High-throughput li plating quantification for fast-charging battery design

ABSTRACT Fast charging of most commercial lithium-ion batteries is limited due to fear of lithium plating on the graphite anode, which is difficult to detect and poses considerable safety

risk. Here we demonstrate the power of simple, accessible and high-throughput cycling techniques to quantify irreversible Li plating spanning data from over 200 cells. We first observe the

effects of energy density, charge rate, temperature and state of charge on lithium plating, use the results to refine a mature physics-based electrochemical model and provide an

interpretable empirical equation for predicting the plating onset state of charge. We then explore the reversibility of lithium plating and its connection to electrolyte design for

preventing irreversible Li accumulation. Finally, we design a method to quantify in situ Li plating for commercially relevant graphite|LiNi0.5Mn0.3Co0.2O2 (NMC) cells and compare with

results from the experimentally convenient Li|graphite configuration. The hypotheses and abundant data herein were generated primarily with equipment universal to the battery researcher,

encouraging further development of innovative testing methods and data processing that enable rapid battery engineering. Access through your institution Buy or subscribe This is a preview of

subscription content, access via your institution ACCESS OPTIONS Access through your institution Access Nature and 54 other Nature Portfolio journals Get Nature+, our best-value

online-access subscription $32.99 / 30 days cancel any time Learn more Subscribe to this journal Receive 12 digital issues and online access to articles $119.00 per year only $9.92 per issue

Learn more Buy this article * Purchase on SpringerLink * Instant access to full article PDF Buy now Prices may be subject to local taxes which are calculated during checkout ADDITIONAL

ACCESS OPTIONS: * Log in * Learn about institutional subscriptions * Read our FAQs * Contact customer support SIMILAR CONTENT BEING VIEWED BY OTHERS _OPERANDO_ IMPEDANCE SPECTROSCOPY WITH

COMBINED DYNAMIC MEASUREMENTS AND OVERVOLTAGE ANALYSIS IN LITHIUM METAL BATTERIES Article Open access 27 February 2025 BENCHMARKING THE REPRODUCIBILITY OF ALL-SOLID-STATE BATTERY CELL

PERFORMANCE Article Open access 18 September 2024 LITHIUM INVENTORY TRACKING AS A NON-DESTRUCTIVE BATTERY EVALUATION AND MONITORING METHOD Article 29 March 2024 DATA AVAILABILITY All data

supporting the findings in this study are available within the paper and the Supplementary Information. Source data are provided with this paper. REFERENCES * Frost & Sullivan. _Global

Li-ion Battery Materials Growth Opportunities_. https://www.marketresearch.com/Frost-Sullivan-v383/Global-Li-ion-Battery-Materials-14856305/ (2021). * Zhang, S. S., Xu, K. & Jow, T. R.

Study of the charging process of a LiCoO2-based Li-ion battery. _J. Power Sources_ 160, 1349–1354 (2006). Article  Google Scholar  * Tobishima, S. I. & Yamaki, J. I. A consideration of

lithium cell safety. _J. Power Sources_ 81–82, 882–886 (1999). Article  Google Scholar  * DNV-GL and Arizona Public Service. _McMicken Battery_ _Energy Storage System Event Technical

Analysis and Recommendations_. https://www.aps.com/-/media/APS/APSCOM-PDFs/About/Our-Company/Newsroom/McMickenFinalTechnicalReport.ashx?la=en&hash=50335FB5098D9858BFD276C40FA54FCE

(2020). * Arora, P., Doyle, M. & White, R. E. Mathematical modeling of the lithium deposition overcharge reaction in lithium-ion batteries using carbon-based negative electrodes. _J.

Electrochem. Soc._ 146, 3543 (1999). Article  Google Scholar  * Tang, M., Albertus, P. & Newman, J. Two-dimensional modeling of lithium deposition during cell charging. _J. Electrochem.

Soc._ 156, A390 (2009). Article  Google Scholar  * Yang, X. G., Ge, S., Liu, T., Leng, Y. & Wang, C. Y. A look into the voltage plateau signal for detection and quantification of lithium

plating in lithium-ion cells. _J. Power Sources_ 395, 251–261 (2018). Article  Google Scholar  * Ren, D. et al. Investigation of lithium plating-stripping process in Li-ion batteries at low

temperature using an electrochemical model. _J. Electrochem. Soc._ 165, A2167–A2178 (2018). Article  Google Scholar  * Colclasure, A. M. et al. Requirements for enabling extreme fast

charging of high energy density Li-ion cells while avoiding lithium plating. _J. Electrochem. Soc._ 166, A1412–A1424 (2019). Article  Google Scholar  * Campbell, I. D., Marzook, M.,

Marinescu, M. & Offer, G. J. How observable is lithium plating? Differential voltage analysis to identify and quantify lithium plating following fast charging of cold lithium-ion

batteries. _J. Electrochem. Soc._ 166, A725–A739 (2019). Article  Google Scholar  * Paul, P. P. et al. A review of existing and emerging methods for lithium detection and characterization in

Li-ion and Li-metal batteries. _Adv. Energy Mater._ 11, 2100372 (2021). Article  Google Scholar  * Fang, C. et al. Quantifying inactive lithium in lithium metal batteries. _Nature_ 572,

511–515 (2019). Article  Google Scholar  * McShane, E. J. et al. Quantification of inactive lithium and solid–electrolyte interphase species on graphite electrodes after fast charging. _ACS

Energy Lett._ 5, 2045–2051 (2020). Article  Google Scholar  * Deng, Z. et al. Towards autonomous high-throughput multiscale modelling of battery interfaces. _Energy Environ. Sci._ 15,

579–594 (2022). Article  Google Scholar  * Kang, K., Meng, Y. S., Bréger, J., Grey, C. P. & Ceder, G. Electrodes with high power and high capacity for rechargeable lithium batteries.

_Science_ 311, 977–980 (2006). Article  Google Scholar  * Qie, L. et al. Nitrogen-doped porous carbon nanofiber webs as anodes for lithium ion batteries with a superhigh capacity and rate

capability. _Adv. Mater._ 24, 2047–2050 (2012). Article  Google Scholar  * Smith, A. J., Burns, J. C., Trussler, S. & Dahn, J. R. Precision measurements of the coulombic efficiency of

lithium-ion batteries and of electrode materials for lithium-ion batteries. _J. Electrochem. Soc._ 157, A196–A202 (2009). Article  Google Scholar  * Dahn, J. R., Burns, J. C. & Stevens,

D. A. Importance of coulombic efficiency measurements in R&D efforts to obtain long-lived Li-ion batteries. _Electrochem. Soc. Interface_ 25, 75–78 (2016). Google Scholar  * Severson, K.

A. et al. Data-driven prediction of battery cycle life before capacity degradation. _Nat. Energy_ 4, 383–391 (2019). Article  Google Scholar  * Attia, P. M. et al. Closed-loop optimization

of fast-charging protocols for batteries with machine learning. _Nature_ 578, 397–402 (2020). Article  Google Scholar  * Aykol, M., Herring, P. & Anapolsky, A. Machine learning for

continuous innovation in battery technologies. _Nat. Rev. Mater._ 5, 725–727 (2020). Article  Google Scholar  * Konz, Z. M., McShane, E. J. & McCloskey, B. D. Detecting the onset of

lithium plating and monitoring fast charging performance with voltage relaxation. _ACS Energy Lett._ 5, 1750–1757 (2020). Article  Google Scholar  * Adam, A., Knobbe, E., Wandt, J. &

Kwade, A. Application of the differential charging voltage analysis to determine the onset of lithium-plating during fast charging of lithium-ion cells. _J. Power Sources_ 495, 229794

(2021). Article  Google Scholar  * Colclasure, A. M. et al. Electrode scale and electrolyte transport effects on extreme fast charging of lithium-ion cells. _Electrochim. Acta_ 337, 135854

(2020). Article  Google Scholar  * Finegan, D. P. et al. Spatial dynamics of lithiation and lithium plating during high-rate operation of graphite electrodes. _Energy Environ. Sci._ 13,

2570–2584 (2020). Article  Google Scholar  * Robertson, D. C. et al. Effect of anode porosity and temperature on the performance and lithium plating during fast-charging of lithium-ion

cells. _Energy Technol._ 9, 2000666 (2021). Article  Google Scholar  * Chen, Y. et al. Operando video microscopy of Li plating and re-intercalation on graphite anodes during fast charging.

_J. Mater. Chem. A_ 9, 23522–23536 (2021). Article  Google Scholar  * Dees, D. W. et al. Apparent increasing lithium diffusion coefficient with applied current in graphite. _J. Electrochem.

Soc._ 167, 120528 (2020). Article  Google Scholar  * Uhlmann, C., Illig, J., Ender, M., Schuster, R. & Ivers-Tiffée, E. In situ detection of lithium metal plating on graphite in

experimental cells. _J. Power Sources_ 279, 428–438 (2015). Article  Google Scholar  * Gao, T. et al. Interplay of lithium intercalation and plating on a single graphite particle. _Joule_ 5,

393–414 (2021). Article  Google Scholar  * Adam, A. et al. Development of an innovative workflow to optimize the fast-charge capability of lithium-ion battery cells. _J. Power Sources_ 512,

230469 (2021). Article  Google Scholar  * Hobold, G. M. et al. Moving beyond 99.9% Coulombic efficiency for lithium anodes in liquid electrolytes. _Nat. Energy_ 6, 951–960 (2021). Article 

Google Scholar  * Gunnarsdóttir, A. B., Amanchukwu, C. V., Menkin, S. & Grey, C. P. Noninvasive in situ NMR study of ‘dead lithium’ formation and lithium corrosion in full-cell lithium

metal batteries. _J. Am. Chem. Soc._ 142, 20814–20827 (2020). Article  Google Scholar  * Wandt, J., Jakes, P., Granwehr, J., Eichel, R. A. & Gasteiger, H. A. Quantitative and

time-resolved detection of lithium plating on graphite anodes in lithium ion batteries. _Mater. Today_ 21, 231–240 (2018). Article  Google Scholar  * Tanim, T. R., Dufek, E. J., Dickerson,

C. C. & Wood, S. M. Electrochemical quantification of lithium plating: challenges and considerations. _J. Electrochem. Soc._ 166, A2689–A2696 (2019). Article  Google Scholar  * Martin,

C., Genovese, M., Louli, A. J., Weber, R. & Dahn, J. R. Cycling lithium metal on graphite to form hybrid lithium-ion/lithium metal cells. _Joule_ 4, 1296–1310 (2020). Article  Google

Scholar  * Cai, W. et al. The boundary of lithium plating in graphite electrode for safe lithium-ion batteries. _Angew. Chem. Int. Ed. Engl._ 60, 13007–13012 (2021). Article  Google Scholar

  * Mei, W., Jiang, L., Liang, C., Sun, J. & Wang, Q. Understanding of Li-plating on graphite electrode: detection, quantification and mechanism revelation. _Energy Storage Mater._ 41,

209–221 (2021). Article  Google Scholar  * Brown, D. E., McShane, E. J., Konz, Z. M., Knudsen, K. B. & McCloskey, B. D. Detecting onset of lithium plating during fast charging of Li-ion

batteries using operando electrochemical impedance spectroscopy. _Cell Rep. Phys. Sci._ 2, 100589 (2021). Article  Google Scholar  * Ho, A. S. et al. 3D detection of lithiation and lithium

plating in graphite anodes during fast charging. _ACS Nano_ 15, 10480–10487 (2021). Article  Google Scholar  * Duangdangchote, S. et al. Effect of fluoroethylene carbonate on the transport

property of electrolytes towards Ni-rich Li-ion batteries with high safety. _Chem. Commun._ 57, 6732–6735 (2021). Article  Google Scholar  * Yan, S. et al. Regulating the growth of lithium

dendrite by coating an ultra-thin layer of gold on separator for improving the fast-charging ability of graphite anode. _J. Energy Chem._ 67, 467–473 (2022). Article  Google Scholar  * Shin,

H., Park, J., Sastry, A. M. & Lu, W. Effects of fluoroethylene carbonate (FEC) on anode and cathode interfaces at elevated temperatures. _J. Electrochem. Soc._ 162, A1683–A1692 (2015).

