• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The present invention is in the field of energy storage components and relates to a method for depositing nano / microparticles, including at least graphene sheets, on a support (8), comprising the steps of: oxidizing at least said graphene sheets; Suspending said nano / microparticles in at least one solution comprising at least water as a solvent; • hydrodynamically instilling each suspension on said substrate (15); • heating said substrate (15), during each spraying, so as to promote the complete evaporation of said solvent from each part of each said spray suspension on said substrate (15) at a temperature less than or equal to one and a half times the temperature of d boiling each said solution and less than or equal to 200 degrees Celsius; • Annealing said deposit (1) after said spraying or at a temperature sufficient to deoxidize at least the oxidized graphene present in said deposit (1) and greater than the temperature of said substrate (15) during the deposition step.
    公开号:FR3032362A1
    申请号:FR1500231
    申请日:2015-02-06
    公开日:2016-08-12
    发明作者:Paolo Bondavalli；Gregory Pognon；Christophe Galindo
    申请人:Thales SA；
    IPC主号:
    专利说明:

    [0001] The invention relates to components for storing energy, in particular capacitors. The capacitors concerned are also called "supercapacitors", characterized by a higher energy density than that of dielectric capacitors and a higher power density than that of batteries. Supercapacitors generally comprise two porous electrodes impregnated with an electrolyte (an ionic salt in generally organic solution, a quaternary ammonium salt such as tetraethylammonium tetrafluoroborate in acetonitrile or propylene carbonate, for example). These electrodes are generally separated by an insulating and porous membrane allowing the circulation of the ions of the electrolyte. The first supercapacitors, called "EDLC" (acronym 15 of "Electrochemical Double Layer Capacitator") are based on a principle equivalent to that of conventional capacitors with polarizable electrodes and an electrolyte acting as a dielectric. Their capacity comes from the organization of a double layer of ions and electrons at the electrolyte / electrode interface. Today, supercapacitors combine, for the storage of energy, a capacitive component resulting from the electrostatic organization of ions near the electrodes and a pseudocapacitive component due to oxidation-reduction reactions in the capacitor. The electrostatic component of the energy storage is effected by a non-homogeneous distribution of the electrolyte ions in the vicinity of the surface of each electrode, under the effect of the potential difference applied between the two electrodes. The electrostatic component of the energy storage confers a potentially high specific power and a very good behavior along the charging and discharging cycles. Materials with a very large ratio of specific surface area to volume, having a porosity adapted to ion storage at this scale, have been developed to increase the capacity of the supercapacitors. The methods of manufacturing these materials have been oriented towards the use of fullerenes, carbon nanotubes, activated carbon, carbon nanowires or CNF and graphene, which are advantageously light, inexpensive, and ecologically clean. Supercapacitors could replace conventional capacitors for applications with high energy demand, including extreme temperatures, vibrations, high acceleration or high salinity. In these environments, the batteries can not operate without their life span being very limited (these conditions apply to radar, motorsport, electrical avionics and military applications for example). Supercapacitors can also be applied to systems that require peaks of energy over short times, of the order of one minute, for acceleration phases of vehicles in land transport (automobiles, trams, buses, so-called devices). "Stop and start" in which energy is recovered during deceleration). 20 Supercapacitors could also be useful for the management of electricity in embedded systems, for the security of electrical installations, the securing of the energy supply of sensitive systems (radio sets, surveillance systems, military field, center of data), 25 in autonomous sensor networks for surveillance applications of industrial sites, complex or sensitive (hospitals, avionics, off-shore platform, oil prospecting, underwater applications) and finally in renewable energies (wind turbines, recovery of atmospheric electrical energy). To enable industrial application, the energy density and power of the supercapacitors must be optimized. In addition, the internal resistance of a supercapacitor is today too high and poorly controlled. Conventional supercapacitors consist of activated carbons with inhomogeneous and unoptimized pore size distributions and use a polymeric binder to insure the mechanical strength of their structure. This binder increases the internal electrical resistance of the capacitor and increases its weight disadvantageously. Inadequate porosity also imposes resistance to ion transfer within the active material. The