Anisotropic Ion Diffusion and Electrochemically Driven Transport in Nanostructured Block Copolymer Electrolytes

Timachova, Ksenia; Villaluenga, Irune; Cirrincione, Lisa; Gobet, Mallory; Bhattacharya, Rajashree; Jiang, Xi; Newman, John; Madsen, Louis A.; Greenbaum, Steven G.; Balsara, Nitash P.

doi:10.1021/acs.jpcb.7b11371

Anisotropic Ion Diffusion and Electrochemically Driven Transport in Nanostructured Block Copolymer Electrolytes

Journal Article · Sun Jan 21 23:00:00 EST 2018 · Journal of Physical Chemistry. B

DOI:https://doi.org/10.1021/acs.jpcb.7b11371· OSTI ID:1601170

^[1]; ^[1]; Cirrincione, Lisa ^[2]; ^[2]; Bhattacharya, Rajashree ^[3]; Jiang, Xi ^[4]; Newman, John ^[3]; ^[5]; Greenbaum, Steven G. ^[2]; ^[1]

Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
City Univ. of New York (CUNY), NY (United States). Hunter College
Univ. of California, Berkeley, CA (United States)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States)

Nanostructured block copolymer electrolytes have the potential to enable solid-state batteries with lithium metal anodes. We present complete continuum characterization of ion transport in a lamellar polystyrene-b-poly(ethylene oxide) copolymer/lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) electrolyte as a function of salt concentration. Electrochemical measurements are used to determine the Stefan–Maxwell salt diffusion coefficients $$^D_{+, 0}$$, $$^D_{-, 0}$$, and $$^D_{+, -}$$. Individual self-diffusion coefficients of the lithium- and TFSI-containing species were measured by pulsed-field gradient NMR (PFG-NMR). The NMR data indicate that salt diffusion is locally anisotropic, and this enables determination of a diffusion coefficient parallel to the lamellae, D_∥, and a diffusion coefficient through defects in the lamellae, D_⊥. We quantify anisotropic diffusion by defining an NMR morphology factor and demonstrate that it is correlated to defect density seen by transmission electron microscopy. We find agreement between the electrochemically determined Stefan–Maxwell diffusion coefficients and the diffusion coefficient D⊥ determined by PFG-NMR. Our work indicates that the performance of nanostructured block copolymer electrolytes in batteries is strongly influenced by ion transport through defects.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: National Science Foundation (NSF); US Department of the Navy, Office of Naval Research (ONR); USDOE

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1601170

Journal Information:: Journal of Physical Chemistry. B, Journal Name: Journal of Physical Chemistry. B Journal Issue: 4 Vol. 122; ISSN 1520-6106

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (35)

