Estimation of Polyelectrolyte Ionic Conductivity Using Molecular Dynamics Method

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Abstract

This paper describes the procedure of developing a protocol for theoretical evaluation of the ionic conductivity of two polyelectrolyte systems consisting of oligomers simulating the lithium form of the Nafion-115 membrane plasticized in one case with dimethyl sulfoxide and in the other case with propylene carbonate. Model systems for theoretical calculations were constructed according to the values of the degree of swelling of the membrane in the mentioned solvents determined experimentally. The protocol for molecular dynamic simulations was selected taking into account the peculiarities of the structure and physicochemical properties of the components of the investigated systems. The analysis of molecular dynamic simulations trajectories included the evaluation of radial distribution functions and self-diffusion coefficients. The author’s code written in the Python language was used to calculate ionic conductivity. The results of the theoretical calculations are in agreement with the experimental data. The modeling approach proposed in this work can be used for relatively fast estimation of ionic conductivity in similar electrolyte systems in a close temperature range up to the phase transition boundary.

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About the authors

P. M. Osherov

Institute of Intelligent Cybernetic Systems, National Research Nuclear University „MEPhI“

Email: liza@icp.ac.ru
Russian Federation, Kashirskoye sh., 31, Moscow, 115409

E. Yu. Evshchik

Federal Research Center for Problems of Chemical Physics and Medical Chemistry, Russian Academy of Sciences; Moscow Institute of Physics and Technology

Author for correspondence.
Email: liza@icp.ac.ru
Russian Federation, 1, Ak. Semyonov Avenue, 1, Chernogolovka, Moscow Region, 142432; Institutskiy per., 9., Dolgoprudny, Moscow region, 141701

A. V. Shikhovtseva

Federal Research Center for Problems of Chemical Physics and Medical Chemistry, Russian Academy of Sciences

Email: liza@icp.ac.ru
Russian Federation, 1, Ak. Semyonov Avenue, 1, Chernogolovka, Moscow Region, 142432

R. Z. Faizullin

Energy Technology Center, Skolkovo Institute of Science and Technology, territory of Skolkovo Innovation Center

Email: liza@icp.ac.ru
Russian Federation, 30 Bolshoi Blvd. 1, Moscow, 121205

E. M. Khamitov

Ufa Institute of Chemistry, Ural Federal Research Center of RAS

Email: liza@icp.ac.ru
Russian Federation, 71, Oktyabrya Ave., Ufa, Republic of Bashkortostan, 450054

S. S. Borisevich

Federal Research Center for Problems of Chemical Physics and Medical Chemistry, Russian Academy of Sciences

Email: liza@icp.ac.ru
Russian Federation, 1, Ak. Semyonov Avenue, 1, Chernogolovka, Moscow Region, 142432

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Supplementary files

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2. Additional materials
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3. Рис. 1. Протокол молекулярно-динамических симуляций. T* – целевые температуры расчета равные 273, 294 (или 293), 313, 333 К. Все остальные настраиваемые параметры были оставлены по умолчанию.

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4. Fig. 2. Protocol for evaluating self-diffusion coefficients and ionic conductivity values.

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5. Fig. 3. Radial distribution functions gij(r) (left axis) and coordination number nij(r) (right axis) for the Li-Nafion-DMSO (a, b, c) and Li-Nafion-PC (g, d, e) systems: between lithium cations and oxygen atoms from sulfonate groups (a, d), between lithium cations and oxygen atoms from DMSO molecules (b) or carbonyl oxygen atoms from PC molecules (d), between lithium cations (c, e).

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6. Fig. 4. Values ​​of ionic conductivity of Li-Nafion-DMSO and Li-Nafion-PC systems depending on temperature, estimated by molecular modeling methods (expressions (7) and (8), (9)) and obtained using experiments conducted in this work and in the study [10].

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7. Oligomeric chains Nafion

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8. Solvent

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