WO2020186307A1 - Électrode en gel de carbone - Google Patents

Électrode en gel de carbone Download PDF

Info

Publication number
WO2020186307A1
WO2020186307A1 PCT/AU2020/050263 AU2020050263W WO2020186307A1 WO 2020186307 A1 WO2020186307 A1 WO 2020186307A1 AU 2020050263 W AU2020050263 W AU 2020050263W WO 2020186307 A1 WO2020186307 A1 WO 2020186307A1
Authority
WO
WIPO (PCT)
Prior art keywords
carbon
battery
electrolyte
particles
anode
Prior art date
Application number
PCT/AU2020/050263
Other languages
English (en)
Inventor
Thomas Maschmeyer
Nathan Coad
Kirsty EVANS
Martin Schneider
Michael Horgan
Original Assignee
Gelion Technologies Pty Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from AU2019900911A external-priority patent/AU2019900911A0/en
Application filed by Gelion Technologies Pty Ltd filed Critical Gelion Technologies Pty Ltd
Priority to AU2020243832A priority Critical patent/AU2020243832A1/en
Publication of WO2020186307A1 publication Critical patent/WO2020186307A1/fr

Links

Classifications

    • 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
    • H01M10/365—Zinc-halogen accumulators
    • 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
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/54—Electrolytes
    • H01G11/58—Liquid electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004—Details
    • H01G9/022—Electrolytes; Absorbents
    • H01G9/025—Solid electrolytes
    • 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
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0085—Immobilising or gelification of electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0088—Composites
    • H01M2300/0091—Composites in the form of mixtures
    • 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

