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Title: Impact of Pore Tortuosity on Electrode Kinetics in Lithium Battery Electrodes: Study in Directionally Freeze-Cast LiNi 0.8 Co 0.15 Al 0.05 O 2 (NCA)

Abstract

The prevailing electrode fabrication method for lithium-ion battery electrodes includes calendering at high pressures to densify the electrode and promote adhesion to the metal current collector. However, this process increases the tortuosity of the pore network in the primary transport direction and imposes severe tradeoffs between electrode thickness and rate capability. With the aim of understanding the impact of pore tortuosity on electrode kinetics, and enabling cell designs with thicker electrodes and improved cost and energy density, we use here freeze-casting, a shaping technique able to produce low-tortuosity structures using ice crystals as a pore-forming agent, to fabricate LiNi0.8Co0.15Al0.05O2 (NCA) cathodes with controlled, aligned porosity. Electrode tortuosity is characterized using two complementary methods, X-ray tomography combined with thermal diffusion simulations, and electrochemical transport measurements. The results allow comparison across a wide range of microstructures, and highlight the large impact of a relatively small numerical change in tortuosity on electrode kinetics. Under galvanostatic discharge, optimized microstructures show a three- to fourfold increase in area-specific capacity compared to typical Li-ion composite electrodes. Hybrid pulse power characterization (HPPC) demonstrates improved power capability, while dynamic stress tests (DST) shows that an area-specific area capacity corresponding to 91% of the NCA galvanostatic C/10 capacity couldmore » be reached.« less

Authors:
ORCiD logo; ; ; ; ;
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Vehicle Technologies Office; USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V); USDOE Office of Science (SC), Basic Energy Sciences (BES); Belgian Science Policy Office; Région Wallone (Belgium); Wallonie-Bruxelles International (Belgium); National Fund for Scientific Research (FNRS) (Belgium)
OSTI Identifier:
1419826
Alternate Identifier(s):
OSTI ID: 1494080
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Published Article
Journal Name:
Journal of the Electrochemical Society
Additional Journal Information:
Journal Name: Journal of the Electrochemical Society Journal Volume: 165 Journal Issue: 2; Journal ID: ISSN 0013-4651
Publisher:
The Electrochemical Society
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; freeze-casting; lithium-ion; tortuosity

Citation Formats

Delattre, Benjamin, Amin, Ruhul, Sander, Jonathan, De Coninck, Joël, Tomsia, Antoni P., and Chiang, Yet-Ming. Impact of Pore Tortuosity on Electrode Kinetics in Lithium Battery Electrodes: Study in Directionally Freeze-Cast LiNi 0.8 Co 0.15 Al 0.05 O 2 (NCA). United States: N. p., 2018. Web. https://doi.org/10.1149/2.1321802jes.
Delattre, Benjamin, Amin, Ruhul, Sander, Jonathan, De Coninck, Joël, Tomsia, Antoni P., & Chiang, Yet-Ming. Impact of Pore Tortuosity on Electrode Kinetics in Lithium Battery Electrodes: Study in Directionally Freeze-Cast LiNi 0.8 Co 0.15 Al 0.05 O 2 (NCA). United States. https://doi.org/10.1149/2.1321802jes
Delattre, Benjamin, Amin, Ruhul, Sander, Jonathan, De Coninck, Joël, Tomsia, Antoni P., and Chiang, Yet-Ming. Thu . "Impact of Pore Tortuosity on Electrode Kinetics in Lithium Battery Electrodes: Study in Directionally Freeze-Cast LiNi 0.8 Co 0.15 Al 0.05 O 2 (NCA)". United States. https://doi.org/10.1149/2.1321802jes.
@article{osti_1419826,
title = {Impact of Pore Tortuosity on Electrode Kinetics in Lithium Battery Electrodes: Study in Directionally Freeze-Cast LiNi 0.8 Co 0.15 Al 0.05 O 2 (NCA)},
author = {Delattre, Benjamin and Amin, Ruhul and Sander, Jonathan and De Coninck, Joël and Tomsia, Antoni P. and Chiang, Yet-Ming},
abstractNote = {The prevailing electrode fabrication method for lithium-ion battery electrodes includes calendering at high pressures to densify the electrode and promote adhesion to the metal current collector. However, this process increases the tortuosity of the pore network in the primary transport direction and imposes severe tradeoffs between electrode thickness and rate capability. With the aim of understanding the impact of pore tortuosity on electrode kinetics, and enabling cell designs with thicker electrodes and improved cost and energy density, we use here freeze-casting, a shaping technique able to produce low-tortuosity structures using ice crystals as a pore-forming agent, to fabricate LiNi0.8Co0.15Al0.05O2 (NCA) cathodes with controlled, aligned porosity. Electrode tortuosity is characterized using two complementary methods, X-ray tomography combined with thermal diffusion simulations, and electrochemical transport measurements. The results allow comparison across a wide range of microstructures, and highlight the large impact of a relatively small numerical change in tortuosity on electrode kinetics. Under galvanostatic discharge, optimized microstructures show a three- to fourfold increase in area-specific capacity compared to typical Li-ion composite electrodes. Hybrid pulse power characterization (HPPC) demonstrates improved power capability, while dynamic stress tests (DST) shows that an area-specific area capacity corresponding to 91% of the NCA galvanostatic C/10 capacity could be reached.},
doi = {10.1149/2.1321802jes},
journal = {Journal of the Electrochemical Society},
number = 2,
volume = 165,
place = {United States},
year = {2018},
month = {1}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1149/2.1321802jes

