Search Menu
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information
Search Scholarly Publications

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 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 lithiummore » 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:
 [1];  [1];  [1];  [2];  [3];  [3];  [4];  [5];  [5];  [6]; ORCiD logo [1]
+ Show Author Affiliations
  1. Boise State Univ., ID (United States)
  2. Purdue Univ., West Lafayette, IN (United States)
  3. Brookhaven National Lab. (BNL), Upton, NY (United States)
  4. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
  5. Northern Illinois Univ., DeKalb, IL (United States)
  6. Univ. of Utah, Salt Lake City, UT (United States)
Publication Date:
Research Org.:
Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)
Sponsoring Org.:
USDOE Office of Science (SC). Basic Energy Sciences (BES) (SC-22); USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1427393
Alternate Identifier(s):
OSTI ID: 1351743
Report Number(s):
LA-UR-18-21408; BNL-113759-2017-JA
Journal ID: ISSN 2050-7488; JMCAET; TRN: US1802857
Grant/Contract Number:  
AC52-06NA25396; SC00112704
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Materials Chemistry. A
Additional Journal Information:
Journal Volume: 5; Journal Issue: 23; Journal ID: ISSN 2050-7488
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; Material Science; 29 ENERGY PLANNING, POLICY, AND ECONOMY; TiO2; lithium ion battery; proton Irradiation; Center for Functional Nanomaterials

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.
Copy to clipboard
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. https://doi.org/10.1039/C7TA01026E
Copy to clipboard
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. https://doi.org/10.1039/C7TA01026E. https://www.osti.gov/servlets/purl/1427393.
Copy to clipboard
@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 = 23,
volume = 5,
place = {United States},
year = {Thu Mar 23 00:00:00 EDT 2017},
month = {Thu Mar 23 00:00:00 EDT 2017}
}
Copy to clipboard
Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1039/C7TA01026E
Copyright Statement
Other availability
Search WorldCat Search WorldCat to find libraries that may hold this journal
Citation Metrics:
Cited by: 33 works
Citation information provided by
Web of Science
Save / Share:
Export Metadata
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.

Works referenced in this record:

Something from Nothing: Enhancing Electrochemical Charge Storage with Cation Vacancies
journal, May 2012

  • Hahn, Benjamin P.; Long, Jeffrey W.; Rolison, Debra R.
  • Accounts of Chemical Research, Vol. 46, Issue 5
  • DOI: 10.1021/ar200238w

Multiple Li Positions inside Oxygen Octahedra in Lithiated TiO 2 Anatase
journal, January 2003

  • Wagemaker, Marnix; Kearley, Gordon J.; van Well, Ad A.
  • Journal of the American Chemical Society, Vol. 125, Issue 3
  • DOI: 10.1021/ja028165q

TiO2 nanotubes: Self-organized electrochemical formation, properties and applications
journal, February 2007

  • Macak, J. M.; Tsuchiya, H.; Ghicov, A.
  • Current Opinion in Solid State and Materials Science, Vol. 11, Issue 1-2
  • DOI: 10.1016/j.cossms.2007.08.004

Lithium Storage in Nanostructured TiO 2 Made by Hydrothermal Growth
journal, February 2004

  • Kavan, Ladislav; Kalbáč, Martin; Zukalová, Markéta
  • Chemistry of Materials, Vol. 16, Issue 3
  • DOI: 10.1021/cm035046g

Ti and O K edges for titanium oxides by multiple scattering calculations: Comparison to XAS and EELS spectra
journal, April 1997

Ti-based compounds as anode materials for Li-ion batteries
journal, January 2012

  • Zhu, Guan-Nan; Wang, Yong-Gang; Xia, Yong-Yao
  • Energy & Environmental Science, Vol. 5, Issue 5
  • DOI: 10.1039/c2ee03410g

Compositional Tuning of Structural Stability of Lithiated Cubic Titania via a Vacancy-Filling Mechanism under High Pressure
journal, February 2013

