Stabilizing lithium plating in polymer electrolytes by concentration-polarization-induced phase transformation

Q. CHENG; T. JIN; Y. MIAO; Z. LIU; J. BOROVILAS; H. ZHANG; S. LIU; S.-Y. KIM; R. ZHANG; H. WANG; X. CHEN; L.-Q. CHEN; J. LI; W. MIN; Y. YANG

doi:10.1016/j.joule.2022.08.001

Stabilizing lithium plating in polymer electrolytes by concentration-polarization-induced phase transformation

Q. CHENG, T. JIN, Y. MIAO, Z. LIU, J. BOROVILAS, H. ZHANG, S. LIU, S.-Y. KIM, R. ZHANG, H. WANG, X. CHEN, L.-Q. CHEN, J. LI, W. MIN, Y. YANG

Research output: Journal Publications › Journal Article (refereed) › peer-review

7 Citations (Scopus)

Abstract

It is widely accepted that concentration polarization in liquid electrolytes promotes whisker growth during metal deposition, and therefore, high salt concentration is favored. Here, we report unexpected opposite behaviors in solid polymer electrolytes: concentration polarization can induce phase transformation in a polyethylene oxide (PEO) electrolyte, forming a new PEO-rich but salt-/plasticizer-poor phase at the lithium/electrolyte interface, as unveiled by stimulated Raman scattering microscopy. The new phase has a significantly higher Young's modulus (∼1–3 GPa) than a bulk polymer electrolyte (<1 MPa). We hereby propose a design rule for PEO electrolytes: their compositions should be near the boundary between single-phase and two-phase regions in the phase diagram so that the applied current can induce the formation of a mechanically rigid PEO-rich phase to suppress lithium whiskers. LiFePO4/PEO/Li cells with concentration-polarization-induced phase transformation can be reversibly cycled 100 times, while cells without such transformation fail within 10 cycles, demonstrating the effectiveness of this strategy. © 2022 Elsevier Inc.

Original language	English
Pages (from-to)	2372-2389
Number of pages	17
Journal	Joule
Volume	6
Issue number	10
DOIs	https://doi.org/10.1016/j.joule.2022.08.001
Publication status	Published - 2022
Externally published	Yes

Bibliographical note

We acknowledge seed funding support from Columbia University’s Research Initiatives in Science & Engineering competition, which started in 2004 to trigger high-risk, high-reward, and innovative collaborations in the basic sciences, engineering, and medicine. Y.Y., Q.C., and T.J. acknowledge the support from the Air Force Office of Scientific Research (FA9550-18-1-0410 and FA9550-20-1-0233). W.M. and Y.M. acknowledge the support from National Science Foundation (grant no. 1904684). L.-Q.C. and Z.L. acknowledge the support from the Department of Energy, Office of Energy Efficiency and Renewable Energy (EERE), under the award #DE-EE0007803 from the Battery Material Research (BMR) program. X.C. and H.W. are thankful for the support of the Office of Naval Research (ONR) under grant no. N00014-18-1-2492 and Army Research Office (ARO) under grant no. W911NF-21-1-0172. J.L. acknowledges support by NSF CBET-2034902. S.-Y.K. gratefully acknowledges partial financial support by the Kwanjeong Scholarship. We also want to thank Prof. William Goddard at Caltech and Dr. Steve Harris at Lawrence berkeley national laboratory for their kind suggestions to this work.

Keywords

ion transport
lithium metal
phase transformation
polymer electrolyte
stimulated Raman microscopy

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10.1016/j.joule.2022.08.001

Cite this

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title = "Stabilizing lithium plating in polymer electrolytes by concentration-polarization-induced phase transformation",

abstract = "It is widely accepted that concentration polarization in liquid electrolytes promotes whisker growth during metal deposition, and therefore, high salt concentration is favored. Here, we report unexpected opposite behaviors in solid polymer electrolytes: concentration polarization can induce phase transformation in a polyethylene oxide (PEO) electrolyte, forming a new PEO-rich but salt-/plasticizer-poor phase at the lithium/electrolyte interface, as unveiled by stimulated Raman scattering microscopy. The new phase has a significantly higher Young's modulus (∼1–3 GPa) than a bulk polymer electrolyte (<1 MPa). We hereby propose a design rule for PEO electrolytes: their compositions should be near the boundary between single-phase and two-phase regions in the phase diagram so that the applied current can induce the formation of a mechanically rigid PEO-rich phase to suppress lithium whiskers. LiFePO4/PEO/Li cells with concentration-polarization-induced phase transformation can be reversibly cycled 100 times, while cells without such transformation fail within 10 cycles, demonstrating the effectiveness of this strategy. {\textcopyright} 2022 Elsevier Inc.",

keywords = "ion transport, lithium metal, phase transformation, polymer electrolyte, stimulated Raman microscopy",

author = "Q. CHENG and T. JIN and Y. MIAO and Z. LIU and J. BOROVILAS and H. ZHANG and S. LIU and S.-Y. KIM and R. ZHANG and H. WANG and X. CHEN and L.-Q. CHEN and J. LI and W. MIN and Y. YANG",

