WO2015053915A1 - Humidification control device - Google Patents

Humidification control device Download PDF

Info

Publication number
WO2015053915A1
WO2015053915A1 PCT/US2014/056241 US2014056241W WO2015053915A1 WO 2015053915 A1 WO2015053915 A1 WO 2015053915A1 US 2014056241 W US2014056241 W US 2014056241W WO 2015053915 A1 WO2015053915 A1 WO 2015053915A1
Authority
WO
WIPO (PCT)
Prior art keywords
control device
humidification control
anode
comonomer
polymer chain
Prior art date
Application number
PCT/US2014/056241
Other languages
French (fr)
Inventor
Glenn Shealy
Brian Levy
Original Assignee
W.L. Gore & Associates, Inc.
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 W.L. Gore & Associates, Inc. filed Critical W.L. Gore & Associates, Inc.
Priority to KR1020167010520A priority Critical patent/KR20160060131A/en
Priority to EP14784143.1A priority patent/EP3055896A1/en
Priority to CN201480055156.8A priority patent/CN105612647A/en
Priority to CA2925861A priority patent/CA2925861A1/en
Priority to JP2016520664A priority patent/JP2017500524A/en
Publication of WO2015053915A1 publication Critical patent/WO2015053915A1/en

Links

Classifications

    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00Fuel cells; Manufacture thereof
    • H01M8/04Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04082Arrangements for control of reactant parameters, e.g. pressure or concentration
    • H01M8/04089Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants
    • H01M8/04119Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants with simultaneous supply or evacuation of electrolyte; Humidifying or dehumidifying
    • H01M8/04126Humidifying
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00Electrolytic production of inorganic compounds or non-metals
    • C25B1/01Products
    • C25B1/02Hydrogen or oxygen
    • C25B1/04Hydrogen or oxygen by electrolysis of water
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B13/00Diaphragms; Spacing elements
    • C25B13/04Diaphragms; Spacing elements characterised by the material
    • C25B13/08Diaphragms; Spacing elements characterised by the material based on organic materials
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/17Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
    • C25B9/19Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
    • C25B9/23Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms comprising ion-exchange membranes in or on which electrode material is embedded
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/70Assemblies comprising two or more cells
    • C25B9/73Assemblies comprising two or more cells of the filter-press type
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D17/00Constructional parts, or assemblies thereof, of cells for electrolytic coating
    • C25D17/002Cell separation, e.g. membranes, diaphragms
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F21LIGHTING
    • F21SNON-PORTABLE LIGHTING DEVICES; SYSTEMS THEREOF; VEHICLE LIGHTING DEVICES SPECIALLY ADAPTED FOR VEHICLE EXTERIORS
    • F21S45/00Arrangements within vehicle lighting devices specially adapted for vehicle exteriors, for purposes other than emission or distribution of light
    • F21S45/30Ventilation or drainage of lighting devices
    • F21S45/33Ventilation or drainage of lighting devices specially adapted for headlamps
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00Fuel cells; Manufacture thereof
    • H01M8/04Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04298Processes for controlling fuel cells or fuel cell systems
    • H01M8/04694Processes for controlling fuel cells or fuel cell systems characterised by variables to be controlled
    • H01M8/04828Humidity; Water content
    • H01M8/04835Humidity; Water content of fuel cell reactants
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00Fuel cells; Manufacture thereof
    • H01M8/10Fuel cells with solid electrolytes
    • H01M8/1004Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30Hydrogen technology
    • Y02E60/36Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30Hydrogen technology
    • Y02E60/50Fuel cells

