JPH07176322A - Electrolytic solution for li secondary battery - Google Patents
Electrolytic solution for li secondary batteryInfo
- Publication number
- JPH07176322A JPH07176322A JP5346211A JP34621193A JPH07176322A JP H07176322 A JPH07176322 A JP H07176322A JP 5346211 A JP5346211 A JP 5346211A JP 34621193 A JP34621193 A JP 34621193A JP H07176322 A JPH07176322 A JP H07176322A
- Authority
- JP
- Japan
- Prior art keywords
- electrolytic solution
- secondary battery
- battery
- mol
- organic compound
- 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.)
- Pending
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
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、充電電圧の高いＬi二
次電池を形成できる電解液に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrolytic solution capable of forming a Li secondary battery having a high charging voltage.
【０００２】[0002]
【従来の技術】Ｌi二次電池において、高起電力、高放
電容量の点より充電電圧の高いことが望まれるが、従来
の非水溶媒にリチウム塩を溶解させてなる電解液を用い
たＬi二次電池にあっては、電解液の分解防止の点より
４．２Ｖを超える電圧での充電は困難であった。かかる
電解液の分解防止は、充放電の繰返しにおける電解液の
劣化防止、ひいては充放電のサイクル寿命の長期化の点
より重要である。2. Description of the Related Art In a Li secondary battery, it is desired that the charging voltage be high in terms of high electromotive force and high discharge capacity, but Li using an electrolyte solution obtained by dissolving a lithium salt in a conventional non-aqueous solvent In the secondary battery, it was difficult to charge the battery at a voltage exceeding 4.2 V from the viewpoint of preventing decomposition of the electrolytic solution. Preventing the decomposition of the electrolytic solution is important from the viewpoint of preventing deterioration of the electrolytic solution during repeated charging / discharging, and thus extending the cycle life of charging / discharging.
【０００３】[0003]
【発明が解決しようとする課題】本発明は、４．２Ｖを
超える電圧、就中４．５Ｖ程度の高電圧で充電しても分
解を生じない電解液、ひいては起電力、放電容量、充放
電のサイクル寿命に優れるＬi二次電池を形成しうる電
解液の開発を課題とする。DISCLOSURE OF THE INVENTION The present invention provides an electrolytic solution which does not decompose even when charged at a voltage exceeding 4.2 V, especially at a high voltage of about 4.5 V, and by extension, electromotive force, discharge capacity and charge / discharge. The development of an electrolyte solution capable of forming a Li secondary battery having an excellent cycle life of 1.
【０００４】[0004]
【課題を解決するための手段】本発明は、非水溶媒にリ
チウム塩を溶解させた電解液に、シアノ基を２個以上有
する有機化合物を０．００１〜０．１モル／ｌの割合で
添加したことを特徴とするＬi二次電池用電解液を提供
するものである。According to the present invention, an organic compound having two or more cyano groups is added to an electrolytic solution prepared by dissolving a lithium salt in a non-aqueous solvent at a ratio of 0.001 to 0.1 mol / l. An electrolyte solution for a Li secondary battery, which is characterized by being added.
【０００５】[0005]
【作用】シアノ基を２個以上有する有機化合物の添加に
より４．２Ｖを超える電圧での充電にても電解液の分解
を抑制でき、起電力、放電容量、充放電のサイクル寿命
に優れるＬi二次電池の形成が可能となる。その電解液
分解の抑制機構は不明であるが本発明者は、シアノ基の
分極による大きな双極子モーメントが高電圧での充電時
における電解液の酸化分解、つまり電子が引き抜かれる
のを抑制するためであると考えている。By adding an organic compound having two or more cyano groups, it is possible to suppress decomposition of the electrolytic solution even when charged at a voltage exceeding 4.2 V, and to have excellent electromotive force, discharge capacity and charge / discharge cycle life. The next battery can be formed. Although the mechanism for suppressing the decomposition of the electrolytic solution is unknown, the present inventor has a large dipole moment due to polarization of the cyano group to prevent oxidative decomposition of the electrolytic solution during charging at a high voltage, that is, to suppress the extraction of electrons. I think it is.
【０００６】[0006]
【実施例】本発明の電解液は、非水溶媒にリチウム塩を
溶解させた電解液に、シアノ基を２個以上有する有機化
合物を０．００１〜０．１モル／ｌの割合で添加したも
のであり、これはＬi二次電池を形成するためのもので
ある。EXAMPLES The electrolytic solution of the present invention was prepared by adding an organic compound having two or more cyano groups at a rate of 0.001 to 0.1 mol / l to an electrolytic solution prepared by dissolving a lithium salt in a non-aqueous solvent. This is for forming a Li secondary battery.
