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The development of new redox flow battery chemistries is hampered by time-consuming organic syntheses and electrochemical characterization of candidate redoxmer molecules. Here, we use Sure Indepen...

Redox flow batteries are attractive for large-scale energy storage due to a combination of high theoretical efficiencies and decoupled power and energy storage capacities. Efforts to significantly increase energy densities by using nonaqueous electrolytes have been impeded by separators with low selectivities. Here, we report nanoporous separators based on aramid nanofibres, which are assembled using a scalable, low cost, spin-assisted layer-by-layer technique. The multilayer structure yields 5 ± 0.5 nm pores, enabling nanofiltration with high selectivity. Further, surface modifications using polyelectrolytes result in enhanced performance. In vanadium acetylacetonate/acetonitrile-based electrolytes, the coated separator exhibits permeabilities an order of magnitude lower and ionic conductivities five times higher than those of a commercial separator. In addition, the coated separators exhibit exceptional stability, showing minimal degradation after more than 100 h of cycling. The low permeability translates into high coulombic efficiency in flow cell charge/discharge experiments performed at cycle times relevant for large-scale applications (5 h)., Nonaqueous redox flow batteries may offer high energy and power densities, but development of separators is key for optimization. Here the authors achieve high coulombic efficiency with a nanoporous aramid nanofibres-based separator with low permeability, high ion conductivity, and exceptional stability.

The practical implementation of nanomaterials in high capacity batteries has been hindered by the large mechanical stresses during ion insertion/extraction processes that lead to the loss of physical integrity of the active layers. The challenge of combining the high ion storage capacity with resilience to deformations and efficient charge transport is common for nearly all battery technologies. Layer-by-layer (LBL/LbL) engineered nanocomposites are able to mitigate structural design challenges for materials requiring the combination of contrarian properties. Herein, we show that materials engineering capabilities of LBL augmented by self-organization of nanoparticles (NPs) can be exploited for constructing multiscale composites for high capacity lithium ion anodes that mitigate the contrarian nature of three central parameters most relevant for advanced batteries: large intercalation capacity, high conductance, and robust mechanics. The LBL multilayers were made from three function-determining components...

In this paper, the current technological state of core-shell nanostructured catalysts is reviewed for oxygen reduction reaction (ORR). The advantages of core-shell catalysts over alloyed ones are discussed and their achievements are summarized. Various core-shell electrocatalysts with advanced nanostructures have shown remarkable activity and stability, demonstrating great potential in proton exchange membrane (PEM) fuel cell applications. The dissolution of core and shell as well as low structure retention in fuel cell operating environments can cause catalyst degradation, which is a major challenge and remains such. To facilitate further efforts in new catalyst development, several research directions are proposed in this paper.

Catholyte materials are used to store positive charge in energized fluids circulating through redox flow batteries (RFBs) for electric grid and vehicle applications. Energy-rich radical cations (RCs) are being considered for use as catholyte materials, but to be practically relevant, these RCs (that are typically unstable, reactive species) need to have long lifetimes in liquid electrolytes under the ambient conditions. Only few families of such energetic RCs possess stabilities that are suitable for their use in RFBs; currently, the derivatives of 1,4-dialkoxybenzene look the most promising. In this study, we examine factors that define the chemical and electrochemical stabilities for RCs in this family. To this end, we used rigid bis-annulated molecules that by design avoid the two main degradation pathways for such RCs, viz., their deprotonation and radical addition. The decay of the resulting RCs are due to the single remaining reaction: O-dealkylation. We establish the mechanism for this reaction and...

New active materials are needed to improve the performance and reduce the cost of non-aqueous redox flow batteries (RFBs) for grid-scale energy storage applications. Efforts to develop better performing materials, which have largely been empirical, would benefit from a better understanding of relationships between structural, electronic and RFB-relevant functional properties. This paper focuses on metal-acetylacetonates, a class of metal coordination complexes that has shown promise for use in RFBs, and describes correlations between their experimentally measured standard potentials, solubilities, and stabilities (cycle lifes), and selected chemical, structural and electronic properties determined from Density Functional Theory (DFT) calculations. The training set consisted of 16 complexes including 5 different metals and 11 different substituents on the acetylacetonate ligand. Standard potentials for those compounds were calculated and are in good agreement with experimentally measured results. A predictive equation based on the solvation energies and dipole moments, two easily computed properties, reasonably modeled the experimentally determined solubilities. Importantly, we were able to identify a descriptor for the stability of acetylacetonates. The experimentally determined stability, quantified as the cycle life to a given degree of degradation, correlated with the percentage of the highest occupied (HOMO) or lowest unoccupied molecular orbital (LUMO) on the metal of the complex. This percentage is influenced by the degree of ligand innocence (irreducibility), and complexes with the most innocent ligands yielded the most stable redox reactions. To this end, VO(acetylacetonate)2 and Fe(acetylacetonate)3, with nearly 80% of the HOMO and LUMO on the metal, possessed the most stable oxidation and reduction half-reactions, respectively. The structure–function relationships and correlations presented in this paper could be used to predict new, highly soluble and stable complexes for RFB applications.

