CN113224330A - Application of copper-based compound multifunctional catalyst in lithium air battery - Google Patents
Application of copper-based compound multifunctional catalyst in lithium air battery Download PDFInfo
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- CN113224330A CN113224330A CN202110500540.6A CN202110500540A CN113224330A CN 113224330 A CN113224330 A CN 113224330A CN 202110500540 A CN202110500540 A CN 202110500540A CN 113224330 A CN113224330 A CN 113224330A
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- Prior art keywords
- copper
- lithium
- catalyst
- air battery
- based compound
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- 239000003054 catalyst Substances 0.000 title claims abstract description 81
- 239000010949 copper Substances 0.000 title claims abstract description 68
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 64
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 61
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 52
- 150000001875 compounds Chemical class 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 239000003792 electrolyte Substances 0.000 claims abstract description 17
- 239000011949 solid catalyst Substances 0.000 claims abstract description 15
- 239000007791 liquid phase Substances 0.000 claims abstract description 13
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 239000002184 metal Substances 0.000 claims abstract description 12
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000011230 binding agent Substances 0.000 claims description 13
- 239000006258 conductive agent Substances 0.000 claims description 13
- -1 copper (i) compound Chemical class 0.000 claims description 12
- 239000000725 suspension Substances 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 238000011068 loading method Methods 0.000 claims description 10
- 239000012528 membrane Substances 0.000 claims description 10
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 claims description 8
- 239000000758 substrate Substances 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims description 5
- 239000003365 glass fiber Substances 0.000 claims description 5
- 238000003837 high-temperature calcination Methods 0.000 claims description 5
- 230000020477 pH reduction Effects 0.000 claims description 5
- 229920000098 polyolefin Polymers 0.000 claims description 5
- 239000002033 PVDF binder Substances 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- 239000002041 carbon nanotube Substances 0.000 claims description 4
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 4
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 3
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 3
- 229910000552 LiCF3SO3 Inorganic materials 0.000 claims description 2
- 229910001290 LiPF6 Inorganic materials 0.000 claims description 2
- 229910000831 Steel Inorganic materials 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
- OVFCVRIJCCDFNQ-UHFFFAOYSA-N carbonic acid;copper Chemical compound [Cu].OC(O)=O OVFCVRIJCCDFNQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910000009 copper(II) carbonate Inorganic materials 0.000 claims description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Inorganic materials [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 2
- 239000011646 cupric carbonate Substances 0.000 claims description 2
- 239000004744 fabric Substances 0.000 claims description 2
- 150000004820 halides Chemical class 0.000 claims description 2
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 2
- 229910003002 lithium salt Inorganic materials 0.000 claims description 2
- 159000000002 lithium salts Chemical class 0.000 claims description 2
- 239000010959 steel Substances 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 15
- 239000001301 oxygen Substances 0.000 abstract description 15
- 229910052760 oxygen Inorganic materials 0.000 abstract description 15
- 238000007599 discharging Methods 0.000 abstract description 8
- 239000007788 liquid Substances 0.000 abstract description 5
- HPGPEWYJWRWDTP-UHFFFAOYSA-N lithium peroxide Chemical compound [Li+].[Li+].[O-][O-] HPGPEWYJWRWDTP-UHFFFAOYSA-N 0.000 abstract description 5
- 238000006722 reduction reaction Methods 0.000 abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 23
- 230000000052 comparative effect Effects 0.000 description 17
- 238000001816 cooling Methods 0.000 description 17
- 239000000047 product Substances 0.000 description 17
- 239000008367 deionised water Substances 0.000 description 16
- 229910021641 deionized water Inorganic materials 0.000 description 16
- 238000000840 electrochemical analysis Methods 0.000 description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 14
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 13
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 13
- 238000010438 heat treatment Methods 0.000 description 13
- 239000011669 selenium Substances 0.000 description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- 229910052736 halogen Inorganic materials 0.000 description 12
- 150000002367 halogens Chemical class 0.000 description 12
- 239000011259 mixed solution Substances 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- 239000013067 intermediate product Substances 0.000 description 11
- 239000002904 solvent Substances 0.000 description 11
- 229910052711 selenium Inorganic materials 0.000 description 10
- 229940091258 selenium supplement Drugs 0.000 description 10
- 238000005303 weighing Methods 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000004729 solvothermal method Methods 0.000 description 9
- 229910052717 sulfur Inorganic materials 0.000 description 9
- 239000011593 sulfur Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 238000001291 vacuum drying Methods 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 6
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 6
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 6
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 5
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 4
- 229910001323 Li2O2 Inorganic materials 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 229920001531 copovidone Polymers 0.000 description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 238000007865 diluting Methods 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 239000001103 potassium chloride Substances 0.000 description 3
- 235000011164 potassium chloride Nutrition 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 239000011781 sodium selenite Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 description 3
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 2
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- 229910003266 NiCo Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 229910052927 chalcanthite Inorganic materials 0.000 description 2
- QTMDXZNDVAMKGV-UHFFFAOYSA-L copper(ii) bromide Chemical compound [Cu+2].[Br-].[Br-] QTMDXZNDVAMKGV-UHFFFAOYSA-L 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- BVTBRVFYZUCAKH-UHFFFAOYSA-L disodium selenite Chemical compound [Na+].[Na+].[O-][Se]([O-])=O BVTBRVFYZUCAKH-UHFFFAOYSA-L 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000012983 electrochemical energy storage Methods 0.000 description 2
- 238000003411 electrode reaction Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 150000002902 organometallic compounds Chemical class 0.000 description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- 235000007715 potassium iodide Nutrition 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 229960001471 sodium selenite Drugs 0.000 description 2
- 235000015921 sodium selenite Nutrition 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 229910021590 Copper(II) bromide Inorganic materials 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 1
- 229910003424 Na2SeO3 Inorganic materials 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- KSEJGFMXRHVZCL-UHFFFAOYSA-M [O-]S(C1=CC=CC=C1)(=O)=O.N.[Na+] Chemical compound [O-]S(C1=CC=CC=C1)(=O)=O.N.[Na+] KSEJGFMXRHVZCL-UHFFFAOYSA-M 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 229940071870 hydroiodic acid Drugs 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
Images
Classifications
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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
-
- 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
-
- 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
- H01M4/8663—Selection of inactive substances as ingredients for catalytic active masses, e.g. binders, fillers
- H01M4/8668—Binders
-
- 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
- H01M4/8663—Selection of inactive substances as ingredients for catalytic active masses, e.g. binders, fillers
- H01M4/8673—Electrically conductive fillers
-
- 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
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
-
- 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
- H01M2004/8689—Positive 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
Abstract
The invention relates to an application of a copper-based compound multifunctional catalyst in a lithium air battery, wherein the copper-based compound is simultaneously used as a solid catalyst and a liquid phase catalyst in the lithium air battery. The lithium-air battery is assembled by taking a copper-based compound as a catalyst to prepare a positive pole piece and a metal lithium piece as a negative pole together with electrolyte and a diaphragm, wherein the electrolyte has certain solubility to the copper-based compound. Compared with the prior art, the multifunctional catalyst of the copper-based compound has the multiple characteristics of a solid catalyst and a liquid catalyst in a discharging process (corresponding to an oxygen reduction reaction) and a charging process (corresponding to a reaction of decomposing and separating out oxygen by lithium peroxide) in the working process of the lithium-air battery, so that the comprehensive performance of the lithium-air battery is improved, and the discharge specific capacity, the energy conversion efficiency, the rate capability and the cycle performance of the battery can be improved.
Description
Technical Field
The invention belongs to the field of lithium air batteries, and particularly relates to an application of a copper-based compound multifunctional catalyst in a lithium air battery.
Background
Lithium air batteries have an extremely high theoretical energy density (11400 Wh. kg)-1) The electrochemical energy storage device is considered as one of the most potential electrochemical energy storage devices, and is expected to become a new generation energy technology for solving the problems of long-distance transportation of electric automobiles and the like. The negative active material of the lithium-air battery is metal lithium, and the positive active material is oxygen from the air, so that the cost can be greatly reduced, and the weight and the volume of the lithium-air battery can be reduced. The battery reaction mechanism is as follows: during the discharging process, the negative electrode metal lithium loses electrons to generate lithium ions and electrons, and then the lithium ions and the electrons are respectively transmitted to the positive electrode through electrolyte inside the battery and an external circuit, and react with oxygen obtained from the air to generate a discharging product lithium peroxide; during charging, lithium peroxide, which is a discharge product on the positive electrode, is decomposed to generate lithium ions, oxygen and electrons, and then the lithium ions and the electrons are respectively transmitted to the negative electrode through the electrolyte and an external circuit to be combined to generate the metal lithium.
However, the lithium-air battery at present still has a series of technical problems of low actual energy density, poor rate performance, short cycle life and the like. The key to the performance of the lithium-air battery is the slow kinetics of the oxygen reduction reaction (ORR, corresponding to the discharge process) and oxygen evolution reaction (OER, corresponding to the charge process) caused by the insulating and insoluble nature of the discharge product, lithium peroxide. Therefore, it is highly desirable to develop a highly efficient catalyst to accelerate the electrode reaction and thus improve the overall performance of the lithium air battery.
In recent years, solid catalysts have been widely used in lithium air batteries, and the performance of the batteries has been improved to some extent. However, when a solid catalyst is used, it reacts with the discharge product Li2O2The contact between the two is solid-solid contact, and the contact area is limited, so that the catalytic activity of the catalyst cannot be fully exerted. Plus the discharge product Li2O2Insoluble, non-conductive characteristics, Li in the course of discharge2O2The accumulation on the surface of the catalyst can cover the active sites on the surface of the catalyst, so that the active sites cannot be directly connected with the oxygen of the active substanceThe contact causes a reduction in the capacity of the battery. Li in direct contact with solid catalyst during charging2O2After decomposition, a void is formed between the two, and the solid catalyst cannot react with the remaining undecomposed Li2O2Contact, and thus, it is difficult to continue the exertion of the activity of the catalyst, resulting in a decrease in charge capacity, an increase in charge overpotential, and a reduction in the cycle life of the battery. To this end, the researchers have proposed solutions using soluble liquid catalysts (also known as Redox catalysts, RMs). It can be uniformly dissolved in electrolyte, and can react with active material and Li in the course of working of battery2O2Form homogeneous solid-liquid contact. During charge/discharge, the liquid phase catalyst is first electrochemically oxidized/reduced and then separately oxidized/reduced with Li2O2And O2The chemical reaction is carried out, the electrode reaction is accelerated, and the comprehensive performance of the battery is improved. However, the liquid phase catalyst inevitably shuttles to and reacts with the lithium metal negative electrode during use due to its mobile characteristics, thereby causing self-discharge, consumption of lithium metal, and shortening of battery life.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide the application of the multifunctional catalyst of the copper-based compound in the lithium air battery, which can improve the specific discharge capacity, the energy conversion efficiency, the rate capability and the cycle performance of the battery.
