Thickness Variation of Conductive Polymer Coatings on Si Anodes for the Improved Cycling Stability in Full Pouch Cells.

Si-dominant anodes for Li-ion batteries provide very high gravimetric and volumetric capacity but suffer from low cycling stability due to an unstable solid electrolyte interphase (SEI). In this work, we improved the cycling performance of Si/NCM pouch cells by coating the Si anodes with the conductive polymer poly(3,4-ethylenedioxythiophene) (PEDOT) prior to cell assembly via an electropolymerization process. The thicknesses of the PEDOT coatings could be adjusted by a facile process parameter variation. Glow-discharge optical emission spectroscopy was used to determine the coating thicknesses on the electrodes prior to the cell assembly. During electrochemical testing, improvements were observed closely linked to the PEDOT coating thickness. Specifically, thinner PEDOT coatings exhibited a higher capacity retention and lower internal resistance in the corresponding pouch cells. For the thinnest coatings, the cell lifetime was 18% higher compared to that of uncoated Si anodes. Postmortem analyses via X-ray photoelectron spectroscopy and cross-sectional scanning electron microscopy revealed a better-maintained microstructure and a chemically different SEI for the PEDOT-coated anodes.

The Optimal Amount of Lithium Difluorophosphate as an Additive for Si-Dominant Anodes in an Application-Oriented Setup.

Fluoroethylene carbonate (FEC) and vinylene carbonate (VC) are considered the most effective electrolyte additives for improving the solid electrolyte interphase (SEI) of Si-containing anodes while lithium difluorophosphate (LiDFP) is known to improve the interphases of cathode materials and graphite. Here, we combine VC, FEC, and different amounts of LiDFP in a highly-concentrated electrolyte to investigate the effect on Si-dominant anodes in detail. Cycle life tests, electrochemical impedance spectroscopy and rate tests with anode potential monitoring were conducted in Si/NCM pouch cells. The results reveal that adding LiDFP to the electrolyte improves all performance criteria of the full cells, with a concentration of 1 wt% being the optimal value for most cases. Post-mortem analyses using scanning electron microscopy and x-ray photoelectron spectroscopy showed that a more beneficial SEI film was formed for higher LiDFP concentrations, which led to less decomposition of electrolyte components and a better-maintained anode microstructure.

Coupled reaction equilibria enable the light-driven formation of metal-functionalized molecular vanadium oxides.

The introduction of metal sites into molecular metal oxides, so-called polyoxometalates, is key for tuning their structure and reactivity. The complex mechanisms which govern metal-functionalization of polyoxometalates are still poorly understood. Here, we report a coupled set of light-dependent and light-independent reaction equilibria controlling the mono- and di-metal-functionalization of a prototype molecular vanadium oxide cluster. Comprehensive mechanistic analyses show that coordination of a Mg2+ ion to the species {(NMe2H2)2[VV12O32Cl]}3- results in formation of the mono-functionalized {(NMe2H2)[(MgCl)VV12O32Cl]}3- with simultaneous release of a NMe2H2+ placeholder cation. Irradiation of this species with visible light results in one-electron reduction of the vanadate, exchange of the second NMe2H2+ with Mg2+, and formation/crystallization of the di-metal-functionalized [(MgCl)2VIVVV11O32Cl]4-. Mechanistic studies show how stimuli such as light or competing cations affect the coupled equilibria. Transfer of this synthetic concept to other metal cations is also demonstrated, highlighting the versatility of the approach.

Stabilizing Decavanadate Cluster as Electrode Material in Sodium and Lithium-ion Batteries.

Decavanadate ([V10 O28 ]6- , {V10 }) clusters are a potential electrode material for lithium and post-lithium batteries; however, their low stability due to the solubility in liquid organic electrolytes has been challenging. These molecular clusters are also prone to transform into solid-state oxides at a moderate temperature needed in the typical electrode fabrication process. Hence, controlling the solubility and improving the thermal stability of compounds are essential to make them more viable options for use as battery electrodes. This study shows a crystal engineering approach to stabilize the cluster with organic guanidinium (Gdm+ ) cation through the hydrogen-bonding interactions between the amino groups of the cation and the anion. The comparison of solubility and thermal stability of the Gdm{V10 } with another cluster bearing tetrabutylammonium (Tba+ ) cation reveals the better stability of cation-anion assembly in the former than the latter. As a result, the Gdm{V10 } delivers better rate capability and cycling stability than Tba{V10 } when tested as anode material in a half-cell configuration of a sodium-ion battery. Finally, the performance of the Gdm{V10 } anode is also investigated in a lithium-ion battery full cell with LiFePO4 cathode.

Reversible Electrodeposition of Potassium-bridged Molecular Vanadium Oxides: A New Approach Towards Multi-Electron Storage.

Molecular metal oxides, so-called polyoxometalates (POMs), have shown outstanding performance as catalysts and lately attracted interest as materials in energy conversion and storage systems due to their capability of storing and exchanging multiple electrons. Here, we report the first example of redox-driven reversible electrodeposition of molecular vanadium oxide clusters, leading to the formation of thin films. The detailed investigation of the deposition mechanism reveals that the reversibility is dependent on the reduction potential. Correlating electrochemical quartz microbalance studies with X-ray photoelectron spectroscopy (XPS) data gave insight into the redox chemistry and oxidation states of vanadium in the deposited films in dependence on the potential window. A multi-electron reduction of the polyoxovanadate cluster, which facilitates the potassium (K+ ) cation-assisted reversible formation of potassium vanadium oxide thin films was confirmed. At anodic potentials, re-oxidation of the polyoxovanadate and complete stripping of the thin film is observed for films deposited at potentials more positive than -500 mV vs. Ag/Ag+ , while electrodeposition at more negative cathodic potential reduces the electrochemical reversibility of the process and increases the stripping overpotential. As proof of principle, we demonstrate the electrochemical performance of the deposited films for potential use in potassium-ion batteries.

Cation-controlled capture of polyoxovanadate-based organic-inorganic 1D architectures.

Metal cations are used to control the selective crystallization of organic-inorganic supramolecular polymers. Two complementary monomers, a dodecanuclear vanadate [V12O32(NO3)]5- and the organic macrocycle cyclen assemble into hybrid host-guest aggregates. In the presence of Ba2+ or La3+, supramolecular polymerization and crystallization is driven by a complex interplay of cyclene protonation, hydrogen-bonding and electrostatics.

A photosensitizer-polyoxometalate dyad that enables the decoupling of light and dark reactions for delayed on-demand solar hydrogen production.

Decoupling the production of solar hydrogen from the diurnal cycle is a key challenge in solar energy conversion, the success of which could lead to sustainable energy schemes capable of delivering H2 independent of the time of day. Here, we report a fully integrated photochemical molecular dyad composed of a ruthenium-complex photosensitizer covalently linked to a Dawson polyoxometalate that acts as an electron-storage site and hydrogen-evolving catalyst. Visible-light irradiation of the system in solution leads to charge separation and electron storage on the polyoxometalate, effectively resulting in a liquid fuel. In contrast to related, earlier dyads, this system enables the harvesting, storage and delayed release of solar energy. On-demand hydrogen release is possible by adding a proton donor to the dyad solution. The system is a minimal molecular model for artificial photosynthesis and enables the spatial and temporal separation of light absorption, fuel storage and hydrogen release.

A General Access Route to High-Nuclearity, Metal-Functionalized Molecular Vanadium Oxides.

Molecular metal oxides are key materials in diverse fields like energy storage and conversion, molecular magnetism and as model systems for solid-state metal oxides. To improve their performance and increase the variety of accessible motifs, new synthetic approaches are necessary. Herein, we report a universal, new precursor to access different metal-functionalized polyoxovanadate (POV) clusters. The precursor is synthesized by a novel solid-state thermal treatment procedure. Solution-phase test reactions at room temperature and pressure show that reaction of the precursor with various metal nitrate salts gives access to a range of metal-functionalized POVs. The first nitrate-templated molecular calcium vanadate cluster is reported. We show that this precursor could open new access routes to POV components for molecular magnetism, energy technologies or catalysis.

Covalent Linkage of BODIPY-Photosensitizers to Anderson-Type Polyoxometalates Using CLICK Chemistry.

The covalent attachment of molecular photosensitizers (PS) to polyoxometalates (POMs) opens new pathways to PS-POM dyads for light-driven charge-transfer and charge-storage. Here, we report a synthetic route for the covalent linkage of BODIPY-dyes to Anderson-type polyoxomolybdates by using CLICK chemistry (i. e. copper-catalyzed azide-alkyne cycloaddition, CuAAC). Photophysical properties of the dyad were investigated by combined experimental and theoretical methods and highlight the role of both sub-components for the charge-separation properties. The study demonstrates how CLICK chemistry can be used for the versatile linkage of organic functional units to molecular metal oxide clusters.

Effect of Heterometal-Functionalization and Template Exchange on the Redox Chemistry of Molecular Vanadium Oxides.

