Proton Conductivity Of Membranes Research Articles

Highly sulfonated poly ether ether ketone chelated with Cu2+ as a proton exchange membrane at sub-zero temperatures

Improving the proton conductivity (σ) of proton exchange membranes at low temperatures is very important for expanding their application areas. Here, sulfonated poly ether ether ketone (SPEEK) membranes were prepared with different sulfonation degrees, and its maximum ion exchange capacity is 3.15 mmol/g for 10 h at 60 °C. Highly sulfonated SPEEK membrane exhibits ultra-high water uptake and excellent proton conductivity of 0.074 S/cm at −25 °C due to its abundant −SO3H. Nevertheless, its high swelling ratio and low mechanical strength are not conducive to the practical application of the membrane. Luckily, by employing the chelation of Cu2+ with −SO3− on the SPEEK chain, Cu2+-coordinated SPEEK membranes were prepared, and they not only retain high −SO3H content but also possess robust mechanical properties and good dimensional stability compared to pristine SPEEK membrane. Meanwhile, the σ of the SPEEK-Cu membrane reaches 0.054 S/cm at −25 °C, and its fuel cell maximum power (Wmax) reaches 0.42 W/cm2 at −10 °C, demonstrating superior low-temperature performance in comparison to other reported materials. Particularly, water states in the prepared membranes are quantified by low-temperature differential scanning calorimetry. Because much more water bound to the plentiful −SO3H and Cu2+ inside the membrane endows it with anti-freezing performance, the decay of the σ and the Wmax for the SPEEK-Cu membrane is retarded at sub-zero temperatures. It is envisioned that composite membranes comprising metal ions such as Cu2+-SPEEK have a high potential for sub-zero fuel cell applications.

Enhancing Performance and Stability of High-Temperature Proton Exchange Membranes through Multiwalled Carbon Nanotube Incorporation into Self-Cross-Linked Fluorenone-Containing Polybenzimidazole.

Addressing critical challenges in enhancing the oxidative stability and proton conductivity of high-temperature proton exchange membranes (HT-PEMs) is pivotal for their commercial viability. This study uncovers the significant capacity of multiwalled carbon nanotubes (MWNTs) to absorb a substantial amount of phosphoric acid (PA). The investigation focuses on incorporating long-range ordered hollow MWNTs into self-cross-linked fluorenone-containing polybenzimidazole (FPBI) membranes. The absorbed PA within MWNTs and FPBI forms dense PA networks within the membrane, effectively enhancing the proton conductivity. Moreover, the exceptional inertness of MWNTs plays a vital role in reinforcing the oxidation resistance of the composite membranes. The proton conductivity of the 1.5% CNT-FPBI membrane is measured at 0.0817 S cm-1 at 160 °C. Under anhydrous conditions at the same temperature, the power density of the 1.5% CNT-FPBI membrane reaches 831.3 mW cm-2. Notably, the power density remains stable even after 200 h of oxidation testing and 250 h of operational stability in a single cell. The achieved power density and long-term stability of the 1.5% CNT-FPBI membrane surpass the recently reported results. This study introduces a straightforward approach for the systematic design of high-performance and robust composite HT-PEMs for fuel cells.

Development and analysis of the physical and electrochemical characteristics of a nano titanium (IV) tungstomolybdate supported on polyethersulfone composite cation exchange membrane

In this study, a series of novel composite membranes were synthesized utilizing polyethersulfone (PES), sulfonated polyethersulfone (SPES) as base polymer and titanium tungstomolybdate (TWM) as an inorganic ion exchange resin. The membranes were fabricated through the solution casting technique. The composite membranes exhibited enhanced thermal and chemical stability, as well as improved oxidative stability. All the composite membranes demonstrated higher hydrophilicity, with the SPES-TWM composite membranes displaying the lowest contact angle of 65°. The composite membranes also displayed favorable water uptake (up to 26% for SPES-TWM) and lower methanol uptake (maximum 12% for SPES-TWM) and better mechanical stability (maximum of 40 MPa for SPES-TWM). The SPES-TWM composite membranes exhibited the maximum ion exchange capacity of 1.32 meq.g−1. The transport number of 0.95 was obtained for SPES-TWM, which is comparable to the Nafion-117 membrane. The proton conductivity of both membranes increased as the temperature increased. The maximum proton conductivity of 6.3 mScm−1 was observed for SPES-TWM at 60 °C.

