聚吡咯/硫复合材料的制备及性能
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摘要
为了抑制穿梭效应,提高锂硫电池的电化学性能,采用一步法制备聚吡咯/硫的复合材料。以过硫酸铵作为氧化剂、乙醇作为分散剂,用化学氧化聚合法制备导电聚吡咯的同时,原位沉积包覆硫,研究过硫酸铵和吡咯单体以不同氧化比反应制备聚吡咯/硫复合材料,并用SEM和TEM测试观察材料的形貌,用恒流充放电测试材料的电化学性能。结果表明:当过硫酸铵与吡咯以1∶1复合时,得到的聚吡咯/硫复合材料有较好的形貌;组装的电池在0.1 C的恒电流充放电测试下,初始放电比容量可以达到943.3 m A·h/g,循环20圈后,放电比容量仍然保持在747.9 mA·h/g,并且每圈的库伦效率都大于97%,表现出了较好的充放电性能和循环稳定性。
In order to inhibit the shuttle effect and improve the electrochemical performance of lithium-sulfur batteries, a one-step method was used to prepare polypyrrole/sulfur composites. Polypyrrole/sulfur composites were obtained by coating sulfur with polypyrrole in-situ deposition that was prepared via chemical oxidative polymerization with ammonium persulfate as oxidant and ethanol as dispersant. The polypyrrole/sulfur composites were prepared by the reaction of ammonium persulfate and pyrrole at different oxidation ratios. The morphology of the material was observed by SEM and TEM. The electrochemical properties of the material were tested by constant current charge and discharge. The results show that when the ammonium persulfate and pyrrole at the ratio of 1 ∶ 1, the polypyrrole/sulfur composite has a better morphology. The initial discharge specific capacity are 943.3 m A·h/g at 0.1 C,and a retention specific capacity of 747.9 m A·h/g after 20 cycles with Coulomb efficiency of above 97% at every cycle, which showed better charge-discharge characteristics and cycle stability.
In order to inhibit the shuttle effect and improve the electrochemical performance of lithium-sulfur batteries, a one-step method was used to prepare polypyrrole/sulfur composites. Polypyrrole/sulfur composites were obtained by coating sulfur with polypyrrole in-situ deposition that was prepared via chemical oxidative polymerization with ammonium persulfate as oxidant and ethanol as dispersant. The polypyrrole/sulfur composites were prepared by the reaction of ammonium persulfate and pyrrole at different oxidation ratios. The morphology of the material was observed by SEM and TEM. The electrochemical properties of the material were tested by constant current charge and discharge. The results show that when the ammonium persulfate and pyrrole at the ratio of 1 ∶ 1, the polypyrrole/sulfur composite has a better morphology. The initial discharge specific capacity are 943.3 m A·h/g at 0.1 C,and a retention specific capacity of 747.9 m A·h/g after 20 cycles with Coulomb efficiency of above 97% at every cycle, which showed better charge-discharge characteristics and cycle stability.
引文
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[18]WU H W,HUANG Y,YANG Y W,et al.Insight into the electrochemical behavior of lithium-sulfur cells assisted by potassium hydroxide activated carbon black and polyaniline nanorods[J].Electrochimica Acta,2016,209:643-653.
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[20]YAN J H,LI B Y,LIU X B.Nano-porous sulfur-polyaniline electrodes for lithium-sulfur batteries[J].Nano Energy,2015,18:245-252.
[2]卢松涛.石墨烯改性锂硫电池正极材料的制备及其电化学性能研究[D].哈尔滨:哈尔滨工业大学,2014.LU S T.Preparation of grapheen-modificated cathode materials for lithium-sulfur battery and their electrochemical properties[D].Harbin:Harbin Institute of Technology,2014(in Chinese).
[3]张凯.锂硫电池正极改性、结构设计及电化学性能研究[D].长沙:中南大学,2014.ZHANG K.Cathode modification,structure design of lithiumsulfur battery and electrochemical performance[D].Changsha:Central South University,2014(in Chinese).
[4]ZHANG S S.Role of LiNO3in rechargeable lithium/sulfur battery[J].Electrochim Acta,2012,70:344-348.
[5]TAO X Y,WANG J G,LIU C,et al.Balancing surface adsorption and diffusion of lithium-polysulfides on nonconductive oxides for lithium-sulfur battery design[J].Nature Communications,2016,7:11203.
[6]SEH Z W,SUN Y M,ZHANG Q F,et al.Designing highenergy lithium-sulfur batteries[J].Chemical Society Reviews,2016,45(20):5605-5634.
[7]MANTHIRAM A,FU Y Z,SU Y S.Challenges and prospects of lithium-sulfur batteries[J].Accounts of Chemical Research,2013,46(5):1125-1134.
[8]ZHAO H B,PENG Z H,WANG W J,et al.Reduced graphene oxide with ultrahigh conductivity as carbon coating layer for high performance sulfur@reduced graphene oxide cathode[J].Journal of Power Sources,2014,245:529-536.
[9]ELAZARI R,SALITRA G,GARSUCH A,et al.Sulfur-impregnated activated carbon fiber cloth as a binder-free cathode for rechargeable Li-S batteries[J].Advanced Materials,2011,23(47):5641-5644.
[10]SUN L,LI M Y,JIANG Y,et al.Sulfur nanocrystals confined in carbon nanotube network as a binder-free electrode for highperformance lithium sulfur batteries[J].Nano Lett,2014,14(7):4044-4049.
[11]SEH Z W,LI W Y,CHA J J,et al.Sulphur-TiO2yolk-shell nanoarchitecture with internal void space for long-cycle lithium-sulphur batteries[J].Nature Communications,2013,4:1331.
[12]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[J].Advanced Energy Materials,2012,2(10):1238-1245.
[13]YUAN G H,WANG H D.Facile synthesis and performance of polypyrrole-coated sulfur nanocomposite as cathode materials for lithium/sulfur batteries[J].Journal of Energy Chemistry,2014,23(5):657-661.
[14]吕羚源.导电聚合物包覆S-C正极材料的制备及电化学性能研究[D].哈尔滨:哈尔滨工业大学,2014.LYU L Y.Investigation on preparation and electrochemical performance of S-C cathode material coated by conductive polymer[D].Harbin:Harbin Institute of Technology,2014(in Chinese).
[15]XIE Y P,ZHAO H B,CHENG H W,et al.Facile large-scale synthesis of core-shell structured sulfur@polypyrrole composite and its application in lithium-sulfur batteries with high energy density[J].Applied Energy,2016,175:522-528.
[16]HYUN J E,LEE P C,TATSUMI I.Preparation and electrochemical properties of sulfur-polypyrrole composite cathodes for electric vehicle applications[J].Electrochimica Acta,2015,176:887-892.
[17]NAKAMURA N,YOKOSHIMA T,NARA H,et al.Suppression of polysulfide dissolution by polypyrrole modification of sulfur-based cathodes in lithium secondary batteries[J].Journal of Power Sources,2015,274:1263-1266.
[18]WU H W,HUANG Y,YANG Y W,et al.Insight into the electrochemical behavior of lithium-sulfur cells assisted by potassium hydroxide activated carbon black and polyaniline nanorods[J].Electrochimica Acta,2016,209:643-653.
[19]WEI P,FAN M Q,CHEN H C,et al.Enhanced cycle performance of hollow polyaniline sphere/sulfur composite in comparison with pure sulfur for lithiume-sulfur batteries[J].Renewable Energy,2016,86:148-153.
[20]YAN J H,LI B Y,LIU X B.Nano-porous sulfur-polyaniline electrodes for lithium-sulfur batteries[J].Nano Energy,2015,18:245-252.