【０００７】非水溶媒としては、リチウム塩を解離す
る、水でない適宜な溶媒を用いうる。その例としては、
エチレンカーボネート、プロピレンカーボネート、スル
ホラン、γ−ブチロラクトン、ジメチルカーボネート、
ジエチルカーボネート、蟻酸メチル、酢酸メチル、１，
２−ジメトキシエタン、テトラヒドロフラン、２−メチ
ルテトラヒドロフラン等を１種又は２種以上用いたもの
などがあげられる。As the non-aqueous solvent, an appropriate solvent which dissociates a lithium salt and is not water can be used. For example,
Ethylene carbonate, propylene carbonate, sulfolane, γ-butyrolactone, dimethyl carbonate,
Diethyl carbonate, methyl formate, methyl acetate, 1,
2-dimethoxyethane, tetrahydrofuran, 2-methyltetrahydrofuran and the like may be used alone or in combination of two or more.
【０００８】リチウム塩としては、Ｌi（錯）イオンを
解離する適宜なリチウム化合物を用いうる。その例とし
ては、ＬiＰＦ6、ＬiＢＦ4、ＬiＣlＯ4、ＬiＣＦ3Ｓ
Ｏ3、ＬiＡsＦ6、ＬiＡlＣl4、ＬiＩなどがあげられ
る。リチウム塩の使用量は、非水溶媒１リットルあたり
０．１〜３モルが一般的であるが、これに限定されず目
的とする電池性能等に応じて適宜に決定してよい。As the lithium salt, an appropriate lithium compound that dissociates Li (complex) ions can be used. Examples include LiPF 6 , LiBF 4 , LiClO 4 , LiCF 3 S.
O 3 , LiAsF 6 , LiAlCl 4 , LiI and the like can be mentioned. The amount of the lithium salt used is generally 0.1 to 3 mol per liter of the non-aqueous solvent, but is not limited to this and may be appropriately determined depending on the desired battery performance and the like.
【０００９】シアノ基を２個以上有する有機化合物とし
ては、非水溶媒に溶解しうる適宜なものを用いうる。そ
の例としては、１，４−ジシアノブタン、１，４−ジシ
アノ−２−ブテン、サクシノニトリル、１，２−ジシア
ノベンゼン、１，３−ジシアノベンゼン、１，４−ジシ
アノベンゼン、１，２−ジシアノシクロブタン、１，１
−ジシアノエチルアセテート、１，６−ジシアノヘキサ
ン、２，３−ジシアノヒドロキノン、４，５−ジシアノ
イミダゾール、１，５−ジシアノペンタン、２，４−ジ
シアノ−３−メチルグルタアミド、９−ジシアノメチレ
ン−２，４，７−トリニトロフルオレン、２，６−ジシ
アノトルエン、テトラシアノエチレン、テトラシアノエ
チレンオキシド、７，７，８，８−テトラシアノキノジ
メタン、１，１，３，３−テトラシアノプロパンなどが
あげられる。As the organic compound having two or more cyano groups, any suitable organic compound soluble in a non-aqueous solvent can be used. Examples thereof include 1,4-dicyanobutane, 1,4-dicyano-2-butene, succinonitrile, 1,2-dicyanobenzene, 1,3-dicyanobenzene, 1,4-dicyanobenzene, 1,2. -Dicyanocyclobutane, 1,1
-Dicyanoethyl acetate, 1,6-dicyanohexane, 2,3-dicyanohydroquinone, 4,5-dicyanoimidazole, 1,5-dicyanopentane, 2,4-dicyano-3-methylglutamide, 9-dicyanomethylene- 2,4,7-Trinitrofluorene, 2,6-dicyanotoluene, tetracyanoethylene, tetracyanoethylene oxide, 7,7,8,8-tetracyanoquinodimethane, 1,1,3,3-tetracyanopropane And so on.
