A High-capacity Benzoquinone Derivative Anode for All-organic Long-cycle Aqueous Proton Batteries.

Quinone compounds, with the ability to uptake protons, are promising electrodes for aqueous batteries. However, their application is limited by the mediocre working potential range and inferior rate performance. Herein, we examined quinones bearing different substituents, and for the first time introduce tetraamino-1,4-benzoquinone (TABQ) as anode material for proton batteries. The strong electron-donating amino groups can effectively narrow the band gap and negatively shift the redox potentials of quinone material. The protonation of amino groups and the amorphization of structure result in the formation of an intermolecular hydrogen-bond network, supporting Grotthuss-type proton conduction in the electrode with a low activation energy of 192.7 meV. The energy storage mechanism revealed by operando FT-IR and ex-situ XPS features a reversible quinone-hydroquinone conversion during cycling. TABQ demonstrates a remarkable specific capacity of 307 mAh g-1 at 1 A g-1, which is the highest among organic proton electrodes. An all-organic proton battery of TABQ//TCBQ has also been developed, achieving exceptional stability of 3500 cycles at room temperature and excellent performance at sub-zero temperatures.

Low-Electronegativity Mn-Contraction of PtMn Nanodendrites Boosts Oxygen Reduction Durability.

Platinum metal (PtM, M=Ni, Fe, Co) alloys catalysts show high oxygen reduction reaction (ORR) activity due to their well-known strain and ligand effects. However, these PtM alloys usually suffer from a deficient ORR durability in acidic environment as the alloyed metal is prone to be dissolved due to its high electronegativity. Herein, we report a new class of PtMn alloy nanodendrite catalyst with low-electronegativity Mn-contraction for boosting the oxygen reduction durability of fuel cells. The moderate strain in PtMn, induced by Mn contraction, yields optimal oxygen reduction activity at 0.53 A mg-1 at 0.9 V versus reversible hydrogen electrode (RHE). Most importantly, we show that relative to well-known high-electronegativity Ni-based Pt alloy counterpart, the PtMn nanodendrite catalyst experiences less transition metals' dissolution in acidic solution and achieves an outstanding mass activity retention of 96 % after 10,000 degradation cycles. Density functional theory calculation reveals that PtMn alloys are thermodynamically more stable than PtNi alloys in terms of formation enthalpy and cohesive energy. The PtMn nanodendrite-based membrane electrode assembly delivers an outstanding peak power density of 1.36 W cm-2 at a low Pt loading and high-performance retention over 50 h operations at 0.6 V in H2 -O2 hydrogen fuel cells.

Efficient Oxygen Evolution and Gas Bubble Release Achieved by a Low Gas Bubble Adhesive Iron-Nickel Vanadate Electrocatalyst.

Surface chemistry is a pivotal prerequisite besides catalyst composition toward advanced water electrolysis. Here, an evident enhancement of the oxygen evolution reaction (OER) is demonstrated on a vanadate-modified iron-nickel catalyst synthesized by a successive ionic layer adsorption and reaction method, which demonstrates ultralow overpotentials of 274 and 310 mV for delivering large current densities of 100 and 400 mA cm-2 , respectively, in 1 m KOH, where vigorous gas bubble evolution occurs. Vanadate modification augments the OER activity by i) increasing the electrochemical surface area and intrinsic activity of the active sites, ii) having an electronic interplay with Fe and Ni catalytic centers, and iii) inducing a high surface wettability and a low-gas bubble-adhesion for accelerated mass transport and gas bubble dissipation at large current densities. Ex situ and operando Raman study reveals the structural evolution of ß-NiOOH and γ-FeOOH phases during the OER through vanadate-active site synergistic interactions. Operando dynamic specific resistance measurement evidences an accelerated gas bubble dissipation by a significant decrease in the variation of the interfacial resistance during the OER for the vanadate-modified surface. Achievement of a high catalytic turnover of 0.12 s-1 suggests metallic oxo-anion modification as a versatile catalyst design strategy for advanced water oxidation.

Monometallic interphasic synergy via nano-hetero-interfacing for hydrogen evolution in alkaline electrolytes.

Electrocatalytic synergy is a functional yet underrated concept in electrocatalysis. Often, it materializes as intermetallic interaction between different metals. We demonstrate interphasic synergy in monometallic structures is as much effective. An interphasic synergy between Ni(OH)2 and Ni-N/Ni-C phases is reported for alkaline hydrogen evolution reaction that lowers the energy barriers for hydrogen adsorption-desorption and facilitates that of hydroxyl intermediates. This makes ready-to-serve Ni active sites and allocates a large amount of Ni d-states at Fermi level to promote charge redistribution from Ni(OH)2 to Ni-N/Ni-C and the co-adsorption of Hads and OHads intermediates on Ni-N/Ni-C moieties. As a result, a Ni(OH)2@Ni-N/Ni-C hetero-hierarchical nanostructure is developed, lowering the overpotentials to deliver -10 and -100 mA cm-2 in alkaline media by 102 and 113 mV, respectively, compared to monophasic Ni(OH)2 catalyst. This study unveils the interphasic synergy as an effective strategy to design monometallic electrocatalysts for water splitting and other energy applications.

