skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Strain Coupling of Conversion-type Fe 3O 4 Thin Films for Lithium Ion Batteries

Abstract

Lithiation/delithiation induces significant stresses and strains into the electrodes for lithium ion batteries, which can severely degrade their cycling performance. Moreover, this electrochemically induced strain can interact with the local strain existing at solid–solid interfaces. It is not clear how this interaction affects the lithiation mechanism. The effect of this coupling on the lithiation kinetics in epitaxial Fe 3O 4 thin film on a Nb-doped SrTiO 3 substrate is investigated. In-situ and ex-situ transmission electron microscopy (TEM) results show that the lithiation is suppressed by the compressive interfacial strain. At the interface between the film and substrate, the existence of Li xFe 3O 4 rock-salt phase during lithiation consequently restrains the film from delamination. 2D phase-field simulation verifies the effect of strain. This work provides critical insights of understanding the solid–solid interfaces of conversion-type electrodes.

Authors:
 [1];  [1];  [2];  [1];  [3];  [3];  [1];  [1];  [4]; ORCiD logo [5]
  1. Brookhaven National Lab. (BNL), Upton, NY (United States)
  2. Academia Sinica, Taipei (Taiwan). Inst. of Physics
  3. Stony Brook Univ., NY (United States). Dept. of Materials Science and Engineering
  4. Academia Sinica, Taipei (Taiwan). Inst. of Physics; National Chiao Tung Univ., Hsinchu (Taiwan). Dept. of Materials Science and Engineering, Dept. of Electrophysics
  5. Brookhaven National Lab. (BNL), Upton, NY (United States); Stony Brook Univ., NY (United States). Dept. of Materials Science and Engineering
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1362155
Alternate Identifier(s):
OSTI ID: 1378794
Report Number(s):
BNL-113888-2017-JA
Journal ID: ISSN 1433-7851; R&D Project: 16060; 16060; KC0403020
Grant/Contract Number:
SC0012704
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Angewandte Chemie (International Edition)
Additional Journal Information:
Journal Name: Angewandte Chemie (International Edition); Journal Volume: 56; Journal Issue: 27; Journal ID: ISSN 1433-7851
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
29 ENERGY PLANNING, POLICY, AND ECONOMY; lithium ion battery; Strain Coupling; Fe3O4; Center for Functional Nanomaterials; conversion electrodes; lithiation; magnetite; strain; thin films

Citation Formats

Hwang, Sooyeon, Meng, Qingping, Chen, Ping-Fan, Kisslinger, Kim, Cen, Jiajie, Orlov, Alexander, Zhu, Yimei, Stach, Eric A., Chu, Ying-Hao, and Su, Dong. Strain Coupling of Conversion-type Fe3O4 Thin Films for Lithium Ion Batteries. United States: N. p., 2017. Web. doi:10.1002/anie.201703168.
Hwang, Sooyeon, Meng, Qingping, Chen, Ping-Fan, Kisslinger, Kim, Cen, Jiajie, Orlov, Alexander, Zhu, Yimei, Stach, Eric A., Chu, Ying-Hao, & Su, Dong. Strain Coupling of Conversion-type Fe3O4 Thin Films for Lithium Ion Batteries. United States. doi:10.1002/anie.201703168.
Hwang, Sooyeon, Meng, Qingping, Chen, Ping-Fan, Kisslinger, Kim, Cen, Jiajie, Orlov, Alexander, Zhu, Yimei, Stach, Eric A., Chu, Ying-Hao, and Su, Dong. Mon . "Strain Coupling of Conversion-type Fe3O4 Thin Films for Lithium Ion Batteries". United States. doi:10.1002/anie.201703168.
@article{osti_1362155,
title = {Strain Coupling of Conversion-type Fe3O4 Thin Films for Lithium Ion Batteries},
author = {Hwang, Sooyeon and Meng, Qingping and Chen, Ping-Fan and Kisslinger, Kim and Cen, Jiajie and Orlov, Alexander and Zhu, Yimei and Stach, Eric A. and Chu, Ying-Hao and Su, Dong},
abstractNote = {Lithiation/delithiation induces significant stresses and strains into the electrodes for lithium ion batteries, which can severely degrade their cycling performance. Moreover, this electrochemically induced strain can interact with the local strain existing at solid–solid interfaces. It is not clear how this interaction affects the lithiation mechanism. The effect of this coupling on the lithiation kinetics in epitaxial Fe3O4 thin film on a Nb-doped SrTiO3 substrate is investigated. In-situ and ex-situ transmission electron microscopy (TEM) results show that the lithiation is suppressed by the compressive interfacial strain. At the interface between the film and substrate, the existence of LixFe3O4 rock-salt phase during lithiation consequently restrains the film from delamination. 2D phase-field simulation verifies the effect of strain. This work provides critical insights of understanding the solid–solid interfaces of conversion-type electrodes.},
doi = {10.1002/anie.201703168},
journal = {Angewandte Chemie (International Edition)},
number = 27,
volume = 56,
place = {United States},
year = {Mon May 29 00:00:00 EDT 2017},
month = {Mon May 29 00:00:00 EDT 2017}
}

