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WO2017205458A1 - Membranes bipolaires à base de nanofibres, procédés pour leur fabrication et applications correspondantes - Google Patents

Membranes bipolaires à base de nanofibres, procédés pour leur fabrication et applications correspondantes Download PDF

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Publication number
WO2017205458A1
WO2017205458A1 PCT/US2017/034162 US2017034162W WO2017205458A1 WO 2017205458 A1 WO2017205458 A1 WO 2017205458A1 US 2017034162 W US2017034162 W US 2017034162W WO 2017205458 A1 WO2017205458 A1 WO 2017205458A1
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Prior art keywords
layer
polymers
poly
polymer
bipolar membrane
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Peter N. Pintauro
Eduardo Pereira
Ryszard Wycisk
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Vanderbilt University
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Vanderbilt University
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Priority to US16/099,771 priority Critical patent/US11011756B2/en
Publication of WO2017205458A1 publication Critical patent/WO2017205458A1/fr
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Priority to US16/360,151 priority patent/US12132239B2/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/20—Manufacture of shaped structures of ion-exchange resins
    • C08J5/22—Films, membranes or diaphragms
    • C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
    • C08J5/2275—Heterogeneous membranes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C08J2371/02—Polyalkylene oxides

Definitions

  • the present invention relates generally to the field of materials, and more specifically related to nano- or micro-fiber-based bipolar membranes, fabricating methods and applications of same.
  • a bipolar membrane typically a laminate of anion-exchange and cation- exchange membranes, has the unique capability to split water at a potential as low as 0.8 V while conventional electrolysis requires at least 1.2 V.
  • BPMs are employed in a number of important industrial processes, including the production of mineral acids, the recovery of organic acids from fermentation processes, pH control, and ion-exchange resin regeneration.
  • the use of BPMs in electrodialysis separations eliminates unwanted salt efflux and disposal problems and offers significant savings in electrical energy consumption.
  • BPMs have also been examined for use in self-humidifying hydrogen/air fuel cells, where the recombination of electrochemically generated hydroxide ions and protons at the bipolar junction produces water that improves membrane and electrode binder hydration, with higher power output at reduced feed gas humidity conditions.
  • Bipolar membranes are fabricated by physically attached pre-fabricated anion-exchange and cation- exchange ionomer films, with water splitting at the planar 2D interface of the two membrane sheets. Delamination (ballooning) can occur at this interface due to pressure build-up during start-ups and shut-downs of batch-type electrodialysis separations.
  • the present invention relates to a bipolar membrane comprising an internal
  • a 3D bipolar interface or junction refers to a region/layer within a bipolar membrane, parallel to the membrane surface, spanning the entire cross section of the membrane, and of finite thickness (ranging from less than 1 micron to 25 microns or more) where there is interpenetration of cation-exchange polymer and anion- exchange polymer domains or fibers.
  • the resulting interpenetrating polymer morphology creates a high area bipolar interface (where anion and cation exchange polymers are in near or close contact).
  • the 3D bipolar junction region/layer may have some micro/nanoporosity or be completely dense with no void space. Catalyst particles may also be co-located in the 3D junction layer.
  • One way to create a 3D bipolar interface is to simultaneously form and deposit (e.g., via electro spinning) cation exchange polymer fibers and anion exchange polymer fibers on a common collector surface, followed by suitable processing of the resulting fiber mat to remove some/all of the void space between fibers.
  • the bipolar membrane further comprises a first layer, a second layer, and a third layer.
  • the first layer comprises a cation exchange region formed of one or more cation exchange polymers.
  • the third layer comprises an anion exchange region formed of one or more anion exchange polymers.
  • the second layer disposed between the first layer and the third layer, comprises a mixture of at least one cation exchange polymer and at least one anion exchange polymer, such that an interface of the at least one cation exchange polymer and the at least one anion exchange polymer construes the internal 3D bipolar interface that has a large area, and the at least one cation exchange polymer in the second layer is connected to the one or more cation exchange polymers of the first layer, and the at least one anion exchange polymer in the second layer is connected to the one or more anion exchange polymers of the third layer.
  • the at least one cation exchange polymer in the second layer is same as or different from the one or more cation exchange polymers of the first layer, and the at least one anion exchange polymer in the second layer is same as or different from the one or more anion exchange polymers of the third layer.
  • the internal 3D bipolar interface comprises a mixture of cation exchange and anion exchange nano fibers or micro fibers.
  • the internal 3D bipolar interface comprises a composite of cation exchange polymer nanofibers or microfibers embedded in anion-exchange polymer matrix.
  • the internal 3D bipolar interface comprises a composite of anion exchange polymer nanofibers or microfibers embedded in cation-exchange polymer matrix.
  • the one or more cation exchange polymers of the first layer comprise at least one of polymers containing protogenic groups including sulfonic, sulfonimide, phosphonic and carboxylic, and their derivatives.
  • the one or more cation exchange polymers of the first layer comprise at least one of poly(arylene ether sulfonic acid), poly(phenylsulfone sulfonic acid), poly(phenylene oxide sulfonic acid), poly(arylene sulfonic acid), poly(phosphazene sulfonic acid), sulfonated polybenzimidazole, perfluoro sulfonic acid polymers, poly(vinylphosphonic acid), poly( acrylic acid), poly(methacrylic acid) and their copolymers,
  • the perfluoro sulfonic acid polymers comprise Nafion®,
  • the one or more cation exchange polymers of the first layer comprise sulfonated poly(ether ether ketone) (SPEEK).
  • the one or more anion exchange polymers of the third layer comprise at least one of polymers containing positive fixed charge groups including quaternary ammonium, guanidinium, phosphonium, and their derivatives.
  • the one or more anion exchange polymers of the third layer comprise at least one of polymers based on polyarylene or on aliphatic hydrocarbon backbone.
  • the one or more anion exchange polymers of the third layer comprises quaternized poly(phenylene oxide) (QPPO).
  • the first layer comprises a mixture of two or more cation exchange polymers
  • the third layer comprises a mixture of two or more anion exchange polymers
  • each of the first layer and the third layer comprises uncharged particles for improving mechanical strength and/or increasing ionic conductivity, wherein the uncharged particles comprise graphene, graphene oxide, carbon nanotubes, short polymer fibers, and sulfonated or aminated polyhedral oligomeric silsesquioxane (POSS) nanoparticles.
  • uncharged particles comprise graphene, graphene oxide, carbon nanotubes, short polymer fibers, and sulfonated or aminated polyhedral oligomeric silsesquioxane (POSS) nanoparticles.
  • a polymer blend of an anion exchange ionomer with one or more charged or uncharged polymers is employed in any of the first, second and third layers.
  • a polymer blend of a cation exchange ionomer with one or more charged or uncharged polymers is employed in the first, second and third layers.
  • At least one of the first, second and third layers is further reinforced with polymer fibers being made of an ion-exchange or uncharged polymer including poly(phenyl sulfone) or poly(phenylene oxide), poly(vinylidene fluoride).
  • polymer fibers being made of an ion-exchange or uncharged polymer including poly(phenyl sulfone) or poly(phenylene oxide), poly(vinylidene fluoride).
  • the 3D bipolar interface comprises catalyst particles.
  • the catalyst particles comprise inorganic and organic particles, or polymers.
  • the catalyst particles comprise poly( vinyl pyridine), poly(ethylene imine), poly( vinyl alcohol), poly(acrylic acid), silica, functionalized silica, Al(OH) 3 , Fe(OH) 3 , Fe 2 0 3 , Ca(OH) 2 , Mg(OH) 2 , FeCl 3 , RuCl 3 , Cr(N0 3 ) 3 , Zr0 2 , sodium metasilicate, graphene oxide and polymers or particles with phosphoric or phosphonic acid groups.
  • the internal 3D bipolar interface is a junction layer of
  • interpenetrating polymer nanofibers or microfibers of anion-exchange polymer and cation- exchange polymer, with or without catalyst particles are interpenetrating polymer nanofibers or microfibers of anion-exchange polymer and cation- exchange polymer, with or without catalyst particles.
  • the interpenetrating polymer fiber junction layer has no void space between the fibers.
  • the interpenetrating polymer fiber junction layer has some void space between the fibers.
  • the invention relates to a fuel cell and/or a electrochemical device, each of which comprises at least one bipolar membrane as disclosed above.
  • the invention in another aspect, relates to a method of fabricating a bipolar membrane.
  • the method includes forming a first layer of one or more cation exchange polymers, a second layer of a mixture of at least one cation exchange polymer and at least one anion exchange polymer, and a third layer one or more anion exchange polymers, wherein the second layer is disposed between the first layer and the third layer, thereby defining a bipolar membrane structure; exposing the bipolar membrane structure to dimethylformamide (DMF) vapor dimethylacetamide (DMAc) vapor or alcohol vapor; and hot-pressing the exposed bipolar membrane structure to fabricate the bipolar membrane.
  • DMF dimethylformamide
  • DMAc dimethylacetamide
  • the bipolar membrane has an internal 3D bipolar interface with a large area construed of the at least one cation exchange polymer and the at least one anion exchange polymer.
  • the at least one cation exchange polymer in the second layer is connected to the one or more cation exchange polymers of the first layer, and the at least one anion exchange polymer in the second layer is connected to the one or more anion exchange polymers of the third layer.
  • the first and third layers are formed by solution casting of dense films or impregnation of reinforcing mats with cation-exchange and anion-exchange polymer solutions.
  • the forming step comprises electro spinning a first solution containing the one or more cation exchange polymers to form the first layer; concurrent co- electro spinning the first solution and a second solution containing one or more anion exchange polymers directly onto the first layer to form the second layer; and electro spinning the second solution directly onto the second layer to form third layer.
  • the method further comprises depositing catalyst particles into the second layer, by electro spinning, electro spraying, airbrushing, or piezoelectric spraying.
  • the forming step comprises electro spinning a first solution containing the one or more cation exchange polymers to form the first layer; co-electrospinning the first solution and a second solution containing one or more anion exchange polymers to form the second layer while continuously electro spraying an aqueous suspension of catalyst particles; electro spinning the second solution to form the third layer; and stacking the second layer on the first layer and the third layer on the second layer to define the bipolar membrane structure.
  • the invention relates to a method of fabricating a bipolar membrane.
  • the method comprises electro spinning electro spinning a first solution containing the one or more cation exchange polymers to form a cation exchange mat; electro spraying an aqueous suspension of catalyst particles on the cation exchange mat;
  • the one or more cation exchange polymers comprise at least one of polymers containing protogenic groups including sulfonic, sulfonimide, phosphonic and carboxylic, and their derivatives.
  • the one or more cation exchange polymers comprise at least one of poly(arylene ether sulfonic acid), poly(phenylsulfone sulfonic acid), poly(phenylene oxide sulfonic acid), poly(arylene sulfonic acid), poly(phosphazene sulfonic acid), sulfonated polybenzimidazole, perfluoro sulfonic acid polymers, poly(vinylphosphonic acid), poly(acrylic acid), poly(methacrylic acid) and their copolymers, carboxyphenoxymethylpolysulfone, and their derivatives.
  • the perfluoro sulfonic acid polymers comprise Nafion®, Aquivion®, or their derivatives.
  • the one or more cation exchange polymers of the first layer comprises sulfonated poly( ether ether ketone) (SPEEK).
  • the one or more anion exchange polymers comprise at least one of polymers containing positive fixed charge groups including quaternary ammonium,
  • the one or more anion exchange polymers comprise at least one of polymers based on polyarylene or on aliphatic hydrocarbon backbone.
  • the one or more anion exchange polymers comprise quaternized poly(phenylene oxide) (QPPO).
  • the catalyst particles comprise inorganic and organic particles, or polymers.
