Self-Healing Proton-Exchange Membranes Composed of Nafion-Poly(vinyl alcohol) Complexes for Durable Direct Methanol Fuel Cells.

PubMed

Li, Yixuan; Liang, Liang; Liu, Changpeng; Li, Yang; Xing, Wei; Sun, Junqi

2018-04-30

Proton-exchange membranes (PEMs) that can heal mechanical damage to restore original functions are important for the fabrication of durable and reliable direct methanol fuel cells (DMFCs). The fabrication of healable PEMs that exhibit satisfactory mechanical stability, enhanced proton conductivity, and suppressed methanol permeability via hydrogen-bonding complexation between Nafion and poly(vinyl alcohol) (PVA) followed by postmodification with 4-carboxybenzaldehyde (CBA) molecules is presented. Compared with pure Nafion, the CBA/Nafion-PVA membranes exhibit enhanced mechanical properties with an ultimate tensile strength of ≈20.3 MPa and strain of ≈380%. The CBA/Nafion-PVA membrane shows a proton conductivity of 0.11 S cm -1 at 80 °C, which is 1.2-fold higher than that of a Nafion membrane. The incorporated PVA gives the CBA/Nafion-PVA membranes excellent proton conductivity and methanol resistance. The resulting CBA/Nafion-PVA membranes are capable of healing mechanical damage of several tens of micrometers in size and restoring their original proton conductivity and methanol resistance under the working conditions of DMFCs. The healing property originates from the reversibility of hydrogen-bonding interactions between Nafion and CBA-modified PVA and the high chain mobility of Nafion and CBA-modified PVA. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Investigation of local environments in Nafion-SiO(2) composite membranes used in vanadium redox flow batteries.

PubMed

Vijayakumar, M; Schwenzer, Birgit; Kim, Soowhan; Yang, Zhenguo; Thevuthasan, S; Liu, Jun; Graff, Gordon L; Hu, Jianzhi

2012-04-01

Proton conducting polymer composite membranes are of technological interest in many energy devices such as fuel cells and redox flow batteries. In particular, polymer composite membranes, such as SiO(2) incorporated Nafion membranes, are recently reported as highly promising for the use in redox flow batteries. However, there is conflicting reports regarding the performance of this type of Nafion-SiO(2) composite membrane in the redox flow cell. This paper presents results of the analysis of the Nafion-SiO(2) composite membrane used in a vanadium redox flow battery by nuclear magnetic resonance (NMR) spectroscopy, X-ray photoelectron spectroscopy (XPS), Fourier Transform Infra Red (FTIR) spectroscopy, and ultraviolet-visible spectroscopy. The XPS study reveals the chemical identity and environment of vanadium cations accumulated at the surface. On the other hand, the (19)F and (29)Si NMR measurement explores the nature of the interaction between the silica particles, Nafion side chains and diffused vanadium cations. The (29)Si NMR shows that the silica particles interact via hydrogen bonds with the sulfonic groups of Nafion and the diffused vanadium cations. Based on these spectroscopic studies, the chemical environment of the silica particles inside the Nafion membrane and their interaction with diffusing vanadium cations during flow cell operations are discussed. This study discusses the origin of performance degradation of the Nafion-SiO(2) composite membrane materials in vanadium redox flow batteries. Copyright © 2011 Elsevier Inc. All rights reserved.

Investigation of Local Environments in Nafion-SiO2 Composite Membranes used in Vanadium Redox Flow Batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vijayakumar, M.; Schwenzer, Birgit; Kim, Soowhan

2012-04-01

The proton conducting polymer composite membranes are of technological interest in many energy devices such as fuel cells and redox flow batteries. In particular, the polymer composite membranes such as SiO2 incorporated Nafion membranes are recently reported as highly promising for the redox flow batteries. However, there is conflicting reports regarding the performance of this Nafion-SiO2 composite membrane in the redox flow cell. This paper presents results of the analysis of the Nafion-SiO2 composite membrane used in a vanadium redox flow battery by nuclear magnetic resonance (NMR) spectroscopy, X-ray photoelectron spectroscopy (XPS), Fourier Transformed Infra Red (FTIR) spectroscopy, and ultravioletmore » visible spectroscopy. The XPS study reveals the chemical identity and environment of vanadium cations accumulated at the surface. On the other hand, the 19F and 29Si NMR measurement explores the nature of the interaction between the silica particles, Nafion side chains and diffused vanadium cations. The 29Si NMR shows that the silica particles interaction via hydrogen bonds to the sulfonic groups of Nafion and diffused vanadium cations. Based on these spectroscopic studies, the chemical environment of the silica particles inside the Nafion membrane and their interaction with diffusing vanadium cations during flow cell operations are discussed. This study discusses the origin of performance degradation of the Nafion-SiO2 composite membrane materials in vanadium redox flow batteries.« less

Proton conductive montmorillonite-Nafion composite membranes for direct ethanol fuel cells

NASA Astrophysics Data System (ADS)

Wu, Xiu-Wen; Wu, Nan; Shi, Chun-Qing; Zheng, Zhi-Yuan; Qi, Hong-Bin; Wang, Ya-Fang

2016-12-01

The preparation of Nafion membranes modified with montmorillonites is less studied, and most relative works mainly applied in direct methanol fuel cells, less in direct ethanol fuel cells. Organic/inorganic composite membranes are prepared with different montmorillonites (Ca-montmorillonite, Na-montmorillonite, K-montmorillonite, Mg-montmorillonite, and H-montmorillonite) and Nafion solution via casting method at 293 K in air, and with balance of their proton conductivity and ethanol permeability. The ethanol permeability and proton conductivity of the membranes are comparatively studied. The montmorillonites can well decrease the ethanol permeability of the membranes via inserted them in the membranes, while less decrease the proton conductivities of the membranes depending on the inserted amount and type of montmorillonites. The proton conductivities of the membranes are between 36.0 mS/cm and 38.5 mS/cm. The ethanol permeability of the membranes is between 0.69 × 10-6 cm2/s and 2.67 × 10-6 cm2/s.

Effectively suppressing vanadium permeation in vanadium redox flow battery application with modified Nafion membrane with nacre-like nanoarchitectures

NASA Astrophysics Data System (ADS)

Zhang, Lesi; Ling, Ling; Xiao, Min; Han, Dongmei; Wang, Shuanjin; Meng, Yuezhong

2017-06-01

A novel self-assembled composite membrane, Nafion-[PDDA/ZrP]n with nacre-like nanostructures was successfully fabricated by a layer-by-layer (LbL) method and used as proton exchange membrane for vanadium redox flow battery applications. Poly(diallyldimethylammonium chloride) (PDDA) with positive charges and zirconium phosphate (ZrP) nanosheets with negative charges can form ultra-thin nacre-like nanostructure on the surface of Nafion membrane via the ionic crosslinking of tightly folded macromolecules. The lamellar structure of ZrP nanosheets and Donnan exclusion effect of PDDA can greatly decrease the vanadium ion permeability and improve the selectivity of proton conductivity. The fabricated Nafion-[PDDA/ZrP]4 membrane shows two orders of magnitude lower vanadium ion permeability (1.05 × 10-6 cm2 min-1) and 12 times higher ion selectivity than those of pristine Nafion membrane at room temperature. Consequently, the performance of vanadium redox flow batteries (VRFBs) assembled with Nafion-[PDDA/ZrP]3 membrane achieved a highly coulombic efficiency (CE) and energy efficiency (EE) together with a very slow self-discharge rate. When comparing with pristine Nafion VRFB, the CE and EE values of Nafion-[PDDA/ZrP]3 VRFB are 10% and 7% higher at 30 mA cm-2, respectively.

Processing and Pretreatment Effects on Vanadium Transport in Nafion Membranes

DOE PAGES

Xie, Wei; Darling, Robert M.; Perry, Mike L.

2015-10-13

Here, this work describes how manufacturing processes and pretreatments affect the proton conductivity and vanadyl permeability of Nafion® and how these properties are altered by running in a cell. Five Nafion membranes were examined: reinforced XL100, dispersion cast NR211 and NR212, and extruded N115 and N117. The membranes were subjected to pretreatments that included annealing at 120°C and immersing in ambient temperature and boiling water and sulfuric acid. Vanadyl permeability varied by ~15X with pretreatment and ~3X with manufacturing process. Variations in ionic conductivity were comparatively modest: ~1.5X with pretreatment and ~1.2X with processing. Differences in permeability can be eliminatedmore » by annealing the extruded membranes above their glass-transition temperature or by immersing in boiling sulfuric acid. The differences induced by processing and pretreatments were largely absent from membranes removed from vanadium redox cells subjected to repeated charge/discharge cycles.« less

Novel Composite Proton Exchange Membrane with Connected Long-Range Ionic Nanochannels Constructed via Exfoliated Nafion-Boron Nitride Nanocomposite.

PubMed

Jia, Wei; Tang, Beibei; Wu, Peiyi

2017-05-03

Nafion-boron nitride (NBN) nanocomposites with a Nafion-functionalized periphery are prepared via a convenient and ecofriendly Nafion-assisted water-phase exfoliation method. Nafion and the boron nitride nanosheet present strong interactions in the NBN nanocomposite. Then the NBN nanocomposites were blended with Nafion to prepare NBN Nafion composite proton exchange membranes (PEMs). NBN nanocomposites show good dispersibility and have a noticeable impact on the aggregation structure of the Nafion matrix. Connected long-range ionic nanochannels containing exaggerated (-SO 3 - ) n ionic clusters are constructed during the membrane-forming process via the hydrophilic and H-bonding interactions between NBN nanocomposites and Nafion matrix. The addition of NBN nanocomposites with sulfonic groups also provides additional proton transportation spots and enhances the water uptake of the composite PEMs. The proton conductivity of the NBN Nafion composite PEMs is significantly increased under various conditions relative to that of recast Nafion. At 80 °C-95% relative humidity, the proton conductivity of 0.5 NBN Nafion is 0.33 S·cm -1 , 6 times that of recast Nafion under the same conditions.

In-situ measurement of electroosmotic drag coefficient in Nafion membrane for the PEMFC.

PubMed

Peng, Zhe; Morin, Arnaud; Huguet, Patrice; Schott, Pascal; Pauchet, Joël

2011-11-10

A new method based on hydrogen pump has been developed to measure the electroosmotic drag coefficient in representative PEMFC operating conditions. It allows eliminating the back-flow of water which leads to some errors in the calculation of this coefficient with previously reported electrochemical methods. Measurements have been performed on 50 μm thick Nafion membranes both extruded and recast. Contrary to what has been described in most of previous published works, the electroosmotic drag coefficient decreases as the membrane water content increases. The same trend is observed for temperatures between 25 and 80 °C. For the same membrane water content, the electroosmotic drag coefficient increases with temperature. In the same condition, there is no difference in drag coefficient for extruded Nafion N112 and recast Nafion NRE212. These results are discussed on the basis of the two commonly accepted proton transport mechanisms, namely, Grotthus and vehicular.

Facilitating Proton Transport in Nafion-Based Membranes at Low Humidity by Incorporating Multifunctional Graphene Oxide Nanosheets.

PubMed

He, Xueyi; He, Guangwei; Zhao, Anqi; Wang, Fei; Mao, Xunli; Yin, Yongheng; Cao, Li; Zhang, Bei; Wu, Hong; Jiang, Zhongyi

2017-08-23

Nafion, as a state-of-the-art solid electrolyte for proton exchange membrane fuel cells (PEMFCs), suffers from drastic decline in proton conductivity with decreasing humidity, which significantly restricts the efficient and stable operation of the fuel cell system. In this study, the proton conductivity of Nafion at low relative humidity (RH) was remarkably enhanced by incorporating multifunctional graphene oxide (GO) nanosheets as multifunctional fillers. Through surface-initiated atom transfer radical polymerization of sulfopropyl methacrylate (SPM) and poly(ethylene glycol) methyl ether methacrylate, the copolymer-grafted GO was synthesized and incorporated into the Nafion matrix, generating efficient paths at the Nafion-GO interface for proton conduction. The Lewis basic oxygen atoms of ethylene oxide (EO) units and sulfonated acid groups of SPM monomers served as additional proton binding and release sites to facilitate the proton hopping through the membrane. Meanwhile, the hygroscopic EO units enhanced the water retention property of the composite membrane, conferring a dramatic increase in proton conductivity under low humidity. With 1 wt % filler loading, the composite membrane displayed the highest proton conductivity of 2.98 × 10 -2 S cm -1 at 80 °C and 40% RH, which was 10 times higher than that of recast Nafion. Meanwhile, the Nafion composite exhibited a 135.5% increase in peak power density at 60 °C and 50% RH, indicating its great application potential in PEMFCs.

Bacterial nanocellulose/Nafion composite membranes for low temperature polymer electrolyte fuel cells

NASA Astrophysics Data System (ADS)

Jiang, Gao-peng; Zhang, Jing; Qiao, Jin-li; Jiang, Yong-ming; Zarrin, Hadis; Chen, Zhongwei; Hong, Feng

2015-01-01

Novel nanocomposite membranes aimed for both proton-exchange membrane fuel cell (PEMFC) and direct methanol fuel cell (DMFC) are presented in this work. The membranes are based on blending bacterial nanocellulose pulp and Nafion (abbreviated as BxNy, where x and y indicates the mass ratio of bacterial cellulose to Nafion). The structure and properties of BxNy membranes are characterized by FTIR, SEM, TG, DMA and EIS, along with water uptake, swelling behavior and methanol permeability tests. It is found that the BxNy composite membranes with reinforced concrete-like structure show excellent mechanical and thermal stability regardless of annealing. The water uptake plus area and volume swelling ratios are all decreased compared to Nafion membranes. The proton conductivities of pristine and annealed B1N9 are 0.071 and 0.056 S cm-1, respectively, at 30 °C and 100% humidity. Specifically, annealed B1N1 exhibited the lowest methanol permeability of 7.21 × 10-7 cm2 s-1. Through the selectivity analysis, pristine and annealed B1N7 are selected to assemble the MEAs. The performances of annealed B1N7 in PEMFC and DMFC show the maximum power densities of 106 and 3.2 mW cm-2, respectively, which are much higher than those of pristine B1N7 at 25 °C. The performances of the pristine and annealed B1N7 reach a level as high as 21.1 and 20.4 mW cm-2 at 80 °C in DMFC, respectively.

Ultrasonic-assisted synthesis of ZrO2 nanoparticles and their application to improve the chemical stability of Nafion membrane in proton exchange membrane (PEM) fuel cells.

PubMed

Taghizadeh, Mohammad Taghi; Vatanparast, Morteza

2016-12-01

Zirconium dioxide (ZrO2) nanoparticles were fabricated successfully via ultrasonic-assisted method using ZrO(NO3)2·H2O, ethylenediamine and hydrazine as precursors in aqueous solution. Morphology, structure and composition of the obtained products were characterized by means of X-ray diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), dynamic light scattering (DLS), Fourier transform infrared spectroscopy (FT-IR) and diffuse reflectance spectroscopy (DRS). Then, the synthesized nanoparticles were used to prepare Nafion/ZrO2 nanocomposite membranes. The properties of the membranes were studied by ion exchange capacity (IEC) proton conductivity (σ), thermal stability and water uptake measurements. The ex-situ Fenton's test was used to investigate the chemical stability of the membranes. From our results, compared with Nafion membrane, the nanocomposite membrane exhibited lower fluoride release and weight loss. Therefore, it can concluded that Nafion/ZrO2 nanocomposite exhibit more chemical stability than the pure Nafion membrane. ATR-FTIR spectra and SEM surface images of membranes also confirm these results. Copyright © 2016 Elsevier Inc. All rights reserved.

Property Enhancement Effects of Side-Chain-Type Naphthalene-Based Sulfonated Poly(arylene ether ketone) on Nafion Composite Membranes for Direct Methanol Fuel Cells.

PubMed

Wang, Baolong; Hong, Lihua; Li, Yunfeng; Zhao, Liang; Zhao, Chengji; Na, Hui

2017-09-20

Nafion/SNPAEK-x composite membranes were prepared by blending raw Nafion and synthesized side-chain-type naphthalene-based sulfonated poly(arylene ether ketone) with a sulfonation degree of 1.35 (SNPAEK-1.35). The incorporation of SNPAEK-1.35 polymer with ion exchange capacity (IEC) of 2.01 mequiv·g -1 into a Nafion matrix has the property enhancement effects, such as increasing IECs, improving proton conductivity, enhancing mechanical properties, reducing methanol crossover, and improving single cell performance of Nafion. Morphology studies show that Nafion/SNPAEK-x composite membranes exhibit a well-defined microphase separation structure depending on the contents of SNPAEK-1.35 polymer. Among them, Nafion/SNPAEK-7.5% with a bicontinuous morphology exhibits the best comprehensive properties. For example, it shows the highest proton conductivities of 0.092 S cm -1 at 25 °C and 0.163 S cm -1 at 80 °C, which are higher than those of recast Nafion with 0.073 S cm -1 at 25 °C and 0.133 S cm -1 at 80 °C, respectively. Nafion/SNPAEK-5.0% and Nafion/SNPAEK-7.5% membranes display an open circuit voltage of 0.77 V and a maximum power density of 47 mW cm -2 at 80 °C, which are much higher than those of recast Nafion of 0.63 V and 24 mW cm -2 under the same conditions. Nafion/SNPAEK-5.0% membrane also has comparable tensile strength (12.7 MPa) to recast Nafion (13.7 MPa), and higher Young's modulus (330 MPa) than that of recast Nafion (240 MPa). By combining their high proton conductivities, comparable mechanical properties, and good single cell performance, Nafion/SNPAEK-x composite membranes have the potential to be polymer electrolyte materials for direct methanol fuel cell applications.

Influence of aminosilane precursor concentration on physicochemical properties of composite Nafion membranes for vanadium redox flow battery applications

NASA Astrophysics Data System (ADS)

Kondratenko, Mikhail S.; Karpushkin, Evgeny A.; Gvozdik, Nataliya A.; Gallyamov, Marat O.; Stevenson, Keith J.; Sergeyev, Vladimir G.

2017-02-01

A series of composite proton-exchange membranes have been prepared via sol-gel modification of commercial Nafion membranes with [N-(2-aminoethyl)-3-aminopropyl]trimethoxysilane. The structure and physico-chemical properties (water uptake, ion-exchange capacity, vanadyl ion permeability, and proton conductivity) of the prepared composite membranes have been studied as a function of the precursor loading (degree of the membrane modification). If the amount of the precursor is below 0.4/1 M ratio of the amino groups of the precursor to the sulfonic groups of Nafion, the composite membranes exhibit decreased vanadium ion permeability while having relatively high proton conductivity. With respect to the use of a non-modified Nafion membrane, the performance of the composite membrane with an optimum precursor loading in a single-cell vanadium redox flow battery demonstrates enhanced energy efficiency in 20-80 mA cm-2 current density range. The maximum efficiency increase of 8% is observed at low current densities.

Physics of transduction in ionic liquid-swollen Nafion membranes

NASA Astrophysics Data System (ADS)

Bennett, Matthew; Leo, Donald

2006-03-01

Ionic polymer transducers are a class of electroactive polymers that are able to generate large strains (1-5%) in response to low voltage inputs (1-5 V). Additionally, these materials generate electrical charge in response to mechanical strain and are therefore able to operate as soft, distributed sensors. Traditionally, ionic polymer transducers have been limited in their application by their hydration dependence. This work seeks to overcome this limitation by replacing the water with an ionic liquid. Ionic liquids are molten salts that exhibit very high thermal and electrochemical stability while also possessing high ionic conductivity. Results have shown that an ionic liquid-swollen ionic polymer transducer can operate for more than 250,000 cycles in air as compared to about 2,000 cycles for a water-swollen transducer. The current work examines the mechanisms of transduction in ionic liquid-swollen transducers based on Nafion polymer membranes. Specifically, the morphology and relevant ion associations within these membranes are investigated by the use of small-angle X-ray scattering (SAXS), Fourier transform infrared spectroscopy (FTIR), and nuclear magnetic resonance spectroscopy (NMR). These results reveal that the ionic liquid interacts with the membrane in much the same way that water does, and that the counterions of the Nafion polymer are the primary charge carriers. The results of these analyses are compared to the macroscopic transduction behavior in order to develop a model of the charge transport mechanism responsible for electromechanical coupling in these membranes.

Enhanced proton conductivity of Nafion hybrid membrane under different humidities by incorporating metal-organic frameworks with high phytic acid loading.

PubMed

Li, Zhen; He, Guangwei; Zhang, Bei; Cao, Ying; Wu, Hong; Jiang, Zhongyi; Tiantian, Zhou

2014-06-25

In this study, phytic acid (myo-inositol hexaphosphonic acid) was first immobilized by MIL101 via vacuum-assisted impregnation method. The obtained phytic@MIL101 was then utilized as a novel filler to incorporate into Nafion to fabricate hybrid proton exchange membrane for application in PEMFC under different relative humidities (RHs), especially under low RHs. High loading and uniform dispersion of phytic acid in MIL 101(Cr) were achieved as demonstrated by ICP, FT-IR, XPS, and EDS-mapping. The phytic@MIL101 was dispersed homogeneously in the Nafion matrix when the filler content was less than 12%. Hybrid membranes were evaluated by proton conductivity, mechanical property, thermal stability, and so forth. Remarkably, the Nafion/phytic@MIL hybrid membranes showed high proton conductivity at different RHs, especially under low RHs, which was up to 0.0608 S cm(-1) and 7.63 × 10(-4) S cm(-1) at 57.4% RH and 10.5% RH (2.8 and 11.0 times higher than that of pristine membrane), respectively. Moreover, the mechanical property of Nafion/phtic@MIL hybrid membranes was substantially enhanced and the thermal stability of membranes was well preserved.

Comparative Experimental Study on Ionic Polymer Mental Composite based on Nafion and Aquivion Membrane as Actuators

NASA Astrophysics Data System (ADS)

Luo, B.; Chen, Z.

2017-11-01

Most ionic polymer mental composites employ Nafion as the polymer matrix, Aquivion can also manufactured as ionic polymer mental composite while research was little. This paper researched on two kinds of ionic polymer mental composite based on Aquivion and Nafion matrix with palladium electrode called Aquivion-IPMC and Nafion-IPMC. The samples were fabricated by the same preparation process. The current and deformation responses of the samples were measured at voltage to characterize the mechano-electrical properties. The experimental observations revealed that shorter flexible side chains in Aquivion-IPMC provide a larger force than Nafion-IPMC, while the displacement properties were similar in two different samples. The results also showed that Aquivion membrane can also replace Nafion to reproduce IPMC application in soft robots, MEMS, and so on.

Enhanced proton conductivity of Nafion composite membrane by incorporating phosphoric acid-loaded covalent organic framework

NASA Astrophysics Data System (ADS)

Yin, Yongheng; Li, Zhen; Yang, Xin; Cao, Li; Wang, Chongbin; Zhang, Bei; Wu, Hong; Jiang, Zhongyi

2016-11-01

Design and fabrication of efficient proton transport channels within solid electrolytes is crucial and challenging to new energy-relevant devices such as proton exchange membrane fuel cells (PEMFCs). In this study, the phosphoric acid (H3PO4) molecules are impregnated into SNW-1-type covalent organic frameworks (COFs) via vacuum assisted method. High loading of H3PO4 in SNW-1 and low guest leaching rate are achieved due to the similar diameter between H3PO4 and micropores in SNW-1. Then the COF-based composite membranes are fabricated for the first time with impregnated COFs (H3PO4@SNW-1) and Nafion matrix. For the composite membranes, the acid-base pairs formed between H3PO4@SNW-1 networks and Nafion optimize the interfacial interactions and hydrophilic domains. The acidic -PO3H2 groups in pores of H3PO4@SNW-1 provide abundant proton transfer sites. As a result, the continuous proton transfer channels with low energy barrier are created. At the filler content of 15 wt%, the composite membrane exhibits a superior proton conductivity of 0.0604 S cm-1 at 51% relative humidity and 80 °C. At the same time, the maximum power density of single fuel cell is 60.3% higher than that of the recast Nafion membrane.

A flexible all-inorganic fuel cell membrane with conductivity above Nafion, and durable operation at 150 °C

NASA Astrophysics Data System (ADS)

Ansari, Y.; Tucker, T. G.; Huang, W.; Klein, I. S.; Lee, S.-Y.; Yarger, J. L.; Angell, C. A.

2016-01-01

The search for fuel cell membranes has focused on carbon backbone polymers, among which Nafion seems to best survive the most severe of the degradation mechanisms - attack by peroxide radicals. Less attention has been given to inorganic membranes because of their generally inflexible nature and lower conductivity, though some SiO2-Nafion composites have shown improved properties. Nafion dominates, despite needing hydration, which then restricts operation to below 100 °C (so CO poisoning problems persist). Described herein is a low cost, flexible, and all-inorganic fiberglass reinforced gel membrane with conductivity exceeding that of Nafion at any temperature above 60 °C. Using Teflon fuel cells, maximum currents > 1 Acm-2 and OCV of 1.03 V at 150 °C are demonstrated. No detectable loss of cell potential was observed over 24 h during 50 mAcm-2 constant current operation at 120 °C while, at 150 °C and maximum power, the degradation rate is intermediate among other high conductivity H3PO4-PBI type membranes. The structure of the membrane is deduced, mainly from 29Si solid state-NMR. The -115 ppm resonance, which is extreme for Q4 Si(O) structures, identifies a zeolite-like SiO2 network, which is ;floppy;. 31P and 1H NMR establish nano-permeating H3PO4 as the source of the exceptional conductivity.

Performance evaluation of microbial electrochemical systems operated with Nafion and supported ionic liquid membranes.

PubMed

Koók, László; Nemestóthy, Nándor; Bakonyi, Péter; Zhen, Guangyin; Kumar, Gopalakrishnan; Lu, Xueqin; Su, Lianghu; Saratale, Ganesh Dattatraya; Kim, Sang-Hyoun; Gubicza, László

2017-05-01

In this work, the performance of dual-chamber microbial fuel cells (MFCs) constructed either with commonly used Nafion ® proton exchange membrane or supported ionic liquid membranes (SILMs) was assessed. The behavior of MFCs was followed and analyzed by taking the polarization curves and besides, their efficiency was characterized by measuring the electricity generation using various substrates such as acetate and glucose. By using the SILMs containing either [C 6 mim][PF 6 ] or [Bmim][NTf 2 ] ionic liquids, the energy production of these MFCs from glucose was comparable to that obtained with the MFC employing polymeric Nafion ® and the same substrate. Furthermore, the MFC operated with [Bmim][NTf 2 ]-based SILM demonstrated higher energy yield in case of low acetate loading (80.1 J g -1 COD in m -2  h -1 ) than the one with the polymeric Nafion ® N115 (59 J g -1 COD in m -2  h -1 ). Significant difference was observed between the two SILM-MFCs, however, the characteristics of the system was similar based on the cell polarization measurements. The results suggest that membrane-engineering applying ionic liquids can be an interesting subject field for bioelectrochemical system research. Copyright © 2017 Elsevier Ltd. All rights reserved.

Water Dynamics in Nafion Fuel Cell Membranes: the Effects of Confinement and Structural Changes on the Hydrogen Bond Network

PubMed Central

Moilanen, David E.; Piletic, Ivan R.; Fayer, Michael D.

2008-01-01

The complex environments experienced by water molecules in the hydrophilic channels of Nafion membranes are studied by ultrafast infrared pump-probe spectroscopy. A wavelength dependent study of the vibrational lifetime of the O-D stretch of dilute HOD in H2O confined in Nafion membranes provides evidence of two distinct ensembles of water molecules. While only two ensembles are present at each level of membrane hydration studied, the characteristics of the two ensembles change as the water content of the membrane changes. Time dependent anisotropy measurements show that the orientational motions of water molecules in Nafion membranes are significantly slower than in bulk water and that lower hydration levels result in slower orientational relaxation. Initial wavelength dependent results for the anisotropy show no clear variation in the time scale for orientational motion across a broad range of frequencies. The anisotropy decay is analyzed using a model based on restricted orientational diffusion within a hydrogen bond configuration followed by total reorientation through jump diffusion. PMID:18728757

Large-scale atomistic and quantum-mechanical simulations of a Nafion membrane: Morphology, proton solvation and charge transport.

PubMed

Komarov, Pavel V; Khalatur, Pavel G; Khokhlov, Alexei R

2013-01-01

Atomistic and first-principles molecular dynamics simulations are employed to investigate the structure formation in a hydrated Nafion membrane and the solvation and transport of protons in the water channel of the membrane. For the water/Nafion systems containing more than 4 million atoms, it is found that the observed microphase-segregated morphology can be classified as bicontinuous: both majority (hydrophobic) and minority (hydrophilic) subphases are 3D continuous and organized in an irregular ordered pattern, which is largely similar to that known for a bicontinuous double-diamond structure. The characteristic size of the connected hydrophilic channels is about 25-50 Å, depending on the water content. A thermodynamic decomposition of the potential of mean force and the calculated spectral densities of the hindered translational motions of cations reveal that ion association observed with decreasing temperature is largely an entropic effect related to the loss of low-frequency modes. Based on the results from the atomistic simulation of the morphology of Nafion, we developed a realistic model of ion-conducting hydrophilic channel within the Nafion membrane and studied it with quantum molecular dynamics. The extensive 120 ps-long density functional theory (DFT)-based simulations of charge migration in the 1200-atom model of the nanochannel consisting of Nafion chains and water molecules allowed us to observe the bimodality of the van Hove autocorrelation function, which provides the direct evidence of the Grotthuss bond-exchange (hopping) mechanism as a significant contributor to the proton conductivity.

Large-scale atomistic and quantum-mechanical simulations of a Nafion membrane: Morphology, proton solvation and charge transport

PubMed Central

Komarov, Pavel V; Khokhlov, Alexei R

2013-01-01

Summary Atomistic and first-principles molecular dynamics simulations are employed to investigate the structure formation in a hydrated Nafion membrane and the solvation and transport of protons in the water channel of the membrane. For the water/Nafion systems containing more than 4 million atoms, it is found that the observed microphase-segregated morphology can be classified as bicontinuous: both majority (hydrophobic) and minority (hydrophilic) subphases are 3D continuous and organized in an irregular ordered pattern, which is largely similar to that known for a bicontinuous double-diamond structure. The characteristic size of the connected hydrophilic channels is about 25–50 Å, depending on the water content. A thermodynamic decomposition of the potential of mean force and the calculated spectral densities of the hindered translational motions of cations reveal that ion association observed with decreasing temperature is largely an entropic effect related to the loss of low-frequency modes. Based on the results from the atomistic simulation of the morphology of Nafion, we developed a realistic model of ion-conducting hydrophilic channel within the Nafion membrane and studied it with quantum molecular dynamics. The extensive 120 ps-long density functional theory (DFT)-based simulations of charge migration in the 1200-atom model of the nanochannel consisting of Nafion chains and water molecules allowed us to observe the bimodality of the van Hove autocorrelation function, which provides the direct evidence of the Grotthuss bond-exchange (hopping) mechanism as a significant contributor to the proton conductivity. PMID:24205452

Characterization of the thermolysis products of Nafion membrane: A potential source of perfluorinated compounds in the environment

NASA Astrophysics Data System (ADS)

Feng, Mingbao; Qu, Ruijuan; Wei, Zhongbo; Wang, Liansheng; Sun, Ping; Wang, Zunyao

2015-05-01

The thermal decomposition of Nafion N117 membrane, a typical perfluorosulfonic acid membrane that is widely used in various chemical technologies, was investigated in this study. Structural identification of thermolysis products in water and methanol was performed using liquid chromatography-electrospray ionization-tandem mass spectrometry (LC/ESI-MS/MS). The fluoride release was studied using an ion-chromatography system, and the membrane thermal stability was characterized by thermogravimetric analysis. Notably, several types of perfluorinated compounds (PFCs) including perfluorocarboxylic acids were detected and identified. Based on these data, a thermolysis mechanism was proposed involving cleavage of both the polymer backbone and its side chains by attack of radical species. This is the first systematic report on the thermolysis products of Nafion by simulating its high-temperature operation and disposal process via incineration. The results of this study indicate that Nafion is a potential environmental source of PFCs, which have attracted growing interest and concern in recent years. Additionally, this study provides an analytical justification of the LC/ESI-MS/MS method for characterizing the degradation products of polymer electrolyte membranes. These identifications can substantially facilitate an understanding of their decomposition mechanisms and offer insight into the proper utilization and effective management on these membranes.

A combined theoretical-experimental study of interactions between vanadium ions and Nafion membrane in all-vanadium redox flow batteries

NASA Astrophysics Data System (ADS)

Intan, Nadia N.; Klyukin, Konstantin; Zimudzi, Tawanda J.; Hickner, Michael A.; Alexandrov, Vitaly

2018-01-01

Vanadium redox flow batteries (VRFBs) are a promising solution for large-scale energy storage, but a number of problems still impede the deployment of long-lifetime VRFBs. One important aspect of efficient operation of VRFBs is understanding interactions between vanadium species and the membrane. Herein, we investigate the interactions between all four vanadium cations and Nafion membrane by a combination of infrared (IR) spectroscopy and density-functional-theory (DFT)-based static and molecular dynamics simulations. It is observed that vanadium species primarily lead to changes in the IR spectrum of Nafion in the SO3- spectral region which is attributed to the interaction between vanadium species and the SO3- exchange sites. DFT calculations of vanadium -Nafion complexes in the gas phase show that it is thermodynamically favorable for all vanadium cations to bind to SO3- via a contact pair mechanism. Car-Parrinello molecular dynamics-based metadynamics simulations of cation-Nafion systems in aqueous solution suggest that V2+ and V3+ species coordinate spontaneously to SO3-, which is not the case for VO2+ and VO2+ . The interaction behavior of the uncycled membrane determined in this study is used to explain the experimentally observed changes in the vibrational spectra, and is discussed in light of previous results on device-cycled membranes.

Dynamics of Nafion membrane swelling in H2O/D2O mixtures as studied using FTIR technique

NASA Astrophysics Data System (ADS)

Bunkin, Nikolai F.; Kozlov, Valeriy A.; Shkirin, Alexey V.; Ninham, Barry W.; Balashov, Anatoliy A.; Gudkov, Sergey V.

2018-03-01

Experiments with Fourier transform spectrometry of Nafion, a water-swollen polymeric membrane, are described. The transmittance spectra of liquid samples and Nafion, soaked in these samples, were studied, depending on the deuterium content in water in the spectral range 1.8-2.15 μm. The experiments were carried out using two protocols: in the first protocol we studied the dynamics of Nafion swelling in H2O + D2O mixtures for the deuterium concentrations 3 < C < 104 ppm, and in the second protocol we studied the dynamics of swelling in pure heavy water (C = 106 ppm). For liquid mixtures in the concentration range 3 < C < 104 ppm, the transmittance spectra are the same, but for Nafion soaked in these fluids, the corresponding spectra are different. It is shown that, in the range of deuterium contents C = 90-500 ppm, the behavior of transmittance of the polymer membrane is non-monotonic. In experiments using the second protocol, the dynamics of diffusion replacement of residual water, which is always present in the bulk of the polymer membrane inside closed cavities (i.e., without access to atmospheric air), were studied. The experimentally estimated diffusion coefficient for this process is ≈6.10-11 cm2/s.

Positron annihilation lifetime study of Nafion/titanium dioxide nano-composite membranes

NASA Astrophysics Data System (ADS)

Lei, M.; Wang, Y. J.; Liang, C.; Huang, K.; Ye, C. X.; Wang, W. J.; Jin, S. F.; Zhang, R.; Fan, D. Y.; Yang, H. J.; Wang, Y. G.

2014-01-01

Positron annihilation lifetime (PAL) technique is applied for investigation of size and number density of free volumes in Nafion/TiO2-nanoparticles composite membrane. The proton transporting ability is correlated with the properties of free volume inside the membrane. It is revealed that composite membrane with 5 wt% of TiO2 nano-fillers exhibits good electrochemical performance under reduced humidity and it can be saturated with water at relative humidity of 50%, under which ionic clusters and proton transporting channels are formed, indicating that composite membranes with 5 wt% of TiO2 nano-fillers are effective electrolyte for fuel cells operated at reduced humidification levels. The results suggest that PAL can be a powerful tool for elucidating the relationship between microstructure and ion transport in polymer electrolyte membranes.

Electrospun sulfonated poly(ether ketone) nanofibers as proton conductive reinforcement for durable Nafion composite membranes

NASA Astrophysics Data System (ADS)

Klose, Carolin; Breitwieser, Matthias; Vierrath, Severin; Klingele, Matthias; Cho, Hyeongrae; Büchler, Andreas; Kerres, Jochen; Thiele, Simon

2017-09-01

We show that the combination of direct membrane deposition with proton conductive nanofiber reinforcement yields highly durable and high power density fuel cells. Sulfonated poly(ether ketone) (SPEK) was directly electrospun onto gas diffusion electrodes and then filled with Nafion by inkjet-printing resulting in a 12 μm thin membrane. The ionic membrane resistance (30 mΩ*cm2) was well below that of a directly deposited membrane reinforced with chemically inert (PVDF-HFP) nanofibers (47 mΩ*cm2) of comparable thickness. The power density of the fuel cell with SPEK reinforced membrane (2.04 W/cm2) is 30% higher than that of the PVDF-HFP reinforced reference sample (1.57 W/cm2). During humidity cycling and open circuit voltage (OCV) hold, the SPEK reinforced Nafion membrane showed no measurable degradation in terms of H2 crossover current density, thus fulfilling the target of 2 mA/cm2 of the DOE after degradation. The chemical accelerated stress test (100 h OCV hold at 90 °C, 30% RH, H2/air, 50/50 kPa) revealed a degradation rate of about 0.8 mV/h for the fuel cell with SPEK reinforced membrane, compared to 1.0 mV/h for the PVDF-HFP reinforced membrane.

The effect of Nafion membrane thickness on performance of all tungsten-cobalt heteropoly acid redox flow battery

NASA Astrophysics Data System (ADS)

Liu, Yiyang; Wang, Haining; Xiang, Yan; Lu, Shanfu

2018-07-01

Recently, we have reported a new all tungsto-cobalt heteropoly acid redox flow battery (all H6[CoW12O40] RFB) with high coulombic efficiency. Because of the relatively large ion size and high negative charge, the tungsto-cobalt heteropoly acid anion is difficult to cross Nafion membrane, which makes it possible to employ thinner Nafion membrane in all H6[CoW12O40] RFB. In this study, three types of Nafion membranes with different thickness, namely, N212 (50 μm), N211 (25 μm), and N-17 (home-made, 17 μm) are used as polymer electrolyte to investigate its effects on the performance of all H6[CoW12O40] RFB. The ion permeability increases while the area specific resistanceas decreases as reducing the membrane thickness. As a result, the RFB with N211 membrane exhibits best comprehensive performance, which exhibites the energy efficiency of 88.6% at current density of 0.10 A cm-2 and the power density of 0.56 W cm-2 at 0.60 A cm-2. Moreover, the battery delivers impressive cycling performance of 100 cycles with an average coulombic efficiency of 99.4%, energy efficiency of 80.0%, and capacity retention of 99.98% per cycle at current density of 0.20 A cm-2.

Coulometric sodium chloride removal system with Nafion membrane for seawater sample treatment.

PubMed

Grygolowicz-Pawlak, Ewa; Sohail, Manzar; Pawlak, Marcin; Neel, Bastien; Shvarev, Alexey; de Marco, Roland; Bakker, Eric

2012-07-17

Seawater analysis is one of the most challenging in the field of environmental monitoring, mainly due to disparate concentration levels between the analyte and the salt matrix causing interferences in a variety of analytical techniques. We propose here a miniature electrochemical sample pretreatment system for a rapid removal of NaCl utilizing the coaxial arrangement of an electrode and a tubular Nafion membrane. Upon electrolysis, chloride is deposited at the Ag electrode as AgCl and the sodium counterions are transported across the membrane. This cell was found to work efficiently at potentials higher than 400 mV in both stationary and flow injection mode. Substantial residual currents observed during electrolysis were found to be a result of NaCl back diffusion from the outer side of the membrane due to insufficient permselectivity of the Nafion membrane. It was demonstrated that the residual current can be significantly reduced by adjusting the concentration of the outer solution. On the basis of ion chromatography results, it was found that the designed cell used in flow injection electrolysis mode reduced the NaCl concentration from 0.6 M to 3 mM. This attempt is very important in view of nutrient analysis in seawater where NaCl is a major interfering agent. We demonstrate that the pretreatment of artificial seawater samples does not reduce the content of nitrite or nitrate ions upon electrolysis. A simple diffusion/extraction steady state model is proposed for the optimization of the electrolysis cell characteristics.

Effect of cations (Na +, Ca 2+, Fe 3+) on the conductivity of a Nafion membrane

NASA Astrophysics Data System (ADS)

Hongsirikarn, Kitiya; Goodwin, James G.; Greenway, Scott; Creager, Stephen

It is known that trace amounts of cations have a detrimental effect on the liquid-phase conductivity of perfluorosulfonated membranes at room temperature. However, the conditions used were very different from typical fuel cell conditions. Recent research has shown the impact of conductivity measurement conditions on NH 4 + contaminated membranes. In this study, the impact of nonproton-containing cations (M n+ = Na +, Ca 2+, and Fe 3+) on Nafion membrane (N-211) conductivity was investigated both in deionized (DI) water at room temperature (∼25 °C) and in the gas phase at 80 °C under conditions similar to in a PEMFC. These conductivities were compared with those of Nafion membranes contaminated with NH 4 + ions. Under the same conditions, the conductivity of a metal cationic-contaminated membrane having the same proton composition (yH+m) was similar, but slightly lower than that of an NH 4 +-contaminated membrane. The conductivity in the purely H +-form of N-211 was more than 12 times greater than the M n+-form form at 25 °C in DI water. At 80 °C, the gas-phase conductivity was 6 times and 125 times greater at 100%RH and 30%RH, respectively. The quantitative results for conductivity and activation energy of contaminated membranes under typical fuel cell conditions are reported here for the first time.

Coarse-grained model of nanoscale segregation, water diffusion, and proton transport in Nafion membranes

NASA Astrophysics Data System (ADS)

Vishnyakov, Aleksey; Mao, Runfang; Lee, Ming-Tsung; Neimark, Alexander V.

2018-01-01

We present a coarse-grained model of the acid form of Nafion membrane that explicitly includes proton transport. This model is based on a soft-core bead representation of the polymer implemented into the dissipative particle dynamics (DPD) simulation framework. The proton is introduced as a separate charged bead that forms dissociable Morse bonds with water beads. Morse bond formation and breakup artificially mimics the Grotthuss hopping mechanism of proton transport. The proposed DPD model is parameterized to account for the specifics of the conformations and flexibility of the Nafion backbone and sidechains; it treats electrostatic interactions in the smeared charge approximation. The simulation results qualitatively, and in many respects quantitatively, predict the specifics of nanoscale segregation in the hydrated Nafion membrane into hydrophobic and hydrophilic subphases, water diffusion, and proton mobility. As the hydration level increases, the hydrophilic subphase exhibits a percolation transition from a collection of isolated water clusters to a 3D network of pores filled with water embedded in the hydrophobic matrix. The segregated morphology is characterized in terms of the pore size distribution with the average size growing with hydration from ˜1 to ˜4 nm. Comparison of the predicted water diffusivity with the experimental data taken from different sources shows good agreement at high and moderate hydration and substantial deviation at low hydration, around and below the percolation threshold. This discrepancy is attributed to the dynamic percolation effects of formation and rupture of merging bridges between the water clusters, which become progressively important at low hydration, when the coarse-grained model is unable to mimic the fine structure of water network that includes singe molecule bridges. Selected simulations of water diffusion are performed for the alkali metal substituted membrane which demonstrate the effects of the counter-ions on

Investigation of Free-Standing Plasmonic Mesoporous Ag/CMK-8-Nafion Composite Membrane for the Removal of Organic Pollutants with 254-nm UV Irradiation

NASA Astrophysics Data System (ADS)

Tseng, Chuan Ming; Chen, Hsin Liang; Lai, Sz Nian; Chen, Ming Shiung; Peng, Chien Jung; Li, Chia Jui; Hung, Wei Hsuan

2017-05-01

"Carbon-based material" has demonstrated a great potential on water purification due to its strong physical adsorption to organic pollutants in the water. Three-dimensional cubic ordered mesoporous carbon (CMK-8), one of the well-known ordered mesoporous carbons, was prepared by using nanocasting method with mesoporous silica (KIT-6) as the template. In this study, CMK-8 blended with Nafion polymer to form a free-standing mesoporous CMK-8-Nafion composite membrane. The synthesis of high crystallinity CMK-8 was characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM). More than 80% methyl orange (MO) removal efficiency was observed under 254-nm UV irradiation after 120 min. Ninety-two percent recycling performance was remained after four recycling tests, which indicated a reliable servicing lifetime for the water purification. Furthermore, an additional layer of plasmonic silver nanoparticles (Ag NPs) was integrated into this CMK-8-Nafion membrane for higher pollutant removal efficiency, attributing from the generation of plasmon-resonance hot electrons from Ag NPs. A 4-in. CMK-8-Nafion composite membrane was also fabricated for the demonstration of potential large-scale utilization.

The platinum microelectrode/Nafion interface - An electrochemical impedance spectroscopic analysis of oxygen reduction kinetics and Nafion characteristics

NASA Technical Reports Server (NTRS)

Parthasarathy, Arvind; Dave, Bhasker; Srinivasan, Supramaniam; Appleby, John A.; Martin, Charles R.

1992-01-01

The objectives of this study were to use electrochemical impedance spectroscopy (EIS) to study the oxygen-reduction reaction under lower humidification conditions than previously studied. The EIS technique permits the discrimination of electrode kinetics of oxygen reduction, mass transport of O2 in the membrane, and the electrical characteristics of the membrane. Electrode-kinetic parameters for the oxygen-reduction reaction, corrosion current densities for Pt, and double-layer capacitances were calculated. The production of water due to electrochemical reduction of oxygen greatly influenced the EIS response and the electrode kinetics at the Pt/Nafion interface. From the finite-length Warburg behavior, a measure of the diffusion coefficient of oxygen in Nafion and diffusion-layer thickness was obtained. An analysis of the EIS data in the high-frequency domain yielded membrane and interfacial characteristics such as ionic conductivity of the membrane, membrane grain-boundary capacitance and resistance, and uncompensated resistance.

Electrochemical performance and transport properties of a Nafion membrane in a hydrogen-bromine cell environment

NASA Technical Reports Server (NTRS)

Baldwin, Richard S.

1987-01-01

The overall energy conversion efficiency of a hydrogen-bromine energy storage system is highly dependent upon the characteristics and performance of the ion-exchange membrane utilized as a half-cell separator. The electrochemical performance and transport properties of a duPont Nafion membrane in an aqueous HBr-Br2 environment were investigated. Membrane conductivity data are presented as a function of HBr concentration and temperature for the determination of ohmic voltage losses across the membrane in an operational cell. Diffusion-controlled bromine permeation rates and permeabilities are presented as functions of solution composition and temperature. Relationships between the degree of membrane hydration and the membrane transport characteristics are discussed. The solution chemistry of an operational hydrogen-bromine cell undergoing charge from 45% HBr to 5% HBr is discussed, and, based upon the experimentally observed bromine permeation behavior, predicted cell coulombic losses due to bromine diffusion through the membrane are presented as a function of the cell state-of-charge.

Characterization of Polyester Cloth as an Alternative Separator to Nafion Membrane in Microbial Fuel Cells for Bioelectricity Generation Using Swine Wastewater.

PubMed

Kim, Taeyoung; Kang, Sukwon; Sung, Je Hoon; Kang, Youn Koo; Kim, Young Hwa; Jang, Jae Kyung

2016-12-28

Polyester cloth (PC) was selected as a prospective inexpensive substitute separator material for microbial fuel cells (MFCs). PC was compared with a traditional Nafion proton exchange membrane (PEM) as an MFC separator by analyzing its physical and electrochemical properties. A single layer of PC showed higher mass transfer ( e.g ., for O₂/H⁺/ions) than the Nafion PEM; in the case of oxygen mass transfer coefficient (k o ), a rate of 50.0 × 10⁻⁵ cm·s⁻¹ was observed compared with a rate of 20.8 × 10⁻⁵ cm/s in the Nafion PEM. Increased numbers of PC layers were found to reduce the oxygen mass transfer coefficient. In addition, the diffusion coefficient of oxygen (D O ) for PC (2.0-3.3 × 10⁻⁶ cm²/s) was lower than that of the Nafion PEM (3.8 × 10⁻⁶ cm²/s). The PC was found to have a low ohmic resistance (0.29-0.38 Ω) in the MFC, which was similar to that of Nafion PEM (0.31 Ω); this resulted in comparable maximum power density and maximum current density in MFCs with PC and those with Nafion PEMs. Moreover, a higher average current generation was observed in MFCs with PC (104.3 ± 15.3 A/m³) compared with MFCs with Nafion PEM (100.4 ± 17.7 A/m³), as well as showing insignificant degradation of the PC surface, during 177 days of use in swine wastewater. These results suggest that PC separators could serve as a low-cost alternative to Nafion PEMs for construction of cost-effective MFCs.

Lithiated Nafion as polymer electrolyte for solid-state lithium sulfur batteries using carbon-sulfur composite cathode

NASA Astrophysics Data System (ADS)

Gao, Jing; Sun, Chunshui; Xu, Lei; Chen, Jian; Wang, Chong; Guo, Decai; Chen, Hao

2018-04-01

Due to flexible property and light weight, the lithiated Nafion membrane swollen with PC (PC-Li-Nafion) has been employed as both solid-state electrolyte and separator to fabricate solid-state Li-S cells. The electrochemical measurements of PC-Li-Nafion membrane show that its Li-ion transference number is 0.928, ionic conductivity of 2.1 × 10-4 S cm-1 can be achieved at 70 °C and its electrochemical window is 0 ∼ +4.1 V vs. Li+/Li. It is observed that the Li dendrites are suppressed by using PC-Li-Nafion membrane due to its single-ion conducting property. The amounts of Li-Nafion resin binder and conductive carbon in the cathode are optimized as 40% and 10% respectively to make a balance of ionic and electronic conductivities. A thin-layer Li-Nafion resin with a thickness of around 2 μm is fabricated between the cathode and PC-Li-Nafion membrane to improve the interfacial contact and further enhance the specific capacity of the cell. When measured at 70 °C, the Li-S cell delivers a reversible specific capacity of 1072.8 mAh g-1 (S) at 0.05 C and 895 mAh g-1 (S) at 1 C. The capacity retention at 1 C is 89% after 100 cycles. These results suggest that high-performance solid-state Li-S cells can be fabricated with the Li-Nafion polymer electrolyte.

In situ nanostructure formation of (micro-hydroxo)bis(micro-carboxylato) diruthenium units in nafion membrane and its utilization for selective reduction of nitrosonium ion in aqueous medium.

PubMed

Kumar, Annamalai Senthil; Tanase, Tomoaki; Iida, Masayasu

2007-01-16

Nanostructured molecular film containing the (micro-hydroxo)bis(micro-carboxylato) diruthenium(III) units, [RuIII2(micro-OH)(micro-CH3COO)2(HBpz3)2]+ ({RuIII2(micro-OH)}), was prepared by an in situ conversion of its micro-oxo precursor, [RuIII2(micro-O)(micro-CH3COO)2(HBpz3)2] ({RuIII2(micro-O)}), in a Nafion membrane matrix, where HBpz3 is hydrotris(1-pyrazolyl)borate. The conversion procedure results in fine nanoparticle aggregates of the {RuIII2(micro-OH)} units in the Nafion membrane (Nf-{RuIII2(micro-OH)}), where an average particle size (4.1 +/- 2.3 nm) is close to the Nafion's cluster dimension of approximately 4 nm. Chemically modified electrodes by using the Nafion molecular membrane films (Nf-{RuIII2(micro-OH)}-MMFEs) were further developed on ITO/glass and glassy carbon electrode (GCE) surfaces, and a selective reduction of nitrosonium ion (NO+), presumably through reaction of a {RuIIRuIII(micro-OH)} mixed-valence state with HNO2, was demonstrated without interference by molecular oxygen in an acidic aqueous solution. The Nf-{RuIII2(micro-OH)}-MMFEs are stable even in a physiological condition (pH 7), where the naked {RuIII2(-OH)} complex is readily transformed into its deprotonated {RuIII2(micro-O)} form, demonstrating an unusual stabilizing effects for the {RuIII2(micro-OH)} unit by the Nafion cluster environment.

Oxygen permeation through Nafion 117 membrane and its impact on efficiency of polymer membrane ethanol fuel cell

NASA Astrophysics Data System (ADS)

Jablonski, Andrzej; Kulesza, Pawel J.; Lewera, Adam

2011-05-01

We investigate oxygen permeation through Nafion 117 membrane in a direct ethanol fuel cell and elucidate how it affects the fuel cell efficiency. An obvious symptom of oxygen permeation is the presence of significant amounts of acetaldehyde and acetic acid in the mixture leaving anode when no current was drawn from the fuel cell (i.e. under the open circuit conditions). This parasitic process severely lowers efficiency of the fuel cell because ethanol is found to be directly oxidized on the surface of catalyst by oxygen coming through membrane from cathode in the absence of electric current flowing in the external circuit. Three commonly used carbon-supported anode catalysts are investigated, Pt, Pt/Ru and Pt/Sn. Products of ethanol oxidation are determined qualitatively and quantitatively at open circuit as a function of temperature and pressure, and we aim at determining whether the oxygen permeation or the catalyst's activity limits the parasitic ethanol oxidation. Our results strongly imply the need to develop more selective membranes that would be less oxygen permeable.

Synthesis and characterization of diverse Pt nanostructures in Nafion.

PubMed

Ingle, N J C; Sode, A; Martens, I; Gyenge, E; Wilkinson, D P; Bizzotto, D

2014-02-25

With the aid of TEM characterization, we describe two distinct Pt nanostructures generated via the electroless reduction of Pt(NH3)4(NO2)2 within Nafion. Under one set of conditions, we produce bundles of Pt nanorods that are 2 nm in diameter and 10-20 nm long. These bundled Pt nanorods, uniformly distributed within 5 μm of the Nafion surface, are strikingly similar to the proposed hydrated nanomorphology of Nafion, and therefore strongly suggestive of Nafion templating. By altering the reaction environment (pH, reductant strength, and Nafion hydration), we can also generate nonregular polyhedron Pt nanoparticles that range in size from a few nanometers in diameter up to 20 nm. These Pt nanoparticles form a dense Pt layer within 100-200 nm from the Nafion surface and show a power-law dependence of particle size and distribution on the distance from the Nafion membrane surface. Control over the distribution and the type of Pt nanostructures in the surface region may provide a cost-effective, simple, and scaleable pathway for enhancing manufacturability, activity, stability, and utilization efficiency of Pt catalysts for electrochemical devices.

Miniaturised enzymatic conductometric biosensor with Nafion membrane for the direct determination of formaldehyde in water samples.

PubMed

Nguyen-Boisse, Thanh-Thuy; Saulnier, Joëlle; Jaffrezic-Renault, Nicole; Lagarde, Florence

2014-02-01

A new conductometric enzyme-based biosensor was developed for the determination of formaldehyde (FA) in aqueous solutions. The biosensor was prepared by cross-linking formaldehyde dehydrogenase from Pseudomonas putida with bovine serum albumin in saturated glutaraldehyde vapours (GA) at the surface of interdigitated gold microelectrodes. Nicotinamide adenine dinucleotide cofactor (NAD(+)) was added in solution at each measurement to maintain enzyme activity. Addition of a Nafion layer over the enzyme modified electrode resulted in a significant increase of biosensor signal due to enhanced accumulation of protons generated by enzymatic reaction at the electrode surface. Different parameters affecting enzyme activity or playing a role in ionic transfer through the Nafion membrane were optimised. In optimal conditions (0.045 mg enzyme, 30 min exposure to GA, 0.3 μL of a 1% (v/v) Nafion solution deposit, measurement in 5 mM phosphate buffer pH 7 containing 20 μM NAD(+)), the biosensor signal was linear up to 10 mM FA, and the detection limit was 18 μM. Relative standard deviations calculated from five consecutive replicates of FA solutions were lower than 5% in the 1-10 mM range. The biosensor was successfully applied to the determination of FA in spiked water samples (tap water and Rhone river water), with recoveries in the 95-110% range.

AC impedance investigations of proton conduction in Nafion(sup TM)

NASA Astrophysics Data System (ADS)

Cahan, B. D.; Wainright, J. S.

1993-12-01

AC impedance spectroscopy has been employed to study the conduction of protons in Nafion 117 polymer electrolyte membrane. Both two- and four-electrode geometries have been used to uniquely distinguish between the membrane impedance and the interfacial impedances. The results show that the impedance of Nafion for frequencies up to 100 kHz is characterized by a pure resistance, similar to conventional liquid electrolytes. The frequency dependent features observed using a two-electrode geometry are shown to be consistent will well-characterized interfacial impedances and do not arise from ionic conduction in the membrane. These results show that previous two-electrode studies reported in the literature have misinterpreted the impedance of the electrode interfaces as belonging to the conduction process in the electrolyte.

Conductivity Analysis of Membranes for High-Temperature PEMFC Applications

DOE Office of Scientific and Technical Information (OSTI.GOV)

Reed, R.; Turner, J.A.

2005-01-01

Low-temperature operation requirements for per-fluorinated membranes are one factor that limits the viability of current fuel cell technology for transportation and other uses. Because of this, high-temperature membrane materials are being researched. The protonic conductivity of organic/inorganic hybrid composites, Nafion® analog material, and heteropoly acid doped Nafion membranes were studied using a BekkTech® conductivity test cell as a hydrogen pump. The goal was to find a high-temperature membrane with sufficient enough conductive properties to replace the currently implemented low-temperature membranes, such as Nafion. Four-point conductivity measurements were taken using a hydrogen pump experiment. Results showed that one of the organic/inorganicmore » membranes that we tested had similar protonic conductivity to Nafion. Nafion analog membranes were shown to have similar to slightly better conductivity than Nafion at high-temperatures. However, like Nafion, performance dropped upon dehydration of the membrane at higher temperatures. Of the heteropoly acid doped Nafion membranes studied, silicotungstic acid was found to be, overall, the most promising for use as a dopant.« less

Mechanical properties and XRD of Nafion modified by 2-hydroxyethylammonium ionic liquids

NASA Astrophysics Data System (ADS)

Garaev, V.; Pavlovica, S.; Reinholds, I.; Vaivars, G.

2013-12-01

In this work, the Nafion 112 membrane impregnated with 2-hydroxyethylammonium carboxylate ionic liquids have been investigated. The used ionic liquids were 2-hydroxyethylammonium formate [HEA]F, acetate [HEA]A and lactate [HEA]L. Prepared composite membranes Nafion/ionic liquid are characterized by mechanical testing, such as tensile test and creep test. It is found that ionic liquids decrease elastic modulus and creep compliance, but do not have significant effect on the tensile strength. Also, composite membranes were studied by wide angle X-ray diffraction. All ionic liquids shift the peak maximum to the lower angle. In this work, only biodegradable ionic liquids were used for composite preparation.

Inducing microstructural changes in Nafion by incorporating graphitic carbon nitride to enhance the vanadium-blocking effect.

PubMed

Wu, Chunxiao; Lu, Shanfu; Zhang, Jin; Xiang, Yan

2018-03-14

Two-dimensional graphitic carbon nitride (g-C 3 N 4 ) nanosheets are introduced into a Nafion matrix to prepare a 'vanadium-blocking' recast Nafion membrane for vanadium redox flow battery (VRFB) applications. After 0.2 wt% g-C 3 N 4 nanosheets are incorporated, the vanadium ion permeability of the composite membrane decreases from 3.3 × 10 -7 cm 2 min -1 to 3.8 × 10 -9 cm 2 min -1 , which is a reduction of two orders of magnitude in comparison to the pristine recast Nafion membrane. This satisfactory result contributes to the physical blocking effect as well as the Donnan effect from the 2D morphology and functional amino groups of g-C 3 N 4 nanosheets. Notably, this work reveals that the g-C 3 N 4 nanosheets can help reinforce the vanadium-blocking effect by changing the microstructure of Nafion in addition to the well-known effects mentioned above. The g-C 3 N 4 nanosheets induce shrinkage in the original spherical structure of the ion cluster and generate a new lamellar structure. Correspondingly, the amorphous phase of Nafion is interrupted, and the membrane crystallinity is reduced. The VRFB with an optimized composite membrane achieves a high coulombic efficiency of 97% and an energy efficiency of 83% at a current density of 160 mA cm -2 . Meanwhile, the battery exhibited excellent lifetime stability during a 100 charge-discharge cycling test.

Synthesis of the diazonium (perfluoroalkyl) benzenesulfonimide monomer from Nafion monomer for proton exchange membrane fuel cells

NASA Astrophysics Data System (ADS)

Mei, Hua; D'Andrea, Dan; Nguyen, Tuyet-Trinh; Nworie, Chima

2014-02-01

One diazonium (perfluoroalkyl) benzenesulfonimide monomer, perfluoro-3, 6-dioxa-4-methyl-7-octene benzenesulfonyl imide, has been synthesized from Nafion monomer for the first time. With trifluorovinyl ether and diazonium precursors, the partially-fluorinated diazonium PFSI monomer can be polymerized and will provide chemically bonding with carbon electrode in proton exchange membrane fuel cells. A systematic study of the synthesis and characterization of this diazonium PFSI monomer has been conducted by varying reaction conditions. The optimized synthesis method has been established in the lab.

Magnetic resonance imaging of water content across the Nafion membrane in an operational PEM fuel cell.

PubMed

Zhang, Ziheng; Martin, Jonathan; Wu, Jinfeng; Wang, Haijiang; Promislow, Keith; Balcom, Bruce J

2008-08-01

Water management is critical to optimize the operation of polymer electrolyte membrane fuel cells. At present, numerical models are employed to guide water management in such fuel cells. Accurate measurements of water content variation in polymer electrolyte membrane fuel cells are required to validate these models and to optimize fuel cell behavior. We report a direct water content measurement across the Nafion membrane in an operational polymer electrolyte membrane fuel cell, employing double half k-space spin echo single point imaging techniques. The MRI measurements with T2 mapping were undertaken with a parallel plate resonator to avoid the effects of RF screening. The parallel plate resonator employs the electrodes inherent to the fuel cell to create a resonant circuit at RF frequencies for MR excitation and detection, while still operating as a conventional fuel cell at DC. Three stages of fuel cell operation were investigated: activation, operation and dehydration. Each profile was acquired in 6 min, with 6 microm nominal resolution and a SNR of better than 15.

Composite polymer membranes for proton exchange membrane fuel cells operating at elevated temperatures and reduced humidities

NASA Astrophysics Data System (ADS)

Zhang, Tao

Proton Exchange Membrane Fuel Cells (PEMFCs) are the leading candidate in the fuel cell technology due to the high power density, solid electrolyte, and low operational temperature. However, PEMFCs operating in the normal temperature range (60-80°C) face problems including poor carbon monoxide tolerance and heat rejection. The poisoning effect can be significantly relieved by operating the fuel cell at elevated temperature, which also improves the heat rejection and electrochemical kinetics. Low relative humidity (RH) operation is also desirable to simplify the reactant humidification system. However, at elevated temperatures, reduced RH PEMFC performance is seriously impaired due to irreversible water loss from presently employed state-of-the-art polymer membrane, Nafion. This thesis focuses on developing polymer electrolyte membranes with high water retention ability for operation in elevated temperature (110-150°C), reduced humidity (˜50%RH) PEMFCs. One approach is to alter Nafion by adding inorganic particles such as TiO2, SiO2, Zr(HPO 4)2, etc. While the presence of these materials in Nafion has proven beneficial, a reduction or no improvement in the PEMFC performance of Nafion/TiO2 and Nafion/Zr(HPO4)2 membranes is observed with reduced particle sizes or increased particle loadings in Nafion. It is concluded that the PEMFC performance enhancement associated with addition of these inorganic particles was not due to the particle hydrophilicity. Rather, the particle, partially located in the hydrophobic region of the membrane, benefits the cell performance by altering the membrane structure. Water transport properties of some Nafion composite membranes were investigated by NMR methods including pulsed field gradient spin echo diffusion, spin-lattice relaxation, and spectral measurements. Compared to unmodified Nafion, composite membranes materials exhibit longer longitudinal relaxation time constant T1. In addition to the Nafion material, sulfonated styrene

Nafion as Cosurfactant: Solubilization of Nafion in Water in the Presence of Pluronics

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kelarakis, Antonios; Giannelis, Emmanuel P.

