WO2005038969A1 - Materiau de fabrication de plaques bipolaires pour piles a combustible, plaque bipolaire a base de ce materiau et pile a combustible comportant cette plaque - Google Patents

Materiau de fabrication de plaques bipolaires pour piles a combustible, plaque bipolaire a base de ce materiau et pile a combustible comportant cette plaque Download PDF

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Publication number
WO2005038969A1
WO2005038969A1 PCT/IT2003/000648 IT0300648W WO2005038969A1 WO 2005038969 A1 WO2005038969 A1 WO 2005038969A1 IT 0300648 W IT0300648 W IT 0300648W WO 2005038969 A1 WO2005038969 A1 WO 2005038969A1
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WO
WIPO (PCT)
Prior art keywords
anyone
graphite
plate
matrix
filler
Prior art date
Application number
PCT/IT2003/000648
Other languages
English (en)
Inventor
Gianpaolo Berta
Original Assignee
Compotec S.P.A.
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 Compotec S.P.A. filed Critical Compotec S.P.A.
Priority to AU2003283799A priority Critical patent/AU2003283799A1/en
Priority to PCT/IT2003/000648 priority patent/WO2005038969A1/fr
Publication of WO2005038969A1 publication Critical patent/WO2005038969A1/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
    • H01M8/0258—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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/58—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising fillers only, e.g. particles, powder, beads, flakes, spheres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/88—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts characterised primarily by possessing specific properties, e.g. electrically conductive or locally reinforced
    • B29C70/882—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts characterised primarily by possessing specific properties, e.g. electrically conductive or locally reinforced partly or totally electrically conductive, e.g. for EMI shielding
    • 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
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—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
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/665—Composites
    • H01M4/666—Composites in the form of mixed 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
    • H01M8/0223—Composites
    • H01M8/0226—Composites in the form of mixtures
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
    • B29C43/003—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor characterised by the choice of material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/0013—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor using fillers dispersed in the moulding material, e.g. metal particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0003—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds having particular electrical or magnetic properties, e.g. piezoelectric
    • B29K2995/0005—Conductive
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2031/00—Other particular articles
    • B29L2031/34—Electrical apparatus, e.g. sparking plugs or parts thereof
    • B29L2031/3468—Batteries, accumulators or fuel cells
    • 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
    • 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
    • H01M8/1007—Fuel cells with solid electrolytes with both reactants being gaseous or vaporised
    • 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
    • Y02E60/10—Energy storage using batteries
    • 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 material having a high thermal and electric conductivity, particularly but not exclusively adapted for manufacturing bipolar plates for 10 fuel cells.
  • the operation heart of fuel cells is the oxidation- reduction process of hydrogen and oxygen molecules to 25 obtain water molecules by releasing electrons and therefore producing a current flow.
  • the electrolyte (enabling transportation of ions H + ) consists 30 for example of a fluorinated polymer containing acid sulphonic groups.
  • the H + ions are in fact transferred into and through the electrolyte exactly by means of the acid sulphonic 35 groups.
  • This material is known under the name of NAFION® for example and is marketed by Dupont .
  • fuel cells generally contemplate the presence of a catalyst, generally a platinum, palladium or also nickel catalyst capable of facilitating dissociation of the hydrogen' atom.
  • a catalyst generally a platinum, palladium or also nickel catalyst capable of facilitating dissociation of the hydrogen' atom.
  • the catalyst surface shall be constantly renewed, i.e. cleared of the reaction products in such a manner that a new hydrogen may reach the catalyst itself thereby allowing the reaction.
  • conductive plates are presently used that consist of bipolar plates of a parallelepiped shape with thickness included between 1 and 2 mm and provided with appropriate switches exactly intended for enabling removal of the reaction products and arrival of new molecules for a good operation of the fuel cell.
  • bipolar plates must necessarily act as electric current collectors and also allow a good dissipation of the produced heat.
  • the plates are made up of a compound consisting of a matrix with a thermosetting base in which graphite fillers are buried in percentages until a maximum of 73%.
  • thermosetting matrix While these bipolar plates with a thermosetting matrix are widely used in the manufacture of fuel cells with a protonic-exchange membrane, they however have some limits and operating drawbacks .
  • thermosetting matrix of which they are made does not allow recycling of the material.
  • the material itself is very brittle so that it is impossible to increase the amount of the graphite filler and often even extraction of the finished product from the mould becomes a problem.
  • use of this compound involves many production rejects connected with a veritable breaking of the finished product.
  • each set consisting of the electrolyte, catalysts and bipolar plates is able to generate rather low potential differences, approximately of 0.4-0.8 volts, so that in each fuel cell the presence of a plurality of these sets is necessary, each with its associated plates.
  • the present invention aims at providing a new material having lower production costs than those of the bipolar plates with a thermosetting base.
  • Another aim of the invention is to provide a material enabling production of a bipolar plate impervious to hydrogen and oxygen flows at the pressures and temperatures of use of the fuel cell.
  • the material intended for manufacturing bipolar plates for fuel cells comprises at least one plastic matrix, that is no longer made of a thermosetting material, but comprises thermoplastic material.
