Commenced in January 2007
Frequency: Monthly
Edition: International
Paper Count: 26

Search results for: nafion

26 Nafion Nanofiber Composite Membrane Fabrication for Fuel Cell Applications

Authors: C. N. Okafor, M. Maaza, T. A. E. Mokrani

Abstract:

A proton exchange membrane has been developed for Direct Methanol Fuel Cell (DMFC). The nanofiber network composite membranes were prepared by interconnected network of Nafion (perfuorosulfonic acid) nanofibers that have been embedded in an uncharged and inert polymer matrix, by electro-spinning. The spinning solution of Nafion with a low concentration (1 wt. % compared to Nafion) of high molecular weight poly(ethylene oxide), as a carrier polymer. The interconnected network of Nafion nanofibers with average fiber diameter in the range of 160-700nm, were used to make the membranes, with the nanofiber occupying up to 85% of the membrane volume. The matrix polymer was cross-linked with Norland Optical Adhesive 63 under UV. The resulting membranes showed proton conductivity of 0.10 S/cm at 25°C and 80% RH; and methanol permeability of 3.6 x 10-6 cm2/s.

Keywords: composite membrane, electrospinning, fuel cell, nanofibers

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25 Development and Characterization of a Polymer Composite Electrolyte to Be Used in Proton Exchange Membranes Fuel Cells

Authors: B. A. Berns, V. Romanovicz, M. M. de Camargo Forte, D. E. O. S. Carpenter

Abstract:

The Proton Exchange Membranes (PEM) are largely studied because they operate at low temperatures and they are suitable for mobile applications. However, There are some deficiencies in their operation, Mainly those that use ethanol as a hydrogen source that require a certain attention. Therefore, This research aimed to develop Nafion® composite membranes, Mixing clay minerals, Kaolin and halloysite to the polymer matrix in order to improve the ethanol molecule retentions and at the same time to keep the system’s protonic conductivity. The modified Nafion/Kaolin, Nafion/Halloysite composite membranes were prepared in weight proportion of 0.5, 1.0 and 1.5. The membranes obtained were characterized as to their ethanol permeability, Protonic conductivity and water absorption. The composite morphology and structure are characterized by SEM and EDX and also the thermal behavior is determined by TGA and DSC. The analysis of the results shows ethanol permeability reduction from 48% to 63%. However, The protonic conductivity results are lower in relation to pure Nafion®. As to the thermal behavior, The Nafion® composite membranes were stable up to a temperature of 325ºC.

Keywords: Polymer-matrix composites (PMCs), thermal properties, nanoclay, differential scanning calorimetry

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24 Nafion Nanofiber Mat in a Single Fuel Cell Test

Authors: Chijioke Okafor, Malik Maaza, Touhami Mokrani

Abstract:

Proton exchange membrane, PEM was developed and tested for potential application in fuel cell. Nafion was electrospun to nanofiber network with the aid of poly(ethylene oxide), PEO, as a carrier polymer. The matrix polymer was crosslinked with Norland Optical Adhesive 63 under UV after compacting and annealing. The welded nanofiber mat was characterized for morphology, proton conductivity, and methanol permeability, then tested in a single cell test station. The results of the fabricated nanofiber membrane showed a proton conductivity of 0.1 S/cm at 25 oC and higher fiber volume fraction; methanol permeability of 3.6x10^-6 cm2/s and power density of 96.1 and 81.2 mW/cm2 for 5M and 1M methanol concentration respectively.

Keywords: fuel cell, nafion, nanofiber, permeability

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23 Preparation and Performance of Polyphenylene Oxide-Based Anion Exchange Membrane for Vanadium Redox Flow Battery

Authors: Mi-Jung Park, Min-Hwa Lim, Ho-Young Jung

Abstract:

A polyphenylene oxide (PPO)-based anion exchange membrane based on the functionalization of bromomethylated PPO using 1-methylimdazole was fabricated for vanadium redox flow application. The imidazolium-bromomethylated PPO (Im-bPPO) showed lower permeability VO2+ ions (2.9×10⁻¹⁴ m²/sec), compared to Nafion 212 (2.3×10⁻¹² m²/sec) and FAP-450 (7.9×10⁻¹⁴ m²/sec). Even though the Im-bPPO membrane has higher permeability, the energy efficiency of the VRFB with the Im-bPPO membrane was slightly lower than that of Nafion and FAP-450. The Im-bPPO membrane exhibits good voltage efficiency compared to FAP-450 and Nafion 212 because of its better ion conductivity. The Im-bPPo membrane showed up good performance, but a decline in performance at later cycles was observed.

Keywords: anion exchange membranes, vanadium redox flow battery, polyphenylene oxide, energy efficiency (EE)

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22 Influence of Electrode Assembly on Catalytic Activation and Deactivation of a PT Film Immobilized H+ Conducting Solid Electrolyte in Electrocatalytic Reduction Reactions

Authors: M. A. Hasnat, M. Amirul Islam, M. A. Rashed, Jamil. Safwan, M. Mahabubul Alam

Abstract:

Symmetric (Cu–Pt|Nafion|Pt–Cu) and asymmetric(Pt|Nafion|Pt–Cu) assemblies were fabricated to study the nitrate reduction processes at the cathode. The electrocatalytic nitrate reduction reactions were performed in these assemblies in order to investigate the prerequisite for the enhanced catalytic activity, electrochemical cell durability as well as preferable product selectivity resulting from the reduction of nitrate at the cathode. It has been observed for the symmetric assembly that Cu particles were oxidized on the anode surface under an applied potential and the resulting copper ions migrated to the cathode surface through the Nafion membrane, which deposited as copper oxide on the cathode surface. The formation of this copper oxide covering layer on the Pt–Cu cathode surface is attributed as the reason for the deactivation of the cathode that governed the reduced nitrate reduction along with increasing nitrite selectivity. These problems were addressed and resolved with the asymmetric design of the electrocatalytic reactor, where enhanced hydrogen evolution activates the surface by eroding the CuO over layer as well as speeding up the slow rate determining hydrogenation reactions.

