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Title: Electron Transfer Governed Crystal Transformation of Tungsten Trioxide upon Li Ions Intercalation

Abstract

Reversible insertion/extraction of ions into a host lattice constitutes the fundamental operating principle of rechargeable battery and electrochromic materials. It is far more commonly observed that insertion of ions into a host lattice can lead to structural evolution of the host lattice, and for the most cases such a lattice evolution is subtle. However, it has never been clear as what kind of factors to control such a lattice structural evolution. Based on tungsten trioxide (WO3) model crystal, we use in situ transmission electron microscopy (TEM) and first principles calculation to explore the nature of Li ions intercalation induced crystal symmetry evolution of WO3. We discovered that Li insertion into the octahedral cavity of WO3 lattice will lead to a low to high symmetry transition, featuring a sequential monoclinic→tetragonal→cubic phase transition. The first principle calculation reveals that the phase transition is essentially governed by the electron transfer from Li to the WO6 octahedrons, which effectively leads to the weakening the W-O bond and modifying system band structure, resulting in an insulator to metal transition. The observation of the electronic effect on crystal symmetry and conductivity is significant, providing deep insights on the intercalation reactions in secondary rechargeable ion batteries andmore » the approach for tailoring the functionalities of material based on insertion of ions in the lattice.« less

Authors:
; ; ; ; ;
Publication Date:
Research Org.:
Pacific Northwest National Laboratory (PNNL), Richland, WA (US), Environmental Molecular Sciences Laboratory (EMSL)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1340869
Report Number(s):
PNNL-SA-120073
Journal ID: ISSN 1944-8244; 48379; KP1704020
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Resource Relation:
Journal Name: ACS Applied Materials and Interfaces; Journal Volume: 8; Journal Issue: 37
Country of Publication:
United States
Language:
English
Subject:
Tungsten trioxide; ion intercalation; phase transformation; in situ TEM; first principles calculation; electron transfer; insulator to metal transition; Environmental Molecular Sciences Laboratory

Citation Formats

Wang, Zhiguo, He, Yang, Gu, Meng, Du, Yingge, Mao, Scott X., and Wang, Chongmin. Electron Transfer Governed Crystal Transformation of Tungsten Trioxide upon Li Ions Intercalation. United States: N. p., 2016. Web. doi:10.1021/acsami.6b06581.
Wang, Zhiguo, He, Yang, Gu, Meng, Du, Yingge, Mao, Scott X., & Wang, Chongmin. Electron Transfer Governed Crystal Transformation of Tungsten Trioxide upon Li Ions Intercalation. United States. doi:10.1021/acsami.6b06581.
Wang, Zhiguo, He, Yang, Gu, Meng, Du, Yingge, Mao, Scott X., and Wang, Chongmin. Wed . "Electron Transfer Governed Crystal Transformation of Tungsten Trioxide upon Li Ions Intercalation". United States. doi:10.1021/acsami.6b06581.
@article{osti_1340869,
title = {Electron Transfer Governed Crystal Transformation of Tungsten Trioxide upon Li Ions Intercalation},
author = {Wang, Zhiguo and He, Yang and Gu, Meng and Du, Yingge and Mao, Scott X. and Wang, Chongmin},
abstractNote = {Reversible insertion/extraction of ions into a host lattice constitutes the fundamental operating principle of rechargeable battery and electrochromic materials. It is far more commonly observed that insertion of ions into a host lattice can lead to structural evolution of the host lattice, and for the most cases such a lattice evolution is subtle. However, it has never been clear as what kind of factors to control such a lattice structural evolution. Based on tungsten trioxide (WO3) model crystal, we use in situ transmission electron microscopy (TEM) and first principles calculation to explore the nature of Li ions intercalation induced crystal symmetry evolution of WO3. We discovered that Li insertion into the octahedral cavity of WO3 lattice will lead to a low to high symmetry transition, featuring a sequential monoclinic→tetragonal→cubic phase transition. The first principle calculation reveals that the phase transition is essentially governed by the electron transfer from Li to the WO6 octahedrons, which effectively leads to the weakening the W-O bond and modifying system band structure, resulting in an insulator to metal transition. The observation of the electronic effect on crystal symmetry and conductivity is significant, providing deep insights on the intercalation reactions in secondary rechargeable ion batteries and the approach for tailoring the functionalities of material based on insertion of ions in the lattice.},
doi = {10.1021/acsami.6b06581},
journal = {ACS Applied Materials and Interfaces},
number = 37,
volume = 8,
place = {United States},
year = {Wed Sep 21 00:00:00 EDT 2016},
month = {Wed Sep 21 00:00:00 EDT 2016}
}