Anion Exchange Membrane Fuel Cells Research Articles

Interlayer Polymerization to Construct a Fully Conjugated Covalent Organic Framework as a Metal-Free Oxygen Reduction Reaction Catalyst for Anion Exchange Membrane Fuel Cells.

Two-dimensional (2D) covalent organic frameworks (COFs) have a multilayer skeleton with a periodic π-conjugated molecular array, which can facilitate charge carrier transport within a COF layer. However, the lack of an effective charge carrier transmission pathway between 2D COF layers greatly limits their applications in electrocatalysis. Herein, by employing a side-chain polymerization strategy to form polythiophene along the nanochannels, a conjugated bridge is constructed between the COF layers. The as-synthesized fully conjugated COF (PTh-COF) exhibits high oxygen reduction reaction (ORR) activity with narrowed energy band gaps. Correspondingly, PTh-COF is tested as a metal-free cathode catalyst for anion exchange membrane fuel cells (AEMFCs) which showed a maximum power density of 176mWcm-2 under a current density of 533mAcm-2. The density functional theory (DFT) calculation reveals that interlayer conjugated polythiophene optimizes the electron cloud distribution, which therefore enhances the ORR performance. This work not only provides new insight into the construction of a fully conjugated covalent organic framework but also promotes the development of new metal-free ORR catalysts.

Dilute RuCo Alloy Synergizing Single Ru and Co Atoms as Efficient and CO‐Resistant Anode Catalyst for Anion Exchange Membrane Fuel Cells

Ruthenium (Ru) is considered a promising candidate catalyst for alkaline hydroxide oxidation reaction (HOR) due to its hydrogen binding energy (HBE) like that of platinum (Pt) and its much higher oxygenophilicity than that of Pt. However, Ru still suffers from insufficient intrinsic activity and CO resistance, which hinders its widespread use in anion exchange membrane fuel cells (AEMFCs). Here, we report a hybrid catalyst (RuCo)NC+SAs/N‐CNT consisting of dilute RuCo alloy nanoparticles and atomically single Ru and Co atoms on N‐doped carbon nanotubes The catalyst exhibits a state‐of‐the‐art activity with a high mass activity of 7.35 A mgRu‐1. More importantly, when (RuCo)NC+SAs/N‐CNT is used as an anode catalyst for AEMFCs, its peak power density reaches 1.98 W cm‐2, which is one of the best AEMFCs properties of noble metal‐based catalysts at present. Moreover, (RuCo)NC+SAs/N‐CNT has superior long‐time stability and CO resistance. The experimental and density functional theory (DFT) results demonstrate that the dilute alloying and monodecentralization of the exotic element Co greatly modulates the electronic structure of the host element Ru, thus optimizing the adsorption of H and OH and promoting the oxidation of CO on the catalyst surface, and then stimulates alkaline HOR activity and CO tolerance of the catalyst.

Dilute RuCo Alloy Synergizing Single Ru and Co Atoms as Efficient and CO-Resistant Anode Catalyst for Anion Exchange Membrane Fuel Cells.

Ruthenium (Ru) is considered a promising candidate catalyst for alkaline hydroxide oxidation reaction (HOR) due to its hydrogen binding energy (HBE) like that of platinum (Pt) and its much higher oxygenophilicity than that of Pt. However, Ru still suffers from insufficient intrinsic activity and CO resistance, which hinders its widespread use in anion exchange membrane fuel cells (AEMFCs). Here, we report a hybrid catalyst (RuCo)NC+SAs/N-CNT consisting of dilute RuCo alloy nanoparticles and atomically single Ru and Co atoms on N-doped carbon nanotubes The catalyst exhibits a state-of-the-art activity with a high mass activity of 7.35 A mgRu-1. More importantly, when (RuCo)NC+SAs/N-CNT is used as an anode catalyst for AEMFCs, its peak power density reaches 1.98 W cm-2, which is one of the best AEMFCs properties of noble metal-based catalysts at present. Moreover, (RuCo)NC+SAs/N-CNT has superior long-time stability and CO resistance. The experimental and density functional theory (DFT) results demonstrate that the dilute alloying and monodecentralization of the exotic element Co greatly modulates the electronic structure of the host element Ru, thus optimizing the adsorption of H and OH and promoting the oxidation of CO on the catalyst surface, and then stimulates alkaline HOR activity and CO tolerance of the catalyst.

