Constructing micro-phase separation structure by multi-arm side chains to improve the property of anion exchange membrane

In order to improve the performance of anion exchange membrane (AEMs) as the core component of alkaline fuel cell, a novel pentamethyl-contained phenolphthalein multi-arm monomer is synthesized. The highly imidazolium-functionalized poly (arylene ether ketone) membrane (Im-PEK-x) are prepared by introducing 1,2-dimethylimidazole as hydrophilic segments. The monomer, polymer and anion exchange membranes are confirmed by ¹H NMR spectra. The well-defined micro-phase separated structure of membranes is conducive to ion transport and the structure is investigated by TEM and SAXS. The imidazolium-functionalized membranes (Im-PEK-0.8) exhibits high ionic conductivity (0.148 S/cm at 80 °C). The tensile strength of Im-PEK-0.8 membrane is 30.06 MPa. Furthermore, after immersing in 60 °C, 2 M NaOH solution for 240 h, the ionic conductivity remains 0.092 S/cm for Im-PEK-0.8. The 1,2-dimethylimidazole enhance alkaline stability by steric effect of the substituent group at the C2 position. All these results indicate that this is a new method to enhance conductivity and stability performance of AEMs.     

Novel multi-channel anion exchange membrane based on poly ionic liquid-impregnated cationic metal-organic frameworks

The “trade-off” effect between hydroxide conductivity and dimensional stability is challenging issue for anion exchange membrane fuel cells (AEMFCs). In this study, the framework of UiO-66-NH₂ is for the first time applied to anion exchange membranes (AEMs). The robust pore walls of UiO-66-NH₂ with mechanical and structural durabilities protect the membrane from the excessive swelling effects (a swelling ratio of 7%). In addition, the framework of UiO-66-NH₂ is directly modified into (UiO-66-NH₂)⁺Cl⁻ as hydroxide conduction channels by anion stripping for the first time. And we construct well-organized ion nanochannels by the in-situ self-assembly of N,N,N′,N' -tetramethyl-1,6-hexanediamine (TMHDA) and allyl bromide within the highly ordered pores of (UiO-66-NH₂)⁺Cl⁻. The obtained QA@(UiO-66-NH₂)⁺Cl⁻ then incorporated into pristine membrane (QAPPO) to fabricate the novel multi-channel AEMs. The hydroxide conductivity of QA@(UiO-66-NH₂)⁺Cl⁻/PPO is up to 123 mS⋅cm⁻¹ at 80 °C, which is greatly improved compared to QAPPO pristine membrane.     

Anionic polysulfone ionomers and membranes containing fluorenyl groups for anionic fuel cells

Poly(arylene ether sulfone) ionomers containing fluorenyl groups and functionalized with benzyltrimethylammonium groups were synthesized through polycondensation, chloromethylation, and amination reactions. The resulting polymers were characterized by ¹H NMR, FT-IR and TGA. Polymer membranes were solvent cast from DMF on Teflon plates to form clear, flexible anion exchange membranes (AEMs). Carbonate anions had conductivities in the AEMs up to 63.12 mS cm⁻¹ at 70 °C and were used in a carbonate fuel cell. The membranes were stable in 1 M carbonate solution (pH 11). However, conductivity loss was observed during soaking in 1 M hydroxide solution (pH > 14) at 50 °C. A carbonate fuel cell operating at room temperature with H₂ at the anode and O₂ and CO₂ at the cathode had a maximum power density of 4.1 mW cm⁻².     

Mechanically robust semi-interpenetrating polymer network via thiol-ene chemistry with enhanced conductivity for anion exchange membranes

Anion exchange membranes (AEMs) have emerged as crucial functional materials in various electrochemical device, such as fuel cell. Both the mechanical property and ionic conductivity play important roles in AEMs. Herein, a series of semi-interpenetrating polymer network AEMs are prepared by introducing flexible polyvinyl alcohol to the rigid photo-crosslinked poly (2,6-dimethyl-1,4-phenylene oxide) network. Such strategy endows AEM with tunable composition and mechanical property. Among these AEMs, membrane with an IEC of 1.46 mmol/g shows the highest mechanical strength of 30.8 MPa and a relatively lower swelling ratio, as well as the highest hydroxide conductivity. Importantly, the alkaline stability of these AEMs has been improved, 66.5% of the hydroxide conductivity is maintained after treatment in 1 M NaOH at 80 °C for 1000 h. Tentative assembly of H₂/O₂ fuel cell at 60 °C with this AEM displays a peak power density of 78 mW/cm². All the results demonstrate that sIPN structure is a promising way to enhance the mechanical property, ionic conductivity, and the alkaline stability of AEMs for the future application in AEMFCs.     

