CN114944526A - Sodium-air battery and cathode electrolyte thereof - Google Patents
Sodium-air battery and cathode electrolyte thereof Download PDFInfo
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- CN114944526A CN114944526A CN202210474556.9A CN202210474556A CN114944526A CN 114944526 A CN114944526 A CN 114944526A CN 202210474556 A CN202210474556 A CN 202210474556A CN 114944526 A CN114944526 A CN 114944526A
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- sodium
- air battery
- catholyte
- ionic liquid
- methylimidazole
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- 239000003792 electrolyte Substances 0.000 title abstract description 19
- 239000002608 ionic liquid Substances 0.000 claims abstract description 47
- 239000011734 sodium Substances 0.000 claims abstract description 31
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 claims abstract description 12
- YAXWOADCWUUUNX-UHFFFAOYSA-N 1,2,2,3-tetramethylpiperidine Chemical compound CC1CCCN(C)C1(C)C YAXWOADCWUUUNX-UHFFFAOYSA-N 0.000 claims abstract description 7
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-Tetramethylpiperidine Substances CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 235000009518 sodium iodide Nutrition 0.000 claims abstract description 4
- MPMSMUBQXQALQI-UHFFFAOYSA-N cobalt phthalocyanine Chemical compound [Co+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 MPMSMUBQXQALQI-UHFFFAOYSA-N 0.000 claims abstract 2
- 239000007784 solid electrolyte Substances 0.000 claims description 29
- -1 sodium hexafluoro-phosphate Chemical compound 0.000 claims description 28
- 239000005486 organic electrolyte Substances 0.000 claims description 25
- 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 18
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 claims description 18
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 18
- 229910052708 sodium Inorganic materials 0.000 claims description 18
- 239000003054 catalyst Substances 0.000 claims description 17
- 159000000000 sodium salts Chemical class 0.000 claims description 12
- 239000002228 NASICON Substances 0.000 claims description 11
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 10
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- 150000003949 imides Chemical class 0.000 claims description 6
- 239000010416 ion conductor Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical compound FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 claims description 3
- GARJMFRQLMUUDD-UHFFFAOYSA-N 1,1-dimethylpyrrolidin-1-ium Chemical compound C[N+]1(C)CCCC1 GARJMFRQLMUUDD-UHFFFAOYSA-N 0.000 claims description 3
- IAZSXUOKBPGUMV-UHFFFAOYSA-N 1-butyl-3-methyl-1,2-dihydroimidazol-1-ium;chloride Chemical compound [Cl-].CCCC[NH+]1CN(C)C=C1 IAZSXUOKBPGUMV-UHFFFAOYSA-N 0.000 claims description 3
- NIHOUJYFWMURBG-UHFFFAOYSA-N 1-ethyl-1-methylpyrrolidin-1-ium Chemical compound CC[N+]1(C)CCCC1 NIHOUJYFWMURBG-UHFFFAOYSA-N 0.000 claims description 3
- ZXLOSLWIGFGPIU-UHFFFAOYSA-N 1-ethyl-3-methyl-1,2-dihydroimidazol-1-ium;acetate Chemical compound CC(O)=O.CCN1CN(C)C=C1 ZXLOSLWIGFGPIU-UHFFFAOYSA-N 0.000 claims description 3
- IBZJNLWLRUHZIX-UHFFFAOYSA-N 1-ethyl-3-methyl-2h-imidazole Chemical compound CCN1CN(C)C=C1 IBZJNLWLRUHZIX-UHFFFAOYSA-N 0.000 claims description 3
- KTUWFYALZIAAGE-UHFFFAOYSA-N 1-methyl-3-octyl-2h-imidazole Chemical compound CCCCCCCCN1CN(C)C=C1 KTUWFYALZIAAGE-UHFFFAOYSA-N 0.000 claims description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 3
- FJWMUAQZNQPQRC-UHFFFAOYSA-N B(F)(F)F.C(CCC)N1CN(C=C1)C Chemical compound B(F)(F)F.C(CCC)N1CN(C=C1)C FJWMUAQZNQPQRC-UHFFFAOYSA-N 0.000 claims description 3
- 229910003249 Na3Zr2Si2PO12 Inorganic materials 0.000 claims description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 3
- XMYKEKBQWCFRPX-UHFFFAOYSA-N [Na].P(=O)(=O)F Chemical compound [Na].P(=O)(=O)F XMYKEKBQWCFRPX-UHFFFAOYSA-N 0.000 claims description 3
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 3
- 235000017281 sodium acetate Nutrition 0.000 claims description 3
- 239000001632 sodium acetate Substances 0.000 claims description 3
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- 229910001495 sodium tetrafluoroborate Inorganic materials 0.000 claims description 3
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- ZRGWIXMPMASFPS-UHFFFAOYSA-N 1-butyl-3-methyl-1,2-dihydroimidazol-1-ium;dihydrogen phosphate Chemical compound OP(O)([O-])=O.CCCC[NH+]1CN(C)C=C1 ZRGWIXMPMASFPS-UHFFFAOYSA-N 0.000 claims 1
- 238000000354 decomposition reaction Methods 0.000 abstract description 13
- 239000007787 solid Substances 0.000 abstract description 13
- 238000000034 method Methods 0.000 abstract description 4
- 238000007086 side reaction Methods 0.000 abstract description 4
- 238000002485 combustion reaction Methods 0.000 abstract description 2
- 230000002708 enhancing effect Effects 0.000 abstract description 2
- 239000003570 air Substances 0.000 description 107
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 19
- 239000000047 product Substances 0.000 description 19
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 13
- 239000002184 metal Substances 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 229910052759 nickel Inorganic materials 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- RFJSVARKFQELLL-UHFFFAOYSA-N 1-ethyl-3-methyl-2h-imidazole;1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical compound CCN1CN(C)C=C1.FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F RFJSVARKFQELLL-UHFFFAOYSA-N 0.000 description 5
- 238000007599 discharging Methods 0.000 description 5
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- QYTDEUPAUMOIOP-UHFFFAOYSA-N TEMPO Chemical class CC1(C)CCCC(C)(C)N1[O] QYTDEUPAUMOIOP-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000010348 incorporation Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- PFUVRDFDKPNGAV-UHFFFAOYSA-N sodium peroxide Chemical compound [Na+].[Na+].[O-][O-] PFUVRDFDKPNGAV-UHFFFAOYSA-N 0.000 description 3
- ZBNMBCAMIKHDAA-UHFFFAOYSA-N sodium superoxide Chemical compound [Na+].O=O ZBNMBCAMIKHDAA-UHFFFAOYSA-N 0.000 description 3
- 229910000144 sodium(I) superoxide Inorganic materials 0.000 description 3
- OWOQXILFSFZPGY-UHFFFAOYSA-N CCN1C=CN(C)C1.O=S(C(F)(F)F)(NS(C(F)(F)F)(=O)=O)=O.O=S(C(F)(F)F)(NS(C(F)(F)F)(=O)=O)=O Chemical compound CCN1C=CN(C)C1.O=S(C(F)(F)F)(NS(C(F)(F)F)(=O)=O)=O.O=S(C(F)(F)F)(NS(C(F)(F)F)(=O)=O)=O OWOQXILFSFZPGY-UHFFFAOYSA-N 0.000 description 2
- NBVHDOZEOGAKLK-UHFFFAOYSA-N [N]=O.CC1C(N(CCC1)C)(C)C Chemical compound [N]=O.CC1C(N(CCC1)C)(C)C NBVHDOZEOGAKLK-UHFFFAOYSA-N 0.000 description 2
- 239000012080 ambient air Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000001404 mediated effect Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- NJMWOUFKYKNWDW-UHFFFAOYSA-N 1-ethyl-3-methylimidazolium Chemical compound CCN1C=C[N+](C)=C1 NJMWOUFKYKNWDW-UHFFFAOYSA-N 0.000 description 1
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000413 hydrolysate Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- YLKTWKVVQDCJFL-UHFFFAOYSA-N sodium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Na+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F YLKTWKVVQDCJFL-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- AEXDMFVPDVVSQJ-UHFFFAOYSA-N trifluoro(trifluoromethylsulfonyl)methane Chemical group FC(F)(F)S(=O)(=O)C(F)(F)F AEXDMFVPDVVSQJ-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
- H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
-
- 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
Abstract
The invention provides a sodium-air battery and a cathode electrolyte thereof. The catholyte comprises an ionic liquid solvent and a redox medium dissolved in the ionic liquid solvent, wherein the redox medium is one or a combination of binuclear cobalt phthalocyanine (II), tetramethylpiperidine oxynitride and sodium iodide. The sodium-air battery comprises the catholyte. The redox mediator contained in the catholyte solution of the present invention is capable of accelerating solid state discharge products (e.g., Na) 2 O 2 And/or NaO 2 ) The decomposition of the sodium-air battery can relieve the problem of discharge termination caused by air electrode blockage by discharge products which are not completely decomposed in the battery circulation process, effectively reduce the charging voltage of the sodium-air battery, improve the round trip efficiency and the circulation stability of the battery, and also avoid the problems of easy decomposition, easy combustion and serious side reaction of sodium-air battery electrolyte of an organic system, thereby enhancing the use safety of the battery.
Description
Technical Field
The invention relates to the technical field of sodium-air batteries, in particular to a sodium-air battery and a cathode electrolyte thereof.
Background
The sodium-air battery mainly includes an organic system sodium-air battery and an organic/water mixed system sodium-air battery, however, the batteries of both systems have certain disadvantages.