An all-metallic nanovesicle for hydrogen oxidation

Abstract Vesicle, a microscopic unit that encloses a volume with an ultrathin wall, is ubiquitous in biomaterials. However, it remains a huge challenge to create its inorganic metal-based artificial counterparts. Here, inspired by the formation of biological vesicles, we proposed a novel biomimetic-strategy to curling the ultrathin nanosheets into nanovesicles, which was driven by the interfacial strain. Trapped by the interfacial strain between initially formed substrate Rh layer and subsequently formed RhRu overlayer, the nanosheet begins to deform to release a certain strain. Density functional theory (DFT) calculations reveal that the Ru atoms make the curling of nanosheet more favorable in thermodynamics. Owing to the unique vesicular structure, the RhRu nanovesicles/C displays excellent hydrogen oxidation reaction (HOR) activity and stability, which has been proven by both the experiments and DFT calculations. Specifically, the HOR mass activity of RhRu nanovesicles/C are 7.52 A mg(Rh+Ru)−1 at an overpotential of 50 mV in rotating disk electrode (RDE) level; this is 24.19 times higher than that of commercial Pt/C (0.31 mA mgPt−1). Moreover, the hydroxide exchange membrane fuel cell (HEMFCs) with RhRu nanovesicles/C displays a peak power density of 1.62 W cm−2 in H2-O2 condition, much better than that of commercial Pt/C (1.18 W cm−2). This work creates a new biomimetic strategy to synthesize inorganic nanomaterials, paving out a pathway for designing catalytic reactors.

Ultralow-Loading Ruthenium-Iridium Fuel Cell Catalysts Dispersed on Zn-N Species-Doped Carbon.

Developing low-loading platinum-group-metal (PGM) catalysts is one of the key challenges in commercializing anion-exchange-membrane-fuel-cells (AEMFCs), especially for hydrogen oxidation reaction (HOR). Here, ruthenium-iridium nanoparticles being deposited on a Zn-N species-doped carbon carrier (Ru6Ir/Zn-N-C) are synthesized and used as an anodic catalyst for AEMFCs. Ru6Ir/Zn-N-C shows extremely high mass activity (5.87AmgPGM -1) and exchange current density (0.92mAcm-2), which is 15.1 and 3.9 times that of commercial Pt/C, respectively. Based on the Ru6Ir/Zn-N-C AEMFCs achieve a peak power density of 1.50Wcm-2, surpassing the state-of-the-art commercial PtRu catalysts and the power ratio of the normalized loading is 14.01WmgPGM anode -1 or 5.89W mgPGM -1 after decreasing the anode loading (87.49µgcm-2) or the total PGM loading (0.111mgcm-2), satisfying the US Department of Energy's PGM loading target. Moreover, the solvent and solute isotope separation method is used for the first time to reveal the kinetic process of HOR, which shows the reaction is influenced by the adsorption of H2O and OH-. The improvement of the hydrogen bond network connectivity of the electric double layer by adjusting the interfacial H2O structure together with the optimized HBE and OHBE is proposed to be responsible for the high HOR activity of Ru6Ir/Zn-N-C.

A novel side‐chain type double‐cation grafted poly (binaphthyl triphenyl piperidine) membranes for anion exchange membrane fuel cells

Recent advancements in anion exchange membrane fuel cells (AEMFCs) have been primarily driven by improvements in anion exchange membranes (AEMs). Aryl ether bond‐free membranes have emerged as a promising avenue for enhancing the  performance of AEMs. In this study, a novel side‐chain polymer, PBTP‐s‐x, possesses double cationic groups, aiming at further enhancing overall performance for AEMs. The use of a twisted stereospecific backbone structure of polymerized binaphthyl and triple biphenyl monomer and grafted side chains of piperidine cationic groups not only improves the microphase separation structure of the membrane, but also improves the alkali resistance. Notably, the PBTP‐s‐100 AEMs exhibit exceptional OH‐ conductivity, reaching up to 138.21 mS cm‐1, and show outstanding mechanical properties with a tensile strength of up to 28 MPa. Additionally, PBTP‐s‐100 displays excellent durability, proved by the NMR spectral consistency and over 80% ion conductivity retention in 1 M NaOH at 60°C for 4 weeks. And PBTP‐s‐100 exhibits a higher Lowest Unoccupied Molecular Orbital (LUMO) and a larger energy gap for LOMO and Highest Occupied Molecular Orbital (HOMO) by density functional theory calculation, which indicates it possesses sterling alkaline stability. These findings highlight the potential of PBTP‐s‐100 as a highly performing polymer structure suitable for AEM.

