Proton Transport Channels Research Articles

Constructing highly durable proton transport channels in polybenzimidazole membranes using highly stable porous carbonized metal organic frameworks

The use of porous materials to construct proton transport channels in high-temperature proton exchange membranes (HT-PEMs) is an effective strategy for improving cell performance. However, most reported metal organic frameworks (MOFs) struggle to maintain stability in highly acidic or alkaline environments, which hinders their application. In this work, highly stable carbonized MOFs based on MIL-101(Cr) are prepared and used as porous materials to construct proton transport channels in HT-PEMs. The porous carbon derived from MOFs exhibits new structures and properties owing to the periodic porous and hybrid structure used to prepare porous carbon with uniform pores. High specific surface area and highly stable proton transport channels are constructed in a phosphoric acid (PA)-doped polybenzimidazole system. The tensile properties and anti-oxidization capacity of prepared membranes are improved as the doping content of carbonized MOFs increased. Meanwhile, the conductivities of prepared membranes increase with increasing amounts of the carbonized MOFs at a similar acid doping level. The membrane noted CM15@OPBI achieves a conductivity of 0.059 S cm−1 and a power density of 648 mW cm−2 at 0 % RH, 160 °C (H2/O2). Moreover, the membrane stably withstands a constant current discharge of 200 mA cm−2 for 200 h under those conditions.

Overcoming the Limitation of Ionomers on Mass Transport and Pt Activity to Achieve High-Performing Membrane Electrode Assembly.

The membrane electrode assembly (MEA) is one of the critical components in proton exchange membrane fuel cells (PEMFCs). However, the conventional MEA cathode with a covered-type catalyst/ionomer interfacial structure severely limits oxygen transport efficiency and Pt activity, hardly achieving the theoretical performance upper bound of PEMFCs. Here, we design a noncovered catalyst/ionomer interfacial structure with low proton transport resistance and high oxygen transport efficiency in the cathode catalyst layer (CL). This noncovered interfacial structure employs the ionomer cross-linked carbon particles as long-range and fast proton transport channels and prevents the ionomer from directly covering the Pt/C catalyst surface in the CL, freeing the oxygen diffusion process from passing through the dense ionomer covering layer to the Pt surface. Moreover, the structure improves oxygen transport within the pores of the CL and achieves more than 20% lower pressure-independent oxygen transport resistance compared to the covered-type structure. Fuel-cell diagnostics demonstrate that the noncovered catalyst/ionomer interfacial structure provides exceptional fuel-cell performance across the kinetic and mass transport-limited regions, with 77% and 67% higher peak power density than the covered-type interfacial structure under 0 kPagauge of oxygen and air conditions, respectively. This alternative interfacial structure provides a new direction for optimizing the electrode structure and improving mass-transport paths of MEA.

A Molten Alkali Approach to Tailor Hydroxyl Groups of Hexaazatrinaphthalene Toward High-Capacity and Low-Potential Anode of Aqueous Proton Batteries.

Hexaazatrinaphthalene (HATN) has attracted a lot of attention in aqueous proton batteries (APBs). However, its redox potential as an anode is insufficiently negative. The introduction of electron-donating substituent groups, such as hydroxyl groups, is considered as a good approach to reduce the redox potential of HATN. Nevertheless, manufacturing hydroxyl-substituted HATN (HATN-OH) requires either expensive precursors or multi-step process, limiting their research. Herein, a straightforward strategy is proposed to synthesize HATN-OH based on the nucleophilic substitution reaction of halogenated HATN in a molten alkali. The redox potential of 1,2,7,8,13,14-hexahydroxy-5,6,11,12,17,18-hexaazatrinaphthalene (34-HATN-6OH) electrode may be lowered by 0.15V in comparison to HATN, and exhibits a high specific capacity, low redox potential, remarkable rate capability, and outstanding long-term cycling performance. The electrochemical redox kinetics is significantly enhanced owing to the formation of rapid proton transport channels created by intermolecular hydrogen bond network. The assembled MnO2||34-HATN-6OH full battery delivers a high discharge voltage (1.16V) and cycling stability (74% capacity retention after 5000 cycles). This study provides a general cost-effective molten alkali approach for the synthesis of hydroxyl-substituted conjugated small molecules from their halogenated counterparts and further enriches the regulation means of electro-chemical performances of organic electrodes for enabling high-capacity and high-voltage APBs.