Preparation and characterization of fluorinated poly(aryl ether oxadiazole)s anion exchange membranes based on imidazolium salts

A series of fluorinated poly(aryl ether oxadiazole)s ionomers based on imidazolium salts (FPAEO-xMIM) were synthesized by quaternization of bromomethylated poly(aryl ether oxadiazole)s (FPAEO-xBrTM) with 1-methyl imidazole as aminating reagent. The anion exchange membranes (AEMs) were prepared by casting method and then immerged in aqueous sodium hydroxide for hydroxide ion exchanging. The structure of the obtained ionomers was characterized by ¹H-NMR and FT-IR measurements. The physical and electrochemical properties of the membranes were also investigated. The hydroxide conductivity of FPAEO-xMIM membranes was higher than 10⁻² S cm⁻¹ at room temperature, while the water uptake and swelling ratio was moderate even at elevated temperature. TGA analysis revealed that the membranes based on imidazolium salts had good thermal stability.     

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.     

Guanidinium cationic covalent organic nanosheets-based anion exchange composite membrane for fuel cells

Covalent organic frameworks (COFs) used for anion exchange membrane fuel cells (AEMFCs) are commonly endowed with ion conductivity by post-synthesis modification. However, this method usually results in uneven distribution of functional groups, low functionalization and severe ion capacity fade. Limited by hydrophobic skeleton and relatively large particle size of COFs, the COFs doping amount of the composite membrane is not high. Here we design and synthesize a series of guanidinium cationic covalent organic nanosheets-based anion exchange composite membranes. The positively charged guanidinium group as a building block can induce COF-DhaTG_Cl self-exfoliation into a few layered nanosheets through strong interlayer repulsion. Then, the nanosheets were introduced into quaternary ammonium-functionalized poly(2,6-dimethyl-1,4-phenyl ether) (QPPO). A series of COF-DhaTG_Cl/PPO composite AEMs was prepared with the highest doping amount of 30 wt% by casting method. The porous structure and repeat cationic guanidinium units on the skeleton will expose ion sites to the target ones, providing faster OH⁻ diffusion kinetics in one-dimensional channels. The OH⁻ conductivity of COF-DhaTG_Cl/PPO-20 composite membrane can reach 148.65 mS/cm at 80 °C. Meanwhile, the composite membrane also exhibits enhanced mechanical strength and alkaline stability with the maximum stress strength of 37.3 MPa and the residual conductivity of 96.29% after immersion in 2 M NaOH solution at 60 °C for two weeks.     

Partially crosslinked comb-shaped PPO-based anion exchange membrane grafted with long alkyl chains: Synthesis,characterization and microbial fuel cell performance

Anion exchange membranes (AEMs) with higher ion exchange capacities (IECw) are limited to applications due to excessive swelling and higher water uptake. Crosslinked macromolecular structures have been a strategy to balance between ionic conductivity and swelling in membranes. However, highly crosslinked AEMs are usually mechanically brittle and poorer in ion transport. Thus we report a series of partially diamine crosslinked (X = 10%, 15%, 20%) comb-shaped AEMs functionalized with dimethylhexadecylammonium groups exhibiting improved flexibility, water uptake and swelling properties over conventional un-crosslinked or fully crosslinked materials. The higher conductivities in these PPO AEM(X) (for example, X = 20%, IECw = 1.96 mmol/g, σ(OH⁻) ~ 67 mS/cm at 80 °C) are attributed to the distinct nanophase separation as observed in SAXS and AFM analyses. Finally, the microbial fuel cell performances of the membranes were compared with commercially available cation and anion exchange membranes.     

