WO2006058356A1 - Solid fuel for fuel cells - Google Patents

Solid fuel for fuel cells Download PDF

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Publication number
WO2006058356A1
WO2006058356A1 PCT/AT2005/000482 AT2005000482W WO2006058356A1 WO 2006058356 A1 WO2006058356 A1 WO 2006058356A1 AT 2005000482 W AT2005000482 W AT 2005000482W WO 2006058356 A1 WO2006058356 A1 WO 2006058356A1
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WO
WIPO (PCT)
Prior art keywords
fuel
polyoxymethylene
cells
hydrous
solid
Prior art date
Application number
PCT/AT2005/000482
Other languages
German (de)
French (fr)
Inventor
Karl Gruber
Original Assignee
Echem Kompetenzzentrum für angewandte Elektrochemie GmbH
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 Echem Kompetenzzentrum für angewandte Elektrochemie GmbH filed Critical Echem Kompetenzzentrum für angewandte Elektrochemie GmbH
Publication of WO2006058356A1 publication Critical patent/WO2006058356A1/en

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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
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
    • H01M8/04201—Reactant storage and supply, e.g. means for feeding, pipes
    • H01M8/04208—Cartridges, cryogenic media or cryogenic reservoirs
    • 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
    • H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
    • H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
    • H01M8/0612—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants from carbon-containing material
    • H01M8/0637—Direct internal reforming at the anode of the fuel cell
    • 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
    • H01M8/1009—Fuel cells with solid electrolytes with one of the reactants being liquid, solid or liquid-charged
    • 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
    • H01M8/2455—Grouping of fuel cells, e.g. stacking of fuel cells with liquid, solid or electrolyte-charged reactants
    • 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
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
    • 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

  • methanol as a fuel has the following disadvantages in direct and indirect conversion into fuel cells:
  • the subject of the present invention is a fuel which is easy to handle and store for use in an electrochemical cell, especially in fuel cells.
  • the invention relates to a fuel for use in fuel cells, which is in solid form and consists wholly or partly of the polymerization of formaldehyde, which are described in part as paraformaldehyde in part as polyoxymethylene exists.
  • the anhydrous high molecular weight polymerization of formaldehyde, the polyoxymethylene, and the hydrous Polyoxymethylenhydrate are suitable as fuel for use in electrochemical energy converters. It is likewise possible to use polyoxymethylene acetates, polyoxymethylene ethers and mixtures of these substances with polyoxymethylene.
  • the fuel is present as a solid in granular form or as a solid material.
  • the fuel is present as a solid peat and its vapor pressure is relatively low, which simplifies handling and minimizes the risk of toxic fumes.
  • the individual fuel grains or bodies can be encapsulated with a protective layer.
  • This protective layer may consist of another plastic, inorganic or organic material or of polyoxymethylene, which has a higher degree of polymerization than the actual fuel itself.
  • High energy densities can be achieved in automotive applications, as the fuel is carried undiluted and in solid form.
  • the energy content is about 4.77 kWh / kg or close to 6kWh / l !!
  • a low vapor pressure of the solid leads to low gaseous pollution of the environment during storage and handling;

Landscapes

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

Abstract

The invention relates to a fuel for using in fuel cells, said fuel being in a solid form and consisting fully or partially of the polymerisation products of the formaldehyde described partly as paraformaldehyde and partly as polyoxymethylene. Especially the anhydrous high-molecular polymerisation products of the formaldehyde, the polyoxymethylenes, and the hydrous polyoxymethylene hydrates are suitable as fuel for using in electrochemical energy converters.

