JPH0541246A - Nonaqueous solvent battery - Google Patents
Nonaqueous solvent batteryInfo
- Publication number
- JPH0541246A JPH0541246A JP3216608A JP21660891A JPH0541246A JP H0541246 A JPH0541246 A JP H0541246A JP 3216608 A JP3216608 A JP 3216608A JP 21660891 A JP21660891 A JP 21660891A JP H0541246 A JPH0541246 A JP H0541246A
- Authority
- JP
- Japan
- Prior art keywords
- aqueous solvent
- battery
- electrolytic solution
- electrolyte
- lithium
- 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.)
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Classifications
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- 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
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- Primary Cells (AREA)
- Secondary Cells (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、非水溶媒電池に関し、
とくに改良された電解液を用いる非水溶媒電池に関す
る。FIELD OF THE INVENTION The present invention relates to a non-aqueous solvent battery,
In particular, it relates to a non-aqueous solvent battery using an improved electrolytic solution.
【０００２】[0002]
【従来の技術】非水溶媒電池は、金属酸化物、硫化物、
フッ化物等を正極とし、リチウム、ナトリウムなどの軽
金属を負極とし、これらの正負極を電解液保持材を介し
て積層した構造を有し、ＤＭＥ、ＴＨＦ、ＰＣのような
非水溶媒に電解質を溶解した電解液を用いている。こう
した非水溶媒電池は、エネルギー密度が高く、信頼性も
高いため、多くの電子機器の電源として使用されてい
る。Non-aqueous solvent batteries include metal oxides, sulfides,
Fluoride is used as a positive electrode, light metal such as lithium and sodium is used as a negative electrode, and these positive and negative electrodes are laminated via an electrolyte holding material. Electrolyte is applied to a non-aqueous solvent such as DME, THF, and PC. It uses a dissolved electrolyte. Since such a non-aqueous solvent battery has high energy density and high reliability, it is used as a power source for many electronic devices.
【０００３】近年、非水溶媒電池の用途の広がりによ
り、時計、カメラ、ラジオなどの電源として使用される
場合には重負荷特性が要求され、一方、ＯＡ機器、家電
製品などに内蔵されるメモリのバックアップ電源に使用
される場合には、長期間にわたる特性の維持、安定性が
要求されるなど、幅広い性能が期待されるようになっ
た。このような期待に対応するために、電池を構成する
正極合剤、電解液組成、電池構造などに関して多くの検
討がなされ、電池の特性レベルも相当向上されてきた。
しかしながら、市場の要求特性はますます厳しく、重負
荷特性を５〜１０年間もの長期間にわたって維持するこ
とが不可欠となってきている。In recent years, due to the widespread use of non-aqueous solvent batteries, heavy load characteristics are required when they are used as power sources for clocks, cameras, radios, etc., on the other hand, memories incorporated in OA equipment, home appliances and the like. When it is used as a backup power source, it has been expected to have a wide range of performance, such as long-term maintenance of characteristics and stability. In order to meet such expectations, many studies have been made on the positive electrode mixture, the composition of the electrolyte, the battery structure, etc. that constitute the battery, and the characteristic level of the battery has been considerably improved.
However, the demanded characteristics of the market are becoming more and more severe, and it is indispensable to maintain the heavy load characteristics for a long period of 5 to 10 years.
【０００４】ところで、従来の非水溶媒電池における電
解液保持材は、負極と正極とを隔離するとともに、より
多量の電解液を保持できるような材質のものが望ましい
とされてきた。すなわち、電解液保持材にできる限り多
量の電解液を保持させ、電池の内部抵抗を下げることに
よって、放電反応を円滑に進めることが可能となる。By the way, it has been considered desirable that the electrolyte holding material in the conventional non-aqueous solvent battery is made of a material capable of separating the negative electrode and the positive electrode and holding a larger amount of the electrolytic solution. That is, the discharge reaction can be smoothly promoted by holding the electrolyte solution holding material as much as possible and reducing the internal resistance of the battery.
【０００５】[0005]
【発明が解決しようとする課題】上記のような電解液保
持材を用いた場合には、貯蔵しない前の電池においては
内部抵抗が低く、重負荷特性も優れた結果が得られるも
のの、長期間貯蔵後では放電による内部抵抗の上昇が著
しくなり、それに伴って重負荷特性も低下し、重負荷特
性を長期間維持しにくいという問題があった。When the above electrolyte holding material is used, the internal resistance of the battery before storage is low, and the excellent heavy load characteristics are obtained, but the battery is not used for a long time. After storage, there was a problem that the internal resistance increased remarkably due to discharge, and the heavy load characteristics deteriorated accordingly, making it difficult to maintain the heavy load characteristics for a long period of time.
【０００６】本発明は、こうした従来の問題点を解決す
るためになされたもので、長期間貯蔵後においても良好
な重負荷特性を維持しうる、高性能の非水溶媒電池を提
供しようとするものである。The present invention has been made in order to solve these conventional problems, and an object of the present invention is to provide a high-performance non-aqueous solvent battery which can maintain a good heavy load characteristic even after long-term storage. It is a thing.
【０００７】[0007]
【課題を解決するための手段】すなわち、本発明の非水
溶媒電池は、正極と、軽金属からなる負極とを電解液保
持材を介して積層した構造を有し、かつ非水溶媒電解液
を用いた非水溶媒電池において、一般式（Ｉ）：That is, the non-aqueous solvent battery of the present invention has a structure in which a positive electrode and a negative electrode made of a light metal are laminated with an electrolytic solution holding material interposed therebetween, and a non-aqueous solvent electrolytic solution is provided. In the non-aqueous solvent battery used, the general formula (I):
【０００８】[0008]
【化２】 [Chemical 2]
【０００９】（式中、Ｒ1 はアルキル基、アラルキル基
又はアリール基を表し、Ｒ2 は水素原子、アルキル基、
アラルキル基又はアリール基を表し、点線は共鳴混成体
構造を表す）で示されるシドノン化合物を含有する非水
溶媒を用いたことを特徴とする。(Wherein R 1 represents an alkyl group, an aralkyl group or an aryl group, R 2 represents a hydrogen atom, an alkyl group,
A non-aqueous solvent containing a sydnone compound represented by an aralkyl group or an aryl group and a dotted line representing a resonance hybrid structure is used.
【００１０】上記のシドノン化合物（Ｉ）は、式IIのよ
うな共鳴構造の混成体である。The sydnone compound (I) described above is a hybrid compound having a resonance structure represented by the formula II.
【００１１】[0011]
【化３】 [Chemical 3]
【００１２】（式中、Ｒ1 及びＲ2 はそれぞれ前述のと
おりである。）(In the formula, R 1 and R 2 are as described above.)
【００１３】本発明に用いられる非水溶媒電解液は、電
解質をシドノン化合物（Ｉ）を含有する非水溶媒に溶解
したものである。The non-aqueous solvent electrolytic solution used in the present invention is obtained by dissolving the electrolyte in a non-aqueous solvent containing the sydnone compound (I).
【００１４】本発明において非水溶媒として用いられる
シドノン化合物は、前述の一般式（Ｉ）で示される。Ｒ
1 としては、メチル、エチル、プロピル、イソプロピ
ル、ブチル、ヘキシル、ヘプチル、オクチル、ノニル、
デシル、ドデシルなどの直鎖状もしくは分岐状のアルキ
ル基；ベンジル、フェニルエチル、フェニルプロピルな
どのアラルキル基；フェニル、トリルなどのアリール基
が例示され、炭素数の増加にしたがって粘度及び融点が
上昇するため、電池の低温特性が悪くなることから、炭
素数１〜６のアルキル基が好ましく、炭素数１〜３のア
ルキル基がとくに好ましい。The sydnone compound used as the non-aqueous solvent in the present invention is represented by the above general formula (I). R
1 is methyl, ethyl, propyl, isopropyl, butyl, hexyl, heptyl, octyl, nonyl,
Examples include linear or branched alkyl groups such as decyl and dodecyl; aralkyl groups such as benzyl, phenylethyl and phenylpropyl; aryl groups such as phenyl and tolyl. Viscosity and melting point increase with increasing carbon number. Therefore, an alkyl group having 1 to 6 carbon atoms is preferable, and an alkyl group having 1 to 3 carbon atoms is particularly preferable, because the low temperature characteristics of the battery are deteriorated.
