WO2008070926A1 - Nanotube and carbon layer nanostructured composites - Google Patents
Nanotube and carbon layer nanostructured composites Download PDFInfo
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- WO2008070926A1 WO2008070926A1 PCT/AU2007/001933 AU2007001933W WO2008070926A1 WO 2008070926 A1 WO2008070926 A1 WO 2008070926A1 AU 2007001933 W AU2007001933 W AU 2007001933W WO 2008070926 A1 WO2008070926 A1 WO 2008070926A1
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- NHLDKDYUMJJCHD-UHFFFAOYSA-N COS(c1ccc(C=C)cc1)(=O)=O Chemical compound COS(c1ccc(C=C)cc1)(=O)=O NHLDKDYUMJJCHD-UHFFFAOYSA-N 0.000 description 1
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- B82B3/00—Manufacture or treatment of nanostructures by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
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- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
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- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/26—Deposition of carbon only
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
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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
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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Definitions
- the present invention relates to nanostructured composites, particularly conducting nanostructured composites for use in the fields of energy conversion, energy storage and also the biomedical field.
- the present invention also relates to a process for preparing the nanostructured composites .
- Electrodes for photochemical cells require a high surface area to enable efficient charge transfer to the electrolyte. Electrodes to be used in devices for charge storage also require a high surface area and high conductivity.
- Bio-electrodes are used to deliver charge to, or sense electric pulses on or within living organisms. Common bio-electrodes include pacemaker electrodes and electrocardiogram (ECG) pads .
- ECG electrocardiogram
- Electrodes for humans are made from Pt and Pt-Ir alloys. Often these metals are coated with titanium nitride or conducting oxides (e.g. RuO 2 or IrO 2 ) to increase their surface area, or adjust their bio- interaction.
- Nanotubes for example carbon nanotubes, present new materials for the construction of electrodes for electrochemical devices . Such electrodes require high conductivity, strength and surface area. The latter two requirements are often incompatible .
- Electrodes composed entirely of carbon nanotubes (bucky paper) have high surface areas but are typically weak, nonflexible, and have insufficient conductivity for practical macroscopic applications .
- nanostructured composites are required to be mechanically robust and preferably with sufficient conductivity for use in applications such as electrodes for energy storage and conversion.
- the present invention provides a nanostructured composite comprising a nanotube network integrated within a carbon layer .
- the composite is conducting.
- the carbon layer is highly conducting, such as, an activated carbon layer (CL) , for example, an amorphous carbon (AC) layer.
- CL activated carbon layer
- AC amorphous carbon
- the nanostructured composite may further comprise a substrate, thus providing a nanostructured composite substrate structure .
- the carbon layer is attached to the substrate.
- attachment we mean physically retained by the substrate .
- the substrate is a metal, resulting in a nanostructured composite substrate structure having metal-like conducting properties.
- the composite is biocompatible resulting in a biomaterial composite.
- the nanotubes and/or the carbon layer may be biocompatible.
- the composite further comprises a substrate, the nanotubes, carbon layer and/or the substrate may be biocompatible .
- the present invention further provides a process for preparing a nanostructured composite or a nanostructured composite substrate structure which comprises the steps of: i) Depositing a metal catalyst on a substrate; ii) chemical vapour deposition (CVD) growth of a nanotube network with a carbon layer underneath from the catalyst on the substrate to form a nanostructured composite substrate structure; and iii) optionally separating the nanostructured composite from the substrate .
- CVD chemical vapour deposition
- the nanotubes are orientated in the nanostructured composite such that they protrude from the carbon layer.
- the nanotubes are partially embedded in the carbon layer, that is, the starting growth point of the nanotube is embedded in the carbon layer and the remaining portion of the nanotube protrudes from the carbon layer.
- the nanotubes grow from the metal nanoparticles formed by reduction of the organic metal catalyst which is embedded in the carbon layer to form intimate connection between the nanotubes and the carbon layer.
- the substrate of step ii) is in the form of a dispersing media, optionally comprising a biomolecule, the dispersing media being cast onto the nanotube layer.
- the present invention further provides an article comprised wholly or partly of the nanostructured composite and/or the nanostructured composite substrate structure described above.
- the article is electrically conducting and examples include electrodes for energy storage and conversion, such as capacitors, hybrid battery capacitors, supercapacitors and batteries; electrodes for use as fuel cells, gas storage mediums and sensors,- and electrodes for use in the biomedical field such as bioelectrodes, biofuel cells and substrates for electrically stimulated bio-growth.