publication of Bondavalli, P., Delfaure, C., Legagneux, P., Pribat, D., 2013, "Supercapacitor electrode based on mixtures of graphite and carbon nanotubes deposited using a dynamic air-brush technical deposition. Journal of the Electrochemical Society, 160 (4), A601-A606, discloses a method of depositing nano- / microparticles of graphene and carbon nanotubes by hydrodynamic spraying of a suspension on a support. This process allows the fabrication of supercapacitors with high energy and power densities, without using polymeric binder, but requires the use of toxic and polluting solvents, such as N-methyl-2-pyrrolidone (NMP) to allow the suspension of the nano- / microparticles. The publication of Youn, HC, Bak, SM, Park, HS, Yoon, SB, Roh, KC, Kim, KB, 2014, "One-step preparation of reduced graphene oxide / carbon nanotube hybrid thin film by electrostatic spray deposition for supercapacitor 20 Applications, "Metals and Materials International, 20 (5), 975-981, discloses the use of graphene oxide and oxidized carbon nanotubes for electrostatic spraying of a suspension on a support for the manufacture of supercapacitors. This method uses heating at 300 degrees Celsius during deposition, useful for the reduction or deoxidation of the carbonaceous structures present, but limits the manufacture of thick layers because the solution evaporates before deposition. This process further uses a water / ethanol mixture as a solvent for the suspension of the oxidized particles. This characteristic decreases the vaporization temperature of the solvent which also promotes evaporation of the solvent before deposition on the substrate and prevents the manufacture of a thick layer. In addition, the use of ethanol in the solvent is toxic and is not ecologically clean. The present invention relates to a process for depositing nano / microparticles, including at least graphene sheets, on a substrate, comprising the steps of: - oxidizing at least said graphene sheets; Suspending said nano / microparticles in at least one solution comprising at least water as a solvent; - hydrodynamic instability spray each suspension on said substrate; heating said substrate, during each spraying, so as to promote the complete evaporation of said solvent from each part of each said spray suspension on said substrate at a temperature less than or equal to one and a half times the boiling temperature of each said solution and less than or equal to 200 degrees Celsius; - Annealing said deposit after said one or more sprays at a temperature sufficient to deoxidize at least the oxidized graphene present in said deposit and greater than the temperature of said substrate during the deposition step. Advantageously, said nanoparticles / microparticles are suspended in a said solution of which said solvent is composed of more than 95% water (H 2 O) by weight and preferably more than 99% by weight water. Advantageously, a plurality of said suspensions are sprayed simultaneously on said substrate. Advantageously, the nano- / microparticles of the deposition process are chosen from carbon nanotubes, carbon nanowires, carbon nanotubes, carbon nanocornes, carbon onions and a mixture of these nanoparticles / microparticles, in which wherein said nano / microparticles are oxidized prior to spraying and wherein said deposition is annealed after said spraying at a temperature sufficient to deoxidize said nano / microparticles. Advantageously, at least one said nanoparticle is wet-oxidized with at least one element selected from sulfuric acid, phosphoric acid, sodium nitrate, nitric acid and potassium permanganate. and hydrogen peroxide. Advantageously, a heating element placed in contact with a support heats said substrate and each said portion of said sprayed suspension on said substrate. Advantageously, said deposit is annealed at a temperature between 200 degrees Celsius and 400 degrees Celsius. The invention also relates to a method for manufacturing an electrode comprising in superposition a deposition of nano- / microparticles and a substrate, said substrate comprising a current collector and said deposition of nano- / microparticles being obtained by a deposition process. previously described. The present invention also relates to an electrode of which said nano / microparticle deposition is obtainable by a previously described method.
    [0002] The present invention also relates to a supercapacitor comprising at least one said electrode described above. The following description presents several embodiments of the device of the invention: these examples are non-limiting of the scope of the invention.
    [0003] These exemplary embodiments have both the essential characteristics of the invention as well as additional features related to the embodiments considered. For the sake of clarity, the same elements will bear the same references in the different figures.
    [0004] By "nanoparticle" is meant particles whose at least the smallest dimension is nanometric, that is to say between 0.1 nm and 100 nm. By "microparticle" is meant particles whose at least the smallest dimension is micrometric, that is to say between 0.1 pm and 100 pm.