Article  Google Scholar  * Kazyak, E., Chen, K. H., Chen, Y., Cho, T. H. & Dasgupta, N. P. Enabling 4C fast charging of lithium-ion batteries by coating graphite with a solid-state

electrolyte. _Adv. Energy Mater._ 12, 2102618 (2022). Article  Google Scholar  * Paul, P. P. et al. Quantification of heterogeneous, irreversible lithium plating in extreme fast charging of

lithium-ion batteries. _Energy Environ. Sci._ 14, 4979–4988 (2021). Article  Google Scholar  * Christensen, J. & Newman, J. Cyclable lithium and capacity loss in Li-ion cells. _J.

Electrochem. Soc._ 152, A818–A829 (2005). Article  Google Scholar  * Gong, C. et al. Revealing the role of fluoride-rich battery electrode interphases by operando transmission electron

microscopy. _Adv. Energy Mater._ 11, 2003118 (2021). Article  MathSciNet  Google Scholar  * Huang, W. et al. Onboard early detection and mitigation of lithium plating in fast-charging

batteries. _Nat. Commun._ 13, 7091 (2022). Article  Google Scholar  * Logan, E. R., Tonita, E. M., Gering, K. L. & Dahn, J. R. A critical evaluation of the advanced electrolyte model.

_J. Electrochem. Soc._ 165, A3350–A3359 (2018). Article  Google Scholar  * Usseglio-Viretta, F. L. E. et al. Resolving the discrepancy in tortuosity factor estimation for Li-ion battery

electrodes through micro-macro modeling and experiment. _J. Electrochem. Soc._ 165, A3403–A3426 (2018). Article  Google Scholar  * Hindmarsh, A. C. et al. SUNDIALS: suite of nonlinear and

differential/algebraic equation solvers. _ACM Trans. Math. Softw._ 31, 363–396 (2005). Article  MathSciNet  MATH  Google Scholar  * Bloom, I. et al. Differential voltage analyses of

high-power, lithium-ion cells 1. Technique and application. _J. Power Sources_ 139, 295–303 (2005). Article  Google Scholar  Download references ACKNOWLEDGEMENTS This work was largely

supported by the Vehicle Technologies Office of the US Department of Energy under the XCEL Fast Charging Program (eXtreme Fast Charge Cell Evaluation of Lithium ion Batteries, XCEL). Part of

this work was authored by the National Renewable Energy Laboratory, operated by the Alliance for Sustainable Energy, LLC, for the US Department of Energy (DOE) under contract

DE-AC36-08GO28308. H.K.B., D.E.B. and E.J.M. acknowledge support from the National Science Foundation Graduate Research Fellowship Program under grant DGE 1106400. T.-Y.H. gratefully

acknowledges support from both the Ministry of Education in Taiwan and UC Berkeley College of Chemistry through the Taiwan Fellowship Program. The authors thank S. Trask, A. Jansen, A.

Dunlop and B. Polzin from the Argonne National Laboratory Cell Analysis, Modeling, and Prototyping (CAMP) facility for providing laminate electrodes used in the study. Z.M.K. thanks J. Heo

for assistance with the design of Fig. 3e. AUTHOR INFORMATION Author notes * Brendan M. Wirtz & Eric J. McShane Present address: Department of Chemical Engineering, Stanford University,

Stanford, CA, USA AUTHORS AND AFFILIATIONS * Department of Chemical and Biomolecular Engineering, University of California, Berkeley, CA, USA Zachary M. Konz, Brendan M. Wirtz, Tzu-Yang

Huang, Helen K. Bergstrom, Matthew J. Crafton, David E. Brown, Eric J. McShane & Bryan D. McCloskey * Energy Storage and Distributed Resources Division, Lawrence Berkeley National

Laboratory, Berkeley, CA, USA Zachary M. Konz, Tzu-Yang Huang, Helen K. Bergstrom, Matthew J. Crafton, David E. Brown, Eric J. McShane & Bryan D. McCloskey * Energy Conversion and

Storage Systems Center, National Renewable Energy Laboratory, Golden, CO, USA Ankit Verma & Andrew M. Colclasure Authors * Zachary M. Konz View author publications You can also search

for this author inPubMed Google Scholar * Brendan M. Wirtz View author publications You can also search for this author inPubMed Google Scholar * Ankit Verma View author publications You can

also search for this author inPubMed Google Scholar * Tzu-Yang Huang View author publications You can also search for this author inPubMed Google Scholar * Helen K. Bergstrom View author

publications You can also search for this author inPubMed Google Scholar * Matthew J. Crafton View author publications You can also search for this author inPubMed Google Scholar * David E.

Brown View author publications You can also search for this author inPubMed Google Scholar * Eric J. McShane View author publications You can also search for this author inPubMed Google

Scholar * Andrew M. Colclasure View author publications You can also search for this author inPubMed Google Scholar * Bryan D. McCloskey View author publications You can also search for this

author inPubMed Google Scholar CONTRIBUTIONS Z.M.K. conceived ideas, performed experiments, developed methods, wrote analysis code and wrote the manuscript and Supplementary Information.

B.M.W. developed Fig. 3 methods and analysis with Z.M.K. and provided continuous project and manuscript feedback. A.V. and A.M.C. performed EChem modelling simulations and wrote the

corresponding manuscript/Supplementary Information sections. T.-Y.H. helped Z.M.K. to build the titration syringe attachment. H.K.B. helped with experiment design for Li plating on copper

and electrolyte conductivity measurements. M.J.C. and T.-Y.H. provided feedback and assistance with titrations. D.E.B. and E.J.M. provided project feedback, troubleshooting ideas and

mentorship. A.M.C. also conceived Fig. 2 experiments with Z.M.K., led EChem model modifications and provided continuous project feedback. B.D.M. was lead project supervisor, conceived ideas

and was primary manuscript editor. All authors edited and provided feedback on the manuscript. CORRESPONDING AUTHOR Correspondence to Bryan D. McCloskey. ETHICS DECLARATIONS COMPETING

INTERESTS The authors declare no competing interests. PEER REVIEW INFORMATION PEER REVIEW INFORMATION _Nature Energy_ thanks Tao Gao and the other, anonymous, reviewer(s) for their

contribution to the peer review of this work. ADDITIONAL INFORMATION PUBLISHER’S NOTE Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional

affiliations. SUPPLEMENTARY INFORMATION SUPPLEMENTARY INFORMATION Supplementary Figs. 1–38, Tables 1–5 and Notes 1–8. SOURCE DATA SOURCE DATA FIG. 1 All data required to reproduce Fig. 1

plots. SOURCE DATA FIG. 2 All data required to reproduce Fig. 2 plots. SOURCE DATA FIG. 3 All data required to reproduce Fig. 3 plots. SOURCE DATA FIG. 4 All data required to reproduce Fig.

4 plots. SOURCE DATA FIG. 5 All data required to reproduce Fig. 5 plots. RIGHTS AND PERMISSIONS Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to

this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the

terms of such publishing agreement and applicable law. Reprints and permissions ABOUT THIS ARTICLE CITE THIS ARTICLE Konz, Z.M., Wirtz, B.M., Verma, A. _et al._ High-throughput Li plating

quantification for fast-charging battery design. _Nat Energy_ 8, 450–461 (2023). https://doi.org/10.1038/s41560-023-01194-y Download citation * Received: 28 June 2022 * Accepted: 05 January

2023 * Published: 02 February 2023 * Issue Date: May 2023 * DOI: https://doi.org/10.1038/s41560-023-01194-y SHARE THIS ARTICLE Anyone you share the following link with will be able to read

this content: Get shareable link Sorry, a shareable link is not currently available for this article. Copy to clipboard Provided by the Springer Nature SharedIt content-sharing initiative