• 专利附录
  • 专利说明
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    • 专利摘要:
    The present invention relates to a transparent photorechargeable electrochemical device, the use of an n-type semiconductor as a positive electrode active material for said transparent photorechargeable electrochemical device, and a method of photorecharging said device.
    公开号:FR3013901A1
    申请号:FR1361775
    申请日:2013-11-28
    公开日:2015-05-29
    发明作者:Frederic Sauvage；Christian Andriamiadamanana；Christel Laberty
    申请人:Centre National de la Recherche Scientifique CNRS；Universite Pierre et Marie Curie Paris 6；Universite de Picardie Jules Verne；
    IPC主号:
    专利说明:

    [0001] The present invention relates to a transparent photorechargeable electrochemical device, the use of an n-type semiconductor as a positive electrode active material for said transparent photorechargeable electrochemical device, and a method of photorecharging said device. In particular, it relates to the field of alkaline batteries, including lithium batteries. Lithium batteries have become indispensable components in many devices that include portable devices, such as mobile phones, computers and light equipment, or heavier devices such as two-wheeled vehicles (bicycles). , mopeds) or four-wheeled vehicles (electric or hybrid motor vehicles). They are also widely studied for use in the field of energy storage. A lithium battery comprises at least one negative electrode and at least one positive electrode between which is placed a solid electrolyte or a separator impregnated with a liquid electrolyte. For example, the liquid electrolyte consists of a lithium salt dissolved in a solvent chosen to optimize the transport and dissociation of the ions. The positive electrode is constituted by a current collector supporting an electrode material which contains at least one positive electrode active material capable of reversibly inserting lithium ions; the negative electrode is constituted by a sheet of lithium metal (possibly supported by a current collector), a lithium alloy or a lithium intermetallic compound (lithium battery), or by a current collector supporting a electrode material which contains at least one negative electrode active material capable of reversibly inserting lithium ions (lithium ion battery). During the operation of the battery, lithium ions pass from one to the other of the electrodes through the electrolyte. During discharge of the battery, an amount of lithium reacts with the positive electrode active material from the electrolyte, and an equivalent amount is introduced into the electrolyte from the active material of the negative electrode, the lithium concentration thus remaining constant in the electrolyte. The insertion of the lithium into the positive electrode is compensated by supplying electrons from the negative electrode via an external circuit. During charging, the reverse phenomena take place. The mass densities of energy currently obtained in the various electrochemical energy storage systems are 200-250 Wh / kg for the best Li-ion batteries, 100-150 Wh / kg for a Na-ion battery, 350 Wh / kg for a Li-S battery, 500 Wh / kg for a lithium-air battery and 50 Wh / kg for a redox flow battery (well known as the "redox-flow battery"). These batteries therefore have relatively low energy mass densities and must be recharged via the power grid, inducing limited amounts of deliverable energy. In addition, over the last decade, devices for transforming solar energy into electrical energy have been proposed. In particular, Grâtzel has developed a photovoltaic cell with photosensitive pigment (well known under the Anglicism dye-sensitized solar cell, DSSc, DSC, or DYSC) comprising a transparent conductive layer of tin-doped tin oxide electricity Sn02 -F, on which is placed a TiO2 titanium oxide photoanode on the surface of which a photosensitive pigment (eg ruthenium polypyridine complex (+ II)) has been grafted, a platinum counter electrode and an iodide / electrolyte triiodide (I / I3-). However, such a photovoltaic cell does not allow the storage of energy. Other systems such as photocapacitors combining two technologies, i.e. a photovoltaic cell and a capacitor, have been developed to allow the storage of directly converted electricity from light energy. In general, such systems include a photoelectrode, a bifunctional internal electrode, i.e., which functions both as cathode and as anode, and which is at the junction with two different electrolytes, and one against -electrode in the capacitor part. However, in order to maintain good performance, the migration and / or the diffusion of the oxidoreducing species towards the capacitor part must be inhibited, inducing difficulties in the manufacture of such systems and in the design of efficient materials. For example, US2009 / 0078307 describes a device coupling two technologies: a photovoltaic cell type DSSc and anionic battery. However, the storage capacities reached are relatively low since they are of the order of 0.01 mAh / cm 2. Tributsch [J. Appl. Phys., 1987, 62, 11, 4597-4605] has therefore proposed photorechargeable batteries using semiconductors capable of reversibly photoinducing the intercalation of metal ions. In particular, Tributsch proposes a photorechargeable battery comprising a photoelectrode comprising a p-type semiconductor such as copper thiosulfate Cu3PS4, a counter-electrode such as a copper wire, and an electrolyte comprising a solution of copper chloride (CuCl) and tetrabutylammoniumperchlorate (TBAPC) in acetonitrile. However, the performances obtained are limited, in particular due to the slow kinetics of the discharge reaction. Moreover, the use of copper does not allow to reach high voltages. Thus, none of the documents of the prior art describes a system that allows both the conversion of light energy into electrical energy and its storage in the form of chemical energy, and having good storage capacities, so as to render said autonomous system vis-à-vis the electrical network, including its recharge under the effect of light waves. The object of the present invention is to provide a transparent photorechargeable electrochemical device