WO2014167063A1 - Pile à combustible à accumulation de charges - Google Patents

Pile à combustible à accumulation de charges Download PDF

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Publication number
WO2014167063A1
WO2014167063A1 PCT/EP2014/057291 EP2014057291W WO2014167063A1 WO 2014167063 A1 WO2014167063 A1 WO 2014167063A1 EP 2014057291 W EP2014057291 W EP 2014057291W WO 2014167063 A1 WO2014167063 A1 WO 2014167063A1
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Prior art keywords
self
charging
anode
fuel cell
cathode
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PCT/EP2014/057291
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English (en)
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Sergey Shleev
Dmitrii PANKRATOV
Zoltan Blum
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Sergey Shleev
Pankratov Dmitrii
Zoltan Blum
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Publication of WO2014167063A1 publication Critical patent/WO2014167063A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8605—Porous electrodes
    • H01M4/8626—Porous electrodes characterised by the form
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61N—ELECTROTHERAPY; MAGNETOTHERAPY; RADIATION THERAPY; ULTRASOUND THERAPY
    • A61N1/00—Electrotherapy; Circuits therefor
    • A61N1/18—Applying electric currents by contact electrodes
    • A61N1/32—Applying electric currents by contact electrodes alternating or intermittent currents
    • A61N1/36—Applying electric currents by contact electrodes alternating or intermittent currents for stimulation
    • A61N1/372—Arrangements in connection with the implantation of stimulators
    • A61N1/378—Electrical supply
    • A61N1/3785—Electrical supply generated by biological activity or substance, e.g. body movement
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8663—Selection of inactive substances as ingredients for catalytic active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/16—Biochemical fuel cells, i.e. cells in which microorganisms function as catalysts
    • 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
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • This invention pertains in general to a fuel cell for use as a power source for miniaturized bio-devices, e.g. a bio-device comprising a contact lens and an electric circuit, where the electric circuit may incorporate components such as a sensor, an antenna, a microchip, an amplifier, and/or a transmitter.
  • a bio-device comprising a contact lens and an electric circuit
  • the electric circuit may incorporate components such as a sensor, an antenna, a microchip, an amplifier, and/or a transmitter.
  • Non-invasive sensing or evaluation of various biomarkers hold great promise for the future, especially if the information gathered can be effortlessly and accurately transferred to an external monitoring site. Focusing on non-invasiveness, and aiming at limited involvement of the individual, the combined efforts will revolutionize the maintenance and treatment of any number of ailments, not only diabetes. To that end, the strict spatial confinement of a contact lens, is singularly well suited as a test bed for the development of micro- and nano-sized implements, and will benefit all areas of realtime biomarker sensing.
  • the available pre-flight information on "smart" or “bionic” lenses refers to over-the-air power securement, based on RF coupling in particular.
  • Other over-the-air protocols not specifically involving lenses, draw on IR and ultrasound.
  • energy is collected by means of a suitable antenna and intrinsically relayed to the circuitry, i.e. the receiver/transmitter and sensor assembly; the results from the sensor are fed into the transmitter and the signal transmitted is eventually decoded in an external receiver.
  • An external RF transmitter (doubling as a data receiver/decoder), to be in some sense worn by the subject, provides the energy needed to drive the lens ensemble.
  • the remaining option is to generate the power necessary by converting in situ available energy into electric energy, i.e. drawing on the mainstay of fuel cell technology.
  • biofuels are present in the lachrymal fluid, e.g. ascorbic acid, dopamine, and glucose, albeit in limited supply.
  • Molecular oxygen (biooxidant) on the other hand, needed to accept the electrons extracted from the fuels, is abundantly available. Indeed, as early as in 2010 a PCT- application entitled “Flexible biofuel cell, device and method” was filed. The application relates to usage of biological fuel cells to power bionic contact lenses (cf. WO 2011/117357).
  • Glucose being the target molecule par excellence as regards the electronic lens protocols that are actively pursued, is a low abundance substance in lachrymal fluid, i.e. about 0.05 mM on average, even if earlier reported values are as high as 0.6 mM.
  • the present invention preferably seeks to mitigate, alleviate or eliminate one or more of the above-identified deficiencies in the art and disadvantages singly or in any combination and solves at least the above-mentioned problems by providing a self-charging fuel cell, which combines the advantages of both
  • the anode and the cathode of the fuel cell respectively comprises a conducting support, wherein said support has means for connecting the electrode to an electric circuit, the support further being provided with a catalyst and a structure for storage of electrical charges generated by a chemical reaction catalyzed by the catalyst, the catalyst being in electric connection with the conducting support and the material for storage of electrical charges.
  • the catalyst is a catalyst for oxidation of a first substrate to release electrons, wherein said electrons are absorbed by the structure for storage of charges, whereby the electrode acts as anode, i.e. negatively charged electrode, if contacted with said first substrate.
  • the catalyst is a catalyst for reduction of a second substrate to absorb electrons, wherein said electrons are released by the structure for storage of charges, whereby the electrode act as cathode, i.e. positively charged electrode, if contacted with said second substrate.
  • a new method for coincident electrical power generation and storage, without using electromagnetic induction, by direct transformation of chemical energy into electric energy, which is stored inside the same device using a hybrid capacitance based on reversible charge-transfer reactions and electrical double-layer capacitance, is disclosed.
  • the fuel cell can be used for short-time very high current and long-time lower current practical applications.
  • the fuel cell can be fabricated as a micro- or even nanoscale charge-storing fuel cell for biomedical devices, such as contact lenses operating in vivo and ex vivo.
  • Fig. 1 is a schematic illustration of a separate electrode 10 (either a negative or positive one), comprising a structure for capacitance 11, a catalyst 12 and a support 13;
  • Fig. 2 is a schematic illustration of a self-charged supercapacitor 20, a negatively polarized electrode 21 versus another one, a positively polarized electrode 22 versus a negative one, a electrical circuit 23 and a switch 24;
  • Fig. 3 is a plot with performance data for an electrode plantinum
  • nanoparticles/polypyrrole/carbon nanotubes based fabricated using polypyrrole/carbon nanotubes composite modified with platinum nanoparticles electrochemically synthesized on polypyrrole/carbon nanotubes;
  • Fig. 4 depicts scanning electron microscope images of a nanocomposite with and without a catalyst, 1 - polypyrrole/carbon nanotubes and 2 - platinum
  • Fig. 5 is a charge/discharge curve of a cathodic electrode based on platinum nanoparticles/polypyrrole/carbon nanotubes composite immobilized on gold electrode;
  • Fig. 6 depicts charge/discharge curves of an anodic electrode based
  • Fig. 7 is a scanning electron microscope image of a structure and a catalyst, polyaniline/carbon nanotubes composite immobilized on a gold electrode;
  • Fig. 8 is charge/discharge curve of an anodic electrode based
  • Fig. 9 is a charge/discharge curve for fuel-cell comprising a platinum nanoparticles/polypyrrole/carbon nanotubes based cathodic electrode and a
  • polyaniline/carbon nanotubes based anodic electrode submerged into 50 mM phosphate buffer, pH 7.4;
  • Fig. 10 is a charge/discharge curve for fuel-cell comprising a platinum nanoparticles/ carbon nanotubes based cathodic electrode and a polyaniline/carbon nanotubes based anodic electrode wherein the anode was submerged into 50 mM phosphate buffer, pH 7.4, and the cathode was submerged into 50 mM NaH 2 P0 4 , pH 4.7 ; Fig.
