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

Title: Essential Role of Spinel ZnFe2O4 Surfaces during Lithiation

Abstract

Spinel zinc ferrite (ZnFe2O4) is a well-known anode material in lithium ion batteries (LIBs) due to its large theoretical capacity. However, the high potentials observed at the initial stage of lithiation observed cannot be captured using a model of Li+ intercalation into the stoichiometric ZnFe2O4 bulk. Here, using density functional theory (DFT) we report for the first time that theZnFe2O4 surfaces are responsible for the measured initial potentials. Among the three identified stable surfaces, ZnFeO2-terminated ZnFe2O4(1 1 0), O-terminated ZnFe2O4(1 1 1) and Zn-terminated ZnFe2O4(1 1 1), both (1 1 1) surfaces display higher lithiation potentials than the (1 1 0) surface, and the estimated potentials based on Zn-terminated (1 1 1) fit well with the experimental observations, while using the models based on ZnFe2O4(1 1 0) and previously ZnFe2O4 bulk, the estimated potentials are much lower. In terms of Li+ diffusion, the Zn-terminated ZnFe2O4(1 1 1) surface is the most active, where the energetically favorable saturation of Li+ on the surface is able to facilitate the process. Our results provide a new strategy for the design of LIB materials, via controlling the particle shape and the associated surface characteristics thus enhancing the discharging performance.

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [2]
  1. Stony Brook Univ., NY (United States)
  2. Brookhaven National Lab. (BNL), Upton, NY (United States); Stony Brook Univ., NY (United States)
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Center for Mesoscale Transport Properties (m2mt); Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1483560
Report Number(s):
BNL-209500-2018-JAAM
Journal ID: ISSN 1944-8244
Grant/Contract Number:  
SC0012704
Resource Type:
Accepted Manuscript
Journal Name:
ACS Applied Materials and Interfaces
Additional Journal Information:
Journal Volume: 10; Journal Issue: 41; Journal ID: ISSN 1944-8244
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; ZnFe2O4; DFT; surface stability; Li absorption; Li diffusion; Li-ion batteries

Citation Formats

Guo, Haoyue, Marschilok, Amy C., Takeuchi, Kenneth J., Takeuchi, Esther S., and Liu, Ping. Essential Role of Spinel ZnFe2O4 Surfaces during Lithiation. United States: N. p., 2018. Web. https://doi.org/10.1021/acsami.8b12869.
Guo, Haoyue, Marschilok, Amy C., Takeuchi, Kenneth J., Takeuchi, Esther S., & Liu, Ping. Essential Role of Spinel ZnFe2O4 Surfaces during Lithiation. United States. https://doi.org/10.1021/acsami.8b12869
Guo, Haoyue, Marschilok, Amy C., Takeuchi, Kenneth J., Takeuchi, Esther S., and Liu, Ping. Wed . "Essential Role of Spinel ZnFe2O4 Surfaces during Lithiation". United States. https://doi.org/10.1021/acsami.8b12869. https://www.osti.gov/servlets/purl/1483560.
@article{osti_1483560,
title = {Essential Role of Spinel ZnFe2O4 Surfaces during Lithiation},
author = {Guo, Haoyue and Marschilok, Amy C. and Takeuchi, Kenneth J. and Takeuchi, Esther S. and Liu, Ping},
abstractNote = {Spinel zinc ferrite (ZnFe2O4) is a well-known anode material in lithium ion batteries (LIBs) due to its large theoretical capacity. However, the high potentials observed at the initial stage of lithiation observed cannot be captured using a model of Li+ intercalation into the stoichiometric ZnFe2O4 bulk. Here, using density functional theory (DFT) we report for the first time that theZnFe2O4 surfaces are responsible for the measured initial potentials. Among the three identified stable surfaces, ZnFeO2-terminated ZnFe2O4(1 1 0), O-terminated ZnFe2O4(1 1 1) and Zn-terminated ZnFe2O4(1 1 1), both (1 1 1) surfaces display higher lithiation potentials than the (1 1 0) surface, and the estimated potentials based on Zn-terminated (1 1 1) fit well with the experimental observations, while using the models based on ZnFe2O4(1 1 0) and previously ZnFe2O4 bulk, the estimated potentials are much lower. In terms of Li+ diffusion, the Zn-terminated ZnFe2O4(1 1 1) surface is the most active, where the energetically favorable saturation of Li+ on the surface is able to facilitate the process. Our results provide a new strategy for the design of LIB materials, via controlling the particle shape and the associated surface characteristics thus enhancing the discharging performance.},
doi = {10.1021/acsami.8b12869},
journal = {ACS Applied Materials and Interfaces},
number = 41,
volume = 10,
place = {United States},
year = {2018},
month = {9}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 2 works
Citation information provided by
Web of Science

