JPH0458149B2 - - Google Patents
Info
- Publication number
- JPH0458149B2 JPH0458149B2 JP19310983A JP19310983A JPH0458149B2 JP H0458149 B2 JPH0458149 B2 JP H0458149B2 JP 19310983 A JP19310983 A JP 19310983A JP 19310983 A JP19310983 A JP 19310983A JP H0458149 B2 JPH0458149 B2 JP H0458149B2
- Authority
- JP
- Japan
- Prior art keywords
- solid electrolyte
- lithium
- battery
- sulfide
- conductivity
- 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 27
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 claims description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 8
- 229910052744 lithium Inorganic materials 0.000 claims description 8
- -1 alkaline earth metal sulfide Chemical class 0.000 claims description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 5
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 5
- 229910001416 lithium ion Inorganic materials 0.000 claims description 5
- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical group [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 claims description 4
- CYQAYERJWZKYML-UHFFFAOYSA-N phosphorus pentasulfide Chemical compound S1P(S2)(=S)SP3(=S)SP1(=S)SP2(=S)S3 CYQAYERJWZKYML-UHFFFAOYSA-N 0.000 claims description 4
- 229910018091 Li 2 S Inorganic materials 0.000 claims description 3
- 239000000203 mixture Substances 0.000 description 7
- JGIATAMCQXIDNZ-UHFFFAOYSA-N calcium sulfide Chemical compound [Ca]=S JGIATAMCQXIDNZ-UHFFFAOYSA-N 0.000 description 4
- 229910001216 Li2S Inorganic materials 0.000 description 2
- CJDPJFRMHVXWPT-UHFFFAOYSA-N barium sulfide Chemical compound [S-2].[Ba+2] CJDPJFRMHVXWPT-UHFFFAOYSA-N 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910018130 Li 2 S-P 2 S 5 Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000003708 ampul Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- XCAUINMIESBTBL-UHFFFAOYSA-N lead(ii) sulfide Chemical compound [Pb]=S XCAUINMIESBTBL-UHFFFAOYSA-N 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- XXCMBPUMZXRBTN-UHFFFAOYSA-N strontium sulfide Chemical compound [Sr]=S XXCMBPUMZXRBTN-UHFFFAOYSA-N 0.000 description 1
- SMDQFHZIWNYSMR-UHFFFAOYSA-N sulfanylidenemagnesium Chemical compound S=[Mg] SMDQFHZIWNYSMR-UHFFFAOYSA-N 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)
- Conductive Materials (AREA)
- Primary Cells (AREA)
Description
(イ) 産業上の利用分野
本発明はリチウムを負極活物質とする固体電解
質電池に係り、特にリチウムイオン導電性の固体
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。現
在、一般に知られている固体電解質のうち比較的
特性が良好なものとしてヨウ化リチウム−アルミ
ナ系或いは硫化リチウム−五硫化リン−ヨウ化リ
チウムの３成分系ガラス状固体電解質があるが、
いずれも室温での導電率は高々１×10-5S／cm程
度である。
(ハ) 発明の目的
本発明の目的とするところは、リチウムイオン
導電率の高い固体電解質を提案し、高率放電特性
に優れた固体電解質電池を提供することにある。
(ニ) 発明の構成
本発明は上記目的を達成すべくなされたものに
してそ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）及び少くとも一種のアルカリ土類金属
硫化物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。
ガラス状固体電解質は次のようにして合成し
た。即ち硫化リチウム（Li2S）、五硫化リン
（P2S5）、ヨウ化リチウム（LiI）及び硫化カルシ
ウム（CaS）、硫化マグネシウム（MgS）、硫化
ストロンチウム（SrS）、硫化バリウム（BaS）
の市販特級試薬を夫々粉砕して400メツシユパス
し250℃で減圧乾燥する。
次にこれらの原料を所定のモル比で混合し石英
アンプル中に真空封入して電気炉で1000℃に加熱
したのち急冷してガラス状固体電解質を得る。
こうして得たガラス状固体電解質を粉砕し400
メツシユパスしたのちプレス成型して径10mmφ、
厚み２mmのペレツトとし、電極としてのリチウム
圧延板を圧着してIKHzの交流ブリツジで抵抗を
測定し導電率を算出した。次表は各種組成におけ
るガラス状固体電解質の20℃での導電率を示す。
(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 a lithium ion conductive 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, among the generally known solid electrolytes, there are glassy solid electrolytes with relatively good properties, such as lithium iodide-alumina type or lithium sulfide-phosphorus pentasulfide-lithium iodide type.
In either case, the conductivity at room temperature is about 1×10 -5 S/cm at most. (c) Object of the invention The object of the invention is to propose a solid electrolyte with high lithium ion conductivity and to provide a solid electrolyte battery with excellent high rate discharge characteristics. (d) Structure of the Invention The present invention has been made to achieve the above object, and its gist is that the present invention comprises a positive electrode, a lithium negative electrode, and a lithium ion conductive solid electrolyte, The electrolyte is a glassy solid electrolyte consisting of lithium sulfide (Li 2 S), phosphorus pentasulfide (P 2 S 5 ), lithium iodide (LiI) and at least one alkaline earth metal sulfide. Found in solid electrolyte batteries. (e) Examples Examples of the present invention will be described in detail below. The glassy solid electrolyte was synthesized as follows. namely lithium sulfide (Li 2 S), phosphorus pentasulfide (P 2 S 5 ), lithium iodide (LiI) and calcium sulfide (CaS), magnesium sulfide (MgS), strontium sulfide (SrS), barium sulfide (BaS).
Each of the commercially available special grade reagents was ground, passed through 400 meshes, and dried under reduced pressure at 250°C. Next, these raw materials are mixed in a predetermined molar ratio, vacuum sealed in a quartz ampoule, heated to 1000°C in an electric furnace, and then rapidly cooled to obtain a glassy solid electrolyte. The glassy solid electrolyte obtained in this way was crushed and
After mesh passing, press molding and diameter 10mmφ.
A pellet with a thickness of 2 mm was made, a rolled lithium plate was bonded as an electrode, and the resistance was measured using an IKHz AC bridge to calculate the conductivity. The following table shows the electrical conductivity of glassy solid electrolytes at 20°C for various compositions.
【表】
上表から明らかなように、Li2S−P2S5−LiIの
３成分系に少くとも一種のアルカリ土類金属硫化
物を添加したものは高い導電率を示し、特に
Li2S：P2S5：LiI：CaS＝23：17：50：10の組成
比のもの或いはLi2S：P2S5：LiI：CaS：MaS＝
23：17：50：５：５の組成比のものに至つては上
記３成分系に比して約２倍強の導電率を示してい
る。
このように導電率が向上する理由は未だ明らか
ではないが、一般にガラス状態における導電率向
上の要因としてはイオンが移動しうる空隙が多数
存在し、且イオンが結晶構造によつて束縛を受け
ないことがあげられる。
本発明による固体電解質においては、二価でリ
チウムよりイオン半径が大きく且ガラス状形成に
障害とならないアルカリ土類金属の硫化物の添加
によつてリチウムイオンの可動性が増大したため
導電率が向上したと考えられる。
次に本発明による固体電解質（試料番号３）を
用いて次のように電池を作成した。
正極合剤としてヨウ化鉛（PbI2）、硫化鉛
（PbS）及び鉛（Pb）粉末を１：１：２のモル比
で混合したものを用い、又負極として厚み1.0mm
のリチウム圧延板を10mmφに打抜いたものを用い
る。
電池組立に際しては、正極合剤300mgと固体電
解質100mgを径10.0φに一体成型したのち固体電解
質の他側にリチウム負極を圧着してなる。
又、比較のために固体電解質として試料番号１
の３成分系を用いることを除いて他は本発明電池
と同様の比較電池を作成した。
第１図はこれらの電池の室温下における電流−
電圧特性、第２図は60℃における56KΩ定負荷放
電特性を夫々示す。尚、図中Ａは本発明電池、Ｂ
は比較電池である。
(ヘ) 発明の効果
上述した如く、固体電解質として硫化リチウ
ム、五硫化リン、ヨウ化リチウム及び少くとも一
種のアルカリ土類金属硫化物よりなるガラス状固
体電解質を用いることにより固体電解質電池の放
電特性を改善しうるものであり、その工業的価値
は極めて大である。[Table] As is clear from the above table, the three-component system of Li 2 S−P 2 S 5 −LiI to which at least one kind of alkaline earth metal sulfide is added exhibits high conductivity, especially
Li2S : P2S5 :LiI:CaS=23:17:50:10 composition ratio or Li2S : P2S5 :LiI: CaS :MaS=
The one with the composition ratio of 23:17:50:5:5 exhibits a conductivity that is about twice as high as that of the above-mentioned three-component system. The reason for this improvement in conductivity is not yet clear, but the general reason for the improvement in conductivity in the glass state is that there are many voids through which ions can move, and ions are not constrained by the crystal structure. There are many things that can be mentioned. In the solid electrolyte of the present invention, the conductivity was improved because the mobility of lithium ions was increased by the addition of alkaline earth metal sulfide, which is divalent and has a larger ionic radius than lithium and does not impede glassy formation. it is conceivable that. Next, a battery was created as follows using the solid electrolyte of the present invention (sample number 3). A mixture of lead iodide (PbI 2 ), lead sulfide (PbS), and lead (Pb) powder at a molar ratio of 1:1:2 was used as the positive electrode mixture, and a 1.0 mm thick mixture was used as the negative electrode.
