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Title: Multi-Stage Structural Transformations in Zero-Strain Lithium Titanate Unveiled by in Situ X-ray Absorption Fingerprints

Journal Article · · Journal of the American Chemical Society
 [1];  [2];  [3];  [4];  [1];  [5];  [6];  [6]; ORCiD logo [7];  [8]; ORCiD logo [9]; ORCiD logo [9];  [2]; ORCiD logo [1]
  1. Brookhaven National Lab. (BNL), Upton, NY (United States). Sustainable Energy Technologies Dept.
  2. Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials
  3. Stony Brook Univ., NY (United States). Dept. of Chemistry
  4. Brookhaven National Lab. (BNL), Upton, NY (United States). Energy and Photon Sciences Directorate
  5. Brookhaven National Lab. (BNL), Upton, NY (United States). National Synchrotron Light Source II
  6. Brookhaven National Lab. (BNL), Upton, NY (United States). Condensed Matter Physics and Materials Science Dept.
  7. Brookhaven National Lab. (BNL), Upton, NY (United States). Chemistry Dept.; Stony Brook Univ., NY (United States). Dept. of Materials Science and Chemical Engineering
  8. Stony Brook Univ., NY (United States). Dept. of Chemistry. Dept. of Materials Science and Chemical Engineering
  9. Stony Brook Univ., NY (United States). Dept. of Chemistry. Dept. of Materials Science and Chemical Engineering; Brookhaven National Lab. (BNL), Upton, NY (United States). Energy and Photon Sciences Directorate
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Zero-strain electrodes, such as spinel lithium titanate (Li4/3Ti5/3O4), are appealing for application in batteries due to their negligible volume change and extraordinary stability upon repeated charge/discharge cycles. On the other hand, this same property makes it challenging to probe their structural changes during the electrochemical reaction. In this paper, we report in situ studies of lithiation-driven structural transformations in Li4/3Ti5/3O4 via a combination of X-ray absorption spectroscopy and ab initio calculations. Based on excellent agreement between computational and experimental spectra of Ti K-edge, we identified key spectral features as fingerprints for quantitative assessment of structural evolution at different length scales. Results from this study indicate that, despite the small variation in the crystal lattice during lithiation, pronounced structural transformations occur in Li4/3Ti5/3O4, both locally and globally, giving rise to a multi-stage kinetic process involving mixed quasi-solid solution/macroscopic two-phase transformations over a wide range of Li concentrations. Finally, this work highlights the unique capability of combining in situ core-level spectroscopy and first-principles calculations for probing Li-ion intercalation in zero-strain electrodes, which is crucial to designing high-performance electrode materials for long-life batteries.

Research Organization:
Brookhaven National Laboratory (BNL), Upton, NY (United States); Stony Brook Univ., NY (United States); Energy Frontier Research Centers (EFRC) (United States). Center for Mesoscale Transport Properties (m2M); Energy Frontier Research Centers (EFRC) (United States). Center for Mesoscale Transport Properties (m2mt); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); BNL Laboratory Directed Research and Development (LDRD) Program; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division
Grant/Contract Number:
SC0012704; SC0012673; FG02-03ER15476; AC02-05CH11231
OSTI ID:
1439804
Alternate ID(s):
OSTI ID: 1489025
Report Number(s):
BNL-114533-2017-JAAM
Journal Information:
Journal of the American Chemical Society, Vol. 139, Issue 46; ISSN 0002-7863
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

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Cited By (5)

Toward Optimal Performance and In-Depth Understanding of Spinel Li 4 Ti 5 O 12 Electrodes through Phase Field Modeling journal February 2018
Atomic-scale structural and chemical evolution of Li3V2(PO4)3 cathode cycled at high voltage window journal May 2019
Identifying the Origin and Contribution of Surface Storage in TiO 2 (B) Nanotube Electrode by In Situ Dynamic Valence State Monitoring journal July 2018
Crystal structure, solid phase diffusion path and coefficient of Zr-doped Li 4 Ti 5 O 12 journal September 2019
Electron-hole theory of the effect of quantum nuclei on the x-ray absorption spectra of liquid water text January 2018

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