• 专利附录
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    • 专利摘要:
    The invention relates to a lithium battery electrode comprising, as active material, an electrochromic material and as an electrically conductive additive, metal nanowires. Use of this electrode to form energy storage devices whose state of charge can be determined by colorimetric tracking.
    公开号:FR3047843A1
    申请号:FR1651173
    申请日:2016-02-12
    公开日:2017-08-18
    发明作者:Adriana Iordache；Lionel Picard；Jonathan Skrzypski；Sebastien Solan
    申请人:Commissariat a lEnergie Atomique CEA；Commissariat a lEnergie Atomique et aux Energies Alternatives CEA；
    IPC主号:
    专利说明:

    ELECTROCHROME ELECTRODE FOR ENERGY STORAGE DEVICE
    DESCRIPTION
    TECHNICAL AREA
    The present invention relates to novel electrodes for an energy storage device, in particular for a lithium battery comprising, as ingredients, a specific active material and a specific electrically conductive material, in particular in order to be able to visualize the state of charge of said electrode by simple color change of the latter. The invention also relates to an energy storage device comprising at least one such electrode.
    The field of the invention can be defined as that of energy storage devices, in particular that of lithium batteries.
    STATE OF THE PRIOR ART
    Energy storage devices are typically electrochemical batteries operating on the principle of electrochemical cells capable of delivering an electric current thanks to the presence in each of them of a pair of electrodes (respectively, a positive electrode and a negative electrode) separated by an electrolyte, the electrodes comprising specific materials capable of reacting in an oxidation-reduction reaction, whereby there is production of electrons at the origin of the electric current and productions of ions that will circulate from one electrode to another through an electrolyte.
    Batteries subscribing to this principle currently the most used are, in particular, lithium batteries, such as lithium-ion batteries. From a functional point of view, the lithium-ion batteries are based on the principle of intercalation-deintercalation or complexation-decomplexation of lithium within the constituent materials of the electrodes of the electrochemical cells of the battery (these materials may also be designated under the denomination of active materials).
    More specifically, the reaction at the origin of the current generation (that is to say when the battery is in discharge mode) involves the transfer, via a lithium ion conductive electrolyte. , lithium cations from a negative electrode which are interposed in the acceptor network of the positive electrode, while electrons from the reaction to the negative electrode will supply the external circuit, which are connected positive electrodes and negative.
    Among the active materials that may form part of at least one of the electrodes, they may be inorganic compounds, which may contain lithium ions in their charging or discharging process according to the invention. polarity of the electrodes; or alternatively organic compounds which are susceptible, by an oxidation-reduction reaction, to complex said lithium ions.
    These active materials are generally used in combination with an electrically conductive additive, such as carbon particles (in particular, carbon black) and also with an additive ensuring the cohesion of the electrode, in which are included the active material and the conductive additive, such an additive may be a polymeric binder, the combination of these ingredients resulting in an opaque and dense mixture.
    With such electrodes comprising such a mixture, it is thus not possible to carry out colorimetric monitoring to determine the state of charge of the electrode, when a change of state of charge is manifested by a change of color of the active material, such a change occurring in particular with electrochromic materials, since the electrically conductive additive masks the color change of the active material.
    Thus, a need is felt to estimate the state of charge of a battery in a simple manner by a simple colorimetric tracking thereof, particularly in the field of portable electronic equipment.
    This need is now filled by the authors of the present invention, who have discovered that by associating with a specific active material a specific electrically conductive additive in an electrode, it has become possible to proceed to the estimation of the state of charge of this electrode by a simple colorimetric tracking thereof.
    STATEMENT OF THE INVENTION
    Thus, the invention relates to an electrode for an energy storage device comprising, as active material, an electrochromic material and as an electrically conductive additive, metal nanowires.
    The term "active material" conventionally means, in the foregoing and the following, the material which is directly involved in the insertion and de-insertion and / or complexation and decomplexation reactions of the ions involved in the storage device. energy, these ions being lithium ions, when the device is a lithium battery.
    By associating an active material of the electrochromic material type with metallic nanowires, as an electrically conductive additive, it is possible to follow the color changes of said electrochromic material as a function of the state of charge of the electrode, without these changes are masked by the conductive additive of electricity, as is the case when it is in particular in the form of carbon black.