Photocatalytic activity study of TiO2 thin films with and without Fe ion implantation
journal, April 2002

  • Zheng, S. K.; Wang, T. M.; Wang, C.
  • Nuclear Instruments and Methods in Physics Research Section B: Beam Interactions with Materials and Atoms, Vol. 187, Issue 4
  • DOI: 10.1016/S0168-583X(01)01159-4

Nanostructures and lithium electrochemical reactivity of lithium titanites and titanium oxides: A review
journal, July 2009

Pseudocapacitive oxide materials for high-rate electrochemical energy storage
journal, January 2014

  • Augustyn, Veronica; Simon, Patrice; Dunn, Bruce
  • Energy & Environmental Science, Vol. 7, Issue 5
  • DOI: 10.1039/c3ee44164d

Size effects on mass transport and storage in lithium batteries
journal, December 2007

Improvement of photocatalytic activity of TiO2 thin film by Sn ion implantation
journal, April 2002

Electronic structure of titania-based nanotubes investigated by EELS spectroscopy
journal, July 2009

Electrochemical energy storage to power the 21st century
journal, July 2011

Synthesis and Li-Ion Insertion Properties of Highly Crystalline Mesoporous Rutile TiO 2
journal, May 2008

  • Wang, Donghai; Choi, Daiwon; Yang, Zhenguo
  • Chemistry of Materials, Vol. 20, Issue 10
  • DOI: 10.1021/cm8002589

Unlocking the Potential of Cation-Disordered Oxides for Rechargeable Lithium Batteries
journal, January 2014

Ion implantation in TiO2: damage production and recovery, lattice site location and electrical conductivity
journal, January 1999

  • Fromknecht, R.; Khubeis, I.; Massing, S.
  • Nuclear Instruments and Methods in Physics Research Section B: Beam Interactions with Materials and Atoms, Vol. 147, Issue 1-4
  • DOI: 10.1016/S0168-583X(98)00551-5

Large Impact of Particle Size on Insertion Reactions. A Case for Anatase Li x TiO 2
journal, April 2007

  • Wagemaker, Marnix; Borghols, Wouter J. H.; Mulder, Fokko M.
  • Journal of the American Chemical Society, Vol. 129, Issue 14
  • DOI: 10.1021/ja067733p

Track creation in SiO2 and BaFe12O19 by swift heavy ions: a thermal spike description
journal, August 1996

  • Toulemonde, M.; Costantini, J. M.; Dufour, Ch.
  • Nuclear Instruments and Methods in Physics Research Section B: Beam Interactions with Materials and Atoms, Vol. 116, Issue 1-4
  • DOI: 10.1016/0168-583X(96)00007-9

Nanomaterials for Rechargeable Lithium Batteries
journal, April 2008

  • Bruce, Peter G.; Scrosati, Bruno; Tarascon, Jean-Marie
  • Angewandte Chemie International Edition, Vol. 47, Issue 16, p. 2930-2946
  • DOI: 10.1002/anie.200702505

Intercalation of Sodium Ions into Hollow Iron Oxide Nanoparticles
journal, January 2013

  • Koo, Bonil; Chattopadhyay, Soma; Shibata, Tomohiro
  • Chemistry of Materials, Vol. 25, Issue 2, p. 245-252
  • DOI: 10.1021/cm303611z

Characteristics and Photocatalytic Properties of Thin Film Prepared by Sputter Deposition and Post-N + Ion Implantation
journal, January 2012

  • Shukur, Haider A.; Sato, Mitsunobu; Nakamura, Isao
  • Advances in Materials Science and Engineering, Vol. 2012
  • DOI: 10.1155/2012/923769

Effect of Diffusion on Lithium Intercalation in Titanium Dioxide
journal, February 2001

  • Koudriachova, Marina V.; Harrison, Nicholas M.; de Leeuw, Simon W.
  • Physical Review Letters, Vol. 86, Issue 7
  • DOI: 10.1103/PhysRevLett.86.1275

