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Corresponding Author

Chang-ming LI(ecmli@swu.edu.cn)

Abstract

Lithium-sulphur (Li-S) battery is regarded as a promising energy storage device because of its high theoretical capacity. However, the low S utilization and short cycling life limit the commercial applications. In this work, nitrogen-doped graphene-like carbon (NGC) materials were synthesized by simply pyrolyzing and carbonizing the mixture of melamine (C3H6N6) and L-cysteine (C3H7NO2S). The graphene-like structure in NGC effectively buffered the volume change of S during the discharge/charge process and improved the cycling stability. Meanwhile, nitrogen-containing functional groups in NGC facilitated the transportation of ions and suppressed the dissolution of polysulphide (PS), enabling a high utilization of S. As expected, the NGC-8 (the mass ratio of melamine and L-cysteine being 8:1)/PS cathode delivered a high initial discharge capacity of 1164.1 mAh·g-1 at 0.2 C and still retained 909.4 mAh·g-1 capacity after 400 cycles with a slow capacity decay rate of 0.05% per cycle. Even at as high as 2 C, a high-rate capacity of 820 mAh·g-1 could be achieved.

Graphical Abstract

Keywords

lithium-sulphur battery, graphene-like carbon, volume change, cycling stability

Publication Date

2020-10-28

Online Available Date

2020-09-21

Revised Date

2020-09-01

Received Date

2020-06-28

References

[1] Yang Y, Zheng G Y, Cui Y. Nanostructured sulfur cathodes[J]. Chemical Society Reviews, 2013,42(7):3018-3032.
doi: 10.1039/c2cs35256g URL pmid: 23325336

[2] Manthiram A, Chung S H, Zu C X. Lithium-sulfur batteries: Progress and prospects[J]. Advanced Materials, 2015,27(12):1980-2006.
URL pmid: 25688969

[3] Rosenman A, Markevich E, Salitra G, et al. Review on Li-sulfur battery systems: an integral perspective[J]. Ad-vanced Energy Materials, 2015,5(16):1500212.

[4] Evers S, Nazar L F. New approaches for high energy density lithium-sulfur battery cathodes[J]. Accounts of Chemical Research, 2013,46(5):1135-1143.
doi: 10.1021/ar3001348 URL pmid: 23054430

[5] Pope M A, Aksay I A. Structural design of cathodes for Li-S batteries[J]. Advanced Energy Materials, 2015,5(16):1500124.

[6] Wang J L, He Y S, Yang J. Sulfur-based composite cathode materials for high-energy rechargeable lithium batteries[J]. Advanced Materials, 2015,27(3):569-575.
doi: 10.1002/adma.201402569 URL pmid: 25256595

[7] Bruce P G, Freunberger S A, Hardwick L J, et al. Li-O2 and Li-S batteries with high energy storage[J]. Nature Materials, 2012,11(1):19-29.
URL pmid: 22169914

[8] L. Ma, Zhuang H L L, Wei S Y, et al. Enhanced Li-S batteries using amine-functionalized carbon nanotubes in the cathode[J]. ACS Nano, 2016,10(1):1050-1059.
doi: 10.1021/acsnano.5b06373 URL pmid: 26634409

[9] Fang R P, Zhao S Y, Hou P X, et al. 3D interconnected electrode materials with ultrahigh areal sulfur loading for Li-S batteries[J]. Advanced Materials, 2016,28(17):3374-3382.
doi: 10.1002/adma.201506014 URL pmid: 26932832

[10] 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.
URL pmid: 19448613

[11] Ji L W, Rao M M, Aloni S, et al. Porous carbon nanofiber-sulfur composite electrodes for lithium/sulfur cells[J]. Energy & Environmental Science, 2011,4(12):5053-5059.

[12] Yao H B, Zheng G Y, Hsu P C, et al. Improving lithium-sulphur batteries through spatial control of sulphur species deposition on a hybrid electrode surface[J]. Nature Communications, 2014,5:3943.
doi: 10.1038/ncomms4943 URL pmid: 24862162

[13] 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.
doi: 10.1038/ncomms11203 URL pmid: 27046216

[14] Ye H, Yin Y X, Xin S, et al. Tuning the porous structure of carbon hosts for loading sulfur toward long lifespan cathode materials for Li-S batteries[J]. Journal of Materials Chemistry A, 2013,1(22):6602-6608.

