A significantly improved membrane for vanadium redox flow battery

A novel sandwich-type sulfonated poly(ether ether ketone) (SPEEK)/tungstophosphoric acid (TPA)/polypropylene (PP) composite membrane for a vanadium redox flow battery (VRB) has been developed with improved properties: the permeability of vanadium ions is greatly reduced and the performance of the VRB cell is greatly increased. The membrane is based on a traditional SPEEK membrane embedded with TPA but PP is used to enhance the membrane for the first time. Although its voltage efficiency (VE) is a little lower than that of a Nafion 212 membrane, it is expected to have good prospects for VRB systems because of its low cost and good performance.     

Vicious cycle during chemical degradation of sulfonated aromatic proton exchange membranes in the fuel cell application

Weak phase separation and vulnerable linking groups between aromatic units are common setbacks of sulfonated aromatic proton exchange membranes (PEMs) from durability point of view. In this study, sulfonated poly(ether ether ketone) (SPEEK) membranes were exposed to Fenton's solution for a specific time, ranging from 10 to 60 minutes. Chemical structure and morphology evolution, decay in mechanical and thermal stability, and H₂ permeability of SPEEK membranes were evaluated during the chemical degradation. Less-entangled polymeric chains with lower average molecular weight of degraded SPEEK samples diminished mechanical rigidity. In addition, reduction of aromatic rings in each repeat unit led to higher thermal decomposition rate. Furthermore, randomly distributed micro-defects in the SPEEK morphology and an increase in water sorption can reduce the fatigue strength of membranes in the wet-dry cycles. Eventually, hydrogen cross-over rate was gradually increased, and henceforth, accelerated destructive radical formation and degradation can be predicted.     

Sulfonic acid functionalized graphene oxide paper sandwiched in sulfonated poly(ether ether ketone): A proton exchange membrane with high performance for semi-passive direct methanol fuel cells

Sulfonated poly(ether ether ketone) (SPEEK) membranes have been deposited on the both sides of a sulfonic acid functionalized graphene oxide (SGO) paper to form a proton exchange membrane (PEM) with a sandwiched structure. The obtained SPEEK/SGO/SPEEK membrane could exhibit proton conductivity close to Nafion^® 112 and lower methanol permeability. The use of this SPEEK/SGO/SPEEK membrane greatly improves the performance of the semi-passive direct methanol fuel cell (DMFC). The semi-passive DMFC with the SPEEK/SGO/SPEEK membrane is found to be capable of delivering the peak power density 60% higher than that with the commercial Nafion^® 112. This, along with its comparable durability to Nafion^® 112, strongly suggests the great promise of using the SPEEK/SGO/SPEEK membrane as the PEM.     

Crosslinked sulfonated poly(ether ether ketone) proton exchange membranes for direct methanol fuel cell applications

In the present study, a series of the crosslinked sulfonated poly(ether ether ketone) (SPEEK) proton exchange membranes were prepared. The photochemical crosslinking of the SPEEK membranes was carried out by dissolving benzophenone and triethylamine photo-initiator system in the membrane casting solution and then exposing the resulting membranes after solvent evaporation to UV light. The physical and transport properties of crosslinked membranes were investigated. The membrane performance can be controlled by adjusting the photoirradiation time. The experimental results showed that the crosslinked SPEEK membranes with photoirradiation 10 min had the optimum performance for proton exchange membranes (PEMs). Compared with the non-crosslinked SPEEK membranes, the crosslinked SPEEK membranes with photoirradiation 10 min markedly improved thermal stabilities and mechanical properties as well as hydrolytic and oxidative stabilities, greatly reduced water uptake and methanol diffusion coefficients with only slight sacrifice in proton conductivities. Therefore, the crosslinked SPEEK membranes with photoirradiation 10 min were particularly promising as proton exchange membranes for direct methanol fuel cell (DMFC) applications.     

