锂-硫电池研究现状及展望

doi:10.13208/j.electrochem.160545

摘要/Abstract

摘要：

锂-硫电池由于具有高比能量以及硫廉价易得等优势而受到人们的广泛关注. 但其实际应用仍面临着来自于正极、电解液以及负极等方面的诸多挑战，具体包括硫正极的溶解、多硫化合物的“穿梭效应”及金属锂负极的枝晶问题. 本文以课题组近期的研究结果为主线，综述了近两年来关于锂-硫电池的研究进展，重点探讨了碳硫复合物正极、硫化锂正极、复合隔膜设计和电解液方面的研究进展，并总结了各方面存在的问题.

关键词: 锂-硫电池, 穿梭效应, 硫正极, 硫化锂正极, 复合隔膜, 电解液

Abstract:

Lithium-sulfur batteries have recently attracted worldwide attention due to the high specific theoretical energy density of sulfur cathode (2600 Wh•kg^-1), low cost and wide availability of sulfur. However, the practical application of lithium-sulfur batteries has been hindered by several challenges, such as the shuttling of polysulfide intermediates, the large volume expansion of sulfur during charge/discharge and the dendrites formation on lithium anode. Foremost among these is the shuttling effect arising from the dissolution of lithium polysulfides intermediate into the electrolyte from the cathode reaction and their diffusion to the anode where they react with metal lithium to form lower-ordered lithium sulfides that then return to the cathode, which results in the poor cycling stability and severe self-discharge. This review summarizes the recent research advances in the sulfur cathode, battery structures, electrolytes and lithium sulfide cathode to mitigate the shuttling effect of lithium polysulfides. The possible solutions proposed by our groups to mitigate the shuttling effect are introduced from the aspects of sulfur cathode, design of composite Celgard, electrolytes and lithium sulfide (Li₂S) cathode. Finally, perspectives and future developments of lithium-sulfur batteries are pointed out based on our previous studies and experiences.

中图分类号:

O646

袁守怡，庞莹，王丽娜，王永刚，夏永姚. 锂-硫电池研究现状及展望[J]. 电化学（中英文）, 2016, 22(5): 453-463.

YUAN Shou-yi, PANG Ying, WANG Li-na, WANG Yong-gang, XIA Yong-yao. Advances and Prospects of Lithium-Sulfur Batteries[J]. Journal of Electrochemistry, 2016, 22(5): 453-463.

参考文献

[1] 吴宇平，袁翔云，董超等. 锂离子电池[M]. 北京：化学工业出版社，2012:3-30.

[2] 黄可龙，王兆翔，刘素琴. 锂离子电池原理与关键技术[M]. 北京：化学工业出版社,2008,5-70.

[3] Armand T.M., Tarascon J.M.. Buiding better batteries. [J] Nature, 2008, 451(7179), 652-657.

[4] Bruce P. G., Freunberger S. A., Hardwick L. J., Tarascon J.M., Li-O₂ and Li-S batteries with high energy storage. [J] Nature Materials, 2012, 11 (1), 19-29.

[5] Manthiram A., Fu Y., Su Y.S. Challenges and Prospects of lithium sulfur batteries.[J] Account of Chemical Research, 2013, 46 (5), 1125-1134.

[6] Manthiram A., Fu Y., Chung S.-H. et al. Rechargeable lithium−sulfur batteries.[J] Chemical Reviews, 2014, 114 (23), 11751-11787.

[7] Yang Y., Zheng G.Y., Cui Y., Nanostructured sulfur cathode.[J] Chemical Society Reviews, 2013, 42(7), 3018-3032.

[8] Ji X.L., Lee K.T. Nazar L.F. A highly ordered nanostructured carbon-sulphur cathode for lithium-sulphur batteries.[J] Nature Materials, 2009, 8(6), 500-506.

[9] Schuster J. He G. Mandlmeier B. et al. Spherical ordered mesoporous carbon nanoparticles with high porosity for lithium–sulfur batteries. [J] Angewandte Chemie International Edition, 2012, 51 (15), 3591-3595

[10] Zhang K., Qin F, Lai Y. et al. Efficient fabrication of hierarchically porous graphene-derived aerogel and its application in lithium sulfur battery. [J] ACS Applied Materials &Interfaces 2016, 8 (9), 6072-6081.

[11] Yang K., Gao Q.M., Yanli Tan, Tian W. Q. et al. Biomass-derived porous carbon with micropores and small mesopores for high-performance lithium-sulfur batteries.[J] Chemistry-A Europe Journal. 2016, 22(10), 3239-3244.

[12] Zhang Z.W., Li Z.Q., Hao F.B. et al. 3D interconnected porous carbon aerogels as sulfur immobilizers for sulfur impregnation for lithium-sulfur batteries with high rate capability and cycling stability. [J] Advanced Functional Materials. 2014, 24(17), 2500-2509.

