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Title: Ambient synthesis, characterization, and electrochemical activity of LiFePO₄ nanomaterials derived from iron phosphate intermediates

Abstract

LiFePO₄ materials have become increasingly popular as a cathode material due to the many benefits they possess including thermal stability, durability, low cost, and long life span. Nevertheless, to broaden the general appeal of this material for practical electrochemical applications, it would be useful to develop a relatively mild, reasonably simple synthesis method of this cathode material. Herein, we describe a generalizable, 2-step methodology of sustainably synthesizing LiFePO₄ by incorporating a template-based, ambient, surfactantless, seedless, U-tube protocol in order to generate size and morphologically tailored, crystalline, phase-pure nanowires. The purity, composition, crystallinity, and intrinsic quality of these wires were systematically assessed using transmission electron microscopy TEM, HRTEM, SEM, XRD, SAED, EDAX and high-resolution synchrotron XRD. From these techniques, we were able to determine that there is an absence of defects present in our wires, supporting the viability of our synthetic approach. Electrochemical analysis was also employed to assess their electrochemical activity. Although our nanowires do not contain any noticeable impurities, we attribute their less than optimal electrochemical rigor to differences in the chemical bonding between our LiFePO₄ nanowires and their bulk-like counterparts. Specifically, we demonstrate for the first time experimentally that the Fe-O3 chemical bond plays an important role inmore » determining the overall conductivity of the material, an assertion which is further supported by recent first principles calculations. Nonetheless, our ambient, solution-based synthesis technique is capable of generating highly crystalline and phase-pure energy-storage-relevant nanowires that can be tailored so as to fabricate different sized materials of reproducible, reliable morphology.« less

Authors:
 [1];  [2];  [3];  [4];  [3];  [3];  [3];  [2];  [4];  [4];  [3];  [4];  [4];  [4]
  1. State Univ. of New York at Stony Brook, Stony Brook, NY (United States);
  2. State Univ. of New York at Stony Brook, Stony Brook, NY (United States); Brookhaven National Lab. (BNL), Upton, NY (United States)
  3. State Univ. of New York at Stony Brook, Stony Brook, NY (United States)
  4. Brookhaven National Lab. (BNL), Upton, NY (United States)
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States); Energy Frontier Research Centers (EFRC) (United States). Center for Mesoscale Transport Properties (m2M)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1193198
Report Number(s):
BNL-107893-2015-JA
Journal ID: ISSN 1998-0124; R&D Project: PM037; MA015MACA; KC0201030; KC0201010
Grant/Contract Number:  
SC0012704; SC0012673
Resource Type:
Accepted Manuscript
Journal Name:
Nano Research
Additional Journal Information:
Journal Volume: 589; Journal ID: ISSN 1998-0124
Publisher:
Springer
Country of Publication:
United States
Language:
English
Subject:
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY; ambient synthesis; template synthesis; cathode material; lithium iron phosphate; nanostructures

Citation Formats

Patete, Jonathan M., Wong, Stanislaus S., Scofield, Megan E., Volkov, Vyacheslav, Koenigsmann, Christopher, Zhang, Yiman, Marschilok, Amy C., Wang, Xiaoya, Bai, Jianming, Han, Jinkyu, Wang, Lei, Wang, Feng, Zhu, Yimei, and Graetz, Jason A. Ambient synthesis, characterization, and electrochemical activity of LiFePO₄ nanomaterials derived from iron phosphate intermediates. United States: N. p., 2015. Web. doi:10.1007/s12274-015-0763-5.
Patete, Jonathan M., Wong, Stanislaus S., Scofield, Megan E., Volkov, Vyacheslav, Koenigsmann, Christopher, Zhang, Yiman, Marschilok, Amy C., Wang, Xiaoya, Bai, Jianming, Han, Jinkyu, Wang, Lei, Wang, Feng, Zhu, Yimei, & Graetz, Jason A. Ambient synthesis, characterization, and electrochemical activity of LiFePO₄ nanomaterials derived from iron phosphate intermediates. United States. doi:10.1007/s12274-015-0763-5.
Patete, Jonathan M., Wong, Stanislaus S., Scofield, Megan E., Volkov, Vyacheslav, Koenigsmann, Christopher, Zhang, Yiman, Marschilok, Amy C., Wang, Xiaoya, Bai, Jianming, Han, Jinkyu, Wang, Lei, Wang, Feng, Zhu, Yimei, and Graetz, Jason A. Sat . "Ambient synthesis, characterization, and electrochemical activity of LiFePO₄ nanomaterials derived from iron phosphate intermediates". United States. doi:10.1007/s12274-015-0763-5. https://www.osti.gov/servlets/purl/1193198.
@article{osti_1193198,
title = {Ambient synthesis, characterization, and electrochemical activity of LiFePO₄ nanomaterials derived from iron phosphate intermediates},
author = {Patete, Jonathan M. and Wong, Stanislaus S. and Scofield, Megan E. and Volkov, Vyacheslav and Koenigsmann, Christopher and Zhang, Yiman and Marschilok, Amy C. and Wang, Xiaoya and Bai, Jianming and Han, Jinkyu and Wang, Lei and Wang, Feng and Zhu, Yimei and Graetz, Jason A.},
abstractNote = {LiFePO₄ materials have become increasingly popular as a cathode material due to the many benefits they possess including thermal stability, durability, low cost, and long life span. Nevertheless, to broaden the general appeal of this material for practical electrochemical applications, it would be useful to develop a relatively mild, reasonably simple synthesis method of this cathode material. Herein, we describe a generalizable, 2-step methodology of sustainably synthesizing LiFePO₄ by incorporating a template-based, ambient, surfactantless, seedless, U-tube protocol in order to generate size and morphologically tailored, crystalline, phase-pure nanowires. The purity, composition, crystallinity, and intrinsic quality of these wires were systematically assessed using transmission electron microscopy TEM, HRTEM, SEM, XRD, SAED, EDAX and high-resolution synchrotron XRD. From these techniques, we were able to determine that there is an absence of defects present in our wires, supporting the viability of our synthetic approach. Electrochemical analysis was also employed to assess their electrochemical activity. Although our nanowires do not contain any noticeable impurities, we attribute their less than optimal electrochemical rigor to differences in the chemical bonding between our LiFePO₄ nanowires and their bulk-like counterparts. Specifically, we demonstrate for the first time experimentally that the Fe-O3 chemical bond plays an important role in determining the overall conductivity of the material, an assertion which is further supported by recent first principles calculations. Nonetheless, our ambient, solution-based synthesis technique is capable of generating highly crystalline and phase-pure energy-storage-relevant nanowires that can be tailored so as to fabricate different sized materials of reproducible, reliable morphology.},
doi = {10.1007/s12274-015-0763-5},
journal = {Nano Research},
number = ,
volume = 589,
place = {United States},
year = {2015},
month = {5}
}

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