La2O3A charge-discharge cycle coulombic efficiency curve;
FIG. 7 shows the electrocatalyst NiMnO obtained in the example3-La2O3Typical charge-discharge cycling voltage curve;
FIG. 8 shows an electrocatalyst NiMnO prepared in example3-La2O3SEM images after charge and discharge cycles.
The fifth embodiment is as follows:
the invention is further described below with reference to the accompanying drawings:
example 1:
the cathode bifunctional electrocatalyst of the molten salt iron-air battery is NiMnO3-La2O3The cathode bifunctional electrocatalyst of the molten salt iron-air battery has the dual-functional activity of catalyzing OER/ORR, has a stable morphology structure similar to that of caramel treats in a high-temperature molten salt environment, and can provide a solid-liquid-gas three-phase region for electrode reaction due to NiMnO3-La2O3Stable at high temperature, and its shape and structure can be maintained before and after useBasically consistent, the electrocatalytic performance has no tendency of attenuation; the preparation method comprises the following steps:
dissolving 7.5 mmol of manganese nitrate, 5 mmol of nickel nitrate and 12.5 mmol of lanthanum nitrate in 50 ml of distilled water, stirring for 30min, dissolving 0.015 mmol of hexadecyl trimethyl ammonium bromide in 20 ml of distilled water, stirring to prepare micellar solution, then adding the prepared micellar solution into a nitrate precursor solution under stirring, and finally adding 50 mmol of urea; adding the mixed solution into a hydrothermal reaction kettle with a polytetrafluoroethylene lining, adding the cut nickel foam into the hydrothermal reaction kettle at 180 DEG CoC, performing hydrothermal reaction for 12 hours, naturally cooling to room temperature, taking out the foamed nickel, repeatedly washing with distilled water, washing with absolute ethyl alcohol, and then washing at 60 DEG CoVacuum drying for 12h under C, and calcining for 6h at 700 ℃ in an electric furnace in air atmosphere to finally obtain NiMnO3-La2O3A cathode electrocatalyst of a molten salt iron air battery.
The OER/ORR performance of an electrocatalyst is evaluated in cyclic voltammograms, and its electrochemical testing is performed as follows: will be loaded with NiMnO3-La2O3The foamed nickel is cut into 0.5cm multiplied by 0.5cm and pressed with a nickel wire to be used as a working electrode, and an anode current collector of an iron sheet (2cm multiplied by 2.5cm) is used as a reference electrode and a counter electrode; to 11.5mol% KCl-45 mol% Li0.87Na0.63K0.50CO343.5mol% LiOH Mixed salt to which 0.5mol of Fe was added2O3And uniformly mixing the mixed salt/kg and 3mol of NaOH/kg, taking the mixture as a molten salt electrolyte, heating the electrolyte to 500 ℃, controlling the working temperature of the battery, and testing the cyclic voltammetry curve of the electrocatalyst by adopting an electrochemical workstation in the air. And (3) testing conditions are as follows: the scan rate was 50 mV/s, and the scan voltage range was: -0.5-1V.
The charge and discharge performance test of the electrocatalyst is carried out according to the following steps: will be loaded with NiMnO3-La2O3The foamed nickel (2cm multiplied by 2.5cm) and a nickel wire are pressed together to be used as a cathode, an iron sheet (2cm multiplied by 2.5cm) is used as an anode current collector, the molten salt electrolyte is added to assemble a molten salt iron air battery, and a battery charge and discharge tester is adopted to test. The test conditions were: at the temperature of 500 ℃, the temperature of the mixture is controlled,in an air environment, charging at constant current of 50 min, standing at open circuit for 1 min, discharging to cut-off voltage of 0.7V with load constant resistance of 100 Ω, and performing cyclic charge-discharge test under the conditions.
Comparative example 1
Dissolving 12.5 mmol of lanthanum nitrate in 50 ml of distilled water, stirring for 30min, dissolving 0.015 mmol of hexadecyl trimethyl ammonium bromide in 20 ml of distilled water, stirring to prepare micellar solution, then adding the prepared micellar solution into a nitrate precursor solution under stirring, and finally adding 50 mmol of urea; adding the mixed solution into a hydrothermal reaction kettle with a polytetrafluoroethylene lining, adding the cut nickel foam into the hydrothermal reaction kettle at 180 DEG CoC, performing hydrothermal reaction for 12 hours, naturally cooling to room temperature, taking out the foamed nickel, repeatedly washing with distilled water, washing with absolute ethyl alcohol, and then washing at 60 DEG CoVacuum drying for 12h under C, and calcining for 6h at 700 ℃ in an electric furnace in air atmosphere to finally obtain La2O3A cathode electrocatalyst of a molten salt iron air battery.
