JPH0487156A - Nonaqueous electrolyte battery - Google Patents
Nonaqueous electrolyte batteryInfo
- Publication number
- JPH0487156A JPH0487156A JP2199519A JP19951990A JPH0487156A JP H0487156 A JPH0487156 A JP H0487156A JP 2199519 A JP2199519 A JP 2199519A JP 19951990 A JP19951990 A JP 19951990A JP H0487156 A JPH0487156 A JP H0487156A
- Authority
- JP
- Japan
- Prior art keywords
- battery
- solvent
- lithium
- vinyl
- discharge characteristics
- 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
- 239000011255 nonaqueous electrolyte Substances 0.000 title claims description 6
- 239000002904 solvent Substances 0.000 claims abstract description 22
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 14
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 13
- BJWMSGRKJIOCNR-UHFFFAOYSA-N 4-ethenyl-1,3-dioxolan-2-one Chemical compound C=CC1COC(=O)O1 BJWMSGRKJIOCNR-UHFFFAOYSA-N 0.000 claims abstract description 6
- 150000001875 compounds Chemical class 0.000 claims abstract description 6
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 4
- 239000000956 alloy Substances 0.000 claims abstract description 4
- LDLDYFCCDKENPD-UHFFFAOYSA-N ethenylcyclohexane Chemical compound C=CC1CCCCC1 LDLDYFCCDKENPD-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000008151 electrolyte solution Substances 0.000 claims description 7
- WTGOBAQKOKRTAN-UHFFFAOYSA-N COC1C=COC=CC1OC Chemical compound COC1C=COC=CC1OC WTGOBAQKOKRTAN-UHFFFAOYSA-N 0.000 claims description 3
- UYMKPFRHYYNDTL-UHFFFAOYSA-N ethenamine Chemical compound NC=C UYMKPFRHYYNDTL-UHFFFAOYSA-N 0.000 claims description 3
- KKBHSBATGOQADJ-UHFFFAOYSA-N 2-ethenyl-1,3-dioxolane Chemical compound C=CC1OCCO1 KKBHSBATGOQADJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000003792 electrolyte Substances 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- -1 vinyl amine Chemical class 0.000 abstract description 2
- 229920002554 vinyl polymer Polymers 0.000 abstract description 2
- MFGFKKVWWFCBST-UHFFFAOYSA-N 4,5-dihydrooxepine Chemical compound C1CC=COC=C1 MFGFKKVWWFCBST-UHFFFAOYSA-N 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 13
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 4
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 3
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
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
【発明の詳細な説明】
（イ）産業上の利用分野
本発明は、リチウム或るいはリチウムを含む合金からな
る負極と、正極と、溶質、及び溶媒からなる電解液と、
を備えた非水系電解液電池に関する。DETAILED DESCRIPTION OF THE INVENTION (a) Field of Industrial Application The present invention provides a negative electrode made of lithium or an alloy containing lithium, a positive electrode, an electrolyte solution made of a solute, and a solvent.
The present invention relates to a non-aqueous electrolyte battery comprising:
（ロ）従来の技術
非水系電解液電池は、ｍ位体積当りのエネルギ密度が高
く、且つ自己放電率が低いという利点を有している。(b) Conventional technology Non-aqueous electrolyte batteries have the advantage of high energy density per m-volume and low self-discharge rate.
ところで電解液を構成する溶質としては一般に過塩素酸
リチウムが用いられているが、この過塩素酸リチウムを
用いた場合には電池の低温放電特性に難があり、また過
塩素酸リチウムは非常に酸化力が大であるため有機溶媒
を酸化してしまうという欠点があった。By the way, lithium perchlorate is generally used as the solute that makes up the electrolyte, but when this lithium perchlorate is used, the low-temperature discharge characteristics of the battery are difficult, and lithium perchlorate is extremely Since it has a large oxidizing power, it has the disadvantage of oxidizing organic solvents.
これを解決する手段として、例えば特開昭５８−６６２
６４号公報や特開昭５８−１６３］７６号公報に示され
ているように、フッ素を含むリチウム塩を溶質として用
い、前記低温放電特性を改善するとともに、有機溶媒の
酸化を抑制する技術があった。As a means to solve this problem, for example, Japanese Patent Laid-Open No. 58-662
As shown in Japanese Patent Laid-open No. 64 and Japanese Patent Application Laid-open No. 58-163/1976, there is a technology that uses a fluorine-containing lithium salt as a solute to improve the low-temperature discharge characteristics and suppress the oxidation of organic solvents. there were.
