Impedance of the Li Electrode in Li / Li x MnO2 Accumulators at Open‐Circuit Voltage

Bojinov, Martin; Geronov, Y.; Pistoia, G.; Pasquali, Marco

doi:10.1149/1.2221040

Cited by 8 publications

(3 citation statements)

References 14 publications

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“…Additionally, there are experimental evidences that the SEI starts forming immediately after the electrode is put in contact with the electrolyte whether under the open circuit voltage , or even by merely immersing it into the electrolyte solution . Thermodynamically, this is not surprising as the solid lithium metal has equivalent reducing power to a Li + + e – pair at 0 V Li/Li + .…”

Section: Resultsmentioning

confidence: 99%

The Electrochemical Mechanisms of Solid–Electrolyte Interphase Formation in Lithium-Based Batteries

2019

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In lithium-based batteries, the solid−electrolyte interphase (SEI) is a layer of material that forms between the negative electrode and the liquid electrolyte; it is produced spontaneously by the breakdown of electrolyte compounds at the highly reducing potentials inherent to these systems. The SEI is perhaps the most important factor controlling the efficiency, safety, and lifetime of lithium batteries, and many empirical approaches have been developed to control the SEI's properties. In this work, we adapt methods from electrocatalysis to allow for the potentialdependent, atomistic simulation of SEI formation on lithium surfaces via electronic structure calculations. We use a computational lithium electrode (CLE) technique, in which the potential scale is thermodynamically linked to the lithium reference electrode, to study the decomposition of ethylene carbonate, one of the most prevalent battery electrolytes, into SEI components on lithium-based surfaces. On Li metal surfaces, we find that the most favorable process is forming the inorganic carbonate phases (accompanied by the liberation of ethylene gas), while forming the organic SEI component lithium ethylene dicarbonate (LiEDC) is unfavorable. In contrast, we find LiEDC to be favorable on the inorganic lithium surfaces (Li 2 CO 3 and Li 2 O). This gives a mechanistic interpretation of a common physical picture of SEI formation: inorganic species (e.g., Li 2 CO 3 ) are formed more heavily near the electrode, while organic species (e.g., LiEDC) are formed more heavily near the electrolyte. Both electrochemical and non-electrochemical pathways are explored and found to have similar energetics at this level of theory. This study rationalizes experimental findings and sets the stage for mechanism-based control of SEI formation.

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Section: Resultsmentioning

confidence: 99%

The Electrochemical Mechanisms of Solid–Electrolyte Interphase Formation in Lithium-Based Batteries

2019

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“…A variety of metal oxides have been studied as cathodes and anodes in rechargeable ion batteries used for electrochemical energy storage. ,,,,− EIS can be a useful technique for researching these materials by providing insight into the corrosion rate of the metal oxide electrode during multiple charge and discharge cycles (i.e., long-term cycling efficiency) and ion diffusion into the metal oxide. The most well-studied type of ion battery using EIS is the Li-ion battery ,,− ,− due to its commercialization in many portable electronics; however, other Na-ion ,,,,, and divalent ion batteries, particularly Zn-ion batteries, ,,− have also been investigated using this technique.…”

Section: Ion Batteriesmentioning

confidence: 99%

“…The reversibility of this process depends greatly on the structure and electrochemical properties of the metal oxide cathode. Oxides such as LiCoO 2 , LiNiO 2 , and LiMnO 2 possess layered structures where Li + ions are able to diffuse in and out of the host oxide. ,,,,, Other important oxides such as spinel LiMn 2 O 4 and its substituted derivatives (e.g., LiNi 0.5 Mn 1.5 O 4 ) possess interstitial sites where the occupancy by Li + is variable. ,,− Importantly, the charge storage capacity of a metal oxide host is limited by the reversible solid-solution range of Li + intercalation in the cathode host structure for a given redox potential of the transition metal cation …”

Section: Ion Batteriesmentioning

confidence: 99%

Electrochemical Impedance Spectroscopy of Metal Oxide Electrodes for Energy Applications

Bredar

Chown

Burton

et al. 2020

ACS Appl. Energy Mater.

678

412

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Metal oxides have been of great importance to the development of energy conversion and storage technologies including heterojunction solar cells, Li-ion batteries, and electrocatalysts/photocatalysts for water splitting and CO2 reduction. The role of metal oxides in these devices has been diverse, from charge transport layers to catalytic surfaces to protective blocking layers. Understanding the fundamental structural and electronic properties of these materials will continue to allow for advancement in the field of renewable energy. Electrochemical impedance spectroscopy (EIS) is one of the most utilized methods to characterize these electrodes in the context of energy applications. The utility of EIS stems from its ability to differentiate multiple interfaces (i.e., solid/electrolyte, solid/solid) within devices on the basis of their frequency response to a modulated potential and the subsequent decoupling of resistive and capacitive circuit components. In this review, the fundamental theory of EIS is first described with a physical and mathematical basis, followed by a discussion of equivalent circuit modeling. The review then covers examples from the literature where EIS has been particularly important in the understanding of electronic properties related to metal oxide electrodes within energy conversion and storage devices. A specific focus is placed on metal oxides that are used as heterojunction solar cells, ion batteries, and photocatalysts/electrocatalysts. Common themes are discussed within each application such as the study of electron and hole diffusion in solar cells, the dependence of recombination reactions and catalysis on surface defect/trap states for solar cells and photocatalysts, and the formation of passivation layers at the solid electrolyte interface in Li-ion batteries.

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Changes in the resistance of electrolyte solutions during contact with lithium electrodes at open circuit potential that reflect the Li surface chemistry

Aurbach

Schechter

2001

Electrochimica Acta

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Impedance of the Li Electrode in Li / Li x MnO2 Accumulators at Open‐Circuit Voltage

Cited by 8 publications

References 14 publications

The Electrochemical Mechanisms of Solid–Electrolyte Interphase Formation in Lithium-Based Batteries

The Electrochemical Mechanisms of Solid–Electrolyte Interphase Formation in Lithium-Based Batteries

Electrochemical Impedance Spectroscopy of Metal Oxide Electrodes for Energy Applications

Changes in the resistance of electrolyte solutions during contact with lithium electrodes at open circuit potential that reflect the Li surface chemistry

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