WO2006017898A1 - Additifs zwittérioniques pour dispositifs électrochimiques - Google Patents

Additifs zwittérioniques pour dispositifs électrochimiques Download PDF

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WO2006017898A1
WO2006017898A1 PCT/AU2005/001237 AU2005001237W WO2006017898A1 WO 2006017898 A1 WO2006017898 A1 WO 2006017898A1 AU 2005001237 W AU2005001237 W AU 2005001237W WO 2006017898 A1 WO2006017898 A1 WO 2006017898A1
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electrolyte
lithium
electrolyte composition
zwitterion
group
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PCT/AU2005/001237
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English (en)
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Douglas Robert Macfarlane
Anthony Frank Hollenkamp
Patrick Craig Howlett
Maria Forsyth
Churat Tiyapiboonchaiya
Jenny Mary Pringle
Nolene Byrne
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Monash University
Commonwealth Scientific And Industrial Research Organisation
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Publication of WO2006017898A1 publication Critical patent/WO2006017898A1/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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0568—Liquid materials characterised by the solutes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
    • H01G9/035—Liquid electrolytes, e.g. impregnating materials
    • 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
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • 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
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • 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
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/14—Cells with non-aqueous electrolyte
    • H01M6/18—Cells with non-aqueous electrolyte with solid electrolyte
    • H01M6/181—Cells with non-aqueous electrolyte with solid electrolyte with polymeric electrolytes
    • 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
    • Y02E60/13—Energy storage using capacitors

Definitions

  • This invention relates to additives for use in electrochemical devices and the use of certain compounds as additives for this application. This invention also relates to electrolytes and electrochemical devices containing these additives.
  • Electrochemical devices are devices such as batteries, including Li-batteries (both Li-ion and Li-metal batteries) , capacitors, hybrid battery/capacitors, fuel cells, electromechanical actuators,, photoelectrochemical solar cells, electrochromic displays and sensors.
  • Li-batteries both Li-ion and Li-metal batteries
  • capacitors hybrid battery/capacitors
  • fuel cells including Li-batteries (both Li-ion and Li-metal batteries) , capacitors, hybrid battery/capacitors, fuel cells, electromechanical actuators,, photoelectrochemical solar cells, electrochromic displays and sensors.
  • Electrochemical devices contain electrolytes within which charge carriers (either ions, also referred to as target ions, or other charge carrying species) can move to enable the function of the given device.
  • charge carriers either ions, also referred to as target ions, or other charge carrying species
  • electrolytes available for use in electrochemical devices.
  • these include gel electrolytes, polyelectrolytes, gel polyelectrolytes, ionic liquids, plastic crystals and other non-aqueous liquids, such as ethylene carbonate, propylene carbonate and diethyl carbonate.
  • the electrolytes used in these devices are required to be electrochemically stable, have high ionic conductivity, a high target ion transport number (i.e. high mobility of the target ion compared to that of other charge carriers) and provide a stable electrolyte
  • the electrolytes should ideally also be thermally stable, and non-flammable.
  • rate capability One significant area in which the electrolytes have room for improvement is with respect to rate capability.
  • lithium batteries these may be primary or, more typically, secondary (rechargeable) batteries.
  • Lithium rechargeable batteries offer advantages over other secondary battery technologies due to their higher gravimetric and volumetric capacities as well as higher specific energy.
  • the two classes of lithium batteries mentioned above differ in that the negative electrode is lithium metal for lithium metal batteries, and is a lithium intercalation material for the "lithium - ion batteries”.
  • lithium metal is the preferred negative electrode material.
  • ⁇ traditional' solvents are used in combination with lithium metal negative electrodes, there is a tendency for the lithium metal electrode to develop a dendritic surface.
  • the dendritic deposits limit cycle life and present a safety hazard due to their ability to short circuit the cell - potentially resulting in fire and explosion.
  • the solid electrolyte interphase is formed on the lithium electrode surface in a lithium metal secondary cell.
  • the SEI is a passivation layer that forms rapidly because of the reactive nature of lithium metal.
  • the SEI has a dual role. Firstly, it forms a passivating film that protects the lithium surface from further reaction with the electrolyte and/or contaminants.
  • the SEI acts as a lithium conductor that allows the passage of charge, as lithium ions, to and from the lithium surface during the charge/discharge cycling of a lithium metal secondary cell.
  • the SEI is also known to form, on the surface of the negative electrode in a Li-ion cell.
  • the SEI is present as a resistive component in the cell and can lead to a reduced cell voltage (and hence cell power) in some cases. It is also thought to be a contributing factor in the formation of dendrites in lithium metal rechargeable cells.
  • an electrolyte composition comprising a non-zwitterionie electrolyte and a zwitterion.
  • an electrochemical device comprising electrolyte composition comprising a non-zwitterionic electrolyte and a zwitterion.
  • the present invention provides for the use of a zwitterion as an additive to an electrolyte.
  • the present invention further provides the use of a zwitterion as an additive to an electrolyte to reduce impedance of ion transport caused by the solid electrolyte interphase.
  • a lithium-based energy storage device comprising the electrolyte composition described above.
  • the lithium-based energy storage device suitably further comprises at least one negative electrode, at least one positive electrode, a case for containing the electrodes and electrolyte, and positive and negative device terminals external to the case.
  • the lithium-based energy storage device may further comprise separators between the negative and positive electrodes.
  • Figure 1 is a schematic view of a battery-like cell in accordance with one embodiment of the invention.
  • Figure 2 is a schematic view of a 3-electrode cell used to conduct testing of the electrolytes.
  • Figure 3a is a cyclic voltammogram of dry N-methyl-N- butylpyrrolidinium, bis (trifluoromethanesulfonyl) imide on
  • Figure 3b is a cyclic voltammogram of dry 0.15 mol/kg N- methyl-N- (n-butanesulfonate) pyrrolidinium / N-methyl-N- butylpyrrolidinium bis (trifluoromethanesulfonyl)imide on Pt working electrode, Pt counter, Ag quasi-reference at 100 mVs -1 . Ambient temperature under argon.
