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Title: Understanding the Effect of Preparative Approaches in the Formation of “Flower-like” Li 4Ti 5O 12 —Multiwalled Carbon Nanotube Composite Motifs with Performance as High-Rate Anode Materials for Li-Ion Battery Applications

Abstract

Herein we highlight the significance of nanoscale attachment modality as an important determinant of observed electrochemical performance. Specifically, controlled loading ratios of multi-walled carbon nanotubes (MWNTs) have been successfully anchored onto the surfaces of a unique “flower-like” Li 4Ti 5O 12 (LTO) micro-scale sphere motif, for the first time, using a number of different and distinctive preparative approaches, including (i) a sonication method, (ii) an in situ direct-deposition approach, (iii) a covalent attachment protocol, as well as (iv) a π-π interaction strategy. In terms of structural characterization, the composites generated by physical sonication as well as non-covalent π-π interactions retained the intrinsic hierarchical “flower-like” morphology and exhibited a similar crystallinity profile as compared with that of pure LTO. By comparison, the composite prepared by an in situ direct deposition approach yielded not only a fragmented LTO structure, likely due to the possible interfering presence of the MWNTs themselves during the relevant hydrothermal reaction, but also a larger crystallite size, owing to the higher annealing temperature associated with its preparation. Finally, the composite created via covalent attachment was covered with an amorphous insulating linker, which probably led to a decreased contact area between the LTO and the MWNTs and hence, amore » lower crystallinity in the resulting composite. In addition electrode tests suggested that the composite generated by π-π interactions out-performed the other three analogous heterostructures, due to a smaller charge transfer resistance as well as a faster Li-ion diffusion. In particular, the LTO-MWNT composite, produced by π-π interactions, exhibited a reproducibly high rate capability as well as a reliably solid cycling stability, delivering 132 mA h g -1 at 50 C, after 100 discharge/charge cycles, including 40 cycles at a high (>20 C) rate. To conclude, such data denote the highest electrochemical performance measured to date as compared with any LTO-carbon nanotube-based composite materials previously reported, under high discharge rate conditions, and tangibly underscore the correlation between preparative methodology and the resulting performance metrics.« less

Authors:
 [1];  [1];  [1];  [1];  [1];  [2];  [2];  [3];  [4]
  1. State University of New York at Stony Brook, Stony Brook, NY (United States). Department of Chemistry
  2. State University of New York at Stony Brook, Stony Brook, NY (United States). Department of Chemistry and Department of Materials Science and Engineering
  3. State University of New York at Stony Brook, Stony Brook, NY (United States). Department of Chemistry and Department of Materials Science and Engineering; Brookhaven National Lab. (BNL), Upton, NY (United States). Energy Sciences Directorate, Interdisciplinary Sciences Building
  4. State University of New York at Stony Brook, Stony Brook, NY (United States). Department of Chemistry ; Brookhaven National Lab. (BNL), Upton, NY (United States). Condensed Matter Physics and Materials Science Division
Publication Date:
Research Org.:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1376152
Report Number(s):
BNL-114102-2017-JA
Journal ID: ISSN 0013-4651
Grant/Contract Number:
SC0012704; SC0012673
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of the Electrochemical Society
Additional Journal Information:
Journal Volume: 164; Journal Issue: 2; Journal ID: ISSN 0013-4651
Publisher:
The Electrochemical Society
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; 36 MATERIALS SCIENCE

Citation Formats

Wang, Lei, Zhang, Yiman, McBean, Coray L., Scofield, Megan E., Yin, Jiefu, Marschilok, Amy C., Takeuchi, Kenneth J., Takeuchi, Esther S., and Wong, Stanislaus S.. Understanding the Effect of Preparative Approaches in the Formation of “Flower-like” Li4Ti5O12 —Multiwalled Carbon Nanotube Composite Motifs with Performance as High-Rate Anode Materials for Li-Ion Battery Applications. United States: N. p., 2017. Web. doi:10.1149/2.1441702jes.
Wang, Lei, Zhang, Yiman, McBean, Coray L., Scofield, Megan E., Yin, Jiefu, Marschilok, Amy C., Takeuchi, Kenneth J., Takeuchi, Esther S., & Wong, Stanislaus S.. Understanding the Effect of Preparative Approaches in the Formation of “Flower-like” Li4Ti5O12 —Multiwalled Carbon Nanotube Composite Motifs with Performance as High-Rate Anode Materials for Li-Ion Battery Applications. United States. doi:10.1149/2.1441702jes.
Wang, Lei, Zhang, Yiman, McBean, Coray L., Scofield, Megan E., Yin, Jiefu, Marschilok, Amy C., Takeuchi, Kenneth J., Takeuchi, Esther S., and Wong, Stanislaus S.. Wed . "Understanding the Effect of Preparative Approaches in the Formation of “Flower-like” Li4Ti5O12 —Multiwalled Carbon Nanotube Composite Motifs with Performance as High-Rate Anode Materials for Li-Ion Battery Applications". United States. doi:10.1149/2.1441702jes. https://www.osti.gov/servlets/purl/1376152.
@article{osti_1376152,
title = {Understanding the Effect of Preparative Approaches in the Formation of “Flower-like” Li4Ti5O12 —Multiwalled Carbon Nanotube Composite Motifs with Performance as High-Rate Anode Materials for Li-Ion Battery Applications},
author = {Wang, Lei and Zhang, Yiman and McBean, Coray L. and Scofield, Megan E. and Yin, Jiefu and Marschilok, Amy C. and Takeuchi, Kenneth J. and Takeuchi, Esther S. and Wong, Stanislaus S.},
abstractNote = {Herein we highlight the significance of nanoscale attachment modality as an important determinant of observed electrochemical performance. Specifically, controlled loading ratios of multi-walled carbon nanotubes (MWNTs) have been successfully anchored onto the surfaces of a unique “flower-like” Li4Ti5O12 (LTO) micro-scale sphere motif, for the first time, using a number of different and distinctive preparative approaches, including (i) a sonication method, (ii) an in situ direct-deposition approach, (iii) a covalent attachment protocol, as well as (iv) a π-π interaction strategy. In terms of structural characterization, the composites generated by physical sonication as well as non-covalent π-π interactions retained the intrinsic hierarchical “flower-like” morphology and exhibited a similar crystallinity profile as compared with that of pure LTO. By comparison, the composite prepared by an in situ direct deposition approach yielded not only a fragmented LTO structure, likely due to the possible interfering presence of the MWNTs themselves during the relevant hydrothermal reaction, but also a larger crystallite size, owing to the higher annealing temperature associated with its preparation. Finally, the composite created via covalent attachment was covered with an amorphous insulating linker, which probably led to a decreased contact area between the LTO and the MWNTs and hence, a lower crystallinity in the resulting composite. In addition electrode tests suggested that the composite generated by π-π interactions out-performed the other three analogous heterostructures, due to a smaller charge transfer resistance as well as a faster Li-ion diffusion. In particular, the LTO-MWNT composite, produced by π-π interactions, exhibited a reproducibly high rate capability as well as a reliably solid cycling stability, delivering 132 mA h g-1 at 50 C, after 100 discharge/charge cycles, including 40 cycles at a high (>20 C) rate. To conclude, such data denote the highest electrochemical performance measured to date as compared with any LTO-carbon nanotube-based composite materials previously reported, under high discharge rate conditions, and tangibly underscore the correlation between preparative methodology and the resulting performance metrics.},
doi = {10.1149/2.1441702jes},
journal = {Journal of the Electrochemical Society},
number = 2,
volume = 164,
place = {United States},
year = {Wed Jan 18 00:00:00 EST 2017},
month = {Wed Jan 18 00:00:00 EST 2017}
}