[15] Puthirath A B, Baburaj A, Kato K, et al. High sulfur content multifunctional conducting polymer composite electrodes for stable Li-S battery[J]. Electrochimica Acta, 2019,306:489-497.

[16] Liu X, Huan J Q, Zhang Q, et al. Nanostructured metal oxides and sulfides for lithium-sulfur batteries[J]. Advanced Materials, 2017,29(20):1601759.

[17] Yilmaz G, Peh S B, Zhao D, et al. Atomic- and molecular-level design of functional metal-organic frameworks (MOFs) and derivatives for energy and environmental applications[J]. Advanced Science, 2019,6(21):1901129.
URL pmid: 31728281

[18] Yang H B, Miao J W, Hung S F, et al. Identification of catalytic sites for oxygen reduction and oxygen evolution in N-doped graphene materials: Development of highly efficient metal-free bifunctional electrocatalyst[J]. Science Advance, 2016,2(4):e1501122.

[19] 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.

[20] Zhou G M, Wang D W, Yin L C, et al. Oxygen bridges between NiO nanosheets and graphene for improvement of lithium storage[J]. ACS Nano, 2012,6(4):3214-3223.
URL pmid: 22424545

[21] Guo J C, Xu Y H, Wang C S. Sulfur-impregnated disordered carbon nanotubes cathode for lithium-sulfur batteries[J]. Nano Letters, 2011,11(10):4288-4294.
doi: 10.1021/nl202297p URL pmid: 21928817

[22] Liu J H, Li W F, Duan L M, et al. A graphene-like oxygenated carbon nitride material for improved cycle-life lithium/sulfur batteries[J]. Nano Letters, 2015,15(8):5137-5142.
doi: 10.1021/acs.nanolett.5b01919 URL pmid: 26148211

[23] Park S, Lee K S, Bozoklu G, et al. Graphene oxide papers modified by divalent ions—enhancing mechanical properties via chemical cross-linking[J]. ACS Nano, 2008,2(3):572-578.
URL pmid: 19206584

[24] Shen W Z, Ren L W, Zhou H, et al. Facile one-pot synjournal of bimodal mesoporous carbon nitride and its function as a lipase immobilization support[J]. Journal of Materials Chemistry, 2011,21(11):3890-3894.

[25] Biniak S, Szymański G, Siedlewski J, et al. The characterization of activated carbons with oxygen and nitrogen surface groups[J]. Carbon, 1997,35(12):1799-1810.

[26] Yang H B, Miao J W, Hung S F, et al. Identification of catalytic sites for oxygen reduction and oxygen evolution in N-doped graphene materials: Development of highly efficient metal-free bifunctional electrocatalyst[J]. Science Advances, 2016,2(4):e1501122.
URL pmid: 27152333

[27] Chen C, Xu G B, Wei X L. A macroscopic three-dimensional tetrapod-separated graphene-like oxygenated Ndoped carbon nanosheet architecture for use in supercapacitors[J]. Journal of Materials Chemistry A, 2016,4(25):9900-9909.

[28] Pei F, Lin L L, Fu A, et al. A two-dimensional porous carbon-modified separator for high-energy-density Li-S batteries[J]. Joule, 2017,2(2):323-336.

[29] Zhu L, Jiang H T, Ran W X, et al. Turning biomass waste to a valuable nitrogen and boron dual-doped carbon aerogel for high performance lithium-sulfur batteries[J]. Applied Surface Science, 2019,489:154-164.

[30] Liu J H, Li W F, Duan L M, et al. A graphene-like oxygenated carbon nitride material for improved cycle-life lithium/sulfur batteries[J]. Nano Letters, 2015,15(8):5137-5142.
URL pmid: 26148211

[31] Yamin H, Gorenshtein A, Penciner J, et al. Oxidation/reduction mechanismsof polysulfidesin THF solutions[J]. Journal of Electrochemstry Society, 1988,135(5):1045-1048.

[32] 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.
doi: 10.1002/adma.201103274 URL pmid: 22052740

[33] Akridge J R, Mikhaylik Y V, White N. Li/S fundamental chemistry and application to high-performance rechargeable batteries[J]. Solid State Ionics, 2004,175(1/4):243-245.

[34] Nelson J, Misra S, Yang Y. et al. In operando X-ray diffraction and transmission X-ray microscopy of lithium sulfur batteries[J]. Journal of the American Chemical Society, 2012,134(14):6337-6343.
URL pmid: 22432568

[35] Jayaprakash N, Shen J, Moganty S S, et al. Porous hollow carbon@sulfur composites for high-power lithium-sulfur batteries[J]. Angewandte Chemie International Edition, 2011,50(26):5904-5908.
doi: 10.1002/anie.201100637 URL pmid: 21591036

[36] Cai J J, Wu C, Zhu Y, et al. Sulfur impregnated N, P co-doped hierarchical porous carbon as cathode for high performance Li-S batteries[J]. Journal of Power Sources, 2017,341:165-174.
doi: 10.1016/j.jpowsour.2016.12.008 URL

[37] Tripathi A K, Verma Y L, Singh R K. Thermal, electrical and structural studies on ionic liquid confined in ordered mesoporous MCM-41[J]. Journal of Materials Chemistry A, 2015,3(47):23809-23820.

[38] Pei F, An T H, Zang J, et al. From hollow carbon spheres to N-doped hollow porous carbon bowls: rational design of hollow carbon host for Li-S batteries[J]. Advanced Energy Materials, 2016,6(8):1502539.

[39] Zheng Z M, Guo H C, Pei F, et al. High sulfur loading in hierarchical porous carbon rods constructed by vertically oriented porous graphene-like nanosheets for Li-S batteries[J]. Advanced Functional Materials. 2016,26(48):8952-8959.

[40] Chen K, Sun Z H, Fang R P, et al. Metal-organic frameworks (MOFs)-derived nitrogen-doped porous carbon anchored on graphene with multifunctional effects for lithium-sulfur batteries[J]. Advanced Functional Materials, 2018,28(38):1707592.

[41] Gao X J, Sun Q, Yang X F, et al. Toward a remarkable Li-S battery via 3D printing[J]. Nano Energy, 2019,56:595-603.

[42] Wu P, Chen L H, Xiao S S, et al. Insight into the positive effect of porous hierarchy in S/C cathodes on the electrochemical performance of Li-S batteries[J]. Nanoscale, 2018,10(25):11861-11868.
URL pmid: 29897083

[43] Zhang H, Gao Q M, Qian W W, et al. Binary hierarchical porous graphene/pyrolytic carbon nanocomposite matrix loaded with sulfur as a high-performance Li-S battery cathode[J]. ACS Applied Materials & Interfaces, 2018,10(22):18726-18733.
doi: 10.1021/acsami.8b03806 URL pmid: 29762008

[44] Zhong M E, Guan J D, Sun J C, et al. Carbon nanodot-decorated alveolate N, O, S tridoped hierarchical porous carbon as efficient electrocatalysis of polysulfide conversion for lithium-sulfur batteries[J]. Electrochimica Acta, 2019,299:600-609.

[45] Kim J, Kang Y, Song S W, et al. Freestanding sulfur-graphene oxide/carbon composite paper as a stable cathode for high performance lithium-sulfur batteries[J]. Electrochimica Acta, 2019,299:27-33.

[46] Duan L F, Zhao L J, Cong H, et al. Plasma treatment for nitrogen-doped 3D graphene framework by a conductive matrix with sulfur for high-performance Li-S batteries[J]. Small, 2019,15(7):1804347.

[47] Wang S X, Zou K X, Qian Y X, et al. Insight to the synergistic effect of N-doping level and pore structure on improving the electrochemical performance of sulfur/N-doped porous carbon cathode for Li-S batteries[J]. Carbon, 2019,144:745-755.

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