CN109994785B - Zinc organic battery and application - Google Patents
Zinc organic battery and application Download PDFInfo
- Publication number
- CN109994785B CN109994785B CN201811645343.8A CN201811645343A CN109994785B CN 109994785 B CN109994785 B CN 109994785B CN 201811645343 A CN201811645343 A CN 201811645343A CN 109994785 B CN109994785 B CN 109994785B
- Authority
- CN
- China
- Prior art keywords
- aqueous electrolyte
- organic solvent
- zinc
- active material
- positive electrode
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 51
- 239000011701 zinc Substances 0.000 title claims abstract description 51
- 239000003960 organic solvent Substances 0.000 claims abstract description 87
- 239000003792 electrolyte Substances 0.000 claims abstract description 86
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 33
- 230000003647 oxidation Effects 0.000 claims abstract description 30
- 239000013543 active substance Substances 0.000 claims abstract description 18
- 230000009467 reduction Effects 0.000 claims abstract description 14
- 239000007864 aqueous solution Substances 0.000 claims abstract description 11
- 230000009471 action Effects 0.000 claims abstract description 7
- 230000005484 gravity Effects 0.000 claims abstract description 6
- 239000007788 liquid Substances 0.000 claims abstract description 6
- 230000000694 effects Effects 0.000 claims abstract description 4
- 238000003487 electrochemical reaction Methods 0.000 claims abstract description 4
- 150000003751 zinc Chemical class 0.000 claims abstract description 4
- 239000007774 positive electrode material Substances 0.000 claims description 78
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 28
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 25
- -1 alkyl ferrocene Chemical compound 0.000 claims description 19
- 229910002804 graphite Inorganic materials 0.000 claims description 17
- 239000010439 graphite Substances 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 150000008040 ionic compounds Chemical class 0.000 claims description 7
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- UGNWTBMOAKPKBL-UHFFFAOYSA-N tetrachloro-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(Cl)=C(Cl)C1=O UGNWTBMOAKPKBL-UHFFFAOYSA-N 0.000 claims description 6
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 claims description 6
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 5
- 239000000194 fatty acid Substances 0.000 claims description 5
- 229930195729 fatty acid Natural products 0.000 claims description 5
- 150000004665 fatty acids Chemical class 0.000 claims description 5
- STOSPPMGXZPHKP-UHFFFAOYSA-N tetrachlorohydroquinone Chemical compound OC1=C(Cl)C(Cl)=C(O)C(Cl)=C1Cl STOSPPMGXZPHKP-UHFFFAOYSA-N 0.000 claims description 5
- 150000001450 anions Chemical class 0.000 claims description 4
- 239000004020 conductor Substances 0.000 claims description 4
- 239000004210 ether based solvent Substances 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- RVWUHFFPEOKYLB-UHFFFAOYSA-N 2,2,6,6-tetramethyl-1-oxidopiperidin-1-ium Chemical compound CC1(C)CCCC(C)(C)[NH+]1[O-] RVWUHFFPEOKYLB-UHFFFAOYSA-N 0.000 claims description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 3
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 3
- 150000003949 imides Chemical class 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 claims description 3
- YZYASTRURKBPPS-UHFFFAOYSA-N C(CCC(=O)OCCCCCC(C)C)(=O)OCCCCCC(C)C.[Na] Chemical compound C(CCC(=O)OCCCCCC(C)C)(=O)OCCCCCC(C)C.[Na] YZYASTRURKBPPS-UHFFFAOYSA-N 0.000 claims description 2
- 239000006183 anode active material Substances 0.000 claims description 2
- 238000004891 communication Methods 0.000 claims description 2
- 239000003759 ester based solvent Substances 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims 4
- 229910052742 iron Inorganic materials 0.000 claims 2
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 claims 2
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 claims 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 claims 1
- 230000008901 benefit Effects 0.000 abstract description 12
- 238000004146 energy storage Methods 0.000 abstract description 10
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 14
- 229910052799 carbon Inorganic materials 0.000 description 14
- 238000006722 reduction reaction Methods 0.000 description 14
- 238000007599 discharging Methods 0.000 description 13
- 239000004743 Polypropylene Substances 0.000 description 10
- 229920001155 polypropylene Polymers 0.000 description 10
- 238000013461 design Methods 0.000 description 9
- 229910052938 sodium sulfate Inorganic materials 0.000 description 9
- 235000011152 sodium sulphate Nutrition 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 8
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 7
- 235000019341 magnesium sulphate Nutrition 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 6
- 229920000049 Carbon (fiber) Polymers 0.000 description 5
- 239000004917 carbon fiber Substances 0.000 description 5
- XYVVCFFJQVMSNN-UHFFFAOYSA-N cyclopenta-1,3-diene iron(2+) 5-octylcyclopenta-1,3-diene Chemical compound [Fe++].c1cc[cH-]c1.CCCCCCCC[c-]1cccc1 XYVVCFFJQVMSNN-UHFFFAOYSA-N 0.000 description 5
- 210000001787 dendrite Anatomy 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- 229940006460 bromide ion Drugs 0.000 description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical compound BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000010248 power generation Methods 0.000 description 4
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 4
- 229960001763 zinc sulfate Drugs 0.000 description 4
- 229910000368 zinc sulfate Inorganic materials 0.000 description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 210000004027 cell Anatomy 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 239000011630 iodine Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 235000005074 zinc chloride Nutrition 0.000 description 3
- 239000011592 zinc chloride Substances 0.000 description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N Caprylic acid Natural products CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- GONOPSZTUGRENK-UHFFFAOYSA-N benzyl(trichloro)silane Chemical compound Cl[Si](Cl)(Cl)CC1=CC=CC=C1 GONOPSZTUGRENK-UHFFFAOYSA-N 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 2
- 229940006461 iodide ion Drugs 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- WRTMQOHKMFDUKX-UHFFFAOYSA-N triiodide Chemical compound I[I-]I WRTMQOHKMFDUKX-UHFFFAOYSA-N 0.000 description 2
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 description 2
- JHUUPUMBZGWODW-UHFFFAOYSA-N 3,6-dihydro-1,2-dioxine Chemical compound C1OOCC=C1 JHUUPUMBZGWODW-UHFFFAOYSA-N 0.000 description 1
- 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 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- BNOODXBBXFZASF-UHFFFAOYSA-N [Na].[S] Chemical compound [Na].[S] BNOODXBBXFZASF-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- HWQXBVHZYDELQG-UHFFFAOYSA-L disodium 2,2-bis(6-methylheptyl)-3-sulfobutanedioate Chemical compound C(CCCCC(C)C)C(C(C(=O)[O-])S(=O)(=O)O)(C(=O)[O-])CCCCCC(C)C.[Na+].[Na+] HWQXBVHZYDELQG-UHFFFAOYSA-L 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- 229910001338 liquidmetal Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- 229940102001 zinc bromide Drugs 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
-
- 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
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
- H01M10/38—Construction or manufacture
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention discloses a zinc organic battery and application thereof, belonging to the field of batteries and comprising a container, wherein the container contains a positive active substance, a positive current collector, an organic solvent, a zinc cathode and an aqueous electrolyte, and the organic solvent and the aqueous electrolyte are immiscible and are layered under the action of gravity due to different densities; the positive active substance has redox activity, has two forms of an oxidation state and a reduction state, and can be reversibly converted through electrochemical reaction; if the positive electrode active substance is liquid and is difficult to dissolve in the aqueous electrolyte, the organic solvent can be omitted, namely the positive electrode active substance can be used as the organic solvent and is layered with the aqueous electrolyte; the main component of the zinc cathode is zinc, and the zinc cathode is soaked in the aqueous electrolyte and is not in contact with an organic solvent; the aqueous electrolyte is an aqueous solution containing a zinc salt. The battery has the advantages of long cycle life, high safety and low preparation cost, can be used as a large rechargeable battery, and meets the application of large-scale energy storage.
Description
Technical Field
The invention belongs to the field of batteries, and particularly relates to a zinc organic battery and application thereof.
Background
Efficient use of new energy sources, such as solar and wind, is a desire to solve human energy problems. The solar energy and the wind energy have the characteristics of intermittency, volatility and randomness, and cannot be matched with the electricity demand of people in time, so that the electric energy generated by the solar energy and the wind energy is stored by an energy storage technology and released when needed.
Among the energy storage technologies, the energy storage battery technology has the advantages of high energy efficiency, no region limitation and the like, and becomes a key development object of all countries in the world.
The battery used as the energy storage of the power grid has performance requirements which are greatly different from other rechargeable batteries, low cost, easy mass production, long cycle life, no environmental pollution, safety and reliability, and the requirement on energy density is not high. Batteries that have been currently attempted for grid energy storage applications include: lead-acid batteries, lithium ion batteries, flow batteries, high-temperature sodium-sulfur batteries, liquid metal batteries and the like, but the problems of high cost, short service life, difficult recycling, potential safety hazards and the like exist, and the requirement of power grid energy storage application cannot be met.
In view of the above drawbacks and needs of improvement of the prior art, it is desirable to develop a new type of battery.
Disclosure of Invention
In view of the above-mentioned drawbacks or needs for improvement in the prior art, the present invention provides a novel battery, which is intended to realize a large-sized rechargeable battery with a long cycle life and high safety at a very low manufacturing cost, and to satisfy the application of large-scale energy storage.
In order to achieve the above objects, according to one aspect of the present invention, there is provided a zinc-organic battery having a container containing a positive active material, a positive current collector, an organic solvent, a zinc negative electrode, and an aqueous electrolyte, wherein,
the organic solvent and the aqueous electrolyte are immiscible, have different densities and can be layered under the action of gravity;
the solubility of the oxidation state of the positive electrode active material in the organic solvent is greater than the solubility in the aqueous electrolyte;
according to another aspect of the present invention, there is also provided a zinc organic battery having a container containing a positive active material, a positive current collector, a zinc negative electrode, and an aqueous electrolyte, wherein,
the positive active substance is liquid and is insoluble in the aqueous electrolyte, and the positive active substance and the aqueous electrolyte have different densities and can be layered under the action of gravity;
for the two aspects, the positive active material has redox activity and has two forms of an oxidation state and a reduction state, the two forms can generate reverse conversion through electrochemical reaction, the two forms have different molar ratios corresponding to different battery charge states, when the oxidation state content is high, the battery is in a high charge state, and when the reduction state content is high, the battery corresponds to a low charge state;
the positive electrode current collector is used for collecting current at the positive electrode;
the zinc cathode is soaked in the aqueous electrolyte and is not contacted with the positive active material;
the aqueous electrolyte is an aqueous solution containing zinc salt.
Further, the positive electrode active material is selected from one of the following four:
first, halogen, an anion formed by a simple halogen or three halogen atoms in an oxidized state, and an ion thereof in a reduced state, including Br2/Br-，I2/I-，Br3 -/Br-，I3 -/I-；
The second, alkylferrocene, in the oxidized form is alkylferrocene (III) ion and in the reduced form is alkylferrocene (II), including octylferrocene ion C18H26Fe(Ⅲ)+Octyl ferrocene C18H26Fe(Ⅱ)；
Thirdly, the positive active material is 2,2,6, 6-tetramethyl piperidine oxide TEMPO with molecular formula C9H18NO,TEMPO+Is the oxidation state of the positive active material, and TEMPO is the reduction state of the positive active material;
fourthly, the positive active material is quinone in oxidation state and corresponding phenol in reduction state, including tetrachloro-p-benzoquinone C6Cl4O2Tetrachlorohydroquinone C6(OH)2Cl4。
Further, the lithium ion battery also comprises an organic ionic compound which is used for balancing the charge state of the positive active material in the charge and discharge processes and ensuring the overall charge neutrality,
the lithium bis (trifluoromethanesulfonylimide) LiTFSI is prepared, and the molecular formula is as follows: CF (compact flash)3SO2)2NLi, sodium diisooctyl succinate sulfonate AOT, molecular formula: COOC8H17)CH2CH(COOC8H17)SO3Na, tetrabutylammonium bistrifluoromethylsulfonimide TBATFSI, molecular formulaComprises the following steps: (CF)3SO2)2N2C16H36。
Further, the battery has two or more positive current collectors that are not in direct communication with each other.
Further, the organic solvent is selected from ether solvents, fatty acids and ester solvents, wherein the ether solvents include tetrahydrofuran (molecular formula is (CH)2)4O), 1, 4-dioxane (molecule is C)4H8O2) Tetraglycol dimethyl ether (molecular formula is CH)3O(CH2CH2O)4CH3)；
The fatty acids include caproic acid (molecular formula C)5H11COOH)；
The ester solvent comprises butyl acetate (CH)3COOC4H9)。
Further, the positive current collector is made of a porous conductive material, the porous conductive material comprises a graphite felt, the positive current collector is located at an interface of the organic solvent and the aqueous electrolyte, and the positive current collector can rotate.
Furthermore, the density of a solution formed by dissolving the positive electrode active material in the organic solvent is lower than that of the aqueous electrolyte, the organic solvent and the positive electrode active material are on the upper layer, the aqueous electrolyte is on the lower layer, and the zinc negative electrode is on the lowest layer, and the zinc negative electrode is soaked in the aqueous electrolyte and is not in contact with the organic solvent.
Furthermore, the density of a solution formed by dissolving the positive electrode active material in the organic solvent is greater than that of an aqueous electrolyte, the organic solvent and the positive electrode active material are in the lower layer, the aqueous electrolyte is in the upper layer, and the zinc cathode is suspended in the upper half part of the aqueous electrolyte and is not in contact with the organic solvent.
Furthermore, the density of a solution formed by dissolving the positive active material in the organic solvent is greater than that of the aqueous electrolyte, the bottom of the container is provided with a plurality of grooves, one part of the grooves is used for placing the zinc cathode, and the other part of the grooves is used for placing the positive active material and the organic solvent.
According to a third aspect of the present invention there is also provided the use of a zinc organic cell as described above in the field of energy storage.
In general, compared with the prior art, the above technical solution contemplated by the present invention can achieve the following beneficial effects:
according to the technical scheme, the battery is automatically divided into three layers of an organic solvent (a positive active substance is dissolved in the organic solvent), an aqueous electrolyte and a zinc cathode or three layers of the positive active substance, the aqueous electrolyte and the zinc cathode under the action of gravity, a positive electrode and a negative electrode are not required to be separated by a diaphragm, and an electrochemical active substance reactant participating in the battery work can be quickly conducted in the aqueous electrolyte or the organic solvent through convection, so that the current density is improved. In addition, the design can not only make the battery play the advantages of stable electrochemical properties of the organic solvent and high solubility to the positive electrode active material, but also prevent the organic solvent from burning by utilizing the aqueous electrolyte, thereby improving the safety of the battery. In addition, the battery has simple raw materials and structure and low manufacturing cost. The cycle life is high since the dendrite problem of the negative electrode can be overcome. Therefore, a large rechargeable battery with a long cycle life and high safety can be realized at a very low manufacturing cost, and the application of large-scale energy storage is satisfied.
Drawings
FIG. 1 is a cross-sectional view of a battery according to examples 1 and 2 of the present invention;
FIG. 2 is a cross-sectional view of a battery according to examples 3 and 4 of the present invention;
FIG. 3 is a sectional view of a battery in example 5 of the invention;
FIG. 4 is a sectional view of a battery in example 6 of the invention;
FIG. 5 is a sectional view of a battery according to example 7 of the present invention;
the same reference numbers will be used throughout the drawings to refer to the same or like elements or structures, wherein:
1-Polypropylene lining of container 2-stainless steel bottom 3-zinc cathode
4-aqueous electrolyte 5-organic solvent and positive active material mixed solution 6-graphite felt
7-carbon rod 8-motor (built-in conductive slip ring) 9-graphite felt plated with zinc
10-cyclotron oscillator
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The invention provides a zinc-organic battery, which is provided with a container, wherein the container contains a positive active substance, a positive current collector, an organic solvent, a zinc cathode and an aqueous electrolyte, wherein the organic solvent and the aqueous electrolyte are immiscible, have different densities and can be automatically layered under the action of gravity, the positive active substance has redox activity and has two forms of an oxidation state and a reduction state, the two forms can be reversibly converted through electrochemical reaction, the different molar ratio proportions correspond to different battery charge states, when the oxidation state content is high, the battery is in a high charge state, and when the oxidation state content is low, the battery is in a low charge state and needs to be charged.
The solubility of the oxidation state of the positive active material in the organic solvent is higher than that of the positive active material in the aqueous electrolyte, so that the oxidation state of the positive active material is enriched in the organic solvent under the action of an extraction mechanism and is not in direct contact with a zinc cathode, and self-discharge is avoided; the solubility of the reduced form of the positive electrode active material in the organic solvent is not particularly required, because the reduced form of the positive electrode active material does not necessarily undergo a redox reaction with the zinc negative electrode even if it is dissolved in the aqueous electrolyte.
If the positive electrode active material is in a liquid state and is insoluble in the aqueous electrolyte, the organic solvent can be omitted, i.e., the positive electrode active material doubles as the organic solvent and is layered with the aqueous electrolyte; the liquid positive active material itself has an advantage as an organic solvent in that the positive active material content ratio is high, resulting in a larger energy density of the battery.
The main component of the zinc cathode is zinc, and the zinc cathode is soaked in the aqueous electrolyte and is not in contact with an organic solvent; when the density of the organic solvent is smaller than that of the aqueous electrolyte, the organic solvent is on the upper layer, the aqueous electrolyte is on the lower layer, and the zinc powder is soaked in the lower half part of the aqueous electrolyte and is not in contact with the organic solvent; when the density of the organic solvent is greater than that of the aqueous electrolyte, the organic solvent is in the lower layer, the aqueous electrolyte is in the upper layer, and the zinc sheet is suspended on the upper half part of the aqueous electrolyte and is not in contact with the organic solvent. The design has the advantages that in the charging process, even if zinc dendrite is generated, the zinc cathode can be ensured not to be directly contacted with the oxidation state of the anode active material in the organic solvent by increasing the amount of the aqueous electrolyte, and the battery does not generate self-generation. In addition, the zinc dendrites can be broken by stirring. During discharging, zinc dendrites generated by charging are oxidized and disappear, namely, the zinc dendrites are oxidized into zinc ions.
The aqueous electrolyte is a sodium sulfate or magnesium sulfate aqueous solution containing zinc salt. The advantage of this design is that a concentration of sodium or magnesium sulfate can promote the delamination of the aqueous solution from the organic solvent and the positive active material, ensuring that the oxidation state of the positive active material in the organic solvent does not come into direct contact with the zinc negative electrode.
The organic ionic compound consists of cations and anions, such as lithium bistrifluoromethylsulfonyl imide (LiTFSI), sodium diisooctyl sulfosuccinate (AOT), tetrabutylammonium bistrifluoromethylsulfonyl imide (TBATFSI). During charging and discharging, anions or cations of the organic ionic compound can migrate between the two phases of the positive electrode active material and the aqueous electrolyte to maintain the electrical neutrality of the two phases.
Further, the positive electrode current collector is made of a porous conductive material, such as graphite felt. The positive electrode current collector is positioned at the interface of the organic solvent and the aqueous electrolyte and can rotate. The positive electrode current collector has the advantages that the positive electrode active material can be promoted to be in contact with the positive electrode current collector through rotation of the positive electrode current collector, and accordingly the capacity of the battery for bearing high-current charging and discharging is improved.
Further, the positive electrode active material is bromine/bromide ion, wherein bromine is an oxidation state of the positive electrode active material, and bromide ion is a reduction state of the positive electrode active material.
Alternatively, the positive electrode active material may be tribromide ion/bromide ion, in which the tribromide ion is an oxidized state of the positive electrode active material and the bromide ion is a reduced state of the positive electrode active material.
Alternatively, the positive electrode active material may be iodine/iodide ion, in which iodine is an oxidized state of the positive electrode active material and iodide ion is a reduced state of the positive electrode active material.
Alternatively, the positive electrode active material may be triiodide/iodide, in which triiodide is an oxidized state of the positive electrode active material and iodide is a reduced state of the positive electrode active material.
Alternatively, the positive electrode active material may be tetrachlorop-benzoquinone/tetrachlorohydroquinone, in which tetrachlorop-benzoquinone is an oxidized state of the positive electrode active material and tetrachlorohydroquinone is a reduced state of the positive electrode active material.
Alternatively, the positive electrode active material may be octyl ferrocene ion/octyl ferrocene, in which the positive electrode active material is octyl ferrocene ion in the oxidized state and octyl ferrocene in the reduced state.
Alternatively, the positive electrode active material may be 2,2,6, 6-tetramethylpiperidine oxide (TEMPO), wherein TEMPO+Is the oxidation state of the positive electrode active material, and TEMPO is the reduction state of the positive electrode active material.
Further, the organic solvent is a fatty acid, such as caproic acid. Alternatively, the organic solvent may be an ether solvent such as tetrahydrofuran, 1, 4-dioxane, or tetraethylene glycol dimethyl ether. Alternatively, the organic solvent may also be an ester solvent, such as butyl acetate.
Of the organic solvents, caproic acid is not miscible with water, and other solvents are not miscible with water, but are not miscible with high-concentration aqueous solutions of sodium sulfate or magnesium sulfate, and thus separate layers. Sodium sulfate or magnesium sulfate can be used as a water removal drying agent in organic synthesis, and their binding capacity with water is greater than that of the above-mentioned solvents, so that water is separated from the organic solvent to form a single phase. The advantage of this design is that by adjusting the concentration of sodium sulfate or magnesium sulfate in the aqueous electrolyte, the proportion of water in the organic solvent can be controlled, thereby optimizing the ionic conductivity and electrochemical stability of the organic solvent. Meanwhile, the organic solvent containing water is not easy to burn, and the safety of the battery is improved.
Further, the battery structure is determined by the difference in density between the organic solvent and the aqueous electrolyte. When the density of a solution formed by dissolving the positive active material in the organic solvent of the battery is smaller than that of the aqueous electrolyte, the organic solvent and the positive active material are on the upper layer, the aqueous electrolyte is on the lower layer, and the zinc cathode is soaked in the aqueous electrolyte and is not in contact with the organic solvent. When the density of a solution formed by dissolving the positive active material in the organic solvent of the battery is greater than that of the aqueous electrolyte, the organic solvent and the positive active material are in the lower layer, the aqueous electrolyte is in the upper layer, and the zinc cathode is soaked in the aqueous electrolyte and is not in contact with the organic solvent.
Furthermore, a plurality of grooves are designed at the bottom of the container, wherein a part of the grooves are used for placing zinc cathodes, and the other part of the grooves are used for placing positive active materials and organic solvents.
Furthermore, the battery of the invention can be designed to have two or more positive current collectors, the positive current collectors are not conducted with each other, and when one part of the positive current collectors is subjected to oxidation reaction, the other part of the positive current collectors can be subjected to reduction reaction. The design has the advantages that the positive current collector with the surface undergoing the reduction reaction in the battery corresponds to the discharge reaction; the positive current collector with the surface subjected to the oxidation reaction corresponds to a charging reaction, and the charging reaction and the discharging reaction can be simultaneously carried out on different positive current collectors. When the battery is charged by the random electric energy output generated by wind power and solar power generation, the oxidation state of the positive active substance generated by charging can be uniformly distributed in the organic solvent through convection, the concentration of the oxidation state of the positive active substance on the surface of the positive current collector subjected to reduction reaction is kept stable, and the continuous operation of the discharging process with stable power output is supported.
In order to further illustrate the process of the present invention, further details are provided below with reference to specific examples.
Example 1
As shown in the attached figure 1 of the specification, a stainless steel tank with an inner diameter of 10 cm, a wall thickness of 0.3 mm and a height of 10 cm and an open top is used as a container; the inner wall surface of the battery is provided with a layer of polypropylene lining with the thickness of 2mm to play the role of insulation, and the bottom of the battery is not provided with the polypropylene lining and is used as a negative current collector of the battery. 5g of zinc powder is put into the container to be used as a zinc cathode and is contacted with the bottom of the stainless steel tube to ensure the conductivity. 30ml of 5mol/L zinc bromide aqueous solution is added into the container to be used as aqueous electrolyte, bromide ions in the aqueous electrolyte are the reduction state of the positive active substance, and the oxidation state of the bromide ions is bromine and tribromide ions. Then 30ml of caproic acid is added as organic solvent, the caproic acid is only slightly soluble in water at room temperature, and most of the caproic acid floats above the aqueous electrolyte to form an independent phase. And a cover made of polypropylene is added above the container, a hole drilled obliquely is formed in the cover, a carbon rod is inserted into the cover, a disc made of graphite felt with the thickness of 1cm is installed at the tail end of the carbon rod, which is positioned at the hexanoic acid/aqueous electrolyte interface, the diameter of the disc is 5cm, the disc is perpendicular to the carbon rod, and an included angle which is larger than 0 and smaller than 90 degrees is formed between the disc and the hexanoic acid/aqueous electrolyte interface. One end of the carbon rod extending out of the top of the container is connected with a motor, and a built-in conductive slip ring enables an external lead to be in good contact with the rotating carbon rod. During the rotation of the carbon rod, the surface of the graphite felt disk is continuously switched between caproic acid and aqueous electrolyte, so that the mass transfer of reactants in the charging and discharging processes can be promoted. The battery can be charged under the external voltage of 1.9V, the charging current can be increased by increasing the rotating speed of the carbon rod, and the charging current can reach 1A under the condition that the rotating speed is 5 seconds for one circle.
When the charging capacity is controlled to be 7000 mAmp, discharging can be carried out later, the voltage of a discharging platform is 1.5V, when the capacity is 6300 mAmp, the coulombic efficiency is 90%, and no obvious capacity and voltage change is seen after 1000 cycles of circulation.
Example 2
The same cell structure as in example 1 was used, with the change of the substances added in the container: 100 g of zinc powder is added into a container to be used as a zinc cathode, and then 20 ml of 1mol/L zinc chloride aqueous solution is added to be used as an aqueous electrolyte. Then 40 ml of 1 mol/L1, 4-dioxane solution of tetrachloro-p-benzoquinone is added, tetrachloro-p-benzoquinone is used as the oxidation state of the positive active material, is insoluble in water, and is tetrachloro-hydroquinone in the reduction state.
After the battery is manufactured, the battery is in a charging state and can be directly discharged, the discharge voltage is 1.1V, and the capacity is 2000 mAmp hours; the charging voltage is 1.5V, and the coulombic efficiency is 95 percent; the discharge capacity after 1000 cycles was 1800 mAmp-hrs.
Example 3
As shown in the attached figure 2 of the specification, a sealed polypropylene storage tank with an inner diameter of 10 cm, a wall thickness of 0.3 mm and a height of 10 cm is used as a container. One twisted carbon fiber is used as a lead and passes through a small hole (the diameter is 0.2mm) at the bottom of the storage tank, and is in good contact with a circular graphite felt with the diameter of 5cm and the thickness of 0.5cm at the bottom in the container, and the sealing performance of the small hole is good. The graphite felt was coated with 5g of zinc. The use of carbon fibers for connecting to an external circuit is advantageous in that the carbon fibers are not corroded by aqueous electrolytes and organic solutions in long-term use. The container is also internally provided with 30ml of aqueous electrolyte, the aqueous electrolyte comprises magnesium sulfate, zinc chloride and ammonium chloride, the concentration of the magnesium sulfate is 150g/L, the concentration of the zinc chloride is 50g/L, the concentration of the ammonium chloride is 50g/L of aqueous solution, 30ml of butyl acetate is used as an organic solvent, 20g of TEMPO is dissolved in the butyl acetate, 50g of AOT is also dissolved in the butyl acetate, and a piece of graphite felt with the diameter of 8cm is used as a positive electrode current collector. And the positive current collector is soaked in the interface of the organic solvent and the aqueous electrolyte and is led out from the upper part of the polypropylene storage tank through a carbon rod. The whole polypropylene storage tank is placed on a platform of a rotary oscillator for rotary oscillation, and convection can be formed in the organic solvent and the aqueous electrolyte of the battery by the design, so that the mass transfer speed is improved.
After the battery is manufactured, the battery is in a discharge state, the battery needs to be charged firstly, and the current density is 100mA/cm2When the rotation speed is 100r/min, the charging voltage is 1.6V, the capacity is 1900mAh, and the charged positive active material is changed from reduced TEMPO to oxidized TEMPO+. Then, discharging can be carried out, the discharging voltage is 1.2V, and the coulombic efficiency is 95%; the discharge capacity after 1000 cycles was 1800 mAmp-hrs. If it is notThe rotating speed is increased to 200r/min, the charging voltage of the battery is 1.55V and the discharging voltage is 1.3V under the same current density, the capacity can be increased to 2200mAh, and the coulomb efficiency is increased to 98%.
Example 4
Using the same cell structure as in example 3, the organic solvent in the container was changed to 30ml of tetrahydrofuran in which 10g of iodine and 30g of TBATFSI were dissolved and the oxidation state of the positive electrode active material was I3 -And I2In the reduced state of I-。
The battery is in a charging state after being manufactured, can be directly discharged, and has the discharge voltage of 1.1V and the discharge capacity of 1500 milliampere hours. And then charging is carried out, the charging voltage is 1.5V, the capacity is 1300 mAmp, the coulombic efficiency in the circulation process is 90%, and the discharge capacity after 1000 cycles is 1000 mAmp.
Example 5
As shown in the attached figure 3 of the specification, a sealed polypropylene storage tank with an inner diameter of 10 cm, a wall thickness of 0.3 mm and a height of 10 cm is used as a container. A twisted carbon fiber is used as a lead wire and passes through a pore (the diameter is 0.2mm) at the bottom of the storage tank to be in good contact with a circular graphite felt with the diameter of 5cm and the thickness of 0.5cm at the bottom in the container, and the pore has good sealing property. The container is also internally provided with 30ml of aqueous electrolyte, and the components of the aqueous electrolyte comprise sodium sulfate and zinc sulfate, wherein the concentration of the sodium sulfate is 50g/L, the concentration of the zinc sulfate is 25g/L of aqueous solution, and 30ml of tetraethylene glycol dimethyl ether is used as an organic solvent, and 30g of octyl ferrocene and 15g of LiTFSI are dissolved in the aqueous solution. A small hole is formed above the container, a carbon rod penetrates through the small hole, one end of the carbon rod is connected with a lead as a negative electrode, the other end of the carbon rod is connected with a graphite felt plated with 5g of zinc, and the contact is good. The galvanized graphite felt is completely soaked in the aqueous electrolyte and is not contacted with the organic solvent.
After the battery is manufactured, the battery is in a discharge state, the battery needs to be charged firstly, the charging voltage is 1.6V, and when the capacity is 2500 milliamperes, the active material of the positive electrode is changed into octyl ferrocene ions in an oxidation state from octyl ferrocene in a reduction state after the battery is charged. Then the battery can be discharged, the discharge voltage is 1.3V, and the coulombic efficiency is 95%; the charge-discharge capacity is not obviously changed after 1000 cycles.
Example 6
As shown in the attached figure 4 of the specification, the carbon rod is changed to be vertical, and the bottom of the polypropylene storage tank is changed to be 16 hemispherical grooves with the radius of 1 cm. Half of the grooves are filled with zinc-plated graphite felts, each graphite felt is plated with 1g of zinc and has the size of 1cm by 0.5cm, carbon fibers are used as the bottom of the groove and a current collector of a negative electrode of a battery, and the other part of the grooves are filled with a mixture of a positive active material and an organic ionic compound, wherein the mixture comprises 30g of positive active material TEMPO and 15g of organic ionic compound LiTFSI which are mixed without organic solvent. The total volume of the aqueous electrolyte is 30ml, and the aqueous electrolyte comprises sodium sulfate and zinc sulfate, wherein the concentration of the sodium sulfate is 30g/L, and the concentration of the zinc sulfate is 25 g/L. The benefit of this design is that TEMPO and LiTFSI are present in a mass ratio of 2: the density of the mixture formed by the step 1 is higher than that of the aqueous electrolyte, so that the energy density of the battery is higher, the circulating coulombic efficiency is better, and the safety and the stability of the whole battery are higher. The oxidation state of the active material of the battery anode is TEMPO+The reduced state is TEMPO.
The battery is in a discharge state after being manufactured, the battery needs to be charged firstly, the charging voltage is 1.5V, and the capacity is 3000 mAmp hours. Then the battery can be discharged, the discharge voltage is 1.3V, and the coulombic efficiency is 98%; the charge-discharge capacity is not obviously changed after 1000 cycles.
Example 7
As shown in fig. 5, the battery of example 1 is modified to use two positive electrode current collectors, namely a first positive electrode and a second positive electrode. The negative electrode adopts a uniform zinc negative electrode and is communicated with an external circuit through the bottom of the stainless steel tank. The second positive electrode is responsible for charging the battery, and the current introduced into the second positive electrode enables the surface of the second positive electrode to generate oxidation reaction, so that the oxidation state concentration of the positive electrode active substance in the organic solvent is increased. The first positive electrode is responsible for discharging the battery, and the surface of the first positive electrode is subjected to reduction reaction, so that the oxidation state concentration of the positive electrode active material in the organic solvent is reduced.
A battery was assembled using an organic solvent, a positive electrode active material, an aqueous electrolyte solution, and a negative electrode at the same concentration as in example 1, and a solar power generation device was connected between the second positive electrode and the negative electrode to charge the battery at a charging voltage of 1.9V; the first positive electrode and the negative electrode are connected with an electric load which comprises two motors of the battery and an LED lamp, the battery is discharged, and the discharge voltage is 1.5V; the battery can stably work for 1 year.
The advantage of this design is that the time decoupling of the power generation and the power utilization can be realized, and the electric energy generated at any time can be stored in the battery through the current between the second positive electrode and the negative electrode; the power demand at any time can also be realized by the discharge current between the first positive electrode and the negative electrode, and the power demand can be satisfied as long as the oxidation state of the positive electrode active material in the organic solvent is not completely consumed.
The second positive electrode and the first positive electrode are not directly conducted, and can be independently charged and discharged, so that the charging and discharging switching required in the use process of the traditional battery with only one positive electrode and one negative electrode is avoided, the battery management system is simplified, and the voltage output is smooth. The design is very suitable for reasonable utilization of wind power and solar power generation.
In the above drawings, 1 is a polypropylene liner of a container, which plays an insulating role, 2 is a stainless steel bottom, 3 is a zinc cathode, 4 is an aqueous electrolyte, 5 is a mixed liquid of an organic solvent and a positive active material, 6 is a graphite felt, which has conductivity, 7 is a carbon rod and also has conductivity, 8 is a motor, a conductive slip ring is arranged in the motor, 9 is a graphite felt plated with zinc, and 10 is a rotary oscillator, which can perform rotary motion.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (8)
1. A zinc-organic battery is characterized by comprising a container, wherein the container contains a positive electrode active material, a positive electrode current collector, an organic solvent, a zinc negative electrode and an aqueous electrolyte,
the organic solvent and the aqueous electrolyte are immiscible, have different densities and can be layered under the action of gravity;
the positive active substance has redox activity, has two forms of an oxidation state and a reduction state, can perform reverse conversion through electrochemical reaction, and has different molar ratios of the oxidation state to the reduction state corresponding to different battery charge states;
the positive electrode current collector is used for collecting current at the positive electrode;
the solubility of the oxidation state of the positive electrode active material in the organic solvent is greater than the solubility in the aqueous electrolyte;
or the positive active substance is liquid and is difficult to dissolve in the aqueous electrolyte, and the positive active substance is used as an organic solvent and can be layered with the aqueous electrolyte;
the zinc cathode is soaked in the aqueous electrolyte and is not in contact with the organic solvent;
the aqueous electrolyte is an aqueous solution containing zinc salt;
and, the positive electrode active material is selected from one of four kinds:
first, halogen, an anion formed by a simple halogen or three halogen atoms in an oxidized state, and an ion thereof in a reduced state, including Br2/Br-，I2/I-，Br3 -/Br-，I3 -/I-；
Second, alkyl ferrocene, in the oxidized state, iron is a +3 valent alkyl ferrocene ion, and in the reduced state, iron is a +2 valent alkyl ferrocene;
thirdly, the reduction state of the positive active material is 2,2,6, 6-tetramethyl piperidine oxide TEMPO, the molecular formula is C9H18NO in the oxidation state TEMPO+；
Fourthly, the oxidation state of the anode active material is tetrachloro p-benzoquinone C6Cl4O2Reduced form of the corresponding tetrachlorohydroquinone C6(OH)2Cl4。
2. The zinc-organic battery according to claim 1, further comprising an organic ionic compound for balancing a charge state of the positive electrode active material during charge and discharge to ensure overall charge neutrality, wherein the organic ionic compound is one selected from the following three types:
the first one, lithium bis (trifluoromethanesulfonylimide), LiTFSI, has the molecular formula: (CF)3SO2)2NLi，
Secondly, the molecular formula of the sodium diisooctyl succinate sulfonate AOT is as follows: (COOC)8H17)CH2CH(COOC8H17)SO3Na，
The third one, tetrabutylammonium bistrifluoromethylsulfonyl imide TBATFSI, molecular formula: (CF)3SO2)2N2C16H36。
3. The zinc-organic cell of claim 1, having two or more positive current collectors that are not in direct electrical communication with each other.
4. The zinc-organic battery according to claim 1, wherein the organic solvent is selected from the group consisting of ether solvents, fatty acids and ester solvents,
ether solvents include tetrahydrofuran, 1, 4-dioxane, tetraethylene glycol dimethyl ether;
fatty acids include caproic acid;
the ester solvent includes butyl acetate.
5. The zinc-organic battery of claim 1, wherein the positive current collector is formed of a porous conductive material comprising graphite felt, the positive current collector is located at an interface of the positive active material and the aqueous electrolyte, and the positive current collector is rotatable.
6. The zinc-organic battery according to claim 1, wherein the density of a solution formed by dissolving the positive electrode active material in the organic solvent is lower than that of the aqueous electrolyte, the organic solvent and the positive electrode active material are in an upper layer, the aqueous electrolyte is in a lower layer, the zinc negative electrode is in a lowermost layer, and the zinc negative electrode is immersed in the aqueous electrolyte and is not in contact with the organic solvent.
7. The zinc-organic battery according to claim 1, wherein the density of a solution formed by dissolving the positive electrode active material in the organic solvent is higher than that of the aqueous electrolyte, the organic solvent and the positive electrode active material are in a lower layer, the aqueous electrolyte is in an upper layer, and the zinc negative electrode is suspended in the upper half of the aqueous electrolyte and is not in contact with the organic solvent.
8. The zinc-organic battery according to claim 1, wherein the organic solvent dissolves the positive electrode active material to form a solution having a density higher than that of the aqueous electrolyte, and the container has a plurality of grooves in a bottom thereof, wherein a part of the grooves is filled with the zinc negative electrode, and another part of the grooves is filled with the positive electrode active material and the organic solvent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811645343.8A CN109994785B (en) | 2018-12-30 | 2018-12-30 | Zinc organic battery and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811645343.8A CN109994785B (en) | 2018-12-30 | 2018-12-30 | Zinc organic battery and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109994785A CN109994785A (en) | 2019-07-09 |
| CN109994785B true CN109994785B (en) | 2021-01-19 |
Family
ID=67129929
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811645343.8A Active CN109994785B (en) | 2018-12-30 | 2018-12-30 | Zinc organic battery and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109994785B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111509306B (en) * | 2020-04-26 | 2021-06-25 | 河北大学 | Electrolyte for rechargeable zinc ion battery, preparation method of electrolyte and rechargeable zinc ion battery |
| US11522192B2 (en) | 2020-07-03 | 2022-12-06 | Huazhong University Of Science And Technology | Zinc organic battery and application thereof |
| CN111769278B (en) * | 2020-07-09 | 2022-02-01 | 北京理工大学 | Water system rechargeable zinc ion battery based on aromatic organic matter positive electrode material and application thereof |
| CN112018420B (en) * | 2020-09-13 | 2021-11-12 | 孟锦涛 | Battery and battery system |
| CN112038683B (en) * | 2020-09-14 | 2023-01-24 | 西南大学 | Liquid organic zinc battery and application thereof |
| CN112928341B (en) * | 2021-01-26 | 2022-04-08 | 华中科技大学 | Drum-type half-flow battery and battery pack |
| CN113346147A (en) * | 2021-05-21 | 2021-09-03 | 华中科技大学 | Double-electrolyte secondary battery |
| CN115347207B (en) * | 2022-10-19 | 2023-04-25 | 深圳大学 | Electrolyte of flow battery and preparation method and application thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108574085A (en) * | 2018-03-22 | 2018-09-25 | 复旦大学 | A kind of low temperature Zinc ion battery |
-
2018
- 2018-12-30 CN CN201811645343.8A patent/CN109994785B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN109994785A (en) | 2019-07-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109994785B (en) | Zinc organic battery and application | |
| CN103022577A (en) | Water system chargeable sodium-ion battery | |
| CN101877412A (en) | Organic single flow battery | |
| CN104393353B (en) | A kind of high magnification and long-life fill room temperature sode cell and preparation method thereof | |
| CN106981371A (en) | A kind of water system electrolyte super capacitance cell | |
| CN103268934B (en) | Preparation method of lithium-sulfur battery positive electrode | |
| CN103441259A (en) | Anode material of high-magnification aqueous alkali metal electrochemical battery and preparation method of anode material | |
| CN109920974A (en) | A kind of preparation method and applications of the electrode material coated with gelatin | |
| CN109546134A (en) | The negative electrode material and sodium-ion battery a kind of sodium-ion battery cathode pre- sodium modification method and obtained | |
| CN103441260A (en) | Aqueous alkaline electrochemical energy storage device | |
| CN106549179B (en) | A kind of organic system lithium quinone flow battery | |
| CN107732180A (en) | A kind of preparation method for water system sodium-ion battery anode composite material | |
| CN104064824A (en) | Water system rechargeable battery | |
| CN105655631A (en) | Incombustible sodium secondary battery, electrolyte thereof and application of incombustible sodium secondary battery | |
| CN108493448A (en) | A kind of diachylon of negative electrode of lead carbon battery, preparation method, negative plate of lead-carbon battery and lead carbon battery | |
| CN109742439A (en) | A kind of novel lithium-sulfur cell porous interlayer material, preparation method and application | |
| CN108400292A (en) | A kind of preparation method and applications of bismuth simple substance nanometer sheet combination electrode | |
| JP2019505967A (en) | Redox flow battery electrolyte and redox flow battery | |
| CN108807912A (en) | A kind of C@SnOx(x=0,1,2)The preparation and application of the mesoporous shape hollow nano spherical structures of@C | |
| CN112234195A (en) | Chargeable and dischargeable water system zinc ion full cell | |
| CN108390110B (en) | Lead-manganese secondary battery | |
| CN106654200B (en) | A kind of electrode material, preparation method and the usage | |
| CN113346147A (en) | Double-electrolyte secondary battery | |
| CN104300169B (en) | A kind of Alkaline Zinc vanadium flow battery | |
| CN112952212A (en) | Aqueous manganese dioxide-metal secondary battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20231115 Address after: Room 703, 7th Floor, Building 4, Modern Service Industry Demonstration Base Phase II, Huazhong University of Science and Technology Science Park, No. 15-1 Daxueyuan Road, Guandong Street, Donghu New Technology Development Zone, Wuhan City, Hubei Province, 430223 Patentee after: Juan energy storage Wuhan Technology Co.,Ltd. Address before: 430074 Hubei Province, Wuhan city Hongshan District Luoyu Road No. 1037 Patentee before: HUAZHONG University OF SCIENCE AND TECHNOLOGY |
|
| TR01 | Transfer of patent right |