  • the catalyst particles comprise poly( vinyl pyridine), poly(ethylene imine), poly( vinyl alcohol), poly(acrylic acid), silica, functionalized silica, Al(OH) 3 , Fe(OH) 3 , Fe 2 0 3 , Ca(OH) 2 , Mg(OH) 2 , FeCl 3 , RuCl 3 , Cr(N0 3 ) 3 , Zr0 2 , sodium metasilicate, graphene oxide and polymers or particles with phosphoric or phosphonic acid groups.
  • FIG. 1 shows schematic of (A) a convention bipolar membrane with a 2-D junction and (B) a bipolar membrane with a 3D nano fiber junction according to one embodiment of the invention.
  • AEL denotes the anion-exchange polymer layer and CEL denotes the cation exchange polymer layer. There is interpenetration of the two layers within the 3D junction region.
  • FIG. 2 shows SEM micrographs of the electrospun SPEEK surface layer (A) before densification (hot-pressing) and (B) after densification (hot-pressing), and SEM micrographs of the final BPM cross-section: (C) the entire cross-section and (D) the magnified junction region, according to one embodiment of the invention.
  • FIG. 3 shows current-voltage curves obtained for the two electrospun BPMs and the solution-cast BPM according to embodiments of the invention.
  • the broken line marks the theoretical water dissociation potential of 0.828 V at about 25 C.
  • Experiments were carried out in a 0.5MNa 2 SO4/BPM/0.5MNa 2 SO4 cell at about 25 ° C.
  • FIG. 4 shows current- voltage curves adapted from the recent publications along with the electrospun 3 ⁇ junction BPM (solid circles, where the data were collected in a
  • 0.5MNa 2 SO 4 /BPM/0.5MNa 2 SC>4 cell at about 25 C) according to embodiments of the invention.
  • the broken line marks the theoretical water dissociation potential of 0.83 V at about 25 C.
  • FIG. 5 shows the performance of three nanofiber-based bipolar membranes where the membranes were made by separately electro spinning the cation exchange, anion exchange and bipolar junction layers, followed by hot pressing the three layers into a single film ⁇ Protocol #ld), according to embodiments of the invention.
  • Three different methods of adding catalytic Al(OH) 3 particles to the junction layer are contrasted in this figure. Experiments were carried out in a 0.5MNa 2 SO 4 /BPM/0.5MNa 2 SO 4 cell at about 25 ° C.
  • FIG. 6 shows the performance of integral three-layer integral electrospun bipolar membranes with different hot pressing conditions using Protocol #2, according to embodiments of the invention. Experiments were carried out in a 0.5MNa 2 SO 4 /BPM/0.5MNa 2 SO 4 cell at about 25 ° C.
  • FIG. 7 shows scanning electron micrographs of the dual fiber junction and cross- sections of a bipolar membrane with a 3D junction with Al(OH) 3 catalyst particles in the junction region according to embodiments of the invention: (A) top-down view of dual fibers in the junction region with Al(OH) 3 nanoparticles (before densification), (B) freeze- fractured cross section of the entire densified membrane with the junction region framed and (C) a magnified view of the framed 3D junction region in (B).
  • FIG. 8 shows the performance of uncatalized nanofiber-based bipolar membrane with variation of junction thickness and morphology, according to embodiments of the invention.
  • BPMs A, B and C were obtained via electro spinning.
  • Solution cast membrane was obtained by separately solution casting anion-echange and cation-exchange polymer films and then hotpressing them together.
  • a commercial Fumasep membrane characteristic is also shown.
  • FIG. 9 shows "self-repair” effect and the performance of nanofiber-based bipolar membrane with variation of junction thickness and morphology, according to embodiments of the invention.
  • the membranes with incompletely eliminated voids (marked “porous") show significant resistive losses, while the remaining membranes show "self-repair” effect, whereby the initial high voltage drop is reduced significantly after a certain critical voltage drop is reached.
  • FIG. 10 shows a comparison of water splitting of three bipolar membranes at progressively increasing current density - cycling from 100 mA/cm 2 to 1000 mA/cm 2 in 0.5M Na 2 S0 4 solution:
  • A Electrospun three layer membrane (made by Protocol #2) with a 3D catalyzed junction (catalyzed by addition of Al(OH) 3 particles) according to embodiments of the invention;
  • B a Fumasep FBM commercial bipolar membrane;
  • C Electrospun membrane with a catalyzed junction made by Protocol #3 (catalyzed by addition of Al(OH) 3 particles) according to embodiments of the invention.
  • FIG. 11 shows photographs of bipolar membranes after a high current density water splitting polarization experiment, where the maximum current density was 1,100 mA/cm".
  • a Fumasep FBM membrane from Fumatech GmbH (left) showing blistering/degradation and a 3D junction electrospun membrane (right).
  • first, second, third, etc. may be used herein to describe various elements, components, regions, layers and/or sections, these elements, components, regions, layers and/or sections should not be limited by these terms. These terms are only used to distinguish one element, component, region, layer or section from another element, component, region, layer or section. Thus, a first element, component, region, layer or section discussed below can be termed a second element, component, region, layer or section without departing from the teachings of the present invention.
  • relative terms such as “lower” or “bottom” and “upper” or “top,” may be used herein to describe one element's relationship to another element as illustrated in the figures. It will be understood that relative terms are intended to encompass different orientations of the device in addition to the orientation shown in the figures. For example, if the device in one of the figures is turned over, elements described as being on the “lower” side of other elements would then be oriented on the “upper” sides of the other elements. The exemplary term “lower” can, therefore, encompass both an orientation of lower and upper, depending on the particular orientation of the figure. Similarly, if the device in one of the figures is turned over, elements described as “below” or “beneath” other elements would then be oriented “above” the other elements. The exemplary terms “below” or “beneath” can, therefore, encompass both an orientation of above and below.
  • the phrase "at least one of A, B, and C" should be construed to mean a logical (A or B or C), using a non-exclusive logical OR. It should be understood that one or more steps within a method may be executed in different order (or concurrently) without altering the principles of the invention.
  • AEL denotes an anion-exchange layer generally made of ionomers and designed to conduct anions
  • CEL denotes a cation exchange layer generally made of ionomers and designed to conduct cations.
  • conducting polymer or "ionomer” generally refers to a polymer that conducts ions. More precisely, the ionomer refers to a polymer that includes repeat units of at least a fraction of ionized units.
  • polyelectrolyte generally refers to a type of ionomer, and particularly a polymer whose repeating units bear an electrolyte group, which will dissociate when the polymer is exposed to aqueous solutions (such as water), making the polymer charged.
  • aqueous solutions such as water
  • polyelectrolytes may be generally referred to as "charged polymers”.
  • the terms “polyelectrolyte fiber” or “charged polymer fiber” generally refer to the polymer fiber formed by polyelectrolytes or the likes.
  • polyelectrolyte, ionomer, and charged polymer can be used interchangeably.
  • the terms “uncharged polymer” or “uncharged (or minimally charged) polymer” generally refer to the polymer that does not effectively conduct ions, particularly to the polymer whose repeating units do not bear an electrolyte group or bear a small number of electrolyte groups, and thus the polymer will not be charged or will have a very small charge when being exposed to aqueous solutions.
  • the terms “uncharged polymer fiber” or “uncharged (or minimally charged) polymer fiber” generally refer to the polymer fiber formed by the uncharged/uncharged (or minimally charged) polymer.
  • bipolar membrane having an internal 3-dimensional (3D) bipolar interface (junction) formed between an anion exchange layer and a cation exchange layer and their applications
  • BPM bipolar membrane
  • junction internal 3-dimensional bipolar interface
  • aspects of the present invention disclosed herein are not limited to being used in connection with one particular type of bipolar membranes such as nano- or micro-fiber-based 3D junction bipolar membranes fabricated by an electro spinning process and may be practiced in connection with other types of bipolar membranes or other types of electrochemical devices such as fuel cells, capacitors and/or batteries without departing from the scope of the present invention disclosed herein.
  • a bipolar membrane is an ion exchange membrane having a cation exchange layer 101 and an anion exchange layer 102, as shown in FIG. 1(A).
  • water can be split inside the membrane and then proton (H + ) and hydroxide ion (OH " ) are generated.
  • This unique function of water splitting is utilized for production of an acid and a base from a corresponding salt in combination with conventional monopolar ion exchange membrane.
  • the present invention relates to a bipolar membrane including an electrospun 3D water splitting junction interpenetrated between the anion-exchange layer (AEL) and the cation-exchange layer (CEL).
  • AEL anion-exchange layer
  • CEL cation-exchange layer
  • the extended electrospun 3D junction leads to improvements in the membrane selectivity (to separate protons and hydroxide ions) and the rate of water splitting (high current densities with a low transmembrane voltage drop), and also leads to greater delamination resistance, due to mechanical interlocking of the two polymer sides of the bipolar membrane.
  • the bipolar membrane having an extended 3D water splitting junction region 120 between the cation exchange layer 110 and the anion exchange layer 130, where there is interpenetration of the two cation and anion exchange layers 110 and 130 within the 3D junction region 120.
  • Such bipolar membrane has an increased interfacial area for water splitting at the junction 120 of the cation exchange polymer layer 110 and the anion exchange polymer layer 130. This morphology is important for at least two reasons: (1) it improves the attachment (adhesion) of the two ion-exchange layers so that ballooning/delamination is minimized or eliminated and (2) the increased bipolar junction area leads to better distribution of the water splitting reaction and lower membrane voltage drop for the same operating current density.
  • the cation exchange layer (mat) 110 of the bipolar membrane is formed of one or more cation exchange polymers.
  • the anion exchange layer (mat) 130 of the bipolar membrane is formed of one or more anion exchange polymers.
  • the 3D junction layer (region) 120 of the bipolar membrane is formed of a mixture of at least one cation exchange polymer and at least one anion exchange polymer and corresponds to an internal 3D bipolar interface of the at least one cation exchange polymer and the at least one anion exchange polymer, which has a large area.
  • the at least one cation exchange polymer in the 3D junction layer 120 is connected to the one or more cation exchange polymers of the cation exchange layer 110, and the at least one anion exchange polymer in the 3D junction layer 120 is connected to the one or more anion exchange polymers of the anion exchange layer 130, as shown in FIG. 1(B).
  • the at least one cation exchange polymer in the 3D junction layer 120 is same as or different from the one or more cation exchange polymers of the cation exchange layer 110, and the at least one anion exchange polymer in the 3D junction layer 120 is same as or different from the one or more anion exchange polymers of the anion exchange layer 130.
  • the cation exchange layer 110 includes the cation exchange nano- or micro-fibers.
  • the anion exchange layer 130 includes the anion exchange nano- or micro-fibers.
  • the internal 3D bipolar interface (junction) 120 includes a mixture of cation exchange and anion exchange nano- or micro-fibers.
  • the one or more cation exchange polymers of the cation exchange layer 110 include at least one of polymers containing protogenic groups including sulfonic, sulfonimide, phosphonic and carboxylic, and their derivatives.
  • the one or more cation exchange polymers include at least one of poly(arylene ether sulfonic acid), poly(phenylsulfone sulfonic acid), poly(phenylene oxide sulfonic acid), poly(arylene sulfonic acid), poly(phosphazene sulfonic acid), sulfonated polybenzimidazole, perfluoro sulfonic acid polymers, poly(vinylphosphonic acid), poly(acrylic acid), poly(methacrylic acid) and their copolymers, carboxyphenoxymethylpolysulfone, and their derivatives.
  • the perfluoro sulfonic acid polymers comprises Nafion®, Aquivion®, or their derivatives.
  • the one or more cation exchange polymers include sulfonated poly(ether ether ketone) (SPEEK).
  • the one or more anion exchange polymers of the anion exchange layer 130 include at least one of polymers containing positive fixed charge groups including quaternary ammonium, guanidinium, phosphonium, and their derivatives.
  • the one or more anion exchange polymers include at least one of polymers based on polyarylene or on aliphatic hydrocarbon backbone.
  • the one or more anion exchange polymers includes quaternized poly(phenylene oxide) (QPPO).
  • the cation exchange layer 110 includes a mixture of two or more cation exchange polymers, and wherein the anion exchange layer 130 includes a mixture of two or more anion exchange polymers.
  • each of the cation exchange layer 110 and the anion exchange layer 130 includes uncharged particles for improving mechanical strength and/or increasing ionic conductivity, where the uncharged e particles includes graphene, graphene oxide, carbon nanotubes, short polymer fibers, and sulfonated or aminated polyhedral oligomeric
  • a polymer blend of an anion exchange ionomer with one or more charged or uncharged polymers is employed in any of the cation exchange layer 110, the 3D bipolar junction 120 and the anion exchange layer 130.
  • a polymer blend of a cation exchange ionomer with one or more charged or uncharged polymers is employed in any of the cation exchange layer 110, the 3D bipolar junction 120 and the anion exchange layer 130.
  • At least one of the cation exchange layer 110, the 3D bipolar junction 120 and the anion exchange layer 130 is further reinforced with polymer fibers being made of an ion-exchange or uncharged polymer including poly(phenyl sulfone) or
  • the 3D bipolar junction 120 includes catalyst particles.
  • the catalyst particles include inorganic and organic particles, or polymers.
  • the catalyst particles include poly( vinyl pyridine), poly(ethylene imine), poly( vinyl alcohol), poly(acrylic acid), silica, functionalized silica, Al(OH) 3 , Fe(OH) 3 , Fe 2 0 3 , Ca(OH) 2 , Mg(OH) 2 , FeCl 3 , RuCl 3 , Cr(N0 3 ) 3 , Zr0 2 , sodium metasilicate, graphene oxide and polymers or particles with phosphoric or phosphonic acid groups.
  • the internal 3D bipolar interface 120 is a junction layer of interpenetrating polymer nano- or micro-fibers of anion-exchange polymer and cation-exchange polymer, with or without catalyst particles.
  • the interpenetrating polymer fiber junction layer 120 has no void space between the fibers.
  • the invention relates to a fuel cell and/or a electrochemical device, each of which comprises at least one bipolar membrane as disclosed above.
  • the invention in another aspect, relates to a method of fabricating a bipolar membrane.
  • the method includes the following steps: (a) forming a cation exchange layer of one or more cation exchange polymers, a 3D bipolar junction layer of a mixture of at least one cation exchange polymer and at least one anion exchange polymer, and an anion exchange layer one or more anion exchange polymers, where the second layer is disposed between the first layer and the third layer, thereby defining a bipolar membrane structure; (b) exposing the bipolar membrane structure to dimethlformamide (DMF) vapor, DMAc vapor or alcohol vapor; and (c) hot-pressing the exposed bipolar membrane structure to fabricate the bipolar membrane.
  • DMF dimethlformamide
  • the bipolar membrane has an internal 3D bipolar interface with an interfacial area construed of the at least one cation exchange polymer and the at least one anion exchange polymer.
  • the at least one cation exchange polymer in the 3D bipolar junction layer is connected to the one or more cation exchange polymers of the cation exchange layer, and the at least one anion exchange polymer in the 3D bipolar junction layer is connected to the one or more anion exchange polymers of the anion exchange layer.
  • the cation and anion exchange layers are formed by solution casting of dense films or impregnation of reinforcing mats with cation-exchange and anion-exchange polymer solutions, respectively.
  • the forming step comprises electro spinning a first solution containing the one or more cation exchange polymers to form the cation exchange layer;
  • the electro spinning process typically involves applying a high voltage electric field to a spinneret needle containing a polymer solution or polymer melt.
  • Mutual charge repulsion on the surface of the solution overcomes the surface tension such as to produce and eject a thin liquid jet of the solution from the tip of the spinneret needle.
  • electrostatic repulsion from surface charges causes the diameter of the jet to narrow.
  • the jet may enter a whipping mode and thereby be stretched and further narrowed due to instabilities in the electric field. Solid fibers are produced as the jet dries and the fibers accumulate on the collector to form a non- woven material.
  • Electro spinning has been used previously for the fabrication of nanofiber composite ion- conducting cation and anion exchange membranes with unique and attractive characteristics for electrochemical devices and processes.
  • nanofiber composite ion- conducting cation and anion exchange membranes with unique and attractive characteristics for electrochemical devices and processes.
  • nanofiber composite ion- conducting cation and anion exchange membranes with unique and attractive characteristics for electrochemical devices and processes.
  • Nafion/polyphenylsulfone membranes were shown to be more durable than commercial Nafion in a hydrogen/air fuel cell [2].
  • nanofiber composite membranes composed of Nafion nano fibers surrounded by PVDF (polyvinylidene fluoride, or polyvinylidene difluoride) showed excellent performance in H 2 /Br 2 regenerative fuel cells, due to low bromine species crossover [3].
  • Recently developed electrospun composite anion-exchange membranes exhibited moderate water swelling, excellent mechanical strength, and high hydroxide ion conductivity, e.g., 0.065 S/cm at room temperature and 0.102 S/cm at 60 C [4].
  • the 3D junction is formed by concurrent dual-fiber electro spinning of an anion-exchange polymer such as quaternized poly(phenylene oxide) (QPPO) and a cation- exchange polymer, such as sulfonated poly(etherether ketone) (SPEEK) into an interpenetrating nano- or micro-fiber network, which after densification, gives a very high interfacial area 3D nonporous bipolar junction between films (layers) of neat QPPO and SPEEK.
  • QPPO quaternized poly(phenylene oxide)
  • SPEEK sulfonated poly(etherether ketone)
  • the method further comprises depositing catalyst particles into the 3D bipolar junction layer, by electrospinning, electro spraying, airbrushing, or piezoelectric spraying.
  • the forming step comprises electrospinning a first solution containing the one or more cation exchange polymers to form the cation exchange layer; co- electro spinning the first solution and a second solution containing one or more anion exchange polymers to form the 3D bipolar junction layer while continuously electro spraying an aqueous suspension of catalyst particles; electrospinning the second solution to form the anion exchange layer; and stacking the 3D bipolar junction layer on the cation exchange layer and the anion exchange layer on the 3D bipolar junction layer to define the bipolar membrane structure.
  • the invention relates to a method of fabricating a bipolar membrane.
  • the method comprises electro spinning electro spinning a first solution containing the one or more cation exchange polymers to form a cation exchange mat; electro spraying an aqueous suspension of catalyst particles on the cation exchange mat;
  • the one or more cation exchange polymers comprise at least one of polymers containing protogenic groups including sulfonic, sulfonimide, phosphonic and carboxylic, and their derivatives.
  • the one or more cation exchange polymers comprise at least one of poly(arylene ether sulfonic acid), poly(phenylsulfone sulfonic acid), poly(phenylene oxide sulfonic acid), poly(arylene sulfonic acid), poly(phosphazene sulfonic acid), sulfonated polybenzimidazole, perfluoro sulfonic acid polymers, poly(vinylphosphonic acid), poly(acrylic acid), poly(methacrylic acid) and their copolymers, carboxyphenoxymethylpolysulfone, and their derivatives.
  • the perfluoro sulfonic acid polymers comprises Nafion®,
  • the one or more cation exchange polymers of the cation exchange layer comprises sulfonated poly(ether ether ketone) (SPEEK).
  • the one or more anion exchange polymers comprise at least one of polymers containing positive fixed charge groups including quaternary ammonium, guanidinium, phosphonium, and their derivatives).
  • the one or more anion exchange polymers comprise at least one of polymers based on polyarylene or on aliphatic hydrocarbon backbone.
  • the one or more anion exchange polymers comprise quaternized poly(phenylene oxide) (QPPO).
  • the catalyst particles comprise inorganic and organic particles, or polymers.
  • the catalyst particles comprise poly( vinyl pyridine), poly(ethylene imine), poly( vinyl alcohol), poly(acrylic acid), silica, functionalized silica, Al(OH) 3 , Fe(OH) 3 , Fe 2 0 3 , Ca(OH) 2 , Mg(OH) 2 , FeCl 3 , RuCl 3 , Cr(N0 3 ) 3 , Zr0 2 , sodium metasilicate, graphene oxide and polymers or particles with phosphoric or phosphonic acid groups.
  • Other embodiments and modifications of the invention can also be implemented as follows.
  • the cation-exchange polymer can be any one of a number of polymers containing protogenic groups (e.g. sulfonic, sulfonimide, phosphonic and carboxylic).
  • examples of such materials include poly(arylene ether sulfonic acid), poly(phenylsulfone sulfonic acid), poly(phenylene oxide sulfonic acid), poly(arylene sulfonic acid), poly(phosphazene sulfonic acid), sulfonated polybenzimidazole, perfluoro sulfonic acid polymers (like Nafion, Aquivion and similar), and also poly(vinylphosphonic acid), poly(acrylic acid), poly(methacrylic acid) and their copolymers, and carboxyphenoxymethylpolysulfone.
  • the anion-exchange polymer can be any of a number of polymers containing positive fixed charge groups (e.g. quaternary ammonium, guanidinium or phosphonium).
  • the polymers can be based on polyarylene or on aliphatic hydrocarbon backbone.
  • the outer ion-exchange layers and the bipolar junction layer of the bipolar membrane can be additionally reinforced with polymer fibers, which can be made of an ion-exchange or uncharged polymer (like poly(phenyl sulfone) or poly(phenylene oxide), poly(vinylidene fluoride). Multi-fiber electro spinning can be conveniently employed to prepare such reinforced layers.
  • the BPM can have a bipolar junction including the cation and anion exchange polymers with or without catalyst particles, where the later may be useful as membranes for self- humidifying fuel cells.
  • Inorganic and organic particles or polymers can be used in the catalyzed junction.
  • the deposition of the catalyst can be accomplished by electro spinning, electro spraying, airbrushing or piezoelectric spraying.
  • the catalyst can be deposited continuously and concurrently with the fiber electro spinning or it can be applied as a single or multiple layers.
  • the outer layer can include mixtures two or more cation exchange polymers or two or more anion exchange polymers.
  • the combination of same charge polymers can improve conductivity/permselectivity balance as well as the mechanical strength of the outside layers through the control of the overall water/salt uptake.
  • the outer layers of the bipolar membrane can include neat cation exchange ionomer or anion exchange ionomer with inert/uncharged particles. The particles can improve mechanical strength and/or increase ionic conductivity.
  • Example particles of the first type could be graphene, graphene oxide, carbon nanotubes, short polymer fibers, and sulfonated or aminated polyhedral oligomeric silsesquioxane (POSS) nanoparticles can serve as example of the second particle type.
  • PES polyhedral oligomeric silsesquioxane
  • the outer layers of the bipolar membrane can be made by solution casting of dense films or the impregnation of reinforcing mats with the appropriate cation-exchange and anion- exchange polymer solutions, followed by solvent evaporation and hot pressing onto the 3D nano- or micro-fiber junction layer.
  • a polymer blend of an anion-exchange ionomer with one or more charged or uncharged polymers can be employed in any of the layers of the bipolar membrane.
  • a polymer blend of a cation-exchange ionomer with one or more charged or uncharged polymers can be used in the outer layer and/or the bipolar junction region.
  • Polymer fibers can be made using an electro spinning process or processes that do not use an electric field, including gas jet fiber processing and centrifugal fiber spinning.
  • the electro spinning solutions were prepared from sulfonated poly(etherether ketone)
  • Table 1 Ion conductivity and IEC of the two ion-exchange polymers used in the exemplary embodiments of the disclosure. The testing was performed with solution cast films.
