氮掺杂空心炭球作为锂离子电池负极材料的研究
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摘要
以聚苯乙烯为模板,聚吡咯为炭前驱体,制备出尺寸均匀的氮掺杂空心炭球(NHCs)。通过N_2吸脱附曲线、X射线光电子能谱、X射线衍射、扫描电子显微镜、透射电子显微镜和循环伏安法等测试方法考察了炭化温度对空心炭球的微观结构与电化学性能的影响。结果表明,制备的空心炭球直径在160 nm左右,氮原子百分含量达到9.69%。0.5 A·g~(-1)的电流密度下,800℃炭化所得空心球经过200次循环可逆容量达到493.4 mA·h·g~(-1),容量保持率为84%;在5 A·g~(-1)的电流密度下,经过1000次循环,可逆容量仍高达265.2 mA·h·g~(-1)。说明所制备的空心球拥有高的可逆容量、良好的倍率性能和长的循环寿命,是一种优异的储锂材料。
Nitrogen-doped hollow carbon spheres(NHCs) were synthesized by using polypyrrole as nitrogen-enriched precursor and polystyrene sphere as template. The morphologies and electrochemical properties of the as-prepared materials were characterized by BET, XPS, XRD, SEM, TEM, and cyclic voltammetry. Results showed that the diameter of the hollow carbon spheres was about 160 nm, and the nitrogen atom content reached 9.69%. When used as anode material of lithium-ion batteries, the NHCs exhibit excellent Li-storage performance. The NHCs carbonized at 800 ℃, gained a reversible specific capacity of 493.4 mA·h·g~(-1) with a retention of 84% after 200 cycles at 0.5 A·g~(-1), and a retention capability of 265.2 mA·h·g~(-1) after 1000 cycles at 5 A·g~(-1). It shows that NHCs have high reversible capacity, preeminent rate performance and long cycle life, which can be an excellent lithium storage material.
Nitrogen-doped hollow carbon spheres(NHCs) were synthesized by using polypyrrole as nitrogen-enriched precursor and polystyrene sphere as template. The morphologies and electrochemical properties of the as-prepared materials were characterized by BET, XPS, XRD, SEM, TEM, and cyclic voltammetry. Results showed that the diameter of the hollow carbon spheres was about 160 nm, and the nitrogen atom content reached 9.69%. When used as anode material of lithium-ion batteries, the NHCs exhibit excellent Li-storage performance. The NHCs carbonized at 800 ℃, gained a reversible specific capacity of 493.4 mA·h·g~(-1) with a retention of 84% after 200 cycles at 0.5 A·g~(-1), and a retention capability of 265.2 mA·h·g~(-1) after 1000 cycles at 5 A·g~(-1). It shows that NHCs have high reversible capacity, preeminent rate performance and long cycle life, which can be an excellent lithium storage material.
引文
[1]楠顶,黄正宏,康飞宇,等.电纺丝制备掺氮多孔炭纳米纤维布用作锂离子电池负极材料[J].新型炭材料, 2016,4(31):393-396.
[2]Lin J, Xu Y L, Wang J, et al. Nitrogen-doped hierarchically porous carbonaceous nanotubes for lithium-ion batteries[J].Chemical Engineering Journal, 2018, 352:964-971.
[3]Huang Q L, Wang S L, Zhang Y, et al. Hollow carbon nanospheres with extremely small size as anode material in lithium-ion batteries with outstanding cycling stability[J].Journal of Physical chemistry, 2016, 120:3139-3144.
[4]Yang Y, Jin S, Zhang Z, et al. Nitrogen-doped hollow carbon nanospheres for high-performance Li-ion batteries[J]. ACS Applied Materials&Interfaces 2017, 9(16):14180-14186.
[5]Xiao M, MengY, Duan C, et al. Nitrogen doped porous onion carbon derived from ionic liquids as the anode materials for lithium ion batteries with high performance[J]. Journal of Electroanalytical Chemistry, 2018, 827:167-174.
[6]Pei F, An T, 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.
[7]Wang D, Xu L, Wang Y, et al. Rational synthesis of porous carbon nanocages and their potential application in high rate supercapacitors[J]. Journal of Electroanalytical Chemistry, 2018, 815:166-174.
[8]Lu W, Guo X, Luo Y, et al. Core-shell materials for advanced batteries[J]. Chemical Engineering Journal, 2019,355:208-237.
[9]Zhang Q, Li M, Meng Y, et al. KOH activated nitrogen doped hard carbon nanotubes as high performance anode for lithium ion batteries[J]. Electronic Materials Letters,2018, 14(6):755-765.
[10]Li H, Wei Y, Ren J, et al. Three-dimensionally ordered hierarchically porous polypyrrole loading sulfur as highperformance cathode for lithium/sulfur batteries[J]. Polymer, 2018, 137:261-268.
[11]Yang M, Zhong Y, Bao J, et al. Achieving battery-level energy density by constructing aqueous carbonaceous supercapacitors with hierarchical porous N-rich carbon materials[J]. Journal of Materials Chemistry A, 2015, 3(21):11387-11394.
[12]Wang J R, Fan H B, Shen Y M, et al. Large-scale templatefree synthesis of nitrogen-doped 3D carbon frameworks as low-cost ultra-long-life anodes for lithium-ion batteries[J].Chemical Engineering Journal, 2019, 357:376-383.