  • the present invention relates to energy storage and generation, in particular batteries.
  • Flow batteries have long been considered to be the most suitable storage technology for utility applications due to their potential long life, deep discharge characteristics and potential low manufacturing cost.
  • Flow batteries differ from other battery technologies in that the electrolyte is pumped over the electrodes, which remain electrochemically inert, storing charge through a change in oxidation state (e.g. vanadium redox) or through an electrodeposition such as the zinc- bromine battery.
  • oxidation state e.g. vanadium redox
  • ZBB zinc-bromine battery
  • a zinc -bromine flow battery consists of two half cells separated by a permeable membrane through which an aqueous zinc bromide/bromine electrolyte is circulated. During the charging step, zinc is electroplated on the anode, and Bn is evolved at the cathode.
  • a molecular complexing agent dissolved in the electrolyte such as A- c t h y 1 - A- in c t h y 1 p y rro 1 i d i n i u in b ro in i dc (MEPBr), is used to reduce the reactivity and vapour pressure of the elemental Bn by complexing the majority of the Bn to MEPBr, forming a so-called polybromide complex (MEPBr n ). This reduces the self-discharge of the battery and improves the safety of the system.
  • This complex is removed from the electrodes via the flowing electrolyte and is stored in an external reservoir.
  • the complex On discharge, the complex is returned to the battery stacks by the operation of a valve or a third pump. Zinc is oxidized to zinc ions on the anodes; the Bn is released from the complex and subsequently reduced to Br ions on the cathodes. Such system may also be operated with various metals and halides other than zinc and bromine. [0005] While operational and economic for some applications, existing zinc -bromine battery technology currently only operates at 15% of the theoretically achievable (based on ZnBn solubility) specific energy due to sub-optimal electrode design, poor fluid dynamics and the inefficient two-phase fluid, gravity- separated complexing of Bn. This limits the battery to non transport and low specific energy and energy density applications.
  • 3D electrodes having a large surface area have been used in conjunction with a conventional liquid electrolyte in zinc-bromine batteries, in an attempt to improve performance.
  • a conventional liquid electrolyte in zinc-bromine batteries in an attempt to improve performance.
  • One example of such a 3D electrode is carbon felt.
  • carbon felt is not a suitable material for commercial manufacture of batteries because of its high cost.
  • a battery comprising an anode, a cathode, and at least one electrolyte disposed between the anode and the cathode, wherein the at least one electrolyte comprises a gelating agent and a composition of carbon particles.
  • the battery may further comprise a halogen in contact with the cathode, and a metal in contact with the anode, wherein during discharge the halogen is reduced at the cathode and the metal is oxidised at the anode.
  • the battery may further comprise a halide in contact with the cathode, and a metal cation in contact with the anode, wherein during charging the halide is oxidised at the cathode and the metal cation is reduced at the anode.
  • the halogen may be bromine.
  • the halide may be bromide.
  • the metal may be zinc.
  • the at least one electrolyte may be a gel.
  • the at least one electrolyte may be an aqueous electrolyte.
  • the gelating agent may comprise silica particles, zeolite particles, aluminium silicate particles, clay particles, or a mixture thereof.
  • the gelating agent may comprise silica particles.
  • the battery may further comprise a separator.
  • the at least one electrolyte may comprise a gelating agent which is silica particles in an amount of 1 to 15 % w/v.
  • the at least one electrolyte may comprise a gelating agent which is silica particles in an amount of about 3 to 5 % w/v.
  • the at least one electrolyte may comprise the composition of carbon particles in an amount of 1 to 40 % w/v.
  • the at least one electrolyte may comprise the composition of carbon particles in an amount of about 5 to 20 % w/v.
  • the composition of carbon particles may comprise one or more types of carbon particles selected from the group consisting of graphite, graphene, vitreous carbon, activated (porous) carbon, carbon nanotubes, expanded graphite, carbon fibre, glassy carbon, shredded carbon felt, carbon black, and carbon foam.
  • the composition of carbon particles may comprise one or more types of carbon particles selected from the group consisting of activated (porous) carbon, expanded graphite, shredded carbon felt, and carbon black.
  • the composition of carbon particles may comprise one type of carbon particles selected from the group consisting of activated (porous) carbon, expanded graphite, shredded carbon felt, and carbon black.
  • the composition of carbon particles may comprise one type of carbon particles which are activated (porous) carbon particles.
  • the composition of carbon particles may comprise one type of carbon particles which are expanded graphite particles.
  • the composition of carbon particles may comprise one type of carbon particles which are shredded carbon felt particles.
  • the composition of carbon particles may comprise one type of carbon particles which are carbon black particles.
  • the composition of carbon particles may comprise two or more types of carbon particles selected from the group consisting of graphite, graphene, vitreous carbon, activated (porous) carbon, carbon nanotubes, expanded graphite, carbon fibre, glassy carbon, shredded carbon felt, carbon black, and carbon foam.
  • the composition of carbon particles may comprise graphite and carbon black.
  • the composition of carbon particles may comprise graphite or expanded graphite, carbon black, and activated carbon.
  • the composition of carbon particles may comprise graphite, carbon black, activated carbon, and carbon fibre.
  • the electrolyte may further comprise a halogen sequestering agent, wherein the halogen sequestering agent (HSA) is an organic compound comprising a moiety capable of sequestering the halogen.
  • HSA halogen sequestering agent
  • the moiety capable of sequestering the halogen may be a quaternary ammonium group, a phosphonium group, or a sulfonium group.
  • the moiety capable of sequestering the halogen may be a quaternary ammonium group.
  • the electrolyte may further comprise at least one additive selected from the group consisting of polyethyleneglycol.
  • the electrolyte may further comprise at least one electrolyte salt selected from KC1, KBr, LiCl, LiBr, NaCl, NaBr, NH 4 C1, NH 4 Br, LiC104, PbCl 2 , PbBr 2 , and PbO.
  • the battery When in use, the battery may be in a vertical configuration.
  • a method of producing a battery comprising providing a cell casing comprising an anode and a cathode, providing a separator between the anode and the cathode, preparing an anolyte by dissolving a metal halide salt, electrolyte salt, HSA and additives, preparing a catholyte by mixing silica and carbon particles in to the anolyte by high shear mixing, filling the cathode cavity with the catholyte, and filling the anode cavity with the anolyte.
  • a battery comprising an anode, a cathode, wherein a halogen is in contact with the cathode and a metal is in contact with the anode, and at least one electrolyte disposed between the anode and the cathode, wherein the at least one electrolyte comprises silica particles and a composition of carbon particles.
  • Figure 1 Exemplary horizontal cell configurations (Figure 1A - horizontal
  • Figure 2 Comparison of energy efficiency (%) of base electrolyte solution with and without the addition of silica for horizontal cell.
  • Figure 3 Comparison of energy efficiency (%) of carbon felt and carbon gel comprising a single type of carbon for horizontal cell.
  • Figure 4 Energy efficiency (%) of blended carbon silica types. Carbon felt is used as a comparison for horizontal cell.
  • Figure 5 Exemplary vertical cell configuration.
  • Figure 8 Comparison of reduction in energy efficiency (%) after 12 h pause for electrolyte, silica, carbon felt and carbon gel compositions for vertical cell.
  • Figure 9 Anode of vertical cell after cycling with base electrolyte only on cathode side. Clear line across the middle of the electrode indicates stratification of bromine-containing electrolyte at the bottom of the cell. Mobility of bromine through liquid electrolyte enabled crossover to Zn side causing corrosion on the Zn deposit.
  • Figure 10 Anode of vertical cell after cycling with silica gel electrolyte (Si and base electrolyte) on cathode side. Stratification of electrolyte is clearly visible (area w/o coating on top of electrode). Crossover of bromine to the anode was clearly reduced.
  • silica gel electrolyte Si and base electrolyte
  • Figure 11 Anode of vertical cell after cycling with carbon felt on cathode side. Carbon felt shows clear signs of stratification (area w/o coating on top of electrode; line through middle of plating). Slight signs of corrosion at bottom of electrode indicate crossover of bromine to anode.
  • Figure 12 Anode of vertical cell after cycling with silica carbon mix gel 1 (Si, activated carbon and base electrolyte) on cathode side. Even plating quality is evident.
  • FIG. 13 Anode of vertical cell after cycling with silica carbon gel 2 (Si, expanded graphite and base electrolyte) on cathode side. Even plating quality is evident.
  • silica carbon gel 2 Si, expanded graphite and base electrolyte
  • Figure 14 Anode of vertical cell after cycling with silica carbon gel 3 (Si, carbon black and base electrolyte) on cathode side. Even plating quality is evident.
  • silica carbon gel 3 Si, carbon black and base electrolyte
  • Figure 15 Anode of vertical cell after cycling with shredded carbon felt fibre gel (Si, shreded carbon felt and base electrolyte) on cathode side. Even plating quality is evident, but line through middle of Zn plating indicates slight stratification.
  • shredded carbon felt fibre gel Si, shreded carbon felt and base electrolyte
  • FIG. 16 Anode of vertical cell after cycling with silica carbon mix gel (Si, activated carbon, expanded graphite, carbon black, and base electrolyte) on cathode side. Excellent plating quality is evident.
  • silica carbon mix gel Si, activated carbon, expanded graphite, carbon black, and base electrolyte
  • Figure 17 Comparison of energy efficiency (%) after 12 h pause of electrolyte, silica, 10% activated carbon gel and 20% activated carbon gel for vertical cell.
  • Figure 18 Comparison of recoverable charge (%) after 12 h pause of electrolyte, silica, 10% activated carbon gel and 20% activated carbon gel for vertical cell.
  • Figure 19 Comparison of reduction in recoverable charge (%) after 12 h pause for electrolyte, silica, 10% activated carbon gel and 20% activated carbon gel for vertical cell.
  • the term“comprising” means“including.” Variations of the word “comprising”, such as“comprise” and“comprises,” have correspondingly varied meanings. [00043] It will be understood that use the term“about” herein in reference to a recited numerical value includes the recited numerical value and numerical values within plus or minus ten per cent of the recited value.
