Challenges and prospects of polyatomic ions' intercalation in the graphite layer for energy storage applications.

Global population explosion has led to the rapid revolution of science and technology, and the high energy demand has necessitated new and efficient energy conversion and storage systems. Lithium ion batteries (LIBs) have a high potential window, high capacity, and high stability, but suffer from high cost and low safety. Therefore, many alternative batteries, including sodium ion batteries (NIBs), potassium (KIBs), aluminum (AIBs), and dual ion batteries (DIBs), have been introduced. One of the key working principles of these batteries is based on cation or anion intercalation in the graphite layers, and leads to the formation of graphite intercalation compounds (GICs). Recently, studies based on determining a reaction mechanism to improve the performance of the batteries have been conducted. In this review, an overview of the work on the reaction mechanism of polyatomic ions intercalated into GICs, the structure of intercalated polyatomic ions, the structure of the accommodated GICs, and their staging is provided. In other words, this review focuses on unraveling and understanding the reaction mechanisms for the intercalation of polyatomic ions into GICs by in situ and ex situ techniques, correlated with computational studies. The current limitations and future prospects of polyatomic ions intercalation batteries are also discussed.

Improving Hydrogen Evolution Activity of Earth-Abundant Cobalt-Doped Iron Pyrite Catalysts by Surface Modification with Phosphide.

Hydrogen is considered as sustainable and environmentally friendly energy for global energy demands in the future. Here a Co-FeS2 catalyst with surface phosphide doping (P/Co-FeS2 ) for hydrogen evolution reaction (HER) in acidic solutions is developed. The P/Co-FeS2 exhibits superior HER electrochemical performance with overpotential of -90 mV at 100 mA cm-2 and Tafel slope of 41 mV/decade and excellent durability.

Intercalation of Zinc Monochloride Cations by Deep Eutectic Solvents for High-Performance Rechargeable Non-aqueous Zinc Ion Batteries.

Zinc ion batteries have been extensively studied with an aqueous electrolyte system. However, the batteries suffer from a limited potential window, gas evolution, cathode dissolution, and dendrite formation on the anode. Considering these limitations, we developed an alternative electrolyte system based on deep eutectic solvents (DESs) because of their low cost, high stability, biodegradability, and non-flammability, making them optimal candidates for sustainable batteries. The DES electrolyte enables reversible Zn plating/stripping and effectively suppresses zinc dendrite formation. Furthermore, in-depth characterizations reveal that the energy storage mechanism can be attributed to [ZnCl]+ ion intercalation and the intermediate complex ion plays a pivotal role in electrochemical reactions, which deliver a high reversible capacity of 310 mAh g-1 at 0.1 A g-1and long-term stability (167 mAh g-1 at a current density of 0.3 A g-1 after 300 cycles, Coulombic efficiency: ∼98%). Overall, this work represents our new finding in rechargeable batteries with the DES electrolyte.

High-Performance Rechargeable Aluminum-Selenium Battery with a New Deep Eutectic Solvent Electrolyte: Thiourea-AlCl3.

Aluminum-sulfur batteries (ASBs) have attracted substantial interest due to their high theoretical specific energy density, low cost, and environmental friendliness, while the traditional sulfur cathode and ionic liquid have very fast capacity decay, limiting cycling performance because of the sluggishly electrochemical reaction and side reactions with the electrolyte. Herein, we demonstrate, for the first time, excellent rechargeable aluminum-selenium batteries (ASeBs) using a new deep eutectic solvent, thiourea-AlCl3, as an electrolyte and Se nanowires grown directly on a flexible carbon cloth substrate (Se NWs@CC) by a low-temperature selenization process as a cathode. Selenium (Se) is a chemical analogue of sulfur with higher electronic conductivity and lower ionization potential that can improve the battery kinetics on the sluggishly electrochemical reaction and the reduction of the polarization where the thiourea-AlCl3 electrolyte can stabilize the side reaction during the reversible conversion reaction of Al-Se alloying processes during the charge-discharge process, yielding a high specific capacity of 260 mAh g-1 at 50 mA g-1 and a long cycling life of 100 times with a high Coulombic efficiency of nearly 93% at 100 mA g-1. The working mechanism based on the reversible conversion reaction of the Al-Se alloying processes, confirmed by the ex situ Raman, XRD, and XPS measurements, was proposed. This work provides new insights into the development of rechargeable aluminum-chalcogenide (S, Se, and Te) batteries.

Three-Dimensional Molybdenum Diselenide Helical Nanorod Arrays for High-Performance Aluminum-Ion Batteries.

The rechargeable aluminum-ion battery (AIB) is a promising candidate for next-generation high-performance batteries, but its cathode materials require more development to improve their capacity and cycling life. We have demonstrated the growth of MoSe2 three-dimensional helical nanorod arrays on a polyimide substrate by the deposition of Mo helical nanorod arrays followed by a low-temperature plasma-assisted selenization process to form novel cathodes for AIBs. The binder-free 3D MoSe2-based AIB shows a high specific capacity of 753 mAh g-1 at a current density of 0.3 A g-1 and can maintain a high specific capacity of 138 mAh g-1 at a current density of 5 A g-1 with 10 000 cycles. Ex situ Raman, XPS, and TEM characterization results of the electrodes under different states confirm the reversible alloying conversion and intercalation hybrid mechanism during the discharge and charge cycles. All possible chemical reactions were proposed by the electrochemical curves and characterization. Further exploratory works on interdigital flexible AIBs and stretchable AIBs were demonstrated, exhibiting a steady output capacity under different bending and stretching states. This method provides a controllable strategy for selenide nanostructure-based AIBs for use in future applications of energy-storage devices in flexible and wearable electronics.

3D CoMoSe4 Nanosheet Arrays Converted Directly from Hydrothermally Processed CoMoO4 Nanosheet Arrays by Plasma-Assisted Selenization Process Toward Excellent Anode Material in Sodium-Ion Battery.

In this work, three-dimensional (3D) CoMoSe4 nanosheet arrays on network fibers of a carbon cloth denoted as CoMoSe4@C converted directly from CoMoO4 nanosheet arrays prepared by a hydrothermal process followed by the plasma-assisted selenization at a low temperature of 450 °C as an anode for sodium-ion battery (SIB) were demonstrated for the first time. With the plasma-assisted treatment on the selenization process, oxygen (O) atoms can be replaced by selenium (Se) atoms without the degradation on morphology at a low selenization temperature of 450 °C. Owing to the high specific surface area from the well-defined 3D structure, high electron conductivity, and bi-metal electrochemical activity, the superior performance with a large sodium-ion storage of 475 mA h g-1 under 0.5-3 V potential range at 0.1 A g-1 was accomplished by using this CoMoSe4@C as the electrode. Additionally, the capacity retention was well maintained over 80 % from the second cycle, exhibiting a satisfied capacity of 301 mA h g-1 even after 50 cycles. The work delivered a new approach to prepare a binary transition metallic selenide and definitely enriches the possibilities for promising anode materials in SIBs with high performances.