    [0005] The nano / microparticle geometries include nano / microfilts, nano / microtiges, nano / microtubes, nano / microcornes, nano / micro onions, and monofilament nano / microfeuilles comprising crystalline or multi-layer layer comprising a plurality of stacked leaflets. A nano-5 / microtube is formed of one or more wound nano- / microfossils. A nano / microfil is a one-dimensional object full of massive material. A nano / microtige is a hollow one-dimensional object. In the case of carbon, a sheet is referred to as "graphene" and is in the form of a two-dimensional carbon crystal of monoatomic thickness and nano- / micrometric size. The carbon nanotubes are known and formed of a sheet of graphene wound into a tube (designated by the acronym of "Single Wall Carbon NanoTube", SWCNT) or several stacked sheets of graphene wound into a tube (designated by the acronym 15 of "Multi Wall Carbon NanoTube", MWCNT). By "electrode" is meant an assembly comprising a deposition of nano / microparticles on a substrate (comprising a current collector which electrically conducts and optionally a layer or a thick material for the mechanical strength of the electrode). The invention will be better understood and other advantages, details and features thereof will become apparent from the following explanatory description, given by way of example with reference to the accompanying drawings, in which: FIG. schematic of an apparatus for producing nanoparticles / nanoparticles according to a method according to the invention; Figure 2 is a schematic representation of two deposits of nano / microparticles and the electrolyte of a supercapacitor; FIG. 3 is a schematic representation illustrating a particular embodiment of a method according to the invention; FIG. 4 is a photograph taken by a scanning electron microscope of the structure of the material of a nanoparticle / microparticle deposit produced by a method according to the invention; FIG. 5 is a photograph taken by a scanning electron microscope of the material structure of a nano- / microparticle deposit made according to a method according to the invention; FIG. 6 is a photograph taken by a scanning electron microscope of the material structure of a nano / microparticle deposit produced by a process according to the invention; FIG. 7 presents cyclic voltammograms obtained from deposits of nanoparticles / microparticles of different compositions; FIG. 8 illustrates the influence of the cycling rate on the capacity of 10 nano / microparticle deposits of different compositions, and FIG. 9 illustrates the value of the specific capacity and energy density of an electrode based on the proportion of oxidized carbon nanotubes in the pulverized suspension.
    [0006] The following description presents several embodiments of the device of the invention: these examples are non-limiting of the scope of the invention. These exemplary embodiments have both the essential characteristics of the invention as well as additional features related to the embodiments considered. For the sake of clarity, the same elements will bear the same references in the different figures. Figure 1 is a schematic representation of an apparatus 3 for producing nano- / microparticle deposition according to a method according to the invention.
    [0007] The apparatus 3 comprises a spraying nozzle 4, a reservoir 5 containing a suspension of nanoparticles and a source of sputtering gas. The nanoparticles comprise oxidized phosphor particles and may comprise, in particular embodiments of the invention, oxidized carbon nanotubes, oxidized carbon nanowires, oxidized carbon nanotubes, oxidized carbon nanocornes and the like. oxidized carbon onions. Other nanoparticles are conceivable. The solvent used for the suspension may advantageously be composed of more than 95% of water (H 2 O) and even more advantageously of more than 99% of water (H 2 O). In particular embodiments of the invention, water 3032362 8 can be mixed with other solvents, in proportions that allow them to remain miscible with water, such as methanol (CH4O), ethanol (C2H60 ), ethylene chloride (DCE), dichlorobenzidine (DCB), N-methyl-2-pyrrolidone (NMP), dimethylformamide (DMF), hexamethylphosphoramide (HMPA), cyclopentanone 5 (C5H80), tetramethylene sulfoxide (TMSO), ε-caprolactone, 1,2-dichlorobenzene, 1,2-dimethylbenzene, bromobenzene, lodobenzene and toluene. Other compounds are conceivable. The sputtering gas is, for example, air. The nozzle 4 is supplied with suspension from the tank 5 and with spray gas from the source 6. The nozzle 4 is able to spray the suspension, fed at low pressure, in microdroplets using the gas supplied at high pressure. . The nozzle 4 is of the airbrush type. The drops are created by hydrodynamic instability between the liquid phase, the gaseous phase and the nozzle 4, that is, in a particular embodiment of the invention, sprayed by the effect of the pressure imposed on water, air and water. the geometry of the nozzle. By "microdroplets" is meant drops of microscopic size, whose diameter is between about 1 and 100 microns. In a particular embodiment of the invention, the apparatus 3 comprises heating elements 7 of the support 8 in the form of resistive heating elements 9, connected to a power supply circuit (not shown) so that the Resistive heating elements 9 emit heat by the Joule effect when they are crossed by an electric current. Alternatively, the apparatus 3 comprises heating elements 7 of the support 8 by induction, comprising for example a plate on which the support 8 is placed with inductors, to induce currents in the plate and generate heat. The apparatus 3 comprises a temperature sensor 10 arranged to measure the temperature of the support 8. In operation, the nozzle 4 generates a spray jet 11 formed of suspension microdroplets projected towards the surface 12 to be coated with the substrate 15. The spray jet 11 reaches the surface 12 to be covered in an impact zone 13 whose shape and dimensions depend in particular on the geometry of the nozzle 4, the adjustment of the nozzle 4 and the position of the nozzle 4 relative to the surface 12 to be covered.
    [0008] The shape and dimensions of the impact zone 13 depend in particular on the angle α at the apex of the cone formed by the spray jet 11 at the outlet of the nozzle 4 and the distance between the outlet of the nozzle 4 and the nozzle. Surface 12 of the substrate 15. They also depend on the pressure of the sputtering gas (related to the spraying gas flow rate) and the flow rate of each slurry. The spray jet 11 is for example conical of revolution, so that it forms an impact zone 13 of generally circular shape. Alternatively, the spray pattern 11 could define an oblong impact zone 13, more elongate in a first direction than in a second direction perpendicular to the first direction. Figure 2 is a schematic representation of two deposits of nano- / microparticles 1 and the electrolyte 2 of a supercapacitor. The storage of the energy is carried out by a non-homogeneous distribution of the ions of the electrolyte 2 in the vicinity of the surface of each deposit of nano- / microparticles 1. During a polarization of the electrodes, several ionic layers can be formed. in the vicinity of the surface of the deposits of nano- / microparticles 1 and have a thickness of the order of a few nanometers, depending on the electrolyte 2 considered and its concentration. The origin of these layers is electrostatic. This process does not involve electrochemical transformation of the material as in the case of accumulators. Figure 2 illustrates the importance of developing materials with very large specific surfaces and having porosity adapted to ion storage at this scale to increase the storage capacity of supercapacitors.
    [0009] In a particular embodiment of the invention, the nano- / microparticles used to form a deposit 1 may be graphene sheets and single-walled carbon nanotubes (SWCNTs).
    [0010] Figure 3 is a schematic representation illustrating a particular embodiment of a method according to the invention. It illustrates the formation of one or more deposits of nanoparticles 1 made on a substrate 15 (having a current collector, conductive and optionally a thick layer for its mechanical strength) superimposed with the support.
    [0011] In a first step, the carbon nanoparticles / nanoparticles are oxidized. The carbon nanoparticles / nanoparticles are, for example, SWCNTs. SWCNTs are dispersed in an equal volume mixture of sulfuric acid and nitric acid for 30 minutes. The mixture is then refluxed for 3 hours.
