Electrochemical stability of thin film LiMn2O4 cathode in organic electrolyte solutions with different compositions at 55 °C

Mohamedi, Mohamed; Takahashi, Daisuke; Itoh, Takashi; Uchida, Isamu

doi:10.1016/s0013-4686(02)00285-2

Cited by 54 publications

(35 citation statements)

References 34 publications

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“…6,7,12 This work confirms that LiBF 4 caused increased gas evolution from electrolyte oxidation in cells with LiBF 4 , as predicted by DFT calculations. 28 Electrolyte solutions of LiBF 4 produce undesirable effects at the negative electrode, as suggested by previous studies.…”

Section: Discussionsupporting

confidence: 85%

“…6 In an effort to stabilize electrolyte solutions, LiBF 4 has often been studied as a replacement for LiPF 6 . [6][7][8][9][10][11][12] The BF 4 − anion has stronger inter and intra molecular forces than its phosphorous-based analogue. The B-F bond in LiBF 4 is less labile than the P-F bond in LiPF 6 , resulting in improved hydrolytic and thermal stability of electrolyte solutions when LiBF 4 is substituted for LiPF 6 .…”

mentioning

confidence: 99%

“…The use of LiBF 4 electrolyte has been observed to reduce R ct of LiMn 2 O 4 positive electrodes seven-fold compared to LiPF 6 , when these electrodes were cycled up to 4.4 V in carbonate solvents. 12 It has been shown that LiBF 4 improves the coulombic efficiency (CE) of positive electrode half cells and reduces the parasitic current due to aluminum current collector corrosion at high potentials. 6,10 These reports suggest LiBF 4 -based electrolytes could be a promising solution to electrolyte instability at the positive electrode at high potentials.…”

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confidence: 99%

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Effect of Substituting LiBF₄for LiPF₆in High Voltage Lithium-Ion Cells Containing Electrolyte Additives

Ellis

Xia

Louli

et al. 2016

J. Electrochem. Soc.

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This work evaluates the performance of LiBF4-containing electrolytes in lithium-ion cells charged to high voltages (>4.4 V) and explores the compatibility of LiBF4 with additives known to improve the performance of LiPF6-based electrolytes. It was found that the benefit imparted by LiBF4 is lost when cells are charged beyond 4.4 V, at which point electrolyte oxidation causes gas evolution and impedance growth. In the case of LiBF4, impedance growth is shown to be due to increased charge transfer resistance at the negative electrode, indicating poor passivation of the negative electrode. Of the additives tested, only those containing prop-1-ene-1,3-sultone benefit cells with LiBF4 electrolyte at high voltage.

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Section: Discussionsupporting

confidence: 85%

mentioning

confidence: 99%

mentioning

confidence: 99%

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Effect of Substituting LiBF₄for LiPF₆in High Voltage Lithium-Ion Cells Containing Electrolyte Additives

Ellis

Xia

Louli

et al. 2016

J. Electrochem. Soc.

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“…In that work, the decomposition of the electrolyte led to the formation of a LiF layer, and the LiF layer was proposed to be responsible for the deterioration of the electrodes. In addition to that work, previous studies show that an unfavorable SEI including LiF forms on LiMn 2 O 4 during cycling at elevated temperature and it is detrimental to the LiMn 2 O 4 cathode material [7][8][9][10][12][13][14]. Thus, it can be concluded that the LiF layer is one of the factor for the degradation of LiMn 2 O 4 at elevated temperature.…”

Section: Introductionmentioning

confidence: 65%

Formation of an SEI on a LiMn2O4 cathode during room temperature charge–discharge cycling studied by soft X-ray absorption spectroscopy at the Fluorine K-edge

et al. 2011

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The solid electrolyte interface (SEI) formation on the surface of LiMn 2 O 4 electrodes during room temperature charge-discharge cycling was studied using soft X-ray absorption spectroscopy at the Fluorine (F) K-edge. LiMn 2 O 4 electrodes without any binder were prepared by electrostatic spray deposition to eliminate the signal originating from the PVDF binder in the F K-edge X-ray absorption spectra. The F K-edge absorption spectra show that the SEI layer forms at a very early stage of cycling. SEI growth takes place during discharge. In addition, LiF formation is accelerated if the discharge step follows a charge step. The F K-edge absorption spectra suggest that the major component of the SEI is LiF.

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“…[10][11][12] LiBF 4 has often been studied as a substitute for LiPF 6 in lithium-ion cells because of its improved thermal and hydrolytic stability. 3,[12][13][14][15][16][17] LiBF 4 has demonstrated several other important advantages over LiPF 6 : improved performance at sub-zero temperatures, improved passivation of the Al current collector, and improved performance at the positive electrode. 1,[3][4][5][6][7][8][9][12][13][14]17 The disadvantages of LiBF 4 are lower conductivity compared to LiPF 6 and poor performance at the negative electrode.…”

mentioning

confidence: 99%

Synergistic Effect of LiPF₆and LiBF₄as Electrolyte Salts in Lithium-Ion Cells

Ellis

Hill

Gering

et al. 2017

J. Electrochem. Soc.

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Recent work shows promise for LiBF 4 as an electrolyte salt for high voltage lithium-ion batteries. LiBF 4 is more hydrolytically stable than LiPF 6 , and in some cases has proved to be more stable at high voltage. This work shows that 1.0 M electrolytes consisting of equal parts LiBF 4 and LiPF 6 have better performance in certain high voltage (4.35 V) lithium-ion cells than electrolytes with LiPF 6 or LiBF 4 alone. This is shown using long-term cycling and ultra-high precision coulometry on lithium-ion cells, with and without electrolyte additives. Ultra-high precision coulometry showed that electrolyte with 1:1 LiPF 6 :LiBF 4 and no other additives performed as well as electrolyte with LiPF 6 and state-of-the-art additive blends in these cells. The synergism between LiPF 6 and LiBF 4 was explored using XPS, symmetric cells and EIS analysis. These show that LiBF 4 reduces impedance growth at the positive electrode, while LiPF 6 improves passivation at the negative electrode.

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Electrochemical stability of thin film LiMn2O4 cathode in organic electrolyte solutions with different compositions at 55 °C

Cited by 54 publications

References 34 publications

Effect of Substituting LiBF₄for LiPF₆in High Voltage Lithium-Ion Cells Containing Electrolyte Additives

Effect of Substituting LiBF₄for LiPF₆in High Voltage Lithium-Ion Cells Containing Electrolyte Additives

Formation of an SEI on a LiMn2O4 cathode during room temperature charge–discharge cycling studied by soft X-ray absorption spectroscopy at the Fluorine K-edge

Synergistic Effect of LiPF₆and LiBF₄as Electrolyte Salts in Lithium-Ion Cells

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Electrochemical stability of thin film LiMn2O4 cathode in organic electrolyte solutions with different compositions at 55 °C

Cited by 54 publications

References 34 publications

Effect of Substituting LiBF4for LiPF6in High Voltage Lithium-Ion Cells Containing Electrolyte Additives

Effect of Substituting LiBF4for LiPF6in High Voltage Lithium-Ion Cells Containing Electrolyte Additives

Formation of an SEI on a LiMn2O4 cathode during room temperature charge–discharge cycling studied by soft X-ray absorption spectroscopy at the Fluorine K-edge

Synergistic Effect of LiPF6and LiBF4as Electrolyte Salts in Lithium-Ion Cells

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Effect of Substituting LiBF₄for LiPF₆in High Voltage Lithium-Ion Cells Containing Electrolyte Additives

Effect of Substituting LiBF₄for LiPF₆in High Voltage Lithium-Ion Cells Containing Electrolyte Additives

Synergistic Effect of LiPF₆and LiBF₄as Electrolyte Salts in Lithium-Ion Cells