JPS6229070A - non-aqueous electrolyte battery - Google Patents
non-aqueous electrolyte batteryInfo
- Publication number
- JPS6229070A JPS6229070A JP60168128A JP16812885A JPS6229070A JP S6229070 A JPS6229070 A JP S6229070A JP 60168128 A JP60168128 A JP 60168128A JP 16812885 A JP16812885 A JP 16812885A JP S6229070 A JPS6229070 A JP S6229070A
- Authority
- JP
- Japan
- Prior art keywords
- battery
- solvent
- present
- aqueous electrolyte
- mixed
- 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
- H01M6/16—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
- 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)
Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】
（イ）産業上の利用分野
本発明はリチクム或いはリチウム合金を活物質とする負
極と、金部の酸化物、硫化物、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
備えた非水電解液電池に関するものである。Detailed Description of the Invention (a) Field of Industrial Application The present invention provides a negative electrode using lithium or lithium alloy as an active material, a positive electrode using an oxide, sulfide, halide, etc. of gold as an active material, The present invention relates to a nonaqueous electrolyte battery that includes a nonaqueous electrolyte that includes a solvent and a solute.
（財）従来の技術
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
溶質としては例えば特公昭４５−４００４１号公報或い
は特公昭５７−３２８６６号公報などに開示されている
ように種々のものが提案されている。具体的には高粘度
溶媒としてプロピレンカーボネート、γ−プチロクグト
ン、スルホラン、エチレンカーボネートなど、低粘度溶
媒としてジメトキシエタン、ジオキソクン、テトラハイ
ドロフランなど、又溶質として過塩素酸リチウム。Prior Art As the solvent and solute constituting the nonaqueous electrolyte used in this type of battery, there are various solvents and solutes as disclosed in, for example, Japanese Patent Publication No. 45-40041 and Japanese Patent Publication No. 57-32866. something is proposed. Specifically, high viscosity solvents include propylene carbonate, γ-butyrokgtone, sulfolane, ethylene carbonate, etc., low viscosity solvents include dimethoxyethane, dioxocone, tetrahydrofuran, etc., and lithium perchlorate is used as a solute.
ホクフブ化すチクムなどが知られている。Chikum, etc., which turn into hokufubu, are known.
さて、近年に至っ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υその一つとして保存
特性の向上が望まれている。Now, in recent years, as the fields of application of this type of battery have expanded, there has been a demand for improvements in battery characteristics, and one of these is the desire to improve storage characteristics.
ところで、電導度及びイオンの拡散の観点から。By the way, from the point of view of conductivity and ion diffusion.
高率放電に適した溶媒としては高置を率で巨億粘度であ
ることが望まれるが、一般に高誘電率の溶媒は粘度が高
く、低粘度の溶媒は誘″を率が低い。As a solvent suitable for high-rate discharge, it is desired that the solvent has a viscosity of 100,000 yen at high temperature, but in general, a solvent with a high dielectric constant has a high viscosity, and a solvent with a low viscosity has a low dielectric constant.
そこで高粘度溶媒と低粘度溶媒とを混合することによシ
、高誘電率で巨億粘度の溶媒が得られる可脆性がある。Therefore, by mixing a high viscosity solvent and a low viscosity solvent, a brittle solvent with a high dielectric constant and a billion viscosity can be obtained.
しかしジメト一エタン、ジオキソラン、テトラハイドロ
フランなどの低粘度溶媒は負極活物質であるリチウムと
反応したり、電池外に蒸発逸散する傾向があり、その結
果として保存特性に問題があった。However, low-viscosity solvents such as dimetho-ethane, dioxolane, and tetrahydrofuran tend to react with lithium, which is the negative electrode active material, or to evaporate out of the battery, resulting in problems with storage characteristics.
ＧＰ啼 発明が解決しようとする問題点本発明は非水
電解液を改良し、保存特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。GP 啼 Problems to be Solved by the Invention The present invention aims to improve a non-aqueous electrolyte and provide a non-aqueous electrolyte battery with excellent storage characteristics.
に）問題点を解決するための手段
本発明は非水電解液を構成する二種以上の混合溶媒のう
ち、低粘度溶媒として一般式、Ｒ１（００Ｈ２０Ｈ２）
ｎＯＲ２ＣＨ１，Ｒ２はＯＨ５。2) Means for Solving the Problems The present invention uses the general formula R1 (00H20H2) as a low viscosity solvent among the two or more mixed solvents constituting the nonaqueous electrolyte.
nOR2CH1, R2 is OH5.
０２Ｈ５，Ｃ３Ｈ７又はＣ４Ｈ９であり、ｎは２乃至４
の整数〕で表わされるポリエチレングリコール系ジアル
キルエーテルを用いることを特徴とするものである。02H5, C3H7 or C4H9, and n is 2 to 4
It is characterized by using a polyethylene glycol-based dialkyl ether represented by the following integer.
（ホ）作 用
上記の一般式で表わされるポリエチレングリコール系ジ
アルキルエーテルを低粘度溶媒として用いることによυ
保存特性に優れた非水電解液電池を得ることができる。(e) Effect By using the polyethylene glycol dialkyl ether represented by the above general formula as a low viscosity solvent, υ
A non-aqueous electrolyte battery with excellent storage characteristics can be obtained.
（へ）実施例 以下本発明の実施例について詳述する。(f) Example Examples of the present invention will be described in detail below.
実施例１
溶媒としてトリエチレングリコールジメチルエーテルと
プロピレンカーボネートとを１：１の体積比で混合した
混合溶媒を用い、この混合溶媒に溶質として過塩素酸リ
チウムを１モル／ｌ溶解したものを電解液とする。Example 1 A mixed solvent in which triethylene glycol dimethyl ether and propylene carbonate were mixed at a volume ratio of 1:1 was used as a solvent, and 1 mol/l of lithium perchlorate as a solute was dissolved in this mixed solvent as an electrolyte. do.
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８５：１０：５の重量比で混合した混合物を加圧成
形し２５０〜６５０℃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
２０．０閤、厚み２．５ｍ、？ｉ池容量１２ＱｍＡＨの
本発明電池を得る。この電池をＡ１とする。The positive electrode is made of manganese dioxide heat-treated in a temperature range of 350 to 430°C as an active material, and this manganese dioxide is mixed with carbon powder as a conductive agent and fluororesin powder as a binder at a weight ratio of 85:10:5. The mixture was pressure-molded and heat-treated at 250 to 650°C, and the negative electrode was a lithium rolled plate punched out to a specified size, with a diameter of 20.0 mm and a thickness of 2.5 m. A battery of the present invention having an i-cell capacity of 12QmAH is obtained. This battery is designated as A1.
実施例２
溶媒としてジエチレングリコールジｎ−ブチルエーテル
とプロピレンカーボネートとを１：１の体積比で混合し
た混合溶媒を用い、この混合溶媒に溶質として過塩素酸
リチウムを１モル／ｌ溶解し念ものを電解液とすること
を除いて他は実施例１と同様の本発明電池Ａ２を作成し
た。Example 2 A mixed solvent of diethylene glycol di-n-butyl ether and propylene carbonate mixed at a volume ratio of 1:1 was used as a solvent, and 1 mol/l of lithium perchlorate was dissolved as a solute in this mixed solvent to electrolyze a hypothetical object. A battery A2 of the present invention was prepared in the same manner as in Example 1 except that it was a liquid.
実施例３
溶媒としてテトラエチレングリコールジメチルエーテル
とプロピレンカーボネートとを１＝１の体積比で混合し
た混合溶媒を用い、この混合溶媒に溶質として過塩素酸
リチウムを１モル／ｌ溶解したものを電解液とすること
を除いて他は実施例１と同様の本発明電池Ａ５を作成し
念。Example 3 A mixed solvent in which tetraethylene glycol dimethyl ether and propylene carbonate were mixed at a volume ratio of 1=1 was used as a solvent, and 1 mol/l of lithium perchlorate as a solute was dissolved in this mixed solvent as an electrolyte. A battery A5 of the present invention was prepared in the same manner as in Example 1 except for the following.
次に、本発明電池の優位性を調べるために、低粘度溶媒
として従来より用いられている１、２ジメトキシエタン
を用い、この１，２ジメトキシエタンとプロピレンカー
ボネートとを１：１の混合比で混合した混合溶媒を用い
ることを除いて他は本発明電池と同様の比較電池Ｂを作
成した。Next, in order to investigate the superiority of the battery of the present invention, 1,2 dimethoxyethane, which has been conventionally used as a low viscosity solvent, was used, and this 1,2 dimethoxyethane and propylene carbonate were mixed at a mixing ratio of 1:1. A comparative battery B was prepared which was the same as the battery of the present invention except that a mixed solvent was used.