High Lithium Electroactivity of Nanometer-Sized Rutile TiO2
journal, June 2006

  • Hu, Y.-S.; Kienle, L.; Guo, Y.-G.
  • Advanced Materials, Vol. 18, Issue 11, p. 1421-1426
  • DOI: 10.1002/adma.200502723

Synthesis and electrochemical evaluation of an amorphous titanium dioxide derived from a solid state precursor
journal, April 2010

Ag/Fe:TiO2 nano-catalysts prepared by Fe ion implantation and Ag nanoparticle deposition by electron beam irradiation
journal, April 2009

  • Qin, Li-Zhao; Liao, Bin; Dong, Xi-Liang
  • Nuclear Instruments and Methods in Physics Research Section B: Beam Interactions with Materials and Atoms, Vol. 267, Issue 7
  • DOI: 10.1016/j.nimb.2009.01.049

Fabrication, characterization and Raman study of TiO2 nanowire arrays prepared by anodic oxidative hydrolysis of TiCl3
journal, April 2001

Raman Line Shapes of Optical Phonons of Different Symmetries in Anatase TiO 2 Nanocrystals
journal, September 2009

  • Sahoo, Satyaprakash; Arora, A. K.; Sridharan, V.
  • The Journal of Physical Chemistry C, Vol. 113, Issue 39
  • DOI: 10.1021/jp9046193

Raman Spectra of Ti O 2 , Mg F 2 , Zn F 2 , Fe F 2 , and Mn F 2
journal, February 1967

Amorphous TiO 2 Nanotube Anode for Rechargeable Sodium Ion Batteries
journal, September 2011

  • Xiong, Hui; Slater, Michael D.; Balasubramanian, Mahalingam
  • The Journal of Physical Chemistry Letters, Vol. 2, Issue 20
  • DOI: 10.1021/jz2012066

High-capacity lithium insertion materials of lithium nickel manganese oxides for advanced lithium-ion batteries: toward rechargeable capacity more than 300 mA h g−1
journal, January 2011

  • Ohzuku, Tsutomu; Nagayama, Masatoshi; Tsuji, Kyoji
  • Journal of Materials Chemistry, Vol. 21, Issue 27
  • DOI: 10.1039/c0jm04325g

Structural evolution during the reaction of Li with nano-sized rutile type TiO2 at room temperature
journal, February 2007

Hollow Iron Oxide Nanoparticles for Application in Lithium Ion Batteries
journal, April 2012

  • Koo, Bonil; Xiong, Hui; Slater, Michael D.
  • Nano Letters, Vol. 12, Issue 5, p. 2429-2435
  • DOI: 10.1021/nl3004286

Ion beam radiation damage effects in rutile (TiO2)
journal, May 1998

  • Hartmann, T.; Wang, L. M.; Weber, W. J.
  • Nuclear Instruments and Methods in Physics Research Section B: Beam Interactions with Materials and Atoms, Vol. 141, Issue 1-4
  • DOI: 10.1016/S0168-583X(98)00134-7

Ion implantation in TiO2: Effect of the charge state on the lattice site occupation
journal, March 1998

  • Meyer, O.; Khubeis, I.; Fromknecht, R.
  • Nuclear Instruments and Methods in Physics Research Section B: Beam Interactions with Materials and Atoms, Vol. 136-138
  • DOI: 10.1016/S0168-583X(97)00866-5

Uncovering the roles of oxygen vacancies in cation migration in lithium excess layered oxides
journal, January 2014

  • Qian, Danna; Xu, Bo; Chi, Miaofang
  • Phys. Chem. Chem. Phys., Vol. 16, Issue 28
  • DOI: 10.1039/C4CP01799D

Nanoscale phase transitions under extreme conditions within an ion track
journal, July 2010

  • Zhang, Jiaming; Lang, Maik; Ewing, Rodney C.
  • Journal of Materials Research, Vol. 25, Issue 7
  • DOI: 10.1557/JMR.2010.0180