しかしながらフッ素を含むリチウム塩を溶質に用いた場
合、電池缶材料が腐食し、電解液中に溶解した電池缶材
料が負極表面に析出するので、電圧降下、放電界１の減
少等を引き起こし、電池の保存特性を劣化させるという
間眺点があった。However, when a fluorine-containing lithium salt is used as a solute, the battery can material corrodes and the battery can material dissolved in the electrolyte is deposited on the negative electrode surface, causing a voltage drop, a decrease in the discharge field 1, etc. There was a point of view that it deteriorated the preservation characteristics of.
これを解決する方法として電解液に硝酸リチウムを添加
させるという技術を本発明者等は先に提案した。As a method to solve this problem, the present inventors previously proposed a technique of adding lithium nitrate to the electrolytic solution.
（ハ）発明が解決しようとする課題
このように溶質側の改良によって溶媒、及び電池缶の酸
化、腐食を抑制し、放電特性、及び保存特性を向上させ
る技術が従来がら種々提案されてきたが、一方の自己放
電率の低下を目的とした技術改良は余り成されていない
。(c) Problems to be Solved by the Invention Various techniques have been proposed in the past to suppress oxidation and corrosion of the solvent and battery can by improving the solute side, and to improve discharge characteristics and storage characteristics. On the other hand, there have not been many technical improvements aimed at reducing the self-discharge rate.
そこで、本発明者等は、自己放電の原因は負極ノチウム
と溶媒との反応に起因することを見出した。Therefore, the present inventors discovered that the cause of self-discharge is due to the reaction between the negative electrode notium and the solvent.
本発明はかかる原因に鑑み、溶媒としてリチウムと反応
しにくい不飽和の炭素−炭素結合を鎖式に有する化合物
を用いて、自己放電特性を改善することを目的とする。In view of these causes, the present invention aims to improve the self-discharge characteristics by using a compound having a chain structure of unsaturated carbon-carbon bonds that are difficult to react with lithium as a solvent.
（ニ）課題を解決するための手段
本発明は、リチウム或るいはリチウムを含む合金からな
る負極と、正極と、溶質と溶媒からなる電解液とを備え
、前記溶媒として、不飽和の炭素−炭素結合を鎖式に有
するビニルエチレンカーボネート、２−ビニル−】、３
〜ジオキソラン、１，２−ジメトキシエチレン、ジビニ
ルエーテル、Ｎ−ビニルイミダゾール、ビニルアミン、
ビニルシクロヘキサンの群から選ばれた少なくとも一つ
の化合物からなる溶媒を用いたものである。(d) Means for Solving the Problems The present invention comprises a negative electrode made of lithium or an alloy containing lithium, a positive electrode, and an electrolytic solution made of a solute and a solvent. Vinyl ethylene carbonate having chain carbon bonds, 2-vinyl-], 3
~dioxolane, 1,2-dimethoxyethylene, divinyl ether, N-vinylimidazole, vinylamine,
A solvent consisting of at least one compound selected from the group of vinylcyclohexane is used.
（ホ）作用
一１―記の如く溶媒として不飽和の炭素−炭素結合を鎖
式に有する化合物を用いたことにより、該溶媒と負極リ
チウムとの反応が極めて少なくなった。(e) Effect 1 As described in 1-1, by using a compound having a chain structure of unsaturated carbon-carbon bonds as a solvent, the reaction between the solvent and the negative electrode lithium was extremely reduced.
