WO2012112818A2 - Réseaux interpénétrants de carbone cristallin et de matériaux électroactifs à l'échelle nanométrique - Google Patents

Réseaux interpénétrants de carbone cristallin et de matériaux électroactifs à l'échelle nanométrique Download PDF

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WO2012112818A2
WO2012112818A2 PCT/US2012/025523 US2012025523W WO2012112818A2 WO 2012112818 A2 WO2012112818 A2 WO 2012112818A2 US 2012025523 W US2012025523 W US 2012025523W WO 2012112818 A2 WO2012112818 A2 WO 2012112818A2
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assembly
nano
recited
graphene
flakes
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WO2012112818A3 (fr
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George Gruner
Xiangfeng Duan
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The Regents Of The University Of California
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Priority to US13/963,973 priority Critical patent/US20140042390A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
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    • B82Y10/00—Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
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    • B82—NANOTECHNOLOGY
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    • H01G11/22—Electrodes
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    • H01L29/02—Semiconductor bodies ; Multistep manufacturing processes therefor
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    • H01L29/16—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by the materials of which they are formed including, apart from doping materials or other impurities, only elements of Group IV of the Periodic System
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    • H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
    • H01L29/68—Types of semiconductor device ; Multistep manufacturing processes therefor controllable by only the electric current supplied, or only the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched
    • H01L29/76—Unipolar devices, e.g. field effect transistors
    • H01L29/772—Field effect transistors
    • H01L29/78—Field effect transistors with field effect produced by an insulated gate
    • H01L29/788—Field effect transistors with field effect produced by an insulated gate with floating gate
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    • C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
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    • C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
    • C01P2004/24—Nanoplates, i.e. plate-like particles with a thickness from 1-100 nanometer
    • H—ELECTRICITY
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    • 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
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    • H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having a potential-jump barrier or a surface barrier
    • H10K10/40—Organic transistors
    • H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
    • H10K10/462—Insulated gate field-effect transistors [IGFETs]
    • H10K10/484—Insulated gate field-effect transistors [IGFETs] characterised by the channel regions

Definitions

  • This invention pertains generally to synthesis schemes and methods for producing networks of carbon containing nanostructures and inorganic nano- scale materials, and more particularly to the synthesis and use of networks of interconnected and interpenetrating networks of crystalline carbon,
  • Electrode materials play a central role in a variety of devices, including energy storage, electronic and opto-electronic devices. Batteries and supercapacitors require electrodes with high electrochemical activity and large electrical conductivity. Opto-electronic devices require light sensitive materials in combination with electrically conductive materials. Solar cells and light emitting diodes (LEDs) also require optically transparent and highly conducting electrodes.
  • Li ion insertion is slow, limiting the power that can be delivered, and the charging time for these batteries is comparatively long.
  • Electrochemical or supercapacitors represent alternative charge
  • Double-layer capacitance normally results from the separation of charge at the interface between high surface area electrodes and liquid electrolytes.
  • the capacitance, and thus the energy storage capacity for double layer supercapacitors where the energy is stored at the interface between the electrode and the electrolyte formed by two carbonaceous electrodes, is proportional to the surface area of the electrodes.
  • Typical energy and power values for double layer supercapacitors are 5 Wh/kg and up to 10 kW/kg respectively.
  • Pseudocapacitance arises from reversible faradaic electrochemical reactions taking place at or near the surface of an electrode over a suitable range of electrical potentials. Transition metal oxides have been shown to be useful electrode materials that utilize pseudocapacitance as the charge storage mechanism. There has been a concentrated effort in recent years to increase the energy storage capacity of supercapacitors and advanced batteries by using materials which have significant electrochemical activity, characteristically due to faradaic reactions at the surface or in the bulk. [0012] In addition to the electrochemical process based charge storage that occurs in batteries and supercapacitors, there is also a need for materials that that display significant electrochemical activity and respond to an external stimulus such as light. Such activity can be used for energy generation devices such as solar cells, and devices such as light emitting diodes. In all these cases the material is in contact with a charge collector in addition to a medium, such as an electrolyte that is inductive of the electrochemical activity.
