WO2005056880A1 - Plaque bipolaire et son procede d'obtention - Google Patents

Plaque bipolaire et son procede d'obtention Download PDF

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Publication number
WO2005056880A1
WO2005056880A1 PCT/ES2003/000629 ES0300629W WO2005056880A1 WO 2005056880 A1 WO2005056880 A1 WO 2005056880A1 ES 0300629 W ES0300629 W ES 0300629W WO 2005056880 A1 WO2005056880 A1 WO 2005056880A1
Authority
WO
WIPO (PCT)
Prior art keywords
projections
bipolar plate
mixture
pressing
temperature
Prior art date
Application number
PCT/ES2003/000629
Other languages
English (en)
Spanish (es)
Inventor
Mikhail Alexandrovich Tsypkin
Ricardo Blach Vizoso
Vladimir-Nikolaevich Fateev
Vladimir Igorevich Porembskiy
Eugeniy Akimovich Bogatchev
Original Assignee
David Systems & Technology, S.L.
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by David Systems & Technology, S.L. filed Critical David Systems & Technology, S.L.
Priority to PCT/ES2003/000629 priority Critical patent/WO2005056880A1/fr
Priority to AU2003288279A priority patent/AU2003288279A1/en
Publication of WO2005056880A1 publication Critical patent/WO2005056880A1/fr

