Study of Mechanisms of Ion Transport in Ion Conducting Glasses

P. Bury ^a), P. Hockicko ^a), M. Jamnický ^b) and I. Jamnický ^a)

^a) Department of Physics, Žilina University, 010 26 Žilina, Slovakia (bury@fel.utc.sk)

^b) Department of Ceramic, Glass and Cement, Slovak Technical University, 812 37 Bratislava

Abstract In the past twenty years, there has been an increase of interest in ion conductive glasses and their possible future practical application. Comparing with the crystalline materials the ionic glasses has several advantages the most important of which are: the absence of grain boundaries, the isotropic properties and the composition variability. The electrical methods have been already proved an effective tool to study the fundamental transport properties of the ionic materials and the conductivity measurements made over a wide range of frequencies and temperatures can characterise different types of transport mechanisms. The purpose of present work is to compare data obtained by electrical measurement (dc and ac conductivity) of ion conductive glasses of the system CuI-CuBr-Cu₂O-(P₂O₅+M₀O₃) for different glass composition and study the ionic hopping motion and relaxation processes connected with the charge mobility. Partial attention is paid also to the problem of the role of composition in this system.

I. Introduction A considerable attention is given in recent years to glassy materials with the fast ion transport called solid state electrolytes because of the possibility of their application in modern electrochemical devices, such as solid-state batteries, electrochronic displays, and sensors as well as for fundamental interest in their ion transport mechanisms [1,2]. The ion conductive glasses have several advantages comparing with crystalline materials because of their easy preparation, their stability and the large available composition ranges.

The investigation of conductivity spectra of ionic glasses can reflects the basic features of the relaxation and transport mechanisms of the mobile ions and the high ion conductivity at room temperature is the most important criterion witch should be meet the fast ion conductive glasses. Here is a good opportunity for glasses containing Cu⁺ conductive ions that have similar electronic configuration and smaller ionic radii in comparison with Ag⁺ ion and could achieve comparable conductivity [3].

While there are many papers on Ag⁺-ion conducting glasses in various glass-forming systems, Cu⁺-ion conducting glasses are only known in very limited glass-forming systems. Phosphate glasses containing Cu⁺ conducting ions are good ionic conductors with room temperature conductivity of the order 10^-3W^-1cm^-1 [4,5]. The highest conductivity has been recorded in systems containing large more fractions of cuprous halides, such as CuI or CuBr. Moreover, if two different kinds of halide anions are mixed into cation conducting glasses [6], a positive deviation of the electrical conductivity from the additivity rule can be observed (mixed anion effect). In this contribution we present some electrical (transport) properties of glasses prepared in the systems CuI-CuBr-Cu₂O-M_mO_n where M_mO_n is P₂O₅ and/or MoO₃. The main purpose of the contribution is to investigate ion transport mechanisms and to determine the relation between glass composition and electrical conductivity.

II. Experimental The preparation of glasses in the system CuI-CuBr-Cu₂O-(P₂O₅+MoO₃) from commercial reagents (Fluka) represented the procedure already described [6]. Batches of 15 g were melted under a dry argon atmosphere to avoid the oxidation of Cu⁺ during melting and mixed in appropriate portion (see Tables 1 and 2) in silica ampoule at 933 K for 90 min. The glass melts were rapidly quenched by pressing them between two brass plates to a final thickness of » 1.5 mm. The resulting discs of 20 mm in diameter were kept between the plates until their temperature decreased to room temperature. Losses in weight during melting were < 1 %. To check the reproducibility of the results, all glasses were prepared three times. Two systems of glasses were prepared to investigate both the role of glass-forming system and the role of cuprous halides produced Cu⁺ ions keeping their ratio 60 mol. % to 40 mol. %.

The samples for electrical conductivity measurements were cylindrical in shape (area » 1 cm², thickness » 1-2 mm). Gold electrodes were sputtered onto the sample surfaces. The frequency and temperature dependencies of electrical conductivity were measured (d.c. and a.c. in the frequency range from 50 Hz up to 1 MHz using FLUKE PM 6306 impedance analyser and in the temperature range of 140-380 K temperature range ~ 100°C. The measured complex impedance allowed us to obtain the bulk d.c. and a.c. conductivity of glass samples by means of the usual impedance analysis.

Table 1 Starting compositions (in mol.%) of glasses prepared in the System I

Glass		Composition	(in mol.%)
sample	CuI	CuBr	Cu2O	P2O5	MoO3
IP	25.000	-	56.250	18.750	-
IPM	25.000	-	46.875	9.375	18.750
BPM	-	25.000	46.875	9.375	18.750
IM	25.000	-	37.500	-	37.500

Table 2 Starting compositions (in mol.%) of glasses prepared in the System II

Glass		Composition	(in mol.%)
sample	CuI	CuBr	Cu2O	P2O5	MoO3
IBPM 2	21.875	3.125	46.875	9.375	18.750
IBPM 3	18.750	6.250	46.875	9.375	18.750
IBPM 5	15.625	9.375	46.875	9.375	18.750
IBPM 1	12.500	12.500	46.875	9.375	18.750
IBPM 4	6.250	18.750	46.875	9.375	18.750

III. Results The measured complex impedance allowed to obtain the bulk d.c. and a.c. conductivity of glass samples of both systems at given temperature range.

The representative results of d.c. conductivity measurement (sample IBPM 2) as a function of temperature are illustrated in Fig. 1. As all of the temperature dependence of d.c. glass conductivity can be fitted by the equation

s = s₀ exp(-E_a/kT), (1)

where E_a is the activation energy, k  is the Boltzman constant and T is the absolute temperature, the temperature dependencies of d.c. conductivity indicates two transport mechanisms with activation energies E_a1, and E_a2 for higher and lower temperatures, respectively. Because the pre-exponential factor s₀ is a function of temperature the factor sT is used in Arrhenius plots of d.c. conductivity. Activation energies calculated from Arhenius plots of d.c. conductivity for all glass samples are summarised in Table 3.

Table 3. Summary of activation energies calculated from Arrhenius plots of d.c. conductivity for glasses of both systems

Glass sample	Ea1 (eV)	Ea2 (eV)	Glass sample	Ea1 (eV)	Ea2 (eV)
IP	0.295	0.500	IBPM 2	0.178	0.394
IPM	0.386	0.402	IBPM 3	0.274	0.405
BPM	0.359	0.382	IBPM 5	0.333	0.402
IM	0.240	0.320	IBPM 1	0.341	0.399
			IBPM 4	0.247	0.383

All the prepared glasses have high ionic conductivity at room temperatures (10^-2 -10^-4 W^-1m^-1). The samples of system II. that contain always the same molar amount of glass-forming components exhibit very close values of activation energies E_a2 characterising the transport mechanisms at lower temperatures. The same activation energy E_a2 have also samples IPM and BPM from system I. but containing the same concentrations of Cu₂O-P₂O₅-MoO₃ components. However, the activation energies E_a1 characterising ion transport at higher temperatures depends on the ratio of CuI to CuBr responsible for Cu⁺ ion concentrations and indicates similar role of both components in the process of Cu⁺ mobile ion governing the conductivity.

The set of frequency dependencies of a.c. conductivity measured at various temperatures is illustrated in Fig. 2 for glass sample IBPM 3 and in Fig. 3 for sample IPM. The obtained a.c. conductivity measurements correspond to the complete conductivity spectra obtained from glassy samples [7,8]. However, because of limited frequency range, only two regimes (II and III) of [7, 8] due to hopping motion separated by slope represented by breaks on individual curves could be recognised, the regime II only at low temperatures yet. While the glass samples of system II. exhibits one slope of brakes, the glass sample IPM exhibits evidently another brakes on the a.c. conductivity spectra indicated another transport hopping process that can be explained by slightly modified jump relaxation model [7].

IV. Conclusion The first experimental investigation of electrical properties both d.c. and a.c. conductivity of ion conductive glasses in system CuI-CuBr-Cu₂O-(P₂O₅+MoO₃) showed the important influence of chemical composition an ion transport mechanisms and indicated more than one possible conductivity mechanism.

However, the further investigation in wider temperature and frequency ranges of glass samples with different compositions and comparing with the results some different measurements should be done for better understanding of ion transport mechanisms in investigated ion conducting glasses.

Acknowledgement This work was partly financially supported by Grants No 1/8308/01 and No 1/9141/02 of the Ministry of Education of the Slovak Republic

References

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