Definitions

  • This disclosure relates to the field of humidification control devices that utilize a membrane electrode assembly (MEA) for humidification control of an enclosure by electrolysis.
  • enclosures may include, but are not limited to, lighting enclosures such as automotive head lamps, vehicle electronic control units, compact photovoltaic arrays, cameras such as surveillance cameras, bar code scanners, battery packs, power control units, fluid reservoirs, charging stations, telecommunication devices, transformer units, hard disk drives and the like.
  • Humidification control devices employing a membrane electrode assembly (MEA) as the dehumidifying element are known.
  • the MEA is configured such that a polymer electrolyte membrane (PEM) is sandwiched between two electrodes, namely an anode and a cathode.
  • PEM polymer electrolyte membrane
  • H + hydrogen
  • O 2_ oxygen
  • the PEM serves as the hydrogen ion exchange membrane and moves the hydrogen ions to the cathode side, which may face the ambient environment.
  • the hydrogen ions react with oxygen in the air to form water molecules.
  • the enclosure is dehumidified by moving the moisture from the anode side of the MEA into the environment on the cathode side.
  • One challenge associated with using an MEA as the dehumidifying element is that the water generated on the cathode side (e.g., outside of the enclosure) tends to diffuse back into the enclosure through the PEM after the enclosure has been dehumidified, a phenomenon referred to as back diffusion.
  • the water diffusing back into the enclosure needs to be removed from the enclosure again, increasing the electric current required to operate the MEA.
  • back diffusion lowers the overall dehumidifying efficiency of the MEA.
  • Dehumidification devices employing MEAs are commercially available.
  • One example is the Rosahl line of dehumidification devices (Westside International, Oxfordshire, UK). These devices typically utilize Nafion® 1 15 (E.I.
  • Nafion® 1 15 is a sulfonated tetrafluoroethylene based fluoropolymer that includes perfluorovinyl ether groups terminated with sulfonated groups that are incorporated onto a tetrafluoroethylene backbone.
  • the overall dehumidifying efficiency of dehumidification elements employing Nafion ® 1 15 as the PEM is limited due to back diffusion. Thicker membrane materials may lower back diffusion to a certain degree. However, the use of thicker membranes increases the material cost of the dehumidifying element significantly.
  • One embodiment is directed to a humidification control device that is configured for controlling the humidity of an enclosure.
  • the humidification control device includes a membrane electrode assembly, the membrane electrode assembly comprising an anode and a cathode, and at least a first proton exchange membrane disposed between the anode and the cathode.
  • the proton exchange membrane comprises a polymeric material comprising a resin that includes a functional TFE copolymer having a polymer chain of TFE and at least one comonomer having a proton conducting functional group pendant to the polymer chain, where the at least one comonomer having a proton conducting functional group pendant to the polymer chain is present in an amount of at least about 0.01 mol.% and not greater than about 7 mol.% of the functional TFE copolymer.
  • the device also includes first and second electrically conductive terminals interconnected to the anode and cathode, respectively, and configured to apply an electric potential across the membrane electrode assembly.
  • the at least one comonomer having a proton conducting functional group pendant to the polymer chain is perfluorosulfonyl vinyl ether (PSVE).
  • PSVE perfluorosulfonyl vinyl ether
  • the polymeric material has an equivalent weight (EW) of at least about 1500, such as at least about 2400.
  • EW equivalent weight
  • the polymeric material is fabricated by extruding a fine powder resin into a tape, calendering the tape, and subjecting the calendered tape to heat-treatment to a temperature greater than the crystalline melting temperature of polytetrafluoroethylene (PTFE) to form a non-porous tape.
  • PTFE polytetrafluoroethylene
  • the polymeric material is fabricated by expanding the resin into a porous functional tetrafluoroethylene (TFE) copolymer material having a microstructure characterized by nodes interconnected by fibrils, and further densifying the porous material and subjecting material to a heat treatment above the crystalline melting temperature of PTFE to form a non-porous structure.
  • TFE tetrafluoroethylene
  • the humidification control device may be configured to be positioned across an aperture of an enclosure to dehumidify a gaseous enclosed volume within an enclosed space defined by the enclosure.
  • a DC voltage source is operatively connected to the first and second electrically conductive terminals.
  • the proton exchange membrane has a thickness of not greater than about 200 ⁇ .
  • the at least one comonomer having a proton conducting functional group pendant to the polymer chain is present in an amount of not greater than about 7 mol.% of the functional TFE copolymer.
  • the proton exchange membrane has a Gurley number of at least about 1000 seconds.
  • an apparatus in another embodiment, includes an enclosure defining an enclosed space and a humidification control device operatively affixed to the enclosure.
  • the humidification control device includes an anode and a cathode, and at least a first proton exchange membrane disposed between the anode and the cathode.
  • the proton exchange membrane comprises a polymeric material comprising a resin that includes a functional TFE copolymer having a polymer chain of TFE and at least one comonomer having a proton conducting functional group pendant to the polymer chain, where the at least one comonomer having a proton conducting functional group pendant to the polymer chain is present in an amount of at least about 0.01 mol.% and not greater than about 7 mol.% of the functional TFE copolymer.
  • First and second electrically conductive terminals are interconnected to the anode and cathode, and a DC voltage source operatively connected to the first and second electrically conductive terminals.
  • the humidification control device is affixed to the enclosure such that the anode is in fluid communication with the enclosed space, e.g., to dehumidify the enclosure.
  • the at least one comonomer having a proton conducting functional group pendant to the polymer chain is PSVE.
  • the polymeric material has an equivalent weight of at least about 1500, such as at least about 2400.
  • the proton exchange membrane has a thickness of not greater than about 200 pm.
  • the at least one comonomer having a proton conducting functional group pendant to the polymer chain may present in an amount of not greater than about 5 mol.% of the functional TFE copolymer.
  • the proton exchange membrane has a Gurley number at least about 1000 seconds.
  • Fig. 1 illustrates a schematic view of a humidification control device.
  • FIG. 2 illustrates a schematic view of an apparatus that includes a dehumidification device that is operatively affixed to an enclosure for dehumidification of an enclosed space.
  • Fig. 1 illustrates a schematic cross-sectional view of a humidity control device 104 in accordance with one embodiment of this disclosure.
  • the humidity control device 104 utilizes a membrane electrode assembly (MEA) 108 as the humidity control element.
  • MEA membrane electrode assembly
  • the MEA 108 includes an anode 112 and a cathode 116, which are separated by a proton exchange membrane (PEM) 120.
  • the humidity control device 104 further includes conductive terminals 124a and 124b that are operatively connected to the anode 112 and to the cathode 116.
  • a voltage source 128 e.g., a DC voltage source
  • protons (H + ) are selectively transported through the PEM 120 to the cathode 116 where they react with O2 (e.g., in the ambient air) to form water in accordance with Equation 2:
  • the electrodes may comprise an electrically conductive material such as particulate carbon and a polymeric binder.
  • the conductive material often includes a catalytic material dispersed thereon that is selected to catalyze the desired reaction at the electrode.
  • the cathode 116 may include a platinum (Pt) catalyst dispersed on particulate carbon to catalyze the oxidation of protons (H + ) to form water.
  • the anode 112 may include a catalyst for the reduction of water, such as a mixture of Pt metal and an iridium compound (e.g., iridium oxide).
  • Electrodes may be prepared using known methods in the art, such as those described in U.S. Patent No. 6,054,230 by Kato and U.S. Patent No. 6,723,464 by Tabata et al.
  • the phenomenon of back diffusion of the water formed at the cathode 116 across the PEM 120 and the anode 112 is illustrated in Fig. 1 by arrow A.
  • Such back diffusion may be present when the external conditions (e.g., adjacent the cathode 116) are ambient with no forced convection to move moisture away from the cathode 116.
  • Such back diffusion lowers the overall efficiency of the MEA 108 by requiring more energy to drive Equation 1 at the anode.
  • the PEM materials of the present disclosure advantageously utilize functional tetrafluoroethylene (TFE) copolymers that improve the overall efficiency of the device (e.g., dehumidification efficiency) when compared to commercial PEM materials such as Nafion ® 1 15.
  • TFE functional tetrafluoroethylene
  • the PEM 120 comprises a functional TFE copolymer.
  • the functional TFE copolymer includes functional groups that are pendant to the polymer chain.
  • the functional TFE copolymer may be formed by copolymerizing TFE with at least one functional comonomer, i.e., a comonomer having at least one functional group.
  • the functional comonomer may advantageously include proton conducting groups, such as, for example, phosphonic acid groups and sulfonic acid groups.
  • the functional comonomer comprises a fluorovinyl ether, such as perfluorosulfonyl vinyl ether (PSVE).
  • the comonomer may be present in the copolymer in a relatively low amount as compared to conventional devices.
  • comonomer may be present in the copolymer in an amount of at least about 0.01 mol.%, such as at least about 0.1 mol.%.
  • the amount of comonomer present in the copolymer should not be greater than about 7 mol.%, or even not greater than about 6 mol.%, such as not greater than about 5 mol.%. It is also desirable that the PEM 120 have a relatively high equivalent weight (EW).
  • the equivalent weight is a characteristic of an ionomer that is equal to the weight of the polymer in acid form that is required to neutralize one equivalent of NaOH. A higher equivalent weight indicates that there are fewer active ionic species (e.g., H + ) present. If it takes more of the polymer to neutralize one equivalent of hydroxyl ions from NaOH, there must be fewer active ionic species within the polymer.
  • the ionic conductivity of the membrane is generally proportional to the number of active ionic species in the polymer.
  • the PEM may have an equivalent weight of at least about 1500, at least about 2000 or at least about 2400. In exemplary embodiments, the equivalent weight of the PEM will not be greater than about 9000.
  • the PEM 120 be relatively thin for efficient operation of the humidification control device 104.
  • the PEM may have a thickness of not greater than about 200 ⁇ , such as not greater than about 150 pm or not greater than about 125 pm.
  • the PEM will have a thickness of at least about 10 pm.
  • U.S. Patent Publication No. 2010/0248324 by Xu et al. describes a method for the manufacture of a porous functional TFE copolymer material that may be utilized in part to produce the PEM according to the present disclosure.
  • Xu et al. describes a method for the manufacture of a functional TFE copolymer fine powder resin. The fine powder resin is then extruded and expanded to form a microporous expanded TFE copolymer film.
  • the functional TFE copolymer should be densified and treated at a temperature above the crystalline melting temperature of PTFE to be substantially non-porous.
  • the functional TFE copolymer material may be extruded to produce a tape, which may further be heat-treated to a temperature greater than crystalline melting temperature of TFE to form a non-porous structure.
  • the functional TFE copolymer material may be expanded into a microstructure characterized by nodes and fibrils. Dense (non-porous) articles may then be formed from the expanded TFE copolymer materials by densification and heating above the crystalline melting temperature of PTFE according to the methods described in U.S. No. Patent 3,953,566 by Gore and/or U.S. Patent No. 7,521 ,010 by Kennedy et al. [0028]
  • the PEM should be resistant to the flow of fluids through the membrane, i.e., the membrane should have a relatively low porosity.
  • the PEM according to the invention may be characterized as having a relatively high Gurley number.
  • the Gurley number is a unit describing the number of seconds required for 100 cm 3 of air to pass through one square inch (in 2 ) of the material.
  • the measurement of a Gurley number is described, for example, in U.S. Patent No. 5,547,551 by Bahar et al,
  • the PEM may have a Gurley number of at least about 1000 seconds, such as at least about 5000 seconds and even at least about 10,000 seconds.
  • the MEA 108 may include gas diffusion layers 132a and 132b which may be disposed on opposite sides of the anode 112 and cathode 116 from the PEM 120.
  • the gas diffusion layers 132a/132b may comprise porous carbon cloth, for example.
  • the device 104 further includes conductive terminals 124a and 124b that are operatively connected to the anode 112 and to the cathode 116 to supply an electric potential from a voltage source 128.
  • Fig. 2 schematically illustrates an apparatus in accordance with the present disclosure that includes a humidity control device 204 (e.g., a dehumidification device) that is operatively affixed to an enclosure 200 to control the humidity within the enclosure by dehumidifying an enclosed space 236 defined by the enclosure 200.
  • the device 204 includes an MEA 208 that may be configured in the manner described with respect to MEA 104 (Fig. 1).
  • the anode 212 faces (e.g., is in fluid communication with) the enclosed space 236.
  • the cathode 216 faces (e.g., is in fluid communication with) an environment that is separated from the enclosed space 236, such as the ambient environment surrounding the enclosure 200.
  • the enclosed space 236 may contain components (e.g., lighting components or electrical components) that require a low relative humidity for optimum operation and/or extended lifetime of the components.
  • components e.g., lighting components or electrical components
  • the device can be utilized in other configurations.
  • the device may be configured such that the cathode faces an enclosed space and the anode faces an ambient environment, such as to increase the humidity in the enclosed space, e.g., to maintain a desired minimum humidity within the enclosed space.
  • a fine powder of TFE-PSVE copolymer containing 3.2 mol.% PSVE was blended with Isopar® K (Exxon Mobile Corp., Fairfax, VA) in the proportion of 0.25 g/g of fine powder.
  • the lubricated powder was compressed in a cylinder to form a pellet and placed into an oven set at about 49°C for about 12 hours.
  • the compressed and heated pellets were extruded to produce a tape that was about 16 cm wide and about 0.78 mm thick.
  • the tape was calendered in a first calendering step to a thickness of about 0.381 mm and was further calendered in a second calendering step to a thickness of about 0.125 mm.
  • This calendered tape was then allowed to dry at room temperature while unrestrained.
  • the calendered and dried tape was then restrained and heated in an oven at about 365°C for about 90 seconds to form a substantially non-porous tape.
  • the resultant non-porous tape was then immersed in isopropyl alcohol (IPA) at about 85°C for about 19 hours followed by immersion in a 20 wt.% KOH aqueous solution at about 125°C for about 72 hours.
  • the tape was then rinsed with deionized water and immersed in 15 wt.% nitric acid at about 125°C for about 48 hours, followed by a deionized water rinse.
  • the tape was then air dried at room temperature.
  • This reacted, non-porous tape comprised a functional TFE copolymer having 3.2 mol.% sulfonic acid functional groups and was used as the PEM material.
  • the equivalent weight (EW) of the PEM material was about 4510.
  • the resulting anode had a Pt loading of about 0.35 mg/cm 2 and an iridium loading of about 0.35 mg/cm 2 .
  • EW 4 wt.% TFE/PSVE copolymer
  • All three layers were nominally 63.5 mm in diameter, but the anode and cathode were about 4 mm smaller in diameter as compared to the PEM to avoid shorting across the PEM.
  • the three layers were then pressed at about 173°C for about five minutes under a pressure of about 1 15 psi.
  • the ePTFE substrate layers in the anode and the cathode were then removed, resulting in a three layered stack.
  • Gas diffusion layers (Carbel ® CL, W.L. Gore & Associates, Newark, DE) were then attached on either side of the three layered stack, one at a time, by heating to about 173°C and contacting with the electrode for about 180 seconds under a pressure of about 1 15 psi.
  • Circular stainless steel current collectors in the form of a screen with attachment tabs were placed on either side of the five-layered MEA construction.
  • the thickness and the overall dehumidifying efficiency of the MEA was measured and reported in Table 1.
  • EXAMPLE 2 A fine powder of TFE-PSVE copolymer, containing 4.7 mol.% PSVE was blended with Isopar ® K (Exxon Mobile Corp., Fairfax, VA) in the proportion of 0.243 g/g of fine powder.
  • the lubricated powder was compressed in a cylinder to form a pellet and was placed into an oven set at about 49°C for about 12 hours.
  • the compressed and heated pellets were ram extruded to produce a tape that was about 5.87 cm wide and about 0.81 mm thick.
  • the tape was calendered in a first calendering step to a thickness of about 0.254 mm.
  • This calendered tape was further calendered in a second calendering step to a thickness of about 0.122 mm.
  • This calendering tape was then restrained and dried at about 250°C. The dried tape was then heated in an oven at about 365°C for about 90 seconds, while restrained, to form a substantially non-porous tape.
  • the resultant non-porous tape was then immersed in I PA at 85°C for about 19 hours followed by immersion in a 20 wt.% KOH aqueous solution at 125°C for about 72 hours.
  • the tape was then rinsed with deionized water and was immersed in 15 wt.% nitric acid at about 125°C for about 48 hours followed by a deionized water rinse.
  • the tape was then air dried at room temperature.
  • This reacted non-porous tape comprised a functional TFE copolymer having 4.7 mol.% sulfonic acid functional groups and was used as the PEM material.
  • the equivalent weight (EW) of the PEM material was 2800.
  • Example 1 A five layered MEA as described in Example 1 was constructed using the PEM material. The thickness and the overall dehumidifying efficiency of the MEA were measured and reported in Table 1.
  • Example 1 An MEA as described in Example 1 was constructed using one layer, two layers and five layers of Nafion ® 1 15 (E.I. DuPont de Nemours and Company, Wilmington, DE) as the PEM material. The equivalent weight of the PEM was 1 100. The thickness and the overall dehumidifying efficiency of these MEAs were measured and reported in Table 1.
  • Nafion ® 1 15 E.I. DuPont de Nemours and Company, Wilmington, DE
  • the equivalent weight of the PEM was 1 100.
  • the thickness and the overall dehumidifying efficiency of these MEAs were measured and reported in Table 1.
  • COMPARATIVE EXAMPLE 2 An MEA as described in Example 1 was constructed using a commercially available PEM material (GORE-SELECT® Part No: GSM650.35) used for fuel cells and comprising 14.8 mol.% PSVE. The equivalent weight of the PEM was 1020. The thickness and the overall dehumidifying efficiency of these MEAs were measured and reported in Table 1 .
  • the MEAs employing the functional TFE copolymers described herein for the PEM provide an overall dehumidification efficiency that is at least 5 times greater than that of an MEA using a single layer of Nafion ® 1 15. Even when the thickness of the Nafion ® 1 15 was increased by a factor of 4x, the dehumidifying efficiency of the MEA disclosed herein was still at least 2x greater.
  • the overall dehumidifying efficiency test reported in Table 1 is a steady state measurement that measures water pumping rate and current draw of an energized MEA with a fixed relative humidity (RH) and temperature on the cathode and anode side.
  • the cathode side temperature and RH are controlled with a dedicated room ventilation system and maintained at about 22°C and about 50% RH respectively. There is no forced air convection over the cathode side of the MEA.
  • the anode side temperature is maintained at about 22°C.
  • a RH of about 22% at this temperature is established by placing the MEA over a Petri dish with a two phase mixture of 6.6 g potassium acetate in 2.2 g of water.
  • the distance between the solution and surface of the anode is minimal, at about 3 mm.
  • the five layer MEA construction is screwed on to a sample holder.
  • the holder/Petri dish assembly is placed on a tared microbalance (Mettler Toledo AG204) and the initial weight (Wo) of the holder/ Petri dish assembly is measured.
  • the doors of the microbalance are opened slightly and a DC power supply (Instek PS-3225D) unit is attached to the electrical leads of the current collector tabs on the MEA.
  • the power supply is connected to an ammeter (Ahlborn ZA9901-AB3) to measure the current.
  • the output from the ammeter is transmitted to a data logger (Ahlborn Almemo 2890-9).
  • the DC power supply is turned on to produce 1.5 volts for 30 minutes and the current is measured during this time period. After 30 minutes, the power supply is turned off by removing the electrical leads attached to the current collector tabs on the MEA. The doors of the balance are closed and the housing/ Petri dish assembly is weighed (Wi).
  • the power supply is re-attached to the MEA and turned on again and the above cycle is repeated three times to measure W2, W3, W4 over a period of 1 .5 hours.
  • the difference in weight between Wi and Wo, W2 and Wi , W3 and W2 and W4 and W3 over time is plotted.
  • the dehumidification efficiency (mg water pumped per Coulomb) is calculated
  • asymptotic value of water pumping rate (mg/sec) asymptotic value of the current density (coulomb/sec, or amp).
  • the method used to determine equivalent weight takes a measured weight of the solid sample and calculates an acid equivalent weight based on the first inflection point of the titration curve near pH 7. Specifically, for each sample, approximately 5 g of the solid sample weighing no more than 0.05 g each are dried in an oven for at least two hours at 80°C under full vacuum ( ⁇ 2 in. Hg). The dried pieces are removed from the oven and placed in a capped container to minimize moisture pickup. After allowing the dried sample to cool to room temperature in the capped container, approximately 0.15 g is quickly weighed into a 100 ml titration cup.
  • the sample of known dry weight is then allowed to soak in the titration cup for 15 minutes in 5 ml of deionized water and 5 ml of ethanol. To the soaked sample, 55 ml of 2. ON NaCI solution is then added.
  • a back titration method using a TIM900 Titration Manager (Radiometer Analytical S.A., Lyon, France) is then started beginning with the addition of 5 ml of 0.05N NaOH solution. The entire blend is then stirred for 15 minutes under a nitrogen blanket prior to the acid titration with 0.01 N HCI solution.
  • the end point near pH 7 is used to calculate both the ion exchange capacity (IEC) and the acid equivalent weight (EW) of the sample according to:

Abstract

A humidification control device and an apparatus implementing the humidification control device is provided. The device includes a membrane electrode assembly (MEA) for the control of humidity in an enclosed space via electrolysis. The MEA includes an anode, a cathode and a proton exchange membrane (PEM) disposed between the anode and the cathode. The PEM is selected to increase the efficiency of the humidification control device by decreasing the back diffusion of water across the PEM. The PEM may include a functional tetrafluoroethylene (TFE) copolymer having a polymer chain of TFE and at least one comonomer having a proton conducting functional group pendant to said polymer chain. The comonomer may be present in an amount from about 0.01 mol. % to about 7 mol. % of the TFE copolymer. In one embodiment, the comonomer is a fluorovinyl ether such as perfluorosulfonyl vinyl ether (PSVE).

Description

HUMIDIFICATION CONTROL DEVICE FIELD
[0001] This disclosure relates to the field of humidification control devices that utilize a membrane electrode assembly (MEA) for humidification control of an enclosure by electrolysis. Such enclosures may include, but are not limited to, lighting enclosures such as automotive head lamps, vehicle electronic control units, compact photovoltaic arrays, cameras such as surveillance cameras, bar code scanners, battery packs, power control units, fluid reservoirs, charging stations, telecommunication devices, transformer units, hard disk drives and the like.
BACKGROUND
[0002] Humidification control devices employing a membrane electrode assembly (MEA) as the dehumidifying element are known. The MEA is configured such that a polymer electrolyte membrane (PEM) is sandwiched between two electrodes, namely an anode and a cathode. When an electric potential is applied across the MEA, water molecules are electrolyzed into hydrogen (H+) and oxygen (O2_) ions on the anode side, which faces the inside of the enclosure. The PEM serves as the hydrogen ion exchange membrane and moves the hydrogen ions to the cathode side, which may face the ambient environment. On the cathode side, the hydrogen ions react with oxygen in the air to form water molecules. Thus, the enclosure is dehumidified by moving the moisture from the anode side of the MEA into the environment on the cathode side.
[0003] One challenge associated with using an MEA as the dehumidifying element is that the water generated on the cathode side (e.g., outside of the enclosure) tends to diffuse back into the enclosure through the PEM after the enclosure has been dehumidified, a phenomenon referred to as back diffusion. The water diffusing back into the enclosure needs to be removed from the enclosure again, increasing the electric current required to operate the MEA. As a result, back diffusion lowers the overall dehumidifying efficiency of the MEA. [0004] Dehumidification devices employing MEAs are commercially available. One example is the Rosahl line of dehumidification devices (Westside International, Oxfordshire, UK). These devices typically utilize Nafion® 1 15 (E.I. DuPont de Nemours and Company, Wilmington, DE) as the PEM. Nafion® 1 15 is a sulfonated tetrafluoroethylene based fluoropolymer that includes perfluorovinyl ether groups terminated with sulfonated groups that are incorporated onto a tetrafluoroethylene backbone. However, the overall dehumidifying efficiency of dehumidification elements employing Nafion® 1 15 as the PEM is limited due to back diffusion. Thicker membrane materials may lower back diffusion to a certain degree. However, the use of thicker membranes increases the material cost of the dehumidifying element significantly.
SUMMARY
[0005] One embodiment is directed to a humidification control device that is configured for controlling the humidity of an enclosure. The humidification control device includes a membrane electrode assembly, the membrane electrode assembly comprising an anode and a cathode, and at least a first proton exchange membrane disposed between the anode and the cathode. The proton exchange membrane comprises a polymeric material comprising a resin that includes a functional TFE copolymer having a polymer chain of TFE and at least one comonomer having a proton conducting functional group pendant to the polymer chain, where the at least one comonomer having a proton conducting functional group pendant to the polymer chain is present in an amount of at least about 0.01 mol.% and not greater than about 7 mol.% of the functional TFE copolymer. The device also includes first and second electrically conductive terminals interconnected to the anode and cathode, respectively, and configured to apply an electric potential across the membrane electrode assembly.
[0006] In one characterization, the at least one comonomer having a proton conducting functional group pendant to the polymer chain is perfluorosulfonyl vinyl ether (PSVE). In another characterization, the polymeric material has an equivalent weight (EW) of at least about 1500, such as at least about 2400. [0007] In another characterization, the polymeric material is fabricated by extruding a fine powder resin into a tape, calendering the tape, and subjecting the calendered tape to heat-treatment to a temperature greater than the crystalline melting temperature of polytetrafluoroethylene (PTFE) to form a non-porous tape. In another characterization, the polymeric material is fabricated by expanding the resin into a porous functional tetrafluoroethylene (TFE) copolymer material having a microstructure characterized by nodes interconnected by fibrils, and further densifying the porous material and subjecting material to a heat treatment above the crystalline melting temperature of PTFE to form a non-porous structure.
[0008] The humidification control device may be configured to be positioned across an aperture of an enclosure to dehumidify a gaseous enclosed volume within an enclosed space defined by the enclosure. In another characterization, a DC voltage source is operatively connected to the first and second electrically conductive terminals. In yet another characterization, the proton exchange membrane has a thickness of not greater than about 200 μηη. In yet another characterization, the at least one comonomer having a proton conducting functional group pendant to the polymer chain is present in an amount of not greater than about 7 mol.% of the functional TFE copolymer. In a further characterization, the proton exchange membrane has a Gurley number of at least about 1000 seconds.
[0009] In another embodiment, an apparatus is provided that includes an enclosure defining an enclosed space and a humidification control device operatively affixed to the enclosure. The humidification control device includes an anode and a cathode, and at least a first proton exchange membrane disposed between the anode and the cathode. The proton exchange membrane comprises a polymeric material comprising a resin that includes a functional TFE copolymer having a polymer chain of TFE and at least one comonomer having a proton conducting functional group pendant to the polymer chain, where the at least one comonomer having a proton conducting functional group pendant to the polymer chain is present in an amount of at least about 0.01 mol.% and not greater than about 7 mol.% of the functional TFE copolymer. First and second electrically conductive terminals are interconnected to the anode and cathode, and a DC voltage source operatively connected to the first and second electrically conductive terminals.
[0010] In a further characterization, the humidification control device is affixed to the enclosure such that the anode is in fluid communication with the enclosed space, e.g., to dehumidify the enclosure. In another characterization, the at least one comonomer having a proton conducting functional group pendant to the polymer chain is PSVE.
[0011] In another characterization, the polymeric material has an equivalent weight of at least about 1500, such as at least about 2400. In yet another characterization, the proton exchange membrane has a thickness of not greater than about 200 pm.
[0012] In yet another characterization, the at least one comonomer having a proton conducting functional group pendant to the polymer chain may present in an amount of not greater than about 5 mol.% of the functional TFE copolymer. In another characterization, the proton exchange membrane has a Gurley number at least about 1000 seconds.
DESCRIPTION OF THE DRAWINGS
[0013] Fig. 1 illustrates a schematic view of a humidification control device.
[0014] Fig. 2 illustrates a schematic view of an apparatus that includes a dehumidification device that is operatively affixed to an enclosure for dehumidification of an enclosed space.
DETAILED DESCRIPTION
[0015] High relative humidity within an enclosure can affect the working characteristics and/or the useful lifetime of component(s) sealed within the enclosure. Such enclosures may therefore be equipped with a humidity control device (e.g., a dehumidification device) that employs an membrane electrode assembly (MEA) as the dehumidifying element. Such enclosures may include, for example, lighting and electronic enclosures that contain sensitive components that may be affected by inadequate humidity control within the enclosure. [0016] Fig. 1 illustrates a schematic cross-sectional view of a humidity control device 104 in accordance with one embodiment of this disclosure. The humidity control device 104 utilizes a membrane electrode assembly (MEA) 108 as the humidity control element. The MEA 108 includes an anode 112 and a cathode 116, which are separated by a proton exchange membrane (PEM) 120. The humidity control device 104 further includes conductive terminals 124a and 124b that are operatively connected to the anode 112 and to the cathode 116. A voltage source 128 (e.g., a DC voltage source) is operatively attached to the conductive terminals 124a and 124b and is configured to apply a voltage across the anode 112 and the cathode 116.
[0017] When a voltage is applied across the anode 112 and the cathode 116, water that is adjacent to the anode 112 is reduced to protons and oxygen in accordance with Equation 1 :
Figure imgf000006_0001
[0018] The protons (H+) are selectively transported through the PEM 120 to the cathode 116 where they react with O2 (e.g., in the ambient air) to form water in accordance with Equation 2:
Figure imgf000006_0002
[0019] Thus, water is removed from the anode side of the device 104 and water is formed on the cathode side of the device 104. As a result, the relative humidity on the anode side decreases (i.e., dehumidification) and the relative humidity on the cathode side increases (i.e., humidification).
[0020] The electrodes (i.e., anode 112 and cathode 116) may comprise an electrically conductive material such as particulate carbon and a polymeric binder. The conductive material often includes a catalytic material dispersed thereon that is selected to catalyze the desired reaction at the electrode. For example, the cathode 116 may include a platinum (Pt) catalyst dispersed on particulate carbon to catalyze the oxidation of protons (H+) to form water. The anode 112 may include a catalyst for the reduction of water, such as a mixture of Pt metal and an iridium compound (e.g., iridium oxide). Other metals or metal compounds that are useful as catalysts for the electrodes will be apparent to those of skill in the art. The electrodes may be prepared using known methods in the art, such as those described in U.S. Patent No. 6,054,230 by Kato and U.S. Patent No. 6,723,464 by Tabata et al.
[0021] The phenomenon of back diffusion of the water formed at the cathode 116 across the PEM 120 and the anode 112 is illustrated in Fig. 1 by arrow A. Such back diffusion may be present when the external conditions (e.g., adjacent the cathode 116) are ambient with no forced convection to move moisture away from the cathode 116. Such back diffusion lowers the overall efficiency of the MEA 108 by requiring more energy to drive Equation 1 at the anode. The PEM materials of the present disclosure advantageously utilize functional tetrafluoroethylene (TFE) copolymers that improve the overall efficiency of the device (e.g., dehumidification efficiency) when compared to commercial PEM materials such as Nafion® 1 15.
[0022] In one embodiment, the PEM 120 comprises a functional TFE copolymer. The functional TFE copolymer includes functional groups that are pendant to the polymer chain. The functional TFE copolymer may be formed by copolymerizing TFE with at least one functional comonomer, i.e., a comonomer having at least one functional group. The functional comonomer may advantageously include proton conducting groups, such as, for example, phosphonic acid groups and sulfonic acid groups. In one particular embodiment, the functional comonomer comprises a fluorovinyl ether, such as perfluorosulfonyl vinyl ether (PSVE).
[0023] According to the embodiments disclosed herein, the comonomer may be present in the copolymer in a relatively low amount as compared to conventional devices. In one particular characterization, comonomer may be present in the copolymer in an amount of at least about 0.01 mol.%, such as at least about 0.1 mol.%. However, the amount of comonomer present in the copolymer should not be greater than about 7 mol.%, or even not greater than about 6 mol.%, such as not greater than about 5 mol.%. It is also desirable that the PEM 120 have a relatively high equivalent weight (EW). The equivalent weight is a characteristic of an ionomer that is equal to the weight of the polymer in acid form that is required to neutralize one equivalent of NaOH. A higher equivalent weight indicates that there are fewer active ionic species (e.g., H+) present. If it takes more of the polymer to neutralize one equivalent of hydroxyl ions from NaOH, there must be fewer active ionic species within the polymer. The ionic conductivity of the membrane is generally proportional to the number of active ionic species in the polymer.
[0024] In accordance with the present disclosure, the PEM may have an equivalent weight of at least about 1500, at least about 2000 or at least about 2400. In exemplary embodiments, the equivalent weight of the PEM will not be greater than about 9000.
[0025] It is also desirable that the PEM 120 be relatively thin for efficient operation of the humidification control device 104. In this regard, it has been found that back diffusion of water in the device 104 can be decreased even when utilizing a relatively thin PEM 120. In this regard, the PEM may have a thickness of not greater than about 200 μιτι, such as not greater than about 150 pm or not greater than about 125 pm. In exemplary embodiments, the PEM will have a thickness of at least about 10 pm.
[0026] U.S. Patent Publication No. 2010/0248324 by Xu et al. describes a method for the manufacture of a porous functional TFE copolymer material that may be utilized in part to produce the PEM according to the present disclosure. Xu et al. describes a method for the manufacture of a functional TFE copolymer fine powder resin. The fine powder resin is then extruded and expanded to form a microporous expanded TFE copolymer film. For the formation of a PEM 120 for use in a humidification control device, the functional TFE copolymer should be densified and treated at a temperature above the crystalline melting temperature of PTFE to be substantially non-porous. Accordingly, in one embodiment, the functional TFE copolymer material may be extruded to produce a tape, which may further be heat-treated to a temperature greater than crystalline melting temperature of TFE to form a non-porous structure.
[0027] In another embodiment, the functional TFE copolymer material may be expanded into a microstructure characterized by nodes and fibrils. Dense (non-porous) articles may then be formed from the expanded TFE copolymer materials by densification and heating above the crystalline melting temperature of PTFE according to the methods described in U.S. No. Patent 3,953,566 by Gore and/or U.S. Patent No. 7,521 ,010 by Kennedy et al. [0028] To function efficiently in an MEA, the PEM should be resistant to the flow of fluids through the membrane, i.e., the membrane should have a relatively low porosity. Thus, the PEM according to the invention may be characterized as having a relatively high Gurley number. The Gurley number is a unit describing the number of seconds required for 100 cm3 of air to pass through one square inch (in2) of the material. The measurement of a Gurley number is described, for example, in U.S. Patent No. 5,547,551 by Bahar et al, Thus, in one embodiment, the PEM may have a Gurley number of at least about 1000 seconds, such as at least about 5000 seconds and even at least about 10,000 seconds.
[0029] As will be appreciated, other components of the MEA 108 may include gas diffusion layers 132a and 132b which may be disposed on opposite sides of the anode 112 and cathode 116 from the PEM 120. The gas diffusion layers 132a/132b may comprise porous carbon cloth, for example. As is noted above, the device 104 further includes conductive terminals 124a and 124b that are operatively connected to the anode 112 and to the cathode 116 to supply an electric potential from a voltage source 128.
[0030] Fig. 2 schematically illustrates an apparatus in accordance with the present disclosure that includes a humidity control device 204 (e.g., a dehumidification device) that is operatively affixed to an enclosure 200 to control the humidity within the enclosure by dehumidifying an enclosed space 236 defined by the enclosure 200. The device 204 includes an MEA 208 that may be configured in the manner described with respect to MEA 104 (Fig. 1). As is illustrated in Fig. 2, the anode 212 faces (e.g., is in fluid communication with) the enclosed space 236. The cathode 216 faces (e.g., is in fluid communication with) an environment that is separated from the enclosed space 236, such as the ambient environment surrounding the enclosure 200. In this manner, moisture may be removed from the enclosed space 236 and vented to the ambient environment. The enclosed space 236 may contain components (e.g., lighting components or electrical components) that require a low relative humidity for optimum operation and/or extended lifetime of the components. [0031] Although illustrated and described as a dehumidification device that is configured to remove moisture from an enclosed space to lower the relative humidity within the enclosed space, it will be appreciated that the device can be utilized in other configurations. For example, the device may be configured such that the cathode faces an enclosed space and the anode faces an ambient environment, such as to increase the humidity in the enclosed space, e.g., to maintain a desired minimum humidity within the enclosed space.
EXAMPLES
[0032] EXAMPLE 1
[0033] A fine powder of TFE-PSVE copolymer containing 3.2 mol.% PSVE was blended with Isopar® K (Exxon Mobile Corp., Fairfax, VA) in the proportion of 0.25 g/g of fine powder. The lubricated powder was compressed in a cylinder to form a pellet and placed into an oven set at about 49°C for about 12 hours. The compressed and heated pellets were extruded to produce a tape that was about 16 cm wide and about 0.78 mm thick. The tape was calendered in a first calendering step to a thickness of about 0.381 mm and was further calendered in a second calendering step to a thickness of about 0.125 mm. This calendered tape was then allowed to dry at room temperature while unrestrained. The calendered and dried tape was then restrained and heated in an oven at about 365°C for about 90 seconds to form a substantially non-porous tape.
