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WO2019245461A1 - Batterie à flux redox à électrolyte aqueux - Google Patents

Batterie à flux redox à électrolyte aqueux Download PDF

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Publication number
WO2019245461A1
WO2019245461A1 PCT/SG2019/050312 SG2019050312W WO2019245461A1 WO 2019245461 A1 WO2019245461 A1 WO 2019245461A1 SG 2019050312 W SG2019050312 W SG 2019050312W WO 2019245461 A1 WO2019245461 A1 WO 2019245461A1
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Prior art keywords
energy storage
battery according
catholyte
anolyte
storage material
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English (en)
Inventor
Qing Wang
Juezhi YU
Li Fan
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National University of Singapore
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National University of Singapore
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—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
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
    • H01M8/184—Regeneration by electrochemical means
    • H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0002—Aqueous electrolytes
    • 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
    • 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
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • This invention discloses a new flow battery system which comprises an aqueous catholyte, aqueous anolyte, cathodic and anodic energy storage materials in a flow battery apparatus.
  • the cathodic and anodic energy storage materials are statically stored in cathodic and anodic tanks, respectively.
  • the electrolytes are pumped through the battery stacks and tanks of the flow battery apparatus to generate electricity during discharge and store energy during the charging process.
  • a flow battery is generally considered to be a rechargeable fuel cell in which an electrolyte containing one or more dissolved electroactive elements flows through an electrochemical cell that reversibly converts chemical energy directly to electricity. Additional electrolyte is stored externally, generally in tanks, and is usually pumped through the cell (or cells) of the reactor, although gravity feed systems are also known. Flow batteries can be rapidly “recharged” by replacing the electrolyte liquid (in a similar way to refilling fuel tanks for internal combustion engines) while simultaneously recovering the spent material for re-energization.
  • a flow battery is just like an electrochemical cell, with the exception that the electrolyte is not stored in the cell around the electrodes. Rather, the ionic solution is stored outside of the cell, and can be fed into the cell in order to generate electricity. The total amount of electricity that can be generated depends on the size of the storage tanks.
  • redox flow batteries examples include the vanadium redox flow battery, polysulfide bromide battery, and (less typically) a uranium redox flow battery.
  • Such redox flow batteries are generally have a low specific energy and low specific power, which makes them too heavy for use in a vehicle and too expensive for stationary energy storage.
  • Organic redox flow batteries have been developed, which appear to overcome these problems.
  • Organic redox flow batteries could be further classified into two categories: Aqueous Organic Redox Flow Batteries (AORFBs) and Non-aqueous Organic Redox Flow Batteries (NAORFBs).
  • AORFBs use water as solvent for electrolyte materials while NAORFBs employ organic solvents to dissolve redox active materials.
  • NAORFBs employ organic solvents to dissolve redox active materials.
  • these batteries tend to have low power performance.
  • a flow battery system comprising:
  • the liquid anolyte comprises an n-type redox mediator selected from one or more of the group consisting of (NH ⁇ S x and, more particularly, viologens, LhSx, Na2S x , and K2S X , wherein x is less than or equal to 8 and greater than or equal to 1.
  • the solid cathodic energy storage material may be selected from one or more of the group consisting of LiFePCU, Na3V2(PC>4)3, NaFePCU, and Prussian blue (e.g. the solid cathodic energy storage material is LiFePCU);
  • the solid cathodic energy storage material may be provided as granules;
  • the liquid catholyte comprises a p-type redox mediator that may be selected from one or more of the group consisting of ferricyanide (M3Fe(CN)6), ferrocyanide (M4Fe(CN)6), ferrocene (CioHioFe) and derivatives thereof (e.g.
  • M di(ethylsulfonic sodium) ferrocene (Ci4Hi6FeS2C>6Na2)), and iodide (Ml), where in each case M is independently selected from the group consisting of Li, Na, K and NFL , optionally wherein the p-type redox mediator is selected from one or more of the group consisting of, and iodide (Ml) (e.g. ferricyanide (MsFe(CN)e) and/or ferrocyanide (M4Fe(CN)6)), where in each case M is independently selected from the group consisting of Li, Na, K and NFL;
  • Ml e.g. ferricyanide (MsFe(CN)e) and/or ferrocyanide (M4Fe(CN)6)
  • the total concentration of the p-type redox mediator present in the catholyte may be from 0.05 M to 1.5 M, such as from 0.1 M to 1 M, such as from 0.3 M to 0.5 M;
  • the solid anodic energy storage material may be selected from one or more of the group consisting of LiTLiPCLK T1P2O7, and NaTL PCLL (e.g. the solid anodic energy storage material is UTi 2 (PC>4)3);
  • the solid anodic energy storage material may be provided as granules
  • the total concentration of the n-type redox mediator present in the anolyte may be from 0.5 M to 3 M, such as from 0.75 M to 2 M, such as around 1 M;
  • the liquid in the catholyte and anolyte may comprise water alone or in combination with an organic solvent suitable for use in a battery (e.g. the liquid in the catholyte and anolyte may be independently selected from water or water in combination with tetraglyme).
  • the battery provided may be one in which: the solid cathodic energy storage material is LiFePCL; the solid anodic energy storage material is LiTLiPCL the aqueous catholyte comprises K4Fe(CN)6 at a concentration of 0.3 M; and the aqueous anolyte comprises U 2 S2 at a concentration of 1 M.
  • Figure 1 Is a schematic illustration of a redox targeting-based aqueous flow lithium battery full cell
  • the insets show the photograph of LiFePCL and LiTi2(PCL)3 granules with diameter of 1.0 mm and 1.5 mm, respectively.
  • Figure 2. Depicts cyclic voltammograms (CV) of redox mediators and the paired solid Li + - storage materials used in the aqueous RFLB. The CV curves of U2S2 and LiTi 2 (P0 4 ) 3 were measured in 0.1 M LiOH aqueous solution, while those of K 4 [Fe(CN) 6 ] and LiFePCL were obtained in 0.1 M LiOH solution with mixed H2O and TEGDME (30 vol.%). The concentration of the respective redox species is 10 mM and the scan rate are 5 mV s -1 .
  • FIG. 1 Cell performance of single molecule aqueous redox targeting flow batteries (ARTFBs). (a) Charge-discharge profile of the full cell (b) Cycling performance of the full cell.
  • This disclosure provides a rechargeable electrochemical energy storage device, i.e., a redox flow battery system that can be configured for different applications, such as powering portable electronic devices and electrical vehicles, storing energy generated from remote power systems such as wind turbine generators and photovoltaic arrays, and providing emergency power as an uninterruptible power source.
  • a rechargeable electrochemical energy storage device i.e., a redox flow battery system that can be configured for different applications, such as powering portable electronic devices and electrical vehicles, storing energy generated from remote power systems such as wind turbine generators and photovoltaic arrays, and providing emergency power as an uninterruptible power source.
  • a flow battery system comprising:
  • the liquid anolyte comprises an n-type redox mediator selected from one or more of the group consisting of (NH ⁇ S x , viologens, LhSx, Na2S x , and K2S X , wherein x is less than or equal to 8 and greater than or equal to 1.
  • the word“comprising” may be interpreted as requiring the features mentioned, but not limiting the presence of other features.
  • the word“comprising” may also relate to the situation where only the components/features listed are intended to be present (e.g. the word“comprising” may be replaced by the phrases“consists of” or“consists essentially of”). It is explicitly contemplated that both the broader and narrower interpretations can be applied to all aspects and embodiments of the present invention.
  • the word“comprising” and synonyms thereof may be replaced by the phrase“consisting of” or the phrase“consists essentially of’ or synonyms thereof and vice versa.
  • the separator divides the cathode from the anode. It can be an electro-active ion conducting membrane (e.g., a lithium or sodium ion conducting membrane).
  • the separator prevents cross-diffusion of the redox mediator and allows for movement of the electro-active ions (e.g., lithium ions, sodium ions, magnesium ions, aluminum ions, silver ions, copper ions, protons, or a combination thereof).
  • the separator may be a lithium phosphorus oxynitride glass, a lithium thiophosphate glass, sodium phosphorus oxynitride glass, a sodium thiophosphate glass, a NASICON-type lithium conducting glass ceramic, a NASICON-type sodium conducting glass ceramic, a Garnet-type lithium or sodium conducting glass ceramic, a ceramic nanofiltration membrane, a lithium or sodium ion-exchange membrane, or suitable combinations thereof.
  • Both electrodes in the battery system i.e. , the cathode and the anode, can be a carbon, a metal, or a combination thereof.
  • these two electrodes Preferably, these two electrodes have high surface area, with or without one or more catalysts, to facilitate the charge collection process. They can be made of a carbon, a metal, or a combination thereof. Examples of an electrode can be found in Skyllas-Kazacos, et. al., Journal of The Electrochemical Society, 158, R55-79 (2011) and Weber, et. al., Journal of Applied Electrochemistry, 41 , 1137-64 (2011).
  • a flow battery according to the current invention is depicted in Fig. 1 a.
  • a flow battery system that includes a solid cathodic energy storage material 30 stored within a catholyte tank 10.
  • a fluid pathway 50 that runs from the catholyte tank 10 to a cathode 70 and back to the catholyte tank 10 and is intended, which is intended to enable the circulation of a liquid catholyte from the storage tank 10 to the cathode 70 and back again.
  • the cathode 70 is separated from the anode 80 by an ion selective membrane 90 disposed therebetween.
  • a fluid pathway 60 runs from the anode 80 to the anolyte tank 20, which holds a solid anodic energy storage material.
  • the fluid pathway 60 is intended to circulate a liquid anolyte from the storage tank 20 to the anode 80 and back again.
  • a current collector 91 , 92 Surrounding the cathode 70, anode, 80 and membrane 90, is a current collector 91 , 92.
  • the catholyte and anolyte may be circulated through the fluid pathways by any suitable means, such as by use of a suitable pumping system.
  • the anode and cathode may be porous to allow flow of the respective electrolytes.
  • solid cathodic energy storage material refers to a material that can lose alkali metal ions in a charging cycle and regain said alkali metal ions in a discharging cycle of a battery. Any suitable solid cathodic energy storage material may be used in the current invention.
  • the cathodic energy storage material can be a metal fluoride (e.g., CuF 2 , FeF 2 , FeF 3 , B1F 3 , COF 2 , and NiF 2 ), a metal oxide (e.g., Mn0 2 , V 2 O5, V 6 O n , Li 2 0 2 ), ⁇ i- c-z Mi- z R0 4 , (Lii- y Z y )MP0 4 , LiM0 2 , LiM 2 C> 4 , Li 2 MSiC> 4 , a partially fluorinated compound (e.g., UMPO 4 F and LiMS0 4 F, preferably, UVPO 4 F, LiFeS0 4 F), Li 2 Mn0 3 .
  • a metal fluoride e.g., CuF 2 , FeF 2 , FeF 3 , B1F 3 , COF 2 , and NiF 2
  • a metal oxide e.g., Mn0
  • the cathodic energy storage material is a nanostructured material with a flat potential.
  • the porosity, particle size, morphology, and microstructure of the solid cathodic electro-active material can be optimized to ensure an effective redox reaction with a p-type redox mediator in the electrolyte.
  • Suitable materials include Na a [Cu b Fe c Mn d Ni e Ti f M g ]0 2 (where: 0 £ a £ 1 ; 0 £ b £ 0.3; 0 £ c £ 0.5; 0 £ d £ 0.6; 0 £ e £ 0.3; 0 £ f £ 0.2; and 0 £ g £ 0.4, and M is selected from one or more of the group consisting of Mo, Zn, Mg, Cr, Co, Zr, Al, Ca, K, Sr, Li, H, Sn, Te, Sb, Nb, Sc, Rb, Cs, and Na), or more particularly, M-Na 2 Fe 2 (CN) 6 .2H 2 0; R-Na 2 Fe 2 (CN) 6 , NVP, and Na 4 Mn 3 (P0 4 ) 2 (P 2 0 7 ).
  • the solid cathodic energy storage material may be LiFePCL.
  • the solid cathodic energy storage material may be provided in any suitable solid form (e.g. in the form of solid plates or a mesh), the material may be provided in the form of granules. When in the form of granules, the solid cathodic energy storage material may take any suitable size and shape.
  • suitable size may include, but is not limited to, granules having an average diameter of from 0.2 mm to 2 mm, such as from 0.5 mm to 1.5 mm, such as from 0.75 mm to 1.25 mm, such as around 1 mm.
  • the outlet for the liquid catholyte may be smaller than the granules or may include a filter or pores that prevent the solid material from exiting the catholyte tank.
  • the liquid catholyte i.e. the electrolyte in the cathodic portion of the flow battery
  • the liquid catholyte requires the presence of a redox mediator.
  • a redox mediator refers to a compound present (e.g., dissolved) in the electrolyte (catholyte or anolyte) that acts as a molecular shuttle transporting charges between the respective electrodes and the energy storage materials upon charging/discharging.
  • a p-type redox mediator transports charges between the cathodic electrode and the cathodic energy storage material.
  • An n-type redox mediator transports charges between the anodic electrode and the anodic energy storage material.
  • the p- type redox mediator upon charging, the p- type redox mediator is reduced on the surface of the cathodic energy storage material and is oxidized on the surface of the cathodic electrode, and the n-type redox mediator is oxidized on the surface of the anodic energy storage material and is reduced on the surface of the anodic electrode.
  • the reverse processes take place.
  • p-type redox mediator that is compatible with the solid cathodic energy storage material and the solvent used as the electrolyte base liquid may be used.
  • Suitable p-type redox mediators that may be mentioned herein include, but are not limited to ferricyanide (M 3 Fe(CN) 6 ), ferrocyanide (M 4 Fe(CN) 6 ), ferrocene (CioHioFe) and derivatives thereof, iodide (Ml) and combinations thereof, where in each case M is independently selected from the group consisting of Li, Na, K and NH 4 .
  • ferricyanide M 3 Fe(CN) 6
  • ferrocyanide M 4 Fe(CN) 6
  • ferrocene CeoHioFe
  • Ml iodide
  • any suitable concentration of the p- type redox mediators may be used.
  • the total concentration of the p-type redox mediator present in the catholyte may be from 0.05 M to 1.5 M, such as from 0.1 M to 1 M, such as from 0.3 M to 0.5 M.
  • Derivatives of ferrocene that may be mentioned herein include ferrocene derivatives having the structure:
  • X is selected from H, F, Cl, Br, I, NO 2 , COOR, C 1-20 alkyl, CF 3 , and COR, in which R is H or C 1-20 alkyl; n is from 0 to 20.
  • ferrocene examples include but are not limited to bromoferrocene, ferrocenylmethyl dimethyl ethyl ammonium bis(trifluoromethanesulfonyl)imide (Fc1 N1 12-TFSI), A/-(pyridin-2-ylmethylene)-1 -(2- (diphenylphosphino) ferrocenyl) ethanamine (FeCp2PPh2RCN), 1 , 1 - dimethylferrocene (DMFc), tetraferrocene, di(ethylsulfonic sodium) ferrocene (Ci4Fli6FeS206Na2), and di(trimethanesulfonic sodium) ferrocene (Ci6Fl22FeS206Na2).
  • bromoferrocene ferrocenylmethyl dimethyl ethyl ammonium bis(trifluoromethanesulfonyl)imide
  • the derivative of ferrocene may be di(trimethanesulfonic sodium) ferrocene (Ci6H22FeS20eNa2) or di(ethylsulfonic sodium) ferrocene (Ci4Hi6FeS2C>6Na2).
  • solid anodic energy storage material refers to a material that can gain alkali metal ions in a charging cycle and lose said alkali metal ions in a discharging cycle of a battery.
  • Any suitable solid anodic energy storage material may be used in the current invention.
  • Such materials include, but are not limited to a carbon-based material, a silicon-based material, a tin-based material, an antimony-based material, a lead-based material, a metal oxide (e.g. a lithium or sodium metal oxide), a sodium metal, and/or the like, which may be utilized singularly or as a mixture of two or more.
  • the carbon-based material may be, for example, soft carbon or hard carbon or a graphite-based material such as artificial graphite, natural graphite, a mixture of artificial graphite and natural graphite, natural graphite coated with artificial graphite, and/or the like.
  • the silicon-based material may be, for example, silicon, a silicon oxide, a silicon-containing alloy, a mixture of the graphite-based material with the foregoing materials, and/or the like.
  • the silicon oxide may be represented by SiO x (0 ⁇ x£2).
  • the silicon-containing alloy may be an alloy including silicon in the largest amount of the total metal elements (e.g., silicon being the metal element that is present in the largest amount of all the metal elements) based on the total amount of the alloy, for example, a Si-AI-Fe alloy.
  • the tin-based material may be, for example, tin, a tin oxide, a tin-containing alloy, a mixture of the graphite-based material with the foregoing materials, and/or the like.
  • the lithium metal oxide may be, for example, a titanium oxide compound such as Li 4 Ti 5 0i 2 , Li 2 Ti 6 0i 3 or Li 2 Ti 3 07.
  • the sodium metal oxide may be, for example, a titanium oxide compound such as Na 2 Ti 3 0 7 or Na 2 Ti 6 0i 3 .
  • Other metal oxides that may be mentioned herein as suitable include, but are not limited to, T1O2, Fe 2 0 3 , Mo0 3 .
  • Particularly suitable materials that may be mentioned herein include, but are not limited to UTi2(P04) 3 , T1P2O7, and NaTi 2 (P0 4 ) 3 and combinations thereof.
  • the solid anodic energy storage material may be UTi 2 (P0 4 ) 3 .
  • the solid anodic energy storage material may be provided in any suitable solid form (e.g.
  • the material may be provided in the form of granules.
  • the solid anodic energy storage material may take any suitable size and shape. Examples of suitable size may include, but is not limited to, granules having an average diameter of from 0.5 mm to 2.5 mm, such as from 0.75 mm to 2 mm, such as from 1 mm to 1.75 mm, such as around 1.5 mm.
  • the outlet for the liquid anodic may be smaller than the granules or may include a filter or pores that prevent the solid material from exiting the anolyte tank.
  • the liquid anolyte (i.e. the electrolyte in the anodic portion of the flow battery) requires the presence of an n-type redox mediator.
  • n-type redox mediator Any suitable n-type redox mediator that is compatible with the solid anodic energy storage material and the solvent used as the electrolyte base liquid may be used.
  • Suitable n-type redox mediators that may be mentioned herein include, but are not limited to (NFU ⁇ S x O r, more particularly, viologens, LhSx, Na2S x , and K2S X , wherein x is less than or equal to 8 and greater than or equal to 1.
  • any suitable concentration of the n-type redox mediators may be used.
  • the total concentration of the n-type redox mediator present in the anolyte may be from 0.5 M to 3 M, such as from 0.75 M to 2 M, such as around 1 M.
  • Viologens are 1 , 1’-disubstituted 4,4’-bipyridinium ions (where the nitrogen atoms of the pyridine rings are substituted by an alkyl group (e.g. Ci to C12 alkyl)), with a suitable counterion (e.g. Cl ⁇ , F-, Br and h).
  • a viologen of this type is paraquat.
  • viologens may include related compounds, such as diquat and bipolaron.
  • p-type and n-type redox mediators are discussed in depth in international application publication number WO 2013/012391 , which is hereby incorporated by reference.
  • the p-type redox mediators mentioned in said document may be used in the currently disclosed battery system, which mediators are discussed below.
  • the p-type redox mediators disclosed in WO 2013/012391 may be a metallocene derivative, a triarylamine derivative, a phenothiazine derivative, a phenoxazine derivative, a carbazole derivative, a transition metal complex, an aromatic derivative, a nitroxide radical, a disulfide, or a combination thereof.
  • the metallocene derivative used as a p-type redox mediator may have the following structure:
  • M can be Fe, Co, Ni, Cr, or V; each of the cyclopentadienyl rings, independently, can be substituted with one or more of the following groups: F, Cl, Br, I, NO 2 , COOR, C 1-20 alkyl, CF 3 , and COR, in which R can be H or C 1-20 alkyl.
  • the triarylamine derivative used as a p-type redox mediator may have the following structure:
  • each of the phenyl rings can be substituted with one or more of the following groups: F, Cl, Br, I, N0 2 , COOR, C 1-20 alkyl, CF 3 , and COR, in which R can be H or C 1-20 alkyl.
  • the phenothiazine derivative and the phenoxazine derivative used as a p-type redox mediator may have the following structure:
  • R a can be H or C 1-20 alkyl
  • X can be O or S
  • each of the aromatic moieties is optionally substituted with one or more of the following groups: F, Cl, Br, I, NO 2 , COOR, R, CF 3 , and COR, in which R can be H or C 1-20 alkyl.
  • the carbazole derivative used as a p-type redox mediator may have one of the following structures:
  • R x can be H or C1-2 0 alkyl and each of the aromatic moieties is optionally substituted with one or more of the following groups: F, Cl, Br, I, NO2, COOR, C1-2 0 alkyl, CF 3 , and COR, in which R can be H or C1-2 0 alkyl.
  • the transition metal complex used as a p-type redox mediator may have one of the following structures:
  • M can be Co, Ni, Fe, Mn, Ru, or Os; each of the aromatic moieties is unsubstituted or is substituted with one or more of the following groups: F, Cl, Br, I, N0 2 , COOR 1 , R 1 , CF 3 , COR 1 , OR 1 , or NR'R", each R' and R" can independently be H or C1-20 alkyl; each of X, Y, and Z can independently be F, Cl, Br, I, NO2, CN, NCSe, NCS, or NCO; and each Q and W ean independently be selected from:
  • each of R1 , R2, R 3 , R 4 , Rs, and R 6 can be F, Cl, Br, I, NO2, COOR', R', CF 3 , COR', OR', or NR'R".
  • each of the aromatic moieties is optionally substituted with one or more of the following groups: F, Cl, Br, I, NO2, COOR', C1-2 0 alkyl, CF 3 , COR', OR', or NR'R", in which each of R' and R", independently, can be H or C1-2 0 alkyl.
  • each Q and W act as bidentate ligands in the transition metal complex.
  • the aromatic derivative used as a p-type redox mediator may have the following structure:
  • each of R1, R 2 , R 3 , R 4 , R5, and R 6 can be Ci- 2 o alkyl, F, Cl, Br, I, N0 2 , COOR', CFs, COR', OR', OP(OR')(OR"), or NR'R", in which each of R' and R", independently, can be H, Ci- 2o alkyl.
  • the nitroxide radical used as a p-type redox mediator may the following structure:
  • each of Ri and R 2 can be C1-20 alkyl or aryl.
  • R1, R 2 , and N together can form a heteroaryl, heteroaraalkyl, or heterocycloalkyl ring.
  • the disulfide used as a p-type redox mediator may the following structure:
  • each of R1 and R 2 can be Ci- 2o alkyl, COOR', CF 3 , COR', OR', or NR'R", in which each of R' and R", independently, can be H or Ci- 2o alkyl.
  • a suitable solvent is water, which may be used alone or in combination with an organic solvent suitable for use in a battery.
  • Suitable organic solvents that may be mentioned herein include, but are not limited to a glyme solvent, a cyclic carbonate (such as propylene carbonate, ethylene carbonate, diethyl carbonate butylene carbonate, fluoroethylene carbonate, chloroethylene carbonate, vinylene carbonate, and/or the like), a linear carbonate (such as dimethyl carbonate, diethyl carbonate, ethylmethyl carbonate, and the like), a cyclic ester (such as g-butyrolactone, y- valerolactone, and the like), a linear ester (such as methyl formate, methyl acetate, methyl butyrate, and the like), a cyclic or linear ether other than a glyme (such as tetrahydrofuran
  • solvents may be used in any suitable weight ratio with respect to the glyme solvent (e.g. tetraglyme).
  • the additional solvents may be selected from one or more of the group selected from propylene carbonate, ethylene carbonate, diethyl carbonate, dimethyl carbonate, ethyl methyl carbonate, tetrahydrofuran, sulfolane, and acetonitrile.
  • the glyme solvent may be selected from one or more of the group consisting of ethylene glycol dimetheyl ether (monoglyme), diglyme, triglyme, tetraglyme, methyl nonafluorobutyl ether (MFE) and analogues thereof.
  • Analogues of tetraglyme (CH3(0(CH2)2)40CH3) that may be mentioned include, but are not limited to, compounds where one or both of its CH3 end members may be modified to either -C2H5 or to -CH2CH2CI, or other similar substitutions.
  • the glyme solvent is tetraglyme.
  • the solvent used in the catholyte and anolyte may be water alone or water in combination with a glyme solvent (e.g. water and tetraglyme).
  • a glyme solvent e.g. water and tetraglyme
  • the catholyte and anolyte also contain a suitable salt to enable electro-active ions (e.g. Na + and Li + ) to be dissolved in the solvent.
  • the source of the electro-active ion can be a salt of the electro-active ion.
  • Suitable salts for lithium-based systems include LiCICU, UCF3SO3, LiN(S02CF3) 2 , LiN(S0 2 C2F 5 )2, LiN(S0 2 F) 2 , LiC(S0 2 CF 3 ) 3 , Li[N(S0 2 C 4 F9)(S02F)], LiCI, LiBr, Lil, L1NO3, U2SO4, lithium bis(oxalato) borate (i.e.
  • Suitable salts for sodium-based system include NaCICU, NaSCN, NaBr, Nal, Na 2 SC> 4 , Na2BioCho, NaCI, NaNOs, Na 3 P0 4 , Na(CF 3 S0 3 ), NaN(CF 3 S0 2 ) 2 , NaN(FS0 2 ), NaN(C 2 F 5 S0 2 )2,
  • the above materials may be present in a concentration of from 0.5 to 2.5 M within the catholyte and anolyte.
  • the catholyte and anolyte may further include various suitable additives such as a negative electrode SEI (Solid Electrolyte Interface) forming agent, a surfactant, and/or the like.
  • suitable additives may be, for example, succinic anhydride, lithium bis(oxalato)borate, sodium bis(oxalato)borate, lithium tetrafluoroborate, a dinitrile compound, propane sultone, butane sultone, propene sultone, 3-sulfolene, a fluorinated allylether, a fluorinated acrylate, carbonates such as vinylene carbonate, vinyl ethylene carbonate and fluoroethylene carbonate and/or the like.
  • succinic anhydride lithium bis(oxalato)borate, sodium bis(oxalato)borate, lithium tetrafluoroborate, a dinitrile compound, propane sultone, butane sultone, propen
  • the concentration of the additives may be any suitable one that is utilized in a sodium-ion battery.
  • Particular additives that may be included in the electrolyte are those selected from one or more of the group consisting of fluoroethylene carbonate (FEC), vinylene carbonate (VC), vinyl ethylene carbonate (VEC), and adiponitrile.
  • FEC fluoroethylene carbonate
  • VC vinylene carbonate
  • VEC vinyl ethylene carbonate
  • adiponitrile adiponitrile
  • the weight to weight ratio of the solid cathodic energy storage material to solid anodic energy storage material in the battery may be from 1 :2 to 2:1 , such as from 1 : 1.5 to 1 : 1 , such as around 0.9: 1.
  • the volume to volume ratio of the catholyte to anolyte in the battery may be from 1 :2 to 2: 1 , such as from 1 : 1 to 1.9: 1 , such as around 1.75: 1.
  • the catholyte and anolyte tanks, the cathode and anode, the ion selective membrane the current collector and the flow paths used herein may be any conventionally used in the field of flow batteries. No particular limitation is placed on these components.
  • the flow battery disclosed herein may contain:
  • Equation (1) and (2) show the electrochemical reactions on the cathode and anode respectively:
  • [Fe(CN) 6 ] 3 is generated on the cathode by the oxidation of [Fe(CN) 6 ] 4 in the catholyte, which then flows into the cathodic tank and delithiates LiFePCU to form FePCU.
  • the reduced species is regenerated when circulates back to the cell, starting a new round of reactions.
  • S 2_ is formed on the anode by the reduction of S2 2 in the anolyte, which then flows into the anodic tank and lithiates LiTi 2 (P0 4 ) 3 to form LhThCPCU During this process, the Li + ions extracted from LiFePCU in the cathodic tank constantly transport through the Li + -conducting membrane and are stored in UTi 2 (P0 4 ) 3 in the anodic tank. In the discharge process, all the above processes proceed conversely.
  • the batteries when water or water and particular non-flammable organic solvents are used in the flow battery (e.g. tetraglyme), the batteries may be much safer to use;
  • the batteries disclosed herein use an alkaline electrolyte, which is less corrosive than the acidic electrolytes used in vanadium flow batteries;
  • the batteries disclosed herein use solid-state materials to store the electrical energy, which enables them to have a much higher volumetric capacity and energy density that conventional flow batteries.
  • Cyclic voltammetry curves for U2S2 and LiTi 2 (P0 4 ) 3 were obtained using a 0.1 M LiOH aqueous solution.
  • CV curves for K4[Fe(CN)6] and LiFePCL were obtained using a 0.1 M LiOH solution containing H2O and tetraethylene glycol dimethyl ether (TEGDME; present in 30 vol.%).
  • the concentration of the respective redox species was 10 mM and the scan rate was 5 mV s -1 .
  • Olivine LiFePCL and rhombohedral UTi2(PC>4)3 have been shown to be robust cathode and anode materials, respectively, for aqueous lithium ion batteries. Their potentials are relatively flat, which is ideal for redox targeting reactions (e.g. see Fig. 1 b and Fig. 2 versus Hg/HgO), and are well within the electrochemical window of water at alkaline conditions. These two materials were chosen for use as the cathodic and anodic energy storage materials, respectively in the battery described in Example 2.
  • the Cyclic voltammograms in Fig. 2 show the redox potential of LiFePCL is 0.21 V (vs. Hg/HgO) in a 0.1 M LiOH electrolyte, and that of UTi 2 (P04)3 is -0.69 V (vs. Hg/HgO) in a 0.1 M LiOH electrolyte.
  • a cathodic redox mediator that pairs with LiFePCL is [Fe(CN) 6 ] 4 /[Fe(CN) 6 ] 3 .
  • polysulfides are noted to have comparable redox potential to that of UTi 2 (P04)2 ⁇
  • the cell had a discharge voltage of around 0.80 V at a current density of 5 mA cnr 2 , and a capacity of 81 mAh of which 30.9% is contributed by the solid material in the catholyte (Fig. 3a).
  • the cell also had a capacity retention of 94.1 % after 30 cycles (Fig. 3b) and a maximum power density of 8 mW cm 2 at a current density of 20 mA cm 2 .

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Abstract

L'invention concerne une batterie à flux redox comprenant des substances de stockage d'énergie solides dans les réservoirs de stockage de catholyte et d'anolyte, un catholyte liquide, un anolyte liquide comprenant un médiateur redox de type n choisi parmi un ou plusieurs constituants dans le groupe constitué par le (NH4)2SX, les viologènes, le Li2Sx, le Na2Sx, et le K2SX, x étant inférieur ou égal à 8 et supérieur ou égal à 1.
PCT/SG2019/050312 2018-06-22 2019-06-24 Batterie à flux redox à électrolyte aqueux Ceased WO2019245461A1 (fr)

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US11228074B2 (en) 2017-05-19 2022-01-18 Apple Inc. Rechargeable battery with anion conducting polymer
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WO2022173785A1 (fr) * 2021-02-11 2022-08-18 University Of Washington Batteries à flux redox aqueuse comprenant des additifs solides à activité redox
FR3127337A1 (fr) 2021-09-23 2023-03-24 IFP Energies Nouvelles Batteries à circulation avec un négolyte à base de viologène et d’un solvant hydro-alcoolique.
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US11228074B2 (en) 2017-05-19 2022-01-18 Apple Inc. Rechargeable battery with anion conducting polymer
US11888112B2 (en) 2017-05-19 2024-01-30 Apple Inc. Rechargeable battery with anion conducting polymer
US11349161B2 (en) 2017-07-24 2022-05-31 Apple Inc. Rechargeable battery with hydrogen scavenger
US12438238B1 (en) 2017-09-21 2025-10-07 Stacked Energy, Inc. Inter-cell connection materials
US11652230B1 (en) 2018-01-12 2023-05-16 Apple Inc. Rechargeable battery with pseudo-reference electrode
US11296351B1 (en) 2018-01-12 2022-04-05 Apple Inc. Rechargeable battery with pseudo-reference electrode
US11367877B1 (en) 2018-09-19 2022-06-21 Apple Inc. Aqueous battery current collectors
US12074276B2 (en) 2018-11-06 2024-08-27 Quantumscape Battery, Inc. Electrochemical cells with catholyte additives and lithium-stuffed garnet separators
US11189855B1 (en) * 2020-04-22 2021-11-30 Apple Inc. Redox mediators as electrolyte additives for alkaline battery cells
WO2022173785A1 (fr) * 2021-02-11 2022-08-18 University Of Washington Batteries à flux redox aqueuse comprenant des additifs solides à activité redox
WO2023046710A1 (fr) 2021-09-23 2023-03-30 IFP Energies Nouvelles Batteries à circulation avec un négolyte à base de viologène et d'un solvant hydro-alcoolique
FR3127337A1 (fr) 2021-09-23 2023-03-24 IFP Energies Nouvelles Batteries à circulation avec un négolyte à base de viologène et d’un solvant hydro-alcoolique.
WO2023121838A1 (fr) * 2021-11-30 2023-06-29 Quantumscape Battery, Inc. Catholytes pour batterie a l'état solide
US11967676B2 (en) 2021-11-30 2024-04-23 Quantumscape Battery, Inc. Catholytes for a solid-state battery
US11962002B2 (en) 2021-12-17 2024-04-16 Quantumscape Battery, Inc. Cathode materials having oxide surface species
CN118367189A (zh) * 2024-06-20 2024-07-19 天津大学 一种添加固相储能材料的全钒液流电池系统

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