中空四氧化三钴纳米球镶嵌的氮掺杂多孔碳纳米纤维: 锂-氧电池氧电极双功能催化剂

doi:10.1016/S1872-2067(21)64017-2

催化学报 ›› 2022, Vol. 43 ›› Issue (6): 1511-1519.DOI: 10.1016/S1872-2067(21)64017-2

中空四氧化三钴纳米球镶嵌的氮掺杂多孔碳纳米纤维: 锂-氧电池氧电极双功能催化剂

陈宏彬^a^,^†, 叶雅倩^a^,^†, 陈鑫智^a, 张利利^b^,^#(), 刘国学^a, 王素清^a, 丁良鑫^a^,^*()

^a华南理工大学化学与化工学院, 广东广州510640
^b郑州大学化工学院, 先进功能材料制造教育部工程研究中心, 河南郑州450001

收稿日期:2021-09-27 接受日期:2021-09-27 出版日期:2022-06-18 发布日期:2022-04-14
通讯作者: 张利利,丁良鑫
作者简介:第一联系人：
^†共同第一作者
基金资助:
国家自然科学基金(21776099);广东省自然科学基金(2019A1515011579)

N-doped porous carbon nanofibers inlaid with hollow Co₃O₄ nanoparticles as an efficient bifunctional catalyst for rechargeable Li-O₂ batteries

Hongbin Chen^a^,^†, Yaqian Ye^a^,^†, Xinzhi Chen^a, Lili Zhang^b^,^#(), Guoxue Liu^a, Suqing Wang^a, Liang-Xin Ding^a^,^*()

^aSchool of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou 510640, Guangdong, China
^bEngineering Research Center of Advanced Functional Material Manufacturing of Ministry of Education, School of Chemical Engineering, Zhengzhou University, Zhengzhou 450001, Henan, China

Received:2021-09-27 Accepted:2021-09-27 Online:2022-06-18 Published:2022-04-14
Contact: Lili Zhang, Liang-Xin Ding
About author:First author contact:
作者简介:^† Contributed equally to this work.
Supported by:
National Natural Science Foundation of China(21776099);Natural Science Foundation of Guangdong Province(2019A1515011579)

摘要/Abstract

摘要：

随着全球人口数量快速增长和科技不断进步, 对能源需求逐步增加, 但化石能源日渐枯竭, 同时环境问题日趋严重. 因此, 亟需开发新型、绿色、高效的能源以及能源装置, 以保障清洁能源的可持续利用. 锂-氧电池因其能量密度高、环境友好等优点受到了人们的广泛关注, 并被认为是替代锂离子电池的新储能系统之一. 然而, 对于锂-氧电池仍需解决诸如能量密度低于理论值、倍率性能差和循环寿命短等难题. 开发高效稳定的氧电极催化剂是解决上述问题的关键手段之一. 在众多潜在的过渡金属氧化物催化剂中, 四氧化三钴因其地壳丰度高、成本低和性能优异等优点成为研究热点.
本文采用静电纺丝技术, 结合热处理技术, 成功制备了中空四氧化三钴纳米球镶嵌的多孔碳纳米纤维复合催化剂(H-Co₃O₄-CNFs), 系统地研究了其氧还原反应(ORR)和析氧反应(OER)的电催化性能, 以及作为锂-氧电池正极催化剂的电化学性能. 结果表明, 在碱性电解质中, H-Co₃O₄-CNFs具有较好的ORR/OER活性, 展现出较好的双功能催化性能. H-Co₃O₄-CNFs作为锂-氧电池的氧电极催化剂材料, 在100 mA g^‒1电流密度下的过电位为1.35 V, 电池的放电比容量达到6134 mAh g^‒1; 当电流密度增加至800 mA g^‒1时, 放电比容量仍能保持68.5%. 在充放电电流密度为100 mA g^‒1, 限制容量为500 mAh g^‒1的条件下, 电池能保持150圈的稳定循环.
H-Co₃O₄-CNFs催化剂较好的催化性能可归因于: (1)氮掺杂的多孔碳纤维具有良好的导电性和快速的电子传输能力; (2)多孔结构增大了电解液和催化剂活性位点的接触面积, 并为放电产物过氧化锂的形成和分解提供了场所. 另外, 其良好的循环性能得益于裸露的Co₃O₄和嵌入纤维中的Co₃O₄形成的两种独立活性位点, 这使其在ORR和OER过程中均有可用的催化活性位点, 并在放电和充电过程中交替发挥作用. 综上, 本文研究结果为高效氧电极催化剂的设计提供了新思路。

