Durable Multiblock Poly(biphenyl alkylene) Anion Exchange Membranes with Microphase Separation for Hydrogen Energy Conversion

Anion exchange membrane fuel cells (AEMFCs) and water electrolysis (AEMWE) show great application potential in the field of hydrogen energy conversion technology. However, scalable anion exchange membranes (AEMs) with desirable properties are still lacking, which greatly hampers the commercialization of this technology. Herein, we propose a series of novel multiblock AEMs based on ether-free poly(biphenyl ammonium-b-biphenyl phenyl)s (PBPA-b-BPPs) that are suitable for use in high performance AEMFC and AEMWE systems because of their well-formed microphase separation structures. The developed AEMs achieved outstanding OH⁻ conductivity (162.2 mS cm⁻¹ at 80 °C) with a low swelling ratio, good alkaline stability, and excellent mechanical durability (tensile strength >31 MPa and elongation at break >147 % after treatment in 2 M NaOH at 80 °C for 3750 h). A PBPA-b-BPP-based AEMFC demonstrated a remarkable peak power density of 2.41 W cm⁻² and in situ durability for 330 h under 0.6 A cm⁻² at 70 °C. An AEMWE device showed a promising performance (6.25 A cm⁻² at 2 V, 80 °C) and outstanding in situ durability for 3250 h with a low voltage decay rate (<28 μV h⁻¹). The newly developed PBPA-b-BPP AEMs thus show great application prospects for energy conversion devices.     

Insight into the hydrogen oxidation electrocatalytic performance enhancement on Ni via oxophilic regulation of MoO_2

Exploring platinum-group-metal(PGM)free electrocatalysts for hydrogen oxidation reaction(HOR)in alkaline media is essential to the progress of anion exchange membrane fuel cells(AEMFCs).In this work,a Ni/MoO₂ heterostructure catalyst with comparable HOR activity in alkaline electrolyte with PGM catalyst was prepared by a simple hydrothermal-reduction method.Remarkably,the Ni/MoO₂ presents a mass kinetic current density of 38.5 mA mgNi^-1 at the overpotential of 50 mV,which is higher than that of the best PGM free HOR catalyst reported by far.Moreover,the HOR performance of Ni/MoO₂ under 100 ppm CO shows negligible fading,together with the superior durability,render it significant potential for application in AEMFCs.A particular mechanistic study indicates that the excellent HOR performance is ascribed to the accelerated Volmer step by the incorporation of MoO₂.The function of MoO₂ was further confirmed by CO striping experiment on Pt/C-MoO₂ that MoO₂ can facilitated OH adsorption thus accelerate the HOR process.On account of the high performance and low cost,the Ni/MoO₂ electrocatalyst encourages the establishment of high performance PGM free catalyst and shows significant potential for application in AEMFCs.     

Migration and Precipitation of Platinum in Anion-Exchange Membrane Fuel Cells

Despite the recent progress in increasing the power generation of Anion-exchange membrane fuel cells (AEMFCs), their durability is still far lower than that of Proton exchange membrane fuel cells (PEMFCs). Using the complementary techniques of X-ray micro-computed tomography (CT), Scanning Electron Microscopy (SEM) and Energy Dispersive X-ray (EDX) spectroscopy, we have identified Pt ion migration as an important factor to explain the decay in performance of AEMFCs. In alkaline media Pt⁺² ions are easily formed which then either undergo dissolution into the carbon support or migrate to the membrane. In contrast to PEMFCs, where hydrogen cross over reduces the ions forming a vertical “Pt line” within the membrane, the ions in the AEM are trapped by charged groups within the membrane, leading to disintegration of the membrane and failure. Diffusion of the metal components is still observed when the Pt/C of the cathode is substituted with a FeCo−N−C catalyst, but in this case the Fe and Co ions are not trapped within the membrane, but rather migrate into the anode, thereby increasing the stability of the membrane.     

