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WO2012161917A1 - Batterie à flux - Google Patents

Batterie à flux Download PDF

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Publication number
WO2012161917A1
WO2012161917A1 PCT/US2012/035165 US2012035165W WO2012161917A1 WO 2012161917 A1 WO2012161917 A1 WO 2012161917A1 US 2012035165 W US2012035165 W US 2012035165W WO 2012161917 A1 WO2012161917 A1 WO 2012161917A1
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WIPO (PCT)
Prior art keywords
battery
flow battery
anolyte
electrode structure
catholyte
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English (en)
Inventor
Nie Luo
Ji Cui
Lizhang Yang
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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
    • H01M8/20—Indirect fuel cells, e.g. fuel cells with redox couple being irreversible
    • 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
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9041—Metals or alloys
    • 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
    • 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

  • the invention relates to storage of electricity in a redox flow electrochemical cell.
  • the redox pairs of the cell are partly or all from the different reduction/oxidation states of complexed metal ions selected from late 3d transition metals of low cost.
  • Reflow battery is one such kind of high potential energy storage device.
  • Figure 1 demonstrates an exemplary structure of a flow battery according to the present invention (in which reference 1 represents a membrane or diaphragm; reference 2 represents a redox species in catholyte; reference 3 represents an electric current collector plate; reference 4 represents conducting porous materials; reference 5 represents a catholyte; and reference 6 represents an anolyte).
  • Figure 2 demonstrates an exemplary structure of a flow battery based on Mn ions (in which reference 1 represents ion exchange membrane; reference 2 represents a redox species in catholyte; reference 3 represents an anolyte; reference 4 represents a catholyte; reference A represents electrode structure A; and reference B represents electrode structure B.
  • reference 1 represents ion exchange membrane
  • reference 2 represents a redox species in catholyte
  • reference 3 represents an anolyte
  • reference 4 represents a catholyte
  • reference A represents electrode structure A
  • reference B represents electrode structure B.
  • Figure 3 is a graph showing a charging/discharging curve of an all Mn based reflow battery.
  • Figure 4 is a graph showing a charging/discharging curve of Fe(CN)-Br 2 reflow battery.
  • Figure 5 is a graph showing a charging/discharging curve of Cu(NH 3 )-Br 2 reflow battery.
  • Reflow battery (or “flow battery”) is also called redox reflow battery. It is a type of battery that uses separate flow of anolyte and catholyte, through battery stack to generate electricity or store electricity.
  • Anolyte and catholyte are the electrolytes in the anode compartment and cathode compartment, respectively. They are also referred to as working solutions.
  • the starting chemical composition of catholyte and anolyte can be the same or can be different.
  • Redox is an abbreviation for oxidation and reduction, which are
  • Complexes also called coordination compounds or chelating complexes, are a type of chemical compounds that consist of atoms or ions in the center and ligand molecules or ions at its surroundings. The chemical bond between the center and ligand is partial or complete coordination bond.
  • One typical example is copper(I) ion complex with ammonia molecule (NH 3 ).
  • NH 3 ammonia molecule
  • Transition metals are the elements located in d block of periodic table.
  • the group number that is assigned to the metal corresponds to the filling of d orbital, from s2dl (group II) to s2d9 (group XI).
  • Late 3d transition metals refer to the group of elements consisting of Mn, Fe,
  • the cathode In electrochemical cell, the cathode is the electrode where reduction occurs when battery is discharging and the anode is the electrode where oxidation occurs when battery is discharging, cathode has high electrode potential and anode has lower electrode potential.
  • the cathode is also called positive electrode and anode negative electrode.
  • Electrode current collector is also referred to as a biopolar plate. It is formed from the anode of one single battery cell fused with the cathode of another single battery cell. Its main function is to provide structure support and to conduct current.
  • Periodation threshold refers to the minimum concentration of particles above which a continuous pathway can be fromed from one electrode to another electrode. Usually the particles have random dispersion in a medium, but they can also be processed to be aligned or to induce low order to control local concentration, particle orientation, inter particle interaction etc. Filler can be a single substance or a mixture of many.
  • Mean particle size D50 is a value describing the size of particles. It refers to the diameter of the particle that corresponds to accumulative numeric distribution of 50%. Its physical meaning is that 50% of particle are bigger than this value and 50% particles are smaller than this value (percentage can be number percentage or volume percentage). For non-spherical shape particles, the diameter refers to the diameter of a particle that has equal volume to the d50 particle.