2011-01-18

Incorporation of Nafion to aqueous solutions of Pluronics adversely impacts micellization due to extensive Nafion/copolymer interactions. Light scattering and zeta potential measurements provide evidence for the formation of sizable and stable Nafion/copolymer complexes, in expense of the neat copolymer micelles. At high copolymer concentrations, the overall interaction diagram of Nafion/copolymer reflects the competitive action of the release of packing constraints due to micellar destabilization induced by Nafion on one hand and the gelator nature of the Nafion on the other. Measurements using a quartz crystal microbalance (QCM-D) show that aqueous solutions of Pluronics (even at very low concentration) can dissolvemore » the Nafion coating on the crystal resonator, while typical low molecular weight ionic surfactants fail to induce similar effects. These studies demonstrate that complexation with this class of copolymers is a facile route to impart dispersibility to Nafion in aqueous environments that otherwise can be achieved through tedious and harsh treatments.« less

Highly Selective Ionic Block Copolymer Membranes

DTIC Science & Technology

2010-11-10

Multicomponent Diffusion and Sorption in an Ionic Polymer Membrane We recently measured the diffusion and sorption of methanol/water mixtures in Nafion (most...methanol feed concentration (17 M). Figure 1 shows one experiment where hydrated Nafion was exposed to a 2 M methanol/water liquid mixture resulting...copolymer membranes revealed several surprising results. Contrary to what has been observed in most ionic polymer membranes (e.g., Nafion ), the proton

Laccase-based biocathodes: Comparison of chitosan and Nafion.

PubMed

El Ichi-Ribault, S; Zebda, A; Laaroussi, A; Reverdy-Bruas, N; Chaussy, D; Belgacem, M N; Suherman, A L; Cinquin, P; Martin, D K

2016-09-21

Chitosan and Nafion(®) are both reported as interesting polymers to be integrated into the structure of 3D electrodes for biofuel cells. Their advantage is mainly related to their chemical properties, which have a positive impact on the stability of electrodes such as the laccase-based biocathode. For optimal function in implantable applications the biocathode requires coating with a biocompatible semi-permeable membrane that is designed to prevent the loss of enzyme activity and to protect the structure of the biocathode. Since such membranes are integrated into the electrodes ultimately implanted, they must be fully characterized to demonstrate that there is no interference with the performance of the electrode. In the present study, we demonstrate that chitosan provides superior stability compared with Nafion(®) and should be considered as an optimum solution to enhance the biocompatibility and the stability of 3D bioelectrodes. Copyright © 2016 Elsevier B.V. All rights reserved.

Morphology Effect on Proton Dynamics in Nafion® 117 and Sulfonated Polyether Ether Ketone

NASA Astrophysics Data System (ADS)

Leong, Jun Xing; Diño, Wilson Agerico; Ahmad, Azizan; Daud, Wan Ramli Wan; Kasai, Hideaki

2016-09-01

We report results of our experimental and theoretical studies on the dynamics of proton conductivity in Nafion® 117 and self-fabricated sulfonated polyether ether ketone (SPEEK) membranes. Knowing that the presence of water molecules in the diffusion process results in a lower energy barrier, we determined the diffusion barriers and corresponding tunneling probabilities of Nafion® 117 and SPEEK system using a simple theoretical model that excludes the medium (water molecules) in the initial calculations. We then propose an equation that relates the membrane conductivity to the tunneling probability. We recover the effect of the medium by introducing a correction term into the proposed equation, which takes into account the effect of the proton diffusion distance and the hydration level. We have also experimentally verified that the proposed equation correctly explain the difference in conductivity between Nafion® 117 and SPEEK. We found that membranes that are to be operated in low hydration environments (high temperatures) need to be designed with short diffusion distances to enhance and maintain high conductivity.

Optimization of a Nafion Membrane-Based System for Removal of Chloride and Fluoride from Lunar Regolith-Derived Water

NASA Technical Reports Server (NTRS)

Anthony, Stephen M.; Santiago-Maldonado, Edgardo; Captain, James G.; Pawate, Ashtamurthy S.; Kenis, Paul J. A.

2012-01-01

A long-term human presence in space will require self-sustaining systems capable of producing oxygen and potable water from extraterrestrial sources. Oxygen can be extracted from lunar regolith, and water contaminated with hydrochloric and hydrofluoric acids is produced as an intermediate in this process. We investigated the ability of Nafion proton exchange membranes to remove hydrochloric and hydrofluoric acids from water. The effect of membrane thickness, product stream flow rate, and acid solution temperature and concentration on water flux, acid rejection, and water and acid activity were studied. The conditions that maximized water transport and acid rejection while minimizing resource usage were determined by calculating a figure of merit. Water permeation is highest at high solution temperature and product stream flow rate across thin membranes, while chloride and fluoride permeation are lowest at low acid solution temperature and concentration across thin membranes. The figure of merit varies depending on the starting acid concentration; at low concentration, the figure of merit is highest across a thin membrane, while at high concentration, the figure of merit is highest at low solution temperature. In all cases, the figure of merit increases with increasing product stream flow rate.

Water permeation through anion exchange membranes

NASA Astrophysics Data System (ADS)

Luo, Xiaoyan; Wright, Andrew; Weissbach, Thomas; Holdcroft, Steven

2018-01-01

An understanding of water permeation through solid polymer electrolyte (SPE) membranes is crucial to offset the unbalanced water activity within SPE fuel cells. We examine water permeation through an emerging class of anion exchange membranes, hexamethyl-p-terphenyl poly (dimethylbenzimidazolium) (HMT-PMBI), and compare it against series of membrane thickness for a commercial anion exchange membrane (AEM), Fumapem® FAA-3, and a series of proton exchange membranes, Nafion®. The HMT-PMBI membrane is found to possess higher water permeabilities than Fumapem® FAA-3 and comparable permeability than Nafion (H+). By measuring water permeation through membranes of different thicknesses, we are able to decouple, for the first time, internal and interfacial water permeation resistances through anion exchange membranes. Permeation resistances on liquid/membrane interface is found to be negligible compared to that for vapor/membrane for both series of AEMs. Correspondingly, the resistance of liquid water permeation is found to be one order of magnitude smaller compared to that of vapor water permeation. HMT-PMBI possesses larger effective internal water permeation coefficient than both Fumapem® FAA-3 and Nafion® membranes (60 and 18% larger, respectively). In contrast, the effective interfacial permeation coefficient of HMT-PMBI is found to be similar to Fumapem® (±5%) but smaller than Nafion®(H+) (by 14%).

Hepatic Transcriptome Responses in Mice (Mus musculus) Exposed to the Nafion Membrane and Its Combustion Products

PubMed Central

Feng, Mingbao; Qu, Ruijuan; Habteselassie, Mussie; Wu, Jun; Yang, Shaogui; Sun, Ping; Huang, Qingguo; Wang, Zunyao

2015-01-01

Nafion 117 membrane (N117), an important polymer electrolyte membrane (PEM), has been widely used for numerous chemical technologies. Despite its increasing production and use, the toxicity data for N117 and its combustion products remain lacking. Toxicity studies are necessary to avoid problems related to waste disposal in landfills and incineration that may arise. In this study, we investigated the histopathological alterations, oxidative stress biomarker responses, and transcriptome profiles in the liver of male mice exposed to N117 and its combustion products for 24 days. An ion-chromatography system and liquid chromatography system coupled to a hybrid quadrupole time-of-flight mass spectrometry were used to analyze the chemical compositions of these combustion products. The transcriptomics analysis identified several significantly altered molecular pathways, including the metabolism of xenobiotics, carbohydrates and lipids; signal transduction; cellular processes; immune system; and signaling molecules and interaction. These studies provide preliminary data for the potential toxicity of N117 and its combustion products on living organisms and may fill the information gaps in the toxicity databases for the currently used PEMs. PMID:26057616

Nonhumidified High-Temperature Membranes Developed for Proton Exchange Membrane Fuel Cells

NASA Technical Reports Server (NTRS)

Kinder, James D.

2005-01-01

Fuel cells are being considered for a wide variety of aerospace applications. One of the most versatile types of fuel cells is the proton-exchange-membrane (PEM) fuel cell. PEM fuel cells can be easily scaled to meet the power and space requirements of a specific application. For example, small 100-W PEM fuel cells are being considered for personal power for extravehicular activity suit applications, whereas larger PEM fuel cells are being designed for primary power in airplanes and in uninhabited air vehicles. Typically, PEM fuel cells operate at temperatures up to 80 C. To increase the efficiency and power density of the fuel cell system, researchers are pursuing methods to extend the operating temperature of the PEM fuel cell to 180 C. The most widely used membranes in PEM fuel cells are Nafion 112 and Nafion 117--sulfonated perfluorinated polyethers that were developed by DuPont. In addition to their relatively high cost, the properties of these membranes limit their use in a PEM fuel cell to around 80 C. The proton conductivity of Nafion membranes significantly decreases above 80 C because the membrane dehydrates. The useful operating range of Nafion-based PEM fuel cells can be extended to over 100 C if ancillary equipment, such as compressors and humidifiers, is added to maintain moisture levels within the membrane. However, the addition of these components reduces the power density and increases the complexity of the fuel cell system.

Optimum concentration gradient of the electrocatalyst, Nafion® and poly(tetrafluoroethylene) in a membrane-electrode-assembly for enhanced performance of direct methanol fuel cells.

PubMed

Liu, Jing Hua; Jeon, Min Ku; Lee, Ki Rak; Woo, Seong Ihl

2010-12-14

A combinatorial library of membrane-electrode-assemblies (MEAs) which consisted of 27 different compositions was fabricated to optimize the multilayer structure of direct methanol fuel cells. Each spot consisted of three layers of ink and a gradient was generated by employing different concentrations of the three components (Pt catalyst, Nafion® and polytetrafluoroethylene (PTFE)) of each layer. For quick evaluation of the library, a high-throughput optical screening technique was employed for methanol electro-oxidation reaction (MOR) activity. The screening results revealed that gradient layers could lead to higher MOR activity than uniform layers. It was found that the MOR activity was higher when the concentrations of Pt catalyst and Nafion ionomer decreased downward from the top layer to the bottom layer. On the other hand, higher MOR activity was observed when PTFE concentration increased downward from the top to the bottom layer.

Study and development of sulfated zirconia based proton exchange fuel cell membranes

NASA Astrophysics Data System (ADS)

Kemp, Brittany Wilson

With the increasing consumption of energy, fuel cells are among the most promising alternatives to fossil fuels, provided some technical challenges are overcome. Proton exchange membrane fuel cells (PEMFCs) have been investigated and improvements have been made, but the problem with NafionRTM, the main membrane for PEMFCs, has not been solved. NafionRTM restricts the membranes from operating at higher temperatures, thus preventing them from working in small electronics. The problem is to develop a novel fuel cell membrane that performs comparably to NafionRTM in PEMFCs. The membranes were fabricated by applying sulfated zirconia, via template wetting, to porous alumina membranes. The fabricated membranes showed a proton conductivity of 0.016 S/cm in comparison to the proton conductivity of Nafion RTM (0.05 S/cm). Both formic acid and methanol had a lower crossover flux through the sulfated zirconia membranes (formic acid- 2.89x10 -7 mols/cm2s and methanol-1.78x10-9 mols/cm2s) than through NafionRTM (formic acid-2.03x10 -8 mols/cm2s methanol-2.42x10-6 mols/cm 2s), indicating that a sulfated zirconia PEMFC may serve as a replacement for NafionRTM.

Optomechanical characterization of proton-exchange membrane fuel cells

NASA Astrophysics Data System (ADS)

Jalani, Nikhil H.; Mizar, Shivananda P.; Choi, Pyoungho; Furlong, Cosme; Datta, Ravindra

2004-08-01

Nafion is widely used as the polymer electrolyte in proton exchange membrane (PEM) fuel cells. The properties that make the Nafion membrane indispensable are the combination of good water uptake, ion-exchange capacity, proton conductivity, gas permeability, and excellent electrochemical stability. The amount of water sorbed in the Nafion membrane is critical as the proton conductivity depends directly on the water content of the membrane which determines the fuel cell performance. The factors which affect the extent of the solvent uptake by Nafion are temperature, ion-exchange capacity, pretreatment of membrane, and the physical state of absorbing water, whether it is in liquid or vapor phase. The water sorption in the membrane is explained in terms of thermodynamic equilibrium of water in the vapor and absorption phases. As the membrane imbibes more water, the membrane matrix expands and exerts a pressure on the pore liquid which affects its chemical potential and limits extent of swelling. The extent of matrix expansion of the membranes depends on the elastic modulus, E, of the membrane, which directly affects the sorption. Hence, it is important to understand the variation of E for Nafion membrane with relative humidity (RH) and temperature. Optoelectronic holography (OEH) techniques are applied to perform quantitative, noninvasive, full field of view investigations to determine temperature and water activity dependence of E. The results obtained confirm that with the increase in temperature, E decreases and the membranes imbibes more water. Such results will allow optimization and realization of fuel cells with improved efficiency and performance.

Effect of morphological properties of ionic liquid-templated mesoporous anatase TiO 2 on performance of PEMFC with Nafion/TiO 2 composite membrane at elevated temperature and low relative humidity

NASA Astrophysics Data System (ADS)

Chen, S. Y.; Han, C. C.; Tsai, C. H.; Huang, J.; Chen-Yang, Y. W.

Three high-purity TiO 2 (anatase) powders (T PF6, T BF4, and T conventional) were prepared by the sol-gel method with/without ionic liquid as template and calcinations at 450 °C. These powders were, then, characterized to investigate their differences in morphological properties. Electrochemical performances of the H 2/O 2 PEMFCs employing the Nafion composite membranes with these three TiO 2 powders as fillers were studied over 80-120 °C under 50% and 95% relative humidity (RH). The result showed that the order of the fillers effect on the performance at 80 and 90 °C was the same as that of the TiO 2 filler's specific surface area (i.e. T PF6 > T conventional > T BF4 > P25, a commercially available nonporous TiO 2 powder). However, the order between T conventional and T BF4 was reversed at 110 and 120 °C under 50% RH. This indicates that the size and the amount of mesopores, which better confined the water molecules, were significant contributing factors to the performances at the higher temperatures. The best power density obtained under 50% RH at 120 °C and a voltage of 0.4 V was from the PEMFC with the T PF6-containing Nafion composite membrane. It was about 5.7 times higher than the value obtained from that with the recast Nafion membrane.

Transport of Zn(OH)4(-2) ions across a polyolefin microporous membrane

NASA Astrophysics Data System (ADS)

Krejci, Ivan; Vanysek, Peter; Trojanek, Antonin

1993-04-01

Transport of ZN(OH)4(2-) ions through modified microporous polypropylene membranes (Celgard 3401, 350140) was studied using polarography and conductometry. Soluble Nafion as an ion exchange modifying agent was applied to the membrane by several techniques. The influence of Nafion and a surfactant on transport of zinc ions through the membrane was studied. A relationship between membrane impedance and the rate of Zn(OH)4(2-) transport was found. The found correlation between conductivity, ion permeability and Nafion coverage suggests a suitable technique of membrane preparation to obtain desired zinc ion barrier properties.

Preparation and characterization of nonaqueous proton-conducting membranes with protic ionic liquids.

PubMed

Lu, Fei; Gao, Xinpei; Yan, Xiaojun; Gao, Hejun; Shi, Lijuan; Jia, Han; Zheng, Liqiang

2013-08-14

Hybrid Nafion membranes were successfully fabricated by incorporating with protic imidazolium ionic liquids 1-(2-aminoethyl)-3-methylimidazolium chloride ([MimAE]Cl), 1-(2-hydroxylethyl)-3-methylimidazolium chloride ([MimHE]Cl), and 1-carboxylmethyl-3-methylimidazolium chloride ([MimCM]Cl) for high-temperature fuel cells. The composite membranes were characterized by impedance spectroscopy, small-angle X-ray scattering (SAXS), scanning electronic microscopy (SEM), and thermogravimetric analysis (TGA). The incorporated protic ionic liquids enhance the doping of phosphoric acid (PA) and result in a relatively high ionic conductivity. The Nafion/10 wt % [MimAE]Cl/PA composite membrane exhibits an ionic conductivity of 6.0 mS/cm at 130 °C without humidification. [MimAE]Cl can swell the Nafion matrix more homogeneously than [MimHE]Cl or [MimCM]Cl, which results in a better ionic conductivity. It is notable that the composite Nafion/IL/PA membranes have a better thermal stability than the pristine Nafion membranes.

Radiation-Grafted Polymer Electrolyte Membranes for Water Electrolysis Cells: Evaluation of Key Membrane Properties.

PubMed

Albert, Albert; Barnett, Alejandro O; Thomassen, Magnus S; Schmidt, Thomas J; Gubler, Lorenz

2015-10-14

Radiation-grafted membranes can be considered an alternative to perfluorosulfonic acid (PFSA) membranes, such as Nafion, in a solid polymer electrolyte electrolyzer. Styrene, acrylonitrile, and 1,3-diisopropenylbenzene monomers are cografted into preirradiated 50 μm ethylene tetrafluoroethylene (ETFE) base film, followed by sulfonation to introduce proton exchange sites to the obtained grafted films. The incorporation of grafts throughout the thickness is demonstrated by scanning electron microscopy/energy-dispersive X-ray spectroscopy (SEM/EDX) analysis of the membrane cross-sections. The membranes are analyzed in terms of grafting kinetics, ion-exchange capacity (IEC), and water uptake. The key properties of radiation-grafted membranes and Nafion, such as gas crossover, area resistance, and mechanical properties, are evaluated and compared. The plot of hydrogen crossover versus area resistance of the membranes results in a property map that indicates the target areas for membrane development for electrolyzer applications. Tensile tests are performed to assess the mechanical properties of the membranes. Finally, these three properties are combined to establish a figure of merit, which indicates that radiation-grafted membranes obtained in the present study are promising candidates with properties superior to those of Nafion membranes. A water electrolysis cell test is performed as proof of principle, including a comparison to a commercial membrane electrode assembly (MEA).

SPEEK/PVDF/PES Composite as Alternative Proton Exchange Membrane for Vanadium Redox Flow Batteries

NASA Astrophysics Data System (ADS)

Fu, Zhimin; Liu, Jinying; Liu, Qifeng

2016-01-01

A membrane consisting of a blend of sulfonated poly(ether ether ketone) (SPEEK), poly(vinylidene fluoride) (PVDF), and poly(ether sulfone) (PES) has been fabricated and used as an ion exchange membrane for application in vanadium redox flow batteries (VRBs). The vanadium ion permeability of the SPEEK/PVDF/PES membrane was one order of magnitude lower than that of Nafion 117 membrane. The low-cost composite membrane exhibited better performance than Nafion 117 membrane at the same operating condition. A VRB single cell with SPEEK/PVDF/PES membrane showed significantly lower capacity loss, higher coulombic efficiency (>95%), and higher energy efficiency (>82%) compared with Nafion 117 membrane. In the self-discharge test, the duration of the cell with the SPEEK/PVDF/PES membrane was nearly two times longer than that with Nafion 117 membrane. Considering these good properties and its low cost, SPEEK/PVDF/PES membrane is expected to have excellent commercial prospects as an ion exchange membrane for VRB systems.

Transport of Zn(OH4)(2-) Ions Across a Polyolefin Microporous Membrane

DTIC Science & Technology

1992-12-22

studied using polarography and conductometry . Soluble Nafion as an ion exchange modifying agent was applied to the membrane by several techniques. The...polypropylene membranes was studied using polarography and conductometry . Soluble Nafion as an ion exchange modifying agent was applied to the membrane by

Characterization of vanadium ion uptake in sulfonated diels alder poly(phenylene) membranes

DOE PAGES

Lawton, Jamie; Jones, Amanda; Tang, Zhijiang; ...

2015-11-28

Sulfonated diels alder poly(phenylene) (SDAPP), alternative aromatic hydrocarbon membranes for vanadium redox flow batteries (VRFBs) are characterized using electron paramagnetic resonance (EPR). Membranes soaked in sulfuric acid and vanadyl sulfate are analyzed to determine the membrane environment in which the vanadyl ion (VO 2+) diffuses in the membranes. These results are compared to Nafion 117 membranes. In contrast to Nafion, the VO 2+ in SDAPP membranes exists in two different environments. The results of analysis of rotational diffusion determined from fits the EPR spectral lineshapes in comparison with previously reported permeation studies and measurements of partitioning functions reported here suggestmore » that the diffusion pathways in SDAPP are very different than in Nafion.« less

Theoretical investigation of local proton conductance in the proton exchange membranes

NASA Astrophysics Data System (ADS)

Singh, Raman K.; Tsuneda, Takao; Miyatake, Kenji; Watanabe, Masahiro

2014-07-01

The hydrated structures of the proton exchange membranes were theoretically investigated using long-range corrected density functional theory to make clear why perfluorinated polymer membrane Nafion is superior to other membranes in the proton conductivity at low humidity. For exploring the possibility of the proton conductance in the vehicle mechanism with low hydration numbers, we examined the relay model of protonated water clusters between the sulfonic acid groups in Nafion and concluded that this relay model may contribute to the high proton conductivity of Nafion with less-hydrated sulfonic acid groups.

Effects of surface roughening of Nafion 117 on the mechanical and physicochemical properties of ionic polymer-metal composite (IPMC) actuators

NASA Astrophysics Data System (ADS)

Wang, Yanjie; Zhu, Zicai; Liu, Jiayu; Chang, Longfei; Chen, Hualing

2016-08-01

In this paper, the surface of a Nafion membrane was roughened by the sandblasting method, mainly considering the change of sandblasting time and powder size. The roughened surfaces were characterized in terms of their topography from the confocal laser scanning microscope (CLSM) and SEM. The key surface parameters, such as Sa (the arithmetical mean deviation of the specified surface profile), SSA (the surface area ratio before and after roughening) and the area measurement on the histogram from the CLSM images, were extracted and evaluated from the roughened membranes. Also, the detailed change in surface and interfacial electrodes were measured and discussed together with the surface resistance, equivalent modulus, capacitance and performances of IPMC actuators based on the roughened membranes. The results show that a suitable sandblasting condition, resulting in the decrease in the bending stiffness and the increase in the interface area closely related to the capacitance, can effectively increase the electromechanical responses of IPMCs. Although the surface roughening by sandblasting caused a considerable lowering of mechanical strength, it was very effective for enlarging the interfacial area between Nafion membrane and the electrode layers, and for forming a penetrated electrode structure, which facilitated improvement of the surface resistance and capacitance characteristics of IPMCs. In this work, a quantitative relationship was built between the topography of Nafion membrane surface and electromechanical performance of IPMCs by means of sandblasting.

Mechanism for degradation of Nafion in PEM fuel cells from quantum mechanics calculations.

PubMed

Yu, Ted H; Sha, Yao; Liu, Wei-Guang; Merinov, Boris V; Shirvanian, Pezhman; Goddard, William A

2011-12-14

We report results of quantum mechanics (QM) mechanistic studies of Nafion membrane degradation in a polymer electrolyte membrane (PEM) fuel cell. Experiments suggest that Nafion degradation is caused by generation of trace radical species (such as OH(●), H(●)) only when in the presence of H(2), O(2), and Pt. We use density functional theory (DFT) to construct the potential energy surfaces for various plausible reactions involving intermediates that might be formed when Nafion is exposed to H(2) (or H(+)) and O(2) in the presence of the Pt catalyst. We find a barrier of 0.53 eV for OH radical formation from HOOH chemisorbed on Pt(111) and of 0.76 eV from chemisorbed OOH(ad), suggesting that OH might be present during the ORR, particularly when the fuel cell is turned on and off. Based on the QM, we propose two chemical mechanisms for OH radical attack on the Nafion polymer: (1) OH attack on the S-C bond to form H(2)SO(4) plus a carbon radical (barrier: 0.96 eV) followed by decomposition of the carbon radical to form an epoxide (barrier: 1.40 eV). (2) OH attack on H(2) crossover gas to form hydrogen radical (barrier: 0.04 eV), which subsequently attacks a C-F bond to form HF plus carbon radicals (barrier as low as 1.00 eV). This carbon radical can then decompose to form a ketone plus a carbon radical with a barrier of 0.86 eV. The products (HF, OCF(2), SCF(2)) of these proposed mechanisms have all been observed by F NMR in the fuel cell exit gases along with the decrease in pH expected from our mechanism. © 2011 American Chemical Society

Development of large-surface Nafion-metal composite actuator and its electrochemical characterization

NASA Astrophysics Data System (ADS)

Noh, Taegeun; Tak, Yong Suk; Nam, Jaedo; Jeon, Jaewook; Kim, Hunmo; Choi, Hyoukryeol; Bae, Sang Sik

2001-07-01

Behaviors of nafion-based actuators are significantly affected by interfacial area between electrode and polymer electrolyte. Replication method was utilized to manufacture a large surface-area composite actuator. Etched aluminum foil was used as a template for replication using liquid nafion solution. Measurement of double layer charging and scanning electron microscopy indicated that interfacial area was greatly increased by replication method. Higher surface area induced a better bending performance of ionic polymer metal composite (IPMC). In parallel, the effect of cations on IPMC was interpreted with constant current experiment, linear sweep voltammetry and electrochemical impedance spectroscopy. For univalent cations, ion size is the most influencing parameter on ionic mobility inside membrane. However, ion-ion interaction affects an ionic mobility for divalent cations.

Fabrication of a nanosize-Pt-embedded membrane electrode assembly to enhance the utilization of Pt in proton exchange membrane fuel cells.

PubMed

Choe, Junseok; Kim, Doyoung; Shim, Jinyong; Lee, Inhae; Tak, Yongsug

2011-08-01

A procedure to locate the Pt nanostructure inside the hydrophilic channel of a Nafion membrane was developed in order to enhance Pt utilization in PEMFCs. Nanosize Pt-embedded MEA was constructed by Cu electroless plating and subsequent Pt electrodeposition inside the hydrophilic channels of the Nafion membrane. The metallic Pt nanostructure fabricated inside the membrane was employed as an oxygen reduction catalyst for a PEMFC and facilitated effective use of the hydrophilic channels inside the membrane. Compared to the conventional MEA, a Pt-embedded MEA with only 68% Pt loading showed better PEMFC performance.

Selectivity of Direct Methanol Fuel Cell Membranes.

PubMed

Aricò, Antonino S; Sebastian, David; Schuster, Michael; Bauer, Bernd; D'Urso, Claudia; Lufrano, Francesco; Baglio, Vincenzo

2015-11-24

Sulfonic acid-functionalized polymer electrolyte membranes alternative to Nafion(®) were developed. These were hydrocarbon systems, such as blend sulfonated polyetheretherketone (s-PEEK), new generation perfluorosulfonic acid (PFSA) systems, and composite zirconium phosphate-PFSA polymers. The membranes varied in terms of composition, equivalent weight, thickness, and filler and were investigated with regard to their methanol permeation characteristics and proton conductivity for application in direct methanol fuel cells. The behavior of the membrane electrode assemblies (MEA) was investigated in fuel cell with the aim to individuate a correlation between membrane characteristics and their performance in a direct methanol fuel cell (DMFC). The power density of the DMFC at 60 °C increased according to a square root-like function of the membrane selectivity. This was defined as the reciprocal of the product between area specific resistance and crossover. The power density achieved at 60 °C for the most promising s-PEEK-based membrane-electrode assembly (MEA) was higher than the benchmark Nafion(®) 115-based MEA (77 mW·cm(-2) vs. 64 mW·cm(-2)). This result was due to a lower methanol crossover (47 mA·cm(-2) equivalent current density for s-PEEK vs. 120 mA·cm(-2) for Nafion(®) 115 at 60 °C as recorded at OCV with 2 M methanol) and a suitable area specific resistance (0.15 Ohm cm² for s-PEEK vs. 0.22 Ohm cm² for Nafion(®) 115).

Selectivity of Direct Methanol Fuel Cell Membranes

PubMed Central

Aricò, Antonino S.; Sebastian, David; Schuster, Michael; Bauer, Bernd; D’Urso, Claudia; Lufrano, Francesco; Baglio, Vincenzo

2015-01-01

Sulfonic acid-functionalized polymer electrolyte membranes alternative to Nafion® were developed. These were hydrocarbon systems, such as blend sulfonated polyetheretherketone (s-PEEK), new generation perfluorosulfonic acid (PFSA) systems, and composite zirconium phosphate–PFSA polymers. The membranes varied in terms of composition, equivalent weight, thickness, and filler and were investigated with regard to their methanol permeation characteristics and proton conductivity for application in direct methanol fuel cells. The behavior of the membrane electrode assemblies (MEA) was investigated in fuel cell with the aim to individuate a correlation between membrane characteristics and their performance in a direct methanol fuel cell (DMFC). The power density of the DMFC at 60 °C increased according to a square root-like function of the membrane selectivity. This was defined as the reciprocal of the product between area specific resistance and crossover. The power density achieved at 60 °C for the most promising s-PEEK-based membrane-electrode assembly (MEA) was higher than the benchmark Nafion® 115-based MEA (77 mW·cm−2 vs. 64 mW·cm−2). This result was due to a lower methanol crossover (47 mA·cm−2 equivalent current density for s-PEEK vs. 120 mA·cm−2 for Nafion® 115 at 60 °C as recorded at OCV with 2 M methanol) and a suitable area specific resistance (0.15 Ohm cm2 for s-PEEK vs. 0.22 Ohm cm2 for Nafion® 115). PMID:26610582

In situ synthesis of nanocomposite membranes: comprehensive improvement strategy for direct methanol fuel cells.

PubMed

Rao, Siyuan; Xiu, Ruijie; Si, Jiangju; Lu, Shanfu; Yang, Meng; Xiang, Yan

2014-03-01

In situ synthesis is a powerful approach to control nanoparticle formation and consequently confers extraordinary properties upon composite membranes relative to conventional doping methods. Herein, uniform nanoparticles of cesium hydrogen salts of phosphotungstic acid (CsPW) are controllably synthesized in situ in Nafion to form CsPW–Nafion nanocomposite membranes with both improved proton conductivity and methanol-crossover suppression. A 101.3% increase of maximum power density has been achieved relative to pristine Nafion in a direct methanol fuel cell (DMFC), indicating a potential pathway for large-scale fabrication of DMFC alternative membranes.

Membrane development for vanadium redox flow batteries.

PubMed

Schwenzer, Birgit; Zhang, Jianlu; Kim, Soowhan; Li, Liyu; Liu, Jun; Yang, Zhenguo

2011-10-17

Large-scale energy storage has become the main bottleneck for increasing the percentage of renewable energy in our electricity grids. Redox flow batteries are considered to be among the best options for electricity storage in the megawatt range and large demonstration systems have already been installed. Although the full technological potential of these systems has not been reached yet, currently the main problem hindering more widespread commercialization is the high cost of redox flow batteries. Nafion, as the preferred membrane material, is responsible for about 11% of the overall cost of a 1 MW/8 MWh system. Therefore, in recent years two main membrane related research threads have emerged: 1) chemical and physical modification of Nafion membranes to optimize their properties with regard to vanadium redox flow battery (VRFB) application; and 2) replacement of the Nafion membranes with different, less expensive materials. This review summarizes the underlying basic scientific issues associated with membrane use in VRFBs and presents an overview of membrane-related research approaches aimed at improving the efficiency of VRFBs and making the technology cost-competitive. Promising research strategies and materials are identified and suggestions are provided on how materials issues could be overcome.

Durable and self-hydrating tungsten carbide-based composite polymer electrolyte membrane fuel cells.

PubMed

Zheng, Weiqing; Wang, Liang; Deng, Fei; Giles, Stephen A; Prasad, Ajay K; Advani, Suresh G; Yan, Yushan; Vlachos, Dionisios G

2017-09-04

Proton conductivity of the polymer electrolyte membranes in fuel cells dictates their performance and requires sufficient water management. Here, we report a simple, scalable method to produce well-dispersed transition metal carbide nanoparticles. We demonstrate that these, when added as an additive to the proton exchange Nafion membrane, provide significant enhancement in power density and durability over 100 hours, surpassing both the baseline Nafion and platinum-containing recast Nafion membranes. Focused ion beam/scanning electron microscope tomography reveals the key membrane degradation mechanism. Density functional theory exposes that OH• and H• radicals adsorb more strongly from solution and reactions producing OH• are significantly more endergonic on tungsten carbide than on platinum. Consequently, tungsten carbide may be a promising catalyst in self-hydrating crossover gases while retarding desorption of and capturing free radicals formed at the cathode, resulting in enhanced membrane durability.The proton conductivity of polymer electrolyte membranes in fuel cells dictates their performance, but requires sufficient water management. Here, the authors report a simple method to produce well-dispersed transition metal carbide nanoparticles as additives to enhance the performance of Nafion membranes in fuel cells.

Biological Fuel Cells and Membranes.

PubMed

Ghassemi, Zahra; Slaughter, Gymama

2017-01-17

Biofuel cells have been widely used to generate bioelectricity. Early biofuel cells employ a semi-permeable membrane to separate the anodic and cathodic compartments. The impact of different membrane materials and compositions has also been explored. Some membrane materials are employed strictly as membrane separators, while some have gained significant attention in the immobilization of enzymes or microorganisms within or behind the membrane at the electrode surface. The membrane material affects the transfer rate of the chemical species (e.g., fuel, oxygen molecules, and products) involved in the chemical reaction, which in turn has an impact on the performance of the biofuel cell. For enzymatic biofuel cells, Nafion, modified Nafion, and chitosan membranes have been used widely and continue to hold great promise in the long-term stability of enzymes and microorganisms encapsulated within them. This article provides a review of the most widely used membrane materials in the development of enzymatic and microbial biofuel cells.

Biological Fuel Cells and Membranes

PubMed Central

Ghassemi, Zahra; Slaughter, Gymama

2017-01-01

Biofuel cells have been widely used to generate bioelectricity. Early biofuel cells employ a semi-permeable membrane to separate the anodic and cathodic compartments. The impact of different membrane materials and compositions has also been explored. Some membrane materials are employed strictly as membrane separators, while some have gained significant attention in the immobilization of enzymes or microorganisms within or behind the membrane at the electrode surface. The membrane material affects the transfer rate of the chemical species (e.g., fuel, oxygen molecules, and products) involved in the chemical reaction, which in turn has an impact on the performance of the biofuel cell. For enzymatic biofuel cells, Nafion, modified Nafion, and chitosan membranes have been used widely and continue to hold great promise in the long-term stability of enzymes and microorganisms encapsulated within them. This article provides a review of the most widely used membrane materials in the development of enzymatic and microbial biofuel cells. PMID:28106711

Anion-conductive membranes with ultralow vanadium permeability and excellent performance in vanadium flow batteries.

PubMed

Mai, Zhensheng; Zhang, Huamin; Zhang, Hongzhang; Xu, Wanxing; Wei, Wenping; Na, Hui; Li, Xianfeng

2013-02-01

Anion exchange membranes prepared from quaternized poly(tetramethyl diphenyl ether sulfone) (QAPES) were first investigated in the context of vanadium flow battery (VFB) applications. The membranes showed an impressive suppression effect on vanadium ions. The recorded vanadium permeability was 0.02×10(-7)-0.09×10(-7) cm(2) min(-1), which was two orders of magnitude lower than that of Nafion 115. The self-discharge duration of a VFB single cell with a QAPES membrane is four times longer than that of Nafion 115. The morphological difference in hydrophilic domains between QAPES and Nafion was confirmed by TEM. After soaking the membranes in VO(2)(+) solution, adsorbed vanadium ions can barely be found in QAPES, whereas the hydrophilic domains of Nafion were stained. In the ex situ chemical stability test, QAPES showed a high tolerance to VO(2)(+) and remained intact after immersion in VO(2)(+) solution for over 250 h. The performance of a VFB single cell assembled with QAPES membranes is equal to or even better than that of Nafion 115 and remains stable in a long-term cycle test. These results indicate that QAPES membranes can be an ideal option in the fabrication of high-performance VFBs with low electric capacity loss. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Temperature dependence of the electrode kinetics of oxygen reduction at the platinum/Nafion interface - A microelectrode investigation

NASA Technical Reports Server (NTRS)

Parthasarathy, Arvind; Srinivasan, Supramanian; Appleby, A. J.; Martin, Charles R.

1992-01-01

Results of a study of the temperature dependence of the oxygen reduction kinetics at the Pt/Nafion interface are presented. This study was carried out in the temperature range of 30-80 C and at 5 atm of oxygen pressure. The results showed a linear increase of the Tafel slope with temperature in the low current density region, but the Tafel slope was found to be independent of temperature in the high current density region. The values of the activation energy for oxygen reduction at the platinum/Nafion interface are nearly the same as those obtained at the platinum/trifluoromethane sulfonic acid interface but less than values obtained at the Pt/H3PO4 and Pt/HClO4 interfaces. The diffusion coefficient of oxygen in Nafion increases with temperature while its solubility decreases with temperature. These temperatures also depend on the water content of the membrane.

High performance membrane-electrode assembly based on a surface-modified membrane

NASA Astrophysics Data System (ADS)

Han, Sangil; Lee, Jang Woo; Kwak, Chan; Chai, Geun Seok; Son, In Hyuk; Jang, Moon Yup; An, Sung Guk; Cho, Sung Yong; Kim, Jun Young; Kim, Hyung Wook; Serov, Alexey Alexandrovych; Yoo, Youngtai; Nam, Kie Hyun

A surface-modified membrane is prepared using a sputtering technique that deposits gold directly on a Nafion ® 115 membrane surface that is roughened with silicon carbide paper. The surface-modified membranes are characterized by means of a scanning electron microscope (SEM), differential scanning calorimetry (DSC), and water contact-angle analysis. A single direct methanol fuel cell (DMFC) with a surface-modified membrane exhibits enhanced performance (160 mW cm -2), while a bare Nafion ® 115 cell yields 113 mW cm -2 at 0.4 V and an operating temperature of 70 °C. From FE-SEM images and CO ad stripping voltammograms, it is also found that the gold layer is composed of clusters of porous nodule-like particles, which indicates that an anode with nodule-like gold leads to the preferential oxidation of carbon monoxide. These results suggest that the topology of gold in the interfacial area and its electrocatalytic nature may be the critical factors that affect DMFC performance.

Inorganic-based proton conductive composite membranes for elevated temperature and reduced relative humidity PEM fuel cells

NASA Astrophysics Data System (ADS)

Wang, Chunmei

Proton exchange membrane (PEM) fuel cells are regarded as highly promising energy conversion systems for future transportation and stationary power generation and have been under intensive investigations for the last decade. Unfortunately, cutting edge PEM fuel cell design and components still do not allow economically commercial implementation of this technology. The main obstacles are high cost of proton conductive membranes, low-proton conductivity at low relative humidity (RH), and dehydration and degradation of polymer membranes at high temperatures. The objective of this study was to develop a systematic approach to design a high proton conductive composite membrane that can provide a conductivity of approximately 100 mS cm-1 under hot and dry conditions (120°C and 50% RH). The approach was based on fundamental and experimental studies of the proton conductivity of inorganic additives and composite membranes. We synthesized and investigated a variety of organic-inorganic Nafion-based composite membranes. In particular, we analyzed their fundamental properties, which included thermal stability, morphology, the interaction between inorganic network and Nafion clusters, and the effect of inorganic phase on the membrane conductivity. A wide range of inorganic materials was studied in advance in order to select the proton conductive inorganic additives for composite membranes. We developed a conductivity measurement method, with which the proton conductivity characteristics of solid acid materials, zirconium phosphates, sulfated zirconia (S-ZrO2), phosphosilicate gels, and Santa Barbara Amorphous silica (SBA-15) were discussed in detail. Composite membranes containing Nafion and different amounts of functionalized inorganic additives (sulfated inorganics such as S-ZrO2, SBA-15, Mobil Composition of Matter MCM-41, and S-SiO2, and phosphonated inorganic P-SiO2) were synthesized with different methods. We incorporated inorganic particles within Nafion clusters

Selective growth of MoS2 for proton exchange membranes with extremely high selectivity.

PubMed

Feng, Kai; Tang, Beibei; Wu, Peiyi

2013-12-26

Proton conductivity and methanol permeability are the most important transport properties of proton exchange membranes (PEMs). The ratio of proton conductivity to methanol permeability is usually called selectivity. Herein, a novel strategy of in situ growth of MoS2 is employed to prepare MoS2/Nafion composite membranes for highly selective PEM. The strong interactions between the Mo precursor ((NH4)2MoS4) and Nafion's sulfonic groups in a suitable solvent environment (DMF) probably lead to a selective growth of MoS2 flakes mainly around the ionic clusters of the resultant MoS2/Nafion composite membrane. Therefore, it would significantly promote the aggregation and hence lead to a better connectivity of these ionic clusters, which favors the increase in proton conductivity. Meanwhile, the existence of MoS2 in the ionic channels effectively prevents methanol transporting through the PEM, contributing to the dramatic decrease in the methanol permeability. Consequently, the MoS2/Nafion composite membranes exhibit greatly increased selectivity. Under some severe conditions, such as 50 °C with 80 v/v% of methanol concentration, an increase in the membrane selectivity by nearly 2 orders of magnitude compared with that of the recast Nafion membrane could be achieved here, proving our method as a very promising way to prepare high-performance PEMs. All these conclusions are confirmed by various characterizations, such as (FE-) SEM, TEM, AFM, IR, Raman, TGA, XRD, etc.

Pressure dependence of the oxygen reduction reaction at the platinum microelectrode/nafion interface - Electrode kinetics and mass transport

NASA Technical Reports Server (NTRS)

Parthasarathy, Arvind; Srinivasan, Supramaniam; Appleby, A. J.; Martin, Charles R.

1992-01-01

The investigation of oxygen reduction kinetics at the platinum/Nafion interface is of great importance in the advancement of proton-exchange-membrane (PEM) fuel-cell technology. This study focuses on the dependence of the oxygen reduction kinetics on oxygen pressure. Conventional Tafel analysis of the data shows that the reaction order with respect to oxygen is unity at both high and low current densities. Chronoamperometric measurements of the transport parameters for oxygen in Nafion show that oxygen dissolution follows Henry's isotherm. The diffusion coefficient of oxygen is invariant with pressure; however, the diffusion coefficient for oxygen is lower when air is used as the equilibrating gas as compared to when oxygen is used for equilibration. These results are of value in understanding the influence of O2 partial pressure on the performance of PEM fuel cells and also in elucidating the mechanism of oxygen reduction at the platinum/Nafion interface.

Tuning the Perfluorosulfonic Acid Membrane Morphology for Vanadium Redox-Flow Batteries.

PubMed

Vijayakumar, M; Luo, Qingtao; Lloyd, Ralph; Nie, Zimin; Wei, Xiaoliang; Li, Bin; Sprenkle, Vincent; Londono, J-David; Unlu, Murat; Wang, Wei

2016-12-21

The microstructure of perfluorinated sulfonic acid proton-exchange membranes such as Nafion significantly affects their transport properties and performance in a vanadium redox-flow battery (VRB). In this work, Nafion membranes with various equivalent weights ranging from 1000 to 1500 are prepared and the morphology-property-performance relationship is investigated. NMR and small-angle X-ray scattering studies revealed their composition and morphology variances, which lead to major differences in key transport properties related to proton conduction and vanadium-ion permeation. Their performances are further characterized as VRB membranes. On the basis of this understanding, a new perfluorosulfonic acid membrane is designed with optimal pore geometry and thickness, leading to higher ion selectivity and lower cost compared with the widely used Nafion 115. Excellent VRB single-cell performance (89.3% energy efficiency at 50 mA·cm -2 ) was achieved along with a stable cyclical capacity over prolonged cycling.

Durable and self-hydrating tungsten carbide-based composite polymer electrolyte membrane fuel cells

DOE PAGES

Zheng, Weiqing; Wang, Liang; Deng, Fei; ...

2017-09-04

Proton conductivity of the polymer electrolyte membranes in fuel cells dictates their performance and requires sufficient water management. Here, we report a simple, scalable method to produce well-dispersed transition metal carbide nanoparticles. We demonstrate that these, when added as an additive to the proton exchange Nafion membrane, provide significant enhancement in power density and durability over 100 hours, surpassing both the baseline Nafion and platinum-containing recast Nafion membranes. Using focused ion beam/scanning electron microscope tomography reveals the key membrane degradation mechanism. Density functional theory exposes that OH• and H• radicals adsorb more strongly from solution and reactions producing OH• aremore » significantly more endergonic on tungsten carbide than on platinum. Consequently, tungsten carbide may be a promising catalyst in self-hydrating crossover gases while retarding desorption of and capturing free radicals formed at the cathode, resulting in enhanced membrane durability.« less

Quaternized adamantane-containing poly(aryl ether ketone) anion exchange membranes for vanadium redox flow battery applications

NASA Astrophysics Data System (ADS)

Zhang, Bengui; Zhang, Shouhai; Weng, Zhihuan; Wang, Guosheng; Zhang, Enlei; Yu, Ping; Chen, Xiaomeng; Wang, Xinwei

2016-09-01

Quaternized adamantane-containing poly(aryl ether ketone) anion exchange membranes (QADMPEK) are prepared and investigated for vanadium redox flow batteries (VRFB) application. The bulky, rigid and highly hydrophobic adamantane segment incorporated into the backbone of membrane material makes QADMPEK membranes have low water uptake and swelling ratio, and the as-prepared membranes display significantly lower permeability of vanadium ions than that of Nafion117 membrane. As a consequence, the VRFB cell with QADMPEK-3 membrane shows higher coulombic efficiency (99.4%) and energy efficiency (84.0%) than those for Nafion117 membrane (95.2% and 80.5%, respectively) at the current density of 80 mA cm-2. Furthermore, at a much higher current density of 140 mA cm-2, QADMPEK membrane still exhibits better coulombic efficiency and energy efficiency than Nafion117 membrane (coulombic efficiency 99.2% vs 96.5% and energy efficiency 76.0% vs 74.0%). Moreover, QADMPEK membranes show high stability in in-situ VRFB cycle test and ex-situ oxidation stability test. These results indicate that QADMPEK membranes are good candidates for VRFB applications.

Transport properties of proton-exchange membranes: Effect of supercritical-fluid processing and chemical functionality

NASA Astrophysics Data System (ADS)

Pulido Ayazo

NafionRTM membranes commonly used in direct methanol fuel cells (DMFC), are tipically limited by high methanol permeability (also known as the cross-over limitation). These membranes have phase segregated sulfonated ionic domains in a perfluorinated backbone, which makes processing challenging and limited by phase equilibria considerations. This study used supercritical fluids (SCFs) as a processing alternative, since the gas-like mass transport properties of SCFs allow a better penetration into the membranes and the use of polar co-solvents influenced their morphology, fine-tuning the physical and transport properties in the membrane. Measurements of methanol permeability and proton conductivity were performed to the NafionRTM membranes processed with SCFs at 40ºC and 200 bar and the co-solvents as: acetone, tetrahydrofuran (THF), isopropyl alcohol, HPLC-grade water, acetic acid, cyclohexanone. The results obtained for the permeability data were of the order of 10 -8-10-9 cm2/s, two orders of magnitude lower than unprocessed Nafion. Proton conductivity results obtained using AC impedance electrochemical spectroscopy was between 0.02 and 0.09 S/cm, very similar to the unprocessed Nafion. SCF processing with ethanol as co-solvent reduced the methanol permeability by two orders of magnitude, while the proton conductivity was only reduced by 4%. XRD analysis made to the treated samples exhibited a decreasing pattern in the crystallinity, which affects the transport properties of the membrane. Also, SAXS profiles of the Nafion membranes processed were obtained with the goal of determining changes produced by the SCF processing in the hydrophilic domains of the polymer. With the goal of searching for new alternatives in proton exchange membranes (PEMs) triblock copolymer of poly(styrene-isobutylene-styrene) (SIBS) and poly(styrene-isobutylene-styrene) SEBS were studied. These sulfonated tri-block copolymers had lower methanol permeabilities, but also lower proton

Proton-conductive nanochannel membrane for fuel-cell applications.

PubMed

Oleksandrov, Sergiy; Lee, Jeong-Woo; Jang, Joo-Hee; Haam, Seungjoo; Chung, Chan-Hwa

2009-02-01

Novel design of proton conductive membrane for direct methanol fuel cells is based on proton conductivity of nanochannels, which is acquired due to the electric double layer overlap. Proton conductivity and methanol permeability of an array of nanochannels were studied. Anodic aluminum oxide with pore diameter of 20 nm was used as nanochannel matrix. Channel surfaces of an AAO template were functionalized with sulfonic groups to increase proton conductivity of nanochannels. This was done in two steps; at first -SH groups were attached to walls of nanochannels using (3-Mercaptopropyl)-trimethyloxysilane and then they were converted to -SO3H groups using hydrogen peroxide. Treatment steps were analyzed by Fourier Transform Infrared spectroscopy and X-ray Photoelectron Spectroscopy. Proton conductivity and methanol permeability were measured. The data show methanol permeability of membrane to be an order of magnitude lower, than that measured of Nafion. Ion conductivity of functionalized AAO membrane was measured by an impedance analyzer at frequencies ranging from 1 Hz to 100 kHz and voltage 50 mV to be 0.15 Scm(-1). Measured ion conductivity of Nafion membrane was 0.05 Scm(-1). Obtained data show better results in comparison with commonly used commercial available proton conductive membrane Nafion, thus making nanochannel membrane very promising for use in fuel cell applications.

Microscopic Analysis of Current and Mechanical Properties of Nafion® Studied by Atomic Force Microscopy

PubMed Central

Hiesgen, Renate; Helmly, Stefan; Galm, Ines; Morawietz, Tobias; Handl, Michael; Friedrich, K. Andreas

2012-01-01

The conductivity of fuel cell membranes as well as their mechanical properties at the nanometer scale were characterized using advanced tapping mode atomic force microscopy (AFM) techniques. AFM produces high-resolution images under continuous current flow of the conductive structure at the membrane surface and provides some insight into the bulk conducting network in Nafion membranes. The correlation of conductivity with other mechanical properties, such as adhesion force, deformation and stiffness, were simultaneously measured with the current and provided an indication of subsurface phase separations and phase distribution at the surface of the membrane. The distribution of conductive pores at the surface was identified by the formation of water droplets. A comparison of nanostructure models with high-resolution current images is discussed in detail. PMID:24958429

Investigation of the Interaction between Nafion Ionomer and Surface Functionalized Carbon Black Using Both Ultrasmall Angle X-ray Scattering and Cryo-TEM

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang, Fan; Xin, Le; Uzunoglu, Aytekin

In making a catalyst ink, the interaction between Nafion ionomer and catalyst support are the key factors that directly affect both ionic conductivity and electronic conductivity of the catalyst layer in a membrane electrode assembly (MEA). One of the major aims of this investigation is to understand the behavior of the catalyst support, Vulcan XC-72 (XC-72) aggregates, in the existence of the Nafion ionomer in a catalyst ink to fill the knowledge gap of the interaction of these components. The dispersion of catalyst ink not only depends on the solvent, but also depends on the interaction of Nafion and carbonmore » particles in the ink. The interaction of Nafion ionomer particles and XC-72 catalyst aggregates in liquid media was studied using ultra small angle x-ray scattering (USAXS) and cryogenic TEM techniques. Carbon black XC-72) and functionalized carbon black systems were introduced to study the interaction behaviors. A multiple curve fitting was used to extract the particle size and size distribution from scattering data. The results suggest that the particle size and size distribution of each system changed significantly in Nafion + XC-72 system, Nafion + NH2-XC72 system, and Nafion + SO3H-XC-72 system, which indicates that an interaction among these components (i.e. ionomer particles and XC-72 aggregates) exists. The cryogenic TEM, which allows for the observation the size of particles in a liquid, was used to validate the scattering results and shows excellent agreement.« less

Mesoscale simulations of confined Nafion thin films.

PubMed

Vanya, P; Sharman, J; Elliott, J A

2017-12-07

The morphology and transport properties of thin films of the ionomer Nafion, with thicknesses on the order of the bulk cluster size, have been investigated as a model system to explain the anomalous behaviour of catalyst/electrode-polymer interfaces in membrane electrode assemblies. We have employed dissipative particle dynamics (DPD) to investigate the interaction of water and fluorocarbon chains, with carbon and quartz as confining materials, for a wide range of operational water contents and film thicknesses. We found confinement-induced clustering of water perpendicular to the thin film. Hydrophobic carbon forms a water depletion zone near the film interface, whereas hydrophilic quartz results in a zone with excess water. There are, on average, oscillating water-rich and fluorocarbon-rich regions, in agreement with experimental results from neutron reflectometry. Water diffusivity shows increasing directional anisotropy of up to 30% with decreasing film thickness, depending on the hydrophilicity of the confining material. A percolation analysis revealed significant differences in water clustering and connectivity with the confining material. These findings indicate the fundamentally different nature of ionomer thin films, compared to membranes, and suggest explanations for increased ionic resistances observed in the catalyst layer.

Mesoscale simulations of confined Nafion thin films

NASA Astrophysics Data System (ADS)

Vanya, P.; Sharman, J.; Elliott, J. A.

2017-12-01

The morphology and transport properties of thin films of the ionomer Nafion, with thicknesses on the order of the bulk cluster size, have been investigated as a model system to explain the anomalous behaviour of catalyst/electrode-polymer interfaces in membrane electrode assemblies. We have employed dissipative particle dynamics (DPD) to investigate the interaction of water and fluorocarbon chains, with carbon and quartz as confining materials, for a wide range of operational water contents and film thicknesses. We found confinement-induced clustering of water perpendicular to the thin film. Hydrophobic carbon forms a water depletion zone near the film interface, whereas hydrophilic quartz results in a zone with excess water. There are, on average, oscillating water-rich and fluorocarbon-rich regions, in agreement with experimental results from neutron reflectometry. Water diffusivity shows increasing directional anisotropy of up to 30% with decreasing film thickness, depending on the hydrophilicity of the confining material. A percolation analysis revealed significant differences in water clustering and connectivity with the confining material. These findings indicate the fundamentally different nature of ionomer thin films, compared to membranes, and suggest explanations for increased ionic resistances observed in the catalyst layer.

Efficiency and temperature dependence of water removal by membrane dryers

NASA Technical Reports Server (NTRS)

Leckrone, K. J.; Hayes, J. M.

1997-01-01

The vapor pressure of water in equilibrium with sorption sites within a Nafion membrane is given by log P(WN) = -3580/T + 10.01, where P(WN) is expressed in Torr and T is the membrane temperature, in kelvin. The efficiency of dryers based on selective permeation of water through Nafion can thus be enhanced by cooling the membrane. Residual water in effluents exceeds equilibrium levels if insufficient time is allowed for water to diffuse to the membrane surface as gas passes through the dryer. For tubular configurations, this limitation can be avoided if L > or = Fc(10(3.8)/120 pi D), where L is the length of the tubular membrane, in centimeters, Fc is the gas flow rate, in mL/ min, and D is the diffusion coefficient for water in the carrier gas at the operating temperature of the dryer, in cm2/s. An efficient dryer that at room temperature dries gas to a dew point of -61 degrees C is described; the same dryer maintained at 0 degrees C yields a dew point of -80 degrees C and removes water as effectively as Mg(ClO4)2 or a dry ice/acetone slush. The use of Nafion membranes to construct devices capable of delivering gas streams with low but precisely controlled humidities is discussed.

Enhancing performance of PEM fuel cells: Using the Au nanoplatelet/Nafion interface to enable CO oxidation under ambient conditions

DOE PAGES

Li, Hongfei; Pan, Cheng; Zhao, Sijia; ...

2016-04-16

We developed a method for fabrication of Au nanoparticle platelets which can be coated onto the Nafion membranes of polymer electrolyte membrane (PEM) fuel cells simply by Langmuir–Blodgett (LB) trough lift off from the air water interface. By incorporating the coated membranes into fuel cells with one membrane electrode assembly (MEA) we enhanced the maximum power output by more than 50% when operated under ambient conditions. An enhancement of more than 200% was observed when 0.1% CO was incorporated into the H 2 input gas stream and minimal enhancement was observed when the PEM fuel cell was operated with 100%more » O 2 gas at the cathode, or when particles were deposited on the electrodes. Density function theory (DFT) calculations were carried out to understand the origin of improved output power. Au NPs with 3-atomic layer in height and 2 nm in size were constructed to model the experimentally synthesized Au NPs. Our results indicated that the Au NPs interacted synergistically with the SO 3 groups, attached at end of Nafion side chains, to reduce the energy barrier for the oxidation of CO occurring at the perimeter of the Au NPs, from 1.292 eV to 0.518 eV, enabling the reaction to occur at T<300 K.« less

Comparing selected morphological models of hydrated Nafion using large scale molecular dynamics simulations

NASA Astrophysics Data System (ADS)

Knox, Craig K.

Experimental elucidation of the nanoscale structure of hydrated Nafion, the most popular polymer electrolyte or proton exchange membrane (PEM) to date, and its influence on macroscopic proton conductance is particularly challenging. While it is generally agreed that hydrated Nafion is organized into distinct hydrophilic domains or clusters within a hydrophobic matrix, the geometry and length scale of these domains continues to be debated. For example, at least half a dozen different domain shapes, ranging from spheres to cylinders, have been proposed based on experimental SAXS and SANS studies. Since the characteristic length scale of these domains is believed to be ˜2 to 5 nm, very large molecular dynamics (MD) simulations are needed to accurately probe the structure and morphology of these domains, especially their connectivity and percolation phenomena at varying water content. Using classical, all-atom MD with explicit hydronium ions, simulations have been performed to study the first-ever hydrated Nafion systems that are large enough (~2 million atoms in a ˜30 nm cell) to directly observe several hydrophilic domains at the molecular level. These systems consisted of six of the most significant and relevant morphological models of Nafion to-date: (1) the cluster-channel model of Gierke, (2) the parallel cylinder model of Schmidt-Rohr, (3) the local-order model of Dreyfus, (4) the lamellar model of Litt, (5) the rod network model of Kreuer, and (6) a 'random' model, commonly used in previous simulations, that does not directly assume any particular geometry, distribution, or morphology. These simulations revealed fast intercluster bridge formation and network percolation in all of the models. Sulfonates were found inside these bridges and played a significant role in percolation. Sulfonates also strongly aggregated around and inside clusters. Cluster surfaces were analyzed to study the hydrophilic-hydrophobic interface. Interfacial area and cluster volume

Interfacial Water-Transport Effects in Proton-Exchange Membranes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kienitz, Brian; Yamada, Haruhiko; Nonoyama, Nobuaki

2009-11-19

It is well known that the proton-exchange membrane is perhaps the most critical component of a polymer-electrolyte fuel cell. Typical membranes, such as Nafion(R), require hydration to conduct efficiently and are instrumental in cell water management. Recently, evidence has been shown that these membranes might have different interfacial morphology and transport properties than in the bulk. In this paper, experimental data combined with theoretical simulations will be presented that explore the existence and impact of interfacial resistance on water transport for Nafion(R) 21x membranes. A mass-transfer coefficient for the interfacial resistance is calculated from experimental data using different permeation cells.more » This coefficient is shown to depend exponentially on relative humidity or water activity. The interfacial resistance does not seem to exist for liquid/membrane or membrane/membrane interfaces. The effect of the interfacial resistance is to flatten the water-content profiles within the membrane during operation. Under typical operating conditions, the resistance is on par with the water-transport resistance of the bulk membrane. Thus, the interfacial resistance can be dominant especially in thin, dry membranes and can affect overall fuel-cell performance.« less

Highly efficient sulfonated polybenzimidazole as a proton exchange membrane for microbial fuel cells

NASA Astrophysics Data System (ADS)

Singha, Shuvra; Jana, Tushar; Modestra, J. Annie; Naresh Kumar, A.; Mohan, S. Venkata

2016-06-01

Although microbial fuel cells (MFCs) represent a promising bio-energy technology with a dual advantage (i.e., electricity production and waste-water treatment), their low power densities and high installation costs are major impediments. To address these bottlenecks and replace highly expensive Nafion, which is a proton exchange membrane (PEM), the current study focuses for the first time on membranes made from an easily synthesizable and more economical oxy-polybenzimidazole (OPBI) and its sulfonated analogue (S-OPBI) as alternate PEMs in single-chambered MFCs. The S-OPBI membrane exhibits better properties, with high water uptake, ion exchange capacity (IEC) and proton conductivity and a comparatively smaller degree of swelling compared to Nafion. The membrane morphology is characterized by atomic force microscopy, and the bright and dark regions of the S-OPBI membrane reveals the formation of ionic domains in the matrix, forming continuous water nanochannels when doped with water. These water-filled nanochannels are responsible for faster proton conduction in S-OPBI than in Nafion; therefore, the power output in the MFC with S-OPBI as the PEM is higher than in other MFCs. The open circuit voltage (460 mV), current generation (2.27 mA) and power density profile (110 mW/m2) as a function of time, as well as the polarization curves, exhibits higher current and power density (87.8 mW/m2) with S-OPBI compared to Nafion as the PEM.

High-performance Fuel Cell with Stretched Catalyst-Coated Membrane: One-step Formation of Cracked Electrode.

PubMed

Kim, Sang Moon; Ahn, Chi-Yeong; Cho, Yong-Hun; Kim, Sungjun; Hwang, Wonchan; Jang, Segeun; Shin, Sungsoo; Lee, Gunhee; Sung, Yung-Eun; Choi, Mansoo

2016-05-23

We have achieved performance enhancement of polymer electrolyte membrane fuel cell (PEMFC) though crack generation on its electrodes. It is the first attempt to enhance the performance of PEMFC by using cracks which are generally considered as defects. The pre-defined, cracked electrode was generated by stretching a catalyst-coated Nafion membrane. With the strain-stress property of the membrane that is unique in the aspect of plastic deformation, membrane electrolyte assembly (MEA) was successfully incorporated into the fuel cell. Cracked electrodes with the variation of strain were investigated and electrochemically evaluated. Remarkably, mechanical stretching of catalyst-coated Nafion membrane led to a decrease in membrane resistance and an improvement in mass transport, which resulted in enhanced device performance.

The transfer behavior of different ions across anion and cation exchange membranes under vanadium flow battery medium

NASA Astrophysics Data System (ADS)

Sun, Jiawei; Li, Xianfeng; Xi, Xiaoli; Lai, Qinzhi; Liu, Tao; Zhang, Huamin

2014-12-01

The transfer behavior of different ions (V2+, V3+, VO2+, VO2+, H+, SO42-) across ion exchange membranes is investigated under vanadium flow battery (VFB) operating condition. VX-20 anion exchange membrane (AEM) and Nafion 115 cation exchange membrane (CEM) are selected to investigate the influence of fixed charged groups on the transfer behavior of different ions. The interaction between different ions and water is discussed in detail aiming to ascertain the variation of different ions in the charge-discharge process. Under the VFB medium, the transfer behavior and function of different ions are very different for the AEM and CEM. V2+ ions at the negative side accumulate when VFB is assembled with Nafion 115, while the VO2+ ions at the positive side accumulate for VX-20. The SO42- ions will transfer across Nafion 115 to balance the charges and the protons can balance the charges of VX-20. Finally the capacity fade mechanism of different membranes is investigated, showing that the capacity decay of VFB assembled with Nafion 115 mainly results from the cross mix of vanadium ions across the membrane, however, for VX-20, the side reactions can be the major reason. This paper provides important information about electrolyte for the application of VFB.

A Low-Cost and High-Performance Sulfonated Polyimide Proton-Conductive Membrane for Vanadium Redox Flow/Static Batteries.