（へ）実施例
○犬産■」
第１図は本発明による舖平型非水系電解液−次電池の断
面図を示し、リチウム金属からなる負極１は負極集電体
２の内面に圧着されており、この負極集電体２はフェラ
イト系ステンレス鋼（ＳＵＳ４３（＋）からなる断面略
コ字状の負極缶３の内底面に固着さｔ″Ｌでいる。−Ｉ
−記負極缶３の周端はポリプロピレン性の絶縁バッキン
グ４の内部に固定されており、絶縁バッキング４の外周
には、ステンレスからなり上記負極缶３とは反対方向に
断面略コ字状を成す正極缶５が固定されている。この正
極缶５の内底面には正極集電体６が固着されており、こ
の正極集電体６の内面には正極７が固定されている。さ
らにこの正極７と前記負極１との間には、電解液が含浸
されたセパレ〜り８が介挿されている。(F) Example ○ Inu-made ■ Figure 1 shows a cross-sectional view of a flat-shaped non-aqueous electrolyte secondary battery according to the present invention, in which a negative electrode 1 made of lithium metal is crimped onto the inner surface of a negative electrode current collector 2. This negative electrode current collector 2 is fixed to the inner bottom surface of a negative electrode can 3 made of ferritic stainless steel (SUS43(+) and having a substantially U-shaped cross section.
- The peripheral end of the negative electrode can 3 is fixed inside an insulating backing 4 made of polypropylene, and the outer periphery of the insulating backing 4 is made of stainless steel and has a substantially U-shaped cross section in the opposite direction to the negative electrode can 3. A positive electrode can 5 is fixed. A positive electrode current collector 6 is fixed to the inner bottom surface of the positive electrode can 5, and a positive electrode 7 is fixed to the inner surface of the positive electrode current collector 6. Further, a separator 8 impregnated with an electrolytic solution is inserted between the positive electrode 7 and the negative electrode 1.
ところで、前記正極７は３５０−４３Ｂの温度範囲で熱
処理した二酸化マンガンを活物質として用い、この二酸
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８：１゜：５の重量比で混
合し、次にこの混合物を加圧成形した後、２５０〜３５
０℃で熱処理して作製した。Incidentally, the positive electrode 7 uses manganese dioxide heat-treated in a temperature range of 350-43B as an active material, and mixes this manganese dioxide, carbon powder as a conductive agent, and fluororesin powder as a binder at a ratio of 8:1. :5 weight ratio, and then pressure molding this mixture.
It was produced by heat treatment at 0°C.
また前記負極１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。Further, the negative electrode 1 was produced by punching a lithium rolled plate into a predetermined size.
そして電解液としては、不飽和の炭素−炭素結合を鎖式
に有するビニルエチレンカーボネートと、１．２−ジメ
トキシエタンとの等体積の混合溶媒に、溶質としてのト
リフルオロメタンスルホン酸リチウム（［、ｉＣＦ、Ｓ
Ｏ，）を１ｍｏｌ／！溶解したものを用いた。As an electrolytic solution, lithium trifluoromethanesulfonate ([, iCF , S
O,) 1 mol/! The dissolved one was used.
これら正負極７．１ 、及び電解液を、セパレータ８を
介して正負極論５，３内に納め、組み立てた電池を、以
下本発明電池Ａと称する。尚、組み立てられた電池の電
池径は２０ ｍ ｍ 、 を池厚は２．５ｍｍ電池容量
は１３０ｎ＋ＡＩ（とした。The positive and negative electrodes 7.1 and the electrolytic solution are housed in the positive and negative electrodes 5 and 3 via the separator 8, and the assembled battery is hereinafter referred to as the battery A of the present invention. The assembled battery had a battery diameter of 20 mm, a cell thickness of 2.5 mm, and a battery capacity of 130 n+AI.
○ル較■ユ
上記ビニルエチレンカーボネートの代）つりに鎖式の炭
素−炭素結合を持たないエチレンカーボネートを用いた
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比較電池Ｘと称する。A battery was produced in the same manner as in the above Example except that ethylene carbonate, which does not have a chain carbon-carbon bond, was used in place of the above vinyl ethylene carbonate. The battery thus produced is referred to as Comparative Battery X.
○試験１
１−配本発明電池Ａと、比較電池Ｘにおいて、初期の放
電特性を調べた。その結果を第２図、及び第３図に示す
。なお、第２図は電池＃１ヶで後、直ちに温度２５℃、
負荷３にΩで放電したときの放電特性図であり、第３図
は電池組立て後、温度６０℃で３ケ月間保存（室温で４
−５年間保存した場合に相当）した後、温度２５℃、負
荷３にΩで放電したときの放電特性図である。○Test 1 1-Distribution The initial discharge characteristics of the battery A of the present invention and the comparative battery X were investigated. The results are shown in FIGS. 2 and 3. In addition, in Figure 2, after using battery #1, the temperature was immediately changed to 25°C.
