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Journal ArticleDOI

A metal-free organic–inorganic aqueous flow battery

09 Jan 2014-Nature (Nature Publishing Group)-Vol. 505, Iss: 7482, pp 195-198

TL;DR: This work describes a class of energy storage materials that exploits the favourable chemical and electrochemical properties of a family of molecules known as quinones, and demonstrates a metal-free flow battery based on the redox chemistry of 9,10-anthraquinone-2,7-disulphonic acid.

AbstractFlow batteries, in which the electro-active components are held in fluid form external to the battery itself, are attractive as a potential means for regulating the output of intermittent renewable sources of electricity; an aqueous flow battery based on inexpensive commodity chemicals is now reported that also has the virtue of enabling further improvement of battery performance through organic chemical design. Flow batteries differ from the conventional type in that the electro-active components of flow batteries are held in fluid form external to the battery itself, enabling such systems to store arbitrarily large amounts of energy. Flow batteries are therefore attractive as a potential means for regulating the output of intermittent sources of electricity such as wind or solar power. But an important limitation of most such systems is the abundance and cost of the electro-active materials. To overcome this limitation, Brian Huskinson and colleagues have developed an aqueous flow battery on the basis of inexpensive, non-metallic commodity chemicals, with the added advantage of enabling the tuning of key battery properties through chemical design. 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 output1,2. 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 form3,4,5. 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 electrocatalysts6,7. 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 chemicals8. 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.

Topics: Battery (electricity) (66%), Flow battery (66%), Energy storage (59%), Electricity generation (54%), Solar power (52%)

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Journal ArticleDOI
16 Apr 2015-Nature
TL;DR: A rechargeable aluminium battery with high-rate capability that uses an aluminium metal anode and a three-dimensional graphitic-foam cathode, found to enable fast anion diffusion and intercalation, and to withstand more than 7,500 cycles without capacity decay.
Abstract: An aluminium-ion battery is reported that can charge within one minute, and offers improved cycle life compared to previous devices; it operates through the electrochemical deposition and dissolution of aluminium at the anode, and the intercalation/de-intercalation of chloroaluminate anions into a novel graphitic-foam cathode. The low cost and useful electrical properties of aluminium suggest that rechargeable Al-ion batteries could offer viable and safe battery technology, but problems with cathode materials, poor cycling performance and other complications have persisted. Here Hongjie Dai and colleagues describe an Al-ion battery that can charge within one minute and offers substantially improved cycle life with little decay in capacity compared to previous devices reported in the literature. The battery operates through the electrochemical deposition and dissolution of Al and intercalation/de-intercalation of chloroaluminate anions into a novel 3D graphitic foam cathode using a non-flammable ionic liquid electrolyte. The development of new rechargeable battery systems could fuel various energy applications, from personal electronics to grid storage1,2. Rechargeable aluminium-based batteries offer the possibilities of low cost and low flammability, together with three-electron-redox properties leading to high capacity3. However, research efforts over the past 30 years have encountered numerous problems, such as cathode material disintegration4, low cell discharge voltage (about 0.55 volts; ref. 5), capacitive behaviour without discharge voltage plateaus (1.1–0.2 volts6 or 1.8–0.8 volts7) and insufficient cycle life (less than 100 cycles) with rapid capacity decay (by 26–85 per cent over 100 cycles)4,5,6,7. Here we present a rechargeable aluminium battery with high-rate capability that uses an aluminium metal anode and a three-dimensional graphitic-foam cathode. The battery operates through the electrochemical deposition and dissolution of aluminium at the anode, and intercalation/de-intercalation of chloroaluminate anions in the graphite, using a non-flammable ionic liquid electrolyte. The cell exhibits well-defined discharge voltage plateaus near 2 volts, a specific capacity of about 70 mA h g–1 and a Coulombic efficiency of approximately 98 per cent. The cathode was found to enable fast anion diffusion and intercalation, affording charging times of around one minute with a current density of ~4,000 mA g–1 (equivalent to ~3,000 W kg–1), and to withstand more than 7,500 cycles without capacity decay.

1,442 citations


Journal ArticleDOI
22 Jan 2016-Science
TL;DR: Lewis reviews the status of solar thermal and solar fuels approaches for harnessing solar energy, as well as technology gaps for achieving cost-effective scalable deployment combined with storage technologies to provide reliable, dispatchable energy.
Abstract: Major developments, as well as remaining challenges and the associated research opportunities, are evaluated for three technologically distinct approaches to solar energy utilization: solar electricity, solar thermal, and solar fuels technologies. Much progress has been made, but research opportunities are still present for all approaches. Both evolutionary and revolutionary technology development, involving foundational research, applied research, learning by doing, demonstration projects, and deployment at scale will be needed to continue this technology-innovation ecosystem. Most of the approaches still offer the potential to provide much higher efficiencies, much lower costs, improved scalability, and new functionality, relative to the embodiments of solar energy-conversion systems that have been developed to date.