Keywords: membrane, nitrate, electrocatalysis, voltammetry, electrolysis

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21 Nafion Multiwalled Carbon Nano Tubes Composite Film Modified Glassy Carbon Sensor for the Voltammetric Estimation of Dianabol Steroid in Pharmaceuticals and Biological Fluids

Authors: Nouf M. Al-Ourfi, A. S. Bashammakh, M. S. El-Shahawi

Abstract:

The redox behavior of dianabol steroid (DS) on Nafion Multiwalled Carbon nano -tubes (MWCNT) composite film modified glassy carbon electrode (GCE) in various buffer solutions was studied using cyclic voltammetry (CV) and differential pulse- adsorptive cathodic stripping voltammetry (DP-CSV) and successfully compared with the results at non modified bare GCE. The Nafion-MWCNT composite film modified GCE exhibited the best electrochemical response among the two electrodes for the electro reduction of DS that was inferred from the EIS, CV and DP-CSV. The modified sensor showed a sensitive, stable and linear response in the concentration range of 5 – 100 nM with a detection limit of 0.08 nM. The selectivity of the proposed sensor was assessed in the presence of high concentration of major interfering species. The analytical application of the sensor for the quantification of DS in pharmaceutical formulations and biological fluids (urine) was determined and the results demonstrated acceptable recovery and RSD of 5%. Statistical treatment of the results of the proposed method revealed no significant differences in the accuracy and precision. The relative standard deviations for five measurements of 50 and 300 ng mL−1 of DS were 3.9 % and 1.0 %, respectively.

Keywords: dianabol steroid, determination, modified GCE, urine

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20 Molecular Dynamics Studies of Main Factors Affecting Mass Transport Phenomena on Cathode of Polymer Electrolyte Membrane Fuel Cell

Authors: Jingjing Huang, Nengwei Li, Guanghua Wei, Jiabin You, Chao Wang, Junliang Zhang

Abstract:

In this work, molecular dynamics (MD) simulation is applied to analyze the mass transport process in the cathode of proton exchange membrane fuel cell (PEMFC), of which all types of molecules situated in the cathode is considered. a reasonable and effective MD simulation process is provided, and models were built and compared using both Materials Studio and LAMMPS. The mass transport is one of the key issues in the study of proton exchange membrane fuel cells (PEMFCs). In this report, molecular dynamics (MD) simulation is applied to analyze the influence of Nafion ionomer distribution and Pt nano-particle size on mass transport process in the cathode. It is indicated by the diffusion coefficients calculation that a larger quantity of Nafion, as well as a higher equivalent weight (EW) value, will hinder the transport of oxygen. In addition, medium-sized Pt nano-particles (1.5~2nm) are more advantageous in terms of proton transport compared with other particle sizes (0.94~2.55nm) when the center-to-center distance between two Pt nano-particles is around 5 nm. Then mass transport channels are found to be formed between the hydrophobic backbone and the hydrophilic side chains of Nafion ionomer according to the radial distribution function (RDF) curves. And the morphology of these channels affected by the Pt size is believed to influence the transport of hydronium ions and, consequently the performance of PEMFC.

Keywords: cathode catalytic layer, mass transport, molecular dynamics, proton exchange membrane fuel cell

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19 Synthesis and Characterization of Sulfonated Aromatic Hydrocarbon Polymers Containing Trifluoromethylphenyl Side Chain for Proton Exchange Membrane Fuel Cell

Authors: Yi-Chiang Huang, Hsu-Feng Lee, Yu-Chao Tseng, Wen-Yao Huang

Abstract:

Proton exchange membranes as a key component in fuel cells have been widely studying over the past few decades. As proton exchange, membranes should have some main characteristics, such as good mechanical properties, low oxidative stability and high proton conductivity. In this work, trifluoromethyl groups had been introduced on polymer backbone and phenyl side chain which can provide densely located sulfonic acid group substitution and also promotes solubility, thermal and oxidative stability. Herein, a series of novel sulfonated aromatic hydrocarbon polyelectrolytes was synthesized by polycondensation of 4,4''''-difluoro-3,3''''- bis(trifluoromethyl)-2'',3''-bis(3-(trifluoromethyl)phenyl)-1,1':4',1'':4'',1''':4''',1''''-quinquephenyl with 2'',3''',5'',6''-tetraphenyl-[1,1':4',1'': 4'',1''':4''',1''''-quinquephenyl]-4,4''''-diol and post-sulfonated was through chlorosulfonic acid to given sulfonated polymers (SFC3-X) possessing ion exchange capacities ranging from 1.93, 1.91 and 2.53 mmol/g. ¹H NMR and FT-IR spectroscopy were applied to confirm the structure and composition of sulfonated polymers. The membranes exhibited considerably dimension stability (10-27.8% in length change; 24-56.5% in thickness change) and excellent oxidative stability (weight remain higher than 97%). The mechanical properties of membranes demonstrated good tensile strength on account of the high rigidity multi-phenylated backbone. Young's modulus were ranged 0.65-0.77GPa which is much larger than that of Nafion 211 (0.10GPa). Proton conductivities of membranes ranged from 130 to 240 mS/cm at 80 °C under fully humidified which were comparable or higher than that of Nafion 211 (150 mS/cm). The morphology of membranes was investigated by transmission electron microscopy which demonstrated a clear hydrophilic/hydrophobic phase separation with spherical ionic clusters in the size range of 5-20 nm. The SFC3-1.97 single fuel cell performance demonstrates the maximum power density at 1.08W/cm², and Nafion 211 was 1.24W/cm² as a reference in this work. The result indicated that SFC3-X are good candidates for proton exchange membranes in fuel cell applications. Fuel cell of other membranes is under testing.

Keywords: fuel cells, polyelectrolyte, proton exchange membrane, sulfonated polymers

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18 A Comparative Study: Influences of Polymerization Temperature on Phosphoric Acid Doped Polybenzimidazole Membranes

Authors: Cagla Gul Guldiken, Levent Akyalcin, Hasan Ferdi Gercel

Abstract:

Fuel cells are electrochemical devices which convert the chemical energy of hydrogen into the electricity. Among the types of fuel cells, polymer electrolyte membrane fuel cells (PEMFCs) are attracting considerable attention as non-polluting power generators with high energy conversion efficiencies in mobile applications. Polymer electrolyte membrane (PEM) is one of the essential components of PEMFCs. Perfluorosulfonic acid based membranes known as Nafion® is widely used as PEMs. Nafion® membranes water dependent proton conductivity which limits the operating temperature below 100ᵒC. At higher temperatures, proton conductivity and mechanical stability of these membranes decrease because of dehydration. Polybenzimidazole (PBI), which has good anhydrous proton conductivity after doped with acids, as well as excellent thermal stability, shows great potential in the application of high temperature PEMFCs. In the present study, PBI polymers were synthesized by solution polycondensation at 190 and 210ᵒC. The synthesized polymers were characterized by FTIR, 1H NMR, and TGA. Phosphoric acid doped PBI membranes were prepared and tested in a PEMFC. The influences of reaction temperature on structural properties of synthesized polymers were investigated. Mechanical properties, acid-doping level, proton conductivity, and fuel cell performances of prepared phosphoric acid doped PBI membranes were evaluated. The maximum power density was found as 32.5 mW/cm² at 120ᵒC.

Keywords: fuel cell, high temperature polymer electrolyte membrane, polybenzimidazole, proton exchange membrane fuel cell

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17 Development of Vacuum Planar Membrane Dehumidifier for Air-Conditioning

Authors: Chun-Han Li, Tien-Fu Yang, Chen-Yu Chen, Wei-Mon Yan

Abstract:

The conventional dehumidification method in air-conditioning system mostly utilizes a cooling coil to remove the moisture in the air via cooling the supply air down below its dew point temperature. During the process, it needs to reheat the supply air to meet the set indoor condition that consumes a considerable amount of energy and affect the coefficient of performance of the system. If the processes of dehumidification and cooling are separated and operated respectively, the indoor conditions will be more efficiently controlled. Therefore, decoupling the dehumidification and cooling processes in heating, ventilation and air conditioning system is one of the key technologies as membrane dehumidification processes for the next generation. The membrane dehumidification method has the advantages of low cost, low energy consumption, etc. It utilizes the pore size and hydrophilicity of the membrane to transfer water vapor by mass transfer effect. The moisture in the supply air is removed by the potential energy and driving force across the membrane. The process can save the latent load used to condense water, which makes more efficient energy use because it does not involve heat transfer effect. In this work, the performance measurements including the permeability and selectivity of water vapor and air with the composite and commercial membranes were conducted. According to measured data, we can choose the suitable dehumidification membrane for designing the flow channel length and components of the planar dehumidifier. The vacuum membrane dehumidification system was set up to examine the effects of temperature, humidity, vacuum pressure, flow rate, the coefficient of performance and other parameters on the dehumidification efficiency. The results showed that the commercial Nafion membrane has better water vapor permeability and selectivity. They are suitable for filtration with water vapor and air. Meanwhile, Nafion membrane has promising potential in the dehumidification process.

Keywords: vacuum membrane dehumidification, planar membrane dehumidifier, water vapour and air permeability, air conditioning

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16 Experimental and Characterization Studies on Micro Direct Methanol Fuel Cell

Authors: S. Muthuraja Soundrapandian, C.K. Subramaniam

Abstract:

A micro Direct Methanol Fuel Cell (DMFC) of 1 cm2 active area with selective sensor materials to sense methanol for redox, has been developed. Among different Pt alloys, Pt-Sn/C was able to produce high current density and repeatability. Membrane Elecctrode Assembly (MEA) of anode catalyst Pt-Sn/C was prepared with nafion as active membrane and Pt black as cathode catalyst. The sensor’s maximum ability to detect the trace levels of methanol in ppm has been analyzed. A compact sensor set up has also been made and the characterization studies were carried out. The acceptable value of current density was derived by the cell and the results are able to fulfill the needs of DMFC technology for the practical applications.

Keywords: DMFC, sensor, MEA, Pt-Sn

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15 Dual-Layer Microporous Layer of Gas Diffusion Layer for Proton Exchange Membrane Fuel Cells under Various RH Conditions

Authors: Grigoria Athanasaki, Veerarajan Vimala, A. M. Kannan, Louis Cindrella

Abstract:

Energy usage has been increased throughout the years, leading to severe environmental impacts. Since the majority of the energy is currently produced from fossil fuels, there is a global need for clean energy solutions. Proton Exchange Membrane Fuel Cells (PEMFCs) offer a very promising solution for transportation applications because of their solid configuration and low temperature operations, which allows them to start quickly. One of the main components of PEMFCs is the Gas Diffusion Layer (GDL), which manages water and gas transport and shows direct influence on the fuel cell performance. In this work, a novel dual-layer GDL with gradient porosity was prepared, using polyethylene glycol (PEG) as pore former, to improve the gas diffusion and water management in the system. The microporous layer (MPL) of the fabricated GDL consists of carbon powder PUREBLACK, sodium dodecyl sulfate as a surfactant, 34% wt. PTFE and the gradient porosity was created by applying one layer using 30% wt. PEG on the carbon substrate, followed by a second layer without using any pore former. The total carbon loading of the microporous layer is ~ 3 mg.cm-2. For the assembly of the catalyst layer, Nafion membrane (Ion Power, Nafion Membrane NR211) and Pt/C electrocatalyst (46.1% wt.) were used. The catalyst ink was deposited on the membrane via microspraying technique. The Pt loading is ~ 0.4 mg.cm-2, and the active area is 5 cm2. The sample was ex-situ characterized via wetting angle measurement, Scanning Electron Microscopy (SEM), and Pore Size Distribution (PSD) to evaluate its characteristics. Furthermore, for the performance evaluation in-situ characterization via Fuel Cell Testing using H2/O2 and H2/air as reactants, under 50, 60, 80, and 100% relative humidity (RH), took place. The results were compared to a single layer GDL, fabricated with the same carbon powder and loading as the dual layer GDL, and a commercially available GDL with MPL (AvCarb2120). The findings reveal high hydrophobic properties of the microporous layer of the GDL for both PUREBLACK based samples, while the commercial GDL demonstrates hydrophilic behavior. The dual layer GDL shows high and stable fuel cell performance under all the RH conditions, whereas the single layer manifests a drop in performance at high RH in both oxygen and air, caused by catalyst flooding. The commercial GDL shows very low and unstable performance, possibly because of its hydrophilic character and thinner microporous layer. In conclusion, the dual layer GDL with PEG appears to have improved gas diffusion and water management in the fuel cell system. Due to its increasing porosity from the catalyst layer to the carbon substrate, it allows easier access of the reactant gases from the flow channels to the catalyst layer, and more efficient water removal from the catalyst layer, leading to higher performance and stability.

