WO2000024796A1 - Novel ion-conducting materials suitable for use in electrochemical applications and methods related thereto - Google Patents
Novel ion-conducting materials suitable for use in electrochemical applications and methods related theretoInfo
- Publication number
- WO2000024796A1 WO2000024796A1 PCT/US1999/019470 US9919470W WO0024796A1 WO 2000024796 A1 WO2000024796 A1 WO 2000024796A1 US 9919470 W US9919470 W US 9919470W WO 0024796 A1 WO0024796 A1 WO 0024796A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- ion
- conducting material
- pek
- sulfonated
- ppsu
- Prior art date
Links
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Definitions
- This invention relates to novel ion-conducting materials suitable for use as solid polymer electrolyte membranes in electrochemical applications including fuel cell systems. More specifically, these novel ion-conducting polymers are based on sulfonated polyaryletherketone polymers or sulfonated polyphenylsulfone polymers, including copolymers, or blends thereof. The present invention also describes novel processes for producing these ion- conducting materials.
- Fuel cells are highly efficient electrochemical energy conversion devices that directly convert the chemical energy derived from renewable fuel into electrical energy.
- Proton-exchange membrane fuel cells have a polymer electrolyte membrane disposed between a positive electrode (cathode) and a negative electrode (anode).
- the polymer electrolyte membrane is composed of an ion-exchange polymer (i.e., ionomer). Its role is to provide a means for ionic transport and prevent mixing of the molecular forms of the fuel and the oxidant.
- Solid polymer electrolyte fuel cells are an ideal source of quiet, efficient, and lightweight power. While batteries have reactants contained within their structure which eventually are used up, fuel cells use air and hydrogen to operate continuously. Their fuel efficiency is high (45 to 50 percent), they do not produce noise, operate over a wide power range (10 watts to several hundred kilowatts), and are relatively simple to design, manufacture and operate. Further, SPEFCs currently have the highest power density of all fuel cell types. In addition, SPEFCs do not produce any environmentally hazardous emissions such as NO x and SO x (typical combustion by-products).
- the traditional SPEFC contains a solid polymer ion-exchange membrane that lies between two gas diffusion electrodes, an anode and a cathode, each commonly containing a metal catalyst supported by an electrically conductive material.
- the gas diffusion electrodes are exposed to the respective reactant gases, the reductant gas and the oxidant gas.
- An electrochemical reaction occurs at each of the two junctions (three phase boundaries) where one of the electrodes, electrolyte polymer membrane and reactant gas interface.
- Ion exchange membranes play a vital role in various electrochemical applications, including that of SPEFCs.
- the ion- exchange membrane has two functions: (1) it acts as the electrolyte that provides ionic communication between the anode and cathode; and (2) it serves as a separator for the two reactant gases (e.g., O 2 and H 2 ).
- the ion- exchange membrane while serving as a good proton transfer membrane, must also have low permeability for the reactant gases to avoid cross-over phenomena that reduce performance of the fuel cell. This is especially important in fuel cell applications in which the reactant gases are under pressure and the fuel cell is operated at elevated temperatures.
- Fuel cell reactants are classified as oxidants and reductants on the basis of their electron acceptor or electron donor characteristics.
- Oxidants include pure oxygen, oxygen-containing gases (e.g., air) and halogens (e.g., chlorine).
- Reductants include hydrogen, carbon monoxide, natural gas, methane, ethane, formaldehyde and methanol.
- Optimized proton and water transports of the membrane and proper water management are also crucial for efficient fuel cell application. Dehydration of the membrane reduces proton conductivity, and excess water can lead to swelling of the membranes. Inefficient removal of by-product water can cause flooding of the electrodes hindering gas access. Both of these conditions lead to poor cell performance.
- SPEFCs have not yet been commercialized due to unresolved technical problems and high overall cost.
- One major deficiency impacting the commercialization of the SPEFC is the inherent limitations of today's leading membrane and electrode assemblies.
- the membranes employed must operate at elevated/high temperatures (>120°C) so as to provide increased power density, and limit catalyst sensitivity to fuel impurities. This would also allow for applications such as on-site cogeneration (high quality waste heat in addition to electrical power).
- Current membranes also allow excessive methanol crossover in liquid feed direct methanol fuel cells (dependent on actual operating conditions, but is typically equivalent to a current density loss of about 50 to 200 mA/cm 2 @ 0.5 V).
- fuel crossover is a parasitic reaction that lowers efficiency, reduces performance and generates heat in the fuel cell. It is highly desirable to minimize the rate of fuel crossover.
- the Nafion® membrane technology is well known in the art and is described in U.S. Patent Nos. 3,282,875 and 4,330,654.
- Unreinforced Nafion® membranes are used almost exclusively as the ion exchange membrane in present SPEFC applications.
- This membrane is fabricated from a copolymer of tetrafluoroethylene (TFE) and a perfluorovinyl ethersulfonyl fluoride.
- the vinyl ether comonomer is copolymerized with TFE to form a melt- processable polymer. Once in the desired shape, the sulfonyl fluoride group is hydrolyzed into the ionic sulfonate form.
- the fluorocarbon component and the ionic groups are incompatible or immiscible (the former is hydrophobic, the latter is hydrophilic). This causes a phase separation, which leads to the formation of interconnected hydrated ionic "clusters".
- the properties of these clusters determine the electrochemical characteristics of the polymer, since protons are conducted through the membrane as they "hop" from one ionic cluster to another. To ensure proton flow, each ionic group needs a minimum amount of water to surround it and form a cluster. If the ionic group concentration is too low (or hydration is insufficient) proton transfer will not occur. At higher ionic group concentrations (or increased hydration levels) proton conductivity is improved, but membrane mechanical characteristics are sacrificed.
- Nafion® membranes There are several mechanisms that limit the performance of Nafion® membranes in fuel cell environments and other electrochemical applications.
- Nafion® is sensitive to heat and can only be used effectively to temperatures of about 100°C. In fact, performance-limiting phenomenon may begin even at temperatures of about 80°C.
- Mechanisms which limit the performance of Nafion® include membrane dehydration, reduction of ionic conductivity, radical formation in the membrane (which can destroy the solid polymer electrolyte membrane chemically), loss of mechanical strength via softening, and increased parasitic losses through high fuel permeation.
- Methanol- crossover not only lowers fuel utilization efficiency but also adversely affects the oxygen cathode performance, significantly lowering cell performance. More specifically, this crossover causes a mixed reaction (oxidation and reduction) to develop on the cathode side, reducing the reaction efficiency.
- the Nafion® membrane/electrode is also very expensive to produce, and as a result it is not (yet) commercially viable. Reducing membrane cost is crucial to the commercialization of SPEFCs. It is estimated that membrane cost must be reduced by at least an order of magnitude from the Nafion® model for SPEFCs to become commercially attractive.
- Gore-Select® Another type of ion-conducting membrane, Gore-Select® (commercially available from W.L. Gore), is currently being developed for fuel cell applications. Gore-Select® membranes are further detailed in a series of U.S. Patents (U.S. 5,635,041, 5,547,551 and 5,599,614).
- Gore discloses a composite membrane consisting of a porous Teflon® film filled with a Nafion® or Nafion®-like ion-conducting solution. Although it has been reported to show high ionic conductance and greater dimensional stability than Nafion® membranes, the Teflon® and Nafion® materials selected and employed by Gore as the film substrate and the ion-exchange material, respectively, may not be appropriate for operation in high-temperature SPEFCs. Teflon® undergoes extensive creep at temperatures above 80°C, and Nafion® and similar ionomers swell and soften above the same temperature. This can result in the widening of interconnected channels in the membrane and allow performance degradation, especially at elevated temperatures and pressures.
- Gore-Select® as well as many other types of perfluorinated ion- conducting membranes (e.g., Aciplex from Asahi Chemical, Flemion® from Asahi Glass, Japan), are just as costly as Nafion®, since these membranes employ a high percentage of perfluorinated ionomers.
- ion-exchange membranes that are less expensive to produce also have been investigated for use in polymer electrolyte membrane fuel cells.
- Poly(trifluorostyrene) copolymers have been studied as membranes for use in polymer electrolyte membrane fuel cells. See e.g., U.S. Patent No. 5,422,411. However, these membranes are suspected to have poor mechanical and film forming properties. In addition, these membranes may be expensive due to the inherent difficulties in processing fluorinated polymers.
- Sulfonated polyaromatic based systems such as those described in U.S. Patent Nos. 3,528,858 and 3,226,361, also have been investigated as membrane materials for SPEFCs. However, these materials suffer from poor chemical resistance and mechanical properties that limit their use in SPEFC applications.
- Solid polymer membranes comprising a sulfonated poly(2,6 dimethyl 1 ,4 phenylene oxide) alone or blended with poly(vinylidene fluoride) also have been investigated. These membranes are disclosed in WO 97/24777. However, these membranes are known to be especially vulnerable to degradation from peroxide radicals.
- PES Sulfonated ⁇ oly(aryl ether ketone)
- U.S. Patent No. 4,268,650 also describes sulfonated PEK polymers.
- the process disclosed in this patent relies on the copolymerization of PEK and polyether ether ketone (PEEK) to control the level of sulfonation in concentrated sulfuric acid. Sulfonation under these conditions is thought to occur exclusively at the ether-phenyl-ether linkages.
- PEEK polyether ether ketone
- U.S. Patent No. 4,273,903 involves a similar process using polyarylethersulphone copolymers. Specifically, this patent discloses the controllable sulfonation of polyarylethersulphone polymers in concentrated sulfuric acid using copolymers of polyetherether sulfone (sulfonatable) and polyethersulfone (less susceptible to sulfonation). This patent also reports that the use of sulfuric acid/oleum, oleum or chlorosulfonic acid will completely sulfonate and/or degrade the polyethersulfone polymer. The sulfonation procedure described in this reference is carried out homogeneously (i.e., putting the polymer into solution before addition of the sulfonating agent.)
- U.S. Patent No. 5,795,496 discloses methods for producing sulfonated polyether ether ketone (PEEK) and sulfonated poly (p-phenylene ether sulfone) (PES) polymer materials for use in fuel cells.
- Target properties of the asymmetric membranes formed using the materials and methods of this patent include a target membrane thickness of 0.05-0.5 mm (equivalent to about 2-20 mils).
- This patent also reports that thinner membranes, e.g., less than 0.05 mm, have poor mechanical strength and dimensional stability.
- This reference also describes cross-linking of these sulfonated polymer materials at temperatures of about 120°C for an unspecified time in order to minimize fuel crossover.
- 4,413,106 provides methods for the heterogeneous sulfonation (i.e., sulfonation of the precipitated polymer/solvent co-crystals) for polyarylethersulfone (PES) polymers in chlorinated hydrocarbon solvents with a sulfonating agent.