    For example, the electrode is deposited on a transparent substrate, which makes it possible to observe the evolution of its color as a function of its state of charge. This substrate can act as a current collector.
    The transparent substrate may be of glass or of flexible plastic material, optionally covered with an electrically conductive layer, for example an electrically conductive ceramic layer, such as a layer of indium oxide and 'tin.
    In the context of the invention, the active material is an electrochromic material, that is to say a material able to change color when an electric charge is applied to it, which means, in the operating context of the energy storage device, when this active material is in a state of discharge.
    This electrochromic material may be an inorganic material such as graphite, bronze-type T1O2 (sometimes designated by the name T1O2-B), vanadium oxide, such as V2O5, V3O7, a mixed lithium-titanium oxide. , such as L4Ti50i2 (sometimes referred to as LTO), lithium phosphates, such as LiFePC> 4 (sometimes referred to as LFP abbreviations).
    This material may also be an organic compound and, more specifically, an organic compound comprising at least one electron acceptor group, such as, for example, a carbonyl group.
    This type of compound, because it comprises an electron-accepting group and therefore capable of being reduced, can thus enter into the constitution of a positive electrode, when the energy storage device is in the process of discharging or in the constitution of a negative electrode, when the energy storage device is in charging process.
    In particular, such a compound may be an aromatic compound, such as a perylene compound, comprising at least one electron acceptor group, such as a carbonyl group or an imide group, a specific compound corresponding to this definition being dianhydrideperylene -3,4,9,10-tetracarboxylic acid (symbolized by the abbreviation PTCDA) corresponding to the following formula (I):
    (I)
    The active material may also be an organic compound having at least one electron donor group, such as, for example, a carboxylate group.
    This type of compound, because it comprises an electron donor group and therefore capable of being oxidized, can thus enter into the constitution of a negative electrode, when the energy storage device is in the process of discharging or in the constitution of a positive electrode, when the energy storage device is in charging process.
    More specifically, it may be an aromatic compound, such as a perylene or phenylene compound, comprising at least one electron donor group, such as a carboxylate group, and more particularly a lithiated carboxylate group, compounds specified in one of the following formulas (II) or (III):
    (II)
    (III)
    Advantageously, the electrochromic material is included in the electrode in a proportion of 45 to 99%, preferably 80 to 98% by weight relative to the total mass of the electrode.
    As mentioned above, the electrodes of the invention also include, as an electrically conductive additive, metal nanowires.
    In what precedes and what follows, the term "nanowire", a wire whose thickness is between 1 and 100 nanometers but whose length can go up to 10 micrometers.
    In addition to the fact that the nanowires do not mask the color changes of the electrochromic material, they make it possible to ensure good electronic conduction and have very low percolation thresholds (of the order of a percentage) within the electrodes.
    These metal nanowires may be metal nanowires chosen from copper, nickel, silver, gold, platinum, titanium, palladium, zinc, aluminum and alloys thereof, metal being advantageously chosen as a function of the range of working potentials of the active material.
    Thus, by way of examples: copper, nickel and silver are particularly suitable for an active material having an electrochemical potential ranging from 0 to 3 V. ° Li / Li +; the gold is particularly suitable for an active material having an electrochemical potential ranging from 1 to 4.5 V. ° Li / Li +; and platinum is particularly suitable for an active material having an electrochemical potential ranging from 0 to 4.5 V. ° Li / Li +.
    More specifically, the nanowires may be copper nanowires or gold nanowires. From a geometric point of view, they may advantageously have a form factor, corresponding to the ratio of the length of the nanowire over its diameter, ranging from 10 to 1,000,000, for example, greater than 30.
    Advantageously, the nanowires are comprised in the electrode in a proportion of 0.1 to 20%, preferably 0.1 to 6% by weight relative to the total mass of the electrode.
    In addition, the electrodes of the invention may comprise a binder, such as a polymeric binder, such as polyvinylidene fluoride (known by the abbreviation PVDF), a mixture comprising carboxymethylcellulose (known by the abbreviation CMC) with a latex of the styrene-butadiene type (known by the abbreviation SBR) or with polyacrylic acid (known by the abbreviation PAA), this binder contributing to improve the electrode strength.
    Also, from a structural point of view, the electrode may be in the form of a composite material comprising a matrix of polymeric binder (s), in which are dispersed charges constituted by the active material and metallic nanowires.
