CN116230873A - Sodium-hydrogen alkaline secondary battery, positive electrode and negative electrode catalyst - Google Patents
Sodium-hydrogen alkaline secondary battery, positive electrode and negative electrode catalyst Download PDFInfo
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- CN116230873A CN116230873A CN202310029053.5A CN202310029053A CN116230873A CN 116230873 A CN116230873 A CN 116230873A CN 202310029053 A CN202310029053 A CN 202310029053A CN 116230873 A CN116230873 A CN 116230873A
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- sodium
- nickel
- negative electrode
- alkaline secondary
- secondary battery
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- 239000003054 catalyst Substances 0.000 title claims abstract description 36
- XONPDZSGENTBNJ-UHFFFAOYSA-N molecular hydrogen;sodium Chemical compound [Na].[H][H] XONPDZSGENTBNJ-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 239000011734 sodium Substances 0.000 claims abstract description 36
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 12
- 239000001257 hydrogen Substances 0.000 claims abstract description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 10
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 8
- 239000003792 electrolyte Substances 0.000 claims abstract description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 31
- 229910052759 nickel Inorganic materials 0.000 claims description 15
- 239000006260 foam Substances 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 229910052708 sodium Inorganic materials 0.000 claims description 9
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 8
- 238000000151 deposition Methods 0.000 claims description 8
- 230000008021 deposition Effects 0.000 claims description 8
- 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 claims description 7
- 238000001354 calcination Methods 0.000 claims description 6
- 150000001868 cobalt Chemical class 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- 239000011572 manganese Substances 0.000 claims description 6
- 150000002751 molybdenum Chemical class 0.000 claims description 6
- 150000002815 nickel Chemical class 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 229910001182 Mo alloy Inorganic materials 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 4
- QZYDAIMOJUSSFT-UHFFFAOYSA-N [Co].[Ni].[Mo] Chemical compound [Co].[Ni].[Mo] QZYDAIMOJUSSFT-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- WBSVIJYYSBSHSI-UHFFFAOYSA-N cobalt nickel oxomolybdenum Chemical compound [Mo]=O.[Ni].[Co] WBSVIJYYSBSHSI-UHFFFAOYSA-N 0.000 claims description 4
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 4
- 229940044175 cobalt sulfate Drugs 0.000 claims description 4
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 239000002270 dispersing agent Substances 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 239000011733 molybdenum Substances 0.000 claims description 4
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 4
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 4
- -1 nickel-cobalt-molybdenum hydroxide Chemical compound 0.000 claims description 4
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 4
- 239000011684 sodium molybdate Substances 0.000 claims description 4
- 235000015393 sodium molybdate Nutrition 0.000 claims description 4
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical group [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 3
- 239000011609 ammonium molybdate Substances 0.000 claims description 3
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 3
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 3
- 229940010552 ammonium molybdate Drugs 0.000 claims description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 3
- 229940071125 manganese acetate Drugs 0.000 claims description 3
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 3
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- 239000001632 sodium acetate Substances 0.000 claims description 3
- 235000017281 sodium acetate Nutrition 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 238000004070 electrodeposition Methods 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 239000011656 manganese carbonate Substances 0.000 claims description 2
- 235000006748 manganese carbonate Nutrition 0.000 claims description 2
- 229940093474 manganese carbonate Drugs 0.000 claims description 2
- 239000011565 manganese chloride Substances 0.000 claims description 2
- 235000002867 manganese chloride Nutrition 0.000 claims description 2
- 229940099607 manganese chloride Drugs 0.000 claims description 2
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- 125000004436 sodium atom Chemical group 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 239000001509 sodium citrate Substances 0.000 claims description 2
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 7
- 238000004146 energy storage Methods 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 4
- 239000007774 positive electrode material Substances 0.000 abstract description 4
- 229910001415 sodium ion Inorganic materials 0.000 abstract description 4
- 150000002431 hydrogen Chemical class 0.000 abstract description 3
- 229910000510 noble metal Inorganic materials 0.000 abstract description 3
- 229910052697 platinum Inorganic materials 0.000 abstract description 3
- 230000003068 static effect Effects 0.000 abstract description 3
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 abstract description 2
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 229910045601 alloy Inorganic materials 0.000 description 5
- 239000000956 alloy Substances 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- 230000010757 Reduction Activity Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Images
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/883—Molybdenum and nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/24—Alkaline accumulators
-
- 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
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/24—Electrodes for alkaline accumulators
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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
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/24—Electrodes for alkaline accumulators
- H01M4/26—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
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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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
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- 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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention discloses a sodium-hydrogen alkaline secondary battery, positive electrode and negative electrode catalyst, the battery comprises Na 0.44 MnO 2 Positive electrode, H 2 A negative electrode, a NaOH electrolyte and a negative electrode catalyst NiCoMo. The battery is suitable for large-scale static energy storage, has low cost and long cycle life, and has excellent low-temperature performance. Na of the battery 0.44 MnO 2 The positive electrode is firstly applied to a novel sodium-hydrogen alkaline secondary battery system and is matched with the existing Na 0.44 MnO 2 Compared with the positive electrode material of the sodium ion battery, the positive electrode is applied to a novel alkaline hydrogen battery systemThe material has more excellent cycle stability, high rate performance and low temperature performance. In addition, the preparation is simple, the energy consumption is low, the cost is low, the method is not limited by resources, the method is green and environment-friendly, and the industrialization is easy to realize. Compared with the existing Pt, ru or rare noble metal catalysts, the hydrogen negative electrode catalyst for the novel sodium-hydrogen alkaline secondary battery has the advantages of low cost, green environment friendliness and suitability for large-scale production.