note = "We acknowledge seed funding support from Columbia University{\textquoteright}s Research Initiatives in Science & Engineering competition, which started in 2004 to trigger high-risk, high-reward, and innovative collaborations in the basic sciences, engineering, and medicine. Y.Y., Q.C., and T.J. acknowledge the support from the Air Force Office of Scientific Research (FA9550-18-1-0410 and FA9550-20-1-0233). W.M. and Y.M. acknowledge the support from National Science Foundation (grant no. 1904684). L.-Q.C. and Z.L. acknowledge the support from the Department of Energy, Office of Energy Efficiency and Renewable Energy (EERE), under the award #DE-EE0007803 from the Battery Material Research (BMR) program. X.C. and H.W. are thankful for the support of the Office of Naval Research (ONR) under grant no. N00014-18-1-2492 and Army Research Office (ARO) under grant no. W911NF-21-1-0172. J.L. acknowledges support by NSF CBET-2034902. S.-Y.K. gratefully acknowledges partial financial support by the Kwanjeong Scholarship. We also want to thank Prof. William Goddard at Caltech and Dr. Steve Harris at Lawrence berkeley national laboratory for their kind suggestions to this work.",

year = "2022",

doi = "10.1016/j.joule.2022.08.001",

language = "English",

volume = "6",

pages = "2372--2389",

journal = "Joule",

issn = "2542-4351",

publisher = "Cell Press",

number = "10",

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TY - JOUR

T1 - Stabilizing lithium plating in polymer electrolytes by concentration-polarization-induced phase transformation

AU - CHENG, Q.

AU - JIN, T.

AU - MIAO, Y.

AU - LIU, Z.

AU - BOROVILAS, J.

AU - ZHANG, H.

AU - LIU, S.

AU - KIM, S.-Y.

AU - ZHANG, R.

AU - WANG, H.

AU - CHEN, X.

AU - CHEN, L.-Q.

AU - LI, J.

AU - MIN, W.

AU - YANG, Y.

N1 - We acknowledge seed funding support from Columbia University’s Research Initiatives in Science & Engineering competition, which started in 2004 to trigger high-risk, high-reward, and innovative collaborations in the basic sciences, engineering, and medicine. Y.Y., Q.C., and T.J. acknowledge the support from the Air Force Office of Scientific Research (FA9550-18-1-0410 and FA9550-20-1-0233). W.M. and Y.M. acknowledge the support from National Science Foundation (grant no. 1904684). L.-Q.C. and Z.L. acknowledge the support from the Department of Energy, Office of Energy Efficiency and Renewable Energy (EERE), under the award #DE-EE0007803 from the Battery Material Research (BMR) program. X.C. and H.W. are thankful for the support of the Office of Naval Research (ONR) under grant no. N00014-18-1-2492 and Army Research Office (ARO) under grant no. W911NF-21-1-0172. J.L. acknowledges support by NSF CBET-2034902. S.-Y.K. gratefully acknowledges partial financial support by the Kwanjeong Scholarship. We also want to thank Prof. William Goddard at Caltech and Dr. Steve Harris at Lawrence berkeley national laboratory for their kind suggestions to this work.

PY - 2022

Y1 - 2022

N2 - It is widely accepted that concentration polarization in liquid electrolytes promotes whisker growth during metal deposition, and therefore, high salt concentration is favored. Here, we report unexpected opposite behaviors in solid polymer electrolytes: concentration polarization can induce phase transformation in a polyethylene oxide (PEO) electrolyte, forming a new PEO-rich but salt-/plasticizer-poor phase at the lithium/electrolyte interface, as unveiled by stimulated Raman scattering microscopy. The new phase has a significantly higher Young's modulus (∼1–3 GPa) than a bulk polymer electrolyte (<1 MPa). We hereby propose a design rule for PEO electrolytes: their compositions should be near the boundary between single-phase and two-phase regions in the phase diagram so that the applied current can induce the formation of a mechanically rigid PEO-rich phase to suppress lithium whiskers. LiFePO4/PEO/Li cells with concentration-polarization-induced phase transformation can be reversibly cycled 100 times, while cells without such transformation fail within 10 cycles, demonstrating the effectiveness of this strategy. © 2022 Elsevier Inc.

AB - It is widely accepted that concentration polarization in liquid electrolytes promotes whisker growth during metal deposition, and therefore, high salt concentration is favored. Here, we report unexpected opposite behaviors in solid polymer electrolytes: concentration polarization can induce phase transformation in a polyethylene oxide (PEO) electrolyte, forming a new PEO-rich but salt-/plasticizer-poor phase at the lithium/electrolyte interface, as unveiled by stimulated Raman scattering microscopy. The new phase has a significantly higher Young's modulus (∼1–3 GPa) than a bulk polymer electrolyte (<1 MPa). We hereby propose a design rule for PEO electrolytes: their compositions should be near the boundary between single-phase and two-phase regions in the phase diagram so that the applied current can induce the formation of a mechanically rigid PEO-rich phase to suppress lithium whiskers. LiFePO4/PEO/Li cells with concentration-polarization-induced phase transformation can be reversibly cycled 100 times, while cells without such transformation fail within 10 cycles, demonstrating the effectiveness of this strategy. © 2022 Elsevier Inc.

KW - ion transport

KW - lithium metal

KW - phase transformation

KW - polymer electrolyte

KW - stimulated Raman microscopy

UR - http://www.scopus.com/inward/record.url?scp=85140138481&partnerID=8YFLogxK

U2 - 10.1016/j.joule.2022.08.001

DO - 10.1016/j.joule.2022.08.001

M3 - Journal Article (refereed)

SN - 2542-4351

VL - 6

SP - 2372

EP - 2389

JO - Joule

JF - Joule

IS - 10

ER -

Stabilizing lithium plating in polymer electrolytes by concentration-polarization-induced phase transformation

Abstract

Bibliographical note

Keywords

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