Temperature-Induced Interface Hybridization of WC Boosts NiCu Activity for Alkaline Hydrogen Oxidation Reaction.

The development of non-precious hydrogen oxidation reaction (HOR) catalysts is a major challenge for the commercialization of Pt-free fuel cells. Herein, a temperature-induced phase hybridization method is reported that greatly improves the catalytic performance of NiCu alloy for the HOR. The migration of W atoms hybridizes the interface of tungsten oxide (WOx) and tungsten carbide (WC) at the onset reduction temperature of WOx, leading to a greatly weakened H binding energy and an optimized OH binding energy, which endows NiCuW/WOx-WC@WC with favorable stability and CO resistance during HOR. The hybridization catalysts deliver a high mass activity of 29.37 mA mg-1 Ni and reach a peak power of 298 mW.cm-2 in H2-O2 anion exchange membrane fuel cells (AEMFCs).

Regulation Strategies for Fe-N-C and Co-N-C Catalysts for the Oxygen Reduction Reaction.

Proton exchange membrane fuel cells (PEMFCs) and alkaline membrane fuel cells (AEMFCs) have received great attention as energy devices of the next generation. Accelerating oxygen reduction reaction (ORR) kinetics is the key to improve PEMFC and AEMFC performance. Platinum-based catalysts are the most widely used catalysts for the ORR, but their high price and low abundance limit the commercialization of fuel cells. Non-noble metal-nitrogen-carbon (M-N-C) is considered to be the most likely material class to replace Pt-based catalysts, among which Fe-N-C and Co-N-C have been widely studied due to their excellent intrinsic ORR performance and have made great progress in the past decades. With the improvement of synthesis technology and a deeper understanding of the ORR mechanism, some reported Fe-N-C and Co-N-C catalysts have shown excellent ORR activity close to that of commercial Pt/C catalysts. Inspired by the progress, regulation strategies for Fe-N-C and Co-N-C catalysts are summarized in this Review from 5 perspectives: (1) coordinated atoms, (2) environmental heteroatoms and defects, (3) dual-metal active sites, (4) metal-based particle promoters, and (5) curved carbon layers. We also make suggestions on some challenges facing Fe-N-C and Co-N-C research.

Investigation of membranes-electrodes assemblies in anion exchange membrane fuel cells (AEMFCs): Influence of ionomer ratio in catalyst layers

Anion exchange membrane fuel cells (AEMFCs) have recently attracted significant attention as low-cost alternative fuel cells to traditional proton exchange membrane fuel cells because of the possible use of platinum-group metal-free electrocatalysts. Over the past decade, new materials dedicated to the alkaline medium, such as anion exchange membranes (AEMs) and anion exchange ionomers (AEIs), have been developed and studied in AEMFCs. However, only a few AEMs and AEIs are commercially available, and there are no ready-to-use membrane electrodes assemblies (MEAs) with the desired AEMs and AEIs. Consequently, the need to manufacture in-house CCMs or GDEs becomes a reality that we must face.This work deals with the influence of ionomer content on the prepared MEAs with the commercial anion exchange membrane and ionomer from Aemion™ Ionomr Innovations AF1–HNN8–2 and AP1–ENN8/HNN8 respectively and by varying the support (gas diffusion layer or membrane). The prepared MEAs were characterized morphologically by SEM and profilometry, as well as electrochemically by AEMFC polarization curves and cyclic voltammetry. In addition, an attempt to investigate water management was made with and without a reference electrode in the cell to understand the behavior of water in an operating AEMFC. Our results show that CCM-based MEAs can undergo deformation during the anion conversion step, leading to weakening of the membrane and hence faster degradation in the fuel cell. On the contrary, no deformation was observed for the GDEs during the anionic conversion, although the results are poorer due to (i) poor interface contact between membrane and GDE that depends on ionomer ratio in the ink and (ii) a high overpotential at the anode due to the production of water that cannot be effectively evacuated.