Developments in Nanostructured Cathode Materials for High-Performance Lithium-Ion Batteries
journal, June 2008

A relationship between structural and electronic order–disorder effects and optical properties in crystalline TiO 2 nanomaterials
journal, January 2015

  • Silva Junior, E.; La Porta, F. A.; Liu, M. S.
  • Dalton Transactions, Vol. 44, Issue 7
  • DOI: 10.1039/C4DT03254C

High-Quality Brookite TiO2 Flowers: Synthesis, Characterization, and Dielectric Performance
journal, August 2009

  • Hu, Wanbiao; Li, Liping; Li, Guangshe
  • Crystal Growth & Design, Vol. 9, Issue 8, p. 3676-3682
  • DOI: 10.1021/cg9004032

N ion irradiation enhancement of photocatalytic activity of TiO2
journal, May 2009

  • Matsunami, N.; Uebayashi, M.; Hirooka, K.
  • Nuclear Instruments and Methods in Physics Research Section B: Beam Interactions with Materials and Atoms, Vol. 267, Issue 8-9
  • DOI: 10.1016/j.nimb.2009.01.097

Engineering nano-composite Li4Ti5O12 anodes via scanning electron-probe fabrication
journal, May 2013

Quantification of crystalline and amorphous content in porous samples from electron energy loss spectroscopy
journal, May 2006

Nonlinear size dependence of anatase TiO2 lattice parameters
journal, June 2006

  • Swamy, Varghese; Menzies, David; Muddle, Barry C.
  • Applied Physics Letters, Vol. 88, Issue 24
  • DOI: 10.1063/1.2213956

FT-Raman Spectroscopic Studies of the Degradation of Titanium Peroxy Gels Made from Metallic Titanium and Hydrogen Peroxide
journal, October 1993

  • Tengvall, Pentti; Vikinge, Trine Platou; Lundström, Ingemar
  • Journal of Colloid and Interface Science, Vol. 160, Issue 1
  • DOI: 10.1006/jcis.1993.1362

Nanostructured materials for advanced energy conversion and storage devices
journal, May 2005

  • Aricò, Antonino Salvatore; Bruce, Peter; Scrosati, Bruno
  • Nature Materials, Vol. 4, Issue 5, p. 366-377
  • DOI: 10.1038/nmat1368

Li2MnO3-stabilized LiMO2 (M = Mn, Ni, Co) electrodes for lithium-ion batteries
journal, January 2007

  • Thackeray, Michael M.; Kang, Sun-Ho; Johnson, Christopher S.
  • Journal of Materials Chemistry, Vol. 17, Issue 30, p. 3112-3125
  • DOI: 10.1039/b702425h

Pseudocapacitive Contributions to Electrochemical Energy Storage in TiO2 (Anatase) Nanoparticles
journal, October 2007

  • Wang, John; Polleux, Julien; Lim, James
  • The Journal of Physical Chemistry C, Vol. 111, Issue 40, p. 14925-14931
  • DOI: 10.1021/jp074464w

Effects of As + ion implantation on the Raman spectra of GaAs: ‘‘Spatial correlation’’ interpretation
journal, January 1984

  • Tiong, K. K.; Amirtharaj, P. M.; Pollak, F. H.
  • Applied Physics Letters, Vol. 44, Issue 1
  • DOI: 10.1063/1.94541

Self-Improving Anode for Lithium-Ion Batteries Based on Amorphous to Cubic Phase Transition in TiO 2 Nanotubes
journal, January 2012

  • Xiong, Hui; Yildirim, Handan; Shevchenko, Elena V.
  • The Journal of Physical Chemistry C, Vol. 116, Issue 4
  • DOI: 10.1021/jp210793u

Nanostructured electrode materials for electrochemical energy storage and conversion
journal, January 2008

  • Manthiram, A.; Vadivel Murugan, A.; Sarkar, A.
  • Energy & Environmental Science, Vol. 1, Issue 6
  • DOI: 10.1039/b811802g

A thermal spike model for nanophase formation in yttrium iron garnet under swift heavy ion beams
journal, February 1997

  • Costantini, J. M.; Brisard, F.; Toulemonde, M.
  • Nuclear Instruments and Methods in Physics Research Section B: Beam Interactions with Materials and Atoms, Vol. 122, Issue 3
  • DOI: 10.1016/S0168-583X(96)00669-6

Constructing Hierarchical Spheres from Large Ultrathin Anatase TiO 2 Nanosheets with Nearly 100% Exposed (001) Facets for Fast Reversible Lithium Storage
journal, May 2010

  • Chen, Jun Song; Tan, Yi Ling; Li, Chang Ming
  • Journal of the American Chemical Society, Vol. 132, Issue 17
  • DOI: 10.1021/ja100102y

Lithium insertion in different TiO2 modifications
journal, September 1988

Size-dependent modifications of the Raman spectrum of rutile TiO2
journal, October 2006

  • Swamy, Varghese; Muddle, Barry C.; Dai, Qing
  • Applied Physics Letters, Vol. 89, Issue 16
  • DOI: 10.1063/1.2364123

Green energy storage materials: Nanostructured TiO2 and Sn-based anodes for lithium-ion batteries
journal, January 2009

  • Deng, Da; Kim, Min Gyu; Lee, Jim Yang
  • Energy & Environmental Science, Vol. 2, Issue 8, p. 818-837
  • DOI: 10.1039/b823474d

Ions implanted into TiO2 rutile single crystals: Lattice disorder, lattice site occupation and conductivity
journal, May 1997

  • Meyer, O.; Khubeis, I.; Fromknecht, R.
  • Nuclear Instruments and Methods in Physics Research Section B: Beam Interactions with Materials and Atoms, Vol. 127-128
  • DOI: 10.1016/S0168-583X(96)01137-8

Li + Ion Insertion in TiO 2 (Anatase). 2. Voltammetry on Nanoporous Films
journal, September 1997

  • Lindström, Henrik; Södergren, Sven; Solbrand, Anita
  • The Journal of Physical Chemistry B, Vol. 101, Issue 39
  • DOI: 10.1021/jp970490q

Finite-size and pressure effects on the Raman spectrum of nanocrystalline anatase Ti O 2
journal, May 2005

    Sort by:
    [ × clear filter / sort ]

    Works referencing / citing this record:

    Effect of proton irradiation on anatase TiO2 nanotube anodes for lithium-ion batteries
    journal, July 2019

    • Smith, Kassiopeia A.; Savva, Andreas I.; Mao, Keyou S.
    • Journal of Materials Science, Vol. 54, Issue 20
    • DOI: 10.1007/s10853-019-03825-w

    A mechanistic study of mesoporous TiO 2 nanoparticle negative electrode materials with varying crystallinity for lithium ion batteries
    journal, January 2020

    • Deng, Changjian; Lau, Miu Lun; Ma, Chunrong
    • Journal of Materials Chemistry A, Vol. 8, Issue 6
    • DOI: 10.1039/c9ta12499c

    TiO 2 nanotubes with different spacing, Fe 2 O 3 decoration and their evaluation for Li-ion battery application
    journal, March 2018

    Modification Induced by Proton Irradiation in Bayfol uv1 7-2 Nuclear Track Detector
    journal, December 2018

    • Nouh, S. A.; Gaballah, N.; Abou Elfadl, A.
    • Radiation Protection Dosimetry, Vol. 183, Issue 4
    • DOI: 10.1093/rpd/ncy165

    Effects of intermediate energy heavy‐ion irradiation on the microstructure of rutile TiO 2 single crystal
    journal, April 2018

    • Smith, Kassiopeia A.; Savva, Andreas I.; Wu, Yaqiao
    • Journal of the American Ceramic Society, Vol. 101, Issue 9
    • DOI: 10.1111/jace.15576
      Sort by:
      [ × clear filter / sort ]

      Similar Records in DOE PAGES and OSTI.GOV collections: