English

Single-Atom Cobalt Coordinated to Oxygen Sites on Graphene for Stable Lithium Metal Anodes

• Shi Haodong ^1,2,3, ,
• Li Yaguang ^1,2, ,
• Lu Pengfei ^1,2, ,
• Wu Zhong-Shuai ^{1,2, ,}

• 1.

  State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning Province, China

• 2.

  Dalian National Laboratory for Clean Energy, Chinese Academy of Sciences, Dalian 116023, Liaoning Province, China

• 3.

  University of Chinese Academy of Sciences, Beijing 100049, China

Corresponding author: Wu Zhong-Shuai, wuzs@dicp.ac.cn

• Received Date: 13 August 2020
  Accepted Date: 08 September 2020
  Revised Date: 08 September 2020
  Available Online: 15 November 2021
• Fund Project:

  The project was supported by the National Key R@D Program of China (2016YBF0100100), the National Natural Science Foundation of China (51872283, 21805273), the Liaoning BaiQianWan Talents Program, Liaoning Revitalization Talents Program (XLYC1807153), the Natural Science Foundation of Liaoning Province (20180510038), Dalian Institute Of Chemical Physics (DICP ZZBS201708, DICP ZZBS201802, DICP I202032), Dalian Institute Of Chemical Physics and Qingdao Institute of Biomass Energy and Bioprocess Technology (DICP&QIBEBT UN201702), and the Dalian National Laboratory For Clean Energy (DNL), CAS, DNL Cooperation Fund, CAS (DNL180310, DNL180308, DNL201912, DNL201915)

Abstract: Lithium (Li)-based batteries are the dominant energy source for consumer electronics, grid storage, and electrified transportation. However, the development of batteries based on graphite anodes is hindered by their limited energy density. With its ultrahigh theoretical capacity (3860 mAh∙g⁻¹), low redox potential (−3.04 V), and satisfactorily low density (0.54 g∙cm⁻³), Li metal is the most promising anode for next-generation high-energy-density batteries. Unfortunately, the limited cycling life and safety issues raised by dendrite growth, unstable solid electrolyte interphase, and "dead Li" have inhibited their practical use. An effective strategy is to develop a suitable lithiophilic matrix for regulating initial Li nucleation behavior and controlling subsequent Li growth. Herein, single-atom cobalt coordinated to oxygen sites on graphene (Co-O-G SA) is demonstrated as a Li plating substrate to efficiently regulate Li metal nucleation and growth. Owing to its dense and more uniform lithiophilic sites than single-atom cobalt coordinated to nitrogen sites on graphene (Co-N-G SA), high electronic conductivity, and high specific surface area (519 m²∙g⁻¹), Co-O-G SA could significantly reduce the local current density and promote the reversibility of Li plating and stripping. As a result, the Co-O-G SA based Li anodes exhibited a high Coulombic efficiency of 99.9% at a current density of 1 mA∙cm⁻² with a capacity of 1 mAh∙cm⁻², and excellent rate capability (high current density of 8 mA∙cm⁻²). Even at a high plating capacity of 6 mAh∙cm⁻², the Co-O-G SA electrode could stably cycle for an ultralong lifespan of 1300 h. In the symmetric battery, the Co-O-G SA based Li anode (Co-O-G SA/Li) possessed a stable voltage profile of 18 mV for 780 h at 1 mA∙cm⁻², and even at a high current density of 3 mA∙cm⁻², its overpotential maintained a small hysteresis of approximately 24 mV for > 550 h. Density functional theory calculations showed that the surface of Co-O-G SA had a stronger interaction with Li atoms with a larger binding energy, −3.1 eV, than that of Co-N-G SA (−2.5 eV), leading to a uniform distribution of metallic Li on the Co-O-G SA surface. More importantly, when matched with a sulfur cathode, the resulting Co-O-G SA/lithium sulfur full batteries exhibited a high capacity of 1002 mAh∙g⁻¹, improved kinetics with a small polarization of 191 mV, and an ultralow capacity decay rate of 0.036% per cycle for 1000 cycles at 0.5C (1C = 1675 mA∙g⁻¹) with a steady Coulombic efficiency of nearly 100%. Therefore, this work provides novel insights into the coordination environment of single atoms for the chemistry of Li metal anodes for high-energy-density batteries.

Key words:
• Single atom
•  /  Coordination environment
•  /  Lithiophilic site
•  /  Li dendrite
•  /  High-energy-density lithium battery

• 1. [1]

     Kang, K.; Meng, Y. S.; Bréger, J.; Grey, C. P.; Ceder, G. Science 2006, 311, 977. doi: 10.1126/science.1122152

  2. [2]

     Choi, J. W.; Aurbach, D. Nat. Rev. Mater. 2016, 1, 16013. doi: 10.1038/natrevmats.2016.13

  3. [3]

     Goodenough, J. B.; Kim, Y. Chem. Mater.2010, 22, 587. doi: 10.1021/cm901452z

  4. [4]

     Armand, M.; Tarascon, J. M. Nature 2008, 451, 652. doi: 10.1038/451652a

  5. [5]

     Shi, H.; Zhang, C. J.; Lu, P.; Dong, Y.; Wen, P.; Wu, Z. S. ACS Nano 2019, 13, 14308. doi: 10.1021/acsnano.0c03042

  6. [6]

     Shi, H.; Qin, J.; Huang, K.; Lu, P.; Zhang, C.; Dong, Y.; Ye, M.; Liu, Z.; Wu, Z. S. Angew. Chem. Int. Ed. 2020, 59, 12147. doi: 10.1002/anie.202004284

  7. [7]

     Cheng, X. B.; Zhang, R.; Zhao, C. Z.; Zhang, Q. Chem. Rev. 2017, 117, 10403. doi: 10.1021/acs.chemrev.7b00115

  8. [8]

     Xu, X.; Wang, S.; Wang, H.; Hu, C.; Jin, Y.; Liu, J.; Yan, H. J. Am. Chem. Soc. 2018, 27, 513. doi: 10.1016/j.jechem.2017.11.010

  9. [9]

     Chen, S.; Niu, C.; Lee, H.; Li, Q.; Yu, L.; Xu, W.; Zhang, J. G.; Dufek, E. J.; Whittingham, M. S.; Meng, S. Joule 2019, 3, 1094. doi: 10.1016/j.joule.2019.02.004

  10. [10]

      冉琴, 孙天霷, 韩冲宇, 张浩楠, 颜剑, 汪靖伦.物理化学学报, 2020, 36, 1912068. doi: 10.3866/PKU.WHXB201912068Ran, Q.; Sun, T.; Han, C.; Zhang, H.; Yan, J.; Wang, J. Acta Phys. -Chim. Sin. 2020, 36, 1912068. doi: 10.3866/PKU.WHXB201912068

  11. [11]

      Ding, F.; Xu, W.; Graff, G. L.; Zhang, J.; Sushko, M. L.; Chen, X.; Shao, Y.; Engelhard, M. H.; Nie, Z.; Xiao, J.; et al. J. Am. Chem. Soc. 2013, 135, 4450. doi: 10.1021/ja312241y

  12. [12]

      Wang, G.; Xiong, X.; Xie, D.; Fu, X.; Ma, X.; Li, Y.; Liu, Y.; Lin, Z.; Yang, C.; Liu, M. Energy Storage Mater. 2019, 23, 701. doi: 10.1016/j.ensm.2019.02.026

  13. [13]

      Zhao, C. Z.; Duan, H.; Huang, J. Q.; Zhang, J.; Zhang, Q.; Guo, Y. G.; Wan, L. J. Sci. China Chem. 2019, 62, 1286. doi: 10.1007/s11426-019-9519-9

  14. [14]

      金锋, 李静, 胡晨吉, 董厚才, 陈鹏, 沈炎宾, 陈立桅.物理化学学报, 2019, 35, 1399. doi: 10.3866/PKU.WHXB201904085Jin, F., Li. J.; Hu, C. J.; Dong, H. C.; Chen, P.; Shen, Y. B.; Chen, L. W. Acta Phys. -Chim. Sin. 2019, 35, 1399. doi: 10.3866/PKU.WHXB201904085

  15. [15]

      朱高龙, 赵辰孜, 袁洪, 南皓雄, 赵铂琛, 侯立鹏, 何传新, 刘全兵, 黄佳琦.物理化学学报, 2021, 37, 2005003. doi: 10.3866/PKU.WHXB202005003Zhu, G.; Zhao, C.; Yuan, H.; Nan, H.; Zhao, B.; Hou, L.; He, C.; Liu, Q.; Huang, J. Acta Phys. -Chim. Sin. 2021, 37, 2005003. doi: 10.3866/PKU.WHXB202005003

  16. [16]

      Zhang, H.; Liao, X.; Guan, Y.; Xiang, Y.; Li, M.; Zhang, W.; Zhu, X.; Ming, H.; Lu, L.; Qiu, J.; et al. Nat. Commun. 2018, 9, 3729. doi: 10.1038/s41467-018-06126-z

  17. [17]

      Zhang, C.; Lyu, R.; Lv, W.; Li, H.; Jiang, W.; Li, J.; Gu, S.; Zhou, G.; Huang, Z.; Zhang, Y.; et al. Adv. Mater. 2019, 31, e1904991. doi: 10.1002/adma.201904991

  18. [18]

      Ni, S.; Tan, S.; An, Q.; Mai, L. J. Energy Chem. 2020, 44, 73. doi: 10.1016/j.jechem.2019.09.031

  19. [19]

      Zhang, R.; Chen, X. R.; Chen, X.; Cheng, X. B.; Zhang, X. Q.; Yan, C.; Zhang, Q. Angew. Chem. Int. Ed. 2017, 56, 7764. doi: 10.1002/ange.201702099

  20. [20]

      Shi, H.; Yue, M.; Zhang, C. J.; Dong, Y.; Lu, P.; Zheng, S.; Huang, H.; Chen, J.; Wen, P.; Xu, Z.; et al. ACS Nano 2020, 14, 8678. doi: 10.1021/acsnano.0c03042

  21. [21]

      Zhang, J. Q.; Zhao, Y. F.; Guo, X.; Chen, C.; Dong, C. L.; Liu, R. S.; Han, C. P.; Li, Y. D.; Gogotsi, Y.; Wang, G. X. Nat. Catal. 2018, 1, 985. doi: 10.1038/s41929-018-0195-1

  22. [22]

      Zhang, J. Q.; Zhao, Y. F.; Chen, C.; Huang, Y. C.; Dong, C. L.; Chen, C. J.; Liu, R. S.; Wang, C. Y.; Yan, K, ; Li, Y. D.; et al. J. Am. Chem. Soc. 2019, 141, 20118. doi: 10.1021/jacs.9b09352

  23. [23]

      Zhao, D.; Chen, Z.; Yang, W. J.; Liu, S. J.; Zhang, X.; Yu, Y.; Cheong, W. C.; Zheng, L. R.; Ren, F. Q.; Ying, G. B.; et al. J. Am. Chem. Soc. 2019, 141, 4086. doi: 10.1021/jacs.8b13579

  24. [24]

      Xu, K.; Zhu, M.; Wu, X.; Liang, J.; Liu, Y.; Zhang, T.; Zhu, Y.; Qian, Y. Energy Storage Mater. 2019, 23, 587. doi: 10.1016/j.ensm.2019.03.025

  25. [25]

      Zhai, P.; Wang, T.; Yang, W.; Cui, S.; Zhang, P.; Nie, A.; Zhang, Q.; Gong, Y. Adv. Energy Mater. 2019, 9, 1804019. doi: 10.1002/aenm.201804019

  26. [26]

      Gu, J.; Zhu, Q.; Shi, Y.; Chen, H.; Zhang, D.; Du, Z.; Yang, S. ACS Nano 2020, 14, 891. doi: 10.1021/acsnano.9b08141

  27. [27]

      Zheng, J.; Engelhard, M. H.; Mei, D.; Jiao, S.; Polzin, B. J.; Zhang, J. G.; Xu, W. Nat. Energy 2017, 2, 17012. doi: 10.1038/nenergy.2017.12

  28. [28]

      Li, Y.; Wu, Z. S.; Lu, P.; Wang, X.; Liu, W.; Liu, Z.; Ma, J.; Ren, W.; Jiang, Z.; Bao, X. Adv. Sci. 2020, 7, 1903089. doi: 10.1002/advs.201903089

  29. [29]

      Xu, Y.; Zhang, W.; Li, Y.; Lu, P.; Wu, Z. S. J. Energy Chem. 2020, 43, 52. doi: 10.1016/j.jechem.2019.08.006

  30. [30]

      Delley, B. J. Chem. Phys. 2000, 113, 7756. doi: 10.1063/1.1316015

  31. [31]

      White, J.; Bird, D. Phys. Rev. B 1994, 50, 4954. doi: 10.1103/PhysRevB.50.4954

  32. [32]

      Perdew, J. P.; Burke, K.; Ernzerhof, M. Phys. Rev. Lett. 1996, 77, 3865. doi: 10.1103/PhysRevLett.77.3865

  33. [33]

      Monkhorst, H. J.; Pack, J. D. Phys. Rev. B 1976, 13, 5188. doi: 10.1103/PhysRevB.13.5188

  34. [34]

      Cui, J.; Yao, S.; Ihsan-Ul-Haq, M.; Wu, J.; Kim, J. K. Adv. Energy Mater. 2019, 9, 1802777. doi: 10.1002/aenm.201802777

  35. [35]

      Sun, W.; Du, L.; Tan, Q.; Zhou, J.; Hu, Y.; Du, C.; Gao, Y.; Yin, G. ACS Appl. Mater. Interfaces 2019, 11, 41258. doi: 10.1021/acsami.9b11830

  36. [36]

      Yang, L.; Shi, L.; Wang, D.; Lv, Y.; Cao, D. Nano Energy 2018, 50, 691. doi: 10.1016/j.nanoen.2018.06.023

  37. [37]

      Cheng, X. B.; Yan, C.; Peng, H. J.; Huang, J. Q.; Yang, S. T.; Zhang, Q. Energy Storage Mater. 2018, 10, 199. doi: 10.1016/j.ensm.2017.03.008

  38. [38]

      Liu, K.; Li, Z.; Xie, W.; Li, J.; Rao, D.; Shao, M.; Zhang, B.; Wei, M. Energy Storage Mater. 2018, 15, 308. doi: 10.1016/j.ensm.2018.05.025

  39. [39]

      Deng, W.; Zhu, W.; Zhou, X.; Liu, Z. Energy Storage Mater. 2018, 15, 266. doi: 10.1016/j.ensm.2018.05.005

  40. [40]

      Chen, W.; Salvatierra, R. V.; Ren, M.; Chen, J.; Stanford, M. G.; Tour, J. M. Adv. Mater. 2020, 2002850. doi: 10.1002/adma.202002850

  41. [41]

      Zhang, R.; Chen, X.; Shen, X.; Zhang, X. Q.; Chen, X. R.; Cheng, X. B.; Yan, C.; Zhao, C. Z.; Zhang, Q. Joule 2018, 2, 764. doi: 10.1016/j.joule.2018.02.001

  42. [42]

      Chen, X.; Chen, X. R.; Hou, T. Z.; Li, B. Q.; Cheng, X. B.; Zhang, R.; Zhang, Q. Sci. Adv. 2019, 5, eaau7728. doi: 10.1126/sciadv.aau7728

  43. [43]

      Yin, Y. X.; Xin, S.; Guo, Y. G.; Wan, L. J. Angew. Chem. Int. Ed. 2013, 52, 13186. doi: 10.1002/anie.201304762

  44. [44]

      Shi, H.; Zhao, X.; Wu, Z. S.; Dong, Y.; Lu, P.; Chen, J.; Ren, W.; Cheng, H. M.; Bao, X. Nano Energy 2019, 60, 743. doi: 10.1016/j.nanoen.2019.04.006

  45. [45]

      Shi, H.; Dong, Y.; Zhou, F.; Chen, J.; Wu, Z. S. J. Phys.: Energy 2018, 1, 015002. doi: 10.1088/2515-7655/aadef6

•