JPH0670905B2 - Solid electrolyte battery - Google Patents
Solid electrolyte batteryInfo
- Publication number
- JPH0670905B2 JPH0670905B2 JP57183324A JP18332482A JPH0670905B2 JP H0670905 B2 JPH0670905 B2 JP H0670905B2 JP 57183324 A JP57183324 A JP 57183324A JP 18332482 A JP18332482 A JP 18332482A JP H0670905 B2 JPH0670905 B2 JP H0670905B2
- Authority
- JP
- Japan
- Prior art keywords
- solid electrolyte
- lithium
- battery
- lii
- electrolyte battery
- 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
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
-
- 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
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Conductive Materials (AREA)
- Primary Cells (AREA)
Description
【発明の詳細な説明】 技術分野 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。TECHNICAL FIELD The present invention relates to a solid electrolyte battery using lithium as a negative electrode active material.
背景技術 この種電池は固体状の電解質を用いるため漏液の心配が
なく、保存性能が優れてい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
電特性に問題があつた。BACKGROUND ART Since this type of battery uses a solid electrolyte, it has the advantages that it does not worry about leakage and has excellent storage performance, but the conductivity of the solid electrolyte is several orders of magnitude lower than that of the liquid electrolyte, and high-rate discharge is possible. There was a problem with the characteristics.
現在、一般に用いられている固体電解質としてヨウ化リ
チウム−アルミナ（LiI−Al2O3）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）、五硫化リ
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が、更に導電性にすぐれた固体電
解質が要望されている。Currently, there is a lithium iodide-alumina (LiI-Al 2 O 3 ) system as a commonly used solid electrolyte, and recently proposed lithium sulfide (Li 2 S) and phosphorus pentasulfide (P 2 S). 5 ) and lithium iodide (LiI) ternary glassy solid electrolytes are available, but solid electrolytes having further excellent conductivity are demanded.
発明の開示 本発明は斯る点に鑑みなされたものであり、その要旨と
するところは、負極活物質としてリチウムを用いる固体
電解質電池において、固体電解質として硫化リチウム
（Li2S）、五硫化リン（P2S5）、ヨウ化リチウム（Li
I）及び水酸化リチウム（LiOH）の４成分系ガラス状固
体電解質を用いることにある。DISCLOSURE OF THE INVENTION The present invention has been made in view of the above points, and a gist thereof is a solid electrolyte battery using lithium as a negative electrode active material, in which lithium sulfide (Li 2 S) and phosphorus pentasulfide are used as a solid electrolyte. (P 2 S 5 ), lithium iodide (Li
I) and the use of a four-component glassy solid electrolyte of lithium hydroxide (LiOH).
以下本発明の実施例について詳述する。Hereinafter, examples of the present invention will be described in detail.
ガラス状固体電解質は次のようにして合成した。即ち、
Li2S、P2S5、LiI及びLiOHは夫々市販の特級試薬を400メ
ッシユ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：P2S5:LiL:LiOH＝30:15:4
5:10のモル比率になるように精秤し乳鉢で混合した。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てガラ
ス状態の固体電解質材を得る。The glassy solid electrolyte was synthesized as follows. That is,
As Li 2 S, P 2 S 5 , LiI and LiOH, commercially available special grade reagents are pulverized to 400 mesh passes and dried under reduced pressure at 250 ° C., respectively. These raw materials are Li 2 S: P 2 S 5 : LiL: LiOH = 30: 15: 4
They were precisely weighed so that the molar ratio was 5:10 and mixed in a mortar. This raw material mixture was sealed in a quartz ampoule in a vacuum and placed in an electric furnace.
After being heated to 900 ° C., it is rapidly cooled to around room temperature to obtain a solid electrolyte material in a glass state.
そしてこの固体電解質材を粉砕して400メッシユパスさ
せたのち、この粉末を３トン／cm2の圧力でプレス成型
して10mmφの４成分系ガラス状固体電解質のペレットを
作成した。Then, this solid electrolyte material was crushed and passed through 400 mesh, and this powder was press-molded at a pressure of 3 ton / cm 2 to prepare pellets of 10 mmφ four-component vitreous solid electrolyte.
