A one-step hard-templating method for the preparation of a hierarchical microporous-mesoporous carbon for lithium-sulfur batteries
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摘要: 采用一步硬模板法炭化酚醛树脂和葡萄糖酸镁制备得到具有大表面积和层次化结构的微孔-中孔炭材料（HMMC）。在炭化过程中，葡萄糖酸镁分解形成纳米氧化镁（MgO）可以作为硬模板。制备得到的HMMC具有高的比表面积（1 560 m2·g-1），大的孔容（2.6 cm3·g-1），可以实现较高硫的负载量，并可以提供硫体积膨胀的空间。此外，相互连通的孔结构和炭骨架也能够提供快速的电子和锂离子的传输通道。因此，与硫复合后得到的碳-硫杂化材料（HMMC-S）在0.3 C电流密度下，初始放电容量高达939 mAh·g-1，经150周循环后容量仍有731 mAh·g-1， 每周的容量损失率仅为0.15%。在较高的电流密度2 C下，其容量仍可达626 mAh·g-1，表现出优异的倍率性能和长循环稳定性。Abstract: Porous carbon materials can increase the conductivity of sulfur and restrain the shuttling of polysulfides in the electrolyte. A hierarchical microporous-mesoporous carbon (HMMC) with a large surface area and pore volume was prepared by the simple one-step carbonization of a mixture of magnesium gluconate (MG) and phenolic resin. The MG was transformed into nanosize magnesium oxide that acted as a hard template during carbonization to create mesopores. The HMMC has a high surface area (~1 560 m2·g-1) and large pore volume (~2.6 cm3·g-1), which provides abundant space for sulfur loading and accommodates volume changes during charge/discharge. The interconnected pore structure and carbon framework ensure fast electron and Li ion transfer. As the cathode of a Li-S battery the sulfur-loaded HMMC has a high discharge capacity of 939 mAh·g-1 at 0.3 C and a reversible capacity of 731 mAh·g-1 after 150 cycles with only a 0.15% capacity fade per cycle. Even at a high rate of 2 C, it still delivers a high discharge capacity of 626 mAh·g-1, showing an excellent rate performance.
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Manthiram A, Chung S H, Zu C. Lithium-sulfur batteries: Progress and prospects[J]. Advanced Materials, 2015, 27(12): 1980-2006. Liang J, Sun Z H, Li F, et al. Carbon materials for Li-S batteries: Functional evolution and performance improvement[J]. Energy Storage Materials, 2016, 2: 76-106. Zhang Q, Cheng X B, Huang J Q, et al. Review of carbon materials for advanced lithium-sulfur batteries[J]. New Carbon Materials, 2014, 29(4): 241-264. Huang J Q, Zhang Q, Wei F. Multi-functional separator/interlayer system for high-stable lithium-sulfur batteries: Progress and Prospects[J]. Energy Storage Materials, 2015, 1: 127-145. Li F F, Lu W, Niu S Z, et al. Preparation and electrochemical performance of a graphene-wrapped carbon/sulphur composite cathode[J]. New Carbon Materials, 2014, 29(4): 309-315. Yu M, Li R, Wu M, et al. Graphene materials for lithium-sulfur batteries[J]. Energy Storage Materials, 2015, 1: 51-73. Lv W, Li Z, Deng Y, et al. Graphene-based materials for electrochemical energy storage devices: Opportunities and challenges[J]. Energy Storage Materials, 2016, 2: 107-138. Zhu L, Zhu W C, Cheng X B, et al. Cathode materials based on carbon nanotubes for high-energy-density lithium-sulfur batteries[J]. Carbon, 2014, 75(8): 161-168. Niu S, Lv W, Zhang C, et al. One-pot self-assembly of graphene/carbon nanotube/sulfur hybrid with three dimensionally interconnected structure for lithium-sulfur batteries[J]. Journal of Power Sources, 2015, 295: 182-189. Xin S, Gu L, Zhao N-H, et al. Smaller sulfur molecules promise better lithium-sulfur batteries[J]. Journal of the American Chemical Society, 2012, 134(45): 18510-18513. Werner J G, Johnson S S, Vijay V, et al. Carbon-sulfur composites from cylindrical and gyroidal mesoporous carbons with tunable properties in lithium-sulfur batteries[J]. Chemistry of Materials, 2015, 27(9): 3349-3357. Xu F, Tang Z, Huang S, et al. Facile synthesis of ultrahigh-surface-area hollow carbon nanospheres for enhanced adsorption and energy storage[J]. Nat Commun, 2015, 6: 7221. Tang Z W, Xu F, Liang Y R, et al. Preparation and electrochemical performance of a hierarchically porous activated carbon aerogel /sulfur cathode for lithium-sulfur batteries[J]. New Carbon Materials, 2015, 30(4): 319-326. Chen S, Sun B, Xie X, et al. Multi-chambered micro/mesoporous carbon nanocubes as new polysulfides reserviors for lithium-sulfur batteries with long cycle life[J]. Nano Energy, 2015, 16(0): 268-280. Liang C, 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. Gorka J, Zawislak A, Choma J, et al. KOH activation of mesoporous carbons obtained by soft-templating[J]. Carbon, 2008, 46(8): 1159-1161. Chen Xa, Xiao Z, Ning X, et al. Sulfur-impregnated, sandwich-type, hybrid carbon nanosheets with hierarchical porous structure for high-performance lithium-sulfur batteries[J]. Advanced Energy Materials, 2014, 4(13): 1301988. Wang J, Wu Y, Shi Z, et al. Mesoporous carbon with large pore volume and high surface area prepared by a co-assembling route for lithium-sulfur batteries[J]. Electrochimica Acta, 2014, 144: 307-314. Morishita T, Tsumura T, Toyoda M, et al. A review of the control of pore structure in MgO-templated nanoporous carbons[J]. Carbon, 2010, 48(10): 2690-2707. Morishige K, Tateishi N. Adsorption hysteresis in ink-bottle pore[J]. The Journal of Chemical Physics, 2003, 119(4): 2301-2306. Li Z, Wu D, Liang Y, et al. Synthesis of well-defined microporous carbons by molecular-scale templating with polyhedral oligomeric silsesquioxane moieties[J]. Journal of the American Chemical Society, 2014, 136(13): 4805-4808. Wu D, Li Z, Zhong M, et al. Templated synthesis of nitrogen-enriched nanoporous carbon materials from porogenic organic precursors prepared by ATRP[J]. Angewandte Chemie International Edition, 2014, 53(15): 3957-3960. Mai W, Sun B, Chen L, et al. Water-dispersible, responsive, and carbonizable hairy microporous polymeric nanospheres[J]. Journal of the American Chemical Society, 2015, 137(41): 13256-13259. Zhang C, Liu D-H, Lv W, et al. A high-density graphene-sulfur assembly: a promising cathode for compact Li-S batteries[J]. Nanoscale, 2015, 7(13): 5592-5597. Xu G, Ding B, Nie P, et al. Hierarchically porous carbon encapsulating sulfur as a superior cathode material for high performance lithium-sulfur batteries[J]. ACS Applied Materials & Interfaces, 2014, 6(1): 194-199. Niu S, Lv W, Zhang C, et al. A carbon sandwich electrode with graphene filling coated by N-doped porous carbon layers for lithium-sulfur batteries[J]. Journal of Materials Chemistry A, 2015, 3(40): 20218-20224. 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 the American Chemical Society, 2011, 133(46): 18522-18525. Ding B, Yuan C, Shen L, et al. Chemically tailoring the nanostructure of graphene nanosheets to confine sulfur for high-performance lithium-sulfur battery[J]. Journal of Materials Chemistry A, 2013, 1(4) : 1096-1101. Zu C, Manthiram A. Hydroxylated graphene-sulfur nanocomposites for high-rate lithium-sulfur batteries[J]. Advanced Energy Materials, 2013, 3(8): 1008-1012. Zhang J, Lv W, Tao Y, et al. Ultrafast high-volumetric sodium storage of folded-graphene electrodes through surface-induced redox reactions[J]. Energy Storage Materials, 2015, 1: 112-118. Niu S, Lv W, Zhou G, et al. N and S co-doped porous carbon spheres prepared using l-cysteine as a dual functional agent for high-performance lithium-sulfur batteries[J]. Chemical Communications, 2015, 51(100): 17720-17723. Kolosnitsyn V S, Kuzmina E V, Karaseva E V, et al. A study of the electrochemical processes in lithium-sulphur cells by impedance spectroscopy[J]. Journal of Power Sources, 2011, 196(3): 1478-1482. -
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