Dendrite initiation and propagation in lithium metal solid

Aug 20, 2023

Nature volume 618, pages 287–293 (2023)Cite this article

54 Altmetric

Metrics details

All-solid-state batteries with a Li anode and ceramic electrolyte have the potential to deliver a step change in performance compared with today's Li-ion batteries1,2. However, Li dendrites (filaments) form on charging at practical rates and penetrate the ceramic electrolyte, leading to short circuit and cell failure3,4. Previous models of dendrite penetration have generally focused on a single process for dendrite initiation and propagation, with Li driving the crack at its tip5,6,7,8,9. Here we show that initiation and propagation are separate processes. Initiation arises from Li deposition into subsurface pores, by means of microcracks that connect the pores to the surface. Once filled, further charging builds pressure in the pores owing to the slow extrusion of Li (viscoplastic flow) back to the surface, leading to cracking. By contrast, dendrite propagation occurs by wedge opening, with Li driving the dry crack from the rear, not the tip. Whereas initiation is determined by the local (microscopic) fracture strength at the grain boundaries, the pore size, pore population density and current density, propagation depends on the (macroscopic) fracture toughness of the ceramic, the length of the Li dendrite (filament) that partially occupies the dry crack, current density, stack pressure and the charge capacity accessed during each cycle. Lower stack pressures suppress propagation, markedly extending the number of cycles before short circuit in cells in which dendrites have initiated.

This is a preview of subscription content, access via your institution

Access Nature and 54 other Nature Portfolio journals

Get Nature+, our best-value online-access subscription

$29.99 / 30 days

cancel any time

Subscribe to this journal

Receive 51 print issues and online access

$199.00 per year

only $3.90 per issue

Rent or buy this article

Get just this article for as long as you need it

$39.95

Prices may be subject to local taxes which are calculated during checkout

The datasets generated and/or analysed during this study are available from the corresponding author on reasonable request.

The computer code generated and used during this study is available from the corresponding author on reasonable request.

Janek, J. & Zeier, W. G. A solid future for battery development. Nat. Energy 1, 16141 (2016).

Article ADS Google Scholar

Famprikis, T., Canepa, P., Dawson, J. A., Islam, M. S. & Masquelier, C. Fundamentals of inorganic solid-state electrolytes for batteries. Nat. Mater. 18, 1278–1291 (2019).

Article ADS CAS PubMed Google Scholar

Ning, Z. et al. Visualizing plating-induced cracking in lithium-anode solid-electrolyte cells. Nat. Mater. 20, 1121–1129 (2021).

Article ADS CAS PubMed Google Scholar

Kasemchainan, J. et al. Critical stripping current leads to dendrite formation on plating in lithium anode solid electrolyte cells. Nat. Mater. 18, 1105–1111 (2019).

Article ADS CAS PubMed Google Scholar

Feldman, L. A. & De Jonghe, L. C. Initiation of mode I degradation in sodium-beta alumina electrolytes. J. Mater. Sci. 17, 517–524 (1982).

Article ADS CAS Google Scholar

Porz, L. et al. Mechanism of lithium metal penetration through inorganic solid electrolytes. Adv. Energy Mater. 7, 1701003 (2017).

Article Google Scholar

Bucci, G. & Christensen, J. Modeling of lithium electrodeposition at the lithium/ceramic electrolyte interface: the role of interfacial resistance and surface defects. J. Power Sources 441, 227186 (2019).

Article CAS Google Scholar

Klinsmann, M., Hildebrand, F. E., Ganser, M. & McMeeking, R. M. Dendritic cracking in solid electrolytes driven by lithium insertion. J. Power Sources 442, 227226 (2019).

Article CAS Google Scholar

Barroso-Luque, L., Tu, Q. & Ceder, G. An analysis of solid-state electrodeposition-induced metal plastic flow and predictions of stress states in solid ionic conductor defects. J. Electrochem. Soc. 167, 20534 (2020).

Article CAS Google Scholar

Zhou, L. et al. High areal capacity, long cycle life 4 V ceramic all-solid-state Li-ion batteries enabled by chloride solid electrolytes. Nat. Energy 7, 83–93 (2022).

Article ADS CAS Google Scholar

Koç, T., Marchini, F., Rousse, G., Dugas, R. & Tarascon, J.-M. In search of the best solid electrolyte-layered oxide pairing for assembling practical all-solid-state batteries. ACS Appl. Energy Mater. 4, 13575–13585 (2021).

Article Google Scholar

Liang, J. et al. A series of ternary metal chloride superionic conductors for high-performance all-solid-state lithium batteries. Adv. Energy Mater. 12, 2103921 (2022).

Article CAS Google Scholar

Tu, Q., Shi, T., Chakravarthy, S. & Ceder, G. Understanding metal propagation in solid electrolytes due to mixed ionic-electronic conduction. Matter 4, 3248–3268 (2021).

Article CAS Google Scholar

Kazyak, E. et al. Li penetration in ceramic solid electrolytes: operando microscopy analysis of morphology, propagation, and reversibility. Matter 2, 1025–1048 (2020).

Article Google Scholar

Scharf, J. et al. Bridging nano- and microscale X-ray tomography for battery research by leveraging artificial intelligence. Nat. Nanotechnol. 17, 446–459 (2022).

Article ADS CAS PubMed Google Scholar

De Jonghe, L. C., Feldman, L. & Beuchele, A. Slow degradation and electron conduction in sodium/beta-aluminas. J. Mater. Sci. 16, 780–786 (1981).

Article ADS Google Scholar

Han, F. et al. High electronic conductivity as the origin of lithium dendrite formation within solid electrolytes. Nat. Energy 4, 187–196 (2019).

Article ADS CAS Google Scholar

Masias, A., Felten, N., Garcia-Mendez, R., Wolfenstine, J. & Sakamoto, J. Elastic, plastic, and creep mechanical properties of lithium metal. J. Mater. Sci. 54, 2585–2600 (2019).

Article ADS CAS Google Scholar

Sedlatschek, T. et al. Large-deformation plasticity and fracture behavior of pure lithium under various stress states. Acta Mater. 208, 116730 (2021).

Article CAS Google Scholar

Doltsinis, I. & Dattke, R. Modelling the damage of porous ceramics under internal pressure. Comput. Methods Appl. Mech. Eng. 191, 29–46 (2001).

Article ADS MATH Google Scholar

Foulk, J. W. III, Johnson, G. C., Klein, P. A. & Ritchie, R. O. On the toughening of brittle materials by grain bridging: promoting intergranular fracture through grain angle, strength, and toughness. J. Mech. Phys. Solids 56, 2381–2400 (2008).

Article ADS CAS MATH Google Scholar

Fricker, H. S. Why does charge concentrate on points? Phys. Educ. 24 157 (1989).

Article ADS Google Scholar

Liu, G. et al. Densified Li6PS5Cl nanorods with high ionic conductivity and improved critical current density for all-solid-state lithium batteries. Nano Lett. 20, 6660–6665 (2020).

Article ADS CAS PubMed Google Scholar

Begley, J. A. & Landes, J. D. in Proc. 1971 National Symposium on Fracture Mechanics—Part II, ASTM STP 514 1–20 (ASTM, 1972).

Huang, Z. & Li, X. Origin of flaw-tolerance in nacre. Sci. Rep. 3, 1693 (2013).

Article ADS PubMed PubMed Central Google Scholar

Kinzer, B. et al. Operando analysis of the molten Li|LLZO interface: understanding how the physical properties of Li affect the critical current density. Matter 4, 1947–1961 (2021).

Article CAS Google Scholar

Lewis, J. A. et al. Role of areal capacity in determining short circuiting of sulfide-based solid-state batteries. ACS Appl. Mater. Interfaces 14, 4051–4060 (2022).

Article CAS PubMed Google Scholar

Hänsel, C. & Kundu, D. The stack pressure dilemma in sulfide electrolyte based Li metal solid-state batteries: a case study with Li6PS5Cl solid electrolyte. Adv. Mater. Interfaces 8, 2100206 (2021).

Article Google Scholar

Doux, J.-M. et al. Stack pressure considerations for room-temperature all-solid-state lithium metal batteries. Adv. Energy Mater. 10, 1903253 (2020).

Article CAS Google Scholar

Haslam, C. G., Wolfenstine, J. B. & Sakamoto, J. The effect of aspect ratio on the mechanical behavior of Li metal in solid-state cells. J. Power Sources 520, 230831 (2022).

Article CAS Google Scholar

Otto, S.-K. et al. In situ investigation of lithium metal–solid electrolyte anode interfaces with ToF-SIMS. Adv. Mater. Interfaces 9, 2102387 (2022).

Article CAS Google Scholar

Baranowski, L. L., Heveran, C. M., Ferguson, V. L. & Stoldt, C. R. Multi-scale mechanical behavior of the Li3PS4 solid-phase electrolyte. ACS Appl. Mater. Interfaces 8, 29573–29579 (2016).

Article CAS PubMed Google Scholar

Oliver, W. C. & Pharr, G. M. Measurement of hardness and elastic modulus by instrumented indentation: advances in understanding and refinements to methodology. J. Mater. Res. 19, 3–20 (2004).

Article ADS CAS Google Scholar

Zhang, T., Feng, Y., Yang, R. & Jiang, P. A method to determine fracture toughness using cube-corner indentation. Scr. Mater. 62, 199–201 (2010).

Article ADS CAS Google Scholar

Cuadrado, N., Casellas, D., Anglada, M. & Jiménez-Piqué, E. Evaluation of fracture toughness of small volumes by means of cube-corner nanoindentation. Scr. Mater. 66, 670–673 (2012).

Article CAS Google Scholar

Di Maio, D. & Roberts, S. G. Measuring fracture toughness of coatings using focused-ion-beam-machined microbeams. J. Mater. Res. 20, 299–302 (2005).

Article ADS Google Scholar

Chen, Y. et al. Measurements of elastic modulus and fracture toughness of an air plasma sprayed thermal barrier coating using micro-cantilever bending. Surf. Coat. Technol. 374, 12–20 (2019).

Article Google Scholar

Download references

P.G.B. is indebted to the Faraday Institution SOLBAT (FIRG007, FIRG008, FIRG026), as well as the Engineering and Physical Sciences Research Council, Enabling Next Generation Lithium Batteries (EP/M009521/1), the University of Oxford experimental equipment upgrade (EP/M02833X/1) and the Henry Royce Institute for Advanced Materials (EP/R0066X/1, EP/S019367/1, EP/R010145/1) for financial support. We thank the Diamond Light Source for the provision of synchrotron radiation beam time (experiment no. MG23980-1) at the I13-2 beamline at the Diamond Light Source. We acknowledge technical and experimental support at the I13-2 beamline by A. J. Bodey.

These authors contributed equally: Ziyang Ning, Guanchen Li, Dominic L. R. Melvin

Department of Materials, University of Oxford, Oxford, UK

Ziyang Ning, Dominic L. R. Melvin, Yang Chen, Junfu Bu, Dominic Spencer-Jolly, Junliang Liu, Bingkun Hu, Xiangwen Gao, Johann Perera, Chen Gong, Shengda D. Pu, Shengming Zhang, Boyang Liu, Gareth O. Hartley, Richard I. Todd, Patrick S. Grant, David E. J. Armstrong, T. James Marrow & Peter G. Bruce

Fujian Science & Technology Innovation Laboratory for Energy Devices (21C Lab), Ningde, China

Ziyang Ning

Department of Engineering Science, University of Oxford, Oxford, UK

Guanchen Li & Charles W. Monroe

James Watt School of Engineering, University of Glasgow, Glasgow, UK

Guanchen Li

The Faraday Institution, Harwell Campus, Didcot, UK

Guanchen Li, Dominic L. R. Melvin, Junfu Bu, Dominic Spencer-Jolly, Xiangwen Gao, Boyang Liu, Gareth O. Hartley, Patrick S. Grant, David E. J. Armstrong, Charles W. Monroe & Peter G. Bruce

Department of Mechanical Engineering, University of Bath, Bath, UK

Yang Chen

Diamond Light Source, Harwell Campus, Didcot, UK

Andrew J. Bodey

Department of Chemistry, University of Oxford, Oxford, UK

Peter G. Bruce

You can also search for this author in PubMed Google Scholar

You can also search for this author in PubMed Google Scholar

You can also search for this author in PubMed Google Scholar

You can also search for this author in PubMed Google Scholar

You can also search for this author in PubMed Google Scholar

You can also search for this author in PubMed Google Scholar

You can also search for this author in PubMed Google Scholar

You can also search for this author in PubMed Google Scholar

You can also search for this author in PubMed Google Scholar

You can also search for this author in PubMed Google Scholar

You can also search for this author in PubMed Google Scholar

You can also search for this author in PubMed Google Scholar

You can also search for this author in PubMed Google Scholar

You can also search for this author in PubMed Google Scholar

You can also search for this author in PubMed Google Scholar

You can also search for this author in PubMed Google Scholar

You can also search for this author in PubMed Google Scholar

You can also search for this author in PubMed Google Scholar

You can also search for this author in PubMed Google Scholar

You can also search for this author in PubMed Google Scholar

You can also search for this author in PubMed Google Scholar

You can also search for this author in PubMed Google Scholar

Z.N., G.L. and D.L.R.M. contributed to all aspects of the research. Z.N., D.L.R.M., D.S.-J., S.D.P., G.O.H. and A.J.B. carried out the operando synchrotron XCT. Z.N. and D.L.R.M. performed the preparation of electrolyte discs and cell assembly. Z.N., D.L.R.M, C.G. and X.G. performed the on-line mass spectrometry. Z.N., D.L.R.M., B.H., B.L. and J.B. performed the plasma FIB imaging. D.L.R.M. and J.B. performed plasma FIB imaging with SIMS. Z.N., D.L.R.M., J.P., J.L. and D.E.J.A. conducted the preparation of microcantilever and mechanical tests. G.L., Y.C. and C.W.M. conducted the modelling. Z.N., G.L., D.L.R.M., D.S.-J., R.I.T., P.S.G., D.E.J.A., T.J.M., C.W.M. and P.G.B. discussed the data. All authors contributed to the interpretation of data. Z.N., D.L.R.M., G.L., C.W.M. and P.G.B. wrote the manuscript, with contributions and revisions from all authors. The project was supervised by C.W.M., T.J.M. and P.G.B.

Correspondence to T. James Marrow, Charles W. Monroe or Peter G. Bruce.

The authors declare no competing interests.

Nature thanks Kelsey Hatzell, Chen-Zi Zhao and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

Publisher's note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

This file contains details of the dendrite initiation and propagation modelling, Supplementary Figs. 1–21 and Supplementary Tables 1–3.

Operando XCT imaging showing the development of a dendrite crack from initiation through propagation to short circuit.

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

Ning, Z., Li, G., Melvin, D.L.R. et al. Dendrite initiation and propagation in lithium metal solid-state batteries. Nature 618, 287–293 (2023). https://doi.org/10.1038/s41586-023-05970-4

Download citation

Received: 02 October 2022

Accepted: 17 March 2023

Published: 07 June 2023

Issue Date: 08 June 2023

DOI: https://doi.org/10.1038/s41586-023-05970-4

Anyone you share the following link with will be able to read this content:

Sorry, a shareable link is not currently available for this article.

Provided by the Springer Nature SharedIt content-sharing initiative

By submitting a comment you agree to abide by our Terms and Community Guidelines. If you find something abusive or that does not comply with our terms or guidelines please flag it as inappropriate.