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Crystalline two-dimensional carbon nitrides with polytriazine imide (PTI) structure are shown to act amphoterically, buffering both HCl and NaOH aqueous solutions, resulting in charged PTI layers that dissolve spontaneously in their aqueous media, particularly for the alkaline solutions. This provides a low energy, green route to their scalable solution processing. Protonation in acid is shown to occur at pyridinic nitrogens, stabilized by adjacent triazines, whereas deprotonation in base occurs primarily at basal plane NH bridges, although NH2 edge deprotonation is competitive. We conclude that mildly acidic or basic pHs are necessary to provide sufficient net charge on the nanosheets to promote dissolution, while avoiding high ion concentrations which screen the repulsion of like-charged PTI sheets in solution. This article is part of the theme issue 'Exploring the length scales, timescales and chemistry of challenging materials (Part 2)'. [ABSTRACT FROM AUTHOR]

The crystalline graphitic carbon nitride, poly-triazine imide (PTI) is highly unusual among layered materials since it is spontaneously soluble in aprotic, polar solvents including dimethylformamide (DMF). The PTI material consists of layers of carbon nitride intercalated with LiBr. When dissolved, the resulting solutions consist of dissolved, luminescent single to multilayer nanosheets of around 60–125 nm in diameter and Li+ and Br− ions originating from the intercalating salt. To understand this unique solubility, the structure of these solutions has been investigated by high-energy X-ray and neutron diffraction. Although the diffraction patterns are dominated by inter-solvent correlations there are clear differences between the X-ray diffraction data of the PTI solution and the solvent in the 4–6 Å−1 range, with real space differences persisting to at least 10 Å. Structural modelling using both neutron and X-ray datasets as a constraint reveal the formation of distinct, dense solvation shells surrounding the nanoparticles with a layer of Br−close to the PTI-solvent interface. This solvent ordering provides a configuration that is energetically favourable underpinning thermodynamically driven PTI dissolution. This article is part of the theme issue 'Exploring the length scales, timescales and chemistry of challenging materials (Part 2)'. [ABSTRACT FROM AUTHOR]

Although proton exchange membranes (PEMs) are widely deployed in an array of commercial applications, limitations linked to their proton conductivity, water retention, and gas permeability still limit ultimate device performance. While ex situ studies have shown additives can enhance membrane stability and mass transport, to date few have demonstrated that these performance enhancements are maintained when tested in commercially relevant electrochemical technologies, such as fuel cells or electrolyzers. Herein, a new multifunctional additive, 2D poly(triazine imide) (PTI), is demonstrated for composite PEMs, which is shown to boost proton conductivity by 37% under optimal high relative humidity (RH) conditions and 67% at low RHs. PTI also enables major improvements (over 55%) in both current and power densities in industrially relevant PEM fuel cells (PEMFCs). Most importantly, in situ and ex situ characterization suggests that the enhanced performance is due to polymer aggregate‐PTI clusters that form with increasing 2D character and improved long‐range connectivity, while acid‐base interactions with pyridinic nitrogen facilitate the critical proton hopping mechanism at all RHs. Hence, this work offers both a new membrane concept with proven benefits for important electrochemical technologies, as well as design principles for future optimization of proton transport and water management within PEMs. [ABSTRACT FROM AUTHOR]

Developing high-performing and scalable electrode materials for supercapacitors and batteries has been of tremendous interest for the world's forthcoming clean and renewable energy transition. As a versatile material, Two-dimensional graphitic carbon nitride (g-CN) has been utilized in electrochemical energy storage (EES) applications due to its nitrogen-rich adsorption sites, cost-effective production, and tunable electronic structure. The electrochemical performance of pristine g-CN has been boosted by forming hybrid architectures with highly conductive carbon-based materials, such as graphene, reduced graphene oxide, carbon nanofibers, carbon nanotubes, and beyond (e.g., MXene). Using such heterogeneous compositions for EES applications has significantly increased in recent years. This study reviews the g-CN/carbon nanomaterial (CNM) hybrids, considering the dimensionality in nanomaterials, and underscores the influence of the material's dimensionality and the synthesis/fabrication routes. The effect of structural and physicochemical changes on the electrode's electrochemical performance after hybridization is presented comparatively. Besides, the comprehensive review outlines challenges and future improvements in g-CN/CNM hybrid materials for outstanding developments in energy storage systems. [Display omitted] • Graphitic carbon nitride (g-CN)/carbon nanomaterial (CNM) hybrids are reviewed for supercapacitor and battery applications. • The impact of the CNM-type on the hybrid electrode's performance is examined through a chemical and physical perspective. • An overview of how hybrid electrode synthesis affects ion/electron transport, surface area, and porosity is provided. • Design-oriented control of the physicochemical properties for enhanced electrochemical performance is exemplified. • g-CN/CNM nanoarchitectures are emphasized as electrode materials with the potential for easy scalability. [ABSTRACT FROM AUTHOR]