The purpose of the invention can be realized by the following technical scheme: the application of multifunctional catalyst of copper-based compound in lithium air battery uses copper-based compound as solid catalyst and liquid phase catalyst simultaneously in lithium air battery.
The method specifically comprises the following steps: the positive pole piece is made of a copper-based compound serving as a catalyst, the metal lithium piece serving as a negative pole, the electrolyte and the diaphragm are assembled into the lithium-air battery, and the electrolyte has certain solubility to the copper-based compound, wherein the solubility range is 0.1-500 mM.
Furthermore, the loading amount of the copper-based compound in the positive pole piece is 0.1-1 mg-cm2。
Further, the positive pole piece is manufactured by the following method: and (3) taking a copper-based compound as a catalyst, dispersing the copper-based compound, a conductive agent and a binder in absolute ethyl alcohol to prepare a suspension, loading the suspension on a substrate, and drying to obtain the positive pole piece.
Further, the mass ratio of the catalyst to the conductive agent to the binder is 3:6:1 or 2:7: 1.
The solid content of the suspension is 0.2-5%.
Further, the conductive agent includes Super P, Ketjen Balck (KB), Vulcan XC-72, BP2000 or carbon nanotubes;
the binder comprises PTFE (polytetrafluoroethylene), PVDF (polyvinylidene fluoride) or PVA (polyvinyl alcohol);
the substrate comprises foamed nickel, carbon paper, carbon cloth, a steel wire mesh or an aluminum mesh.
Further, the copper-based compound comprises a copper (I) compound and a copper (II) compound;
wherein the copper (I) compound comprises Cu2O、Cu2S、Cu2Se or cuprous halide;
the copper (II) compound comprises CuO, CuS, CuSe and CuSO4、CuCO3、Cu(NO3)2Or a copper halide.
Furthermore, the copper-based compound is prepared by a solvothermal method, a solvothermal composite high-temperature calcination method, a direct reaction method or an acidification method.
Further, the electrolyte comprises LiTFSI/TEGDME (lithium bis (trifluoromethanesulfonylimide)/tetraethylene glycol dimethyl ether), LiCF3SO3TEGDME (lithium trifluoromethanesulfonate/tetraethyleneglycol dimethyl ether), LiTFSI/DMSO (lithium bistrifluoromethanesulfonimide/dimethyl sulfoxide), LiClO4DMSO (lithium perchlorate/dimethyl sulfoxide), LiTFSI/DME (lithium bis (trifluoromethanesulfonylimide)/dimethyl ether), LiPF6/EC:DMC[1:1(v/v)](lithium hexafluorophosphate/ethylene carbonate and dimethyl carbonate in a volume ratio of 1:1), wherein the concentration of the lithium salt is 0.1-10M.
Furthermore, the diaphragm is a double-layer diaphragm composed of a polyolefin porous membrane and a glass fiber membrane.
The solvothermal method comprises the following steps: weighing a copper source, a sulfur source or a selenium source or a halogen source according to a stoichiometric ratio, uniformly dispersing the copper source, the sulfur source or the selenium source or the halogen source in a solvent, transferring the solvent to a high-pressure reaction kettle, heating to the temperature of 100 ℃ and 300 ℃, preserving the heat for 5-30h, naturally cooling to room temperature, repeatedly washing and drying to obtain a catalyst;
wherein the copper source comprises copper metal simple substance, copper chloride, carbonate, nitrate, acetate or metal organic compound; the sulfur source comprises elemental sulfur, thiourea and thioacetamide; the selenium source comprises elemental selenium and sodium selenite; halogen sources include potassium chloride, potassium iodide, potassium fluoride, and potassium bromide; the solvent comprises deionized water, ethanol, ethylene glycol, ethylenediamine, dimethyl sulfoxide and ammonia water.
Adding a sulfur source and simultaneously adding sodium dodecyl benzene sulfonate, cetyl trimethyl ammonium bromide and stearic acid as surfactants; adding a selenium source and a halogen source, and simultaneously adding polyvinylpyrrolidone, copovidone and derivatives thereof as doping agents; when no sulfur source, selenium source or halogen source is added, sodium hydroxide, sodium carbonate and sodium bicarbonate can be added as regulators.
The solvent thermal composite high-temperature calcination method comprises the following steps: weighing a copper source, a sulfur source or a selenium source or a halogen source according to a stoichiometric ratio, uniformly dispersing the copper source, the sulfur source or the selenium source or the halogen source in a solvent, transferring the solvent to a high-pressure reaction kettle, heating to the temperature of 100 ℃ and 300 ℃, preserving the heat for 5-30h, naturally cooling to the room temperature, repeatedly washing and drying to obtain an intermediate product. Grinding and sieving the intermediate product, placing the intermediate product in a quartz boat and in the middle of a tube furnace, and performing argon protection at 2-5 ℃ for min-1The temperature is raised to 400-1000 ℃ and kept for 1-4h, and the final product is obtained after natural cooling to room temperature.