Nitrogen‐doped Carbon–CoOx Nanohybrids: A Precious Metal Free Cathode that Exceeds 1.0 W cm−2 Peak Power and 100 h Life in Anion‐Exchange Membrane Fuel Cells

Efficient and durable nonprecious metal electrocatalysts for the oxygen reduction (ORR) are highly desirable for several electrochemical devices, including anion exchange membrane fuel cells (AEMFCs). Here, a 2D planar electrocatalyst with CoO_x embedded in nitrogen‐doped graphitic carbon (N‐C‐CoO_x) was created through the direct pyrolysis of a metal–organic complex with a NaCl template. The N‐C‐CoO_x catalyst showed high ORR activity, indicated by excellent half‐wave (0.84 V vs. RHE) and onset (1.01 V vs. RHE) potentials. This high intrinsic activity was also observed in operating AEMFCs where the kinetic current was 100 mA cm^?2 at 0.85 V. When paired with a radiation‐grafted ETFE powder ionomer, the N‐C‐CoO_x AEMFC cathode was able to achieve extremely high peak power density (1.05 W cm^?2) and mass transport limited current (3 A cm^?2) for a precious metal free electrode. The N‐C‐CoO_x cathode also showed good stability over 100 hours of operation with a voltage decay of only 15 % at 600 mA cm^?2 under H₂/air (CO₂‐free) reacting gas feeds. The N‐C‐CoO_x cathode catalyst was also paired with a very low loading PtRu/C anode catalyst, to create AEMFCs with a total PGM loading of only 0.10 mg_Pt‐Ru cm^?2 capable of achieving 7.4 W mg^?1_PGM as well as supporting a current of 0.7 A cm^?2 at 0.6 V with H₂/air (CO₂ free)—creating a cell that was able to meet the 2019 U.S. Department of Energy initial performance target of 0.6 V at 0.6 A cm^?2 under H₂/air with a PGM loading <0.125 mg cm^?2 with AEMFCs for the first time.     

季铵盐阴离子交换膜研究进展

近年来,阴离子交换膜燃料电池的发展受到了广泛关注.开发具有碱稳定性能优异,电导率高的阴离子交换膜(AEMs)材料成为了研究的热点.AEMs主要由聚合物骨架和阳离子基团组成,这两者是影响膜碱稳定性和电导率的重要因素.本文综述了季铵盐类阴离子交换膜聚合物骨架结构中含有醚氧键和不含醚氧键的烷基季铵盐AEMs、N-螺环季铵盐A...     

Boosting Hydrogen Oxidation Activity of Ni in Alkaline Media through Oxygen‐Vacancy‐Rich CeO2/Ni Heterostructures

The search for highly efficient platinum group metal (PGM)‐free electrocatalysts for the hydrogen oxidation reaction (HOR) in alkaline electrolytes remains a great challenge in the development of alkaline exchange membrane fuel cells (AEMFCs). Here we report the synthesis of an oxygen‐vacancy‐rich CeO₂/Ni heterostructure and its remarkable HOR performance in alkaline media. Experimental results and density functional theory (DFT) calculations indicate the electron transfer between CeO₂ and Ni could lead to thermoneutral adsorption free energies of H* (ΔG_H*). This, together with the promoted OH* adsorption strength derived from the abundance of oxygen vacancies in the CeO₂ species, contributes to the excellent HOR performance with the exchange current density and mass activity of 0.038 mA cm_Ni^?2 and 12.28 mA mg_Ni^?1, respectively. This presents a new benchmark for PGM‐free alkaline HOR and opens a new avenue toward the rational design of high‐performance PGM‐free electrocatalysts for alkaline HOR.     

Confined‐Space Alloying of Nanoparticles for the Synthesis of Efficient PtNi Fuel‐Cell Catalysts

The efficiency of polymer electrolyte membrane fuel cells is strongly depending on the electrocatalyst performance, that is, its activity and stability. We have designed a catalyst material that combines both, the high activity for the decisive cathodic oxygen reduction reaction associated with nanoscale Pt alloys, and the excellent durability of an advanced nanostructured support. Owing to the high specific activity and large active surface area, the catalyst shows extraordinary mass activity values of 1.0 A mg_Pt^?1. Moreover, the material retains its initial active surface area and intrinsic activity during an extended accelerated aging test within the typical operation range. This excellent performance is achieved by confined‐space alloying of the nanoparticles in a controlled manner in the pores of the support.     

High‐Performance Bismuth‐Doped Nickel Aerogel Electrocatalyst for the Methanol Oxidation Reaction

Low‐cost, non‐noble‐metal electrocatalysts are required for direct methanol fuel cells, but their development has been hindered by limited activity, high onset potential, low conductivity, and poor durability. A surface electronic structure tuning strategy is presented, which involves doping of a foreign oxophilic post‐transition metal onto transition metal aerogels to achieve a non‐noble‐metal aerogel Ni₉₇Bi₃ with unprecedented electrocatalytic activity and durability in methanol oxidation. Trace amounts of Bi are atomically dispersed on the surface of the Ni₉₇Bi₃ aerogel, which leads to an optimum shift of the d‐band center of Ni, large compressive strain of Bi, and greatly increased conductivity of the aerogel. The electrocatalyst is endowed with abundant active sites, efficient electron and mass transfer, resistance to CO poisoning, and outstanding performance in methanol oxidation. This work sheds light on the design of high‐performance non‐noble‐metal electrocatalysts.     