关键词: 锂氧电池, 双功能催化剂, 四氧化三钴, 氮掺杂碳纤维, 氧还原反应, 析氧反应

Abstract:

Stable and high-efficiency bifunctional catalysts for the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are desired for the practical application of Li-O₂ batteries with excellent rate performance and cycle stability. Herein, a novel hybrid bifunctional catalyst with carbon nanofibers inlaid with hollow Co₃O₄ nanoparticles and separate active sites for ORR and OER were prepared and applied in Li-O₂ batteries. Benefiting from the synergistic effect of unique porous structural features and high electrocatalytic activity of hollow Co₃O₄ intimately bound to N-doped carbon nanofibers, the assembled Li-O₂ batteries with novel catalyst exhibited high specific capacity, excellent rate capability, and cycle stability up to 150 cycles under a capacity limitation of 500 mAh g^-1 at a current density of 100 mA g^-1. The facile synthesis and preliminary results in this work show the as-prepared catalyst as a promising bifunctional electrocatalyst for applications in metal-air batteries, fuel cells, and electrocatalysis.

Key words: Li-O₂ batteries, Bifunctional catalyst, Co₃O₄, N-doped carbon nanofibers, Oxygen reduction reaction, Oxygen evolution reaction

陈宏彬, 叶雅倩, 陈鑫智, 张利利, 刘国学, 王素清, 丁良鑫. 中空四氧化三钴纳米球镶嵌的氮掺杂多孔碳纳米纤维: 锂-氧电池氧电极双功能催化剂[J]. 催化学报, 2022, 43(6): 1511-1519.

Hongbin Chen, Yaqian Ye, Xinzhi Chen, Lili Zhang, Guoxue Liu, Suqing Wang, Liang-Xin Ding. N-doped porous carbon nanofibers inlaid with hollow Co₃O₄ nanoparticles as an efficient bifunctional catalyst for rechargeable Li-O₂ batteries[J]. Chinese Journal of Catalysis, 2022, 43(6): 1511-1519.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(21)64017-2

https://www.cjcatal.com/CN/Y2022/V43/I6/1511

图/表 8

Scheme 1. Schematic diagram of the fabrication process of H-Co3O4-CNFs.

Fig. 1. (a) XRD patterns of H-Co3O4-CNFs, Co-CNFs and CNFs. (b) TGA curves of H-Co3O4-CNFs measured from 25 to 800 °C under air atmosphere.

Fig. 2. XPS profiles of survey (a), C 1s (b), N 1s (c), and Co 2p (d) for H-Co3O4-CNFs.

Fig. 3. (a) TEM image of H-Co3O4-CNFs and the particle diameter distribution of hollow Co3O4 particles. (b) TEM image of a single H-Co3O4-CNF. (c) HRTEM image of a single hollow Co3O4 nanoparticle. (d) HRTEM image of part of a single hollow Co3O4 nanoparticle, the top-left inset is an enlarged HRTEM image and top-right inset is the corresponding SAED pattern. (e) HRTEM image of partially graphite carbon on the edge of the porous carbon nanofiber. (f) HRTEM image of partially graphitized carbon.

Fig. 4. (a) ORR polarization curves of H-Co3O4-CNFs, CNFs, and commercial Pt/C at a rotating speed of 1600 r/min. (b) OER polarization curves of H-Co3O4-CNFs, CNFs, and commercial Pt/C. All measurements were conducted in 0.1 mol/L KOH aqueous solution at a sweep rate of 5 mV s-1.

Fig. 5. (a) Cyclic voltammogram of Li-O2 batteries with H-Co3O4-CNFs/KB, CNFs/KB, and bare KB in the voltage range of 2.0-4.5 V at a scan rate of 0.2 mV s-1. (b) Initial discharge/charge curves of Li-O2 batteries with H-Co3O4-CNFs/KB, CNFs/KB, and bare KB at a current density of 100 mA g-1; Comparison of discharge capacities (c) and capacity retention rate (d) of Li-O2 batteries with these three catalysts at current densities of 100, 200, 400, and 800 mA g-1. (e) Cyclic performance of Li-O2 batteries under a capacity limitation of 500 mAh g-1 at a current density of 100 mA g-1.

Fig. 6. SEM images of H-Co3O4-CNFs under different charge/discharge situations. (a) The pristine state. (b) Discharge to 500 mAh g-1. (c) Full discharge. (d) Full charge. (e) TEM image of H-Co3O4-CNFs under a full discharge state. (f) HRTEM image of discharge product particle. (g) enlarged HRTEM image of the discharge product. (h) SAED pattern of discharge product.

Fig. 7. Optimized structures of Li2O2 cluster adsorption on a clean C surface (a) and clean Co3O4 (311) surface (b). Li2O2 cluster adsorption on a C site (c) and compound interface (d) of C-modified Co3O4 (311) (green, blue, red, and purple spheres represent the C, Co, O, and Li atoms, respectively).

参考文献

[1]	C. F. Shih, T. Zhang, J. Li, C. Bai, Joule, 2018, 2, 1925-1949.
[2]	C. Wang, Z. Zhang, W. Liu, Q. Zhang, X.-G. Wang, Z. Xie, Z. Zhou, Angew. Chem. Int. Ed., 2020, 59, 17856-17863.
[3]	L. Zhang, P. Lu, Y. Luo, J. Y. Zheng, W. Ma, L.-X. Ding, H. Wang, J. Mater. Chem. A, 2021, 9, 9609-9615.
[4]	F. Xiao, Y.-C. Wang, Z.-P. Wu, G. Chen, F. Yang, S. Zhu, K. Siddharth, Z. Kong, A. Lu, J.-C. Li, C.-J. Zhong, Z.-Y. Zhou, M. Shao, Adv. Mater., 2021, 33, 2006292.
[5]	J.-J. Xu, X.-B. Zhang, Nat. Energy, 2017, 2, 17133.
[6]	L. Liu, H. Guo, L. Fu, S. Chou, S. Thiele, Y. Wu, J. Wang, Small, 2021, 17, 1903854.
[7]	J. Lai, H. Liu, Y. Xing, L. Zhao, Y. Shang, Y. Huang, N. Chen, L. Li, F. Wu, R. Chen, Adv. Funct. Mater., 2021, 2101831.
[8]	P. Zhang, M. Ding, X. Li, C. Li, Z. Li, L. Yin, Adv. Energy Mater., 2020, 10, 2001789.
[9]	J.-B. Park, S. H. Lee, H.-G. Jung, D. Aurbach, Y.-K. Sun, Adv. Mater., 2018, 30, 1704162.
[10]	V. Rai, K. P. Lee, D. Safanama, S. Adams, D. J. Blackwood, ACS Appl. Energy Mater., 2020, 3, 9417-9427.
[11]	J. Li, L. Hou, M. Yu, Q. Li, T. Zhang, H. Sun, ChemElectroChem, 2021, 8, 1.
[12]	X. Tian, X. F. Lu, B. Y. Xia, X. W. Lou, Joule, 2020, 4, 45-68.
[13]	K. Zhang, R. Zou, Small, 2021, 17, 2100129.
[14]	Y. Zhang, S. Zhang, J. Ma, A. Huang, M. Yuan, Y. Li, G. Sun, C. Chen, C. Nan, ACS Appl. Mater. Interfaces, 2021, 13, 39239-39247.
[15]	D. Cao, L. Zheng, Q. Li, J. Zhang, Y. Dong, J. Yue, X. Wang, Y. Bai, G. Tan, C. Wu, Nano Lett., 2021, 21, 5225-5232.
[16]	J. Li, C. Shu, A. Hu, Z. Ran, M. Li, R. Zheng, J. Long, Chem. Eng. J., 2020, 381, 122678.
[17]	Q. Guo, C. Zhang, C. Zhang, S. Xin, P. Zhang, Q. Shi, D. Zhang, Y. You, J. Energy Chem., 2020, 41, 185-193.
[18]	Z.-L. Jiang, G.-L. Xu, Z. Yu, T.-H. Zhou, W.-K. Shi, C.-S. Luo, H.-J. Zhou, L.-B. Chen, W.-J. Sheng, M. Zhou, L. Cheng, R. S. Assary, S.-G. Sun, K. Amine, H. Sun, Nano Energy, 2019, 64, 103896.
[19]	Y. Huang, J. Chen, X. Zhang, Y. Zan, X. Wu, Z. He, H. Wang, Q. Li, Chem. Eng. J., 2016, 296, 28-34.
[20]	Y. Tian, X. Liu, L. Xu, D. Yuan, Y. Dou, J. Qiu, H. Li, J. Ma, Y. Wang, D. Su, S. Zhang, Adv. Funct. Mater., 2021, 31, 2101239.
[21]	H. Xia, Q. Xie, Y. Tian, Q. Chen, M. Wen, J. Zhang, Y. Wang, Y. Tang, S. Zhang, Nano Energy, 2021, 84, 105877.
[22]	G. Yue, J. Liu, J. Han, D. Qin, Q. Chen, J. Shao, Chin. J. Catal., 2018, 39, 1951-1959.
[23]	T. Zhao, Y. Yao, Y. Yuan, M. Wang, F. Wu, K. Amine, J. Lu, Nano Energy, 2021, 82, 105782.
[24]	H. J. Yan, B. Xu, S. Q. Shi, C. Y. Ouyang, J. Appl. Phys., 2012, 112, 104316.
[25]	Y. Li, J. Wang, X. Li, D. Geng, M. N. Banis, R. Li, X. Sun, Electrochem. Commun., 2012, 18, 12-15.
[26]	S. Hyun, V. Kaker, A. Sivanantham, J. Hong, S. Shanmugam, ACS Appl. Mater. Interfaces, 2021, 13, 17699-17706.
[27]	G. Liu, B. Wang, L. Xu, P. Ding, P. Zhang, J. Xia, H. Li, J. Qian, Chin. J. Catal., 2018, 39, 790-799.
[28]	Z. Jiang, H. Sun, W. Shi, T. Zhou, J. Hu, J. Cheng, P. Hu, S. Sun, Nano Res., 2019, 12, 1555-1562.
[29]	R. Gao, Z. Yang, L. Zheng, L. Gu, L. Liu, Y. Lee, Z. Hu, X. Liu, ACS Catal., 2018, 8, 1955-1963.
[30]	Y. Zhang, M. Hu, M. Yuan, G. Sun, Y. Li, K. Zhou, C. Chen, C. Nan, Y. Li,, Nano Res., 2019, 12, 299-302.
[31]	C. Tomon, A. Krittayavathananon, S. Sarawutanukul, S. Duangdangchote, N. Phattharasupakun, K. Homlamai, M. Sawangphruk, Electrochim. Acta, 2021, 367, 137490.
[32]	Y. Zhang, L. Feng, W. Zhan, S. Li, Y. Li, X. Ren, P. Zhang, L. Sun, ACS Appl. Energy Mater., 2020, 3, 4014-4022.
[33]	T. Sharifi, F. Nitze, H. R. Barzegar, C.-W. Tai, M. Mazurkiewicz, A. Malolepszy, L. Stobinski, T. Wagberg, Carbon, 2012, 50, 3535-3541.
[34]	S. Wang, L. Xia, L. Yu, L. Zhang, H. Wang, X. W. Lou, Adv. Energy Mater., 2016, 6, 1502217.
[35]	D. Guo, R. Shibuya, C. Akiba, S. Saji, T. Kondo, J. Nakamura, Science, 2016, 351, 361-365.
[36]	F. Zhang, C. Yuan, J. Zhu, J. Wang, X. Zhang, X. W. Lou, Adv. Funct. Mater., 2013, 23, 3909-3915.
[37]	Y. Zhao, X. Zhang, Sci. Rep., 2021, 11, 6825.
[38]	Q. Chen, X. Tan, Y. Liu, S. Liu, M. Li, Y. Gu, P. Zhang, S. Ye, Z. Yang, Y. Yang, J. Mater. Chem. A, 2020, 8, 5773-5811.

中空四氧化三钴纳米球镶嵌的氮掺杂多孔碳纳米纤维: 锂-氧电池氧电极双功能催化剂

N-doped porous carbon nanofibers inlaid with hollow Co₃O₄ nanoparticles as an efficient bifunctional catalyst for rechargeable Li-O₂ batteries

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中空四氧化三钴纳米球镶嵌的氮掺杂多孔碳纳米纤维: 锂-氧电池氧电极双功能催化剂

N-doped porous carbon nanofibers inlaid with hollow Co3O4 nanoparticles as an efficient bifunctional catalyst for rechargeable Li-O2 batteries

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N-doped porous carbon nanofibers inlaid with hollow Co₃O₄ nanoparticles as an efficient bifunctional catalyst for rechargeable Li-O₂ batteries