CN107293826A - A kind of high energy density charge-discharge battery being made up of metal and peroxide and its application - Google Patents
A kind of high energy density charge-discharge battery being made up of metal and peroxide and its application Download PDFInfo
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- CN107293826A CN107293826A CN201611235783.7A CN201611235783A CN107293826A CN 107293826 A CN107293826 A CN 107293826A CN 201611235783 A CN201611235783 A CN 201611235783A CN 107293826 A CN107293826 A CN 107293826A
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- alkali metal
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- high energy
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 38
- 239000002184 metal Substances 0.000 title claims abstract description 38
- 150000002978 peroxides Chemical class 0.000 title claims abstract description 15
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 7
- 239000003792 electrolyte Substances 0.000 claims abstract description 30
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 27
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 25
- 150000003839 salts Chemical class 0.000 claims abstract description 20
- 239000007864 aqueous solution Substances 0.000 claims abstract description 19
- 229920000642 polymer Polymers 0.000 claims abstract description 18
- 230000004888 barrier function Effects 0.000 claims abstract description 17
- 239000007787 solid Substances 0.000 claims abstract description 14
- 239000005486 organic electrolyte Substances 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 239000000956 alloy Substances 0.000 claims abstract description 10
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 10
- 239000002608 ionic liquid Substances 0.000 claims abstract description 9
- 239000000017 hydrogel Substances 0.000 claims abstract description 7
- 229910001413 alkali metal ion Inorganic materials 0.000 claims abstract description 6
- 230000002441 reversible effect Effects 0.000 claims abstract description 6
- 229910052744 lithium Inorganic materials 0.000 claims description 18
- 239000005518 polymer electrolyte Substances 0.000 claims description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 229920001577 copolymer Polymers 0.000 claims description 6
- 239000011737 fluorine Substances 0.000 claims description 6
- 229910052731 fluorine Inorganic materials 0.000 claims description 6
- 239000000499 gel Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- -1 siloxanes Chemical class 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 5
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 4
- 239000002033 PVDF binder Substances 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 229910020343 SiS2 Inorganic materials 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 150000001336 alkenes Chemical class 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 230000005611 electricity Effects 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 150000002739 metals Chemical class 0.000 claims description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 4
- 229910052701 rubidium Inorganic materials 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 229910052792 caesium Inorganic materials 0.000 claims description 3
- 239000003575 carbonaceous material Substances 0.000 claims description 3
- 239000002019 doping agent Substances 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 125000000962 organic group Chemical group 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 2
- 229910012226 MBF4 Inorganic materials 0.000 claims description 2
- 229910018953 MClO4 Inorganic materials 0.000 claims description 2
- 229910016079 MPF6 Inorganic materials 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 2
- 238000005868 electrolysis reaction Methods 0.000 claims description 2
- 125000001153 fluoro group Chemical group F* 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- 150000004820 halides Chemical class 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 150000002460 imidazoles Chemical class 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- 229910052909 inorganic silicate Inorganic materials 0.000 claims description 2
- 229910052745 lead Inorganic materials 0.000 claims description 2
- 229910052976 metal sulfide Inorganic materials 0.000 claims description 2
- 229920000058 polyacrylate Polymers 0.000 claims description 2
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 150000003222 pyridines Chemical class 0.000 claims description 2
- 238000006467 substitution reaction Methods 0.000 claims description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims 1
- 239000005864 Sulphur Substances 0.000 claims 1
- 229910052977 alkali metal sulfide Inorganic materials 0.000 claims 1
- 239000002585 base Substances 0.000 claims 1
- 150000007942 carboxylates Chemical class 0.000 claims 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims 1
- 150000003462 sulfoxides Chemical class 0.000 claims 1
- 238000005516 engineering process Methods 0.000 abstract description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 11
- 210000004027 cell Anatomy 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 7
- 239000000446 fuel Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 239000011149 active material Substances 0.000 description 5
- 229910021389 graphene Inorganic materials 0.000 description 5
- 239000012528 membrane Substances 0.000 description 5
- 238000007789 sealing Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 4
- 239000004926 polymethyl methacrylate Substances 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 229910032387 LiCoO2 Inorganic materials 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 210000001787 dendrite Anatomy 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000006245 Carbon black Super-P Substances 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910009496 Li1.5Al0.5Ge1.5 Inorganic materials 0.000 description 1
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- 229910019398 NaPF6 Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- ZWWZGWFNRITNNP-UHFFFAOYSA-N carbonic acid;ethene Chemical compound C=C.OC(O)=O ZWWZGWFNRITNNP-UHFFFAOYSA-N 0.000 description 1
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000002659 electrodeposit Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 239000003500 flue dust Substances 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 1
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Inorganic materials [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 1
- 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 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 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
- 229910052759 nickel Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 125000001979 organolithium group Chemical group 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000001291 vacuum drying 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
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention belongs to electrochemical technology field, specially a kind of high energy density charge-discharge battery being made up of metal and peroxide and its application.The barrier film of the battery is the solid that alkali metal ion reversible can pass through, and negative pole is the alloy containing alkali metal or containing alkali metal, just the mixed aqueous solution extremely containing peroxide (ROOR ') and metal salt；The electrolyte of negative side is organic electrolyte, polymer dielectric or ionic liquid electrolyte or their mixture, and the electrolyte of side of the positive electrode is the aqueous solution or hydrogel of metalline.This kind of battery has very high energy density and good cycle performance, and cost is low, storage and release available for electric power.
Description
Technical field
The invention belongs to electrochemical technology field, and in particular to a kind of high-energy being made up of metal and peroxide is close
Charge-discharge battery and its application are spent, the application of the battery constituted the invention further relates to the metal and peroxide.
Background technology
In fossil energy increasingly exhausted, environmental pollution increasingly serious today, electric automobile can reduce greenhouse gases and have
The discharge of evil flue dust, its development and application increasingly gets more and more people's extensive concerning.In order to realize sustainable development, exploitation and
Turn into the grand strategy target of countries in the world using new energy.Wherein, electrochemical energy is because of its energy conversion efficiency and energy
Density height, noise-less pollution, the advantage that can be optionally combined and move, as one of most important research topic.Electrochmical power source exists
Development and utilization has been obtained in terms of high-tech device, green low-energy consumption transport and regenerative resource.Lithium metal is due to matter
Metric density is low, and energy density is high, the features such as electrode potential most negative (- 3.046V) and high electronic conductance, in recent decades, with it
Based on the lithium battery that develops become studied in electrochemical energy with the emphasis of application (referring to：Wu Yuping, Dai Xiaobing,
Horse army flag, the pre- river of journey《Lithium ion battery-application and practice》).At present, commercial lithium-ion batteries are in small-sized movement
It is widely used in storage facilities；But price is high, poor safety performance and the low problem of energy density, governs
Further development of the lithium ion battery on New-energy electric vehicle.
Lithium-air battery is as a kind of new lithium battery system, using lithium metal as GND (anode), in air
Oxygen be positive active material (negative electrode), with the ultra high energy density close to fossil energy, although lithium-air battery
Show good application prospect.However, the practical road of the commodity of lithium-air battery is still very long, some critical problems
Still have to be solved：Organic solvent is to the unstable of oxygen, and cycle performance is poor, and the oxygen in air has a variety of objectionable impurities for example
The problems such as carbon dioxide, dust, moisture, limits the application of conventional organolithium air cell system (referring to Peter always
Bruce etc., Nat.Mater., 2012 year, volume 11, the 19-29 pages).Can using the lithium-air battery system of mixed solvent
The insoluble product for solving to produce during charging blocks air electrode, and then can improve cycle performance, while using gelatin polymer
Electrolyte effectively suppresses generation (Wang Xujiong, Qu Qunting, Liu Lili, Hou Yuyang, Wu Yuping, the name of Li dendrite as cushion
Claim：A kind of high energy density charge-discharge lithium battery, Chinese invention patent:201210195152.2, in June, 2012 date of application
14 days).