- Composites are generally described as materials made from two or more constituent materials which remain separate and distinct within the finished structure.
- constituent materials are of two types, generally described as matrix and reinforcement materials. It is generally understood that the matrix material surrounds and supports the reinforcement material and a type of synergism is achieved that produces a material with enhanced properties .
- nanostructured composites are provided in which the nanotubes are viewed as the matrix material, and the carbon layer, to which they are attached, is viewed as the reinforcement of the composite.
- a more robust material is provided compared with (for example) electrodes composed entirely of carbon nanotubes (bucky paper) .
- Nanotubes are typically small cylinders made of organic or inorganic materials.
- Known types of nanotubes include carbon nanotubes, inorganic nanotubes and peptidyl nanotubes .
- Inorganic nanotubes include WS 2 and metal oxide nanotubes such as oxides of titanium and molybdenum.
- the nanotubes are carbon nanotubes (CNTs) .
- CNTs are sheets of graphite that have been rolled up into cylindrical tubes .
- the basic repeating unit of the graphite sheet consists of hexagonal rings of carbon atoms, with a carbon-carbon bond length of about 1.45 A.
- the nanotubes may be single-walled nanotubes (SWNTs) , double walled carbon nanotubes (DWNTs) and/or multi-walled nanotubes (MWNTs) .
- a typical SWNT has a diameter of about 0.7 to 1.4nm.
- nanotubes provide them with unique physical properties .
- Nanotubes may have up to 100 times the mechanical strength of steel and can be up to several mm in length. They exhibit the electrical characteristics of either metals or semiconductors, depending on the degree of chirality or twist of the nanotube . Different forms of nanotubes are known as armchair, zigzag and chiral nanotubes. The electronic properties of carbon nanotubes are determined in part by the diameter and therefore the v form' of the nanotube .
- carbon nanotubes are suitable materials for electrochemical capacitors.
- the nanotubes are oriented in the composite of the present invention such that they protrude from the carbon layer.
- the nanotubes are partially embedded in the carbon layer, that is, a portion of one end of the nanotube is embedded in the carbon layer and the remaining portion of the nanotube protrudes from the carbon layer.
- the nanotubes grow from the metal nanoparticles formed by reduction of the organic metal catalyst which is embedded in the carbon layer to form intimate connection between the nanotubes and the carbon layer.
- the nanocomposite is prepared via a process involving a metal catalyst deposited on a substrate. In the process, the metal nanoparticles of the catalyst become embedded in the carbon layer and it may be said that the nanotubes grow from these metal nanoparticles, resulting in intimate connection between the nanotubes and the carbon layer.
- the nanotubes of the nanocomposite are preferably unaligned nanotubes which are capable of forming three- dimensional entangled networks .
- the nanotubes may be single-walled nanotubes (SWNTs) , double-walled nanotubes (DWNTs) and/or multi-walled nanotubes (MWNTs) .
- SWNTs single-walled nanotubes
- DWNTs double-walled nanotubes
- MWNTs multi-walled nanotubes
- the nanotubes are unaligned, multi-walled nanotubes, typically termed: an unaligned, multiwall nanotube networks or forests.
- the nanotubes are preferably unaligned multi-wall carbon nanotubes (MWNTS) of an average length greater than 1 ⁇ m, preferably greater than 50 ⁇ m, more preferably greater than 100 ⁇ m, and an external diameter of 10-100 nm, preferably 20-40 nm.
- MNTS multi-wall carbon nanotubes
- Aligned carbon nanotubes are highly ordered and considered to have good electrochemical properties. However, the composites containing unaligned nanotubes also show good electrochemical properties, in some circumstances superior to vertically aligned nanotubes grown in the same furnace.
- the nanotubes are oriented in the nanocomposite such that they protrude from the carbon layer.
- the carbon layer is preferably conducting and in such an embodiment, the conducting carbon layer means the previous requirement of depositing metal contacts on the nanotubes to obtain a conducting material is avoided. Growth of the nanotubes from the carbon layer itself results in the nanotubes being integrated within the carbon layer.
- the carbon layer is preferably an activated carbon layer (CL) such as an amorphous carbon (AC) layer, more preferably a non-graphitised carbon layer.
- an activated carbon layer such as an amorphous carbon (AC) layer, more preferably a non-graphitised carbon layer.
- the carbon layer is less than lO ⁇ m, preferably less than 5 ⁇ m, more preferably less than 1 ⁇ m in thickness.
- SEM imaging shows a uniformly dense continuous AC film with nano-sized porosity.
- XRD spectra shows the AC layer to be disordered, but activated, AC.
