WO2018060680A1 - Systèmes améliorés de stockage de charges polymères - Google Patents

Systèmes améliorés de stockage de charges polymères Download PDF

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WO2018060680A1
WO2018060680A1 PCT/GB2017/052821 GB2017052821W WO2018060680A1 WO 2018060680 A1 WO2018060680 A1 WO 2018060680A1 GB 2017052821 W GB2017052821 W GB 2017052821W WO 2018060680 A1 WO2018060680 A1 WO 2018060680A1
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thin film
storage device
derivatives
group
type
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PCT/GB2017/052821
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Jonathan Pillow
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Cambridge Display Technology Limited
Sumitomo Chemical Company Limited
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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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
    • H01M4/602—Polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/31—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain
    • C08G2261/314—Condensed aromatic systems, e.g. perylene, anthracene or pyrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/31—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain
    • C08G2261/314—Condensed aromatic systems, e.g. perylene, anthracene or pyrene
    • C08G2261/3142—Condensed aromatic systems, e.g. perylene, anthracene or pyrene fluorene-based, e.g. fluorene, indenofluorene, or spirobifluorene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/31—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain
    • C08G2261/316—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain bridged by heteroatoms, e.g. N, P, Si or B
    • C08G2261/3162—Arylamines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/50—Physical properties
    • C08G2261/51—Charge transport
    • 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

Definitions

  • This invention relates to polymer charge-storage systems, and particularly to new materials for thin-film charge-storage devices, such as battery/supercapacitor hybrids, which enable the reduction in thickness of the charge-storage device and an increase in energy density.
  • the invention also relates to a method of manufacturing these devices.
  • Thin film batteries generally achieve high energy densities but typically provide low power due reversible coulombic reactions occurring at the electrodes, involving charge transfer and ion diffusion in electrode materials, thereby kinetically limiting the power delivery as well as the recharging time.
  • supercapacitors store energy through accumulation of ions on the electrode surface, i.e. through a coulombic charge storage process, so that supercapacitors may provide more power per unit mass than batteries and enable burst power supply for electric vehicles, for example.
  • Thin film charge-storage devices comprising n- and p-type electroactive conjugated polymers have previously been demonstrated to offer good conductivity of both ions and charges that allow them to act as redox-active materials in charge-storage devices ⁇ see e.g. US 4,442,187 A). In these, they show properties of both batteries and supercapacitors, depending on a number of factors including the degree of shielding of each charge from the next one along the polymer chain, and the relative mobility of charges and ions within the polymer layers.
  • the p-type polymer in the electroactive polymer layer (4) at the anode side (5) becomes positively charged, and anions from the electrolyte move in to compensate the charge.
  • both polymers return to their neutral states, and ions return to the solution.
  • a characteristic feature of such a device is that two different ions are required, which both typically originate in a liquid form inside the separating membrane between the two electroactive polymer materials and frequently take the form of an ionic liquid. Accordingly, such a configuration requires the separator layer to store all ionic species in the discharged state.
  • the separator must have a sufficient thickness to satisfactorily perform as an ion reservoir (typically about one third or more of the overall thickness of the electroactive layers), which imposes limitations on the dimensions of the overall charge storage device, the current output, and also the internal resistance.
  • This invention describes a thin film charge -storage device, wherein one of the electroactive polymers exists in an ionic form in the discharged state, in which it includes a mobile counter-ion of the same polarity that it will accept during the charging process.
  • the thin film charge- storage device of the present invention there is only the need for one ion to migrate from one polymer layer through the separator to the second polymer layer, rather than for two ions to migrate from the separator into the two respective polymer layers.
  • the separator can be substantially thinner (until it merely acts as an ion-transporting separator) and can also be more finely optimized to carry the single ionic species.
  • the present invention relates to comprising an n-type electroactive polymer layer, a p-type electroactive polymer layer and a separator between the electroactive polymer layers, wherein, in a discharged state of the thin film charge-storage device, one of the p-type or the n-type electroactive polymers has a repeating unit comprising a covalently attached ionic group which is ionically bound to a mobile counter- ion.
  • the present invention relates to a method of manufacturing a thin film charge-storage device comprising an n-type electroactive polymer layer, a p-type electroactive polymer layer and a separator between the electroactive polymer layers, wherein the method comprises a step of depositing one of the p-type or the n-type electroactive polymers in a state, wherein its repeating units comprise a covalently attached ionic group which is ionically bound to a mobile counter-ion.
  • FIG. 1 a schematically illustrates the general architecture of a conventional electroactive polymer-based charge-storage device and the electron flow and ion movement during charge.
  • FIG. 1 b schematically illustrates the electron flow and ion movement during discharge.
  • FIG. 2a schematically illustrates the function of a charge -storage device comprising an anionic p-type electroactive polymer according to the present invention during charge.
  • FIG. 2b schematically illustrates the electron flow and ion movement during discharge.
  • FIG. 3a schematically i!!ustrates the function of a charge-storage device comprising a cationic n-type electroactive polymer according to the present invention during charge.
  • FIG. 3b schematically illustrates the electron flow and ion movement during discharge.
  • the present invention relates to a thin film charge-storage device comprising an n- type electroactive polymer layer, a p-type electroactive polymer layer and a separator between the electroactive polymer layers, wherein, in a discharged state of the thin film charge-storage device, one of the p-type or the n-type electroactive polymers has a repeating unit comprising a covalently attached ionic group which is ionical!y bound to a mobile counter-ion.
  • electroactive polymer denotes a polymer which exhibits variable physical and/or chemical properties resulting from an electrochemical reaction within the polymer upon application of an external electrical potential, and must be thus distinguished from electrochemicaily inert materials or insulating materials, such as conventional electrolytes and porous separator layer supports.
  • the electroactive polymer comprising a covalently bound ionic group exhibits repeating units containing both an electroactive unit and a unit comprising the covalently bound ionic group to which a mobile counterion is attached. It is to be noted that both units may be separate or be combined within a single unit.
  • electroactive unit generally denotes a structural motif in the electroactive polymer which is capable of accepting (n-type) or donating (p-type) an electron in the presence of an electrical field so as to carry the electrical charge -1 or +1 , which may be present in the form of unpaired electrons, the latter often residing in the HOMO (for a cation) or LUMO (for an anion) of the molecular species.
  • the electroactive polymer comprising the covalently bound ionic group may be described by the following general formula (1 ): wherein at least one of the groups Yi to Y3 comprise an electroactive (n-type or p-type) unit and at least one of the groups Yi to Y3 comprise a covalently bound ionic group to which a mobile counter-ion is attached; wherein both the electroactive unit and the ionic group may be separate or be combined within a single unit; and wherein the group Yi to Ya neither comprising the electroactive unit nor the covalentiy bound ionic group, if present, may be a single bond or an in-chain conjugated aromatic or heteroaromatic group, for example.
  • the material providing for the electroactive units may be selected from electroactive substances known in the art.
  • the p-type electroactive polymers are not particularly limited and may be appropriately selected from standard electron donating conjugated organic polymers which are readily oxidized in relation to a high workfunction electrode so as to form stable oxidation products. Suitable compounds will be known to the person skilled in the art and are described in the literature.
  • the p-type conjugated organic polymer is a co-polymer including alternating, random or block copolymers.
  • polymers selected from conjugated hydrocarbon or heterocyclic polymers may be mentioned.
  • in-chain conjugated (co- ⁇ polymers comprising as monomer units one or more selected from the group consisting of acene, aniline, azulene, benzofuran, fluorene, furan, indenofluorene, indole, phenylene, pyrazoline, pyrene, pyridazine, pyridine, diarylalkylamine, triarylamine, phenylene vinylene, 3-substituted thiophene, 3,4-bisubstituted thiophene, selenophene, 3-substituted selenophene, 3,4-bisubstituted selenophene, bisthiophene, terthiophene, bisselenophene, terselenophene, thieno[2,3-b]thiophene, thieno[3,2-b]thiophene, benzothiophene, benzo[1 ,2-
  • n-type electroactive polymers are also not particularly limited and may be suitably selected from electron accepting materials which are readily reduced in relation to a low workfunction electrode so as to form stable reduction products.
  • Suitable n-type polymers will be known to the skilled artisan and may consist of a mixture of a plurality of electron accepting materials.
  • Preferred examples of n-type organic semiconductors are in- chain conjugated (co-)poiymers of monomers selected from the group of fluoreny! derivatives, heteroaromatic hydrocarbons (such as e.g. benzothiadiazoles and its derivatives, triazine derivatives (e.g.
  • the separator is not particularly limited and may be made of known materials that are chemically and electrochemica!ly unreactive with respect to the charges and to the electrode polymer materials in their neutral and charged states. Typically, the separator contacts the n-type and p-type electroactive polymer layers such that the transport of ions is facilitated.
  • porous polymeric materials e.g. polyethylene, polypropylene, polyester, PTFE or cellulose-based polymers
  • ion-conductive polymer membranes e.g. NationalTM
  • (electronically non-conductive) gel electrolytes e.g.
  • Polymers, when used as a separator, should be resistant towards dissolution by the electrolyte, which may be appropriately achieved by methods known to the skilled artisan (e.g. by suitable selection of materials or by cross-linking).
  • electroactive polymer as used in the present invention may generally comprise cross-linking units, i.e. functional groups which enable to bond the polymer chains, which may be appropriately chosen by the skilled artisan.
  • electroactive polymer layers may consist of the electroactive polymers, the layers may comprise further materials that are conventionally used in the preparation of polymeric films for thin film devices.
  • electroactive polymer layers may be combined with one or more layers that may be polymeric or non-polymeric (e.g. a current collector layer) and/or comprise material embedded into the respective polymer films (e.g. a conductive material for electrode connection etc.).
  • Suitable materials for current collector layers include material that is selected from the group consisting of porous graphite, porous, highly doped inorganic semiconductor, highly doped conjugated polymer, carbon nanotubes or carbon particles dispersed in a non-conjugated polymer matrix, aluminum, silver, platinum, gold, palladium, tungsten, indium, zinc, copper, nickel, iron, lead, lead oxide, tin oxide, indium tin oxide, graphite, doped silicon, doped germanium, doped gallium arsenide, doped polyaniline, doped polypyrrole, doped polythlophene, and their derivatives.
  • the thin film charge-storage device according to the present invention may also comprise additional layers, such as one or more encapsulation layers, for example.
  • the thin film charge-storage device of the present invention is a battery/supercapacitor hybrid.
  • the electrolyte for use in the thin film charge-storage device of the present invention is not particularly limited and may be suitably selected by the skilled artisan depending on the chosen separator and polymer materials as well as the mobile ionic species. While not being limited thereto, it may be preferable to use electrolytes that are liquid at room temperature (25°C). As examples thereof, electrolyte salts dissolved in appropriate solvents as commonly used in the art or ionic liquids that are typically liquid below 100 °C may be mentioned, the latter including, but not being limited to ammonium-, imidazolium-, phosphonium-, pyridinium-, pyrrolidinium-, and sulfonium-based ionic liquids. As the use of ionic liquids allows volatile and hazardous conventional solvents to be eliminated and improves the operational stability of these devices, ionic liquids may be preferable as liquid electrolytes.
  • each of the n-type and p-type electroactive layers containing the continuous, solid and porous electroactive polymer material may be chosen appropriately depending on the required purpose and is typically in a range of between 0.05 to 500 pm.
  • the separator layer thickness may likewise be appropriately selected by the skilled artisan depending on the purpose.
  • the separator thickness is typically about one third or more of the overall thickness of the electroactive layers since the separator must store both the anionic and cationic mobile species in the discharged state of the device.
  • the separator layer thickness may be reduced to a thickness of 25% or less, usually 20% or less, in embodiments 15% or less of the overall thickness of the electroactive layers without substantially affecting the energy density within each electroactive polymer layer, which enables manufacturing of thinner devices without compromising their performance and which have remarkably improved charge-storage density (up to 50% increase).
  • the separator thickness is 20 ⁇ or less, preferably 10 m or less.
  • the p-type polymer exhibits in a discharged state of the thin film charge-storage device a repeating unit comprising a covendingiy bound anionic group to which a mobile cation is attached.
  • the n-type polymer is substantially non-ionic in the discharged state of the thin film charge-storage device.
  • FIGS. 2A and 2B show the electron flow and ion movement during charge (Fig. 2A) and discharge (Fig. 2B).
  • the p-type polymer P N " in layer (4a) comprises a covendingiy bound anionic group to which a mobile cation is attached.
  • the mobile cations move towards the n-type polymer layer (2) to counterbalance the growing negative charge formed by electrochemical reduction (Fig. 2A).
  • the mobile cations move towards the p-type polymer and bind to their covendingiy bound anionic groups (Fig. 2 B).
  • the separator may be substantially thinner and may also be more finely optimized to carry the single ionic species.
  • the mobile cation is not particularly limited any may be suitably selected by the skilled artisan depending on its stability, mass and/or ease of movement.
  • Suitable organic cations may be derived from known imidazolium derivatives, pyrrolidinium derivatives, isoquinolinium derivatives, alkylsulfonium derivatives, ammonium derivatives, phosphonium derivatives and aminium derivatives typically used in ionic liquids. Specific examples thereof are disclosed in S. Zhang et al., J. Phys. Chem. Ref. Data 2006, 35(4), 1477-1481.
  • the mobile cation is selected from any of imidazolium derivatives, pyrrolidinium derivatives, phosphonium derivatives, pyridinium derivatives, asymmetric aliphatic quaternary ammonium derivatives, guanidinium derivatives.
  • monovalent or divalent metal cations may be advantageously used, of which Na + , Li + , Mg 2+ , Ca s+ and Zn 2+ are preferred examples.
  • Li + is particularly favourable as it is lightweight, relatively non-toxic and may be used with a variety of known separator materials designed to selectively transport Li + .
  • Divalent metal cations, such as Mg 2+ are capable of transporting two charges in their +11 state, which enables very fast ion movement, particularly when compared to bulkier organic ion species.
  • the anionic group covalently bound in the repeating unit may be an in- chain or a pendant anionic group, a pendant anionic group is preferable.
  • the anionic group is not particularly limited as long as it is stable and capable of electrically neutralizing the mobile cation.
  • the anionic group is selected from any of a carbanion, -CCV.-SCV, -O-, -BF 3 " , -NCF 3 -, -NCN " , or -S " .
  • the p-type polymer generally comprises repeating units containing both an eiectroactive unit (i.e. a structural motif in the eiectroactive polymer which is capable of donating (p-type) an electron in the presence of an electrical field so as to carry the electrical charge +1) and a unit comprising covalently bound anionic group to which a mobile cation is attached, wherein both units may be separate or be combined within a single unit, as will be further explained below.
  • the eiectroactive unit is usually in the main chain of the polymer, it may alternatively or additionally be also provided pendant from the polymer.
  • the repeating unit comprises one or more of a fluorenyl derivative, a phenyiene derivative, an aniline derivative, a dialkylarylamine, a diary!alkyiamine, a diarylamine, a triarylamine, a substituted or unsubstituted in-chain conjugated aromatic hydrocarbon and/or a heteroaromatic hydrocarbon. More preferably, the repeating unit comprises an arylamine derivative and/or a fluorenyl derivative.
  • Ri to F1 ⁇ 2 may be independently selected from hydrogen, a halogen, a d- C 2 o alkyi, a Ci-C 20 alkoxy, a C1-C20 haloafkyl or a substituted or unsubstituted C 6 -C 3 o aryl group, with hydrogen being preferable;
  • Zi and Z 2 independently represent a C 1 -C 2 0 alkylene group, a C1-C20 ether group, a Ci-C 20 haloalkylene or a substituted or unsubstituted C-6-C30 aryl group, at least one of the groups comprising one or more anionic groups which are preferably selected from any of a carbanion, -CO2VSO3 " , -O " , -BF3 " , - NCF3 " , -NCN “ , or -S ⁇ as a substituent.
  • the redox active unit is electrically neutral and there is a separate negative charge provided for by the anionic group
  • the negatively charged species is also the species that is oxidized.
  • the negative charge must be stabilized to an extent where unwanted chemical transformation is prevented while still enabling to be electrochemically ionized.
  • an electronegative heteroatom e.g. oxygen, nitrogen or sulphur
  • the energy level of the electron to be low enough to enable a sufficient energy difference with the n-type material or by the use of aromatic derealization, provided that the resulting unpaired electron (radical) is also sufficiently stable that it does not undergo unwanted chemical transformation.
  • stable radicals are known in the art, such as galvinoxyl and its derivatives, for example. While not being limited thereto, preferred carbanionic structures are exemplified below in conjunction with general formulae (2-4) and (2-5):
  • a preferred embodiment of a substituted or unsubstituted in-chain conjugated aromatic hydrocarbon includes a repeating unit comprising a stabilized carbanion according to general formula (2-4) that has a low-lying HOMO:
  • F1 ⁇ 2 to R 16 and Ris may be independently selected from hydrogen, a halogen, a Ci -C 20 alkyl, a Ci -C 20 aikoxy, a Ci-C 20 haloalkyl or a substituted or unsubstituted Ce-Cao aryl group, with hydrogen being preferable;
  • D is selected from any of oxygen, sulfur or C(CN)2;
  • Ri 7 represents a C1 -C20 haloalkyl, a Ce-C 3 o aryl group or a second redox-active unit, each of which may be unsubstituted or substituted by one or more electron withdrawing groups, such as e.g. a halogen, preferably fluorine.
  • Such systems can be formed in-situ from more stable and readily available material according to the following reaction scheme, wherein L represents a leaving group which may be suitably selected by the skilled artisan, such as CO2 or formaldehyde, for exam le:
  • CO2 as L
  • the material could be encapsuiated after removal of the leaving group L so that the CO2 could be released, or it could be simply allowed to remain in the battery or to diffuse slowly out.
  • a repeating unit comprising a structural motif which allows stabilization through aromatic derealization is shown in general formula (2-5):
  • R 22 to R29 may be independently selected from hydrogen, a halogen, a C1-C20 alkyl, a C1-C20 aikoxy, a C1-C20 haloalkyl or a substituted or unsubstituted C-6-C30 aryl group, with hydrogen being preferable; and Ar 1 and Ar 2 may be independently selected from a C6-C30 aryl group, which may have one or more substituent(s), preferably (a) substituent(s) selected from a C1-C20 alkyl group. In a further preferred embodiment, Ar 1 and Ar 2 are trimethylphenylene groups.
  • the resulting radical species may be stabilized according to the following scheme:
  • the pendant ionic group does not need to be attached directly to the electroactive unit, and the eiectroactive polymer may comprise the covalently attached ionic group and the redox-active group in two different structural motifs or co-monomers.
  • a preferred example of such as structure is general formula (2-6), which represents a combination of an arylamine derivative and/or a fluorenyl derivative:
  • R 3 o to F 4 may be independently selected from hydrogen, a halogen, a Ci- C-20 alkyl, a Ci-C 20 alkoxy, a C1-C20 haioalkyl or a substituted or unsubstituted Ce-Cao aryl group, with hydrogen being preferable;
  • R45 may independently represent any of hydrogen, a C1-C20 alkyl, a C1-C20 alkoxy, a C1-C20 haioalkyl or a substituted or unsubstituted C6-C30 aryl group or a second redox-active unit, with a C3-C18 alkyl group or C1-C20 haioalkyl having a solubiiising function being preferred;
  • FUe may independently represent any of hydrogen, a C1-C20 alkyl, a C1-C20 alkoxy, a ⁇ - ⁇ 2 ⁇ haioalkyl or a substituted or unsubsti
  • the covalently attached ionic groups form the electroactive units of the electroactive polymer, which may be accomplished by positioning at least two electroactive units in the polymer so that upon oxidation, a ir-bond rearrangement is achieved rather than leaving an unpaired electron (in analogy to the mechanism described with respect to genera! formula (2-5)). This can enable higher charge densities and also a higher electrochemical stability.
  • R 54 to Rei may be independently selected from hydrogen, a halogen, a Ci- C-20 alkyl, a C1-C20 alkoxy, a C1-C20 haloalkyl or a substituted or unsubstituted C6-C30 aryl group, with hydrogen being preferable; and Z5 and Z 6 are selected from any of -O " or -S ⁇ , preferably -O " .
  • the structural formulae (2-1) to (2-5), (2-7) and (2-8) may be comprised in the p-type polymer the sole monomers, as substructures of monomers, or as co-monomers or substructures thereof which form a part of the p-type polymer (which may be an alternating, random or block copolymer).
  • Devices comprising n-type polymers with covalently bound cationic group may be comprised in the p-type polymer the sole monomers, as substructures of monomers, or as co-monomers or substructures thereof which form a part of the p-type polymer (which may be an alternating, random or block copolymer).
  • the n-type polymer exhibits in a discharged state of the thin film charge-storage device a repeating unit comprising an covalently attached cationic group to which a mobile anion is ionically bound, in this configuration, it is preferable that the p-type polymer is substantially non-ionic in the discharged state of the thin film charge-storage device.
  • the mobile anion is not particularly limited any may be suitably selected by the skilled artisan depending on the purpose. Suitable anions include, but are not limited to chloride, perch!orate, bromide, iodide, tetrafluoroborate, 1 -carbon icosahedral, methylcarbonicosahedral, ethylcarbonicosahedrai, propylcarbonicosahedral, butylcarbonicosahedral, hexachloride-1 -carbon icosahedral, hexabromide-1 -carbon icosahedral, bis-(2-methy!lactato)borate, bis(oxalato)borate, bis(malonato)borate, bis(salicylato)borate, tetraphenylborate, tetrakis-
  • Preferred examples include fluoroalky!sulfonyiimides (e.g. bis((triffuoromethyl)sulfony!imide (TFSI), fiuoroalkylsulfonates (e.g. trifluoromethansulfonate ( Tf)), tetrafluoroborate (BF 4 ), hexafluorophosphate (PFe ) and hexafluoroantimony (SbFe " ).
  • FSSI bis((triffuoromethyl)sulfony!imide
  • fiuoroalkylsulfonates e.g. trifluoromethansulfonate ( Tf)
  • BF 4 tetrafluoroborate
  • PFe hexafluorophosphate
  • SBFe hexafluoroantimony
  • covalently bound cationic group may be an in-chain or a pendant cationic group, a pendant cationic group is preferable.
  • the cationic group is not particularly limited as long as it is stable and capable of electrically neutralizing the mobile anion.
  • the cationic group may be a nitrogen-containing cationic group derived from imidazolium derivatives, pyrrolidinium derivatives, isoquinolinium derivatives, a!kylsulfonium derivatives, ammonium derivatives, phosphonium derivatives and aminium derivatives.
  • the cationic group is a nitrogen-containing cationic group selected from pyridinium, imidazolium, -NF , and derivatives thereof, R being independently selected from a C1 -C20 alkyl, a C1 -C20 alkoxy, a C1 -C20 haloalkyl or a substituted or unsubstituted C6-C30 aryl group.
  • the n-type polymer generally comprises repeating units containing both an eiectroactive unit (i.e. a structural motif in the eiectroactive polymer which is capable of accepting an electron in the presence of an electrical field so as to carry the electrical charge -1) and a unit comprising a covalently attached anionic group to which a mobile counter-cation is ionically bound, wherein both units may be separate or be combined within a single unit, as will be further explained below.
  • the electroactive unit is usually in the main chain of the polymer, it may alternatively or additionally be also provided pendant from the polymer.
  • the n-type polymer is an in-chain conjugated ⁇ copolymer of monomers selected from the group of fluorenyl derivatives, heteroaromatic hydrocarbons (such as e.g. benzothiadiazoles and its derivatives, triazine derivatives (e.g. 1 ,3,5-triazine derivatives), azafluorene derivatives, quinoxalines), conjugated aromatic hydrocarbons (e.g. arenes, acenes), and carbonyi-based monomers (such as fluorenone derivatives).
  • heteroaromatic hydrocarbons such as e.g. benzothiadiazoles and its derivatives, triazine derivatives (e.g. 1 ,3,5-triazine derivatives), azafluorene derivatives, quinoxalines), conjugated aromatic hydrocarbons (e.g. arenes, acenes), and carbonyi-based monomers (such as fluorenone derivatives).
  • the repeating unit constituting the n-type polymer comprises a fluorenyl derivative and/or a heteroaromatic hydrocarbon, the heteroaromatic hydrocarbon being preferably selected from benzothiadiazole derivatives, triazine derivatives, azafluorene derivatives, or quinoxalines.
  • R 6 2 may be selected from hydrogen, a halogen, a C1-C20 alkyl, a C1-C20 alkoxy, a C1-C20 haloalkyl or a substituted or unsubstituted Ce-C3o aryl group, with hydrogen being preferable; and wherein Xi is represented by a group -Sp-A; with Sp being a spacer group selected from a single bond, a C1 -C20 alkylene, a C1 -C20 ether group, a G-C20 haloalkylene group or a substituted or unsubstituted C6-C30 arylene group, the spacer group being preferably an C1-C10 alkylene group; and A being a cationic group, preferably a nitrogen-containing cationic group selected from pyridinium, imidazolium, -NFV, and derivatives thereof, R being independently selected from a C1-C20 alkyl, a C1
  • R 6 3 to Res may be selected from hydrogen, a halogen, a C1-C20 alkyl, a C1-C20 alkoxy, a C C-20 haloalkyl or a substituted or unsubstituted C-6-C30 aryl group, with hydrogen being preferable;
  • R 6 g is a group capable of accepting an electron in the presence of an electrical field;
  • X 2 is represented by a group -Sp-A; with Sp being a spacer group selected from a single bond, a C1-C20 alkylene, a C1-C20 ether group, a Ci-C 20 haioalkylene group or a substituted or unsubstituted C6-C30 arylene group, the spacer group being preferably an C1 -C10 alkylene group; and
  • A being a cationic group, preferably a nitrogen-containing cationic group selected from pyridinium, imidazolium, - NR 3 +
  • R70 to R7? may be selected from hydrogen, a halogen, a C1 -C20 alkyl, a C1 -C20 alkoxy, a Ci-Cao haloalkyl or a substituted or unsubstituted C6-C30 aryl group, with hydrogen being preferable; and wherein X 3 is represented by a group -Sp-A; with Sp being a spacer group selected from a single bond, a C1-C20 alkylene, a C1 -C20 ether group, a Ci-C 20 haioalkylene group or a substituted or unsubstituted C-6-C30 arylene group, the spacer group being preferably an C1 -C10 alkylene group; and A being a cationic group, preferably a nitrogen-containing cationic group selected from pyridinium, imidazolium, - NR 3 + , and derivatives thereof, R being independently selected from a C1-C
  • a further aspect of the present invention relates to a method of manufacturing a thin film charge-storage device comprising an n-type electroactive polymer layer, a p-type electroactive polymer layer and a separator between the electroactive polymer layers, wherein the method comprises a step of depositing one of the p-type or the n-type electroactive polymers in a state, wherein its repeating units comprise a covalently attached ionic group to which a mobile counter-ion is ionically bound.

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  • Electric Double-Layer Capacitors Or The Like (AREA)
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Abstract

Un dispositif de stockage de charge à film mince comprend une couche de polymère électroactif de type n, une couche de polymère électroactif de type p et un séparateur entre les couches de polymère électroactif, dans un état déchargé du dispositif de stockage de charge de film mince, l'un des polymères électroactifs de type p ou de type n a une unité de répétition comprenant un groupe ionique lié de manière covalente auquel est attaché un contre-ion mobile, ce qui permet la fabrication de dispositifs plus minces sans compromettre leur performance et/ou de dispositifs ayant une densité de stockage de charge remarquablement améliorée.
PCT/GB2017/052821 2016-09-28 2017-09-21 Systèmes améliorés de stockage de charges polymères WO2018060680A1 (fr)

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Cited By (2)

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EP3588634A1 (fr) 2018-06-27 2020-01-01 Evonik Operations GmbH Matériau d'électrode organique amélioré
WO2020126200A1 (fr) 2018-12-17 2020-06-25 Evonik Operations Gmbh Électrolyte solide pour batteries organiques

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US20150332141A1 (en) * 2014-05-13 2015-11-19 Arizona Board Of Regents On Behalf Of Arizona State University Redox active polymer devices and methods of using and manufacturing the same
US20150333331A1 (en) * 2014-05-13 2015-11-19 Arizona Board Of Regents On Behalf Of Arizona State University Electrochemical energy storage devices comprising self-compensating polymers

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US20150332141A1 (en) * 2014-05-13 2015-11-19 Arizona Board Of Regents On Behalf Of Arizona State University Redox active polymer devices and methods of using and manufacturing the same
US20150333331A1 (en) * 2014-05-13 2015-11-19 Arizona Board Of Regents On Behalf Of Arizona State University Electrochemical energy storage devices comprising self-compensating polymers

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3588634A1 (fr) 2018-06-27 2020-01-01 Evonik Operations GmbH Matériau d'électrode organique amélioré
WO2020002032A1 (fr) 2018-06-27 2020-01-02 Evonik Operations Gmbh Matériau d'électrode organique amélioré
CN111919318A (zh) * 2018-06-27 2020-11-10 赢创运营有限公司 改善的有机电极材料
WO2020126200A1 (fr) 2018-12-17 2020-06-25 Evonik Operations Gmbh Électrolyte solide pour batteries organiques

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