Highly enhanced proton conductivity of single-step-functionalized graphene oxide/nafion electrolyte membrane towards improved hydrogen fuel cell performance

Acidic group functionalized graphene oxide (GO) as a filler to the state-of-art Nafion electrolytes are regarded as potential materials towards next-generation fuel cell application. However, the tedious synthesis process for GO functionalization, and aggravated chemical durability at high temperatures demands the scientific community to design suitable Nafion-based functionalized GO electrolytes with superior proton conductivity and power density at actual fuel cell conditions i.e., 80 °C and 100% relative humidity (RH). Herein, a potential single-step-phosphorylated graphene oxide (sPGO) modified Nafion (sPGO/NF) is introduced to simultaneously multifold the proton conductivity, chemical durability, and power density of Nafion. Under actual fuel cell conditions, the sPGO/NF exhibits maximum proton conductivity (0.306 Scm⁻¹) which is 1.7-fold and 1.6-fold higher than that of rNF and GO/NF, respectively. Moreover, sPGO/NF achieves the maximum power density of 0.652 Wcm⁻² (80 °C, 100% RH), much higher than the rNF (0.51 Wcm⁻²) and GO/NF (0.53 Wcm⁻²) at same condition.     

Preparation of high-performance polymer electrolyte nanocomposites through nanoscale silica particle dispersion

Nano-level dispersion with a minimum amount of non-porous and surface-functionalized nanoparticles is a key to tune physically a common polymer material with poor durability to a powerful material with excellent stability even under harsh fuel cell conditions. Surfactants composed of hydrophobic cores and hydrophilic outer shells are used to assist a homogenous distribution of surface-treated (hydrophilic and hydrophobic) silica nanoparticles. In particular, their effect on nanoparticle dispersion is conspicuous in polymer electrolyte nanocomposites containing hydrophilic surface-treated silica. The hydrophilic silica acts as an additional proton conductor in the acid electrolyte medium, leading to improved proton conductivity without any negative side-effects on the mechanical and chemical durability of the membrane material. The well-distributed hydrophilic silica nanoparticles are beneficial in preventing methanol permeation via compact polymer packing and in strengthening the membrane stability under hot aqueous conditions. Finally, the efficacy of the nano-level dispersion is electrochemically verified in terms of high single-cell performance and further extended life time as a result of a synergistic effect of improved proton conductivity, reduced methanol permeability and excellent hydrolytic durability.     

Chemical durability of thin pore-filling membrane in open-circuit voltage hold test

Long-term chemical stability of proton exchange membranes in polymer electrolyte fuel cells (PEFCs) is an important issue for widespread commercialization. Here, we report on the chemical stability of a membrane-electrode assembly with a 7 μm thick pore-filling membrane (porous substrate filled with high ion exchange capacity perfluorosulfonic acid (PFSA) polymer) using an open-circuit voltage hold test. The very thin pore-filling membrane shows comparable chemical durability to Nafion 211. Interestingly, the pore-filling membrane shows a different degradation behavior from Nafion 211 due to the use of chemically and mechanically stable porous substrate, with no thickness change and little amounts of fluorine leakages are observed in the pore-filling membrane compared to membrane thinning and large amounts of fluorine leakage in Nafion 211. The thin pore-filling membrane shows promise for application in PEFCs, as it balances high fuel cell performance at high temperature and low relative humidity with high chemical durability.     

Surface-modified Nafion membrane by oleylamine-stabilized Pd nanoparticles for DMFC applications

The surface of Nafion was modified by applying palladium nanoparticles as methanol barrier materials to decrease methanol crossover and improve the performance of fuel cells. The properties of the Pd-modified membrane, in terms of conductivity, methanol permeability, percentage of liquid uptake as well as the performance of its membrane electrode assembly (MEA) in the direct methanol fuel cell, were analyzed and compared with those using bare Nafion. The modified membrane showed considerable improvement on reducing methanol loss without decreasing proton conductivity. The DMFC performance of modified membrane was superior to that of bare Nafion both at a typical fuel state of 2 M and at high concentration of 5 M, implying that the palladium-modified Nafion can be a good alternative approach for DMFC applications.     

Acid doped polybenzimidazoles based membrane electrode assembly for high temperature proton exchange membrane fuel cell: A review

High temperature proton exchange membrane fuel cells (HT-PEMFCs) are proficient clean energy conversion devices for automotive and stationary applications. HT-PEMFC could mitigate the CO poisoning, humidity and heat management, and sluggish of oxygen reduction reaction (ORR). Acid doped polybenzimidazoles (PBIs)/functionalized PBIs polymer electrolyte membranes are familiar uses for HT-PEMFC because of high proton conductivity with thermo-mechanical stability. Proton conductivity of PBI membranes is greatly promising by acid doping dimension and cell operating temperature. PBI reactive sites (=NH) and acidic anions prominently contribute the proton transfer through the prolonged hydrogen bonding network. Coating and sprayed methods are prominent techniques for fabrication of gas diffusion electrodes (GDEs), although shrinkage and hairline surface cracks observed on GDEs. Multi walled carbon nanotubes (MWCNTs) has been compromising unique characteristics for steady carbon support materials. Moreover, PTFE and PVDF can be used as catalyst binder to reduce corrosion rate. In this review, it has been focused the PBIs membrane, acid doping, GDEs, MEA and durability of MEA.     

Investigation of the effects of SPEEK and its clay composite membranes on the performance of Direct Borohydride Fuel Cell

In this study, composite cation exchange membranes (CEM) were developed. With the experience from widely studied proton exchange membrane fuel cells (PEMFC), sulfonated polyether ether ketone (SPEEK) was prepared to be a more effective and cheaper ionomer alternative to the industry standard Nafion ®. SPEEK polymer membrane can reach sufficient ionic conductivities but have some mechanical and chemical stability problems (at a high degree of sulfonations (DS)). Therefore, in order to optimize the membrane, composite mixing with a well-known organic/inorganic clays called Cloisite® 15A, Cloisite ® 30B and MMT were used. Test cells for both single-cell and conductivity were designed and constructed. The ionic conductivity cell was different than the ones used in most studies, measuring conductivity in-plane with 4 probes using EIS. The membranes were characterized for their proton conductivity with electrochemical impedance spectroscopy (EIS), for DS with H NMR, water uptake, and fuel cell performance tests. First results showed that the acidic sulfonic groups of SPEEK interacted with organic/inorganic clays and as a result of partial barrier the ionic conductivity was decreased but power densities were increased. SPEEK-Cloisite® 30B composite membrane has given 40 mW/cm² power density value which is higher than pure SPEEK membrane (35 mW/cm²). The proton conductivities of the final composite membranes were close to bare SPEEK membranes which are 0,065 and 0,075 S/cm for SPEEK-Cloisite ® 30B and pristine SPEEK, respectively.     

Synthesis and characterization of polyvinyl alcohol copolymer/phosphomolybdic acid-based crosslinked composite polymer electrolyte membranes

Polymer electrolyte membrane fuel cells (PEMFCs) are very promising as future energy source due to their high-energy conversion efficiency and will help to solve the environmental concerns of energy production. Polymer electrolyte membrane (PEM) is recognised as the key element for an efficient PEMFC. Chemically crosslinked composite membranes consisting of a poly(vinyl alcohol-co-vinyl acetate-co-itaconic acid) (PVACO) and phosphomolybdic acid (PMA) have been prepared by solution casting and evaluated as proton conducting polymer electrolytes. The proton conductivity of the membranes is investigated as a function of PMA composition, crosslinking density and temperature. The membranes have also been characterized by FTIR spectroscopy, TGA, AFM and TEM. The proton conductivity of the composite membranes is of the order of 10⁻³ S cm⁻¹ and shows better resistance to methanol permeability than Nafion 117 under similar measurement conditions.     