Description

Fester Brennstoff für BrennstoffzellenSolid fuel for fuel cells
Beschreibungdescription
Brennstoffzellen wurden schon Ende des 19. Jahrhunderts als die theoretisch effizienteste Methode erkannt, chemische Energie direkt in elektrische Energie umzusetzen. Von den vielen vorgeschlagenen Brennstoffen ließ sich zunächst jedoch nur Wasserstoff problemlos umsetzen, da die kinetischen Hemmungen für die anodische Oxidation von Wasserstoff an den bekannten Katalysatormaterialen (v.a. Platin) gering sind. Um die Schwierigkeiten die bei der Handhabung und Speicherung von Wasserstoff auftreten zu umgehen, wurde schon bald vorgeschlagen, "wasserstoffreiche" chemische Verbindungen wie z.B. Hydrazin, Ammoniak oder Methanol als Brennstoff zu verwenden. Es stellte sich jedoch heraus, daß die kinetischen Hemmungen für die direkte anodische Oxidation dieser Brennstoffe an den bekannten Katalysatormaterialien zu hoch sind, um technisch brauchbare Leistungen zu erzielen. Da jedoch Methanol viel einfacher zu handhaben und zu speichern ist als Wasserstoff, stellt er nach wie vor einen attraktiven Brennstoff für brennstoffzellen-betriebene Geräte (vom Laptop bis zum Automobil) dar.At the end of the 19th century, fuel cells were recognized as the most theoretically efficient way of converting chemical energy directly into electrical energy. Of the many proposed fuels, however, initially only hydrogen could be implemented without any problems since the kinetic inhibitions for the anodic oxidation of hydrogen on the known catalyst materials (especially platinum) are low. In order to avoid the difficulties encountered in the handling and storage of hydrogen, it has soon been suggested to use "hydrogen-rich" chemical compounds, e.g. Hydrazine, ammonia or methanol to use as fuel. However, it has been found that the kinetic inhibitions for the direct anodic oxidation of these fuels to the known catalyst materials are too high to achieve technically useful performances. However, since methanol is much easier to handle and store than hydrogen, it is still an attractive fuel for fuel cell powered devices (from the laptop to the automobile).
Methanol als Brennstoff weist allerdings bei direkter wie indirekter Umsetzung in Brennstoffzellen folgende Nachteile auf:However, methanol as a fuel has the following disadvantages in direct and indirect conversion into fuel cells:
- flüssig bei Normaltemperatur- liquid at normal temperature
- relativ hohe Toxizität sowohl flüssig als auch gasförmig- relatively high toxicity both liquid and gaseous
- Schwierigkeit bei Handhabung durch hohen Dampfdruck (vergleichbar mit Benzin)Difficulty in handling by high vapor pressure (comparable to gasoline)
Bei direkter Umsetzung in DMFCs:For direct implementation in DMFCs:
- Leistungsverlust durch Methanol " Grosso ver"- Power loss due to methanol "Grosso ver"
- hohe Überspannungen bei Oxidation an den bekannten Katalysatoren- high overvoltages in the oxidation of the known catalysts
- Vergiftung von Pt Katalysatoren durch bei der Reaktion entstehende CO- artige Adsorbate- poisoning of Pt catalysts by CO-type adsorbates formed during the reaction
Gegenstand der vorgestellten Erfindung ist ein Brennstoff, der einfach zu handhaben und zu speichern ist, für die Verwendung in einer elektrochemischen Zelle, insbesondere in Brennstoffzellen.The subject of the present invention is a fuel which is easy to handle and store for use in an electrochemical cell, especially in fuel cells.
Gegenstand der Erfindung ist ein Brennstoff für die Verwendung in Brennstoffzellen, der in fester Form vorliegt und ganz oder teilweise aus den Polymerisationsprodukten des Formaldehyds, die zum Teil als Paraformaldehyd zum Teil als Polyoxymethylene beschrieben werden, besteht. Insbesondere die wasserfreien hochmolekularen Polymerisationsprodukte des Formaldehys, die Polyoxymethylene, sowie die wasserhaltigen Polyoxymethylenhydrate sind als Brennstoff für den Einsatz in elektrochemischen Energiewandlern geeignet. Ebenso können Polyoxymethylenacetate, Polyoxymethylenether sowie Mischungen dieser Stoffe mit Polyoxymethylen eingesetzt werden.The invention relates to a fuel for use in fuel cells, which is in solid form and consists wholly or partly of the polymerization of formaldehyde, which are described in part as paraformaldehyde in part as polyoxymethylene exists. In particular, the anhydrous high molecular weight polymerization of formaldehyde, the polyoxymethylene, and the hydrous Polyoxymethylenhydrate are suitable as fuel for use in electrochemical energy converters. It is likewise possible to use polyoxymethylene acetates, polyoxymethylene ethers and mixtures of these substances with polyoxymethylene.