Hydrogen peroxide (H2O2) it is a kind of widely known compound being made up of hydrogen and oxygen element, replaced as oxidant
Oxygen (O2) and widely use, it is a kind of potential new energy carrier of tool.H2O2Oxidation-reduction process be two electronics electrification
Course of reaction is learned, with quick dynamics of oxidation-reduction, and is widely studied, and hydrogen peroxide is not as carbon containing
Fuel, its reaction product is oxygen or water, belongs to no pollution and the discharge of zero carbon product, and these products are widely present in
It is environmentally friendly among nature；Liquid hydroperoxide is than gaseous oxygen (O simultaneously2) be stored more easily and handle.Therefore it is based on
The exploitation of the fuel cell of hydrogen peroxide is constantly subjected to the extensive concern of people (referring to Energy such as Yusuke Yamada
Environ.Sci., 2011, volume 4, the 2822-2825 pages).In recent years, H2O2Generally replace O2It is low as some
The oxidant of geothermal liquid fuel cell, such as Metal semi-fuel cells, direct borohydride fuel cell, direct hydrazine fuel cell
Deng.But the voltage of these fuel cells is low, it is impossible to carry out discharge and recharge, the utilization ratio of resource is low.
The content of the invention
It is an object of the invention to provide a kind of high energy density charge-discharge battery being made up of metal and peroxide and
It is applied, and to overcome lithium-air battery organic solvent to the unstable of oxygen, the insoluble product produced during charging blocks air electricity
Pole, the problems such as cycle performance difference and air need to come in from outside.
The high energy density charge-discharge battery that the present invention is provided, is made up of barrier film, negative pole, positive pole and electrolyte, wherein：
(1) barrier film is solid, and alkali metal ion reversible can pass through the barrier film；
(2) negative pole contains alkali metal, or containing the alloy between alkali metal, or contain alkali metal and other metals
The alloy of composition；
(3) mixed aqueous solution just extremely containing peroxide (ROOR ') and metal salt；
(4) electrolyte is divided into the electrolyte of negative side and the electrolyte of side of the positive electrode；The electrolyte of negative side is organic
Electrolyte, polymer dielectric or ionic liquid electrolyte, or their mixture；The electrolyte of side of the positive electrode is metalline
The aqueous solution or hydrogel.
In the present invention, described barrier film is alkali metal containing inorganic oxide, alkali metal containing sulfide or alkali metal containing salt
Full solid state polymer electrolyte, or be the mixture between them；Described alkali metal containing inorganic oxide is MTi2
(PO4)3、M4Ge0.5V0.5O4、M4SiO4、MZr(PO4)2、MB2(PO4)3Or M2O- P2O5-B2O3Deng (wherein M be Li, Na, K, Rb
Or Cs, it is as follows) ternary system, or these alkali metal containing inorganic oxides dopant；Described alkali metal containing sulfide is
M2S-GeS2-SiS2Or M3PO4-GeS2-SiS2Etc. ternary system, or these dopants containing metal sulfide；It is described to contain metal
The full solid state polymer electrolyte of salt is polyethylene glycol oxide, the Kynoar or metalline of metalline of metalline
Siloxanes single-ion polymer electrolyte, or partly or entirely fluorine substitution metalline olefines single-ion polymer electricity
Xie Zhi.
In the present invention, as negative material, wherein described alkali metal includes Li, Na, Rb or Cs；Described other gold
Category includes Mg, Al, B, Si, Ga, In, Sn or Pb.
In the present invention, as the electrolyte of negative side, wherein：
Described organic electrolyte is the solution for being dissolved with metal salt in organic solvent；Described metal salt includes
MClO4、MBF4、MPF6, MBOB or MTFSI, described organic solvent is acetonitrile, tetrahydrofuran, vinyl carbonate, propylene carbonic acid
One or more in ester, diethyl carbonate, dimethyl carbonate or dimethyl sulfoxide (DMSO).