Wherein the copper source comprises copper metal simple substance, copper chloride, carbonate, nitrate, acetate or metal organic compound; the sulfur source comprises elemental sulfur, thiourea and thioacetamide; the selenium source comprises elemental selenium and sodium selenite; halogen sources include potassium chloride, potassium iodide, and potassium bromide; the solvent comprises deionized water, ethanol, ethylene glycol, ethylenediamine, dimethyl sulfoxide and ammonia water.
Adding a selenium source and a halogen source, and simultaneously adding polyvinylpyrrolidone, copovidone and derivatives thereof as doping agents; when no sulfur source, selenium source or halogen source is added, sodium hydroxide, sodium carbonate and sodium bicarbonate can be added as regulators.
The direct reaction method comprises the following steps: weighing copper oxide and halogen acid according to a stoichiometric ratio, reacting for 1-10h, filtering, vacuum drying the product, and grinding to obtain a final product; the halogen acid comprises: hydrochloric acid, hydroiodic acid, hydrofluoric acid, and hydrobromic acid.
The acidification method comprises the following steps: adding a certain amount of acid solvent into an acid-resistant reactor, slowly adding copper powder at room temperature under stirring, reacting for 1-10h, diluting the solution with water, vacuum-filtering, acidifying the clear filtrate with nitric acid, concentrating, cooling, crystallizing, centrifuging, and drying to obtain a final product; the acid solvent includes: sulfuric acid, nitric acid, hydrochloric acid.
Compared with the prior art, the invention has the following beneficial effects:
1. compared with the traditional solid catalyst, the copper-based compound multifunctional catalyst for the lithium air battery disclosed by the invention has the advantage that in the electrode made of the copper-based compound, the copper-based compound can be dissolved in the electrolyte of the lithium air battery to a certain extent. By controlling the solubility of the copper-based compound in the electrolytic solution, a state in which the solid-state catalyst and the liquid-phase catalyst coexist can be formed in the lithium-air battery. Therefore, when the copper-based compound is used for the lithium-air battery, the copper-based compound not only can play the role of a traditional solid catalyst, but also can be used as a liquid phase catalyst to further improve the performance of the battery; compared with the liquid-phase catalyst, the copper-based compound catalytic material has low solubility and small dissolving amount in the electrolyte, so that the self-discharge and the lithium metal negative electrode loss caused by the shuttling effect can be reduced. Therefore, the use of the copper-based compound as a multifunctional catalyst integrating a solid-phase catalyst and a liquid-phase catalyst can greatly improve the comprehensive performance of the lithium-air battery.
2. The multifunctional catalyst of the copper-based compound has the multiple characteristics of a solid catalyst and a liquid catalyst in a discharging process (corresponding to an oxygen reduction reaction) and a charging process (corresponding to a reaction of decomposing and separating out oxygen by lithium peroxide) in the working process of the lithium-air battery, so that the comprehensive performance of the lithium-air battery is improved, and the specific discharge capacity, the energy conversion efficiency, the rate capability and the cycle performance of the battery can be improved.
Drawings
FIG. 1 is an SEM image of flower-like CuS prepared in example 1;
FIG. 2 is an XRD pattern of flower-like CuS prepared in example 1;
FIG. 3 shows examples 1 to 14, comparative example 1 in which Super P was used alone, and comparative example 2 in which NiCo was used2S4Solid catalyst, comparative example 3 lithium air battery performance using LiI liquid phase catalyst.
Detailed Description
The present invention will be described in detail with reference to the accompanying drawings and specific embodiments, which are implemented on the premise of the technical solution of the present invention, and give detailed embodiments and specific operation procedures, but the protection scope of the present invention is not limited to the following embodiments.
Example 1: flower-shaped CuS prepared by solvothermal method and application thereof in lithium-air battery
Weighing 1mol of CuSO4·5H2O, 2mol of sulfur powder and 1mol of hexadecyl trimethyl ammonium bromide are fully dissolved in 60mL of ethylene glycol, the mixture is magnetically stirred for 3 hours, the uniformly mixed solution is placed into a 100mL high-pressure reaction kettle, the temperature is kept for 24 hours after the mixture is heated to 150 ℃, then the mixture is naturally cooled to room temperature, and finally the obtained product is repeatedly washed by deionized water and is dried in vacuum at 100 ℃ for 12 hours to obtain the catalyst flower-shaped CuS. Fig. 1 and 2 are SEM and XRD patterns, respectively, of the resulting flower-like CuS material.
Flower-shaped CuS is used as a multifunctional catalyst material, Super P is used as a conductive agent, PTFE is used as a binder, the mixture is dispersed into 30mL of absolute ethyl alcohol according to the mass ratio of 3:6:1 of the catalyst, the conductive agent and the binder, and the mixture is magnetically stirred for 4 hours to obtain a solid content of 029% suspension, loading the uniformly mixed suspension on a foamed nickel substrate by a spraying method, and vacuum drying at 60 ℃ overnight to obtain the catalyst loading of about 0.5 mg-cm-2The positive electrode plate of (2).
A self-made improved Swagelock die is adopted, a positive plate is used as a positive electrode, a metal lithium plate is used as a negative electrode, a polyolefin porous membrane and a glass fiber membrane are double-layer diaphragms, 1M LiTFSI/TEGDME is used as electrolyte, and the lithium-air battery is assembled in an argon glove box with the water content and the oxygen content lower than 0.1 ppm.