Sulfonated PEEK-based polymers in PEMFC and DMFC applications: A review

Nowadays, polymer electrolyte membrane fuel cells (PEMFCs) and direct methanol fuel cells (DMFCs) are devices known for using proton conducting membranes. From a conceptual point of view, DMFC and PEMFC systems are very similar, except for being supplied by different fuels such as methanol and hydrogen, respectively. Commonly, PEMFCs are performed at temperature lower than 100 °C owing to the failure of the electrochemical performances of Nafion. Nevertheless, taking into account the poisoning effect of CO on the fuel cell catalyst (conventionally based on Pt), the ideal working temperature of the PEMFCs should be above 100 °C, where CO poisoning could be drastically reduced or avoided. Today, Nafion is recognized as the most used proton exchange membrane in the market, useful for both PEMFC and DMFC applications. It is based on a perfluorinated polymer and shows good thermal stability and high proton conductivity as main benefits. On the contrary, Nafion is an expensive material and suffers high fuel crossover (particularly, methanol crossover in DMFC applications) besides the proton conductivity loss above 100 °C. Therefore, in the last decades many scientists paid special attention on the development of new materials based on non-fluorinated polymers as an alternative to Nafion. One of the most promising class of is represented by the polyetheretherketone (PEEK). According to the specialized literature, interesting performances in terms of proton conductivity and thermo-chemical properties as well as low fuel crossover and costs are noticeable for sulfonated PEEK-based polymers. Indeed, many scientific applications are devoted to modify PEEK polymer for manufacturing membranes alternative to Nafion for both PEMFC and DMFC applications. Among them, important methods are exploited for preparing electrolyte membranes from PEEK such as: a) PEEK electrophilic sulfonation (S-PEEK); b) S-PEEK and non-functional polymers blending; c) S-PEEK, heteropolycompounds and poly-ether-imide doping with inorganic acids, etc.     

Sulfonated poly(arylene ether sulfone) nanocomposite electrolyte membrane for fuel cell applications: A review

Polymer electrolyte membrane (PEM) fuel cells are considered a promising technology for generating power with water as a byproduct. Recently, sulfonated poly(arylene ether sulfone) (SPAES) has emerged as a most suitable alternative for PEM applications because of its high proton conductivity, high CO tolerance, and low fuel crossover. However, the existing SPAES polymeric membrane materials have poor chemical reactivity, mechanical processability, and thermal usability. Thus, the effects of mixing inorganic nanomaterials with SPAES polymers on proton conductivity, power density, fuel crossover, thermal and chemical stability, and durability are discussed in this review. Further, the progress in preparation methods and fuel cell characteristics by the addition of silica, clay, heteropolyacids (HPA), and carbon nanotubes (CNTs) in polymer membrane materials for PEM applications is also discussed.     

Improving the performance of sulfonated polymer membrane by using sulfonic acid functionalized hetero-metallic metal-organic framework for DMFC applications

Proton transport played a crucial part in the fuel cells, sensors, and batteries. The electrolyte used in fuel cells should possess high proton conductivity and good chemical stability. Herein, taking advantage of the high proton conductivity of metal-organic framework (MOF) and the good chemical stability of branched polymers, a new heterometallic mediated MOF (Zr-Cr-SO₃H) is synthesized and utilized as a filler in the highly branched sulfonated polymer (BSP). In addition, Zr-SO₃H MOF is also prepared for comparison. Transmission electron microscope study shows that the prepared MOF particles are spherical in size and interconnected through nanosheets. The optimized quantity of MOFs inside the polymer matrix improves the water sorption, mechanical property, and proton conductivity. The composite membranes display an improved open-circuit voltage than the pristine BSP membrane. By comparing the Zr-SO₃H MOF incorporated composite membrane, Zr-Cr-SO₃H MOF incorporated composite membranes display higher proton conductivity and peak power density in a single-cell test. In particular, the single-cell fabricated with Zr-Cr-SO₃H MOF incorporated composite membrane is able to reach the peak power density of 64.6 mWcm⁻² at 60°C, which is 26% greater than the Nafion 212 membrane. Furthermore, this work offers a new strategy for the utilization of hetero-metal MOF as a filler for proton exchange membrane applications.     

