CN106654465B - Promote the electrolyte and lithium-air battery of carbonate decomposition - Google Patents
Promote the electrolyte and lithium-air battery of carbonate decomposition Download PDFInfo
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- CN106654465B CN106654465B CN201510713942.9A CN201510713942A CN106654465B CN 106654465 B CN106654465 B CN 106654465B CN 201510713942 A CN201510713942 A CN 201510713942A CN 106654465 B CN106654465 B CN 106654465B
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- China
- Prior art keywords
- lithium
- catalyst
- electrolyte
- air battery
- phthalocyanine
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 74
- 238000000354 decomposition reaction Methods 0.000 title claims abstract description 30
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 title claims abstract description 23
- 239000003054 catalyst Substances 0.000 claims abstract description 87
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 25
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 23
- 239000003960 organic solvent Substances 0.000 claims abstract description 20
- 150000001875 compounds Chemical class 0.000 claims abstract description 19
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 19
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 19
- -1 phthalocyanine transition metal Chemical class 0.000 claims abstract description 19
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 17
- 230000001737 promoting effect Effects 0.000 claims abstract description 4
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 claims description 42
- 229910052744 lithium Inorganic materials 0.000 claims description 38
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 30
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 24
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical group 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 claims description 17
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 15
- 229910052759 nickel Inorganic materials 0.000 claims description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 239000011701 zinc Substances 0.000 claims description 6
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 5
- 229910052748 manganese Inorganic materials 0.000 claims description 5
- 239000011572 manganese Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 239000008246 gaseous mixture Substances 0.000 claims description 4
- 239000002608 ionic liquid Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 claims description 4
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical group O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 3
- 229910006069 SO3H Inorganic materials 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 3
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 3
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 3
- WDGKXRCNMKPDSD-UHFFFAOYSA-N lithium;trifluoromethanesulfonic acid Chemical compound [Li].OS(=O)(=O)C(F)(F)F WDGKXRCNMKPDSD-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 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 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- OLBVUFHMDRJKTK-UHFFFAOYSA-N [N].[O] Chemical compound [N].[O] OLBVUFHMDRJKTK-UHFFFAOYSA-N 0.000 claims description 2
- MIQWEMDDUPSLRW-UHFFFAOYSA-N [O].O=C=O Chemical compound [O].O=C=O MIQWEMDDUPSLRW-UHFFFAOYSA-N 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 238000005868 electrolysis reaction Methods 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 238000009825 accumulation Methods 0.000 abstract description 3
- 239000007787 solid Substances 0.000 abstract description 2
- 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 description 24
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 17
- 238000000034 method Methods 0.000 description 16
- 239000000306 component Substances 0.000 description 14
- 229910002092 carbon dioxide Inorganic materials 0.000 description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 12
- 229910001416 lithium ion Inorganic materials 0.000 description 12
- 229910052760 oxygen Inorganic materials 0.000 description 12
- 239000001301 oxygen Substances 0.000 description 12
- 239000002002 slurry Substances 0.000 description 12
- 238000005273 aeration Methods 0.000 description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 9
- WFLRGOXPLOZUMC-UHFFFAOYSA-N [Li].O=C=O Chemical compound [Li].O=C=O WFLRGOXPLOZUMC-UHFFFAOYSA-N 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 9
- 239000001569 carbon dioxide Substances 0.000 description 9
- XMNPAWRFUJJEOS-UHFFFAOYSA-N carbonic acid;lithium Chemical compound [Li].[Li].OC(O)=O XMNPAWRFUJJEOS-UHFFFAOYSA-N 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 8
- 239000006260 foam Substances 0.000 description 8
- 229910001220 stainless steel Inorganic materials 0.000 description 8
- 239000010935 stainless steel Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 238000007599 discharging Methods 0.000 description 7
- 239000007772 electrode material Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 238000005259 measurement Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 238000005553 drilling Methods 0.000 description 4
- 239000011152 fibreglass Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000013019 agitation Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000004088 simulation Methods 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 229940026085 carbon dioxide / oxygen Drugs 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 229940113088 dimethylacetamide Drugs 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- HPGPEWYJWRWDTP-UHFFFAOYSA-N lithium peroxide Chemical compound [Li+].[Li+].[O-][O-] HPGPEWYJWRWDTP-UHFFFAOYSA-N 0.000 description 2
- 239000006210 lotion Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 229910001428 transition metal ion Inorganic materials 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 241000218691 Cupressaceae Species 0.000 description 1
- 208000032953 Device battery issue Diseases 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910000552 LiCF3SO3 Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000006183 anode active material Substances 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- JYYOBHFYCIDXHH-UHFFFAOYSA-N carbonic acid;hydrate Chemical compound O.OC(O)=O JYYOBHFYCIDXHH-UHFFFAOYSA-N 0.000 description 1
- PNEFIWYZWIQKEK-UHFFFAOYSA-N carbonic acid;lithium Chemical compound [Li].OC(O)=O PNEFIWYZWIQKEK-UHFFFAOYSA-N 0.000 description 1
- MMCOUVMKNAHQOY-UHFFFAOYSA-N carbonoperoxoic acid Chemical compound OOC(O)=O MMCOUVMKNAHQOY-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000002372 labelling Methods 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- NYAVNTYRFWSLQL-UHFFFAOYSA-N lithium oxygen(2-) titanium(4+) Chemical compound [Li+].[O--].[O--].[Ti+4] NYAVNTYRFWSLQL-UHFFFAOYSA-N 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 229920003240 metallophthalocyanine polymer Polymers 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
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
- H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
-
- 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 present invention provides the electrolyte and lithium-air battery that promote carbonate decomposition.Specifically, the invention discloses a kind of for promoting the electrolyte of carbonate decomposition, which includes lithium salts, organic solvent and catalyst, and wherein catalyst is double-core or multi-nuclear phthalocyanine transition metal complex compound.The invention also discloses corresponding lithium-air batteries.Lithium-air battery of the present invention uses the carbonate decomposition catalyst system of solution phase, the case where overcoming poor electric contact between carbonate and solid electrode, to can effectively reduce the decomposition electric potential of carbonate, the lithium carbonate accumulation in air electrode can be effectively reduced, and then improve the cycle performance of battery.
