AFM Investigation of Solid Electrolyte Interphase on HOPG Anode in Sodium Ion Battery

doi:10.15541/jim20160472

Abstract

Abstract:

Chemical and morphological structures of solid electrolyte interphase (SEI) play a vital role in sodium-ion battery (NIB). Up to date, SEI remains the least understood component in NIB due to its trace presence, delicate chemical nature, heterogeneity in morphology, elusive formation mechanism, and lack of reliable in situ quantitative characterization tools. SEI morphological evolution during the first cyclic voltammetry and the thickness of SEI after first discharging-charging cycle on highly oriented pyrolytic graphite (HOPG) surface were investigated by using in situ electrochemical atomic force microscopy (EC-AFM). Complemented by an ex situ XPS analysis, the differences in interfacial features and fundamental constitution of SEI formation in ethylene carbonate (EC) and fluoroethylene carbonate (FEC)-based electrolytes on HOPG electrode surface were revealed. In 1 mol/L NaClO₄/EC/DMC electrolyte, dense films were formed at the step edges, while thinner films were observed on the basal plane. In 1 mol/L NaClO₄/EC/DMC electrolyte, stable films with doubled layer structures were formed on HOPG electrode after initial electrochemical cycling. The upper layer was composed of large particles, which was soft and easy to be scrapped off by AFM tip while the under layer was composed of dense small particles.

Key words: sodium ion battery, solid electrolyte interphase, electrochemical atomic force microscopy, electrolyte

CLC Number:

TQ174

WANG Shu-Wei, HU He-Feng, WANG De-Yu, SHEN Cai. AFM Investigation of Solid Electrolyte Interphase on HOPG Anode in Sodium Ion Battery[J]. Journal of Inorganic Materials, 2017, 32(6): 596-602.

Figures/Tables 8

Fig. 1 Cyclic voltammogram of HOPG electrode in 1 mol/L NaClO4/EC/DMC and 1 mol/L NaClO4/FEC/DMC at scan rate of 0.5 mV/s

Fig. 2 In situ AFM images of HOPG electrode cycled at a scanning rate of 0.5 mV/s between 3.0 and 0 V in 1 mol/L NaClO4/EC/DMC(a) During discharging, potential range of 3.0-2.84 V; (b) During discharging, potential range of 0.24-0.04 V; (c) The potential is sweeped from 0.04 V to 0 V then rised to 0.13 V; (d) During charging, potential range of 2.98-3.0 V. The arrow indicates AFM scanning direction

Fig. 3 (a) AFM image of HOPG electrode after first CV cycle in the 1 mol/L NaClO4/EC/DMC; (b) AFM image of the HOPG anode after the SEI in the middle of the image being scraped off and (c) cross-section analysis of the location marked by blue line

Fig. 4 In situ AFM images of HOPG electrode cycled at a scanning rate of 0.5 mV/s between 3.0 and 0.0 V in 1 mol/L NaClO4/FEC/DMC(a) During discharging, potential range of 3.0-2.85 V; (b) During discharging, potential range of 1.06-0.93 V; (c) During discharging, potential range: of 0.93-0.80 V; (d) During discharging, the potential range of 0.66-0.52 V; (e) The potential is sweeped from 0.01 V to 0 V then rised to 0.17 V; (f) During charging, the potential range of 2.90-3.0 V; The arrow indicates AFM scanning direction

Fig. 5 (a) AFM image of HOPG electrode after first CV cycle in the 1 mol/L NaClO4/FEC/DMC; (b) AFM image of the HOPG anode after the SEI in the middle of the image being scraped off; and (c) cross-section analysis of the location marked by blue line

Fig. 6 (a) AFM image of under SEI layer on HOPG electrode after first CV cycle in the 1 mol/L NaClO4/FEC/DMC; (b) AFM image of the HOPG anode after the SEI in the middle of the image being scraped off; (c) cross-section analysis of the location marked by blue line

Fig. 7 XPS spectra of the SEI on HOPG electrode cycled at a scanning rate of 0.5 mV/s between 3.0 and 0 V in the EC/DMC and FEC/DMC electrolytes

Table 1 Atomic concentrations of C, O, Na, Cl and F obtained from XPS

HOPG		Atomic concentration /%
HOPG		C	O	Na	Cl	F
1 mol/L NaClO₄ /EC/DMC	Before etching	80.22	16.63	2.56	0.59	-
1 mol/L NaClO₄ /EC/DMC	After etching	83.16	11.62	3.42	1.80	-
1 mol/L NaClO₄ /FEC/DMC	Before etching	77.90	12.36	4.18	0.87	4.69
1 mol/L NaClO₄ /FEC/DMC	After etching	78.02	5.21	6.95	2.03	7.79

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