Electrochemistry
Online ISSN : 2186-2451
Print ISSN : 1344-3542
ISSN-L : 1344-3542
Volume 91, Issue 4
Displaying 1-7 of 7 articles from this issue
Regular Papers
Articles
  • Taichi NAKAMURA, Kingo ARIYOSHI
    2023 Volume 91 Issue 4 Pages 047001
    Published: April 07, 2023
    Released on J-STAGE: April 07, 2023
    Advance online publication: March 11, 2023
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    A major factor in the capacity fading of lithium-ion batteries is the imbalance in the state-of-charge (SOC) between the positive and negative electrodes, which is caused by the difference in the side-reaction current between the two electrodes. Therefore, it is crucial to understand these side reactions to extend battery life. There are two types of side-reaction current, ISR: “intrinsic”-ISR results from electrolyte decomposition, while “additional”-ISR results from the reaction of decomposition products. The “additional”-ISR is closely related to crosstalk reactions. In this study, we conducted overdischarge tests on Li[Li1/3Ti5/3]O4 (LTO)/Li[Li0.1Al0.1Mn1.8]O4 (LAMO) cells with the SOC of the positive and negative electrodes intentionally imbalanced to understand the nature of the “additional”-ISR. While the cell capacity initially increased after the overdischarge, the recovered capacity decreased in subsequent cycles. This phenomenon can be explained well by a side-reaction model that considers the oxidant generated in the cell due to overdischarge, which indicates that the concentrations of oxidants and reductants in the cell are important for the ISR.

  • Emiri KATO, Ryoichi ISHIMATSU, Jun MIZUNO, Takashi KASAHARA
    2023 Volume 91 Issue 4 Pages 047002
    Published: April 18, 2023
    Released on J-STAGE: April 18, 2023
    Advance online publication: March 14, 2023
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    We demonstrated that the electrogenerated chemiluminescence (ECL) performances of 5,6,11,12-tetraphenyltetracene (rubrene)-based devices can be significantly enhanced by using an emitting assist dopant. We prepared an ECL solution by dissolving rubrene and 4-(di-p-tolylamino)-4′-[(di-p-tolylamino)styryl]stilbene (DPAVB) in an organic solvent. A microfluidic ECL cell having the prepared solution exhibited a bright yellow ECL emission from rubrene with a maximum luminance of 292 cd m−2 at 6.0 V and a maximum current efficiency of 4.50 cd A−1 at 5.5 V. Moreover, a current efficiency of over 3.0 cd A−1 was maintained from 3.0 to 6.5 V. Furthermore, the device lifetime was improved in comparison with the rubrene solution without DPAVB. The emission mechanism was discussed using cyclic voltammogram data. The DPAVB molecule was found to be more readily oxidized and more difficult to be reduced than rubrene. The excited rubrene molecules were expected to be produced efficiently in the device by the electron transfer reactions between rubrene•− and DPAVB•+ as well as rubrene•− and rubrene•+. Based on the findings, we concluded that the enhanced device characteristics were primarily attributed to the well-balanced generation of radical cations and anions.

  • Di WANG, Jinkwang HWANG, Keigo KUBOTA, Kazuhiko MATSUMOTO, Rika HAGIWA ...
    2023 Volume 91 Issue 4 Pages 047003
    Published: April 18, 2023
    Released on J-STAGE: April 18, 2023
    Advance online publication: March 15, 2023
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    Sodium-sulfur (Na-S) batteries are promising energy storage systems for renewable energy sources which redeem an intermittent energy source. This study reports the effects of the Na[SO3CF3] fraction in an inorganic Na[SO3CF3]-Cs[N(SO2CF3)2] ionic liquid electrolyte (x(Na[SO3CF3]) = 0.2, 0.3, and 0.4) on the performance of Na-S batteries. Measurements of physicochemical and electrochemical properties demonstrated that decrease in the Na[SO3CF3] fraction decreases viscosity and increases ionic conductivity and the solubility of polysulfides into the ionic liquid, which contributes to the enhanced capacity in the low potential region during discharging.

  • Minami KATO, Nobuhiko TAKEICHI, Hikaru SANO
    2023 Volume 91 Issue 4 Pages 047004
    Published: April 20, 2023
    Released on J-STAGE: April 20, 2023
    Advance online publication: March 21, 2023
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    Some of the Benzimidazole-linked polymers (BILPs) are a class of porous organic polymers that have high porosities, large specific surface areas, and high thermal and chemical stability. Owing to these properties, BILPs can be used in various applications including solid electrolytes for renewable energy utilization. In this study, we carried out the boran-modification of a kind of BILPs, in order to increase the Li ion conductivity by decreases the interaction between lithium ions and the anion backbone. The resulting B-TFB-HAB-BILP materials have an ionic conductivity of 2.9 × 10−6 S cm−1 at 30 °C, which increases to 1.4 × 10−4 S cm−1 at room temperature with the addition of the ionic liquid, PP13[TFSA]. This can be attributed to the suppression of resistance at the grain boundary. A coin cell with an organic cathode active material, B-TFB-HAB-BILP/PP13[TFSA] as the quasi-solid electrolyte, and Li foil as the anode exhibited an initial discharge capacity of 223 mAh g−1 (76 % of theoretical capacity). Our study can aid in the realization of organic rechargeable batteries with high gravimetric energy density.

  • Daisuke TAKIMOTO, Keisuke SUZUKI, Sho HIDESHIMA, Wataru SUGIMOTO
    2023 Volume 91 Issue 4 Pages 047005
    Published: April 20, 2023
    Released on J-STAGE: April 20, 2023
    Advance online publication: March 29, 2023
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    The pseudocapacitive flowable electrodes typically show high energy density because of the contribution of the faradaic charge of redox-active organic materials and the electric double layer charge of carbon materials. However, the redox reaction kinetics of organic molecules are slow due to poor diffusion kinetics. We recently reported that a pseudocapacitive flowable electrode exhibited bell-shaped cyclic voltammograms (peak separation (ΔEp) = 0 mV); specifically, the molecules were confined within slit-shaped graphitic micropores of activated carbon (AC). Herein, we studied the relationship between charge storage and the reaction mechanism to tailor the electrochemical performance of a pseudocapacitive flowable electrode by half-cell study. The results show that the redox reaction of the confined molecules entailed a charge-transfer-controlled mechanism, while the unconfined molecules exhibited a mass-transfer-controlled system. This difference inhibited the fast charging and discharging of the pseudocapacitive flowable electrode. This study demonstrates that half-cell studies are crucial for clarifying the relationship between the charge storage and rate performances of pseudocapacitive flowable electrodes.

  • Rongbo WEI, Wei LIU, Zesong GAO, Dong YANG, Qiangqiang LIAO
    2023 Volume 91 Issue 4 Pages 047006
    Published: April 25, 2023
    Released on J-STAGE: April 25, 2023
    Advance online publication: March 18, 2023
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    Pipecolyldithiocarbamic Acid (PIPDTC) is actually considered as a potential corrosion inhibitor. The inhibition behavior of PIPDTC is appropriately confirmed by electrochemical measurements accompanied with spectra characterization techniques and DFT calculations. The consequences point out that chemically adsorbed PIPDTC molecule is an outstanding corrosion inhibitor with corrosion efficiency of 99.87 % at 298 K and a great thermal stability ascribed to the Cu-S binding, implying that PIPDTC could be a tangible alternative as the prospective corrosion inhibitor for applications in marine industry.

  • Daigo TERUTSUKI, Shuhei YAMAGUCHI, Yuina ABE, Hiroya ABE, Matsuhiko NI ...
    2023 Volume 91 Issue 4 Pages 047007
    Published: April 28, 2023
    Released on J-STAGE: April 28, 2023
    Advance online publication: March 30, 2023
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    A porous microneedle (PMN)-based potentiometric ion sensor for transdermal monitoring of electrolytes in the interstitial fluid was developed. The carbon coating with an ion-selective membrane was formed on half of the needle tip as the working electrode, while the Ag/AgCl reference electrode was mounted on the PMN chip. This design of a single needle-type configuration allows lower invasive transdermal sensing than the conventional system with multiple needle electrodes. The fabricated potentiometric sensor showed the near-Nernstian responses to Na+ concentration in the excised pig skin, demonstrating the applicability for monitoring intradermal electrolytes.

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