that can both store energy and be recharged under the effect of light waves. In particular, the present invention aims to overcome all or in part the aforementioned drawbacks and to provide a transparent photorechargeable electrochemical device that recharges under the effect of light waves in a few minutes regardless of its discharge level, which presents a power density and a power significantly increased compared to those devices proposed in the prior art, and finally that solves the problem of intermittent cycles of light. The first subject of the present invention is therefore a transparent photorechargeable electrochemical device, said device being characterized in that it comprises: a positive electrode comprising a conductive transparent support on which is deposited a positive electrode film, said electrode film positive electrode comprising an n-type semiconductor as a positive electrode active material, said n-type semiconductor having a bandgap width Eg and being capable of interposing and de-interposing ions of an alkali metal M1 ; a negative electrode comprising a member selected from said alkali metal M1, an alloy of said alkali metal M1, and an intermetallic compound of said alkali metal M1; and a non-aqueous liquid electrolyte comprising a salt of said alkali metal M1 and an organic solvent; said positive and negative electrodes respectively having electrode potentials E1 and E2, with E1> E2, E1 and E2 being calculated with respect to the electrode potential of the torque M1 ± / M1 °. In the present invention, the term "transparent device (or carrier)" means a device (or a carrier) that passes light waves (i.e., light). The light waves may comprise electromagnetic waves whose wavelength corresponds to the visible spectrum, or between the wavelengths 380 and 780 nm, the electromagnetic waves located in the near-infrared domains, or between the wavelengths. 780 and 3000 nm, and the electromagnetic waves located in a part of the ultraviolet domains, that is to say between the wavelengths 310 and 380 nm. Electromagnetic waves whose wavelength corresponds to the visible spectrum, or between the wavelengths 380 and 780 nm, are particularly preferred. By "conductive" support is meant a support which has a conductivity of from 10-1 S / cm to about 103 S / cm. The transparent photorechargeable electrochemical device according to the invention operates under the effect of light waves coming from all types of sources, that is to say from both a natural source (sun) and an artificial source ( lamps). In addition, it is able to recharge under the effect of light waves in minutes regardless of its level of discharge, to recharge occasionally in the dark when it has been exposed for some time to a source of light. light waves, and it has very good electrochemical performance, in particular thanks to the sufficiently fast photorecharge process which compensates for its discharge if it occurs under illumination. In addition, said device makes it possible to integrate more or less energy-consuming electrical elements 10 in geographical areas devoid of a general power supply network and to reduce the cost of producing and storing the solar kWh. In a preferred embodiment, the electrode potentials E1 and E2 are between 0 and 5 volts relative to the torque M1 ± / M1 °. In a particular embodiment, the device according to the invention is hermetic. In a particular embodiment, the alkali metal M1 of the device according to the invention is chosen from lithium, sodium and potassium. In a particular embodiment, the n-type semiconductor of the transparent photorechargeable electrochemical device according to the invention is chosen from metal oxides, metal phosphates, metal sulfates and metal oxalates, in wherein said metals are selected from Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, Hf, Ta , W, Re, Os, Ir, Pt, Au, Hg, Rf, Db, Sg, Bh, Hs, Mt, Ds, Rg, Cn and Bi. The metals are preferably selected from Ti, Fe, Mn, Co, Ni, Sn, Ru, Bi, V, Cr, Cu, Nb, Mo and Zn. By way of example of metal oxides, mention may in particular be made of TiO 2, Fe 2 O 3, Fe 3 O 4, MnO 2, CoO, Co 3 O 4, NiO, SnO 2, RuO 2, Bi 2 O 3, V0 2, V 2 O 5, Cr 2 O 3, CuO, Cu 2 O, Nb 2 O 5, MoO 3. ZnO. The n-type semiconductor is preferably TiO 2. By way of example of metal phosphates, mention may be made in particular of: the olivines corresponding to the formula MM'PO4, in which M = Li or Na and M '= Fe, Co, Mn, Ni or a mixture thereof, fluorinated, hydroxylated and oxygenated derivatives corresponding to the formulas MxM "PO4F, MxM" PO4.0H and MxM "PO4.0, in which M has the same definition as above, M" = Fe, Co, Mn, Ni , V or Ti and x is from 0 to 2, the carbonophosphates having the formula M3M'PO4CO3, in which M and M 'have the same definitions as above, and finally - the pyrophosphates corresponding to the formula MxM'P207 where M, M 'and x have the same definitions as above. By way of example of metal sulphates, mention may in particular be made of the materials corresponding to the formulas MUS04) 3, MM "SO4F and MxM" OSO4, in which M, M ', M "and x have the same definitions as hereinafter Examples of oxalates of metals include those compounds of the formula M2M '(C204) 2, wherein M and M' have the same definitions as above. The n-type suitable for the present invention is preferably titanium oxide (TiO 2), and even more preferably titanium anatase oxide (TiO 2 anatase) in the present invention. and E2 are measured with respect to the electrode potential of M1 ± / M1 °, and E1> E2, where the electron energy potentials E1 'and E2' respectively are considered positive and negative of the device of the present invention, one would have the inverse relation El '<E2' since El 'and E2' would be measured with respect to the zero of the electronic energy scale, ie, with respect to the energy of the electron in a vacuum. When the value of E1 approaches the value of E2 while respecting El> E2, the transparent photorechargeable electrochemical device according to the invention accumulates chemical energy during the absorption of light through the reaction of dice. -intercalation of the ions of the alkali metal M1, which occurs during the oxidation