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:

  Dalian Institute Of Chemical Physics DICP ZZBS201708

  Dalian Institute Of Chemical Physics and Qingdao Institute of Biomass Energy and Bioprocess Technology DICP&QIBEBT UN201702

  the Dalian National Laboratory For Clean Energy (DNL), CAS, DNL Cooperation Fund, CAS DNL180308

  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)

  Dalian Institute Of Chemical Physics DICP I202032

  the National Natural Science Foundation of China 51872283

  the Natural Science Foundation of Liaoning Province 20180510038

  the Dalian National Laboratory For Clean Energy (DNL), CAS, DNL Cooperation Fund, CAS DNL180310

  Dalian Institute Of Chemical Physics DICP ZZBS201802

  the Dalian National Laboratory For Clean Energy (DNL), CAS, DNL Cooperation Fund, CAS DNL201912

  the National Natural Science Foundation of China 21805273

  the Liaoning BaiQianWan Talents Program, Liaoning Revitalization Talents Program XLYC1807153

  the National Key R@D Program of China 2016YBF0100100

  the Dalian National Laboratory For Clean Energy (DNL), CAS, DNL Cooperation Fund, CAS 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

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