1,050 citations


Additional excerpts

  • ...Electrochemical couples being developed include aqueous vanadium as V, Zn-Br, V-Cr, Fe-Cr, or H2/Br2 systems (54), as well as quinonehydroquinone redox species (55)....

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Journal ArticleDOI
TL;DR: The state-of-the-art progress toward mechanisms, new materials, and novel device designs for supercapacitors is summarized and key technical challenges are highlighted regarding further research in this thriving field.
Abstract: Notably, many significant breakthroughs for a new generation of supercapacitors have been reported in recent years, related to theoretical understanding, material synthesis and device designs. Herein, we summarize the state-of-the-art progress toward mechanisms, new materials, and novel device designs for supercapacitors. Firstly, fundamental understanding of the mechanism is mainly focused on the relationship between the structural properties of electrode materials and their electrochemical performances based on some in situ characterization techniques and simulations. Secondly, some emerging electrode materials are discussed, including metal–organic frameworks (MOFs), covalent organic frameworks (COFs), MXenes, metal nitrides, black phosphorus, LaMnO3, and RbAg4I5/graphite. Thirdly, the device innovations for the next generation of supercapacitors are provided successively, mainly emphasizing flow supercapacitors, alternating current (AC) line-filtering supercapacitors, redox electrolyte enhanced supercapacitors, metal ion hybrid supercapacitors, micro-supercapacitors (fiber, plane and three-dimensional) and multifunctional supercapacitors including electrochromic supercapacitors, self-healing supercapacitors, piezoelectric supercapacitors, shape-memory supercapacitors, thermal self-protective supercapacitors, thermal self-charging supercapacitors, and photo self-charging supercapacitors. Finally, the future developments and key technical challenges are highlighted regarding further research in this thriving field.

995 citations


Journal ArticleDOI

690 citations


Journal ArticleDOI
27 Jul 2018-Science
TL;DR: Methods for achieving inverse design, which aims to discover tailored materials from the starting point of a particular desired functionality, are reviewed.
Abstract: The discovery of new materials can bring enormous societal and technological progress. In this context, exploring completely the large space of potential materials is computationally intractable. Here, we review methods for achieving inverse design, which aims to discover tailored materials from the starting point of a particular desired functionality. Recent advances from the rapidly growing field of artificial intelligence, mostly from the subfield of machine learning, have resulted in a fertile exchange of ideas, where approaches to inverse molecular design are being proposed and employed at a rapid pace. Among these, deep generative models have been applied to numerous classes of materials: rational design of prospective drugs, synthetic routes to organic compounds, and optimization of photovoltaics and redox flow batteries, as well as a variety of other solid-state materials.

688 citations


References
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Peter E. Blöchl1
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Abstract: An approach for electronic structure calculations is described that generalizes both the pseudopotential method and the linear augmented-plane-wave (LAPW) method in a natural way. The method allows high-quality first-principles molecular-dynamics calculations to be performed using the original fictitious Lagrangian approach of Car and Parrinello. Like the LAPW method it can be used to treat first-row and transition-metal elements with affordable effort and provides access to the full wave function. The augmentation procedure is generalized in that partial-wave expansions are not determined by the value and the derivative of the envelope function at some muffin-tin radius, but rather by the overlap with localized projector functions. The pseudopotential approach based on generalized separable pseudopotentials can be regained by a simple approximation.

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Abstract: The formal relationship between ultrasoft (US) Vanderbilt-type pseudopotentials and Bl\"ochl's projector augmented wave (PAW) method is derived. It is shown that the total energy functional for US pseudopotentials can be obtained by linearization of two terms in a slightly modified PAW total energy functional. The Hamilton operator, the forces, and the stress tensor are derived for this modified PAW functional. A simple way to implement the PAW method in existing plane-wave codes supporting US pseudopotentials is pointed out. In addition, critical tests are presented to compare the accuracy and efficiency of the PAW and the US pseudopotential method with relaxed core all electron methods. These tests include small molecules $({\mathrm{H}}_{2}{,\mathrm{}\mathrm{H}}_{2}{\mathrm{O},\mathrm{}\mathrm{Li}}_{2}{,\mathrm{}\mathrm{N}}_{2}{,\mathrm{}\mathrm{F}}_{2}{,\mathrm{}\mathrm{BF}}_{3}{,\mathrm{}\mathrm{SiF}}_{4})$ and several bulk systems (diamond, Si, V, Li, Ca, ${\mathrm{CaF}}_{2},$ Fe, Co, Ni). Particular attention is paid to the bulk properties and magnetic energies of Fe, Co, and Ni.

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