Xiaodi Ren

A Low-Overpotential Potassium–Oxygen Battery Based on Potassium Superoxide

Li-O(2) battery is regarded as one of the most promising energy storage systems for future applications. However, its energy efficiency is greatly undermined by the large overpotentials of the discharge (formation of Li(2)O(2)) and charge (oxidation of Li(2)O(2)) reactions. The parasitic reactions of electrolyte and carbon electrode induced by the high charging potential cause the decay of capacity and limit the battery life. Here, a K-O(2) battery is report that uses K(+) ions to capture O(2)(-) to form the thermodynamically stable KO(2) product. This allows for the battery to operate through the one-electron redox process of O(2)/O(2)(-). Our studies confirm the formation and removal of KO(2) in the battery cycle test. Furthermore, without the use of catalysts, the battery shows a low discharge/charge potential gap of less than 50 mV at a modest current density, which is the lowest one that has ever been reported in metal-oxygen batteries.

Integrating a redox-coupled dye-sensitized photoelectrode into a lithium-oxygen battery for photoassisted charging.

With a high theoretical specific energy, the non-aqueous rechargeable lithium-oxygen battery is a promising next-generation energy storage technique. However, the large charging overpotential remains a challenge due to the difficulty in electrochemically oxidizing the insulating lithium peroxide. Recently, a redox shuttle has been introduced into the electrolyte to chemically oxidize lithium peroxide. Here, we report the use of a triiodide/iodide redox shuttle to couple a built-in dye-sensitized titanium dioxide photoelectrode with the oxygen electrode for the photoassisted charging of a lithium-oxygen battery. On charging under illumination, triiodide ions are generated on the photoelectrode, and subsequently oxidize lithium peroxide. Due to the contribution of the photovoltage, the charging overpotential is greatly reduced. The use of a redox shuttle to couple a photoelectrode and an oxygen electrode offers a unique strategy to address the overpotential issue of non-aqueous lithium-oxygen batteries and also a distinct approach for integrating solar cells and batteries.

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.

Dimeric [Mo2S12]2− Cluster: A Molecular Analogue of MoS2 Edges for Superior Hydrogen‐Evolution Electrocatalysis

Proton reduction is one of the most fundamental and important reactions in nature. MoS2 edges have been identified as the active sites for hydrogen evolution reaction (HER) electrocatalysis. Designing molecular mimics of MoS2 edge sites is an attractive strategy to understand the underlying catalytic mechanism of different edge sites and improve their activities. Herein we report a dimeric molecular analogue [Mo2 S12 ](2-) , as the smallest unit possessing both the terminal and bridging disulfide ligands. Our electrochemical tests show that [Mo2 S12 ](2-) is a superior heterogeneous HER catalyst under acidic conditions. Computations suggest that the bridging disulfide ligand of [Mo2 S12 ](2-) exhibits a hydrogen adsorption free energy near zero (-0.05 eV). This work helps shed light on the rational design of HER catalysts and biomimetics of hydrogen-evolving enzymes.

Understanding Side Reactions in K–O2 Batteries for Improved Cycle Life

Superoxide based metal-air (or metal-oxygen) batteries, including potassium and sodium-oxygen batteries, have emerged as promising alternative chemistries in the metal-air battery family because of much improved round-trip efficiencies (>90%). In order to improve the cycle life of these batteries, it is crucial to understand and control the side reactions between the electrodes and the electrolyte. For potassium-oxygen batteries using ether-based electrolytes, the side reactions on the potassium anode have been identified as the main cause of battery failure. The composition of the side products formed on the anode, including some reaction intermediates, have been identified and quantified. Combined experimental studies and density functional theory (DFT) calculations show the side reactions are likely driven by the interaction of potassium with ether molecules and the crossover of oxygen from the cathode. To inhibit these side reactions, the incorporation of a polymeric potassium ion selective membrane (Nafion-K(+)) as a battery separator is demonstrated that significantly improves the battery cycle life. The K-O2 battery with the Nafion-K(+) separator can be discharged and charged for more than 40 cycles without increases in charging overpotential.

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.

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).

Potassium Superoxide: A Unique Alternative for Metal–Air Batteries

Lithium-oxygen (Li-O2) batteries have been envisaged and pursued as the long-term successor to Li-ion batteries, due to the highest theoretical energy density among all known battery chemistries. However, their practical application is hindered by low energy efficiency, sluggish kinetics, and a reliance on catalysts for the oxygen reduction and evolution reactions (ORR/OER). In a superoxide battery, oxygen is also used as the cathodic active medium but is reduced only to superoxide (O2•-), the anion formed by adding an electron to a diatomic oxygen molecule. Therefore, O2/O2•- is a unique single-electron ORR/OER process. Since the introduction of K-O2 batteries by our group in 2013, superoxide batteries based on potassium superoxide (KO2) have attracted increasing interest as promising energy storage devices due to their significantly lower overpotentials and costs. We have selected potassium for building the superoxide battery because it is the lightest alkali metal cation to form the thermodynamically stable superoxide (KO2) product. This allows the battery to operate through the proposed facile one-electron redox process of O2/KO2. This strategy provides an elegant solution to the long-lasting kinetic challenge of ORR/OER in metal-oxygen batteries without using any electrocatalysts. Over the past five years, we have been focused on understanding the electrolyte chemistry, especially at the electrode/electrolyte interphase, and the electrolytes stability in the presence of potassium metal and superoxide. In this Account, we examine our advances and understanding of the chemistry in superoxide batteries, with an emphasis on our systematic investigation of K-O2 batteries. We first introduce the K metal anode electrochemistry and its corrosion induced by electrolyte decomposition and oxygen crossover. Tuning the electrolyte composition to form a stable solid electrolyte interphase (SEI) is demonstrated to alleviate electrolyte decomposition and O2 cross-talk. We also analyze the nucleation and growth of KO2 in the oxygen electrode, as well its long-term stability. The electrochemical growth of KO2 on the cathode is correlated with the rate performance and capacity. Increasing the surface area and reducing the O2 diffusion pathway are identified as critical strategies to improve the rate performance and capacity. Li-O2 and Na-O2 batteries are further compared with the K-O2 chemistry regarding their pros and cons. Because only KO2 is thermodynamically stable at room temperature, K-O2 batteries offer reversible cathode reactions over the long-term while the counterparts undergo disproportionation. The parasitic reactions due to the reactivity of superoxide are discussed. With the trace side products quantified, the overall superoxide electrochemistry is highly reversible with an extended shelf life. Lastly, potential anode substitutes for K-O2 batteries are reviewed, including the K3Sb alloy and liquid Na-K alloy. We conclude with perspectives on the future development of the K metal anode interface, as well as the electrolyte and cathode materials to enable improved reversibility and maximized power capability. We hope this Account promotes further endeavors into the development of the K-O2 chemistry and related material technologies for superoxide battery research.