• Operando synchrotron X-ray study on Phosphorus and Platinum migration. • Graphene-related-material applied as interventional materials for comparison. • X-ray Absorption Near Edge Structure applied to study chemical structural change. • Conducting mechanistic studies via the three-phase interface. • Performance and durability of high-temperature proton exchange membrane fuel cells. The application of high-temperature proton exchange membrane fuel cells (HT-PEMFCs) addresses challenges in water management, fuel purity, and overheating under high current density. However, phosphoric acid (PA) migration hinders their development. This study uses synchrotron-based X-ray fluorescence spectroscopy to investigate PA and catalyst migration. Interventions with single-layer graphene and electrochemically exfoliated graphene oxide improve performance and durability. X-ray absorption spectroscopy provides insights into relevant mechanisms, advancing understanding of membrane electrode assembly preparation and the intricate influences of PA and catalyst migration on performance and durability in HT-PEMFCs. [ABSTRACT FROM AUTHOR]

Poly(ethylene oxide) (PEO) is a promising solid electrolyte material for solid‐state lithium–sulfur (Li–S) batteries, but low intrinsic ionic conductivity, poor mechanical properties, and failure to hinder the polysulfide shuttle effect limits its application. Herein, a polymer of intrinsic microporosity (PIM) is synthesized and applied as an organic framework to comprehensively enhance the performance of PEO by forming a composite electrolyte (PEO‐PIM). The unique structure of PIM‐1 not only enhances the mechanical strength and hardness over the PEO electrolyte by an order of magnitude, increasing stability toward the metallic lithium anode but also increases its ionic conductivity by lowering the degree of crystallinity. Furthermore, the PIM‐1 is shown to effectively trap lithium polysulfide species to mitigate against the detrimental polysulfide shuttle effect, as electrophilic 1,4‐dicyanooxanthrene functional groups possess higher binding energy to polysulfides. Benefiting from these properties, the use of PEO‐PIM composite electrolyte has achieved greatly improved rate performance, long‐cycling stability, and excellent safety features for solid‐state Li‐S batteries. This methodology offers a new direction for the optimization of solid polymer electrolytes. [ABSTRACT FROM AUTHOR]

Atomically dispersed transition metal‐nitrogen‐carbon catalysts are emerging as low‐cost electrocatalysts for the oxygen reduction reaction in fuel cells. However, a cost‐effective and scalable synthesis strategy for these catalysts is still required, as well as a greater understanding of their mechanisms. Herein, iron, nitrogen co‐doped carbon spheres (Fe@NCS) have been prepared via hydrothermal carbonization and high‐temperature post carbonization. It is determined that FeN4 is the main form of iron existing in the obtained Fe@NCS. Two different precursors containing Fe2+ and Fe3+ are compared. Both chemical and structural differences have been observed in catalysts starting from Fe2+ and Fe3+ precursors. Fe2+@NCS‐A (starting with Fe2+ precursor) shows better catalytic activity for the oxygen reduction reaction. This catalyst is studied in an anion exchange membrane fuel cell. The high open‐circuit voltage demonstrates the potential approach for developing high‐performance, low‐cost fuel cell catalysts. [ABSTRACT FROM AUTHOR]

Although lithium, and other alkali ion, batteries are widely utilized and studied, many of the chemical and mechanical processes that underpin the materials within, and drive their degradation/failure, are not fully understood. Hence, to enhance the understanding of these processes various ex situ, in situ and operando characterization methods are being explored. Recently, electrochemical atomic force microscopy (EC‐AFM), and related techniques, have emerged as crucial platforms for the versatile characterization of battery material surfaces. They have revealed insights into the morphological, mechanical, chemical, and physical properties of battery materials when they evolve under electrochemical control. This critical review will appraise the progress made in the understanding batteries using EC‐AFM, covering both traditional and new electrode–electrolyte material junctions. This progress will be juxtaposed against the ability, or inability, of the system adopted to embody a truly representative battery environment. By contrasting key EC‐AFM literature with conclusions drawn from alternative characterization tools, the unique power of EC‐AFM to elucidate processes at battery interfaces is highlighted. Simultaneously opportunities for complementing EC‐AFM data with a range of spectroscopic, microscopic, and diffraction techniques to overcome its limitations are described, thus facilitating improved battery performance. [ABSTRACT FROM AUTHOR]

Polymer electrolyte fuel cells (PEFCs) are a promising replacement for the fossil fuel–dependent automotive and energy sectors. They have become increasingly commercialized in the last decade; however, significant limitations on durability and performance limit their commercial uptake. Catalyst layer (CL) design is commonly reported to impact device power density and durability; although, a consensus is rarely reached due to differences in testing conditions, experimental design, and types of data reported. This is further exacerbated by aspects of CL design such as catalyst support, proton conduction, catalyst, fabrication, and morphology, being significantly interdependent; hence, a wider appreciation is required in order to optimize performance, improve durability, and reduce costs. Here, the cutting‐edge research within the field of PEFCs is reviewed, investigating the effect of different manufacturing techniques, electrolyte distribution, support materials, surface chemistries, and total porosity on power density and durability. These are critically appraised from an applied perspective to inform the most relevant and promising pathways to make and test commercially viable cells. This holistic view of the competing aspects of CL design and preparation will facilitate the development of optimized CLs, especially the incorporation of novel catalyst support materials. [ABSTRACT FROM AUTHOR]