Polyacrylonitrile-based electrolytes: How processing and residual solvent affect ion transport and stability

Liu, Changhao; Sacci, Robert; Sahore, Ritu; Veith, Gabriel; Dudney, Nancy; Chen, Xi

doi:10.1016/j.jpowsour.2022.231165

Polyacrylonitrile-based electrolytes: How processing and residual solvent affect ion transport and stability

Journal Article · Wed Feb 23 00:00:00 EST 2022 · Journal of Power Sources

DOI:https://doi.org/10.1016/j.jpowsour.2022.231165· OSTI ID:1876287

Liu, Changhao ^[1]; ^[1]; ^[1]; ^[1]; ^[1]; ^[1]

Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

Polyacrylonitrile (PAN) is one of the alternative candidate polymer hosts to form solid polymer electrolytes (SPEs) besides the widely used poly(ethylene oxide). In this study, we systematically investigate the processing of PAN based SPEs containing lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt, using dimethylformamide (DMF) as the solvent. The effects of PAN processing procedure including solution mixing, casting, and drying on the morphology, ion transport, solvation structure, Li and oxidative stability of PAN electrolytes are thoroughly examined. In particular, four drying conditions are investigated and the amount of residual DMF is accurately determined using infrared (IR) spectroscopy. Varying the drying conditions can lead to five orders of magnitude decrease in the ionic conductivity. As DMF content decreases, the SPE's stability again Li metal dramatically improves. The practical oxidative stability is also strongly affected by the residual DMF content, ranging from 2.5 V to 3.5 V, much lower than reported values. Finally, the role of the residual DMF solvent is elucidated. DMF content vitally influences ion solvation structure at different concentration regimes, which ultimately dictates the ion conduction mechanism and oxidative stability of PAN based SPEs. This thorough study lays the groundwork for future development of PAN based electrolytes.

View Accepted Manuscript (DOE)

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1876287

Alternate ID(s):: OSTI ID: 1961689

Journal Information:: Journal of Power Sources, Journal Name: Journal of Power Sources Vol. 527; ISSN 0378-7753

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

References (36)

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
Practical performances of Li-ion polymer batteries with LiNi0.8Co0.2O2, MCMB, and PAN-based gel electrolyte Akashi, Hiroyuki; Shibuya, Mashio; Orui, Ken Journal of Power Sources, Vol. 112, Issue 2 https://doi.org/10.1016/S0378-7753(02)00465-2	journal	November 2002
Conductive behaviour of lithium ions in polyacrylonitrile Yang, C. R.; Perng, J. T.; Wang, Y. Y. Journal of Power Sources, Vol. 62, Issue 1 https://doi.org/10.1016/S0378-7753(96)02414-7	journal	September 1996
Ion solvation and ion association in lithium trifluoromethanesulfonate solutions in three aprotic solvents. An FT-Raman spectroscopic study Alı́a, Jose M.; Edwards, Howell G. M. Vibrational Spectroscopy, Vol. 24, Issue 2 https://doi.org/10.1016/S0924-2031(00)00073-4	journal	December 2000
High-performance gel-type lithium electrolyte membranes Appetecchi, G. Electrochemistry Communications, Vol. 1, Issue 2 https://doi.org/10.1016/S1388-2481(99)00011-9	journal	February 1999
Study on ionic transport mechanism and interactions between salt and polymer chain in PAN based solid polymer electrolytes containing LiCF3SO3 Yoon, Hae-Kwon; Chung, Won-Sub; Jo, Nam-Ju Electrochimica Acta, Vol. 50, Issue 2-3 https://doi.org/10.1016/j.electacta.2004.01.095	journal	November 2004
Electrospun hydrophilic fumed silica/polyacrylonitrile nanofiber-based composite electrolyte membranes Jung, Hong-Ryun; Ju, Dong-Hyuk; Lee, Wan-Jin Electrochimica Acta, Vol. 54, Issue 13 https://doi.org/10.1016/j.electacta.2009.01.039	journal	May 2009
Development of polyacrylonitrile-based polymer electrolytes incorporated with lithium bis(trifluoromethane)sulfonimide for application in electrochromic device Sim, L. N.; Sentanin, F. C.; Pawlicka, A. Electrochimica Acta, Vol. 229 https://doi.org/10.1016/j.electacta.2017.01.098	journal	March 2017
All solid-state polymer electrolytes for high-performance lithium ion batteries Yue, Liping; Ma, Jun; Zhang, Jianjun Energy Storage Materials, Vol. 5 https://doi.org/10.1016/j.ensm.2016.07.003	journal	October 2016
Preparation and electrochemical characterization of gel polymer electrolyte based on electrospun polyacrylonitrile nonwoven membranes for lithium batteries Raghavan, Prasanth; Manuel, James; Zhao, Xiaohui Journal of Power Sources, Vol. 196, Issue 16 https://doi.org/10.1016/j.jpowsour.2010.10.089	journal	August 2011
High discharge capacity solid composite polymer electrolyte lithium battery Chen, Y. T.; Chuang, Y. C.; Su, J. H. Journal of Power Sources, Vol. 196, Issue 5 https://doi.org/10.1016/j.jpowsour.2010.11.058	journal	March 2011
Challenges and issues facing lithium metal for solid-state rechargeable batteries Mauger, A.; Armand, M.; Julien, C. M. Journal of Power Sources, Vol. 353 https://doi.org/10.1016/j.jpowsour.2017.04.018	journal	June 2017
Beyond PEO—Alternative host materials for Li + -conducting solid polymer electrolytes Mindemark, Jonas; Lacey, Matthew J.; Bowden, Tim Progress in Polymer Science, Vol. 81 https://doi.org/10.1016/j.progpolymsci.2017.12.004	journal	June 2018
Inorganic Solid-State Electrolytes for Lithium Batteries: Mechanisms and Properties Governing Ion Conduction Bachman, John Christopher; Muy, Sokseiha; Grimaud, Alexis Chemical Reviews, Vol. 116, Issue 1 https://doi.org/10.1021/acs.chemrev.5b00563	journal	December 2015
Structural and Electrochemical Properties of Li Ion Solvation Complexes in the Salt-Concentrated Electrolytes Using an Aprotic Donor Solvent, N , N -Dimethylformamide Fujii, Kenta; Wakamatsu, Hideaki; Todorov, Yanko The Journal of Physical Chemistry C, Vol. 120, Issue 31 https://doi.org/10.1021/acs.jpcc.6b04542	journal	July 2016
The Compensation Effect in the Vogel–Tammann–Fulcher (VTF) Equation for Polymer-Based Electrolytes Diederichsen, Kyle M.; Buss, Hilda G.; McCloskey, Bryan D. Macromolecules, Vol. 50, Issue 10 https://doi.org/10.1021/acs.macromol.7b00423	journal	May 2017
Ionic Conductivity Enhancement of Polymer Electrolytes with Ceramic Nanowire Fillers Liu, Wei; Liu, Nian; Sun, Jie Nano Letters, Vol. 15, Issue 4, p. 2740-2745 https://doi.org/10.1021/acs.nanolett.5b00600	journal	March 2015
Composite Polymer Electrolytes with Li ₇ La ₃ Zr ₂ O ₁₂ Garnet-Type Nanowires as Ceramic Fillers: Mechanism of Conductivity Enhancement and Role of Doping and Morphology Yang, Ting; Zheng, Jin; Cheng, Qian ACS Applied Materials & Interfaces, Vol. 9, Issue 26 https://doi.org/10.1021/acsami.7b03806	journal	June 2017
Challenges in Lithium Metal Anodes for Solid-State Batteries Hatzell, Kelsey B.; Chen, Xi Chelsea; Cobb, Corie L. ACS Energy Letters, Vol. 5, Issue 3 https://doi.org/10.1021/acsenergylett.9b02668	journal	February 2020
Characterization of PAN-Based Gel Electrolytes. Electrochemical Stability and Lithium Cyclability Dautzenberg, G.; Croce, F.; Passerini, S. Chemistry of Materials, Vol. 6, Issue 4 https://doi.org/10.1021/cm00040a032	journal	April 1994
Vapor Pressure–Temperature Nomographs Lippincott, Samuel B.; Lyman, Margaret M. Industrial & Engineering Chemistry, Vol. 38, Issue 3 https://doi.org/10.1021/ie50435a022	journal	March 1946
Unusual Stability of Acetonitrile-Based Superconcentrated Electrolytes for Fast-Charging Lithium-Ion Batteries Yamada, Yuki; Furukawa, Keizo; Sodeyama, Keitaro Journal of the American Chemical Society, Vol. 136, Issue 13, p. 5039-5046 https://doi.org/10.1021/ja412807w	journal	March 2014
How Strong Is the C ^α −H···OC Hydrogen Bond? Vargas, Rubicelia; Garza, Jorge; Dixon, David A. Journal of the American Chemical Society, Vol. 122, Issue 19 https://doi.org/10.1021/ja993600a	journal	May 2000
A New Class of Ionically Conducting Fluorinated Ether Electrolytes with High Electrochemical Stability Amanchukwu, Chibueze V.; Yu, Zhiao; Kong, Xian Journal of the American Chemical Society, Vol. 142, Issue 16 https://doi.org/10.1021/jacs.9b11056	journal	April 2020
Interactions between Polyacrylonitrile and Solvents: Density Functional Theory Study and Two-Dimensional Infrared Correlation Analysis Wu, Qing-Yun; Chen, Xiao-Na; Wan, Ling-Shu The Journal of Physical Chemistry B, Vol. 116, Issue 28 https://doi.org/10.1021/jp304167f	journal	July 2012
Glyme–Lithium Salt Equimolar Molten Mixtures: Concentrated Solutions or Solvate Ionic Liquids? Ueno, Kazuhide; Yoshida, Kazuki; Tsuchiya, Mizuho The Journal of Physical Chemistry B, Vol. 116, Issue 36 https://doi.org/10.1021/jp307378j	journal	August 2012
Progress in nitrile-based polymer electrolytes for high performance lithium batteries Hu, Pu; Chai, Jingchao; Duan, Yulong Journal of Materials Chemistry A, Vol. 4, Issue 26 https://doi.org/10.1039/C6TA02907H	journal	January 2016
Influence of Salt Content on Polymer Dissolution and Ionic Association in Polymer Electrolyte Wang, Zhaoxiang; Gao, Weidong; Huang, Xuejie Electrochemical and Solid-State Letters, Vol. 4, Issue 8 https://doi.org/10.1149/1.1383429	journal	January 2001
X-Ray Diffraction and Vibrational Spectroscopic Studies on PAN-LiTFSI Polymer Electrolytes Li, Jingze; Huang, Xuejie; Chen, Liquan Journal of The Electrochemical Society, Vol. 147, Issue 7 https://doi.org/10.1149/1.1393585	journal	January 2000
High Voltage Lithium Polymer Cells Using a PAN-Based Composite Electrolyte Panero, S.; Satolli, D.; D’Epifano, A. Journal of The Electrochemical Society, Vol. 149, Issue 4, p. A414-A417 https://doi.org/10.1149/1.1454139	journal	January 2002
Electrochemical and Spectroscopic Properties of Electrospun PAN-Based Fibrous Polymer Electrolytes Choi, S. W.; Kim, J. R.; Jo, S. M. Journal of The Electrochemical Society, Vol. 152, Issue 5 https://doi.org/10.1149/1.1887166	journal	January 2005
Hazard Investigations of LiClO4 / Dioxolane Electrolyte Newman, G. H.; Francis, R. W.; Gaines, L. H. Journal of The Electrochemical Society, Vol. 127, Issue 9 https://doi.org/10.1149/1.2130056	journal	September 1980
Thermal Stability of a Propylene Carbonate Electrolyte Jasinski, Raymond; Carroll, Susan Journal of The Electrochemical Society, Vol. 117, Issue 2 https://doi.org/10.1149/1.2407468	journal	January 1970
Performance of “Polymer-in-Salt” Electrolyte PAN-LiTFSI Enhanced by Graphene Oxide Filler Wu, Bo; Wang, Liping; Li, Zhiling Journal of The Electrochemical Society, Vol. 163, Issue 10 https://doi.org/10.1149/2.0531610jes	journal	January 2016
A Critical Review for an Accurate Electrochemical Stability Window Measurement of Solid Polymer and Composite Electrolytes Méry, Adrien; Rousselot, Steeve; Lepage, David Materials, Vol. 14, Issue 14 https://doi.org/10.3390/ma14143840	journal	July 2021
Formation of Stable Interphase of Polymer-in-Salt Electrolyte in All-Solid-State Lithium Batteries Gao, Hongcai; Grundish, Nicholas S.; Zhao, Yongjie Energy Material Advances, Vol. 2021 https://doi.org/10.34133/2021/1932952	journal	January 2021

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