Isothermal Microcalorimetry: Insight into the Impact of Crystallite Size and Agglomeration on the Lithiation of Magnetite, Fe3O4

Huie, Matthew M.; Bock, David C.; Bruck, Andrea M.; Tallman, Killian R.; Housel, Lisa M.; Wang, Lei; Thieme, Juergen; Takeuchi, Kenneth J.; Takeuchi, Esther S.; Marschilok, Amy C.

doi:10.1021/acsami.8b20636

Title: Isothermal Microcalorimetry: Insight into the Impact of Crystallite Size and Agglomeration on the Lithiation of Magnetite, Fe₃O₄

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Abstract

Magnetite, Fe₃O₄, holds significant interest as a Li-ion anode material because of its high theoretical capacity (926 mAh/g) associated with multiple electron transfers per cation center. Notably, both crystallite size and agglomeration influence ion transport. This report probes the effects of crystallite size (12 and 29 nm) and agglomeration on the reactions involved with the formation of the surface electrolyte interphase on Fe₃O₄. Isothermal microcalorimetry (IMC) was used here to determine the parasitic heat evolved during lithiation by considering the total heat measured, cell polarization, and entropic contributions. Interestingly, the 29 nm Fe₃O₄-based electrodes produced more parasitic heat than the 12 nm samples (1346 vs 1155 J/g). This observation was explored using scanning electron microscopy (SEM) and X-ray fluorescence (XRF) mapping in conjunction with spatially resolved X-ray absorption spectroscopy (XAS). SEM imaging of the electrodes revealed more agglomerates for the 12 nm material, affirmed by XRF maps. Further, XAS results suggest that Li⁺ transport is more restricted for the smaller crystallite size (12 nm) material, attributed to its greater degree of agglomeration. These results rationalize the IMC data, where agglomerates of the 12 nm material limit solid electrolyte interphase formation and parasitic heat generation during lithiation of Fe₃O₄.

Authors:

Huie, Matthew M. ^[1]; Bock, David C. ^[2]; Bruck, Andrea M. ^[3]; Tallman, Killian R. ^[1]; Housel, Lisa M. ^[1];

^[3]; Thieme, Juergen ^[4];

^[5];

^[6];

^[6]

Stony Brook Univ., NY (United States). Dept. of Materials Science and Chemical Engineering
Brookhaven National Lab. (BNL), Upton, NY (United States). Energy and Photon Sciences Directorate
Stony Brook Univ., NY (United States). Dept. of Chemistry
Brookhaven National Lab. (BNL), Upton, NY (United States). National Synchrotron Light Source II
Stony Brook Univ., NY (United States). Dept. of Materials Science and Chemical Engineering. Dept. of Chemistry
Stony Brook Univ., NY (United States). Dept. of Materials Science and Chemical Engineering. Dept. of Chemistry; Brookhaven National Lab. (BNL), Upton, NY (United States). Energy and Photon Sciences Directorate

Publication Date:: Thu Jan 24 00:00:00 EST 2019

Research Org.:: Energy Frontier Research Centers (EFRC) (United States). Center for Mesoscale Transport Properties (m2mt); Brookhaven National Lab. (BNL), Upton, NY (United States); Stony Brook Univ., NY (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)

OSTI Identifier:: 1502799

Report Number(s):: BNL-211424-2019-JAAM
Journal ID: ISSN 1944-8244

Grant/Contract Number:: SC0012704; SC0012673; 1109408

Resource Type:: Accepted Manuscript

Journal Name:: ACS Applied Materials and Interfaces

Additional Journal Information:: Journal Volume: 11; Journal Issue: 7; Journal ID: ISSN 1944-8244

Publisher:: American Chemical Society (ACS)

Country of Publication:: United States

Language:: English

Subject:: 25 ENERGY STORAGE; aggregation; energy storage; isothermal microcalorimetry; lithium battery; magnetite; surface electrolyte interphase

Citation Formats


                    Huie, Matthew M., Bock, David C., Bruck, Andrea M., Tallman, Killian R., Housel, Lisa M., Wang, Lei, Thieme, Juergen, Takeuchi, Kenneth J., Takeuchi, Esther S., and Marschilok, Amy C. Isothermal Microcalorimetry: Insight into the Impact of Crystallite Size and Agglomeration on the Lithiation of Magnetite, Fe3O4.  United States: N. p., 2019. 
Web.  doi:10.1021/acsami.8b20636.

