William D. McCulloch

Aqueous Lithium–Iodine Solar Flow Battery for the Simultaneous Conversion and Storage of Solar Energy

Integrating both photoelectric-conversion and energy-storage functions into one device allows for the more efficient solar energy usage. Here we demonstrate the concept of an aqueous lithium-iodine (Li-I) solar flow battery (SFB) by incorporation of a built-in dye-sensitized TiO2 photoelectrode in a Li-I redox flow battery via linkage of an I3(-)/I(-) based catholyte, for the simultaneous conversion and storage of solar energy. During the photoassisted charging process, I(-) ions are photoelectrochemically oxidized to I3(-), harvesting solar energy and storing it as chemical energy. The Li-I SFB can be charged at a voltage of 2.90 V under 1 sun AM 1.5 illumination, which is lower than its discharging voltage of 3.30 V. The charging voltage reduction translates to energy savings of close to 20% compared to conventional Li-I batteries. This concept also serves as a guiding design that can be extended to other metal-redox flow battery systems.

Solar-powered electrochemical energy storage: an alternative to solar fuels

Because of the intermittent nature of solar radiation, being able to simultaneously convert and store solar energy is a significant advance for efficiently harnessing solar energy. Solar fuels have already been recognized as a promising method towards this goal and have attracted tremendous research interest recently. Alternatively, this goal can also be achieved by using the solar-powered electrochemical energy storage (SPEES) strategy, which integrates a photoelectrochemical cell and an electrochemical cell into a single device. The integrated device is able to harvest solar energy and store it in situ within the device via a photocharging process and also distribute the energy as electric power when needed. This essay reviews the past SPEES research and analyzes its future prospects with a special emphasis on chemical design and material choices. We hope that the article will help draw more research attention to this field and stimulate additional exciting investigations toward more efficient solar energy utilization.

MoS2 as a long-life host material for potassium ion intercalation

Electrochemical potassium ion intercalation into two-dimensional layered MoS2 was studied for the first time for potential applications in the anode in potassium-based batteries. X-ray diffraction analysis indicated that an intercalated potassium compound, hexagonal K0.4MoS2, formed during the intercalation process. Despite the size of K+, MoS2 was a long-life host for repetitive potassium ion intercalation and de-intercalation with a capacity retention of 97.5% after 200 cycles. The diffusion coefficient of the K+ ions in KxMoS2 was calculated based on the Randles–Sevcik equation. A higher K+ intercalation ratio not only encountered a much slower K+ diffusion rate in MoS2, but also induced MoS2 reduction. This study shows that metal dichalcogenides are promising potassium anode materials for emerging K-ion, K-O2, and K-S batteries.

Reversible Dendrite-Free Potassium Plating and Stripping Electrochemistry for Potassium Secondary Batteries

Rechargeable potassium metal batteries have recently emerged as alternative energy storage devices beyond lithium-ion batteries. However, potassium metal anodes suffer from poor reversibility during plating and stripping processes due to their high reactivity and unstable solid electrolyte interphase (SEI). Herein, it is reported for the first time that a potassium bis(fluoroslufonyl)imide (KFSI)-dimethoxyethane (DME) electrolyte forms a uniform SEI on the surface of potassium enabling reversible potassium plating/stripping electrochemistry with high efficiency (∼99%) at ambient temperature. Furthermore, the superconcentrated KFSI-DME electrolyte shows excellent electrochemical stability up to 5 V (vs K/K+) which enables good compatibility with high-voltage cathodes. Full cells with potassium Prussian blue cathodes are demonstrated. Our work contributes toward the understanding of potassium plating/stripping electrochemistry and paves the way for the development of potassium metal battery technologies.

Layer-transferred MoS2/GaN PN diodes

Electrical and optical characterization of two-dimensional/three-dimensional (2D/3D) p-molybdenum disulfide/n-gallium nitride (p-MoS2/n-GaN) heterojunction diodes are reported. Devices were fabricated on high-quality, large-area p-MoS2 grown by chemical vapor deposition on sapphire substrates. The processed devices were transferred onto GaN/sapphire substrates, and the transferred films were characterized by X-ray diffraction (XRD) and atomic force microscopy (AFM). On-axis XRD spectra and surface topology obtained from AFM scans were consistent with previously grown high-quality, continuous MoS2 films. Current-voltage measurements of these diodes exhibited excellent rectification, and capacitance-voltage measurements were used to extract a conduction band offset of 0.23 eV for the transferred MoS2/GaN heterojunction. This conduction band offset was confirmed by internal photoemission measurements. The energy band lineup of the MoS2/GaN heterojunction is proposed here. This work demonstrates the potential...

Concentrated Electrolyte for the Sodium–Oxygen Battery: Solvation Structure and Improved Cycle Life

Alkali metal-oxygen batteries are of great interests for energy storage because of their unparalleled theoretical energy densities. Particularly attractive is the emerging Na-O2 battery because of the formation of superoxide as the discharge product. Dimethyl sulfoxide (DMSO) is a promising solvent for this battery but its instability towards Na makes it impractical in the Na-O2 battery. Herein we report the enhanced stability of Na in DMSO solutions containing concentrated sodium trifluoromethanesulfonimide (NaTFSI) salts (>3 mol kg-1 ). Raman spectra of NaTFSI/DMSO electrolytes and ab initio molecular dynamics simulation reveal the Na+ solvation number in DMSO and the formation of Na(DMSO)3 (TFSI)-like solvation structure. The majority of DMSO molecules solvating Na+ in concentrated solutions reduces the available free DMSO molecules that can react with Na and renders the TFSI anion decomposition, which protects Na from reacting with the electrolyte. Using these concentrated electrolytes, Na-O2 batteries can be cycled forming sodium superoxide (NaO2 ) as the sole discharge product with improved long cycle life, highlighting the beneficial role of concentrated electrolytes for Na-based batteries.

Probing Mechanisms for Inverse Correlation between Rate Performance and Capacity in K–O2 Batteries

Owing to the formation of potassium superoxide (K+ + O2 + e- = KO2), K-O2 batteries exhibit superior round-trip efficiency and considerable energy density in the absence of any electrocatalysts. For further improving the practical performance of K-O2 batteries, it is important to carry out a systematic study on parameters that control rate performance and capacity to comprehensively understand the limiting factors in superoxide-based metal-oxygen batteries. Herein, we investigate the influence of current density and oxygen diffusion on the nucleation, growth, and distribution of potassium superoxide (KO2) during the discharge process. It is observed that higher current results in smaller average sizes of KO2 crystals but a larger surface coverage on the carbon fiber electrode. As KO2 grows and covers the cathode surface, the discharge will eventually end due to depletion of the oxygen-approachable electrode surface. Additionally, higher current also induces a greater gradient of oxygen concentration in the porous carbon electrode, resulting in less efficient loading of the discharge product. These two factors explain the observed inverse correlation between current and capacity of K-O2 batteries. Lastly, we demonstrate a reduced graphene oxide-based K-O2 battery with a large specific capacity (up to 8400 mAh/gcarbon at a discharge rate of 1000 mA/gcarbon) and a long cycle life (over 200 cycles).

High current density 2D/3D MoS2/GaN Esaki tunnel diodes

The integration of two-dimensional materials such as transition metal dichalcogenides with bulk semiconductors offer interesting opportunities for 2D/3D heterojunction-based device structures without any constraints of lattice matching. By exploiting the favorable band alignment at the GaN/MoS2 heterojunction, an Esaki interband tunnel diode is demonstrated by transferring large area Nb-doped, p-type MoS2 onto heavily n-doped GaN. A peak current density of 446 A/cm2 with repeatable room temperature negative differential resistance, peak to valley current ratio of 1.2, and minimal hysteresis was measured in the MoS2/GaN non-epitaxial tunnel diode. A high current density of 1 kA/cm2 was measured in the Zener mode (reverse bias) at −1 V bias. The GaN/MoS2 tunnel junction was also modeled by treating MoS2 as a bulk semiconductor, and the electrostatics at the 2D/3D interface was found to be crucial in explaining the experimentally observed device characteristics.

Transferred large area single crystal MoS2 field effect transistors

Transfer of epitaxial, two-dimensional (2D) MoS2 on sapphire grown via synthetic approaches is a prerequisite for practical device applications. We report centimeter-scale, single crystal, synthesized MoS2 field effect transistors (FETs) transferred onto SiO2/Si substrates, with a field-effect mobility of 4.5 cm2 V−1 s−1, which is among the highest mobility values reported for the transferred large-area MoS2 transistors. We demonstrate simple and clean transfer of large-area MoS2 films using deionized water, which can effectively avoid chemical contamination. The transfer method reported here allows standard i-line stepper lithography process to realize multiple devices over the entire film area.

A self-limiting layer-by-layer etching technique for 2H-MoS2

We report controlled layer-by-layer removal of large-area, sulfurized, single-crystal molybdenum disulfide (MoS2) films using a digital etching technique, which utilizes oxidation and removal of the oxidized layer. We demonstrate a self-limiting oxidation process where Mo oxide covered the surface of MoS2. A constant etching rate of one monolayer/cycle and the uniformity of the etching process were also verified. We show that the etching of an integer number of MoS2 layers can be precisely controlled. No noticeable film quality degradation was observed after multiple cycles of digital etching, as confirmed by Raman mapping of the ratio of the and A1g peak intensities.