Described polymer dielectric includes all solid state polymer dielectric or gel polymer electrolyte, described
Full solid state polymer electrolyte is the silicon of the polyethylene glycol oxide, the Kynoar of metalline or metalline of metalline
Oxygen alkane single-ion polymer electrolyte, or the metalline olefines single-ion polymer electricity replaced for part or all of fluorine
Xie Zhi, or be their mixture；Described gel polymer electrolyte is the polyoxyalkylene containing above-mentioned organic electrolyte
The single polymers or copolymer of hydrocarbon, the polymer of acrylonitrile or copolymer, the polymer of acrylate or copolymer, Fluorine containing olefine.
Described ionic liquid electrolyte is containing BF4 -Or CF3SO3 -Anionoid or containing imidazoles, pyridines, sulphur class
The ionic liquid of cation.
In the present invention, the catalyst of described positive pole is carbon material, metal and its oxide or hydroxide, metal
And its compound of oxide and carbon material, just extremely contain peroxide (ROOR ') and aqueous solution of alkali metal salt.Wherein peroxide
R, R ' can be with identical in compound (ROOR '), can also be different, can be H or organic group.
In the present invention, as the electrolyte of side of the positive electrode, wherein：The aqueous solution or the hydrogel electrolysis of described metalline
Matter includes being dissolved with the aqueous solution or hydrogel electrolyte of inorganic metal salt or organic metal salt；Described inorganic metal salt bag
Include halide, sulfide, sulfate, nitrate or the carbonate of alkali metal；Described organic metal salt includes the carboxylic acid of metal
The sulfonate of salt or metal.
The high-energy-density aqueous solution charge-discharge battery that the present invention is provided, its structural representation such as Fig. 1, the electrochemistry of generation
Reaction is as follows：
Negative reaction：
Wherein R, R ' it is H or organic group.
The high energy density charge-discharge battery is due to using alkali metal for negative pole, and peroxide is positive pole, therefore actual energy
Metric density is high.Due to (hydrogen) oxide that discharging product is metal, the electrode polarization of electrochemical process does not have lithium // air cell
Greatly.Due to use metal ion can be made reversible by solid be used as barrier film, metallic dendrite can not pass through barrier film, therefore, peace
Full performance is very good；It is organic electrolyte, polymer dielectric or ionic liquid electrolyte, alkali gold in negative pole side simultaneously
Category is highly stable, can occur reversible dissolving and electrodeposit reaction；And the reaction occurred at positive pole side, electric discharge was
Redox reaction between oxide and metal hydroxides MOR；In addition, the use of solid membrane avoids water to negative pole
Migration, while being also prevented from the electrolyte or solvent of negative side to the migration of side of the positive electrode.The energy of the aqueous solution charge-discharge battery
Metric density is high, with very excellent stability and cycle performance.
The present invention also provides application of the high energy density charge-discharge battery in terms of electric power storage and release.
The charge-discharge battery of the present invention has high energy density, and with very excellent stability and cycle performance.
Brief description of the drawings
Fig. 1 is the high energy density charge-discharge battery structure schematic diagram that metal of the present invention is constituted with peroxide.Wherein,
M：Alkali metal or its alloy；M+：Alkali metal ion.
Fig. 2 is embodiment 1 (a) positive pole aqueous solution three-electrode system cyclic voltammetry curve.
Fig. 3 is embodiment 1 (b) using charging and discharging currents as 0.14mA/cm2Constant volume 3000mAh/g carries out discharge and recharge first
With the charging and discharging curve of the 100th circulation.
Embodiment
As shown in Figure 1, Figure 2, it will be described in more detail below by embodiment and comparative example, but the protection model of the present invention
Enclose and be not limited to these embodiments.
Comparative example 1
Graphite using high power capacity (372mAh/g) is negative electrode active material, and reversible capacity is 145mAh/g LiCoO2For
The active material of positive pole, using Super-P as conductive agent, Kynoar as adhesive, N- methyl-pyrrolidons be solvent,
Stir into after uniform slurry, be respectively coated on copper foil and aluminium foil, cathode pole piece and anode pole piece is made.Due in battery
The capacity of middle negative pole is somewhat excessive, therefore, and the actual utilization capacity of negative pole is 350mAh/g.By cathode pole piece and positive pole pole
After piece vacuum drying, with Celgard porous olefin film (model 2400) for barrier film, alkali metal-ion battery core is wound into, is put
In the aluminum hull for entering square.Laser seal, is then dried in vacuo, from liquid injection port injection electrolyte (Zhangjiagang Cathay Huarong
LB315).Chemical conversion, partial volume, are then driven into liquid injection port by steel ball, cell sealing are obtained by negative pole of graphite, LiCoO2For
The alkali metal-ion battery of positive pole.Tested with 1C electric current, be charged as first carrying out constant current with 1C, be charged to after 4.2V
Constant pressure is changed to, charging process is terminated when electric current is 0.1C；Discharge current is 1C, and final voltage is 3.0V.According to test knot
Really, average discharge volt and the energy density obtained according to the active material weight of electrode are obtained.For the sake of more convenient,
These data summarizations are in table 1.
Comparative example 2
By negative pole of lithium piece, Ni nets be negative current collector, with the Li containing 1mol/L2SO4Solution is positive pole, graphite electrode
For plus plate current-collecting body, using component as 19.75Li2O-6.17Al2O3-37.04GeO2- 37.04P2O5Ceramic membrane be barrier film, bear
Pole side is organic electrolyte (LB315 of Zhangjiagang Cathay Huarong).After sealing, obtain with LiMn2O4It is negative pole for positive pole, lithium
Charge-discharge lithium battery.With 0.1mA/cm2Electric current tested, be charged as with 0.1mA/cm2Constant-current charge is carried out, is charged to
4.25V；Discharge current is 0.1mA/cm2, final voltage is 3.7V.According to test result, it is same obtain average discharge volt and
The energy density obtained according to the active material weight of electrode.For the sake of more convenient, these data are also summarized in table 1.
Embodiment 1
Except the electrode of positive pole uses the catalyst of graphene coated nickel cobalt (alloy) positive pole, glass-carbon electrode is anode collection
Body, the aqueous solution of side of the positive electrode is to contain 10wt.%H2O2With 0.5mol/l Li2SO4The aqueous solution, it is other with the phase of comparative example 2
Together, obtain by negative pole of lithium metal, H2O2For the aqueous solution charge-discharge battery of positive pole.With 0.14mA/cm2Electric current surveyed
Examination, is charged as with 0.14mA/cm2Constant-current charge is carried out, constant volume charging capacity is 3000mAh/g；Discharge current is 0.14mA/
cm2, constant volume discharge capacity is 3000mAh/g.It is same to obtain average discharge volt and according to electrode catalyst according to test result
The energy density that the active material weight of agent is obtained.For the sake of more convenient, these data are also summarized in table 1.Circulation volt
Peace curve is shown in Fig. 2, and the charging and discharging curve of discharge and recharge, first charge-discharge and the 100th discharge and recharge is carried out with constant volume 3000mAh/g
See Fig. 3.
Embodiment 2
By negative pole of Na metals, copper foil be negative current collector, nitrogen-doped graphene is the catalyst of positive pole, and vitreous carbon is
Plus plate current-collecting body, to contain 10wt.%H2O2、1.0mol/l Na2SO4Solution be positive pole, using component as
Li1.5Al0.5Ge1.5P3S12Ceramic membrane be barrier film, negative side be organic electrolyte (be dissolved in mass ratio 1：1 ethene carbonic acid
The 1.0mol/l NaClO of ester, methyl ethyl carbonate in the mixed solvent4Electrolyte).After sealing, obtain with N doping graphite
The aqueous solution charge-discharge battery that alkene is the catalyst of positive pole, sodium is negative pole.With 0.1mA/cm2Constant current, permanent electric capacity
(3000mAh/g) carries out charge-discharge test.It is same to obtain average discharge volt and the catalysis according to positive pole according to test result
The energy density that the substance weight of agent is obtained.For the sake of more convenient, these data are also summarized in table 1.
Embodiment 3
Using Na (70wt.%)-Li (30wt.%) alloys as the catalyst that negative pole, nitrogen-doped graphene are positive pole, glass
Carbon is plus plate current-collecting body, to contain 5wt.%H2O20.5mol/lNa2SO4Solution is positive pole, with component 0.75Na2O-
0.3Al2O3-0.4P2O5-0.1TiO2Ceramic membrane be barrier film, negative side be gel polymer electrolyte (porous Kynoar
(PVDF) and polymethyl methacrylate (PMMA) composition composite membrane PVDF/PMMA/PVDF and organic electrolyte (1mol/l
NaPF6Solution) composition).After sealing, the discharge and recharge lithium of catalyst using nitrogen-doped graphene as positive pole, sodium for negative pole is obtained
Battery.With 0.1mA/cm2Constant current, permanent electric capacity (3000mAh/g) carry out charge-discharge test.According to test result, equally obtain
Obtain average discharge volt and the energy density obtained according to the substance weight of the catalyst of positive pole.For the sake of more convenient,
These data are also summarized in table 1.
Embodiment 4
To be pressed with the nickel screen of lithium (90wt.%)-magnesium (10wt.%) alloy as negative pole, nitrogen-doped graphene is urged for positive pole
Agent, glass-carbon electrode is plus plate current-collecting body, to contain 20wt.%H2O25mol/l LiNO3The aqueous solution for positive pole, with
4wt.%LiTFSI+2.5wt.%Nafion117 (product of du pont company) lithium salts+43.5wt.%PEO+
50wt.% (19.75Li2O-6.17Al2O3-37.04GeO2-37.04P2O5) all solid state film of composition is barrier film, negative side is
(dissolving 3wt.% poly- (methyl methacrylate) organic electrolyte be (Zhangjiagang Cathay Huarong for gel polymer electrolyte
)), LB315 the side of the positive electrode of barrier film uses sodium carboxymethylcellulose that average pore size is 50% for 200nm, porosity as water
Organosol polymeric carrier.After sealing, obtain with H2O2For positive pole, the water that lithium (90wt.%)-magnesium (10wt.%) alloy is negative pole
Solution charge-discharge battery.With 0.1mA/cm2The permanent electric capacity 3000mAh/g of constant current carry out charge-discharge test.According to test knot
Really, the same energy density for obtaining average discharge volt and being obtained according to the active material weight of electrode.In order to more convenient
For the sake of, these data are also summarized in table 1.
The experimental data summary sheet of table 1.
* negative material is calculated by the lithium quality of reaction, the catalyst quality of positive pole is participated in.
The above-described embodiments are merely illustrative of preferred embodiments of the present invention, not to the present invention's
Spirit and scope are defined, under the premise of design concept of the present invention is not departed from, and ordinary skill technical staff is to this in this area
The all variations and modifications that the technical scheme of invention is made, all should fall into protection scope of the present invention, and the present invention is claimed
Technology contents have all been recorded in detail in the claims.
Claims (10)
1. a kind of high energy density charge-discharge battery being made up of metal and peroxide, by barrier film, negative pole, positive pole and electrolyte
Composition, it is characterized in that：
(1) barrier film is solid, and alkali metal ion reversible can pass through the barrier film；
(2) negative pole contains alkali metal, or containing the alloy between alkali metal, or constituted containing alkali metal and other metals
Alloy；
(3) mixed aqueous solution just extremely containing peroxide (ROOR ') and metal salt；
(4) electrolyte is divided into the electrolyte of negative side and the electrolyte of side of the positive electrode；The electrolyte of negative side is organic electrolysis
Liquid, polymer dielectric or ionic liquid electrolyte or their mixture；The electrolyte of side of the positive electrode is water-soluble for metalline
Liquid or hydrogel.
2. high energy density charge-discharge battery according to claim 1, it is characterized in that described barrier film be alkali metal containing without
The full solid state polymer electrolyte of machine oxide, alkali metal containing sulfide or alkali metal containing salt, or be the mixing between them
Thing；Described alkali metal containing inorganic oxide is MTi2(PO4)3、M4Ge0.5V0.5O4、M4SiO4、MZr(PO4)2、MB2(PO4)3Or
M2O-P2O5-B2O3, wherein M be Li, Na, K, Rb or Cs, or these alkali metal containing inorganic oxides dopant；Described contains alkali
Metal sulfide is M2S-GeS2-SiS2Or M3PO4-GeS2-SiS2Etc. ternary system, or these doping containing metal sulfide
Thing；The full solid state polymer electrolyte of the metalline is polyethylene glycol oxide, the polyvinylidene fluoride of metalline of metalline
The siloxanes single-ion polymer electrolyte of alkene or metalline, or the metalline olefines that partly or entirely fluorine replaces are isolated
Sub- polymer dielectric.
3. the high energy density charge-discharge battery according to claims 1 or 2, it is characterized in that wherein described alkali metal bag
Include Li, Na, Rb or Cs；Described other metals include Mg, Al, B, Si, Ga, In, Sn or Pb.
4. the high energy density charge-discharge battery according to any one in claim 1-3, it is characterized in that the negative side
Electrolyte include organic electrolyte, polymer dielectric or ionic liquid electrolyte.
5. high energy density charge-discharge battery according to claim 4, it is characterized in that described organic electrolyte is to have
The solution of metal salt is dissolved with machine solvent；Described metal salt includes MClO4、MBF4、MPF6, MBOB or MTFSI, it is described
Organic solvent is acetonitrile, tetrahydrofuran, vinyl carbonate, propylene carbonate, diethyl carbonate, dimethyl carbonate or diformazan
One or more in base sulfoxide.
6. high energy density charge-discharge battery according to claim 4, it is characterized in that described polymer dielectric includes
All solid state polymer dielectric or gel polymer electrolyte, described full solid state polymer electrolyte is the poly- of metalline
The siloxanes single-ion polymer electrolyte of ethylene oxide, the Kynoar of metalline or metalline, or be part
Or the metalline olefines single-ion polymer electrolyte of whole fluorine substitutions, or be their mixture；Described gel
Polymer dielectric is the polyoxygenated alkene containing above-mentioned organic electrolyte, the polymer of acrylonitrile or copolymer, acrylate
Polymer or copolymer, the single polymers or copolymer of Fluorine containing olefine.
7. high energy density charge-discharge battery according to claim 4, it is characterized in that described ionic liquid electrolyte is
Containing BF4 -Or CF3SO3 -Anionoid or containing imidazoles, pyridines, sulphur cationoid ionic liquid.
8. high energy density charge-discharge battery according to claim 1, it is characterized in that the catalyst of described positive pole is carbon
The compound of material, metal and its oxide or hydroxide, metal and its oxide and carbon material, just extremely contains peroxidating
Thing (ROOR ') and aqueous solution of alkali metal salt.
9. the high energy density charge-discharge battery according to claim 1 or 8, it is characterized in that the peroxide
R, R ' can be with identical in (ROOR '), can also be different, can be H or organic group；Containing gold in the electrolyte of the side of the positive electrode
Belong to the aqueous solution or the hydrogel electricity that the aqueous solution or hydrogel electrolyte of salt include being dissolved with inorganic metal salt or organic metal salt
Xie Zhi；Described inorganic metal salt includes halide, sulfide, sulfate, nitrate or the carbonate of alkali metal；Described has
Machine metal salt includes the carboxylate of metal or the sulfonate of metal.
10. the application of the high energy density charge-discharge battery according to any one in claim 1-9, it is characterized in that should answer
With the storage and release for electric energy.
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| US20060094928A1 (en) * | 2004-11-02 | 2006-05-04 | Samsung Sdi Co., Ltd. | Fuel cell for microcapsule-type robot and microcapsule-type robot powered by the same |
| CN1921198A (en) * | 2006-09-12 | 2007-02-28 | 崔骥 | Liquid cathode fuel battery |
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