WO2010063888A1 - Couche de catalyseur pour applications électrochimiques - Google Patents

Couche de catalyseur pour applications électrochimiques Download PDF

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Publication number
WO2010063888A1
WO2010063888A1 PCT/FI2009/050973 FI2009050973W WO2010063888A1 WO 2010063888 A1 WO2010063888 A1 WO 2010063888A1 FI 2009050973 W FI2009050973 W FI 2009050973W WO 2010063888 A1 WO2010063888 A1 WO 2010063888A1
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Prior art keywords
catalyst
membrane
catalyst layer
electrode assembly
membrane electrode
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PCT/FI2009/050973
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English (en)
Inventor
Pertti Kauranen
Ali Harlin
Pirjo HEIKKILÄ
Lisa WICKSTRÖM
Eino Sivonen
Jari Keskinen
Antti Pasanen
Original Assignee
Valtion Teknillinen Tutkimuskeskus
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Publication of WO2010063888A1 publication Critical patent/WO2010063888A1/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
    • H01M4/88—Processes of manufacture
    • H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/0007—Electro-spinning
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/18—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of unsaturated nitriles, e.g. polyacrylonitrile, polyvinylidene cyanide
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
    • D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
    • D01F9/21—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F9/22—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyacrylonitriles
    • 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
    • H01M4/88—Processes of manufacture
    • H01M4/8803—Supports for the deposition of the catalytic active composition
    • H01M4/881—Electrolytic membranes
    • 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
    • H01M4/90—Selection of catalytic material
    • H01M4/9008—Organic or organo-metallic compounds
    • 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
    • H01M4/90—Selection of catalytic material
    • H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
    • 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
    • H01M4/90—Selection of catalytic material
    • H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
    • H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
    • 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
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • 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
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
    • H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
    • 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
    • H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
    • 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

