JPH065622B2 - Non-aqueous electrolyte battery - Google Patents
Non-aqueous electrolyte batteryInfo
- Publication number
- JPH065622B2 JPH065622B2 JP59108761A JP10876184A JPH065622B2 JP H065622 B2 JPH065622 B2 JP H065622B2 JP 59108761 A JP59108761 A JP 59108761A JP 10876184 A JP10876184 A JP 10876184A JP H065622 B2 JPH065622 B2 JP H065622B2
- Authority
- JP
- Japan
- Prior art keywords
- battery
- aqueous electrolyte
- present
- mixed solvent
- methyltetrahydrofuran
- 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/06—Electrodes for primary cells
-
- 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
- H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
- H01M6/162—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte
- H01M6/164—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte by the solvent
-
- 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
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Primary Cells (AREA)
Description
【発明の詳細な説明】 (イ) 産業上の利用分野 本発明はチリウム、ナトリウムなどの軽金属或いはそれ
らの合金を活物質とする負極と、金属の酸化物、硫化物
或いはハロゲン化物などを活物質とする正極と、溶媒と
溶質とからなる非水電解液とを備えた非水電解電池に関
するものである。DETAILED DESCRIPTION OF THE INVENTION (a) Field of Industrial Application The present invention relates to a negative electrode having a light metal such as tylium or sodium or an alloy thereof as an active material, and an oxide, a sulfide or a halide of a metal as an active material. And a nonaqueous electrolytic solution containing a solvent and a solute.
(ロ) 従来技術 この種電池に用いられる非水電解液を構成する溶媒及び
溶質として種々のものが提案されている。(B) Conventional technology Various solvents and solutes have been proposed as constituents of the non-aqueous electrolyte used in this type of battery.
具体的には例えば特公昭57-32866号公報に開示されてい
るように、溶媒としてプロピレンカーボネート、γ−ブ
チロラクトン、ジメトキシエタン、ジオキソラン、テト
ラハイドラフランなど、又溶質として過塩素酸リチウ
ム、ホウフッ化リチウムなどが知られている。Specifically, for example, as disclosed in JP-B-57-32866, as a solvent, propylene carbonate, γ-butyrolactone, dimethoxyethane, dioxolane, tetrahydrafuran, etc., and as a solute, lithium perchlorate, lithium borofluoride. Are known.
又、正極活物質については二酸化マンガンやフッ化炭素
を用いた非水電解電池が提案され、且実用化に至ってい
る。As a positive electrode active material, a nonaqueous electrolytic battery using manganese dioxide or fluorocarbon has been proposed and has been put into practical use.
さて、近年においてはこの種電池の適用分野の拡大に伴
い電池特性の改善が要望されており、その一つとして保
存後の低温放電特性の向上が望まれている。Now, in recent years, there has been a demand for improvement in battery characteristics with the expansion of application fields of this type of battery, and as one of them, improvement in low-temperature discharge characteristics after storage is desired.
(ハ) 発明の目的 本発明は特に二酸化マンガンを正極活物質とする水電解
液電池において、非水電解液を改良して保存後の低温放
電性に優れた非水電解液電池を提供することを目的とす
る。(C) Object of the invention The present invention provides a non-aqueous electrolyte battery that is excellent in low-temperature discharge property after storage by improving the non-aqueous electrolyte solution, particularly in a water electrolyte battery using manganese dioxide as a positive electrode active material. With the goal.