Synthesis of poly N-aryl piperidinium membrane and ionomer for anion exchange membrane fuel cell applications

Ether free backbones have recently attracted widespread attention in anion exchange membrane fuel cells (AEMFCs). Here we report the synthesis of two poly N-aryl piperidinium (PNAP) membranes from their monomers by the polycondensation method using trifluoromethanesulfonic acid as a catalyst. Density functional theory identifies the chemical reaction, and the radial distribution function represents the interactions between a water molecule and a functional group of PNAP membranes. The performance of the anion exchange membrane can be enhanced by varying the monomer ratios of PNAP. An optimized PNAP-2 membrane exhibits a hydroxide conductivity of 183 mS cm−1 at 90 °C and PNAP-2 ionomers with Pt/C catalysts display a greater half-wave potential (E1/2) of 0.81 V and a lower Tafel value of 65 mV dec−1. In fuel cell tests, a PNAP-2 ionomer alongside a 60% platinum-on-carbon (Pt/C) membrane electrode assembly achieved a peak power density of 2.07 W cm−2. The PNAP-2 remained stable for more than 230 h at a constant current density of 0.3 A cm−2. PNAP-2 also displays exceptional resistance to alkaline conditions, lasting for more than 1000 h in both 1 M and 5 M NaOH solutions at 60 °C.

An improvement on the electrocatalytic performance of ZIF-67 by in situ self-growing CNTs on surface

Efficient and robust oxygen reduction reaction (ORR) catalysts are essential for the development of high-performance anion-exchange membrane fuel cells (AEMFC). To enhance the electrochemical performance of metal–organic frameworks of cobalt-based zeolite imidazolium skeleton (ZIF-67), this study reported a novel ZIF-67-4@CNT by in situ growing carbon nanotubes (CNTs) on the surface of ZIF-67 via a mild two-step pyrolysis/oxidation treatment. The electrochemical results showed that the as-prepared ZIF-67-4@CNT after CTAB modification exhibited excellent catalytic activity with good stability, with Eonset, E1/2, and Ilimit, respectively were 0.98 V (versus RHE), 0.87 V (versus RHE) and 6.04 mA cm−2@1600 rpm, and a current retention rate of about 94.21% after polarized at 0.80 V for 10 000 s, which were all superior to that of the commercial 20 wt% Pt/C. The excellent ORR catalytic performance was mainly attributed to the large amount of the in situ growing CNTs on the surface, encapsulated with a wide range of valence states of metallic cobalt.

Hybrid high-performance oxygen reduction reaction Fe–N–C electrocatalyst for anion exchange membrane fuel cells

Atomically dispersed active sites and hierarchical porosity in Fe–N–C catalyst materials are essential for efficient oxygen reduction reaction (ORR) electrocatalysis and effective mass transport, respectively. However, the majority of these catalysts fail to deliver outstanding electrocatalytic activity and stumble when used as cathode materials in fuel cells. Herein, we developed a catalyst with partially transformed metallic Fe into Fe-Nx sites embedded in the carbonaceous matrix, and its excellent electrocatalytic performance is attributed to the hybrid nanoparticles and built-in Fe-Nx site structures. The optimized Fe@Fe–N–C catalyst was tested for ORR performance both ex-situ using the rotating (ring)-disk electrode technique and in an anion exchange membrane fuel cell (AEMFC). The Fe@Fe–N–C electrocatalyst exhibited remarkably enhanced ORR activity in alkaline media with a half-wave potential of 0.822 V vs. reversible hydrogen electrode (RHE) and showed the maximum power density (Pmax) of 242 mW cm−2 in an AEMFC test, surpassing the peak power density obtained from the Pt/C cathode catalyst (Pmax = 220 mW cm−2) under H2–O2 conditions. Therefore, the study provides a promising prospect for designing improved, cost-effective, and noble metal-free electrocatalysts for achieving high performance in AEMFCs.

