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WO2008128341A1 - Piles à combustible redox à combustible direct - Google Patents

Piles à combustible redox à combustible direct Download PDF

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Publication number
WO2008128341A1
WO2008128341A1 PCT/CA2008/000732 CA2008000732W WO2008128341A1 WO 2008128341 A1 WO2008128341 A1 WO 2008128341A1 CA 2008000732 W CA2008000732 W CA 2008000732W WO 2008128341 A1 WO2008128341 A1 WO 2008128341A1
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WIPO (PCT)
Prior art keywords
fuel
redox
concentration
cathode
methanol
Prior art date
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Ceased
Application number
PCT/CA2008/000732
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English (en)
Inventor
David P. Wilkinson
Khalid Fatih
Alan Illicic
François Girard
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
University of British Columbia
National Research Council of Canada
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University of British Columbia
National Research Council of Canada
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Publication of WO2008128341A1 publication Critical patent/WO2008128341A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8605—Porous electrodes
    • H01M4/8615—Bifunctional electrodes for rechargeable cells
    • 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
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • 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
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
    • H01M8/04197—Preventing means for fuel crossover
    • 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
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1009—Fuel cells with solid electrolytes with one of the reactants being liquid, solid or liquid-charged
    • H01M8/1011—Direct alcohol fuel cells [DAFC], e.g. direct methanol fuel cells [DMFC]
    • 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
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1009—Fuel cells with solid electrolytes with one of the reactants being liquid, solid or liquid-charged
    • H01M8/1011—Direct alcohol fuel cells [DAFC], e.g. direct methanol fuel cells [DMFC]
    • H01M8/1013—Other direct alcohol fuel cells [DAFC]
    • 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 relates to direct-fuel fuel cells and in particular to direct fuel redox fuel cells, their use, and operation.
  • direct-fuel fuel cell One type of fuel cell operating directly on liquid fuel (“direct-fuel fuel cell”) is a direct methanol fuel cell (DMFC).
  • DMFC direct methanol fuel cell
  • fuels that can also be used in a direct-fuel fuel cell, such as ethanol and formic acid.
  • a DMFC is a type of proton exchange membrane fuel cell which uses liquid methanol as a fuel and oxygen as an oxidant. The electrochemical reactions for this type of fuel cell are as follows:
  • Direct-fuel fuel cells like the DMFC have some important advantages over conventional gaseous air / reformate proton exchange membrane (PEM) fuel cells. Such advantages include no separate humidification requirement, no separate cooling requirement, and no fuel processor which can potentially lead to significant simplification of the fuel cell and system.
  • PEM proton exchange membrane
  • Platinum Group Metal (PGM) catalyst loadings used to compensate for poor reaction rate kinetics, are primarily responsible for high cost. Performance issues are related to poor reaction rate kinetics and more importantly fuel crossover from the anode to the cathode, which leads to both a fuel loss and depolarization of the cathode. Practically, this means that only lower concentrations of the fuel can be used (in order to reduce crossover) which reduces the reaction kinetics. Currently, low fuel concentrations or alternative membrane materials are used to help minimize fuel crossover.
  • a method of operating a direct-fuel redox fuel cell comprising: supplying a catholyte to a platinum group metal (PGM)-free cathode of the fuel cell, wherein at least one of the catholyte and cathode includes a redox couple; and supplying an electroactive organic fuel to an anode of the fuel cell at a concentration between a concentration that does not result in fuel cross-over that has more than a 10% negative effect on voltage or a 24 mV voltage loss at any given current density, and a maximum stoichiometric concentration of the fuel.
  • PGM platinum group metal
  • the fuel concentration can be in a range selected from the group consisting of: 2 M and a maximum stoichiometric concentration of the fuel; 4 M and a maximum stoichiometric concentration of the fuel; 6 M and a maximum stoichiometric concentration of the fuel; and 8 M and a maximum stoichiometric concentration of the fuel.
  • the fuel can be selected from the group consisting of electroactive alcohols, electroactive organic acids, and eleectroactive ethers.
  • the fuel can one or combination of: propanol, methanol, formic acid, ethanol, dimethylether, dimethoxymethane, trimethoxy methane, and Trioxane.
  • the fuel can be an aqueous methanol solution in which case the maximum stoichiometric concentration is the equimolar methanol / water stoichiometric amount of 16.7 M.
  • the fuel can be an aqueous formic acid solution in which case the maximum stoichiometric concentration is the equimolar formic acid / water stoichiometric amount of 18 M.
  • the fuel can be pure formic acid in which case the maximum stoichiometric concentration is 26.5 M.
  • the redox couple can be selected from the group consisting of: metal ions, organic redox couples, and complexed metal ions.
  • the redox couple can be selected from the group consisting of: ferrous / ferric ions (Fe +2 / Fe +3 ); Fe(phenanthroline) 3 3+ / Fe(phenanthroline) 3 2+ ; VO 2 + / VO 2+ ; and o-Toluidine (CH 3 C 6 H 4 NH 2 ) / (o-Toluidine) " , and Ce 4+ / Ce 3+ .
  • the method can further comprise the step of regenerating a reduced redox couple using a regenerator selected from the group consisting of: a chemical regenerator, electrochemical regenerator, a photochemical regenerator and combinations thereof.
  • a regenerator selected from the group consisting of: a chemical regenerator, electrochemical regenerator, a photochemical regenerator and combinations thereof.
  • the regenerator can be a chemical regenerator comprising active carbon catalyst.
  • the fuel cell can be operated such that the cathotyte is discharged from the cathode without regeneration of the redox couple.
  • Such application can be found, for example, in single use or
  • the catholyte can comprise an aqueous redox couple catholyte solution. Alternatively or additionally, at least some of the redox couple can be attached to the cathode surface.
  • Another aspect of the invention relates to the use of a direct fuel redox fuel cell at a fuel concentration between a concentration that does not result in a fuel cross-over that has more than a 10% negative effect on overall voltage performance at a given current density, and a maximum stoichiometric concentration of the fuel, wherein the fuel cell comprises a platinum group metal (PGM)-free cathode assembly.
  • the fuel can be selected from the group consisting of methanol, formic acid, ethanol, dimethylether, dimethoxymethane, trimethoxy methane, and Trioxane.
  • FIG. 1 is a schematic of a liquid fuel fed direct methanol redox fuel cell (DMRFC) according to an embodiment of the invention.
  • DMRFC direct methanol redox fuel cell
  • Figures 2 and 3 respectively illustrate the components of a prior art DMFC and the DMRFC of Figure 1 using methanol as the liquid fuel.
  • Figures 4 and 5 respectively illustrate the components of a prior art formic acid fuel cell (FAFC) and a formic acid redox fuel cell (FARFC) using formic acid as the liquid fuel.
  • FAFC formic acid fuel cell
  • FARFC formic acid redox fuel cell
  • Figure 6 is a graph illustrating the effect of fuel concentration on DMFC and DMRFC fuel cell performance.
  • Figure 7 is a graph illustrating the effect of fuel concentration on FAFC and FARFC fuel cell performance.
  • Figure 8 is a schematic of a column reactor for chemically regenerating oxidized redox oxidant.
  • DFRFC direct fuel redox fuel cells
  • the DFRFC is designed to use high concentrations of liquid electroactive organic fuel (e.g. methanol, ethanol, formic acid) without leading to a decrease in performance.
  • liquid electroactive organic fuel e.g. methanol, ethanol, formic acid
  • the DFRFC does not use platinum group metal (PGM) catalyst since redox couples do not require a PGM catalyst at the cathode for acceptable reaction rate kinetics; further, catalytic materials for the redox couple such as carbon are selective to the redox couple only.
  • PGM platinum group metal
  • the DFRFC is embodied in either a single pass type fuel cell wherein the redox couple is passed through the fuel cell once and is not regenerated (e.g. for disposable cartridge applications), or the redox couple is regenerated using regenerators which are tolerant to the high fuel concentrations, such as chemical, photochemical and electrochemical regenerators.
  • the DFRFC can operate using a range of fuel concentrations that would otherwise tend to cause significant cross-over of fuel which would cause a cathode to depolarize in a conventional (non-redox) direct-fuel fuel cell, and to harm micro-organisms in known microbial redox couple regenerators.
  • such higher fuel concentrations can be introduced to improve mass transfer and reaction rate kinetics at the anode without introducing additional complications.
  • the DFRFC 1 can be a direct methanol redox fuel cell (DMRFC) which uses a redox couple for the catholyte in combination with a liquid methanol fuel anolyte.
  • the DMRFC 1 includes an anode assembly 10 containing an anode 12 and an anolyte flow field 14 for flowing an anolyte solution (fuel) to the anode 12; a cathode assembly 16 containing a cathode 18 and a catholyte flow field 20 for flowing a catholyte solution to the cathode
  • PEM 22 sandwiched between the anode 12 and cathode 18. It is noted that although a PEM is used in this embodiment, other types of ionically conductive electrolyte separators can be used, depending on the fuel and as known to one skilled in the art.
  • the anode flow field 14 is a separator plate with a flow channel extending across the face of the separator plate 14 facing the anode 12; the flow channel can have a serpentine configuration as shown in Figure 3, or have another configuration as is known in the art for DMFC anodes.
  • the anode 12 comprises Pt / Ru anode catalyst on porous carbon fiber paper.
  • the PEM 22 can be any suitable membrane known for use with direct fuel cells, and for example, can be a Nafion 117 membrane.
  • the cathode flow field 20 is a separator plate having a recessed pocket in the face of the separator plate facing the cathode 18.
  • the cathode 18 is a sheet of porous carbon fiber paper.
  • the cathode for the redox couple is a non-noble metal material such as carbon, which will not catalyze oxidation of methanol, i.e., it is selective to the redox couple only.
  • the cathode can be made from any suitable chemically inert electrically conducting material as known in the art, such as nickel and stainless steel. To avoid catalytic depolarization, platinum group metals are excluded from the cathode assembly.
  • the anode assembly 10 is provided with a fuel supply manifold (not shown) having an inlet, which supplies aqueous methanol fuel to the flow channels of the anode separator plate 14 and an outlet which removes spent fuel from the anode assembly 10.
  • the cathode assembly 16 is provided with a redox oxidant manifold (not shown) having an inlet which supplies an aqueous redox oxidant to the pocket of the cathode separator plate 20, and an outlet which removes spent redox oxidant from the cathode assembly 16.
  • suitable redox oxidants include metal ions, e.g., Fe +3 , which can be provided as an electrolyte soluble salt, e.g. FeNH 4 (SO 4 ⁇ ⁇
  • Examples of other suitable redox couples are provided later in this description.
  • spent redox oxidant includes reduced oxidant that must be regenerated (oxidized) before being used again in catholyte.
  • the regeneration function could be integrated into the cathode assembly, (to increase gravimetric and volumetric power density) or could be a separate system reactor that is in the recirculation loop of the catholyte for the fuel cell.
  • a chemical regenerator 22 is fluidly coupled to the inlet and outlet of the cathode oxidant manifold and is used to oxidize the redox oxidant that was reduced in the cathode.
  • a suitable chemical regenerator is a column reactor with static packing elements containing catalyst particles, such as Katapak S reactor elements where wire gauze is used to hold small catalyst particles.
  • a suitable catalyst is active carbon that is packed in Katapak S reactor elements.
  • Such a chemical regenerator is operated at an elevated oxygen pressure of 4.7 Bar and temperature of 120 0 C, with a catalyst packing density of 7.1 - 142 Kg catalyst / m 3 .
  • the chemical regenerator 22 can be a batch, continuous slurry and packed bed type reactor.
  • regenerators instead of a chemical regenerator, other types of regenerators or combinations thereof can be used as is known in the art, such as electrochemical regenerators and photochemical regenerators.
  • the industry-accepted upper limit of fuel concentration is about 1 to 2 M methanol in aqueous solution; any higher concentration will result in a rate of methanol cross-over that would depolarize conventional DMFC catalyst and harm micro-organisms in known microbial redox couple regenerators to an extent that makes practical application of DMFC unfeasible.
  • the maximum methanol concentration in a conventional DMFC should be less than 1 M (corresponds to 3
  • the fuel concentration range for the DMRFC 1 of the present embodiment can be between 2 M and 16.7 M.
  • the methanol concentration range for the DMRFC 1 can be one of 4 M to 16.7 M; 6 M to 16.7 M; and 8 M to 16.7 M.
  • the DFRFC 1 can be a direct formic acid redox fuel cell (DFARFC) which uses a redox couple for the catholyte in combination with a liquid formic acid fuel anolyte.
  • DFARFC direct formic acid redox fuel cell
  • the DFARFC 1 includes an anode assembly 10 containing an anode 12 and an anolyte flow field 14 for flowing an anolyte solution to anode; a cathode assembly 16 containing a cathode 18 and a catholyte flow field 20 for flowing a catholyte solution to the cathode, and a PEM 22 [sandwiched between the anode 12 and cathode 18.
  • another type of ionically conductive electrolyte separator could be used for different fuels as is known to one skilled in the art.
  • the DFARFC cathode flow field 20 is a separator plate having a recessed pocket in the face of the separator plate facing the cathode 18.
  • the cathode 18 comprises a multi-layer porous carbon fiber paper.
  • concentrations of liquid fuel up to the stoichiometric amount required for the reaction could be used which would improve performance and the system water requirements.
  • formic acid is used as the liquid fuel
  • stoichiometry permits the use of pure formic acid, and thus the fuel concentration could be as high as 26.5M.
  • a direct fuel redox fuel cell which comprises a single pass catholyte flow field. That is, the redox couple fed into the cathode assembly and reacted at the cathode is not regenerated; the reduced redox oxidant is discharged from the fuel cell. Otherwise, the fuel cell is identical to the embodiments previously described.
  • the fuel cell When employing methanol as the fuel, the fuel cell resembles that shown in Figure 1 and 3, and when employing formic acid as the fuel, the fuel cell resembles that shown in Figure 5.
  • Such a fuel cell is expected to be employed in disposable applications, and can be packaged for example as a single use cartridge that will be discarded once the fuel and oxidant are exhausted.
  • the direct methanol redox fuel cell can be operated at methanol concentrations between 2 M up to the maximum stoichiometric concentration for methanol, or alternatively between one of 2M and 16.7 M,
  • the direct redox fuel cell can be operated with any concentration of formic acid up to the up to 26.5 M with the balance being water or other solvents.
  • DMRFC and DFARFC embodiments as described above are only a few ways to design a direct fuel redox fuel cell. Many possible design variations are possible which would not be possible in conventional fuel cell technology, e.g., the Direct Methanol Fuel Cell, etc. Some possible design variations are as follows:
  • metal ions have mainly been targeted here for the redox system in the DMRFC 1 it is possible to use organic redox couples or complexed metal ions (e.g., metallocenes) which may provide a better selection of voltage potentials, and may prevent or significantly reduce redox crossover to the anode due to steric hindrance effects, etc. One would expect complexation to have some impact on the kinetics of the electron transfer reaction.
  • organic redox couples or complexed metal ions e.g., metallocenes
  • Some types of redox couples include ferrous / ferric ions (Fe +2 / Fe +3 ); Fe(phenanthroline) 3 3+ / Fe(phenanthroline) 3 2+ ; VO 2 + / VO 2+ ; and o- Toluidine (CH 3 C 6 H 4 NH 2 ) / (o-Toluidine) " , and Ce 4+ / Ce 5+ .
  • Exemplary reactions are shown as follows:
  • the redox couple should have adequate solubility in the electrolyte, and the reduction potential should be as high as possible but below the oxidant (for regeneration) reduction potential (e.g., for O 2 ⁇ 1.23 V vs SHE). Also, some of the redox couple types could be attached (fixed) to the electrode surface, e.g., the modified electrode approach.
  • Membrane development and membrane surface functionality could be specific to the DMRFC 1 to prevent fuel and redox species cross-over.
  • Both conventional direct methanol and formic acid fuel cells and direct methanol and formic acid redox fuel cells used an anode separator plate having a serpentine flow channel for flow of an anolyte solution therethrough, an anode having Pt / Ru anode catalyst on carbon fiber paper, and a Nafion 117 PEM.
  • the use and construction of such fuel cell components are well known in the art and not described in detail here.
  • Both conventional direct methanol and formic acid fuel cells used a conventional cathode separator plate having a serpentine flow field and a cathode having Pt cathode catalyst on carbon fiber paper.
  • both the direct methanol and direct formic acid redox fuel cells used a cathode separator plate having a square recess with a depth of 1 mm, and a Pt-free carbon fiber paper cathode placed in the square recess;
  • the DMRFC used a single layer of such carbon fiber paper
  • the DFARFC used a six layer carbon fiber paper cathode.
  • Aqueous methanol fuel solution was supplied to the serpentine flow channel in the anode separator plate for both the conventional DMFC and the
  • Air was supplied to the flow channel in the cathode separator plate for the DMFC and an aqueous ferrous / ferric ion (Fe +2 / Fe +3 ) redox couple catholyte solution was supplied to the recess of the cathode separator plate in the DMRFC.
  • aqueous formic acid fuel solution was supplied to the serpentine flow channel in the anode separator plate for both the conventional DFAFC and the DFARFC. Air was supplied to the flow channel in the cathode separator plate for the DFAFC and an aqueous ferrous / ferric ion (Fe +2 / Fe +3 ) redox couple catholyte solution was supplied to the pocket of the cathode separator plate in the DFARFC.
  • the redox couple was kept at a constant concentration of 0.9 M total Fe. Slightly higher concentrations (1 M) are possible, but precipitation of the electroactive species may be an issue above 0.9M. In general, the concentration range should be less than the limit for saturation and therefore, precipitation.
  • the electrochemical reactions of each system are outlined in Figures 2-5. Half cell reaction potentials are given relative to the Standard Hydrogen Electrode (SHE).
  • Figure 7 illustrates Effect of fuel concentration on DFAFC
  • FAFC Formic Acid Fuel Cell
  • FARFC Formic Acid Redox Fuel Cell
  • the OCV of redox based systems is not negatively affected by high fuel concentrations. Instead, the advantages of using a high fuel concentration are observed through enhanced cell performance, likely as a result of improved reaction kinetics and improved mass transport at the anode. In particular, it is expected that other high fuel concentrations such as: greater than 2 M, 4 M, 6 M, 8 M, 10 M, 12 M, and 14 M will enjoy the performance advantages as found for the 16.7 M CH 3 OH and 18 M HCOOH experiments.
  • the redox based systems reported here are not susceptible to cathode depolarization and can accommodate high fuel concentrations. It has been shown that although conventional systems exhibit a decrease in overall cell performance with increasing fuel concentration, the redox based systems demonstrate improved cell performance at high fuel concentrations. Such systems represent a new type of fuel cell and can employ a wide variety of liquid fuels or redox couples.

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  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Manufacturing & Machinery (AREA)
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Abstract

L'invention divulguée comporte sur des piles à combustible redox à combustible direct employant des concentrations élevées en combustible liquide, par exemple du méthanol, de l'éthanol et de l'acide formique. L'invention concerne une pile à combustible redox à méthanol direct (DMRFC) et une pile à combustible redox à acide formique direct (DFARFC). Le comportement de polarisation de ces deux systèmes est comparé à celui d'une pile à combustible à méthanol direct (DMFC) et à celui d'une pile à combustible à acide formique (FAFC) classiques dans des concentrations en combustible similaires. Il a été observé que les piles à combustible classiques avec des concentrations élevées en combustible liquide souffrent de la traversée du combustible et d'une dépolarisation de la cathode, ce qui conduit à une réduction significative de l'efficacité, tandis que les systèmes à base redox selon l'invention, qui ne contiennent aucun catalyseur de métal noble au niveau de la cathode, ont révélé une amélioration de l'efficacité de la pile avec des concentrations en combustible plus élevées.
PCT/CA2008/000732 2007-04-19 2008-04-18 Piles à combustible redox à combustible direct Ceased WO2008128341A1 (fr)

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US90783507P 2007-04-19 2007-04-19
US60/907,835 2007-04-19

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WO2011107794A3 (fr) * 2010-03-02 2012-01-12 Acal Energy Ltd Piles à combustible
US8722227B2 (en) 2008-06-12 2014-05-13 Massachusetts Institute Of Technology High energy density redox flow device
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EP3213956A1 (fr) * 2008-06-12 2017-09-06 Massachusetts Institute Of Technology Dispositif d'écoulement redox à haute densité d'énergie
US11342567B2 (en) 2008-06-12 2022-05-24 Massachusetts Institute Of Technology High energy density redox flow device
EP2684734A1 (fr) * 2008-06-12 2014-01-15 Massachusetts Institute Of Technology Dispositif d'écoulement redox à haute densité d'énergie
US8722227B2 (en) 2008-06-12 2014-05-13 Massachusetts Institute Of Technology High energy density redox flow device
US8722226B2 (en) 2008-06-12 2014-05-13 24M Technologies, Inc. High energy density redox flow device
US9786944B2 (en) 2008-06-12 2017-10-10 Massachusetts Institute Of Technology High energy density redox flow device
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