Keywords: gas diffusion layer, microporous layer, proton exchange membrane fuel cells, relative humidity

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14 Garnet-based Bilayer Hybrid Solid Electrolyte for High-Voltage Cathode Material Modified with Composite Interface Enabler on Lithium-Metal Batteries

Authors: Kumlachew Zelalem Walle, Chun-Chen Yang

Abstract:

Solid-state lithium metal batteries (SSLMBs) are considered promising candidates for next-generation energy storage devices due to their superior energy density and excellent safety. However, recent findings have shown that the formation of lithium (Li) dendrites in SSLMBs still exhibits a terrible growth ability, which makes the development of SSLMBs have to face the challenges posed by the Li dendrite problem. In this work, an inorganic/organic mixture coating material (g-C3N4/ZIF-8/PVDF) was used to modify the surface of lithium metal anode (LMA). Then the modified LMA (denoted as g-C₃N₄@Li) was assembled with lithium nafion (LiNf) coated commercial NCM811 (LiNf@NCM811) using a bilayer hybrid solid electrolyte (Bi-HSE) that incorporated 20 wt.% (vs. polymer) LiNf coated Li6.05Ga0.25La3Zr2O11.8F0.2 ([email protected]) filler faced to the positive electrode and the other layer with 80 wt.% (vs. polymer) filler content faced to the g-C₃N₄@Li. The garnet-type Li6.05Ga0.25La3Zr2O11.8F0.2 (LG0.25LZOF) solid electrolyte was prepared via co-precipitation reaction process from Taylor flow reactor and modified using lithium nafion (LiNf), a Li-ion conducting polymer. The Bi-HSE exhibited high ionic conductivity of 6.8  10–4 S cm–1 at room temperature, and a wide electrochemical window (0–5.0 V vs. Li/Li+). The coin cell was charged between 2.8 to 4.5 V at 0.2C and delivered an initial specific discharge capacity of 194.3 mAh g–1 and after 100 cycles it maintained 81.8% of its initial capacity at room temperature. The presence of a nano-sheet g-C3N4/ZIF-8/PVDF as a composite coating material on the LMA surface suppress the dendrite growth and enhance the compatibility as well as the interfacial contact between anode/electrolyte membrane. The g-C3N4@Li symmetrical cells incorporating this hybrid electrolyte possessed excellent interfacial stability over 1000 h at 0.1 mA cm–2 and a high critical current density (1 mA cm–2). Moreover, the in-situ formation of Li3N on the solid electrolyte interface (SEI) layer as depicted from the XPS result also improves the ionic conductivity and interface contact during the charge/discharge process. Therefore, these novel multi-layered fabrication strategies of hybrid/composite solid electrolyte membranes and modification of the LMA surface using mixed coating materials have potential applications in the preparation of highly safe high-voltage cathodes for SSLMBs.

Keywords: high-voltage cathodes, hybrid solid electrolytes, garnet, graphitic-carbon nitride (g-C3N4), ZIF-8 MOF

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13 Correlation between Defect Suppression and Biosensing Capability of Hydrothermally Grown ZnO Nanorods

Authors: Mayoorika Shukla, Pramila Jakhar, Tejendra Dixit, I. A. Palani, Vipul Singh

Abstract:

Biosensors are analytical devices with wide range of applications in biological, chemical, environmental and clinical analysis. It comprises of bio-recognition layer which has biomolecules (enzymes, antibodies, DNA, etc.) immobilized over it for detection of analyte and transducer which converts the biological signal into the electrical signal. The performance of biosensor primarily the depends on the bio-recognition layer and therefore it has to be chosen wisely. In this regard, nanostructures of metal oxides such as ZnO, SnO2, V2O5, and TiO2, etc. have been explored extensively as bio-recognition layer. Recently, ZnO has the attracted attention of researchers due to its unique properties like high iso-electric point, biocompatibility, stability, high electron mobility and high electron binding energy, etc. Although there have been many reports on usage of ZnO as bio-recognition layer but to the authors’ knowledge, none has ever observed correlation between optical properties like defect suppression and biosensing capability of the sensor. Here, ZnO nanorods (ZNR) have been synthesized by a low cost, simple and low-temperature hydrothermal growth process, over Platinum (Pt) coated glass substrate. The ZNR have been synthesized in two steps viz. initially a seed layer was coated over substrate (Pt coated glass) followed by immersion of it into nutrient solution of Zinc nitrate and Hexamethylenetetramine (HMTA) with in situ addition of KMnO4. The addition of KMnO4 was observed to have a profound effect over the growth rate anisotropy of ZnO nanostructures. Clustered and powdery growth of ZnO was observed without addition of KMnO4, although by addition of it during the growth, uniform and crystalline ZNR were found to be grown over the substrate. Moreover, the same has resulted in suppression of defects as observed by Normalized Photoluminescence (PL) spectra since KMnO4 is a strong oxidizing agent which provides an oxygen rich growth environment. Further, to explore the correlation between defect suppression and biosensing capability of the ZNR Glucose oxidase (Gox) was immobilized over it, using physical adsorption technique followed by drop casting of nafion. Here the main objective of the work was to analyze effect of defect suppression over biosensing capability, and therefore Gox has been chosen as model enzyme, and electrochemical amperometric glucose detection was performed. The incorporation of KMnO4 during growth has resulted in variation of optical and charge transfer properties of ZNR which in turn were observed to have deep impact on biosensor figure of merits. The sensitivity of biosensor was found to increase by 12-18 times, due to variations introduced by addition of KMnO4 during growth. The amperometric detection of glucose in continuously stirred buffer solution was performed. Interestingly, defect suppression has been observed to contribute towards the improvement of biosensor performance. The detailed mechanism of growth of ZNR along with the overall influence of defect suppression on the sensing capabilities of the resulting enzymatic electrochemical biosensor and different figure of merits of the biosensor (Glass/Pt/ZNR/Gox/Nafion) will be discussed during the conference.

Keywords: biosensors, defects, KMnO4, ZnO nanorods

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12 Chemical Stability and Characterization of Ion Exchange Membranes for Vanadium Redox Flow Batteries

Authors: Min-Hwa Lim, Mi-Jeong Park, Ho-Young Jung

Abstract:

Imidazolium-brominated polyphenylene oxide (Im-bPPO) is based on the functionalization of bromomethylated poly(2,6-dimethyl-1,4-phenylene oxide) (BPPO) using 1-Methylimdazole. For the purpose of long cycle life of vanadium redox battery (VRB), the chemical stability of Im-bPPO, sPPO (sulfonated 2,6-dimethyl-1,4-phenylene oxide) and Fumatech membranes were evaluated firstly in the 0.1M vanadium (V) solution dissolved in 3M sulfuric acid (H2SO4) for 72h, and UV analyses of the degradation products proved that ether bond in PPO backbone was vulnerable to be attacked by vanadium (V) ion. It was found that the membranes had slightly weight loss after soaking in 2 ml distilled water included in STS pressure vessel for 1 day at 200◦C. ATR-FT-IR data indicated before and after the degradation of the membranes. Further evaluation on the degradation mechanism of the menbranes were carried out in Fenton’s reagent solution for 72 h at 50 ◦C and analyses of the membranes before and after degradation confirmed the weight loss of the membranes. The Fumatech membranes exhibited better performance than AEM and CEM, but Nafion 212 still suffers chemical degradation.

Keywords: vanadium redox flow battery, ion exchange membrane, permeability, degradation, chemical stability

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11 Synthesis and Characterization of SiO2/PVA/ SPEEK Composite Membrane for Proton Exchange Membrane Fuel Cell

Authors: M. Yusuf Ansari, Asad Abbas

Abstract:

Proton exchange membrane (PEM) fuel cell is a very efficient and promising energy conversion device. Although Nafion® is considered as benchmark materials for membrane used in PEM fuel cell, it has limitations that restrict its uses. Alternative materials for the membrane is always a challenging field for researchers. Sulfonated poly(ether ether ketone) (SPEEK) is one of the promising material for membrane due to its chemical and mechanical stability and lower cost. In this work, SPEEK is synthesized, and property booster such as silica nanoparticles and polyvinyl alcohol (PVA) are also added to analyse changes in properties such as water uptake, IEC, and conductivity. It has been found that adding PVA support high water uptake and proton conductivity but at large amount of PVA reduces the proton conductivity due to very high water uptake. Adding silica enhances water uptake and proton conductivity.

Keywords: PEM Membrane, sulfonated poly (ether ether ketone) (SPEEK), silica fumes (SiO2), polyvinyl alcohol (PVA)

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10 Ionic Polymer Actuators with Fast Response and High Power Density Based on Sulfonated Phthalocyanine/Sulfonated Polysulfone Composite Membrane

Authors: Taehoon Kwon, Hyeongrae Cho, Dirk Henkensmeier, Youngjong Kang, Chong Min Koo

Abstract:

Ionic polymer actuators have been of interest in the bio-inspired artificial muscle devices. However, the relatively slow response and low power density were the obstacles for practical applications. In this study, ionic polymer actuators are fabricated with ionic polymer composite membranes based on sulfonated poly(arylene ether sulfone) (SPAES) and copper(II) phthalocyanine tetrasulfonic acid (CuPCSA). CuPCSA is an organic filler with very high ion exchange capacity (IEC, 4.5 mmol H+/g) that can be homogeneously dispersed on the molecular scale into the SPAES membrane. SPAES/CuPCSA actuators show larger ionic conductivity, mechanical properties, bending deformation, exceptional faster response to electrical stimuli, and larger mechanical power density (3028 W m–3) than Nafion actuators. This outstanding actuation performance of SPAES/CuPCSA composite membrane actuators makes them attractive for next generation transducers with high power density, which are currently developed biomimetic devices such as endoscopic surgery.

Keywords: actuation performance, composite membranes, ionic polymer actuators, organic filler

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9 A Saltwater Battery Inspired by the Membrane Potential Found in Biological Cells

Authors: Ross Lee, Pritpal Singh, Andrew Jester

Abstract:

As the world transitions to a more sustainable energy economy, the deployment of energy storage technologies is expected to increase to develop a more resilient grid system. However, current technologies are associated with various environmental and safety issues throughout their entire lifecycle; therefore, new battery technology is necessary for grid applications to curtail these risks. Biological cells, such as human neurons and electrolytes in the electric eel, can serve as a more sustainable design template for a new bio-inspired (i.e., biomimetic) battery. Within biological cells, an electrochemical gradient across the cell membrane forms the membrane potential, which serves as the driving force for ion transport into/out of the cell, akin to the charging/discharging of a battery cell. This work serves as the first step to developing such a biomimetic battery cell, starting with the fabrication and characterization of ion-selective membranes to facilitate ion transport through the cell. Performance characteristics (e.g., cell voltage, power density, specific energy, roundtrip efficiency) for the cell under investigation are compared to incumbent battery technologies and biological cells to assess the readiness level for this emerging technology. Using a Na⁺-Form Nafion-117 membrane, the cell in this work successfully demonstrated behavior similar to human neurons; these findings will inform how cell components can be re-engineered to enhance device performance.

Keywords: battery, biomimetic, electrolytes, human neurons, ion-selective membranes, membrane potential

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8 AC Electro-Kinetics, Bipolar Current and Concentration-Polarization in a Microchannel-Nafion Membrane System

Authors: Sinwook Park, Gilad Yossifon

Abstract:

The presence of a floating electrode array located within the depletion layer formed due to concentration-polarization (CP) across a microchannel-membrane device, produces not only induced-charge electro-osmosis (ICEO) vortex and but also a bipolar current resulting from faradaic reactions. It has been shown that there exists an optimal SiO2 layer thickness of ~50nm which is sufficient to suppress bipolar currents (at least up to 5V applied voltage) but still enables ICEO vortices that stir the depletion layer, thereby affecting its I-V response. This effect is pronounced beyond the limiting current where the existence of the depletion layer results in increased local electric field due to decreased solution conductivity. This comprehensive study of the interaction of embedded electrodes with the induced CP in microchannel-perm selective medium systems, allows one to choose the thickness of the thin dielectric coating to either enhance the mixing as a means to control the diffuse layer, or suppress it, for example, in the case where electrodes are intended for local measurements of the solution conductivity with minimal invasion. In addition, the use of alternating-current electro-osmosis by activating electrodes results in further enhancement of the fluid stirring and opens new routes for on-demand spatiotemporal control of the CP length. In addition, the use of embedded heaters within the depletion layer generates electro-thermal vortices that in turn also control the CP length.

Keywords: AC electrokinetics, microchannel, concentration-polarization, bipolar current

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7 Effect of Synthesis Parameters on Crystal Size and Perfection of Mordenite and Analcime

Authors: Zehui Du, Chaiwat Prapainainar, Paisan Kongkachuichay, Paweena Prapainainar

Abstract:

The aim of this work was to obtain small crystalline size and high crystallinity of mordenites and analcimes, by modifying the aging time, agitation, water content, crystallization temperature and crystallization time. Two different hydrothermal methods were studied. Both methods used Na2SiO3 as the silica source, NaAlO2 as the aluminum source, and NaOH as the alkali source. The first method used HMI as the template while the second method did not use the template. Mordenite crystals with spherical shape and bimodal in size of about 1 and 5 µm were obtained from the first method using conditions of 24 hr aging time, 170°C and 24 hr crystallization. Modernites with high crystallinity were formed using agitation system in the crystallization process. It was also found that the aging time of 2 hr and 24 hr did not much affect the formation of mordenite crystals. Analcime crystals were formed in spherical shape and facet on surface with the size between 13-15 µm by the second method using the conditions of 30 minutes aging time, 170°C and 24 hr crystallization without calcination. By increasing water content, the crystallization process was slowed down and resulted in smaller analcime crystals. Larger size of analcime crystals were observed when the samples were calcined at 300°C and 580°C. Higher calcination temperature led to higher crystal growth and resulted in larger crystal size. Finally, mordenite and analcime was used as fillers in zeolite/Nafion composite membrane to solve the fuel cross over problem in direct alcohol fuel cell.

Keywords: analcime, hydrothermal synthesis, mordenite, zeolite

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6 Amperometric Biosensor for Glucose Determination Based on a Recombinant Mn Peroxidase from Corn Cross-linked to a Gold Electrode

Authors: Anahita Izadyar, My Ni Van, Kayleigh Amber Rodriguez, Ilwoo Seok, Elizabeth E. Hood

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Using a recombinant enzyme derived from corn and a simple modification, we fabricated a facile, fast, and cost-beneficial biosensor to measure glucose. The Nafion/ Plant Produced Mn Peroxidase (PPMP)– glucose oxidase (GOx)- Bovine serum albumin (BSA) /Au electrode showed an excellent amperometric response to detect glucose. This biosensor is capable of responding to a wide range of glucose—20.0 µM−15.0 mM and has a lower detection limit (LOD) of 2.90µM. The reproducibility response using six electrodes is also very substantial and indicates the high capability of this biosensor to detect a wide range of 3.10±0.19µM to 13.2±1.8 mM glucose concentration. Selectivity of this electrode was investigated in an optimized experimental solution contains 10% diet green tea with citrus containing ascorbic acid (AA), and citric acid (CA) in a wide concentration of glucose at 0.02 to 14.0mM with an LOD of 3.10µM. Reproducibility was also investigated using 4 electrodes in this sample and shows notable results in the wide concentration range of 3.35±0.45µM to of 13.0 ± 0.81 mM. We also used other voltammetry methods to evaluate this biosensor. We applied linear sweep voltammetry (LSV) and this technique shows a wide range of 0.10−15.0 mM to detect glucose with a lower detection limit of 19.5µM. The performance and strength of this enzyme biosensor were the simplicity, wide linear ranges, sensitivities, selectivity, and low limits of detection. We expect that the modified biosensor has the potential for monitoring various biofluids.

Keywords: plant-produced manganese peroxidase, enzyme-based biosensors, glucose, modified gold electrode, glucose oxidase

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5 Polymer Nanostructures Based Catalytic Materials for Energy and Environmental Applications

Authors: S. Ghosh, L. Ramos, A. N. Kouamé, A.-L. Teillout, H. Remita

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Catalytic materials have attracted continuous attention due to their promising applications in a variety of energy and environmental applications including clean energy, energy conversion and storage, purification and separation, degradation of pollutants and electrochemical reactions etc. With the advanced synthetic technologies, polymer nanostructures and nanocomposites can be directly synthesized through soft template mediated approach using swollen hexagonal mesophases and modulate the size, morphology, and structure of polymer nanostructures. As an alternative to conventional catalytic materials, one-dimensional PDPB polymer nanostructures shows high photocatalytic activity under visible light for the degradation of pollutants. These photocatalysts are very stable with cycling. Transmission electron microscopy (TEM), and AFM-IR characterizations reveal that the morphology and structure of the polymer nanostructures do not change after photocatalysis. These stable and cheap polymer nanofibers and metal polymer nanocomposites are easy to process and can be reused without appreciable loss of activity. The polymer nanocomposites formed via one pot chemical redox reaction with 3.4 nm Pd nanoparticles on poly(diphenylbutadiyne) (PDPB) nanofibers (30 nm). The reduction of Pd (II) ions is accompanied by oxidative polymerization leading to composites materials. Hybrid Pd/PDPB nanocomposites used as electrode materials for the electrocatalytic oxidation of ethanol without using support of proton exchange Nafion membrane. Hence, these conducting polymer nanofibers and nanocomposites offer the perspective of developing a new generation of efficient photocatalysts for environmental protection and in electrocatalysis for fuel cell applications.