Analysis of mechanism of Nafion® conductivity change due to hot pressing treatment

In previous work, the authors observed that multiple hot-pressing cycles of Nafion 212 prior to Proton Exchange Membrane Fuel Cell (PEMFC) operation was found to result in significant performance gains. In order to further explore this effect, Nafion 212 samples were subjected to various thermal treatments and then to various analytical techniques in order to probe whether changes to the membrane contributed to these performance gains in a substantial way. Electrochemical Impedance Spectroscopy (EIS) measurement sought to validate that the treatment caused a proton conductivity change. Thermogravimetric Analysis (TGA) and Fourier Transform Infrared Spectroscopy (FTIR) measurements were implemented to determine whether chemical changes in the membrane occurred. Results suggest that the hot pressing treatment causes a significant effect in the electrical properties of Nafion 212, however the physical change that occurs in the polymer is not chemical in nature. Further analysis attempts to support the idea that the change in proton conductivity is due to water channel reconfiguration in the membrane, activated by elevated temperature and compressive stress at the glass transition temperature of the Nafion 212.     

Anhydrous proton conducting membranes for PEM fuel cells based on Nafion/Azole composites

Proton conducting membranes are the most crucial part of energy generating electrochemical systems such as polymer electrolyte membrane fuel cells (PEMFCs). In this work, Nafion based proton conducting anhydrous composite membranes were prepared via two different approaches. In the first, commercial Nafion115 and Nafion112 were swelled in the concentrated solution of azoles such as 1H-1,2,4-triazole (Tri), 3-amino-1,2,4-triazole (ATri) and 5-aminotetrazole (ATet) as heterocyclic protogenic solvents. In the second, the proton conducting films were cast from the Nafion/Azole solutions. The partial protonation of azoles in the anhydrous membranes were studied by Fourier transform infrared (FT-IR) spectroscopy. Thermal properties were investigated via thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). TGA results showed that Nafion/ATri and Nafion/ATet electrolytes are thermally stable at least up to 200 °C. Methanol permeability measurements showed that the composite membranes have lower methanol permeability compared to Nafion112. Nafion115/ATri system has better conductivity at 180 °C, exceeding 10⁻³ S/cm compared to other Nafion/heterocycle systems under anhydrous conditions.     

Stabilizing phosphotungstic acid in Nafion membrane via targeted silica fixation for high-temperature fuel cell application

With PWA as proton transfer and silica as water retainer, stable phosphotungstic acid/silica/Nafion (PWA/Si–N) composite membrane is non-destructively fabricated and exhibits excellent stability and high temperature proton conductivity. Compared with pristine Nafion, high temperature proton conductivity is significantly enhanced due to the collaboration between –SO₃H ionic clusters and the in-situ filled silica embedded PWA nanoparticles. PWA is stabilized in the ionic clusters via in-situ catalyzing the hydrolysis silica precursor targeted filled into the –SO₃H ionic clusters. Stable proton conductivity of the PWA/Si–N membrane at 110 °C and 60% RH is high to 0.058 S/cm, which is 2.4 folds of that of Nafion. At the same time, the composite membrane still maintains good mechanical and thermal stability. As a result, high temperature fuel cell performance of the composite membrane is improved by 41% compared with the pristine Nafion membrane. The in-situ coating method proved to be an effective method to solve the stability of PWA in Nafion membrane, especially the inorganic oxide with good hygroscopicity as the modifier.     