  • the present invention relates to a catalyst layer for electrochemical applications, especially to a composite catalyst layer structure, a membrane electrode assembly, and methods for preparing those.
  • the catalyst layer of proton exchange membrane (PEM) fuel cell should be quite thin (typically 5 - 20 ⁇ m) in order to be effective.
  • the catalyst layer is traditionally prepared by making a printing ink of carbon powder supported noble metal catalyst and dissolved PEM ionomer.
  • the catalyst layer is either printed directly on the electrolyte membrane or the gas diffusion layer carbon paper or indirectly on a polymer film from which it is transferred onto the membrane.
  • the catalyst coated membrane is then laminated with carbon papers or catalyst coated carbon papers are laminated with the electrolyte membrane for a five layer structure.
  • the carbon supported catalyst powders are prepared either by chemical reduction of precursor salts in a batch process, (as disclosed by the patent US-5,068,161 ), or by continuous aerosol synthesis (as disclosed by the patents US-6,338,809, US-6, 103,393).
  • One limitation of such catalyst layer is that the electrolyte may form electric insulation between the catalyst particles which may limit the electronic conductivity of the layer. This limitation could be overcome by using a continuous carbon web structure as the supporting structure for the noble metal catalyst.
  • Electrospinning is a method that can be used in the production of polymeric nanofibres. Polymer solution is drawn into nanosized fibres utilizing electric field arranged between the solution and a collector. Electrospinning equipment is typically consisting of nozzles through which the solution is fed into electric field, but electrospinning can also be obtained from free solution surface. Electrical forces accelerate the solution towards the collector forming polymer jets, which undergo instabilities such as whipping. Instabilities are largely responsible for the high stretching of the jet and the nanosized diameters of the obtained fibres. In addition to neat polymers, solutions containing additives and fillers can also be used to functionalize fibres for use in specific applications.
  • the nanosized structure of electrospun fibre web has intrinsic properties, such as small fibre diameter, small pore size, and high surface area, which are advantageous for many applications.
  • Electrospun webs can be used as a carrier for subsequent fixation of various substances onto the fibre surfaces as well as for their direct implementation into the fibre.
  • Polymeric nanofibres can be used as precursor fibres, which are carbonized into carbon nanofibres. This kind of approach can be used in order to prepare support carbon nanostructure for the deposition of noble metal catalyst.
  • Electrospun fibres can be functionalized using additives and fillers of many kinds in order to improve the electrospinnability and properties of electrospun fibres.
  • U.S. patent US7229944 describes a method for preparation of catalyst structure utilizing electrospinning method. This method includes preparation of electrospun neat polyacrylonithle (PAN) or PAN/platinum structure which is carbonized. Neat carbon web is subsequently coated with platinum (Pt).
  • PAN polyacrylonithle
  • Pt platinum
  • Korean patent KR 715155 (KR application KR10-2005-0037241 ) describes utilization of electrospinning in preparation of catalyst layer.
  • This patent publication includes preparation of carbon nanotube (CNT) containing electrospun composite web, which is carbonized, but instead of the direct use of the carbonized web as the catalyst support, the carbon web is ground up into stable fibres, which are coated with the catalyst and then used in preparation of catalyst structure thus involving more processing steps.
  • CNT carbon nanotube
  • a catalyst layer for electrochemical applications which include a composite catalyst support structure, which comprises polymer precursor and carbon nanotubes and/or carbon nanofibres.
  • the composite catalyst support structure may be formed by electrospinning of a carbonizable polymer precursor and carbon nanotubes and/or carbon nanofibres.
  • the composite catalyst support structure may further be converted to a carbonized composite web by subsequent heat treatment (carbonization). After the heat treatment a catalyst material may be deposited onto the carbonized composite web by physical or chemical methods.
  • a carbonizable polymer precursor may be polyacrylonithle (PAN), pitch, polyvinyl alcohol (PVA), polybenzimidatzole, polypyrrole or suchlike polymer having high carbon yield.
  • a method of heat treatment forming carbonized composite web is provided.
  • Polymer/CNT/CNF composite web is heat treated at 200-350 0 C in oxidizing atmosphere.
  • Heat treatment in inert atmosphere is carried out at 300-3000 0 C, preferably at 300- 1800 0 C.
  • the heat treatment steps are carried out continuously as roll-to-roll processes.
  • the thickness of the carbonized composite web is from 1 to 50 microns, preferably from 2 to 20 microns.
  • the catalyst material may be platinum or platinum alloy, e.g. Pt-Ru, Pt-Pd, Pt-Co, Pt-Ni, Pt-Co-Cr, Pt-Co- Mn, an organometallic compound like Co-Tetraphenylporphyhne, Fe- Tetraphenylporphyhne, Co-Tetramethoxyphenylporphyhne or Co- Phthalocyanine, silver or nickel, perovskite or spinel, e.g. Lao,iCao,9MnO3 or MnC ⁇ 2 ⁇ 4 .
  • Catalyst material may also be deposited as nanoparticles the size of which is from 1 to 20 nm, preferably from 2 to 10 nm.
  • Catalyst material may be deposited using physical methods like physical vapour deposition (PVD), chemical vapour deposition (CVD), arc discharge, atomic layer deposition (ALD) or liquid flame spray.
  • Catalyst material may also be deposited using chemical methods like reduction of precursor salts by methods known as microemulsion, impregnation, colloidal method or electrodeposition.
  • a membrane electrode assembly (MEA) for a membrane fuel cell e.g. polymer electrolyte membrane, direct methanol, direct ethanol or anion exchange membrane fuel cell, comprises electrodes which are produced according to a first aspect of the invention and that the electrodes are laminated with the electrolyte membrane.
  • MEA membrane electrode assembly
  • one electrode layer may be laminated on each side of the membrane or alternatively more than one electrode layer may be laminated on one or both sides of the membrane.
  • same catalyst material is used on both sides of the membrane or alternatively different catalyst materials may be used on different sides of the membrane.
  • one or more electrode layers are pretreated with the electrolyte solution before a lamination step.
  • Electrode layers may be also pretreated with a hydrophobic agent, e.g. polytetrafluoroethylene (PTFE), before the lamination step.
  • PTFE polytetrafluoroethylene
  • a lamination may be performed by hot pressing.
  • additional pieces of carbon paper or cloth may be laminated with the electrolyte membrane and the catalyst layers.
  • a membrane fuel cell e.g. polymer electrolyte membrane, direct methanol, direct ethanol or anion exchange membrane fuel cell, which use membrane electrode assemblies comprising electrodes which are produced according to first aspect of the invention, and that the electrodes are laminated with the electrolyte membrane.
  • Electrospinning is one processing method for polymeric nanosized fibres, thin nonwovens and fibre webs, which enables implementation substances such as carbon nanotubes (CNT) or carbon nanofibres (CNF) or both into the polymeric fibres
  • CNT and CNF fillers can act as reinforcement components, but they may also modify the electrical and surface properties of the electrospun fibres, nonwovens and fibre webs.
  • Composite fibres, containing CNTs or CNFs, are more stable in the carbonization process since CNTs nor CNFs do not shrink during heat treatment.
  • Electrospun nanosized fibres have characteristically high specific surface area and thus electrospun fibres and fibre webs may be used as effective carrier for subsequent fixation of substances such as catalyst onto fibre surfaces.
  • the specific surface area can further be increased by CNT or CNF addition.
  • the carbonized electrospun composite structure (carbonized composite web) thus produced is thin and shows improved electrical conductivity and mechanical strength over carbonized electrospun PAN nonwovens without CNT or CNF addition.
  • Fig.1 shows a schematic view of a catalyst layer and membrane electrode assembly
  • Fig. 2 shows a schematic view of roll-to-roll process of heat treatment
  • Fig. 3 shows a schematic view of producing membrane electrode assembly by roll-to-roll process
  • the invention provides a composite catalyst layer structure, which comprises carbonized composite web and catalytic material. These composite catalyst layer structures may further be used as electrodes of a membrane electrode assembly.
  • Composite catalyst structure for example for an electrochemical cell, is produced by electrospinning e.g. co-electrospinning of a carbonizable polymer, such as polyacrylonithle (PAN) or alike, and carbon nanotube (CNT) or nanofibre (CNF) composite nonwoven (composite support structure) followed by carbonization of the structure (carbonized composite web) and direct deposition of a catalytic material on it.
  • a carbonizable polymer such as polyacrylonithle (PAN) or alike
  • CNT carbon nanotube
  • CNF nanofibre
  • an essential part of the present invention is that it includes increment of CNTs or CNFs or both into electrospun structure.
  • CNTs or CNFs can be used as fillers in electrospun fibres, by adding them into spinning dope.
  • the length of carbon nanotubes of nanofibres may be preferably less than 20 microns. Diameter preferably from 2 to 200 nm.
  • the amount of CNT and/or CNF filler is preferably at most 10 weight-%.
  • Fig. 1 shows a schematic view of a membrane electrode assembly 1 according to one embodiment of the invention.
  • the structure is formed of an electrolyte membrane 2, a catalyst layer structure 4, 4 * and a carbon paper or cloth 6, 6 ⁇
  • the catalyst layer 4, 4 ' comprises a fibrous carbonized nonwoven web structure 8 where the carbonized fibres comprise carbon nanotubes and/or carbon nanofibres 10 and have catalytic material particles 12 supported on the fibres.
  • Fig 2. shows a schematic view of a continuous roll-to-roll heat treatment process.
  • Electrospun composite support structure is reeled off from the roll 3 and conveyed on a conveyor through a heat treatment at 200-350 0 C in oxidizing atmosphere in an oven 5 and reeled up on a roll 7.
  • Another heat treatment to produce carbonized composite structure may be carried out using the same procedure but in the difference heat treated in inert atmosphere at 300-3000 0 C, preferably at 300-1800 0 C .