Amphoteric ion exchange membrane synthesized by direct polymerization for vanadium redox flow battery application

Novel sulfonated poly (fluorenyl ether ketone) with pendant quaternary ammonium groups (SPFEKA) was successfully synthesized by one-pot copolymerization of bis(4-fluoro-3-sulfophenyl)sulfone disodium salt, 4,4′-difluorobenzophenone, bisphenol fluorene and 2,2′-dimethylaminemethylene-9,9′-bis(4-hydroxyphenyl) fluorene (DABPF). The chemical structures were confirmed by FT-IR, and ¹H NMR. The thermal properties were fully investigated by TGA. The synthesized copolymers SPFEKAs are soluble in aprotic solvents, and can be cast into membranes on a glass plate from their N,N′-dimethylacetamide (DMAc) solution. A new kind of amphoteric ion exchange membrane (AIEM) was obtained by immersed SPFEKA into 1 M sulfuric acid. The proton conductivities of these membranes are comparable to the most reported sulfonated polymers under the same conditions. The permeability of vanadium ions in vanadium redox flow battery (VRB) was effectively suppressed by introducing quaternary ammonium groups for Donnan exclusion effect. AIEM-20% possess a only 4.4% vanadium ion permeability of Nafion 115. Cell performance tests showed that the VRB assembled with AIEM-20% shows the highest coulombic efficiency (CE) at the current density of 50 mA/cm², because of its lowest VO²⁺ permeability. In conclusion, these ionomers could be promising candidates for ion-exchange membranes for VRB applications.     

Improving the proton conductivity of proton exchange membranes via incorporation of HPW-functionalized mesoporous silica nanospheres into SPEEK

A highly stable composite proton exchange membrane (PEM) was developed by loading phosphotungstic acid in mesoporous silica nanospheres (HPW@MSNs) and blending with sulfonated poly (ether ether ketone) (SPEEK). The SPEEK/HPW@MSNs-0.5 membrane exhibits enhanced comprehensive performance, such as improved and stable proton conductivity and increased methanol barrier property. The proton conductivity decreased by 15.10% after 240 h at 60 °C and was 1.9 times lower than that of the SPEEK/HPW membrane. The selectivity of the SPEEK/HPW@MSNs-0.5 membrane was about 2.0 times that of the pure SPEEK membrane and 3.4 times that of the SPEEK/HPW membrane.     

Sulfonated poly(tetramethydiphenyl ether ether ketone) membranes for vanadium redox flow battery application

Sulfonated poly(tetramethydiphenyl ether ether ketone) (SPEEK) with various degree of sulfonation is prepared and first used as ion exchange membrane for vanadium redox flow battery (VRB) application. The vanadium ion permeability of SPEEK40 membrane is one order of magnitude lower than that of Nafion 115 membrane. The low cost SPEEK membranes exhibit a better performance than Nafion at the same operating condition. VRB single cells with SPEEK membranes show very high energy efficiency (>84%), comparable to that of the Nafion, but at much higher columbic efficiency (>97%). In the self-discharge test, the duration of the cell with the SPEEK membrane is two times longer than that with Nafion 115. The membrane keeps a stable performance after 80-cycles charge-discharge test.     

Electrospun multifunctional sulfonated carbon nanofibers for design and fabrication of SPEEK composite proton exchange membranes for direct methanol fuel cell application

Microstructural construction of a polymer/inorganic filler interface in organic/inorganic composite proton exchange membranes is a key to design of high performance proton conducting materials. Here, carbon nanofibers (CNFs) prepared through electrospun were successfully sulfonated to improve interfacial compatibility between the sulfonated poly(ether ether ketone) (SPEEK) and the sulfonated CNFs (SCNFs) via hydrogen bonding interaction. In addition, carbon nanofiber mats were successfully sheared into short lengths to facilitate dispersion of the SCNFs in the composite membranes. To demonstrate the effectiveness of the SCNFs on improvement of properties of the composite membranes, key physical quantities, i.e. mechanical strength, proton conductivity and methanol permeation were measured and systematically compared with the results of the neat SPEEK and Nafion 117 membranes. It was found that doping with the SCNFs of various contents could profoundly influence the physical properties of the composite membranes. In particular, mechanical strength, proton conductivity and methanol permeability prevention of the composite membranes were significantly enhanced upon incorporation of the SCNFs as fillers. The study provides useful insight into the investigation of the SCNFs based composite membranes for fuel cell applications.     

Enhancement of proton conductivity of polymer electrolyte membrane enabled by sulfonated nanotubes

Proton exchange membrane (PEM) with high proton conductivity is crucial to the commercial application of PEM fuel cell. Herein, sulfonated halloysite nanotubes (SHNTs) with tunable sulfonic acid group loading were synthesized and incorporated into sulfonated poly(ether ether ketone) (SPEEK) matrix to prepare nanocomposite membranes. Physicochemical characterization suggests that the well-dispersed SHNTs enhance the thermal and mechanical stabilities of nanocomposite membranes. The results of water uptake, ionic exchange capacity, and proton conductivity corroborate that the embedded SHNTs interconnect the ionic channels in SPEEK matrix and donate more continuous ionic networks. These networks then serve as proton pathways and allow efficient proton transfer with low resistance, affording enhanced proton conductivity. Particularly, incorporating 10% SHNTs affords the membrane a 61% increase in conductivity from 0.0152 to 0.0245 S cm⁻¹. This study may provide new insights into the structure-properties relationships of nanotube-embedded conducting membranes for PEM fuel cell.     

Investigation of the effects of AMPS-modified nanoclay on fuel cell performance of sulfonated aromatic proton exchange membranes

Here we describe preparation and characterization of a series of nanocomposite polyelectrolytes based on partially sulfonated poly (ether ether ketone) (SPEEK) and organically modified montmorillonite (MMT). Optimum degree of sulfonation for SPEEK is selected based on its transport properties. MMT is modified via ion exchange reaction using a 2-acrylamido-2-methylpropanesulfonic acid (AMPS) as a functional modifier. AMPS-MMT at different loadings is introduced into the SPEEK matrices via the solution intercalation technique. Also, the nanocomposite membranes are fabricated using SPEEK and commercially available nanoclays like Cloisite Na (Na-MMT) and Cloisite 15A. Transport properties, proton conductivity and methanol permeability of the fabricated composite membranes are evaluated. Presence of AMPS-MMT significantly decreases the activation energy needed for proton conductivity. A membrane based on SPEEK/AMPS-MMT-3 wt% is selected as an optimum formulation which exhibits a high selectivity and power density at the elevated methanol concentrations. Moreover, it is found that the optimum nanocomposite membrane not only provides higher power output compared to the neat SPEEK and Nafion^®117 membranes, but also exhibits a higher open circuit voltage (OCV) in comparison with pristine SPEEK and commercial Nafion^® 117 membranes. Owing to the desirable transport and electrochemical properties SPEEK/AMPS-MMT nanocomposite can be considered as an alternative membrane for direct methanol fuel cell applications.     

An effective strategy to enhance the performance of the proton exchange membranes based on sulfonated poly(ether ether ketone)s

We report an effective and facile approach to enhance the dimensional and chemical stability of sulfonated poly(ether ether ketone) (SPEEK) type proton exchange membranes through simple polymer blending for fuel cell applications, using commercial available materials. The polymeric blends with sulfonated poly(aryl ether sulfone)s (SPAES) were simply fabricated by a three-component system, which contained SPEEK (10–50 wt%, 1.83 mmol/g), and SPAES-40 (1.72 mmol/g)/SPAES-50 (2.04 mmol/g) at 1:1 in weight. The SPAES-40 was selected for mechanical and dimensional stability reinforcing, while SPAES-50 for the good polymer compatibility. The obtained SPEEK/SPAES blend membranes showed depressed water uptake, better dimensional and oxidative stability, together with higher proton conductivity beyond 70 °C than the pristine SPEEK membrane. The apparent improvements in membrane properties were associated with the homogeneous dispersion of SPEEK and both SPAES copolymers inside the membranes as well as the rearrangements of the polymeric chains. The SPEEK content should be properly controlled in the range of 10–40% (B10 to B40). In a H₂/O₂ fuel cell test, B30 showed a maximum power density of 700 mW/cm², which was 1.6 times as high as that of B40 at 80 °C under 100% RH. The further cross-linking treatment produced more ductile and enduring blend membranes, indicating an appreciable prospective for fuel cell applications.     

