A Mathematical Model for the Lithium-Ion Negative Electrode Solid Electrolyte Interphase

Christensen, Jake; Newman, John

doi:10.1149/1.1804812

Cited by 293 publications

(246 citation statements)

References 54 publications

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“…Surface reactions will lead to a modification of the interface conditions. Transport within a SEI requires the addition of another thermodynamic phase with appropriate transport coefficients [38]. Volumetric reactions require the inclusion of the reacting species and the information on the reaction kinetics [20].…”

Section: Discussionmentioning

confidence: 99%

Thermodynamic consistent transport theory of Li-ion batteries

Latz

Zausch

2011

Journal of Power Sources

188

220

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Most Li ion insertion batteries consist of a porous cathode, a separator filled with electrolyte and an anode, which very often also has some porous structure. The solid part especially in the cathode is usually produced by mixing a powder of the actual active particles, in which Li ions will be intercalated, binder and carbon black to enhance the electronic conductivity of the electrode. As a result the porous structure of the electrodes is very complex, leading to complex potential, ion and temperature distributions within the electrodes. The intercalation and deintercalation of ions cannot be expected to be homogeneously distributed over the electrode due to the different transport properties of electrolyte and active particles in the electrode and the complex three-dimensional pore structure of the electrode. The influence of the final microstructure on the distribution of temperature, electric potential and ions within the electrodes is not known in detail, but may influence strongly the onset of degradation mechanisms. For being able to numerically simulate the transport phenomena, the equations and interface conditions for ion, charge and heat transport within the complex structure of the electrodes and through the electrolyte filled separator are needed. We will present a rigorous derivation of these equations based exclusively on general principles of nonequilibrium thermodynamics. The theory is thermodynamically consistent i.e. it guarantees strictly positive entropy production. The irreversible and reversible sources of heat are derived within the theory. Especially the various contribution to the Peltier heat due to the intercalation of ions are obtained as a result of the theory

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Section: Discussionmentioning

confidence: 99%

Thermodynamic consistent transport theory of Li-ion batteries

Latz

Zausch

2011

Journal of Power Sources

188

220

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“…20,21 However, Etacheri et al showed that substantial improvement can be achieved by using fluoroethylene carbonate (FEC) as electrolyte additive, which significantly reduces irreversible capacities and leads to improved cycling stability. 22 In particular, a reduction of the irreversible capacity by roughly 50% was observed when FEC was used in comparison to FEC-free electrolytes.…”

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confidence: 99%

“…19 Even though the particle cracking can be prevented, mathematical modeling suggests that the SEI formed on the silicon particles cracks during the volumetric changes, causing a continuous electrolyte consumption and loss of active lithium. 20,21 However, Etacheri et al showed that substantial improvement can be achieved by using fluoroethylene carbonate (FEC) as electrolyte additive, which significantly reduces irreversible capacities and leads to improved cycling stability. 22 In particular, a reduction of the irreversible capacity by roughly 50% was observed when FEC was used in comparison to FEC-free electrolytes.…”

mentioning

confidence: 99%

Consumption of Fluoroethylene Carbonate (FEC) on Si-C Composite Electrodes for Li-Ion Batteries

Jung

Metzger

Haering

et al. 2016

J. Electrochem. Soc.

264

311

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The electrolyte additive fluoroethylene carbonate (FEC) is known to significantly improve the lifetime of Li-ion batteries with silicon anodes. In this work, we show that FEC can indeed improve the lifetime of silicon-carbon composite anodes but is continuously consumed during electrochemical cycling. By the use of 19 F-NMR spectroscopy and charge/discharge cycling we demonstrate that FEC is only capable to stabilize the cell performance as long as FEC is still remaining in the cell. Its total consumption causes a significant increase of the cell polarization leading to a rapid capacity drop. We show with On-line Electrochemical Mass Spectrometry (OEMS) that the presence of FEC in the electrolyte prohibits the reduction of other electrolyte components almost entirely. Consequently, the cumulative irreversible capacity until the rapid capacity drop correlates linearly with the specific amount of FEC (in units of μmol FEC /mg electrode ) in the cell. The latter quantity therefore determines the lifetime of silicon anodes rather than the concentration of FEC in the electrolyte. By correlating the cumulative irreversible capacity and the specific amount of FEC in the cell, we present an easy tool to predict how much cumulative irreversible capacity can be tolerated until all FEC will be consumed in either half-cells or full-cells. We further demonstrate that four electrons are consumed for the reduction of one FEC molecule and that one carbon dioxide molecule is released for every FEC molecule that is reduced. Using all information from this study and combining it with previous reports in literature, a new reductive decomposition mechanism for FEC is proposed yielding CO 2 , LiF, In the emerging market of electric vehicles (EVs), the development of batteries with higher energy density and improved cycle-life is essential.1 However, their penetration of the mass market significantly depends on cost and the available driving range.2 The US Advanced Battery Consortium (USABC) defined the target value of 235 Wh/kg (at a C/3 rate) on a battery level until 2020.3 As outlined in the recent review by Andre et al., 4 reaching this goal requires an increase of the energy density of today's batteries by a factor of roughly 2 to 2.5 and can only be achieved by the development and integration of novel anode and cathode active materials. A critical element to reach this goal is the implementation of anode active materials with much higher specific capacity than currently used graphite anodes (372 mAh/g 1,5,6 ), with silicon being considered as the most likely next generation anode material due to its high natural abundance and very high theoretical specific capacity of roughly 3600 mAh/g (corresponding to the Li 15 Si 4 phase 7 ). The alloying of silicon with lithium is accompanied by large structural changes, resulting in a volume increase by 310% upon full lithiation.5,7-11 These huge volumetric changes upon lithium insertion and extraction are responsible for the generally shorter cycle-life of silicon electrode materials comp...

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“…[43][44][45][46][47][48][49] J. Newman has conducted very detailed analysis of porous carbon electrodes in non-aqueous LIB electrolytes. [45][46][47][48][49] Some limiting cases have been demonstrated depending on the porosity (pore size distribution, electrolyte concentration, etc).The most common and fundamental source of capacity fade in successful Li-ion batteries (which manage to resist degradation over hundreds of cycles) is the loss of lithium to the solid-electrolyte interphase (SEI), which typically forms at the negatively charged electrode during recharging. 50 NIBs and LIBs are both subject to the same limitations in the anode-electrolyte interfacial reaction; the solid electrolyte interphase (SEI) on an anode with the electrochemical potential below ∼1 V vs Na/Na + is vital to make a NIB kinetically stable.…”

mentioning

confidence: 99%

Alkali-Metal Insertion Processes on Nanospheric Hard Carbon Electrodes: An Electrochemical Impedance Spectroscopy Study

Väli

Jänes

Lust

2017

J. Electrochem. Soc.

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In this study, we report the results of electrochemical impedance spectroscopy data modelling of various battery half-cells with different alkali metal (Li, Na, K) salts. Test results of electrochemical half-cells were evaluated for the D-glucose derived hard carbon negative electrode in 1.0 M LiPF 6 + EC:DMC (1:1 volume ratio), 1.0 M NaPF 6 + EC:DMC (1:1), 1.0 M NaClO 4 + PC, 0.8 M KPF 6 + EC:DEC (1:1) and 0.8 M KPF 6 + EC:DMC (1:1) solutions at 0.5 mV s −1 potential scan rate measured within the potential region from 0.05 V to 1.2 V (vs Me/Me + ) (where Me is Li, Na or K). Modelling of electrochemical impedance spectroscopy data was employed to characterize alkali metal insertion processes in/on D-glucose derived hard carbon anode. Detailed analysis of impedance data shows that Newman equivalent circuit modified with a constant phase element can be applied for calculation of impedance spectra and fitting of calculated data to experimental ones, using non-linear least square root fitting method. Equivalent circuit fit parameters depend strongly on electrolyte composition. Very slow processes have been observed for KPF 6 Lithium-ion batteries (LIBs) are currently dominating the global portable electronics and electric vehicles market, but as the demand for LIBs rises, lithium (Li) supply might soon become the limiting factor to LIB production.1 Li and cobalt (Co) supply are under risk according to a study by British Geological Survey.2 The matter gets even worse as the need for grid-scale energy storage increases with the integration of intermittent renewable technologies such as photovoltaics and wind into the grid. Thus, a large-scale implementation of energy storage requires a battery technology that is based on cheap and abundant raw materials. Fortunately, potential alternatives do exist, because both sodium (Na) and potassium (K) have only slightly different electrochemical properties than Li and are 1000 times more abundant in the Earth's crust than Li.3-5 While the first sodium-sulfur batteries (Na-S) date back to 1968, 6 intensive research on room-temperature sodium-ion batteries has only started in recent years. 4 Hard carbons (HCs) are currently the most promising and simplest anode materials for sodium-ion batteries (NIBs). They are extensively investigated and used in some commercial Na-ion battery cells.7 Although, there are numerous papers analyzing the synthesis and electrochemical characterization of hard carbons in [8][9][10][11][12][13][14][15][16] Na-ion 17-31 battery cells, only some papers on K-ion 32,33 battery (KIB) cells have been published. There are no systematic studies on how the same carbon electrode performs in half-cells with all three Li + , Na + and K + cation containing electrolytes and how the metal cation properties affect the charge-transfer kinetics on/in the electrode.Carbon anode materials are generally divided into three classes: graphite, non-graphitized glass-like carbon (hard carbon) which cannot be graphitized even when heat-treated at very high temperature, and sof...

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A Mathematical Model for the Lithium-Ion Negative Electrode Solid Electrolyte Interphase

Cited by 293 publications

References 54 publications

Thermodynamic consistent transport theory of Li-ion batteries

Thermodynamic consistent transport theory of Li-ion batteries

Consumption of Fluoroethylene Carbonate (FEC) on Si-C Composite Electrodes for Li-Ion Batteries

Alkali-Metal Insertion Processes on Nanospheric Hard Carbon Electrodes: An Electrochemical Impedance Spectroscopy Study

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