Phosphoric Acid Retention Research Articles

Polymeric ionic liquids and piperidinium synergistically improve proton conductivity and acid retention of polybenzimidazole-based proton exchange membranes

Amino-type polybenzimidazole is prepared, then ionic liquid with three nitrogen positive sites ([CTDTr]Br3) is polymerized into polymeric ionic liquids (PILs) by in-situ radical polymerization, and AmPBI-CTDTr-Px membranes were prepared by piperidinium (PPd) and [CTDTr]Br3 combination to cross-linked with AmPBI. Following treatment with KOH and phosphoric acid (PA), the ion pairs (N+ - H2PO4-) generated in the composite membrane system can enhance proton conductivity and facilitate proton transport. The AmPBI-CTDTr-Px membranes shown exceptional PA retention as a result of the alkaline properties of both [CTDTr]Br3 and PPd, which can engage in acid-base interactions with phosphoric acid. Specifically, the proton conductivity of AmPBI-CTDTr-P5 at 180 °C is 129.7 mS cm-1, which is 2.52 times that of pure membranes. Acid retention of AmPBI-CTDTr-P5 at 80 °C/40% RH and 160 °C are 64.4% and 84%.

Antioxidant Sulfide‐Linked Polymer Membrane with Inherent Microporosity Enables Fuel Cells to Achieve Outstanding Power Density and Durability Over a Wide Temperature Range

AbstractConventional phosphoric acid (PA) doped polybenzimidazole are regarded as the most promising materials for high‐temperature proton exchange membrane fuel cells (HT‐PEMFCs). Yet, their practical application has been hindered by their high production cost, poor oxidation stability, and loss of PA at low temperatures. Here, a polymer of intrinsic microporosity containing “sulfide‐linkage” radical‐sacrificial‐agent is designed with good solubility and high PA retention, which enables it to operate for long periods at 80–180 °C. Specifically, the “sulfide‐linkage” radical‐sacrificial‐agent enabled PSBI‐IM to be durable for 100 h with mass retention still higher than 90%, and the capillary effect of the micropores enabled PSBI‐IM/PA to retain more than 60% of PA under high humidity. After rational optimization, the cell assembled with PSBI‐IM/PA achieved a power density of 1.62 W cm−2 with a specific power of 2.7 W mg−1 and an operating time of more than 500 h (0.2/0.4 A cm−2@160 °C). In addition, the voltage drop is only 5% even after 40 h of accelerated stress testing at 0.4 A cm−2@ 80 °C. Therefore, the PSBI‐IM/PA can be stabilized over a wide temperature range from 80 to 160 °C, providing a new material for the HT‐PEMFCs with flexible operational temperature.

Quaternized poly(aryl imidazolium) containing bulky binaphthyl group as proton exchange membrane for high-temperature fuel cells

The low power output and high phosphoric acid (PA) leakage are the main constraints restricting the commercialization of PA-doped high-temperature proton exchange membranes (HT-PEMs). Ionized imidazoles have been shown to be an effective strategy to improve PA retention, however, less research has been conducted on the fractional free volume (FFV) of the backbone of the main chain on PA loss. Herein, novel imidazolium ions polymer (PQBN-4-IM) material with bulky binaphthyl (BN) group was prepared as PA-doped HT-PEM using a one-step superoxid acid catalyzed polycondensation and subsequent methylation process. The rigidity and hydrophobicity of the BN group promote PQBN-4-IM PEM to produce more obvious microphase separation morphology and large FFV, which is beneficial for forming better ion transport channels and excellent PA interaction. Notably, the PA-doped PQBN-4-IM (PQBN-4-IM/PA) membrane has the highest proton conductivity (90.26 mS cm−1, 180 ℃) and peak power density (PPD) (802.5 mW cm−2, 180 ℃) than PQTP-4-IM/PA and m-PBI/PA HT-PEMs. Moreover, the PQBN-4-IM/PA membrane has higher PA retention at 80 ℃/40 % relative humidity (RH), 40 ℃/60 % RH, or immersed in water due to enhancement on ion-pair interactions by microstructure. Under the accelerated stress test (AST) of the fuel cell (FC), the PQBN-4-IM/PA membrane loses only 12.22 % of PPD after 200 cycles at 80 ℃, which exhibits higher PPD retention than that of the PQBP-4-IM/PA (70.23 %), PQTP-4-IM/PA (74.36 %) and m-PBI/PA (65.25 %) membranes, and shows excellent durability of cell performance for more than 1000 h without significant voltage decay at 160 °C. Thus, the outstanding performance suggests that the microstructure and morphology of imidazolium ions polymer membranes significantly influence proton conductivity, performance, and the durability of a cell.

