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Title: MIL-101(Fe) as a lithium-ion battery electrode material: a relaxation and intercalation mechanism during lithium insertion

Abstract

The electrochemical performance of a MIL-101(Fe) metal–organic framework (MOF) as a lithium ion battery electrode is reported for the first time. Iron metal centers can be electrochemically activated. The Fe3+/Fe2+ redox couple is electrochemically active, but not reversible over many cycles. A comparison between ex situ and in operando X-ray absorption spectroscopy (XAS) on the Fe K-edge is presented. Our results indicate that the capacity fade is related to a time dependent, irreversible oxidation of Fe2+ to Fe3+. These results are key in proving the importance of in operando XAS measurements. The MOF side reaction with an electrolyte has been computationally modeled. These results provide further insights on the mechanism responsible for the MOF lack of reversibility. Future guidelines for improving the reversibility of MOFs used as electrodes in Li-ion batteries based on the fine-tuning of the electronic structure of the material are proposed.

Authors:
 [1];  [1];  [1];  [1];  [2];  [1];  [1];  [1];  [1]
  1. Univ. of California, San Diego, CA (United States)
  2. Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Publication Date:
Research Org.:
Univ. of California, San Diego, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1781416
Grant/Contract Number:  
FG02-08ER46519
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of Materials Chemistry. A
Additional Journal Information:
Journal Volume: 3; Journal Issue: 8; Journal ID: ISSN 2050-7488
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; Lithium ion battery; metal-organic frameworks; synchrotron; powder X-ray diffraction; X-ray absorption spectroscopy; electronic structure; density functional theory

Citation Formats

Shin, JaeWook, Kim, Min, Cirera, Jordi, Chen, Shawn, Halder, Gregory J., Yersak, Thomas A., Paesani, Francesco, Cohen, Seth M., and Meng, Ying Shirley. MIL-101(Fe) as a lithium-ion battery electrode material: a relaxation and intercalation mechanism during lithium insertion. United States: N. p., 2015. Web. doi:10.1039/c4ta06694d.
Shin, JaeWook, Kim, Min, Cirera, Jordi, Chen, Shawn, Halder, Gregory J., Yersak, Thomas A., Paesani, Francesco, Cohen, Seth M., & Meng, Ying Shirley. MIL-101(Fe) as a lithium-ion battery electrode material: a relaxation and intercalation mechanism during lithium insertion. United States. https://doi.org/10.1039/c4ta06694d
Shin, JaeWook, Kim, Min, Cirera, Jordi, Chen, Shawn, Halder, Gregory J., Yersak, Thomas A., Paesani, Francesco, Cohen, Seth M., and Meng, Ying Shirley. 2015. "MIL-101(Fe) as a lithium-ion battery electrode material: a relaxation and intercalation mechanism during lithium insertion". United States. https://doi.org/10.1039/c4ta06694d. https://www.osti.gov/servlets/purl/1781416.
@article{osti_1781416,
title = {MIL-101(Fe) as a lithium-ion battery electrode material: a relaxation and intercalation mechanism during lithium insertion},
author = {Shin, JaeWook and Kim, Min and Cirera, Jordi and Chen, Shawn and Halder, Gregory J. and Yersak, Thomas A. and Paesani, Francesco and Cohen, Seth M. and Meng, Ying Shirley},
abstractNote = {The electrochemical performance of a MIL-101(Fe) metal–organic framework (MOF) as a lithium ion battery electrode is reported for the first time. Iron metal centers can be electrochemically activated. The Fe3+/Fe2+ redox couple is electrochemically active, but not reversible over many cycles. A comparison between ex situ and in operando X-ray absorption spectroscopy (XAS) on the Fe K-edge is presented. Our results indicate that the capacity fade is related to a time dependent, irreversible oxidation of Fe2+ to Fe3+. These results are key in proving the importance of in operando XAS measurements. The MOF side reaction with an electrolyte has been computationally modeled. These results provide further insights on the mechanism responsible for the MOF lack of reversibility. Future guidelines for improving the reversibility of MOFs used as electrodes in Li-ion batteries based on the fine-tuning of the electronic structure of the material are proposed.},
doi = {10.1039/c4ta06694d},
url = {https://www.osti.gov/biblio/1781416}, journal = {Journal of Materials Chemistry. A},
issn = {2050-7488},
number = 8,
volume = 3,
place = {United States},
year = {2015},
month = {1}
}

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Facile synthesis of Fe-MOF/RGO and its application as a high performance anode in lithium-ion batteries
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