Composite membranes based on a novel benzimidazole grafted PEEK and SPEEK for fuel cells

Poly(ether ether ketone) (PEEK) and sulfonated poly(ether ether ketone) (SPEEK, IEC = 2.07 mequiv.g⁻¹) have been synthesized via nucleophilic aromatic substitution reaction. Bromomethylated poly(ether ether ketone) (PEEK-Br) is then prepared and reacted with 2-benzimidazolethiol to obtain the benzimidazole grafted poly(ether ether ketone) (PEEK-BI). The structures of PEEK-Br and PEEK-BI are characterized by ¹H NMR spectra. Composite membranes based on SPEEK and PEEK-BI are prepared and their properties used for fuel cells are studied in detail. The results show that the composite membranes exhibit greatly improved mechanical properties as well as reduced water uptake and methanol permeability compared with the pristine SPEEK membrane. The increased oxidative stability and selectivity indicate that the composite membranes are promising to be used as proton exchange membranes.     

A facile,effective thermal crosslinking to balance stability and proton conduction for proton exchange membranes based on blend sulfonated poly(ether ether ketone)/sulfonated poly(arylene ether sulfone)

The development of hydrocarbon polymer electrolyte membranes with high proton conductivities and good stability as alternatives to perfluorosulfonic acid membranes is an ongoing research effort. A facile and effective thermal crosslinking method was carried out on the blended sulfonated poly (ether ether ketone)/poly (aryl ether sulfone) (SPEEK/SPAES) system. Two SPEEK polymers with ion exchange capacities (IECs) of 1.6 and 2.0 mmol g^?1 and one SPAES polymer (2.0 mmol g^?1) were selected to create different blends. The effect of thermal crosslinking on the fundamental properties of the membranes, especially their physicochemical stability and electrochemical performance, were investigated in detail. The homogeneous and flexible thermally-crosslinked SPEEK/SPAES membranes displayed excellent mechanical toughness (27–46 Mpa), suitable water uptake (<60%), high dimensional stability (swelling ratio < 15%) and large proton conductivity (>120 mS cm^?1) at 80 °C. The thermal crosslinking membranes also show significantly enhanced hydrolytic (<2.5%) and oxidative stability (<2%). Fuel cell with t-SPEEK/SPAES (1:2:2) membrane achieves a power density of 665 mW cm^?2 at 80 °C.     

Multi-functionalized acid-base double-shell nanotubes are incorporated into the proton exchange membrane to cope with low humidity conditions

Proton exchange membranes (PEM) with high proton conductivity and water retention are critical to the commercial application of proton exchange membrane fuel cells (PEMFC). In this study, acid-base double-shell nanotubes with carboxylate inner shell and an imidazole outer shell (DSNT-A@B) are synthesized via continuous distillation-precipitation polymerization using halloysite nanotubes (HNTs) as seeds. Then, it is incorporated into sulfonated poly (ether ether ketone) matrix to prepare composite membranes. The carboxylic inner shell can increase the content of combined water, thereby giving the composite membrane higher water retention. The imidazole shell acts as basic shell to create acid-base pairs with the membrane and inner shell to promote proton conductivity following the Grotthuss mechanism. The results show that when the blending amount is 5 wt%, the proton conductivity of the composite membrane reaches 0.336 S/cm at 80 °C and 100% relative humidity (RH), which is twice as high as that of the original membrane. In particular, the water loss of SPEEK/DSNT-A@B-10 composite membrane is only 54.55% at 40 °C and 20% RH, which is 32.77% lower than the SPEEK membrane. Therefore, this DSNT-A@B/SPEEK composite membrane can be used as a potential candidate for high temperature and low humidity fuel cells.     

