Research Papers

The Effect of Solvent on the Capacity Retention in a Germanium Anode for Lithium Ion Batteries

[+] Author and Article Information
Kuber Mishra

Department of Chemical Engineering,
University of South Carolina,
Columbia, SC 29208

Wu Xu, Ruiguo Cao, Jie Xiao, Ji-Guang Zhang

Pacific Northwest National Laboratory,
Energy and Environment Directorate,
Richland, WA 99354

Mark H. Engelhard

Environmental Molecular Sciences Laboratory,
Pacific Northwest National Laboratory,
Richland, WA 99354

Xiao-Dong Zhou

Department of Chemical Engineering,
University of South Carolina,
Columbia, SC 29208;
Department of Chemical Engineering,
Institute for Materials Research and Innovation,
University of Louisiana at Lafayette,
Lafayette, LA 70503
e-mail: zhou@louisiana.edu

1Corresponding author.

Manuscript received August 24, 2017; final manuscript received March 28, 2018; published online September 12, 2018. Assoc. Editor: San Ping Jiang. The United States Government retains, and by accepting the article for publication, the publisher acknowledges that the United States Government retains, a nonexclusive, paid-up, irrevocable, worldwide license to publish or reproduce the published form of this work, or allow others to do so, for United States Government purposes.

J. Electrochem. En. Conv. Stor. 15(4), 041012 (Sep 12, 2018) (7 pages) Paper No: JEECS-17-1108; doi: 10.1115/1.4039860 History: Received August 24, 2017; Revised March 28, 2018

A thin and mechanically stable solid electrolyte interphase (SEI) is desirable for a stable cyclic performance in a lithium ion battery. For the electrodes that undergo a large volume expansion, such as Si, Ge, and Sn, the presence of a robust SEI layer can improve the capacity retention. In this work, the role of solvent choice on the electrochemical performance of Ge electrode is presented by a systematic comparison of the SEI layers in ethylene carbonate (EC)-based and fluoroethylene carbonate (FEC)-based electrolytes. The results show that the presence of FEC as a cosolvent in a binary or ternary solvent electrolyte results in an excellent capacity retention of ∼85% after 200 cycles at the current density of 500 mA g−1; while EC-based electrode suffers a rapid capacity degradation with a capacity retention of just 17% at the end of 200 cycles. Post analysis by an extensive use of X-ray photoelectron spectroscopy (XPS) was carried out, which showed that the presence of Li2O in FEC-based SEIs was the origin for the improved electrochemical performance.

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Grahic Jump Location
Fig. 1

Specific capacity and Coulombic efficiency of the Ge electrode with 1 M LiPF6 in (a) EC–DMC (1:1 by vol), (b) FEC–DMC (1:1 by vol), (c) EC–DMC–DEC (1:1:1 by vol), and (d) FEC–DMC–DEC (1:1:1 by vol). (a) and (b) were obtained at the current density of 500 mA/g; while (c) and (d) were at 800 mA/g.

Grahic Jump Location
Fig. 2

Differential capacity plots for the Ge electrode in (a) EC-based electrolyte and (b) FEC-based electrolyte

Grahic Jump Location
Fig. 3

(a) X-ray photoelectron spectroscopy spectrum for the pristine Ge electrode, (b) wide scan XPS spectra for for the electrodes in EC- and FEC-based electrolytes after 200 cycles, and (c) expanded portion of the selected region of XPS spectra for XPS spectra for the electrode cycled in EC- and FEC-based electrolyte

Grahic Jump Location
Fig. 4

X-ray photoelectron spectroscopy narrow scan spectrum: O 1 s for (a) EC-based and (b) FEC-based SEIs; C 1 s for (c) EC-based and (d) FEC-based SEI; Li 1 s for (e) EC-based and (f) FEC-based SEI; and F 1 s for (g) EC-based and (h) FEC-based SEI

Grahic Jump Location
Fig. 5

Scanning electron microscopy images of Ge electrode (a) pristine, (b) cycled for 200 cycles in EC:DMC:DEC (1:1:1 by vol), and (c) cycled for 200 cycles in FEC:DMC:DEC (1:1:1 by vol) at the current density of 800 mA/g

Grahic Jump Location
Fig. 6

Nyquist plots for FEC-based cells and EC-based cells. (a) 50 cycles, (b) 100 cycles, and (c) an equivalent circuit model for the analysis of Nyquist plots.



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