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Deep eutectic solvents (DESs) were considered as a potential electrolyte because of their low price, harmless to environment and wider electrochemical window potential compared to water. In this work, Fe(Ⅲ)/Fe(Ⅱ) and Zn(Ⅱ)/Zn redox couples were used as the positive and negative active materials, respectively, in a DES system using choline chloride and ethylene glycol in a molar ratio of 1:2 (ethaline). The possible working mechanism of the battery was studied by cyclic voltammetry, spectroscopic and simulation methods. The effects of different temperatures, concentrations of zinc ions in the anolyte and current densities on battery performance were evaluated. The results showed that the designed zinc-iron battery should preferably be operated at a current density of 0.5 mA cm-2 and the temperature of 313~323 K, which will improve the energy efficiency and maintain a high coulombic efficiency. The variation of cycle performance test presents a different pattern from the usual batteries, which is due to the effect of RO- group. At 313 K and 0.5 mA cm-2, the coulombic efficiency increases from 14.1% to 100.2% after 46 cycles, and then remains at about 100% during the rest 54 cycles, which demonstrates a good cycle stability of DES-based zinc-iron battery., (© 2024 Wiley‐VCH GmbH.)

Recent advances in 3D printing have enabled the manufacture of porous electrodes which cannot be machined using traditional methods. With micron-scale precision, the pore structure of an electrode can now be designed for optimal energy efficiency, and a 3D printed electrode is not limited to a single uniform porosity. As these electrodes scale in size, however, the total number of possible pore designs can be intractable; choosing an appropriate pore distribution manually can be a complex task. To address this challenge, we adopt an inverse design approach. Using physics-based models, the electrode structure is optimized to minimize power losses in a flow reactor. The computer-generated structure is then printed and benchmarked against homogeneous porosity electrodes. We show how an optimized electrode decreases the power requirements by 16% compared to the best-case homogeneous porosity. Future work could apply this approach to flow batteries, electrolyzers, and fuel cells to accelerate their design and implementation., (© 2024. The Author(s).)

Understanding the oxidation/reduction dynamics of secondary microparticles formed from agglomerated nanoscale primary particles is crucial for advancing electrochemical energy storage technologies. In this study, the behavior of individual copper hexacyanoferrate (CuHCF) microparticles is explored at both global and local scales combining scanning electrochemical microscopy (SECM), for electrochemical interrogation of a single, but global-scale microparticle, and optical microscopy monitoring to obtain a higher resolution dynamic image of the local electrochemistry within the same particle. Chronoamperometric experiments unveil a multistep oxidation/reduction process with varying dynamics. On the one hand, the global SECM analysis enables quantifying the charge transfer as well as its dynamics at the single microparticle level during the oxidation/reduction cycles by a redox mediator in solution. These conditions allow mimicking the charge storage processes in these particles when they are used as solid boosters in redox flow batteries. On the other hand, optical imaging with sub-particle resolution allows the mapping of local conversion rates and state-of-charge within individual CuHCF particles. These maps reveal that regions of different material loadings exhibit varying charge storage capacities and conversion rates. The findings highlight the significance of porous nanostructures and provide valuable insights for designing more efficient energy storage materials., (© 2024 The Authors. Small published by Wiley‐VCH GmbH.)

Bromine-based flow batteries (BFB) have always suffered from poor kinetics due to the sluggish Br 3 - /Br - redox, hindering their practical applications. Developing cathode materials with high catalytic activity is critical to address this challenge. Herein, the in-depth investigation for the free energy of the bromine redox electrode is conducted initially through DFT calculations, establishing the posterior desorption during oxidation as the rate-determining step. An urchin-like titanium nitride hollow sphere (TNHS) composite is designed and synthesized as the catalyst for bromine redox. The large difference in Br - and Br 3 during the oxidation process, liberating active sites timely to enable smooth ongoing reactions. Besides, the urchin-like microporous/mesoporous structure of TNHS provides abundant active surface for bromine redox reactions, and ample cavities for the bromine accommodation. The inherently high conductivity of TNHS enables facile electron transfer through multiple channels. Consequently, zinc-bromide flow batteries with TNHS catalyst exhibit significantly enhanced kinetics, stably operating at 80 mA cm - with 82.78% energy efficiency. Overall, this study offers a solving strategy and catalyst design approach to the sluggish kinetics that has plagued bromine-based flow batteries.3 - during the oxidation process, liberating active sites timely to enable smooth ongoing reactions. Besides, the urchin-like microporous/mesoporous structure of TNHS provides abundant active surface for bromine redox reactions, and ample cavities for the bromine accommodation. The inherently high conductivity of TNHS enables facile electron transfer through multiple channels. Consequently, zinc-bromide flow batteries with TNHS catalyst exhibit significantly enhanced kinetics, stably operating at 80 mA cm -2 with 82.78% energy efficiency. Overall, this study offers a solving strategy and catalyst design approach to the sluggish kinetics that has plagued bromine-based flow batteries., (© 2024 Wiley‐VCH GmbH.)

Pyridoxal hydrochloride, a vitamin B 6 vitamer, was synthetically converted to a series of diverse redox-active benzoyl pyridinium salts. Cyclic voltammetry studies demonstrated redox reversibility under basic conditions, and two of the most promising salts were subjected to laboratory-scale flow battery tests involving galvanostatic cycling at 10 mM in 0.1 M NaOH. In these tests, the battery was charged completely, corresponding to the transfer of two electrons to the electrolyte, but no discharge was observed. Both CV analysis and electrochemical simulations confirmed that the redox wave observed in the experimental voltammograms corresponds to a two-electron process. To explain the irreversibility in the battery tests, we conducted bulk electrolysis with the benzoyl pyridinium salts, affording the corresponding benzylic secondary alcohols. Computational studies suggest that the reduction proceeds in three consecutive steps: first electron transfer (ET), then proton-coupled electron transfer (PCET) and finally proton transfer (PT) to give the secondary alcohol. 1 H NMR deuterium exchange studies indicated that the last PT step is not reversible in 0.1 M NaOH, rendering the entire redox process irreversible. The apparent reversibility observed in CV at the basic media likely arises from the slow rate of the PT step at the timescale of the measurement., (© 2024 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)

Redox flow batteries (RFBs) are a promising technology for long-duration energy storage; but they suffer from inefficiencies in part due to the overvoltages at the electrode surface. In this work, more than 70 electrode treatments are reviewed that are previously shown to reduce the overvoltages and improve performance for vanadium RFBs (VRFBs), the most commercialized RFB technology. However, identifying treatments that improve performance the most and whether they are industrially implementable is challenging. This study attempts to address this challenge by comparing treatments under similar operating conditions and accounting for the treatment process complexity. The different treatments are compared at laboratory and industrial scale based on criteria for VRFB performance, treatment stability, economic feasibility, and ease of industrial implementation. Thermal, plasma, electrochemical oxidation, CO 2 treatments, as well as Bi, Ag, and Cu catalysts loaded on electrodes are identified as the most promising for adoption in large scale VRFBs. The similarity in electrode treatments for aqueous-organic RFBs (AORFBs) and VRFBs is also identified. The need of standardization in RFBs testing along with fundamental studies to understand charge transfer reactions in redox active species used in RFBs moving forward is emphasized., (© 2023 The Authors. Advanced Science published by Wiley-VCH GmbH.)

Vanadium flow battery (VFB) is one of the most reliable stationary electrochemical energy-storage technologies, and a membrane with high vanadium resistance and proton conductivity is essential for manufacturing high-performance VFBs. In this study, a two-dimensional (2D) MFI-type zeolite membrane was fabricated from zeolite nanosheet modules, which displayed excellent vanadium resistance (0.07 mmol L -1 h -1 ) and proton conductivity (0.16 S cm -1 ), yielding a coulombic efficiency of 93.9 %, a voltage efficiency of 87.6 %, and an energy efficiency of 82.3 % at 40 mA cm -2 . The self-discharge period of a VFB equipped with 2D MFI-type zeolite membrane increased up to 116.2 h, which was significantly longer than that of the commercial perfluorinated sulfonate membrane (45.9 h). Furthermore, the corresponding battery performance remained stable over 1000 cycles (>1500 h) at 80 mA cm -2 . These findings demonstrate that 2D MFI-type membranes are promising ion-conductive membranes applicable for stationary electrochemical energy-storage devices., (© 2023 Wiley-VCH GmbH.)

Neutral aqueous flow batteries with common traits of the redox flow batteries, such as the independence of energy and power, scalability and operational flexibility, and additional merits of outstanding safety and low corrosivity show great promise for storing massive electrical energy from solar and wind energy. Particularly, the ferricyanide/ferrocyanide ([Fe(CN) 6 ] 3-/4- ) couple has been intensively employed as redox mediator to store energy in the catholyte ascribed to its abundance, low corrosivity, remarkable redox reversibility and stability. However, the low energy density arising from poor solubility of [Fe(CN) 6 ] 3-/4- restricts their commercial applications for energy storage systems. In this study, the practical energy density of a [Fe(CN) 6 ] 3-/4- -based catholyte is significantly boosted from 10.5 to 92.8 Wh L -1 by combining the counter-ion effect and the single-molecule redox-targeting (SMRT) reactions between [Fe(CN) 6 ] 3-/4- and Prussian blue (Fe 4 [Fe(CN) 6 ] 3 , PB)/Prussian white (PW). Paired with concentrated K 2 S anolyte, we demonstrate a neutral aqueous SMRT-based PB-Fe/S flow battery with ultra-long lifespan over 7000 cycles (4500 h) and ultra-low chemical cost of electrolytes in the cell as 19.26 $ kWh -1 . Remarkably, under the influences of SMRT reactions in the presence of PB granules in the catholyte, the capacity after 7000 cycles of the PB-Fe/S flow battery is 181.8 % of the initial capacity without PB., (© 2023 Wiley-VCH GmbH.)

