Abstract:
Rechargeable aluminum batteries (RABs) are extensively developed due to their cost-effectiveness, eco-friendliness, and low flammability and the earth abundance of their electrode materials. However, the commonly used RAB ionic liquid (IL) electrolyte is highly moisture-sensitive and corrosive. To address these problems, a 4-ethylpyridine/AlCl3 IL is proposed. The effects of the AlCl3 to 4-ethylpyridine molar ratio on the electrode charge–discharge properties are systematically examined. A maximum graphite capacity of 95 mAh g−1 is obtained at 25 mA g−1. After 1000 charge–discharge cycles, ≈85% of the initial capacity can be retained. In situ synchrotron X-ray diffraction is employed to examine the electrode reaction mechanism. In addition, low corrosion rates of Al, Cu, Ni, and carbon-fiber paper electrodes are confirmed in the 4-ethylpyridine/AlCl3 IL. When opened to the ambient atmosphere, the measured capacity of the graphite cathode is only slightly lower than that found in a N2-filled glove box; moreover, the capacity retention upon 100 cycles is as high as 75%. The results clearly indicate the great potential of this electrolyte for practical RAB applications.
Transition metal high-entropy oxides (HEOs) are an attractive class of anode materials for high-performance lithium-ion batteries (LIBs). However, owing to the multiple electroactive centers of HEOs, the Li+ storage mechanism is complex and debated in the literature. In this work, operando quick-scanning X-ray absorption spectroscopy (XAS) is used to study the lithiation/delithiation mechanism of the Cobalt-free spinel (CrMnFeNiCu)3O4 HEO. A monochromator oscillation frequency of 2 Hz is used and 240 spectra are integrated to achieve a 2 min time resolution. High-photon-flux synchrotron radiation is employed to increase the XAS sensitivity. The results indicate that the Cu2+ and Ni2+ cations are reduced to their metallic states during lithiation but their oxidation reactions are less favorable compared to the other elements upon delithiation. The Mn2+/3+ and Fe2+/3+ cations undergo two-step conversion reactions to form metallic phases, with MnO and FeO as the intermediate species, respectively. During delithiation, the oxidation of Mn occurs prior to that of Fe. The Cr3+ cations are reduced to CrO and then Cr0 during lithiation. A relatively large overpotential is required to activate the Cr reoxidation reaction. The Cr3+ cations are found after delithiation. These results can guide the material design of HEOs for improving LIB performance.