A facile fabrication of functionalized rGO crosslinked chemically stable polysulfone-based anion exchange membranes with enhanced performance

Introducing more ionic conductive groups in polymer-based anion exchange membranes (AEMs) can improve the ion exchange capacity and further overcome the disadvantage of low ion conductivity for AEMs. However, the excessive swelling of AEMs caused by exorbitant IEC value may reduce the dimensional stability of membranes. So it is extremely important to modify the structures of AEMs. Herein, we proposed a facile strategy to construct reduced graphene oxide (rGO) stable crosslinked polysulfone-based AEMs with improved properties. rGO was non-covalently modified with pyrene-containing tertiary amine small molecule and polymer via π-π interactions. The as-prepared functionalized rGO (TrGO and PrGO) as both cross-linkers and fillers to fabricate quaternized polysulfone (QPSU)-based AEMs (CQPSU-X-TrGO and CQPSU-X-PrGO) for the first time. The cross-linked membranes can tighten the internal packing structure, and enhance the alkaline resistance, ion conductivity and oxidative stability of AEMs. Furthermore, the hydrophilicity and flexibility of the CQPSU-X-PrGO membranes were significantly improved as compared with that of CQPSU-X-TrGO membranes. PrGO-crosslinked membranes (CQPSU-2%-PrGO, σ_OH⁻ = 117.7 mS/cm) displayed higher ionic conductivities at 80 °C than TrGO-crosslinked membranes (CQPSU-1%-TrGO, σ_OH⁻ = 87.2 mS/cm). The remarkable nanophase separation can be observed in the CQPSU-X-PrGO membranes by TEM. This feasible strategy can be efficiently used to prepare new type of crosslinked organic-inorganic nanohybrid AEMs with excellent chemical stability and high ionic conductivity.     

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.     

Application of 2D nanomaterial MXene in anion exchange membranes for alkaline fuel cells: Improving ionic conductivity and power density

Two types of new 2D MXenes (LiF–Ti₃C₂T_x and NH₄HF₂–Ti₃C₂T_x) were prepared by selective etching of Ti₃AlC₂ with LiF/HCl and NH₄HF₂ aqueous solutions, respectively, and they were introduced as nanofillers into quaternized polysulfone/polyquaternium-10 (QPSU/PQ-10) anion exchange membranes (AEMs) with semi-interpenetrating polymer network, thereby preparing two types of MXene-doped QPSU/PQ-10 AEMs. The resulting MXene-doped QPSU/PQ-10 AEMs have obvious nanoscale microphase-separated morphologies, and their ionic conductivity and power density are significantly improved compared with the pristine QPSU/PQ-10 AEM. Among them, the ionic conductivity and power density of NH₄HF₂–Ti₃C₂T_x MXene-doped AEM can reach 88.76 mS/cm at 80 °C and 106.28 mW/cm² at 60 °C, respectively, which are 26.3% and 37.5% higher than those of the pristine QPSU/PQ-10 AEM. Additionally, the MXene-doped QPSU/PQ-10 AEMs with semi-interpenetrating network have moderate water uptake and swelling ratio, excellent thermal and mechanical properties, as well as good oxidation resistance and alkaline stability, which can meet the application requirements of AEMs for fuel cells, exhibiting their bright application prospects in fuel cells.     

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.     

Crosslinked anion exchange membranes with regional intensive ion clusters prepared from quaternized branched polyethyleneimine/quaternized polysulfone

A series of anion exchange membranes (AEMs) with regionally dense ion clusters are prepared by crosslinking quaternized polysulfone (QPSU) with quaternized branched polyethyleneimine (QBPEI). For the as-prepared QPSU/QBPEI AEMs, the hydrophilic QBPEI forms locally aggregated ion clusters in the QPSU matrix, which can promote the formation of an obvious microphase separation structure in the membrane. The QPSU/QBPEI-3 AEM with an ion exchange capacity of 1.88 meq/g exhibits the best performance, achieving a reasonably high ionic conductivity of 66.14 mS/cm at 80 °C and showing good oxidation stability and alkali resistance. Finally, the maximum power density of a single H₂/O₂ fuel cell with QPSU/QBPEI-3 AEM reaches 75.34 mW/cm² at 80 °C. The above results indicate that QBPEI with a dendritic structure and abundant anionic conductive groups has a good application prospect in the preparation of AEMs with locally aggregated ion clusters and microphase separation structures.     

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.     

