Enhancing Surface Strain of Intermetallic Fuel Cell Catalysts by Composition-Induced Phase Transition.

The lattice parameter of platinum-based intermetallic compounds (IMCs), which correlates with the intrinsic activity of the oxygen reduction reaction (ORR), can be modulated by crystal phase engineering. However, the controlled preparation of IMCs with unconventional crystal structures remains highly challenging. Here, we demonstrate the synthesis of carbon-supported PtCu-based IMC catalysts with an unconventional L10 structure by a composition-regulated strategy. Experiment and machine learning reveal that the thermodynamically favorable structure changes from L11 to L10 when slight Cu atoms are substituted with Co. Benefiting from crystal-phase-induced strain enhancement, the prepared L10-type PtCu0.8Co0.2 catalyst exhibits much-enhanced mass and specific activities of 1.82 A mgPt-1 and 3.27 mA cmPt-2, which are 1.91 and 1.73 times higher than those of the L11-type PtCu catalyst, respectively. Our work highlights the important role of crystal phase in determining the surface strain of IMCs, and opens a promising avenue for the rational preparation of IMCs with different crystal phases by doping.

Efficient water-related failure detection in PEM fuel cells: Combining a PEMFCs fractional order impedance model with FFT-PWM techniques and artificial neural network classification.

Water management and early detection of faults in proton exchange membrane fuel cells (PEMFCs) are among the most critical constraints that limit the optimal spread of this type of energy. Consequently, it is necessary to enhance the reliability and durability of PEMFCs by developing an approach to diagnose and identify water failure modes. This paper proposes an effective and simple method to detect, diagnose, and classify various water failure modes in PEMFCs using a hybrid diagnostic approach. This approach combines the PEMFC fractional order impedance model (FOIM) with fast Fourier transform pulse width modulation (FFT-PWM) techniques and artificial neural network pattern recognition (ANN-PR) classification. The results show an accurate match between the electrochemical impedance spectroscopy (EIS) experimental data, the Nyquist impedance spectra of FOIM, and the FFT-PWM algorithm as a proposed alternative technique to EIS measurements. Learning of ANN-PR was performed using the frequency spectrum amplitude (FSA) database of the voltage and current signals produced by the PEMFCs FOIM DC/DC boost converter, which was generated using the FFT-PWM algorithm. The ANN-PR achieved low values for error accuracy, with the Low Square Error and Learning Error reaching 6.676 × 10-19 and 1.888 × 10-16, respectively. The elements inside the confusion matrix and the rest of the matrices confirm that the proposed model's accuracy, precision, recall, and high F1 score reached 100%. Furthermore, all predictions made by the ANN-PR model were consistently accurate across all areas of failure detection. Overall, the proposed method helps in analyzing, diagnosing, and classifying fuel cell failure modes such as flooding and drying, which may simplify the health assessment of PEMFC.

Using the IL-TEM Technique to Understand the Mechanism and Improve the Durability of Platinum Cathode Catalysts for Proton-Exchange Membrane Fuel Cells.

Proton-exchange membrane fuel cells are one of the most promising energy conversion technologies for both automotive and stationary applications. Scientists are testing a number of solutions to increase the durability of cells, especially catalysts, which are the most expensive component. These solutions include, among others, the modification of the composition and morphology of supported nanoparticles, the platinum-support interface, and the support itself. A detailed understanding of the mechanism of platinum degradation and the subsequent improvement of the durability of the entire cell requires the development of methods for effectively monitoring the behavior of catalytic nanoparticles under various cell operating conditions. The Identical-Location Transmission Electron Microscopy (IL-TEM) method makes it possible to visually track structural and morphological changes in the catalyst directly. Because the tests are performed with a liquid electrolyte imitating a membrane, they provide better control of the degradation conditions and, consequently, facilitate the understanding of nanoparticle degradation processes in various operating conditions. This review is primarily intended to disseminate knowledge about this technique to scientists using electron microscopy in the study of energy materials and to draw attention to issues related to the characterization of the structure of carbon supports.

Structural and Transport Properties of Hydrophilic and Hydrophobic Modified Ionomers in Proton Exchange Membrane Fuel Cells.

The sluggish commercial application of proton exchange membrane fuel cells (PEMFCs) with low Pt loading is chiefly hindered by concentration polarization loss, particularly at high current density regions. Addressing this, our study concentrates on the ionomer membranes in the cathode catalyst layer (CCL) and explores the potential of incorporating additional hydrophilic or hydrophobic components to modify these ionomers. Therefore, an all-atom model was constructed and for the ionomer and hydrophilic and hydrophobic modifications were implemented via incorporating SiO2 and PTFE, respectively. The investigation was conducted via molecular dynamics (MD) simulations to predict the morphology and structure of the ionomer and analyze the kinetic properties of oxygen molecules and protons. The simulation results elaborate that the hydrophilic and hydrophobic modifications favor the phase separation and the self-diffusion coefficients of oxygen molecules and protons are enhanced. Considering the hydration level of the ionomer films, hydrophilic modification facilitates mass transfer under low-hydration-level conditions, while hydrophobic modification is more effective in optimizing mass transfer as the hydration level increases. The optimal contents of SiO2 and PTFE for each hydration level in this work are 9.6% and 45%, respectively. This work proposes a reliable model and presents a detailed analysis of hydrophilic and hydrophobic modifications, which provides theoretical guidance for quantitative preparations of various composite membranes.

Hf and Co Dual Single Atoms Co-Doped Carbon Catalyst Enhance the Oxygen Reduction Performance.

Single-atom metal-doped M-N-C (M═Fe, Co, Mn, or Ni) catalysts exhibit excellent catalytic activity toward oxygen reduction reactions (ORR). However, their performance still has a large gap considering the demand for their practical applications. This study reports a high-performance dual single-atom doped carbon catalyst (HfCo-N-C), which is prepared by pyrolyzing Co and Hf co-doped ZIF-8 . Co and Hf are atomically dispersed in the carbon framework and coordinated with N to form Co-N4 and Hf-N4 active moieties. The synergetic effect between Co-N4 and Hf-N4 significantly enhance the catalytic activity and durability of the catalyst. In an acidic medium, the ORR half-wave potential (E1/2) of the catalyst is up to 0.82 V , which is much higher than that of the Co-N-C catalyst without Hf co-doping (0.80 V). The kinetic current density of the catalyst is up to 2.49 A cm-2 at 0.85 V , which is 1.74 times that of the Co-N-C catalyst without Hf co-doping. Moreover, the catalyst exhibits excellent cathodic performance in single proton exchange membrane fuel cells and Zn-air batteries. Furthermore, Hf co-doping can effectively suppress the formation of H2O2, resulting in significantly improved stability and durability.

Symmetry-Induced Regulation of Pt Strain Derived from Pt3 Ga Intermetallic for Boosting Oxygen Reduction Reaction.

Pt-based fuel cell catalysts with excellent activity and stability for proton-exchange membrane fuel cells (PEMFCs) have been developed through strain regulation in recent years. Herein, this work demonstrates that symmetry-induced strain regulation of Pt surface of PtGa intermetallic compounds can greatly enhance the catalytic performance of the oxygen reduction reaction (ORR). With the strain environment varies derived from the lattice mismatch of analogous PtGa core but different symmetry, the Pt surface of the PtGa alloy and the Pt3 Ga (Pm 3 ¯ $\bar{3}$ m) precisely realize 0.58% and 2.7% compressive strain compared to the Pt3 Ga (P4/mmm). Experimental and theoretical results reveal that when the compressive stress of the Pt lattice increases, the desorption process of O* intermediates becomes accelerated, which is conducive to oxygen reduction. The Pt3 Ga (Pm 3 ¯ $\bar{3}$ m) with high symmetry and compressive Pt surface exhibit the highest mass and specific activities of 2.18 A mgPt -1 and 5.36 mA cm-2 , respectively, which are more than one order of magnitude higher than those of commercial Pt/C catalysts. This work demonstrates that material symmetry can be used to precisely modulate Pt surface stress to enhance the ORR, as well as provide a distinct platform to investigate the relationship between Pt compressibility and catalytic activity.

Oxidation of Aqueous Phosphorous Acid Electrolyte in Contact with Pt Studied by X-ray Photoemission Spectroscopy.