PubMed

Li, Jinchao; Yuan, Xiaodong; Liu, Suqin; He, Zhen; Zhou, Zhi; Li, Aikui

2017-09-27

A novel side-chain-type fluorinated sulfonated polyimide (s-FSPI) membrane is synthesized for vanadium redox batteries (VRBs) by high-temperature polycondensation and grafting reactions. The s-FSPI membrane has a vanadium ion permeability that is over an order of magnitude lower and has a proton selectivity that is 6.8 times higher compared to those of the Nafion 115 membrane. The s-FSPI membrane possesses superior chemical stability compared to most of the linear sulfonated aromatic polymer membranes reported for VRBs. Also, the vanadium redox flow/static batteries (VRFB/VRSB) assembled with the s-FSPI membranes exhibit stable battery performance over 100- and 300-time charge-discharge cycling tests, respectively, with significantly higher battery efficiencies and lower self-discharge rates than those with the Nafion 115 membranes. The excellent physicochemical properties and VRB performance of the s-FSPI membrane could be attributed to the specifically designed molecular structure with the hydrophobic trifluoromethyl groups and flexible sulfoalkyl pendants being introduced on the main chains of the membrane. Moreover, the cost of the s-FSPI membrane is only one-fourth that of the commercial Nafion 115 membrane. This work opens up new possibilities for fabricating high-performance proton-conductive membranes at low costs for VRBs.

Dispersion of Rod-like Particles of Nafion in Salt-Free Water/1-Propanol and Water/Ethanol Solutions.

PubMed

Yamaguchi, Makoto; Matsunaga, Takuro; Amemiya, Kazuki; Ohira, Akihiro; Hasegawa, Naoki; Shinohara, Kazuhiko; Ando, Masaki; Yoshida, Toshihiko

2014-12-26

The dispersion of perfluorinated sulfonic acid ionomers in catalyst inks is an important factor controlling the performance of catalyst layers in membrane electrode assemblies of proton exchange membrane fuel cells (PEMFCs). The effect of water/alcohol composition on the dispersion of H-Nafion in water/1-propanol and water/ethanol solutions was studied by dynamic light scattering (DLS), small-angle X-ray scattering (SAXS), and (19)F nuclear magnetic resonance ((19)F NMR) spectroscopy. Hydrodynamic radii calculated from DLS decay profiles and the radii and interparticle distance of rod-like particles derived from SAXS profiles showed almost the same dependence on alcohol concentration. 1-Propanol was more effective than ethanol to induce changes in the characteristic lengths of the rod-like particles. The motional narrowing in the (19)F NMR spectra by addition of 1-propanol indicates selective solvation of the rod-like particles. We suppose this might have decreased their radii and induced their elongation, which eventually led to extension of the ordered regions as observed in the hydrodynamic radii. Our study helps to clarify the dispersion of Nafion in aqueous alcohol solutions, which has implications for the performance of PEMFCs.

High-performance Fuel Cell with Stretched Catalyst-Coated Membrane: One-step Formation of Cracked Electrode

PubMed Central

Kim, Sang Moon; Ahn, Chi-Yeong; Cho, Yong-Hun; Kim, Sungjun; Hwang, Wonchan; Jang, Segeun; Shin, Sungsoo; Lee, Gunhee; Sung, Yung-Eun; Choi, Mansoo

2016-01-01

We have achieved performance enhancement of polymer electrolyte membrane fuel cell (PEMFC) though crack generation on its electrodes. It is the first attempt to enhance the performance of PEMFC by using cracks which are generally considered as defects. The pre-defined, cracked electrode was generated by stretching a catalyst-coated Nafion membrane. With the strain-stress property of the membrane that is unique in the aspect of plastic deformation, membrane electrolyte assembly (MEA) was successfully incorporated into the fuel cell. Cracked electrodes with the variation of strain were investigated and electrochemically evaluated. Remarkably, mechanical stretching of catalyst-coated Nafion membrane led to a decrease in membrane resistance and an improvement in mass transport, which resulted in enhanced device performance. PMID:27210793

Vanadium Redox Flow Batteries Using meta-Polybenzimidazole-Based Membranes of Different Thicknesses.

PubMed

Noh, Chanho; Jung, Mina; Henkensmeier, Dirk; Nam, Suk Woo; Kwon, Yongchai

2017-10-25

15, 25, and 35 μm thick meta-polybenzimidazole (PBI) membranes are doped with H 2 SO 4 and tested in a vanadium redox flow battery (VRFB). Their performances are compared with those of Nafion membranes. Immersed in 2 M H 2 SO 4 , PBI absorbs about 2 mol of H 2 SO 4 per mole of repeat unit. This results in low conductivity and low voltage efficiency (VE). In ex-situ tests, meta-PBI shows a negligible crossover of V 3+ and V 4+ ions, much lower than that of Nafion. This is due to electrostatic repulsive forces between vanadium cations and positively charged protonated PBI backbones, and the molecular sieving effect of PBI's nanosized pores. It turns out that charge efficiency (CE) of VRFBs using meta-PBI-based membranes is unaffected by or slightly increases with decreasing membrane thickness. Thick meta-PBI membranes require about 100 mV larger potentials to achieve the same charging current as thin meta-PBI membranes. This additional potential may increase side reactions or enable more vanadium ions to overcome the electrostatic energy barrier and to enter the membrane. On this basis, H 2 SO 4 -doped meta-PBI membranes should be thin to achieve high VE and CE. The energy efficiency of 15 μm thick PBI reaches 92%, exceeding that of Nafion 212 and 117 (N212 and N117) at 40 mA cm -2 .

Magnetically aligned nanodomains: application in high-performance ion conductive membranes.

PubMed

Hasani-Sadrabadi, Mohammad Mahdi; Majedi, Fatemeh Sadat; Coullerez, Géraldine; Dashtimoghadam, Erfan; VanDersarl, Jules John; Bertsch, Arnaud; Moaddel, Homayoun; Jacob, Karl I; Renaud, Philippe

2014-05-28

Polyelectrolyte-coated magnetic nanoparticles were prepared by decorating the surface of superparamagnetic iron oxide nanoparticles (SPIONs) with crosslinked chitosan oligopolysaccharide (CS). These positively charged particles (CS-SPIONs) were then added to a negatively charged polymer (Nafion), and cast into membranes under an applied magnetic field. TEM and SAXS measurements confirmed this process created aligned, cylindrical nanodomains in the membranes. This was also indirectly confirmed by proton conductivity values. The strong electrostatic interaction between chitosan and Nafion prevented oxygen permeability and water evaporation at elevated temperatures through the proton conductive channels. The resultant proton exchange membranes showed lower conduction dependency to relative humidity, which is highly desirable for hydrogen fuel cells. The fuel cell performance tests were performed on the designed polyelectrolyte membrane by hydrogen-oxygen single cells at elevated temperature (120 °C) and low relative humidity.

Nafion-coating of the electrodes improves the flow-stability of the Ag/SiO2/Ag2O electroosmotic pump.

PubMed

Shin, Woonsup; Zhu, Enhua; Nagarale, Rajaram Krishna; Kim, Chang Hwan; Lee, Jong Myung; Shin, Samuel Jaeho; Heller, Adam

2011-06-15

When a current or a voltage is applied across the ceramic membrane of the nongassing Ag/Ag(2)O-SiO(2)-Ag/Ag(2)O pump, protons produced in the anodic reaction 2Ag(s) + H(2)O → Ag(2)O(s) + 2H(+) + 2e(-) are driven to the cathode, where they are consumed by the reaction Ag(2)O(s) + H(2)O + 2e(-) → 2Ag(s) + 2 OH(-). The flow of water is induced by momentum transfer from the electric field-driven proton-sheet at the surface of the ceramic membrane. About 10(4) water molecules flowed per reacted electron. Because dissolved ions decrease the field at the membrane surface, the flow decreases upon increasing the ionic strength. For this reason Ag(+) ions introduced through the anodic reaction and by dissolution of Ag(2)O decrease the flow. Their accumulation is reduced by applying Nafion-films to the electrodes. The 20 μL min(-1) flow rate of 6 mm i.d. pumps with Nafion coated electrodes operate daily for 5 min at 1 V for 1 month, for 70 h when the pump is pulsed for 30 s every 30 min, and for 2 h when operating continuously.

Simple fabrication of 12 μm thin nanocomposite fuel cell membranes by direct electrospinning and printing

NASA Astrophysics Data System (ADS)

Breitwieser, Matthias; Klose, Carolin; Klingele, Matthias; Hartmann, Armin; Erben, Johannes; Cho, Hyeongrae; Kerres, Jochen; Zengerle, Roland; Thiele, Simon

2017-01-01

Direct membrane deposition (DMD) was recently introduced as a novel polymer electrolyte membrane fabrication method. Here, this approach is extended to fabricate 12 μm thin nanocomposite fuel cell membranes. Poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) nanofibers are directly electrospun onto gas diffusion electrodes. By inkjet-printing Nafion ionomer dispersion into the pore space of PVDF-HFP nanofiber mats, composite membranes of 12 μm thickness were fabricated. At 120 °C and 35% relative humidity, stoichiometric 1.5/2.5 H2/air flow and atmospheric pressure, the power density of the DMD fuel cell (0.19 W cm-2), was about 1.7 times higher than that of the reference fuel cell (0.11 W cm-2) with Nafion HP membrane and identical catalyst. A lower ionic resistance and, especially at 120 °C, a reduced charge transfer resistance is found compared to the Nafion HP membrane. A 100 h accelerated stress test revealed a voltage decay of below 0.8 mV h-1, which is in the range of literature values for significantly thicker reinforced membranes. Finally, this novel fabrication approach enables new degrees of freedom in the design of complex composite membranes. The presented combination of scalable deposition techniques has the potential to simplify and thus reduce cost of composite membrane fabrication at a larger scale.

NMR and Electrochemical Investigation of the Transport Properties of Methanol and Water in Nafion and Clay-Nanocomposites Membranes for DMFCs

PubMed Central

Nicotera, Isabella; Angjeli, Kristina; Coppola, Luigi; Aricò, Antonino S.; Baglio, Vincenzo

2012-01-01

Water and methanol transport behavior, solvents adsorption and electrochemical properties of filler-free Nafion and nanocomposites based on two smectite clays, were investigated using impedance spectroscopy, DMFC tests and NMR methods, including spin-lattice relaxation and pulsed-gradient spin-echo (PGSE) diffusion under variable temperature conditions. Synthetic (Laponite) and natural (Swy-2) smectite clays, with different structural and physical parameters, were incorporated into the Nafion for the creation of exfoliated nanocomposites. Transport mechanism of water and methanol appears to be influenced from the dimensions of the dispersed platelike silicate layers as well as from their cation exchange capacity (CEC). The details of the NMR results and the effect of the methanol solution concentration are discussed. Clays particles, and in particular Swy-2, demonstrate to be a potential physical barrier for methanol cross-over, reducing the methanol diffusion with an evident blocking effect yet nevertheless ensuring a high water mobility up to 130 °C and for several hours, proving the exceptional water retention property of these materials and their possible use in the DMFCs applications. Electrochemical behavior is investigated by cell resistance and polarization measurements. From these analyses it is derived that the addition of clay materials to recast Nafion decreases the ohmic losses at high temperatures extending in this way the operating range of a direct methanol fuel cell. PMID:24958179

TiO2/bi A-SPAES(Ds 1.0) composite membranes for proton exchange membrane in direct methanol fuel cell (DMFC).

PubMed

Zhang, Ni; Zhong, Chuanqing; Xie, Bing; Liu, Huiling; Wang, Xingzu

2014-09-01

A series of TiO2/bi A-SPAES(Ds 1.0) composite membranes with various contents of nano-sized TiO2 particles were prepared through sol-gel method. Scanning electron microscopy (SEM) images indicated the TiO2 particles were well dispersed within polymer matrix. These membranes were used for proton exchange membrane (PEM) for performance evaluation in direct methanol fuel cell (DMFC). These composite membranes showed good thermal stability and mechanical strength. It was found that the water uptake of these membranes enhanced with the TiO2 amount increasing in these composite membranes. Meanwhile, the introduction of TiO2 particles increased the proton conductivity and reduced the methanol permeability. The proton conductivities of these composite membranes with 8% TiO2 particles (0.120 S/cm and 0.128 S/cm) were higher than those of Nafion 117 membrane (0.114 S/cm and 0.117 S/cm) at 80 degrees C and 100 degrees C. Specially, the methanol diffusion coefficient (1.2 x 10(-7) cm2/s) of the composite membrane with 8% TiO2 content was much lower than that of Nafion 117 membrane (2.1 x 10(-6) cm2/s). As a result, the TiO2/bi A-SPAES composite membrane was considered as a promising material for PEM in DMFC.

Membrane water-flow rate in electrolyzer cells with a solid polymer electrolyte (SPE)

NASA Astrophysics Data System (ADS)

Li, Xiaojin; Qu, Shuguo; Yu, Hongmei; Hou, Ming; Shao, Zhigang; Yi, Baolian

Water-flow rate across Nafion membrane in SPE electrolyzer cells was measured and modelled. From the analysis of water transport mechanisms in SPE water electrolysis, the water-flow rate through membrane can be described by the electro-osmotic drag. The calculated electro-osmotic drag coefficients, n d, for the membrane in SPE electrolysis cells at different temperatures were compared with literature and in good agreement with those of Ge et al. and Ise et al. To describe the water-flow rate through membrane more accurately, a linear fit of n d as a function of temperature for the membrane in SPE water electrolysis was proposed in this paper. This paper studied the membrane water-flow rate experimentally and mathematically, which is of importance in the designing and optimization of the process of SPE water electrolysis. This paper also provided a novel method for measuring the electro-osmotic drag coefficient of Nafion membrane in contact with liquid water, acid and methanol solutions, etc.

Characterization of Sulfonated Diels-Alder Poly(phenylene) Membranes for Electrolyte Separators in Vanadium Redox Flow Batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tang, Zhijiang; Lawton, Jamie S.; Sun, Che-Nan

2014-09-03

Here, sulfonated Diels-Alder poly(phenylene) (SDAPP) membranes were synthesized and characterized as potential electrolyte separators for vanadium redox flow batteries. The SDAPP membranes studied had ion exchange capacities of 1.4, 1.8 and 2.3 meq/g. Transmission electron microscopy imaging shows that the ionic domains in SDAPP are roughly 0.5 nm in dimension, while Nafion has a hydrophilic phase width of around 5 nm. The sulfuric acid uptake by SDAPP was higher than that for Nafion, but the materials had similar water uptake from solutions of various sulfuric acid concentrations. In equilibration with sulfuric acid concentrations ranging from 0–17.4 mol·kg -1, SDAPP withmore » a IEC of 2.3 meq/g had the highest conductivity, ranging from 0.21 to 0.05 S·cm -1, while SDAPP with a IEC of 1.8 had conductivity close to Nafion 117, ranging from 0.11 to 0.02 S·cm -1. With varying sulfuric acid concentration and temperature, vanadium permeability in SDAPP is positively correlated to the membrane's IEC. The vanadium permeability of SDAPP 2.3 is similar to that of Nafion, but permeability values for SDAPP 1.8 and SDAPP 1.4 are substantially lower. The vanadium permeation decreases with increasing electrolyte sulfuric acid concentration. Lastly, vanadium diffusion activation energy is about 20 kJ·mol -1 in both SDAPP and Nafion.« less

Nafion coated sulfur-carbon electrode for high performance lithium-sulfur batteries

NASA Astrophysics Data System (ADS)

Tang, Qiwei; Shan, Zhongqiang; Wang, Li; Qin, Xue; Zhu, Kunlei; Tian, Jianhua; Liu, Xuesheng

2014-01-01

In this paper, a nafion coated electrode is prepared to improve the performance of lithium sulfur batteries. It is demonstrated from a series of measurements that the nafion layer is quite effective in reducing shuttle effect and enhancing the stability and the reversibility of the electrode. When measured under the rate of 0.2 C, the initial discharge capacity of the nafion coated electrode can reach 1084 mAh g-1, with a Columbic efficiency of about 100%. After 100 charge/discharge cycles, this electrode can also deliver a reversible capacity of as high as 879 mAh g-1. Significantly, the charge-transfer resistance of the electrode tends to be reducing after coated with an appropriate thickness of nafion film. The cation conductivity as well as anion inconductivity is considered to be the dominant factor for the superior electrochemical properties.

Polyarylenethioethersulfone Membranes for Fuel Cells (Postprint)

DTIC Science & Technology

2010-01-01

The Electrochemical SocietyProton exchange membrane fuel cells PEMFCs are an attrac- tive power source due to their energy efficiency and...standard in PEMFC technology.3,4 Nafion membranes have a polytetrafluoro- ethylene PTFE backbone, which provides thermal and chemical stability, and...diffusion layers to fabricate MEAs. Single-cell test (H- PEMFC ).— MEAs were positioned in a single-cell fixture with graphite blocks as current

An Evaluation of the Performance and Economics of Membranes and Separators in Single Chamber Microbial Fuel Cells Treating Domestic Wastewater.

PubMed

Christgen, Beate; Scott, Keith; Dolfing, Jan; Head, Ian M; Curtis, Thomas P

2015-01-01

The cost of materials is one of the biggest barriers for wastewater driven microbial fuel cells (MFCs). Many studies use expensive materials with idealistic wastes. Realistically the choice of an ion selective membrane or nonspecific separators must be made in the context of the cost and performance of materials available. Fourteen membranes and separators were characterized for durability, oxygen diffusion and ionic resistance to enable informed membrane selection for reactor tests. Subsequently MFCs were operated in a cost efficient reactor design using Nafion, ethylene tetrafluoroethylene (ETFE) or polyvinylidene fluoride (PVDF) membranes, a nonspecific separator (Rhinohide), and a no-membrane design with a carbon-paper internal gas diffusion cathode. Peak power densities during polarisation, from MFCs using no-membrane, Nafion and ETFE, reached 67, 61 and 59 mWm(-2), and coulombic efficiencies of 68±11%, 71±12% and 92±6%, respectively. Under 1000 Ω, Nafion and ETFE achieved an average power density of 29 mWm(-2) compared to 24 mWm(-2) for the membrane-less reactors. Over a hypothetical lifetime of 10 years the generated energy (1 to 2.5 kWhm(-2)) would not be sufficient to offset the costs of any membrane and separator tested.

An Evaluation of the Performance and Economics of Membranes and Separators in Single Chamber Microbial Fuel Cells Treating Domestic Wastewater

PubMed Central

Christgen, Beate; Scott, Keith; Dolfing, Jan; Head, Ian M.; Curtis, Thomas P.

2015-01-01

The cost of materials is one of the biggest barriers for wastewater driven microbial fuel cells (MFCs). Many studies use expensive materials with idealistic wastes. Realistically the choice of an ion selective membrane or nonspecific separators must be made in the context of the cost and performance of materials available. Fourteen membranes and separators were characterized for durability, oxygen diffusion and ionic resistance to enable informed membrane selection for reactor tests. Subsequently MFCs were operated in a cost efficient reactor design using Nafion, ethylene tetrafluoroethylene (ETFE) or polyvinylidene fluoride (PVDF) membranes, a nonspecific separator (Rhinohide), and a no-membrane design with a carbon-paper internal gas diffusion cathode. Peak power densities during polarisation, from MFCs using no-membrane, Nafion and ETFE, reached 67, 61 and 59 mWm-2, and coulombic efficiencies of 68±11%, 71±12% and 92±6%, respectively. Under 1000Ω, Nafion and ETFE achieved an average power density of 29 mWm-2 compared to 24 mWm-2 for the membrane-less reactors. Over a hypothetical lifetime of 10 years the generated energy (1 to 2.5 kWhm-2) would not be sufficient to offset the costs of any membrane and separator tested. PMID:26305330

Improved oxygen reduction reaction catalyzed by Pt/Clay/Nafion nanocomposite for PEM fuel cells.

PubMed

Narayanamoorthy, B; Datta, K K R; Eswaramoorthy, M; Balaji, S

2012-07-25

A novel Pt nanoparticle (Pt NP) embedded aminoclay/Nafion (Pt/AC/N) nanocomposite catalyst film was prepared for oxygen reduction reaction by sol-gel method. The prepared nanocomposite films were surface characterized using XRD and TEM and thermal stability was studied by TGA. The prepared film has firmly bound Pt NP and could exhibit an improved electro-reduction activity compared to vulcan carbon/Nafion supported Pt NP (Pt/VC/N). Moreover, the Pt/AC/N film possessed good stability in the acidic environment. The limiting current density of the Pt/AC/N film with 35.4 μg/cm(2) of Pt loading was found to be 4.2 mA/cm(2), which is 30% higher than that of the Pt/VC/N. The maximum H2O2 intermediate formation was found to be ∼1.6% and the reaction found to follow a four electron transfer mechanism. Accelerated durability test for 2000 potential cycles showed that ca. 78% of initial limiting current was retained. The results are encouraging for possible use of the Pt/AC/N as the free-standing electrocatalyst layer for polymer electrolyte membrane fuel cells.

Enhanced Proton Conductivity and Methanol Permeability Reduction via Sodium Alginate Electrolyte-Sulfonated Graphene Oxide Bio-membrane

NASA Astrophysics Data System (ADS)

Shaari, N.; Kamarudin, S. K.; Basri, S.; Shyuan, L. K.; Masdar, M. S.; Nordin, D.

2018-03-01

The high methanol crossover and high cost of Nafion® membrane are the major challenges for direct methanol fuel cell application. With the aim of solving these problems, a non-Nafion polymer electrolyte membrane with low methanol permeability and high proton conductivity based on the sodium alginate (SA) polymer as the matrix and sulfonated graphene oxide (SGO) as an inorganic filler (0.02-0.2 wt%) was prepared by a simple solution casting technique. The strong electrostatic attraction between -SO3H of SGO and the sodium alginate polymer increased the mechanical stability, optimized the water absorption and thus inhibited the methanol crossover in the membrane. The optimum properties and performances were presented by the SA/SGO membrane with a loading of 0.2 wt% SGO, which gave a proton conductivity of 13.2 × 10-3 Scm-1, and the methanol permeability was 1.535 × 10-7 cm2 s-1 at 25 °C, far below that of Nafion (25.1 × 10-7 cm2 s-1) at 25 °C. The mechanical properties of the sodium alginate polymer in terms of tensile strength and elongation at break were improved by the addition of SGO.

Mechanical and transport properties of layer-by-layer electrospun composite proton exchange membranes for fuel cell applications.

PubMed

Mannarino, Matthew M; Liu, David S; Hammond, Paula T; Rutledge, Gregory C

2013-08-28

Composite membranes composed of highly conductive and selective layer-by-layer (LbL) films and electrospun fiber mats were fabricated and characterized for mechanical strength and electrochemical selectivity. The LbL component consists of a proton-conducting, methanol-blocking poly(diallyl dimethyl ammonium chloride)/sulfonated poly(2,6-dimethyl-1,4-phenylene oxide) (PDAC/sPPO) thin film. The electrospun fiber component consists of poly(trimethyl hexamethylene terephthalamide) (PA 6(3)T) fibers in a nonwoven mat of 60-90% porosity. The bare mats were annealed to improve their mechanical properties, which improvements are shown to be retained in the composite membranes. Spray LbL assembly was used as a means for the rapid formation of proton-conducting films that fill the void space throughout the porous electrospun matrix and create a fuel-blocking layer. Coated mats as thin as 15 μm were fabricated, and viable composite membranes with methanol permeabilities 20 times lower than Nafion and through-plane proton selectivity five and a half times greater than Nafion are demonstrated. The mechanical properties of the spray coated electrospun mats are shown to be superior to the LbL-only system and possess intrinsically greater dimensional stability and lower mechanical hysteresis than Nafion under hydrated conditions. The composite proton exchange membranes fabricated here were tested in an operational direct methanol fuel cell. The results show the potential for higher open circuit voltages (OCV) and comparable cell resistances when compared to fuel cells based on Nafion.

Electrically driven ion separations and nanofiltration through membranes coated with polyelectrolyte multilayers

NASA Astrophysics Data System (ADS)

White, Nicholas

Polyelectrolyte multilayer (PEM) films deposited using the layer-by-layer (LBL) method are attractive for their simple deposition, tailorable nature, scalability, and charge or size-based selectivity for solutes. This dissertation explores ion separations in electrodialysis (ED) and solute removal through nanofiltration with PEMs deposited on polymer membranes. ED membranes typically exhibit modest selectivities between monovalent and divalent ions. In contrast, this work shows that K+/Mg 2+ ED selectivities reach values >1000 when using Nafion 115 cation-exchange membranes coated with multilayer poly(4-styrenesulfonate) (PSS)/protonated poly(allylamine) (PAH) films. For comparison, the corresponding K+ /Mg2+ selectivity of bare Nafion 115 is <2. However, water-splitting at strongly overlimiting current densities may lead to a local pH increase close to the membrane surface and alter film permeability or allow passage of Mg(OH)x species to decrease selectivity. When the source phase contains high salt concentrations, the K+ transference number approaches unity and the K+/Mg2+ selectivity is >20,000, presumably because the applied current is below the limiting value for K+ and H+ transport is negligible at this high K+ concentration. The high selectivities of these membranes may enable electrodialysis applications such as purification of salts that contain divalent or trivalent ions. The high ED selectivities of (PAH/PSS)5PAH-coated Nafion membranes translate to separations with Li+/Co2+ and K +/La3+. Even with adsorption of only 3 polyelectrolyte layers, Nafion membranes exhibit a Li+/Co2+ selectivity >23. However, the resistance to monovalent-ion passage does not decrease significantly with fewer polyelectrolyte layers. At overlimiting currents, hydroxides from water splitting form insoluble metal hydroxides to foul the membrane. With 0.1 M source-phase salt concentrations, transference numbers for monovalent cations approach unity and selectivities are >5000

Aqueous liquid feed organic fuel cell using solid polymer electrolyte membrane

NASA Technical Reports Server (NTRS)

Olah, George A. (Inventor); Surampudi, Subbarao (Inventor); Vamos, Eugene (Inventor); Halpert, Gerald (Inventor); Narayanan, Sekharipuram R. (Inventor); Frank, Harvey A. (Inventor); Prakash, G. K. Surya (Inventor)

1997-01-01

A liquid organic fuel cell is provided which employs a solid electrolyte membrane. An organic fuel, such as a methanol/water mixture, is circulated past an anode of a cell while oxygen or air is circulated past a cathode of the cell. The cell solid electrolyte membrane is preferably fabricated from Nafion.TM.. Additionally, a method for improving the performance of carbon electrode structures for use in organic fuel cells is provided wherein a high surface-area carbon particle/Teflon.TM.-binder structure is immersed within a Nafion.TM./methanol bath to impregnate the electrode with Nafion.TM.. A method for fabricating an anode for use in a organic fuel cell is described wherein metal alloys are deposited onto the electrode in an electro-deposition solution containing perfluorooctanesulfonic acid. A fuel additive containing perfluorooctanesulfonic acid for use with fuel cells employing a sulfuric acid electrolyte is also disclosed. New organic fuels, namely, trimethoxymethane, dimethoxymethane, and trioxane are also described for use with either conventional or improved fuel cells.

Hierarchical Nafion enhanced carbon aerogels for sensing applications

NASA Astrophysics Data System (ADS)

Weng, Bo; Ding, Ailing; Liu, Yuqing; Diao, Jianglin; Razal, Joselito; Lau, King Tong; Shepherd, Roderick; Li, Changming; Chen, Jun

2016-02-01

This work describes the fabrication of hierarchical 3D Nafion enhanced carbon aerogels (NECAGs) for sensing applications via a fast freeze drying method. Graphene oxide, multiwalled carbon nanotubes and Nafion were mixed and extruded into liquid nitrogen followed by the removal of ice crystals by freeze drying. The addition of Nafion enhanced the mechanical strength of NECAGs and effective control of the cellular morphology and pore size was achieved. The resultant NECAGs demonstrated high strength, low density, and high specific surface area and can achieve a modulus of 20 kPa, an electrical conductivity of 140 S m-1, and a specific capacity of 136.8 F g-1 after reduction. Therefore, NECAG monoliths performed well as a gas sensor and as a biosensor with high sensitivity and selectivity. The remarkable sensitivity of 8.52 × 103 μA mM-1 cm-2 was obtained in dopamine (DA) detection, which is two orders of magnitude better than the literature reported values using graphene aerogel electrodes made from a porous Ni template. These outstanding properties make the NECAG a promising electrode candidate for a wide range of applications. Further in-depth investigations are being undertaken to probe the structure-property relationship of NECAG monoliths prepared under various conditions.This work describes the fabrication of hierarchical 3D Nafion enhanced carbon aerogels (NECAGs) for sensing applications via a fast freeze drying method. Graphene oxide, multiwalled carbon nanotubes and Nafion were mixed and extruded into liquid nitrogen followed by the removal of ice crystals by freeze drying. The addition of Nafion enhanced the mechanical strength of NECAGs and effective control of the cellular morphology and pore size was achieved. The resultant NECAGs demonstrated high strength, low density, and high specific surface area and can achieve a modulus of 20 kPa, an electrical conductivity of 140 S m-1, and a specific capacity of 136.8 F g-1 after reduction. Therefore, NECAG

Fast stack activation procedure and effective long-term storage for high-performance polymer electrolyte membrane fuel cell

NASA Astrophysics Data System (ADS)

Yang, Seung Yong; Seo, Dong-Jun; Kim, Myeong-Ri; Seo, Min Ho; Hwang, Sun-Mi; Jung, Yong-Min; Kim, Beom-Jun; Yoon, Young-Gi; Han, Byungchan; Kim, Tae-Young

2016-10-01

Time-saving stack activation and effective long-term storage are one of most important issues that must be resolved for the commercialization of polymer electrolyte membrane fuel cell (PEMFC). Herein, we developed the cost-effective stack activation method to finish the whole activation within 30 min and the long-term storage method by using humidified N2 without any significant decrease in cell's performance for 30 days. Specifically, the pre-activation step with the direct injection of DI water into the stack and storage at 65 or 80 °C for 2 h increases the distinctive phase separation between the hydrophobic and hydrophilic regions in Nafion membrane, which significantly reduces the total activation time within 30 min. Additionally, the long-term storage with humidified N2 has no effect on the Pt oxidation and drying of Nafion membrane for 30 days due to its exergonic reaction in the cell. As a result, the high water content in Nafion membrane and the decrease of Pt oxidation are the critical factors that have a strong influence on the activation and long-term storage for high-performance PEMFC.

Polyarylenethioethersulfone Membranes for Fuel Cells (Postprint)

DTIC Science & Technology

2007-09-01

2007. 0013-4651/2007/1549/B960/9/$20.00 © The Electrochemical SocietyProton exchange membrane fuel cells PEMFCs are an attrac- tive power source...DuPont have become the commercially available standard in PEMFC technology.3,4 Nafion membranes have a polytetrafluoro- ethylene PTFE backbone, which...Inc. were used as anode and cathode gas diffusion layers to fabricate MEAs. Single-cell test (H- PEMFC ).— MEAs were positioned in a single-cell fixture

Sensor Properties of Field-Effect Transistors Based on Graphene Oxide and Nafion Films with Proton Conductivity

NASA Astrophysics Data System (ADS)

Smirnov, V. A.; Mokrushin, A. D.; Denisov, N. N.; Dobrovolsky, Yu. A.

2018-07-01

The proton conductivity of graphene oxide (GO) and Nafion films was studied depending on the humidity and voltage on electrodes. The electric properties of the films were similar, but the mobility of positive charges in Nafion was approximately two orders of magnitude higher than in GO. In GO films, the negative ion current with a positive voltage bias was up to 10% of the proton current, while in Nafion films it was almost absent (<1%). The sensors based on GO and Nafion films were most effective at humidity (RH) in the range 20-80%.

Conductivity in zeolite-polymer composite membranes for PEMFCs

NASA Astrophysics Data System (ADS)

Sancho, T.; Soler, J.; Pina, M. P.

Structured materials, such as zeolites can be candidates to be used as electrolytes in proton exchange membrane fuel cells (PEMFC) to substitute polymeric membranes, taking advantage of their higher chemical and thermal stability and their specific adsorption properties. The possibility to work at temperatures of nearly 150 °C would make easy the selection of the fuel, decreasing the influence of CO in the catalyst poisoning, and it would also improve the kinetics of the electrochemical reactions involved. In this work, four zeolites and related materials have been studied: mordenite, NaA zeolite, umbite and ETS-10. In special, the influence of relative humidity and temperature have been carefully explored. A conductivity cell was designed and built to measure in cross direction, by using the electrochemical impedance spectroscopy. The experimental system was validated using Nafion ® as a reference material by comparing the results with bibliography data. Samples were prepared by pressing the zeolite powders, with size of 1 μm on average, using polymer PVDF (10 wt.%) as a binder. The results here obtained, in spite of not reaching the absolute values of the Nafion ® ones, show a lower effect of the dehydration phenomenon on the conduction performance in the temperature range studied (from room temperature to 150 °C). This increase of the operation temperature range would give important advantages to the PEMFC. ETS-10 sample shows the best behaviour with respect to conductivity exhibiting an activation energy value comparable with reported for Nafion ® membrane.

Novel crosslinked membranes based on sulfonated poly(ether ether ketone) for direct methanol fuel cells.

PubMed

Zhu, Yuanqin; Zieren, Shelley; Manthiram, Arumugam

2011-07-14

Novel covalently crosslinked membranes based on sulfonated poly(ether ether ketone) and carboxylated polysulfone exhibit much lower methanol crossover and better performance in direct methanol fuel cells at 65 °C in 1 and 2 M methanol solutions compared to Nafion 115 membranes.

Reduction of methanol crossover by thin cracked metal barriers at the interface between membrane and electrode in direct methanol fuel cells

NASA Astrophysics Data System (ADS)

Kim, Sungjun; Jang, Segeun; Kim, Sang Moon; Ahn, Chi-Yeong; Hwang, Wonchan; Cho, Yong-Hun; Sung, Yung-Eun; Choi, Mansoo

2017-09-01

This work reports the successful reduction in methanol crossover by creating a thin cracked metal barrier at the interface between a Nafion® membrane and an electrode in direct methanol fuel cells (DMFCs). The cracks are generated by simple mechanical stretching of a metal deposited Nafion® membrane as a result of the elastic mismatch between the two attached surfaces. The cracked metal barriers with varying strains (∼0.5 and ∼1.0) are investigated and successfully incorporated into the DMFC. Remarkably, the membrane electrode assembly with the thin metal crack exhibits comparable ohmic resistance as well as reduction of methanol crossover, which enhanced the device performance.

Impedance Spectroscopic Investigation of Proton Conductivity in Nafion Using Transient Electrochemical Atomic Force Microscopy (AFM)

PubMed Central

Hink, Steffen; Wagner, Norbert; Bessler, Wolfgang G.; Roduner, Emil

2012-01-01

Spatially resolved impedance spectroscopy of a Nafion polyelectrolyte membrane is performed employing a conductive and Pt-coated tip of an atomic force microscope as a point-like contact and electrode. The experiment is conducted by perturbing the system by a rectangular voltage step and measuring the incurred current, followed by Fourier transformation and plotting the impedance against the frequency in a conventional Bode diagram. To test the potential and limitations of this novel method, we present a feasibility study using an identical hydrogen atmosphere at a well-defined relative humidity on both sides of the membrane. It is demonstrated that good quality impedance spectra are obtained in a frequency range of 0.2–1000 Hz. The extracted polarization curves exhibit a maximum current which cannot be explained by typical diffusion effects. Simulation based on equivalent circuits requires a Nernst element for restricted diffusion in the membrane which suggests that this effect is based on the potential dependence of the electrolyte resistance in the high overpotential region. PMID:24958175

Correlating Humidity-Dependent Ionically Conductive Surface Area with Transport Phenomena in Proton-Exchange Membranes

DOE Office of Scientific and Technical Information (OSTI.GOV)

He, Qinggang; Kusoglu, Ahmet; Lucas, Ivan T.

2011-08-01

The objective of this effort was to correlate the local surface ionic conductance of a Nafion? 212 proton-exchange membrane with its bulk and interfacial transport properties as a function of water content. Both macroscopic and microscopic proton conductivities were investigated at different relative humidity levels, using electrochemical impedance spectroscopy and current-sensing atomic force microscopy (CSAFM). We were able to identify small ion-conducting domains that grew with humidity at the surface of the membrane. Numerical analysis of the surface ionic conductance images recorded at various relative humidity levels helped determine the fractional area of ion-conducting active sites. A simple square-root relationshipmore » between the fractional conducting area and observed interfacial mass-transport resistance was established. Furthermore, the relationship between the bulk ionic conductivity and surface ionic conductance pattern of the Nafion? membrane was examined.« less

Spectroscopic determination of anthraquinone in kraft pulping liquors using a membrane interface

Treesearch

X.S. Chai; X.T. Yang; Q.X. Hou; J.Y. Zhu; L.-G. Danielsson

2003-01-01

A spectroscopic technique for determining AQ in pulping liquor was developed to effectively separate AQ from dissolved lignin. This technique is based on a flow analysis system with a Nafion membrane interface. The AQ passed through the membrane is converted into its reduced form, AHQ, using sodium hydrosulfite. AHQ has distinguished absorption characteristics in the...

Development and characterization of membrane electrode assembly of direct methanol fuel cells using hydrocarbon membranes and supported catalysts

NASA Astrophysics Data System (ADS)

Huang, Xiaoming

Direct methanol fuel cell (DMFC) is an attractive power source for portable applications in the near future, due to the high energy density of liquid methanol. Towards commercialization of the DMFC, several technical and economic challenges need to be addressed though. The present study aims at developing and characterizing high performance membrane electrode assemblies (MEAs) for the DMFCs by using a hydrocarbon type membrane (PolyFuel 62) and supported catalysts (PtRu/C). First, methanol and water transport properties in the PolyFuel 62 membrane were examined by various material characterization methods. Compared with the currently used perflurosulfonated Nafion 212 membrane, the PolyFuel membrane has lower methanol crossover, especially at high testing temperature. In addition, based on results of water diffusivity test, water diffusion through the PolyFuel membrane was also lower compared with the Nafion membrane. In order to check the possible impacts of the low methanol and water diffusivities in the PolyFuel membrane, a MEA with this new type of membrane was developed and its performance was compared with a Nafion MEA with otherwise identical electrodes and GDLs. The results showed anode performance was identical, while cathode performance of the PolyFuel MEA was lower. More experiments combined with a transmission line model revealed that low water transport through the PolyFuel membrane resulted in a higher proton resistance in the cathode electrode and thus, leading to a low cathode performance. Thus increasing the water content in the cathode electrode is critical for using the PolyFuel membrane in the DMFC MEA. Then, a low loading carbon supported catalyst, PtRu/C, was prepared and tested as the anode electrode in a MEA of the DMFC. Compared with performance of an unsupported MEA, we could find that lower performance in the supported MEA was due to methanol transport limitation because of the denser and thicker supported catalyst layer. Accordingly, an

Morphological and electromechanical characterization of ionic liquid/Nafion polymer composites

NASA Astrophysics Data System (ADS)

Bennett, Matthew; Leo, Donald

2005-05-01

Ionic liquids have shown promise as replacements for water in ionic polymer transducers. Ionic liquids are non-volatile and have a larger electrochemical stability window than water. Therefore, transducers employing ionic liquids can be operated for long periods of time in air and can be actuated with higher voltages. Furthermore, transducers based on ionic liquids do not exhibit the characteristic back relaxation that is common with water-swollen materials. However, the physics of transduction in the ionic liquid-swollen materials is not well understood. In this paper, the morphology of Nafion/ionic liquid composites is characterized using small-angle X-ray scattering (SAXS). The electromechanical transduction behavior of the composites is also investigated. For this testing, five different counterions and two ionic liquids are used. The results reveal that both the morphology and transduction performance of the composites is affected by the identity of the ionic liquid, the cation, and the swelling level of ionic liquid within the membrane. Specifically, speed of response is found to be lower for the membranes that were exchanged with the smaller lithium and potassium ions. The response speed is also found to increase with increased content of ionic liquid. Furthermore, for the two ionic liquids studied, the actuators swollen with the less viscous ionic liquid exhibited a slower response. The slower speed of response corresponds to less contrast between the ionically conductive phase and the inert phase of the polymer. This suggests that disruption of the clustered morphology in the ionic liquid-swollen membranes as compared to water-swollen membranes attenuates ion mobility within the polymer. This attenuation is attributed to swelling of the non-conductive phase by the ionic liquids.

Characterization of proton exchange membrane materials for fuel cells by solid state nuclear magnetic resonance

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kong, Zueqian

2010-01-01

Solid-state nuclear magnetic resonance (NMR) has been used to explore the nanometer-scale structure of Nafion, the widely used fuel cell membrane, and its composites. We have shown that solid-state NMR can characterize chemical structure and composition, domain size and morphology, internuclear distances, molecular dynamics, etc. The newly-developed water channel model of Nafion has been confirmed, and important characteristic length-scales established. Nafion-based organic and inorganic composites with special properties have also been characterized and their structures elucidated. The morphology of Nafion varies with hydration level, and is reflected in the changes in surface-to-volume (S/V) ratio of the polymer obtained by small-anglemore » X-ray scattering (SAXS). The S/V ratios of different Nafion models have been evaluated numerically. It has been found that only the water channel model gives the measured S/V ratios in the normal hydration range of a working fuel cell, while dispersed water molecules and polymer ribbons account for the structures at low and high hydration levels, respectively.« less

Polymer Electrolyte Membranes for Water Photo-Electrolysis

PubMed Central

Aricò, Antonino S.; Girolamo, Mariarita; Siracusano, Stefania; Sebastian, David; Baglio, Vincenzo; Schuster, Michael

2017-01-01

Water-fed photo-electrolysis cells equipped with perfluorosulfonic acid (Nafion® 115) and quaternary ammonium-based (Fumatech® FAA3) ion exchange membranes as separator for hydrogen and oxygen evolution reactions were investigated. Protonic or anionic ionomer dispersions were deposited on the electrodes to extend the interface with the electrolyte. The photo-anode consisted of a large band-gap Ti-oxide semiconductor. The effect of membrane characteristics on the photo-electrochemical conversion of solar energy was investigated for photo-voltage-driven electrolysis cells. Photo-electrolysis cells were also studied for operation under electrical bias-assisted mode. The pH of the membrane/ionomer had a paramount effect on the photo-electrolytic conversion. The anionic membrane showed enhanced performance compared to the Nafion®-based cell when just TiO2 anatase was used as photo-anode. This was associated with better oxygen evolution kinetics in alkaline conditions compared to acidic environment. However, oxygen evolution kinetics in acidic conditions were significantly enhanced by using a Ti sub-oxide as surface promoter in order to facilitate the adsorption of OH species as precursors of oxygen evolution. However, the same surface promoter appeared to inhibit oxygen evolution in an alkaline environment probably as a consequence of the strong adsorption of OH species on the surface under such conditions. These results show that a proper combination of photo-anode and polymer electrolyte membrane is essential to maximize photo-electrolytic conversion. PMID:28468242

Polymer Electrolyte Membranes for Water Photo-Electrolysis.

PubMed

Aricò, Antonino S; Girolamo, Mariarita; Siracusano, Stefania; Sebastian, David; Baglio, Vincenzo; Schuster, Michael

2017-04-29

Water-fed photo-electrolysis cells equipped with perfluorosulfonic acid (Nafion ® 115) and quaternary ammonium-based (Fumatech ® FAA3) ion exchange membranes as separator for hydrogen and oxygen evolution reactions were investigated. Protonic or anionic ionomer dispersions were deposited on the electrodes to extend the interface with the electrolyte. The photo-anode consisted of a large band-gap Ti-oxide semiconductor. The effect of membrane characteristics on the photo-electrochemical conversion of solar energy was investigated for photo-voltage-driven electrolysis cells. Photo-electrolysis cells were also studied for operation under electrical bias-assisted mode. The pH of the membrane/ionomer had a paramount effect on the photo-electrolytic conversion. The anionic membrane showed enhanced performance compared to the Nafion ® -based cell when just TiO₂ anatase was used as photo-anode. This was associated with better oxygen evolution kinetics in alkaline conditions compared to acidic environment. However, oxygen evolution kinetics in acidic conditions were significantly enhanced by using a Ti sub-oxide as surface promoter in order to facilitate the adsorption of OH species as precursors of oxygen evolution. However, the same surface promoter appeared to inhibit oxygen evolution in an alkaline environment probably as a consequence of the strong adsorption of OH species on the surface under such conditions. These results show that a proper combination of photo-anode and polymer electrolyte membrane is essential to maximize photo-electrolytic conversion.

Studies on Molecular and Ion Transport in Silicalite Membranes and Applications as Ion Separator for Redox Flow Battery

NASA Astrophysics Data System (ADS)

Yang, Ruidong

Microporous zeolite membranes have been widely studied for molecular separations based on size exclusion or preferential adsorption-diffusion mechanisms. The MFI-type zeolite membranes were also demonstrated for brine water desalination by molecular sieving effect. In this research, the pure silica MFI-type zeolite (i.e. silicalite) membrane has been for the first time demonstrated for selective permeation of hydrated proton (i.e. H3O+) in acidic electrolyte solutions. The silicalite membrane allows for permeation of H 3O+ ions, but is inaccessible to the large hydrated multivalent vanadium ions due to steric effect. The silicalite membrane has been further demonstrated as an effective ion separator in the all-vanadium redox flow battery (RFB).The silicalite is nonionic and its proton conductivity relies on the electric field-driven H3O+ transport through the sub nanometer-sized pores under the RFB operation conditions. The silicalite membrane displayed a significantly reduced self-discharge rate because of its high proton-to-vanadium ion transport selectivity. However, the nonionic nature of the silicalite membrane and very small diffusion channel size render low proton conductivity and is therefore inefficient as ion exchange membranes (IEMs) for practical applications. The proton transport efficiency may be improved by reducing the membrane thickness. However, the zeolite thin films are extremely fragile and must be supported on mechanically strong and rigid porous substrates. In this work, silicalite-Nafion composite membranes were synthesized to achieve a colloidal silicalite skin on the Nafion thin film base. The "colloidal zeolite-ionic polymer" layered composite membrane combines the advantages of high proton-selectivity of the zeolite layer and the mechanical flexibility and low proton transport resistance of the ionic polymer membrane. The composite membrane exhibited higher proton/vanadium ion separation selectivity and lower electrical resistance than

Electrocatalytic response of poly(cobalt tetraaminophthalocyanine)/multi-walled carbon nanotubes-Nafion modified electrode toward sulfadiazine in urine*

PubMed Central

Hong, Xiao-ping; Zhu, Yan; Zhang, Yan-zhen

2012-01-01

A highly sensitive amperometric sulfadiazine sensor fabricated by electrochemical deposition of poly(cobalt tetraaminophthalocyanine) (poly(CoIITAPc)) on the surface of a multi-walled carbon nanotubes-Nafion (MWCNTs-Nafion) modified electrode is described. This electrode showed a very attractive performance by combining the advantages of CoIITAPc, MWCNTs, and Nafion. Compared with the bare glassy carbon electrode (GCE) and the MWCNTs-Nafion modified electrode, the electrocatalytic activity of poly(CoIITAPc)-coated MWCNTs-Nafion GCE generated greatly improved electrochemical detections toward sulfadiazine including low oxidation potential, high current responses, and good anti-fouling performance. The oxidation peak currents of sulfadiazine obtained on the new modified electrode increased linearly while increasing the concentration of sulfadiazine from 0.5 to 43.5 μmol/L with the detection limit of 0.17 μmol/L. PMID:22661213

Power generation using different cation, anion, and ultrafiltration membranes in microbial fuel cells.

PubMed

Kim, Jung Rae; Cheng, Shaoan; Oh, Sang-Eun; Logan, Bruce E

2007-02-01

Proton exchange membranes (PEMs) are often used in microbial fuel cells (MFCs) to separate the liquid in the anode and cathode chambers while allowing protons to pass between the chambers. However, negatively or positively charged species present at high concentrations in the medium can also be used to maintain charge balance during power generation. An anion exchange membrane (AEM) produced the largest power density (up to 610 mW/m2) and Coulombic efficiency (72%) in MFCs relative to values achieved with a commonly used PEM (Nafion), a cation exchange membrane (CEM), or three different ultrafiltration (UF) membranes with molecular weight cut offs of 0.5K, 1K, and 3K Daltons in different types of MFCs. The increased performance of the AEM was due to proton charge-transfer facilitated by phosphate anions and low internal resistance. The type of membrane affected maximum power densities in two-chamber, air-cathode cube MFCs (C-MFCs) with low internal resistance (84-91 omega for all membranes except UF-0.5K) but not in two-chamber aqueous-cathode bottle MFCs (B-MFCs) due to their higher internal resistances (1230-1272 omega except UF-0.5K). The UF-0.5K membrane produced very high internal resistances (6009 omega, B-MFC; 1814omega, C-MFC) and was the least permeable to both oxygen (mass transfer coefficient of k(O) = 0.19 x 10(-4) cm/s) and acetate (k(A) = 0.89 x 10(-8) cm/s). Nafion was the most permeable membrane to oxygen (k(O) = 1.3 x 10(-4) cm/s), and the UF-3K membrane was the most permeable to acetate (k(A) = 7.2 x 10(-8) cm/s). Only a small percent of substrate was unaccounted for based on measured Coulombic efficiencies and estimates of biomass production and substrate losses using Nafion, CEM, and AEM membranes (4-8%), while a substantial portion of substrate was lost to unidentified processes for the UF membranes (40-89%). These results show that many types of membranes can be used in two-chambered MFCs, even membranes that transfer negatively charged

Proton conducting membranes for high temperature fuel cells with solid state water free membranes

NASA Technical Reports Server (NTRS)

Narayanan, Sekharipuram R. (Inventor); Yen, Shiao-Pin S. (Inventor)

2006-01-01

A water free, proton conducting membrane for use in a fuel cell is fabricated as a highly conducting sheet of converted solid state organic amine salt, such as converted acid salt of triethylenediamine with two quaternized tertiary nitrogen atoms, combined with a nanoparticulate oxide and a stable binder combined with the converted solid state organic amine salt to form a polymeric electrolyte membrane. In one embodiment the membrane is derived from triethylenediamine sulfate, hydrogen phosphate or trifiate, an oxoanion with at least one ionizable hydrogen, organic tertiary amine bisulfate, polymeric quaternized amine bisulfate or phosphate, or polymeric organic compounds with quaternizable nitrogen combined with Nafion to form an intimate network with ionic interactions.

Investigation of Proton Conductivity of Cation-Exchanged, Sulfonated Poly(b-Styrene-b-Isobutylene-b-Styrene) Membranes

DTIC Science & Technology

2009-09-01

solvents. Similar behavior was observed for Nafion -117 (also a polymer with ionic SO3H clusters) by other researchers (14). Results shown in this...pattern was only valid for ionic S-SIBS membranes exchanged with cations; neither acid form of SIBS-97-H nor Nafion -117 fell on this line. In order...10  vi INTENTIONALLY LEFT BLANK. 1 1. Introduction Research in ionic polymers has been gaining popularity in the scientific community

Al2O3 Disk Supported Si3N4 Hydrogen Purification Membrane for Low Temperature Polymer Electrolyte Membrane Fuel Cells.

PubMed

Liu, Xiaoteng; Christensen, Paul A; Kelly, Stephen M; Rocher, Vincent; Scott, Keith

2013-12-05

Reformate gas, a commonly employed fuel for polymer electrolyte membrane fuel cells (PEMFCs), contains carbon monoxide, which poisons Pt-containing anodes in such devices. A novel, low-cost mesoporous Si3N4 selective gas separation material was tested as a hydrogen clean-up membrane to remove CO from simulated feed gas to single-cell PEMFC, employing Nafion as the polymer electrolyte membrane. Polarization and power density measurements and gas chromatography showed a clear effect of separating the CO from the gas mixture; the performance and durability of the fuel cell was thereby significantly improved.

Concentration Dependence of VO2+ Crossover of Nafion for Vanadium Redox Flow Batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lawton, Jamie; Jones, Amanda; Zawodzinski, Thomas A

2013-01-01

The VO2+ crossover, or permeability, through Nafion in a vanadium redox flow battery (VRFB) was monitored as a function of sulfuric acid concentration and VO2+ concentration. A vanadium rich solution was flowed on one side of the membrane through a flow field while symmetrically on the other side a blank or vanadium deficit solution was flowed. The blank solution was flowed through an electron paramagnetic resonance (EPR) cavity and the VO2+ concentration was determined from the intensity of the EPR signal. Concentration values were fit using a solution of Fick s law that allows for the effect of concentration changemore » on the vanadium rich side. The fits resulted in permeability values of VO2+ ions across the membrane. Viscosity measurements of many VO2+ and H2SO4 solutions were made at 30 60 C. These viscosity values were then used to determine the effect of the viscosity of the flowing solution on the permeability of the ion. 2013 The Electrochemical Society. [DOI: 10.1149/2.004306jes] All rights reserved.« less

Voltammetric determination of Cd2+ based on the bifunctionality of single-walled carbon nanotubes-Nafion film.

PubMed

Sun, Dong; Xie, Xiafeng; Cai, Yuepiao; Zhang, Huajie; Wu, Kangbing

2007-01-02

In the presence of Nafion, single-walled carbon nanotubes (SWNTs) were easily dispersed into ethanol, resulting in a homogeneous SWNTs/Nafion suspension. After evaporating ethanol, a SWNTs/Nafion film with bifunctionality was constructed onto glassy carbon electrode (GCE) surface. Attributing to the strong cation-exchange ability of Nafion and excellent properties of SWNTs, the SWNTs/Nafion film-coated GCE remarkably enhances the sensitivity of determination of Cd(2+). Based on this, an electrochemical method was developed for the determination of trace levels of Cd(2+) by anodic stripping voltammetry (ASV). In pH 5.0 NaAc-HAc buffer, Cd(2+) was firstly exchanged and adsorbed onto SWNTs/Nafion film surface, and then reduce at -1.10 V. During the positive potential sweep, reduced cadmium was oxidized, and a well-defined stripping peak appeared at -0.84 V, which can be used as analytical signal for Cd(2+). The linear range is found to be from 4.0 x 10(-8) to 4.0 x 10(-6) mol L(-1), and the lowest detectable concentration is estimated to be 4.0 x 10(-9) mol L(-1). Finally, this method was successfully employed to detect Cd(2+) in water samples.

AC impedance and conductivity study of alkali salt form [of] perfluorosulfonate ionomer membranes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zaluski, C.S.; Xu, G.

1994-02-01

AC impedance studies were performed on Na+ and K+ alkali salt forms of the short sidechain perfluorosulfonate ionomer (PFSI) membrane films. With impressive performances of 4 A/cm[sup 2] current density and power densities near 2.5 W/cm[sup 2], the acid forms of these short sidechain PFSI are very promising candidates for use in fuel cells for future electric vehicles. Since, at present, little is known about the exact transport mechanisms for the ionic species within PFSIs, an ac impedance study of the Na+ and K+ forms has been performed. It is hoped that this will provide some insight and understanding ofmore » the transport mechanisms in the PFSI and thus will aid in the development and optimization of fuel cells. Results suggest that there are marked differences with respect to host environments within the Dow membrane as compared to Nafion[reg sign] long sidechain PFSI membrane films. Impedance spectra of the Dow salt form membranes displaying two distinct relaxation peaks while the spectra for all forms of Nafion reveal only a single peak. This second low temperature peak in the Dow membrane has been attributed to a much larger [OH[sup [minus

A novel crosslinking strategy for preparing poly(vinyl alcohol)-based proton-conducting membranes with high sulfonation

NASA Astrophysics Data System (ADS)

Tsai, Chun-En; Lin, Chi-Wen; Hwang, Bing-Joe

This study synthesizes poly(vinyl alcohol) (PVA)-based polymer electrolyte membranes by a two-step crosslinking process involving esterization and acetal ring formation reactions. This work also uses sulfosuccinic acid (SSA) as the first crosslinking agent to form an inter-crosslinked structure and a promoting sulfonating agent. Glutaraldehyde (GA) as the second crosslinking agent, reacts with the spare OH group of PVA and forms, not only a dense structure at the outer membrane surface, but also a hydrophobic protective layer. Compared with membranes prepared by a traditional one-step crosslinking process, membranes prepared by the two-step crosslinking process exhibit excellent dissolution resistance in water. The membranes become water-insoluble even at a molar ratio of SO 3H/PVA-OH as high as 0.45. Moreover, the synthesized membranes also exhibit high proton conductivities and high methanol permeability resistance. The current study measures highest proton conductivity of 5.3 × 10 -2 S cm -1 at room temperature from one of the synthesized membranes, higher than that of the Nafion ® membrane. Methanol permeability of the synthesized membranes measures about 1 × 10 -7 cm 2 S -1, about one order of magnitude lower than that of the Nafion ® membrane.

Intermolecular ionic cross-linked sulfonated poly(ether ether ketone) membranes containing diazafluorene for direct methanol fuel cell applications

NASA Astrophysics Data System (ADS)

Liang, Yu; Gong, Chenliang; Qi, Zhigang; Li, Hui; Wu, Zhongying; Zhang, Yakui; Zhang, Shujiang; Li, Yanfeng

2015-06-01

A series of novel ionic cross-linking sulfonated poly(ether ether ketone) (SPEEK) membranes containing the diazafluorene functional group are synthesized to reduce the swelling ratio and methanol permeability for direct methanol fuel cell (DMFC) applications. The ionic cross-linking is realized by the interaction between sulfonic acid groups and pyridyl in diazafluorene. The prepared membranes exhibit good mechanical properties, adequate thermal stability, good oxidative stability, appropriate water uptake and low swelling ratio. Moreover, the ionic cross-linked membranes exhibit lower methanol permeability in the range between 0.56 × 10-7 cm2 s-1 and 1.8 × 10-7 cm2 s-1, which is lower than Nafion 117, and they exhibit higher selectivity than Nafion 117 at 30 °C on the basis of applicable proton conductivity.

Sulfonated Holey Graphene Oxide (SHGO) Filled Sulfonated Poly(ether ether ketone) Membrane: The Role of Holes in the SHGO in Improving Its Performance as Proton Exchange Membrane for Direct Methanol Fuel Cells.

PubMed

Jiang, Zhong-Jie; Jiang, Zhongqing; Tian, Xiaoning; Luo, Lijuan; Liu, Meilin

2017-06-14

Sulfonated holey graphene oxides (SHGOs) have been synthesized by the etching of sulfonated graphene oxides with concentrated HNO 3 under the assistance of ultrasonication. These SHGOs could be used as fillers for the sulfonated aromatic poly(ether ether ketone) (SPEEK) membrane. The obtained SHGO-incorporated SPEEK membrane has a uniform and dense structure, exhibiting higher performance as proton exchange membranes (PEMs), for instance, higher proton conductivity, lower activation energy for proton conduction, and comparable methanol permeability, as compared to Nafion 112. The sulfonated graphitic structure of the SHGOs is believed to be one of the crucial factors resulting in the higher performance of the SPEEK/SHGO membrane, since it could increase the local density of the -SO 3 H groups in the membrane and induce a strong interfacial interaction between SHGO and the SPEEK matrix, which improve the proton conductivity and lower the swelling ratio of the membrane, respectively. Additionally, the proton conductivity of the membrane could be further enhanced by the presence of the holes in the graphitic planes of the SHGOs, since it provides an additional channel for transport of the protons. When used, direct methanol fuel cell with the SPEEK/SHGO membrane is found to exhibit much higher performance than that with Nafion 112, suggesting potential use of the SPEEK/SHGO membrane as the PEMs.

Gold Nanoparticles-Enhanced Proton Exchange Membrane (PEM) Fuel Cell

NASA Astrophysics Data System (ADS)

Li, Hongfei; Pan, Cheng; Liu, Ping; Zhu, Yimei; Adzic, Radoslav; Rafailovich, Miriam

Proton exchange membrane fuel cells have drawn great attention and been taken as a promising alternated energy source. One of the reasons hamper the wider application of PEM fuel cell is the catalytic poison effect from the impurity of the gas flow. Haruta has predicted that gold nanoparticles that are platelet shaped and have direct contact with the metal oxide substrate to be the perfect catalysts of the CO oxidization, yet the synthesis method is difficult to apply in the Fuel Cell. In our approach, thiol-functionalized gold nanoparticles were synthesized through two-phase method developed by Brust et al. We deposit these Au particles with stepped surface directly onto the Nafion membrane in the PEM fuel cell by Langmuir-Blodgett method, resulting in over 50% enhancement of the efficiency of the fuel cell. DFT calculations were conducted to understand the theory of this kind of enhancement. The results indicated that only when the particles were in direct surface contact with the membrane, where AuNPs attached at the end of the Nafion side chains, it could reduce the energy barrier for the CO oxidation that could happen at T<300K.

Ion-exchange composite membranes pore-filled with sulfonated poly(ether ether ketone) and Engelhard titanosilicate-10 for improved performance of vanadium redox flow batteries

NASA Astrophysics Data System (ADS)

Kim, Jihoon; Lee, Yongkyu; Jeon, Jae-Deok; Kwak, Seung-Yeop

2018-04-01

A series of ion-exchange membranes for vanadium redox flow batteries (VRBs) are prepared by filling the pores of a poly(tetrafluoroethylene) (PTFE) substrate with sulfonated poly(ether ether ketone) (SPEEK) and microporous Engelhard titanosilicate-10 (ETS-10). The effects of ETS-10 incorporation and PTFE reinforcement on membrane properties and VRB single-cell performance are investigated using various characterization tools. The results show that these composite membranes exhibit improved mechanical properties and reduced vanadium-ion permeabilities owing to the interactions between ETS-10 and SPEEK, the suppressed swelling of PTFE, and the unique ETS-10 framework. The composite membrane with 3 wt% ETS-10 (referred to as "SE3/P") exhibits the best membrane properties and highest ion selectivity. The VRB system with the SE3/P membrane exhibits higher cell capacity, higher cell efficiency, and lower capacity decay than that with a Nafion membrane. These results indicate that this composite membrane has potential as an alternative to Nafion in VRB systems.

Pendant dual sulfonated poly(arylene ether ketone) proton exchange membranes for fuel cell application

NASA Astrophysics Data System (ADS)

Nguyen, Minh Dat Thinh; Yang, Sungwoo; Kim, Dukjoon

2016-10-01

Poly(arylene ether ketone) (PAEK) possessing carboxylic groups at the pendant position is synthesized, and the substitution degree of pendant carboxylic groups is controlled by adjusting the ratio of 4,4-bis(4-hydroxyphenyl)valeric acid and 2,2-bis(4-hydroxyphenyl)propane. Dual sulfonated 3,3-diphenylpropylamine (SDPA) is grafted onto PAEK as a proton-conducting moiety via the amidation reaction with carboxylic groups. The transparent and flexible membranes with different degrees of sulfonation are fabricated so that we can test and compare their structure and properties with a commercial Nafion® 115 membrane for PEMFC applications. All prepared PAEK-SDPA membranes exhibit good oxidative and hydrolytic stability from Fenton's and high temperature water immersion test. SAXS analysis illustrates an excellent phase separation between the hydrophobic backbone and hydrophilic pendant groups, resulting in big ionic clusters. The proton conductivity was measured at different relative humidity, and its behavior was analyzed by hydration number of the membrane. Among a series of membranes, some samples (including B20V80-SDPA) show not only higher proton conductivity, but also higher integrated cell performance than those of Nafion® 115 at 100% relative humidity, and thus we expect these to be good candidate membranes for proton exchange membrane fuel cells (PEMFCs).

Low Permeable Hydrocarbon Polymer Electrolyte Membrane for Vanadium Redox Flow Battery.

PubMed

Jung, Ho-Young; Moon, Geon-O; Jung, Seunghun; Kim, Hee Tak; Kim, Sang-Chai; Roh, Sung-Hee

2017-04-01

Polymer electrolyte membrane (PEM) confirms the life span of vanadium redox flow battery (VRFB). Products from Dupont, Nafion membrane, is mainly used for PEM in VRFB. However, permeation of vanadium ion occurs because of Nafion’s high permeability. Therefore, the efficiency of VRFB decreases and the prices becomes higher, which hinders VRFB’s commercialization. In order to solve this problem, poly(phenylene oxide) (PPO) is sulfonated for the preparation of low-priced hydrocarbon polymer electrolyte membrane. sPPO membrane is characterized by fundamental properties and VRFB cell test.

Study on corrosion migrations within catalyst-coated membranes of proton exchange membrane electrolyzer cells

DOE PAGES

Mo, Jingke; Steen, Stuart; Kang, Zhenye; ...

2017-10-09

The corrosion of low-cost, easily manufactured metallic components inside the electrochemical environment of proton exchange membrane electrolyzer cells (PEMECs) has a significant effect on their performance and durability. Here, 316 stainless steel (SS) mesh was used as a model liquid/gas diffusion layer material to investigate the migration of corrosion products in the catalyst-coated membrane of a PEMEC. Iron and nickel cation particles were found distributed throughout the anode catalyst layer, proton exchange membrane, and cathode catalyst layer, as revealed by scanning transmission electron microscopy and energy dispersive X-ray spectroscopy. Our results indicate the corrosion products of 316 SS are transportedmore » from anode to cathode through the nanochannels of the Nafion membrane, resulting in impeded proton transport and overall PEMEC performance loss.« less

Study on corrosion migrations within catalyst-coated membranes of proton exchange membrane electrolyzer cells

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mo, Jingke; Steen, Stuart; Kang, Zhenye

The corrosion of low-cost, easily manufactured metallic components inside the electrochemical environment of proton exchange membrane electrolyzer cells (PEMECs) has a significant effect on their performance and durability. Here, 316 stainless steel (SS) mesh was used as a model liquid/gas diffusion layer material to investigate the migration of corrosion products in the catalyst-coated membrane of a PEMEC. Iron and nickel cation particles were found distributed throughout the anode catalyst layer, proton exchange membrane, and cathode catalyst layer, as revealed by scanning transmission electron microscopy and energy dispersive X-ray spectroscopy. Our results indicate the corrosion products of 316 SS are transportedmore » from anode to cathode through the nanochannels of the Nafion membrane, resulting in impeded proton transport and overall PEMEC performance loss.« less

Fatigue and creep to leak tests of proton exchange membranes using pressure-loaded blisters

NASA Astrophysics Data System (ADS)

Li, Yongqiang; Dillard, David A.; Case, Scott W.; Ellis, Michael W.; Lai, Yeh-Hung; Gittleman, Craig S.; Miller, Daniel P.

In this study, three commercially available proton exchange membranes (PEMs) are biaxially tested using pressure-loaded blisters to characterize their resistance to gas leakage under either static (creep) or cyclic fatigue loading. The pressurizing medium, air, is directly used for leak detection. These tests are believed to be more relevant to fuel cell applications than quasi-static uniaxial tensile-to-rupture tests because of the use of biaxial cyclic and sustained loading and the use of gas leakage as the failure criterion. They also have advantages over relative humidity cycling test, in which a bare PEM or catalyst coated membrane is clamped with gas diffusion media and flow field plates and subjected to cyclic changes in relative humidity, because of the flexibility in allowing controlled mechanical loading and accelerated testing. Nafion ® NRE-211 membranes are tested at three different temperatures and the time-temperature superposition principle is used to construct stress-lifetime master curve. Tested at 90 °C, 2%RH extruded Ion Power ® N111-IP membranes have a longer lifetime than Gore™-Select ® 57 and Nafion ® NRE-211 membranes.

Al2O3 Disk Supported Si3N4 Hydrogen Purification Membrane for Low Temperature Polymer Electrolyte Membrane Fuel Cells

PubMed Central

Liu, Xiaoteng; Christensen, Paul A.; Kelly, Stephen M.; Rocher, Vincent; Scott, Keith

2013-01-01

Reformate gas, a commonly employed fuel for polymer electrolyte membrane fuel cells (PEMFCs), contains carbon monoxide, which poisons Pt-containing anodes in such devices. A novel, low-cost mesoporous Si3N4 selective gas separation material was tested as a hydrogen clean-up membrane to remove CO from simulated feed gas to single-cell PEMFC, employing Nafion as the polymer electrolyte membrane. Polarization and power density measurements and gas chromatography showed a clear effect of separating the CO from the gas mixture; the performance and durability of the fuel cell was thereby significantly improved. PMID:24957065

Guided cracking of electrodes by stretching prism-patterned membrane electrode assemblies for high-performance fuel cells.

PubMed

Ahn, Chi-Yeong; Jang, Segeun; Cho, Yong-Hun; Choi, Jiwoo; Kim, Sungjun; Kim, Sang Moon; Sung, Yung-Eun; Choi, Mansoo

2018-01-19

Guided cracks were successfully generated in an electrode using the concentrated surface stress of a prism-patterned Nafion membrane. An electrode with guided cracks was formed by stretching the catalyst-coated Nafion membrane. The morphological features of the stretched membrane electrode assembly (MEA) were investigated with respect to variation in the prism pattern dimension (prism pitches of 20 μm and 50 μm) and applied strain (S ≈ 0.5 and 1.0). The behaviour of water on the surface of the cracked electrode was examined using environmental scanning electron microscopy. Guided cracks in the electrode layer were shown to be efficient water reservoirs and liquid water passages. The MEAs with and without guided cracks were incorporated into fuel cells, and electrochemical measurements were conducted. As expected, all MEAs with guided cracks exhibited better performance than conventional MEAs, mainly because of the improved water transport.

Ionomer-Membrane Water Processing Methods

NASA Technical Reports Server (NTRS)

MacCallum, Taber K. (Inventor); Kelsey, Laura (Inventor)

2016-01-01

This disclosure provides water processing apparatuses, systems, and methods for recovering water from wastewater such as urine. The water processing apparatuses, systems, and methods can utilize membrane technology for extracting purified water in a single step. A containment unit can include an ionomer membrane, such as Nafion(TradeMark) over a hydrophobic microporous membrane, such as polytetrafluoroethylene (PTFE). The containment unit can be filled with wastewater, and the hydrophobic microporous membrane can be impermeable to liquids and solids of the wastewater but permeable to gases and vapors of the wastewater, and the ionomer membrane can be permeable to water vapor but impermeable to one or more contaminants of the gases and vapors. The containment unit can be exposed to a dry purge gas to maintain a water vapor partial pressure differential to drive permeation of the water vapor, and the water vapor can be collected and processed into potable water.

Ionomer-Membrane Water Processing Apparatus

NASA Technical Reports Server (NTRS)

MacCallum, Taber K. (Inventor); Kelsey, Laura (Inventor)

2016-01-01

This disclosure provides water processing apparatuses, systems, and methods for recovering water from wastewater such as urine. The water processing apparatuses, systems, and methods can utilize membrane technology for extracting purified water in a single step. A containment unit can include an ionomer membrane, such as Nafion(Registered Trademark), over a hydrophobic microporous membrane, such as polytetrafluoroethylene (PTFE). The containment unit can be filled with wastewater, and the hydrophobic microporous membrane can be impermeable to liquids and solids of the wastewater but permeable to gases and vapors of the wastewater, and the ionomer membrane can be permeable to water vapor but impermeable to one or more contaminants of the gases and vapors. The containment unit can be exposed to a dry purge gas to maintain a water vapor partial pressure differential to drive permeation of the water vapor, and the water vapor can be collected and processed into potable water.

Ionomer-Membrane Water Processing Apparatus

NASA Technical Reports Server (NTRS)

MacCallum, Taber K. (Inventor); Kelsey, Laura Katrina (Inventor)

2017-01-01

This disclosure provides water processing apparatuses, systems, and methods for recovering water from wastewater such as urine. The water processing apparatuses, systems, and methods can utilize membrane technology for extracting purified water in a single step. A containment unit can include an ionomer membrane, such as Nafion.RTM., over a hydrophobic microporous membrane, such as polytetrafluoroethylene (PTFE). The containment unit can be filled with wastewater, and the hydrophobic microporous membrane can be impermeable to liquids and solids of the wastewater but permeable to gases and vapors of the wastewater, and the ionomer membrane can be permeable to water vapor but impermeable to one or more contaminants of the gases and vapors. The containment unit can be exposed to a dry purge gas to maintain a water vapor partial pressure differential to drive permeation of the water vapor, and the water vapor can be collected and processed into potable water.

Introduction of gold nanoparticles into myoglobin-Nafion film for direct electrochemistry application.

PubMed

Xie, Wenting; Kong, Linlin; Kan, Meixiu; Han, Dongmei; Wang, Xueji; Zhang, Hui-Min

2010-10-01

An effective myoglobin-Nafion film is prepared by introducing gold nanoparticles in through a simple procedure by ion-exchange combined with electrochemical reduction. Gold nanoparticles are highly dispersed in myoglobin-Nafion film with an average size of 2.3 +/- 0.2 nm. The electrochemical behavior of myoglobin entrapped in the film has been carefully investigated with cyclic voltammetry. The results show that the introduction of gold nanoparticles into myoglobin-Nafion film makes the direct electron transfer of myoglobin efficient. A pair of well-defined redox peaks for myoglobin heme Fe(II)/Fe(III) is observed with a formal potential of -0.150 V in 0.1 M phosphate buffer (pH 7.0). The electrochemical parameters of myoglobin in the composite film are further calculated with the results of the electron-transfer rate constant (k(s)) as 0.93 s(-1) and the charge transfer coefficient (alpha) as 0.69. The experimental results also demonstrate that the immobilized myoglobin retains its electrocatalytic activity for the reduction of hydrogen peroxide and the catalytic reduction peak of myoglobin appear in a linear relationship with H2O2 concentration in the range of 10.0-235.0 microM with correlation coefficient of 0.9970. Thus fabricated Au/Mb/Nafion electrode should give a new approach for developing redox protein or enzyme-based biosensors.

Synthesis and Characterization of Polymer-Metal Nanostructured Membranes

DTIC Science & Technology

ions creating unique polymer -metal nanostructured membranes. A comprehensive materials characterization study was performed to understand their...fluoropolymers were also investigated. First the polymer -metal nanostructure of Nafion with several counter-ions was studied upon supercritical fluid CO2...processing. Then, novel fluorinated block copolymers were synthesized using atom transfer radical polymerization (ATRP) and their resulting nanostructure was

New High-Temperature Membranes Developed for Proton Exchange Membrane Fuel Cells

NASA Technical Reports Server (NTRS)

Kinder, James D.

2004-01-01

Fuel cells are receiving a considerable amount of attention for potential use in a variety of areas, including the automotive industry, commercial power generation, and personal electronics. Research at the NASA Glenn Research Center has focused on the development of fuel cells for use in aerospace power systems for aircraft, unmanned air vehicles, and space transportation systems. These applications require fuel cells with higher power densities and better durability than what is required for nonaerospace uses. In addition, membrane cost is a concern for any fuel cell application. The most widely used membrane materials for proton exchange membrane (PEM) fuel cells are based on sulfonated perfluorinated polyethers, typically Nafion 117, Flemion, or Aciplex. However, these polymers are costly and do not function well at temperatures above 80 C. At higher temperatures, conventional membrane materials dry out and lose their ability to conduct protons, essential for the operation of the fuel cell. Increasing the operating temperature of PEM fuel cells from 80 to 120 C would significantly increase their power densities and enhance their durability by reducing the susceptibility of the electrode catalysts to carbon monoxide poisoning. Glenn's Polymers Branch has focused on developing new, low-cost membranes that can operate at these higher temperatures. A new series of organically modified siloxane (ORMOSIL) polymers were synthesized for use as membrane materials in a high-temperature PEM fuel cell. These polymers have an organic portion that can allow protons to transport through the polymer film and a cross-linked silica network that gives the polymers dimensional stability. These flexible xerogel polymer films are thermally stable, with decomposition onset as high as 380 C. Two types of proton-conducting ORMOSIL films have been produced: (1) NASA-A, which can coordinate many highly acid inorganic salts that facilitate proton conduction and (2) NASA-B, which has been

Characterization of a membrane-based, electrochemically driven pumping system using aqueous electrolyte solutions.

PubMed

Norman, Mya A; Evans, Christine E; Fuoco, Anthony R; Noble, Richard D; Koval, Carl A

2005-10-01

Electrokinetic flow provides a mechanism for a variety of fluid pumping schemes. The design and characterization of an electrochemically driven pump that utilizes porous carbon electrodes, iodide/triiodide redox electrolytes, and Nafion membranes is described. Fluid pumping by the cell is reversible and controlled by the cell current. Chronopotentiometry experiments indicate that the total available fluid that can be pumped in a single electrolysis without gas evolution is determined solely by the initial concentration of electrolyte and the applied current. The magnitude of the fluid flow at a given current is determined by the nature of the cation in the electrolyte and by the water absorption properties of the Nafion membrane. For 1 M aqueous electrolytes, pumping rates ranging from 1 to 14 microL/min were obtained for current densities of 10-30 mA/cm2 of membrane area. Molar volume changes for the I3-/I- redox couple and for the alkali cation migration contribute little to the observed volumetric flow rates; the magnitude of the flow is dominated by the migration-induced flow of water.

Bioacceptable and calcification-resistant membranes and interfaces for implantable sensors and devices

NASA Astrophysics Data System (ADS)

Galeska, Izabela Ewa

The rational design and characterization of biocompatible, semipermeable and calcification resistant materials to serve as an outer membrane for implantable glucose biosensors, was the primary focus of this research. Multilayered films of polyanions (i.e. Nafion(TM), a perfluorinated ionomer, and Humic Acids (HAs), naturally occurring biopolymers), fabricated by layer-by-layer self-assembly with oppositely charged ferric ions were investigated as potential membranes. Spectroscopic ellipsometry and quartz crystal microbalance studies point towards a stepwise film growth, with growth rates of 47 and 24.3 nm per layer (for Nafion and HAs respectively) that can be altered depending on the pH and ionic strength of the polyanion solution. Nafion/Fe3+ assembled films exhibited an order of magnitude lower calcification as compared to dip-coated Nafion films and did not require annealing to impart insolubility. Similarly the HAs/Fe3+ films were also devoid of calcification, even after four-week immersion in DMEM cell culture media. Significantly, in vivo studies on the HAs/Fe3 films point to their biocompatibility as demonstrated by mild tissue reaction. These results, along with controllable glucose permeability, could prove vital in prolonging the lifetime of implantable biosensors. Additionally in effort to minimize tissue trauma upon implantation, novel poly(lactic-co-glycolic acid) (PLGA) microsphere/poly(vinyl alcohol) (PVA) hydrogel composites were investigated for dexamethasone delivery. A release rate of 25 to 40% over one month, following a zero order profile, was achieved by preferential adsorption of surface active polyacids (poly(acrylic acid), Nafion and HAs) on the hydrogel dispersed microspheres. Environmental scanning electron microscopy investigation on the degradation mechanism of the microspheres pointed towards their slow homogeneous degradation in the PVA hydrogels that was significantly surface-accelerated in the presence of polyacids. The physico

An ``Alternating-Curvature'' Model for the Nanometer-scale Structure of the Nafion Ionomer, Based on Backbone Properties Detected by NMR

NASA Astrophysics Data System (ADS)

Schmidt-Rohr, Klaus; Chen, Q.

2006-03-01

The perfluorinated ionomer, Nafion, which consists of a (-CF2-)n backbone and charged side branches, is useful as a proton exchange membrane in H2/O2 fuel cells. A modified model of the nanometer-scale structure of hydrated Nafion will be presented. It features hydrated ionic clusters familiar from some previous models, but is based most prominently on pronounced backbone rigidity between branch points and limited orientational correlation of local chain axes. These features have been revealed by solid-state NMR measurements, which take advantage of fast rotations of the backbones around their local axes. The resulting alternating curvature of the backbones towards the hydrated clusters also better satisfies the requirement of dense space filling in solids. Simulations based on this ``alternating curvature'' model reproduce orientational correlation data from NMR, as well as scattering features such as the ionomer peak and the I(q) ˜ 1/q power law at small q values, which can be attributed to modulated cylinders resulting from the chain stiffness. The shortcomings of previous models, including Gierke's cluster model and more recent lamellar or bundle models, in matching all requirements imposed by the experimental data will be discussed.

Two-port transmission line technique for dielectric property characterization of polymer electrolyte membranes.

PubMed

Lu, Zijie; Lanagan, Michael; Manias, Evangelos; Macdonald, Digby D

2009-10-15

Performance improvements of perfluorosulfonic acid membranes, such as Nafion and Flemion, underline a need for dielectric characterization of these materials toward a quantitative understanding of the dynamics of water molecules and protons within the membranes. In this Article, a two-port transmission line technique for measuring the complex permittivity spectra of polymeric electrolytes in the microwave region is described, and the algorithms for permittivity determination are presented. The technique is experimentally validated with liquid water and polytertrafluoroethylene film, whose dielectric properties are well-known. Further, the permittivity spectra of dry and hydrated Flemion SH150 membranes are measured and compared to those of Nafion 117. Two water relaxation modes are observed in the microwave region (0.045-26 GHz) at 25 degrees C. The higher-frequency process observed is identified as the cooperative relaxation of bulk-like water, whose amount was found to increase linearly with water content in the polymer. The lower-frequency process, characterized by longer relaxation times in the range of 20-70 ps, is attributed to water molecules that are loosely bound to sulfonate groups. The loosely bound water amount was found to increase with hydration level at low water content and levels off at higher water contents. Flemion SH150, which has an equivalent weight of 909 g/equiv, displays higher dielectric strengths for both of these water modes as compared to Nafion 117 (equivalent weight of 1100 g/equiv), which probably reflects the effect of equivalent weight on the polymers' hydrated structure, and in particular its effect on the extended ionic cluster domains.

Water Uptake Profile In a Model Ion-Exchange Membrane: Conditions For Water-Rich Channels

DTIC Science & Technology

2014-12-01

these issues, more research is needed to improve their performance. Aqueous alkaline electrolytes such as potassium hydroxide (KOH) trace their begin...1.2 Water distribution Motivation Hydroxide ion transport through the membrane is fundamentally dependent on the amount and distribution of water...hydrophilic-to-hydrophobic ratio, for several reasons. First, this is the case for Nafion, the gold standard for PEM membranes; its unique pore structure

Proton-conducting ionic liquid-based Proton Exchange Membrane Fuel Cell membranes: The key role of ionomer-ionic liquid interaction

NASA Astrophysics Data System (ADS)

Martinez, Mathieu; Molmeret, Yannick; Cointeaux, Laure; Iojoiu, Cristina; Leprêtre, Jean-Claude; El Kissi, Nadia; Judeinstein, Patrick; Sanchez, Jean-Yves

The paper deals with the synthesis and characterisation of proton-conducting ionic liquids (PCILs) and their polymer electrolytes obtained by blending modified Nafion membranes with different concentrations of PCILs. The PCILs are obtained by the neutralization of triethylamine with different organic acids. The first part of the paper studies the influence of acidity and acid structure on PCIL thermal and electrochemical performance, while the second part examines membrane conductivity and reveals it to depend more on PCIL structure than on its intrinsic conductivity. At 130 °C, conductivities exceeding 10 mS cm -1 were obtained in fully anhydrous conditions.

Advances in the high performance polymer electrolyte membranes for fuel cells.

PubMed

Zhang, Hongwei; Shen, Pei Kang

2012-03-21

This critical review tersely and concisely reviews the recent development of the polymer electrolyte membranes and the relationship between their properties and affecting factors like operation temperature. In the first section, the advantages and shortcomings of the corresponding polymer electrolyte membrane fuel cells are analyzed. Then, the limitations of Nafion membranes and their alternatives to large-scale commercial applications are discussed. Secondly, the concepts and approaches of the alternative proton exchange membranes for low temperature and high temperature fuel cells are described. The highlights of the current scientific achievements are given for various aspects of approaches. Thirdly, the progress of anion exchange membranes is presented. Finally, the perspectives of future trends on polymer electrolyte membranes for different applications are commented on (400 references).

Hydrophobic asymmetric ultrafiltration PVDF membranes: an alternative separator for VFB with excellent stability.

PubMed

Wei, Wenping; Zhang, Huamin; Li, Xianfeng; Zhang, Hongzhang; Li, Yun; Vankelecom, Ivo

2013-02-14

Polyvinylidene fluoride (PVDF) ultrafiltration membranes were investigated for the first time in vanadium redox flow battery (VFB) applications. Surprisingly, PVDF ultrafiltration membranes with hydrophobic pore walls and relatively large pore sizes of several tens of nanometers proved able to separate vanadium ions and protons efficiently, thus being suitable as a VFB separator. The ion selectivity of this new type of VFB membrane could be tuned readily by controlling the membrane morphology via changes in the composition of the membrane casting solution, and the casting thickness. The results showed that the PVDF membranes offered good performances and excellent stability in VFB applications, where it could, performance-wise, truly substitute Nafion in VFB applications, but at a much lower cost.

Novel structure design of composite proton exchange membranes with continuous and through-membrane proton-conducting channels

NASA Astrophysics Data System (ADS)

Wang, Hang; Tang, Chenxiao; Zhuang, Xupin; Cheng, Bowen; Wang, Wei; Kang, Weimin; Li, Hongjun

2017-10-01

The primary goal of this study is to develop a high-performanced proton exchange membrane with the characteristics of through-membrane and continuous solution blown nanofibers as proton-conducting channels. The curled sulfonated phenolphthalein poly (ether sulfone) and poly (vinylidene fluoride) nanofibers were separately fabricated through the solution blowing process which is a new nanofiber fabricating method with high productivity, then they were fabricated into a sandwich-structured mat. Then this sandwich-structured mat was hot-pressed to form the designed structure using different melting temperatures of the two polymers by melting and making poly (vinylidene fluoride) flow into the phenolphthalein poly (ether sulfone) nanofiber mat. The characteristics of the composite membrane, such as morphology and performance of the membrane, were investigated. The characterization results proved the successful preparation of the membrane structure. Performance results showed that the novel structured membrane with through-membrane nanofibers significantly improved water swelling and methanol permeability, though its conductivity is lower than that of Nafion, the cell performance showed comparable results. Therefore, the novel structure design can be considered as a promising method for preparing of proton exchange membranes.

Effect of "bridge" on the performance of organic-inorganic crosslinked hybrid proton exchange membranes via KH550

NASA Astrophysics Data System (ADS)

Han, Hailan; Li, Hai Qiang; Liu, Meiyu; Xu, Lishuang; Xu, Jingmei; Wang, Shuang; Ni, Hongzhe; Wang, Zhe

2017-02-01

A series of novel organic-inorganic crosslinked hybrid proton exchange membranes were prepared using sulfonated poly(arylene ether ketone sulfone) polymers containing carboxyl groups (C-SPAEKS), (3-aminopropyl)-triethoxysilane (KH550), and tetraethoxysilane (TEOS). KH550 acted as a "bridge" after reacting with carboxyl and sulfonic groups of C-SPAEKS to form covalent and ionic crosslinked structure between the C-SPAEKS and SiO2 phase. The crosslinked hybrid membranes (C-SPAEKS/K-SiO2) were characterized by FT-IR spectroscopy, TGA, and electrochemistry, etc. The thermal stability, mechanical properties and proton conductivity of the crosslinked hybrid membranes were improved by the presence of both crosslinked structure and inorganic phase. The proton conductivity of C-SPAEKS/K-SiO2-8 was recorded as 0.110 S cm-1, higher than that of Nafion® (0.028 S cm-1) at 120 °C. Moreover, the methanol permeability of the C-SPAEKS/K-SiO2-8 was measured as 3.86 × 10-7 cm2 s-1, much lower than that of Nafion® 117 membranes (29.4 × 10-7 cm2 s-1) at 25 °C.

Durability of PEM Fuel Cell Membranes

NASA Astrophysics Data System (ADS)

Huang, Xinyu; Reifsnider, Ken

Durability is still a critical limiting factor for the commercialization of polymer electrolyte membrane (PEM) fuel cells, a leading energy conversion technology for powering future hydrogen fueled automobiles, backup power systems (e.g., for base transceiver station of cellular networks), portable electronic devices, etc. Ionic conducting polymer (ionomer) electrolyte membranes are the critical enabling materials for the PEM fuel cells. They are also widely used as the central functional elements in hydrogen generation (e.g., electrolyzers), membrane cell for chlor-alkali production, etc. A perfluorosulfonic acid (PFSA) polymer with the trade name Nafion® developed by DuPont™ is the most widely used PEM in chlor-alkali cells and PEM fuel cells. Similar PFSA membranes have been developed by Dow Chemical, Asahi Glass, and lately Solvay Solexis. Frequently, such membranes serve the dual function of reactant separation and selective ionic conduction between two otherwise separate compartments. For some applications, the compromise of the "separation" function via the degradation and mechanical failure of the electrolyte membrane can be the life-limiting factor; this is particularly the case for PEM in hydrogen/oxygen fuel cells.

Square-wave stripping voltammetric determination of caffeic acid on electrochemically reduced graphene oxide-Nafion composite film.

PubMed

Filik, Hayati; Çetintaş, Gamze; Avan, Asiye Aslıhan; Aydar, Sevda; Koç, Serkan Naci; Boz, İsmail

2013-11-15

An electrochemical sensor composed of Nafion-graphene nanocomposite film for the voltammetric determination of caffeic acid (CA) was studied. A Nafion graphene oxide-modified glassy carbon electrode was fabricated by a simple drop-casting method and then graphene oxide was electrochemically reduced over the glassy carbon electrode. The electrochemical analysis method was based on the adsorption of caffeic acid on Nafion/ER-GO/GCE and then the oxidation of CA during the stripping step. The resulting electrode showed an excellent electrocatalytical response to the oxidation of caffeic acid (CA). The electrochemistry of caffeic acid on Nafion/ER-GO modified glassy carbon electrodes (GCEs) were studied by cyclic voltammetry and square-wave adsorption stripping voltammetry (SW-AdSV). At optimized test conditions, the calibration curve for CA showed two linear segments: the first linear segment increased from 0.1 to 1.5 and second linear segment increased up to 10 µM. The detection limit was determined as 9.1×10(-8) mol L(-1) using SW-AdSV. Finally, the proposed method was successfully used to determine CA in white wine samples. Copyright © 2013 Elsevier B.V. All rights reserved.

Post-irradiation time effects on the graft of poly(ethylene-alt-tetrafluoroethylene) (ETFE) films for ion exchange membrane application

NASA Astrophysics Data System (ADS)

Geraldes, Adriana N.; Zen, Heloísa A.; Ribeiro, Geise; Ferreira, Henrique P.; Souza, Camila P.; Parra, Duclerc F.; Santiago, Elisabete I.; Lugão, Ademar B.

2010-03-01

Grafting of styrene followed by sulfonation onto poly(ethylene-alt-tetrafluoroethylene) (ETFE) was studied for synthesis of ion exchange membranes. Radiation-induced grafting of styrene onto ETFE films was investigated after simultaneous irradiation (in post-irradiation condition) using a 60Co source. The ETFE films were irradiated at 20 kGy dose at room temperature and chemical changes were monitored after contact with styrene for grafting. The post-irradiation time was established at 14 days when the films were remained in styrene/toluene 1:1 v/v. After this period the grafting degree was evaluated in the samples. The grafted films were sulfonated using chlorosulfonic acid and 1, 2-dichloroethane 20:80 (v/v) at room temperature for 5 h. The membranes were analyzed by infrared spectroscopy (FTIR), differential scanning calorimeter (DSC), thermogravimetric measurements (TG) and degree of grafting (DOG). The ion exchange capacity (IEC) of membranes was determined by acid-base titration and the values for ETFE membranes were achieved higher than Nafion ® films. Preliminary single cell performance was made using pure H 2 and O 2 as reactants at a cell temperature of 80 °C and atmospheric gas pressure. The fuel cell performance of ETFE films was satisfactory when compared to state-of-art Nafion ® membranes.

The quintuple-shape memory effect in electrospun nanofiber membranes

NASA Astrophysics Data System (ADS)

Zhang, Fenghua; Zhang, Zhichun; Liu, Yanju; Lu, Haibao; Leng, Jinsong

2013-08-01

Shape memory fibrous membranes (SMFMs) are an emerging class of active polymers, which are capable of switching from a temporary shape to their permanent shape upon appropriate stimulation. Quintuple-shape memory membranes based on the thermoplastic polymer Nafion, with a stable fibrous structure, are achieved via electrospinning technology, and possess a broad transition temperature. The recovery of multiple temporary shapes of electrospun membranes can be triggered by heat in a single triple-, quadruple-, quintuple-shape memory cycle, respectively. The fiber morphology and nanometer size provide unprecedented design flexibility for the adjustable morphing effect. SMFMs enable complex deformations at need, having a wide potential application field including smart textiles, artificial intelligence robots, bio-medical engineering, aerospace technologies, etc in the future.

Water uptake, ionic conductivity and swelling properties of anion-exchange membrane

NASA Astrophysics Data System (ADS)

Duan, Qiongjuan; Ge, Shanhai; Wang, Chao-Yang

2013-12-01

Water uptake, ionic conductivity and dimensional change of the anion-exchange membrane made by Tokuyama Corporation (A201 membrane) are investigated at different temperatures and water activities. Specifically, the amount of water taken up by membranes exposed to water vapor and membranes soaked in liquid water is determined. The water uptake of the A201 membrane increases with water content as well as temperature. In addition, water sorption data shows Schroeder's paradox for the AEMs investigated. The swelling properties of the A201 membrane exhibit improved dimensional stability compared with Nafion membrane. Water sorption of the A201 membrane occurs with a substantial negative excess volume of mixing. The threshold value of hydrophilic fraction in the A201 membrane for ionic conductivity is around 0.34, above which, the conductivity begins to rise quickly. This indicates that a change in the connectivity of the hydrophilic domains occurs when hydrophilic fraction approaches 0.34.

Electrokinetic Response of Charge-Selective Nanostructured Polymeric Membranes

NASA Astrophysics Data System (ADS)

Schiffbauer, Jarrod; Li, Diya; Gao, Feng; Phillip, William; Chang, Hsueh-Chia

2017-11-01

Nanostructured polymeric membranes, with a tunable pore size and ease of surface molecular functionalization, are a promising material for separations, filtration, and sensing applications. Recently, such membranes have been fabricated wherein the ion selectivity is imparted by self-assembled functional groups through a two-step process. Amine groups are used to provide a positive surface charge and acid groups are used to yield a negative charge. The membranes can be fabricated as either singly-charged or patterned/mosaic membranes, where there are alternating regions of amine- lined or acid-lined pores. We demonstrate that such membranes, in addition to having many features in common with other charge selective membranes (i.e. AMX or Nafion), display a unique single-membrane rectification behavior. This is due to the asymmetric distribution of charged functional groups during the fabrication process. We demonstrate this rectification effect using both dc current-voltage characteristics as well as dc-biased electrical impedance spectroscopy. Furthermore, surface charge changes due to dc concentration polarization and generation of localized pH shifts are monitored using electrical impedance spectroscopy. (formerly at University of Notre Dame).

Acid-doped polymer nanofiber framework: Three-dimensional proton conductive network for high-performance fuel cells

NASA Astrophysics Data System (ADS)

Tanaka, Manabu; Takeda, Yasushi; Wakiya, Takeru; Wakamoto, Yuta; Harigaya, Kaori; Ito, Tatsunori; Tarao, Takashi; Kawakami, Hiroyoshi

2017-02-01

High-performance polymer electrolyte membranes (PEMs) with excellent proton conductivity, gas barrier property, and membrane stability are desired for future fuel cells. Here we report the development of PEMs based on our proposed new concept "Nanofiber Framework (NfF)." The NfF composite membranes composed of phytic acid-doped polybenzimidazole nanofibers (PBINf) and Nafion matrix show higher proton conductivity than the recast-Nafion membrane without nanofibers. A series of analyses reveal the formation of three-dimensional network nanostructures to conduct protons and water effectively through acid-condensed layers at the interface of PBINf and Nafion matrix. In addition, the NfF composite membrane achieves high gas barrier property and distinguished membrane stability. The fuel cell performance by the NfF composite membrane, which enables ultra-thin membranes with their thickness less than 5 μm, is superior to that by the recast-Nafion membrane, especially at low relative humidity. Such NfF-based high-performance PEM will be accomplished not only by the Nafion matrix used in this study but also by other polymer electrolyte matrices for future PEFCs.

Interface-designed Membranes with Shape-controlled Patterns for High-performance Polymer Electrolyte Membrane Fuel Cells

PubMed Central

Jeon, Yukwon; Kim, Dong Jun; Koh, Jong Kwan; Ji, Yunseong; Kim, Jong Hak; Shul, Yong-Gun

2015-01-01

Polymer electrolyte membrane fuel cell is a promising zero-emission power generator for stationary/automotive applications. However, key issues, such as performance and costs, are still remained for an economical commercialization. Here, we fabricated a high-performance membrane electrode assembly (MEA) using an interfacial design based on well-arrayed micro-patterned membranes including circles, squares and hexagons with different sizes, which are produced by a facile elastomeric mold method. The best MEA performance is achieved using patterned Nafion membrane with a circle 2 μm in size, which exhibited a very high power density of 1906 mW/cm2 at 75 °C and Pt loading of 0.4 mg/cm2 with 73% improvement compared to the commercial membrane. The improved performance are attributed to the decreased MEA resistances and increased surface area for higher Pt utilization of over 80%. From these enhanced properties, it is possible to operate at lower Pt loading of 0.2 mg/cm2 with an outstanding performance of 1555 mW/cm2 and even at air/low humidity operations. PMID:26552839

Interface-designed Membranes with Shape-controlled Patterns for High-performance Polymer Electrolyte Membrane Fuel Cells

NASA Astrophysics Data System (ADS)

Jeon, Yukwon; Kim, Dong Jun; Koh, Jong Kwan; Ji, Yunseong; Kim, Jong Hak; Shul, Yong-Gun

2015-11-01

Polymer electrolyte membrane fuel cell is a promising zero-emission power generator for stationary/automotive applications. However, key issues, such as performance and costs, are still remained for an economical commercialization. Here, we fabricated a high-performance membrane electrode assembly (MEA) using an interfacial design based on well-arrayed micro-patterned membranes including circles, squares and hexagons with different sizes, which are produced by a facile elastomeric mold method. The best MEA performance is achieved using patterned Nafion membrane with a circle 2 μm in size, which exhibited a very high power density of 1906 mW/cm2 at 75 °C and Pt loading of 0.4 mg/cm2 with 73% improvement compared to the commercial membrane. The improved performance are attributed to the decreased MEA resistances and increased surface area for higher Pt utilization of over 80%. From these enhanced properties, it is possible to operate at lower Pt loading of 0.2 mg/cm2 with an outstanding performance of 1555 mW/cm2 and even at air/low humidity operations.

Synthesis of Long-Chain-Branched (LCB) Polysulfones for Multifunctional Transport Membranes

DTIC Science & Technology

2010-09-01

R.; Dutta, N. K. Interfacial Interactions in Aprotic Ionic Liquid Based Protonic Membrane and Its Correlation with High Temperature Conductivity...rigidity. The series of novel polymers was characterized for chemical structure, thermal transitions, and molecular weight. Ionic conductivity was tested...Although much progress exists based on perfluorosulfonated platforms ( Nafion , σ ≈ 10-1 – 10-2 S/cm) new and more complicated parameters arise as

Regulating the Membrane Transport Activity and Death of Cells via Electroosmotic Manipulation.

PubMed

Hui, Tsz Hin; Kwan, Kin Wah; Chun Yip, Timothy Tak; Fong, Hong Wai; Ngan, Kai Cheong; Yu, Miao; Yao, Shuhuai; Wan Ngan, Alfonso Hin; Lin, Yuan

2016-06-21

Although the volume of living cells has been known to heavily influence their behavior and fate, a method allowing us to control the cell size in a programmable manner is still lacking. Here, we develop a technique in which precise changes in the cellular volume can be conveniently introduced by varying the voltage applied across a Nafion membrane that separates the culture medium from a reservoir. It is found that, unlike sudden osmotic shocks, active ion transport across the membrane of leukemia K562 cells will not be triggered by a gradual change in the extracellular osmolarity. Furthermore, when subjected to the same applied voltage, different lung and nasopharyngeal epithelial cancer cells will undergo larger volumetric changes and have a 5-10% higher death rate compared to their normal counterparts. We show that such distinct response is largely caused by the overexpression of aquaporin-4 in tumor cells, with knockout of this water channel protein resulting in a markedly reduced change in the cellular volume. Finally, by taking into account the exchange of water/ion molecules across the Nafion film and the cell membrane, a theoretical model is also proposed to describe the voltage-induced size changes of cells, which explain our experimental observations very well. Copyright © 2016 Biophysical Society. Published by Elsevier Inc. All rights reserved.

Palladium-bacterial cellulose membranes for fuel cells.

PubMed

Evans, Barbara R; O'Neill, Hugh M; Malyvanh, Valerie P; Lee, Ida; Woodward, Jonathan

2003-07-01

Bacterial cellulose is a versatile renewable biomaterial that can be used as a hydrophilic matrix for the incorporation of metals into thin, flexible, thermally stable membranes. In contrast to plant cellulose, we found it catalyzed the deposition of metals within its structure to generate a finely divided homogeneous catalyst layer. Experimental data suggested that bacterial cellulose possessed reducing groups capable of initiating the precipitation of palladium, gold, and silver from aqueous solution. Since the bacterial cellulose contained water equivalent to at least 200 times the dry weight of the cellulose, it was dried to a thin membranous structure suitable for the construction of membrane electrode assemblies (MEAs). Results of our study with palladium-cellulose showed that it was capable of catalyzing the generation of hydrogen when incubated with sodium dithionite and generated an electrical current from hydrogen in an MEA containing native cellulose as the polyelectrolyte membrane (PEM). Advantages of using native and metallized bacterial cellulose membranes in an MEA over other PEMs such as Nafion 117 include its higher thermal stability to 130 degrees C and lower gas crossover.

Preventing the dissolution of lithium polysulfides in lithium-sulfur cells by using Nafion-coated cathodes.

PubMed

Oh, Soo Jung; Lee, Jun Kyu; Yoon, Woo Young

2014-09-01

The principal drawback of lithium-sulfur batteries is the dissolution of long-chain lithium polysulfides into the electrolyte, which limits cycling performance. To overcome this problem, we focused on the development of a novel cathode as well as anode material and designed Nafion-coated NiCrAl/S as a cathode and lithium powder as an anode. Nafion-coated NiCrAl/S cathode was synthesized using a two-step dip-coating technique. The lithium-powder anode was used instead of a lithium-foil anode to prohibit dendrite growth and to improve on the electrochemical behaviors. The cells showed an initial discharge capacity of about 900 mA g(-1) and a final discharge capacity of 772 mA g(-1) after 100 cycles at 0.1 C-rate. Scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS) demonstrate that using the Nafion-coated NiCrAl/S cathode can suppress the dissolution of long-chain lithium polysulfides. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Considerations of the Effects of Naphthalene Moieties on the Design of Proton-Conductive Poly(arylene ether ketone) Membranes for Direct Methanol Fuel Cells.

PubMed

Wang, Baolong; Hong, Lihua; Li, Yunfeng; Zhao, Liang; Wei, Yuxue; Zhao, Chengji; Na, Hui

2016-09-14

Novel sulfonated poly(arylene ether ketones) (SDN-PAEK-x), consisting of dual naphthalene and flexible sulfoalkyl groups, were prepared via polycondensation, demethylation, and sulfobutylation grafting reaction. Among them, SDN-PAEK-1.94 membrane with the highest ion exchange capacity (IEC = 2.46 mequiv·g(-1)) exhibited the highest proton conductivity, which was 0.147 S· cm(-1) at 25 °C and 0.271 S·cm(-1) at 80 °C, respectively. The introduction of dual naphthalene moieties is expected to achieve much enhanced properties compared to those of sulfonated poly(arylene ether ketones) (SNPAEK-x), consisting of single naphthalene and flexible sulfoalkyl groups. Compared with SNPAEK-1.60 with a similar IEC, SDN-PAEK-1.74 membrane showed higher proton conductivity, higher IEC normalized conductivity, and higher effective proton mobility, although it had lower analytical acid concentration. The SDN-PAEK-x membranes with IECs higher than 1.96 mequiv·g(-1) also exhibited higher proton conductivity than that of recast Nafion membrane. Furthermore, SDN-PAEK-1.94 displayed a better single cell performance with a maximum power density of 60 mW·cm(-2) at 80 °C. Considering its high proton conductivity, excellent single cell performance, good mechanical stabilities, low membrane swelling, and methanol permeability, SDN-PAEK-x membranes are promising candidates as alternative polymer electrolyte membranes to Nafion for direct methanol fuel cell applications.

Fullerene reinforced ionic polymer transducer

NASA Astrophysics Data System (ADS)

Jung, J. H.; Cheng, T. H.; Oh, I. K.

2009-07-01

Novel fullerene reinforced nano-composite transducers based on nafion were developed inorder to improve the ionic polymer metal composite transducer. The fullerene reinforced nano-composite membranes were fabricated by recasting method with 0.1 and 0.5 weight percentage of a Fullerenes. Stress-Strain tests showed tremendous increase in stiffness and modulus of the nano-composite membranes even at these minute concentrations of Fullerenes. Ionic exchange capacity analysis and proton conductivity test were performed to calculate the electrical property of the composite films. Water uptake was measured to understand the liquid adsorbing characteristics of the membranes. Also, tip displacement of the nano-composite membrane transducer was investigated under AC excitations with various magnitudes and frequencies. Furthermore, the generated energy was measured from external sinusoidal physical input vibration with several displacements and frequencies by using a mechanical shaker. As a result, the fullerene reinforced nanocomposite membrane based on nafion shows higher stiffness and Young's modulus than that of pure nafion membrane. Also, the nano-composite membrane had better water uptake and proton conductivity than the pure membrane. Fullerene reinforced nano-composite membrane transducer actuates to a much larger deformations than pure nafion membrane transducer. The developed membrane transducer dissipates more energy from the physical input vibration than that of unfilled(or virgin) Nafion membrane transducer.

A novel branched side-chain-type sulfonated polyimide membrane with flexible sulfoalkyl pendants and trifluoromethyl groups for vanadium redox flow batteries

NASA Astrophysics Data System (ADS)

Li, Jinchao; Liu, Suqin; He, Zhen; Zhou, Zhi

2017-04-01

A novel branched side-chain-type sulfonated polyimide (6F-s-bSPI) membrane with accessible branching agents of melamine, hydrophobic trifluoromethyl groups (sbnd CF3), and flexible sulfoalkyl pendants is prepared by a high-temperature polycondensation and post-sulfonation method for use in vanadium redox flow batteries (VRFBs). The chemical structure of the 6F-s-bSPI membrane is confirmed by ATR-FTIR and 1H NMR spectra. The physico-chemical properties of the as-prepared 6F-s-bSPI membrane are systematically investigated and found to be strongly related to the specially designed structure. The 6F-s-bSPI membrane offers a reduced cost and possesses a significantly lowered vanadium ion permeability (1.18 × 10-7 cm2 min-1) compared to the linear SPI (2.25 × 10-7 cm2 min-1) and commercial Nafion 115 (1.36 × 10-6 cm2 min-1) membranes, prolonging the self-discharge duration of the VRFBs. In addition, the VRFB assembled with a 6F-s-bSPI membrane shows higher coulombic (98.3%-99.7%) and energy efficiencies (88.4%-66.12%) than that with a SPI or Nafion 115 membrane under current densities ranging from 20 to 100 mA cm-2. Moreover, the VRFB with a 6F-s-bSPI membrane delivers a stable cycling performance over 100 cycles with no decline in coulombic and energy efficiencies. These results show that the branched side-chain-type structure is a promising design to prepare excellent proton conductive membranes.

Carbon Nanotube-Based Membrane for Light-Driven, Simultaneous Proton and Electron Transport

DOE PAGES

Pilgrim, Gregory A.; Amori, Amanda R.; Hou, Zhentao; ...

2016-12-07

Here we discuss the photon driven transport of protons and electrons over hundreds of microns through a membrane based on vertically aligned single walled carbon nanotubes (SWNTs). Electrons are photogenerated in colloidal CdSe quantum dots that have been noncovalently attached to the carbon nanotube membrane and can be delivered at potentials capable of reducing earth-abundant molecular catalysts that perform proton reduction. Proton transport is driven by the electron photocurrent and is shown to be faster through the SWNT based membrane than through the commercial polymer Nafion. Furthermore, the potential utility of SWNT membranes for solar water splitting applications is demonstratedmore » through their excellent proton and electron transport properties as well as their ability to interact with other components of water splitting systems, such as small molecule electron acceptors.« less

Proton Transfer in Perfluorosulfonic Acid Fuel Cell Membranes with Differing Pendant Chains and Equivalent Weights.

PubMed

Thomaz, Joseph E; Lawler, Christian M; Fayer, Michael D

2017-05-04

Proton transfer in the nanoscopic water channels of polyelectrolyte fuel cell membranes was studied using a photoacid, 8-hydroxypyrene-1,3,6-trisulfonic acid sodium salt (HPTS), in the channels. The local environment of the probe was determined using 8-methoxypyrene-1,3,6-trisulfonic acid sodium salt (MPTS), which is not a photoacid. Three fully hydrated membranes, Nafion (DuPont) and two 3M membranes, were studied to determine the impact of different pendant chains and equivalent weights on proton transfer. Fluorescence anisotropy and excited state population decay data that characterize the local environment of the fluorescent probes and proton transfer dynamics were measured. The MPTS lifetime and anisotropy results show that most of the fluorescent probes have a bulk-like water environment with a relatively small fraction interacting with the channel wall. Measurements of the HPTS protonated and deprotonated fluorescent bands' population decays provided information on the proton transport dynamics. The decay of the protonated band from ∼0.5 ns to tens of nanoseconds is in part determined by dissociation and recombination with the HPTS, providing information on the ability of protons to move in the channels. The dissociation and recombination is manifested as a power law component in the protonated band fluorescence decay. The results show that equivalent weight differences between two 3M membranes resulted in a small difference in proton transfer. However, differences in pendant chain structure did significantly influence the proton transfer ability, with the 3M membranes displaying more facile transfer than Nafion.

Optical-Electrical-Chemical Engineering of PEDOT:PSS by Incorporation of Hydrophobic Nafion for Efficient and Stable Perovskite Solar Cells.

PubMed

Ma, Shuang; Qiao, Wenyuan; Cheng, Tai; Zhang, Bing; Yao, Jianxi; Alsaedi, Ahmed; Hayat, Tasawar; Ding, Yong; Tan, Zhan'ao; Dai, Songyuan

2018-01-31

In PIN-type perovskite solar cells (PSCs), the hydroscopicity and acidity of the poly(3,4-ethylenedioxythiophene)-poly(styrene-sulfonate) (PEDOT:PSS) hole transport layer (HTL) have critical influences on the device stability. To eliminate these problems, Nafion, the hydrophobic perfluorosulfonic copolymer, is incorporated into PEDOT:PSS by a simple spin-coating process. For the modified film, Nafion/PSSH (poly(styrene sulfonate) acid) acts as an electron-blocking layer on the surface and the PEDOT-rich domain tends to gather into larger particles with better interchain charge transfer inside the film. Consequently, the modified PEDOT:PSS HTL shows enhanced conductivity and light transmittance as well as more favorable work function, ending up with the increased short-circuit current density (J sc ) and open-circuit voltage (V oc ) of the device. Finally, PSCs with Nafion-modified HTLs achieve the best power conversion efficiency of 16.72%, with 23.76% improvement compared with PEDOT:PSS-only devices (13.51%). Most importantly, the device stability is obviously enhanced because of the hydrophobicity and chemical and mechanical stability of the Nafion polymer that is enriched on the surface of the PEDOT:PSS film.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Reed, David M.; Thomsen, Edwin C.; Wang, Wei

Three Nafion membranes of similar composition but different thicknesses were operated in a 3-cell 1kW class all vanadium mixed acid redox flow battery. The influence of current density on the charge/discharge characteristics, coulombic and energy efficiency, capacity fade, operating temperature and pressure drop in the flow circuit will be discussed and correlated to the Nafion membrane thickness. Material costs associated with the Nafion membranes, ease of handling the membranes, and performance impacts will also be discussed.

A sugar-template manufacturing method for microsystem ion-exchange membranes

NASA Astrophysics Data System (ADS)

Festarini, Rio V.; Pham, Minh-Hao; Liu, Xinyue; Barz, Dominik P. J.

2017-07-01

In this work, we report on a novel method for producing ion-exchange membranes that can be integrated directly into polydimethylsiloxane-based micro devices. Ionomers such as NafionTM, a copolymer with high conductivity and selectivity to small cations, are generally incompatible with common micro device materials due to the chemical inertness of the tetrafluoroethylene-based skeleton and the swelling in aqueous solutions. Hence, we introduce a microfabrication concept where we use consolidated sugar granules as a template to produce a porous polydimethylsiloxane scaffold. Ionomer and scaffold are combined to a composite membrane where the cohesion of these incompatible materials is of rather mechanical nature; i.e. the ionomer is physically entrapped in the scaffold. Electrochemical impedance spectroscopy measurements reveal the excellent membrane conductivity for the upper electrolyte concentrations tested in this work.

Nafion induced surface confinement of oxygen in carbon-supported oxygen reduction catalysts

DOE PAGES

Chlistunoff, Jerzy; Sansinena, Jose -Maria

2016-11-17

We studied the surface confinement of oxygen inside layers of Nafion self-assembled on carbon-supported oxygen reduction reaction (ORR) catalysts. It is demonstrated that oxygen accumulates in the hydrophobic component of the polymer remaining in contact with the carbon surface. Furthermore, the amount of surface confined oxygen increases with the degree of carbon surface graphitization, which promotes the self-assembly of the polymer. Planar macrocyclic ORR catalysts possessing a delocalized system of π electrons such as Co and Fe porphyrins and phthalocyanines have virtually no effect on the surface confinement of oxygen, in accordance with their structural similarity to graphitic carbon surfacesmore » where they adsorb. Platinum particles in carbon-supported ORR catalysts with high metal contents (20%) disrupt the self-assembly of Nafion and virtually eliminate the oxygen confinement, but the phenomenon is still observed for low Pt loading (4.8%) catalysts.« less

Nafion induced surface confinement of oxygen in carbon-supported oxygen reduction catalysts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chlistunoff, Jerzy; Sansinena, Jose -Maria

We studied the surface confinement of oxygen inside layers of Nafion self-assembled on carbon-supported oxygen reduction reaction (ORR) catalysts. It is demonstrated that oxygen accumulates in the hydrophobic component of the polymer remaining in contact with the carbon surface. Furthermore, the amount of surface confined oxygen increases with the degree of carbon surface graphitization, which promotes the self-assembly of the polymer. Planar macrocyclic ORR catalysts possessing a delocalized system of π electrons such as Co and Fe porphyrins and phthalocyanines have virtually no effect on the surface confinement of oxygen, in accordance with their structural similarity to graphitic carbon surfacesmore » where they adsorb. Platinum particles in carbon-supported ORR catalysts with high metal contents (20%) disrupt the self-assembly of Nafion and virtually eliminate the oxygen confinement, but the phenomenon is still observed for low Pt loading (4.8%) catalysts.« less

Investigation of grafted ETFE-based polymer membranes as alternative electrolyte for direct methanol fuel cells

NASA Astrophysics Data System (ADS)

Aricò, A. S.; Baglio, V.; Cretı̀, P.; Di Blasi, A.; Antonucci, V.; Brunea, J.; Chapotot, A.; Bozzi, A.; Schoemans, J.

Low cost ethylene-tetrafluoroethylene (ETFE)-based grafted membranes have been prepared by a process based on electron beam irradiation, subsequent grafting, cross-linking and sulfonation procedure. Two different grafted membranes varying by their grafting and cross-linking levels have been investigated for applications in direct methanol fuel cells (DMFCs) operating between 90 and 130 °C. DMFC assemblies based on these membranes showed cell resistance and performance values comparable to Nafion 117. Stable electrochemical performance was recorded during 1 month of cycled operation. Tailoring of grafting and cross-linking properties allows a significant reduction of methanol cross-over while maintaining suitable conductivity and performance levels.

Non-covalent bonding interaction of surfactants with functionalized carbon nanotubes in proton exchange membranes for fuel cell applications.

PubMed

Sayeed, M Abu; Kim, Young Ho; Park, Younjin; Gopalan, A I; Lee, Kwang-Pill; Choi, Sang-June

2013-11-01

Dispersion of functionalized multiwalled carbon nanotubes (MWCNTs) in proton exchange membranes (PEMs) was conducted via non-covalent bonding between benzene rings of various surfactants and functionalized MWCNTs. In the solution casting method, dispersion of functionalized MWCNTs in PEMs such as Nafion membranes is a critical issue. In this study, 1 wt.% pristine MWCNTs (p-MWCNTs) and oxidized MWCNTs (ox-MWCNTs) were reinforced in Nafion membranes by adding 0.1-0.5 wt.% of a surfactant such as benzalkonium chloride (BKC) as a cationic surfactant with a benzene ring, Tween-80 as a nonanionic surfactant without a benzene ring, sodium dodecylsulfonate (SDS) as an anionic surfactant without a benzene ring, or sodium dodecylben-zenesulfonate (SDBS) as an anionic surfactant with a benzene ring and their effects on the dispersion of nanocomposites were then observed. Among these surfactants, those with benzene rings such as BKC and SDBS produced enhanced dispersion via non-covalent bonding interaction between CNTs and surfactants. Specifically, the surfactants were adsorbed onto the surface of functionalized MWCNTs, where they prevented re-aggregation of MWCNTs in the nanocomposites. Furthermore, the prepared CNTs reinforced nanocomposite membranes showed reduced methanol uptake values while the ion exchange capacity values were maintained. The enhanced properties, including thermal property of the CNTs reinforced PEMs with surfactants, could be applicable to fuel cell applications.

Random and Block Sulfonated Polyaramides as Advanced Proton Exchange Membranes

DOE PAGES

Kinsinger, Corey L.; Liu, Yuan; Liu, Feilong; ...

2015-10-09

We present here the experimental and computational characterization of two novel copolyaramide proton exchange membranes (PEMs) with higher conductivity than Nafion at relatively high temperatures, good mechanical properties, high thermal stability, and the capability to operate in low humidity conditions. The random and block copolyaramide PEMs are found to possess different ion exchange capacities (IEC) in addition to subtle structural and morphological differences, which impact the stability and conductivity of the membranes. SAXS patterns indicate the ionomer peak for the dry block copolymer resides at q = 0.1 Å –1, which increases in amplitude when initially hydrated to 25% relativemore » humidity, but then decrease in amplitude with additional hydration. This pattern is hypothesized to signal the transport of water into the polymer matrix resulting in a reduced degree of phase separation. Coupled to these morphological changes, the enhanced proton transport characteristics and structural/mechanical stability for the block copolymer are hypothesized to be primarily due to the ordered structure of ionic clusters that create connected proton transport pathways while reducing swelling upon hydration. Interestingly, the random copolymer did not possess an ionomer peak at any of the hydration levels investigated, indicating a lack of any significant ionomer structure. The random copolymer also demonstrated higher proton conductivity than the block copolymer, which is opposite to the trend normally seen in polymer membranes. However, it has reduced structural/mechanical stability as compared to the block copolymer. In conclusion, this reduction in stability is due to the random morphology formed by entanglements of polymer chains and the adverse swelling characteristics upon hydration. Therefore, the block copolymer with its enhanced proton conductivity characteristics, as compared to Nafion, and favorable structural/mechanical stability, as compared to the

Performance enhancement of direct ethanol fuel cell using Nafion composites with high volume fraction of titania

NASA Astrophysics Data System (ADS)

Matos, B. R.; Isidoro, R. A.; Santiago, E. I.; Fonseca, F. C.

2014-12-01

The present study reports on the performance enhancement of direct ethanol fuel cell (DEFC) at 130 °C with Nafion-titania composite electrolytes prepared by sol-gel technique and containing high volume fractions of the ceramic phase. It is found that for high volume fractions of titania (>10 vol%) the ethanol uptake of composites is largely reduced while the proton conductivity at high-temperatures is weakly dependent on the titania content. Such tradeoff between alcohol uptake and conductivity resulted in a boost of DEFC performance at high temperatures using Nafion-titania composites with high fraction of the inorganic phase.

Composite polymer electrolyte containing ionic liquid and functionalized polyhedral oligomeric silsesquioxanes for anhydrous PEM applications.

PubMed

Subianto, Surya; Mistry, Mayur K; Choudhury, Namita Roy; Dutta, Naba K; Knott, Robert

2009-06-01

A new type of supported liquid membrane was made by combining an ionic liquid (IL) with a Nafion membrane reinforced with multifunctional polyhedral oligomeric silsesquioxanes (POSSs) using a layer-by-layer strategy for anhydrous proton-exchange membrane (PEM) application. The POSS was functionalized by direct sulfonation, and the sulfonated POSS (S-POSS) was incorporated into Nafion 117 membranes by the infiltration method. The resultant hybrid membrane shows strong ionic interaction between the Nafion matrix and the multifunctional POSS, resulting in increased glass transition temperature and thermal stability at very low loadings of S-POSS (1%). The presence of S-POSS has also improved the proton conductivity especially at low humidities, where it shows a marked increase due to its confinement in the ionic domains and promotes water uptake by capillary condensation. In order to achieve anhydrous conductivity, the IL 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (BMI-BTSI) was incorporated into these membranes to provide proton conduction in the absence of water. Although the incorporation of an IL shows a plasticizing effect on the Nafion membrane, the S-POSS composite membrane with an IL shows a higher modulus at high temperatures compared to Nafion 117 and a Nafion-IL membrane, with significantly higher proton conductivity (5 mS/cm at 150 degrees C with 20% IL). This shows the ability of the multifunctional POSS and IL to work symbiotically to achieve the desirable proton conductivity and mechanical properties of such membranes by enhancing the ionic interaction within the material.

Effects of Block Length and Membrane Processing Conditions on the Morphology and Properties of Perfluorosulfonated Poly(arylene ether sulfone) Multiblock Copolymer Membranes for PEMFC.

PubMed

Assumma, Luca; Nguyen, Huu-Dat; Iojoiu, Cristina; Lyonnard, Sandrine; Mercier, Régis; Espuche, Eliane

2015-07-01

Perfluorosulfonated poly(arylene ether sulfone) multiblock copolymers have been shown to be promising as proton exchange membranes. The commonly used approach for preparation of the membrane is solvent casting; the properties of the resulting membranes are very dependent on the membrane processing conditions. In this paper, we study the effects of block length, selectivity of the solvent, and thermal treatment on the membrane properties such as morphology, water uptake, and ionic conductivity. DiMethylSulfOxide (DMSO), and DiMethylAcetamide (DMAc) were selected as casting solvents based on the Flory-Huggins parameter calculated by inversion gas chromatography (IGC). It was found that the solvent selectivity has a mild impact on the mean size of the ionic domains and the expansion upon swelling, while it dramatically affects the supramolecular ordering of the blocks. The membranes cast from DMSO exhibit more interconnected ionic clusters yielding higher conductivities and water uptake as compared to membranes cast from DMAc. A 10-fold increase in proton conductivity was achieved after thermal annealing of membranes at 150 °C, and the ionomers with longer block lengths show conductivities similar to Nafion at 80 °C and low relative humidity (30%).

Nafion(TM) Coats For Electrodes In Liquid-Feed Fuel Cells

NASA Technical Reports Server (NTRS)

Narayanan, Sekharipuram R.; Surampudi, Subbarao; Halpert, Gerald; Vamos, Eugene; Frank, Harvey A.

1995-01-01

Coating or impregnation with commercially available material enables oxidation of organic liquid fuels. Nafion(TM) investigated for use in application because of known combination of desirable characteristics: It is perfluorinated, hydrophilic, proton-conducting ion-exchange polymer exhibiting relatively high thermal and electrochemical stability and not detrimental to kinetics of electrochemical processes. Available in solubilized form and used to apply stable coats to surfaces of electrodes.

Semi-interpenetrating polymer network proton exchange membranes with narrow and well-connected hydrophilic channels

NASA Astrophysics Data System (ADS)

Fang, Chunliu; Toh, Xin Ni; Yao, Qiaofeng; Julius, David; Hong, Liang; Lee, Jim Yang

2013-03-01

Four series of semi-interpenetrating polymer network (SIPN) membranes are fabricated by thermally cross-linking aminated BPPO (brominated poly(2,6-dimethyl-1,4-phenylene oxide)) with different epoxide cross-linkers in the presence of sulfonated PPO (SPPO). The cross-link structure and hydrophobicity are found to impact the membrane morphology strongly - smaller and more hydrophobic cross-links form narrow and well-connected hydrophilic channels whereas bulky and less hydrophobic cross-links form wide but less-connected hydrophilic channels. The membranes of the former can support facile proton transport and suppress methanol crossover to result in higher proton conductivity and lower methanol permeability than the membranes of the latter. The membranes are also fabricated into membrane electrode assemblies (MEAs) and tested in single-stack direct methanol fuel cells (DMFCs). It is found that some of these SIPN membranes can surpass Nafion® 117 in maximum power density, demonstrating their potential as a proton exchange membrane (PEM) for the DMFCs.

Electrochemical Detection of p-Aminophenol by Flexible Devices Based on Multi-Wall Carbon Nanotubes Dispersed in Electrochemically Modified Nafion

PubMed Central

Scandurra, Graziella; Antonella, Arena; Ciofi, Carmine; Saitta, Gaetano; Lanza, Maurizio

2014-01-01

A conducting composite prepared by dispersing multi-walled carbon nanotubes (MWCNTs) into a host matrix consisting of Nafion, electrochemically doped with copper, has been prepared, characterized and used to modify one of the gold electrodes of simply designed electrochemical cells having copier grade transparency sheets as substrates. Electrical measurements performed in deionized water show that the Au/Nafion/Au-MWCNTs–Nafion:Cu cells can be successfully used in order to detect the presence of p-aminophenol (PAP) in water, without the need for any supporting electrolyte. The intensity of the redox peaks arising when PAP is added to deionized water is found to be linearly related to the analyte in the range from 0.2 to 1.6 μM, with a detection limit of 90 nM and a sensitivity of 7 μA·(μM−1)·cm−2. PMID:24854357

Composite Electrolyte Membranes from Partially Fluorinated Polymer and Hyperbranched, Sulfonated Polysulfone

PubMed Central

Subianto, Surya; Roy Choudhury, Namita; Dutta, Naba

2013-01-01

Macromolecular modification of poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF) was done with various proportions of sulfonic acid terminated, hyperbranched polysulfone (HPSU) with a view to prepare ion conducting membranes. The PVDF-co-HFP was first chemically modified by dehydrofluorination and chlorosulfonation in order to make the membrane more hydrophilic as well as to introduce unsaturation, which would allow crosslinking of the PVDF-co-HFP matrix to improve the stability of the membrane. The modified samples were characterized for ion exchange capacity, morphology, and performance. The HPSU modified S-PVDF membrane shows good stability and ionic conductivity of 5.1 mS cm−1 at 80 °C and 100% RH for blends containing 20% HPSU, which is higher than the literature values for equivalent blend membranes using Nafion. SEM analysis of the blend membranes containing 15% or more HPSU shows the presence of spherical domains with a size range of 300–800 nm within the membranes, which are believed to be the HPSU-rich area. PMID:28348282

Bio-functionalization of electro-synthesized polypyrrole surface by heme enzyme using a mixture of Nafion and glutaraldehyde as synergetic immobilization matrix: Conformational characterization and electrocatalytic studies

NASA Astrophysics Data System (ADS)

ElKaoutit, Mohammed; Naranjo-Rodriguez, Ignacio; Domínguez, Manuel; Hidalgo-Hidalgo-de-Cisneros, José Luis

2011-10-01

Use of a mixture of Nafion and glutaraldehyde as new immobilization matrix was described. The percentage of Nafion was optimized to prevent denaturation of horseradish peroxidase enzyme after its crosslinkage with glutaraldehyde on electro-synthesized polypyrrole surface. Topographic study by Atomic Force Microscopy (AFM) shows that the enzyme seems to have been introduced inside the ionic cluster of Nafion. The characterization of the resulting bio-interfaces by UV-vis and FT-IR shows that the intra-crosslinkage phenomena caused by the use of glutaraldehyde can be eliminated by the optimization of the concentration of Nafion additive. The secondary structure contents of native and immobilized enzyme were analyzed by a Gaussian curve fitting of the respective FT-IR spectra in the amide I region. Immobilized enzyme presented notable increasing percentages of globular and short helical structure compared with native enzyme. This indicates that immobilized enzyme was folded which is in accordance with AFM studies and supports the enzyme entrance inside ionic clutter of Nafion. Thanks to synergic effects of the polypyrrole conducting polymer and the perfluorosulfonic acid polymer Nafion, HRP enzyme was immobilized in its "native" state, the resulting biosensor was able to sense peroxide without any chemical mediator and can be categorized as third generation.

Preparation of a self-humidifying membrane electrode assembly for fuel cell and its performance analysis

NASA Astrophysics Data System (ADS)

Wang, Cheng; Mao, Zongqiang; Xu, Jingming; Xie, Xiaofeng; Yang, Lizhai

2003-10-01

A novel nano-porous material SiO2-gel was prepared. After being purified by H2O2, then protonized by H2SO4 and desiccated in vacuum, the SiO2-gel, mixed with Nafion solution, was coated between an electrode and a solid electrolyte, which made a new type of self-humidifying membrane electrode assembly. The SiO2 powder was characterized by FTIR, BET and XRD. The surface of the electrodes was characterized by SEM and EDS. The performances of the self-humidifying membrane electrodes were analyzed by polarization discharge and AC impedance under the operation modes of external humidification and self-humidification respectively. Experimental-results indicated that the SiO2 powder held super-hydrophilicity, and the layer of SiO2 and Nafion polymer between electrode and solid electrolyte expanded three-dimension electrochemistry reac-tion area, maintained stability of catalyst layer and enhanced back-diffusion of water from cathode to anode, so the PEM Fuel cell can generate electricity at self-humidification mode. The power density of single PEM fuel cell reached 1.5 W/cm2 under 0.2 Mpa, 70°C and dry hydrogen and oxygen.

Highly selective dopamine electrochemical sensor based on electrochemically pretreated graphite and nafion composite modified screen printed carbon electrode.

PubMed

Ku, Shuhao; Palanisamy, Selvakumar; Chen, Shen-Ming

2013-12-01

Herein, we report a highly selective dopamine electrochemical sensor based on electrochemically pretreated graphite/nafion composite modified screen printed carbon (SPC) electrode. Electrochemically activated graphite/nafion composite was prepared by using a simple electrochemical method. Scanning electron microscope (SEM) used to characterize the surface morphology of the fabricated composite electrode. The SEM result clearly indicates that the graphitic basal planes were totally disturbed and leads to the formation of graphite nanosheets. The composite modified electrode showed an enhanced electrocatalytic activity toward the oxidation of DA when compared with either electrochemical pretreated graphite or nafion SPC electrodes. The fabricated composite electrode exhibits a good electrocatalytic oxidation toward DA in the linear response range from 0.5 to 70 μM with the detection limit of 0.023 μM. The proposed sensor also exhibits very good selectivity and stability, with the appreciable sensitivity. In addition, the proposed sensor showed satisfactory recovery results toward the commercial pharmaceutical DA samples. Copyright © 2013 Elsevier Inc. All rights reserved.

Composite plasma polymerized sulfonated polystyrene membrane for PEMFC

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nath, Bhabesh Kumar; Khan, Aziz; Chutia, Joyanti, E-mail: jchutiaiasst@gmail.com

2015-10-15

Highlights: • Methyl methane sulfonate (MMS) is used as the sulfonating agent. • The proton conductivity of the membrane is found to be 0.141 S cm{sup −1}. • Power density of fuel cell with styrene/MMS membrane is 0.5 W cm{sup −2}. • The membrane exhibits thermal stability up to 140 °C. - Abstract: This work presents the introduction of an organic compound methyl methane sulfonate (MMS) for the first time in fabrication of polystyrene based proton exchange membrane (PEM) by plasma polymerization process. The membrane is fabricated by co-polymerizing styrene and MMS in capacitively coupled continuous RF plasma. The chemicalmore » composition of the plasma polymerized polymer membrane is investigated using Fourier Transform Infrared Spectroscopy which reveals the formation of composite structure of styrene and MMS. The surface morphology studied using AFM and SEM depicts the effect of higher partial pressure of MMS on surface topography of the membrane. The proton transport property of the membrane studied using electrochemical impedance spectroscopy shows the achievement of maximum proton conductivity of 0.141 S cm{sup −1} which is comparable to Nafion 117 membrane. Fuel cell performance test of the synthesized membrane shows a maximum power density of 500 mW cm{sup −2} and current density of 0.62 A cm{sup −2} at 0.6 V.« less

High temperature polymers for proton exchange membrane fuel cells

NASA Astrophysics Data System (ADS)

Einsla, Brian Russel

Novel proton exchange membranes (PEMs) were investigated that show potential for operating at higher temperatures in both direct methanol (DMFC) and H 2/air PEM fuel cells. The need for thermally stable polymers immediately suggests the possibility of heterocyclic polymers bearing appropriate ion conducting sites. Accordingly, monomers and random disulfonated poly(arylene ether) copolymers containing either naphthalimide, benzoxazole or benzimidazole moieties were synthesized via direct copolymerization. The ion exchange capacity (IEC) was varied by simply changing the ratio of disulfonated monomer to nonsulfonated monomer in the copolymerization step. Water uptake and proton conductivity of cast membranes increased with IEC. The water uptake of these heterocyclic copolymers was lower than that of comparable disulfonated poly(arylene ether) systems, which is a desirable improvement for PEMs. Membrane electrode assemblies were prepared and the initial fuel cell performance of the disulfonated polyimide and polybenzoxazole (PBO) copolymers was very promising at 80°C compared to the state-of-the-art PEM (NafionRTM); nevertheless these membranes became brittle under operating conditions. Several series of poly(arylene ether)s based on disodium-3,3'-disulfonate-4,4 '-dichlorodiphenylsulfone (S-DCDPS) and a benzimidazole-containing bisphenol were synthesized and afforded copolymers with enhanced stability. Selected properties of these membranes were compared to separately prepared miscible blends of disulfonated poly(arylene ether sulfone) copolymers and polybenzimidazole (PBI). Complexation of the sulfonic acid groups with the PBI structure reduced water swelling and proton conductivity. The enhanced proton conductivity of NafionRTM membranes has been proposed to be due to the aggregation of the highly acidic side-chain sulfonic acid sites to form ion channels. A series of side-chain sulfonated poly(arylene ether sulfone) copolymers based on methoxyhydroquinone was

Inverted Fuel Cell: Room-Temperature Hydrogen Separation from an Exhaust Gas by Using a Commercial Short-Circuited PEM Fuel Cell without Applying any Electrical Voltage.

PubMed

Friebe, Sebastian; Geppert, Benjamin; Caro, Jürgen

2015-06-26

A short-circuited PEM fuel cell with a Nafion membrane has been evaluated in the room-temperature separation of hydrogen from exhaust gas streams. The separated hydrogen can be recovered or consumed in an in situ olefin hydrogenation when the fuel cell is operated as catalytic membrane reactor. Without applying an outer electrical voltage, there is a continuous hydrogen flux from the higher to the lower hydrogen partial pressure side through the Nafion membrane. On the feed side of the Nafion membrane, hydrogen is catalytically split into protons and electrons by the Pt/C electrocatalyst. The protons diffuse through the Nafion membrane, the electrons follow the short-circuit between the two brass current collectors. On the cathode side, protons and electrons recombine, and hydrogen is released. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Preparation and characterization of self-crosslinked organic/inorganic proton exchange membranes

NASA Astrophysics Data System (ADS)

Zhong, Shuangling; Cui, Xuejun; Dou, Sen; Liu, Wencong

A series of silicon-containing sulfonated polystyrene/acrylate (Si-sPS/A) nanoparticles are successfully synthesized via simple emulsion polymerization method. The Si-sPS/A latexes show good film-forming capability and the self-crosslinked organic/inorganic proton exchange membranes are prepared by pouring the Si-sPS/A nanoparticle latexes into glass plates and drying at 60 °C for 10 h and 120 °C for 2 h. The potential of the membranes in direct methanol fuel cells (DMFCs) is characterized preliminarily by studying their thermal stability, ion-exchange capacity, water uptake, methanol diffusion coefficient, proton conductivity and selectivity (proton conductivity/methanol diffusion coefficient). The results indicate that these membranes possess excellent thermal stability and methanol barrier due to the existence of self-crosslinked silica network. In addition, the proton conductivity of the membranes is in the range of 10 -3-10 -2 S cm -1 and all the membranes show much higher selectivity in comparison with Nafion ® 117. These results suggest that the self-crosslinked organic/inorganic proton exchange membranes are particularly promising in DMFC applications.

Porous poly(benzimidazole) membrane for all vanadium redox flow battery

NASA Astrophysics Data System (ADS)

Luo, Tao; David, Oana; Gendel, Youri; Wessling, Matthias

2016-04-01

Porous poly(benzimidazole) (PBI) membranes of low vanadium ions permeability are described for an all vanadium redox flow battery (VRFB). The PBI membrane was prepared by a water vapour induced phase inversion process of a PBI polymer solution. The membrane has a symmetrical cross-sectional morphology. A low water permeability of 16.5 L (m2 h bar)-1 indicates the high hydraulic resistance stemming from a closed cell morphology with nanoporous characteristics. The PBI membrane doped with 2.5 M H2SO4 shows a proton conductivity of 16.6 mS cm-1 and VO2+ permeability as low as 4.5 × 10-8 cm2 min-1. The stability test of dense PBI membrane in VO2+ solution indicates good chemical stability. An all vanadium redox flow battery (VRFB) operated with the porous PBI membrane shows 98% coulombic efficiency and more than 10% higher energy efficiency compared to VRFB operated with Nafion 112 at applied current densities of 20-40 mA cm-2. High in situ stability of the porous PBI membrane was confirmed by about 50 cycles of continuous charge and discharge operation of the battery.

Influence of solvents on species crossover and capacity decay in non-aqueous vanadium redox flow batteries: Characterization of acetonitrile and 1, 3 dioxolane solvent mixture

NASA Astrophysics Data System (ADS)

Bamgbopa, Musbaudeen O.; Almheiri, Saif

2017-02-01

The importance of the choice of solvent in a non-aqueous redox flow battery (NARFB) cannot be overemphasized. Several studies demonstrated the influence of the solvent on electrolyte performance in terms of reaction rates, energy/power densities, and efficiencies. In this work, we investigate capacity decay as a direct consequence of varying reactant crossover rates through membranes in different solvent environments. Specifically, we demonstrate the superiority of an 84/16 vol% acetonitrile/1,3 dioxolane solvent mixture over pure acetonitrile in terms of energy efficiency (up to 89%) and capacity retention for vanadium NARFBs - while incorporating a Nafion 115 membrane. The permeability of Nafion to the vanadium acetylacetonate active species is an order of magnitude lower when pure acetonitrile is replaced by the solvent mixture. A method to estimate relative membrane permeability is formulated from numerical analysis of self-discharge experimental data. Furthermore, tests on a modified Nafion/SiO2 membrane, which generally offered low species permeability, also show that different solvents alter membrane permeability. Elemental and morphological analyses of cycled Nafion and NafionSi membranes in different solvent environments indicate that different crossover rates induced by the choice of solvent during cycling are due to changes in the membrane microstructure, intrinsic permeability, swelling rates, and chemical stability.

Multiplex lithography for multilevel multiscale architectures and its application to polymer electrolyte membrane fuel cell

NASA Astrophysics Data System (ADS)

Cho, Hyesung; Moon Kim, Sang; Sik Kang, Yun; Kim, Junsoo; Jang, Segeun; Kim, Minhyoung; Park, Hyunchul; Won Bang, Jung; Seo, Soonmin; Suh, Kahp-Yang; Sung, Yung-Eun; Choi, Mansoo

2015-09-01

The production of multiscale architectures is of significant interest in materials science, and the integration of those structures could provide a breakthrough for various applications. Here we report a simple yet versatile strategy that allows for the LEGO-like integrations of microscale membranes by quantitatively controlling the oxygen inhibition effects of ultraviolet-curable materials, leading to multilevel multiscale architectures. The spatial control of oxygen concentration induces different curing contrasts in a resin allowing the selective imprinting and bonding at different sides of a membrane, which enables LEGO-like integration together with the multiscale pattern formation. Utilizing the method, the multilevel multiscale Nafion membranes are prepared and applied to polymer electrolyte membrane fuel cell. Our multiscale membrane fuel cell demonstrates significant enhancement of performance while ensuring mechanical robustness. The performance enhancement is caused by the combined effect of the decrease of membrane resistance and the increase of the electrochemical active surface area.

New High Performance Water Vapor Membranes to Improve Fuel Cell Balance of Plant Efficiency and Lower Costs

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wagener, Earl; Topping, Chris; Morgan, Brad

Hydrogen fuel cells are currently one of the more promising long term alternative energy options and out of the range of fuel cell technologies under development, proton exchange membranes [PEMs] have the advantage of being able to deliver high power density at relatively low operating temperatures. This is essential for systems such as fuel cell vehicles (FCV) and many stationary applications that undergoing frequent on/off cycling. One of the biggest challenges for PEM systems is the need to maintain a high level of hydration in the cell to enable efficient conduction of protons from the anode to the cathode. Inmore » addition to significant power loss, low humidity conditions lead to increased stress on the membranes which can result in both physical and chemical degradation. Therefore, an effective fuel cell humidifier can be critical for the efficient operation and durability of the system under high load and low humidity conditions. The most common types of water vapor transport (WVT) devices are based on water permeable membrane based separators. Successful membranes must effectively permeate water vapor while restricting crossover of air, and be robust to the temperature and humidity fluctuations experienced in fuel cell systems. DOE sponsored independent evaluations indicate that balance of plant components, including humidification devices, make up more than half of the cost of current automotive fuel cell systems. Despite its relatively widespread us in other applications, the current industry standard perfluorosulfonic acid based Nafion® remains expensive compared with non-perfluorinated polymer membranes. During Phase II of this project, we demonstrated the improved performance of our semi-fluorinated perfluorocyclobutyl polymer based membranes compared with the current industry standard perfluorosulfonic acid based Nafion®, at ~ 50% lower cost. Building on this work, highlights of our Phase IIB developments, in close collaboration with leading

Studies on Methanol Crossover in Liquid-Feed Direct Methanol Pem Fuel Cells

NASA Technical Reports Server (NTRS)

Narayanan, S. R.

1995-01-01

The performance of liquid feed direct methanol fuel cells using various types of Nafion membranes as the solid polymer electrolyte have been studied. The rate of fuel crossover and electrical performance has been measured for cells with Nafion membranes of various thicknesses and equivalent weights. The crossover rate is found to decrease with increasing thickness and applied current. The dependence of crossover rate on current density can be understood in terms of a simple linear diffusion model which suggests that the crossover rate can be influenced by the electrode structure in addition to the membrane. The studies suggest that Nafion EW 1500 is a very promising alternate to Nafion EW 1100 for direct methanol fuel cells.

Voltammetric determination of In3+ based on the bifunctionality of a multi-walled carbon nanotubes-nafion modified electrode.

PubMed

Li, Junhua; Zhang, Fuxing; Wang, Jianqiu; Xu, Zhifeng; Zeng, Rongying

2009-05-01

Due to the strong cation-exchange ability of Nafion and the excellent properties of multi-walled carbon nanotubes (MWCNTs), a highly sensitive and mercury-free method of determining trace levels of In(3+) has been established based on the bifunctionality of a MWCNTs/Nafion modified glassy carbon electrode (GCE). The MWCNTs/Nafion modified GCE detects In(3+) in a 0.01 M HAc-NaAc buffer solution at pH 5.0 using anodic stripping voltammetry (ASV). The experimental results suggest that a sensitive anodic stripping peak appears at -0.58 V on anodic stripping voltammograms, which can be used as an analytical signal for the determination of In(3+). A good linear relationship between the stripping peak currents and the In(3+) concentration is obtained, covering the concentration range from 5.0 x 10(-10) to 2.0 x 10(-7) M, with a correlation coefficient of 0.999; the detection limit is 1.0 x 10(-11) M. This proposed method has been applied to detect In(3+) as a new way.

Evolution of nano-rheological properties of Nafion¯ thin films during pH modification by strong base treatment: A static and dynamic force spectroscopy study

NASA Astrophysics Data System (ADS)

Eslami, Babak; López-Guerra, Enrique A.; Raftari, Maryam; Solares, Santiago D.

2016-04-01

Addition of a strong base to Nafion® proton exchange membranes is a common practice in industry to increase their overall performance in fuel cells. Here, we investigate the evolution of the nano-rheological properties of Nafion thin films as a function of the casting pH, via characterization with static and dynamic, contact and intermittent-contact atomic force microscopy (AFM) techniques. The addition of KOH causes non-monotonic changes in the viscoelastic properties of the films, which behave as highly dissipative, softer materials near neutral pH values, and as harder, more elastic materials at extreme pH values. We quantify this behavior through calculation of the temporal evolution of the compliance and the glassy compliance under static AFM measurements. We complement these observations with dynamic AFM metrics, including dissipated power and virial (for intermittent-contact-mode measurements), and contact resonance frequency and quality factor (for dynamic contact-mode measurements). We explain the non-monotonic material property behavior in terms of the degree of ionic crosslinking and moisture content of the films, which vary with the addition of KOH. This work focuses on the special case study of the addition of strong bases, but the observed mechanical property changes are broadly related to water plasticizing effects and ionic crosslinking, which are also important in other types of films.

Proton exchange membrane materials for the advancement of direct methanol fuel-cell technology

DOEpatents

Cornelius, Christopher J [Albuquerque, NM

2006-04-04

A new class of hybrid organic-inorganic materials, and methods of synthesis, that can be used as a proton exchange membrane in a direct methanol fuel cell. In contrast with Nafion.RTM. PEM materials, which have random sulfonation, the new class of materials have ordered sulfonation achieved through self-assembly of alternating polyimide segments of different molecular weights comprising, for example, highly sulfonated hydrophilic PDA-DASA polyimide segment alternating with an unsulfonated hydrophobic 6FDA-DAS polyimide segment. An inorganic phase, e.g., 0.5 5 wt % TEOS, can be incorporated in the sulfonated polyimide copolymer to further improve its properties. The new materials exhibit reduced swelling when exposed to water, increased thermal stability, and decreased O.sub.2 and H.sub.2 gas permeability, while retaining proton conductivities similar to Nafion.RTM.. These improved properties may allow direct methanol fuel cells to operate at higher temperatures and with higher efficiencies due to reduced methanol crossover.

Enhancement of fuel cell performance with less-water dependent composite membranes having polyoxometalate anchored nanofibrous interlayer

NASA Astrophysics Data System (ADS)

Abouzari-lotf, Ebrahim; Jacob, Mohan V.; Ghassemi, Hossein; Ahmad, Arshad; Nasef, Mohamed Mahmoud; Zakeri, Masoumeh; Mehdipour-Ataei, Shahram

2016-09-01

Polyoxometalate immobilized nanofiber was used to fabricate low gas permeable layer for composite membranes designed for proton exchange membrane fuel cell (PEMFC) operating at low relative humidity (RH). The composite membranes revealed enhanced proton conductivity in dry conditions compared with state-of-the-art pristine membrane (Nafion 112, N112). This was coupled with a low fuel crossover inheriting the composite membranes about 100 mV higher OCV than N112 when tested in PEMFC at 60 °C and 40% RH. A maximum power density of up to 930 mW cm-2 was also achieved which is substantially higher than the N112 under similar conditions (577 mW cm-2). Such remarkable performance enhancement along with undetectable leaching of immobilized polyoxometalate, high dimensional stability and low water uptake of the composite membranes suggest a strong potential for PEMFC under low RH operation.

Biaxial fatigue crack propagation behavior of perfluorosulfonic-acid membranes

NASA Astrophysics Data System (ADS)

Lin, Qiang; Shi, Shouwen; Wang, Lei; Chen, Xu; Chen, Gang

2018-04-01

Perfluorosulfonic-acid membranes have long been used as the typical electrolyte for polymer-electrolyte fuel cells, which not only transport proton and water but also serve as barriers to prevent reactants mixing. However, too often the structural integrity of perfluorosulfonic-acid membranes is impaired by membrane thinning or cracks/pinholes formation induced by mechanical and chemical degradations. Despite the increasing number of studies that report crack formation, such as crack size and shape, the underlying mechanism and driving forces have not been well explored. In this paper, the fatigue crack propagation behaviors of Nafion membranes subjected to biaxial loading conditions have been investigated. In particular, the fatigue crack growth rates of flat cracks in responses to different loading conditions are compared, and the impact of transverse stress on fatigue crack growth rate is clarified. In addition, the crack paths for slant cracks under both uniaxial and biaxial loading conditions are discussed, which are similar in geometry to those found after accelerated stress testing of fuel cells. The directions of initial crack propagation are calculated theoretically and compared with experimental observations, which are in good agreement. The findings reported here lays the foundation for understanding of mechanical failure of membranes.

The effect of ionic membrane properties on the performance of ionic polymer-metal composite (IPMC) actuator

NASA Astrophysics Data System (ADS)

Jho, Jae Y.; Han, Man J.; Park, Jong H.; Lee, Jang Y.; Wang, Hyuck S.

2005-05-01

On purpose to overcome the limit of conventional ionic polymer-metal composites (IPMC) using the commercial ionic membranes, novel IPMCs with radiation-grafted ion-exchange membranes were prepared. Poly(vinylidenefluoride-co-hexafluoropropylene) (PVDF-co-HFP) and poly(ethylene-co-tetrafluoroethylene) (ETFE) were radiation-grafted with styrene, and then sulfonated. The properties of the membranes were modulated by controlling the amount of polystyrene sulfonic acid (PSSA) groups in the membranes. The amount of PSSA groups were tuned by controlling the total absorbed dose of γ-ray. The membranes were characterized by measuring the water-uptake, the ion-exchange capacity, and the ion conductivity. The performance of the IPMCs using these membranes were analyzed with laser displacement meter. They exhibited much larger bending displacement in comparison with Nafion-based IPMC. With increasing the amount of PSSA groups, the maximum displacement and the bending speed were remarkably increased. The results made sure that the property of ion-exchange membrane was the key element affecting the actuation performance of IPMC.

Multiplex lithography for multilevel multiscale architectures and its application to polymer electrolyte membrane fuel cell

PubMed Central

Cho, Hyesung; Moon Kim, Sang; Sik Kang, Yun; Kim, Junsoo; Jang, Segeun; Kim, Minhyoung; Park, Hyunchul; Won Bang, Jung; Seo, Soonmin; Suh, Kahp-Yang; Sung, Yung-Eun; Choi, Mansoo

2015-01-01

The production of multiscale architectures is of significant interest in materials science, and the integration of those structures could provide a breakthrough for various applications. Here we report a simple yet versatile strategy that allows for the LEGO-like integrations of microscale membranes by quantitatively controlling the oxygen inhibition effects of ultraviolet-curable materials, leading to multilevel multiscale architectures. The spatial control of oxygen concentration induces different curing contrasts in a resin allowing the selective imprinting and bonding at different sides of a membrane, which enables LEGO-like integration together with the multiscale pattern formation. Utilizing the method, the multilevel multiscale Nafion membranes are prepared and applied to polymer electrolyte membrane fuel cell. Our multiscale membrane fuel cell demonstrates significant enhancement of performance while ensuring mechanical robustness. The performance enhancement is caused by the combined effect of the decrease of membrane resistance and the increase of the electrochemical active surface area. PMID:26412619

The suitability of monopolar and bipolar ion exchange membranes as separators for biological fuel cells.

PubMed

Harnisch, Falk; Schröder, Uwe; Scholz, Fritz

2008-03-01

A proton exchange (Nafion-117), a cation exchange (Ultrex CMI7000), an anion exchange (Fumasep FAD), and a bipolar (FumasepFBM) membrane have been studied to evaluate the principle suitability of ion exchange membranes as separators between the anode and the cathode compartment of biological fuel cells. The applicability of these membranes is severely affected by the neutral pH, and the usually low ionic strength of the electrolyte solutions. Thus, the ohmic resistance of the monopolar membranes was found to greatly increase at neutral pH and at decreasing electrolyte concentrations. None of the studied membranes can prevent the acidification of the anode and the alkalization of the cathode compartment, which occurs in the course of the fuel cell operation. Bipolar membranes are shown to be least suitable for biofuel cell application since they show the highest polarization without being able to prevent pH splitting between the anode and cathode compartments.

Development of materials for mini DMFC working at room temperature for portable applications

NASA Astrophysics Data System (ADS)

Coutanceau, C.; Koffi, R. K.; Léger, J.-M.; Marestin, K.; Mercier, R.; Nayoze, C.; Capron, P.

Methanol permeability measurements and direct methanol fuel cell tests were performed at room temperature with different commercially available or recast Nafion ® membranes and sulfonated polyimide (SPI) membranes. Power densities as high as 20 mW cm -2 could be obtained with Nafion ® 115. However, in order to meet the technological requirements for portable applications, thinner membranes have to be considered. As the MeOH crossover increases greatly (from (7 to 20) × 10 -8 mol s -1 cm -2) while Nafion ® membranes thickness decreases, non-perfluorinated polymers having high IEC are promising candidates for DMFC working at room temperature. The development catalysts tolerant to methanol is also relevant for this application. In spite of the low permeability to MeOH of SPI membranes, the obtained electrical performance with E-TEK electrodes based MEAs was lower than that obtained with Nafion ® membranes. No significant increase of performances was neither evidenced by using homemade PtCr(7:3)/C and PtRu(4:1)/C catalysts instead of E-TEK electrodes with recast Nafion ® based MEAs. However, MEAs composed with thin SPI membranes (50 μm) and homemade PtCr/C catalysts gave very promising results (18 mW cm -2). Based on experimental observations, a speculative explanation of this result is given.

Full cell study of Diels Alder poly(phenylene) anion and cation exchange membranes in vanadium redox flow batteries

DOE PAGES

Pezeshki, Alan M.; Fujimoto, Cy; Sun, Che -Nan; ...

2015-11-14

In this paper, we report on the performance of Diels Alder poly(phenylene) membranes in vanadium redox flow batteries. The membranes were functionalized with quaternary ammonium groups to form an anion exchange membrane (QDAPP) and with sulfonic acid groups to form a cation exchange membrane (SDAPP). Both membrane classes showed similar conductivities in the battery environment, suggesting that the ion conduction mechanism in the material is not strongly affected by the moieties along the polymer backbone. The resistance to vanadium permeation in QDAPP was not improved relative to SDAPP, further suggesting that the polarity of the functional groups do not playmore » a significant role in the membrane materials tested. Both QDAPP and SDAPP outperformed Nafion membranes in cycling tests, with both achieving voltage efficiencies above 85% while maintaining 95% coulombic efficiency while at a current density of 200 mA/cm 2.« less

Low-Cost Proton Conducting Membranes for PEM Fuel Cells

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hu, Hongxing

Proton exchange membrane (PEM) is the key component in PEM fuel cells that critically determines the system performance and its economic viability. Presently, the state-of-the-art PEMs, such as Nafion membranes, are based on perfluorosulfonic acid (PFSA) ionomers. But these ionomer materials are expensive, particularly at the low volumes that will be needed for initial commercialization. Besides, they are not suitable for fuel cells operated beyond 100°C, because of the limitations connected to the humidification requirement of such membrane materials, limiting the maximum operating temperature to about 90°C. Fuel cells for transportation applications are required to operate in a wide temperaturemore » range from –20°C to 120°C. Low-cost PEMs with capabilities in a range of temperature and humidity conditions are urgently needed to meet the DOE fuel cell targets for transportation applications. Amsen Technologies LLC chooses to address the DOE call with a novel reinforced PEM approach based on new, non-PFSA proton conducting ionomers developed from our previous DOE SBIR projects. Along with this approach is the use of very cheap, ultra thin and highly porous microporous polymer meshes as the support for the membrane. The new PEM is expected to have significant cost advantages over traditional PEMs. The microporous polyolefin support costs $2-3/m 2; and the new ionomers that Amsen has developed are estimated at ~$250/kg at the higher end including material costs and labor costs (which may go down in the future as the processing is optimized and production scaled up). These have led to an estimate of total material cost for the membrane at $11 to $12/m 2, offering high potential of meeting the DOE cost targets (≤$20/m 2) after adding processing cost and profit margin. The Phase I results have successfully demonstrated that it is very promising to develop the intended low-cost, high-performance PEM membrane. Suitable material system has been identified, and

Oriented MOF-polymer Composite Nanofiber Membranes for High Proton Conductivity at High Temperature and Anhydrous Condition

PubMed Central

Wu, Bin; Pan, Jiefeng; Ge, Liang; Wu, Liang; Wang, Huanting; Xu, Tongwen

2014-01-01

The novel oriented electrospun nanofiber membrane composed of MOFs and SPPESK has been synthesized for proton exchange membrane fuel cell operating at high temperature and anhydrous conditions. It is clear that the oriented nanofiber membrane displays the higher proton conductivity than that of the disordered nanofiber membrane or the membrane prepared by conventional solvent-casting method (without nanofibers). Nanofibers within the membranes are significantly oriented. The proton conductivity of the oriented nanofiber membrane can reach up to (8.2 ± 0.16) × 10−2 S cm−1 at 160°C under anhydrous condition for the highly orientation of nanofibers. Moreover, the oxidative stability and resistance of methanol permeability of the nanofibers membrane are obviously improved with an increase in orientation of nanofibers. The observed methanol permeability of 0.707 × 10−7 cm2 s−1 is about 6% of Nafion-115. Consequently, orientated nanofibers membrane is proved to be a promising material as the proton exchange membrane for potential application in direct methanol fuel cells. PMID:25082522

Nafion covered core-shell structured Fe3O4@graphene nanospheres modified electrode for highly selective detection of dopamine.

PubMed

Zhang, Wuxiang; Zheng, Jianzhong; Shi, Jiangu; Lin, Zhongqiu; Huang, Qitong; Zhang, Hanqiang; Wei, Chan; Chen, Jianhua; Hu, Shirong; Hao, Aiyou

2015-01-01

Nafion covered core-shell structured Fe3O4@graphene nanospheres (GNs) modified glassy carbon electrode (GCE) was successfully prepared and used for selective detection dopamine. Firstly, the characterizations of hydro-thermal synthesized Fe3O4@GNs were investigated by scanning electron microscopy (SEM), transmission electron microscopy (TEM) and Raman spectroscopy. Then Fe3O4@GNs/Nafion modified electrode exhibited excellent electrocatalytic activity toward the oxidations of dopamine (DA). The interference test showed that the coexisted ascorbic acid (AA) and uric acid (UA) had no electrochemical interference toward DA. Under the optimum conditions, the broad linear relationship was obtained in the experimental concentration from 0.020 μM to 130.0 μM with the detection limit (S/N=3) of 0.007 μM. Furthermore, the core-shell structured Fe3O4@GNs/Nafion/GCE was applied to the determination of DA in real samples and satisfactory results were got, which could provide a promising platform to develop excellent biosensor for detecting DA. Copyright © 2014 Elsevier B.V. All rights reserved.

CeO2 nanocubes-graphene oxide as durable and highly active catalyst support for proton exchange membrane fuel cell

PubMed Central

Lei, M.; Wang, Z. B.; Li, J. S.; Tang, H. L.; Liu, W. J.; Wang, Y. G.

2014-01-01

Rapid degradation of cell performance still remains a significant challenge for proton exchange membrane fuel cell (PEMFC). In this work, we develop novel CeO2 nanocubes-graphene oxide nanocomposites as durable and highly active catalyst support for proton exchange membrane fuel cell. We show that the use of CeO2 as the radical scavenger in the catalysts remarkably improves the durability of the catalyst. The catalytic activity retention of Pt-graphene oxide-8 wt.% CeO2 nanocomposites reaches as high as 69% after 5000 CV-cycles at a high voltage range of 0.8–1.23 V, in contrast to 19% for that of the Pt-graphene oxide composites. The excellent durability of the Pt-CeO2 nanocubes-graphene oxide catalyst is attributed to the free radical scavenging activity of CeO2, which significantly slows down the chemical degradation of Nafion binder in catalytic layers, and then alleviates the decay of Pt catalysts, resulting in the excellent cycle life of Pt-CeO2-graphene oxide nanocomposite catalysts. Additionally, the performance of single cell assembled with Nafion 211 membrane and Pt-CeO2-graphene oxide catalysts with different CeO2 contents in the cathode as well as the Pt-C catalysts in the anode are also recorded and discussed in this study. PMID:25491655

CeO2 nanocubes-graphene oxide as durable and highly active catalyst support for proton exchange membrane fuel cell.

PubMed

Lei, M; Wang, Z B; Li, J S; Tang, H L; Liu, W J; Wang, Y G

2014-12-10

Rapid degradation of cell performance still remains a significant challenge for proton exchange membrane fuel cell (PEMFC). In this work, we develop novel CeO2 nanocubes-graphene oxide nanocomposites as durable and highly active catalyst support for proton exchange membrane fuel cell. We show that the use of CeO2 as the radical scavenger in the catalysts remarkably improves the durability of the catalyst. The catalytic activity retention of Pt-graphene oxide-8 wt.% CeO2 nanocomposites reaches as high as 69% after 5000 CV-cycles at a high voltage range of 0.8-1.23 V, in contrast to 19% for that of the Pt-graphene oxide composites. The excellent durability of the Pt-CeO2 nanocubes-graphene oxide catalyst is attributed to the free radical scavenging activity of CeO2, which significantly slows down the chemical degradation of Nafion binder in catalytic layers, and then alleviates the decay of Pt catalysts, resulting in the excellent cycle life of Pt-CeO2-graphene oxide nanocomposite catalysts. Additionally, the performance of single cell assembled with Nafion 211 membrane and Pt-CeO2-graphene oxide catalysts with different CeO2 contents in the cathode as well as the Pt-C catalysts in the anode are also recorded and discussed in this study.

CeO2 nanocubes-graphene oxide as durable and highly active catalyst support for proton exchange membrane fuel cell

NASA Astrophysics Data System (ADS)

Lei, M.; Wang, Z. B.; Li, J. S.; Tang, H. L.; Liu, W. J.; Wang, Y. G.

2014-12-01

Rapid degradation of cell performance still remains a significant challenge for proton exchange membrane fuel cell (PEMFC). In this work, we develop novel CeO2 nanocubes-graphene oxide nanocomposites as durable and highly active catalyst support for proton exchange membrane fuel cell. We show that the use of CeO2 as the radical scavenger in the catalysts remarkably improves the durability of the catalyst. The catalytic activity retention of Pt-graphene oxide-8 wt.% CeO2 nanocomposites reaches as high as 69% after 5000 CV-cycles at a high voltage range of 0.8-1.23 V, in contrast to 19% for that of the Pt-graphene oxide composites. The excellent durability of the Pt-CeO2 nanocubes-graphene oxide catalyst is attributed to the free radical scavenging activity of CeO2, which significantly slows down the chemical degradation of Nafion binder in catalytic layers, and then alleviates the decay of Pt catalysts, resulting in the excellent cycle life of Pt-CeO2-graphene oxide nanocomposite catalysts. Additionally, the performance of single cell assembled with Nafion 211 membrane and Pt-CeO2-graphene oxide catalysts with different CeO2 contents in the cathode as well as the Pt-C catalysts in the anode are also recorded and discussed in this study.

Micro Galvanic Cell To Generate PtO and Extend the Triple-Phase Boundary during Self-Assembly of Pt/C and Nafion for Catalyst Layers of PEMFC.

PubMed

Long, Zhi; Gao, Liqin; Li, Yankai; Kang, Baotao; Lee, Jin Yong; Ge, Junjie; Liu, Changpeng; Ma, Shuhua; Jin, Zhao; Ai, Hongqi

2017-11-08

The self-assembly powder (SAP) with varying Nafion content was synthesized and characterized by XRD, XPS, HRTEM, and mapping. It is observed that the oxygen from oxygen functional groups transfers to the surface of Pt and generate PtO during the process of self-assembly with the mechanism of micro galvanic cell, where Pt, carbon black, and Nafion act as the anode, cathode and electrolyte, respectively. The appearance of PtO on the surface of Pt leads to a turnover of Nafion structure, and therefore more hydrophilic sulfonic groups directly contact with Pt, and thus the triple-phase boundary (TPB) has been expanded.

Acceleration Techniques for Recombination of Gases in Electrolysis Microactuators with Nafion®-Coated Electrocatalyst

PubMed Central

Sheybani, Roya; Meng, Ellis

2015-01-01

Recombination of electrolysis gases (oxidation of hydrogen and reduction of oxygen) is an important factor in operation efficiency of devices employing electrolysis such as actuators and also unitized regenerative fuel cells. Several methods of improving recombination speed and repeatability were developed for application to electrolysis microactuators with Nafion®-coated catalytic electrodes. Decreasing the electrolysis chamber volume increased the speed, consistency, and repeatability of the gas recombination rate. To further improve recombination performance, methods to increase the catalyst surface area, hydrophobicity, and availability were developed and evaluated. Of these, including in the electrolyte pyrolyzed-Nafion®-coated Pt segments contained in the actuator chamber accelerated recombination by increasing the catalyst surface area and decreasing the gas transport diffusion path. This approach also reduced variability in recombination encountered under varying actuator orientation (resulting in differing catalyst/gas bubble proximity) and increased the rate of recombination by 2.3 times across all actuator orientations. Repeatability of complete recombination for different generated gas volumes was studied through cycling. PMID:26251561

High-power direct ethylene glycol fuel cell (DEGFC) based on nanoporous proton-conducting membrane (NP-PCM)

NASA Astrophysics Data System (ADS)

Peled, E.; Livshits, V.; Duvdevani, T.

We recently reported the development of a new nanoporous proton-conducting membrane (NP-PCM) and have applied it in a direct methanol fuel cell (DMFC) and in other direct oxidation fuel cells. The use of the NP-PCM in the DMFC offers several advantages over the Nafion-based DMFC including lower membrane cost, lower methanol crossover which leads to a much higher fuel utilization and higher conductivity. In this work, we found that the 90 °C swelling of the NP-PCM is only 5-8% and that the diffusion constant of methanol at 80-130 °C is higher by a factor of 1.5-3 than that of ethylene glycol (EG). The maximum power density of methanol/oxygen and EG/oxygen FCs equipped with a 100 μm thick NP-PCMs is 400 and 300 mW/cm 2 respectively, higher than that for a DMFC based on Nafion 115 (260 mW/cm 2 [Eletrochem. Solid-State Lett. 4 (4) (2001) A31]. This puts the DEGFC in direct competition with both DMFC and indirect methanol FC. Ethylene glycol (EG) is well known in the automobile industry and in contrast to methanol, its distribution infrastructure already exists, thus it is a promising candidate for practical electric vehicles.

Nafion®-catalyzed microwave-assisted Ritter reaction: An atom-economic solvent-free synthesis of amides

EPA Science Inventory

An atom-economic solvent-free synthesis of amides by the Ritter reaction of alcohols and nitriles under microwave irradiation is reported. This green protocol is catalyzed by solid supported Nafion®NR50 with improved efficiency and reduced waste production.

Tackling capacity fading in vanadium flow batteries with amphoteric membranes

NASA Astrophysics Data System (ADS)

Oldenburg, Fabio J.; Schmidt, Thomas J.; Gubler, Lorenz

2017-11-01

Capacity fading and poor electrolyte utilization caused by electrolyte imbalance effects are major drawbacks for the commercialization of vanadium flow batteries (VFB). The influence of membrane type (cationic, anionic, amphoteric) on these effects is studied by determining the excess and net flux of each vanadium ion in an operating VFB assembled with a cation exchange membrane (CEM), Nafion® NR212, an anion exchange membrane (AEM), Fumatech FAP-450, and an amphoteric ion exchange membrane (AIEM) synthesized in-house. It is shown that the net vanadium flux, accompanied by water transport, is directed towards the positive side for the CEM and towards the negative side for the AEM. The content of cation and anion exchange groups in the AIEM is adjusted via radiation grafting to balance the vanadium flux between the two electrolyte sides. With the AIEM the net vanadium flux is significantly reduced and capacity fading due to electrolyte imbalances can be largely eliminated. The membrane's influence on electrolyte imbalance effects is characterized and quantified in one single charge-discharge cycle by analyzing the content of the four different vanadium species in the two electrolytes. The experimental data recorded herewith conclusively explains the electrolyte composition after 80 cycles.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Haryadi, E-mail: haryadi@polban.ac.id; Gunawan, Y. B.; Harjogi, D.

The modification of Nafion 117 - TMSP (trimethoxysylilprophanthiol) composite membrane has been conducted by in-situ sol-gel method followed by characterization of structural and properties of material using spectroscopic techniques. The performance of composite membrane has then been examined in the single stack module of Fe-Cr Redox Flow Battery. It was found that the introduction of silica from TMSP through sol-gel process within the Nafion 117 membrane produced composite membrane that has slightly higher proton conductivity values as compared to the pristine of Nafion 117 membrane observed by electrochemical impedance spectroscopy. The degree of swelling of water in the composite membranemore » demonstrated greatly reduced than a pristine Nafion 117 signifying low water cross over. The SEM-EDX measurements indicated that there was no phase separation occurred suggesting that silica nanoparticles are distributed homogeneously within the composite membrane. The composite membrane used as separator in the system of Fe-Cr Redox Flow Battery revealed no cross mixing (crossover) occurred between anolyte and catholyte in the system as observed from the total voltage measurements that closed to the theoretical value. The battery efficiency generally increased as the volume of the electrolytes enlarged.« less

A proton-exchange membrane prepared by the radiation grafting of styrene and silica into polytetrafluoroethylene films

NASA Astrophysics Data System (ADS)

Yu, Hongyan; Shi, Jianheng; Zeng, Xinmiao; Bao, Mao; Zhao, Xinqing

2009-07-01

A polytetrafluoroethylene (PTFE) based organic-inorganic hybrid proton-exchange membrane was prepared from simultaneous radiation grafting of styrene (St) into porous PTFE membrane with the in situ sol-gel reaction of tetraethoxysilane (TEOS) followed by sulfonation in fuming sulfonic acid. The effect of radiation on the sol-gel reaction was studied. The results show that radiation promotes the sol-gel reaction with the help of St at room temperature. Incorporated silica gel helps to produce higher degree of grafting (DOG). SEM analysis was conducted to confirm that the inorganic silicon oxide was introduced to produce hybrid membrane in this work. The proton conductivity of membrane evaluated using electrochemical impedance spectroscopy is much higher (14.3×10 -2 S cm -1) than that of Nafion ® 117 at temperature of 80 °C with acceptable water uptake 51 wt%.

Room temperature aerobic oxidation of amines by a nanocrystalline ruthenium oxide pyrochlore nafion composite catalyst.

PubMed

Venkatesan, Shanmuganathan; Kumar, Annamalai Senthil; Lee, Jyh-Fu; Chan, Ting-Shan; Zen, Jyh-Myng

2012-05-14

The aerobic oxidation of primary amines to their respective nitriles has been carried out at room temperature using a highly reusable nanocrystalline ruthenium oxide pyrochlore Nafion composite catalyst (see figure). Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Operando μ-Raman study of the actual water content of perfluorosulfonic acid membranes in the fuel cell

NASA Astrophysics Data System (ADS)

Peng, Zhe; Badets, Vasilica; Huguet, Patrice; Morin, Arnaud; Schott, Pascal; Tran, Thi Bich Hue; Porozhnyy, Mikhaël; Nikonenko, Victor; Deabate, Stefano

2017-07-01

Operando μ-Raman spectroscopy is used to probe the water distribution across Nafion® and Aquivion™ membranes in the operating fuel cell. The through-plane water concentration profile is obtained with μm resolution at the middle of the active surface, both at the gas distribution channel and at the under-lands areas. Depth-resolved measurements carried out at room temperature show that the water content of both membranes increases with the increase of the feed gas relative humidity and decreases with the increase of stoichiometry. At given relative humidity and stoichiometry conditions, the water content first increases at the fuel cell start-up and, then, decreases progressively with the increase of the current density delivered by the cell. The water loss is due to the concomitant rise of pressure drops and of the cell inner temperature, the latter giving the larger contribution. Pressure drops are related to the increase of the feed gases fluxes while temperature rise is due to increasing ohmic losses and heat from the electrochemical reaction. Compared to Nafion, Aquivion exhibits larger water content, but similar dehydration rate as a function of ohmic losses, and larger water accumulation at the under-lands area compared to channel.

Luminescence Probe Studies of Ionomers. I. Steady-State Measurements from Nafion Membrane.

DTIC Science & Technology

1985-02-03

Bu4N+ was monitored by titrating the released protons with NaOH. Bu4N+ uptake by Na+ membranes was assumed to be the same as uptake by acidic form...spaced excited states (21). Because of their solvent sensitivity, 1,5-DNS derivatives may also be used as polarity probes (20). The acid -base... acid . The basic (unprotonated) form of the DNS derivative used here (DA+ ) shows *absorption maxima at ca. 325 and 245 nm (aqueous solution, pH 6.8

Permselective SPEEK/Nafion Composite-Coated Separator as a Potential Polysulfide Crossover Barrier Layer for Li-S Batteries.

PubMed

Babu, Dasari Bosu; Giribabu, Krishnan; Ramesha, Kannadka

2018-06-13

Minimizing the shuttle effect by constraining polysulfides to the cathode compartment and activating the passive layer between cathode and separator are highly important for improving the Li-S cell performance, Coulombic efficiency, and cycle life. Here, we report a submicron thin coating of permselective sulfonated poly(ether ether ketone) (SPEEK) composite layer on the separator that would reduce polysulfide crossover, imparting a significant improvement in cycle life. It is observed that SPEEK increases the stability, and adding Nafion improves the capacity value. Among different ratios of Nafion and SPEEK (25:75, 50:50, and 75:25), the composite with a SPEEK/Nafion ratio of 50:50 showed a controlled shuttle effect with a stable cell capacity of 600 mA h g -1 up to 300 cycles. This modified separator with permselective coatings not only reduces the polysulfide shuttle but also improves the wettability and interfacial contact, which results in an improvement in average cell potential and lithium diffusivity. It is demonstrated here that the combination of functional (ionomer coating on separator) and nonfunctional (extra cathode layer) physical barriers effectively suppresses the polysulfide crossover and improves the electrochemical performance of Li-S batteries. The cell shows an initial capacity of 1300 mA h g -1 and a capacity retention of 650 mA h g -1 over 500 cycles with a 6 mg/cm 2 sulfur loading.

Enhanced proton transport in nanostructured polymer electrolyte/ionic liquid membranes under water-free conditions.

PubMed

Kim, Sung Yeon; Kim, Suhan; Park, Moon Jeong

2010-10-05

Proton exchange fuel cells (PEFCs) have the potential to provide power for a variety of applications ranging from electronic devices to transportation vehicles. A major challenge towards economically viable PEFCs is finding an electrolyte that is both durable and easily passes protons. In this article, we study novel anhydrous proton-conducting membranes, formed by incorporating ionic liquids into synthetic block co-polymer electrolytes, poly(styrenesulphonate-b-methylbutylene) (S(n)MB(m)), as high-temperature PEFCs. The resulting membranes are transparent, flexible and thermally stable up to 180 °C. The increases in the sulphonation level of S(n)MB(m) co-polymers (proton supplier) and the concentration of the ionic liquid (proton mediator) produce an overall increase in conductivity. Morphology effects were studied by X-ray scattering and electron microscopy. Compared with membranes having discrete ionic domains (including Nafion 117), the nanostructured membranes revealed over an order of magnitude increase in conductivity with the highest conductivity of 0.045 S cm(-1) obtained at 165 °C.

Elimination of a pollution associated with chromic acid during the electro-deposition of Cr(III) using appropriate anodic and membrane materials in a double film bath.

PubMed

Jiang, Xiaojun; Chen, Wenchao; Xu, Hongbo

2009-01-01

A method using trivalent chromium has been used to replace hexavalent chromium for the electro-deposition of chromium. Using a tri-chamber bath system various anodic materials and membranes were evaluated to minimize the production of environmentally and health damaging chromic acid. By measuring the absorbance of Cr(VI) at 640 nm, the results indicate that the use of a titanium plated ruthenium (Ti-Ru) anode produces the least amount of chromic acid byproduct compared to lead-gold alloy and graphite anodes. The concentration of Cr(VI) in the immediate vicinity of the Ti-Ru anode decreased from 0.389 mg/L to 0 during a 40-min deposition period. The use of a Nafion(TM) quaternary cation exchange membrane portioning the buffer and anode selectively prevented Cr(III) from entering the anode compartment whilst allowing the migration of H(+) to maintain overall voltaic continuity. It has been demonstrated that the use of a Ti-Ru anode with a Nafion(TM) membrane can eliminate the production of chromic acid associated with the electro-deposition of chromium plate thereby preventing its health damaging exposure to plant operators and preventing discharge of Cr(VI) into the environment. Addition of a surfactant improved current efficiency by 34.7%.

Electrochemistry and electrocatalysis of myoglobin immobilized in sulfonated graphene oxide and Nafion films.

PubMed

Chen, Guiying; Sun, Hong; Hou, Shifeng

2016-06-01

In this study, sulfonated graphene oxide (SGO) was synthesized and characterized by Fourier transform infrared (FT-IR) spectroscopy and X-ray photoelectron spectroscopy (XPS). It was used to make Mb-SGO-Nafion composite films by coating myoglobin (Mb) on the glassy carbon electrodes (GCE). Positions of the Soret absorption bands suggested that Mb retained its native conformation in the films. Mb-SGO-Nafion film modified electrode showed a pair of well-defined and nearly reversible cyclic voltammetry peaks at around -0.39 V versus saturated calomel electrode (SCE) in pH 7.0 buffers, characteristic of heme Fe(III)/Fe(II) redox couples. Electrochemical parameters such as electron transfer rate constant (ks) and formal potential (E(o')) were estimated by fitting the data of square-wave voltammetry with nonlinear regression analysis. Experimental data demonstrated that the electron transfer between Mb and electrode was greatly facilitated and showed good electrocatalytic properties toward various substrates, such as H2O2 and NaNO2, with significant lowering of reduction overpotential. Copyright © 2016. Published by Elsevier Inc.

Novel sulfonated polyimide/zwitterionic polymer-functionalized graphene oxide hybrid membranes for vanadium redox flow battery

NASA Astrophysics Data System (ADS)

Cao, Li; Kong, Lei; Kong, Lingqian; Zhang, Xingxiang; Shi, Haifeng

2015-12-01

Hybrid membranes (SPI/ZGO) composed of sulfonated polyimide (SPI) and zwitterionic polymer-functionalized graphene oxide (ZGO) are fabricated via a solution-casting method for vanadium redox flow battery (VRB). Successful preparation of ZGO fillers and SPI/ZGO hybrid membranes are demonstrated by FT-IR, XPS and SEM, indicating that ZGO fillers is homogeneously dispersed into SPI matrix. Through controlling the interfacial interaction between SPI matrix and ZGO fillers, the physicochemical properties, e.g., vanadium ion barrier and proton transport pathway, of hybrid membranes are tuned via the zwitterionic acid-base interaction in the hybrid membrane, showing a high ion selectivity and good stability with the incorporated ZGO fillers. SPI/ZGO-4 hybrid membrane proves a higher cell efficiencies (CE: 92-98%, EE: 65-79%) than commercial Nafion 117 membrane (CE: 89-94%, EE: 59-70%) for VRB application at 30-80 mA cm-2. The assembled VRB with SPI/ZGO-4 membrane presents a stable cycling charge-discharge performance over 280 times, which demonstrates its excellent chemical stability under the strong acidic and oxidizing conditions. SPI/ZGO hybrid membranes show a brilliant perspective for VRB application.

Role of the electric field in selective ion filtration in nanostructures.

PubMed

Park, Yong; Kim, Sueon; Jang, In Hyuk; Nam, Young Suk; Hong, Hiki; Choi, Dukhyun; Lee, Won Gu

2016-02-21

Nafion has received great attention as a proton conductor that can block negative ions. Here, we report the effect of a Nafion coating on an anodic aluminium oxide (AAO) nanoporous membrane on its function of ion rejection and filtering depending on the electric field. In our experiments, Nafion, once coated, was used to repel the negative ions (anions) from the coated surface, and then selectively allowed positive ions (cations) to pass through the nanopores in the presence of an electric field. To demonstrate the proof-of-concept validation, we coated Nafion solution onto the surface of AAO membranes with 20 nm nanopores average diameter at different solution concentration levels. Vacuum filtration methods for Nafion coating were vertically applied to the plane of an AAO membrane. An electric field was then applied to the upper surface of the Nafion-coated AAO membrane to investigate if ion rejection and filtering was affected by the presence of the electric field. Both anions and cations could pass through the AAO nanopores without an electric field applied. However, only cations could well pass through the AAO nanopores under an electric field, thus effectively blocking anions from passing through the nanopores. This result shows that ion filtration of electrons has been selectively performed while the system also works as a vital catalyst in reactivating Nafion via electrolysis. A saturated viscosity ratio of Nafion solution for the coating was also determined. We believe that this approach is potentially beneficial for better understanding the fundamentals of selective ion filtration in nanostructures and for promoting the use of nanostructures in potential applications such as ion-based water purification and desalination system at the nanoscale in a massively electrically integrated format.

Chemical and radiation crosslinked polymer electrolyte membranes prepared from radiation-grafted ETFE films for DMFC applications

NASA Astrophysics Data System (ADS)

Chen, Jinhua; Asano, Masaharu; Yamaki, Tetsuya; Yoshida, Masaru

To develop a highly chemically stable polymer electrolyte membrane for application in a direct methanol fuel cell (DMFC), doubly crosslinked membranes were prepared by chemical crosslinking using bifunctional monomers, such as divinylbenzene (DVB) and bis(p, p-vinyl phenyl) ethane (BVPE), and by radiation crosslinking. The membranes were prepared by grafting of m, p-methylstyrene (MeSt) and p-tert-butylstyrene (tBuSt) into poly(ethylene- co-tetrafluoroethylene) (ETFE) films and subsequent sulfonation. The effects of the DVB and BVPE crosslinkers on the grafting kinetics and the properties of the prepared membranes, such as water uptake, proton conductivity and chemical stability were investigated. Radiation crosslinking was introduced by irradiation of the ETFE base film, the grafted film or the sulfonated membrane. The membrane crosslinked by DVB and BVPE crosslinkers and post-crosslinked by γ-ray irradiation of the corresponding grafted film possessed the highest chemical stability among the prepared membranes, a significantly lower methanol permeability compared to Nafion ® membranes, and a better DMFC performance for high methanol feed concentration. Therefore, this doubly crosslinked membrane was promising for application in a DMFC where relatively high methanol concentration could be fed.

Friedel-Crafts Crosslinked Highly Sulfonated Polyether Ether Ketone (SPEEK) Membranes for a Vanadium/Air Redox Flow Battery.

PubMed

Merle, Géraldine; Ioana, Filipoi Carmen; Demco, Dan Eugen; Saakes, Michel; Hosseiny, Seyed Schwan

2013-12-30

Highly conductive and low vanadium permeable crosslinked sulfonated poly(ether ether ketone) (cSPEEK) membranes were prepared by electrophilic aromatic substitution for a Vanadium/Air Redox Flow Battery (Vanadium/Air-RFB) application. Membranes were synthesized from ethanol solution and crosslinked under different temperatures with 1,4-benzenedimethanol and ZnCl2 via the Friedel-Crafts crosslinking route. The crosslinking mechanism under different temperatures indicated two crosslinking pathways: (a) crosslinking on the sulfonic acid groups; and (b) crosslinking on the backbone. It was observed that membranes crosslinked at a temperature of 150 °C lead to low proton conductive membranes, whereas an increase in crosslinking temperature and time would lead to high proton conductive membranes. High temperature crosslinking also resulted in an increase in anisotropy and water diffusion. Furthermore, the membranes were investigated for a Vanadium/Air Redox Flow Battery application. Membranes crosslinked at 200 °C for 30 min with a molar ratio between 2:1 (mol repeat unit:mol benzenedimethanol) showed a proton conductivity of 27.9 mS/cm and a 100 times lower VO2+ crossover compared to Nafion.

Confocal Raman Microscopy for the Determination of Protein and Quaternary Ammonium Ion Loadings in Biocatalytic Membranes for Electrochemical Energy Conversion and Storage

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cai, Rong; Abdellaoui, Sofiene; Kitt, Jay P.

Here, the need to immobilize active enzyme, while ensuring high rates of substrate turnover and electronic charge transfer with an electrode, is a centrally important challenge in the field of bioelectrocatalysis. In this work, we demonstrate the use of confocal Raman microscopy as a tool for quantitation and molecular-scale structural characterization of ionomers and proteins within biocatalytic membranes to aid in the development of energy efficient biofuel cells. A set of recently available short side chain Aquivion ionomers spanning a range of equivalent weight (EW) suitable for enzyme immobilization was investigated. Aquivion ionomers (790 EW, 830 EW and 980 EW)more » received in the proton-exchanged (SO 3H) form were treated with tetra-n-butylammonium bromide (TBAB) to neutralize the ionomer and expand the size of ionic domains for enzyme incorporation. Through the use of confocal Raman microscopy, membrane TBA+ ion content was predicted in calibration studies to within a few percent of the conventional titrimetric method across the full range of TBA + : SO 3 - ratios of practical interest (0.1 to 1.7). Protein incorporation into membranes was quantified at the levels expected in biofuel cell electrodes. Furthermore, features associated with the catalytically active, enzyme-coordinated copper center were evident between 400 cm -1 - 500 cm -1 in spectra of laccase catalytic membranes, demonstrating the potential to interrogate mechanistic chemistry at the enzyme active site of biocathodes under fuel cell reaction conditions. When benchmarked against the 1100 EW Nafion ionomer in glucose/air enzymatic fuel cells (EFCs), EFCs with laccase air-breathing cathodes prepared from TBA + modified Aquivion ionomers were able to reach maximum power densities (P max) up to 1.5 times higher than EFCs constructed with cathodes prepared from TBA + modified Nafion. The improved performance of EFCs containing the short side chain Aquivion ionomers relative to Nafion is

Confocal Raman Microscopy for the Determination of Protein and Quaternary Ammonium Ion Loadings in Biocatalytic Membranes for Electrochemical Energy Conversion and Storage

DOE PAGES

Cai, Rong; Abdellaoui, Sofiene; Kitt, Jay P.; ...

2017-11-14

Here, the need to immobilize active enzyme, while ensuring high rates of substrate turnover and electronic charge transfer with an electrode, is a centrally important challenge in the field of bioelectrocatalysis. In this work, we demonstrate the use of confocal Raman microscopy as a tool for quantitation and molecular-scale structural characterization of ionomers and proteins within biocatalytic membranes to aid in the development of energy efficient biofuel cells. A set of recently available short side chain Aquivion ionomers spanning a range of equivalent weight (EW) suitable for enzyme immobilization was investigated. Aquivion ionomers (790 EW, 830 EW and 980 EW)more » received in the proton-exchanged (SO 3H) form were treated with tetra-n-butylammonium bromide (TBAB) to neutralize the ionomer and expand the size of ionic domains for enzyme incorporation. Through the use of confocal Raman microscopy, membrane TBA+ ion content was predicted in calibration studies to within a few percent of the conventional titrimetric method across the full range of TBA + : SO 3 - ratios of practical interest (0.1 to 1.7). Protein incorporation into membranes was quantified at the levels expected in biofuel cell electrodes. Furthermore, features associated with the catalytically active, enzyme-coordinated copper center were evident between 400 cm -1 - 500 cm -1 in spectra of laccase catalytic membranes, demonstrating the potential to interrogate mechanistic chemistry at the enzyme active site of biocathodes under fuel cell reaction conditions. When benchmarked against the 1100 EW Nafion ionomer in glucose/air enzymatic fuel cells (EFCs), EFCs with laccase air-breathing cathodes prepared from TBA + modified Aquivion ionomers were able to reach maximum power densities (P max) up to 1.5 times higher than EFCs constructed with cathodes prepared from TBA + modified Nafion. The improved performance of EFCs containing the short side chain Aquivion ionomers relative to Nafion is

Crosslinked anion exchange membranes with primary diamine-based crosslinkers for vanadium redox flow battery application

NASA Astrophysics Data System (ADS)

Cha, Min Suc; Jeong, Hwan Yeop; Shin, Hee Young; Hong, Soo Hyun; Kim, Tae-Ho; Oh, Seong-Geun; Lee, Jang Yong; Hong, Young Taik

2017-09-01

A series of polysulfone-based crosslinked anion exchange membranes (AEMs) with primary diamine-based crosslinkers has been prepared via simple a crosslinking process as low-cost and durable membranes for vanadium redox flow batteries (VRFBs). Chloromethylated polysulfone is used as a precursor polymer for crosslinked AEMs (CAPSU-x) with different degrees of crosslinking. Among the developed AEMs, CAPSU-2.5 shows outstanding dimensional stability and anion (Cl-, SO42-, and OH-) conductivity. Moreover, CAPSU-2.5 exhibits much lower vanadium ion permeability (2.72 × 10-8 cm2 min-1) than Nafion 115 (2.88 × 10-6 cm2 min-1), which results in an excellent coulombic efficiency of 100%. The chemical and operational stabilities of the membranes have been investigated via ex situ soaking tests in 0.1 M VO2+ solution and in situ operation tests for 100 cycles, respectively. The excellent chemical, physical, and electrochemical properties of the CAPSU-2.5 membrane make it suitable for use in VRFBs.

Development of cesium phosphotungstate salt and chitosan composite membrane for direct methanol fuel cells.

PubMed

Xiao, Yanxin; Xiang, Yan; Xiu, Ruijie; Lu, Shanfu

2013-10-15

A novel composite membrane has been developed by doping cesium phosphotungstate salt (CsxH3-xPW12O40 (0≤x≤3), Csx-PTA) into chitosan (CTS/Csx-PTA) for application in direct methanol fuel cells (DMFCs). Uniform distribution of Csx-PTA nanoparticles has been achieved in the chitosan matrix. The proton conductivity of the composite membrane is significantly affected by the Csx-PTA content in the composite membrane as well as the Cs substitution in PTA. The highest proton conductivity for the CTS/Csx-PTA membranes was obtained with x=2 and Cs2-PTA content of 5 wt%. The value is 6×10(-3) S cm(-1) and 1.75×10(-2) S cm(-1) at 298 K and 353 K, respectively. The methanol permeability of CTS/Cs2-PTA membrane is about 5.6×10(-7), 90% lower than that of Nafion-212 membrane. The highest selectivity factor (φ) was obtained on CTS/Cs2-PTA-5 wt% composite membrane, 1.1×10(4)/Scm(-3)s. The present study indicates the promising potential of CTS/Csx-PTA composite membrane as alternative proton exchange membranes in direct methanol fuel cells. Copyright © 2013 Elsevier Ltd. All rights reserved.

Fuel-Cell Electrolytes Based on Organosilica Hybrid Proton Conductors

NASA Technical Reports Server (NTRS)

Narayan, Sri R.; Yen, Shiao-Pin S.

2008-01-01

A new membrane composite material that combines an organosilica proton conductor with perfluorinated Nafion material to achieve good proton conductivity and high-temperature performance for membranes used for fuel cells in stationary, transportation, and portable applications has been developed. To achieve high proton conductivities of the order of 10(exp -1)S/cm over a wide range of temperatures, a composite membrane based on a new class of mesoporous, proton-conducting, hydrogen-bonded organosilica, used with Nafion, will allow for water retention and high proton conductivity over a wider range of temperatures than currently offered by Nafion alone. At the time of this reporting, this innovation is at the concept level. Some of the materials and processes investigated have shown good proton conductivity, but membranes have not yet been prepared and demonstrated.

Membranes with well-defined ions transport channels fabricated via solvent-responsive layer-by-layer assembly method for vanadium flow battery.

PubMed

Xu, Wanxing; Li, Xianfeng; Cao, Jingyu; Zhang, Hongzhang; Zhang, Huamin

2014-02-06

In this work we presented a general strategy for the fabrication of membranes with well-defined ions transport channels through solvent-responsive layer-by-layer assembly (SR-LBL). Multilayered poly (diallyldimethylammonium chloride) (PDDA) and poly (acrylic acid) (PAA) complexes were first introduced on the inner pore wall and the surface of sulfonated poly (ether ether ketone)/poly (ether sulfone) (PES/SPEEK) nanofiltration membranes to form ions transport channels with tuned radius. This type of membranes are highly efficient for the separators of batteries especially vanadium flow batteries (VFBs): the VFBs assembled with prepared membranes exhibit an outstanding performance in a wide current density range, which is much higher than that assembled with commercial Nafion 115 membranes. This idea could inspire the development of membranes for other flow battery systems, as well as create further progress in similar areas such as fuel cells, electro-dialysis, chlor-alkali cells, water electrolysis and so on.

Membranes with well-defined ions transport channels fabricated via solvent-responsive layer-by-layer assembly method for vanadium flow battery

PubMed Central

Xu, Wanxing; Li, Xianfeng; Cao, Jingyu; Zhang, Hongzhang; Zhang, Huamin

2014-01-01

In this work we presented a general strategy for the fabrication of membranes with well-defined ions transport channels through solvent-responsive layer-by-layer assembly (SR-LBL). Multilayered poly (diallyldimethylammonium chloride) (PDDA) and poly (acrylic acid) (PAA) complexes were first introduced on the inner pore wall and the surface of sulfonated poly (ether ether ketone)/poly (ether sulfone) (PES/SPEEK) nanofiltration membranes to form ions transport channels with tuned radius. This type of membranes are highly efficient for the separators of batteries especially vanadium flow batteries (VFBs): the VFBs assembled with prepared membranes exhibit an outstanding performance in a wide current density range, which is much higher than that assembled with commercial Nafion 115 membranes. This idea could inspire the development of membranes for other flow battery systems, as well as create further progress in similar areas such as fuel cells, electro-dialysis, chlor-alkali cells, water electrolysis and so on. PMID:24500376

Synthesis and characterization of sulfonate polystyrene-lignosulfonate-alumina (SPS-LS-Al{sub 2}O{sub 3}) polyblends as electrolyte membranes for fuel cell

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gonggo, Siang Tandi, E-mail: standigonggo@yahoo.com

2015-09-30

The new type of electrolyte membrane materials has been prepared by blend sulfonated polystyrene (SPS), lignosulfonate (LS), and alumina (SPS-LS-Al{sub 2}O{sub 3}) by casting polymer solution. The resulting polymer electrolyte membranes were then characterized by functional groups analysis, mechanical properties, water uptake, ion exchange capacity, and proton conductivity. SPS-LS-Al{sub 2}O{sub 3} membranes with alumina composition various have been proven qualitatively by analysis of functional groups. Increasing the Al{sub 2}O{sub 3} ratio resulted in higher ion exchange capacity (IEC), mechanical strength and proton conductivity, but water uptake decreased. The SPS-LS-Al{sub 2}O{sub 3} blend showed higher proton conductivity than Nafion 117.

Nanoscale current imaging of the conducting channels in proton exchange membrane fuel cells.

PubMed

Bussian, David A; O'Dea, James R; Metiu, Horia; Buratto, Steven K

2007-02-01

The electrochemically active area of a proton exchange membrane fuel cell (PEMFC) is investigated using conductive probe atomic force microscopy (CP-AFM). A platinum-coated AFM tip is used as a nanoscale cathode in an operating PEMFC. We present results that show highly inhomogeneous distributions of conductive surface domains at several length scales. At length scales on the order of the aqueous domains of the membrane, approximately 50 nm, we observe single channel electrochemistry. I-V curves for single conducting channels are obtained, which yield insight into the nature of conductive regions across the PEM. In addition, we demonstrate a new characterization technique, phase current correlation microscopy, which gives a direct measure of the electrochemical activity for each aqueous domain. This shows that a large number ( approximately 60%) of the aqueous domains present at the surface of an operating Nafion membrane are inactive. We attribute this to a combination of limited aqueous domain connectivity and catalyst accessibility.

Adsorption stripping voltammetry of phenol at Nafion-modified glassy carbon electrode in the presence of surfactants.

PubMed

Yi, H; Wu, K; Hu, S; Cui, D

2001-12-24

In this paper, a new voltammetric method for the determination of phenol is described. In pH 8.00 phosphate buffer and in the presence of long-chain cationic surfactant-cetyltrimethylammonium bromide-phenol has a very sensitive oxidation peak at 0.47 V (vs. SCE) on the Nafion-modified glassy carbon electrode (GCE). The experimental parameters, such as supporting electrolyte and pH values, amounts of Nafion, varieties and concentration of surfactants, accumulation potential and time, as well as scan rate were optimized. The peak current is linear with the concentration of phenol in the range from 8x10(-9) to 1x10(-5) M, and the detection limit is 1x10(-9) M after being accumulated at -0.50 V (vs. SCE) for 3 min. Trace levels of phenol in water samples were determined by using this voltammetric method, the average recovery was calculated to be 99.56%.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zheng, Weiqing; Wang, Liang; Deng, Fei

Proton conductivity of the polymer electrolyte membranes in fuel cells dictates their performance and requires sufficient water management. Here, we report a simple, scalable method to produce well-dispersed transition metal carbide nanoparticles. We demonstrate that these, when added as an additive to the proton exchange Nafion membrane, provide significant enhancement in power density and durability over 100 hours, surpassing both the baseline Nafion and platinum-containing recast Nafion membranes. Using focused ion beam/scanning electron microscope tomography reveals the key membrane degradation mechanism. Density functional theory exposes that OH• and H• radicals adsorb more strongly from solution and reactions producing OH• aremore » significantly more endergonic on tungsten carbide than on platinum. Consequently, tungsten carbide may be a promising catalyst in self-hydrating crossover gases while retarding desorption of and capturing free radicals formed at the cathode, resulting in enhanced membrane durability.« less

Effect of end-group cross-linking on transport properties of sulfonated poly(phenylene sulfide nitrile)s for proton exchange membranes

NASA Astrophysics Data System (ADS)

Kang, Na Rae; Lee, So Young; Shin, Dong Won; Hwang, Doo Sung; Lee, Kang Hyuck; Cho, Doo Hee; Kim, Ji Hoon; Lee, Young Moo

2016-03-01

A series of end-group cross-linked membranes (Az-XESPSN) were prepared by click reaction to investigate the effects of cross-linking on the morphology and proton transport properties of proton exchange membranes. The morphological transformations resulting from thermal annealing and cross-linking were observed by means of atomic force microscopy (AFM) and transmission electron microscopy (TEM). Compared to the non-cross-linked ESPSN membranes, the Az-XESPSN membranes exhibited lower water uptake and improved mechanical and chemical stabilities. In addition, the Az-XESPSN membranes exhibited higher proton conductivities (0.018-0.028 S cm-1) compared to those of the ESPSN membranes (0.0044-0.0053 S cm-1) and Nafion 212 (0.0061 S cm-1), particularly in conditions of elevated temperature (120 °C) and low relative humidity (35%). Such enhancements can be attributed to a synergistic effect of well-defined hydrophilic ionic clusters and triazole groups that function as proton carriers under anhydrous conditions. Furthermore, the Az-XESPSN membranes exhibited significantly enhanced single cell performance and long-term stability compared to those of ESPSN membranes.

Low Crossover Polymer Electrolyte Membranes for Direct Methanol Fuel Cells

NASA Technical Reports Server (NTRS)

Prakash, G. K. Surya; Smart, Marshall; Atti, Anthony R.; Olah, George A.; Narayanan, S. R.; Valdez, T.; Surampudi, S.

1996-01-01

Direct Methanol Fuel Cells (DMFC's) using polymer electrolyte membranes are promising power sources for portable and vehicular applications. State of the art technology using Nafion(R) 117 membranes (Dupont) are limited by high methanol permeability and cost, resulting in reduced fuel cell efficiencies and impractical commercialization. Therefore, much research in the fuel cell field is focused on the preparation and testing of low crossover and cost efficient polymer electrolyte membranes. The University of Southern California in cooperation with the Jet Propulsion Laboratory is focused on development of such materials. Interpenetrating polymer networks are an effective method used to blend polymer systems without forming chemical links. They provide the ability to modify physical and chemical properties of polymers by optimizing blend compositions. We have developed a novel interpenetrating polymer network based on poly (vinyl - difluoride)/cross-linked polystyrenesulfonic acid polymer composites (PVDF PSSA). Sulfonation of polystyrene accounts for protonic conductivity while the non-polar, PVDF backbone provides structural integrity in addition to methanol rejection. Precursor materials were prepared and analyzed to characterize membrane crystallinity, stability and degree of interpenetration. USC JPL PVDF-PSSA membranes were also characterized to determine methanol permeability, protonic conductivity and sulfur distribution. Membranes were fabricated into membrane electrode assemblies (MEA) and tested for single cell performance. Tests include cell performance over a wide range of temperatures (20 C - 90 C) and cathode conditions (ambient Air/O2). Methanol crossover values are measured in situ using an in-line CO2 analyzer.

Amphoteric Ion-Exchange Membranes with Significantly Improved Vanadium Barrier Properties for All-Vanadium Redox Flow Batteries.

PubMed

Nibel, Olga; Rojek, Tomasz; Schmidt, Thomas J; Gubler, Lorenz

2017-07-10

All-vanadium redox flow batteries (VRBs) have attracted considerable interest as promising energy-storage devices that can allow the efficient utilization of renewable energy sources. The membrane, which separates the porous electrodes in a redox flow cell, is one of the key components in VRBs. High rates of crossover of vanadium ions and water through the membrane impair the efficiency and capacity of a VRB. Thus, membranes with low permeation rate of vanadium species and water are required, also characterized by low resistance and stability in the VRB environment. Here, we present a new design concept for amphoteric ion-exchange membranes, based on radiation-induced grafting of vinylpyridine into an ethylene tetrafluoroethylene base film and a two-step functionalization to introduce cationic and anionic exchange sites, respectively. During long-term cycling, redox flow cells containing these membranes showed higher efficiency, less pronounced electrolyte imbalance, and significantly reduced capacity decay compared to the cells with the benchmark material Nafion 117. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Investigations of the ex situ ionic conductivities at 30 degrees C of metal-cation-free quaternary ammonium alkaline anion-exchange membranes in static atmospheres of different relative humidities.

PubMed

Varcoe, John R

2007-03-28

This article presents the first systematic study of the effect of Relative Humidity (RH) on the water content and hydroxide ion conductivity of quaternary ammonium-based Alkaline Anion-Exchange Membranes (AAEMs). These AAEMs have been developed specifically for application in alkaline membrane fuel cells, where conductivities of >0.01 S cm(-1) are mandatory. When fully hydrated, an ETFE-based radiation-grafted AAEM exhibited a hydroxide ion conductivity of 0.030 +/- 0.005 S cm(-1) at 30 degrees C without additional incorporation of metal hydroxide salts; this is contrary to the previous wisdom that anion-exchange membranes are very low in ionic conductivity and represents a significant breakthrough for metal-cation-free alkaline ionomers. Desirably, this AAEM also showed increased dimensional stability on full hydration compared to a Nafion-115 proton-exchange membrane; this dimensional stability is further improved (with no concomitant reduction in ionic conductivity) with a commercial AAEM of similar density but containing additional cross-linking. However, all of the AAEMs evaluated in this study demonstrated unacceptably low conductivities when the humidity of the surrounding static atmospheres was reduced (RH = 33-91%); this highlights the requirement for continued AAEM development for operation in H(2)/air fuel cells with low humidity gas supplies. Preliminary investigations indicate that the activation energies for OH(-) conduction in these quaternary ammonium-based solid polymer electrolytes are typically 2-3 times higher than for H(+) conduction in acidic Nafion-115 at all humidities.

Diffusive transfer to membranes as an effective interface between gel electrophoresis and mass spectrometry

NASA Astrophysics Data System (ADS)

Ogorzalek Loo, Rachel R.; Mitchell, Charles; Stevenson, Tracy I.; Loo, Joseph A.; Andrews, Philip C.

1997-12-01

Diffusive transfer was examined as a blotting method to transfer proteins from polyacrylamide gels to membranes for ultraviolet matrix-assisted laser desorption ionization (MALDI) mass spectrometry. The method is well-suited for transfers from isoelectric focusing (IEF) gels. Spectra have been obtained for 11 pmol of 66 kDa albumin loaded onto an IEF gel and subsequently blotted to polyethylene. Similarly, masses of intact carbonic anhydrase and hemoglobin were obtained from 14 and 20 pmol loadings. This methodology is also compatible with blotting high molecular weight proteins, as seen for 6 pmol of the 150 kDa monoclonal antibody anti-[beta]-galactosidase transferred to Goretex. Polypropylene, Teflon, Nafion and polyvinylidene difluoride (PVDF) also produced good spectra following diffusive transfer. Only analysis from PVDF required that the membrane be kept wet prior to application of matrix. Considerations in mass accuracy for analysis from large-area membranes with continuous extraction and delayed extraction were explored, as were remedies for surface charging. Vapor phase CNBr cleavage was applied to membrane-bound samples for peptide mapping.

Optimized anion exchange membranes for vanadium redox flow batteries.

PubMed

Chen, Dongyang; Hickner, Michael A; Agar, Ertan; Kumbur, E Caglan

2013-08-14

In order to understand the properties of low vanadium permeability anion exchange membranes for vanadium redox flow batteries (VRFBs), quaternary ammonium functionalized Radel (QA-Radel) membranes with three ion exchange capacities (IECs) from 1.7 to 2.4 mequiv g(-1) were synthesized and 55-60 μm thick membrane samples were evaluated for their transport properties and in-cell battery performance. The ionic conductivity and vanadium permeability of the membranes were investigated and correlated to the battery performance through measurements of Coulombic efficiency, voltage efficiency and energy efficiency in single cell tests, and capacity fade during cycling. Increasing the IEC of the QA-Radel membranes increased both the ionic conductivity and VO(2+) permeability. The 1.7 mequiv g(-1) IEC QA-Radel had the highest Coulombic efficiency and best cycling capacity maintenance in the VRFB, while the cell's voltage efficiency was limited by the membrane's low ionic conductivity. Increasing the IEC resulted in higher voltage efficiency for the 2.0 and 2.4 mequiv g(-1) samples, but the cells with these membranes displayed reduced Coulombic efficiency and faster capacity fade. The QA-Radel with an IEC of 2.0 mequiv g(-1) had the best balance of ionic conductivity and VO(2+) permeability, achieving a maximum power density of 218 mW cm(-2) which was higher than the maximum power density of a VRFB assembled with a Nafion N212 membrane in our system. While anion exchange membranes are under study for a variety of VRFB applications, this work demonstrates that the material parameters must be optimized to obtain the maximum cell performance.

Charge Dynamics and Bending Actuation in Aquivion Membrane Swelled with Ionic Liquids.

PubMed

Lin, Junhong; Liu, Yang; Zhang, Q M

2011-01-21

The actuation strain and speed of ionic electroactive polymer (EAP) actuators are mainly determined by the charge transport through the actuators and excess ion storage near the electrodes. We employ a recently developed theory on ion transport and storage to investigate the charge dynamics of short-side-chain Aquivion® (Hyflon®) membranes with different uptakes of ionic liquid (IL) 1-ethyl-3-methylimidazolium trifluoromethanesulfonate (EMI-Tf). The results reveal the existence of a critical uptake of ionic liquids above which the membrane exhibit a high ionic conductivity (σ>5×10(-2) mS/cm). Especially, we investigate the charge dynamics under voltages which are in the range for practical device operation (~1 volts and higher). The results show that the ionic conductivity, ionic mobility, and mobile ion concentration do not change with the applied voltage below 1 volt (and for σ below 4 volts). The results also show that bending actuation of the Aquivion membrane with 40 wt% EMI-Tf is much larger than that of Nafion, indicating that the shorter flexible side chains improve the electromechanical coupling between the excess ions and the membrane backbones, while not affect the actuation speed.

Charge Dynamics and Bending Actuation in Aquivion Membrane Swelled with Ionic Liquids

PubMed Central

Lin, Junhong; Liu, Yang; Zhang, Q. M.

2011-01-01

The actuation strain and speed of ionic electroactive polymer (EAP) actuators are mainly determined by the charge transport through the actuators and excess ion storage near the electrodes. We employ a recently developed theory on ion transport and storage to investigate the charge dynamics of short-side-chain Aquivion® (Hyflon®) membranes with different uptakes of ionic liquid (IL) 1-ethyl-3-methylimidazolium trifluoromethanesulfonate (EMI-Tf). The results reveal the existence of a critical uptake of ionic liquids above which the membrane exhibit a high ionic conductivity (σ>5×10−2 mS/cm). Especially, we investigate the charge dynamics under voltages which are in the range for practical device operation (~1 volts and higher). The results show that the ionic conductivity, ionic mobility, and mobile ion concentration do not change with the applied voltage below 1 volt (and for σ below 4 volts). The results also show that bending actuation of the Aquivion membrane with 40 wt% EMI-Tf is much larger than that of Nafion, indicating that the shorter flexible side chains improve the electromechanical coupling between the excess ions and the membrane backbones, while not affect the actuation speed. PMID:21339839

Friedel–Crafts Crosslinked Highly Sulfonated Polyether Ether Ketone (SPEEK) Membranes for a Vanadium/Air Redox Flow Battery

PubMed Central

Merle, Géraldine; Ioana, Filipoi Carmen; Demco, Dan Eugen; Saakes, Michel; Hosseiny, Seyed Schwan

2014-01-01

Highly conductive and low vanadium permeable crosslinked sulfonated poly(ether ether ketone) (cSPEEK) membranes were prepared by electrophilic aromatic substitution for a Vanadium/Air Redox Flow Battery (Vanadium/Air-RFB) application. Membranes were synthesized from ethanol solution and crosslinked under different temperatures with 1,4-benzenedimethanol and ZnCl2 via the Friedel–Crafts crosslinking route. The crosslinking mechanism under different temperatures indicated two crosslinking pathways: (a) crosslinking on the sulfonic acid groups; and (b) crosslinking on the backbone. It was observed that membranes crosslinked at a temperature of 150 °C lead to low proton conductive membranes, whereas an increase in crosslinking temperature and time would lead to high proton conductive membranes. High temperature crosslinking also resulted in an increase in anisotropy and water diffusion. Furthermore, the membranes were investigated for a Vanadium/Air Redox Flow Battery application. Membranes crosslinked at 200 °C for 30 min with a molar ratio between 2:1 (mol repeat unit:mol benzenedimethanol) showed a proton conductivity of 27.9 mS/cm and a 100 times lower VO2+ crossover compared to Nafion. PMID:24957118

Capillary-valve-based fabrication of ion-selective membrane junction for electrokinetic sample preconcentration in PDMS chip.

PubMed

Liu, Vincent; Song, Yong-Ak; Han, Jongyoon

2010-06-07

In this paper, we report a novel method for fabricating ion-selective membranes in poly(dimethylsiloxane) (PDMS)/glass-based microfluidic preconcentrators. Based on the concept of capillary valves, this fabrication method involves filling a lithographically patterned junction between two microchannels with an ion-selective material such as Nafion resin; subsequent curing results in a high aspect-ratio membrane for use in electrokinetic sample preconcentration. To demonstrate the concentration performance of this high-aspect-ratio, ion-selective membrane, we integrated the preconcentrator with a surface-based immunoassay for R-Phycoerythrin (RPE). Using a 1x PBS buffer system, the preconcentrator-enhanced immunoassay showed an approximately 100x improvement in sensitivity within 30 min. This is the first time that an electrokinetic microfluidic preconcentrator based on ion concentration polarization (ICP) has been used in high ionic strength buffer solutions to enhance the sensitivity of a surface-based immunoassay.

Anion- or Cation-Exchange Membranes for NaBH4/H2O2 Fuel Cells?

PubMed

Sljukić, Biljana; Morais, Ana L; Santos, Diogo M F; Sequeira, César A C

2012-07-19

Direct borohydride fuel cells (DBFC), which operate on sodium borohydride (NaBH4) as the fuel, and hydrogen peroxide (H2O2) as the oxidant, are receiving increasing attention. This is due to their promising use as power sources for space and underwater applications, where air is not available and gas storage poses obvious problems. One key factor to improve the performance of DBFCs concerns the type of separator used. Both anion- and cation-exchange membranes may be considered as potential separators for DBFC. In the present paper, the effect of the membrane type on the performance of laboratory NaBH4/H2O2 fuel cells using Pt electrodes is studied at room temperature. Two commercial ion-exchange membranes from Membranes International Inc., an anion-exchange membrane (AMI-7001S) and a cation-exchange membrane (CMI-7000S), are tested as ionic separators for the DBFC. The membranes are compared directly by the observation and analysis of the corresponding DBFC's performance. Cell polarization, power density, stability, and durability tests are used in the membranes' evaluation. Energy densities and specific capacities are estimated. Most tests conducted, clearly indicate a superior performance of the cation-exchange membranes over the anion-exchange membrane. The two membranes are also compared with several other previously tested commercial membranes. For long term cell operation, these membranes seem to outperform the stability of the benchmark Nafion membranes but further studies are still required to improve their instantaneous power load.

Producing intricate IPMC shapes by means of spray-painting and printing (Conference Presentation)

NASA Astrophysics Data System (ADS)

Trabia, Sarah; Olsen, Zakai; Hwang, Taeseon; Kim, Kwang Jin

2017-04-01

Ionic Polymer-Metal Composites (IPMC) are common soft actuators that are Nafion® based and plated with a conductive metal, such as platinum, gold, or palladium. Nafion® is available in three forms: sheets, pellets, and water dispersion. Nafion® sheets can be cut to the desired dimensions and are best for rectangular IPMCs. However, the user is not able to change the thickness of these sheets by stacking and melting because Nafion® does not melt. A solution to this is Nafion® pellets, which can melt. These can be used for extrusion and injection molding. Though Nafion® pellets can be melted, they are difficult to work with, making the process quite challenging to master. The last form is Nafion® Water Dispersion, which can be used for casting. Casting can produce the desired thickness, but it does not solve the problem of achieving complex contours. The current methods of fabrication do not allow for complex shapes and structures. To solve this problem, two methods are presented: painting and printing. The painting method uses Nafion® Water Dispersion, an airbrush, and vinyl stencils. The stencils can be made into any shape with detailed edges. The printing method uses Nafion® pellets that are extruded into filaments and a commercially available 3D printer. The models are drawn in a Computer-Aided Drawing (CAD) program, such as SolidWorks. The produced Nafion® membranes will be compared with a commercial Nafion® membrane through a variety of tests, including Fourier Transform Infrared Spectroscopy, Scanning Electron Microscope, Thermogravimetric Analysis, Dynamic Mechanical Analysis, and Optical Microscope.

Bio-electrochemical characterization of air-cathode microbial fuel cells with microporous polyethylene/silica membrane as separator.

PubMed

Kircheva, Nina; Outin, Jonathan; Perrier, Gérard; Ramousse, Julien; Merlin, Gérard; Lyautey, Emilie

2015-12-01

The aim of this work was to study the behavior over time of a separator made of a low-cost and non-selective microporous polyethylene membrane (RhinoHide®) in an air-cathode microbial fuel cell with a reticulated vitreous carbon foam bioanode. Performances of the microporous polyethylene membrane (RhinoHide®) were compared with Nafion®-117 as a cationic exchange membrane. A non-parametric test (Mann-Whitney) done on the different sets of coulombic or energy efficiency data showed no significant difference between the two types of tested membrane (p<0.05). Volumetric power densities were ranging from 30 to 90 W·m(-3) of RVC foam for both membranes. Similar amounts of biomass were observed on both sides of the polyethylene membrane illustrating bacterial permeability of this type of separator. A monospecific denitrifying population on cathodic side of RhinoHide® membrane has been identified. Electrochemical impedance spectroscopy (EIS) was used at OCV conditions to characterize electrochemical behavior of MFCs by equivalent electrical circuit fitted on both Nyquist and Bode plots. Resistances and pseudo-capacitances from EIS analyses do not differ in such a way that the nature of the membrane could be considered as responsible. Copyright © 2015 Elsevier B.V. All rights reserved.

Hydrodeoxygenation of bio-derived phenols to hydrocarbons using RANEY Ni and Nafion/SiO2 catalysts.

PubMed

Zhao, Chen; Kou, Yuan; Lemonidou, Angeliki A; Li, Xuebing; Lercher, Johannes A

2010-01-21

A simple, green, cost- and energy-efficient route for converting phenolic components in bio-oil to hydrocarbons and methanol has been developed, with nearly 100% yields. In the heterogeneous catalysts, RANEY Ni acts as the hydrogenation catalyst and Nafion/SiO(2) acts as the Brønsted solid acid for hydrolysis and dehydration.

Preparation of nano-structured polymeric proton conducting membranes for use in fuel cells.

PubMed

Alberti, Giulio; Casciola, Mario; Pica, Monica; Di Cesare, Giusi

2003-03-01

We briefly discuss the state of the art of polymer electrolyte membrane fuel cells and suggest that the main obstacles to the commercial development of these fuel cells are essentially the high costs and poor characteristics of present proton conducting membranes. A strategy for the preparation of improved nanocomposite membranes based on the introduction of proton conducting lamell? in the polymeric matrix of present ionomeric membranes is then discussed. Due to their high proton conductivity (in some cases even higher than 10(-1) S cm(-1)), tailor made lamellae obtained by exfoliation of superacid metal (IV) phosphonates are particularly suitable for the preparation of these hybrid membranes. The expected positive influence of the dispersed lamellae on important properties of proton conducting membranes, such as swelling, mechanical resistance, proton transport, and diffusion of methanol, are also discussed. The methods used to obtain good lamellar dispersions into ionomeric polymers and the preparation and main characteristics of some hybrid membranes are also briefly described. The presence of nanoparticles of metal phosphonates in the electrodic interfaces Nafion/Pt already considerably improves the electrochemical characteristics of fuel cells in the temperature range 80-130 degrees C. The increased working temperature of the fuel cell considerably reduces CO poisoning of the platinum electrodes and allows better control of the cooling system, thus overcoming important obstacles to the development of medium temperature PEM fuel cells.

Advances in proton-exchange membranes for fuel cells: an overview on proton conductive channels (PCCs).

PubMed

Wu, Liang; Zhang, Zhenghui; Ran, Jin; Zhou, Dan; Li, Chuanrun; Xu, Tongwen

2013-04-14

Proton-exchange membranes (PEM) display unique ion-selective transport that has enabled a breakthrough in high-performance proton-exchange membrane fuel cells (PEMFCs). Elemental understanding of the morphology and proton transport mechanisms of the commercially available Nafion® has promoted a majority of researchers to tune proton conductive channels (PCCs). Specifically, knowledge of the morphology-property relationship gained from statistical and segmented copolymer PEMs has highlighted the importance of the alignment of PCCs. Furthermore, increasing efforts in fabricating and aligning artificial PCCs in field-aligned copolymer PEMs, nanofiber composite PEMs and mesoporous PEMs have set new paradigms for improvement of membrane performances. This perspective profiles the recent development of the channels, from the self-assembled to the artificial, with a particular emphasis on their formation and alignment. It concludes with an outlook on benefits of highly aligned PCCs for fuel cell operation, and gives further direction to develop new PEMs from a practical point of view.

Preparation of new crosslinking agents and additives for use in polymer electrolyte membranes (PEMs) for fuel cell applications

NASA Astrophysics Data System (ADS)

Zhou, Yangliu

The most commonly used proton conductive membrane in polymer electrolyte membrane fuel cells (PEMFC) and direct methanol fuel cells (DMFC) studies to date is DuPont's NafionRTM, which is a perfluorinated copolymer of tetrafluoroethylene (TFE) and perfluorovinyl ether with a pendant sulfonic acid group. A focus of this work is to find ways to improve the performance of NafionRTM membranes. Crosslinking the TFE chains of fluorinated ionomeric copolymers to improve their thermal and mechanical stability is a proven route to this goal. A straightforward synthetic route to perfluorinated divinyl ethers of the formula CF2=CFO(CF 2)3[OCF(CF3)CF2]mOCF=CF 2 (m = 0-1) has been demonstrated. The compounds CF2=CFO(CF 2)3OCF=CF2 and CF2=CFO(CF2) 3OCF(CF3)CF2OCF=CF2 were prepared and characterized by GC-MS, 13C and 19F NMR, and gas-IR spectroscopy. Synthetic routes to fluorosulfato-tetrafluoropropionyl fluoride [FSO3CF2CF2C(O)F] and difluoromalonyl difluoride [F(O)CCF2C(O)F] with improved yields were found. The second focus of the dissertation was the development of fluorous triarylphosphines for use as new doping materials for the modification of NafionRTM membranes and for use as ligands in catalysts for biphasic catalysis. The synthesis and characterization of a series of new polyhexafluoropropylene oxide derivatives for preparation of fluorous triarylphosphines and phosphonium salts was studied, such as F[CF(CF3)CF2O] 4CF(CF3)CH2CH2I, F[CF(CF3)CF 2O]4CF(CF3)CH=CH2, F[CF(CF3)CF 2O]4CF(CF3) CH2CH2C6H5, and F[CF(CF 3)CF2O]4CF(CF3)CH2CH 2C6H4Br. In a separate study, the photochlorination of 2,2,3,3-tetrafluoro-1-propanol (HCF2CF2CH2OH) and 2,2,3,3-tetrafluoropropyl 2,2,3,3-tetrafluoropropionate [HCF2CF2C(O)OCH2 CF2CF2H] with super diazo blue light (lambda max = 420 nm) were investigated. The photochemical products are different from those obtained under mercury light (lambda = 253.7nm). A new compound ClCF2CF2C(O)OC(H)ClCF2CF2Cl was prepared and characterized by GC-MS, elemental

High performance anode based on a partially fluorinated sulfonated polyether for direct methanol fuel cells operating at 130 °C

NASA Astrophysics Data System (ADS)

Mack, Florian; Gogel, Viktor; Jörissen, Ludwig; Kerres, Jochen

2014-06-01

Due to the disadvantages of the Nafion polymer for the application in the direct methanol fuel cell (DMFC) especial at temperatures above 100 °C several polymers of the hydrocarbon type have already been investigated as membranes and ionomers in the DMFC. Among them were nonfluorinated and partially fluorinated arylene main-chain hydrocarbon polymers. In previous work, sulfonated polysulfone (sPSU) has been applied as the proton-conductive binder in the anode of a DMFC, ending up in good and stable performance. In continuation of this work, in the study presented here a polymer was prepared by polycondensation of decafluorobiphenyl and bisphenol AF. The formed polymer was sulfonated after polycondensation by oleum and the obtained partially fluorinated sulfonated polyether (SFS) was used as the binder and proton conductor in a DMFC anode operating at a temperature of 130 °C. The SFS based anode with 5% as ionomer showed comparable performance for the methanol oxidation to Nafion based anodes and significant reduced performance degradation versus Nafion and sPSU based anodes on the Nafion 115 membrane. Membrane electrode assemblies (MEAs) with the SFS based anode showed drastically improved performance compared to MEAs with Nafion based anodes during operation with lower air pressure at the cathode.

Properties investigation of sulfonated poly(ether ether ketone)/polyacrylonitrile acid-base blend membrane for vanadium redox flow battery application.

PubMed

Li, Zhaohua; Dai, Wenjing; Yu, Lihong; Liu, Le; Xi, Jingyu; Qiu, Xinping; Chen, Liquan

2014-11-12

Acid-base blend membrane prepared from sulfonated poly(ether ether ketone) (SPEEK) and polyacrylonitrile (PAN) was detailedly evaluated for vanadium redox flow battery (VRFB) application. SPEEK/PAN blend membrane exhibited dense and homogeneous cross-section morphology as scanning electron microscopy and energy-dispersive X-ray spectroscopy images show. The acid-base interaction of ionic cross-linking and hydrogen bonding between SPEEK and PAN could effectively reduce water uptake, swelling ratio, and vanadium ion permeability, and improve the performance and stability of blend membrane. Because of the good balance of proton conductivity and vanadium ion permeability, blend membrane with 20 wt % PAN (S/PAN-20%) showed higher Coulombic efficiency (96.2% vs 91.1%) and energy efficiency (83.5% vs 78.4%) than Nafion 117 membrane at current density of 80 mA cm(-2) when they were used in VRFB single cell. Besides, S/PAN-20% membrane kept a stable performance during 150 cycles at current density of 80 mA cm(-2) in the cycle life test. Hence the SPEEK/PAN acid-base blend membrane could be used as promising candidate for VRFB application.

Influence of water and membrane microstructure on the transport properties of proton exchange membrane fuel cells

NASA Astrophysics Data System (ADS)

Siu, Ana Rosa

Proton transport in proton exchange membranes (PEMs) depends on interaction between water and acid groups covalently bound to the polymer. Although the presence of water is important in maintaining the PEM's functions, a thorough understanding of this topic is still lacking. The objective of this work is to provide a better understanding of how the nature water, confined to ionic domains of the polymer, influences the membrane's ability to transport protons, methanol and water. Understanding this topic will facilitate development of new materials with favorable transport properties for fuel cells use. Five classes of polymer membranes were used in this work: polyacrylonitrile-graft-poly(styrenesulfonic) acid (PAN-g-macPSSA); poly(vinylidene difluoride) irradiation-graft-poly(styrenesulfonic) acid (PVDF-g-PSSA); poly(ethylenetetrafluoroethylene) irradiation-graft-poly(styrenesulfonic) acid (ETFE-gPSSA); PVDF-g-PSSA with hydroxyethylmethacrylate (HEMA); and perfluorosulfonic acid membrane (Nafion). The nature of water within the polymers (freezable versus non-freezable states) was measured by systematically freezing samples, and observing the temperature at which water freezes and the amount of heat released in the process. Freezing water-swollen membranes resulted in a 4-fold decrease in the proton conductivity of the PEM. Activation energies of proton transport before and after freezing were ˜ 0.15 eV and 0.5 eV, consistent with proton transport through liquid water and bound water, respectively. Reducing the content of water in membrane samples decreased the amount of freezable and non-freezable water. Calorimetric measurements of membranes in various degrees of hydration showed that water molecules became non-freezable when lambda, (water molecules per sulfonic acid group) was less than ˜14. Proton conduction through membranes containing only non-freezable water was demonstrated to be feasible. Diffusion experiments showed that the permeability of methanol

Electrochemical detection of DNA damage induced by acrylamide and its metabolite at the graphene-ionic liquid-Nafion modified pyrolytic graphite electrode.

PubMed

Qiu, Yanyan; Qu, Xiangjin; Dong, Jing; Ai, Shiyun; Han, Ruixia

2011-06-15

A new electrochemical biosensor for directly detecting DNA damage induced by acrylamide (AA) and its metabolite was presented in this work. The graphene-ionic liquid-Nafion modified pyrolytic graphite electrode (PGE) was prepared, and then horseradish peroxidase (HRP) and natural double-stranded DNA were alternately assembled on the modified electrode by the layer-by-layer method. The PGE/graphene-ionic liquid-Nafion and the construction of the (HRP/DNA)(n) film were characterized by electrochemical impedance spectroscopy. With the guanine signal in DNA as an indicator, the damage of DNA was detected by differential pulse voltammetry after PGE/graphene-ionic liquid-Nafion/(HRP/DNA)(n) was incubated in AA solution or AA+H(2)O(2) solution at 37°C. This method provides a new model to mimic and directly detect DNA damage induced by chemical pollutants and their metabolites in vitro. The results indicated that, in the presence of H(2)O(2), HRP was activated and catalyzed the transformation of AA to glycidamide, which could form DNA adducts and induce more serious damage of DNA than AA. In order to further verify these results, UV-vis spectrophotometry was also used to investigate DNA damage induced by AA and its metabolites in solution and the similar results were obtained. Copyright © 2011 Elsevier B.V. All rights reserved.

Effect of separator and inoculum type on electricity generation and microbial community in single-chamber microbial fuel cells.

PubMed

Yu, Jaecheul; Park, Younghyun; Lee, Taeho

2014-04-01

Single-chamber microbial fuel cell (SMFC)-I consisted of 4 separator-electrode assemblies (SEAs) with two types of cation exchange membrane (CEM: Nafion and CMI 7000) and an anion exchange membrane (AEM: AMI 7001). SMFC-II consisted of 4 SEAs with Nafion and three types of nonwoven fabric. SMFC-I and -II were inoculated with anaerobic digested and activated sludge, respectively, and operated under fed-batch mode. In SMFC I, AEM-SEA showed a maximum power density (PDmax). Nafion-SEA showed a PDmax in SMFC II, which was similar to that of Nafion-SEA of SMFC I. Although different bacteria were developed in SMFC-I (Deltaproteobacteria and Firmicutes) and SMFC-II (Gammaproteobacteria, Betaproteobacteria and Bacteroidetes), the inoculum type little affects electricity generation. Variations of pH and oxygen in biofilm have influenced microbial community structure and electricity generation according to the electrode and separator material. Although the electricity generation of non-woven fabric-SEA was less than that of Nafion-SEA, the use of non-woven fabrics is expected to reduce the construction and operating costs of MFCs.

Detection of Guanine and Adenine Using an Aminated Reduced Graphene Oxide Functional Membrane-Modified Glassy Carbon Electrode

PubMed Central

Li, Di; Yang, Xiao-Lu; Xiao, Bao-Lin; Geng, Fang-Yong; Hong, Jun; Sheibani, Nader; Moosavi-Movahedi, Ali Akbar

2017-01-01

A new electrochemical sensor based on a Nafion, aminated reduced graphene oxide and chitosan functional membrane-modified glassy carbon electrode was proposed for the simultaneous detection of adenine and guanine. Fourier transform-infrared spectrometry (FTIR), transmission electron microscopy (TEM), and electrochemical methods were utilized for the additional characterization of the membrane materials. The prepared electrode was utilized for the detection of guanine (G) and adenine (A). The anodic peak currents to G and A were linear in the concentrations ranging from 0.1 to 120 μM and 0.2 to 110 μM, respectively. The detection limits were found to be 0.1 μM and 0.2 μM, respectively. Moreover, the modified electrode could also be used to determine G and A in calf thymus DNA. PMID:28718793

Anion- or Cation-Exchange Membranes for NaBH4/H2O2 Fuel Cells?

PubMed Central

Šljukić, Biljana; Morais, Ana L.; Santos, Diogo M. F.; Sequeira, César A. C.

2012-01-01

Direct borohydride fuel cells (DBFC), which operate on sodium borohydride (NaBH4) as the fuel, and hydrogen peroxide (H2O2) as the oxidant, are receiving increasing attention. This is due to their promising use as power sources for space and underwater applications, where air is not available and gas storage poses obvious problems. One key factor to improve the performance of DBFCs concerns the type of separator used. Both anion- and cation-exchange membranes may be considered as potential separators for DBFC. In the present paper, the effect of the membrane type on the performance of laboratory NaBH4/H2O2 fuel cells using Pt electrodes is studied at room temperature. Two commercial ion-exchange membranes from Membranes International Inc., an anion-exchange membrane (AMI-7001S) and a cation-exchange membrane (CMI-7000S), are tested as ionic separators for the DBFC. The membranes are compared directly by the observation and analysis of the corresponding DBFC’s performance. Cell polarization, power density, stability, and durability tests are used in the membranes’ evaluation. Energy densities and specific capacities are estimated. Most tests conducted, clearly indicate a superior performance of the cation-exchange membranes over the anion-exchange membrane. The two membranes are also compared with several other previously tested commercial membranes. For long term cell operation, these membranes seem to outperform the stability of the benchmark Nafion membranes but further studies are still required to improve their instantaneous power load. PMID:24958292

Photosynthetic solar cell using nanostructured proton exchange membrane for microbial biofilm prevention.

PubMed

Lee, Dong Hyun; Oh, Hwa Jin; Bai, Seoung Jae; Song, Young Seok

2014-06-24

Unwanted biofilm formation has a detrimental effect on bioelectrical energy harvesting in microbial cells. This issue still needs to be solved for higher power and longer durability and could be resolved with the help of nanoengineering in designing and manufacturing. Here, we demonstrate a photosynthetic solar cell (PSC) that contains a nanostructure to prevent the formation of biofilm by micro-organisms. Nanostructures were fabricated using nanoimprint lithography, where a film heater array system was introduced to precisely control the local wall temperature. To understand the heat and mass transfer phenomena behind the manufacturing and energy harvesting processes of PSC, we carried out a numerical simulation and experimental measurements. It revealed that the nanostructures developed on the proton exchange membrane enable PSC to produce enhanced output power due to the retarded microbial attachment on the Nafion membrane. We anticipate that this strategy can provide a pathway where PSC can ensure more renewable, sustainable, and efficient energy harvesting performance.

Alkaline direct alcohol fuel cells using an anion exchange membrane

NASA Astrophysics Data System (ADS)

Matsuoka, Koji; Iriyama, Yasutoshi; Abe, Takeshi; Matsuoka, Masao; Ogumi, Zempachi

Alkaline direct alcohol fuel cells using an OH-form anion exchange membrane and polyhydric alcohols were studied. A high open circuit voltage of ca. 800 mV was obtained for a cell using Pt-Ru/C (anode) and Pt/C (cathode) at 323 K, which was about 100-200 mV higher than that for a DMFC using Nafion ®. The maximum power densities were in the order of ethylene glycol > glycerol > methanol > erythritol > xylitol. Silver catalysts were used as a cathode catalyst to fabricate alkaline fuel cells, since silver catalyst is almost inactive in the oxidation of polyhydric alcohols. Alkaline direct ethylene glycol fuel cells using silver as a cathode catalyst gave excellent performance because higher concentrations of fuel could be supplied to the anode.

Functionalizing Carbon Nanotubes and Related Nanostructures for Various Applications

DTIC Science & Technology

2009-11-14

emitter very interesting. Specifically, their initial tests on the wetting property of ionic liquid propellants appeared quite promising. During the...tolerant membrane for DMFC based on Nafion /polyaniline nanowires, and (6) sieve-layer mediated solar cell based on ZnPc/Si p-n junctions. On-chip wafer...reported here: (i) the AOARD-07-4077 Final Report 1114/2009, Chen LC 5 methanol-tolerant fuel cell membrane based on polyaniline nanowires and Nafion

A multilayer membrane amperometric glucose sensor fabricated using planar techniques for large-scale production.

PubMed

Matsumoto, T; Saito, S; Ikeda, S

2006-03-23

This paper reports on a multilayer membrane amperometric glucose sensor fabricated using planar techniques. It is characterized by good reproducibility and suitable for large-scale production. The glucose sensor has 82 electrode sets formed on a single glass substrate, each with a platinum working electrode (WE), a platinum counter electrode (CE) and an Ag/AgCl reference electrode (RE). The electrode sets are coated with a membrane consisting of five layers: gamma-aminopropyltriethoxysilane (gamma-APTES), Nafion, glucose oxidase (GOX), gamma-APTES and perfluorocarbon polymer (PFCP), in that order. Tests have shown that the sensor has acceptably low dispersion (relative standard deviation, R.S.D.=42.9%, n=82), a wide measurement range (1.11-111 mM) and measurement stability over a 27-day period. Measurements of the glucose concentration in a control human urine sample demonstrated that the sensor has very low dispersion (R.S.D.=2.49%, n=10).

Advanced Double Layer Capacitor

DTIC Science & Technology

1989-07-01

Membrane and Electrode Assemblies The Nafion electrolyte was introduced into the electrode by two different methods: 1) mixing of the Nafion solution with... electroosmotic transport of water, allows some liquid electrolyte to permeate into the structure, which causes partial flooding. On the basis of these...solution of Nafion 117) was mixed with the RuO x powder. The solvent was then allowed to evaporate and the resulting composite powder was crushed and

New biosensing platforms based on the layer-by-layer self-assembling of polyelectrolytes on Nafion/carbon nanotubes-coated glassy carbon electrodes.

PubMed

Rivas, Gustavo A; Miscoria, Silvia A; Desbrieres, Jacques; Barrera, Gustavo D

2007-01-15

We are proposing for the first time the use of a Nafion/multi-walled carbon nanotubes dispersion deposited on glassy carbon electrodes (GCE) as a new platform for developing enzymatic biosensors based on the self-assembling of a chitosan derivative and different oxidases. The electrodes are obtained by deposition of a layer of Nafion/multi-wall carbon nanotubes dispersion on glassy carbon electrodes, followed by the adsorption of a chitosan derivative as polycation and glucose oxidase, l-aminoacid oxidase or polyphenol oxidase, as polyanions and biorecognition elements. The optimum configuration for glucose biosensors has allowed a highly sensitive (sensitivity=(0.28+/-0.02)muAmM(-1), r=0.997), fast (4s in reaching the maximum response), and highly selective (0% interference of ascorbic acid and uric acid at maximum physiological levels) glucose quantification at 0.700V with detection and quantification limits of 0.035 and 0.107mM, respectively. The repetitivity for 10 measurements was 5.5%, while the reproducibility was 8.4% for eight electrodes. The potentiality of the new platform was clearly demonstrated by using the carbon nanotubes/Nafion layer as a platform for the self-assembling of l-aminoacid oxidase and polyphenol oxidase. Therefore, the platform we are proposing here, that combines the advantages of nanostructured materials with those of the layer-by-layer self-assembling of polyelectrolytes, opens the doors to new and exciting possibilities for the development of enzymatic and affinity biosensors using different transdution modes.

Pore-Size-Tuned Graphene Oxide Frameworks as Ion-Selective and Protective Layers on Hydrocarbon Membranes for Vanadium Redox-Flow Batteries.

PubMed

Kim, Soohyun; Choi, Junghoon; Choi, Chanyong; Heo, Jiyun; Kim, Dae Woo; Lee, Jang Yong; Hong, Young Taik; Jung, Hee-Tae; Kim, Hee-Tak

2018-05-07

The laminated structure of graphene oxide (GO) membranes provides exceptional ion-separation properties due to the regular interlayer spacing ( d) between laminate layers. However, a larger effective pore size of the laminate immersed in water (∼11.1 Å) than the hydrated diameter of vanadium ions (>6.0 Å) prevents its use in vanadium redox-flow batteries (VRFB). In this work, we report an ion-selective graphene oxide framework (GOF) with a d tuned by cross-linking the GO nanosheets. Its effective pore size (∼5.9 Å) excludes vanadium ions by size but allows proton conduction. The GOF membrane is employed as a protective layer to address the poor chemical stability of sulfonated poly(arylene ether sulfone) (SPAES) membranes against VO 2 + in VRFB. By effectively blocking vanadium ions, the GOF/SPAES membrane exhibits vanadium-ion permeability 4.2 times lower and a durability 5 times longer than that of the pristine SPAES membrane. Moreover, the VRFB with the GOF/SPAES membrane achieves an energy efficiency of 89% at 80 mA cm -2 and a capacity retention of 88% even after 400 cycles, far exceeding results for Nafion 115 and demonstrating its practical applicability for VRFB.

Better Proton-Conducting Polymers for Fuel-Cell Membranes

NASA Technical Reports Server (NTRS)

Narayan, Sri; Reddy, Prakash

2012-01-01

Polyoxyphenylene triazole sulfonic acid has been proposed as a basis for development of improved proton-conducting polymeric materials for solid-electrolyte membranes in hydrogen/air fuel cells. Heretofore, the proton-conducting membrane materials of choice have been exemplified by a family of perfluorosulfonic acid-based polymers (Nafion7 or equivalent). These materials are suitable for operation in the temperature of 75 to 85 C, but in order to reduce the sizes and/or increase the energy-conversion efficiencies of fuel-cell systems, it would be desirable to increase temperatures to as high as 120 C for transportation applications, and to as high as 180 C for stationary applications. However, at 120 C and at relative humidity values below 50 percent, the loss of water from perfluorosulfonic acid-based polymer membranes results in fuel-cell power densities too low to be of practical value. Therefore, membrane electrolyte materials that have usefully high proton conductivity in the temperature range of 180 C at low relative humidity and that do not rely on water for proton conduction at 180 C would be desirable. The proposed polyoxyphenylene triazole sulfonic acid-based materials have been conjectured to have these desirable properties. These materials would be free of volatile or mobile acid constituents. The generic molecular structure of these materials is intended to exploit the fact, demonstrated in previous research, that materials that contain ionizable acid and base groups covalently attached to thermally stable polymer backbones exhibit proton conduction even in the anhydrous state.

Application of Novel Anion-Exchange Blend Membranes (AEBMs) to Vanadium Redox Flow Batteries.

PubMed

Cho, Hyeongrae; Krieg, Henning M; Kerres, Jochen A

2018-06-19

Both cation-exchange membranes and anion-exchange membranes are used as ion conducting membranes in vanadium redox flow batteries (VRFBs). Anion-exchange membranes (AEMs) are applied in vanadium redox flow batteries due to the high blocking property of vanadium ions via the Donnan exclusion effect. In this study, novel anion-exchange blend membranes (AEBMs) were prepared, characterized, and applied in VRFBs. Bromomethylated poly(2,6-dimethyl-1,4-phenylene oxide), poly[(1-(4,4′-diphenylether)-5-oxybenzimidazole)-benzimidazole] (PBI-OO) and sulfonated polyether sulfone polymer were combined to prepare 3-component AEBMs with 1,2,4,5-tetramethylimidazole (TMIm) for quaternization. 3-component AEBMs showed significantly enhanced chemical and mechanical properties compared with those of 2-component AEBMs, resulting in an improved performance in VRFBs. The compositions of the anion-exchange polymers in 3-component AEBMs were systematically varied to optimize the AEBMs for the redox-flow battery application. While the 3-component AEBMs showed comparable efficiencies with Nafion ® 212 membranes, they displayed improved vanadium ions cross-over as was confirmed by open circuit voltage tests and capacity fade tests conducted in VRFBs. In addition, one of the synthesized 3-component AEBM had a superior coulombic efficiency and capacity retention in a charging⁻discharging test over 300 cycles at a current density of 40 mA/cm². It can thus be concluded that 3-component AEBMs are promising candidates for long-term operation in VRFBs.

Proton-conducting membranes based on benzimidazole polymers for high-temperature PEM fuel cells. A chemical quest.

PubMed

Asensio, Juan Antonio; Sánchez, Eduardo M; Gómez-Romero, Pedro

2010-08-01

The development of high-temperature PEM fuel cells (working at 150-200 degrees C) is pursued worldwide in order to solve some of the problems of current cells based on Nafion (CO tolerance, improved kinetics, water management, etc.). Polybenzimidazole membranes nanoimpregnated with phosphoric acid have been studied as electrolytes in PEMFCs for more than a decade. Commercially available polybenzimidazole (PBI) has been the most extensively studied and used for this application in membranes doped with all sorts of strong inorganic acids. In addition to this well-known polymer we also review here studies on ABPBI and other polybenzimidazole type membranes. More recently, several copolymers and related derivatives have attracted many researchers' attention, adding variety to the field. Furthermore, besides phosphoric acid, many other strong inorganic acids, as well as alkaline electrolytes have been used to impregnate benzimidazole membranes and are analyzed here. Finally, we also review different hybrid materials based on polybenzimidazoles and several inorganic proton conductors such as heteropoly acids, as well as sulfonated derivatives of the polymers, all of which contribute to a quickly-developing field with many blooming results and useful potential which are the subject of this critical review (317 references).

Electrochemistry of hemoglobin entrapped in a Nafion/nano-ZnO film on carbon ionic liquid electrode.

PubMed

Sun, Wei; Zhai, ZiQin; Wang, DanDan; Liu, ShuFeng; Jiao, Kui

2009-02-01

A stable composite film composed of the ionomer Nafion, the ZnO nanoparticle and the protein hemoglobin was cast on the surface of an ionic liquid modified carbon paste electrode (CILE) to establish a modified electrode denoted as Nafion/nano-ZnO/Hb/CILE. UV-vis and FT-IR spectrum showed that hemoglobin in the film retained its native conformation. The electrochemical behaviors of hemoglobin entrapped in the film were carefully investigated with cyclic voltammetry. A pair of well-defined and quasi-reversible redox voltammetric peaks for Hb Fe(III)/Fe(II) was obtained with the standard potential (E(0)') located at -0.344 V (vs. SCE) in phosphate buffer solution (PBS, pH 7.0), which was attributed to the direct electron transfer of Hb with electrode in the microenvironments of ZnO nanoparticle and ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate (BMIMPF(6)). The electrochemical parameters of Hb in the composite film were further carefully calculated with the results of the electron-transfer rate constant (k(s)) as 0.139 s(-1), the charge transfer coefficient (alpha) as 0.413 and the number of electron transferred (n) as 0.95. The Hb modified electrode showed good electrocatalytic ability toward the reduction of trichloroacetic acid (TCA).

Searching for a new ionomer for 3D printable ionic polymer-metal composites: Aquivion as a candidate

NASA Astrophysics Data System (ADS)

Trabia, Sarah; Olsen, Zakai; Kim, Kwang J.

2017-11-01

The work presented in this paper introduces Aquivion as a potential candidate for additive manufacturing of ionomeric polymers for the application of IPMCs. First, Aquivion was characterized and compared with Nafion to show that it has the similar qualities, with the major difference being the ionic conductivity. Ionic polymer-metal composites (IPMCs) were fabricated using off-the-shelf membranes of Nafion and Aquivion. The actuation tests showed improved performance for an IPMC with Aquivion as the base compared to an IPMC with a Nafion base. With these results in mind, additive manufacturing of unique shapes using Aquivion filament was studied. A 3D printer was modified to work with Aquivion filament and the polymer was printed into various shapes. Using the printed membranes, IPMCs were fabricated using an electroless plating process. Nafion-based and printed Aquivion-based IPMCs were tested for their performance in back relaxation, frequency driven actuation, blocking force, and mechano-electric sensing. The printed Aquivion-based IPMCs performed comparably to Nafion-based IPMC in back relaxation and showed significantly improved performance in frequency driven actuation, blocking force generation, and mechano-electric sensing.

Colorimetric detection of endogenous hydrogen sulfide production in living cells

NASA Astrophysics Data System (ADS)

Ahn, Yong Jin; Lee, Young Ju; Lee, Jaemyeon; Lee, Doyeon; Park, Hun-Kuk; Lee, Gi-Ja

2017-04-01

Hydrogen sulfide (H2S) has received great attention as a third gaseous signal transmitter, following nitric oxide and carbon monoxide. In particular, H2S plays an important role in the regulation of cancer cell biology. Therefore, the detection of endogenous H2S concentrations within biological systems can be helpful to understand the role of gasotransmitters in pathophysiology. Although a simple and inexpensive method for the detection of H2S has been developed, its direct and precise measurement in living cells remains a challenge. In this study, we introduced a simple, facile, and inexpensive colorimetric system for selective H2S detection in living cells using a silver-embedded Nafion/polyvinylpyrrolidone (PVP) membrane. This membrane could be easily applied onto a polystyrene microplate cover. First, we optimized the composition of the coating membrane, such as the PVP/Nafion mixing ratio and AgNO3 concentration, as well as the pH of the Na2S (H2S donor) solution and the reaction time. Next, the in vitro performance of a colorimetric detection assay utilizing the silver/Nafion/PVP membrane was evaluated utilizing a known concentration of Na2S standard solution both at room temperature and at 37 °C in a 5% CO2 incubator. As a result, the sensitivity of the colorimetric assay for H2S at 37 °C in the incubator (0.0056 Abs./μM Na2S, R2 = 0.9948) was similar to that at room temperature (0.0055 Abs./μM Na2S, R2 = 0.9967). Moreover, these assays were less sensitive to interference from compounds such as glutathione, L-cysteine (Cys), and dithiothreitol than to the H2S from Na2S. This assay based on the silver/Nafion/PVP membrane also showed excellent reproducibility (2.8% RSD). Finally, we successfully measured the endogenous H2S concentrations in live C6 glioma cells by s-(5‧-adenosyl)-L-methionine stimulation with and without Cys and L-homocysteine, utilizing the silver/Nafion/PVP membrane. In summary, colorimetric assays using silver/Nafion

Chemicals and energy co-generation from direct hydrocarbons/oxygen proton exchange membrane fuel cell

NASA Astrophysics Data System (ADS)

Li, W. S.; Lu, D. S.; Luo, J. L.; Chuang, K. T.

A proton exchange membrane fuel cell for chemicals and energy co-generation was set up with hydrocarbons ethane, propane and butane as fuels, and the electrochemical performance of the cell was studied by using linear potential sweep, alternating current impedance and gas chromatography. The cell performance can be improved to a great extent by increasing the platinum load in the catalyst, by treating the membrane with phosphoric acid and by elevating temperature. The improvement of cell performance by the increase of platinum load is ascribed to the increase of reaction sites for hydrocarbon oxidation, that by phosphoric acid treatment to the increase of proton conductivity in Nafion membrane, and that by elevating temperature to the improvement in thermodynamic as well as kinetic aspects. Only a small fraction of the hydrocarbon is converted to carbon dioxide in this cell during its power generation. The current efficiency is 5% for the conversion of ethane to carbon dioxide in the ethane/oxygen fuel cell with 20% carbon-supported platinum as catalyst and phosphoric acid-treated membrane as proton exchange membrane at 0.2 V, 80 °C and ambient pressure. The reaction activity of hydrocarbons at the anode is in the order of propane, butane and ethane. The possible chemicals produced from the cell were hydrocarbons with more than six carbons, which are inactive at the anode under cell conditions.

Fabrication of polymer electrolyte membrane fuel cell MEAs utilizing inkjet print technology

NASA Astrophysics Data System (ADS)

Towne, Silas; Viswanathan, Vish; Holbery, James; Rieke, Peter

Utilizing drop-on-demand technology, we have successfully fabricated hydrogen-air polymer electrolyte membrane fuel cells (PEMFC), demonstrated some of the processing advantages of this technology and have demonstrated that the performance is comparable to conventionally fabricated membrane electrode assemblies (MEAs). Commercial desktop inkjet printers were used to deposit the active catalyst electrode layer directly from print cartridges onto Nafion ® polymer membranes in the hydrogen form. The layers were well-adhered and withstood simple tape peel, bending and abrasion tests and did so without any post-deposition hot press step. The elimination of this processing step suggests that inkjet-based fabrication or similar processing technologies may provide a route to less expensive large-scale fabrication of PEMFCs. When tested in our experimental apparatus, open circuit voltages up to 0.87 V and power densities of up to 155 mW cm -2 were obtained with a catalyst loading of 0.20 mg Pt cm -2. A commercially available membrane under identical, albeit not optimized test conditions, showed about 7% greater power density. The objective of this work was to demonstrate some of the processing advantages of drop-on-demand technology for fabrication of MEAs. It remains to be determined if inkjet fabrication offers performance advantages or leads to more efficient utilization of expensive catalyst materials.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vijayakumar, M.; Luo, Qingtao; Lloyd, Ralph

The microstructure of the perfluorinated sulfonic acid proton exchange membranes such as Nafion significantly affects their transport properties and performance in a vanadium redox flow battery (VRB). In this work, Nafion membranes with various equivalent weights (EW) ranging from 1000 to 1500 are prepared and the structure-property-performance relationship is investigated. Nuclear magnetic resonance (NMR) and small-angle X-ray scattering (SAXS) studies revealed their composition and morphology variances, which lead to major differences in key transport properties related to proton conduction and vanadium ion permeation. Their performances are further characterized as VRB membranes. Based on those understanding, a new perfluorosulfonic acid membranemore » is designed with optimal pore geometry and thickness, leading to higher ion selectivity and lower cost compared with the widely used Nafion® 115. Excellent VRB single-cell performance (89.3% energy efficiency at 50mA∙cm-2) was achieved along with a stable cyclical capacity over prolonged cycling.« less

Sulfonated polyphenylene polymers

DOEpatents

Cornelius, Christopher J.; Fujimoto, Cy H.; Hickner, Michael A.

2007-11-27

Improved sulfonated polyphenylene compositions, improved polymer electrolyte membranes and nanocomposites formed there from for use in fuel cells are described herein. The improved compositions, membranes and nanocomposites formed there from overcome limitations of Nafion.RTM. membranes.

Composite proton exchange membrane based on sulfonated organic nanoparticles

NASA Astrophysics Data System (ADS)

Pitia, Emmanuel Sokiri

As the world sets its sight into the future, energy remains a great challenge. Proton exchange membrane (PEM) fuel cell is part of the solution to the energy challenge because of its high efficiency and diverse application. The purpose of the PEM is to provide a path for proton transport and to prevent direct mixing of hydrogen and oxygen at the anode and the cathode, respectively. Hence, PEMs must have good proton conductivity, excellent chemical stability, and mechanical durability. The current state-of-the-art PEM is a perfluorosulfonate ionomer, Nafion®. Although Nafion® has many desirable properties, it has high methanol crossover and it is expensive. The objective of this research was to develop a cost effective two-phase, composite PEM wherein a dispersed conductive organic phase preferentially aligned in the transport direction controls proton transport, and a continuous hydrophobic phase provides mechanical durability to the PEM. The hypothesis that was driving this research was that one might expect better dispersion, higher surface to volume ratio and improved proton conductivity of a composite membrane if the dispersed particles were nanometer in size and had high ion exchange capacity (IEC, = [mmol sulfonic acid]/gram of polymer). In view of this, considerable efforts were employed in the synthesis of high IEC organic nanoparticles and fabrication of a composite membrane with controlled microstructure. High IEC, ~ 4.5 meq/g (in acid form, theoretical limit is 5.4 meq/g) nanoparticles were achieved by emulsion copolymerization of a quaternary alkyl ammonium (QAA) neutralized-sulfonated styrene (QAA-SS), styrene, and divinylbenzene (DVB). The effects of varying the counterion of the sulfonated styrene (SS) monomer (alkali metal and QAA cations), SS concentration, and the addition of a crosslinking agent (DVB) on the ability to stabilize the nanoparticles to higher IECs were assessed. The nanoparticles were ion exchanged to acid form. The extent of ion

A Nanostructured Sensor Based on Gold Nanoparticles and Nafion for Determination of Uric Acid

PubMed Central

Stozhko, Natalia; Bukharinova, Maria; Galperin, Leonid; Brainina, Khiena

2018-01-01

The paper discusses the mechanism of uric acid (UA) electrooxidation occurring on the surface of gold nanoparticles. It has been shown that the electrode process is purely electrochemical, uncomplicated with catalytic stages. The nanoeffects observed as the reduction of overvoltage and increased current of UA oxidation have been described. These nanoeffects are determined by the size of particles and do not depend on the method of particle preparation (citrate and “green” synthesis). The findings of these studies have been used to select a modifier for carbon screen-printed electrode (CSPE). It has been stated that CSPE modified with gold nanoparticles (5 nm) and 2.5% Nafion (Nf) may serve as non-enzymatic sensor for UA determination. The combination of the properties of nanoparticles and Nafion as a molecular sieve at the selected pH 5 phosphate buffer solution has significantly improved the resolution of the sensor compared to unmodified CSPE. A nanostructured sensor has demonstrated good selectivity in determining UA in the presence of ascorbic acid. The detection limit of UA is 0.25 μM. A linear calibration curve has been obtained over a range of 0.5–600 μM. The 2.5%Nf/Au(5nm)/CSPE has been successfully applied to determining UA in blood serum and milk samples. The accuracy and reliability of the obtained results have been confirmed by a good correlation with the enzymatic spectrophotometric analysis (R2 = 0.9938) and the “added−found” technique (recovery close to 100%). PMID:29509718

Increasing the proton conductivity of sulfonated polyether ether ketone by incorporating graphene oxide: Morphology effect on proton dynamics

NASA Astrophysics Data System (ADS)

Leong, Jun Xing; Diño, Wilson Agerico; Ahmad, Azizan; Daud, Wan Ramli Wan; Kasai, Hideaki

2018-03-01

We synthesized graphene oxide-sulfonated polyether ether ketone (GO-SPEEK) composite membrane and compare its proton conductivity with that of Nafion® 117 and SPEEK membranes. From experimental measurements, we found that GO-SPEEK has better proton conductivity (σGO-SPEEK = 3.8 × 10-2 S cm-1) when compared to Nafion® 117 (σNafion = 2.4 × 10-2 S cm-1) and SPEEK (σSPEEK = 2.9 × 10-3 S cm-1). From density functional theory (DFT-) based total energy calculations, we found that GO-SPEEK has the shortest proton diffusion distance among the three membranes, yielding the highest tunneling probability. Hence, GO-SPEEK exhibits the highest conductivity. The short proton diffusion distance in GO-SPEEK, as compared to Nafion® 117 and SPEEK, can be attributed to the presence of oxygenated functional groups of GO in the polymer matrix. This also explains why GO-SPEEK requires the lowest hydration level to reach its maximum conductivity. Moreover, we have successfully shown that the proton conductivity σ is related to the tunneling probability T, i.e., σ = σ‧ exp(-1/T). We conclude that the proton diffusion distance and hydration level are the two most significant factors that determine the membrane’s good conductivity. The distance between ionic sites of the membrane should be small to obtain good conductivity. With this short distance, lower hydration level is required. Thus, a membrane with short separation between the ionic sites can have enhanced conductivity, even at low hydration conditions.

Comparative study of bending characteristics of ionic polymer actuators containing ionic liquids for modeling actuation

NASA Astrophysics Data System (ADS)

Kikuchi, Kunitomo; Sakamoto, Takumi; Tsuchitani, Shigeki; Asaka, Kinji

2011-04-01

Ionic polymer metal composites (IPMCs) that can operate in air have recently been developed by incorporating an ionic liquid in ionic polymers. To understand transduction in these composites, it is important to determine the role of the ionic liquid in the ionic polymer (Nafion®), to identify the counter cation, and to investigate the interaction of IPMCs with water vapor in the air. We used Fourier-transform infrared spectroscopy to analyze three Nafion® membranes, which were soaked in mixtures of water and an ionic liquid (1-ethyl-3-methyl-imidazolium tetrafluoroborate (EMIBF4), 1-buthyl-3-methyl-imidazolium tetrafluoroborate (BMIBF4), and 1-buthyl-3-methyl-imidazolium hexafluorophosphate (BMIPF6)). The results demonstrate that only cations (EMI+ and BMI+) in the ionic liquids are taken into the Nafion® membranes as counter ions and that the water content of the membranes in air is less than ˜4% that of Nafion® swollen with water. Based on the experimental results, a transduction model is proposed for an IPMC with an ionic liquid. In this model, bending is caused by local swelling due to the volume effect of the bulky counter cations. This model can explain 30-50% of the experimentally observed bending curvature.

An electrochemically enhanced solid-phase microextraction approach based on a multi-walled carbon nanotubes/Nafion composite coating.

PubMed

Zeng, Jingbin; Chen, Jinmei; Song, Xinhong; Wang, Yiru; Ha, Jaeho; Chen, Xi; Wang, Xiaoru

2010-03-12

In this paper, we proposed an approach using a multi-walled carbon nanotubes (MWCNTs)/Nafion composite coating as a working electrode for the electrochemically enhanced solid-phase microextraction (EE-SPME) of charged compounds. Suitable negative and positive potentials were applied to enhance the extraction of cationic (protonated amines) and anionic compounds (deprotonated carboxylic acids) in aqueous solutions, respectively. Compared to the direct SPME mode (DI-SPME) (without applying potential), the EE-SPME presented more effective and selective extraction of charged analytes primarily via electrophoresis and complementary charge interaction. The experimental parameters relating to extraction efficiency of the EE-SPME such as applied potentials, extraction time, ionic strength, sample pH were studied and optimized. The linear dynamic range of developed EE-SPME-GC for the selected amines spanned three orders of magnitude (0.005-1mugmL(-1)) with R(2) larger than 0.9933, and the limits of detection were in the range of 0.048-0.070ngmL(-1). All of these characteristics demonstrate that the proposed MWCNTs/Nafion EE-SPME is an efficient, flexible and versatile sampling and extraction tool which is ideally suited for use with chromatographic methods. Copyright (c) 2010 Elsevier B.V. All rights reserved.

Design of flexible polyphenylene proton-conducting membrane for next-generation fuel cells.

PubMed

Miyake, Junpei; Taki, Ryunosuke; Mochizuki, Takashi; Shimizu, Ryo; Akiyama, Ryo; Uchida, Makoto; Miyatake, Kenji

2017-10-01

Proton exchange membrane fuel cells (PEMFCs) are promising devices for clean power generation in automotive, stationary, and portable applications. Perfluorosulfonic acid (PFSA) ionomers (for example, Nafion) have been the benchmark PEMs; however, several problems, including high gas permeability, low thermal stability, high production cost, and environmental incompatibility, limit the widespread dissemination of PEMFCs. It is believed that fluorine-free PEMs can potentially address all of these issues; however, none of these membranes have simultaneously met the criteria for both high performance (for example, proton conductivity) and durability (for example, mechanical and chemical stability). We present a polyphenylene-based PEM (SPP-QP) that fulfills the required properties for fuel cell applications. The newly designed PEM exhibits very high proton conductivity, excellent membrane flexibility, low gas permeability, and extremely high stability, with negligible degradation even under accelerated degradation conditions, which has never been achieved with existing fluorine-free PEMs. The polyphenylene PEM also exhibits reasonably high fuel cell performance, with excellent durability under practical conditions. This new PEM extends the limits of existing fluorine-free proton-conductive materials and will help to realize the next generation of PEMFCs via cost reduction as well as the performance improvement compared to the present PFSA-based PEMFC systems.

Design of flexible polyphenylene proton-conducting membrane for next-generation fuel cells

PubMed Central

Miyake, Junpei; Taki, Ryunosuke; Mochizuki, Takashi; Shimizu, Ryo; Akiyama, Ryo; Uchida, Makoto; Miyatake, Kenji

2017-01-01

Proton exchange membrane fuel cells (PEMFCs) are promising devices for clean power generation in automotive, stationary, and portable applications. Perfluorosulfonic acid (PFSA) ionomers (for example, Nafion) have been the benchmark PEMs; however, several problems, including high gas permeability, low thermal stability, high production cost, and environmental incompatibility, limit the widespread dissemination of PEMFCs. It is believed that fluorine-free PEMs can potentially address all of these issues; however, none of these membranes have simultaneously met the criteria for both high performance (for example, proton conductivity) and durability (for example, mechanical and chemical stability). We present a polyphenylene-based PEM (SPP-QP) that fulfills the required properties for fuel cell applications. The newly designed PEM exhibits very high proton conductivity, excellent membrane flexibility, low gas permeability, and extremely high stability, with negligible degradation even under accelerated degradation conditions, which has never been achieved with existing fluorine-free PEMs. The polyphenylene PEM also exhibits reasonably high fuel cell performance, with excellent durability under practical conditions. This new PEM extends the limits of existing fluorine-free proton-conductive materials and will help to realize the next generation of PEMFCs via cost reduction as well as the performance improvement compared to the present PFSA-based PEMFC systems. PMID:29075671

Development of the anode bipolar plate/membrane assembly unit for air breathing PEMFC stack using silicone adhesive bonding

NASA Astrophysics Data System (ADS)

Kim, Minkook; Lee, Dai Gil

2016-05-01

Polymer electrolyte membrane fuel cells (PEMFC) exhibit a wide power range, low operating temperature, high energy density and long life time. These advantages favor PEMFC for applications such as vehicle power sources, portable power, and backup power applications. With the push towards the commercialization of PEMFC, especially for portable power applications, the overall balance of plants (BOPs) of the systems should be minimized. To reduce the mass and complexity of the systems, air-breathing PEMFC stack design with open cathode channel configuration is being developed. However, the open cathode channel configuration incurs hydrogen leakage problem. In this study, the bonding strength of a silicon adhesive between the Nafion membrane and the carbon fiber/epoxy composite bipolar plate was measured. Then, an anode bipolar plate/membrane assembly unit which was bonded with the silicone adhesive was developed to solve the hydrogen leakage problem. The reliability of the anode bipolar plate/membrane assembly unit was estimated under the internal pressure of hydrogen by the FE analysis. Additionally, the gas sealability of the developed air breathing PEMFC unit cell was experimentally measured. Finally, unit cell performance of the developed anode bipolar plate/membrane assembly unit was tested and verified under operating conditions without humidity and temperature control.

Stability and Degradation Mechanisms of Radiation-Grafted Polymer Electrolyte Membranes for Water Electrolysis.

PubMed

Albert, Albert; Lochner, Tim; Schmidt, Thomas J; Gubler, L

2016-06-22

Radiation-grafted membranes are a promising alternative to commercial membranes for water electrolyzers, since they exhibit lower hydrogen crossover and area resistance, better mechanical properties, and are of potentially lower cost than perfluoroalkylsulfonic acid membranes, such as Nafion. Stability is an important factor in view of the expected lifetime of 40 000 h or more of an electrolyzer. In this study, combinations of styrene (St), α-methylstyrene (AMS), acrylonitrile (AN), and 1,3-diisopropenylbenzene (DiPB) are cografted into 50 μm preirradiated poly(ethylene-co-tetrafluoroethylene) (ETFE) base film, followed by sulfonation to produce radiation-grafted membranes. The stability of the membranes with different monomer combinations is compared under an accelerated stress test (AST), and the degradation mechanisms are investigated. To mimic the conditions in an electrolyzer, in which the membrane is always in contact with liquid water at elevated temperature, the membranes are immersed in water for 5 days at 90 °C, so-called thermal stress test (TST). In addition to testing in air atmosphere tests are also carried out under argon to investigate the effect of the absence of oxygen. The water is analyzed with UV-vis spectroscopy and ion chromatography. The ion exchange capacity (IEC), swelling degree, and Fourier transform infrared (FTIR) spectra of the membranes are compared before and after the test. Furthermore, energy-dispersive X-ray (EDX) spectroscopic analysis of the membrane cross-section is performed. Finally, the influence of the TST to the membrane area resistance and hydrogen crossover is measured. The stability increases along the sequence St/AN, St/AN/DiPB, AMS/AN, and AMS/AN/DiPB grafted membrane. The degradation at the weak-link, oxygen-induced degradation, and hydrothermal degradation are proposed in addition to the "swelling-induced detachment" reported in the literature. By mitigating the possible paths of degradation, the AMS

Cerium Ion Mobility and Diffusivity Rates in Perfluorosulfonic Acid Membranes Measured via Hydrogen Pump Operation

DOE PAGES

Baker, Andrew M.; Babu, Siddharth Komini; Mukundan, Rangachary; ...

2017-09-21

Ion mobility and diffusivity coefficients were determined for cerium ions in Nafion XL perfluorosulfonic acid ionomer membranes at 100% and 50% relative humidity in a conductivity cell using a hydrogen pump. We quantified Ce ion migration profiles as a function of charge transfer through the cell using X-ray fluorescence (XRF). To decouple simultaneous effects of Ce ion mobility and back-diffusion which occur due to potential and concentration gradients, respectively, a one-dimensional model was developed and fit to these intermittent XRF profiles. The resulting mobility and diffusivity coefficients demonstrate the dramatic effects of potential and concentration gradients on Ce ion migrationmore » during PEM fuel cell operation.« less

Cerium Ion Mobility and Diffusivity Rates in Perfluorosulfonic Acid Membranes Measured via Hydrogen Pump Operation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Baker, Andrew M.; Babu, Siddharth Komini; Mukundan, Rangachary

Ion mobility and diffusivity coefficients were determined for cerium ions in Nafion XL perfluorosulfonic acid ionomer membranes at 100% and 50% relative humidity in a conductivity cell using a hydrogen pump. We quantified Ce ion migration profiles as a function of charge transfer through the cell using X-ray fluorescence (XRF). To decouple simultaneous effects of Ce ion mobility and back-diffusion which occur due to potential and concentration gradients, respectively, a one-dimensional model was developed and fit to these intermittent XRF profiles. The resulting mobility and diffusivity coefficients demonstrate the dramatic effects of potential and concentration gradients on Ce ion migrationmore » during PEM fuel cell operation.« less

Electrically facilitated molecular transport. Analysis of the relative contributions of diffusion, migration, and electroosmosis to solute transport in an ion-exchange membrane.

PubMed

Bath, B D; White, H S; Scott, E R

2000-02-01

Electrically facilitated molecular transport in an ion-exchange membrane (Nafion, 1100 equiv wt) has been studied using a scanning electrochemical microscope. The transport rates of ferrocenylmethyltrimethylammonium (a cation), acetaminophen (a neutral molecule), and ascorbate (an anion) through approximately 120-micron-thick membranes were measured as a function of the iontophoretic current passed across the membrane (-1.0 to +1.0 A/cm2). Transport rates were analyzed by employing the Nernst-Planck equation, modified to account for electric field-driven convective transport. Excellent agreement between experimental and theoretical values of the molecular flux was obtained using a single fitting parameter for each molecule (electroosmotic drag coefficient). The electroosmotic velocity of the neutral molecule, acetaminophen, was shown to be a factor of approximately 500 larger than that of the cation ferrocenylmethyltrimethylammonium, a consequence of the electrostatic interaction of the cation with the negatively charged pore walls of the ion-exchange membrane. Electroosmotic transport of ascorbate occurred at a negligible rate due to repulsion of the anion by the cation-selective membrane. These results suggest that electroosmotic velocities of solute molecules are determined by specific chemical interactions of the permeant and membrane and may be very different from the average solution velocity. The efficiency of electroosmotic transport was also shown to be a function of the membrane thickness, in addition to membrane/solute interactions.

Uncertainty Quantification of Nonlinear Electrokinetic Response in a Microchannel-Membrane Junction

NASA Astrophysics Data System (ADS)

Alizadeh, Shima; Iaccarino, Gianluca; Mani, Ali

2015-11-01

We have conducted uncertainty quantification (UQ) for electrokinetic transport of ionic species through a hybrid microfluidic system using different probabilistic techniques. The system of interest is an H-configuration consisting of two parallel microchannels that are connected via a nafion junction. This system is commonly used for ion preconcentration and stacking by utilizing a nonlinear response at the channel-nafion junction that leads to deionization shocks. In this work, the nafion medium is modeled as many parallel nano-pores where, the nano-pore diameter, nafion porosity, and surface charge density are independent random variables. We evaluated the resulting uncertainty on the ion concentration fields as well as the deionization shock location. The UQ methods predicted consistent statistics for the outputs and the results revealed that the shock location is weakly sensitive to the nano-pore surface charge and primarily driven by nano-pore diameters. The present study can inform the design of electrokinetic networks with increased robustness to natural manufacturing variability. Applications include water desalination and lab-on-a-chip systems. Shima is a graduate student in the department of Mechanical Engineering at Stanford University. She received her Master's degree from Stanford in 2011. Her research interests include Electrokinetics in porous structures and high performance computing.

Sensitive HIV-1 detection in a homogeneous solution based on an electrochemical molecular beacon coupled with a nafion-graphene composite film modified screen-printed carbon electrode.

PubMed

Li, Bo; Li, Zhengliang; Situ, Bo; Dai, Zong; Liu, Qinlan; Wang, Qian; Gu, Dayong; Zheng, Lei

2014-02-15

A novel electrochemical sensing assay for sensitive determination of HIV-1 in a homogeneous solution has been developed using an electrochemical molecular beacon combined with a nafion-graphene composite film modified screen-printed carbon electrode (nafion-graphene/SPCE). The electrochemical molecular beacon (CAs-MB), comprising a special recognition sequence for the conserved region of the HIV-1 gag gene and a pair of carminic acid molecules as a marker, can indicate the presence of the HIV-1 target by its on/off electrochemical signal behavior. It is suitable for direct, electrochemical determination of HIV-1, thereby simplifying the detection procedure and improving the signal-to-noise (S/N) ratio. To further improve the sensitivity, the nafion-graphene/SPCE was used to monitor changes in the CAs-MB, which has notable advantages, such as being ultrasensitive, inexpensive, and disposable. Under optimized conditions, the peak currents showed a linear relationship with the logarithm of target oligonucleotide concentrations ranging from 40 nM to 2.56 μM, with a detection limit of 5 nM (S/N=3). This sensing assay also displays a good stability, with a recovery of 88-106.8% and RSD<7% (n=5) in real serum samples. This work may lead to the development of an effective method for early point-of-care diagnosis of HIV-1 infection. © 2013 Elsevier B.V. All rights reserved.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wei, Xiaoliang; Nie, Zimin; Luo, Qingtao

Driven by the motivation of searching for low-cost membrane alternatives, a novel nanoporous polytetrafluoroethylene/silica composite separator has been prepared and evaluated for its use in all-vanadium mixed-acid redox flow battery. This separator consisting of silica particles enmeshed in a polytetrafluoroethylene fibril matrix has no ion exchange capacity and is featured with unique nanoporous structures, which function as the ion transport channels in redox flow battery operation, with an average pore size of 38nm and a porosity of 48%. This separator has produced excellent electrochemical performance in the all-vanadium mixed-acid system with energy efficiency delivery comparable to Nafion membrane and superiormore » rate capability and temperature tolerance. The separator also demonstrates an exceptional capacity retention capability over extended cycling, offering additional operational latitude towards conveniently mitigating the capacity decay that is inevitable for Nafion. Because of the inexpensive raw materials and simple preparation protocol, the separator is particularly low-cost, estimated to be at least an order of magnitude more inexpensive than Nafion. Plus the proven chemical stability due to the same backbone material as Nafion, this separator possesses a good combination of critical membrane requirements and shows great potential to promote market penetration of the all-vanadium redox flow battery by enabling significant reduction of capital and cycle costs.« less

The performance and long-term stability of low-cost separators in single-chamber bottle-type microbial fuel cells.

PubMed

Kondaveeti, Sanath; Kakarla, Ramesh; Kim, Hong Suck; Kim, Byung-Goon; Min, Booki

2018-02-01

This study evaluates long-term stability of low-cost separators in single-chamber bottle-type microbial fuel cells with domestic wastewater. Low-cost separators tested in this study were nonwoven fabrics (NWF) of polypropylene (PP80, PP100), textile fabrics of polyphenylene sulfide (PPS), sulfonated polyphenylene sulfide (SPPS), and cellulose esters. NWF PP80 separator generated the highest power density of 280 mW/m 2 , which was higher than with ion-exchange membranes (cation exchange membrane; CEM = 271 mW/m 2 , cation exchange membrane; CMI = 196 mW/m 2 , Nafion = 260 mW/m 2 ). MFC operations with other size-selective separators such as SPPS, PPS, and cellulose esters exhibited power densities of 261, 231, and 250 mW/m 2 , respectively. During a 280-day operation, initial power density of PP80 (278 mW/m 2 ) was decreased to 257 mW/m 2 , but this decrease was smaller than with others (Nafion: 265-230 mW/m 2 ; PP100: 220-126 mW/m 2 ). The anode potential of around -430 mV did not change much with all separators in the long-term operation, but the initial cathode potential gradually decreased. Fouling analysis suggested that the presence of carbonaceous substance on Nafion and PP80 after 280 days of operation and Nafion was subject to be more biofouling.

Effects of Cationic Pendant Groups on Ionic Conductivity for Anion Exchange Membranes: Structure Conductivity Relationships

NASA Astrophysics Data System (ADS)

Kim, Sojeong; Choi, Soo-Hyung; Lee, Won Bo

Anion exchange membranes(AEMs) have been widely studied due to their various applications, especially for Fuel cells. Previous proton exchange membranes(PEMs), such as Nafions® have better conductivity than AEMs so far. However, technical limitations such as slow electrode kinetics, carbon monoxide (CO) poisoning of metal catalysts, high methanol crossover and high cost of Pt-based catalyst detered further usages. AEMs have advantages to supplement its drawbacks. AEMs are environmentally friendly and cost-efficient. Based on the well-defined block copolymer, self-assembled morphology is expected to have some relationship with its ionic conductivity. Recently AEMs based on various cations, including ammonium, phosphonium, guanidinium, imidazolium, metal cation, and benzimidazolium cations have been developed and extensively studied with the aim to prepare high- performance AEMs. But more fundamental approach, such as relationships between nanostructure and conductivity is needed. We use well-defined block copolymer Poly(styrene-block-isoprene) as a backbone which is synthesized by anionic polymerization. Then we graft various cationic functional groups and analysis the relation between morphology and conductivity. Theoretical and computational soft matter lab.

Determination of As in tobacco by using electrochemical hydride generation at a Nafion® solid polymer electrolyte cell hyphenated with atomic fluorescence spectrometry

NASA Astrophysics Data System (ADS)

Yang, Qinghua; Gan, Wuer; Deng, Yun; Sun, Huihui

2011-11-01

In the present work, a novel solid polymer electrolyte hydride generation (SPE-HG) cell was developed. The home-made SPE-HG cell, mainly composed of three components (Nafion®117 membrane for separating and H + exchanging, a soft graphite felt cathode and a Ti mesh modified by Ir anode), was employed for detecting As by coupling to atomic fluorescence spectrometry (AFS). The H + generated by electrolysis of pure water in anode chamber transferred to cathode chamber through SPE, and immediately reacted with As 3 + to generate AsH 3. The relative mechanisms and operation conditions for hydride generation of As were investigated in detail. The developed cell employed water as an alternative of acid anolyte, with virtues of low-cost, more than 6 months lifetime and environment friendly compared with the conventional cell. Under the optimized conditions, the limit of determination of As 3 + for sample blank solution was 0.12 μg L - 1 , the RSD was 2.9% for 10 consecutive measurements of 5 μg L - 1 As 3 + standard solution. The accuracy of the method was verified by the determination of As in the reference Tea (GBW07605) and the developed method was successfully applied to determine trace amounts of As in tobacco samples with recovery from 97% to 103%.

Theoretical and computational studies of renewable energy materials: Room temperature ionic liquids and proton exchange membranes

NASA Astrophysics Data System (ADS)

Feng, Shulu

2011-12-01

Two kinds of renewable energy materials, room temperature ionic liquids (RTILs) and proton exchange membranes (PEMs), especially Nafion, are studied by computational and theoretical approaches. The ultimate purpose of the present research is to design novel materials to meet the future energy demands. To elucidate the effect of alkyl side chain length and anion on the structure and dynamics of the mixtures, molecular dynamics (MD) simulations of three RTILs/water mixtures at various water mole fractions: 1-butyl-3-methylimidazolium (BMIM+)/BF4-, 1-octyl-3-methylimidazolium (OMIM+)/BF4-, and OMIM +/Cl- are performed. Replacing the BMIM + cation with OMIM+ results in stronger aggregation of the cations as well as a slower diffusion of the anions, and replacing the BF4- anion with Cl- alters the water distribution at low water mole fractions and slows diffusion of the mixtures. Potential experimental manifestations of these behaviors in both cases are provided. Proton solvation properties and transport mechanisms are studied in hydrated Nafion, by using the self-consistent multistate empirical valence bond (SCI-MS-EVB) method. It is found that by stabilizing a more Zundel-like (H5O 2+) structure in the first solvation shells, the solvation of excess protons, as well as the proton hydration structure are both influenced by the sulfonate groups. Hydrate proton-related hydrogen bond networks are observed to be more stable than those with water alone. In order to characterize the nature of the proton transport (PT), diffusive motion, Arrhenius activation energies, and transport pathways are calculated and analyzed. Analysis of diffusive motion suggests that (1) a proton-hopping mechanism dominates the proton transport for the studied water loading levels and (2) there is an obvious degree of anti-correlation between the proton hopping and the vehicular transport. The activation energy drops rapidly with an increasing water content when the water loading level is smaller

Lead Research and Development Activity for DOE's High Temperature, Low Relative Humidity Membrane Program (Topic 2)

DOE Office of Scientific and Technical Information (OSTI.GOV)

James Fenton, PhD; Darlene Slattery, PhD; Nahid Mohajeri, PhD

2012-09-05

The Department of Energy’s High Temperature, Low Relative Humidity Membrane Program was begun in 2006 with the Florida Solar Energy Center (FSEC) as the lead organization. During the first three years of the program, FSEC was tasked with developing non-Nafion® proton exchange membranes with improved conductivity for fuel cells. Additionally, FSEC was responsible for developing protocols for the measurement of in-plane conductivity, providing conductivity measurements for the other funded teams, developing a method for through-plane conductivity and organizing and holding semiannual meetings of the High Temperature Membrane Working Group (HTMWG). The FSEC membrane research focused on the development of supportedmore » poly[perfluorosulfonic acid] (PFSA) – Teflon membranes and a hydrocarbon membrane, sulfonated poly(ether ether ketone). The fourth generation of the PFSA membrane (designated FSEC-4) came close to, but did not meet, the Go/No-Go milestone of 0.1 S/cm at 50% relative humidity at 120 °C. In-plane conductivity of membranes provided by the funded teams was measured and reported to the teams and DOE. Late in the third year of the program, DOE used this data and other factors to decide upon the teams to continue in the program. The teams that continued provided promising membranes to FSEC for development of membrane electrode assemblies (MEAs) that could be tested in an operating fuel cell. FSEC worked closely with each team to provide customized support. A logic flow chart was developed and discussed before MEA fabrication or any testing began. Of the five teams supported, by the end of the project, membranes from two of the teams were easily manufactured into MEAs and successfully characterized for performance. One of these teams exceeded performance targets, while the other requires further optimization. An additional team developed a membrane that shows great promise for significantly reducing membrane costs and increasing membrane lifetime.« less

Polyvinylpyrrolidone-based semi-interpenetrating polymer networks as highly selective and chemically stable membranes for all vanadium redox flow batteries

NASA Astrophysics Data System (ADS)

Zeng, L.; Zhao, T. S.; Wei, L.; Zeng, Y. K.; Zhang, Z. H.

2016-09-01

Vanadium redox flow batteries (VRFBs) with their high flexibility in configuration and operation, as well as long cycle life are competent for the requirement of future energy storage systems. Nevertheless, due to the application of perfluorinated membranes, VRFBs are plagued by not only the severe migration issue of vanadium ions, but also their high cost. Herein, we fabricate semi-interpenetrating polymer networks (SIPNs), consisting of cross-linked polyvinylpyrrolidone (PVP) and polysulfone (PSF), as alternative membranes for VRFBs. It is demonstrated that the PVP-based SIPNs exhibit extremely low vanadium permeabilities, which contribute to the well-established hydrophilic/hydrophobic microstructures and the Donnan exclusion effect. As a result, the coulombic efficiencies of VRFBs with PVP-based SIPNs reach almost 100% at 40 mA cm-2 to 100 mA cm-2; the energy efficiencies are more than 3% higher than those of VRFBs with Nafion 212. More importantly, the PVP-based SIPNs exhibit a superior chemical stability, as demonstrated both by an ex situ immersion test and continuously cycling test. Hence, all the characterizations and performance tests reported here suggest that PVP-based SIPNs are a promising alternative membrane for redox flow batteries to achieve superior cell performance and excellent cycling stability at the fraction of the cost of perfluorinated membranes.

Hollow Fiber Space Suit Water Membrane Evaporator Development for Lunar Missions

NASA Technical Reports Server (NTRS)

Bue, Grant C.; Trevino, Luis A.; Hanford, Anthony J.; Mitchell, Keith

2009-01-01

The Space Suit Water Membrane Evaporator (SWME) is the baseline heat rejection technology selected for development for the Constellation lunar suit. The Hollow Fiber (HoFi) SWME is being considered for service in the Constellation Space Suit Element (CSSE) Portable Life Support Subsystem (PLSS) to provide cooling to the thermal loop through water evaporation to the vacuum of space. Previous work described the test methodology and planning to compare the test performance of three commercially available hollow fiber materials as alternatives to the sheet membrane prototype for SWME: 1) porous hydrophobic polypropylene, 2) porous hydrophobic polysulfone, and 3) ion exchange through nonporous hydrophilic modified Nafion. Contamination tests were performed to probe for sensitivities of the candidate SWME elements to organics and non-volative inorganics expected to be found in the target feedwater source, i.e., potable water provided by the vehicle. The resulting presence of precipitate in the coolant water could plug pores and tube channels and affect the SWME performance. From this prior work, a commercial porous hydrophobic hollow fiber was selected to satisfy both the sensitivity question and the need to provide 800 W of heat rejection. This paper describes the trade studies, the design methodology, and the hollow fiber test data used to design a full

Asymmetric bi-layer PFSA membranes as model systems for the study of water management in the PEMFC.

PubMed

Peng, Z; Peng, A Z; Morin, A; Huguet, P; Lanteri, Y; Deabate, S

2014-10-14

New bi-layer PFSA membranes made of Nafion® NRE212 and Aquivion™ E79-05s with different equivalent weights are prepared with the aim of managing water repartition in the PEMFC. The membrane water transport properties, i.e. back-diffusion and electroosmosis, as well as the electrochemical performances, are compared to those of state-of-art materials. The actual water content (the inner water concentration profile across the membrane thickness) is measured under operation in the fuel cell by in situ Raman microspectroscopy. The orientation of the equivalent weight gradient with respect to the water external gradient and to the proton flow direction affects the membrane water content, the water transport ability and, thus, the fuel cell performances. Higher power outputs, related to lower ohmic losses, are observed when the membrane is assembled with the lower equivalent weight layer (Aquivion™) at the anode side. This orientation, corresponding to enhanced water transport by back-flow while electroosmosis remains unaffected, results in the higher hydration of the membrane and of the anode active layer during operation. Also, polarization data suggest a different water repartition in the fuel cell along the on-plane direction. Even if the interest in multi-layer PFSA membranes as perspective electrolytes for PEMFCs is not definitively attested, these materials appear to be excellent model systems to establish relationships between the membrane transport properties, the water distribution in the fuel cell and the electrochemical performances. Thanks to the micrometric resolution, in situ Raman microspectroscopy proves to be a unique tool to measure the actual hydration of the membrane at the surface swept by the hydrated feed gases during operation, so that it can be used as a local probe of the water concentration evolution along the gas distribution channels according to changing working conditions.

Influence of electrostatic interactions on the morphology and properties of blends containing perfluorinated ionomers

NASA Astrophysics Data System (ADS)

Taylor, Eric Paul

2002-01-01

The first goal of this research project was to investigate the influence of the electrostatic interactions within the ion-containing domains of Nafion RTM perfluorosulfonate ionomer (PFSI) on the morphology and resultant properties of blend systems with poly(propylene imine) dendrimers of a variety of generational sizes and poly(vinylidene fluoride) (PVDF). Perfluorosulfonate ionomers (PFSIs) are a commercially successful class of semi-crystalline, ion-containing polymers whose most extensive application is in use as a polymer electrolytic membrane in fuel cell applications. NafionRTM was blended and high temperature solution processed with poly(propylene imine) dendrimer as the minor component in order to increase the efficiency of direct methanol fuel cells by decreasing methanol crossover without significant loss of protonic conductivity. The preferential insertion of the dendrimer into the ionic cluster due to proton transfer reactions and the creation of ammonium-sulfonate ion pairs served to alter the transport properties through the ionic network of the membrane. In the second major system investigated, blends of poly(vinylidene fluoride) (PVDF) with NafionRTM, a perfluorosulfonate ionomer, have been prepared and examined in terms of the crystallization kinetics and crystal morphology of the PVDF component in the blend. DSC analysis showed faster rates of bulk crystallization when PVDF was crystallized in the presence of Na+-form NafionRTM suggesting a high degree of phaseseparation in this blend system and an increase in the nucleation density. NafionRTM neutralized with alkylammonium-form counterions display an increase in blend compatibility with PVDF with an increase in the alkylammonium counterion size. As the alkylammonium counterion size increases, the strength of the electrostatic network within the ionic domains of Nafion RTM decrease resulting in a reduction in the driving force for ionic aggregation. Thus, a decrease is observed in the crystal

A Survey of Power Source Options for a Compact Battery Charger for Soldier Applications

DTIC Science & Technology

2008-12-01

virtually any flammable liquid could be used as a fuel. Research on linear engines, enabled by developments in power control and linear electrical...the use of atmospheric oxygen. Molten carbonate and phosphoric acid fuel cells use hot corrosive liquid electrolytes and are best applied to...cells using DuPont’s NAFION membranes began at General Electric and Ballard Industries in the early 1980s. NAFION is a fluoropolymer with

Fuel cell catalyst layers containing short-side-chain perfluorosulfonic acid ionomers

NASA Astrophysics Data System (ADS)

Peron, Jennifer; Edwards, Dave; Haldane, Mark; Luo, Xiaoyan; Zhang, Yongming; Holdcroft, Steven; Shi, Zhiqing

Porous catalyst layers (CLs) containing short-side-chain (SSC) perfluorosulfonic acid (PFSA) ionomers of different ion exchange capacity (IEC: 1.3, 1.4 and 1.5 meq g -1) were deposited onto Nafion 211 to form catalyst-coated membranes. The porosity of SSC-PFSA-based CLs is larger than Nafion-CL analogues. CLs incorporating SSC ionomer extend the current density of fuel cell polarization curves at elevated temperature and lower relative humidity compared to those based on long-side chain PFSA (e.g., Nafion)-based CLs. Fuel cell polarization performance was greatly improved at 110 °C and 30% relative humidity (RH) when SSC PFSI was incorporated into the catalyst layer.

Concentration Effects of Polymer Electrolyte Membrane Degradation Products on Oxygen Reduction Activity for Three Platinum Catalysts

DOE PAGES

Christ, J. M.; Neyerlin, K. C.; Richards, R.; ...

2014-10-04

A rotating disk electrode (RDE) along with cyclic voltammetry (CV) and linear sweep voltammetry (LSV), were used to investigate the impact of two model compounds representing degradation products of Nafion and 3M perfluorinated sulfonic acid membranes on the electrochemical surface area (ECA) and oxygen reduction reaction (ORR) activity of polycrystalline Pt, nano-structured thin film (NSTF) Pt (3M), and Pt/Vulcan carbon (Pt/Vu) (TKK) electrodes. ORR kinetic currents (measured at 0.9 V and transport corrected) were found to decrease linearly with the log of concentration for both model compounds on all Pt surfaces studied. Ultimately, model compound adsorption effects on ECA weremore » more abstruse due to competitive organic anion adsorption on Pt surfaces superimposing with the hydrogen underpotential deposition (HUPD) region.« less

Effect of the structure of imidazolium cations in [BF4](-)-type ionic liquids on direct electrochemistry and electrocatalysis of horseradish peroxidase in Nafion films.

PubMed

Lu, Lu; Huang, Xirong; Qu, Yinbo

2011-10-01

The direct electrochemistry and bioelectrocatalysis of horseradish peroxidase (HRP) in Nafion films at glassy carbon electrode (GCE) was investigated in three [BF(4)](-)-type room-temperature ionic liquids (ILs) to understand the structural effect of imidazolium cations. The three ILs are 1-ethyl-3-methylimidazolium tetrafluoroborate ([Emim][BF(4)]), 1-butyl-3-methylimidazolium tetrafluoroborate ([Bmim][BF(4)]) and 1-hexyl-3-methylimidazolium tetrafluoroborate ([Hmim][BF(4)]). A small amount of water in the three ILs is indispensable for maintaining the electrochemical activity of HRP in Nafion films, and the optimum water contents decrease with the increase of alkyl chain length on imidazole ring. Analysis shows that the optimum water contents are primarily determined by the hydrophilicity of ILs used. In contrast to aqueous medium, ILs media facilitate the direct electron transfer of HRP, and the electrochemical parameters obtained in different ILs are obviously related to the nature of ILs. The direct electron transfer between HRP and GCE is a surface-confined quasi-reversible single electron transfer process. The apparent heterogeneous electron transfer rate constant decreases gradually with the increase of alkyl chain length on imidazole ring, but the changing extent is relatively small. The electrocatalytic reduction current of H(2)O(2) at the present electrode decreases obviously with the increase of alkyl chain length, and the mass transfer of H(2)O(2) via diffusion in ILs should be responsible for the change. In addition, the modified electrode has good stability and reproducibility; the ability to tolerate high levels of F(-) has been greatly enhanced due to the use of Nafion film. When an appropriate mediator is included in the sensing layer, a sensitive nonaqueous biosensor could be fabricated. Copyright © 2011 Elsevier B.V. All rights reserved.

Electrochemically Promoted Organic Isomerization Reactions at Polymer Electrolyte Fuel Cell Cathodes

DTIC Science & Technology

2011-01-04

fuel cells ( PEMFCs ) incorporate an ionomer membrane (e.g., Nafion 117) for support of electro- catalytic layers and proton conduction between the...central to PEMFC electrocatalysis. For example, a spin coated Nafion layer on polycrystalline Pt enhances electrocatalysis.7,8 Little is known about...CO Poisoning Effect in PEMFCs Operational at Temperatures up to 200°C. Journal of the Electrochemical Society, 2003. 150(12): p. A1599-A1605. 21

Analyzing Structural Changes of Fe-N-C Cathode Catalysts in PEM Fuel Cell by Mößbauer Spectroscopy of Complete Membrane Electrode Assemblies.

PubMed

Kramm, Ulrike I; Lefèvre, Michel; Bogdanoff, Peter; Schmeißer, Dieter; Dodelet, Jean-Pol

2014-11-06

The applicability of analyzing by Mößbauer spectroscopy the structural changes of Fe-N-C catalysts that have been tested at the cathode of membrane electrode assemblies in proton exchange membrane (PEM) fuel cells is demonstrated. The Mößbauer characterization of powders of the same catalysts was recently described in our previous publication. A possible change of the iron species upon testing in fuel cell was investigated here by Mößbauer spectroscopy, energy-dispersive X-ray cross-sectional imaging, and neutron activation analysis. Our results show that the absorption probability of γ rays by the iron nuclei in Fe-N-C is strongly affected by the presence of Nafion and water content. A detailed investigation of the effect of an oxidizing treatment (1.2 V) of the non-noble cathode in PEM fuel cell indicates that the observed activity decay is mainly attributable to carbon oxidation causing a leaching of active iron sites hosted in the carbon matrix.

Separators used in microbial electrochemical technologies: Current status and future prospects.

PubMed

Daud, Siti Mariam; Kim, Byung Hong; Ghasemi, Mostafa; Daud, Wan Ramli Wan

2015-11-01

Microbial electrochemical technologies (METs) are emerging green processes producing useful products from renewable sources without causing environmental pollution and treating wastes. The separator, an important part of METs that greatly affects the latter's performance, is commonly made of Nafion proton exchange membrane (PEM). However, many problems have been identified associated with the Nafion PEM such as high cost of membrane, significant oxygen and substrate crossovers, and transport of cations other than protons protons and biofouling. A variety of materials have been offered as alternative separators such as ion-exchange membranes, salt bridges, glass fibers, composite membranes and porous materials. It has been claimed that low cost porous materials perform better than PEM. These include J-cloth, nylon filter, glass fiber mat, non-woven cloth, earthen pot and ceramics that enable non-ion selective charge transfer. This paper provides an up-to-date review on porous separators and plots directions for future studies. Copyright © 2015 Elsevier Ltd. All rights reserved.

Electrochemical CO2 Reduction via Gas-Phase Catholyte

NASA Astrophysics Data System (ADS)

Carter, Brittany E.; Nesbitt, Nathan T.; D'Imperio, Luke A.; Naughton, Jeffrey R.; Courtney, Dave T.; Shepard, Steve; Burns, Michael J.; Vermaas, David A.; Smith, Wilson A.; Naughton, Michael J.

Reducing CO2 to CO through electrolysis, for the eventual conversion to hydrocarbons, provides a path towards utility-scale seasonal storage of renewable energy. Electrochemical reduction of CO2 has previously been achieved using a two chamber system. The chambers are typically separated by a semipermeable Nafion membrane, with an oxygen evolution catalyst anode on one side, a gold cathode on the other, and a solution containing CO2 on both sides. If instead, CO2 gas was in the second chamber, the reaction should yield more CO formed from CO2 at a given overpotential; this would result from the increased concentration of CO2 at the cathode surface and more facile mass transport of the CO and CO2. With liquid in one chamber and gas in the other, electrolysis is performed by integrating the cathode onto the semipermeable Nafion membrane. This membrane electrode assembly is fabricated via nanoimprint lithography (NIL), simultaneously achieving high active surface area and permeability. Challenges to the Nafion NIL process, and the performance of the system in CO2 reduction, will be presented. This material is based upon work supported by the National Science Foundation Graduate Research Fellowship under Grant No. (DGE-1258923).

Organic fuel cell methods and apparatus

NASA Technical Reports Server (NTRS)

Narayanan, Sekharipuram R. (Inventor); Frank, Harvey A. (Inventor); Halpert, Gerald (Inventor); Surampudi, Subbarao (Inventor); Prakash, G. K. Surya (Inventor); Vamos, Eugene (Inventor); Olah, George A. (Inventor)

2001-01-01

A liquid organic fuel cell is provided which employs a solid electrolyte membrane. An organic fuel, such as a methanol/water mixture, is circulated past an anode of a cell while oxygen or air is circulated past a cathode of the cell. The cell solid electrolyte membrane is preferably fabricated from Nafion.TM.. Additionally, a method for improving the performance of carbon electrode structures for use in organic fuel cells is provided wherein a high surface-area carbon particle/Teflon.TM.-binder structure is immersed within a Nafion.TM./methanol bath to impregnate the electrode with Nafion.TM.. A method for fabricating an anode for use in a organic fuel cell is described wherein metal alloys are deposited onto the electrode in an electro-deposition solution containing perfluorooctanesulfonic acid. A fuel additive containing perfluorooctanesulfonic acid for use with fuel cells employing a sulfuric acid electrolyte is also disclosed. New organic fuels, namely, trimethoxymethane, dimethoxymethane, and trioxane are also described for use with either conventional or improved fuel cells.

Organic fuel cell methods and apparatus

NASA Technical Reports Server (NTRS)

Surampudi, Subbarao (Inventor); Narayanan, Sekharipuram R. (Inventor); Vamos, Eugene (Inventor); Halpert, Gerald (Inventor); Olah, George A. (Inventor); Frank, Harvey A. (Inventor); Prakash, G. K. Surya (Inventor)

2004-01-01

A liquid organic, fuel cell is provided which employs a solid electrolyte membrane. An organic fuel, such as a methanol/water mixture, is circulated past an anode of a cell while oxygen or air is circulated past a cathode of the cell. The cell solid electrolyte membrane is preferably fabricated from Nafion.TM.. Additionally, a method for improving the performance of carbon electrode structures for use in organic fuel cells is provided wherein a high surface-area carbon particle/Teflon.TM.-binder structure is immersed within a Nafion.TM./methanol bath to impregnate the electrode with Nafion.TM.. A method for fabricating an anode for use in a organic fuel cell is described wherein metal alloys are deposited onto the electrode in an electro-deposition solution containing perfluorooctanesulfonic acid. A fuel additive containing perfluorooctanesulfonic acid for use with fuel cells employing a sulfuric acid electrolyte is also disclosed. New organic fuels, namely, trimethoxymethane, dimethoxymethane, and trioxane are also described for use with either conventional or improved fuel cells.

Organic fuel cell methods and apparatus

NASA Technical Reports Server (NTRS)

Frank, Harvey A. (Inventor); Halpert, Gerald (Inventor); Surampudi, Subbarao (Inventor); Olah, George A. (Inventor); Vamos, Eugene (Inventor); Narayanan, Sekharipuram R. (Inventor); Prakash, G. K. Surya (Inventor)

2008-01-01

A liquid organic, fuel cell is provided which employs a solid electrolyte membrane. An organic fuel, such as a methanol/water mixture, is circulated past an anode of a cell while oxygen or air is circulated past a cathode of the cell. The cell solid electrolyte membrane is preferably fabricated from Nafion.TM.. Additionally, a method for improving the performance of carbon electrode structures for use in organic fuel cells is provided wherein a high surface-area carbon particle/Teflon.TM.-binder structure is immersed within a Nafion.TM./methanol bath to impregnate the electrode with Nafion.TM.. A method for fabricating an anode for use in a organic fuel cell is described wherein metal alloys are deposited onto the electrode in an electro-deposition solution containing perfluorooctanesulfonic acid. A fuel additive containing perfluorooctanesulfonic acid for use with fuel cells employing a sulfuric acid electrolyte is also disclosed. New organic fuels, namely, trimethoxymethane, dimethoxymethane, and trioxane are also described for use with either conventional or improved fuel cells.

Enhanced Proton Conductivity of Sulfonated Hybrid Poly(arylene ether ketone) Membranes by Incorporating an Amino-Sulfo Bifunctionalized Metal-Organic Framework for Direct Methanol Fuel Cells.

PubMed

Ru, Chunyu; Li, Zhenhua; Zhao, Chengji; Duan, Yuting; Zhuang, Zhuang; Bu, Fanzhe; Na, Hui

2018-03-07

Novel side-chain-type sulfonated poly(arylene ether ketone) (SNF-PAEK) containing naphthalene and fluorine moieties on the main chain was prepared in this work, and a new amino-sulfo-bifunctionalized metal-organic framework (MNS, short for MIL-101-NH 2 -SO 3 H) was synthesized via a hydrothermal technology and postmodification. Then, MNS was incorporated into a SNF-PAEK matrix as an inorganic nanofiller to prepare a series of organic-inorganic hybrid membranes (MNS@SNF-PAEK-XX). The mechanical property, methanol resistance, electrochemistry, and other properties of MNS@SNF-PAEK-XX hybrid membranes were characterized in detail. We found that the mechanical strength and methanol resistances of these hybrid membranes were improved by the formation of an ionic cross-linking structure between -NH 2 of MNS and -SO 3 H on the side chain of SNF-PAEK. Particularly, the proton conductivity of these hybrid membranes increased obviously after the addition of MNS. MNS@SNF-PAEK-3% exhibited the proton conductivity of 0.192 S·cm -1 , which was much higher than those of the pristine membrane (0.145 S·cm -1 ) and recast Nafion (0.134 S·cm -1 ) at 80 °C. This result indicated that bifunctionalized MNS rearranged the microstructure of hybrid membranes, which could accelerate the transfer of protons. The hybrid membrane (MNS@SNF-PAEK-3%) showed a better direct methanol fuel cell performance with a higher peak power density of 125.7 mW/cm 2 at 80 °C and a higher open-circuit voltage (0.839 V) than the pristine membrane.

Performance of gas diffusion layer from coconut waste for proton exchange membrane fuel cell

NASA Astrophysics Data System (ADS)

Widodo, H.; Destyorini, F.; Insiyanda, D. R.; Subhan, A.

2017-04-01

The performance of Gas Diffusion Layer (GDL) synthesized from coconut waste. Gas Diffusion Layer (GDL), produced from coconut waste, as a part of Proton Exchange Membrane Fuel Cell (PEMFC) component, has been characterized. In order to know the performance, the commercial products were used as the remaining parts of PEMFC. The proposed GDL possesses 69% porosity for diffusion of Hydrogen fuel and Oxygen, as well as for transporting electron. With the electrical conductivity of 500 mS.cm-1, it also has hydrophobic properties, which is important to avoid the reaction with water, with the contact angle of 139°. The 5 × 5 cm2 GDL paper was co-assembled with the catalyst, Nafion membrane, bipolar plate, current collector, end plate to obtain single Stack PEMFC. The performance was examined by flowing fuel and gas with the flow rate of 500 and 1000 ml.min-1, respectively, and analyse the I-V polarization curve. The measurements were carried out at 30, 35, and 40°C for 5 cycles to ensure the repeatability. The results shows that the current density and the maximum power density reaches 203 mA.cm-2 and 143 mW.cm-2, respectively, with a given voltage 0.6 V, at 40°C.

Elucidating interactions of ionic liquids with polymer films using confocal Raman spectroscopy.

PubMed

Schäfer, Thomas; Di Paolo, Roberto E; Franco, Ricardo; Crespo, João G

2005-05-28

We report on the molecular interactions between room-temperature ionic liquids (RTILs) and Nafion and PDMS membranes, proving that in contact with these polymers RTILs behave like electrolytes rather than solvents.

A Cation-containing Polymer Anion Exchange Membrane based on Poly(norbornene)

NASA Astrophysics Data System (ADS)

Beyer, Frederick; Price, Samuel; Ren, Xiaoming; Savage, Alice

Cation-containing polymers are being studied widely for use as anion exchange membranes (AEMs) in alkaline fuel cells (AFCs) because AEMs offer a number of potential benefits including allowing a solid state device and elimination of the carbonate poisoning problem. The successful AEM will combine high performance from several orthogonal properties, having robust mechanical strength even when wet, high hydroxide conductivity, and the high chemical stability required for long device lifetimes. In this study, we have synthesized a model cationic polymer that combines three of the key advantages of Nafion. The polymer backbone based on semicrystalline atactic poly(norbornene) offers good mechanical properties. A flexible, ether-based tether between the backbone and fixed cation charged species (quaternary ammonium) should provide the low-Tg, hydrophilic environment required to facilitate OH- transport. Finally, methyl groups have been added at the beta position relative to the quaternary ammonium cation to prevent Hoffman elimination, one mechanism by which AEMs are neutralized in a high pH environment. In this poster, we will present our findings on mechanical properties, morphology, charge transport, and chemical stability of this material.

High temperature proton exchange membranes with enhanced proton conductivities at low humidity and high temperature based on polymer blends and block copolymers of poly(1,3-cyclohexadiene) and poly(ethylene glycol)

DOE PAGES

Deng, Shawn; Hassan, Mohammad K.; Nalawade, Amol; ...

2015-09-16

Hot (at 120 °C) and dry (20% relative humidity) operating conditions benefit fuel cell designs based on proton exchange membranes (PEMs) and hydrogen due to simplified system design and increasing tolerance to fuel impurities. In this paper, presented are preparation, partial characterization, and multi-scale modeling of such PEMs based on cross-linked, sulfonated poly(1,3-cyclohexadiene) (xsPCHD) blends and block copolymers with poly(ethylene glycol) (PEG). These low cost materials have proton conductivities 18 times that of current industry standard Nafion at hot, dry operating conditions. Among the membranes studied, the blend xsPCHD-PEG PEM displayed the highest proton conductivity, which exhibits a morphology withmore » higher connectivity of the hydrophilic domain throughout the membrane. Simulation and modeling provide a molecular level understanding of distribution of PEG within this hydrophilic domain and its relation to proton conductivities. Finally, this study demonstrates enhancement of proton conductivity at high temperature and low relative humidity by incorporation of PEG and optimized sulfonation conditions.« less

Diffusion of neutral and ionic species in charged membranes: boric acid, arsenite, and water.

PubMed

Goli, Esmaiel; Hiemstra, Tjisse; Van Riemsdijk, Willem H; Rahnemaie, Rasoul; Malakouti, Mohammad Jafar

2010-10-15

Dynamic ion speciation using DMT (Donnan membrane technique) requires insight into the physicochemical characteristics of diffusion in charged membranes (tortuosity, local diffusion coefficients) as well as ion accumulation. The latter can be precluded by studying the diffusion of neutral species, such as boric acid, B(OH)₃⁰(aq), arsenite, As(OH)₃⁰(aq), or water. In this study, the diffusion rate of B(OH)₃⁰ has been evaluated as a function of the concentration, pH, and ionic strength. The rate is linearly dependent on the concentration of solely the neutral species, without a significant contribution of negatively charged species such as B(OH)₄⁻, present at high pH. A striking finding is the very strong effect (factor of ~10) of the type of cation (K(+), Na(+), Ca(2+), Mg(2+), Al(3+), and H(+)) on the diffusion coefficient of B(OH)₃⁰ and also As(OH)₃⁰. The decrease of the diffusion coefficient can be rationalized as an enhancement of the mean viscosity of the confined solution in the membrane. The diffusion coefficients can be described by a semiempirical relationship, linking the mean viscosity of the confined solute of the membrane to the viscosity of the free solution. In proton-saturated membranes, as used in fuel cells, viscosity is relatively more enhanced; i.e., a stronger water network is formed. Extraordinarily, our B(OH)₃-calibrated model (in HNO₃) correctly predicts the reported diffusion coefficient of water (D(H₂O)), measured with ¹H NMR and quasi-elastic neutron scattering in H(+)-Nafion membranes. Upon drying these membranes, the local hydronium, H(H₂O)(n)(+), concentration and corresponding viscosity increase, resulting in a severe reduction of the diffusion coefficient (D(H₂O) ≈ 5-50 times), in agreement with the model. The present study has a second goal, i.e., development of the methodology for measuring the free concentration of neutral species in solution. Our data suggest that the free concentration can be

Electroactive nanostructured polymer actuators fabricated using sulfonated styrenic pentablock copolymer/montmorillonite/ionic liquid nanocomposite membranes

NASA Astrophysics Data System (ADS)

Lee, Jang-Woo; Hong, Soon Man; Koo, Chong Min

2014-08-01

High-bendable, air-operable ionic polymer-metal composite (IPMC) actuators composed of electroactive nanostructured middle-block sulfonated styrenic pentablock copolymer (SSPB)/sulfonated montmorillonite (s-MMT) nanocomposite electrolyte membranes with bulky imidazolium ionic liquids (ILs) incorporated were fabricated and their bending actuation performances were evaluated. The SSPB-based IPMC actuators showed larger air-operable bending displacements, higher displacement rates, and higher energy efficiency of actuations without conventional IPMC bottlenecks, including back relaxation and actuation instability during actuation in air, than the Nafion counterpart. Incorporation of s-MMT into the SSPB matrix further enhanced the actuation performance of the IPMC actuators in terms of displacement, displacement rate, and energy efficiency. The remarkably high performance of the SSPB/s-MMT/IL IPMCs was considered to be due to the microphase-separated large ionic domains of the SSPB (the average diameter of the ionic domain: ca. 20 nm) and the role of s-MMT as an ionic bridge between the ionic domains, and the ion pumping effect of the bulky imidazolium cations of the ILs as well. The microphase-separated nanostructure of the composite membranes caused a high dimensional stability upon swelling in the presence of ILs, which effectively preserved the original electrode resistance against swelling, leading to a high actuation performance of IPMC.

Nanometer-scale water- and proton-diffusion heterogeneities across water channels in polymer electrolyte membranes.

PubMed

Song, Jinsuk; Han, Oc Hee; Han, Songi

2015-03-16

Nafion, the most widely used polymer for electrolyte membranes (PEMs) in fuel cells, consists of a fluorocarbon backbone and acidic groups that, upon hydration, swell to form percolated channels through which water and ions diffuse. Although the effects of the channel structures and the acidic groups on water/ion transport have been studied before, the surface chemistry or the spatially heterogeneous diffusivity across water channels has never been shown to directly influence water/ion transport. By the use of molecular spin probes that are selectively partitioned into heterogeneous regions of the PEM and Overhauser dynamic nuclear polarization relaxometry, this study reveals that both water and proton diffusivity are significantly faster near the fluorocarbon and the acidic groups lining the water channels than within the water channels. The concept that surface chemistry at the (sub)nanometer scale dictates water and proton diffusivity invokes a new design principle for PEMs. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Increasing the operation temperature of polymer electrolyte membranes for fuel cells: From nanocomposites to hybrids

NASA Astrophysics Data System (ADS)

Licoccia, Silvia; Traversa, Enrico

Among the possible systems investigated for energy production with low environmental impact, polymeric electrolyte membrane fuel cells (PEMFCs) are very promising as electrochemical power sources for application in portable technology and electric vehicles. For practical applications, operating FCs at temperatures above 100 °C is desired, both for hydrogen and methanol fuelled cells. When hydrogen is used as fuel, an increase of the cell temperature produces enhanced CO tolerance, faster reaction kinetics, easier water management and reduced heat exchanger requirement. The use of methanol instead of hydrogen as a fuel for vehicles has several practical benefits such as easy transport and storage, but the slow oxidation kinetics of methanol needs operating direct methanol fuel cells (DMFCs) at intermediate temperatures. For this reason, new membranes are required. Our strategy to achieve the goal of operating at temperatures above 120 °C is to develop organic/inorganic hybrid membranes. The first approach was the use of nanocomposite class I hybrids where nanocrystalline ceramic oxides were added to Nafion. Nanocomposite membranes showed enhanced characteristics, hence allowing their operation up to 130 °C when the cell was fuelled with hydrogen and up to 145 °C in DMFCs, reaching power densities of 350 mW cm -2. The second approach was to prepare Class II hybrids via the formation of covalent bonds between totally aromatic polymers and inorganic clusters. The properties of such covalent hybrids can be modulated by modifying the ratio between organic and inorganic groups and the nature of the chemical components allowing to reach high and stable conductivity values up to 6.4 × 10 -2 S cm -1 at 120 °C.

NafionxAE-based polymer actuators with ionic liquids as solvent incorporated at room temperature

NASA Astrophysics Data System (ADS)

Kikuchi, Kunitomo; Tsuchitani, Shigeki

2009-09-01

Nafion®-based ionic polymer-metal composites (IPMCs), with ionic liquids as solvent, were fabricated by exchanging counterions to ionic liquids at room temperature. Ion exchange is performed by only immersing IPMC in a mixture of de-ionized water and ionic liquids at room temperature for 48 h. The fabricated IPMCs exhibited a bending curvature the same as or larger than that of conventional IPMCs with ionic liquids, formed by ion exchange to ionic liquids at an elevated temperature up to about 100 °C, and also had long-term stability in operation in air, with a fluctuation smaller than 21% in bending curvature during a 180 min operation. The effective ion exchange to ionic liquids in the present method is probably due to an increase in diffusion speed of ionic liquids into IPMC by adsorption of water in a Nafion® membrane. It is a surprise that among IPMCs with ionic liquids 1-ethyl-3-methyl-imidazolium tetrafluoroborate, 1-buthyl-3-methyl-imidazolium tetrafluoroborate (BMIBF4), and 1-buthyl-3-methyl-imidazolium hexafluorophosphate (BMIPF6), IPMC with water-insoluble BMIPF6 exhibited a larger bending curvature than that IPMC with water-miscible BMIBF4. This might be due to effective incorporation of BMIPF6 into IPMC, since BMIPF6 has a higher affinity with IPMC than with water in the mixture of water and BMIPF6. From measurements of complex impedance and step voltage response of the driving current of IPMCs with ionic liquid, they are expressed by an equivalent circuit of a parallel combination of a serial circuit of membrane resistance of Nafion® and electric double layer capacitance at metal electrodes, with membrane capacitance of Nafion®, in a frequency range higher than about 0.1 Hz. The difference in magnitude of bending curvature in three kinds of IPMCs with ionic liquids is mainly due to the difference in bending response speed coming from the difference in the membrane resistance.

Sulfonated poly(ether sulfone)s containing pyridine moiety for PEMFC.

PubMed

Jang, Hohyoun; Islam, Md Monirul; Lim, Youngdon; Hossain, Md Awlad; Cho, Younggil; Joo, Hyunho; Kim, Whangi; Jeon, Heung-Seok

2014-10-01

Sulfonated poly(ether sulfone)s with varied degree of sulfonation (DS) were prepared via post-sulfonation of synthesized pyridine based poly(ether sulfone) (PPES) using concentrated sulfuric acid as sulfonating agent. The DS was varied with different mole ratio of 4,4'-(2,2-diphenylethenylidene)diphenol, DHTPE in the polymer unit. PPES copolymers were synthesized by direct polycondensation of pyridine unit with bis-(4-fluorophenyl)-sulfone, 4, 4'-sulfonyldiphenol and DHTPE. The structure of the resulting PPES copolymer membranes with different sulfonated units were studied by 1H NMR spectroscopy and thermogravimetric analysis (TGA). Sorption experiments were conducted to observe the interaction of sulfonated polymer with water. The ion exchange capacity (IEC) and proton conductivity were evaluated according to the increase of DS. The water uptake (WU) of the resulting membranes was in the range of 17-58%, compared to that of Nafion 211 28%. The membranes provided proton conductivities of 65-95 mS/cm in contrast to 103 mS/cm of Nafion 211.

Low vanadium ion permeabilities of sulfonated poly(phthalazinone ether ketone)s provide high efficiency and stability for vanadium redox flow batteries

NASA Astrophysics Data System (ADS)

Chen, Liyun; Zhang, Shouhai; Chen, Yuning; Jian, Xigao

2017-07-01

A series of novel sulfonated poly(phthalazinone ether ketone)s containing pendant phenyl moieties (SPPEK-Ps) are synthesized and thoroughly characterized. The chemical structures of the polymers are confirmed by 1H NMR and FTIR analysis. The physicochemical properties and single cell performance of SPPEK-P membranes are systematically evaluated, revealing that the membranes are thermally, chemically and mechanically stable. The area resistances of SPPEK-P-90 and SPPEK-P-100 are 0.75 Ω cm2 and 0.34 Ω cm2, respectively. SPPEK-P membranes are impermeable to the bulky hydrated VO2+ ion and exhibited low V3+ ion permeability (SPPEK-P-90, 2.53 × 10-5 cm min-1) (Nafion 115 membrane: 9.0 × 10-4 cm min-1). Tests of SPPEK-P-90 in vanadium redox flow batteries (VRFBs) demonstrate a comparable columbic efficiency (CE) and energy efficiency (EE) to that of Nafion 115, where the CE is 98% and the EE is 83% at 60 mA cm-2. Moreover, the SPPEK-P-90 membrane exhibits stable performance in cell over 100 charge-discharge cycles (∼450 h).

Biologically inspired highly efficient buoyancy engine

NASA Astrophysics Data System (ADS)

Akle, Barbar; Habchi, Wassim; Abdelnour, Rita; Blottman, John, III; Leo, Donald

2012-04-01

Undersea distributed networked sensor systems require a miniaturization of platforms and a means of both spatial and temporal persistence. One aspect of this system is the necessity to modulate sensor depth for optimal positioning and station-keeping. Current approaches involve pneumatic bladders or electrolysis; both require mechanical subsystems and consume significant power. These are not suitable for the miniaturization of sensor platforms. Presented in this study is a novel biologically inspired method that relies on ionic motion and osmotic pressures to displace a volume of water from the ocean into and out of the proposed buoyancy engine. At a constant device volume, the displaced water will alter buoyancy leading to either sinking or floating. The engine is composed of an enclosure sided on the ocean's end by a Nafion ionomer and by a flexible membrane separating the water from a gas enclosure. Two electrodes are placed one inside the enclosure and the other attached to the engine on the outside. The semi-permeable membrane Nafion allows water motion in and out of the enclosure while blocking anions from being transferred. The two electrodes generate local concentration changes of ions upon the application of an electrical field; these changes lead to osmotic pressures and hence the transfer of water through the semi-permeable membrane. Some aquatic organisms such as pelagic crustacean perform this buoyancy control using an exchange of ions through their tissue to modulate its density relative to the ambient sea water. In this paper, the authors provide an experimental proof of concept of this buoyancy engine. The efficiency of changing the engine's buoyancy is calculated and optimized as a function of electrode surface area. For example electrodes made of a 3mm diameter Ag/AgCl proved to transfer approximately 4mm3 of water consuming 4 Joules of electrical energy. The speed of displacement is optimized as a function of the surface area of the Nafion

High power density proton exchange membrane fuel cells

NASA Technical Reports Server (NTRS)

Murphy, Oliver J.; Hitchens, G. Duncan; Manko, David J.

1993-01-01

Proton exchange membrane (PEM) fuel cells use a perfluorosulfonic acid solid polymer film as an electrolyte which simplifies water and electrolyte management. Their thin electrolyte layers give efficient systems of low weight, and their materials of construction show extremely long laboratory lifetimes. Their high reliability and their suitability for use in a microgravity environment makes them particularly attractive as a substitute for batteries in satellites utilizing high-power, high energy-density electrochemical energy storage systems. In this investigation, the Dow experimental PEM (XUS-13204.10) and unsupported high platinum loading electrodes yielded very high power densities, of the order of 2.5 W cm(exp -2). A platinum black loading of 5 mg per cm(exp 2) was found to be optimum. On extending the three-dimensional reaction zone of fuel cell electrodes by impregnating solid polymer electrolyte into the electrode structures, Nafion was found to give better performance than the Dow experimental PEM. The depth of penetration of the solid polymer electrolyte into electrode structures was 50-70 percent of the thickness of the platinum-catalyzed active layer. However, the degree of platinum utilization was only 16.6 percent and the roughness factor of a typical electrode was 274.

Ionic polymer-metal composite actuators based on triple-layered polyelectrolytes composed of individually functionalized layers.

PubMed

Lee, Jang-Woo; Yoo, Young-Tai; Lee, Jae Yeol

2014-01-22

Ionic polymer-metal composite (IPMC) actuators based on two types of triple-layered Nafion composite membranes were prepared via consecutive solution recasting and electroless plating methods. The triple-layered membranes are composed of a Nafion layer containing an amphiphilic organic molecule (10-camphorsulfonic acid; CSA) in the middle section (for fast and large ion conduction) and two Nafion/modified inorganic composite layers in the outer sections (for large accumulation/retention of mobile ions). For construction of the two types of IPMCs, sulfonated montmorillonite (MMT) and polypyrrole (PPy)-coated alumina fillers were incorporated into the outer layers. Both the triple-layered IPMCs exhibited 42% higher tip displacements at the maximum deflections with a negligible back-relaxation, 50-74% higher blocking forces, and more rapid responses under 3 V dc, compared with conventional single-layered Nafion-IPMCs. Improvements in cyclic displacement under a rectangular voltage input of 3 V at 1 Hz were also made in the triple-layered configurations. Compared with single-layered IPMCs consisting of the identical compositions with the respective outer composite layers, the bending rates and energy efficiencies of both the triple-layered IPMCs were significantly higher, although the blocking forces were a bit lower. These remarkable improvements were attributed to higher capacitances and Young's moduli as well as a more efficient transport of mobile ions and water through the middle layer (Nafion/CSA) and a larger accumulation/retention of the mobile species in the outer functionalized inorganic composite layers. Especially, the triple-layered IPMC with the PPy-modified alumina registered the best actuation performance among all the samples, including a viable actuation even at a low voltage of 1.5 V due to involving efficient redox reactions of PPy with the aid of hygroscopic alumina.

