EP3254292A1 - Procede de depot de nanoparticules et de microparticules carbonees oxydees - Google Patents
Procede de depot de nanoparticules et de microparticules carbonees oxydeesInfo
- Publication number
- EP3254292A1 EP3254292A1 EP16706982.2A EP16706982A EP3254292A1 EP 3254292 A1 EP3254292 A1 EP 3254292A1 EP 16706982 A EP16706982 A EP 16706982A EP 3254292 A1 EP3254292 A1 EP 3254292A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- nano
- microparticles
- substrate
- carbon
- deposit
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 81
- 239000011859 microparticle Substances 0.000 title claims abstract description 76
- 238000000034 method Methods 0.000 title claims abstract description 37
- 238000000151 deposition Methods 0.000 title claims abstract description 35
- 229910052799 carbon Inorganic materials 0.000 title claims description 24
- 239000000758 substrate Substances 0.000 claims abstract description 34
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 33
- 239000000725 suspension Substances 0.000 claims abstract description 31
- 230000008021 deposition Effects 0.000 claims abstract description 27
- 238000005507 spraying Methods 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000002904 solvent Substances 0.000 claims abstract description 16
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 238000001704 evaporation Methods 0.000 claims abstract description 7
- 230000008020 evaporation Effects 0.000 claims abstract description 7
- 238000009835 boiling Methods 0.000 claims abstract description 3
- 230000001590 oxidative effect Effects 0.000 claims abstract description 3
- 239000002041 carbon nanotube Substances 0.000 claims description 19
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 19
- 230000008569 process Effects 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 12
- 239000007921 spray Substances 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 241000234282 Allium Species 0.000 claims description 7
- 235000002732 Allium cepa var. cepa Nutrition 0.000 claims description 7
- 239000002070 nanowire Substances 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 238000000137 annealing Methods 0.000 claims description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 238000005137 deposition process Methods 0.000 claims description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 239000012286 potassium permanganate Substances 0.000 claims description 2
- 235000010344 sodium nitrate Nutrition 0.000 claims description 2
- 239000004317 sodium nitrate Substances 0.000 claims description 2
- 238000003303 reheating Methods 0.000 abstract 1
- 239000002109 single walled nanotube Substances 0.000 description 17
- 239000000463 material Substances 0.000 description 12
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 10
- 239000003792 electrolyte Substances 0.000 description 10
- 239000002245 particle Substances 0.000 description 9
- 150000002500 ions Chemical class 0.000 description 8
- 239000003990 capacitor Substances 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 238000009826 distribution Methods 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- 230000001351 cycling effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000002071 nanotube Substances 0.000 description 4
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 238000004544 sputter deposition Methods 0.000 description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- LPDSNGAFAJYVKH-UHFFFAOYSA-N 4-(4-aminophenyl)-2,3-dichloroaniline Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C(Cl)=C1Cl LPDSNGAFAJYVKH-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 2
- 239000003570 air Substances 0.000 description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 2
- 239000011852 carbon nanoparticle Substances 0.000 description 2
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 2
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000002048 multi walled nanotube Substances 0.000 description 2
- 230000008520 organization Effects 0.000 description 2
- ISXOBTBCNRIIQO-UHFFFAOYSA-N tetrahydrothiophene 1-oxide Chemical compound O=S1CCCC1 ISXOBTBCNRIIQO-UHFFFAOYSA-N 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical class C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- 229910013553 LiNO Inorganic materials 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000010616 electrical installation Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004110 electrostatic spray deposition (ESD) technique Methods 0.000 description 1
- 238000007590 electrostatic spraying Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012913 prioritisation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000009718 spray deposition Methods 0.000 description 1
- -1 tetraethylammonium tetrafluoroborate Chemical compound 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/007—After-treatment
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/20—Graphite
- C01B32/21—After-treatment
- C01B32/23—Oxidation
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
- H01G11/28—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features arranged or disposed on a current collector; Layers or phases between electrodes and current collectors, e.g. adhesives
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/22—Electronic properties
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Definitions
- the invention relates to components for energy storage, 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.
