层层自组装MoS2多晶片增强锂硫电池性能

doi:10.12028/j.issn.2095-4239.2019.0007

储能科学与技术 ›› 2019, Vol. 8 ›› Issue (3): 523-531.doi: 10.12028/j.issn.2095-4239.2019.0007

层层自组装MoS₂多晶片增强锂硫电池性能

姚琳¹, 周玲¹, 李世雄¹, 李晓敏¹, 何凯¹, 何青泉², 宰建陶¹, 任奇志¹, 钱雪峰¹

1 上海交通大学化学化工学院, 上海 200240;
2 上海大学环境与工程学院, 上海 200444

收稿日期:2019-01-18 修回日期:2019-02-19 出版日期:2019-05-01 发布日期:2019-02-20
通讯作者: REN Qizhi,associate professor,research interests:metalloporphyrin-polymer composite system and its applicationin biomimetic enzyme catalysts.E-mail:qzren@sjtu.edu.cn
作者简介:YAO Lin (1993-),female,master,research interests:the cathodeof Li-S batteires and its electeochemical performances.E-mail:yao2411076588@sjtu.edu.cn
基金资助:
National Natural Science Foundation of China (21771124, 21673273 and 21371120), National Basic Research Program of China (2014CB239702), Science and Technology Commission of Shanghai Municipality (17ZR1441200, 18230743400), Shanghai Rising-Star Program (18QA1402400), Scientific Innovation Talent of Henan Province (174200510017) and China Postdoctoral Science Foundation (2017M611529 and 2017M621445).

Edge-rich MoS₂ nanosheets for high performance self-supporting Li-S batteries

YAO Lin¹, ZHOU Ling¹, LI Shixiong¹, LI Xiaomin¹, HE Kai¹, HE Qingquan², ZAI Jiantao¹, REN Qizhi¹, QIAN Xuefeng¹

1 School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, Shanghai 200240, China;
2 School of Environmental and Chemical Engineering, Shanghai University, Shanghai 200444, China

Received:2019-01-18 Revised:2019-02-19 Online:2019-05-01 Published:2019-02-20
Supported by:
National Natural Science Foundation of China (21771124, 21673273 and 21371120), National Basic Research Program of China (2014CB239702), Science and Technology Commission of Shanghai Municipality (17ZR1441200, 18230743400), Shanghai Rising-Star Program (18QA1402400), Scientific Innovation Talent of Henan Province (174200510017) and China Postdoctoral Science Foundation (2017M611529 and 2017M621445).

摘要/Abstract

摘要： 提高硫的电化学活性和抑制多硫离子的溶解是提高锂硫电池性能的关键问题。层状二维金属硫化物的边缘位点相对于平面位点具有更强的吸附多硫离子的能力。然而利用液相法控制合成具有丰富边缘位点的层状二维过渡金属硫化物材料仍是一个挑战。本文以碳布作为导电基体，设计生长了由小尺寸单层S-Mo-S单元通过层层自组装而成的MoS₂多晶纳米片（V-MoS₂/CC）。探究了该复合材料作为活性物质S载体时对锂硫电池倍率性能和循环稳定性的影响。垂直生长的MoS₂纳米片暴露较多的S-Mo-S层边缘活性位点，不仅可以使得随后负载的硫单质的尺寸保持在纳米级（5～10 nm），而且对多硫化锂的催化转化及抑制溶解具有一定程度的促进作用。同时，基底材料碳布的存在使得电极材料无需添加导电剂和黏结剂且提高了整体导电性。使用V-MoS₂/CC@S复合材料组装而成的半电池，在1 C和2 C下循环400和800圈后比容量维持在857 mA·h/g和579 mA·h/g。

关键词: 锂硫电池, 边缘位点, 催化转化, 自支撑

Abstract: Despite the high theoretical energy density and specifc capacity, the practical application of Li-S battery is still impeded because of the low electrical conductivity of sulfur and the dissolution of lithium polysulfides in electrolyte. Edge sites of 2D layered transition metal dichalcogenides have been show advantages than in-plane sites on preventing the shuttling effects of polysulfdes. While the synthesis of 3D hierarchical MoS₂ structures with abundant active edge sites is still a challenge. Herein, vertically aligned MoS₂ nanosheets with richly exposed (002) plane edges on the carbon cloth were fabricated via hydrothermal process and served as the host of sulfur to improve its electrochemical performance. Besides the carbon cloth as ideal supporting material to facilitate electron/ion transport, edge-rich layered MoS₂ nanosheets with abundant dangling Mo-S bonds can localized the size of sulfur particles to 5~10 nm, which results a high utilization of active substances (~1174 mA·h·g^-1 at 0.1 C) and improve the reversibility and polysulfde redox kinetics. Furthermore, the edge sites have strong rules to absorb and catalyze the conversion of polysulfdes. Therefore, the self-supporting cathode can deliver a specifc discharge capacity (based on sulfur) of 857 mA·h·g^-1 at 1 C after 400 cycles and 579 mA·h·g^-1 at 2 C after 800 cycles.

