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Size dependent behavior of Fe3O4 crystals during electrochemical (de)lithiation: an in situ X-ray diffraction, ex situ X-ray absorption spectroscopy, transmission electron microscopy and theoretical investigation

Journal Article · · Physical Chemistry Chemical Physics. PCCP
DOI:https://doi.org/10.1039/c7cp03312e· OSTI ID:1402423
 [1];  [1];  [1];  [2];  [3];  [3];  [1];  [4];  [2];  [5];  [2];  [2]
  1. Brookhaven National Lab. (BNL), Upton, NY (United States)
  2. Stony Brook Univ., Stony Brook, NY (United States)
  3. Columbia Univ., New York, NY (United States)
  4. American Physical Society, Ridge, NY (United States)
  5. Brookhaven National Lab. (BNL), Upton, NY (United States); Stony Brook Univ., Stony Brook, NY (United States)
+ Show Author Affiliations
Here, the iron oxide magnetite, Fe3O4, is a promising conversion type lithium ion battery anode material due to its high natural abundance, low cost and high theoretical capacity. While the close packing of ions in the inverse spinel structure of Fe3O4 enables high energy density, it also limits the kinetics of lithium ion diffusion in the material. Nanosizing of Fe3O4 to reduce the diffusion path length is an effective strategy for overcoming this issue and results in improved rate capability. However, the impact of nanosizing on the multiple structural transformations that occur during the electrochemical (de)lithiation reaction in Fe3O4 is poorly understood. In this study, the influence of crystallite size on the lithiation-conversion mechanisms in Fe3O4 is investigated using complementary X-ray techniques along with transmission electron microscopy (TEM) and continuum level simulations on electrodes of two different Fe3O4 crystallite sizes. In situ X-ray diffraction (XRD) measurements were utilized to track the changes to the crystalline phases during (de)lithiation. X-ray absorption spectroscopy (XAS) measurements at multiple points during the (de)lithiation processes provided local electronic and atomic structural information. Tracking the crystalline and nanocrystalline phases during the first (de)lithiation provides experimental evidence that (1) the lithiation mechanism is non-uniform and dependent on crystallite size, where increased Li+ diffusion length in larger crystals results in conversion to Fe0 metal while insertion of Li+ into spinel-Fe3O4 is still occurring, and (2) the disorder and size of the Fe metal domains formed when either material is fully lithiated impacts the homogeneity of the FeO phase formed during the subsequent delithiation.
Research Organization:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Organization:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Grant/Contract Number:
SC0012704
OSTI ID:
1402423
Alternate ID(s):
OSTI ID: 1425178
OSTI ID: 1375344
OSTI ID: 1389045
Report Number(s):
BNL--114433-2017-JA; BNL-114491-2017-JAAM
Journal Information:
Physical Chemistry Chemical Physics. PCCP, Journal Name: Physical Chemistry Chemical Physics. PCCP Journal Issue: 31 Vol. 19; ISSN 1463-9076; ISSN PPCPFQ
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English

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Cited By (7)

The Systematic Refinement for the Phase Change and Conversion Reactions Arising from the Lithiation of Magnetite Nanocrystals journal November 2019
Scalable Synthesis of an Artificial Polydopamine Solid‐Electrolyte‐Interface‐Assisted 3D rGO/Fe 3 O 4 @PDA Hydrogel for a Highly Stable Anode with Enhanced Lithium‐Ion‐Storage Properties journal January 2019
In Situ Probing Multiple-Scale Structures of Energy Materials for Li-Ion Batteries journal May 2019
Synthesis and structural characterization of iron-cementite nanoparticles encapsulated in carbon matrix journal January 2020
Multi-electron transfer enabled by topotactic reaction in magnetite journal April 2019
Probing enhanced lithium-ion transport kinetics in 2D holey nanoarchitectured electrodes journal August 2018
Application of Operando X-ray Diffractometry in Various Aspects of the Investigations of Lithium/Sodium-Ion Batteries journal November 2018

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