High‐Performance Anion Exchange Membrane Fuel Cells Enabled by Nitrogen Configuration Optimization in Graphene‐Coated Nickel for Enhanced Hydrogen Oxidation

Anion exchange membrane fuel cell (AEMFC) technology is attracting intensive attention, due to its great potential by using non‐precious‐metal catalysts (NPMCs) in the cathode and cheap bipolar plate materials in alkaline media. However, in such case, the kinetics of hydrogen oxidation reaction (HOR) in the anode is two orders of magnitude sluggish than that of acidic electrolytes, which is recognized as the grand challenge in this field. Herein, we report the rationally designed Ni nanoparticles encapsulated by N‐doped graphene layers (Ni@NG) using a facile pyrolysis strategy. Based on the density functional theory calculations and electrochemical performance analysis, it is witnessed that the rich Pyridinic‐N within the graphene shell optimizes the binding energy of the intermediates, thus enabling the fundamentally enhanced activity for HOR with robust stability. As a proof of concept, the resultant Ni@NG sample as the anode with a low loading (1.8 mg cm−2) in AEMFCs delivers a high peak power density of 500 mW cm−2, outperforming all of those of NPMC‐based analogs ever reported.

Recent Developments of Metal-N-C Catalysts Toward Oxygen Reduction Reaction for Anion Exchange Membrane Fuel Cell: A Review

<p>Metal-N-C (MNC) catalysts have been anticipated as promising candidates for oxygen reduction reaction (ORR) to achieve low-cost polymer electrolyte membrane fuel cells. The structure of the M-N<sub>x</sub> moiety enabled a high catalytic activity that was not observed in previously reported transition metal nanoparticle-based catalysts. Despite progress in non-precious metal catalysts, the low density of active sites of MNCs, which resulted in lower single-cell performance than Pt/C, needs to be resolved for practical application. This review focused on the recent studies and methodologies aimed to overcome these limitations and develop an inexpensive catalyst with excellent activity and durability in an alkaline environment. It included the possibility of non-precious metals as active materials for ORR catalysts, starting from Co phthalocyanine as ORR catalyst and the development of methodologies (e.g., metal-coordinated N-containing polymers, metal-organic frameworks) to form active sites, M-N<sub>x</sub> moieties. Thereafter, the motivation, procedures, and progress of the latest research on the design of catalyst morphology for improved mass transport ability and active site engineering that allowed the promoted ORR kinetics were discussed.</p>

Stabilizing the Catalyst Layer for Durable and High Performance Alkaline Membrane Fuel Cells and Water Electrolyzers.

Anion exchange membrane (AEM) fuel cells (AEMFCs) and water electrolyzers (AEMWEs) suffer from insufficient performance and durability compared with commercialized energy conversion systems. Great efforts have been devoted to designing high-quality AEMs and catalysts. However, the significance of the stability of the catalyst layer has been largely disregarded. Here, an in situ cross-linking strategy was developed to promote the interactions within the catalyst layer and the interactions between catalyst layer and AEM. The adhesion strength of the catalyst layer after cross-linking was improved 7 times compared with the uncross-linked catalyst layer due to the formation of covalent bonds between the catalyst layer and AEM. The AEMFC can be operated under 0.6 A cm-2 for 1000 h with a voltage decay rate of 20 μV h-1. The related AEMWE achieved an unprecedented current density of 15.17 A cm-2 at 2.0 V and was operated at 0.5, 1.0, and 1.5 A cm-2 for 1000 h.

Highly Active MoS2‐MXenes Hybrid Electrocatalysts Towards the Oxygen Reduction Reaction

AbstractIn this work, catalytic performance of MoS2 supported on Mo2TiC2 and Ti3C2 MXenes towards the oxygen reduction reaction (ORR) was studied. These materials were synthesised through an etching route of MAX phases as precursors of MXenes, followed by a hydrothermal treatment to coat them with MoS2. This procedure generated MoS2 nanospheres covering the MXenes, which were verified by SEM‐EDX mapping, Raman spectroscopy and XPS. Activity of these materials towards ORR was studied by RRDE, comparing its performance with that of individual MoS2 and MXenes. As main features, it was demonstrated that production of HOO− occurring on the composites decreases in comparison with individual materials. Long‐term stability tests performed in O2‐saturated electrolyte showed a drop in the activity of the materials due to the increase in the production of HOO−, although no morphological or compositional changes were observed. Despite this result, the improvement of the catalytic properties of the individual materials means that these composites can be considered as candidates to be used as supports of active non‐noble metal nanoparticles in the cathodes of anion exchange membrane fuel cells (AEMFCs).