Figures / Tables:

Figure 1 Figure 1: Phase diagram and the corresponding structures of stable terminations of ZnFe2O4 (1 0 0), (1 1 0) and (1 1 1) surfaces.

Save / Share:

Works referenced in this record:

Li-storage and cyclability of urea combustion derived ZnFe2O4 as anode for Li-ion batteries
journal, January 2008


Facile shape design and fabrication of ZnFe 2 O 4 as an anode material for Li-ion batteries
journal, January 2014

  • Zhong, Xiao-Bin; Jin, Bo; Yang, Zhi-Zheng
  • RSC Adv., Vol. 4, Issue 98
  • DOI: 10.1039/c4ra09912e

Carbon Coated ZnFe 2 O 4 Nanoparticles for Advanced Lithium-Ion Anodes
journal, November 2012

  • Bresser, Dominic; Paillard, Elie; Kloepsch, Richard
  • Advanced Energy Materials, Vol. 3, Issue 4
  • DOI: 10.1002/aenm.201200735

Electrochemical lithium storage of a ZnFe 2 O 4 /graphene nanocomposite as an anode material for rechargeable lithium ion batteries
journal, January 2014

  • Rai, Alok Kumar; Kim, Sungjin; Gim, Jihyeon
  • RSC Adv., Vol. 4, Issue 87
  • DOI: 10.1039/c4ra08414d

Preparation of ZnFe 2 O 4 nanostructures and highly efficient visible-light-driven hydrogen generation with the assistance of nanoheterostructures
journal, January 2015

  • Song, Hui; Zhu, Liping; Li, Yaguang
  • Journal of Materials Chemistry A, Vol. 3, Issue 16
  • DOI: 10.1039/c5ta00737b

Synthesis of floriated ZnFe2O4 with porous nanorod structures and its photocatalytic hydrogen production under visible light
journal, January 2010

  • Lv, Hongjin; Ma, Liang; Zeng, Peng
  • Journal of Materials Chemistry, Vol. 20, Issue 18
  • DOI: 10.1039/b919897k

NH3 molecule adsorption on spinel-type ZnFe2O4 surface: A DFT and experimental comparison study
journal, June 2018


First-principles study of Ti3AC2 (A=Si, Al) (001) surfaces
journal, August 2007


Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996


Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996


Projector augmented-wave method
journal, December 1994


Generalized Gradient Approximation Made Simple
journal, October 1996

  • Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
  • Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
  • DOI: 10.1103/physrevlett.77.3865

    Works referencing / citing this record:

    A network of porous carbon/ZnCo 2 O 4 nanotubes derived from shell-hybridized worm-like micelles for lithium storage
    journal, January 2019

    • Li, Huiya; Lv, Leilei; Wang, Weichong
    • Journal of Materials Chemistry A, Vol. 7, Issue 39
    • DOI: 10.1039/c9ta07869j

    Rationalization of Diversity in Spinel MgFe 2 O 4 Surfaces
    journal, September 2019

    • Guo, Haoyue; Marschilok, Amy C.; Takeuchi, Kenneth J.
    • Advanced Materials Interfaces, Vol. 6, Issue 22
    • DOI: 10.1002/admi.201901218

    Density Functional Theory for Battery Materials
    journal, September 2019

    • He, Qiu; Yu, Bin; Li, Zhaohuai
    • ENERGY & ENVIRONMENTAL MATERIALS, Vol. 2, Issue 4
    • DOI: 10.1002/eem2.12056

      Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.