  • Choice of the organic matrix has fallen on polyolefins having a more or less crystalline base and on polyesters and/or polyamides.
  • thermoplastic materials usable as the matrix appeared to be polypropylene due to its good workability at low temperatures .
  • thermoplastic base enables a cheap production of the manufactured article and simultaneously the observance of the required shapes during the injection and moulding steps, in addition to usability at the work conditions (generally temperatures included between 50 and 100 °C, gas pressures ranging from the atmospheric pressure to about 2 bars, in a mainly aqueous medium) .
  • a filler comprising graphite and/or carbon black is distributed in the thermoplastic matrix.
  • the filler may only consist either of graphite or of carbon black, may comprise percent combinations of the same products or also other materials, provided they are conductive.
  • the filler is added in such percentages, form and sizes that an electric and thermal conductivity of the material is allowed.
  • the filler (comprising graphite) shall constitute at least 70% by weight of the material and shall preferably be included between 75 and 95% of same.
  • the optimal per cent values by weight of the filler appears to be between 80% and 90%.
  • the graphite filler utilised in the present invention is of the synthetic type because this allows a better control in the dimensional distribution of same as compared with natural graphite.
  • the particles of powdered graphite have an average diameter included between 40 and 80 -10 "5 metres with a preferred value approximately of 60-10 "6 metres; in addition, at least 10-20% (preferably 15%) Of the graphite has a diameter exceeding 100 -10 "6 metres.
  • a graphite provided with a low shape ratio appeared to be the best for the purposes of the invention. It is known in fact that graphite has a structure consisting of superposed planes in which conductivity is only present along the planes and not at right angles thereto.
  • graphite is very anisotropic. It is also to be pointed out that the material in accordance with the present invention is also adapted to be injected into a mould in a direction substantially ⁇ transverse to the thickness of the plate to be made. Now, during this physical injection process, graphite has a tendency to lay in a direction parallel to the plane of injection therefore ensuring a better thermal and electric conductivity along this direction.
  • the bipolar plate with a parallelepiped shape must on the contrary ensure an optimal electric and thermal conductivity in a direction perpendicular to its faces, i.e. along its thickness. Therefore selection of graphite having a shape ratio as low as possible becomes of a fundamental importance; in this way the graphite material will tend to take the most isotropic possible arrangement in the volume of the bipolar plate, even when injected into a mould.
  • the graphite particles are required to be substantially in contact with each other within the matrix.
  • the obtained material enables manufacture of conductive components (bipolar plates for heat/current dissipation%) by preparing a mixture and/or a compound of the mentioned material which will be directly supplied in its definitive shape so that any further possible working on the workpiece will be avoided.
  • the finished product will have a heat and current conductivity in a direction longitudinal to the moulding flow as well.
  • the required amount of graphite (or filler) can be incorporated in a single passage while simultaneously controlling size and integrity of same.
  • the compound thus, obtained can. be also .directly injected into suitable moulds the shape of which matches that of the bipolar plate to be manufactured thereby allowing a finished product already provided with the necessary shapes to be obtained, which finished product will also have higher mechanical features than the bipolar plates made of thermosetting material.
  • the bipolar plate of thermoplastic material is provided with a flat base of parallelepiped shape with a thickness included between 0.5 and 4 mm, preferably of 1.6 mm.
  • a predetermined number of channels are present on the main face of said bipolar plate, which channels have an extension substantially parallel to the face plane and the hollow depth of which is in the order of 10 "3 metres.
  • each face has a plurality of channels parallel to each other exactly intended for removal of the reaction products from the catalyst.
  • the minimum thermal conductivity of the material is higher than 5 Wirf-'-K "1 and is generally higher than 10-20 Wm ⁇ K -1 .
  • the material allows a correct dissipation of the heat generated in the electrochemical process so that the system can operate at a temperature that is as constant as possible'.
  • the material also has low resistivity values, lower than 5 ⁇ cm, preferably lower than 250 '10 "3 ⁇ cm and more preferably lower than 100-10 ⁇ 3 ⁇ cm.
  • resistivity values are to be measured in a direction orthogonal to the moulding flow (direction Z) ; in fact usually graphites present on the market tend to direct their maximum conductivity in a direction longitudinal to the moulding flow (plane X Y) and use of graphites having undoubtedly low (even lower than 5) anisotropy values in current conduction is therefore fundamental .
  • the bipolar plate thus obtained can be incorporated into the appropriate fuel cells intended for production of electric energy for example, in which at least one protonic-exchange membrane is present which is associated with a catalyst in turn cooperating with at least one bipolar plate in accordance with the above description.
  • the invention achieves important advantages.
  • the obtained material also allows a direct moulding of the bipolar plate that must not be further worked. This enables an important saving of materials and production costs.
  • the material thus made has mechanical features greatly higher than those of the corresponding plates having a thermosetting base, and a much lower cost.
  • thermoplastic base can be recycled and therefore has less problems in terms of environmental impact.
  • the obtained material is able to be also injection moulded while still ensuring optimal thermal and electric conductivity features in the direction of the plate thickness.
  • the same material appeared excellent in its work conditions (i.e. with temperatures included between 50 and 100°C, in a mainly aqueous medium and with a gas pressure between 1 and 2 atmospheres) .
  • this material can be used not only for producing bipolar plates for fuel cells, but also for possible further conductive elements in batteries of any nature and others.

