Dependence on Crystal Size of the Nanoscale Chemical Phase Distribution and Fracture in Li x FePO 4

Yu, Young-Sang; Kim, Chunjoong; Shapiro, David A.; Farmand, Maryam; Qian, Danna; Tyliszczak, Tolek; Kilcoyne, A. L. David; Celestre, Rich; Marchesini, Stefano; Joseph, John; Denes, Peter; Warwick, Tony; Strobridge, Fiona C.; Grey, Clare P.; Padmore, Howard; Meng, Ying Shirley; Kostecki, Robert; Cabana, Jordi

doi:10.1021/acs.nanolett.5b01314

Title: Dependence on Crystal Size of the Nanoscale Chemical Phase Distribution and Fracture in Li _x FePO ₄

Abstract

The performance of battery electrode materials is strongly affected by inefficiencies in utilization kinetics and cycle life as well as size effects. Observations of phase transformations in these materials with high chemical and spatial resolution can elucidate the relationship between chemical processes and mechanical degradation. Soft X-ray ptychographic microscopy combined with X-ray absorption spectroscopy and electron microscopy creates a powerful suite of tools that we use to assess the chemical and morphological changes in lithium iron phosphate (LiFePO₄) micro- and nanocrystals that occur upon delithiation. All sizes of partly delithiated crystals were found to contain two phases with a complex correlation between crystallographic orientation and phase distribution. However, the lattice mismatch between LiFePO₄ and FePO₄ led to severe fracturing on microcrystals, whereas no mechanical damage was observed in nanoplates, indicating that mechanics are a principal driver in the outstanding electrode performance of LiFePO₄ nanoparticles. These results demonstrate the importance of engineering the active electrode material in next generation electrical energy storage systems, which will achieve theoretical limits of energy density and extended stability. This work establishes soft X-ray ptychographic chemical imaging as an essential tool to build comprehensive relationships between mechanics and chemistry that guide this engineering design.

Authors:

Yu, Young-Sang ^[1]; Kim, Chunjoong ^[2]; Shapiro, David A. ^[3]; Farmand, Maryam ^[3]; Qian, Danna ^[4]; Tyliszczak, Tolek ^[3]; Kilcoyne, A. L. David ^[3]; Celestre, Rich ^[3]; Marchesini, Stefano ^[3]; Joseph, John ^[5]; Denes, Peter ^[3]; Warwick, Tony ^[3]; Strobridge, Fiona C. ^[6]; Grey, Clare P. ^[7]; Padmore, Howard ^[3]; Meng, Ying Shirley ^[4]; Kostecki, Robert ^[8]; Cabana, Jordi ^[2]

Department of Chemistry, University of Illinois at Chicago, Chicago, Illinois 60607, United States, Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States, Department of NanoEngineering, University of California, San Diego, La Jolla, California 92121, United States, Energy Storage and Distributed Resources Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States
Department of Chemistry, University of Illinois at Chicago, Chicago, Illinois 60607, United States
Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States
Department of NanoEngineering, University of California, San Diego, La Jolla, California 92121, United States
Engineering Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States
Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge CB2 1EW, United Kingdom
Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge CB2 1EW, United Kingdom, Department of Chemistry, Stony Brook University, Stony Brook, New York 11794, United States
Energy Storage and Distributed Resources Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States

Publication Date:: Thu Jun 18 00:00:00 EDT 2015

Research Org.:: Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Energy Frontier Research Centers (EFRC) (United States). Northeastern Center for Chemical Energy Storage (NECCES)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Advanced Scientific Computing Research (ASCR)

OSTI Identifier:: 1185242

Alternate Identifier(s):: OSTI ID: 1524031

Grant/Contract Number:: AC02-05CH11231; SC0012583; SC0001294

Resource Type:: Published Article

Journal Name:: Nano Letters

Additional Journal Information:: Journal Name: Nano Letters Journal Volume: 15 Journal Issue: 7; Journal ID: ISSN 1530-6984

Publisher:: American Chemical Society

Country of Publication:: United States

Language:: English

Subject:: 36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; High resolution chemical imaging; battery materials; redox phase transformations; chemo-mechanical coupling; LiFePO4

Citation Formats


                    Yu, Young-Sang, Kim, Chunjoong, Shapiro, David A., Farmand, Maryam, Qian, Danna, Tyliszczak, Tolek, Kilcoyne, A. L. David, Celestre, Rich, Marchesini, Stefano, Joseph, John, Denes, Peter, Warwick, Tony, Strobridge, Fiona C., Grey, Clare P., Padmore, Howard, Meng, Ying Shirley, Kostecki, Robert, and Cabana, Jordi. Dependence on Crystal Size of the Nanoscale Chemical Phase Distribution and Fracture in Li x FePO 4.  United States: N. p., 2015. 
Web.  doi:10.1021/acs.nanolett.5b01314.

