Decomposition reaction of LiPF6-based electrolytes for lithium ion cells

Kawamura, Takahiro; Okada, Shigeto; Yamaki, Jun Ichi

doi:10.1016/j.jpowsour.2005.05.084

Cited by 367 publications

(330 citation statements)

References 11 publications

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“…The new film, which is indicated by the presence of O-C=O environments within the surface film of only vibrated cells, reforms in its place. As first presented in [38] and summarized in Table 1, the cell level manifestation of this reaction is a reduction in cell capacity and an increase in impedance.…”

Section: Discussionmentioning

confidence: 87%

“…The XPS data fitting used is consistent for most of the chemical environments studied, however, there are variances in the percentage values of some C-O and O-C=O components between vibrated cells, as shown in Figure 4 and recorded in Table 3. The difference in these values may relate to the inherent differences in cell performance between identical cell types, as shown in [38].…”

Section: Further Workmentioning

confidence: 99%

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Impact of Vibration on the Surface Film of Lithium-Ion Cells

et al. 2017

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Cylindrical 18650-type lithium-ion cells are being utilized more often for automotive applications. This introduces error in calculating expected lifetime due to varied usage conditions accelerating or reducing material damage. One such usage condition is vibration, which has been shown to impact the electrical performance over extended periods. Within this study X-ray photoelectron spectroscopy (XPS) has been performed on nickel manganese cobalt (NMC) cells subjected to vibration. This study found that vibration causes the removal of the selectively-formed surface film created during a cell's first cycles and replaces it with the surface film from electrolyte decomposition. The surface films formed by vibration are composed of much higher concentrations of organic electrolyte decomposition products than the film from the control cell. The impact of this chemical mechanism is an increased level of cell degradation. This is exhibited in increased capacity fade and cell impedance. This is the first study presented within the academic literature which has identified an electro-mechanical mechanism responsible for the performance degradation in lithium-ion cells from vibration.

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Section: Discussionmentioning

confidence: 87%

Section: Further Workmentioning

confidence: 99%

Impact of Vibration on the Surface Film of Lithium-Ion Cells

et al. 2017

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“…4d and 4e show the compositional histograms of the ratios, obtained from the data pixels of There should be some reasons to drive the above reaction. The most probable reason is the existence of HF or any other species in a LiPF 6 -salt based electrolyte 10,[23][24][25][26] and reactions, relevant to Li extraction by contact with them. [27][28][29] Generally, the reaction of electrode materials and electrolyte species is accompanied with the generation of LiF and other fluoride or phosphate compounds.…”

Section: Results and Disscusionmentioning

confidence: 99%

Spontaneous Li-Ion Transfer from Spinel Li₄Ti₅O₁₂Surfaces: Deterioration at Li₄Ti₅O₁₂/Electrolyte Interfaces Stored at Room Temperature

Kitta

Akita

Kohyama

2015

J. Electrochem. Soc.

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Spinel lithium titanium oxide (LTO; Li 4 Ti 5 O 12 ) is one of attractive negative electrode materials for high-performance lithium-ion batteries. We studied the changes of LTO-electrode surfaces in contact with liquid electrolytes without electrochemical operation, as the basic state of a stored cell. The electrochemical properties of the LTO-crystal electrode were greatly deteriorated after soaking in a liquid electrolyte (1 M LiPF 6 in PC) for 2 weeks at room temperature. Spinel LTO structure was changed into rock-salt like structure at the surface region. Spinel lithium titanate (LTO; Li 4 Ti 5 O 12 ) is one of the attractive negative electrode materials for high-performance lithium-ion batteries (LIBs), due to its superior cycle stability with high-rate chargedischarge performance.1 These excellent properties of LTO are concerned with the negligible lattice-parameter change and the simple phase conversion mechanism between the spinel LTO phase and the Li-inserted LTO phase (Li 7 Ti 5 O 12 ) with ordered rock-salt structure. 2,3The chemical stability or electrochemical durability of LTO-based electrodes is crucial to design high-performance LIBs for power sources of electrical vehicles or for large-scale energy storage, which requires high safety, long-life performance, and robustness. For this purpose, we have to understand not only the bulk-electrode phenomena, but also the phenomena at solid-electrode/liquid-electrolyte interfaces, such as solvation-desolvation, Li-ion absorption-desorption, and transfer as well as so-called solid electrolyte interface (SEI) formation. For LTO/liquid-electrolyte interfaces, several studies were performed under some electrochemical conditions. The reactions at LTO surfaces in contact with liquid electrolytes were also investigated in our previously study. 4 We revealed irreversible surface morphology changes during the 1st charge-discharge cycle. After the 1 st cycle, we observed the generation of the surface layer of a Li-rich phase (Li 2 TiO 3 ) with cubic rock-salt structure. 4 This surface layer on a LTO crystal would be some kind of SEI and contribute to the stability or efficiency of charge-discharge cycles. While the electrochemical reactions or associated structural changes at electrode surfaces have been studied under the electrochemical operation, the reactions or associated changes in the static condition are also important to fully understand the performance of electrodes. Especially, the basic interactions between electrode surfaces and liquid electrolytes before or after the charge-discharge operation should greatly affect a lot of battery phenomena, such as self-discharging, 5 alternation of electrode materials and electrolyte, 6-9 decomposition of electrolyte molecules and gas-generation, 5,10-12 which often lead to the deterioration of electrochemical performance and safety of battery cells. 13,14 As for the LTO-electrode/liquid-electrolyte interfaces in the static condition, the decomposition reaction of solvate molecules and the structural changes at ele...

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“…About LiPF 6 with air exposure, both the TEY and PFY spectrum shape are very similar to that of Li 3 PO 4 , but the shoulder peak at 2154.5 eV (red dashed line) can be seen only spectra of LiPF 6 with air exposure. This origin is not clear yet, but may originate from POF 3 , POF 2 (OH) or other materials generated by hydrolyzed LiPF 6 [Kawamura et al, 2006]. [Momma & Izumi, 2008].…”

Section: Transfer Vessel System For Anaerobic Samplesmentioning

confidence: 99%

XAFS Measurement System in the Soft X-ray Region for Various Sample Conditions and Multipurpose Measurements

Nakanishi¹,

Ohta²

2012

Advanced Topics in Measurements

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Decomposition reaction of LiPF6-based electrolytes for lithium ion cells

Cited by 367 publications

References 11 publications

Impact of Vibration on the Surface Film of Lithium-Ion Cells

Impact of Vibration on the Surface Film of Lithium-Ion Cells

Spontaneous Li-Ion Transfer from Spinel Li₄Ti₅O₁₂Surfaces: Deterioration at Li₄Ti₅O₁₂/Electrolyte Interfaces Stored at Room Temperature

XAFS Measurement System in the Soft X-ray Region for Various Sample Conditions and Multipurpose Measurements

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Decomposition reaction of LiPF6-based electrolytes for lithium ion cells

Cited by 367 publications

References 11 publications

Impact of Vibration on the Surface Film of Lithium-Ion Cells

Impact of Vibration on the Surface Film of Lithium-Ion Cells

Spontaneous Li-Ion Transfer from Spinel Li4Ti5O12Surfaces: Deterioration at Li4Ti5O12/Electrolyte Interfaces Stored at Room Temperature

XAFS Measurement System in the Soft X-ray Region for Various Sample Conditions and Multipurpose Measurements

Contact Info

Product

Resources

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Spontaneous Li-Ion Transfer from Spinel Li₄Ti₅O₁₂Surfaces: Deterioration at Li₄Ti₅O₁₂/Electrolyte Interfaces Stored at Room Temperature