The most outstanding problems of the organic system sodium-air battery are that discharge products cannot be dissolved in the electrolyte, the discharge products with poor conductivity cause too high charging polarization and the discharge products incompletely decomposed during the circulation block the air electrode to cause discharge termination, and the organic system sodium-air battery also has the problems that the electrolyte is attacked by air superoxide radical to decompose, the self-inflammable characteristic causes worried safety performance and H in the ambient air 2 O、CO 2 The problem of side reactions generating by-products, etc. occurs seriously, resulting in excessively high charging polarization and low round-trip efficiency, which seriously affect the practical application of the sodium-air battery of the organic system.
In the organic/aqueous mixed sodium-air battery, the aqueous electrolyte has the problems of easy volatilization, change of the concentration of the electrolyte and CO in the air 2 The influence of (2) causes by-products such as carbonate, etc., resulting in unstable discharge voltage and limited cycle life, etc.
Disclosure of Invention
In view of the deficiencies in the prior art, it is an object of the present invention to address one or more of the problems in the prior art as set forth above. For example, it is an object of the present invention to provide a catholyte solution which is both safe and stable, and which is capable of decomposing the discharge products of sodium-air batteries.
One aspect of the present invention provides a sodium-air battery catholyte solution, which may include an ionic liquid solvent and a redox mediator dissolved in the ionic liquid solvent, wherein the redox mediator is one or a combination of more of cobalt (II) binuclear phthalocyanine, tetramethylpiperidine nitroxide and sodium iodide.
In one exemplary embodiment of the sodium-air battery catholyte of the present invention, the concentration of the redox mediator in the catholyte may be no less than 0.01 mol/L.
In one exemplary embodiment of the sodium-air battery catholyte of the present invention, sodium salt dissolved in the ionic liquid solvent may also be included at a concentration of not less than 0.01 mol/L.
In one exemplary embodiment of the sodium-air battery catholyte of the present invention, the sodium salt may be one or more combinations of sodium bistrifluoromethylsulfonyl imide, sodium chloride, sodium acetate, sodium borofluoride, sodium phosphofluoride, sodium hexafluoro-phosphate, and sodium tetrafluoroborate.
In one exemplary embodiment of the sodium-air battery catholyte of the present invention, the ionic liquid may be a pyrrolidine-based ionic liquid or an imidazole-based ionic liquid. The pyrrolidine ionic liquid can be one or more of N, N-dimethyl pyrrolidinium bis (trifluoromethylsulfonyl) imide, N-dimethyl pyrrolidinium tetrafluoroborate, N-methylethylpyrrolidinium (trifluoromethylsulfonyl) imide and N, N-methylethylpyrrolidinium tetrafluoroborate; the imidazole ionic liquid can be one or more of 1-ethyl-3-methylimidazole bis-trifluoromethanesulfonimide, 1-butyl-3-methylimidazole chloride salt, 1-ethyl-3-methylimidazole acetate, 1-butyl-3-methylimidazole boron fluoride salt, 1-butyl-3-methylimidazole phosphate fluoride salt, 1-allyl-3-methylimidazole chloride salt, 1-octyl-3-methylimidazole hexafluoro phosphate, 1-butyl-3-methylimidazole tetrafluoroborate and 1-ethyl-3-methylimidazole tetrafluoroborate.
Another aspect of the invention provides a sodium-air battery that may include a catholyte as described above.
In an exemplary embodiment of the sodium-air battery of the invention, the sodium-air battery may further comprise an organic electrolyte and a solid electrolyte for separating the organic electrolyte from the cathode electrolyte, wherein the organic electrolyte is 0.1-1 mol/L NaClO 4 /[(EC+DMC)+FEC]And the proportion of water in the organic electrolyte is less than 6 ppm.
In one exemplary embodiment of the sodium-air battery of the invention, the solid electrolyte is Na 3 Zr 2 Si 2 PO 12 NASICON structure fast ion conductor or beta-Al 2 O 3 Sodium aluminate fast ion conductor of type (III).
In one exemplary embodiment of a sodium-air battery of the invention, the redox mediator-mediated solid state discharge product is Na 2 O 2 Or NaO 2 。
Compared with the prior art, the beneficial effects of the invention at least comprise at least one of the following:
(1) the invention takes the ionic liquid as the solvent of the cathode electrolyte, avoids the problem of easy volatilization of the aqueous electrolyte, and improves the round-trip efficiency and the cycle life of the sodium-air battery; simultaneously, the electrolyte in the organic system sodium-air battery is prevented from being subjected to H in the air 2 O、O 2 The problem of generating byproducts due to serious decomposition is influenced.
(2) The redox mediator contained in the catholyte solution of the present invention is capable of accelerating solid state discharge products (e.g., Na) 2 O 2 And/or NaO 2 ) The decomposition of the sodium-air battery solves the problem of discharge termination caused by blockage of an air electrode by a discharge product which is not completely decomposed in the battery circulation process, effectively reduces the charging voltage of the sodium-air battery, improves the round trip efficiency and the circulation stability of the battery, and also avoids the problems of easy decomposition, easy combustion and serious side reaction of the sodium-air battery electrolyte of an organic system, thereby enhancing the use safety of the battery.