of the transition metal present in the n-type semiconductor. This photo-oxidation of the n-type semiconductor results from the charge separation phenomenon that takes place during the absorption of light. This phenomenon occurs mainly in the electron depletion zone of the n-type semiconductor where a large accumulation of electron holes on the surface of said n-type semiconductor occurs. In a particular embodiment, the n-type semiconductor has a forbidden bandwidth Eg of at most about 4.0 eV, and preferably from about 0.4 eV to about 3.5 eV, and still more more preferred from 1.2 eV to 3.5 eV. In a particular embodiment, said positive electrode film comprising said n-type semiconductor as a positive electrode active material has a thickness of about 0.1 to 25 μm, and preferably 0, About 5 to 15 pm. In a particular embodiment, the n-type semiconductor is in the form of nanoparticles, that is to say it can comprise particles with a diameter ranging from about 2 to about 50 nm, preferably of diameter ranging from from about 2 to about 20 nm, and even more preferably from about 2 to about 10 nm in diameter. When the n-type semiconductor particles have a diameter of less than 2 nm, the electrolyte can not easily penetrate into said positive electrode film and thus impregnate it effectively. When the n-type semiconductor particles have a diameter greater than 50 nm, the intercalation of the alkali metal ions M1 into the n-type semiconductor becomes difficult and therefore may become incomplete. In a particular embodiment, the n-type semiconductor has a specific surface area measured by the B.E.T. from about 20 m 2 / g to about 500 m 2 / g, and preferably from about 150 m 2 / g to about 400 m 2 / g, and still more preferably from about 230 m 2 / g to about 310 m 2 / g. Due to the fact that it is in the form of nanoparticles and has a large specific surface area, the n-type semiconductor has a high surface reactivity. Thus, the insertion and conduction of the alkali metal ions M1 into said n-type semiconductor is facilitated. In a particular embodiment, the positive electrode film has a mesoporous structure. In a particular embodiment, the n-type semiconductor is at least about 90 wt.%, Preferably at least about 95 wt.%, And still more preferably at least about 98 wt. total mass of the positive electrode film. The salt of the alkali metal M1 used in the liquid electrolyte of the device according to the invention may be chosen for example from lithium salts such as LiPF 6, LiAsF 6, LiClO 4, LiBF 4, LiCl 4 BO 8, Li (C 2 F 5 SO 2) 2 N, Li [ (C2F5) 3PF3], LiCF3SO3, LiCH3SO3, LiN (SO2CF3) 2 and LiN (SO2F) 2, sodium salts such as NaCIO4, NaBF4, NaPF6, Na2SO4, NaNO3, Na3PO4, Na2CO3, sodium bis (trifluoromethanesulfonyl) imide (NaTFSI), sodium bis (perfluoroalkylsulfonyl) methane, sodium tris (perfluoroalkylsulfonyl) methane, and potassium salts such as KPF6, KAsF6, KCIO4, KBF4, KCF3SO3, KCH3SO3 and KN (SO2CF3) 2. Among such salts, MIPF6 (M1 = Li, Na or K) are particularly preferred. The organic solvent used in the liquid electrolyte of the device 15 according to the invention makes it possible to optimize the transport and dissociation of the ions of the alkali metal M1. It may comprise one or more aprotic polar compounds selected from linear or cyclic carbonates, linear or cyclic ethers, linear or cyclic esters, linear or cyclic sulfones, sulfonamides and nitriles. The organic solvent preferably comprises at least two carbonates selected from ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate and methyl and ethyl carbonate. The positive electrode film of the device according to the invention may further comprise an agent generating an electronic conductivity, said electronic conductivity generating agent being selected to extract and conduct the electrons while not absorbing light or by absorbing the light as little as possible, that is to say with a lower absorption proportion to that of the n-type semiconductor. The electronic conductivity generating agent suitable for the present invention is preferably selected from carbon black, SP carbon, acetylene black, carbon fibers and nanofibers, carbon nanotubes, and semi-metallic fibers. -metal and one of their mixtures. When used, the agent generating an electronic conductivity generally represents at most about 15% by weight, and preferably at most about 5% by weight, and even more preferably at most 3% relative to the total mass. positive electrode film.
    [0002] Preferably, the positive electrode film of the invention does not comprise an agent generating an electronic conductivity. In a particular embodiment, the positive electrode film of the device according to the invention may further comprise a binder, said binder being chosen so as to improve the cohesion between the particles of active material and / or between the particles of active ingredient and electronic conductivity generating agent if present. Said binder must not absorb light. The binder suitable for the present invention is preferably chosen from cellulose derivatives such as hydroxyethylcellulose, fluoropolymers such as PVDF and PVDF-HFP. When the binder is used, it generally represents at most about 5% by weight, and preferably at most about 3% by weight, based on the total mass of the positive electrode film. Preferably, the positive electrode film of the invention does not comprise a binder.
    [0003] In a particular embodiment, the positive electrode film of the device according to the invention further comprises additives such as dyes and / or light reflectors. Preferably, the positive electrode film comprises at least one dye and / or at least one light reflector.
    [0004] Dyes can absorb more light and thus improve the use of light. By way of example of dyes, mention may especially be made of polypyridined complexes of ruthenium (+ II), osmium (+ II), iron (+ II) or copper (+ II), organic molecules of the donor type -TT-acceptor, and other organic molecules such as perilenes diimides, squaraines, phthalocyanines, anthocyanins, indolines, coumarins, or eosin Y. The positive electrode film may comprise at most 2% approximately, and preferably at most about 1% by weight of dyes.