  • a temperature of between 80 °C and 150 °C is inclusive of a temperature of 80 °C and a temperature 150 °C.
  • % w/v means g/mL x 100.
  • 1 g in 100 mL is equal to 1 % w/v.
  • the volume referred to in“% w/v” refers to the volume of base electrolyte prior to addition of gelating agent or carbon particles.
  • The“oxidant” refers to the element which is reduced during discharge of the battery.
  • the “reductant” refers to the element which is oxidised during the discharge of the battery. This terminology may be applied to each element regardless of whether the battery is charging or discharging. Accordingly, during charging the“oxidant” is oxidised and the“reductant” is reduced.
  • the halogen species may be referred to as the oxidant and the metal species may be referred to as the reductant.
  • The“anode” refers to the electrode at which the reductant is oxidised during discharge of the battery.
  • The“cathode” refers to the electrode at which the oxidant is reduced during discharge of the battery. This terminology may be applied to each electrode regardless of whether the battery is charging or discharging. Accordingly, during charging, the oxidant is oxidised at the cathode and the reductant is reduced at the anode. For example, the halogen is reduced and oxidised at the cathode, and the metal is oxidised and reduced at the anode.
  • references to the“anode side” or“cathode side” of the battery refer to the electrolyte between the anode and the separator, and the electrolyte between the cathode and the separator, respectively.
  • the present specification relates to a gel electrolyte for a battery, comprising carbon particles dispersed in a gel, such as a silica gel.
  • the battery is of a type that generates electrical energy by the oxidation of a metal and the reduction of a halogen (henceforth a halogen battery).
  • the reductant which often comprises elemental metal, is oxidised at the anode to produce metal cations.
  • the halogen species typically a molecular halogen, is reduced to halide ions.
  • the oxidation reaction of a divalent metal at the anode during battery discharge may be represented by the forward direction of Equation 1 :
  • Equation 2 The reduction reaction at the cathode during battery discharge may be represented by the forward direction of Equation 2: ...Equation 2
  • halogen such as bromine
  • the halogen should be confined to the cathode side of the battery and the concentration of the halogen should be uniform throughout the cathode and cathode-side electrolyte.
  • a gel electrolyte comprising carbon particles dispersed in a gel, such as a silica gel, provides effective halogen management and superior battery performance, compared to other 3D electrode materials such as carbon felt in conjunction with a liquid electrolyte.
  • Superior performance of batteries of the invention may include one or more of the following advantages: • Improvement of cathode performance due to uniform halide distribution on the cathode electrode surface and reduced stratification.
  • the battery of the invention comprises an anode and a cathode.
  • the anode is the electrode at which the oxidation reaction takes place during discharge.
  • the cathode is the electrode at which the reduction reaction takes place during discharge.
  • An electrode is an electrical conductor used to make contact with a non-metallic part of a circuit.
  • the anode and cathode may comprise any suitable material, typically an inert conductor. Suitable anode materials include carbon-filled polymers, carbon fibre felts, metals (including zinc), alloys, conductive organic polymers, conductive metallo-organic polymers, and binder-held carbon powders.
  • Suitable cathode materials include inert metals such as platinum, carbon fibre felts, halogen resistant metals, conductive oxides, carbon-filled polymers, and binder-held carbon powders.
  • the anode and the cathode may each comprise a collector which is typically a conductive plate or mesh which is connected to the wires of an external circuit.
  • the battery comprises an oxidant and reductant, which, in the operation of the battery, react in spatially separated half-reactions to generate electrical energy. This is known as discharge.
  • The“oxidant” refers to the element which is reduced during discharge of the battery.
  • the “reductant” refers to the element which is oxidised during the discharge of the battery.
  • the oxidant is a halogen, that is, one of fluorine, chlorine, bromine or iodine.
  • the oxidant is molecular halogen (i.e. F 2 , Cb, Bn or I 2 ).
  • the reductant is a metal, which may be selected from the group consisting of Zn, Mg, Ca, K, Na, Al, Fe, and Ni.
  • the reductant may be an elemental metal (e.g. elemental Zn, Mg, Ca, K, Na, Al, Fe, or Ni).
  • the halogen is in contact with the cathode, where it is reduced during discharge and the metal is in contact with the anode, where it is oxidised during discharge.
  • the battery of the invention may contain a redox couple comprising a metal ion in two different oxidation states, such as Fe 2+ /Fe 3+ or Mh 2+ /Mhq 2 ⁇
  • the higher oxidation state metal ion is the oxidant (e.g. Fe 3+ )
  • the lower oxidation state metal ion is the reductant, (e.g. Fe 2+ ).
  • the discharged battery of the invention comprises a halide that is derived from the halogen. That is, during the discharge of the battery the molecular halogen (i.e. F 2 , CI 2 , Br 2 or I 2 ) is reduced to the corresponding halide (i.e. F , CT, Br or G). For example, Br 2 is reduced to Br during discharge of the battery, thus the Br is derived from Br 2 .
  • the halogen from which the halide is derived may also be referred to as the halogen of the halide.
  • the discharged battery of the invention also comprises a cation derived from the metal. That is, during discharge of the battery the elemental metal (e.g.
  • Zn Mg, Ca, K, Na, Al, Fe, or Ni is reduced to the corresponding metal cation (e.g. Zn 2+ , Mg 2+ , Ca 2+ , K + , Na + , Al 3+ , Fe 2+ , or Ni 3+ ).
  • Zn metal is oxidised to Zn 2+ during discharge of the battery, thus the Zn 2+ is derived from Zn metal.
  • the battery of the invention has a charged state wherein the oxidant is a halogen species which is a molecular halogen e.g. CI 2 , Br 2 , h, etc. and the reductant is a metal species which is a metal.
  • the oxidant is a halogen species which is a molecular halogen e.g. CI 2 , Br 2 , h, etc.
  • the reductant is a metal species which is a metal.
  • the battery of the invention also has a discharged state wherein the oxidant is a halogen species which is a halide anion e.g. CT, Br , G, etc.
  • the reductant is a metal species which is a metal cation, e.g. Zn 2+ , Mg 2+ , etc. (the oxidised state of the metal).
  • oxidant and reductant which may be used with the battery of the invention are zinc and bromine, magnesium and bromine, or sodium and chlorine.
  • the oxidant is preferably a molecular bromine, and the reductant is preferably zinc metal.
  • the battery of the invention may comprise a separator, which is a semipermeable barrier disposed between the cathode and the anode.
  • A“semipermeable barrier” refers to a material which is typically electrically non-conductive and allows electrolyte ions to move between the anode and the cathode sides of the battery to balance charge, but reduces the diffusion of the oxidant and reductant between the two sides of the battery.
  • Other roles of the separator may also include providing a controlled space between the anode and cathode to ensure an evenly distributed electro-chemical potential, and to provide a physical barrier to dendrites and other uneven deposits of the oxidant and/or reductant species.
  • the battery of the invention comprises an electrolyte disposed between the anode and the cathode.
  • the electrolyte contains a dissolved electrolyte salt which provide ionic neutrality for the charges formed at the cathode and anode during charging and discharging.
  • the dissolved electrolyte salt may be KC1, KBr, LiCl, LiBr, NaCl, NaBr, NH4CI, NFBBr, L1CIO4, PbCb, PbBn, or PbO.
  • the salt may be KC1.
  • the electrolyte may contain water.
  • the electrolyte may contain no water.
  • the battery of the invention may comprise two different electrolytes: a catholyte disposed between the cathode and the separator, and an anolyte disposed between the anode and the separator. At least the catholyte is the“carbon gel” of the invention.
  • the battery of the invention comprises the carbon gel as the catholyte only.
  • the battery of the invention comprises the carbon gel as both the catholyte and the anolyte.
  • the electrolyte also comprises the redox species.
  • the electrolyte comprises a salt of the metal redox species.
  • a salt of the metal redox species For example, an acetate, nitrate, sulfate, triflate permanganate, oxide, hydroxide, dichromate, perchlorate, or halide salt salt of Zn 2+ , Mg 2+ , Ca 2+ , K + , Na + , Al 3+ , Fe 2+ , or Ni 3+ .
  • the electrolyte may comprise one, two, three, four or more salts of the metal redox species.
  • the electrolyte may comprise zinc bromide, zinc chloride, or a mixture of zinc bromide and zinc chloride.
  • the electrolyte comprises the halogen redox species.
  • the catholyte may comprise bromine, chlorine or iodine.
  • the electrolyte may also comprise additives. Additives may serve, for example to stabilise the carbon gel and/or to disperse the carbon particles.
  • additives are polymers, including cationic, anionic, and neutral polymers. A wide range of polymers maybe used to stabilise a gel.
  • a polymer additive is polyethylene glycol (PEG).
  • PEG may be used in an amount of between 1 to 5 % w/v, or 2 to 4, or 4% w/v.
  • the PEG may have a molecular weight of 1000 to 10,000, or 2000-8000, or 6000 gmol 1 .
  • the electrolyte may contain no additives.
  • the electrolyte comprises a gel in which is dispersed a composition of carbon particles. This is referred to as the“carbon gel”.
  • the gel may be an aqueous gel.
  • a gelating agent is a compound which forms a gel when mixed with a solvent.
  • the gelating agent may comprise silica particles.
  • the silica particles may be porous silica, including mesoporous silica or microporous amorphous silica, semi-crystalline or crystalline silica (such as an all-silica zeolite).
  • the silica particles are preferably fumed silica.
  • the diameter of the silica particles may be about 0.01 to 100 pm, it may be about 0.01 to 10, 0.01 to 25, 0.01 to 50, 0.01 to 75, 0.1 to 10, 0.1 to 25, 0.1 to 50, 0.1 to 75, 0.1 to 100, 1 to 25, 1 to 50, 1 to 75, 1 to 100, 10 to 25, 10 to 50, 10 to 75, 10 to 100, 25 to 50, 50 to 75, 75 to 100, 0.01 to 50, or about 50 to 100 pm.
  • the particle size of the silica is about 0.2 to 30 pm.
  • the electrolyte may comprise silica particles in an amount of about 1 to 15 % w/v of the electrolyte composition, or about 1 to 3, 1 to 5, 1 to 7, 2 to 5, 5 to 7, 1 to 5, 5 to 10, or about 10 to 15 % w/v.
  • the electrolyte may comprise silica particles in an amount of about 1 % w/v, or about 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 or about 15 % w/v.
  • the electrolyte comprises silica particles in an amount of about 3 % w/v of the electrolyte composition.
  • the electrolyte comprises silica particles in an amount of about 5 % w/v of the electrolyte composition.
  • the silica acts as a thickening agent, and causes the aqueous electrolyte to form a gel. The use of a gel electrolyte reduces halide stratification, which in turn allows for more even charge distribution across the electrode.
  • the gelating agent may comprise aluminium silicate particles.
  • the gelating agent may comprise particles of a zeolite.
  • the aluminium silicate may be a zeolite.
  • the aluminium silicate may be a solid or layered (e.g. a clay), or a porous aluminosilicate, including mesoporous aluminosilicate or microporous amorphous, semi-crystalline or crystalline aluminosilicate (such as found in zeolites).
  • suitable aluminosilicates include MCM41, ZSM-5, and USY.
  • the carbon gel comprises a composition of carbon particles.
  • the composition of carbon particles may contain one type of carbon particle, or it may contain two, three, four, five, six, seven, eight, nine, ten, or more types of carbon particles.
  • the carbon particles may comprise one or more types of carbon particle selected from the group consisting of graphite, graphene, vitreous carbon, activated (porous) carbon, carbon nanotubes, expanded graphite, carbon fibre, glassy carbon, carbon black, carbon foam.
  • the total amount of carbon particles in the electrolyte may be about 1 to 40 % w/v of the electrolyte composition, or about 1 to 5, 5 to 10, 10 to 20, 10 to 30, 10 to 40, 20 to 30, 30 to 40, 5 to 20, or about 3 to 20 % w/v.
  • the total amount of carbon particles in the electrolyte may be about 1, 2, 3, 4, 5, 6, 7, 7.5, 8, 9, or 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 30, or 40 % w/v.
  • the electrolyte comprises one type of carbon particle, it may be present in an amount of about 3 to 40 % w/v, or about 3 to 20 % w/v, or about 3, 4, 5, 6, 7, 8, 9, 10, 11, 12,
  • the electrolyte comprises one type of carbon particle, it is present in an amount of about 5 to 10, or in an amount of about 5 to 20, or in an amount of about 5 to 40 % w/v of the electrolyte composition.
  • the electrolyte comprises two types of carbon particle
  • each may be present in an amount of about 2 to 10 % w/v, or about 5 to 10 % w/v, or about 2, 2.5, 3, 3.5, or 4, 5, 6, 7, 8, 9, or 10 % w/v.
  • each is present in an amount of about 3 % w/v (giving a total amount of carbon particles of 6 % w/v of the electrolyte composition).
  • the electrolyte comprises three types of carbon particle, each may be present in an amount of about 1 to 5 % w/v, or about 1, 1.5, 2, 2.5, 3, 4 or 5 % w/v.
  • each is present in an amount of about 3.3 % w/v (giving a total amount of carbon particles of 10 % w/v of the electrolyte composition).
  • the electrolyte comprises four types of carbon particle, each is present in an amount of about 1 to 3 % w/v of the electrolyte composition, or about 1, 1.5, 2, 2.5, or 3 % w/v.
  • each is present in an amount of about 2 % w/v of the electrolyte composition (giving a total amount of carbon particles of 8 % w/v of the electrolyte composition).
  • Exemplary two carbon compositions include graphite and carbon black, carbon black and carbon nanotubes, graphite and carbon fibre, activated carbon and expanded graphite, activated carbon and carbon black, and activated carbon and graphite.
  • Exemplary three carbon compositions include graphite, activated carbon, and carbon nanotubes, activated carbon, carbon black and expanded graphite, and graphene, expanded graphite, and carbon black.
  • Exemplary four carbon compositions include graphite, carbon black, activated carbon, and carbon fibre, and graphene, carbon nanotubes, activated carbon, and carbon black.
  • the carbon particles, being conductive, reduce the cell resistance by reducing the non-conductive cell gap, reducing the energy loss associated with transport distances of the active species.
  • the electrolyte may further comprise a halogen sequestering agent (HSA).
  • HSA is an organic compound comprising a moiety capable of sequestering the halogen redox species.
  • the moiety capable of sequestering the halogen may be a quaternary ammonium group, a phosphonium group, or a sulfonium group.
  • the moiety capable of sequestering the halogen is a quaternary ammonium group.
  • the HSA may be an ionic liquid comprising a quaternary ammonium group.
  • the HSA may comprise (a) one or more anions selected from the group consisting of bromide, chloride, iodide,
  • the HSA may be 1- methylethypyrrolidinium bromide.
  • Battery according to the invention and method of assembly 1 -( 1 -methoxymethyl)- 1 -methylpyrrolidinium, -( 1 -methoxymethyl)- 1 -methylpyrrolidinium, tetrabutylphosphonium, tributyloctylphosphonium, tributyl(2-methoxyethyl)phosphonium, tributyl-tert-butylphosphonium, tributyl( 1 -methoxymethyl)phosphonium, tetraethylammonium, tetrabutylammonium, tributyloctylammonium, tributyl(2-methoxyethyl)ammonium, tributyl(l- methoxymethyl)ammonium, and tributyl-tert-butylammonium.
  • the HSA may be 1- methylethypyr
  • the battery according to the invention comprises an anode and a cathode as described above, which are separated by an electrolyte disposed between the anode and the cathode.
  • the battery may also comprise a separator disposed between the anode and the cathode.
  • a current collector may be in contact with the anode and with the cathode, to connect the cell to an external circuit.
  • An exemplary schematic of the battery of the invention is depicted in Figure 1.
  • Electrolyte 1 (the anolyte) and Electrolyte 2 (the catholyte) as depicted in Figure 1 may be the same or may be different.
  • the battery according to the invention When in use, that is, when being charged or discharged, the battery according to the invention may be in a horizontal configuration or in a vertical configuration. In use, the battery according to the invention may be in a horizontal configuration. Alternatively, in use, the battery according to the invention may be in a vertical configuration. In a horizontal configuration, the surfaces of the electrodes that are in contact with electrolyte are substantially parallel to the ground. In the horizontal configuration, the anode may be positioned above the cathode.
  • the anode may be positioned above the cathode (see Figures 1A and IB).
  • the surfaces of the electrodes that are in contact with electrolyte are substantially perpendicular to the ground. Batteries in a vertical configuration are particularly prone to stratification, which leads to uneven metal plating and the formation of dendrites.
  • a battery according to the invention comprising the carbon gel electrolyte may have improved performance in a vertical orientation due to reduced
  • the battery may be assembled in a charged state, comprising elemental metal and molecular halogen.
  • the battery may be prepared in a discharged state comprising metal halide dissolved in the electrolyte.
  • the metal ions will be reduced to elemental metal at the anode and the halide will be oxidised to molecular halogen at the cathode, resulting in the catholyte comprising dissolved molecular halogen.
  • the battery according to the invention may be prepared by (i) providing a cell casing comprising an anode and a cathode, and optionally current collectors (ii) providing a separator between the anode and the cathode (iii) preparing the anolyte by dissolving the metal halide salt, electrolyte salt, HSA and additives (iv) preparing the catholyte by mixing silica and carbon particles in to the anolyte by high shear mixing (v) filling the cathode cavity with the catholyte (vi) filling the anode cavity with the anolyte.
  • the catholyte solution comprising the carbon gel may be filled into both the anode cavity and the cathode cavity.
  • a base electrolyte solution was prepared containing ZnB n (2.5 M), ZnCh (0.5 M), KC1 (1.5 M), 1-methylethypyrrolidinium bromide (1 M) and polyethyleneglycol (MW6000, 0.94 % w/v).
  • the activated carbon used is activated carbon having dso of 10-15 pm.
  • the carbon black used is carbon black having DBP absorption of 360 cm 3 /100 g (9g method), BET surface area of 800 m 2 /g, and primary particle radius of 39.5 nm.
  • the expanded graphite used is expanded graphite having dso of between 20 and 75 pm, and powder density of 120 g/L.
  • the graphite used is graphite having particle size ⁇ 44 pm.
  • fumed silica (3 % w/v, 0.02-30 pm particle size) is mixed into the base electrolyte solution through high shear mixing.
  • carbon particles of various types were mixed into the base electrolyte solution, through high shear mixing.
  • carbon compositions comprising a single type of carbon, 7.5 % w/v of that carbon type was added.
  • the carbon composition contains two types of carbon, 3 % w/v of each carbon was added (total of 6 % w/v).
  • the carbon composition contains four types of carbon, 2 % w/v of each carbon was added (total of 8 % w/v carbon).
  • a cell according to Figure 1 was prepared.
  • the cell is composed of two carbon plastic electrodes, and a polymeric plastic membrane.
  • the cathode cavity was filled with carbon gel electrolyte, and the anode cavity was filled with the base electrolyte.
  • the cell was then sealed and cycled at a current density of 10 mA/cm 2 .
  • Carbon felt was used in replacement of both the silica and carbon, and the carbon only.
  • the base electrolyte solution was used, with the electrolyte being soaked into the felt prior to cell assembly.
  • a base electrolyte solution was prepared containing ZnBn (2.5 M), ZnCE (0.5 M), KC1 (1.5 M), 1-methylethypyrrolidinium bromide (1 M) and polyethyleneglycol (MW6000, 0.94 % w/v).
  • fumed silica (0.02-30 mih particle size) is mixed into the base electrolyte solution through high shear mixing.
  • carbon particles of various types were mixed into the base electrolyte solution, through high shear mixing.
  • a cell according to Figure 5 was prepared.
  • the cell is composed of two carbon plastic electrodes, and a polymeric plastic membrane.
  • the cathode cavity was filled with carbon gel electrolyte, and the anode cavity was filled with the base electrolyte.
  • the cell was then sealed and cycled at 0.25 C for 4 h.
  • Each cell was then cycled with a 12 h pausing test. Cells were run in for three cycles, then energy efficiency measurements were taken for five cycles, followed by a 12 hour pause, then one further cycle. The 12 h pause between testing induces stratification in the electrolyte.
  • the energy efficiency (%) is reported in Figures 6 and 7.
  • Energy efficiency values are an average of the five runs post-run-in over four cells (total of 20 values), and an average over four cells for the one cycle after 12 h pause (total of four values). Energy efficiency is calculated as above for the horizontal cell configuration.
  • a common issue with silica gel is the drop in charge capacity over time.
  • the self discharge of silica carbon gel with 10% w/v activated carbon content is more stable in the long term than either liquid electrolyte only or silica gel electrolyte.
  • By increasing the content of activated carbon to 20% w/v the recoverable charge is greatly improved. Also observed is a reduction in stratification in vertical configuration, which is further improved with increase in activated carbon content.

Abstract

La présente invention concerne une batterie, comprenant une anode, une cathode et au moins un électrolyte disposé entre l'anode et la cathode, l'au moins un électrolyte comprenant un agent gélifiant et une composition de particules de carbone.
PCT/AU2020/050263 2019-03-19 2020-03-19 Électrode en gel de carbone WO2020186307A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2020243832A AU2020243832A1 (en) 2019-03-19 2020-03-19 Carbon gel electrode

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AU2019900911 2019-03-19
AU2019900911A AU2019900911A0 (en) 2019-03-19 Carbon gel electrode

Publications (1)

Publication Number Publication Date
WO2020186307A1 true WO2020186307A1 (fr) 2020-09-24

Family

ID=72518903

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/AU2020/050263 WO2020186307A1 (fr) 2019-03-19 2020-03-19 Électrode en gel de carbone

Country Status (3)

Country Link
AU (1) AU2020243832A1 (fr)
TW (1) TW202046547A (fr)
WO (1) WO2020186307A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113270640A (zh) * 2021-05-12 2021-08-17 徐文忠 固体电解质

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5851694A (en) * 1996-06-19 1998-12-22 Kashima-Kita Electric Power Corporation Redox flow type battery
WO2017142990A1 (fr) * 2016-02-17 2017-08-24 Eos Energy Storage, Llc Électrolyte à base d'halogène contenant du carbone
US20180211794A1 (en) * 2013-10-09 2018-07-26 Nicolo Brambilla Advanced electrolytes for high temerature energy storage device

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5851694A (en) * 1996-06-19 1998-12-22 Kashima-Kita Electric Power Corporation Redox flow type battery
US20180211794A1 (en) * 2013-10-09 2018-07-26 Nicolo Brambilla Advanced electrolytes for high temerature energy storage device
WO2017142990A1 (fr) * 2016-02-17 2017-08-24 Eos Energy Storage, Llc Électrolyte à base d'halogène contenant du carbone

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113270640A (zh) * 2021-05-12 2021-08-17 徐文忠 固体电解质

Also Published As

Publication number Publication date
TW202046547A (zh) 2020-12-16
AU2020243832A1 (en) 2021-07-15

Similar Documents

Publication Publication Date Title
Hao et al. Deeply understanding the Zn anode behaviour and corresponding improvement strategies in different aqueous Zn-based batteries
Yin et al. Electrochemical zinc ion capacitors: fundamentals, materials, and systems
Li et al. Issues and future perspective on zinc metal anode for rechargeable aqueous zinc‐ion batteries
Xie et al. Manipulating ion concentration to boost two‐electron Mn4+/Mn2+ redox kinetics through a colloid electrolyte for high‐capacity zinc batteries
Yao et al. Advanced post‐potassium‐ion batteries as emerging potassium‐based alternatives for energy storage
KR101503879B1 (ko) 마그네슘 하이브리드 전지 및 이의 제조 방법
US8802265B2 (en) Method for storing electrical energy in ionic liquids
Xing et al. Highly reversible zinc-ion battery enabled by suppressing vanadium dissolution through inorganic Zn2+ conductor electrolyte
JP6859317B2 (ja) 半固体フローＬｉ／Ｏ２電池
Cui et al. A high-voltage and stable zinc-air battery enabled by dual-hydrophobic-induced proton shuttle shielding
US20170214077A1 (en) Electrolyte System For Rechargeable Flow Battery
Qiu et al. Porous hydrated ammonium vanadate as a novel cathode for aqueous rechargeable Zn-ion batteries
Guo et al. Opportunities and challenges of zinc anodes in rechargeable aqueous batteries
US9748564B2 (en) Electrode compositions and related energy storage devices
US11121402B2 (en) Aqueous manganese ion battery
CN111279525A (zh) 适用于高能电池使用的改进型电化学电芯
Dong et al. Titanium-manganese electrolyte for redox flow battery
Das et al. Enabling a stable high-power lithium-bromine flow battery using task-specific ionic liquids
EP3565048A1 (fr) Batterie redox
Yin et al. Review and Perspectives on Anodes in Rechargeable Aqueous Zinc-Based Batteries
WO2020186307A1 (fr) Électrode en gel de carbone
Li et al. Halogen enabled aqueous flow cells for large-scale energy storage: current status and perspectives
She et al. Rechargeable Aqueous Zinc–Halogen Batteries: Fundamental Mechanisms, Research Issues, and Future Perspectives
JP6050387B2 (ja) フラーレンのイオン性液体中の懸濁液を有する電気化学半電池を有するガルバニ電池を備えた電気化学エネルギー貯蔵装置又はエネルギー変換装置
KR20170026574A (ko) 배터리

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 20773491

Country of ref document: EP

Kind code of ref document: A1

DPE1 Request for preliminary examination filed after expiration of 19th month from priority date (pct application filed from 20040101)
ENP Entry into the national phase

Ref document number: 2020243832

Country of ref document: AU

Date of ref document: 20200319

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 20773491

Country of ref document: EP

Kind code of ref document: A1