  • 1 1 is a principal scheme of a self-charging supercapacitor (the assembly is the same for a fuel cell) comprising an anodic electrode based polyaniline/carbon nanotubes composite immobilized on one gold electrode and a cathodic electrode based on platinum nanoparticles polypirrole/carbon nanotubes composite immobilized on another gold electrode;
  • Fig. 12 depicts photographs (I) and scanning electron microscopy images (II)
  • Fig. 13 depicts charge/discharge curves (discharging at a constant load of 500
  • a fuel-cell comprising a enzymatic (Corynascus thermophilus cellobiose dehydrogenase) cathodic electrode and a enzymatic (Myrothecium verrucaria bilirubin oxidase) anodic electrode (4 h charging)
  • a fuel-cell comprising a enzymatic (Corynascus thermophilus cellobiose dehydrogenase) cathodic electrode and a enzymatic (Myrothecium verrucaria bilirubin oxidase) anodic electrode (1 h charging) ;
  • Fig. 14 is a principal scheme of a fuel cell comprising a enzymatic (Corynascus thermophilus cellobiose dehydrogenase) cathodic electrode and a enzymatic
  • Fig. 15 is plot for comparison of various electrical devices (from Halper and Ellenbogen, 2006, with additions and changes);
  • Fig. 16 is a principal concept scheme of bioelectronics (adopted from Willner and Katz, 2005);
  • Fig. 17 depicts images of nanostrutured biomodified gold electrodes in various situations in vitro, ex vivo and in vivo (adopted from Framtidens forskning in Svenska Dagbladet, 20/06-2012);
  • Fig. 18 is a principal scheme of possible electron transfer pathways in a self- charging device.
  • Fig. 19 is an image of a structure and a catalyst according to an embodiment, which shows scanning electron microscopy image of platinum/polypyrrole/carbon nanotube nanocomposite - positively self-charging (by oxygen electroreduction) cathode.
  • Bioelectronics (Fig. 16) is a rapidly progressing interdisciplinary research field, which aims to integrate biomaterials (proteins, enzymes, organelles, living cells, etc.) and electronic elements into functional bioelectronic devices.
  • biomaterials proteins, enzymes, organelles, living cells, etc.
  • electronic elements such as electrodes, chips, and piezoelectric crystals
  • hybrid systems including biofuel cells, biosensors, biodiodes, biotransistors, or even bioelectronic circuitries.
  • Proteins and enzymes are surprisingly good electronic conductors, resembling the solid-state counterparts, or, in other words, they are per se "dopable" bio-electronic nanomaterials.
  • bioelectronic devices based on 3D nanobiostructures, viz. enzymatic fuel cells, biosensors, and even a biotransistor, have already been assembled and tested in vitro, ex vivo, and even in vivo in the art.
  • Electrochemical capacitors also called “supercapacitors” or “ultracapacitors” are rechargeable devices, which can store significantly larger amounts of electrical energy than conventional capacitors, reaching capacitance values as high as thousands of Farads (F).
  • the devices are nowadays designed using advanced, mostly carbon based nanomaterials, e.g. nanotubes, nanoparticles, graphene, etc. Carbon based
  • electrochemical capacitors are considered as revolutionary energy storage devices owing to their excellent properties, such as e.g. higher energy density and conductivity, lower cost, and robustness. Also, electrochemical capacitors can be considerably miniaturized while maintaining very high specific capacitances. It should be noted, however, that these devices do not produce electrical energy themselves and hence need to be charged externally. Thus, they are not suitable as power source for miniaturized devices, such as implants and non-invasive devices e.g. a contact lens with electronics.
  • enzymatic fuel cells are energy generating biodevices belonging to a biological fuel cell family that employs oxidoreductases as anodic and cathodic catalysts. Based on the electron interchange between electrodes and redox enzymes, enzymatic fuel cells are divided into two groups, viz. mediated and direct electron transfer (MET and DET, respectively) based biofuel cells.
  • the direct electron transfer group is of special interest, since such biodevices are membrane(separator)-, cofactor-, and mediator-less. Indeed, the direct electron transfer concept allows significant simplification and miniaturization, along with very low toxicity.
  • nanostructured electrodes based on carbon and metals e.g. carbon nanotubes and nanoparticles modified electrodes
  • carbon nanotubes and nanoparticles modified electrodes are currently used to design very efficient enzymatic fuel cells.
  • critical parameters achieved e.g. the power density of biological fuel cells in general and enzymatic fuel cells in particular, even for enzymatic fuel cells built from nanobiocomposites, are very far from those realized in
  • biofuel cells are their possible use as electric power sources for implanted devices, in which they could replace conventional limited life-time batteries, since the biofuels (e.g. glucose) and biooxidants (e.g. molecular oxygen) for biofuel cells are both readily available in living organisms.
  • biofuels e.g. glucose
  • biooxidants e.g. molecular oxygen
  • implanted biodevices will employ the same energy source and metabolic mechanism as the organism in question.
  • Several recent papers describe direct electron transfer based biofuel cells operating in animals, e.g. snails, clams, lobsters, and rats. However, the reported power densities (usually ⁇ 100 ⁇ W cm 2 ) are much lower compared to the biofuel cells tested in vitro.
  • both elements i.e. electrochemical and enzymatic fuel cell, are built from nano(bio)composites (Fig. 12), as described further below.
  • a polyaniline/carbon nanotubes composite was prepared.
  • Graphite foil was used as a supporting conducting material for the supercapacitor (Fig. 12A).
  • Fig. 12.BII shows a scanning electron microscope image of the polyaniline/carbon nanotubes composite immobilized on the graphite foil. A specific capacitance of about 110 F g "1 (0.6 F cm "2 ) was registered for the
  • nanobiostructures based on gold nanoparticles and two redox enzymes viz. Corynascus thermophilus cellobiose dehydrogenase and Myrothecium verrucaria bilirubin oxidase as cathodic and anodic bioelements, respectively, were prepared.
  • graphite foil was used to create three-dimensional (3D) bioanodes and biocathodes to further increase surface area and thus the capacitance of the electrodes (Fig. 12A).
  • Bilirubin oxidase was directly immobilized on gold nanoparticle modified electrodes (Fig. 14, right electrode) forming an efficient biocathode, known to operate in simple buffers and complex human physiological fluids.
  • the design of bioanodes is more involved and a modification of the gold nanostructured surface with a self-assembled thiol monolayer for proper immobilization of cellobiose dehydrogenase is essential (Fig. 14, left electrode).
