GUO Meng-qing, HUANG Jia-qi, KONG Xiang-yi, PENG Hong-jie, SHUI Han, QIAN Fang-yuan, ZHU Lin, ZHU Wan-cheng, ZHANG Qiang. Hydrothermal synthesis of porous phosphorus-doped carbon nanotubes and their use in the oxygen reduction reaction and lithium-sulfur batteries[J]. NEW CARBOM MATERIALS, 2016, 31(3): 352-362.
Citation: GUO Meng-qing, HUANG Jia-qi, KONG Xiang-yi, PENG Hong-jie, SHUI Han, QIAN Fang-yuan, ZHU Lin, ZHU Wan-cheng, ZHANG Qiang. Hydrothermal synthesis of porous phosphorus-doped carbon nanotubes and their use in the oxygen reduction reaction and lithium-sulfur batteries[J]. NEW CARBOM MATERIALS, 2016, 31(3): 352-362.

Hydrothermal synthesis of porous phosphorus-doped carbon nanotubes and their use in the oxygen reduction reaction and lithium-sulfur batteries

Funds:  National Natural Scientific Foundation of China (21306103, 21422604);National Basic Research Program of China (2015CB932500).
  • Received Date: 2016-05-10
  • Accepted Date: 2016-06-28
  • Rev Recd Date: 2016-06-09
  • Publish Date: 2016-06-28
  • The many uses of carbon nanotubes (CNTs) depend not only on their intrinsic physical properties, but also on their tunable chemical components. Exploring a low-temperature method for the incorporation of phosphorus atoms in the carbon framework is expected to change the chemical properties of CNTs. Here, phosphorus-functionalized CNTs (PCNTs) were prepared by the direct hydrothermal treatment of a CNT-H3PO4 mixture at 170℃. The PCNTs had a high phosphorus content of 1.66 at%, a specific surface area of 132 m2·g-1, and an improved thermal stability with a weight loss peak at 694℃ during oxidation in pure oxygen. They showed good electrocatalytic activity for the oxygen reduction reaction with an onset potential of 0.20 V vs Hg/Hg2Cl2, an electron transfer number of 2.60, and a larger current density as well as improved cyclic stability compared with pristine CNTs. PCNTs were also used as conductive scaffolds for the cathode in lithium-sulfur batteries. The cathode delivered an initial discharge capacity of 1 106 mAh·g-1, a capacity retention of 80% from 0.1 to 1.0 C, and a low decay rate of 0.25% per cycle during 100 cycles.
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  • [1]
    Su D S, Zhang J, Frank B, et al. Metal-free heterogeneous catalysis for sustainable chemistry[J]. ChemSusChem, 2010, 3: 169-180.
    Liu Z W, Peng F, Wang H J, et al. Phosphorus-doped graphite layers with high electrocatalytic activity for the O2 reduction in an alkaline medium[J]. Angew Chem Int Ed, 2011, 50: 3257-3261.
    Yang D S, Bhattacharjya D, Inamdar S, et al. Phosphorus-doped ordered mesoporous carbons with different lengths as efficient metal-free electrocatalysts for oxygen reduction reaction in alkaline media[J]. J Am Chem Soc, 2012, 134: 16127-16130.
    Yang D S, Bhattacharjya D, Song M Y, et al. Highly efficient metal-free phosphorus-doped platelet ordered mesoporous carbon for electrocatalytic oxygen reduction[J]. Carbon, 2014, 67: 736-743.
    Tian G L, Zhao M, Yu D, et al. Nitrogen-doped graphene/carbon nanotube hybrids: In situ formation on bifunctional catalysts and their superior electrocatalytic activity for oxygen evolution/reduction reaction[J]. Small, 2014, 10: 2251-2259.
    Wang C, Sun L, Zhou Y, et al. P/N co-doped microporous carbons from H3PO4-doped polyaniline by in situ activation for supercapacitors[J]. Carbon, 2013, 59: 537-546.
    Zhang C Z, Mahmood N, Yin H, et al. Synthesis of phosphorus-doped graphene and its multifunctional applications for oxygen reduction reaction and lithium ion batteries[J]. Adv Mater, 2013, 25: 4932-4937.
    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]. Adv Funct Mater, 2014, 24: 1243-1250.
    Song J, Shen W Z, Wang J G, et al. Superior carbon-based CO2 adsorbents prepared from poplar anthers[J]. Carbon, 2014, 69: 255-263.