【００１０】就中、１，４−ジシアノブタン、１，４−
ジシアノ−２−ブテン、サクシノニトリル、１，４−ジ
シアノベンゼン、１，６−ジシアノヘキサン、１，５−
ジシアノペンタン、２，６−ジシアノトルエン、テトラ
シアノエチレン、７，７，８，８−テトラシアノキノジ
メタン、１，１，３，３−テトラシアノプロパンなどが
好ましく用いられる。Among them, 1,4-dicyanobutane, 1,4-
Dicyano-2-butene, succinonitrile, 1,4-dicyanobenzene, 1,6-dicyanohexane, 1,5-
Dicyanopentane, 2,6-dicyanotoluene, tetracyanoethylene, 7,7,8,8-tetracyanoquinodimethane, 1,1,3,3-tetracyanopropane and the like are preferably used.
【００１１】シアノ基を２個以上有する有機化合物は、
１種又は２種以上を添加してよく、添加量は電解液に対
して０．００１〜０．１モル／ｌが適当でありる。その
添加量が０．００１モル／ｌ未満では電解液の分解防止
効果に乏しく、０．１モル／ｌを超えると充放電時の酸
化還元反応が妨げられる。シアノ基を２個以上有する有
機化合物の好ましい添加量は、電解液に対して０．００
５〜０．０５モル／ｌである。The organic compound having two or more cyano groups is
One kind or two or more kinds may be added, and the addition amount is appropriately 0.001 to 0.1 mol / l with respect to the electrolytic solution. If the amount added is less than 0.001 mol / l, the effect of preventing decomposition of the electrolytic solution is poor, and if it exceeds 0.1 mol / l, the redox reaction during charge / discharge is hindered. The preferable addition amount of the organic compound having two or more cyano groups is 0.00 with respect to the electrolytic solution.
It is 5 to 0.05 mol / l.
【００１２】電解液の形成は、非水溶媒にリチウム塩と
シアノ基を２個以上有する有機化合物を所定の割合で溶
解させることにより行うことができる。その場合、必要
に応じ２−メチルフラン、チオフェン、ピロール、クラ
ウンエーテル等のデンドライトの成長を抑制するための
有機添加物などを添加することもできる。The electrolyte solution can be formed by dissolving a lithium salt and an organic compound having two or more cyano groups in a non-aqueous solvent at a predetermined ratio. In that case, if necessary, organic additives such as 2-methylfuran, thiophene, pyrrole, and crown ether for suppressing the growth of dendrites can be added.
【００１３】本発明の電解液は、Ｌi二次電池を形成す
るためのものであるが、形成するＬi二次電池について
はかかる電解液を用いる点を除いて特に限定はない。従
って正極や負極等の形成材について特に限定はないし、
また電池形態等についても特に限定はない。電解液は、
形成目的の電池形態等に応じてそのまま用いる方式や、
支持体に保持させた方式などの適宜な方式で用いること
ができる。The electrolytic solution of the present invention is for forming a Li secondary battery, but the Li secondary battery to be formed is not particularly limited except that such an electrolytic solution is used. Therefore, there is no particular limitation on the forming material such as the positive electrode and the negative electrode,
Further, there is no particular limitation on the battery form or the like. The electrolyte is
A method that is used as it is according to the form of the battery for which it is formed,
It can be used in an appropriate method such as a method of holding it on a support.
【００１４】ちなみに正極としては、例えばＭｎＯ2、
ＬｉＣｏＯ2、ＬiwＣo1-x-yＭxＰyＯ2+z（ただし、Ｍは
１種又は２種以上の遷移金属、ｗは０＜ｗ≦２、ｘは０
≦ｘ＜１、ｙは０＜ｙ＜１、ｚは−１≦ｚ≦４であ
る。）、あるいはＬiないしＬi・Ｃoのリン酸塩及び／
又はＣoないしＬi・Ｃoの酸化物を成分として１モルの
Ｌiあたり０．１モル以上のＣoと０．２モル以上のＰを
含有するもの等を活物質とするものなどがあげられる。Incidentally, as the positive electrode, for example, MnO 2 ,
LiCoO 2 , Li w Co 1-xy M x P y O 2 + z (where M is one or more transition metals, w is 0 <w ≦ 2, and x is 0).
≦ x <1, y is 0 <y <1, and z is −1 ≦ z ≦ 4. ), Or Li or Li · Co phosphate and /
Alternatively, the active material may be, for example, an oxide containing Co or Li · Co and containing 0.1 mol or more of Co and 0.2 mol or more of P per 1 mol of Li as an active material.
