JP3281098B2 - Composite solid electrolyte and method for producing the same - Google Patents
Composite solid electrolyte and method for producing the sameInfo
- Publication number
- JP3281098B2 JP3281098B2 JP06135993A JP6135993A JP3281098B2 JP 3281098 B2 JP3281098 B2 JP 3281098B2 JP 06135993 A JP06135993 A JP 06135993A JP 6135993 A JP6135993 A JP 6135993A JP 3281098 B2 JP3281098 B2 JP 3281098B2
- Authority
- JP
- Japan
- Prior art keywords
- alumina
- solid electrolyte
- coating layer
- producing
- nasicon
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Secondary Cells (AREA)
- Fuel Cell (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、蓄電池、燃料電池、イ
オンセンサー、湿度センサー又はイオン交換膜等に利用
される複合固体電解質およびその製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composite solid electrolyte used for a storage battery, a fuel cell, an ion sensor, a humidity sensor, an ion exchange membrane and the like, and a method for producing the same.
【０００２】[0002]
【従来の技術】β−アルミナ（Ｎａ2Ｏ・ＸＡｌ2Ｏ
3（Ｘは９〜１１の数を示す）、格子定数ａ0＝０．５５
９４，Ｃ0＝２．２５３ｎｍ）またはβ”−アルミナ
（Ｎａ2Ｏ・ＸＡｌ2Ｏ3（Ｘは５〜７の数を示す）、格
子定数ａ0＝０．５５９５，Ｃ0＝３．３９３ｎｍ）は、
通常の固体に比べて著しく点欠陥濃度の高い物質であっ
てＮａ+のイオン伝導率が極めて高いため、従来より固
体電解質、燃料電池等に利用されている。 2. Description of the Related Art β-alumina (Na 2 O.XAl 2 O)
3 (X is a number of 9-11), the lattice constant a 0 = 0.55
94, C 0 = 2.253 nm) or β ″ -alumina (Na 2 O.XAl 2 O 3 (X represents a number of 5 to 7), lattice constant a 0 = 0.5595, C 0 = 3.393 nm )
Since it is a substance having a much higher point defect concentration than ordinary solids and having an extremely high ionic conductivity of Na + , it has been conventionally used for solid electrolytes, fuel cells, and the like.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、β−ア
ルミナ及びβ”−アルミナは、Ｎａ+が非常に動き易い
反面、Ｈ2Ｏと反応し易い。このため、β−アルミナ及
びβ”−アルミナからなる固体電解質は水分の多い環境
下では容易に崩れ易く、耐水性、耐湿性等の耐環境性に
対して非常に問題があった。However, β-alumina and β ″ -alumina are very easy for Na + to move, but are liable to react with H 2 O. Therefore, β-alumina and β ″ -alumina are difficult to be converted from β-alumina and β ″ -alumina. The solid electrolyte easily breaks down in an environment with a lot of moisture, and has a serious problem with respect to environmental resistance such as water resistance and moisture resistance.
【０００４】このため、β−アルミナ又はβ”−アルミ
ナの表面に、耐水、耐湿用のガラス膜を設けることも考
えられるが、この場合は一般にイオン伝導度が悪化して
しまうという問題がある。For this reason, it is conceivable to provide a water-resistant and moisture-resistant glass film on the surface of β-alumina or β ″ -alumina. However, in this case, there is a problem that ionic conductivity generally deteriorates.
【０００５】本発明は上記事情に鑑みてなされたもので
あり、イオン伝導度が良好でかつ耐水性、耐湿性等の耐
環境性にも優れた固体電解質及びその製造方法を提供す
ることを目的とする。The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a solid electrolyte having good ionic conductivity and excellent environmental resistance such as water resistance and moisture resistance, and a method for producing the same. And
【０００６】[0006]
【課題を解決するための手段】請求項１記載の複合固体
電解質では、β−アルミナまたはβ”−アルミナ系固体
電解質の表面に、Ｎａｓｉｃｏｎ［Ｎａ1+XＺｒ2ＳｉX
Ｐ3-XＯ12（ここで、０≦Ｘ≦３）］を主成分とする被
覆層を設けたことを課題を解決するための手段とした。In the composite solid electrolyte according to the present invention, the surface of β-alumina or β ″ -alumina solid electrolyte is coated with Nasicon [Na 1 + X Zr 2 Si X
The provision of a coating layer containing P 3-X O 12 (where 0 ≦ X ≦ 3)] as a main component is a means for solving the problem.