The lithium air battery charging and discharging performance test is carried out on LAND battery test equipment (Wuhan blue electronic Co., Ltd.), the battery is placed in an oxygen glove box with the water content lower than 0.1ppm, the battery is kept still for 2 hours in the oxygen atmosphere before the test, the discharging cut-off voltage of the battery is 2.0V, and the current density is 200 mA.g-1After the discharge, the battery is charged with the same capacity at the same current density, and a battery charge-discharge curve is obtained. The specific discharge capacity is limited to 1000 mAh.g-1The current density is 100mA · g-1And the discharge cutoff voltage is 2.0V, so that a cycle performance curve is obtained. The specific capacity and the current density were calculated based on the mass of the carbon material Super P used for the positive electrode.
The performance of a lithium air battery with CuS as the multifunctional catalyst is shown in fig. 3. It can be seen that the specific discharge capacity of the lithium-air battery based on the CuS multifunctional catalyst reaches 3255.4mAh g-1The cycle life of the catalyst reaches 103 circles, which is obviously higher than that of comparative example 1 which uses Super P only and comparative example 2 which uses NiCo2S4Solid catalyst, comparative example 3 lithium air battery using LiI liquid phase catalyst. As can be seen from Table 1, the use of Super P alone and NiCo alone in comparative example 1 and comparative example 2 were compared2S4The solid catalyst and the lithium-air battery using the LiI liquid catalyst in comparative example 3 have the advantages that the charging voltage of the lithium-air battery based on the CuS multifunctional catalyst is reduced, the discharging voltage of the lithium-air battery is increased, and the polarization phenomenon in the charging and discharging processes of the battery is effectively reduced, so that the energy conversion efficiency of the lithium-air battery is improved.
TABLE 1 Charge-discharge voltage and difference value of lithium air battery of example 1 and comparative examples 1 to 3
| Catalyst and process for preparing same | Discharge voltage plateau/V | Charging voltage plateau/V | Voltage difference/V between charge and discharge |
| Example 1 | 2.547 | 4.307 | 1.76 |
| Comparative example 1 | 2.513 | 4.436 | 1.923 |
| Comparative example 2 | 2.539 | 4.324 | 1.785 |
| Comparative example 3 | 2.537 | 4.316 | 1.779 |
Example 2: carambola-shaped CuS prepared by solvothermal method and application thereof in lithium-air battery
Weighing 1mol of CuSO4·5H2O, 2mol of sulfur powder and 1mol of tenAnd fully dissolving the dialkyl benzene sulfonic acid ammonium sodium into 60mL of glycol, magnetically stirring for 2h, putting the uniformly mixed solution into a 100mL high-pressure reaction kettle, heating to 150 ℃, preserving the temperature for 30h, naturally cooling to room temperature, repeatedly washing the obtained product with deionized water, and vacuum-drying at 100 ℃ for 12h to obtain the carambola-shaped CuS catalyst. A positive electrode sheet was prepared, a lithium air battery was assembled, and electrochemical tests were performed in the same manner as in example 1. The specific discharge capacity and the number of cycles of the battery are shown in fig. 3, from which it can be seen that: the specific discharge capacity of the lithium-air battery reaches 3070.1mAh g-1The number of cycles is 86.
Example 3: solvothermal method for preparing Cu2S and application thereof in lithium-air battery
0.3g of CuCl is weighed out2And 0.4g of thiourea is dissolved in 30mL of ethylenediamine solvent, ultrasonic treatment is carried out for 30min, the uniformly mixed solution is put into a 50mL high-pressure reaction kettle, heating is carried out until the temperature reaches 100 ℃, heat preservation is carried out for 20h, then natural cooling is carried out until the temperature reaches room temperature, finally the obtained product is repeatedly washed by deionized water and is dried in vacuum at 60 ℃ for 4h to obtain the catalyst Cu2And S. A positive electrode sheet was prepared, a lithium air battery was assembled, and electrochemical tests were performed in the same manner as in example 1. The specific discharge capacity and the number of cycles of the battery are shown in fig. 3, from which it can be seen that: the specific discharge capacity of the lithium-air battery reaches 2896 mAh.g-1The number of cycles is 90 cycles.
Example 4: CuSe prepared by solvothermal method and application thereof in lithium-air battery
Weighing 1mmol of CuCl, 1mmol of selenium powder and 0.5mmol of polyvinylpyrrolidone, dissolving in 80mL of deionized water, performing ultrasonic treatment for 30min, putting the uniformly mixed solution into a 100mL high-pressure reaction kettle, heating to 120 ℃, keeping the temperature for 5h, then naturally cooling to room temperature, finally repeatedly washing the obtained product with deionized water, and performing vacuum drying at 60 ℃ for 24h to obtain the catalyst CuSe. A positive electrode sheet was prepared, a lithium air battery was assembled, and electrochemical tests were performed in the same manner as in example 1. The specific discharge capacity and the number of cycles of the battery are shown in fig. 3, from which it can be seen that: the specific discharge capacity of the lithium-air battery reaches 3190mAh g-1The number of cycles was 97 cycles.