  • Figure 4a is a cyclic voltammogram of dry 0.5 mol/kg lithium bis (trifluoromethanesulfonyl) imide / N-methyl-N- butylpyrrolidinium bis (trifluoromethanesulfonyl) imide.
  • Figure 4b is a cyclic voltammogram of dry 0.5 mol/kg lithium bis (trifluoromethanesulfonyl) imide / N-methyl-N- butylpyrrolidinium bis (trifluoromethanesulfonyl) imide with 0.15 mol/kg N-methyl-N- (n-butanesulfonate) pyrrolidinium.
  • Figure 5a is a cyclic voltammogram of dry 0.5 mol/kg lithium bis (trifluoromethanesulfonyl)imide / N-methyl-N- propylpyrrolidinium bis (trifluoromethanesulfonyl)imide.
  • Figure 5b is a Cyclic voltammogram of 0.5 mol/kg lithium bis (trifluoromethanesulfonyl)imide / N-methyl-N- propylpyrrolidinium bis (trifluoromethanesulfonyl) imide with 0.15 mol/kg N-meth ⁇ l-N- (n-butanesulfonate) pyrrolidinium.
  • Figure 6a is a cyclic voltammogram of 50/50 poly(lithium 2-acrylamido-2-methyl-1-propanesulfonic acid-co-dimethyl acrylamide) / N,N'-dimethylacetamide / ethylenecarbonate gel (P(AMPSLi-c-DM ⁇ ) / DMA / EC) .
  • Figure 6b is a cyclic voltammogram for 50/50 P(AMPSLi-c- DMAA) / 1-butylimidazolium-3-(n-butanesulfonate) / DMA / EC gel.
  • Figure 6c is a graph of 7 Li diffusion coefficients in the 50/50 P(AMPSLi-c-DMAA) / DMA / EC polyelectrolyte gel, as a function of temperature, with and without the 1- butylimidazolium-3- (n-butanesulfonate) zwitterion.
  • Figure 7a is a graph showing the effect of zwitterion (1- butylimidazolium-3- (n-butanesulfonate) ) addition on the conductivity of the polyelectrolyte system with 10:90 P(AMPSLi-c-DMAA) in propylene carbonate (PC) and 10:90 P(AMPSLi-c-DMAA)-TiO 2 in PC.
  • Figure 7b is a graph showing the effect of zwitterion (1- butylimidazolium-3- (n-butanesulfonate) ) addition on the conductivity of the polyelectrolyte system with 10:90 poly(lithium methyl acrylate-co-dimethyl acrylamide) (P(MALi-c-DMAA)) in polyethylene glycol (PEG) .
  • Figure 8 is a graph showing the effect of zwitterion (1- butylimidazolium-3- (n-butanesulfonate) ) addition on the conductivity of the 50:50 P(AMPSLi-c-DMM ⁇ ) copolymer system.
  • the lithium ion concentration was varied by adjusting the total polymer content, while keeping the ratio of zwitterion: (DMA/EC) co-solvent constant.
  • Figure 9a shows 7 Li NMR spectra of the polyelectrolyte gels (i) with zwitterion (1-butylimidazolium-3- (n- butanesulfonate) ) and (ii) without zwitterion.
  • the gels contain 10:90 P(AMPSLi-c-DMAA) copolymer/zwitterions/PC at a weight ratio of (i) 1:1:9 and (ii) 1:0:9.
  • Figure 9b is a graph of 7 Li ion diffusion coefficients of the same 10:90 P(AMPSLi-c-DMAA) copolymer in PC systems of Figure 9a, across a range of temperatures, measured using pulse-field-gradient NMR.
  • Figure 10 is a graph showing the effect of zwitterion (1- butylimidazolium-3- (n-butanesulfonate) ) on the conductivity of PAMPSLi in the absence of solvent.
  • Figure 11 is a graph of peak current vs. zwitterion concentration (N-methyl-N- (n-butanesulfonate) pyrrolidinium) for a conventional electrolyte (1 M LiPF 6 in EC:DEC 1:1 by volume - EC ethylene carbonate, DEC - diethyl carbonate) at room temperature. Cyclic voltamogram on a nickel substrate at 100 mVs -1 , Li counter electrode, Li quasi-reference electrode.
  • Figure 12a shows a comparison of the voltage response of a symmetrical lithium cell containing 0.5 mol/kg lithium bis (trifluoromethanesulfonyl) imide / N-methyl-N- propylpyrrolidinium bis (trifluoromethanesulfonyl)imide under galvanic cycling (2 mAcm -2 ) with and without the addition of 0.15 mol/kg N-methyl-N-(n-butanesulfonate) pyrrolidinium at 40 °C.
  • Figure 12b shows a comparison of the voltage response of a symmetrical lithium cell containing 0.5 mol/kg lithium bis (trifluoromethanesulfonyl)imide / N-methyl-N- propylpyrrolidinium bis (trifluoromethanesulfonyl) imide under galvanic cycling (8 mAcm -2 ) with and without the addition of 0.15 mol/kg N-methyl-N- (n-butanesulfonate) pyrrolidinium at 80 °C.
  • Figure 13a shows a plot of the cell resistance as a function of applied current density of a symmetrical lithium cell at 40 °C containing 0.5 mol/kg lithium bis (trifluoromethanesulfonyl)imide / N-methyl-N- propylpyrrolidinium bis (trifluoromethanesulfonyl) imide with and without the addition of zwitterion (0.15 mol/kg N-methyl-N- (n-butanesulfonate) pyrrolidinium) under galvanic cycling.
  • the cell resistance is obtained by dividing the voltage of the cell at the end of the tenth cycle (e.g., from example 12a) by the applied current density.