A 10 mmφ punched lithium rolled plate is used. When assembling the battery, 300 mg of the positive electrode mixture and 100 mg of the solid electrolyte are integrally molded to a diameter of 10.0φ, and then a lithium negative electrode is crimped onto the other side of the solid electrolyte. Also, for comparison, sample number 1 was used as a solid electrolyte.
A comparative battery was prepared which was otherwise similar to the battery of the present invention except that a three-component system was used. Figure 1 shows the current of these batteries at room temperature.
Voltage characteristics. Figure 2 shows the 56KΩ constant load discharge characteristics at 60°C. In addition, in the figure, A is a battery of the present invention, and B is a battery of the present invention.
is a comparison battery. (f) Effects of the invention As mentioned above, the discharge characteristics of a solid electrolyte battery can be improved by using a glassy solid electrolyte made of lithium sulfide, phosphorus pentasulfide, lithium iodide, and at least one kind of alkaline earth metal sulfide as a solid electrolyte. can be improved, and its industrial value is extremely large.
第１図及び第２図は本発明電池と比較電池との
特性比較図であり、第１図は室温下における電流
−電圧特性、第２図は60℃における56KΩ定負荷
放電特性を夫々示す。
Ａ……本発明電池、Ｂ……比較電池。
FIGS. 1 and 2 are characteristic comparison diagrams of the battery of the present invention and a comparison battery. FIG. 1 shows the current-voltage characteristics at room temperature, and FIG. 2 shows the 56KΩ constant load discharge characteristics at 60°C. A...Battery of the present invention, B...Comparison battery.
Claims (1)
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）及び少くとも一
種のアルカリ土類金属硫化物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 device comprising 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 lithium iodide (LiI). and a solid electrolyte battery comprising a glassy solid electrolyte made of at least one kind of alkaline earth metal sulfide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19310983A JPS6084772A (en) | 1983-10-14 | 1983-10-14 | Solid electrolyte battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19310983A JPS6084772A (en) | 1983-10-14 | 1983-10-14 | Solid electrolyte battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6084772A JPS6084772A (en) | 1985-05-14 |
| JPH0458149B2 true JPH0458149B2 (en) | 1992-09-16 |
Family
ID=16302393
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19310983A Granted JPS6084772A (en) | 1983-10-14 | 1983-10-14 | Solid electrolyte battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6084772A (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5590836B2 (en) | 2009-09-09 | 2014-09-17 | 公立大学法人大阪府立大学 | Sulfide solid electrolyte |
| JP5521899B2 (en) * | 2010-08-26 | 2014-06-18 | トヨタ自動車株式会社 | Sulfide solid electrolyte material and lithium solid state battery |
| JP2013103851A (en) * | 2011-11-11 | 2013-05-30 | Nippon Chem Ind Co Ltd | Lithium iodide anhydrate, method for producing lithium iodide anhydrate, solid electrolyte and lithium ion battery |
| JP6374741B2 (en) * | 2014-09-22 | 2018-08-15 | 公立大学法人大阪府立大学 | Solid electrolyte for all solid state secondary battery, method for producing the same, and all solid state secondary battery including the same |
| JP6568141B2 (en) * | 2017-04-27 | 2019-08-28 | 古河機械金属株式会社 | Solid electrolyte material for lithium ion battery and method for producing solid electrolyte material for lithium ion battery |
| CN111344812B (en) * | 2017-11-14 | 2022-07-22 | 出光兴产株式会社 | Sulfide-based solid electrolyte containing metal element and method for producing same |
| CN111029662A (en) * | 2019-12-30 | 2020-04-17 | 江苏智泰新能源科技有限公司 | Preparation method of sulfide electrolyte material |
-
1983
- 1983-10-14 JP JP19310983A patent/JPS6084772A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6084772A (en) | 1985-05-14 |
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