JPH0574486A - Nonaqueous electrolyte battery - Google Patents
Nonaqueous electrolyte batteryInfo
- Publication number
- JPH0574486A JPH0574486A JP3230090A JP23009091A JPH0574486A JP H0574486 A JPH0574486 A JP H0574486A JP 3230090 A JP3230090 A JP 3230090A JP 23009091 A JP23009091 A JP 23009091A JP H0574486 A JPH0574486 A JP H0574486A
- Authority
- JP
- Japan
- Prior art keywords
- battery
- solvent
- lithium
- electrolytic solution
- nonaqueous electrolyte
- 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
-
- 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
- Primary Cells (AREA)
- Secondary Cells (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、正極と、リチウムを活
物質とする負極と、溶媒及び溶質から成る非水系電解液
とを備えた非水系電解液電池に関し、特に非水系電解液
の溶媒の改良に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a non-aqueous electrolytic solution battery provided with a positive electrode, a negative electrode using lithium as an active material, and a non-aqueous electrolytic solution comprising a solvent and a solute, and particularly to a solvent for the non-aqueous electrolytic solution. Regarding the improvement of.
【０００２】[0002]
【従来の技術】この種の電池は、高電圧，高エネルギー
密度を有するので、近年、様々な用途に用いられてい
る。加えて、上記電池は水溶液系電解液を用いた電池と
比べて保存特性等に優れており、高信頼性を有するとい
う利点もある。しかしながら、負極に用いられるリチウ
ムは還元性が非常に高いため、電解液と接触してリチウ
ムの表面に電解液の還元成分から成る皮膜が生成するこ
とになる。この場合、上記皮膜の性質によっては不都合
が生じることがあるため、皮膜の性質は電池の保存特性
等に多大の影響を与えることになる。特に、長期保存に
おいては重要な影響を及ぼす。2. Description of the Related Art Batteries of this kind have been used for various purposes in recent years because they have high voltage and high energy density. In addition, the above-described battery has excellent storage characteristics and the like as compared with a battery using an aqueous electrolyte solution, and has an advantage of having high reliability. However, since lithium used for the negative electrode has a very high reducibility, it comes into contact with the electrolytic solution to form a film made of a reducing component of the electrolytic solution on the surface of lithium. In this case, inconvenience may occur depending on the properties of the film, and thus the properties of the film have a great influence on the storage characteristics and the like of the battery. In particular, it has an important effect on long-term storage.
【０００３】ここで、上記皮膜の性質は、電解液の種類
と密接な関係があることが一般に知られており、現在で
も種々の溶媒や添加剤についての研究が盛んに行われて
いる。しかしながら、未だ充分な特性を有する電解液を
見出すことができない。Here, it is generally known that the properties of the above-mentioned film are closely related to the type of the electrolytic solution, and even now, various solvents and additives are being actively studied. However, it has not been possible to find an electrolytic solution having sufficient characteristics.
【０００４】[0004]
【発明が解決しようとする課題】本発明はかかる現状に
鑑みてなされたものであり、保存特性や放電特性及び二
次電池においてはサイクル特性を向上させることができ
る非水系電解液電池を提供することを目的とする。SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and provides a non-aqueous electrolyte battery capable of improving storage characteristics, discharge characteristics, and cycle characteristics of secondary batteries. The purpose is to
【０００５】[0005]
【課題を解決するための手段】本発明は上記目的を達成
するために、正極と、リチウムを活物質とする負極と、
溶媒及び溶質から成る非水系電解液とを備えた非水系電
解液電池において、前記非水系電解液の溶媒は、主溶媒
と、この主溶媒の少なくとも一部が不飽和結合された溶
媒とが含有されていることを特徴とする。In order to achieve the above object, the present invention comprises a positive electrode, a negative electrode containing lithium as an active material, and
In a non-aqueous electrolytic solution battery comprising a non-aqueous electrolytic solution comprising a solvent and a solute, the solvent of the non-aqueous electrolytic solution contains a main solvent and a solvent in which at least a part of this main solvent is unsaturated-bonded. It is characterized by being.
