EP1461840A1 - Membranes biocompatibles stabilisees de copolymeres blocs et piles a combustible produites a l'aide de ces dernieres - Google Patents
Membranes biocompatibles stabilisees de copolymeres blocs et piles a combustible produites a l'aide de ces dernieresInfo
- Publication number
- EP1461840A1 EP1461840A1 EP02768453A EP02768453A EP1461840A1 EP 1461840 A1 EP1461840 A1 EP 1461840A1 EP 02768453 A EP02768453 A EP 02768453A EP 02768453 A EP02768453 A EP 02768453A EP 1461840 A1 EP1461840 A1 EP 1461840A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- polypeptide
- biocompatible membrane
- membrane
- anode
- synthetic polymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Classifications
-
- 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
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
- H01M8/103—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having nitrogen, e.g. sulfonated polybenzimidazoles [S-PBI], polybenzimidazoles with phosphoric acid, sulfonated polyamides [S-PA] or sulfonated polyphosphazenes [S-PPh]
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
- C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
- C08J5/2218—Synthetic macromolecular compounds
- C08J5/2256—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions other than those involving carbon-to-carbon bonds, e.g. obtained by polycondensation
-
- 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
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
- H01M8/1027—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having carbon, oxygen and other atoms, e.g. sulfonated polyethersulfones [S-PES]
-
- 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
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
- H01M8/1037—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having silicon, e.g. sulfonated crosslinked polydimethylsiloxanes
-
- 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
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1041—Polymer electrolyte composites, mixtures or blends
- H01M8/1044—Mixtures of polymers, of which at least one is ionically conductive
-
- 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
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
- H01M8/1081—Polymeric electrolyte materials characterised by the manufacturing processes starting from solutions, dispersions or slurries exclusively of polymers
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2383/10—Block- or graft-copolymers containing polysiloxane sequences
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0082—Organic polymers
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- the solution may also include a solubilizing detergent additives and other materials as desirable.
- the synthetic polymer material in a preferred embodiment, consists of at least one block copolymer.
- the synthetic polymer material includes at least one polymer, copolymer or block copolymer with the proviso that when the synthetic copolymer materials includes at least one block copolymer, the synthetic polymer material also includes at least one polymer or copolymer.
- the synthetic polymer material includes at least one stabilizing polymer.
- Figure 4a is a cross-sectional view of an aperture having a beveled edge and a biocompatible membrane
- Biocompatible membranes in accordance with the present invention can be formed from any synthetic polymer material that, when associated with one or more polypeptides as described herein, meet the objectives of the present invention.
- the average x value is 68, and the average y value is 15.
- This is an A-B-A block copolymer in which the "C" recited in the formula does not necessarily equate with the "C” designation of an A-B-C block copolymer.
- the polymer illustrated above can provide relatively large membranes that can incorporate functional proteins.
- the methacrylate moieties at the ends of the polymer molecules allow for free-radical mediated crosslinking after incorporating protein to add greater mechanical stability.
- Biocompatible membranes such as this, particularly those that are nonionic, have greater stability to higher voltage differences between the anode and cathode .
- the macroinitiators were prepared by equilibrating mixtures of 3- cyanopropylmethylcyclosiloxanes (DxCN) and dilithium diphenylsilanediolate (DLDPS) .
- Particularly preferred polymers capable of stabilizing biocompatible membranes include, without limitation, polyethylene glycol having an average molecular weight of between about 2,000 and about 10,000, polyethylene oxide having an average molecular weight of between about 2,000 and about 10,000, poly acrylamide having an average molecular weight of between about 5,000 and 15,000 daltons.
- procedures useful for polymerization include chemical polymerization with radical-forming or propagating agents and polymerization via photochemical radical generation with or without further radical propagating agents . Parameters can be adjusted depending on such conditions as the membrane material, the size of biocompatible membrane segments, the structure of the support, and the like. Care should be taken to minimize the damage to the polypeptide.
