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Title: A scheme for the generation of Fe–P networks to search for low-energy LiFePO 4 crystal structures

Abstract

Herein we present a network generation scheme to explore the structural diversity of LiFePO 4, which is an important cathode material in Li-ion batteries. With our scheme, networks of Fe and P atoms were initially constructed as the backbone structures using structural motifs for the FeP x and FeP x configurations, obtained from existing structural databases. Then, O atoms were added, resulting in the formation of PO 4 tetrahedra and different types of Fe–O polyhedra. Finally, Li atoms were inserted into the vacancies within the generated FePO 4 structures. We searched structures with FeO 4, FeO 5, or FeO 6 polyhedra (unit cell with sizes of up to 4 formula units) and obtained ~8 times more low-energy structures through our database than through existing databases. Furthermore, using our more comprehensive structural database, we unveiled a number of rules for identifying low-energy structures. These improved results complement the existing databases and are valuable for further research on structural transformations in similar materials by changing lithium or sodium cation populations.

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3];  [4]; ORCiD logo [2]; ORCiD logo [2];  [1];  [1];  [2];  [4]
  1. CAS Key Laboratory of Strongly-Coupled Quantum Matter Physics; Department of Physics; University of Science and Technology of China; Hefei 230026; China
  2. Ames Laboratory; US DOE; Ames; USA
  3. Collaborative Innovation Center for Optoelectronic Semiconductors and Efficient Devices; Department of Physics; Xiamen University; Xiamen 361005; China
  4. International Center for Quantum Design of Functional Materials (ICQD); Hefei National Laboratory for Physical Sciences at the Microscale; University of Science and Technology of China; Hefei 230026; China
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory-National Energy Research Scientific Computing Center
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division
OSTI Identifier:
1493602
DOE Contract Number:  
AC02-07CH11358
Resource Type:
Journal Article
Journal Name:
Journal of Materials Chemistry. A
Additional Journal Information:
Journal Volume: 5; Journal Issue: 28; Journal ID: ISSN 2050-7488
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English

Citation Formats

Lv, Xiaobao, Zhao, Xin, Wu, Shunqing, Wu, Ping, Sun, Yang, Nguyen, Manh Cuong, Shi, Yongliang, Lin, Zijing, Wang, Cai-Zhuang, and Ho, Kai-Ming. A scheme for the generation of Fe–P networks to search for low-energy LiFePO4 crystal structures. United States: N. p., 2017. Web. doi:10.1039/c7ta02532g.
Lv, Xiaobao, Zhao, Xin, Wu, Shunqing, Wu, Ping, Sun, Yang, Nguyen, Manh Cuong, Shi, Yongliang, Lin, Zijing, Wang, Cai-Zhuang, & Ho, Kai-Ming. A scheme for the generation of Fe–P networks to search for low-energy LiFePO4 crystal structures. United States. doi:10.1039/c7ta02532g.
Lv, Xiaobao, Zhao, Xin, Wu, Shunqing, Wu, Ping, Sun, Yang, Nguyen, Manh Cuong, Shi, Yongliang, Lin, Zijing, Wang, Cai-Zhuang, and Ho, Kai-Ming. Sun . "A scheme for the generation of Fe–P networks to search for low-energy LiFePO4 crystal structures". United States. doi:10.1039/c7ta02532g.
@article{osti_1493602,
title = {A scheme for the generation of Fe–P networks to search for low-energy LiFePO4 crystal structures},
author = {Lv, Xiaobao and Zhao, Xin and Wu, Shunqing and Wu, Ping and Sun, Yang and Nguyen, Manh Cuong and Shi, Yongliang and Lin, Zijing and Wang, Cai-Zhuang and Ho, Kai-Ming},
abstractNote = {Herein we present a network generation scheme to explore the structural diversity of LiFePO4, which is an important cathode material in Li-ion batteries. With our scheme, networks of Fe and P atoms were initially constructed as the backbone structures using structural motifs for the FePx and FePx configurations, obtained from existing structural databases. Then, O atoms were added, resulting in the formation of PO4 tetrahedra and different types of Fe–O polyhedra. Finally, Li atoms were inserted into the vacancies within the generated FePO4 structures. We searched structures with FeO4, FeO5, or FeO6 polyhedra (unit cell with sizes of up to 4 formula units) and obtained ~8 times more low-energy structures through our database than through existing databases. Furthermore, using our more comprehensive structural database, we unveiled a number of rules for identifying low-energy structures. These improved results complement the existing databases and are valuable for further research on structural transformations in similar materials by changing lithium or sodium cation populations.},
doi = {10.1039/c7ta02532g},
journal = {Journal of Materials Chemistry. A},
issn = {2050-7488},
number = 28,
volume = 5,
place = {United States},
year = {2017},
month = {1}
}

