High-Capacity Rechargeable Li/Cl2 Batteries with Graphite Positive Electrodes

Guanzhou Zhu; Peng Liang; Cheng-Liang Huang; Cheng-Chia Huang; Yuan-Yao Li; Shu-Chi Wu; Jiachen Li; Feifei Wang; Xin Tian; Wei-Hsiang Huang; Shi-Kai Jiang; Wei-Hsuan Hung; Hui Chen; Meng-Chang Lin; Bing-Joe Hwang; Hongjie Dai

doi:10.1021/jacs.2c07826

High-Capacity Rechargeable Li/Cl₂ Batteries with Graphite Positive Electrodes

J Am Chem Soc. 2022 Dec 14;144(49):22505-22513. doi: 10.1021/jacs.2c07826. Epub 2022 Nov 30.

Authors

Guanzhou Zhu¹, Peng Liang¹, Cheng-Liang Huang^{2

3}, Cheng-Chia Huang², Yuan-Yao Li², Shu-Chi Wu¹, Jiachen Li¹, Feifei Wang¹, Xin Tian¹, Wei-Hsiang Huang^{4

5}, Shi-Kai Jiang⁶, Wei-Hsuan Hung⁷, Hui Chen⁸, Meng-Chang Lin⁸, Bing-Joe Hwang⁶, Hongjie Dai¹

Affiliations

¹ Department of Chemistry and Bio-X, Stanford University, Stanford, California94305, United States.
² Department of Chemical Engineering, National Chung Cheng University, Chia-Yi62102, Taiwan.
³ Department of Electrical Engineering, National Chung Cheng University, Chia-Yi62102, Taiwan.
⁴ Graduate Institute of Applied Science and Technology, National Taiwan University of Science and Technology, Taipei10607, Taiwan.
⁵ National Synchrotron Radiation Research Center, Hsinchu30076, Taiwan.
⁶ Department of Chemical Engineering, National Taiwan University of Science and Technology, Taipei10607, Taiwan.
⁷ Institute of Materials Science and Engineering, National Central University, Taoyuan City32001, Taiwan.
⁸ College of Electrical Engineering and Automation, Shandong University of Science and Technology, Qingdao, Shandong Province, 266590, P. R. China.

PMID: 36450002
DOI: 10.1021/jacs.2c07826

Abstract

Developing new types of high-capacity and high-energy density rechargeable batteries is important to future generations of consumer electronics, electric vehicles, and mass energy storage applications. Recently, we reported ∼3.5 V sodium/chlorine (Na/Cl₂) and lithium/chlorine (Li/Cl₂) batteries with up to 1200 mAh g^-1 reversible capacity, using either a Na or a Li metal as the negative electrode, an amorphous carbon nanosphere (aCNS) as the positive electrode, and aluminum chloride (AlCl₃) dissolved in thionyl chloride (SOCl₂) with fluoride-based additives as the electrolyte [Zhu et al., Nature, 2021, 596 (7873), 525-530]. The high surface area and large pore volume of aCNS in the positive electrode facilitated NaCl or LiCl deposition and trapping of Cl₂ for reversible NaCl/Cl₂ or LiCl/Cl₂ redox reactions and battery discharge/charge cycling. Here, we report an initially low surface area/porosity graphite (DGr) material as the positive electrode in a Li/Cl₂ battery, attaining high battery performance after activation in carbon dioxide (CO₂) at 1000 °C (DGr_ac) with the first discharge capacity ∼1910 mAh g^-1 and a cycling capacity up to 1200 mAh g^-1. Ex situ Raman spectroscopy and X-ray diffraction (XRD) revealed the evolution of graphite over battery cycling, including intercalation/deintercalation and exfoliation that generated sufficient pores for hosting LiCl/Cl₂ redox. This work opens up widely available, low-cost graphitic materials for high-capacity alkali metal/Cl₂ batteries. Lastly, we employed mass spectrometry to probe the Cl₂ trapped in the graphitic positive electrode, shedding light into the Li/Cl₂ battery operation.