Citation: LYU Kangjie, PENG Yanqiu, XIAO Li, LU Juntao, ZHUANG Lin. Atomistic Understanding of the Peculiar Dissolution Behavior of Alkaline Polymer Electrolytes in Alcohol/Water Mixed Solvents[J]. Acta Physico-Chimica Sinica, ;2019, 35(4): 378-384. doi: 10.3866/PKU.WHXB201805031 shu

Atomistic Understanding of the Peculiar Dissolution Behavior of Alkaline Polymer Electrolytes in Alcohol/Water Mixed Solvents

LYU Kangjie ¹ ,
PENG Yanqiu ¹ ,
XIAO Li ^1,, ,
LU Juntao ¹ ,
ZHUANG Lin ^1,2,,

1.
Hubei Key Lab of Electrochemical Power Sources, College of Chemistry and Molecular Sciences, Wuhan 430072, P. R. China
2.
Institute for Advanced Studies, Wuhan University, Wuhan 430072, P. R. China

Corresponding author: XIAO Li, chem.lily@whu.edu.cn ZHUANG Lin, lzhuang@whu.edu.cn
Received Date: 9 April 2018
Revised Date: 2 May 2018
Accepted Date: 2 May 2018
Available Online: 3 April 2018
Fund Project: the National Natural Science Foundation of China 21633008The project was supported by the National Key Research and Development Program of China (2016YFB0101203) and the National Natural Science Foundation of China (91545205, 21633008)the National Key Research and Development Program of China 2016YFB0101203the National Natural Science Foundation of China 91545205

Self-aggregated quaternary ammonium polysulfone (aQAPS) is a high-performance alkaline polymer electrolyte that has been applied in alkaline polymer electrolyte fuel cells (APEFCs). For a long time, N, N-dimethyl formamide (DMF) has been considered the best solvent to dissolve aQAPS, but the high boiling point of DMF makes it hard to remove from the electrodes, which potentially poisons the electrocatalysts. Our recent experiments have shown that although aQAPS is unable to dissolve in ethanol, n-propanol, or water, it can dissolve in the mixture of these alcohols and water. This peculiar dissolution behavior significantly facilitates the fabrication of the membrane electrode assembly (MEA) for APEFCs, even though it has not been understood. In this work, atomistic molecular dynamics (MD) simulations were employed to study the dissolution behavior of aQAPS in different solvents, including water, methanol, ethanol, n-propanol, DMF, and the mixture of these non-aqueous solvents and water. The conformation of the aQAPS chain in pure solvents agreed well with the dissolution behavior observed in the experiments, even though in the water-containing mixed solvents, the aQAPS chain tended to be in a more contracted state. The simulations further revealed that the water component in the mixed solvents played dual roles. On one hand, the hydrocarbon chain of aQAPS was compressed to a contracted state upon the addition of water, because of the hydrophobic effect. On the other hand, water can drive the dissociation of the counterion (Cl^– ), which led to an enhancement in the solute-solvent interaction energy and thus facilitated the dissolution of aQAPS. In most mixed solvents, the compensation of these two interactions resulted in a general increase in the total solute-solvent interaction energy; therefore, the addition of water was energetically favorable for the dissolution of aQAPS. This study not only furthers our fundamental understanding of the dissolution behavior of polyelectrolytes but also is technologically significant for the development of better APEFCs.
- Alkaline polymer electrolyte,
- Dissolution,
- Alcohol/water mixed solvents,
- Molecular dynamics simulation
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