(ニ) 発明の構成 上記目的を達成するための本発明に係る非水電解液電池
は、リチウム、ナトリウムなどの軽金属或いはそれらの
合金を活物質とする負極と、二酸化マンガンを活物質と
する正極と、溶媒と溶質とからなる非水電解液とを備え
るものであって、前記溶媒が、プロピレンカーボネート
と２−メチルテトラハイドロフランとを含む混合溶媒、
γ−ブチロラクトンと２−メチルテトラハイドロフラン
とを含む混合溶媒、又は、ジオキソランと２−メチルテ
トラハイドロフランとを含む混合溶媒であるものであ
る。(D) Configuration of the invention The non-aqueous electrolyte battery according to the present invention for achieving the above object is a negative electrode having a light metal such as lithium or sodium or an alloy thereof as an active material, and a positive electrode having manganese dioxide as an active material. And a non-aqueous electrolytic solution comprising a solvent and a solute, wherein the solvent is a mixed solvent containing propylene carbonate and 2-methyltetrahydrofuran,
It is a mixed solvent containing γ-butyrolactone and 2-methyltetrahydrofuran or a mixed solvent containing dioxolane and 2-methyltetrahydrofuran.
(ホ) 実施例 以下本発明の実施例について詳述する。(E) Example Hereinafter, an example of the present invention will be described in detail.
実施例１． 溶媒としてプロピレンカーボネート（PC）と２−メチル
テトラハイドロフラン（2Me-THF）とを混合比１：１で
混合した混合溶媒を用い、この混合溶媒に溶質として過
塩素酸リチウム（ＬｉＣｌＯ４）を１モル／溶解した
ものを電解液とする。Example 1. A mixed solvent prepared by mixing propylene carbonate (PC) and 2-methyltetrahydrofuran (2Me-THF) at a mixing ratio of 1: 1 was used as a solvent, and lithium perchlorate (LiClO 4 ) was used as a solute in the mixed solvent. Mol / dissolved is used as the electrolytic solution.
正極は350〜430℃の温度範囲で熱処理した二酸化マンガ
ンを活物質としこの二酸化マンガンと、導電剤としての
カーボン粉末及び結着剤としてのフッ素樹脂粉末とを8
5：10：５の重量比で混合した混合物を加圧成形し250〜
350℃で熱処理したものを用い、又負極はリチウム圧延
板を所定寸法に打抜いたものを用いて径20.0mm、厚み2
5.5mm、電池容量120mAHの本発明電池を作成した、この
電池をＡ１とする。The positive electrode uses manganese dioxide heat-treated in the temperature range of 350 to 430 ° C. as an active material, the manganese dioxide, carbon powder as a conductive agent and fluororesin powder as a binder.
The mixture was mixed at a weight ratio of 5: 10: 5 and pressure-molded to give 250-
Use the one heat-treated at 350 ℃, and the negative electrode punched out from a rolled lithium plate to the specified size. Diameter 20.0 mm, thickness 2
A battery of the present invention having 5.5 mm and a battery capacity of 120 mAH was prepared, and this battery is designated as A 1 .
実施例２． 溶媒としてγ−ブチラクトン（γ-BL）と２−メチルテ
トラハイドロフランとを混合比１：１で混合した混合溶
媒を用いることを除いては他は実施例１と同様の本発明
電池を作成した。この電池をＡ２とする。Example 2. A battery of the present invention was produced in the same manner as in Example 1 except that a mixed solvent obtained by mixing γ-butyrolactone (γ-BL) and 2-methyltetrahydrofuran at a mixing ratio of 1: 1 was used as the solvent. . This battery is designated as A 2 .
実施例３． 溶媒としてジオキソラ（DOXL）と２−メチルテトラハイ
ドロフランとを混合比１：１で混合した混合溶媒を用い
ることを除いて他は実施例１と同様の本発明電池を作成
した。この電池をＡ３とする。Example 3. A battery of the present invention was prepared in the same manner as in Example 1 except that a mixed solvent obtained by mixing dioxola (DOXL) and 2-methyltetrahydrofuran at a mixing ratio of 1: 1 was used as the solvent. This battery is designated as A 3 .
比較例 次に本発明電池の優位性を調べるために３種の比較電池
Ｂ、Ｃ及びＤを作成した。Comparative Example Next, three types of comparative batteries B, C and D were prepared in order to examine the superiority of the battery of the present invention.
