Characterization and electrochemical performance of the spinel LiMn2O4 prepared from -MnO2

The preparation and characterization of the spinel LiMn₂O₄ obtained by solid state reaction from quasi-amorphous -MnO₂ is reported. A well-defined highly pure spinel was characterized from X-ray diffractograms. The average manganese valence of -MnO₂ and spinel samples was found to be 3.89±0.01 and 3.59±0.01, respectively. The electrochemical performance of the spinel was evaluated through cyclic voltammetry and chronopotentiometry. The voltammetric profiles obtained at 1 mV/s for the LiMn₂O₄ electrode in 1 M LiClO₄ dissolved in a 2:1 mixture of ethylene carbonate and dimethyl carbonate showed typical peaks for the lithium insertion/extraction reactions. The charge capacity of this electrode was found to be 110 mA h g⁻¹ for the first charge/discharge cycles.     

球磨法制备锌酸钙研究

应用球磨法制备锌酸钙,并研究制备过程的影响因素.XRD,TG DTA等测试表明,合成的锌酸钙化学组成为Ca(OH)2·2Zn(OH)2·2H2O.粉末微电极和模拟电池实验显示该材料具有良好的循环可逆性.     

吡唑基镁卤化物/四氢呋喃可充镁电池电解液

将不同配比的吡唑与格氏试剂反应制得的吡唑基镁卤化物/四氢呋喃(THF)溶液用作可充镁电池电解液,采用循环伏安和恒电流充放电测试研究了该电解液的镁沉积-溶出性能和氧化分解电位;并通过X射线衍射(XRD)和扫描电镜(SEM)对沉积物的组分和形貌进行了分析.结果表明,吡唑上的取代基、吡唑与格氏试剂的反应配比对电解液的电化学性能都有影响.1 mol·L-11-甲基吡唑-PhMgCl(1:1摩尔比)/THF反应配制的电解液在不锈钢(SS)集流体的阳极氧化分解电位达到2.4 V(vs Mg/Mg2+),并具有镁沉积-溶出电位低、循环稳定性高、配制方便的特点,有希望应用于实际的可充镁电池体系中.     

Revealing the Interfacial Chemistry of Fluoride Alkyl Magnesium Salts in Magnesium Metal Batteries

Exploring promising electrolyte-system with high reversible Mg plating/stripping and excellent stability is essential for rechargeable magnesium batteries (RMBs). Fluoride alkyl magnesium salts (Mg(OR^F)₂) not only possess high solubility in ether solvents but also compatible with Mg metal anode, thus holding a vast application prospect. Herein, a series of diverse Mg(OR^F)₂ were synthesized, among them, perfluoro-tert-butanol magnesium (Mg(PFTB)₂)/AlCl₃/MgCl₂ based electrolyte demonstrates highest oxidation stability, and promotes the in situ formation of robust solid electrolyte interface. Consequently, the fabricated symmetric cell sustains a long-term cycling over 2000 h, and the asymmetric cell exhibits a stable Coulombic efficiency of 99.5 % over 3000 cycles. Furthermore, the Mg||Mo₆S₈ full cell maintains a stable cycling over 500 cycles. This work presents guidance for understanding structure–property relationships and electrolyte applications of fluoride alkyl magnesium salts.     

Hydrated Eutectic Electrolytes Stabilizing Quasi-Underpotential Mg Plating/Stripping for High-Voltage Mg Batteries

Aqueous rechargeable Mg batteries (ARMBs) usually fail from severe anode passivation, alternatively, executing quasi-underpotential Mg plating/stripping chemistry (UPMC) on a proper heterogeneous metal substrate is a crucial remedy. Herein, a stable UPMC on Zn substrate is initially achieved in new hydrated eutectic electrolytes (HEEs), delivering an ultralow UPMC overpotential and high energy/voltage plateau of ARMBs. The unique eutectic property remarkably expands the lower limit of electrochemical stability window (ESW) of HEEs and undermines the competition between hydrogen evolution/corrosion reactions and UPMC, enabling a reversible UPMC. The UPMC is carefully revealed by multiple characterizations, which shows a low overpotential of 50 mV at 0.1 mA cm⁻² over 550 h. With sulfonic acid-doped polyaniline (SPANI) cathodes, UPMC-based full cells show high energy/power densities of 168.6 Wh kg⁻¹/2.1 kWh kg⁻¹ and voltage plateau of 1.3 V, far overwhelming conventional aqueous systems.     

Synergistic Fe−Se Atom Pairs as Bifunctional Oxygen Electrocatalysts Boost Low-Temperature Rechargeable Zn-Air Battery

Herein, we successfully construct bifunctional electrocatalysts by synthesizing atomically dispersed Fe−Se atom pairs supported on N-doped carbon (Fe−Se/NC). The obtained Fe−Se/NC shows a noteworthy bifunctional oxygen catalytic performance with a low potential difference of 0.698 V, far superior to that of reported Fe-based single-atom catalysts. The theoretical calculations reveal that p-d orbital hybridization around the Fe−Se atom pairs leads to remarkably asymmetrical polarized charge distributions. Fe−Se/NC based solid-state rechargeable Zn-air batteries (ZABs−Fe−Se/NC) present stable charge/discharge of 200 h (1090 cycles) at 20 mA cm⁻² at 25 °C, which is 6.9 times of ZABs−Pt/C+Ir/C. At extremely low temperature of −40 °C, ZABs−Fe−Se/NC displays an ultra-robust cycling performance of 741 h (4041 cycles) at 1 mA cm⁻², which is about 11.7 times of ZABs−Pt/C+Ir/C. More importantly, ZABs−Fe−Se/NC could be operated for 133 h (725 cycles) even at 5 mA cm⁻² at −40 °C.     

Electrochemical lithium insertion in β-MoO<Subscript>3</Subscript>: novel Li<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>MoO<Subscript>3</Subscript> bronzes

New lithium molybdenum bronzes have been synthesized by electrochemical lithium insertion. Through electrochemical spectroscopy techniques we have detected that lithium insertion proceeds at least in a two-step reduction process. The maximum amount of lithium inserted in β-MoO₃ leads to a high specific capacity of the cell of 370 Ah kg^–1. However, this capacity was lost after the first charge-discharge cycle, resulting in a total loss of 25%, due to structural transformations. The structural study of the insertion process showed that each step of the process can be associated with the formation of different single phases of variable composition, Li _x MoO₃. Electronic Publication     

Electrochemical and structural study of LiCoPO<Subscript>4</Subscript>-based electrodes

LiCoPO₄ samples were synthesized by two different techniques (high-temperature solid-state reaction and lower-temperature synthesis using NH₄CoPO₄·H₂O as precursor) and tested as cathode materials for 5-V lithium batteries. An irreversible lithium deinsertion was observed for the high-temperature sample. In contrast, the application of lower-temperature synthesis led to a significant improvement of the lithium storage reversibility. Different delithiation mechanisms in LiCoPO₄ were found for the samples obtained by different synthetic techniques. The nature of capacity fading during cycling of the cells is discussed.     

A series of spinel phase cathode materials prepared by a simple hydrothermal process for rechargeable lithium batteries

A series of spinel-structured materials have been prepared by a simple hydrothermal procedure in an aqueous medium. The new synthetic method is time and energy saving i.e., no further thermal treatment and extended grinding. The main experimental process involved the insertion of lithium into electrolytic manganese dioxide with glucose as a mild reductant in an autoclave. Both the hydrothermal temperature and the presence of glucose play the critical roles in determining the final spinel integrity. Particular electrochemical performance has also been systematically explored, and the results show that Al³⁺, F⁻ co-substituted spinels have the best combination of initial capacity and capacity retention among all these samples, exhibited the initial capacity of 115 mAh/g and maintained more than 90% of the initial value at the 50th cycle.     

Zinc tetrathiomolybdate as novel anodes for rechargeable lithium batteries

An ever first attempt has been made to investigate the anode performance characteristics of zinc tetrathiomolybdate. The poor crystallined zinc tetrathiomolybdate was prepared by precipitation method from Na₂MoO₄, ZnSO₄·7H₂O, and CH₃CSNH₂ as starting materials. Galvanostatic data in the voltage range of 0.01–2.0 V up to 20 cycles at a rate of 100 mA g⁻¹ revealed that the material gave high reversible capacities and good performance.