JPH0686588B2 - Method for producing lithium ion conductive solid electrolyte - Google Patents
Method for producing lithium ion conductive solid electrolyteInfo
- Publication number
- JPH0686588B2 JPH0686588B2 JP2068583A JP6858390A JPH0686588B2 JP H0686588 B2 JPH0686588 B2 JP H0686588B2 JP 2068583 A JP2068583 A JP 2068583A JP 6858390 A JP6858390 A JP 6858390A JP H0686588 B2 JPH0686588 B2 JP H0686588B2
- Authority
- JP
- Japan
- Prior art keywords
- ion
- solid electrolyte
- glass
- lithium
- lithium ion
- 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 - Lifetime
Links
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims description 20
- 229910001416 lithium ion Inorganic materials 0.000 title claims description 20
- 239000007784 solid electrolyte Substances 0.000 title claims description 19
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 239000011521 glass Substances 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 8
- -1 halogen ion Chemical class 0.000 claims description 7
- 150000001450 anions Chemical class 0.000 claims description 5
- 150000002500 ions Chemical class 0.000 claims description 5
- 229910001413 alkali metal ion Inorganic materials 0.000 claims description 4
- 150000001768 cations Chemical class 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 3
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 claims description 3
- 229910001422 barium ion Inorganic materials 0.000 claims description 3
- 229910001424 calcium ion Inorganic materials 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 claims description 3
- 229910001414 potassium ion Inorganic materials 0.000 claims description 3
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 claims description 2
- NCMHKCKGHRPLCM-UHFFFAOYSA-N caesium(1+) Chemical compound [Cs+] NCMHKCKGHRPLCM-UHFFFAOYSA-N 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000010409 thin film Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 229910052792 caesium Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 229910052740 iodine Chemical group 0.000 description 2
- 239000011630 iodine Chemical group 0.000 description 2
- 239000011244 liquid electrolyte Substances 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000004017 vitrification Methods 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical group [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910001508 alkali metal halide Inorganic materials 0.000 description 1
- 150000008045 alkali metal halides Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 229910001615 alkaline earth metal halide Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229940006460 bromide ion Drugs 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000004455 differential thermal analysis Methods 0.000 description 1
- 239000002001 electrolyte material Substances 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005816 glass manufacturing process Methods 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229940006461 iodide ion Drugs 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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
Landscapes
- Conductive Materials (AREA)
- Primary Cells (AREA)
- Secondary Cells (AREA)
Description
【発明の詳細な説明】 産業上の利用分野 本発明は、リチウム電池の電解質材料として有用な新規
なリチウムイオン導電性固体電解質の製造方法に関す
る。TECHNICAL FIELD The present invention relates to a method for producing a novel lithium ion conductive solid electrolyte useful as an electrolyte material for a lithium battery.
従来の技術 固体電解質材料を液体電解質材料に代えて電池に利用す
ると、液体電解質材料を用いた電池にみられる液漏れ破
損や電極物質の溶出といった問題を解消できる上に、薄
膜化や小型化が容易になるなど多くの利点がある。この
ような電池としてリチウムイオン導電性固体電解質材料
を用い、リチウム金属を負極活物質とするリチウム電池
が知られている。このリチウムイオン導電性固体電解質
材料としては、大別して有機ポリマー系、無機結晶系及
び無機ガラス系がある。有機ポリマー系は、成形性に優
れ、薄膜化が容易であるものの、機械的強度や熱的安定
性に乏しいという欠点があるし、また、無機結晶系は、
熱的安定性に富み高温での使用にも耐えるものの、多結
晶体であるために結晶粒界におけるIRドロップにより導
電率が低下し、成形性が良好でなく、薄膜化が困難であ
るという欠点がある。一方、無機ガラス系は、成形性に
富み薄膜化が可能であり、粒界におけるIRドロップがな
いなどの長所を有するので、高いイオン導電性を有する
材料が見い出されればリチウム電池への応用の可能性は
高い。Conventional technology If a solid electrolyte material is used in a battery instead of a liquid electrolyte material, problems such as liquid leakage damage and electrode substance elution found in a battery using a liquid electrolyte material can be solved, and thinning and downsizing can be achieved. There are many advantages such as ease. As such a battery, a lithium battery using a lithium ion conductive solid electrolyte material and using lithium metal as a negative electrode active material is known. The lithium ion conductive solid electrolyte material is roughly classified into an organic polymer system, an inorganic crystal system and an inorganic glass system. The organic polymer system is excellent in moldability and can be easily formed into a thin film, but has a drawback that it is poor in mechanical strength and thermal stability, and the inorganic crystal system is
Although it has excellent thermal stability and can withstand use at high temperatures, it is a polycrystalline material, so its conductivity drops due to IR drops at the crystal grain boundaries, resulting in poor moldability and difficulty in thinning. There is. On the other hand, the inorganic glass type has advantages such as high moldability, thin film formation, and no IR drop at the grain boundary. Therefore, if a material with high ionic conductivity is found, it can be applied to lithium batteries. The nature is high.
