Aryl ether-free polymer electrolytes for electrochemical and energy devices.

Anion exchange polymers (AEPs) play a crucial role in green hydrogen production through anion exchange membrane water electrolysis. The chemical stability of AEPs is paramount for stable system operation in electrolysers and other electrochemical devices. Given the instability of aryl ether-containing AEPs under high pH conditions, recent research has focused on quaternized aryl ether-free variants.

Alkaline Stability of Anion-Exchange Membranes.

Recently, the development of durable anion-exchange membrane fuel cells (AEMFCs) has increased in intensity due to their potential to use low-cost, sustainable components. However, the decomposition of the quaternary ammonium (QA) cationic groups in the anion-exchange membranes (AEMs) during cell operation is still a major challenge. Many different QA types and functionalized polymers have been proposed that achieve high AEM stabilities in strongly alkaline aqueous solutions.

Isoindolinium Groups as Stable Anion Conductors for Anion-Exchange Membrane Fuel Cells and Electrolyzers.

Anion-exchange membrane (AEM) fuel cells (AEMFCs) and water electrolyzers (AEMWEs) have gained strong attention of the scientific community as an alternative to expensive mainstream fuel cell and electrolysis technologies. However, in the high pH environment of the AEMFCs and AEMWEs, especially at low hydration levels, the molecular structure of most anion-conducting polymers breaks down because of the strong reactivity of the hydroxide anions with the quaternary ammonium (QA) cation functional groups that are commonly used in the AEMs and ionomers. Therefore, new highly stable QAs are needed to withstand the strong alkaline environment of these electrochemical devices.

Influence of Headgroups in Ethylene-Tetrafluoroethylene-Based Radiation-Grafted Anion Exchange Membranes for CO Electrolysis.

The performance of zero-gap CO electrolysis (COE) is significantly influenced by the membrane's chemical structure and physical properties due to its effects on the local reaction environment and water/ion transport. Radiation-grafted anion-exchange membranes (RG-AEM) have demonstrated high ionic conductivity and durability, making them a promising alternative for COE. These membranes were fabricated using two different thicknesses of ethylene-tetrafluoroethylene polymer substrates (25 and 50 μm) and three different headgroup chemistries: benzyl-trimethylammonium, benzyl--methylpyrrolidinium, and benzyl--methylpiperidinium (MPIP).

Disentangling water, ion and polymer dynamics in an anion exchange membrane.

Semipermeable polymeric anion exchange membranes are essential for separation, filtration and energy conversion technologies including reverse electrodialysis systems that produce energy from salinity gradients, fuel cells to generate electrical power from the electrochemical reaction between hydrogen and oxygen, and water electrolyser systems that provide H fuel. Anion exchange membrane fuel cells and anion exchange membrane water electrolysers rely on the membrane to transport OH ions between the cathode and anode in a process that involves cooperative interactions with HO molecules and polymer dynamics. Understanding and controlling the interactions between the relaxation and diffusional processes pose a main scientific and critical membrane design challenge.

3D-Zipped Interface: In Situ Covalent-Locking for High Performance of Anion Exchange Membrane Fuel Cells.

Polymer electrolyte membrane fuel cells can generate high power using a potentially green fuel (H ) and zero emissions of greenhouse gas (CO ). However, significant mass transport resistances in the interface region of the membrane electrode assemblies (MEAs), between the membrane and the catalyst layers remains a barrier to achieving MEAs with high power densities and long-term stabilities. Here, a 3D-interfacial zipping concept is presented to overcome this challenge.

Reshaping the Cathodic Catalyst Layer for Anion Exchange Membrane Fuel Cells: From Heterogeneous Catalysis to Homogeneous Catalysis.

In anion exchange membrane fuel cells, catalytic reactions occur at a well-defined three-phase interface, wherein conventional heterogeneous catalyst layer structures exacerbate problems, such as low catalyst utilization and limited mass transfer. We developed a structural engineering strategy to immobilize a molecular catalyst tetrakis(4-methoxyphenyl)porphyrin cobalt(II) (TMPPCo) on the side chains of an ionomer (polyfluorene, PF) to obtain a composite material (PF-TMPPCo), thereby achieving a homogeneous catalysis environment inside ion-flow channels, with greatly improved mass transfer and turnover frequency as a result of 100 % utilization of the catalyst molecules. The unique structure of the homogeneous catalysis system comprising interconnected nanoreactors exhibits advantages of low overpotential and high fuel-cell power density.

