JP4714856B2 - Crystallized glass and method for producing the same - Google Patents
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Description
本発明は、リチウムイオンが層間イオンである雲母結晶が主結晶相で、リチウムイオンがキャリアーとなることでイオン伝導性を示し、熱的に安定で、機械加工が容易である結晶化ガラスおよびその製造方法に関するものである。 The present invention, mica crystals in the main crystal phase of lithium ions is interstitial ions, show ion conductivity by Li Chiumuio down becomes a carrier, thermally stable, machined easily der Ru crystallization The present invention relates to glass and a method for producing the same.
層間イオンが主としてカリウムイオンである雲母結晶を主結晶相とした焼成体および結晶化ガラスは機械加工が容易な快削性セラミックスとして知られており、また、電気的には絶縁材料として公知され、電気的絶縁材料としての利用が検討されている。（例えば特許文献１参照）また、本発明で採り上げるリチウムイオン、ナトリウムイオンあるいはカルシウムイオンが層間イオンである雲母結晶は膨潤性雲母として知られ、その中でもナトリウムイオンが層間イオンである膨潤性雲母はイオン交換体としての応用が検討されている（特許文献２参照）が、いずれのイオンが層間イオンであっても電気的にイオン伝導性を示すことは全く知られていない。また、それらの膨潤性雲母結晶を焼成体あるいは結晶化ガラスのようにバルク状にすると、その膨潤性のゆえに、層間に空気中の水分をも取り入れ、自然崩壊してしまう。 A fired body and crystallized glass whose main crystal phase is a mica crystal in which interlayer ions are mainly potassium ions are known as free-cutting ceramics that are easy to machine, and are electrically known as insulating materials, Use as an electrically insulating material is being studied. (For example, refer to Patent Document 1) Further, the mica crystal in which lithium ion, sodium ion or calcium ion taken up in the present invention is an interlayer ion is known as a swellable mica, and among them, the swellable mica in which a sodium ion is an interlayer ion is an ion. Although application as an exchanger has been studied (see Patent Document 2), it has not been known at all that any ion is an interlayer ion and electrically exhibits ion conductivity. In addition, when these swellable mica crystals are made into a bulk shape such as a fired body or crystallized glass, moisture in the air is also taken in between layers due to the swelling property, and spontaneously collapses.
現在、ガラスのイオン伝導体の中で伝導率が室温で１０‐３Ｓ／ｃｍを超えるものとしては、リンを含む酸化物ガラス（例えば特許文献３参照）および硫化物ガラス（例えば特許文献４参照）が知られている。しかし、ケイ酸塩系のガラスが室温で１０‐３Ｓ／ｃｍを超える伝導率を示した例はない。 Currently, among the ionic conductors of glass, those having a conductivity exceeding 10 −3 S / cm at room temperature include oxide glasses containing phosphorus (see, for example, Patent Document 3) and sulfide glasses (see, for example, Patent Document 4). )It has been known. However, there is no example in which silicate-based glass has a conductivity exceeding 10 −3 S / cm at room temperature.
本発明は、従来から知られているリチウムイオン、ナトリウムイオンあるいはカルシウムイオンが層間イオンである膨潤性雲母結晶が主結晶相の焼成体および結晶化ガラスが電気的にイオン伝導体であることを示す。そして、イオン伝導性およびバルク状にしても自然崩壊しないような高い耐水性を有する焼成体および結晶化ガラス並びにその製造方法を提供することを目的とする。 The present invention shows that a conventionally known swellable mica crystal in which lithium ions, sodium ions or calcium ions are interlayer ions is a main crystal phase fired body and crystallized glass is an electrically ionic conductor. . And it aims at providing the sintered body and crystallized glass which have high water resistance which does not collapse naturally even if it is ion-conductive and bulk form, and its manufacturing method.
また、（０００５）に記載した結晶化ガラスのなかで、イオン伝導性およびバルク状にしても自然崩壊しないような高い耐水性に加え、快削性および透光性を有する結晶化ガラス並びにその製造方法を提供することを目的とする。 Among the crystallized glass described in (0005), in addition to ion conductivity and high water resistance that does not spontaneously collapse even when in bulk, crystallized glass having free-cutting property and translucency, and its production It aims to provide a method.
