WO2007106082A1 - Pile à combustible ayant un saturateur anticongélation à entrée d'agent réactif - Google Patents

Pile à combustible ayant un saturateur anticongélation à entrée d'agent réactif Download PDF

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Publication number
WO2007106082A1
WO2007106082A1 PCT/US2006/008802 US2006008802W WO2007106082A1 WO 2007106082 A1 WO2007106082 A1 WO 2007106082A1 US 2006008802 W US2006008802 W US 2006008802W WO 2007106082 A1 WO2007106082 A1 WO 2007106082A1
Authority
WO
WIPO (PCT)
Prior art keywords
antifreeze
reactant
saturator
molecular weight
fuel cell
Prior art date
Application number
PCT/US2006/008802
Other languages
English (en)
Inventor
Nikunj Gupta
Sergei F. Burlatsky
Shubhro Ghosh
Patrick L. Hagans
Original Assignee
Utc Fuel Cells, Llc
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 Utc Fuel Cells, Llc filed Critical Utc Fuel Cells, Llc
Priority to PCT/US2006/008802 priority Critical patent/WO2007106082A1/fr
Publication of WO2007106082A1 publication Critical patent/WO2007106082A1/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
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04007—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids related to heat exchange
    • H01M8/04029—Heat exchange using liquids
    • 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
    • H01M8/04089—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants
    • H01M8/04119—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants with simultaneous supply or evacuation of electrolyte; Humidifying or dehumidifying
    • H01M8/04126—Humidifying
    • 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
    • H01M8/04197—Preventing means for fuel crossover
    • 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
    • H01M2008/1095—Fuel cells with polymeric electrolytes
    • 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
    • H01M8/04007—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids related to heat exchange
    • H01M8/04067—Heat exchange or temperature measuring elements, thermal insulation, e.g. heat pipes, heat pumps, fins
    • H01M8/04074—Heat exchange unit structures specially adapted for fuel cell
    • 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 fuel cells that are suited for usage in transportation vehicles, portable power plants, or as stationary power plants, and the invention especially relates to a fuel cell having a saturator for humidifying reactant streams passing through reactant inlets of the fuel cell.
  • Fuel cells are well known and are commonly used to produce electrical current from hydrogen containing reducing fluid fuel and oxygen containing oxidant reactant streams to power electrical apparatus such as generators and transportation vehicles .
  • start up of a fuel cell in cold weather presents many challenges.
  • a major problem is related to rapid temperature change during initial start up of the fuel cell.
  • Upon start up in sub-freezing ambient temperatures meaning below 0 degrees Centigrade "0.0 0 C."
  • a fuel cell may transition to temperatures beyond 30 0 C within a few seconds.
  • the incoming fuel and oxidant reactant streams typically have a very low relative humidity. This may result in a rapid drying out of the proton exchange membrane (“PEM”) electrolyte .
  • PEM proton exchange membrane
  • the separation membrane or enthalpy exchange barrier permits pure water to pass through into reactant streams while restricting passage of antifreeze components of the antifreeze solution. It is also known to use "direct antifreeze solutions", as disclosed in the aforesaid patent to Condit et al., that pass through porous water transport plates of thermal management systems to thereby assist in humidification of reactant streams within the fuel cell. Such direct antifreeze solutions include properties of being organic, of not wetting cathode catalysts, and of being non-volatile at fuel cell operating temperatures.
  • Patent 6,911,274 that issued on June 28, 2005 to Michels et al, which patent is also owned by the owner of all rights in this application, discloses that it is also known to use a high molecular weight direct antifreeze solution within a porous water transport plate to aid in humidification of reactant streams passing adjacent the porous water transport plate.
  • the high molecular weight direct antifreeze solution disclosed in Michels et al . preferably includes a polyethylene glycol having a molecular weight ranging from 200 to 8,000 atomic mass units ("AMU").
  • AMU atomic mass units
  • the invention is a fuel cell for producing electrical energy from a first reactant stream and a second reactant stream.