- PES polyarylethersulfone
- PES polymers of formula (PH-SO 2 -Ph-O) are known to crystallize from a variety of solvents, such as CH 2 C1 2 , DMF, DMAc. The crystallization is promoted by agitation or addition of non-solvents, and is highly dependent upon reaction conditions. Polymer/solvent intercrystallites ( ⁇ 1 micron diameter) form as a suspension in a surplus amount of the solvent. The amount of sulfonating agent added controls the degree of sulfonation. Temperatures are indicated as being preferable from -10 to 25°C.
- U.S. Patent No. 5,013,765 reports the controllable sulfonation of aromatic PES polymers using sulfur trioxide (sulfonating agent) and sulfuric acid (solvent).
- sulfuric acid content must be less than 6% wt (based upon the solvent) and that the temperature must be ⁇ 30°C in order to control side reactions and degradation.
- Chlorosulfonic acid and oleum as sulfonating agents are discouraged since they can lead to an excessive degree of sulfonation and/or polymer degradation.
- this patent indicates that controllable sulfonation using these agents is not possible.
- This patent also reports that use of sulfur trioxide in concentrated sulfuric acid can produce sulfonated polymers without by-products or degradation products, especially in the case of O-Ph-SO 2 - Ph based polymers.
- a central object of the present invention is to provide novel ion- conducting materials suitable for use in a broad range of electrochemical applications, including fuel cell systems.
- these novel ion-conducting materials are based on sulfonated polyaryletherketone (PEK) homopolymers or PEK copolymers, or blends thereof.
- these novel ion- conducting materials are based on sulfonated polyphenylsulfone (PPSU) homopolymers or PPSU copolymers, or blends thereof.
- the class of PEK and PPSU homopolymers, copolymers, and blends thereof disclosed herein may include any desired substituents, provided that such substituents do not substantially impair properties desired for the intended use of the polymer, as may readily be determined by one of ordinary skill in the art. Such properties may include ionic conductivity, chemical and structural stability, swelling properties and so forth. Accordingly, as used herein, PEK and PPSU homopolymers, copolymers and blends thereof, include both substituted and unsubstituted PEK and PPSU polymers.
- Another object of this invention is to provide novel processes for producing such ion-conducting materials.
- One preferred ion-conducting material in accordance with the present invention comprises at least one polyaryletherketone (PEK) homopolymer or at least one PEK copolymer, or blends thereof (sometimes referred to hereinafter as "PEK based ion-conducting materials"), wherein the PEK homopolymer is sulfonated and the ion-conducting material is devoid of ether-phenyl-ether linkages.
- PEK polyaryletherketone
- the PEK homopolymer comprises repeating units of the formula
- phenyl rings may be substituted or unsubstituted.
- the PEK based ion-conducting materials have an IEC from at least about 0.5 meq. ⁇ g to at least about 4 meq./g.
- the PEK based ion-conducting materials may further comprise sulfone crosslinkages and/or antioxidants.
- the PEK based ion-conducting materials of the present invention may be halogenated, e.g., brominated or chlorinated, in order to further enhance stability.
- the PEK based ion-conducting materials of the present invention are useful in the preparation of solid polymer electrolyte membranes.
- One preferred method of producing ion-conducting materials devoid of ether-phenyl-ether linkages suitable for use in electrochemical applications in accordance with the present invention comprises: providing a solution of at least one PEK homopolymer; adding a sulfonating agent to the PEK homopolymer solution to form a sulfonated PEK homopolymer; and isolating the sulfonated PEK homopolymer from the solution.
- Preferred sulfonating agents for use in this method comprise at least one of sulfur trioxide, concentrated sulfuric acid and fuming sulfuric acid. In some methods, it is preferred that the sulfonating agent has a free sulfur trioxide content of about 0 (about 100% sulfuric acid) to about 30 wt.% (about 70% sulfuric acid).
- the PEK homopolymer solution is maintained at a reaction temperature from about 10°C to about 60°C.
- One preferred method of isolating the sulfonated PEK based ion- conducting material comprises re-precipitating the sulfonated PEK homopolymer into water, water saturated with sodium chloride, methanol or other non-solvent.
- antioxidants are added to the sulfonated PEK homopolymer, either prior to or following isolation of the sulfonated PEK homopolymer.
- the PEK based ion-conducting materials are crosslinked, particularly when the ion-conducting material is in the H+ (acid) form.
- the PEK based ion-conducting material undergoes a halogenation step.
- Another ion-conducting material in accordance with the present invention comprises at least one sulfonated polyphenylsulfone (PPSU) homopolymer or PPSU copolymer or blends thereof (sometimes referred to hereinafter as "PPSU based ion-conducting materials").
- PPSU polyphenylsulfone
- One preferred PPSU based ion-conducting material comprises repeating units of the formula
- phenyl rings may be substituted or unsubstituted.
- the PPSU based ion-conducting materials of the present invention have an IEC from at least about 0.5 meq./g to about 4 meq./g. In some embodiments, these materials further comprise sulfone crosslinkages and/or antioxidants.
- PPSU based ion-conducting materials of the present invention may be used in the preparation of solid polymer electrolyte membranes.
- Such solid polymer electrolyte membrane may contain sulfone crosslinkages.
- One method of producing PPSU based ion-conducting materials of the present invention which are suitable for use in electrochemical applications comprises: providing a solution of a PPSU polymer; allowing the PPSU polymer to precipitate from the solution; adding a sulfonating agent comprising sulfur trioxide to the solution to form a sulfonated PPSU polymer, wherein the sulfur trioxide is diluted in solvent comprising a chlorinated hydrocarbon; and isolating the sulfonated PPSU polymer from the solution.
- Methylene chloride is one preferred chlorinated hydrocarbon solvent for use in the present invention.
- the method further comprises purifying the ion- conducting material to remove overly sulfonated or degraded fractions of the PPSU based ion-conducting material. This is accomplished in one preferred method by re-dissolving the sulfonated PPSU polymer in a solvent, and re- precipitating the sulfonated PPSU polymer into water, water saturated with sodium chloride, methanol or other non-solvent.
- the method of forming PPSU based ion-conducting polymers of the present invention may further comprise crosslinking the ion-conducting material, especially when the ion-conducting material is in the H+ form.
- the preferred methods may also comprise adding antioxidants to the sulfonated PPSU polymer, either before or following isolation of the sulfonated PPSU polymer.
- Yet other preferred methods include halogenating, e.g., chlorinating or brominating PPSU based ion-conducting materials.
- the present invention relates to novel ion-conducting materials which may be used to produce solid polymer electrolyte membranes (SPEMs). These materials could also be used in composite SPEMs comprising a substrate polymer and ion-conducting material component.
- SPEMs solid polymer electrolyte membranes
- novel ion-conducting materials and SPEMs of the present invention are designed to address the present shortcomings of today's leading solid polymer electrolyte membranes, e.g., Nafion® and other Naf ⁇ on®-like membranes, such as Gore-Select®.
- Materials and membranes of the present invention may be used in a host of electrochemical applications, including but not limited to, polarity-based chemical separations; electrolysis; fuel cells and batteries; pervaporation; reverse osmosis - water purification, gas separation; dialysis separation; industrial electrochemistry, such as choralkali production and other electrochemical applications; water splitting and subsequent recovery of acids and bases from waste water solutions; use as a super acid catalyst; use as a medium in enzyme immobilization, for example; or use as an electrode separator in conventional batteries.
- electrochemical applications including but not limited to, polarity-based chemical separations; electrolysis; fuel cells and batteries; pervaporation; reverse osmosis - water purification, gas separation; dialysis separation; industrial electrochemistry, such as choralkali production and other electrochemical applications; water splitting and subsequent recovery of acids and bases from waste water solutions; use as a super acid catalyst; use as a medium in enzyme immobilization, for example; or use as an electrode separator in conventional batteries.
- Such processes generally comprise providing a solution of a polyaryletherketone (PEK) homopolymer, PEK copolymer or blends thereof, or a polyphenyl sulfone (PPSU) homopolymer, PPSU copolymer or blends thereof; adding a sulfonating agent to the polymer solution; and isolating the sulfonated polymer from the solution.
- Post-processing steps i.e., purification, cross-linking, use of antioxidants, chlorination or bromination of the aromatic polymer backbone
- the ion-conducting material comprises a sulfonated PEK homopolymer, PEK copolymer or a blend thereof.
- PEK homopolymer has the repeating unit shown below:
- the phenyl rings of the PEK homopolymer may be substituted or unsubstituted.
- the PEK hompolymer, PEK copolymer or blends thereof be sulfonated in the absence of ether-phenyl-ether linkages (e.g., in the absence of PEKPEEK copolymerization).
- PEK homopolymer e.g., available from Victrex USA
- concentrated sulfuric acid e.g., available from Victrex USA
- Slow addition of oleum reacts with the water present in the solution producing a more concentrated form of sulfuric acid solvent that eventually contains free SO 3 (after all the water has reacted).
- Further addition of oleum increases the sulfonating power of the solution.
- the water content is lowered, thereby increasing the sulfonating power of the solution.
- Care must be taken to avoid excessive SO 3 content or overheating of the solution in order to minimize polymer degradation.
- Overhead stirring of the solution and a room temperature water bath are highly recommended. Maintenance of the concentration of the reactant acid solution is critical. As these solutions are hygroscopic, they tend to change concentration due to moisture absorption with every exposure to air. Careful monitoring of their density can be used to check concentration. Titration may be used to monitor concentration.
- the sulfonated PEK based ion-conducting product can be isolated by precipitation into water provided that the extent of sulfonation has not made it water soluble (methanol / water or water saturated with salt may also provide for a high degree of sulfonation). Longer reaction times or a larger excess of sulfur trioxide will cause more sulfonation.
- Preferable temperature ranges for the reaction are as follows: 0-80°C including chilling the initial PEK polymer solution before, after, or during the addition of the oleum. However, since pure H 2 SO 4 solutions will freeze at approximately 10°C, it is preferable to maintain a temperature between 10-60°C.
- reaction conditions include using a free SO 3 content of between about 0 (about 100% sulfuric acid) to about 30 wt.% (about 70% sulfuric acid).
- Optimal content is dependent upon other reaction conditions (i.e., temperature), but generally SO 3 content is preferred to be between l-25wt.%.
- the final concentration of polymer depends upon the starting sulfuric acid concentration, the free SO 3 level desired, and the concentration of fuming sulfuric acid added. Generally preferred concentration ranges include the following:
- 10wt.% polymer ( ⁇ 5-30wt.%) in concentrated sulfuric acid (preferably 80-100%, more preferably 90-99%).
- Oleum SO 3 /H 2 SO 4
- a free SO 3 content is preferably between 10-60wt.%, more preferably approximately 20- 30wt.%.
- pure SO 3 also may be used under the appropriate conditions.
- reaction conditions may be tailored to produce sulfonated PEK based ion-conducting materials having IECs from at least about 0.5 to at least about 4 meq./g.
- ion-conducting materials comprising sulfonated PEK homopolymers, copolymers or blends thereof, can be isolated via direct precipitation into water (or salt water) depending on the level of sulfonation.
- sulfonated PEK may not be sufficient for long-term use in fuel cells, many electrochemical applications do not require hydrolytic stability at this level.
- the ion- conducting material comprises at least one of a sulfonated PPSU homopolymer, PPSU copolymer or blends thereof.
- This polymer has the repeating unit shown below:
- the phenyl rings of the PPSU polymer may be substituted or unsubstituted.
- controllable sulfonation of PPSU homopolymers, copolymers and blends thereof can be achieved using a methylene chloride (solvent)/ sulfur trioxide (sulfonating agent) system.
- One preferred process of the present invention for preparing PPSU based ion-conducting materials is described as follows: the polymer is first dissolved in a suitable solvent, preferably methylene chloride or another non-reactive solvent, e.g., halogenated hydrocarbons or nitrobenzene and the like. The polymer solution is allowed to stir until the polymer precipitates and a slush-like suspension is formed. Sulfonation is performed by admixture of the PPSU polymer suspension and a sulfonating agent, preferably, sulfur trioxide. The amount of sulfonating agent added controls the degree of sulfonation. Preferably, temperatures are maintained between -10 to 25°C.
- the methods for preparing PPSU based ion-conducting materials of the present invention may be further optimized by additional dilution of the polymer solution with solvent and extending the addition time of the sulfonating agent.
- concentration ranges for the PPSU based ion- conducting materials of the present invention include the following: 5-30wt.%, preferably 10-20wt% (initial polymer solution, before dilution of any excess solvent).
- This method can be used to produce highly sulfonated polymeric films (IEC of at least about 0.5 meq./g to at least about 4.0 meq./g), with equally high conductivity (IC of at least about 0.01 to about 0.5 S/cm) and minimal polymeric degradation.
- IEC highly sulfonated polymeric films
- IC electrical conductivity
- heterogeneity of the sulfonated PPSU based ion-conducting polymers may result from the sulfonation procedure. Heterogeneity may not be severe enough to cause the polymer to precipitate during the sulfonation procedure, but some distribution may exist as the polymer crystallites sulfonate from the outside in. That is, some portions of the sulfonated polymer may be so highly sulfonated as to be water soluble (possibly leaching out during fuel cell operation) or otherwise degraded.
- the purification procedure involves re-dissolving the ion-conducting polymer in a suitable solvent (e.g., NMP), and re-precipitating it into water or saturated NaCl solution. Re-precipitation of the ion-conducting polymer into saturated salt solution has been shown to result in a high yield of the ion- conducting polymer, while removing polymer that has been excessively sulfonated or degraded.
- a suitable solvent e.g., NMP
- the stability of the ion-conducting materials of the present invention may be enhanced by several post-processing steps. These steps include the following: (i) cross-linking the ion-conducting polymer in the H+ form to develop sulfone cross-links; (ii) addition of small amounts of antioxidants (insoluble) into the ion-conducting polymer; and (iii) chlorination / bromination of the ion-conducting polymer backbone, thereby reducing degradation sites.
- Crosslinking methods can provide or enhance peroxide stability.
- U.S. Patent No. 5,795,496 describes a method of crosslinking ion-conducting polymers via the SO 3 H groups (sulfonic acid groups) to form sulfone crosslinks between polymer chains.
- This method entails sulfonating the polymer (e.g., PEEK) using concentrated sulfuric acid, casting of a film, then heating the film to a temperature of 120°C under vacuum. It is the heating step which causes the crosslinking to occur.
- crosslinking procedure results in decreased ionic conductivity, water adsorbtion and swelling of the polymer.
- adjustments can be made to the crosslinking procedures employed in order to minimize the sacrifice of ionic conductivity.
- additives can also provide or enhance peroxide stability of the PEK and PPSU based ion-conducting materials of the present invention.
- Polymer additives can be used as radical scavengers within the ion-conducting component of the ion-conducting material or SPEM. Examples of these include Irganox 1135 (Primary Phenolic Antioxidant, commercially available from Ciba Geigy) and DTTDP (Di(tridecyl) Thiodipropionate, Secondary Antioxidant, commercially available from Hampshire).
- PEK and PPSU based ion-conducting materials of the present invention may be used to produce SPEMs using standard membrane casting techniques. Such techniques are well known to the skilled artisan.
- films can be made by dissolving the polymer in a suitable solvent and casting onto a glass plate (or other surface). More specifically, the ion conducting polymer can be dissolved in n-methyl pyrrolidone (NMP), filtered, and then cast onto the substrate. The films are slowly evaporated in a low humidity chamber, then dried in a vacuum oven to fully densify. Once dry the films can be removed from the casting substrate by immersion in water.
- NMP n-methyl pyrrolidone
- the PEK and PPSU based ion-conducting materials and SPEMs of the present invention have limited methanol permeability (limited methanol diffusivity and solubility) even at elevated temperatures and pressures, are substantially chemically stable to acids and free radicals, and thennally/hydrolytically stable to temperatures of at least about 100°C.
- the PEK and PPSU based ion-conducting membranes of the present invention have an ion-exchange capacity (IEC) of >1.0meq/g dry membrane (preferably, 1.5 to 2.0meq/g) and are highly ion-conducting (preferably, from about 0.01 to about 0.5S/cm, more preferably, to greater than about 0.1 S/cm or ⁇ 10 ⁇ cm resistivity).
- IEC ion-exchange capacity
- Ion-conducting materials and SPEMs of the present invention are durable, substantially defect-free, and dimensionally stable (less than about 20% change in dimension wet to dry), preferably even above temperatures of at least about 100°C.
- Particularly preferred PEK and PPSU based ion-conducting materials have the ability to survive operation in fuel cells (i.e., H 2 /O 2 , methanol) for at least about 5000 hours (e.g., automotive applications).
- fuel cells i.e., H 2 /O 2 , methanol
- the PEK and PPSU based ion-conducting materials for use in the present invention may be substituted or unsubstituted. These materials may be present as homopolymers, copolymers, or other blends.
- the class of PEK and PPSU homopolymers, copolymers, and blends thereof disclosed herein may include any desired substituents, provided that such substituents do not substantially impair properties desired for the intended use of the polymer, as may readily be determined by one of ordinary skill in the art. Such properties may include ionic conductivity, chemical and structural stability, swelling properties and so forth.
- the utility of blending polymers to form a PEK and PPSU based ion- conducting material of the present invention is in optimizing each of their properties. Unlike simple mixing, blending does not create a composite material with two dispersed components. Rather, the blend is uniform in composition throughout. It may be useful to blend a sulfonated polymer with an unsulfonated one to optimize swelling, fuel crossover resistance, conductivity, peroxide resistance, hydrolytic stability and the like. Similarly, the blending of two sulfonated polymers might allow improved properties over each individual component. This concept may also be employed to improve the strength, cost, processability or stability of the ion-conducting materials of the present invention.
- relatively low cost ion-conducting materials of the present invention may be produced which exhibit improved power density and reduced sensitivity to carbon monoxide in hydrogen fuel.
- Ion-conducting materials of the present invention also alleviate water management problems which limit the efficiency of present Nafion® membrane- based fuel cells.
- Ion-conducting materials of the present invention exhibit resistance to degradation and hydrolysis, as well as resistance to stress-induced creep. Ion-conducting materials of the present invention exhibit high ionic conductivity, high resistance to dehydration, high mechanical strength, chemical stability during oxidation and hydrolysis, low gas permeability to limit parasitic losses, and stability at elevated temperatures and pressures.
- Ion-conducting materials of the present invention are resistant to methanol crossover when used in a direct methanol fuel cell. This results in high efficiency and improved cell performance.
- Ion-conducting materials of the present invention utilize relatively low cost starting materials and fabrication methods, and therefore can be produced at a fraction of the cost of those membranes employing Nafion® and Nafion®-like ionomers.
- Ion-conducting materials of the present invention of the present invention act as a barrier against reactants (H 2 , O 2 and methanol permeation) in fuel cell applications.
- Surfactants or surface active agents having a hydrophobic portion and hydrophilic portion may be utilized in producing ion-conducting materials of the present invention of the present invention. These agents are well known in the art and include Triton X-100 (commercially available from Rohm & Haas of Philadelphia, PA).
- Compatibilizers may also be employed in producing membranes of the present invention.
- "compatibilizers” refer to agents that aid in the blendability of two or more polymers that would otherwise be resistant to such blending. Examples include block copolymers containing connecting segments of each component.
- the PEK and PPSU based ion-conducting materials, SPEMs and methods of the present invention will be further illustrated by the Table and Examples below.
- Boil deionized water in separate beakers on hotplate. 4. Place films into boiling water.
- Ion-conducting polymeric samples can be crosslinked in the acid (H+) form to improve ICP stability. Normally, crosslinking is performed in vacuum, to exclude oxygen from the system (which can cause ICP charring). The vacuum oven should be preheated to temperatures of at least about 200°C. The ICP sample is then heated in the vacuum oven for a prolonged period of time. The ICP sample should be tested before and after crosslinking for IEC and peroxide stability in order to evaluate long term membrane stability. See e.g., Example 5 below.
- Ion-conducting materials of the present invention may be used to produce
- films can be made by dissolving the polymer in a suitable solvent and casting onto a glass plate (or other surface).
- the ion conducting polymer can be dissolved in n-methyl py ⁇ olidone (NMP), filtered, and then cast onto the substrate.
- NMP n-methyl py ⁇ olidone
- the films are slowly evaporated in a low humidity chamber, then dried in a vacuum oven to fully densify. Once dry the films can be removed from the casting substrate by immersion in water.
- Aromatic PES polymers can be sulfonated to controlled degrees of substitution with sulfonating agents. The degree of substitution is controlled by the choice of and mole ratio of sulfonating agent to aromatic rings of the polymer, by the reaction temperature and by the time of the reaction. This procedure offers a method for carrying out sulfonation in a heterogeneous manner, i.e., sulfonation of precipitated polymer crystals.
- the polymer preferably a polyethersulfone
- the appropriate solvent preferably methylene chloride
- Sulfonation is carried out by simple admixture of the suspension with a sulfonating agent. Suitable agents include chorosulfonic acid and, preferably, sulfur trioxide (Allied chemicals stabilized Sulfan B® in CH 2 C1 2 ).
- the sulfonating agent used should be in sufficient proportion to introduce a number of sulfonate groups onto the polymer that is within the range of between 0.4: 1 to 5: 1 per polymer repeat unit, although this is not critical.
- the temperature at which sulfonation takes place is critical to limiting the side reactions but varies with the type of polymer (a preferable temperature is within the range of from -50° to 80°C, preferably -10° to +25°C).
- the sulfonated polymer may be separated from the reaction mixture by conventional techniques such as by filtration, washing and drying.
- the polymer products of the process of the invention may be neutralized with the addition of a base, such as sodium bicarbonate, when desired and converted to the alkali salts thereof.
- a base such as sodium bicarbonate
- the alkali salts of the polymer products of the invention may be used for the same purposes as the parent acid polymers.
- Concentrated sulfuric acid is used as the solvent in this procedure.
- the content of the sulfonating agent, sulfur trioxide is based on the total amount of pure (100%) anhydrous) sulfuric acid present in the reaction mixture, and is kept to a value of less than 6% by weight throughout the entire sulfonation.
- the sulfur trioxide may be mixed in dissolved form (oleum, fuming sulfuric acid) with concentrated sulfuric acid. The concentration of the starting sulfuric acid and oleum were determined by measuring their density immediately before use in the reactions.
- the temperature of the reaction mixture is kept at less than +30°C throughout the reaction.
- the sulfonation procedure is stopped with the addition of water to the reaction mixture or by pouring the reaction mixture into water.
- the polymer is first dried in high vacuum at room temperature to constant weight, then dissolved in concentrated sulfuric acid.
- Oleum is then added drop-wise over a period of hours with constant cooling below +30°C, and with stirring. When all of the oleum has been added, the reaction mixture is stirred for a further period of hours at the same temperature.
- the resultant viscous solution is then run into water and the precipitated polymer is filtered off.
- the polymer is then washed with water until the washings no longer are acidic, and it is then dried.
- films are immersed in distilled H 2 O and boiled for a period of 30 minutes.
- the films are then placed in a solution of 1.5N H 2 SO 4 at room temperature and soaked for a period of 30 minutes. This is repeated three separate times to ensure proper H+ ion exchange into the membrane.
- Films are rinsed free of acid (pH of rinse water > 5.0) and placed into separate beakers, each filled with a saturated solution of NaCl.
- the salt solution is boiled for a period of three hours.
- the films, which are now in the Na+ form are removed from the salt solution, rinsed with distilled water and padded to remove excess water. Now a wet weight and thickness of the sample are measured.
- the films While in the Na+ form, the films are dried in an air oven at a temperature of 60°C. The dry weight and thickness of the films are measured and the percent water content is calculated. The salt solutions are titrated with 0.1N NaOH to a phenolphthalein endpoint and IEC dry (meq/g) values calculated.
- Transverse ionic conductivity measurements are performed on film samples in order to determine the specific resistance (ohm*cm 2 ).
- film samples Prior to the ionic conductivity measurements, film samples are exchanged into the H+ form using the standard procedure discussed above. To measure the ionic conductivity, the film samples are placed in a die consisting of platinum-plated niobium plates. The sample size tested is 25cm 2 .
- Measurements are converted to specific resistance by calculating the ratio of thickness over conductivity (ohm*cm2).
- Accelerated degradation testing is carried out using 3% H 2 O 2 solution with 4 ppm Fe++ added as an accelerator.
- the films are tested for a period of 8 hours at a temperature of 68°C.
- the percent degradation of IEC was measured in the film samples after the test. After 8 hours, the films are removed from solution, and re- exchanged using 1.5 N H 2 SO 4 .
- the IEC is recalculated, and the test result expressed as the % loss in IEC. This test simulates long term (several thousand hours) of actual fuel cell operation. For H 2 O 2 , fuel cells, ⁇ 10% IEC degradation in this test would be considered acceptable.
- reaction mixtures were permitted to stir at ice bath temperatures for another 2.5 hours, then the reaction was stopped by adding approximately 10 ml of deionized water to each of the reaction mixtures.
- reaction mixtures (white dispersions) were recovered by filtration using a glass frit.
- Products (white powder) were washed 3X with 100 ml portions of dichloromethane. The washed products were then permitted to air dry in the hood. 20%) solutions of the dried products were made in NMP and cast on soda lime glass plates. The freshly cast films were left to stand in a dry box with a relative humidity of less than 5% for a period of 24 hours. The cast films were heated at 70°C under full dynamic vacuum for an hour prior to floating the films off with deionized water. The floated films were then permitted to air dry overnight.
- the 100% and 150% sulfonated products swell greatly in water and become opaque, but when films are dry they shrink and become clear once again.
- the mechanical strength of these films allows creasing while resisting tearing.
- Films of the 100% and 150% products are not soluble in boiling water, and under these conditions also maintain their mechanical properties.
- the sulfonated polymers were dried overnight, dissolved in NMP (at 20wt.%) and then precipitated into a large excess of distilled water, followed by soaking in sodium bicarbonate solution (to convert to the sodium salt form).
- sample B was added to approximately 4 liters of acetone.
- the acetone caused the collapse of the water swollen polymer which was then isolated by filtration. It also caused a significant portion to dissolve, which was isolated by drying of the acetone / water mixture (Sample B-l).
- Samples B and B-l contained approximately the same amount of polymer, but showed varying properties. In particular, the sulfonated polymer that was not extracted into acetone showed a slightly lower IEC, and a significantly lower water up-take.
- PEK polymer 30.00g was dissolved in 270g of concentrated sulfuric acid (93.5wt.%>) under nitrogen, sti ⁇ ed by an overhead mechanical sti ⁇ er. The polymer was dispersed over several days to form a dark red thick solution.