  • Oxidizing and carbonizing heat treatment steps of the composite support structure may be carried out as individual steps or as a continuous process.
  • Fig 3. shows a schematic view of producing membrane electrode assembly by continuous roll-to-roll process.
  • a electrolyte membrane 2 is reeled off from the roll 3 and the catalyst layer structure 4 and 4 ' are applied and laminated 5 onto it. Further carbon paper or cloth 6 and 6 ' are laminated and after that thus formed membrane electrode assembly 1 is reeled up on a roll 7.
  • membrane electrode assembly may also be produced through a multi-stage process, wherein the different layers are laminated together individually.
  • Heat treatment process of composite support structure, deposition of catalyst layer on it, and further process to produce a membrane electrode assembly may also be carried out continuously.
  • the following nonlimiting examples are provided to further illustrate the present invention.
  • Example 1 According to one embodiment of the invention the catalyst support layer and the membrane electrolyte assembly may be produced as follows.
  • Electrospinning solution containing PAN and CNTs in dimethylformamide (DMF) is prepared by first dissolving small amount of PAN into DMF with the aid of heat and stirring. After that CNTs are added and dispersed with ultrasonic homogenizer. Small amount of polymer acts as a dispersing agent without increasing the viscosity, which would slow down the dispersing of the CNTs. When homogenous dispersion is obtained rest of the polymer is dissolved. The final polymer concentration should be high enough in order to ensure the sufficient viscoelastic forces to hold the jet coherent during the electrospinning process so that fibrous structures are formed. The sufficient amount depends on the molecular weight of the polymer and the structure of the polymer chain.
  • the solution is fed into nozzle system and electric field applied.
  • PAN is very responsive to process parameters especially when conductive CNTs increase the conductivity of the solution.
  • CNTs in composite solution increase the conductivity of the solution and thus increase the electrical forces of the process. Too high voltage and too high flow rate of the solution may cause the formation of 3-dimensional fibre structures instead of thin fibrous sheet.
  • Electrospun composite fibres are collected onto suitable substrate. Precursor fibre web is removed from the substrate and, if necessary, calandered in order to compress the precursor web without affecting the fibrous structure. Preparation of precursor web is then followed by well known heat treatment steps to convert the PAN precursor to carbon structure at temperatures of 200 - 3000 0 C. CNT or CNF addition to the electrospinning process will lead to smaller shrinkage of fibres during the carbonization process and improved mechanical and electrical properties of the carbonized web.
  • Platinum or platinum alloy nanoparticles are then deposited onto the carbonized web using well known physical or chemical deposition methods, e.g. PVD, CVD, ALD, liquid flame, reduction of precursor salts or electrodeposition.
  • PVD physical or chemical deposition methods
  • CVD chemical vapor deposition
  • ALD atomic layer deposition
  • liquid flame reduction of precursor salts or electrodeposition.
  • different spinel or perovskite type oxides, organic macrocycles, silver or nickel can be used as catalyst materials in alkaline environment.
  • one or more layers of the catalysed webs are laminated on both sides of the electrolyte membrane by hot pressing to form a so called membrane- electrolyte-assembly (MEA).
  • MEA membrane- electrolyte-assembly
  • the catalyzed webs can be treated with an electrolyte (e.g. Nafion) solution before the lamination to improve the protonic conductivity of the catalyst layer.
  • electrolyte e.g. Nafion
  • Electrospun web was prepared from solution containing 13.3 % PAN in dimethylformamide. Viscosity of the solution was 1290 centipoise (cP). Solution was electrospun to web having basis weight of 10 g/m 2 . Electrospinning was conducted with continuous electrospinning equipment with following parameters: nozzle size 0.4 mm, number of nozzles 40, spinning distance 150 mm, spinning voltage 28 kV. Electrospun fibres have diameter of 480 ⁇ 160 nm and their surface was smooth. Appearance of fibres is presented in Fig. 4.
  • Electrospun composite web was prepared from solution containing 13 % PAN and 0.25 % of CNT (NanocylTM, Nanocyl s.a Belgium, NC7000 - MWCNT 90% C purity for industrial applications, av. diameter 9.5 nm, av. length 1.5 ⁇ m) in dimethylformamide. Viscosity of the solution was 2320 cP. Sol ution was electrospun to web having basis weig ht of 1 0 g/m 2 . Electrospinning was conducted with continuous electrospinning equipment with following parameters: nozzle size 0.4 mm, number of nozzles 40, spinning distance 150 mm, spinning voltage 28 kV. Electrospun fibres contained approximately 1 ,9 wt% of CNT.
  • Fibres have diameter of 430 ⁇ 110 nm and the tips of CNTs could be seen on their surface. Appearance of fibres is presented in Fig. 5. where the nanotubes are seen as surface roughness. For example, in Fig. 5 the nanotubes on the surface of the fibre are seen inside the white circles.
  • the PAN/CNT composite web was stabilized and carbonized using the same parameters as in Example 2.
  • Table 1 shows some properties of nonwoven PAN and PAN/CNT webs.
  • the shrinkage was measured as the reduction of the web width.