Enhancement of fuel cell properties in polyethersulfone and sulfonated poly (ether ether ketone) membranes using metal oxide nanoparticles for proton exchange membrane fuel cell

The proton exchange membrane (PEM) was synthesized using polyethersulfone (PES), sulfonated poly (ether ether ketone) (SPEEK) and nanoparticles. The metal oxide nanoparticles such as Fe₃O₄, TiO₂ and MoO₃ were added individually to the polymer blend (PES and SPEEK). The polymer composite membranes exhibit excellent features regarding water uptake, ion exchange capacity and proton conductivity than the pristine PES membrane. Since the presence of sulfonic acid groups provides by added SPEEK and the unique properties of inorganic nanoparticles (Fe₃O₄, TiO₂ and MoO₃) helps to interconnect the ionic domain by the absorption of more water molecules thereby enhance the conductivity value. The proton conductivity of PES, SPEEK, PES/SPEEK/Fe₃O₄, PES/SPEEK/TiO₂ and PES/SPEEK/MoO₃ membranes were 0.22 × 10^?4 S/cm, 5.18 × 10^?4 S/cm, 3.57 × 10^?4 S/cm, 4.57 × 10^?4 S/cm and 2.67 × 10^?4 S/cm respectively. Even though the blending of PES with SPEEK has reduced the conductivity value to a lesser extent, hydrophobic PES has vital role in reducing the solvent uptake, swelling ratio and improves hydrolytic stability. Glass transition temperature (T_g) of the membranes were determined from DSC thermogram and it satisfies the operating condition of fuel cell system which guarantees the thermal stability of the membrane for fuel cell application.     

Improving the proton conductivity of sulfonated poly (ether ether ketone) membranes by incorporating a crystalline nanoassembly of trimesic acid and melamine

A novel proton exchange membrane was synthesized by embedding a crystalline which was nano-assembled through trimesic acid and melamine (TMA·M) into the matrix of the sulfonated poly (ether ether ketone) (SPEEK) to enhance the proton conductivity of the SPEEK membrane. Fourier transform infrared indicated that hydrogen bonds existed between SPEEK and TMA·M. XRD and SEM indicated that TMA·M was uniformly distributed within the matrix of SPEEK, and no phase separation occurred. Thermogravimetric analysis showed that this membrane could be applied as high temperature proton exchange membrane until 250 °C. The dimensional stability and mechanical properties of the composite membranes showed that the performance of the composite membranes is superior to that of the pristine SPEEK. Since TMA·M had a highly ordered nanostructure, and contained lots of hydrogen bonds and water molecules, the proton conductivity of the SPEEK/TMA·M-20% reached 0.00513 S cm⁻¹ at 25 °C and relative humidity 100%, which was 3 times more than the pristine SPEEK membrane, and achieved 0.00994 S cm⁻¹ at 120 °C.     

Sulfonated poly(arylene ether sulfone) as a methanol-barrier layer in multilayer membranes for direct methanol fuel cells

Novel poly(arylene ether sulfone) copolymers containing different amount of pendant sulfonic acid groups have been synthesized by an aromatic substitution polymerization reaction. The properties of the synthesized sulfonated poly(diphenylsulfone-diphenol) (SDPS-DP) copolymers depend on the sulfonic acid group content in the copolymers. Although all the copolymers show good thermal stability, low liquid uptake, and low methanol crossover, they exhibit lower proton conductivity than Nafion or sulfonated poly(ether ether ketone) (SPEEK). Taking advantage of the low methanol crossover, multilayer membranes consisting of the SDPS-DP copolymer as a methanol-barrier center layer and SPEEK as the proton-conducting outer layers have been fabricated and characterized. The SPEEK/SDPS-DP-60/SPEEK multilayer membranes with an optimized center layer thickness are found to exhibit better performance and higher power density in DMFC than plain SPEEK and Nafion 115 membranes.     