Description
Technical Field
The invention relates to the technical field of novel sodium-hydrogen alkaline secondary batteries, in particular to a sodium-hydrogen alkaline secondary battery, an anode and a cathode catalyst.
Background
The secondary battery (Rechargeable battery) is also called a rechargeable battery or a storage battery, and is a battery that can be continuously used by activating an active material by charging after discharging the battery. By utilizing the reversibility of chemical reaction, a new battery can be built, namely, after one chemical reaction is converted into electric energy, the chemical system can be repaired by using the electric energy, and then the chemical reaction is converted into electric energy, so the secondary battery (rechargeable battery) is called. The main rechargeable batteries in the market include nickel-hydrogen batteries, nickel-cadmium batteries, lead-acid (or lead-storage) batteries, lithium ion batteries, polymer lithium ion batteries and the like.
With the expansion of the applications of alkaline secondary batteries, development of alkaline secondary batteries with less self-discharge, suitability for large-scale static energy storage, low cost, long cycle life, excellent low-temperature performance and more convenient use is desired. The lithium ion secondary battery is a typical alkaline secondary battery, but has certain defects in price, safety, cyclicity and the like, so that development of a novel alkaline secondary battery which has the remarkable advantages of low price, high safety, good cycle performance and the like compared with the lithium ion secondary battery and has a great application prospect in the field of large-scale energy storage is urgently needed.
In addition, the current alkaline secondary battery cathode HER/HOR catalyst is always limited to noble metals Pt, ru, alloy or oxides thereof, which has the effect of increasing the cost of the battery cathode catalyst and further influencing the cost of the battery, so that the development of the cheap HER/HOR catalyst has very important significance and value. In the prior study, the NiMoCo alloy has proved to be effective for the catalytic reaction of HER/HOR, is an ideal catalyst for HER/HOR in alkaline environment, but no document or patent report exists at present on the application of the NiMoCo alloy to the novel negative electrode catalyst of alkaline secondary batteries.
Disclosure of Invention
Based on the technical problems, the invention aims to provide a positive electrode, a battery and a negative electrode catalyst of a sodium-hydrogen alkaline secondary battery.
The present invention provides a sodium-hydrogen alkaline secondary battery comprising Na 0.44 MnO 2 Positive electrode, H 2 A negative electrode, a NaOH electrolyte and a negative electrode catalyst NiCoMo.
The invention also protects a positive electrode of the sodium-hydrogen alkaline secondary battery, wherein the positive electrode is Na 0.44 MnO 2 The specific preparation method comprises the following steps: taking a sodium source and a manganese source with a certain molar ratio, adding 3mL of alcohol as a dispersing agent, grinding for 0.5-1.5 h, calcining for 6-10 h, and naturally cooling to room temperature to obtain Na 0.44 MnO 2 And a positive electrode.
Further, the molar ratio of the sodium source to the sodium atoms and the manganese atoms in the manganese source is 0.4-0.5.
Further, the sodium source is one or two of sodium carbonate, sodium acetate or sodium citrate; the manganese source is one or two of manganese carbonate, manganese acetate or manganese chloride.
Further, the grinding time is 1h; the calcination reaction temperature is 750-850 ℃ and the time is 9h.
