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Title: Three-dimensional electronic resistivity mapping of solid electrolyte interphase on Si anode materials

Abstract

Silicon is a promising candidate for the lithium ion battery (LIB) anode because of the order-of-magnitude improvement in capacity over current state-of-the-art graphite anodes. In systems featuring both C and Si anodes, electronic resistivity of the solid-electrolyte interphase (SEI) layer is a critical factor for preventing continuous electrolyte-decomposition reactions at the electrode/electrolyte interface. However, the in-situ measurement of SEI electronic resistance has been complicated by ion transport and electronic contributions from other parts of the battery circuit. Ex-situ measurements of SEI resistivity at microscopic scales are also lacking. We report on a nanometer-resolution three-dimensional technique that enables ex-situ mapping of electronic resistivity of SEI formed on a model single-crystalline wafer Si anode. Our novel experimental approach uses scanning spreading-resistance microscopy resistance imaging and mechanical depth profiling. In addition to resistance mapping, this method also provides an alternative technique for locating buried interfaces, where mechanical or electronic properties differ sufficiently between layers. Further validation of this method was obtained by resistance mapping of a reference sample with a designed a-Si:H layer stack of different doping concentrations. The results show relatively uniform lateral resistivity distribution of the SEIs but steep decreases in resistivity in the vertical direction. Resistivity vs. depth profiles aremore » highly dependent on cycling conditions, but they generally show a resistivity decrease from the most superficial levels of SEI and a thickness increase with continued cycling prior to SEI stabilization. The most prominent resistivity increase was observed on SEI formed in Gen2 electrolyte (EC:EMC [3:7 by wt.] + 1.2 M LiPF6) with 10 wt% fluoroethylene carbonate additive; this result may partially explain the significant improvements of sustained electrochemical cycling and coulombic efficiency observed with this electrolyte additive. Our approach provides a novel and unparalleled three-dimensional approach in characterizing electronic resistivity, which contributes significantly to understanding SEI formation and the intrinsic properties critical to battery performance.« less

Authors:
 [1];  [2];  [3];  [4];  [4];  [4];  [5];  [4];  [4];  [4];  [4]
  1. National Renewable Energy Lab. (NREL), Golden, CO (United States); Colorado School of Mines, Golden, CO (United States)
  2. National Renewable Energy Lab. (NREL), Golden, CO (United States); Yeungnam Univ., Gyeongsan (Korea, Republic of)
  3. Univ. of Colorado, Boulder, CO (United States)
  4. National Renewable Energy Lab. (NREL), Golden, CO (United States)
  5. Colorado School of Mines, Golden, CO (United States)
Publication Date:
Research Org.:
National Renewable Energy Lab. (NREL), Golden, CO (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V)
OSTI Identifier:
1485565
Report Number(s):
NREL/JA-5K00-72015
Journal ID: ISSN 2211-2855
Grant/Contract Number:  
AC36-08GO28308
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Nano Energy
Additional Journal Information:
Journal Volume: 55; Journal Issue: C; Journal ID: ISSN 2211-2855
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; scanning probe microscopy; scanning spreading resistance; microscopy; electronic properties; solid electrolyte interphase; silicon; anode materials; lithium ion battery

Citation Formats

Stetson, Caleb, Yoon, Taeho, Coyle, Jaclyn, Nemeth, William, Young, Matt, Norman, Andrew, Pylypenko, Svitlana, Ban, Chunmei, Jiang, Chun-Sheng, Al-Jassim, Mowafak, and Burrell, Anthony. Three-dimensional electronic resistivity mapping of solid electrolyte interphase on Si anode materials. United States: N. p., 2018. Web. doi:10.1016/j.nanoen.2018.11.007.
Stetson, Caleb, Yoon, Taeho, Coyle, Jaclyn, Nemeth, William, Young, Matt, Norman, Andrew, Pylypenko, Svitlana, Ban, Chunmei, Jiang, Chun-Sheng, Al-Jassim, Mowafak, & Burrell, Anthony. Three-dimensional electronic resistivity mapping of solid electrolyte interphase on Si anode materials. United States. https://doi.org/10.1016/j.nanoen.2018.11.007
Stetson, Caleb, Yoon, Taeho, Coyle, Jaclyn, Nemeth, William, Young, Matt, Norman, Andrew, Pylypenko, Svitlana, Ban, Chunmei, Jiang, Chun-Sheng, Al-Jassim, Mowafak, and Burrell, Anthony. Mon . "Three-dimensional electronic resistivity mapping of solid electrolyte interphase on Si anode materials". United States. https://doi.org/10.1016/j.nanoen.2018.11.007. https://www.osti.gov/servlets/purl/1485565.
@article{osti_1485565,
title = {Three-dimensional electronic resistivity mapping of solid electrolyte interphase on Si anode materials},
author = {Stetson, Caleb and Yoon, Taeho and Coyle, Jaclyn and Nemeth, William and Young, Matt and Norman, Andrew and Pylypenko, Svitlana and Ban, Chunmei and Jiang, Chun-Sheng and Al-Jassim, Mowafak and Burrell, Anthony},
abstractNote = {Silicon is a promising candidate for the lithium ion battery (LIB) anode because of the order-of-magnitude improvement in capacity over current state-of-the-art graphite anodes. In systems featuring both C and Si anodes, electronic resistivity of the solid-electrolyte interphase (SEI) layer is a critical factor for preventing continuous electrolyte-decomposition reactions at the electrode/electrolyte interface. However, the in-situ measurement of SEI electronic resistance has been complicated by ion transport and electronic contributions from other parts of the battery circuit. Ex-situ measurements of SEI resistivity at microscopic scales are also lacking. We report on a nanometer-resolution three-dimensional technique that enables ex-situ mapping of electronic resistivity of SEI formed on a model single-crystalline wafer Si anode. Our novel experimental approach uses scanning spreading-resistance microscopy resistance imaging and mechanical depth profiling. In addition to resistance mapping, this method also provides an alternative technique for locating buried interfaces, where mechanical or electronic properties differ sufficiently between layers. Further validation of this method was obtained by resistance mapping of a reference sample with a designed a-Si:H layer stack of different doping concentrations. The results show relatively uniform lateral resistivity distribution of the SEIs but steep decreases in resistivity in the vertical direction. Resistivity vs. depth profiles are highly dependent on cycling conditions, but they generally show a resistivity decrease from the most superficial levels of SEI and a thickness increase with continued cycling prior to SEI stabilization. The most prominent resistivity increase was observed on SEI formed in Gen2 electrolyte (EC:EMC [3:7 by wt.] + 1.2 M LiPF6) with 10 wt% fluoroethylene carbonate additive; this result may partially explain the significant improvements of sustained electrochemical cycling and coulombic efficiency observed with this electrolyte additive. Our approach provides a novel and unparalleled three-dimensional approach in characterizing electronic resistivity, which contributes significantly to understanding SEI formation and the intrinsic properties critical to battery performance.},
doi = {10.1016/j.nanoen.2018.11.007},
url = {https://www.osti.gov/biblio/1485565}, journal = {Nano Energy},
issn = {2211-2855},
number = C,
volume = 55,
place = {United States},
year = {2018},
month = {11}
}

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