  • Figure 13b shows a plot of the cell resistance of a symmetrical lithium cell as a function of applied current density at 40 °C containing 0.5 mol/kg lithium bis (trifluoromethanesulfonyl) imide / N-methyl-N- propylpyrrolidinium bis (trifluoromethanesulfonyl) imide with and without the addition of zwitterion (0.15 mol/kg N-methyl-N- (n-butanesulfonate) pyrrolidinium) under galvanic cycling.
  • the cell resistance is obtained by dividing the voltage of the cell at the end of the tenth cycle (e.g. , from example 12b) by the applied current density.
  • Figure 14a shows a 3D plot of impedance spectra obtained from a symmetrical lithium cell at 40 °C containing 0.5 m ⁇ l/3:g lithium bis (trifluor ⁇ aethanesulfonyl) imide / M- methyl-M-propylpyrrolidinium bis (trifluoromethanesulfonyl)imide.
  • Each impedance spectrum is plotted against the current density (the Z axis) applied during the previous ten cycles.
  • Figure 14b shows a 3D plot of impedance spectra obtained from a symmetrical lithium cell at 40 °C containing 0.5 mol/kg lithium bis (trifluoromethanesulfonyl)iinide / N- methyl-N-propylpyrrolidinium bis (trifluoromethanesulfonyl)imide with added zwitterion (0.15 mol/kg if-methyl-U- (n-butanesulfonate) pyrrolidinium) .
  • Each impedance spectrum is plotted against the current density (the Z axis) applied during the previous ten cycles.
  • Figure 15a shows a 3D plot of impedance spectra obtained from a symmetrical lithium cell at 80 °C containing 0.5 mol/kg lithium bis (trifluoromethanesulfonyl) imide / N- methyl-N-propylpyrrolidinium bis (trifluoromethanesulfonyl)imide. Each impedance spectrum is plotted against the current density (the Z axis) applied during the previous ten cycles.
  • Figure 15b shows a 3D plot of impedance spectra obtained from a symmetrical lithium cell at 80 °C containing 0.5 mol/kg lithium bis (trifluoromethanesulfonyl) imide / N- methyl-N-propylpyrrolidinium bis (trifluoromethanesulfonyl)imide with added zwitterion (0.15 mol/kg N-methyl-N- (n-butanesulfonate) pyrrolidinium) .
  • Each impedance spectrum is plotted against the current density (the Z axis) applied during the previous ten cycles.
  • Figure 16 shows the cell voltage against time for two complete charge-discharge cycles for a battery cell containing 0.15 mol/kg N-methyl-N- (n-butanesulfonate) pyrrolidinium zwitterion in 0.5 mol/kg lithium bis (trifluoromethanesulfonyl)imide / N-methyl-N- but ⁇ lpyrrolidinium bis (trifluoromethanesulfonyl) imide as the electrolyte.
  • Figure 17 is a cyclic voltammogram of 4wt% of the zwitterion N-methyl-N- (n-butanesulfonate) pyrrolidinium in 1 mol/L solution of LiCF 3 SO 3 in propylene carbonate, compared with a voltammogram of the same solution containing no zwitterion.
  • Zwitterions are a well-known class of compounds, and are generally understood to be compounds containing both a positive (cation) and a negative (anion) charge (at the iso-electric point for the zwitterion) .
  • Zwitterions encompass the compounds of the structure:
  • X + -Y-Z " in which: X + represents the cation component, Y represents the linking group, and Z- represents the anion component.
  • zwitterions exhibiting electrochemical stability, which can be judged by the ability of the zwitterion to resist oxidation and reduction at a polarised electrode. This can be demonstrated by using cyclic voltammetry to measure the electrode response at extreme potentials.
  • the atom providing the positive charge to the cation component of the zwitterion is preferably selected from N, P and ⁇ s.
  • the cation components may be categorised into a number of subclasses, including the unsaturated heterocyclic cations, the saturated heterocyclic cations, and the non- cyclic quaternary cations.
  • the unsaturated heterocyclic cations encompass the substituted and unsubstituted pyridiniums, pyridaziniums, pyrimidiniums, pyraziniums, imidazoliums, p ⁇ razoliums, thiazoliums, oxazoliums and triazoliums, two-ring system equivalents thereof (such as isoindoliniums) and so forth. These ring systems may be attached to the linking group via any atom thereof.
  • the general class of unsaturated heterocyclic cations may be divided into a first subgroup encompassing pyridiniums, pyridaziniums, pyrimidiniums, pyraziniums, pyrazoliums, thiazoliums, oxazoliums, triazoliums, and multi-ring (i.e., two or more rings) unsaturated heterocyclic ring systems such as the isoindoliniums, on the one hand, and a second subgroup encompassing imidazoliums, on the other.
  • R 1 to R each independently represent a bond to the linking group Y, H, alkyl, haloalkyl, thio, alkylthio, haloalkylthio, or any other substituent within the classes outlined below, with the proviso that at least one of the
  • R groups present represents a bond to a linking group Y.
  • the saturated heterocyclic cations encompass the pyrrolidiniums, piperaziniums, piperidiniums, and the phosphorous and arsenic derivatives thereof. These rings may be attached to the linking group via any atom thereof, such as the heteroatom, or a carbon atom of the ring or a substituent thereon.
  • R 1 to R 12 each independently represent a bond to the linking group Y, H, alkyl, haloalkyl, thio, alkylthio, haloalkylthio, or any other substituent within the classes outlined below, with the proviso that at least one of the R groups present represents a bond to a linking group Y.
  • non-cyclic quaternary cations encompass the quaternary ammonium, phosphonium and arsenic derivatives.
  • R 1 to R 4 each independently represent a bond to the linking group Y, H, alkyl, haloalkyl, thio, alkylthio, haloalkylthio, or any other substituent within the classes outlined below, with the proviso that at least one of the R groups present represents a bond to a linking group Y.