Nitrogen-Rich Covalent Organic Frameworks Composited High-Temperature Proton Exchange Membranes with Ultralow Volume Expansion and Reduced Phosphoric Acid Leakage.

Phosphoric acid (PA) leakage and volume expansion are critical factors limiting long-term stable operation of PA-doped polybenzimidazole (PBI) for high-temperature proton exchange membrane fuel cells. Enhancing the interaction between the polymer matrix and PA provides an effective way to minimize PA loss and inhibit excessive membrane swelling. The covalent organic frameworks (COFs) are helpful in improving the performance of PA-PBI membranes due to the robust frameworks, adjustable structures, and good compatibility with polymers. Here, in this work, we synthesized porous COFs named TTA-DFP containing triazine rings and pyridine groups at room temperature for as short as 2 h without oxygen isolation. TTA-DFP was then blended with commercial poly[2,2'-(p-oxidiphenylene)-5,5'-benzimidazole] (OPBI) to prepare composite membranes. The abundant alkaline N sites in TTA-DFP exhibit strong interactions with PA and OPBI, which not only provide more proton transport pathways to promote proton conduction but also immobilize PA in acidophilic micropores to reduce PA leakage. The composite membranes exhibit a much lower volume swelling ratio than that of the OPBI membrane. The PA retention of the composite membrane after 120 h of treatment at 80 °C and 40% relative humidity can reach as high as 84.6%. Particularly, the proton conductivity of the composite membrane doped with 15 wt% TTA-DFP achieves 0.112 S cm-1 at 180 °C without humidification with a swelling ratio of 24.1%. In addition, it has an optimal peak power density of 824.4 mW cm-2 at 180 °C, which is 1.7 times that of the OPBI membrane. The stability of the composite membrane is much better than that of OPBI at a current density of 0.3 A cm-2 at 140 °C for 120 h.

Sulfonating and polyhedral oligomeric silsesquioxane crosslinking in one step to build multiple proton pathways for proton exchange membrane fuel cells over a wide temperature range

Developing proton exchange membrane fuel cells (PEMFCs) operating over a wide temperature range can avoid additional internal/external heating or cooling devices for the PEMFCs operating. Polybenzimidazole (PBI) doped with phosphoric acid (PA) exhibits significant potential in high-temperature proton exchange membrane fuel cells (HT-PEMFCs). Nevertheless, the traditional PA-PBI membranes are limited to operating within 140∼180 °C. In this work, a sulfonated polyhedral oligomeric silsesquioxane crosslinked polybenzimidazole membrane enriched pyridine and diazafluorene (CSPBI-X) is prepared where the sulfonation and crosslinking are accomplished by one-step heating. The theoretical calculations confirm that PA molecules have strong interactions with sulfonic acid groups and nitrogen-containing groups, enabling the membrane to achieve proton conductivity in a wide temperature range (80–180 °C). Moreover, the cross-linked sulfonated membranes have excellent PA retention ratio as high as 83.8% under 80 °C and 40% relative humidity for 120 h. Remarkably, with the acid doping level of 7.6, the proton conductivity of the CSPBI-20 membrane reaches 0.0491 S cm−1 and 0.145 S cm−1 at 80 °C and 180 °C in dry state, respectively. The highest power density of the CSPBI-20 at 80, 100, 120, 140, 160, and 180 °C is 257.3, 362.9, 485.3, 604.6, 755.3, and 956.1 mW cm−2, respectively.

