WO2013160816A1 - Électrode, dispositif la comprenant et son procédé de fabrication - Google Patents
Électrode, dispositif la comprenant et son procédé de fabrication Download PDFInfo
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- WO2013160816A1 WO2013160816A1 PCT/IB2013/053164 IB2013053164W WO2013160816A1 WO 2013160816 A1 WO2013160816 A1 WO 2013160816A1 IB 2013053164 W IB2013053164 W IB 2013053164W WO 2013160816 A1 WO2013160816 A1 WO 2013160816A1
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- WIPO (PCT)
- Prior art keywords
- nanostructure
- layer
- silicon
- protective layer
- electrode
- Prior art date
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 8
- 239000002086 nanomaterial Substances 0.000 claims abstract description 93
- 239000010410 layer Substances 0.000 claims abstract description 61
- 239000011241 protective layer Substances 0.000 claims abstract description 60
- 239000000463 material Substances 0.000 claims abstract description 48
- 239000003989 dielectric material Substances 0.000 claims abstract description 28
- 229910052751 metal Inorganic materials 0.000 claims abstract description 28
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- 239000004065 semiconductor Substances 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000010703 silicon Substances 0.000 claims description 64
- 229910052710 silicon Inorganic materials 0.000 claims description 63
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 61
- 229920001940 conductive polymer Polymers 0.000 claims description 25
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 15
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 15
- 239000002861 polymer material Substances 0.000 claims description 14
- 238000005229 chemical vapour deposition Methods 0.000 claims description 12
- 229910052732 germanium Inorganic materials 0.000 claims description 12
- 239000010931 gold Substances 0.000 claims description 12
- 238000007254 oxidation reaction Methods 0.000 claims description 11
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(iv) oxide Chemical compound O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 claims description 10
- 230000003647 oxidation Effects 0.000 claims description 10
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 9
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 9
- 229910052737 gold Inorganic materials 0.000 claims description 9
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 8
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- 239000010936 titanium Substances 0.000 claims description 6
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- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 229920001062 poly(2,7-carbazoles) Polymers 0.000 claims description 5
- 229920001065 poly(3,6-carbazoles) Polymers 0.000 claims description 5
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 claims description 5
- 229910045601 alloy Inorganic materials 0.000 claims description 4
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- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 4
- 229910052735 hafnium Inorganic materials 0.000 claims description 4
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 150000003233 pyrroles Chemical class 0.000 claims description 4
- 229910001220 stainless steel Inorganic materials 0.000 claims description 4
- 239000010935 stainless steel Substances 0.000 claims description 4
- 239000005977 Ethylene Substances 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
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- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims 1
- 229910052733 gallium Inorganic materials 0.000 claims 1
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- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims 1
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- 239000004020 conductor Substances 0.000 abstract description 6
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- 239000003054 catalyst Substances 0.000 description 9
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- 230000015572 biosynthetic process Effects 0.000 description 8
- LRESCJAINPKJTO-UHFFFAOYSA-N bis(trifluoromethylsulfonyl)azanide;1-ethyl-3-methylimidazol-3-ium Chemical compound CCN1C=C[N+](C)=C1.FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F LRESCJAINPKJTO-UHFFFAOYSA-N 0.000 description 6
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- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 5
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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
- H01G11/22—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
- H01G11/04—Hybrid capacitors
-
- 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
-
- 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
- H01G11/48—Conductive polymers
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L28/00—Passive two-terminal components without a potential-jump or surface barrier for integrated circuits; Details thereof; Multistep manufacturing processes therefor
- H01L28/40—Capacitors
- H01L28/60—Electrodes
-
- 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 an electrode, to a device for storing and restoring electrical energy comprising it, and to a method for manufacturing this electrode.
- the electrodes are very widely used in many fields, and in particular, in the storage and restitution of electrical energy devices.
- the key point is the developed surface of the electrodes.