(3) The sodium-air battery has long cycle service life, high safety performance and strong practicability and wide applicability.
Drawings
The above and other objects and features of the present invention will become more apparent from the following description taken in conjunction with the accompanying drawings, in which:
fig. 1 is a charge-discharge curve diagram of the sodium-air batteries prepared in example 1 and comparative example 1 at room temperature.
Fig. 2 is a charge-discharge graph of the sodium-air battery prepared in example 2 at room temperature.
Fig. 3 is a charge-discharge graph of the sodium-air battery prepared in example 3 at room temperature.
Fig. 4 is a charge-discharge graph of the sodium-air battery prepared in example 4 at room temperature.
Fig. 5 is a charge-discharge graph of the sodium-air battery prepared in example 5 at room temperature.
Fig. 6 is a charge-discharge graph of the sodium-air battery prepared in example 6 at room temperature.
Fig. 7 is a charge-discharge graph of the sodium-air battery prepared in example 7 at room temperature.
Detailed Description
Hereinafter, a sodium-air battery and a catholyte thereof according to the present invention will be described in detail with reference to the accompanying drawings and exemplary embodiments.
In particular, in one aspect, the introduction of the catholyte of the present invention through a Redox Mediator (RM) may enable the catholyte to accelerate the decomposition of solid discharge products. During the discharge process of the sodium-air battery of the ionic liquid mixed system, polycrystalline sodium peroxide (Na) is formed on the surface of a cathode due to the reduction of oxygen 2 O 2 ) And sodium superoxide (NaO) 2 ) Polycrystalline sodium peroxide and sodium superoxide are insoluble and poorly conducting discharge products that slowly and incompletely dissolve during charging and discharging resulting in severe blockage of gas channels, ultimately resulting in high charge voltage and poor cycling performance of sodium-air batteries. Incorporation of a Redox Mediator (RM) which acts as an electrode surface with Na during charging of a sodium-air battery 2 O 2 And NaO 2 Mobile charge carriers in between, to Na 2 O 2 And NaO 2 Mediated effect, charge transfer is based on reversible redox RM ⇌ RM + +e − Upper, RM + In Na 2 O 2 、NaO 2 And liquid electrolyte, and the reaction 2RM takes place + +Na 2 O 2 →2Na + +O 2 +2RM and RM + +NaO 2 →Na + +O 2 + RM, by RM + With Na 2 O 2 、NaO 2 Reacting, reacting with Na 2 O 2 、NaO 2 Decompose into sodium ions and oxygen, thereby accelerating the decomposition of solid discharge products, and play a role inThe function of the catalyst for decomposing solid discharge products.
On the other hand, the redox medium is added into the ionic liquid and is used for mixed system sodium-air battery catholyte, so that the problem of short battery cycle life caused by easy volatilization of aqueous electrolyte can be avoided, and the problems that organic catholyte is easy to decompose and burn and is easy to generate side reaction are solved. Moreover, by introducing the redox medium into the ionic liquid, the problem that the discharge product is difficult to decompose when the ionic liquid is used as the catholyte is fundamentally solved, and the reduction of the charging voltage of the sodium-air battery can be effectively avoided.
One aspect of the invention provides a sodium-air battery catholyte. In one exemplary embodiment of the sodium-air battery catholyte of the present invention, the catholyte may include an ionic liquid solvent and a redox mediator dissolved in the ionic liquid solvent, wherein the redox mediator may be one or a combination of more of cobalt (II) binuclear phthalocyanine, tetramethylpiperidine nitroxide, and sodium iodide.
In the above, the sodium-air battery is a sodium-air battery of an ionic liquid mixed system. As described herein above, the use of ionic liquids as solvents, in combination with the incorporation of redox mediators, can accelerate the formation of polycrystalline sodium peroxide (Na) on the cathode surface during battery charging 2 O 2 ) And sodium superoxide (NaO) 2 ) Thereby improving the round trip efficiency of the battery, and simultaneously avoiding the battery and low cycling stability caused by volatilization and instability of the electrolyte.
Further, the concentration of the redox mediator in the catholyte is not less than 0.01mol/L, e.g., greater than 0.05mol/L, greater than 0.08mol/L, greater than 0.12mol/L, greater than 0.27mol/L, greater than 0.34mol/L, greater than 0.47mol/L, greater than 1.58mol/L, greater than 2.74mol/L, greater than 3.84mol/L, greater than 5.89mol/L, greater than 7.84mol/L, greater than 15.8mol/L, and the like. It should be understood, of course, that the incorporation of redox mediators into the catholyte solution described herein promotes the decomposition of solid discharge products, even small amounts, e.g., 0.005mol/L or 0.008 mol/L. In some embodiments, the amount of redox mediator added may be controlled below the saturation concentration in the ionic liquid solvent in order to conserve the amount of redox mediator used in order to increase the utilization of the redox mediator. It will be understood, of course, that saturation is not intended to limit the maximum amount of redox mediator added, and that exceeding the saturation concentration of the redox mediator does not affect the effects described herein. Preferably, the concentration of the redox mediator in the catholyte can be controlled between 0.5mol/L and 1 mol/L. The charging voltage of the sodium-air battery can be effectively reduced due to the introduction of the redox mediator, and the charging voltage of the sodium-air battery is related to the concentration of the redox mediator. In contrast, the concentration of the oxidation medium of 0.5mol/L to 1mol/L can reduce the charging voltage of the sodium-air battery to a lower value, and the reduction of the charging voltage is not obvious along with the continuous increase of the concentration of the oxidation-reduction medium; if the concentration of the redox medium is less than 0.5mol/L, compared with the charging voltage corresponding to the concentration of the redox medium of 0.5 mol/L-1 mol/L, the charging voltage value is still larger, a more ideal value is not achieved, and the decomposition rate of the solid discharge product is slower. Therefore, the concentration of the redox mediator in the catholyte is preferably controlled to be 0.5mol/L to 1 mol/L. For example, the concentration of the oxidizing medium may be 0.7mol/L, 0.8mol/L, or 0.9 mol/L.
Further, the catholyte can also comprise sodium salt dissolved in the ionic liquid solvent at a concentration of not less than 0.01mol/L, and the addition of the sodium salt can further increase the ionic conductivity of the electrolyte. For example, the concentration of the sodium salt can be greater than 0.03mol/L, greater than 0.09mol/L, greater than 0.13mol/L, greater than 0.27mol/L, greater than 0.58mol/L, greater than 1.23mol/L, greater than 2.37mol/L, greater than 3.48mol/L, greater than 6.74mol/L, greater than 10.32mol/L, and the like. It will of course be appreciated that the concentration of sodium salt may be below the saturation concentration of the ionic liquid or may be above the saturation concentration of the ionic liquid, in contrast to the preferred amount of sodium salt added below the saturation concentration of the ionic liquid for the purpose of sodium salt conservation.
Further, the sodium salt may be one or more of bis (trifluoromethyl) sulfonyl imide sodium, sodium chloride, sodium acetate, sodium borofluoride, sodium phosphofluoride, sodium hexafluoro phosphate and sodium tetrafluoroborate in combination. Of course, it is to be understood that other sodium salts conventional in the art may be used.
Further, the ionic liquid can be pyrrolidine ionic liquid or imidazole ionic liquid. The pyrrolidine ionic liquids may be one or more combinations of N, N-dimethylpyrrolidinium bis (trifluoromethylsulfonyl) imide (DMPTFSI), N-dimethylpyrrolidinium tetrafluoroborate (DMPBF4), N-methylethylpyrrolidinium (trifluoromethylsulfonyl) imide (EMPTFSI), N-methylethylpyrrolidinium tetrafluoroborate (EMPBF 4). The imidazole ionic liquid can be one or more of 1-ethyl-3-methylimidazole bis-trifluoromethanesulfonimide, 1-butyl-3-methylimidazole chloride salt, 1-ethyl-3-methylimidazole acetate, 1-butyl-3-methylimidazole boron fluoride salt, 1-butyl-3-methylimidazole phosphate fluoride salt, 1-allyl-3-methylimidazole chloride salt, 1-octyl-3-methylimidazole hexafluoro phosphate, 1-butyl-3-methylimidazole tetrafluoroborate and 1-ethyl-3-methylimidazole tetrafluoroborate. Of course, it should be understood that the ionic liquid may also be other ionic liquids known in the art.
Another aspect of the invention provides a sodium-air battery. In one exemplary embodiment of the sodium-air cell of the present invention, the sodium-air cell comprises the catholyte described herein above.
In some embodiments, the structure of a sodium-air battery may include, in order from the negative electrode to the positive electrode, a negative metal sodium, an organic electrolyte, a solid electrolyte, a catholyte, and an air positive electrode, wherein the organic electrolyte is separated from the catholyte by the solid electrolyte. It is to be understood that it is known in the art to assemble negative metal sodium, organic electrolyte, solid electrolyte, catholyte, and air cathode into a sodium-air battery.
Further, the organic electrolyte can be NaClO with the concentration of 0.1-1 mol/L 4 /[(EC+DMC)+FEC]The volume ratio of EC to DMC can be 1 (0-4), the volume ratio of FEC can be (1-4) vol%, EC is ethylene carbonate, DMC is dimethyl carbonate, FEC is fluoroethylene carbonate, and organic electrolyteThe water content in the hydrolysate is less than 6 ppm. For example, the volume ratio of EC to DMC may be 1:1, and the volume ratio of FEC may be 1 vol%; the organic electrolyte contains less than 5ppm, less than 4ppm, less than 3ppm, less than 2ppm or less than 1ppm of water. Of course, it should be understood that the organic electrolytes described herein may also be carbonates and other organic electrolytes known in the art.