【０００６】[0006]
【作用】上述した如く、リチウムの表面は電解液の還元
生成物である薄い皮膜によって覆われており、この皮膜
の性質によって電池の特性が異なることになる。例え
ば、この皮膜が非常に緻密で且つイオン絶縁性のもので
あれば、保存特性はある程度向上するが、電池の内部イ
ンピーダンスが上昇し、更に充分な放電特性（二次電池
の場合には充放電特性）を得ることができない。また、
上記皮膜とリチウムとの密着性が充分でない場合には、
皮膜が脱落し易くなるため、新たに出現するリチウム表
面が電解液と反応し、負極容量が低下したり、長期の保
存による特性が劣化する。As described above, the surface of lithium is covered with a thin film which is a reduction product of the electrolytic solution, and the characteristics of the battery differ depending on the properties of this film. For example, if this film is very dense and has ion-insulating properties, the storage characteristics will improve to some extent, but the internal impedance of the battery will increase, and moreover, sufficient discharge characteristics (in the case of a secondary battery, charging / discharging will occur). Characteristic) cannot be obtained. Also,
If the adhesion between the film and lithium is not sufficient,
Since the film is likely to fall off, the newly appearing lithium surface reacts with the electrolytic solution, and the capacity of the negative electrode decreases, and the characteristics due to long-term storage deteriorate.
【０００７】このようなことを考慮すれば、上記皮膜と
しては以下に示すような特性を有することが望ましい。
リチウム表面への密着性に優れ且つ緻密である。この
ような特性を有していれば、電解液とリチウムとの反応
がリチウム内部まで進行するのを防ぐことができる。
イオン導電性に優れている。In view of the above, it is desirable that the above film has the following characteristics.
It has excellent adhesion to the lithium surface and is dense. With such characteristics, the reaction between the electrolytic solution and lithium can be prevented from proceeding to the inside of lithium.
Excellent ionic conductivity.
【０００８】このような特性を有していれば、電池の内
部インピーダンスが上昇するのを抑制することができ
る。そこで、本発明者は、電解液の溶媒として種々の溶
媒を検討した。その結果、主溶媒に、主溶媒の少なくと
も一部を不飽和化した溶媒が添加されていれば、放電特
性やサイクル特性が優れると共に保存特性も向上するこ
とを見出した。With such characteristics, it is possible to prevent the internal impedance of the battery from rising. Therefore, the present inventor examined various solvents as the solvent of the electrolytic solution. As a result, they have found that if a solvent in which at least a part of the main solvent is unsaturated is added to the main solvent, the discharge characteristics and the cycle characteristics are excellent and the storage characteristics are improved.
【０００９】これは、溶媒の少なくとも一部を不飽和化
すれば、リチウム負極に優先的に吸着され、この結果リ
チウム負極表面に安定な保護膜が形成される。特に、主
溶媒の少なくとも一部を不飽和化した溶媒を添加した場
合には、分子レベルにおける主溶媒との混合性にも優れ
ることになるため、薄くて、且つ緻密で均質な被膜が生
成されることになる。このように、リチウム負極表面に
生成される被膜が薄ければ、リチウムイオン導電性に優
れ、また、上記被膜が緻密で均質であれば電解液とリチ
ウムとの反応がリチウム内部まで進行しない。This is because if at least a part of the solvent is desaturated, it is preferentially adsorbed on the lithium negative electrode, and as a result, a stable protective film is formed on the surface of the lithium negative electrode. In particular, when a solvent in which at least a part of the main solvent is desaturated is added, the mixing property with the main solvent at the molecular level is also excellent, so that a thin, dense and uniform film is formed. Will be. Thus, if the coating film formed on the surface of the lithium negative electrode is thin, the lithium ion conductivity is excellent, and if the coating film is dense and homogeneous, the reaction between the electrolytic solution and lithium does not proceed to the inside of lithium.
【００１０】このような理由によって、放電特性や保存
特性を向上させることができる。尚、このような効果
は、一次電池，二次電池を問わず出現するものである
が、特に二次電池においては、充電時に析出する活性な
リチウムが電解液と反応するのを抑制することができる
ため、サイクル寿命も向上させることができる。For these reasons, the discharge characteristics and storage characteristics can be improved. It should be noted that such an effect appears regardless of whether the battery is a primary battery or a secondary battery, but particularly in a secondary battery, it is possible to suppress the reaction of active lithium deposited during charging with an electrolytic solution. Therefore, the cycle life can be improved.
【００１１】[0011]
【実施例】（第１実施例）本発明の第１実施例を、第１
図乃至第３図に基づいて、以下に説明する。尚、本第１
実施例及び下記第２実施例においては、非水系電解液一
次電池について説明する。 〔実施例〕第１図は本発明の一実施例に係る偏平型非水
系電解液一次電池の断面図であり、リチウム金属から成
る負極２は負極集電体７の内面に圧着されており、この
負極集電体７はフェライト系ステンレス鋼（ＳＵＳ４３
０）から成る断面略コ字状の負極缶５の内底面に固着さ
れている。上記負極缶５の周端はポリプロピレン製の絶
縁パッキング８の内部に固定されており、絶縁パッキン
グ８の外周にはステンレスから成り上記負極缶５とは反
対方向に断面略コ字状を成す正極缶４が固定されてい
る。この正極缶４の内底面には正極集電体６が固定され
ており、この正極集電体６の内面には正極１が固定され
ている。この正極１と前記負極２との間には、本発明の
主要部を成す電解液が含浸されたセパレータ３が介装さ
れている。尚、電池寸法は直径２０．０mm、厚み２．５
mmである。(First Embodiment) The first embodiment of the present invention is
A description will be given below with reference to FIGS. In addition, this first
In Examples and the second example below, a non-aqueous electrolyte primary battery will be described. [Examples] FIG. 1 is a cross-sectional view of a flat type non-aqueous electrolyte primary battery according to an example of the present invention, in which a negative electrode 2 made of lithium metal is pressure-bonded to an inner surface of a negative electrode current collector 7. This negative electrode current collector 7 is made of ferritic stainless steel (SUS43
(0) is fixed to the inner bottom surface of the negative electrode can 5 having a substantially U-shaped cross section. A peripheral end of the negative electrode can 5 is fixed inside an insulating packing 8 made of polypropylene, and an outer periphery of the insulating packing 8 is made of stainless steel and has a substantially U-shaped cross section in a direction opposite to the negative electrode can 5. 4 is fixed. The positive electrode current collector 6 is fixed to the inner bottom surface of the positive electrode can 4, and the positive electrode 1 is fixed to the inner surface of the positive electrode current collector 6. Between the positive electrode 1 and the negative electrode 2, a separator 3 impregnated with an electrolytic solution, which is a main part of the present invention, is interposed. The battery size is 20.0 mm in diameter and 2.5 in thickness.
mm.
【００１２】ここで、前記正極１は、以下のようにして
作製した。先ず、３５０〜４３０℃の温度範囲で熱処理
した活物質である二酸化マンガンと、導電剤としてのカ
ーボン粉末と、結着剤としてのフッ素樹脂粉末とを８
５：１０：１５の重量比で混合する。次いで、この混合
物を加圧成型した後、２５０〜３５０℃の温度範囲で熱
処理することにより作製した。Here, the positive electrode 1 was manufactured as follows. First, 8 parts of manganese dioxide, which is an active material heat-treated in the temperature range of 350 to 430 ° C., carbon powder as a conductive agent, and fluororesin powder as a binder, are added.
Mix at a weight ratio of 5:10:15. Next, this mixture was pressure-molded and then heat-treated in the temperature range of 250 to 350 ° C.
【００１３】一方、前記負極２は、リチウム圧延板を所
定寸法に打ち抜くことにより作製した。また、上記電解
液としては、エチレンカーボネート（以下、ＥＣと略
す）と、ブチレンカーボネート（以下、ＢＣと略す）
と、１，２−ジメトキシエタン（以下、ＤＭＥと略す）
との混合溶媒（体積比２：２：６）に、添加剤としてビ
ニレンカーボネート（以下、ＶＣと略す）を上記ＥＣに
対する体積比で３％添加し、更にトリフルオロメタンス
ルホン酸リチウム（ＬｉＣＦ3 ＳＯ3 ）を上記溶媒に対
して１モル／リットルの割合で添加したものを用いた。On the other hand, the negative electrode 2 was produced by punching a rolled lithium plate into a predetermined size. Further, as the electrolytic solution, ethylene carbonate (hereinafter abbreviated as EC) and butylene carbonate (hereinafter abbreviated as BC) are used.
And 1,2-dimethoxyethane (hereinafter abbreviated as DME)
3% by volume of vinylene carbonate (hereinafter abbreviated as VC) as an additive in a mixed solvent (volume ratio 2: 2: 6) with respect to the above EC, and further lithium trifluoromethanesulfonate (LiCF 3 SO 3 1) was added to the above solvent at a ratio of 1 mol / liter.
【００１４】このようにして作製した電池を、以下
（Ａ）電池と称する。 〔比較例１〕電解液に、ＶＣを添加しない他は、上記実
施例と同様にして電池を作製した。このようにして作製
した電池を、以下（Ｗ）電池と称する。 〔実験１〕上記本発明の（Ａ）電池と比較例の（Ｗ）電
池とにおける保存前後の放電特性を調べたので、それら
の結果をそれぞれ図２及び図３に示す。尚、実験条件
は、３００Ωの定抵抗放電という条件であり、また、保
存条件は６０℃の恒温槽中で３カ月保存するという条件
である。また、各電池を５個づつ用いた。The battery thus manufactured is hereinafter referred to as (A) battery. [Comparative Example 1] A battery was produced in the same manner as in the above-described example except that VC was not added to the electrolytic solution. The battery thus manufactured is hereinafter referred to as a (W) battery. [Experiment 1] The discharge characteristics of the battery (A) of the present invention and the battery (W) of the comparative example before and after storage were examined. The results are shown in FIGS. 2 and 3, respectively. The experimental condition is a constant resistance discharge of 300Ω, and the storage condition is a condition of storing in a constant temperature bath at 60 ° C. for 3 months. Also, five batteries were used for each.
【００１５】図２及び図３から明らかなように、保存前
の放電特性では両者に差異はないが、保存後の放電特性
においては本発明の（Ａ）電池は比較例の（Ｗ）電池に
比べて向上していることが認められる。 〔実験２〕上記本発明の（Ａ）電池と比較例の（Ｗ）電
池とにおける、保存前後の電池内部インピーダンスを測
定したので、その結果を下記表１に示す。また、各電池
５個づつ用いた。As is clear from FIGS. 2 and 3, there is no difference in the discharge characteristics before storage, but in the discharge characteristics after storage, the battery (A) of the present invention is comparable to the battery (W) of the comparative example. It is recognized that it is improved compared to the above. [Experiment 2] The internal impedances of the battery (A) of the present invention and the battery (W) of the comparative example were measured before and after storage. The results are shown in Table 1 below. Also, 5 batteries were used for each battery.
【００１６】[0016]
【表１】 [Table 1]
【００１７】表１より明らかなように、保存前は両者に
差異は認められないが、保存期間を経過するにしたがっ
て比較例の（Ｗ）電池は本発明の（Ａ）電池に比べて電
池内部インピーダンスが増加することが認められる。こ
のように電池内部インピーダンスが増加することに起因
して、上記実験１で示す如く保存後の放電特性が低下す
るものと考えられる。As is clear from Table 1, no difference is observed between the two before storage, but as the storage period elapses, the battery (W) of the comparative example has a more internal structure than the battery (A) of the present invention. It is observed that the impedance increases. It is considered that the discharge characteristic after storage is deteriorated as shown in Experiment 1 due to the increase in the internal impedance of the battery.
【００１８】（第２実施例） 〔実施例〕電解液として、プロピレンカーボネート（以
下、ＰＣと略す）とテトラヒドロフラン（以下、ＴＨＦ
と略す）との等体積混合溶媒に、添加剤としてフラン
（以下、Ｆと略す）を上記ＴＨＦに対する体積比で０．
５％添加し、更にトリフルオロメタンスルホン酸リチウ
ムを上記溶媒に対して１モル／リットルの割合で溶解さ
せたものを用る他は、上記第１実施例の実施例と同様に
して電池を作製した。(Second Embodiment) [Example] As an electrolytic solution, propylene carbonate (hereinafter abbreviated as PC) and tetrahydrofuran (hereinafter THF)
In an equal volume mixed solvent with furan (hereinafter abbreviated as F) as an additive at a volume ratio of 0.1 to THF.
A battery was made in the same manner as in the above-mentioned Example of Example 1 except that 5% was added and lithium trifluoromethanesulfonate was dissolved in the above solvent at a ratio of 1 mol / liter. ..
【００１９】このようにして作製した電池を、以下
（Ｂ）電池と称する。 〔比較例〕電解液にＦを添加しない他は、上記実施例と
同様にして電池を作製した。このようにして作製した電
池を、以下（Ｘ）電池と称する。 〔実験〕上記本発明の（Ｂ）電池と比較例の（Ｘ）電池
とにおける、保存前後の電池内部インピーダンスを測定
したので、その結果を下記表２に示す。尚、各電池を５
個づつ用いた。The battery thus manufactured is hereinafter referred to as (B) battery. [Comparative Example] A battery was produced in the same manner as in the above-described example except that F was not added to the electrolytic solution. The battery thus manufactured is hereinafter referred to as (X) battery. [Experiment] The internal impedances of the battery (B) of the present invention and the battery (X) of the comparative example were measured before and after storage. The results are shown in Table 2 below. In addition, each battery is 5
Used individually.
【００２０】[0020]
【表２】 [Table 2]
【００２１】表２より明らかなように、保存前は両者に
差異は認められないが、保存期間を経過するにしたがっ
て比較例の（Ｘ）電池は本発明の（Ｂ）電池に比べて電
池内部インピーダンスが増加することが認められる。ま
た、図示はしないが、このように電池内部インピーダン
スが増加することに起因して、比較例の（Ｘ）電池は保
存後の放電特性が低下するといことを実験により確認し
ている。As is clear from Table 2, there is no difference between the two before storage, but as the storage period elapses, the battery (X) of the comparative example has a better internal structure than the battery (B) of the present invention. It is observed that the impedance increases. Although not shown, it has been confirmed by experiments that the discharge characteristic after storage of the battery (X) of the comparative example deteriorates due to the increase of the battery internal impedance as described above.
【００２２】（第３実施例）本発明の第３実施例を、図
４に基づいて、以下に説明する。尚、本第３実施例及び
下記の第４実施例においては非水系電解液二次電池につ
いて述べる。 〔実施例〕正極として、予めリチウムを含有させた正極
活物質であるマンガン酸化物と、導電剤としてのアセチ
レンブラックと、結着剤としてのフッ素樹脂とを８５：
１０：５の重量比で混合したものを用いると共に、下記
表３に示す電解液を用いる他は、前記第１実施例の実施
例と同様にして電池を作製した。(Third Embodiment) A third embodiment of the present invention will be described below with reference to FIG. In the third embodiment and the fourth embodiment below, a non-aqueous electrolyte secondary battery will be described. [Example] As a positive electrode, manganese oxide, which is a positive electrode active material containing lithium in advance, acetylene black as a conductive agent, and a fluororesin as a binder were mixed with 85:
A battery was produced in the same manner as in the above-described Example 1 except that the mixture having a weight ratio of 10: 5 was used and the electrolytic solution shown in Table 3 below was used.
【００２３】このようにして作製した電池を、以下
（Ｃ）電池と称する。 〔比較例〕下記表３に示す電解液を用いる他は、上記実
施例と同様にして電池を作製した。このようにして作製
した電池を、以下（Ｙ）電池と称する。The battery thus manufactured is hereinafter referred to as (C) battery. [Comparative Example] A battery was produced in the same manner as in the above-described example except that the electrolytic solution shown in Table 3 below was used. The battery thus manufactured is hereinafter referred to as (Y) battery.
【００２４】[0024]
【表３】 [Table 3]
【００２５】〔実験１〕上記本発明の（Ｃ）電池と比較
例の（Ｙ）電池とのサイクル特性を調べたので、その結
果を図４に示す。尚、実験条件は、充電電流２ｍＡで４
時間充電した後、放電電流２ｍＡで４時間放電するとい
う条件であり、放電時間内に電池電圧が２Ｖとなった時
点で電池寿命とした。また、図４においては５つの電池
の平均値を示している。[Experiment 1] The cycle characteristics of the battery (C) of the present invention and the battery (Y) of the comparative example were examined. The results are shown in FIG. The experimental conditions were 4 at a charging current of 2 mA.
After the battery was charged for an hour, the battery was discharged at a discharge current of 2 mA for 4 hours, and the battery life was defined as the time when the battery voltage reached 2 V within the discharging time. Moreover, in FIG. 4, the average value of five batteries is shown.
【００２６】図４から明らかなように、本発明の（Ｃ）
電池は比較例の（Ｙ）電池と比べて、サイクル特性が飛
躍的に向上していることが認められる。 〔実験２〕上記ＶＣのＥＣに対する添加量（体積比）を
変化させて、添加量とサイクル特性との関係を調べたの
でその結果を図５に示す。尚、実験条件は上記実験１と
同様の条件である。但し、溶質としてはヘキサフルオロ
リン酸リチウム（ＬｉＰＦ 6 、溶媒に対して１モル／リ
ットルの割合で添加）を用いている。As is apparent from FIG. 4, (C) of the present invention.
The battery has better cycle characteristics than the (Y) battery of the comparative example.
It is recognized that it has improved dramatically. [Experiment 2] Addition amount (volume ratio) of VC to EC
By changing it, we investigated the relationship between the amount added and cycle characteristics.
The results are shown in FIG. The experimental conditions are the same as those in Experiment 1 above.
The conditions are similar. However, hexafluoro is used as the solute.
Lithium phosphate (LiPF 6, 1 mol / l of solvent
(Added in the proportion of the bottle).
【００２７】図５から明らかなように、ＶＣを０．０１
wt％以上添加すればサイクル特性が向上していることが
認められる。但し、１０％を超えるとサイクル特性が低
下する。したがって、ＶＣの添加量は０．０１〜１０％
の範囲であることが望ましく、特に１〜３％の範囲であ
ることが望ましい。上記の範囲が好ましいのは、０．０
１％以下では添加効果が余り発揮されない一方、１０％
以上であればリチウム負極に生成される被膜の厚みが大
きくなり過ぎるため電池の内部インピーダンスが上昇す
るという理由によるものと考えられる。As is clear from FIG. 5, VC is 0.01
It is recognized that the cycle characteristics are improved by adding more than wt%. However, if it exceeds 10%, the cycle characteristics deteriorate. Therefore, the addition amount of VC is 0.01 to 10%.
It is desirable to be in the range of, and it is particularly desirable to be in the range of 1 to 3%. The above range is preferably 0.0
If it is less than 1%, the effect of addition is not so good, while it is 10%.
It is considered that the reason is that the thickness of the coating film formed on the lithium negative electrode becomes too large and the internal impedance of the battery rises if the above is satisfied.
【００２８】（第４実施例） 〔実施例〕電解液として、γ−ブチロラクトン（以下、
γ−ＢＬと略す）とＤＭＥとの等体積混合溶媒に、添加
剤として２（５Ｈ）−フラノン（以下、ＦＮと略す）を
上記γ−ＢＬに対する体積比で１０％添加し、更にヘキ
サフルオロリン酸リチウムを上記溶媒に対して１モル／
リットルの割合で溶解させたものを用いる他は、前記第
３実施例の実施例と同様にして電池を作製した。(Fourth Embodiment) [Example] As an electrolytic solution, γ-butyrolactone (hereinafter, referred to as
2 (5H) -furanone (hereinafter abbreviated as FN) as an additive is added to an equal volume mixed solvent of γ-BL) and DME in an amount of 10% in terms of volume ratio to γ-BL, and hexafluoroline is further added. Lithium acid is 1 mol / based on the above solvent
A battery was produced in the same manner as in the above-mentioned third example except that the one dissolved at a rate of 1 liter was used.
【００２９】このようにして作製した電池を、以下
（Ｄ）電池と称する。 〔比較例〕電解液としてＦＮを添加しない他は、上記実
施例と同様にして電池を作製した。このようにして作製
した電池を、以下（Ｚ）電池と称する。 〔実験〕上記本発明の（Ｄ）電池と比較例の（Ｚ）電池
とのサイクル特性を調べたので、その結果を図６に示
す。尚、実験条件は、前記第３実施例の実験１と同様の
条件であり、且つ図６においては５つの電池の平均値を
示している。The battery thus manufactured is hereinafter referred to as (D) battery. [Comparative Example] A battery was produced in the same manner as in the above-described example except that FN was not added as an electrolytic solution. The battery thus manufactured is hereinafter referred to as (Z) battery. [Experiment] The cycle characteristics of the battery (D) of the present invention and the battery (Z) of the comparative example were examined, and the results are shown in FIG. The experimental conditions are the same as those of Experiment 1 of the third embodiment, and in FIG. 6, the average value of five batteries is shown.
【００３０】図６から明らかなように、本発明の（Ｄ）
電池は比較例の（Ｚ）電池と比べて、サイクル特性が飛
躍的に向上していることが認められる。 〔その他の事項〕電解液の主溶媒としては、上記Ｐ
Ｃ，ＥＣ等に限定するものではなく、例えば、２−メチ
ルテトラヒドロフラン（２−ＭｅＴＨＦ）、１，３−ジ
オキソラン（ＤＯＬ）、４−メチル−１，３−ジオキソ
ラン（４−ＭｅＤＯＬ）等であっても良い。電解液の
溶質としては、上記トリフルオロメタンスルホン酸リチ
ウム等に限定するものではなく、例えば、テトラフルオ
ロホウ酸リチウム（ＬｉＢＦ4 ）、テトラフルオロヒ酸
リチウム（ＬｉＡｓＦ6 ）、ヘキサフルオロアンチモン
酸リチウム（ＬｉＳｂＦ6 ）等から成る群から選択され
るフッ素系ルイス酸リチウム塩であってもよい。正極
としては、Ｍｎ酸化物に限定するものではなく、Ｃｏ、
Ｎｉ、Ｖ、Ｃｒ等の酸化物であっても良い。主溶媒の
割合は上記実施例の割合に限定するものではなく、１０
％以上含有していれば良い。As is apparent from FIG. 6, (D) of the present invention.
It is recognized that the battery has dramatically improved cycle characteristics as compared with the battery (Z) of the comparative example. [Other matters] As the main solvent of the electrolytic solution, P
It is not limited to C, EC and the like, and examples thereof include 2-methyltetrahydrofuran (2-MeTHF), 1,3-dioxolane (DOL), 4-methyl-1,3-dioxolane (4-MeDOL) and the like. Is also good. The solute of the electrolytic solution is not limited to the above-mentioned lithium trifluoromethanesulfonate and the like, and examples thereof include lithium tetrafluoroborate (LiBF 4 ), lithium tetrafluoroarsenate (LiAsF 6 ), lithium hexafluoroantimonate (LiSbF). It may be a fluorine-based Lewis acid lithium salt selected from the group consisting of 6 ) and the like. The positive electrode is not limited to Mn oxide, but Co,
It may be an oxide such as Ni, V, or Cr. The proportion of the main solvent is not limited to the proportion in the above-mentioned example, and is 10
It suffices if the content is at least%.
