Coordination dynamics between fuel cell and battery technologies in the transition to clean cars.

Significant progress reconciling economic activities with a stable climate requires radical and rapid technological change in multiple sectors. Here, we study the case of the automotive industry's transition to electric vehicles, which involved choosing between two different technologies: fuel cell electric vehicles (FCEVs) or battery electric vehicles (BEVs). We know very little about the role that such technological uncertainty plays in shaping the strategies of firms, the efficacy of technological and climate policies, and the speed of technological transitions. Here, we explain that the choice between these two technologies posed a global and multisectoral coordination game, due to technological complementarities and the global organization of the industry's markets and supply chains. We use data on patents, supply-chain relationships, and national policies to document historical trends and industry dynamics for these two technologies. While the industry initially focused on FCEVs, around 2008, the technological paradigm shifted to BEVs. National-level policies had a limited ability to coordinate global players around a type of clean car technology. Instead, exogenous innovation spillovers from outside the automotive sector played a critical role in solving this coordination game in favor of BEVs. Our results suggest that global and cross-sectoral technology policies may be needed to accelerate low-carbon technological change in other sectors, such as shipping or aviation. This enriches the existing theoretical paradigm, which ignores the scale of interdependencies between technologies and firms.

A first principles analysis of potential-dependent structural evolution of active sites in Fe-N-C catalysts.

Fe-N-C (iron-nitrogen-carbon) electrocatalysts have emerged as potential alternatives to precious metal-based materials for the oxygen reduction reaction (ORR). However, the structure of these materials under electrochemical conditions is not well understood, and their poor stability in acidic environments poses a formidable challenge for successful adoption in commercial fuel cells. To provide molecular-level insights into these complex phenomena, we combine periodic density functional theory (DFT) calculations, exhaustive treatment of coadsorption effects for ORR reaction intermediates, including O and OH, and comprehensive analysis of solvation stabilization effects to construct voltage-dependent ab initio thermodynamic phase diagrams that describe the in situ structure of the active sites. These structures are further linked to activity and stability descriptors that can be compared with experimental parameters such as the half-wave potential for ORR and the onset potential for carbon corrosion and CO2 evolution. The results indicate that pyridinic Fe sites at zigzag carbon edges, as well as other edge sites, exhibit high activity for ORR compared to sites in the bulk. However, edges neighboring the active sites are prone to instability via overoxidation and consequent site loss. The results suggest that it could be beneficial to synthesize Fe-N-C catalysts with small sizes and large perimeter edge lengths to enhance ORR activity, while voltage fluctuations should be limited during fuel cell operation to prevent carbon corrosion of overoxidized edges.

Chirality enhances oxygen reduction.

Controlled reduction of oxygen is important for developing clean energy technologies, such as fuel cells, and is vital to the existence of aerobic organisms. The process starts with oxygen in a triplet ground state and ends with products that are all in singlet states. Hence, spin constraints in the oxygen reduction must be considered. Here, we show that the electron transfer efficiency from chiral electrodes to oxygen (oxygen reduction reaction) is enhanced over that from achiral electrodes. We demonstrate lower overpotentials and higher current densities for chiral catalysts versus achiral ones. This finding holds even for electrodes composed of heavy metals with large spin-orbit coupling. The effect results from the spin selectivity conferred on the electron current by the chiral assemblies, the chiral-induced spin selectivity effect.

A completely precious metal-free alkaline fuel cell with enhanced performance using a carbon-coated nickel anode.

SignificanceWe present a groundbreaking advance in completely nonprecious hydrogen fuel cell technologies achieving a record power density of 200 mW/cm2 with Ni@CNx anode and Co-Mn cathode. The 2-nm CNx coating weakens the O-binding energy, which effectively mitigates the undesirable surface oxidation during hydrogen oxidation reaction (HOR) polarization, leading to a stable fuel cell operation for Ni@CNx over 100 h at 200 mA/cm2, superior to a Ni nanoparticle counterpart. Ni@CNx exhibited a dramatically enhanced tolerance to CO relative to Pt/C, enabling the use of hydrogen gas with trace amounts of CO, critical for practical applications. The complete removal of precious metals in fuel cells lowers the catalyst cost to virtually negligible levels and marks a milestone for practical alkaline fuel cells.

Enhancing CO Tolerance in PEMFC Anodes via Thermal Oxidation Induced RuO2 Blocking Shell on a PtRu/C Catalyst.

CO poisoning in Pt-based anode catalysts significantly hampers the proton exchange membrane fuel cell (PEMFC) performance. Despite great advances in CO-tolerant catalysts, their effectiveness is often limited to fundamental three-electrode systems, which is inadequate for practical PEMFC applications. Herein, we present a straightforward thermal oxidation strategy for constructing a Ru oxide blocking layer on commercial PtRu/C through a one-step Ru-segregation-and-oxidation process. The resulting 0.7 nm thick Ru oxide layer effectively inhibits CO adsorption while maintaining hydrogen oxidation activity. PtRu@RuO2/C demonstrates exceptional CO tolerance, enduring 1% CO in rotating disk electrode tests, an ∼10-fold improvement compared to that of PtRu/C. Crucially, it retains high HOR activity and CO tolerance in PEMFC, with negligible polarization curve loss in the presence of 100 ppm CO. Notably, 85% HOR activity is retained after a 4 h stability test. This enhancement contributes to the Ru oxide layer decelerating CO adsorption kinetics, rather than promoting CO oxidation via the classic bifunctional mechanism.

Bioinspired Heterogeneous Construction of Lignocellulose-Reinforced COF Membranes for Efficient Proton Conduction.

The exponential interest in covalent organic frameworks (COFs) arises from the direct correlation between their diverse and intriguing properties and the modular design principle. However, the insufficient interlamellar interaction among COF nanosheets greatly hinders the formation of defect-free membranes. Therefore, developing a methodology for the facile fabrication of these materials remains an enticing and highly desirable objective. Herein, ultrahigh proton conductivity and superior stability are achieved by taking advantage of COF composite membranes where 2D TB-COF nanosheets are linked by 1D lignocellulosic nanofibrils (LCNFs) through π-π and electrostatic interactions to form a robust and ordered structure. Notably, the high concentration of -SO3 H groups within the COF pores and the abundant proton transport paths at COFs-LCNFs interfaces impart composite membranes ultrahigh proton conductivity (0.348 S cm-1 at 80 °C and 100% RH). Moreover, the directional migration of protons along the stacked nanochannels of COFs is facilitated by oxygen atoms on the keto groups, as demonstrated by density functional theory (DFT) calculations. The simple design concept and reliable operation of the demonstrated mixed-dimensional composite membrane are expected to provide an ideal platform for next-generation conductive materials.

Gradient Functional Layer Anode for Carbonate-Superstructured Solid Fuel Cells with Ethane Fuel.

Carbonate-superstructured solid fuel cells (CSSFCs) are an emerging type of fuel cells with high flexibility of fuels. However, using ethane fuel for solid fuel cells is a great challenge due to serious degradation of their anodes. Herein, this critical issue is solved by creating a novel gradient functional layer anode for CSSFCs. First, a finer-scale anode with a larger surface area is demonstrated to provide more active sites for the internal reforming reaction of ethane, achieving a 60% higher ethane conversion rate and 40% lower polarization resistance than conventional anodes. Second, incorporating a gradient functional layer into the anode results in an additional 50% enhancement in the peak power density of CSSFCs to a record high value (up to 241 mW cm-2) with dry ethane fuel at a low temperature of 550 °C, which is even comparable to the power density of conventional solid oxide fuel cells above 700 °C. Furthermore, the CSSFC with the gradient anode exhibits excellent durability for over 200 h. This finding provides a new strategy to develop efficient anodes for hydrocarbon fuels.

Humidity-Induced Degradation Mapping of Pt3Co ORR Catalyst for PEFC by In-Operando Electrochemistry and Ex Situ SAXS.

Understanding the degradation mechanisms of Pt-alloy catalysts is crucial for enhancing their durability. This study investigates the impact of relative humidity on Pt and Pt3Co catalysts using potential-cycling-based accelerated stress tests. Two conditions are investigated: 100% relative humidity on both sides, and a gradient with 30% at the anode and over 100% at the cathode. Pt3Co demonstrates sensitivity, with 77% performance loss and reductions in electrocatalyst surface area. Results demonstrate a 30% decrease in potential loss for Pt catalysts and a 77% increase for Pt3Co catalysts, indicating significant performance degradation in high humidity conditions, with Pt3Co exhibiting greater sensitivity. Measurements of electrochemically active surface area reinforce these findings. Resistance analysis using electrochemical impedance spectroscopy using equivalent circuit modeling reveals a threefold increase in Pt3Co MEAs' cathode charge transfer resistance and mass transport resistance during accelerated stress tests. Local current distribution analysis highlights differences between Pt catalyst and Pt3Co, with the latter displaying dealloying effects. Small-angle X-ray scattering reveals changes in particle and cluster sizes, indicating structural changes. Scanning electron microscopy highlights catalyst and membrane thickness variations, suggesting heterogeneity in Pt3Co. Under humidity gradients, Ostwald ripening plays a significant role in altering the catalyst's Pt3Co structure and subsequently impacting its performance.

