WO2013048603A1 - Batteries à flux redox comprenant de multiples éléments électro-actifs - Google Patents

Batteries à flux redox comprenant de multiples éléments électro-actifs Download PDF

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WO2013048603A1
WO2013048603A1 PCT/US2012/044117 US2012044117W WO2013048603A1 WO 2013048603 A1 WO2013048603 A1 WO 2013048603A1 US 2012044117 W US2012044117 W US 2012044117W WO 2013048603 A1 WO2013048603 A1 WO 2013048603A1
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electrolyte
positive
negative
redox
stable
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PCT/US2012/044117
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English (en)
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Wei Wang
Liyu Li
Zhenguo Yang
Zimin Nie
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Battelle Memorial Institute
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Priority claimed from US13/246,444 external-priority patent/US9960443B2/en
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Publication of WO2013048603A1 publication Critical patent/WO2013048603A1/fr

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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
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
    • 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

  • a redox How battery stores electrical energy in reduced and oxidized species dissolved in two separate electrolyte solutions.
  • the negative electrolyte and the positive electrolyte circulate through two cell electrodes separated by an ion conducting membrane or separator.
  • Redox flow batteries are advantageous for energy storage because they are capable of tolerating fluctuating power supplies, repetitive charge/discharge cycles at maximum rates, overcharging, overdischarging, and because cycling can be initiated at any state of charge.
  • the present invention includes redox flow battery (RFB) systems having a negative electrolyte, a positive electrolyte, and a membrane between the positive and negative electrol ytes.
  • the systems comprise at least two electrochemical! ⁇ ' active redox elements in the negative electrolyte, the positive electrolyte, or both.
  • the RFB systems embodied by the present invention employ at least two active redox pairs in the negative half cell, the positive half cell, or both half cells.
  • a RFB system comprises a positive hal f cell and a negative hal f cell.
  • the half cells are separated by an ion-conductive membrane or separator.
  • the positive hal f cell contains a positive electrolyte and the negative half cell contains a negati ve electrolyte.
  • the positive electrolyte and negative electrolyte- are solutions comprising eleclrochemical ly active elements in di fferent oxidation states.
  • the electrochemical! ⁇ ' active elements in the positive electrolyte and the negative electrolyte couple as redox pairs.
  • the positive electrolyte/negative electrolyte are continuously circulating through the positive/negative electrodes, respectively, where the redox reactions proceed providing the conversion between electrochemical energy and electrical energy or vice-versa.
  • Positive and negative electrodes are electrically connected through current collectors with the external load to finish the circuit.
  • the positive electrolyte comprises V" " and V" ' as well as Fe 2+ and FV
  • the negative electrolyte comprises V ⁇ " and V ">+ .
  • the relative volumes of the negative electrolyte and positive electrolyte should be selected to appropriately balance the electrochemical reactions.
  • the negative electrolyte volume which contains the common V and V J+ species, should be approximately twice that of the positive electrolyte, which contains V 4 ' and V° ⁇ as well as Fe 2' ' and Fe J+ .
  • the total concentrations of each of the V ⁇ VV 5 *, Fe 7Fe 3 ⁇ V 2 7V ⁇ is greater than 1 .
  • the negative electrolyte and positive electrolyte aqueous solutions can comprise CI ' , SO.f ⁇ or both.
  • the concentration ratio can be between 1 : 10 and 1 0: 1 .
  • the ratio is between 1 :3 and 3 : 1 .
  • the negative electrolyte and positive electrolyte can comprise Cr 2 ' , Cr" , or both.
  • the positive electrolyte can comprise V ' and V '
  • the negative electrolyte comprises Cr 2 ' and Cr J ⁇ as well as V 2' ' and V 3" .
  • the negative electrolyte can comprise Zn and the positive electrolyte can comprise one or more halogens.
  • the negative electrolyte and positive electrolyte can comprise organic, rather than aqueous, solutions.
  • the RFB systems of the present invention can further comprise electrodes in contact with the electrolyte solutions as well as a redox catalyst in the negative electrolyte and/or the positive electrolyte to improve the kinetics of the reduction and/or oxidation reactions.
  • the cell temperature of the RFB system is less than 60 °C during operation without an external temperature control device.
  • the temperature is between -20 °C and 50 °C.
  • a RFB battery system has a membrane separating a negative electrolyte and a positive electrolyte and employs at least two active redox pairs in the RFB positive half cell.
  • the positive electrolyte comprises V " ' + and ⁇ y ⁇ as well as Fe 2" " and FV ⁇
  • the negative electrolyte comprises V 2 " and V j l , and the volume of the negative electrolyte is approximately twice that of the positive electrolyte.
  • the negative electrolyte also comprises Fe 2 ' . but it is not active.
  • the negative electrolyte and positive electrolyte are aqueous solutions comprising CI ' , SO 4 2" . or a mixture of both.
  • Fig. 1 is a graph of current versus voltage comparing all-vanadium RFBs using chloride-containing and siilfate-containing supporting solutions.
  • Fig. 3 compares cyclic performances of vanadium chloride RFB systems and vanadium sulfate RFB systems.
  • 10018 J Fig. 4 compares cyclic voltammetry curves of a vanadium-chloride-sulfaie solution and a vanadium sulfate solution.
  • Fig. 5 is a graph of equilibrium concentrations of chlorine in the positive side of a vanadium-chloride-sulfate cell at various states of charge.
  • Fig. 6 is a diagram depicting structures of VO2 " in sulfuric acid (a) and in hydrochloric acid (b).
  • J Fig. 7 is a graph of cyclic coulombic efficiency, voltage efficiency, and energy efficiency for a vanadium-chloride-sul fate FB system.
  • Fig. 8 are cyclic voltammetry curves in a FcA' and Cl-containing solution using two different electrodes.
  • Fig- 9 contains graphs demonstrating the electrochemical performance of an Fe/V redox flow cell using a Cl-containing supporting solution.
  • Fig. 1 0 shows cyclic Coulombic efficiency, voltage efficiency, and energy efficiency (a) as well as cell charge capacity and charge energy density change (b) for a Fe/V cell employing S-Radel as membrane.
  • Fig. 1 l - 1 I d contains graphs showing the electrochemical performance of a hybrid Fe/V RFB system according to embodiments of the present invention.
  • Fig. 12a- 12c contains graphs showing cycling performance of a hybrid Fe/V RFB system in the voltage window of 1 .1— 1 .7 V .
  • RFBs have been challenges for RFB technologies.
  • One of the main problems facing current RFBs is the intrinsically low energy density compared with other reversible energy storage systems such as lithium-ion batteries. With the voltage limitation of the aqueous systems, this problem has historically been approached by increasing the active species concentration in the electrolyte. However, solubility and stability issues limit the maximum concentration of the active redox ions in the electrolyte solutions.
  • Multi-electron materials and processes can be utilized to meet the need for high energy and high power density.
  • multiple electron transfer from single element is probably difficult to realize due to the narrow voltage window limited by the water electrolysis.
  • the energy density (based on electrolyte only) of a RFB uti lizing multiple electrons thus can be expressed as in the equation I .
  • Equation 1 energy density £ , is expressed in unit volume V (including both positive electrolyte and negative electrolyte), where C, is the concentration of each active redox species and " is the voltage of each redox reaction, /- "' is the Faraday constant, and V is the positive electrolyte volume (using negative electrolyte volume would yield the same result).
  • C is the concentration of each active redox species and " is the voltage of each redox reaction
  • /- "' is the Faraday constant
  • V the positive electrolyte volume (using negative electrolyte volume would yield the same result).
  • Embodiments of the present invention encompass RFB systems utilizing multiple redox pairs in the positive half cell, the negative half cell, or in both.
  • an RFB system can use both V ' VV 3 ' vs. V 2 7V + and Fe 2 7Fe + vs. V 2 V 3+ redox couples.
  • All-vanadium RFB systems and Fe/V RFB systems have each been previously described in detail (see U. S. Patent Application
  • Figures 1-12 show a variety of embodiments and aspects of the present invention.
  • Figures 1-7 show aspects of an all-vanadium RFB system.
  • Figures 8-10 show aspects of an Fe/V RFB system.
  • Figures 11-12 show aspects of a RFB system utilizing multiple redox reactions.
  • Electrochemical reversibility of the V 4T / V ' couple was similar to that of a sulfate system, but that of the V ? : 7 V ' was significantly improved in the chloride system.
  • tiie peak potential difference is 0.351 V in the sulfate system and 0.509 V in the chloride system.
  • the species in the chloride solution forms VO ⁇ C FbO)!.. which is a more stable neutral species than VC CI-bO y]', the species commonly formed in the sulfate solution.
  • V 2r ; V" and V' ⁇ in the chloride solution have a similar structure to that in the sulfate solution.
  • the half cell reaction shown in Eq. (2) lor the positive pole describes well the electrochemistry.
  • the standard potential of this hall " cell reaction is expected to be slightly higher than that of the conventional sulfate system resulting from a different ⁇ /:,r species. By forming this new structure., the thermal stability of the V 5 ⁇ in the chloride solution was significantly improved.
  • - E° 1.0V + a V vs. NHE
  • Chlorine has much higher solubility in water than oxygen; Henry's constant of chlorine and oxygen in water at 25 C C is 0.062 mol/L-atm and 0.0013 moI/L.-atm.
  • the equilibrium potential of Eq. (4) and (5) was calculated for 2.3 M V in 10 i total chloride system, and is shown in Fig.2 (b) as a function of SOC. Based on the data. VO ? 1 is thermodynamically stable from oxygen evolution below an 80% SOC. and from chlorine evolution below a 98% SOC. To maintain saturation of chlorine in the electrolyte solution, the flow battery is preferably operated in a closed system. A closed system is also advantageous to prevent rapid oxidation of V 2+ and V j l' by air and to minimize electrolyte loss.
  • electrode overpotential can contribute to gas evolution.
  • the equilibrium potential of reaction (4) is higher than that of reaction (5 ). but oxygen evolution can be negligible compared to chlorine evolution because of a higher overpotential on the electrode.
  • the chlorine evolution overpotential on a graphite porous electrode was 0. 12 V at 25°C at charge current of 22 mA/cm " for a Zn/Cl battery (see . Watanabe. T. Touhara. New Mat. New Processes. ! ( 1 98 1 ) 62).
  • This overpotential was higher than that of the oxidation reaction in Eq. (2 ) above. Therefore, the chlorine evolution reaction can be negligible except for an SOC of -1 00 %. Because the electrode overpotential of chlorine evolution decreases with increasing temperature, charging is preferably controlled below SOC of 90-95% to prevent chlorine evolution, especially at elevated temperature.
  • V 'V in the sulfate solution exists as a form of
  • V0 2 (I 2 0)3] ' With increasing temperature, this complex decomposed into VO(OH)3 and HjCT. and then VO(OH) 3 is converted into a precipitate of V 2 05 - 3 H 2 0.
  • V " ⁇ is believed to exist as a stable neutral form of V0 2 C1(H 2 0) 2 in the chloride solution. Regardless, the supporting solutions comprising CI " can enable better stability at higher temperature.
  • V 5 ⁇ (V0 2 ⁇ ) 2 8 5 0 -5 Stable (>20 d)
  • the tank containing the electrolyte is preferably insulated to maintain waste heal from the flow battery, which can be approximately 20% of total energy. Operation above the freezing temperature, energy density can be improved by approx imate!)' 35% owi ng to higher vanadium concentration compared to the sul fate system . Stabilization of the V J I species at the lower temperature can be achieved by using a supporting solution containing both SO 4 2" and CI ' , as is described in greater detail elsewhere herein.
  • Typical energy efficiency of vanadium redox flow batteries is about 80%;
  • novel all vanadium chloride flow battery can be stably operated in a comparable energy efficiency to the sulfate system, while delivering energy density of - 38 Wh/L 30 % higher than the sulfate system.
  • Chlorine evolution or V 5 ' ' electrolyte stability in the chloride solution was not an issue under closed operation conditions.
  • Electrolyte for the all vanadium chloride systems described above was prepared by dissolving V2O3 in concentrated HC1 (38%).
  • the electrolyte for the all vanadium sulphate system was fabricated by dissolving VOSO 4 ⁇ 3.8 H 2 0 in sul furic acid (95.8%).
  • the effect of different discharging current densities was evaluated in the first 5 cycles with the same charging current of 50 niA cm 2 .
  • the How cell was charged to 1.7 V and then discharged to 0.8 V.
  • Alter thai the How cell was cycled between 1.6 V and 1.2 V at 50 mA/cm 2 .
  • V 5 ' (VO 2* ) 2 8 5 -5 Stable (>10d)
  • the supportin solution in a VRFB system can comprise CI " either as a SO.] 2" and CI " mixture or comprising Cf as the only anion.
  • the use of mixed SO4 "* and CI " in the supporting solution is not limited to vanadium-based redox How batteries. Chloride and sulfate ions in the supporting solution can help stabilize relatively higher concentrations of other cations as well.
  • J Fig.4 shows the cyclic voltammetry curve of a solution containing 2.5 M VOSO.i and 6 M HQ. This curve is similar to that of a solution containing 1.5 M VOS0 4 and 3.5 M H2SO 4 .
  • Fig.5. the equilibrium concentrations of Ch gas in a vanadium su! ate- chloride positive electrolyte solution (containing 2.5 !vl vanadium.2.5 M sulfate, and 6 !vl chloride) under different stale-of-chargc (SOC) conditions were calculated according to Reaction 12. Under normal Mow battery operation conditions (i.e. T ⁇ 40°C and SOC ⁇
  • the equilibrium concentration of Cl 2 gas is less than 10 ppm. Due to its high solubility in water (0.57 g Cb per 1 00 g water at 30°C). most of the Cb gas generated should be dissolved in the positive electrolyt solutions. At high temperatures, SOC values higher than 80% are preferably avoided to minimize the C gas evolution. Nevertheless, a closed system can be used to minimize continuous Cb gas generation and to prevent Cb gas emission to the environment. Such closed systems are commonly required for the conventional vanadium sulfate flow battery system to prevent oxidation of V 2 r and V j r by Cb in air, and to prevent water loss from electrolyte solutions.