Works referenced in this record:

‘Crystal Genes’ in Metallic Liquids and Glasses
journal, March 2016

  • Sun, Yang; Zhang, Feng; Ye, Zhuo
  • Scientific Reports, Vol. 6, Issue 1
  • DOI: 10.1038/srep23734

Review of LiFePO 4 Phase Transition Mechanisms and New Observations from X-ray Absorption Spectroscopy
journal, January 2013

  • Love, Corey T.; Korovina, Anna; Patridge, Christopher J.
  • Journal of The Electrochemical Society, Vol. 160, Issue 5
  • DOI: 10.1149/2.023305jes

A Critical Review of the Li Insertion Mechanisms in LiFePO 4 Electrodes
journal, January 2013

  • Malik, Rahul; Abdellahi, Aziz; Ceder, Gerbrand
  • Journal of The Electrochemical Society, Vol. 160, Issue 5
  • DOI: 10.1149/2.029305jes

Molecular Geometry Optimization with a Genetic Algorithm
journal, July 1995


Robust diamond-like Fe-Si network in the zero-strain Na FeSiO4 cathode
journal, September 2016


Fe–Si networks in Na 2 FeSiO 4 cathode materials
journal, January 2016

  • Wu, P.; Wu, S. Q.; Lv, X.
  • Physical Chemistry Chemical Physics, Vol. 18, Issue 34
  • DOI: 10.1039/C6CP05135A

Developments of lithium-ion batteries and challenges of LiFePO4 as one promising cathode material
journal, May 2009


Lithium batteries: Status, prospects and future
journal, May 2010


Generalized Gradient Approximation Made Simple [Phys. Rev. Lett. 77, 3865 (1996)]
journal, February 1997


Exploration of tetrahedral structures in silicate cathodes using a motif-network scheme
journal, October 2015

  • Zhao, Xin; Wu, Shunqing; Lv, Xiaobao
  • Scientific Reports, Vol. 5, Issue 1
  • DOI: 10.1038/srep15555

Inorganic structure prediction with GRINSP
journal, March 2005


Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996


First principles phonon calculations in materials science
journal, November 2015


Phospho-olivines as Positive-Electrode Materials for Rechargeable Lithium Batteries
journal, April 1997

  • Padhi, A. K.
  • Journal of The Electrochemical Society, Vol. 144, Issue 4, p. 1188-1194
  • DOI: 10.1149/1.1837571

Fast Parallel Algorithms for Short-Range Molecular Dynamics
journal, March 1995


Embedded-atom method: Derivation and application to impurities, surfaces, and other defects in metals
journal, June 1984


Commentary: The Materials Project: A materials genome approach to accelerating materials innovation
journal, July 2013

  • Jain, Anubhav; Ong, Shyue Ping; Hautier, Geoffroy
  • APL Materials, Vol. 1, Issue 1
  • DOI: 10.1063/1.4812323

Olivine LiFePO 4 : the remaining challenges for future energy storage
journal, January 2015

  • Wang, Jiajun; Sun, Xueliang
  • Energy & Environmental Science, Vol. 8, Issue 4
  • DOI: 10.1039/C4EE04016C

VESTA 3 for three-dimensional visualization of crystal, volumetric and morphology data
journal, October 2011


Electron-energy-loss spectra and the structural stability of nickel oxide: An LSDA+U study
journal, January 1998

  • Dudarev, S. L.; Botton, G. A.; Savrasov, S. Y.
  • Physical Review B, Vol. 57, Issue 3, p. 1505-1509
  • DOI: 10.1103/PhysRevB.57.1505