Design rules for liquid crystalline electrolytes for enabling dendrite-free lithium metal batteries
Abstract
Dendrite-free electrodeposition of lithium metal is necessary for the adoption of high energy-density rechargeable lithium metal batteries. Here, we demonstrate a mechanism of using a liquid crystalline electrolyte to suppress dendrite growth with a lithium metal anode. A nematic liquid crystalline electrolyte modifies the kinetics of electrodeposition by introducing additional overpotential due to its bulk-distortion and anchoring free energy. By extending the phase-field model, we simulate the morphological evolution of the metal anode and explore the role of bulk-distortion and anchoring strengths on the electrodeposition process. We find that adsorption energy of liquid crystalline molecules on a lithium surface can be a good descriptor for the anchoring energy and obtain it using first-principles density functional theory calculations. Unlike other extrinsic mechanisms, we find that liquid crystals with high anchoring strengths can ensure smooth electrodeposition of lithium metal, thus paving the way for practical applications in rechargeable batteries based on metal anodes.
- Publication Date:
- Sponsoring Org.:
- USDOE Advanced Research Projects Agency - Energy (ARPA-E)
- OSTI Identifier:
- 1671829
- Grant/Contract Number:
- AR0000774
- Resource Type:
- Published Article
- Journal Name:
- Proceedings of the National Academy of Sciences of the United States of America
- Additional Journal Information:
- Journal Name: Proceedings of the National Academy of Sciences of the United States of America Journal Volume: 117 Journal Issue: 43; Journal ID: ISSN 0027-8424
- Publisher:
- Proceedings of the National Academy of Sciences
- Country of Publication:
- United States
- Language:
- English
Citation Formats
Ahmad, Zeeshan, Hong, Zijian, and Viswanathan, Venkatasubramanian. Design rules for liquid crystalline electrolytes for enabling dendrite-free lithium metal batteries. United States: N. p., 2020.
Web. doi:10.1073/pnas.2008841117.
Ahmad, Zeeshan, Hong, Zijian, & Viswanathan, Venkatasubramanian. Design rules for liquid crystalline electrolytes for enabling dendrite-free lithium metal batteries. United States. https://doi.org/10.1073/pnas.2008841117
Ahmad, Zeeshan, Hong, Zijian, and Viswanathan, Venkatasubramanian. Fri .
"Design rules for liquid crystalline electrolytes for enabling dendrite-free lithium metal batteries". United States. https://doi.org/10.1073/pnas.2008841117.
@article{osti_1671829,
title = {Design rules for liquid crystalline electrolytes for enabling dendrite-free lithium metal batteries},
author = {Ahmad, Zeeshan and Hong, Zijian and Viswanathan, Venkatasubramanian},
abstractNote = {Dendrite-free electrodeposition of lithium metal is necessary for the adoption of high energy-density rechargeable lithium metal batteries. Here, we demonstrate a mechanism of using a liquid crystalline electrolyte to suppress dendrite growth with a lithium metal anode. A nematic liquid crystalline electrolyte modifies the kinetics of electrodeposition by introducing additional overpotential due to its bulk-distortion and anchoring free energy. By extending the phase-field model, we simulate the morphological evolution of the metal anode and explore the role of bulk-distortion and anchoring strengths on the electrodeposition process. We find that adsorption energy of liquid crystalline molecules on a lithium surface can be a good descriptor for the anchoring energy and obtain it using first-principles density functional theory calculations. Unlike other extrinsic mechanisms, we find that liquid crystals with high anchoring strengths can ensure smooth electrodeposition of lithium metal, thus paving the way for practical applications in rechargeable batteries based on metal anodes.},
doi = {10.1073/pnas.2008841117},
journal = {Proceedings of the National Academy of Sciences of the United States of America},
number = 43,
volume = 117,
place = {United States},
year = {2020},
month = {10}
}
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1073/pnas.2008841117
https://doi.org/10.1073/pnas.2008841117
Other availability
Search WorldCat to find libraries that may hold this journal
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.
Works referenced in this record:
Quantitative phase-field modeling of dendritic growth in two and three dimensions
journal, April 1998
- Karma, Alain; Rappel, Wouter-Jan
- Physical Review E, Vol. 57, Issue 4
Molecular order at the free surface of a nematic liquid crystal from light reflectivity measurements
journal, April 1971
- Bouchiat, M. A.; Langevin-Cruchon, D.