[0034] The resultant non-porous tape was then immersed in isopropyl alcohol (IPA) at about 85°C for about 19 hours followed by immersion in a 20 wt.% KOH aqueous solution at about 125°C for about 72 hours. The tape was then rinsed with deionized water and immersed in 15 wt.% nitric acid at about 125°C for about 48 hours, followed by a deionized water rinse. The tape was then air dried at room temperature. This reacted, non-porous tape comprised a functional TFE copolymer having 3.2 mol.% sulfonic acid functional groups and was used as the PEM material. The equivalent weight (EW) of the PEM material was about 4510. [0035] The cathode layer was formed by casting a dispersion of platinum on carbon black (Pt/C) and a TFE/PSVE copolymer (EW=800) in ethanol and water on an expanded PTFE substrate having a thickness of about 0.16 mm and a density of about 0.59 g/cm3. After casting the dispersion onto the substrate, the dispersion was dried at about 140°C. The resulting cathode layer had a Pt loading of about 0,4 mg/cm2.
[0036] The anode layer was formed by casting a dispersion of Pt black, iridium oxide and TFE/PSVE copolymer (EW=800) in ethanol and water on an expanded PTFE substrate having a thickness of about 0.16 mm and density of about 0.59 g/cm3. The resulting anode had a Pt loading of about 0.35 mg/cm2 and an iridium loading of about 0.35 mg/cm2.
[0037] The PEM material was placed between the anode and the cathode layer. To ensure good bonding of the PEM and the electrodes, the PEM layer was painted with a dispersion containing 4 wt.% TFE/PSVE copolymer (EW=800), 4 wt.% water and balance ethanol, and was then dried using a hair drier.
[0038] All three layers (cathode, PEM, anode) were nominally 63.5 mm in diameter, but the anode and cathode were about 4 mm smaller in diameter as compared to the PEM to avoid shorting across the PEM.
[0039] The three layers were then pressed at about 173°C for about five minutes under a pressure of about 1 15 psi. The ePTFE substrate layers in the anode and the cathode were then removed, resulting in a three layered stack. Gas diffusion layers (Carbel® CL, W.L. Gore & Associates, Newark, DE) were then attached on either side of the three layered stack, one at a time, by heating to about 173°C and contacting with the electrode for about 180 seconds under a pressure of about 1 15 psi.
[0040] Circular stainless steel current collectors in the form of a screen with attachment tabs were placed on either side of the five-layered MEA construction. The thickness and the overall dehumidifying efficiency of the MEA was measured and reported in Table 1.
EXAMPLE 2 [0041] A fine powder of TFE-PSVE copolymer, containing 4.7 mol.% PSVE was blended with Isopar® K (Exxon Mobile Corp., Fairfax, VA) in the proportion of 0.243 g/g of fine powder. The lubricated powder was compressed in a cylinder to form a pellet and was placed into an oven set at about 49°C for about 12 hours. The compressed and heated pellets were ram extruded to produce a tape that was about 5.87 cm wide and about 0.81 mm thick. The tape was calendered in a first calendering step to a thickness of about 0.254 mm. This calendered tape was further calendered in a second calendering step to a thickness of about 0.122 mm. This calendering tape was then restrained and dried at about 250°C. The dried tape was then heated in an oven at about 365°C for about 90 seconds, while restrained, to form a substantially non-porous tape.
[0042] The resultant non-porous tape was then immersed in I PA at 85°C for about 19 hours followed by immersion in a 20 wt.% KOH aqueous solution at 125°C for about 72 hours. The tape was then rinsed with deionized water and was immersed in 15 wt.% nitric acid at about 125°C for about 48 hours followed by a deionized water rinse. The tape was then air dried at room temperature. This reacted non-porous tape comprised a functional TFE copolymer having 4.7 mol.% sulfonic acid functional groups and was used as the PEM material. The equivalent weight (EW) of the PEM material was 2800.
[0043] A five layered MEA as described in Example 1 was constructed using the PEM material. The thickness and the overall dehumidifying efficiency of the MEA were measured and reported in Table 1.
COMPARATIVE EXAMPLE 1
[0044] An MEA as described in Example 1 was constructed using one layer, two layers and five layers of Nafion® 1 15 (E.I. DuPont de Nemours and Company, Wilmington, DE) as the PEM material. The equivalent weight of the PEM was 1 100. The thickness and the overall dehumidifying efficiency of these MEAs were measured and reported in Table 1.
COMPARATIVE EXAMPLE 2 [0045] An MEA as described in Example 1 was constructed using a commercially available PEM material (GORE-SELECT® Part No: GSM650.35) used for fuel cells and comprising 14.8 mol.% PSVE. The equivalent weight of the PEM was 1020. The thickness and the overall dehumidifying efficiency of these MEAs were measured and reported in Table 1 .
[0046] As illustrated in Table 1 , for a comparable thickness, the MEAs employing the functional TFE copolymers described herein for the PEM provide an overall dehumidification efficiency that is at least 5 times greater than that of an MEA using a single layer of Nafion® 1 15. Even when the thickness of the Nafion® 1 15 was increased by a factor of 4x, the dehumidifying efficiency of the MEA disclosed herein was still at least 2x greater.
TABLE 1
Figure imgf000013_0001
TEST METHODS [0047] Overall Dehumidifying Efficiency Test
[0048] The overall dehumidifying efficiency test reported in Table 1 is a steady state measurement that measures water pumping rate and current draw of an energized MEA with a fixed relative humidity (RH) and temperature on the cathode and anode side.
[0049] The cathode side temperature and RH are controlled with a dedicated room ventilation system and maintained at about 22°C and about 50% RH respectively. There is no forced air convection over the cathode side of the MEA.
[0050] The anode side temperature is maintained at about 22°C. A RH of about 22% at this temperature is established by placing the MEA over a Petri dish with a two phase mixture of 6.6 g potassium acetate in 2.2 g of water. The distance between the solution and surface of the anode is minimal, at about 3 mm.
[0051] The five layer MEA construction is screwed on to a sample holder. The holder/Petri dish assembly is placed on a tared microbalance (Mettler Toledo AG204) and the initial weight (Wo) of the holder/ Petri dish assembly is measured. The doors of the microbalance are opened slightly and a DC power supply (Instek PS-3225D) unit is attached to the electrical leads of the current collector tabs on the MEA. The power supply is connected to an ammeter (Ahlborn ZA9901-AB3) to measure the current. The output from the ammeter is transmitted to a data logger (Ahlborn Almemo 2890-9).
[0052] The DC power supply is turned on to produce 1.5 volts for 30 minutes and the current is measured during this time period. After 30 minutes, the power supply is turned off by removing the electrical leads attached to the current collector tabs on the MEA. The doors of the balance are closed and the housing/ Petri dish assembly is weighed (Wi).
[0053] The power supply is re-attached to the MEA and turned on again and the above cycle is repeated three times to measure W2, W3, W4 over a period of 1 .5 hours. The difference in weight between Wi and Wo, W2 and Wi , W3 and W2 and W4 and W3 over time is plotted. The dehumidification efficiency (mg water pumped per Coulomb) is calculated
asymptotic value of water pumping rate (mg/sec) asymptotic value of the current density (coulomb/sec, or amp).
Determination of Equivalent Weight
[0055] The method used to determine equivalent weight takes a measured weight of the solid sample and calculates an acid equivalent weight based on the first inflection point of the titration curve near pH 7. Specifically, for each sample, approximately 5 g of the solid sample weighing no more than 0.05 g each are dried in an oven for at least two hours at 80°C under full vacuum (~ 2 in. Hg). The dried pieces are removed from the oven and placed in a capped container to minimize moisture pickup. After allowing the dried sample to cool to room temperature in the capped container, approximately 0.15 g is quickly weighed into a 100 ml titration cup. The sample of known dry weight is then allowed to soak in the titration cup for 15 minutes in 5 ml of deionized water and 5 ml of ethanol. To the soaked sample, 55 ml of 2. ON NaCI solution is then added. A back titration method using a TIM900 Titration Manager (Radiometer Analytical S.A., Lyon, France) is then started beginning with the addition of 5 ml of 0.05N NaOH solution. The entire blend is then stirred for 15 minutes under a nitrogen blanket prior to the acid titration with 0.01 N HCI solution. The end point near pH 7 is used to calculate both the ion exchange capacity (IEC) and the acid equivalent weight (EW) of the sample according to:
[5 ml NaOH x 0.05 N] -
[Volume HQ (ml) X 0,01 N]
IEC (meq/g) =
Dried loiiomer Solid Weight (g)}
EW (g eq) = 1000 j IEC (meq/g) [0056] The dried ionomer solid weight (e.g., in the denominator) is equal to the sample weight. The arithmetic mean of the measured results from two different samples of each membrane is reported as the Equivalent Weight.
[0057] While various embodiments of the present invention have been described in detail, it is apparent that modifications and adaptations of those embodiments will occur to those skilled in the art. However, is to be expressly understood that such modifications and adaptations are within the spirit and scope of the present invention.

Claims

What is Claimed is:
1 . A humidification control device configured for controlling the humidity of an enclosure, said humidification control device comprising: a membrane electrode assembly, said membrane electrode assembly comprising: an anode and a cathode; at least a first proton exchange membrane disposed between said anode and said cathode, said proton exchange membrane comprising a polymeric material comprising a resin that includes a functional TFE copolymer having a polymer chain of TFE and at least one comonomer having a proton conducting functional group pendant to said polymer chain, wherein said at least one comonomer having a proton conducting functional group pendant to said polymer chain is present in an amount of at least about 0.01 mol.% and not greater than about 7 mol.% of said functional TFE copolymer; and first and second electrically conductive terminals interconnected to said anode and cathode, respectively, and configured to apply an electric potential across said membrane electrode assembly.
2. The humidification control device of Claim 1 , wherein said at least one comonomer having a proton conducting functional group pendant to said polymer chain is PSVE.
3. The humidification control device of Claim 1 , wherein said polymeric material has an equivalent weight of at least about 1500.
4. The humidification control device of Claim 1 , wherein said polymeric material has an equivalent weight of at least about 2400.
5. The humidification control device of Claim 1 , wherein said polymeric material is fabricated by extruding a fine powder resin into a tape, calendering said tape, and subjecting said calendered tape to heat-treatment to a temperature greater than the crystalline melting temperature of PTFE to form a non-porous tape.
6. The humidification control device of Claim 1 , wherein said polymeric material is fabricated by expanding said resin into a porous functional TFE copolymer material having a micro structure characterized by nodes interconnected by fibrils, and further densifying said porous material to form a non-porous structure.
7. The humidification control device of Claim 1 , wherein said membrane electrode assembly is configured to be positioned across an aperture of an enclosure to dehumidify a gaseous enclosed volume within an enclosed space defined by said enclosure.
8. The humidification control device of Claim 1 , further comprising a DC voltage source operatively connected to said first and second electrically conductive terminals.
9. The humidification control device of Claim 1 , wherein said proton exchange membrane has a thickness of not greater than about 200 μητι.
.
10. The humidification control device of Claim 1 , wherein said at least one comonomer having a proton conducting functional group pendant to said polymer chain is present in an amount of not greater than about 5 mol.% of said functional TFE copolymer.
1 1. The humidification control device of Claim 1 , wherein said proton exchange membrane has a Gurley number of at least about 1000 seconds.
12. An apparatus, comprising: an enclosure defining an enclosed space; and a humidification control device operatively affixed to said enclosure, said humidification control device comprising an anode and a cathode; at least a first proton exchange membrane disposed between said anode and said cathode, said proton exchange membrane comprising a polymeric material comprising a resin that includes a functional TFE copolymer having a polymer chain of TFE and at least one comonomer having a proton conducting functional group pendant to said polymer chain, wherein said at least one comonomer having a proton conducting functional group pendant to said polymer chain is present in an amount of at least about 0.01 mol.% and not greater than about 7 mol.% of said functional TFE copolymer; and first and second electrically conductive terminals interconnected to said anode and cathode; and a DC voltage source operatively connected to said first and second electrically conductive terminals.
13. The apparatus of Claim 12, wherein said humidification control device is affixed to said enclosure such that said anode is in fluid communication with said enclosed space.
14. The apparatus of Claim 12, wherein said at least one comonomer having a proton conducting functional group pendant to said polymer chain is PSVE.
15. The apparatus of Claim 12, wherein said polymeric material has an equivalent weight of at least about 1500.
16. The apparatus of Claim 12, wherein said polymeric material has an equivalent weight of at least about 2400.
17. The apparatus of Claim 12, wherein said proton exchange membrane has a thickness of not greater than about 200 pm.
.
18. The apparatus of Claim 12, wherein said at least one comonomer having a proton conducting functional group pendant to said polymer chain is present in an amount of not greater than about 5 mol.% of said functional TFE copolymer.
19. The apparatus of Claim 12, wherein said proton exchange membrane has a Gurley number of at least about 1000 seconds.
PCT/US2014/056241 2013-10-07 2014-09-18 Humidification control device WO2015053915A1 (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
KR1020167010520A KR20160060131A (en) 2013-10-07 2014-09-18 Humidification control device
EP14784143.1A EP3055896A1 (en) 2013-10-07 2014-09-18 Humidification control device
CN201480055156.8A CN105612647A (en) 2013-10-07 2014-09-18 Humidification control device
CA2925861A CA2925861A1 (en) 2013-10-07 2014-09-18 Humidification control device
JP2016520664A JP2017500524A (en) 2013-10-07 2014-09-18 Humidification control device

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US14/047,065 US20150096884A1 (en) 2013-10-07 2013-10-07 Humidification Control Device
US14/047,065 2013-10-07

Publications (1)

Publication Number Publication Date
WO2015053915A1 true WO2015053915A1 (en) 2015-04-16

Family

ID=51703391

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2014/056241 WO2015053915A1 (en) 2013-10-07 2014-09-18 Humidification control device

Country Status (7)

Country Link
US (1) US20150096884A1 (en)
EP (1) EP3055896A1 (en)
JP (1) JP2017500524A (en)
KR (1) KR20160060131A (en)
CN (1) CN105612647A (en)
CA (1) CA2925861A1 (en)
WO (1) WO2015053915A1 (en)

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11365485B2 (en) * 2015-11-23 2022-06-21 Ffi Ionix Ip, Inc. Ozone generator system
CN106400047A (en) * 2016-09-29 2017-02-15 中国科学院大连化学物理研究所 Isothermal dehumidification oxygen-enriched electrochemical device and application
KR102651962B1 (en) * 2016-12-14 2024-03-28 현대자동차주식회사 M0isture electrolysis apparatus for headlamp
CN106949571B (en) 2017-03-09 2023-04-25 华南理工大学 Electrochemical dehumidification device based on screen type amphoteric ion exchange membrane electrode
KR102556419B1 (en) * 2017-09-22 2023-07-17 스카이어, 아이엔씨. Air-water extraction system
US10593372B2 (en) 2018-07-20 2020-03-17 Seagate Technology Llc Dehumidifying devices, and data storage devices having one or more dehumidifying devices
US10734035B1 (en) * 2018-07-30 2020-08-04 Seagate Technology Llc Humidity control system for heat-assisted magnetic recording hard disk drive
US11783867B2 (en) 2019-08-07 2023-10-10 Seagate Technology Llc Electronic device that includes a composition that can actively generate and release a gaseous oxidizing agent component into an interior space of the electronic device, and related subassemblies and methods
US11763853B2 (en) 2019-08-07 2023-09-19 Seagate Technology Llc Electronic device that includes a composition that can actively generate and release a gaseous oxidizing agent component into an interior space of the electronic device, and related subassemblies and methods
US11024343B2 (en) * 2019-08-07 2021-06-01 Seagate Technology Llc Electronic device that includes a composition that can actively generate and release a gaseous oxidizing agent component into an interior space of the electronic device, and related subassemblies and methods
US11270739B1 (en) 2021-02-09 2022-03-08 Seagate Technology Llc Electronic device that includes one or more reactants that generate a gaseous oxidizing agent component inside the electronic device, and related subassemblies and methods
CN116288521B (en) * 2023-05-22 2023-09-29 山东赛克赛斯氢能源有限公司 Integrated PEM (PEM) electrolysis system and humidity control method

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3953566A (en) 1970-05-21 1976-04-27 W. L. Gore & Associates, Inc. Process for producing porous products
EP0064838A1 (en) * 1981-05-01 1982-11-17 E.I. Du Pont De Nemours And Company Composite membrane/electrode, electrochemical cell and electrolysis process
US5484512A (en) * 1992-01-08 1996-01-16 Shinko Pantec Co., Ltd. Methods and apparatuses for producing high purity oxygen and hydrogen
US5547551A (en) 1995-03-15 1996-08-20 W. L. Gore & Associates, Inc. Ultra-thin integral composite membrane
US6054230A (en) 1994-12-07 2000-04-25 Japan Gore-Tex, Inc. Ion exchange and electrode assembly for an electrochemical cell
US6723464B2 (en) 2000-05-31 2004-04-20 Japan Gore-Tex, Inc. Membrane-electrode-assembly with solid polymer electrolyte
US20060171065A1 (en) * 2005-02-03 2006-08-03 Hitachi Global Storage Technologies Netherlands B.V. Hard disk drive with humidity control using membrane electrode assembly
US7521010B2 (en) 2004-04-23 2009-04-21 Gore Enterprise Holdings, Inc. Fluoropolymer barrier material
US20100248324A1 (en) 2009-03-24 2010-09-30 Ping Xu Expandable Functional TFE Copolymer Fine Powder, the Expandable Functional Products Obtained Therefrom and Reaction of the Expanded Products

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0290917A (en) * 1988-09-28 1990-03-30 Mitsubishi Electric Corp Dehumidifier
JPH0380913A (en) * 1989-08-23 1991-04-05 Mitsubishi Electric Corp Control box
JPH04200616A (en) * 1990-11-30 1992-07-21 Mitsubishi Electric Corp Dehumidifying device
US5273694A (en) * 1992-08-28 1993-12-28 E. I. Du Pont De Nemours And Company Process for making ion exchange membranes and films
US5599614A (en) * 1995-03-15 1997-02-04 W. L. Gore & Associates, Inc. Integral composite membrane
JPH0952018A (en) * 1995-08-18 1997-02-25 Opt D D Melco Lab:Kk Dehumidifier
AU2928397A (en) * 1996-04-30 1997-11-19 W.L. Gore & Associates, Inc. Integral multi-layered ion-exchange composite membranes
JP3984743B2 (en) * 1999-01-13 2007-10-03 三菱電機株式会社 Humidity controller
US7094851B2 (en) * 2001-12-06 2006-08-22 Gore Enterprise Holdings, Inc. Low equivalent weight ionomer
US6861489B2 (en) * 2001-12-06 2005-03-01 Gore Enterprise Holdings, Inc. Low equivalent weight ionomer
US8652705B2 (en) * 2005-09-26 2014-02-18 W.L. Gore & Associates, Inc. Solid polymer electrolyte and process for making same
JP4967001B2 (en) * 2009-03-13 2012-07-04 ミズ株式会社 Method for producing hydrogen-containing biological fluid and apparatus therefor
US8658707B2 (en) * 2009-03-24 2014-02-25 W. L. Gore & Associates, Inc. Expandable functional TFE copolymer fine powder, the expanded functional products obtained therefrom and reaction of the expanded products
JP5638433B2 (en) * 2011-03-24 2014-12-10 株式会社東芝 Electrolyzer and refrigerator

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3953566A (en) 1970-05-21 1976-04-27 W. L. Gore & Associates, Inc. Process for producing porous products
EP0064838A1 (en) * 1981-05-01 1982-11-17 E.I. Du Pont De Nemours And Company Composite membrane/electrode, electrochemical cell and electrolysis process
US5484512A (en) * 1992-01-08 1996-01-16 Shinko Pantec Co., Ltd. Methods and apparatuses for producing high purity oxygen and hydrogen
US6054230A (en) 1994-12-07 2000-04-25 Japan Gore-Tex, Inc. Ion exchange and electrode assembly for an electrochemical cell
US5547551A (en) 1995-03-15 1996-08-20 W. L. Gore & Associates, Inc. Ultra-thin integral composite membrane
US6723464B2 (en) 2000-05-31 2004-04-20 Japan Gore-Tex, Inc. Membrane-electrode-assembly with solid polymer electrolyte
US7521010B2 (en) 2004-04-23 2009-04-21 Gore Enterprise Holdings, Inc. Fluoropolymer barrier material
US20060171065A1 (en) * 2005-02-03 2006-08-03 Hitachi Global Storage Technologies Netherlands B.V. Hard disk drive with humidity control using membrane electrode assembly
US20100248324A1 (en) 2009-03-24 2010-09-30 Ping Xu Expandable Functional TFE Copolymer Fine Powder, the Expandable Functional Products Obtained Therefrom and Reaction of the Expanded Products

Also Published As

Publication number Publication date
JP2017500524A (en) 2017-01-05
US20150096884A1 (en) 2015-04-09
EP3055896A1 (en) 2016-08-17
CN105612647A (en) 2016-05-25
CA2925861A1 (en) 2015-04-16
KR20160060131A (en) 2016-05-27

Similar Documents

Publication Publication Date Title
EP3055896A1 (en) Humidification control device
CN108570686B (en) System and method for regulating carbon dioxide concentration in indoor atmosphere
Lobato et al. PBI-based polymer electrolyte membranes fuel cells: temperature effects on cell performance and catalyst stability
US6733915B2 (en) Gas diffusion backing for fuel cells
Kim et al. High ion and lower molecular transportation of the poly vinylidene fluoride–hexa fluoro propylene hybrid membranes for the high temperature and lower humidity direct methanol fuel cell applications
EP0853824A2 (en) Flow field structures for membrane electrode assemblies of fuel cells
WO2007004716A1 (en) Separating membrane for fuel cell
WO1997013287A9 (en) Flow field structures for membrane electrode assemblies of fuel cells
Wu et al. A reversible water electrolyser with porous PTFE based OH− conductive membrane as energy storage cells
JP2007165306A (en) Membrane-electrode assembly of fuel cell and its manufacturing method
KR20070104405A (en) Method for reducing degradation in a fuel cell
US3595700A (en) Method of making electrode
Zugic et al. Enhanced performance of the solid alkaline fuel cell using PVA-KOH membrane
JP5002911B2 (en) Measuring method of electroosmotic water volume EOW per proton in power generation evaluation in direct methanol fuel cell (DMFC)
JP2008288065A (en) Electrolyte membrane, membrane-electrode assembly, fuel cell, and manufacturing method of electrolyte membrane
CA2685798C (en) Membraneless fuel cell and method of operating same
JP4925091B2 (en) PROTON CONDUCTIVE COMPOSITE ELECTROLYTE MEMBRANE AND METHOD FOR PRODUCING THE SAME
EP2202830A1 (en) Membrane electrode assembly and fuel cell
CN101978536A (en) Membrane electrode assembly and fuel cell
JP2002319421A (en) Starting method and manufacturing method of solid polymer fuel cell
Ferreira-Aparicio et al. Influence of the cathode catalyst layer thickness on the behaviour of an air breathing PEM fuel cell
JP2001259431A (en) Composite catalyst and method of manufacturing the same
JP5843682B2 (en) Diffusion layer structure of fuel cell
JP2002289202A (en) Method for lowering fuel cell cathode activating overvoltage
JP2006079840A (en) Electrode catalyst for fuel cell, and mea for fuel cell using this

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 14784143

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2925861

Country of ref document: CA

REEP Request for entry into the european phase

Ref document number: 2014784143

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 2014784143

Country of ref document: EP

ENP Entry into the national phase

Ref document number: 2016520664

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 20167010520

Country of ref document: KR

Kind code of ref document: A