The oxidation of the aqueous H3PO3 in contact with Pt was investigated for a fundamental understanding of the Pt/aqueous H3PO3 interaction with the goal of providing a comprehensive basis for the further optimization of high-temperature polymer electrolyte membrane fuel cells (HT-PEMFCs). Ion-exchange chromatography (IEC) experiments suggested that in ambient conditions, Pt catalyzes H3PO3 oxidation to H3PO4 with H2O. X-ray photoelectron spectroscopy (XPS) on different substrates, including Au and Pt, previously treated in H3PO3 solutions was conducted to determine the catalytic abilities of selected metals toward H3PO3 oxidation. In situ ambient pressure hard X-ray photoelectron spectroscopy (AP-HAXPES) combined with the "dip-and-pull" method was performed to investigate the state of H3PO3 at the Pt|H3PO3 interface and in the bulk solution. It was shown that whereas H3PO3 remains stable in the bulk solution, the catalyzed oxidation of H3PO3 by H2O to H3PO4 accompanied by H2 generation occurs in contact with the Pt surface. This catalytic process likely involves H3PO3 adsorption at the Pt surface in a highly reactive pyramidal tautomeric configuration.

Preparation and Characterization of Dopamine-Modified Carbon Fiber Paper Composites for Gas Diffusion Layers.

Carbon fibers (CFs) cannot be directly used for the preparation of CF paper because of their chemically inert nature. Herein, the surface of CFs was modified using the spontaneous oxidative self-polymerization of dopamine. By taking full advantage of the spontaneous oxidation and self-polymerization properties of PD to maintain the maximum strength of CFs, a polydopamine-modified CF paper (PDA-CFP) with excellent performance was prepared using PD-modified CFs (PDA-CFs). This increased the proportion of hydrophilic functional groups on the surface of carbon fibers, increased the O/C ratio on the CF surface by 6 times, and improved the bond strength between the modified CF and the adhesive by making full use of the interaction force between polydopamine and PVA fibers. In this way, the primary properties of the CF paper were improved. Overall, the results showed that the dispersion of CF was considerably improved with dopamine modification. In addition, the primary physical properties of PDA-CFP were better than those of virgin CF paper (CFP-0). PDA-CFP exhibited a maximum tensile strength of 2.04 kN·m-1, a minimum resistivity of 0.06055 Ω·cm-1, and a minimum porosity of 72.4%. The tightness was increased by up to 12.1%.

Defect-Engineered ZIF-Derived Non-Pt Cathode Catalyst at 1.5 mg cm-2 Loading for Proton Exchange Membrane Fuel Cells.

Due to the sluggish kinetics of the oxygen reduction reaction (ORR) by non-Pt based catalyst, high loading of catalyst is required to achieve satisfactory fuel cell performance, which inevitably leads to the increase of the catalyst layer thickness with serious mass transport resistance. Herein, a defective zeolitic imidazolate framework (ZIF) derived Co/Fe-N-C catalyst with small mesopores (2-4 nm) and high density of CoFe atomic active sites are prepared by regulating the Fe dosage and pyrolysis temperature. Molecular dynamics simulation and electrochemical tests indicate that > 2 nm mesopores show insignificant influence on the diffusion process of O2 and H2 O molecules, leading to the high utilization of active sites and low mass transport resistance. The proton exchange membrane fuel cell (PEMFC) shows a high-power density of 755 mW cm-2 with only 1.5 mg cm-2 of non-Pt catalyst in the cathode. No apparent performance loss caused by concentration difference can be observed, in particular in the high current density region (1 A cm-2 ). This work emphasizes the importance of small mesopore design in the Co/Fe-N-C catalyst, which is anticipated to provide essential guidance for the application of non-Pt catalysts.

Numerical Study on Thermal Stress of High Temperature Proton Exchange Membrane Fuel Cells during Start-Up Process.

High-temperature proton-exchange membrane fuel cells (HT-PEMFCs) with phosphoric-doped polybenzimidazole (PBI) membranes have a higher operating temperature compared to the PEMFCs operating below 373.15 K. The fuel cell is first heated from room temperature to the minimum operating temperature to avoid the generation of liquid water. The existence of liquid water can result in the loss of phosphoric acid and then affect the cell performance. In this study, the start-up process of HT-PEMFCs is numerically studied by establishing a three-dimensional non-isothermal mathematical model. Preheated gas is supplied into gas flow channels to heat the fuel cell, and then voltage load is applied to accelerate the start-up process. Effects of voltage (0.9 V, 0.7 V and 0.5 V) and flow arrangement (co-flow and counter flow) on temperature, current density, proton conductivity and stress distributions of fuel cells are examined. It is found that the maximum stress is increased when a lower voltage is adopted, and the counter-flow arrangement provides a more uniform stress distribution than that of co-flow arrangement.