【００１５】また負極としては、例えばリチウムやリチ
ウム合金などからなるものがあげられる。そのリチウム
合金としては、例えばＬiとＡl、Ｍg、Ｐb、Ｓn、Ｉn、
Ｂi、Ａg、Ｂａ、Ｃａ、Ｈg、Ｐd、Ｐt、Ｓr等の金属や
Ｃとの２元又は３元以上の適宜な合金を用いることがで
きる。また必要に応じてＳi、Ｃd、Ｚn、Ｌa等を添加し
たものなどや、ＬiとＰbの合金にＬa等を添加して機械
的特性を改善したものなども用いうる。The negative electrode may be made of lithium or a lithium alloy. Examples of the lithium alloy include Li and Al, Mg, Pb, Sn, In,
Appropriate binary or ternary alloys with metals such as Bi, Ag, Ba, Ca, Hg, Pd, Pt, and Sr, and C can be used. If necessary, Si, Cd, Zn, La or the like may be added, or an alloy of Li and Pb may be added with La or the like to improve mechanical properties.
【００１６】さらにコイン型やボタン型の電池、あるい
はテープ状物の正・負極を巻回した形態の電池などを形
成する場合に、正・負極間に介在させるセパレータの形
成も例えばポリプロピレン等からなる多孔性ポリマーフ
ィルムや不織布、ガラスフィルター、あるいはゲル状物
質等に電解液を含浸させたり、充填する方式などの従来
に準じた適宜な方式で行うことができる。Further, when forming a coin-type or button-type battery, or a battery in which positive and negative electrodes are wound with a tape-like material, the separator interposed between the positive and negative electrodes is also made of polypropylene or the like. It can be carried out by an appropriate method according to a conventional method such as a method of impregnating or filling an electrolytic solution into a porous polymer film, a non-woven fabric, a glass filter, a gel-like substance or the like.
【００１７】なおテープ状の正・負極は、例えば活物質
を必要に応じてアセチレンブラックやケッチェンブラッ
ク等の導電材料及びポリテトラフルオロエチレンやポリ
エチレン、ポリオレフィンオキシドやポリビニルアルコ
ール、あるいは固体電解質等の結着剤と共にキャスティ
ング方式や圧縮成形方式、ロール成形方式、ドクターブ
レード方式などの適宜な方式で成形する方式などにより
形成することができる。またかかる正・負極を、集電体
テープに半田付け、ろう付け、超音波溶接、スポット溶
接、バインダ樹脂による塗布付着等の適宜な方式で接着
して用いることもできる。The tape-shaped positive and negative electrodes may be made of a conductive material such as acetylene black or Ketjen black, and a binder such as polytetrafluoroethylene, polyethylene, polyolefin oxide or polyvinyl alcohol, or a solid electrolyte, if necessary. It can be formed by an appropriate method such as a casting method, a compression molding method, a roll molding method, a doctor blade method and the like together with the binder. The positive and negative electrodes may be bonded to a current collector tape by an appropriate method such as soldering, brazing, ultrasonic welding, spot welding, coating with a binder resin, or the like.
【００１８】前記の集電体テープとしては、例えば銅、
アルミニウム、銀、ニッケルなどの導電性テープが用い
られる。かかる集電体テープは、例えばニッケルや鉄な
どのリチウムと反応しにくい導体又は／及び銀、銅、亜
鉛、マグネシウム、アルミニウム、カルシウム、バリウ
ム、ビスマス、インジウム、鉛、白金、パラジウム、ス
ズなどの液体リチウムと親和性の導体で被覆されていて
もよい。Examples of the current collector tape include copper,
A conductive tape made of aluminum, silver, nickel or the like is used. Such a current collector tape is, for example, a conductor that is difficult to react with lithium such as nickel or iron or / and a liquid such as silver, copper, zinc, magnesium, aluminum, calcium, barium, bismuth, indium, lead, platinum, palladium, tin. It may be covered with a conductor having an affinity with lithium.
【００１９】形成したＬi二次電池に対する充電は、一
定電流を連続して通電する方式やパルス電源を用いてパ
ルス電流を供給する方式などの適宜な方式にて行うこと
ができる。パルス電流による充電方式では、通電・停止
が繰り返されるため濃度変化が抑制されてデンドライト
がより成長しにくい利点がある。The Li secondary battery thus formed can be charged by an appropriate method such as a method of continuously supplying a constant current or a method of supplying a pulse current using a pulse power source. The charging method using a pulse current has the advantage that dendrites are more difficult to grow because the concentration change is suppressed because energization / stopping is repeated.