【００１５】Ｒ2 としては水素原子のほか、Ｒ1 と同じ
範囲のものが例示され、Ｒ1 と同一でも異なっていても
よい。Ｒ2 としては水素原子又は炭素数１〜３のアルキ
ル基が好ましい。[0015] In addition to hydrogen atoms as R 2, of the same range as R 1 are exemplified, it may be the same or different and R 1. R 2 is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
【００１６】本発明の非水溶媒電解液において、溶媒と
してシドノン（Ｉ）を他の非水溶媒と併用して混合溶媒
を形成しても差支えない。シドノンと併用できる非水溶
媒としては、ジメトキシエタン（ＤＭＥ）、テトラヒド
ロフラン（ＴＨＦ）、２−メチルテトラヒドロフラン、
アセトニトリル、ジオキソラン、プロピレンカーボネー
ト（ＰＣ）、エチレンカーボネート、γ−ブチロラクト
ン（γ−ＢＬ）などが例示される。該混合溶媒中のシド
ノンの量は５容量％以上が好ましく、１０容量％以上が
さらに好ましい。In the non-aqueous solvent electrolytic solution of the present invention, Sidnon (I) may be used as a solvent in combination with another non-aqueous solvent to form a mixed solvent. Examples of the non-aqueous solvent that can be used in combination with sydnone include dimethoxyethane (DME), tetrahydrofuran (THF), 2-methyltetrahydrofuran,
Acetonitrile, dioxolane, propylene carbonate (PC), ethylene carbonate, γ-butyrolactone (γ-BL) and the like are exemplified. The amount of sydnone in the mixed solvent is preferably 5% by volume or more, more preferably 10% by volume or more.
【００１７】本発明に用いられる電解質としては、たと
えばＬｉＢＦ4 、ＬｉＰＦ6 、ＬｉＣｌＯ4 、ＬｉＡｓ
Ｆ6 、ＬｉＣＦ3 ＳＯ3 、ＬｉＡｌＣｌ4 から選ばれる
１種又は２種以上のリチウム塩を用いることができる。
このようなリチウム塩は、溶媒中に０．２〜１．５モル
／リットル溶解することが望ましい。この理由は、この
範囲を逸脱すると、導電率の低下と、リチウムの充放電
効率の低下を招く恐れがあるからである。Examples of the electrolyte used in the present invention include LiBF 4 , LiPF 6 , LiClO 4 , and LiAs.
One or more lithium salts selected from F 6 , LiCF 3 SO 3 and LiAlCl 4 can be used.
It is desirable that such a lithium salt be dissolved in a solvent in an amount of 0.2 to 1.5 mol / liter. The reason for this is that if it deviates from this range, the conductivity and the lithium charging / discharging efficiency may decrease.
【００１８】非水溶媒電解液は、電池容器内に収容する
前にあらかじめ水分及び不純物を除去する目的で、不溶
性吸着材で処理するか、又は通電処理するか、あるいは
これらの両方の処理を施すことが望ましい。The non-aqueous solvent electrolyte is treated with an insoluble adsorbent, or subjected to electric current treatment, or both treatments for the purpose of removing moisture and impurities in advance before being stored in the battery container. Is desirable.
【００１９】上記の不溶性吸着材による処理は、たとえ
ば前記の電解液中に、活性アルミナやモレキュラーシー
ブなど、電解液と反応しない不溶性吸着材を加えて撹拌
した後、不溶性吸着材をろ過などにより分離する方法、
又は不溶性吸着材を充填したカラムに電解液を流通させ
る方法を採用することができる。The treatment with the above-mentioned insoluble adsorbent is carried out by, for example, adding an insoluble adsorbent which does not react with the electrolytic solution, such as activated alumina or molecular sieve, to the above-mentioned electrolytic solution, stirring and separating the insoluble adsorbent by filtration or the like. how to,
Alternatively, a method in which the electrolytic solution is passed through a column filled with an insoluble adsorbent can be adopted.