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                    Huie, Matthew M., Bock, David C., Bruck, Andrea M., Tallman, Killian R., Housel, Lisa M., Wang, Lei, Thieme, Juergen, Takeuchi, Kenneth J., Takeuchi, Esther S., & Marschilok, Amy C. Isothermal Microcalorimetry: Insight into the Impact of Crystallite Size and Agglomeration on the Lithiation of Magnetite, Fe3O4.  United States.  https://doi.org/10.1021/acsami.8b20636

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                    Huie, Matthew M., Bock, David C., Bruck, Andrea M., Tallman, Killian R., Housel, Lisa M., Wang, Lei, Thieme, Juergen, Takeuchi, Kenneth J., Takeuchi, Esther S., and Marschilok, Amy C. Thu .  
"Isothermal Microcalorimetry: Insight into the Impact of Crystallite Size and Agglomeration on the Lithiation of Magnetite, Fe3O4".  United States.  https://doi.org/10.1021/acsami.8b20636.  https://www.osti.gov/servlets/purl/1502799.

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@article{osti_1502799,

  title        = {Isothermal Microcalorimetry: Insight into the Impact of Crystallite Size and Agglomeration on the Lithiation of Magnetite, Fe3O4},

  author       = {Huie, Matthew M. and Bock, David C. and Bruck, Andrea M. and Tallman, Killian R. and Housel, Lisa M. and Wang, Lei and Thieme, Juergen and Takeuchi, Kenneth J. and Takeuchi, Esther S. and Marschilok, Amy C.},

  abstractNote = {Magnetite, Fe3O4, holds significant interest as a Li-ion anode material because of its high theoretical capacity (926 mAh/g) associated with multiple electron transfers per cation center. Notably, both crystallite size and agglomeration influence ion transport. This report probes the effects of crystallite size (12 and 29 nm) and agglomeration on the reactions involved with the formation of the surface electrolyte interphase on Fe3O4. Isothermal microcalorimetry (IMC) was used here to determine the parasitic heat evolved during lithiation by considering the total heat measured, cell polarization, and entropic contributions. Interestingly, the 29 nm Fe3O4-based electrodes produced more parasitic heat than the 12 nm samples (1346 vs 1155 J/g). This observation was explored using scanning electron microscopy (SEM) and X-ray fluorescence (XRF) mapping in conjunction with spatially resolved X-ray absorption spectroscopy (XAS). SEM imaging of the electrodes revealed more agglomerates for the 12 nm material, affirmed by XRF maps. Further, XAS results suggest that Li+ transport is more restricted for the smaller crystallite size (12 nm) material, attributed to its greater degree of agglomeration. These results rationalize the IMC data, where agglomerates of the 12 nm material limit solid electrolyte interphase formation and parasitic heat generation during lithiation of Fe3O4.},

  doi          = {10.1021/acsami.8b20636},

  journal      = {ACS Applied Materials and Interfaces},

  number       = 7,

  volume       = 11,

  place        = {United States},

  year         = {Thu Jan 24 00:00:00 EST 2019},

  month        = {Thu Jan 24 00:00:00 EST 2019}

}

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Title: Isothermal Microcalorimetry: Insight into the Impact of Crystallite Size and Agglomeration on the Lithiation of Magnetite, Fe3O4

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Title: Isothermal Microcalorimetry: Insight into the Impact of Crystallite Size and Agglomeration on the Lithiation of Magnetite, Fe₃O₄