  • the linking group Y may be any chain of atoms that links together or tethers the cation and anion components. These may be hydrocarbon chains such as alkyl, alkenyl or alkynyl (straight chain, branched or cyclic) , optionally containing heteroatoms in the chain or in branches thereof, such as 0, S, N and P, therefore encompassing ethers, amines, amides, with the chain being optionally substituted by any of the substituents outlined below, being a substituent that does not adversely affect electrochemical stability of the zwitterion or conductivity of the electrolyte composition containing the zwitterion.
  • the optional linking group substituents are selected from halo, nitrile, haloalkyl,, amine, amide, imine, sulfonyl and the like.
  • the linking group is at least 2 atoms in length.
  • the upper limit of the length is determined by practical considerations such as effectiveness of the zwitterion as the linking group length increases as compared with molecular weight and cost, as well as physical factors such as ⁇ fiscosity.
  • the linking group will be between 2 and 8 atoms in length.
  • the linking group is suitably an optionally substituted alkyl group.
  • This may be a C2 - C8 alkyl group, for instance.
  • the optional substituents in each case may be any one or more groups that do not adversely affect electrochemical stability of the zwitterion and/or the conductivity of the electrolyte composition containing the zwitterion.
  • the groups from which the substituents may be selected are alkyl, alkenyl, alkynyl, aryl, halo, haloalkyl, haloalkenyl, haloalkynyl, haloaryl, hydroxy, alkoxy, alkenyloxy, aryloxy, benzyloxy, haloalkoxy, haloalkenyloxy, haloaryloxy, nitro, cyano, nitroalkyl, nitroalkenyl, nitroalkynyl, nitroaryl, nitroheterocyclyl, amino, alkylamino, dialkylamino, alkenylamino, alkynylamino, arylamino, diarylamino, benzylamin
  • Halo refers to any of the halogens F, Cl, I and Br. References to haloalkyl and the like mean that the subject group is partially or fully halogenated.
  • alkyl denotes straight chain, branched or mono- or poly- cyclic alkyl, preferably Cl-30 alkyl or cycloalkyl.
  • straight chain and branched alkyl include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, hexyl, octyl, dodecyl, 1-methylundecyl and the like.
  • alkenyl and alkynyl have a corresponding meaning, with the proviso that they contain between 2 and 30 atoms.
  • any anion component that can be linked by one atom to the linking group Y, and supports the electrochemical stability of the zwitterion may be used.
  • the atom providing the negative charge of the anion component of the zwitterion may be selected from S, C, P, N, O or B.
  • the possible components may be categorised into a number of subclasses, as follows:
  • anions containing a carbon nitrogen bond such as cyanamide compounds.
  • This class encompasses -CH 2 SO 3 and -CF 2 SO 3 - as examples - i.e. any carbonyl chain partially or full fluorinated containing an anionic sulfonate group.
  • Ethylenedisulfonylamide and its perfluorinated analogue Ethylenedisulfonylamide and its perfluorinated analogue.
  • (x) sulfonyl amides generally including the bis amides and the part or perfluorinated versions thereof, and including specifically -C-CH 2 -SO 2 -)-N--SO 2 -CH 3 , -(-CF 2 -
  • Caryl groups, such as toluene sulfonate anions and xylene sulfonate anions.
  • the preferred classes are those outlined in groups (i) , (vi) , (x) , (xi) , (xii) and (xiii) .
  • the advantage of using a zwitterion over an ionic liquid (without zwitterion additive) in an electrochemical system is that although the ionic conductivity of the ionic liquid is usually very high, the contribution is not entirely the result of target ion migration. In other words, even with the addition of target ions, the ionic liquid component ions also migrate along the potential gradient. Since a zwitterion contains cations and anions that are physically tethered together, they do not migrate along the potential gradient. Zwitterions have also been shown to be effective at dissociating lithium in polymer/polyelectrolyte systems. Zwitterions are therefore shown to be effective at dissociating the target ion, which may lead to enhanced rate capabilities when used as the electrolyte in electrochemical devices.
  • the basic electrolyte to which the zwitterion is added is non-zwitterionie (thus distinguishing it from the additive) .
  • the electrolyte may be from any of the classes of known electrolytes, including polymers, polymer gels, polyeleetrolytes, polyelectrolyte gels, traditional solvents, ionic liquids or any other electrolyte material.
  • composition is used in its broadest sense to cover any compositions made up of any matter, including liquids, solids, membranes, gels and so forth.
  • the electrolyte generally further comprises mobile ions (otherwise referred to as target ions) of any suitable type.
  • Suitable mobile ions for various embodiments may be selected from the group consisting of lithium, hydrogen, sodium, magnesium, aluminium and zinc. According to one embodiment, the mobile ions are lithium.
  • the lithium ions may be present or introduced into the electrolyte in a number of different ways, depending on the nature of the electrolyte.
  • the lithium ions are the counterions to the negatively charged polymer.
  • they are added as lithium salts. This is sometimes referred to as doping.
  • the lithium is added to the solvent as a lithium salt, as in the case of LiPF 6 .
  • the lithium ions are generally incorporated into the electrolyte by the addition of a lithium salt, consisting of lithium ions and counterions.
  • a lithium salt consisting of lithium ions and counterions.
  • the lithium ions and counterions dissociate, and are effectively a solute to the room temperature ionic liquid solvent.
  • the counterions are the same as the anion of the room temperature ionic liquid, then the lithium addition can be considered to be doping of the electrolyte. In other words, doping can be considered as a cation substitution.
  • the concentration of lithium can be between 0.01% and 90% of the overall electrolyte composition by weight, preferably between 1 and 49% by weight. It is generally simpler to refer to the lithium concentration of the electrolyte in moles of lithium ions per kilogram of total electrolyte, and in this unit the lithium is suitably present in an amount of from 0.01 to 2.0 mol/kg, preferably 0.1 - 1.5 mol/kg, and most preferably 0.2 - 0.6 mol/kg.