Keywords: conducting polymer, swollen hexagonal mesophases, solar photocatalysis, electrocatalysis, water depollution

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4 Effect of N2-cold Plasma Treatment of Carbon Supports on the Activity of Pt3Pd3Sn2/C Towards the Dimethyl Ether Oxidation

Authors: Medhanie Gebremedhin Gebru, Alex Schechter

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Dimethyl ether (DME) possesses several advantages over other small organic molecules such as methanol, ethanol, and ammonia in terms of providing higher energy density, being less toxic, and having lower Nafion membrane crossover. However, the absence of an active and stable catalyst has been the bottleneck that hindered the commercialization of direct DME fuel cells. A Vulcan XC72 carbon-supported ternary metal catalyst, Pt₃Pd₃Sn₂/C is reported to have yielded the highest specific power density (90 mW mg-¹PGM) as compared to other catalysts tested fordirect DME fuel cell (DDMEFC). However, the micropores and sulfur groups present in Vulcan XC72 hinder the fuel utilization by causing Pt agglomeration and sulfur poisoning. Vulcan XC72 having a high carbon sp³ hybridization content, is also prone to corrosion. Therefore, carbon supports such as multi-walled carbon nanotube (MWCNT), black pearl 2000 (BP2000), and their cold N2 plasma-treated counterpartswere tested to further enhance the activity of the catalyst, and the outputs with these carbons were compared with the originally used support. Detailed characterization of the pristine and carbon supports was conducted. Electrochemical measurements in three-electrode cells and laboratory prototype fuel cells were conducted.Pt₃Pd₃Sn₂/BP2000 exhibited excellent performance in terms of electrochemical active surface area (ECSA), peak current density (jp), and DME oxidation charge (Qoxi). The effect of the plasma activation on the activity improvement was observed only in the case of MWCNT while having little or no effect on the other carbons. A Pt₃Pd₃Sn₂ supported on the optimized mixture of carbons containing 75% plasma-activated MWCNT and 25% BP2000 (Pt₃Pd₃Sn₂/75M25B) provided the highest reported power density of 117 mW mg-1PGM using an anode loading of1.55 mgPGMcm⁻².

Keywords: DME, DDMEFC, ternary metal catalyst, carbon support, plasma activation

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3 Influence of a Cationic Membrane in a Double Compartment Filter-Press Reactor on the Atenolol Electro-Oxidation

Authors: Alan N. A. Heberle, Salatiel W. Da Silva, Valentin Perez-Herranz, Andrea M. Bernardes

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Contaminants of emerging concern are substances widely used, such as pharmaceutical products. These compounds represent risk for both wild and human life since they are not completely removed from wastewater by conventional wastewater treatment plants. In the environment, they can be harm even in low concentration (µ or ng/L), causing bacterial resistance, endocrine disruption, cancer, among other harmful effects. One of the most common taken medicine to treat cardiocirculatory diseases is the Atenolol (ATL), a β-Blocker, which is toxic to aquatic life. In this way, it is necessary to implement a methodology, which is capable to promote the degradation of the ATL, to avoid the environmental detriment. A very promising technology is the advanced electrochemical oxidation (AEO), which mechanisms are based on the electrogeneration of reactive radicals (mediated oxidation) and/or on the direct substance discharge by electron transfer from contaminant to electrode surface (direct oxidation). The hydroxyl (HO•) and sulfate (SO₄•⁻) radicals can be generated, depending on the reactional medium. Besides that, at some condition, the peroxydisulfate (S₂O₈²⁻) ion is also generated from the SO₄• reaction in pairs. Both radicals, ion, and the direct contaminant discharge can break down the molecule, resulting in the degradation and/or mineralization. However, ATL molecule and byproducts can still remain in the treated solution. On this wise, some efforts can be done to implement the AEO process, being one of them the use of a cationic membrane to separate the cathodic (reduction) from the anodic (oxidation) reactor compartment. The aim of this study is investigate the influence of the implementation of a cationic membrane (Nafion®-117) to separate both cathodic and anodic, AEO reactor compartments. The studied reactor was a filter-press, with bath recirculation mode, flow 60 L/h. The anode was an Nb/BDD2500 and the cathode a stainless steel, both bidimensional, geometric surface area 100 cm². The solution feeding the anodic compartment was prepared with ATL 100 mg/L using Na₂SO₄ 4 g/L as support electrolyte. In the cathodic compartment, it was used a solution containing Na₂SO₄ 71 g/L. Between both solutions was placed the membrane. The applied currents densities (iₐₚₚ) of 5, 20 and 40 mA/cm² were studied over 240 minutes treatment time. Besides that, the ATL decay was analyzed by ultraviolet spectroscopy (UV/Vis). The mineralization was determined performing total organic carbon (TOC) in TOC-L CPH Shimadzu. In the cases without membrane, the iₐₚₚ 5, 20 and 40 mA/cm² resulted in 55, 87 and 98 % ATL degradation at the end of treatment time, respectively. However, with membrane, the degradation, for the same iₐₚₚ, was 90, 100 and 100 %, spending 240, 120, 40 min for the maximum degradation, respectively. The mineralization, without membrane, for the same studied iₐₚₚ, was 40, 55 and 72 %, respectively at 240 min, but with membrane, all tested iₐₚₚ reached 80 % of mineralization, differing only in the time spent, 240, 150 and 120 min, for the maximum mineralization, respectively. The membrane increased the ATL oxidation, probably due to avoid oxidant ions (S₂O₈²⁻) reduction on the cathode surface.