  • the charge-storing fuel cell fabricated using graphite support and biodevices based on gold electrodes, show similar parameters, viz. 0.6 V OCV and a maximal power density of about 20 ⁇ W cm "2 at a cell voltage of about 0.5 V in 50 mM glucose.
  • the complete membrane-, separator-, cofactor-, mediator-less biodevice i.e. the charge-storing fuel cell
  • the open circuit voltage was monitored until a maximal value of about 0.4 V was obtained; stabilization of the voltage suggested that the charge-storing fuel cell was fully charged in ca. 2 h (Fig. 13, curve 2).
  • the charge-storing fuel cell was discharged by applying a constant load of 500 ⁇ , and the open circuit voltage drop was registered.
  • the initial current density delivered by the biodevice was 3.2 mA cm "2 .
  • Significant electric power (initially 1.2 mW cm "2 compared to ca.
  • the self-charging biosupercapacitor (charge-storing fuel cell) was also tested by charge/discharge cycling, using about 1 h charging time only.
  • the self-charging biosupercapacitor charge- storing fuel cell
  • the self-charging biosupercapacitor provided a maximum of 1.2 mW cm "2 at 0.38 V.
  • the power output was improved by a factor of about 60 in comparison to state-of-the-art biofuel cells, albeit operating in pulsed power mode.
  • biosupercapacitors operating in solutions containing different alcohols, carbohydrates, or other energy rich compounds.
  • a similar approach can be used to design biosupercapacitors operating in solutions containing different alcohols, carbohydrates, or other energy rich compounds.
  • biofuels e.g. glucose
  • the concept is not limited thereto.
  • a self-charging capacitor or charge-storing fuel cell charges both electrodes in the self- charging fuel cell simultaneously, using different catalysts and a method for operating a self-charging capacitor (charge-storing fuel cell).
  • a charge-storing fuel cell 20 comprises a self-charging anode 21 and a self-charging cathode 22.
  • the anode 21 comprises a conducting support 13.
  • the support 13 has means for connecting the anode 21 to an electric circuit 23.
  • the support 13 is further provided with a catalyst 12 and a structure 11 for storage of electrical charges.
  • the charges are generated by a chemical reaction catalyzed by the catalyst 12, the catalyst 12 being in electric connection with the conducting support 13 and the material for storage of electrical charges 11.
  • the catalyst 12 is a catalyst 12 for oxidation of a first substrate. This release electrons, and the electrons are absorbed by the structure 11 for storage of charges, whereby the electrode 10 acts as anode 21 (i.e.
  • the self-charging cathode 22 comprises a conducting support 13.
  • the support 13 has means for connecting the cathode 22 to an electric circuit 23.
  • the support 13 is further provided with a catalyst and a structure 11 for storage of electrical charges.
  • the charges are generated by a chemical reaction catalyzed by the catalyst 12, the catalyst 12 being in electric connection with the conducting support 13 and the material 11 for storage of electrical charges.
  • the catalyst 12 is a catalyst 12 for reduction of a second substrate. This absorbs electrons, and the electrons are released by the structure 11 for storage of charges, whereby the electrode 10 act as cathode 22 (i.e. positively charged electrode), if contacted with said second substrate.
  • the special advantage for both having a bioanode and biocathode includes reaching high enough voltage/current (power/effect) for a contact lens application. While the steady state voltage /current not will differ from conventional bio-fuel cells, the ability to store charges implies that higher voltages (currents), and also and more importantly higher effects may be reached temporarily. Typically, as already discussed, the time over which the effect may be increased is sufficient to operate miniaturized circuitry, such as biosensors implemented in a contact lens, intermittently. As can be seen from the appended figures, the voltage (i.e.
  • microbial fuel cells i.e. fuel cells having an electrode (anode) based on living electrochemically active microorganisms
  • microbial fuel cells can be improved by making use of capacitive anodes with electrochemically active microorganisms.
  • capacitive anodes enable renewable energy storage in microbial fuel cells.
  • the performance of the electrodes was not significantly improved. For instance, the obtained current densities were 1.02 ⁇ 0.04 A/m 2 for capacitive electrodes compared to 0.79 ⁇
  • the present inventors were able to design novel devices, self-charging capacitors, or, in other words, charge-storing fuel cells, significantly improving the performance of the conventional fuel cell. Further, by providing electrodes not merely relying on the double-layer capacitor principle, but hybrid capacitance, the performance of the fuel cell could be improved even further, as discussed more in detail below.
  • biosupercapacitors are based on "green" natural renewable catalysts, redox enzymes, which can be produced at very low costs.
  • biodevices i.e. biofuel cells, bio-batteries, and also biosupercapacitors, compared to conventional devices, is scientifically insignificant, but practically extraordinary important. According to an EU regulation, conventional batteries cannot be used in disposable devices (European Union Directive 2006 on Batteries and Accumulators (http://www.epa.gov). Because of this law many electronic companies in Europe (including Swedish companies, e.g.
  • the charge-storing fuel cell or alternatively, the self- charging capacitor, is built from high-end nanomaterials in a monocoque fashion, i.e. the fuel cell electrodes also serve as the capacitor.
  • hybrid capacitance i.e. double layer as well as electrochemical charging of the capacitor entity, is relied on, thus enabling the storage of significant amounts of electric energy.
  • the fuel cell component draws on bioanodes and biocathodes with immobilized enzymes working in direct electron transfer modes, eliminating the need for mediators and making the electrode-enzyme interaction straightforward and less technically demanding.
  • the conducting support of the self-charging anode is made from a metal.
  • a metal is e.g. gold, silver, platinum, copper, or nickel.
  • Carbon based materials can be also employed, or combinations, or composites thereof.
  • the conducting support of the self-charging cathode may be made from a metal, e.g. gold, silver, platinum, copper, or nickel, a carbon based material, or combinations or composites thereof.
  • the charge-storing fuel cell has a conducting support of the self-charging cathode with a conductivity of from 10 to 630,000 S cm 1 .
  • the conducting support of the self-charging cathode may have a conductivity of from 10 to 630,000 S cm "1 .
  • the first group includes materials with an extended electrical double layer (EDL) wherein capacitive effect occur at the electrode/electrolyte interface (electrostatically), e.g. activated carbons, carbon nanotubes, carbon fibers, graphene etc. [G. Lota, K. Fic, E. Frackowiak. Energy
  • the second group consists of so-called pseudocapacitive materials (transitional metal oxides, nitrides and conducting polymers), where capacitance is realized by Faradaic reactions at the electrode/electrolyte interface, in addition to the double layer capacitance [D. Choi, G. Blomgren, P. Kumta. Advanced Materials, 2006, 18, 1178- 1182; A. Rudge, J. Davey, I. Raistrick, S. Gottesfeld, J. Ferraris. J. Power Sources, 1994, 47, 89-107.].
  • Metal oxides and nitrides have high specific capacitance but their usage is limited under ex vivo conditions, e.g. in contact lenses, because of high specific weight and high toxicity.
  • hybrid materials which combine the pseudocapacitive effect and electrical double layer capacitance are the way to increase the overall specific capacitance and stability during the charge/discharge process.
  • the structure of the self-charging anode for storage of electrical charges is designed in manner such that electric energy may be stored electrostatically and electrochemically.
  • the structure of the self- charging cathode for storage of electrical charges is designed in manner such that electric energy may be stored electrostatically and electrochemically.
  • the structure of the self-charging anode for storage of charges may comprise a conductive polymer.
  • the structure of the self-charging cathode for storage of charges may comprise a conductive polymer.
  • the backbone of such conductive polymers may consists of conjugated aromatic cycles, such as polypyrrole, polyfluorene, polyphenylene, polypyrene, polyazulene, polynaphthalene, polycarbazole, polyindole, polyazepine, polythiophene, poly(3,4-ethylenedioxythiophene), poly(p-phenylene sulfide), polystyrene and their derivatives, or/and copolymers thereof, conjugated double bonds, such as polyacetylene and its derivatives, conjugated aromatic cycles and double bonds, such as poly(p-phenylenevinylene) and its derivatives, etc.
  • the structure for storage of charges of the self-charging anode and/or cathode comprise a conductive material having intrinsic electrostatic capacitance from 10 F g "1 up to 1000 F g "1 ;
  • Examples of materials for providing such properties include carbon nanotubes and nanohorns, metal and alloy nanoparticles, graphene, nanoporous and mesoporous metal and carbon electrodes.
  • the self-charging anode and/or the self-charging cathode comprises a combination of a conductive material having intrinsic electrostatic capacitance from 10 F g "1 up to 1000 F g "1 ; preferably also with a highly developed surface from 10 m 2 kg "1 up to 1000 m 2 kg "1 , e.g. carbon nanotubes and nanohorns, metal and alloy nanoparticles, graphene, nanoporous and mesoporous metal and carbon electrodes, and a conductive polymer, e.g.
  • a conductive polymer having a backbone consisting of conjugated aromatic cycles such as polypyrrole, polyfluorene, polyphenylene, polypyrene, polyazulene, polynaphthalene, polycarbazole, polyindole, polyazepine, polythiophene, poly(3,4-ethylenedioxythiophene), poly(p-phenylene sulfide), polystyrene and their derivatives, or/and copolymers thereof, conjugated double bonds, such as polyacetylene and its derivatives, conjugated aromatic cycles and double bonds, such as poly(p-phenylenevinylene) and its derivatives.
  • conjugated aromatic cycles such as polypyrrole, polyfluorene, polyphenylene, polypyrene, polyazulene, polynaphthalene, polycarbazole, polyindole, polyazepine, polythiophene, poly(3,4-ethylenedioxythiophene), poly(p-phenylene
  • hybrid materials manifest impressive biocompatibility in cell cultures and even in human blood, while carbon nanomaterials are well known catalysts for the generation of active oxygen species, which makes the perspective of their usage in contact lenses in direct contact with tear fluid dubious.
  • the catalyst of the self- charging anode is selected from the group consisting of of inorganic catalysts, such as nanoparticles of metals, alloys and metal oxides and nanotubes of metal, alloys, and metal oxides, organic catalysts, such as tetracyanoquinodimethane, tetrathiafulvalene, and polyaniline, or/and biological materials, e.g. redox proteins, such as cytochromes, azurin, and plasocyanin, redox enzymes, such as dehydrogenases (e.g. cellobiose and glucose dehydrogenases), oxidases, such as pyranose and glucose oxidases.
  • the catalyst of the self-charging anode is selected from the group consisting of organic catalysts, such as
  • redox enzymes such as cellobiose and glucose dehydrogenases, pyranose and glucose oxidases.
  • the catalyst of the self- charging cathode is selected from the group consisting of inorganic catalysts, such as nanoparticles of metals, alloys, and metal oxides, and nanotubes of metals, alloys, and metal oxides; organic catalysts, such as quinines; or/and biological materials, e.g. redox proteins, such as cytochromes, myoglobin, or haemoglobin, redox enzymes, such as multicopper oxidases (e.g. laccase, bilirubin oxidase, ascorbate oxidase, ceruloplasmin, or tyrosinase), or terminal cytochrome c oxidase.
  • inorganic catalysts such as nanoparticles of metals, alloys, and metal oxides, and nanotubes of metals, alloys, and metal oxides
  • organic catalysts such as quinines
  • biological materials e.g. redox proteins, such as cytochromes, myoglobin
  • the catalyst of the self-charging cathode is selected from the group consisting metals, alloys, and metal oxides, and nanotubes of metals, alloys, and metal oxides; or/and biological materials, e.g. redox enzymes, such as multicopper oxidases (e.g. laccase, bilirubin oxidase, ascorbate oxidase, ceruloplasmin, or tyrosinase), or terminal cytochrome c oxidase.
  • multicopper oxidases e.g. laccase, bilirubin oxidase, ascorbate oxidase, ceruloplasmin, or tyrosinase
  • terminal cytochrome c oxidase e.g. laccase, bilirubin oxidase, ascorbate oxidase, ceruloplasmin, or tyrosinase
  • a charge-storing fuel cell can have a self-charging anode built from just one material.
  • an anode can be based only on conducting organic polymers, e.g. doped polyaniline. This polymer is highly conducting (e.g., a few mS cm "1 , thus, it can serve as a conducting support for connecting the electrode to an electric circuit. It also has high
  • electrochemical capacitance up to 3400 F g "1 (vide supra), and serves as a structure for storage of electrical charges. It is also a good electrocatalyst for different fuels, e.g., ascorbate, which is present in human lachrymal liquid at high concentrations.
  • a self- charging cathode can be made from a metal, e.g. nano-/mesoporous platinum. Metals are highly conducting and they usually serve as a conducting support for connecting the electrode to an electric circuit. Platinum is a very good electrocatalyst for oxygen electroreductions directly to water without formation of highly reactive oxygen species.
  • the first and second substrate is provided by submerging the anode and the cathode into a solution comprising said first and second substrate.
  • a solution is for example an aqueous solution, comprising said first and second substrate.
  • a solution is preferably a body fluid, such as blood, sweat, saliva, and specifically human lachrymal liquid.
  • the first substrate of the charge-storing fuel cell is selected from a group consisting of glucose, ascorbate, and dopamine, which is available in several body fluids.
  • the second substrate of the charge-storing fuel cell is oxygen, which is found in aqueous solutions such as body fluids.
  • typical catalysts include gold or enzymes (glucose oxidase, glucose dehydrogenase) for glucose, polyaniline or tetrathiafulvalene for ascorbate, and ferrocene for dopamine.
  • typical catalysts include platinum or enzymes (multicopper oxidases, cytochrome terminal oxidase) for oxygen.
  • the designed nanocomposites will have a very high specific double layer capacitance because of the large surface area.
  • nanomaterials will be further modified with suitable conducting organic polymers, e.g. polyaniline, polypyrrole, polythiophene and substituted derivatives thereof, i.e. redox active nanocomposites will be produced.
  • suitable conducting organic polymers e.g. polyaniline, polypyrrole, polythiophene and substituted derivatives thereof, i.e. redox active nanocomposites will be produced.
  • suitable conducting organic polymers e.g. polyaniline, polypyrrole, polythiophene and substituted derivatives thereof, i.e. redox active nanocomposites will be produced.
  • redox active nanocomposites will be produced for synthesis of organic polymers chemical and enzymatic procedures will be employed using previously developed protocols.
  • two types of nanobiocomposite will be assembled, i.e. anodic and cathodic, based on glucose oxidizing and oxygen reducing enzymes, viz. glucose oxidase (EC 1.1.3.4), cellobiose dehydrogenase (EC 1.1.99.18), and glucose dehydrogenase (EC 1.1.5.2), as well as blue multicopper oxidases, viz. laccase (EC 1.10.3.2) and bilirubin oxidase (EC 1.3.3.5).
  • glucose oxidase EC 1.1.3.4
  • cellobiose dehydrogenase EC 1.1.99.18
  • glucose dehydrogenase EC 1.1.5.2
  • blue multicopper oxidases viz. laccase (EC 1.10.3.2) and bilirubin oxidase (EC 1.3.3.5).
  • the structure of the self-charging anode for storage of electrical charges and said catalyst of the self-charging anode are in electric connection with each other via the conducting support and not directly.
  • the structure of the self-charging cathode for storage of electrical charges and said catalyst of the self-charging cathode may be in electric connection with each other via the conducting support and not directly.
  • the bioelectrodes can be either bioanodes, storing electrons from
  • both electrodes need to be three-dimensional, and also intrinsically redox active, i.e. they should be able to handle parallel capacitive processes and store electric energy electrostatically (due to double layer capacitance), as well as electrochemically (due to reversible faradaic charge-transfer reactions) (Fig. 18).
  • bioelectrocatalytic function the electrodes should be properly modified with suitable bioelements, i.e. active and stable anodic (biofuel oxidizing) and cathodic (biooxidant reducing) redox enzymes (Fig. 18). Electric connection between bioelements and electrodes
  • bioanodes and biocathodes may be done by varying the ratios between nanomaterials, redox enzymes, and organic polymers in synthesized nanobiocomposites.
  • the following parameters may be targeted: (i) enzymatic fuel cell mode - current densities close to mA cm "2 , open circuit potentials of the cathode and anode, -400 mV and +800 mV, respectively (pH 7.4), and long-term stability of the electrodes more than 10 days in operation with month shelf life time; (ii) electrochemical capacitor mode - specific capacitance close to 500 F g "1 and a half self- discharge time close to a month.
  • the capacitor and the biofuel cell both are built from nanobiocomposites, viz. polyaniline/carbon nanotubes and redox enzymes/gold nanoparticles.
  • the self-charged, membrane- and mediator-less biosupercapacitor operating in a glucose containing buffer (pH 7.4) provides a maximum power density of 1.2 mW cm "2 at an operating voltage of 0.38 V.
  • Embodiments of the present invention does not only relate to the charge storing fuel cell as such, but also to methods for operating it. As has been shown the fuel cell may be operated intermittently to provide an increased effect.
  • operating of the charge storing fuel cell as described herein thus comprises the steps of: (a) Providing a first substrate to the anode, whereby charging of the anode is initiated, (b) Providing a second substrate to the cathode, whereby charging of the cathode is initiated, (c) Closing the electric circuit for a first time, whereby the fuel cell starts to discharge and a current flows through the electric circuit, (d) Disconnecting the electric circuit while a first substrate to the anode and a second substrate to the cathode are still provided, (e) Closing the electric circuit for a second time, whereby the capacitor or fuel cell starts to discharge once more and a current flows through the electric circuit, (f) Optionally repeating steps (d) and (e) one or several times.
  • the circuit of the fuel cell is closed before the voltage over the anode and cathode ceases to increase. This can be seen in the charge/discharge curve of a fuel cell in figure 10. Between points (4) and (5) of figure 10, the voltage increases during charging, and at (5) the circuit is closed while the voltage over the anode and cathode is still increasing.
  • the circuit of the fuel cell is closed once the voltage over said anode and cathode is at least 10% of the maximum voltage at steady state, but less than 90% of the maximum voltage at steady state. Run in this way, the fuel cell can drive a component with a higher power demand, for instance a transmitter, in a pulsed manner, when sufficient power has been stored.
  • the first and second substrate is provided by submerging the anode and the cathode into a solution comprising said first and second substrate.
  • a solution is aqueous.
  • the first and second substrate may be provided by applying the lens to the eye of the intended wearer.
  • the circuit of the fuel cell is disconnected before the voltage over the anode and cathode ceases to decrease. This can be seen in the charge/discharge curve of a fuel cell in figure 10. Between points (3) and (4) of figure 10, the voltage decreases during discharge, and at (4) the circuit is disconnected before the voltage over the anode and cathode ceases to decrease. In this manner, the fuel cell is operated only when providing power increased over the steady state.
  • the charge storing fuel cell or capacitor is operated with the circuit closed, and under provision of said first and second substrate, after the voltage over the anode and cathode has ceased to decrease, i.e. running the charge storing fuel cell at steady state after discharging. In this way, the fuel cell can continuously drive a component with a low power demand.
  • the anode and the cathode not also are charged by applying voltage over them. This could be beneficial if there is a power surplus from another charge generating apparatus.
  • Nitrogen additionally purified using a Gas Clean Filters from Varian BV (Middelburg, Netherlands), and oxygen were obtained from AGA Gas AB
  • phosphate buffer saline 50 mM phosphate buffer, pH 7.4, containing 0.15 M NaCl (phosphate buffer saline) was prepared with water (18 ⁇ cm) purified with a PURELAB UHQ II system from ELGA Labwater (High Wycombe, UK).
  • thermophilus cellobiose dehydrogenase and Myrothecium verrucaria bilirubin oxidase were obtained as kind gifts from Dr. Roland Ludwig (Vienna, Austria) and Amano Enzyme Inc. (Nagoya, Japan), respectively.
  • Electrochemical measurements were carried out using a ⁇ Type
  • Ultrasonication has been done using Ultrasonic Cleaner XB2 from VWR International Ltd. (East Grinstead, West Wales, UK).
  • SEM images were obtained using a high resolution scanning electron microscope EVO LS 10 from Zeiss in field immersion mode at 15 kV accelerating voltage and 36 pA current.
  • SEM images were obtained using a high- resolution scanning electron microscope, Nova NanoLab 600 from FEI (Hillsboro, OR, USA) in field immersion mode at 15 kV accelerating voltage and 36 pA beam current.