Direct borohydride fuel cells: A selected review of their reaction mechanisms,electrocatalysts, and influence of operating parameters on their performance

Direct borohydride fuel cells (DBFC) oxidize an easily-stored energy-dense borohydride fuel (sodium borohydride: NaBH₄), that in theory reacts ca. 400 mV below H₂ and produces 8 electrons per BH₄^- anion. However, the borohydride oxidation reaction (BOR) does not fully meet these promises in practice: the electrocatalyst nature, structure and state-of-surface, and the operating conditions (pH, BH₄^- concentration, temperature, fluxes) noticeably influence the BOR kinetics and mechanism. Nickel and platinum-based catalysts both have assets for the BOR. DBFCs can only yield decent performance if their separator combines high ion-conductivity and efficient separation of the reactants; cation-exchange membranes, anion-exchange membranes, bipolar membranes and porous separators all have their own advantages and drawbacks. Besides the anode, the choice of separator must consider the DBFC cathode reaction, where oxygen (usually from air) or hydrogen peroxide are reduced, provided adapted catalysts are used. All these aspects drive the DBFC performance and stability/durability.     

On-line mass spectrometry study of carbon corrosion in polymer electrolyte membrane fuel cells

The electrochemical corrosion of carbon catalyst supports in polymer electrolyte membrane (PEM) fuel cells is investigated by monitoring the generation of CO₂ using an on-line mass spectrometer at a constant potential of 1.4 V. Our results suggest that carbon supports with a high degree of graphitization are more corrosion-resistant, which results in a dramatic improvement of the catalyst durability. We also show that CO₂ measurements performed using on-line mass spectrometry represent a time-effective and reliable method for studying the electrochemical corrosion of carbon supports in PEM fuel cells.     

基于阳离子交换基团的阴离子交换膜研究进展

近年来,阴离子交换膜燃料电池的发展受到了广泛关注。 开发具有碱稳定性能优异、电导率高的阴离子交换膜材料成为了研究的热点。 阴离子交换膜(AEM)主要由聚合物骨架和阳离子基团组成,除了聚合物骨架结构,离子交换基团是影响膜碱稳定性和电导率的重要因素,因此,设计离子基团是提高膜性能的重要手段之一。 本文综述了近年来功能基团分别为季铵、胍基、咪唑鎓盐、季鏻、金属配合物、N-螺环季铵盐、哌啶和吡咯等阳离子交换基团的AEM的研究进展,其中包括不同种类阳离子交换基团的AEM的结构,碱稳定性能和OH^-电导率,同时对于含有阳离子交换基团的AEM的结构设计进行了分析和展望。     

Facile Synthesis of PdCu Echinus‐Like Nanocrystals as Robust Electrocatalysts for Methanol Oxidation Reaction

Exploiting high‐performance and inexpensive electrocatalysts for methanol electro‐oxidation is conductive to promoting the commercial application of direct methanol fuel cells. Here, we present a facile synthesis of echinus‐like PdCu nanocrystals (NCs) via a one‐step and template‐free method. The echinus‐like PdCu NCs possess numerous straight and long branches which can provide abundant catalytic active sites. Owing to the novel nanoarchitecture and electronic effect of the PdCu alloy, the echinus‐like PdCu NCs display high electrocatalytic performance toward methanol oxidation reaction in an alkaline medium. The mass activity of echinus‐like PdCu NCs is 1202.1 mA mg_Pd^?1, which is 3.7 times that of Pd/C catalysts. In addition, the echinus‐like structure, as a kind of three‐dimensional self‐supported nanoarchitecture, endows PdCu NCs with significantly enhanced stability and durability. Hence, the echinus‐like PdCu NCs hold prospect of being employed as electrocatalysts for direct alcohol fuel cells.     

High-Performance Bismuth-Doped Nickel Aerogel Electrocatalyst for the Methanol Oxidation Reaction

Low-cost, non-noble-metal electrocatalysts are required for direct methanol fuel cells, but their development has been hindered by limited activity, high onset potential, low conductivity, and poor durability. A surface electronic structure tuning strategy is presented, which involves doping of a foreign oxophilic post-transition metal onto transition metal aerogels to achieve a non-noble-metal aerogel Ni₉₇Bi₃ with unprecedented electrocatalytic activity and durability in methanol oxidation. Trace amounts of Bi are atomically dispersed on the surface of the Ni₉₇Bi₃ aerogel, which leads to an optimum shift of the d-band center of Ni, large compressive strain of Bi, and greatly increased conductivity of the aerogel. The electrocatalyst is endowed with abundant active sites, efficient electron and mass transfer, resistance to CO poisoning, and outstanding performance in methanol oxidation. This work sheds light on the design of high-performance non-noble-metal electrocatalysts.     