【００２０】上記の通電処理は、たとえば電解液中にリ
チウムからなる電極を正極として侵漬し、かつリチウム
又はリチウム以外の金属からなる電極を負極として浸漬
した後、これら正極及び負極の間に定電流又は定電圧で
連続波もしくはパルスを印加して、負極上にリチウムを
析出させるか、析出と溶解を繰り返す方法を採用するこ
とができる。The above energization treatment is carried out by, for example, immersing an electrode made of lithium as a positive electrode in an electrolytic solution and an electrode made of lithium or a metal other than lithium as a negative electrode, and then applying a constant voltage between the positive electrode and the negative electrode. A method of applying a continuous wave or a pulse with a current or a constant voltage to deposit lithium on the negative electrode, or repeating deposition and dissolution can be adopted.
【００２１】また本発明の非水溶媒電池において、正極
としては、たとえば二酸化マンガン、酸化銅、フッ化黒
鉛などが挙げられる。In the non-aqueous solvent battery of the present invention, examples of the positive electrode include manganese dioxide, copper oxide, graphite fluoride and the like.
【００２２】本発明の非水溶媒電池において、負極を構
成する軽金属又はその合金としては、たとえばリチウ
ム、アルミニウム、リチウム−アルミニウム合金などが
挙げられる。In the non-aqueous solvent battery of the present invention, examples of the light metal or its alloy forming the negative electrode include lithium, aluminum and lithium-aluminum alloy.
【００２３】さらに、本発明の非水溶媒電池において、
電解液保持材は、ポリプロピレン不織布などが用いられ
る。Further, in the non-aqueous solvent battery of the present invention,
A polypropylene nonwoven fabric or the like is used as the electrolyte holding material.
【００２４】[0024]
【作用】本発明によれば、非水溶媒電解液の非水溶媒と
してシドノン化合物（Ｉ）を用いることによって、負極
軽金属と前記電解液との反応による該軽金属の劣化を抑
制でき、貯蔵特性に優れた非水溶媒電池を得ることがで
きる。According to the present invention, by using the sydnone compound (I) as the non-aqueous solvent of the non-aqueous solvent electrolytic solution, deterioration of the light metal due to the reaction between the negative electrode light metal and the electrolytic solution can be suppressed, and the storage characteristics can be improved. An excellent non-aqueous solvent battery can be obtained.
【００２５】すなわち、電解質として用いる、たとえば
ＬｉＰＦ6 やＬｉＢＦ4 は、水分や熱に不安定であるた
め、分解してＰＦ5やＢＦ3 などのルイス酸を生成す
る。このようなルイス酸は、溶媒と反応し易く、リチウ
ムなどの軽金属を劣化させる不純物を生成する。That is, for example, LiPF 6 and LiBF 4, which are used as the electrolyte, are unstable to water and heat and therefore decompose to produce Lewis acids such as PF 5 and BF 3 . Such a Lewis acid easily reacts with a solvent and produces impurities that deteriorate light metals such as lithium.
【００２６】本発明によると、ルイス酸による酸化反応
に強いシドノン化合物（Ｉ）を用いることによって、溶
媒とルイス酸との反応を抑制でき、その結果、リチウム
などの軽金属で構成される負極を劣化させる不純物の生
成を減少できる。According to the present invention, the reaction between the solvent and the Lewis acid can be suppressed by using the sydnone compound (I) which is strong against the oxidation reaction by the Lewis acid, and as a result, the negative electrode composed of a light metal such as lithium is deteriorated. It is possible to reduce the generation of impurities.
【００２７】また、上記のシドノン化合物（Ｉ）の誘電
率は、たとえば、３−メチルシドノン：１４４．０（４
０℃）、３−プロピルシドノン：９５．０（２５℃）、
３−イソプロピルシドノン：６６．０（６０℃）、３−
ブチルシドノン：５２．８（２５℃）であり、ＰＣ：６
４．４（２５℃）、ＤＭＥ：７．２０（２５℃）、γ−
ＢＬ：３９．１（２５℃）、ＴＨＦ：７．５８（２５
℃）などの他の有機溶媒に比較して高い。さらに、たと
えば３−プロピルシドノンは、低温（０℃付近）におい
て非常に高い誘電率を示す。このことから、シドノン化
合物を非水溶媒電解液の溶媒として用いると、その高い
誘電率により、低温時においても、電解質であるリチウ
ム塩をイオン解離しやすく、このことから、他の有機溶
媒を用いた時よりも低温作動特性に優れた非水溶媒電池
を得ることができる。The dielectric constant of the above sydnone compound (I) is, for example, 3-methylsydnone 144.0 (4
0 ° C.), 3-propylsydnone: 95.0 (25 ° C.),
3-Isopropylsydnone: 66.0 (60 ° C), 3-
Butylsidone: 52.8 (25 ° C), PC: 6
4.4 (25 ° C), DME: 7.20 (25 ° C), γ-
BL: 39.1 (25 ° C), THF: 7.58 (25
Higher than other organic solvents such as (° C). Furthermore, for example, 3-propylsydnone has a very high dielectric constant at low temperatures (around 0 ° C.). From this, when a sydnone compound is used as a solvent for a non-aqueous solvent electrolyte, its high dielectric constant facilitates ion dissociation of the lithium salt, which is the electrolyte, even at low temperatures. It is possible to obtain a non-aqueous solvent battery having excellent low-temperature operation characteristics as compared with the case where it is used.
