Solid State Ionics

Volume 192, Issue 1, 16 June 2011, Pages 134136

Proceedings of the 17th International Conference on Solid State Ionics

New bismuth ion conducting solid electrolyte

Hirokazu Katayama, Shinji Tamura, Nobuhito Imanaka ,
Department of Applied Chemistry, Faculty of Engineering, Osaka University, 2-1 Yamadaoka, Suite, Osaka 565-0871, Japan Received 26 August 2009. Revised 27 March 2010. Accepted 28 May 2010. Available online 29 June 2010. http://dx.doi.org/10.1016/j.ssi.2010.05.059, How to Cite or Link Using DOI Permissions & Reprints

Abstract
A new trivalent bismuth ion conducting solid electrolyte, (BixGe1 x)4/(4 x)Ta(PO4)3, was successfully developed by selecting the NASICON-type GeTa(PO4)3 as the mother solid. Although bismuth has two kinds of valence states of + 3 and + 5, it was clear that pure trivalent Bi3+ ion conduction, without any electronic conduction by a valence change of bismuth in the oxygen pressure range over 10 3 Pa, was realized by selecting the crystal structure and constituents of the solid.

Keywords
Trivalent cation; Bismuth ion; NASICON-type

1. Introduction
In solid state ionics, it is a commonly accepted idea that ions whose valence state changes easily are inappropriate candidates for conducting ion species in solids due to the appearance of electronic (e or h+) conduction. In fact, most conducting ion species in solids reported are ions that stably hold a single valence state, such as Na+[1], Li+[2], Mg2+[3], O2[4], Al3+[5] and [6], R3+ (R: rare earths) [7] and [8], Zr4+[9], and Hf4+[10]. Although some cations with various valence states have also been reported as conducting ion species in solids, the valency of these cations in the ion conducting solids was the lowest one, such as Cu+(alternative valence: + 2) [11], Mn2+ (alternative: + 7) [12], Co2+ (alternative: + 3) [12], and Ni2+ (alternative: + 3) [12]. For trivalent cation conductors, all the trivalent cations whose possible valency is only + 3 are reported to migrate in solids, except for B3+ and Ga3+ which generally cannot form ionic crystals but form covalent ones that is an unsuitable characteristic for an ion conducting solid electrolyte. Even though bismuth is known to have two valence states of + 3 and + 5, the stable valence state is + 3, similar to the case for the above described Cu+, Mn2+, Co2+, and Ni2+ ions. Therefore, if the bismuth ion holds only the trivalent state in a certain crystal, we can develop a trivalent Bi 3+ cation

conductor by strict selection of the appropriate crystal structure and its constituents. While a Bi3+- -alumina single crystal, wherein monovalent Na+ ions were exchanged for trivalent Bi3+ ions by the ion exchange method, has been reported as a bismuth ion conductor [13], the degree of Bi3+ ion exchange was only ca. 70%. This indicates the possibility of conduction by Na+ ions remaining in the -alumina single crystal. Thus, a pure Bi3+ ion conducting solid has not yet been developed. Up to now, we have clarified that both the selection of the mother crystal structure and the introduction of higher valent cations than the conducting trivalent cation into the structure are essential to develop pure trivalent cation conducting solids. We have successfully developed various kinds of NASICON (Na+ super ionic conductor)-type trivalent cation conductors, whose composition is expressed as (M3+xM4+1 x)4/(4 x)M5+(PO4)3 (M, M, and M are trivalent, tetravalent, and pentavalent cations, respectively)[6] and [8]. In this study, we selected Bi3+ as a new kind of conducting trivalent cation species in solids, and prepared NASICON-type (BixGe1 x)4/(4 x)Ta(PO4)3 by artificially designing the constituents of the solid to realize pure Bi3+ ion conduction without any valence change of bismuth. The ion conducting properties of this solid were investigated.

2. Experimental
(BixGe1 x)4/(4 x)Ta(PO4)3 (0.0 x 0.20) solids were synthesized by the Pechini method [14]. Bi2O3 was dissolved in nitric acid, and GeCl4 and TaCl5 were separately dissolved in ethanol. These solutions were dropped into citric acid (CA) with a molar ratio of [CA]:[M] = 2:1 ([M] = [Bi3+] + [Ge4+] + [Ta5+] + [P5+]). After stirring at 80 C for 12 h, stoichiometric amount of (NH4)2HPO4 aqueous solution and the appropriate amount of ethylene glycol (EG) (molar ratio: [EG] = 4[CA]) were dropped into the citric acid solution, and esterification between CA and EG was accelerated by heating to 150 C to produce a viscous gel. The gel was heated with a gas burner to yield a black powder. This black powder was calcined at 700 C for 6 h in air. These samples obtained were identified by X-ray powder diffraction (XRD) analysis using Cu-K radiation (MultiFlex, Rigaku). The XRD data were collected by a step-scanning method in the 2 range between 10 and 70 with a step width of 0.04. The lattice volume of the samples was calculated from the XRD peak angles with -Al2O3 as a standard powder. After identification of the sample, the powder was pelletized and sintered at 950 C for 12 h in air. For the electrical conductivity measurements, platinum electrodes were formed on the centers of both surfaces of the sintered sample pellet by printing platinum paste and heating at 900 C for 2 h in air. The AC conductivity of the samples was measured by a complex impedance method in the frequency range between 5 Hz and 13 MHz (Hewlett-Packard precision LCR meter, 4192A) in various oxygen pressures ranging from 10 14 Pa to 105 Pa controlled by O2, He, and COCO2 gas mixtures. For polarization measurements, the DC to AC conductivity ratio ( DC / AC) was obtained as a function of time in O2 (Po2: 105 Pa) and He (Po2: 60 Pa) atmospheres at 900 C. In order to directly demonstrate the conducting species in the (Bi0.1Ge0.9)40/39Ta(PO4)3 solid, DC electrolysis was carried out by applying a DC voltage of 6 V at 900 C for 22 days in atmospheric air. After the electrolysis, the cathodic surface of the sample pellet was analyzed by electron probe microanalysis (EPMA, EPMA-1500, Shimadzu).

3. Results and discussion

From the X-ray powder diffraction (XRD) analyses of the prepared samples, it was clear that a single phase of NASICON-type structures were successfully obtained for the samples with x 0.10 while a secondary phase of BiPO4 appeared for the solids with x > 0.10, as shown in Fig. 1. Furthermore, the lattice volume of the NASICON-type phase in the prepared samples linearly increased with increasing x in the single phase region (x 0.10) as depicted in Fig. 2, because the ionic radius of Bi3+ (0.117 nm [coordination number (CN): 6] [15]) is larger than that of Ge4+ (0.067 nm [CN: 6] [15]). Since the lattice volume of the NASICON-type phase did not expand any more in the two-phase mixture region (x > 0.10), it was clear that the solid solubility limit composition forming the single phase of the NASICON-type structure is x = 0.10.
Fig. 1. XRD patterns from (BixGe1 x)4/(4 x)Ta(PO4)3 (x = 0.0 (a), 0.05 (b), 0.075 (c), 0.10 (d), 0.125 (e), 0.15 (f), 0.20 (g)) solids. View thumbnail images Fig. 2. Compositional dependencies of the lattice volume of the NASICON-type phase (), and electrical conductivity at 900 C in air () for the (BixGe1 x)4/(4 x)Ta(PO4)3 (0.0 x 0.20) solids. View thumbnail images

Fig. 2 presents the compositional dependence of the AC conductivity at 900 C in air for the (BixGe1 x)4/(4 x)Ta(PO4)3 (0.0 x 0.20) solids. In the single phase region of the NASICON-type structure (x 0.10), the conductivity monotonically increased with increasing Bi content (x). In the two-phase mixture region (x > 0.10), on the other hand, the conductivity decreased due to the appearance of the impurity phase of BiPO4. This phenomenon also supports the idea that the compositional limit for obtaining the single phase of NASICON-type structure is x = 0.10. In order to confirm the appearance of electronic conduction in the (BixGe1 x)4/ (4 x)Ta(PO4)3 (0.0 x 0.20) solids caused by the valence change of Bi, the AC conductivities of the (Bi0.1Ge0.9)40/39Ta(PO4)3 solid, which shows the highest conductivity among the samples prepared, were measured in various atmospheres whose oxygen pressure was varied from 10 14 Pa to 105 Pa at 900 C. Although the AC conductivity was maintained at a constant value in the atmosphere whose oxygen pressure was over 10 3 Pa, as shown inFig. 3, a clear increase in the AC conductivity was observed in the Po2 range below 10 3 Pa, indicating the appearance of n-type electronic conduction. Since it is known that Bi3+ in the compounds can be reduced to the metallic state in a reducing atmosphere at high temperature, e.g. metallic Bi was obtained by annealing Bi2O3 in an atmosphere with oxygen pressure less than 10 7 Pa at 670 C [16], the Bi cation in the (Bi0.1Ge0.9)40/39Ta(PO4)3 solid might be reduced to the metallic state in such a reducing condition of low oxygen pressure region of < 10 3 Pa at 900 C.
Fig. 3. Oxygen pressure dependence of AC conductivity for the (Bi0.1Ge0.9)40/39Ta(PO4)3 solid at 900 C. View thumbnail images

For investigating the possibility of oxide anion conduction in the (Bi0.1Ge0.9)40/39Ta(PO4)3 solid, we studied the polarization behavior in both O2 (Po2: 105 Pa) and He (Po2: 60 Pa) atmospheres at 900 C, which can provide information on the contribution of oxide anion conduction to total conductivity [5]. If the oxide anion conducts in solids, we will obtain a high DC / AC value in high Po2 atmospheres. In the present case, the DC / AC ratios after 30 min in O2 and He atmospheres reached 0.019 and 0.048, respectively. These results suggest that oxide anion conduction in the (Bi0.1Ge0.9)40/39Ta(PO4)3 solid is also excluded and the predominant conducting species in the (Bi0.1Ge0.9)40/39Ta(PO4)3 solid are limited to cations (Bi3+, Ge4+, Ta5+ and P5+) in atmospheres with oxygen pressures over 10 3 Pa. In addition, we can estimate the cationic

transference number in the (Bi0.1Ge0.9)40/39Ta(PO4)3 solid from the equation [1 (DC / AC)] to be 0.981 in an O2 atmosphere [5]. In order to directly demonstrate Bi3+ ion conduction in the (Bi0.1Ge0.9)40/39Ta(PO4)3 solid, DC electrolysis was carried out by using two platinum plates as ion-blocking electrodes. By applying a DC voltage higher than the decomposition voltage (the decomposition voltage at 900 C was preliminarily investigated to be ca. 0.15 V), only the conducting cation species is forced to continuously and macroscopically migrate toward the cathodic direction. As a result, evidence of the migration of the conducting cationic species can be found at or near the cathodic surface with which the platinum ion-blocking electrode is in contact. After DC electrolysis by the application of 6 V at 900 C for 22 days in atmospheric air, elemental distribution inside the sample pellet was investigated by line EPMA measurements; the results are shown in Fig. 4. Clear segregation was observed only for Bi near the cathodic surface. Bi segregation inside the sample pellet indicates that the Bi ion migrated from the anodic side through the sample. Also, segregation did not occur by sample decomposition at the cathodic surface. This result clearly demonstrates that only Bi ion migration occurs in the (Bi0.1Ge0.9)40/39Ta(PO4)3 solid.
Fig. 4. Setup for DC electrolysis and EPMA line analysis results for cationic species in the (Bi0.1Ge0.9)40/39Ta(PO4)3 solid. View thumbnail images

4. Conclusions
We have for the first time succeeded in developing a pure trivalent Bi3+ ion conducting solid electrolyte, (BixGe1 x)4/(4 x)Ta(PO4)3, without any electronic conduction caused by the valence change of Bi in atmospheres with oxygen pressure over 10 3 Pa, by strictly selecting a NASICONtype structure and the constituent ions. Among the samples prepared, the compositional limit to form a single phase of the NASICON-type structure is x = 0.10, and the highest ion conductivity was obtained for the (Bi0.1Ge0.9)40/39Ta(PO4)3 (x = 0.10) solid.

Acknowledgment
This work has been supported in part by a Grant-in-Aid for Science Research (No. 21750208) from theMinistry of Education, Culture, Sports, Science and Technology (MEXT) of Japan.

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