The identity of active sites for redox reactions within vanadium redox flow batteries (VRFBs) isstill controversial despite decades of research into the matter. Here, we use density functional theory to examine the premise of selected surface functional groups as active sites and provide mechanistic insights into the reaction pathway for the positive electrode reaction. The adsorption of electroactive species on phenol and carbene-like edge carbon sites was compared using model aromatic clusters. Phenol groups were not favorable sites for the chemisorption of VO 2 + in either V-down or O-down approach In contrast, carbene-like edge carbon sites readily adsorbed VO 2 + via an oxygen-down approach, mimicking gas-phase CO 2 adsorption mechanisms. Subsequent steps to complete the reaction pathway are a series of proton adsorptions and reaction products desorption. The rate-determining step for a reaction pathway using an edge site is VO 2+ desorption step with a Gibbs energy of activation of +84 kcal mol -1 ., (© 2023 The Authors. ChemSusChem published by Wiley-VCH GmbH.)

All vanadium flow batteries (VFBs) are considered one of the most promising large-scale energy storage technology, but restricts by the high manufacturing cost of V 3.5+ electrolytes using the current electrolysis method. Here, a bifunctional liquid fuel cell is designed and proposed to produce V 3.5+ electrolytes and generate power energy by using formic acid as fuels and V 4+ as oxidants. Compared with the traditional electrolysis method, this method not only does not consume additional electric energy, but also can output electric energy. Therefore, the process cost of producing V 3.5+ electrolytes is reduced by 16.3%. This fuel cell has a maximum power of 0.276 mW cm -2 at an operating current of 1.75 mA cm -2 . Ultraviolet-visible spectrum and potentiometric titration identify the oxidation state of prepared vanadium electrolytes is 3.48 ± 0.06, close to the ideal 3.5. VFBs with prepared V 3.5+ electrolytes deliver similar energy conversion efficiency and superior capacity retention to that with commercial V 3.5+ electrolytes. This work proposes a simple and practical strategy to prepare V 3.5+ electrolytes., (© 2023 The Authors. Advanced Science published by Wiley-VCH GmbH.)

Conventional ion-selective membranes, that is ion-exchange and porous membranes, are unable to perform high conductivity and selectivity simultaneously due to the contradictions between their ion selecting and conducting mechanisms. In this work, a bifunctional ion-selective layer is developed via the combination of nanoporous boron nitride (PBN) and ion exchange groups from Nafion to achieve high ion conductivity through dual ion conducting mechanisms as well as high ion selectivity. A template-free method is adopted to synthesize flake-like PBN, which is further enmeshed with Nafion resin to form the bifunctional layer coated onto a porous polyetherimide membrane. The double-layer membrane exhibits excellent ion selectivity (1.49 × 10 8 mS cm -3  min), which is 22 times greater than that of the pristine porous polyetherimide membrane, with outstanding ion conductivity (64 mS cm -1 ). In a vanadium flow battery, the double-layer membrane achieves a high Coulombic efficiency of 97% and outstanding energy efficiency of 91% at 40 mA cm -2 with a stable cycling performance for over 700 cycles at 100 mA cm -2 . PBN with ion exchange groups may therefore offer a potential solution to the limitation between ion selectivity and conductivity in ion-selective membranes., (© 2023 Wiley-VCH GmbH.)

Poly(ether sulfone) (PES) is a kind of polymer materials with excellent electrical insulation and acid/alkali stability. PES can be operated at high temperature continuously for a long time and still maintain excellent property stability in the environments with rapidly changed temperature, namely, great thermostability. Moreover, PES has low molding shrinkage, good dimensional stability and excellent film-forming characteristics. Compared with inorganic membranes, PES-based membranes have lower cost, which have received more attention and wide recognition in the field of clean energy technologies in recent years, such as flow batteries, fuel cells, water treatment, and gas separation. Therefore, this review summarizes the research status and prospect of the utilization of PES-based membranes in clean energy fields, in order to further promote their development and application., (© 2022 Wiley-VCH GmbH.)

Developing low-cost all-iron hybrid redox flow batteries (RFBs) presents a practical alternative to the high-cost all-vanadium RFBs and is deemed vital for grid-scale energy storage applications. However, the intrinsically poor Fe anode reversibility associated with the deposition and dissolution of metallic iron greatly limits the cycling performance and long-term stability of all-iron hybrid RFBs. Herein, a highly reversible and dendrite-free Fe anode is reported for all-iron RFBs through regulation of polar solvent dimethyl sulfoxide (DMSO) on FeCl 2 anolyte, which simultaneously reshapes Fe 2+ solvation structure and induces controllable oriented Fe deposition. Combining both experimental and theoretical analyses, the polar DMSO additives prove effective in replacing H 2 O molecule from the primary solvation shell of Fe 2+ cation via the Fe 2+ -O (DMSO) bond and meanwhile induces a fine-grained Fe nucleation on the preferred Fe (110) plane, which are responsible for the minimized hydrogen evolution and dendrite-free Fe deposition that significantly enhance Fe anode reversibility. The all-iron RFB based on the proposed FeCl 2 -DMSO anolyte demonstrates an excellent combination of peak power density of 134 mW cm -2 , high energy efficiency of 75% at 30 mA cm -2 , and high capacity retention of 98.6% over 200 cycles, which presents the best performance of all-iron RFBs among previously reported research., (© 2022 Wiley-VCH GmbH.)

Redox flow batteries (RFBs) stand out as a promising energy storage system to solve the grid interconnection problems of renewable energy. Membranes play a critical role in regulating the performance of RFBs, and the selectivity is commonly controlled via either size exclusion or Donnan exclusion. Membranes typically account for 40% of the stack cost of RFBs, and it is essential to develop cost-effective membranes with high selectivity to achieve widespread application. Here, a type of membrane composed of highly abundant materials derived in nature, based on a scalable fabrication process, is reported. Moreover, high selectivity is achieved attributed to the host-guest interactions between membranes and redox species, which effectively alleviate the crossover of redox-active molecules. By incorporating starch into a chitosan matrix for zinc-iodine RFBs, the highly selective recognition of starch and chitosan (host) toward triiodide (guest) builds a "wall" to block the triiodide-based active materials, meanwhile, the conducting properties of such a membrane are not compromised. The proof-of-concept battery delivers a Coulombic efficiency of 98.6% and energy efficiency of 77.4% at a current density of 80 mA cm -2 , showing the promise of such a novel and cost-effective membrane design beyond traditional selectivity chemistry., (© 2022 Wiley-VCH GmbH.)

Aqueous redox flow batteries (RFBs) are promising candidates for low-cost, grid-scale energy storage. However, the polymer-based membranes that are used in most prototypical systems fail to prevent crossover of small-molecule reactants, which results in high rates of capacity fade. In this work, we explore the feasibility of a von Alpen sodium superionic conductor Na 3.1 Zr 1.55 Si 2.3 P 0.7 O 11 (NaSICON) as an RFB membrane by examining its resistance, permeability, and interfacial morphology as a function of electrolyte composition and temperature . The resistance of NaSICON is stable for several weeks while immersed in neutral to strongly alkaline ([OH - ] = 3 M) aqueous electrolytes, and its permeability to polysulfide-based and permanganate-based small-molecule RFB reactants is negligible compared to that of Nafion. The glassy phase of the NaSICON microstructure at the membrane-electrolyte interface is susceptible to some etching while in contact with aqueous electrolytes containing sodium ions. This etching becomes more extensive when potassium ions are present in the electrolyte, leading in certain instances to complete disintegration of the membrane. A ∼0.7 mm-thin NaSICON membrane can nevertheless support over three weeks of cycling of a ferrocyanide|permanganate flow cell in a strongly alkaline electrolyte ([OH - ] = 3 M), with apparently negligible reactant crossover and very low capacity fade (<0.04%/day). NaSICON's area-specific resistance also decreases dramatically with increasing temperature and decreasing membrane thickness; there is a 5.6× reduction from a 1.19 mm-thick membrane at 18 °C (101 Ωcm 2 ) to a 0.61 mm-thick one at 70 °C (18 Ωcm 2 ). Lowering the thickness of the membrane to 0.1 mm or lower will result in power densities at above ambient temperatures that are comparable to power densities of polymer membrane-containing flow cells. This work highlights the promise of ceramic membranes as effective separators in RFBs operating under neutral pH to strongly alkaline pH conditions.

Stable and soluble redox-active nitroxyl radicals are highly desired for high-capacity and long-life aqueous zinc hybrid flow batteries (AZHFBs). Here we report a "π-π" conjugated imidazolium and "p-π" conjugated acetylamino co-functionalized 2,2,6,6-tetramethylpiperidine-N-oxyl (MIAcNH-TEMPO) as stable catholyte for AZHFBs. The incorporation of double-conjugate substituents could delocalize the electron density of the N-O head and thus remarkably stabilize the radical and oxoammonium forms of TEMPO, avoiding the side reaction of ring-opening. Consequently, the applied MIAcNH-TEMPO/Zn AZHFB demonstrates the hardly time-dependent stability with a constant capacity retention of 99.95 % per day over 16.7 days at a high concentration catholyte of 1.5 M and high current density of 50 mA cm -2 . This proposed molecular engineering strategy based on electron density regulation of redox-active structures displays an attractive efficacy and thus represents a remarkable advance in high-performance AZHFBs., (© 2022 Wiley-VCH GmbH.)

Redox flow batteries (RFBs) have attracted more attention due to their ability of decoupling energy and power, but their low energy density has greatly restricted their applications. Semisolid flow batteries (SSFBs) are a kind of RFBs, but they have high energy density. However, there is a lack of research on semisolid anolytes, and thus the application of SSFBs is still in its infancy. In this work, a low-potential (0.6 V vs Li/Li + ) CuSi 2 P 3 @C-LiPAA composite is synthesized through a simple high-energy mechanical ball milling and impregnation method based on the CuSi 2 P 3 (CSP) compound; then, it is used to prepare a semisolid anolyte, which is able to achieve a high volumetric capacity of 400 Ah L -1 in static mode and 320 Ah L -1 in intermittent-flow mode. This is the highest volumetric capacity of anolyte so far. The effect of adding binder to a composite is also discussed for the first time, which makes the connection between the composite particles closer and the semisolid suspension more uniform so as to obtain stable electrochemical performance. At the same time, through pairing respectively with two types of catholytes, liquid 10-methylphenothiazine (MPT) and semisolid LiFePO 4 (LFP), a single-cell voltage of 3 V and more than 100 stable cycles with the Coulombic efficiency of 99% have been achieved by CSP-MPT and CSP-LFP full-cell systems. The result fully demonstrates the applicability of the prepared CSP semisolid anolyte. The synthesis method of adding a binder to the composite in this work also provides a direction for optimizing the suspension for other active materials to be applied to SSFBs in the future.

Reversible electrodeposition of metals at liquid-solid interfaces is a requirement for long cycle life in rechargeable batteries that utilize metals as anodes. The process has been studied extensively from the perspective of the electrochemical transformations that impact reversibility, however, the fundamental challenges associated with maintaining morphological control when a intrinsically crystalline solid metal phase emerges from an electrolyte solution have been less studied, but provide important opportunities for progress. A crystal growth stabilization method to reshape the initial growth and orientation of crystalline metal electrodeposits is proposed here. The method takes advantage of polymer-salt complexes (PEG-Zn 2+ -aX - ) (a = 1,2,3) formed spontaneously in aqueous electrolytes containing zinc (Zn 2+ ) and halide (X - ) ions to regulate electro-crystallization of Zn. It is shown that when X = Iodine (I), the complexes facilitate electrodeposition of Zn in a hexagonal closest packed morphology with preferential orientation of the (002) plane parallel to the electrode surface. This facilitates exceptional morphological control of Zn electrodeposition at planar substrates and leads to high anode reversibility and unprecedented cycle life. Preliminary studies of the practical benefits of the approach are demonstrated in Zn-I2 full battery cells, designed in both coin cell and single-flow battery cell configurations., (© 2021 Wiley-VCH GmbH.)

Solid boosters are an emerging concept for improving the performance and especially the energy storage density of the redox flow batteries, but thermodynamical and practical considerations of these systems are missing, scarce or scattered in the literature. In this paper we will formulate how these systems work from the point of view of thermodynamics. We describe possible pathways for charge transfer, estimate the overpotentials required for these reactions in realistic conditions, and illustrate the range of energy storage densities achievable considering different redox electrolyte concentrations, solid volume fractions and solid charge storage densities. Approximately 80% of charge storage capacity of the solid can be accessed if redox electrolyte and redox solid have matching redox potentials. 100 times higher active areas are required from the solid boosters in the tank to reach overpotentials of <10 mV.

Widespread adoption of redox flow batteries (RFBs) for renewable energy storage is inhibited by a relatively high cost of storage. This is due largely to typical RFBs requiring two flows, two external tanks, and expensive ion-exchange membranes. Here, we propose a potentially inexpensive Zn-Br 2 RFB which is membraneless and requires only a single flow. The flow is an emulsion consisting of a continuous, Br 2 -poor aqueous phase and a dispersed, Br 2 -rich polybromide phase, pumped through the channel separating anode and cathode. With our prototype cell, we explore the effect of polybromide-phase volume fraction and Br 2 concentration on cell performance and plating efficiencies. We demonstrate high discharge currents of up to 270 mA/cm 2 , plating efficiencies up to 88 %, and dendriteless plating up to the highest Zn loading investigated of 250 mAh/cm 2 . We provide mechanistic insights into cell behavior and elucidate paths towards unlocking ultra-low-cost single-flow RFBs with multiphase flow., (© 2020 Wiley-VCH GmbH.)

The elaborate spatial arrangement and immobilization of highly active electrocatalysts inside porous substrates are crucial for vanadium redox flow batteries capable of high-rate charging/discharging and stable operation. Herein, a type of bismuth nanosphere/carbon felt is devised and fabricated via the carbothermic reduction of nanostructured bismuth oxides. The bismuth nanospheres with sizes of ≈25 nm are distributed on carbon fiber surfaces in a highly dispersed manner and its density reaches up to ≈500 pcs µm -2 , providing abundant active sites. Besides, a unique bismuth nanosphere semi-embedded carbon fiber structure with strong interfacial BiC chemical bonding is spontaneously formed during carbothermic reactions, offering an excellent mechanical stability under flowing electrolytes. It shows that the bismuth nanosphere semi-embedded carbon felt can effectively promote V(II)/V(III) redox reactions with appreciable catalytic activity. The battery with the present electrode sustains an energy efficiency of 77.1 ± 0.2% and an electrolyte utilization of 57.2 ± 0.2% even when a current density up to 480 mA cm -2 is applied, which are remarkably higher than those of batteries with the bismuth nanoparticle/carbon felt synthesized by the electrodeposition method (62.6 ± 0.1%, 23.6 ± 0.2%). Further, the battery with the present electrode demonstrates a stable energy efficiency retention of 98.2% after 1000 cycles., (© 2020 Wiley-VCH GmbH.)

Flow batteries (FBs) are one of the most attractive candidates for stationary energy storage and vital in realizing the wide application of renewable energies. Membranes play an important role in isolating redox couples while transporting ions to close the internal electrical circuit. Therefore, membranes with high selectivity and conductivity are highly important. Among different membranes, a composite membrane with independent design of support layer and thin selective top layer becomes one of the most promising candidates to break the trade-off between selectivity and conductivity. In this Review, recent studies on composite membranes for FBs and the principles of membrane design in different systems are discussed and summarized. Finally, the future direction on membrane design for different FBs is presented, which will provide an extensive, comprehensive reference to design and construct high-performance composite membranes for FBs., (© 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Alternatives of commercial lithium-ion batteries (LIBs) have drawn huge attention due to the large demand of energy storage systems and the lack of resources for traditional LIBs. Promising candidates include but are not limited to Li-S batteries, organic batteries and flow batteries. However, the dissolution of active materials and the consequent shuttle effect, as one of the main challenges in these candidates, always leads to significant capacity loss and poor cycling life. The rising two-dimensional (2D) materials, with well-defined structures and attractive physical and chemical properties, provide a new vision to solve these problems via suppressing the shuttle of the dissolved active materials. Herein, we present a minireview on the advances and perspectives of 2D materials as ionic sieves for inhibiting the shuttle effect in batteries., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Proton exchange membranes are at the heart of various technologies utilizing electrochemical storage of intermittent energy sources and powering electrical devices. Current state of the art membranes are based on perfluorosulfonic acid, introduced more than a half century ago. Low specificity to protons accompanied by permeance by other species is one of the main impediments for various promising applications in green technologies in an energy sustainable economy. Here we present composite membranes that are exclusively proton selective and do not allow crossover of any ionic or molecular species other than protons. Membranes have high proton conductivity and exceptional mechanical and chemical stability and thus may significantly improve performance of hydrogen-based technologies such as electrolyzers, various kinds of fuel cells, and flow batteries in the future.

Flow batteries (FBs) have become a central topic recently, due to their promising prospect of addressing the issues of the random and intermittent nature of renewable energy sources. However, the successful industrialization of current FB systems is still limited by their relatively low energy densities and high cost. Research and development into novel aqueous FB systems with high energy density, high safety, and low cost are accordingly urgently required. Some novel aqueous FB systems have been explored in recent years to overcome issues of traditional FBs and vanadium FBs, in particular. Further modifications have also been made to improve their performance. In this review, appealing novel aqueous FB systems, such as zinc- and quinone-based FB systems, are reviewed, in terms of the operating principles, advantages, drawbacks, corresponding performance, and subsequent modifications. Moreover, recent investigations and advancements, and prospective research directions for novel aqueous FB systems, are summarized. Therefore, this review will provide guidance and perspectives for developing new aqueous FB systems., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A zinc-iodine flow battery (ZIFB) with long cycle life, high energy, high power density, and self-healing behavior is prepared. The long cycle life was achieved by employing a low-cost porous polyolefin membrane and stable electrolytes. The pores in the membrane can be filled with a solution containing I 3 - that can react with zinc dendrite. Therefore, by consuming zinc dendrite, the battery can self-recover from micro-short-circuiting resulting from overcharging. By using KI, ZnBr 2 , which is 8 times higher than the currently reported ZIFBs. Furthermore, a stack with an output of 700 W was assembled and continuously run for more than 300 cycles. We believe this ZIFB can lead the way to development of new-generation, high-performance flow batteries.-2 , which is 8 times higher than the currently reported ZIFBs. Furthermore, a stack with an output of 700 W was assembled and continuously run for more than 300 cycles. We believe this ZIFB can lead the way to development of new-generation, high-performance flow batteries., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Electrospun custom made flow battery electrodes are imaged in 3D using X-ray computed tomography. A variety of computational methods and simulations are applied to the images to determine properties including the porosity, fiber size, and pore size distributions as well as the material permeability and flow distributions. The simulations are performed on materials before and after carbonization to determine the effect it has in the internal microstructure and material properties. It is found that the deposited fiber size is constantly changing throughout the electrospinning process. The results also show that the surfaces of the fibrous material are the most severely altered during carbonization and that the rest of the material remained intact. Pressure driven flow is modeled using the lattice Boltzmann method and excellent agreement with experimental results is found. The simulations coupled with the material analysis also demonstrate the highly heterogeneous nature of the flow. Most of the flow is concentrated to regions with high porosity while regions with low porosity shield other pores and starve them of flow. The importance of imaging these materials in 3D is highlighted throughout., (© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Flow batteries (FBs) are one of the most promising stationary energy-storage devices for storing renewable energy. However, commercial progress of FBs is limited by their high cost and low energy density. A neutral zinc-iron FB with very low cost and high energy density is presented. By using highly soluble FeCl 2 /ZnBr 2 species, a charge energy density of 56.30 Wh L -1 can be achieved. DFT calculations demonstrated that glycine can combine with iron to suppress hydrolysis and crossover of Fe 3+ /Fe 2+ . The results indicated that an energy efficiency of 86.66 % can be obtained at 40 mA cm -2 and the battery can run stably for more than 100 cycles. Furthermore, a low-cost porous membrane was employed to lower the capital cost to less than $ 50 per kWh, which was the lowest value that has ever been reported. Combining the features of low cost, high energy density and high energy efficiency, the neutral zinc-iron FB is a promising candidate for stationary energy-storage applications., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Salinity gradient energy can be directly converted into electrical power by using reverse electrodialysis (RED) and other technologies, but reported power densities have been too low for practical applications. Herein, the RED stack performance was improved by using 2,6-dihydroxyanthraquinone and ferrocyanide as redox couples. These electrolytes were then used in a flow battery to produce an integrated RED stack and flow battery (RED-FB) system capable of capturing, storing, and discharging salinity gradient energy. Energy captured from the RED stack was discharged in the flow battery at a maximum power density of 3.0 kW m -2 -anode, which was similar to the flow batteries charged by electrical power and could be used for practical applications. Salinity gradient energy captured from the RED stack was recovered from the electrolytes as electricity with 30 % efficiency, and the maximum energy density of the system was 2.4 kWh m -3 -anolyte. The combined RED-FB system overcomes many limitations of previous approaches to capture, store, and use salinity gradient energy from natural or engineered sources., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

In this study, a new mechanism for the reduction of vanadyl acetylacetonate, VO(acac) 2 , to vanadium acetylacetonate, V(acac) 3 , is introduced. V(acac) 3 has been studied for use in redox flow batteries (RFBs) for some time; however, contamination by moisture leads to the formation of VO(acac) 2 . In previous work, once this transformation occurs, it is no longer reversible because there is a requirement for extreme low potentials for the reduction to occur. Here, we propose that, in the presence of excess acetylacetone (Hacac) and free protons (H + ), the reduction can take place between 2.25 and 1.5 V versus Na/Na + via a one-electron-transfer reduction. This reduction can take place in situ during discharge in a novel hybrid Na-based flow battery (HNFB) with a molten Na-Cs alloy as the anode. The in situ recovery of V(acac) 3 during discharge is shown to allow the Coulombic efficiency of the HNFB to be ≈100 % with little or no capacity decay over cycles. In addition, utilizing two-electron-transfer redox reactions (i.e., V 3+ /V 4+ and V 2+ /V 3+ redox couples) per V ion to increase the energy density of RFBs becomes possible owing to the in situ recovery of V(acac) 3 during discharge. The concept of in situ recovery of material can lead to more advances in maintaining the cycle life of RFBs in the future., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Carbon-based suspension electrodes are currently intensively investigated for emerging electrochemical systems, such as flow batteries, flow capacitors, and capacitive deionization cells. The main limitation of such electrodes is their low electric conductivity, which is typically orders of magnitude lower than that of traditional static carbon electrodes. Two main categories of suspension electrodes exist: 1) slurry electrodes where particles are not significantly affected by gravity, and 2) fluidized bed electrodes where particles are affected by gravity. We introduce a novel category that we term "combined" suspension electrodes, which combine dilute slurries and dense fluidized beds. We present experimental measurements of the electrochemical impedance and electric conductivity of two combined electrodes. For one set of materials, the measured electric conductivity of the combined electrode is at least an order of magnitude above the fluidized bed and slurry components alone, demonstrating that a synergetic effect can be achieved when adding dilute slurry to dense fluidized bed. For a second set of materials, results show that the combined electrode conductivity is lower than the slurry component alone, a counter-intuitive result, demonstrating that increasing electrode carbon loading does not always enhance the electric conductivity., (© 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The electrolyte is one of the most important components of the vanadium redox flow battery and its properties will affect cell performance and behavior in addition to the overall battery cost. Vanadium exists in several oxidation states with significantly different half-cell potentials that can produce practical cell voltages. It is thus possible to use the same element in both half-cells and thereby eliminate problems of cross-contamination inherent in all other flow battery chemistries. Electrolyte properties vary with supporting electrolyte composition, state-of-charge, and temperature and this will impact on the characteristics, behavior, and performance of the vanadium battery in practical applications. This Review provides a broad overview of the physical properties and characteristics of the vanadium battery electrolyte under different conditions, together with a description of some of the processing methods that have been developed to produce vanadium electrolytes for vanadium redox flow battery applications., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A newly prepared type of carbon felt with oxygen-rich phosphate groups is proposed as a promising electrode with good stability for all-vanadium redox flow batteries (VRFBs). Through direct surface modification with ammonium hexafluorophosphate (NH4 PF6 ), phosphorus can be successfully incorporated onto the surface of the carbon felt by forming phosphate functional groups with -OH chemical moieties that exhibit good hydrophilicity. The electrochemical reactivity of the carbon felt toward the redox reactions of VO(2+) /VO2 (+) (in the catholyte) and V(3+) /V(2+) (in the anolyte) can be effectively improved owing to the superior catalytic effects of the oxygen-rich phosphate groups. Furthermore, undesirable hydrogen evolution can be suppressed by minimizing the overpotential for the V(3+) /V(2+) redox reaction in the anolyte of the VRFB. Cell-cycling tests with the catalyzed electrodes show improved energy efficiencies of 88.2 and 87.2 % in the 1(st) and 20(th)  cycles compared with 83.0 and 81.1 %, respectively, for the pristine electrodes at a constant current density of 32 mA cm(-2) . These improvements are mainly attributed to the faster charge transfer allowed by the integration of the oxygen-rich phosphate groups on the carbon-felt electrode., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Zeolites are crystalline microporous aluminosilicates with periodic arrangements of cages and well-defined channels, which make them very suitable for separating ions of different sizes, and thus also for use in battery applications. Herein, an ultra-thin ZSM-35 zeolite flake was introduced onto a poly(ether sulfone) based porous membrane. The pore size of the zeolite (ca. 0.5 nm) is intermediary between that of hydrated vanadium ions (>0.6 nm) and protons (<0.24 nm). The resultant membrane can thus be used to perfectly separate vanadium ions and protons, making this technology useful in vanadium flow batteries (VFB). A VFB with a zeolite-coated membrane exhibits a columbic efficiency of >99 % and an energy efficiency of >81 % at 200 mA cm(-2), which is by far the highest value ever reported. These convincing results indicate that zeolite-coated membranes are promising in battery applications., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The technical features of solid-electrode batteries (e.g., high energy density, relatively low capital cost ($/kWh)) and flow batteries (e.g., long cycle life, design flexibility) are highly complementary. It is therefore extremely desirable to integrate their advantages into a single storage device for large-scale energy storage applications where lifetime cost ($/kW-h/cycle) is an extremely important parameter. Here, we demonstrate a non-Li-based-flow battery concept that replaces the aqueous solution of redox-active molecules found in typical redox flow batteries with suspensions of hydrophilic carbon particles ("solid suspension electrodes") coated with earth-abundant redox-active metals. The solid suspension electrodes charge by depositing earth-abundant redox-active metals onto the carbon particle suspension, which are then stripped during discharge operation. The electrical contact to the solid suspension electrodes is fed through fixed redox-inert hydrophobic carbon current collectors through "contact charge transfer" mechanism. The hydrophobicity of the current collectors prevents direct plating of redox-active metals onto their surfaces. The above concept was successfully used to demonstrate several non-Li-based battery chemistries including zinc-copper, zinc-manganese oxide, zinc-bromine, and zinc-sulfur, providing a pathway for potential applications in medium and large-scale electrical energy storage.

In this study, we have investigated the key factors dictating the cyclic performance of a new type of hybrid sodium-based flow batteries (HNFBs) that can operate at room temperature with high cell voltages (>3 V), multiple electron transfer redox reactions per active ion, and decoupled design of power and energy. HNFBs are composed of a molten Na-Cs alloy anode, flowing aqueous catholyte, and a Na-β″-Al2O3 solid electrolyte as the separator. The surface functionalization of graphite felt electrodes for the flowing aqueous catholyte has been studied for its effectiveness in enhancing V(2+)/V(3+), V(3+)/V(4+), and V(4+)/V(5+) redox couples. The V(4+)/V(5+) redox reaction has been further investigated at different cell operation temperatures for its cyclic stability and how the properties of the solid electrolyte membrane play a role in cycling. These fundamental understandings provide guidelines for improving the cyclic performance and stability of HNFBs with aqueous catholytes. We show that the HNFB with aqueous V-ion catholyte can reach high storage capacity (∼70% of the theoretical capacity) with good Coulombic efficiency (90% ± 1% in 2-30 cycles) and cyclic performance (>99% capacity retention for 30 cycles). It demonstrates, for the first time, the potential of high capacity HNFBs with aqueous catholytes, good capacity retention and long cycling life. This is also the first demonstration that Na-β″-Al2O3 solid electrolyte can be used with aqueous electrolyte at near room temperature for more than 30 cycles.

A redox-active supercooled liquid is obtained by forming a "solvate ionic liquid" from a mixture of a stabilized organic radical and a specific Li salt and stabilizing the mixture further below their melting points. As a catholyte, the addition of an appropriate amount of water helps to enhance the electrochemical advantage while maintaining its supercooled nature and the liquid shows a high energy density of 200 W h L(-1) with reversible charge/discharge., (© 2015 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)