【００２０】実施例１ 蒸留精製したエチレンカーボネートとジメチルカーボネ
ートの５０／５０（体積比）混合溶媒に８０℃で２４時
間真空乾燥処理したＬiＢＦ4を１モル／ｌの濃度で溶解
させ、その溶液に１，４−ジシアノ−２−ブテンを０．
０１モル／ｌの割合で添加して電解液を得た。なおこの
電解液の含水量は、カールフィッシャー水分計による測
定で２０ppm以下であった。Example 1 LiBF 4 vacuum-dried at 80 ° C. for 24 hours in a 50/50 (volume ratio) mixed solvent of distilled and purified ethylene carbonate and dimethyl carbonate was dissolved at a concentration of 1 mol / l, and the solution was dissolved in the solution. 1,4-dicyano-2-butene was added to 0.
An electrolyte solution was obtained by adding at a ratio of 01 mol / l. The water content of this electrolytic solution was 20 ppm or less as measured by a Karl Fischer moisture meter.
【００２１】実施例２ １，４−ジシアノ−２−ブテンに代えてサクシノニトリ
ルを０．０１モル／ｌの割合で添加したほかは実施例１
に準じて電解液を得た。Example 2 Example 1 was repeated except that succinonitrile was added at a rate of 0.01 mol / l in place of 1,4-dicyano-2-butene.
An electrolytic solution was obtained according to.
【００２２】比較例１ １，４−ジシアノ−２−ブテンを添加しないほかは実施
例１に準じて電解液を得た。Comparative Example 1 An electrolytic solution was obtained in the same manner as in Example 1 except that 1,4-dicyano-2-butene was not added.
【００２３】比較例２ １，４−ジシアノ−２−ブテンの添加割合を０．０００
１モル／ｌとしたほかは実施例１に準じて電解液を得
た。Comparative Example 2 The addition ratio of 1,4-dicyano-2-butene was 0.000.
An electrolytic solution was obtained in the same manner as in Example 1 except that the amount was 1 mol / l.
【００２４】比較例３ １，４−ジシアノ−２−ブテンの添加割合を１モル／ｌ
としたほかは実施例１に準じて電解液を得た。Comparative Example 3 The addition ratio of 1,4-dicyano-2-butene was 1 mol / l.
An electrolytic solution was obtained in the same manner as in Example 1 except that.
【００２５】比較例４ １，４−ジシアノ−２−ブテンに代えてシアノ基が１個
のクロトノニトリルを０．０１モル／ｌの割合で添加し
たほかは実施例１に準じて電解液を得た。Comparative Example 4 An electrolytic solution was prepared in the same manner as in Example 1 except that crotononitrile having one cyano group was added at a rate of 0.01 mol / l in place of 1,4-dicyano-2-butene. Obtained.
【００２６】評価試験 実施例、比較例で得た電解液を厚さ及び直径が２５μm
の多孔性ポリプロピレンフィルムに含浸させてセパレー
タを形成し、そのセパレータの上下に正極と負極を配置
してコイン型のＬi二次電池セルを形成し、それに充放
電電流０．５ｍＡ、充電電圧４．５Ｖ、放電電圧２．７
５Ｖの条件で充放電を繰り返してサイクル特性を調べ
た。前記の結果を表１に示した。なお表１では、実施例
１の場合の１サイクル目を１００とし、これを基準に他
の場合を評価した。Evaluation Tests The electrolytic solutions obtained in the examples and comparative examples were prepared to have a thickness and diameter of 25 μm.
3. A porous polypropylene film was impregnated to form a separator, and a positive electrode and a negative electrode were arranged above and below the separator to form a coin-type Li secondary battery cell, on which a charge / discharge current of 0.5 mA and a charge voltage of 4. 5V, discharge voltage 2.7
The charge and discharge were repeated under the condition of 5 V to examine the cycle characteristics. The results are shown in Table 1. In Table 1, the first cycle of Example 1 was set to 100, and other cases were evaluated based on this.