Example 5: solvothermal method for preparing Cu2Se and application thereof in lithium-air battery
Weighing 2mmol of Cu (NO)3)2·3H2O、1mmol Na2SeO3And 0.2mmol of copovidone are fully dissolved in 30mL of deionized water and ethanol mixed solution (the volume ratio is 1:1), the mixture is magnetically stirred for 2 hours, the uniformly mixed solution is placed into a 50mL high-pressure reaction kettle, the heating is carried out to 180 ℃, the heat preservation is carried out for 30 hours, then the natural cooling is carried out to the room temperature, finally the obtained product is repeatedly washed by deionized water and is dried in vacuum at 100 ℃ for 8 hours to obtain the catalyst Cu2And (5) Se. A positive electrode sheet was prepared, a lithium air battery was assembled, and electrochemical tests were performed in the same manner as in example 1. The specific discharge capacity and the number of cycles of the battery are shown in fig. 3, from which it can be seen that: the specific discharge capacity of the lithium-air battery reaches 2807mAh g-1The number of cycles is 84 cycles.
Example 6: CuCl prepared by solvothermal method and application thereof in lithium-air battery
Weighing 2mol of CuCl2·2H2Dissolving O, 1.5mmol KCl and 2.5mmol polyvinylpyrrolidone in 20mL ethanol solution, magnetically stirring for 3h, putting the uniformly mixed solution into a 50mL high-pressure reaction kettle, heating to 300 ℃, keeping the temperature for 5h, naturally cooling to room temperature, repeatedly washing the obtained product with deionized water, and vacuum-drying at 100 ℃ for 12h to obtain the catalyst CuCl. A positive electrode sheet was prepared, a lithium air battery was assembled, and electrochemical tests were performed in the same manner as in example 1. The specific discharge capacity and the number of cycles of the battery are shown in fig. 3, from which it can be seen that: the specific discharge capacity of the lithium-air battery reaches 2917mAh & g-1The number of cycles is 80 cycles.
Example 7: solvent thermal method for preparing CuBr and application of CuBr in lithium air battery
Weigh 3mmol of CuSO4·5H2Dissolving O, 2mmol KBr and 1.5mmol copovidone in 60mL deionized water and ethanol mixed solution (volume ratio is 2:1), magnetically stirring for 1.5h, placing the uniformly mixed solution into a 100mL high-pressure reaction kettle, heating to 220 ℃, preserving heat for 6h, naturally cooling to room temperature, and finally cooling to room temperatureAnd repeatedly washing the obtained product with deionized water and drying the washed product in vacuum at 80 ℃ for 5 hours to obtain a catalyst CuBr. A positive electrode sheet was prepared, a lithium air battery was assembled, and electrochemical tests were performed in the same manner as in example 1. The specific discharge capacity and the number of cycles of the battery are shown in fig. 3, from which it can be seen that: the specific discharge capacity of the lithium-air battery reaches 2796mAh g-1The number of cycles is 89.
Example 8: CuO prepared by solvothermal method and application thereof in lithium-air battery
Weigh 2.5mmol of Cu (NO)3)2·3H2O and 4mmol Na2CO3Dissolving in 50mL of deionized water, magnetically stirring for 2h, putting the uniformly mixed solution into a 100mL high-pressure reaction kettle, heating to 185 ℃, preserving the temperature for 30h, naturally cooling to room temperature, repeatedly washing the obtained product with deionized water, and vacuum-drying at 60 ℃ for 12h to obtain the catalyst CuO. A positive electrode sheet was prepared, a lithium air battery was assembled, and electrochemical tests were performed in the same manner as in example 1. The specific discharge capacity and the number of cycles of the battery are shown in fig. 3, from which it can be seen that: the specific discharge capacity of the lithium-air battery reaches 2887 mAh.g-1The number of cycles is 95 cycles.
Example 9: solvent-thermal composite high-temperature calcination method for preparing Cu2S and application thereof in lithium-air battery
Weigh 1mmol of Cu (NO)3)2And 2mmol thioacetamide is dissolved in 30mL ethylene glycol, the mixture is magnetically stirred for 30min, the uniformly mixed solution is placed in a 50mL high-pressure reaction kettle, the temperature is kept for 30h after the heating to 100 ℃, then the mixture is naturally cooled to room temperature, the obtained intermediate product is repeatedly washed by deionized water and is dried in vacuum for 6h at 80 ℃ to obtain an intermediate product, the intermediate product is ground and sieved, then the intermediate product is placed in a quartz boat and placed in the middle of a tube furnace, and the temperature is 5 ℃ per min under the argon atmosphere-1Heating to 400 ℃, keeping the temperature for 4h, and then cooling to room temperature to obtain the catalyst Cu2And S. A positive electrode sheet was prepared, a lithium air battery was assembled, and electrochemical tests were performed in the same manner as in example 1. The specific discharge capacity and the number of cycles of the battery are shown in fig. 3, from which it can be seen that:the specific discharge capacity of the lithium-air battery reaches 3150mAh g-1The number of cycles is 92.