  • the amount of mobile ion added is determined as that concentration which produces the optimum active ion flux in the device. This often corresponds approximately with the optimum conductivity point.
  • the zwitterionic additive is suitably used in a molar ratio of 3:1 to 0.01:1 ( [zwitterion] : [cation] ) preferably 2:1 to 0.05:1, most preferably 1.5:1 to 0.1:1, with respect to mobile ions in the electrolyte.
  • the ideal molar ratio differs according to the type of solvent (e.g., polymer, ionic liquid or aprotic solvent) and is dictated by the conflicting forces of increasing dissociation and increasing viscosity which occur with the addition of the zwitterion.
  • the ideal molar ratio is a function of the properties of the zwitterion, the solvent, the mobile ion (salt) and any other additives which might be present.
  • the electrolyte composition may further comprise any other diluents, solvents or any other additives.
  • Gelling additives may be used to impart gel properties. Gels may be considered to be "quasi-solids" as they have some structural properties, but retain the conductive properties of the liquid.
  • the gelling additives may be selected from inorganic particulate materials (sometimes referred to as nanocomposites or nano-fillers, being fine particulate inorganic composites) . Amongst these, examples are SiO 2 , TiO 2 and Al 2 O 3 . Other gelling additives are the polymer gelling additives.
  • Suitable additives are polyelectrolytes, other zwitterionic compounds, and other electrolytes.
  • these additives are shown to improve the deposit morphology and efficiency of the lithium cycling process and are also claimed for this invention.
  • One of the additives also provides a quasi-solid gel material while retaining the conductivity of the liquid. This offers specific benefits over liquids in that it enables the fabrication of flexible, compact, laminated all solid-state devices free from leakage and in varied geometries.
  • the electrolyte composition may further comprise a gelling additive in a weight ratio of 0.01 to 20 wt% with respect to the electrolyte, preferably 1 to 10 wt%.
  • solvents such as organic solvents.
  • Preferred organic solvents are water immiscible organic solvents.
  • the organic solvent may be used in an amount of 0-90 wt%, preferably 10-70 wt%.
  • the electrolyte compositions may be prepared by the addition of a zwitterion to a mobile ion-containing electrolyte, optionally together with further additives, and/or solvent and/or polymer and/or polyelectrolyte.
  • ⁇ cosolvent can be used to dissolve all of the components.
  • the composition should be mixed until homogeneous and then the cosolvent removed and the mixture dried according to the appropriate procedure for the type of electrolyte (e.g., ionic liquids and polymers can be dried under vacuum at elevated temperatures, other solvents must be distilled off at reduced pressure) .
  • the liquid compositions may be degassed with a stream of dry argon to remove dissolved gases and residual water.
  • electrochemical devices broadly encompasses all devices containing an electrolyte, such as batteries, including Li-batteries (both Li-ion and Li-metal batteries) , capacitors, hybrid battery/capacitors, fuel cells, electromechanical actuators, photoelectrochemical solar cells, electrochromic displays and sensors.
  • batteries including Li-batteries (both Li-ion and Li-metal batteries) , capacitors, hybrid battery/capacitors, fuel cells, electromechanical actuators, photoelectrochemical solar cells, electrochromic displays and sensors.
  • the term energy storage device encompasses any device that stores or holds electrical energy, and encompasses batteries, supercapacitors and asymmetric (hybrid) battery- supercapacitors.
  • the term battery encompasses single cells.
  • Lithium based energy storage devices are ones that contain lithium ions in the electrolyte.
  • Lithium battery encompasses both lithium ion batteries and lithium metal batteries.
  • Lithium ion batteries and lithium metal batteries are well known and understood devices, the typical general components of which are well known in the art of the invention.
  • Secondary lithium batteries are lithium batteries which are rechargeable.
  • the combination of the electrolyte and negative electrode of such batteries must be such as to enable both plating/alloying (or intercalation) of lithium onto the electrode (i.e. charging) and stripping/de- alloying (or de-intercalation) of lithium from the electrode (i.e. discharging) .
  • the electrolyte is required to have a high stability towards lithium, for instance approaching ⁇ 0V vs. Li/Li + .
  • the electrolyte cycle life is also required to be sufficiently good, for instance at least 100 cycles (for some applications), and for others, at least 1000 cycles.
  • the general components of a secondary lithium battery are well known and understood in the art of the invention.
  • the principal components are: a battery case, of any suitable shape, standard or otherwise, which is made from an appropriate material for containing the electrolyte, such as aluminium or steel, and usually not plastic; battery terminals of a typical configuration; at least one negative electrode; at least one positive electrode; optionally, a separator for separating the negative electrode from the positive electrode (for liquid electrolytes - for polymer electrolytes these are not required as the polymer separates the electrodes) ; and an electrolyte (in this case,, the electrolyte composition described abo-sre) .
  • the negative electrode comprises a metal substrate, which acts as a current collector, and a negative electrode material.
  • the negative electrode material can be lithium metal, a lithium alloy forming material, or a lithium intercalation material; lithium can be reduced onto/into any of these materials electrochemically in the device.
  • the metal substrate underlying the lithium may be any suitable metal or alloy, and may for instance be formed from one or more of the metals Pt, Au, Ti, Al, W, Cu or Hi.
  • the metal substrate is Cu or Ni.
  • the negative electrode surface may be formed either in situ or as a native film.
  • native film is well understood in the art, and refers to a surface film that is formed on the electrode surface upon exposure to a controlled environment prior to contacting the electrolyte. The exact identity of the film will depend on the conditions under which it is formed, and the term encompasses these variations.
  • the surface may alternatively be formed in situ, by reaction of the negative electrode surface with the electrolyte. The use of a native film is preferred.
  • the positive electrode is formed from any typical lithium intercalation material, such as transition metal oxides and their lithium compounds.
  • transition metal oxide composite material is mixed with binder such as a polymeric binder, and any appropriate conductive additives such as graphite, before being applied to or formed into a current collector of appropriate shape.