  • the fuel cell includes a proton exchange membrane (“PEM”) electrolyte secured between a first catalyst and a second catalyst; a first reactant inlet secured in fluid communication with the first catalyst for directing the first reactant stream to flow adjacent the first catalyst; a second reactant inlet secured in fluid communication with the second catalyst for directing the second reactant stream to flow adjacent the second catalyst; and, a sealed coolant plate secured in heat exchange relationship with the catalysts wherein the plate is configured to direct a coolant stream to pass through the plate to remove heat from the fuel cell.
  • PEM proton exchange membrane
  • An antifreeze saturator is secured in fluid communication with one of the first reactant inlet or the second reactant inlet.
  • the saturator is configured to contain a high molecular weight direct antifreeze solution and to direct the reactant stream to pass through the liquid antifreeze and back into the reactant inlet.
  • the high molecular weight direct antifreeze solution preferably includes as an antifreeze component a polyethylene glycol having a molecular weight ranging from 200 to 8,000 atomic mass units (hereafter "AMU") •
  • the high molecular weight direct antifreeze component may also be selected from the group consisting of ethylene oxide chains terminated by functional alkyl and/or hydroxyl groups, linear alcohols, branched alcohols, polyethylene glycols, methoxypolyethylene glycols, dimethoxypolyethylene glycols, triethylene glycols, and tetraethylene glycols, and mixtures thereof, each member of the group having a molecular weight ranging from 400 to 8,000 AMU.
  • An exemplary high molecular weight direct antifreeze is polyethylene glycol having a molecular weight of 400 (hereafter "PEG 400”) .
  • PEG 400 produces a direct antifreeze solution with a freezing point of minus twenty (-20) degrees Centigrade (hereafter “ 0 C”) at a concentration of 50.6 weight percent (hereafter “wt.%”), balance water, compared to 45.4 wt.% for a glycerol antifreeze solution to obtain the same freezing point.
  • the corresponding mole fraction that determines thermophysical properties of antifreeze solutions is only 4.4 mole percent for the PEG 400, but 14.5 mole percent for the glycerol for the same -20 0 C freezing point of the high molecular weight direct antifreeze solution. Therefore, the PEG 400 has very little effect on the vapor pressure of water within the solution.
  • Such a high molecular weight direct antifreeze solution thus provides for achieving 90 percent ("%") relative humidity within reactant streams passing through and over the solution, even at fuel cell operating temperatures as high as 80 degrees centigrade (“ 0 C") .
  • Use of an appropriate amount of PEG 400 may produce a high molecular direct weight antifreeze solution having a freezing temperature as low as -40 0 C.
  • the PEG 400 has a near zero or virtually negligible vapor pressure through possible operating temperatures of a fuel cell ranging between about -40 0 C and about 100 0 C. Consequently, molecules of the antifreeze component of the high molecular weight direct antifreeze solution do not escape the liquid antifreeze solution into the gaseous fuel and/or oxidant reactant streams passing through and over the solution, thereby leaving the reactant streams humidified with virtually pure water.
  • the fuel cell includes a first antifreeze saturator secured in fluid communication with the first reactant inlet, and a second antifreeze saturator secured in fluid communication with the second reactant inlet.
  • the sealed coolant plate may be a component of a coolant loop that directs flow of the coolant stream from the sealed coolant loop through a coolant feed line, a coolant pump, a coolant heat exchanger, a coolant pressure control valve, and back into the coolant plate.
  • the first and second antifreeze saturators may also be in fluid communication with the coolant feed line to selectively supply portions of the coolant stream to the saturators .
  • Figure 1 is a simplified schematic representation of a fuel cell having first and second reactant inlet antifreeze saturators constructed in accordance with the present invention.
  • a fuel cell having a reactant inlet antifreeze saturator is shown in FIG. 1, and is generally designated by the reference numeral 10.
  • the fuel cell 10 includes a proton exchange membrane (“PEM”) electrolyte 12 secured between a first catalyst 14, such as cathode catalyst, and a second catalyst 16, such as an anode catalyst.
  • a first reactant inlet 18 is secured in fluid communication with the first catalyst 14 for directing a first reactant stream, such as a process oxidant stream, from a first reactant storage source 19 adjacent the first catalyst 14, such as through a first flow field 20.
