JPS59151770A - Solid electrolyte battery - Google Patents
Solid electrolyte batteryInfo
- Publication number
- JPS59151770A JPS59151770A JP2507383A JP2507383A JPS59151770A JP S59151770 A JPS59151770 A JP S59151770A JP 2507383 A JP2507383 A JP 2507383A JP 2507383 A JP2507383 A JP 2507383A JP S59151770 A JPS59151770 A JP S59151770A
- Authority
- JP
- Japan
- Prior art keywords
- solid electrolyte
- lithium
- glass
- lii
- li2s
- 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.)
- Granted
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/18—Cells with non-aqueous electrolyte with solid electrolyte
Abstract
Description
【発明の詳細な説明】
（イ）産業上の利用分野
本発明は負極活物質としてリチウムを用いる固体電解質
電池に関するものである。DETAILED DESCRIPTION OF THE INVENTION (a) Field of Industrial Application The present invention relates to a solid electrolyte battery using lithium as a negative electrode active material.
（ロ）従来技術
この種電池は固体電解質を用いるため漏液の心配がなく
、保存性能が優れるという利点を有するが、固体電解質
の導電率は液状電解質に比して数段低く高率放電特性に
問題があった。現在、一般に用いられている固体電解質
としてはヨウ化リチウム−アルミナ系があり、又最近提
案されているものとして硫化リチウム（Ｌｉ２Ｓ）、三
硫化リン（Ｐ２Ｓ５）及びヨウ化リチウム（ＬｉＩ）の
３成分系ガラス状固体電解質がある。(b) Conventional technology Since this type of battery uses a solid electrolyte, there is no need to worry about leakage, and it has the advantage of excellent storage performance. However, the conductivity of the solid electrolyte is several orders of magnitude lower than that of the liquid electrolyte, and it has high rate discharge characteristics. There was a problem. Currently, the solid electrolyte commonly used is lithium iodide-alumina, and recently proposed solid electrolytes include lithium sulfide (Li2S), phosphorus trisulfide (P2S5), and lithium iodide (LiI). There are glassy solid electrolytes.
ｅ→ 目 的
本発明は上記従来の固体電解質に比して更に高導電性を
有する固体電解質の開発を目的とし、この種電池の性能
向上を計るものである
に）構 成
本発明の要旨とするところは、正極と、リチウム負極と
、リチウムイオン導電性固体電解質とを備えるものであ
って、固体電解質が硫化リチウム（ＬｉｚＳ）、二硫化
ゲル？−’−ウム（Ｇｅ、Ｓ ２ 、）及びヨウ化リチ
ウム（Ｌｉ Ｉ ）の３成分系ガラス状固体電解質であ
ることを特徴とする固体電解質電池にある。e→ Purpose The purpose of the present invention is to develop a solid electrolyte having higher conductivity than the conventional solid electrolytes mentioned above, and to improve the performance of this type of battery.) Structure: Summary of the present invention However, it is equipped with a positive electrode, a lithium negative electrode, and a lithium ion conductive solid electrolyte, and the solid electrolyte is lithium sulfide (LizS), disulfide gel? A solid electrolyte battery is characterized in that it is a ternary glassy solid electrolyte of -'-ium (Ge, S2, ) and lithium iodide (LiI).
件）実施例 以下本発明の実施例について詳述する。Case) Example Examples of the present invention will be described in detail below.
ガラス状固抹電解質は次のように合成した。即ちＬｉｚ
Ｓ、Ｇｅ５２及びＬｉＩは夫々市販の特級試薬を４００
メ・リシュパスするまで粉砕し２５０℃で減圧乾燥した
ものを用いる。これらの原料をＬｉ２Ｓ：Ｇｅ５ｚ：Ｌ
ｉＩ＝３０：１５：５５のモル比率になるように秤量し
乳鉢で混合した。この原料混合物を真空中で石英アンプ
ルに封入し電気炉で９００℃に加熱した後、急激に室温
付近まで冷却しガラス状態の固体電解質材を得る。次い
でこれを粉砕して４００メツシユパスさせたのち、この
粉末を３トン／ｄの圧力でプレス成型して６成分系のガ
ラス状固体電解質を作成した。The glassy solid electrolyte was synthesized as follows. That is, Liz
S, Ge52 and LiI were each commercially available special grade reagents.
The material used is one that has been pulverized until it passes through the mesh and dried under reduced pressure at 250°C. These raw materials are Li2S:Ge5z:L
They were weighed and mixed in a mortar so that the molar ratio was iI=30:15:55. This raw material mixture is sealed in a quartz ampoule in vacuum, heated to 900° C. in an electric furnace, and then rapidly cooled to around room temperature to obtain a solid electrolyte material in a glass state. Next, this was pulverized and subjected to 400 mesh passes, and then this powder was press-molded at a pressure of 3 tons/d to create a six-component glassy solid electrolyte.
第１図は上述の本発明による固体電解質（ａｌの導電率
一温度特性を示し、測定は固体電解質の内面にリチウム
板を圧着して測定用試料とし、この試料の抵抗を１ＫＨ
ｚの交流ブリッジで測定して導電率を算出した。尚、図
中（ｂｌはＬ１２５−Ｐ２Ｓ５−ＬｉＩの３成分系ガラ
ス状固体電解質、（りはＬｉＩ−Ａ、／２０３系固体電
解質の場合を夫々示す。Figure 1 shows the electrical conductivity-temperature characteristics of the solid electrolyte (Al) according to the present invention, and the measurement was carried out by pressing a lithium plate onto the inner surface of the solid electrolyte as a measurement sample, and the resistance of this sample was 1KH.
The conductivity was calculated by measuring with an AC bridge of z. In the figure, (bl shows the case of a three-component glassy solid electrolyte of L125-P2S5-LiI, and (li shows the case of LiI-A, /203 system solid electrolyte, respectively).
第１図より本発明による固体電解質（ａｌの導電率は従
来の固体電解質（ｂ）或いは（Ｃ）に比して高い値を示
しているが、その理由は第一に固体電解質′がガラス状
態であるためリチウムイオンの移動が円滑に行なわれる
こと、第二に二硫化ゲルマニウム（ＧｅＳｚ）の添加に
よりガラス状態が一層安定化されたことが考えられろう
次にこれらの各固体電解質（ａｌ（ｂｌ及び（Ｃ）を用
いて電池（Ａ）（Ｂｌ及び（Ｃ１を作成した。各電池と
も負極として厚み１．０麿のリチウム圧延板を１０螺φ
に打抜いたものを用い、又正極合剤としてヨウ化鉛（Ｐ
ｂＩ２）、硫化鉛（ｐｂｓ）及び鉛粉末を１：１：２の
モル比でＨしたものを用いた。電池の作成に際しては、
１０．８ａφの成型金型に正極合剤３３０ダを入れ均一
に配置したのち、固体電解質材７０呼を入れ、ついでリ
チウム板を載置し、全体を５トン／ｄで加圧成型して得
る。As shown in Figure 1, the conductivity of the solid electrolyte (al) according to the present invention is higher than that of the conventional solid electrolyte (b) or (C). The reason for this is first that the solid electrolyte ' is in a glass state. Therefore, it is thought that the movement of lithium ions is carried out smoothly, and secondly, the glass state is further stabilized by the addition of germanium disulfide (GeSz). Next, each of these solid electrolytes (al(bl) Batteries (A) (Bl and (C1) were prepared using B and (C). For each battery, a lithium rolled plate with a thickness of 1.0 mm was used as a negative electrode with a diameter of 10 screws.
lead iodide (P) was used as the positive electrode mixture.
bI2), lead sulfide (PBS), and lead powder in a molar ratio of 1:1:2 were used. When making batteries,
After putting 330 da of positive electrode mixture into a 10.8aφ mold and arranging it uniformly, 70 dabs of solid electrolyte material were put in, then a lithium plate was placed, and the whole was molded under pressure at 5 tons/d. .