The invention also protects a negative electrode catalyst of the sodium-hydrogen alkaline secondary battery, wherein the negative electrode catalyst is NiCoMo, and comprises a foam nickel substrate and nickel-cobalt-molybdenum alloy, nickel-cobalt-molybdenum oxide or nickel-cobalt-molybdenum hydroxide thereon.
Further, the foam nickel substrate comprises one or more of copper, iron, aluminum, titanium, zinc and magnesium.
Further, in the nickel-cobalt-molybdenum alloy, the nickel-cobalt-molybdenum oxide and the nickel-cobalt-molybdenum hydroxide, the proportion of metal nickel, cobalt and molybdenum satisfies the condition that nickel > molybdenum > cobalt; the specific preparation adopts an electrodeposition method, nickel salt, cobalt salt and molybdenum salt are dissolved in deionized water, and three-electrode deposition is carried out on biological, wherein the working electrode is foam nickel, the counter electrode is a carbon rod, the reference electrode is an Ag/AgCl electrode, the voltage is-2.1V to-0.6V, and the deposition time is 14-50 min.
Further, the nickel salt is one or two of nickel sulfate, nickel chloride or nickel acetate; the cobalt salt is one or two of cobalt sulfate, cobalt chloride or cobalt acetate; the molybdenum salt is sodium molybdate and/or ammonium molybdate.
The invention also protects the application of the negative electrode catalyst, and the negative electrode catalyst NiCoMo is applied to hydrogen negative electrode catalysts of all novel alkaline secondary batteries.
Compared with the prior art, the invention has the following beneficial effects:
the sodium-hydrogen alkaline secondary battery is a novel alkaline secondary battery, and the battery is applicable to large-scale static energy storage, low in cost, long in cycle life and excellent in low-temperature performance. Na of the battery 0.44 MnO 2 The positive electrode is firstly applied to a novel sodium-hydrogen alkaline secondary battery system and is matched with the existing Na 0.44 MnO 2 Compared with the positive electrode material of the sodium ion battery, the positive electrode material is applied to a novel alkaline hydrogen battery system, and has more excellent cycle stability, high rate performance and low temperature performance. In addition, the preparation is simple, the energy consumption is low, the cost is low, the method is not limited by resources, the method is green and environment-friendly, and the industrialization is easy to realize. Compared with the existing Pt, ru or rare noble metal catalysts, the hydrogen negative electrode catalyst for the novel sodium-hydrogen alkaline secondary battery has the advantages of low cost, green environment friendliness and suitability for large-scale production.
Drawings
FIG. 1 is a schematic diagram of the charge and discharge process of a sodium-hydrogen alkaline secondary battery according to the present invention;
FIG. 2 is a view of the Na of the present invention 0.44 MnO 2 5um scanning electron microscope image of the positive electrode;
FIG. 3 is a view of the Na of the present invention 0.44 MnO 2 A 1um scanning electron microscope image of the positive electrode;
FIG. 4 is a view of the Na of the present invention 0.44 MnO 2 20um scanning electron microscope image of the positive electrode;
FIG. 5 is a view of the Na of the present invention 0.44 MnO 2 An X-ray element energy spectrum of the positive electrode;
FIG. 6 is a view of the Na of the present invention 0.44 MnO 2 An X-ray diffraction pattern of the positive electrode;
FIG. 7 is a view of the Na of the present invention 0.44 MnO 2 Cycling performance and corresponding coulombic efficiency of the positive electrode at a current density of 1C;
FIG. 8 is a view of the Na of the present invention 0.44 MnO 2 The positive electrode is charged and discharged under the current density of 1CCurve (voltage interval 0.6-1.5V);
FIG. 9 is a scanning electron microscope image of NiMoCo deposited on nickel foam according to the present invention;
FIG. 10 is an X-ray glancing view of a NiMoCo alloy of the present invention deposited on a gold foil;
FIG. 11 is a graph of hydrogen reduction (HER) polarization for the negative electrode catalyst NiMoCo of the present invention;
FIG. 12 is a graph showing the polarization of Hydrogen Oxide (HOR) of the negative electrode catalyst NiMoCo of the present invention.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in connection with the embodiments, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
A sodium-hydrogen alkaline secondary battery comprising Na 0.44 MnO 2 Positive electrode, H 2 A negative electrode, naOH electrolyte and a negative electrode catalyst NiCoMo; during charging, the positive electrode releases sodium ions, and the negative electrode generates hydrogen; during discharge, sodium ions are embedded into the positive electrode material, negative electrode hydrogen is oxidized into protons, and the chemical reaction is as follows:
and (3) a positive electrode: na (Na) 0.269 MnO 2 +0.29Na + +0.29e - ＝Na 0.559 MnO 2 ；
And (3) a negative electrode: 0.145H 2 +0.29OH - -0.29e - ＝0.29H 2 O；
Total reaction:
Na 0.269 MnO 2 +0.29Na + +0.145H 2 +0.29OH - ＝Na 0.559 MnO 2 +0.29H 2 O；
the principle of the charge and discharge process is shown in figure 1.