本発明者らは、このような無機ガラス系の長所に着目
し、研究を重ねた結果、ハロゲン化リチウムを主成分と
する高い導電性を有するガラスを完成した。このガラス
は室温で10-9〜10-6S/cmの導電性を有し、リチウム電池
への応用が可能であるが、ガラス転移温度が40〜70℃程
度であることから、例えばガラス転移温度以上ではガラ
スは粘弾性挙動を示し、制御不可能な状態で変形し、結
晶化して使用困難となるなど使用条件が制約される欠点
がある。The present inventors have focused their attention on the advantages of such an inorganic glass system and, as a result of repeated research, have completed a glass containing lithium halide as a main component and having high conductivity. This glass has a conductivity of 10 -9 to 10 -6 S / cm at room temperature and can be applied to lithium batteries, but since it has a glass transition temperature of 40 to 70 ° C, for example, glass transition Above the temperature, glass exhibits viscoelastic behavior, deforms in an uncontrollable state, and crystallizes to make it difficult to use.
発明が解決しようとする課題 本発明は、このような事情の下、前記の無機ガラス系固
体電解質の特性を十分保持したまま、製造が容易であ
り、成形性に富み薄膜化が容易である上に、高イオン導
電率を有し、しかも液化温度が高く使用可能な温度範囲
が広くて高温での使用も可能な新規なリチウムイオン導
電性固体電解質の製造方法を提供することを目的として
なされたものである。DISCLOSURE OF THE INVENTION The present invention, under such circumstances, is easy to manufacture while maintaining the characteristics of the above-mentioned inorganic glass-based solid electrolyte sufficiently, and is easy to form into a thin film with high moldability. In addition, it has been made for the purpose of providing a method for producing a novel lithium ion conductive solid electrolyte having a high ionic conductivity, a high liquefaction temperature, a wide usable temperature range and use at high temperature. It is a thing.
課題を解決するための手段 本発明者らは、前記の好ましい性質を有する新規なリチ
ウムイオン導電性固体電解質の製造方法を開発するため
に種々研究を重ねた結果、ハロゲン化リチウムを主成分
とし、所定のアルカリ土類金属イオンと所定のアルカリ
金属イオンをハロゲン化物として所定の割合で含有して
成るガラス組成物を所定温度で熱処理することによって
結晶化物が得られること、また、この結晶化物が優れた
リチウムイオン導電率を有することを見い出し、この知
見に基づいて本発明を完成するに至った。Means for Solving the Problems The present inventors have conducted various studies in order to develop a method for producing a novel lithium-ion conductive solid electrolyte having the above-mentioned preferable properties, and contain lithium halide as a main component, A crystallized product can be obtained by heat-treating a glass composition containing a predetermined alkaline earth metal ion and a predetermined alkali metal ion as a halide in a predetermined ratio at a predetermined temperature, and the crystallized product is excellent. Further, they have found that they have lithium ion conductivity, and have completed the present invention based on this finding.