Description
Technical field
The present invention relates to lithium-air battery fields, more particularly, to the electrolyte and lithium air for promoting carbonate decomposition
Battery.
Background technique
Lithium-air battery is the highest energy storage device of theoretical energy density, is the developing direction of electrochmical power source.Due to anode
Active material has highest specific capacity (3.81Ahg without being stored in inside battery, negative electrode active material lithium metal-1) and only
The slightly above current potential of calcium metal system.Therefore the theoretical energy density of lithium-air battery is much higher than current lithium ion battery, reaches
11680Wh·g-1, close with gasoline, it is considered to be ultimate secondary cell.
The composition of lithium-air battery includes: to be positive using lithium metal as cathode with the porous electrode that the materials such as active carbon are constituted
Pole is connected with electrolyte or solid electrolyte between positive and negative anodes.
The working principle of lithium-air battery are as follows: during discharge, positive oxygen obtains electronics, also by electrochemistry
Original generates lithium peroxide in conjunction with lithium ion, and the lithium metal of cathode loses electronics and is oxidized to lithium ion and migrates to anode；It fills
In electric process, positive lithium peroxide loses electronics oxygenolysis, generates oxygen and lithium ion, and the lithium ion of cathode then obtains
Electron reduction is lithium metal.
Contain about 0.3 ‰ carbon dioxide in the air of nature, and carbon dioxide often uses electrolyte in lithium-air battery
Solubility in solvent is much higher than oxygen, therefore in lithium-air battery actual motion, carbon dioxide can be with discharging product (peroxide
Change lithium or lithia) reacting generates lithium carbonate, or directly generates lithium carbonate with Li+, oxygen and electron reaction.In addition, electric
Side reaction decomposition can occur in battery operation for solution liquid and positive electrode (generally active carbon), can equally generate lithium carbonate.
Carbonate is non-conductive at normal temperature, often uses electrolyte insoluble in lithium-air battery.It is commonly filled in lithium-air battery
Under electric potential, main decomposition reactional equation are as follows:
2M2CO3→4M++2CO2+O2+4e- E0=3.82V M=Li, Na, K
Since the overpotential of this oxidative decomposition is big (> 0.675V), in lithium-air battery and lithium-titanium dioxide
Electrode material surface can be covered in carbon/aeration cell operational process, hindered active material transmission, increased battery polarization.It is many
Research shows that the main reason for accumulation of lithium carbonate is lithium-air battery failure.
In order to reduce the activation energy and overpotential of lithium carbonate decomposition, need using suitable catalyst, but current lithium carbonate
The research of decomposition catalyst extremely lacks, and the lithium carbonate decomposition catalyst for having been found catalytic effect at present has: gold, platinum, oxidation
Nickel.These catalyst are solid-state.Also it is solid-state since it is catalyzed object lithium carbonate, good portion is being contacted with catalyst
After dividing lithium carbonate to decompose, catalyst can not play catalytic action to undesirable lithium carbonate decomposition is in contact with it.
In conclusion still lacking the lithium-air battery for efficiently lithium carbonate being promoted to decompose and method in the prior art.
Summary of the invention
The purpose of the present invention is to provide a kind of lithium-air battery for efficiently lithium carbonate being promoted to decompose and methods.
It is a further object of the present invention to provide a kind of carbon for the efficient lithium-air battery for promoting lithium carbonate to decompose
Sour lithium decomposition catalyst, and the electrolyte containing the decomposition catalyst.
In the first aspect of the present invention, a kind of electrolyte that can be used for lithium-air battery is provided, the electrolyte contains
There are lithium salts, organic solvent and catalyst,
Wherein the catalyst is double-core or multi-nuclear phthalocyanine transition metal complex compound.