  • binder such as a polymeric binder
  • any appropriate conductive additives such as graphite
  • the separator may be of any type known in the art, including glass fibre separators and polymeric separators, particularly micropor ⁇ us polyolefins.
  • the battery will be in the form of a single cell, although multiple cells are possible.
  • the cell or cells may be in plate or spiral form, or any other form.
  • the negative electrode and positive electrode are in electrical connection with the battery terminals.
  • a supercapacitor comprises: a device case; - terminals for electrical connection; at least one negative electrode, which may be formed from a "double layer capacitor” type of material, such as a mixture of conductive carbon and highly activated (high surface area) carbon, which are bound to a metallic substrate (current collector) , or from a pseudocapacitive redox material, displaying pseudocapacitive behaviour; - at least one positive electrode,, of one of the types described above in relation to the negative electrode; optionally, a separator for maintaining physical separation of the negative and positive electrode ; and the electrolyte composition as described herein.
  • Asymmetric (hybrid) battery-supercapacitors are devices in which one battery electrode is combined with one supercapacitor electrode to yield an energy storage device which has properties that are intermediate between those of batteries and supercapacitors.
  • an asymmetric battery-supercapacitor comprises: a device case; terminals for electrical connection; a negative electrode; a positive electrode; - a separator for maintaining physical separation of the positive and negative electricity; and the electrolyte as described herein, wherein one of said negative electrode and positive electrode is a battery electrode, and the other electrode is a double-layer capacitor electrode.
  • the negative electrode is a battery negative electrode, such as a lithium intercalation material or a lithium metal electrode
  • the positive electrode is a double layer capacitor positive electrode, typically a high surface area carbon electrode material bonded to a metal substrate.
  • the negative electrode is a double layer capacitor electrode, typically a high surface area carbon electrode material bonded to a metal substrate
  • the positive electrode is a battery electrode, such as one that contains a lithium intercalation material.
  • the electrolyte may contain some lithium ions, but need not do so. Accordingly, in this embodiment of the invention, the presence of lithium ions is optional.
  • N-methyl-N-(n-butanes ⁇ lfonate) pyrrolidini ⁇ m zwitterion N-methylpyrrolidine (4.1 mL, 0.04 moles) was added to a solution of I,4-butane sultone (4 ml, 0.04 moles) in acetone (50 ml) and the solution stirred under N 2 for 6 days at room temperature, during which time the product slowly formed as a white precipitate. This was removed by filtration under nitrogen, the product washed three times with acetone (3x20 ml) and dried under vacuum. The product was obtained as a hygroscopic white powder, melting point 322 °C.
  • N-methyl-N- (n-propanesulfonate) pyrrolidini ⁇ u ⁇ zwitterion N-methylpyrrolidine (4.7 mL, 0.0456 moles) was added to a solution of 1,3-propane sultone (4 ml, 0.0456 moles) in acetonitrile (50 ml) and the solution stirred under H 2 for 6 days at room, temperature, during which time the product slowly formed as a white precipitate. This was removed by filtration under nitrogen, the product washed three times with acetone (3x20 ml) and dried under vacuum. The product was obtained as a hygroscopic white powder, melting point 320 °C.
  • 1-butylimidazolium-3-n-butanesulfonate was synthesized following the procedure of Yoshisawa et al. for analogous z witter ionic species.
  • 1-butylimidazole (15 g, 0.1208 moles) was added to a solution of 1,4-butane sultone (12.36 ml, 0.1208 moles) in acetone (50 ml) and the solution stirred under N 2 for 6 days at room temperature, during which time the product slowly formed as a white precipitate. This was removed by filtration under nitrogen, the product washed three times with acetone (20 ml) and dried under vacuum.
  • the copolymer-type polyelectrolytes, P(AMPSLi-c-DMAA) and P(MALi-c-DMAA) were prepared by free-radical polymerization of DMA (Aldrich) and AMPSLi, or MALi, obtained by neutralization of AMPS or MA (Aldrich) with lithium carbonate (Aldrich) , and 0.15 mol% of potassium persulphate (M&B) as initiator. Polymerisation was carried out at 50°C for 2 hours and then at room temperature for 24 hours. The copolymers (solid powder) were dried under vacuum (80 torr) at 65°C for at least 3 days.
  • the polyelectrolyte gels of P(AMPSLi-c-DM ⁇ ) were prepared by raising the copolymer with PC, with or without zwitterion, at elevated temperatures for more than one day.
  • PEG200 was used as the solvent.
  • the zwitterion was used at a weight ratio of copolymer/zwitterion/solvent of 1:1:9 in Example 5.
  • Example 5 the polyelectrolyte-TiO 2 system, TiO 2 was polymerised In situ by mixing the monomers in the ratio of 10 mol% of AMPSLi and 90 mol% of DMAA in PC, with or without zwitterions.
  • concentration of polyelectrolyte, PC and zwitterions was the same as in the above system of Example 5.
  • the ionic liquid electrolyte compositions containing zwitterions were prepared by the addition of the zwitterion to the electrolyte at room temperature, mixing and drying under vacuum at elevated temperatures.
  • the solutions were degassed with a stream of dry argon to remove dissolved gases and residual water.
  • the molecular solvent electrolyte compositions containing zwitterions were prepared by the addition of the zwitterion to the electrolyte (battery grade) at room temperature, the resulting solution was mixed thoroughly.
  • 'Battery' like cells were fabricated using resealable stainless steel cells which were developed in-house, as illustrated in Figure 1.
  • the basic design incorporated a case 1, electrodes 2a and 2b, a separator 3 incorporating electrolyte, polypropylene sleeves 4, a socket head screw 5, and a Teflon gasket 6 to seal, and electrically isolate, the two halves of the cell.
  • Stack pressure in the cell was maintained fojf means of a spring 7, which applied ⁇ 1 kgc ⁇ f 2 stack pressure perpendicular to the electrode surface.