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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
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/0204—Non-porous and characterised by the material
    • H01M8/0223—Composites
    • H01M8/0226—Composites in the form of mixtures
    • 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
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/0258—Collectors; Separators, e.g. bipolar separators; Interconnectors characterised by the configuration of channels, e.g. by the flow field of the reactant or coolant
    • H01M8/026—Collectors; Separators, e.g. bipolar separators; Interconnectors characterised by the configuration of channels, e.g. by the flow field of the reactant or coolant characterised by grooves, e.g. their pitch or depth
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/60—Constructional parts of cells
    • C25B9/65—Means for supplying current; Electrode connections; Electric inter-cell connections
    • 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
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/0258—Collectors; Separators, e.g. bipolar separators; Interconnectors characterised by the configuration of channels, e.g. by the flow field of the reactant or coolant
    • 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
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/0258—Collectors; Separators, e.g. bipolar separators; Interconnectors characterised by the configuration of channels, e.g. by the flow field of the reactant or coolant
    • H01M8/0263—Collectors; Separators, e.g. bipolar separators; Interconnectors characterised by the configuration of channels, e.g. by the flow field of the reactant or coolant having meandering or serpentine paths
    • 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
    • H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
    • H01M8/2457—Grouping of fuel cells, e.g. stacking of fuel cells with both reactants being gaseous or vaporised
    • 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
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/0204—Non-porous and characterised by the material
    • H01M8/0213—Gas-impermeable carbon-containing materials
    • 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
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/0204—Non-porous and characterised by the material
    • H01M8/0221—Organic resins; 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 present invention relates to a bipolar plate for application in the automotive, naval, energy, chemical and electrochemical industries, in particular it is useful in electrolysis to obtain chlorine, and may have application in the manufacture of fuel elements with membrane-electrode set.
  • Bipolar plates composed of a central part and peripheral parts located in opposite arrangement with respect to the central part are known.
  • the central part on one or both sides there are parallel longitudinal channels for the distribution of the flow of gaseous reagents that are limited by conductive projections of the current whose ends connect the peripheral parts.
  • the peripheral parts of the plates there are through holes that, once assembled the set of adjacent plates, form longitudinal channels for the improvement of the circulation and distribution of the electrolyte flows
  • bipolar plates The problem of these bipolar plates is in the uniform non-distribution of the flow, and in the limited space for the distribution of the gaseous reagent flows, determined by the large number of parallel longitudinal channels.
  • the method for obtaining bipolar plates is known, which includes the mixing of powdered graphite carbon components and a corrosion-resistant cohesion thermoplastic material, cold pressing of the powder mixture into a mold at 14500 Pa, the heating at 150 ° C, the pressure drop to 2000 kPa, the temperature rise to 205 ° C, and the pressure rise again to 14500 kPa, with a final phase of gradual pressure decrease and temperature (see description of patent RU 2187578).
  • Bipolar plates composed of a central part and peripheral parts located around the central part are known.
  • Labyrinth grooves are placed on one or two sides of the central part for the distribution of the gaseous reagent flows Longitudinal Y-shaped [, which form functional conductive projections of each other with their extremities located in the same plane, with a central hole and two diagonally arranged for the circulation and distribution of electrolyte flows.
  • holes are placed for block assembly.
  • the peripheral and central parts are separated by a cohesion element located in the perimeter of the central part.
  • the closest technical solution refers to a method of obtaining bipolar plates, which includes the preparation of a mixture of thermo-rigid resin of a certain composition in a volatile solvent, the mixing of the carbon aggregate with the prepared solution until reaching a homogeneous state , drying, pressing and thermal hardening (US patent application No. US2002 / 0037448.
  • thermal hardening is carried out not simultaneously but after pressing the piece.
  • drying the mixture at low temperature does not guarantee the removal of a large number of volatile components of the cohesion material, which prevents the pressing of microscopic amounts of the material of the bipolar plates, especially in the areas of the conductive projections. of the current, which serve to allow electrical contact and mechanical attachment of the current collector to the catalytic layer. This can lead to the formation of defective areas at the base of the projections, and to the rupture of these during the operation, assembly and exploitation of the elements of the fuel cell.
  • the objective of the proposed invention is to obtain bipolar plates with conductive projections of the free form and placement current with a height of between 0.3 to 2.0 mm by the mold pressing method of an electrically conductive composite material on a base of dispersed aggregates of carbon and thermo-rigid resin, as well as in the increase of the effectiveness in the transport of reagents and diversion of the products of the reaction.
  • the expected thermal result is an improvement in the operating properties of the bipolar plates and the fuel element as a whole.
  • the bipolar plate is composed of peripheral parts and a central part with prismatic conductive projections with a square or rectangular base or with a cylindrical or conical shape with a circular or elliptical base whose diameter or distance between more distant points of the base is between 0.5-3.0 mm, extending a height between 0.3 and 2.0 mm with variable or constant section with its free upper ends located in the same plane as the peripheral parts, and whose Distance between centers of projections is 1.0 to 4.0 mm.