This is a discharge characteristic diagram when discharging at Ω into load 3. Figure 3 shows the discharge characteristics when the battery is assembled and stored at a temperature of 60°C for 3 months (at room temperature for 4 months).
This is a discharge characteristic diagram when the battery is discharged at a temperature of 25° C. and a load of 3 to a load of Ω after the battery has been stored for -5 years.
上記第２．３図から明らかなように、本発明電池Ａと比
較電池Ｘとは初期の放電特性では同等の値を示している
。しかしながら、保存後の放電特性を比較すると、本発
明電池Ａの方が比較電池Ｘより長時間（略］Ｏｈの差）
高い放電電圧を示し、長期保存後でも内部インピーダン
スの増加が抑制されていることが分かる。As is clear from FIG. 2.3 above, the battery A of the present invention and the comparative battery X have the same initial discharge characteristics. However, when comparing the discharge characteristics after storage, the battery A of the present invention lasts longer than the comparative battery X (difference in Oh)
It shows a high discharge voltage, and it can be seen that the increase in internal impedance is suppressed even after long-term storage.
また、長期保存後の前記両電池Ａ、Ｘを分解したところ
、比較電池Ｘでは負極リチウム表面が黒く変色していた
のに対し、本発明電池へではそのような現象は見られな
かった。Further, when both batteries A and X were disassembled after long-term storage, the negative electrode lithium surface of comparative battery X was discolored black, whereas such a phenomenon was not observed in the battery of the present invention.
この結果より、比較電池Ｘでは保存中にエチレンカーボ
ネートがリチウム負極と反応し、この結果保存後の放電
特性が低下したものと考えられる。From this result, it is considered that in Comparative Battery X, ethylene carbonate reacted with the lithium negative electrode during storage, and as a result, the discharge characteristics after storage deteriorated.
一方、本発明電池Ａのように電解液の溶媒としてビニル
エチレンカーボネートを用いると、電子供す性のビニル
基がエチレンカーボネートと負極Ｊチウムとの反応を抑
制し、この結果、保存後の放電特性の低下を防止できた
ものと考えられる。On the other hand, when vinyl ethylene carbonate is used as a solvent for the electrolyte as in the battery A of the present invention, the electron-resistant vinyl group suppresses the reaction between ethylene carbonate and the negative electrode J thium, resulting in poor discharge characteristics after storage. It is thought that the decline could have been prevented.
○炎鼻■１
電解液の溶質としてＬｉＰＦ、を用い、溶媒として不飽
和の炭素−炭素結合を鎖式に有する２−ビニル−１，３
−ジオキンランとプロピレンカーボネートとの等体積の
混合溶媒を用いた他は、上記実施例Ｉと同様にして電池
を作製した。○Flame Nose■1 LiPF is used as the solute of the electrolyte, and 2-vinyl-1,3 having unsaturated carbon-carbon bonds in a chain form is used as the solvent.
- A battery was produced in the same manner as in Example I above, except that a mixed solvent of equal volumes of dioquinrane and propylene carbonate was used.
このようにして作製した電池を、以下本発明電池Ｂと称
す。The battery thus produced is hereinafter referred to as the battery B of the present invention.
○埼軟■ユ
次に、２−ビニル−１，３−ジオキソランの代わりに鎖
式の炭素−炭素結合を持たない１．３−ジオキソランを
用いる他は上記実施例２と同様にして電池を作製した。○ Saisoft ■ Yu Next, a battery was produced in the same manner as in Example 2 above, except that 1,3-dioxolane, which does not have a chain carbon-carbon bond, was used instead of 2-vinyl-1,3-dioxolane. did.
このようにして作製した電池を以Ｆ比較電池）′と称す
る。The battery thus produced is hereinafter referred to as F comparative battery)'.