The alkali degradation of LDPE-based radiation-grafted anion-exchange membranes studied using different e methods.

Radiation-grafted anion-exchange membranes (RG-AEM) in alkaline membrane fuel cells (AEMFC) exhibit promising performances (low resistances, high power outputs and reasonably high alkali stabilities). Much research is focused on developing AEMs with enhanced chemical stabilities in the OH-forms at temperatures >60 °C. This study contributes towards this effort by providing a comparison of three different methods of screening alkali stabilities (where different laboratories conducted experiments on exactly the same batches of RG-AEM).

Practical Technique To Measure the Chemical Stability of Anion-Exchange Membranes under Conditions Simulating the Fuel Cell Environment.

Anion-exchange membrane (AEM) degradation during fuel cell operation represents the main challenge that hampers the implementation of AEM fuel cells (AEMFCs). Reported degradation values of AEMs are difficult to reproduce as no standard methods are used. The present use of different techniques based on exposure of membranes to aqueous KOH solutions under different conditions and measuring different outputs during time does not allow for a reliable and meaningful comparison of reported degradation data of different AEMs.

Using operando techniques to understand and design high performance and stable alkaline membrane fuel cells.

There is a need to understand the water dynamics of alkaline membrane fuel cells under various operating conditions to create electrodes that enable high performance and stable, long-term operation. Here we show, via operando neutron imaging and operando micro X-ray computed tomography, visualizations of the spatial and temporal distribution of liquid water in operating cells. We provide direct evidence for liquid water accumulation at the anode, which causes severe ionomer swelling and performance loss, as well as cell dryout from undesirably low water content in the cathode.

Textile-based non-invasive lithium drug monitoring: A proof-of-concept study for wearable sensing.

Flexible wearable chemical sensors are emerging tools which target diagnosis and monitoring of medical conditions. One of the potential applications of wearable chemical sensors is therapeutic drug monitoring for drugs that have a narrow therapeutic range such as lithium. We have investigated the possibility of developing a fibre-based device for non-invasive lithium drug monitoring in interstitial fluid.

Electron Communication of Bacillus subtilis in Harsh Environments.

Elucidating the effect of harsh environments on the activities of microorganisms is important in revealing how microbes withstand unfavorable conditions or evolve mechanisms to counteract those effects, many of which involve electron transfer phenomena. Here we show that the non-acidophilic and non-thermophilic Bacillus subtilis is able to maintain activity after being subjected to extreme temperatures (100°C for up to 8 h) and acidic environments (pH = 1.50 for over 2 years).

Nitrogen-doped Carbon-CoO Nanohybrids: A Precious Metal Free Cathode that Exceeds 1.0 W cm 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 embedded in nitrogen-doped graphitic carbon (N-C-CoO ) was created through the direct pyrolysis of a metal-organic complex with a NaCl template. The N-C-CoO catalyst showed high ORR activity, indicated by excellent half-wave (0.

Fabrication and Optimization of Fiber-Based Lithium Sensor: A Step toward Wearable Sensors for Lithium Drug Monitoring in Interstitial Fluid.

A miniaturized, flexible fiber-based lithium sensor was fabricated from low-cost cotton using a simple, repeatable dip-coating technique. This lithium sensor is highly suited for ready-to-use wearable applications and can be used directly without the preconditioning steps normally required with traditional ion-selective electrodes. The sensor has a stable, rapid, and accurate response over a wide Li concentration range that spans over the clinically effective and the toxic concentration limits for lithium in human serum.

The first anion-exchange membrane fuel cell to exceed 1 W cm at 70 °C with a non-Pt-group (O) cathode.

Anion-exchange membrane fuel cells face two challenges: performance and durability. Addressing the first, we demonstrate high performance with both O and CO-free air supplies, even when using a Ag/C cathode. This was enabled by the development of a radiation-grafted anion-exchange membrane that was less than 30 μm thick when hydrated.

Effect of cationic molecules on the oxygen reduction reaction on fuel cell grade Pt/C (20 wt%) catalyst in potassium hydroxide (aq, 1 mol dm(-3)).