The effect of nitrogen positive sites on the proton conductivity and acid stability of polybenzimidazole-based proton exchange membranes

High-temperature proton exchange membranes (HT-PEMs) based on amino-type polybenzimidazole (AmPBI) and double-bonded ionic liquids (ILs) are prepared. To prevent leakage of ILs, three kinds of polymeric ionic liquids (PILs) with different nitrogen positive sites are synthesized through in-situ free radical polymerization, and then the AmPBI-PIL membranes are prepared. The ion pairs (N+ - H2PO4−) formed after treatment with KOH and PA have a good effect on both proton conductivity and PA retention. After acid doping, the nitrogen positive sites in the PILs form ion pairs with PA, which serves as a jumping site for protons and promotes proton transport. The excellent proton conductivity and PA remaining of the AmPBI-PIL membranes are noteworthy. In particular, the proton conductivity of AmPBI-CTDTr is as high as 184.9 mS cm−1 at 180 °C, and the acid reservation is 83 % at 160 °C after 240 h. AmPBI-CTDTr has a 550.9 mW cm−2 peak power density when it is anhydrous at 160 °C.

Sulfo ethyl cellulose/Nafion composite for high‐temperature proton exchange membrane

AbstractThis study investigated the potential enhancement of proton conductivity in Nafion membranes through the incorporation of sulfo ethyl cellulose (SEC) at varying weight ratios (5 and 10 wt.%). Results indicated that increasing the weight ratio of SEC led to improvements in water absorption, activation energy, and proton conductivity within the composite membranes. Specifically, the composite membrane exhibited a significant increase in proton conductivity, reaching up to 170 mS cm−1, in contrast to the pristine Nafion membrane which recorded 40.08 mS cm−1, particularly at temperatures exceeding 120°C. At the sub‐molecular level, Fourier transfer inferred spectroscopy (FTIR) analysis of Nafion/SEC membranes unveiled cross‐linking interactions occurring between the sulfo acid groups of Nafion chains and the hydroxyls within the SEC matrix. Moreover, X‐ray diffraction (XRD) findings of the composite membranes were instrumental in identifying crystalline phases, orientation, and structural features. The results indicated variations in atomic radius and alterations in lattice parameters at the nanoscale, induced by heightened surface forces resulting from the inclusion of SEC in the Nafion matrix. This phenomenon leads to a reduction in crystallite size, accompanied by an increase in peak broadening and surface area within the composite membranes. Such changes signify a clear interaction between SEC and Nafion, as confirmed by both scanning electron microscopy and thermal gravimetry analyses. Taken together, these findings strongly indicate that the cross‐linked composite membranes utilizing SEC‐Nafion hold significant promise as proton exchange membranes.

The strategy of micropore confinement via organic macrocyclic cavities for designing novel high-performance proton exchange membranes

The high-temperature hydrogen proton exchange membrane fuel cell is considered a disruptive technology for future energy applications. However, the weak binding strength between the proton carriers (phosphoric acid molecules) with polymer chains reduces the operational stability and proton transfer efficiency at conditions of high temperature and low humidity. In this work, a strategy of micropore confinement via organic macrocyclic cavities (sulfonic calix[4]arenes, sulfonic calix[8]arenes, sulfonated β-cyclodextrin) was developed for designing novel mixed matrix membranes functioning as high-temperature hydrogen proton exchange membranes. Benefitting from the confined micropores constructed by supramolecular cavities, the obtained mixed matrix membranes showed a higher uptake and retention capability of phosphoric acid as well as lower membrane swelling, yielding an enhanced proton conductivity. The proton conductivity of the mixed matrix membranes was 2–3 times higher while the conductivity attenuation was only 58.6% comparing with neat PBI membrane, (140℃, relative humidity = 0). In addition, due to the good compatibility caused by hydrogen bonding between fillers and polymer chains, the volume swelling was only 14% and the mechanical strength of the obtained mixed matrix membranes increased. We believe the strategy of micropore confinement via organic macrocyclic cavities for designing the novel mixed matrix membranes is thought to be of great significance for the research on high-temperature proton exchange membrane.

