Influences of Additives on the Formation of a Solid Electrolyte Interphase on MnO Electrode Studied by Atomic Force Microscopy and Force Spectroscopy

Abstract Li-ion battery performance and life cycle strongly depend on a passivation layer called solid-electrolyte interphase (SEI). Its structure and composition are studied in great details, while its formation process remains elusive due to difficulty of in situ measurements of battery electrodes. Here we provide a facile methodology for in situ atomic force microscopy (AFM) measurements of SEI formation on cross-sectioned composite battery electrodes allowing for direct observations of SEI formation on various types of carbonaceous negative electrode materials for Li-ion batteries. Using this approach, we observed SEI nucleation and growth on highly oriented pyrolytic graphite (HOPG), MesoCarbon MicroBeads (MCMB) graphite, and non-graphitizable amorphous carbon (hard carbon). Besides the details of the formation mechanism, the electrical and mechanical properties of the SEI layers were assessed. The comparative observations revealed that the electrode potentials for SEI formation differ depending on the nature of the electrode material, whereas the adhesion of SEI to the electrode surface clearly correlates with the surface roughness of the electrode. Finally, the same approach applied to a positive LiNi1/3Mn1/3Co1/3O2 electrode did not reveal any signature of cathodic SEI thus demonstrating fundamental differences in the stabilization mechanisms of the negative and positive electrodes in Li-ion batteries.

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In Situ Atomic Force Microscopy Study of Initial Solid Electrolyte Interphase Formation on Silicon Electrodes for Li-Ion Batteries

ACS Applied Materials & Interfaces ◽

10.1021/am500363t ◽

2014 ◽

Vol 6 (9) ◽

pp. 6672-6686 ◽

Cited By ~ 80

Author(s):

Anton Tokranov ◽

Brian W. Sheldon ◽

Chunzeng Li ◽

Stephen Minne ◽

Xingcheng Xiao

Keyword(s):

Atomic Force Microscopy ◽

Solid Electrolyte ◽

Solid Electrolyte Interphase ◽

Microscopy Study ◽

Li Ion Batteries ◽

Atomic Force Microscopy Study ◽

Force Microscopy ◽

Atomic Force ◽

Li Ion

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Understanding the Surface Film Formation on Si Electrodes in Lithium Secondary Batteries with Atomic Force Microscopy

Journal of Nanoscience and Nanotechnology ◽

10.1166/jnn.2020.17815 ◽

2020 ◽

Vol 20 (8) ◽

pp. 4985-4989

Author(s):

Hee-Youb Song ◽

Sung-Su Kim ◽

Paul Maldonado Nogales ◽

Soon-Ki Jeong

Keyword(s):

Atomic Force Microscopy ◽

Solid Electrolyte ◽

Electrolyte Solution ◽

Ethylene Carbonate ◽

Solid Electrolyte Interphase ◽

Electrolyte Solutions ◽

Decomposition Reaction ◽

Lithium Secondary Batteries ◽

Force Microscopy ◽

Atomic Force

The solid electrolyte interphase formation on the negative electrodes of lithium secondary batteries has been considered as one of the principal issues limiting the performance of batteries. Si is an attractive electrode material for improving energy density of lithium secondary batteries because of its high specific theoretical capacity (4200 mAh g−1). However, solid electrolyte interphase formation on Si-based electrodes have not been clearly understood in spite of its significance. Herein, the solid electrolyte interphase formation on Si electrodes in electrolyte solutions containing ethylene carbonate or propylene carbonate was investigated by using in-situ atomic force microscopy. Large and irreversible capacity fade in SiO electrodes was confirmed in both electrolyte solutions through cyclic voltammetry and charge/discharge testing. The in-situ atomic force microscopy results indicated that the decomposition reaction occurred in the ethylene carbonate-based electrolyte solution at a potential of ~0.68 V, while the lithium alloying reaction occurred below 0.25 V during the first reduction process. The decomposition reaction was more vigorous and occurred at a higher potential in the propylene carbonate-based electrolyte solution, resulting in the formation of a thick solid electrolyte interphase film. These results suggest that the solid electrolyte interphase formation on Si electrodes is strongly influenced by the composition of the electrolyte solution.

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