Poly(isatin-piperidinium-terphenyl) anion exchange membranes with improved performance for direct borohydride fuel cells

In this work, an effective design strategy for anion exchange membranes (AEMs) incorporating ether-bond free and piperidinium cationic groups promote chemical stability. A series of poly (isatin-piperidium-terphenyl) based AEMs were synthesized by superacid catalyzed polymerization reaction, followed by quaternization. The effect of functionalization on the performance of poly (isatin-N-dimethyl piperidinium triphenyl) (PIDPT-x) AEMs was investigated. Highly reactive N-propargylisatin was introduced into the backbone to achieve high molecular weight polymers (η_a = 2.06–3.02 dL g⁻¹) leading to robust mechanical properties, as well as modulating 1.78–2.00 mmol g⁻¹ of the ion exchange capacity (IEC) of the AEMs by feeding. Apart from that, the rigid non-ionized isatin-terphenyl segment provides AEMs improved dimensional stability with a swelling ratio of less than 12% at 80 °C. Among them, PIDPT-90 exhibited a higher OH⁻ conductivity of 105.6 mS cm⁻¹ at 80 °C. The alkali-stabilized PIDPT-85 AEM was presented, in which OH⁻ conductivity retention maintained 85.6% in a 2 M NaOH at 80 °C after 1632 h. Afterward, the direct borohydride fuel cells (DBFC) with PIDPT-90 membrane as a separator showed an open-circuit voltage of 1.63 V and a peak power density of 75.5 mWcm⁻² at 20 °C. This work demonstrates the potential of poly (isatin- N-dimethyl piperidinium triphenyl) as AEM for fuel cells.     

Synthesis and characterization of crosslinked poly (vinyl alcohol)/layered double hydroxide composite polymer membranes for alkaline direct ethanol fuel cells

The low ionic conductivity and low thermal stability of conventional quaternary ammonium group functionalized anion-exchange membranes (AEM) are two key parameters that limit the performance of AEM direct ethanol fuel cells (AEM DEFCs). The present work is to address these issues by synthesizing crosslinked poly (vinyl alcohol)/layered double hydroxide (PVA/LDH) hybrid membranes with solution casting method. The experimental results indicate that incorporating 20 wt.% LDH into the PVA resulted in not only a higher ionic conductivity, but also a lower ethanol permeability. The performance test of the DEFC using the PVA/LDH hybrid membrane shows that the fuel cell can yield a power density of 82 mW cm⁻² at 80 °C, which is much higher than that of the AEM DEFC employing the quaternary ammonium group functionalized membrane. A constant current discharge test shows that the PVA/20LDH membrane can be operated stably at relatively high temperatures.     

Pendent piperidinium-functionalized blend anion exchange membrane for fuel cell application

Alkaline anion exchange membrane fuel cell has fast cathode reactions and thus allows the use of low cost electrocatalysts. However, its practical application is hindered by the low hydroxide ion conductivity and alkaline stability of AEM. In this study, pendent piperidinium functionalized polyetheretherketone is synthesized and blended with polybenzimidazole for fabrication of composite anion exchange membrane. The pendent piperidinium functionalized side chains can create well-connected ionic transporting channels and thus impart the blend membranes high hydroxide conductivity (61.5–72.8 mS cm⁻¹ at 80 °C) and good tensile strength (42.8–58.9 MPa). Due to the strong interactions between polybenzimidazole and piperidinium groups of the polymers as confirmed by Fourier transform infrared spectroscopy, the piperidinium functionalized blend anion exchange membrane can retain 95% of its original OH⁻ conductivity value when treated in 1 M KOH at 60 °C for 576 h. The single fuel cell assembled with the membrane can yield a peak power density of 87 mW cm⁻² at 80 °C. Our work provides a new and effective method to balance the hydroxide conductivity and alkaline stability of anion exchange membranes.     

