三维网状结构Ru/石墨烯/碳纳米管复合材料作为锂氧电池正极催化剂的性能

doi:10.7503/cjcu2080706

高等学校化学学报 ›› 2019, Vol. 40 ›› Issue (6): 1271.doi: 10.7503/cjcu2080706

三维网状结构Ru/石墨烯/碳纳米管复合材料作为锂氧电池正极催化剂的性能

尹艳红, 李珂, 董红玉, 金城, 肖星路, 高怡琮, 杨书廷()

河南师范大学化学化工学院, 动力电源及关键材料国家-地方联合工程实验室, 动力电源及关键材料河南省协同创新中心, 新乡 453007

收稿日期:2018-10-19 出版日期:2019-06-10 发布日期:2019-03-27
作者简介:
联系人简介: 杨书廷, 男, 博士, 教授, 主要从事锂离子电池和新型储能系统方面的研究. E-mail: shutingyang@foxmail.com
基金资助:
国家自然科学基金青年科学基金(批准号: 51502082)、河南省科技攻关项目(批准号: 182102210079)和河南省科技创新人才计划项目(批准号: 174100510015)资助.

Performance of Ru/graphene/carbon Nanotube Composites with Three-dimensional Network Structure as Positive Electrode Catalysts for Lithium Oxygen Batteries^†

YIN Yanhong, LI Ke, DONG Hongyu, JIN Cheng, XIAO Xinglu, GAO Yicong, YANG Shuting()

College of Chemistry and Chemical Engineering,National and Local Joint Engineering Laboratory of Motive Power and Key Materials, Power Supply and Key Materials Henan Collaborative Innovation Center, Henan Normal University, Xinxiang 453007, China

Received:2018-10-19 Online:2019-06-10 Published:2019-03-27
Supported by:
† Supported by the National Natural Science Foundation of China Youth Science Foundation(No.51502082), the Science and Technology Project of Henan Province, China(No.182102210079) and the Science and Technology Innovation Talents Program of Henan Province, China(No.174100510015).

摘要/Abstract

摘要：

利用物理浸渍和冷冻干燥等方法制备了具有三维网状结构的Ru/石墨烯/碳纳米管复合材料, 对该材料的结构、形貌及电化学性能进行了表征和研究. 结果表明, 当Ru含量为30%, 热处理温度为500 ℃时, 材料的催化性能最优. 将其用作锂氧电池的正极催化剂, 以50 mA/g电流密度进行首次充放电时, 放电比容量约为5800 mA·h/g, 且在放电比容量为4000 mA·h/g以内时, 其极化电压仅为0.9 V; 当以50 mA/g电流密度进行恒容(500 mA·h/g)充放电循环时, 在极化电压低于1.1 V时, 仍能稳定循环12周. 复合材料电催化机理的研究结果表明, 三维网状结构不仅提供了O₂和Li⁺的传输通道, 更增加了放电产物Li₂O₂的储存场所. 金属钌纳米粒子的负载既增加了复合材料的反应活性位点, 又促进了放电产物Li₂O₂的分解.

关键词: 锂氧电池, 催化剂, 复合材料, 极化电压

Abstract:

Ru/graphene/carbon nanotube composites with three-dimensional network structure were prepared by physical impregnation and freeze drying. When the Ru content was 30%(mass fraction) and the heat treatment temperature was 500 ℃, the catalytic performance of the composite was optimal. When the composite was used as a cathode catalyst for lithium oxygen batteries, it exhibited excellent battery performance. When the first charge and discharge were performed at a current density of 50 mA/g, the discharge capacity density was about 5800 mA·h/g, and when the discharge capacity density was within 4000 mA·h/g, the polarization voltage was only was 0.9 V; when a constant-capacitance(500 mA·h/g) charge-discharge cycle was performed at a current density of 50 mA/g, the battery was stable for 12 cycles even when the polarization voltage was lower than 1.1 V. The three-dimensional network structure not only provided a transmission channel for O₂ and Li⁺, but also increased the storage location of the discharge product Li₂O₂. The loading of the metal ruthenium nanoparticles not only increased the reactive site of the composite, but also promoted the decomposition of the discharge product Li₂O₂.