Novel ETFE based radiation grafted poly(styrene sulfonic acid-co-methacrylonitrile) proton conducting membranes with increased stability

Styrene radiation grafted ETFE based proton conducting membranes are subject to degradation under fuel cell operating conditions and show a poor stability. Lifetimes exceeding 250 h can only be achieved with crosslinked membranes. In this study, a novel approach based on the increase of the intrinsic oxidative stability of uncrosslinked membranes is reported. Hence, the co-grafting of styrene with methacrylonitrile (MAN), which possesses a protected α-position and strong dipolar pendant nitrile group, onto 25 μm ETFE base film was investigated. Styrene/MAN co-grafted membranes were compared to a styrene based membrane in durability tests in single H₂/O₂ fuel cells. It is shown that the incorporation of MAN considerably improves the chemical stability, yielding fuel cell lifetimes exceeding 1000 h. The membrane preparation based on the co-grafting of styrene and MAN offers the prospect of tuning the MAN content and introduction of a crosslinker to enhance the oxidative stability of the resulting fuel cell membranes.     

Atomically Dispersed Zn-Pyrrolic-N4 Cathode Catalysts for Hydrogen Fuel Cells

To achieve practical application of fuel cell, it is vital to develop highly efficient and durable Pt-free catalysts. Herein, we prepare atomically dispersed ZnNC catalysts with Zn-Pyrrolic-N₄ moieties and abundant mesoporous structure. The ZnNC-based anion-exchange membrane fuel cell (AEMFC) presents an ultrahigh peak power density of 1.63 and 0.83 W cm⁻² in H₂-O₂ and H₂-air (CO₂-free), and also exhibits long-term stability with more than 120 and 100 h for H₂-air (CO₂-free) and H₂-O₂, respectively. Density functional calculations further unveil that the Zn-Pyrrolic-N₄ structure is the origin of high activity of as-synthesized ZnNC catalyst, while the Zn-Pyridinic-N₄ moiety is inactive for oxygen reduction reaction (ORR), which successfully explain the puzzle why most Zn-metal-organic framework -derived ZnNC catalysts in previous reports did not present good ORR activity because of their Zn-Pyridinic-N₄ moieties. This work offers a new route for speeding up development of AEMFCs.     

Instantaneous Free Radical Scavenging by CeO2 Nanoparticles Adjacent to the Fe−N4 Active Sites for Durable Fuel Cells

To achieve the Fe−N−C materials with both high activity and durability in proton exchange membrane fuel cells, the attack of free radicals on Fe−N₄ sites must be overcome. Herein, we report a strategy to effectively eliminate radicals at the source to mitigate the degradation by anchoring CeO₂ nanoparticles as radicals scavengers adjacent (Sca^ad-CeO2) to the Fe−N₄ sites. Radicals such as ⋅OH and HO₂⋅ that form at Fe−N₄ sites can be instantaneously eliminated by adjacent CeO₂, which shortens the survival time of radicals and the regional space of their damage. As a result, the CeO₂ scavengers in Fe−NC/Sca^ad-CeO2 achieved ∼80 % elimination of the radicals generated at the Fe−N₄ sites. A fuel cell prepared with the Fe−NC/Sca^ad-CeO2 showed a smaller peak power density decay after 30,000 cycles determined with US DOE PGM-relevant AST, increasing the decay of Fe−NC_Phen from 69 % to 28 % decay.     

Elastic and durable multi-cation-crosslinked anion exchange membrane based on poly(styrene-b-(ethylene-co-butylene)-b-styrene)