【０００７】ここで、Ｎａｓｉｃｏｎを主成分とする被
覆層はＮａｓｉｃｏｎのみから成るものの他に、副成分
としてＺｒＯ2やガラス相を含むものであっても良く、
用途に応じてイオン伝導度や耐環境性を考慮して適宜許
容範囲を定めるのが良い。しかし、イオン伝導度を優先
すればＮａｓｉｃｏｎ含有量の高い方が好ましい。Here, the coating layer containing Nasicon as a main component may be a layer containing ZrO 2 or a glass phase as an auxiliary component in addition to a layer consisting of Nasicon alone.
It is preferable that an allowable range is appropriately determined in consideration of ionic conductivity and environmental resistance depending on the application. However, if priority is given to ionic conductivity, a higher Nasicon content is preferred.
【０００８】請求項２記載の複合固体電解質の製造方法
では、β−アルミナまたはβ”−アルミナ系固体電解質
の表面に、化学液相法によって上記Ｎａｓｉｃｏｎを主
成分とする被覆層を形成することを課題を解決するため
の手段とした。According to a second aspect of the present invention, in the method for producing a composite solid electrolyte, a coating layer containing Nasicon as a main component is formed on a surface of a β-alumina or β ″ -alumina solid electrolyte by a chemical liquid phase method. It is a means to solve the problem.
【０００９】ここで、上記化学液相法としては、金属ア
ルコキシド、有機金属化合物等の原料を用いたゾルゲル
法等が好適である。また、上記化学液相法によってＮａ
ｓｉｃｏｎを主成分とする被覆層を形成する場合の膜厚
は、０．０１〜１０μｍが好ましく、１μｍ程度が最適
である。０．０１μｍ未満では、均一な被覆層が得られ
ず耐水性、耐湿性等の耐環境性を改善するための効果が
小さくなり、１０μｍを越えると低温域におけるイオン
伝導度が悪くなると共に上記被覆層が剥がれ易くなる。Here, as the chemical liquid phase method, a sol-gel method using raw materials such as metal alkoxides and organometallic compounds is suitable. Further, Na is obtained by the chemical liquid phase method described above.
When forming a coating layer containing silicon as a main component, the thickness is preferably 0.01 to 10 μm, and most preferably about 1 μm. When the thickness is less than 0.01 μm, a uniform coating layer cannot be obtained, and the effect of improving environmental resistance such as water resistance and moisture resistance is reduced. The layer is easily peeled.
【００１０】請求項３記載の複合固体電解質の製造方法
では、β−アルミナまたはβ”−アルミナ系固体電解質
の表面に、気相成長法によって上記Ｎａｓｉｃｏｎを主
成分とする被覆層を形成することを課題を解決するため
の手段とした。According to a third aspect of the present invention, there is provided a method for producing a composite solid electrolyte, comprising forming a coating layer containing Nasicon as a main component on a surface of a β-alumina or β ″ -alumina solid electrolyte by a vapor phase growth method. It is a means to solve the problem.
【００１１】上記気相成長法としては、ＣＶＤ法（化学
気相成長法）、ＰＶＤ法（物理気相蒸着法）等が好適で
ある。As the above-mentioned vapor phase growth method, a CVD method (chemical vapor deposition method), a PVD method (physical vapor deposition method) and the like are suitable.
【００１２】また、気相法によって被覆層を形成する場
合の膜厚は、１ｎｍ〜１μｍが好ましく、特に０．１〜
１μｍが望ましい。１ｎｍ未満では、被覆層の均一性に
乏しくまた被覆層自身の劣化により耐環境性を改善する
ための効果が小さくなり、１μｍを越えると、時間がか
かりコスト高になる。When the coating layer is formed by a vapor phase method, the thickness is preferably 1 nm to 1 μm, particularly 0.1 to 1 μm.
1 μm is desirable. When the thickness is less than 1 nm, the uniformity of the coating layer is poor, and the effect of improving the environmental resistance is reduced due to the deterioration of the coating layer itself.
【００１３】[0013]
【作用】Ｎａｓｉｃｏｎは、ＮａＯとＡｌ2Ｏ3が層状構
造をなすβ−アルミナ及びβ”−アルミナとは異なり、
Ｚｒ−Ｓｉ−Ｐ−Ｏの三次元網目構造中にＮａ+を含有
している構造をとっている。この構造上の相違により、
Ｎａｓｉｃｏｎ中のＮａ+はβ−アルミナ等のそれに比
べてＨ2Ｏと反応しにくいものと推定される。従って、
β−アルミナまたはβ”−アルミナ上にＮａｓｉｃｏｎ
層を被覆することによって、耐水性が改善される。Nasicon is different from β-alumina and β ″ -alumina in which NaO and Al 2 O 3 form a layered structure.
It has a structure in which Na + is contained in a three-dimensional network structure of Zr—Si—PO. Due to this structural difference,
It is presumed that Na + in Nasicon is less likely to react with H 2 O than that of β-alumina or the like. Therefore,
Nasicon on β-alumina or β ″ -alumina
By coating the layer, the water resistance is improved.
【００１４】また、Ｎａｓｉｃｏｎ自体も特に高温域に
おいてはイオン伝導度に優れているので、Ｎａｓｉｃｏ
ｎ層を被覆したβ−アルミナのイオン伝導度は良好に維
持され、一方低温域においても被覆層の厚さを薄くする
ことによってβ−アルミナのイオン伝導度は良好に維持
される。Further, Nasicon itself has excellent ionic conductivity especially in a high temperature range, and
The ionic conductivity of β-alumina coated with the n-layer is well maintained, while the ionic conductivity of β-alumina is well maintained even in a low temperature range by reducing the thickness of the coating layer.
【００１５】[0015]
【実施例１】ジルコニウムブトキシド；Ｚｒ（ＯＣ
4Ｈ9）4溶液（Huls社製）４０ｇにトリエタノールアミ
ン；（ＨＯＣ2Ｈ4）3Ｎ １０．９５ｇを加えて攪拌し、
エタノール１００mlを添加した。これにオルトケイ酸テ
トラエチル；Ｓｉ（ＯＣ2Ｈ5）4２１．７２ｇ，リン酸
トリエチル；（Ｃ2Ｈ5Ｏ）3ＰＯ ９．４９５ｇ，ナトリ
ウムメトキシド；ＣＨ3ＯＮａ ８．４５９ｇを入れて加
熱、攪拌した。これにエタノール１００mlで薄めた水２
０．６４ｇを徐々に加えて加水分解を行った。この溶液
中に２０×２０×５ｍｍの寸法のβ−アルミナ片を浸漬
してコートした。その後、１２００℃×２時間で焼成し
て被覆層を形成したβ−アルミナ片を得た。被覆層につ
いてＸ線回折法にて結晶相を調べたところ、Ｎａｓｉｃ
ｏｎ（Ｎａ3Ｚｒ2Ｓｉ2ＰＯ12, Ｎａ3.4Ｚｒ2Ｓｉ2.4Ｐ
0.6Ｏ12）と少量のＺｒＯ2が確認された。膜厚は２〜３
μｍであった。Example 1 Zirconium butoxide; Zr (OC
10.95 g of triethanolamine; (HOC 2 H 4 ) 3 N was added to 40 g of 4 H 9 ) 4 solution (manufactured by Huls), and the mixture was stirred.
100 ml of ethanol were added. This tetraethylorthosilicate; Si (OC 2 H 5) 4 21.72g, triethyl phosphate; (C 2 H 5 O) 3 PO 9.495g, sodium methoxide; CH 3 heating put ONa 8.459g, Stirred. Water 2 diluted with 100 ml of ethanol
Hydrolysis was performed by gradually adding 0.64 g. A β-alumina piece having a size of 20 × 20 × 5 mm was immersed in the solution to coat. Then, it was fired at 1200 ° C. for 2 hours to obtain a β-alumina piece having a coating layer formed thereon. When the crystal phase of the coating layer was examined by an X-ray diffraction method,
on (Na 3 Zr 2 Si 2 PO 12 , Na 3.4 Zr 2 Si 2.4 P
0.6 O 12 ) and a small amount of ZrO 2 were confirmed. The film thickness is 2-3
μm.
【００１６】この被覆層を形成したβ−アルミナ片とし
ないものとで、可逆電極を用いた直接法で３００℃にお
けるイオン伝導度を測定したところ、被覆層を形成した
β−アルミナ片では０．３７Ω-1ｃｍ-1、被覆層を形成
していないものでは０．４２Ω-1ｃｍ-1であった。When the ionic conductivity at 300 ° C. was measured by a direct method using a reversible electrode between the β-alumina piece having the coating layer and the non-β-alumina piece having the coating layer, the β-alumina piece having the coating layer had a ionic conductivity of 0.3%. 37Ω -1 cm -1, but not to form a coating layer was 0.42Ω -1 cm -1.
【００１７】次にこの被覆層を形成したβ−アルミナ片
を湿度７５％、４０℃の恒温恒湿槽に入れ、１週間放置
した。また、比較のために被覆層を形成していないβ−
アルミナ片（寸法２０×２０×５ｍｍ）を入れて同様に
放置した。Next, the β-alumina piece on which the coating layer was formed was placed in a constant temperature / humidity bath at a humidity of 75% and a temperature of 40 ° C., and allowed to stand for one week. Further, for comparison, β-
Alumina pieces (dimensions 20 × 20 × 5 mm) were put and left in the same manner.
【００１８】その結果、Ｎａｓｉｃｏｎ被覆層を形成し
たβ−アルミナ片では変化が見られなかったが、被覆層
を形成していないβ−アルミナ片では、表面が溶け出し
たようになり、腐食が起こっていた。As a result, no change was observed in the β-alumina piece having the Nasicon coating layer formed thereon. I was
【００１９】[0019]
【実施例２】原料として、ジルコニウムブトキシド；Ｚ
ｒ（ＯＣ4Ｈ9）4，リン酸トリエチル；（Ｃ2Ｈ5Ｏ）3Ｐ
Ｏ，ナトリウムイソプロポキシド；ＮａＯＣ3Ｈ7，シリ
コンエトキシド；Ｓｉ（ＯＣ2Ｈ5）4を使用し、ＭＯＣ
ＶＤ（Metal Organic Chemical Vapor Deposition）装
置を用いて被覆を行った。Example 2 Zirconium butoxide; Z as raw material
r (OC 4 H 9 ) 4 , triethyl phosphate; (C 2 H 5 O) 3 P
O, sodium isopropoxide; NaOC 3 H 7 , silicon ethoxide; Si (OC 2 H 5 ) 4 and MOC
Coating was performed using a VD (Metal Organic Chemical Vapor Deposition) apparatus.
【００２０】まず、原料を１００〜１８０℃で加熱して
原料蒸気を得た。次いで、これをキャリアガスであるＡ
ｒでβ−アルミナ基板上に運び、ここでキャリアガスＡ
ｒにＯ2を体積基準で２０〜３０％混合し、１〜１０Tor
r程度の圧力で約９０分間析出処理を行った。この際、
成膜温度は外熱式反応炉において９００〜１１００℃に
設定した。First, the raw material was heated at 100 to 180 ° C. to obtain a raw material vapor. Next, this is used as the carrier gas A
r onto the β-alumina substrate, where the carrier gas A
r is mixed with 20-30% by volume of O 2 , and 1-10 Torr
A precipitation treatment was performed at a pressure of about r for about 90 minutes. On this occasion,
The film formation temperature was set at 900 to 1100 ° C. in an external heating type reaction furnace.
【００２１】その結果、厚さ約２００ｎｍの被覆層を有
するβ−アルミナ基板を得た。この被覆層について薄膜
Ｘ線回折法にて結晶相を調べたところ、Ｎａｓｉｃｏｎ
（Ｎａ3Ｚｒ2Ｓｉ2ＰＯ12）の存在が確認された。As a result, a β-alumina substrate having a coating layer having a thickness of about 200 nm was obtained. The crystal phase of this coating layer was examined by a thin film X-ray diffraction method.
The presence of (Na 3 Zr 2 Si 2 PO 12 ) was confirmed.
【００２２】実施例１と同様にしてイオン伝導度を測定
した結果、被覆層を形成していないものが０．４２Ω-1
ｃｍ-1（３００℃）であるのに対して、被覆層を形成し
たものでは０．４０Ω-1ｃｍ-1（３００℃）であり、被
覆層を形成してもイオン伝導度を良好に維持できること
が判明した。The ion conductivity was measured in the same manner as in Example 1. As a result, 0.42 Ω −1 was obtained without the coating layer.
cm.sup.- 1 (300.degree. C.), but 0.40 .OMEGA..sup.- 1 cm.sup.- 1 (300.degree. C.) in the case where the coating layer was formed. It turns out that it can be done.
【００２３】さらに、このＮａｓｉｃｏｎを被覆したβ
−アルミナ基板に、実施例１と同様の耐湿性試験を行っ
た結果、表面に変化が見られず、良好な耐水性を示し
た。Furthermore, β coated with this Nasicon
The same moisture resistance test as in Example 1 was performed on the alumina substrate. As a result, no change was observed on the surface, and good water resistance was exhibited.
【００２４】[0024]
【発明の効果】以上説明したように請求項１記載の複合
固体電解質では、β−アルミナまたはβ”−アルミナ系
固体電解質の表面に、Ｎａｓｉｃｏｎを主成分とする被
覆層を設けたものであるので、イオン伝導度を良好に維
持しつつ、耐水性、耐湿性等の耐環境性を改善すること
ができる。As described above, in the composite solid electrolyte according to the first aspect, a coating layer containing Nasicon as a main component is provided on the surface of a β-alumina or β ″ -alumina solid electrolyte. In addition, environmental resistance such as water resistance and moisture resistance can be improved while maintaining good ion conductivity.
【００２５】請求項２記載の複合固体電解質の製造方法
では、β−アルミナまたはβ”−アルミナ系固体電解質
の表面に、化学液相法によって上記Ｎａｓｉｃｏｎを主
成分とする被覆層を形成する方法であるので、低コスト
で膜厚の大きいものまで容易に製造することができる。According to a second aspect of the present invention, there is provided a method for producing a composite solid electrolyte, the method comprising forming a coating layer containing Nasicon as a main component on a surface of a β-alumina or β ″ -alumina solid electrolyte by a chemical liquid phase method. As a result, it is possible to easily produce a film having a large thickness at a low cost.
【００２６】請求項３記載の複合固体電解質の製造方法
では、β−アルミナまたはβ”−アルミナ系固体電解質
の表面に、気相成長法によって上記Ｎａｓｉｃｏｎを主
成分とする被覆層を形成する方法であるので、イオン伝
導度が良好で耐環境性に優れた複合固体電解質を製造す
ることができる。According to a third aspect of the present invention, there is provided a method for producing a composite solid electrolyte, comprising forming a coating layer containing Nasicon as a main component on a surface of a β-alumina or β ″ -alumina solid electrolyte by a vapor phase growth method. As a result, a composite solid electrolyte having good ionic conductivity and excellent environmental resistance can be manufactured.
Claims (3)
電解質の表面に、Ｎａｓｉｃｏｎ［Ｎａ1+XＺｒ2ＳｉX
Ｐ3-XＯ12（ここで、０≦Ｘ≦３）］を主成分とする被
覆層が設けられていることを特徴とする複合固体電解
質。(1) Nasicon [Na 1 + X Zr 2 Si X is coated on the surface of β-alumina or β ″ -alumina solid electrolyte.
P 3-X O 12 (where 0 ≦ X ≦ 3)].
電解質の表面に、化学液相法によってＮａｓｉｃｏｎ
［Ｎａ １＋Ｘ Ｚｒ ２ Ｓｉ Ｘ Ｐ ３−Ｘ Ｏ １２ （ここで、０
≦Ｘ≦３）］を主成分とする被覆層を形成することを特
徴とする複合固体電解質の製造方法。Wherein β- alumina or beta "- to the surface of the alumina-based solid electrolyte by chemical liquid phase N Asicon
[Na 1 + X Zr 2 Si X P 3-X O 12 ( where 0
.Ltoreq.X.ltoreq.3)] . A method for producing a composite solid electrolyte, comprising:
電解質の表面に、気相成長法によってＮａｓｉｃｏｎ
［Ｎａ １＋Ｘ Ｚｒ ２ Ｓｉ Ｘ Ｐ ３−Ｘ Ｏ １２ （ここで、０
≦Ｘ≦３）］を主成分とする被覆層を形成することを特
徴とする複合固体電解質の製造方法。3. β- alumina or beta "- to the surface of the alumina-based solid electrolyte, by the vapor deposition N Asicon
[Na 1 + X Zr 2 Si X P 3-X O 12 ( where 0
.Ltoreq.X.ltoreq.3)] . A method for producing a composite solid electrolyte, comprising:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP06135993A JP3281098B2 (en) | 1993-02-26 | 1993-02-26 | Composite solid electrolyte and method for producing the same |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP06135993A JP3281098B2 (en) | 1993-02-26 | 1993-02-26 | Composite solid electrolyte and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06256076A JPH06256076A (en) | 1994-09-13 |
| JP3281098B2 true JP3281098B2 (en) | 2002-05-13 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP06135993A Expired - Fee Related JP3281098B2 (en) | 1993-02-26 | 1993-02-26 | Composite solid electrolyte and method for producing the same |
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| Country | Link |
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| JP (1) | JP3281098B2 (en) |
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