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

Abstract

L'invention concerne un matériau à haute conductivité thermique et électrique obtenu, qui comprend une matrice de matériau thermoplastique dans laquelle sont noyés des matériaux de remplissage conducteurs contenant plus de 70 % en poids de graphite. Ce matériau peut être obtenu par injection, par injection-compression, par compression ou extrusion. Ces opérations permettent d'obtenir directement un produit fini conducteur déjà pourvu d'une géométrie et d'une forme définitives.
PCT/IT2003/000648 2003-10-21 2003-10-21 Materiau de fabrication de plaques bipolaires pour piles a combustible, plaque bipolaire a base de ce materiau et pile a combustible comportant cette plaque WO2005038969A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
AU2003283799A AU2003283799A1 (en) 2003-10-21 2003-10-21 Material for manufacturing bipolar plates for fuel cells, bipolar plate made of said material and fuel sell comprising said plate
PCT/IT2003/000648 WO2005038969A1 (fr) 2003-10-21 2003-10-21 Materiau de fabrication de plaques bipolaires pour piles a combustible, plaque bipolaire a base de ce materiau et pile a combustible comportant cette plaque

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/IT2003/000648 WO2005038969A1 (fr) 2003-10-21 2003-10-21 Materiau de fabrication de plaques bipolaires pour piles a combustible, plaque bipolaire a base de ce materiau et pile a combustible comportant cette plaque

Publications (1)

Publication Number Publication Date
WO2005038969A1 true WO2005038969A1 (fr) 2005-04-28

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/IT2003/000648 WO2005038969A1 (fr) 2003-10-21 2003-10-21 Materiau de fabrication de plaques bipolaires pour piles a combustible, plaque bipolaire a base de ce materiau et pile a combustible comportant cette plaque

Country Status (2)

Country Link
AU (1) AU2003283799A1 (fr)
WO (1) WO2005038969A1 (fr)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999049530A1 (fr) * 1998-03-20 1999-09-30 Osaka Gas Company Limited Separateur pour element a combustible et son procede de production
JP2002100377A (ja) * 2000-09-20 2002-04-05 Kawasaki Steel Corp 燃料電池用セパレータおよび燃料電池
EP1315223A1 (fr) * 2000-06-29 2003-05-28 Osaka Gas Company Limited Composition conductrice pour separateur de pile a combustible de type a polymere solide, separateur de pile a combustible de type a polymere solide, pile a combustible de type a polymere solide et systeme de pile a combustible de type a polymere solide utilisant ce separateur

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999049530A1 (fr) * 1998-03-20 1999-09-30 Osaka Gas Company Limited Separateur pour element a combustible et son procede de production
EP1315223A1 (fr) * 2000-06-29 2003-05-28 Osaka Gas Company Limited Composition conductrice pour separateur de pile a combustible de type a polymere solide, separateur de pile a combustible de type a polymere solide, pile a combustible de type a polymere solide et systeme de pile a combustible de type a polymere solide utilisant ce separateur
JP2002100377A (ja) * 2000-09-20 2002-04-05 Kawasaki Steel Corp 燃料電池用セパレータおよび燃料電池

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Derwent World Patents Index; AN 1999-580521, XP002269122 *
PATENT ABSTRACTS OF JAPAN vol. 2002, no. 08 5 August 2002 (2002-08-05) *

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