ТИПЫ ПОЛИМЕРОВ ДЛЯ МЕМБРАН ТОПЛИВНЫХ ЭЛЕМЕНТОВ

The work reflects a list of polymer materials used in the world to create proton-conducting mem-branes for low-temperature fuel cells. An analysis of the structure, physicochemical properties, condi-tions for the synthesis of polymers and operational characteristics of the membranes obtained on their basis was carried out

Robust and highly proton conductive COF composite membranes for fuel cell and electrochemical hydrogen compression

Robust and highly conductive proton exchange membrane (PEM) is the unremitting pursuit of numerous electrochemical energy technologies such as fuel cell and the emerging electrochemical hydrogen compression. Ionic covalent organic framework nanosheets (iCONs) with long-range ordered nanochannels and abundant ionic groups show substantial potential as next-generation PEM materials. However, it is challenging to assemble iCONs into membranes with both robustness and flexibility due to the electrostatic repulsion and rigid framework. Herein, we propose a hydrogen-bond binding strategy to fabricate sulfonic iCON (SCON) composite membranes by co-assembling tannic acid (TA) nanoaggregates and SCONs. The abundant and dynamically reversible hydrogen-bond interactions introduced by TA nanoaggregates establish effective linkage between SCONs and allow some restricted movements, endowing membranes with remarkably improved mechanical properties. The stacked SCONs construct long-range ordered nanochannels with well-arranged sulfonic groups in membranes, and the hydrogen-bond networks further facilitate the proton transport through Grotthuss mechanism. Consequently, TA/SCON composite membranes displays significantly enhanced tensile strength of 101.9 MPa, good flexibility and high proton conductivity of 490.1 mS cm−1 at 80 °C and 100 % RH simultaneously. This hydrogen-bond binding strategy offers a promising approach to fabricate robust and highly conductive PEMs for various proton-conducting applications.

Sulfonated poly(ether ether ketone)-Protic ionic Liquid-Based anhydrous Proton-Conducting composite polymer electrolyte membranes for High-Temperature fuel cell applications

A high-temperature polymer electrolyte membrane fuel cell (PEMFC) has enormous potential to produce clean energy with minimal environmental pollution along with high energy density and conversion efficiency. In the present work, anhydrous proton-conducting polymer electrolyte membranes for prospective high-temperature fuel cell application were successfully prepared using different protic ionic liquids (PILs) and sulfonated poly(ether ether ketone) (SPEEK). The protic ionic liquids (PILs), 2-hydroxyethylammonium formate, diethylmethyl ammonium triflate, 1-ethylimidazolium bis(trifluoromethylsulfonyl)imide, 1,2-dimethyl imidazolium bis(trifluoro methylsulfonyl)imide, and diethylmethylammonium methanesulfonate were selected based on their favorable physicochemical properties. The effect of the incorporation of the PIL on the structural, thermal, and electrical transport properties of the composite SPEEK polymer electrolyte membranes was studied. The prepared polymer electrolyte membranes (PEMs) were characterized using Fourier transform infrared (FTIR) spectroscopy, thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), X-ray diffractometry (XRD), and electrochemical impedance spectroscopy (EIS) techniques. FTIR results indicated an interaction between the PIL and the SPEEK, which resulted in homogeneous and flexible membranes. The DSC results confirmed good miscibility and elucidated plasticizing effect of the incorporated PIL on the SPEEK polymer matrix. All the PEMs showed good thermal stability and high-temperature anhydrous proton conductivity, achieving best proton conductivity, ≈8 × 10–3 S cm−1 at 120 °C and low activation energy ≈0.26 eV, making it suitable for prospective high-temperature PEMFC applications.

A High-Proton Conductivity All-Biomass Proton Exchange Membrane Enabled by Adenine and Thymine Modified Cellulose Nanofibers.