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  • Doped motifs offer an intriguing structural pathway toward improving conductivity for battery applications. Specifically, Ca-doped, three-dimensional “flower-like” Li 4–xCa xTi 5O 12 (“x” = 0, 0.1, 0.15, and 0.2) micrometer-scale spheres have been successfully prepared for the first time using a simple and reproducible hydrothermal reaction followed by a short calcination process. The products were experimentally characterized by means of X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS) mapping, inductively coupled plasma optical emission spectrometry (ICP-OES), X-ray photoelectron spectroscopy (XPS), cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and galvanostatic charge–discharge testing. Calcium dopantmore » ions were shown to be uniformly distributed within the LTO structure without altering the underlying “flower-like” morphology. The largest lattice expansion and the highest Ti 3+ ratios were noted with XRD and XPS, respectively, whereas increased charge transfer conductivity and decreased Li +-ion diffusion coefficients were displayed in EIS for the Li 4–xCa xTi 5O 12 (“x” = 0.2) sample. The “x” = 0.2 sample yielded a higher rate capability, an excellent reversibility, and a superior cycling stability, delivering 151 and 143 mAh/g under discharge rates of 20C and 40C at cycles 60 and 70, respectively. In addition, a high cycling stability was demonstrated with a capacity retention of 92% after 300 cycles at a very high discharge rate of 20C. In addition, first-principles calculations based on density functional theory (DFT) were conducted with the goal of further elucidating and understanding the nature of the doping mechanism in this study. The DFT calculations not only determined the structure of the Ca-doped Li 4Ti 5O 12, which was found to be in accordance with the experimentally measured XPD pattern, but also yielded valuable insights into the doping-induced effect on both the atomic and electronic structures of Li 4Ti 5O 12.« less
  • Graphical abstract: Discharge capacity versus cycle number of Li{sub 4}Ti{sub 5}O{sub 12} samples synthesized by (a) CTAB-assisted sol-gel and (b) normal sol-gel method. Highlights: {yields} CTAB-assisted sol-gel route for the synthesis of nano-size Li{sub 4}Ti{sub 5}O{sub 12}. {yields} CTAB directs the microstructure of the gels and helps to control the particle size of Li{sub 4}Ti{sub 5}O{sub 12}. {yields} Li{sub 4}Ti{sub 5}O{sub 12} exhibits promising cycling performance with initial capacity of 174 mAh g{sup -1} and sustains {approx}94% beyond 30 cycles. -- Abstract: A simple CTAB-assisted sol-gel technique for synthesizing nano-sized Li{sub 4}Ti{sub 5}O{sub 12} with promising electrochemical performance as anodemore » material for lithium ion battery is reported. The structural and morphological properties are investigated by X-ray diffraction (XRD) and scanning electron microscopy (SEM), respectively. The electrochemical performance of both samples (with and without CTAB) calcined at 800 {sup o}C is evaluated using Swagelok{sup TM} cells by galvanostatic charge/discharge cycling at room temperature. The XRD pattern for sample prepared in presence of CTAB and calcined at 800 {sup o}C shows high-purity cubic-spinel Li{sub 4}Ti{sub 5}O{sub 12} phase (JCPDS no. 26-1198). Nanosized-Li{sub 4}Ti{sub 5}O{sub 12} calcined at 800 {sup o}C in presence of CTAB exhibits promising cycling performance with initial discharge capacity of 174 mAh g{sup -1} ({approx}100% of theoretical capacity) and sustains a capacity value of 164 mAh g{sup -1} beyond 30 cycles. By contrast, the sample prepared in absence of CTAB under identical reaction conditions exhibits initial discharge capacity of 140 mAh g{sup -1} (80% of theoretical capacity) that fades to 110 mAh g{sup -1} after 30 cycles.« less