  • the 3D junction membranes according one embodiment of the invention were fabricated using a sequence of four steps: (1) electro spinning of a cation-exchange mat, (2) concurrent co-electrospinning of cation-exchange and anion-exchange polymer mixture onto the cation-exchange mat, (3) electro spinning of anion-exchange polymer directly onto the mixed cation-exchange/anion-exchange layer, and (4) densification of the entire three-layer mat by exposure to either dimethlformamide (DMF) or alcohol (e.g. methanol or ethanol) vapor (which caused the fibers to soften and flow) followed by hot-pressing (which resulted in complete pore closure).
  • DMF dimethlformamide
  • alcohol e.g. methanol or ethanol
  • the Protocol #1 trilayer membrane can also be made by (1) solution casting separate outer layers of cation-exchange and anion-exchange polymers, (2) concurrent co-electrospinning of cation-exchange and anion-exchange polymer mixture (with or without the addition of catalyst particles) for the junction layer, and (3) pressing together the three separate layers with fiber mat densification.
  • Table 2 Electro spinning conditions used for the fabrication of the bipolar junction. Solution Collector Humidity (ml/h) Voltage
  • the predicted weight ratio of SPEEK to QPPO in the 3D junction layer was close to about 1: 1.
  • Two bipolar membranes were fabricated with different thickness of the junction (about 3 ⁇ and about 6 ⁇ ), as determined by SEM analysis of the membrane cross-sections. SEM and membrane density analyses confirmed complete mat densification via DMAc, DMF or alcohol vapor exposure and hot-pressing. There were no defect pores in the outer layers, with well-defined dual-polymer composite junction between the SPEEK and QPPO layers.
  • (planar) junction BPM made by solution casting and pressing two films composed of SPEEK and QPPO layers, and two electrospun BPMs with 3D junctions according to embodiments of the invention: Membrane A with a 12 ⁇ layer of SPEEK, a 12 ⁇ layer of QPPO and a 3 ⁇ thick junction, and Membrane B with a 12 ⁇ layer of SPEEK, a 12 ⁇ layer of QPPO, and a 6 ⁇ thick junction.
  • the electrochemical BPM characterization was performed at room temperature in a two- compartment cell, equipped with Ag/AgCl reference electrodes inside Luggin capillaries and with working Pt/Ir flag electrodes, where the compartments were filled with a 0.5MNa 2 SO 4 solution. That is, experiments were carried out in a 0.5MNa 2 SO 4 /BPM/0.5MNa 2 SO 4 cell at about 25 C.
  • the resultant current-voltage curves for the two electrospun BPMs and the solution-cast BPM at about 25 C are shown in FIG. 3, where the broken line marks the theoretical water dissociation potential of 0.828 V at 25 ° C. Up to about 200 niA/cm 2 , no limiting current was obtained for any of the three bipolar membranes, indicating sufficient water transport rates to replenish that water which is split into H + and OH " at the junction.
  • the solution-cast membrane with a planar 2D junction exhibited a relatively high ionic resistance (the slope of the I-V curve was not large), with a high membrane voltage drop of 2.0 V at 100 niA/cm , presumably due to imperfect bipolar junction/bonding of the two polymer layers and the greater thicknesses of the SPEEK and QPPO layers (50 ⁇ each).
  • Another advantage of the morphology of the BPMs according to embodiments of the invention is an improved resistance to delamination due to interlocking of the interpenetrating networks of cationic and anionic fibers. It is also important to note that during the concurrent electro spinning of anion and cation exchange polymers for the 3D junction region, the SPEEK and QPPO fibers intermix in essentially the dry state (due to rapid solvent evaporation between the spinneret tip and fiber collector surface), thus avoiding/preventing anion-cation fixed-charge site neutralization and the resultant increase in interfacial resistance that can occur at the BPM junction during a sequential film wet casting fabrication procedure.
  • FIG. 4 shows current- voltage curves adapted from the recent publications along with the electrospun 3 ⁇ thick 3D junction BPM (solid circles, where the data were collected in a 0.5MNa 2 SO 4 /BPM/0.5MNa 2 SO 4 cell at about 25 C) according to one embodiment of the present invention.
  • the broken line marks the theoretical water dissociation potential of 0.83 V at 25 C.
  • the I-V polarization behavior of the electrospun 3D junction bipolar membrane is contrasted with five PBM membranes in the literature with 2D junctions. None of the published data matches the performance of the 3D junction electrospun membrane according to one embodiment of the present invention.
  • junction region in the 3D nanofiber membrane contained no catalyst to promote water splitting, whereas many of the other films in FIG. 4 had some kind of catalytic material/sublayer at the 2D junction, e.g., cationic resin microparticles in the membrane from Hao [5], polyethyleneimine in Wes sling's LbL membrane [1], copper phthalocyanine nano fibers from Zhou [6] and polyvinylpiridine in Wessling [7].
  • catalytic material/sublayer at the 2D junction e.g., cationic resin microparticles in the membrane from Hao [5], polyethyleneimine in Wes sling's LbL membrane [1], copper phthalocyanine nano fibers from Zhou [6] and polyvinylpiridine in Wessling [7].
  • nanofiber-based bipolar membranes were made with catalytic particles at the bipolar 3D junction according to embodiments of the invention.
  • FumaTechFBM membranes supposedly have a poly(acrylic acid/poly(vinylpyridine) salt complex at the junction).
  • aluminum hydroxide was selected as the catalyst to be incorporated into the bipolar 3D junction.
  • the good catalytic action of insoluble hydroxides of chromium and iron can also be utilized to practice the invention.
  • other multivalent metal compounds and amines were also used as the catalysts.
  • a method for integral bipolar membrane fabrication with Al(OH) 3 nanoparticles which is referred to "Protocol #2" hereinafter, is as follows: (1) electro spinning SPEEK fibers (e.g., about 100 ⁇ layer), (2) co-electro spinning a dual fiber layer from SPEEK and QPPO fibers while continuously electro spraying an Al(OH) 3 aqueous suspension (e.g., about 10 nm particles in water with a few drops of Triton X-100 non-ionic surfactant, where the particle concentration was about 0.5-1.0% in water), (3) electro spinning QPPO fibers (e.g., about 75 ⁇ layer), (4) exposing the mat to DMAc, DMF or alcohol vapor for about 55-30 min, and (5) hot-pressing the mat for about 10 min at about 120 C and about 15000 lb force.