An effective strategy to enhance phosphoric acid retention and proton conductivity stability: Construction of proton transfer channels with starch rather than H3PO4

To enhance the phosphoric acid (PA) retention as well as maintain high proton conductivity of phosphoric acid doped proton exchange membranes at high temperature, we successfully design a series of phosphoric acid doped biobased composite membranes by incorporation of starch and graphene oxide (GO) into poly arylene ether ketones (PAEK). Proton transfer channels should be mainly built through dense hydrogen bonds formed from massive oxygen-containing groups of starch mainchain, which is confirmed by Molecular dynamics (MD) simulation, FT-IR and XRD analysis. The dense hydrogen-bond structure could construct fast proton transfer channels with extreme low doping level (0.00484 molH3PO4). The excellent PA retention properties with almost unchanged proton conductivity at high temperature (200 °C) for 600 min indicates that PA molecules are firmly fixed into membranes. Thus, in this study, we suggest a novel strategy for stablizing proton conductivity at high temperature and improving PA retention properties of PA doped membranes, which is building dense hydrogen-bond structure with low PA doping level.Based on the results in this study and the Grotthuss proton transfer mechanism, dense hydrogen-bonds from oxygen-containing groups in polymer backbones should be more stable than hydrogen-bonds from massive H3PO4 molecules with high acid doping levels to promote proton conduction.

Imidazole and triazine framed porous aromatic framework with rich proton transport sites for high performance high-temperature proton exchange membranes

Phosphoric acid-doped polybenzimidazole (PA-PBI) membranes for high-temperature proton exchange membranes (HT-PEMs) exhibit low proton conductivity under low phosphoric acid loading and poor mechanical properties under high phosphoric acid loading. In order to overcome these disadvantages, a novel kind of porous aromatic framework framed with imidazole and triazine groups (PAF-227) was designed and synthesized, phosphoric acid (PA) was incorporated into PAF-227 by utilizing vacuum-assisted infusion to yield the product PAF-227-PA. Subsequently, this dopant was combined with polybenzimidazole (OPBI) to create the PAF-227-PA/OPBI composite high-temperature proton exchange membranes (HT-PEMs). The PAF-227-PA/OPBI exhibited high proton conductivity (0.24 S cm−1) at 200 °C, as well as a favorable mechanical property (6.73 MPa) and a high PA absorption rate (250.2 %), and the peak power density of the fabricated fuel cells was significantly increased to 678.21 mW cm−2 at 200 °C with the Pt loading of 0.3 mg cm−2. The basic sites of PAF-227 framed with rigid imidazole and triazine groups can anchoring the PA to achieve a high PA retention rate through the acid-basic interaction with PA, and provide sufficient proton conduction sites by forming hydrogen bonds with PA, and synergized with OPBI membranes to form a multiple hydrogen bond and proton transfer network for enhanced mechanical properties and dimensional thermal stability. Thus, this work provided a novel approach to the preparation of HT-PEMs, which exhibited excellent overall performance for HT-PEMs fuel cells.

Understanding Phosphoric Acid Dynamics in High-Temperature Pemfcs: Mechanisms and Durability of PA-PBI and Ion-Pair-Based Systems.

High-Temperature polymer electrolyte membrane fuel cells (HT-PEMFCs) can operate at > 100 oC under anhydrous conditions, providing benefits such as system simplification and superior contaminant tolerance. Most researches on HT-PEMFC have focused on PA-PBI-based system since 1995, however the durability of this system is still on controversial. Some insisted the stable operation of PA-PBI HT-PEMFC, which showed the stability under mild conditions such as low current density about 0.2 A cm-2, while others pointed out the instability specifically under accelerated stress conditions with higher current densities above 0.6 A cm-2, lower ( < 140 oC) or higher ( > 180 oC) operating temperatures, or dynamic protocols like start-up/shut-down cycles, etc.This limited durability of PA-PBI HT-PEMFC is known to be related to acid loss from the membrane-electrode-assemblies (MEAs). Several mechanisms were proposed to explain the linear and nonlinear acid loss behaviors. PA evaporation and steam-distillation are known to explain the constant PA loss. Despite the extensive efforts on mechanisms and acid loss mitigation strategies, current PA-PBI systems still struggle against the limited durability due to PA loss. To improve the durability of HT-PEMFC, a novel system was introduced based on the quaternary ammonium-biphosphate ion-pair coordinated PEM [1]. Due to a stronger interaction in the ion-pair PEMs, the durability was also improved by alleviating the PA loss during PEMFC operation. Nonetheless, the acid retention mechanism of this novel system is not explored yet.Here, we investigate the mechanisms of PA loss and PA retention within electrodes of both PA-PBI-based and ion-pair-based HT-PEMFC systems. Through PA energetics studies and experimental investigations under controlled stress conditions, we elucidate distinct PA loss/retention mechanisms in these systems, leading to different durability behaviors. Our findings offer insights for enhancing the durability of both HT-PEMFC systems [2].[1] Lim, K. H.; Lee, A. S.; Atanasov, V.; Kerres, J.; Park, E. J.; Adhikari, S.; Maurya, S.; Manriquez, L. D.; Jung, J.; Fujimoto, C.; Matanovic, I.; Jankovic, J.; Hu, Z.; Jia, H.; Kim, Y. S. Protonated phosphonic acid electrodes for high power heavy-duty vehicle fuel cells, Nature Energy, 7, 248 (2022).[2] Lim, K. H.; Matanovic, I.; Maurya, S.; Kim, Y.; Castro, E. S.; Jang, J-H.; Park, H.; Kim, Y. S. High temperature polymer electrolyte membrane fuel cells with high phosphoric acid retention, ACS Energy Letters, 8, 529 (2023).

Intrinsically Microporous Ion-Pair Membranes for HT-PEMFCs

Fuel cells are electrochemical devices with high energy efficiency expected to be applied economically and eco-friendly across various energy sectors. Low-temperature polymer electrolyte membrane fuel cells (LT-PEMFCs) using Nafion operates at a relatively low operating temperature (60-80°C) and fully hydration condition. HT-PEMFC is operable at high temperatures (140-180°C), but requires anhydrous conditions to avoid loss of doped phosphoric acid (PA). In this presentation, polymer membranes designed through with intrinsic microporosity were synthesized through super acid polycondensation. We demonstrated that high proton conductivity (106.33 mS cm-1 at 180℃) is obtained by forming phosphoric acid filled ion-channels within the interconnected microporous structure. Moreover, ion-pair coordinated PIMs are fabricated by methylation of PIMs to improve PA retention even under humidified conditions. It is suggested that the water tolerance of ion-pair coordinated PIMs is improved and can be operated under various conditions regardless of humidification and operating temperature and exceptional membrane electrode assembly performance and durability achieved even under humidified reformate gas conditions.

Highly acid-stable high-temperature proton exchange membrane: Azide-based polymeric ionic liquids for the enhancement of amino-polybenzimidazole

Polybenzimidazole (PBI) is commonly used for high-temperature proton exchange membranes. However, it is undeniably challenging for phosphoric acid (PA)-doped PBI membranes to have both high proton conductivity and excellent long-term stability. In this study, a series of polymer ionic liquid composite PBI membranes were fabricated. These membranes are made using two azide-functional ionic liquids and amino-polybenzimidazole, adjusting the amount of the two ionic liquids. The ionic pairs offered by the ionic liquids positively impact the transportation of protons and the stability of PA through the replacement of anions. It is noteworthy that crosslinked amino-polybenzimidazole membranes containing functional polymeric ionic liquids have proton conductivity of up to 131.7 mS cm−1 at 180 °C, and the PA retention after 240 h at 160 °C under humidity-free conditions is 86.5 %. In addition, the membrane is used in membrane electrodes with hydrogen and oxygen at the anode and cathode, respectively, exhibiting a peak power density of 694.6 mW cm−2 at 160 °C. And the voltage decay rate is 0.28 mV h−1 after long-term test. The findings indicate that membranes made of functional polymeric ionic liquids crosslinked with amino-polybenzimidazoleprovide a new strategy to enhance fuel cell durability.

High-performance polybenzimidazole composite membranes doped with nitrogen-rich porous nanosheets for high-temperature fuel cells

Traditional phosphoric acid (PA) doped polybenzimidazole (PBI) membranes encounter many issues when used in high-temperature proton exchange membrane fuel cell (HT-PEMFC), including the loss of PA within the membrane and limitations on conductivity. The mixed matrix membranes (MMMs) synergistically combine the advantages of pore fillers and polymer matrix, making them promising candidates for HT-PEMs. Interface compatibility is the main factor affecting the further development of MMMs. This research presented OPBI composite membranes filled with porous nanosheets, featuring average pore diameters of 2.83 nm, 3.38 nm, and 2.60 nm, respectively. The high aspect ratio and plentiful nitrogen components of the nanosheets increase the π-π and hydrogen bonding interactions with the polymer matrix, resulting in outstanding interface compatibility and mechanical properties of MMMs. The results of theoretical calculations indicate that there is a stronger interaction energy between the nanosheets and PA molecules, and the abundant pore structure within the nanosheets facilitates the absorption of PA molecules, leading to the formation of a continuous PA network. Consequently, MMMs exhibited enhanced proton conductivity, as well as improved PA absorption and retention. Furthermore, the effect of pore size distribution of nanofillers on the performance of MMMs were investigated. Membranes composed of nanosheets with large pore size showed a higher conductivity of 176.7 mS cm−1 at 200 °C, leading to excellent performance and stability in assembled H2/O2 fuel cells. This work offers valuable insights into the design of MMMs and high-performance HT-PEMs.

Introduction of polymeric ionic liquids containing quaternary ammonium groups to construct high-temperature proton exchange membranes with high proton conductivity and stability

A series of membrane materials suitable for high-temperature proton exchange membranes (HT-PEM) were successfully prepared by introducing polymeric ionic liquids (PILs) containing quaternary ammonium groups into ether-bonded polybenzimidazole (OPBI). The structure of the cross-linked membrane has a strong interaction with phosphoric acid (PA), which enhances proton transport and PA retention. To ensure better overall performance of the cross-linked membrane, the optimal PIL content is 30 wt% (OPBI-PIL-30 %). The PA uptake of OPBI-PIL-30 % membrane was 323.24 %, and the proton conductivity at 180 ℃ was 113.94 mS cm−1, which was much higher than that of OPBI membrane. It is noteworthy that the PA retention of OPBI-PIL-30 % membrane could reach 71.38 % after 240 h of testing under the harsh environment of 80 ℃/40 % RH. The membrane showed better acid retention capacity of 86.89 % at 160 ℃ under anhydrous environment. The OPBI-PIL-20 % membrane achieved the maximum power density of 436.19 mW cm−2, attributed to its favorable mechanical characteristics and proton conductivity. By these excellent properties, it is shown that OPBI-PIL-X membranes containing quaternary ammonium groups have the potential to be applied in high temperature proton exchange membrane fuel cells (HT-PEMFCs).

Effects of different ratios of flexible links and rigid structures in side chains on membrane properties for HT-PEM applications

A series of grafted polybenzimidazoles with ratios of flexible links and rigid structures in side chains based on amino polybenzimidazole (AmPBI) was successfully prepared by simple N-substitution reaction. Due to the adequate number of amino groups on the AmPBI backbone, sufficient N–H sites reduce consumption of imidazole group during grafting reactions, while simultaneously elevating the number of proton transfer site. The grafted polybenzimidazole membranes with ratios of flexible links and rigid structures in side chains have excellent properties especially in the phosphoric acid (PA) uptake, pretty swelling ratio and proton conductivity. Importantly, PA uptake, swelling ratio, mechanical property, proton conductivity and power density can be controlled by changing the ratios of flexible links and rigid structures. The grafted membrane (AmPBI-P3) with the longer flexible link in the side chain shows a low swelling ratio of 128.62%, which is lower than that of other AmPBI-PX and AmPBI. Moreover, AmPBI-P3 shows a high proton conductivity of 126.9 mS cm−1 which is about 1.74 times higher than pure AmPBI (73.1 mS cm−1) and still reaches 91.4 mS cm−1 at 180 °C after the PA retention capacity test under 160 °C/0%RH for 240 h. A great power density of 738.5 mW/cm2 at 180 °C with dry H2–O2 and no backpressure is impressive among many reported membranes.

Polymers of intrinsic microporosity with alkaline pyrrolidine and piperidine functional groups for high-temperature proton exchange membranes

Recently, the polymers of intrinsic microporosity (PIMs) exhibit good potential in high-temperature proton exchange membrane fuel cells (HT-PEMFCs) due to their tunable microporosity and functionality. In this paper, alkaline pyrrolidine and piperidine functional groups were introduced onto PIM-1 via the classical Mannich reaction obtaining PIM-1/PIM-Py-50 and PIM-1/PIM-MePi-50. It was found that, compared with commercial Meta-polybenzimidazole (m-PBI) membrane, PIMs membranes showed superior retention of phosphoric acid (PA) and conductivity due to their grafting alkaline groups and rich micropores. After equilibration under 80 °C/40 % relative humidity (RH) for 150 h, the PA retention of PA doped PIM-1/PIM-Py-50 (PIM-1/PIM-Py-50/PA) and PA doped PIM-1/PIM-MePi-50 (PIM-1/PIM-MePi-50/PA) membranes were 74.13 % and 68.52 %, respectively, much higher than PA doped m-PBI (m-PBI/PA) (45.73 %). PIMs membranes maintain excellent dimensional and conductivity stability at 160 °C operating conditions, e.g. PIM-1/PIM-Py-50/PA membrane showed area swelling retention and volume swelling retention of 84.69 % and 82.19 % after 230 h at 160 °C. In addition, with the similar PA uptake, PIMs membranes displayed higher conductivity and peak power density (PPD) at 160 °C. In the accelerated stress test (AST) the PPD of the fuel cell (FC) with the PIM-1/PIM-Py-50/PA membrane remained 81.25 % after 200 aggressive start-up/shut-down cycles at 80 °C. Therefore, PIM-based membranes alkaline groups exhibit a wider temperature operating window, providing theoretical guidance for the design and study of the next generation of high-temperature proton exchange membranes (HT-PEMs).

