Time-pH and Time-Humidity Scaling of Ionic Conductivity Spectra of Polyelectrolyte Multilayers

IF 2.9 3区化学 Q3 CHEMISTRY, PHYSICAL

Physical Chemistry Chemical Physics Pub Date : 2024-10-09 DOI:10.1039/d4cp03482a

Jannis Schlicke, Cornelia Cramer, Monika Schönhoff

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引用次数: 0

Abstract

In this systematic study, ionic conductivity spectra of poly(diallyl-dimethylammonium)/ poly(acrylic acid) (PDADMA/PAA)n polyelectrolyte multilayers (PEMs) are investigated regarding superposition principles. In this context, charge transport as well as charge compensation processes in polyelectrolyte assemblies are discussed. The validity of different scaling concepts is tested to differentiate between changes in the mobility and charge carrier density, caused by the variation of a parameter X, where X is either relative humidity during measurement, or salt concentration or pH during preparation. For the first time, time-X scaling for conductivity spectra of PEMs is reported for all three parameters X, resulting in individual mastercurves. Furthermore, a super-mastercurve can be obtained including variations of all three parameters. Changes in plasticization caused by either varied humidity, pH or ionic strength imply non-constant charge carrier mobilities in accordance with a Summerfield-type of scaling, while the charge carrier density remains constant. Interestingly, for preparation conditions which favor extrinsic charge compensation, significant deviations from such Summerfield-type scaling are observed, indicating a variation of the number density of mobile charge carriers with humidity.

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聚电解质多层膜离子电导率谱的时间-pH 和时间-湿度刻度

在这项系统研究中，根据叠加原理对聚（二烯丙基二甲基铵）/聚（丙烯酸）（PDADMA/PAA）n 聚电解质多层膜（PEMs）的离子电导率光谱进行了研究。在此背景下，讨论了聚电解质组件中的电荷传输和电荷补偿过程。测试了不同缩放概念的有效性，以区分参数 X 变化引起的迁移率和电荷载流子密度的变化，其中 X 是测量过程中的相对湿度，或制备过程中的盐浓度或 pH 值。首次报告了针对所有三个参数 X 的 PEM 电导率光谱的时间-X 缩放，从而产生了单独的主曲线。此外，还可获得包括所有三个参数变化的超主曲线。湿度、pH 值或离子强度变化引起的塑化变化意味着电荷载流子迁移率不恒定，这符合夏菲尔德（Summerfield）类型的比例关系，而电荷载流子密度则保持恒定。有趣的是，在有利于外在电荷补偿的制备条件下，观察到与这种夏菲尔德型比例关系的显著偏差，表明移动电荷载流子的数量密度随湿度的变化而变化。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Physical Chemistry Chemical Physics 化学-物理：原子、分子和化学物理

CiteScore

5.50

自引率

9.10%

发文量

2675

审稿时长

2.0 months

期刊介绍： Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.