    [0005] Light reflectors are materials having a high refractive index, preferably ranging from 1.5 to 4. They make it possible to better confine the light in the n-type semiconductor. By way of example of light reflectors, there may be mentioned macropores, photonic crystals (eg SiO 2 / TiO 2), plasmonic structures and all semiconductor or insulating oxides whose particle size is comparable to the lengths of wave of the incident light which one wishes to make reflect. Preferably, the semiconductor oxides are chosen from TiO 2 anatase, TiO 2 rutile, SiO 2, ZrO 2, Nb 2 O 5 and the compounds of the family of the following perovskites: SrTiO 3, CaTiO 3 and BaTiO 3. By way of example, the positive electrode film of the device according to the invention may comprise anatase TiO 2 particles with a diameter ranging from 4 to 6 nm as an n-type semiconductor, and anatase TiO 2 particles. diameter of 400 to 800 nm as a light reflector. The anatase TiO2 particles having a diameter of 400 to 800 nm reflect light that has not been absorbed by the n-type semiconductor. Preferably, the light reflector is different from the n-type semiconductor. The positive electrode film may comprise at most about 15% by weight, and preferably at most about 5% by weight of light reflectors. In a particular embodiment, the conductive transparent support is a conductive transparent glass of the FTO type (fluorine-doped tin oxide), of the ITO type (indium-doped tin oxide), or of the ZITO type ( tin oxide doped with indium and zinc). In a particular embodiment, said conductive transparent support has a thickness ranging from 100 to 4000 pm approximately, and preferably from 500 to 3000 pm approximately. In a particular embodiment, the device according to the invention is connected to a device for measuring potential and current in order to evaluate and monitor the state of charge of said device. Techniques for obtaining the positive electrode film with a mesoporous structure are well known to those skilled in the art. By way of example, the n-type semiconductor is mixed with an organic solvent (e.g., terpineol) and an organic compound (e.g., derived from cellulose) to form a paste. The dough is then calcined to decompose the organic compound while evaporating the solvent. At the end of the calcination, the organic compound is no longer present within the positive electrode film of the invention. A cellulose derivative may be hydroxyethylcellulose, methylcellulose, hydroxypropylmethylcellulose or carboxymethylcellulose.
    [0006] Techniques for depositing the positive electrode film comprising the n-type semiconductor on said transparent conductive support in the device according to the invention are techniques well known to those skilled in the art. They may include screen printing (well known under the Anglicism "screen-printing"), pulsed laser ablation or the sol-gel technique associated with soaking-removal (well known under the dip-coating "Anglicism"). ). It is a second object of the present invention to use an n-type semiconductor as a positive electrode active material for the transparent photorechargeable electrochemical device according to the invention as defined above. Said n-type semiconductor used as a positive electrode active material in the transparent photorechargeable electrochemical device according to the invention may be said n-type semiconductor as described above. It is a third object of the present invention to provide a photorecharge method of the transparent photorechargeable electrochemical device according to the present invention, said method being characterized in that it comprises the following step: i) exposing said device, preferably on the said device comprising said positive electrode, to a source of light waves for at least 30 minutes, and preferably for at least 1 hour, to obtain said recharged device. In said method, the device before step i) is either fully discharged or at least partially discharged, the discharge having occurred by using said device as a "battery" to power an electrical device, such as a mobile phone , a computer, etc. When the device before step i) is completely discharged, it can not be used before step i) as "battery" to power an electrical device during step i) . On the other hand, during step i), the device can be used as a "battery" to power an electrical appliance concomitantly with step i), provided that the device consumes less energy than that produced during said step i. ), that is during the absorption of light waves. In a particular embodiment, step i) can be performed as many times as necessary, especially when the user of said device still has a light wave source for recharging said device. In this method, no electricity input is required to recharge said device. In a particular embodiment, the light wave source is a white lamp. In an even more particular embodiment, the lightwave source has an intensity ranging from 1 to 3000 mW / cm 2, and preferably from 10 to 300 mW / cm 2. The present invention also relates to a method of charging in the black of the transparent electrochemical photorechargeable device 25 according to the present invention, said method being characterized in that it comprises the following steps: i ') the exposure of said device, Preferably, on the side of said device comprising said positive electrode, at a source of light waves for at least 10 hours, and preferably for at least 12 hours, the use of the device of step i ') to feed an electrical apparatus, and iii ') the relaxation in the dark of the device of step ii') for at least 6 hours, and preferably for at least 12 hours, to obtain said reloaded device. Prior to step i '), the device is preferably fully charged. After step ii '), the device is preferably completely discharged.
    [0007] In a particular embodiment, steps ii ') and iii') can be successively repeated one or more times, preferably once. This method can be applied when the user of said device initially has a source of light waves, then no longer has access for a few days to any source of light waves.
