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Title: Functionalization of 2D materials for enhancing OER/ORR catalytic activity in Li–oxygen batteries

Abstract

A major barrier toward the practical application of lithium-oxygen batteries is the high overpotential caused by the precipitation of oxygen-reduction products at the cathode, resulting in poor cyclability. By combining first-principle calculations and reactive molecular dynamics simulations, we show that surface functionalization of 2D MXene nanosheets offers a high degree of tunability of the catalytic activity for oxygen-reduction and oxygen evolution reactions (ORR/OER). We show that the controlled creation of active vacancy sites on the MXene surface enhances ORR in excess of a factor of 60 compared to graphene based cathode materials. Furthermore, we find that increasing the ratio of fluorine vs. oxygen termination of the functionalized Ti4N3-MXene catalyst reduces the charge overpotential by up to 70% and 80% compared with commercial platinum-on-carbon and graphene catalysts, respectively. These results provide direct guidance toward the rational design of functionalized 2D materials for modulating the catalytic activity for a wide range of electrocatalytic applications.

Authors:
ORCiD logo; ORCiD logo; ;
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Center for Mechanistic Control of Water-Hydrocarbon-Rock Interactions in Unconventional and Tight Oil Formations (CMC-UF); Stanford Univ., CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1619756
Alternate Identifier(s):
OSTI ID: 1759004
Grant/Contract Number:  
AC02-05CH11231; SC0019165
Resource Type:
Published Article
Journal Name:
Communications Chemistry
Additional Journal Information:
Journal Name: Communications Chemistry Journal Volume: 2 Journal Issue: 1; Journal ID: ISSN 2399-3669
Publisher:
Springer Nature
Country of Publication:
United Kingdom
Language:
English
Subject:
25 ENERGY STORAGE; Batteries; Two-dimensional materials

Citation Formats

Ostadhossein, Alireza, Guo, Jack, Simeski, Filip, and Ihme, Matthias. Functionalization of 2D materials for enhancing OER/ORR catalytic activity in Li–oxygen batteries. United Kingdom: N. p., 2019. Web. https://doi.org/10.1038/s42004-019-0196-2.
Ostadhossein, Alireza, Guo, Jack, Simeski, Filip, & Ihme, Matthias. Functionalization of 2D materials for enhancing OER/ORR catalytic activity in Li–oxygen batteries. United Kingdom. https://doi.org/10.1038/s42004-019-0196-2
Ostadhossein, Alireza, Guo, Jack, Simeski, Filip, and Ihme, Matthias. Tue . "Functionalization of 2D materials for enhancing OER/ORR catalytic activity in Li–oxygen batteries". United Kingdom. https://doi.org/10.1038/s42004-019-0196-2.
@article{osti_1619756,
title = {Functionalization of 2D materials for enhancing OER/ORR catalytic activity in Li–oxygen batteries},
author = {Ostadhossein, Alireza and Guo, Jack and Simeski, Filip and Ihme, Matthias},
abstractNote = {A major barrier toward the practical application of lithium-oxygen batteries is the high overpotential caused by the precipitation of oxygen-reduction products at the cathode, resulting in poor cyclability. By combining first-principle calculations and reactive molecular dynamics simulations, we show that surface functionalization of 2D MXene nanosheets offers a high degree of tunability of the catalytic activity for oxygen-reduction and oxygen evolution reactions (ORR/OER). We show that the controlled creation of active vacancy sites on the MXene surface enhances ORR in excess of a factor of 60 compared to graphene based cathode materials. Furthermore, we find that increasing the ratio of fluorine vs. oxygen termination of the functionalized Ti4N3-MXene catalyst reduces the charge overpotential by up to 70% and 80% compared with commercial platinum-on-carbon and graphene catalysts, respectively. These results provide direct guidance toward the rational design of functionalized 2D materials for modulating the catalytic activity for a wide range of electrocatalytic applications.},
doi = {10.1038/s42004-019-0196-2},
journal = {Communications Chemistry},
number = 1,
volume = 2,
place = {United Kingdom},
year = {2019},
month = {8}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1038/s42004-019-0196-2

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Cited by: 3 works
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Works referenced in this record:

A Molten Salt Lithium–Oxygen Battery
journal, February 2016

  • Giordani, Vincent; Tozier, Dylan; Tan, Hongjin
  • Journal of the American Chemical Society, Vol. 138, Issue 8
  • DOI: 10.1021/jacs.5b11744

Exploring MXenes as Cathodes for Non‐Aqueous Lithium–Oxygen Batteries: Design Rules for Selectively Nucleating Li 2 O 2
journal, March 2018