In another preferred example, the catalyst has two or more phthalocyanine rings, and with phenyl ring between phthalocyanine ring
It is connected.
In another preferred example, 2~8 contained by the catalyst, preferably 2-6 phthalocyanine ring.
In another preferred example, the phthalocyanine transition metal complex compound has following formula I structure:
In formula,
Each M can be identical or different, and independently selected from: Fe, Co, NI, Mn, Zn, Cu；
Each R can be identical or different, and independently selected from: nothing, H ,-SO3H、-SO3Z ,-COOH ,-COOZ, C1-C6 alkane
Base ,-O-C1-C6 alkyl ,-CONH2；
Z is alkali metal (such as Na, K, Li)；
N is the integer (i.e. 0,1,2,3,4,5 or 6) of 0-6, preferably 0-4 integer (i.e. 0,1,2,3 or 4).
In another preferred example, in the catalyst molecule contain metal selected from the group below ion: iron, cobalt, nickel, copper,
Zinc, manganese, or combinations thereof.
In another preferred example, the valence state of the ion of the metal is divalent, trivalent or tetravalence.
In another preferred example, the content of the catalyst is 0.00001-1mol/L electrolyte.
In another preferred example, the catalyst is soluble catalyst.
In another preferred example, the organic solvent is aprotic solvent.
In another preferred example, solvability of the catalyst in aprotic organic solvent is greater than 0.0001mol/
L is more preferably 0.0001-1mol/L, is more preferably 0.001-0.1mol/L.
In another preferred example, the organic solvent is selected from the group: diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, four
Glycol dimethyl ether, dimethyl sulfoxide, ionic liquid or combinations thereof.
In another preferred example, the lithium salts is selected from the group: lithium perchlorate, bis-trifluoromethylsulfoandimide lithium, hexafluoro phosphorus
Sour lithium, lithium nitrate, trifluoromethanesulfonic acid lithium, or combinations thereof.
In another preferred example, the content of the lithium salts is 0.001-5mol/L, preferably 0.01-2mol/L, more preferably
Ground 0.1-1mol/L electrolyte.
In the second aspect of the present invention, a kind of electrolyte (or electrolyte) product that can be used for lithium-air battery is provided,
Described electrolyte (or electrolyte) product includes that the first component lithium salts, the second component catalyst and optional third component have
Solvent,
Wherein the first component lithium salts, the second component catalyst and third component organic solvent respectively can independently place or
The mixing of any two component is placed or three component mixing are placed.
In another preferred example, the first component lithium salts, the second component catalyst and third component organic solvent are respectively only
It stands up and sets.
In another preferred example, the catalyst is dissolved in solvent selected from the group below: ethyl alcohol, ether, diethylene glycol
Dimethyl ether, tetraethyleneglycol dimethyl ether, dimethyl acetamide, dimethyl sulfoxide, or combinations thereof.
In the third aspect of the present invention, a kind of lithium-air battery is provided, which is characterized in that including air cathode, metal
Electrolyte described in cathode of lithium and first aspect present invention.
In another preferred example, the work atmosphere of the battery is pure oxygen, oxygen-nitrogen gaseous mixture (volume ratio 1:99-
99:1), normal air or carbon dioxide-oxygen mixture (volume ratio 0.1:99.9-67:33).
In another preferred example, the lithium-air battery also includes diaphragm, shell and battery auxiliary system.
In the fourth aspect of the present invention, the purposes of a kind of double-core or multi-nuclear phthalocyanine transition metal complex compound is provided,
It is used to prepare the catalyst or electrolyte of carbonate decomposition in catalysis lithium-air battery；Or it is used to prepare lithium-air battery.
In another preferred example, the lithium-air battery is high-energy density lithium-air cell device.
It should be understood that within the scope of the present invention, above-mentioned each technical characteristic of the invention and in below (eg embodiment) specifically
It can be combined with each other between each technical characteristic of description, to form a new or preferred technical solution.As space is limited, herein
No longer tire out one by one and states.
Detailed description of the invention
Fig. 1 is to show the structure of representative double-core (or multicore) metal phthalocyanine complex of the present invention.
Fig. 2 is to charge to positive difference using lithium-carbonic acid lithium battery of representative electrolyte in an example of the invention
Positive X ray diffracting spectrum after current potential.Electrolyte concrete component are as follows: lithium salts is 1mol/L bis-trifluoromethylsulfoandimide lithium, is urged
Agent is 0.005mol/L binuclear phthalocyanine cobalt, and organic solvent is tetraethyleneglycol dimethyl ether.Comparison map is to be added without in electrolyte
The battery of catalyst charges to the positive X ray diffracting spectrum after positive different potentials.
