High electronic conductivity as the origin of lithium dendrite formation within solid electrolytes

Fudong Han; Andrew S. Westover; Jie Yue; Xiulin Fan; Fei Wang; Miaofang Chi; Donovan N. Leonard; Nancy J. Dudney; Howard Wang; Chunsheng Wang

doi:10.1038/s41560-018-0312-z

High electronic conductivity as the origin of lithium dendrite formation within solid electrolytes

Fudong Han, Andrew S. Westover, Jie Yue, Xiulin Fan, Fei Wang, Miaofang Chi, Donovan N. Leonard, Nancy J. Dudney, Howard Wang, Chunsheng Wang

Research output: Contribution to journal › Article › peer-review

1188 Scopus citations

Abstract

Solid electrolytes (SEs) are widely considered as an ‘enabler’ of lithium anodes for high-energy batteries. However, recent reports demonstrate that the Li dendrite formation in Li ₇ La ₃ Zr ₂ O ₁₂ (LLZO) and Li ₂ S–P ₂ S ₅ is actually much easier than that in liquid electrolytes of lithium batteries, by mechanisms that remain elusive. Here we illustrate the origin of the dendrite formation by monitoring the dynamic evolution of Li concentration profiles in three popular but representative SEs (LiPON, LLZO and amorphous Li ₃ PS ₄ ) during lithium plating using time-resolved operando neutron depth profiling. Although no apparent changes in the lithium concentration in LiPON can be observed, we visualize the direct deposition of Li inside the bulk LLZO and Li ₃ PS ₄ . Our findings suggest the high electronic conductivity of LLZO and Li ₃ PS ₄ is mostly responsible for dendrite formation in these SEs. Lowering the electronic conductivity, rather than further increasing the ionic conductivity of SEs, is therefore critical for the success of all-solid-state Li batteries.

Original language	English
Pages (from-to)	187-196
Number of pages	10
Journal	Nature Energy
Volume	4
Issue number	3
DOIs	https://doi.org/10.1038/s41560-018-0312-z
State	Published - Mar 1 2019

Bibliographical note

Publisher Copyright:
© 2019, The Author(s), under exclusive licence to Springer Nature Limited.

Funding

C.W. and F.H. gratefully acknowledge support by the Army Research Office (Award No. W911NF1510187) and the National Science Foundation (Award No. 1805159). A.S.W. and N.J.D. acknowledge support from the US Department of Energy, Advanced Research Projects Agency for Energy (ARPA-E), IONICS Program (Award No. DE-AR0000775). H.W. acknowledges the support of NIST Award 70NANB12H238, and the use of the cold neutron facility at the NIST Center for Neutron Research. The SEM test was supported by Nanostructures for Electrical Energy Storage (NEES), an Energy Frontier Research Center funded by the US Department of Energy, Office of Science, Office of Basic Energy Sciences under Award No. DESC0001160. The FIB–SEM was performed at the Center for Nanophase Materials Sciences at Oak Ridge National Lab, which is a DOE-BES supported user facility. C.W. and F.H. also acknowledge the support of the Maryland Nanocenter and its AIMLab and FabLab. We also thank B. Dunn for valuable discussions and R. G. Downing, H. Chen-Mayer and J. L. Weaver for the help on the NDP measurement.

Funders	Funder number
Office of Basic Energy Sciences
US Department of Energy
National Science Foundation	1805159
National Institute of Standards and Technology	70NANB12H238
Army Research Office	W911NF1510187
Office of Science
Advanced Research Projects Agency - Energy

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

Access to Document

10.1038/s41560-018-0312-z

Cite this

@article{fdd5be538a554113a11ec5d106b38f37,

title = "High electronic conductivity as the origin of lithium dendrite formation within solid electrolytes",

abstract = " Solid electrolytes (SEs) are widely considered as an {\textquoteleft}enabler{\textquoteright} of lithium anodes for high-energy batteries. However, recent reports demonstrate that the Li dendrite formation in Li 7 La 3 Zr 2 O 12 (LLZO) and Li 2 S–P 2 S 5 is actually much easier than that in liquid electrolytes of lithium batteries, by mechanisms that remain elusive. Here we illustrate the origin of the dendrite formation by monitoring the dynamic evolution of Li concentration profiles in three popular but representative SEs (LiPON, LLZO and amorphous Li 3 PS 4 ) during lithium plating using time-resolved operando neutron depth profiling. Although no apparent changes in the lithium concentration in LiPON can be observed, we visualize the direct deposition of Li inside the bulk LLZO and Li 3 PS 4 . Our findings suggest the high electronic conductivity of LLZO and Li 3 PS 4 is mostly responsible for dendrite formation in these SEs. Lowering the electronic conductivity, rather than further increasing the ionic conductivity of SEs, is therefore critical for the success of all-solid-state Li batteries.",