  • Redox materials are a combination of high and low oxidation state of the same materials.
  • Cu(II) which stands for plus two valent copper ion or Cu 2+
  • Cu(I) which stands for plus one valent copper ion or Cu +
  • the form of high or low oxidation state element can exist in the forms of neutral molecule or ions, such as complexes formed between the ions and water, hydroxide, oxygen containing ligand, nitrogen containing ligands.
  • Mn 7+ /Mn 6+ Mn 7+ exists in the form of permanganate MnO 4 -, and Mn 6+ exist in the form of manganate Mn0 4 2 .
  • Cu 2+ /Cu + Cu 2+ and Cu + can exist in the form of their complexes with water, ammonia, and ligands, and mixture of ligands.
  • redox pairs refer to both coordinated or non-coordinated metal ion redox pair, unless otherwise specified.
  • Ligand refers to a type of compounds that can form coordination complexes with any one of the late 3d transition elements.
  • the ligand comprises one or more functional groups: organic amino (primary, secondary, or tertiary amino groups, aromatic or non-aromatic amino groups), phosphonate, thioalcohol, phosphate, hydroxyl, ammonia (NH 3 ), or can be selected from a group consisting of bromide, chloride, fluoride, iodide, and cyanide.
  • water and hydroxides can also be ligands, however, due to the ubiquitous nature of water and hydroxides, they are not considered as ligand in the present disclosure.
  • Ligand can be mono-dentate or multi-dentate. Examples of multi- dentate ligand include 2, 2'- bispyridine, oxalate, citrate, EDTA. Multi-dentate ligand can also takes the form of a ring such as crown ether.
  • Ligand coordinated metal ions generally take the form of the following formula [M(X)(L) s ] a+ , where M is a metal, X is the valence state denoted in roman numeric numbers I, II, III, etc, L is the ligand which can be anions or neutral molecules, s is an integer selected from 2-6, and a is the total charge of this coordination complex.
  • This formula also describes the mixed ligand coordination complex wherein the L can be chosen from more than one type of ligand molecules. When more than one valence states are involved, such as between Fe(III) and Fe(II), they form ligand coordinated redox pair.
  • carboxylate or “phthalate”, or “salicylate” include “carboxylic acid”, “phthalic acid” or “salicylic acid”, respectively, and denote both free acid and salt forms of the ligands.
  • Redox pairs formed by halogens of different oxidation states refer to redox pair among zero valence halogen, minus one valence halogen and halogen oxyacids.
  • the zero valence halogen include chlorine, bromine, iodine, and interhalogen compounds having the formula of [X n Y m ] w , in which each of X and Y is CI, Br, or I, X can be equal to Y; n and m are integers from 1-6, w is the total charge, usually from -3 to 0.
  • Halogen oxyacids have the general formula: [XO p ] _1 , in which p is an integer from 1-4, and X is CI, Br or I.
  • an electrochemical flow battery which comprises an electrode structure A, an electrode structure B, a catholyte, an anolyte, and characterized in that:
  • said anolyte is in contact with electrode structure B, and the said anolyte is based on one or a mixture of the following ligand-coordinated redox pair:
  • said battery has a separating membrane or an ion exchange membrane, spatially positioned in between the electrode structure A and B;
  • the catholyte or anolyte according to present invention has hydroxide anions in the concentration range of 10 ⁇ 10 -30 mol/L, preferably at 10 ⁇ 2 -30 mol/L.
  • the catholyte according to present invention contains at least one of the following redox pairs: coordinated or non-coordinated Cu 3+ /Cu 2+ , coordinated or non-coordinated Mn 7+ /Mn 6+ , those formed by halogens of different oxidation states, those formed by halogen oxy acids of different oxidation states.
  • Mn, Fe, and Cu are chosen as anolyte redox species to lower the materials cost for the battery.
  • Mn, Cu, and Fe are currently priced at 1/10, 1/4, and 1/30 of V, respectively.
  • the three elements are widely abundant in earth's crust and have multiple valence state. All three elements have excellent redox properties and are beneficial for energy storage batteries.
  • current invention focuses on these three metals, the concept of using ligands with metal ions can be applied to other metals as well.
  • the anolyte according to present invention is chosen from late 3d transition metals, that is, Mn, Cu, and Fe. Accordingly, the following anolyte design can be implemented.
  • the anolyte can be based on Mn redox species including the following redox pair : Mn 3+ /HMn0 2 Mn 3+ /Mn 2+ ,
  • the anolyte can also contain at least one ligand and said ligand can form coordination compounds with the Mn species mentioned above.
  • the anolyte can be in contact with electrode structure B.
  • the anolyte can be based on Cu 2+ /Cu + or Fe 3+ /Fe 2+ , and the anolyte can be in contact with electrode structure B.
  • a mixture of redox species can be used for anolyte, such as mixing two of the three following redox pairs in one anolyte solution: Mn /Mn , Cu /Cu , and Fe 3+ /Fe 2+ , in which x and y are integers from 1 to 6, and x is greater than y.
  • the concentration of the metal ion redox species is above 0.2 mol/L, preferably above 1.0 mol/L, and more preferably above 2.0 mol/L.
  • acid or base can be generated and large pH swing can occur. This requires the redox species to maintain high solubility even in the presence of high pH swings. This can be especially challenging when the pH is at high level due to poorer solubility of most metal ions at high H.
  • ligands are added into the electrolyte to improve the solubility of metal ions in neutral or high pH. In acidic pH, the presence of ligands can also help to stabilize the metal species that has lower solubility even at a low pH value.
  • the ligand that forms complexes with metal ions can include one or more functional groups, such as organic amine (primary, secondary, or tertiary, aromatic or non-aromatic), phosphonate, thioalcohol, phosphate, hydroxyl, or ammonia (NH 3 ), or can be selected from a group consisting of bromide, chloride, fluoride, iodide, cyanide.
  • functional groups including carboxylate, alkoxy, aldehyde, and ketone can also help in stabilizing the redox species in either catholyte or anolyte.
  • Ligand can be mono-dentate or multi-dentate.
  • Examples of multi-dentate ligand include 2, 2'- bispyridine, oxalate, citrate, and EDTA.
  • Multi-dentate ligand can also take the form of a ring such as crown ether. In both anolyte and catholyte, the ligand concentration lies in the range of 0.02-30 mol/L.
  • Use of these ligands can greatly improve the redox species' solubility and/or dispersibility during charging and discharging, hence stabilized voltage is achieved.
  • use of ammonia helps stabilized the Cu 2+ /Cu + redox pair in relative alkaline condition and avoids the copper species from precipitation out of electrolyte.
  • Other multi-dentate ligands such as EDTA, polyethyleneimine, oligo-ethyleneimine are also effect ligand for complexing to late 3d metals.
  • MnCl 4 bipy MnF 2 NH 3 , Mn(NH 3 ) 6 (CN) 2 , Mn(NH 3 ) 2 (CN) 2 , Mn(SCN) 2 ,
  • Ligands having both sulfonate and carboxylate groups such as sulfosuccinic acid and sulfophthahc acid can also be used as ligands that can boost solubility of complexed metal ions for flow batteries using transition metals as redox species.
  • Another group of ligands can be chosen from multi-substituted aromatic-ring containing carboxylates in their acids or their salt forms, which include
  • carboxylic groups can be directly attached to the ring or indirectly via one methylene (CH 2 ) group. It is also to be understood that the carboxylic group (or groups) can be randomly attached to the ring and not necessarily following a certain order.
  • the benezenedicarboxylic acids can consist of 1,2-, or 1,3-, and 1,4- benzenedicarboxylic acids.
  • Yet another group of ligands for complexing late 3d transition metals are the mono-, di- or trisulfonates of the above mentioned aromatic ring- containing carboxylates. Representative compounds are 4-sulfophthalic acid, 5-sulfo- 1,2,4-benzenetricarboxylic acid.
  • multi-substituted aromatic ring containing phenol, quinolinol, or naphthols can also be chosen to complex the late 3d transition metals.
  • These compounds include salicylic acid, 5-sulfosalicylic acid, 5-bromosalicylic acid, 5- chlorosalicylic acid, 4,5-dihydroxybenzene-l,3-disulfonic acid, 8-hydroxyquinoline and its sulfonate-substituted derivatives, and pyrocatechol and its sulfonoated derivatives.
  • the aromatic rings on the above mentioned ligands can greatly improve the ligands' electrochemical stability due to resonance structures of the rings, and the multi- substitution by complexing and/or solubilizing groups such as carboxylate, phenolate, and sulfonate can further improve the solubility of the final complexed metals, thereby increasing the current density of the flow battery.
  • a mixture of a multi-substituted aromatic ring-containing ligand and one or a few less expensive traditional ligands such as phosphonate ions, phosphate ions, oxalate ions, halogen ions, thiosulfate, cyanate, thiocyanate, citrate, tartarate, and other carboxylate group-containing ligands.
  • organophosphonates and phosphonocarboxylates can also be used to complex late 3d transition metals for improving stability and/or battery output power.
  • This group of compounds includes the acid or the salt form of the following compounds:
  • ATMP amino trimethylene phosphonic acid
  • EDTMPA ethylene diamine terra (methylene phosphonic acid)
  • DTPMPA diethylene triamine penta
  • HMDTMPA hexamethylenediaminetetra (methylenephosphonic acid) HMDTMPA, polyamino polyether methylene phosphonate (PAPEMP), and
  • the battery's catholyte can contain Mn /Mn .
  • Mn can exist in the form of permanganate (Mn0 4 ), and Mn can exist in the form of manganite (Mn0 4 2 ).
  • Br 2 /Br , BrO Br 2 , or Br0 3 Br 2 can be used in the catholyte.
  • Mn 3+ /Mn 2+ in the anolyte the Mn 2+ can exist in several forms, one of which is HMn0 2 .
  • Mn 3+ can be complexed Mn 3+ .
  • Preferred ligand for complexed Mn 3+ is NH 3 .
  • ligands include CN ⁇ 1 , OH "1 , multidendate such as EDTA, ethylenediamine, or a mixture of ligands. Use of ligands can greatly reduce the precipitation of insoluble species such as Mn0 2 during battery charging and discharging.
  • Mn based anode redox pair is Mn 5+ /Mn 2+ .
  • Fe ions as anolyte redox species
  • the anolyte preferably contains cyanide ions, and iron ions and cyanide ions form coordination compounds with cyanides.
  • the catholyte of the battery can contain Br 2 /Br , BrO 7Br 2 , or Br0 3 7Br 2 .
  • the solution preferably contains ammonia or organic amine compounds, or carboxylic acids such as small molecule carboxylic acids (e.g., citric acid or tartaric acid) or polymers containing carboxylic acid groups (e.g., poly(acrylic acid) or poly(maleic acid)).
  • carboxylic acids such as small molecule carboxylic acids (e.g., citric acid or tartaric acid) or polymers containing carboxylic acid groups (e.g., poly(acrylic acid) or poly(maleic acid)).
  • the ammonia, carboxylic acids, or amines can form coordination compounds with copper ions.
  • the catholyte of the battery can contain Br 2 /Br , BrO 7Br 2 , or Br0 3 Br 2 .
  • halogen of different valence states or halogen oxy acid of different valence states can be used.
  • halogen of different valence states or halogen oxy acid of different valence states can be used.
  • Br 2 /Br the halogen of different valence states or halogen oxy acid of different valence states
  • BrO Br 2 , and Br0 3 7Br 2 are suitable choice of catholyte redox species in providing oxidizing power for the battery.
  • chlorine and iodine can also have different valence states and form different oxy acids that have higher standard potential than anode redox species.
  • the elemental halogen can be coordinated with halide ions to form complexed halogen such as Br 3 which has higher solubility than Br 2 .
  • the catholyte typically needs to be in contact with electrode structure A which is the cathode.
  • Electrode structure A and B are consisted of conducting electric current collector plate and conducting porous materials and there is electric contact between the two. Electrode structure A functions as the cathode and provide a place where cathode redox species can receive electrons. Electrode structure B functions as the anode and provides a place where anode redox species can give off electrons.
  • the electrode structure A and/or B preferably includes at least one porous or high surface area conducting material, which can be selected from porous metals (such as porous nickel, porous titanium), porous carbon materials (such as carbon powder, carbon non-woven fiber, carbon woven fiber, graphite powder, carbon nanotube), conducting polymers including those polymers with intrinsic high conductivity and those polymer composites that are compounded with intrinsic conductive materials.
  • porous metals such as porous nickel, porous titanium
  • porous carbon materials such as carbon powder, carbon non-woven fiber, carbon woven fiber, graphite powder, carbon nanotube
  • conducting polymers including those polymers with intrinsic high conductivity and those polymer composites that are compounded with intrinsic conductive materials.
  • Examples of intrinsic conducting polymers include polyaniline and polypyrrole.
  • Polymer composite usually contains polymer that is not intrinsically conducting but when compounded with an intrinsic conducting material in highly dispersed form at above percolation threshold, exhibit good conductivity.
  • the electrode structure A and/or B preferably contain at least one catalyst, which is selected from the elemental form or compound form of at least one of the following elements: Ti, V, Cr, Co, Ni, Zr, Nb, Mo, Ru, Rh, Pd, Au, and Pb.
  • the battery generally includes a membrane or diaphragm that separates the two electrodes (i.e., the cathode and the anode).
  • a membrane or diaphragm that separates the two electrodes (i.e., the cathode and the anode).
  • One purpose of the membrane or diaphragm is to minimize the crossover of the electrolytes which can lower battery efficiency.
  • Preferred membranes include perfluorinated polymers such as NAFION (by Dupont), Flemion and Aciplex, and perfluorinated membrane produced by Dow Chemical.
  • the membrane can be selected from: ion exchange membranes, meso and microporous membranes, and nanofiltration membranes. It is required that the membrane material is stable under electrochemical
  • the conducting porous materials of electrodes preferably have conductivity of above 10 "3 S/m, more preferably above 1 S/m, and even more preferably above 100 S/m.
  • the void volume preferably is above 10%, and more preferably above 25%.
  • the conducting plate with roughness above 0.5 micron can also be used without use of conducting porous materials.
  • the electrode structure is made of the electric current collector plate which has roughness above 0.5 micron.
  • the conducting porous materials can be selected from the following: porous nickel, carbon black, porous titanium, non-woven carbon fiber, woven carbon fiber, graphite powder, and carbon nanotube.
  • the electric current collector plate within electrode structures A and B is in electric contact with the conducting porous materials, so that electric current can be collected from conducting porous material to current collector.
  • Electrode structures A and B generally have certain mechanical rigidity because they need to provide space for electrolyte to flow within, and need to be chemically stable in the presence of an electrolyte. In addition, electrode structures A and B can provide the path of least electrical resistance when charging and discharging the battery.
  • a catalyst on the electrode structure A or B can be selected from the elemental form or compound containing at least one the following elements: Ti, V, Cr, Co, Ni, Zr, Nb, Mo, Ru, Rh, Pd, Au, and Pb.
  • the catalyst can be dispersed onto conducting porous materials, such as dispersed onto porous carbon based materials. These catalysts can improve the redox reaction rate on the porous materials. These catalysts can optionally have certain degree of solubility in electrolyte, however, dispersed onto the conducting porous materials is the preferred method of using the catalyst in the present battery.
  • the current collector is coated with a conducting polymer composite coating to reduce the corrosion of the current collector plate in electrolyte.
  • the battery according to present invention has preferred charging voltage less than 1.5 V, and preferably less than 1.23 V, so that the water electrolysis is minimized.
  • Charging and discharging voltages can be tuned by use of a catalyst, redox species, ligand and external charging/discharging control circuit.
  • the choice of the ligand and redox species determines the thermodynamic voltage.
  • the charging voltage is usually above 1.5 V and evolution of hydrogen or oxygen will occur regardless of electrode materials choices, which may put extra stress on battery stacks.
  • the Mn-Br 2 battery and Cu-Br 2 battery have lower charging voltages than 1.23V, thereby minimizing the energy waste by water electrolysis and disruption of electrolyte composition due to oxygen or hydrogen evolution.
  • the battery according to present invention can be used for energy storage application in general.
  • Such energy storage device is particularly suitable for wind power station, solar power station, micro-electric grid, peak shaving, smart grid energy storage, underwater vehicles, and ship propulsion power source.
  • Figure 1 shows the section view of the battery used for example 1-3.
  • the membrane used was Nafion perfluoro membrane that separated the electrode structures A and B.
  • Catholyte 5 and anolyte 6 were in contact with electrode structures A and B, respectively.
  • an external voltage was applied to the battery while the electrolytes were flowing using peristaltic pumps.
  • the device was connected to an external load so that battery was discharged.
  • the outer side of electrode structures A and B was made of current collector plate 3 and inner side was made of conducting porous materials 4.
  • Example 1 Complexed all Mn reflow battery
  • the Mn species in catholyte and anolyte were both 1 mol/1, the voltage was determined to be IV.
  • the electrode current collector was made of graphite and the conducting porous materials were made of carbon cloth.
  • the apparent surface area of the electrode was 20 cm 2 .
  • the anolyte and catholyte both contained 8 mol/L KOH. Therefore, enough K 2 (Mn0 4 ) was dissolved in 8 mol/1 KOH so that active Mn solubility was 1 mol/L.
