Tunable metal hydroxide-organic frameworks for catalysing oxygen evolution.

The oxygen evolution reaction is central to making chemicals and energy carriers using electrons. Combining the great tunability of enzymatic systems with known oxide-based catalysts can create breakthrough opportunities to achieve both high activity and stability. Here we report a series of metal hydroxide-organic frameworks (MHOFs) synthesized by transforming layered hydroxides into two-dimensional sheets crosslinked using aromatic carboxylate linkers. MHOFs act as a tunable catalytic platform for the oxygen evolution reaction, where the π-π interactions between adjacent stacked linkers dictate stability, while the nature of transition metals in the hydroxides modulates catalytic activity. Substituting Ni-based MHOFs with acidic cations or electron-withdrawing linkers enhances oxygen evolution reaction activity by over three orders of magnitude per metal site, with Fe substitution achieving a mass activity of 80 A [Formula: see text] at 0.3 V overpotential for 20 h. Density functional theory calculations correlate the enhanced oxygen evolution reaction activity with the MHOF-based modulation of Ni redox and the optimized binding of oxygenated intermediates.

Interrogation of the Reaction Mechanism in a Na-O2 Battery Using In Situ Transmission Electron Microscopy.

Critical factors that govern the composition and morphology of discharge products are largely unknown for Na-O2 batteries. Here we report a reversible oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) process in a sodium-oxygen battery observed using in situ environmental-transmission electron microscopy (TEM) experiment. The reaction mechanism and phase evolution are probed using in situ electron diffraction and TEM imaging. The reversible ORR and OER cycling lies upon the nanosized copper clusters that were formed in situ by sodiation of CuS. In situ electron diffraction revealed the formation of NaO2 initially, which then disproportionated into orthorhombic and hexagonal Na2O2 and O2. Na2O2 was the major final ORR product that uniformly covered the whole wire-shape cathode. This uniform product morphology largely increased the application feasibility of Na-O2 batteries in industry. In the following OER process, the Na2O2 transformed to NaO2, which resulted in volume expansion at first, and then the NaO2 decomposed to sodium ions and O2 gas. Galvanostatic charge/discharge profiles of CuS in real Na-O2 cells revealed a maximum capacity over 3 mAh cm-2 with a discharge cutoff voltage of 1.8 V and high cycling stability. The nanosized copper catalyst plays a dominating role in controlling the morphology, chemical composition of discharge products, and reversibility of this Na-O2 battery. Our finding shines light on the exploration of effective catalysts for the Na-O2 battery.

An N-Heterocyclic-Carbene-Derived Distonic Radical Cation.

We present the discovery of a novel radical cation formed through one-electron oxidation of an N-heterocyclic carbene-carbodiimide (NHC-CDI) zwitterionic adduct. This compound possesses a distonic electronic structure (spatially separate spin and charge regions) and displays persistence under ambient conditions. We demonstrate its application in a redox-flow battery exhibiting minimal voltage hysteresis, a flat voltage plateau, high Coulombic efficiency, and no performance decay for at least 100 cycles. The chemical tunability of NHCs and CDIs suggests that this approach could provide a general entry to redox-active NHC-CDI adducts and their persistent radical ions for various applications.

Molecular Design of Stable Sulfamide- and Sulfonamide-based Electrolytes for Aprotic Li-O2 Batteries.

Electrolyte instability is one of the most challenging impediments to enabling Lithium-Oxygen (Li-O2) batteries for practical use. The use of physical organic chemistry principles to rationally design new molecular components may enable the discovery of electrolytes with stability profiles that cannot be achieved with existing formulations. Here, we report on the development of sulfamide- and sulfonamide-based small molecules that are liquids at room temperature, capable of dissolving reasonably high concentration of Li salts (e.g., LiTFSI), and are exceptionally stable under the harsh chemical and electrochemical conditions of aprotic Li-O2 batteries. In particular, N,N-dimethyl-trifluoromethanesulfonamide was found to be highly resistant to chemical degradation by peroxide and superoxide, stable against electrochemical oxidation up to 4.5 VLi, and stable for > 90 cycles in a Li-O2 cell when cycled at < 4.2 VLi. This study provides guiding principles for the development of next-generation electrolyte components based on sulfamides and sulfonamides.

Synergistic oxygen reduction of dual redox catalysts boosting the power of lithium-air battery.

The development of rechargeable Li-air batteries has been confronted by the critical challenges of large overpotential loss, low achievable capacity, and prohibitively poor cycling and power performance. Surface passivation and pore clogging of the cathode due to the formation of Li2O2 during discharge result in sluggish interfacial charge transfer and have an impact on the mass transport of Li+ ions and O2 in the electrode, consequently giving rise to large voltage hysteresis and premature termination of discharge with low power performance. Here we report a redox flow lithium-oxygen cell with a modified redox electrolyte to tackle these issues. With the assistance of redox mediators, the cell presents substantially enhanced power performance in O2 and dry air during discharge. Through in situ spectroelectrochemical measurements and theoretical calculations, an oxygen reduction intermediate was unequivocally identified. By judiciously optimizing the redox electrolyte, the cell operates at near complete utilization of Li metal upon multiple refueling. The redox flow lithium-oxygen cell demonstrated here is envisaged to provide a pragmatic approach for the implementation of lithium-oxygen battery chemistry and to pave the way for advanced large-scale energy storage.

Unleashing the Power and Energy of LiFePO4-Based Redox Flow Lithium Battery with a Bifunctional Redox Mediator.

Redox flow batteries, despite great operation flexibility and scalability for large-scale energy storage, suffer from low energy density and relatively high cost as compared to the state-of-the-art Li-ion batteries. Here we report a redox flow lithium battery, which operates via the redox targeting reactions of LiFePO4 with a bifunctional redox mediator, 2,3,5,6-tetramethyl-p-phenylenediamine, and presents superb energy density as the Li-ion battery and system flexibility as the redox flow battery. The battery has achieved a tank energy density as high as 1023 Wh/L, power density of 61 mW/cm2, and voltage efficiency of 91%. Operando X-ray absorption near-edge structure measurements were conducted to monitor the evolution of LiFePO4, which provides insightful information on the redox targeting process, critical to the device operation and optimization.

Proton enhanced dynamic battery chemistry for aprotic lithium-oxygen batteries.

Water contamination is generally considered to be detrimental to the performance of aprotic lithium-air batteries, whereas this view is challenged by recent contrasting observations. This has provoked a range of discussions on the role of water and its impact on batteries. In this work, a distinct battery chemistry that prevails in water-contaminated aprotic lithium-oxygen batteries is revealed. Both lithium ions and protons are found to be involved in the oxygen reduction and evolution reactions, and lithium hydroperoxide and lithium hydroxide are identified as predominant discharge products. The crystallographic and spectroscopic characteristics of lithium hydroperoxide monohydrate are scrutinized both experimentally and theoretically. Intriguingly, the reaction of lithium hydroperoxide with triiodide exhibits a faster kinetics, which enables a considerably lower overpotential during the charging process. The battery chemistry unveiled in this mechanistic study could provide important insights into the understanding of nominally aprotic lithium-oxygen batteries and help to tackle the critical issues confronted.

High-energy density nonaqueous all redox flow lithium battery enabled with a polymeric membrane.

Redox flow batteries (RFBs) are considered one of the most promising large-scale energy storage technologies. However, conventional RFBs suffer from low energy density due to the low solubility of the active materials in electrolyte. On the basis of the redox targeting reactions of battery materials, the redox flow lithium battery (RFLB) demonstrated in this report presents a disruptive approach to drastically enhancing the energy density of flow batteries. With LiFePO4 and TiO2 as the cathodic and anodic Li storage materials, respectively, the tank energy density of RFLB could reach ~500 watt-hours per liter (50% porosity), which is 10 times higher than that of a vanadium redox flow battery. The cell exhibits good electrochemical performance under a prolonged cycling test. Our prototype RFLB full cell paves the way toward the development of a new generation of flow batteries for large-scale energy storage.

Dual redox catalysts for oxygen reduction and evolution reactions: towards a redox flow Li-O2 battery.

A redox flow lithium-oxygen battery (RFLOB) by using soluble redox catalysts with good performance was demonstrated for large-scale energy storage. The new device enables the reversible formation and decomposition of Li2O2 via redox targeting reactions in a gas diffusion tank, spatially separated from the electrode, which obviates the passivation and pore clogging of the cathode.

Catalyst engineering for lithium ion batteries: the catalytic role of Ge in enhancing the electrochemical performance of SnO2(GeO2)0.13/G anodes.

The catalytic role of germanium (Ge) was investigated to improve the electrochemical performance of tin dioxide grown on graphene (SnO(2)/G) nanocomposites as an anode material of lithium ion batteries (LIBs). Germanium dioxide (GeO(20) and SnO(2) nanoparticles (<10 nm) were uniformly anchored on the graphene sheets via a simple single-step hydrothermal method. The synthesized SnO(2)(GeO(2))0.13/G nanocomposites can deliver a capacity of 1200 mA h g(-1) at a current density of 100 mA g(-1), which is much higher than the traditional theoretical specific capacity of such nanocomposites (∼ 702 mA h g(-1)). More importantly, the SnO(2)(GeO(2))0.13/G nanocomposites exhibited an improved rate, large current capability (885 mA h g(-1) at a discharge current of 2000 mA g(-1)) and excellent long cycling stability (almost 100% retention after 600 cycles). The enhanced electrochemical performance was attributed to the catalytic effect of Ge, which enabled the reversible reaction of metals (Sn and Ge) to metals oxide (SnO(2) and GeO(2)) during the charge/discharge processes. Our demonstrated approach towards nanocomposite catalyst engineering opens new avenues for next-generation high-performance rechargeable Li-ion batteries anode materials.

3D graphene supported MoO2 for high performance binder-free lithium ion battery.

In this work, we report the synthesis of MoO2 nanoparticles grown on three dimensional graphene (3DG) via the reduction of α-MoO3 nanobelts through a facile chemical vapor deposition (CVD) approach under argon protection gas environment. In this synthesis approach, the presence of hydrophobic 3DG promoted the Volmer-Weber growth of MoO2 nanoparticles (30-60 nm). The as-prepared MoO2-3DG nanocomposite was directly used as a binder-free anode electrode for lithium ion batteries (LIBs) without additives and exhibited excellent electrochemical performance. It delivered high reversible capacities of 975.4 mA h g(-1) and 537.3 mA h g(-1) at the current densities of 50 and 1000 mA g(-1), respectively. Moreover, the electrode also showed an increased capacity from 763.7 mA h g(-1) to 986.9 mA h g(-1) after 150 discharge and charge cycles at a current density of 200 mA g(-1). The enhanced electrochemical performance of MoO2-3DG nanocomposite electrode may be attributed to the synergistic effects of MoO2 nanoparticles and 3DG layers. This facile CVD synthesis process presents a feasible route for large-scale production of high performance, environmentally friendly electrode. In addition, this process also has the potential of being utilized in other materials for energy storage devices application.