[13]Li Y, Zheng S, Liu X, et al. Conductive microporous covalent triazine-based framework for high-performance electrochemical capacitive energy storage[J]. Angewandte Chemie, 2018, 57(27):7992-7996.
[14]Yang M, Zhou Z. Recent breakthroughs in supercapacitors boosted by nitrogen-rich porous carbon materials[J].Advanced Science, 2017, 4(8):1600408.
[15]Wang L, Yang C L, Dou S, et al. Nitrogen-doped hierarchically porous carbon networks:synthesis and applications in lithium-ion battery, sodium-ion battery and zincair battery[J]. Electrochimica Acta, 2016, 219:592-603.
[16]Xu Z, Zhuang X, Yang C, et al. Nitrogen-doped porous carbon superstructures derived from hierarchical assembly of polyimide nanosheets[J]. Advanced Materials, 2016, 28(10):1981-1987.
[17]Zhang Y, Ma Q, Wang S, et al. Poly(vinyl alcohol)-assisted fabrication of hollow carbon spheres/reduced graphene oxide nanocomposites for high-performance lithium-ion battery Anodes[J]. ACS Nano, 2018, 12(5):4824-4834.
[18]Xu C P, Niu D C, Zheng N, et al. Facile synthesis of nitrogen-doped double-shelled hollow mesoporous carbon nanospheres as high-performance anode materials for lithium ion batteries[J]. ACS Sustainable Chemistry&Engineering, 2018, 6:5999-6007.
[2]Lin J, Xu Y L, Wang J, et al. Nitrogen-doped hierarchically porous carbonaceous nanotubes for lithium-ion batteries[J].Chemical Engineering Journal, 2018, 352:964-971.
[3]Huang Q L, Wang S L, Zhang Y, et al. Hollow carbon nanospheres with extremely small size as anode material in lithium-ion batteries with outstanding cycling stability[J].Journal of Physical chemistry, 2016, 120:3139-3144.
[4]Yang Y, Jin S, Zhang Z, et al. Nitrogen-doped hollow carbon nanospheres for high-performance Li-ion batteries[J]. ACS Applied Materials&Interfaces 2017, 9(16):14180-14186.
[5]Xiao M, MengY, Duan C, et al. Nitrogen doped porous onion carbon derived from ionic liquids as the anode materials for lithium ion batteries with high performance[J]. Journal of Electroanalytical Chemistry, 2018, 827:167-174.
[6]Pei F, An T, 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.
[7]Wang D, Xu L, Wang Y, et al. Rational synthesis of porous carbon nanocages and their potential application in high rate supercapacitors[J]. Journal of Electroanalytical Chemistry, 2018, 815:166-174.
[8]Lu W, Guo X, Luo Y, et al. Core-shell materials for advanced batteries[J]. Chemical Engineering Journal, 2019,355:208-237.
[9]Zhang Q, Li M, Meng Y, et al. KOH activated nitrogen doped hard carbon nanotubes as high performance anode for lithium ion batteries[J]. Electronic Materials Letters,2018, 14(6):755-765.
[10]Li H, Wei Y, Ren J, et al. Three-dimensionally ordered hierarchically porous polypyrrole loading sulfur as highperformance cathode for lithium/sulfur batteries[J]. Polymer, 2018, 137:261-268.
[11]Yang M, Zhong Y, Bao J, et al. Achieving battery-level energy density by constructing aqueous carbonaceous supercapacitors with hierarchical porous N-rich carbon materials[J]. Journal of Materials Chemistry A, 2015, 3(21):11387-11394.
[12]Wang J R, Fan H B, Shen Y M, et al. Large-scale templatefree synthesis of nitrogen-doped 3D carbon frameworks as low-cost ultra-long-life anodes for lithium-ion batteries[J].Chemical Engineering Journal, 2019, 357:376-383.
[13]Li Y, Zheng S, Liu X, et al. Conductive microporous covalent triazine-based framework for high-performance electrochemical capacitive energy storage[J]. Angewandte Chemie, 2018, 57(27):7992-7996.
[14]Yang M, Zhou Z. Recent breakthroughs in supercapacitors boosted by nitrogen-rich porous carbon materials[J].Advanced Science, 2017, 4(8):1600408.
[15]Wang L, Yang C L, Dou S, et al. Nitrogen-doped hierarchically porous carbon networks:synthesis and applications in lithium-ion battery, sodium-ion battery and zincair battery[J]. Electrochimica Acta, 2016, 219:592-603.
[16]Xu Z, Zhuang X, Yang C, et al. Nitrogen-doped porous carbon superstructures derived from hierarchical assembly of polyimide nanosheets[J]. Advanced Materials, 2016, 28(10):1981-1987.
[17]Zhang Y, Ma Q, Wang S, et al. Poly(vinyl alcohol)-assisted fabrication of hollow carbon spheres/reduced graphene oxide nanocomposites for high-performance lithium-ion battery Anodes[J]. ACS Nano, 2018, 12(5):4824-4834.
[18]Xu C P, Niu D C, Zheng N, et al. Facile synthesis of nitrogen-doped double-shelled hollow mesoporous carbon nanospheres as high-performance anode materials for lithium ion batteries[J]. ACS Sustainable Chemistry&Engineering, 2018, 6:5999-6007.