  • V0 2 ' cations, and SO ⁇ 2' anions can help stabilize V J ' cations.
  • Both CI “ and SO 4 2" anions can stabilize V 2 " cations.
  • a sulfuric acid and hydrochloric acid mixture can stabilize high concentrations oi ' all four vanadium cations.
  • Table 5 gives the stability of different V n+ cations in two mixed SO.j 2" and CI " solutions at -5°C to 40°C. Without ' optimization, about 2.5 M of all four V" cations were effectively stabilized in the 2.5 M
  • V J+ was only stable for about 8 days at -5°C. Precipitation of VOCI was observed. Due to the large amount of heat generation during the operation of a VRFB system, it is not difficult to keep the cell temperature of the electrolytes higher than -5 "C even when the ambient temperature is -5 °C or lower. Also, since a VRFB system is always operated under 80 to 90 % state-of-charge and siate-of-discharge conditions, the highest concentration of V JT in a 3 M all vanadium How battery system is 2.7 M (mixing with 0.3 M V 2t ., at the end of 90% discharge) or 2.4 M (mixing with 0.6 V 2' ⁇ at the end of 80% discharge). Therefore, in one embodiment, by using a sulfuric acid and hydrochloric acid mixture as the supporting solution, the VRFB system uses a supporting solution with a total vanadium concentration higher than 3 M.
  • V' specie V" + [Ml IT
  • a diagram depicts the molecular structure of
  • this structure one CI " anion, two O 2" anions, and two H 2 0 molecules complex with one ⁇ /:>T in the first coordination shell.
  • V '1" ' is controlled by the solubility of VOS0 4 .
  • the stability of V j r is controlled by the solubility of VOC1.
  • the improvement of V 4'1" stability is due to the decrease of SO. ' concentration in the solution, and the improvement of V " " ' stabi lity is due to the decrease o f CI " concentration.
  • V 2 t cation is stable in both CI " and S(3 ⁇ 4 2" -containmg solutions.
  • Cell operation conditions 10 cm" flow cell. Charged to 1 .7V by 50 mA/cnr current.
  • the experiment details related to the al l-vanadium RFBs using mixed SO.f — CP supporting solutions are as follows.
  • the flow cells consisted of two graphite electrodes, two gold-coated copper current collectors, two PTFE gaskets, and a National® 1 1 7 membrane. The active area of the electrode and the membrane was about 1 0 cm " .
  • An Arbin battery tester was used to evaluate the performance of flow cells and to control the charging and discharging of the electrolytes.
  • a Solartron 1287 potentiostat was employed for cyclic voltammetry (CV) experiments. The flow rate was fixed at 20 m L/min, which was controlled by a peristaltic pump.
  • a balanced flow cell contained about 50 mL negative electrolyte and 50 m l. positive electrolyte.
  • the cell was nomially charged at a currenl density of 50 mA/cm 2 to 1 .7 V and discharged to 0.8 V with a current density of 25 to 1 00 mA/cm 2 .
  • Cell cycling tests were performed at 90% state-of- charge and state-of-discharge at a fixed charging and discharging current density of 50 mA/cm 2 .
  • V “ ' , V J+ . V' 1 ' ' and V ' used in this work were prepared electrochemically in How cells using VOSC (from Alfa Aesar) and VCI3 as starting chemicals.
  • VCI3 solutions were prepared by dissolving V 7O3 (from Al fa Aesar) in F1C1 solutions.
  • the electrolyte stability tests were carried out in polypropylene tubes at -5°C, ambient temperature. 40°C. 50°C, and 60°C, using about 5 ml solution for each sample. During the stability tests, the samples were kept static without any agitation, and were monitored daily by naked eye for the formation of precipitation. Solution viscosity was measured using a Ubbelohde calibrated viscometer lube.
  • Yet another embodiment of the present invention encompasses a redox flow battery system based on the redox couple of Fe and V.
  • the negative electrolyte comprises V 2 i and V ⁇ in the supporting solution while the positive electrolyte comprises Fe 2 ' and Fe J i in the supporting solution.
  • the Fe/V system of the present invention can provide siyni Meant benefits whi le circumventing some of the intrinsic issues of conventional systems.
  • certain embodiments of the Fe/V system do not use catalysts and/or high-temperature management systems, which add to the complexity and cost of the system.
  • the evolution of l-h gas during charging is minimized since the working potential of V " '7 V " " ⁇ (- 0.25 V) is considerably higher than that of others, such as Cr 2 '7 Cr " (- 0.41 V).
  • the Fe " '7 FV redox couple is electi chemically reversible and can be less oxidative than other common ionic species, such as V 4 ' / V 3 ". which can result in higher stability at high temperatures while avoiding expensive, oxidation-resistant membrane materials, such as sulfonated tetrafluoroethylene based fliioropolymer-copolymer.
  • Figure 8 (a) and (b) show CV results of 1 .5 Fe and V in a 1 VI hydrochloric acid supporting solution using glassy carbon and graphite felt electrode, respectively.
  • the current density is normalized to the geometrical area of the working electrode.
  • Similar CV spectra were observed on both the glassy carbon and graphite fell working electrode with the graphite felt electrode demonstrating higher over potential due to the low conducti vity.
  • Two redox peaks were observed indicating two redox reactions, Fe j r / Fe " ' for the positive and
  • V 2 ' / V J ' for the negative. More importantly, no significant hydrogen evolution current was observed at potentials below the V j r reduction peak, indicating that no significant gas evolution occurred at the negative electrode during the charging process when employing a V 2" / V J+ redox couple. Oxidation and reduction peaks appear in the forward and reverse scans on the positive side, which revealed a reversible redox couple of fV / Fe 2 ' with a potential at approximately 0.5 V. Similarly, there is no anodic current observed associated with evolution of the Cl 2 and/or 0 2 gas. Thus, the Fe ⁇ ' / Fe 2 ⁇ and V JT / V r redox couples in chloride supporting solution can be used in the negative and positive hal f cells according to embodiments of the present invention.
  • FIG. 3 shows the results of Fe/V flow cell testing with a NAF!O 1 1 7 membrane.
  • a plot of cell voltage versus time is given in Fig. 3 (a).
  • Fig. 3 (b) demonstrates the cell voltage profile with respect to the cell capacity and the cell SOC. The SOC is calculated against the maximum charge capacity.
  • a uti lization ratio of close to 100% can be achieved.
  • the Fe/V eel ! demonstrated stable columbic efficiency of -97%, energy efficiency of -78%. and voltage efficiency of - 80% as shown in Fig. 3 (c).
  • the Fe/V cell also demonstrated excellent capacity and energy density retention capabil ity as shown in Fig. 3 (d) with 0. 1 % loss per cycle in charge capacity over 50 cycles.
  • tetrafluoroelhylene based fluoropolymer-copolymer membranes.
  • Suitable alternative membranes can include, but are not limited to. hydrocarbon-based commercially avai lable ion-exchange membranes; for example. SELEMI ON* anion exchange membrane (APS. from Asahi Glass, Japan). SELE ION* cation exchange membrane (C V. from Asahi Glass.
  • S-RADEL® sul ibnated poly(phenylsuibne) membrane
  • micro-porous separators typically used in lithium battery, for example; CELGARD* 8, micro-porous separator (Celgard, USA) .
  • the energy density of Fe/V RFB systems can be improved by using a supporting solution comprising S0 ⁇ 2 ⁇ C1 " mixed ions to increase the reactant concentration in the negative electrolyte and positive electrolyte.
  • a supporting solution comprising S0 ⁇ 2 ⁇ C1 " mixed ions to increase the reactant concentration in the negative electrolyte and positive electrolyte.
  • the solubility of Fe 2 ' and Fe J+ ions * is higher in H 2 SG ⁇
  • One embodiment of a multiple electron RFB system includes a hybrid Fe/V RFB battery.
  • the hybrid Fe/V RFB can comprise both Fe 2"0 ' and V '' l/r " redox couples in positive electrolyte and V " " J+ redox couple and Fe 2 ' in negative electrolyte.
  • the electrolyte of a mixed solution comprising 1 .5M Fe 2 ' , 1 .5M V ' '" ⁇ I .5 SO.f' ⁇ and 3.S. CT : hereafter denoted as l .5Fe/V-3.8HCl : was prepared by dissolving VOSO. ⁇ (Sigma-Aldrich, 99%) and FeCL (Sigma-Aldrich, 98%) in concentrated HCl (Sigma-Aldrich, 37%>) at room
  • FIG. 1 l a - l i d includes a cyclic Voltammeiry (CV) spectrum (a) on glassy- carbon electrode in the 1 .5 Fe/V-3.81 1Cl electrolyte at 10 mV/s scan rate as well as the electrochemical performance of a Fe/V mixed acid redox flow cell with 1 .5Fe/V-3.8HCl electrolyte in each half-cell and NR212 as the membrane.
  • CV Voltammeiry
  • Figure 1 l b shows a Cell-voltage profile with respect to cell capacity during a typical charge/discharge process.
  • Figure 1 l c shows Cyclic Coulombic efficiency (CE). voltage efficiency (VE), and energy efficiency (EE) as a function of cycle number.
  • Figure 1 I d shows variation of specific volumetric capacity and discharge energy density with cycle number.
  • a hybrid RFB system can be constructed with two similar equilibrium cell potentials with that of the V/V and Fe/V redox flow batteries.
  • the voltage plateau at -0.9V during charge and at -0.75V during discharge correspond to the Fe 2 ,' /Fe J+ vs. V ⁇ 7V j l redox couple., while the voltage plateau at—1 .5 V during charge and - 1 .35 V during discharge represent the V' TV 3 ' vs. V 2 7V ' ; redox reaction.
  • Figure 1 l c shows the efficiencies of the Fe/V hybrid cel l with the sulfate- chloride mixed acid electrolyte up to 100 cycles, in which a columbic efficiency of -96%. a voltage efficiency of—83% were achieved leading to an overall energy efficiency of -80%.
  • the Fe/V hybrid How battery also presented excellent capacity retention as shown in the Figure 1 I d with no obvious capacity loss throughout the 1 00 cycles.
  • the discharge energy density representing the ultimate capability of the cell to deliver the useful energy is also plotted in Figure 1 I d. in which approximately 25 Wh/l. of specific volumetric energy density was obtained over 100 cycles of electrochemical cycling. The calculation was based on the total electrolyte volume in both negative and positive hal f cells.
  • the Fe/V hybrid cell Compared with the Fc/V cell using the sul late-chloride mixed acid electrolyte, the Fe/V hybrid cell achieved a >60% increase in the speciiic volumetric energy density attributed to the contribution from the second redox reaction pair.
  • the excellent electrochemical performance of the Fe/V hybrid cel l is attributed to the improved energy density of a flow battery system by util izing multiple electron transfer as discussed previously.
  • the flow cell achieved an average energy density of -23 Wh/L. It is well known that the VRB system often suffered from substantial capacity loss due to several contributing factors, such as hydrogen evolution, air oxidation of V(I I). and the different diffusion rates of the vanadium ions across the membrane., all disturbing the SOC balance between the two half cells causing significant capacity decay. Unexpectedly, by adding an extra redox couple into the cell reaction, the ' Fe/V hybrid flow battery not only attained a relatively higher energy density, but also accomplished stable capacity over extended cycling which enables the system to operate with minimal electrolyte maintenance. It is worth noting that the capacity retention capability of a hybrid redox flow battery can be significantly impacted by alternating the available active redox couples.
  • V " '/V J ' redox couple into the Fe/V flow battery system significantly increases the operational voltage of the system leading to a much improved system energy density, while exhibiting excellent capacity retention capability from the Fe/V system demonstrating hundred cycles of stable cycling without noticeable capacity fading. Consequently'; the fuel utilization ratio in a Fe/V hybrid ilow battery system is much higher than even the Fe/V RFB by exploiting the 'V.V 5 " vs. V 2+ /V 3+ redox couple.
  • the vanadium electrolyte can count for -35% of the system capital cost mainly due to the high and volatile price of the vanadium resource. From a cost perspective, it can therefore be important to compare the different redox (low batteries in terms of the energy performance per unit vanadium source consumed.
  • the energy densities per mole of vanadium of the different vanadium related redox How battery systems are thus listed in the Table 8. Table 8. Energy density per mole of vanadium of the different vanadium related redox flo batteries at the current density of 50mA/cm " . ⁇
  • the Fe/V hybrid flow battery system achieves the highest value representing the most effective use of the vanadium source among the di fferent systems, which is originated from the successful substitution of the V " ' ' 7V ' ' with the low-cost Fe 2 Fe ""' ' .

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Abstract

Introduire de multiples réactions d'oxydoréduction ayant une plage de tension appropriée peut améliorer la densité d'énergie de systèmes de batterie à flux redox (RFB). Un exemple de l'invention comprend des systèmes RFB utilisant de multiples paires redox dans la demi-cellule positive, la demi-cellule négative ou les deux. De tels systèmes RFB peuvent comprendre un électrolyte négatif, un électrolyte positif et une membrane entre l'électrolyte négatif et l'électrolyte positif, au moins deux éléments électrochimiquement actifs existant dans l'électrolyte négatif, l'électrolyte positif ou les deux.