【００３１】[0031]
【発明の効果】以上説明したように本発明によれば、主
溶媒の少なくとも一部を不飽和化した溶媒を添加してい
るので、分子レベルにおいて主溶媒との混合性が優れる
ことになる。したがって負極表面に生成される被膜が薄
く、且つ緻密で均質となる。これらのことから、保存特
性や放電特性及びサイクル特性を飛躍的に向上すること
ができるといった効果を奏する。As described above, according to the present invention, since the solvent in which at least a part of the main solvent is unsaturated is added, the mixing property with the main solvent is excellent at the molecular level. Therefore, the coating film formed on the surface of the negative electrode is thin, dense and uniform. As a result, storage characteristics, discharge characteristics, and cycle characteristics can be dramatically improved.
【図１】本発明の第１実施例に係る偏平型非水系電解液
一次電池の断面図である。FIG. 1 is a cross-sectional view of a flat type non-aqueous electrolyte primary battery according to a first embodiment of the present invention.
【図２】本発明の（Ａ）電池と比較例の（Ｗ）電池とに
おける保存前の放電特性を示すグラフである。FIG. 2 is a graph showing discharge characteristics of a battery of the present invention (A) and a battery of a comparative example (W) before storage.
【図３】本発明の（Ａ）電池と比較例の（Ｗ）電池とに
おける保存後の放電特性を示すグラフである。FIG. 3 is a graph showing discharge characteristics after storage in the battery (A) of the present invention and the battery (W) of the comparative example.
【図４】本発明の（Ｃ）電池と比較例の（Ｙ）電池とに
おけるサイクル特性を示すグラフである。FIG. 4 is a graph showing cycle characteristics of a battery (C) of the present invention and a battery (Y) of a comparative example.
【図５】ＶＣ添加量とサイクル数との関係を示すグラフ
である。FIG. 5 is a graph showing the relationship between the amount of VC added and the number of cycles.
【図６】本発明の（Ｄ）電池と比較例の（Ｚ）電池とに
おけるサイクル特性を示すグラフである。FIG. 6 is a graph showing cycle characteristics of the battery (D) of the present invention and the battery (Z) of the comparative example.
１ 正極 ２ 負極 1 Positive electrode 2 Negative electrode
───────────────────────────────────────────────────── フロントページの続き (72)発明者 大下 竜司 守口市京阪本通２丁目18番地 三洋電機株 式会社内 (72)発明者 古川 修弘 守口市京阪本通２丁目18番地 三洋電機株 式会社内 ─────────────────────────────────────────────────── ─── Continued Front Page (72) Inventor Ryuji Oshita 2-18 Keihan Hondori, Moriguchi City Sanyo Electric Co., Ltd. (72) Inventor Nobuhiro Furukawa 2-18 Keihan Hondori, Moriguchi Sanyo Electric Co., Ltd. In the company
Claims (1)
と、溶媒及び溶質から成る非水系電解液とを備えた非水
系電解液電池において、 前記非水系電解液の溶媒は、主溶媒と、この主溶媒の少
なくとも一部が不飽和結合された溶媒とが含有されてい
ることを特徴とする非水系電解液電池。1. A non-aqueous electrolyte battery comprising a positive electrode, a negative electrode using lithium as an active material, and a non-aqueous electrolyte solution comprising a solvent and a solute, wherein the solvent of the non-aqueous electrolyte solution is a main solvent, A non-aqueous electrolyte battery comprising a solvent in which at least a part of the main solvent is unsaturatedly bonded.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3230090A JP3066126B2 (en) | 1991-09-10 | 1991-09-10 | Non-aqueous electrolyte battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3230090A JP3066126B2 (en) | 1991-09-10 | 1991-09-10 | Non-aqueous electrolyte battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0574486A true JPH0574486A (en) | 1993-03-26 |
| JP3066126B2 JP3066126B2 (en) | 2000-07-17 |
Family
ID=16902393
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3230090A Expired - Lifetime JP3066126B2 (en) | 1991-09-10 | 1991-09-10 | Non-aqueous electrolyte battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3066126B2 (en) |
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| WO2022054696A1 (en) | 2020-09-14 | 2022-03-17 | 住友精化株式会社 | Additive for non-aqueous electrolyte, non-aqueous electrolyte, and power storage device |
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