Comparative example 2
Dissolving 7.5 mmol of manganese nitrate and 5 mmol of nickel nitrate in 50 ml of distilled water, stirring for 30min, dissolving 0.015 mmol of hexadecyl trimethyl ammonium bromide in 20 ml of distilled water, stirring to prepare micelle liquid, then adding the prepared micelle liquid into a nitrate precursor solution under stirring, and finally adding 50 mmol of urea; adding the mixed solution into a hydrothermal reaction kettle with a polytetrafluoroethylene lining, adding the cut nickel foam into the hydrothermal reaction kettle at 180 DEG CoC, performing hydrothermal reaction for 12 hours, naturally cooling to room temperature, taking out the foamed nickel, repeatedly washing with distilled water, washing with absolute ethyl alcohol, and then washing at 60 DEG CoVacuum drying for 12h under C, and calcining for 6h at 700 ℃ in an electric furnace in air atmosphere to finally obtain NiMnO3A cathode electrocatalyst of a molten salt iron air battery.
Characterization of the crystal structures of the electrocatalysts obtained in this example, comparative example 1 and comparative example 2 by X-ray diffraction method is shown in FIG. 1, and it can be concluded that the catalysts obtained in the examples are NiMnO3-La2O3The composition of (1). The catalysts obtained in comparative examples 1 and 2 were La respectively2O3And NiMnO3。
FIG. 2 shows an electrocatalyst, NiMnO, prepared in the examples3-La2O3The photographs show that the catalyst exhibits a three-level structure: SEM photographs (a) and (b) at magnifications of 2000 × and 2830 × showed that the catalyst layer was densely grown on the surface of the nickel foam; SEM photograph (c) at 11720X magnification shows that the catalyst is formed of NiMnO3-La2O3Composition of (i) wherein La2O3With nanoparticles distributed in NiMnO3A periphery; SEM photograph (d) at 3 ten thousand magnification and the inset therein (100 ten thousand magnification) shows that NiMnO in the prepared composition3The nano-particles are combined into a cuboid structure similar to the caramel treats.
FIG. 3 shows the electrocatalyst NiMnO obtained in the example3-La2O3The cyclic voltammetry performance curve can show that an oxidation peak and a reduction peak respectively appear at the potential of 0.65V and-0.04V, and the cyclic voltammetry performance curve has better catalytic OER and ORR performances.
FIG. 4 shows the electrocatalyst NiMnO obtained in the example3-La2O3The electrocatalyst was operated for 196 h steadily for a total of 250 charge-discharge cycles according to the charge-discharge cycle performance curve.
FIG. 5 shows the electrocatalyst NiMnO obtained in the example3-La2O3The charging medium voltage and the discharging medium voltage curve of the charging and discharging cycles show that the charging medium voltage of 250 charging and discharging cycles is between 1.4 and 1.5V, and the discharging medium voltage is about 1.14V.
FIG. 6 shows the electrocatalyst NiMnO obtained in the example3-La2O3According to the coulombic efficiency curve of the charge-discharge cycle, the coulombic efficiency average value of 250 charge-discharge cycles is 95.8%, and the highest coulombic efficiency can reach 99.8%.
FIG. 7 shows the electrocatalyst NiMnO obtained in the example3-La2O3Typical charge-discharge cycle voltage curves of the catalyst show a comparison of the charge voltage and discharge voltage curves of the catalyst at 1 st, 50 th, 100 th, 150 th, 200 th and 250 th cyclesGood overlap, indicating that the electrocatalyst performance does not decay from start to finish; secondly, the charging platform is relatively gentle, which shows that the charging polarization is not obvious, and the discharging curve shows a relatively high flat discharging platform, which shows that the catalyst has excellent discharging performance.
FIG. 8 shows an electrocatalyst NiMnO prepared in example3-La2O3From the SEM images after the charge and discharge cycles, it can be seen that the supported catalyst layer was still closely attached to the nickel foam after 250 charge and discharge cycles without any shedding or deformation, and more importantly, the catalyst micro-morphology and structure were not significantly changed from before the charge and discharge use.
The foregoing embodiments illustrate the principles, principal features and advantages of the invention, and it will be understood by those skilled in the art that the invention is not limited to the foregoing embodiments, which are merely illustrative of the principles of the invention, and that various changes and modifications may be made therein without departing from the scope of the principles of the invention.
Claims (5)
1. A cathode bifunctional electrocatalyst of a molten salt iron-air battery is characterized in that: the cathode bifunctional electrocatalyst of the molten salt iron-air battery is NiMnO3-La2O3The cathode bifunctional electrocatalyst of the molten salt iron-air battery has the dual-functional activity of catalyzing OER/ORR, has a stable morphology structure similar to that of caramel treats in a high-temperature molten salt environment, and can provide a solid-liquid-gas three-phase region for electrode reaction due to NiMnO3-La2O3The catalyst is stable at high temperature, the appearance and the structure of the catalyst are basically consistent before and after the catalyst is used, and the electrocatalytic performance has no tendency of attenuation; the preparation method comprises the following steps:
the method comprises the following steps: dissolving manganese nitrate, nickel nitrate and lanthanum nitrate in distilled water, and stirring and mixing uniformly to form a nitrate precursor solution, wherein the molar ratio of the manganese nitrate to the nickel nitrate to the lanthanum nitrate is 1.5:1: 2.5; dissolving 0.005-0.03mmol of hexadecyl trimethyl ammonium bromide in distilled water, stirring to prepare micellar solution, then adding 10-30ml of prepared micellar solution into a nitrate precursor solution under stirring, and finally adding 20-80mmol of urea to obtain a mixed solution;
step two: adding the mixed solution obtained in the step one into a hydrothermal reaction kettle with a polytetrafluoroethylene lining, putting the cut foamed nickel into the hydrothermal reaction kettle, sealing the hydrothermal reaction kettle, carrying out hydrothermal reaction for 12 hours at 180 ℃, naturally cooling the hydrothermal reaction product to room temperature, taking out the foamed nickel, repeatedly washing the foamed nickel with distilled water, washing the washed foamed nickel with absolute ethyl alcohol, and carrying out vacuum drying for 12 hours at 60 ℃ to obtain foamed nickel loaded with an electrocatalyst precursor;
step three: and (3) placing the foamed nickel loaded with the electrocatalyst precursor obtained in the step two into an electric furnace, calcining for 6 hours at 700 ℃ in an air atmosphere, and finally preparing the NiMnO3-La2O3 molten salt iron air battery cathode dual-function electrocatalyst loaded with foamed nickel in which NiMnO3-La2O3 grows in situ.
2. The molten salt iron-air battery cathode dual-function electrocatalyst according to claim 1, characterized in that: in the first step, 7.5 mmol of manganese nitrate, 5 mmol of nickel nitrate and 12.5 mmol of lanthanum nitrate are dissolved in 50 ml of distilled water, the mixture is stirred for 30min, 0.015 mmol of hexadecyl trimethyl ammonium bromide is dissolved in 20 ml of distilled water, the mixture is stirred to prepare micellar solution, then the prepared micellar solution is added into a nitrate precursor solution under stirring, and finally 50 mmol of urea is added to obtain a mixed solution.
3. The application of the cathode bifunctional electrocatalyst of the molten salt iron-air battery according to claim 1 or 2 in a molten salt iron-air battery.
4. The application of the cathode bifunctional electrocatalyst of the molten salt iron-air battery according to claim 3 in a molten salt iron-air battery is characterized in that: loading with in-situ growth NiMnO3-La2O3The foamed nickel and the nickel wire are pressed together to be used as a cathode, and the molten salt iron air battery is assembled by adding molten salt electrolyte into an iron sheet anode current collector.
5. According to claim 4The cathode bifunctional electrocatalyst of the molten salt iron-air battery is applied to the molten salt iron-air battery, and is characterized in that: the molten salt electrolyte is prepared from 11.5mol% KCl to 45mol% Li0.87Na0.63K0.50CO343.5mol% LiOH Mixed salt to which 0.5mol of Fe was added2O3Mixed salt/kg and 3mol of NaOH/kg, and evenly mixed to form the water-based paint.
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