Fig. 3 (a) is lithium-carbon dioxide/aeration cell using representative electrolyte in an example of the invention
1000mAh/gcarbonConstant volume charging and discharging curve.Electrolyte concrete component are as follows: lithium salts is 1mol/L bis-trifluoromethylsulfoandimide lithium,
Catalyst is 0.005mol/L binuclear phthalocyanine cobalt, and organic solvent is tetraethyleneglycol dimethyl ether, current density 100mA/gcarbon,
Measurement atmosphere is 1atm CO2-O2(volume ratio 2:1).Fig. 3 (b) is lithium-carbon dioxide/oxygen that catalyst is added without in electrolyte
The charging and discharging curve in pneumoelectric pond.
Fig. 4 is the 500mAh/g using the lithium-air battery of representative electrolyte in an example of the inventioncarbonIt is fixed
Hold the final voltage change curve of charge and discharge cycles.Electrolyte concrete component are as follows: lithium salts is 1mol/L bis-trifluoromethylsulfoandimide
Lithium, catalyst are 0.005mol/L binuclear phthalocyanine cobalt, and organic solvent is tetraethyleneglycol dimethyl ether, current density 100mA/
gcarbon, measurement atmosphere is 1atm N2-O2(volume ratio 78:22).Correlation curve is to be added without catalyst, Yi Ji electricity in electrolyte
Solve the 500mAh/g that the lithium-air battery of 0.005mol/L monokaryon Cobalt Phthalocyanine is added in liquidcarbonThe termination of constant volume charge and discharge cycles
Voltage change curve.
Specific embodiment
The present inventor after extensive and in-depth study, develop for the first time it is novel for lithium-air battery, efficiently promote
Into the electrolyte of carbonate decomposition, which includes lithium salts, organic solvent and soluble catalyst, wherein soluble catalyst
Including double-core or multi-nuclear phthalocyanine transition metal complex compound (such as binuclear phthalocyanine cobalt or six core FePCs etc.).Experiment shows
Had using corresponding lithium-air battery prepared by novel electrolyte of the present invention by the carbonate decomposition catalyst system of solution phase
The case where effect overcomes poor electric contact between carbonate and solid electrode, to significantly reduce the decomposition electric potential of carbonate, therefore
The lithium carbonate accumulation in air electrode can be reduced, effectively so as to improve the cycle performance of battery.It completes on this basis
The present invention.
Double-core or multi-nuclear phthalocyanine transition metal complex compound (catalyst)
In the present invention, catalyst is core component.By largely screening and testing, present inventors have surprisingly found that, with
Other substances are compared, and double-core or multi-nuclear phthalocyanine transition metal complex compound are particularly suitable as being catalyzed carbonic acid in lithium-air battery
The catalyst that salt decomposes.
On the one hand, double-core or multi-nuclear phthalocyanine transition metal complex compound are dissolvable in water or are scattered in suitable organic solvent
In, form the carbonate decomposition catalyst system of solution phase；On the other hand, double-core or multi-nuclear phthalocyanine transition metal complex compound exist
Efficient catalytic activity can be still kept in multiple charge and discharge process, therefore is particularly suitable for lithium-air battery, and its performance is obvious
Better than conventional catalysts such as gold, platinum, nickel oxide.
In the present invention, typical soluble catalyst may be selected to be double-core or multi-nuclear phthalocyanine transition-metal coordination chemical combination
Object.
Typical catalyst of the invention has the feature that with two or more phthalocyanine ring structures, and phthalocyanine ring knot
It is connected between structure with phenyl ring.Phthalocyanine ring center is identical or different metal ion, through coordinate bond in conjunction with phthalocyanine ring.Phthalein
The phenyl ring unsubstituted of cyanines ring side, or contain other one or more substituent groups (such as sulfo group, carboxyl substituent group).With phthalocyanine
Ring combines or the metal ion of coordination includes (but being not limited to): Co, Fe, Mn, Ni, Zn, Cu or combinations thereof.
A kind of typical phthalocyanine transition metal complex compound has following formula I structure:
In formula,
Each M can be identical or different, and independently selected from: Fe, Co, NI, Mn, Zn, Cu；
Each R can be identical or different, and independently selected from: nothing, H ,-SO3H、-SO3Z ,-COOH ,-COOZ, C1-C6 alkane
Base ,-O-C1-C6 alkyl ,-CONH2；
Z is alkali metal (such as Na, K, Li)；
N is the integer (i.e. 0,1,2,3,4,5 or 6) of 0-6, preferably 0-4 integer (i.e. 0,1,2,3 or 4).
In another preferred example, the quantity of R is 1-2, preferably 1 on each phenyl ring.
In a preferred embodiment, it is described with multiple redox centers dissolvable redox mediator (or
Catalyst) it is binuclear metallo phthalocyanine or six core metal phthalocyanines.
In a preferred embodiment, there are two phthalocyanine rings for the catalyst tool.
In another preferred example, the example of particularly preferred compound of formula I includes (but being not limited to): binuclear phthalocyanine cobalt,
Six core FePCs, binuclear phthalocyanine cobalt manganese (II) etc..The structure of part representative compound is as shown in Figure 1.