A novel approach to pulsed laser deposition of platinum catalyst on carbon particles for use in polymer electrolyte membrane fuel cells.

The research undertaken aimed to develop an efficient Pt-based catalyst for polymer electrolyte membrane fuel cells (PEMFCs) by using a cost-effective and efficient physical method to deposit platinum nanoparticles (PtNPs) on carbon supports directly from the platinum target. The method developed avoids the chemical functionalization of the carbon substrate and the chemical synthesis of PtNPs during catalyst fabrication. Platinum was deposited on carbon particles at room temperature using a pulsed laser deposition (PLD) system equipped with an ArF excimer laser (λ = 193 nm). The uniform deposition of PtNPs on carbon supports was achieved thanks to a specially designed electromechanical system that mixed the carbon support particles during platinum deposition. In the studies, Vulcan XC-72R carbon black powder, a popular material used as support in the anodes and cathodes of PEMFCs, and a porous carbon material with a high degree of graphitization were used as carbon supports. The best electrochemical measurement results were obtained for Pt deposited on Vulcan XC-72R. The peak power density measured for this material in a membrane electrode assembly (MEA) of a PEMFC (fed with H2/Air) was 0.41 W/cm2, which is a good result compared to 0.57 W/cm2 obtained for commercial 20% Pt Vulcan XC-72R. This result was achieved with three times less Pt catalyst on the carbon support compared to the commercial catalyst, which means that a higher catalyst utilization factor was achieved.

Sustainable Plant-Based Biopolymer Membranes for PEM Fuel Cells.

Carboxycellulose nanofibers (CNFs) promise to be a sustainable and inexpensive alternative material for polymer electrolyte membranes compared to the expensive commercial Nafion membrane. However, its practical applications have been limited by its relatively low performance and reduced mechanical properties under typical operating conditions. In this study, carboxycellulose nanofibers were derived from wood pulp by TEMPO oxidation of the hydroxyl group present on the C6 position of the cellulose chain. Then, citric acid cross-linked CNF membranes were prepared by a solvent casting method to enhance performance. Results from FT-IR spectroscopy, 13C NMR spectroscopy, and XRD reveal a chemical cross-link between the citric acid and CNF, and the optimal fuel cell performance was obtained by cross-linking 70 mL of 0.20 wt % CNF suspension with 300 µL of 1.0 M citric acid solution. The membrane electrode assemblies (MEAs), operated in an oxygen atmosphere, exhibited the maximum power density of 27.7 mW cm-2 and the maximum current density of 111.8 mA cm-2 at 80 °C and 100% relative humidity (RH) for the citric acid cross-linked CNF membrane with 0.1 mg cm-2 Pt loading on the anode and cathode, which is approximately 30 times and 22 times better, respectively, than the uncross-linked CNF film. A minimum activation energy of 0.27 eV is achieved with the best-performing citric acid cross-linked CNF membrane, and a proton conductivity of 9.4 mS cm-1 is obtained at 80 °C. The surface morphology of carboxycellulose nanofibers and corresponding membranes were characterized by FIB/SEM, SEM/EDX, TEM, and AFM techniques. The effect of citric acid on the mechanical properties of the membrane was assessed by tensile strength DMA.

Ultrasmall, Coating-Free, Pyramidal Platinum Nanoparticles for High Stability Fuel Cell Oxygen Reduction.

Ultrasmall (<5 nm diameter) noble metal nanoparticles with a high fraction of {111} surface domains are of fundamental and practical interest as electrocatalysts, especially in fuel cells; the nanomaterial surface structure dictates its catalytic properties, including kinetics and stability. However, the synthesis of size-controlled, pure Pt-shaped nanocatalysts has remained a formidable chemical challenge. There is an urgent need for an industrially scalable method for their production. Here, a one-step approach is presented for the preparation of single-crystal pyramidal nanocatalysts with a high fraction of {111} surface domains and a diameter below 4 nm. This is achieved by harnessing the shape-directing effect of citrate molecules, together with the strict control of oxidative etching while avoiding polymers, surfactants, and organic solvents. These catalysts exhibit significantly enhanced durability while, providing equivalent current and power densities to highly optimized commercial Pt/C catalysts at the beginning of life (BOL). This is even the case when they are tested in full polymer electrolyte membrane fuel cells (PEMFCs), as opposed to rotating disk experiments that artificially enhance electrode kinetics and minimize degradation. This demonstrates that the {111} surface domains in pyramidal Pt nanoparticles (as opposed to spherical Pt nanoparticles) can improve aggregation/corrosion resistance in realistic fuel cell conditions, leading to a significant improvement in membrane electrode assembly (MEA) stability and lifetime.

Reducing Irreversible Performance Losses via a Graphene Oxide Buffer Layer for Proton-Exchange Membrane Fuel Cells.

Alloy catalysts are promising for proton-exchange membrane fuel cells but are difficult to realize high-durability operation because the dissolution of Pt-M (M = Co, Ni, etc.) metals inevitably accelerates irreversible performance degradation. Here, we propose a buffer layer solution that inserts a trace layer of a graphene oxide (GO) film between the PEM and the alloy catalyst layer to mitigate the poison effect. To distinguish the irreversible and reversible losses, two typical recovery procedures (shutdown and JRC-based protocols) being part of a fuel cell dynamic load cycle durability test are characterized. The electrochemical evaluation reveals that GO-1 µg/cm2 enables a higher initial performance and stability. Furthermore, the GO buffer layer design allows the realization of membrane electrode assemblies with a highly homogeneous current density distribution and a low accessible mass transport resistance. Thanks to the ion sieving effect in the GO buffer layer, high anti-poisoning and stability during the accelerated stress test process are ensured.

Impact of Membrane Phosphoric Acid Doping Level on Transport Phenomena and Performance in High Temperature PEM Fuel Cells.

In this work, a three-dimensional mathematical model including the fluid flow, heat transfer, mass transfer, and charge transfer incorporating electrochemical reactions was developed and applied to investigate the transport phenomena and performance in high-temperature proton exchange membrane fuel cells (HT-PEMFCs) with a membrane phosphoric acid doping level of 5, 7, 9, 11. The cell performance is evaluated and compared in terms of the polarization curve. The distributions of temperature, oxygen mass fraction, water mass fraction, proton conductivity, and local current density of four cases are given and compared in detail. Results show that the overall performance and local transport characteristics are significantly affected by the membrane phosphoric acid doping level.

Microporous Layer Containing CeO2-Doped 3D Graphene Foam for Proton Exchange Membrane Fuel Cells at Varying Operating Conditions.

To improve the interfacial mass-transfer efficiency, microporous layers (MPLs) containing CeO2 nanorods and the CeO2 nano-network were prepared for proton exchange membrane fuel cells (PEMFCs). In order to minimize the contact resistance, the three-dimensional (3D) graphene foam (3D-GF) was used as the carrier for the deposition of CeO2 nanorods and the nano-network. The CeO2-doped 3D-GF anchored at the interface between the catalyst layer and microporous layer manufactured several novel functional protrusions. To evaluate the electrochemical property, the normal MPL, the MPL containing raw 3D-GF, and MPLs containing different kinds of CeO2-doped 3D-GF were used to assemble the membrane electrode assemblies (MEAs). Measurements show that the CeO2-doped 3D-GF improved the reaction kinetics of the cathode effectively. In addition, the hydrophilic CeO2-doped 3D-GF worked as the water receiver to prevent the dehydration of MEAs at dry operating condition. Besides, at a high current density or humid operating condition, the CeO2-doped 3D-GF provided the pathway for water removal. Compared with the CeO2 nanorods, the CeO2 nano-network on 3D-GF revealed a higher adaptability at varying operating conditions. Hence, such composition and structure design of MPL is a promising strategy for the optimization of high-performance PEMFCs.

Phase Transformation Dynamics in Sulfate-Loaded Lanthanide Triphosphonates. Proton Conductivity and Application as Fillers in PEMFCs.

Phase transformation dynamics and proton conduction properties are reported for cationic layer-featured coordination polymers derived from the combination of lanthanide ions (Ln3+) with nitrilo-tris(methylenephosphonic acid) (H6NMP) in the presence of sulfate ions. Two families of materials are isolated and structurally characterized, i.e., [Ln2(H4NMP)2(H2O)4](HSO4)2·nH2O (Ln = Pr, Nd, Sm, Eu, Gd, Tb, Er, Yb; n = 4-5, Series I) and [Ln(H5NMP)]SO4·2H2O (Ln = Pr, Nd, Eu, Gd, Tb; Series II). Eu/Tb bimetallic solid solutions are also prepared for photoluminescence studies. Members of families I and II display high proton conductivity (10-3 and 10-2 S·cm-1 at 80 °C and 95% relative humidity) and are studied as fillers for Nafion-based composite membranes in PEMFCs, under operating conditions. Composite membranes exhibit higher power and current densities than the pristine Nafion membrane working in the range of 70-90 °C and 100% relative humidity and with similar proton conductivity.

A Molecular Model of PEMFC Catalyst Layer: Simulation on Reactant Transport and Thermal Conduction.

Minimizing platinum (Pt) loading while reserving high reaction efficiency in the catalyst layer (CL) has been confirmed as one of the key issues in improving the performance and application of proton exchange membrane fuel cells (PEMFCs). To enhance the reaction efficiency of Pt catalyst in CL, the interfacial interactions in the three-phase interface, i.e., carbon, Pt, and ionomer should be first clarified. In this study, a molecular model containing carbon, Pt, and ionomer compositions is built and the radial distribution functions (RDFs), diffusion coefficient, water cluster morphology, and thermal conductivity are investigated after the equilibrium molecular dynamics (MD) and nonequilibrium MD simulations. The results indicate that increasing water content improves water aggregation and cluster interconnection, both of which benefit the transport of oxygen and proton in the CL. The growing amount of ionomer promotes proton transport but generates additional resistance to oxygen. Both the increase of water and ionomer improve the thermal conductivity of the C. The above-mentioned findings are expected to help design catalyst layers with optimized Pt content and enhanced reaction efficiency, and further improve the performance of PEMFCs.

Electronic Transport and Corrosion Mechanisms of Graphite-Like Nanocrystalline Carbon Films Used on Metallic Bipolar Plates in Proton-Exchange Membrane Fuel Cells.

Nanocrystalline carbon films, which consist of graphite-like nanocrystals within an amorphous carbon matrix, have recently attracted extensive theoretical and experimental attention. Understanding the electronic transport and corrosion mechanisms of graphite-like nanocrystalline carbon films (GNCFs) is essential for their application in proton-exchange membrane fuel cells (PEMFCs). So far, limited progress has been made on the electronic or atomistic understanding of how the degree of structural order and grain boundaries affect the electronic transport and corrosion behaviors of GNCFs. In this work, using the Landauer-Büttiker formula merged with first-principles density functional theory, the conductance of GNCFs is presented as a function of their crystallinity. As the crystallinity decreases, the electron states around the Fermi level are found to be more spatially localized, thus hindering the electronic transport of GNCFs. Additionally, a systemic picture of the chemical reactivity of nanostructured surface in GNCFs toward typical particles existing in PEMFCs is drawn by ab initio molecular dynamics simulations. Systemic experimental investigations on the corrosion mechanisms of GNCFs used in PEMFCs have been conducted in this work. Compared with pure amorphous carbon films, the GNCFs exhibit higher corrosion current densities due to the preferential corrosion in the larger slit pores at the grain boundaries, but their stability in interfacial contact resistance is significantly improved by the embedded graphite-like nanocrystals, which have high levels of resistance to oxygen chemical adsorptions and act as high-speed ways to transport electrons.

Impact of N-Substituent and pKa of Azole Rings on Fuel Cell Performance and Phosphoric Acid Loss.

The influence of N-substituent and pKa of azole rings has been investigated for the performance of high-temperature polymer electrolyte membrane fuel cells (HT-PEMFCs). Imidazole, benzimidazole, and triazole groups were functionalized on the side chains of poly(phenylene oxide), respectively. Each azole group is categorized by their N-substituent into two types: unsubstituted and methyl-substituted azoles. The membranes with methyl-substituted azoles showed higher phosphoric acid (PA) doping levels with an average increase of 20% compared to those with unsubstituted azoles in the full-doped states. However, unsubstituted azoles more effectively improved the proton conductivity and the membrane with unsubstituted imidazole (IMPPO-H) showed a high anhydrous proton conductivity of 153 mS/cm at 150 °C. In contrast, the membranes with methyl-substituted azoles showed a higher PA retention with an average increase of 81% compared to those with unsubstituted azoles. The higher PA retention of methyl-substituted azoles also led to the higher fuel cell performance with the maximum increase of 95% in the power density. It was also revealed that higher pKa of azoles enhanced the PA retention and the fuel cell performance. Based on the experimental results of PA retention and density functional theory calculations, the PA loss mechanism was also proposed.