聚苯胺包覆蛋白石页岩/硫复合材料的制备及其电化学性能

doi:10.15541/jim20170023

摘要/Abstract

摘要：

以蛋白石页岩为载硫体, 通过化学沉积法制备蛋白石页岩/硫复合材料, 再利用化学氧化聚合法在其表面包覆一层聚苯胺, 制备出一种新型的蛋白石页岩/硫-聚苯胺复合材料, 作为锂硫电池的正极材料。SEM、TEM和BET等测试结果表明蛋白石页岩呈层状多孔结构, 小尺寸硫在材料内分布均匀,聚苯胺包覆的厚度约为400 nm。电化学性能测试表明, 蛋白石页岩/硫-聚苯胺正极活化后放电比容量最高达到1164.93 mAh/g, 在0.5C (1.0C=1675 mA/g)倍率下, 循环300次后放电比容量为539.30 mAh/g, 库伦效率始终保持在95%以上, 说明蛋白石页岩具有良好的吸附性, 同时导电聚苯胺包覆层具有双效固硫的作用, 有利于吸附多硫化物和抑制穿梭效应。

关键词: 蛋白石页岩, 聚苯胺, 正极材料, 锂硫电池

Abstract:

Opal shale/S composite was prepared by loading sulfur on opal shale via solution-based reaction- deposition method, and then polyaniline (PANI) was covered on the as-prepared opal shale/S composite by means of chemical oxidative polymerization method, which was used as cathode material of lithium-sulfur battery. Scanning electron microscope (SEM), transmission electron microscope (TEM), and Brunauer-Emmett-Teller (BET) characterization were conducted, and the results indicated that opal shale had a layered porous structure. As-prepared sulfur with small size was distributed uniformly in the composite. The PANI with around thickness of 400 nm was coated on the surface of the opal shale/S composite. Constant current charge-discharge tests showed that opal shale/S-PANI cathode obtained a maximum discharge specific capacity of 1164.93 mAh/g after activation and retained a discharge specific capacity of 539.30 mAh/g after 300 cycles at the current rate of 0.5C (1.0C=1675 mA/g). The coulombic efficiency of opal shale/S-PANI cathode always maintained more than 95%, indicating that opal shale with excellent adsorption properties and conductive PANI coating had double fixation effect for sulfur, which was beneficial to adsorb polysulfide and inhibit the shuttle effect.

Key words: opal shale, polyaniline, cathode material, lithium-sulfur battery

中图分类号:

O646

柴二亚, 潘俊安, 袁国龙, 程豪, 安峰, 谢淑红. 聚苯胺包覆蛋白石页岩/硫复合材料的制备及其电化学性能[J]. 无机材料学报, 2017, 32(11): 1165-1170.

CHAI Er-Ya, PAN Jun-An, YUAN Guo-Long, CHENG Hao, AN Feng, XIE Shu-Hong. Preparation and Electrochemical Property of Polyaniline Coated Opal Shale/Sulfur Composite[J]. Journal of Inorganic Materials, 2017, 32(11): 1165-1170.

图/表 8

图1 硫(a)、蛋白石页岩(b)、蛋白石页岩/硫(c)和蛋白石页岩/硫-聚苯胺(d)的XRD图谱

Fig. 1 XRD patterns of S (a), opal shale (b), opal shale/S (c) and opal shale/S-PANI (d)

图2 蛋白石页岩(a, b), 蛋白石页岩/硫(c, d), 蛋白石页岩/硫-聚苯胺(e, f)的SEM和TEM照片

Fig. 2 SEM and TEM morphologies of opal shale (a,b), opal shale/S (c, d), and opal shale/S-PANI (e, f), respectively

图3 蛋白石页岩、蛋白石页岩/硫和蛋白石页岩/硫-聚苯胺的氮气等温吸脱附图(a)和孔径分布图(b)

Fig. 3 Nitrogen adsorption-desorption isotherms (a) and BJH pore size distribution (b) of opal shale, opal shale/S and opal shale/S-PANI

图4 蛋白石页岩/硫-聚苯胺的热重分析曲线

Fig. 4 Thermo gravimetric analysis (TGA) curve of opal shale/S-PANI

图5 蛋白石页岩/硫和蛋白石页岩/硫-聚苯胺在0.5C倍率下的循环性能图(a)和倍率性能图(b)

Fig. 5 (a) Cycling performance and the corresponding coulombic efficiency at 0.5C rate; (b) rate capability under different discharge rate of the opal shale/S and opal shale/S- PANI

图6 蛋白石页岩/硫-聚苯胺的循环伏安曲线

Fig. 6 Cyclic voltammetry curves of opal shale/S-PANI after the first cycle and 300th cycle at 0.5C rate

图7 0.5C倍率下蛋白石页岩/硫-聚苯胺的充放电曲线图

Fig. 7 Galvanostatic discharge-charge profiles of opal shale/ S-PANI at 0.5C rate

图8 蛋白石页岩/硫-聚苯胺的交流阻抗图

Fig. 8 Electrochemical impedance spectroscopy of opal shale/S- PANI after the first cycle and 300th cycle at 0.5C rate

参考文献 23

[1]	HU J J, LI G R, GAO X P.Current status, problems and challenges in lithium-sulfur batteries.Journal of Inorganic Materials, 2013, 28(11): 1181-1186.
[2]	YANG Y, ZHENG G Y, CUI Y.Nanostructured sulfur cathodes.Chemical Society Reviews, 2013, 42(7): 3018-3032.
[3]	BRUCE P G, FREUNBERGER S A, HARDWICK L J,et al. Li-O2 and Li-S batteries with high energy storage. Nature Materials, 2011, 11(1): 19-29.
[4]	JI X L, NAZAR L F.Advances in Li-S batteries.Journal of Materials Chemistry, 2010, 20(44): 9821-9826.
[5]	ZHENG J M, GU M, WANG C M,et al. Controlled nucleation and growth process of Li2S2/Li2S in lithium-sulfur batteries. Journal of the Electrochemical Society, 2013, 160(11): A1992-A1996.
[6]	SAH Z W, LI W Y, CHA J J,et al. Sulphur-TiO2 yolk-shell nanoarchitecture with internal void space for long-cycle lithium- sulphur batteries. Nature Communications, 2013, 4: 1331-1336.
[7]	MIKHAYLIK Y V, AKRIDGE J R.Polysulfide shuttle study in the Li/S battery system.Journal of the Electrochemical Society, 2004, 151(11): A1969-A1976.
[8]	JI X L, EVERS S, BLACK R,et al. Stabilizing lithium-sulphur cathodes using polysulphide reservoirs. Nature Communications, 2011, 2: 325-331.
[9]	KIM M, KANG S H, MANUEL J,et al. Investigation into the role of silica in lithium polysulfide adsorption for lithium sulfur battery. Materials Research Bulletin, 2015, 69: 29-35.
[10]	ZHAO X F, HE C Y, LI X L.A novel adsorbent material opal shale.North Environment, 2005, 30(2): 62-63.
[11]	YANG D F, WEI C D, NING W K,et al. Structure and adsorption properties of nenjiang opal shale. Journal of Jilin University(Earth Science Edition), 2010, 40(5): 1061-1065.
[12]	LI X L, ZHAO X F, ZHANG J L.Study on decolorization of new adsorption material opal shale.North Environment, 2004, 29(1): 37-38.
[13]	KIM J H, SEO J, CHOI J,et al. Synergistic ultrathin functional polymer-coated carbon nanotube interlayer for high performance lithium-sulfur batteries. ACS Applied Materials & Interfaces, 2016, 8(31): 20092-20099.
[14]	SUN Q, HE B, ZHANG X Q,et al. Engineering of hollow core-shell interlinked carbon spheres for highly stable lithium- sulfur batteries. ACS Nano, 2015, 9(8): 8504-8513.
[15]	WU F, CHEN J Z, CHEN R J,et al. Sulfur/polythiophene with a core/shell structure: synthesis and electrochemical properties of the cathode for rechargeable lithium batteries. The Journal of Physical Chemistry C, 2011, 115(13): 6057-6063.
[16]	LI G C, LI G R, YE S H,et al. A polyaniline-coated sulfur/carbon composite with an enhanced high-rate capability as a cathode material for lithium/sulfur batteries. Advanced Energy Materials, 2012, 2(10): 1238-1245.
[17]	ZHOU W D, YU Y C, CHEN H,et al. Yolk-shell structure of polyaniline-coated sulfur for lithium-sulfur batteries. Journal of the American Chemical Society, 2013, 135(44): 16736-16743.
[18]	GUSTAFSSON G, CAO Y, TREACY G M,et al. Flexible light- emitting diodes made from soluble conducting polymers. Nature, 1992, 357(6378): 477-479.
[19]	KRUK M, JARONIEC M.Gas adsorption characterization of ordered organic-inorganic nanocomposite materials.Chemistry of Materials, 2001, 13(10): 3169-3183.
[20]	WANG Z D, ZHANG M L, MEI H Y,et al. The physical chemistry explanation of the capillary condensation and the circuit of adsorption-desorption. Xinjiang Petroleum Geology, 2002, 23(3): 233-235.
[21]	LI W Y, ZHENG G Y, YANG Y,et al. High-performance hollow sulfur nanostructured battery cathode through a scalable, room temperature, one-step, bottom-up approach. Proceedings of the National Academy of Sciences, 2013, 110(18): 7148-7153.
[22]	ATEBAMBA J M, MOSKON J, PEJOVNIK S,et al. On the interpretation of measured impedance spectra of insertion cathodes for lithium-ion batteries. Journal of the Electrochemical Society, 2010, 157(11): A1218-A1228.
[23]	CHEN J J, JIA X, SHE Q J,et al. The preparation of nano- sulfur/MWCNTs and its electrochemical performance. Electrochimica Acta, 2010, 55(27): 8062-8066.