Promote the electrolyte of carbonate decomposition
The present invention provides a kind of electrolyte (or being " electrolyte of the present invention ") that can effectively facilitate carbonate decomposition, described
Electrolyte in contain soluble, efficient catalytic carbonate decomposition catalyst, lithium salts and organic solvent.
It should be understood that can contain a kind of compound of formula I in electrolyte of the invention, two or more Formulas I can also be contained
Compound.For example, can the mixture containing binuclear phthalocyanine cobalt and six core FePCs.
In the present invention, workable electrolyte solvent is not particularly limited, and can be any suitable for lithium-air battery
Solvent, including organic solvent, especially non-proton organic solvent.In the present invention, representative examples of solvents include (but
It is not limited to): polyether solvent (such as diethylene glycol dimethyl ether, triethylene glycol dimethyl ether or tetraethyleneglycol dimethyl ether), ionic liquid
Body, dimethyl acetamide or dimethyl sulfoxide (DMSO), or combinations thereof.
In the present invention, workable lithium salts is not particularly limited, and can be any lithium salts suitable for lithium-air battery.
In the present invention, representative examples of lithium salts includes (but being not limited to): lithium perchlorate (LiClO4), bis-trifluoromethylsulfoandimide
Lithium (LiTFSI), lithium hexafluoro phosphate (LiPF6), lithium nitrate (LiNO3) or trifluoromethanesulfonic acid lithium (LiCF3SO3)。
Lithium-air battery and application
The present invention in addition to provide a kind of carbonate decomposition catalyst for being dissolvable in water electrolyte for lithium-air battery and
Electrolyte additionally provides corresponding lithium-air battery.
In the present invention, lithium-air battery further includes other than including lithium-aeration cell containing electrolyte of the present invention
Lithium-carbon dioxide/aeration cell containing electrolyte of the present invention.Lithium-carbon dioxide/aeration cell of the invention is a kind of available
In the testing tool of the catalytic capability of assessment lithium carbonate decomposition catalyst.
Lithium-carbon dioxide/aeration cell is one kind using lithium as cathode, is that anode is living with the gaseous mixture of carbon dioxide and oxygen
Property substance battery, can be considered and artificially improve the lithium-air battery of gas concentration lwevel.
Lithium-carbon dioxide/aeration cell working principle are as follows: during discharge, positive oxygen obtains electronics, passes through
Electrochemical reduction generates superoxide radical, then generates peroxycarbonic acid root, mistake with the carbon dioxide reaction being dissolved into electrolyte
Oxygen carbonate continues to generate lithium carbonate and oxygen with superoxide radical reaction and in conjunction with lithium ion, and the lithium metal of cathode loses
De-electromation is oxidized to lithium ion and migrates to anode；In charging process, positive lithium carbonate loses electronics oxygenolysis, generates oxygen
Gas, carbon dioxide and lithium ion, and it is lithium metal that the lithium ion of cathode, which then obtains electron reduction,.
As used herein, carbon dioxide enriched degree is improved in lithium-carbon dioxide/aeration cell, therefore can be used for
Assess the catalytic capability of lithium carbonate decomposition catalyst.
Test method
In the present invention, the property of conventional method test catalyst of the present invention, electrolyte or lithium-air battery can be used
Can, especially it is catalyzed the performance of carbonate decomposition.
In testing, measurement atmosphere is preferably one of following gas: N2:O2The simulation of=78:22 (v/v) is dry empty
Gas or CO2:O2Carbon dioxide/oxygen mixture of=2:1 (v/v).
Main advantages of the present invention include:
(a) lithium carbonate that the present invention provides a kind of solution phase for the first time decomposes catalyst system, in the system, catalyst pair
Good catalytic action is played in lithium carbonate decomposition.
(b) unique catalyst of the invention, which uses, has two or more redox centers (transition metal ions),
And pass through the joining dissolvable redox mediator of conjugatedπbond between these redox centers as catalyst.It is this to urge
Agent can be dissolved in electrolyte, the free diffusing between carbonate and electrode material, therefore, in battery charging process, i.e.,
Make there are a large amount of carbonate to accumulate, catalyst, which remains on, can remain well contacting between electrode material.
(c) in unique catalyst of the invention, with conjugatedπbond phase between redox center (transition metal ions)
Connection, therefore, on same current potential, compared to the monokaryon dissolvable redox mediator of single redox center, this double-core
Or multicore redox mediators can provide more redox charge numbers, therefore have to polyelectron redox reaction higher
Catalytic capability, thus can effectively clear lithium air battery positive electrode generation lithium carbonate, improve cycle performance of battery.
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In the following examples, the experimental methods for specific conditions are not specified, usually according to conventional strip
Part, or according to the normal condition proposed by manufacturer.Unless otherwise stated, otherwise percentage and number are mass percent and quality
Number.
Abbreviation:
BiCoPc: binuclear phthalocyanine cobalt (II), structural formula are the I-d in Fig. 1.
In the examples below that, all material is marketable material, such as binuclear phthalocyanine cobalt (biCoPc) double-core or multicore
Phthalocyanine transition metal complex compound is purchased from Shanghai Di Bai chemicals Technology Co., Ltd..
