Impedance Study on the Electrochemical Lithium Intercalation into Natural Graphite Powder

Funabiki, Atsushi; Inaba, Masaaki; Ogumi, Zempachi; Yuasa, Shin‐ichi; Otsuji, Junhiko; Tasaka, Akimasa

doi:10.1149/1.1838231

Cited by 284 publications

(175 citation statements)

References 5 publications

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“…In practice, both slopes of the second and third domains are lower than what is predicted by De Levie's and Newman's porous electrode models. 41,42 Deviation from 45…”

Section: Resultsmentioning

confidence: 99%

Determination of Tortuosity Using Impedance Spectra Analysis of Symmetric Cell

Malifarge

Delobel

Delacourt

2017

J. Electrochem. Soc.

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An approach to increase the autonomy of batteries developed for transportation applications, without changing currently-used positive and negative active materials, is to increase the battery energy density by increasing the active material loading (mg.cm −2 ) of the electrodes. A direct consequence of a higher loading is the increase of mass transport-related issues across the electrode porosity. Therefore, the optimization of the porous electrode structure is mandatory to facilitate the access of lithium ions to the whole electrode volume. In this regard, pore tortuosity is a key parameter whose determination is not so straightforward. Although tomography techniques and corresponding analyses are promising methods to acquire precise geometrical information about porous electrode, they hardly can be used as a routine technique. In this work, a transmission-line-model analysis of the electrochemical impedance diagram of symmetric cells containing porous electrodes in blocking condition, i.e. without any charge transfer reaction, is proposed in order to readily derive pore tortuosity. The method is applied to a set of graphite electrodes composed of anisotropic particles. Lithium-ion technology is the leading contender for transportation applications such as plug-in, hybrid, and electric vehicles.1,2 It offers the highest energy density among the different existing battery technologies such as nickel metal hydride (NiMH), nickel cadmium (NiCd), and lead acid.3 Additionally, Li-ion batteries exhibit good electrochemical and thermal stability, 4,5 long life, low self-discharge rate and good charge/discharge rate capability.6-10 Nevertheless, today's electric vehicle performance still need improvement in terms of autonomy, recharge time, and cost, in order to approach internalcombustion-engine-vehicle capabilities.9,11 Increasing electrode loading is one of the most straightforward way to increase energy density and thereby the vehicle range. However, high-loading electrodes will suffer larger power limitations, which might be a problem, in particular during fast charging of the battery pack. Power limitations will mostly arise because of lithium-ion transport limitations across the electrode porosity and are known to increase with the electrode thickness or with a decrease of the porosity.To predict power limitations of an actual electrode design, accurate modeling of mass transport is desired. Nowadays, the most popular and efficient battery model is the so-called Newman's model that relies on the porous electrode theory.12 The porous electrode is described as the superposition of the liquid and solid phases that are defined by their respective volume fraction and interfacial surface area. Electrode properties are averaged over volume elements which are small compared to the overall dimension of the system but large compared to the pore details. Therefore, the pore detail is neglected and the electrode geometry is fully described by its thickness, the interfacial area per unit volume of electrode, and volume fract...

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“…In practice, both slopes of the second and third domains are lower than what is predicted by De Levie's and Newman's porous electrode models. 41,42 Deviation from 45…”

Section: Resultsmentioning

confidence: 99%

Determination of Tortuosity Using Impedance Spectra Analysis of Symmetric Cell

Malifarge

Delobel

Delacourt

2017

J. Electrochem. Soc.

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“…The microscopic device showed very high impedance under the open circuit condition, compared with macroscopic cells. 2,3 Time lapse movie A movie of Li intercalation is compiled from time lapse imaging data, and is available in the attachment. Figure S3.…”

Section: Apparent High Overpotential and Parallel Reaction Modelmentioning

confidence: 99%

“…1 Lithium intercalated graphite shows a rich phase diagram and is widely used as the anode in batteries and other electrochemical energy storage systems. Understanding Li intercalation is a critical technological problem that has been studied principally using electrochemical methods: [2][3][4][5][6][7][8] potentiostatic intermittent titration (PITT), galvanostatic intermittent titration (GITT), electrochemical impedance spectroscopy (EIS), and slow scan rate cyclic voltammetry(CV). Additional information on elementary atomic hopping steps of Li transport has also been obtained from nuclear magnetic resonance.…”

Section: Introductionmentioning

confidence: 99%

Li Intercalation into Graphite: Direct Optical Imaging and Cahn–Hilliard Reaction Dynamics

Guo

Smith

et al. 2016

J. Phys. Chem. Lett.

103

134

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“…Despite the fact that we use simulation parameters from the literature, the experimental data and model predictions qualitatively agree well though there are some deviations (especially at higher C-rates and lower temperatures). Despite simplifying assumptions used in the model (i.e., state-of-charge-dependence of the diffusion coefficient, 37 the graphite staging, 38 and isotropy of lithium migration 39 ) excellent predictions were obtained. To further improve the accuracy of the model, it would be important to incorporate the above phenomena and to acquire model parameters for the same material used in this work.…”

Section: Appendix Bmentioning

confidence: 99%

Examination of Graphite Particle Cracking as a Failure Mode in Lithium-Ion Batteries: A Model-Experimental Study

Takahashi

Srinivasan

2015

J. Electrochem. Soc.

111

104

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Capacity fade in lithium-ion batteries remains an area of active research, with failure of the graphite anode thought to be an important contributor. While the formation of the solid electrolyte interphase and the subsequent loss of cyclable lithium have been well studied, mechanical degradation remains an area where ambiguity remains. While there appears to be little experimental evidence that suggest that macroscopic particle cracking occurs, mathematical models have suggested that this phenomenon is likely. The goal of this paper is to clarify this ambiguity by combining experimental cycling, mathematical stress modeling, and post-mortem microscopy. We experimentally determine an average diffusion coefficient of lithium in graphite using a thin-layer electrode and use this information in a diffusion-induced stress model. Our results suggest that cracking is not likely during lithiation due to the proximity of equilibrium potential to the cutoff potential. On delithiation, at 25 • C, even at 30 C rate cracking is unlikely while at −10 • C, a rate of 10 C can lead to particle cracking. By extrapolating the results of the thin-layer electrode to a thick porous electrode, we found that graphite cracking is unlikely to occur during typical vehicle operations. In recent years, there have been numerous studies on lithium-ion batteries for vehicle applications. [1][2][3][4][5] Of particular interest are the various degradation mechanisms encountered when operating the battery under severe conditions (i.e., wide temperature ranges and high Crates) typical for vehicle applications.6 One likely degradation mechanism is the mechanical breakdown of the active materials. Lithium insertion (or extraction) into (or out of) the lattice of the active materials causes volume change (expansion and contraction), resulting in stress generation and possible fracture of the particles. For example, in graphite anodes, crack generation can expose new surfaces to the electrolyte, leading to further formation of the solid electrolyte interphase (SEI) 7,8 and/or particle isolation from the electronic network, leading to impedance growth, loss of cyclable lithium, and capacity fade.Mathematical models, based on diffusion-induced stress generation, have been used to investigate particle fracture and have suggested that graphite particle cracking is likely under certain conditions. [9][10][11][12][13] For the diffusion-induced stress model, diffusion coefficient in solid phase is a key parameter to determine the concentration gradient in the particle, which in turn affects the stress generated.9 However, there is a wide disparity in the measured diffusion coefficient of lithium in graphite, ranging from 10 −16 to 10 −11 m 2 /s. [14][15][16][17][18][19] This wide range can be attributed to different kinds of graphite used in these studies in addition to different techniques used to extract the diffusion coefficient. Model predictions would suggest that for the lower value of diffusion coefficient (1.0 × 10 −14 m 2 /s) particle cracking durin...

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Impedance Study on the Electrochemical Lithium Intercalation into Natural Graphite Powder

Cited by 284 publications

References 5 publications

Determination of Tortuosity Using Impedance Spectra Analysis of Symmetric Cell

Determination of Tortuosity Using Impedance Spectra Analysis of Symmetric Cell

Li Intercalation into Graphite: Direct Optical Imaging and Cahn–Hilliard Reaction Dynamics

Examination of Graphite Particle Cracking as a Failure Mode in Lithium-Ion Batteries: A Model-Experimental Study

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