Citation Metrics:
Cited by: 9 works
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Figures / Tables:

Figure 1 Figure 1: Scheme of a freeze-casting stage as used in the present work. Adapted from “Biomaterials by freeze casting”, by Wegst et al., 2010, Phil. Trans. R. Soc. A, 368, p. 2099–2121. Adapted with permission.

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Works referenced in this record:

Tough, Bio-Inspired Hybrid Materials
journal, December 2008


On the origin and application of the Bruggeman correlation for analysing transport phenomena in electrochemical systems
journal, May 2016

  • Tjaden, Bernhard; Cooper, Samuel J.; Brett, Daniel JL
  • Current Opinion in Chemical Engineering, Vol. 12
  • DOI: 10.1016/j.coche.2016.02.006

High-energy electrode investigation for plug-in hybrid electric vehicles
journal, February 2011


A comprehensive understanding of electrode thickness effects on the electrochemical performances of Li-ion battery cathodes
journal, June 2012


Materials Challenges and Opportunities of Lithium Ion Batteries
journal, January 2011

  • Manthiram, Arumugam
  • The Journal of Physical Chemistry Letters, Vol. 2, Issue 3
  • DOI: 10.1021/jz1015422

On the Theory of Mixed Conduction with Special Reference to Conduction in Silver Sulfide Group Semiconductors
journal, November 1961

  • Yokota, Isaaki
  • Journal of the Physical Society of Japan, Vol. 16, Issue 11
  • DOI: 10.1143/JPSJ.16.2213

Battery materials for ultrafast charging and discharging
journal, March 2009

  • Kang, Byoungwoo; Ceder, Gerbrand
  • Nature, Vol. 458, Issue 7235, p. 190-193
  • DOI: 10.1038/nature07853

Characterization of Electronic and Ionic Transport in Li 1- x Ni 0 . 8 Co 0.15 Al 0.05 O 2 (NCA)
journal, January 2015

  • Amin, Ruhul; Ravnsbæk, Dorthe Bomholdt; Chiang, Yet-Ming
  • Journal of The Electrochemical Society, Vol. 162, Issue 7
  • DOI: 10.1149/2.0171507jes

Optimizing Areal Capacities through Understanding the Limitations of Lithium-Ion Electrodes
journal, November 2015

  • Gallagher, Kevin G.; Trask, Stephen E.; Bauer, Christoph
  • Journal of The Electrochemical Society, Vol. 163, Issue 2
  • DOI: 10.1149/2.0321602jes

Characterization of high-power lithium-ion cells during constant current cycling
journal, July 2003


Biomimetic gradient scaffold from ice-templating for self-seeding of cells with capillary effect
journal, July 2015


Electric powertrain modeling of a fuel cell hybrid electric vehicle and development of a power distribution algorithm based on driving mode recognition
journal, September 2010


Bioinspired Scaffolds with Varying Pore Architectures and Mechanical Properties
journal, December 2013

  • Porter, Michael M.; Imperio, Russ; Wen, Matthew
  • Advanced Functional Materials, Vol. 24, Issue 14
  • DOI: 10.1002/adfm.201302958

Unidirectional Freezing of Ceramic Suspensions: In Situ X-ray Investigation of the Effects of Additives
journal, December 2013

  • Delattre, Benjamin; Bai, Hao; Ritchie, Robert O.
  • ACS Applied Materials & Interfaces, Vol. 6, Issue 1
  • DOI: 10.1021/am403793x

Magnetically aligned graphite electrodes for high-rate performance Li-ion batteries
journal, July 2016

  • Billaud, Juliette; Bouville, Florian; Magrini, Tommaso
  • Nature Energy, Vol. 1, Issue 8
  • DOI: 10.1038/nenergy.2016.97

High-performance battery electrodes via magnetic templating
journal, July 2016


Novel functionally graded acicular electrode for solid oxide cells fabricated by the freeze-tape-casting process
journal, September 2012


Microstructural Analysis of an LSCF Cathode Using In Situ Tomography and Simulation
journal, October 2013


Laminated Adsorbents with Very Rapid CO 2 Uptake by Freeze-Casting of Zeolites
journal, March 2013

  • Ojuva, Arto; Akhtar, Farid; Tomsia, Antoni P.
  • ACS Applied Materials & Interfaces, Vol. 5, Issue 7
  • DOI: 10.1021/am400122r

Freeze-cast hydroxyapatite scaffolds for bone tissue engineering applications
journal, April 2008


Bioinspired Hydroxyapatite/Poly(methyl methacrylate) Composite with a Nacre-Mimetic Architecture by a Bidirectional Freezing Method
journal, November 2015


Design of Battery Electrodes with Dual-Scale Porosity to Minimize Tortuosity and Maximize Performance
journal, December 2012

  • Bae, Chang-Jun; Erdonmez, Can K.; Halloran, John W.
  • Advanced Materials, Vol. 25, Issue 9
  • DOI: 10.1002/adma.201204055

Freeze-Casting of Porous Ceramics: A Review of Current Achievements and Issues
journal, March 2008


Macro- and micro-designed chitosan-alginate scaffold architecture by three-dimensional printing and directional freezing
journal, January 2016


Quantifying tortuosity in porous Li-ion battery materials
journal, March 2009


Freeze casting of hydroxyapatite scaffolds for bone tissue engineering
journal, November 2006


    Works referencing / citing this record:

    Diffusion‐Limited C‐Rate: A Fundamental Principle Quantifying the Intrinsic Limits of Li‐Ion Batteries
    journal, November 2019

    • Heubner, Christian; Schneider, Michael; Michaelis, Alexander
    • Advanced Energy Materials, Vol. 10, Issue 2
    • DOI: 10.1002/aenm.201902523

    High‐Voltage Performance of Ni‐Rich NCA Cathodes: Linking Operating Voltage with Cathode Degradation
    journal, August 2019

    • David, Lamuel; Mohanty, Debasish; Geng, Linxiao
    • ChemElectroChem, Vol. 6, Issue 22
    • DOI: 10.1002/celc.201901338

    Synthesis and electrochemical characterization of Cr-doped lithium-rich Li1.2Ni0.16Mn0.56Co0.08-xCrxO2 cathodes
    journal, October 2018


    Coral-like directional porosity lithium ion battery cathodes by ice templating
    journal, January 2018

    • Huang, Chun; Grant, Patrick S.
    • Journal of Materials Chemistry A, Vol. 6, Issue 30
    • DOI: 10.1039/c8ta05049j

    Probing and quantifying cathode charge heterogeneity in Li ion batteries
    journal, January 2019

    • Zhang, Yuxin; Yang, Zhijie; Tian, Chixia
    • Journal of Materials Chemistry A, Vol. 7, Issue 41
    • DOI: 10.1039/c9ta06977a

    Modeling and Simulation of Pore Morphology Modifications using Laser-Structured Graphite Anodes in Lithium-Ion Batteries
    journal, September 2019

    • Kraft, Ludwig; Habedank, Jan B.; Frank, Alexander
    • Journal of The Electrochemical Society, Vol. 167, Issue 1
    • DOI: 10.1149/2.0062001jes

    Requirements for Enabling Extreme Fast Charging of High Energy Density Li-Ion Cells while Avoiding Lithium Plating
    journal, January 2019

    • Colclasure, Andrew M.; Dunlop, Alison R.; Trask, Stephen E.
    • Journal of The Electrochemical Society, Vol. 166, Issue 8
    • DOI: 10.1149/2.0451908jes

    High-rate lithium ion energy storage to facilitate increased penetration of photovoltaic systems in electricity grids
    journal, January 2019

    • Lennon, Alison; Jiang, Yu; Hall, Charles
    • MRS Energy & Sustainability, Vol. 6
    • DOI: 10.1557/mre.2019.4

    Production and Characterization of a Silica-Alumina Membrane Using Novel Tubular Freeze-Cast Substrates
    journal, January 2019