Title: Characterization of the structure and chemistry of the solid–electrolyte interface by cryo-EM leads to high-performance solid-state Li-metal batteries

Abstract

Solid-state lithium-metal (Li⁰) batteries are gaining traction for electric vehicle applications because they replace flammable liquid electrolytes with a safer, solid-form electrolyte that also offers higher energy density and better resistance against Li dendrite formation. Solid polymer electrolytes (SPEs) are highly promising candidates because of their tunable mechanical properties and easy manufacturability; however, their electrochemical instability against lithium metal (Li⁰), mediocre conductivity, and poorly understood Li⁰/SPE interphases have prevented extensive application in real batteries. In particular, the origin of the low Coulombic efficiency (CE) associated with SPEs remains elusive, as the debate continues as to whether it originates from unfavored interfacial reactions or lithium dendritic growth and dead lithium formation. In this work, we use state-of-the-art cryo-electromicroscopy (cryoEM) imaging and spectroscopic techniques to characterize the structure and chemistry of the interface between Li⁰ and a polyacrylate-based SPE. Contradicting the conventional knowledge, we find that no protective interphase forms, owing to the sustained reactions between deposited Li dendrites and polyacrylic backbones and succinonitrile plasticizer. Due to the reaction induced volume change, large amounts of cracks form inside the Li dendrites with a stress corrosion-cracking behavior, indicating that Li0cannot be passivated in this SPE system. Based on this observation, we then introducemore » additive engineering leveraging on the knowledge of liquid electrolytes, and demonstrate that the Li⁰ surface can be effectively protected against corrosion using fluoroethylene carbonate (FEC), leading to densely packed Li⁰ domes with conformal and stable solid-electrolyte interphases (SEIs) films. Owing to the high room temperature ionic conductivity of 1.01 mS/cm^-1, the high transference number of 0.57 and the stabilized lithium electrolyte interface, this improved new SPE delivers an excellent lithium plating/stripping CE of 99% and 1800 hours of stable cycling in Li||Li symmetric cells (0.2 mA/cm^-2, 1mAh/cm^-2). Furthermore, this improved cathodic stability along with the high anodic stability enables record high cycle life of >2000 cycles for Li||LiFePO₄ and >400 cycles for Li||LiCoO₂ full cells.« less

Authors:

Lin, Ruoqian  ^[1];

• Search DOE PAGES for author "Lin, Ruoqian"
• Search DOE PAGES for ORCID "0000-0003-3907-2231"

He, Yubin ^[2]; Wang, Chunyang  ^[2];

• Search DOE PAGES for author "Wang, Chunyang"
• Search DOE PAGES for ORCID "0000-0001-8461-3952"

Zou, Peichao ^[2]; Hu, Enyuan  ^[1];

• Search DOE PAGES for author "Hu, Enyuan"
• Search DOE PAGES for ORCID "0000-0002-1881-4534"

Yang, Xiao-Qing  ^[1];

• Search DOE PAGES for author "Yang, Xiao-Qing"
• Search DOE PAGES for ORCID "0000-0002-3625-3478"

Xu, Kang ^[3]; Xin, Huolin L.  ^[2]

• Search DOE PAGES for author "Xin, Huolin L."
• Search DOE PAGES for ORCID "0000-0002-6521-868X"

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+ Show Author Affiliations

1. Brookhaven National Lab. (BNL), Upton, NY (United States)
2. Univ. of California, Irvine, CA (United States)
3. US Army Research Lab., Adelphi, MD (United States)

Publication Date:

Thu Jun 30 00:00:00 EDT 2022

Research Org.:

Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Org.:

USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Vehicle Technologies Office; USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division; National Science Foundation (NSF)

OSTI Identifier:

1875482

Report Number(s):

BNL-223116-2022-JAAM
Journal ID: ISSN 1748-3387

Grant/Contract Number:  

SC0012704; SC0021204; CHE-1338173; DMR-2011967

Resource Type:

Accepted Manuscript

Journal Name:

Nature Nanotechnology

Additional Journal Information:

Journal Volume: 17; Journal ID: ISSN 1748-3387

Publisher:

Nature Publishing Group

Country of Publication:

United States

Language:

English

Subject:

25 ENERGY STORAGE