Separators and Membranes for Advanced Alkaline Water Electrolysis.

Traditionally, alkaline water electrolysis (AWE) uses diaphragms to separate anode and cathode and is operated with 5-7 M KOH feed solutions. The ban of asbestos diaphragms led to the development of polymeric diaphragms, which are now the state of the art material. A promising alternative is the ion solvating membrane. Recent developments show that high conductivities can also be obtained in 1 M KOH. A third technology is based on anion exchange membranes (AEM); because these systems use 0-1 M KOH feed solutions to balance the trade-off between conductivity and the AEM's lifetime in alkaline environment, it makes sense to treat them separately as AEM WE. However, the lifetime of AEM increased strongly over the last 10 years, and some electrode-related issues like oxidation of the ionomer binder at the anode can be mitigated by using KOH feed solutions. Therefore, AWE and AEM WE may get more similar in the future, and this review focuses on the developments in polymeric diaphragms, ion solvating membranes, and AEM.

Performance degradation and mitigation of high temperature polybenzimidazole-based polymer electrolyte membrane fuel cells.

To meet challenges associated with climate changes due to the continuous increase in global energy demand, implementation of hydrogen and fuel cell technologies, especially the polymer electrolyte membrane type, are recognized as potential solutions. The high temperature polymer electrolyte membrane fuel cell based on acid doped polybenzimidazoles has attracted enormous R&D attention due to the simplified construction and operation of the power system. In order to improve the reliability and lifetime of the technology, studies on material degradation and mitigation are essential. The present work is a comprehensive review of the current knowledge on degradation mechanisms of the fuel cell components including the acid loss, polymer oxidation and catalyst instability due to the metal dissolution and carbon support corrosion. The durability results are updated according to the categories of steady state and dynamic operations. Durability protocols, diagnostic techniques and mitigation strategies are also discussed.

Electrode Separators for the Next-Generation Alkaline Water Electrolyzers.

Multi-gigawatt-scale hydrogen production by water electrolysis is central in the green transition when it comes to storage of energy and forming the basis for sustainable fuels and materials. Alkaline water electrolysis plays a key role in this context, as the scale of implementation is not limited by the availability of scarce and expensive raw materials. Even though it is a mature technology, the new technological context of the renewable energy system demands more from the systems in terms of higher energy efficiency, enhanced rate capability, as well as dynamic, part-load, and differential pressure operation capability. New electrode separators that can support high currents at small ohmic losses, while effectively suppressing gas crossover, are essential to achieving this. This Focus Review compares the three main development paths that are currently being pursued in the field with the aim to identify the advantages and drawbacks of the different approaches in order to illuminate rational ways forward.

Low Pt loading for high-performance fuel cell electrodes enabled by hydrogen-bonding microporous polymer binders.

A key challenge for fuel cells based on phosphoric acid doped polybenzimidazole membranes is the high Pt loading, which is required due to the low electrode performance owing to the poor mass transport and severe Pt poisoning via acid absorption on the Pt surface. Herein, these issues are well addressed by design and synthesis of effective catalyst binders based on polymers of intrinsic microporosity (PIMs) with strong hydrogen-bonding functionalities which improve phosphoric acid binding energy, and thus preferably uphold phosphoric acid in the vicinity of Pt catalyst particles to mitigate the adsorption of phosphoric acid on the Pt surface. With combination of the highly mass transport microporosity, strong hydrogen-bonds and high phosphoric acid binding energy, the tetrazole functionalized PIM binder enables an H2-O2 cell to reach a high Pt-mass specific peak power density of 3.8 W mgPt-1 at 160 °C with a low Pt loading of only 0.15 mgPt cm-2.

Studies on Anion Exchange Membrane and Interface Properties by Electrochemical Impedance Spectroscopy: The Role of pH.

Ion-exchange membranes (IEMs) represent a key component in various electrochemical energy conversion and storage systems. In this study, electrochemical impedance spectroscopy (EIS) was used to investigate the effects of structural changes of anion exchange membranes (AEMs) on the bulk membrane and interface properties as a function of solution pH. The variations in the physico/electrochemical properties, including ion exchange capacity, swelling degree, fixed charge density, zeta potentials as well as membrane and interface resistances of two commercial AEMs and cation exchange membranes (CEMs, as a control) were systematically investigated in different pH environments. Structural changes of the membrane surface were analyzed by Fourier transform infrared and X-ray photoelectron spectroscopy. Most notably, at high pH (pH > 10), the membrane (Rm) and the diffusion boundary layer resistances (Rdbl) increased for the two AEMs, whereas the electrical double layer resistance decreased simultaneously. This increase in Rm and Rdbl was mainly attributed to the deprotonation of the tertiary amino groups (-NR2H+) as a membrane functionality. Our results show that the local pH at the membrane-solution interface plays a crucial role on membrane electrochemical properties in IEM transport processes, particularly for AEMs.

Electroreduction of CO2to ethanol by electrochemically deposited Cu-lignin complexes on Ni foam electrodes.

A low cost, non-toxic and highly selective catalyst based on a Cu-lignin molecular complex is developed for CO2electroreduction to ethanol. Ni foam (NF), Cu-Ni foam (Cu-NF) and Cu-lignin-Ni foam (Cu-lignin-NF) were prepared by a facile and reproducible electrochemical deposition method. The electrochemical CO2reduction activity of Cu-lignin-NF was found to be higher than Cu-NF. A maximum faradaic efficiency of 23.2% with current density of 22.5 mA cm-2was obtained for Cu-lignin-NF at -0.80 V (versus RHE) in 0.1 M Na2SO4towards ethanol production. The enhancement of catalytic performance is attributed to the growth of the number of active sites and the change of oxidation states of Cu and NF due to the presence of lignin.

Insights and Challenges for Applying Bipolar Membranes in Advanced Electrochemical Energy Systems.

Bipolar membranes (BPMs) are gaining interest in energy conversion technologies. These membranes are composed of cation- and anion-exchange layers, with an interfacial layer in between. This gives the freedom to operate in different conditions (pH, concentration, composition) at both sides. Such membranes are used in two operational modes, forward and reverse bias. BPMs have been implemented in various electrochemical applications, like water and CO2 electrolyzers, fuel cells, and flow batteries, while BPMs are historically designed for acid/base production. Therefore, current commercial BPMs are not optimized, as the conditions change per application. Although the ideal BPM has highly conductive layers, high water dissociation kinetics, long lifetime, and low ion crossover, each application has its own priorities to be competitive in its field. We describe the challenges and requirements for future BPMs, and identify existing developments that can be leveraged to develop BPMs toward the scale of practical applications.

Advancement toward Polymer Electrolyte Membrane Fuel Cells at Elevated Temperatures.

Elevation of operational temperatures of polymer electrolyte membrane fuel cells (PEMFCs) has been demonstrated with phosphoric acid-doped polybenzimidazole (PA/PBI) membranes. The technical perspective of the technology is simplified construction and operation with possible integration with, e.g., methanol reformers. Toward this target, significant efforts have been made to develop acid-base polymer membranes, inorganic proton conductors, and organic-inorganic composite materials. This report is devoted to updating the recent progress of the development particularly of acid-doped PBI, phosphate-based solid inorganic proton conductors, and their composite electrolytes. Long-term stability of PBI membranes has been well documented, however, at typical temperatures of 160°C. Inorganic proton-conducting materials, e.g., alkali metal dihydrogen phosphates, heteropolyacids, tetravalent metal pyrophosphates, and phosphosilicates, exhibit significant proton conductivity at temperatures of up to 300°C but have so far found limited applications in the form of thin films. Composite membranes of PBI and phosphates, particularly in situ formed phosphosilicates in the polymer matrix, showed exceptionally stable conductivity at temperatures well above 200°C. Fuel cell tests at up to 260°C are reported operational with good tolerance of up to 16% CO in hydrogen, fast kinetics for direct methanol oxidation, and feasibility of nonprecious metal catalysts. The prospect and future exploration of new proton conductors based on phosphate immobilization and fuel cell technologies at temperatures above 200°C are discussed.

Design of Monovalent Ion Selective Membranes for Reducing the Impacts of Multivalent Ions in Reverse Electrodialysis.

Reverse electrodialysis (RED) represents one of the most promising membrane-based technologies for clean and renewable energy production from mixing water solutions. However, the presence of multivalent ions in natural water drastically reduces system performance, in particular, the open-circuit voltage (OCV) and the output power. This effect is largely described by the "uphill transport" phenomenon, in which multivalent ions are transported against the concentration gradient. In this work, recent advances in the investigation of the impact of multivalent ions on power generation by RED are systematically reviewed along with possible strategies to overcome this challenge. In particular, the use of monovalent ion-selective membranes represents a promising alternative to reduce the negative impact of multivalent ions given the availability of low-cost materials and an easy route of membrane synthesis. A thorough assessment of the materials and methodologies used to prepare monovalent selective ion exchange membranes (both cation and anion exchange membranes) for applications in (reverse) electrodialysis is performed. Moreover, transport mechanisms under conditions of extreme salinity gradient are analyzed and compared for a better understanding of the design criteria. The ultimate goal of the present work is to propose a prospective research direction on the development of new membrane materials for effective implementation of RED under natural feed conditions.

Preparation of super-hydrophilic polyphenylsulfone nanofiber membranes for water treatment.

Electrospun nanofiber membrane-supported thin film composite (TFC) membranes exhibit great potential in water purification. In this work, electrospun polyphenylsulfone (PPSU) nanofiber membranes were prepared and modified by heat and plasma treatments. The resulting membranes were used as support layers for biomimetic TFC-based forward osmosis membranes. Thermal treatment transformed a loose non-woven nanofiber structure into a robust interconnected 3-dimensional PPSU network displaying a 930% increase in elastic modulus, 853% increase in maximum stress, and two-fold increase in breaking strain. Superior hydrophilicity of PPSU nanofiber membranes was achieved by low-pressure plasma treatment, changing the contact angle from 137° to 0°. The fabricated exemplary TFC-based forward osmosis membrane showed an osmotic water flux J w > 14 L m-2 h-1 with a very low reserve salt flux J s (J s/J w = 0.08 g L-1) demonstrating the potential for making high quality membranes for water treatment using PPSU-based support layers for TFC membranes.

Ion-Exchange-Induced Selective Etching for the Synthesis of Amino-Functionalized Hollow Mesoporous Silica for Elevated-High-Temperature Fuel Cells.

As differentiated from conventional synthetic processes, amino-functionalized hollow mesoporous silica (NH2-HMS) has been synthesized using a new and facile strategy of ion-exchange-induced selective etching of amino-functionalized mesoporous silica (NH2-meso-silica) by an alkaline solution. Nuclear magnetic resonance (NMR) spectroscopy and in situ time-resolved small-angle X-ray scattering (SAXS) reveal that ion-exchange-induced selective etching arises from the gradient distribution of OH- in the NH2-meso-silica nanospheres. Moreover, the ion-exchange-induced selective etching mechanism is verified through a successful synthesis of hollow mesoporous silica. After infiltration with phosphotungstic acid (PWA), PWA-NH2-HMS nanoparticles are dispersed in the poly(ether sulfone)-polyvinylpyrrolidone (PES-PVP) matrix, forming a hybrid PWA-NH2-HMS/PES-PVP nanocomposite membrane. The resultant nanocomposite membrane with an optimum loading of 10 wt % of PWA-NH2-HMS showed an enhanced proton conductivity of 0.175 S cm-1 and peak power density of 420 mW cm-2 at 180 °C under anhydrous conditions. Excellent durability of the hybrid composite membrane fuel cell has been demonstrated at 200 °C. The results of this study demonstrated the potential of the facile synthetic strategy in the fabrication of NH2-HMS with controlled mesoporous structure for application in nanocomposite membranes as a technology platform for elevated-temperature proton exchange membrane fuel cells.

Covalently cross-linked sulfone polybenzimidazole membranes with poly(vinylbenzyl chloride) for fuel cell applications.

Covalently cross-linked polymer membranes were fabricated from poly(aryl sulfone benzimidazole) (SO(2)PBI) and poly(vinylbenzyl chloride) (PVBCl) as electrolytes for high-temperature proton-exchange-membrane fuel cells. The cross-linking imparted organo insolubility and chemical stability against radical attack to the otherwise flexible SO(2)PBI membranes. Steady phosphoric acid doping of the cross-linked membranes was achieved at elevated temperatures with little swelling. The acid-doped membranes exhibited increased mechanical strength compared to both pristine SO(2)PBI and poly[2,2'-(m-phenylene)-5,5'-bibenzimidazole] (mPBI). The superior characteristics of the cross-linked SO(2)PBI membranes allowed higher acid doping levels and, therefore, higher proton conductivity. Fuel-cell tests with the cross-linked membranes demonstrated a high open circuit voltage and improved power performance and durability.

Regiospecific one-pot synthesis of diaryliodonium tetrafluoroborates from arylboronic acids and aryl iodides.

Diaryliodonium salts have recently received considerable attention as mild arylation reagents in organic synthesis. This paper describes a regiospecific, sequential one-pot synthesis of symmetrical and unsymmetrical diaryliodonium tetrafluoroborates, which are the most popular salts in metal-catalyzed arylations. The protocol is fast and high-yielding and has a large substrate scope. Furthermore, the corresponding diaryliodonium triflates can conveniently be obtained via an in situ anion exchange.