The Anode/Electrolyte Interface

Peled, E.; Golodnitsky, D.; Penciner, J.

doi:10.1002/9783527611676.ch18

Cited by 33 publications

(48 citation statements)

References 71 publications

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“…It has been proposed previously that polymeric species form in the SEI layer of Li-ion anodes upon lithiation of the anodes. ,, In order to evaluate the size of this polymer, we use T 1 relaxation time measurements from the lithiated anodes and compare these with corresponding measurements from the PEO polymers. Spin–lattice (T 1 ) relaxation times of compounds yield information about the relative size, motion, and viscosity of the species.…”

Section: Resultsmentioning

confidence: 99%

Identification of Li-Ion Battery SEI Compounds through ⁷Li and ¹³C Solid-State MAS NMR Spectroscopy and MALDI-TOF Mass Spectrometry

Huff

Tavassol

Esbenshade

et al. 2015

ACS Appl. Mater. Interfaces

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Solid-state (7)Li and (13)C MAS NMR spectra of cycled graphitic Li-ion anodes demonstrate SEI compound formation upon lithiation that is followed by changes in the SEI upon delithiation. Solid-state (13)C DPMAS NMR shows changes in peaks associated with organic solvent compounds (ethylene carbonate and dimethyl carbonate, EC/DMC) upon electrochemical cycling due to the formation of and subsequent changes in the SEI compounds. Solid-state (13)C NMR spin-lattice (T1) relaxation time measurements of lithiated Li-ion anodes and reference poly(ethylene oxide) (PEO) powders, along with MALDI-TOF mass spectrometry results, indicate that large-molecular-weight polymers are formed in the SEI layers of the discharged anodes. MALDI-TOF MS and NMR spectroscopy results additionally indicate that delithiated anodes exhibit a larger number of SEI products than is found in lithiated anodes.

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Section: Resultsmentioning

confidence: 99%

Identification of Li-Ion Battery SEI Compounds through ⁷Li and ¹³C Solid-State MAS NMR Spectroscopy and MALDI-TOF Mass Spectrometry

Huff

Tavassol

Esbenshade

et al. 2015

ACS Appl. Mater. Interfaces

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“…An ideal SEI is electronically insulating and protects, on the one hand, the electrolyte from further degradation reactions and, on the other hand, the interphase itself from unwanted continuous growth. Additionally, in the case of layered structure-based electrodes, e.g., graphite, an effective SEI allows only the passage of Li ions and thus prevents co-intercalation of other ions or solvent molecules, which can cause an exfoliation of the electrode material. − With regard to the latter, the application of IL-based electrolytes in combination with graphite electrodes is limited as co-intercalation of the respective cation of the IL may occur. , For carbonate-based electrolytes competitive reactions between electrode passivation and solvent co-intercalation, leading to exfoliation, was investigated by Aurbach et al It could be shown that co-intercalation of solvent molecules may be kinetically favored depending on the electrolyte system and the active surface area of the graphite electrode. , Therefore, it can be assumed that these competitive reactions also take place for IL-based electrolytes resulting in cation co-intercalation into the graphitic structure . This limitation, however, is not present for lithium metal batteries (LMBs) as lithium metal is utilized as anode material instead of graphite or other layered structures enabling intercalation processes .…”

Section: Introductionmentioning

confidence: 99%

Is the Cation Innocent? An Analytical Approach on the Cationic Decomposition Behavior of N-Butyl-N-methylpyrrolidinium Bis(trifluoromethanesulfonyl)imide in Contact with Lithium Metal

et al. 2020

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The stability of the ionic liquid (IL) N-butyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (Pyr14TFSI) against lithium metal at room temperature was investigated by gas chromatography/mass spectrometry (GC/MS), solid phase microextraction gas chromatography/mass spectrometry (SPME-GC/MS), and gas chromatography/high-resolution mass spectrometry (GC/HR-MS). The focus of this work is the degradation behavior and mechanism of the Pyr14 + cation in the presence of lithium metal as the anion participation in the formation of the solid electrolyte interphase (SEI) in IL-based systems has been, and continues to be, well described. N-Butyl-N-methyl-N-but-3-eneamine could be identified as a decomposition product for the first time. The existence of this compound was validated by chemical ionization (CI) experiments as well as with high-resolution results and the comparison with N,N-dibutyl-N-methylamine (DBMA) as a reference substance. Additionally, N-methylpyrrolidine (NMP) was identified as well as an analogue of N,N-dibutyl-N-methylamine, whose molecular structure could not be conclusively determined. The special feature of this finding is the terminal vinyl group of the N-butyl-N-methyl-N-but-3-eneamine which could generally enable polymerization reactions. It suggests that the Pyr14 + cation is not “innocent” and can participate in the formation of an organic layer at the surface of lithium metal. Therefore, this work contributes to a better understanding of the aging behavior of Pyr14TFSI or pyrrolidinium-based ILs in general.

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“…It is believed that SEI film characteristics such as their mechanical and thermodynamics properties govern the lifetime to a significant extent. 1 During cycling, the electrode undergoes volume expansions and contractions, which may result in fractures of SEI films. Dissolution of the film may expose the electrode surface to the electrolyte, prompting reactions with the electrolyte that reduce the cell capacity.…”

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Solubility of Lithium Salts Formed on the Lithium-Ion Battery Negative Electrode Surface in Organic Solvents

Tasaki¹,

Goldberg²,

Lian³

et al. 2009

J. Electrochem. Soc.

316

259

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The solubility of lithium salts in dimethyl carbonate ͑DMC͒ found in solid electrolyte interface ͑SEI͒ films was determined. The salt-DMC solutions evaporated, and the salts were transferred into water for ion conductivity measurements. The salts examined included lithium carbonate ͑Li 2 CO 3 ͒, lithium oxalate ͓͑LiCO 2 ͒ 2 ͔, lithium fluoride ͑LiF͒, lithium hydroxide ͑LiOH͒, lithium methyl carbonate ͑LiOCO 2 CH 3 ͒, and lithium ethyl carbonate ͑LiOCO 2 C 2 H 5 ͒. The salt molarity in DMC ranged from 9.6 ϫ 10 −4 mol L −1 ͑LiOCO 2 CH 3 ͒ to 9 ϫ 10 −5 mol L −1 ͑Li 2 CO 3 ͒ in the order of LiOCO 2 CH 3 Ͼ LiOCO 2 C 2 H 5 Ͼ LiOH Ͼ LiF Ͼ ͑LiCO 2 ͒ 2 Ͼ Li 2 CO 3. X-ray photoelectron spectroscopy measurements on SEI films on the surface of the negative electrode taken from a commercial battery after soaking in DMC for 1 h suggested that the films can dissolve. Separately, the heat of dissolution of the salts was calculated from computer simulations for the same salts, including lithium oxide ͑Li 2 O͒, lithium methoxide ͑LiOCH 3 ͒, and dilithium ethylene glycol dicarbonate ͓͑CH 2 OCO 2 Li͒ 2 :LiEDC͔ in both DMC and ethylene carbonate ͑EC͒. The results from the computer simulations suggested that the order in which the salt was likely to dissolve in both DMC and EC was LiEDC Ͼ LiOCO 2 CH 3 Ͼ LiOH Ͼ LiOCO 2 C 2 H 5 Ͼ LiOCH 3 Ͼ LiF Ͼ ͑LiCO 2 ͒ 2 Ͼ Li 2 CO 3 Ͼ Li 2 O. This order agreed with the experiment in DMC within the experimental error. Both experiment and computer simulations showed that the organic salts are more likely to dissolve in DMC than the inorganic salts. The calculations also predicted that the salts dissolve more likely in EC than in DMC in general. Moreover, the results from the study were used to discuss the capacity fading mechanism during the storage of lithium-ion batteries.

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The Anode/Electrolyte Interface

Cited by 33 publications

References 71 publications

Identification of Li-Ion Battery SEI Compounds through ⁷Li and ¹³C Solid-State MAS NMR Spectroscopy and MALDI-TOF Mass Spectrometry

Identification of Li-Ion Battery SEI Compounds through ⁷Li and ¹³C Solid-State MAS NMR Spectroscopy and MALDI-TOF Mass Spectrometry

Is the Cation Innocent? An Analytical Approach on the Cationic Decomposition Behavior of N-Butyl-N-methylpyrrolidinium Bis(trifluoromethanesulfonyl)imide in Contact with Lithium Metal

Solubility of Lithium Salts Formed on the Lithium-Ion Battery Negative Electrode Surface in Organic Solvents

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The Anode/Electrolyte Interface

Cited by 33 publications

References 71 publications

Identification of Li-Ion Battery SEI Compounds through 7Li and 13C Solid-State MAS NMR Spectroscopy and MALDI-TOF Mass Spectrometry

Identification of Li-Ion Battery SEI Compounds through 7Li and 13C Solid-State MAS NMR Spectroscopy and MALDI-TOF Mass Spectrometry

Is the Cation Innocent? An Analytical Approach on the Cationic Decomposition Behavior of N-Butyl-N-methylpyrrolidinium Bis(trifluoromethanesulfonyl)imide in Contact with Lithium Metal

Solubility of Lithium Salts Formed on the Lithium-Ion Battery Negative Electrode Surface in Organic Solvents

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Identification of Li-Ion Battery SEI Compounds through ⁷Li and ¹³C Solid-State MAS NMR Spectroscopy and MALDI-TOF Mass Spectrometry

Identification of Li-Ion Battery SEI Compounds through ⁷Li and ¹³C Solid-State MAS NMR Spectroscopy and MALDI-TOF Mass Spectrometry