Deciphering Electrolyte Dominated Na⁺ Storage Mechanisms in Hard Carbon Anodes for Sodium-Ion Batteries

Liu, Guiyu; Wang, Zhiqiang; Yuan, Huimin; Yan, Chunliu; Hao, Rui; Zhang, Fangchang; Luo, Wen; Wang, Hongzhi; Cao, Yulin; Gu, Shuai; Zeng, Chun; Li, Yingzhi; Wang, Zhenyu; Qin, Ning; Luo, Guangfu; Lu, Zhouguang

2023-10-01

10.1002/advs.202305414

ADVANCED SCIENCE   Impact Factor & Quartile

2198-3844

Although hard carbon (HC) demonstrates superior initial Coulombic efficiency, cycling durability, and rate capability in ether-based electrolytes compared to ester-based electrolytes for sodium-ion batteries (SIBs), the underlying mechanisms responsible for these disparities remain largely unexplored. Herein, ex situ electron paramagnetic resonance (EPR) spectra and in situ Raman spectroscopy are combined to investigate the Na storage mechanism of HC under different electrolytes. Through deconvolving the EPR signals of Na in HC, quasi-metallic-Na is successfully differentiated from adsorbed-Na. By monitoring the evolution of different Na species during the charging/discharging process, it is found that the initial adsorbed-Na in HC with ether-based electrolytes can be effectively transformed into intercalated-Na in the plateau region. However, this transformation is obstructed in ester-based electrolytes, leading to the predominant storage of Na in HC as adsorbed-Na and pore-filled-Na. Furthermore, the intercalated-Na in HC within the ether-based electrolytes contributes to the formation of a uniform, dense, and stable solid-electrolyte interphase (SEI) film and eventually enhances the electrochemical performance of HC. This work successfully deciphers the electrolyte-dominated Na+ storage mechanisms in HC and provides fundamental insights into the industrialization of HC in SIBs.

electrolyte electron paramagnetic resonance hard carbon in situ Raman sodium storage mechanism

SCI

English

First ; Corresponding

This work was financially supported by the Basic Research Project of the Science and Technology Innovation Commission of Shenzhen (no. JCYJ20220818100418040), Shenzhen Key Laboratory of Interfacial Science and Engineering of Materials (no. ZDSYS20200421111[JCYJ20220818100418040] ; Basic Research Project of the Science and Technology Innovation Commission of Shenzhen[ZDSYS20200421111401738] ; Shenzhen Key Laboratory of Interfacial Science and Engineering of Materials[U22A20439] ; Center for Computational Science and Engineering[2019B030301001] ; Guangdong Provincial Key Laboratory of Computational Science and Material Design[2017ZT07C062] ; Introduced Innovative Ramp;D Team of Guangdong[JCYJ20200109141412308]

Chemistry ; Science & Technology - Other Topics ; Materials Science

Chemistry, Multidisciplinary ; Nanoscience & Nanotechnology ; Materials Science, Multidisciplinary

WOS:001093848600001

WILEY

Web of Science

Southern Univ Sci & Technol, Dept Mat Sci & Engn, Shenzhen Key Lab Interfacial Sci & Engn Mat, Shenzhen 518055, Peoples R China

Liu, Guiyu,Wang, Zhiqiang,Yuan, Huimin,et al. Deciphering Electrolyte Dominated Na⁺ Storage Mechanisms in Hard Carbon Anodes for Sodium-Ion Batteries[J]. ADVANCED SCIENCE,2023.

Liu, Guiyu.,Wang, Zhiqiang.,Yuan, Huimin.,Yan, Chunliu.,Hao, Rui.,...&Lu, Zhouguang.(2023).Deciphering Electrolyte Dominated Na⁺ Storage Mechanisms in Hard Carbon Anodes for Sodium-Ion Batteries.ADVANCED SCIENCE.

Liu, Guiyu,et al."Deciphering Electrolyte Dominated Na⁺ Storage Mechanisms in Hard Carbon Anodes for Sodium-Ion Batteries".ADVANCED SCIENCE (2023).