第１図は上述の本発明による固体電解質（ａ）の導電率
−温度特性を示し、測定は固体電解質の両面にリチウム
板を圧着して測定用試料としこの試料の抵抗値を1KHzの
交流ブリッジで測定して導電率を算出した。FIG. 1 shows the conductivity-temperature characteristics of the solid electrolyte (a) according to the present invention described above. The measurement is carried out by pressing a lithium plate on both sides of the solid electrolyte to prepare a measurement sample, and the resistance value of this sample is an AC bridge of 1 KHz And the conductivity was calculated.
尚、図中（ｂ）はLi2S−P2S5−LiIの３成分系ガラス状
固定電解質の場合、又（ｃ）はLiI−Al2O3系固体電解質
の場合である。In FIG. (B) in the case of three-component glassy solid electrolyte of Li 2 S-P 2 S 5 -LiI, also (c) is a case of LiI-Al 2 O 3 based solid electrolyte.
次に本発明による固定電解質（ａ）、Li2S−P2S5−LiI
系ガラス状固体電解質（ｂ）及びLiI−Al2O3系固体電解
質（ｃ）を用いて電池（Ａ）、（Ｂ）及び（Ｃ）を作成
した。各電池とも負極として厚み1.0mmのリチウム圧延
板を10mmφに打抜いたものを用い、又正極合剤としてヨ
ウ化鉛（PbI2）、硫化鉛（pbS）及び鉛粉末を1:1:2のモ
ル比で混合したものを用いた。Next, the fixed electrolyte (a) according to the present invention, Li 2 S-P 2 S 5 -LiI
System glassy solid electrolyte (b) and a battery using LiI-Al 2 O 3 based solid electrolyte (c) (A), was created (B) and (C). For each battery, a 1.0 mm thick rolled lithium plate was punched out to a diameter of 10 mm as the negative electrode, and lead iodide (PbI 2 ), lead sulfide (pbS) and lead powder of 1: 1: 2 were used as the positive electrode mixture. The mixture was used in a molar ratio.
電池の作成に際しては10.8mmφの成型金型に正極合剤33
0mgを入れ均一に配置したのち、固体電解質材70mgを入
れ、ついでリチウム板を載置し全体を５トン／cm2でプ
レス成型して得る。When making a battery, add a positive electrode mixture 33 to a 10.8 mmφ molding die.
After placing 0 mg and uniformly arranging it, 70 mg of a solid electrolyte material is placed, then a lithium plate is placed and the whole is press-molded at 5 ton / cm 2 .
第２図はこれら電池の温度60℃、負荷56KΩにおける放
電特性図である。FIG. 2 is a discharge characteristic diagram of these batteries at a temperature of 60 ° C. and a load of 56 KΩ.
発明の効果 本発明電池によれば、固体電解質のイオン導電率が従来
の固体電解質に比して高いため電池特性の向上が計れ
る。その理由を考察するに、本発明電池に用いた固定電
解質はガラス状態であるので各原子は結晶状態のように
規則正しく配列されていないため、結晶格子に拘束され
ずに動けるイオンができやすく、又イオンの移動すべき
空の位置が存在しやすいと共にLiOHのOH種がイオンの移
動を促進させるためであると考えられる。EFFECTS OF THE INVENTION According to the battery of the present invention, the ionic conductivity of the solid electrolyte is higher than that of the conventional solid electrolyte, so that the battery characteristics can be improved. Considering the reason, since the fixed electrolyte used in the battery of the present invention is in a glass state and thus the atoms are not regularly arranged like a crystalline state, it is easy to generate ions that can move without being restricted by a crystal lattice, and It is thought that this is because the vacant positions where the ions should move tend to exist and the OH species of LiOH promote the movement of the ions.
尚、本実施例においては固体電解質の組成についてLi
2S：P2S5:LiI:LiOH＝30:15:45:10のモル比率の場合を例
示したが、Li2S及びP2S5については２〜65モル％、LiI
及びLiOHについては５〜85モル％の各範囲内で適用しう
る。In this example, the composition of the solid electrolyte is Li
2 S: P 2 S 5 : LiI: LiOH = 30: 15: 45: 10 was used as an example, but for Li 2 S and P 2 S 5 , 2 to 65 mol%, LiI
With respect to LiOH, it can be applied within the range of 5 to 85 mol%.
第１図は固体電解質の導電率−温度特性図、第２図は電
池の放電特性図を夫々示す。 （Ａ）……本発明電池、（Ｂ）（Ｃ）……従来電池。FIG. 1 is a conductivity-temperature characteristic diagram of the solid electrolyte, and FIG. 2 is a discharge characteristic diagram of the battery. (A) ... Battery of the present invention, (B) (C) ... Conventional battery.
Claims (1)
導電性固体電解質とを備えるものであつて、前記固体電
解質が硫化リチウム（Li2S）、五硫化リン（P2S5）、ヨ
ウ化リチウム（LiI）及び水酸化リチウム（LiOH）の４
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。1. A positive electrode, a lithium negative electrode, and a lithium ion conductive solid electrolyte, wherein the solid electrolyte is lithium sulfide (Li 2 S), phosphorus pentasulfide (P 2 S 5 ), or iodide. 4 of lithium (LiI) and lithium hydroxide (LiOH)
A solid electrolyte battery, which is a component-type glassy solid electrolyte.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57183324A JPH0670905B2 (en) | 1982-10-19 | 1982-10-19 | Solid electrolyte battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57183324A JPH0670905B2 (en) | 1982-10-19 | 1982-10-19 | Solid electrolyte battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5973851A JPS5973851A (en) | 1984-04-26 |
| JPH0670905B2 true JPH0670905B2 (en) | 1994-09-07 |
Family
ID=16133708
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57183324A Expired - Lifetime JPH0670905B2 (en) | 1982-10-19 | 1982-10-19 | Solid electrolyte battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0670905B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101489608B1 (en) * | 2010-08-26 | 2015-02-03 | 도요타 지도샤（주） | Sulfide solid electrolyte material and lithium solid state battery |
| US10008735B2 (en) | 2009-12-16 | 2018-06-26 | Toyota Jidosha Kabushiki Kaisha | Method of producing a sulfide solid electrolyte material, sulfide solid electrolyte material, and lithium battery |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4585714A (en) * | 1985-06-28 | 1986-04-29 | Union Carbide Corporation | Quaternary vitreous solid lithium cation conductive electrolyte |
| 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 |
| WO2005101549A1 (en) | 2004-04-01 | 2005-10-27 | Sumitomo Electric Industries Ltd. | Negative electrode member for secondary lithium battery and process for producing the same |
| JP4580149B2 (en) * | 2003-04-24 | 2010-11-10 | 出光興産株式会社 | Lithium ion conductive sulfide glass manufacturing method and lithium ion conductive sulfide glass ceramic manufacturing method |
| TWI415140B (en) * | 2003-04-24 | 2013-11-11 | Idemitsu Kosan Co | Lithium-ion conductive sulfide glass and glass-ceramic manufacturing method, and a solid-state battery using the same |
| WO2010092692A1 (en) * | 2009-02-16 | 2010-08-19 | トヨタ自動車株式会社 | Power storage device system, motor driver and mobile body using this system |
| JP5508646B2 (en) * | 2011-05-27 | 2014-06-04 | トヨタ自動車株式会社 | Solid secondary battery system and method for producing regenerated solid secondary battery |
| JP6309344B2 (en) * | 2014-03-19 | 2018-04-11 | 出光興産株式会社 | Solid electrolyte and battery |
-
1982
- 1982-10-19 JP JP57183324A patent/JPH0670905B2/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10008735B2 (en) | 2009-12-16 | 2018-06-26 | Toyota Jidosha Kabushiki Kaisha | Method of producing a sulfide solid electrolyte material, sulfide solid electrolyte material, and lithium battery |
| US10707518B2 (en) | 2009-12-16 | 2020-07-07 | Toyota Jidosha Kabushiki Kaisha | Method of producing a sulfide solid electrolyte material, sulfide solid electrolyte material, and lithium battery |
| KR101489608B1 (en) * | 2010-08-26 | 2015-02-03 | 도요타 지도샤（주） | Sulfide solid electrolyte material and lithium solid state battery |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5973851A (en) | 1984-04-26 |
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