Xia Cao

Bio: Xia Cao is an academic researcher. The author has contributed to research in topics: Diluent & Alkali metal. The author has an hindex of 1, co-authored 2 publications receiving 1 citations.

Electrolyte for stable cycling of rechargeable alkali metal and alkali ion batteries

Abstract: Localized superconcentrated electrolytes (LSEs) and electrochemical devices including the LSEs are disclosed The LSE includes an active salt, a solvent in which the active salt is soluble, and a diluent in which the active salt is insoluble or poorly soluble, wherein the diluent includes a fluorinated orthoformate

Liquefied Gas Electrolytes for Electrochemical Energy Storage Devices

Abstract: Separating charges is a gas Solid and liquid electrolytes allow for charges or ions to move while keeping anodes and cathodes separate. Separation prevents short circuits from occurring in energy storage devices. Rustomji et al. show that separation can also be achieved by using fluorinated hydrocarbons that are liquefied under pressure. The electrolytes show excellent stability in both batteries and capacitors, particularly at low temperatures. Science, this issue p. eaal4263 Electrolytes based on liquefied gas solvents show excellent conductivity at low temperatures. INTRODUCTION The vast majority of electrolyte research for electrochemical energy storage devices, such as lithium-ion batteries and electrochemical capacitors, has focused on liquid-based solvent systems because of their ease of use, relatively high electrolytic conductivities, and ability to improve device performance through useful atomic modifications on otherwise well-understood solvent molecules. However, with a delicate balance between electrochemical stability, ionic conductivity, temperature, and safety, there has understandably been little change over a number of decades in the electrolyte composition, which consists primarily of carbonate-type solvents and provides limited improvement in device performance. RATIONALE It is often assumed that molecules that are gaseous at room temperature are typically nonpolar and have low intermolecular attraction, which prevents them from condensing at room temperature. Although this may be true in general, there are a number of reasonably polar molecules that are gaseous at room temperature. It is hypothesized that these relatively polar gaseous molecules, when liquefied under pressure, could dissolve salts at room temperature to form liquefied gas electrolytes. Although a number of potential solvents were explored, the present study focuses on the use of hydrofluorocarbons, which are nontoxic and have relatively strong chemical bonds, allowing for a wide electrochemical window. Although these solvents generally have moderate dielectric constants, their exceptionally low viscosity allows for a superior solvent dielectric-fluidity factor that is higher than commonly used solvents, potentially allowing for relatively high electrolytic conductivities. Last, the low melting points of the solvents studied could allow for substantial improvements in device operation at low temperatures. Although they may require modified processes for manufacturability, the pressures of the proposed chemistry are moderate, and the solvents are compatible with commonly used separator and electrode materials. RESULTS All tests were conducted in high-pressure vessels in which the solvents were in a liquefied state under their own vapor pressure. We found that electrochemical capacitors that have a liquefied gas electrolyte based on difluoromethane (CH2F2) have an exceptionally wide operation temperature from –78° to +65°C, with similar resistance and capacitance to conventional devices. Further, we demonstrate an increase in operation voltage to 3.0 V—equivalent to a 23% increase in energy density—under accelerated life conditions. The use of a liquefied gas electrolyte based on fluoromethane (CH3F) show platting and stripping efficiencies on lithium metal of ~97% over hundreds of cycles under aggressive testing (1 mA cm−2, 1 C cm−2 each cycle), with no evidence of dendritic growth. This impressive behavior on lithium metal is thought to be due to the particular combination of an exceptionally low viscosity, high vapor pressure, and LiF chemical reduction products on the anode surface. The same fluoromethane-based liquefied gas electrolyte shows good cycling and rate performance on a LiCoO2 cathode. We demonstrate a high discharge capacity retention of 60.6% at –60°C, which is thought to be due to an ideal solid electrolyte interphase formed on the electrodes as observed through x-ray photoelectron spectroscopy analysis. Last, we show that there is a substantial drop in electrolytic conductivity at elevated temperatures because of salt precipitation out from solution as the supercritical point is approached (~+40° to 80°C) and recovery in the conductivity as the temperature is lowered. This reversible mechanism is demonstrated to effectively shutdown operation in an electrochemical capacitor device and may similarly enable reversible battery shutdown at increased temperatures, mitigating the potential of thermal runaway and improving safety. CONCLUSION A succinct background and demonstration of liquefied gas electrolytes for both electrochemical capacitors and lithium batteries are presented and show potential for substantial improvements in low-temperature operation, energy density, and safety. With their superior electrochemical and physical properties, further exploration and development of these liquefied gas solvents is warranted for their use in next-generation energy storage devices and beyond. Illustration of the electrolytic conductivity and pressure with temperature of the studied liquefied gas electrolytes. The electrolyte solvent is liquefied from a gaseous state under pressure. Exceptionally high electrolytic conductivities are observed at low temperatures. Further, a sharp drop in conductivity occurs as the salt precipitates near the supercritical temperature, which allows for a reversible shutdown mechanism to mitigate battery thermal runaway. Electrochemical capacitors and lithium-ion batteries have seen little change in their electrolyte chemistry since their commercialization, which has limited improvements in device performance. Combining superior physical and chemical properties and a high dielectric-fluidity factor, the use of electrolytes based on solvent systems that exclusively use components that are typically gaseous under standard conditions show a wide potential window of stability and excellent performance over an extended temperature range. Electrochemical capacitors using difluoromethane show outstanding performance from –78° to +65°C, with an increased operation voltage. The use of fluoromethane shows a high coulombic efficiency of ~97% for cycling lithium metal anodes, together with good cyclability of a 4-volt lithium cobalt oxide cathode and operation as low as –60°C, with excellent capacity retention.

Electrolytes for high-voltage lithium batteries

Abstract: In the aim of achieving higher energy density in lithium (Li) ion batteries (LIBs), both industry and academia show great interest in developing high-voltage LIBs (>4.3 V). However, increasing the charge cutoff voltage of the commercial LIBs causes severe degradation of both the positive electrode materials and conventional LiPF₆-oragnocarbonate electrolytes. Consequently, LIBs using conventional LiPF₆-organocarbonate electrolytes suffer from a short cycle life when operated at higher charge cutoff voltages. In this review, the aging mechanisms associated with high-voltage LIBs are analyzed, and the countermeasures from the electrolyte design are discussed.