Tetramethyl poly(aryl ether ketone) modified by DABCO cationic polymer for high temperature proton exchange membrane fuel cells

Rationally constructing proton transport channel within high temperature proton exchange membranes (HT-PEMs) plays a critical role in lowering the mass transfer resistance and thus improving the performance of HT-PEM fuel cells (HT-PEMFCs). We herein designed a microphase-separated structure to promote proton transmitting by incorporating 1,4-Diazabicyclo[2.2.2]octane (DABCO) cationic polymer into tetramethyl poly(aryl ether ketone) (TMPAEK). The flexible and cationic segments afforded a polarity difference from TMPAEK, resulting in easier phosphoric acid adsorption. High proton conductivity of 135 mS cm−1 was obtained under anhydrous conditions at 150 °C. Besides, the hydrophilic domains that containing N-heterocycle could stabilize phosphoric acid through hydrogen bonding interactions, resulting in high phosphoric acid retention of ∼80 % after 288 h test. A Peak power density of 496 mW cm−2 was achieved in non-humidified H2/O2 without back pressure at 140 °C, which was higher than that of m-PBI under the same conditions. This work not only paved a way to tailor the ion conductivity of membrane, but also provided a highly competitive membrane for HT-PEMFCs.

High-performance and robust high-temperature polymer electrolyte membranes with moderate microphase separation by implementation of terphenyl-based polymers

Acid loss and plasticization of phosphoric acid (PA)-doped high-temperature polymer electrolyte membranes (HT-PEMs) are critical limitations to their practical application in fuel cells. To overcome these barriers, poly(terphenyl piperidinium)s constructed from the m- and p-isomers of terphenyl were synthesized to regulate the microstructure of the membrane. Highly rigid p-terphenyl units prompt the formation of moderate PA aggregates, where the ion-pair interaction between piperidinium and biphosphate is reinforced, leading to a reduction in the plasticizing effect. As a result, there are trade-offs between the proton conductivity, mechanical strength, and PA retention of the membranes with varied m/p-isomer ratios. The designed PA-doped PTP-20m membrane exhibits superior ionic conductivity, good mechanical strength, and excellent PA retention over a wide range of temperature (80–160 °C) as well as satisfactory resistance to harsh accelerated aging tests. As a result, the membrane presents a desirable combination of performance (1.462 W cm−2 under the H2/O2 condition, which is 1.5 times higher than that of PBI-based membrane) and durability (300 h at 160 °C and 0.2 A cm−2) in the fuel cell. The results of this study provide new insights that will guide molecular design from the perspective of microstructure to improve the performance and robustness of HT-PEMs.

Grafting of Amine End-Functionalized Side-Chain Polybenzimidazole Acid-Base Membrane with Enhanced Phosphoric Acid Retention Ability for High-Temperature Proton Exchange Membrane Fuel Cells.

A high phosphoric acid uptake and retention capacity are crucial for the high performance and stable operation of phosphoric acid/polybenzimidazole (PA/PBI)-based high-temperature proton exchange membranes. In this work, amine end-functionalized side-chain grafted PBI (AGPBI) with different grafting degrees are synthesized to enhance both the phosphoric acid uptake and the acid retention ability of the accordingly formed membranes. The optimized acid-base membrane exhibits a PA uptake of 374.4% and an anhydrous proton conductivity of 0.067 S cm-1 at 160 °C, with the remaining proton conductivity percentages of 91.0% after a 100 h stability test. The accordingly fabricated membrane electrode assembly deliver peak power densities of 0.407 and 0.638 W cm-2 under backpressure of 0 and 200 kPa, which are significantly higher than 0.305 and 0.477 W cm-2 for the phosphoric acid-doped unmodified PBI membrane under the same conditions.

Enhanced performance of high-temperature proton exchange membranes via polyfluorene cross-linked zwitterionic liquid

A satisfactory trade-off between physical/chemical stability and conductivity is crucial for high-temperature proton exchange membrane (HT-PEM) applications. Herein, a series of ether-free polyfluorenes cross-linked with zwitterionic liquids possessing both quaternary ammonium (QA+) and sulfonate ion (–SO3−) were prepared as crosslinked cHFTP–VIPSx via UV irradiation. Compared with non-crosslinked HFTP–TMA, crosslinked cHFTP–VIPSx exhibited enhanced conductivity, dimensional stability, oxidation stability, and phosphoric acid retention, which are attributed to the well-developed crosslinked structure and incorporated –SO3- groups. The as-fabricated H2/air single cell with a cross-linked cHFTP–VIPS30 achieved a higher peak power density (728 mW cm−2) than that of uncross-linked HFTP–TMA (287 mW cm−2) at 120 °C. Considering their enhanced performance, these cHFTP–VIPSx membranes cross-linked with zwitterionic liquid are promising HT-PEM materials for fuel cells.

Confined Nano-Channels Incorporated with Multi-Quaternized Cations for Highly Phosphoric Acid Retention HT-PEMs.

Developing a new strategy to retain phosphoric acid (PA) to improve the performance and durability of high-temperature proton exchange membrane fuel cell (HT-PEMFC) remains a challenge. Here, a strategy for ion-restricted catcher microstructure that incorporates PA-doped multi-quaternized poly(fluorene alkylene-co-biphenyl alkylene) (PFBA) bearing confined nanochannels is reported. Dynamic analysis reveals strong interaction between side chains and PA molecules, confirming that the microstructure can improve PA retention. The PFBA linked with triquaternary ammonium side chain (PFBA-tQA) shows the highest PA retention rate of 95%. Its H2/O2 fuel cell operates within 0.6% voltage decay at 160°C/0% RH, and it also runs over 100h at 100°C/49% RH under external humidification. This combination of high PA retention, and chemical and dimensional stability fills a gap in the HT-PEMFC field, which requires strict moisture control at 90-120°C to prevent acid leaching, simplifying the start-up procedure of HT-PEMFC without preheating.

Incorporating 2D porous organic polymer nanosheets into high-temperature proton-exchange membranes for low H3PO4 loss

Phosphoric acid (PA)-doped ion exchange membranes have been recognized as a classical high-temperature proton exchange membrane (HT-PEM) material. Nonetheless, the leaching of PA from membranes occurs progressively during operation, inevitably diminishing overall performance. In this study, we present a novel approach for crafting two-dimensional porous organic polymer nanosheets (NS-POPs) synthesized through nano-interfacial azo-coupling polymerization. The prepared NS-POPs possessed different pore structures with main pore sizes of 0.55 nm and 1.19 nm, which were derived from the discrepancy of monomer structure. Subsequently, the NS-POPs were successfully incorporated into polybenzimidazole to create mixed-matrix membranes due to the good interface compatibility, characterized by homogeneity and stability facilitated by the 2D nature of NS-POPs. As a comparison, POPs with non-2D properties prepared by the solution method cannot be successfully obtained in good MMMs due to poor dispersibility and interface compatibility. Furthermore, the profusion of pore structures and the presence of N/O-rich functional groups in NS-POPs significantly enhance their PA uptake capacity with up to 289 %, consequently boosting proton conductivity. As a result, the composite membrane doped with NS-POPs demonstrated a maximum conductivity of up to 143 mS cm−1 at 180 °C, which is approximately 2.97 times that of pure membrane. And the peak power density of H2/O2 fuel cell based on the composite membrane was 378 mW cm−2, which was higher than PBI. Most significantly, the confinement effect exerted by the small pores in NS-POPs enables composite membranes to maintain a higher PA retention of up to 74 % even after a 48 h of high-temperature and high-humidity treatment. Our study introduces an innovative and straightforward approach to synthesizing porous organic polymer nanosheets. This work not only advances the understanding of the impact of interface compatibility on composite membrane fabrication, but also establishes a versatile technology for modulating pore size and managing PA leaching in HT-PEMs.