Composite solid polymer electrolyte preparation

Abstract The chapter begins by discussing the characters and composition of polymer electrolytes for electrochromic devices. It then describes the four types of the polymer electrolytes dry solid polymer electrolyte, gel polymer electrolyte, porous gel polymer electrolyte and composite solid polymer electrolyte, their preparation procedures and properties especially ion conductivity of the samples. Finally, new types of polymer electrolytes including proton-conducting, alkaline, single ionic polymer electrolytes and electrolytes with ionic liquids are also introduced. 

Skotheim et al. [286, 357, 362] have performed in situ electrochemistry and XPS measurements using a solid polymer electrolyte (based on poly (ethylene oxide) (PEO) [363]), which provides a large window of electrochemical stability and overcomes many of the problems associated with UHV electrochemistrty. The use of PEO as an electrolyte has also been investigated by Prosperi et al. [364] who found slow diffusion of the dopant at room temperature as would be expected, and Watanabe et al. have also produced polypyrrole/solid polymer electrolyte composites [365], The electrochemistry of chemically prepared polypyrrole powders has also been investigated using carbon paste electrodes [356, 366] with similar results to those found for electrochemically-prepared material. 

Lawrence, R. J., and Wood, L. D. Method of making solid polymer electrolyte catalytic electrodes and electrode made thereby. U.S. Patent 4,272,353,1981. Fedkiw, P. S., and Her, W. H. An impregnation-reduction method to prepare electrodes on Naifon SPE. Journal of the Electrochemical Society 1989 136 899-900. Aldebert, P, Novel-Cattin, R, Pineri, M., Millet, P, Doumain, G., and Durand, R. Preparation and characterization of SPE composites for electrolyzers and fuel cells. Solid State Ionics 1989 35 3-9. 

N. Fujiwara, K. Asaka, Y. Nishimura, K. Oguro and E. Torikai, Preparation of gold-solid polymer electrolyte composites as electric stimuli-responsive materials, Chem. Mater., 2000, 12, 1750-1754. 

H. Takenaka, E. Torikai, Y. Kawami, N. Wakabayashi and T. Sakai, Studies on solid polymer electrolyte water electrolysis II. Preparation methods for membrane-electro-catalyst composite, Denki Kagaku (J. Electrochem. Soc. Jpn.), 1985, 53, 261. 

P. Millet, R. Durand, E. Dartyge, G. Tourillon and A. Fontaine, Preparation of metallic Platinum into Nafion ionomer membranes. 1. Experimental results, J. Electrochem. Soc., 1993, 140, 1373 P. Millet, F. Andolfatto and R. Durand, Preparation of solid polymer electrolyte composites investigation of the precipitation process, J. Appl. Electrochem., 1995, 25, 227. 

The PVA (Mw 1,25,000, Aldrich), Orthophosphoric acid (H PO ) (Ranbaxy, India) and nano particles of AEj03 (50 mn. Sigma) were used for the preparation of NCPE films. The films of Solid Polymer Electrolyte (PVA + HjPO ) and Nano Composite Polymer Electrolyte (PVA + H3PO + Al Oj) in different filler wt% ratios were prepared by solution cast technique. Grantdes of PVA were dissolved in triply distilled water and stirred magnetically for 10-12 hr to obtain a clear and homogeneous solution. A known amount of H3PO was added to it and stirred continuously until a viscous solution was obtained. A part of solution was poured into the Teflon Petri dishes to get SPE thin film and in another part of the solution, nano-sized Al Oj was added in different wt % to get NCPE thin films. The prepared thin films were rinsed with benzene/methanol to remove any volatile impurities present in it. 

Fedkiw Jr PS. Preparing in situ electrocatalytic films in solid polymer electrolyte membranes, composite microelectrode structures produced thereby and chloralkali process utilizing the same. United States patent US 4959132. 1990 Sep 25. 

Figure 5.5 Chemical plating of gold onto the surface of the ion exchange polymer using a cationic gold complex such as dichlorophenanthrolinegold (III) (Reprinted with permission from Fujiwara, N., Asaka, K., Nishimura, Y. et al. Preparation of Gold-Solid Polymer Electrolyte Composites As Electric Stimuli-Responsive Materials, Chem. of Mat., 12 (6), 1750—4. Copyright (1999) American Chemical Society).

It is possible to prepare composites of nonconducting polymer/inorganic salt by dispersing inorganic salts in the organic matrix via complexation. The electrical conductivity of such materials has been well established in view of their importance as solid polymer electrolytes in solid state batteries (14J5). 

Fujiwara N, Asaka K, Nishimura Y et al (2000) Preparation of gold — solid polymer electrolyte composites as electric stimuli-responsive materials. Chem Mater 12(6) 1750-1754 Fukushima T, Asaka K, Kosaka A et al (2005) Fully plastic actuator through layer-by-layer casting with ionic-liquid-based bucky gel. Angew Chem hit Ed 44 2410-2413 Gao R, Wang D, Heflin JR et al (2012) Imidazolium sulfonate-containing pentablock copolymer-ionic liquid membranes for electroactive actuators. J Mater Chem 22 13473-13476 Gogotsi Y, Nikitin A, Ye H et al (2003) Nanoporous carbide-derived carbon with tunable pore size. Nat Mater 2(9) 591-594... 

A more compact reactor design takes advantage of solid polymer electrolytes (SPEs). Hence, cast Nafion membrane and SPEEK were prepared, and used as cationic SPE whereas alkali-doped poly (vinyl alcohol), PVA and Amberlyst resin composites were made, and used as anionic SPE. These SPEs were combined with a cathode made of copper, electrodeposited onto porous carbon paper, and an anode consisting of Pt/C on the carbon paper. The main electroreduction products were formic acid, methanol, formaldehyde, carbon monoxide and methane, while undesired hydrogen gas by-product was also detected [120]. 

Typically, the solid-state electrolyte can function as both a substrate and separator in the fabrication of a flexible supercapacitor by two steps. For instance, a freestanding PVA/ H3PO4 film was obtained by first casting the gel electrolyte on a glass slide and then peeled off from the glass. It had been further sandwiched between two composite electrodes that were prepared from conducting polymers and nanoparticles to produce the flexible supercapacitor (Fig. 9.3G) (Liu et al., 2010,2013b). 

PEO (4 X 106 mw) and PVP (1.3 x 105 mw) were used to prepare solid polymer blend electrolytes by solntion cast technique. Films (thicknesses 160 pm) of pure blend of PEO/PVP (70 30) and various compositions of NaF complexed films of... 

Jo et al prepared and characterised Gel polymer electrolytes composed of methy methacrylete-styrene copolymers (PMS) and electrolyte solution (LiT-FSI in EC/DMQ. Depending on the molar composition of the copolymer, these gel polymer electrolytes exhibited different electrochemical and mechanical properties. In order to investigate the physical interactions among organic solvents, polymer, and lithium ions occurred in the gel polymer electrolyte, Raman spectroscopy and solid state Li NMR spin-spin relaxation measurements were performed. 

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