  • a first reactant outlet 22 directs the first reactant stream out of the fuel cell 10.
  • a second reactant inlet 24 is secured in fluid communication with the second catalyst 16 for directing a second reactant stream, such as a hydrogen rich reducing fluid, from a second reactant stream source 25, adjacent the second catalyst 16, such as through a second flow field 26.
  • a second reactant outlet 28 directs the second reactant stream out of the fuel cell 10.
  • a sealed coolant plate 30 is secured in heat exchange relationship with the catalysts 14, 16, such as adjacent the first flow field 20, as shown in FIG. 2.
  • the sealed coolant plate 30 is configured to direct flow of a coolant stream through the plate 30 to remove heat generated during operation of the fuel cell 10 in a manner well known in the art.
  • sealed it is meant that the cooling stream may not pass through the plate 30 directly into the adjacent fuel cell components, such as into the first flow field 30.
  • the sealed coolant plate 30 may also be a component of a coolant loop 32 for directing flow of the cooling stream from the sealed coolant plate 30 through a coolant feed line 34, a coolant pump 36, a coolant heat exchanger 38, a coolant pressure control valve 40, and back into the sealed coolant plate 30.
  • the coolant pressure control valve 40 may be utilized in a manner described in the above referenced patents to produce a pressure within the sealed coolant plate that is lower than a pressure of the reactant stream passing through the adjacent first flow field 20 to thereby minimize passage of the coolant stream from the plate 30 into the flow field 20 in the event of a leak in the plate 30.
  • a first antifreeze saturator 42 is secured in fluid communication with the first reactant inlet 18 so that the first reactant inlet 18 directs the first reactant stream to pass into direct contact with a high molecular weight direct antifreeze solution 44 contained within the first saturator 42.
  • the first saturator 42 is configured so that the first reactant stream is directed to pass as bubbles through the direct antifreeze solution 44 within the saturator 42 as shown schematically in FIG. 1, or alternatively, to pass over the direct antifreeze solution 44.
  • a second antifreeze saturator 46 is secured in fluid communication with the second reactant inlet 24 so that the second reactant inlet 24 directs the second reactant stream to pass into direct contact with the high molecular weight direct antifreeze solution 44 contained within the second antifreeze saturator 46.
  • the second saturator 46 is preferably configured so that the second reactant stream may pass directly through the high molecular weight direct antifreeze solution 44 as bubbles, or alternatively may pass over the direct antifreeze solution 44.
  • the reactant streams pass in fluid communication with the high molecular weight direct antifreeze solution within the first or second saturator 42, 46.
  • the fuel cell 10 may also include a saturator re-supply means for re-supplying the first and second antifreeze saturators 42, 46.
  • the saturator re- supply means may include an antifreeze solution re-supply line 48 secured between the coolant loop 32 and the first and second saturators 42, 46 and including a saturator re-supply valve 50 means for selectively re-supplying the saturators 42, 46 with a high molecular weight antifreeze solution within the coolant loop 32.
  • the saturator re-supply means may also include a water re- supply line 52 secured between a fuel cell product water condenser 53, a water separator 54 and the cathode reactant outlet 22.
  • the water re-supply line 52 would include a water separator control valve 56 to selectively direct a cathode exhaust stream into the condenser 53 and the separator 54 to collect the fuel cell product water, in a manner known in the art.
  • the water re-supply line 52 could also be secured through the saturator re-supply valve means 50, such as a three-way valve, to selectively direct the fuel cell product water into the saturators 42, 46.
  • the saturator re-supply valve means may include the single three-way valve 50, or any combination of valves known in the art that could achieve the functions described herein.
  • the fuel cell 10 would employ control means (not shown) in communication with the re-supply valve means 50 known in the art for controlling maintenance of an optimal volume and concentration of the high molecular weight direct antifreeze solution in the first and second saturators 42, 46 through use of the saturator re-supply means.