Embodiment 1
Electrolyte No.1 and lithium-air battery No.1
The method of dispersed catalyst is as follows: 0.005mol/L binuclear phthalocyanine cobalt (biCoPc) and 1mol/L LiTFSI is molten
Solution is configured to electrolyte in tetraethyleneglycol dimethyl ether (TEGDME).As a comparison, by 0.005mol/L monokaryon Cobalt Phthalocyanine (CoPc)
It is dissolved in tetraethyleneglycol dimethyl ether (TEGDME) with 1mol/L LiTFSI, is configured to electrolyte.Meanwhile it preparing and being free of catalyst
1mol/L LiTFSI/TEGDME electrolyte.
It is as follows to prepare lithium-carbonic acid lithium battery method: 0.15g is passed through to the Li of ball milling2CO3With 0.15g Ketjen
5mL N-Methyl pyrrolidone (NMP) is added in the highly conductive carbon black of Black EC600JD (KB), is added 0.026g polyimides (PI)
Obtaining electrode material slurry as binder, after magnetic agitation 2h will then be coated with by slurry even application to foam nickel surface
The nickel foam of slurry moves into baking oven, moves into vacuum drying oven after drying at 80 DEG C, is dried in vacuo 12h at 120 DEG C, uses slicer
The disk of diameter 14mm is cut to as lithium air battery positive electrode pole piece, control KB load capacity is 1 ± 0.2mg/cm2.By positive pole
Piece is taped against on the CR2032 battery stainless steel anode cover of drilling (as oxygen channel) in advance, is placed on anode pole piece
Whatman GF/D fibreglass diaphragm is added dropwise 140 μ L with or without the electrolyte of catalyst, it is made sufficiently to infiltrate diaphragm,
In the metal lithium sheet that diaphragm places 0.2mm thickness as cathode, stainless steel negative electrode casing is placed above metal lithium sheet, finally
Battery is pressed using tablet press machine, button lithium-carbonic acid lithium battery is made.
The charging curve of resulting button lithium-carbonic acid lithium battery is tested using new prestige battery test system, charging current is close
Degree is 0.15mA, charge cutoff to different potentials (as shown in Figure 2), measurement atmosphere N2:O2The simulation of=78:22 (v/v) is dry
Dry air.
X-ray diffraction test is carried out to the battery pole piece after charging complete, the battery of catalyst is not used to charge to
4.55V(vs.Li+/ Li), anode pole piece still has visible Li2CO3Residual, and charged to using the battery of biCoPc catalyst
4.35V Li2CO3It decomposes completely, shows that Li can be effectively reduced in biCoPc catalyst2CO3The current potential of decomposition.
Embodiment 2
Electrolyte No.2 and lithium-air battery No.2
The method of dispersed catalyst is as follows: 0.005mol/L binuclear phthalocyanine cobalt (biCoPc) and 1mol/L LiTFSI is molten
Solution is configured to electrolyte in tetraethyleneglycol dimethyl ether (TEGDME).As a comparison, by 0.005mol/L monokaryon Cobalt Phthalocyanine (CoPc)
It is dissolved in tetraethyleneglycol dimethyl ether (TEGDME) with 1mol/L LiTFSI, is configured to electrolyte.Meanwhile it preparing and being free of catalyst
1mol/L LiTFSI/TEGDME electrolyte.
It is as follows to prepare lithium-carbonic acid lithium battery method: by the Li of 1.30~1.50mg isotope labelling2 13CO3With Ketjen
1mL N-Methyl pyrrolidone (NMP) is added in the highly conductive carbon black of Black EC600JD (KB) 1:1 in mass ratio, and 5mg polyamides is added
Imines (PI) is used as binder, and electrode material slurry is obtained after ultrasonic disperse 2h, by slurry even application to foam nickel surface, with
The nickel foam for being coated with slurry is moved into baking oven afterwards, vacuum drying oven is moved into after drying at 80 DEG C, is dried in vacuo 12h at 120 DEG C,
Slicer is used to be cut to the disk of diameter 14mm as lithium air battery positive electrode pole piece, control KB load capacity is 0.5 ± 0.2mg/
cm2.Anode pole piece is taped against on the CR2032 battery stainless steel anode cover of drilling (as oxygen channel) in advance, in anode pole piece
Upper placement Whatman GF/D fibreglass diaphragm is added dropwise 140 μ L with or without the electrolyte of catalyst, infiltrates it sufficiently
Diaphragm places stainless steel cathode in the metal lithium sheet that diaphragm places 0.2mm thickness as cathode above metal lithium sheet
Shell finally presses battery using tablet press machine, and button lithium-carbonic acid lithium battery is made.
Constant current charge, current density are carried out to resulting lithium-carbonic acid lithium battery using difference electrochemistry mass spectrograph in situ
25mA/gcarbon, charge cutoff current potential 4.55V (vs.Li+/ Li), it is collected simultaneously gaseous products and is analyzed by mass spectrometry.