- the carbon layer may contain a metal or combination of metals originating from the metal catalyst utilized in the process of preparing a composite.
- the metal originating from the metal catalyst may be a transition metal such as palladium, iron, rhodium, nickel, molybdenum and/or cobalt, preferably iron, nickel or cobalt.
- the metal content of the carbon layer may be less than 20%, preferably less than 10%, more preferably less than 5% (obtained from Energy Dispersive X-Ray Analysis) . At such a small concentration, the metal content alone could not be considered to be responsible for the conductivity of the carbon layer.
- the composite is flexible and robust.
- the carbon layer adds strength to the composite yet maintains sufficient flexibility to enable it to be shaped for a variety of uses.
- the composite can be of varying thickness.
- the thickness of the composite is 1 -100 ⁇ m, more preferably 5 - 50 ⁇ m, most preferably about 20 ⁇ m making it suitable for use in flexible thin supercapacitors and as anode materials for batteries such as Li-ion rechargeable batteries.
- the composite may further comprise a substrate, thus providing a nanostructured composite substrate structure.
- a substrate is utilised in the preparation of the nanocomposite of the present invention. It provides the surface onto which the catalyst film is prepared and from which the nanotube network with a carbon layer underneath are grown. Growth of nanotubes requires high temperatures, usually of the order of around 500 0 C and greater. This step can be achieved using CVD involving a substrate capable of withstanding the high temperatures required for nanotube growth in an inert atmosphere, for example, Ar or N 2 gas.
- the substrate can be conducting or non-conducting.
- Suitable examples of conducting substrates include glassy carbon; metals or metal foils, for example, copper, iron, nickel, platinum and aluminium metals or metal foils,- metal coated quartz plates and glassy slides; carbon paper such as carbon fiber paper,- carbon,- carbon nanotube fibre; and carbon nanotube paper.
- non-conducting substrates include quartz, silicon wafers, glassy slides and inorganic composites, for example metal oxide films.
- the nanocomposite is separated from the substrate on which it is prepared and utilized alone.
- the composite may be transferred to another substrate with properties suited to a desired application.
- the substrate may be chosen from those listed above, or can be chosen from any other substrates, not necessarily capable of withstanding the high temperatures required for nanotube growth, such as non-polymeric materials for example metals and polymeric materials .
- the use of a metal substrate results in a composite substrate structure having metal-like conducting properties.
- metal substrates include platinum, metal foils for example copper foils for use in rechargeable batteries and aluminium foils for use in capacitors, metal-coated membranes, metal coated textiles and metal coated polymers fibres .
- the polymeric substrates may include Poly (styrene- ⁇ - isobutylene- ⁇ -styrene) (SIBS) which is a soft, elastomeric triblock copolymer that is an effective biomaterial due to its superior biostability and biocompatibility.
- SIBS Poly (styrene- ⁇ - isobutylene- ⁇ -styrene)
- polymeric substrates include electronic conductors such as polyethylene dioxythiophene (PEDOT) , soluble pyrroles, polythiophenes and/or polyanilines; acrylate polymers; acrylic acid polymers; polyacrylic esters; polyacrylamides; polyacrylonitriles; chlorinated polymers; fluorinated polymers; styrenic polymers,- polyurethanes ; natural rubber,- synthetic rubber polymers; vinylchloride- acrylate polymers; and copolymers thereof.
- PEDOT polyethylene dioxythiophene
- soluble pyrroles soluble pyrroles
- polythiophenes and/or polyanilines
- acrylate polymers acrylic acid polymers; polyacrylic esters; polyacrylamides; polyacrylonitriles; chlorinated polymers; fluorinated polymers; styrenic polymers,- polyurethanes ; natural rubber,- synthetic rubber polymers; vinylchloride- acrylate polymers;
- polymeric substrates include, but are not limited to, poly(vinyl acetate), poly(acrylic acid), poly(methyl methacrylate) , polyacrylamide, polyacrylonitrile, polyvinylpropionate, polystyrene, polytetrafluoroethylene, poly(vinyl chloride), poly (vinylidene chloride), poly(vinyl chloride-ethylene) , poly(vinyl chloride-propylene) , poly (styrene-co- butadiene) , styrene-acrylate copolymers, ethylene-vinyl chloride copolymer, poly (vinyl acetate-acrylate) , poly (vinyl acetate-ethylene) and combinations thereof.
- the nanotubes, carbon layer and/or substrate can be chemically modified, for example by attaching biomolecules, catalysts and/or additional conductors .
