This article provides an up-to-date perspective on the use of anion-exchange membranes in fuel cells, electrolysers, redox flow batteries, reverse electrodialysis cells, and bioelectrochemical systems (e.g. microbial fuel cells). The aim is to highlight key concepts, misconceptions, the current state-of-the-art, technological and scientific limitations, and the future challenges (research priorities) related to the use of anion-exchange membranes in these energy technologies. All the references that the authors deemed relevant, and were available on the web by the manuscript submission date (30th April 2014), are included.

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Anion-exchange membranes in electrochemical energy systems

Covalent organic frameworks (COFs) are a class of crystalline porous organic polymers with permanent porosity and highly ordered structures. Unlike other polymers, a significant feature of COFs is that they are structurally predesignable, synthetically controllable, and functionally manageable. In principle, the topological design diagram offers geometric guidance for the structural tiling of extended porous polygons, and the polycondensation reactions provide synthetic ways to construct the predesigned primary and high-order structures. Progress over the past decade in the chemistry of these two aspects undoubtedly established the base of the COF field. By virtue of the availability of organic units and the diversity of topologies and linkages, COFs have emerged as a new field of organic materials that offer a powerful molecular platform for complex structural design and tailor-made functional development. Here we target a comprehensive review of the COF field, provide a historic overview of the chemistry of the COF field, survey the advances in the topology design and synthetic reactions, illustrate the structural features and diversities, scrutinize the development and potential of various functions through elucidating structure-function correlations based on interactions with photons, electrons, holes, spins, ions, and molecules, discuss the key fundamental and challenging issues that need to be addressed, and predict the future directions from chemistry, physics, and materials perspectives.

Covalent Organic Frameworks: Design, Synthesis, and Functions.

Flexible solid-state supercapacitors (FSSCs) are frontrunners in energy storage device technology and have attracted extensive attention owing to recent significant breakthroughs in modern wearable electronics In this study, we review the state-of-the-art advancements in FSSCs to provide new insights on mechanisms, emerging electrode materials, flexible gel electrolytes and novel cell designs The review begins with a brief introduction on the fundamental understanding of charge storage mechanisms based on the structural properties of electrode materials The next sections briefly summarise the latest progress in flexible electrodes (ie, freestanding and substrate-supported, including textile, paper, metal foil/wire and polymer-based substrates) and flexible gel electrolytes (ie, aqueous, organic, ionic liquids and redox-active gels) Subsequently, a comprehensive summary of FSSC cell designs introduces some emerging electrode materials, including MXenes, metal nitrides, metal–organic frameworks (MOFs), polyoxometalates (POMs) and black phosphorus Some potential practical applications, such as the development of piezoelectric, photo-, shape-memory, self-healing, electrochromic and integrated sensor-supercapacitors are also discussed The final section highlights current challenges and future perspectives on research in this thriving field

Towards flexible solid-state supercapacitors for smart and wearable electronics

In the past few decades, there has been a wide research interest in titanium dioxide (TiO2) nanomaterials due to their applications in photocatalytic hydrogen generation and environmental pollution removal. Improving the optical absorption properties of TiO2 nanomaterials has been successfully demonstrated to enhance their photocatalytic activities, especially in the report of black TiO2 nanoparticles. The recent progress in the investigation of black TiO2 nanomaterials has been reviewed here, and special emphasis has been given on their fabrication methods along with their various chemical/physical properties and applications.

Black titanium dioxide (TiO2) nanomaterials

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Studies in Surface Science and Catalysis

One promising approach to reduce the cost of fuel cell systems is to develop hydroxide exchange membrane fuel cells (HEMFCs), which open up the possibility of platinum-group-metal-free catalysts and low-cost bipolar plates. However, scalable alkaline polyelectrolytes (hydroxide exchange membranes and hydroxide exchange ionomers), a key component of HEMFCs, with desired properties are currently unavailable, which presents a major barrier to the development of HEMFCs. Here we show hydroxide exchange membranes and hydroxide exchange ionomers based on poly(aryl piperidinium) (PAP) that simultaneously possess adequate ionic conductivity, chemical stability, mechanical robustness, gas separation and selective solubility. These properties originate from the combination of the piperidinium cation and the rigid ether-bond-free aryl backbone. A low-Pt membrane electrode assembly with a Ag-based cathode using PAP materials showed an excellent peak power density of 920 mW cm−2 and operated stably at a constant current density of 500 mA cm−2 for 300 h with H2/CO2-free air at 95 °C. A key challenge for hydroxide exchange membrane fuel cells is the development of membranes with both high ionic conductivity and mechanical strength. Here the authors report a high-performance family of poly(aryl piperidinium) membranes enabling promising durability and power density.

Poly(aryl piperidinium) membranes and ionomers for hydroxide exchange membrane fuel cells

An Efficient Direct Ammonia Fuel Cell for Affordable Carbon-Neutral Transportation

The rapid growth of intermittent renewable energy (e.g., wind and solar) demands low-cost and large-scale energy storage systems for smooth and reliable power output, where redox-flow batteries (RFBs) could find their niche. In this work, we introduce the first all-soluble all-iron RFB based on iron as the same redox-active element but with different coordination chemistries in alkaline aqueous system. The adoption of the same redox-active element largely alleviates the challenging problem of cross-contamination of metal ions in RFBs that use two redox-active elements. An all-soluble all-iron RFB is constructed by combining an iron–triethanolamine redox pair (i.e., [Fe(TEOA)OH]−/[Fe(TEOA)(OH)]2–) and an iron–cyanide redox pair (i.e., Fe(CN)63–/Fe(CN)64–), creating 1.34 V of formal cell voltage. Good performance and stability have been demonstrated, after addressing some challenges, including the crossover of the ligand agent. As exemplified by the all-soluble all-iron flow battery, combining redox pairs o...

All-Soluble All-Iron Aqueous Redox-Flow Battery

Hydrogen is an ideal alternative energy carrier to generate power for all of society's energy demands including grid, industrial, and transportation sectors. Among the hydrogen production methods, water electrolysis is a promising method because of its zero greenhouse gas emission and its compatibility with all types of electricity sources. Alkaline electrolyzers (AELs) and proton exchange membrane electrolyzers (PEMELs) are currently used to produce hydrogen. AELs are commercially mature and are used in a variety of industrial applications, while PEMELs are still being developed and find limited application. In comparison with AELs, PEMELs have more compact structure and can achieve higher current densities. Recently, however, an alternative technology to PEMELs, hydroxide exchange membrane electrolyzers (HEMELs), has gained considerable attention due to the possibility to use platinum group metal (PGM)-free electrocatalysts and cheaper membranes, ionomers, and construction materials and its potential to achieve performance parity with PEMELs. Here, the state-of-the-art AELs and PEMELs along with the current status of HEMELs are discussed in terms of their positive and negative aspects. Additionally discussed are electrocatalyst, membrane, and ionomer development needs for HEMELs and benchmark electrocatalysts in terms of the cost-performance tradeoff.

Yun Zhao

Papers

Poly(aryl piperidinium) membranes and ionomers for hydroxide exchange membrane fuel cells

An Efficient Direct Ammonia Fuel Cell for Affordable Carbon-Neutral Transportation

All-Soluble All-Iron Aqueous Redox-Flow Battery

A Roadmap to Low-Cost Hydrogen with Hydroxide Exchange Membrane Electrolyzers.

Crosslinked poly(vinylbenzyl chloride) with a macromolecular crosslinker for anion exchange membrane fuel cells