New tris- and pentakis-fused donors containing extended tetrathiafulvalenes: New positive electrode materials for rechargeable batteries

Shintaro Iwamoto; Yuu Inatomi; Daisuke Ogi; Satoshi Shibayama; Yukiko Murakami; Minami Kato; Kazuyuki Takahashi; Kazuyoshi Tanaka; Nobuhiko Hojo; Yohji Misaki

doi:10.3762/bjoc.11.128

New tris- and pentakis-fused donors containing extended tetrathiafulvalenes: New positive electrode materials for rechargeable batteries

Beilstein J Org Chem. 2015 Jul 8:11:1136-47. doi: 10.3762/bjoc.11.128. eCollection 2015.

Authors

Affiliations

¹ Department of Applied Chemistry, Graduate School of Science and Engineering, Ehime University, 3 Bunkyo-cho, Matsuyama, Ehime 790-8577, Japan ; Department, Molecular Engineering, Graduate School of Engineering, Kyoto University, Katsura, Kyoto 615-8520, Japan.
² Department of Applied Chemistry, Graduate School of Science and Engineering, Ehime University, 3 Bunkyo-cho, Matsuyama, Ehime 790-8577, Japan ; Panasonic Corporation, 1006 Kadoma, Kadoma, Osaka 571-8501, Japan.
³ Department of Applied Chemistry, Graduate School of Science and Engineering, Ehime University, 3 Bunkyo-cho, Matsuyama, Ehime 790-8577, Japan.
⁴ Department of Chemistry, Graduate School of Science, Kobe University, 1-1 Rokkodai-cho, Nada-ku, Kobe 657-8501, Japan.
⁵ Department, Molecular Engineering, Graduate School of Engineering, Kyoto University, Katsura, Kyoto 615-8520, Japan.
⁶ Panasonic Corporation, 1006 Kadoma, Kadoma, Osaka 571-8501, Japan.
⁷ Department of Applied Chemistry, Graduate School of Science and Engineering, Ehime University, 3 Bunkyo-cho, Matsuyama, Ehime 790-8577, Japan ; Elements Strategy Initiative for Catalysts and Batteries (ESICB), Kyoto University, Katsura, Kyoto 615-8520, Japan.

Abstract

Derivatives of tris-fused TTF extended with two ethanediylidenes (5), tris- and pentakis-fused TTFs extended with two thiophene-2,5-diylidenes (6-9) were successfully synthesized. Cyclic voltammograms of the tetrakis(n-hexylthio) derivative of 5 and 7 (5d, 7d) consisted of two pairs of two-electron redox waves and two pairs of one-electron redox waves. On the other hand, four pairs of two-electron redox waves and two pairs of one-electron redox waves were observed for the tetrakis(n-hexylthio) derivative of 9 (9d). Coin-type cells using the bis(ethylenedithio) derivatives of 5 (5b), 6 (6b) and the tetrakis(methylthio) derivatives of 5 (5c) and 8 (8c) as positive electrode materials showed initial discharge capacities of 157-190 mAh g(-1) and initial energy densities of 535-680 mAh g(-1). The discharge capacities after 40 cycles were 64-86% of the initial discharge capacities.

Keywords: cyclic voltammetry; positive electrode materials; rechargeable battery; redox; tetrathiafulvalene.