    [0008] EXAMPLE OF PREPARATION OF A TRANSPARENT PHOTORECHARGEABLE ELECTROCHEMICAL DEVICE 1.1 Preparation of TiO2 anatase "as an n-type semiconductor" 30 ml of titanium isopropoxide (Ti (OiPr) 4) was added to 300 ml of water and then the solution The resulting mixture was stirred vigorously for about 4 hours until complete hydrolysis. The white precipitate obtained was then filtered under vacuum or centrifuged, washed several times with water and then with ethanol, and dried at room temperature. Said dried precipitate was then placed in the presence of an aqueous solution at 0.1 mol / liter of NH4F for 7 days at 60 ° C. TiO2 nanoparticles with a diameter ranging from about 4 to 6 nm and a surface area of about 235-300 m2 / g (B.E.T. method). 1.2 Preparation of the positive electrode comprising a transparent conductive support on which a ositive electrode film containing the anatase TiO 2 as obtained above is deposited. The positive electrode has been obtained by serigraphically depositing on a transparent conductive support FTO a printable paste comprising 12 g of anatase TiO 2 as prepared above in step 1.1, 7.2 g of hydroxyethyl cellulose and 65 g of terpineol. The paste generally comprises 22% by weight of hydroxyethylcellulose viscosity ranging from 30 to 50 mPas, and 38% by weight of hydroxyethylcellulose viscosity ranging from 5 to 15 mPas for 65 g of terpineol and regardless of the initial amount of TiO 2 in said dough. After drying the printable paste on the support and calcining, a positive electrode comprising a transparent conductive support on which is deposited a positive electrode film comprising only TiO 2 was obtained. Silk screen printing was performed with a screen printing apparatus sold under the trade name Precima by the company TIFLEX. The surface area of said positive electrode was determined from the size of the screen. The thickness of said positive electrode was measured using a device sold under the trade name DEKTAK III by Veeco. The porosity of said positive electrode has been calculated from the ratio between the actual mass of the electrode and the theoretical mass determined from its dimensions. The obtained positive electrode had a surface area of 0.16 cm 2, a thickness of 12 dam and a porosity of about 50%. 1.3 Assembly of the Photorechargeable Electrochemical Device The device according to the invention was obtained by placing in an argon-filled glove box a transparent white glass photoelectrochemical cell comprising: the electrode as prepared above at step 1.2 as a positive electrode, a lithium foil as a negative electrode and reference electrode, and a 1 mol / L solution of LiPF 6 lithium salt in an organic solvent ethylene carbonate dimethyl carbonate (1/1 by weight) as a liquid electrolyte. The attached FIG. 1 shows the operating principle of the device according to the invention. During the discharge (FIG. 1a), the principle of operation of the device is analogous to that of a conventional battery, that is, an insertion of electrons and lithium ions occurs at the same time. positive electrode allowing its reduction accompanied by an oxidation reaction of lithium metal to lithium ions at the negative electrode. In a conventional device, this reaction can be reversed, that is to say that during recharging, the oxidation of the positive electrode induces a release of electrons and lithium ions accompanied by a Negative electrode reduction reaction of lithium ions to lithium metal (Figure 1b).
    [0009] This reaction enables the battery to be recharged by means of an external supply of electricity (eg electrical distribution network). This recharging can however be obtained by substituting the connection of the battery to the external electricity network thanks to the illumination of the photo-active electrode which will induce a separation of the electron / hole pairs in the depletion zone of the semiconductor of type n (Figures 1c and 1d). BV and BC respectively represent the valence and conduction bands. The minority charge carriers will then migrate to the surface of the n-type semiconductor particles (i.e. TiO2) leading to the oxidation of Ti3 + to Ti4 +, and by compensation of the charges extract the lithium contained in said particles. The electrons are transported and collected to lead to the negative electron reduction reaction and thus realize the photoelectrochemical reaction. 1.4 Study of the behavior of the device according to the invention in a closed circuit in the dark and in the presence of a source of light waves The attached FIG. 2 shows the current density of the electrochemical device of the invention as obtained hereinafter. above (in mA / cm 2) as a function of the potential with respect to the Li / Li torque (in volts, V). The curve with the empty circles illustrates the behavior of the electrochemical device of the invention during the discharge in the absence of illumination (in the dark), while the curve with solid circles illustrates the behavior of the electrochemical device of the invention. during the discharge when the positive electrode (TiO2) is subjected to a source of light waves of intensity of the order of 3000 mW / cm2. The two curves were recorded at a scanning speed of 0.5 mV / s until a voltage of 1.5 V (vs. Li ± / Li) was obtained. The application of a voltage or a current in the different experiments (i.e. closed circuit) makes it possible to discharge the device electrochemically. We recall, however, that the discharge of the device occurs naturally when it is used as a "battery" to power an electrical device, that is to say without application of voltage or current (i.e. open circuit). In the absence of light waves, the discharge curve obtained (open circles) is strictly analogous to that obtained for a conventional non-transparent lithium battery consisting of a positive electrode comprising TiO 2 (without transparent conductive support) and of a negative electrode comprising lithium metal. It shows the insertion of lithium into the n-type TiO2 anatase semiconductor inducing, on the one hand, the partial reduction of the Ti4 + transition metal to Ti3 + and, on the other hand, a color change of the electrode passing from white. (characteristic of TiO2) to an intense blue. This color change results from the formation of a new intermediate band in the band structure of the material related to the electron-rich character of the Ti3 + 3d-0 2p orbital. The insertion and deinsertion of lithium under these conditions takes place at a redox potential of about 1.8 V (vs. Li + / Li) at equilibrium. The integration of said curve as a function of time makes it possible to give an experimental value of gravimetric capacity of 69 mAh / g approximately. However, this value is lower than the theoretical value of 168 mAh / g, which corresponds to an insertion of approximately 0.5 Li + per form unit. This difference in value can be explained on the one hand by the absence in the positive electrode as prepared of an agent generating an electronic conduction such as carbon and on the other hand by the lithium insertion regime used. in this example which is relatively high. However, when the positive electrode (TiO2) is subjected to a source of light waves of intensity of the order of 3000 mW / cm 2, the insertion of lithium into the n-type semiconductor TiO2 anatase to excited state proceeds in a quite different way. The discharge curve obtained (solid circles) shows the beginning of the insertion of lithium towards 3 V, a first wave of reduction towards 2.4 V, then a succession of cathode phenomena up to 1.7 V and finally a peak well defined at 1.58 V. The current density reaches values of the order of 4.8 mA / cm2 (at 1.58 V), while in the dark (curve with open circles) the current density maximum is 0.73 mA / cm2 (at 1.5 V). The value of the gravimetric capacitance in the presence of a light source is then 619 mAh / g, this value is clearly higher than the values obtained theoretically and experimentally in the dark. Such a discharge capacity would correspond to about two lithium inserted per form unit.