Exploring the Potential of α-MnO<sub>2</sub>/ Carbon Nanotubes for Improved Oxygen Reduction Reaction Performance at the Cathode of Alkaline Fuel Cells

In the field of fuel cell technology, the development of cost-effective catalysts is crucial for the commercialization of Alkaline Membrane Fuel Cells (AMFCs). Platinum (Pt) has traditionally been employed as the catalyst in AMFCs, but its high cost poses a major barrier to widespread adoption. In this study, a new catalyst material was developed by incorporating Manganese Dioxide (α-MnO2) into Carbon Nanotubes (CNTs) using hydrothermal synthesis techniques. The synthesized catalyst was characterized using Scanning Electron Microscopy (SEM) and X-ray diffraction (XRD), and its electrocatalytic activity was evaluated through Linear Sweep Voltammetry (LSV) and CV through Rotating Disc Electrode (RDE) experiments. The results showed that the α-MnO2-CNT composite displayed strong durability in the alkaline environment and high electrocatalytic activity for oxygen reduction reaction (ORR). The LSV measurements revealed a current density of -4.1 mA/cm2 and an overpotential of -0.3V relative to Standard Calomel Electrode (SCE) in a 0.1M KOH electrolyte. Additionally, the α-MnO2-CNT composite displayed high methanol tolerance and long-term stability compared to commercial Pt/C catalysts. This study demonstrates that the use of α-MnO2-CNT as a cost-effective alternative to Pt has the potential to facilitate the commercialization of AMFC technology.

Transient Distribution of Water in an Anion Exchange Membrane Fuel Cell Monitored by Operando Coherent Anti-Stokes Raman Scattering Spectroscopy

Transient Distribution of Water in an Anion Exchange Membrane Fuel Cell Monitored by Operando Coherent Anti-Stokes Raman Scattering Spectroscopy

A novel anion exchange membrane comprised of three aromatic units for fuel cells

Anion exchange membrane fuel cell (AEMFC) has made great progress recently due to the continuous improvement of anion exchange membrane (AEM). Aryl ether bond-free membranes are considered to be promising for improving the overall performance of AEMs. Here, we present a copolymer consisting of m-terphenyl, diphenyl ethane and biphenyl (PMDBP) to further enhance the microphase separation structure by introducing a third structural unit, biphenyl. Meanwhile, the more compact biphenyl structure enhances the mechanical strength of AEMs. Specifically, PMDBP AEMs possess superior OH- conductivity (up to 113 mS cm−1) and excellent mechanical properties (tensile strength up to 42 MPa). Furthermore, the PMDBP has an outstanding single-cell performance with a peak power density (PPD) of up to 95 mW cm−2 with a platinum-carbon (Pt/C) catalyst at 80°C in H2-air. In addition, PMDBP is provided with excellent durability, including NMR spectral consistency and over 90% ion conductivity retention in 1 M NaOH at 60°C for 720 h. This study provided a copolymer structure suitable for anion exchange membrane that can provide excellent performance for fuel cells and electrolyzers.

High-temperature inorganic anion exchange membranes based on layered double hydroxides for anion exchange membrane fuel cell applications

Anion-exchange membrane fuel cells (AEMFCs) have garnered substantial attention over the past two decades due to their numerous advantages, positioning them as promising alternatives to proton exchange membrane fuel cells (PEMFCs). However, their rapid development faces notable challenges, including the limited high-temperature and alkaline stability of anion-exchange membranes due to the incorporation of cationic functional groups, as well as intricate preparation processes. In this study, we propose a high-temperature inorganic anion exchange membrane based on layered double hydroxide doped with K2CO3 prepared by a simple process. This innovative approach optimizes the ionic transport pathway within the LDHs inorganic membrane and enhances water retention performance at elevated temperatures. The maximum cross-plane ionic conductivity of the membrane can reach up to 10−2 S cm−1. Remarkably, the peak power density attains an impressive level of 215.2 mW cm−2 at 110 °C and 200 kPa during the fuel cell testing.