- One particularly useful method involves using peroxide at a neutral pH, followed by acidification.
- NADH dehydrogenase or, NADH:ubiquinone oxidoreductase
- Complex I can be isolated from over-expressing E. coli by the method described by Spehr et al . using solubilization with dodecyl maltoside.
- the solvent used in producing the synthetic polymer material solution is preferably selected to be miscible with both the water used (the polypeptide solution often includes water) and at least one of the synthetic polymer materials (polymer, copolymer and/or block copolymer) .
- the term "solution" as used herein generally encompasses suspensions as well .
- Appropriate solvents may include, without limitation, low molecular weight aliphatic alcohols and diols of between 1 and 12 carbons such as methanol, ethanol, 2-propanol, isopropanol, 1-propanol, aryl alcohols such as phenols, benzyl alcohols, low molecular weight aldehydes and ketones such as acetone, methyl ethyl ketone, cyclic compounds such as benzene, cyclohexane, toluene and tetrahydrofuran, halogenated solvents such as dichloromethane and chloroform, and common solvent materials such as 1,4-dioxane, normal alkanes (C 2 -C ⁇ 2 ) and water.
- aryl alcohols such as phenols, benzyl alcohols, low molecular weight aldehydes and ketones such as acetone, methyl ethyl ketone
- cyclic compounds such as
- One or more polypeptides are placed in solution or suspension, either separately or by being added to the existing polymer solution or suspension.
- solvent used to solubilize the synthetic polymer materials is the same, or of similar characteristics and solubility to that which can solubilize the polypeptide, it is usually more convenient to add the polypeptide to the polymer solution or suspension directly. Otherwise, the two or more solutions or suspensions containing the synthetic polymer materials and the polypeptide must be mixed, possibly with an additional cosolvent or solubilizer. Most often, the solvent used for the polypeptide is aqueous.
- One method of forming a biocompatible membrane, including a hydrogen-bonding rich stabilizing polymer is as follows:
- the membranes can be completely or substantially completely dried in a vacuum apparatus, or desiccator. Membranes so formed may be stored dried in vacuum or desiccated, if desired. Where the biocompatible membrane incorporates cross-linking moieties, such as methacrylates, and will be used in a fuel cell, the following procedure can be used:
- Supports or substrates with high natural surface charge densities such as Kapton and Teflon, are in some embodiments preferred. As noted above, these can be used to form the anode/cathode barrier without the use of surface electrodes.
- Substrate 42 is often preferably dielectric.
- Biocompatible membranes used in the invention are optionally stabilized against a solid support.
- One method for accomplishing such stabilization uses sulfur-mediated linkages of lipid-related molecules to glue, tether or bond metal surfaces or surfaces of another solid support to biocompatible membranes.
- a porous support can be coated with a sacrificial or removable filler layer, and the coated surface smoothed by, for example, polishing.
- Such a porous support can include any of the proton-conductive polymeric membranes discussed, typically so long as the proton-conductive polymeric membrane can be smoothed following coating, and is stable to the processing described below.
- One useful porous support is glass frit.
- the smoothed surface is then coated (with prior cleaning as necessary) with metal, such as with a first layer of chrome and an overcoat of gold.
- the sacrificial material is then removed, such as by dissolution, taking with it the metallization over the pores but leaving a metallized surface surrounding the pores.
- the sacrificial layer can comprise photoresist, paraffin, cellulose resins (such as ethyl cellulose), and the like.
- membrane 61 is formed within aperture 49 in perforated substrate 42, such that it does not necessarily contact either anode 44 or cathode 45.
- these figures are not to scale and that the membrane may be thicker or thinner than the electrode and may be thicker or thinner than the perforated substrate 42.
- biocompatible membrane 61 is not disposed between the anode 44 and cathode 45.
- biocompatible membrane 61 is disposed between anode 44 and cathode 45 in Figure 3d.
- the combination of the substrate 42 and biocompatible membrane 61 (along with the anode 44 in Figure 3b) form a structure that can also be referred to as a barrier.