Reverse Hydrogen Spillover on Metal Oxides for Water-Promoted Catalytic Oxidation Reactions.

Understanding the water-involved mechanism on metal oxide surface and the dynamic interaction of water with active sites is crucial in solving water poisoning in catalytic reactions. Herein, this work solves this problem by designing the water-promoted function of metal oxides in the ethanol oxidation reaction. In situ multimodal spectroscopies unveil that the competitive adsorption of water-dissociated *OH species with O2 at Sn active sites results in water poisoning and the sluggish proton transfer in CoO-SnO2 imparts water-resistant effect. Carbon material as electron donor and proton transport channel optimizes the Co active sites and expedites the reverse hydrogen spillover from CoO to SnO2. The water-promoted function arises from spillover protons facilitating O2 activation on the SnO2 surface, leading to crucial *OOH intermediate formation for catalyzing C-H and C-C cleavage. Consequently, the tailored CoO-C-SnO2 showcases a remarkable 60-fold enhancement in ethanol oxidation reaction compared to bare SnO2 under high-humidity conditions.

A novel comb-shaped polybenzimidazoles crosslinked sulfonic acid functionalized polyphosphazenes high temperature proton exchange membrane

Designing high temperature proton exchange membranes (HTPEMs) with high H+ conductivity and long durability has been challenging. Here, a comb-shaped polybenzimidazoles (CbPBI) and crosslinkable polyoxy (benzenesulfonic acid) phazenes (PBSP) proton conductors are prepared, then they are used to fabricate a series of PBSP-CbPBI membranes with good comprehensive performances. CbPBI provides high flexibility and large free volume, which facilitates the construction of proton transport channels. And PBSP is the bifunctional proton conductor and crosslinker that introduces abundant sulfonic acid groups while retaining the crosslinkable property. By strongly chemical binding with CbPBI, the basicity of the imidazole ring is enhanced, avoiding the leaching of PBSP, thus enabling the overall crosslinked membrane to exhibit a durable intrinsic proton conductivity. Benefiting from the construction of the dual crosslinked network (covalent and ionic crosslinking), the oxidative stability, dimensional stability, and fuel-blocking properties of the PBSP-CbPBI membranes perform well. The proton conductivity of PBSP(50)-CbPBI membrane reaches 0.163, 0.084, 0.057, and 0.043 S/cm, respectively, at 180 °C and different relative humidity (100 % RH, 50 % RH, 30 % RH, and 0 RH). Enduring hot-washing for 96 h, the less decay of membrane in conductivity and weight demonstrates good durability. The design strategy such as the construction of monolithic crosslinked macromolecular structures in PBSP-CbPBI membranes shows wide application prospects in HTPEMs.

Nucleobase-mediated hydrogen bonding crosslinked highly sulfonated poly(ether ether ketone) electrodialysis membranes for efficient waste acid recovery

Electrodialysis is a promising technology for waste acid recovery with the advantages of low energy consumption and high efficiency. In this work, two nucleobase-modified highly sulfonated poly(ether ether ketone) with adenine (SPEEK-50A) and thymine (SPEEK-50T) were successfully synthesized. Then, a series of blending SPEEK-50Ax/50Ty membranes with varying molar ratios of these two functionalized SPEEKs were fabricated by solution casting. The hydrogen bonding crosslinked structure of ‘A-T base pairs’, as well as the acid-base interactions between the incorporated nucleobases and SO3H groups of the polymer backbone, not only enhanced the mechanical properties and thermal stability of the blending membranes, but more importantly, it successfully addressed the over-swelling issue of highly sulfonated SPEEK membrane. The SPEEK-50Ax/50Ty membranes exhibited tensile strengths between 59.3 and 72.3 MPa, which is 2.2–2.6 times that of the pristine SPEEK membrane. And the water uptake of the blending membranes reduced from 116 % to 14.6–19.2 %, while the swelling ratio decreased from 27.1 % to 5.86–6.60 %. The proton affinity of the multiple basic N atoms in nucleobases, as well as the ‘A-T base pairs’ hydrogen bonding network and acid-base interactions between nucleobases and SO3H groups, all can serve as effective proton transport channels. Additionally, the charge repulsion effect of protonated nucleobases and the crosslinking structure is beneficial to the permselectivity. Therefore, the fabricated blending SPEEK-50Ax/50Ty membranes exhibited superior H+ flux (1.66–1.73 mmol m−2 s−1) and enhanced H+/Fe2+ permselectivity (40.3–43.2). The SPEEK-50A0.5/50T0.5 membrane demonstrated a H+ flux of 1.70 mmol m−2 s−1 and a H+/Fe2+ permselectivity of 43.2, which is 2.8 times that of the pristine SPEEK membrane, surpassing both commercially available and recently reported membranes. Therefore, the nucleobase-modified blending SPEEK-50Ax/50Ty membranes might be potential candidates for the efficient recovery of acid from pickling wastewater.