Dense 1,2,4,5-tetramethylimidazolium-functionlized anion exchange membranes based on poly(aryl ether sulfone)s with high alkaline stability for water electrolysis

Anion exchange membranes with enough alkaline stability and ionic conductivity are essential for water electrolysis. In this work, a class of anion exchange membranes (PAES-TMI-x) with dense 1,2,4,5-tetramethylimidazolium side chains based on poly(aryl ether sulfone)s are prepared by aromatic nucleophilic polycondensation, radical substitution and Menshutkin reaction. Their chemical structure and hydrophilic/hydrophobic phase morphology are characterized by hydrogen nuclear magnetic resonance (¹H NMR) and atomic force microscope (AFM), respectively. The water uptake, swelling ratio and ionic conductivity for PAES-TMI-x are in the range of 23.8%–48.3%, 8.3%–14.3% and 18.22–96.31 mS/cm, respectively. These AEMs exhibit high alkaline stability, and the ionic conductivity for PAES-TMI-0.25 remains 86.8% after soaking in 2 M NaOH solution at 80 °C for 480 h. The current density of 1205 mA/cm² is obtained for the water electrolyzer equipped with PAES-TMI-0.25 in 2 M NaOH solution at 2.0 V and 80 °C, and the electrolyzer also has good operation stability at current density of 500 mA/cm². This work is expected to provide a valuable reference for the selection and design of cations in high-performance AEMs for water electrolysis.     

Cross-linked anion exchange membranes with flexible,long-chain,bis-imidazolium cation cross-linker

Herein, poly (phenylene) oxide (PPO)-based cross-linked anion exchange membranes (AEMs) with flexible, long-chain, bis-imidazolium cation cross-linkers are designed and synthesized. Although the cross-linked membranes possess high ion exchange capacity (IEC) values of up to 3.51–3.94 meq g⁻¹, they have a low swelling degree and good mechanical strength because of their cross-linked structure. Though the membranes with the longest flexible bis-imidazolium cation cross-linker (BMImH-PPO) possess the lowest IEC among these PPO-based AEMs, they show the highest conductivity (24.10 mS cm⁻¹ at 20 °C) and highest power density (325.7 mW cm⁻² at 60 °C) because of the wide hydrophilic/hydrophobic microphase separation in the membranes that promote the construction of ion transport channels, as confirmed by atom force microscope (AFM) images and the small angle X-ray scattering (SAXS) analyses. Furthermore, the BMImH-PPO samples exhibit good chemical stability (10% and 6% decrease in IEC and conductivity, respectively, in 2 M KOH at 80 °C for 480 h, and a 22% decrease in weight in Fenton's reagent at 60 °C for 120 h), making such cross-linked AEMs potentially applicable in alkaline anion exchange membrane fuel cells.     

Construction of ion transport channels by grafting flexible alkyl imidazolium chain into functional poly(arylene ether ketone sulfone) as anion exchange membranes

A new series of imidazolium-functionalized anion exchange membranes (AEMs), based on poly (arylene ether ketone sulfone) containing pendant amino groups (Am-PAEKS) have been prepared. The structure of the copolymers is characterized by FT-IR and ¹H NMR spectra. The properties of the imidazolium-functionalized Am-PAEKS (Im-Am-PAEKS) including ionic conductivity, dimensional stability, thermal stability, fuel cell performance and mechanical property are investigated thoroughly. The hydroxide conductivities of the prepared membranes are in the range of 1.1 × 10^?2–13.9 × 10^?2 S cm^?1 (20–80 °C). The membranes exhibit excellent alkaline stability including high thermal stability and mechanical property after soaking in 2 M NaOH aqueous solution for 300 h. This study indicates that the imidazolium-functionalized membranes containing pedant amino groups have the potential to be applied in alkaline fuel cells.     

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.     

Novel poly(carbazole-butanedione) anion exchange membranes constructed by obvious microphase separation for fuel cells

To develop anion exchange membranes with excellent chemical stability and high performance. A series of quaternary ammonium functionalized (hydrophilic) hydrophobic rigid poly (carbazole-butanedione) (HOCB-TMA-x) anion exchange membranes were prepared, where x represents the percentage content of hydrophobic unit octylcarbazole (OCB). Due to the introduction of hydrophobic rigid unit octylcarbazole and hexyl flexible side chain, the hydrophilic-hydrophobic microstructure of AEMs was developed. The AEMs exhibit excellent overall performance, specifically the low swelling ratio HOCB-TMA-30 membrane exhibits the highest OH^? conductivity of 152.9 mS/cm at 80 °C. Furthermore, the ionic conductivity of AEM decreased by only 9.5% after 2250 h of immersion in 1 M NaOH. The maximum peak power density of a single cell with a current density of 4.38 A/cm² at 80 °C was 1.85 W/cm².     

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.