- biocompatible composite and/or substrate structure When biomolecules are attached, a biocompatible composite and/or substrate structure is produced which may function as a biomaterial .
- biomolecule generally refers to molecules or polymers of the type found within living organisms or cells and chemical compounds interacting with such molecules .
- biological polyelectrolytes such as hyaluronic acid (HA) , chitosan, heparin, chondroitin sulphate, polyglycolic acid (PGA) , polylactic acid (PLA) , polyamides, poly-2-hydroxy-butyrate (PHB) , polycaprolactone (PCL), poly (lactic-co-glycolic) acid (PLGA) , protamine sulfate, polyallylamine, polydiallyldimethylammonium, polyethyleneimine, eudragit, gelatin, spermidine, albumin, polyacrylic acid, sodium alginate, polystyrene sulfonate, carrageenin, carboxymethylcellulose; nucleic acids such as DNA, cDNA, RNA, oligonucleotide, oligoribonucleotide
- Polyelectrolytes are polymers having ionically dissociable groups, which can be a component or substituent of the polymer chain. Usually, the number of these ionically dissociable groups in the polyelectrolytes is so large that the polymers in dissociated form (also called polyions) are water-soluble. Depending on the type of dissociable groups, polyelectrolytes are typically classified as polyacids and polybases . When dissociated, polyacids form polyanions, with protons being split off, which can be inorganic, organic and biopolymers . Polybases contain groups which are capable of accepting protons, e.g., by reaction with acids, with a salt being formed.
- the biomolecule may include functional groups to allow further control of the biointeraction such as biomolecules which convey active ingredients for example drugs, hormones, growth factors or antibiotics.
- the biomolecule can also be chosen depending on the desired application, for example, if the composite was to be used to promote or inhibit adhesion of certain cell types it may be advantageous to use biomolecules which promote nerve or endothelial cell growth or inhibit smooth muscle cell growth (fibroblasts) .
- the biomolecule can include a monomer for example pyrrole and/or an oxidant, for example FeCl 3 .
- biomolecule can be rendered conductive by subsequent electrochemical or chemical oxidation if one or more monomers are present, or by vapour phase polymerisation if one or more oxidants are present in the substrate .
- More than one biomolecule may be present in the nanocomposite and/or substrate of the present invention.
- the choice of the biomolecule will be determined by the end use of the composite or composite substrate structure .
- the nanotube surface may also be modified with an additional conductor such as metals by sputter coating or electrodeposition, or a conducting polymer by solution chemical or vapour phase polymerisation or by electrodeposition.
- an additional conductor such as metals by sputter coating or electrodeposition, or a conducting polymer by solution chemical or vapour phase polymerisation or by electrodeposition.
- the process for preparing the nanostructured composite or a nanostructured composite substrate structure includes the steps of : i) depositing a metal catalyst on a substrate; ii) chemical vapour deposition (CVD) growth of a nanotube network with a carbon layer underneath from the catalyst on the substrate to form a nanostructured composite substrate structure; and iii) optionally separating the nanostructured composite from the substrate .
- CVD chemical vapour deposition
- the first step involves depositing a metal catalyst film on a substrate .
- the substrate provides the surface onto which a catalyst film is prepared, from which the nanotubes are grown, and on which the carbon layer is formed.
- the catalyst can be any catalyst suitable for catalysing nanotube growth.
- the metal catalyst may be an organic metal catalyst or an inorganic metal catalyst, preferably an organic metal salt catalyst.
- a organic metal catalyst includes a metal-carbon bond.
- the carbon of this metal-carbon bond is nucleophilic and capable of giving rise to a carbon-carbon bond. It is hypothesised that this initiates the growth of nanotubes, in particular carbon nanotubes .
- the metal of the metal catalyst can be a transition metal such as palladium, iron, thodium, nickel, molybdenum and cobalt, preferably iron, nickel or cobalt.
- Suitable organic salts include optionally substituted aryl or heteroaryl sufonates for example, toluenesulfonate, alkyl benzene sulfonates and pyridinesulfonates; and carboxylic acid salts such as acetates or acetylacetonates .
- organic metal salt catalysts as are as follows:
- the catalyst film can be prepared by dissolving a metal salt with an organic compound in a solvent and depositing this on a substrate.
- a catalyst film can be prepared by mixing FeCl 3 with NaCSA in a molar ratio of 1:1, in an organic solvent, for example ethanol .
- the catalyst can be directly deposited on the substrate from organic solvents, such as ethanol.
- organic solvents such as ethanol.
- the organic solvent can then be removed prior to the second step by annealing.
- the catalyst film can be deposited using any suitable known technique, such as, spin coating.
- the catalyst forms a stable, thin film on the substrate.
- the film may be of suitable thickness to catalyse growth of nanotubes.
- the catalyst film is ⁇ 50 ⁇ m, more preferably ⁇ 10 ⁇ m in thickness.
- Fig. 7 shows that carbon nanotubes grown from Fe(III)DBS (see Fig 7a) have shorter but larger diameter nanotubes when compared with those grown from Fe(III)PS (see Fig 7b) and the Fe(IlDpTS (see Fig 7c) .
- the metal catalyst which provided the highest quality carbon nanotubes with the greatest porosity carbon nanotube forest were grown from Fe(III)pTS.
- the sheet resistances of the resulting carbon layer of the nanocomposite were also influenced by choice of catalyst.
- the sheet resistances were found to be 46 ⁇ , 86 ⁇ , 65 ⁇ and 57 ⁇ per square for the Fe (III) pTS, Fe(III)DBS, Fe(III)PS and Fe(III)CSA respectively.
- Fe(III)PTS is the most preferred catalyst as it produces most conductive composites .
- the second step of the preparation of the nanocomposite involves CVD growth of the nanotube network with the carbon layer underneath from the catalyst film on the substrate.
- a carbon source is utilized, preferably a gaseous carbon source . It has been noted that in the absence of a carbon source, the resistance of the carbon layer is found to be approximately 5k ⁇ . Addition of a carbon source to the growth step lowers the resistance of the carbon layer by a factor of greater than 100, thus making it much more conductive.
- Examples of carbon sources include alkanes, alkenes, alkynes and/or aryls and derivatives thereof. Suitable examples of alkanes are methane, ethane, propane, isopropane, butane, isobutane, sec-butane, tert-butane, pentane, neopentane, hexane and the like.
- alkenes are ethylene, propene, 1-butene, 2- butene, 2-methyl propene, 3 , 3-dimethyl-1-butene, 4-methyl- 2-pentene, 1, 3-butadiene, 2-methyl-1, 3-butadiene, isoprene, (2E, 4E) -2, 4-hexadiene, cyclopentene, cyclohexene, 1, 2-dimethylcyclopentene, 5-methyl-l, 3- cyclohexadiene and the like .
- alkynes are: acetylene, propyne, 1-butyne, 2-butyne, 3-methyl-l- butyne, 1-pentyne, 2-pentyne, 1-hexyne, 2-hexyne, 3- hexyne, 3 , 3-dimethyl-1-butyne, 1-octyne, 1-nonyne, 1- decyne and the like .
- Suitable examples of aryls include phenyl , naphthyl , tetrahydronaphthyl , indane and biphenyl .
- the carbon source is methane, ethylene and/or acetylene.
- the CVD is initially carried out at 500 0 C under Ar/H 2 gas flow to reduce the metal catalyst to metal nanoparticles .
- the growth phase then follows which is preferably carried out at 800 0 C.
- the preparation of the composite utilises an organic ferric salt as a catalyst and acetylene as a carbon source. Even further preferably, it utilizes Fe(III) pTS as the catalyst and acetylene as the carbon source .
- the composite can be optionally removed from the substrate.
- the composite could then be transferred to another substrate with properties suited to a desired application.
- polymer or metal films can be deposited and cured on top of the nanotube layer prior to removal from the substrate .
- the composites and composite substrate structures of the present invention are suitable for a variety of applications.
- the embodiment in which the nanocomposite is conducting makes it suitable for use in the fields of energy conversion and storage and in materials and devices that require conducting high surface area materials, such as electrodes for capacitors, hybrid battery/capacitors, supercapacitors, batteries, fuel cells, electrocatalysts, gas storage mediums, sensors, actuators, electromechanical actuators, photoelectrochemical solarcells and/or bioelectodes for electrical stimulation of cells and tissue.
- Composites of entangled carbon nanotubes and AC on copper foil substrates are suitable for use in rechargeable batteries .
- Composites of entangled carbon nanotubes and AC on aluminum foil substrates are suitable for use in capacitors .
- Composites of entangled carbon nanotubes and AC on carbon paper substrates are suitable for use in fuel cells.
- Composites of entangled carbon nanotubes and AC on membranes substrates are suitable for use in actuators.
- the composites may be biocompatible and together with their conducting properties make them suitable for medical applications that require electrostimulation, the passage of an electrical current or electrical sensing such as bio-electrodes, biofuel cells or as substrates for electrically stimulated bio-growth.