PCT/US2012/044117 2011-09-27 2012-06-26 Batteries à flux redox comprenant de multiples éléments électro-actifs WO2013048603A1 (fr)

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US13/246,444 US9960443B2 (en) 2010-09-28 2011-09-27 Redox flow batteries having multiple electroactive elements
US13/246,444 2011-09-27

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Cited By (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8691413B2 (en) 2012-07-27 2014-04-08 Sun Catalytix Corporation Aqueous redox flow batteries featuring improved cell design characteristics
US8753761B2 (en) 2012-07-27 2014-06-17 Sun Catalytix Corporation Aqueous redox flow batteries comprising metal ligand coordination compounds
ITBO20130635A1 (it) * 2013-11-21 2015-05-22 Delprosens S R L Metodo per misurare lo stato di carica di una batteria a flusso redox, e corrispondente sistema di misura
US9382274B2 (en) 2012-07-27 2016-07-05 Lockheed Martin Advanced Energy Storage, Llc Aqueous redox flow batteries featuring improved cell design characteristics
US9559374B2 (en) 2012-07-27 2017-01-31 Lockheed Martin Advanced Energy Storage, Llc Electrochemical energy storage systems and methods featuring large negative half-cell potentials
US9692077B2 (en) 2012-07-27 2017-06-27 Lockheed Martin Advanced Energy Storage, Llc Aqueous redox flow batteries comprising matched ionomer membranes
US9768463B2 (en) 2012-07-27 2017-09-19 Lockheed Martin Advanced Energy Storage, Llc Aqueous redox flow batteries comprising metal ligand coordination compounds
US9837679B2 (en) 2014-11-26 2017-12-05 Lockheed Martin Advanced Energy Storage, Llc Metal complexes of substituted catecholates and redox flow batteries containing the same
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US9899694B2 (en) 2012-07-27 2018-02-20 Lockheed Martin Advanced Energy Storage, Llc Electrochemical energy storage systems and methods featuring high open circuit potential
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US10253051B2 (en) 2015-03-16 2019-04-09 Lockheed Martin Energy, Llc Preparation of titanium catecholate complexes in aqueous solution using titanium tetrachloride or titanium oxychloride
US10320023B2 (en) 2017-02-16 2019-06-11 Lockheed Martin Energy, Llc Neat methods for forming titanium catecholate complexes and associated compositions
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US10343964B2 (en) 2016-07-26 2019-07-09 Lockheed Martin Energy, Llc Processes for forming titanium catechol complexes
US10377687B2 (en) 2016-07-26 2019-08-13 Lockheed Martin Energy, Llc Processes for forming titanium catechol complexes
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US10644342B2 (en) 2016-03-03 2020-05-05 Lockheed Martin Energy, Llc Coordination complexes containing monosulfonated catecholate ligands and methods for producing the same
US10741864B2 (en) 2016-12-30 2020-08-11 Lockheed Martin Energy, Llc Aqueous methods for forming titanium catecholate complexes and associated compositions
US10930937B2 (en) 2016-11-23 2021-02-23 Lockheed Martin Energy, Llc Flow batteries incorporating active materials containing doubly bridged aromatic groups

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4786567A (en) * 1986-02-11 1988-11-22 Unisearch Limited All-vanadium redox battery
US4814241A (en) * 1986-03-15 1989-03-21 Director-General, Agency Of Industrial Science And Technology Electrolytes for redox flow batteries
US20080292964A1 (en) * 2005-06-20 2008-11-27 George Christopher Kazacos Perfluorinated Membranes and Improved Electrolytes for Redox Cells and Batteries
US20110189549A1 (en) * 2010-01-29 2011-08-04 Samsung Electronics Co., Ltd. Redox flow battery
US20110223450A1 (en) * 2008-07-07 2011-09-15 Enervault Corporation Cascade Redox Flow Battery Systems

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4786567A (en) * 1986-02-11 1988-11-22 Unisearch Limited All-vanadium redox battery
US4814241A (en) * 1986-03-15 1989-03-21 Director-General, Agency Of Industrial Science And Technology Electrolytes for redox flow batteries
US20080292964A1 (en) * 2005-06-20 2008-11-27 George Christopher Kazacos Perfluorinated Membranes and Improved Electrolytes for Redox Cells and Batteries
US20110223450A1 (en) * 2008-07-07 2011-09-15 Enervault Corporation Cascade Redox Flow Battery Systems
US20110189549A1 (en) * 2010-01-29 2011-08-04 Samsung Electronics Co., Ltd. Redox flow battery

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* Cited by examiner, † Cited by third party
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US9865893B2 (en) 2012-07-27 2018-01-09 Lockheed Martin Advanced Energy Storage, Llc Electrochemical energy storage systems and methods featuring optimal membrane systems
US9559374B2 (en) 2012-07-27 2017-01-31 Lockheed Martin Advanced Energy Storage, Llc Electrochemical energy storage systems and methods featuring large negative half-cell potentials
US10483581B2 (en) 2012-07-27 2019-11-19 Lockheed Martin Energy, Llc Electrochemical energy storage systems and methods featuring large negative half-cell potentials
US9382274B2 (en) 2012-07-27 2016-07-05 Lockheed Martin Advanced Energy Storage, Llc Aqueous redox flow batteries featuring improved cell design characteristics
US9899694B2 (en) 2012-07-27 2018-02-20 Lockheed Martin Advanced Energy Storage, Llc Electrochemical energy storage systems and methods featuring high open circuit potential
US9692077B2 (en) 2012-07-27 2017-06-27 Lockheed Martin Advanced Energy Storage, Llc Aqueous redox flow batteries comprising matched ionomer membranes
US9768463B2 (en) 2012-07-27 2017-09-19 Lockheed Martin Advanced Energy Storage, Llc Aqueous redox flow batteries comprising metal ligand coordination compounds
US10707513B2 (en) 2012-07-27 2020-07-07 Lockheed Martin Energy, Llc Aqueous redox flow batteries comprising metal ligand coordination compounds
US10164284B2 (en) 2012-07-27 2018-12-25 Lockheed Martin Energy, Llc Aqueous redox flow batteries featuring improved cell design characteristics
US8753761B2 (en) 2012-07-27 2014-06-17 Sun Catalytix Corporation Aqueous redox flow batteries comprising metal ligand coordination compounds
US8691413B2 (en) 2012-07-27 2014-04-08 Sun Catalytix Corporation Aqueous redox flow batteries featuring improved cell design characteristics
US9991544B2 (en) 2012-07-27 2018-06-05 Lockheed Martin Advanced Energy Storage, Llc Aqueous redox flow batteries comprising metal ligand coordination compounds
US9991543B2 (en) 2012-07-27 2018-06-05 Lockheed Martin Advanced Energy Storage, Llc Aqueous redox flow batteries featuring improved cell design characteristics
US10014546B2 (en) 2012-07-27 2018-07-03 Lockheed Martin Advanced Energy Storage, Llc Aqueous redox flow batteries comprising metal ligand coordination compounds
US10056639B2 (en) 2012-07-27 2018-08-21 Lockheed Martin Energy, Llc Aqueous redox flow batteries featuring improved cell design characteristics
US10651489B2 (en) 2012-07-27 2020-05-12 Lockheed Martin Energy, Llc Electrochemical energy storage systems and methods featuring optimal membrane systems
ITBO20130635A1 (it) * 2013-11-21 2015-05-22 Delprosens S R L Metodo per misurare lo stato di carica di una batteria a flusso redox, e corrispondente sistema di misura
US9837679B2 (en) 2014-11-26 2017-12-05 Lockheed Martin Advanced Energy Storage, Llc Metal complexes of substituted catecholates and redox flow batteries containing the same
US10734666B2 (en) 2014-11-26 2020-08-04 Lockheed Martin Energy, Llc Metal complexes of substituted catecholates and redox flow batteries containing the same
US10253051B2 (en) 2015-03-16 2019-04-09 Lockheed Martin Energy, Llc Preparation of titanium catecholate complexes in aqueous solution using titanium tetrachloride or titanium oxychloride
US10316047B2 (en) 2016-03-03 2019-06-11 Lockheed Martin Energy, Llc Processes for forming coordination complexes containing monosulfonated catecholate ligands
US10644342B2 (en) 2016-03-03 2020-05-05 Lockheed Martin Energy, Llc Coordination complexes containing monosulfonated catecholate ligands and methods for producing the same
US9938308B2 (en) 2016-04-07 2018-04-10 Lockheed Martin Energy, Llc Coordination compounds having redox non-innocent ligands and flow batteries containing the same
US10343964B2 (en) 2016-07-26 2019-07-09 Lockheed Martin Energy, Llc Processes for forming titanium catechol complexes
US10377687B2 (en) 2016-07-26 2019-08-13 Lockheed Martin Energy, Llc Processes for forming titanium catechol complexes
US10065977B2 (en) 2016-10-19 2018-09-04 Lockheed Martin Advanced Energy Storage, Llc Concerted processes for forming 1,2,4-trihydroxybenzene from hydroquinone
US10930937B2 (en) 2016-11-23 2021-02-23 Lockheed Martin Energy, Llc Flow batteries incorporating active materials containing doubly bridged aromatic groups
US10497958B2 (en) 2016-12-14 2019-12-03 Lockheed Martin Energy, Llc Coordinatively unsaturated titanium catecholate complexes and processes associated therewith
US10741864B2 (en) 2016-12-30 2020-08-11 Lockheed Martin Energy, Llc Aqueous methods for forming titanium catecholate complexes and associated compositions
US10320023B2 (en) 2017-02-16 2019-06-11 Lockheed Martin Energy, Llc Neat methods for forming titanium catecholate complexes and associated compositions

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