Abstract

L'invention porte sur une structure de catalyseur pour cellule électrochimique qui est produite par électro-filage d'un non-tissé composite de polyacrylonitrile (PAN) et de nanotube de carbone (CNT) ou de nanofibre de carbone (CNF) suivi par la carbonisation de la structure et le dépôt d'un catalyseur sur celle-ci. Un procédé d'électro-filage permet une mise en œuvre de substances telles que des CNT dans la fibre, et des fibres électro-filées ayant une surface spécifique typiquement élevée peuvent être utilisées comme support pour une fixation subséquente de substances tel qu'un catalyseur aux surfaces des fibres. La structure ainsi produite est mince et présente une conductivité électrique et une résistance mécanique améliorées par rapport à des non-tissés PAN électro-filés carbonisés sans ajout de CNT ni de CNF.
PCT/FI2009/050973 2008-12-02 2009-12-02 Couche de catalyseur pour applications électrochimiques WO2010063888A1 (fr)

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FI20086154A FI20086154A0 (fi) 2008-12-02 2008-12-02 Katalyyttirakenne
FI20086154 2008-12-02

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CN102336759A (zh) * 2011-07-21 2012-02-01 首都师范大学 一种平面双核金属酞菁配合物的制备方法
EP2600452A4 (fr) * 2010-07-29 2016-07-27 Nisshinbo Holdings Inc Électrode pour pile à combustible
EP2633581A4 (fr) * 2010-10-27 2017-03-15 Vanderbilt University Électrode en nanofibres et son procédé de fabrication
CN107915496A (zh) * 2017-11-17 2018-04-17 张豫鹏 一种大面积二维有机‑无机钙钛矿薄膜的制备方法
CN108286127A (zh) * 2018-02-02 2018-07-17 南京工业大学 一种疏水疏油纳米纤维膜的制备方法
CN112864435A (zh) * 2021-01-08 2021-05-28 杭州廖仕科技有限公司 一种碳纳米管接枝聚丙烯腈纤维的复合纤维膜的制法和应用
CN114243036A (zh) * 2021-12-27 2022-03-25 广东省武理工氢能产业技术研究院 一种多孔氮杂碳纳米纤维氧还原催化剂及其制备方法

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WO2010010990A1 (fr) * 2008-07-25 2010-01-28 Amomedi Co., Ltd. Electrode pour pile à combustible comprenant une couche de catalyseur et une couche de diffusion de gaz intégrées à un réseau de nanofibres, procédé de préparation associé et pile à combustible l’utilisant

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EP2633581A4 (fr) * 2010-10-27 2017-03-15 Vanderbilt University Électrode en nanofibres et son procédé de fabrication
US9905870B2 (en) 2010-10-27 2018-02-27 Vanderbilt University Nanofiber electrode and method of forming same
CN102336759A (zh) * 2011-07-21 2012-02-01 首都师范大学 一种平面双核金属酞菁配合物的制备方法
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CN108286127A (zh) * 2018-02-02 2018-07-17 南京工业大学 一种疏水疏油纳米纤维膜的制备方法
CN112864435A (zh) * 2021-01-08 2021-05-28 杭州廖仕科技有限公司 一种碳纳米管接枝聚丙烯腈纤维的复合纤维膜的制法和应用
CN112864435B (zh) * 2021-01-08 2022-09-30 腾强科技(北京)有限责任公司 一种碳纳米管接枝聚丙烯腈纤维的复合纤维膜的制法和应用
CN114243036A (zh) * 2021-12-27 2022-03-25 广东省武理工氢能产业技术研究院 一种多孔氮杂碳纳米纤维氧还原催化剂及其制备方法
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