    [0010] During the discharge process, the positive electrode of the device according to the invention undergoes a photorecharge reverse reaction allowing a continuous regeneration of the latter. In other words, the applied potential induces a lithium insertion and the absorption of the light leads to the lithium electrochemical extraction inverse reaction enabling the initial state of the electrode to be partly or completely photoregenerated. according to the conditions of discharge. The appended FIG. 3 shows the potential with respect to the Li + / Li pair (in volts, V) as a function of the surface capacitance of the electrochemical device of the invention (in pAh / cm 2) in the black.
    [0011] The appended FIG. 4 shows the potential with respect to the Li + / Li pair (in volts, V) as a function of the surface capacitance of the electrochemical device of the invention (in mAh / cm 2) when the positive electrode (TiO 2) is subjected a source of light waves of intensity of the order of 3000 mW / cm2. Figures 3 and 4 were recorded by applying a current density of -100 pA / cm2 between 1.5 V and 3 V (vs. Li ± / Li). The insertion of lithium in the dark (FIG. 3) leads to a discharge / charge curve similar to that obtained for a conventional lithium battery consisting of a positive electrode comprising TiO 2 and a negative electrode comprising lithium metal. with the exception of a higher irreversible capacity in this example which is explained by the absence of carbon (agent generating an electronic conductivity) in the positive electrode as prepared above. At the first discharge, the surface capacity is about 0.75 mAh / cm 2 at 1.5 V and is accompanied by a rapid color change of the electrode from white to blue. When the insertion of lithium is carried out in the presence of a light wave source (FIG. 4), under the same experimental conditions as those indicated above, an excellent surface capacity of 18.6 mAh / cm 2 is reached, which corresponds to a gravimetric capacity of 10.4 Ah / g. In addition, the insertion potential obtained is much higher than in the dark since it is between 2.8 and 3.05 V, which corresponds to an energy density of more than 30 kWh / kg. This great value is far superior to all values obtained with existing electrochemical storage technologies. In addition, during the discharge, the electrode remained white or weakly bluish at the end of the experiment. These performances can be explained by the competition between the insertion of lithium into the structure imposed by the applied current density of 100 pA / cm 2 of electrode and the inverse photocurrent generated by the separation of the charges taking place in the depletion zone. which leads to the concomitant photorecharge of the electrode by an oxidation reaction. 1.5 Photorecharge of the device according to the invention in the presence of a source of light waves The appended FIG. 5 (curve represented by points A, B, D, F and G) shows the potential with respect to the Li ± / Li pair (in volts, V) as a function of the surface capacitance of the electrochemical device of the invention (in pAh / cm 2) when said device has been subjected to the following steps: a first discharge in the dark by applying a current density of 100 pA / cm2, the potential of the open-circuit cell up to 1.5 V (vs. Li ± / Li) (closed circuit) (Fig. 5, curve AB), - exposure to a light wave source d intensity of the order of 3 W / cm 2 for one hour (open circuit) (FIG. 5, curve BD), - second discharge in the dark by applying a current density of 100 μA / cm 2, of the potential of the cell. open circuit up to 1.5 V (vs. Li ± / Li) (closed circuit) (Fig. 5, curve DF), and - exposure to a wave source Luminous intensity of the order of 3000 mW / cm2 for one hour (open circuit) (Figure 5, F-G curve). The appended FIG. 5 (curve represented by the points A, B, C and E) shows the potential with respect to the Li Li / Li pair (in volts, V) as a function of the surface capacitance of the electrochemical device of the invention (in pAh / cm2) when said device was subjected to the following steps: - a first discharge in the dark by applying a current density of 100 pA / cm 2, the potential of the open-circuit cell up to 1.5 V (vs Li ± / Li) (closed circuit) (Figure 5, curve AB), - a relaxation in the dark for one hour (open circuit) (Figure 5, curve BC), - a second discharge in the dark by applying a density current of 100 μA / cm 2, the potential of the open circuit cell up to 1.5 V (vs. Li ± / Li) (closed circuit) (Figure 5, EC curve).
    [0012] Figure 5 shows that the potential for the following two curves: the first curve represented by the points A, B, D, F and G and the second curve represented by the points A, B, C and E is very different. Indeed, in the dark the equilibrium potential reached is 1.86 V (vs. Li ± / Li) while in the presence of light waves, the latter is 2.97 V (vs. Li ± / Li). On the other hand, the device which has undergone a relaxation period in the dark delivers a weak capacitance which corresponds to the remaining capacitance during the second discharge, while the device which has undergone a period of exposure to a source of waves luminaires delivers a surface capacity of 607 pAh / cm2 almost equivalent to that of 695 pAh / cm2 obtained during the first cycle. FIG. 5 thus shows, on the one hand, that the absorption of light leads to a photorecharge phenomenon and, on the other hand, that this phenomenon is reversible "from an electrochemical point of view" (ie the capacity delivered to the second cycle is almost equivalent to that obtained in the first cycle).
    [0013] In addition, a color change from intense blue to white (characteristic TiO2 color) of the positive electrode during the 1 hour relaxation period is observed. This color change of the positive electrode is indicative of the photorecharge reaction of the device. FIG. 6 shows the potential with respect to the torque Li ± / Li (in volts, 30 V) as a function of time (in hours) when the device has been subjected to the following steps: - a first discharge in the dark by applying a density current of 100 pA / cm 2, the potential of the open circuit cell up to 1.5 V (vs. Li ± / Li) (closed circuit) (Figure 6, curve AB), - exposure to a source of intensity of light waves of the order of 3000 mW / cm 2 for one hour (open circuit) (FIG. 6, curve BC).
    [0014] Figure 6 also shows the evolution of the color of the positive electrode during illumination as a function of time (photographs at 0 min, 10 min, 20 min, 30 min, 40 min and 50 min). From Figure 6 it can be seen that photorecharge occurs in less than one hour. 1.6 Recharging the Device According to the Invention in the Dark The previously charged device according to the invention was subjected to the following steps: exposure to a source of light waves of intensity of the order of 3000 mW / cm 2 for twelve hours (open circuit), - a discharge in the dark by applying a current density of 100 pA / cm 2, the potential of the open-circuit cell up to 1.5 V (vs. Li ± / Li) ( closed circuit), - a period of relaxation in the dark for 1 hour, 6 hours or 12 hours (open circuit).
    [0015] Figure 7 shows the potential with respect to the Li ± / Li pair (in volts, V) as a function of time (in hours) during the relaxation period in the dark, when this is 1 hour (curve with the squares empty), 6 hours (curve with empty circles), and 12 hours (curve with solid circles).
    [0016] FIG. 8 shows the current density (in mA / cm 2) as a function of the potential with respect to the Li ± / Li pair (in volts, V) during the relaxation period in the dark, when this is 1 hour ( curve with empty squares), 6 hours (curve with empty circles), and 12 hours (curve with solid circles).
    [0017] FIG. 8 shows that the current densities correspond to current densities recorded in the black and are therefore 10-fold lower than those previously recorded in the presence of a light-wave source. The electrochemical profile is different from that obtained in the black and closer to that obtained in the presence of a source of light waves. The integration of the three curves makes it possible to calculate the gravimetric discharge capacity which is between 46 and 51 mAh / g, comparable to that obtained in the dark (see Figure 2). The evolution of the open circuit potential is comparable to that observed during exposure to a light wave source (see Figure 6), except that in this case the time to reach the value of 3 V is much more important (12 hours). Indeed, it has been shown previously that a complete photorecharge took only one hour.
    [0018] The results therefore show that one or two recharges are still possible in the dark even if charging takes a little longer. This is a unique property that is highlighted here. This should at least partly solve the inherent problem of intermittency of solar energy; the proposed device can be recharged at least partially in the dark. The problem of intermittency is also partly solved thanks to the bifunctionality of the positive photo-active electrode which can deliver a continuous current in the presence of a natural source of light waves, and discharge at night while delivering a current density of 100 pA / cm 2. At the end of the night, the positive electrode still in operation, photo-regenerates and can support many cycles day / night while delivering energy constantly.
    权利要求:
    Claims (18)
    [0001]
    REVENDICATIONS1. Transparent photorechargeable electrochemical device, said device being characterized in that it comprises: a positive electrode comprising a conductive transparent support on which a positive electrode film is deposited, said positive electrode film comprising an n-type semiconductor; as a positive electrode active material, said n-type semiconductor having a band gap Eg and being capable of interposing and de-interposing alkali metal ions M1; a negative electrode comprising an element chosen from said alkali metal M1, an alloy of said alkali metal M1, and an intermetallic compound of said alkali metal M1; a nonaqueous liquid electrolyte comprising a salt of said alkali metal M1 and an organic solvent; and said positive and negative electrodes respectively having electrode potentials E1 and E2, with E1> E2, E1 and E2 being calculated with respect to the electrode potential of the torque M1 ± / M1 °.
    [0002]
    2. Device according to claim 1, characterized in that the alkali metal M1 is selected from lithium, sodium and potassium.
    [0003]
    3. Device according to claim 1 or 2, characterized in that the n-type semiconductor is selected from metal oxides, metal phosphates, metal sulfates, and metal oxalates, wherein said metals are selected from Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Rf, Db, Sg, Bh, Hs, Mt, Ds, Rg, Cn and Bi.
