JP5580327B2 - バナジウム電池 - Google Patents
バナジウム電池 Download PDFInfo
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- JP5580327B2 JP5580327B2 JP2011537271A JP2011537271A JP5580327B2 JP 5580327 B2 JP5580327 B2 JP 5580327B2 JP 2011537271 A JP2011537271 A JP 2011537271A JP 2011537271 A JP2011537271 A JP 2011537271A JP 5580327 B2 JP5580327 B2 JP 5580327B2
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- vanadium
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- secondary battery
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- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims description 334
- 229910052720 vanadium Inorganic materials 0.000 title claims description 333
- 239000007787 solid Substances 0.000 claims description 275
- 150000003682 vanadium compounds Chemical class 0.000 claims description 161
- 238000007254 oxidation reaction Methods 0.000 claims description 89
- 239000000203 mixture Substances 0.000 claims description 84
- 230000003647 oxidation Effects 0.000 claims description 75
- 239000000243 solution Substances 0.000 claims description 75
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 72
- 239000000126 substance Substances 0.000 claims description 62
- 239000004020 conductor Substances 0.000 claims description 48
- 238000006722 reduction reaction Methods 0.000 claims description 47
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 44
- 229910052799 carbon Inorganic materials 0.000 claims description 43
- 238000004519 manufacturing process Methods 0.000 claims description 33
- VLOPEOIIELCUML-UHFFFAOYSA-L vanadium(2+);sulfate Chemical compound [V+2].[O-]S([O-])(=O)=O VLOPEOIIELCUML-UHFFFAOYSA-L 0.000 claims description 33
- 230000009467 reduction Effects 0.000 claims description 31
- 239000007864 aqueous solution Substances 0.000 claims description 30
- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical compound [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 0.000 claims description 29
- 229910000352 vanadyl sulfate Inorganic materials 0.000 claims description 25
- 229940041260 vanadyl sulfate Drugs 0.000 claims description 24
- 229910001456 vanadium ion Inorganic materials 0.000 claims description 23
- 150000001768 cations Chemical class 0.000 claims description 20
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 19
- 239000004917 carbon fiber Substances 0.000 claims description 19
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 10
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000004744 fabric Substances 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000006228 supernatant Substances 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 3
- 239000002759 woven fabric Substances 0.000 claims description 2
- 229910021550 Vanadium Chloride Inorganic materials 0.000 claims 5
- RPESBQCJGHJMTK-UHFFFAOYSA-I pentachlorovanadium Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[V+5] RPESBQCJGHJMTK-UHFFFAOYSA-I 0.000 claims 5
- NFVUDQKTAWONMJ-UHFFFAOYSA-I pentafluorovanadium Chemical compound [F-].[F-].[F-].[F-].[F-].[V+5] NFVUDQKTAWONMJ-UHFFFAOYSA-I 0.000 claims 4
- 150000001805 chlorine compounds Chemical class 0.000 claims 2
- CRFFKOZWRYKDEG-UHFFFAOYSA-N fluoro hypofluorite vanadium Chemical compound [V].FOF CRFFKOZWRYKDEG-UHFFFAOYSA-N 0.000 claims 2
- 150000004677 hydrates Chemical class 0.000 claims 2
- JIVAUNNAFASXPY-UHFFFAOYSA-N O(OCl)Cl.[V] Chemical compound O(OCl)Cl.[V] JIVAUNNAFASXPY-UHFFFAOYSA-N 0.000 claims 1
- ZHXZNKNQUHUIGN-UHFFFAOYSA-N chloro hypochlorite;vanadium Chemical compound [V].ClOCl ZHXZNKNQUHUIGN-UHFFFAOYSA-N 0.000 claims 1
- 239000011149 active material Substances 0.000 description 131
- 238000000034 method Methods 0.000 description 60
- 150000003839 salts Chemical class 0.000 description 54
- 150000003681 vanadium Chemical class 0.000 description 53
- 239000003792 electrolyte Substances 0.000 description 39
- 239000003014 ion exchange membrane Substances 0.000 description 37
- 238000006243 chemical reaction Methods 0.000 description 29
- 239000000843 powder Substances 0.000 description 28
- 150000002500 ions Chemical class 0.000 description 27
- 210000004027 cell Anatomy 0.000 description 26
- 239000007788 liquid Substances 0.000 description 24
- 238000003860 storage Methods 0.000 description 19
- 239000000499 gel Substances 0.000 description 13
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 12
- 230000008859 change Effects 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 8
- 239000002002 slurry Substances 0.000 description 8
- 229910000351 vanadium(III) sulfate Inorganic materials 0.000 description 8
- OYCGXLKTCYDJNJ-UHFFFAOYSA-H vanadium;trisulfate Chemical compound [V].[V].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OYCGXLKTCYDJNJ-UHFFFAOYSA-H 0.000 description 8
- 238000010586 diagram Methods 0.000 description 7
- 239000012528 membrane Substances 0.000 description 7
- 239000011651 chromium Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000007772 electrode material Substances 0.000 description 6
- 239000008151 electrolyte solution Substances 0.000 description 6
- -1 hydrogen ions Chemical class 0.000 description 6
- 229910052697 platinum Inorganic materials 0.000 description 6
- 230000005587 bubbling Effects 0.000 description 5
- 238000007599 discharging Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 230000003068 static effect Effects 0.000 description 5
- 229910052684 Cerium Inorganic materials 0.000 description 4
- 239000011245 gel electrolyte Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000006479 redox reaction Methods 0.000 description 4
- ZFMRDIPUJPGRCY-UHFFFAOYSA-J vanadium(4+);disulfate Chemical compound [V+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZFMRDIPUJPGRCY-UHFFFAOYSA-J 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- ZMFKXOMVFFKPEC-UHFFFAOYSA-D [V+5].[V+5].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O Chemical compound [V+5].[V+5].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZMFKXOMVFFKPEC-UHFFFAOYSA-D 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 230000002950 deficient Effects 0.000 description 3
- 229940021013 electrolyte solution Drugs 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000011017 operating method Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000007784 solid electrolyte Substances 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229940126062 Compound A Drugs 0.000 description 2
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 239000010432 diamond Substances 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 150000000703 Cerium Chemical class 0.000 description 1
- 229910021555 Chromium Chloride Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- SGKSVUJIDVGBTP-UHFFFAOYSA-L [V+3].[O-]S([O-])(=O)=O Chemical group [V+3].[O-]S([O-])(=O)=O SGKSVUJIDVGBTP-UHFFFAOYSA-L 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 description 1
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 230000007257 malfunction Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- KJDNAUVRGACOHX-UHFFFAOYSA-N sulfuric acid;vanadium Chemical compound [V].OS(O)(=O)=O KJDNAUVRGACOHX-UHFFFAOYSA-N 0.000 description 1
- 125000005287 vanadyl group Chemical group 0.000 description 1
- 239000003643 water by type Substances 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
- 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
- H01M50/497—Ionic conductivity
-
- 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
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T29/00—Metal working
- Y10T29/49—Method of mechanical manufacture
- Y10T29/49002—Electrical device making
- Y10T29/49108—Electric battery cell making
Description
上記目的を達成するために、本発明の一つの実施形態に従うバナジウム電池は、酸化及び還元反応によって2価及び3価の間で酸化数が変化するバナジウム又はそのようなバナジウムを含む固体バナジウム塩若しくは錯塩を含み、負極となる表面を含む第一のバナジウム化合物と、還元及び酸化反応によって5価及び4価の間で酸化数が変化するバナジウム又はそのようなバナジウムを含む固体バナジウム塩若しくは錯塩を含み、正極となる表面を含む第二のバナジウム化合物と、第一及び第二のバナジウム化合物に挟まれ、イオンを選択的に通過させるセパレータと、を含むことを特徴とする。
図1乃至図11を参照しながら、本発明の一つの実施形態に従うバナジウム電池の概要及び製造方法について説明する。
図12乃至18を参照しながら、本発明のある実施形態に従う固体バナジウム・レドックス二次電池の動作特性を別の実施形態に従う固体バナジウム・レドックス二次電池と比較をしながら説明する。
Claims (15)
- 負極を構成し、負極となる表面を含む第一のバナジウム混合物と、
正極を構成し、正極となる表面を含む第二のバナジウム混合物と、
前記第一のバナジウム混合物と前記第二のバナジウム混合物とに挟まれる、セパレータとを含む、固体バナジウム・レドックス二次電池であって、
前記第一のバナジウム混合物が、
少なくとも、酸化又は還元反応によって2価及び3価の間で酸化数が変化する固体の第一のバナジウム化合物を含み、
前記第二のバナジウム混合物が、
少なくとも、還元又は酸化反応によって5価及び4価の間で酸化数が変化する固体の第二のバナジウム化合物を含み、
前記第一のバナジウム化合物は、バナジウムの硫酸塩、バナジウムの塩化物、バナジウムのフッ化物、バナジウムの錯塩及びこれらの水和物からなる群から選ばれる少なくとも1種の化合物から選択され、
前記第二のバナジウム化合物は、バナジウムの硫酸塩、バナジウムの塩化物、バナジウムのフッ化物、バナジウムの錯塩及びこれらの水和物からなる群から選ばれる少なくとも1種の化合物から選択される、固体バナジウム・レドックス二次電池。 - 前記第一のバナジウム化合物及び/又は前記第二のバナジウム化合物が、バナジウムの硫酸塩であり、
前記第一のバナジウム化合物がバナジウムの硫酸塩である場合、
硫酸バナジウム(II)・n水和物及び/又は硫酸バナジウム(III)・n水和物であり、
前記第二のバナジウム化合物がバナジウムの硫酸塩である場合、
硫酸バナジル(IV)、オキシ硫酸バナジウム(IV)・n水和物及びジオキシ硫酸バナジウム(V)・n水和物からなる群から選ばれる少なくとも1種の化合物である、請求項1に記載の固体バナジウム・レドックス二次電池。 - 前記第一のバナジウム化合物及び/又は前記第二のバナジウム化合物が、バナジウムの塩化物であり、
前記第一のバナジウム化合物がバナジウムの塩化物である場合、
塩化バナジウム(II)・n水和物及び/又は塩化バナジウム(III)・n水和物であり、
前記第二のバナジウム化合物がバナジウムの塩化物である場合、
オキシ塩化バナジウム(IV)・n水和物及び/又はジオキシ塩化バナジウム(V)・n水和物である、請求項1又は2に記載の固体バナジウム・レドックス二次電池。 - 前記第一のバナジウム化合物及び/又は前記第二のバナジウム化合物が、バナジウムのフッ化物であり、
前記第一のバナジウム化合物が、バナジウムのフッ化物である場合、
フッ化バナジウム(II)・n水和物及び/又はフッ化バナジウム(III)・n水和物であり、
前記第二のバナジウム化合物が、バナジウムのフッ化物である場合、
オキシフッ化バナジウム(IV)・n水和物及び/又はジオキシフッ化バナジウム(V)・n水和物である、請求項1に記載の固体バナジウム・レドックス二次電池。 - 前記第一のバナジウム混合物及び/又は前記第二のバナジウム混合物が、さらに、硫酸及び/又はシリカを含む請求項1〜4の何れか1項記載の固体バナジウム・レドックス二次電池。
- 前記第一のバナジウム混合物及び/又は前記第二のバナジウム混合物が、高い粘度を有するゲルである、請求項1〜5の何れか1項記載の固体バナジウム・レドックス二次電池。
- 前記第一のバナジウム混合物及び/又は前記第二のバナジウム混合物が、さらに導電性物質を含み、
前記第一のバナジウム化合物及び/又は前記第二のバナジウム化合物が、前記導電性物質の表面に担持されている、請求項1〜6の何れか1項記載の固体バナジウム・レドックス二次電池。 - 前記導電性物質は炭素を含む、請求項7に記載の固体バナジウム・レドックス二次電池。
- 前記導電性物質が、カーボンファイバー、カーボンフェルト、カーボンペーパー、炭素編地、炭素織地及び炭素布からなる群から選ばれる少なくとも1種の材料で構成される、請求項8に記載の固体バナジウム・レドックス二次電池。
- 負極及び/又は正極が、スタック構造を有してなる、請求項1〜9の何れか1項記載の固体バナジウム・レドックス二次電池。
- 請求項1〜4の何れか1項記載の第一のバナジウム化合物又は第二のバナジウム化合物の水溶液に、導電性物質を浸し、前記水溶液を乾燥させるステップを含む、
請求項1〜10の何れか1項記載の固体バナジウム・レドックス二次電池の第一のバナジウム混合物及び/又は第二のバナジウム混合物の製造方法。 - 前記水溶液を、
4価のバナジウムイオン又はバナジウムを4価の状態で含む陽イオンを含む溶液を電解還元又は電解酸化を行うことにより得る、請求項11に記載の固体バナジウム・レドックス二次電池の第一のバナジウム混合物及び/又は第二のバナジウム混合物の製造方法。 - 前記水溶液を酸素を含む環境下に置いた後で、乾燥させる、請求項12に記載の固体バナジウム・レドックス二次電池の第一のバナジウム混合物及び/又は第二のバナジウム混合物の製造方法。
- 前記水溶液の上澄み及び沈殿物を乾燥させる、請求項12に記載の固体バナジウム・レドックス二次電池の第一のバナジウム混合物及び/又は第二のバナジウム混合物の製造方法。
- 請求項11〜14の何れか1項記載の第一のバナジウム混合物及び/又は第二のバナジウム混合物の製造方法を行うステップを有する、固体バナジウム・レドックス電池の製造方法。
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