- the first type is electrochemical double layer capacitor (EDLC) supercapacitors, which are electrical energy storage devices that store and release energy through the separation of ionic charges at the interface between a electrode and an electrolyte.
- EDLC electrochemical double layer capacitor
- these supercapacitors As the stored energy is inversely proportional to the thickness of the double layer, these supercapacitors have a very high energy density compared to conventional dielectric capacitors.
- a second type of supercapacitor is represented by pseudo-capacitive supercapacitors.
- pseudocapacitive supercapacitors There are two main categories of pseudocapacitive supercapacitors: supercapacitors based on metal oxides and those based on intrinsically conductive polymers.
- the electrochemical capacity is due to reversible oxidation-reduction reactions occurring on the surface of the electrode material in the presence of electrolyte when a voltage is applied. These materials must therefore be able to undergo rapid oxidation-reduction reactions involving a maximum number of oxidation levels in a potentials window compatible with the electrochemical stability of the electrolyte used.
- a third type of supercapacitor is represented by supercapacitors based on metal oxides.
- the electrochemical capacity is due to oxidation-reduction reactions at the surface and in the volume of the material of the electrode.
- This quantity depends on the quantity of charges transferred, which itself depends on the applied voltage.
- the oxides of the transition metals have a high number of oxidation states.
- They can be prepared with a large surface area and some oxides are electronically conductive.
- the fourth type of supercapacitor is represented by supercapacitors based on electronically conductive polymers.
- Intrinsic electronic conductive polymers can receive electrons by electrochemical reduction (negative doping, n-doping) or electrons by oxidation (positive doping, p-doping).
- the doping / dedoping phenomenon is electrochemically reversible, the intrinsic electronic conductive polymers can store charges and restore them in supercapacitor and battery applications.
- the electronically conductive polymers have high electrochemical capacities because the doping / dedoping process involves all the mass and the volume of the polymer.
- silicon nanowires have been studied for use in supercapacitors. Silicon nanowires were first observed in 1964.
- VLS vapor-liquid-solid
- nanowires was then used to describe this new type of nanostructures.
- VLS nanowires The growth of VLS nanowires has received strong interest in the potential of this new type of material in nanoelectronics, NEMS, sensors, photovoltaic energy, biosensor.
- branched nanostructures consist of a trunk of silicon material (the nanowire itself) from which the substructures are elaborated (the branches).
- silicon nano-trees represent a unique opportunity to radically improve the performance of micro-super-capacitors thanks to their specific architectures and their extremely large surface area.
- silicon nanowires to increase the effective surfaces of the electrodes of supercapacitors, but also of all the electrochemical devices, and in particular of storage and restitution of electrical energy.
- the object of the invention is to obtain electrodes with a very large active surface whose supercapacity is stable over time.
- the invention proposes to create a controlled interface between the silicon or any other conductive or semiconductor material constituting the electrode, and the electrolyte.
- the invention proposes an electrode comprising a support, made of a conductive or semi-conductive material, this support comprising, on at least one of its surfaces, at least one nanostructure made of a semiconductor material, characterized in that it further comprises a protective layer of a material selected from a dielectric material having an intrinsic capacitance of between 1.5 10 -6 and 10 10 -6 F / cm 2 and a metal, said layer having a thickness less than the height of said nanostructure, and covering the at least one nanostructure.
- the intrinsic capacity of a material is understood to mean the capacity of this material alone (for example in the absence of an electrolyte for an electrode).
- the support is made of a conductive or semiconductive material selected from stainless steel, carbon, silicon, germanium, gallium arsenide (GaAs), alloys in all proportions of silicon and germanium (SiGe) , and indium phosphide (InP).
- a conductive or semiconductive material selected from stainless steel, carbon, silicon, germanium, gallium arsenide (GaAs), alloys in all proportions of silicon and germanium (SiGe) , and indium phosphide (InP).
- the support is silicon.