Block copolymer electrolytes for rechargeable lithium batteries Young, Wen-Shiue; Kuan, Wei-Fan; Epps, Thomas H. Journal of Polymer Science Part B: Polymer Physics, Vol. 52, Issue 1 https://doi.org/10.1002/polb.23404	journal	November 2013
Electrochemical measurement of transference numbers in polymer electrolytes Evans, James; Vincent, Colin A.; Bruce, Peter G. Polymer, Vol. 28, Issue 13 https://doi.org/10.1016/0032-3861(87)90394-6	journal	December 1987
Cation and anion diffusion in the amorphous phase of the polymer electrolyte (PEO) 8LiCF3SO3 Bhattacharja, S.; Smoot, S.; Whitmore, D. Solid State Ionics, Vol. 18-19 https://doi.org/10.1016/0167-2738(86)90132-3	journal	January 1986
Estimation of Li+ transport number in polymer electrolytes by the combination of complex impedance and potentiostatic polarization measurements Watanabe, M. Solid State Ionics, Vol. 28-30 https://doi.org/10.1016/0167-2738(88)90303-7	journal	September 1988
ABA Triblock Brush Polymers: Synthesis, Self-Assembly, Conductivity, and Rheological Properties Bates, Christopher M.; Chang, Alice B.; Momčilović, Nebojša Macromolecules, Vol. 48, Issue 14 https://doi.org/10.1021/acs.macromol.5b00880	journal	July 2015
Effect of Molecular Weight and Salt Concentration on Ion Transport and the Transference Number in Polymer Electrolytes Timachova, Ksenia; Watanabe, Hiroshi; Balsara, Nitash P. Macromolecules, Vol. 48, Issue 21 https://doi.org/10.1021/acs.macromol.5b01724	journal	October 2015
Structure and Ionic Conductivity of Polystyrene- block -poly(ethylene oxide) Electrolytes in the High Salt Concentration Limit Chintapalli, Mahati; Le, Thao N. P.; Venkatesan, Naveen R. Macromolecules, Vol. 49, Issue 5 https://doi.org/10.1021/acs.macromol.5b02620	journal	February 2016
Anisotropic Ionic Conductivity in Block Copolymer Membranes by Magnetic Field Alignment Majewski, Pawel W.; Gopinadhan, Manesh; Jang, Woo-Sik Journal of the American Chemical Society, Vol. 132, Issue 49 https://doi.org/10.1021/ja107309p	journal	December 2010
An NMR and Ionic Conductivity Study of Ion Dynamics in Liquid Poly(ethylene oxide)-Based Electrolytes Doped with LiN(SO₂CF₃)₂ Hayamizu, Kikuko; Sugimoto, Kyoko; Akiba, Etsuo The Journal of Physical Chemistry B, Vol. 106, Issue 3 https://doi.org/10.1021/jp013035+	journal	December 2001
Pulse-Gradient Spin-Echo ¹ H, ⁷ Li, and ¹⁹ F NMR Diffusion and Ionic Conductivity Measurements of 14 Organic Electrolytes Containing LiN(SO ₂ CF ₃ ) ₂ Hayamizu, Kikuko; Aihara, Yuichi; Arai, Shigemasa The Journal of Physical Chemistry B, Vol. 103, Issue 3 https://doi.org/10.1021/jp9825664	journal	January 1999
Anisotropy of Diffusion in a Lamellar Styrene−Isoprene Block Copolymer Hamersky, Mark W.; Tirrell, Matthew; Lodge, Timothy P. Langmuir, Vol. 14, Issue 24 https://doi.org/10.1021/la980140a	journal	November 1998
Self-Diffusion in a Lamellar and Gyroid (Ordered) Diblock Copolymer Investigated Using Pulsed Field Gradient NMR Rittig, Frank; Kärger, Jörg; Papadakis, Christine M. Macromolecules, Vol. 34, Issue 4 https://doi.org/10.1021/ma0011183	journal	January 2001
Effect of Molecular Weight on the Mechanical and Electrical Properties of Block Copolymer Electrolytes Singh, Mohit; Odusanya, Omolola; Wilmes, Gregg M. Macromolecules, Vol. 40, Issue 13 https://doi.org/10.1021/ma0629541	journal	June 2007
Ionic Conductivity, Capacitance, and Viscoelastic Properties of Block Copolymer-Based Ion Gels Zhang, Sipei; Lee, Keun Hyung; Frisbie, C. Daniel Macromolecules, Vol. 44, Issue 4 https://doi.org/10.1021/ma102435a	journal	February 2011
Phase Behavior and Ionic Conductivity of Lithium Perchlorate-Doped Polystyrene- b -poly(2-vinylpyridine) Copolymer Naidu, Sudhakar; Ahn, Hyungju; Gong, Jinsam Macromolecules, Vol. 44, Issue 15 https://doi.org/10.1021/ma200429v	journal	August 2011
Thermodynamic and Structural Changes in Ion-Containing Symmetric Diblock Copolymers: A Small-Angle X-ray Scattering Study Gunkel, Ilja; Thurn-Albrecht, Thomas Macromolecules, Vol. 45, Issue 1 https://doi.org/10.1021/ma201334h	journal	December 2011
Ionic Conductivities of Block Copolymer Electrolytes with Various Conducting Pathways: Sample Preparation and Processing Considerations Young, Wen-Shiue; Epps, Thomas H. Macromolecules, Vol. 45, Issue 11 https://doi.org/10.1021/ma300362f	journal	May 2012
Charge Transport in Nanostructured PS–PEO–PS Triblock Copolymer Electrolytes Bouchet, R.; Phan, T. N. T.; Beaudoin, E. Macromolecules, Vol. 47, Issue 8 https://doi.org/10.1021/ma500420w	journal	April 2014
Anisotropic Diffusion and Morphology in Perfluorosulfonate Ionomers Investigated by NMR Li, Jing; Wilmsmeyer, Kyle G.; Madsen, Louis A. Macromolecules, Vol. 42, Issue 1 https://doi.org/10.1021/ma802106g	journal	January 2009
Effect of Molecular Weight and Salt Concentration on Conductivity of Block Copolymer Electrolytes Panday, Ashoutosh; Mullin, Scott; Gomez, Enrique D. Macromolecules, Vol. 42, Issue 13 https://doi.org/10.1021/ma900451e	journal	July 2009
Anisotropic Proton Conduction in Aligned Block Copolymer Electrolyte Membranes at Equilibrium with Humid Air Park, Moon Jeong; Balsara, Nitash P. Macromolecules, Vol. 43, Issue 1 https://doi.org/10.1021/ma901980b	journal	January 2010
Anisotropy and Transport in Poly(arylene ether sulfone) Hydrophilic−Hydrophobic Block Copolymers Hou, Jianbo; Li, Jing; Madsen, Louis A. Macromolecules, Vol. 43, Issue 1 https://doi.org/10.1021/ma902070h	journal	January 2010
Mechanisms Underlying Ion Transport in Lamellar Block Copolymer Membranes Ganesan, Venkat; Pyramitsyn, Victor; Bertoni, Colleen ACS Macro Letters, Vol. 1, Issue 4 https://doi.org/10.1021/mz300051x	journal	March 2012
Simultaneous Conduction of Electronic Charge and Lithium Ions in Block Copolymers Patel, Shrayesh N.; Javier, Anna E.; Stone, Greg M. ACS Nano, Vol. 6, Issue 2 https://doi.org/10.1021/nn2045664	journal	January 2012
Lithium diffusion in lithium nitride by pulsed-field gradient NMR Wang, Zhongli; Gobet, Mallory; Sarou-Kanian, Vincent Physical Chemistry Chemical Physics, Vol. 14, Issue 39 https://doi.org/10.1039/c2cp42391j	journal	January 2012
1H, 7Li, and 19F nuclear magnetic resonance and ionic conductivity studies for liquid electrolytes composed of glymes and polyetheneglycol dimethyl ethers of CH3O(CH2CH2O)nCH3 (n=3–50) doped with LiN(SO2CF3)2 Hayamizu, Kikuko; Akiba, Etsuo; Bando, Toshinori The Journal of Chemical Physics, Vol. 117, Issue 12 https://doi.org/10.1063/1.1501279	journal	September 2002
Use of the Stimulated Echo in NMR Diffusion Studies Tanner, J. E. The Journal of Chemical Physics, Vol. 52, Issue 5 https://doi.org/10.1063/1.1673336	journal	March 1970
Restricted lithium ion dynamics in PEO-based block copolymer electrolytes measured by high-field nuclear magnetic resonance relaxation Huynh, Tan Vu; Messinger, Robert J.; Sarou-Kanian, Vincent The Journal of Chemical Physics, Vol. 147, Issue 13 https://doi.org/10.1063/1.4993614	journal	October 2017
Physical properties of solid polymer electrolyte PEO(LiTFSI) complexes Gorecki, W.; Jeannin, M.; Belorizky, E. Journal of Physics: Condensed Matter, Vol. 7, Issue 34 https://doi.org/10.1088/0953-8984/7/34/007	journal	August 1995
Polymer Electrolytes Hallinan, Daniel T.; Balsara, Nitash P. Annual Review of Materials Research, Vol. 43, Issue 1 https://doi.org/10.1146/annurev-matsci-071312-121705	journal	July 2013
The Measurement of a Complete Set of Transport Properties for a Concentrated Solid Polymer Electrolyte Solution Ma, Yanping Journal of The Electrochemical Society, Vol. 142, Issue 6 https://doi.org/10.1149/1.2044206	journal	January 1995
Salt Diffusion Coefficients in Block Copolymer Electrolytes Mullin, Scott A.; Stone, Gregory M.; Panday, Ashoutosh Journal of The Electrochemical Society, Vol. 158, Issue 6 https://doi.org/10.1149/1.3563802	journal	January 2011
Negative Transference Numbers in Poly(ethylene oxide)-Based Electrolytes Pesko, Danielle M.; Timachova, Ksenia; Bhattacharya, Rajashree Journal of The Electrochemical Society, Vol. 164, Issue 11 https://doi.org/10.1149/2.0581711jes	journal	January 2017
Relationship between Steady-State Current in Symmetric Cells and Transference Number of Electrolytes Comprising Univalent and Multivalent Ions Balsara, Nitash P.; Newman, John Journal of The Electrochemical Society, Vol. 162, Issue 14 https://doi.org/10.1149/2.0651514jes	journal	January 2015
Application of NMR Spectroscopy to Study Diffusion Anisotropy in Polycrystalline Samples Zibrowius, Β.; Caro, J.; Kärger, J. Zeitschrift für Physikalische Chemie, Vol. 269O, Issue 1 https://doi.org/10.1515/zpch-1988-269122	journal	January 1988

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