Example 2
Positive electrode Na of sodium-hydrogen alkaline secondary battery 0.44 MnO 2 The preparation method comprises the steps of taking 0.25mol of sodium carbonateNa 2 CO 3 ) 1mol manganese carbonate (MnCO 3 ) Adding 3mL of alcohol as a dispersing agent, grinding for 1h in a mortar, transferring the ground material into a muffle furnace, calcining at 750-850 ℃ for reaction for 9h, naturally cooling to room temperature, and preserving in a glove box for standby to obtain Na 0.44 MnO 2 And a positive electrode.
Na 0.44 MnO 2 The positive electrode shows a uniform rod-like morphology, about 1.5-2.5 μm wide and several to tens of micrometers long, and is shown in a scanning electron microscope (see fig. 2-4 for details). The composition of the material is confirmed by a spectral scan of the elements (see figure 5 for details); the successful synthesis of Na was further confirmed by X-ray scanning diffraction patterns 0.44 MnO 2 A positive electrode (see fig. 6 for details); after the full cell is assembled, the cycle performance and the corresponding coulombic efficiency are tested, the capacity is 60mAh/g at the multiplying power of 1C, no obvious attenuation is generated after 100 cycles, and the expected cycle can be more than 10000 cycles (see figure 7 for details); the voltage interval between charge and discharge can be seen to be 0.6-1.5V according to the charge and discharge curve (see figure 8 for details).
Example 3
Positive electrode Na of sodium-hydrogen alkaline secondary battery 0.44 MnO 2 Preparation method comprises collecting 0.2mol sodium acetate (CH) 3 COONa) 0.5mol of manganese acetate (C 4 H 6 MnO 4 ) Adding 3mL of alcohol as a dispersing agent, grinding for 1.5h in a mortar, transferring the ground material into a muffle furnace, calcining at 750-850 ℃ for reaction for 10h, naturally cooling to room temperature, and preserving in a glove box for standby to obtain Na 0.44 MnO 2 And a positive electrode.
Example 4
A preparation method of a negative electrode catalyst NiCoMo of a sodium-hydrogen alkaline secondary battery comprises the steps of dissolving nickel salt, cobalt salt and molybdenum salt in deionized water, taking prepared 0.248M nickel sulfate solution, 0.049M sodium molybdate solution and 0.006M cobalt sulfate solution, and carrying out three-electrode deposition on biological, wherein a working electrode is foam nickel, a counter electrode is a carbon rod, a reference electrode is an Ag/AgCl electrode, the voltage is-2.1V, and the deposition time is 14min.
A scanning electron microscope photograph deposited on the foam nickel is shown in fig. 9, and in order to avoid the influence of the foam nickel, the foam nickel is deposited on a gold foil, and an X-ray diffraction pattern is shown in fig. 10; distinct peaks of NiCoMo alloy appear at 45 ° and the synthesized NiCoMo catalyst was tested for hydrogen reduction/oxidation (HER/HOR) (see fig. 11 and 12 for details), from which it can be seen that NiCoMo exhibits excellent hydrogen reduction/oxidation activity.
Example 5
A preparation method of a negative electrode catalyst NiCoMo of a sodium-hydrogen alkaline secondary battery comprises the steps of dissolving nickel salt, cobalt salt and molybdenum salt in deionized water, taking prepared salt solution of 0.248M nickel sulfate, nickel chloride, 0.049M sodium molybdate, ammonium molybdate and 0.006M cobalt sulfate and cobalt chloride, and carrying out three-electrode deposition on biological matters, wherein a working electrode is foam nickel, a counter electrode is a carbon rod, a reference electrode is an Ag/AgCl electrode, the voltage is-0.6V, and the deposition time is 50min.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. A sodium-hydrogen alkaline secondary battery, characterized in that the battery comprises Na 0.44 MnO 2 Positive electrode, H 2 A negative electrode, a NaOH electrolyte and a negative electrode catalyst NiCoMo.