- Physics Letters A, Vol. 34, Issue 6
Extending phase field models of solidification to polycrystalline materials
journal, December 2003
- Warren, James A.; Kobayashi, Ryo; Lobkovsky, Alexander E.
- Acta Materialia, Vol. 51, Issue 20
Projector augmented-wave method
journal, December 1994
- Blöchl, P. E.
- Physical Review B, Vol. 50, Issue 24, p. 17953-17979
Liquid crystalline lithium-ion electrolytes derived from biodegradable cyclodextrin
journal, January 2019
- Champagne, Pier-Luc; Ester, David; Bhattacharya, Amit
- Journal of Materials Chemistry A, Vol. 7, Issue 19
Phase-Field Formulation for Quantitative Modeling of Alloy Solidification
journal, August 2001
- Karma, Alain
- Physical Review Letters, Vol. 87, Issue 11
Structured electrolytes to suppress dendrite growth in high energy density batteries: Structured electrolytes to suppress dendrite growth
journal, May 2016
- Tan, Jinwang; Ryan, Emily M.
- International Journal of Energy Research, Vol. 40, Issue 13
Ultrathin Two-Dimensional Atomic Crystals as Stable Interfacial Layer for Improvement of Lithium Metal Anode
journal, September 2014
- Yan, Kai; Lee, Hyun-Wook; Gao, Teng
- Nano Letters, Vol. 14, Issue 10
Phase-Field Simulation of Solidification
journal, August 2002
- Boettinger, W. J.; Warren, J. A.; Beckermann, C.
- Annual Review of Materials Research, Vol. 32, Issue 1
Engineered liquid crystal anchoring energies with nanopatterned surfaces
journal, January 2015
- Gear, Christopher; Diest, Kenneth; Liberman, Vladimir
- Optics Express, Vol. 23, Issue 2
Solid Electrolyte: the Key for High-Voltage Lithium Batteries
journal, October 2014
- Li, Juchuan; Ma, Cheng; Chi, Miaofang
- Advanced Energy Materials, Vol. 5, Issue 4
Lithium dendrite growth mechanisms in liquid electrolytes
journal, November 2017
- Jana, Aniruddha; García, R. Edwin
- Nano Energy, Vol. 41
Phase-Field Simulations of Lithium Dendrite Growth with Open-Source Software
journal, June 2018
- Hong, Zijian; Viswanathan, Venkatasubramanian
- ACS Energy Letters, Vol. 3, Issue 7
Ion Transport in Glassy Side-Group Liquid Crystalline Polymer Electrolytes
journal, July 1999
- Imrie, Corrie T.; Ingram, Malcolm D.; McHattie, Gillian S.
- Advanced Materials, Vol. 11, Issue 10
The Mechanism of the Dendritic Electrocrystallization of Zinc
journal, January 1969
- Diggle, J. W.; Despic, A. R.; Bockris, J. O'M.
- Journal of The Electrochemical Society, Vol. 116, Issue 11
Artificial Protection Film on Lithium Metal Anode toward Long-Cycle-Life Lithium-Oxygen Batteries
journal, August 2015
- Liu, Qing-Chao; Xu, Ji-Jing; Yuan, Shuang
- Advanced Materials, Vol. 27, Issue 35
Nano-Segregated Polymeric Film Exhibiting High Ionic Conductivities
journal, November 2005
- Kishimoto, Kenji; Suzawa, Tomoyuki; Yokota, Tomoki
- Journal of the American Chemical Society, Vol. 127, Issue 44
Suppressing Dendritic Lithium Formation Using Porous Media in Lithium Metal-Based Batteries
journal, February 2018
- Li, Nan; Wei, Wenfei; Xie, Keyu
- Nano Letters, Vol. 18, Issue 3
Evaluation of Current, Future, and Beyond Li-Ion Batteries for the Electrification of Light Commercial Vehicles: Challenges and Opportunities
journal, January 2017
- Sripad, Shashank; Viswanathan, Venkatasubramanian
- Journal of The Electrochemical Society, Vol. 164, Issue 11
Toward Safe Lithium Metal Anode in Rechargeable Batteries: A Review
journal, July 2017
- Cheng, Xin-Bing; Zhang, Rui; Zhao, Chen-Zi
- Chemical Reviews, Vol. 117, Issue 15
Nonaqueous Liquid Electrolytes for Lithium-Based Rechargeable Batteries
journal, October 2004
- Xu, Kang
- Chemical Reviews, Vol. 104, Issue 10, p. 4303-4418
From Nanostructured Liquid Crystals to Polymer-Based Electrolytes
journal, August 2010
- Kato, Takashi
- Angewandte Chemie International Edition, Vol. 49, Issue 43
Phase-field modeling of solid electrolyte interface (SEI) influence on Li dendritic behavior
journal, March 2018
- Yurkiv, Vitaliy; Foroozan, Tara; Ramasubramanian, Ajaykrishna
- Electrochimica Acta, Vol. 265
Surface Anchoring of Liquid Crystal Molecules on Various Substrates
journal, January 1983
- Castellano, Joseph A.
