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.

An ultrafast rechargeable aluminium-ion battery

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.

http://science.sciencemag.org/content/sci/351/6271/aad1920.full.pdf

Research opportunities to advance solar energy utilization

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.

Latest advances in supercapacitors: from new electrode materials to novel device designs.

Flow 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.

/pdf/a-metal-free-organic-inorganic-aqueous-flow-battery-396v1vayid.pdf

A metal-free organic–inorganic aqueous flow battery

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.

http://science.sciencemag.org/content/sci/361/6400/360.full.pdf

Inverse molecular design using machine learning: Generative models for matter engineering

We report the performance of a hydrogen–chlorine electrochemical cell with a chlorine electrode employing a low precious metal content alloy oxide electrocatalyst for the chlorine electrode: (Ru0.09Co0.91)3O4. The cell employs a commercial hydrogen fuel cell electrode and transports protons through a Nafion membrane in both galvanic and electrolytic mode. The peak galvanic power density exceeds 1 W cm−2, which is twice previous literature values. The precious metal loading of the chlorine electrode is below 0.15 mg Ru cm−2. Virtually no activation losses are observed, allowing the cell to run at nearly 0.4 W cm−2 at 90% voltage efficiency. We report the effects of fluid pressure, electrolyte acid concentration, and hydrogen-side humidification on overall cell performance and efficiency. A comparison of our results to the model of Rugolo et al. [Rugolo et al., J. Electrochem. Soc., 2012, 159, B133] points out directions for further performance enhancement. The performance reported here gives these devices promise for applications in carbon sequestration and grid-scale electrical energy storage.

A high power density, high efficiency hydrogen–chlorine regenerative fuel cell with a low precious metal content catalyst

We have demonstrated the performance of an aqueous redox flow battery composed of a negative electrode consisting of a redox couple between anthraquinone di-sulfonate and its corresponding hydroquinone, and a positive electrode consisting of a redox couple between hydrobromic acid and bromine. The peak power density is approximately 0.6 W/cm2. After 750 deep cycles, the average discharge capacity retention is 99.84% per cycle and the average current efficiency is 98.35%.

/pdf/cycling-of-a-quinone-bromide-flow-battery-for-large-scale-2ayzf9k3sn.pdf

Cycling of a Quinone-Bromide Flow Battery for Large-Scale Electrochemical Energy Storage

The invention provides an electrochemical cell based on a new chemistry for a flow battery for large scale, e.g., gridscale, electrical energy storage. Electrical energy is stored chemically at an electrochemical electrode by the protonation of small organic molecules called quinones to hydroquinones. The proton is provided by a complementary electrochemical reaction at the other electrode. These reactions are reversed to deliver electrical energy. A flow battery based on this concept can operate as a closed system. The flow battery architecture has scaling advantages over solid electrode batteries for large scale energy storage.

Small organic molecule based flow battery

Flow batteries are of interest for low-cost grid-scale electrical energy storage in the face of rising electricity production from intermittent renewables like wind and solar. We report on investigations of redox couples based on the reversible protonation of small organic molecules called quinones. These molecules can be very inexpensive and may therefore offer a low cost per kWh of electrical energy storage. Furthermore they are known to rapidly undergo oxidation and reduction with high reversibility under some conditions, suggesting the possibility of high current density operation, which could lead to low cost per kW. We report cyclic voltammetry measurements for 1,4-parabenzoquinone in neutral pH aqueous solution using a three-electrode setup. We report full fuel cell measurements as well, utilizing p-benzoquinone in an acidic solution as a positive electrode material and a hydrogen negative electrode, where current densities in excess of 240 mA cm -2 have been achieved to date. These initial results indicate that the quinone/hydroquinone redox couple is a promising candidate for use in redox flow batteries.

/pdf/novel-quinone-based-couples-for-flow-batteries-8jzo1kc87b.pdf

Brian Huskinson

Papers

A metal-free organic–inorganic aqueous flow battery

A high power density, high efficiency hydrogen–chlorine regenerative fuel cell with a low precious metal content catalyst

Cycling of a Quinone-Bromide Flow Battery for Large-Scale Electrochemical Energy Storage

Small organic molecule based flow battery

Novel Quinone-Based Couples for Flow Batteries