Batteries based on divalent metals, such as the Zn/Zn2+ pair, represent attractive alternatives to lithium-ion chemistry due to their high safety, reliability, earth-abundance, and energy density. However, archetypal Zn batteries are bulky, inflexible, non-rechargeable, and contain a corrosive electrolyte. Suppression of the anodic growth of Zn dendrites is essential for resolution of these problems and requires materials with nanoscale mechanics sufficient to withstand mechanical deformation from stiff Zn dendrites. Such materials must also support rapid transport Zn2+ ions necessary for high Coulombic efficiency and energy density, which makes the structural design of such materials a difficult fundamental problem. Here, we show that it is possible to engineer a solid Zn2+ electrolyte as a composite of branched aramid nanofibers (BANFs) and poly(ethylene oxide) by using the nanoscale organization of articular cartilage as a blueprint for its design. The high stiffness of the BANF network combined with t...

Micrometre-sized particles covered with stiff, nanoscale spikes are shown to exhibit long-term colloidal stability in both hydrophilic and hydrophobic media, without the need for chemical coating, owing to the effect of the spikes on the contact area and, consequently, the force between the particles. The conventional way of persuading hydrophobic particles to form colloidal suspensions in water — and hydrophilic particles to disperse in oil — is to camouflage the particles chemically with surfactants, organic tethers, adsorbed polymers or other agents that impart affinity for the solvent. Joong Hwan Bahng et al. now show that surface corrugation provides a very effective alternative strategy for dispersing particles in a wide range of solvents. The team produce micrometre-sized 'hedgehog' particles that are coated with stiff nanospikes and exhibit long-term colloidal stability in both hydrophilic and hydrophobic media. This unusual dispersion behaviour challenges current theories and deepens our understanding of colloidal interparticle interactions. The technique may have technological uses, as it provides particles that function in both organic and aqueous media. Hydrophobic particles in water and hydrophilic particles in oil aggregate, but can form colloidal dispersions if their surfaces are chemically camouflaged with surfactants, organic tethers, adsorbed polymers or other particles that impart affinity for the solvent and increase interparticle repulsion1,2. A different strategy for modulating the interaction between a solid and a liquid uses surface corrugation, which gives rise to unique wetting behaviour3,4,5. Here we show that this topographical effect can also be used to disperse particles in a wide range of solvents without recourse to chemicals to camouflage the particles’ surfaces: we produce micrometre-sized particles that are coated with stiff, nanoscale spikes and exhibit long-term colloidal stability in both hydrophilic and hydrophobic media. We find that these ‘hedgehog’ particles do not interpenetrate each other with their spikes, which markedly decreases the contact area between the particles and, therefore, the attractive forces between them. The trapping of air in aqueous dispersions, solvent autoionization at highly developed interfaces, and long-range electrostatic repulsion in organic media also contribute to the colloidal stability of our particles. The unusual dispersion behaviour of our hedgehog particles, overturning the notion that like dissolves like, might help to mitigate adverse environmental effects of the use of surfactants and volatile organic solvents, and deepens our understanding of interparticle interactions and nanoscale colloidal chemistry.

Current collectors are essential features of batteries and many other electronic devices being responsible for efficient charge transport to active electrode materials. Three-dimensional (3D), high surface area current collectors considerably improve the performance of cathodes and anodes in batteries, but their technological implementation is impeded by the complexity of their preparation, which needs to be simple, fast, and energy efficient. Here we demonstrate that field-stimulated assembly of ∼3 nm copper nanoparticles (NPs) enables the preparation of porous Cu NP films. The use of NP dispersions enables 30× reduction of the deposition current for making functional 3D coatings. In addition to high surface area, lattice-to-lattice connectivity in the self-assembly of NPs in 3D structures enables fast charge transport. The mesoscale dimensions of out-of-plane features and the spacing between them in Cu films made by field-stimulated self-assembly of NPs provides promising morphology for current collection in lithium ion batteries (LIBs). Half-cell electrochemical models based on self-assembled films show improved specific capacity, total capacity, and cycling performance compared to traditional flat and other 3D current collectors. While integration of active electrode material into the 3D topography of the current collector needs to be improved, this study indicates that self-assembled NP films represent a viable manufacturing approach for 3D electrodes.

