晶须形中空多孔氮掺杂复合碳电极材料的制备及电化学性能研究

doi:10.11949/j.issn.0438-1157.20180270

化工学报 ›› 2018, Vol. 69 ›› Issue (S1): 115-122.DOI: 10.11949/j.issn.0438-1157.20180270

• 材料化学工程与纳米技术 • 上一篇下一篇

晶须形中空多孔氮掺杂复合碳电极材料的制备及电化学性能研究

刘羽^1,2, 贺鑫^1,2, 周文英^1,2, 廖丹葵^1,2, 崔学民^1,2, 苏耀恩^1,2, 童张法^1,2

1 广西大学化学化工学院, 广西南宁 530004;
2 广西碳酸钙产业化工程院, 广西南宁 530004c

收稿日期:2018-03-14 修回日期:2018-06-11 出版日期:2018-09-30 发布日期:2018-09-30
通讯作者: 童张法,E-mail:zhftong@sina.com
基金资助:
广西科技重大专项（AA16380050）；广西自然科学基金项目（2016GXNSFGA380003）。

Preparation and electrochemical properties of whisker-shaped hollow porous nitrogen-doped composite carbon electrode materials

LIU Yu^1,2, HE Xin^1,2, ZHOU Wenying^1,2, LIAO Dankui^1,2, CUI Xuemin^1,2, SU Yao'en^1,2, TONG Zhangfa^1,2

1 School of Chemistry and Chemical Engineering, Guangxi University, Nanning 530004, Guangxi, China;
2 Guangxi Engineering Academy of Calcium Carbonate Industrialization, Nanning 530004, Guangxi, China

Received:2018-03-14 Revised:2018-06-11 Online:2018-09-30 Published:2018-09-30
Supported by:
supported by the Major Science and Technology Foundation of Guangxi (AA16380050) and the Natural Science Foundation of Guangxi (2016GXNSFGA380003).

摘要/Abstract

摘要：

中空多孔碳因其低密度、大孔容、高比表面积以及优良的电导率，被视为一种理想的电负极材料。以纳米碳酸钙晶须为模板剂，负载聚多巴胺薄膜与氧化石墨烯，作为碳源与氮源，制备出晶须形中空多孔碳材料（Cw-GO），应用于锂离子电池负极。碳化过程中，碳酸钙晶须经高温分解释放出大量二氧化碳，刺破碳前体壳层，具有高效扩孔功能。利用扫描电子显微镜（SEM）、透射电子显微镜（TEM）、氮气吸附-脱附仪对样品形貌和结构进行了表征，利用循环伏安（CV）、阻抗谱（EIS）、循环充放电（GCD）对样品进行电化学性能检测。结果表明，复合材料Cw-GO在500 mA·g^-1的电流密度下，其初始放电比容量可达到1185.9 mA·h·g^-1，在循环200次后，比容量为921.8 mA·h·g^-1，库仑效率基本保持在99.4%，表现出优异的电化学性能。

关键词: 中空多孔碳, 碳酸钙晶须, 氧化石墨烯, 锂离子电池

Abstract:

Hollow porous carbon is considered as an ideal material for the negative electrode due to its low density, large pore volume, high specific surface area and good electrical conductivity. A facile approach for preparing hollow whisker porous carbon material (Cw-GO) for the negative electrode of Lithium-ion battery is proposed by using polydopamine and graphene oxide as carbon and nitrogen source, and CaCO₃ whisker as a template agent. The activator CO₂, is generated from whisker template and make a great contribution to high specific surface area (SSA) during carbonizing process. The morphology and structure of sample are characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM) and volumetric adsorption analyzer. The electrochemical characteristics of sample is investigated by cyclic voltammetry (CV), impedance spectroscopy (EIS) and cyclic charge-discharge (GCD). Cw-GO shows the first discharge capacity of 1185.9 mA·h·g^-1 under the current density of 500 mA·g^-1, and decreased to 921.8 mA·h·g^-1 through 200 cycles, the coulomb efficiency remains at 99.4%.

Key words: hollow porous carbon, whisker calcium carbonate, graphene oxide, lithium-ion battery

中图分类号:

TQ127.1

刘羽, 贺鑫, 周文英, 廖丹葵, 崔学民, 苏耀恩, 童张法. 晶须形中空多孔氮掺杂复合碳电极材料的制备及电化学性能研究[J]. 化工学报, 2018, 69(S1): 115-122.