【００２８】なお、前記の組成の非水溶媒電解液を電池
容器内に収容する前に、あらかじめ不溶性吸着材に接触
させる処理、及び／又は通電処理を施すことによって、
リチウムなどの軽金属負極と前記の非水電解液との反応
による該軽金属の劣化を顕著に抑制でき、貯蔵性が極め
て良好な非水溶媒電池を得ることができる。これは、前
記の処理により電解液中の不純物が除去され、高純度の
非水電解液が得られるからである。なお、本発明は、コ
イン形をはじめ、円筒形、扁平形、角形などの各種の形
状の非水溶媒電池に適用できる。Before containing the non-aqueous solvent electrolyte having the above-mentioned composition in the battery container, it is possible to contact the insoluble adsorbent with a non-aqueous solvent and / or to apply an electric current.
It is possible to remarkably suppress the deterioration of the light metal due to the reaction between the light metal negative electrode such as lithium and the non-aqueous electrolytic solution, and it is possible to obtain a non-aqueous solvent battery having an excellent storage property. This is because impurities in the electrolytic solution are removed by the above treatment, and a highly pure non-aqueous electrolytic solution is obtained. The present invention can be applied to non-aqueous solvent batteries having various shapes such as a coin shape, a cylindrical shape, a flat shape, and a rectangular shape.
【００２９】[0029]
【発明の効果】以上詳述したように、本発明によれば、
非水溶媒電解液の非水溶媒としてシドノン化合物（Ｉ）
を用いることによって、長期間貯蔵後においても良好な
重負荷特性を維持しうる、高性能な非水溶媒電池を提供
できる。As described in detail above, according to the present invention,
Sydnone compound (I) as non-aqueous solvent of non-aqueous solvent electrolyte
By using, it is possible to provide a high-performance non-aqueous solvent battery capable of maintaining good heavy load characteristics even after long-term storage.
【００３０】[0030]
【実施例】以下、本発明の実施例を、図１を参考にして
詳細に説明する。Embodiments of the present invention will be described in detail below with reference to FIG.
【００３１】実施例１ 図１において、正極端子を兼ねるステンレス製電池容器
１内に、電解二酸化マンガンを加熱焼成して得た活物
質、アセチレンブラック及びポリテトラフルオロエチレ
ンからなり、円板状に加圧成形した正極２を収納した。
この正極２の上に、ポリプロピレン不織布からなり、式
(III) で示される３−プロピルシドノンに０．５モル／
リットルの過塩素酸リチウムを溶解して調製した電解液
を含浸した電解液保持材３を配置した。Example 1 In FIG. 1, in a stainless steel battery container 1 also serving as a positive electrode terminal, an active material obtained by heating and calcining electrolytic manganese dioxide, acetylene black and polytetrafluoroethylene were used. The pressure-formed positive electrode 2 was stored.
On this positive electrode 2, a polypropylene non-woven fabric
0.5 mol / mol of 3-propylsidone represented by (III)
An electrolytic solution holding material 3 impregnated with an electrolytic solution prepared by dissolving liter of lithium perchlorate was arranged.