Nanocellulose fiber materials were considered promising biomaterials due to their excellent biodegradability, biocompatibility, high hydrophilicity, and cost-effectiveness. However, their low proton conductivity significantly limited their application as proton exchange membranes. The methods previously reported to increase their proton conductivity often introduced non-biodegradable groups and compounds, which resulted in the loss of the basic advantages of this natural polymer in terms of biodegradability. In this work, a green and sustainable strategy was developed to prepare cellulose-based proton exchange membranes that could simultaneously meet sustainability and high-performance criteria. Adenine and thymine were introduced onto the surface of tempo-oxidized nanocellulose fibers (TOCNF) to provide many transition sites for proton conduction. Once modified, the proton conductivity of the TOCNF membrane increased by 31.2 times compared to the original membrane, with a specific surface area that had risen from 6.1 m²/g to 86.5 m²/g. The wet strength also increased. This study paved a new path for the preparation of environmentally friendly membrane materials that could replace the commonly used non-degradable ones, highlighting the potential of nanocellulose fiber membrane materials in sustainable applications such as fuel cells, supercapacitors, and solid-state batteries.

Phosphate-grafted polyethyleneimine-induced multifunctional cerium oxide as an antioxidant for simultaneously enhancing the proton conductivity and durability of proton exchange membranes

Phosphate-grafted polyethyleneimine-induced multifunctional cerium oxide as an antioxidant for simultaneously enhancing the proton conductivity and durability of proton exchange membranes

Enhancement of comprehensive performance of high-temperature and low-humidity proton exchange membranes: Crosslinking of trifunctional proton conductor with branched polybenzimidazole

In order to improve the proton conductivity and antioxidant stability of proton exchange membranes (PEMs) at wide relative humidity (RH), composite membranes cross-linked with tribranched polybenzimidazole (TaPBI) and poly(azido-1-propanesulfonic acid −2,2′- methylsulfonic acid −5,5′-bis-benzimidazole) polyphosphazenes (PSBI) (TaPBI-PSBI) are prepared. TaPBI, as a branched polybenzimidazole, exhibits a large free volume. The trifunctional proton conductor PSBI-Na incorporates abundant flexible acidic groups and basic sites to enhance proton conductivity, and cross-linking groups to increase its binding strength with PBI. By casting and cross-linking, the proton conductivity, mechanical properties, and oxidation resistance of the TaPBI-PSBI membranes are significantly improved. The generation of cross-linked structures in the membranes is demonstrated by FT-IR. SEM shows that the surface of composite membrane is smooth and free of through holes. The elements are uniformly distributed. The TEM shows microphase separation occurs in the TaPBI-PSBI membrane, facilitating the formation of the continuous proton channels. The proton conductivity of TaPBI-PSBI (40) composite membrane reaches 0.170, 0.081, 0.059, and 0.037 S cm−1 at 180 °C, 100%, 50%, 30%, and 0% RH, respectively. The composite membrane is demonstrated the outstanding stability with the small decrease of proton conductivity and mass after durability testing of 96 h. The composite membrane exhibits high comprehensive performances as HT-PEM.

Anchoring of Fe-MIL-101-NH2 to the Polymer Membrane Matrix through the Hinsberg Reaction to Promote Conductivity of SPEEK Membranes.

SCPEEK@MOF proton exchange membranes, where SCPEEK is sulfinyl chloride polyether ether ketone and MOF is a metal-organic framework, were prepared by doping Fe-MIL-101-NH2 into polymers. The amino group in the MOF and the -SOCl2 group in thionyl chloride polyether ether ketone cross-link to form a covalent bond through the Hinsberg reaction, and the prepared composite membrane has stronger stability than other electrostatic interactions and simple physical doping composite membranes. The formation of covalent bonds improves the water absorption of the composite membrane, which makes it easy for water molecules to form hydrogen bonds. Moreover, SPEEK as a proton conductive polymer and the synergy of MOFs improve the proton conductivity of composite membranes. The composite membranes were characterized by Fourier transform infrared spectroscopy, powder X-ray diffraction, scanning electron microscopy, and atomic force microscopy. The swelling rate, water absorption, mechanical stability, ion exchange capacity, and proton conductivity of the pure sulfonated polyether ether ketone (SPEEK) membrane were compared with those of the mechanically doped SPEEK/MOF membrane and the composite membrane SCPEEK@MOF doped with different ratios of Fe-MIL-101-NH2, and all of the SCPEEK@MOF showed superior performance. When the Fe-MIL-101-NH2 loading rate of the composite membrane is 2%, the proton conductivity of the composite membrane can reach 0.202 S cm-1 at 363 K and a 98% relative humidity, which is much higher than that of the SPEEK/MOF membrane obtained by simple physical doping under the same conditions.