すなわち、本発明は、陽イオン成分が、イオン数量に基
づき、（Ａ）リチウムイオン45〜60％、（Ｂ）カルシウ
ムイオン及びバリウムイオンの中から選ばれた少なくと
も１種のアルカリ土類金属イオン５〜15％及び（Ｃ）カ
リウムイオン及びセシウムイオンの中から選ばれた少な
くとも１種のアルカリ金属イオン25〜50％から成り、か
つ陰イオン成分が塩素イオン、臭素イオン及びヨウ素イ
オンの中から選ばれた少なくとも１種のハロゲンイオン
から成る組成を有するガラスを50〜100℃で熱処理して
結晶化することを特徴とするリチウムイオン導電性固体
電解質の製造方法を提供するものである。That is, in the present invention, the cation component has at least one alkaline earth metal ion 5 selected from the group consisting of (A) lithium ion 45 to 60% and (B) calcium ion and barium ion, based on the number of ions. .About.15% and (C) 25 to 50% of at least one alkali metal ion selected from potassium ion and cesium ion, and the anion component is selected from chloride ion, bromide ion and iodide ion. Another object of the present invention is to provide a method for producing a lithium ion conductive solid electrolyte, which comprises heat-treating glass having a composition of at least one kind of halogen ion at 50 to 100 ° C. to crystallize the glass.
本発明方法において、原料として用いられるガラスは、
陽イオン成分が、イオン数量に基づき、（Ａ）成分であ
るリチウムイオンを45〜60％、（Ｂ）成分である、カル
シウムイオン及びバリウムイオンの中から選ばれた少な
くとも１種のアルカリ土類金属イオンを５〜15％、及び
（Ｃ）成分である、カリウムイオン及びセシウムイオン
の中から選ばれた少なくとも１種のアルカリ金属イオン
を25〜50％それぞれ含有することが必要である。このよ
うな組成範囲を逸脱するとガラス化することが困難にな
る。In the method of the present invention, the glass used as a raw material is
Based on the number of ions, the cation component is 45 to 60% of lithium ion which is the component (A), and at least one alkaline earth metal selected from calcium ion and barium ion which is the component (B). It is necessary to contain 5 to 15% of the ions, and 25 to 50% of the component (C), that is, at least one alkali metal ion selected from potassium ions and cesium ions. When it deviates from such a composition range, it becomes difficult to vitrify.
この（Ｂ）成分及び（Ｃ）成分は、ガラス化を容易にす
る作用がある。The components (B) and (C) have the function of facilitating vitrification.
次に、これらの陽イオン成分と組合わせる陰イオンとし
ては塩素イオン、臭素イオン、ヨウ素イオンの中から選
ばれた少なくとも１種のハロゲンイオンが用いられる
が、これらが２種以上の混合イオンである場合にはその
主要成分となる陰イオンは、全陰イオンの数量に基づき
90％以上を占めるのが望ましい。Next, at least one halogen ion selected from chlorine ion, bromine ion, and iodine ion is used as the anion combined with these cation components, and these are mixed ions of two or more kinds. In some cases, the main anion is based on the total anion quantity.
It is desirable to occupy 90% or more.
このガラスは、無色透明であり、リチウムイオンを主成
分として多く含むため、室温でのイオン導電率は10-6S/
cmにも達する。また、このガラスについてリチウムイオ
ンの輸率は１であるのに対し、電子伝導性及びリチウム
イオン以外のイオン導電性は実質上存しない。This glass is colorless and transparent, and contains a large amount of lithium ions as its main component, so the ionic conductivity at room temperature is 10 -6 S /
It reaches to cm. Further, while the transport number of lithium ions in this glass is 1, electronic conductivity and ionic conductivity other than lithium ions are substantially absent.
本発明方法においては、このガラスを50〜100℃で熱処
理して結晶化することにより、固体電解質を製造する。
この熱処理は、通常10〜60分間行われる。In the method of the present invention, a solid electrolyte is produced by heat-treating this glass at 50 to 100 ° C. to crystallize it.
This heat treatment is usually performed for 10 to 60 minutes.
このようにして得られた固体電解質は、全体的に緻密で
あり、液化温度が高いという特性を有する。The solid electrolyte thus obtained has characteristics that it is dense as a whole and has a high liquefaction temperature.
本発明方法において原料として用いられるガラスは、一
般的なガラス製造法、例えば融液を冷却する方法などに
より製造される。すなわち、所定のハロゲン化物原料を
所定の組成になるように秤量、混合し、石英ガラスや白
金製等のるつぼを用いて450〜550℃で溶融させる。この
原料としては、塩化リチウム、臭化リチウム又はヨウ化
リチウムなどのハロゲン化リチウムを必須とし、MX（Ｍ
はカリウム及び／又はセシウムであり、Ｘは塩素、臭素
又はヨウ素である）で表わされる少なくとも１種のアル
カリ金属ハロゲン化物及びＭ′Ｘ′２（Ｍ′はカルシウ
ム及び／又はバリウムであり、Ｘ′は塩素、臭素又はヨ
ウ素である）で表わされる少なくとも１種のアルカリ土
類金属ハロゲン化物が用いられる。溶融中、時々かきま
ぜてやると15〜30分程度で均質化する。得られた溶融液
を金属製等の型枠に流し込み冷却することにより、ガラ
ス化される。ガラス作製の全過程において製造系に混入
する水分や酸素はガラス化を困難にするので、ガラス作
製は窒素、アルゴン等の不活性ガスの雰囲気、特にグロ
ーブボックス中で行うのが好ましい。このようにして得
られたガラスの厚さは通常は0.05〜1mm程度である。The glass used as a raw material in the method of the present invention is manufactured by a general glass manufacturing method, for example, a method of cooling a melt. That is, predetermined halide raw materials are weighed and mixed so as to have a predetermined composition, and melted at 450 to 550 ° C. using a crucible made of quartz glass or platinum. As this raw material, lithium halide such as lithium chloride, lithium bromide or lithium iodide is essential, and MX (M
Is potassium and / or cesium, X is chlorine, bromine or iodine) and at least one alkali metal halide M'X ' 2 (M' is calcium and / or barium, X ' Is chlorine, bromine or iodine) and at least one alkaline earth metal halide is used. During the melting, stirring occasionally gives homogenization in about 15 to 30 minutes. The obtained melt is poured into a mold made of metal or the like and cooled to be vitrified. Moisture and oxygen mixed in the manufacturing system in the whole process of making glass make vitrification difficult, so it is preferable to carry out glass making in an atmosphere of an inert gas such as nitrogen or argon, particularly in a glove box. The thickness of the glass thus obtained is usually about 0.05 to 1 mm.
発明の効果 本発明方法によれば、ガラスを原料とするので、ガラス
の段階で成形上制御しやすく成形性に富み、薄膜化が容
易であり、このように容易に薄膜等に成形したものを熱
処理して結晶化することにより、容易にリチウムイオン
導電性固体電解質を製造することができる。しかも、こ
のようにして得られたリチウムイオン導電性固体電解質
は、結晶化物で緻密であり、粒界におけるIRドロップが
小さく、高イオン導電率を有し、例えば100℃でのリチ
ウムイオン導電率が10-5S/cmにも達し、しかも液化温度
が200〜350℃と高く使用可能な温度範囲が広いという顕
著な効果を奏する。Effects of the Invention According to the method of the present invention, since glass is used as a raw material, it is easy to control in molding at the stage of glass, rich in moldability, and easy to form a thin film. By heat treatment and crystallization, a lithium ion conductive solid electrolyte can be easily manufactured. Moreover, the lithium ion conductive solid electrolyte thus obtained is a crystallized and dense, IR drop in the grain boundary is small, has a high ionic conductivity, for example, lithium ion conductivity at 100 ℃ It has a remarkable effect that the liquefaction temperature is as high as 200 to 350 ° C. and the usable temperature range is wide, reaching 10 −5 S / cm.
従って、本発明方法で得られたのリチウムイオン導電性
固体電解質は、例えばリチウム電池の固体電解質などと
して利用することができる。Therefore, the lithium ion conductive solid electrolyte obtained by the method of the present invention can be used, for example, as a solid electrolyte of a lithium battery.
実施例 次に、実施例によって本発明をさらに詳細に説明する。EXAMPLES Next, the present invention will be described in more detail with reference to Examples.
実施例１ LiI 1.17g、KI 0.21g、CsI 1.32g及びBaI20.31gを秤量
し、石英ガラスるつぼを用いて、470℃で15分間溶融混
合した。融液を金属プレートに流し出し、別の金属プレ
ートで押さえつけることによって直径約30mm、厚さ0.5m
mの無色透明円板状ガラスを得た。このガラスを60℃で3
0分間熱処理し、結晶化させ所望の円板状導電性固体電
解質試料を得た。以上の操作はすべて窒素雰囲気のグロ
ーブボックス内で行った。得られた試料について組成を
求めるとともに示差熱分析により液化温度を求めた。そ
の結果を表に示す。Example 1 1.17 g of LiI, 0.21 g of KI, 1.32 g of CsI and 0.31 g of BaI 2 were weighed and melt-mixed for 15 minutes at 470 ° C. using a quartz glass crucible. Pour the melt onto a metal plate and press it down with another metal plate to obtain a diameter of about 30 mm and a thickness of 0.5 m.