Hydrophilic treatment poly(tetrafluoroethylene) reinforced sulfonated poly(ether ether ketone) composite membrane for proton exchange membrane fuel cell application

A reinforced composite membrane based on SPEEK (sulfonated poly ether ether ketone) and porous PTFE substrate (polytetrafluoroethylene) is fabricated and investigated for proton exchange membrane fuel cell application. In order to improve the combination between SPEEK polymer and PTFE matrix, PTFE substrate is hydrophilically pretreated by naphthalene sodium solution. The experimental results indicate that SPEEK can impregnate into treated PTFE substrate (abbreviated as trPTFE) more easily. The variation of PTFE surface property before and after treatment is characterized by water contact angle experiment and ATR-FTIR technique. The impregnated status of SPEEK polymer in PTFE matrix is also characterized by ATR-FTIR. According to the appearance photo of two composite membranes, it is showed that SPEEK/trPTFE composite membrane has more uniform and homogeneous morphology. Moreover, the mechanical property of SPEEK/trPTFE composite membrane also has an advantage over pristine SPEEK membrane. Due to the reinforced effect of trPTFE substrate, thinner composite membrane can be applied in single cell evolution and achieves better performance as a result.     

Sulfonated poly(ether ether ketone) membranes with sulfonated graphene oxide fillers for direct methanol fuel cells

Sulfonated organosilane functionalized graphene oxides (SSi-GO) synthesized through the grafting of graphene oxide (GO) with 3-mercaptopropyl trimethoxysilane and subsequent oxidation have been used as a filler in sulfonated poly(ether ether ketone) (SPEEK) membranes. The incorporation of SSi-GOs greatly increases the ion-exchange capacity (IEC), water uptake, and proton conductivity of the membrane. With well-controlled contents of SSi-GOs, the composite membranes exhibit higher proton conductivity and lower methanol permeability than Nafion^® 112 and Nafion^® 115, making them particularly attractive as proton exchange membranes (PEMs) for direct methanol fuel cells (DMFC). The composite membrane with optimal SSi-GOs content exhibit over 38 and 17% higher power densities, respectively, than Nafion^® 112 and Nafion^® 115 membranes in DMFCs, offering the possibilities to reduce the DMFC membrane cost significantly while keeping high-performance.     

Sulfonated poly(ether ether ketone)/poly(ether sulfone) composite membranes as an alternative proton exchange membrane in microbial fuel cells

Custom-made proton exchange membranes (PEM) are synthesized by incorporating sulfonated poly(ether ether ketone) (SPEEK) in poly(ether sulfone) (PES) for electricity generation in microbial fuel cells (MFCs). The composite PES/SPEEK membranes at various composition of SPEEK are prepared by the phase inversion method. The membranes are characterized by measuring roughness, proton conductivity, oxygen diffusion, water crossover and electrochemical impedance. The conductivity of hydrophobic PES membrane increases when a small amount (3–5%) of hydrophilic SPEEK is added. The electrochemical impedance spectra shows that the conductivity and capacitance of PES/SPEEK composite membranes during MFC operation are reduced from 6.15 × 10⁻⁷ to 6.93 × 10⁻⁵ (3197 Ω–162 Ω) and from 3.00 × 10⁻⁷ to 1.56 × 10⁻³ F, respectively when 5% of SPEEK added into PES membrane. The PES/SPEEK 5% membrane has the highest performance compared to other membranes with a maximum power density of 170 mW m⁻² at the maximum current density of 340 mA m⁻². However, the interfacial reaction between the membrane and the cathode with Pt catalyst indicates moderate reaction efficiency compared to other membranes. The COD removal efficiency of MFCs with composite membrane PES/SPEEK 5% is nearly 26-fold and 2-fold higher than that of MFCs with Nafion 112 and Nafion 117 membranes respectively. The results suggest that the PES/SPEEK composite membrane is a promising alternative to the costly perfluorosulfonate membranes presently used as separators in MFC systems.