Electrolytes polycrystalline materials

A commonly inexpensive way to prepare solid electrolytes is the formation of monolithic samples. Depending on the required phases and final compounds, a large variety of preparation methods are known. These methods usually provide polycrystalline materials. 

It has been illustrated that polycrystalline materials can be operated in regenerative electrolytic solar cells yielding substantial fractions of the respectable energy conversion efficiency obtained by using single crystals. Pressure-sintered electrodes of CdSe subsequently doped with Cd vapor have presented solar conversion efficiencies approaching 3/4 of those exhibited by single-crystal CdSe electrodes in alkaline polysulfide PEC [84]. 

Sodium /3-aluminas (often known as simply /3-aluminas ) are examples of solid electrolytes, i,e. compounds which permit fast ionic motion (here of sodium ions) within a solid lattice, While /3-aluminas conduct reasonably well at room temperature ( 1 S/m for polycrystalline material), they are generally used at temperatures over 300°C where their conductance is greater than 10 S/m. ( Ambient solid electrolytes and batteries based on these will be considered in the next chapter.)... 

Electrodeposits from simple salt electrolytes often exhibit macroscopically rough, faceted surfaces that are associated with epitaxial and/or columnar growth of large-grained polycrystalline materials. The addition of certain additives leads to substantial grain refinement, often into the nanometer range, and randomization of... 

The discovery of a solid conductor of sodium ions by Kummer and Weber made possible the construction of sodium-sulfur cells which utilize molten or dissolved reactants separated by the ceramic electrolyte j3-(cf. Fig. 12), or, usually, j3"-alumina. The latter ceramic has a three Al-0 spinel block structure, a molar ratio of Al203-Na20 = 5, and contains 1-4% of MgO or Li20. The resistivity of the polycrystalline material at 350°C is about 5 H cm, -4 times lower than that of alumina. Other recently reported solid Na ion conductors containing phosphorus oxides do not seem to be stable in contact with sodium at elevated temperatures. ... 

Most of the reported electrochemistry with solid electrodes involves polycrystalline materials. Such electrodes consist of a variety of small domains with different crystal faces and edges presented to the contacting electrolyte. As discussed below, different crystal faces exhibit different properties (e.g., PZC or work function) so that the behavior observed at a polycrystalline electrode represents an average of that for a number of different crystal... 

Zinc sulfide, with its wide band gap of 3.66 eV, has been considered as an excellent electroluminescent (EL) material. The electroluminescence of ZnS has been used as a probe for unraveling the energetics at the ZnS/electrolyte interface and for possible application to display devices. Fan and Bard [127] examined the effect of temperature on EL of Al-doped self-activated ZnS single crystals in a persulfate-butyronitrile solution, as well as the time-resolved photoluminescence (PL) of the compound. Further [128], they investigated the PL and EL from single-crystal Mn-doped ZnS (ZnS Mn) centered at 580 nm. The PL was quenched by surface modification with U-treated poly(vinylferrocene). The effect of pH and temperature on the EL of ZnS Mn in aqueous and butyronitrile solutions upon reduction of per-oxydisulfate ion was also studied. EL of polycrystalline chemical vapor deposited (CVD) ZnS doped with Al, Cu-Al, and Mn was also observed with peaks at 430, 475, and 565 nm, respectively. High EL efficiency, comparable to that of singlecrystal ZnS, was found for the doped CVD polycrystalline ZnS. In all cases, the EL efficiency was about 0.2-0.3%. 

Figure 16. Model In PC based electrolytes, solvent co-intercalation, gas formation and crevice formation in polycrystalline graphite materials are inter-related reactions. In fact, there is a subsequence of reactions (1) PC co-intercalation, (2) gas formation, (3) crevice formation ultimately resulting in exfoliation and macroscopic destruction of graphite [40],...

Water is involved in most of the photodecomposition reactions. Hence, nonaqueous electrolytes such as methanol, ethanol, N,N-d i methyl forma mide, acetonitrile, propylene carbonate, ethylene glycol, tetrahydrofuran, nitromethane, benzonitrile, and molten salts such as A1C13-butyl pyridium chloride are chosen. The efficiency of early cells prepared with nonaqueous solvents such as methanol and acetonitrile were low because of the high resistivity of the electrolyte, limited solubility of the redox species, and poor bulk and surface properties of the semiconductor. Recently, reasonably efficient and fairly stable cells have been prepared with nonaqueous electrolytes with a proper design of the electrolyte redox couple and by careful control of the material and surface properties [7], Results with single-crystal semiconductor electrodes can be obtained from table 2 in Ref. 15. Unfortunately, the efficiencies and stabilities achieved cannot justify the use of singlecrystal materials. Table 2 in Ref. 15 summarizes the results of liquid junction solar cells prepared with polycrystalline and thin-film semiconductors [15]. As can be seen the efficiencies are fair. Thin films provide several advantages over bulk materials. Despite these possibilities, the actual efficiencies of solid-state polycrystalline thin-film PV solar cells exceed those obtained with electrochemical PV cells [22,23]. 

Compounds of the I—VII group in the periodic table are known to exhibit good ionic conductivity and have attracted much attention as possible candidates for solid electrolytes. A typical family of compounds is Lil, CuCl, CuBr, and Agl. Historically, polycrystalline solid electrolytes were noticed to show significantly higher ionic conductivity than bulk crystals, since a half century ago. Furthermore, a large increase in conductivity was reported for the system of the mixture of a solid electrolyte such as CuCl (1) and Agl (2) with submicrometer particles of several sorts of insulating materials. In this case, the size of the metal halide itself was on the order of a micrometer or larger. It was also reported that the enhanced conductivity was approximately proportional to the inverse of the size of the electrolyte substances (2). Hence it is natural to make an effort to obtain fine particles of metal halides in order to get better conductivity. 

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