Keywords: contaminants of emerging concern, advanced electrochemical oxidation, atenolol, cationic membrane, double compartment reactor

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2 Performance Optimization of Polymer Materials Thanks to Sol-Gel Chemistry for Fuel Cells

Authors: Gondrexon, Gonon, Mendil-Jakani, Mareau

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Proton Exchange Membrane Fuel Cells (PEMFCs) seems to be a promising device used for converting hydrogen into electricity. PEMFC is made of a Membrane Electrode Assembly (MEA) composed of a Proton Exchange Membrane (PEM) sandwiched by two catalytic layers. Nowadays, specific performances are targeted in order to ensure the long-term expansion of this technology. Current polymers used (perfluorinated as Nafion®) are unsuitable (loss of mechanical properties) for the high-temperature range. To overcome this issue, sulfonated polyaromatic polymers appear to be a good alternative since it has very good thermomechanical properties. However, their proton conductivity and chemical stability (oxidative resistance to H2O2 formed during fuel cell (FC) operating) are very low. In our team, we patented an original concept of hybrid membranes able to fulfill the specific requirements for PEMFC. This idea is based on the improvement of commercialized polymer membrane via an easy and processable stabilization thanks to sol-gel (SG) chemistry with judicious embeded chemical functions. This strategy is thus breaking up with traditional approaches (design of new copolymers, use of inorganic charges/additives). In 2020, we presented the elaboration and functional properties of a 1st generation of hybrid membranes with promising performances and durability. The latter was made by self-condensing a SG phase with 3(mercaptopropyl)trimethoxysilane (MPTMS) inside a commercial sPEEK host membrane. The successful in-situ condensation reactions of the MPTMS was demonstrated by measures of mass uptakes, FTIR spectroscopy (presence of C-Haliphatics) and solid state NMR 29Si (T2 & T3 signals of self-condensation products). The ability of the SG phase to prevent the oxidative degradation of the sPEEK phase (thanks to thiol chemical functions) was then proved with H2O2 accelerating tests and FC operating tests. A 2nd generation made of thiourea functionalized SG precursors (named HTU & TTU) was made after. By analysing in depth the morphologies of these different hybrids by direct space analysis (AFM/SEM/TEM) and reciprocal space analysis (SANS/SAXS/WAXS), we highlighted that both SG phase morphology and its localisation into the host has a huge impact on the PEM functional properties observed. This relationship is also dependent on the chemical function embedded. The hybrids obtained have shown very good chemical resistance during aging test (exposed to H2O2) compared to the commercial sPEEK. But the chemical function used is considered as “sacrificial” and cannot react indefinitely with H2O2. Thus, we are now working on a 3rd generation made of both sacrificial/regenerative chemical functions which are expected to inhibit the chemical aging of sPEEK more efficiently. With this work, we are confident to reach a predictive approach of the key parameters governing the final properties.

Keywords: fuel cells, ionomers, membranes, sPEEK, chemical stability

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1 Beyond Power Density: Unexpected Scaling-Laws in Reverse-Electro-Dialysis Membrane Characterization Question the Relevance of Measurement Protocols

Authors: Timothee Derkenne, Annie Colin, Corentin Tregouet

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Due to the rising energy demand and the severe environmental crisis, a worldwide reduction of conventional fossil fuel consumption is needed. As a renewable and clean energy resource, blue energy is osmotic energy released during the mixing procedure of solutions of different salinity. Naturally, an irreversible mixing of river water and sea water happens at the estuary. A precise and engineering control of this mixing enables blue energy harvesting. The worldwide salinity gradient energy could reach 2.4-2.6 TW, which is comparable to the daily power demand over the globe. Since the beginning of blue-energy harvesting research, a lot of advances have been made in membrane design and nanofluidic diffusion-osmotic transport, but the efficiency gap of 6 orders of magnitude between nano-scale designs and industrial power plants remains unsolved. Just after synthesis, selective membranes are benchmarked on very small samples on the basis of the output power. It is usually calculated based on the membrane resistance per unit area and the measured Donnan potential. This method of power per unit area based on membrane resistance is, therefore, a key point to compare several devices and their efficiency. A classical electrochemical cell has been used to place a Nafion selective membrane of varying area between two electrodes. The membrane resistance and power density have been experimentally measured. Homogeneous salt concentration or gradient of concentration have been used to measure different parameters. This systematic study shows that for classical measurement cells, the membrane resistance is inversely proportional to the square root of its area. Whereas it's currently assumed in the literature that the resistance and the area of a membrane are inversely proportional. This assumption leads to a power density independent of the measurement. That’s why it is used as a criterion to compare membranes and devices. This result has a big impact on the reliability of the power density announced in the literature for different devices: the smaller the area of the tested membrane, the higher the output power density from 0,5 W/m² to 150 W/m² for the same membrane (salt ratio of 100). This leads to overly optimistic extrapolation of electrical performances for membranes engineered and tested at sub-millimeter sizes that will be industrially used at meter sizes. The results are explained by a theoretical modeling that describes the effect of the access resistance at the scale of the membrane. It shows why the area mismatch between the membrane and the electrodes could add a new resistance in the system that wasn’t taken into account before. Experimental data and theoretical modeling are corroborating without any adjustment parameters. Consequently, the power per unit area obtained at the micro-scale cannot be extrapolated a priori to larger membranes. So, the comparison is biased between large-scale commercially available membranes and nano-engineered microscale membranes. This raises the urgent need for new indicators or standard measurement protocols. Based on this work, a few recommendations are formulated to perform scalable and meaningful measurements of membrane resistance and power density.

Keywords: blue energy, nanofluidics, selective membrane, access resistance

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