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Title: Effect of proton irradiation on anatase TiO2 nanotube anodes for lithium-ion batteries

Journal Article · · Journal of Materials Science

The role of defects in the charge transfer and transport properties of electrode materials for lithium-ion batteries has recently garnered increased interest. It is widely known that ion irradiation promotes the formation of defects within a crystalline solid. Within all ion species used for irradiation, protons are expected to create primarily simple Frenkel pair point defects without significantly changing the stoichiometry of the damaged region of the target material. This work investigates the effect of proton irradiation at varying temperatures on the electrochemical properties of anatase TiO2 nanotube (TiO2-NT) electrode for lithium-ion battery applications. Anatase TiO2-NTs are irradiated at both room temperature (25 °C) and 250 °C and compared with non-irradiated control specimens. Characterization by Raman spectroscopy and XRD suggests that the irradiation at both temperatures does not alter the long-range order of the nanotubes. Yet, high-resolution TEM reveals that defect clusters are formed upon irradiation and increase in size with increasing temperature. Both irradiated samples exhibit increased capacity and enhanced rate capability compared with the non-irradiated control, which can be explained by increased storage sites as well as improved Li+ diffusivity due to the presence of irradiation-induced defects. This study presents a unique perspective on pathways to engineer functional nanostructured electrode materials by tailoring irradiation conditions.

Research Organization:
Los Alamos National Laboratory (LANL), Los Alamos, NM (United States); Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Organization:
USDOE Office of Science (SC). Basic Energy Sciences (BES) (SC-22); USDOE National Nuclear Security Administration (NNSA); National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division
Grant/Contract Number:
89233218CNA000001; AC52-06NA25396; AC04-94AL85000; DMR-1408949; DMR-1838604; DMR-1838605; AC02-06CH11357
OSTI ID:
1558076
Alternate ID(s):
OSTI ID: 1566146
Report Number(s):
LA-UR-19-26408
Journal Information:
Journal of Materials Science, Vol. 54, Issue 20; ISSN 0022-2461
Publisher:
SpringerCopyright Statement
Country of Publication:
United States
Language:
English

References (90)

Nanomaterials for Rechargeable Lithium Batteries journal April 2008
Green energy storage materials: Nanostructured TiO2 and Sn-based anodes for lithium-ion batteries journal January 2009
Nanostructures and lithium electrochemical reactivity of lithium titanites and titanium oxides: A review journal July 2009
Ti-based compounds as anode materials for Li-ion batteries journal January 2012
Structural and thermal parameters for rutile and anatase journal August 1991
Lithium insertion in different TiO2 modifications journal September 1988
Nanostructured materials for advanced energy conversion and storage devices journal May 2005
Constructing Hierarchical Spheres from Large Ultrathin Anatase TiO 2 Nanosheets with Nearly 100% Exposed (001) Facets for Fast Reversible Lithium Storage journal May 2010
Lithium Storage in Nanostructured TiO 2 Made by Hydrothermal Growth journal February 2004
Size effects on mass transport and storage in lithium batteries journal December 2007
Nanostructured electrode materials for electrochemical energy storage and conversion journal January 2008
Large Impact of Particle Size on Insertion Reactions. A Case for Anatase Li x TiO 2 journal April 2007
Developments in Nanostructured Cathode Materials for High-Performance Lithium-Ion Batteries journal June 2008
Ultrafine TiO2 nanocrystalline anchored on nitrogen-doped amorphous mesoporous hollow carbon nanospheres as advanced anode for lithium ion batteries journal February 2019
Multiple phase N-doped TiO2 nanotubes/TiN/graphene nanocomposites for high rate lithium ion batteries at low temperature journal May 2019
Uniformly distributed TiO2 nanorods on reduced graphene oxide composites as anode material for high rate lithium ion batteries journal January 2019
Issues and challenges facing rechargeable lithium batteries journal November 2001
Alternative Li-Ion Battery Electrode Based on Self-Organized Titania Nanotubes journal January 2009
Effects of proton irradiation on structural and electrochemical charge storage properties of TiO 2 nanotube electrodes for lithium-ion batteries journal January 2017
Compositional Tuning of Structural Stability of Lithiated Cubic Titania via a Vacancy-Filling Mechanism under High Pressure journal February 2013
Something from Nothing: Enhancing Electrochemical Charge Storage with Cation Vacancies journal May 2012
Intercalation of Sodium Ions into Hollow Iron Oxide Nanoparticles journal January 2013
Hollow Iron Oxide Nanoparticles for Application in Lithium Ion Batteries journal April 2012
Defect generation in TiO 2 nanotube anodes via heat treatment in various atmospheres for lithium-ion batteries journal January 2018
Radiation damage evolution in ceramics journal September 2009
Characteristics of microstructural evolution of radiation damage in ceramics under fusion environment journal March 1991
Defect production in ceramics journal November 1997
Irradiation effects in amorphous ZrO 2 journal January 1973
Electron-irradiation-induced nucleation and growth in amorphous LaPO 4 , ScPO 4 , and zircon journal July 1997
Ion beam induced epitaxial recrystallization of alumina thin films deposited on sapphire journal December 1995
The crystallization of amorphous ZrO2 by thermal heating and by ion bombardment journal June 1970
Ion irradiation induced nucleation and growth of nanoparticles in amorphous silicon carbide at elevated temperatures journal July 2018
In-situ TEM study of radiation-induced amorphization and recrystallization of hydroxyapatite journal December 2018
Electron‐beam‐induced crystallization of isolated amorphous regions in Si, Ge, GaP, and GaAs journal July 1995
Transient thermal process after a high-energy heavy-ion irradiation of amorphous metals and semiconductors journal December 1992
Transient thermal processes in heavy ion irradiation of crystalline inorganic insulators journal May 2000
Models and mechanisms of irradiation-induced amorphization in ceramics journal May 2000
Cooperative effect of electronic and nuclear stopping on ion irradiation damage in silica journal November 2012
Atomistic simulations of MeV ion irradiation of silica journal May 2013
A coupled effect of nuclear and electronic energy loss on ion irradiation damage in lithium niobate journal February 2016
Ion–solid interactions at the extremes of electronic energy loss: Examples for amorphous semiconductors and embedded nanostructures journal February 2015
Effects of intermediate energy heavy‐ion irradiation on the microstructure of rutile TiO 2 single crystal journal April 2018
Ionization-induced annealing of pre-existing defects in silicon carbide journal August 2015
Synergy of inelastic and elastic energy loss: Temperature effects and electronic stopping power dependence journal January 2016
Characteristics and Photocatalytic Properties of Thin Film Prepared by Sputter Deposition and Post-N + Ion Implantation journal January 2012
Experimental and atomistic modeling study of ion irradiation damage in thin crystals of the TiO 2 polymorphs journal June 2008
Structural evolution of TiO2 nanocrystalline thin films by thermal annealing and swift heavy ion irradiation journal April 2009
Defects in rutile and anatase polymorphs of TiO 2 : kinetics and thermodynamics near grain boundaries journal September 2011
Density and structural effects in the radiation tolerance of TiO 2 polymorphs journal August 2013
Effects of Xe-ion irradiation at high temperature on single crystal rutile journal December 2002
Ion beam radiation damage effects in rutile (TiO2) journal May 1998
“Black” TiO 2 Nanotubes Formed by High-Energy Proton Implantation Show Noble-Metal- co -Catalyst Free Photocatalytic H 2 -Evolution journal September 2015
Amorphous TiO 2 Nanotube Anode for Rechargeable Sodium Ion Batteries journal September 2011
Self-Improving Anode for Lithium-Ion Batteries Based on Amorphous to Cubic Phase Transition in TiO 2 Nanotubes journal January 2012
Electropolishing valve metals with a sulfuric acid-methanol electrolyte at low temperature journal August 2018
Raman Spectroscopy for Chemical Analysis book January 2000
Raman spectra of titanium dioxide journal May 1982
Raman spectra of titanium dioxide (anatase, rutile) with identified oxygen isotopes (16, 17, 18) journal January 2012
Raman Spectra of Ti O 2 , Mg F 2 , Zn F 2 , Fe F 2 , and Mn F 2 journal February 1967
Asymmetric Lattice Vibrational Characteristics of Rutile TiO 2 as Revealed by Laser Power Dependent Raman Spectroscopy journal October 2013
Raman spectrum of anatase, TiO2 journal December 1978
Raman Line Shapes of Optical Phonons of Different Symmetries in Anatase TiO 2 Nanocrystals journal September 2009
Electron-beam induced recrystallization in amorphous apatite journal January 2007
Size dependence of radiation-induced amorphization and recrystallization of synthetic nanostructured CePO4 monazite journal May 2013
Electron irradiation induced crystallization of amorphous MgAl2O4 journal November 1996
Low energy electron-beam-induced recrystallization of continuous GaAs amorphous foils journal September 1997
Ion beam induced epitaxial crystallization of α-Al2O3 at room temperature
  • Sina, Younes; Ishimaru, Manabu; McHargue, Carl J.
  • Nuclear Instruments and Methods in Physics Research Section B: Beam Interactions with Materials and Atoms, Vol. 321 https://doi.org/10.1016/j.nimb.2013.12.012
journal February 2014
Amorphization and recrystallization of single-crystalline hydrogen titanate nanowires by N + ion irradiation journal June 2014
Radiation Response of Nanocrystalline Rutile (TiO2) journal July 2009
Nanosized Rutile (TiO 2 ) Thin Film upon Ion Irradiation and Thermal Annealing journal October 2011
Design of Radiation Tolerant Nanostructured Metallic Multilayers journal August 2012
Interface-enhanced defect absorption between epitaxial anatase TiO2 film and single crystal SrTiO3 journal November 2011
Exploring long-time response to radiation damage in MgO
  • Uberuaga, B. P.; Smith, R.; Cleave, A. R.
  • Nuclear Instruments and Methods in Physics Research Section B: Beam Interactions with Materials and Atoms, Vol. 228, Issue 1-4 https://doi.org/10.1016/j.nimb.2004.10.055
journal January 2005
Nuclear stopping power of antiprotons journal October 2017
Antiproton Slowing Down in H 2 and He and Evidence of Nuclear Stopping Power journal January 1995
Disordered 3 D Multi-layer Graphene Anode Material from CO 2 for Sodium-Ion Batteries journal April 2016
Electrochemical Impedance Spectroscopy book February 2008
Solid‐State Electrochemical Kinetics of Li‐Ion Intercalation into Li1 − xCoO2: Simultaneous Application of Electroanalytical Techniques SSCV, PITT, and EIS journal January 1999
Impedance Analysis of Silicon Nanowire Lithium Ion Battery Anodes journal June 2009
Preparation and electrochemical properties of Ag-modified TiO2 nanotube anode material for lithium–ion battery journal March 2007
Application of A-C Techniques to the Study of Lithium Diffusion in Tungsten Trioxide Thin Films journal January 1980
Structural and Kinetic Characterization of Lithium Intercalation into Carbon Anodes for Secondary Lithium Batteries journal January 1995
Remarkably improved field emission of TiO2 nanotube arrays by annealing atmosphere engineering journal October 2015
Conductivity of TiO2 nanotubes: Influence of annealing time and temperature journal July 2010
A review of conduction phenomena in Li-ion batteries journal December 2010
Radiation stability of nanoclusters in nano-structured oxide dispersion strengthened (ODS) steels journal March 2013
Thermal conductivity degradation of ceramic materials due to low temperature, low dose neutron irradiation journal April 2005
Issues and challenges facing rechargeable lithium batteries book October 2010
Characteristics of microstructural evolution of radiation damage in ceramics under fusion environment journal March 1991
Raman Spectroscopy for Chemical Analysis journal April 2001

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