WO2011131959A1 - Batterie redox - Google Patents

Batterie redox Download PDF

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Publication number
WO2011131959A1
WO2011131959A1 PCT/GB2011/050659 GB2011050659W WO2011131959A1 WO 2011131959 A1 WO2011131959 A1 WO 2011131959A1 GB 2011050659 W GB2011050659 W GB 2011050659W WO 2011131959 A1 WO2011131959 A1 WO 2011131959A1
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WIPO (PCT)
Prior art keywords
hydroquinone
quinone
battery
electrode
derivative
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PCT/GB2011/050659
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English (en)
Inventor
Andrew P. Doherty
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The Queen's University Of Belfast
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Publication of WO2011131959A1 publication Critical patent/WO2011131959A1/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
    • 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 the use of quinones in the form of molten salts (ionic liquids) in energy storage applications.
  • a rechargeable electric battery comprising ionic liquid quinones and a method for producing such.
  • Redox batteries work by spontaneously, and simultaneously, performing an oxidation reaction (i.e., loss of electrons (e " )) at one electrode and a reduction reaction (i.e., gain of electrons) at another electrode where the electrons lost/gained flow through a circuit from one electrode to the other.
  • an oxidation reaction i.e., loss of electrons (e " )
  • a reduction reaction i.e., gain of electrons
  • the battery's "trick" is to separate A and C into compartments where the anode and cathode are electronically connected in a circuit (for electron flow) and ionically connected with some type of ion-conducting membrane (e.g. a solid polymer electrolyte (SPE)) which allows positively charged ions (usually H + ) to flow from the anode chamber to the cathode chamber to maintain electroneutrality. If the oxidation and reduction reaction are reversible, the battery can be recharged for reuse.
  • SPE solid polymer electrolyte
  • Non-rechargeable batteries are known and commonly used.
  • Zinc-carbon batteries have been known for many years. However, these batteries are associated with significant problems, in particular with regard to short and unpredictable shelf-life. Batteries comprising zinc powder as the anode, and manganese dioxide as the cathode are also well known.
  • alkaline batteries have a high energy density and a long shelf life compared to zinc-carbon batteries. Their capacity is strongly dependent on the load applied as the faster an alkaline battery is drained, the greater the percentage of its load is dissipated as heat. As such, alkaline batteries can be very inefficient.
  • Alkaline batteries contain hazardous materials, in particular potassium hydroxide and Zn 2+ and are difficult to dispose of.
  • Non-rechargeable battery Other forms of non-rechargeable battery are also commonly known, including lithium batteries.
  • Lithium batteries comprise lithium, or a lithium compound as an anode. These batteries are reliable and have a long shelf life compared to other types of non-rechargeable battery. They can generate relatively high voltages, commonly up to 3V, and can support heavy current devices and maintain a high current for relatively long periods of time.
  • lithium batteries are associated with rapid discharge of high currents which can lead to overheating. As such, lithium batteries can constitute an explosion risk. Furthermore, it is difficult to dispose of lithium batteries due to their incorporation of hazardous materials such as lithium.
  • rechargeable battery Several types are also commonly known, including lead/sulphuric acid batteries, nickel/cadmium batteries, nickel metal hydride batteries, lithium ion batteries and lithium ion polymer batteries.
  • the energy storage capacity (Watts per m 3 ) of known rechargeable batteries is generally also limited due to the difficulties of manufacturing these batteries on a very large scale.
  • known rechargeable batteries generally incorporate volatile materials and may constitute an overheating, fire or explosion risk.
  • rechargeable batteries are associated with toxic emissions including emissions of Pb, Cd, Ni and hydroxide, and are difficult to dispose of.
  • WO 2006/003395 discloses molten salts comprising quinone derivatives, a method of manufacturing such salts and their use in the production of hydrogen peroxide.
  • the disclosure made in WO 2006/003395 discloses molten salts comprising quinone derivatives, a method of manufacturing such salts and their use in the production of hydrogen peroxide.
  • a rechargeable battery comprising a first electrode and a second electrode separated by an ion-conducting barrier, wherein in its charged state, said rechargeable battery includes a molten salt comprising quinone or quinone derivative A having the structure of Formula I at the first electrode and a molten salt comprising hydroquinone or hydroquinone derivative B having the structure of Formula II or the structure of Formula III at the second electrode:
  • the rechargeable battery includes the molten salt comprising quinone or quinone derivative A at the first electrode, said first electrode acting as a cathode, and the molten salt comprising
  • the rechargeable battery includes the molten salt comprising the reduced quinone or quinone derivative A (i.e., the hydroquinone derivatives thereof) at the first electrode, said first electrode acting as an anode, and the molten salt comprising the oxidised hydroquinone or hydroquinone derivative B (i.e., the quinone derivatives thereof) at the second electrode, said second electrode acting as a cathode.
  • the rechargeable battery In the charged state, the rechargeable battery includes the molten salt comprising quinone or quinone derivative A in its oxidised form, i.e.
  • the rechargeable battery includes a molten salt comprising quinone or quinone derivative A in its reduced form, i.e. having the structure of Formula IB:
  • the rechargeable battery includes the molten salt comprising hydroquinone or hydroquinone derivative B in its oxidised form, i.e. having the structure of Formula lib or Formula lllb:
  • the battery of the present invention may be recharged by causing charge to flow in the opposite direction through the oxidation of the reduced form of quinone or quinone derivative A according to reaction scheme 1 b, and the reduction of the oxidised form of hydroquinone or hydroquinone derivative B according to reaction scheme 2b or reaction scheme 3b.
  • batteries comprising ionic liquid electrolytes are known, such ionic liquids do not participate in the electron transfer reactions of known batteries.
  • the molten salts of the batteries of the present invention participate in the electron transfer reactions.
  • the battery of the present invention is charged and discharged through the oxidation and reduction of the quinones and quinone derivatives of the molten salts.
  • the reactants of the redox reactions of the battery of the present invention are in liquid form and this provides important advantages over known batteries. In particular, the risks of fire or explosion are minimised.
  • the molten salt may be a liquid condensed phase material.
  • the molten salt is a liquid condensed phase quinone or quinone derivative, or hydroquinone or hydroquinone derivative.
  • the first and/or second electrode comprises a platinum electrode.
  • the platinum electrode comprises a platinum mesh.
  • the first and/or second electrode may comprise a material selected from the list comprising platinum, gold, platinium coated titanium, gold coated titanium and glassy carbon foam.
  • the ion-conducting barrier is formed from solid polymer electrolyte (SPE).
  • SPE may be Nafion®, in particular National® 1 17.
  • the ion-conducting barrier is formed from a perfluorinated polymer possessing fixed sulfonate groups. Typically, the perfluorinated polymer possessing fixed sulfonate groups is protonated.
  • quinone or quinone derivative B has the structure of Formula III.
  • hydroquinone or hydroquinone derivative B may have the structure of a four or five ring hydroquinone system.
  • the molten salt comprises the quinone or quinone derivative, or the hydroquinone or hydroquinone derivative B, and an anionic or cationic counter-ion. Where the quinone or quinone derivative is cationic, the counter-ion is anionic and vice versa.
  • the molten salt consists of cations and anions only.
  • the molten salt may consist essentially, or alternatively exclusively, of the quinone or quinone derivative, or the hydroquinone or hydroquinone derivative, and an anionic or cationic counter-ion.
  • the molten salt further comprises a further ionic liquid which does not comprise a quinone or hydroquinone or derivatives thereof.
  • the further ionic liquid may comprise the same counter ion as the quinone or hydroquinone or derivative thereof.
  • the further ionic liquid may comprise bis(trifluoromethyl-sulphonyl) imide as an anion.
  • the molten salts comprising quinone or quinone derivative A, or hydroquinone or hydroquinone derivative B are in liquid form, suitably in the form of an ionic liquid, typically having a melting point of 100 ° C or less, generally in the form of an ionic liquid having a melting point of 50 ° C or less, preferably in the form of an ionic liquid having a melting point of below 25 °C.
  • the molten salts of the battery of the present invention are in a pure, condensed phase, and are not diluted in any solvent. Thus, the molten salts may be undiluted.
  • the concentration of redox sites at the first and second electrodes of the battery of the present invention is typically at least 5 to 10 times higher than known redox flow- through batteries, in particular known rechargeable batteries where the anionic and cationic species are generally dissolved in a solvent.
  • This increase in the number of redox sites at the electrodes of the present invention leads to a corresponding increase in redox reactions, and a corresponding intensification in electrical energy storage capacity relative to batteries comprising redox reagents dissolved in solvents.
  • the quinone or quinone derivatives, or the hydroquinone or hydroquinone derivatives, of the battery of the present invention may be dissolved in one or more solvents.
  • suitable solvents include water, ionic liquids, glycols, alkylene carbonates such as propylenecarbonate, polyethers such as dimethoxyethane, CO2 and supercritical CO2.
  • the difference in redox potential ( ⁇ ) between the redox reactions of quinone or quinone derivative A and hydroquinone or hydroquinone derivative B is at least 0.0V; typically at least 1 .0V; advantageously at least 1 .5V.
  • the redox potential (EO) of quinone or quinone derivative A may be 0.5V or more, typically 0.6V or more.
  • the redox potential (E0) of hydroquinone or hydroquinone derivative B may be -0.5V or less, typically -0.6V or less, suitably -1 .0V or less, advantageously -1.2V or less.
  • the number of electrons involved in the redox reactions of quinone or quinone derivative A and hydroquinone or hydroquinone derivative B determines the current of the battery.
  • the power of the battery is also related to the number of electrons involved in the redox reactions, where power is the product of the current and the difference in redox potential ( ⁇ ) between the redox reactions of quinone or quinone derivative A and hydroquinone or hydroquinone derivative B.
  • ⁇ difference in redox potential
  • hydroquinone or hydroquinone derivative B according to reaction scheme 2a or reaction scheme 3a.
  • the current of the battery of the present invention is as high as, or higher than, most known redox flow-through batteries, in particular most known rechargeable batteries.
  • the current density of the battery of the present invention is 0.5 Amp/cm 2 of electrode area or more.
  • the battery of the present invention can support heavy current devices, and can maintain a high current for relatively long periods of time.
  • the voltage generated by the battery of the present invention is as high as, or higher than, most known redox flow-through batteries, in particular most known rechargeable batteries.
  • the battery of the present invention can be recharged reliably with relatively limited energy input relative to recharging processes for known rechargeable batteries.
  • the battery of the present invention can reliably be recharged numerous times.
  • the recharging process typically results in the battery becoming fully recharged, or recharged up to at least 90% of its initial redox potential, suitably at least 95% of its initial redox potential, advantageously up to approximately 100% of its initial redox potential. Accordingly, the battery of the present invention has a long and predictable shelf-life relative to known rechargeable redox flow-through batteries.
  • the battery of the present invention is charge balanced.
  • the battery of the present invention is typically an enclosed system, nothing is added and nothing is taken away through the redox reactions which take place therein. Accordingly, the battery of the present invention is also mass balanced.
  • the battery of the present invention may be scaled up easily and efficiently.
  • Energy storage capacity is a function of volume and thus increasing the volume of quinone or quinone derivative A and
  • hydroquinone or hydroquinone derivative B used increases the energy storage capacity of the battery of the present invention.
  • the volume of quinone or quinone derivative A should be increased by the same molar proportion as the increase in hydroquinone or hydroquinone derivative B for the energy storage capacity to be scaled up accordingly.
  • the energy storage capacity of the battery of the present invention is at least 0.01 Amp hour per cm 3 of liquid, suitably at least 0.1 Amp hour per cm 3 of liquid, advantageously 1 Amp hour per cm 3 of liquid.
  • the ion-conducting barrier of the present invention physically separates quinone or quinone derivative A from hydroquinone or hydroquinone derivative B whilst allowing ions to flow therethrough.
  • the ion-conducting barrier allows positively charged ions such as H + to flow therethrough.
  • Any known ion-conducting barrier may be used.
  • the ion-conducting barrier is formed from solid polymer electrolyte (SPE), such as that sold under the trade mark National® (in particular Nafion® 1 17) which is a perfluorinated polymer possessing fixed sulfonate groups.
  • SPE solid polymer electrolyte
  • the perfluorinated polymer possessing fixed sulfonate groups can be protonated by boiling in acid to obtain a very effective membrane.
  • the anode and/or cathode may be formed from any material known for such applications.
  • the anode and/or cathode are formed from carbon.
  • the anode and/or cathode may be formed from carbon having an electrocatalyst dispersed thereon, wherein the electrocatalyst is typically a precious metal or alloy such as Pt, Pt/Ru or Au.
  • the electrocatalyst may also be directly dispersed onto the ion- conducting barrier.
  • quinone or quinone derivative A has the structure as shown below:
  • hydroquinone or hydroquinone derivative B has the structure as shown below:
  • hydroquinone or hydroquinone derivative B has the structure as shown below:
  • R1 to R7 may independently be A; hydrogen; C1 to C10 linear, branched chain or cyclic alkyl groups; aryl; heterocycles; CI, Br, I, CN; OH or O2 wherein said alkyl and aryl substituents may themselves be substituted or unsubstituted;
  • A may represent an anion hetero-atom species. If the quinone or quinone derivative is cationic, or the
  • hydroquinone or hydroquinone derivative is cationic, A may represent a cationic hetero-atom species;
  • A typically represents SO 3" , COO “ , O- HPO3 " , O-PO3 2" or R-O-SO3 " and
  • R1 - R7 may independently represent imidazolium, piperidinium, pyridinium, phosphonium, pyrazinium, quaternary amine, ammonium species or derivatives thereof; or one or more of the ring atoms may be a quaternised heteroatom and each quaternised heteroatom may
  • A represents hydrogen, a CI to C10 linear, branched chain or cyclic alkyl group; an aryl group; a heterocycle group; CI, Br, I, CN; OH or NO 2 wherein said alkyl and aryl substituents may themselves be substituted or unsubstituted.
  • a and optionally one or more of R1 to R3 may independently represent imidazolium, piperidinium, pyridinium, phosphonium, pyrazinium, quaternary amine, ammonium species or derivatives thereof;
  • ring atoms may be a quaternised heteroatom and A may represent hydrogen; a CI to C10 linear, branched chain or cyclic alkyl group; an aryl group; a heterocycle group; CI, Br, I, CN; OH or NO2 wherein said alkyl and aryl substituents may themselves be substituted or unsubstituted.
  • any ring atom of any one of the Formulae may be a heteroatom, such as N, S, O or P, that may suitably be quaternised to form a cationic species.
  • Formulae may be anywhere on any of the rings.
  • aryl includes for example phenyl, polyphenyl, benzyl and similar moieties.
  • quinone derivative includes quinone derivatives, naphthoquinone and derivatives thereof, anthroquinone and derivatives thereof and, unless the context dictates otherwise, the hydroquinone derivatives of the aforementioned compounds.
  • the A group of the quinone or quinone derivative A, or the hydroquinone or hydroquinone derivative B is S0 3 " , COO “ , O-HPO 3 " , O-PO3 2 or R-O-SO3 " .
  • the quinone or quinone derivative B has the structure as shown below:
  • hydroquinone and hydroquinone derivative B will, or course, have a corresponding hydroquinone-type structure.
  • the cation (Ca ) of the molten salt is suitably an aliphatic or aromatic hydrocarbon species typically possessing a hetero-atom, such as N, S, P and O.
  • the aliphatic or aromatic hydrocarbon species typically possessing a hetero-atom, such as N, S, P and O.
  • hydrocarbon species may be substituted or unsubstituted, typically with one or more of any substituted or unsubstituted alkane, alkene, alkyne or aromatic hydrocarbon or any halogen group such as a fluorocarbon group.
  • the cation may comprise one or more amine, amide, nitrile, halogen, ether, alcohol, thiol, acid, ester, aldehyde, ketone or phosphine group.
  • the cation comprises a branched alkyl chain such as a fluorinated branched alkyl chain. In one embodiment the cation is
  • the cation may be selected from the group consisting of imidazolium, piperidinium, pyridinium, phosphonium, pyrrolidinium, pyrazinium, quaternary amine, ammonium species and derivatives thereof.
  • the cation is selected from the group consisting of imidazolium, piperidinium, phosphonium quaternary amine and ammonium species.
  • Cat + is an imidazolium cation it is preferably a cation of Formula IV:
  • R Formula VII In one embodiment the cation is tetradecyltrihexylphosphonium and has the structure:
  • R 1 to R 7 may independently be hydrogen, a substituted or unsubstituted C to C10 linear or branched alkyl chain, a substituted or unsubstituted cyclic alkyl group, an aryl group, CN, OH, NO 2 , SO 3 or COO " .
  • Cat + is a quaternary amine it is preferably of the form NR 4 + where each R group is independently a substituted or unsubstituted C1 to C20 linear or branched alkyl chain or a substituted or unsubstituted cyclic alkyl group.
  • the alkyl groups may be substituted with one or more alkane, alkyne or aromatic hydrocarbon or any halogen group such as a fluorocarbon group.
  • the cation is tetraalkylammonium or tetraalkylphosphonium.
  • the anion of the molten salt is suitable anionic species such as PF 6 , tetrafluoroborate, bistriflimide, triflate, fluoroalkylsulfonates , nitrate, a phosphate such as
  • the anion is dicyanamide or bistriflimide.
  • the redox reactions of the battery of the present invention generally proceed at temperatures of 100 °C or less; typically 25 ° C or less.
  • the redox reactions of the battery of the present invention proceed at temperatures of between 10 and 100 °C. Typically oxygen is excluded from the battery of the present invention. Generally the redox reactions proceed within a closed system, suitably under an inert atmosphere such as N 2 , if necessary.
  • the quinones or quinone derivatives of the battery of the present invention are generally non-volatile under the normal operating conditions of the battery.
  • the quinones or quinone derivatives, or the hydroquinone or hydroquinone derivatives, of the present invention are generally in liquid form; either in pure liquid form or dissolved in a solvent.
  • the battery of the present invention is mass and charge balanced and generally operates as a closed system. As such, the battery of the present invention does not dry out under normal operating conditions.
  • the battery of the present invention poses a very low fire, explosion or toxicity risk compared to known batteries, in particular compared to known batteries having a similar energy storage capacity.
  • the battery of the present invention does not generally include any metal compounds.
  • the battery of the present invention does not generally include any molten metals.
  • the battery of the present invention does not generally comprise any corrosive electrolytes.
  • the battery of the present invention is comparatively environmentally benign.
  • the battery of the present invention can be disposed of easily without risk of toxic emissions therefrom, and this provides an important advantage over known batteries.
  • the battery of the present invention may be in any known form, including hand held batteries to charge, for instance toys or music equipment; fuel cells for the storage of energy generated through solar, wave,
  • the battery of the present invention is in the form of a very large volume energy storage cell, where the battery of the present invention has an energy storage capacity proportional to stored liquid volume.
  • the battery of the present invention is in the form of an energy storage cell having an energy storage capacity up to GW depending on stored volume of liquids for the storage of wind, wave, hydroelectric or solar energy.
  • the battery of the present invention can be formed in known, standard types of redox flow battery apparatus.
  • quinone or quinone derivatives A and the hydroquinone or hydroquinone derivatives B may be provided in known membrane electrode assemblies (MEA) as shown in Figure 1 .
  • MEA membrane electrode assemblies
  • Such ME A have a proven reliability established following long and extensive use in energy delivery (fuel cells) and storage (flow-through redox batteries) applications.
  • the MEA is formed from a solid polymer electrolyte, such as that sold under the trade mark National®.
  • the ion- conducting barrier typically physically separates a first chamber housing the quinone or quinone derivative A from a second chamber housing the hydroquinone or hydroquinone derivative B.
  • the chambers are typically formed from a conducting material such as metal or a conducting plastic, or an insulating material. Where the chambers are constructed form a conducting material, these may directly contact the anode/cathode bonded to the MEA, around its periphery, to provide simple electric connection (suitably through the current collectors as shown in Figure 1). Where the chambers are constructed form a non-conducting material, contacts with the anode/cathode may be made with a metallic component or
  • redox-active liquids may be "stored" in reservoirs from which they will be pumped to their respective electrodes for charging and discharging. Obviously, since the electrode reactions are mass/charge balance, this will be an entirely closed system.
  • Figure 1 comprises; 2: stainless steel body
  • a quinone or quinone derivative A having the structure of Formula I, and hydroquinone or hydroquinone derivative B having the structure of Formula II or the structure of Formula III (as shown above) in energy storage applications, wherein energy is stored through the flow of charge from a first electrode to a second electrode through the oxidation of the reduced form of quinone or quinone derivative A according to the reaction shown in scheme 1 b (as shown above) and the reduction of the oxidised form of hydroquinone or hydroquinone derivative B according to reaction scheme 2b or 3b (as shown above).
  • Energy is spontaneously released through allowing the flow of charge in the reverse direction, i.e. through the spontaneous oxidation of hydroquinone or hydroquinone derivative B according to reaction scheme 2a or 3a (as shown above) and the contemporaneous reduction of quinone or quinone derivative A according to reaction scheme 1 a (as shown above).
  • a method of producing a rechargeable battery comprising the steps of: providing a first electrode and a second electrode, separated by an ion- conducting barrier;
  • quinone or quinone derivative A having the structure of Formula 1 (as shown above) at the cathode in the charged state and quinone or quinone derivative B having the structure of Formula II (as shown above) or the structure of Formula III (as shown above) at the anode in the charged state:
  • the rechargeable battery is as described above.
  • Figure 1 shows a known MEA battery arrangement
  • Figure 2 shows a cyclic voltammogram of the compound of Example 1 ;
  • Figure 3 shows a cyclic voltammogram of the compound of Example 2;
  • Figure 4 shows a cyclic voltammogram of the compound of Example 3;
  • Figure 5 shows a cyclic voltammogram of the compound of Example 4;
  • Figure 6 shows a cyclic voltammogram of 0.01 M [BMIM][HQS] in 0.1 M TBATFB/ACN using a carbon macro working electrode, Ag/AgCI reference and Pt wire auxiliary;
  • Figures 7a to 7c show plots of the square root of the sweep rate ( ⁇ 1/2 ) versus cathodic current (i pc ) for 0.01 M [B IM][HQS] in 0.1 M TBATFB/ACN using different working electrodes;
  • Figure 8 shows a cyclic voltammogram of 0.01 M [BMIM][HQS] in pure [BMIM][NTF 2 ] using a carbon macro electrode, Ag/AgCI reference and Pt wire auxiliary at different sweep rates;
  • Figures 9a to 9c show plots of the square root of the sweep rate ( ⁇ /2 ) versus cathodic current (i pc ) for 0.01 M [BMIM][HQS] in pure [BMIM][NTF 2 ] using different working electrodes;
  • Figure 10 shows cyclic voltammetry of pure [BMIM][HQS] using a carbon macro working electrode, Ag/AgCI reference and Pt wire auxiliary;
  • Figure 1 1 shows cyclic voltammetry of pure [BMIM][HQS] using a gold micro working electrode (diameter 100 ⁇ ), Ag/AgCI reference and Pt wire auxiliary;
  • Figures 12a to 12c show plots of ⁇ 1 2 versus i pc of pure [BMIM][HQS] using the different working electrodes for a carbon macro working electrode, a platinum macro working electrode and a gold macro working electrode, respectively;
  • Figure 13 shows cyclic voltammograms of 0.01 M [P14666][HQS] in 0.1 M TBATFB ACN using a carbon macro electrode at different sweep rates;
  • Figures 14a to 14c show plots of the square root of the sweep rate ( ⁇ ) versus cathodic current (i pc ) for 0.01 M [P14666][HQS] in 0.1 M TBATFB ACN using different working electrodes;
  • Figure 15 shows a cyclic voltammogram of 0.01 [P14666][HQS] in pure [P14666][NTF2] using a carbon macro working electrode, Ag/AgCI reference and Pt wire auxiliary;
  • Figures 16a to 16c show plots of ⁇ 1/2 versus i pc of pure 0.01 M
  • Figure 17 shows cyclic voltammograms of 0.01 M [P14666][NQS] in 0.1 M TBATFB ACN using a carbon macro electrode at different sweep rates;
  • Figures 18a and 18b show a plot of ⁇ 1/2 vs. i pc for 0.01 M [P14666][NQS] in 0.1 M TBATFB ACN using a carbon macro working electrode and a gold macro working electrode, respectively;
  • Figure 19 shows the cyclic voltammograms of 0.01 M [P14666][AQS] in 0.1 M TBATFB ACN using a carbon macro electrode at different sweep rates;
  • Figures 20a to 20c show plots of ⁇ 1/2 vs. i pc for 0.01 M [P14666][AQS] in 0.1 M TBATFB ACN using a carbon macro working electrode, a platinum macro working electrode and a gold macro working electrode respectively;
  • Figure 21 shows the cyclic voltammogram of 0.01 M [P14666][AQS] in pure [P14666][NTF 2 ] using a carbon working electrode, Ag/AgCI reference and Pt wire auxiliary electrode;
  • Figures 22a to 22c show plots of ⁇ 1 /2 vs. i pc for 0.01 M [P14666][AQS] pure [P14666][NTF 2 ] using a carbon macro working electrode, a platinum working electrode and a gold working electrode respectively;
  • Figure 23 shows cyclic voltammograms of 0.01 M [C14H30N][HQS] in 0.1 M TBATFB using a carbon macro working electrode, Ag/AgCI reference and a Pt wire auxiliary electrode;
  • Figures 24a to 24c show plots of ⁇ 1 " vs. i pc for for 0.01 M [C14H30N][HQS] in 0.1 M TBATFB ACN using a carbon macro working electrode, a platinum working electrode and a gold working electrode respectively;
  • Figure 25 shows cyclic voltammograms of 0.01 M [C14H30N][HQS] in pure [C14H30N][NTF 2 ] using a carbon macro working electrode;