- the composites exhibit sufficient conductivity, electrochemical capacitance and mechanical properties to be used directly as electrodes implanted into living organisms for the purpose of electrical sensing and stimulation. Specific applications include pacemaker electrodes, ECG pads, biosensors, muscle stimulation, epilepsy control and electrical stimulated cell regrowth.
- Electrodes for biological implants typically consist of platinum or iridium and their derivatives.
- Embodiments of the present invention provide electrically conducting nanocomposites that may contain biomolecules .
- Biomolecules such as chitosan are currently used in conjunction with many implants in the human body.
- functional groups may be added to chitosan to allow further control of the bio-interaction.
- the bio-compatibility of carbon nanotubes is not known, however initial studies show great promise. Therefore, potentially a new bio-electrode which is robust and efficient may be produced. These bio- electrodes should also be efficient and robust.
- Fig. 1 Several Scanning Electron Micrograph (SEM) and optical images of free standing CNT/AC paper; (a) digital image of the upper surface of the CNT/AC, after CVD growth on a 40cm2 quartz plate; (b) digital image of the underneath surface of the AC layer when removed from the substrate.
- SEM Scanning Electron Micrograph
- the reflectivity of the layer is visible from the reflected image of the photographer easily observed in the image; (c) digital image of CNT/AC paper removed from the quartz substrate and rolled onto glass rods, indicating the flexibility and mechanical robustness of both sides of the CNT/AC composite paper, (d) SEM image of the top surface of the film, showing a dense entanglement of carbon nanotubes; (e) SEM image of the cross section of the CNT/AC paper,- showing an obvious 'intersection' between the AC layer (indicated by the white arrow) and the upper carbon nanotube network layer,- and (f) SEM image of the underneath of the AC layer, showing densely packed but still porous morphology.
- FIG. 2 High resolution scanning electron microscopy images of the CNT-AC intersection region, showing intimate contact between the outer nanotube shell and the amorphous carbon layer (left image) .
- Right image is a higher magnification image of one region in the left image, which suggests that the CNT is growing out through the AC layer and not merely on top of it .
- Fig. 3 Cyclic voltammograms performed in a conventional three-electrode cell where the working electrode was: (a) CNT/AC paper and (b) commercial MWCNT mat (NanoLab, Boston) in aqueous 1 mM K4Fe (CN) 6/1.0 M NaNO3 under identical experimental conditions.
- the y-axis is displayed as Amps/g so direct comparison between the two different morphologies can be made.
- Scan rate 5 mV s-1.
- Fig. 4 Digital and SEM images of free-standing CNT/AC/metal paper, (a) digital image of CNT/AC on copper foil, (b) SEM image of CNT layer on copper foil.
- Fig. 5 Schematic illustration of a procedure for the preparation of CNT/AC paper in accordance with an embodiment of the invention: (a) spin-coating a thin Fe(III) pTS film (1 to 5 ⁇ m) onto cleaned quartz plate; (b) thermal CVD growth of multi-wall carbon nanotubes with a highly conductive carbon layer underneath using acetylene as carbon source; (c) free-standing paper peeled off from quartz plate.
- Fig. 7 Scanning Electron Microscope images of the top surface of free standing CNT/AC papers grown from; (a) Fe(III) DBS, (b) Fe(III) PS, and (c) Fe(III) pTS . Images are shown at the same magnification.
- Fig. 8 Overlay of cyclic voltammograms obtained using a free-standing CNT/AC paper as working electrode at varying scan rates in aqueous 1.
- OM NaNO 3 Platinum mesh and Ag/AgCl counter and references electrodes made up a conventional three-electrode cell. Data from these voltammograms at 0.2V were used to calculate the specific capacitance values in the paper.
- Fig. 9 Digital and SEM images of free-standing CNT/AC/metal papers, (a) digital image of CNT/AC on aluminium foil, (b) SEM image of CNT layer on aluminium foil, and (c) cross section SEM image of CNT/AC/aluminium paper .
- Fig. 10 Scanning Electron Micrograph (SEM) images of CNT modified carbon fiber paper, showing a dense entanglement of carbon nanotubes which entirely covers the individual carbon fibers whilst still retaining the microporous nature of the host carbon fiber paper; (b) higher resolution image of the carbon fibre indicated in (a) ; inset (c) Transmission Electron Microscopy (TEM) image of an individual multi-wall carbon nanotube grown on the CFP.
- SEM Scanning Electron Micrograph
- TEM Transmission Electron Microscopy
- Fig. 11 Raman spectra of (a) blank carbon fiber paper and (b) CNTs modified carbon fiber paper, using 632.8 nm diode laser excitation on 900 lines/mm grating at room temperature .
- Fig. 12 The first to fiftieth charge/discharge profiles of the CNT/CFP electrode when working as the anode material in a commercial CR2032 coin cell.
- the current density was 0.05 mA cm '2
- Fig. 13 Discharge capacity vs. cycle number for CNTs deposited on /CFP at different charge/discharge rate; (a) 0.05 mA cm “2 , (b) 0.20 mA cm “2 , and (c) 0.50 mA cm “2 .
- Fig. 14 SEM images of CNT nanoweb deposited on a platinum sheet .
- Fig.15 Overlay of Cyclic voltammograms obtained using (a) a CNT nanoweb and (b) pure platinum sheet as the working electrode in perilymph solution at the scan rate of 100 mV s "1 . Data form these voltammograms are used to compare the electroactivity of CNT nanoweb with Pt sheet in bioenvironment .
- Fig. 16 Overlay of Linear sweep voltammograms (vs. Ag/AgCl) for oxygen reduction at PPy/Co-TPP modified CNT Nanoweb electrode in 0.5 M H 2 SO 4 aqueous solution (under O 2 atmosphere) . Scan rate: 10 mV s "1 .
- the CNT Nanoweb is modified by Co-incorporated porphyrin (oxygen reduction catalyst) containing polypyrrole film for electrocatalytic oxygen reduction reaction.
- Electrochemical experiments were performed in a standard three-electrode system, using the CNT/AC paper as working electrode, platinum mesh and Ag/AgCl as counter and reference electrodes respectively, in 0.01 M K 4 Fe (CN) 6 /0.1M NaNo 3 , using an eDAQ e-corder (401) and potentiostat/galvanostat (EA160) with Chart v5.1.2/EChem v 2.0.2 software (AD Instruments).
- a l ⁇ m thin film of the catalyst (Fe (III) /TS/DBS or /PS were spin coated onto a quartz plate (3 mm thick, 4xl ⁇ cm) using a commercial spin coater (Laurell Tech) at a speed of 1000 rpm from a 10% (w/w) Fe (III)TS/ethanol solution.
- the catalyst film was then annealed in a conventional oven at 60-80 0 C for up to 5 min until the film colour changed to a darker yellow, indicating that the ethanol solvent had evaporated.
- Chemical Vapour Deposition was carried out using a commercially available Thermal CVD System (Atomate) allowing software control over gas flow, furnace temperature and deposition time .
- the system was flushed with argon (Ar, 150 ml/min) for 30 min, then the temperature of the furnace was increased under a gas flow of Ar (200ml/min) and H 2 (20 ml/min) , until it reached 500 0 C.
- the furnace temperature was then held at 500 0 C for 10 min, which reduces the iron (III) to iron nanoparticles .
- the temperature was increased again, up to 800 0 C, whereupon acetylene (C 2 H 2 ) was introduced for 30 min, at the gas flow rates of Ar (200ml/min) , C 2 H 2 (10ml/min) and H 2 (3 ml/min) for the growth of the carbon nanotube films. Finally, the acetylene and hydrogen gases were turned off, while the Ar (150 ml/min) was continuously flushed through the furnace until the temperature was less than 100 0 C. The product was cooled to room temperature, over 2 h. Faster cooling results in defects in the CNT structure.
- the resultant CNT films mode from the catalyst Fe (III) /TS (Fig. Ia) were observed to be vastly different to those grown under conventional conditions . It was apparent that during CNT growth, a very reflective layer was formed beneath the carbon film (Fig. Ib) .
- the resultant carbon nanotube/amorphous carbon (CNT/AC) paper appeared on the quartz plate as a matt-black layer above (Fig. Ia) a flexible and shiny AC layer underneath (Fib. Ib) . the CNT/AC paper could easily be removed from the substrate and this free-standing film could be rolled around a glass rod without visible signs of degradation (Fig. Ic) .
- the nanotubes in the CNT forest are multi- wall carbon nanotubes (MWNT) of an average length >100 ⁇ m and an external diameter of 20-40 ran.
- MWNT multi- wall carbon nanotubes
- FIG. 2 shows that CNT grown from Fe(III)DBS (Fig.7a) have shorter but larger diameters nanotubes when compared with those grown from Fe(III)PS (Fig.7b) and Fe (III)pTS (Fig.7c).