l-Ascorbic acid as an alternative fuel for direct oxidation fuel cells

l-Ascorbic acid (AA) was directly supplied to polymer electrolyte fuel cells (PEFCs) as an alternative fuel. Only dehydroascorbic acid (DHAA) was detected as a product released by the electrochemical oxidation of AA via a two-electron transfer process regardless of the anode catalyst used. The ionomer in the anode may inhibit the mass transfer of AA to the reaction sites by electrostatic repulsion. In addition, polymer resins without an ionic group such as poly(vinylidene fluoride) and poly(vinyl butyral) were also useful for reducing the contact resistance between Nafion membrane and carbon black used as an anode, although an ionomer like Nafion is needed for typical PEFCs. A reaction mechanism at the two-phase boundaries between AA and carbon black was proposed for the anode structure of DAAFCs, since lack of the proton conductivity was compensated by AA. There was too little crossover of AA through a Nafion membrane to cause a serious technical problem. The best performance (maximum power density of 16 mW cm⁻²) was attained with a Vulcan XC72 anode that included 5 wt.% Nafion at room temperature, which was about one-third of that for a DMFC with a PtRu anode.     

Theoretical studies on the proton dissociation and degradation of sulfonated polyethylene electrolyte membrane

Proton dissociation property and chemical stability of precisely sulfonated polyethylene, p21SA, has been investigated by theoretical calculations. The results show that proton in model compound is spontaneously dissociated when hydration number is 3, while in a folded structure, only required a hydration number of 2.5, lower than Nafion. Evidently, its good proton dissociation property and folded structure are contributed to the outstanding proton conductivity of p21SA. The chemical stability of p21SA membrane is evaluated by the bond dissociation energy and chemical degradation mechanism calculations, which discloses that C–S bond is the weakest for p21SA backbone. The most favorable degradation routes are H atom abstraction by radicals followed by C–S bond scission. We hope this work can provide some ideas for the performance improvement of p21SA membrane analogues used in proton electrolyte membrane fuel cells.     

Development of perfluorosulfonic acid polymer-based hybrid composite membrane with alkoxysilane functionalized polymer for vanadium redox flow battery

A new kind of alkoxy silane functionalized polymer (ASFP) is synthesized by selectively functionalized carboxyl groups as a novel inorganic precursor polymer to prepare organic-inorganic hybrid membrane for vanadium redox flow battery (VRFB) system. The novel hybrid membrane has been fabricated by interconnection between hydrophilic domains of Nafion and ASFP functional group. The effective concentration of ASFP for hybrid membrane is 25% (wt/wt). The proton conductivity and selectivity of the hybrid membrane are comparable with those of the Nafion212 membrane, which is mainly attributed by the presence of additional hydrophilic domains in the hybrid membrane. The proton conductivity and ion exchange capacity of the Nafion-ASFP (75:25) membrane is 0.061 S/cm and 0.68 meq/g, respectively. Remarkably, the Nafion-ASFP membrane shows a low vanadium permeability (1.259 × 10⁻⁷ cm²/min) and high selectivity, which is an excellent advantage. As a result, the hybrid membrane shows comparable efficiency performance with Nafion212 over 50 cycles. Notably, the VRFB unit cell with Nafion-ASFP membrane achieves higher coulombic efficiency than Nafion212. The hybrid membrane reveals a new route to develop an alternative fluorinated polymer membrane with numerous advantages especially cost-effectiveness, homogeneous dispersion of inorganic silica precursor materials in the hybrid membrane without deterioration of mechanical strength, and lower vanadium ion crossover for VRFB system.     