- the thickness of substrate 42 is for example between about 15 micrometer ( ⁇ m) to about 5 millimeters, preferably from about 15 to about 1,000 micrometers, and more preferably, from about 15 micrometer to about 30 micrometers.
- the width of the perforations or pores is, for example, from about 1 micrometer to about 1,500 micrometers, more preferably about 20 to about 200 micrometers, and even more preferably, about 60 to about 140 micrometers. About 100 micrometers is particularly preferred.
- perforations or pores comprise in excess of about 30% of the area of any area of the dielectric substrate involved in transport between the chambers, such as from about 50 to about 75% of the area.
- the thickness of the biocompatible membrane in accordance with the present invention can be adjusted by known techniques such as controlling the volume introduced to a particular size pore, perforation, pan or tray, etc.
- the thickness of the membrane will be dictated largely by its composition and function.
- a membrane intended to include a transmembrane proton transporting complex such as complex I must be thick enough to provide sufficient support and orientation to the enzyme complex. It should not, however, be so thick as to prevent effective transportation of the proton across the membrane.
- the membranes will range from between about 10 nanometers to 100 micrometers or even thicker.
- biocompatible membranes useful for transporting protons in a fuel cell have been successful at thicknesses of 10 nanometers up to 10 micrometers. Again, thicker membranes are possible.
- the reduced cofactor or electron carrier can next interact with the polypeptides, in this case, the dehydrogenase function of Complex I embedded in a biocompatible membrane in accordance with the present invention.
- the Complex I liberates protons from the NADH molecule, as well as electrons.
- the electrons might flow directly to the anode. However, more often, they are taken up by a transfer mediator, which then transports the electrons to the anode.
- soluble enzymes that are adapted to use or otherwise can accommodate quinone-based electron carriers.
- Such enzymes are, for example, described in: Pommier et al . , "A second phenazine methosulphate-linked formate dehydrogenase isoenzyme in Escherichia coli," Biochim Biophys Acta. 1107 (2) : 305-13 , 1992. ("The diversity of reactions involving formate dehydrogenases is apparent in the structures of electron acceptors which include pyridine nucleotides, 5-deazaflavin, quinones, and ferredoxin”); Ferry, J.G. "Formate dehydrogenase” FEMS Microbiol. Rev.
- a solution useful for producing a biocompatible membrane in accordance with the present invention was produced as follows: 7% w/v (70 mg) of a block copolymer (poly (2-methyloxazoline) - polydimethyl siloxane-poly (2-methyl (oxazoline) having an average molecular weight of 2KD-5KD-2KD was dissolved in an 95%v/v / 5%v/v ethanol/water solvent mixture with stirring using a magnetic stirrer. Six microliters of this solution was removed and mixed with four microliters of a solution containing 0.015% w/v dodecyl maltoside, 40 micrograms of Complex I (10 mg/ml) in water. This is then mixed.
- a block copolymer poly (2-methyloxazoline) - polydimethyl siloxane-poly (2-methyl (oxazoline) having an average molecular weight of 2KD-5KD-2KD was dissolved in an 95%v/v / 5%v
- a solution useful for producing a biocompatible membrane in accordance with the present invention can be prepared generally as described in Example No. 6, however, the solvent used to dissolve the synthetic polymer material included 9.5% v/v ethanol, 0.5% v/v water, 40% v/v acetone, and 40% v/v hexane. Examples Nos. 19-24
- the synthetic polymer material used can be a mixture of two block copolymers, both of which are poly (2-methyloxazoline) - polydimethylsiloxane-poly (2-methyloxazoline) , (5% w/v) one of which having an average molecular weight of 2kD-5kD-2kD and the other 3kD-7kD-3kD and the ratio of the first block copolymer to the second being about 33% to 67% of the total polymer used w/w.
