Beta-alumina-based sintered compact and its production method

Abstract

To provide a dense beta-alumina-based sintered compact having a high ionic conductivity as a solid electrolyte by firing at a low temperature to suppress the volatilization of Na.sub.2O and its production method. By adding RNbO.sub.3 which is a material having a low melting point to a beta-alumina powder, followed by firing, it is possible to obtain a beta-alumina-based sintered compact having a low firing temperature and containing, as the main component, dense β″ alumina crystals which are free from anomalous grain growth during the firing process.

Claims

1. A beta-alumina-based sintered compact, comprising: a beta-alumina crystalline phase having Na.sub.2O and Al.sub.2O.sub.3 as main components; and an RNbO.sub.3 crystalline phase; wherein R is at least one element selected from the group consisting of Li, Na, and K.

2. The beta-alumina-based sintered compact according to claim 1, wherein the beta-alumina crystalline phase comprises a β″ alumina crystalline phase.

3. The beta-alumina-based sintered compact according to claim 1, wherein R is Na.

4. The beta-alumina-based sintered compact according to claim 1, comprising NiO as a component.

5. The beta-alumina-based sintered compact according to claim 4, wherein a chemical composition of the beta-alumina-based sintered compact, based on oxides, is: from 8 to 15 mass % of Na.sub.2O; from 5 to 30 mass % of Nb.sub.2O.sub.5; from 1 to 10 mass % of NiO; and a remainder of Al.sub.2O.sub.3.

6. A method for producing the beta-alumina-based sintered compact as defined in claim 1, comprising: mixing a beta-alumina powder and an RNbO.sub.3 powder; and molding and firing the mixture; wherein R is at least one element selected from the group consisting of Li, Na, and K.

7. The method for producing the beta-alumina-based sintered compact according to claim 6, wherein firing the mixture comprises firing at a temperature of less than 1450° C.

8. The method for producing the beta-alumina-based sintered compact according to claim 6, wherein the beta-alumina powder comprises β″ alumina.

9. The method for producing the beta-alumina-based sintered compact according to claim 6, wherein R is Na.

10. The method for producing the beta-alumina-based sintered compact according to claim 6, wherein the beta-alumina powder comprises NiO.

11. The method for producing the beta-alumina-based sintered compact according to claim 10, wherein a chemical composition of the beta-alumina-based sintered compact, based on oxides, is from 8 to 15 mass % of Na.sub.2O; from 5 to 30 mass % of Nb.sub.2O.sub.5; from 1 to 10 mass % of NiO; and a remainder of Al.sub.2O.sub.3.

12. A beta-alumina-based sintered compact, comprising: as chemical components, based on oxides, Na.sub.2O and Al.sub.2O.sub.3; and as a crystalline phase, a beta alumina crystalline phase and an RNbO.sub.3 crystalline phase; wherein R is at least one element selected from the group consisting of Li, Na, and K.

13. The beta-alumina-based sintered compact according to claim 12, wherein the beta-alumina crystalline phase comprises a β″ alumina crystalline phase.

14. The beta-alumina-based sintered compact according to claim 12, wherein R is Na.

15. The beta-alumina-based sintered compact according to claim 12, comprising NiO.

16. The beta-alumina-based sintered compact according to claim 15, wherein a chemical composition of the beta-alumina-based sintered compact, based on oxides, is: from 8 to 15 mass % of Na.sub.2O, from 5 to 30 mass % of Nb.sub.2O.sub.5; from 1 to 10 mass % of NiO; and a remainder of Al.sub.2O.sub.3.

Description

BRIEF DESCRIPTION OF DRAWING

(1) FIG. 1 is a SEM image in fracture cross-section of the sintered compact in Example 1.

DESCRIPTION OF EMBODIMENT

(2) Now, an embodiment of the present invention will be described in detail.

(3) The beta-alumina-based sintered compact of the present invention is a sintered compact having a beta-alumina crystalline phase, wherein an RNbO.sub.3 crystalline phase and a beta-alumina crystalline phase are contained.