  • Lee, Andrew; Krishnamurthy, Dilip; Viswanathan, Venkatasubramanian
  • ChemSusChem, Vol. 11, Issue 12
  • DOI: 10.1002/cssc.201801224

Mechanism and performance of lithium–oxygen batteries – a perspective
journal, January 2017

  • Mahne, Nika; Fontaine, Olivier; Thotiyl, Musthafa Ottakam
  • Chemical Science, Vol. 8, Issue 10
  • DOI: 10.1039/C7SC02519J

Screening for Superoxide Reactivity in Li-O 2 Batteries: Effect on Li 2 O 2 /LiOH Crystallization
journal, February 2012

  • Black, Robert; Oh, Si Hyoung; Lee, Jin-Hyon
  • Journal of the American Chemical Society, Vol. 134, Issue 6
  • DOI: 10.1021/ja2111543

Projector augmented-wave method
journal, December 1994


O2 reduction by lithium on Au(111) and Pt(111)
journal, July 2010

  • Xu, Ye; Shelton, William A.
  • The Journal of Chemical Physics, Vol. 133, Issue 2
  • DOI: 10.1063/1.3447381

A stable cathode for the aprotic Li–O2 battery
journal, September 2013

  • Ottakam Thotiyl, Muhammed M.; Freunberger, Stefan A.; Peng, Zhangquan
  • Nature Materials, Vol. 12, Issue 11
  • DOI: 10.1038/nmat3737

Anisotropic Surface Modulation of Pt Catalysts for Highly Reversible Li–O 2 Batteries: High Index Facet as a Critical Descriptor
journal, August 2018


Greatly improved electrochemical performance of lithium–oxygen batteries with a bimetallic platinum–copper alloy catalyst
journal, August 2015


The Carbon Electrode in Nonaqueous Li–O2 Cells
journal, December 2012

  • Ottakam Thotiyl, Muhammed M.; Freunberger, Stefan A.; Peng, Zhangquan
  • Journal of the American Chemical Society, Vol. 135, Issue 1, p. 494-500
  • DOI: 10.1021/ja310258x

Tailoring deposition and morphology of discharge products towards high-rate and long-life lithium-oxygen batteries
journal, September 2013

  • Xu, Ji-Jing; Wang, Zhong-Li; Xu, Dan
  • Nature Communications, Vol. 4, Issue 1
  • DOI: 10.1038/ncomms3438

Hierarchically Porous Graphene as a Lithium–Air Battery Electrode
journal, November 2011

  • Xiao, Jie; Mei, Donghai; Li, Xiaolin
  • Nano Letters, Vol. 11, Issue 11
  • DOI: 10.1021/nl203332e

A new method to prevent degradation of lithium–oxygen batteries: reduction of superoxide by viologen
journal, January 2015

  • Yang, L.; Frith, J. T.; Garcia-Araez, N.
  • Chemical Communications, Vol. 51, Issue 9
  • DOI: 10.1039/C4CC09208B

Cathode reaction mechanism on the h-BN/Ni (111) heterostructure for the lithium-oxygen battery
journal, March 2016


Synthesis and Characterization of 2D Molybdenum Carbide (MXene)
journal, February 2016

  • Halim, Joseph; Kota, Sankalp; Lukatskaya, Maria R.
  • Advanced Functional Materials, Vol. 26, Issue 18
  • DOI: 10.1002/adfm.201505328

Role of Surface Structure on Li-Ion Energy Storage Capacity of Two-Dimensional Transition-Metal Carbides
journal, April 2014

  • Xie, Yu; Naguib, Michael; Mochalin, Vadym N.
  • Journal of the American Chemical Society, Vol. 136, Issue 17
  • DOI: 10.1021/ja501520b

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


Experimental and theoretical characterization of ordered MAX phases Mo 2 TiAlC 2 and Mo 2 Ti 2 AlC 3
journal, September 2015

  • Anasori, Babak; Dahlqvist, Martin; Halim, Joseph
  • Journal of Applied Physics, Vol. 118, Issue 9
  • DOI: 10.1063/1.4929640

Development of the ReaxFF Reactive Force Field for Describing Transition Metal Catalyzed Reactions, with Application to the Initial Stages of the Catalytic Formation of Carbon Nanotubes
journal, January 2005

  • Nielson, Kevin D.; van Duin, Adri C. T.; Oxgaard, Jonas
  • The Journal of Physical Chemistry A, Vol. 109, Issue 3
  • DOI: 10.1021/jp046244d

Nonaqueous Li–Air Batteries: A Status Report
journal, October 2014

  • Luntz, Alan C.; McCloskey, Bryan D.
  • Chemical Reviews, Vol. 114, Issue 23
  • DOI: 10.1021/cr500054y

High-Temperature Oxidation of SiC-Based Composite: Rate Constant Calculation from ReaxFF MD Simulations, Part II
journal, March 2013

  • Newsome, David A.; Sengupta, Debasis; van Duin, Adri C. T.
  • The Journal of Physical Chemistry C, Vol. 117, Issue 10
  • DOI: 10.1021/jp307680t

Effect of Synthesis on Quality, Electronic Properties and Environmental Stability of Individual Monolayer Ti 3 C 2 MXene Flakes
journal, November 2016

  • Lipatov, Alexey; Alhabeb, Mohamed; Lukatskaya, Maria R.
  • Advanced Electronic Materials, Vol. 2, Issue 12
  • DOI: 10.1002/aelm.201600255

Elastic properties of 2D Ti 3 C 2 T x MXene monolayers and bilayers
journal, June 2018

  • Lipatov, Alexey; Lu, Haidong; Alhabeb, Mohamed
  • Science Advances, Vol. 4, Issue 6
  • DOI: 10.1126/sciadv.aat0491

Development of a ReaxFF potential for Pd/O and application to palladium oxide formation
journal, July 2013

  • Senftle, Thomas P.; Meyer, Randall J.; Janik, Michael J.
  • The Journal of Chemical Physics, Vol. 139, Issue 4
  • DOI: 10.1063/1.4815820

Disproportionation in Li–O2 Batteries Based on a Large Surface Area Carbon Cathode
journal, October 2013

  • Zhai, Dengyun; Wang, Hsien-Hau; Yang, Junbing
  • Journal of the American Chemical Society, Vol. 135, Issue 41, p. 15364-15372
  • DOI: 10.1021/ja403199d

Identifying Capacity Limitations in the Li/Oxygen Battery Using Experiments and Modeling
journal, January 2011

  • Albertus, Paul; Girishkumar, G.; McCloskey, Bryan
  • Journal of The Electrochemical Society, Vol. 158, Issue 3
  • DOI: 10.1149/1.3527055

Pressure Dependence of the Oxygen Reduction Reaction at the Platinum Microelectrode/Nafion Interface: Electrode Kinetics and Mass Transport
journal, January 1992

  • Parthasarathy, Arvind
  • Journal of The Electrochemical Society, Vol. 139, Issue 10
  • DOI: 10.1149/1.2068992

Mechanistic Evolution of Aprotic Lithium-Oxygen Batteries
journal, March 2017


A redox shuttle to facilitate oxygen reduction in the lithium air battery
journal, January 2013


Computational Study of Low Interlayer Friction in Ti n +1 C n ( n = 1, 2, and 3) MXene
journal, April 2017

  • Zhang, Difan; Ashton, Michael; Ostadhossein, Alireza
  • ACS Applied Materials & Interfaces, Vol. 9, Issue 39
  • DOI: 10.1021/acsami.7b09895

Methane Activation at the Pd/CeO 2 Interface
journal, December 2016

  • Senftle, Thomas P.; van Duin, Adri C. T.; Janik, Michael J.
  • ACS Catalysis, Vol. 7, Issue 1
  • DOI: 10.1021/acscatal.6b02447

On the Efficacy of Electrocatalysis in Nonaqueous Li–O 2 Batteries
journal, November 2011

  • McCloskey, Bryan D.; Scheffler, Rouven; Speidel, Angela
  • Journal of the American Chemical Society, Vol. 133, Issue 45
  • DOI: 10.1021/ja207229n

Nitrogen-Doped Graphene as Efficient Metal-Free Electrocatalyst for Oxygen Reduction in Fuel Cells
journal, February 2010

  • Qu, Liangti; Liu, Yong; Baek, Jong-Beom
  • ACS Nano, Vol. 4, Issue 3, p. 1321-1326
  • DOI: 10.1021/nn901850u

Understanding Catalytic Activity Trends in the Oxygen Reduction Reaction
journal, December 2017


Two-Dimensional Nanocrystals Produced by Exfoliation of Ti3AlC2
journal, August 2011

  • Naguib, Michael; Kurtoglu, Murat; Presser, Volker
  • Advanced Materials, Vol. 23, Issue 37, p. 4248-4253
  • DOI: 10.1002/adma.201102306

Special points for Brillouin-zone integrations
journal, June 1976

  • Monkhorst, Hendrik J.; Pack, James D.
  • Physical Review B, Vol. 13, Issue 12, p. 5188-5192
  • DOI: 10.1103/PhysRevB.13.5188

Two-Dimensional Molybdenum Carbide (MXene) as an Efficient Electrocatalyst for Hydrogen Evolution
journal, August 2016


A Mo 2 C/Carbon Nanotube Composite Cathode for Lithium–Oxygen Batteries with High Energy Efficiency and Long Cycle Life
journal, February 2015


ReaxFF:  A Reactive Force Field for Hydrocarbons
journal, October 2001

  • van Duin, Adri C. T.; Dasgupta, Siddharth; Lorant, Francois
  • The Journal of Physical Chemistry A, Vol. 105, Issue 41
  • DOI: 10.1021/jp004368u

CNT Sheet Air Electrode for the Development of Ultra-High Cell Capacity in Lithium-Air Batteries
journal, April 2017

  • Nomura, Akihiro; Ito, Kimihiko; Kubo, Yoshimi
  • Scientific Reports, Vol. 7, Issue 1
  • DOI: 10.1038/srep45596

A high-energy-density lithium-oxygen battery based on a reversible four-electron conversion to lithium oxide
journal, August 2018


Stability of Glyme Solvate Ionic Liquid as an Electrolyte for Rechargeable Li−O 2 Batteries
journal, February 2017

  • Kwon, Hoi-Min; Thomas, Morgan L.; Tatara, Ryoichi
  • ACS Applied Materials & Interfaces, Vol. 9, Issue 7
  • DOI: 10.1021/acsami.6b14449

Limitations in Rechargeability of Li-O 2 Batteries and Possible Origins
journal, September 2012

  • McCloskey, B. D.; Bethune, D. S.; Shelby, R. M.
  • The Journal of Physical Chemistry Letters, Vol. 3, Issue 20
  • DOI: 10.1021/jz301359t

All-carbon-nanofiber electrodes for high-energy rechargeable Li–O2 batteries
journal, January 2011

  • Mitchell, Robert R.; Gallant, Betar M.; Thompson, Carl V.
  • Energy & Environmental Science, Vol. 4, Issue 8
  • DOI: 10.1039/c1ee01496j

Binary Mixtures of Highly Concentrated Tetraglyme and Hydrofluoroether as a Stable and Nonflammable Electrolyte for Li–O 2 Batteries
journal, July 2018

  • Zhao, Qin; Zhang, Yuhang; Sun, Guiru
  • ACS Applied Materials & Interfaces, Vol. 10, Issue 31
  • DOI: 10.1021/acsami.8b08346

Influence of Li2O2 morphology on oxygen reduction and evolution kinetics in Li–O2 batteries
journal, January 2013

  • Gallant, Betar M.; Kwabi, David G.; Mitchell, Robert R.
  • Energy & Environmental Science, Vol. 6, Issue 8, p. 2518-2528
  • DOI: 10.1039/c3ee40998h

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

Transition Metal-Promoted V 2 CO 2 (MXenes): A New and Highly Active Catalyst for Hydrogen Evolution Reaction
journal, June 2016


Soft self-consistent pseudopotentials in a generalized eigenvalue formalism
journal, April 1990


Parallel reactive molecular dynamics: Numerical methods and algorithmic techniques
journal, April 2012


Ti 3 C 2 MXene as a High Capacity Electrode Material for Metal (Li, Na, K, Ca) Ion Batteries
journal, June 2014

  • Er, Dequan; Li, Junwen; Naguib, Michael
  • ACS Applied Materials & Interfaces, Vol. 6, Issue 14
  • DOI: 10.1021/am501144q

Lithium−Air Battery: Promise and Challenges
journal, June 2010

  • Girishkumar, G.; McCloskey, B.; Luntz, A. C.
  • The Journal of Physical Chemistry Letters, Vol. 1, Issue 14
  • DOI: 10.1021/jz1005384

Li–O2 and Li–S batteries with high energy storage
journal, January 2012

  • Bruce, Peter G.; Freunberger, Stefan A.; Hardwick, Laurence J.
  • Nature Materials, Vol. 11, Issue 1, p. 19-29
  • DOI: 10.1038/nmat3191

2D metal carbides and nitrides (MXenes) for energy storage
journal, January 2017


Reactivity of Carbon in Lithium–Oxygen Battery Positive Electrodes
journal, September 2013

  • Itkis, Daniil M.; Semenenko, Dmitry A.; Kataev, Elmar Yu.
  • Nano Letters, Vol. 13, Issue 10
  • DOI: 10.1021/nl4021649

Effect of Metal Ion Intercalation on the Structure of MXene and Water Dynamics on its Internal Surfaces
journal, March 2016

  • Osti, Naresh C.; Naguib, Michael; Ostadhossein, Alireza
  • ACS Applied Materials & Interfaces, Vol. 8, Issue 14
  • DOI: 10.1021/acsami.6b01490