Facile construction of poly(arylene ether)s-based anion exchange membranes bearing pendent N-spirocyclic quaternary ammonium for fuel cells

Anion exchange membrane (AEM) fuel cells have received significant attention due to their low fuel permeability and the use of non-platinum catalysts. However, the development of AEMs with robust chemical stability and high conductivity is still a great challenge. Herein, we prepare a new type of partially fluorinated backbone bearing pendent N-spirocyclic quaternary ammonium (QA) cations via a facile Williamson reaction, which displays great potential for fuel cells. The integration of the two substructures (a fluorinated moiety into a polymer backbone and a pendent cation structure) is beneficial for the fabrication of a well-defined micro-phase separation structure, thereby facilitating the construction of a highly-efficient ion transporting pathway. Correspondingly, the resulting AEM (PAENQA-1.0), despite its a relatively low ionic exchange capacity (0.93 meq g⁻¹) demonstrates a conductivity of 63.1 mS cm⁻¹ (80 °C). Meanwhile, the constrained ring conformation of N-spirocyclic QA results in improved stability of the AEMs.     

Study on the partially cross-linked poly(styrene-b-(ethylene-co-butylene)-b-styrene) anion exchange membrane remotely (spaced hexyl) grafted double cation separated by different alkyl groups

In order to improve the alkali stability and OH⁻ conductivity of Poly (styrene-b-(ethylene-co-butylene)-b-styrene) (SEBS)-based anion exchange membranes (AEMs), double cations with different alkyl intervals are remotely grafted onto the SEBS skeleton with hexyl as a linker through reactions such as acylation and ketone reduction. Then, SEBS-0.8Cn-0.2C6 cross-linked membranes were prepared to study the effect of the length of the alkyl chain between the dications on the ion transport and other properties. The OH⁻ conductivity of SEBS-0.8C4-0.2C6 cross-linked membrane can reach 85.27 mS cm⁻¹ at 80 °C, and the peak power density can reach 225 mW cm⁻² at a current density of 450 mA cm⁻². As the dicationic spacer alkyl chains became longer, the swelling rate and water uptake of the membranes increased, resulting in significant improvements in mechanical properties and chemical stability. After soaking in 2 M NaOH solution at 80 °C for 1200 h, the conductivity of SEBS-0.8C6-0.2C6 decreased by only 5.76%. Optimizing the side chain structure of SEBS skeleton can effectively improve the comprehensive performance of AEM.     

Facile self-crosslinking to improve mechanical and durability of polynorbornene for alkaline anion exchange membranes

Crosslinking is a valid approach to enhance the mechanical and durability performance of anion exchange membranes (AEMs). Herein, a facile and effective self-crosslinking strategy, with no need for an additional crosslinker or a catalyzer, is proposed. A series of tunable self-crosslinking and ion conduction polynorbornene membranes are designed. The 5-norbornene-2-methylene glycidyl ether (NB-MGE) component which affords self-crosslinking enhances dimensional stability, while the flexible 5-norbornene-2-alkoxy-1-hexyl-3-methyl imidazolium chloride (NB-O-Im⁺Cl⁻) hydrophilic unit contributes high conductivity. The crosslinking significantly decreases the water uptake, and water swelling ratio provides excellent solvent-resistance and enhances the thermal and mechanical properties. Additionally, crosslinked rPNB-O-Im-x AEMs exhibit desirable alkaline stability. Impressively, the rPNB-O-Im-30 (IEC = 1.377) shows a moderate ion conductivity (61.8 m S cm⁻¹, 80 °C), with a suppressed water absorption and 88.17% initial OH⁻ conductivity is maintained after treated for 240 h with a 1.0 M NaOH solution at 60 °C. Suitably assessed of rPNB-O-Im-30 AEM reveals a 98.4 mW cm⁻² peak power density reached at a current density of about 208 mA cm⁻². The report offers a facile and effectual preparative technique for preparing dimensional and alkaline stable AEMs for fuel cells applications.     

Development of crosslinked SEBS-based anion exchange membranes for water electrolysis: Investigation of the crosslinker effect

SEBS (styrene-b-(ethylene-co-butylene)-b-styrene)) is a non-aryl-ether-type tri-block copolymer widely used as an anion exchange membrane (AEM) material due to its excellent alkaline stability and phase separation properties. However, low tensile strength due to the aliphatic chains and the poor physical properties of the SEBS-based membranes limit their practical application for AEM water electrolysis (AEMWE) or AEM fuel cell (AEMFC). In this study, three types of crosslinked AEMs were prepared using bromohexyl pentafluorobenzyl SEBS as a polymer backbone, and three different crosslinkers, dimethyl amine (DMA), tetramethyl diaminohexane (TMHA), and tris(dimethyl aminomethyl) phenol (TDMAP). Once introduced, these crosslinking agents were converted into the corresponding conducting head groups. The thermal, chemical, physical, and electrical properties of the obtained crosslinked membranes were then investigated for use in AEMWE. In particular, the TDMAP-50x-SEBS membrane with 50% degree of crosslinking experienced hydrogen bonding with water and OH⁻ due to the presence of OH groups in the structure of the crosslinking agent (TDMAP). Because of this, the membrane showed an improved morphology and high conductivity (20 °C: 31.8 mS cm⁻¹, 80 °C: 109.9 mS cm⁻¹). In addition, TDMAP induced physical crosslinking by hydrogen bonding between molecules so that the corresponding membrane (TDMAP-50x-SEBS) exhibited high alkaline and oxidative stability and good mechanical properties. This SEBS-based membrane has a tensile strength of 18.0 MPa and Young's modulus of 165.14 MPa. The WE single-cell test (1 M KOH solution at 70 °C) using TDMAP-50x-SEBS also showed a cell performance of 1190 mA cm⁻² at 2.0 V. This is 126% higher than the cell performance measured for FAA-3-50, a commercialized AEM material, under the same conditions.     

Novel quaternized carbon dots modified polysulfone-based anion exchange membranes with improved performance

At present, low conductivity and poor chemical stability are still the biggest challenges in the research on anion exchange membranes (AEMs). Herein, novel nanocomposite AEMs were first constructed by introducing quaternized carbon dots (QCDs) into the imidized polysulfone matrix (Im-PSU). QCDs were synthesized by quaternization of CDs derived from citric acid and ethylenediamine. The physicochemical properties and electrochemical properties of the nanocomposite AEMs were significantly improved due to the introduction of QCDs. It was found that the QCDs can improve the ion transport channel of the nanocomposite AEMs. Compared with pure Im-PSU AEM, the OH⁻ conductivity and physicochemical properties of the nanocomposite membranes were enhanced, and the OH⁻ conductivity of ImPSU-1.0%-QCDs composite membrane can reach 109.3 mS cm⁻¹ at 80 °C, and 61.2% initial OH⁻ conductivity was maintained in 1.0 M NaOH solution for 500 h at 60 °C. Our research proves that the nanofiller with a small size can better improve the performance of composite AEMs, and provide an efficient strategy for future research work in the design and preparation of AEMs.     

The effect of electrode parameters on the performance of anion exchange polymer membrane fuel cells

An investigation of several electrode parameters on performance of an alkaline membrane fuel cell is described. The studied parameters were: ionomer content, anode and cathode catalyst layer thickness, electrode aminating agent and membrane thickness.It was found that an optimum ionomer content depended on a balance between the OH⁻ ion/water mobility and the oxygen solubility/diffusivity through it and which varied with temperature. Thick catalyst layers were necessary for the anode as thin anode catalyst layers suffered from flooding. 40%Pt/C provided the best thickness (with loading of 0.4 mg_Pt cm⁻²) for cathodes operating with air.An aminated low density poly(ethylene-co-vinyl benzyl chloride) (LDPE-VBC) membrane was shown to be a good membrane for an alkaline membrane fuel cell, giving conductivities up to 0.13 S cm⁻¹ at 80 °C. A Membrane Electrode Assembly (MEA) utilizing this membrane with fully hydrated thickness of 57 μm produced good peak power density, at a high potential of 500 mV, of 337 mW cm⁻² with air (1 bar gauge) at 60 °C.     

Branched poly(ether ether ketone) based anion exchange membrane for H2/O2 fuel cell

High-performance anion exchange membranes (AEMs) are in need for practical application of AEM fuel cells. Novel branched poly(ether ether ketone) (BPEEK) based AEMs were prepared by the copolymerization of phloroglucinol, methylhydroquinone and 4,4′-difluorobenzophenone and following functionalization. The effects of the branched polymer structures and functional groups on the membrane's properties were investigated. The swelling ratios of all the membranes were kept below 15% at room temperature and had good dimensional stability at elevated temperatures. The branching degree has almost no effect on the dimensional change, but plays a great role in tuning the nanophase separation structure. The cyclic ammonium functionalized membrane showed a lower conductivity but a much better stability than imidazolium one. The BPEEK-3-Pip-53 membrane with the branching degree of 3% and piperidine functionalization degree of 53% showed the best performances. The ionic conductivity was 43 mS cm⁻¹ at 60 °C. The ionic conductivity in 1 M KOH at 60 °C after 336 h was 75% of its initial value (25% loss of conductivity), and the IEC was 83% of its initial value (17% loss of IEC), suggesting good alkaline stability. The peak energy density (60 °C) of the single H₂/O₂ fuel cell with BPEEK-3-Pip-53 membrane reached 133 mW cm⁻² at 260 mA cm⁻².     

Performance characteristics of air-breathing anion-exchange membrane direct ethanol fuel cells

An air-breathing direct ethanol fuel cell (DEFC) with an anion-exchange membrane (AEM) and Pt-free electrodes is designed and investigated. Particular attention is paid to studying the performance characteristics of the air-breathing AEM DEFC. Experimental results reveal that this air-breathing AEM DEFC yields a peak power density as high as 38 mW cm⁻² at room temperature, which is comparable to the conventional Pt-based proton exchange membrane direct methanol fuel cells (PEM DMFCs). The overshoot/undershoot behaviors of both the cell voltage and cell temperature are avoided in the air-breathing AEM DEFC due to the use of ethanol-tolerant cathode catalyst. It is also found that the cathode water flooding behavior occurs in this air-breathing AEM DEFC, thus lowering the cell performance.     

Preparation and characterization of a polyvinyl alcohol grafted bis-crown ether anion exchange membrane with high conductivity and strong alkali stability

A new type of symmetrical bis-crown ether is prepared by connecting dibenzo-18-crown-6 ether on both sides of the chromotropic acid, and then grafting the aforementioned bis-crown ether onto polyvinyl alcohol matrix to prepare a series of anion exchange membranes (AEMs), which their have high conductivity and strong alkali stability. These synthesized membranes were named B-C_X%-P AEMs (x is the mass percentage of the symmetrical bis-crown ether (B–C)). Then, the chemical structure of aforementioned AEMs were verified by means of ¹H NMR, FT-IR and UV. Meanwhile, the OH⁻ conductivity, alkaline stability and single cell performance of the synthesized membrane were also investigated. The results revealed that the conductivity of B–C_30%-P membrane is the highest at 80 °C (235 mS cm⁻¹), and the power density is also the highest (197 mW cm⁻²), and the alkali stability of the membrane synthesized in this paper was also improved. The conductivity at 80 °C was only reduced by 4%, which was obtained by immersing the B–C_30%-P membrane immersed in 6 mol L⁻¹ KOH solution for 168 h, which the aforementioned results proved that the synthesized membrane in this research had excellent OH⁻ conductivity and alkaline stability.     

Effects of hydrolysis degree on ion-doped anion exchange membranes in direct borohydride fuel cells

Herein, polyvinyl alcohol based anion exchange membranes (AEMs) doped with various cobalt and chloride salts are synthesized to investigate the structure-performance relationship of ion-doped AEMs systemically. The performances of ion-doped AEMs are found to be related to the hydrolysis degree (DH) of the doped anions and cations. It is found that cations with varying DH transformed into hydroxides with different sizes and dispersions, which plays a key role in determining the structures and properties of cation-doped AEMs. On the other hand, weak-acid anions remained in the AEMs after alkali immersion, hindering OH⁻ conduction and leading to the degradation of the anion-doped AEMs. High DH cations mildly react with the matrix and transform into more dispersive complexes, while low DH anions are replaced by OH⁻.The direct borohydride fuel cell using CuCl₂-doped AEM exhibits a maximum power density of 202.4 mW cm⁻² at 30 °C.     