  • the highlights can be placed freely and neatly on the board, in the form of chess boxes, rhombuses, circles, spirals, or labyrinth.
  • the objective pursued is achieved because between drying and pressing the mixture is subjected to an annealing at a temperature between 50 and 60 ° C lower than the thermal hardening temperature of the mixture, and the pressing is carried out with a repeated load up to 15-20 mPa pressure, while heating to the point of thermal hardening of the mixture.
  • the annealing is carried out with a gradual increase in temperature over 10 to 15 hours and the subsequent maintenance of the temperature reached for between 1 and 2 hours, and the pressing is carried out with a temperature of the active element of the Upper press 1.5-2 times at annealing temperature.
  • thermo-rigid resin acetone
  • thermo-rigid resin of any composition in the pressing mixture allows conductive projections of the current and bipolar plates to be formed without defects as a whole by the agglutination mechanism with liquid phase, which disappears just after its appearance, despite continuous heating.
  • sequence of phenomena that take place during the course of the main operations for the manufacture of bipolar plates is as follows:
  • thermo-rigid cohesive polymer Formation of a thin layer of thermo-rigid cohesive polymer on the surface of the particles of the carbon aggregate during the preparation of the mixture, its drying and subsequent annealing.
  • Annealing prior to pressing is necessary due to the presence in agglomerated mixtures of a large number of volatile components that hinder effective pressing.
  • a higher temperature during annealing can produce unwanted processes of premature hardening of the cohesive in microscopic amounts of the mixture, and a lower temperature is not effective.
  • An important parameter is the pressure during pressing.
  • the pressing pressure depends on the specific type of aggregate and must not exceed the extraction value of the liquid cohesive mixture: 20 mPa.
  • a low pressing pressure (less than 15 mPa) does not provide an effective understanding of the bipolar plate, especially in the area of the current conductors.
  • the formation of the due structure of the subsurface layer according to the proposed method takes place by the introduction of a pore forming agent (ammonium carbonate, polyethylene glycol, polyethylene) in the composition of the initial mixture for pressing, in a 0.1 -3.0% (weight) in relation to the solid components of the mixture.
  • a pore forming agent ammonium carbonate, polyethylene glycol, polyethylene
  • the pore forming agent included in the initial mixture does not hinder the hardening of the cohesive, and when decomposing during the process thermal and pressing during hardening, it forms a microporous structure of the plate, and consequently also of the subsurface layer (at a depth of 1-2 microns).
  • Figure 1. Shows a plan view of the bipolar plate.
  • Figure 2. Shows a sectional view of the bipolar plate represented in the previous figure according to A-A.
  • the bipolar plate object of this invention consists of a central part (1) and a peripheral part (2).
  • the central part has projections (3), whose upper free ends are in the same plane as the peripheral part (2), have a height a between 0.3 and 2 mm and a diameter or distance b between more points distant from its base between 0.5 and 3.0 mm.
  • the projections are spaced with a distance between centers c comprised between 1.0 and 4.0 mm and allow, with a large area and volume of passage of the gaseous reagent flows, to distribute the tensions (pressures) in all directions.
  • the projections can be shaped like a cylinder, sectioned pyramid, prism, and / or sectioned cone.
  • Bipolar plates are manufactured as described below: First, dispersed carbon components are combined to form a homogeneous mixture, with a certain amount of thermo-rigid resin solvent. As dispersed carbon components, graphite, soot, chopped fiber, powdered coke, etc. can be used.
  • the prepared mixture periodically stirred, is then placed for drying at room temperature, so that the main quantity of volatile components is eliminated.
  • a semi-finished material can be obtained, for example, from granules for a subsequent manufacturing process of bipolar plates. Subsequently, after performing a visual exam, you cover the dry mixture at a temperature between 50 and 60 ° C lower than the thermal hardening temperature.
  • the annealed mixture is then pressed at a pressure of 15-20 mPa in a mold, whose punches have channels that will shape the conductive projections of the current during pressing and hardening.
  • the heating of the mold with the mixture takes place, from annealing temperature to hardening temperature.
  • the mold After maintaining the hardening temperature of 0.5-1 hours, the mold is removed from the press and cooled in the air.
  • the suspension of the dry mixture was introduced into the mold, which was placed in the oven, heating it for 13.5-14 hours until reaching a temperature of 90 ° C, which was then maintained for 2 hours.
  • the visual control of the bipolar plate showed the absence on the surface of the bipolar plate (including the areas of the current conductors) of scratches, defects and fissures, and detachments of the material of the bipolar plate at the boundary between the zones of the conductive projections of the current and the base of the plate.
  • EXAMPLE 2 The bipolar plate was manufactured with a composition and method analogous to that of Example 1, with the difference that the projections are shaped like a truncated cone of 3.0 mm in diameter at the base, 2.5 mm at the end upper, a height of 2.0 mm, and a distance between its centers of 4.00 mm. Before and after performing the hardness test, no defects were detected on the surface or on the projections.
  • the volume resistivity value was 0.030 ⁇ -crn.
  • EXAMPLE 3 The bipolar plate was manufactured with a configuration and method analogous to that of example 1, with the difference that 31 g of epoxy-phenolic cohesive No. 560 produced by FGUP GNC "VIAM" were used as thermal hardening cohesive.
  • the volume resistivity value was 0.017 ⁇ • cm.
  • EXAMPLE 4 The bipolar plate was manufactured with a configuration and method analogous to that of Example 1, with the difference that 3.5 g (3.0% by weight) of pore-forming agent were added to the initial pressing mixture (high pressure polyethylene).
  • the volume resistivity value was 0.028 ⁇ • cm.
  • the porosity of the subsurface layer (depth up to 100 microns), measured by water absorption, was 2.8%.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Electrochemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Composite Materials (AREA)
  • Fuel Cell (AREA)