    [0012] The SWCNTs are then oxidized. They can be recovered by vacuum filtering the mixture and washing with several hundred milliliters of water until a neutral pH of the filtrate. The product is dried under vacuum at 70 ° C for several days. The graphene oxide particles can be obtained commercially. In a second step, suspensions of each of the various particles can be prepared in deionized water by sonication for one hour, at a concentration of between 5 μg.mL-1 and 50 mg.mL-1 and preferably between 50 μg. pg.m1: 1 and 5 mg.mL-1. The various suspensions can then be pooled in a single suspension and the suspension sonicated for one hour. In a third step, the nano- / microparticles are deposited on the current collector of the substrate 15. The deposition is carried out by spraying by hydrodynamic instability of the suspension, on a substrate 15 heated to a temperature preferably greater than 100.degree. preferably less than or equal to 200 ° C, or even 150 ° C: the temperature must be sufficient to allow rapid evaporation of drops deposited by spraying and thus avoid the effect "coffee stain", that is to say a distribution surface of nano- / microparticles adsorbed non-homogeneous. On the other hand, too high a temperature, such as that presented in the method presented by Youn et al. would cause total evaporation of the drops during their journey between the nozzle 4 and the support 8, thus preventing adsorption or controlled and effective attachment. At a minimum, the method of Youn et al. requires the use of a high slurry volume to compensate for the total evaporation induced by a high temperature of a high proportion of the pulverized slurry. In a fourth step, the deposit 1 is annealed at a temperature above 200 ° C to deploy the accessible surfaces of the electrolyte 2 in the deposition of nano- / microparticles 1, reduce or deoxidize graphene oxide and oxidized nanotubes and increase the conductivity of the nano-microparticle deposition 1. This step is necessary because the deposition temperature is too low to reduce or deoxidize the nano- / microparticles of the deposit 1. This step has two distinct advantages over the process. Presented by Youn et al: on the one hand, annealing allows the nano / microparticles to be deoxidized at an effective temperature while keeping a lower temperature during the spraying (and the related advantages presented in the previous paragraph). On the other hand annealing can be done in a controlled manner, for example by imposing an equal annealing time for all the particles deposited. Disadvantageously, in the process presented by Youn et al., The particles deposited at the beginning of the spraying will undergo a different annealing time from the particles deposited at the end of the spraying. In this embodiment of the process according to the invention, a hierarchization of the two types of carbon structures takes place during spray deposition on the substrate 15 heated by the support 8, which makes it possible to vaporize the water instantaneously. This hierarchization is illustrated in FIG. 4, FIG. 5 and FIG. 6. FIGS. 4, 5 and 6 are photographs taken by a scanning electron microscope of the material structure of a nano-microparticle deposit. performed according to a process according to the invention. They illustrate the hierarchical structure whose production is described above: the nanotubes of oxidized carbons are interposed between the layers of oxidized graphene. The homogeneous distribution of the two structures is already potentially initiated in the suspension before spraying, via possible esterifications between the hydroxyl and carboxylic groups of each of the two oxidized carbonaceous structures. In a particular and different embodiment of the invention, other oxidized carbon structures may be introduced into the spray suspension, such as carbon nanowires, carbon nanotubes, carbon nanocornes and carbon onions.
    [0013] Figure 7 shows cyclic voltammograms obtained from nano / microparticle deposits 1 of different compositions. The different measurements are carried out at a scanning speed of 20 mV.s-1, in a three-electrode arrangement: the electrode comprising a nano- / microparticle deposit 1, an Ag / AgCl electrode and a LiNO 3 electrode. 3 molars. Curve (a) corresponds to a nano- / microparticle deposit obtained according to a process of the invention using oxidized graphene nanoparticles / microparticles. Curve (b) corresponds to a nano- / microparticle deposit 1 obtained according to a process of the invention using oxidized graphene nano- / microparticles and oxidized carbon nanotubes mixed in equal proportions by mass. Curve (c) corresponds to a nano- / microparticle deposit 1 obtained using pulverized oxidized carbon nanotubes. Curve (d) corresponds to a nano- / microparticle deposition 1 obtained using nano- / microparticles of graphene and pulverized carbon nanotubes (previously unoxidized materials suspended in an NMP solvent). Finally, the curve (e) corresponds to a deposition of nano- / microparticles 1 made of disordered carpet or "bucky paper" of carbon nanotubes and graphene in mass proportion of 50% / 50%. The rectangular shape of the various cyclic voltammograms of FIG. 7 illustrates the capacitance of the different electrodes measured. Figure 7 further illustrates an increase in the measured current density when the nanoparticle / microparticle deposits 1 are made from oxidized nano / microparticles (curves (a), (b) and (c)).
    [0014] FIG. 8 illustrates the influence of the cycling rate on the specific capacitance of electrodes covered with a deposit of nano / microparticles 1 of different compositions. Curve (f) corresponds to a nano / microparticle deposit 1 obtained according to a process of the invention using oxidized graphene nano / microparticles and oxidized SWCNTs, in a proportion by mass of 25% / 75% respectively, and sprayed onto a substrate heated to 200 ° C. Heating the substrate at 170 ° C gives similar results. Curve (g) corresponds to a deposition of nano / microparticles 1 obtained according to a process of the invention using oxidized graphene nano- / microparticles, curve (h) corresponds to a deposition of nano- / microparticles 1 obtained in spraying with oxidized SWCNTs, curve (i) corresponds to a nano- / microparticle deposit 1 based on "bucky paper" with SWCNT, curve (j) corresponds to a nano- / microparticle deposit 1 made from activated carbon paste (as in conventional supercapacitors) and curve (k) corresponds to a deposition of nano-3032362 13 / microparticles based on "bucky paper" with a mixture of oxidized nano / graphene microparticles and SWCNT oxidized. For all cycling rates, FIG. 8 shows that the specific capacitances are higher in the case of electrodes whose nanoparticle / nanoparticle deposits are made via the spraying method compared to the methods of manufacture using bucky paper "and activated carbon paste. In addition, FIG. 8 illustrates that among the nano-/ microparticle deposits 1 produced by sputtering, the specific capacitances of the electrodes obtained according to a process of the invention are higher than those of the electrode 10 manufactured with deposits 1 of SWCNT oxidized (alone). The crossing of the curves (f) and (g) shows the interest of an interaction between oxidized nano- / microparticles of graphene and oxidized SWCNT to keep a high specific capacity even at high cycling speed. In addition, curve (f) illustrates that the interaction between oxidized graphene nanoparticles / microparticles and oxidized SWCNTs makes it possible to keep relatively stationary specific capacitance values. FIG. 9 illustrates the value of the specific capacitance and energy density of an electrode as a function of the proportion of oxidized SWCNTs in the pulverized suspension, when using an electrode obtained by a process of FIG. invention using oxidized graphene nano- / microparticles and oxidized SWCNTs. The specific capacity and the energy density are optimal for a mass proportion of SWCNT between 0 and 25%.
    权利要求:
    Claims (10)
    [0001]
    REVENDICATIONS1. A method of depositing nano- / microparticles, including at least graphene sheets, on a substrate (15), comprising the steps of: - oxidizing at least said graphene sheets; suspending said nano / microparticles in at least one solution comprising at least water as a solvent; - hydrodynamically instilling each suspension on said substrate (15); heating said substrate (15), during each spraying, so as to promote the complete evaporation of said solvent from each part of each said spray suspension on said substrate (15) at a temperature less than or equal to one and a half times the temperature of boiling each said solution and less than or equal to 200 degrees Celsius; - Annealing said deposit (1) after said one or more sprays at a temperature sufficient to deoxidize at least the oxidized graphene present in said deposit (1) and greater than the temperature of said substrate (15) during the deposition step.
    [0002]
    2. Deposition process according to the preceding claim wherein said nano / microparticles are suspended in said solution of which said solvent is composed of more than 95% water (H2O) by weight and preferably more than 99% water. in mass.
    [0003]
    3. deposition process according to the preceding claims wherein a plurality of said suspensions are sprayed simultaneously on said substrate (15).
    [0004]
    4. A deposition method according to one of the preceding claims wherein said nano- / microparticles are selected from carbon nanotubes, carbon nanowires, carbon nanotypes, carbon nanocornes, carbon onions and a mixture of these nano- / microparticles, wherein said nanoparticles / nanoparticles are oxidized before spraying and wherein said deposit (1) is annealed after said spraying at a temperature sufficient to deoxidize said nanoparticles / microparticles.
    [0005]
    5. Method according to one of the preceding claims wherein at least one said nanoparticle is wet-oxidized with at least one element selected from sulfuric acid, phosphoric acid, sodium nitrate, nitric acid, potassium permanganate and hydrogen peroxide.
    [0006]
    6. A deposition method according to one of the preceding claims wherein a heating element (7) brought into contact with a support (8) heats said substrate (15) and each said portion of said sprayed suspension on said substrate (15) .
    [0007]
    7. Deposit method according to one of the preceding claims wherein said deposit (1) is annealed at a temperature between 200 degrees Celsius and 400 degrees Celsius.
    [0008]
    8. A method of manufacturing an electrode, comprising in superposition a deposition of nano- / microparticles (1) and a substrate (15), said substrate (15) comprising a current collector, said deposition of nano- / microparticles (1). ) being obtained by a method according to one of the preceding claims.
    [0009]
    9. Electrode of which said deposition of nano- / microparticles (1) is obtainable by a method according to one of claims 1 to 7.
    [0010]
    10. Supercapacitor comprising at least one said electrode according to the preceding claim.
    类似技术:
    公开号 | 公开日 | 专利标题
    Korenblit et al.2012|In situ studies of ion transport in microporous supercapacitor electrodes at ultralow temperatures
    EP3254292A1|2017-12-13|Method of depositing oxidized carbon-based microparticles and nanoparticles
    Lee et al.2015|High performance flexible supercapacitor electrodes composed of ultralarge graphene sheets and vanadium dioxide
    US9312078B2|2016-04-12|Patterned graphite oxide films and methods to make and use same
    Portet et al.2005|High power density electrodes for carbon supercapacitor applications
    Fan et al.2007|High electroactivity of polyaniline in supercapacitors by using a hierarchically porous carbon monolith as a support
    US8699207B2|2014-04-15|Electrodes synthesized from carbon nanostructures coated with a smooth and conformal metal adlayer
    US9136536B2|2015-09-15|Method of making cohesive carbon assembly and its applications
    KR101995465B1|2019-07-03|Electrode structure having roll shape, electrode and electric device including the electrode structure, and method of manufacturing the electrode structure
    Lochmann et al.2018|Nanoimprint lithography of nanoporous carbon materials for micro-supercapacitor architectures
    Brousse et al.2018|Laser-scribed Ru organometallic complex for the preparation of RuO2 micro-supercapacitor electrodes on flexible substrate
    Guerra et al.2019|ZnO/Carbon nanowalls shell/core nanostructures as electrodes for supercapacitors
    Shulga et al.2018|Preparation of graphene oxide-humic acid composite-based ink for printing thin film electrodes for micro-supercapacitors
    Du et al.2017|A Three‐Layer All‐In‐One Flexible Graphene Film Used as an Integrated Supercapacitor
    RU2572840C2|2016-01-20|Metal foil with conductive layer and manufacturing method thereof
    Gupta et al.2016|Electrostatic layer-by-layer self-assembled graphene/multi-walled carbon nanotubes hybrid multilayers as efficient ‘all carbon’supercapacitors
    Lee et al.2021|Outstanding Low‐Temperature Performance of Structure‐Controlled Graphene Anode Based on Surface‐Controlled Charge Storage Mechanism
    EP3649663A1|2020-05-13|Method for preparing an electrode comprising a substrate, aligned carbon nanotubes and a metal oxide deposited by oxidative deposition, the electrode and uses thereof.
    EP3459095B1|2021-08-11|Method of manufacturing a supercapacitor
    KR20170004075A|2017-01-11|Three-dimensional electrode structure including graphene-metal, preparing method of the same, and three-dimensional capacitor electrode including the same
    KR101940795B1|2019-01-21|Electrode structure having roll shape, electrode and electric device including the electrode structure, and method of manufacturing the electrode structure
    FR2981509A1|2013-04-19|COLLECTOR-ELECTRODE ASSEMBLY FOR INTEGRATING AN ELECTRIC ENERGY STORAGE DEVICE
    US10804043B2|2020-10-13|Method of preparing core-shell structure nanoparticle using structure-guided combustion waves
    Haro2020|From cluster design to energy storage device engineering
    Bettini2013|Synthesis and electrochemical investigation of cluster assembled carbon thin films
    同族专利:
    公开号 | 公开日
    CN107408462B|2021-03-23|
    JP2018508992A|2018-03-29|
    WO2016124756A1|2016-08-11|
    CN107408462A|2017-11-28|
    KR20170116066A|2017-10-18|
    FR3032362B1|2020-05-29|
    US20180025853A1|2018-01-25|
    EP3254292A1|2017-12-13|
    AU2016214292A1|2017-08-31|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US20100221531A1|2007-10-12|2010-09-02|Sang Keun Oh|Carbon nanotube conductive layer using spray coating and preparing method thereof|
    US20130059195A1|2011-09-02|2013-03-07|Semiconductor Energy Laboratory Co., Ltd.|Electrode for power storage device and power storage device|
    US20130133925A1|2011-10-24|2013-05-30|Samsung Electro-Mechanics Co., Ltd.|Graphene transparent electrode and method for manufacturing the same|
    US20140242293A1|2013-02-26|2014-08-28|Quantumscape Corporation|Inorganic films using a cascaded source for battery devices|
    WO2013100382A1|2011-12-31|2013-07-04|제일모직주식회사|Preparation method of graphene-carbon nanotube composite using spray pyrolysis, and graphene-carbon nanotube composite prepared thereby|
    US9530531B2|2013-02-21|2016-12-27|Nanotek Instruments, Inc.|Process for producing highly conducting and transparent films from graphene oxide-metal nanowire hybrid materials|
    US20140272199A1|2013-03-14|2014-09-18|Yi-Jun Lin|Ultrasonic spray coating of conducting and transparent films from combined graphene and conductive nano filaments|
    US8871296B2|2013-03-14|2014-10-28|Nanotek Instruments, Inc.|Method for producing conducting and transparent films from combined graphene and conductive nano filaments|
    TW201504363A|2013-07-16|2015-02-01|Enerage Inc|Graphene printing ink and preparation method of graphene circuit|
    CN103400632B|2013-07-17|2016-05-11|常州二维碳素科技股份有限公司|A kind of Graphene dopant material and application thereof|
    CN103396573B|2013-08-22|2015-07-22|电子科技大学|Preparation method of compound nano film|RU2644579C1|2016-12-13|2018-02-13|Сергей Иванович Жебелев|Method of assembly of nanomaterials from graphene|
    GB201707428D0|2017-05-09|2017-06-21|Applied Graphene Mat Plc ]|Composite moulding materials|
    CN113244931A|2020-02-11|2021-08-13|中国石油化工股份有限公司|Catalyst and method for catalytic oxidation deoxidation of unsaturated hydrocarbon-containing gas|
    FR3110281A1|2020-05-14|2021-11-19|Thales|Nanostructured electrode for supercapacitor|
    法律状态:
    2016-01-25| PLFP| Fee payment|Year of fee payment: 2 |
    2016-08-12| PLSC| Publication of the preliminary search report|Effective date: 20160812 |
    2017-01-26| PLFP| Fee payment|Year of fee payment: 3 |
    2018-01-26| PLFP| Fee payment|Year of fee payment: 4 |
    2020-01-27| PLFP| Fee payment|Year of fee payment: 6 |
    2021-01-26| PLFP| Fee payment|Year of fee payment: 7 |
    2022-01-27| PLFP| Fee payment|Year of fee payment: 8 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1500231|2015-02-06|
    FR1500231A|FR3032362B1|2015-02-06|2015-02-06|PROCESS FOR THE DEPOSITION OF NANOPARTICLES AND OXIDIZED CARBON MICROPARTICLES|FR1500231A| FR3032362B1|2015-02-06|2015-02-06|PROCESS FOR THE DEPOSITION OF NANOPARTICLES AND OXIDIZED CARBON MICROPARTICLES|
    EP16706982.2A| EP3254292A1|2015-02-06|2016-02-05|Method of depositing oxidized carbon-based microparticles and nanoparticles|
    JP2017541337A| JP2018508992A|2015-02-06|2016-02-05|Method for depositing oxidized carbon-based microparticles and nanoparticles|
    AU2016214292A| AU2016214292A1|2015-02-06|2016-02-05|Method of depositing oxidized carbon-based microparticles and nanoparticles|
    PCT/EP2016/052541| WO2016124756A1|2015-02-06|2016-02-05|Method of depositing oxidized carbon-based microparticles and nanoparticles|
    US15/548,710| US20180025853A1|2015-02-06|2016-02-05|Method of depositing oxidized carbon-based microparticles and nanoparticles|
    KR1020177024642A| KR20170116066A|2015-02-06|2016-02-05|Method of depositing oxidized carbon-based microparticles and nanoparticles|
    CN201680013301.5A| CN107408462B|2015-02-06|2016-02-05|Method for depositing oxidized carbon-based microparticles and nanoparticles|
    [返回顶部]