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ACS Applied Materials & Interfaces
Article . 2024 . Peer-reviewed
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Slow Voltage Relaxation of Silicon Nanoparticles with a Chemo-Mechanical Core–Shell Model

Authors: Köbbing, Lukas; Kuhn, Yannick; Horstmann, Birger;

Slow Voltage Relaxation of Silicon Nanoparticles with a Chemo-Mechanical Core–Shell Model

Abstract

Silicon presents itself as a high-capacity anode material for lithium-ion batteries with a promising future. The high ability for lithiation comes along with massive volume changes and a problematic voltage hysteresis, causing reduced efficiency, detrimental heat generation, and a complicated state-of-charge estimation. During slow cycling, amorphous silicon nanoparticles show a larger voltage hysteresis than after relaxation periods. Interestingly, the voltage relaxes for at least several days, which has not been physically explained so far. We apply a chemo-mechanical continuum model in a core-shell geometry interpreted as a silicon particle covered by the solid-electrolyte interphase to account for the hysteresis phenomena. The silicon core (de)lithiates during every cycle while the covering shell is chemically inactive. The visco-elastoplastic behavior of the shell explains the voltage hysteresis during cycling and after relaxation. We identify a logarithmic voltage relaxation, which fits with the established Garofalo law for viscosity. Our chemo-mechanical model describes the observed voltage hysteresis phenomena and outperforms the empirical Plett model. In addition to our full model, we present a reduced model to allow for easy voltage profile estimations. The presented results support the mechanical explanation of the silicon voltage hysteresis with a core-shell model and encourage further efforts into the investigation of the silicon anode mechanics.

Country
Germany
Keywords

Chemical Physics (physics.chem-ph), Condensed Matter - Materials Science, Silicon Voltage Relaxation, Materials Science (cond-mat.mtrl-sci), FOS: Physical sciences, Solid-Electrolyte Interphase (SEI), SEI Mechanics, Physics - Applied Physics, Applied Physics (physics.app-ph), Voltage Relaxation, Lithium-Ion Batteries, Voltage Hysteresis, Chemo-Mechanical Core-Shell Model, Silicon Anode, Visco-elastoplastic Model, Physics - Chemical Physics, Garofalo Viscosity, Silicon-SEI Mechanics

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    popularity
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    Top 10%
    influence
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    impulse
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selected citations
These citations are derived from selected sources.
This is an alternative to the "Influence" indicator, which also reflects the overall/total impact of an article in the research community at large, based on the underlying citation network (diachronically).
BIP!Citations provided by BIP!
popularity
This indicator reflects the "current" impact/attention (the "hype") of an article in the research community at large, based on the underlying citation network.
BIP!Popularity provided by BIP!
influence
This indicator reflects the overall/total impact of an article in the research community at large, based on the underlying citation network (diachronically).
BIP!Influence provided by BIP!
impulse
This indicator reflects the initial momentum of an article directly after its publication, based on the underlying citation network.
BIP!Impulse provided by BIP!
4
Top 10%
Average
Average
Green
hybrid