Der Brennstoff liegt als Feststoff in Granulatform oder als Vollmaterial vor. Der Brennstoff liegt als Feststorf vor und sein Dampfdruck ist relativ gering, was die Handhabung vereinfacht und die Gefährdung durch giftige Dämpfe auf ein Mindestmaß reduziert. Zusätzlich können erfindungsgemäß die einzelnen Brennstoffkörner oder -körper mit einer Schutzschicht abgekapselt werden. Diese Schutzschicht kann aus einem anderen Kunststoff, anorganischen oder organischen Material bestehen oder aus Polyoxymethylen, das einen höheren Polymerisationsgrad als der eigentliche Brennstoff selbst aufweist. Die Vorteile des erfindungsgemäßen Brennstoffes sind:The fuel is present as a solid in granular form or as a solid material. The fuel is present as a solid peat and its vapor pressure is relatively low, which simplifies handling and minimizes the risk of toxic fumes. In addition, according to the invention, the individual fuel grains or bodies can be encapsulated with a protective layer. This protective layer may consist of another plastic, inorganic or organic material or of polyoxymethylene, which has a higher degree of polymerization than the actual fuel itself. The advantages of the fuel according to the invention are:
- die direkte anodische Oxidation führt zu geringeren Verlusten durch Überspannungen als die Verwendung von Methanol;- the direct anodic oxidation leads to lower losses due to overvoltages than the use of methanol;
- der Leistungsverlust durch parasitäre Stoffströme durch den Elektrolyt, insbesondere durch eine Polymerelektrolytmembran, kann verhindert oder eingedämmt werden;- The loss of power due to parasitic material flows through the electrolyte, in particular through a polymer electrolyte membrane, can be prevented or contained;
- es können billigere Katalysatormaterialien eingesetzt werden, da der geschwindigkeitsbestimmende erste Schritt der Methanoloxidation entfällt;- Can use cheaper catalyst materials, since the rate-limiting first step of methanol oxidation is omitted;
- die aus der Methanoloxidation bekannten Vergiftungserscheinungen an den Elektroden können vermieden oder vermindert werden;- The known from methanol oxidation symptoms of poisoning at the electrodes can be avoided or reduced;
- es können hohe Energiedichten bei automobilen Anwendungen erreicht werden , da der Brennstoff unverdünnt und in fester Form mitgeführt wird. Der Energieinhalt liegt bei etwa 4,77 kWh/kg bzw. nahe bei 6kWh/l !!;- High energy densities can be achieved in automotive applications, as the fuel is carried undiluted and in solid form. The energy content is about 4.77 kWh / kg or close to 6kWh / l !!
- die Handhabung und Speicherung dieses festen Brennstoffes ist bei weitem einfacher als die flüssigen Methanols oder Wasserstoffs;the handling and storage of this solid fuel is far simpler than the liquid methanol or hydrogen;
- dies führt in weiterer Folge zu einfacheren und billigeren Tanksystemen;- this subsequently leads to simpler and cheaper tank systems;
- ein geringer Dampfdruck des Feststoffes führt zu geringen gasförmigen Belastungen der Umwelt während der Speicherung und Handhabung;- A low vapor pressure of the solid leads to low gaseous pollution of the environment during storage and handling;
- durch Kapselung des Brennstoffes kann eine Gefährdung der Umwelt weitgehend ausgeschlossen werden;- By encapsulating the fuel, a risk to the environment can be largely excluded;
- der Brennstoff liegt bei Normaldruck als Feststoff vor,- daher können die Gefahrenpotentiale die von Hochdrucktanks (z.B.Wasserstoffdrucktanks mit 600 bar) ausgehen, vermieden werden. - The fuel is present as a solid at normal pressure, - therefore, the potential hazards of high-pressure tanks (eg 600 bar hydrogen pressure tanks) can be avoided.