author = "Fudong Han and Westover, {Andrew S.} and Jie Yue and Xiulin Fan and Fei Wang and Miaofang Chi and Leonard, {Donovan N.} and Dudney, {Nancy J.} and Howard Wang and Chunsheng Wang",

note = "Publisher Copyright: {\textcopyright} 2019, The Author(s), under exclusive licence to Springer Nature Limited.",

year = "2019",

month = mar,

day = "1",

doi = "10.1038/s41560-018-0312-z",

language = "English",

volume = "4",

pages = "187--196",

journal = "Nature Energy",

issn = "2058-7546",

publisher = "Nature Research",

number = "3",

}

TY - JOUR

T1 - High electronic conductivity as the origin of lithium dendrite formation within solid electrolytes

AU - Han, Fudong

AU - Westover, Andrew S.

AU - Yue, Jie

AU - Fan, Xiulin

AU - Wang, Fei

AU - Chi, Miaofang

AU - Leonard, Donovan N.

AU - Dudney, Nancy J.

AU - Wang, Howard

AU - Wang, Chunsheng

PY - 2019/3/1

Y1 - 2019/3/1

N2 - Solid electrolytes (SEs) are widely considered as an ‘enabler’ of lithium anodes for high-energy batteries. However, recent reports demonstrate that the Li dendrite formation in Li 7 La 3 Zr 2 O 12 (LLZO) and Li 2 S–P 2 S 5 is actually much easier than that in liquid electrolytes of lithium batteries, by mechanisms that remain elusive. Here we illustrate the origin of the dendrite formation by monitoring the dynamic evolution of Li concentration profiles in three popular but representative SEs (LiPON, LLZO and amorphous Li 3 PS 4 ) during lithium plating using time-resolved operando neutron depth profiling. Although no apparent changes in the lithium concentration in LiPON can be observed, we visualize the direct deposition of Li inside the bulk LLZO and Li 3 PS 4 . Our findings suggest the high electronic conductivity of LLZO and Li 3 PS 4 is mostly responsible for dendrite formation in these SEs. Lowering the electronic conductivity, rather than further increasing the ionic conductivity of SEs, is therefore critical for the success of all-solid-state Li batteries.

AB - Solid electrolytes (SEs) are widely considered as an ‘enabler’ of lithium anodes for high-energy batteries. However, recent reports demonstrate that the Li dendrite formation in Li 7 La 3 Zr 2 O 12 (LLZO) and Li 2 S–P 2 S 5 is actually much easier than that in liquid electrolytes of lithium batteries, by mechanisms that remain elusive. Here we illustrate the origin of the dendrite formation by monitoring the dynamic evolution of Li concentration profiles in three popular but representative SEs (LiPON, LLZO and amorphous Li 3 PS 4 ) during lithium plating using time-resolved operando neutron depth profiling. Although no apparent changes in the lithium concentration in LiPON can be observed, we visualize the direct deposition of Li inside the bulk LLZO and Li 3 PS 4 . Our findings suggest the high electronic conductivity of LLZO and Li 3 PS 4 is mostly responsible for dendrite formation in these SEs. Lowering the electronic conductivity, rather than further increasing the ionic conductivity of SEs, is therefore critical for the success of all-solid-state Li batteries.

UR - http://www.scopus.com/inward/record.url?scp=85059958577&partnerID=8YFLogxK

U2 - 10.1038/s41560-018-0312-z

DO - 10.1038/s41560-018-0312-z

M3 - Article

AN - SCOPUS:85059958577

SN - 2058-7546

VL - 4

SP - 187

EP - 196

JO - Nature Energy

JF - Nature Energy

IS - 3

ER -

High electronic conductivity as the origin of lithium dendrite formation within solid electrolytes

Abstract

Bibliographical note

Funding

UN SDGs

Access to Document

Other files and links

Fingerprint

Cite this