  • Polyaniline/carbon nanotube composite was prepared following a previously published protocol [L. Li, Z.-Y. Qin, X. Liang, Q.-Q. Fan, Y.-Q. Lu, W.-H. Wu, M.-F. Zhu, J. Phys. Chem. C 2009, 113, 5502 - 5507]. Briefly, carbon nanotubes were heated at 90°C with concentrated (65%) nitric acid for 5 h, cooled, filtered, washed with deionised water and acetone, and finally dried at 110°C for 5 h.
  • FIG 12 depicting a photograph of the foil (A) modified with the polyaniline/carbon nanotube composite (B) purchased from Mineral Seal Corp.
  • NanoTechCentre Ltd. (Tambov, Russia) had outer and inner diameters of 20-50 and 5- 10 nm, respectively, with lengths up to 2 ⁇ .
  • the precipitated polypyrrole/carbon nanotube composite was filtered off and washed with distilled water and ethanol and finally dried at 75°C for 24 h. Fabricated composite was dispersed in ethanol (5 mg ml "1 ) under the ultrasonication for 5 h and pipetted on the top of gold electrode (0.3 mg). The thus obtained polypyrrole/carbon nanotube composite was immobilized on gold electrode by direct physical absorption from ethanol suspension. After drying the electrode was submerged into 1 mM K 2 PtCl 6 solution with 0.1 M KC1 as the supporting electrolyte. Electrodeposition of platinum on the polypyrrole/carbon nanotube surface was implemented by applying 9 potential steps from 0.5 to -0.7 V with the duration time of each step of 400 s. Thus, platinum nanoparticle/polypyrrole/carbon nanotube composite modified gold electrode was obtained serving as a charge-storing cathodic electrode.
  • Gold nanoparticles with an average diameter of about 60 nm were synthesized following a previously reported citrate-reduction procedure.
  • Fuel cell comprising a platinum nanoparticle/polypyrrole/carbon nanotube based cathodic electrode and a polyaniline/carbon nanotube based anodic electrode
  • a charge-storing fuel cell was provided (cf. FIG 11).
  • the fuel cell may also be seen as self-charged supercapacitor depending on how it is operated.
  • Fuel cell comprising a enzymatic (Corynascus thermophilus cellobiose dehydrogenase) cathodic electrode and a enzymatic (Myrothecium verrucaria bilirubin oxidase) anodic electrode
  • the fuel cell comprises a support (carbon foil), a structure (polyaniline/carbon nanotubes composite), as well as anodic and cathodic biological catalysts (cellobiose
  • the electrochemical capacitor was built using a graphite foil modified with a
  • the structure bilirubin oxidase in FIG. 14 was taken from the know crystal structure (PDB 2XLL) and cellobiose dehydrogenase was rendered using the cytochrome and the FAD domains of the enzyme from Phanerochaete chrysosporium (PDB 1D7D and lNAA, respectively). Protein globule - ribbons; copper ions - in spheres, heme - in spheres, FAD - in spheres, and carbohydrates - sticks.
  • the performance of the polyaniline/carbon nanotube based electrode according to above was assessed by submerging the electrode into phosphate buffer saline, pH 7.4 and recording its potential over time. Charge/discharge curves were obtained (cf. FIG. 6) for: 1 - polyaniline/carbon nanotube based electrode charging at a constant current density of 10 mA g "1 and discharging at a constant load of 10 kD.
  • the composite material based electrode can be externally charged and discharged many times, i.e. the electrode is functioning as an anode of a supercapacitor.
  • polyaniline/carbon nanotube based electrode submerged into 1 mM ascorbic acid in phosphate buffer saline, pH 7.4 using the following sequence:
  • the electrode can be self-charged without external charging.
  • the composite material based electrode can be self-charged and externally discharges many times.
  • the polyaniline/carbon nanotubes composite immobilized on a gold electrode was studied by scanning electron microscopy.
  • the polyaniline/carbon nanotubes composite immobilized on a gold electrode has a core-shell structure, a uniform non-agglutinated polyaniline layers on carbon nanotubes, maximizing the active capacitive surface.
  • the electrode composed of polyaniline/carbon nanotubes had specific capacitance of about 110 F g "1 (0.6 F cm “2 ), when the separator-less device was employed in air saturated phosphate buffer saline/glucose at pH 7.4. This value is expected for polyaniline/carbon nanotubes based supercapacitors using carbon supports, with typical specific capacitances of a few hundreds F g "1 .
  • the capacitive performance of the electrode was assessed by submerging the electrode into solution of 50 mM glucose/phosphate buffer saline, pH 7.4 by charge/discharge cycling during 95 min, showing initial (at the discharge onset) and final (at the end of the discharging process) power outputs equal to 740 ⁇ W cm “2 and 38 ⁇ W cm “2 , respectively, with excellent reproducibility at least for four cycles (Fig. 13, curve 1).
  • the composite material based electrode can be externally charged and discharged many times, i.e. the electrode is functioning as a cathode of a supercapacitor.
  • curve 2 the open circuit potential of the composite material based electrode increases, when the electrode is submerged in an oxidant (molecular oxygen) containing solution, i.e. the electrode can be self-charged without external charging.
  • curve 2 the composite material based electrode can be self-charged and externally discharges many times.
  • the surface of the platinum nanoparticle/polypyrrole/carbon nanotube (1- without platinum (ctrl.) and 2 - with platinum) composite was studied by scanning electron microscopy. As can be seen from FIG 4 the surface of the composite is different in the presence//absence of platinum (catalyst).
  • Charge/discharge curve for the self-charging fuel cell submerged into 50 mM phosphate buffer saline, pH 7.4 (cf. FIG. 9) was provided by:
  • the measured open circuit voltage of the charge- storing fuel cell increases, when the device is submerged into a fuel/oxidant
  • the device When the circuit is closed, the device is discharging providing electrical power with a concomitant voltage drop.
  • charge/discharge curve for the self-charging fuel cell wherein the anode was submerged into 50 mM phosphate buffer, pH 7.4, whereas the cathode was submerged into 50 mM NaH 2 P0 4 , pH 4.7 was provided by:
  • the device When the circuit is closed, the device is discharging providing electrical power with a concomitant voltage drop.
  • the enzymatic fuel cell was evaluated in air saturated phosphate buffer saline containing 50 mM glucose.
  • the open circuit voltage was monitored until a maximal value of about 0.4 V was obtained; stabilization of the voltage suggested that the fuel- cell was fully charged in ca. 2 h (Fig. 13, curve 2).
  • the fuel-cell was discharged by applying a constant load of 500 ⁇ , and the open circuit voltage drop was registered.
  • the initial current density delivered by the fuel-cell was 3.2 mA cm "2 .
  • Significant electric power (initially 1.2 mW cm “2 compared to ca. 0.02 mW cm “2 obtained for the glucose/oxygen gold nanoparticle direct electron transfer based bio fuel cell under the same conditions) was supplied by the self-charging
  • biosupercapacitor for at least 50 min with an obvious drop in the power density down to the 20 ⁇ W cm "2 biofuel cell base level.
  • the fuel cell was also tested by charge/discharge cycling, using about 1 h charging time only. Initial (at the onset) and final (at the end of discharging process) power outputs of about 0.42 mW cm “2 and 0.04 mW cm “2 , respectively, were reproducibly recorded, even though some degradation of the biodevice was observed (Fig. 13, curve 3). To conclude, an unprecedented and highly efficient self-charging biodevice was realized, characterized, and tested. The fuel cell provided a maximum of 1.2 mW cm "2 at 0.38 V. Thus, the power output was improved by a factor of 60 in comparison to state-of-the-art biofuel cells, albeit operating in pulsed power mode.
  • Mathematical modeling is done based on prevalent (bio)electrochemical appreciations of complex redox systems including the De Levie and Butler- Volmer models, as well as Marcus theory of electron transfer using MathCAD 15 program.
  • Faradaic responses from both bioelements and conducting organic polymers will be analyzed, assuming a correspondence to a reversible electron transfer process using Marcus theory and the Butler- Volmer model, or, alternatively, an irreversible electron transfer process:
  • l ° at is the current of the biocatalytic l diff j s me diffusion limited current.
  • i ET nFA mal k o r exp p ( E E ') j (according to the Butler-Volmer model,
  • i ET riFA real k o rex (1 a)n'F(E E"') j (according to the Butler-Volmer model,
  • (' ) can be calculated taking into account the standard Marcus equation for nonadiabatic electron transfer in combination with the Fermi-Dirac distribution, since electron transfer can occur to or from any Fermi level of the electrode:
  • a self-charging and charge-storing electrode comprising a conducting support, wherein said support has means for connecting the electrode to an electric circuit, the support further being provided with a catalyst and a structure for storage of electrical charges generated by a chemical reaction catalyzed by the catalyst, the catalyst being in electric connection with the conducting support and the material for storage of electrical charges, wherein
  • the catalyst is a catalyst for oxidation of a first substrate to release electrons, wherein said electrons are absorbed by the structure for storage of charges, whereby the electrode acts as anode, i.e. negatively charged electrode, if contacted with said first substrate; or
  • the catalyst is a catalyst for reduction of a second substrate to absorb electrons, wherein said electrons are released by the structure for storage of charges, whereby the electrode act as cathode, i.e. positively charged electrode, if contacted with said second substrate.
  • said structure for storage of charges comprises a conductive material having intrinsic electrostatic capacitance from 10 F g "1 up to 1000 F g "1 ; preferably with a highly developed surface from 10 m 2 kg "1 up to 1000 m 2 kg "1 .
  • said conductive material is a nanomaterial, such as carbon nanotubes and nanohorns, metal and alloy nanoparticles, graphene, nanoporous and mesoporous metal and carbon electrodes.
  • said structure for storage of charges comprises a conductive polymer.
  • the polymer backbone of said conductive polymer consists of conjugated aromatics, such as polypyrrole, polyfluorene, polyphenylene, polypyrene, polyazulene, polynaphthalene, polycarbazole, polyindole, polyazepine, polythiophene, poly(3,4- ethylenedioxythiophene), poly(p-phenylene sulfide), polystyrene and their derivatives, or/and copolymers thereof, conjugated double bonds, such as polyacetylene and its derivatives, conjugated aromatics and double bonds, such as poly(p-phenylenevinylene) and its derivatives, etc.
  • conjugated aromatics such as polypyrrole, polyfluorene, polyphenylene, polypyrene, poly
  • said structure for storage of charges comprises a combination of a conductive material according to example 5 or 6, and a conductive polymer according to example 7 or 8; preferably the conductive polymer being immobilized on the conductive material.
  • the catalyst is connected to the conducting support at a distance of less than 3 nm between the support and the catalyst; preferably no electron shuttle is being present between the catalyst and the conducting support.
  • said conducting support is made from a metal, e.g. silver, copper, nickel, platinum, or gold, a carbon based material, or combinations or composites thereof.
  • said first substrate is selected from the group consisting of hydrogen; ascorbate; carbohydrates, e.g. glucose, fructose, lactose, sucrose, maltose, cellulose, or starch; alcohols, e.g.
  • methanol, ethanol, propanol, pentanol isopropyl alcohol, butyl alcohol, ethane- 1,2-diol, propane- 1,2-diol, prop-2-ene-l-ol, 3,7-dimethylocta-2,6-dien-l-ol, cyclohexane- 1,2,3, 4,5, 6-hexol, or 2 - (2-propyl)-5-methyl-cyclohexane-l-ol;
  • neurotransmitters e.g. dopamine, epinephrine, histamine, serotonin, acetylcholine, adenosine, anandamide, or nitric oxide
  • amino acids e.g. gycine, leucine, histidine, lysine, phenylalanine, tyrosine, proline, asparagine, glutamine, or its derivatives.
  • redox proteins cytochromes, azurin, plasocyanin, etc
  • redox enzymes dehydrogenases (cellobiose and glucose dehydrogenases), oxidases (pyranoseand glucose oxidases, etc), organelles (mitochondria, chloroplasts, etc), and whole living cells.
  • redox proteins cytochromes, myoglobin, haemoglobin, etc
  • redox enzymes multicopper oxidases (laccase, bilirubin oxidase, ascorbate oxidase, ceruloplasmin, tyrosinase,etc), terminal cytochrome c oxidase, etc), organelles (mitochondria, peroxisomes, etc) and whole living cells.
  • a self-charging capacitor said capacitor comprising a self-charging anode according to any one of the examples 13 to 15, and a self-charging cathode according to any one of the examples 16 to 18, the self-charging capacitor having a first and a second means for connecting the anode and the cathode, respectively, to an electric circuit.
  • a charge-storing fuel cell said fuel cell comprising a self-charging anode according to any one of the examples 13 to 15 and a self-charging cathode according to any one of the examples 16 to 18, the charge-storing fuel cell having a first and a second means for connecting the anode and the cathode, respectively, to an electric circuit.
  • steps d) and e) optionally repeating steps d) and e) one or several times.
  • method further comprises the step of operating the fuel cell or capacitor with the circuit closed and under provision of said first and second substrate also once the voltage over said anode and cathode has ceased to decrease, i.e. at steady state after discharging.

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Abstract

L'invention concerne une électrode pour la génération et l'entreposage synchrones d'énergie électrique, sans utiliser d'induction électromagnétique, par la transformation directe d'énergie chimique en énergie électrique et l'entreposage de celle-ci dans le même dispositif, à l'aide d'une caractéristique de capacité hybride basée sur des réactions à transfert de charges réversibles et une capacité électrique à double couche. L'invention concerne également une pile à combustible à autochargement basée sur des électrodes à double fonction pour l'extraction et l'entreposage d'électricité à partir de systèmes biologiques et artificiels. La pile à combustible peut être utilisée en association avec des fluides biologiques, tels que le sang, la sueur, la salive et le liquide lacrymal ainsi qu'avec des fluides artificiels comprenant des jus et des liqueurs, contenant de substrats riches en énergie tels que des hydrates de carbone, des alcools et des aminoacides.