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                    Yu, Young-Sang, Kim, Chunjoong, Shapiro, David A., Farmand, Maryam, Qian, Danna, Tyliszczak, Tolek, Kilcoyne, A. L. David, Celestre, Rich, Marchesini, Stefano, Joseph, John, Denes, Peter, Warwick, Tony, Strobridge, Fiona C., Grey, Clare P., Padmore, Howard, Meng, Ying Shirley, Kostecki, Robert, & Cabana, Jordi. Dependence on Crystal Size of the Nanoscale Chemical Phase Distribution and Fracture in Li x FePO 4.  United States.  https://doi.org/10.1021/acs.nanolett.5b01314

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                    Yu, Young-Sang, Kim, Chunjoong, Shapiro, David A., Farmand, Maryam, Qian, Danna, Tyliszczak, Tolek, Kilcoyne, A. L. David, Celestre, Rich, Marchesini, Stefano, Joseph, John, Denes, Peter, Warwick, Tony, Strobridge, Fiona C., Grey, Clare P., Padmore, Howard, Meng, Ying Shirley, Kostecki, Robert, and Cabana, Jordi. Thu .  
"Dependence on Crystal Size of the Nanoscale Chemical Phase Distribution and Fracture in Li x FePO 4".  United States.  https://doi.org/10.1021/acs.nanolett.5b01314.

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@article{osti_1185242,

  title        = {Dependence on Crystal Size of the Nanoscale Chemical Phase Distribution and Fracture in Li x FePO 4},

  author       = {Yu, Young-Sang and Kim, Chunjoong and Shapiro, David A. and Farmand, Maryam and Qian, Danna and Tyliszczak, Tolek and Kilcoyne, A. L. David and Celestre, Rich and Marchesini, Stefano and Joseph, John and Denes, Peter and Warwick, Tony and Strobridge, Fiona C. and Grey, Clare P. and Padmore, Howard and Meng, Ying Shirley and Kostecki, Robert and Cabana, Jordi},

  abstractNote = {The performance of battery electrode materials is strongly affected by inefficiencies in utilization kinetics and cycle life as well as size effects. Observations of phase transformations in these materials with high chemical and spatial resolution can elucidate the relationship between chemical processes and mechanical degradation. Soft X-ray ptychographic microscopy combined with X-ray absorption spectroscopy and electron microscopy creates a powerful suite of tools that we use to assess the chemical and morphological changes in lithium iron phosphate (LiFePO4) micro- and nanocrystals that occur upon delithiation. All sizes of partly delithiated crystals were found to contain two phases with a complex correlation between crystallographic orientation and phase distribution. However, the lattice mismatch between LiFePO4 and FePO4 led to severe fracturing on microcrystals, whereas no mechanical damage was observed in nanoplates, indicating that mechanics are a principal driver in the outstanding electrode performance of LiFePO4 nanoparticles. These results demonstrate the importance of engineering the active electrode material in next generation electrical energy storage systems, which will achieve theoretical limits of energy density and extended stability. This work establishes soft X-ray ptychographic chemical imaging as an essential tool to build comprehensive relationships between mechanics and chemistry that guide this engineering design.},

  doi          = {10.1021/acs.nanolett.5b01314},

  journal      = {Nano Letters},

  number       = 7,

  volume       = 15,

  place        = {United States},

  year         = {Thu Jun 18 00:00:00 EDT 2015},

  month        = {Thu Jun 18 00:00:00 EDT 2015}

}

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Figure 1: Representative scanning electron microscopy (SEM), together with high resolution transmission electron microscopy (HRTEM) images of Li_xFePO₄ (A,B) S-2 and (C,D) S-3C. A representative SEM image for S-1 is shown in Figure S3. The insets in B and D show the Fourier transformation patterns produced from the regions markedmore »

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Title: Dependence on Crystal Size of the Nanoscale Chemical Phase Distribution and Fracture in Li x FePO 4

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Title: Dependence on Crystal Size of the Nanoscale Chemical Phase Distribution and Fracture in Li _x FePO ₄