Journal Article:
Free Publicly Available Full Text
This content will become publicly available on May 29, 2018
Publisher's Version of Record

Save / Share:
  • An alcoholysis exchange between tris(hydroxymethyl)ethane (THME-H{sub 3}) or tris(hydroxymethyl)propane (THMP-H{sub 3}) and group IV metal isopropoxides yields compounds of the general formula (THMR){sub 2}M{sub 4}(OCHMe{sub 2}){sub 10}[M = Ti (R = E, 1; P, 2); Zr (R = E, 3; P, 4)]. 1 and 2 are formed in toluene, at ambient glovebox temperatures, and adopt a typical fused-M{sub 3}O{sub 12} structure where each titanium atom is surrounded by six oxygens in a slightly distorted face-shared bioctahedral arrangement. All of the oxygens of the central core are from the THMR ligand, present as {mu}-O and {mu}{sub 3}-O oxygen bridges. Generation ofmore » 3 or 4 requires heating in toluene at reflux temperatures. The zirconium atoms of 3 possess an extremely distorted edge-shared bioctahedral geometry where the central core consists of a Zr{sub 4}O{sub 8} ring (eight oxygens: six from THME ligands and two from isopropoxide ligands). Each of the zirconium atoms is six-coordinated with four bridging oxygens and two terminal isopropoxide ligands. Spincast deposited films generated from toluene solutions of 1 and 3 indicate that increased uniformity of the films and decreased hydrolysis occur in comparison to the cases of Ti(OCHMe{sub 2}){sub 4}, 5, and [Zr(OCHMe{sub 2}){sub 4}{center_dot}HOCHMe{sub 2}]{sub 2}, 6, respectively.« less
  • Graphical abstract: - Highlights: • Carbon-coated Fe{sub 3}O{sub 4} nanoflakes have been synthesized by hydrothermal method. • The nanocomposite electrode shows a large reversible capacity up to 740 mAh g{sup −1}. • The nanocomposite electrode shows promising cycling stability and rate capability. - Abstract: The carbon-coated Fe{sub 3}O{sub 4} nanoflakes were synthesized by partial reduction of monodispersed hematite (Fe{sub 2}O{sub 3}) nanoflakes with carbon coating. The carbon-coated Fe{sub 3}O{sub 4} nanoflakes were characterized by X-ray diffraction, Raman spectroscopy, field emission scanning electron microscopy, transmission electron microscopy, and galvanostatic charge/discharge measurements. It has been demonstrated that Fe{sub 2}O{sub 3} can bemore » completely converted to Fe{sub 3}O{sub 4} during the reduction process and carbon can be successfully coated on the surface of Fe{sub 3}O{sub 4} nanoflakes, forming a conductive matrix. As anode material for lithium-ion batteries, the carbon-coated Fe{sub 3}O{sub 4} nanoflakes exhibit a large reversible capacity up to 740 mAh g{sup −1} with significantly improved cycling stability and rate capability compared to the bare Fe{sub 2}O{sub 3} nanoflakes. The superior electrochemical performance of the carbon-coated Fe{sub 3}O{sub 4} nanoflakes can be attributed to the synthetic effects between small particle size and highly conductive carbon matrix.« less
  • Fe{sub 3}O{sub 4}–CNTs nanocomposites with a particle size of ∼80 nm have been synthesized through an organic-free hydrothermal synthesis strategy by using Sn(OH){sub 6}{sup 2−} as an inorganic dispersant, and served as anode materials of lithium ion batteries. Nano-sized and micro-sized Fe{sub 3}O{sub 4} without CNTs have also been prepared for comparison. The cycle performances of the as-obtained Fe{sub 3}O{sub 4} are highly size-dependent. The Fe{sub 3}O{sub 4}–CNTs nanocomposites can deliver reversible discharge capacity of ∼700 mA h/g at a current density of 50 mA/g after 50 cycles. The discharge capacity of the micro-sized Fe{sub 3}O{sub 4} decreased to 171more » mA h/g after 50 cycles. Our work not only provides new insights into the inorganic dispersant assisted hydrothermal synthesis of metal oxides nanocrystals but also gives guidance for finding new nanocomposites as anode materials of lithium ion batteries. - Graphical abstract: Fe{sub 3}O{sub 4}–CNTs nanocomposites have been prepared through an inorganic dispersant assisted hydrothermal synthesis strategy, and served as anode materials of lithium ion batteries with enhanced performance. - Highlights: • Sn(OH){sub 6}{sup 2−} is a good inorganic dispersant for the hydrothermal synthesis of nano Fe{sub 3}O{sub 4}. • The cycle performances of nano Fe{sub 3}O{sub 4} anode are much better than that of micro Fe{sub 3}O{sub 4} anode. • Compositing CNTs can enhance the cycle performances of nano Fe{sub 3}O{sub 4} anode.« less