Chronoamperometric measurements and modeling of nucleation and growth, and moving boundary stages during electrochemical lithiation of graphite electrode

Levi, Mikhael D.; Markevich, Elena; Wang, C.; Aurbach, Doron

doi:10.1016/j.jelechem.2005.11.037

Cited by 16 publications

(5 citation statements)

References 18 publications

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“…We attribute the complex transient behavior when the potential is lowered to 0.665 V to the interaction of multiple processes in the early stages of Sn-Li 2 Sn 5 phase transformation. Levi et al 18 have observed similar transient behavior in current measurements at the beginning of potentiostatic lithiation of graphite electrodes. They suggested that the initial rapid decrease in the current density may be related to double layer charging at the surface, Li insertion into the anode and nucleation barrier for phase transformation.…”

Section: Measurements Of Stress and Current During Lithiation-severalmentioning

confidence: 65%

Measurements of the Phase and Stress Evolution during Initial Lithiation of Sn Electrodes

Chen

Chason

Guduru

2017

J. Electrochem. Soc.

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We have measured the phase kinetics and stress evolution during potentiostatic lithiation of Sn thin film layers to form the first lithiated phase (Li 2 Sn 5 ). Real-time measurements of the wafer curvature are used to determine the stress evolution during lithiation; the corresponding layer structure is determined from the measured charge and confirmed with cross-sectional focused-ion beam (FIB) images and X-ray diffraction (XRD). Prior to new phase formation, a 20-hour conditioning step is used to form a solid-electrolyte interphase (SEI) layer. The Stress in the SEI and Sn layers are determined by stress measurements carried on different thicknesses of Sn film. When the potential is lowered to initiate Li 2 Sn 5 formation, both the electrochemical current and stress exhibit a complex transient behavior as Li 2 Sn 5 phase nucleates and grows. The stress evolution in this regime is attributed to rate-dependent plasticity in the Sn layer. At longer times, as the new phase propagates into Sn, a steady-state is reached that enables us to determine the stress in the Li 2 Sn 5 layer. The phase evolution in the steady-state regime is analyzed with a kinetic model that enables us to estimate the Li diffusivity in Li 2 Sn 5 and the reaction rate coefficient controlling the phase transformation.

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Section: Measurements Of Stress and Current During Lithiation-severalmentioning

confidence: 65%

Measurements of the Phase and Stress Evolution during Initial Lithiation of Sn Electrodes

Chen

Chason

Guduru

2017

J. Electrochem. Soc.

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“…We report direct all-optical reflectance imaging of Li intercalation kinetics into a lithographically defined, single crystal of bulk graphite. Classical diffusion models fail to capture the propagating phase fronts and concentration profiles, but we show, for the first time, that the recently developed Cahn-Hillard reaction (CHR) theory of nonequilibrium phase separating systems , can quantitatively describe our observations, using a periodic two-layer free energy model with novel generalized Butler–Volmer kinetics. Strong Li interactions create alternating, distinct Li concentrations between adjacent graphene layers that form three stable phases: both layers full, both empty, and alternating full and empty layers in checkerboard patterns.…”

mentioning

confidence: 86%

“…While the initial formation of dilute stage 1′ involves diffusion of Li from the edge, the formation of the more concentrated phases is a complex problem of solid state chemical kinetics. Existing intercalation models assume that diffusion within each phase is rate-limiting, ,− as originally discussed by Wagner and used to interpret electrochemical measurements, but this is only valid for solid solutions. Naïve application of the diffusion equation cannot capture the spontaneous formation of phase boundaries upon phase separation, nor capture the alternating stage 2 structure.…”

Section: Observation and Simulationmentioning

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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“…43 Levi et al report activation energies of 14.4 kJ mol −1 and 22 kJ mol −1 for the stages III and I, respectively. 42,44 Other sources report values between 20 and 40 kJ mol −1 , [45][46][47] although activation energies as low as 5 kJ mol −1 are reported at SOC = 0. 48 The high scattering of the values is due on one side to the intrinsic uncertainty of the diffusion measurements, but also to the fact that the activation energy varies with the type of graphite utilized, i.e.…”

Section: Effect Of Temperature: Activation Energies For the Lithium D...mentioning

confidence: 99%

Direct Determination of Diffusion Coefficients in Commercial Li-Ion Batteries

Cabañero

Boaretto

Röder

et al. 2018

J. Electrochem. Soc.

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Diffusion coefficients are important parameters for the characterization of new electrode materials, but they are also essential for the study of cell aging and as input parameters in battery modeling. In this report, the applicability of the galvanostatic intermittent titration technique (GITT) on commercial cells is studied. A GITT protocol is applied on a set of commercial cells with graphite anodes and various cathode materials. The cell response is then compared with the ones of the individual electrodes, obtained in three-electrode and half-cell configurations. In particular, mostly due to the particular potential profile of graphite, the full cell GITT response corresponds to the anode and cathode response at low and high state of charge, respectively. Therefore, it is possible to estimate the diffusion coefficients of the individual electrodes by a simple experiment on commercial cells, although only in limited ranges of SOC. If the experiments are performed at different temperatures, it is also possible to determine the activation energies of the diffusion coefficients. In conclusion, GITT allows an estimation of the diffusivity data in commercial cells, and can be therefore used as fast analytical tool for the study of aging and for the modeling of lithium-ion batteries.

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Chronoamperometric measurements and modeling of nucleation and growth, and moving boundary stages during electrochemical lithiation of graphite electrode

Cited by 16 publications

References 18 publications

Measurements of the Phase and Stress Evolution during Initial Lithiation of Sn Electrodes

Measurements of the Phase and Stress Evolution during Initial Lithiation of Sn Electrodes

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

Direct Determination of Diffusion Coefficients in Commercial Li-Ion Batteries

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