    [0004]
    4. Device according to claim 3, characterized in that the metals are selected from Ti, Fe, Mn, Co, Ni, Sn, Ru, Bi, V, Cr, Cu, Nb, Mo and Zn.
    [0005]
    5. Device according to claim 3 or 4, characterized in that the metal oxides are chosen from TiO 2, Fe 2 O 3, Fe 3 O 4, MnO 2, CoO, Co 3 O 4, NiO, SnO 2, RuO 2, Bi 2 O 3, V0 2, V 2 O 5, Cr 2 O 3, CuO, Cu 2 O , Nb2O5, Mo03 and ZnO.
    [0006]
    6. Device according to any one of the preceding claims, characterized in that the n-type semiconductor is TiO2.
    [0007]
    7. Device according to claim 3 or 4, characterized in that the metal phosphates are chosen from: - olivines corresponding to the formula MM'PO4, - fluorinated derivatives, hydroxylated and oxygenated with the formulas MxM "PO4F, MxM" PO4.0H and MxM "PO4.0, - carbonophosphates corresponding to the formula M3M'PO4CO3, and - pyrophosphates corresponding to the formula MxM'R207, in which M = Li or Na, M '= Fe, Co, Mn, Ni or a mixture thereof, M "= Fe, Co, Mn, Ni, V or Ti, and x ranges from 0 to 2.
    [0008]
    8. Device according to claim 3 or 4, characterized in that the metal sulphates are chosen from the materials corresponding to the formulas M'2 (SO4) 3, MM "SO4F and MxM" OSO4, in which M = Li or Na, M '= Fe, Co, Mn, Ni or a mixture thereof, and M "= Fe, Co, Mn, Ni, V or Ti.
    [0009]
    9. Device according to claim 3 or 4, characterized in that the oxalates of metals are chosen from the compounds corresponding to the formula M2M '(C204) 2, in which M = Li or Na and M' = Fe, Co, Mn , Ni or a mixture thereof.
    [0010]
    10. Device according to any one of the preceding claims, characterized in that the n-type semiconductor has a forbidden bandwidth Eg of at most 4.0 eV.
    [0011]
    11. Device according to any one of the preceding claims, characterized in that the n-type semiconductor comprises particles with a diameter ranging from 2 to 50 nm.
    [0012]
    12. Device according to any one of the preceding claims, characterized in that the n-type semiconductor has a specific surface area measured by the B.E.T. method. ranging from 20 m2 / g to 500 m2 / g.
    [0013]
    13. Device according to any one of the preceding claims, characterized in that the positive electrode film has a mesoporous structure.
    [0014]
    14. Device according to any one of the preceding claims, characterized in that the positive electrode film further comprises at least one dye and / or at least one light reflector.
    [0015]
    15. Device according to any one of the preceding claims, characterized in that the conductive transparent support is a conductive transparent glass type FTO type ITO, or type ZITO.
    [0016]
    16. A method for photorecharging a transparent photorechargeable electrochemical device as defined in any one of claims 1 to 15, characterized in that it comprises the following step: i) the exposure of said device, preferably on the said device comprising said positive electrode, to a source of light waves for at least 30 minutes, and preferably for at least 1 hour, to obtain said recharged device.
    [0017]
    17. Method for charging in the dark of a transparent electrochemical photorechargeable device as defined in any one of claims 1 to 15, characterized in that it comprises the following steps: i ') the exposure of said device, preferably on the side of said device comprising said positive electrode, at a source of light waves for at least 10 hours, ii ') using the device of step i') to power an electrical apparatus, and (iii ') the relaxation in the dark of the device of step ii ') for at least 6 hours, to obtain said reloaded device.
    [0018]
    18. Use of an n-type semiconductor as a positive electrode active material for a transparent electrochemical charge device as defined in any one of claims 1 to 15.5.
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    同族专利:
    公开号 | 公开日
    KR20160102444A|2016-08-30|
    JP2017503339A|2017-01-26|
    EP3075024A1|2016-10-05|
    US10333181B2|2019-06-25|
    JP6581983B2|2019-09-25|
    KR102303020B1|2021-09-23|
    US20180175463A1|2018-06-21|
    WO2015079170A1|2015-06-04|
    EP3075024B1|2018-12-26|
    FR3013901B1|2017-03-24|
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    法律状态:
    2016-10-24| PLFP| Fee payment|Year of fee payment: 4 |
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    优先权:
    申请号 | 申请日 | 专利标题
    FR1361775A|FR3013901B1|2013-11-28|2013-11-28|ELECTROCHEMICAL DEVICE AUTOPHOTORECHARGEABLE|FR1361775A| FR3013901B1|2013-11-28|2013-11-28|ELECTROCHEMICAL DEVICE AUTOPHOTORECHARGEABLE|
    US15/100,107| US10333181B2|2013-11-28|2014-11-27|Transparent autophotorechargeable electrochemical device|
    KR1020167017333A| KR102303020B1|2013-11-28|2014-11-27|Transparent self-photorechargeable electrochemical device|
    JP2016534701A| JP6581983B2|2013-11-28|2014-11-27|Transparent automatic photorechargeable electrochemical device|
    PCT/FR2014/053056| WO2015079170A1|2013-11-28|2014-11-27|Transparent self-photorechargeable electrochemical device|
    EP14814969.3A| EP3075024B1|2013-11-28|2014-11-27|Transparent self-photorechargeable electrochemical device|
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