- an electrolyte an ionic salt in generally organic solution, a quaternary ammonium salt such as tetraethylammonium tetrafluoroborate in acetonitrile or propylene carbonate, for example.
- the first supercapacitors known as “EDLC” (acronym for “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.
- EDLC Electrochemical Double Layer Capacitator
- 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.
- Supercapacitors could replace conventional capacitors for applications with high energy demands, 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 energy peaks on short times, of the order of a minute, for acceleration phases of vehicles in land transport (automobiles, trams, buses, devices called “ stop and start "in which energy is recovered during deceleration).
- Supercapacitors could also be useful for managing electricity in embedded systems, for securing electrical installations, securing the energy supply of sensitive systems (radio sets, surveillance systems, military field, radio control center). data), in autonomous sensor networks for surveillance applications of industrial sites, complex or sensitive (hospitals, avionics, offshore platform, oil prospecting, submarine applications) and finally in renewable energies (wind turbines, recovery of atmospheric electric energy).
- sensitive systems radio sets, surveillance systems, military field, radio control center. data
- autonomous sensor networks for surveillance applications of industrial sites, complex or sensitive (hospitals, avionics, offshore platform, oil prospecting, submarine applications) and finally in renewable energies (wind turbines, recovery of atmospheric electric energy).
- the energy density and power of supercapacitors must be optimized.
- the internal resistance of a supercapacitor is today too high and poorly controlled.
- the usual supercapacitors consist of activated carbons with inhomogeneous and unoptimized pore size distributions and use a polymeric binder to ensure the mechanical strength of their structure. This binder
- the present invention relates to a process for depositing nano- / microparticles, including at least graphene sheets, on a substrate, comprising the steps of:
- said nanoparticles / microparticles are suspended in a said solution in which said solvent is composed of more than 95% water (H 2 0) by weight and preferably more than 99% by weight water.
- a plurality of said suspensions are sprayed simultaneously on said substrate.
- the nano- / microparticles of the deposition process are chosen from carbon nanotubes, carbon nanowires, carbon nanotypes, carbon nanocornes, carbon onions and a mixture of these nanoparticles / microparticles, in which 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.
- At least one said wet nanoparticle is oxidized with at least one element selected from sulfuric acid, acid and phosphoric acid, sodium nitrate, nitric acid, potassium permanganate and hydrogen peroxide.
- a heating element placed in contact with a support heats said substrate and each said part of said sprayed suspension on said substrate.
- 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 method described. previously.
- the present invention also relates to an electrode of which said nano- / microparticle deposition can be obtained by a method described above.
- said deposition of the electrode comprises at least graphene and a type of said nano- / microparticles chosen from carbon nanotubes, carbon nanowires, carbon nanotubes, carbon nanocornes and carbon onions.
- the present invention also relates to a supercapacitor comprising at least one said electrode described above.
- nanoparticle is understood to mean particles of which at least the smallest of the dimensions is nanometric, that is to say between 0.1 nm and 100 nm.
- microparticle is meant particles of which at least the smallest of the dimensions is micrometric, that is to say between 0.1 ⁇ and 100 ⁇ .
- Nano- / microparticle geometries include nano- / microfilts, nano- / microtiges, nano- / microtubes, nano- / microcornes, nano- / micro onions, and monofilament-type nano- / microfeuilles comprising a layer. crystalline or multifile comprising several stacked leaflets.
- a nano- / 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.
- a sheet is designated by the term “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 for "Multi Wall Carbon NanoTube", MWCNT).
- electrode an assembly comprising a deposition of nanoparticles / microparticles on a substrate (comprising a current collector which leads electrically and optionally a layer or a thick material for the mechanical strength of the electrode).
- FIG. 1 is a schematic representation of an apparatus for producing nano- / microparticle deposition 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;
- Figure 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 produced according to a process according to the invention.
- FIG. 6 is a photograph taken by a scanning electron microscope of the structure of the material of a nano-microparticle deposit produced according to a method 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 nano- / microparticle deposit capacity of different compositions
- FIG. 9 illustrates the value of the specific capacity and the energy density of an electrode as a function of the proportion of oxidized carbon nanotubes in the pulverized suspension.
- Figure 1 is a schematic representation of an apparatus 3 for producing nano- / microparticle deposition according to a method according to the invention.
- the apparatus 3 comprises a spray nozzle 4, a reservoir 5 containing a suspension of nano / microparticles and a source of spray gas 6.
- the nano- / microparticles comprise oxidized graphene particles and may comprise, in particular embodiments of the invention, oxidized carbon nanotubes, oxidized carbon nanowires, nanotubes oxidized carbon, oxidized carbon nanocornes and 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% water (H 2 O).
- the water may be mixed with other solvents, in proportions that allow them to remain miscible with water, such as methanol (CH 4 0), ethanol (C 2 H 6 O), ethylene chloride (DCE), dichlorobenzidine (DCB), N-methyl-2-pyrrolidone (NMP), dimethylformamide (DMF), hexamethylphosphoramide (HMPA), cyclopentanone (C 5 H 8 O), tetramethylene sulfoxide (TMSO), ⁇ -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 spray gas from the source 6.
- the nozzle 4 is suitable for spraying 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. geometry of the nozzle.
- microdroplets drops of microscopic size, whose diameter is between about 1 and 100 microns.
- 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 elements Resistive heating elements 9 emit heat by the Joule effect when an electric current passes through them.
- 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.
- the nozzle 4 In operation, the nozzle 4 generates a spray jet 1 1 formed of suspension microdroplets projected towards the surface 12 to be covered with substrate 15.
- the spray jet 1 1 reaches the surface 12 to be covered in an impact zone 13, the shape and dimensions of which depend in particular on the geometry of the nozzle 4, the adjustment of the nozzle 4 and the position of the nozzle. the nozzle 4 relative to the surface 12 to be covered.
- the shape and the dimensions of the impact zone 13 depend in particular on the angle ⁇ at the apex of the cone formed by the spray jet 1 1 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 suspension.
- the spray jet 1 1 is for example conical of revolution, so that it forms an impact zone 13 of generally circular shape.
- the spray jet 1 1 could define an oblong impact zone 13, more elongated in a first direction than in a second direction perpendicular to the first.
- 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.
- several ionic layers may 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.
- the nano- / microparticles used to form a deposit 1 may be graphene sheets and single-walled carbon nanotubes (SWCNT).
- 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.
- 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. 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.
- a second step it is possible to prepare suspensions of each of the different particles in deionized water by sonication for one hour, at a concentration of between 5 ⁇ g.mL -1 and 50 mg ml -1 and preferably between 50 ⁇ g.mL "1 and 5 mg.mL " 1 .
- the various suspensions can then be combined into a single suspension and the suspension sonicated for one hour.
- 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 ° C. and preferentially 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 surface distribution nano- / microparticles adsorbed non-homogeneous.
- a temperature too high such as that presented in the method presented by Youn et al.
- the method of Youn et al. requires the use of a high suspension volume for to compensate for the total evaporation induced by a high temperature of a high proportion of the pulverized suspension.
- 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 deposition of nano- / microparticles 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 advantages which are linked to and presented in the previous paragraph).
- annealing can be done in a controlled manner, for example by imposing an equal annealing time for all the particles deposited.
- annealing time for all the particles deposited.
- FIGS. 4, 5 and 6 are photographs taken by a scanning electron microscope of the material structure of a nano-microparticle deposit 1 made according to a method 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 carbonaceous structures may be introduced into the suspension such as carbon nanowires, carbon nanotubes, carbon nanocornes and carbon onions.
- FIG. 7 presents cyclic voltammograms obtained from nanoparticles / microparticle deposits 1 of different compositions.