Hybrid Membrane of Sulfonated Poly(aryl ether ketone sulfone) Modified by Molybdenum Clusters with Enhanced Proton Conductivity.

Developing novel proton exchange membranes (PEMs) with low cost and superior performance to replace Nafion is of great significance. Polyoxometalate-doped sulfonated poly(aryl ether ketone sulfone) (SPAEKS) allows for the amalgamation of the advantages in each constituent, thereby achieving an optimized performance for the hybrid PEMs. Herein, the hybrid membranes by introducing 2MeIm-{Mo132} into SPAEKS are obtained. Excellent hydrophilic properties of 2MeIm-{Mo132} can help more water molecules be retained in the hybrid membrane, providing abundant carriers for proton transport and proton hopping sites to build successive hydrophilic channels, thus lowering the energy barrier, accelerating the proton migration, and significantly fostering the proton conductivity of hybrid membranes. Especially, SP-2MIMo132-5 exhibits an enhanced proton conductivity of 75mScm-1 at 80°C, which is 82.9% higher than pristine SPAEKS membrane. Additionally, this membrane is suitable for application in proton exchange membrane fuel cells, and a maximum power density of 266.2mWcm-2 can be achieved at 80°C, which far exceeds that of pristine SPAEKS membrane (54.6mWcm-2). This work demonstrates that polyoxometalate-based clusters can serve as excellent proton conduction sites, opening up the choice of proton conduction carriers in hybrid membrane design and providing a novel idea to manufacture high-performance PEMs.

Numerical investigation of parameter distributions in high-temperature PEMFCs under various cooling surface temperature gradients

Non-uniform current density distribution can lead to localized hotspots, resulting in shortened lifespans of fuel cells. The temperature distributions on the bipolar plate cooling surface significantly influence various parameters within a fuel cell. This study develops a mathematical model for a high-temperature proton exchange membrane fuel cell (HT-PEMFC) to simulate its operation in four different directions of temperature gradient on the cooling surface. The distributions of membrane temperature, proton conductivity, oxygen concentration, activation loss, and current density were obtained to clarify the interaction mechanism between cooling surface temperature and these parameters in fuel cell. The results show that the membrane temperature and proton conductivity increase and the oxygen concentrations decrease with increasing cooling surface temperature. A lower temperature in the catalyst layer regions leads to a decrease in the current density. In particular, when the cooling surface temperature distribution is characterized by a temperature decrease in the upstream area with a high reactant concentration and an increase in the downstream area with a low reactant concentration, the fuel cell has an excellent current density uniformity, which reaches 92.61 % at a voltage of 0.6 V and a cooling surface temperature difference of 10 K.

Hydrogen-Bonded Metal-Organic Framework Nanosheet as a Proton Conducting Membrane for an H2 /O2 Fuel Cell.

Proton-conducting metal-organic frameworks (MOFs) have attracted attention as potential electrolytes for fuel cells. However, research progress in utilizing MOFs as electrolytes for fuel cells has been limited, mainly due to challenges associated with issues such as the fabrication of MOF membranes, and hydrogen crossover through the MOF's pores. Here, we report proton conductivity and fuel cell performance of a self-standing membrane prepared from of a bismuth subgallateMOF nanosheets with non-porous structure are reported. The fabricated MOF nanosheet membrane with no binding agent exhibitsed structural anisotropy. The proton conductivity in the membrane thickness direction (4.4×10-3 Scm-1 ) at 90°C and RH 100% is observed to be higher than that in the in-plane direction of the membrane (3.3×10-5 Scm-1 ). The open circuit voltage (OCV) of a fuel cell with ≈120µm proton conducting membrane is 1.0V. The non-porous nature of the MOF nanosheets contributes to the relatively high OCV. A fuel cell using ≈40µm membrane as proton conducting electrolyte records a maximum of 25mWcm-2 power density and a maximum of 109mAcm-2 current density with 0.91V OCV at 80°C in humid conditions.

Cerium based metal-organic framework as the efficient radical quencher for proton exchange membrane fuel cells

Durability is one of the most key problems for the widespread commercialization of proton exchange membrane fuel cells (PEMFCs). Proton exchange membranes (PEMs) are pivotal components of the PEMFCs and their chemical stability is thus an important for the PEMFCs reliability. The incorporation of Ce-based radical quenchers such as ceria in PEMs can obviously alleviate the chemical deterioration of PEMs. Nevertheless, cell performance may decrease due to the presence of Ce-based radical quenchers. Therefore, a trade-off between cell performance and chemical stability of Ce-based radical quenchers containing PEM appears. To solve this issue, we developed a Ce-based metal organic framework Ce-BTC MOF with high radical trapping and proton-conducting properties. The Ce-BTC MOFs are introduced into the PFSA membrane to enhance the chemical stability and proton conductivity of the PFSA membrane. The PFSA/Ce-BTC membrane showed a maximum power density of 1.71 W/cm2 at 75 °C under 80％RH. After OCV test, PFSA/Ce-BTC membrane exhibited a decay of 0.56 mV/h after 120 h; pristine PFSA and Nafion membrane exhibited accelerated decay (for pristine PFSA, 1.72 mV/h; for Nafion membrane, 2.36 mV/h). Therefore, introduction of Ce-BTC MOFs offers an active defence approach to enhance the chemical stability of PEMFCs without sacrificing their cell performance.

Incorporation of multilayered double hydroxides/sepiolite augments proton conductivity performance in low sulfonated polyether sulfone octyl sulfonamide

AbstractLow-sulfonation-level polyether sulfone octyl sulfonamide (LSPSO) was blended with a layered double hydroxides (LDHs, Mg2AlCl)/sepiolite nanostructure clay as a filler to create an electrolyte membrane for fuel cell applications. Comprehensive characterization of the composite membranes was conducted, encompassing Fourier-transform infrared spectroscopy, X-ray diffraction, mechanical stability assessment, thermal gravimetric analysis, ion exchange capability, swelling characteristics, water uptake performance, and electrochemical impedance spectroscopy analysis. In comparison to the pristine LSPSO membrane, the presence of LDHs/sepiolite nanoarchitecture material within LSPSO exhibited superior water retention and proton conductivity values, especially at elevated temperatures. The proton conductivity of the composite membranes reached approximately 250 mS/cm, while the unmodified LSPSO membrane only achieved 35 mS/cm at 100 °C. Moreover, LSPSO composite membranes demonstrated enhanced chemical and thermal stability along with higher proton conductivity when compared to pristine LSPSO membranes. These findings highlight the potential of developing tailored LSPSO composite membranes to advance the prospects of commercial applications in proton exchange membrane fuel cells.

Utilization of cellulose-based carbon nanodots in sulfonated polysulfone based membrane for direct methanol fuel cell

Sulfonated polysulfone (SPS) composite membranes consisting of cellulose-based carbon nanodots (CNDs) were successfully prepared as a proton exchange membrane (PEM) for direct methanol fuel cell (DMFC) applications. The CNDs were prepared using the top-down hydrothermal method. The structure transformation from cellulose to CNDs was confirmed by the FTIR and XRD analysis. The particle size of CNDs was between 1 and 3 nm. The particles exhibited good optical properties. The incorporation of CND into matrix polymer increased the thermal stability of the membranes. Morphology analysis of the SPS/CND composite membranes revealed that CNDs had been successfully dispersed within the SPS polymer matrix. The cross-linking between SPS and CNDs enhanced the proton conductivity of the composite membranes compared to the pristine SPS membrane. The SPS/CND-1 (1 wt%) exhibited the highest selectivity with a proton conductivity of 35.5 mS.cm−1 and a methanol permeability of 3.50 × 10−6 cm2.s−1. The experimental results indicate that the incorporation of CNDs into the SPS membrane also decreased the amount of methanol that can pass through the membrane when used in DMFCs.

Proton-conducting membranes based on Nafion® synthesized by using nanodiamond platform

New method of emulsion synthesis of Nafion®-type copolymer composition by using nanodiamond platform has been proposed and implemented. Produced polymeric coagulate saturated with diamonds (4.1 % wt.) possessed increased ionic capacity of the copolymer comparative to the analogue without diamonds. SEM patterns for coagulate membranes showed labyrinthine structures with diamonds integrated into copolymer without any segregation. This structuring provided necessary elastic and strength properties of new type membranes for hydrogen fuel cells. In new membranes synchrotron experiments exhibited a network of ionic channels which ensured a proton conductivity by one order of magnitude higher than that for the analogue produced of premade components.