  • the temperature of the battery was controlled at 50°C.
  • MnCl 2 1 mol/L MnCl 2 was dissolved in 8 mol/L KOH as anolyte precursor solution.
  • the MnCl 2 solution was electrochemically oxidized to Mn 3+ in the presence of 2M ammonia. Ammonia greatly increased the trivalent Mn solubility.
  • the anolyte and catholyte prepared in this manner were charged and discharged according to Figure 3.
  • Example 3 Complexed Cu-Br reflow battery in alkaline pH
  • m can be 4 and n can be 3, water and hydroxide anions can also participate in forming coordination compounds.
  • 1 M [Cu(NH 3 ) 4 (H 2 0)x] 2+ solution was injected into anode structure and 75 mL catholyte (1 M NaBr) was injected into catholyte.
  • the battery was charged at constant current density of 20 mA/cm 2 for 1 hour.
  • Figure 5 shows the characteristic charging/discharging chart. As shown in Figure 5, this battery had an excellent voltage profile and its charge/discharge voltages liedbelow that of water hydrolysis but not much lower. The voltage profile is relatively flat in both charging and discharging process.
  • Example 4 Complexed Cu-Br reflow battery in acidic pH
  • the soluble Cu(I) in acidic medium could be made directly from mixing HBr and CuBr powder at > 1 : 1 molar ratio, and good solubility of Cu(I) was obtained due to excellent complexing power of bromide ions. Once bromine was introduced at the cathode, the flow battery was ready to operate (discharge) without charging.
  • a CuBr powder without extra bromide source was used as a source for Cu(I) at the anode.
  • a functional battery could not be made due to poor solubility of CuBr without extra bromide (well below 0.1 g/L level) as a ligand.
  • Examples 5-7 are examples of using complexed iron as anode electrolyte. All these examples used a 0.3 M Br 2 /Br ⁇ redox as the catholyte and 0.1 M Fe(III)/Fe(II) as the anolyte. The only variables were the ligand type and the ligand concentration. pH were adjusted using NaOH. In these examples, all cells were initially charged to 95% state of charge and discharged to 50% state of charge, at a constant current density of 20 mA/cm 2 .

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Abstract

La présente invention concerne une batterie à flux électrochimique pour le stockage d'énergie électrique, ladite batterie utilisant des matériaux réactifs d'anode (le matériau étant oxydé pendant la décharge de la batterie) choisis parmi la forme ionique complexée des métaux de transition ultérieurs 3d, c'est-à-dire le Mn, le Fe et le Cu. La batterie a un coût extrêmement faible grâce à l'utilisation de ces métaux relativement bon marchés.
PCT/US2012/035165 2011-05-20 2012-04-26 Batterie à flux Ceased WO2012161917A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US201161488163P 2011-05-20 2011-05-20
US61/488,163 2011-05-20
CN201110203069.0 2011-07-20
CN2011102030690A CN102790233A (zh) 2011-05-20 2011-07-20 液流型电化学电池

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WO2012161917A1 true WO2012161917A1 (fr) 2012-11-29

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Cited By (16)

* Cited by examiner, † Cited by third party
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US20140099569A1 (en) * 2012-10-04 2014-04-10 Seoul National University R&Db Foundation Organic electrolyte solution and redox flow battery including the same
WO2014197842A1 (fr) * 2013-06-07 2014-12-11 General Electric Company Cathodes pouvant fonctionner dans une réaction électrochimique, et cellules, dispositifs et procédés associés
US20150111117A1 (en) * 2011-05-23 2015-04-23 University Of Kentucky Research Foundation HYBRID FLOW BATTERY AND Mn/Mn ELECTROLYTE SYSTEM
WO2016044586A3 (fr) * 2014-09-17 2016-09-01 Case Western Reserve University Batteries à circulation à base de cuivre
EP3005458A4 (fr) * 2013-05-10 2016-12-07 Uchicago Argonne Llc Electrodes à nanoélectrocarburant rechargeables et dispositifs pour des batteries à flux à densité énergétique élevée
US9899695B2 (en) 2015-05-22 2018-02-20 General Electric Company Zinc-based electrolyte compositions, and related electrochemical processes and articles
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CN117096370B (zh) * 2023-10-17 2024-01-09 江苏恒安储能科技有限公司 一种新型液流电池端电极及其装配的液流电池
CN117976951A (zh) * 2023-12-26 2024-05-03 北京化工大学 一种全铁水系液流电池负极电解液
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