  • Figures 26a to 26c show plots of ⁇ 1/2 vs. i pc for 0.01 M [C14H30N][HQS] in pure [C14H30N][NTF 2 ] using a carbon macro working electrode, a platinum working electrode and a gold working electrode respectively;
  • Figure 27 shows cyclic voltammograms of 0.01 M [C14H30N][AQS] in 0.1 M TBATFB ACN using a carbon macro working electrode;
  • Figures 28a to 28c show plots of ⁇ 1 2 vs. i pc for 0.01 M [C14H30N][AQS] in 0.1 M TBATFB ACN using a carbon macro working electrode, a platinum working electrode and a gold working electrode respectively;
  • Figure 29 shows cyclic voltammograms of 0.01 M [C14H30N][AQS] in pure [C14H30N][NTF 2 ] using a carbon macro working electrode;
  • Figure 30 shows a plot of ⁇ 1/2 vs. i pc 0.01 M [C14H30N][AQS] in pure
  • Figure 31 shows a cell set-up used to study the pairs of ionic liquids in accordance with the present invention
  • Figure 32 shows a cyclic voltammogram of a [P14666][HQS] /
  • Figure 33 shows the Nyquist plot of a [P14666][HQS] / [P14666][AQS] redox couple
  • Figure 34 shows the change in open circuit potential with time after a current of 100mA has been applied to the HQS side of a battery cell
  • Figure 35 shows the change in the open circuit potential before and after the application of 100 ⁇ for 4 hours.
  • Figure 36 shows the change in the open circuit potential before and after the application of -100 ⁇ for 5 hours.
  • the voltammetry displayed in Figures 2 to 5 is indicative of a reversible 2- electron 2-proton reduction process (i.e. negative current) occurring on the negative voltage sweep, leading to the corresponding anthrahydroquinone species, which is reoxidised via a 2-electron 2-proton oxidation process (positive current) on the positive voltage sweep.
  • a reversible 2- electron 2-proton reduction process i.e. negative current
  • anthrahydroquinone species which is reoxidised via a 2-electron 2-proton oxidation process (positive current) on the positive voltage sweep.
  • the following quinone-based ionic liquid was prepared and the storage capacity of a battery comprising this ionic liquid was investigated as detailed above.
  • the following quinone-based ionic liquid was prepared and the storage capacity of a battery comprising this ionic liquid was investigated as detailed above.
  • the following quinone-based ionic liquid was prepared and the storage capacity of a battery comprising this ionic liquid was investigated as detailed above.
  • the following quinone-based ionic liquid was prepared and the storage capacity of a battery comprising this ionic liquid was investigated as detailed above.
  • NTF2 bis(trifluoromethyl-sulphonyl) imide
  • C14H30N 1-methyl-octyl-pyridinium
  • [HQS] hydroquinone sulfonate
  • [AQS] 1 ,4-anthraquinone sulfonate.
  • the electrochemical analysis was performed using a standard three electrode cell under an inert nitrogen atmosphere (which was degassed prior to use).
  • a silver/silver chloride (Ag/AgCI) reference electrode and platinum wire auxiliary electrode were used.
  • a Voltalab PGZ301 potentiostat and a Sycopel AEW2 potentiostat (with attached Faraday cage) were used to record the voltammetry performed in this study. Cyclic voltammetry was used to analysis the oxidation/reduction of the quinones involved. For hydroquinone liquids the potential was swept from 0 to 1300 to - 800mV. For naphthaquinone and anthraquinone based liquids the potential was swept from 0 to -1800 mV. Three cycles were recorded. Ohmic compensation was applied to all voltammetry recorded using the Voltalab potentiostat but not to the voltammetry obtained using the Sycopel potentiostat. Example 5 - ⁇
  • Figure 6 shows a summary of the CVs for this solution at different sweep rates using a carbon macro electrode.
  • Tables 2 to 5 show a summary of the electrochemical data obtained including the values for the oxidation potential (E pc ) and the reduction potential (E pa ), cathodic and anodic currents (i pc and i pa ), the change in potential ( ⁇ ⁇ ) and ratio of cathodic to anodic current (i pc /i P a). It should be noted that all currents have been baseline corrected and corrected for area.
  • Figures 7a-7c show plots of the square root of the sweep rate ( ⁇ 1/2 ) versus cathodic current (i pc ) using the different working electrodes.
  • ⁇ ⁇ can be attributed to the fact that the reduction peak occurs at a less positive potential when a gold working electrode is used (E pa ranges from 0.218V at slower sweep rates to 0.094V at faster sweep rates for gold, whilst for carbon it ranges from 0.485V to 0.379V and 0.378V to 0.350V for platinum).
  • E pa ranges from 0.218V at slower sweep rates to 0.094V at faster sweep rates for gold
  • carbon ranges from 0.485V to 0.379V and 0.378V to 0.350V for platinum.