- Molecular Crystals and Liquid Crystals, Vol. 94, Issue 1-2
Design principles for self-forming interfaces enabling stable lithium-metal anodes
journal, October 2020
- Zhu, Yingying; Pande, Vikram; Li, Linsen
- Proceedings of the National Academy of Sciences
Enabling fast charging – A battery technology gap assessment
journal, November 2017
- Ahmed, Shabbir; Bloom, Ira; Jansen, Andrew N.
- Journal of Power Sources, Vol. 367
Predicting surface anchoring: molecular organization across a thin film of 5CB liquid crystal on silicon
journal, January 2012
- Pizzirusso, A.; Berardi, R.; Muccioli, L.
- Chem. Sci., Vol. 3, Issue 2
Electric-Field-Responsive Lithium-Ion Conductors of Propylenecarbonate-Based Columnar Liquid Crystals
journal, April 2009
- Shimura, Harutoki; Yoshio, Masafumi; Hamasaki, Atsushi
- Advanced Materials, Vol. 21, Issue 16, p. 1591-1594
Phase field kinetics of lithium electrodeposits
journal, December 2014
- Ely, David R.; Jana, Aniruddha; García, R. Edwin
- Journal of Power Sources, Vol. 272
Modulation of dendritic patterns during electrodeposition: A nonlinear phase-field model
journal, December 2015
- Chen, Lei; Zhang, Hao Wei; Liang, Lin Yun
- Journal of Power Sources, Vol. 300
Anomalous Scaling of the Surface Width during Cu Electrodeposition
journal, January 2001
- Huo, S.; Schwarzacher, W.
- Physical Review Letters, Vol. 86, Issue 2
Understanding shape entropy through local dense packing
journal, October 2014
- van Anders, Greg; Klotsa, Daphne; Ahmed, N. Khalid
- Proceedings of the National Academy of Sciences, Vol. 111, Issue 45
Universal chemomechanical design rules for solid-ion conductors to prevent dendrite formation in lithium metal batteries
journal, April 2020
- Fu, Chengyin; Venturi, Victor; Kim, Jinsoo
- Nature Materials, Vol. 19, Issue 7
Effect of Additives on Lithium Cycling Efficiency
journal, January 1994
- Hirai, Toshiro; Yoshimatsu, Isamu; Yamaki, Jun‐ichi
- Journal of The Electrochemical Society, Vol. 141, Issue 9, p. 2300-2305
Molecular theories and structure. Some effects of molecular structural change on liquid crystalline properties
journal, January 1971
- Gray, G. W.; Harrison, K. J.
- Symposia of the Faraday Society, Vol. 5
Towards in Silico Liquid Crystals. Realistic Transition Temperatures and Physical Properties for n -Cyanobiphenyls via Molecular Dynamics Simulations
journal, January 2009
- Tiberio, Giustiniano; Muccioli, Luca; Berardi, Roberto
- ChemPhysChem, Vol. 10, Issue 1
Free Energy of a Nonuniform System. III. Nucleation in a Two‐Component Incompressible Fluid
journal, September 1959
- Cahn, John W.; Hilliard, John E.