Key words: Lithium-oxygen battery, Catalyst, Composite material, Polarization voltage

中图分类号:

O646

TrendMD:

尹艳红, 李珂, 董红玉, 金城, 肖星路, 高怡琮, 杨书廷. 三维网状结构Ru/石墨烯/碳纳米管复合材料作为锂氧电池正极催化剂的性能. 高等学校化学学报, 2019, 40(6): 1271.

YIN Yanhong,LI Ke,DONG Hongyu,JIN Cheng,XIAO Xinglu,GAO Yicong,YANG Shuting. Performance of Ru/graphene/carbon Nanotube Composites with Three-dimensional Network Structure as Positive Electrode Catalysts for Lithium Oxygen Batteries^†. Chem. J. Chinese Universities, 2019, 40(6): 1271.

图/表 13

Fig.1 SEM image of RGC-2-500 composite at different magnifications

Fig.2 SEM image(A) and EDS diagram of C(B), O(C) and Ru(D)

Fig.3 TEM image of RGC-2-500 composites(A) and lattice fringes and selected area electron diffraction patterns of Ru nanoparticles(B)

Fig.4 Ru3p(A) and Ru3d(B) XPS spectra of RGC-2-500 composites

Fig.5 Thermogravimetric curve of RGC-2-500 composites in O2 atmosphere(A) and XPS diagram of RGC-2-500 composites after heat treatment at 1000 ℃(B, C)

Fig.6 TG-DSC curves of RGC-2 in N2 atmosphere(A) and XRD patterns of RGC-2, RGC-2-300, RGC-2-500 and RGC-2-850 composites(B)

Fig.7 Nitrogen adsorption-desorption isotherms(A) and specific surface area(B) of RGC-2, RGC-2-300, RGC-2-500 and RGC-2-850 a. RGC-2; b. RGC-2-300; c. RGC-2-500; d. RGC-2-850.

Fig.8 Cyclic voltammograms at a rate of 50 mV/s(A, D), oxygen reduction reaction curves(B, E) and oxygen evolution reaction curves(C, F) at a rotation rate of 1600 r/min and a scanning rate of 10 mV/s

Fig.9 KL curves of RGC-2-500(A), Pt/C(B) during the ORR processes at different rotation rates and chronoamperometric responses for the ORR of RGC-2-500 and Pt/C at a rotation rate of 1600 r/min for 10000 s(C)

Fig.10 Galvanostatic discharge/charge curves of Li-O2 batteries with RGC-2, RGC-2-300, RGC-2-500 and RGC-2-850 as the cathode catalyst at a current density of 50 mA/g in the voltage range of 2.0—4.2 V(vs. Li+ /Li)

Fig.11 Charge-discharge curves of RGC-2(A), RGC-2-300(B), RGC-2-500(C) and RGC-2-850(D) as cathode catalyst at 50 mA/g with a limited specific capacity of 500 mA·h/g

Fig.12 SEM images of the pole piece after charging and discharging with GRC-2-500 composite as cathode electrode catalyst for Li-O2 battery under current density of 50 mA/g and limited capacity of 500 mA·h/g (A) Original cathode electrode; (B) discharged cathode electrode; (C) charged cathode electrode.

Fig.13 XRD patterns of the pole piece after charging and discharging with GRC-2-500 composite as cathode electrode catalyst for Li-O2 battery under current density of 50 mA/g and limited capacity of 500 mA·h/g

参考文献 32

[1]	Salunkhe R. R., Lee Y. H., Chang K. H., Li J. M., Simon P., Tang J., Torad N. L., Hu C. C., Yamauchi Y., Chemistry-A European Journal,2014, 20(43), 13838-13852
[2]	Salunkhe R. R., Tang J., Kobayashi N., Kim J., Ide Y., Tominaka S., Kim J. H., Yamauchi Y., Chemical Science,2016, 7(9), 5704-5713
[3]	Salunkhe R. R., Hsu S. H., Wu K. C. W., Yamauchi Y., Chem. Sus. Chem.,2014, 7(6), 1551-1556
[4]	Yue H. Y., Wang Q. X., Zhang X., Hua S., Ma H., Yue D. Y., Yang S. T., Chem. J. Chinese Universities,2015, 36(4), 745-750
	(岳红云,王秋娴,张雪,华双,马华,岳东媛,杨书廷.高等学校化学学报, 2015, 36(4), 745-750)
[5]	Pramanik M., Tsujimoto Y., Malgras V., Dou S. X., Kim J. H., Yamauchi Y., Chemistry of Materials,2015, 27(3), 1082-1089
[6]	Hwang S. M., Lim Y. G., Kim J. G., Heo Y. U., Lim J. H., Yamauchi Y., Park M. S., Kim Y. J., Dou S. X., Kim J. H., Nano Energy,2014, 10, 53-62
[7]	Xue H., Zhao J., Tang J., Gong H., He P., Zhou H., Yamauchi Y., He J., Chemistry-A European Journal,2016, 22(14), 4915-4923
[8]	Tan G., Chong L., Amine R., Lu J., Liu C., Yuan Y., Wen J., He K., Bi X., Guo Y., Wang H. H., Shahbazian-Yassar R., Al Hallaj S., Miller D. J., Liu D., Amine K., Nano Letters,2017, 17(5), 2959-2966
[9]	Chen Y., Freunberger S. A., Peng Z., Fontaine O., Bruce P. G., Nature Chemistry,2013, 5, 489-494
[10]	Wang Z. L., Xu D., Xu J. J., Zhang L. L., Zhang X. B., Advanced Functional Materials,2012, 22(17), 3699-3705
[11]	Xu J., Ma J., Fan Q., Guo S., Dou S., Advanced Materials,2017, 29(28), 1606454
[12]	Yuan M., Yang Y., Nan C., Sun G., Li H., Ma S., Applied Surface Science,2018, 444, 312-319
[13]	Tian F., Radin M. D., Siegel D. J., Chemistry of Materials,2014, 26(9), 2952-2959
[14]	Guo X., Liu P., Han J., Ito Y., Hirata A., Fujita T., Chen M., Advanced Materials,2015, 27(40), 6137-6143
[15]	Guo Z., Zhou D., Dong X., Qiu Z., Wang Y., Xia Y., Advanced Materials,2013, 25(39), 5668-5672
[16]	Cao Y., Zheng M. S., Cai S., Lin X., Yang C., Hu W., Dong Q. F., Journal of Materials Chemistry A,2014, 2(44), 18736-18741
[17]	Feng J. X., Xu H., Dong Y. T., Ye S. H., Tong Y. X., Li G. R., Angew. Chem. Int. Ed.,2016, 55(11), 3694-3698
[18]	Lu X. F., Gu L. F., Wang J. W., Wu J. X., Liao P. Q., Li G. R., Advanced Materials,2017, 29(3), 1604437
[19]	Feng N., He P., Zhou H., Advanced Energy Materials,2016, 6(9), 1502303
[20]	Zhang W., Zhu J., Ang H., Zeng Y., Xiao N., Gao Y., Liu W., Hng H. H., Yan Q., Nanoscale,2013, 5(20), 9651-9658
[21]	Luo L., Liu B., Song S., Xu W., Zhang J. G., Wang C., Nature Nanotechnology,2017, 12, 535
[22]	Qiu D., Bu G., Zhao B., Lin Z., Pu L., Pan L., Shi Y., Materials Letters,2015, 141, 43-46
[23]	Read J., Journal of the Electrochemical Society, 2002, 149(9), A1190-A1195
[24]	Ishiguro K., Nemori H., Sunahiro S., Nakata Y., Sudo R., Matsui M., Takeda Y., Yamamoto O., Imanishi N., Journal of the Electrochemical Society,2014, 161(5), A668-A674
[25]	Zhang J., Li P., Wang Z., Qiao J., Rooney D., Sun W., Sun K., Journal of Materials Chemistry A,2015, 3(4), 1504-1510
[26]	Feng J. X., Ye S. H., Xu H., Tong Y. X., Li G. R., Advanced Materials,2016, 28(23), 4698-4703
[27]	Lin X., Cao Y., Cai S., Fan J., Li Y., Wu Q.-H., Zheng M., Dong Q., Journal of Materials Chemistry A,2016, 4(20), 7788-7794
[28]	Yi G., Xing B., Zeng H., Wang X., Zhang C., Cao J., Chen L., Journal of Nanomaterials,2017, 2017, 1-10
[29]	Zhao G., Zhang D., Yu J., Xie Y., Hu W., Jiao F., Ceramics International,2017, 43(17), 15080-15088
[30]	Kim M., Nam D. H., Park H. Y., Kwon C., Eom K., Yoo S., Jang J., Kim H. J., Cho E., Kwon H., Journal of Materials Chemistry A,2015, 3(27), 14284-14290
[31]	Cui L., Lv G., He X., Journal of Power Sources,2015, 282, 9-18
[32]	Li F., Chen Y., Tang D. M., Jian Z., Liu C., Golberg D., Yamada A., Zhou H., Energy & Environmental Science,2014, 7(5), 1648-1652

三维网状结构Ru/石墨烯/碳纳米管复合材料作为锂氧电池正极催化剂的性能

Performance of Ru/graphene/carbon Nanotube Composites with Three-dimensional Network Structure as Positive Electrode Catalysts for Lithium Oxygen Batteries^†

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 13

参考文献 32

相关文章 15

编辑推荐

Metrics

本文评价

[1]	秦永吉, 罗俊. 单原子催化剂在CO₂转化中的应用[J]. 高等学校化学学报, 2022, 43(9): 20220300.
[2]	范建玲, 唐灏, 秦凤娟, 许文静, 谷鸿飞, 裴加景, 陈文星. 氮掺杂超薄碳纳米片复合铂钌单原子合金催化剂的电化学析氢性能[J]. 高等学校化学学报, 2022, 43(9): 20220366.
[3]	林治, 彭志明, 贺韦清, 沈少华. 单原子与团簇光催化：竞争与协同[J]. 高等学校化学学报, 2022, 43(9): 20220312.
[4]	程前, 杨博龙, 吴文依, 向中华. S掺杂Fe-N-C高活性氧还原反应催化剂[J]. 高等学校化学学报, 2022, 43(9): 20220341.
[5]	滕镇远, 张启涛, 苏陈良. 聚合物单原子光催化剂的载流子分离和表面反应机制[J]. 高等学校化学学报, 2022, 43(9): 20220325.
[6]	王茹玥, 魏呵呵, 黄凯, 伍晖. 单原子材料的冷冻合成[J]. 高等学校化学学报, 2022, 43(9): 20220428.
[7]	楚宇逸, 兰畅, 罗二桂, 刘长鹏, 葛君杰, 邢巍. 单原子铈对弱芬顿效应活性位点氧还原稳定性的提升[J]. 高等学校化学学报, 2022, 43(9): 20220294.
[8]	杨静怡, 李庆贺, 乔波涛. 铱单原子和纳米粒子在N₂O分解反应中的协同催化[J]. 高等学校化学学报, 2022, 43(9): 20220388.
[9]	林高鑫, 王家成. 单原子掺杂二硫化钼析氢催化的进展和展望[J]. 高等学校化学学报, 2022, 43(9): 20220321.
[10]	任诗杰, 谯思聪, 刘崇静, 张文华, 宋礼. 铂单原子催化剂同步辐射X射线吸收谱的研究进展[J]. 高等学校化学学报, 2022, 43(9): 20220466.
[11]	汪思聪, 庞贝贝, 刘潇康, 丁韬, 姚涛. XAFS技术在单原子电催化中的应用[J]. 高等学校化学学报, 2022, 43(9): 20220487.
[12]	韦春洪, 蒋倩, 王盼盼, 江成发, 刘岳峰. 贵金属Pt促进Co基费托合成催化剂的原子尺度结构分析[J]. 高等学校化学学报, 2022, 43(8): 20220074.
[13]	张昕昕, 许狄, 王艳秋, 洪昕林, 刘国亮, 杨恒权. CO₂加氢制低碳醇CuFe基催化剂中的Mn助剂效应[J]. 高等学校化学学报, 2022, 43(7): 20220187.
[14]	赵润瑶, 纪桂鹏, 刘志敏. 吡咯氮配位单原子铜催化剂的电催化二氧化碳还原性能[J]. 高等学校化学学报, 2022, 43(7): 20220272.
[15]	周雷雷, 程海洋, 赵凤玉. Pd基多相催化剂上CO₂加氢反应的研究进展[J]. 高等学校化学学报, 2022, 43(7): 20220279.

三维网状结构Ru/石墨烯/碳纳米管复合材料作为锂氧电池正极催化剂的性能

Performance of Ru/graphene/carbon Nanotube Composites with Three-dimensional Network Structure as Positive Electrode Catalysts for Lithium Oxygen Batteries†

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 13

参考文献 32

相关文章 15

编辑推荐

Metrics

本文评价

Performance of Ru/graphene/carbon Nanotube Composites with Three-dimensional Network Structure as Positive Electrode Catalysts for Lithium Oxygen Batteries^†