High performance direct liquid fuel cells powered by xylose or glucose

In this work, we report the first abiotic, direct liquid fuel cells powered by the monosaccharide xylose using both a fully alkaline fuel cell (with anion exchange membrane) and a split pH fuel cell (with cation exchange membrane). We also report that the same fuel cells can be used with the monosaccharide glucose to produce much higher maximum power density than previously reported for abiotic, direct glucose fuel cells. This first alkaline direct xylose fuel cell (DXFC) produces a maximum power density of 57 mW cm⁻² at optimum conditions, while the split pH DXFC produces a maximum power density of 160 mW cm⁻². Our significantly improved alkaline direct glucose fuel cell (DGFC) produces 90 mW cm⁻² at optimum conditions, while the split pH DGFC produces 189 mW cm⁻². In addition to being high performing, these sugar molecules are naturally abundant, renewable, and known to convert to valuable products such as gluconic acid, glucaric acid, and xylonic acid during electrochemical oxidation. Other fuel cell and electrochemical cell data is also reported herein to understand the role of pH and fuel concentrations on behavior toward the electrochemical oxidation of these sugar molecules in alkaline media.     

Simultaneously enhanced hydroxide conductivity and mechanical properties of quaternized chitosan/functionalized carbon nanotubes composite anion exchange membranes

Low-cost biopolymer chitosan has received considerable attention in the field of anion exchange membranes (AEMs) because it can be easily quaternized and avoids the carcinogenic chloromethylation step. Simultaneously increasing the ionic conductivity and improving mechanical properties of quaternized chitosan (QCS) is key for its high-performance application. In this study, new composite AEMs consisting of QCS and functionalized carbon nanotubes (CNTs) were prepared. CNTs were coated with a thick silica layer onto which high-density quaternary ammonium groups were then grafted. The insulator silica coating effectively prohibits electron conduction among nanotubes and the grafted –NR₃⁺ provides new OH⁻ conductive sites. Incorporating 5 wt% functionalized CNTs into the matrix enhanced ionic conductivity to 42.7 mS cm⁻¹ (80 °C) which was approximately 2 times higher than that of pure QCS. The effective dispersion of CNTs and appropriate interfacial bonding between nanofiller and QCS improved the mechanical properties of AEMs, including both the strength and toughness of the composite membranes. An alkaline direct methanol fuel cell equipped with the composite membrane (5% functionalized CNTs loading) produced an maximum power density of 80.8 mW cm⁻² (60 °C), which was 57% higher than that of pure QCS (51.5 mW cm⁻²). This study broadens the application of natural polymers and provides a new way to design and fabricate composite AEMs with both improved mechanical properties and electrochemical performance.     

End-group crosslinked hexafluorobenzene contained anion exchange membranes

A kind of anion exchange membranes (AEMs) with CC bond end-group crosslinked structure was synthesized successfully. Unlike the traditional aliphatic AEMs, the AEMs were prepared in this work by a strategy to realize the CC bond thermal end-group crosslinking reaction, exhibiting an obvious microphase separation structure and a suitable dimensional stability. The well-defined ion channels constructed in the AEMs guarantee the fast OH⁻ conduction, as confirmed via physical and chemical characterization. The conductivity was dramatically enhanced due to the effective ion channels and increased ion exchange capacity. Among the as-prepared AEMs, the PHFB-VBC-DQ-80% AEM has a conductivity of 135.80 mS cm⁻¹ at 80 °C. The single cell based on PHFB-VBC-DQ-80% can achieve a power density of 141.7 mW cm⁻² at a current density of 260 mA cm⁻² at 80 °C. The AEMs show good thermal stability verified by a thermogravimetric analyzer (TGA). Furthermore, the ionic conductivity of PHFB-VBC-DQ-80% only decreased by 7.1% after being soaked in a 2 M NaOH solution at 80 °C for 500 h.     