Polyoxometalates (POMs) have emerged as material of interest in many applications such as energy storage and conversion due to their redox activity and molecularly defined structure. However, especially for polyoxovanadates a lack of understanding between structural modifications and physicochemical properties remains. The present study leverages a lacunary dodecavanadate to systematically investigate the electronic effect of heterometal functionalization. While structural distortion affects the stability of the cluster, the redox potentials correlate with the overall cluster charge. Furthermore, we report the first bromide-templated analogue of this cluster family. While the halide anion is crucial for the formation of the cluster, no major effect on the electrochemical properties is observed. By improving the understanding of structure-property relationship in this work, we hope to enable a more predictable tuning of redox-properties of polyoxovandates.

Electrocatalytic Oxygen Evolution by Hierarchically Structured Cobalt-Iron Composites.

The development of scalable routes to highly active and efficient oxygen evolution reaction (OER) electrocatalysts based on earth-abundant materials is crucial for post-fossil fuel energy schemes. Here, we demonstrate how commercial copper foam electrodes can be functionalized for water oxidation using a facile electrodeposition process. The resulting composite electrode features hierarchically structured cobalt-iron-based catalyst particles, which offer channel-like structures for the transport of electrolyte and release of oxygen gas bubbles. We report high electrocatalytic OER performance as demonstrated by high current densities at low overpotentials (293 mV at j = 50 mA cm-2) and long-term stability under technologically relevant alkaline conditions (>24 h in 1.0 M aqueous KOH).

Molecular Vanadium Oxides for Energy Conversion and Energy Storage: Current Trends and Emerging Opportunities.

Molecular vanadium oxides, or polyoxovanadates (POVs), have recently emerged as a new class of molecular energy conversion/storage materials, which combine diverse, chemically tunable redox behavior and reversible multielectron storage capabilities. This Review explores current challenges, major breakthroughs, and future opportunities in the use of POVs for energy conversion and storage. The reactivity, advantages, and limitations of POVs are explored, with a focus on their use in lithium and post-lithium-ion batteries, redox-flow batteries, and light-driven energy conversion. Finally, emerging themes and new research directions are critically assessed to provide inspiration for how this promising materials class can advance research in sustainable energy technologies.

Electronic Consequences of Ligand Substitution at Heterometal Centers in Polyoxovanadium Clusters: Controlling the Redox Properties through Heterometal Coordination Number.

The rational control of the electrochemical properties of polyoxovanadate-alkoxide clusters is dependent on understanding the influence of various synthetic modifications on the overall redox processes of these systems. In this work, the electronic consequences of ligand substitution at the heteroion in a heterometal-functionalized cluster was examined. The redox properties of [V5 O6 (OCH3 )12 FeCl] (1-[V5 FeCl]) and [V5 O6 (OCH3 )12 Fe]X (2-[V5 Fe]X; X=ClO4 , OTf) were compared in order to assess the effects of changing the coordination environment around the iron center on the electrochemical properties of the cluster. Coordination of a chloride anion to iron leads to an anodic shift in redox events. Theoretical modelling of the electronic structure of these heterometal-functionalized clusters reveals that differences in the redox profiles of 1-[V5 FeCl] and 2-[V5 Fe]X arise from changes in the number of ligands surrounding the iron center (e.g., 6-coordinate vs. 5-coordinate). Specifically, binding of the chloride to the sixth coordination site appears to change the orbital interaction between the iron and the delocalized electronic structure of the mixed-valent polyoxovanadate core. Tuning the heterometal coordination environment can therefore be used to modulate the redox properties of the whole cluster.

Redox-inactive ions control the redox-activity of molecular vanadium oxides.

Polyoxometalates are key materials for energy conversion and storage due to their unique chemical tunability and electrochemical reactivity. Herein, we report that functionalization of molecular vanadium oxides, polyoxovanadates, with redox-inert Ca2+ cations leads to a significant increase in their electron storage capabilities. The electrochemical performance of the Ca2+-functionalized dodecavanadate [Ca2V12O32Cl(DMF)3]2- (={Ca 2 V 12 }) was thus compared with that of the precursor compound (H2NMe2)2[V12O32Cl]3- (={V 12 }). {Ca 2 V 12 } can store up to five electrons per cluster, while {V 12 } only shows one reversible redox transition. In initial studies, we demonstrated that {Ca 2 V 12 } can be used as an active material in lithium-ion cathodes. Our results show how redox-inert cations can be used as structural and electrostatic stabilizers, leading to major changes in the redox-chemistry of polyoxovanadates.

Bottom-up Design of Bimetallic Cobalt-Molybdenum Carbides/Oxides for Overall Water Splitting.

Earth-abundant transition-metal-based catalysts for electrochemical water splitting are critical for sustainable energy schemes. In this work, we use a rational design method for the synthesis of ultrasmall and highly dispersed bimetallic CoMo carbide/oxide particles deposited on graphene oxide. Thermal conversion of the molecular precursors [H3 PMo12 O40 ], Co(OAc)2 ⋅4 H2 O and melamine in the presence of graphene oxide gives the mixed carbide/oxide (Co6 Mo6 C2 /Co2 Mo3 O8 ) nanoparticle composite deposited on highly dispersed, N,P-doped carbon. The resulting composite shows outstanding electrocatalytic water-splitting activity for both the oxygen evolution and hydrogen evolution reaction, and superior performance to reference samples including commercial 20 % Pt/C & IrO2 . Electrochemical and other materials analyses indicate that Co6 Mo6 C2 is the main active phase in the composite, and the N,P-doping of the carbon matrix increases the catalytic activity. The facile design could in principle be extended to multiple bimetallic catalyst classes by tuning of the molecular metal oxide precursor.

Water Purification and Microplastics Removal Using Magnetic Polyoxometalate-Supported Ionic Liquid Phases (magPOM-SILPs).

Filtration is an established water-purification technology. However, due to low flow rates, the filtration of large volumes of water is often not practical. Herein, we report an alternative purification approach in which a magnetic nanoparticle composite is used to remove organic, inorganic, microbial, and microplastics pollutants from water. The composite is based on a polyoxometalate ionic liquid (POM-IL) adsorbed onto magnetic microporous core-shell Fe2 O3 /SiO2 particles, giving a magnetic POM-supported ionic liquid phase (magPOM-SILP). Efficient, often quantitative removal of several typical surface water pollutants is reported together with facile removal of the particles using a permanent magnet. Tuning of the composite components could lead to new materials for centralized and decentralized water purification systems.

Reply to Comment on Stabilization of Low-Valent Iron(I) in a High-Valent Vanadium(V) Oxide Cluster.

The authors of the Communication "Stabilization of Low-Valent Iron(I) in a High-Valent Vanadium(V) Oxide Cluster" reply to a Comment by Dr. Sproules, who offered an alternative interpretation of the metal oxidation states in the two electron reduced iron vanadate (NH2 Me2 )[(FeCl)V12 O32 Cl]4- .

Top-down synthesis of polyoxometalate-like sub-nanometer molybdenum-oxo clusters as high-performance electrocatalysts.

The top-down fabrication of catalytically active molecular metal oxide anions, or polyoxometalates, is virtually unexplored, although these materials offer unique possibilities, for catalysis, energy conversion and storage. Here, we report a novel top-down route, which enables the scalable synthesis and deposition of sub-nanometer molybdenum-oxo clusters on electrically conductive mesoporous carbon. The new approach uses a unique redox-cycling process to convert crystalline MoIVO2 particles into sub-nanometer molecular molybdenum-oxo clusters with a nuclearity of ∼1-20. The resulting molybdenum-oxo cluster/carbon composite shows outstanding, stable electrocatalytic performance for the oxygen reduction reaction with catalyst characteristics comparable to those of commercial Pt/C. This new material design could give access to a new class of highly reactive polyoxometalate-like metal oxo clusters as high-performance, earth abundant (electro-)catalysts.

From molecular to colloidal manganese vanadium oxides for water oxidation catalysis.

The spontaneous, sonication-driven conversion of a molecular manganese vanadium oxide water oxidation catalyst, (n-Bu4N)3[Mn4V4O17(OAc)3] × 3H2O, into colloidal manganese vanadium oxide particles (average particle size ca. 70 nm) together with their stability and chemical water oxidation activity is reported. The nanoparticulate metal oxide colloid (approximate composition: VMn5O10·ca. 6H2O·ca. 0.2nBu4N+) is formed spontaneously when the molecular precursor is sonicated in water. The particles show water oxidation activity when combined with CeIV as the oxidant, are stable even under highly acidic reaction conditions and can be recovered and reused.

Stabilization of Low-Valent Iron(I) in a High-Valent Vanadium(V) Oxide Cluster.

Low-valent iron centers are critical intermediates in chemical and bio-chemical processes. Herein, we show the first example of a low-valent FeI center stabilized in a high-valent polyoxometalate framework. Electrochemical studies show that the FeIII -functionalized molecular vanadium(V) oxide (DMA)[FeIII ClVV12 O32 Cl]3- (DMA=dimethylammonium) features two well-defined, reversible, iron-based electrochemical reductions which cleanly yield the FeI species (DMA)[FeI ClVV12 O32 Cl]5- . Experimental and theoretical studies including electron paramagnetic resonance spectroscopy and density functional theory computations verify the formation of the FeI species. The study presents the first example for the seemingly paradoxical embedding of low-valent metal species in high-valent metal oxide anions and opens new avenues for reductive electron transfer catalysis by polyoxometalates.