Preparation and study on H–MoS2/SLS modified SPI@SPEEK blend proton exchange membrane with balanced proton conductivity and stability

Proton exchange membranes (PEMs) are the core components of fuel cells, and research has long focused on how to balance their proton conductivity and durability. In this work, a series of homogeneous blend of sulfonated polyimide (SPI) and sulfonated polyether ether ketone (SPEEK) hybrid membranes with were constructed refined with sulfonated MoS2 (H–MoS2) and sodium lignosulfonate (SLS). The results showed that the tensile strength of the films was enhanced by 39.4% (67.84 MPa) compared to the base film. The composite films incorporating 1 wt% H-MoS2 and 2 wt% SLS has excellent proton conductivity, which can reach 50.24 mS/cm at 80°C and 100% humidity. The embed hybrid structure constructed by H–MoS2 and SLS, which not only effectively solves the limitations of the proton transport channel of traditional polymer materials, but also provides abundant proton transport sites, which provides a new strategy for preparing high-performance PEM.

Multi-scale revealing how real catalyst layer interfaces dominate the local oxygen transport resistance in ultra-low platinum PEMFC

In view of a catalyst layer (CL) with low-Pt causing higher local transport resistance of O2 (Rlocal), we propose a multi-study methodology that combines CO poisoning, the limiting current density method, and electrochemical impedance spectroscopy to reveal how real CL interfaces dominate Rlocal. Experimental results indicate that the ionomer is not evenly distributed on the catalyst surface, and the uniformity of ionomer distribution does not show a positive correlation with the ionomer content. When the ionomer coverage on the supported catalyst surface is below 20 %, the ECSA is only 10 m2·g−1, and the ionomer coverage on the supported catalyst surface reaches 60 %, the ECSA is close to 40 m2·g−1. The ECSA has a positive correlation with ionomer coverage. Because the ECSA is measured by CO poisoning, it can be inferred that the platinum contacted with ionomer can generate effective active sites. Furthermore, a more uniform distribution of ionomer can create additional proton transport channels and reduce the distance for oxygen transport from the catalyst layer bulk to the active sites. A higher ECSA and a shorter distance for oxygen transport will reduce the Rlocal, leading to better performance.

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.

Proton exchange membranes with functionalized sulfonimide and phosphonic acid groups for next-generation fuel cells operating at 120 °C

Proton exchange membrane fuel cells (PEMFCs) face a significant challenge when operating in high-temperature and low-humidity environments, the hydrocarbon-based polymers that are sulfonated or phosphonated can’t meet the demand for achieving high performance. Modifying perfluorosulfonyl fluoride (PFSF) through meticulous design of side-chain chemical structures and introducing functionalized sulfonimide and phosphonic acid groups. Membranes derived from a perfluorocarbon backbone and polyacid side chain structures exhibit distinct microphase separation. The sulfonimide group exhibits hyper-acidic properties, whereas the phosphonic acid group functions as proton acceptor and donor. These two groups work synergistically to establish a distinct proton transport channel. The robust adsorption between acidic functional groups and water molecules enhances the diffusion of water molecules, resulting in an increase in proton conductivity. Moreover, Density Functional Theory (DFT) calculations reveal that the phosphonic acid group of the side chain has difficulty forming anhydrides. The prepared perfluorosulfonimide-phosphonic acid (PFSNPA) proton exchange membrane demonstrates an impressive conductivity of 263 mS·cm−1 at 120 °C. In H2/Air fuel cell tests, PFSNPA achieves an outstanding output power of 1076.1 mW·cm−2 at 120 °C and 40 % RH. This study introduces a new approach for designing and fabricating proton exchange membrane materials for high-temperature fuel cells.

Covalent Benzenesulfonic Functionalization of a Graphene Nanopore for Enhanced and Selective Proton Transport.

