Ion Dynamics in Solid Polyelectrolyte Materials

Cramer, Cornelia; Akgöl, Yahya; Imre, Árpád W.; Bhide, Amthra; Schönhoff, Monika

doi:10.1524/zpch.2009.6072

Cited by 7 publications

(8 citation statements)

References 36 publications

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“…Another way is extrapolating the conductivity to low frequencies while neglecting the polarization effects according to a fitting procedure using a reference curve. The latter procedure was described earlier [19,44] and yields dc values which are in very good agreement with the Nyquist fit method, as we showed by a direct comparison [36].…”

Section: Conductivities Of Pemsupporting

confidence: 81%

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Mechanisms of Ion Conduction in Polyelectrolyte Multilayers and Complexes

Schönhoff¹,

Imre

Bhide

et al. 2010

Zeitschrift Für Physikalische Chemie

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This paper reviews the progress made in understanding of the mechanisms of ion conduction in polyelectrolyte multilayers (PEM) and polyelectrolyte complexes (PEC). The basis are experimental conductivity data obtained by impedance spectroscopy as a function of relative humidity and temperature, respectively. Mechanically stable thin films of PEM have interesting perspectives as ion conductors, however, being prepared by self-assembly, their stoichiometry and content of ionic charge carriers is unknown. Therefore PEC act as a model material with a variable stoichiometry and known ion content.Employing poly(sodium 4-styrene sulfonate) (NaPSS) and poly(diallyldimethyl ammoniumchloride) (PDADMAC), we present conductivity spectra of dried polyelectrolyte complexes of type x NaPSS · (1 − x)PDADMAC as a function of temperature and composition, respectively. The dependence of the dc conductivity is discussed along with scaling properties of the spectra. The results show that the conductivity is always determined by the sodium ions, even in PEC with an excess of PDADMAC. The ion dynamics and transport mechanisms are, however, different in PDADMAC-rich than in NaPSS-rich PEC.PEM of different polyionic compounds are investigated in dependence on relative humidity. A general law of an exponential increase of the dc conductivity with relative humidity is found. Absolute values of the conductivity and the strength of the humidity dependence are different for different polyion materials, however, they do not depend on the type of small counterion employed in layer formation. Therefore, it is concluded that in hydrated PEM, protons are the dominant charge carriers.For both PEM and PEC we show that the MIGRATION concept developed by Funke and co-workers can be used for describing the experimental spectra over wide ranges in frequency. This implies that forward-backward hopping motions of small ions play a vital role in solid polyelectrolyte materials. Apart from these potentially successful hops, localized motions of charged particles are found to influence the conductivity spectra as well.

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Section: Conductivities Of Pemsupporting

confidence: 81%

“…Figure 13 shows one conductivity spectrum of 0.60 NaPSS · 0.40 PDADMAC taken at 393 K. The dashed line was obtained on the basis of the MIGRATION concept with the model parameter K = 2.4, see also Ref. [44].…”

Section: Modeling Of Pec Spectramentioning

confidence: 99%

Mechanisms of Ion Conduction in Polyelectrolyte Multilayers and Complexes

Schönhoff¹,

Imre

Bhide

et al. 2010

Zeitschrift Für Physikalische Chemie

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“…This includes friends and colleagues both inside and outside SFB 458, as well as KF's past coworkers. To name just a few, in alphabetical order, we would especially like to thank A. Bunde Besides thanking our friends at SFB 458 for an atmosphere of intense engagement and healthy exchange of views, we also would like to cite a few relevant results of theirs [110][111][112][113][114][115][116][117][118][119][120][121][122][123][124][125][126] which have added new insights while addressing issues complementary to those treated in this overview.…”

Section: Acknowledgementmentioning

confidence: 99%

First and Second Universalities: Expeditions Towards and Beyond

Funke¹,

Banhatti

Laughman³

et al. 2010

Zeitschrift Für Physikalische Chemie

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“…Additionally, the ionic strength of the preparation solution is varied to investigate the effect of shielding. Results obtained for PEMs are further compared to those for PDADMA/PAA polyelectrolyte complexes (PECs), which serve as a reference system with a defined composition, in order to discuss the relevant charge carriers. , …”

Section: Introductionmentioning

confidence: 99%

“…Results obtained for PEMs are further compared to those for PDADMA/PAA polyelectrolyte complexes (PECs), which serve as a reference system with a defined composition, in order to discuss the relevant charge carriers. 36,37 Finally, postpreparational treatments of PEMs in LiCl solutions at varying pH are tested. These treatments assess the possibility of Li + incorporation via a pH-driven approach based on the generation of negative excess charges inside the multilayer assembly.…”

Section: ■ Introductionmentioning

confidence: 99%

Ionic Conductivity Enhancement of Polyelectrolyte Multilayers by Variation of Charge Balance

et al. 2020

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Three different approaches to enhance the dc conductivity of poly(diallyldimethylammonium)/ poly(acrylic acid) (PDADMA/PAA) n polyelectrolyte multilayers (PEMs) are investigated. The first two approaches concern the effect of varied preparation conditions. First, an increase of the pH value of preparation modifies the charge degree of PAA and results in dc conductivities increased by more than 1 order of magnitude. In a second approach, PEMs are prepared in the presence of 0.1 M LiCl solutions. The increase of the conductivities at a higher charge degree of PAA is further amplified as compared to the preparation from water: The dc conductivity increases from (8 ± 2) nS•cm −1 at pH 3 to (6 ± 2) μS•cm −1 for pH 8.5. This strong effect is attributed to enhanced ion mobilities caused by increased hydration, and is discussed with regard to film composition and structure. The third approach involves successive postpreparational treatments of (PDADMA/PAA) n PEMs prepared at pH 4. Such multilayers are immersed into 0.1 M LiCl solutions of stepwise increasing pH to modify the charge balance. The structural changes induced by postpreparational treatment are elucidated by in situ studies utilizing attenuated total reflection infrared spectroscopy (ATR-IR). Upon pH treatment the PAA dissociation is enhanced only in the presence of salt, and the conductivities increase exponentially with pH. Two mechanisms of charge balancing are discussed to explain the adjustment of the films induced by postpreparational treatment: (i) intrinsic charge adjustment by partial desorption of PAA and the relocation of PDADMA and (ii) extrinsic charge compensation by Li + ion incorporation. Though extrinsic compensation by Li + ions may be involved, the dominant influence on film conductivity is not an enhanced charge carrier density but rather a highly ionic polymer matrix environment, which promotes hydration and thus exponentially enhances charge carrier mobility.

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Ion Dynamics in Solid Polyelectrolyte Materials

Cited by 7 publications

References 36 publications

Mechanisms of Ion Conduction in Polyelectrolyte Multilayers and Complexes

Mechanisms of Ion Conduction in Polyelectrolyte Multilayers and Complexes

First and Second Universalities: Expeditions Towards and Beyond

Ionic Conductivity Enhancement of Polyelectrolyte Multilayers by Variation of Charge Balance

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