A review of quaternized polyvinyl alcohol as an alternative polymeric membrane in DMFCs and DEFCs

Direct methanol fuel cells (DMFCs) and direct ethanol fuel cells (DEFCs) have emerged as alternative power generators for portable devices and household appliances because of their easy and fast production of electricity, as well as high energy conversion to provide high-power density. However, several critical factors limit the commercialization of DMFCs and DEFCs, particularly issues related to polymer electrolyte membranes, including the high-cost production of Nafion membranes and cell degradation caused by high fuel crossover and dehydration. This review paper provides an overview of the current status and challenges in quaternized polyvinyl alcohol (QPVA)-based membranes as an alternative polymer electrolyte membrane for DMFCs and DEFCs. The main advantages of using QPVA-based membranes in fuel cells are reduced cost production of membrane, fuel-crossover minimization, and competitive conductivity with Nafion membrane. The effects of modifying the QPVA-based membrane, especially on conductivity properties, fuel crossover, uptake condition, mechanical, thermal, and chemical properties, and single-cell performance are comprehensively discussed. The best performances of DMFCs and DEFCs with utilizing QPVA-based membrane are reported as 272 and 144 mW cm⁻², respectively. This paper is the first to highlight the current status and challenges of QPVA-based membranes for DMFCs and DEFCs applications.     

Polymer electrolyte membrane with magnetic nanoparticles containing benzimidazole terminals: An approach to induce proton transfer species on membrane surface

Proton conductive species incorporated in polymer electrolyte membrane (PEM), in general, are randomly existed in the membrane, and this limits the proton transfer efficiency. The present work proposes an approach to align the proton conductive species on the PEM surface so that the first contact of proton species from anode effectively initiates proton transfer efficiently. By simply conjugating benzimidazole (Bz) with magnetic nanoparticles (MagNPs) followed by applying magnetic field, Bz can be induced and aligned on the surface of sulfonated poly (ether ether ketone) (SPEEK) membrane and this results in 10% increment of the proton conductivity. The present work demonstrates a simple way to create a pathway on the membrane surface for proton hopping to improve the proton conductivity.     

Properties and fuel cell performance of a Nafion-based,sulfated zirconia-added,composite membrane

The effect of an acidic inorganic additive, i.e. sulfated zirconia, on Nafion-based polymer electrolytes is evaluated by comparing the properties in terms of conductivity and fuel cell performance of a composite sulfated zirconia-added Nafion membrane with those of an additive-free Nafion membrane. The peculiar surface properties of the selected filler promote a higher hydration level and a higher conductivity for the composite membrane under unsaturated conditions, i.e. at 20% RH. Tests on H₂-air fully humidified cells, monitored at 70 °C and at atmospheric pressure, reveal small differences when passing from a plain Nafion to a composite Nafion/sulfated zirconia membrane as electrolyte. However, remarkably great improvements are observed for the composite membrane-based cell when the comparison tests are run at low relative humidity and high temperature, this outlining the beneficial role of the sulfated zirconia additive.     

Understanding of temperature-dependent performance of short-side-chain perfluorosulfonic acid electrolyte and reinforced composite membrane

The short-side-chain (SSC) perfluorosulfonic acid (PFSA) membranes are important candidates as membrane electrolytes applied for high temperature or low relative humidity (RH) proton exchange membrane fuel cells. In this paper, the fuel cell performance, proton conductivity, proton mobility, and water vapor absorption of SSC PFSA electrolytes and the reinforced SSC PFSA/PTFE composite membrane are investigated with respect to temperature. The pristine SSC PFSA membrane and reinforced SSC composite membrane show better fuel cell performance and proton conductivity, especially at high temperature and low relative humidity conditions, compared to the long-side-chain (LSC) Nafion membrane. Under the same condition, the proton mobility of SSC PFSA membranes is lower than that of the LSC PFSA membrane. The water vapor uptake values for Nafion 211 membrane, pristine SSC PFSA membrane and SSC PFSA/PTFE composite membrane are 9.62, 11.13, and 11.53 respectively at 40 °C and they increase to 9.89, 12.55 and 13.09 respectively at 120 °C. The high water content of SSC PFSA membrane makes it maintain high performance even at elevated temperatures.