LIU Yu, HE Xin, ZHOU Wenying, LIAO Dankui, CUI Xuemin, SU Yao'en, TONG Zhangfa. Preparation and electrochemical properties of whisker-shaped hollow porous nitrogen-doped composite carbon electrode materials[J]. CIESC Journal, 2018, 69(S1): 115-122.

参考文献 30

[1]	WANG H L, CASALONGUE H S, LIANG Y Y, et al. Ni(OH)2 nanoplates grown on grapheme as advanced electrochemical pseudo capacitor materials[J]. J. Am. Chem. Soc., 2010, 132:7472-7477.
[2]	WU Y P, MA J Q, DAI X B, et al. Lithium Ion Batteries:Practice Applications[M]. Beijing:Chemical Industry Press, 2004.
[3]	李巧乐, 燕映霖, 杨蓉, 等. 锂硫电池用玉米苞叶基活性炭/硫复合正极材料的电化学性能[J]. 化工学报, 2017, 68(11):4376-4382. LI Q L, YAN Y L, YANG R, et al. Electrochemical performance of activated carbon derived from corn bracts/sulfur composite cathode material for lithium-sulfur batteries[J]. CIESC Journal, 2017, 68(11):4376-4382.
[4]	SU L W, JING Y, ZHOU Z. Li ion battery materials with core-shell nanostructures[J]. Nanoscale, 2011, 3(10):3967-3983.
[5]	张金龙, 佟微, 漆汉宏. 锂电池发展浅谈[J]. 电源技术, 2017, (9):1377-1379. ZHANG J L, TONG W, QI H H. Discussion of lithium battery development[J]. Power Technology, 2017, (9):1377-1379.
[6]	PAIER J, ASAHI R, NAGOYA A, et al. Cu2ZnSnS4 as a potential photovoltaic material:a hybrid Hartree-Fock density functional theory study[J]. Physical Review B, 2009, 79(11):115126.
[7]	宋刘斌, 唐福利, 肖忠良, 等. 含导电聚苯胺类锂离子电池复合材料的现状及发展趋势[J]. 化工学报, 2017, 68(7):2631-2640. SONG L B, TANG F L, XIAO Z L, et al. Current status and development trend of conductive polyaniline lithium-ion battery composites[J]. CIESC Journal, 2017, 68(7):2631-2640.
[8]	LU W, YUAN D, ZHAO D, et al. Porous polymer networks:synthesis, porosity, and applications in gas storage/separation[J]. Chem. Mater., 2010, 22:5964-5972.
[9]	YANG Q H, XU W H, TOMITA A, et al. The template synthesis of double coaxial carbon nanotubes with nitrogen-doped and boron-doped multiwalls[J]. J. Am. Chem. Soc., 2005, 127(25):8956-8957.
[10]	WANG Y, ZOU H, ZENG S, et al. A one-step carbonization route towards nitrogen-doped porous carbon hollow spheres with ultrahigh nitrogen content for CO2 adsorption[J]. Chemi. Commun., 2015, 51(62):12423-12426.
[11]	郑远远, 姚金环, 姜吉琼, 等. 纳米多孔NiO类空心微球负极材料的制备与储锂性能[J]. 化工学报, 2017, 68(6):2596-2603. ZHENG Y Y, YAO J H, JIANG J Q, et al. Preparation and lithium storage performance of nanoporous hollow microspheres-like NiO anode materials[J]. CIESC Journal, 2017, 68(6):2596-2603.
[12]	ROBERTS A D, LI X, ZHANG H. Porous carbon spheres and monoliths:morphology control, pore size tuning and their applications as Li-ion battery anode materials[J]. Chem. Soc. Rev., 2014, 43(13):4341-4356.
[13]	LEE H J, CHOI S, OH M. Well-dispersed hollow porous carbon spheres synthesized by direct pyrolysis of core-shell type metal-organic frameworks and their sorption properties[J]. Chemi. Commun., 2014, 50(34):4492-4495.
[14]	HAN Y, DONG X, ZHANG C, et al. Hierarchical porous carbon hollow-spheres as a high performance electrical double-layer capacitor material[J]. J. Power Sources, 2012, 211:92-96.
[15]	HOU J, CAO T, IDREES F, et al. A co-sol-emulsion-gel synthesis of tunable and uniform hollow carbon nanospheres with interconnected mesoporous shells[J]. Nanoscale, 2015, 8(1):451-457.