  • the fuel cell 10 also includes a first reactant inlet valve 58 secured on the first reactant inlet 18 for selectively permitting and terminating passage of the first reactant stream through the first reactant inlet 18, and a second reactant inlet valve 60 secured to the second reactant inlet 24 for selectively permitting or terminating passage of the second reactant stream through the second reactant inlet.
  • the high molecular weight direct antifreeze solution 44 preferably includes as an antifreeze component a polyethylene glycol having a molecular weight ranging from 200 to 8,000 atomic mass units (hereafter "AMU") .
  • the high molecular weight direct antifreeze comnponent may also be selected from the group consisting of e.thylene oxide chains terminated by functional alkyl and/or hydroxyl groups, linear alcohols, branched alcohols, polyethylene glycols, methoxypolyethylene glycols, dimethoxypolyethylene glycols, triethylene glycols, and tetraethylene glycols, and mixtures thereof, each member of the group having a molecular weight ranging from about 400 to about 8,000 AMU.
  • the phrase "a molecular weight of about” means plus or minus 10.
  • an exemplary high molecular weight direct antifreeze is polyethylene glycol having a molecular weight of about 400 (hereafter "PEG 400”) .
  • PEG 400 produces a direct antifreeze solution 44 with a freezing point of minus twenty (-20) degrees Centigrade (hereafter “ 0 C”) at a concentration of 50.6 weight percent (hereafter “wt.%”), balance water, compared to 45.4 wt.% for a glycerol antifreeze solution to obtain the same freezing point.
  • the corresponding mole fraction that determines thermophysical properties of antifreeze solutions is only 4.4 mole percent for the PEG 400, but 14.5 mole percent for the glycerol for the same -20 0 C freezing point of the high molecular weight direct antifreeze solution. Therefore, the PEG 400 direct antifreeze solution 44 has very little effect on the vapor pressure of water within the solution. Such a high molecular weight direct antifreeze solution 44 thus provides for achieving 90 percent ("%") relative humidity within reactant streams passing through and over the solution, even at fuel cell operating temperatures as high as 80 degrees centigrade (“ 0 C") .
  • the PEG 400 has a near zero or virtually negligible vapor pressure through possible operating temperatures of a fuel cell ranging between about -40 0 C and about 100 0 C. Consequently, molecules of the antifreeze component of the high molecular weight direct antifreeze solution 44 do not escape the liquid antifreeze solution into the gaseous fuel and/or oxidant reactant streams passing through and/or over the solution, thereby leaving the reactant streams humidified with virtually pure water.
  • the fuel cell 10 may be configured to include only one of the antifreeze saturators 42, 48 secured in fluid communication with either the first reactant inlet 18 or second reactant inlet 24.
  • specific operating conditions of a fuel cell 10 may indicate that adequate humidification of its PEM electrolyte 12 can be achieved through usage of a antifreeze saturator 42 secured in fluid communication with the first or cathode catalyst 14 because the particular stored hydrogen rich reducing fluid utilized as the second reactant stream may have a satisfactory relative humidity adjacent the second or anode catalyst 16.
  • the present invention also includes a method of humidifying a reactant stream of the fuel cell 10 by passing at least one of the first or second reactant streams in direct contact with a high molecular weight direct antifreeze solution 44 within an antifreeze saturator 42, 46, and then directing the at least one of the first or second reactant streams from the saturator 42, 46 through either a first flow field 20 adjacent a first catalyst 14 supported adjacent the PEM electrolyte 12 or a second flow field 26 adjacent a second catalyst 16 supported adjacent the PEM electrolyte 12.
  • the invention includes the method of humidifying a reactant stream while starting the fuel cell 10 as described above when the temperature of the fuel cell 10 is below 0 0 C.
  • the present invention has been disclosed with respect to the described and illustrated fuel cell 10 having at least one reactant inlet antifreeze saturator 42, it is to be understood that the invention is not to be limited to those alternatives and embodiments.
  • the fuel cell 12 may be one of many similar fuel cells secured in a cooperative relationship within a well known fuel cell stack assembly, wherein first and/or the second reactant inlets are integral with common manifolds and related plumbing of the cell stack assembly, in a manner well known in the art. Accordingly, reference should be made primarily to the following claims rather than the foregoing description to determine the scope of the invention.

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  • 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)

Abstract

L'invention concerne une pile à combustible (10) qui inclut un électrolyte à membrane PEM (12) fixé entre un premier catalyseur (14) et un second catalyseur (16), ainsi qu'une plaque de refroidissement scellée (30). Au moins un saturateur anticongélation (42, 46) est fixé en communication par fluide avec l'un d'un premier ou d'un second flux d'agent réactif. Le saturateur (42, 46) contient une solution d'anticongélation directe à poids moléculaire élevé et dirige le flux d'agent réactif pour qu'il traverse le liquide d'anticongélation et revienne dans une ouverture d'entrée d'agent réactif (18, 24) de la pile à combustible (10). La solution d'anticongélation directe à poids moléculaire élevé inclut de préférence comme composant d'anticongélation un polyéthylène glycol présentant un poids moléculaire s'étendant de 200 à 8000 AMU. Un agent préféré d'anticongélation directe à poids moléculaire élevé est un polyéthylène glycol présentant un poids moléculaire d'environ 400. La solution d'anticongélation résiste à la congélation et humidifie le flux d'agent réactif avec uniquement de l'eau.
PCT/US2006/008802 2006-03-10 2006-03-10 Pile à combustible ayant un saturateur anticongélation à entrée d'agent réactif WO2007106082A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/US2006/008802 WO2007106082A1 (fr) 2006-03-10 2006-03-10 Pile à combustible ayant un saturateur anticongélation à entrée d'agent réactif

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US2006/008802 WO2007106082A1 (fr) 2006-03-10 2006-03-10 Pile à combustible ayant un saturateur anticongélation à entrée d'agent réactif

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WO2007106082A1 true WO2007106082A1 (fr) 2007-09-20

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6416891B1 (en) * 1999-11-22 2002-07-09 Utc Fuel Cells, Llc Operating system for a direct antifreeze cooled fuel cell power plant
US20020102448A1 (en) * 1999-07-22 2002-08-01 Breault Richard D. Direct antifreeze cooled fuel cell
US6428916B1 (en) * 1999-12-20 2002-08-06 Utc Fuel Cells, Llc Coolant treatment system for a direct antifreeze cooled fuel cell assembly
US6548200B2 (en) * 2001-04-10 2003-04-15 Utc Fuel Cells, Llc Cold starting of gasoline fueled fuel cell
US20050064261A1 (en) * 2003-09-22 2005-03-24 Breault Richard D. Internal PEM fuel cell water management

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020102448A1 (en) * 1999-07-22 2002-08-01 Breault Richard D. Direct antifreeze cooled fuel cell
US6416891B1 (en) * 1999-11-22 2002-07-09 Utc Fuel Cells, Llc Operating system for a direct antifreeze cooled fuel cell power plant
US6428916B1 (en) * 1999-12-20 2002-08-06 Utc Fuel Cells, Llc Coolant treatment system for a direct antifreeze cooled fuel cell assembly
US6548200B2 (en) * 2001-04-10 2003-04-15 Utc Fuel Cells, Llc Cold starting of gasoline fueled fuel cell
US20050064261A1 (en) * 2003-09-22 2005-03-24 Breault Richard D. Internal PEM fuel cell water management

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