- the various 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 to 3 electrode.
- the curve (a) corresponds to a nano- / microparticle deposit obtained according to a process of the invention using oxidized graphene nanoparticles / microparticles.
- the curve (b) corresponds to a nano-microparticle deposit 1 obtained.
- the curve (c) corresponds to a deposition of nano- / microparticles 1 obtained using nanotubes
- the curve (d) corresponds to a deposition of nano- / microparticles 1 obtained using nano- / microparticles of graphene and pulverized carbon nanotubes (unoxidized materials in the meadow). alable, suspended in an NMP solvent)
- 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% .
- FIG. 7 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 measured current density when nano- / microparticle 1 deposits are made from oxidized nano- / microparticles (curves (a), (b) and (c)).
- FIG. 8 illustrates the influence of the cycling speed on the specific capacitance of electrodes covered with a deposit of nano-microparticles 1 of different compositions.
- Curve (f) corresponds to a deposition of nano-microparticles 1 obtained according to a process of the invention using oxidized graphene nanoparticles / microparticles and oxidized SWCNTs, in a mass proportion of 25% / 75% respectively and pulverized. on 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 method of the invention using oxidized nano- / microparticles of graphene
- curve (h) corresponds to a deposition of nano- / microparticles 1 obtained by spraying oxidized SWCNT
- curve (i) corresponds to a deposit of nano- / microparticles 1 based on "bucky paper” with SWCNT
- the curve (j) corresponds to a deposit of nano- / microparticles 1 made from activated carbon paste (as in conventional supercapacitors)
- the curve (k) corresponds to a deposit of nano- / microparticles based on "bucky paper” with a mixture of oxidized nano- / microparticles of graphene and oxidized SWCNTs.
- FIG. 8 illustrates that among the nanoparticle deposits 1 produced by sputtering, the specific capacitances of the electrodes obtained according to a method of the invention are higher than those of the electrode manufactured with deposits 1 of SWCNT. oxidized (alone).
- curve (f) 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.
- curve (f) illustrates that the interaction between oxidized graphene nano- / microparticles and oxidized SWCNT 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 according to a method of FIG. 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%.
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Nanotechnology (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Composite Materials (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR1500231A FR3032362B1 (fr) | 2015-02-06 | 2015-02-06 | Procede de depot de nanoparticules et de microparticules carbonees oxydees |
PCT/EP2016/052541 WO2016124756A1 (fr) | 2015-02-06 | 2016-02-05 | Procede de depot de nanoparticules et de microparticules carbonees oxydees |
Publications (1)
Publication Number | Publication Date |
---|---|
EP3254292A1 true EP3254292A1 (fr) | 2017-12-13 |
Family
ID=53673980
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP16706982.2A Withdrawn EP3254292A1 (fr) | 2015-02-06 | 2016-02-05 | Procede de depot de nanoparticules et de microparticules carbonees oxydees |
Country Status (8)
Country | Link |
---|---|
US (1) | US20180025853A1 (fr) |
EP (1) | EP3254292A1 (fr) |
JP (1) | JP2018508992A (fr) |
KR (1) | KR20170116066A (fr) |
CN (1) | CN107408462B (fr) |
AU (1) | AU2016214292A1 (fr) |
FR (1) | FR3032362B1 (fr) |
WO (1) | WO2016124756A1 (fr) |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
RU2644579C1 (ru) * | 2016-12-13 | 2018-02-13 | Сергей Иванович Жебелев | Способ сборки наноматериалов из графена |
GB201707428D0 (en) * | 2017-05-09 | 2017-06-21 | Applied Graphene Mat Plc ] | Composite moulding materials |
KR102655394B1 (ko) * | 2019-04-02 | 2024-04-09 | 삼성디스플레이 주식회사 | 표시 장치의 제조 장치 및 표시 장치의 제조 방법 |
CN110090605B (zh) * | 2019-05-14 | 2024-05-10 | 黄琛 | 一种功能性纳米微球的制备设备 |
CN113244931B (zh) * | 2020-02-11 | 2022-05-03 | 中国石油化工股份有限公司 | 催化剂以及含不饱和烃气体的催化氧化脱氧方法 |
FR3110281B1 (fr) | 2020-05-14 | 2022-08-19 | Thales Sa | Electrode nanostructurée pour supercondensateur |
CN113649252B (zh) * | 2021-08-18 | 2022-12-27 | 中国科学院重庆绿色智能技术研究院 | 喷涂制备微纳多级自补偿结构及其柔性压力传感器 |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR100895521B1 (ko) * | 2007-10-12 | 2009-04-30 | (주)탑나노시스 | 스프레이 코팅을 이용한 탄소나노튜브 투명도전막 및 그제조방법 |
JP6034621B2 (ja) * | 2011-09-02 | 2016-11-30 | 株式会社半導体エネルギー研究所 | 蓄電装置の電極および蓄電装置 |
KR101388695B1 (ko) * | 2011-10-24 | 2014-04-28 | 삼성전기주식회사 | 그래핀 투명전극 및 이의 제조방법 |
WO2013100382A1 (fr) * | 2011-12-31 | 2013-07-04 | 제일모직주식회사 | Procédé de préparation d'un composite graphène-nanotubes de carbone à l'aide de pyrolyse par pulvérisation et composite graphène-nanotubes de carbone préparé par ce procédé |
US9530531B2 (en) * | 2013-02-21 | 2016-12-27 | Nanotek Instruments, Inc. | Process for producing highly conducting and transparent films from graphene oxide-metal nanowire hybrid materials |
US9017777B2 (en) * | 2013-02-26 | 2015-04-28 | Quantumscape Corporation | Inorganic films using a cascaded source for battery devices |
US20140272199A1 (en) * | 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 (en) * | 2013-03-14 | 2014-10-28 | Nanotek Instruments, Inc. | Method for producing conducting and transparent films from combined graphene and conductive nano filaments |
TW201504363A (zh) * | 2013-07-16 | 2015-02-01 | Enerage Inc | 石墨烯油墨及石墨烯線路的製作方法 |
CN103400632B (zh) * | 2013-07-17 | 2016-05-11 | 常州二维碳素科技股份有限公司 | 一种石墨烯掺杂材料及其应用 |
CN103396573B (zh) * | 2013-08-22 | 2015-07-22 | 电子科技大学 | 一种复合纳米薄膜的制备方法 |
-
2015
- 2015-02-06 FR FR1500231A patent/FR3032362B1/fr active Active
-
2016
- 2016-02-05 US US15/548,710 patent/US20180025853A1/en not_active Abandoned
- 2016-02-05 WO PCT/EP2016/052541 patent/WO2016124756A1/fr active Application Filing
- 2016-02-05 KR KR1020177024642A patent/KR20170116066A/ko not_active Application Discontinuation
- 2016-02-05 JP JP2017541337A patent/JP2018508992A/ja active Pending
- 2016-02-05 AU AU2016214292A patent/AU2016214292A1/en not_active Abandoned
- 2016-02-05 CN CN201680013301.5A patent/CN107408462B/zh active Active
- 2016-02-05 EP EP16706982.2A patent/EP3254292A1/fr not_active Withdrawn
Also Published As
Publication number | Publication date |
---|---|
AU2016214292A1 (en) | 2017-08-31 |
KR20170116066A (ko) | 2017-10-18 |
CN107408462A (zh) | 2017-11-28 |
FR3032362B1 (fr) | 2020-05-29 |
JP2018508992A (ja) | 2018-03-29 |
CN107408462B (zh) | 2021-03-23 |
US20180025853A1 (en) | 2018-01-25 |
FR3032362A1 (fr) | 2016-08-12 |
WO2016124756A1 (fr) | 2016-08-11 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP3254292A1 (fr) | Procede de depot de nanoparticules et de microparticules carbonees oxydees | |
Korenblit et al. | In situ studies of ion transport in microporous supercapacitor electrodes at ultralow temperatures | |
Lee et al. | High performance flexible supercapacitor electrodes composed of ultralarge graphene sheets and vanadium dioxide | |
Fan et al. | High electroactivity of polyaniline in supercapacitors by using a hierarchically porous carbon monolith as a support | |
Lee et al. | Outstanding low‐temperature performance of structure‐controlled graphene anode based on surface‐controlled charge storage mechanism | |
US20140120453A1 (en) | Patterned graphite oxide films and methods to make and use same | |
US8699207B2 (en) | Electrodes synthesized from carbon nanostructures coated with a smooth and conformal metal adlayer | |
KR101995465B1 (ko) | 롤 형태를 갖는 전극 구조체, 이를 채용한 전극 및 전기소자, 및 상기 전극 구조체의 제조방법 | |
Guerra et al. | ZnO/Carbon nanowalls shell/core nanostructures as electrodes for supercapacitors | |
Shulga et al. | Preparation of graphene oxide-humic acid composite-based ink for printing thin film electrodes for micro-supercapacitors | |
Jang et al. | Activated carbon nanocomposite electrodes for high performance supercapacitors | |
KR20100095628A (ko) | 금속 내포 수상 탄소 나노 구조물, 탄소 나노 구조체, 금속 내포 수상 탄소 나노 구조물의 제작방법, 탄소 나노 구조체의 제작방법, 및 캐패시터 | |
EP3649663B1 (fr) | Procédé de préparation d'une électrode comprenant un support, des nanotubes de carbone alignés et un oxyde métallique déposé par voie oxydante, ladite électrode et ses utilisations. | |
Du et al. | A Three‐Layer All‐In‐One Flexible Graphene Film Used as an Integrated Supercapacitor | |
US10804043B2 (en) | Method of preparing core-shell structure nanoparticle using structure-guided combustion waves | |
Kim et al. | Maximizing volumetric energy density of all-graphene-oxide-supercapacitors and their potential applications for energy harvest | |
Soam et al. | Controlling the shell microstructure in a low-temperature-grown SiNWs and correlating it to the performance of the SiNWs-based micro-supercapacitor | |
JP2023508762A (ja) | 高純度のバインダーフリー炭素質電極を有するスーパーキャパシタセル | |
WO2007132077A1 (fr) | Composition catalytioue a base de charbon actif catalytioue et nanotubes de carbone, procede de fabrication, electrode et supercondensateur comprenant le composite catalytioue | |
Boulanger et al. | Spray deposition of supercapacitor electrodes using environmentally friendly aqueous activated graphene and activated carbon dispersions for industrial implementation | |
EP3459095B1 (fr) | Procede de fabrication de supercondensateur | |
US9472354B2 (en) | Electrodes for capacitors from mixed carbon compositions | |
EP2769395B1 (fr) | Assemblage collecteur-électrode apte à être intégré dans un dispositif de stockage d'énergie électrique | |
KR20170016908A (ko) | 롤 형태를 갖는 전극 구조체, 이를 채용한 전극 및 전기소자, 및 상기 전극 구조체의 제조방법 | |
KR20170004075A (ko) | 그래핀-금속을 포함하는 3 차원 전극 구조체, 이의 제조 방법, 및 이를 포함하는 3 차원 캐패시터용 전극 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE |
|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE |
|
17P | Request for examination filed |
Effective date: 20170728 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
AX | Request for extension of the european patent |
Extension state: BA ME |
|
DAV | Request for validation of the european patent (deleted) | ||
DAX | Request for extension of the european patent (deleted) | ||
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: EXAMINATION IS IN PROGRESS |
|
17Q | First examination report despatched |
Effective date: 20210331 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN |
|
18D | Application deemed to be withdrawn |
Effective date: 20210811 |