  • the size of the current i P a and i pc
  • Figures 7a - 7c show the plots of ⁇ 1/2 vs. i pc are not purely linear and as expected for quasi-reversible behaviour there are some deviations from linearity, particularly at slower sweep rates. These plots have been used to calculate the diffusion coefficients (Table 6) for the macro working electrodes using Randles-Sevcik equation 3 which can be simplified at 298K to Equation 1 .
  • i p ⁇ 2.69xlO*)n2AC 0 Di&2 (Eqn. 1)
  • i p the current (A)
  • n the number of electrons
  • A the electrode area (cm 2 )
  • C 0 the concentration (molcnrf 3 )
  • D 0 the diffusion coefficient (cm 2 s “1 )
  • ⁇ the sweep rate (V s "1 ).
  • Equation 3 a different equation (Equation 3) must be used to calculate the diffusion coefficient for a micro electrode system.
  • i d is the current
  • n is the number of electrons
  • F is the current
  • [BMIM][NTF 2 ] also exhibits a quasi-reversible oxidation/reduction profile.
  • the size of the current for the oxidation of the hydroquinone is significantly larger than that for the corresponding reduction, which as mentioned previously is due to the difference in kinetics of the two processes 2 .
  • the reduction peak completely disappears as previously observed in the acetonitrile solution.
  • Table 1 1 As Figure 8 shows 0.01 M [BMIM][HQS] in pure [BMIM][NTF 2 ] exhibits a similar oxidation/reduction pattern to that which was previously observed in 0.1 M TBATFB ACN ( Figure 6) i.e. a large oxidation peak coupled with a smaller reduction peak (there are additional peaks in the NTF 2 system which may be due to impurities in the system e.g. oxygen). The oxidation and reduction potentials are slightly less positive than those observed previously in 0.1 M TBATFB ACN.
  • the oxidation potential of 0.01 M [BMIM][HQS] in pure [BMIM][NTF 2 ] using a carbon macro working electrode at 0.05 Vs "1 was 0.831 V whilst the oxidation potential for the same concentration of [BMIM][HQS] in 0.1 M TBAFTB ACN using the same carbon macro electrode at the same sweep rate was 1 .044V (the corresponding reduction potentials were 0.365V and 0.464V respectively resulting in ⁇ ⁇ values of 0.466V and 0.580V).
  • Figure 10 shows cyclic voltammetry of pure [BMIM][HQS] using a carbon macro working electrode, Ag/AgCI reference and Pt wire auxiliary. The voltammetry at a number of different sweep rates is shown.
  • Figure 1 1 shows cyclic voltammetry of pure [BMIM][HQS] using a gold micro working electrode (diameter 100 ⁇ ), Ag/AgCI reference and Pt wire auxiliary. The voltammetry at a number of different sweep rates is shown.
  • Tables 12 - 15 show a summary of CV data obtained using different working electrodes for pure [BMIM][HQS]. All the potentials are quoted against an Ag/AgCI reference electrode.
  • Figures 12a - 12c show plots of ⁇ 1 2 versus ipc using the different working electrodes for a carbon macro working electrode, a platinum macro working electrode and a gold macro working electrode, respectively.
  • Figure 13 shows the cyclic voltammetry of this solution obtained using a carbon macro working electrode, Ag/AgCI reference electrode and Pt wire auxiliary electrode. The voltammetry at a number of sweep rates is shown.
  • Tables 16 - 19 show a summary of the key electrochemical data obtained from the analysis of 0.01 M [P14666][HQS] in 0.1 M TBATFB ACN using different working electrodes.
  • Figure 17 shows the CV of 0.01 M [P14666][NQS] in 0.1 M TBATFB ACN obtained using a carbon macro working electrode, Ag/AgCI reference and Pt wire auxiliary.
  • the relevant electrochemical data for this electrode and the others tested is summarised in Tables 25 - 26.
  • [P14666][NQS] in 0.1 M TBATFB ACN exhibits voltammetry which is typical for a naphthaquinone derivative. Both reduction and re-oxidation occur at negative potentials and are reversible.
  • Table 27 A summary of the diffusion coefficients obtained (from Figures 18a and 18b) using the different working electrodes tested are shown in Table 27. The data for the platinum macro electrode is not shown as the voltammetry obtained was unusual and was most probably caused by an artefact on the electrode surface.
  • FIG. 19 An example of some CVs obtained at different sweep rates using a solution of 0.01 M [P14666][AQS] in 0.1 M TBATFB are shown in Figure 19.
  • the working electrode used was a carbon macro electrode, the reference electrode Ag/AgCI and the auxiliary electrode Pt wire.
  • Tables 28 - 30 show a summary of the key electrochemical derived from the CV of this solution using a number of different working electrodes.
  • [P14666][AQS] in 0.1 M TBATFB ACN exhibits a reversible two- step, two- electron reduction/oxidation profile which occurs at negative potentials.
  • the diffusion coefficients for the systems have been calculated from plots of ⁇ 1/2 vs. ip C ( Figures 20a - 20c) and are summarised in Table 31.
  • [P14666][NTF2] is shown in Figure 21.
  • the working electrode used was a carbon macro electrode; Ag/AgCI reference and Pt wire auxiliary electrode were also used.
  • Tables 32 - 34 show a summary of the key
  • [P14666][NTF 2 ] is the same as that which has previously been observed in 0.1 M TBATFB ACN. Unlike the naphthaquinone equivalent which displayed irreproducible voltammetry the anthraquinone derivative appears to display more reproducible voltammetry, however, it should be noted that there are some inconsistencies which became evident over time and as the working electrode is varied. Investigations into these effects are continuing at present.
  • the diffusion coefficients for 0.01 M [P14666][AQS] in pure [P14666][NTF 2 ] obtained from Figures 22a - 22c are shown in Table 35.
  • this solution exhibits untypical electrochemistry for the oxidation and re-reduction of a hydroquinone species.
  • the exact cause of this effect is not known however, it is thought to be due to one of two effects - either the presence of chloride or a form a self electro-catalysis which has previously been identified in hydroquinone's in aqueous un-buffered media (Chaudhari et al.) 5 .
  • the effect is essentially caused by the development of a surface confined quinone layer at the electrode surface which results in the hydroquinone getting oxidised at two different catalytic centres.
  • FIG. 31 A prototype cell which allowed the testing of the chosen redox active ionic liquid couple was designed and built.
  • the cell body was constructed from brass.
  • This cell was basically a compact version of an H shaped cell which is conventionally used to study transport through membranes. It consisted of two chambers which were separated by a protonated membrane (the membrane is used to facilitate proton transfer and to ensure the two components remain separated). Each chamber was filled with one of the redox active ionic liquids and the cell connected through simple screws to a potentiostat. This is shown in Figure 31 , which comprises:
  • the cell described in Figure 31 was constructed using a PTFE body instead of a brass body - this was done to eliminate the adverse chemical reactions which were observed using brass and to try and improve the performance of the cell.
  • the electrode arrangement within the cell was also altered, i.e. a platinum mesh electrode was added into each cell half.
  • the platinum was placed in a number of positions within the cell including in direct contact with the membrane but this arrangement was not found to be suitable, i.e. there was no change to the open circuit potential when different currents were applied to the cell. Instead, the platinum mesh was carefully folded to create small 'cups' which were placed in the cavities within the PTFE cell in direct contact with the ionic liquids.
  • a small piece of platinum/iridium wire was threaded through each mesh to the exterior of cell and the wire was connected to the potentiostat.
  • the results from the impedance spectroscopy of the cell were mixed - but generally displayed a semi-circle in the high frequency region of the plot.
  • the lower frequency region was typically very noisy but there was no obvious Warburg behaviour.
  • An example of the plot obtained is shown in Figure 33.
  • the impedance spectrum was recorded using the HQS side of the cell as the working electrode and the AQS side of the cell as the counter electrode.
  • the reference was clipped to the counter electrode.
  • the spectrum was recorded from 100 kHz to 200 Hz.
  • the applied potential was 1000mV.
  • Tables 51 b and 52b show the change to the OCP following each impedance spectrum. As Tables 51 b and 52b show the open circuit potential only changes by a small amount after the impedance has been run and decays very quickly again back to near its original value.
  • a potentiostat was used to apply small currents to the cell and to measure the change which occurred to the open circuit potential of the cell as a result.
  • the results of the trials performed are shown below (Example 13 and Example 14). It is important to note that as expected once the cell had been subjected to a change it never regained its initial open circuit potential. In addition to this once a current has been applied the OCP
  • Example 13 Working electrode pure fP146661fHQS], auxiliary and reference pure fP14666irAQSl. PTFE cell.
  • Open circuit potential recorded after charging (recorded over 120 minutes): 1382 - 1278 mV
  • Figure 35 shows the change in the open circuit potential before and after the application of 100 ⁇ for 4 hours.
  • Table 53 shows the calculation of charge passed and mass of material converted during charging for
  • Figure 36 shows the change in the open circuit potential before and after the application of -100 ⁇ for 5 hours.
  • Table 54 shows the calculation of charge passed and mass of material converted during charging for
  • a glass version of the cell described above was also prepared. It should be noted that although the cell body has changed the working principles of the cell remain the same, i.e. the membrane type and electrodes used were the same. The key advantages of using a cell of this type are that filling the cell is much simpler and a visual check can be kept on the cell components. The same types of trials as those performed previously using the PTFE cell were performed. A sample of the results for the oxidation of hydroquinone side of the cell are summarised below. As a comparison of these results with the results shown previously for the PTFE cell indicate as expected the two cells act in the same way.

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Abstract

L'invention porte sur une batterie rechargeable comprenant une première électrode et une seconde électrode séparées par une barrière conductrice des ions, ladite batterie rechargeable comprenant, dans son état chargé, un sel fondu comprenant de la quinone, ou un dérivé de quinone A ayant la structure de la Formule (I) telle que décrite, au niveau de la première électrode, et un sel fondu comprenant de l'hydroquinone, ou un dérivé d'hydroquinone B ayant la structure de la Formule (II) ou de la Formule (III) telles que décrites, au niveau de la seconde électrode. Durant le processus de décharge, la charge circule de la seconde électrode à la première électrode par la réduction de la quinone ou du dérivé de quinone A selon le schéma réactionnel 1a tel que décrit, et de l'oxydation de l'hydroquinone ou du dérivé d'hydroquinone B selon le schéma réactionnel 2a ou le schéma réactionnel 3a tel que décrit.
PCT/GB2011/050659 2010-04-19 2011-03-31 Batterie redox WO2011131959A1 (fr)

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