- The Journal of Chemical Physics, Vol. 31, Issue 3
High electric conductivity of liquid crystals formed by ordered self-assembly of nonionic surfactant N,N-bis(2-hydroxyethyl)dodecanamide in water
journal, January 2015
- Zhang, Yan; Li, Dechun; Li, Yaping
- Soft Matter, Vol. 11, Issue 9
Unified derivation of phase-field models for alloy solidification from a grand-potential functional
journal, September 2011
- Plapp, Mathis
- Physical Review E, Vol. 84, Issue 3
Stable lithium electrodeposition in liquid and nanoporous solid electrolytes
journal, August 2014
- Lu, Yingying; Tu, Zhengyuan; Archer, Lynden A.
- Nature Materials, Vol. 13, Issue 10
Surface Anchoring of Nematic Liquid Crystals
journal, December 1988
- Yokoyama, H.
- Molecular Crystals and Liquid Crystals Incorporating Nonlinear Optics, Vol. 165, Issue 1
Stability of Electrodeposition at Solid-Solid Interfaces and Implications for Metal Anodes
journal, August 2017
- Ahmad, Zeeshan; Viswanathan, Venkatasubramanian
- Physical Review Letters, Vol. 119, Issue 5
Rapini-Papoular Constants in a Model Nematic Liquid Crystal
journal, September 1997
- Stelzer, Joachim; Longa, Lech; Trebin, Hans-Rainer
- Molecular Crystals and Liquid Crystals Science and Technology. Section A. Molecular Crystals and Liquid Crystals, Vol. 304, Issue 1
Metal Electrode Surfaces Can Roughen Despite the Constraint of a Stiff Electrolyte
journal, January 2019
- McMeeking, Robert M.; Ganser, Markus; Klinsmann, Markus
- Journal of The Electrochemical Society, Vol. 166, Issue 6
Dendrite-Free Lithium Deposition with Self-Aligned Nanorod Structure
journal, November 2014
- Zhang, Yaohui; Qian, Jiangfeng; Xu, Wu
- Nano Letters, Vol. 14, Issue 12
Rapid multiphase-field model development using a modular free energy based approach with automatic differentiation in MOOSE/MARMOT
journal, May 2017
- Schwen, D.; Aagesen, L. K.; Peterson, J. W.
- Computational Materials Science, Vol. 132
Phase-Field Models for Microstructure Evolution
journal, August 2002
- Chen, Long-Qing
- Annual Review of Materials Research, Vol. 32, Issue 1
Lithium dendrite growth mechanisms in polymer electrolytes and prevention strategies
journal, January 2017
- Barai, Pallab; Higa, Kenneth; Srinivasan, Venkat
- Physical Chemistry Chemical Physics, Vol. 19, Issue 31
Quantitative phase-field modeling of dendritic electrodeposition
journal, July 2015
- Cogswell, Daniel A.
- Physical Review E, Vol. 92, Issue 1
Ionic conductivity in crystalline polymer electrolytes
journal, August 2001
- Gadjourova, Zlatka; Andreev, Yuri G.; Tunstall, David P.
- Nature, Vol. 412, Issue 6846
Liquid-Crystalline Electrolytes for Lithium-Ion Batteries: Ordered Assemblies of a Mesogen-Containing Carbonate and a Lithium Salt
journal, December 2014
- Sakuda, Junji; Hosono, Eiji; Yoshio, Masafumi
- Advanced Functional Materials, Vol. 25, Issue 8
The Impact of Elastic Deformation on Deposition Kinetics at Lithium/Polymer Interfaces
journal, January 2005
- Monroe, Charles; Newman, John
- Journal of The Electrochemical Society, Vol. 152, Issue 2
Electrochemical potential window of battery electrolytes: the HOMO–LUMO misconception
journal, January 2018
- Peljo, Pekka; Girault, Hubert H.
- Energy & Environmental Science, Vol. 11, Issue 9
Towards High-Safe Lithium Metal Anodes: Suppressing Lithium Dendrites via Tuning Surface Energy
journal, July 2016
- Wang, Dong; Zhang, Wei; Zheng, Weitao
- Advanced Science, Vol. 4, Issue 1
Lithium metal anodes for rechargeable batteries
journal, January 2014
- Xu, Wu; Wang, Jiulin; Ding, Fei
- Energy Environ. Sci., Vol. 7, Issue 2
Alignment of Liquid Crystals with Patterned Isotropic Surfaces
journal, March 2001
- Lee, B. -w.
- Science, Vol. 291, Issue 5513
Über die Erzeugung der Anisotropie von Oberflächen
journal, January 1928
- Zocher, H.; Coper, K.
- Zeitschrift für Physikalische Chemie, Vol. 132U, Issue 1
Mathematics and liquid crystals
journal, April 2017
- Ball, J. M.
- Molecular Crystals and Liquid Crystals, Vol. 647, Issue 1
The Effect of Interfacial Deformation on Electrodeposition Kinetics
journal, January 2004
- Monroe, Charles; Newman, John
- Journal of The Electrochemical Society, Vol. 151, Issue 6
Orientation of liquid crystals by surface coupling agents
journal, April 1973
- Kahn, Frederic J.
- Applied Physics Letters, Vol. 22, Issue 8
Real-space grid implementation of the projector augmented wave method
journal, January 2005
- Mortensen, J. J.; Hansen, L. B.; Jacobsen, K. W.
- Physical Review B, Vol. 71, Issue 3
First Observation of a n-Doped Quasi-One-Dimensional Electronically-Conducting Discotic Liquid Crystal
journal, November 1994
- Boden, Neville; Borner, Ruth C.; Bushby, Richard J.
- Journal of the American Chemical Society, Vol. 116, Issue 23
MOOSE: A parallel computational framework for coupled systems of nonlinear equations
journal, October 2009
- Gaston, Derek; Newman, Chris; Hansen, Glen
- Nuclear Engineering and Design, Vol. 239, Issue 10
Imaging of liquid crystals using a tunnelling microscope
journal, June 1988
- Foster, J. S.; Frommer, J. E.
- Nature, Vol. 333, Issue 6173
Resolution of the Modulus versus Adhesion Dilemma in Solid Polymer Electrolytes for Rechargeable Lithium Metal Batteries
journal, January 2012
- Stone, G. M.; Mullin, S. A.; Teran, A. A.
- Journal of The Electrochemical Society, Vol. 159, Issue 3
Alignment of Liquid Crystals by Grooved Surfaces
journal, January 1973
- Berreman, Dwight W.
- Molecular Crystals and Liquid Crystals, Vol. 23, Issue 3-4
Surface-produced alignment of liquid crystals
journal, January 1973
- Kahn, F. J.; Taylor, G. N.; Schonhorn, H.
- Proceedings of the IEEE, Vol. 61, Issue 7
Nonlinear phase-field model for electrode-electrolyte interface evolution
journal, November 2012
- Liang, Linyun; Qi, Yue; Xue, Fei
- Physical Review E, Vol. 86, Issue 5
Imaging of liquid crystals with tunneling microscopy
journal, January 1989
- Spong, J. K.; LaComb, L. J.; Dovek, M. M.
- Journal de Physique, Vol. 50, Issue 15
New Type of Li Ion Conductor with 3D Interconnected Nanopores via Polymerization of a Liquid Organic Electrolyte-Filled Lyotropic Liquid-Crystal Assembly
journal, November 2009
- Kerr, Robert L.; Miller, Seth A.; Shoemaker, Richard K.
- Journal of the American Chemical Society, Vol. 131, Issue 44
One-dimensional electronic conductivity in discotic liquid crystals
journal, November 1988
- Boden, N.; Bushby, R. J.; Clements, J.
- Chemical Physics Letters, Vol. 152, Issue 1
Anchoring energy enhancement and pretilt angle control of liquid crystal alignment on polymerized surfaces
journal, September 2015
- Weng, Libo; Liao, Pei-Chun; Lin, Chen-Chun
- AIP Advances, Vol. 5, Issue 9
Machine Learning Enabled Computational Screening of Inorganic Solid Electrolytes for Suppression of Dendrite Formation in Lithium Metal Anodes
journal, August 2018
- Ahmad, Zeeshan; Xie, Tian; Maheshwari, Chinmay
- ACS Central Science, Vol. 4, Issue 8
Suppression of Lithium Dendrite Growth Using Cross-Linked Polyethylene/Poly(ethylene oxide) Electrolytes: A New Approach for Practical Lithium-Metal Polymer Batteries
journal, May 2014
- Khurana, Rachna; Schaefer, Jennifer L.; Archer, Lynden A.
- Journal of the American Chemical Society, Vol. 136, Issue 20
Solid Surface Shape and the Alignment of an Adjacent Nematic Liquid Crystal
journal, June 1972
- Berreman, Dwight W.
- Physical Review Letters, Vol. 28, Issue 26
Dendrite-Free Lithium Deposition via Self-Healing Electrostatic Shield Mechanism
journal, March 2013
- Ding, Fei; Xu, Wu; Graff, Gordon L.
- Journal of the American Chemical Society, Vol. 135, Issue 11, p. 4450-4456
A Comparative Study of Synthetic Graphite and Li Electrodes in Electrolyte Solutions Based on Ethylene Carbonate-Dimethyl Carbonate Mixtures
journal, January 1996
- Aurbach, D.
- Journal of The Electrochemical Society, Vol. 143, Issue 12
Electroconvection in a Viscoelastic Electrolyte
journal, March 2019
- Li, Gaojin; Archer, Lynden A.; Koch, Donald L.
- Physical Review Letters, Vol. 122, Issue 12
Surface effects and anchoring in liquid crystals
journal, March 1991
- Jerome, B.
- Reports on Progress in Physics, Vol. 54, Issue 3
An Artificial Solid Electrolyte Interphase with High Li-Ion Conductivity, Mechanical Strength, and Flexibility for Stable Lithium Metal Anodes
journal, December 2016
- Liu, Yayuan; Lin, Dingchang; Yuen, Pak Yan
- Advanced Materials, Vol. 29, Issue 10
Fluoroethylene Carbonate Additives to Render Uniform Li Deposits in Lithium Metal Batteries
journal, January 2017
- Zhang, Xue-Qiang; Cheng, Xin-Bing; Chen, Xiang
- Advanced Functional Materials, Vol. 27, Issue 10
Ion volumes: a comparison
journal, September 2002
- Marcus, Yizhak; Donald Brooke Jenkins, H.; Glasser, Leslie
- Journal of the Chemical Society, Dalton Transactions, Issue 20
Role of anisotropy in determining stability of electrodeposition at solid-solid interfaces
journal, October 2017
- Ahmad, Zeeshan; Viswanathan, Venkatasubramanian
- Physical Review Materials, Vol. 1, Issue 5
Onset of dendritic growth in lithium/polymer cells
journal, July 2001
- Rosso, M.; Gobron, T.; Brissot, C.
- Journal of Power Sources, Vol. 97-98
A new class of Solvent-in-Salt electrolyte for high-energy rechargeable metallic lithium batteries
journal, February 2013
- Suo, Liumin; Hu, Yong-Sheng; Li, Hong
- Nature Communications, Vol. 4, Issue 1
Theory of Chemical Kinetics and Charge Transfer based on Nonequilibrium Thermodynamics
journal, June 2012
- Bazant, Martin Z.
- Accounts of Chemical Research, Vol. 46, Issue 5
Descriptors for Electrolyte-Renormalized Oxidative Stability of Solvents in Lithium-Ion Batteries
journal, October 2019
- Pande, Vikram; Viswanathan, Venkatasubramanian
- The Journal of Physical Chemistry Letters, Vol. 10, Issue 22
Status and challenges in enabling the lithium metal electrode for high-energy and low-cost rechargeable batteries
journal, December 2017
- Albertus, Paul; Babinec, Susan; Litzelman, Scott
- Nature Energy, Vol. 3, Issue 1
Prospect of Thermal Shock Induced Healing of Lithium Dendrite
journal, March 2019
- Hong, Zijian; Viswanathan, Venkatasubramanian
- ACS Energy Letters, Vol. 4, Issue 5
Nonlinear phase field model for electrodeposition in electrochemical systems
journal, December 2014
- Liang, Linyun; Chen, Long-Qing
- Applied Physics Letters, Vol. 105, Issue 26
High rate and stable cycling of lithium metal anode
journal, February 2015
- Qian, Jiangfeng; Henderson, Wesley A.; Xu, Wu
- Nature Communications, Vol. 6, Issue 1