Inorganic cathodes of rechargeable Mg batteries suffer from limited selections, while organic materials provide more options. Herein, three conjugated dianhydrides, pyromellitic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride and 3,4,9,10-perylenetetracarboxylic dianhydride are comparatively investigated to elucidate the effects of conjugated structure on the Mg 2 + storage performances. It is observed that the reversible Mg 2 + storage capacity is more dependent on the conjugated structure than carbonyl numbers. Ex-situ mechanism study illustrates that the extended conjugated structure delocalizes the electron density, hence enhancing carbonyl enolization and increasing the Mg 2 + storage capacity. Furthermore, the largely conjugated structure buffers the charge density change during repeated magnesiation/demagnesiation resulting in better cyclability. Prominently, 3,4,9,10-perylenetetracarboxylic dianhydride shows a high Mg 2 + storage capacity (160 mAh g À 1 ) and a good cycling stability (80 % capacity retention after 100 cycles) with the largest conjugated structure. This work provides a low-cost cathode for rechargeable Mg batteries that can be utilized for designing high-performance organic Mg battery cathodes.
The electrocatalytic activities of the MnO2/C composites are examined in Li-O2 cells as the cathode catalysts. Hierarchically mesoporous carbon-supported manganese oxide (MnO2/C) composites are prepared using a combination of soft template and hydrothermal methods. The composites are characterized by X-ray powder diffraction, scanning electron microscopy, transmission electron microscopy, small angle X-ray scattering, The Brunauer–Emmett–Teller (BET) measurements, galvanostatic charge-discharge methods, and rotating ring-disk electrode (RRDE) measurements. The electrochemical tests indicate that the MnO2/C composites have excellent catalytic activity towards oxygen reduction reactions (ORRs) due to the larger surface area of ordered mesoporous carbon and higher catalytic activity of MnO2. The O2 solubility, diffusion rates of O2 and O2•− coefficients (DO2 and DO2•−), the rate constant (kf) for producing O2•−, and the propylene carbonate (PC)-electrolyte decomposition rate constant (k) of the MnO2/C material were measured by RRDE experiments in the 0.1 M TBAPF6/PC electrolyte. The values of kf and k for MnO2/C are 4.29 × 10−2 cm·s−1 and 2.6 s−1, respectively. The results indicate that the MnO2/C cathode catalyst has higher electrocatalytic activity for the first step of ORR to produce O2•− and achieves a faster PC-electrolyte decomposition rate.
The electrocatalytic activities of Mn3O4/C composites are studied in lithium–oxygen (Li–O2) batteries as cathode catalysts. The Mn3O4/C composites are fabricated using ultrasonic spray pyrolysis (USP) with organic surfactants as the carbon sources. The physical and electrochemical performance of the composites is characterized by X-ray diffraction, scanning electron microscopy, particle size analysis, Brunauer–Emmett–Teller (BET) measurements, elemental analysis, galvanostatic charge–discharge methods and rotating ring-disk electrode (RRDE) measurements. The electrochemical tests demonstrate that the Mn3O4/C composite that is prepared using Trition X-114 (TX114) surfactant has higher activity as a bi-functional catalyst and delivers better oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) catalytic performance in Li–O2 batteries because there is a larger surface area and particles are homogeneous with a meso/macro porous structure. The rate constant (kf) for the production of superoxide radical (O2•−) and the propylene carbonate (PC)-electrolyte decomposition rate constant (k) for M3O4/C and Super P electrodes are measured using RRDE experiments and analysis in the 0.1 M tetrabutylammonium hexafluorophosphate (TBAPF6)/PC electrolyte. The results show that TX114 has higher electrocatalytic activity for the first step of ORR to generate O2•− and produces a faster PC-electrolyte decomposition rate.
Rechargeable Mg batteries (RMBs) are advantageous large‐scale energy‐storage devices because of the high abundance and high safety, but exploring high‐performance cathodes remains the largest difficulty for their development. Compared with oxides and sulfides, selenides show better Mg‐storage performance because the weaker interaction with the Mg2+ cation favors fast kinetics. Herein, nanorod‐like FeSe2 was synthesized and investigated as a cathode for RMBs. Compared with microspheres and microparticles, nanorods exhibit higher capacity and better rate capability with a smaller particle size. The FeSe2 nanorods show a high capacity of 191 mAh g−1 at 50 mA g−1 and a good rate performance of 39 mAh g−1 at 1000 mA g−1. Ex situ characterizations demonstrate the Mg2+ intercalation mechanism for FeSe2, and a slight conversion reaction occurs on the surface of the particles. The capacity fading is mainly because of the dissolution of Fe2+, which is caused by the reaction between Fe2+ and Cl− of the electrolyte during the charge process on the surface of the particles. The surface of FeSe2 is mainly selenium after long cycling, which may also dissolve in the electrolyte during cycling. The present work develops a new type of Mg2+ intercalation cathode for RMBs. More importantly, the fading mechanism revealed herein has considered the specificity of Mg battery electrolyte and would assist a better understanding of selenide cathodes for RMBs.
Oxygen reduction reactions (ORR) at the O2 cathode in nonaqueous electrolytes are known to influence the performance of Li-O2 batteries. In this work, we created two ordered mesoporous MnOx/C and TiO2/C composites by a simple hydrothermal process. The composites were characterized by X-ray powder diffraction, scanning electron microscopy, transmission electron microscopy, small angle X-ray scattering, BET measurements, galvanostatic charge-discharge methods. Their ORR kinetics and mechanism have been investigated in Li-O2 batteries by using the rotating disk electrode (RDE) and rotating ring-disk electrode (RRDE) measurements. The electrochemical tests indicate that the MnO2/C composites have excellent catalytic activity towards ORR due to the larger surface area of order mesoporous carbon and higher catalytic activity of MnO2.
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