Scheelite-structured composite metal oxide with oxygen ionic conductivity

A composite metal oxide represented by the formulaMa1−xMbxMcO4+x/2,wherein Ma is at least one element selected from alkaline earth metals, Mb is at least one element selected from lanthanoids, Mc is at least one element selected from Mo and W, and x is from about 0.1 to about 0.5.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority to and the benefit of Korean Patent Application No. 10-2013-0018832, filed on Feb. 21, 2013, and all the benefits accruing therefrom under 35 U.S.C. §119, the content of which is incorporated herein in its entirety by reference.

BACKGROUND

The present disclosure relates to materials with oxygen ionic conductivity, and more particularly, to a composite metal oxide with oxygen ionic conductivity. The composite metal oxide with oxygen ionic conductivity, for example, may be used as solid electrolyte and electrode material of a solid oxide fuel cell (“SOFC”). For other example, the composite metal oxide with oxygen ionic conductivity may be used in an oxygen sensor, an oxygen pump, and an oxygen permeating membrane.

2. Description of the Related Art

An SOFC unit cell includes a solid electrolyte and an electrode. Accordingly, the electrical characteristics of the solid electrolyte and the electrode are closely related to the performance of the SOFC. In particular, the ionic conductivity of the solid electrolyte and the ionic conductivity of the electrode material are important factors that determine the ohmic resistance and polarization resistance of the SOFC unit cell. Therefore, research has focused on the development of ion conductive materials for decades. Mixed oxides which have been suggested as materials for the solid electrolyte and electrode material of an SOFC usually have high electron mobility and high hole mobility but low oxygen ion mobility. Thus, only few materials with suitable ion conductivity have been discovered. Some materials with high ionic conductivity include those having a fluorite structure such as YSZ (yttria-stabilized zirconia: Y-doped ZrO2), CSZ (Ca-doped ZrO2), and GDC (Gd-doped CeO2). Other materials with high ionic conductivity include those having a Perovskite structure such as LSGM (Sr, Mg-doped LaGaO3).

Thus, there remains an unmet need for materials having improved oxygen ion conductivity.

SUMMARY

According to an aspect, the present disclosure provides a composite metal oxide represented by the formula
Ma1−xMbxMcO4+x/2,
wherein Mais at least one element selected from alkaline earth metals, Mbis at least one element selected from lanthanoids, Mcis at least one element selected from Mo and W, and x is from about 0.1 to about 0.5.

According to another aspect, the present disclosure provides a solid electrolyte layer including a composite metal oxide represented by the formula
Ma1−xMbxMcO4+x/2,
wherein Mais at least one element selected from alkaline earth metals, Mbis at least one element selected from lanthanoids, Mcis at least one element selected from Mo and W, and x is from about 0.1 to about 0.5.

According to another aspect, the present disclosure provides a reaction barrier layer including a composite metal oxide represented by the formula
Ma1−xMbxMcO4+x/2,
wherein Mais at least one element selected from alkaline earth metals, Mbis at least one element selected from lanthanoids, Mcis at least one element selected from Mo and W, and x is from about 0.1 to about 0.5.

According to another aspect, the present disclosure provides a fuel cell including a cathode, a solid electrolyte layer, an anode, an optional first reaction barrier layer disposed between the cathode and the solid electrolyte layer, and an optional second reaction barrier layer disposed between the anode and the solid electrolyte layer, wherein at least one of the cathode, the solid electrolyte layer, the anode, the first reaction barrier layer, and the second reaction barrier layer includes a composite metal oxide represented by the formula
Ma1−xMbxMcO4+x/2,
wherein Mais at least one element selected from alkaline earth metals, Mbis at least one element selected from lanthanoids, Mcis at least one element selected from Mo and W, and x is from about 0.1 to about 0.5.

DETAILED DESCRIPTION

In an aspect of the present disclosure, a composite metal oxide is described in further detail as set forth hereunder.

In an embodiment, the present disclosure provides a composite metal oxide represented by the formula
Ma1−xMbxMcO4+x/2,
wherein Mais at least one element selected from alkaline earth metals, Mbis at least one element selected from lanthanoids, Mcis at least one element selected from Mo and W, and x is from about 0.1 to about 0.5.

In the present disclosure, Mais at least one element selected from alkaline earth metals. Alkaline earth metals are elements that belong to Group 2 of the periodic table. Alkaline earth metals include Be, Mg, Ca, Sr, Ba, Ra, and Ubn. In an embodiment, Mamay be at least one element selected from Be, Mg, Ca, Sr, Ba, Ra, and Ubn. In another embodiment, Mamay be at least one element selected from Ca, Sr, and Ba.

In the present disclosure, Mcis at least one element selected from Mo and W. In an embodiment, Mcmay be Mo; W; or Mo1−zWz(0<z<1). In another embodiment, z may be from about 0.01 to about 0.50.

In the present disclosure, x is from about 0.1 to about 0.5. While not wanting to be bound by theory, as the value of x increases, a content of the secondary phase (which may be an unintended phase or an undesirable phase) increases. When x is too large the amount of the secondary phase may become undesirable, thereby interconnecting the secondary phases and thus significantly decreasing ionic conductivity. In contrast, when x is too small, the amount of oxygen, which serves as an ion conducting carrier, i.e., the value of (4+x/2), may be insufficient, significantly reducing ionic conductivity.

An embodiment of a composite metal oxide represented by Ma1−xMbxMcO4+x/2may have a scheelite structure. In a general view, the scheelite structure has a tetragonal structure. In addition, in a local view of the scheelite structure, MoO4in SrMoO4form regular tetrahedra wherein Sr is disposed between the MoO4regular tetrahedrons.

Examples of composite metal oxides with a scheelite structure include SrMoO4, and SrMoWO4. However, these metal oxides do not have suitable ionic conductivity. In an aspect of the present disclosure, the composite metal oxide represented by Ma1−xMbxMcO4+x/2has a scheelite structure and superior ionic conductivity. While not wanting to be bound by theory, it is believed that the superior ionic conductivity is due to the following reasons: in SrMoO4not doped with La, the structure of MoO4is close to a regular tetrahedron, and thus the bond lengths of all four Mo—O bonds are the same. However, after La is doped into SrMoO4, the structure of MoO4turns into an irregular tetrahedron. Accordingly, an oxygen position with a different energy is generated. Thereby, interstitial oxygen, which is introduced to provide electroneutrality, becomes present within an irregular MoO4structure; and it is the unstable, charged interstitial oxygen that contributes to ion conductivity.

An embodiment of a solid electrolyte layer according to another aspect of the present disclosure comprises a composite metal oxide represented by the formula
Ma1−xMbxMcO4+x/2,
wherein Mais at least one element selected from alkaline earth metals, Mbis at least one element selected from lanthanoids, Mcis at least one element selected from Mo and W, and x is from about 0.1 to about 0.5.

An embodiment of a reaction barrier layer according to another aspect of the present disclosure comprises a composite metal oxide represented by the formula
Ma1−xMbxMcO4+x/2,
wherein Mais at least one element selected from alkaline earth metals, Mbis at least one element selected from lanthanoids, Mcis at least one element selected from Mo and W, and x is from about 0.1 to about 0.5.
In another aspect, the present disclosure provides a fuel cell including a cathode, a solid electrolyte layer, an anode, an optional first reaction barrier layer disposed between the cathode and the solid electrolyte layer, and an optional second reaction barrier layer disposed between the anode and the solid electrolyte layer, wherein at least one of the cathode, the solid electrolyte layer, the anode, the first reaction barrier layer, and the second reaction barrier layer comprises a composite metal oxide represented by the formula
Ma1−xMbxMcO4+x/2,
wherein Mais at least one element selected from alkaline earth metals, Mbis at least one element selected from lanthanoids, Mcis at least one element selected from Mo and W, and x is from about 0.1 to about 0.5.

In an embodiment, in addition to a fuel cell, the composite metal oxide represented by the formula Ma1−xMbxMcO4+x/2may be applied to provide an oxygen probe, a chemical membrane reactor, an oxygen separation membrane, an oxygen pump, a hydrogen separation membrane, a hydrogen pump, a hydrogen gas sensor, a steam sensor, a hydrocarbon sensor, a hydrogen extraction, a hydrogen pressure controller, isotope enrichment, tritium technology, steam electrolysis, H2S electrolysis, HCl electrolysis, hydrogenation of a hydrocarbon, dehydrogenation, NH3formation, and an electrochemical device such as an electrochemical cell, an electrochromic device, or a gas sensor.

Hereinafter, one or more embodiments are described in greater detail using Examples; however, the present disclosure is not limited thereto.

EXAMPLES

Examples 1 to 7

Preparation of Composite Metal Oxides

Composite metal oxides according to an embodiment of the present disclosure were prepared via a conventional ceramic manufacturing process. The composition of the composite metal oxides prepared is shown in Table 1 below.

Precursors used in the examples were SrCO3(99.9 weight %, Aldrich), La2O3(99.9 weight %, Aldrich), MoO3(99.5 weight %, Alfa Aesar) and WO3(99.99 weight %, Aldrich). The amount of composite metal oxide powders prepared in each example was 10 grams (g). First, the powders of the precursors were weighed based on a molar ratio of metal elements, added along with 40 mL of ethanol into a Nalgene bottle containing zirconia balls, and subjected to a ball milling for 6 hours. Then, the mixed powder was dried in the air, and calcined in the air at 1,000° C. for 3 hours to obtain a composite metal oxide powder with a scheelite structure. The obtained composite metal oxide powder was added into a metal mold and pressed to obtain a composite metal oxide pellet with a diameter of 10 millimeters (mm) and a thickness of 5 mm. Then, cold isostatic pressing (“CIP”) was performed to increase the molding density of the composite metal oxide pellet. The pressure during CIP was 200 megaPascals (MPa), which was maintained for 5 minutes. Then, the composite metal oxide pellet was sintered at 1,250° C. for 10 hours for its densification (i.e., increasing of density).

Measurement of Electric Conductivity

The resistance of a sintered composite metal oxide pellet was measured according to 2-probe AC method and 4-probe DC method. The device used for the 2-probe AC method was Model 7260 (Materials Mates Co., Ltd.), and that for the 4-probe DC method was Model 2400 (Keithley Co., Ltd.). The range of frequency used in the 2-probe AC method was from 10 MHz to 1 Hz. The resistance of a specimen was measured while controlling temperature and oxygen partial pressure. The oxygen partial pressure PO2was 10−5atm≦PO2≦1 atm. The oxygen partial pressure was controlled by mixing oxygen gas and nitrogen gas.

Measurement of Electromotive Force (EMF)

In order to identify the charge carrier of a specimen, EMF was measured. First, a composite metal oxide pellet with a diameter of 25 mm and a thickness 1 mm was formed by using the composite metal oxide powders prepared in Examples 1 to 7 using a metal mold. The composite metal oxide pellet was sintered under the same condition as in Examples 1 to 7 to obtain a sintered composite metal oxide pellet. In order to control the gas atmosphere at both ends of the specimen, two alumina tubes were used. At one end of the specimen, the oxygen partial pressure (P1) was maintained at 1 atm using oxygen gas, whereas at the other end, the oxygen partial pressure (P2) was varied from 1 atm to 5×10−4atm. In order to measure EMF, electrodes were formed at both ends of the specimen using Pt-paste, and Pt-wires were connected to the electrodes.

XRD Analysis

An XRD analysis was performed to confirm whether a calcined composite metal oxide powder had an intended phase.FIG. 1shows an XRD pattern of the calcined composite metal oxide powder. The calcined composite metal oxide powders obtained in Examples 1 to 7 were all confirmed to have a scheelite phase. However, a little amount of the secondary phase was detected in all of the calcined composite metal oxide powders obtained in Examples 1 to 7, and as the amount of La as a dopant increased, the peak of the secondary phase became higher. The composition of the secondary phase was La2Mo2O9. However, as shown inFIG. 2, the effect of the La2Mo2O9phase on the electric characteristics of a specimen is not significant.FIG. 2shows a Scanning Electron Microscope (“SEM”) image of calcined composite metal oxide powder (Sr0.70La0.30Mo O4) obtained in Example 4. The composition described inFIG. 2was obtained by an analysis of Energy Dispersive Spectrometer (“EDS”). As shown inFIG. 2, La-rich phases, i.e., La2Mo2O9phases are not connected to each other but are present sporadically on the grain boundary of SrMoO4-based grains.FIG. 3shows a graph illustrating the volume of a crystal lattice calculated from the peak location of an XRD pattern ofFIG. 1according to La doping concentration. As shown inFIG. 3, the volume rapidly decreases until x=0.2, and then slowly until x=0.4. This indicates that doping can be performed well on the crystal lattice of SrMoO4until La=0.2, but only part of La can be doped and the rest of La cannot be doped when La has a higher content. The secondary phase is formed by the undoped La.

Electric Conductivity

An impedance pattern of the sintered composite metal oxide pellet (Sr0.50La0.50Mo O4:SLM50) obtained in Example 6 was measured according to the 2-probe AC method and the result is shown inFIG. 4. InFIG. 4, the semicircle region (high frequency region) indicates an impedance pattern generated by the resistance of a specimen. That is, the diameter of the semicircle is the resistance of the specimen. The subsequent linear region (low frequency region) indicates a pattern corresponding to the resistance of an electrode. InFIG. 4, figures are represented in log (frequency) value. What is to be noted inFIG. 4is a size of the semicircle according to a gas atmosphere. As shown inFIG. 4, the change in a gas atmosphere did not change the size of the semicircle, which indicates that the charge carrier of the specimen is not electrons but oxygen ions. This is because the electronic conduction in oxides generally depends on oxygen partial pressure. In general, oxygen ion conductivity is independent of an oxygen atmosphere.

The conductivity according to the temperature of the sintered composite metal oxide pellets obtained in Example 2 (Sr0.85La0.15Mo O4:SLM15), Example 4 (Sr0.70La0.30MoO4:SLM30), Example 5 (Sr0.60La0.40Mo O4:SLM40), and Example 6 (Sr0.50La0.50Mo O4:SLM50), measured via the 2-probe AC method and 4-probe DC method, is shown inFIG. 5. The conductivity of each specimen increased as the amount of the dopant (La) increased. This is because La was incorporated into an Sr position, thereby, interstitial oxygen was introduced to provide the electroneutrality of the specimen, and the amount of the interstitial oxygen increased in proportion to the amount of La. The ion conductivity of yttria stabilized zirconia (“YSZ”) shown in Table 5 was cited from “S. Skinner, Materials Today, 2003, pp. 30-37”. Surprisingly, the conductivity of SLM50 was shown to be comparable to that of YSZ, the representative solid electrolyte material of an SOFC. As confirmed by the impedance measurement according to a gas atmosphere, the conductivity is ion conductivity. The high conductivity of SLM50 is quite unexpected considering that the conductivity is ion conductivity.

The conductivity of SLM40 according to oxygen partial pressure is shown inFIG. 6. As shown inFIG. 6, the change in oxygen partial pressure did not affect the conductivity. From this, it can be speculated that the conductivity of the composite metal oxide of the present disclosure is ion conductivity.

FIG. 7is a result of EMF measurements of SLM40. As shown inFIG. 7, as P2 decreased (i.e., as the difference between P1 and P2 increases) the EMF value increased. Further, the EMF value matched well with the theoretical value of the specimen having ionic conductivity. The solid lines inFIG. 8represent theoretical values. Based on these results, it was confirmed that the charge carrier of the specimen is oxygen ion.

FIG. 8shows the result of conductivity according to temperature measured for SLM50 and SLMW specimens. FromFIG. 8, it was confirmed that the replacement of Mo, a hexavalent element, with W, another hexavalent element, still resulted in excellent conductivity.