Understanding the Evolution of Lithium Dendrites at LiAlLaZrO Grain Boundaries Via Operando Microscopy Techniques

Overview

Journal Nat Commun

Specialty Biology

Date 2023 Mar 9

PMID 36894536

Authors

Chao Zhu

Till Fuchs

Stefan A L Weber

Felix H Richter

Gunnar Glasser

Franjo Weber

Hans-Jurgen Butt

Jurgen Janek

Rudiger Berger

Affiliations

Soon will be listed here.

Abstract

The growth of lithium dendrites in inorganic solid electrolytes is an essential drawback that hinders the development of reliable all-solid-state lithium metal batteries. Generally, ex situ post mortem measurements of battery components show the presence of lithium dendrites at the grain boundaries of the solid electrolyte. However, the role of grain boundaries in the nucleation and dendritic growth of metallic lithium is not yet fully understood. Here, to shed light on these crucial aspects, we report the use of operando Kelvin probe force microscopy measurements to map locally time-dependent electric potential changes in the LiAlLaZrO garnet-type solid electrolyte. We find that the Galvani potential drops at grain boundaries near the lithium metal electrode during plating as a response to the preferential accumulation of electrons. Time-resolved electrostatic force microscopy measurements and quantitative analyses of lithium metal formed at the grain boundaries under electron beam irradiation support this finding. Based on these results, we propose a mechanistic model to explain the preferential growth of lithium dendrites at grain boundaries and their penetration in inorganic solid electrolytes.

Citing Articles

Atomic mechanism of lithium dendrite penetration in solid electrolytes.

Zhang B, Yuan B, Yan X, Han X, Zhang J, Tan H Nat Commun. 2025; 16(1):1906.

PMID: 39994244 PMC: 11850858. DOI: 10.1038/s41467-025-57259-x.

Dendrite formation in solid-state batteries arising from lithium plating and electrolyte reduction.

Liu H, Chen Y, Chien P, Amouzandeh G, Hou D, Truong E Nat Mater. 2025; .

PMID: 39890877 DOI: 10.1038/s41563-024-02094-6.

Compositional flexibility in irreducible antifluorite electrolytes for next-generation battery anodes.

Landgraf V, Tu M, Cheng Z, Vasileiadis A, Wagemaker M, Famprikis T J Mater Chem A Mater. 2024; 13(5):3562-3574.

PMID: 39723171 PMC: 11665506. DOI: 10.1039/d4ta07521h.

Study on terrain acquisition and processing technology of BDS-3 auxiliary mountain highway.

Lin G, Li S, Wang J, Li Y, Qin J, Yan R Sci Rep. 2024; 14(1):24991.

PMID: 39443606 PMC: 11500386. DOI: 10.1038/s41598-024-74877-5.

Spontaneous grain refinement effect of rare earth zinc alloy anodes enables stable zinc batteries.

Chen M, Gong Y, Zhao Y, Song Y, Tang Y, Zeng Z Natl Sci Rev. 2024; 11(7):nwae205.

PMID: 39071097 PMC: 11275459. DOI: 10.1093/nsr/nwae205.

References

Famprikis T, Canepa P, Dawson J, Islam M, Masquelier C . Fundamentals of inorganic solid-state electrolytes for batteries. Nat Mater. 2019; 18(12):1278-1291. DOI: 10.1038/s41563-019-0431-3. View

Sun Y, Gorobstov O, Mu L, Weinstock D, Bouck R, Cha W . X-ray Nanoimaging of Crystal Defects in Single Grains of Solid-State Electrolyte LiAlLaZrO. Nano Lett. 2021; 21(11):4570-4576. DOI: 10.1021/acs.nanolett.1c00315. View

Wang C, Fu K, Kammampata S, McOwen D, Samson A, Zhang L . Garnet-Type Solid-State Electrolytes: Materials, Interfaces, and Batteries. Chem Rev. 2020; 120(10):4257-4300. DOI: 10.1021/acs.chemrev.9b00427. View

Ma C, Rangasamy E, Liang C, Sakamoto J, More K, Chi M . Corrigendum: Excellent Stability of a Lithium-Ion-Conducting Solid Electrolyte upon Reversible Li(+)/H(+) Exchange in Aqueous Solutions. Angew Chem Int Ed Engl. 2015; 54(4):1063. DOI: 10.1002/anie.201500056. View

Schirmeisen A, Taskiran A, Fuchs H, Bracht H, Murugavel S, Roling B . Fast interfacial ionic conduction in nanostructured glass ceramics. Phys Rev Lett. 2007; 98(22):225901. DOI: 10.1103/PhysRevLett.98.225901. View

Liu F, Xu R, Wu Y, Boyle D, Yang A, Xu J . Dynamic spatial progression of isolated lithium during battery operations. Nature. 2021; 600(7890):659-663. DOI: 10.1038/s41586-021-04168-w. View

Dawson J, Canepa P, Famprikis T, Masquelier C, Islam M . Atomic-Scale Influence of Grain Boundaries on Li-Ion Conduction in Solid Electrolytes for All-Solid-State Batteries. J Am Chem Soc. 2017; 140(1):362-368. DOI: 10.1021/jacs.7b10593. View

Lu Y, Chen J . Prospects of organic electrode materials for practical lithium batteries. Nat Rev Chem. 2023; 4(3):127-142. DOI: 10.1038/s41570-020-0160-9. View

Harrison J, Waldow D, Cox P, Giridharagopal R, Adams M, Richmond V . Noncontact Imaging of Ion Dynamics in Polymer Electrolytes with Time-Resolved Electrostatic Force Microscopy. ACS Nano. 2018; 13(1):536-543. DOI: 10.1021/acsnano.8b07254. View

10.

Schonenberger , Alvarado . Observation of single charge carriers by force microscopy. Phys Rev Lett. 1990; 65(25):3162-3164. DOI: 10.1103/PhysRevLett.65.3162. View

11.

Krauskopf T, Hartmann H, Zeier W, Janek J . Toward a Fundamental Understanding of the Lithium Metal Anode in Solid-State Batteries-An Electrochemo-Mechanical Study on the Garnet-Type Solid Electrolyte LiAlLaZrO. ACS Appl Mater Interfaces. 2019; 11(15):14463-14477. DOI: 10.1021/acsami.9b02537. View

12.

Mascaro A, Wang Z, Hovington P, Miyahara Y, Paolella A, Gariepy V . Measuring Spatially Resolved Collective Ionic Transport on Lithium Battery Cathodes Using Atomic Force Microscopy. Nano Lett. 2017; 17(7):4489-4496. DOI: 10.1021/acs.nanolett.7b01857. View

13.

Buschmann H, Dolle J, Berendts S, Kuhn A, Bottke P, Wilkening M . Structure and dynamics of the fast lithium ion conductor "Li7La3Zr2O12". Phys Chem Chem Phys. 2011; 13(43):19378-92. DOI: 10.1039/c1cp22108f. View

14.

Chang W, May R, Wang M, Thorsteinsson G, Sakamoto J, Marbella L . Evolving contact mechanics and microstructure formation dynamics of the lithium metal-LiLaZrO interface. Nat Commun. 2021; 12(1):6369. PMC: 8569160. DOI: 10.1038/s41467-021-26632-x. View

15.

Bergmann V, Weber S, Ramos F, Nazeeruddin M, Gratzel M, Li D . Real-space observation of unbalanced charge distribution inside a perovskite-sensitized solar cell. Nat Commun. 2014; 5:5001. DOI: 10.1038/ncomms6001. View

16.

Liu X, Garcia-Mendez R, Lupini A, Cheng Y, Hood Z, Han F . Local electronic structure variation resulting in Li 'filament' formation within solid electrolytes. Nat Mater. 2021; 20(11):1485-1490. DOI: 10.1038/s41563-021-01019-x. View

17.

Kohn P, Schroter K, Thurn-Albrecht T . Interfacial polarization and field-induced orientation in nanostructured soft-ion conductors. Phys Rev Lett. 2009; 102(21):216101. DOI: 10.1103/PhysRevLett.102.216101. View

18.

Xie J, Lu Y . A retrospective on lithium-ion batteries. Nat Commun. 2020; 11(1):2499. PMC: 7237495. DOI: 10.1038/s41467-020-16259-9. View

19.

Balke N, Jesse S, Morozovska A, Eliseev E, Chung D, Kim Y . Nanoscale mapping of ion diffusion in a lithium-ion battery cathode. Nat Nanotechnol. 2010; 5(10):749-54. DOI: 10.1038/nnano.2010.174. View

20.

Xie X, Xing J, Hu D, Gu H, Chen C, Guo X . Lithium Expulsion from the Solid-State Electrolyte LiLaZrTaO by Controlled Electron Injection in a SEM. ACS Appl Mater Interfaces. 2018; 10(6):5978-5983. DOI: 10.1021/acsami.7b17276. View