Deficiencies of cathode materials severely limit cycling performance and discharge rates of Li batteries. The key problem is that cathode materials must combine multiple properties: high lithium ion intercalation capacity, electrical/ionic conductivity, porosity, and mechanical toughness. Some materials revealed promising characteristics in a subset of these properties, but attaining the entire set of often contrarian characteristics requires new methods of materials engineering. In this paper, we report high surface area 3D composite from reduced graphene oxide loaded with LiFePO4 (LFP) nanoparticles made by layer-by-layer assembly (LBL). High electrical conductivity of the LBL composite is combined with high ionic conductivity, toughness, and low impedance. As a result of such materials properties, reversible lithium storage capacity and Coulombic efficiency were as high as 148 mA h g(-1) and 99%, respectively, after 100 cycles at 1 C. Moreover, these composites enabled unusually high reversible charge-discharge rates up to 160 C with a storage capacity of 56 mA h g(-1), exceeding those of known LFP-based cathodes, some of them by several times while retaining high content of active cathode material. The study demonstrates that LBL-assembled composites enable resolution of difficult materials engineering tasks.

The practical application of non-aqueous redox flow batteries (NRFBs) sets stringent requirements on the electrochemical stability of the redox active materials. In the redox pair for NRFBs, the high-potential species is referred to as the catholyte, which is oxidized into the radical cation state in the charging process. Hydroquinone ethers are a key class of catholyte materials, but the intermolecular reaction between the radical cations is a dominating decomposition pathway of the catholyte during functioning. In order to increase the electrochemical stability of the catholyte materials, the introduction of bulky alkyl spacers at 2,5- positions of the arene ring is commonly used as a strategy in the molecular design to suppress this type of undesirable side reaction. However, the unsubstituted 3,6- positions that are favored for the electrochemical reversibility are responsible for the radical cation reaction in the long-time cycling. Tetrasubstitution of the arene core with either primary or secondary alkyl groups often leads to a compromised redox reversibility. This talk will describe a tetrasubstituted hydroquinone ether-based catholyte molecule that retains excellent redox reversibility and illustrates exceptional stability. Unique bicyclic alkyl groups are incorporated to the molecular scaffold, eliminating the bimolecular reaction between the radical cations. A hybrid NRFB using such catholyte has been operated for over 150 charge-discharge cycles with minimal loss of capacity.

1,4-Dimethoxybenzene derivatives are materials of choice for use as catholytes in non-aqueous redox flow batteries, as they exhibit high open-circuit potentials and excellent electrochemical reversibility. However, chemical stability of these materials in their oxidized form needs to be improved. Disubstitution in the arene ring is used to suppress parasitic reactions of their radical cations, but this does not fully prevent ring-addition reactions. By incorporating bicyclic substitutions and ether chains into the dialkoxybenzenes, a novel catholyte molecule, 9,10-bis(2-methoxyethoxy)-1,2,3,4,5,6,7,8-octahydro-1,4:5,8-dimethanenoanthracene (BODMA), is obtained and exhibits greater solubility and superior chemical stability in the charged state. A hybrid flow cell containing BODMA is operated for 150 charge–discharge cycles with a minimal loss of capacity.

Hydroquinone ethers are a key class of catholyte materials for non-aqueous redox flow batteries, showing high open-circuit potential, electrochemical reversibility and chemical tunability. However, the instability of many hydroquinone ethers, particular to electrochemical oxidation, limits their applicability. 2,5-dialkylation of the benzene core has been by far the only effective chemical approach to suppress the side reactions of the corresponding radical cations, restricting the chemical space of structures from which to choose. This talk will describe a bicyclo-alkyl substitution strategy that yields a hydroquinone ether with unprecedentedly high electrochemical stability. The influences of different substituents on the electrochemical properties are investigated. The electrochemical stability is determined via a full flow cell using a benzothiadiazole-based anolyte. In addition, the low impedance shown in the single electrolyte flow cell indicates its great promises as catholyte for high-performance non-aqueous redox flow batteries.

Dendrite growth threatens the safety of batteries by piercing the ion-transporting separators between the cathode and anode. Finding a dendrite-suppressing material that combines high modulus and high ionic conductance has long been considered a major technological and materials science challenge. Here we demonstrate that these properties can be attained in a composite made from Kevlar-derived aramid nanofibres assembled in a layer-by-layer manner with poly(ethylene oxide). Importantly, the porosity of the membranes is smaller than the growth area of the dendrites so that aramid nanofibres eliminate 'weak links' where the dendrites pierce the membranes. The aramid nanofibre network suppresses poly(ethylene oxide) crystallization detrimental for ion transport, giving a composite that exhibits high modulus, ionic conductivity, flexibility, ion flux rates and thermal stability. Successful suppression of hard copper dendrites by the composite ion conductor at extreme discharge conditions is demonstrated, thereby providing a new approach for the materials engineering of solid ion conductors.