Key words: lithium-sulfur battery, edge sites, catalytic conversion, self-supporting

中图分类号:

TM911

姚琳, 周玲, 李世雄, 李晓敏, 何凯, 何青泉, 宰建陶, 任奇志, 钱雪峰. 层层自组装MoS₂多晶片增强锂硫电池性能[J]. 储能科学与技术, 2019, 8(3): 523-531.

YAO Lin, ZHOU Ling, LI Shixiong, LI Xiaomin, HE Kai, HE Qingquan, ZAI Jiantao, REN Qizhi, QIAN Xuefeng. Edge-rich MoS₂ nanosheets for high performance self-supporting Li-S batteries[J]. Energy Storage Science and Technology, 2019, 8(3): 523-531.

参考文献

[1] MANTHIRAM A, FU Y, CHUNG S H, et al. Rechargeable lithiumsulfur batteries[J]. Chemical Reviews, 2014, 114(23):11751-11787.
[2] WU F, CHEN S, SROT V, et al. A sulfur-limonene-based electrode for lithium-sulfur batteries:High-performance by self-protection[J]. Advanced Materials, 2018, 30(13):doi:10.1002/adma.201706643.
[3] MANTHIRAM A, CHUNG S H, ZU C, et al. Lithium-sulfur batteries:Progress and prospects[J]. Advanced Materials, 2015, 27(12):1980-2006.
[4] PANG Q, LIANG X, KWOK C Y, et al. Advances in lithium-sulfur batteries based on multifunctional cathodes and electrolytes[J]. Nature Energy, 2016, 1(9):doi:10.1038/NENERGY.2016.132.
[5] CHUNG W J, GRIEBEL J J, KI E T, et al. The use of elemental sulfur as an alternative feedstock for polymeric materials[J]. Nature Chemistry, 2013, 5(6):518-524.
[6] YIN Y X, XIN S, GUO Y G, et al. Lithium-sulfur batteries:Electrochemistry, materials, and prospects[J]. Angewandte Chemie International Edition, 2013, 52(50):13186-13200.
[7] LIU X, J. HUANG J Q, ZHANG Q, et al. Nanostructured metal oxides and sulfdes for lithium-sulfur batteries[J]. Advanced Materials, 2017, 29(20):doi:10.1002/adma.201601759.
[8] ZHANG R, CHENG X B, ZHAO C Z, et al. Conductive nanostructured scaffolds render low local current density to inhibit lithium dendrite growth[J]. Advanced Materials, 2016, 28(11):2155-2162.
[9] REHMAN S, GUO S J, HOU Y L, et al. Rational design of Si/SiO₂@hierarchical porous carbon spheres as effcient polysulfde reservoirs for high-performance Li-S battery[J]. Advanced Materials, 2016, 28(16):3167-3172.
[10] ZHOU G M, PEI S F, LI L, et al. A graphene-pure-sulfur sandwich structure for ultrafast, long-life lithium-sulfur batteries[J]. Advanced Materials, 2014, 26(4):625-631.
[11] YUAN Z, PENG H J, HOU T Z, et al. Powering lithium-sulfur battery performance by propelling polysulfide redox at sulfiphilic hosts[J]. Nano Letters, 2016, 16(1):519-527.
[12] MA Z L, LI Z, HU K, et al. The enhancement of polysulfide absorbsion in Li-S batteries by hierarchically porous CoS₂/carbon paper interlayer[J]. Journal of Power Source, 2016, 325:71-78.
[13] MA L, WEI S Y, ZHUANG H L, et al. Hybrid cathode architectures for lithium batteries based on TiS₂ and sulfur[J]. J. Mater. Chem. A 2015, 3(39):19857-19866.
[14] ZHANG S S, TRAN D T, et al. Pyrite FeS₂ as an effcient adsorbent of lithium polysulphide for improved lithium-sulphur batteries[J]. Journal of Materials Chemistry A, 2016, 4(12):4371-4374.
[15] YANG Y, FEI H L, RUAN G D, et al. Vertically aligned WS₂ nanosheets for water splitting[J]. Advanced Functional Materials, 2015, 25(39):6199-6204.
[16] LI Y F, WU D H, ZHOU Z, et al. Enhanced Li adsorption and diffusion on MoS₂ zigzag nanoribbons by edge effects:A computational study[J]. The Journal of Physical Chemistry Letters, 2012, 3(16):2221-2227.
[17] XU X D, LIU W, KIM Y, et al. Nanostructured transition metal sulfdes for lithium ion batteries:Progress and challenges[J]. Nano Today, 2014, 9(5):604-630.
[18] JUNG Y, SHEN J, LIU Y, et al. Metal seed layer thickness-induced transition from vertical to horizontal growth of MoS₂ and WS₂[J]. Nano Letters, 2014, 14(12):6842-6849.
[19] JARAMILLO T F, JØRGENSEN K P, BONDE J, et al. Identifcation of active edge sites for electrochemical H₂ evolution from MoS₂ nanocatalysts[J]. Science, 2007, 317(5834):100-102.
[20] LI D J, MAITI U N, LIM J, et al. Molybdenum sulfde/N-doped CNT forest hybrid catalysts for high-performance hydrogen evolution reaction[J]. Nano Letters, 2014, 14(3):1228-1233.
[21] VOIRY D, SALEHI M, SILVA R, et al. Conducting MoS₂ nanosheets as catalysts for hydrogen evolution reaction[J]. Nano Letters, 2013, 13(12):6222-6227.
[22] XIE J F, ZHANG H, LI S, et al. Defect-rich MoS₂ ultrathin nanosheets with additional active edge sites for enhanced electrocatalytic hydrogen evolution[J]. Advanced Materials, 2013, 25(40):5807-5813.
[23] TANG K, WANG X F, LI Q, et al. High edge selectivity of in situ electrochemical Pt deposition on edge-rich layered WS₂ nanosheets[J]. Advanced Materials, 2018, 30(7):doi:10.1002/adma.201704779.
[24] ZHANG Z Y, WU S L, CHENG J Y, et al. MoS₂ nanobelts with (002) plane edges-enriched flat surfaces for high-rate sodium and lithium storage[J]. Energy Storage Materials, 2018, 15:65-74.
[25] WANG H T, ZHANG Q F, YAO H B, et al. High electrochemical selectivity of edge versus terrace sites in two-dimensional layered MoS₂ materials[J]. Nano Letters, 2014, 14(12):7138-7144.
[26] LI X M, QIAN T Y, ZAI J T, et al. Co stabilized metallic 1T_d MoS₂ monolayers:Bottom-up synthesis and enhanced capacitance with ultralong cycling stability[J]. Materials Today Energy, 2018, 7:10-17.
[27] WANG H L, YANG Y, LIANG Y Y, et al. Graphene-wrapped sulfur particles as a rechargeable lithium-sulfur battery cathode material with high capacity and cycling stability[J]. Nano Letters, 2011, 11(7):2644-2647.
[28] ZHAO M Q, LIU X F, ZHANG Q, et al. Graphene/single-walled carbon nanotube hybrids:One-step catalytic growth and applications for highrate Li-S batteries[J]. ACS Nano, 2012, 6(12):10759-10769.
[29] LI X M, ZAI J T, XIANG S, et al. Regeneration of metal sulfdes in the delithiation process:The key to cyclic stability[J]. Advanced Energy Materials, 2016, 6(19):doi:10.10020/aenm.2016010565.
[30] MA L, ZHUANG H L, WEI S Y, et al. Enhanced Li-S batteries using amine-functionalized carbon nanotubes in the cathode[J]. ACS Nano, 2015, 10(1):1050-1059.
[31] WANG T L, SUN C L, YANG M Z, et al. Phase-transformation engineering in MoS₂ on carbon cloth as flexible binder-free anode for enhancing lithium storage[J]. Journal of Alloy and Compounds, 2017, 716(5):112-118.
[32] QU Q T, GAO T, ZHENG H Y, et al. Strong surface-bound sulfur in conductive MoO₂ matrix for enhancing Li-S battery performance[J]. Advanced Materials Interfaces, 2015, 2(7):doi:10.1002/admi.201500048.
[33] ZHANG Y, ZAI J T, HE K, et al. Fe₃C nanoparticles encapsulated in highly crystalline porous graphite:Salt-template synthesis and enhanced electrocatalytic oxygen evolution activity and stability[J]. Chemical Communication, 2018, 54(25):3158-3161.
[34] LEI T Y, CHEN W, HUANG J W, et al. Multi-functional layered WS₂ nanosheets for enhancing the performance of lithium-sulfur batteries[J]. Advanced Energy Materials, 2016, 7(4):doi:10.1002/aenm.201601843.
[35] PANG Q, KUNDU D, CUISINIER M, et al. Surface-enhanced redox chemistry of polysulphides on a metallic and polar host for lithium-sulphur batteries[J]. Nature Communication, 2014, 5:doi:10.1038/ncomms5759.
[36] MA L B, ZHANG W J, WANG L, et al. Strong capillarity, chemisorption, and electrocatalytic capability of crisscrossed nanostraws enabled flexible, high-rate, and long-cycling lithium-sulfur batteries[J]. ACS Nano, 2018, 12(5):4868-4876.
[37] YAO J, MEI T, CUI Z Q, et al. Hollow carbon spheres with TiO₂ encapsulated sulfur and polysulfides for long-cycle lithium-sulfur batteries[J]. Chemical Engineering Journal, 2017, 330:644-650.
[38] WANG M, ZAI J T, LI B, et al. Hierarchical Cu_2-xSe nanotubes constructed by two-unit-cell-thick nanosheets:Room-temperature synthesis and promoted electrocatalytic activity towards polysulfdes[J]. Journal of Materials Chemistry A, 2016, 4(13):4790-4796.
[39] GHAZI Z A, HE X, KHATTAK A M, et al. MoS₂/Celgard separator as effcient polysulfde barrier for long-life lithium-sulfur batteries[J]. Advanced Materials, 2017, 29(21):doi:10.1002/adma.201606817.

层层自组装MoS₂多晶片增强锂硫电池性能

Edge-rich MoS₂ nanosheets for high performance self-supporting Li-S batteries

PDF

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 15

编辑推荐

Metrics

本文评价

[1]	孙玉琦, 魏凤, 周洪, 周超峰. 专利视域下全球锂硫电池技术竞争态势分析[J]. 储能科学与技术, 2022, 11(5): 1657-1666.
[2]	魏超超, 余创, 吴仲楷, 彭林峰, 程时杰, 谢佳. Li₃PS₄ 固态电解质的研究进展[J]. 储能科学与技术, 2022, 11(5): 1368-1382.
[3]	陈志城, 李宗旭, 蔡玲, 刘易斯. 柔性金属空气电池的发展现状及未来展望[J]. 储能科学与技术, 2022, 11(5): 1401-1410.
[4]	孙春水, 郭德才, 陈剑. 碳化木耳多孔碳的制备及在硫正极中的应用[J]. 储能科学与技术, 2021, 10(6): 2060-2068.
[5]	郭德超, 郭义敏, 张啟文, 慈祥云, 何凤荣. 锂离子电池用无溶剂干法电极的制备及其性能研究[J]. 储能科学与技术, 2021, 10(4): 1311-1316.
[6]	朱鑫鑫, 蒋伟, 万正威, 赵澍, 李泽珩, 王利光, 倪文斌, 凌敏, 梁成都. 固态锂硫电池电解质及其界面问题研究进展[J]. 储能科学与技术, 2021, 10(3): 848-862.
[7]	谢彬, 孙嘉楠. 基于机械仿真和测试的高比能量锂硫电池模组开发[J]. 储能科学与技术, 2021, 10(2): 586-597.
[8]	闫梦蝶, 李晖, 凌敏, 潘慧霖, 张强. 基于溶解沉积机制锂硫电池的研究进展简评[J]. 储能科学与技术, 2020, 9(6): 1606-1613.
[9]	陆贇, 梁嘉宁, 朱用, 李峥嵘, 胡冶州, 陈科, 王得丽. 有机物衍生的锂硫电池正极材料研究进展[J]. 储能科学与技术, 2020, 9(5): 1454-1466.
[10]	吴湘江, 何丰, 曹余良, 艾新平. 电解液组成对固相转化机制硫电极性能的影响[J]. 储能科学与技术, 2020, 9(2): 331-338.
[11]	王维坤, 王安邦, 金朝庆. 锂硫电池的实用化挑战[J]. 储能科学与技术, 2020, 9(2): 593-597.
[12]	叶戈, 袁洪, 赵辰孜, 朱高龙, 徐磊, 侯立鹏, 程新兵, 何传新, 南皓雄, 刘全兵, 黄佳琦, 张强. 全固态锂硫电池正极中离子输运与电子传递的平衡[J]. 储能科学与技术, 2020, 9(2): 339-345.
[13]	王久林. 锂硫二次电池之我见[J]. 储能科学与技术, 2020, 9(1): 1-4.
[14]	杨慧军, 傅璟, 陈加航, 郭城, 郭瑞, 解晶莹, 王久林. 高安全锂硫电池电解液研究进展[J]. 储能科学与技术, 2018, 7(6): 1060-1068.
[15]	胡策军, 杨积瑾, 王航超, 陈一帆, 张茸茸, 刘文, 孙晓明. 锂硫电池安全性问题现状及未来发展态势[J]. 储能科学与技术, 2018, 7(6): 1082-1093.