Example 10: solvent-thermal composite high-temperature calcination method for preparing Cu2O and application thereof in lithium air battery
Weigh 3mmol of CuSO4Dissolving 40mg of NaOH in 25mL of ammonia water, magnetically stirring for 2 hours, putting the uniformly mixed solution into a 50mL high-pressure reaction kettle, heating to 300 ℃, preserving heat for 5 hours, naturally cooling to room temperature, repeatedly washing the obtained intermediate product with deionized water, vacuum-drying at 60 ℃ for 4 hours to obtain an intermediate product, grinding and sieving the intermediate product, putting the intermediate product into a quartz boat, putting the quartz boat in the middle of a tube furnace, and carrying out 2 ℃ min under the argon atmosphere-1Heating the solution to 1000 ℃, keeping the temperature for 1h, and then cooling the solution to room temperature to obtain the catalyst Cu2And O. A positive electrode sheet was prepared, a lithium air battery was assembled, and electrochemical tests were performed in the same manner as in example 1. The specific discharge capacity and the number of cycles of the battery are shown in fig. 3, from which it can be seen that: the specific discharge capacity of the lithium-air battery reaches 3082mAh g-1The number of cycles is 82.
Example 11: preparation of CuCl by direct reaction method2And its application in lithium air battery
Weighing 0.5mol of CuO and 20mL of HCl with the concentration of 10%, stirring and reacting for 10h, then filtering, and grinding the product after vacuum to obtain the catalyst CuCl2. A positive electrode sheet was prepared, a lithium air battery was assembled, and electrochemical tests were performed in the same manner as in example 1. The specific discharge capacity and the number of cycles of the battery are shown in fig. 3, from which it can be seen that: the specific discharge capacity of the lithium-air battery reaches 2892 mAh.g-1The number of cycles was 97 cycles.
Example 12: preparation of CuBr by direct reaction method2And its application in lithium air battery
Weighing 0.5mol of CuO and 80mL of HBr with the concentration of 48%, stirring for reaction for 1h, filtering, drying the product in vacuum, and grinding to obtain the catalyst CuBr2. A positive electrode sheet was prepared, a lithium air battery was assembled, and electrochemical measurements were made in the same manner as in example 1And (6) testing. The specific discharge capacity and the number of cycles of the battery are shown in fig. 3, from which it can be seen that: the specific discharge capacity of the lithium-air battery reaches 2794mAh g-1The number of cycles is 86.
Example 13: preparation of Cu (NO) by acidification method3)2And its application in lithium air battery
Adding 50mL of concentrated nitric acid into an acid-resistant reactor, slowly adding 25mg of copper powder at room temperature under stirring, reacting for 10h, diluting the solution with water, vacuum-filtering, acidifying the clear filtrate with nitric acid, concentrating, cooling, crystallizing, centrifuging, and drying to obtain the catalyst Cu (NO)3)2. A positive electrode sheet was prepared, a lithium air battery was assembled, and electrochemical tests were performed in the same manner as in example 1. The specific discharge capacity and the number of cycles of the battery are shown in fig. 3, from which it can be seen that: the specific discharge capacity of the lithium-air battery reaches 2858 mAh.g-1The number of cycles is 93.
Example 14: preparation of CuSO by acidification method4And its application in lithium air battery
Adding 30mL of sulfuric acid into an acid-resistant reactor, slowly adding 30mg of copper powder at room temperature under stirring, reacting for 1h, diluting the solution with water, vacuum-filtering, acidifying the clear filtrate with sulfuric acid, concentrating, cooling, crystallizing, centrifuging, and drying to obtain a catalyst CuSO4. A positive electrode sheet was prepared, a lithium air battery was assembled, and electrochemical tests were performed in the same manner as in example 1. The specific discharge capacity and the number of cycles of the battery are shown in fig. 3, from which it can be seen that: the specific discharge capacity of the lithium-air battery reaches 2947mAh g-1The number of cycles was 81 cycles.
Comparative example 1: application of Super P in lithium-air battery
The catalyst in example 1 was replaced with Super P, and the other steps were the same as in example 1, to prepare a positive electrode sheet, assemble a lithium air battery in the same manner as in example 1, and perform an electrochemical test. The specific discharge capacity and the number of cycles of the battery are shown in fig. 3, from which it can be seen that: the specific discharge capacity of the lithium-air battery is 1980.4mAh g-1The number of cycles is 32.
Comparative example 2: solid catalyst NiCo2S4Application in lithium air battery
With NiCo2S4For the positive electrode catalyst material, a positive electrode sheet was prepared, a lithium air battery was assembled, and an electrochemical test was performed in the same manner as in example 1. The specific discharge capacity and the number of cycles of the battery are shown in fig. 3, from which it can be seen that: the specific discharge capacity of the lithium-air battery is 2589 mAh.g-1The number of cycles is 79 cycles.
Comparative example 3: application of liquid phase catalyst LiI in lithium air battery
LiI is used as a liquid-phase catalyst and dissolved in electrolyte, the Super P pole piece prepared in comparative example 1 is adopted as a positive pole piece, the lithium-air battery is assembled by the same method as that of example 1, and an electrochemical test is carried out. The specific discharge capacity and the number of cycles of the battery are shown in fig. 3, from which it can be seen that: the specific discharge capacity of the lithium-air battery is 2597.8mAh g-1The number of cycles is 74 cycles.
Example 15
Using the flower-shaped CuS prepared in example 1 as a multifunctional catalyst material, adopting a carbon nano tube as a conductive agent and PVDF as a binder, dispersing the carbon nano tube as the conductive agent and the PVDF as a binder into absolute ethyl alcohol according to the mass ratio of the catalyst to the conductive agent to the binder of 3:6:1, magnetically stirring for 4 hours to obtain a suspension with the solid content of 0.2%, loading the uniformly mixed suspension on a foam nickel substrate by a spraying method, and vacuum drying at 60 ℃ overnight to obtain the flower-shaped CuS with the loading of about 0.1 mg-cm-2The positive electrode plate of (2).