Unveiling Local Aging Patterns Following Accelerated Stress Testing of High-Performance Polymer Electrolyte Fuel Cells.

This study presents an in-depth analysis of heterogeneous aging patterns in membrane electrode assemblies (MEAs) subjected to diverse accelerated stress test (AST) conditions, simulating carbon corrosion (CC AST) and Pt particle size growth in fully humidified (Pt AST-Wet) and underhumidified (Pt AST-Dry) H2/N2 atmospheres. Multimodal characterization techniques are used to focus on heterogeneous aging patterns, primarily examining the variations in current distributions and Pt particle size maps. The findings reveal distinct characteristics of current distributions for all the AST cases, with substantial changes and strong current gradients in the CC AST case, indicative of severe performance degradation. Notably, despite significant differences in Pt particle size growth at the end-of-life (EOL), the Pt AST-Wet and Pt AST-Dry cases show minor changes in spatial current distributions. Moreover, a preferential growth of Pt particles under serpentine flow field bends in the Pt AST-Wet case is observed for the first time. This study provides crucial insights into the role of mass transport properties in shaping fuel cell performance, and highlights the need to consider factors beyond electrochemically-active surface area (ECSA) when assessing fuel cell durability.

Concave Structural Carbon Co-Doped with Iron Atom Pairs and Nitrogen as Ultra-High Performance Catalyst Toward Oxygen Reduction.

It is crucial to rationally design and synthesize atomic-scale transition metal-doped carbon catalysts with high electrocatalytic activity to achieve a high-efficient oxygen reduction reaction (ORR). Herein, an electrocatalyst comprised of Fe-Fe dual atom pairs and N-doped concave carbon are reported (N-CC@Fe DA) that achieves ultrahigh electrocatalytic ORR activity. The catalyst is prepared by a gaseous doping approach, with zeolitic imidazolate framework-8 (ZIF-8) as the carbon framework precursor and cyclopentadienyliron dicarbonyl dimer as the Fe-Fe atom pair precursor. The catalyst exhibits high cathodic ORR catalytic performance in an alkaline Zn/air battery and proton exchange membrane fuel cell (PEMFC), yielding peak power densities of 241 mW cm-2 and 724 mW cm-2, respectively, compared to 127 mW cm-2 and 1.20 W cm-2 with conventional Pt/C catalysts as cathodes. The presence of Fe atom pairs coordinate with N atoms is revealed by X-ray photoelectron spectroscopy (XPS) and X-ray absorption spectroscopy (XAS) analysis, and Density Functional Theory (DFT) calculation results show that the Fe-Fe pair structure is beneficial for adsorbing oxygen molecules, activating the O─O bond, and desorbing OH* intermediates formed during oxygen reduction, resulting in a more efficient oxygen reaction. The findings may provide a new pathway for preparing ultra-high-performance doped carbon catalysts with Fe-Fe atom pair structures.

Anhydrous Proton Conduction Through a Chemically Robust Electrolyte Enabling a High-Temperature Non-Precious Metal Catalyzed Fuel Cell.

Fuel cells offer great promise for portable electricity generation, but their use is currently limited by their low durability, excessive operating temperatures, and expensive precious metal electrodes. It is therefore essential to develop fuel cell systems that can perform effectively using more robust electrolyte materials, at reasonable temperatures, with lower-cost electrodes. Recently, proton exchange membrane fuel cells have attracted attention due to their generally favorable chemical stability and quick start-up times. However, in most membrane materials, water is required for proton conduction, severely limiting operational temperatures. Here, for the first time it is demonstrated that when acidified, PAF-1 can conduct protons at high temperatures, via a unique framework diffusion mechanism. It shows that this acidified PAF-1 material can be pressed into pellets with high proton conduction properties even at high temperatures and pellet thickness, highlighting the processibility, and ease of use of this material. Furthermore, a fuel cell is shown with high power density output is possible using a non-precious metal copper electrode. Acid-doped PAF-1 therefore represents a significant step forward in the potential for a broad-purpose fuel cell due to it being cheap, robust, efficient, and easily processible.

Simultaneously Geometrical and Electronic Modulation of L10-PtZn by Trace Ge Boosts High-performance Oxygen Reduction Reaction.