Claims

Ansprüche: Claims:
1.) Brennstoff für die anodische Oxidation in elektrochemischen Zellen, insbesondere in Brennstoffzellen, dadurch gekennzeichnet, daß der Brennstoff in fester Form als Granulat oder Festkörper vorliegt und aus 0,1 bis 100%, vorzugsweise aus 85 bis 100% Polyoxymethylen oder Polyoxymethylenhydrat, oder Polyoxymethylenacetat oder Polyoxymethylenether oder Mischungen dieser Verbindungen besteht.1.) fuel for anodic oxidation in electrochemical cells, in particular in fuel cells, characterized in that the fuel is present in solid form as granules or solids and from 0.1 to 100%, preferably from 85 to 100% polyoxymethylene or Polyoxymethylenhydrat, or Polyoxymethylene acetate or polyoxymethylene ethers or mixtures of these compounds.
2.) Brennstoff für die anodische Oxidation in elektrochemischen Zellen, insbesondere in Brennstoffzellen, dadurch gekennzeichnet, daß der Brennstoff in fester Form als Granulat oder Festkörper vorliegt und aus 0,1 bis 100% vorzugsweise aus 85 bis 100% wasserhaltigem Polyoxymethylen oder wasserhaltigem Polyoxymethylenhydrat, oder wasserhaltigem Polyoxymethylenacetat oder wasserhaltigem Polyoxymethylenether oder Mischungen dieser Verbindungen besteht.2.) fuel for anodic oxidation in electrochemical cells, in particular in fuel cells, characterized in that the fuel is present in solid form as granules or solids and from 0.1 to 100%, preferably from 85 to 100% hydrous polyoxymethylene or hydrous Polyoxymethylenhydrat, or hydrous polyoxymethylene acetate or hydrous polyoxymethylene ether or mixtures of these compounds.
3.) Brennstoff nach Anspruch 1-2 dadurch gekennzeichnet, daß der Polymerisationsgrad des Polyoxymethylens, Polyoxymethylenhydrats, Polyoxymethylenacetats oder Polyoxymethylenethers zwischen 2 und 10000, vorzugsweise zwischen 1 und 150 liegt.3.) fuel according to claim 1-2, characterized in that the degree of polymerization of the polyoxymethylene, Polyoxymethylenhydrats, Polyoxymethylenacetats or Polyoxymethylenethers is between 2 and 10,000, preferably between 1 and 150.
4.) Brennstoff nach Anspruch 1-3 dadurch gekennzeichnet, daß der Brennstoff in einer Kapsel oder einem Behältnis gespeichert vorliegt. 4.) Fuel according to claim 1-3, characterized in that the fuel is stored in a capsule or a container.
PCT/AT2005/000482 2004-12-03 2005-12-02 Solid fuel for fuel cells WO2006058356A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AT0203804A AT500783B8 (en) 2004-12-03 2004-12-03 SOLID FUEL FOR FUEL CELLS
ATA2038/2004 2004-12-03

Publications (1)

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WO2006058356A1 true WO2006058356A1 (en) 2006-06-08

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DE (1) DE102005005878A1 (en)
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE557447C (en) * 1928-09-25 1932-08-23 Werner Schilt Dr Process for the production of solid, flammable polymers of formaldehyde
GB972425A (en) * 1962-04-28 1964-10-14 Hoechst Ag Copolymers of trioxane and process for preparing them
US4493878A (en) * 1982-04-23 1985-01-15 Hitachi, Ltd. Fuel element for liquid fuel cell and a liquid fuel cell
US5127922A (en) * 1989-09-15 1992-07-07 Bension Rouvain M Candles with colored flames

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1937837A1 (en) * 1969-07-25 1971-01-28 Forgber Dipl Ing Hans Fuel cell with solid fuel and liquid oxidising - agent
US20020076602A1 (en) * 2000-12-18 2002-06-20 More Energy Ltd. Direct liquid fuel cell and a novel binary electrode therefor

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE557447C (en) * 1928-09-25 1932-08-23 Werner Schilt Dr Process for the production of solid, flammable polymers of formaldehyde
GB972425A (en) * 1962-04-28 1964-10-14 Hoechst Ag Copolymers of trioxane and process for preparing them
US4493878A (en) * 1982-04-23 1985-01-15 Hitachi, Ltd. Fuel element for liquid fuel cell and a liquid fuel cell
US5127922A (en) * 1989-09-15 1992-07-07 Bension Rouvain M Candles with colored flames

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DE102005005878A1 (en) 2006-06-08
AT500783B8 (en) 2007-02-15
AT500783A4 (en) 2006-03-15
AT500783B1 (en) 2006-03-15

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