The electrochemical oxidation of vanadium acetylacetonate produces vanadyl acetylacetonate limiting its use in non-aqueous redox flow batteries. The vanadyl has also drawn little interest as a catholyte active species despite its favorable voltage potential (0.7V vs. Ag/Ag+). This is mainly due to its low solubility (0.05M) in acetonitrile. Our recent bulk electrolysis studies, however, indicate that the reduction of vanadyl is highly reversible. For example, there was no capacity fade for >100 cycles at 70% state of charge. In this paper, we investigate the charge storage capabilities and stability of vanadyl acetylacetonate. Long term (10+ days) charge/discharge experiments are performed with vanadium acetyacetonate as the anolyte at various C-rates. While the relationship of increasing coulombic efficiency with increasing C-rates seems obvious at first, further analysis by normalizing the coulombic inefficiency with cycle time shows that the parasitic reaction rate of these experiments are identical. This suggests that the degradation in each experiment is independent of cycle number, but simply dependent on time. We attributed these parasitic reactions to either active species crossover or material degradation. Permeability experiments and shelf life studies are then performed to quantify the individual contributions of crossover and material degradation to the observed parasitic reactions. The results suggest that crossover accounts for more than 95% of the inefficiency during charge/discharge, while degradation of the catholyte and anolyte have minimal contribution. This work emphasizes the growing need for better membranes and separators for non-aqueous redox flow batteries. Work is also ongoing to further improve the stability and solubility of vanadyl acetylacetonate using design strategies previously reported for vanadium acetylacetonate.

Redox flow batteries (RFBs) possess a unique combination of attractive attributes including decoupled power and energy storage capacities, low cost, and high efficiencies, and are promising for large-scale energy storage. A significant challenge in the development of high energy density, non-aqueous systems is the lack of selective membrane/separator materials. This paper describes a novel nanoporous separator based on aramid nanofibers (ANF) produced using a spin-coating, layer-by-layer technique. The multilayer structure yields 5 nm pores, enabling nanofiltration and high selectivities, in terms of the transport of species with differing sizes. Vanadium acetylacetonate (V(acac)3), a candidate for non-aqueous RFB electrolytes, was used as the model active species. It’s permeability through the ANF separator was an order of magnitude lower than that for Celgard 2325, a commercial separator while the support conductivities were comparable. The combined effect resulted in a doubling of the coulombic and energy efficiencies for cells using V(acac)3 based electrolytes. For asymmetric cells with solutions of V(acac)3 as the negative electrolyte and ferrocene as the positive electrolyte, a 60% improvement in coulombic efficiency was achieved using the ANF separator over Celgard. The results demonstrate the feasibility of using ANF separators for symmetric and asymmetric non-aqueous RFBs and encourages further development.

Lithium ion batteries commonly utilize layered oxide materials as the cathode, where lithium is intercalated and deintercalated between the layers in the crystal structure during cycling. The repeated lithium insertion and extraction can cause stress on the material, leading to fracture. Additionally, the extent of lithiation may cause phase changes in the layered structure that are sometimes irreversible. These changes to the material cause capacity loss and reduce the battery cycle life. This research focuses on nanostructuring layered oxides to enhance their cyclability and power capabilities. In particular, vanadium oxide xerogels were modified by adding pillaring molecules between the layers to increase the interlayer spacing. Vanadium oxide xerogels possess attractive capacities but suffer from significant capacity fade due to distortion of the crystal structure. We hypothesize that the pillars will enhance thermal and mechanical stability by reducing the strain on the structure and increasing lithium ion mobility, thereby increasing the cycle life and high rate capacities. Aluminum Keggin ions were used as pillaring agents for the vanadium oxide xerogels. X-ray diffraction showed an interlayer spacing increase from 1.14 to 1.32 nm after pillaring, consistent with the size of the keggin ions (~1.3 nm), while still maintaining the layered V2O5 xerogel crystalline structure (Figure 1). Elemental analysis indicated an aluminum loading of 9 wt% in the pillared material. The pillared materials also demonstrate increased thermal stability and rate capabilities during cycling in coin cells, with capacities over 60% higher than those of the unpillared V2O5 xerogel. Additionally, the pillared materials retained more capacity during cycling at C/2. Pillaring the layered vanadium oxide xerogels improved both capacity retention and battery lifetime. Figure 1. Diffraction patterns for V2O5 xerogel (a), pillared V2O5 xerogel (b), and pillared V2O5 xerogel after heat treatment in either air (c) or nitrogen (d). The dotted line is intended as a guide for the eye. Figure 1