[16]	吴启强, 包永忠. 偏氯乙烯共聚物/纳米水滑石复合材料及多孔炭的制备与表征[J]. 化工学报, 2011, 62(4):1130-1135. WU Q Q, BAO Y Z. Preparation and characterization of vinylidene chloride copolymer/nanometer hydrotalcite composites and porous carbons[J]. CIESC Journal, 2011, 62(4):1130-1135.
[17]	HE X, SUN H J, ZHU M P, et al. N-doped porous graphitic carbon with multi-flaky shell hollow structure prepared using a green and ‘useful’ template of CaCO3 for VOC fast adsorption and small peptide enrichment[J]. Chemi. Commun., 2017, 53:3442-3445.
[18]	贺鑫, 尹大伟, 赵祯霞, 等. 超重力场中影响碳酸钙晶须断裂的影响因素分析[J]. 高校化学工程学报, 2016, 30(6):1359-1365. HE X, YIN D W, ZHAO Z X, et al. Influencing factors on the fracture of calcium carbonate whiskers in hypergravity field[J]. Journal of Chemical Engineering of Chinese Universities, 2016, 30(6):1359-1365.
[19]	NEIMARK A V, SIN K S W, THOMMES M. Surface Area and Porosity[M]. Weinheim:Wiley-VCH Verlag GmbH & Co. KGaA, 2008.
[20]	STEPHANIE L C, EVAN U. Comparison of effect of nitrogen and surface modification of porous carbon on the performance of Supercapacitors[J]. Sci. China Mater., 2015, 58(7):521-533.
[21]	FAN S S, ZHONG H, YU H T, et al. Hollow and hierarchical Na2Li2Ti6O14 microspheres with high electrochemical performance as anode material for lithium-ion battery[J]. Sci. China Mater., 2017, 60(5):427-437.
[22]	WU Y P, WAN C R, JIANG C Y, et al. Mechanism of lithium storage in low temperature carbon[J]. Carbon, 1999, 37:1901-1908.
[23]	GAN L, GUO H J, WANG Z X, et al. A facile synthesis of graphite/silicon/graphene spherical composite anode for lithium-ion batteries[J]. Electrochim. Acta, 2013, 104(8):117-123.
[24]	CHANG Y C, SOHN H J. Electrochemical impedance analysis for lithium ion intercalation into graphitized carbons[J]. J. Electrochem. Soc., 2000, 147:50-58.
[25]	XING Z, JU Z C, ZHAO Y L, et al. One——pot hydrothermal synthesis of nitrogen-doped graphene as high-performance anode materials for lithium ion batteries[J]. Sci. Res., 2016, 6:26146.
[26]	王力臻, 蔡洪波, 古书华, 等. 直流刻蚀铝集流体对LiC0O2正极性能的影响[J]. 电池, 2008, 38(5):3-5. WANG L Z, CAI H B, GU S H, et al. Effect of DC etching aluminums current collector on performance of LiC0O2 positive electrode[J]. Battery Bimonthly, 2008, 38(5):3-5.
[27]	TATSUYA N, SHINGO O, NORIKO Y, et a1. Electrochemical performance of cathodes prepared on current collector with different surface morphologies[J]. J. Power Sources, 2013, 244:532-537.
[28]	TANG J, YANG J, ZHOU X Y, Synthesis and characterisation of sponge-like carbon anode materials for lithium ion batteries[J]. Mater. Lett., 2013, 109(15):253-256.
[29]	SAIKIA D, WANG T H, CHOU C J, et al. A comparative study of ordered mesoporous carbons with different pore structures as anode materials for lithium-ion batteries[J]. RSC Advances, 2015, 5(53):42922-42930.
[30]	尤春琴, 罗民, 阚夏梅, 等. 皱褶表面介孔镍钴硫化物微球的制备及其超电性能[J]. 应用化学. 2015, 32(12):1455-1461. YOU C Q, LUO M, KAN X M, et al. One-step hydrothermal synthesis of mesoporous ruffle-like sulfide microspheres for supercapacitors[J]. Chin. J. Chem. Eng., 2015, 32(12):1455-1461.

晶须形中空多孔氮掺杂复合碳电极材料的制备及电化学性能研究

Preparation and electrochemical properties of whisker-shaped hollow porous nitrogen-doped composite carbon electrode materials

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