  • both electrodes were formed from lithium metal. This was formed from lithium metal foil (Jkldrich 99.9 % - thickness 180 ⁇ m) , which was washed with hexane and brushed with a polyethylene brush
  • Glass fibre mats or microporous polyolefin sheets were cut to sise and used as the separators.
  • the positive electrode (2a) was prepared by coating an aluminium foil with an active material formulation.
  • the active material (AM) was LiCoO 2 .
  • the electrode coating was prepared by weighing the components in the following ratios; AM - 80%, Graphite (KS 4 ) - 7%, Carbon Black - 3%, PVdF - 10%.
  • the solid components were mixed in a mortar and pestle and a quantity of dimethy1acetamide (DMAc ⁇ 130%) was added slowly with mixing to form a slurry.
  • the slurry was transferred to a beaker and heated (low heat) with constant stirring until the mixture had reached the correct consistency.
  • the slurry was then applied to the current collector (aluminium) using the doctor blade technique.
  • the resulting coated foil was then dried at 60 °C for several hours prior to drying under vacuum at 60 °C for greater than 24 hours.
  • Galvanostatic cycling of battery-like cells The symmetrical cells were tested by applying a galvanic square wave and monitoring the voltage response of the cell. Each cycle was set to pass a constant amount of lithium of 0.1 Gc ⁇ f 2 of lithium. The applied current was increased sequentially at ten cycle intervals until the voltage response of the cell began to increase dramatically. M, dramatic increase in the voltage response indicates that the lithium redox process is no longer able to sustain the applied current and another process (most likely solvent reduction) has begun to supply the required current. In most cases this type of process is likely to be poorly reversible and will result in the consumption of components of the electrolyte and will ultimately result in failure of the cell. Thus, an experiment of this type pro-rides a comparison of the rate capability of the electrolyte with and ifithout the addition of zwitterion.
  • electrochemical impedance spectroscopy was performed. This measurement provides information about the resistive and capacitive response of the cell when it is at rest. In this way it is possible to monitor the various resistive components of the cell after each cycling period to determine whether the incremental increase in applied current has had any effect on the components of the cell. A cell in which the lithium redox process has been able to maintain the required current density will not exhibit significant (detrimental) change in its impedance response. These measurements also allow comparison of the magnitude of the resistances present in the symmetrical cells with and without the addition of zwitterion.
  • C refers to the C rate of the cell which corresponds to the current required to charge the cell to its theoretical capacity in 1 hr, thus C/10 is the current required to charge the cell in 10 hours.
  • the theoretical capacity was determined from the mass of AM coated onto the aluminium foil; in the case of the LiCoO 2 the specific capacity used was 150 mAh/g.
  • the cells were charged at the C/10 current up to a voltage of 4.2 V and discharged at the C/10 current down to a voltage of 3.0 V.
  • the electrochemical measurements were performed in a 3- electrode cell 8, consisting of a platinum (or copper or nickel) working electrode (WE) 9, a lithium quasi- reference electrode (RE) 10, and a lithium counter electrode (CE) 11.
  • WE platinum (or copper or nickel) working electrode
  • RE lithium quasi- reference electrode
  • CE lithium counter electrode
  • Li/Li + Li(s) is oxidised to Li + (dissolution) , producing a positive current (corresponding to discharging a Li metal cell) . Integrating the curves provides a measure of the amount of charge deposited (reduced Li + ) and the amount of charge stripped (oxidised Li(s) . In this case the ratio of [oxidised Li (s) :reduced Li + ] provides a measure of the efficiency of the deposition/dissolution process. An efficiency of less than 100% indicates that the deposited lithium has reacted with the electrolyte and/or contaminants to produce a product that is not electrochemically reversible.
  • Example 1 This example compares the results of cyclic voltammetry tests on an electrolyte without zwitterion additive, and with zwitterion additive, and show that the addition of the zwitterion does not adversely affect the electrochemical stability and high reversibility.
  • Fig. 3a The electrochemical stability of N-meth ⁇ l-N- butylpyrrolidinium bis (trifluoromethanesulfonyl)imide ionic liquid electrolyte was determined by cyclic voltammetry using a silver quasi-reference electrode and Pt working and counter electrodes (Fig. 3a) . Large irreversible oxidation or reduction peaks were not observed indicating that degradation of the electrolyte had not occurred within the potential region of the experiment.
  • Fig 3b shows the electrochemical stability of the above electrolyte with 0.15 mol/kg N-meth ⁇ l-N- (n- butanesulfonate) pyrrolidinium zwitterions added and again no large irreversible oxidation or reduction peaks were observed.
  • This example compares the cyclic voltamograms for an electrolyte containing lithium ions (0.5 mol/kg) with and without zwitterion additive, and shows that the addition of zwitterion does not adversely impact on electrochemical stability, and moreover gives rise to a greater peak height, representing higher rate capability.
  • the electrochemical stability of a 0.5 mol/kg lithium bis (trifluoromethanesulfonyl)imide / N-methyl-N- butylpyrrolidinium bis (trifluoromethanesulfonyl) imide on a lithium electrode deposited on to a Cu substrate is determined by cyclic voltammetry (Fig. 4a.) . High reversibility of the lithium deposition/dissolution process is observed with no indication of degradation of the electrolyte.
  • Fig 4b shows the electrochemical stability of the above electrolyte with 0.15 mol/kg N- methyl-N- (n-butanesulfonate) pyrrolidinium zwitterion added and again high reversibility of the lithium deposition/dissolution process was observed. Comparison of the peak currents in the two figures indicates that lithium transport (and hence rate capability) is enhanced in the presence of the zwitterion.
  • the electrochemical stability of a 0.5 mol/kg lithium bis(trifluoromethanesulfonyl)imide in N-methyl-N- propylpyrrolidinium bis (trifluoromethanesulfonyl) imide on a lithium electrode deposited on to a Cu substrate is determined by cyclic voltammetry (Fig. 3a.) . High reversibility is observed with no indication of degradation of the electrolyte.