This study investigates the effect of 1 mmol dm(-3) concentrations of a selection of small cationic molecules on the performance of a fuel cell grade oxygen reduction reaction (ORR) catalyst (Johnson Matthey HiSPEC 3000, 20 mass% Pt/C) in aqueous KOH (1 mol dm(-3)). The cationic molecules studied include quaternary ammonium (including those based on bicyclic systems) and imidazolium types as well as a phosphonium example: these serve as fully solubilised models for the commonly encountered head-groups in alkaline anion-exchange membranes (AAEM) and anion-exchange ionomers (AEI) that are being developed for application in alkaline polymer electrolyte fuel cells (APEFCs), batteries and electrolysers. Both cyclic and hydrodynamic linear sweep rotating disk electrode voltammetry techniques were used.

Interplay between water uptake, ion interactions, and conductivity in an e-beam grafted poly(ethylene-co-tetrafluoroethylene) anion exchange membrane.

We demonstrate that the true hydroxide conductivity in an e-beam grafted poly(ethylene-co-tetrafluoroethylene) [ETFE] anion exchange membrane (AEM) is as high as 132 mS cm(-1) at 80 °C and 95% RH, comparable to a proton exchange membrane, but with very much less water present in the film. To understand this behaviour we studied ion transport of hydroxide, carbonate, bicarbonate and chloride, as well as water uptake and distribution. Water uptake of the AEM in water vapor is an order of magnitude lower than when submerged in liquid water.

Impact of 1 mmol dm(-3) concentrations of small molecules containing nitrogen-based cationic groups on the oxygen reduction reaction on polycrystalline platinum in aqueous KOH (1 mol dm(-3)).

Alkaline anion-exchange membranes (AAEMs) containing cationic head-groups (e.g. involving quaternary ammonium and imidazolium groups) are of interest with regard to application in alkaline polymer electrolyte fuel cells (APEFCs).

An optimised glucose oxidase bioelectrode exhibiting high performance direct electron transfer.

A glucose oxidase (GOd) bioelectrode exhibiting high performance, direct electron transfer (DET) has been prepared. Unprecedented redox peak current densities of 1 mA cm(-2) were observed alongside a clear electrochemical response to glucose. This system shows potential as a low cost, high performance enzymatic bioelectrode.

Dynamic changes in the microbial community composition in microbial fuel cells fed with sucrose.

The performance and dynamics of the bacterial communities in the biofilm and suspended culture in the anode chamber of sucrose-fed microbial fuel cells (MFCs) were studied by using denaturing gradient gel electrophoresis (DGGE) of PCR-amplified partial 16S rRNA genes followed by species identification by sequencing. The power density of MFCs was correlated to the relative proportions of species obtained from DGGE analysis in order to detect bacterial species or taxonomic classes with important functional role in electricity production. Although replicate MFCs showed similarity in performance, cluster analysis of DGGE profiles revealed differences in the evolution of bacterial communities between replicate MFCs.

Spatiotemporal development of the bacterial community in a tubular longitudinal microbial fuel cell.

The spatiotemporal development of a bacterial community in an exoelectrogenic biofilm was investigated in sucrose-fed longitudinal tubular microbial fuel cell reactors, consisting of two serially connected modules. The proportional changes in the microbial community composition were assessed by polymerase chain reaction-denaturing gradient gel electrophoresis (DGGE) and DNA sequencing in order to relate them to the performance and stability of the bioelectrochemical system. The reproducibility of duplicated reactors, evaluated by cluster analysis and Jaccard's coefficient, shows 80-90% similarity in species composition.

A one-compartment fructose/air biological fuel cell based on direct electron transfer.

The construction and characterization of a one-compartment fructose/air biological fuel cell (BFC) based on direct electron transfer is reported. The BFC employs bilirubin oxidase and d-fructose dehydrogenase adsorbed on a cellulose-multiwall carbon nanotube (MWCNT) matrix, reconstituted with an ionic liquid, as the biocathode and the bioanode for oxygen reduction and fructose oxidation reactions, respectively. The performance of the bioelectrode was investigated by chronoamperometric and cyclic voltammetric techniques in a standard three-electrode cell, and the polarization and long-term stability of the BFC was tested by potentiostatic discharge.

Techniques for the study and development of microbial fuel cells: an electrochemical perspective.

Microbial fuel cells (MFCs) represent a clean and renewable energy resource. To date, power generation in MFCs is severely limited. In order to improve performance, a wide range of techniques have been utilised for a fundamental scientific understanding of the components and processes and also to investigate MFC performance bottlenecks.