- Solutions useful for producing a biocompatible membrane in accordance with the present invention can be prepared generally as described in Examples Nos. 6-10 respectively, however the synthetic polymer used can be a mixture of 5% w/v of poly(2- methyloxazoline) -polydimethylsiloxane- poly (2-methyloxazoline) having an average molecular weight of 2kD-5kD-2kD in a solvent of 50%v/v acetone, 50%v/v heptane mixed with a solution of 5% w/v polystyrene of about 250,000 in molecular weight in 50%v/v acetone, 50%v/v octane in the proportion of 80%v/v block copolymer, 20% v/v polystyrene.
- Example No. 89 hen 6 microliters of that solution was mixed with sufficient polypeptide solution of the type described in Example 1 a final solution was produced including 0.0075, 0.015, 0.030, 0.045 and 0.060% w/v dodecyl maltoside and 0.75, 1.5, 3.0, 4.5 and 6.0% w/w polypeptide relative to synthetic polymer materials respectively.
- Example No. 89
- a solution useful for producing a biocompatible membrane in accordance with the present invention was prepared generally as described in Example No. 88 above, however, the surfactant used in the polypeptide solution included a mixture of a polymeric surfactant sold under the trademark DISPERPLAST, lot no. 31J022 from BYK Chemie, Wallingford CT and the same concentration of dodecyl maltoside specified in Example No. 88.
- the final concentration of the polymeric surfactant was diluted to 0.135%v/v of the supplied concentration in the final solution. Examples No. 98-102
Abstract
La présente invention concerne une membrane biocompatible stabilisée, utile dans des piles à combustible. Un substrat (42) perforé présentant des perforations (49) constitue une anode (44) perforée et une cathode (45) perforée. Une membrane biocompatible (61) est formée dans les ouvertures et affleure avec l'anode (44) ou peut être fixée à la cathode (45) adjacente. La membrane biocompatible (61) peut comprendre un ou plusieurs polypeptides (62,63).
Applications Claiming Priority (21)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US123021 | 1998-07-27 | ||
US33911701P | 2001-12-11 | 2001-12-11 | |
US339117P | 2001-12-11 | ||
US35748102P | 2002-02-15 | 2002-02-15 | |
US35736702P | 2002-02-15 | 2002-02-15 | |
US357481P | 2002-02-15 | ||
US357367P | 2002-02-15 | ||
US123008 | 2002-04-15 | ||
US10/123,039 US20030129469A1 (en) | 2001-04-13 | 2002-04-15 | Fuel cell with fuel concentrate metering |
PCT/US2002/011719 WO2002086999A1 (fr) | 2001-04-13 | 2002-04-15 | Pile a combustible enzymatique |
US10/123,020 US20030087144A1 (en) | 2001-04-13 | 2002-04-15 | Enzymatic fuel cell with fixed dehydrogenase enzyme |
US123022 | 2002-04-15 | ||
US10/123,022 US20030198859A1 (en) | 2002-04-15 | 2002-04-15 | Enzymatic fuel cell |
WOPCT/US02/11719 | 2002-04-15 | ||
US10/123,021 US20030198858A1 (en) | 2001-04-13 | 2002-04-15 | Enzymatic fuel cell with membrane bound redox enzyme |
US123039 | 2002-04-15 | ||
US123020 | 2002-04-15 | ||
US10/123,008 US20030087141A1 (en) | 2001-04-13 | 2002-04-15 | Dual membrane fuel cell |
US213477 | 2002-08-07 | ||
US10/213,477 US20030049511A1 (en) | 2001-04-13 | 2002-08-07 | Stabilized biocompatible membranes of block copolymers and fuel cells produced therewith |