Further, the solid electrolyte may be Na 3 Zr 2 Si 2 PO 12 NASICON structure fast ion conductor or beta-Al 2 O 3 Sodium aluminate fast ion conductor of type (III). By using NASICON for the mixed-system sodium-air battery solid electrolyte (also referred to as "separator") described herein, the problems of shuttling of redox mediators and corrosion of the negative sodium metal can be prevented, enabling stable operation of the sodium-air battery in ambient air. In addition, due to the incombustible property and the non-volatile property of the catholyte, the sodium-air battery can operate under the extreme temperature condition, and the catholyte described herein can enable the sodium-air battery to have lower charge-discharge polarization and stronger environmental applicability, greatly improve the performance and the use safety of the battery, and simultaneously have a longer cycle life than that of an organic/water mixed system sodium-air battery, and have strong practicability and wide applicability.
Further, the air positive electrode of the sodium-air battery may be supported with a catalyst. By loading a catalyst on the air anode, the discharge platform of the sodium-air battery can be further improved by matching with the catholyte described herein, and the energy conversion efficiency of the battery is improved. In particular, the catalyst is capable of reacting to solid state discharge products (Na) in direct contact therewith 2 O 2 And/or NaO 2 ) Decomposition proceeds, but decomposition of the solid discharge products is limited by contact with the catalyst, and solid discharge products that are not in contact with the catalyst do not undergo decomposition. The addition of the redox medium described herein can cooperate with the catalyst to decompose the solid discharge product not directly contacting the catalyst without affecting the performance of the catalyst, thereby improving the thoroughness of the decomposition of the solid oxidation product and further improving the sodium-ion activityRound trip energy utilization and cycle stability of air cells. The catalysts described herein may be perovskite-type catalysts, MOFs, heteroatom-doped carbon materials, Fe metal-type catalysts, monatomic-type catalysts, nanoclusters, nanoparticles, and the like. Of course, it is to be understood that the catalysts described herein may be other catalysts known to those skilled in the art.
Further, the air positive electrode may be pressed from a catalyst and a conductive mesh. The conductive mesh may be a nickel mesh. Of course, it should be understood that the air anodes described herein may be known to those skilled in the art.
For a better understanding of the present invention, the following further illustrates the contents of the present invention with reference to specific examples, but the contents of the present invention are not limited to the following examples.
The sodium-air batteries of the following examples and comparative examples were prepared by the following procedure:
and 2, dripping the cathode electrolyte on the solid electrolyte, putting carbon paper and a conductive nickel net on the positive conductive die, and assembling to obtain the sodium-air battery.
The sodium-air battery structures of the following examples and comparative examples include an anode metal sodium, an organic electrolyte, a solid electrolyte, a catholyte, and an air cathode in this order from the anode to the cathode, wherein the organic electrolyte and the catholyte are separated by the solid electrolyte.
Example 1
In this example, the sodium-air battery is constructed as follows: the thickness of the metal sodium of the negative electrode is 0.5mm, and the sectional area is 0.785cm 2 (ii) a The organic electrolyte is NaClO with the concentration of 1mol/L 4 /[(EC+DMC)(1:1)+lvol%FEC](ii) a The solid electrolyte is an NASICON solid electrolyte diaphragm with the thickness of 1.2mm and the diameter of 16 mm; the cathode electrolyte is 1-ethyl-3-methylimidazole bistrifluoromethylsulfonyl imide solution of 1mol/L tetramethyl piperidine nitrogen oxide; the air anode is made of carbon paper and is conductiveAnd pressing a nickel net.
The sodium-air battery of this example was subjected to charge and discharge performance tests under the following conditions: the reaction is carried out in an environment with room temperature and relative humidity of 80%.
Comparative example 1
In comparison with example 1, the catholyte of comparative example 1 was a pure 1-ethyl-3-methylimidazolium bistrifluoromethylsulfonimide ionic liquid without the addition of tetramethylpiperidine nitroxide, the rest being the same as example 1.
The charge and discharge curves of example 1 and comparative example 1 are shown in fig. 1, in which curve a is the charge and discharge curve of the battery prepared in example 1, and curve b is the charge and discharge curve of the battery prepared in comparative example 1. The discharge voltage of the sodium-air battery prepared in example 1 reaches 1.8V, the charging voltage is obviously reduced to 3.1V (value after the charging voltage is stabilized), the discharge voltage is smaller than that of the sodium-air battery without the addition of the redox medium, the round-trip efficiency is 59.11%, and the charging and discharging platform of the battery is relatively stable, which indicates that the ionic liquid with the addition of the redox medium can obviously reduce the charging voltage of the mixed system sodium-air battery and the battery can be charged and discharged normally.