An improved Swagelock die is adopted, an anode plate is used as an anode, a metal lithium plate is used as a cathode, a polyolefin porous membrane and a glass fiber membrane are double-layer diaphragms, 0.1M LiTFSI/TEGDME is used as electrolyte, and the lithium-air battery is assembled in an argon glove box with the water and oxygen contents lower than 0.1 ppm.
The performance of the lithium air battery obtained was tested using the method of example 1: the specific discharge capacity is 2957.9mAh g-1The energy conversion efficiency is 67%, and the number of cycles is 89. The rate capability is as follows: in thatCurrent densities of 100, 200 and 300mA g-1When used, the capacity retention rates of the batteries were 100%, 90.12% and 87.89%, respectively.
Example 16
Using the flower-shaped CuS prepared in example 1 as a multifunctional catalyst material, using Ketjen Balck as a conductive agent and PVA as a binder, dispersing the materials into absolute ethyl alcohol according to the mass ratio of the catalyst to the conductive agent to the binder of 2:7:1, magnetically stirring for 4 hours to obtain a suspension with a solid content of 5%, loading the uniformly mixed suspension on a carbon paper substrate by a coating method, and drying the carbon paper substrate at 60 ℃ in vacuum overnight to obtain the flower-shaped CuS with a loading amount of about 1 mg-cm-2The positive electrode plate of (2).
Adopting an improved Swagelock die, taking a positive pole piece as a positive pole, a metal lithium piece as a negative pole, a polyolefin porous membrane and a glass fiber membrane as double-layer diaphragms, and 10M LiClO4and/DMSO is electrolyte, and the lithium-air battery is assembled in an argon glove box with the content of water and oxygen lower than 0.1 ppm.
The performance of the lithium air battery obtained was tested using the method of example 1: the specific discharge capacity is 3088.7mAh g-1The energy conversion efficiency is 64%, and the number of cycles is 87. The rate capability is as follows: at current densities of 100, 200 and 300mA · g-1The capacity retention of the battery was 100%, 89.65% and 87.38%, respectively.
It should be noted that the present invention is not limited to the above-mentioned embodiments, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the protection scope of the present invention.
Claims (10)
1. The application of the multifunctional catalyst of the copper-based compound in the lithium air battery is characterized in that the copper-based compound is used as a solid catalyst and a liquid phase catalyst simultaneously in the lithium air battery.
2. The application of the multifunctional copper-based compound catalyst in the lithium-air battery according to claim 1, wherein the copper-based compound is used as the catalyst to prepare a positive electrode plate, the metal lithium plate is used as a negative electrode, and the positive electrode plate, the metal lithium plate, the electrolyte and the diaphragm are assembled together to form the lithium-air battery, wherein the electrolyte has a certain solubility on the copper-based compound, and the solubility range is 0.1-500 mM.
3. The application of the multifunctional catalyst of copper-based compound in the lithium-air battery as claimed in claim 2, wherein the loading amount of the copper-based compound in the positive electrode plate is 0.1-1 mg-cm2。
4. The application of the multifunctional catalyst of copper-based compound in the lithium-air battery according to claim 2 or 3, wherein the positive pole piece is prepared by the following method: and (3) taking a copper-based compound as a catalyst, dispersing the copper-based compound, a conductive agent and a binder in absolute ethyl alcohol to prepare a suspension, loading the suspension on a substrate, and drying to obtain the positive pole piece.
5. The application of the multifunctional catalyst of copper-based compound in the lithium air battery as claimed in claim 4, wherein the mass ratio of the catalyst, the conductive agent and the binder is 3:6:1 or 2:7: 1;
the solid content of the suspension is 0.2-5%.
6. The use of the multifunctional catalyst of claim 4, wherein the conductive agent comprises Super P, Ketjen Balck, Vulcan XC-72, BP2000 or carbon nanotubes;
the binder comprises PTFE, PVDF or PVA;
the substrate comprises foamed nickel, carbon paper, carbon cloth, a steel wire mesh or an aluminum mesh.
7. The use of a copper-based compound multifunctional catalyst in a lithium air battery according to claim 1 or 2, wherein the copper-based compound comprises a copper (i) compound and a copper (ii) compound;
wherein the copper (I) compound comprises Cu2O、Cu2S、Cu2Se or cuprous halide;
the copper (II) compound comprises CuO, CuS, CuSe and CuSO4、CuCO3、Cu(NO3)2Or a copper halide.
8. The use of the multifunctional catalyst of claim 6 wherein the copper-based compound is prepared by solvothermal, solvothermal-combined high-temperature calcination, direct reaction or acidification.
9. The use of the multifunctional catalyst of claim 1 wherein the electrolyte comprises LiTFSI/TEGDME, LiCF3SO3/TEGDME、LiTFSI/DMSO、LiClO4/DMSO、LiTFSI/DME、LiPF6/EC:DMC[1:1(v/v)]Wherein the concentration of the lithium salt is 0.1-10M.
10. The use of the multifunctional catalyst for copper-based compounds according to claim 1 in a lithium air battery, wherein the separator is a double-layer separator comprising a polyolefin porous membrane and a glass fiber membrane.
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