さらに、（０００５）に記載した結晶化ガラスと同組成で、リチウムイオンあるいはカルシウムイオンがキャリアーとなり、伝導率が５×１０‐３Ｓ／ｃｍを超える高いイオン伝導性を示す透明なフッ素含有ケイ酸塩ガラス並びにその製造方法を提供することを目的とする。 Further, a transparent fluorine-containing silicic acid having the same composition as the crystallized glass described in (0005), wherein lithium ions or calcium ions serve as carriers and have a high ion conductivity exceeding 5 × 10 −3 S / cm. It aims at providing salt glass and its manufacturing method.
請求項１に係る結晶化ガラスは、重量％で表示して４〜５％のＬｉ ２ Ｏ、１４〜２０％のＭｇＯ、９〜１３％のＡｌ ２ Ｏ ３ 、４８〜５６％のＳｉＯ ２ 、１４〜２０％のＭｇＦ ２ の組成からなり、イオン伝導性及び透光性を備え、リチウムイオンが層間イオンである雲母結晶を主結晶相とすることを特徴とする。なお、イオン伝導性は、伝導率を四端子法で測定したことによって見出された。 The crystallized glass according to claim 1 is expressed in terms of % by weight, 4-5% Li 2 O, 14-20% MgO, 9-13% Al 2 O 3 , 48-56% SiO 2 , It has a composition of 14 to 20% MgF 2 , has ion conductivity and translucency, and has a mica crystal in which lithium ions are interlayer ions as a main crystal phase. Incidentally, ion-conductivity was found by the measurement of heat Shiruberitsu a four-terminal method.
請求項２に係る結晶化ガラスの製造方法は、重量％で表示して４〜５％のＬｉ ２ Ｏ、１４〜２０％のＭｇＯ、９〜１３％のＡｌ ２ Ｏ ３ 、４８〜５６％のＳｉＯ ２ 、１４〜２０％のＭｇＦ ２ の組成からなる原料組成物を混合し、この原料組成物を５００〜９５０℃で加熱して原料中の無機塩を分解し、無機塩を分解した後の原料組成物を容器に封入して溶融した後、５５０〜６５０℃で熱処理して歪み抜きし、さらに６００〜７００℃で熱処理して雲母を結晶化させることを特徴とする。 The method for producing crystallized glass according to claim 2 is expressed in terms of % by weight of 4 to 5% Li 2 O, 14 to 20% MgO, 9 to 13% Al 2 O 3 , and 48 to 56%. SiO 2, a mixture of raw material composition having a composition 14 to 20% of the MgF 2, the raw material composition was heated at from 500 to 950 ° C. to decompose the inorganic salt in the feedstock, after decomposing the inorganic salt The raw material composition is sealed in a container and melted, then heat treated at 550 to 650 ° C. to remove strain, and further heat treated at 600 to 700 ° C. to crystallize mica.
以下に本発明に係る結晶化ガラスおよびその製造方法について詳細に説明する。 Hereinafter, the crystallized glass and the method for producing the same according to the present invention will be described in detail.
リチウムイオン伝導性を示すガラスの組成は重量％で表示して３〜６％のＬｉ２Ｏ、１２〜２２％のＭｇＯ、７〜１３％のＡｌ２Ｏ３、４７〜６４％のＳｉＯ２、１０〜２３％のＭｇＦ２の組成で、それらの組成範囲内でガラスが得られ、それよりも各組成が多い場合でも、少ない場合でもガラスは得られない。 Li-Ion 3-6% of Li 2 O to view the composition of the glasses exhibiting conductivity in weight percent 12 to 22% of MgO, 7 to 13% of Al 2 O 3, 47-64% of SiO 2, With a composition of 10 to 23% MgF 2 , glass is obtained within the composition range, and glass is not obtained even when there are more or less than each composition.
上記（００１９）に記載した組成として原料組成物を混合後、５００〜９５０℃で加熱して原料中の無機塩を分解する。加熱した後の原料組成物を容器に封入し、高温で溶融する。この原料組成物の封入は溶融の際に起こる原料の揮散を防ぐためのものである。溶融して得られたガラスを歪み抜きするために、５５０〜６５０℃で熱処理する。このようにしてリチウムイオン伝導性を示すガラスが得られる。 After mixing the raw material composition as the composition described in (0019) above, the mixture is heated at 500 to 950 ° C. to decompose the inorganic salt in the raw material. The heated raw material composition is sealed in a container and melted at a high temperature. The enclosing of the raw material composition is for preventing volatilization of the raw material that occurs during melting. In order to remove the distortion of the glass obtained by melting, heat treatment is performed at 550 to 650 ° C. Thus glass is obtained showing a lithium ion conductivity.
上記（００２０）に記載した方法で得られるイオン伝導性を示すガラスを６５０〜８００℃で再び熱処理すると、雲母がガラスから析出する。６５０℃より低い温度での熱処理では雲母は析出せず、８００℃より高い温度での熱処理ではアルミノケイ酸リチウムなどの雲母ではない結晶の析出量が非常に多くなる。このようにしてリチウムイオン伝導性を示す結晶化ガラスが得られる。また、この結晶化ガラスは快削性を示す。 When the glass showing ion conductivity obtained by the method described in the above (0020) is heat-treated again at 650 to 800 ° C., mica precipitates from the glass. In the heat treatment at a temperature lower than 650 ° C., mica does not precipitate, and in the heat treatment at a temperature higher than 800 ° C., the amount of crystals that are not mica such as lithium aluminosilicate is very large. Thus crystallized glass is obtained showing a lithium ion conductivity. Moreover, this crystallized glass exhibits free-cutting properties.
上記（００１９）に記載した組成のなかで、特に、重量％で表示して４〜５％のＬｉ２Ｏ、１４〜２０％のＭｇＯ、９〜１３％のＡｌ２Ｏ３、４８〜５６％のＳｉＯ２、１４〜２０％のＭｇＦ２の組成として（００２０）に記載した方法により作製するガラスは無色透明であり、このガラスは透明なリチウムイオン伝導体となる。また、その無色透明なガラスを６００〜７００℃で０〜４時間の熱処理で雲母を結晶化させて得られる結晶化ガラスは透明性を保つ。このようにして得られる結晶化ガラスは水中でも崩壊しないような高い耐水性、高いイオン伝導率、快削性および透光性を有する。 Among the compositions described in (0019) above, in particular, 4-5% Li 2 O, 14-20% MgO, 9-13% Al 2 O 3 , 48-56% expressed in weight percent. The glass produced by the method described in (0020) as the composition of SiO 2 and 14 to 20% MgF 2 is colorless and transparent, and this glass becomes a transparent lithium ion conductor. Moreover, the crystallized glass obtained by crystallizing the colorless and transparent glass by heat treatment at 600 to 700 ° C. for 0 to 4 hours maintains the transparency. The crystallized glass thus obtained has high water resistance, high ionic conductivity, free machinability and translucency that do not collapse even in water.
参考例として、ナトリウムイオン伝導性を示す焼成体は重量％で表示して０〜２１％のＮａ２Ｏ、１７〜３２％のＭｇＯ、１２〜３５％のＡｌ２Ｏ３、１２〜４５％のＳｉＯ２、０〜２６％のＮａＦ、０〜１７％のＭｇＦ２の組成で、それよりも各組成が多い場合でも、少ない場合でも焼成体の主結晶相であるナトリウム雲母が生成しない。 As a reference example, the calcined body exhibiting sodium ion conductivity is expressed in terms of% by weight, 0 to 21% Na 2 O, 17 to 32% MgO, 12 to 35% Al 2 O 3 , and 12 to 45%. The composition of SiO 2 , 0 to 26% NaF and 0 to 17% MgF 2 does not produce sodium mica, which is the main crystal phase of the fired body, even when there are more or less than each composition.
上記（００２３）に記載した組成として原料粉末を混合後、成形して成形体とし、その成形体を容器に封入し、８００〜１２００℃で加熱し、原料の固相反応によって雲母が生成する。成形体を容器に封入するのは焼成の際に起こる原料の揮散を防ぐためのものである。８００℃より低い温度での熱処理では雲母は生成せず、１２００℃より高い温度での熱処理では原料が溶融、あるいは雲母ではない他の結晶が生成し雲母が十分に生成しない。このようにしてナトリウムイオン伝導性を示す焼成体が得られる。 After mixing the raw material powder as the composition described in the above (0023), it is molded into a molded body, the molded body is sealed in a container, heated at 800 to 1200 ° C., and mica is generated by a solid phase reaction of the raw material. The purpose of enclosing the molded body in the container is to prevent volatilization of the raw material that occurs during firing. In the heat treatment at a temperature lower than 800 ° C., mica is not generated, and in the heat treatment at a temperature higher than 1200 ° C., the raw material is melted or other crystals that are not mica are generated, and mica is not sufficiently generated. Thus fired body showing the sodium ion conductivity is obtained.
上記（００２３）に記載した組成として原料組成物を混合後、５００〜９５０℃で加熱して原料中の無機塩を分解する。加熱した後の原料組成物を容器に封入し、高温で溶融する。原料組成物を封入するには溶融の際に起こる原料の揮散を防ぐためである。溶融して得られたガラスを粉末状とした後、成形して成形体とする。そのガラス粉末成形体を、６５０〜１０００℃で熱処理して、雲母結晶を析出させる。６５０℃より低い温度での熱処理では雲母は生成せず、１０００℃より高い温度での熱処理では原料が溶融、あるいは雲母ではない他の結晶が多量に生成し、雲母が十分に生成しない。このようにしてナトリウムイオン伝導性を示す結晶化ガラスが得られる。 After mixing the raw material composition as the composition described in (0023) above, the mixture is heated at 500 to 950 ° C. to decompose the inorganic salt in the raw material. The heated raw material composition is sealed in a container and melted at a high temperature. The purpose of enclosing the raw material composition is to prevent volatilization of the raw material that occurs during melting. The glass obtained by melting is powdered and then molded into a molded body. The glass powder compact is heat treated at 650 to 1000 ° C. to precipitate mica crystals. In the heat treatment at a temperature lower than 650 ° C., mica is not generated, and in the heat treatment at a temperature higher than 1000 ° C., the raw material is melted or other crystals that are not mica are generated in a large amount, and mica is not generated sufficiently. Thus crystallized glass is obtained which indicates a sodium ion conductivity.
参考例として、カルシウムイオン伝導性を示す結晶化ガラスおよび請求項７に記載されたカルシウムイオン伝導性を示すガラスの組成は重量％で表示して６〜１０％のＣａＯ、１８〜２０％のＭｇＯ、１１〜１８％のＡｌ２Ｏ３、３８〜４５％のＳｉＯ２、１５〜２４％のＭｇＦ２の組成で、それらの組成範囲内でガラスが得られ、それよりも各組成が多い場合でも、少ない場合でもガラスは得られない。 As a reference example, the composition of the crystallized glass exhibiting calcium ion conductivity and the glass exhibiting calcium ion conductivity described in claim 7 is expressed in terms of% by weight, 6 to 10% CaO, 18 to 20% MgO. Even if the composition is 11-18% Al 2 O 3 , 38-45% SiO 2 , 15-24% MgF 2 , glass is obtained within the composition range, and each composition is more than that. Even if it is small, glass cannot be obtained.
上記（００２６）に記載した組成として原料組成物を混合後、５００〜９５０℃で加熱して原料中の無機塩を分解する。加熱した後の原料組成物を容器に封入し、高温で溶融する。この原料組成物の封入は溶融の際に起こる原料の揮散を防ぐためのものである。溶融して得られたガラスを歪み抜きするために、６００〜８００℃で熱処理する。このようにしてカルシウムイオン伝導性を示すガラスが得られる。また、このガラスは透明である。 After mixing a raw material composition as a composition described in the above (0026), it is heated at 500 to 950 ° C. to decompose inorganic salts in the raw material. The heated raw material composition is sealed in a container and melted at a high temperature. The enclosing of the raw material composition is for preventing volatilization of the raw material that occurs during melting. In order to remove distortion of the glass obtained by melting, heat treatment is performed at 600 to 800 ° C. Thus glass is obtained showing a mosquito Rushiumuion conductivity. This glass is transparent.
上記（００２７）に記載した方法で得られるイオン伝導性を示す透明なガラスをさらに７５０〜１０００℃で再び熱処理すると、雲母がガラスから析出する。７５０℃より低い温度での熱処理では十分に雲母は析出せず、１０００℃より高い温度での熱処理では、雲母が熱分解する。このようにしてカルシウムイオン伝導性を示す結晶化ガラスが得られる。また、この結晶化ガラスは快削性を示す。 When the transparent glass showing ion conductivity obtained by the method described in (0027) above is further heat-treated at 750 to 1000 ° C., mica is precipitated from the glass. Mica is not sufficiently precipitated by heat treatment at a temperature lower than 750 ° C., and mica is thermally decomposed by heat treatment at a temperature higher than 1000 ° C. Thus crystallized glass is obtained which indicates a mosquito Rushiumuion conductivity. Moreover, this crystallized glass exhibits free-cutting properties.
上記（００２８）に記載した熱処理条件で、特に、７５０〜８００℃で熱処理して得られる雲母を主結晶相とした結晶化ガラスはイオン伝導性および快削性だけではなく、水中でも崩壊しないほどの高い耐水性を有する。また、上記（００２８）に記載した熱処理条件で、特に、８００〜８５０℃で熱処理して得られる雲母を主結晶相とした結晶化ガラスはイオン伝導性および快削性だけではなく、空気中では自然崩壊しない耐水性を有する。
次に、本発明を実施例によりさらに詳細に説明するが、本発明はこれらの例によってなんら限定されるものではない。
Under the heat treatment conditions described in the above (0028), in particular, the crystallized glass whose main crystal phase is mica obtained by heat treatment at 750 to 800 ° C. is not only ionic conductivity and free-cutting property, but also does not collapse in water. High water resistance. In addition, in the heat treatment conditions described in the above (0028), in particular, crystallized glass having mica obtained by heat treatment at 800 to 850 ° C. as a main crystal phase has not only ion conductivity and free-cutting properties, but also in air. It has water resistance that does not spontaneously collapse.
EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
リチウムイオン伝導性を示す結晶化ガラスおよびガラスに関わる実施組成例、雲母が結晶化する熱処理条件例および物性例を表１に示す。これらの結晶化ガラスおよびガラスは原料として酸化マグネシウム、酸化アルミニウム、酸化ケイ素、炭酸リチウムおよびフッ化マグネシウムを用い、それらを表１に示す組成になるように秤取して混合し、炭酸リチウムを分解して炭酸ガスを放出させるために９００℃で１時間加熱する。その後、原料混合物を白金容器中に封入し、１４５０℃で２時間溶融し、炉外放冷して無色透明のガラスとする。それを示差熱分析によって求めたガラス転移温度よりも約２０℃高い温度（５５０〜６５０℃）で加熱することにより、ガラスのひずみ抜きを行う。このようにして作製した無色透明のガラスが表１のNo.1および No.2である。さらに、得られたガラスを結晶化させるために６５０〜９００℃で２〜４時間熱処理する。このようにして作製した結晶化ガラスが表１のNo.3〜No.6である。No.1および No.2のガラスは室温で１０‐２Ｓ／ｃｍを超える高い伝導率を示す。また、No.4は水中でも崩壊しないような高い耐水性、３×１０‐３Ｓ／ｃｍ（５０℃において）を超える高いイオン伝導率、快削性および透光性を有する結晶化ガラスである。
（表１）
Implementation composition example involving forming crystallized glass and glass showing a lithium-ion conductivity, showing the heat treatment conditions Examples and properties Example mica crystallizes in Table 1. These crystallized glass and glass use magnesium oxide, aluminum oxide, silicon oxide, lithium carbonate and magnesium fluoride as raw materials, weigh and mix them so as to have the composition shown in Table 1, and decompose lithium carbonate And heated at 900 ° C. for 1 hour to release carbon dioxide. Thereafter, the raw material mixture is sealed in a platinum container, melted at 1450 ° C. for 2 hours, and allowed to cool outside the furnace to form colorless and transparent glass. The glass is de-strained by heating it at a temperature (550 to 650 ° C.) that is about 20 ° C. higher than the glass transition temperature determined by differential thermal analysis. The colorless and transparent glasses thus prepared are No. 1 and No. 2 in Table 1. Furthermore, in order to crystallize the obtained glass, it heat-processes at 650-900 degreeC for 2 to 4 hours. The crystallized glasses thus produced are No. 3 to No. 6 in Table 1. The No. 1 and No. 2 glasses exhibit high conductivity exceeding 10 −2 S / cm at room temperature. No. 4 is a crystallized glass having high water resistance that does not collapse even in water, high ion conductivity exceeding 3 × 10 −3 S / cm (at 50 ° C.), free-cutting property and translucency. .
(Table 1)
ナトリウムイオン伝導性を示す焼成体および結晶化ガラスに関わる実施組成例、雲母が生成あるいは結晶化する熱処理条件例および物性例を表２に示す。焼成体は原料として酸化マグネシウム、酸化アルミニウム、酸化ケイ素およびフッ化ナトリウムを用い、それらを表２のNo.7およびNo.8に示す組成になるように秤取して混合し、その原料混合物を静水圧成形によって成形体とする。それを白金容器中に封入した後、８００〜１２００℃で焼成することによってナトリウム雲母（Na2Mg6Al2Si6O20F4あるいはNa4Mg6Al4Si4O20F4など）が生成し、雲母結晶焼成体となる。また、結晶化ガラスおよびガラスは原料として酸化マグネシウム、酸化アルミニウム、酸化ケイ素、炭酸ナトリウムおよびフッ化マグネシウムを用い、それらを表２のNo.9およびNo.10に示す組成になるように秤取して混合し、炭酸ナトリウムを分解して炭酸ガスを放出させるために９００℃で１時間加熱する。その後、原料混合物を白金容器中に封入し、１５５０℃で２時間溶融し、氷水中に投入して急冷することでガラスとする。このガラスを細かく粉砕して微粉末とし、それを静水圧成形によって成形体とする。それを白金容器中に封入した後、６５０〜１０００℃で２時間熱処理して雲母を結晶化させ、結晶化ガラスとする。表２のNo.7〜No.10はすべて室温で３×１０‐３Ｓ／ｃｍを超える高い伝導率を示す。また、その中のNo.9は水中でも崩壊しないほどの耐水性を示す。
（表２）
Table 2 shows examples of the composition relating to the fired body and crystallized glass exhibiting sodium ion conductivity, examples of heat treatment conditions and physical properties for generating or crystallizing mica. The calcined product uses magnesium oxide, aluminum oxide, silicon oxide and sodium fluoride as raw materials, weigh and mix them so as to have the compositions shown in No. 7 and No. 8 of Table 2, and mix the raw material mixture. Formed by isostatic pressing. Sodium mica (Na 2 Mg 6 Al 2 Si 6 O 20 F 4 or Na 4 Mg 6 Al 4 Si 4 O 20 F 4 etc.) is fired at 800-1200 ° C after enclosing it in a platinum container. It produces | generates and becomes a mica crystal sintered body. Crystallized glass and glass use magnesium oxide, aluminum oxide, silicon oxide, sodium carbonate and magnesium fluoride as raw materials, and weigh them so that they have the compositions shown in No. 9 and No. 10 of Table 2. And heat at 900 ° C. for 1 hour to decompose sodium carbonate and release carbon dioxide. Thereafter, the raw material mixture is sealed in a platinum container, melted at 1550 ° C. for 2 hours, put into ice water, and rapidly cooled to obtain glass. This glass is finely pulverized into a fine powder, which is formed into a molded body by isostatic pressing. After enclosing it in a platinum container, it is heat-treated at 650 to 1000 ° C. for 2 hours to crystallize the mica to obtain crystallized glass. No. 7 to No. 10 in Table 2 all show high conductivity exceeding 3 × 10 −3 S / cm at room temperature. Moreover, No. 9 in it shows water resistance so that it does not disintegrate in water.
(Table 2)
カルシウムイオン伝導性を示す結晶化ガラスおよびガラスに関わる実施組成例、雲母が結晶化する熱処理条件例および物性例を表３に示す。これらの結晶化ガラスおよびガラスは原料として酸化マグネシウム、酸化アルミニウム、酸化ケイ素、炭酸カルシウムおよびフッ化マグネシウムを用い、それらを表３に示す組成となるように秤取して混合し、炭酸カルシウムを分解して炭酸ガスを放出させるために９００℃で１時間加熱する。その後、原料混合物を白金容器中に封入し、１４５０℃で２時間溶融し、炉外放冷して無色透明のガラスとする。それを示差熱分析によって求めたガラス転移温度よりも約２０℃高い温度（６００〜６５０℃）で加熱することにより、ガラスのひずみ抜きを行う。このようにして作製した無色透明のガラスが表３のNo.11およびNo.12である。さらに、得られたガラスを７５０〜１０００℃で２時間熱処理して雲母を結晶化させる。このようにして作製した結晶化ガラスが表３のNo.13およびNo.14である。No.11〜No.14は５×１０‐３Ｓ／ｃｍを超える高い伝導率を示し、特に、No.14は水中でも崩壊しないような高い耐水性、高いイオン伝導率および快削性を有する結晶化ガラスである。
（表３）
Table 3 shows examples of crystallized glass exhibiting calcium ion conductivity, examples of composition relating to glass, examples of heat treatment conditions for crystallizing mica, and examples of physical properties. These crystallized glass and glass use magnesium oxide, aluminum oxide, silicon oxide, calcium carbonate and magnesium fluoride as raw materials, weigh and mix them so as to have the composition shown in Table 3, and decompose calcium carbonate And heated at 900 ° C. for 1 hour to release carbon dioxide. Thereafter, the raw material mixture is sealed in a platinum container, melted at 1450 ° C. for 2 hours, and allowed to cool outside the furnace to form colorless and transparent glass. The glass is de-strained by heating it at a temperature (600 to 650 ° C.) that is about 20 ° C. higher than the glass transition temperature determined by differential thermal analysis. The colorless and transparent glasses thus prepared are No. 11 and No. 12 in Table 3. Furthermore, the obtained glass is heat-treated at 750 to 1000 ° C. for 2 hours to crystallize mica. The crystallized glasses thus prepared are No. 13 and No. 14 in Table 3. No.11 to No.14 show high conductivity exceeding 5 × 10 −3 S / cm, and in particular, No.14 has high water resistance, high ionic conductivity and free machinability that do not collapse even in water. Crystallized glass.
(Table 3)
以上のように本発明で提供されるリチウム、ナトリウムあるいはカルシウムがキャリアーとなりイオン伝導性を示す焼成体、結晶化ガラスおよびガラスは固体電解質として電池やセンサーの材料として利用できる。そのなかで快削性を示す結晶化ガラスは他のセラミックスあるいはガラスの電解質と異なり機械加工が容易であるため、機械加工に必要とするコストを大幅に低減できる。さらに、そのなかで透明な結晶化ガラスは、エレクトロクロミックディスプレイの固体電解質などディスプレイ材料として、また、機械加工が容易な光学材料として利用できる。
As described above, the fired body, crystallized glass, and glass that exhibit ion conductivity by using lithium, sodium, or calcium as a carrier according to the present invention can be used as a battery or sensor material as a solid electrolyte. Among them, crystallized glass exhibiting free-cutting properties is easy to machine unlike other ceramics or glass electrolytes, so that the cost required for machining can be greatly reduced. In addition, transparent crystallized glass can be used as a display material such as a solid electrolyte of an electrochromic display and as an optical material that can be easily machined.
Claims (2)
この原料組成物を５００〜９５０℃で加熱して原料中の無機塩を分解し、
無機塩を分解した後の原料組成物を容器に封入して溶融した後、
５５０〜６５０℃で熱処理して歪み抜きし、さらに６００〜７００℃で熱処理して雲母を結晶化させることを特徴とする、イオン伝導性及び透光性を備え、リチウムイオンが層間イオンである雲母結晶を主結晶相とする結晶化ガラスの製造方法。 From a composition of 4-5% Li 2 O, 14-20% MgO, 9-13% Al 2 O 3 , 48-56% SiO 2 , 14-20% MgF 2 expressed in weight%. Mixing raw material composition
This raw material composition is heated at 500 to 950 ° C. to decompose inorganic salts in the raw material,
After the raw material composition after decomposing the inorganic salt is sealed in a container and melted,
A mica having ion conductivity and translucency, wherein lithium ions are interlayer ions, characterized in that the strain is removed by heat treatment at 550 to 650 ° C., and further, the mica is crystallized by heat treatment at 600 to 700 ° C. A method for producing crystallized glass having crystals as a main crystal phase .
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