- the 1 and 3 hour products were washed several times with deionized water, soaked overnight in approximately 0.5M NaOH solution, then washed until a neutral pH was achieved. These were blotted dry and placed in the vacuum oven overnight at 50°C. Dried samples were dissolved in NMP to make a 20wt. % solution. This required heating overnight at 60°C. Films of approx. 6 mils were cast onto a freshly cleaned glass plate. After two days of drying the films were removed by immersion into deionized water.
- Ion-conducting polymeric samples can be crosslinked in the acid (H+) form to improve ICP stability. Normally, crosslinking is performed in vacuum, to exclude oxygen from the system (can cause ICP charring).
- SPPSU was crosslinked in a vacuum oven preheated to temperatures of 200, 225 and 250°C for durations of up to 8 hours. Under these conditions, samples showed a slight IEC loss ( ⁇ 10%>), and little improvement in long term stability (peroxide test). More severe conditions were employed by exposing samples to 250°C in full vacuum for more than 20 hours. Peroxide testing did not show any considerable difference between SPPSU crosslinked films and SPPSU controls until heated for at least 32 hours.
- the SPPSU films crosslinked at 250°C for 32 hours and 72 hours maintained their film integrity during the peroxide accelerated life test.
- the IEC of these test samples decreased significantly. Specifically, a loss of 63%o (1.90 to 0.69 meg/g) for the 32 hour sample and a loss of 73% (1.90 meg/g to 0.51 meq./g) for the 72 hour crosslinked SPPSU films was calculated. It is anticipated that many of the SO 3 H acid groups form aromatic sulfone (Ar- SO 2 -Ar) crosslinks between polymer chains. This trend confirms that crosslinking (H+ form) of sulfonated polymers can be used to improve long term membrane stability.
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JP2000578363A JP2003503510A (en) | 1998-08-28 | 1999-08-26 | Novel ion conductive material suitable for use in electrochemical applications and related methods |
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CA002342221A CA2342221A1 (en) | 1998-08-28 | 1999-08-26 | Novel ion-conducting materials suitable for use in electrochemical applications and methods related thereto |
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US5438082A (en) * | 1992-06-13 | 1995-08-01 | Hoechst Aktiengesellschaft | Polymer electrolyte membrane, and process for the production thereof |
-
1999
- 1999-08-26 EP EP99965719A patent/EP1115769A1/en not_active Withdrawn
- 1999-08-26 AU AU21424/00A patent/AU2142400A/en not_active Abandoned
- 1999-08-26 CA CA002342221A patent/CA2342221A1/en not_active Abandoned
- 1999-08-26 WO PCT/US1999/019470 patent/WO2000024796A1/en not_active Application Discontinuation
- 1999-08-26 JP JP2000578363A patent/JP2003503510A/en not_active Withdrawn
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US5362836A (en) * | 1992-06-11 | 1994-11-08 | Hoechst Aktiengesellschaft | Polymer electrolytes and their preparation |
US5438082A (en) * | 1992-06-13 | 1995-08-01 | Hoechst Aktiengesellschaft | Polymer electrolyte membrane, and process for the production thereof |
US5561202A (en) * | 1992-06-13 | 1996-10-01 | Hoechst Aktiengesellschaft | Polymer electrolyte membrane, and process for the production thereof |
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US7754844B2 (en) | 2002-10-08 | 2010-07-13 | Toyo Boseki Kabushiki Kaisha | Polyarylene ether compound containing sulfonic acid group, composition containing same, and method for manufacturing those |
US7910248B2 (en) * | 2003-04-28 | 2011-03-22 | Sumitomo Chemical Company, Limited | Aromatic-polyether-type ion-conductive ultrahigh molecular weight polymer, intermediate therefor, and process for producing these |
EP1680821A4 (en) * | 2003-08-28 | 2008-03-26 | Hoku Scient Inc | Composite electrolyte with crosslinking agents |
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US7736539B2 (en) | 2004-01-13 | 2010-06-15 | Johnson Matthey Public Limited Company | Ion-conducting polymers and membranes comprising them |
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US8252481B2 (en) | 2004-07-09 | 2012-08-28 | Nissan Motor Co., Ltd. | Fuel cell system and solid polymer electrolyte film |
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US8216727B2 (en) | 2004-11-10 | 2012-07-10 | Toyo Boseki Kabushiki Kaisha | Aromatic hydrocarbon based proton exchange membrane and direct methanol fuel cell using same |
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US7595373B2 (en) | 2005-12-20 | 2009-09-29 | General Electric Company | Sulfonated polyaryletherketone-polyethersulfone block copolymers |
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WO2010072715A1 (en) * | 2008-12-23 | 2010-07-01 | Basf Se | Non-rechargeable thin-film batteries having anionically-functionalized polymers as separators |
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US10862151B2 (en) | 2015-08-17 | 2020-12-08 | National Institute For Materials Science | Polyphenylsulfone-based proton conducting polymer electrolyte, proton conducting solid polymer electrolyte membrane, electrode catalyst layer for solid polymer fuel cells, method for producing electrode catalyst layer for slid polymer fuel cells, and fuel cell |
Also Published As
Publication number | Publication date |
---|---|
CA2342221A1 (en) | 2000-05-04 |
JP2003503510A (en) | 2003-01-28 |
AU2142400A (en) | 2000-05-15 |
WO2000024796A8 (en) | 2000-09-14 |
EP1115769A1 (en) | 2001-07-18 |
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