The result shows that lithium-carbonic acid lithium battery initiation of charge the current potential for being added to biCoPc is down to 4.15V, Li2 13CO3It decomposes
It generates13CO2With the Li of addition2 13CO3Molar ratio is increased to 58.13%.Than the molar ratio of the lithium-air battery in comparative example 1
It is higher by 6 times.
Comparative example 1
Electrolyte No.C1 and lithium-air battery No.C1
Binuclear phthalocyanine cobalt (biCoPc) in embodiment 2 is replaced with into monokaryon Cobalt Phthalocyanine (CoPc), other conditions are constant.
Lithium-carbonic acid the lithium battery for being added to CoPc compares the lithium-carbonic acid lithium battery for being not added with catalyst, initiation of charge current potential
4.07V, Li are down to by 4.25V2 13CO3Decompose generation13CO2With the Li of addition2 13CO3Molar ratio is increased to by 0.94%
9.89%.
Embodiment 3
Electrolyte No.3 and lithium-air battery No.3
The method of dispersed catalyst is as follows: by 0.005mol/L biCoPc and 1mol/L LiClO4It is dissolved in DMSO, is matched
Electrolyte is made.Meanwhile preparing the 1mol/L LiClO for being free of catalyst4/ DMSO electrolyte.
It is as follows to prepare lithium-carbon dioxide/aeration cell method: taking KB 0.15g, 0.45mL 6wt% polytetrafluoro is added
Ethylene (PTFE) lotion as dispersing agent, obtains electrode material slurry after magnetic agitation 2h as binder and 5mL deionized water
The nickel foam for being coated with slurry is then moved into baking oven, dries and move back at 80 DEG C by material by slurry even application to foam nickel surface
Enter vacuum drying oven, be dried in vacuo 12h at 120 DEG C, slicer is used to be cut to the disk of diameter 14mm as lithium air battery positive electrode
Pole piece, control KB load capacity are 1 ± 0.2mg/cm2.Anode pole piece is taped against to the CR2032 of drilling (as oxygen channel) in advance
On battery stainless steel anode cover, Whatman GF/D fibreglass diaphragm is placed on anode pole piece, and 140 μ L are added dropwise and contain or not
Electrolyte containing catalyst makes it sufficiently infiltrate diaphragm, places the metal lithium sheet of 0.2mm thickness as cathode in diaphragm,
Stainless steel negative electrode casing is placed above metal lithium sheet, finally presses battery using tablet press machine, and button lithium-carbon dioxide/oxygen is made
Pneumoelectric pond.
Resulting button lithium-carbon dioxide/aeration cell charging and discharging curve is tested using new prestige battery test system, is filled
Discharge current density is 0.15mA, measurement atmosphere CO2:O2The gaseous mixture of=2:1 (v/v).
Compared to the battery for not using catalyst, 0.3V is improved using the cell discharge voltage of biCoPc catalyst, and is filled
Piezoelectric voltage reduces 0.5V, as shown in Figure 3.
Embodiment 4
Electrolyte No.4 and lithium-air battery No.4
BiCoPc in embodiment 3 is replaced with into six core sulfonated phthalocyanine iron (purchased from the limited public affairs of Shanghai flute cypress chemicals technology
Department), other conditions are constant.Compared to the battery for not using catalyst, improved using the cell discharge voltage of biCoPc catalyst
0.2V, and charging voltage reduces 0.4V, cycle life was improved by 4 weeks to 21 weeks.
Embodiment 5
Electrolyte No.5 and lithium-air battery No.5
The method of dispersed catalyst is as follows: 0.005mol/L binuclear phthalocyanine cobalt (biCoPc) and 1mol/L LiTFSI is molten
Solution is configured to electrolyte in tetraethyleneglycol dimethyl ether (TEGDME).As a comparison, by 0.005mol/L monokaryon Cobalt Phthalocyanine (CoPc)
It is dissolved in tetraethyleneglycol dimethyl ether (TEGDME) with 1mol/L LiTFSI, is configured to electrolyte.Meanwhile it preparing and being free of catalyst
1mol/L LiTFSI/TEGDME electrolyte.
The method for preparing lithium-air battery is as follows: taking KB 0.15g, is added 0.45mL 6wt% polytetrafluoroethylene (PTFE) (PTFE)
Lotion as dispersing agent, obtains electrode material slurry after magnetic agitation 2h, by slurry as binder and 5mL deionized water
The nickel foam for being coated with slurry is then moved into baking oven to foam nickel surface by even application, is moved into vacuum after drying at 80 DEG C and is dried
Case is dried in vacuo 12h at 120 DEG C, and the disk for using slicer to be cut to diameter 14mm is controlled as lithium air battery positive electrode pole piece
KB load capacity is 1 ± 0.2mg/cm2.Anode pole piece is taped against to the CR2032 battery stainless steel of drilling (as oxygen channel) in advance
On anode cover, Whatman GF/D fibreglass diaphragm is placed on anode pole piece, and the electrolysis that 140 μ L contain biCoPc is added dropwise
Liquid makes it sufficiently infiltrate diaphragm, diaphragm place 0.2mm thickness metal lithium sheet as cathode, above metal lithium sheet
Stainless steel negative electrode casing is placed, finally presses battery using tablet press machine, button lithium-air battery is made.
The charging and discharging curve of resulting button lithium-air battery is tested using new prestige battery test system, charging and discharging currents are close
Degree is 0.15mA, measurement atmosphere N2:O2The simulation dry air of=78:22 (v/v).Battery charging and discharging containing biCoPc
Cycle life is 47 weeks, compared to 21 weeks and significantly improving for 30 weeks containing CoPc catalyst for being free of catalyst, as shown in Figure 4.
All references mentioned in the present invention is incorporated herein by reference, independent just as each document
It is incorporated as with reference to such.In addition, it should also be understood that, after reading the above teachings of the present invention, those skilled in the art can
To make various changes or modifications to the present invention, such equivalent forms equally fall within model defined by the application the appended claims
It encloses.
Claims (13)
1. a kind of electrolyte for promoting lithium carbonate to decompose that can be used for lithium-air battery, which is characterized in that the electrolyte contains
There are lithium salts, organic solvent and catalyst,
Wherein the catalyst is multi-nuclear phthalocyanine transition metal complex compound；
The catalyst has multiple phthalocyanine rings, and is connected between phthalocyanine ring with phenyl ring；
The organic solvent is selected from the group: diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethyleneglycol dimethyl ether, dimethyl
Sulfoxide, ionic liquid or combinations thereof.
2. electrolyte as described in claim 1, which is characterized in that the catalyst contains 2~8 phthalocyanine rings.
3. electrolyte as described in claim 1, which is characterized in that the catalyst contains 2~6 phthalocyanine rings.
4. electrolyte as described in claim 1, which is characterized in that the catalyst is phthalocyanine transition-metal coordination chemical combination
Object, with following formula I structure:
In formula,
Each M can be identical or different, and independently selected from: Fe, Co, Ni, Mn, Zn, Cu；
Each R can be identical or different, and independently selected from: H ,-SO3H、-SO3Z ,-COOH ,-COOZ, C1-C6 alkyl ,-O-
C1-C6 alkyl ,-CONH2；
Z is alkali metal；
N is the integer of 0-6.
5. electrolyte as claimed in claim 4, which is characterized in that containing metal selected from the group below in the catalyst molecule
Ion: iron, cobalt, nickel, copper, zinc, manganese, or combinations thereof；Wherein, the ionic valence condition of the metal is divalent, trivalent or tetravalence.
6. electrolyte as claimed in claim 4, which is characterized in that the content of the catalyst is 0.00001-1mol/L.
7. electrolyte as described in claim 1, which is characterized in that the lithium salts is selected from the group: lithium perchlorate, double fluoroforms
Sulfimide lithium, lithium hexafluoro phosphate, lithium nitrate, trifluoromethanesulfonic acid lithium, or combinations thereof.
8. a kind of electrolyte product that can be used for lithium-air battery, which is characterized in that the electrolyte product includes first group
Divide lithium salts, the second component catalyst and third component organic solvent,
Wherein the first component lithium salts, the second component catalyst and third component organic solvent respectively independently place or any two
Component mixing is placed；
Second component catalyst is multi-nuclear phthalocyanine transition metal complex compound, and the catalyst has multiple phthalocyanines
Ring, and be connected between phthalocyanine ring with phenyl ring；
The third component organic solvent is selected from the group: diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol diformazan
Ether, dimethyl sulfoxide, ionic liquid or combinations thereof.
9. a kind of lithium-air battery, which is characterized in that including air cathode, lithium anode and electrolysis described in claim 1
Liquid.
10. lithium-air battery as claimed in claim 9, which is characterized in that the work atmosphere of the lithium-air battery is pure
Oxygen, oxygen-nitrogen gaseous mixture, normal air or carbon dioxide-oxygen mixture.
11. lithium-air battery as claimed in claim 9, which is characterized in that the lithium-air battery also includes diaphragm, shell
And battery auxiliary system.
12. a kind of purposes of multi-nuclear phthalocyanine transition metal complex compound, which is characterized in that be used to prepare catalysis lithium-air battery
The catalyst or electrolyte of middle carbonate decomposition；
Wherein, the multi-nuclear phthalocyanine transition metal complex compound has multiple phthalocyanine rings, and with phenyl ring phase between phthalocyanine ring
Connection.
13. purposes as claimed in claim 12, which is characterized in that the lithium-air battery is high-energy density lithium-air
Battery device.
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| CN109378491A (en) * | 2018-09-27 | 2019-02-22 | 山东大学 | A kind of lithium-air battery and preparation method thereof |
| CN109411817B (en) * | 2018-10-30 | 2020-10-27 | 中南大学 | Lithium ion battery or lithium sulfur battery electrolyte |
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