PCT/US2002/025148 WO2003054995A1 (fr) | 2001-12-11 | 2002-08-08 | Membranes biocompatibles stabilisees de copolymeres blocs et piles a combustible produites a l'aide de ces dernieres |
Publications (1)
Publication Number | Publication Date |
---|---|
EP1461840A1 true EP1461840A1 (fr) | 2004-09-29 |
Family
ID=56290321
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP02768453A Withdrawn EP1461840A1 (fr) | 2001-12-11 | 2002-08-08 | Membranes biocompatibles stabilisees de copolymeres blocs et piles a combustible produites a l'aide de ces dernieres |
Country Status (6)
Country | Link |
---|---|
EP (1) | EP1461840A1 (fr) |
JP (1) | JP2005528463A (fr) |
AU (1) | AU2002331014A1 (fr) |
CA (1) | CA2470107A1 (fr) |
MX (1) | MXPA04005698A (fr) |
WO (1) | WO2003054995A1 (fr) |
Families Citing this family (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7241521B2 (en) | 2003-11-18 | 2007-07-10 | Npl Associates, Inc. | Hydrogen/hydrogen peroxide fuel cell |
US7977394B2 (en) | 2005-05-03 | 2011-07-12 | GM Global Technology Operations LLC | Triblock copolymers with acidic groups |
US7459505B2 (en) | 2005-05-03 | 2008-12-02 | General Motors Corporation | Block copolymers with acidic groups |
JP2007173041A (ja) * | 2005-12-22 | 2007-07-05 | Toyota Motor Corp | 燃料電池および燃料電池用電解質層 |
US7993792B2 (en) | 2006-07-26 | 2011-08-09 | GM Global Technology Operations LLC | Polymer blocks for PEM applications |
US8492460B2 (en) | 2006-07-28 | 2013-07-23 | GM Global Technology Operations LLC | Fluorinated polymer blocks for PEM applications |
FR2909292B1 (fr) * | 2006-12-04 | 2009-01-30 | Univ Grenoble 1 | Procede et dispositif de variation du ph d'une solution |
ES2717599T3 (es) * | 2007-06-29 | 2019-06-24 | Univ Grenoble 1 | Dispositivo de membrana artificial biomimética |
JP5181576B2 (ja) * | 2007-08-17 | 2013-04-10 | ソニー株式会社 | 燃料電池の製造方法、燃料電池および電子機器 |
KR101770241B1 (ko) * | 2010-03-17 | 2017-08-23 | 경상대학교산학협력단 | 연료 전지 및 전원 공급 시스템 |
JP6071316B2 (ja) * | 2012-08-08 | 2017-02-01 | 東京応化工業株式会社 | 組成物及びパターン形成方法 |
RU178485U1 (ru) * | 2017-12-28 | 2018-04-05 | Федеральное государственное бюджетное учреждение "Национальный исследовательский центр "Курчатовский институт" | Анод для биотопливного элемента из карбонизованного волокнистого материала |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NL9002764A (nl) * | 1990-12-14 | 1992-07-01 | Tno | Elektrode, voorzien van een polymeerbekleding met een daaraan gebonden redox-enzym. |
US6500571B2 (en) * | 1998-08-19 | 2002-12-31 | Powerzyme, Inc. | Enzymatic fuel cell |
-
2002
- 2002-08-08 MX MXPA04005698A patent/MXPA04005698A/es unknown
- 2002-08-08 EP EP02768453A patent/EP1461840A1/fr not_active Withdrawn
- 2002-08-08 JP JP2003555612A patent/JP2005528463A/ja active Pending
- 2002-08-08 CA CA002470107A patent/CA2470107A1/fr not_active Abandoned
- 2002-08-08 WO PCT/US2002/025148 patent/WO2003054995A1/fr not_active Application Discontinuation
- 2002-08-08 AU AU2002331014A patent/AU2002331014A1/en not_active Abandoned
Non-Patent Citations (1)
Title |
---|
See references of WO03054995A1 * |
Also Published As
Publication number | Publication date |
---|---|
CA2470107A1 (fr) | 2003-07-03 |
MXPA04005698A (es) | 2005-06-20 |
WO2003054995A1 (fr) | 2003-07-03 |
AU2002331014A1 (en) | 2003-07-09 |
JP2005528463A (ja) | 2005-09-22 |
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