第１図及び第２図は本発明電池と比較電池との放電特性
比較図で°あって、第１図は電池組立後直ちに２５℃に
おいて５にΩの定抵抗で放電した時の初期特性、又第２
図は電池組立後、６０℃で３ケ月間保存したのち２５℃
において５にΩの定抵抗で放電した時の保存特性を夫々
示す。Figures 1 and 2 are diagrams comparing the discharge characteristics of the battery of the present invention and a comparative battery. Also second
The figure shows the battery being assembled and stored at 60°C for 3 months before being stored at 25°C.
5 shows the storage characteristics when discharged with a constant resistance of Ω.
第１図及び第２図よυ本発明電池ＡＩ、Ａ２及びＡ５は
比較電池Ｂに比して初期特性ではほとんど差異がないが
、保存特性では顕著に特性改善が認められる。As shown in FIGS. 1 and 2, the batteries AI, A2, and A5 of the present invention have almost no difference in initial characteristics compared to comparative battery B, but a marked improvement in storage characteristics is observed.
尚１本発明電池と比較電池とを第２図の条件下で保存し
た後、電解液量（初期値１５０＊）を測では５Ｐ９の減
少が認められた。1. After storing the battery of the present invention and the comparative battery under the conditions shown in FIG. 2, the amount of electrolyte (initial value 150*) was measured, and a decrease in 5P9 was observed.
又、第３図は本発明電池Ａ１における混合溶媒の混合比
率と放電容量との関係を示す図である。Moreover, FIG. 3 is a diagram showing the relationship between the mixing ratio of the mixed solvent and the discharge capacity in the battery A1 of the present invention.
（ト） 発明の効果
上述した如く１本発明によれば保存特性に優れた非水電
解液電池を得ることができる。(G) Effects of the Invention As described above, according to the present invention, a non-aqueous electrolyte battery with excellent storage characteristics can be obtained.
本発明電池の効果を考察するに１本発明電池の非水電解
液に用いた低粘度溶媒としての一般式。To consider the effects of the battery of the present invention, the following is a general formula for a low viscosity solvent used in the non-aqueous electrolyte of the battery of the present invention.
Ｒ１（ＯＯＨ２０Ｈ２）ｎＯＲ２ＣＨ１，：Ｒ２はＯＨ
Ｍ、Ｃ２Ｔ（５，Ｃ３Ｈ７又はＣＪ４Ｈ９であシ、ｎは
２乃至４の整数〕で表わされるポリエチレングリコール
系ジアルキルエーテルが他の従来の低粘度溶媒、即ちジ
メトキシエタン、ジオキソクン。R1(OOH20H2)nOR2CH1,:R2 is OH
Polyethylene glycol dialkyl ether represented by M, C2T (5, C3H7 or CJ4H9, n is an integer from 2 to 4) is used as other conventional low viscosity solvents, such as dimethoxyethane and dioxocone.
テトラハイドロフランなどに比して、負極活物質として
のリチウムと反応せず、且蒸発逸散し難いものであるこ
とに起因すると考えられる。This is thought to be due to the fact that it does not react with lithium as a negative electrode active material and is difficult to evaporate and dissipate compared to tetrahydrofuran and the like.
尚、低粘度溶媒としてのポリエチレングリコール系ジア
ルキルエーテルと組合せる高粘度溶媒の例として実施例
ではプロピレンカーボネートのみを例示したが、その他
にγ−ブチロラクトン、スルホラン、エチレンカーボネ
ートなども用いることができる。In addition, although only propylene carbonate was illustrated in the examples as an example of a high viscosity solvent to be combined with the polyethylene glycol dialkyl ether as a low viscosity solvent, γ-butyrolactone, sulfolane, ethylene carbonate, etc. can also be used.
第１図及び第２図は本発明電池と比較電池との放電特性
比較図であって、第１図は初期特性、第２図は保存特性
を夫々示す。又、第３図は本発明電池における混合溶媒
の混合比率と電池放電容量との関係を示す図である。
（Ａｔ）（Ａ２）（Ａｓ）・・・本発明電池、Ｃ８戸・
・比較電池。FIGS. 1 and 2 are comparison diagrams of discharge characteristics between a battery of the present invention and a comparative battery, with FIG. 1 showing initial characteristics and FIG. 2 showing storage characteristics, respectively. Moreover, FIG. 3 is a diagram showing the relationship between the mixing ratio of the mixed solvent and the battery discharge capacity in the battery of the present invention. (At) (A2) (As)...Battery of the present invention, C8 units.
・Comparison battery.
Claims (1)
と、正極と、溶媒と溶質とからなる非水電解液とを備え
るものであつて、前記溶媒は少くとも二種以上の混合溶
媒よりなり、一種が一般式、Ｒ＿１（ＯＣＨ＿２ＣＨ＿
２）＿ｎＯＲ＿２〔Ｒ＿１、Ｒ＿２はＣＨ＿３、Ｃ＿２
Ｈ＿５、Ｃ＿３Ｈ＿７又はＣ＿４Ｈ＿９であり、ｎは２
乃至４の整数〕で表わされるポリエチレングリコール系
ジアルキルエーテルであることを特徴とする非水電解液
電池。(1) A device comprising a negative electrode using lithium or a lithium alloy as an active material, a positive electrode, and a non-aqueous electrolyte comprising a solvent and a solute, where the solvent is a mixed solvent of at least two or more types, One type is the general formula, R_1(OCH_2CH_
2)_nOR_2 [R_1, R_2 are CH_3, C_2
H_5, C_3H_7 or C_4H_9, and n is 2
A non-aqueous electrolyte battery characterized by being a polyethylene glycol-based dialkyl ether represented by an integer from 1 to 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60168128A JPH0665043B2 (en) | 1985-07-30 | 1985-07-30 | Non-aqueous electrolyte battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60168128A JPH0665043B2 (en) | 1985-07-30 | 1985-07-30 | Non-aqueous electrolyte battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6229070A true JPS6229070A (en) | 1987-02-07 |
| JPH0665043B2 JPH0665043B2 (en) | 1994-08-22 |
Family
ID=15862358
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60168128A Expired - Lifetime JPH0665043B2 (en) | 1985-07-30 | 1985-07-30 | Non-aqueous electrolyte battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0665043B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0317351A2 (en) | 1987-11-20 | 1989-05-24 | Showa Denko Kabushiki Kaisha | Secondary battery |
| JPH01268713A (en) * | 1988-04-20 | 1989-10-26 | Sumitomo Bakelite Co Ltd | Epoxy resin composition for sealing semiconductor |
| US5219684A (en) * | 1990-05-16 | 1993-06-15 | Her Majesty The Queen In Right Of Canada, As Represented By The Province Of British Columbia | Electrochemical cells containing a safety electrolyte solvent |
| EP0757399A1 (en) * | 1995-07-25 | 1997-02-05 | Sumitomo Chemical Company, Limited | Non-aqueous electrolyte and lithium secondary battery |
| WO2000016427A1 (en) * | 1998-09-11 | 2000-03-23 | Mitsui Chemicals Inc. | Nonaqueous electrolytic liquid and secondary batter with nonaqueous electrolytic liquid |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5389941A (en) * | 1977-01-19 | 1978-08-08 | Accumulateurs Fixes | Electrolyte for lithium primary cell |
-
1985
- 1985-07-30 JP JP60168128A patent/JPH0665043B2/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5389941A (en) * | 1977-01-19 | 1978-08-08 | Accumulateurs Fixes | Electrolyte for lithium primary cell |
| JPS5912570A (en) * | 1977-01-19 | 1984-01-23 | サフト・ソシエテ・デ・ザキユミユラツ−ル・フイクス・エ・ド・トラクシオン | High energy secondary battery |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0317351A2 (en) | 1987-11-20 | 1989-05-24 | Showa Denko Kabushiki Kaisha | Secondary battery |
| JPH01268713A (en) * | 1988-04-20 | 1989-10-26 | Sumitomo Bakelite Co Ltd | Epoxy resin composition for sealing semiconductor |
| US5219684A (en) * | 1990-05-16 | 1993-06-15 | Her Majesty The Queen In Right Of Canada, As Represented By The Province Of British Columbia | Electrochemical cells containing a safety electrolyte solvent |
| EP0757399A1 (en) * | 1995-07-25 | 1997-02-05 | Sumitomo Chemical Company, Limited | Non-aqueous electrolyte and lithium secondary battery |
| WO2000016427A1 (en) * | 1998-09-11 | 2000-03-23 | Mitsui Chemicals Inc. | Nonaqueous electrolytic liquid and secondary batter with nonaqueous electrolytic liquid |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0665043B2 (en) | 1994-08-22 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |