WO2014197012A1 - Anodes hybrides pour batteries de flux redox - Google Patents

Anodes hybrides pour batteries de flux redox Download PDF

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Publication number
WO2014197012A1
WO2014197012A1 PCT/US2014/015696 US2014015696W WO2014197012A1 WO 2014197012 A1 WO2014197012 A1 WO 2014197012A1 US 2014015696 W US2014015696 W US 2014015696W WO 2014197012 A1 WO2014197012 A1 WO 2014197012A1
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Prior art keywords
electrode
rfb
redox
redox couple
hybrid
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PCT/US2014/015696
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English (en)
Inventor
Wei Wang
Jie Xiao
Xiaoliang Wei
Jun Liu
Vincent L. Sprenkle
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Battelle Memorial Institute Inc
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Battelle Memorial Institute Inc
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Priority claimed from US13/912,516 external-priority patent/US20130273459A1/en
Priority claimed from US14/166,389 external-priority patent/US9214695B2/en
Application filed by Battelle Memorial Institute Inc filed Critical Battelle Memorial Institute Inc
Publication of WO2014197012A1 publication Critical patent/WO2014197012A1/fr
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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
    • H01M12/00—Hybrid cells; Manufacture thereof
    • H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
    • 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
    • H01M4/96—Carbon-based electrodes
    • 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
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/381—Alkaline or alkaline earth metals elements
    • H01M4/382—Lithium
    • 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
    • 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

  • Li-based nonaqueous RFBs which can exhibit high energy density and high energy efficiency, can suffer from relatively unstable anodes that limit the cycle life of the RFB.
  • the anode instability can be caused by dendrite growth and/or failure of the solid electrolyte interface (SEI) layer.
  • Li-based nonaqueous RFBs can operate at current densities that are at least ten times higher than conventional, non-flowing lithium-ion batteries. Therefore, improved energy storage devices with stable electrochemical performance and improved safety are needed to enable devices requiring electrical power as well as those benefitting from efficient energy storage.
  • RFB can refer to a single cell or a stack of cells, wherein each cell comprises a first half cell, a second half cell, and terminals allowing current to flow into and out of the cell.
  • Each half cell can comprise an electrode and/or an electrolyte.
  • a half-cell can further comprise a current collector.
  • the embodiments described herein comprise a first half cell separated by a separator or membrane from a second half cell containing the solid hybrid electrode.
  • the first half cell comprises a first redox couple dissolved in a solution or contained in a suspension.
  • the solid hybrid electrode comprises a first electrode electrically connected to a second electrode, thereby resulting in an equipotential between the first and second electrodes.
  • the electrical connection can be a physical connection by contact and/or through a wire or connector.
  • Some embodiments can further comprise a reservoir containing a supply of the first redox couple dissolved in the solution or contained in the suspension, the reservoir connected to the first half cell via a conduit and a flow regulator.
  • Other embodiments, alternatively or in addition, can further comprise a fluid circulator to induce flow in an electrolyte in the second half cell.
  • equipotential can encompass minor deviations from a theoretical equipotential (i.e., a pseudo-equipotential).
  • the first electrode and second electrode should, in principle, have the same potential. However, in some instances, it can take significant time to reach equilibrium and equal potential. Thus, the potentials of the first and second electrodes may be very close, but may not be quite equal. In preferred embodiments, the potential differences between the first and second electrode is negligible.
  • the first and second electrodes are connected in parallel to function as an electrode.
  • the first and second electrodes can be separated by a separator or membrane or can be exposed directly one to another.
  • the first and second electrodes can be in direct contact or can be separated by some volume.
  • the first and second electrodes remain in contact during operation and not merely prior to initial cycling.
  • the second electrode is not merely an initial source of electroactive metal to be incorporated into the first electrode (i.e., intercalated, deposited, etc.).
  • the first electrode functions as a drain for metal ions and helps to decouple the contamination problem, or undesired reactions, on the second electrode throughout operation of the device.
  • the first electrode comprises a conductive solid material and the second electrode comprises a solid electroactive metal.
  • the first electrode comprises a carbon electrode.
  • carbon electrodes include, but are not limited to, conductive carbon materials such as graphite, hard carbon, carbon black, carbon fibers, graphene, graphite felt, carbon nanotubes, and combinations thereof.
  • the second electrode comprises a solid electroactive metal.
  • solid electroactive metals can include, but are not limited to, Li, Na, K, Zn, Si, Mg, Ca, Al, Sn, Fe, and combinations thereof.
  • the redox couple can comprise a redox active organic, inorganic, or organometallic compound.
  • redox active organic compounds can include, but are not limited to, TEMPO, anthroquinones, DBBB, sulfides, disulfides, polysulfides, nitroxyl radicals, galvinoxyl radicals, carbonyl compounds, quinones and quinone derivatives, TEMPO, metallocenes ferrocenes, carbazoles, tertiary amines, 2,5-di-tert-butyl-l,4-dialkoxybenzenes, quinoxalines, phthalocyanines, porphyrins, pyrazines, and combinations thereof.
  • redox active inorganic compounds can include, but are not limited to, sulfur and sulfur compounds, selenium and selenium compounds, iodides and polyiodides, bromides and polybromides, chlorides and polychlorides, and combinations thereof.
  • the redox active couple in the first half cell comprises polysulfides.
  • the polysulfides can comprise Li x S y , wherein x is from 0 to 4, and y is from 1 to 8.
  • redox active organometallic compounds can include, but are not limited to, ferrocene compounds including structure- modified ferrocene ionic liquids.
  • the first redox couple has a concentration greater than 0.1 M in the liquid solvent. In other embodiments, the first redox couple has a concentration greater than or equal to 0.5 M.
  • the first electrode of the solid hybrid electrode comprises a conductive carbon material and further comprises a metalated carbon during charging and discharging of the RFB.
  • the first electrode comprises metal ions intercalated therein, deposited thereon, or both.
  • the carbon electrode is maintained in a metalated carbon state.
  • Traditional energy storage devices are typically metalated during a charge process but demetalated during a discharge process.
  • loss of metalated carbon from the carbon electrode is compensated by the metal electrode (the second electrode) of the hybrid anode.
  • the carbon electrode can be viewed as a sink to drain metal ions from the metal electrode. Furthermore, in some instances, metal ions can return to the metal anode instead of to the carbon electrode as metalated carbon when charging.
  • a RFB has a first half cell comprising a first redox couple dissolved in a solution or contained in a suspension at a concentration greater than 0.1 M, a second half cell comprising a solid hybrid electrode, and a separator or membrane between the first and second half cells.
  • the solid hybrid electrode comprises a first electrode electrically connected to a second electrode, thereby resulting in an equipotential between the first and second electrodes.
  • the electrical connection can be a physical connection by contact and/or through a wire or connector.
  • the first electrode comprises a conductive solid material and the second electrode comprises Li as an electroactive metal.
  • This document also describes methods of operating an RFB having a first half cell comprising a first redox couple dissolved in a solution or contained in a suspension, a second half cell comprising a solid hybrid electrode, and a separator or membrane between the first and second half cells.
  • the methods comprise operating a first electrode and a second electrode at an equipotential, wherein the hybrid electrode comprises the first connected to the second electrode, the first electrode comprising a conductive solid material and the second electrode comprising a solid electroactive material.
  • the methods can further comprise metalating the first electrode with metal from the second electrode.
  • the second electrode is maintained in a metalated state throughout operation of the energy storage device.
  • the method can comprise extracting metal ions from the second electrode through the metalated material of the first electrode.
  • the method can comprise intercalating metal ions in the second electrode, depositing metal ions on the second electrode, or both.
  • the method can further comprise controllably flowing the first redox couple dissolved in the solution or contained in the suspension from a reservoir to the first half cell via a conduit and a flow regulator, the reservoir containing a supply of the first redox couple dissolved in the solution or contained in the suspension.
  • the method can comprise circulating an electrolyte in the second half cell.
  • Figures 1 A - ID are discharge-charge profiles, cycle stability and Coulombic efficiency plots for traditional Li-S cells at various current rates.
  • Figures 2A - 2C include SEM micrographs of lithium foil anodes after cycling in traditional Li-S cells.
  • Figures 3 A and 3B depict different configurations of hybrid anodes in energy storage devices according to embodiments of the present invention.
  • Figures 4A - 4D are discharge-charge profiles, cycle stability and Coulombic efficiency plots at various current rates for Li-S battery having hybrid anodes according to embodiments of the present invention.
  • Figure 5 is a plot of discharge capacity as a function of cycle number for a Li-S battery having a hybrid anode according to embodiments of the present invention with varying amounts of carbon in the structure.
  • Figures 6A - 6D include SEM micrographs of hybrid anodes before and after operation of Li-S batteries according to embodiments of the present invention.
  • Figure 7 depicts a scheme for reacting a ferrocene to yield a ferrocene ionic liquid according to embodiments of the present invention.
  • Figures 8A - 8C include (a) CV scans of ferrocene and FclNl 12-TFSI in a 1.0 M LiTFSI electrolyte; (b) CV scans of FclNl 12-TFSI in a 1.0 M LiTFSI electrolyte at different scan rates according to embodiments of the present invention.
  • Figures 9A - 9C include plots depicting electrochemical performance of the Li
  • Figures 10A - 10B include plots depicting the cycling performance of the Li
  • FIG. 2A shows the top view of the Li anode after cycling. The surface is covered with a thick passivation layer and is characterized by large cracks caused by electrolyte depletion.
  • Figure 2B reveals that the Li foil became highly porous, consisting of tubular and irregular particles.
  • the cross-sectional SEM micrograph in Figure 2C shows that the passivation layer is more than 100 ⁇ thick. More importantly, at higher magnification, cross-sectional SEM and sulfur elemental mapping indicate an extensive (>100 ⁇ thick) reaction zone where the Li metal is penetrated by sulfur.
  • Embodiments of the present invention can address, at least in part, these problems.
  • the use of the hybrid electrode, according to embodiments described herein can result in the interfacial redox reaction being shifted away from the surface of the electroactive metal.
  • the connection in parallel of the first and second electrodes of the hybrid electrode in one sense, forms a shorted cell where the first electrode is maintained in a metalated form at equilibrium state and also maintains a pseudo-equal potential with the second electrode. As such it functions as a dynamic "pump" that supplies electroactive metal ions as necessary.
  • the first electrode also functions as an effective SEI layer of electroactive metal.
  • the hybrid electrode can be employed in RFBs or in non-flowing cells.
  • a lithium-sulfur RFB employs a first half cell comprising sulfur and/or sulfur compounds flowing through the half cell as a redox couple.
  • the second half cell employs a hybrid anode comprising a graphite electrode and a lithium metal electrode connected with each other.
  • the RFB is configured such that the graphite is in the lithiated state during operation and functions as a dynamic "pump" that supplies Li + ions while minimizing direct contact between soluble polysulfides and Li metal. Therefore, the continuous corrosion and contamination of Li anode during repeated cycling can be largely mitigated.
  • a conductive solid electrode 301 i.e., first electrode
  • an electroactive metal electrode 302 i.e., second electrode
  • a conductive material can be utilized to contact a significant portion or surface of the first electrode.
  • a metal wire cloth can contacting a face of the first electrode can help connect the first and second electrodes.
  • a hybrid anode separator 305 can be placed between the conductive solid and metal electrodes.
  • the separator can be a porous polymeric separator, a porous ceramic separator, or a membrane.
  • the hybrid anode separator can be absent (see Fig. 3B).
  • the first electrode comprises metal ions 306 transferred from the second electrode and intercalated and/or adsorbed at the first electrode. In some instances, a region around the first electrode can develop wherein byproducts can accumulate, deposit and/or contaminate. During discharge, metal ions will move 309 toward the first half cell 303 through a separator 304.
  • the separator can be a ceramic or polymer porous separator or membrane.
  • the first half cell can further comprise a reservoir containing a supply of the first redox couple dissolved in a solvent or contained in a suspension.
  • the reservoir can be fluidly connected to the first half cell via conduits and flow regulators that provide the flowable material from the reservoir in a batch or continuous fashion.
  • Circular arrows 310 depict the shuttling of dissolved ionic species between the anode and cathode. As shown in Figure 3B, the first electrode 301 and the second electrode
  • the conductive solid material of the first electrode will be immediately discharged and will be maintained in the metalated state because the hybrid anode is in one sense a shorted metal/conductive material cell.
  • Figure 4A shows the voltage profiles at different current densities of a non- flowing Li-S cell utilizing a hybrid anode as described herein.
  • the data demonstrates the performance of the hybrid anode.
  • the cell which is not a RFB configuration, includes a cathode comprising sulfur and/or sulfur compounds and a hybrid anode.
  • the hybrid anode comprises a graphite electrode and a lithium metal electrode.
  • the cell delivered a reversible capacity of greater than 900 mAh g "1 at 1.37 A g "1 ( ⁇ 0.8 C). Even at a high rate of 13.79 A g "1 ( ⁇ 8C), more than 450 mA g "1 capacity was demonstrated.
  • FIGS. 4C and 4D compare the long term cycling performance at different current densities along with Coulombic efficiencies of Li-S cells that contain hybrid anodes according to embodiments of the present invention.
  • a significantly improved cycling stability was observed at all rates. For example, at 0.6125 A g "1 , although initial capacity loss is still observed, the capacity becomes extremely stable after 50 cycles, maintaining approximately 850 mAh g "1 for more than 200 cycles (Figure 4C).
  • the Columbic efficiency is also nearly 100% over the entire cycling test due to the absence of overcharging in the cells. Similar performance is further observed at higher discharge rates (see Figure
  • the first electrode is metalated.
  • the graphite electrode can comprise lithiated carbon. Similar metalation of the first electrode can occur in flowing configurations of RFBs described elsewhere herein.
  • the lithiated carbon can be a physical barrier that interferes with the traditional concentration gradient of soluble species in the electrolyte. Physical absorption of polysulfides on the graphite surface reduces further transport of soluble intermediates onto the lithium metal anode. Control cells in which Li foil and graphite electrodes were not connected in parallel, yet were in physical contact, confirm that embodiments of the present invention can minimize the reaction of polysulfides with the Li metal anode.
  • a metalated first electrode can function as a pump to supply electroactive metal ions during discharge.
  • the metalated first electrode in a RFB having hybrid anodes described herein can supply metal ions during discharge.
  • the hybrid electrode has a first electrode comprising graphite and a second electrode comprising Li.
  • the graphite electrode can be lithiated by the lithium electrode.
  • lithiated graphite can function as a dynamic "pump" that continuously drains Li + ions from Li metal reservoir and ejects Li + ions on demand.
  • LiC 6 carbon atoms
  • S moles of carbon atoms
  • the discharge capacity can be determined by LiC 6 on the anode side because Li + ions are mainly provided from LiC 6 as described previously.
  • Three different S:C 6 ratios (all greater than 1/2) were compared and Figure 5 shows that the initial discharge capacity is proportional to the moles of graphite, while the total Li + ions available from Li metal was identical in all cases.
  • the major electrochemical reaction occurs between the cathode, which comprises sulfur and/or sulfur compounds, and the carbon electrode, which comprises LiC 6 , in the hybrid anode.
  • the cathode which comprises sulfur and/or sulfur compounds
  • the carbon electrode which comprises LiC 6
  • a simple non-flowing LiC 6 /S cell using the same sulfur/sulfur compound-containing cathode combined with a prelithated graphite anode shows poor electrochemical performance.
  • the carbon materials have an electrochemical reduction potential very close to Li/ Li + (to facilitate Li + extraction) combined with a low surface area to reduce undesired side reactions with sulfur species.
  • the hybrid electrode in a way that the potential of the first electrode (eg. graphite) is slightly higher or lower than that of the second electrode (metal electrode), so that the first electrode will act as a buffer between the second electrode (metal electrode) and the active species from the positive electrode or electrolyte to avoid the unwanted side reactions.
  • metal ions can diffuse back to the second electrode where they are redeposited.
  • One issue is to determine if the metal ions will preferentially deposit on the second electrode or the metalated portions on the first electrode of the hybrid electrode.
  • SEM micrographs of the Li-graphite hybrid electrode described above are shown in Figure 6. The micrographs exhibit the "as prepared" graphite surface of the hybrid anode ( Figure 6A) and the same surface after 1000 charge/discharge cycles at a 1C rate ( Figure 6B) in a non-flowing Li-S cell. Little morphological change has occurred after extensive cycling yet the surface is rich in sulfur as determined by elemental mapping.
  • a high-performance non-aqueous RFB has a first half cell comprising a redox active organic compound dissolved in an organic liquid supporting solution, a second half cell comprising a hybrid anode having first and second electrodes connected in parallel, and a separator between the first and second half cells.
  • the redox active organic compound comprises a ferrocene (Fc)-based catholyte as a redox couple in an organic liquid supporting electrolyte and the separator comprises a polyethylene-based microporous separator.
  • the hybrid anode has a first electrode comprising graphite felt and a second electrode comprising Li metal.
  • a Li metal anode rather than a hybrid anode, the stability of the RFB is significantly decreased, especially at high concentrations of the first redox couple.
  • a RFB similar to the Li-organic non-aqueous RFB (LORFB) described above that does not utilize the hybrid anode is limited in its performance and cyclability.
  • One LORFB without a hybrid anode achieved a high cell voltage of 3.49 V.
  • the molecular structure of the ferrocene is modified with an IL functional group to increase its solubility. Absent the hybrid anode, to protect the deteriorating dendrite growth on the Li anode surface and to stabilize the solid electrolyte interface (SEI), a fluoroethylene carbonate (FEC) additive was used in the electrolyte.
  • SEI solid electrolyte interface
  • the catholyte of the first half cell in the instant embodiment contained lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) as the supporting electrolyte in a carbonate solvent mixture of ethylene carbonate (EC)/propylene carbonate (PC)/ethyl methyl carbonate (EMC) at a weight ratio of 4:1 :5.
  • LiTFSI lithium bis(trifluoromethanesulfonyl)imide
  • EC ethylene carbonate
  • PC propylene carbonate
  • EMC ethyl methyl carbonate
  • the ferrocene structure was chemically modified to include a polar IL pendant of tetraalkylammonium-TFSI (see Fig. 7), thereafter refered as FclNl 12-TFSI, to increase its solubility in the polar solvent system.
  • the ferrocene-based IL compound (FclNl 12-TFSI) was prepared via a nucleophilic substitution of a commercially available ferrocene derivative, (dimethylaminomethyl)ferrocene (FclNl 1), with bromoethane in acetonitrile, to produce the dimethyl ethyl ferrocenylmethyl ammonium bromide (FclNl 12-Br), followed by exchange of the Br with TFSI in deionized water to afford the final product FclNl 12-TFSI at an overall yield of 91%.
  • a commercially available ferrocene derivative (dimethylaminomethyl)ferrocene (FclNl 1)
  • bromoethane in acetonitrile
  • the resulted FclNl 12-TFSI shows a dramatically enhanced solubility of 1.7 M in the EC PC/EMC solvent system, and of 0.85 M in the electrolyte of 1.2 M LiTFSI in EC/PC/EMC.
  • the FclNl 12-TFSI exhibits well-defined oxidation and reduction potentials of 3.60 V and 3.38 V versus Li/Li + , respectively, yielding a higher half- wave potential (3.49 V) than that of the non-functionalized ferrocene at 3.26 V. Because of the electron- withdrawing effect of the positively charged ammonium pendant (i.e., 1N + 112), the FclNl 12-TFSI shows a 0.23 V positive shift in the redox potential compared to the ferrocene, which benefits the
  • Fc IN 112-TFSI LORFB which did not employ a hybrid electrode, was demonstrated in a laboratory flow cell with a catholyte concentration of 0.1 M FclNl 12- TFSI in 1.0 M LiTFSI in EC/PC/EMC with 5wt% FEC as an SEI-stabilizing additive.
  • FclNl 12-TFSI flow cell in Figure 9A show small discrepancies between the charge and discharge capacities, which indicates that the flow cell features low self-discharge.
  • a fuel utilization ratio of 82% was achieved in a single cell even at a current density as high as 3.5 mA cm "2 .
  • Figure 9C shows the specific capacities and discharge energy density of the 0.1M Li
  • the flow cell exhibited an excellent capability to maintain stable capacity over extended cycling with capacity retention of 95% throughout the 100 cycles.
  • the stable capacity originated primarily from the highly stabilized SEI on the Li anode surface, which suppressed the direct contact between the Li metal and the oxidized ferrocene species (Fc + ) and the corresponding self-discharge reactions.
  • the same flow cell employing a hybrid anode according to embodiments of the present invention exhibited stable cycling.
  • the hybrid anode comprised a graphite felt electrode connected in parallel with a Li foil, wherein the graphite felt and the Li were separated by a Celgard porous separator.
  • a separator can provide improved protection to the SEI layer.
  • the graphite felt electrode can function as the intercalation anode material to minimize lithium metal deposition. Meanwhile, the graphite felt is electrically connected to the Li foil via a stainless steel mesh to harvest the same redox potential of the Li/Li + redox couple.
  • Figures 10A and 10B show the cycling efficiencies, and the volumetric specific capacities and discharge energy density of the 0.8 M Li
  • a relatively stable EE of 76% was achieved despite a gradual increase in the CE (85% to 91%) and drop in the VE (87% to 83%).
  • the flow cell exhibited moderate capacity retention.
  • a volumetric discharge energy density of ⁇ 53 Wh L "1 was delivered in the initial cycles, which is about twice of that of practical VRB systems (-25 Wh L "1 ).
  • the CE at the 0.8 M catholyte concentration is lower due to longer charge/discharge durations yielding more self- discharge, and the VE is also lower due to decreased conductivity of the catholyte solution.
  • Embodiments of the present invention which have a hybrid anode comprising first and second electrodes (e.g., graphite felt and Li metal, respectively) connected in parallel can result in retardation of dendrite formation and proliferation without sacrificing any of the cell potential.
  • first and second electrodes e.g., graphite felt and Li metal, respectively
  • the anode side can be engineered to have static FclNl 12 electrolyte or flowing FclNl 12 electrolyte.

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Abstract

Selon l'invention, des batteries de flux redox (RFB) ayant des électrodes hybrides solides peuvent résoudre au moins les problèmes de consommation de matériau actif, de passivation d'électrode, et de croissance de dendrite d'électrode métallique qui peuvent être caractéristiques de batteries traditionnelles, spécialement celles fonctionnant à des densités de courant élevées. Les RFB possèdent chacune une première demi-cellule contenant un premier couple redox dissous dans une solution ou contenu dans une suspension. La solution ou suspension peut circuler depuis un réservoir vers la première demi-cellule. Une seconde demi-cellule contient l'électrode hybride solide, qui possède une première électrode connectée à une seconde électrode, conduisant ainsi à un équipotentiel entre les première et seconde électrodes. Les première et seconde demi-cellules sont séparées par un séparateur ou une membrane.
PCT/US2014/015696 2013-06-07 2014-02-11 Anodes hybrides pour batteries de flux redox Ceased WO2014197012A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US13/912,516 US20130273459A1 (en) 2012-04-04 2013-06-07 Ionic Conductive Chromophores and Nonaqueous Redox Flow Batteries
US13/912,516 2013-06-07
US14/166,389 US9214695B2 (en) 2012-04-04 2014-01-28 Hybrid anodes for redox flow batteries
US14/166,389 2014-01-28

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US5436093A (en) * 1993-04-30 1995-07-25 California Institute Of Technology Method for fabricating carbon/lithium-ion electrode for rechargeable lithium cell
US20110189520A1 (en) * 2008-06-12 2011-08-04 24M Technologies, Inc. High energy density redox flow device
US20120135278A1 (en) * 2009-06-09 2012-05-31 Tomohisa Yoshie Redox flow battery
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Title
WEI WANG ET AL.: "Anthraquinone with tailored structure for a nonaqueous metal-organic redox flow battery", CHEMICAL COMMUNICATIONS, vol. 48, no. 53, 2012, pages 6669 - 6671, XP055163586, DOI: doi:10.1039/c2cc32466k *

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