[13] Li D, Han F, Wang S, et al. High sulfur loading cathodes fabricated using peapod like, large pore volume mesoporous carbon for lithium sulfur batteries.[J] ACS Applied Materials&Interfaces. 2013, 5(6), 2208-2213.

[14] Liang C.D., Dudney N.J. , Howe J.Y., Hierarchically structured sulfur/carbon nanocomposite material for

high-energy lithium battery[J] Chemistry of Materials, 2009, 21(19), 4724-4730.

[15] Zhang B., Lai Cai, Zhou Z, et al. Preparation and electrochemical properties of sulfur acetylene black composites as cathode material [J] Electrochimica Acta, 2009,54(14), 3708-3713.

[16] He G., Ji X.L. Nazar L.F., High “C” rate Li-S cathode: sulfur imbibed bimodal porous carbons[J] Energy&Environmental Science, 2011, 4(8), 2878-2883.

[17] Zhang B., Qin X., Lai G. R., et al. Enhancement of long stability of sulfur cathode by encapsulating sulfur into micropores of carbon spheres. [J] Energy & Environmental Science. 2010, 3(10),1531-1537.

[18] Xin S, Gu L., Zhao N.-H., et al. Smaller sulfur molecules promise better lithium-sulfur batteries. [J] Journal of American Chemistry Society. 2012, 134(45), 18510−18513.

[19] Li Z., Yuan L., Yi Z., et al. Insight into the electrode mechanism in lithium-sulfur batteries with ordered microporous carbon confined sulfur as the cathode. [J] Advanced Energy Materials. 2014, 4(7), 1301473.

[20] Li Z., Jiang Y., Yuan L., et al. A highly ordered meso@microporous carbon-supported sulfur@smaller sulfur core-shell structured cathode for Li-S Batteries. [J] ACS Nano. 2014, 8(9), 9295-9303.

[21] Wang J.L., Yang J., Wang C.R.,et al. Sulfur composite cathode materials for rechargeable lithium batteries. [J] Advanced Functional Materials, 2003, 13(6), 487-492.

[22] Xiao L.F., Cao Y.L. Xiao J., et al. A soft approach to encapsulate sulfur: polyaniline nanotubes for lithium-sulfur batteries with long cycle life. [J] Advanced Materials. 2012, 24(9), 1176-1181.

[23] Li W.Y., Zhang Q.F., Zheng G.Y., et al. Understanding the role of different conductive polymers in improving the nanostructured sulfur cathode performance. [J] Nano Letters, 2013, 13(11), 5534-5540.

[24] Zheng G.Y., Zhang Q.F., Cha J., et al. Amphiphilic surface modification of hollow carbon nanofibers for improved cycle life of lithium sulfur batteries. [J] Nano Letters, 2013, 13(3), 1265-1270.

[25] Qiu Y., Li W.F., Zhao W., et al. High-rate, ultralong cycle-Life lithium/sulfur batteries enabled by nitrogen-doped graphene [J] Nano Letters, 2014, 14(8), 4821-4827.

[26] Song J.X., Xu T., Gordin M.L., et al. Nitrogen-doped mesoporous carbon promoted chemical adsorption of sulfur and fabrication of high-areal-capacity sulfur cathode with exceptional cycling stability for lithium-sulfur batteries [J] Advanced Functional Materials, 2014, 24(9), 1243-1250.

[27] Yuan S.Y., Bao L., Wang L.N., et al. Graphene-supported nitrogen and boron rich carbon layer for improved performance of lithium-sulfur batteries due to enhanced chemisorption of lithium polysulfides. [J] Advanced Energy Materials, 2016, 6(5), 1501733.

[28] Song J.X, Gordin M., Xu T.,et al. Strong lithium polysulfide chemisorption on electroactive sites of nitrogen-doped carbon composites for high-performance lithium-sulfur battery cathodes. [J] Angewandte Chemie International Edition. 2015, 54(14), 4325-4329.

[29] Pang Q., Tang J.T., He H., et al. A nitrogen and sulfur dual-doped carbon derived from polyrhodanine@cellulose for advanced lithium-sulfur batteries. [J] Advanced Materials. 2015, 27(39), 6021-6028.

[30] Wang H.L., Yang Y., Liang Y., et al. Graphene-Wrapped Sulfur Particles as a Rechargeable LithiumSulfur Battery Cathode Material with High Capacity and Cycling Stability. [J] Nano Letters, 2011, 11(7), 2644-2647.

[31] Ji L.W., Rao M.M., Zheng H.M., et al. Graphene oxide as a sulfur immobilizer in high performance lithium/sulfur cells. [J] Journal of American Chemistry Society. 2011, 133(46), 18522-18525.

[32] Liang X., Hart C., Pang Q., et al. A highly efficient polysulfide mediator for lithium-sulfur batteries. [J] Nature Communications. 2015, 6, 5682.

[33] Chen R. J., Zhao T., Lu J., et al. Graphene-based three-dimensional hierarchical sandwich-type architecture for high-performance Li/S batteries.[J]. Nano Letters, 2013, 13(10), 4642.

[34] Zhao M.Q., Liu X.F., Zhang Q., et al. Graphene/single-walled carbon nanotube hybrids: one-step catalytic growth and applications for high-rate Li-S batteries.[J] ACS Nano, 2012, 6(12), 10759-10769.

[35] Yuan S.Y., Guo Z.Y., Wang L.N., et al. Leaf-like graphene-oxide wrapped sulfur for high-performance lithium-sulfur Battery.[J] Advanced Science, 2015, 2(8), 1500071.

[36] Younesi R., Veith M., Johansson P., et al. Lithium salts for advanced lithium batteries: Li-metal, Li-O_2, and Li-S. [J] Energy& Environmental Science, 2015, 8(7), 1905-1922.

[37] Zhang S. S. The role of LiNO₃ in rechargeable lithium/sulfur battery.[J] Electrochimica Acta, 2012, 70, 78-86.

[38] Suo L.M., Hu Y.S., Li H., et al. A new class of Solvent-in-Salt electrolyte for high-energy rechargeable metallic lithium batteries. [J] Nature Communications, 2013, 4, 1481.

[39] Li W.Y., Yao H.B., Yan K., et al. The synergetic effect of lithium polysulfide and lithium nitrate to prevent lithium dendrite growth. [J] Nature Communications, 2015, 6, 7436.

[40] Gordin M.L., Dai F., Chen S.R., et al., Bis(2,2,2-trifluoroethyl) ether as an electrolyte co-solvent for mitigating self-discharge in lithium-sulfur batteries. [J] ACS Applied Materials&Interfaces, 2014, 6(11), 8006-8010.

[41] Wang L.N., Liu J.Y., Yuan S.Y., et al., To mitigate self-discharge of lithium-sulfur batteries by optimizing ionic liquid electrolytes. [J] Energy&Environmental Science, 2016, 9(1), 224-231.

[42]Wang J.L., Lin F.J., Jia H., et al. Towards a Safe Lithium-Sulfur Battery with a Flame-Inhibiting Electrolyte and a Sulfur-Based Composite Cathode. [J] Angewandte Chemie International Edition, 2014, 53(38), 10099-10104.

[43] Su Y.S., Manthiram A. Lithium-sulphur batteries with a microporous carbon paper as a bifunctional interlayer. [J], Nature Communications , 2012, 3, 1166.

[44] Chung S-H., Manthiram A., Bifunctional separator with a light-weight carbon-coating for dynamically and statically stable lithium-sulfur batteries.[J] Advanced Functional Materials, 2014, 24(33), 5209-5216.

[45] Chung S-H., Manthiram A., High-performance Li-S batteries with an ultra-lightweight MWCNT-coated separator. [J] Journal of Physical Chemistry Letters, 2014, 5,(11) 1978-1983.

[46] 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, 2013, 25(4), 625-631.

[47] Wang L.N., Liu J.Y., Haller S., et al. A scalable hybrid separator for a high performance lithium-sulfur battery. [J] Chemical Communication , 2015, 51(32), 6996-6999.

[48] Nan C.Y., Lin Z., Liao H.G., et al., Durable Carbon-Coated Li₂S Core-Shell Spheres for High Performance Lithium/Sulfur Cells. [J] Journal of the American Chemical Society, 2014, 136(12), 4659-4663.

[49] Qiu Y.C., Rong G.L., Yang J., et al., Highly nitridated graphene-Li₂S cathodes with stable modulated cycles. [J] Advanced Energy Materials, 2015, 5(23), 1501369.

[50] Seh Z. W., Yu J.H., Li W.Y., et al., Two-dimensional layered transition metal disulphides for effective encapsulation of high-capacity lithium sulphide cathodes. [J] Nature Communications, 2014, 5, 5017.

[51]Zu C.X., Klein M., Manthiram A., et al. Activated Li₂S as a high-performance cathode for rechargeable lithium-sulfur batteries. [J] Advanced Energy Materials, 2014, 5(22),3986-3991.

[52] Wang L.N., Wang Y.G., Xia Y.Y., A high performance lithium-ion sulfur battery based on a Li₂S cathode using a dual-phase electrolyte. [J] Energy&Environmental Science, 2015, 8(5), 1551-1558.