○試験２
上記本発明電池Ｂ、及び比？２電池Ｙの初期の放電特性
と、保存後の放電特性とを、前記試験１と同様の条件で
調べた。その結果を夫々第４図、及び第５図に示す。こ
れら第４．５図から明らかなように初期の放電特性は両
電池Ｂ、Ｙ共に同等であるが、保存後の放電特性は、比
較電池Ｙより本発明電池Ｂの方が優れている（略］５ｈ
の差）ことが分かる。○Test 2 Above invention battery B and ratio? 2 The initial discharge characteristics and discharge characteristics after storage of Battery Y were investigated under the same conditions as Test 1 above. The results are shown in FIGS. 4 and 5, respectively. As is clear from these Figures 4.5, the initial discharge characteristics are the same for both batteries B and Y, but the discharge characteristics after storage are better for the battery B of the present invention than for the comparative battery Y (approximately ]5h
(difference).
○にムＡ１
前記実施例１、及び実施例２では非水系の一次電池につ
いて本発明電池を説明したが、次に非水系二次電池に適
用した実施例３について説明する。In Example 1 and Example 2, the battery of the present invention was explained using a non-aqueous primary battery. Next, Example 3 applied to a non-aqueous secondary battery will be described.
この非水系二次電池の構造は前記第１図に示す扁平型−
次電池と同じであるが、正極７の活物質として充電可能
なマンガン酸化物を用いた点が異なっており、また、そ
の電解液としては、不飽和の炭素−炭素結合を鎖式に有
するビニルエチレンカーボネートと、１．２−ジメトキ
シエタンとの等体積の混合溶媒に、溶質としてのトリフ
ルオロメタンスルホン酸リチウムをＩｍｏｌ／ｆ溶解し
たものを用いた点が異なっている。The structure of this non-aqueous secondary battery is a flat type shown in FIG.
It is the same as the next battery, but differs in that rechargeable manganese oxide is used as the active material of the positive electrode 7, and the electrolyte is made of vinyl having unsaturated carbon-carbon bonds in a chain form. The difference is that lithium trifluoromethanesulfonate as a solute was dissolved in Imol/f of a mixed solvent of ethylene carbonate and 1,2-dimethoxyethane in equal volumes.
このようにして作製した電池を本発明電池Ｃと称する。The battery thus produced is referred to as the battery C of the present invention.
○を枚■ユ
上記実施例３のビニルエチレンカーボネートの代わりに
鎖式の炭素−炭素結合を持たないエチレンカーボネート
を用いた他は本発明電池Ｃと同様゛にして比較電池Ｚを
得た。Comparative battery Z was obtained in the same manner as battery C of the present invention except that ethylene carbonate having no chain carbon-carbon bond was used in place of the vinyl ethylene carbonate of Example 3.
○試験３
前記本発明電池Ｃと、比較電池Ｚとの充放電サイクル試
験を行ってその特性を調べた。ここでは、充放Ｓ電流を
２ｍＡ、充電時間を３時間とし、充放電の繰り返しによ
り端子電圧が２．Ｏｖに達するまでの放電サイクル数を
取った。電池組立て直後にサイクル試験を行った結果を
第６図に示し、６０℃で；３ケ月保存後にサイクル試験
を行った結果を第７図に夫々示す。○Test 3 A charge/discharge cycle test was conducted on the battery C of the present invention and the comparative battery Z to examine their characteristics. Here, the charging/discharging S current is 2 mA, the charging time is 3 hours, and the terminal voltage increases to 2.0 mA by repeating charging and discharging. The number of discharge cycles until reaching Ov was taken. The results of a cycle test conducted immediately after battery assembly are shown in FIG. 6, and the results of a cycle test conducted after storage at 60° C. for 3 months are shown in FIG. 7, respectively.
１−記第６，７図から初期のサイクル特性は両電池Ｃ１
Ｚとも同等であるが、本発明電池Ｃは保存後のサイクル
特性に関して、比較電池Ｚよりも優れている（略２５回
の差）ことが分かる。1- From Figures 6 and 7, the initial cycle characteristics are for both batteries C1.
It can be seen that the battery C of the present invention is superior to the comparison battery Z in terms of cycle characteristics after storage (difference of about 25 cycles), although the battery C is also similar to the battery Z.
本発明は上記溶媒材料の他、１．２−ジメトキシエチレ
ン、ジビニルエーテル、Ｎ−ビニルイミダゾール、ビニ
ルアミン、ビニルシクロヘキサンも同様の効果を生じる
ことを確認した。In the present invention, it has been confirmed that, in addition to the above solvent materials, 1,2-dimethoxyethylene, divinyl ether, N-vinylimidazole, vinylamine, and vinylcyclohexane also produce similar effects.
（ト）発明の詳細
な説明したように本発明によれば、電池の保存中に溶媒
が負極と反応することを抑制することができるので、初
期の放電特性のみならず、保存後の放電特性を改善する
ことができる。この結果、非水系電解液電池の性能を飛
躍的に向−トさせることができ、その工業的価値は極め
て大きい。(g) As described in detail, according to the present invention, it is possible to suppress the solvent from reacting with the negative electrode during storage of the battery, so that it is possible to suppress not only the initial discharge characteristics but also the discharge characteristics after storage. can be improved. As a result, the performance of the non-aqueous electrolyte battery can be dramatically improved, and its industrial value is extremely large.
第１図は本発明電池の縦断面図、第２図は本発明電池Ａ
及び比較電池Ｘにおける初期の放電特性を示す図、第３
図は本発明電池Ａ及び比較電池Ｘにおける保存後の放電
特性を示す図、第４図は本発明電池Ｂ及び比較電池Ｙに
おける初期の放電特性を示す図、第５図は本発明電池Ｂ
及び比Ｉ２を池）′における保存後の放電特性を示す図
、第６図は本発明電池Ｃ及び比較電池Ｚにおける初期の
サイクル特性を示す図、第７図は本発明電池Ｃ及び比Ｖ
ｉ主電池における保存後のサイクル特性を示す図である
。
Ａ、Ｂ、Ｃ・・本発明電池、
ｘ、ｙ、ｚ・・・比較電池、
１ 負極、
２・・負極集電体、
３・・・負極缶、
４・・絶縁バッキング、
５ 正極缶、
６ ・負極集電体、
７ ・負極、
８・・・セパレータ。FIG. 1 is a longitudinal cross-sectional view of a battery of the present invention, and FIG. 2 is a battery A of the present invention.
FIG. 3 shows the initial discharge characteristics of comparative battery X.
The figure shows the discharge characteristics after storage of the battery A of the present invention and the comparative battery
FIG. 6 is a diagram showing the initial cycle characteristics of the invention battery C and comparative battery Z. FIG. 7 is a diagram showing the initial cycle characteristics of the invention battery C and the comparison battery Z.
FIG. 3 is a diagram showing the cycle characteristics of the i-main battery after storage. A, B, C...Battery of the present invention, x, y, z...Comparison battery, 1. Negative electrode, 2.. Negative electrode current collector, 3.. Negative electrode can, 4.. Insulating backing, 5. Positive electrode can. 6 - Negative electrode current collector, 7 - Negative electrode, 8... Separator.
Claims (1)
極と、正極と、溶質と溶媒からなる電解液とを備え、前
記溶媒として、不飽和の炭素−炭素結合を鎖式に有する
ビニルエチレンカーボネート、２−ビニル−１、３−ジ
オキソラン、１、２−ジメトキシエチレン、ジビニルエ
ーテル、Ｎ−ビニルイミダゾール、ビニルアミン、ビニ
ルシクロヘキサンの群から選ばれた少なくとも一つの化
合物からなる溶媒を用いたことを特徴とする非水系電解
液電池。(1) A negative electrode made of lithium or an alloy containing lithium, a positive electrode, and an electrolytic solution made of a solute and a solvent, the solvent being vinyl ethylene carbonate having a chain of unsaturated carbon-carbon bonds; It is characterized by using a solvent consisting of at least one compound selected from the group of 2-vinyl-1,3-dioxolane, 1,2-dimethoxyethylene, divinyl ether, N-vinylimidazole, vinylamine, and vinylcyclohexane. Non-aqueous electrolyte battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2199519A JP2962782B2 (en) | 1990-07-26 | 1990-07-26 | Non-aqueous electrolyte battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2199519A JP2962782B2 (en) | 1990-07-26 | 1990-07-26 | Non-aqueous electrolyte battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0487156A true JPH0487156A (en) | 1992-03-19 |
| JP2962782B2 JP2962782B2 (en) | 1999-10-12 |
Family
ID=16409178
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2199519A Expired - Fee Related JP2962782B2 (en) | 1990-07-26 | 1990-07-26 | Non-aqueous electrolyte battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2962782B2 (en) |
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