A fundamental understanding of proton transport through graphene nanopores, defects, and vacancies is essential for advancing two-dimensional proton exchange membranes (PEMs). This study employs ReaxFF molecular dynamics, metadynamics, and density functional theory to investigate the enhanced proton transport through a graphene nanopore. Covalently functionalizing the nanopore with a benzenesulfonic group yields consistent improvements in proton permeability, with a lower activation barrier (≈0.15 eV) and increased proton selectivity over sodium cations. The benzenesulfonic functionality acts as a dynamic proton shuttle, establishing a favorable hydrogen-bonding network and an efficient proton transport channel. The model reveals an optimal balance between proton permeability and selectivity, which is essential for effective proton exchange membranes. Notably, the benzenesulfonic-functionalized graphene nanopore system achieves a theoretically estimated proton diffusion coefficient comparable to or higher than the current state-of-the-art PEM, Nafion. Ergo, the benzenesulfonic functionalization of graphene nanopores, firmly holds promise for future graphene-based membrane development in energy conversion devices.

Construction of proton transport channels and performance Modulation of phosphotungstic acid hybrid proton exchange membranes for direct methanol fuel cell

Serving as the central part of a direct-methanol fuel cell (DMFC), a proton exchange membrane (PEM) is used to conduct protons, isolate electrons and fuel, and ensure the proper operation of the battery. The novel hybrid proton exchange membrane (PEM) proposed in the present work is comprised of polyethyleneimine (PEI) and polyvinyl alcohol (PVA) doped with phosphotungstic acid (PWA). PEI provides numerous locations for PWA anchoring and allows for the creation of efficient and continuous proton transport channels over long distances. PEI can be cross-linked with PVA through Glutaraldehyde (GA), which not only suppresses the disadvantage of PVA as a proton exchange membrane that tends to swell after water absorption and leads to deformation, but also the hydrogen-bonded network structure formed after cross-linking is conducive to proton hopping conduction, which synergistically improves the proton conduction rate of PEMs. A good compromise between the amount of PWA doping and the electrochemical properties of PEMs can result in optimal performance. Compared to other reported PEMs that use hetero-poly acids or other inorganic acids, PVA/PEI-PWA2 PEM exhibits superior overall properties. The highest proton conductivity of PVA/PEI-PWA2 is 124.3 mS cm−1 at 80 °C, the highest peak power density can reach 109.8 mW cm−2 (301.8 mA cm−2) at 60 °C, and the methanol barrier performance and selective permeability are 4.95 × 10−7 cm2 s−1 and 12.32 × 104 S s cm−3, respectively.

Magnetically aligned composite membranes based on sulfonated poly(ether ether ketone) and phosphotungstic acid-loaded magnetic nanoparticles for fuel cell

In this work, phosphotungstic acid (HPW)-loaded polydopamine-coated magnetic nanoparticles (DMNPs@HPW) were prepared and incorporated into sulfonated poly(ether ether ketone) (SPEEK) matrix with magnetic field assistance to construct aligned channels to shorten proton transport pathways. The structure of the prepared composite membranes (M-SP/DMNPs@HPW) with magnetic field-induced proton channels was confirmed by SEM. The proton conductivity of M-SP/DMNPs@HPW-2 was significantly improved, with in-plane proton conductivity (σ//) of 159.3 mS/cm and through-plane proton conductivity (σ⊥) of 129.2 mS/cm in the hydrated state at 80 °C, which were 1.31 and 1.57 times higher than the pristine SPEEK membrane, due to the strong acidity of HPW and acid-base interaction of amine and sulfonic acid groups. Meanwhile, the σ⊥ of M-SP/DMNPs@HPW-2 was 1.14 times higher than that of SP/DMNPs@HPW-2 membrane prepared without magnetic field assistance. The fuel cell power output of M-SP/DMNPs@HPW-2 was 433 mW/cm2, while SP/DMNPs@HPW-2 and pristine SPEEK membranes tested under the same conditions were 360 mW/cm2 and 277 mW/cm2, respectively. The hydrogen crossover of M-SP/DMNPs@HPW-2 was slightly increased compared to SP/DMNPs@HPW-2 due to the construction of through-plane proton transport channels in the membrane.

Electrode informatics accelerated the optimization of key catalyst layer parameters in direct methanol fuel cells.

As the core component of direct methanol fuel cells, the catalyst layer plays the key role as a species, proton and electron transport channel. However, due to the complexity of the system, optimizing its performance involves a large number of experiments and high costs. In this study, finite element simulation combined with machine learning model was constructed to accelerate power density prediction and evaluate the influence of catalyst layer parameters on the maximum power density of direct methanol fuel cells. We built a fuel cell simulation model corresponding to different parameters, obtaining a database of more than 200 sets of 19 eigenvalues, and then used different machine learning models for training and prediction. Finally, three tree-integration methods were selected to rank the importance of 19 characteristic parameters. In addition, we performed a high-throughput screening of 200 000 different parameter combinations based on sequential model-based algorithm configuration. We selected the top 10 parameter combinations with high expected improvement scores and employed them into a numerical simulation model. The results show that a majority of the polarization curves obtained from the top combinations exceed the maximum power density of the original database. This method greatly saves the time of collecting fuel cell data for experiments and speeds up the parameter optimization process.

(Invited) Research Progress of Electrocatalyst and MEA of PEM Fuel Cell and Water Electrolyser

The successful commercialization of PEM fuel cell and water electrolyser is determined by the performance, durability, and cost of electrocatalyst and MEA. Compared with conventional electrodes, nanoarray electrodes feature enhanced mass transport thanks to continuous proton and electron transport channels. Herein, a series of nanoarray electrodes were developed directly as the electrodes for PEM fuel cells and water electrolysers. A catalyst layer based on porous Pt−Ni nanobelt arrays were prepared by the magnetron sputtering of Pt and Ni on a sacrificed template, followed by acid etching. The porous Pt−Ni nanobelt arrays-based catalyst layer exhibited superior fuel cell performance in H2/air conditions and RH 40%. The performance of the MEA with porous Pt−Ni nanobelt arrays reached 366.6 and 597.6 mW cm−2 with Pt loadings of 36.5 μg cm−2/36.5 μg cm−2 and 108.9 μg cm−2/108.9 μg cm−2 at the cathode/anode, respectively. Besides, a WO3 nanoarray electrode with a heterogeneous IrRu coating was prepared via a facile electrodeposition approach. The obtained IrRu@WO3 electrode exhibits a competitive overpotential of 245 mV at 10 mA cm−2. A single cell enables a current density of 4.5 A cm−2 at 2.13 V with the Ir loading of 115 mg cm−2. The nanoarray structure remains unchanged in a single-cell during a 500-h stability test. In sum, these work highlights a new approach to enhance the performance and durability for PEM fuel cells and water electrolysers.

Superprotonic Conductivity of Guanidinium Organosulfonate Hydrogen-Bonded Organic Frameworks with Nanotube-Shaped Proton Transport Channels.

Grasping proton transport pathways and mechanisms is vital for the application of fuel cell technology. Herein, we screened four guanidinium organosulfonate charge-assisted hydrogen-bonded organic frameworks (HOFs), namely, GBBS, G 3 TSPHB, G 4 TSP, and G 6 HSPB, which possess high hydrogen-bonded density proton transport networks shaped like nanotubes. These materials were prepared by self-assembly through charge-assisted interactions between guanidinium cations and organosulfonate anions, as well as by host-guest regulation. At 80 °C and 93% RH, the proton conductivity of GBBS, G 3 TSPHB, G 4 TSP, and G 6 HSPB can reach 4.56 × 10-2, 2.55 × 10-2, 4.01 × 10-2, and 1.2 × 10-1 S cm-1, respectively, with superprotonic conductivity. Doping G 6 HSPB into the Nafion matrix prepared composite membranes for testing the performance of fuel cells. At 80 °C and 98% RH, the proton conductivity of 9%-G 6 HSPB@Nafion reached a maximum value of 1.14 × 10-1 S cm-1, which is 2.8 times higher than recast Nafion. The results showed that charge-assisted HOFs with high proton channel density have better proton transport properties, providing a reference for the design of highly proton-conducting materials.

Poly(aryl ether sulfone ketone) with densely sulfonated structural units facilitate microphase separation to promote proton transport

The development of high-performance and low-cost membrane materials is crucial for proton exchange membrane fuel cells. To improve the proton conductivity, we designed a novel multiple phenyls monomer. Then, we synthesize a series of sulfonated poly(aryl ether sulfone ketone) membranes (SPAESK-x). The hydrophilic groups are densely distributed in units after sulfonation, which can form large hydrophilic ion clusters and provide more connected channels for proton transport. The large hydrophilic ion clusters facilitate the separation of hydrophilic and hydrophobic phases to form wider proton transport channels. The SPAESK-15 membrane achieves a high proton conductivity (181.0 mS cm-1) at 80 °C. The novel monomer and polymers are budget and simple to synthesize, offering the possibility of large-scale preparation. Overall, the novel structure has the potential to develop high-performance electrolyte materials.