Developing a highly active, durable, and low-platinum-based electrocatalyst for the cathodic oxygen reduction reaction (ORR) is for breaking the bottleneck of large-scale applications of proton exchange membrane fuel cells (PEMFCs). Herein, ultrafine PtZn intermetallic nanoparticles with low Pt-loading and trace germanium (Ge) involvement confined in the nitrogen-doped porous carbon (Ge-L10-PtZn@N-C) are reported. The Ge-L10-PtZn@N-C exhibit superior ORR activity with a mass activity of 3.04 A mg-1 Pt and specific activity of 4.69 mA cm-2, ≈12.2- and 10.2-times improvement compared to the commercial Pt/C (20%) at 0.90 V in 0.1 m KOH. The cathodic catalyst Ge-L10-PtZn@N-C assembled in the PEMFC shows encouraging peak power densities of 316.5 (at 0.86 V) and 417.2 mW cm-2 (at 0.91 V) in alkaline and acidic fuel-cell, respectively. The combination of experiment and density functional theory calculations (DFT) results robustly reveal that the participation of trace Ge can not only trigger a "growth site locking effect" to effectively inhibit nanoparticle growth, bring miniature nanoparticles, enhance dispersion uniformity, and achieve the exposure of the more electrochemical active site, but also effectively modulates the electronic structure, hence optimizing the adsorption/desorption of the oxygen intermediates.

Facile Deficiency Engineering in a Cobalt-Free Perovskite Air Electrode to Achieve Enhanced Performance for Protonic Ceramic Fuel Cells.

As a crucial component responsible for the oxygen reduction reaction (ORR), cobalt-rich perovskite-type cathode materials have been extensively investigated in protonic ceramic fuel cell (PCFC). However, their widespread application at a commercial scale is considerably hindered by the high cost and inadequate stability. In response to these weaknesses, the study presents a novel cobalt-free perovskite oxide, Ba0.95La0.05(Fe0.8Zn0.2)0.95O3-δ (BLFZ0.95), with the triple-conducting (H+|O2-|e-) property as an active and robust air electrode for PCFC. The B-site deficiency state contributes significantly to the optimization of crystal and electronic structure, as well as the increase in oxygen vacancy concentration, thus in turn favoring the catalytic capacity. As a result, the as-obtained BLFZ0.95 electrode demonstrates exceptional electrochemical performance at 700 °C, representing extremely low area-specific resistance of 0.04 Ω cm2 in humid air (3 vol.% H2O), extraordinarily high peak power density of 1114 mW cm-2, and improved resistance against CO2 poisoning. Furthermore, the outstanding long-term durability is achieved without visible deterioration in both symmetrical and single cell modes. This study presents a simple but crucial case for rational design of cobalt-free perovskite cathode materials with appreciable performance via B-site deficiency regulation.

Formation of Disordered High-Entropy-Alloy Nanoparticles for Highly Efficient Hydrogen Electrocatalysis.

Nanoparticles composed of high-entropy alloys (HEA NPs) exhibit remarkable performance in electrocatalytic processes such as hydrogen evolution and oxidations. In this study, two types of quinary HEA NPs of PtRhPdIrRu, are synthesized, featuring disordered and crystallized nanostructures, both with and without a boiling mixture. The disordered HEA NPs (d-HEA NPs) with a size of 3.5 nm is synthesized under intense boiling conditions, attributed to improved heat and mass transfer during reduction of precursors and particle growth. The disordered HEA NPs displayed an exceptionally high turnover frequency of 33.1 s-1 at an overpotential of 50 mV, surpassing commercial Pt NPs in acidic electrolytes by 5.4 times. Additionally, d-HEA NPs exhibited superior stability at a constant electrolyzing current of 50 mA cm-2 compared to commercial Pt NPs. When employed as the anodic catalyst in an H2-O2 fuel cell, d-HEA NPs demonstrated a remarkable high current power density of 15.3 kW per gram of noble metal. Consequently, these findings highlight the potential of d-HEA NPs in electrochemical applications involving hydrogen.

In Situ Pt Migration Enabled Resurrection of Electrocatalyst and Fuel Cell Device.

In direct methanol fuel cells (DMFCs), the poisoning of noble metals is considered to be a major impediment to their commercial development. Here, it is found that the loss of surface Pt is one main reason for the attenuation of catalyst performance during long-time methanol oxidation reaction (MOR). A strategy to realize in situ resurrection of the deactivated catalyst by migrating Pt atoms inside to the surface is innovatively proposed. A high-activity Pt-SnO2 is designed, whose MOR activity is resurrected to 97.4% of the initial value. Based on this, the multiple resurrection of a DMFC device is also achieved for the first time. This work provides a new approach for the solution of catalyst deactivation and the development of sustainable catalysts as well as fuel cells.