(4) The RNbO.sub.3 crystalline phase contained in the beta-alumina-based sintered compact of the present invention has a function as a binding reinforcement agent for grain boundary of beta-alumina particles, whereby the production of a solid electrolyte having a long life span and a high reliability, can be realized. An RNbO.sub.3 powder to be a source of the RNbO.sub.3 crystalline phase is a sintering agent having a low melting point, which becomes a liquid phase state at the time of firing and accelerates the sintering of beta-alumina. Spaces among the beta-alumina crystalline particles are filled with the RNbO.sub.3 in the liquid phase state, which makes a sintered compact dense.

(5) When the alkali metal element (R) in the RNbO.sub.3, is Na element, the above function can be maximally obtained. Thus, it is preferred that an NaNbO.sub.3 crystalline phase is present in the beta-alumina-based sintered compact, or it is preferred to use an NaNbO.sub.3 powder as a sintering agent.

(6) In the beta-alumina-based sintered compact of the present invention, the beta-alumina crystalline phase may contain a small amount of a β alumina crystalline phase, however, it is preferred that the beta-alumina crystalline phase consists mostly of a β″ alumina crystalline phase from the viewpoint of the ionic conductivity. In order to improve the ionic conductivity, it is more preferred for that the beta-alumina crystalline phase consists solely of a β″ alumina crystalline phase.

(7) The beta-alumina-based sintered compact of the present invention preferably contains a stabilizer for stably maintaining the β″ alumina crystalline structure. It is preferred that the stabilizer has not only an effect to stabilize the crystalline structure but also an effect to prevent the anomalous grain growth during the firing process, particularly the process in which a liquid phase exists.

(8) As the stabilizer, NiO is preferred, since not only the β″ alumina crystalline structure can be maintained, but also the anomalous grain growth can be prevented during firing, and the sintered compact is made to be dense. Further, it is more preferred that NiO is contained in the beta-alumina crystalline phase in the sintered compact, and it is further preferred that NiO is contained in the β″ alumina crystalline structure.

(9) Further, the presence of the crystalline phase can be confirmed by the identification by means of an X-ray diffraction apparatus.

(10) It is preferred that the chemical composition of the beta-alumina-based sintered compact of the present invention comprises, based on oxides, from 8 to 15 mass % of Na.sub.2O, from 5 to 30 mass % of Nb.sub.2O.sub.5 and the rest being Al.sub.2O.sub.3.

(11) Further, it is more preferred that the beta-alumina-based sintered compact of the present invention contains NiO as a stabilizer, and the chemical composition comprises, based on oxides, from 8 to 15 mass % of Na.sub.2O, from 5 to 30 mass % of Nb.sub.2O.sub.5, from 1 to 10 mass % of NiO and the rest being Al.sub.2O.sub.3.

(12) Now, the reasons why respective chemical components are limited to the above ranges will be described.

(13) Sodium oxide (Na.sub.2O) is an essential component to form a beta-alumina phase. The content is preferably from 8 to 15 mass %. If the content is less than 8 mass %, the beta-alumina phase cannot be sufficiently formed, and if the content exceeds 15 mass %, excess sodium aluminate remains in the crystalline phase, and thereby the ionic conductivity deteriorates. The content is more preferably from 9 to 14 mass %, further preferably from 10 to 13 mass %.

(14) Niobium oxide (Nb.sub.2O.sub.5) is a material for the RNbO.sub.3 phase. The content is preferably from 5 to 30 mass %. If the content is less than 5 mass %, a dense sintered compact cannot be obtained. Further, if the content exceeds 30 mass %, the ionic conductivity deteriorates. So as to be dense and improve the ionic conductivity, the content is more preferably from 6.5 to 28 mass %, further preferably from 8 to 25 mass %.

(15) Nickel oxide (NiO) is a stabilizer for the β″ alumina crystalline structure. The content is preferably from 1 to 10 mass %. If the content is less than 1 mass % or exceeds 10 mass %, the β″ alumina crystalline structure tends to be unstable. Further, at the time of firing, it causes the anomalous grain growth, and thereby, a dense sintered compact having a high ionic conductivity cannot be obtained. Thus, the content is more preferably from 3 to 6.5 mass %, further preferably from 4.5 to 5.5 mass %.

(16) Aluminum oxide (Al.sub.2O.sub.3) is an essential component to form the beta-alumina phase. The content is controlled so that the total amount with other components would be 100 mass %.

(17) The chemical composition can be quantitatively measured by means of a fluorescent X-ray analysis.

(18) Further, the beta-alumina-based sintered compact of the present invention preferably has a relative density of at least 97% and an open porosity of at most 0.5 vol % so as to attain densification. The open porosity is more preferably at most 0.3 vol %. When the relative density is high, particularly when the open porosity is low, the ionic conductivity and the mechanical strength are improved, and as a solid electrolyte, more preferred one can be obtained. The relative density and the open porosity can be measured by means of the Archimedes method.

(19) Now, the method for producing the beta-alumina-based sintered compact in the embodiment of the present invention will be explained. Here, NaNbO.sub.3 is used as a kind of RNbO.sub.3, and NiO is used as a stabilizer, however, the present invention is not restricted thereto.

(20) The beta-alumina-based sintered compact in the embodiment is produced by mixing a beta-alumina powder and an NaNbO.sub.3 powder, and molding and firing the mixture.

(21) The beta-alumina powder is produced as follows. A sodium carbonate (Na.sub.2CO.sub.3) powder, an alumina (Al.sub.2O.sub.3) powder and a nickel oxide (NiO) powder are prepared. These material powders are weighed so as to be in the predetermined proportions such that Na.sub.2CO.sub.3 would be from 15 to 17 mass % of the total mass of Na.sub.2CO.sub.3, Al.sub.2O.sub.3 and NiO (Na.sub.2CO.sub.3+Al.sub.2O.sub.3+NiO), Al.sub.2O.sub.3 would be from 78 to 80 mass %, and NiO would be from 5 to 7 mass %. These powders are mixed by using a ball mill or the like to obtain a mixed powder. Here, material powders to be used are not particularly restricted, so long as a sintered compact has a beta-alumina crystalline phase.

(22) The mixed powder is put in a heat resistant container such as an alumina crucible and calcinated at from 1,000 to 1,300° C. in air to synthesize a beta-alumina powder containing NiO as a stabilizer. Here, the retention time is preferably, for example, from 1 to 10 hours. Further, CO.sub.2 component in sodium carbonate evaporates in the calcination.

(23) On the other hand, the NaNbO.sub.3 powder is produced as follows. A sodium carbonate (Na.sub.2CO.sub.3) powder and a niobium oxide (Nb.sub.2O.sub.5) powder are prepared. These material powders are weighed so as to be in the predetermined proportions such that Na.sub.2CO.sub.3 would be from 28 to 29 mass % of the total mass of Na.sub.2CO.sub.3 and Nb.sub.2O.sub.5 (Na.sub.2CO.sub.3+Nb.sub.2O.sub.5), and Nb.sub.2O.sub.5 would be from 71 to 72 mass %, followed by mixing by a ball mil or the like to obtain a mixed powder. Here, material powders to be used are not particularly restricted, so long as they will form the chemical composition of NaNbO.sub.3 in the following calcination step.

(24) The obtained mixed powder is put in a heat resistant container such as an alumina crucible and calcinated at from 800 to 1,000° C. in air to synthesize an NaNbO.sub.3 powder. Here, the retention time is preferably from about 1 to 10 hours. Further, CO.sub.2 component in sodium carbonate evaporates in the calcination.

(25) The beta-alumina powder and the NaNbO.sub.3 powder thus produced are weighed so as to be in the predetermined proportions such that the beta-alumina powder would be from 50 to 93 mass % of the total mass of the beta-alumina powder and the NaNbO.sub.3 powder, and the NaNbO.sub.3 powder would be from 7 to 50 mass %. Here, if the NaNbO.sub.3 is less than 7 mass %, a dense sintered compact cannot be obtained. Further, if NaNbO.sub.3 exceeds 50 mass %, the ionic conductivity of the sintered compact deteriorates. It is preferred that the content of the beta-alumina powder is from 70 to 88 mass %, and the content of NaNbO.sub.3 is from 12 to 30 mass % from the viewpoint of densification and high ionic conductivity. It is further preferred that the content of beta-alumina powder is from 78 to 86 mass %, and the content of NaNbO.sub.3 is from 14 to 22 mass %.

(26) After weighing, the powders are mixed and pulverized by a wet method until the average particle size becomes at most 10 μm, preferably at most 2 μm, followed by drying to obtain a mixed powder. By making the average particle size of the powder small, a dense sintered compact can be produced. In the present specification, the average particle size is a value measured by means of a laser diffraction method. Further, the pulverization method is not particularly restricted, and for example, pulverization can be carried out by a ball mill, an attritor, a beads mill or a jet mill.

(27) Further, a mixed powder of the beta-alumina powder and the NaNbO.sub.3 powder can be simultaneously produced as described below without separately producing a beta-alumina powder and an NaNbO.sub.3 powder and mixing them. First, a sodium carbonate (Na.sub.2CO.sub.3) powder, an alumina (Al.sub.2O.sub.3) powder, a nickel oxide (NiO) powder and a niobium oxide (Nb.sub.2O.sub.5) powder are prepared. These material powders are weighed so as to be in the predetermined proportions such that Na.sub.2CO.sub.3 would be from 16 to 25 mass % of the total mass of Na.sub.2CO.sub.3, Al.sub.2O.sub.3, NiO and Nb.sub.2O.sub.5 (Na.sub.2CO.sub.3+Al.sub.2O.sub.3+NiO+Nb.sub.2O.sub.5), NiO would be from 3 to 6 mass %, Nb.sub.2O.sub.5 would be from 7 to 35 mass % and the rest would be Al.sub.2O.sub.3, followed by mixing by a ball mill or the like to obtain a mixed powder.

(28) The mixed powder is put in a heat resistant container such as an alumina crucible and calcinated at from 1,000 to 1,300° C. in air to synthesize a mixed powder of the beta-alumina powder and the NaNbO.sub.3 powder. Here, the retention time is preferably, for example, from 1 to 10 hours. Further, when the calcination temperature is at least 1,000° C., the reaction sufficiently proceeds, and the density of a sintered compact using this powder is made to be sufficiently high. Further, when the calcination temperature is at most 1,300° C., the hardness of the powder is suitable, whereby time for pulverization can be preferably reduced. The calcination temperature is more preferably from 1,000 to 1,200° C., and in such a case, the reaction sufficiently proceeds, whereby an excellent mixed powder of which pulverization time is relatively short can be obtained. As described above, the obtained mixed powder is pulverized by a wet method until the particle size becomes at most 10 μm, preferably at most 2 μm, followed by drying to obtain a mixed powder.

(29) The mixed powder of the beta-alumina powder and the NaNbO.sub.3 powder thus obtained is formed into a predetermined shape to obtain a molded product. The molding method is not particularly restricted, and a conventional molding method may be used. For example, molding can be carried out by hydrostatic press by applying a pressure of from 100 to 200 MPa. Otherwise, a mixture formed by adding an organic binder to the mixed powder may be kneaded and formed into a predetermined shape by a press molding, an extrusion molding, a sheet forming or the like. The shape obtained by the molding is not particularly restricted, and depending on applications, it may be formed into various shapes.

(30) The molded product is fired in air at a temperature of less than 1,450° C. for from 1 to 12 hours. If the firing temperature is too low, the effect of the liquid phase sintering by molten NaNbO.sub.3 is insufficient, and a dense sintered compact cannot be obtained. On the other hand, if the firing temperature is too high, Na.sub.2O volatilizes, such being undesirable. Thus, the firing temperature is preferably at least 1,350° C. and less than 1,450° C., more preferably from 1,375 to 1,425° C.

(31) The retention time at the highest temperature is not particularly restricted, and for example, it is from 1 to 12 hours, preferably from 2 to 5 hours. The firing atmosphere is not particularly restricted, for example, the air atmosphere, oxygen atmosphere, inert atmosphere such as nitrogen atmosphere or argon atmosphere or reductive atmosphere such as hydrogen or mixed atmosphere of hydrogen and nitrogen may be selected. Among them, the air atmosphere is preferred, since a relatively simple electric furnace may be used.

EXAMPLES

(32) Now, Examples of the present invention will be described. However, it should be understood that the present invention is by no means restricted to the following Examples. Ex. 1 to 4 are Working Examples of the present invention, and Ex. 5 and 6 are Comparative Examples.

(33) <Production of Sintered Compact>

(34) In Ex. 1 to 4, a sodium carbonate (Na.sub.2CO.sub.3) powder (manufactured by Kanto Chemical Co., Inc., guaranteed reagent), an α-alumina (Al.sub.2O.sub.3) powder (manufactured by Sumitomo Chemical Co., Ltd., tradename: AKP50) and a nickel oxide (NiO) powder (manufactured by Koujundo Chemical Lab. Co., Ltd., 3N product) were weighed in proportions of 15.4 mass %, 78.9 mass % and 5.7 mass % respectively. They were mixed by a dry ball mill for 24 hours.

(35) The obtained mixed powder was put in an alumina crucible and calcinated at 1,250° C. for 5 hours in air to synthesize a beta-alumina powder containing NiO as a stabilizer. The calcinated powder cooled to room temperature was made the agglomeration broken by passing it through a mesh having openings of 850 μm to regulate the particle size.

(36) On the other hand, a sodium carbonate (Na.sub.2CO.sub.3) powder and a niobium oxide (Nb.sub.2O.sub.5) powder (manufactured by Koujundo Chemical Lab. Co., Ltd., 3N/1 micrometer product) were weighed in proportions of 28.5 mass % and 71.5 mass % respectively and mixed by a dry ball mill for 24 hours.

(37) The obtained mixed powder was put in an alumina crucible and calcinated in air at 950° C. for 5 hours to synthesize an NaNbO.sub.3 powder. The calcinated powder cooled to room temperature was made the agglomeration broken by passing it through a mesh having openings of 850 μm to regulate the particle size.

(38) The obtained beta-alumina powder and NaNbO.sub.3 powder were weighed to constitute the composition of the mixed powder shown in Table 1, followed by mixing and pulverization by a wet ball mill for 96 hours by using ethanol as a dispersant and a yttria stabilized ball made of zirconia (manufactured by Nikkato Corporation, tradename: YTZ ball). Then, the slurry was dried, to obtain a mixed powder in each of Ex. 1 to 4.

(39) In Ex. 5, a beta-alumina powder was synthesized and made the agglomeration broken in the same manner as in Ex. 1 to 4 to obtain a beta-alumina powder.

(40) Then, the mixed powders of Ex. 1 to 4 and the beta-alumina powder of Ex. 5 were respectively molded by means of a hydrostatic press at room temperature at 180 MPa and then fired by heating at 1,400° C. for 2 hours in air.

(41) In Ex. 6, a sodium carbonate (Na.sub.2CO.sub.3) powder, an α-alumina (Al.sub.2O.sub.3) powder and a lithium carbonate (Li.sub.2CO.sub.3) powder (manufactured by Junsei Chemical Co., Ltd., guaranteed reagent) were used as the material powder, its composition would be 14.1 mass %, 84.2 mass % and 1.7 mass % respectively. The mixed powder was fired in the same manner as in Ex. 5. Here, the firing temperature was controlled at 1,500° C.

(42) In Ex. 1 to 5, the chemical composition of the obtained sintered compact was analyzed by using a fluorescent X-ray analysis apparatus (manufactured by Rigaku Corporation, apparatus name: RIX3000). In Table 1, the mixing ratio of the beta-alumina and the NaNbO.sub.3 powder and the chemical composition of the sintered compact obtained from results of the chemical composition analysis of the sintered compact by the fluorescent X-ray analysis are shown. The results of the fluorescent X-ray analysis are the proportions (mass %) of respective components, when the total mass of Na.sub.2O, Al.sub.2O.sub.3, Nb.sub.2O.sub.5 and NiO is 100 mass %. Further, in the obtained sintered compact, the total content of materials other than Na.sub.2O, Al.sub.2O.sub.3, Nb.sub.2O.sub.5 and NiO was less than 1 mass %, per the total sintered compact.

(43) TABLE-US-00001 TABLE 1 Contents of powder (mass %) Beta- Composition of sintered compact (mass %) Ex. alumina NaNbO.sub.3 Na.sub.2O Al.sub.2O.sub.3 Nb.sub.2O.sub.5 NiO 1 90 10 10.6 75.8 8.1 5.5 2 85 15 11.0 71.6 12.2 5.2 3 80 20 11.5 67.4 16.2 4.9 4 75 25 11.9 63.2 20.3 4.6 5 100 0 9.6 84.3 0 6.1

(44) The crystal phase construction and properties (relative density, opening porosity, conductivity and appearance after left in air for 30 days) of the sintered compacts obtained in Ex. 1 to 6 were measured as follows. Results are shown in Table 2.

(45) <Measurement and Evaluation Methods of Physical Properties, Etc.>

(46) (a) Crystalline Phase

(47) The crystalline phase was identified by an X-ray diffraction apparatus (manufactured by Rigaku Corporation, apparatus name: RINT2000). (b) Relative Density and Opening Porosity

(48) The bulk density and the opening porosity of the sintered compact were measured by an Archimedes method defined by JIS R1634. The ratio to the theoretical density of the bulk density is the relative density. In Ex. 1 to 5, the theoretical density of beta-alumina is 3.36 g/cm.sup.3, that of NaNbO.sub.3 is 4.44 g/cm.sup.3, and the theoretical density in Ex. 1 to 5 was calculated based on the proportion in each content of powder shown in Table 1. In Ex. 6, a value of 3.21 g/cm.sup.3 was used as the theoretical density. (c) Conductivity

(49) As the ionic conductivity of the sintered compact, the conductivity was measured by means of a complex impedance plot method at 25° C. and at 110° C. (d) Appearance After Left in Air for 30 Days

(50) The appearance of the obtained sintered compact before and after left in air for 30 days was observed.

(51) TABLE-US-00002 TABLE 2 Property of sintered compact Relative Opening Crystalline density porosity Conductivity (S/cm) Outer appearance after Ex. phase (%) (vol %) 25° C. 110° C. left in air for 30 days 1 β″-alumina, 97.0 0.29 0.001 0.01 Not changed NaNbO.sub.3 2 β″-alumina, 99.2 Less 0.003 0.03 Not changed NaNbO.sub.3 than 0.01 3 β″-alumina, 99.7 Less 0.003 0.03 Not changed NaNbO.sub.3 than 0.01 4 β″-alumina, 99.6 0.02 0.002 0.02 Not changed NaNbO.sub.3 5 β″-alumina 60.4 38.9 Not measured due Breakage/cracks to breakage/cracks observed 6 β″-alumina, 98.7 1.1 2 × 10.sup.−6 4 × 10.sup.−6 Breakage/cracks β-alumina observed

INDUSTRIAL APPLICABILITY

(52) According to the present invention, a beta-alumina-based sintered compact which is dense and has a high ionic conductivity can be stably produced. Further, by using such a beta-alumina-based sintered compact as a solid electrolyte for a storage battery, a storage battery which has a long life span and a high reliability can be produced.

(53) Even though as a conductive element, Na.sup.+ is replaced by another alkali metal ion such as Li.sup.+, a beta-alumina-based sintered compact which is dense and has a high ionic conductivity can be similarly produced. In such a case, the beta-alumina-based sintered compact can be used as a solid electrolyte for an all solid state lithium ion cell.