Amino-substituted binuclear phthalocyanines bonding with multi-wall carbon nanotube as efficient electrocatalysts for li

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Amino-substituted binuclear phthalocyanines bonding with multi-wall carbon nanotube as efficient electrocatalysts for lithium-thionyl chloride battery Yan Gao1, Liangting Chen1, Guangfa Hu2, Xiao Wang1, Gai Zhang3, Ying Zheng4, Jianshe Zhao1,a) 1

Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of Ministry of Education, Shaanxi Key Laboratory of Physico-Inorganic Chemistry, College of Chemistry & Materials Science, Northwest University, Xi’an 710069, China Research Institute of Shaanxi Yanchang Petroleum Group Corp. Ltd., Xi’an 710075, China 3 School of Materials and Chemical Engineering, Xi’an Technological University, Xi’an 710021, China 4 Department of Chemical Engineering, University of New Brunswick, Fredericton, New Brunswick E3B 5A3, Canada a) Address all correspondence to this author. e-mail: [email protected] 2

Received: 16 November 2018; accepted: 23 January 2019

In this work, carbon nanotubes (CNTs)-templated binuclear metallophthalocyanines (MTAPcCF3)2C (M = Mn, Fe, Co, Ni, Cu, Zn) assemblies (MTAPcCF3)2C–COOH–CNTs are designed and obtained. Whereafter, the structure and morphology of target products are analyzed by many means such as infrared, X-ray diffraction, X-ray photoelectron spectroscopy, and scanning electron microscopy. The electrocatalytic performances of lithiumthionyl chloride battery catalyzed by (MTAPcCF3)2C–COOH–CNTs were carried out. The result shows that all catalysts can improve the battery performance including the discharge time and the initial voltage. The catalytic performance of (MTAPcCF3)2C–COOH–CNTs is ordered following the central metal: Mn > Fe > Ni > Co > Cu > Zn. The cell capacity catalyzed by optimal catalyst (MnTAPcCF3)2C–COOH–CNTs can expand to 28.08 mAˑh, with increase by 142.07%, and the (MnTAPcCF3)2C–COOH–CNTs can extend the discharge time to 551.6 s. Besides, the reaction mechanism is presented on the basis of cyclic voltammetry measurements.

Introduction Lithium/thionyl chloride battery is a nonaqueous system battery and applied in many fields such as aerospace, military, armarium, and so on [1, 2, 3, 4, 5]. Li/SOCl2 battery has some unique advantages and is one of the most applied batteries in recent years. The advantages of Li/SOCl2 battery include high voltage, high specific energy, high energy density, few pollution, low price, and long life in the storage [2, 6, 7]. Like all batteries, this battery also include anode, cathode, and electrolyte [8, 9, 10, 11, 12, 13]. The anode and cathode materials are composed of lithium metal and carbon, respectively. And the nonaqueous electrolyte is the mixture of SOCl2 and LiAlCl4. During the discharge process, lithium ion is obtained by losing electron of lithium metal and embedded in the anode material [14]. At the same time, SOCl2 is reduced, and the LiCl, SO2, and S appear during the reduction process [Eqs. (1)–(3)]. The LiCl leads to passive film formation on the surface of the cathode, and the

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production of S is deposited in the electrolyte. So the battery syste