N-spirocyclic ammonium-functionalized graphene oxide-based anion exchange membrane for fuel cells

Graphene oxide (GO) is a potential material in the electrode and membrane of polymer electrolyte membrane fuel cells due to its unique structure and various oxygen-containing functional groups. A class of three-layered GO/poly (phenylene oxide) for AEMs was prepared in this work. GO was functionalized with highly stable 6-azonia-spiro [5.5]undecane groups and used as a fast hydroxide conductor, named ASU-GO. Functionalized by N-spirocyclic cations, poly (phenylene oxide) (PIPPO) was then combined with ASU-GO and GO to fabricate the ASU-GO/PIPPO and GO/PIPPO. Notably, the maximum hydroxide conductivity of the ASU-GO/PIPPO was 73.7 mS cm⁻¹ at 80 °C, which was 3 times higher than that of the GO/PIPPO. The enhancement in hydroxide conductivity was due to the changes in the hydroxide transport mechanism and the poor stacked structure of the ASU-GO layer. Only 10.8% drops in hydroxide conductivity of ASU-GP/PIPPO after the alkaline test (1 M KOH at 80 °C for 700 h). Furthermore, the ASU-GO/PIPPO-50 membrane showed a maximum peak power density of 102 mW cm⁻², demonstrating the prepared membrane was promising in the AEM applications.     

Degradation of guanidinium-functionalized anion exchange membrane during alkaline environment

A guanidinium-functionalized anion exchange membrane (AEM) was prepared and characterized. The AEM stability in an alkaline environment and transition structures during the degradation process were studied with DFT (density functional theory)/B3LYP method, 6-31 + G (d) basis set. Experimental results and theoretical analysis showed that the second step (Step 2′) of degradation reaction was the control procedure; guanidinium cation was unstable under alkaline condition. It had lower energy barriers, which decided it was easier for the degradation reaction to occur in high pH environment. The ionic conductivity of AEM was 2.4 × 10⁻² S cm⁻¹ at 80 °C. However, the AEM soaked in 1 M NaOH solution, fragments were found after 10 days. The FTIR analysis showed that the structure of the membrane had been changed due to the attack of hydroxide ion. A new substance, tetramethylurea, had produced.     

Block copolymer anion exchange membrane containing polymer of intrinsic microporosity for fuel cell application

High hydroxide conductivity and good stability of anion exchange membranes (AEMs) is the guarantee that anion exchange membrane fuel cells (AEMFCs) yield high power output for a long time. Balanced conductivity and stability can be better guaranteed by adopting a relatively low ion exchange capacity (IEC) while reducing the ion transport resistance Herein, a novel block copolymer AEM was designed and synthesized, which contains hydrophobic polymer of intrinsic microporosity (PIM) blocks and hydrophilic, quaternized polysulfone (PSF) blocks. The PIM block imparts high free volume to the membrane so that the resistance of hydroxide ion transport can be reduced; meanwhile, the hydrophilic block can self-assemble more easily to produce a better developed hydrophilic microphase, which may function as efficient channels for hydroxide ion transport. Both transmission electron microscopy images and small-angle X-ray scattering patterns suggested that the resulting AEM possessed a microphase separated morphology. The membrane showed a conductivity of 52.6 mS cm^-l at 80 °C with a relatively low IEC of 0.91 mmol g^?1. It also exhibited a good dimensional stability, swelling ratio maintained almost constant (ca. 17%) at 25 to 80 °C. The assembled H₂/O₂ fuel cell yielded a peak power density of 270 mW cm^?2 at 560 mA cm^?2. Our work demonstrates that incorporation of PIM in an AEM by means of block polymerization is an efficient way of promoting microphase separation and facilitating ion transport.     

Ultra-low catalyst loading cathode electrode for anion-exchange membrane fuel cells

A new cathode architecture for anion-exchange membrane fuel cells (AEMFCs) is proposed and fabricated by direct deposition of palladium (Pd) particles onto the surface of the micro-porous layer (MPL) that is interfaced with a backing layer. The MPL is composed of carbon nanotubes while the backing layer is made of a carbon paper. The sputter-deposited electrode with a worm-like shape not only extends the electrochemical active surface area, but also facilitates the oxygen transport. This new cathode, albeit with a Pd loading as low as 0.035 mg cm⁻², enables the peak power density of an AEM direct ethanol fuel cell to be as high as 88 mW cm⁻² (at 60 °C), which is even higher than that using a conventional cathode with a 15-times higher Pd loading. The significance of the present work lies in the fact that the new sputter-deposited electrode is more suitable for fuel-electrolyte-fed fuel cells than the conventional electrode designed for proton-exchange membrane fuel cells (PEMFCs).