  • Fig 3b shows the electrochemical stability of the above electrolyte with 0.15 mol/kg N-methyl-N-(n-butanesulfonate) pyrrolidinium zwitterion and again high reversibility was observed. Comparison of the peak currents in the two figures indicates that lithium transport is enhanced in the presence of the zwitterion.
  • This example repeats the work of Example 2 with a polyelectrolyte in place of the ionic liquid electrolyte and again shows stability and enhanced rate capability with the addition of zwitterion.
  • Example 5 The zwitterion is a white powder at room temperature, of melting point 152 °C, with an inherently low conductivity ( ⁇ 10 -7 S cm -1 at 70°C) .
  • the applicability of this material as a lithium ion dissociator in a range of lithium polyelectrolyte systems was first examined using a random copolymer of 10 wt% lithium 2-acrylamido-2-methyl-1- propanesulfonic acid (AMPSLi) and 90 wt% N, W- dimethylacryl amide (DMA ⁇ ) .
  • the copolymer is a transparent solid material, P(AMPSLi-c-DMA ⁇ ) , at room temperature.
  • Figure 7a also demonstrates the effect of the zwitterion on the polyelectrolyte system to which nanoparticulate inorganic filler has been added.
  • Such nanocomposites have been much studied for the purposes of increasing lithium ion mobility.
  • the zwitterionic dissociation enhancement effect is additive to the mechanisms that enhance conduction in the nanocomposites.
  • the results show that even when the polyelectrolyte system already contains a nanosized filler, 6 wt% TiO 2 , to enhance the conductivity, addition of the zwitterion results in a further doubling of the conductivity ( Figure 7a) .
  • lithium ion concentration and conductivity are similar for both systems, with a maximum at around 0.047 mole fraction of Li + , above which the conductivity begins to fall slowly. This is considered to be a result of repulsion of the increased number of charges on the polymer backbone, which causes the polymer chains to condense into tight coils, restricting the movement of the lithium ions in the dissociated state between the chains. This effect falls off at high lithium concentrations, and is the basis for the so-called lithium-ion condensation phenomenon.
  • a second possible explanation is that as the lithium concentration in the polyelectrolyte is increased, the local molecular motion is decreased through interaction between the lithium ion and the solvent system.
  • Tg glass transition temperatures
  • the viability of using these materials in lithium batteries has been tested by cyclic voltammetry.
  • the materials reversibly deposit lithium onto a copper substrate at rates up to 10m&,cia ⁇ 2 (for the 1.5:1:9 weight ratio system of 50:50 P(IMPSLi-c-DMiyk) + zwitterion + DM_%/EC (1:2 wt%) ) .
  • the onset of the decomposition peak was observed at >4.5 V (versus Li) making it suitable for a range of well-known high-voltage materials.
  • Example 5 show that the addition of a zwitterionic species to a range of lithium polyelectrolyte gels is extremely effective in enhancing the dissociation of lithium ions from the polymer backbone, a key requirement in the optimization of electrolyte systems for lithium-ion secondary batteries.
  • Utilization of this new lithium ion dissociator has resulted in ionic conductivities up .to seven times greater than the pure polyelectrolyte systems, and NMR analysis has confirmed that this conductivity increase is a direct result of increased lithium ion mobility within these systems.
  • the widespread applicability of this method has been demonstrated, with significant conductivity enhancements observed on addition of zwitterion to a number of different copolymer and solvent systems. Indeed, even in systems that already contain an optimum amount of traditional ion dissociator, the conductivity can be doubled again by the addition of zwitterion.
  • the zwitterion would provide a polar medium for movement of the lithium ion through the polyelectrolyte, with the zwitterion allotting eoulombic screening of the anionic charges on the polymer.
  • the lithium preferentially interacts with the sulphonate group on the zwitterion, rather than the sulphonate group on the polymer, thereby increasing dissociation of the lithium from the polymer backbone, but the possible reason for this is not clear.
  • Example 6 N-methyl-N(n-propanesulfonate) pyrrolidinium zwitterion was added to a commercial electrolyte used in applications such as mobile or cell phones (1M LiPF 6 in ethylene carbonate:diethyl carbonate in ratio of 1:1 by volume) .
  • the zwitterion was used in molar ratios compared to the 1M LiPF 6 of 0.0, 0.1, 0.2, 0.3, 0.4, 0.5 and 1.0.
  • the cyclic voltamograms showed that, as the viscosity of the system increased, with increasing addition of zwitterion, the peak current decreased, as expected due to the reduced mobility of the Li in the increasingly viscous system.
  • the cell at 80 °C exhibits an even more pronounced difference, with the cell containing zwitterions able to maintain 8 mAcm -2 of applied current for 0.1 Ccm -2 of lithium without apparent detriment to the cell voltage response.
  • the plots shown in Figures 13a and 13b summarise the data obtained from, the galvanic square wave experiments.
  • a cell which is able to maintain the applied current densitj through the action of " a reversible process (i.e., Li + ⁇ £> Li°) there should be no significant change in the resistance of the cell. It is apparent that the addition of zwitterions allows the cell to operate at approximately double the rate (i.e.

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Abstract

Electrolytes zwittérioniques tels que le N-méthyl-N (n-butanesulfonate) pyrrolidinium, ajoutées à des compositions électrolytiques telles que les polyélectrolytes, les électrolytes ioniques liquides et les électrolytes moléculaires solvantes (par exemple, l’hexafluorophosphate de lithium) pour augmenter la conductivité des espèces ioniques, telles que le lithium, dans l’électrolyte. Ceci s’applique aux dispositifs de stockage d’énergie à base de lithium, tels que les piles ou les supercondensateurs.
PCT/AU2005/001237 2004-08-20 2005-08-17 Additifs zwittérioniques pour dispositifs électrochimiques WO2006017898A1 (fr)

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