A3:Notes

Topic: Inhomogeneity in tortuosity in through plane direction of a porous

electrode

I-Estimating tortuosity using diffusion model and experiments:

1. Tortuosity even when being widely used is a poorly understood concept and so,
suggests that a better approach may be to define tortuosity in terms of the underlying
flux of material or electrical current with respect to the forces which drive this flow.[8]
2. Numerical simulation is used to explore influence of particle shape and overall
porosity on the liquid phase conductivity inside porous networks, such as electrodes or
separators. The models used here imply that spherical or slightly prolate ellipsoidal
particles should be preferred for batteries.[4]

II-Estimating tortuosity using transmission line model model:

1. A new analytical approach is proposed, that is a combination of the transmission line

model theory for cylindrical pores and electrochemical impedance spectroscopy using
symmetric cells.[12]
2. Transmission line model is used with constant phase elements instead of capacitors.
Impedance spectroscopy measurements are used to obtain the tortuosities of
separators and electrodes.[1]
3. Here, in another experiment a two-point correlation function that deconstructs the
pore network into its essential attributes which solves the problem of incorrectness in
model due to inhomogeneity and anisotropy.[3]

III-Estimating tortuosity using tomography and modelling:

1. The effect of electrode processing on the tortuosity of inhouse fabricated porous

electrodes is investigated, using 3D reconstructed microstructures obtained by
synchrotron x-ray tomography and using this discusses the validity of the bruggeman
relation for porous electrodes.[10]
2. Tomographic data of a commercial electrode is used directly in a model to see the
transport process through its pore space and from that it is suggested that large local
variation of tortuosity is a reason for reduced battery life.[2]
3. In another research, synchrotron radiation X-ray tomographic microscopy is
performed on transition metal oxide-based porous electrodes to obtain statistically
significant volume 3D reconstructions of the microstructure. The microstructure
 datasets can be used to study electrode properties like porosity, tortuosity, electrode
anisotropy, and homogeneity, or as realistic geometries for 3D electrochemical
simulations.[5]
4. Moreover, to understand the impact of the pore structure on ion conductivity, the 3D
pore geometry of the diaphragms was characterized with synchrotron x-ray
absorption tomography.[7]
5. Tomography study has also been conducted using a focused ion beam-scanning
electron microscope to explain the 3D microstructure of LiCoO2 phase in Li-ion battery
positive electrode.[15]

IV-Estimating tortuosity using software:

1. An open source software application called “Bruggeman Estimator” is presented that

allows a user to estimate the tortuosity of a porous electrode.[9]

References:

1. Clennell, M. B. (1997). Tortuosity: a guide through the maze. Geological Society,

London, Special Publications, 122(1), 299-344.
2. Patel, K. K., Paulsen, J. M., & Desilvestro, J. (2003). Numerical simulation of porous
networks in relation to battery electrodes and separators. Journal of power
sources, 122(2), 144-152.
3. Ogihara, N., Kawauchi, S., Okuda, C., Itou, Y., Takeuchi, Y., & Ukyo, Y. (2012).
Theoretical and experimental analysis of porous electrodes for lithium-ion batteries by
electrochemical impedance spectroscopy using a symmetric cell. Journal of The
Electrochemical Society, 159(7), A1034.
4. Landesfeind, J., Hattendorff, J., Ehrl, A., Wall, W. A., & Gasteiger, H. A. (2016).
Tortuosity determination of battery electrodes and separators by impedance
spectroscopy. Journal of The Electrochemical Society, 163(7), A1373.
5. Mistry, A., & Mukherjee, P. P. (2019). Deconstructing electrode pore network to learn
transport distortion. Physics of Fluids, 31(12), 122005.
6. Chung, D. W., Ebner, M., Ely, D. R., Wood, V., & García, R. E. (2013). Validity of the
Bruggeman relation for porous electrodes. Modelling and Simulation in Materials
Science and Engineering, 21(7), 074009.
7. Kehrwald, D., Shearing, P. R., Brandon, N. P., Sinha, P. K., & Harris, S. J. (2011).
Local tortuosity inhomogeneities in a lithium battery composite electrode. Journal of
The Electrochemical Society, 158(12), A1393.
8. Ebner, M., Geldmacher, F., Marone, F., Stampanoni, M., & Wood, V. (2013). X‐ray
tomography of porous, transition metal oxide based lithium ion
battery electrodes. Advanced Energy Materials, 3(7), 845-850.
9. Wiedenmann, D., Keller, L., Holzer, L., Stojadinović, J., Münch, B., Suarez, L., ... &
Grobéty, B. (2013). Three‐dimensional pore structure and ion conductivity of porous
ceramic diaphragms. AIChE Journal, 59(5), 1446-1457.
10. Wilson, J. R., Cronin, J. S., Barnett, S. A., & Harris, S. J. (2011). Measurement of three-
dimensional microstructure in a LiCoO2 positive electrode. Journal of Power
Sources, 196(7), 3443-3447.
11. Ebner, M., & Wood, V. (2014). Tool for tortuosity estimation in lithium ion
battery porous electrodes. Journal of The Electrochemical Society, 162(2), A3064.