The characterization of dielectric properties of platinum-Nafion-poly(3,4-ethylenedioxythiophene) system

NASA Astrophysics Data System (ADS)

Kim, Hyo-Seok

The generation of electrical energy by piezoelectric polymer when mechanically stressed has motivated the investigation of poly(vinylidenefluoride-trifluoro ethylene) (PVDF-TrFE) devices as implantable physiological power supplies. The fragility, specific weight, and rigidity of traditional piezoelectric ceramics used have limited their applicability, although the concept of using piezoelectric elements as mechanically actuated electric power generators for implanted organs has been exploited to some extent. In contrast, piezoelectric polymers are flexible, light, resistant to mechanical fatigue, and efficient as voltage generators. Thus, they can be considered as a source for generating, through mechanical deformation, the electric power needed to fuel implanted artificial organs or to trigger assisting devices such as cardiac pacemakers. This study demonstrates the feasibility of power generation devices that create current from mechanical deformation. One type of power generating device is PVDF-TrFE copolymer and, when built on the pacemaker's lead, can use the motion of the heart as its power source. The other type of device is a Pt-Nafion-PEDOT (PNP) composite device which is fabricated using Perfluorosulfonate ionomeric polymer (Nafion) and conductive polymer, Poly(3,4-ethylenedioxythiophene), by electrochemical synthesis. The device will enable passive location-specific stimulation, thus mimicking the contraction signal of the normal heart. It can generate its own power and may therefore make the battery-lifetime longer. In other applications of these materials is an ultrasound transducer and receiver. Ultrasound transducer/receivers using PNP composite and PVDF as a reference transducer/receiver were studied in order to detect and locate the depth of material (alloy metal, polymer gel) by a pulse-echo method. In a time of flight (TOF) measurement, a transmitter emits short packets of ultrasound waves toward the surface of object in tissue, where they are

High Temperature Polymers for use in Fuel Cells

NASA Technical Reports Server (NTRS)

Peplowski, Katherine M.

2004-01-01

NASA Glenn Research Center (GRC) is currently working on polymers for fuel cell and lithium battery applications. The desire for more efficient, higher power density, and a lower environmental impact power sources has led to interest in proton exchanges membrane fuels cells (PEMFC) and lithium batteries. A PEMFC has many advantages as a power source. The fuel cell uses oxygen and hydrogen as reactants. The resulting products are electricity, heat, and water. The PEMFC consists of electrodes with a catalyst, and an electrolyte. The electrolyte is an ion-conducting polymer that transports protons from the anode to the cathode. Typically, a PEMFC is operated at a temperature of about 80 C. There is intense interest in developing a fuel cell membrane that can operate at higher temperatures in the range of 80 C- 120 C. Operating the he1 cell at higher temperatures increases the kinetics of the fuel cell reaction as well as decreasing the susceptibility of the catalyst to be poisoned by impurities. Currently, Nafion made by Dupont is the most widely used polymer membrane in PEMFC. Nafion does not function well above 80 C due to a significant decrease in the conductivity of the membrane from a loss of hydration. In addition to the loss of conductivity at high temperatures, the long term stability and relatively high cost of Nafion have stimulated many researches to find a substitute for Nafion. Lithium ion batteries are popular for use in portable electronic devices, such as laptop computers and mobile phones. The high power density of lithium batteries makes them ideal for the high power demand of today s advanced electronics. NASA is developing a solid polymer electrolyte that can be used for lithium batteries. Solid polymer electrolytes have many advantages over the current gel or liquid based systems that are used currently. Among these advantages are the potential for increased power density and design flexibility. Automobiles, computers, and cell phones require

High performance polymer chemical hydrogel-based electrode binder materials for direct borohydride fuel cells

NASA Astrophysics Data System (ADS)

Choudhury, Nurul A.; Ma, Jia; Sahai, Yogeshwar; Buchheit, Rudolph G.

Novel, cost-effective, high-performance, and environment-friendly electrode binders, comprising polyvinyl alcohol chemical hydrogel (PCH) and chitosan chemical hydrogel (CCH), are reported for direct borohydride fuel cells (DBFCs). PCH and CCH binders-based electrodes have been fabricated using a novel, simple, cost-effective, time-effective, and environmentally benign technique. Morphologies and electrochemical performance in DBFCs of the chemical hydrogel binder-based electrodes have been compared with those of Nafion ® binder-based electrodes. Relationships between the performance of binders in DBFCs with structural features of the polymers and the polymer-based chemical hydrogels are discussed. The CCH binder exhibited better performance than a Nafion ® binder whereas the PCH binder exhibited comparable performance to Nafion ® in DBFCs operating at elevated cell temperatures. The better performance of CCH binder at higher operating cell temperatures has been ascribed to the hydrophilic nature and water retention characteristics of chitosan. DBFCs employing CCH binder-based electrodes and a Nafion ®-117 membrane as an electrolyte exhibited a maximum peak power density of about 589 mW cm -2 at 70 °C.

Electrochemistry and electrocatalysis of hemoglobin in Nafion/nano-CaCO3 film on a new ionic liquid BPPF6 modified carbon paste electrode.

PubMed

Sun, Wei; Gao, Ruifang; Jiao, Kui

2007-05-03

Room temperature ionic liquid N-butylpyridinium hexafluorophosphate (BPPF6) was used as a binder to construct a new carbon ionic liquid electrode (CILE), which exhibited enhanced electrochemical behavior as compared with the traditional carbon paste electrode with paraffin. By using the CILE as the basal electrode, hemoglobin (Hb) was immobilized on the surface of the CILE with nano-CaCO3 and Nafion film step by step. The Hb molecule in the film kept its native structure and showed good electrochemical behavior. In pH 7.0 Britton-Robinson (B-R) buffer solution, a pair of well-defined, quasi-reversible cyclic voltammetric peaks appeared with cathodic and anodic peak potentials located at -0.444 and -0.285 V (vs SCE), respectively, and the formal potential (E degrees') was at -0.365 V, which was the characteristic of Hb Fe(III)/Fe(II) redox couples. The formal potential of Hb shifted linearly to the increase of buffer pH with a slope of -50.6 mV pH-1, indicating that one electron transferred was accompanied with one proton transportation. Ultraviolet-visible (UV-vis) and Fourier transform infrared (FT-IR) spectroscopy studies showed that Hb immobilized in the Nafion/nano-CaCO3 film still remained its native arrangement. The Hb modified electrode showed an excellent electrocatalytic behavior to the reduction of H2O2, trichloroacetic acid (TCA), and NaNO2.

High-temperature passive direct methanol fuel cells operating with concentrated fuels

NASA Astrophysics Data System (ADS)

Zhao, Xuxin; Yuan, Wenxiang; Wu, Qixing; Sun, Hongyuan; Luo, Zhongkuan; Fu, Huide

2015-01-01

Conventionally, passive direct methanol fuel cells (DMFC) are fed with diluted methanol solutions and can hardly be operated at elevated temperatures (>120 °C) because the ionic conductivity of Nafion-type proton exchange membranes depends strongly on water content. Such a system design would limit its energy density and power density in mobile applications. In this communication, a passive vapor feed DMFC capable of operating with concentrated fuels at high temperatures is reported. The passive DMFC proposed in this work consists of a fuel reservoir, a perforated silicone sheet, a vapor chamber, two current collectors and a membrane electrode assembly (MEA) based on a phosphoric acid doped polybenzimidazole (PBI) membrane. The experimental results reveal that the methanol crossover through a PBI membrane is substantially low when compared with the Nafion membranes and the PBI-based passive DMFC can yield a peak power density of 37.2 mW cm-2 and 22.1 mW cm-2 at 180 °C when 16 M methanol solutions and neat methanol are used respectively. In addition, the 132 h discharge test indicates that the performance of this new DMFC is quite stable and no obvious performance degradation is observed after activation, showing its promising applications in portable power sources.

End of project report on degradation processes in hydrogen fuel cells.

DOT National Transportation Integrated Search

2008-01-01

Proton exchange membrane (PEM) fuel cells are one of the most popular types of fuel cells. They operate similarly to others with the electrolyte material inbetween the electrodes being a patented polymer called Nafion, made by DuPont. This polyelec...

Sensitivity of Hollow Fiber Spacesuit Water Membrane Evaporator Systems to Potable Water Constituents, Contaminants and Air Bubbles

NASA Technical Reports Server (NTRS)

Bue, Grant C.; Trevino, Luis A.; Fritts, Sharon; Tsioulos, Gus

2008-01-01

The Spacesuit Water Membrane Evaporator (SWME) is the baseline heat rejection technology selected for development for the Constellation lunar suit. The first SWME prototype, designed, built, and tested at Johnson Space Center in 1999 used a Teflon hydrophobic porous membrane sheet shaped into an annulus to provide cooling to the coolant loop through water evaporation to the vacuum of space. This present study describes the test methodology and planning and compares the test performance of three commercially available hollow fiber materials as alternatives to the sheet membrane prototype for SWME, in particular, a porous hydrophobic polypropylene, and two variants that employ ion exchange through non-porous hydrophilic modified Nafion. Contamination tests will be performed to probe for sensitivities of the candidate SWME elements to ordinary constituents that are expected to be found in the potable water provided by the vehicle, the target feedwater source. Some of the impurities in potable water are volatile, such as the organics, while others, such as the metals and inorganic ions are nonvolatile. The non-volatile constituents will concentrate in the SWME as evaporated water from the loop is replaced by the feedwater. At some point in the SWME mission lifecycle as the concentrations of the non-volatiles increase, the solubility limits of one or more of the constituents may be reached. The resulting presence of precipitate in the coolant water may begin to plug pores and tube channels and affect the SWME performance. Sensitivity to macroparticles, lunar dust simulant, and air bubbles will also be investigated.

Reliability of high-strain ionomeric polymer transducers fabricated using the novel direct assembly process

NASA Astrophysics Data System (ADS)

Akle, Barbar; Nawshin, Saila; Leo, Donald

2006-03-01

Ionomeric polymer transducers have received considerable attention in the past several years. These actuators, sometimes referred to as artificial muscles, have the ability to generate large bending strain and moderate stress at low applied voltages. Typically, ionic polymer actuators are composed of Nafion-117 membranes with platinum electrodes and are saturated with water diluents. Recently the authors have developed a novel fabrication technique named the Direct Assembly Process (DAP), which allowed good control on electrode morphology and composition. The DAP consists of spraying two high surface area metal-ionomer electrodes on a Nafion membrane. A single- walled carbon nanotubes (SWNT) and ruthenium dioxide (RuO II) hybrid electrode was sprayed on a Formamide hydrated Nafion-117 membrane using the DAP method. This transducer was shown to generate 9.4% peak-peak strain under the application of +/-2V at a strain rate of 1%/sec. Furthermore using the DAP one is capable of incorporating several types of diluents in ionomeric polymer transducers. Transducers with ionic liquid diluents are demonstrated to operate in air for long periods of time. In this work we will present a reliability study of transducers fabricated using the DAP. Each transducer is tested under a frequency range of 0.2Hz to 1Hz, and a potential of +/-1V to +/-3V. Water hydrated transducers dehydrates and stop moving within 5 minutes while operating in air under +/-2V. Transducers with Formamide diluents operate for 20,000 cycles under +/-1.5V and 0.5Hz (around 11hrs), while they degrade in less than 3000 cycles under +/-2V and 0.5Hz. Ionic liquid based transducers are demonstrated to operate in air for over 400,000 with little loss in performance, and over 1 million cycle with a loss of only 43%. Actuators with several electrode compositions are fabricated and a correlation between the reliability of ionic liquid-ionic polymer transducers and maximum strain will be presented. This correlation

Same-View Nano-XAFS/STEM-EDS Imagings of Pt Chemical Species in Pt/C Cathode Catalyst Layers of a Polymer Electrolyte Fuel Cell.

PubMed

Takao, Shinobu; Sekizawa, Oki; Samjeské, Gabor; Nagamatsu, Shin-ichi; Kaneko, Takuma; Yamamoto, Takashi; Higashi, Kotaro; Nagasawa, Kensaku; Uruga, Tomoya; Iwasawa, Yasuhiro

2015-06-04

We have made the first success in the same-view imagings of 2D nano-XAFS and TEM/STEM-EDS under a humid N2 atmosphere for Pt/C cathode catalyst layers in membrane electrode assemblies (MEAs) of polymer electrolyte fuel cells (PEFCs) with Nafion membrane to examine the degradation of Pt/C cathodes by anode gas exchange cycles (start-up/shut-down simulations of PEFC vehicles). The same-view imaging under the humid N2 atmosphere provided unprecedented spatial information on the distribution of Pt nanoparticles and oxidation states in the Pt/C cathode catalyst layer as well as Nafion ionomer-filled nanoholes of carbon support in the wet MEA, which evidence the origin of the formation of Pt oxidation species and isolated Pt nanoparticles in the nanohole areas of the cathode layer with different Pt/ionomer ratios, relevant to the degradation of PEFC catalysts.

Impact of the water symmetry factor on humidification and cooling strategies for PEM fuel cell stacks

NASA Astrophysics Data System (ADS)

Picot, D.; Metkemeijer, R.; Bezian, J. J.; Rouveyre, L.

In this paper, experimental water and thermal balances with three proton exchange membrane fuel cells (PEMFC) are proposed. On the test facility of Ecole des Mines de Paris, three De Nora SPA fuel cell stacks have been successfully studied: An 1 kW e prototype using Nafion® 117, a 5 and a 10 kW e module using Nafion® 115. The averaged water symmetry factor determines strategies to avoid drying membrane. So, we propose analytical solutions to find compromises between humidification and cooling conditions, which determines outlet temperatures of gases. For transport applications, the space occupied by the power module must be reduced. One of the main efforts consists in decreasing the operative pressure. Thus, if adequate cooling power is applied, we show experimentally and theoretically the possibility to use De Nora PEM fuel cells with low pressure, without specific external humidification.

Selective deposition of nanostructured ruthenium oxide using Tobacco mosaic virus for micro-supercapacitors in solid Nafion electrolyte

NASA Astrophysics Data System (ADS)

Gnerlich, Markus; Ben-Yoav, Hadar; Culver, James N.; Ketchum, Douglas R.; Ghodssi, Reza

2015-10-01

A three-dimensional micro-supercapacitor has been developed using a novel bottom-up assembly method combining genetically modified Tobacco mosaic virus (TMV-1Cys), photolithographically defined micropillars and selective deposition of ruthenium oxide on multi-metallic microelectrodes. The three-dimensional microelectrodes consist of a titanium nitride current collector with two functionalized areas: (1) gold coating on the active electrode area promotes TMV-1Cys adhesion, and (2) sacrificial nickel pads dissolve in ruthenium tetroxide plating solution to produce ruthenium oxide on all electrically connected areas. The microfabricated electrodes are arranged in an interdigitated pattern, and the capacitance per electrode has been measured as high as 203 mF cm-2 with solid Nafion electrolyte. The process integration of bio-templated ruthenium oxide with microfabricated electrodes and solid electrolyte is an important advance towards the energy storage needs of mass produced self-sufficient micro-devices.

Selective deposition of nanostructured ruthenium oxide using Tobacco mosaic virus for micro-supercapacitors in solid Nafion electrolyte

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gnerlich, Markus; Ben-Yoav, Hadar; Culver, James N.

A three-dimensional micro-supercapacitor has been developed using a novel bottom-up assembly method combining genetically modified Tobacco mosaic virus (TMV-1Cys), photolithographically defined micropillars and selective deposition of ruthenium oxide on multi-metallic microelectrodes. The three-dimensional microelectrodes consist of a titanium nitride current collector with two functionalized areas: (1) gold coating on the active electrode area promotes TMV-1Cys adhesion, and (2) sacrificial nickel pads dissolve in ruthenium tetroxide plating solution to produce ruthenium oxide on all electrically connected areas. The microfabricated electrodes are arranged in an interdigitated pattern, and the capacitance per electrode has been measured as high as 203 mF cm-2 withmore » solid Nafion electrolyte. The process integration of bio-templated ruthenium oxide with microfabricated electrodes and solid electrolyte is an important advance towards the energy storage needs of mass produced self-sufficient micro-devices.« less

Mechanisms of proton transfer in Nafion: elementary reactions at the sulfonic acid groups.

PubMed

Sagarik, Kritsana; Phonyiem, Mayuree; Lao-ngam, Charoensak; Chaiwongwattana, Sermsiri

2008-04-21

Proton transfer reactions at the sulfonic acid groups in Nafion were theoretically studied, using complexes formed from triflic acid (CF3SO3H), H3O+ and H2O, as model systems. The investigations began with searching for potential precursors and transition states at low hydration levels, using the test-particle model (T-model), density functional theory (DFT) and ab initio calculations. They were employed as starting configurations in Born-Oppenheimer molecular dynamics (BOMD) simulations at 298 K, from which elementary reactions were analyzed and categorized. For the H3O+-H2O complexes, BOMD simulations suggested that a quasi-dynamic equilibrium could be established between the Eigen and Zundel complexes, and that was considered to be one of the most important elementary reactions in the proton transfer process. The average lifetime of H3O+ obtained from BOMD simulations is close to the lowest limit, estimated from low-frequency vibrational spectroscopy. It was demonstrated that proton transfer reactions at -SO3H are not concerted, due to the thermal energy fluctuation and the existence of various quasi-dynamic equilibria, and -SO3H could directly and indirectly mediate proton transfer reactions through the formation of proton defects, as well as the -SO3- and -SO3H2+ transition states.

Ion-exchange synthesis and magneto-optical spectra of colored magnetic thin films composed of metal(II) hexacyanochromate(III).

PubMed

Tozawa, Masanori; Ohkoshi, Shin-ichi; Kojima, Norimichi; Hashimoto, Kazuhito

2003-05-21

Magnetic thin films composed of hexacyanochromate-based magnets, MII1.5[CrIII(CN)6].ZH2O (M = Co, Ni, Cu), were prepared on a transparent Nafion membrane by an ion-exchange process and their Faraday spectra were observed in the visible region.

Determination of heavy metals in mussel and oyster samples with tris (2,2‧-bipyridyl) ruthenium (II)/graphene/Nafion® modified glassy carbon electrodes

NASA Astrophysics Data System (ADS)

Palisoc, Shirley T.; Uy, Donald Jans S.; Natividad, Michelle T.; Lopez, Toni Beth G.

2017-11-01

Tris (2,2‧-bipyridyl)ruthenium(II)/graphene/Nafion® modified glassy carbon electrodes (GCEs) were fabricated using the drop coating method. The modified electrode was used as the working electrode in differential pulse voltammetry (DPV) for the determination of lead, cadmium, and copper in mussel and oyster samples. The concentration of Tris (2,2‧-bipyridyl) ruthenium (II) and graphene were varied while those of Nafion®, methanol, and ethanol were held constant in the coating solution. The morphology and elemental composition of the fabricated electrodes were analyzed by scanning electron microscopy and energy-dispersive x-ray spectroscopy. Cyclic voltammetry (CV) was done to investigate the reversibility and stability of the modified electrodes. The modified electrode with the best figures of merit was utilized for the detection of copper (Cu2+), lead (Pb2+) and cadmium (Cd2+) via DPV. This was the electrode modified with 4 mg [Ru (bpy)3]2+ and 3 mg graphene. The anodic current and metal concentration showed linear relationship in the range of 48 ppb-745 ppb for Pb2+, 49 ppb-613 ppb for Cd2+, and 28 ppb-472 ppb for Cu2+. The limits of detection for lead, cadmium, and copper were 48 ppb, 49 ppb, and 28 ppb, respectively. Results from atomic absorption spectrometry (AAS) were compared with those measured with DPV. Lead, cadmium, and copper were in mussels, oysters, and sea water. In addition, DPV was able to detect other metals such as zinc, iron, tin and mercury in sea water samples and some samples of oysters.

Characterization and Modification of Electrospun Fiber Mats for Use in Composite Proton Exchange Membranes

NASA Astrophysics Data System (ADS)

Mannarino, Matthew Marchand

conducting material or forms a continuous fuel-blocking film. The LbL component consists of a proton-conducting, methanolimpermeable poly(diallyl dimethyl ammonium chloride)/sulfonated poly(2,6-dimethyl 1,4-phenylene oxide) (PDAC/sPPO) thin film. The electrospun fiber component consists of PA 6(3)T fibers of average diameter between 400 and 800 nm, in a nonwoven matrix of 60-90% porosity depending on the temperature of thermal annealing utilized to improve the mechanical properties. This thesis demonstrates the versatility and flexibility of this fabrication technique, since any ion conducting LbL system may be sprayed onto any electrospun fiber mat, allowing for independent control of functionality and mechanical properties. The mechanical properties of the spray coated electrospun mats are shown to be superior to the LbL-only system, and possess intrinsically greater dimensional stability and lower mechanical hysteresis than Nafion under hydration cycling. The electrochemical selectivity of the composite LbL-electrospun membrane is found to be superior to Nafion, which makes them a viable alternative proton exchange membrane for fuel cell applications. The composite proton exchange membranes fabricated in this work were tested in an operational direct methanol fuel cell, with results showing the capability for higher open circuit voltages (OCV) and comparable cell resistances when compared to Nafion. (Copies available exclusively from MIT Libraries, libraries.mit.edu/docs - docs@mit.edu)

Highly stable ionic-covalent cross-linked sulfonated poly(ether ether ketone) for direct methanol fuel cells

NASA Astrophysics Data System (ADS)

Lei, Linfeng; Zhu, Xingye; Xu, Jianfeng; Qian, Huidong; Zou, Zhiqing; Yang, Hui

2017-05-01

A novel ionic cross-linked sulfonated poly(ether ether ketone) containing equal content of sulfonic acid and pendant tertiary amine groups (TA-SPEEK) has been initially synthesized for the application in direct methanol fuel cells (DMFCs). By adjusting the ratio of p-xylene dibromide to tertiary amine groups of TA-SPEEK, a series of ionic-covalent cross-linked membranes (C-SPEEK-x) with tunable degree of cross-linking are prepared. Compared with the pristine membrane, the ionic and ionic-covalent cross-linked proton exchange membranes (PEMs) exhibit reduced methanol permeability and improved mechanical properties, dimensional and oxidative stability. The proton conductivity and methanol selectivity of protonated TA-SPEEK and C-SPEEK-x at 25 °C is up to 0.109 S cm-1 and 3.88 × 105 S s cm-3, respectively, which are higher than that of Nafion 115. The DMFC incorporating C-SPEEK-25 exhibits a maximum power density as high as 35.3 mW cm-2 with 4 M MeOH at 25 °C (31.8 mW cm-2 for Nafion 115). Due to the highly oxidative stability of the membrane, no obvious performance degradation of the DMFC is observed after more than 400 h operation, indicating such cost-effective ionic-covalent cross-linked membranes have substantial potential as alternative PEMs for DMFC applications.

Extended dynamic model for ion diffusion in all-vanadium redox flow battery including the effects of temperature and bulk electrolyte transfer

NASA Astrophysics Data System (ADS)

Badrinarayanan, Rajagopalan; Zhao, Jiyun; Tseng, K. J.; Skyllas-Kazacos, Maria

2014-12-01

As with all redox flow batteries, the Vanadium Redox flow Battery (VRB) can suffer from capacity loss as the vanadium ions diffuse at different rates leading to a build-up on one half-cell and dilution on the other. In this paper an extended dynamic model of the vanadium ion transfer is developed including the effect of temperature and bulk electrolyte transfer. The model is used to simulate capacity decay for a range of different ion exchange membranes that are being used in the VRB. The simulations show that Selemion CMV and Nafion 115 membranes have similar behavior where the impact of temperature on capacity loss is highest within the first 100 cycles. The results for Selemion AMV membrane however are seen to be very different where the capacity loss at different temperatures observed to increase linearly with increasing charging/discharging cycles. The model is made more comprehensive by including the effect of bulk electrolyte transfer. A volume change of 19% is observed in each half-cell for Nafion 115 membrane based on the simulation parameters. The effect of this change in volume directly affects concentration, and the characteristics are analyzed for each vanadium species as well as the overall concentration in the half-cells.

Homogeneous coating of ionomer on electrocatalyst assisted by polybenzimidazole as an adhesive layer and its effect on fuel cell performance

NASA Astrophysics Data System (ADS)

Yang, Zehui; Fujigaya, Tsuyohiko; Nakashima, Naotoshi

2015-12-01

The fabrication of homogeneous ionomer distribution in fuel cell catalyst layers is necessary and important to improve the platinum utilization as well as the power density. Here, we focus on the effect of poly[2,2‧-(2,6-pyridine)-5,5‧-bibenzimidazole] (PyPBI) wrapped on multi-walled carbon nanotubes (MWNTs) for anchoring Nafion ionomer to the electrocatalyst, in which PyPBI functions as the binding sites for platinum nanoparticles (Pt-NPs) used as a catalyst. Based on the result using a control composite without having PyPBI, a strong interaction of the Nafion onto the PyPBI layer is recognized. Importantly, we find that the membrane-electrode assembly (MEA) shows a much higher maximum power density than that of the MEA without PyPBI. A homogeneous coating of Nafion on the electrocatalyst using the PyPBI forms a long-range network of the ionomer, leading to an improved Pt-NP utilization efficiency as well as an enhanced power density of the MEA.

Acid and alkali doped PBI electrolyte in electrochemical system

NASA Astrophysics Data System (ADS)

Xing, Baozhong

In this work the conductivity of blank PBI membrane, acid doped PBI and alkaline doped PBI was systematically studied. A new methodology for sorption kinetics study in electrolyte solution has been established by monitoring the conductivity change during the sorption process. The model of the doping process and mechanism of conductivity are proposed. The performance of PBI (doped under optimum conditions) in fuel cell as PEM was evaluated. The experimental results show that the blank PBI in acid solution is an ionic insulator. It clarified the long time confusion in this area. The acid doped PBI membrane is an ionic conductor. The conductivity increases with the concentration of the acid solution. In high concentration acid solution, the conductivity increases with the type of acid in the order: H2SO 4 > H3PO4 > HClO4 > HNO3 > HCl. The kinetics of the doping process was studied, by a continuous method. The ionic conductivity mechanism was established. The PBI membranes doped with H2SO4 and H3PO4 exhibit better performance than NafionRTM. The doped FBI has more resistance to CO poison. 3% CO in H2 has little effect on the H3PO 4 doped PBI membrane at 185°C. The conductivity of the alkali doped PBI membrane changes with the concentration of the alkaline solution and the type of the alkalis. The conductivity has a maximum in KOH and NaOH solution. The maximum conductivity in KOH is higher than in NaOH and LiOH. It is about 5 times of that of NafionRTM in alkaline solution. The two-step sorption process in alkaline solution was observed. The first step is the permeation process of the alkalis in the PBI membrane. The permeation is the results of diffusion and interaction. It is concluded that the permeation process is controlled by the rate of interaction between the alkali and PBI molecule. The second step is the relaxation process in the membrane. This step contributes more to the conductivity for the membrane than the first step. The ionic conductivity mechanism

Advances in solid polymer electrolyte fuel cell technology with low-platinum-loading electrodes

NASA Technical Reports Server (NTRS)

Srinivasan, Supramaniam; Ticianelli, E. A.; Derouin, C. R.; Redondo, A.

1987-01-01

The Gemini Space program demonstrated the first major application of fuel cell systems. Solid polymer electrolyte fuel cells were used as auxiliary power sources in the spacecraft. There has been considerable progress in this technology since then, particularly with the substitution of Nafion for the polystyrene sulfonate membrane as the electrolyte. Until recently the performance was good only with high platinum loading (4 mg/sq cm) electrodes. Methods are presented to advance the technology by (1) use of low platinum loading (0.35 mg/sq cm) electrodes; (2) optimization of anode/membrane/cathode interfaces by hot pressing; (3) pressurization of reactant gases, which is most important when air is used as cathodic reactant; and (4) adequate humidification of reactant gases to overcome the water management problem. The high performance of the fuel cell with the low loading of platinum appears to be due to the extension of the three dimensional reaction zone by introduction of a proton conductor, Nafion. This was confirmed by cyclic voltammetry.

High-pressure nuclear magnetic resonance studies of fuel cell membranes

NASA Astrophysics Data System (ADS)

Mananga, Eugene Stephane

This thesis focuses on the use of high pressure NMR to study transport properties in electrolyte membranes used for fuel cells. The main concern is in studying the self-diffusion coefficients of ions and molecules in membranes and solutions, which can be used to characterize electrolytes in fuel cells. For this purpose, a high-pressure fringe field NMR method to study transport properties in material systems useful for fuel cell and battery electrolytes, was designed, developed, and implemented. In this investigation, pressure is the thermodynamic variable to obtain additional information about the ionic transport process, which could yield the crucial parameter, activation volume. Most of the work involves proton NMR, with additional investigations of others nuclei, such as fluorine, phosphorus and lithium. Using the FFG method, two fuel cell membrane types (NAFION-117, SPTES), and different dilutions of phosphoric acid were investigated, as was LiTf salt in Diglyme solution, which is used as a lithium battery electrolyte. In addition to high-pressure NMR diffusion measurements carried out in the fringe field gradient for the investigation of SPTES, pulse field gradient spin echo NMR was also used to characterize the water diffusion, in addition to measuring diffusion rates as a function of temperature. This second method allows us to measure distinct diffusion coefficients in cases where the different nuclear (proton) environments can be resolved in the NMR spectrum. Polymer electrolyte systems, in which the mobility of both cations and anions is probed by NMR self-diffusion measurements using standard pulsed field gradient methods and static gradient measurements as a function of applied hydrostatic pressure, were also investigated. The material investigated is the low molecular weight liquid diglyme/LiCF3SO3 (LiTf) complexes which can be used as electrolytes in lithium batteries. Finally, high-pressure diffusion coefficient measurements of phosphoric acid in

Furfural Production from d-Xylose and Xylan by Using Stable Nafion NR50 and NaCl in a Microwave-Assisted Biphasic Reaction.

PubMed

Le Guenic, Sarah; Gergela, David; Ceballos, Claire; Delbecq, Frederic; Len, Christophe

2016-08-22

Pentose dehydration and direct transformation of xylan into furfural were performed in a water-cyclopentyl methyl ether (CPME) biphasic system under microwave irradiation. Heated up between 170 and 190 °C in the presence of Nafion NR50 and NaCl, d-xylose, l-arabinose and xylan gave furfural with maximum yields of 80%, 42% and 55%, respectively. The influence of temperature and reaction time on the reaction kinetics was discussed. This study was also completed by the survey of different reactant ratios, such as organic layer-water or catalyst-inorganic salt ratios. The exchange between proton and cation induced by an excess of NaCl was monitored, and a synergetic effect between the remaining protons and the released HCl was also discovered.

Determination of O₂ Mass Transport at the Pt | PFSA Ionomer Interface under Reduced Relative Humidity.

PubMed

Novitski, David; Holdcroft, Steven

2015-12-16

Oxygen mass transport resistance through the ionomer component in the cathode catalyst layer is considered to contribute overpotential losses in polymer electrolyte membrane fuel cells. Whereas it is known that water uptake, water transport, and proton conductivity are reduced upon reducing relative humidity, the effect on oxygen mass transport remains unknown. We report a two-electrode approach to determine mass transport coefficients for the oxygen reduction reaction in air at the Pt/perfluorosulfonic acid ionomer membrane interface between 90 and 30% RH at 70 °C using a Pt microdisk in a solid state electrochemical cell. Potential-step chronoamperometry was performed at specific mass-transport limiting potentials to allow for the elucidation of the oxygen diffusion coefficient (D(bO2)) and oxygen concentration (c(bO2)). In our efforts, novel approaches in data acquisition, as well as analysis, were examined because of the dynamic nature of the membrane under lowered hydration conditions. Linear regression analysis reveals a decrease in oxygen permeability (D(bO2c(bO2)) by a factor of 1.7 and 3.4 from 90 to 30% RH for Nafion 211 membrane and membranes cast from Nafion DE2020 ionomer solutions, respectively. Additionally, nonlinear curve fitting by way of the Shoup-Szabo equation is employed to analyze the entire current transient during potential step controlled ORR. We also report on the presence of an RH dependence of our previously reported time-dependency measurements for O2 mass transport coefficients.

Understanding Anion, Water, and Methanol Transport in a Polyethylene- b -poly(vinylbenzyl trimethylammonium) Copolymer Anion-Exchange Membrane for Electrochemical Applications

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sarode, Himanshu N.; Yang, Yuan; Motz, Andrew R.

Herein, we report the anion and water transport properties of an anion-exchange membrane (AEM) comprising a block copolymer of polyethylene and poly- (vinylbenzyl trimethylammonium) (PE-b-PVBTMA) with an ion-exchange capacity (IEC) of 1.08 mequiv/g. The conductivity varied little among the anions CO3 2-, HCO3 -, and F-, with a value of Ea ≈ 20 kJ/mol and a maximum fluoride conductivity of 34 mS/cm at 90 °C and 95% relative humidity. The Br- conductivity showed a transition at 60 °C. Pulsed gradient stimulated spin echo nuclear magnetic resonance (PGSE NMR) experiments showed that water diffusion in this AEM is heterogeneous and ismore » affected by the anion present, being fastest in the presence of F-. We determined the methanol self-diffusion in this membrane and observed that it is lower than that in Nafion 117, because of the lower water uptake. This article reports the first measurements of 13C-labeled bicarbonate self-diffusion in an AEM using PGSE NMR spectrometry, which was found to be significantly slower than F- self-diffusion. Back-calculation of the bicarbonate conductivity using the Nernst-Einstein equation gave a value that was significantly lower than the measured value, implying that bicarbonate transport involves OH- in the transport mechanism. Fourier transform infrared spectroscopy, PGSE NMR spectrometry, and small-angle X-ray scattering (SAXS) indicated the presence of different types of waters present in the membrane at different length scales. The SAXS data indicated that there is a water-rich region within the hydrophilic domains of the polymer that has a temperature dependence in intensity at 95% relative humidity (RH).« less

Efficient electrolyzer for CO2 splitting in neutral water using earth-abundant materials.

PubMed

Tatin, Arnaud; Comminges, Clément; Kokoh, Boniface; Costentin, Cyrille; Robert, Marc; Savéant, Jean-Michel

2016-05-17

Low-cost, efficient CO2-to-CO+O2 electrochemical splitting is a key step for liquid-fuel production for renewable energy storage and use of CO2 as a feedstock for chemicals. Heterogeneous catalysts for cathodic CO2-to-CO associated with an O2-evolving anodic reaction in high-energy-efficiency cells are not yet available. An iron porphyrin immobilized into a conductive Nafion/carbon powder layer is a stable cathode producing CO in pH neutral water with 90% faradaic efficiency. It is coupled with a water oxidation phosphate cobalt oxide anode in a home-made electrolyzer by means of a Nafion membrane. Current densities of approximately 1 mA/cm(2) over 30-h electrolysis are achieved at a 2.5-V cell voltage, splitting CO2 and H2O into CO and O2 with a 50% energy efficiency. Remarkably, CO2 reduction outweighs the concurrent water reduction. The setup does not prevent high-efficiency proton transport through the Nafion membrane separator: The ohmic drop loss is only 0.1 V and the pH remains stable. These results demonstrate the possibility to set up an efficient, low-voltage, electrochemical cell that converts CO2 into CO and O2 by associating a cathodic-supported molecular catalyst based on an abundant transition metal with a cheap, easy-to-prepare anodic catalyst oxidizing water into O2.

Microfluidic paper-based biomolecule preconcentrator based on ion concentration polarization.

PubMed

Han, Sung Il; Hwang, Kyo Seon; Kwak, Rhokyun; Lee, Jeong Hoon

2016-06-21

Microfluidic paper-based analytical devices (μPADs) for molecular detection have great potential in the field of point-of-care diagnostics. Currently, a critical problem being faced by μPADs is improving their detection sensitivity. Various preconcentration processes have been developed, but they still have complicated structures and fabrication processes to integrate into μPADs. To address this issue, we have developed a novel paper-based preconcentrator utilizing ion concentration polarization (ICP) with minimal addition on lateral-flow paper. The cation selective membrane (i.e., Nafion) is patterned on adhesive tape, and this tape is then attached to paper-based channels. When an electric field is applied across the Nafion, ICP is initiated to preconcentrate the biomolecules in the paper channel. Departing from previous paper-based preconcentrators, we maintain steady lateral fluid flow with the separated Nafion layer; as a result, fluorescent dyes and proteins (FITC-albumin and bovine serum albumin) are continuously delivered to the preconcentration zone, achieving high preconcentration performance up to 1000-fold. In addition, we demonstrate that the Nafion-patterned tape can be integrated with various geometries (multiplexed preconcentrator) and platforms (string and polymer microfluidic channel). This work would facilitate integration of various ICP devices, including preconcentrators, pH/concentration modulators, and micro mixers, with steady lateral flows in paper-based platforms.

Operando fuel cell spectroscopy

NASA Astrophysics Data System (ADS)

Kendrick, Ian Michael

The active state of a catalyst only exists during catalysis (1) provided the motivation for developing operando spectroscopic techniques. A polymer electrolyte membrane fuel cell (PEMFC) was designed to interface with commercially available instruments for acquisition of infrared spectra of the catalytic surface of the membrane electrode assembly (MEA) during normal operation. This technique has provided insight of the complex processes occurring at the electrode surface. Nafion, the solid electrolyte used in most modern-day polymer electrolyte membrane fuel cells (PEMFC), serves many purposes in fuel cell operation. However, there is little known of the interface between Nafion and the electrode surface. Previous studies of complex Stark tuning curves of carbon monoxide on the surface of a platinum electrode were attributed the co-adsorption of bisulfite ions originating from the 0.5M H2SO4 electrolyte used in the study(2). Similar tuning curves obtained on a fuel cell MEA despite the absence of supplemental electrolytes suggest the adsorption of Nafion onto platinum (3). The correlation of spectra obtained using attenuated total reflectance spectroscopy (ATR) and polarization modulated IR reflection-absorption spectroscopy (PM-IRRAS) to a theoretical spectrum generated using density functional theory (DFT) lead to development of a model of Nafion and platinum interaction which identified participation of the SO3- and CF3 groups in Nafion adsorption. The use of ethanol as a fuel stream in proton exchange membrane fuel cells provides a promising alternative to methanol. Relative to methanol, ethanol has a greater energy density, lower toxicity and can be made from the fermentation of biomass(4). Operando IR spectroscopy was used to study the oxidation pathway of ethanol and Stark tuning behavior of carbon monoxide on Pt, Ru, and PtRu electrodes. Potential dependent products such as acetaldehyde, acetic acid and carbon monoxide are identified as well as previously

Electrochemical delignification of wood pulp using polyoxometalate mediators

Treesearch

R.S. Reiner; E.L. Springer; R.H. Atalla

2003-01-01

It has been found that polyoxometalates (POMs) can act as mediators in the electrochemical oxidation of lignin in pulps. An electrochemical cell, with a Nafion® membrane separating the anode and cathode compartments, was used in the delignification experiments. A softwood kraft pulp was placed in the anode compartment with a buffered 0.01M solution of the...

New electrocatalysts for unitized regenerative fuel cell: Pt-Ir alloy deposited on the proton exchange membrane surface by impregnation-reduction method.

PubMed

Wan, Chieh-Hao; Wu, Chun-Lin; Lin, Meng-Tsun; Shih, Chihhsiong

2010-07-01

In this paper, a modified technique to prepare Pt-Ir catalyst layer on the proton exchange membrane (PEM) surface using the impregnation-reduction (IR) method is proposed to improve the electrocatalytic activity as well as the life cycle of the bifunctional oxygen electrode (BOE). The resulted electrocatalysts were characterized by the Scanning Electron Microscopy (SEM), X-ray Diffraction (XRD), Electron Probe Micro-Analysis (EPMA), and Transmission Electron Microscope (TEM). The electrocatalytic properties of the Pt-Ir layer on PEM surface for the oxygen reduction and water oxidation reactions as well as the life cycle of MEA were investigated. Experimental results showed that the Ir particles were dispersed densely in the platinum layer through the modified IR technique. The atomic ratio of Pt over Ir elements was 9:1, and the resulted thickness of the obtained Pt-Ir catalyst layer was about 1.0 microm. The Pt-Ir catalyst layer was composed of Pt layer doped with Ir nano-particles comprising nano Pt-Ir alloy phase. The large surface area of Ir core with Pt shell particles and the presence of nano Pt-Ir alloy phase led to a higher electrocatalytic activity of BOE. Due to the good binding between the Nafion membrane and the Pt-Ir alloy catalyst, as well as the composite structure of the resulted Pt-Ir, the life cycle of Unitized Regenerative Fuel Cell (URFC) is improved through this novel BOE.

Nafion/lead nitroprusside nanoparticles modified carbon ceramic electrode as a novel amperometric sensor for L-cysteine.

PubMed

Razmi, H; Heidari, H

2009-05-01

This work describes the electrochemical and electrocatalytic properties of carbon ceramic electrode (CCE) modified with lead nitroprusside (PbNP) nanoparticles as a new electrocatalyst material. The structure of deposited film on the CCE was characterized by energy dispersive X-ray (EDX), Fourier transform infrared (FTIR), and scanning electron microscopy (SEM). The cyclic voltammogram (CV) of the PbNP modified CCE showed two well-defined redox couples due to [Fe(CN)5NO](3-)/[Fe(CN)5NO](2-) and Pb(IV)/Pb(II) redox reactions. The modified electrode showed electrocatalytic activity toward the oxidation of L-cysteine and was used as an amperometric sensor. Also, to reduce the fouling effect of L-cysteine and its oxidation products on the modified electrode, a thin film of Nafion was coated on the electrode surface. The sensor response was linearly changed with L-cysteine concentration in the range of 1 x 10(-6) to 6.72 x 10(-5)mol L(-1) with a detection limit (signal/noise ratio [S/N]=3) of 0.46 microM. The sensor sensitivity was 0.17 microA (microM)(-1), and some important advantages such as simple preparation, fast response, good stability, interference-free signals, antifouling properties, and reproducibility of the sensor for amperometric determination of L-cysteine were achieved.

Omniphobic Membrane for Robust Membrane Distillation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lin, SH; Nejati, S; Boo, C

2014-11-01

In this work, we fabricate an omniphobic microporous membrane for membrane distillation (MD) by modifying a hydrophilic glass fiber membrane with silica nanoparticles followed by surface fluorination and polymer coating. The modified glass fiber membrane exhibits an anti-wetting property not only against water but also against low surface tension organic solvents that easily wet a hydrophobic polytetrafluoroethylene (PTFE) membrane that is commonly used in MD applications. By comparing the performance of the PTFE and omniphobic membranes in direct contact MD experiments in the presence of a surfactant (sodium dodecyl sulfate, SDS), we show that SDS wets the hydrophobic PTFE membranemore » but not the omniphobic membrane. Our results suggest that omniphobic membranes are critical for MD applications with feed waters containing surface active species, such as oil and gas produced water, to prevent membrane pore wetting.« less

Biopores/membrane proteins in synthetic polymer membranes.

PubMed

Garni, Martina; Thamboo, Sagana; Schoenenberger, Cora-Ann; Palivan, Cornelia G

2017-04-01

Mimicking cell membranes by simple models based on the reconstitution of membrane proteins in lipid bilayers represents a straightforward approach to understand biological function of these proteins. This biomimetic strategy has been extended to synthetic membranes that have advantages in terms of chemical and mechanical stability, thus providing more robust hybrid membranes. We present here how membrane proteins and biopores have been inserted both in the membrane of nanosized and microsized compartments, and in planar membranes under various conditions. Such bio-hybrid membranes have new properties (as for example, permeability to ions/molecules), and functionality depending on the specificity of the inserted biomolecules. Interestingly, membrane proteins can be functionally inserted in synthetic membranes provided these have appropriate properties to overcome the high hydrophobic mismatch between the size of the biomolecule and the membrane thickness. Functional insertion of membrane proteins and biopores in synthetic membranes of compartments or in planar membranes is possible by an appropriate selection of the amphiphilic copolymers, and conditions of the self-assembly process. These hybrid membranes have new properties and functionality based on the specificity of the biomolecules and the nature of the synthetic membranes. Bio-hybrid membranes represent new solutions for the development of nanoreactors, artificial organelles or active surfaces/membranes that, by further gaining in complexity and functionality, will promote translational applications. This article is part of a Special Issue entitled: Lipid order/lipid defects and lipid-control of protein activity edited by Dirk Schneider. Copyright © 2016. Published by Elsevier B.V.

Near-ambient solid polymer fuel cell

NASA Technical Reports Server (NTRS)

Holleck, G. L.

1993-01-01

Fuel cells are extremely attractive for extraterrestrial and terrestrial applications because of their high energy conversion efficiency without noise or environmental pollution. Among the various fuel cell systems the advanced polymer electrolyte membrane fuel cells based on sulfonated fluoropolymers (e.g., Nafion) are particularly attractive because they are fairly rugged, solid state, quite conductive, of good chemical and thermal stability and show good oxygen reduction kinetics due to the low specific adsorption of the electrolyte on the platinum catalyst. The objective of this program is to develop a solid polymer fuel cell which can efficiently operate at near ambient temperatures without ancillary components for humidification and/or pressurization of the fuel or oxidant gases. During the Phase 1 effort we fabricated novel integral electrode-membrane structures where the dispersed platinum catalyst is precipitated within the Nafion ionomer. This resulted in electrode-membrane units without interfacial barriers permitting unhindered water diffusion from cathode to anode. The integral electrode-membrane structures were tested as fuel cells operating on H2 and O2 or air at 1 to 2 atm and 10 to 50 C without gas humidification. We demonstrated that cells with completely dry membranes could be self started at room temperature and subsequently operated on dry gas for extended time. Typical room temperature low pressure operation with unoptimized electrodes yielded 100 mA/cm(exp 2) at 0.5V and maximum currents over 300 mA/cm(exp 2) with low platinum loadings. Our results clearly demonstrate that operation of proton exchange membrane fuel cells at ambient conditions is feasible. Optimization of the electrode-membrane structure is necessary to assess the full performance potential but we expect significant gains in weight and volume power density for the system. The reduced complexity will make fuel cells also attractive for smaller and portable power supplies and as

Environmentally Controlled Infrared Spectroscopy System for Fundamental Studies of Polymer Electrolyte Membranes

DTIC Science & Technology

2015-10-15

to state-of- hydration . Polarization modulated infrared reflection- absorption spectroscopy experiments are enabled by the use of a spin-coater to coat...NAME(S) AND ADDRESS (ES) U.S. Army Research Office P.O. Box 12211 Research Triangle Park, NC 27709-2211 SPEEK, Nafion, Ionomers, state-of- hydration ...enabled correlation of the exchange site structure to state-of- hydration . Polarization modulated infrared reflection-absorption spectroscopy experiments

Membranes, methods of making membranes, and methods of separating gases using membranes

DOEpatents

Ho, W. S. Winston

2012-10-02

Membranes, methods of making membranes, and methods of separating gases using membranes are provided. The membranes can include at least one hydrophilic polymer, at least one cross-linking agent, at least one base, and at least one amino compound. The methods of separating gases using membranes can include contacting a gas stream containing at least one of CO.sub.2, H.sub.2S, and HCl with one side of a nonporous and at least one of CO.sub.2, H.sub.2S, and HCl selectively permeable membrane such that at least one of CO.sub.2, H.sub.2S, and HCl is selectively transported through the membrane.

Advanced Materials for PEM-Based Fuel Cell Systems

DOE Office of Scientific and Technical Information (OSTI.GOV)

James E. McGrath; Donald G. Baird; Michael von Spakovsky

2005-10-26

Proton exchange membrane fuel cells (PEMFCs) are quickly becoming attractive alternative energy sources for transportation, stationary power, and small electronics due to the increasing cost and environmental hazards of traditional fossil fuels. Two main classes of PEMFCs include hydrogen/air or hydrogen/oxygen fuel cells and direct methanol fuel cells (DMFCs). The current benchmark membrane for both types of PEMFCs is Nafion, a perfluorinated sulfonated copolymer made by DuPont. Nafion copolymers exhibit good thermal and chemical stability, as well as very high proton conductivity under hydrated conditions at temperatures below 80 degrees C. However, application of these membranes is limited due tomore » their high methanol permeability and loss of conductivity at high temperatures and low relative humidities. These deficiencies have led to the search for improved materials for proton exchange membranes. Potential PEMs should have good thermal, hydrolytic, and oxidative stability, high proton conductivity, selective permeability, and mechanical durability over long periods of time. Poly(arylene ether)s, polyimides, polybenzimidazoles, and polyphenylenes are among the most widely investigated candidates for PEMs. Poly(arylene ether)s are a promising class of proton exchange membranes due to their excellent thermal and chemical stability and high glass transition temperatures. High proton conductivity can be achieved through post-sulfonation of poly(arylene ether) materials, but this most often results in very high water sorption or even water solubility. Our research has shown that directly polymerized poly(arylene ether) copolymers show important advantages over traditional post-sulfonated systems and also address the concerns with Nafion membranes. These properties were evaluated and correlated with morphology, structure-property relationships, and states of water in the membranes. Further improvements in properties were achieved through incorporation of

[Effect of Membrane Wettability on Membrane Fouling and Chemical Durability of SPG Membranes].

PubMed

Zhang, Jing; Xiao, Tai-min; Zhang, Jing; Cao, Li-ya; Du, Ya-wei; Liu, Chun; Zhang, Lei

2015-05-01

Shirasu porous glass (SPG) membranes have been applied for microbubble aeration in aerobic wastewater treatment. In the present study, both hydrophilic and hydrophobic SPG membranes were used in a microbubble-aerated biofilm reactor with online chemical cleaning, and their membrane fouling and chemical durability were determined to be strongly dependent on the membrane wettability. The fouling layer formed on the surface of both membranes was confirmed to be mainly organic fouling, and the hydrophobic membrane showed a relatively stronger resistance to the organic fouling. The severe chemical corrosion of the hydrophilic membrane was observed due to exposure to the alkaline sodium hypochlorite solution used for chemical cleaning, which resulted in significant increases in the median pore diameter and the porosity. On the other hand, the pore structure of the hydrophobic membrane changed slightly when exposed to the alkaline sodium hypochlorite solution, suggesting its strong alkali-resistance due to the non-wetting surface. However, the surface hydrophobic groups of hydrophobic membrane could be oxidized by sodium hypochlorite solution, resulting in more wettable membrane surface. The hydrophobic membrane also showed better performance in the respects of oxygen transfer, contaminant removal and energy-saving. Therefore, the hydrophobic membrane seemed more appropriate to be applied for microbubble aeration in aerobic wastewater treatment process.

Integration of a highly ordered gold nanowires array with glucose oxidase for ultra-sensitive glucose detection.

PubMed

Cui, Jiewu; Adeloju, Samuel B; Wu, Yucheng

2014-01-27

A highly sensitive amperometric nanobiosensor has been developed by integration of glucose oxidase (GO(x)) with a gold nanowires array (AuNWA) by cross-linking with a mixture of glutaraldehyde (GLA) and bovine serum albumin (BSA). An initial investigation of the morphology of the synthesized AuNWA by field emission scanning electron microscopy (FESEM) and field emission transmission electron microscopy (FETEM) revealed that the nanowires array was highly ordered with rough surface, and the electrochemical features of the AuNWA with/without modification were also investigated. The integrated AuNWA-BSA-GLA-GO(x) nanobiosensor with Nafion membrane gave a very high sensitivity of 298.2 μA cm(-2) mM(-1) for amperometric detection of glucose, while also achieving a low detection limit of 0.1 μM, and a wide linear range of 5-6000 μM. Furthermore, the nanobiosensor exhibited excellent anti-interference ability towards uric acid (UA) and ascorbic acid (AA) with the aid of Nafion membrane, and the results obtained for the analysis of human blood serum indicated that the device is capable of glucose detection in real samples. Copyright © 2013 Elsevier B.V. All rights reserved.

Electrochemical performance and durability of carbon supported Pt catalyst in contact with aqueous and polymeric proton conductors.

PubMed

Andersen, Shuang Ma; Skou, Eivind

2014-10-08

Significant differences in catalyst performance and durability are often observed between the use of a liquid electrolyte (e.g., sulfuric acid), and a solid polymer electrolyte (e.g., Nafion). To understand this phenomenon, we studied the electrochemical behavior of a commercially available carbon supported platinum catalyst in four different electrode structures: catalyst powder (CP), catalyst ionomer electrode (CIE), half membrane electrode assembly (HMEA), and full membrane electrode assembly (FMEA) in both ex situ and in situ experiments under a simulated start/stop cycle. We found that the catalyst performance and stability are very much influenced by the presence of the Nafion ionomers. The proton conducting phase provided by the ionomer and the self-assembled electrode structure render the catalysts a higher utilization and better stability. This is probably due to an enhanced dispersion, an improved proton-catalyst interface, the restriction of catalyst particle aggregation, and the improved stability of the ionomer phase especially after the lamination. Therefore, an innovative electrode HMEA design for ex-situ catalyst characterization is proposed. The electrode structure is identical to the one used in a real fuel cell, where the protons transport takes place solely through solid state proton conducting phase.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pezeshki, Alan M.; Fujimoto, Cy; Sun, Che -Nan

In this paper, we report on the performance of Diels Alder poly(phenylene) membranes in vanadium redox flow batteries. The membranes were functionalized with quaternary ammonium groups to form an anion exchange membrane (QDAPP) and with sulfonic acid groups to form a cation exchange membrane (SDAPP). Both membrane classes showed similar conductivities in the battery environment, suggesting that the ion conduction mechanism in the material is not strongly affected by the moieties along the polymer backbone. The resistance to vanadium permeation in QDAPP was not improved relative to SDAPP, further suggesting that the polarity of the functional groups do not playmore » a significant role in the membrane materials tested. Both QDAPP and SDAPP outperformed Nafion membranes in cycling tests, with both achieving voltage efficiencies above 85% while maintaining 95% coulombic efficiency while at a current density of 200 mA/cm 2.« less

Ionic Liquids for Advanced Materials

DTIC Science & Technology

2008-12-01

optical clarity to completely opacity with increased amounts of ionic liquid . This transition was not previously observed in Nafion ® membranes swollen...1 IONIC LIQUIDS FOR ADVANCED MATERIALS Timothy E. Long, Sean M. Ramirez, Randy Heflin, Harry W. Gibson, Louis A. Madsen, Donald J. Leo, Nakhiah...is to develop a micromechanical model for the electrochemomechanical transduction mechanisms in newly synthesized ionic liquid polymers in order to

The effect of acute microgravity on mechanically-induced membrane damage and membrane-membrane fusion events

NASA Technical Reports Server (NTRS)

Clarke, M. S.; Vanderburg, C. R.; Feeback, D. L.; McIntire, L. V. (Principal Investigator)

2001-01-01

Although it is unclear how a living cell senses gravitational forces there is no doubt that perturbation of the gravitational environment results in profound alterations in cellular function. In the present study, we have focused our attention on how acute microgravity exposure during parabolic flight affects the skeletal muscle cell plasma membrane (i.e. sarcolemma), with specific reference to a mechanically-reactive signaling mechanism known as mechanically-induced membrane disruption or "wounding". Both membrane rupture and membrane resealing events mediated by membrane-membrane fusion characterize this response. We here present experimental evidence that acute microgravity exposure can inhibit membrane-membrane fusion events essential for the resealing of sarcolemmal wounds in individual human myoblasts. Additional evidence to support this contention comes from experimental studies that demonstrate acute microgravity exposure also inhibits secretagogue-stimulated intracellular vesicle fusion with the plasma membrane in HL-60 cells. Based on our own observations and those of other investigators in a variety of ground-based models of membrane wounding and membrane-membrane fusion, we suggest that the disruption in the membrane resealing process observed during acute microgravity is consistent with a microgravity-induced decrease in membrane order.

The Effect of Acute Microgravity on Mechanically-Induced Membrane Damage and Membrane-Membrane Fusion Events

NASA Technical Reports Server (NTRS)

Clarke, Mark, S. F.; Vanderburg, Charles R.; Feedback, Daniel L.

2001-01-01

Although it is unclear how a living cell senses gravitational forces there is no doubt that perturbation of the gravitational environment results in profound alterations in cellular function. In the present study, we have focused our attention on how acute microgravity exposure during parabolic flight affects the skeletal muscle cell plasma membrane (i.e. sarcolemma), with specific reference to a mechanically-reactive signaling mechanism known as mechanically-induced membrane disruption or "wounding". This response is characterized by both membrane rupture and membrane resealing events mediated by membrane-membrane fusion. We here present experimental evidence that acute microgravity exposure can inhibit membrane-membrane fusion events essential for the resealing of sarcolemmal wounds in individual human myoblasts. Additional evidence to support this contention comes from experimental studies that demonstrate acute microgravity exposure also inhibits secretagogue-stimulated intracellular vesicle fusion with the plasma membrane in HL-60 cells. Based on our own observations and those of other investigators in a variety of ground-based models of membrane wounding and membrane-membrane fusion, we suggest that the disruption in the membrane resealing process observed during acute microgravity is consistent with a microgravity-induced decrease in membrane order.

Sheet Membrane Spacesuit Water Membrane Evaporator

NASA Technical Reports Server (NTRS)

Bue, Grant; Trevino, Luis; Zapata, Felipe; Dillion, Paul; Castillo, Juan; Vonau, Walter; Wilkes, Robert; Vogel, Matthew; Frodge, Curtis

2013-01-01

A document describes a sheet membrane spacesuit water membrane evaporator (SWME), which allows for the use of one common water tank that can supply cooling water to the astronaut and to the evaporator. Test data showed that heat rejection performance dropped only 6 percent after being subjected to highly contaminated water. It also exhibited robustness with respect to freezing and Martian atmospheric simulation testing. Water was allowed to freeze in the water channels during testing that simulated a water loop failure and vapor backpressure valve failure. Upon closing the backpressure valve and energizing the pump, the ice eventually thawed and water began to flow with no apparent damage to the sheet membrane. The membrane evaporator also serves to de-gas the water loop from entrained gases, thereby eliminating the need for special degassing equipment such as is needed by the current spacesuit system. As water flows through the three annular water channels, water evaporates with the vapor flowing across the hydrophobic, porous sheet membrane to the vacuum side of the membrane. The rate at which water evaporates, and therefore, the rate at which the flowing water is cooled, is a function of the difference between the water saturation pressure on the water side of the membrane, and the pressure on the vacuum side of the membrane. The primary theory is that the hydrophobic sheet membrane retains water, but permits vapor pass-through when the vapor side pressure is less than the water saturation pressure. This results in evaporative cooling of the remaining water.

A sensitive label-free amperometric CEA immunosensor based on graphene-nafion nanocomposite film as an enhanced sensing platform.

PubMed

Li, Yan; Yang, Wei-Kang; Fan, Man-Qi; Liu, Ao

2011-01-01

A novel approach to fabricate a label-free amperometric immunosensor for the detection of carcinoembryonic antigen (CEA) was described. Herein, methylene blue (MB), gold nanoparticles (AuNPs) and carcinoembryonic antibody (anti-CEA) were layer-by-layer assembled on the graphene-Nafion nanocomposite film-modified electrode by means of a self-assembling technique and the opposite-charged adsorption. Subsequently, the stepwise self-assembling procedure of the immunosensor was further characterized by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The factors influencing the performance of the resulting immunosensor were studied in detail. The developed procedure showed improved features, including larger amount and higher immunoactivity of the immobilized antibody and repeatable regeneration of the sensor, as well as direct, rapid and simple determination for the antigen without multiple separation and labeling steps. The immunosensor could detect the target protein in a range of 0.5 to 120 ng/mL with a limit of 0.17 ng/mL (at 3σ). Finally, the immunosensing system was evaluated on several clinical samples. Analytical results were found to be in satisfactory agreement with those detected by the enzyme-linked immunosorbent assay (ELISA) method, indicating that this new method was a promising alternative tool for clinical diagnosis.

Tuning of Nafion® by HKUST-1 as coordination network to enhance proton conductivity for fuel cell applications

NASA Astrophysics Data System (ADS)

Kim, Hee Jin; Talukdar, Krishan; Choi, Sang-June

2016-02-01

Metal-organic frameworks can be intentionally coordinated to achieve improved proton conductivity because they have highly ordered structures and modular nature that serve as a scaffold to anchor acidic groups and develop efficient proton transfer pathways for fuel cell application. Using the concept of a coordination network, the conductivity of Nafion® was tuned by the incorporation of HKUST-1. It has CuII-paddle wheel type nodes and 1,3,5-benzenetricarboxylate struts, feature accessible sites that provides an improved protonic channel depending on the water content. In spite of the fact that HKUST-1 is neutral, coordinated water molecules are contributed adequately acidic by CuII to supply protons to enhance proton conductivity. Water molecules play a vital part in transfer of proton as conducting media and serve as triggers to change proton conductivity through reforming hydrogen bonding networks by water adsorption/desorption process. Increased ion exchange capacity and proton conductivity with lower water uptake of the H3PO4-doped material, and improved thermal stability (as confirmed by thermogravimetric analysis) were achieved. The structure of HKUST-1 was confirmed via field emission scanning electron microscopy and X-ray diffraction, while the porosity and adsorption desorption capacity were characterized by porosity analysis.

Recent Advances in Pd-Based Membranes for Membrane Reactors.

PubMed

Arratibel Plazaola, Alba; Pacheco Tanaka, David Alfredo; Van Sint Annaland, Martin; Gallucci, Fausto

2017-01-01

Palladium-based membranes for hydrogen separation have been studied by several research groups during the last 40 years. Much effort has been dedicated to improving the hydrogen flux of these membranes employing different alloys, supports, deposition/production techniques, etc. High flux and cheap membranes, yet stable at different operating conditions are required for their exploitation at industrial scale. The integration of membranes in multifunctional reactors (membrane reactors) poses additional demands on the membranes as interactions at different levels between the catalyst and the membrane surface can occur. Particularly, when employing the membranes in fluidized bed reactors, the selective layer should be resistant to or protected against erosion. In this review we will also describe a novel kind of membranes, the pore-filled type membranes prepared by Pacheco Tanaka and coworkers that represent a possible solution to integrate thin selective membranes into membrane reactors while protecting the selective layer. This work is focused on recent advances on metallic supports, materials used as an intermetallic diffusion layer when metallic supports are used and the most recent advances on Pd-based composite membranes. Particular attention is paid to improvements on sulfur resistance of Pd based membranes, resistance to hydrogen embrittlement and stability at high temperature.

Inverse colloidal crystal membranes for hydrophobic interaction membrane chromatography.

PubMed

Vu, Anh T; Wang, Xinying; Wickramasinghe, S Ranil; Yu, Bing; Yuan, Hua; Cong, Hailin; Luo, Yongli; Tang, Jianguo

2015-08-01

Hydrophobic interaction membrane chromatography has gained interest due to its excellent performance in the purification of humanized monoclonal antibodies. The membrane material used in hydrophobic interaction membrane chromatography has typically been commercially available polyvinylidene fluoride. In this contribution, newly developed inverse colloidal crystal membranes that have uniform pores, high porosity and, therefore, high surface area for protein binding are used as hydrophobic interaction membrane chromatography membranes for humanized monoclonal antibody immunoglobulin G purification. The capacity of the inverse colloidal crystal membranes developed here is up to ten times greater than commercially available polyvinylidene fluoride membranes with a similar pore size. This work highlights the importance of developing uniform pore size high porosity membranes in order to maximize the capacity of hydrophobic interaction membrane chromatography. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Radiolytic preparation and characterization of hydrophilic poly(acrylonitrile-co-vinylsulfonate)-grafted porous poly(tetrafluoroethylene) substrates