- the nanostructure is a semiconductor material selected from silicon, germanium, gallium arsenide, alloys in all proportions of silicon and germanium and indium phosphide.
- the nanostructure is silicon.
- this material is preferably chosen from SiO 2 , a hafhiurn silicate, a zirconium silicate, hafnium dioxide, zirconium dioxide, silicon nitride, ruthenium (RuO 2 ), manganese dioxide (MnO 2 ), vanadium oxide (V 2 O 5 ), iron oxide (Fe 3 O 4 ).
- the dielectric material is Si0 2 .
- this metal is preferably selected from gold (Au), platinum (Pt), silver (Ag), nickel (Ni), and titanium (Ti) and thickness of this layer is between 2 and 20 nm inclusive, preferably between 3 and 20 nm inclusive, more preferably between 3 and 8 nm
- the electrode according to the invention further comprises a layer of an intrinsically conductive polymer material, on the protective layer of a dielectric material or metal, this layer of an intrinsically conductive polymer material and the protective layer.
- a dielectric material or metal having a total thickness less than the height of the nanostructure, preferably between 2 and 20 nm, more preferably between, even more preferably between 3 and 8 nm.
- the intrinsically conductive polymer material is chosen from poly (3,4-diethylenedioxythiophenes), poly (2,7 carbazoles), poly (3,6 carbazoles), poly (anilines) and poly (pyrroles). .
- the intrinsically conductive polymer material is poly (3,4-ethylene dioxythiophene).
- the invention also proposes a device for storing and restoring electrical energy, characterized in that it comprises at least one electrode according to the invention.
- the device according to the invention comprises at least two identical electrodes according to the invention.
- the device according to the invention comprises at least two electrodes, one of which is an electrode according to the invention and the other is made of carbon, preferably with a large specific surface area (> 1500 m 2 / boy Wut).
- the invention also proposes a method for manufacturing an electrode comprising a support made of a conductive or semiconductor material, this support comprising, on at least one of its surfaces, at least one nanostructure made of a semiconductor material, characterized in it comprises a step of forming a protective layer of a material selected from a dielectric material having an intrinsic capacitance of between 1.5 10- and 10 10 -F / cm and a metal, on said nanostracture, this layer having a thickness less than the height of said nanostructure.
- the nanostructure is obtained by chemical vapor deposition (CVD) of the semiconductor material, on said surface of the support.
- CVD chemical vapor deposition
- the protective layer is deposited by chemical or thermal oxidation of the material constituting the nanostructure.
- This protective layer can also be obtained by nitriding the material constituting said nanostructure.
- the method of the invention further comprises a step of depositing a layer of a conductive polymer on the protective layer of a dielectric material or metal, this layer made of a polymer material intrinsic conductor and the layer of a dielectric material or metal having a total thickness less than the height of the nanostructure.
- the intrinsically conductive polymer material is poly (3,4-ethylene dioxythiophene).
- FIG. 1 shows the evolution of the voltage as a function of time in gai vano static charge / discharge cycles of a device composed of two electrodes according to the invention comprising nanostructures made of oxidized silicon.
- the working electrode is in oxidized N + silicon and the counter-electrode in oxidized P + + silicon, and the electrolyte is NEt 4 BF 4 , PC, 1M.