  • electro spinning SPEEK fibers e.g., about 100 ⁇ layer
  • Protocol #1 involves the separate electro spinning of the three layers of a BPM, followed by hot pressing and vapor exposure, as discussed above.
  • Protocol #1A the Al(OH) 3 particles were added to the separately electrospun junction layer and then the three separate electrospun fiber mats were hot pressed to form a bipolar membrane.
  • another method for integral bipolar membrane fabrication which is referred to "Protocol #3" hereinafter, includes: (1) electro spinning SPEEK fibers (e.g., about 100 ⁇ layer), (2) electro spraying an aqueous suspension of Al(OH) 3 particles, (3) electro spining a QPPO fiber layer, (4) processing the two-layer mat by exposing to DMAc, DMF or alcohol vapor followed by hot pressing.
  • Experimental data from three duplicate nano fiber bipolar membranes made by this Protocol #3 are shown in FIG. 7.
  • FIG. 5 shows the performance of three nanofiber-based bipolar membranes where the bipolar membranes were made by separately electro spinning the cation exchange, anion exchange and bipolar junction layers, followed by hot pressing the three layers into a single film ⁇ Protocol #1A). Experiments were carried out in a 0.5MNa 2 SO 4 /BPM/0.5MNa 2 SO 4 cell at about 25 C.
  • bipolar membranes formed by three different methods of adding catalytic Al(OH) 3 particles to the junction layer have very different the performance, compared to the performance of a commercial BPM from FumaTech. As shown in FIG. 5, the three layer film with electro sprayed Al(OH) 3 particles performed best, better than the commercial film, i.e., the water splitting voltage for the nanofiber-based membrane was lower than that for the FumaTech BPM.
  • integral electrospun 3D junction BPMs with catalysts were fabricated and evaluated.
  • the three layers of the bipolar membrane were electrospun sequentially followed by fiber mat processing to melt the fibers and remove defect voids.
  • FIG. 6 shows the performance of integral three-layer integral electrospun bipolar membranes with different hot pressing conditions using Protocol #2.
  • An important advantage of the new 3D junction BPM morphology is an improved resistance to delamination due to interpenetration and interlocking of cationic and anionic fibers. This is especially important at moderate/high operating current densities, where severe ion/water concentration gradients can create differential polymer swelling of the anion and cation exchange layers, leading to blistering (film separation) at the interfacial junction.
  • the improved performance and mechanical stability of the 3D junction membrane (made by Protocol #2) is evident in the high current density polarization curves in FIG. 10. Membranes were evaluated for water splitting at room temperature using a current density cycling protocol where the maximum applied current density for a given polarization experiments was successively increased from 100 mA/cm 2 to 1100 mA/cm 2.
  • the invention discloses, among other things, a bipolar membrane with a 3-D fibrous bipolar interface, where nano- or micro-fibers of one ion exchange polymer come in contact with an oppositely charged ion exchange polymer.
  • this bipolar interface has a large area.
  • the bipolar membrane can be used for industrial- scale electrodialysis separations and salt splitting, without membrane degradation.

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Abstract

L'invention concerne une membrane bipolaire comprenant un mat échangeur de cations d'un ou de plusieurs polymères échangeurs de cations, un mat échangeur d'anions d'un ou de plusieurs polymères échangeurs d'anions et une interface bipolaire 3D interne, disposée entre les couches échangeuses de cations et d'anions, comprenant un mélange d'au moins un polymère échangeur de cations et d'au moins un polymère échangeur d'anions, de telle sorte qu'une interface dudit au moins un polymère échangeur de cations et dudit au moins un polymère échangeur d'anions est l'interface bipolaire 3D interne qui présente une grande surface et ledit au moins un polymère échangeur de cations dans l'interface bipolaire 3D est relié audit au moins un polymère échangeur de cations de la couche échangeuse de cations et ledit au moins un polymère échangeur d'anions dans l'interface bipolaire 3D est relié audit au moins un polymère échangeur d'anions de la couche échangeuse d'anions.
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DE102019104402A1 (de) * 2018-10-26 2020-04-30 Deutsches Zentrum für Luft- und Raumfahrt e.V. Elektrochemischer Reaktor und Verfahren zum Umwandeln von chemischer Reaktionsenergie in elektrische Energie
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US11268200B2 (en) 2019-05-20 2022-03-08 University Of Oregon Bipolar membranes
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WO2023151941A1 (fr) 2022-02-11 2023-08-17 Fujifilm Manufacturing Europe Bv Membranes
CN114643083A (zh) * 2022-03-11 2022-06-21 福建师范大学 一种含金属酞菁衍生物水解离催化剂的单片型聚三氟氯乙烯双极膜及其制备方法
CN114643083B (zh) * 2022-03-11 2023-12-05 福建师范大学 一种含金属酞菁衍生物水解离催化剂的单片型聚三氟氯乙烯双极膜及其制备方法
WO2025014368A1 (fr) * 2023-07-11 2025-01-16 Stichting Wetsus, European Centre Of Excellence For Sustainable Water Technology Procédé d'assemblage en continu d'une membrane bipolaire, membrane bipolaire, et utilisation de ladite membrane bipolaire
NL2035348B1 (en) * 2023-07-11 2025-01-24 Stichting Wetsus European Centre Of Excellence For Sustainable Water Tech Method for continuously assembling a bipolar membrane, bipolar membrane, and use of said bipolar membrane
CN117654650A (zh) * 2023-12-21 2024-03-08 上海纳米技术及应用国家工程研究中心有限公司 一种改性离子交换膜的制备方法及其产品
CN118248891A (zh) * 2024-05-28 2024-06-25 中石油深圳新能源研究院有限公司 双极性复合膜及其制备方法及应用

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