Abstract

Les plaques bipolaires sont formées par une partie centrale (1) et des parties périphériques (2), la partie centrale présente des protubérances conductrices de courant (3) dont les extrémités supérieures sont placées sur le même plan que les parties périphériques (2) et présentent une hauteur comprise entre 0,3 et 2 mm et une distance entre des points plus distants de la base comprise entre 0,5 et 3,0 mm. Les protubérances (3) sont espacées par une distance entre les centres de protubérances (3) comprise entre 1,0 et 4,0 mm. Le procédé d'obtention consiste essentiellement à effectuer, entre le séchage et la compression d'un mélange formé par une résine thermodurcissable, un dissolvant volatil et des poudres de carbone, une recuisson à une température inférieure comprise entre 50 et 60 °C à la température de thermodurcissage du mélange, ainsi que la compression est effectuée jusqu'à obtention d'une pression entre 15 et 20 mPa en même temps que l'on réalise le chauffage.
PCT/ES2003/000629 2003-12-12 2003-12-12 Plaque bipolaire et son procede d'obtention WO2005056880A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
PCT/ES2003/000629 WO2005056880A1 (fr) 2003-12-12 2003-12-12 Plaque bipolaire et son procede d'obtention
AU2003288279A AU2003288279A1 (en) 2003-12-12 2003-12-12 Bipolar plate and production method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/ES2003/000629 WO2005056880A1 (fr) 2003-12-12 2003-12-12 Plaque bipolaire et son procede d'obtention

Publications (1)

Publication Number Publication Date
WO2005056880A1 true WO2005056880A1 (fr) 2005-06-23

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WO (1) WO2005056880A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102016121506A1 (de) * 2016-11-10 2018-05-17 Audi Ag Bipolarplatte sowie Brennstoffzelle mit einer solchen

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4214969A (en) * 1979-01-02 1980-07-29 General Electric Company Low cost bipolar current collector-separator for electrochemical cells
US4690748A (en) * 1985-12-16 1987-09-01 The Dow Chemical Company Plastic electrochemical cell terminal unit
WO1988001310A2 (fr) * 1986-08-21 1988-02-25 Hydrogen Systems N.V. Systeme de plaquettes bipolaires destinees a etre utilisees dans des cellules electrochimiques
US20030068542A1 (en) * 2001-09-26 2003-04-10 Dainippon Ink And Chemicals, Inc. Bipolar plate for fuel cell, method for manufacturing the bipolar plate, and fuel cell using the bipolar plate

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4214969A (en) * 1979-01-02 1980-07-29 General Electric Company Low cost bipolar current collector-separator for electrochemical cells
US4690748A (en) * 1985-12-16 1987-09-01 The Dow Chemical Company Plastic electrochemical cell terminal unit
WO1988001310A2 (fr) * 1986-08-21 1988-02-25 Hydrogen Systems N.V. Systeme de plaquettes bipolaires destinees a etre utilisees dans des cellules electrochimiques
US20030068542A1 (en) * 2001-09-26 2003-04-10 Dainippon Ink And Chemicals, Inc. Bipolar plate for fuel cell, method for manufacturing the bipolar plate, and fuel cell using the bipolar plate

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102016121506A1 (de) * 2016-11-10 2018-05-17 Audi Ag Bipolarplatte sowie Brennstoffzelle mit einer solchen

Also Published As

Publication number Publication date
AU2003288279A1 (en) 2005-06-29

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