Example 2
In this example, the sodium-air battery is constructed as follows: the thickness of the metal sodium is 0.5mm, and the area is 0.785cm 2 (ii) a The organic electrolyte is NaClO with the concentration of 1mol/L 4 /[(EC+DMC)(1:1)+lvol%FEC](ii) a The solid electrolyte is a NASICON solid electrolyte diaphragm with the thickness of 1.5mm and the diameter of 16 mm; the catholyte is a 1-ethyl-3-methylimidazole bistrifluoromethanesulfonimide solution consisting of 0.5mol/L NaTFSI sodium salt and 1mol/L tetramethyl piperidine oxynitride; the air anode is formed by pressing carbon paper and a conductive nickel net.
And (3) testing the charge and discharge performance: the reaction is carried out in an environment with room temperature and relative humidity of 80%.
The charge-discharge curve of the sodium-air battery is shown in fig. 2, and it can be seen from the graph that the discharge voltage of the sodium-air battery reaches 1.4V, the charge voltage reaches 3.2V, and the charge-discharge platform of the battery is relatively stable, which indicates that the catholyte mixed system sodium-air battery based on the ionic liquid of the present example can be charged and discharged normally.
Example 3
In this example, the sodium-air battery is constructed as follows: the thickness of the metal sodium is 0.5mm, and the area is 0.785cm 2 (ii) a NaClO with 1mol/L organic electrolyte 4 /[(EC+DMC)(1:1)+lvol%FEC](ii) a The solid electrolyte is a NASICON solid electrolyte diaphragm with the thickness of 1.5mm and the diameter of 16 mm; the cathode ionic liquid is 1-ethyl-3-methylimidazole bistrifluoromethanesulfonimide solution consisting of 1mol/L NaTFSI sodium salt and 1mol/L tetramethyl piperidine nitrogen oxide; the air anode is formed by pressing carbon paper and a conductive nickel net.
And (3) testing the charge and discharge performance: the reaction is carried out in an environment with room temperature and relative humidity of 80%.
The charge-discharge curve of the sodium-air battery is shown in fig. 3, and it can be seen from the graph that the discharge voltage of the sodium-air battery of the example reaches 1.24V, the charge voltage reaches 3.2V, and the charge-discharge platform of the battery is relatively stable, which shows that the ionic liquid of the example can significantly reduce the charge voltage of the mixed sodium-air battery and the battery can be normally charged and discharged.
Example 4
In this example, the sodium-air battery is constructed as follows: the thickness of the metal sodium is 0.5mm, and the area is 0.785cm 2 (ii) a The organic electrolyte is 1mol/L NaClO 4 /[(EC+DMC)(1:1)+lvol% FEC](ii) a The solid electrolyte is a NASICON solid electrolyte diaphragm with the thickness of 1.5mm and the diameter of 16 mm; the catholyte is a 1-ethyl-3-methylimidazole bistrifluoromethanesulfonylimide solution consisting of 0.5mol/L NaTFSI sodium salt and 0.5mol/L tetramethylpiperidine oxynitride; the air anode is formed by pressing carbon paper and a conductive nickel net.
And (3) testing the charge and discharge performance: the reaction is carried out in an environment with room temperature and relative humidity of 80%.
The charge and discharge curves of the sodium-air battery are shown in fig. 4, and it can be seen from the graph that the discharge voltage of the sodium-air battery of the example is 1.37V, the charge voltage is 3.15V, and the charge and discharge platform of the battery is relatively stable, which shows that the ionic liquid of the example can significantly reduce the charge voltage of the mixed sodium-air battery and the battery can be charged and discharged normally.
Example 5
In this example, the sodium-air battery is constructed as follows: the thickness of the metallic sodium is 0.5mm, and the area is 0.785cm 2 (ii) a The organic electrolyte is 1mol/L NaClO 4 /[(EC+DMC)(1:1)+lvol% FEC](ii) a The solid electrolyte is an NASICON solid electrolyte diaphragm with the thickness of 1.5mm and the diameter of 16 mm; the catholyte is a 1-ethyl-3-methylimidazole bistrifluoromethanesulfonimide solution consisting of 0.5mol/L NaTFSI sodium salt and 1mol/L tetramethyl piperidine oxynitride; the air anode is formed by pressing carbon paper loaded with nano nickel and a conductive nickel net.
And (3) testing the charge and discharge performance: the reaction is carried out in an environment with room temperature and relative humidity of 80%.
The charging and discharging curve of the sodium-air battery is shown in fig. 5, and it can be seen from the figure that the discharging voltage of the sodium-air battery of the example reaches 2.1V, the charging voltage reaches 3.38V, and meanwhile, the charging and discharging platform of the battery is relatively stable, which shows that the ionic liquid of the example can significantly reduce the charging voltage of the mixed system sodium-air battery, and the battery can be normally charged and discharged.