Anion exchange membranes (AEMs), as the core component of the new generation anion exchange membrane fuel cells (AEMFCs), directly determine the performance and the lifetime of this energy conversion device. Here, AEMs with pendant multiple quaternary ammonium anchored onto the poly(styrene-b-(ethylene-co-butylene)-b-styrene) (SEBS) backbone are synthesized. The comb-shaped copolymer SEBS-C16 is synthesized with N,N-dimethyl-1-hexadecylamine and chloromethylated SEBS to improve solubility, then the multi-cation crosslinker is prepared and grafted on the above backbone to fabricate a series of flexible multi-cation crosslinked SEBS-based AEMs (SEBS-C16-xC4, where x% is the ratio of the crosslinker to polystyrene block) with practical properties. The obtained SEBS-C16-20C4 membrane exhibits a microphase separated morphology with an interdomain spacing of 18.87 nm. Benefited from the ion channels, SEBS-C16-20C4 shows high conductivity of 77.78 mS/cm at 80°C. Additionally, the prepared SEBS-C16-20C4 membrane with ion exchange capacity of 2.35 mmol/g also exhibits enhanced alkaline stability (5.87% hydroxide conductivity decrease in 2 M NaOH solution at 80°C after 1,700 hr) and improved mechanical properties, compared with the non-crosslinked SEBS-C16 sample. Furthermore, AEMFC single cell performance is evaluated with the SEBS-C16-20C4 membrane, and a maximum power density of 182 mW/cm² is achieved at 80°C under H₂/O₂ conditions.     

Designing Thiophene-Enriched Fully Conjugated 3D Covalent Organic Framework as Metal-Free Oxygen Reduction Catalyst for Hydrogen Fuel Cells

The application of three-dimensional (3D) covalent organic frameworks (COFs) in renewable energy fields is greatly limited due to their non-conjugated skeletons. Here, we design and successfully synthesize a thiophene-enriched fully conjugated 3D COF (BUCT-COF-11) through an all-thiophene-linked saddle-shaped building block (COThTh-CHO). The BUCT-COF-11 exhibits excellent semiconducting property with intrinsic metal-free oxygen reduction reaction (ORR) activity. Using the COF as cathode catalyst, the assembled anion-exchange membrane fuel cells (AEMFCs) exhibited a high peak power density up to 493 mW cm⁻². DFT calculations reveal that thiophene introduction in the COF not only improves the conductivity but also optimizes the electronic structure of the sample, which therefore boosts the ORR performance. This is the first report on the application of COFs as metal-free catalysts in fuel cells, demonstrating the great potential of fully conjugated 3D COFs as promising semiconductors in energy fields.     

Controllable Synthesis of Ultrathin NiCo2O4 Nanosheets Incorporated onto Composite Nanotubes for Efficient Oxygen Reduction

Exploring non‐precious‐metal‐based oxygen reduction reaction (ORR) electrocatalysts featuring high efficiency, low cost, and environmental friendliness is of great importance for the broad applications of fuel cells and metal–air batteries. In this work, ultrathin NiCo₂O₄ nanosheets deposited on 1D SnO₂ nanotubes (SNT) were successfully fabricated through a productive electrospinning technique followed by a sintering and low‐temperature coprecipitation strategy. This hierarchically engineered architecture has ultrathin NiCo₂O₄ nanosheets uniformly and fully erected on both walls of tubular SNTs, which results in improved electrochemical activity as an ORR catalyst, in terms of positive onset potential and high current density, as well as superior tolerance to crossover effects and long‐term durability with respect to the commercial Pt/C catalyst. The excellent performance of SNT@NiCo₂O₄ composites may originate from their rationally designed hierarchical tubular nanostructure with completely exposed active sites and interconnected 1D networks for efficient electron and electrolyte transfer; this makes these composite nanotubes promising candidates to replace platinum‐based catalysts for practical fuel cell and metal–air battery applications.     

Phase Evolution and Electrochemical Properties of Nanometric Samarium Oxide for Stable Protonic Ceramic Fuel Cells

Electrochemical properties of metal oxide have a strong correlation with the crystalline structures. In this work, the effect of calcination temperature on the phase evolution and electrochemical properties of Sm₂O₃ was systematically evaluated. The results demonstrate that the sample calcinated at 700 °C (SM-700) is composed of a pure cubic phase while it begins to convert into a monoclinic phase at a temperature above 800 °C and fully converts into a monoclinic phase at 1100 °C. Moreover, the evolution process causes atomic redistribution, and more oxygen vacancies are formed in cubic phase Sm₂O₃, contributing to the improved ionic conductivity. The ionic conductivity of 0.138 S cm⁻¹ and maximum power density of 895 mW cm⁻² at 520 °C are achieved using SM-700 as electrolyte for protonic ceramic fuel cell (PCFC). The cubic structure remains stable in the durability testing process and the SM-700 based fuel cell delivers enhanced stability of 140 mW cm⁻² for 100 h. This research develops a calcination evolution process to improve the ionic conductivity and fuel cell performance of the Sm₂O₃ electrolyte for stable PCFC.