比較電池Ｂは溶媒としてプロピレンカーボネートとジメ
トキシエタン（DME）とを混合比１：１で混合した混合
溶媒を用いることを除いて他は実施例１と同様である。Comparative battery B is the same as Example 1 except that a mixed solvent obtained by mixing propylene carbonate and dimethoxyethane (DME) at a mixing ratio of 1: 1 was used as the solvent.
比較電池Ｃは溶媒としてプロピレンカーボネートとテト
ラハイドロフラン（THF）とを混合比１：１で混合した
混合溶媒を用いることを除いて他は実施例１と同様であ
る。Comparative battery C is the same as Example 1 except that a mixed solvent obtained by mixing propylene carbonate and tetrahydrofuran (THF) at a mixing ratio of 1: 1 is used as the solvent.
比較電池Ｄは正極物質としてフッ化炭素を用いることを
除いて他は実施例１と同様である。Comparative Battery D is the same as Example 1 except that fluorocarbon was used as the positive electrode material.
第１図及び第２図はこれらの電池の放電特性図であっ
て、第１図は電池組立後、直ちに−20℃において10ＫΩ
の定抵抗で放電した時の放電特性図、第２図は電池組立
後、60℃で３ケ月保存したのち、−20℃において10ＫΩ
の定抵抗で放電した時の充電特性図である。1 and 2 are discharge characteristic diagrams of these batteries, and Fig. 1 shows 10 KΩ at -20 ° C immediately after assembling the batteries.
Fig. 2 shows the discharge characteristics when discharged with the constant resistance of Fig. 2. Fig. 2 shows that after assembling the battery, it was stored at 60 ° C for 3 months and then at 10 ° C at 10KΩ.
FIG. 6 is a charge characteristic diagram when discharging with a constant resistance of FIG.
第１図及び第２図から明白なるように、電池組立直後の
低温放電特性では本発明電池の優位性はそれほど認めら
れないが、保存後の低温放電特性では本発明電池の優位
性がより顕著である。As is clear from FIGS. 1 and 2, the battery of the present invention is not so superior in low-temperature discharge characteristics immediately after battery assembly, but the battery of the present invention is more remarkable in low-temperature discharge characteristics after storage. Is.
第３図乃至第５図は本発明における各種混合溶媒の混合
比と正極の含液率と関係を示す図であり、図中(Ｉ)は二
酸化マンガン正極、(ＩＩ)はフッ化炭素正極の場合を夫
々示す。3 to 5 are views showing the relationship between the mixing ratio of various mixed solvents and the liquid content of the positive electrode in the present invention, in which (I) is a manganese dioxide positive electrode and (II) is a fluorocarbon positive electrode. Each case is shown.
第３図乃至第５図より本発明における混合溶媒は特に正
極活物質として二酸化マンガンを用いた場合に含液率が
高く、電池特性を向上しうることが伺える。From FIGS. 3 to 5, it can be seen that the mixed solvent in the present invention has a high liquid content particularly when manganese dioxide is used as the positive electrode active material, and can improve the battery characteristics.
第６図乃至第８図は本発明における各種混合溶媒混合比
と、電池組立後60℃で３ケ月保存したのち−25℃におい
て10ＫΩの定抵抗で放電した時の電池放電容量との関係
を示す図である。FIGS. 6 to 8 show the relationship between the mixing ratio of various mixed solvents in the present invention and the battery discharge capacity when the battery is stored at 60 ° C. for 3 months and then discharged at a constant resistance of 10 KΩ at −25 ° C. It is a figure.
(ヘ) 発明の効果 上述した如く、本発明によれば保存後の低温放電特性に
優れた非水電解電池を得ることができるものであり、こ
の種電池の用途拡大に資するところ極めて大である。(F) Effects of the invention As described above, according to the present invention, a non-aqueous electrolytic battery having excellent low-temperature discharge characteristics after storage can be obtained, which is extremely large in contributing to expansion of applications of this type of battery. .
尚、本発明電池の実施例において溶質としては過塩素酸
リチウムの場合のみを例示したが、これに限定されるこ
となくリチウムトリフロルオロメタンスルホネート或い
はリチウムデカクロロデカボレートなども適用できる。In the examples of the battery of the present invention, only the case of using lithium perchlorate as the solute is illustrated, but the present invention is not limited to this, and lithium trifluorooromethanesulfonate or lithium decachlorodecaborate can also be applied.
又、負極活物質としてナトリウムを用いることもでき、
その場合には溶質として過塩素酸ナトリウムや塩化ナト
リウムの如きナトリウム塩が適用される。Also, sodium can be used as the negative electrode active material,
In that case, a sodium salt such as sodium perchlorate or sodium chloride is applied as the solute.
第１図及び第２図は電池の低温放電特性図であって、第
１図は初期放電特性図、第２図は保存後の放電特性図で
ある。第３図乃至第５図は各種混合溶媒の混合比と正極
の含液率との関係を示す図、第６図乃至第８図は各種混
合溶媒の混合比と電池の放電容量との関係を示す図であ
る。 （Ａ１)(Ａ２)(Ａ３）…本発明電池、(Ｂ)(Ｃ)(Ｄ)…比
較電池。FIG. 1 and FIG. 2 are low temperature discharge characteristic diagrams of the battery, FIG. 1 is an initial discharge characteristic diagram, and FIG. 2 is a discharge characteristic diagram after storage. FIGS. 3 to 5 show the relationship between the mixing ratio of various mixed solvents and the liquid content of the positive electrode, and FIGS. 6 to 8 show the relationship between the mixing ratio of various mixed solvents and the discharge capacity of the battery. FIG. (A 1 ) (A 2 ) (A 3 ) ... Battery of the present invention, (B) (C) (D) ... Comparative battery.
Claims (1)
それらの合金を活物質とする負極と、二酸化マンガンを
活物質とする正極と、溶媒と溶質とからなる非水電解液
とを備えるものであって、前記溶媒が、プロピレンカー
ボネートと２−メチルテトラハイドロフランとを含む混
合溶媒、γ−ブチロラクトンと２−メチルテトラハイド
ロフランとを含む混合溶媒、又は、ジオキソランと２−
メチルテトラハイドロフランとを含む混合溶媒であるこ
とを特徴とする非水電解液電池。1. A negative electrode using a light metal such as lithium or sodium or an alloy thereof as an active material, a positive electrode using manganese dioxide as an active material, and a non-aqueous electrolyte containing a solvent and a solute. The solvent is a mixed solvent containing propylene carbonate and 2-methyltetrahydrofuran, a mixed solvent containing γ-butyrolactone and 2-methyltetrahydrofuran, or dioxolane and 2-.
A non-aqueous electrolyte battery, which is a mixed solvent containing methyltetrahydrofuran.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59108761A JPH065622B2 (en) | 1984-05-29 | 1984-05-29 | Non-aqueous electrolyte battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59108761A JPH065622B2 (en) | 1984-05-29 | 1984-05-29 | Non-aqueous electrolyte battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60253166A JPS60253166A (en) | 1985-12-13 |
| JPH065622B2 true JPH065622B2 (en) | 1994-01-19 |
Family
ID=14492829
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59108761A Expired - Lifetime JPH065622B2 (en) | 1984-05-29 | 1984-05-29 | Non-aqueous electrolyte battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH065622B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0227664A (en) * | 1988-07-18 | 1990-01-30 | Matsushita Electric Ind Co Ltd | Nonaqueous electrolyte battery |
| CN116259741A (en) * | 2021-12-10 | 2023-06-13 | 张家港市国泰华荣化工新材料有限公司 | A sodium manganese primary battery |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IL61085A (en) * | 1980-09-19 | 1983-07-31 | Univ Ramot | Nonaqueous sulfur cell |
-
1984
- 1984-05-29 JP JP59108761A patent/JPH065622B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60253166A (en) | 1985-12-13 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |