Electrolytes for advanced batteries

Blomgren, G. E.

doi:10.1016/s0378-7753(99)00188-3

Cited by 98 publications

(73 citation statements)

References 15 publications

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“…The time dependence was set to be proportional to the square root of time as reported by several researchers. [86][87][88][89][90][91] The cycle number dependence can come from the SEI repair at the surface of the Si-alloy particles due to the volume changes upon lithiation and delithiation. In these fits, the possibility of lithium plating was ignored since no plating was observed in cells cycled at C/2.…”

Section: Impedance Of Individual Electrodes Of Lco/si-alloy:graphite mentioning

confidence: 99%

Studies of the Capacity Fade Mechanisms of LiCoO₂/Si-Alloy: Graphite Cells

Petibon

Chevrier

Aiken

et al. 2016

J. Electrochem. Soc.

128

137

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The capacity fade mechanisms of LiCoO 2 /Si-alloy:graphite pouch cells filled with a 1M LiPF 6 EC:EMC:FEC (27:63:10) electrolyte were studied using galvanostatic cycling, electrochemical impedance spectroscopy on symmetric cells, gas-chromatography and differential voltage analysis. Analysis of the gas generated during the first cycle indicated that FEC reacts at the negative electrode following a 1-electron reduction pathway and other pathways that do not lead to the formation of gaseous products. An analysis of the electrolyte showed that FEC is continuously consumed during the first 80% of the first charge (formation cycle). Typical cells charged and discharged at 40 • C showed a gradual capacity loss for the first 250 cycles followed by a sudden capacity drop associated with a large polarization growth. Analysis of the electrolyte showed that this sudden failure is associated with the depletion of FEC. The capacity loss as well as the consumption of FEC prior to the sudden failure was fitted using a model that includes a time dependence and a cycle number dependence. The time dependence was associated with the thickening solid electrolyte interface at the surface of the negative electrode particles (Si-alloy and graphite) and the cycle number dependence was associated with the solid electrolyte interface repair at the surface of Si-alloy particles during repeated expansion and contraction. Cost reduction and an increase in the volumetric energy density of Li-ion cells can possibly be attained using silicon-based negative electrodes.1-3 While these benefits have been known for many years, commercial implementation remains limited due to silicon's inherent challenges.Si-based electrodes can suffer from particle pulverization upon cycling (e.g. micron sized silicon), 1,4-7 can have loss of electronic contact between particles after repeated expansion and contraction during cycling, 2,8-10 can have high irreversible first cycle coulombic efficiency 11,[12][13][14][15] and can have low coulombic efficiency (compared to graphite electrodes) during cycling. 1,16,17 The root cause of these challenges is the large volume expansion 1,18 of the material during lithiation and subsequent contraction during delithiation. Several issues have been solved through the use of either nanosized Si or nanostructured Si. For instance the use of nanosized Si particles solves some of the pulverization problems encountered by micron sized Si particles. 1,4,11,[19][20][21] However, nanosized Si still suffers from inter-particle contact loss during cycling as well as low coulombic efficiency due to large specific surface area. 1,16In a recent publication, Chevrier et al. 16 presented a rational way to design commercially relevant Si-based negative electrodes. They showed that confining nano-domains of silicon in an alloy matrix suppresses particle pulverization and greatly reduces the surface area of Si exposed to the electrolyte. This approach yields materials with lower first cycle irreversible capacity (IRC) loss, better coulombic e...

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Section: Impedance Of Individual Electrodes Of Lco/si-alloy:graphite mentioning

confidence: 99%

Studies of the Capacity Fade Mechanisms of LiCoO₂/Si-Alloy: Graphite Cells

Petibon

Chevrier

Aiken

et al. 2016

J. Electrochem. Soc.

128

137

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“…(4-7). Many researchers studying the failure of Li-ion batteries have identified this capacity loss vs t 1/2 (or equivalent) relationship and have demonstrated that their models fit experimental data very well [16,85,92,95,122].…”

Section: The Growth Rate Of Sei Filmmentioning

confidence: 99%

“… pq (4)(5)(6)(7)(8)(9)(10)(11)(12)(13)(14)(15)(16)(17)(18) where is carrier hole mobility, and q is electron charge.…”

Section:  mentioning

confidence: 99%

Diagnosis of Electrochemical Impedance Spectroscopy in Lithium-Ion Batteries

Zhuang¹,

Qiu²,

Xu³

et al. 2012

Lithium Ion Batteries - New Developments

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“…Yoshida et al 5 first reported the formation of DEDOHC (referred to as a transesterification byproduct) in LIBs with 1 M LiPF 6 /EC+DEC (1:1 v/v) electrolyte. Other groups have detected DEDOHC formation by gas chromatography-mass spectroscopy (GC-MS), [6][7][8] and storage tests imply that this product is catalyzed by lithium alkoxide. 8,9 Poly-EC has also been identified to be a product of EC electrolyte degradation, initiated by a Lewis acid such as PF 5 9-11 .…”

Section: Introductionmentioning

confidence: 99%

Identification of Diethyl 2,5-Dioxahexane Dicarboxylate and Polyethylene Carbonate as Decomposition Products of Ethylene Carbonate Based Electrolytes by Fourier Transform Infrared Spectroscopy

et al. 2014

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The formation of passive films on electrode by electrolyte decomposition plays a crucial role in maintaining the reversibility of Li ion batteries (LIBs); however the understanding of the electrolyte decomposition process is still lacking. In this study, we investigated the decomposition of an electrolyte based on ethylene carbonate (EC) solvent, and identified the decomposition products on Sn and Ni surface by matching the IR spectra to that of synthesized reference compounds. The reference compounds diethyl 2,5-dioxahexane dicarboxylate (DEDOHC) and polyethylene carbonate (poly-EC) were synthesized and the chemical structures were characterized by nuclear magnetic resonance (NMR) andFourier transform infrared (FTIR) spectroscopy. Peak assignments were made based on quantum chemical (Hartree-Fock) calculations. By introducing the synthesized product compounds into the electrolyte, we studied the effect of Li-ion solvation on the IR spectra and were able to match the spectra of the decomposition products on Sn and Ni electrode surfaces to those of DEDOHC and poly-EC for the first time. This study clearly demonstrated the importance to include solvation effects in the IR spectra of reference compounds in identification of electrolyte decomposition products in LIBs.2

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Electrolytes for advanced batteries

Cited by 98 publications

References 15 publications

Studies of the Capacity Fade Mechanisms of LiCoO₂/Si-Alloy: Graphite Cells

Studies of the Capacity Fade Mechanisms of LiCoO₂/Si-Alloy: Graphite Cells

Diagnosis of Electrochemical Impedance Spectroscopy in Lithium-Ion Batteries

Identification of Diethyl 2,5-Dioxahexane Dicarboxylate and Polyethylene Carbonate as Decomposition Products of Ethylene Carbonate Based Electrolytes by Fourier Transform Infrared Spectroscopy

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Electrolytes for advanced batteries

Cited by 98 publications

References 15 publications

Studies of the Capacity Fade Mechanisms of LiCoO2/Si-Alloy: Graphite Cells

Studies of the Capacity Fade Mechanisms of LiCoO2/Si-Alloy: Graphite Cells

Diagnosis of Electrochemical Impedance Spectroscopy in Lithium-Ion Batteries

Identification of Diethyl 2,5-Dioxahexane Dicarboxylate and Polyethylene Carbonate as Decomposition Products of Ethylene Carbonate Based Electrolytes by Fourier Transform Infrared Spectroscopy

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Studies of the Capacity Fade Mechanisms of LiCoO₂/Si-Alloy: Graphite Cells

Studies of the Capacity Fade Mechanisms of LiCoO₂/Si-Alloy: Graphite Cells