- the AC layer After re-introduction of acetylene the AC layer begins to develop the characteristics of the intergrated CNT/AC paper, confirming that both acetylene and an organic catalyst are integral to creating the superior electrode material . It is anticipated that barrier effects that plague conventional composite materials are overcome in this instance as there is intimate connection between two carbon layers (see Fig.2a and 2b) . This also explains the extremely low resistance values measured along, and more importantly, through the CNT/AC paper.
- Fig. 10b indicates that a dense entanglement of CNTs have entirely covered the individual carbon fibers (Fig. 11) whilst still maintaining the overall porous microstructure of the carbon fiber paper.
- SEM image of the root/tip area of the fiber (Fig. 10c) highlights the extremely porous nature of the CNT network. This suggests that the deposited carbon nanotubes on each carbon fiber are all highly accessible during the electrochemical cycling process, significantly increasing the electroactive surface area, which is a key parameter for electrochemical devices.
- the tangled CNT/CFP composites are mechanically robust, without any visual signs of degradation, suggesting that the underlying carbon layer (formed during the CNT growth process) is strongly adhered to the carbon fiber network.
- the resulting CNT modified CFP can then be directly used as an electrode material in assembling electrochemical devices without further treatment. Alternatively, the modified CFP could also be used as a template for further chemical modification.
- a 1 cm 2 CNT/CFP electrode was assembled into a rechargeable Li-ion coin cell in an argon-filled glove box (Mbraum, Unilab, Germany) for battery testing (Neware, Electronic Co.) using 1.0 M LiPFg in ethylene carbonate/dimethyl carbonate (50:50) (Merch KgaA, Germany) as the electrolyte.
- the cell was cycled at room temperature between 0.0IV and 2.00V under different constant charge/discharge current densities (0.05, 0.10, 0.20, and 0.50 mA cm "2 ) for the time required to reach the potential limit.
- the reversible capacities as a function of the cycle number are shown in Fig. 13, demonstrating the viability of the CNT/CFP as an anode material.
- the initial reversible capacity is as high as 643 mAh g "1 under the constant discharge rate of 0.05 mA cm "2 .
- the electrochemical performance of the CNT/CFP electrode displayed an inherent long-term cycling stability, which is in stark contrast to the decrease in discharge capacity normally observed during the cycling of CNT-based electrodes 10 .
- the CNT/CFP electrode still demonstrated a significant, fully reversible capacity of 546 mAh g "1 (Fig.3a), which is much higher than the theoretical capacity of graphite (372 mAh g "1 ) when used as an anode 11.
- CNT electrodes produced using this new process will have significant impact in areas involving charge storage and/or transfer.
- Metal electrodes are of considerable commercial interest to the energy storage industry, e.g., copper foils for rechargeable batteries and aluminum for capacitors .
- the versatility of the process is demonstrated in Fig. 4 where it is shown that CNT/CL composite (using the growth parameters described previously) is produced directed on copper as well as other conductive and nonconductive substrates without further modification.
- a CNT/CL/Cu composite material is observed.
- the catalyst was only coated on half of the substrate to clearly show the underlying substrate.
- the contact resistance between the CL layer and the copper foil is approximately 1.0 to 2. O ⁇ and the resistance between the CNT web and the copper foil is in the same range.
- a major advantage of this new process is that it can produce 3D structured CNT/CL networks on any substrate providing two conditions are met: i) the substrate is capable of withstanding the growth temperature of the furnace (>600°C) ; and ii) the organic catalyst forms a stable thin film.
- the substrate is capable of withstanding the growth temperature of the furnace (>600°C) ; and ii) the organic catalyst forms a stable thin film.
- a major advantage of this process is that it can produce these CNT/AC films on any substrate providing two conditions are met: (i) the substrate is capable of withstanding the growth temperature of the furnace (>600°C) ; and (ii) , that the organic catalyst (Fe(III)TS) forms a stable thin film.
- the organic catalyst (Fe(III)TS) forms a stable thin film.
- the process for preparing these high-surface area CNT electrodes is simple, cost effective, and easy to scale.
- the CNT electrodes are expected to find use as flexible, thin supercapacitors and as anode materials for Li-ion rechargeable batteries and also in areas that require nanostructured electrodes for interfacing to biological systems in the pursuit of more effective nanobionic technologies .
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- 2007-12-14 KR KR1020097014204A patent/KR20090105924A/en not_active Application Discontinuation
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Also Published As
Publication number | Publication date |
---|---|
KR20090105924A (en) | 2009-10-07 |
CN101600646A (en) | 2009-12-09 |
JP2010512298A (en) | 2010-04-22 |
AU2007332084A1 (en) | 2008-06-19 |
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