Example 6
In this example, the sodium-air battery is constructed as follows: the thickness of the metal sodium is 0.5mm, and the area is 0.785cm 2 (ii) a The organic electrolyte is 1mol/L NaClO 4 /[(EC+DMC)(1:1)+lvol%FEC](ii) a The solid electrolyte is an NASICON solid electrolyte diaphragm with the thickness of 1.5mm and the diameter of 16 mm; the catholyte is 1-ethyl-3-methylimidazole bistrifluoromethanesulfonimide solution consisting of 1mol/L NaTFSI and 0.5mol/L tetramethylpiperidine oxynitride; the air anode is formed by pressing Pt/C loaded carbon paper and a conductive nickel net.
And (3) testing the charge and discharge performance: the reaction is carried out in an environment with room temperature and relative humidity of 80%.
The charge and discharge curves of the sodium-air battery are shown in fig. 6, and it can be seen from the graph that the discharge voltage of the sodium-air battery of the example reaches 2.0V, the charge voltage reaches 3.3V, and simultaneously, the charge and discharge platform of the battery is relatively stable, which indicates that the charge voltage of the mixed sodium-air battery can be significantly reduced by the functionalized ionic liquid, and the battery can be charged and discharged normally.
Example 7
In this example, Na-blankThe gas cell is constructed as follows: the thickness of the metal sodium is 0.3mm, and the area is 0.785cm 2 (ii) a The organic electrolyte is 1mol/L NaClO 4 /[(EC+DMC)(1:1)+lvol% FEC](ii) a The solid electrolyte is an NASICON solid electrolyte diaphragm with the thickness of 1.2mm and the diameter of 16 mm; the catholyte is a 1-ethyl-3-methylimidazole bistrifluoromethanesulfonimide solution consisting of 0.5mol/L NaTFSI sodium salt and 1mol/L tetramethyl piperidine oxynitride; the air anode is formed by pressing Pt/C loaded carbon paper and a conductive nickel net.
And (3) testing the cyclic charge and discharge performance: the reaction is carried out in an environment with room temperature and relative humidity of 80%.
The cycle charge and discharge curves of the test results are shown in fig. 7, and it can be seen from the graph that the battery of this example can be stably cycled for 250 hours, indicating that the battery can be charged and discharged for a long time.
Although the present invention has been described above in connection with exemplary embodiments, it will be apparent to those skilled in the art that various modifications and changes may be made to the exemplary embodiments of the present invention without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. A sodium-air battery catholyte comprising an ionic liquid solvent and a redox mediator dissolved in the ionic liquid solvent, wherein,
the redox medium is one or more of binuclear cobalt (II) phthalocyanine, tetramethylpiperidine oxynitride and sodium iodide.
2. The sodium-air battery catholyte of claim 1 wherein the concentration of the redox mediator in the catholyte is not less than 0.01 mol/L.
3. The sodium-air battery catholyte according to claim 1 or 2, further comprising sodium salt dissolved in the ionic liquid solvent at a concentration of not less than 0.01 mol/L.
4. The sodium-air battery catholyte according to claim 3 wherein the sodium salt is one or more combinations of sodium bistrifluoromethylsulphonylimide, sodium chloride, sodium acetate, sodium borofluoride, sodium phosphofluoride, sodium hexafluoro-phosphate and sodium tetrafluoroborate.
5. The sodium-air battery catholyte according to claim 1, 2 or 4 wherein the ionic liquid is a pyrrolidine-based ionic liquid or an imidazole-based ionic liquid.
6. The sodium-air battery catholyte according to claim 5 wherein the pyrrolidine ionic liquid is one or more combinations of N, N-dimethylpyrrolidinium bis (trifluoromethylsulfonyl) imide, N-dimethylpyrrolidinium tetrafluoroborate, N-methylethylpyrrolidinium (trifluoromethylsulfonyl) imide and N, N-methylethylpyrrolidinium tetrafluoroborate; the imidazole ionic liquid is one or more of 1-ethyl-3-methylimidazole bistrifluoromethylsulfonyl imide, 1-butyl-3-methylimidazole chloride salt, 1-ethyl-3-methylimidazole acetate, 1-butyl-3-methylimidazole boron fluoride salt, 1-butyl-3-methylimidazole phosphate, 1-allyl-3-methylimidazole chloride salt, 1-octyl-3-methylimidazole hexafluoro-phosphonium, 1-butyl-3-methylimidazole tetrafluoroborate and 1-ethyl-3-methylimidazole tetrafluoroborate.
7. A sodium-air battery comprising the sodium-air battery catholyte of any one of claims 1 to 5.
8. The sodium-air battery of claim 7, further comprising an organic electrolyte and a solid electrolyte for separating the organic electrolyte from the catholyte, wherein,
the organic electrolyte is 0.1-1 mol/L NaClO 4 /[(EC+DMC)+FEC]And the water content in the organic electrolyte is not higher than 6 ppm.
9. The sodium-air battery of claim 8, wherein the solid electrolyte is Na 3 Zr 2 Si 2 PO 12 NASICON structure fast ion conductor or beta-Al 2 O 3 Sodium aluminate fast ion conductor of type (III).
10. The sodium-air battery of claim 7, 8 or 9, further comprising a catalyst-loaded air positive electrode.
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