  • the present invention is directed to charge-storage materials that can be used in a variety of applications including composites, electronic devices, sensors, photodetectors, batteries, ultracapacitors, solar cells and other devices that use electrodes.
  • the invention is also directed to graphene- functionalized pyrene conjugates and graphene transistor arrays.
  • the invention provides
  • Nano-scale material is a finite sized material with at least one dimension that is less than 100 nm.
  • nano-scale materials include nanoparticles, nanowires, nanobelts, nanotubes and nanosheets.
  • the nano-scale materials can also have different functionalities. For example, some materials can have large electrochemical activity when in contact with an electrolyte. Other materials may include light sensitive materials, or oxides that are electrically conducting and optically transparent.
  • Nano-scale materials may also be conductive such as carbon nanotubes, carbon nanosheets, metal nanowires, activated carbon or carbon black nanoparticles.
  • An electrically conducting nanostructured network that provides the combined functions of a charge collector and a charge conductor in an energy storage device is used to illustrate the invention.
  • an interconnected network, or film formed from finite sized sheets, called “flakes" of charge storage and electrically conducting materials between a source and drain is described.
  • Other nanometer sized particles of conductors or metal oxides can also be used with the conductive network or with oxide network.
  • a composite electrode architecture in another embodiment, includes nano-sheets of an oxide material, such as titanium oxide, together with a nanostructured carbon such as graphene sheets or carbon nanotubes.
  • the carbon-oxide scaffold provides (1 ) high surface area, (2) high electrical conductivity, and (3) the network of the nano-sheets of the oxide material provides the high surface area for faradaic surface reactions.
  • oxide flakes are oxide materials, such as ⁇ 2 composed of single or few sheets, typically less than 10 sheets of the material, where at least one length or width dimension is less than 100 nm.
  • Graphene is defined as sheets of carbon atoms bonded together in a two-dimensional honeycomb lattice structure one atom thick that possess remarkable in-plane mechanical, thermal, optical and electronic properties.
  • Graphene is electrically and thermally conductive and has a comparatively high fracture strength, Young's modulus and functional surface area. These properties make graphene a good candidate for use in electrode applications.
  • Graphene flakes are defined as single or multiple layers of graphene sheets having either length or width less than 100 nm.
  • the graphene flakes and nano-scale materials form an interconnected network, in contrast to two films (a graphene film and a film composed of nanoparticles) on top of each other.
  • the graphene flakes act as a conducting channel of a transistor that can be formed into an array of transistors.
  • an interconnected network of carbon nanostructures such as grapheme flakes and nano-scale charge retaining materials in the form of nanoparticles, nanowires or nanosheets is provided.
  • the graphene flakes can be in direct contact with another flake or tethered by a conductive nanotubes or nanowires in one embodiment.
  • Another aspect of the invention is to provide an interconnected network of grapheme flakes and nano-scale materials that form continuous pathways between a source and a drain.
  • a further aspect of the invention is to provide an interpenetrating
  • nano-scale materials such as activated carbon, carbon nanotubes, metal nanowires and carbon black.
  • Another aspect of the invention is to provide an interpenetrating
  • the second nano-scale electroactive material can be the same material as the first in a different form or it can be a different material from the first in any form.
  • a thin film transistor with a graphene and oxide composite is provided.
  • Yet another aspect of the invention is to provide a transistor using
  • porphyrin or pyrene-tethered quantum dots that can be conjugated onto graphene transistors through ⁇ - ⁇ interaction for light-sensing devices.
  • Another aspect of the invention is to provide a graphene transistor array where each transistor element is functionalized with a different nano-scale functional material.
  • FIG. 1 is a schematic top view of a network of interconnected carbon nanostructures such as sheets of graphene bridging a source and drain.
  • FIG. 2 is a schematic top view of an interconnected network of
  • FIG. 3 is a schematic top view of interconnected networks of grapheme flakes and nano-scale materials where both networks form a continuous path between the source and drain.
  • FIG. 4 is a schematic top view of an interpenetrating network of
  • FIG. 5 is a schematic top view of an interpenetrating network of
  • FIG. 6 is a diagram depicting molecular conjugation through a ⁇ - ⁇
  • FIG. 7A depicts a porphyrin and FIG. 7B depicts pyrene-tethered
  • quantum dots that can be conjugated onto graphene transistors through ⁇ - ⁇ interactions for use in light-sensing devices.
  • FIG. 8 is a schematic diagram of a graphene transistor array where each transistor element is functionalized with different nano-scale functional material.
  • FIG. 1 through FIG. 5 for illustrative purposes several embodiments of the interpenetrating networked films of the present invention are depicted generally in FIG. 1 through FIG. 5 and the associated methods for producing the films. It will be appreciated that the methods may vary as to the specific steps and sequence and the film architecture may vary as to structural details, without departing from the basic concepts as disclosed herein. The method steps are merely exemplary of the order that these steps may occur. The steps may occur in any order that is desired, such that it still performs the goals of the claimed invention.
  • FIG. 1 an embodiment of a network 10 of conductive nanostructures is schematically shown.
  • the term “nanostructured network” or “interpenetrating network” is intended to refer to randomly and/or semirandomly ordered nanostructures that are in electrical connection with each other.
  • An “interpenetrating network” may also include two or more
  • a nanostructured network is organized from nano-scale components that can be in a variety of forms and from a variety of materials.
  • the term nano-scale component is intended to have a broad meaning to include any nanoparticle structure or form that has at least one dimension that is less than approximately 100 nm and greater than approximately 1 nm and may include nanotubes, fullerenes, nanowires, nanoribbons, nanosheets, nanoplates, and nanorods, etc.
  • the nano-scale materials may be in the form of nanowires.
  • Nanowires may include, but are not limited to, metallic nanowires (e.g., Ag, Ni, Pt, Au), semiconducting nanowires (e.g., InP, Si, GaN), oxide nanowires (e.g., NiO, S1O2, T1O2, MnO2, M0O3, V 2 O 5 , and RUO2) as well as organic nanowires and inorganic nanowires such as ZnO nanowires, ITO nanowires, polyaniline nanofibers and Si nanowires.
  • metallic nanowires e.g., Ag, Ni, Pt, Au
  • semiconducting nanowires e.g., InP, Si, GaN
  • oxide nanowires e.g., NiO, S1O2, T1O2, MnO2, M0O3, V 2 O 5 , and RUO2
  • organic nanowires and inorganic nanowires such as ZnO nanowires, ITO nanowires, polyaniline nanofibers and Si nano
  • Nanowire includes any structure that has at least one dimension between about 1 nm and 100 nm, and an aspect ratio with respect to that dimension of at least 10 (e.g., a carbon nanotube with a diameter of 10 nm and a length of 1000 nm).
  • Nanowire networks may comprise at least one interconnected network of such nanowires (e.g., wherein nanowire density of a network or of multiple networks is above a percolation threshold). Nanowire networks may also comprise multiple interpenetrating networks (e.g., first and second networks of nanowires, the elements of which are interspersed).
  • the nano-scale material is a nanosheet that is ideally a single sheet of a regular arrangement of the constituent atoms.
  • Nanosheets may also include laminations of multiple sheets of the above dimensions. Nanosheets can be made from carbon or an oxide or some other electroactive or electrochemical material.
  • the nano-scale components 12 forming a conductive nanostructure 18 of the interpenetrating network assembly 10 illustrated in FIG. 1 are preferably graphene flakes.
  • Graphene flakes are generally graphene nanosheets defined as a single sheet or layer of carbon atoms, in a hexagonal
  • nanosheet is ideally a single sheet or layer of a material in a highly regular configuration of the atoms within the sheet, multiple sheets of up to 10 sheets or layers are also considered to be suitable graphene flakes.
  • the networks described herein may also have single, double and triple nanosheets of graphene together with some fraction of multiple sheets exceeding three sheets.
  • the network assemblies 10 illustrated in FIG. 1 through FIG. 5 refer to a base nanostructure of flakes of graphene 12 that form at least one continuous pathway across the nanostructure 18 of flakes from one electrode to the other.
  • the conductive network assembly 10 may also include other conductive nanoparticles besides graphene as shown in FIG. 4 and FIG. 5.
  • graphene flakes may be connected to other graphene flakes directly and/or by conductive nanoparticles such as metallic nanowires of carbon nanotubes.
  • the interpenetrating network 10 is an assembly of at least two different types of nano-scale materials, with one of the nanostructures 18 composed of flakes 12 of a conductive crystalline carbon material such as graphene.
  • the conductive graphene nanostructure 18 forms a network of continuous pathways between the two electrodes 14, 16 and the other nano-scale materials may or may not form a continuous pathway between the two electrodes.
  • the "source” and “drain” are given a broad definition that may include any electrically conducting material such as a metal like aluminum or copper, a conducting paste or a conducting liquid such as an electrolyte.
  • the oxide nanoparticles 20 are in functional
  • oxide nanoparticles 20 are used as an illustration, it will be understood that other nanoparticles of electroactive or electrochemical materials may also be used.
  • both the conductive nanostructure 18 and a nanostructure 22 of interconnected oxide nanoparticles 20 form continuous pathways between the source 14 and the drain 16.
  • the graphene 12 components of the conductive network 18 and the oxide nanoparticle components 20 of the oxide nanostructure 22 are also in functional proximity to each other.
  • the functionality of the interconnected conductive 18 and capacitive 22 nanostructures can be accentuated with other nano-scale materials.
  • conductive nanoparticles such as metal nanowires, semiconductor nanowires or carbon nanotubes can be incorporated as part of the conductive nanostructure 18.
  • nano-scale oxide materials could also be included in the capacitive oxide nanostructure 22.
  • the capacitive oxide nanostructure 22 could be formed from nanosheets of one type of oxide and the additional nano-scale oxide material could be oxide nanowires of the same oxide or a different oxide.
  • FIG. 4 illustrates one embodiment of an interconnected network with a nanostructure of three components, namely, graphene 18 with oxide
  • nanoparticles 20 as well as conductive nanoparticles 24 that are functionally associated with the graphene network 18 and the oxide nanoparticles 20.
  • the network of graphene flakes, nano-scale materials and nano-scale conductive materials can also be configured to have two, three or four nanostructured networks forming continuous pathways between the source 14 and drain 16.
  • the carbon nano-scale conductive material is a material with at least one dimension less than 100 nm. Examples include carbon nanowires, nanobelts, nanotubes and nanosheets. Carbon nanoparticles 24 can be made of activated carbon, carbon nanotubes, and carbon black. Nanoparticles of carbon containing polymers such as polyaniline can also be used.
  • Carbon nanotubes can be made from rolled-up sheets of graphene and can also have multiple sheets of carbon atoms forming single wall, double wall and multiwalled nanotubes.
  • Graphene and carbon nanotubes differ from other nano-scale carbonaceous materials such as carbon black and activated carbon in the structure.
  • the network illustrated in FIG. 5 shows a conductive network 18 of graphene sheets 12, a capacitive network 22 of oxides 20, and a network 26 of conductive nanoparticles such as carbon nanoparticles 24.
  • interconnected network 18, 22, 26 is connected with the other networks and all bridge the source 14 and drain 16 so that all three networks form a continuous path between the source 14 and drain 16. Similar constructions can be made with all four components.