    The electrodes of the invention are intended to enter into the constitution of energy storage devices, such as: batteries operating with alkaline ions, such as lithium batteries, sodium batteries; batteries operating with alkaline earth ions, such as magnesium batteries; batteries operating with organic ions.
    Also, the invention also relates to an energy storage device, such as a lithium battery, comprising at least one electrochemical cell comprising two electrodes of opposite polarity, respectively a positive electrode and a negative electrode, separated by an electrolyte. at least one of the electrodes being an electrode as defined above, namely an electrode comprising, as active material, an electrochromic material and as an electrically conductive additive, metal nanowires.
    The characteristics defined above for the electrodes of the invention may be repeated on behalf of energy storage devices comprising such electrodes.
    For example, when the electrochromic material is an organic compound comprising at least one electron-withdrawing group, the electrode of the invention may be a positive electrode, that is to say an electrode which acts as a cathode (therefore is the seat of a reduction), when the generator delivers current (that is to say when it is in the process of discharge) or can be a negative electrode, which acts as a cathode (thus is the seat of 'a reduction), when the generator is in charging process. By way of examples, when the positive electrode comprises, as electrochromic material, an organic compound comprising at least one electron-withdrawing group, the negative electrode may in particular be a lithium metal electrode.
    Each of the electrodes is generally in contact with a current collector.
    In particular, the current collector may advantageously be for the electrode comprising, as active material, an electrochromic material and, as an electrically conductive additive, metallic nanowires, a transparent substrate on which the electrode may be deposited. this transparent substrate may be, for example, a glass or flexible plastic material substrate, optionally covered with an electrically conductive layer, for example an electrically conductive ceramic layer, such as a layer in indium and tin oxide.
    The current collector may be in the form of a foil or metal grid, for example copper or aluminum.
    The two electrodes of opposite polarity (ie, the positive electrode and the negative electrode) are separated by an electrolyte, and more specifically, an electrolyte conductive of ions, for example lithium ions (when the device is a battery lithium), sodium ions (when the device is a sodium battery), magnesium ions (when the device is a magnesium battery) or organic ions (when the device is a battery powered by organic ions ).
    This ion-conducting electrolyte may be a liquid electrolyte, comprising at least one salt in one or more solvents, for example a lithium salt (when the device is a lithium battery), a sodium salt (when the device is a sodium battery), a magnesium salt (when the device is a magnesium battery) or a salt comprising an organic ion (when the device is a battery operating with organic ions). By way of examples of lithium salt, mention may be made of C104, LiAsF6, LiFF6, UBF4, LiRfSO3, CH3SO3, LiN (RfSC2) 2, Rf being chosen from F or a perfluoroalkyl group containing from 1 to 8 carbon atoms, lithium trifluoromethanesulfonylimide (known by the abbreviation LiTFSI), lithium bis (oxalato) borate (known by the abbreviation LiBOB), lithium bis (perfluorethylsulfonyl) imide (also known as LiBETI), fluoroalkylphosphate lithium (known by the abbreviation LiFAP), lithium 4,5-dicyano-2-trifluoromethylimidazolide (known by the abbreviation LiTDI). As examples of solvents, mention may be made of: the aprotic polar organic solvents, for example an aprotic polar solvent chosen from carbonate solvents, ether solvents, ester solvents, sulphone solvents and nitrile solvents; or else practical solvents, such as water.
    In addition, the electrolyte can be made to imbibe at least one separator element disposed between the two electrodes of the battery.
    Alternatively, the ion-conducting electrolyte may be a polymer electrolyte or a gelled electrolyte. By way of example, a device according to the invention is a lithium battery comprising an electrochemical cell comprising: an electrode according to the invention, namely, more specifically, a positive electrode comprising, as electrochromic material, a compound organic compound of formula (I) as defined above, as an electrically conductive additive, copper nanowires and a polymeric binder, for example, polyvinylidene fluoride; a negative electrode made of lithium metal; and an electrolyte disposed between said positive electrode and said negative electrode, said electrolyte comprising a lithium salt and at least one organic solvent of the carbonates family.
    More specifically, the electrolyte may comprise a LiPFe lithium salt and a mixture of carbonate solvents, for example a ternary mixture comprising ethylene carbonate, dimethyl carbonate and ethyl methyl carbonate.
    Another example according to the invention is a lithium battery comprising an electrochemical cell, which electrochemical cell comprises: an electrode according to the invention, namely, more specifically, a negative electrode comprising, as electrochromic material, an organic compound of formula (I) as defined above, as an electrically conductive additive, copper nanowires and a polymeric binder, for example, polyvinylidene fluoride; a positive electrode comprising, as active material,
    LiFePO4; and an electrolyte disposed between said positive electrode and said negative electrode, said electrolyte comprising a lithium salt and at least one organic solvent of the carbonates family.
    Finally, another example according to the invention is a lithium battery comprising an electrochemical cell comprising: an electrode according to the invention, namely, more specifically, a positive electrode comprising, as electrochromic material, Ü 4Ti50i 2, as an additive; conductor of electricity, copper nanowires and a polymeric binder, for example, polyvinylidene fluoride; a negative electrode comprising, as active material, metallic lithium; and an electrolyte disposed between said positive electrode and said negative electrode, said electrolyte comprising a lithium salt and at least one organic solvent of the carbonates family.
    Advantageously, the devices of the invention are packaged in a transparent envelope, thus making it possible to visualize the electrode comprising an electrochromic material and thus the evolution of its color as a function of the state of charge of the electrode concerned. It is specified that the envelope surrounds the constituent elements of the battery, namely, the electrodes and the electrolyte.
    This transparent envelope may be, for example, polyethylene, polyethylene terephthalate or polypropylene.
    The devices of the invention are particularly suitable for the fields of application, in which the direct visualization of the state of charge of the batteries is an asset, as is the case with the field of portable electronic equipment, such as telephony. mobile, technical textiles, watchmaking.
    Finally, the invention finally relates to the use of metal nanowires in an electrode for an energy storage device, such as a lithium battery, comprising, as active material, an electrochromic material, for visualizing the state of charging said electrode by color change thereof.
    The characteristics of the metal nanowires, the electrode and the electrochromic material defined above can be used for this use. Other characteristics will appear better on reading the additional description which follows, which relates to an exemplary embodiment of electrodes and batteries according to the invention.
    Of course, the following example is given as an illustration of the subject of the invention and does not constitute, in any case, a limitation of this object.
    BRIEF DESCRIPTION OF THE DRAWINGS
    Figure 1 is an exploded view of a battery according to the invention.
    FIG. 2 is a graph illustrating charge-discharge curves (ie the evolution of the potential E (in V vs. Li + / Li °) as a function of the specific capacitance C (in mAh.g'1) with two compliant batteries to the invention and a battery not in accordance with the invention.
    FIG. 3 is a graph illustrating a cycling curve (ie the change in intensity I (in mA) as a function of the potential E (in V vs. Li + / Li °)) obtained by cyclic voltammetry with a battery according to the invention.
    FIG. 4 is a cycling curve (the evolution of the intensity I (in mA) as a function of the potential E (in V vs. PTCDA)) obtained by cyclic voltammetry with the battery of example 2.
    FIG. 5 is a graph illustrating charge-discharge curves (ie the evolution of the potential E (in V vs. Li + / Li °) as a function of the capacitance C (in mAh)) with the battery of example 2 .
    FIG. 6 is a graph illustrating charge-discharge curves (ie the evolution of the potential E (in V vs. Li + / Li °) as a function of the specific capacitance C (in mAh.g'1)) with the battery of Example 3.
    FIG. 7 is a curve illustrating the evolution of the specific capacitance C (in mAh / g) as a function of the number of cycles N for the battery of example 3.
    DETAILED PRESENTATION OF PARTICULAR EMBODIMENTS EXAMPLE 1
    This example illustrates the preparation of two batteries according to the invention, each of these batteries comprising, as illustrated in the exploded view of Figure 1 attached in the appendix, the following elements: a positive electrode 3 comprising, as active material, dianhydrideperylene-3,4,9,10-tetracarboxylic acid (PTCDA), as an electrically conductive additive, copper nanowires, and as a polymeric binder, polyvinylidene fluoride, which electrode is deposited on a current collector 5; a negative electrode 7 made of lithium metal, which electrode is deposited on a current collector 9; an electrolyte impregnating a separator composed of two superimposed disks 11 and 15 (a Celgard® disc and a Viledon® disc), said electrolyte being a liquid electrolyte composed of a mixture of ethylene carbonate (1/3 by volume ), ethyl and methyl carbonate (1/3 by volume) and dimethyl carbonate (1/3 by volume) and 1 mol / L of LIPF6- a) Preparation of copper nanowires
    First, a solution of 2000 mL of 15 mol.L1 NaOH is prepared in a 3 liter flask by dissolving 1200 g of NaOH in 2000 mL of deionized water (hereinafter referred to as the first solution).
    In parallel, a solution of 0.2 mol.L1 copper nitrate is prepared by adding 4.65 g of Cu (NO 3 h in 100 ml of deionized water.
    This solution is added to the first solution, then 30 mL of ethylenediamine (EDA) and 2.5 mL of hydrazine hydrate (35% by weight) are added.
    The reaction medium is heated at 80 ° C. for one hour with vigorous stirring.
    The solution changes from a royal blue color to a reddish brown color indicating the formation of metallic copper nanowires.
    The nanowires are collected by centrifugation and washed with an aqueous solution containing 3% by weight of hydrazine and finally they are stored in a flask under an argon atmosphere containing a solution of the same type (3% by weight of hydrazine). ) to prevent their oxidation.
    The copper nanowires obtained have a form factor (which corresponds to the ratio between the length and the diameter of the nanowires) greater than 30 with a length estimated by scanning electron microscopy at about 5 μιτι and an estimated diameter by scanning electron microscopy. about 150 nm. b) Preparation of electrodes according to the invention
    In a first step, a suspension is prepared comprising copper nanowires prepared in step a) mentioned above, polyvinylidene fluoride (PVDF) and N-methylpyrrolidone (NMP) in respective mass contents of 1%, , 5% and 98.5%, the whole being dispersed for 1 hour in a sonotrode. Then dianhydride-3,4,9,10-tetracarboxylic acid (PTCDA) and PVDF / NMP are added to the suspension, the mixture being dispersed by means of a dispermat. This results in an ink comprising 86% by weight of PTCDA, 4% by weight of copper nanowires and 10% by weight of polyvinylidene fluoride (the% by weight being expressed relative to the total weight of these three ingredients).
    According to a first variant, the aforementioned ink is deposited on a copper strip and is then dried in an oven at 55 ° C. for 24 hours. Then it is proceeded to the cutting of a circular piece of 14 mm in diameter using a punch, said piece then being dried in a
    Buchi at 80 ° C for 48 hours, the resulting part constituting a positive electrode (called first electrode) deposited on a copper collector.
    According to a second variant, the aforementioned ink is deposited by spraying with an airbrush gun onto a transparent plate covered with a stencil consisting of a glass substrate coated with a layer of indium oxide and of tin. The resulting part is then dried in an oven at 55 ° C. for 24 hours, whereby a second positive electrode results. c) Preparation of batteries according to the invention A first battery according to the invention is prepared from the first electrode defined in paragraph b) above.
    More specifically, this first battery is a battery of the button cell type, comprising respectively: a lithium metal negative electrode disk; the first positive electrode defined in paragraph b); and a separator consisting of the superposition of a Viledon® disk (reference FS2207-25-DA WA) (which is a membrane of non-woven polyolefin fibers (polypropylene / polyethylene)) and a Celgard® disk ( reference C2400) (which is a polypropylene membrane), which separator is impregnated with an electrolyte composed of a mixture of ethylene carbonate (1/3 by volume), of ethyl and methyl carbonate (1/3 volume) and dimethyl carbonate (1/3 by volume) and 1 mol / L of LFPE6.
    A second battery according to the invention is prepared from the second electrode defined in paragraph b) above.
    More specifically, this second battery is a battery of the type flexible pouch (corresponding to the English terminology "Pouch Cell"), comprising respectively: a negative electrode disc lithium metal; the second positive electrode defined in paragraph b); and a separator consisting of the superposition of a Viledon® disk (reference FS2207-25-DA WA) (which is a membrane of non-woven polyolefin fibers (polypropylene / polyethylene)) and a Celgard® disk ( reference C2400) (which is a polypropylene membrane), which separator is impregnated with an electrolyte composed of a mixture of ethylene carbonate (1/3 by volume), of ethyl and methyl carbonate (1/3 by volume) and dimethyl carbonate (1/3 by volume) and 1 mol / L of LFPF6-
    This second battery is placed in a flexible polyethylene transparent envelope, so as to be able to visualize the color changes of the positive electrode according to its state of charge.
    This second battery is subjected to a discharge process, which, from a chemical point of view, corresponds to the reduction of the PTCDA, and for this battery, the color evolution of the battery is examined through the transparent flexible envelope. positive electrode.
    As the discharge progresses, we observe a transition from a red color to a much darker color, which tends towards the violet.
    Thanks to the electrodes and batteries of the invention, it is thus possible to simply display the state of charge of the battery by simply changing the color of the positive electrode.
    In parallel, the electrochemical performances of the batteries according to the invention were also tested.
    Thus, it was proceeded to the realization of a charge / discharge profile with the first battery in comparison with a battery not in accordance with the invention, in which the copper nanowires were replaced by carbon black Super type P, the proportion of ingredients of the positive electrode being respectively 75% by mass for the PTCDA, 20% by weight for the carbon black and 5% by weight for the PVDF.
    The curves are shown in FIG. 2, with curve a) for the first battery, curve b) for the second battery and curve c) for the battery not in accordance with the invention.
    They have a relatively similar profile, attesting to the fact that copper nanowires do not disturb the electrochemical performance of batteries.
    A cyclic voltammetric test with the first battery was also carried out, consisting of cycling between 1.8 V and 3.2 V. Li + / Li ° at a scanning rate of 0.1 mV.s1, the cycling curve being shown in FIG. 3. This figure shows a reduction peak at 2.8 V, which corresponds to the reduction peak of the carbonyl function and an oxidation peak at 2.3 V, which corresponds to the oxidation peak of the enolate functions thus created, these two peaks attesting to the reversibility of the PTDCA. EXAMPLE 2
    This example illustrates the preparation of a battery of the button-button type according to the invention, said battery comprising: a negative electrode comprising, as active material, dianhydrideperylene-3,4,9,10-tetracarboxylic acid (PTCDA), as an electrically conductive additive, copper nanowires, and as a polymeric binder, polyvinylidene fluoride, which electrode is deposited on a current collector; an electrode comprising, as active material, LiFePC> 4, which is deposited on a current collector; an electrolyte impregnating a separator composed of two superposed disks (a Celgard® disk and a Viledon® disc), said electrolyte being a liquid electrolyte composed of a mixture of ethylene carbonate (1/3 by volume), ethyl and methyl carbonate (1/3 by volume) and dimethyl carbonate (1/3 by volume) and 1 mol / L of LFIF6.
    This battery is prepared according to the same methods as those described in Example 1, except that the positive electrode of Example 1 becomes the negative electrode in this example 2 and the positive electrode of this example 2 includes LiFePCU.
    With this battery, a cyclic voltammetric test was carried out, consisting of cycling between 0.2 V and 1.5 V. Li + / Li0 at a scanning rate of 0.01 mV.s.sup.-1, the cycling curve being shown in FIG. 4. This figure shows a reduction peak at 1.8 V, which corresponds to at the peak of reduction of the anhydride function and an oxidation peak at 0.7 V, which corresponds to the oxidation peak of the carboxylate functions thus created, these two peaks attesting to the reversibility of the PTDCA.
    It was also proceeded to the realization of a charge / discharge profile with a speed of C / 10 with this battery, 5 cycles of charge / discharge having been carried out, the curves of 5 cycles being reported in FIG. curves are superimposed, which attests to the stability of the battery. EXAMPLE 3
    This example illustrates the preparation of a battery of the button-button type according to the invention, said battery comprising: a positive electrode comprising, as active material, ϋ4ΪΪ5θΐ2, as an electrically conductive additive, copper nanowires, and as a polymeric binder, polyvinylidene fluoride, which electrode is deposited on a current collector; a negative lithium metal electrode, which is deposited on a current collector; an electrolyte impregnating a separator composed of two superposed disks (a Celgard® disk and a Viledon® disc), said electrolyte being a liquid electrolyte composed of a mixture of ethylene carbonate (1/3 by volume), ethyl and methyl carbonate (1/3 by volume) and dimethyl carbonate (1/3 by volume) and 1 mol / L of LIPF6-
    The active material Ü4Ti50i2 is an electrochromic material capable of changing from a white color to a dark blue color depending on its state of charge.
    This battery is prepared according to the same methods as those described in Example 1, except that it was necessary to prepare the positive electrode according to the following protocol.
    A solution containing the copper nanowires, polyvinylidene fluoride fluoride (PVdF) and N-methylpyrrolidone (NMP) was prepared by dispersing with a sonotrode for 1 hour, this solution comprising 1% by mass of copper nanowires, , 5% by mass of PVDF and 98.5% by mass NMP. Then Li.sub.2 O.sub.3 O.sub.4 is added and the mixture is dispersed at dispermat. The colored ink thus obtained has a composition of about 90% Li 4 Ti 2 O 2, 4% copper nanowires and 6% PVdF. This ink was coated on copper collectors, then dried in an oven at 55 ° C for 24 hours. An electrode 14 mm in diameter was cut with a punch and then dried in a Buchi at 80 ° C for 48 hours.
    With this battery, a charging / discharging profile with a C / 10 speed was also implemented with this battery, 5 charge / discharge cycles having been carried out, the 5-cycle curves being transferred to the Figure 6. These curves are superimposed, which shows the stability of the battery.
    The evolution of the specific capacitance C (in mAh / g) was also determined as a function of the number of cycles N, the results being reported in FIG. 7. It appears that the specific capacity remains substantially constant at course of 25 cycles implemented.
    权利要求:
    Claims (25)
    [1" id="c-fr-0001]
    1. Electrode for energy storage device comprising, as active material, an electrochromic material and as an electrically conductive additive, metal nanowires.
    [2" id="c-fr-0002]
    2. Electrode according to claim 1, which is deposited on a transparent substrate.
    [3" id="c-fr-0003]
    An electrode according to claim 1 or 2, wherein the electrochromic material is an organic compound.
    [4" id="c-fr-0004]
    4. An electrode according to any one of claims 1 to 3, wherein the electrochromic material is an organic compound comprising at least one electron acceptor group.
    [5" id="c-fr-0005]
    An electrode according to any one of the preceding claims, wherein the electrochromic material is an aromatic compound comprising at least one electron acceptor group.
    [6" id="c-fr-0006]
    An electrode according to any one of the preceding claims, wherein the electrochromic material is a perylene compound comprising at least one electron acceptor group.
    [7" id="c-fr-0007]
    An electrode according to any one of claims 4 to 6, wherein the electron acceptor group is a carbonyl group.
    [8" id="c-fr-0008]
    8. Electrode according to any one of the preceding claims, wherein the electrochromic material is a compound of formula (I) below:

    (I)
    [9" id="c-fr-0009]
    An electrode according to any one of claims 1 to 3, wherein the electrochromic material is an organic compound having at least one electron donor group.
    [10" id="c-fr-0010]
    An electrode according to any one of claims 1 to 3 or 9, wherein the electrochromic material is an organic compound having an electron donating group, which is a carboxylate group.
    [11" id="c-fr-0011]
    An electrode according to any one of claims 1 to 3, 9 or 10, wherein the electrochromic material is a perylene or phenylene compound having at least one electron donating group, such as a carboxylate group.
    [12" id="c-fr-0012]
    12. Electrode according to any one of claims 1 to 3, 9, 10 or 11, wherein the electrochromic material is a compound corresponding to one of the following formulas (II) or (III):

    (II)

    (III)
    [13" id="c-fr-0013]
    13. Electrode according to any one of the preceding claims, wherein the metal nanowires are metal nanowires selected from copper, nickel, silver, gold, platinum, titanium, palladium, zinc, aluminum and alloys thereof.
    [14" id="c-fr-0014]
    An electrode according to any one of the preceding claims, wherein the metal nanowires are copper or gold nanowires.
    [15" id="c-fr-0015]
    15. An electrode according to any one of the preceding claims, wherein the metal nanowires have a form factor, corresponding to the ratio of the length of the nanowire over its diameter, ranging from 10 to 1000000.
    [16" id="c-fr-0016]
    An electrode according to any one of the preceding claims, which comprises a polymeric binder.
    [17" id="c-fr-0017]
    An electrode according to claim 1 or 2, wherein the electrochromic material is an inorganic material.
    [18" id="c-fr-0018]
    18. An electrode according to claim 1, 2 or 17, wherein the electrochromic material is an inorganic material selected from graphite, the bronze form T1O2, a vanadium oxide, such as V2O5, V3O7, a mixed lithium and lithium oxide. titanium, such as ϋ4ΤΪ5θΐ2, a lithium phosphate, such as LiFePO4.
    [19" id="c-fr-0019]
    19. An energy storage device comprising at least one electrochemical cell comprising two electrodes of opposite polarity, respectively a positive electrode and a negative electrode, separated by an electrolyte, at least one of the electrodes being an electrode as defined according to FIG. any one of claims 1 to 18.
    [20" id="c-fr-0020]
    20. Device according to claim 19, which is a lithium battery.
    [21" id="c-fr-0021]
    21. Device according to claim 19 or 20, which is a lithium battery comprising an electrochemical cell comprising: a positive electrode comprising, as electrochromic material, an organic compound of formula (I) as defined in claim 8, as an additive conductor of electricity, copper nanowires and a polymeric binder, for example, polyvinylidene fluoride; a negative electrode made of lithium metal; and an electrolyte disposed between said positive electrode and said negative electrode, said electrolyte comprising a lithium salt and at least one organic solvent of the carbonates family.
    [22" id="c-fr-0022]
    22. Device according to claim 19 or 20, which is a lithium battery comprising an electrochemical cell comprising: a negative electrode comprising, as electrochromic material, an organic compound of formula (I) as defined in claim 8, as an additive conductor of electricity, copper nanowires and a polymeric binder, for example, polyvinylidene fluoride; a positive electrode comprising, as active material, LiFePO4; and an electrolyte disposed between said positive electrode and said negative electrode, said electrolyte comprising a lithium salt and at least one organic solvent of the carbonates family.
    [23" id="c-fr-0023]
    23. Device according to claim 19 or 20, which is a lithium battery comprising an electrochemical cell comprising: a positive electrode comprising, as electrochromic material, L4Ti50i2, as an electrically conductive additive, copper nanowires and a binder; polymer, for example, polyvinylidene fluoride; a negative electrode comprising, as active material, metallic lithium; and an electrolyte disposed between said positive electrode and said negative electrode, said electrolyte comprising a lithium salt and at least one organic solvent of the carbonates family.
    [24" id="c-fr-0024]
    24. Device according to any one of claims 19 to 23, which is packaged in a transparent envelope.
    [25" id="c-fr-0025]
    25. Use of metal nanowires in an electrode for an energy storage device comprising, as active material, an electrochromic material, for visualizing the state of charge of said electrode by color change thereof.
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    同族专利:
    公开号 | 公开日
    FR3047843B1|2018-03-09|
    JP2019510340A|2019-04-11|
    EP3414788B1|2019-11-20|
    EP3414788A1|2018-12-19|
    US20190036122A1|2019-01-31|
    WO2017137591A1|2017-08-17|
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    法律状态:
    2017-02-28| PLFP| Fee payment|Year of fee payment: 2 |
    2017-08-18| PLSC| Publication of the preliminary search report|Effective date: 20170818 |
    2018-02-26| PLFP| Fee payment|Year of fee payment: 3 |
    2020-02-28| PLFP| Fee payment|Year of fee payment: 5 |
    2021-02-26| PLFP| Fee payment|Year of fee payment: 6 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1651173A|FR3047843B1|2016-02-12|2016-02-12|ELECTROCHROME ELECTRODE FOR ENERGY STORAGE DEVICE|
    FR1651173|2016-02-12|FR1651173A| FR3047843B1|2016-02-12|2016-02-12|ELECTROCHROME ELECTRODE FOR ENERGY STORAGE DEVICE|
    JP2018542139A| JP2019510340A|2016-02-12|2017-02-10|Electrochromic electrodes for energy storage devices|
    US16/077,234| US20190036122A1|2016-02-12|2017-02-10|Electrochromic electrode for energy storage device|
    PCT/EP2017/053055| WO2017137591A1|2016-02-12|2017-02-10|Electrochromic electrode for energy storage device|
    EP17704017.7A| EP3414788B1|2016-02-12|2017-02-10|Electrochromic electrode for energy storage device|
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