第２図及び第３図はこれら電池の電池特性比較図であり
、９Ｊ２図は室温における電流−電圧特性図、又第３図
は温度６０℃、負荷５６にΩにおける放電特性図である
。FIGS. 2 and 3 are comparison diagrams of battery characteristics of these batteries, and FIG. 9J2 is a current-voltage characteristic diagram at room temperature, and FIG. 3 is a discharge characteristic diagram at a temperature of 60° C. and a load of 56 Ω.
（へ）効 果
第２図及び第３図より゛本発明電池の特性は従来電池に
比して優れていることがわかる。(f) Effects From FIGS. 2 and 3, it can be seen that the characteristics of the battery of the present invention are superior to those of the conventional battery.
これは、本発明電池に用いた固体電解質カイ、Ｌｉ５２
、Ｇｅ５２及びＬｉＩの６成分系ガラス状固体電解質よ
りなり、固体電解質の導電率が高く、且安定化している
ので高温の条件下でも分解することがないという利点に
基づくものである。This is the solid electrolyte Li52 used in the battery of the present invention.
This is based on the advantage that the solid electrolyte has high conductivity and is stabilized, so that it does not decompose even under high temperature conditions.
尚、本実施例においては固体電解質の組成番こつ比率の
場合を例示し＄、Ｌｉ５２Ｇ！２０〜４０モ／ｌ／％、
９ｅＳ２は５〜２０モル％、Ｌｉ Ｉ Ｇｔ ４０〜７
５モル％の組成範囲内においてもガラス化カイ可能であ
る。In this example, the composition ratio of the solid electrolyte is exemplified as $, Li52G! 20-40 mo/l/%,
9eS2 is 5-20 mol%, Li I Gt 40-7
Vitrification is possible even within the composition range of 5 mol%.
第１図は固体電解質の導電率一温度特性図、第２図及び
第３図は電池特性を示し、第２図Ｇま電流−電圧特性図
、第３図は放電特性図を夫々示す。
四・・・本発明電池、（Ｂｌ（Ｃ’ｌ・・・従来電池。
第１図
、ゑｉ４ ｔ’ｃ〕
１０’／Ｔ＋に−１）FIG. 1 is a conductivity-temperature characteristic diagram of a solid electrolyte, FIGS. 2 and 3 are battery characteristics, FIG. 2 is a current-voltage characteristic diagram, and FIG. 3 is a discharge characteristic diagram. 4...Battery of the present invention, (Bl (C'l... Conventional battery. Fig. 1, ゑi4 t'c〕 10'/T+ -1)
Claims (1)
体電解質とを備えるものであって、前記固体電解質が硫
化リチウム（Ｌｉ２Ｓ）、二硫化ゲルマニウム（ＧｅＳ
２）及びヨウ化リチウム（Ｌｉｌ）の６成分系ガラス状
固体電解質であることを特徴とする固体電解質電池。(2) A device comprising a positive electrode, a lithium negative electrode, and a lithium ion conductive solid electrolyte, wherein the solid electrolyte includes lithium sulfide (Li2S), germanium disulfide (GeS), and a lithium ion conductive solid electrolyte.