A colorless transparent disk-shaped glass of m was obtained. This glass at 60 ° C for 3
It was heat-treated for 0 minutes and crystallized to obtain a desired disc-shaped conductive solid electrolyte sample. All the above operations were performed in a nitrogen atmosphere glove box. The composition of the obtained sample was determined and the liquefaction temperature was determined by differential thermal analysis. The results are shown in the table.
また、銀ペーストをこの円板状試料の両面に塗り電極と
し、交流インピーダンス法によって導電率を測定した。
その結果を図面に示す。これから分かるように、このも
のの100℃でのリチウムイオン導電率は4.6×10-6S/cmで
あった。Further, silver paste was applied to both surfaces of this disk-shaped sample as electrodes, and the electrical conductivity was measured by the AC impedance method.
The results are shown in the drawing. As can be seen from this, the lithium ion conductivity at 100 ° C. of this product was 4.6 × 10 −6 S / cm.
実施例２、３ 組成を変えたこと及び熱処理温度を実施例２では80℃、
実施例３では70℃としたこと以外は実施例１と同様にし
て所望の固体電解質試料を得た。Examples 2 and 3 The composition was changed and the heat treatment temperature was 80 ° C. in Example 2.
In Example 3, a desired solid electrolyte sample was obtained in the same manner as in Example 1 except that the temperature was 70 ° C.
得られた試料について実施例１と同様にして組成、液化
温度及び導電率を求めた。その結果を表に示す。The composition, liquefaction temperature and conductivity of the obtained sample were determined in the same manner as in Example 1. The results are shown in the table.
図面は、本発明方法で得られた固体電解質のイオン導電
率の温度に対する依存性を示すグラフである。The drawing is a graph showing the temperature dependence of the ionic conductivity of the solid electrolyte obtained by the method of the present invention.
Claims (1)
（Ａ）リチウムイオン45〜60％、（Ｂ）カルシウムイオ
ン及びバリウムイオンの中から選ばれた少なくとも１種
のアルカリ土類金属イオン５〜15％及び（Ｃ）カリウム
イオン及びセシウムイオンの中から選ばれた少なくとも
１種のアルカリ金属イオン25〜50％から成り、かつ陰イ
オン成分が塩素イオン、臭素イオン及びヨウ素イオンの
中から選ばれた少なくとも１種のハロゲンイオンから成
る組成を有するガラスを50〜100℃で熱処理して結晶化
することを特徴とするリチウムイオン導電性固体電解質
の製造方法。1. The cation component is based on the number of ions,
(A) lithium ion 45 to 60%, (B) at least one kind of alkaline earth metal ion selected from calcium ion and barium ion, 5 to 15%, and (C) selected from potassium ion and cesium ion. Glass having a composition of 25 to 50% of at least one alkali metal ion and an anion component of at least one halogen ion selected from chlorine ion, bromine ion and iodine ion. A method for producing a lithium ion conductive solid electrolyte, which comprises crystallizing by heat treatment at 100 ° C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2068583A JPH0686588B2 (en) | 1990-03-19 | 1990-03-19 | Method for producing lithium ion conductive solid electrolyte |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2068583A JPH0686588B2 (en) | 1990-03-19 | 1990-03-19 | Method for producing lithium ion conductive solid electrolyte |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03269079A JPH03269079A (en) | 1991-11-29 |
| JPH0686588B2 true JPH0686588B2 (en) | 1994-11-02 |
Family
ID=13377959
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2068583A Expired - Lifetime JPH0686588B2 (en) | 1990-03-19 | 1990-03-19 | Method for producing lithium ion conductive solid electrolyte |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0686588B2 (en) |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5834571A (en) * | 1981-08-24 | 1983-03-01 | Toshiba Corp | Solid electrolyte battery |
| JPS5851675A (en) * | 1981-09-24 | 1983-03-26 | Toshiba Corp | Agc circuit |
-
1990
- 1990-03-19 JP JP2068583A patent/JPH0686588B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH03269079A (en) | 1991-11-29 |
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