【００３２】[0032]
【化４】 [Chemical 4]
【００３３】電池容器１の開口部に、パッキン４を介し
て、負極端子を兼ねるステンレスからなる封口板５を液
密に設け、かつ容器１内の該封口板５の内面には金属リ
チウムからなる負極６を着設した。このような構造の、
直径２０mm、厚さ２．５mmの非水溶媒電池を作成した。A sealing plate 5 made of stainless steel and also serving as a negative electrode terminal is liquid-tightly provided in the opening of the battery container 1 via a packing 4, and the inner surface of the sealing plate 5 in the container 1 is made of metallic lithium. The negative electrode 6 was attached. With such a structure,
A non-aqueous solvent battery having a diameter of 20 mm and a thickness of 2.5 mm was prepared.
【００３４】実施例２ 非水溶媒電解液として、濃度０．５モル／リットルの過
塩素酸リチウム（ＬｉＣｌＯ4 ）を３−プロピルシドノ
ンとＤＭＥの混合溶媒（混合体積比率５０：５０）に溶
解した組成のものを用いた以外、実施例１と同じ構成の
非水溶媒電池を組み立てた。Example 2 As a non-aqueous solvent electrolyte, lithium perchlorate (LiClO 4 ) having a concentration of 0.5 mol / liter was dissolved in a mixed solvent of 3-propylsydnone and DME (mixing volume ratio 50:50). A non-aqueous solvent battery having the same configuration as in Example 1 was assembled except that the one having the above composition was used.
【００３５】比較例１ 非水溶媒電解液として、濃度０．５モル／リットルの過
塩素酸リチウム（ＬｉＣｌＯ4 ）をＰＣに溶解した電解
液を用いた以外は、実施例１と同じ構成の非水溶媒電池
を組み立てた。Comparative Example 1 A non-aqueous solvent electrolytic solution having the same constitution as in Example 1 except that an electrolytic solution prepared by dissolving lithium perchlorate (LiClO 4 ) having a concentration of 0.5 mol / liter in PC was used. A water solvent battery was assembled.
【００３６】比較例２ 非水溶媒電解液として０．５モル／リットル濃度の過塩
素酸リチウム（ＬｉＣｌＯ4 ）をＰＣとＤＭＥの混合溶
媒（混合体積比率５０：５０）に溶解した組成のものを
用いた以外は、実施例１と同じ構成の非水溶媒電池を組
み立てた。Comparative Example 2 A non-aqueous solvent electrolyte having a composition in which 0.5 mol / liter concentration of lithium perchlorate (LiClO 4 ) was dissolved in a mixed solvent of PC and DME (mixing volume ratio 50:50). A non-aqueous solvent battery having the same configuration as in Example 1 except that it was used was assembled.
【００３７】測定例 本発明による実施例１、２ならびに従来技術による比較
例１、２の非水溶媒電池について、６０℃で長期間貯蔵
加速試験を行った後、それぞれの電池を放電深度１％及
び８０％において、７０Ω、２０msのパルス印加を行っ
た際の閉路電圧値を、それぞれ図２及び図３に示す。ま
た、放電深度１％及び８０％における電池の内部抵抗値
をそれぞれ図４及び図５に示す。なお、図２〜図５中の
Ａ及びＢはそれぞれ実施例１及び２で作製した電池の特
性を示す曲線、Ｃ及びＤはそれぞれ比較例１及び２で作
製した電池の特性を示す曲線である。図２〜図５に示す
ように、実施例の非水溶媒電池は、長期間貯蔵及び放電
進行による内部抵抗の変化がきわめて小さく、閉路電圧
の劣化も少ないことがわかる。Measurement Example The non-aqueous solvent batteries of Examples 1 and 2 according to the present invention and Comparative Examples 1 and 2 according to the prior art were subjected to a long-term accelerated storage test at 60 ° C., and then the respective batteries were discharged at a discharge depth of 1%. 2 and 3 show the closed circuit voltage values when a pulse of 70Ω and 20 ms was applied at 80% and 80%, respectively. Further, the internal resistance values of the battery at the discharge depths of 1% and 80% are shown in FIGS. 4 and 5, respectively. 2 to 5, A and B are curves showing the characteristics of the batteries manufactured in Examples 1 and 2, respectively, and C and D are curves showing the characteristics of the batteries manufactured in Comparative Examples 1 and 2, respectively. .. As shown in FIGS. 2 to 5, it can be seen that the non-aqueous solvent batteries of Examples have very little change in internal resistance due to long-term storage and discharge progress and little deterioration in closed circuit voltage.
【図１】本発明の一実施例を示す非水溶媒電池の断面図
である。FIG. 1 is a cross-sectional view of a non-aqueous solvent battery showing an embodiment of the present invention.
【図２】放電深度１％において、７０Ω、２０msのパル
ス印加を行った際の閉路電圧と貯蔵日数の関係を示すグ
ラフである。FIG. 2 is a graph showing the relationship between the closed circuit voltage and the number of days of storage when a pulse of 70Ω and 20 ms is applied at a discharge depth of 1%.
【図３】放電深度８０％において、７０Ω、２０msのパ
ルス印加を行った際の閉路電圧と貯蔵日数の関係を示す
グラフである。FIG. 3 is a graph showing the relationship between the closed circuit voltage and the number of storage days when a pulse of 70Ω and 20 ms is applied at a discharge depth of 80%.
【図４】放電深度１％における内部抵抗と貯蔵日数の関
係を示すグラフである。FIG. 4 is a graph showing the relationship between the internal resistance and the number of storage days at a discharge depth of 1%.
【図５】放電深度８０％における内部抵抗と貯蔵日数の
関係を示すグラフである。FIG. 5 is a graph showing the relationship between the internal resistance and the number of storage days at a discharge depth of 80%.
１ 電池容器 ２ 正極 ３ 電解液保持材 ４ パッキン ５ 封口板 ６ 負極 Ａ 実施例１の電池 Ｂ 実施例２の電池 Ｃ 比較例１の電池 Ｄ 比較例２の電池 DESCRIPTION OF SYMBOLS 1 Battery container 2 Positive electrode 3 Electrolyte holding material 4 Packing 5 Sealing plate 6 Negative electrode A Battery of Example 1 Battery B of Example 2 Battery C of Comparative Example 1 Battery D of Comparative Example 2
Claims (1)
保持材を介して積層した構造を有し、かつ非水溶媒電解
液を用いた非水溶媒電池において、一般式（Ｉ）： 【化１】 （式中、Ｒ1 はアルキル基、アラルキル基又はアリール
基を表し、Ｒ2 は水素原子、アルキル基、アラルキル基
又はアリール基を表し、点線は共鳴混成体構造を表す）
で示されるシドノン化合物を含有する非水溶媒を用いた
ことを特徴とする非水溶媒電池。1. A non-aqueous solvent battery having a structure in which a positive electrode and a negative electrode made of a light metal are laminated with an electrolytic solution holding material interposed therebetween, and a non-aqueous solvent battery using a non-aqueous solvent electrolytic solution has the general formula (I): Chemical 1] (In the formula, R 1 represents an alkyl group, an aralkyl group or an aryl group, R 2 represents a hydrogen atom, an alkyl group, an aralkyl group or an aryl group, and a dotted line represents a resonance hybrid structure)
A non-aqueous solvent battery comprising a non-aqueous solvent containing a sydnone compound represented by:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3216608A JP3004778B2 (en) | 1991-08-02 | 1991-08-02 | Non-aqueous solvent battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3216608A JP3004778B2 (en) | 1991-08-02 | 1991-08-02 | Non-aqueous solvent battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0541246A true JPH0541246A (en) | 1993-02-19 |
| JP3004778B2 JP3004778B2 (en) | 2000-01-31 |
Family
ID=16691098
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3216608A Expired - Fee Related JP3004778B2 (en) | 1991-08-02 | 1991-08-02 | Non-aqueous solvent battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3004778B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110911747A (en) * | 2019-11-29 | 2020-03-24 | 桑德新能源技术开发有限公司 | Electrolyte additive, electrolyte and lithium ion battery |
-
1991
- 1991-08-02 JP JP3216608A patent/JP3004778B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110911747A (en) * | 2019-11-29 | 2020-03-24 | 桑德新能源技术开发有限公司 | Electrolyte additive, electrolyte and lithium ion battery |
| CN110911747B (en) * | 2019-11-29 | 2021-06-08 | 桑德新能源技术开发有限公司 | Electrolyte additive, electrolyte and lithium ion battery |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3004778B2 (en) | 2000-01-31 |
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