【００２７】なお前記において正極は、炭酸リチウムと
塩基性炭酸コバルトとリン酸含有率８５％のリン酸水溶
液をＬi：Ｃo：Ｐ＝１：０．５：０．５の原子比で混合
し、それをアルミナ製坩堝に入れて９００℃で２４時間
加熱処理し、リチウムのリン酸塩とリチウム・コバルト
のリン酸塩とコバルト酸化物の混合物（活物質）を形成
し、それをボールミルで粉砕して粒径２０μm以下の粉
末とし、その粉末８重量部、アセチレンブラック１重量
部及びポリフッ化ビニリデン１重量部を混合してその１
００ｍｇをニッケルメッシュ上にプレス成形し、直径２
０mmの円板状正極としたものであり、負極は厚さ０．２
mmの金属リチウムシートを直径２０mmに打ち抜きその片
面にニッケルメッシュを圧着して円板状負極としたもの
である。In the above positive electrode, lithium carbonate, basic cobalt carbonate and an aqueous phosphoric acid solution having a phosphoric acid content of 85% are mixed at an atomic ratio of Li: Co: P = 1: 0.5: 0.5, It is put in an alumina crucible and heat-treated at 900 ° C. for 24 hours to form a mixture of lithium phosphate, lithium cobalt phosphate and cobalt oxide (active material), which is crushed by a ball mill. Powder having a particle size of 20 μm or less, and mixed with 8 parts by weight of the powder, 1 part by weight of acetylene black and 1 part by weight of polyvinylidene fluoride
Press molding of 00mg onto nickel mesh, diameter 2
It is a disk-shaped positive electrode with a thickness of 0 mm, and the negative electrode has a thickness of 0.2.
A metal lithium sheet having a diameter of 20 mm is punched out to have a diameter of 20 mm, and a nickel mesh is press-bonded to one surface of the sheet to form a disk-shaped negative electrode.
【００２８】[0028]
【表１】 [Table 1]
【００２９】[0029]
【発明の効果】本発明によれば、分解しにくい電解液が
得られて４．２Ｖを超える高電圧で安定に充電すること
ができ、起電力、放電容量、充放電のサイクル寿命に優
れるＬi二次電池を形成することができる。EFFECTS OF THE INVENTION According to the present invention, an electrolyte solution which is difficult to decompose can be obtained and can be stably charged at a high voltage exceeding 4.2 V, and it is excellent in electromotive force, discharge capacity and charge / discharge cycle life. A secondary battery can be formed.
Claims (1)
液に、シアノ基を２個以上有する有機化合物を０．００
１〜０．１モル／ｌの割合で添加したことを特徴とする
Ｌi二次電池用電解液。1. An organic compound having two or more cyano groups is added to an electrolytic solution prepared by dissolving a lithium salt in a non-aqueous solvent in an amount of 0.001.
An electrolytic solution for a Li secondary battery, which is added at a ratio of 1 to 0.1 mol / l.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5346211A JPH07176322A (en) | 1993-12-21 | 1993-12-21 | Electrolytic solution for li secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5346211A JPH07176322A (en) | 1993-12-21 | 1993-12-21 | Electrolytic solution for li secondary battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH07176322A true JPH07176322A (en) | 1995-07-14 |
Family
ID=18381864
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5346211A Pending JPH07176322A (en) | 1993-12-21 | 1993-12-21 | Electrolytic solution for li secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07176322A (en) |
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| US11424482B2 (en) | 2013-02-27 | 2022-08-23 | Mitsubishi Chemical Corporation | Nonaqueous electrolyte solution and nonaqueous electrolyte battery using same |
| US9666905B2 (en) | 2013-03-04 | 2017-05-30 | Daikin Industries, Ltd. | Electrolytic solution, electrochemical device, lithium ion secondary battery, and module |
| JP2014216317A (en) * | 2013-04-25 | 2014-11-17 | 三星エスディアイ株式会社Ｓａｍｓｕｎｇ ＳＤＩ Ｃｏ．，Ｌｔｄ． | Additive for electrolyte of lithium battery, organic electrolytic solution, and lithium battery |
| KR20140127741A (en) * | 2013-04-25 | 2014-11-04 | 삼성에스디아이 주식회사 | Additive for electrolyte of lithium battery, organic electrolytic solution comprising the same and Lithium battery using the solution |
| US10243242B2 (en) | 2013-12-20 | 2019-03-26 | Daikin Industries, Ltd. | Electrolytic solution, electrochemical device, lithium-ion secondary cell, and module |
| US10062926B2 (en) | 2014-03-27 | 2018-08-28 | Daikin Industries, Ltd. | Electrolyte solution, electrochemical device, lithium ion secondary battery, and module |
| US10424813B2 (en) | 2015-03-16 | 2019-09-24 | Mitsubishi Chemical Corporation | Non-aqueous electrolyte solution and non-aqueous electrolyte secondary battery using same |
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| US10680233B2 (en) * | 2016-11-15 | 2020-06-09 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | Method for manufacturing an electrode for an accumulator |
| US10686174B2 (en) | 2016-11-15 | 2020-06-16 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | Method for manufacturing a separating membrane for an accumulator |
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