    Strelko V V, Kuts V S, Thrower P A. On the mechanism of possible influence of heteroatoms of nitrogen, boron and phosphorus in a carbon matrix on the catalytic activity of carbons in electron transfer reactions[J]. Carbon, 2000, 38: 1499-1503.
    Lee Y J, Radovic L R. Oxidation inhibition effects of phosphorus and boron in different carbon fabrics[J]. Carbon, 2003, 41: 1987-1997.
    Wu X X, Radovic L R. Inhibition of catalytic oxidation of carbon/carbon composites by phosphorus[J]. Carbon, 2006, 44: 141-151.
    Some S, Kim J, Lee K, et al. Highly air-stable phosphorus-doped n-type graphene field-effect transistors[J]. Adv Mater, 2012, 24: 5481-5486.
    Li R, Wei Z D, Gou X L, et al. Phosphorus-doped graphene nanosheets as efficient metal-free oxygen reduction electrocatalysts[J]. RSC Adv, 2013, 3: 9978-9984.
    Wu J, Yang Z R, Li X W, et al. Phosphorus-doped porous carbons as efficient electrocatalysts for oxygen reduction[J]. J Mater Chem A, 2013, 1: 9889-9896.
    Choi C H, Park S H, Woo S I. Binary and ternary doping of nitrogen, boron, and phosphorus into carbon for enhancing electrochemical oxygen reduction activity[J]. ACS Nano, 2012, 6: 7084-7091.
    Yu D S, Xue Y H, Dai L M. Vertically aligned carbon nanotube arrays co-doped with phosphorus and nitrogen as efficient metal-free electrocatalysts for oxygen reduction[J]. J Phys Chem Lett, 2012, 3: 2863-2870.
    Jagtoyen M, Derbyshire F. Activated carbons from yellow poplar and white oak by H3PO4 activation[J]. Carbon, 1998, 36: 1085-1097.
    Puziy A M, Poddubnaya O I, Martinez-Alonso A, et al. Synthetic carbons activated with phosphoric acid Ⅱ. Porous structure[J]. Carbon, 2002, 40: 1507-1519.
    Kucukayan-Dogu G, Sen H S, Yurdakul H, et al. Synthesis of phosphorus included multiwalled carbon nanotubes by pyrolysis of sucrose[J]. J Phys Chem C, 2013, 117: 24554-24560.
    Zuo S L, Yang J X, Liu J L. Effects of the heating history of impregnated lignocellulosic material on pore development during phosphoric acid activation[J]. Carbon, 2010, 48: 3293-3295.
    Romero-Anaya A J, Lillo-Rodenas M A, de Lecea C S M, et al. Hydrothermal and conventional H3PO4 activation of two natural bio-fibers[J]. Carbon, 2012, 50: 3158-3169.
    Yue Z R, Economy J, Mangun C L. Preparation of fibrous porous materials by chemical activation 2. H3PO4 activation of polymer coated fibers[J]. Carbon, 2003, 41: 1809-1817.
    Zhao X C, Zhang Q, Zhang B, et al. Dual-heteroatom-modified ordered mesoporous carbon: Hydrothermal functionalization, structure, and its electrochemical performance[J]. J Mater Chem, 2012, 22: 4963-4969.
    Fan X, Yu C, Ling Z, et al. Hydrothermal synthesis of phosphate-functionalized carbon nanotube-containing carbon composites for supercapacitors with highly stable performance[J]. ACS Appl Mater Interfaces, 2013, 5: 2104-2110.
    Peng H J, Huang J Q, Zhao M Q, et al. Nanoarchitectured graphene/CNT@ porous carbon with extraordinary electrical conductivity and interconnected micro/mesopores for lithium-sulfur batteries[J]. Adv Funct Mater, 2014, 24: 2772-2781.
    Kim M J, Jean I Y, Seo J M, et al. Graphene phosphonic acid as an efficient flame retardant[J]. ACS Nano, 2014, 8: 2820-2825.
    Hayashi J, Kazehaya A, Muroyama K, et al. Preparation of activated carbon from lignin by chemical activation[J]. Carbon, 2000, 38: 1873-1878.
    Guo Y P, Rockstraw D A. Physical and chemical properties of carbons synthesized from xylan, cellulose, and kraft lignin by H3PO4 activation[J]. Carbon, 2006, 44: 1464-1475.
    Zhao L, Baccile N, Gross S, et al. Sustainable nitrogen-doped carbonaceous materials from biomass derivatives[J]. Carbon, 2010, 48: 3778-3787.
    Ramasahayam S K, Nasini U B, Bairi V, et al. Microwave assisted synthesis and characterization of silicon and phosphorous co-doped carbon as an electrocatalyst for oxygen reduction reaction[J]. RSC Adv, 2014, 4: 6306-6313.
    Jo G, Sanetuntikul J, Shanmugam S. Boron and phosphorous-doped graphene as a metal-free electrocatalyst for the oxygen reduction reaction in alkaline medium[J]. RSC Adv, 2015, 5: 53637-53643.
    Zhang Q, Cheng X B, Huang J Q, et al. Review of carbon materials for advanced lithium-sulfur batteries[J]. New Carbon Mater, 2014, 29: 241-264.
    Xu F, Tang Z W, Huang S Q, et al. Facile synthesis of ultrahigh-surface-area hollow carbon nanospheres for enhanced adsorption and energy storage[J]. Nat Commun, 2015, 6: 7221.
    Shi J L, Tang C, Peng H, et al. 3D mesoporous graphene: CVD self-assembly on porous oxide templates and applications in high-stable Li-S batteries[J]. Small, 2015, 11: 5243-5252.
    TANG Zhi-wei, XU Fei, LIANG Ye-ru, et al. Preparation and electrochemical performance of a hierarchically porous activated carbon aerogel/sulfur cathode for lithium-sulfur batteries[J]. New Carbon Mater, 2015, 30: 319-326. (唐志伟, 徐 飞, 梁业如, 等. 层次孔活性炭气凝胶/硫复合正极材料的制备及其电化学性能[J]. 新型炭材料, 2015, 30: 319-326.
    Zhou G M, Yin L C, Wang D W, et al. Fibrous hybrid of graphene and sulfur nanocrystals for high-performance lithium-sulfur batteries[J]. ACS Nano, 2013, 7: 5367-5375.
    Gu X X, Tong C J, Lai C, et al. A porous nitrogen and phosphorous dual doped graphene blocking layer for high performance Li-S batteries[J]. J Mater Chem A, 2015, 3: 16670-16678.
    Liang J, Sun Z H, Li F, et al. Carbon materials for Li-S batteries: Functional evolution and performance improvement[J]. Energy Storage Mater, 2016, 2: 76-106.
    Sun F G, Wang J T, Chen H C, et al. High efficiency immobilization of sulfur on nitrogen-enriched mesoporous carbons for Li-S batteries[J]. ACS Appl Mater Interfaces, 2013, 5: 5630-5638.
    Peng H J, Hou T, Zhang Q, et al. Strongly coupled interfaces between heterogeneous carbon host and sulfur-containing guest for highly-stable lithium-sulfur batteries: Mechanistic insight into capacity degradation[J]. Adv Mater Interfaces, 2014, 1: 1400227.
    Tang C, Zhang Q, Zhao M, et al. Nitrogen-doped aligned carbon nanotube/graphene sandwiches: Facile catalytic growth on bifunctional natural catalysts and their applications as scaffolds for high-rate lithium-sulfur batteries[J]. Adv Mater, 2014, 26: 6100-6105.
    Niu S Z, Lv W, Zhou G M, 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]. Chem Commun, 2015, 51: 17720-17723.
    Zhou G M, Zhao Y B, Manthiram A. Dual-confined flexible sulfur cathodes encapsulated in nitrogen-doped double-shelled hollow carbon spheres and wrapped with graphene for Li-S batteries[J]. Adv Energy Mater, 2015, 5: 1402263.
    Huang J Q, Zhang Q, Wei F. Multi-functional separator/interlayer system for high-stable lithium-sulfur batteries: Progress and prospects[J]. Energy Storage Mater, 2015, 1: 127-145.
    Aurbach D, Pollak E, Elazari R, et al. On the surface chemical aspects of very high energy density, rechargeable Li-sulfur batteries[J]. J Electrochem Soc, 2009, 156: A694-A702.
    Huang J Q, Zhang Q, Zhang S M, et al. Aligned sulfur-coated carbon nanotubes with a polyethylene glycol barrier at one end for use as a high efficiency sulfur cathode[J]. Carbon, 2013, 58: 99-106.
    Kim K H, Jun Y S, Gerbec J A, et al. Sulfur infiltrated mesoporous graphene-silica composite as a polysulfide retaining cathode material for lithium-sulfur batteries[J]. Carbon, 2014, 69: 543-551.
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