  • one preferred interpenetrating network configuration has a
  • the interpenetrating network film 10 of connected graphene flakes provides at least one electrical conduction path between the two ends of the film and is disposed on an appropriate substrate.
  • Exemplary methods of depositing the graphene film onto a substrate include, but are not limited to, vacuum filtration, spray-coating, dip-coating, drop-coating and/or casting, roll-coating, transfer-stamping, slot-die coating, curtain coating, gravure printing, flexoprinting and/or inkjet printing.
  • a filtering method can be used to remove the solvent and surfactant to form an electrode.
  • networks can also be adapted to other devices besides charge storage devices.
  • the well defined carbon chemistry readily allows hetero- integration of graphene with many different molecular systems resulting in devices that can respond to specific physical, chemical or biological stimulation.
  • the edges of graphene or graphene nanostructures are usually terminated with a large number of carboxylic groups. These groups can be activated using reagents such as 1 - ethyl-3-(3-dimethylaminopropyl) carbodiimide (EDC) to react with amine residues on biomolecules such as proteins or other biologically active molecules.
  • EDC 1 - ethyl-3-(3-dimethylaminopropyl) carbodiimide
  • the surface of a graphene sheet can interact with pyrene (or other planar ⁇ -electron system through a ⁇ - ⁇ interaction), on which link molecules can be introduced to further link to selected receptor molecules as shown in FIG. 6.
  • link molecules can be introduced to further link to selected receptor molecules as shown in FIG. 6.
  • Transistors with a single sheet of graphene as the conducting channel can also be used as a platform.
  • the transistor configuration allows the carrier number and mobility to be separately examined - in contrast to simple resistance measurements where the two are combined into one measured parameter. This permits a detailed examination of fundamental quantities such as charge transfer at the nano-scale interface.
  • the exceptionally high mobility ( ⁇ ) of graphene transistors leads to extraordinarily high voltage (charge) sensitivity.
  • the conducting channel graphene transistors are formed by a single layer of carbon atoms (and also that of nanoribbon or nanomesh is formed by nano- scale channels of single atom thick graphene) with the largest achievable surface to bulk ratio. Thus the binding of any charged molecules can result in a large change in the overall conductance to ensure the best sensitivity possible.
  • the well-defined graphene surface with highly delocalized ⁇ electrons, and graphene edge carboxylic groups can enable facile chemical modification and immobilization of receptor molecules for the selective detection of specific analytes that bind only to the receptors.
  • graphene transistors are interfaced with light sensitive molecules and species.
  • Two species, porphyrines and quantum dots are preferably used as shown in FIG. 7A and FIG. 7B.
  • environmental stimulus (light) induced changes of the electron configurations occur and these changes translate into changes of the charge transfer between these species and graphene - leading to changes in the
  • metalloporphyrins with different spectral responses, may be used for the functionalization of graphene.
  • the use of various metals (such as Cu , Ni , Zn 2+ , Fe 3+ ) will allow the coordination of the interactions between the porphyrin derivatives and graphene within the hybrids and produce individual graphene- porphyrine assemblies with different spectral responses.
  • the preferred quantum dots that will be suitable for use are various semiconductors including CdSe, CdS, CdSe/ZnS. These are anchored by pyrene
  • these individual transistors can be arranged into highly integrated graphene-molecular device arrays.
  • the two-dimensional nature of graphene can readily allow the fabrication of large arrays of graphene transistors.
  • Selective functionalization and graphene transistors in such an array with different receptor molecules can enable a highly parallel and multiplexed detection system.
  • an independently addressable device array can be achieved through an active matrix control circuit as illustrated schematically in FIG. 8.
  • the active matrix control circuit can be fabricated using conventional silicon electronics, onto which the graphene transistors can be fabricated and integrated with each pixel.
  • the individual elements of the matrix are interfaced with light sensitive species that respond to different wavelengths. These species - porphyrines or quantum dots - with different spectral response characteristics, together with the appropriate interrogation electronics will permit a simple color sensor. Large dynamic range will be achieved by using transistors with different characteristics, and also with varying the density/number of light sensitive species that are attached. Similarly, a sensor array with different elements such as markers of certain types of cancers can also be produced.
  • the fabrication of arrays of multiplexed sensors requires selective functionalization of each graphene transistor with distinct receptors. This can be achieved with multiple techniques, including microarray molecular photolithography, dip-pen nanolithography and selective electrochemistry.
  • the first method co-deposited graphene flakes and the nano-scale material using different dispersants for the two species. Each species was dispersed in separate solvents, sonicated to achieve appropriate dispersion, and sprayed using a nozzle that deposits both materials at the same time. Changing the concentration of the materials, and changing the deposition rate will lead to a different concentration of the material species in the composite films.
  • oxide nanoparticles were mixed with carbon graphene flakes and polyvinylidene fluoride (PVDF) binder in N-methyl-2-pyrrolidone that created a slurry.
  • PVDF polyvinylidene fluoride
  • a stainless steel sheet was cut into an appropriate length and width and the slurry was painted onto the stainless steel.
  • the typical mass of active material targeted was approximately 2 - 3 mg.
  • the electrode/current collector was placed into an oven for 24 hours to evaporate the solvent and to create a robust electrode. Following this, the electrodes were placed into a vacuum desiccator for storage for at least an additional 24 hours. Finally, electrodes were prepared with various percentages of graphene.
  • the second method dispersed the two species in the same liquid with a one-step simultaneous exfoliation and deposition of graphene with metal oxides.
  • graphene was dispersed in N-methylpyrrolidone (NMP) by sonication for a period of 1 hour.
  • NMP N-methylpyrrolidone
  • V 2 O 5 powder was mixed with de-ionized water at a high concentration and sonicated until the particles disappeared and the solvent turned yellow.
  • a solvent blend with a ratio of 4:1 NMP:H 2 O was then created to form a stable dispersion containing both V 2 O 5 and graphene. This mixture was drop cast onto a metal plate and the solvents were evaporated by heating in an oven at 120°C for 1 hour.
  • DMF Dimethylformannide
  • DMA ⁇ , ⁇ -Dimethylacetamide
  • GBL r -butyrolactone
  • DMEU 1 ,3-dimethyl-2-innidazolidinone
  • Stable graphene sheet dispersions were prepared in tetrabutylammonium (TBA) hydroxide mixed with dimethylformamide (DMF). Individual MnO2 nanosheets were prepared in a TBA hydroxide solution. A stable dispersion containing both nanosheets are created by mixing of solvents in a ratio of 4:1 DMF:TBA. The mixture was drop cast onto a metal plate and the solvents were evaporated by heating in an oven at 120°C for 1 hour. TBA was removed by repeated washing with deionized water.
  • TBA tetrabutylammonium
  • DMF dimethylformamide
  • TiCI titanium tetrachloride
  • HAI hydrochloric acid
  • PEI polyethylene imine
  • the mixture was covered by aluminum foil and placed into an oven. The presence of TiO 2 was evidenced by the presence of a white powder.
  • Graphene flakes were added to the solution and mixed with a magnetic stirrer. The mixture was then stirred and refluxed. The resulting suspension was centrifuged and the excess liquid was decanted off. The remaining slurry was then filtered and washed with distilled water followed by ethanol. Electrodes were prepared by depositing the slurry onto an appropriate surface.
  • T1O2 nanosheets were produced by a simple hydrothermal route using tetrabutyl titanate, Ti(OBu) 4 , as a source and hydrofluoric acid solution as the solvent. The two were mixed in an autoclave at high temperature, above 180°C. After cooling to room temperature, centrifugation was used to separate the product, followed by washing ethanol and water. The TiO 2 nanosheets that were produced were stable and could be stored in ethanol for electrode processing.
  • Graphene flakes were then mixed with a polyvinylidene fluoride (PVDF) binder (5 wt.%) in N-methyl-2-pyrrolidone solvent. The mixture was then sonicated for 1 hour. The T1O2 nanosheets dispersed in ethanol were then added to the mixture and sonicated. The resulting slurry was drop cast onto a stainless steel current collector of an appropriate length and width. The electrode/current collector was placed into an oven to evaporate the solvent and to create a robust electrode.
  • PVDF polyvinylidene fluoride
  • nanosheets was deposited directly from the solution on top of the graphene networks fabricated followed by incubation and rapid shaking of the electrode.
  • the graphene network acts rather as the current collector whereas the additional coating is the active material.
  • This geometry is fundamentally different from composites where all materials are mixed together and potentially interrupting the current paths within the graphene network.
  • nanosheets and graphene flakes can lead to electrodes that have high specific capacitance C/gr and high electrical conductivity.
  • other nano-structured carbons such as activated carbons can also be incorporated into the structure.
  • nanosheets of T1O2 anatase
  • Electrodes with three components may also possess properties
  • Electrodes containing oxide nanosheets, graphene and activated carbon were produced as an illustration. In this example,
  • nanosheets of TiO 2 (anatase) have an electrochemical capacitance of
  • the electrodes take advantage of both the high conductivity of the graphene and the high specific capacitance of the oxides.
  • the direct electrical contact between the two species ensures that the charges generated by the electrochemical reaction at the surface of the oxide materials will be transferred to the graphene network. Thus high energy density and high power density are ensured.
  • an asymmetric supercapacitor may be assembled with an anode comprising interpenetrating networks of carbon graphene and oxide nanoparticles and a cathode comprising interpenetrating networks of graphene and a carbonaceous material (e.g., activated carbon).
  • a carbonaceous material e.g., activated carbon
  • one or both of the interpenetrating networks of graphene and nanoparticles may have a density above a percolation threshold; or the combined interpenetrating networks of nanowires may have a density above a percolation threshold where neither network alone has a density above a percolation threshold.
  • asymmetric supercapacitors may be constructed that have one electrode that provides significantly larger capacitance Ci than the other electrode C 2 .
  • an asymmetric supercapacitor can reliably operate at operating voltages up to about 2V— almost double that of commercially available symmetric capacitors. This higher operating voltage allows an almost a four-fold increase in energy density. Combined, these factors provide an energy density potentially up to eight times that of an electric double layer capacitor.
  • Capacitances exceeding C 200F/g are readily obtained for a variety of carbon materials, including aerogels, activated carbons and carbon- conducting polymer composites. Capacitances up to 800F/gr have been reported for ruthenium oxides, and 800F/gr for M0O 3 . Assuming the latter value and a voltage window of 1 .6V, performance of asymmetric
  • supercapacitors according to embodiments of the present invention can achieve an energy density of 30 Wh/kg.
  • Electrochromic (EC) devices often require flexible transparent
  • ITO Indium-Tin-Oxide
  • PDOT/PSS poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate)
  • Graphene films that incorporate nanowires can be used as transparent electrodes, and a conducting polymer, polyaniline (PANI), can be used as the electrochromic active material.
  • PANI polyaniline
  • the color of PANI can be electrochemically tuned by applying different potentials and the use of PANI as the active material for EC devices has been previously demonstrated using ITO on glass as the transparent electrodes.
  • Another advantage of using PANI is that it can be conveniently deposited on the electrodes via a simple electrochemical reaction in an acidic solution. PANI can be electrochemically grown on even ultrathin transparent graphene networks, which can then be immediately used for EC devices.
  • Light emitting diodes can also be fabricated using graphene composite films as anodes, in combination with other transparent materials such as indium tin oxide ITO.
  • ITO indium tin oxide
  • the ITO component provides the high transparency, the graphene flakes providing the high mechanical flexibility needed for many applications.
  • An interpenetrating network assembly comprising a network of connected flakes of nano-scale crystalline carbon; and nano-particles of an electrochemical material in contact with the carbon flakes.
  • material is a material selected from the group of materials consisting essentially of an oxide, a sulphide and a selenide.
  • oxide material is an oxide selected from the group of oxides consisting essentially of NiO, SiO 2 , TiO 2 , MnO 2 , MoO 3 , V 2 O 5 , and RuO 2 .
  • conductive nano-particles selected from the group of particles consisting essentially of Ag nanowires, ZnO nanowires, ITO nanowires, semiconducting nanowires, polyaniline nanofibers, carbon nanotubes, activated carbon and carbon black.
  • material is a material selected from the group of materials consisting essentially of an oxide, a sulphide and a selenide.
  • An interpenetrating network assembly comprising a source and a drain; a network of connected flakes of nano-scale crystalline carbon bridging the source and the drain; and nano-scale particles of an electrochemical material interconnected with the carbon flakes.
  • electrochemical material is a material selected from the group of materials consisting essentially of an oxide, a sulphide or a selenide.
  • electrochemical material is an oxide selected from the group of oxides consisting essentially of NiO, SiO 2 , TiO 2 , MnO 2 , MoO 3 , V 2 O 5 , and RuO 2 .
  • An interpenetrating network assembly comprising a source and a drain; a network of connected flakes of graphene bridging the source and the drain; a network of connected nano-scale flakes of an electrochemical material in contact with said carbon flakes bridging the source and the drain;
  • nanoparticles of an electrical conductor in contact with the interconnected flakes of electrochemical material and flakes of graphene in contact with the interconnected flakes of electrochemical material and flakes of graphene; and nanoparticles of a second electrochemical material in contact with said interconnected flakes of electrochemical material, nanoparticles of electrical conductor and flakes of graphene.
  • conductive nano-particles are selected from the group of particles consisting essentially of metallic nanowires, semiconductor nanowires, ZnO nanowires, ITO nanowires, polyaniline nanofibers, Si nanowires, and Ni nanowires.
  • conductive nano-particles are selected from the group of particles consisting essentially of activated carbon, carbon nanotubes, and carbon black.
  • conductive nano-particles are conductive nanowires made from the group of conductors consisting essentially of Ag, Ni, Pt, Au, InP, Si, and GaN.
  • electrochemical material is an oxide selected from the group of oxides consisting essentially of NiO, SiO 2 , TiO 2 , MnO 2 , MoO 3 , V 2 O 5 , and RuO 2 .
  • electrochemical material is the form of nanowires.
  • a sensor assembly comprising a source and a drain; a single graphene flake bridging the source and the drain; and at least one receptor molecule that changes electronic conformation in response to an

Abstract

L'invention concerne un ensemble réseau interpénétrant avec un réseau de flocons connectés de carbone cristallin nanométriques et de particules nanométriques d'un matériau électroactif interconnecté avec les flocons de carbone. Les ensembles réseaux conviennent particulièrement à des applications de stockage d'énergie qui utilisent des matériaux électroactifs d'oxydes de métaux et un seul collecteur de charge ou une source et un drain. Les réseaux interpénétrants de flocons de graphène et de nanofeuilles d'oxyde de métal peuvent former des passages indépendants entre la source et le drain. Les matériaux conducteurs nanométriques comme des nanofils, des nanotubes de carbone, du charbon activé ou du noir de carbone peuvent être inclus comme partie du réseau conducteur pour améliorer le transfert de charge.
PCT/US2012/025523 2011-02-16 2012-02-16 Réseaux interpénétrants de carbone cristallin et de matériaux électroactifs à l'échelle nanométrique WO2012112818A2 (fr)

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