Michael P. Marshak

A metal-free organic–inorganic aqueous flow battery

As the fraction of electricity generation from intermittent renewable sources—such as solar or wind—grows, the ability to store large amounts of electrical energy is of increasing importance. Solid-electrode batteries maintain discharge at peak power for far too short a time to fully regulate wind or solar power output. In contrast, flow batteries can independently scale the power (electrode area) and energy (arbitrarily large storage volume) components of the system by maintaining all of the electro-active species in fluid form. Wide-scale utilization of flow batteries is, however, limited by the abundance and cost of these materials, particularly those using redox-active metals and precious-metal electrocatalysts. Here we describe a class of energy storage materials that exploits the favourable chemical and electrochemical properties of a family of molecules known as quinones. The example we demonstrate is a metal-free flow battery based on the redox chemistry of 9,10-anthraquinone-2,7-disulphonic acid (AQDS). AQDS undergoes extremely rapid and reversible two-electron two-proton reduction on a glassy carbon electrode in sulphuric acid. An aqueous flow battery with inexpensive carbon electrodes, combining the quinone/hydroquinone couple with the Br2/Br− redox couple, yields a peak galvanic power density exceeding 0.6 W cm−2 at 1.3 A cm−2. Cycling of this quinone–bromide flow battery showed >99 per cent storage capacity retention per cycle. The organic anthraquinone species can be synthesized from inexpensive commodity chemicals. This organic approach permits tuning of important properties such as the reduction potential and solubility by adding functional groups: for example, we demonstrate that the addition of two hydroxy groups to AQDS increases the open circuit potential of the cell by 11% and we describe a pathway for further increases in cell voltage. The use of π-aromatic redox-active organic molecules instead of redox-active metals represents a new and promising direction for realizing massive electrical energy storage at greatly reduced cost.

Alkaline quinone flow battery

A solution for scalable-flow batteries Flow batteries, in which the redox active components are held in tanks separate from the active part of the cell, offer a scalable route for storing large quantities of energy. A challenge for their large-scale development is to avoid formulations that depend on toxic transition metal ions. Lin et al. show that quinones can be dissolved in alkaline solutions and coupled with ferricyanides to make a flow cell battery (see the Perspective by Perry). This gives scope for developing flow cells with very low costs, high efficiencies at practical power densities, simplicity of operation, and inherent safety. Science, this issue p. 1529; see also p. 1452 A flow battery is designed with low-toxicity, Earth-abundant materials. [Also see Perspective by Perry] Storage of photovoltaic and wind electricity in batteries could solve the mismatch problem between the intermittent supply of these renewable resources and variable demand. Flow batteries permit more economical long-duration discharge than solid-electrode batteries by using liquid electrolytes stored outside of the battery. We report an alkaline flow battery based on redox-active organic molecules that are composed entirely of Earth-abundant elements and are nontoxic, nonflammable, and safe for use in residential and commercial environments. The battery operates efficiently with high power density near room temperature. These results demonstrate the stability and performance of redox-active organic molecules in alkaline flow batteries, potentially enabling cost-effective stationary storage of renewable energy.

Cobalt in a bis-β-diketiminate environment.

The reaction of Co(2)(mesityl)(4) with acetonitrile leads to the formation of a planar, low spin, bis-β-diketiminate cobalt(II) complex, (1-mesitylbutane-1,3-diimine)(2)Co (1). EPR spectroscopy, magnetic studies, and DFT calculations reveal the Co(II) ion to reside in a tetragonal ligand field with a (2)B(2)(d(yz))(1) ground state electronic configuration. Oxidation of 1 with ferrocenium hexafluorophosphate furnishes (1-mesitylbutane-1,3-diimine)(2)Co(THF)(2)PF(6) (2). The absence of significant changes in the metal-ligand bond metrics of the X-ray crystal structures of 1 and 2 supports ligand participation in the oxidation event. Moreover, no significant changes in C-C or C-N bond lengths are observed by X-ray crystallography upon oxidation of a β-diketiminate ligand, in contrast to typical redox noninnocent ligand platforms.

Chromium(IV) Siloxide

The reaction of Na(OSi(t)Bu(2)Me) with CrCl(3) yields solid [Cr(OSi(t)Bu(2)Me)(3)](n) (1), which can be crystallized in the presence of excess Na(OSi(t)Bu(2)Me) to yield [Na(THF)][Cr(OSi(t)Bu(2)Me)(4)] (2). This complex is oxidized to yield Cr(OSi(t)Bu(2)Me)(4) (3), a crystalline chromium(IV) siloxide complex that is air- and moisture-stable. Electronic spectroscopic analysis of the absorption spectrum of 3 indicates a particularly weak ligand field (Δ(T) = 7940 cm(-1)) and covalent Cr-O bonding. 3 provides the first structural and spectroscopic characterization of a homoleptic chromium(IV) siloxide complex and provides a benchmark for tetrahedral chromium(IV) ions residing in solid oxide lattices.

Bulky β-Diketones Enabling New Lewis Acidic Ligand Platforms

The synthesis of a sterically encumbered β-diketone ligand (Aracac) substituted with 2,6-(2,4,6-Me3C6H2)2C6H3 is described. Coordination complexes of the type M(Aracac)2Cl(solv) (M = Ti, V, Cr; solv = THF, CH3CN) were prepared by the reaction of Aracac with MCl3 (M = V, Cr) or with TiCl4 to generate Ti(Aracac)2Cl2, followed by reduction. These complexes show a trend of alternating the cis/trans geometric preference with increasing dn electron count (n = 0, 1, 2, 3), which is rationalized in part by the unusual ability of β-diketonates to behave as either a weak π donor or a π acceptor in the cis and trans geometries, respectively. In this way, the bis-β-diketonate platform can accommodate the varying electronic demands of the coordinated metal ion. These results demonstrate the ability to limit the coordination of β-diketonates on metal complexes for the first time, providing a chemically robust and coordinatively versatile platform for mechanistic investigations, metal functionalization, and improved catalyst design.