2) and a six-component glassy solid electrolyte of lithium iodide (Lil).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2507383A JPH0670906B2 (en) | 1983-02-16 | 1983-02-16 | Solid electrolyte battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2507383A JPH0670906B2 (en) | 1983-02-16 | 1983-02-16 | Solid electrolyte battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59151770A true JPS59151770A (en) | 1984-08-30 |
| JPH0670906B2 JPH0670906B2 (en) | 1994-09-07 |
Family
ID=12155747
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2507383A Expired - Lifetime JPH0670906B2 (en) | 1983-02-16 | 1983-02-16 | Solid electrolyte battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0670906B2 (en) |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5085953A (en) * | 1990-09-18 | 1992-02-04 | Eveready Battery Company, Inc. | Vitreous compositions based on Li3 PO4 and LiPO3 as network formers and network modifiers |
| US6277524B1 (en) | 1997-12-09 | 2001-08-21 | Toyota Jidosha Kabushiki Kaisha | Lithium-ion-conductive solid electrolyte and solid-electrolyte lithium battery |
| WO2012026238A1 (en) * | 2010-08-26 | 2012-03-01 | Toyota Jidosha Kabushiki Kaisha | Sulfide solid electrolyte material and lithium solid state battery |
| WO2013005085A1 (en) * | 2011-07-06 | 2013-01-10 | Toyota Jidosha Kabushiki Kaisha | Sulfide solid electrolyte material, lithium solid-state battery, and method for producing sulfide solid electrolyte material |
| KR20130056204A (en) | 2010-02-26 | 2013-05-29 | 제온 코포레이션 | All solid state secondary battery and method for manufacturing all solid state secondary battery |
| WO2017213156A1 (en) | 2016-06-09 | 2017-12-14 | 日本ゼオン株式会社 | Binder composition for solid electrolyte batteries and slurry composition for solid electrolyte batteries |
| WO2018012380A1 (en) | 2016-07-12 | 2018-01-18 | 日本ゼオン株式会社 | Binder composition for solid electrolyte batteries |
| KR20180041091A (en) | 2015-08-27 | 2018-04-23 | 니폰 제온 가부시키가이샤 | Binder composition for all solid state batteries |
| KR20180050603A (en) | 2015-09-10 | 2018-05-15 | 니폰 제온 가부시키가이샤 | Binder composition for all solid state batteries |
| WO2018163776A1 (en) | 2017-03-10 | 2018-09-13 | 日本ゼオン株式会社 | Binder for all-solid-state batteries, binder composition for all-solid-state batteries and method for producing binder composition for all-solid-state batteries |
| KR20190045182A (en) | 2016-09-06 | 2019-05-02 | 니폰 제온 가부시키가이샤 | A binder composition for all solid batteries, a slurry composition for all solid batteries, an electrode for all solid batteries, |
| WO2019116964A1 (en) | 2017-12-15 | 2019-06-20 | 日本ゼオン株式会社 | Binder composition for all-solid secondary battery, slurry composition for all-solid secondary battery, functional layer for all-solid secondary battery, and all-solid secondary battery |
| US10797304B2 (en) | 2015-03-25 | 2020-10-06 | Zeon Corporation | All-solid-state secondary battery |
| US10797343B2 (en) | 2015-09-16 | 2020-10-06 | Zeon Corporation | Binder for all-solid-state secondary batteries, and all-solid-state secondary battery |
-
1983
- 1983-02-16 JP JP2507383A patent/JPH0670906B2/en not_active Expired - Lifetime
Cited By (27)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5085953A (en) * | 1990-09-18 | 1992-02-04 | Eveready Battery Company, Inc. | Vitreous compositions based on Li3 PO4 and LiPO3 as network formers and network modifiers |
| US6277524B1 (en) | 1997-12-09 | 2001-08-21 | Toyota Jidosha Kabushiki Kaisha | Lithium-ion-conductive solid electrolyte and solid-electrolyte lithium battery |
| KR20130056204A (en) | 2010-02-26 | 2013-05-29 | 제온 코포레이션 | All solid state secondary battery and method for manufacturing all solid state secondary battery |
| US10193185B2 (en) | 2010-08-26 | 2019-01-29 | Toyota Jidosha Kabushiki Kaisha | Sulfide solid electrolyte material and lithium solid state battery |
| CN103081206A (en) * | 2010-08-26 | 2013-05-01 | 丰田自动车株式会社 | Sulfide solid electrolyte material and lithium solid state battery |
| US9356315B2 (en) | 2010-08-26 | 2016-05-31 | Toyota Jidosha Kabushiki Kaisha | Sulfide solid electrolyte material and lithium solid state battery |
| WO2012026238A1 (en) * | 2010-08-26 | 2012-03-01 | Toyota Jidosha Kabushiki Kaisha | Sulfide solid electrolyte material and lithium solid state battery |
| WO2013005085A1 (en) * | 2011-07-06 | 2013-01-10 | Toyota Jidosha Kabushiki Kaisha | Sulfide solid electrolyte material, lithium solid-state battery, and method for producing sulfide solid electrolyte material |
| KR20230034420A (en) | 2015-03-25 | 2023-03-09 | 니폰 제온 가부시키가이샤 | All-solid secondary battery |
| US10797304B2 (en) | 2015-03-25 | 2020-10-06 | Zeon Corporation | All-solid-state secondary battery |
| KR20180041091A (en) | 2015-08-27 | 2018-04-23 | 니폰 제온 가부시키가이샤 | Binder composition for all solid state batteries |
| US10622633B2 (en) | 2015-09-10 | 2020-04-14 | Zeon Corporation | Binder composition for all-solid-state battery |
| KR20180050603A (en) | 2015-09-10 | 2018-05-15 | 니폰 제온 가부시키가이샤 | Binder composition for all solid state batteries |
| US10797343B2 (en) | 2015-09-16 | 2020-10-06 | Zeon Corporation | Binder for all-solid-state secondary batteries, and all-solid-state secondary battery |
| WO2017213156A1 (en) | 2016-06-09 | 2017-12-14 | 日本ゼオン株式会社 | Binder composition for solid electrolyte batteries and slurry composition for solid electrolyte batteries |
| KR20190016021A (en) | 2016-06-09 | 2019-02-15 | 니폰 제온 가부시키가이샤 | Binder compositions for solid electrolyte batteries and slurry compositions for solid electrolyte batteries |
| US10985401B2 (en) | 2016-06-09 | 2021-04-20 | Zeon Corporation | Binder composition for solid electrolyte battery and slurry composition for solid electrolyte battery |
| KR20190029520A (en) | 2016-07-12 | 2019-03-20 | 니폰 제온 가부시키가이샤 | Binder composition for solid electrolyte battery |
| US10862128B2 (en) | 2016-07-12 | 2020-12-08 | Zeon Corporation | Binder composition for solid electrolyte battery |
| WO2018012380A1 (en) | 2016-07-12 | 2018-01-18 | 日本ゼオン株式会社 | Binder composition for solid electrolyte batteries |
| KR20190045182A (en) | 2016-09-06 | 2019-05-02 | 니폰 제온 가부시키가이샤 | A binder composition for all solid batteries, a slurry composition for all solid batteries, an electrode for all solid batteries, |
| US11145866B2 (en) | 2016-09-06 | 2021-10-12 | Zeon Corporation | Binder composition for all-solid-state battery, slurry composition for all-solid-state battery, electrode for all-solid-state battery, and all-solid-state battery |
| KR20190123283A (en) | 2017-03-10 | 2019-10-31 | 니폰 제온 가부시키가이샤 | All-solid-state battery binder, all-solid-state battery binder composition, and all-solid-state battery binder composition manufacturing method |
| WO2018163776A1 (en) | 2017-03-10 | 2018-09-13 | 日本ゼオン株式会社 | Binder for all-solid-state batteries, binder composition for all-solid-state batteries and method for producing binder composition for all-solid-state batteries |
| KR20200097688A (en) | 2017-12-15 | 2020-08-19 | 니폰 제온 가부시키가이샤 | Binder composition for all-solid secondary batteries, slurry composition for all-solid secondary batteries, functional layer for all-solid secondary batteries, and all-solid secondary batteries |
| WO2019116964A1 (en) | 2017-12-15 | 2019-06-20 | 日本ゼオン株式会社 | Binder composition for all-solid secondary battery, slurry composition for all-solid secondary battery, functional layer for all-solid secondary battery, and all-solid secondary battery |
| US11557766B2 (en) | 2017-12-15 | 2023-01-17 | Zeon Corporation | Binder composition for all-solid-state secondary battery, slurry composition for all-solid-state secondary battery, functional layer for all-solid-state secondary battery, and all-solid-state secondary battery |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0670906B2 (en) | 1994-09-07 |
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