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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106450399A (zh) * 2016-11-11 2017-02-22 青岛大学 一种基于微生物表面共展示顺序酶的高性能淀粉/氧气燃料电池
WO2017062272A1 (fr) * 2015-10-06 2017-04-13 Case Western Reserve University Électrodes à capacité de charge élevée conçues pour permettre un blocage de conduction nerveuse par courant continu
CN109307699A (zh) * 2018-09-21 2019-02-05 西北师范大学 基于埃洛石纳米管和石墨烯的电化学传感器的制备和应用
CN109742411A (zh) * 2018-12-06 2019-05-10 东南大学 一种多巴胺修饰石墨烯微生物燃料电池阳极的制备方法
CN109881484A (zh) * 2019-02-02 2019-06-14 东华大学 一种静电负载的多层涂层纱线或织物材料的制备方法
CN110071297A (zh) * 2019-04-29 2019-07-30 西安交通大学 一种微生物燃料电池生物阳极及其制备方法
CN112310333A (zh) * 2019-07-23 2021-02-02 珠海冠宇电池股份有限公司 一种硫化物极片材料、其制备方法及锂电池
CN114023981A (zh) * 2021-07-26 2022-02-08 中国人民解放军军事科学院军事医学研究院 复合催化级联反应在葡萄糖燃料电池中的应用
WO2023137278A1 (fr) * 2022-01-11 2023-07-20 University Of Maryland, Baltimore Applications de formiate déshydrogénase o2 insensible

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004079848A2 (fr) * 2003-03-03 2004-09-16 Yissum Research Development Company Of The Hebrew University Of Jerusalem Nouvelle electrode presentant une sortie de puissance commutable et accordable et pile a combustible utilisant cette electrode
WO2007147947A2 (fr) * 2006-06-19 2007-12-27 Valtion Teknillinen Tutkimuskeskus Structures de film mince innovantes
WO2008058165A2 (fr) * 2006-11-06 2008-05-15 Akermin, Inc. Ensembles empilages de bioanodes et de biocathodes
WO2009131452A1 (fr) 2008-04-24 2009-10-29 Stichting Wetsus Centre Of Excellence For Sustainable Water Technology Dispositif et procédé permettant de réaliser une réaction électrochimique biologiquement catalysée
WO2011117357A2 (fr) 2010-03-24 2011-09-29 Tautgirdas Ruzgas Pile flexible à combustible biologique, dispositif et procédé associés
US20130034760A1 (en) * 2011-08-02 2013-02-07 Otts Daniel B Biocompatible wire battery

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004079848A2 (fr) * 2003-03-03 2004-09-16 Yissum Research Development Company Of The Hebrew University Of Jerusalem Nouvelle electrode presentant une sortie de puissance commutable et accordable et pile a combustible utilisant cette electrode
WO2007147947A2 (fr) * 2006-06-19 2007-12-27 Valtion Teknillinen Tutkimuskeskus Structures de film mince innovantes
WO2008058165A2 (fr) * 2006-11-06 2008-05-15 Akermin, Inc. Ensembles empilages de bioanodes et de biocathodes
WO2009131452A1 (fr) 2008-04-24 2009-10-29 Stichting Wetsus Centre Of Excellence For Sustainable Water Technology Dispositif et procédé permettant de réaliser une réaction électrochimique biologiquement catalysée
WO2011117357A2 (fr) 2010-03-24 2011-09-29 Tautgirdas Ruzgas Pile flexible à combustible biologique, dispositif et procédé associés
US20130034760A1 (en) * 2011-08-02 2013-02-07 Otts Daniel B Biocompatible wire battery

Non-Patent Citations (7)

* Cited by examiner, † Cited by third party
Title
A. RUDGE; J. DAVEY; I. RAISTRICK; S. GOTTESFELD; J. FERRARIS, J. POWER SOURCES, vol. 47, 1994, pages 89 - 107
B. KUILA; B. NANDAN; M. BOHME; A. JANKE; M. STAMM., CHEM. COMMUN., 2009, pages 5749 - 5751
D. CHOI; G. BLOMGREN; P. KUMTA, ADVANCED MATERIALS, vol. 18, 2006, pages 1178 - 1182
DEEKE, A., SLEUTELS ET AL.: "Capacitive bioanodes enable renewable energy storage in microbial fuel cells", ENVIRONMENTAL SCIENCE AND TECHNOLOGY, vol. 46, 2012, pages 3554 - 3560
G. LOTA; K. FIC, E. FRACKOWIAK, ENERGY ENVIRON. SCI., vol. 4, 2011, pages 1592 - 1605
J. YOO; K. BALAKRISHNAN; J. HUANG; V. MEUNIER; B. SUMPTER; A. SRIVASTA; M. CONWAY; A. REDDY; J. YU; R. VAJTAI, NANO LETTERS, vol. 11, 2011, pages 1423 - 1427
L. LI; Z.-Y. QIN; X. LIANG; Q.-Q. FAN; Y.-Q. LU; W.-H. WU; M.-F. ZHU, J. PHYS. CHEM. C, vol. 113, 2009, pages 5502 - 5507

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WO2017062272A1 (fr) * 2015-10-06 2017-04-13 Case Western Reserve University Électrodes à capacité de charge élevée conçues pour permettre un blocage de conduction nerveuse par courant continu
US10828485B2 (en) 2015-10-06 2020-11-10 Case Western Reserve University High-charge capacity electrodes to deliver direct current nerve conduction block
CN106450399A (zh) * 2016-11-11 2017-02-22 青岛大学 一种基于微生物表面共展示顺序酶的高性能淀粉/氧气燃料电池
CN109307699A (zh) * 2018-09-21 2019-02-05 西北师范大学 基于埃洛石纳米管和石墨烯的电化学传感器的制备和应用
CN109742411A (zh) * 2018-12-06 2019-05-10 东南大学 一种多巴胺修饰石墨烯微生物燃料电池阳极的制备方法
CN109881484A (zh) * 2019-02-02 2019-06-14 东华大学 一种静电负载的多层涂层纱线或织物材料的制备方法
CN109881484B (zh) * 2019-02-02 2021-07-30 东华大学 一种静电负载的多层涂层纱线或织物材料的制备方法
CN110071297A (zh) * 2019-04-29 2019-07-30 西安交通大学 一种微生物燃料电池生物阳极及其制备方法
CN112310333A (zh) * 2019-07-23 2021-02-02 珠海冠宇电池股份有限公司 一种硫化物极片材料、其制备方法及锂电池
CN114023981A (zh) * 2021-07-26 2022-02-08 中国人民解放军军事科学院军事医学研究院 复合催化级联反应在葡萄糖燃料电池中的应用
CN114023981B (zh) * 2021-07-26 2023-10-27 中国人民解放军军事科学院军事医学研究院 复合催化级联反应在葡萄糖燃料电池中的应用
WO2023137278A1 (fr) * 2022-01-11 2023-07-20 University Of Maryland, Baltimore Applications de formiate déshydrogénase o2 insensible

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