Towards the Reduction of Pt Loading in High Temperature Proton Exchange Membrane Fuel Cells - Effect of Fe-N-C in Pt-Alloy Cathodes.

Pt poisoning by phosphate in high temperature proton exchange membrane fuel cells (HT-PEMFC) leads to loadings up to 1 mgPt cm-2 per electrode of costly materials. While cheaper Fe-N-C catalysts are unaffected by phosphate deactivation and contribute to the catalysis of the oxygen reduction reaction, their volumetric activity is substantially lower. In this study, the effect of Pt-loading reduced hybrid cathodes for HT-PEMFC is investigated using commercial Celtec®-P-based assembling. A promising effect of Fe-N-C incorporation in terms of acid attraction and activity retention is found. A longer activation (230 h, 0.3 A cm-2 ) for the hybrid membrane electrode assembly (MEA) is necessary, due to the slower acid distribution within Fe-N-Cs. This study shows the potential of Pt-content reduction by up to 25 % compared to standard MEA using hybrid electrodes. Moreover, important insights for future strategies of cell activation are revealed for these hybrid MEAs.

Large-scale physically accurate modelling of real proton exchange membrane fuel cell with deep learning.

Proton exchange membrane fuel cells, consuming hydrogen and oxygen to generate clean electricity and water, suffer acute liquid water challenges. Accurate liquid water modelling is inherently challenging due to the multi-phase, multi-component, reactive dynamics within multi-scale, multi-layered porous media. In addition, currently inadequate imaging and modelling capabilities are limiting simulations to small areas (<1 mm2) or simplified architectures. Herein, an advancement in water modelling is achieved using X-ray micro-computed tomography, deep learned super-resolution, multi-label segmentation, and direct multi-phase simulation. The resulting image is the most resolved domain (16 mm2 with 700 nm voxel resolution) and the largest direct multi-phase flow simulation of a fuel cell. This generalisable approach unveils multi-scale water clustering and transport mechanisms over large dry and flooded areas in the gas diffusion layer and flow fields, paving the way for next generation proton exchange membrane fuel cells with optimised structures and wettabilities.

Fe-N-C/Fe nanoparticle composite catalysts for the oxygen reduction reaction in proton exchange membrane fuel cells.

Replacing Pt-based catalysts with cost-effective, highly efficient, and durable platinum group metal-free catalysts for the oxygen reduction reaction (ORR) is crucial for commercializing hydrogen fuel cells. Herein, we present a highly active Fe-N-C electrocatalyst that contains both Fe nanoparticles and FeNx active sites derived from an Fe-doped carbonized zeolitic imidazolate framework (ZIF-8). It is found that adjusting the doping amount of Fe in the Fe-doped ZIF-8 precursor alters the morphology of the catalyst after heat treatment. The Fe-N-C-300 composite catalyst with the optimized Fe doping amount exhibits excellent activity, good stability, and remarkable methanol tolerance in the challenging acid environment. This study reveals that a suitable amount of Fe nanoparticles in the catalyst can alter the structure of the FeNx active moieties and increase three-phase boundaries to boost the mass transport, thus leading to improved fuel cell performance. This will have implications for using Fe-N-C catalysts in real applications, as the formation of Fe NPs during the synthesis and reaction is almost inevitable.

In Situ and Operando Characterization of Proton Exchange Membrane Fuel Cells.

For proton exchange membrane fuel cells (PEMFCs) to become a mainstream energy source, significant improvements in their performance, durability, and efficiency are necessary. To improve their durability, there must be a solid understanding of how the structural and electrochemical processes are affected during operation to propose mitigation strategies. To this aim, in situ and operando characterization techniques can locally identify structural and electrochemical processes, which cannot be captured using conventional techniques. Linking these properties in the same geometric area has been challenging due to its inherent limitations, such as sample size and imaging resolution. This has created a knowledge gap in structure-to-electrochemical performance relationships as operation and degradation unevenly affect different areas of the cell. In the recent past, catalyst layer degradation, hot spots, and water management have been structurally and electrochemically visualized in the same geometric area, revealing new interactions. To further the research in this direction, these interconnected fields are reviewed, followed by a roadmap for in situ characterization of PEMFCs, treating structural and electrochemical processes as a unified subject. With this approach, the knowledge of the degradation of PEMFCs will be significantly improved.