Continuous Ultrathin Zwitterionic Covalent Organic Framework Membrane Via Surface-Initiated Polymerization Toward Superior Water Retention.

Efficient construction of proton transport channels in proton exchange membranes maintaining conductivity under varied humidity is critical for the development of fuel cells. Covalent organic frameworks (COFs) hold great potential in providing precise and fast ion transport channels. However, the preparation of continuous free-standing COF membranes retaining their inherent structural advantages to realize excellent proton conduction performance is a major challenge. Herein, a zwitterionic COF material bearing positive ammonium ions and negative sulphonic acid ions is developed. Free-standing COF membrane with adjustable thickness is constructed via surface-initiated polymerization of COF monomers. The porosity, continuity, and stability of the membranes are demonstrated via the transmission electron microscopy (TEM), atomic force microscopy (AFM), and scanning electron microscopy (SEM) characterization. The rigidity of the COF structure avoids swelling in aqueous solution, which improves the chemical stability of the proton exchange membranes and improves the performance stability. In the higher humidity range (50-90%), the prepared zwitterionic COF membrane exhibits superior capability in retaining the conductivity compared to COF membrane merely bearing sulphonic acid group. The established strategy shows the potential for the application of zwitterionic COF in the proton exchange membrane fuel cells.

Phosphorylated poly(ethylene-co-vinyl alcohol) doping for enhanced proton conductivity and mechanical properties of side chain–type sulfonated poly(aryl ether ketone) proton-exchange membranes

Phosphorylated poly (ethylene-co-vinyl alcohol) (PEVOH) was synthesized and blended with side chain–type sulfonated poly (aryl ether ketone) (SPAEK) to prepare SPAEK proton-exchange membranes with improved physicochemical and electrochemical properties. The results indicate that PEVOH doping helps improve the mechanical properties and proton conductivity of the membranes. The addition of PEVOH not only enhances proton transport but also provides proton transport channels for the membranes at a high temperature and low humidity, leading to excellent fuel cell performance and low ohmic resistance. The interaction between sulfonic acid and phosphonic acid side chain groups leads to the excellent nano-phase separation under microscopic morphology. This forms a large hydrogen bonding network between the acidic and amphoteric groups, which facilitates proton transport at low relative humidities.

Effect of temperature and external electric field on proton transport in ordered and amorphous proton exchange membranes: A molecular dynamics study

Proton exchange membrane (PEM) is a key component of proton exchange membrane fuel cell, and its proton conductivity directly affects the performance of fuel cell. Imparting order to Nafion molecules is one of potential effective approaches that can significantly improve the proton transport performance of PEM, but the underlying mechanism of this effect as well as the regulatory mechanism is unknown. In order to investigate the regulatory mechanism of temperature, electric field, and water content on the transport mechanism of the PEM and compare the transport properties between ordered and amorphous membranes, this study examined the proton migration rate of ordered and amorphous membranes under different electric field and water contents at 300 K and 350 K with molecular dynamics methods. The simulation results indicate that the ordered PEM exhibits better proton conductivity compared with the amorphous PEM due to its ordered structure with smoothly connected proton transport channels. The proton conductivity of the ordered PEM with a water content of 16 exhibits a remarkably high proton conductivity of 0.153 S/cm at a temperature of 350 K. Additionally, it was found that increasing electric field intensity, temperature, and hydration level can enhance the diffusion of water molecules and hydrated protons and improve the proton conductivity of the PEM. Especially, at low electric field intensity, ordered PEM demonstrates superior proton conductivity compared to amorphous PEM. However, as the electric field strength increases to 0.7 V/nm, the proton diffusion behaviour of amorphous PEM gradually surpasses that of ordered PEM. Moreover, the electric field can enhance the anisotropic diffusion behaviour of PEM. As the electric field increases from 0 V/nm to 0.7 V/nm, the diffusion coefficient parallel to the direction of the electric field increases by three orders of magnitude, while the diffusion coefficient perpendicular to the direction of the electric field increases by only one order of magnitude.