Hysteresis and current dependence of the graphite anode color in a lithium-ion cell and analysis of lithium plating at the cell edge

Grimsmann, Florian; Gerbert, T.; Brauchle, Felix; Gruhle, A.; Parisi, J.; Knipper, Martin

doi:10.1016/j.est.2017.10.015

Cited by 54 publications

(45 citation statements)

References 26 publications

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“…This shell-to-core lithiation of graphite particles confirms the current view in the literature (Grimsmann et al, 2018;Bauer et al, 2017Bauer et al, , 2016. In the context of lithium-ion batteries, this means that it applies to many anode and cathode active materials (e.g.…”

Section: Resultssupporting

confidence: 88%

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Li-ion half-cells studied operando during cycling by small-angle neutron scattering

et al. 2020

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Small-angle neutron scattering (SANS) was recently applied to the in situ and operando study of the charge/discharge process in Li-ion battery full-cells based on a pouch cell design. Here, this work is continued in a half-cell with a graphite electrode cycled versus a metallic lithium counter electrode, in a study conducted on the SANS-1 instrument of the neutron source FRM II at the Heinz Maier-Leibnitz Zentrum in Garching, Germany. It is confirmed that the SANS integrated intensity signal varies as a function of graphite lithiation, and this variation can be explained by changes in the squared difference in scattering length density between graphite and the electrolyte. The scattering contrast change upon graphite lithiation/delithiation calculated from a multi-phase neutron scattering model is in good agreement with the experimentally measured values. Due to the finite coherence length, the observed SANS contrast, which mostly stems from scattering between the (lithiated) graphite and the electrolyte phase, contains local information on the mesoscopic scale, which allows the development of lithiated phases in the graphite to be followed. The shape of the SANS signal curve can be explained by a core-shell model with step-wise (de)lithiation from the surface. Here, for the first time, X-ray diffraction, SANS and theory are combined to give a full picture of graphite lithiation in a half-cell. The goal of this contribution is to confirm the correlation between the integrated SANS data obtained during operando measurements of an Li-ion half-cell and the electrochemical processes of lithiation/delithiation in micro-scaled graphite particles. For a deeper understanding of this correlation, modelling and experimental data for SANS and results from X-ray diffraction were taken into account. research papers J. Appl. Cryst. (2020). 53, 210-221 Johannes Hattendorff et al. SANS operando study of Li-ion half-cells 211 research papers 212 Johannes Hattendorff et al. SANS operando study of Li-ion half-cells J. Appl. Cryst. (2020). 53, 210-221 Figure 2An operando X-ray diffractogram recorded from the Li/graphite half-cell cycled at C/5, showing the presence of well defined lithiation stages, which indicates good homogeneity across the electrode. J. Appl. Cryst. (2020). 53, 210-221 Johannes Hattendorff et al. SANS operando study of Li-ion half-cells 219 Figure 9An illustration of the calculation mesh and the coherence volumes centred at each mesh element k, (a) for small particles and (b) for a large particle with two phases, e.g. active material and electrolyte or solvent. One square is of the order of 30 nm.

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Section: Resultssupporting

confidence: 88%

“…The SANS data analysis suggests that graphite stage coexistence evolves directly on a particle scale. This shell-to-core lithiation of graphite particles confirms the current view in the literature (Grimsmann et al, 2018;Bauer et al, 2017Bauer et al, , 2016.…”

Section: Resultssupporting

confidence: 87%

Li-ion half-cells studied operando during cycling by small-angle neutron scattering

et al. 2020

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“…The marked distinction between the intercalation and deintercalation processes has been seen previously using other experimental methods. 3,5,22,26,34 For instance, galvanostatic intermittent titration was used to identify a delay in the LiC 12 → LiC 6 transformation, which was attributed to a slow nucleation step in the creation of the lithium-rich phase. 34 (In the reverse process, the generation of lithium “holes” does not require nucleation and proceeds without delay.)…”

Section: Discussionmentioning

confidence: 99%

“…In another example, ex situ optical observations of opened Li-ion cells revealed color differences, which persisted regardless of waiting time, between charging and discharging anodes at the same SOC. 22…”

Section: Discussionmentioning

confidence: 99%

Irreversibility at macromolecular scales in the flake graphite of the lithium-ion battery anode

Lodico

Lai

Woodall

et al. 2019

Journal of Power Sources

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Charging a commercial lithium-ion battery intercalates lithium into the graphite-based anode, creating various lithium carbide structures. Despite their economic importance, these structures and the dynamics of their charging-discharging transitions are not well-understood. We have videoed single microcrystals of high-quality, natural graphite undergoing multiple lithiation-delithiation cycles. Because the equilibrium lithium-carbide compounds corresponding to full, half, and one-third charge are gold, red, and blue respectively, video observations give direct insight into both the macromolecular structures and the kinematics of charging and discharging. We find that the transport during the first lithiation is slow and orderly, and follows the core-shell or shrinking annuli model with phase boundaries moving at constant velocities (i.e. non-diffusively). Subsequent lithiations are markedly different, showing transport that is both faster and disorderly, which indicates that the initially pristine graphite is irreversibly and considerably altered during the first cycle. In all cases deintercalation is not the time-reverse of intercalation. These findings both illustrate how lithium enters nearly defect-free host material, and highlight the differences between the idealized case and an actual, cycling graphite anode.

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“…the lithium content in the electrode materials) in Battery Management Systems, for example, relies on this interpretation of the OCV [19,20]. But a hysteresis between lithiation and delithiation of the measureable OCV is generally observed even for Li/graphite half cells [2,21,1,22,23,7,24,12], suggesting that the full cell OCV is not a simple function of the thermodynamic ground state. The lack of a clear one-to-one relationship between the OCV and the state of charge could lead to incorrect battery management and control decisions, leading to lithium plating and safety issues.…”

Section: Introductionmentioning

confidence: 99%

Voltage hysteresis during lithiation/delithiation of graphite associated with meta-stable carbon stackings

Mercer

Peng

Soares

et al. 2020

Preprint

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Cell voltage is a fundamental quantity used to monitor and control Li-ion batteries. The open circuit voltage (OCV) is of particular interest as it is believed to be a thermodynamic quantity, free of kinetic effects and history and, therefore, "simple" to interpret. Here we show that the OCV characteristics of graphite show hysteresis between charge and discharge that does not solely originate from Li dynamics and that the OCV is in fact history dependent. Combining First Principles calculations with temperature-controlled electrochemical measurements, we identify a residual hysteresis that persists even at elevated temperatures of greater than 50°C due to differences in the phase succession between charge and discharge. Experimental entropy profiling, as well as energies and volume changes determined from First Principles calculations, suggest that the residual hysteresis is associated with different host lattice stackings of carbon and is related to Li disorder across planes in stage II configurations.

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Hysteresis and current dependence of the graphite anode color in a lithium-ion cell and analysis of lithium plating at the cell edge

Cited by 54 publications

References 26 publications

Li-ion half-cells studied operando during cycling by small-angle neutron scattering

Li-ion half-cells studied operando during cycling by small-angle neutron scattering

Irreversibility at macromolecular scales in the flake graphite of the lithium-ion battery anode

Voltage hysteresis during lithiation/delithiation of graphite associated with meta-stable carbon stackings

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