Polymer electrolytes polyelectrolytes

Monovalent cations are good deflocculants for clay—water sHps and produce deflocculation by a cation exchange process, eg, Na" for Ca ". Low molecular weight polymer electrolytes and polyelectrolytes such as ammonium salts (see Ammonium compounds) are also good deflocculants for polar Hquids. Acids and bases can be used to control pH, surface charge, and the interparticle forces in most oxide ceramic—water suspensions. 

A membrane ionomer, in particular a polyelectrolyte with an inert backbone such as Nation . They require a plasticizer (typically water) to achieve good conductivity levels and are associated primarily, in their protonconducting form, with solid polymer-electrolyte fuel cells. 

In steric stabilization the colloids are covered with a polymer sheath stabilizing the sol against coagulation by electrolytes. In sensitization or adsorption flocculation, the addition of very small concentrations of polymers or polyelectrolytes leads to destabilization (Lyklema, 1985). 

Two general types of polymer electrolytes have been intensively investigated, polymer-salt complexes and polyelectrolytes. A typical polymer-salt complex consists of a coordinating polymer, usually a polyether, in which a salt, e.g. LiC104, is dissolved. Fig. 5.1(a). Both anions and cations can be mobile in these types of electrolytes. By contrast, polyelectrolytes contain charged groups, either cations or anions, covalently attached to the polymer. Fig. 5.1(h), so only the counterion is mobile. 

Fig. 5.1 Contrast between (a) a polymer electrolyte containing a salt MX and (b) a polyelectrolyte in which the anion is attached to the polymer.

Note 2 The terms polyelectrolyte, polymer electrolyte, and polymeric electrolyte should not be confused with the term solid polymer electrolyte. 

The electrical properties of polyelectrolyte complexes are more closely related to those of biologically produced solids. The extremely high relative dielectric constants at low frequencies and the dispersion properties of salt-containing polyelectrolyte complexes have not been reported for other synthetic polymers. Neutral polyelectrolyte complexes immersed in dilute salt solution undergo marked changes in alternating current capacitance and resistance upon small variations in the electrolyte concentration. In addition, their frequency-dependence is governed by the nature of the microions. As shown in... 

Perfluorosulfonic acid (PFSA) - polyelectrolyte PEO polyethylene oxide), and polymer electrolyte... 

In polyelectrolyte gels the variation of pH or salt concentration (cs) causes a swelling or shrinkage. Therefore, in this case chemical energy is transformed to mechanical work (artificial muscles). An increase of cs (or a decrease of temperature) makes the gel shrink. Usually, the shrinking process occurs smoothly, but under certain conditions a tiny addition of salt leads to the collapse of the gel [iii, iv]. Hydration of macroions also plays an important role, e.g., in the case of proton-conductive polymers, such as -> Nafion, which are applied in -rfuel cells, -> chlor-alkali electrolysis, effluent treatment, etc. [v]. Polyelectrolytes have to be distinguished from the solid polymer electrolytes [vi] (- polymer electrolytes) inasmuch as the latter usually contain an undissociable polymer and dissolved small electrolytes. 

Gibbs monolayers are widespread. The simplest system is that of the surface of a fully miscible binary liquid. More complex ones are monolayers of uncharged molecules adsorbed from dilute solutions (example aliphatic alcohols from aqueous solution) electrolytes surfactants (non-ionic or ionic) polymers and polyelectrolytes and yet more. On the other hand, the methods for characterizing... 

Fundamental investigation of the system at the molecular level. This requires investigations of the structure of the solid/liquid interface, namely the structure of the electrical double layer (for charge-stabiUsed suspensions), adsorption of surfactants, polymers and polyelectrolytes and conformation of the adsorbed layers (e.g., the adsorbed layer thickness). It is important to know how each of these parameters changes with the conditions, such as temperature, solvency of the medium for the adsorbed layers, and the effect of addition of electrolytes. 

Over the past 10 years, research into water-soluble ferrocene-based polymers and polyelectrolytes has increased.168-175 Vancso and co-workers have reported the preparation and self-assembly of anionic and cationic polyelectrolytes.171,172 Polyanionic, 89, and polycationic, 90, ferrocene-based electrolytes are two examples of such polyelectrolytes.170... 

The definition of a solid polymer electrolyte should not be confused with that of a polymeric electrolyte [whose macromolecules contains ionic or ionizable groups, or both). Polyelectrolytes can be either synthetic or natural [12,16-18, 20-23]. 

FIGURE 2.81 Schematic diagrams of (a) dry solid-state polymer electrolyte (e.g., PEO/Li+), (b) gel polymer electrolyte, and (c) polyelectrolyte. (Zhong, C. et al. 2015. A review of electrolyte materials and compositions for electrochemical supercapacitors. Chemical Society Reviews 44 7484-7539. Reproduced by permission of The Royal Society of Chemistry.)... 

Preparation of solid-state electrochemical devices require that conventional fluid solution electrolytes be replaced with a solid ion conductor. Solid electrolytes have been widely studied, primarily for the development of high energy-density batteries. Classes of solid state electrolytes include classical solids such as the p-aluminas, polyelectrolytes such as Nation, gel electrolytes and polymer electrolytes. For the purpose of developing solid-state electrochemical devices, polymer electrolytes are promising, because they are easily confined to microelectrochemical arrays/and are gas permeable. 

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