JPH0430151B2 - - Google Patents
Info
- Publication number
- JPH0430151B2 JPH0430151B2 JP2095984A JP2095984A JPH0430151B2 JP H0430151 B2 JPH0430151 B2 JP H0430151B2 JP 2095984 A JP2095984 A JP 2095984A JP 2095984 A JP2095984 A JP 2095984A JP H0430151 B2 JPH0430151 B2 JP H0430151B2
- Authority
- JP
- Japan
- Prior art keywords
- solid electrolyte
- battery
- lithium
- lii
- present
- 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
Links
- 239000007784 solid electrolyte Substances 0.000 claims description 28
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 claims description 11
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 claims description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 5
- 229910052744 lithium Inorganic materials 0.000 claims description 5
- 239000011149 active material Substances 0.000 claims description 3
- 229940119177 germanium dioxide Drugs 0.000 claims description 3
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 2
- 229910001416 lithium ion Inorganic materials 0.000 claims description 2
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 2
- 239000000203 mixture Substances 0.000 description 6
- 230000006866 deterioration Effects 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910018068 Li 2 O Inorganic materials 0.000 description 1
- 229910018130 Li 2 S-P 2 S 5 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000003708 ampul Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical compound [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- CYQAYERJWZKYML-UHFFFAOYSA-N phosphorus pentasulfide Chemical compound S1P(S2)(=S)SP3(=S)SP1(=S)SP2(=S)S3 CYQAYERJWZKYML-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
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
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Primary Cells (AREA)
- Conductive Materials (AREA)
Description
(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
体電解質電池に係り、特に固体電解質の改良に関
するものである。
(ロ) 従来技術
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、保存性能に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。
現在、一般的に用いられている固体電解質とし
ては、例えば特公昭56−9785号公報に開示されて
いるようにLiI−Al2O3系があるが、その導電率
は室温で５×10-6Ｓ／cm〜１×10-5Ｓ／cm程度で
ある。
さて、近年に至つて例えば特開昭58−1974号公
報或いは特開昭58−189967号公報に開示されてい
るように五硫化リン（P2S5）、硫化リチウム（Li2
Ｓ）及びヨウ化リチウム（LiI）の三成分系から
なるガラス状固体電解質が提案されている。ガラ
ス状固体電解質の場合、単結晶や層状の固体電解
質に比してイオンは結晶格子の束縛を受けないた
め移動しやすくなり、又イオンの移動できる空隙
も多くなるため導電率が向上するという利点があ
る。
ところが前述のP2S5−Li2Ｓ−LiI系固体電解質
は硫化物を主体としており、長期間の放電、保存
において硫黄の遊離が起り易く、その結果導電率
が低下し電池特性が劣下するという問題があつ
た。
(ハ) 発明の目的
本発明の目的とするところは長期間の放電、保
存においても安定で且良好な導電率を有した新規
な組成のガラス状固体電解質を提案し、以つてこ
の種電池の特性改善を計ることにある。
(ニ) 発明の構成
本発明は正極と、リチウムを活物質とする負極
と、リチウムイオン導電性固体電解質とを備える
ものであつて、前記固体電解質が酸化リチウム
（Li2Ｏ）、二酸化ゲルマニウム（GeO2）及びヨウ
化リチウム（LiI）よりなる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。
(ホ) 実施例
以下本発明の実施例について詳述する。
固体電解質の作成
酸化リチウム（Li2Ｏ）−二酸化ゲルマニウム
（GeO2）−ヨウ化リチウム（LiI）系ガラス状固体
電解質を次のようにして得た。
即ち、Li2Ｏ，GeO2及びLiIを夫々粉砕、乾燥
したのち所定のモル比で混合する。次にこの混合
物を石英ガラスアンプル中に真空封入し電気炉で
1000℃、20分間加熱したのち急冷する。このよう
にして得た各種組成比の本発明固体電解質の導電
率を下表に示す。
(a) Industrial Application Field The present invention relates to a solid electrolyte battery using lithium as a negative electrode active material, and particularly relates to improvement of the solid electrolyte. (b) Prior art 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. There was a problem with high rate discharge characteristics. Currently, a commonly used solid electrolyte is the LiI-Al 2 O 3 system as disclosed in Japanese Patent Publication No. 56-9785, but its conductivity is 5 × 10 - at room temperature. 6 S/cm to 1×10 -5 S/cm. Now, in recent years, phosphorus pentasulfide (P 2 S 5 ) and lithium sulfide (Li 2
A glassy solid electrolyte consisting of a ternary system of lithium iodide (S) and lithium iodide (LiI) has been proposed. In the case of glassy solid electrolytes, compared to single crystal or layered solid electrolytes, ions are not constrained by the crystal lattice, making them easier to move, and there are more voids in which ions can move, which has the advantage of improving conductivity. There is. However, the aforementioned P 2 S 5 -Li 2 S-LiI solid electrolyte is mainly composed of sulfide, and sulfur is likely to be liberated during long-term discharge and storage, resulting in a decrease in conductivity and deterioration in battery characteristics. There was a problem. (c) Purpose of the Invention The purpose of the present invention is to propose a glassy solid electrolyte with a new composition that is stable even during long-term discharge and storage and has good conductivity, and to improve the performance of this type of battery. The purpose is to measure the improvement of characteristics. (D) Structure of the Invention The present invention comprises a positive electrode, a negative electrode containing lithium as an active material, and a lithium ion conductive solid electrolyte, wherein the solid electrolyte contains lithium oxide (Li 2 O), germanium dioxide ( A solid electrolyte battery is characterized in that it is a glassy solid electrolyte made of G e O 2 ) and lithium iodide (LiI). (e) Examples Examples of the present invention will be described in detail below. Preparation of Solid Electrolyte A lithium oxide ( Li2O )-germanium dioxide ( GeO2 )-lithium iodide ( LiI ) based glassy solid electrolyte was obtained as follows. That is, Li 2 O, G e O 2 and LiI are ground and dried, respectively, and then mixed in a predetermined molar ratio. Next, this mixture was vacuum sealed in a quartz glass ampoule and heated in an electric furnace.
Heat at 1000℃ for 20 minutes and then rapidly cool. The electrical conductivities of the solid electrolytes of the present invention having various composition ratios thus obtained are shown in the table below.
【表】
電池の作成
次に上表の固体電解質（試料No.２）を用いて電
池を作成した。負極としてリチウム圧延板を10mm
に打抜いたものを使用し、又正極合剤としては
活物質であるヨウ化鉛（PbI2）と導電剤でなる黒
鉛粉末を90：10の重量比で混合したるものを用い
た。
電池の作成に際しては、10.0mmの成型金型に
正極合剤400mg及び固体電解質材100mgを充填して
一体成型し、ついで固体電解質側に前記リチウム
負極を圧着する。この電池をＡとする。
次に、比較のために従来のLi2Ｓ−P2S5−LiI系
固体電解質を用いる以外、他は実施例と同一の電
池Ｂを作製した。
図は本発明電池Ａと従来電池Ｂとを60℃、
270kΩ負荷で放電した時の放電特性を示す。
(ハ) 発明の効果
図から明らかなように本発明電池は従来電池に
比して優れた放電特性を示している。
この理由は固体電解質の安定性に関係する。即
ち、従来のP2S5−Li2Ｓ−LiI係では硫化物を主体
としており、硫化物は分解しやすく、特に高温、
長期間の放電に際しては分解による固体電解質の
劣化、遊離した硫黄による正、負極の劣化は無視
できず、その結果電池の放電特性の低下を招く。
これに対して、本発明電池に用いたガラス状固
体電解質は酸化物を基質としており安定性に優れ
ているため、電池の放電特性を改善しうるのであ
る。[Table] Creating a battery Next, a battery was created using the solid electrolyte (sample No. 2) shown in the above table. 10mm lithium rolled plate as negative electrode
The positive electrode mixture used was a mixture of lead iodide (PbI 2 ) as an active material and graphite powder as a conductive agent at a weight ratio of 90:10. When creating a battery, a 10.0 mm mold is filled with 400 mg of the positive electrode mixture and 100 mg of the solid electrolyte material and integrally molded, and then the lithium negative electrode is crimped onto the solid electrolyte side. This battery is called A. Next, for comparison, a battery B was fabricated which was the same as in Example except that a conventional Li 2 S-P 2 S 5 -LiI solid electrolyte was used. The figure shows battery A of the present invention and conventional battery B at 60°C.
Shows the discharge characteristics when discharging with a 270kΩ load. (c) Effects of the invention As is clear from the figure, the battery of the present invention exhibits superior discharge characteristics compared to the conventional battery. The reason for this is related to the stability of the solid electrolyte. In other words, the conventional P 2 S 5 -Li 2 S-LiI system mainly consists of sulfides, and sulfides are easily decomposed, especially at high temperatures.
During long-term discharge, deterioration of the solid electrolyte due to decomposition and deterioration of the positive and negative electrodes due to liberated sulfur cannot be ignored, resulting in a decrease in the discharge characteristics of the battery. On the other hand, the glassy solid electrolyte used in the battery of the present invention has an oxide as a substrate and has excellent stability, so that the discharge characteristics of the battery can be improved.
図は本発明電池と従来電池との放電特性比較図
である。
Ａ……本発明電池、Ｂ……従来電池。
The figure is a comparison diagram of discharge characteristics between a battery of the present invention and a conventional battery. A...Battery of the present invention, B...Conventional battery.
Claims (1)
チウムイオン導電性固体電解質とを備えるもので
あつて、前記固体電解質が酸化リチウム（Li2
Ｏ）、二酸化ゲルマニウム（GeO2）及びヨウ化リ
チウム（LiI）よりなる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 negative electrode using lithium as an active material, and a lithium ion conductive solid electrolyte, the solid electrolyte being lithium oxide (Li 2
A solid electrolyte battery characterized in that it is a glassy solid electrolyte made of O), germanium dioxide (G e O 2 ), and lithium iodide (LiI).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2095984A JPS60165061A (en) | 1984-02-07 | 1984-02-07 | Solid electrolyte battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2095984A JPS60165061A (en) | 1984-02-07 | 1984-02-07 | Solid electrolyte battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60165061A JPS60165061A (en) | 1985-08-28 |
| JPH0430151B2 true JPH0430151B2 (en) | 1992-05-20 |
Family
ID=12041713
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2095984A Granted JPS60165061A (en) | 1984-02-07 | 1984-02-07 | Solid electrolyte battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60165061A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2565937Y2 (en) * | 1991-11-22 | 1998-03-25 | 長野日本無線 株式会社 | Portable radio connector cover |
| US5312623A (en) * | 1993-06-18 | 1994-05-17 | The United States Of America As Represented By The Secretary Of The Army | High temperature, rechargeable, solid electrolyte electrochemical cell |
-
1984
- 1984-02-07 JP JP2095984A patent/JPS60165061A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60165061A (en) | 1985-08-28 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |