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Title: Effects of proton irradiation on structural and electrochemical charge storage properties of TiO 2 nanotube electrodes for lithium-ion batteries

Abstract

The effects of proton irradiation on nanostructured metal oxides have been investigated. Recent studies suggest that the presence of structural defects (e.g. vacancies and interstitials) in metal oxides may enhance the material's electrochemical charge storage capacity. A new approach to introduce defects in electrode materials is to use ion irradiation as it can produce a supersaturation of point defects in the target material. In this work we report the effect of low-energy proton irradiation on amorphous TiO 2 nanotube electrodes at both room temperature and high temperature (250 °C). Upon room temperature irradiation the nanotubes demonstrate an irradiation-induced phase transformation to a mixture of amorphous, anatase, and rutile domains while showing a 35% reduction in capacity compared to anatase TiO 2. On the other hand, the high temperature proton irradiation induced a disordered rutile phase within the nanotubes as characterized by Raman spectroscopy and transmission electron microscopy, which displays an improved capacity by 20% at ~240 mA h g –1 as well as improved rate capability compared to an unirradiated anatase sample. Voltammetric sweep data were used to determine the contributions from diffusion-limited intercalation and capacitive processes and it was found that the electrodes after irradiation had more contributions frommore » diffusion in lithium charge storage. Finally, our work suggests that tailoring the defect generation through ion irradiation within metal oxide electrodes could present a new avenue for designing advanced electrode materials.« less

Authors:
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Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN); Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); USDOE Office of Science (SC). Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1427393
Alternate Identifier(s):
OSTI ID: 1351743
Report Number(s):
BNL-113759-2017-JA; LA-UR-18-21408
Journal ID: ISSN 2050-7488; JMCAET; R&D Project: 16060; 16060; KC0403020
Grant/Contract Number:
SC00112704; AC52-06NA25396
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of Materials Chemistry. A
Additional Journal Information:
Journal Volume: 2017; Journal ID: ISSN 2050-7488
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
29 ENERGY PLANNING, POLICY, AND ECONOMY; TiO2; lithium ion battery; proton Irradiation; Center for Functional Nanomaterials; 25 ENERGY STORAGE; Material Science

Citation Formats

Smith, Kassiopeia A., Savva, Andreas I., Deng, Changjian, Wharry, Janelle P., Hwang, Sooyeon, Su, Dong, Wang, Yongqiang, Gong, Jue, Xu, Tao, Butt, Darryl P., and Xiong, Hui. Effects of proton irradiation on structural and electrochemical charge storage properties of TiO 2 nanotube electrodes for lithium-ion batteries. United States: N. p., 2017. Web. doi:10.1039/C7TA01026E.
Smith, Kassiopeia A., Savva, Andreas I., Deng, Changjian, Wharry, Janelle P., Hwang, Sooyeon, Su, Dong, Wang, Yongqiang, Gong, Jue, Xu, Tao, Butt, Darryl P., & Xiong, Hui. Effects of proton irradiation on structural and electrochemical charge storage properties of TiO 2 nanotube electrodes for lithium-ion batteries. United States. doi:10.1039/C7TA01026E.
Smith, Kassiopeia A., Savva, Andreas I., Deng, Changjian, Wharry, Janelle P., Hwang, Sooyeon, Su, Dong, Wang, Yongqiang, Gong, Jue, Xu, Tao, Butt, Darryl P., and Xiong, Hui. Thu . "Effects of proton irradiation on structural and electrochemical charge storage properties of TiO 2 nanotube electrodes for lithium-ion batteries". United States. doi:10.1039/C7TA01026E. https://www.osti.gov/servlets/purl/1427393.
@article{osti_1427393,
title = {Effects of proton irradiation on structural and electrochemical charge storage properties of TiO 2 nanotube electrodes for lithium-ion batteries},
author = {Smith, Kassiopeia A. and Savva, Andreas I. and Deng, Changjian and Wharry, Janelle P. and Hwang, Sooyeon and Su, Dong and Wang, Yongqiang and Gong, Jue and Xu, Tao and Butt, Darryl P. and Xiong, Hui},
abstractNote = {The effects of proton irradiation on nanostructured metal oxides have been investigated. Recent studies suggest that the presence of structural defects (e.g. vacancies and interstitials) in metal oxides may enhance the material's electrochemical charge storage capacity. A new approach to introduce defects in electrode materials is to use ion irradiation as it can produce a supersaturation of point defects in the target material. In this work we report the effect of low-energy proton irradiation on amorphous TiO2 nanotube electrodes at both room temperature and high temperature (250 °C). Upon room temperature irradiation the nanotubes demonstrate an irradiation-induced phase transformation to a mixture of amorphous, anatase, and rutile domains while showing a 35% reduction in capacity compared to anatase TiO2. On the other hand, the high temperature proton irradiation induced a disordered rutile phase within the nanotubes as characterized by Raman spectroscopy and transmission electron microscopy, which displays an improved capacity by 20% at ~240 mA h g–1 as well as improved rate capability compared to an unirradiated anatase sample. Voltammetric sweep data were used to determine the contributions from diffusion-limited intercalation and capacitive processes and it was found that the electrodes after irradiation had more contributions from diffusion in lithium charge storage. Finally, our work suggests that tailoring the defect generation through ion irradiation within metal oxide electrodes could present a new avenue for designing advanced electrode materials.},
doi = {10.1039/C7TA01026E},
journal = {Journal of Materials Chemistry. A},
number = ,
volume = 2017,
place = {United States},
year = {Thu Mar 23 00:00:00 EDT 2017},
month = {Thu Mar 23 00:00:00 EDT 2017}
}

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  • The effects of proton irradiation on nanostructured metal oxides have been investigated. Recent studies suggest that the presence of structural defects (e.g. vacancies and interstitials) in metal oxides may enhance the material's electrochemical charge storage capacity. A new approach to introduce defects in electrode materials is to use ion irradiation as it can produce a supersaturation of point defects in the target material. In this work we report the effect of low-energy proton irradiation on amorphous TiO 2 nanotube electrodes at both room temperature and high temperature (250 °C). Upon room temperature irradiation the nanotubes demonstrate an irradiation-induced phase transformationmore » to a mixture of amorphous, anatase, and rutile domains while showing a 35% reduction in capacity compared to anatase TiO 2. On the other hand, the high temperature proton irradiation induced a disordered rutile phase within the nanotubes as characterized by Raman spectroscopy and transmission electron microscopy, which displays an improved capacity by 20% at ~240 mA h g –1 as well as improved rate capability compared to an unirradiated anatase sample. Voltammetric sweep data were used to determine the contributions from diffusion-limited intercalation and capacitive processes and it was found that the electrodes after irradiation had more contributions from diffusion in lithium charge storage. Finally, our work suggests that tailoring the defect generation through ion irradiation within metal oxide electrodes could present a new avenue for designing advanced electrode materials.« less
  • The electrochemical reactions of lithium with layered composite electrodes ({chi})LiMn{sub 0.5}Ni{sub 0.5}O{sub 2} {center_dot} (1 - {chi})Li{sub 2}TiO{sub 3} were investigated at low voltages. The metal oxide 0.95LiMn{sub 0.5}Ni{sub 0.5}O{sub 2}{center_dot}0.05Li{sub 2}TiO{sub 3} (x=0.95) which can also be represented in layered notation as Li(Mn{sub 0.46}Ni{sub 0.46}Ti{sub 0.05}Li{sub 0.02})O{sub 2}, can react with one equivalent of lithium during an initial discharge from 3.2 to 1.4 V vs. Li{sup 0}. The electrochemical reaction, which corresponds to a theoretical capacity of 286 mAh/g, is hypothesized to form Li{sub 2}(Mn{sub 0.46}Ni{sub 0.46}Ti{sub 0.05}Li{sub 0.02})O{sub 2} that is isostructural with Li{sub 2}MnO{sub 2} and Li{submore » 2}NiO{sub 2}. Similar low-voltage electrochemical behavior is also observed with unsubstituted, standard LiMn{sub 0.5}Ni{sub 0.5}O{sub 2} electrodes (x=1). In situ X-ray absorption spectroscopy (XAS) data of Li(Mn{sub 0.46}Ni{sub 0.46}Ti{sub 0.05}Li{sub 0.02})O{sub 2} electrodes indicate that the low-voltage (<1.8 V) reaction is associated primarily with the reduction of Mn{sup 4+} to Mn{sup 2+}. Symmetric rocking-chair cells with the configuration Li(Mn{sub 0.46}Ni{sub 0.46}Ti{sub 0.05}Li{sub 0.02})O{sub 2}/Li(Mn{sub 0.46}Ni{sub 0.46}Ti{sub 0.05}Li{sub 0.02})O{sub 2} were tested. These electrodes provide a rechargeable capacity in excess of 300 mAh/g when charged and discharged over a 3.3 to -3.3 V range and show an insignificant capacity loss on the initial cycle. These findings have implications for combating the capacity-loss effects at graphite, metal-alloy, or intermetallic negative electrodes against lithium metal-oxide positive electrodes of conventional lithium-ion cells.« less
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