Enhancement of Catalytic Activity via Inevitable Reconstruction of the Ni-Mo Interface for Alkaline Hydrogen Oxidation.

The inevitable oxidation of nickel-metal-based catalysts exposed to the air will lead to instability and poor reproducibility of a catalytic interface, which is usually ignored and greatly hinders their application for the catalysis of alkaline hydrogen oxidation. The details on the formation of a world-class nickel-based HOR catalyst Ni3-MoOx/C-500 are reported via an interfacial reconstruction triggered by passive oxidation upon air exposure. Interfacial reconstruction, initiated with various Ni-Mo metal ratios and annealing temperature, can fine-tune the Ni-Mo interface with an increased work function and a reduced d-band center. The optimized Ni3-MoOx/C exhibits a record high mass activity of 102.8 mA mgNi -1, a top-level exchange current density of 76.5 µA cmNi -2, and exceptional resistance to CO poisoning at 1000 ppm CO for hours. The catalyzed alkaline exchange membrane fuel cell exhibits a maximum power output of 600 mW cm-2 and excellent stability, ranking it as one of the most active non-precious metals HOR catalysts to date.

Elucidation of the Transport Properties of Calcium-Doped High Entropy Rare Earth Aluminates for Solid Oxide Fuel Cell Applications.

Solid oxide fuel cells (SOFCs) are paving the way to clean energy conversion, relying on efficient oxygen-ion conductors with high ionic conductivity coupled with a negligible electronic contribution. Doped rare earth aluminates are promising candidates for SOFC electrolytes due to their high ionic conductivity. However, they often suffer from p-type electronic conductivity at operating temperatures above 500 °C under oxidizing conditions caused by the incorporation of oxygen into the lattice. High entropy materials are a new class of materials conceptualized to be stable at higher temperatures due to their high configurational entropy. Introducing this concept to rare earth aluminates can be a promising approach to stabilize the lattice by shifting the stoichiometric point of the oxides to higher oxygen activities, and thereby, reducing the p-type electronic conductivity in the relevant oxygen partial pressure range. In this study, the high entropy oxide (Gd,La,Nd,Pr,Sm)AlO3 is synthesized and doped with Ca. The Ca-doped (Gd,La,Nd,Pr,Sm)AlO3 compounds exhibit a higher ionic conductivity than most of the corresponding Ca-doped rare earth aluminates accompanied by a reduction of the p-type electronic conductivity contribution typically observed under oxidizing conditions. In light of these findings, this study introduces high entropy aluminates as a promising candidate for SOFC electrolytes.

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 (5.87 A mgPGM -1) and exchange current density (0.92 mA cm-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 1.50 W cm-2, surpassing the state-of-the-art commercial PtRu catalysts and the power ratio of the normalized loading is 14.01 W mgPGM anode -1 or 5.89 W mgPGM -1 after decreasing the anode loading (87.49 µg cm-2) or the total PGM loading (0.111 mg cm-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.

Revealing Local Grain Boundary Chemistry and Correlating it with Local Mass Transport in Mixed-Conducting Perovskite Electrodes.

Grain boundary (GB) mass transport, and chemistry exert a pronounced influence on both the performance and stability of electrodes for solid oxide electrochemical cells. Lanthanum strontium cobalt ferrite (LSCF6428) is applied as a model mixed ionic and electronic conducting (MIEC) perovskite oxide. The cation-vacancy distribution at the GBs is studied at both single and multi-grain scales using high-resolution characterization techniques and computational approaches. The accumulation of oxygen vacancies ( V O · · $V_O^{ \cdot \cdot }$ ) in the GB region, rather than necessarily at the GB core, results in an enhancement of the oxygen diffusivity by 3 - 4 orders of magnitude along the GBs (Dgb). At 350 °C, the oxygen tracer diffusion coefficient (D*) is measured as 2.5 × 10-14 cm2 s-1. The Dgb is determined to be 2.8 × 10-10 cm2 s-1 assuming a crystallographic GB width (δcrystal) of 1 nm, and 2.5 × 10-11 cm2 s-1 using a chemically measured δchem of 11.10 nm by atom probe tomography (APT). The origin of the concomitant changes in the cation composition is also investigate. In addition to the host cations, strong Na segregation is detected at all the GBs examined. Despite the low (ppm) level of this impurity, its presence can affect the space charge potential (Φ0). This, in turn, will influence the evolution of GB chemistry.

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

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