- FIG. 2 shows the evolution of the surface capacitance of a device with two oxidized silicon nanostructure electrodes (curve denoted Np-100) and the electrolyte is of NEt 4 BF 4 , PC, 1M, as a function of the number of cycles. galvanostatic charge / discharge, the cycling being performed at plus or minus 5 ⁇ . ⁇ 2 between 0.01V and IV,
- FIG. 3 shows, on the one hand, the cyclic voltammetric curve at 2 mV.s -1 of a nanostructured P ++ doped silicon sample (curve noted prior art) and, on the other hand, that of a sample. of oxidized nanostructured P ++ doped silicon (curve noted invention) obtained in a free bath using an electrolyte which is 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide (EMI-TFSI) (ionic liquid),
- EMI-TFSI 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide
- FIG. 4 represents the evolution over time of cyclic voltammetry curves at 20 mV.s.sup.- 1 of an electrode according to the invention comprising nanostructures made of oxidized N + + silicon, and the electrolyte is 1-ethyl-3- methylimidazolium bis (trifluoromethylsulfonyl) imide (EMI-TFSI) (ionic liquid),
- EMI-TFSI 1-ethyl-3- methylimidazolium bis (trifluoromethylsulfonyl) imide
- FIG. 5 shows the cyclic voltammetric curve between -1 V and -0.3 V vs Ag / Ag + at 20 mV.s -1 obtained with a device comprising a nano-structured P ++ doped silicon-coated working electrode covered with a protective layer of gold, in a free bath, using, as the electrolyte, NE4BF4, PC, 1M, as reference electrode an Ag + / Ag electrode and a counter-electrode in Pt, and
- FIG. 6 shows the static galvano charge / discharge curve obtained with the same device as in FIG. 5.
- the aim of the invention is to provide electrodes, in particular for energy storage and retrieval devices, and more particularly for supercapacitive supercapacitors and / or supercapacitors, whose electrodes comprise a three-dimensional silicon structure, the nanostructures having a high surface density.
- the invention therefore proposes to use nanostructures, for example made of silicon, whose morphology and nano structuring makes it possible to increase the exchange surface at the electrode / electrolyte interface very strongly.
- the invention proposes to deposit, on the nanostructures, a layer of a dielectric material and / or electroactive that will have a function of protecting the nano structure.
- Such a nanostructured electrode when it is silicon, can be directly integrated into a microelectronic circuit.
- the invention proposes an electrode comprising a support made of a conductive or semi-conducting material comprising on at least one of its surfaces at least one nanostructure made of a semiconductor material.
- the conducting or semiconductor material whose support is constituted is preferably chosen from stainless steel, carbon, silicon, germanium, gallium arsenide (AsGa), silicon and germanium alloys (SiGe ), and indium phosphide (InP).
- the support is made of silicon.
- the nanostructures made of a semiconductor material will preferably be made of a semiconductor material chosen from silicon, germanium, gallium arsenide, an alloy of silicon and germanium and indium phosphide.
- the nanostructures are made of silicon.
- nanostructures can be obtained by catalyzed growth in chemical vapor deposition.
- the nanostructures When the support of the electrodes is in silicon, the nanostructures will be obtained as well by epitaxial growth or vapor deposition (CVD) as by etching the structures directly in the silicon.
- CVD vapor deposition
- the growth will be only by crystal growth or CVD.
- the invention is based on the surprising discovery that when a protective layer of a material is dielectric having an intrinsic capacitance of between 1.5 10 -6 and 10 10 -6 F / cm 2 is a metal and a thickness of some nanometers, is formed on the nanostructures, the electrode thus obtained has, in the presence of an electrolyte, surprising capacitive responses for applications, in particular supercapacitors, in the presence of organic electrolytes, ionic liquids or ionogels.
- This protective layer should not have a thickness greater than the height of the nanostructures: it must not completely fill the interstructure space. In other words, it should not make the surface of the electrode flat because otherwise the interest of structuring is lost.
- the layer is conformal, that is to say that it will follow the shapes of the nanostructure.
- This layer is also uniform over the entire surface of the nanostructures. In other words, it will have to completely cover the nanostructures, and have in all points of these nanostructures a sufficient thickness to protect them effectively.
- This thickness depends on the density of the nanostructures.
- the thickness of the protective layer coating the nanostructures should not exceed 20 nm and should not be less than 2 nm.
- the thickness of the protective layer will be greater than or equal to 3 nm.
- This protective layer must also be sufficiently covering to protect the surface of the nanostructures, and in the case of a layer of a dielectric material, to maintain a high capacity of the electrode in the presence of an electrolyte.
- Preferred dielectric materials for forming this protective layer are the oxides and nitrides of transition elements such as SiO 2 , silicon nitride, high-k materials such as hafnium silicate, zirconium silicate, hafnium dioxide and zirconium dioxide.
- the protective layer gives the nanostructure a passive protection.
- the dielectric material may also be a ruthenium oxide (RuO 2 ), a manganese dioxide (MnO 2 ), a vanadium oxide (V 2 O 5), an iron oxide (Fe 3 O 4 ).
- RuO 2 ruthenium oxide
- MnO 2 manganese dioxide
- V 2 O 5 vanadium oxide
- Fe 3 O 4 iron oxide
- the protective layer actively protects the nanostructures: in addition to its role of protecting the nanostructures, the layer has a charge accumulation action that is added to the electrolyte charges.
- the dielectric material is SiO 2 or silicon nitride or a high-k material
- the desired m 2 capacity of the electrode is as high as possible with a continuous protective layer.
- the intrinsic capacity of the material taken alone.
- a protective layer with a thickness of less than 2 nm is not sufficiently protective and the capacity per m 2 of the layer formed is only 1.73 x 10 -6 F / cm. 2 .
- the protective layer in the case of Si0 2 , should preferably have a thickness greater than or equal to 3 nm.
- the protective layer should have a thickness greater than 2 nm and less than 8 nm, more preferably between 3 and 8 nm.
- a layer with a thickness greater than or equal to 8 nm is too large with a capacity per cm 2 - 9.6 x 10 -6 F / cm 2 .
- the capacity must be between 1.73 x 10 -6 and 9.6 x 10 -6 F / cm 2 or more generally 1, 5 10 '6-10 10 -6 F / cm 2 .
- the protective layer should have, with these materials, a thickness between 2 and 20 nm, preferably between 5 and 20 nm.
- This protective layer may be formed by chemical or thermal oxidation.
- the chemical route consists in quenching the support-nanostructure assembly in an oxidizing acid solution such as sulfuric acid or nitric acid.
- the oxidation reaction will be self-limited by the formation of the SiO 2 layer of nanometric thickness.
- the thermal pathway consists in carrying out thermal annealing in an oxidizing atmosphere.
- This technique is totally mastered in the microelectronics industry. It makes it possible to obtain SiO 2 layers with a thickness of the order of one nanometer.
- the formed layer conforms to the shape of the nanostructures (it conforms) and completely covers the surface of the nanostructures with a sufficient thickness.
- a layer of SiO 2 having these properties it must be formed by one of the means described above. Indeed, a simple oxidation by exposure to oxygen in the air, as in the case of the formation of native silicon oxide on silicon nanostructures, does not make it possible to obtain a continuous protective layer and a thickness in all points sufficient to play the role of protection of the protective layer according to the invention.
- the formation of the protective layer can be carried out by chemical vapor deposition (CVD) of a dielectric material different from SiO 2 , for example RuO 2 or MnO 2 .
- CVD chemical vapor deposition
- the deposit must be a conformal deposit, that is to say that the thickness of the layer formed must follow very precisely the contours of the nanostructures, to maintain the interest of the nano structuration.
- this protective layer can be further improved by covering this protective layer by means of an electroactive layer made of an intrinsically conductive polymer material.
- conductive polymers are conductive materials that improve the current densities and therefore the power and energy of the capacitors and add to the protective layer volume type capacity.
- Suitable conductive polymers will be apparent to those skilled in the art but they are preferably selected from poly (3,4-ethylene dioxythiophenes), poly (2,7 carbazoles), poly (3,6 carbazoles), poly (anilines) and poly (pyrroles).
- this layer of intrinsic conductive polymers on the protective layer formed can be carried out electrochemically (for example by electropolymerization) or by sublimation or by evaporation or by conventional deposition (spin coating, resin deposit ).
- the thickness of this protective layer can be controlled by measuring the synthesis charge, for example by coulometry.
- This thickness will be adjusted to preserve the nanostructuration of the son constituting the nanostructures.
- the total thickness of the protective layer and the conductive polymer layer must not make nanostructure disappear due to the nanostructures, and the total thickness of these two layers must not be equal to or exceed the height of the nanostructures.
- the electrode of the invention can be used in a device for storing and restoring electrical energy.
- Such a storage device generally comprises at least two electrodes.
- At least two of these electrodes may both be electrodes according to the invention, advantageously identical.
- the other carbon electrode of large specific surface area.
- the electrode when it is an electrode according to the invention, it is an electrode whose support is silicon, the nanostructure then being grown on this support and being itself in silicon.
- the protective layer covering the nanostructure is then preferably a silica layer (Si0 2 ) obtained by oxidation of the silicon surface.
- this electrode whose support and nanostructures are made of silicon and are coated with a layer of silicon oxide, also comprises a layer of conductive polymer, which is poly (3,4 ethylene dioxythiophene).
- the electrodes according to the invention are manufactured by a process which is also an object of the invention.
- This method comprises a step of forming, on at least one nanostructure, a semiconductor material formed on a support made of a material semiconductor or conductor, a protective layer of a material selected from a dielectric material having an intrinsic capacitance of between 1.5 10 -6 and 10 10 -F / cm and a metal, which layer has a thickness less than height of the nanostructure.
- the height of the nanostructure corresponds to the distance between the surface of the support and the surface of the nanostructure, when taken in the same plane.
- the support of the electrodes is preferably made of a conductive or semiconductor material selected from stainless steel, carbon, silicon, germanium, gallium arsenide, alloys of silicon and germanium and indium phosphide .
- the support is silicon.
- the nanostructure it is preferably a semiconductor material selected from silicon, germanium, gallium arsenide, alloys of silicon and germanium, and indium phosphide.
- it is silicon.
- nanostructure we mean both a wire, a nanowire, a nano-tree, etc.
- Such a nanostructure must have a form factor greater than 5, advantageously greater than 20, and more preferably greater than 100. This form factor applies to wires, branches and tree trunks.
- this dielectric material is preferably chosen from silica, hafnium silicate, zirconium silicate, hafnium dioxide, zirconium dioxide and silicon nitride. , ruthenium dioxide (RuO 2 ), manganese dioxide (MnO 2 ), vanadium oxide (V 2 O 5), iron oxide (Fe 3 O 4 ).
- Hafnium silicate, zirconium silicate, hafnium dioxide and zirconium dioxide are so-called "high-k" materials.
- this layer is a silica layer, in particular when the nanostructure and / or the support are made of silicon.
- the layer of dielectric material can be formed by simple oxidation of the surface of the nanostructure and / or the support.
- the so-called protective layer and nanostructuration of the nanostructure may also be metal.
- the metal is selected from gold (Au), platinum (Pt), silver (Ag), nickel (Ni) and titanium (Ti) and the thickness of this layer must be between 2 and 20 nm inclusive, preferably between 3 and 20 nm, more preferably between 3 and 8 nm inclusive, to form a sufficiently protective layer while maintaining a good capacity.
- the electrode manufacturing method of the invention further comprises a step of depositing a layer of an intrinsically conductive polymer material on the protective layer of a dielectric material or metal.
- this layer of an intrinsically conductive polymer material is a layer of a material chosen from poly (3,4-ethylene dioxythiophenes), poly (2,7 carbazoles), poly (3,6 carbazoles), poly ( anilines) and poly (pyrroles).
- this layer is poly (3,4-ethylene dioxythiophene).
- the thickness of these two layers must be less than the height of the nanostructure. It must also be, regardless of the fact that only one or two layers are deposited on the nanostructures, layer (s) deposited (s) conformably on the nanostructure, that is to say, marrying the forms of nanostructure.
- a catalyst metal here gold, is deposited on a silicon support. This metal is the seat of the growth of 3D silicon nanostructures.
- the shaping of the catalyst is obtained by dewetting a thin film of the metal by heating, which leads to the formation of nanodroplets.
- the shaping of the catalyst can also be carried out by depositing colloidal metal catalyst.
- the second step is then the formation of the nanostructures from the deposited metal.
- the nanostructures are made of silicon and are obtained by chemical vapor deposition using silane.
- Branched structures are obtained using the catalysts on the main trunk.
- These catalysts can come from:
- a new catalyst deposit after trunk growth ii) a new catalyst deposit after trunk growth.
- the silicon nanostructures will form one or two electrodes depending on the final component. Thus, if the final component must have a low price, only one electrode will be formed, but to have high performance two electrodes according to the invention will be used.
- the third step is the step of creating the protective layer of the nanostructures.
- the nanostructures being silicon
- chemical oxidation is the simplest solution to implement to obtain a silica layer on the nanostructures.
- this protective layer by sublimation or evaporation.
- the height of the nanostructures is 10 ⁇ , which corresponds to their length, and the protective layer has a thickness of 3 nm.
- the nanowires have a diameter of 100 nm and are coated with a protective layer of Si0 2 with a thickness of 3 nm.
- the device further comprises:
- organic electrolyte which is a solution of tetraethylammonium tetrafluoroborate, in propylene carbonate at a concentration of 1 mol.L -1 (NEt 4 BF 4 , PC, 1M),
- This device has been tested in galvanostatic charge / discharge cycle.
- the cycling is carried out at plus or minus 5 ⁇ A / cm between 0.01V and IV.
- FIG. 1 represents the variation of the potential in volts as a function of the cycling time of the device of example 1. As can be seen in FIG. 1, the shape of the cycle is almost ideal and characteristic of that of a supercapacitor.
- the electrode of Example 1 was coated in addition to a layer of an intrinsically conductive polymer material which is here poly (3,4-ethylene dioxythiophene).
- This layer is deposited in this example by voltammetry.
- Example 2 With the same electrode of Example 1, a so-called free-bath device (that is to say without separator and in a large volume of electrolyte, here of the order of 5 ml) with an electrolyte was manufactured. which was 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide (EMI-TFSI) which is an ionic liquid.
- EMI-TFSI 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide
- the electrode according to the invention has a surface of 0.2 cm 2 , the counter electrode was platinum and the reference electrode Ag / Ag + .
- Example 3 The same device as in Example 3 was manufactured, but the silicon nanowire array was not oxidized, as in the prior art.
- Example 3 The devices of Example 3 and Comparative Example were tested in cyclic voltammetry at 2mV.s- 1 using an Ag + / Ag reference electrode.
- the curve denoted "invention” is the curve obtained with the device of example 3 and the curve denoted “prior art” is the cyclic voltametry curve obtained with the device of the comparative example.
- the cyclic voltammetric curve of the device of example 3 is similar to that of a supercapacitor (horizontal curve) while the cyclic voltammetric curve of the device of the comparative example is not. not.
- curves obtained are shown in FIG. 4 in which the curve noted (1) represents the cyclic voltametry curve at the initial moment and the curve noted (2) represents the cyclic voltametry curve obtained after 2 hours of cycling.
- An electrode according to the invention was manufactured with a protective layer of gold.
- silicon nanowires were grown on an N + doped silicon substrate by CVD (chemical vapor deposition), using silane.
- the catalyst used was gold colloids 50 nm in diameter. Silicon nanowires of about 50 nm in diameter and about 5 ⁇ in length, N + doped, were obtained at a density of about 5 ⁇ 10 8 nanowires / cm 2 .
- Silicon nanowires, forming the nanostructures, were coated with a protective layer of gold with a thickness of 8 nm, by evaporation of gold.
- the electrode obtained was used in an electrochemical test setup comprising 3 electrodes, a working electrode, which is the one obtained above, a reference electrode Ag + / Ag and a counter-electrode in platinum (Pt). .
- the electrode used was a solution of NEUBF 4 , PC, 1M, as in Example 1.
- the curve obtained is very close to that of a supercapacitor.
- This device has also been tested in charge cycles and static galvano discharge.
- this curve is close to that obtained with a supercapacitor.
- the surface capacitance of this device was calculated from these two curves: the average surface capacitance is 45 ⁇ . ⁇ , which is more important than the average surface capacitance of the same device but in which the protective layer is a layer of silicon oxide, this capacity being 26 ⁇ -2 .
- the device of this example can therefore store more energy than the device in which the protective layer is a silicon oxide layer because the energy stored by a device is proportional to its average surface capacity.
- Example 4 A device identical to that of Example 4 but having no protective layer does not have a capacitive behavior.
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Abstract
Description
Claims
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KR1020147032807A KR20150005647A (ko) | 2012-04-23 | 2013-04-22 | 전극, 이를 포함하는 장치 및 이의 제조방법 |
EP13725820.8A EP2842142A1 (fr) | 2012-04-23 | 2013-04-22 | Électrode, dispositif la comprenant et son procédé de fabrication |
US14/396,523 US20150332859A1 (en) | 2012-04-23 | 2013-04-22 | Electrode, Device Including Same And Manufacturing Method Thereof |
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EP3282461B1 (fr) | 2016-08-12 | 2020-05-06 | Commissariat à l'Energie Atomique et aux Energies Alternatives | Électrode revêtue avec un polymères rédox contenant des unités diones, leur procédé de préparation et leurs utilisations |
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US7880318B1 (en) * | 2007-04-27 | 2011-02-01 | Hewlett-Packard Development Company, L.P. | Sensing system and method of making the same |
US20110045349A1 (en) * | 2009-08-24 | 2011-02-24 | Applied Materials, Inc. | 3d approach on battery and supercapacitor fabrication by initiation chemical vapor deposition techniques |
WO2011094642A1 (fr) * | 2010-01-29 | 2011-08-04 | Illuminex Corporation | Anode nano-composite pour batteries de haute capacité et procédés de formation associés |
WO2012067943A1 (fr) * | 2010-11-15 | 2012-05-24 | Amprius, Inc. | Électrolytes destinés à des piles rechargeables |
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2012
- 2012-04-23 FR FR1253690A patent/FR2989838B1/fr not_active Expired - Fee Related
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2013
- 2013-04-22 US US14/396,523 patent/US20150332859A1/en not_active Abandoned
- 2013-04-22 EP EP13725820.8A patent/EP2842142A1/fr not_active Withdrawn
- 2013-04-22 WO PCT/IB2013/053164 patent/WO2013160816A1/fr active Application Filing
- 2013-04-22 KR KR1020147032807A patent/KR20150005647A/ko not_active Application Discontinuation
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US7880318B1 (en) * | 2007-04-27 | 2011-02-01 | Hewlett-Packard Development Company, L.P. | Sensing system and method of making the same |
US20110045349A1 (en) * | 2009-08-24 | 2011-02-24 | Applied Materials, Inc. | 3d approach on battery and supercapacitor fabrication by initiation chemical vapor deposition techniques |
WO2011094642A1 (fr) * | 2010-01-29 | 2011-08-04 | Illuminex Corporation | Anode nano-composite pour batteries de haute capacité et procédés de formation associés |
WO2012067943A1 (fr) * | 2010-11-15 | 2012-05-24 | Amprius, Inc. | Électrolytes destinés à des piles rechargeables |
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US20150332859A1 (en) | 2015-11-19 |
FR2989838B1 (fr) | 2017-01-13 |
EP2842142A1 (fr) | 2015-03-04 |
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