2. The positive electrode of sodium-hydrogen alkaline secondary battery according to claim 1, wherein the Na 0.44 MnO 2 The positive electrode is prepared by the following steps: taking a sodium source and a manganese source with a certain molar ratio, adding 3mL of alcohol as a dispersing agent, grinding for 0.5-1.5 h, calcining for 6-10 h, and naturally cooling to room temperature to obtain Na 0.44 MnO 2 And a positive electrode.
3. The positive electrode of a sodium-hydrogen alkaline secondary battery according to claim 2, wherein the molar ratio of sodium atoms to manganese atoms in the sodium source to the manganese source is 0.4 to 0.5.
4. The positive electrode of a sodium-hydrogen alkaline secondary battery according to claim 2, wherein the sodium source is one or two of sodium carbonate, sodium acetate or sodium citrate; the manganese source is one or two of manganese carbonate, manganese acetate or manganese chloride.
5. The positive electrode of a sodium-hydrogen alkaline secondary battery according to claim 2, wherein the grinding time is 1h; the calcination reaction temperature is 750-850 ℃ and the time is 9h.
6. The negative electrode catalyst for sodium-hydrogen alkaline secondary battery according to claim 1, wherein the negative electrode catalyst NiCoMo comprises a foam nickel substrate and thereon a nickel-cobalt-molybdenum alloy, a nickel-cobalt-molybdenum oxide or a nickel-cobalt-molybdenum hydroxide.
7. The negative electrode catalyst for sodium-hydrogen alkaline secondary battery according to claim 6, wherein the foam nickel substrate comprises one or more of copper, iron, aluminum, titanium, zinc and magnesium.
8. The negative electrode catalyst for sodium-hydrogen alkaline secondary battery according to claim 6, wherein the ratio of metallic nickel, cobalt, molybdenum in the nickel-cobalt-molybdenum alloy, nickel-cobalt-molybdenum oxide, and nickel-cobalt-molybdenum hydroxide satisfies nickel > molybdenum > cobalt; the specific preparation adopts an electrodeposition method, nickel salt, cobalt salt and molybdenum salt are dissolved in deionized water, and three-electrode deposition is carried out on biological, wherein the working electrode is foam nickel, the counter electrode is a carbon rod, the reference electrode is an Ag/AgCl electrode, the voltage is-2.1V to-0.6V, and the deposition time is 14-50 min.
9. The negative electrode catalyst for sodium-hydrogen alkaline secondary battery according to claim 8, wherein the nickel salt is one or two of nickel sulfate, nickel chloride or nickel acetate; the cobalt salt is one or two of cobalt sulfate, cobalt chloride or cobalt acetate; the molybdenum salt is sodium molybdate and/or ammonium molybdate.
10. The use of a negative electrode catalyst for sodium-hydrogen alkaline secondary batteries according to claim 6, wherein the negative electrode catalyst NiCoMo is used for hydrogen negative electrode catalysts of all novel alkaline secondary batteries.
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| CN104319424A (en) * | 2014-11-06 | 2015-01-28 | 中国科学技术大学 | Water-system sodium ion battery as well as manufacturing method and application thereof |
| CN113363411A (en) * | 2021-05-31 | 2021-09-07 | 中国科学技术大学 | Positive electrode for nickel-hydrogen secondary battery, preparation method of positive electrode and nickel-hydrogen secondary battery |
| CN113363629A (en) * | 2021-06-03 | 2021-09-07 | 中国科学技术大学 | Aqueous carbon-hydrogen secondary battery |
| CN113832489A (en) * | 2021-11-03 | 2021-12-24 | 昆明理工大学 | Foam nickel loaded nickel-copper-manganese metal nano electro-catalyst and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104319424A (en) * | 2014-11-06 | 2015-01-28 | 中国科学技术大学 | Water-system sodium ion battery as well as manufacturing method and application thereof |
| CN113363411A (en) * | 2021-05-31 | 2021-09-07 | 中国科学技术大学 | Positive electrode for nickel-hydrogen secondary battery, preparation method of positive electrode and nickel-hydrogen secondary battery |
| CN113363629A (en) * | 2021-06-03 | 2021-09-07 | 中国科学技术大学 | Aqueous carbon-hydrogen secondary battery |
| CN113832489A (en) * | 2021-11-03 | 2021-12-24 | 昆明理工大学 | Foam nickel loaded nickel-copper-manganese metal nano electro-catalyst and preparation method thereof |
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