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Title: Mechanism of electrochemical lithiation of a metal-organic framework without redox-active nodes

Abstract

Metal-organic frameworks (MOFs) have many potential uses for separations, storage, and catalysis, but their use as intercalation hosts for batteries has been scarce. In this article, we examine the mechanism of Li insertion in a MOF to provide guidance to future design efforts in this area. As a model system, we choose UiO-66, a MOF with the formula (Zr6O4(OH)4)4 (1,4-benzenedicarboxylate)6, as an electrode material for lithium-ion batteries; this MOF is of special interest because the zirconium is not redox active. We report both quantum mechanical characterization of the mechanism and experimental studies in which the material is synthesized as nanoparticles to reduce diffusion lengths for lithium ions and increase the contact area with a conductive carbon phase. The calculated changes in the IR spectra of UiO-66 and lithiated UiO-66 are consistent with the experimental FTIR results. Here we found experimentally that this MOF can maintain a specific discharge capacity of at least 118 mAh/g for 30 lithiation and delithiation cycles at a rate of C/5, exhibiting good cyclability. Density functional electronic structure calculations show that the charge transfer during lithiation is mainly from Li to node oxygens and carboxylate oxygens, that is, it involves anions rather than cations or aromaticmore » rings, and they provide a mechanistic understanding of the potential for increased Li capacity because the theoretical capacity of UiO-66 with Li at the oxygens in the metal oxide nodes and the carboxylate linkers is more than 400 mAh/g. The lithiation process greatly decreases the bandgap of UiO-66, which is expected to increase its electronic conductivity. Finally, the electrode material was also characterized by X-ray diffraction and scanning electron microscopy, which were consistent in confirming that smaller particle sizes were obtained in lower-temperature syntheses.« less

Authors:
 [1]; ORCiD logo [2];  [3];  [3];  [3]; ORCiD logo [2];  [3]
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  1. Shanghai Univ. of Engineering Science, Shanghai (China). College of Chemistry and Chemical Engineering; Univ. of Minnesota, Minneapolis, MN (United States). Dept. of Chemistry
  2. Univ. of Minnesota, Minneapolis, MN (United States). Dept. of Chemistry, and Dept. of Chemistry, Chemical Theory Center, and Supercomputing Inst.
  3. Univ. of Minnesota, Minneapolis, MN (United States). Dept. of Chemistry
Publication Date:
Research Org.:
Univ. of Minnesota, Minneapolis, MN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1471092
Alternate Identifier(s):
OSTI ID: 1253396
Grant/Contract Number:  
SC0008662; AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 144; Journal Issue: 19; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE

Citation Formats

Tang, Bohejin, Huang, Shuping, Fang, Yuan, Hu, Jinbo, Malonzo, Camille, Truhlar, Donald G., and Stein, Andreas. Mechanism of electrochemical lithiation of a metal-organic framework without redox-active nodes. United States: N. p., 2016. Web. doi:10.1063/1.4948706.
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Tang, Bohejin, Huang, Shuping, Fang, Yuan, Hu, Jinbo, Malonzo, Camille, Truhlar, Donald G., & Stein, Andreas. Mechanism of electrochemical lithiation of a metal-organic framework without redox-active nodes. United States. https://doi.org/10.1063/1.4948706
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Tang, Bohejin, Huang, Shuping, Fang, Yuan, Hu, Jinbo, Malonzo, Camille, Truhlar, Donald G., and Stein, Andreas. Tue . "Mechanism of electrochemical lithiation of a metal-organic framework without redox-active nodes". United States. https://doi.org/10.1063/1.4948706. https://www.osti.gov/servlets/purl/1471092.
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@article{osti_1471092,
title = {Mechanism of electrochemical lithiation of a metal-organic framework without redox-active nodes},
author = {Tang, Bohejin and Huang, Shuping and Fang, Yuan and Hu, Jinbo and Malonzo, Camille and Truhlar, Donald G. and Stein, Andreas},
abstractNote = {Metal-organic frameworks (MOFs) have many potential uses for separations, storage, and catalysis, but their use as intercalation hosts for batteries has been scarce. In this article, we examine the mechanism of Li insertion in a MOF to provide guidance to future design efforts in this area. As a model system, we choose UiO-66, a MOF with the formula (Zr6O4(OH)4)4 (1,4-benzenedicarboxylate)6, as an electrode material for lithium-ion batteries; this MOF is of special interest because the zirconium is not redox active. We report both quantum mechanical characterization of the mechanism and experimental studies in which the material is synthesized as nanoparticles to reduce diffusion lengths for lithium ions and increase the contact area with a conductive carbon phase. The calculated changes in the IR spectra of UiO-66 and lithiated UiO-66 are consistent with the experimental FTIR results. Here we found experimentally that this MOF can maintain a specific discharge capacity of at least 118 mAh/g for 30 lithiation and delithiation cycles at a rate of C/5, exhibiting good cyclability. Density functional electronic structure calculations show that the charge transfer during lithiation is mainly from Li to node oxygens and carboxylate oxygens, that is, it involves anions rather than cations or aromatic rings, and they provide a mechanistic understanding of the potential for increased Li capacity because the theoretical capacity of UiO-66 with Li at the oxygens in the metal oxide nodes and the carboxylate linkers is more than 400 mAh/g. The lithiation process greatly decreases the bandgap of UiO-66, which is expected to increase its electronic conductivity. Finally, the electrode material was also characterized by X-ray diffraction and scanning electron microscopy, which were consistent in confirming that smaller particle sizes were obtained in lower-temperature syntheses.},
doi = {10.1063/1.4948706},
journal = {Journal of Chemical Physics},
number = 19,
volume = 144,
place = {United States},
year = {Tue May 17 00:00:00 EDT 2016},
month = {Tue May 17 00:00:00 EDT 2016}
}
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Works referenced in this record:

Mixed-Valence Li/Fe-Based Metal–Organic Frameworks with Both Reversible Redox and Sorption Properties
journal, April 2007

  • Férey, Gérard; Millange, Franck; Morcrette, Mathieu
  • Angewandte Chemie International Edition, Vol. 46, Issue 18
  • DOI: 10.1002/anie.200605163

Generalized Gradient Approximation Made Simple
journal, October 1996

  • Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
  • Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
  • DOI: 10.1103/PhysRevLett.77.3865

High-capacity organic positive-electrode material based on a benzoquinone derivative for use in rechargeable lithium batteries
journal, December 2010

Influence of the Benzoquinone Sorption on the Structure and Electrochemical Performance of the MIL-53(Fe) Hybrid Porous Material in a Lithium-Ion Battery
journal, April 2009

  • de Combarieu, G.; Morcrette, M.; Millange, F.
  • Chemistry of Materials, Vol. 21, Issue 8
  • DOI: 10.1021/cm8032324

Projector augmented-wave method
journal, December 1994

Ionic Conductivity in the Metal-Organic Framework UiO-66 by Dehydration and Insertion of Lithium tert -Butoxide
journal, March 2013

  • Ameloot, Rob; Aubrey, Michael; Wiers, Brian M.
  • Chemistry - A European Journal, Vol. 19, Issue 18
  • DOI: 10.1002/chem.201300326

Hybrid functionals based on a screened Coulomb potential
journal, May 2003

  • Heyd, Jochen; Scuseria, Gustavo E.; Ernzerhof, Matthias
  • The Journal of Chemical Physics, Vol. 118, Issue 18
  • DOI: 10.1063/1.1564060

Metal-organic frameworks for lithium ion batteries and supercapacitors
journal, March 2015

Ion Conductivity and Transport by Porous Coordination Polymers and Metal–Organic Frameworks
journal, June 2013

  • Horike, Satoshi; Umeyama, Daiki; Kitagawa, Susumu
  • Accounts of Chemical Research, Vol. 46, Issue 11
  • DOI: 10.1021/ar300291s

Disclosing the Complex Structure of UiO-66 Metal Organic Framework: A Synergic Combination of Experiment and Theory
journal, April 2011

  • Valenzano, Loredana; Civalleri, Bartolomeo; Chavan, Sachin
  • Chemistry of Materials, Vol. 23, Issue 7, p. 1700-1718
  • DOI: 10.1021/cm1022882

From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999

Conjugated dicarboxylate anodes for Li-ion batteries
journal, January 2009

  • Armand, M.; Grugeon, S.; Vezin, H.
  • Nature Materials, Vol. 8, Issue 2, p. 120-125
  • DOI: 10.1038/nmat2372

MIL-101(Fe) as a lithium-ion battery electrode material: a relaxation and intercalation mechanism during lithium insertion
journal, January 2015

  • Shin, JaeWook; Kim, Min; Cirera, Jordi
  • Journal of Materials Chemistry A, Vol. 3, Issue 8
  • DOI: 10.1039/C4TA06694D

Metal Nanocrystals Embedded in Single Nanocrystals of MOFs Give Unusual Selectivity as Heterogeneous Catalysts
journal, September 2014

  • Na, Kyungsu; Choi, Kyung Min; Yaghi, Omar M.
  • Nano Letters, Vol. 14, Issue 10
  • DOI: 10.1021/nl503007h

The Scherrer Formula for X-Ray Particle Size Determination
journal, November 1939

Modeling the Partial Atomic Charges in Inorganometallic Molecules and Solids and Charge Redistribution in Lithium-Ion Cathodes
journal, November 2014

  • Wang, Bo; Li, Shaohong L.; Truhlar, Donald G.
  • Journal of Chemical Theory and Computation, Vol. 10, Issue 12
  • DOI: 10.1021/ct500790p

Synthesis and Characterization of Amine-Functionalized Mixed-Ligand Metal–Organic Frameworks of UiO-66 Topology
journal, August 2014

  • Chavan, Sachin M.; Shearer, Greig C.; Svelle, Stian
  • Inorganic Chemistry, Vol. 53, Issue 18
  • DOI: 10.1021/ic500607a

A flexible ligand-based wavy layered metal–organic framework for lithium-ion storage
journal, May 2015

Facile synthesis and supercapacitive properties of Zr-metal organic frameworks (UiO-66)
journal, January 2015

  • Tan, Yueyue; Zhang, Wei; Gao, Yilong
  • RSC Advances, Vol. 5, Issue 23
  • DOI: 10.1039/C4RA11896K

Water Stable Zr-Benzenedicarboxylate Metal-Organic Frameworks as Photocatalysts for Hydrogen Generation
journal, August 2010

  • Gomes Silva, Cláudia; Luz, Ignacio; Llabrés i. Xamena, Francesc X.
  • Chemistry - A European Journal, Vol. 16, Issue 36
  • DOI: 10.1002/chem.200903526

Redox-Active Metal-Centered Oxalato Phosphate Open Framework Cathode Materials for Lithium Ion Batteries
journal, April 2012

  • Nagarathinam, Mangayarkarasi; Saravanan, Kuppan; Phua, Eunice Jia Han
  • Angewandte Chemie International Edition, Vol. 51, Issue 24
  • DOI: 10.1002/anie.201200210

An exceptionally stable functionalized metal–organic framework for lithium storage
journal, January 2015

  • Lin, Yichao; Zhang, Qiuju; Zhao, Chongchong
  • Chemical Communications, Vol. 51, Issue 4
  • DOI: 10.1039/C4CC07149B

Exploration of vanadium benzenedicarboxylate as a cathode for rechargeable lithium batteries
journal, March 2015

Thermal stability of LiPF6 salt and Li-ion battery electrolytes containing LiPF6
journal, October 2006

Facile Shape Control of Co 3 O 4 and the Effect of the Crystal Plane on Electrochemical Performance
journal, August 2012

Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996

Computational exploration of newly synthesized zirconium metal–organic frameworks UiO-66, -67, -68 and analogues
journal, January 2014

  • Yang, Li-Ming; Ganz, Eric; Svelle, Stian
  • J. Mater. Chem. C, Vol. 2, Issue 34
  • DOI: 10.1039/C4TC00902A

Diamondoid-Structured Cu-Dicarboxylate-based Metal-Organic Frameworks as High-Capacity Anodes for Lithium-Ion Storage
journal, October 2014

  • Senthil Kumar, R.; Nithya, C.; Gopukumar, S.
  • Energy Technology, Vol. 2, Issue 11
  • DOI: 10.1002/ente.201402076

A facile synthesis of UiO-66, UiO-67 and their derivatives
journal, January 2013

  • Katz, Michael J.; Brown, Zachary J.; Colón, Yamil J.
  • Chemical Communications, Vol. 49, Issue 82
  • DOI: 10.1039/c3cc46105j

Reversible Lithium Storage in Manganese 1,3,5-Benzenetricarboxylate Metal–Organic Framework with High Capacity and Rate Performance
journal, July 2015

  • Maiti, Sandipan; Pramanik, Atin; Manju, Unnikrishnan
  • ACS Applied Materials & Interfaces, Vol. 7, Issue 30
  • DOI: 10.1021/acsami.5b03414

Lithium storage in a metal organic framework with diamondoid topology – a case study on metal formates
journal, January 2010

  • Saravanan, Kuppan; Nagarathinam, Mangayarkarasi; Balaya, Palani
  • Journal of Materials Chemistry, Vol. 20, Issue 38
  • DOI: 10.1039/c0jm01671c

Lewis Acid–Base Interactions between Polysulfides and Metal Organic Framework in Lithium Sulfur Batteries
journal, April 2014

  • Zheng, Jianming; Tian, Jian; Wu, Dangxin
  • Nano Letters, Vol. 14, Issue 5
  • DOI: 10.1021/nl404721h

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

A new local density functional for main-group thermochemistry, transition metal bonding, thermochemical kinetics, and noncovalent interactions
journal, November 2006

  • Zhao, Yan; Truhlar, Donald G.
  • The Journal of Chemical Physics, Vol. 125, Issue 19, Article No. 194101
  • DOI: 10.1063/1.2370993

Shape-controlled synthesis and lithium-storage study of metal-organic frameworks Zn4O(1,3,5-benzenetribenzoate)2
journal, September 2006

Three-Dimensional Metal Scaffold Supported Bicontinuous Silicon Battery Anodes
journal, May 2012

  • Zhang, Huigang; Braun, Paul V.
  • Nano Letters, Vol. 12, Issue 6
  • DOI: 10.1021/nl204551m

Charge Model 5: An Extension of Hirshfeld Population Analysis for the Accurate Description of Molecular Interactions in Gaseous and Condensed Phases
journal, February 2012

  • Marenich, Aleksandr V.; Jerome, Steven V.; Cramer, Christopher J.
  • Journal of Chemical Theory and Computation, Vol. 8, Issue 2, p. 527-541
  • DOI: 10.1021/ct200866d

Cathode Composites for Li–S Batteries via the Use of Oxygenated Porous Architectures
journal, October 2011

  • Demir-Cakan, Rezan; Morcrette, Mathieu; Nouar, Farid
  • Journal of the American Chemical Society, Vol. 133, Issue 40
  • DOI: 10.1021/ja2062659

Synthesis, Structure, Characterization, and Redox Properties of the Porous MIL-68(Fe) Solid
journal, July 2010

  • Fateeva, Alexandra; Horcajada, Patricia; Devic, Thomas
  • European Journal of Inorganic Chemistry, Vol. 2010, Issue 24
  • DOI: 10.1002/ejic.201000486

A New Zirconium Inorganic Building Brick Forming Metal Organic Frameworks with Exceptional Stability
journal, October 2008

  • Cavka, Jasmina Hafizovic; Jakobsen, Søren; Olsbye, Unni
  • Journal of the American Chemical Society, Vol. 130, Issue 42, p. 13850-13851
  • DOI: 10.1021/ja8057953

One-pot synthesis of a metal–organic framework as an anode for Li-ion batteries with improved capacity and cycling stability
journal, February 2014

Calculation of semiconductor band gaps with the M06-L density functional
journal, February 2009

  • Zhao, Yan; Truhlar, Donald G.
  • The Journal of Chemical Physics, Vol. 130, Issue 7, Article No. 074103
  • DOI: 10.1063/1.3076922

Semiempirical GGA-type density functional constructed with a long-range dispersion correction
journal, January 2006

  • Grimme, Stefan
  • Journal of Computational Chemistry, Vol. 27, Issue 15, p. 1787-1799
  • DOI: 10.1002/jcc.20495

Lithium-Based 3D Coordination Polymer with Hydrophilic Structure for Sensing of Solvent Molecules
journal, September 2008

  • Liu, Ying-Ya; Zhang, Jian; Xu, Fen
  • Crystal Growth & Design, Vol. 8, Issue 9
  • DOI: 10.1021/cg701173x

In situ Fe XAFS of reversible lithium insertion in a flexible metal organic framework material
journal, October 2009

  • Combarieu, Guillaume de; Hamelet, Stéphane; Millange, Franck
  • Electrochemistry Communications, Vol. 11, Issue 10
  • DOI: 10.1016/j.elecom.2009.08.008

Metal Oxide-Coated Three-Dimensional Graphene Prepared by the Use of Metal-Organic Frameworks as Precursors
journal, December 2013

  • Cao, Xiehong; Zheng, Bing; Rui, Xianhong
  • Angewandte Chemie International Edition, Vol. 53, Issue 5
  • DOI: 10.1002/anie.201308013

Formation of Fe 2 O 3 Microboxes with Hierarchical Shell Structures from Metal–Organic Frameworks and Their Lithium Storage Properties
journal, October 2012

  • Zhang, Lei; Wu, Hao Bin; Madhavi, Srinivasan
  • Journal of the American Chemical Society, Vol. 134, Issue 42
  • DOI: 10.1021/ja307475c

Detailed Structure Analysis of Atomic Positions and Defects in Zirconium Metal–Organic Frameworks
journal, October 2014

  • Øien, Sigurd; Wragg, David; Reinsch, Helge
  • Crystal Growth & Design, Vol. 14, Issue 11
  • DOI: 10.1021/cg501386j

Monitoring the Solid-State Electrochemistry of Cu(2,7-AQDC) (AQDC = Anthraquinone Dicarboxylate) in a Lithium Battery: Coexistence of Metal and Ligand Redox Activities in a Metal–Organic Framework
journal, November 2014

  • Zhang, Zhongyue; Yoshikawa, Hirofumi; Awaga, Kunio
  • Journal of the American Chemical Society, Vol. 136, Issue 46
  • DOI: 10.1021/ja508197w

A layered oxalatophosphate framework as a cathode material for Li-ion batteries
journal, January 2013

  • Shahul Hameed, A.; Nagarathinam, Mangayarkarasi; Schreyer, Martin
  • Journal of Materials Chemistry A, Vol. 1, Issue 18
  • DOI: 10.1039/c3ta10464h

Metal–organic frameworks as platforms for clean energy
journal, January 2013

  • Li, Shun-Li; Xu, Qiang
  • Energy & Environmental Science, Vol. 6, Issue 6
  • DOI: 10.1039/c3ee40507a
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