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Title: Direct electrochemical generation of supercooled sulfur microdroplets well below their melting temperature

Abstract

Supercooled liquid sulfur microdroplets were directly generated from polysulfide electrochemical oxidation on various metal-containing electrodes. The sulfur droplets remain liquid at 155 °C below sulfur’s melting point ( T m = 115 °C), with fractional supercooling change ( T m − T sc )/ T m larger than 0.40. In operando light microscopy captured the rapid merging and shape relaxation of sulfur droplets, indicating their liquid nature. Micropatterned electrode and electrochemical current allow precise control of the location and size of supercooled microdroplets, respectively. Using this platform, we initiated and observed the rapid solidification of supercooled sulfur microdroplets upon crystalline sulfur touching, which confirms supercooled sulfur’s metastability at room temperature. In addition, the formation of liquid sulfur in electrochemical cell enriches lithium-sulfur-electrolyte phase diagram and potentially may create new opportunities for high-energy Li-S batteries.

Authors:
ORCiD logo [1];  [2];  [2];  [2];  [2];  [2];  [2];  [2];  [2];  [3];  [2];  [4];  [2]
  1. Stanford Univ., Stanford, CA (United States); Georgia Inst. of Technology, Atlanta, GA (United States)
  2. Stanford Univ., Stanford, CA (United States)
  3. Stanford Univ., Stanford, CA (United States); Zhejiang Univ. of Technology, Hangzhou (China)
  4. Stanford Univ., Stanford, CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V)
OSTI Identifier:
1493456
Alternate Identifier(s):
OSTI ID: 1489413
Grant/Contract Number:  
AC02-76SF00515; Battery Materials Research (BMR) Program; Battery500 Consortium
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Proceedings of the National Academy of Sciences of the United States of America
Additional Journal Information:
Journal Volume: 116; Journal Issue: 3; Journal ID: ISSN 0027-8424
Publisher:
National Academy of Sciences, Washington, DC (United States)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; supercooled liquids; liquid sulfur droplets; in situ optical microscopy; Li-S; batteries; crystallization

Citation Formats

Liu, Nian, Zhou, Guangmin, Yang, Ankun, Yu, Xiaoyun, Shi, Feifei, Sun, Jie, Zhang, Jinsong, Liu, Bofei, Wu, Chun -Lan, Tao, Xinyong, Sun, Yongming, Cui, Yi, and Chu, Steven. Direct electrochemical generation of supercooled sulfur microdroplets well below their melting temperature. United States: N. p., 2019. Web. doi:10.1073/pnas.1817286116.
Liu, Nian, Zhou, Guangmin, Yang, Ankun, Yu, Xiaoyun, Shi, Feifei, Sun, Jie, Zhang, Jinsong, Liu, Bofei, Wu, Chun -Lan, Tao, Xinyong, Sun, Yongming, Cui, Yi, & Chu, Steven. Direct electrochemical generation of supercooled sulfur microdroplets well below their melting temperature. United States. doi:10.1073/pnas.1817286116.
Liu, Nian, Zhou, Guangmin, Yang, Ankun, Yu, Xiaoyun, Shi, Feifei, Sun, Jie, Zhang, Jinsong, Liu, Bofei, Wu, Chun -Lan, Tao, Xinyong, Sun, Yongming, Cui, Yi, and Chu, Steven. Wed . "Direct electrochemical generation of supercooled sulfur microdroplets well below their melting temperature". United States. doi:10.1073/pnas.1817286116.
@article{osti_1493456,
title = {Direct electrochemical generation of supercooled sulfur microdroplets well below their melting temperature},
author = {Liu, Nian and Zhou, Guangmin and Yang, Ankun and Yu, Xiaoyun and Shi, Feifei and Sun, Jie and Zhang, Jinsong and Liu, Bofei and Wu, Chun -Lan and Tao, Xinyong and Sun, Yongming and Cui, Yi and Chu, Steven},
abstractNote = {Supercooled liquid sulfur microdroplets were directly generated from polysulfide electrochemical oxidation on various metal-containing electrodes. The sulfur droplets remain liquid at 155 °C below sulfur’s melting point ( T m = 115 °C), with fractional supercooling change ( T m − T sc )/ T m larger than 0.40. In operando light microscopy captured the rapid merging and shape relaxation of sulfur droplets, indicating their liquid nature. Micropatterned electrode and electrochemical current allow precise control of the location and size of supercooled microdroplets, respectively. Using this platform, we initiated and observed the rapid solidification of supercooled sulfur microdroplets upon crystalline sulfur touching, which confirms supercooled sulfur’s metastability at room temperature. In addition, the formation of liquid sulfur in electrochemical cell enriches lithium-sulfur-electrolyte phase diagram and potentially may create new opportunities for high-energy Li-S batteries.},
doi = {10.1073/pnas.1817286116},
journal = {Proceedings of the National Academy of Sciences of the United States of America},
number = 3,
volume = 116,
place = {United States},
year = {Wed Jan 02 00:00:00 EST 2019},
month = {Wed Jan 02 00:00:00 EST 2019}
}

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Works referenced in this record:

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