JPH05205745A - Organic electrolyte battery - Google Patents
Organic electrolyte batteryInfo
- Publication number
- JPH05205745A JPH05205745A JP3874392A JP3874392A JPH05205745A JP H05205745 A JPH05205745 A JP H05205745A JP 3874392 A JP3874392 A JP 3874392A JP 3874392 A JP3874392 A JP 3874392A JP H05205745 A JPH05205745 A JP H05205745A
- Authority
- JP
- Japan
- Prior art keywords
- battery
- electrolyte
- negative electrode
- positive electrode
- organic solvent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
- H01M6/162—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte
- H01M6/166—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte by the solute
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明はポリアセン系骨格構造を
含有する有機半導体を電極に用いた小型で大容量のコイ
ン型（ボタン型）有機電解質電池に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a small-sized and large-capacity coin-type (button-type) organic electrolyte battery using an organic semiconductor containing a polyacene skeleton structure as an electrode.
【０００２】[0002]
【従来の技術】本願出願人の出願に係る特開昭６０−１
７０１６３号公報にはポリアセン系骨格構造を含有する
有機半導体を正極及び負極とする有機電解質電池が開示
されている。該電池は高容量、長寿命であり、かつ安全
性に優れるという特長を有しているが、コイン型（ボタ
ン型）電池として実用化するに際しては幾多の問題点が
残されていた。特に高温保存（７０℃，２．５Ｖ印加）
後の電気特性、就中、内部抵抗が高温保存前の値と比較
すると大きく増加してしまうという問題があった。2. Description of the Related Art Japanese Patent Application Laid-Open No. 60-1
Japanese Patent No. 70163 discloses an organic electrolyte battery in which an organic semiconductor containing a polyacene skeleton structure is used as a positive electrode and a negative electrode. The battery has the features of high capacity, long life, and excellent safety, but many problems remain when it is put to practical use as a coin-type (button-type) battery. Especially high temperature storage (70 ℃, 2.5V applied)
There was a problem that the electrical characteristics after that, and in particular, the internal resistance was greatly increased as compared with the value before storage at high temperature.
【０００３】[0003]
【発明が解決しようとする課題】本発明者等は上述の問
題点に鑑み鋭意研究を重ねた結果、特定の電解液を用い
ることにより、上記既存技術の問題を解決できることを
見い出し、本発明を完成したものであってその目的とす
るところは、高温保存特性に優れたコイン型（ボタン
型）電池を提供するにある。As a result of intensive studies conducted by the present inventors in view of the above problems, they have found that the problems of the above-mentioned existing techniques can be solved by using a specific electrolytic solution, and the present invention has been made. The purpose of the completed battery is to provide a coin-type (button-type) battery having excellent high-temperature storage characteristics.
【０００４】[0004]
【課題を解決するための手段】本発明の上記目的は、負
極缶とポリアセン系骨格構造を含有する有機半導体から
成る電極と、セパレーターと、正極缶と、有機電解液と
を構成部材として含むコイン型有機電解質電池であっ
て、有機電解液が下記式で示されるテトラアルキルホス
ホニウム塩の有機溶媒溶液であることを特徴とする有機
電解質電池。The above object of the present invention is a coin including a negative electrode can, an electrode made of an organic semiconductor containing a polyacene skeleton structure, a separator, a positive electrode can, and an organic electrolyte as constituent members. Type organic electrolyte battery, wherein the organic electrolytic solution is a solution of a tetraalkylphosphonium salt represented by the following formula in an organic solvent.
【化２】 （ただし、式中Ｒ1 ，Ｒ2 ，Ｒ3 及びＲ4 はアルキル基
を表わし、これらは同一であっても異なっていてもよ
い）により達成される。[Chemical 2] (In the formula, R 1 , R 2 , R 3 and R 4 represent an alkyl group, and these may be the same or different).
【０００５】本発明の電池に供する電解液は上記テトラ
アルキルホスホニウム塩を有機溶媒に溶解した溶液であ
り、各々充分に乾燥、精製した後、調製するのが望まし
い。有機溶媒としては非プロトン性有機溶媒が好まし
く、プロピレンカーボネート、又はプロピレンカーボネ
ートとエチレンカーボネートの混合溶媒を用いると電池
の耐圧を高く設定でき特に好ましい。また電解液は少な
くとも０．５ｍｏｌ／ l以上の濃度で調製され、特に好
ましくは０．８ｍｏｌ／ l〜１．５ｍｏｌ／ lの濃度で
調製される。本発明において重要なことはテトラアルキ
ルホスホニウム塩を電解質に用いることである。テトラ
アルキルホスホニウム塩としては種々のものが適用可能
であるが、テトラエチルホスホニウムテトラフルオロボ
レート〔（Ｃ2 Ｈ5 ）4 ＰＢＦ4 〕が特に好ましい。後
で述べるポリアセン系骨格構造を有する不溶不融性基体
を正極，負極に用いた場合、テトラアルキルホスホニウ
ム塩を電解質に用いるとテトラエチルアンモニウムテト
ラフルオロボレート〔（Ｃ2 Ｈ5 ）ＮＢＦ4 〕を用いた
ときに比し、高温保存後の内部抵抗の上昇が著しく抑止
される。一般にテトラアルキルホスホニウム塩とテトラ
アルキルアンモニウム塩のいずれも耐電圧性が高いと報
告されているが、本発明においてはその理由は定かでは
ないが、テトラアルキルホスホニウム塩を電解液に用い
ることにより上述の問題点を解決するに至ったのであ
る。The electrolytic solution used in the battery of the present invention is a solution of the above-mentioned tetraalkylphosphonium salt dissolved in an organic solvent, and it is desirable to prepare it after sufficiently drying and purifying each. As the organic solvent, an aprotic organic solvent is preferable, and use of propylene carbonate or a mixed solvent of propylene carbonate and ethylene carbonate is particularly preferable because the withstand voltage of the battery can be set high. The electrolytic solution is prepared at a concentration of at least 0.5 mol / l or more, and particularly preferably at a concentration of 0.8 mol / l to 1.5 mol / l. What is important in the present invention is the use of a tetraalkylphosphonium salt in the electrolyte. Although various tetraalkylphosphonium salts can be applied, tetraethylphosphonium tetrafluoroborate [(C 2 H 5 ) 4 PBF 4 ] is particularly preferable. When an insoluble and infusible substrate having a polyacene-based skeleton structure, which will be described later, is used for the positive electrode and the negative electrode, tetraethylphosphonium tetrafluoroborate [(C 2 H 5 ) NBF 4 ] was used when a tetraalkylphosphonium salt was used as the electrolyte. In contrast, the increase in internal resistance after storage at high temperature is significantly suppressed. Generally, it is reported that both the tetraalkylphosphonium salt and the tetraalkylammonium salt have high withstand voltage, but in the present invention, the reason is not clear, but by using the tetraalkylphosphonium salt in the electrolytic solution, It came to solve the problem.
【０００６】本発明の電池の正極及び負極はポリアセン
系骨格構造を含有する有機半導体を含む。該有機半導体
は特開昭６０−１７０１６３号公報に記載される不溶不
融性基体であり、これは芳香族系縮合ポリマーの熱処理
物であって、水素原子／炭素原子の原子比が０．０５〜
０．５、ＢＥＴ法による比表面積が６００ｍ2 ／ｇ以上
であるポリアセン系骨格構造を有する不溶不融性基体で
ある。原料としての芳香族系縮合ポリマーは、例えばフ
ェノール性水酸基を有する芳香族炭化水素化合物とアル
デヒド類との縮合物である。芳香族炭化水素化合物とし
ては、例えばフェノール、クレゾール、キシレノールの
ごときいわゆるフェノール類が好適であるが、これらに
限られない。アルデヒドとしては、ホルムアルデヒド、
アセトアルデヒド、フルフラール等を使用することがで
き、ホルムアルデヒドが好適である。フェノールアルデ
ヒド縮合物としては、ノボラック型又はレゾール型或は
それらの複合物のいずれであってもよい。The positive electrode and the negative electrode of the battery of the present invention include an organic semiconductor containing a polyacene skeleton structure. The organic semiconductor is an insoluble, infusible substrate described in JP-A-60-170163, which is a heat-treated product of an aromatic condensation polymer and has an atomic ratio of hydrogen atoms / carbon atoms of 0.05. ~
0.5, an insoluble and infusible substrate having a polyacene-based skeleton structure having a BET specific surface area of 600 m 2 / g or more. The aromatic condensation polymer as a raw material is, for example, a condensation product of an aromatic hydrocarbon compound having a phenolic hydroxyl group and an aldehyde. Suitable aromatic hydrocarbon compounds include, but are not limited to, so-called phenols such as phenol, cresol, and xylenol. As the aldehyde, formaldehyde,
Acetaldehyde, furfural, etc. can be used, with formaldehyde being preferred. The phenol aldehyde condensate may be a novolac type, a resol type, or a complex thereof.
【０００７】該不溶不融性基体は、上記の如き芳香族系
縮合ポリマーの熱処理物であって例えば次のようにして
製造することができる。前記した芳香族系縮合ポリマー
に塩化亜鉛、リン酸ナトリウム等の無機塩を混合する。
混入する量は、無機塩の種類及び目的とする電極の形
状、性能によって異なるが、重量比で１０／１〜１／７
が好ましい。このようにして得られた無機塩と芳香族系
縮合ポリマーの混合物を、フィルム状、板状等の目的と
する形となし、５０〜１８０℃の温度で２〜９０分間加
熱することにより硬化成形する。かくして得られた硬化
体を、次いで非酸化性雰囲気中で３５０〜８００℃の温
度、好ましくは３５０〜７００℃の温度、特に好ましく
は４００〜６００℃の温度まで加熱する。この熱処理に
よって芳香族系縮合ポリマーは、脱水素脱水反応をおこ
し、芳香環の縮合反応によって、ポリアセン系骨格構造
が形成される。The insoluble and infusible substrate is a heat-treated product of the aromatic condensation polymer as described above and can be produced, for example, as follows. An inorganic salt such as zinc chloride or sodium phosphate is mixed with the aromatic condensation polymer described above.
The amount to be mixed depends on the type of the inorganic salt, the shape and performance of the intended electrode, but the weight ratio is 10/1 to 1/7.
Is preferred. The mixture of the inorganic salt and the aromatic condensation polymer thus obtained is formed into a desired shape such as a film or a plate, and the mixture is cured by heating at a temperature of 50 to 180 ° C. for 2 to 90 minutes. To do. The cured product thus obtained is then heated in a non-oxidizing atmosphere to a temperature of 350 to 800 ° C, preferably 350 to 700 ° C, particularly preferably 400 to 600 ° C. By this heat treatment, the aromatic condensation polymer undergoes a dehydrogenation dehydration reaction, and a polyacene skeleton structure is formed by the condensation reaction of the aromatic ring.
【０００８】この反応は熱縮合重合の一種であり、反応
度は最終生成物の水素原子／炭素原子（以後Ｈ／Ｃと云
う）で表される原子数比によって表わされる。不溶不融
性基体のＨ／Ｃの値は０．０５〜０．５、好ましくは
０．１〜０．３５である。得られた熱処理体を水あるい
は希塩酸等で十分洗浄することによって、熱処理体中に
含まれている無機塩を除去する。その後、これを乾燥す
ると、ＢＥＴ法による比表面積が６００ｍ2 ／ｇ以上の
不溶不融性基体を得る。This reaction is a kind of thermal condensation polymerization, and the degree of reaction is represented by the number ratio of hydrogen atoms / carbon atoms (hereinafter referred to as H / C) in the final product. The H / C value of the insoluble and infusible substrate is 0.05 to 0.5, preferably 0.1 to 0.35. The inorganic salt contained in the heat-treated body is removed by thoroughly washing the obtained heat-treated body with water, diluted hydrochloric acid or the like. Then, this is dried to obtain an insoluble and infusible substrate having a BET specific surface area of 600 m 2 / g or more.
【０００９】本発明のコイン型（ボタン型）有機電解質
電池の実施態様の一例を図１に示す。同図において、１
は負極缶、２は負極、３はセパレーター、４は正極、５
は正極缶、６は絶縁パッキンである。正極缶５と負極缶
１の間は絶縁パッキンが、正極４と負極２の間はセパレ
ーター３が、短絡しない様に配置されており、正極缶５
をかしめることにより、電池を封止している。電解液は
正極４、負極２及びセパレーター３に含ませてある。し
たがってセパレーター３は電解液を含むことができる
様、多孔性ポリプロピレンフィルム、ガラス繊維不織布
等が好ましく用いられる。An example of the embodiment of the coin type (button type) organic electrolyte battery of the present invention is shown in FIG. In the figure, 1
Is a negative electrode can, 2 is a negative electrode, 3 is a separator, 4 is a positive electrode, 5
Is a positive electrode can and 6 is an insulating packing. An insulating packing is arranged between the positive electrode can 5 and the negative electrode can 1 and a separator 3 is arranged between the positive electrode 4 and the negative electrode 2 so as not to short-circuit.
The battery is sealed by caulking. The electrolytic solution is contained in the positive electrode 4, the negative electrode 2 and the separator 3. Therefore, as the separator 3, a porous polypropylene film, a glass fiber nonwoven fabric, or the like is preferably used so that the separator 3 can contain an electrolytic solution.
【００１０】[0010]
【発明の効果】本発明に係るテトラアルキルホスホニウ
ム塩の有機溶媒溶液を電解液として使用することによ
り、特段の高温保存性を有する有機電解質電池が得られ
た。以下実施例により本発明を具体的に説明する。By using the solution of the tetraalkylphosphonium salt according to the present invention in the organic solvent as an electrolytic solution, an organic electrolyte battery having a particular high temperature storability was obtained. The present invention will be specifically described below with reference to examples.
【００１１】[0011]
【実施例】水溶性レゾール（約６０％濃度）／塩化亜鉛
／水を重量比で１０／２５／４の割合で混合した水溶液
をフィルムアプリケーターでガラス板上に成膜した。次
に成膜した水溶液上にガラス板を被せ、水分が蒸発しな
いようにして約１００℃の温度で１時間加熱して硬化さ
せることにより硬化体を得た。該硬化体をシリコニット
電気炉中に入れ窒素気流中で４０℃／時間の速度で昇温
し、５００℃まで熱処理を行い、その後希塩酸、熱水で
十分に洗浄することによりポリアセン系骨格構造を含有
する有機半導体を得た。Example An aqueous solution prepared by mixing water-soluble resol (about 60% concentration) / zinc chloride / water in a weight ratio of 10/25/4 was formed on a glass plate with a film applicator. Next, a glass plate was covered on the formed aqueous solution, and heated at a temperature of about 100 ° C. for 1 hour so as to prevent water from evaporating, and cured to obtain a cured product. The polyacene-based skeleton structure is contained by placing the cured product in a silicon knit electric furnace, heating it at a rate of 40 ° C./hour in a nitrogen stream, performing heat treatment to 500 ° C., and then sufficiently washing it with dilute hydrochloric acid and hot water An organic semiconductor was obtained.
【００１２】該有機半導体の電気伝導度は１０-4（Ωｃ
ｍ）-1であり、元素分析によるＨ／Ｃの値は０．２７、
ＢＥＴ法による比表面積は２１００ｍ2 ／ｇであった。
次に該有機半導体をボールミルを用いて粉砕し、粉末と
し、この粉末にポリ四フッ化エチレン５重量％、カーボ
ンブラック１０重量％を加え、混合、混練した後加圧成
形することにより厚さ０．７ｍｍの電極シートを得た。
該電極シートを１５φｍｍに打抜き正極及び負極とし図
１に示される様な２０２０型（直径２０ｍｍ，厚さ２ｍ
ｍ）のコイン型電池を１０個組立てた。以下の測定値は
１０個の電池について測定した値の平均値である。The electric conductivity of the organic semiconductor is 10 −4 (Ωc).
m) -1 , and the H / C value by elemental analysis is 0.27,
The specific surface area according to the BET method was 2100 m 2 / g.
Next, the organic semiconductor is crushed using a ball mill to obtain a powder, and 5% by weight of polytetrafluoroethylene and 10% by weight of carbon black are added to this powder, and the mixture is mixed and kneaded and then pressure-molded to obtain a thickness of 0. A 0.7 mm electrode sheet was obtained.
The electrode sheet was punched out into a diameter of 15 mm to form a positive electrode and a negative electrode, and a 2020 type (diameter 20 mm, thickness 2 m as shown in FIG.
10 coin-type batteries of m) were assembled. The following measured values are average values of the values measured for 10 batteries.
【００１３】セパレーター３としては、厚さ１００μｍ
のガラス繊維からなる不織布を用いた。また正極缶及び
負極缶はステンレス製である。負極缶１と負極２、正極
４と正極缶５はカーボン系導電性接着剤を用いて接着し
た。電解液として１．０ｍｏｌ／ l （Ｃ2 Ｈ5 ）4 Ｐ
ＢＦ4 プロピレンカーボネート溶液を用い、正極４、セ
パレーター３、負極２に合わせて０．２０ｃｃ注入し
た。The separator 3 has a thickness of 100 μm.
The non-woven fabric made of the glass fiber of was used. The positive electrode can and the negative electrode can are made of stainless steel. The negative electrode can 1 and the negative electrode 2, and the positive electrode 4 and the positive electrode can 5 were bonded using a carbon-based conductive adhesive. 1.0 mol / l (C 2 H 5 ) 4 P as electrolyte
Using a BF 4 propylene carbonate solution, 0.20 cc was injected according to the positive electrode 4, the separator 3 and the negative electrode 2.
【００１４】電極及び各構成部材は十分に乾燥し水分を
除いた後、Ｎ2 ドライボックス中で電池を組立てた。該
電池の作成時の電圧は０Ｖであり１ｋＨｚ時の交流イン
ピーダンスは２．１Ωであった。該電池に、室温で外部
電源により、２．５Ｖの電圧を１時間印加することによ
り電池を充電した。充電後の起電力は２．５Ｖであっ
た。次に２ｍＡで定電流放電を行ったところ、電池の電
圧が０Ｖになるまで１．２４時間を要した。引き続いて
該電池を２．５Ｖの電圧を印加しかつ７０℃の高温下に
１７０時間保存した。保存後電池を室温で２時間ショー
トし電池電圧を０Ｖとした後交流インピーダンスを測定
したところ１１．３Ωであった。After the electrode and each component were thoroughly dried to remove water, the battery was assembled in an N 2 dry box. The voltage at the time of making the battery was 0 V, and the AC impedance at 1 kHz was 2.1Ω. The battery was charged by applying a voltage of 2.5 V to the battery with an external power source at room temperature for 1 hour. The electromotive force after charging was 2.5V. Next, when constant current discharge was performed at 2 mA, it took 1.24 hours until the voltage of the battery reached 0V. Subsequently, the battery was applied with a voltage of 2.5 V and stored at a high temperature of 70 ° C. for 170 hours. After storage, the battery was short-circuited at room temperature for 2 hours, the battery voltage was set to 0 V, and then the AC impedance was measured and found to be 11.3Ω.
【００１５】〔比較例〕電解液に１．０ｍｏｌ／ l
（Ｃ2 Ｈ5 ）4 ＮＢＦ4 のプロピレンカーボネート溶液
を用いる以外は実施例と同様に電池を組立て高温保存特
性を測定した。電池作成時の電池電圧は０Ｖであり１ｋ
Ｈｚ時の交流インピーダンスは２．０Ωであった。また
実施例と同様にして充放電したところ、その放電時間は
１．２６時間であり、初期特性に電解液依存性はなかっ
た。次に実施例と同様の方法で高温保存し、保存後の交
流インピーダンスを測定したところ２６．５Ωであり、
初期に比較して１０倍以上に増大していた。（Ｃ
2Ｈ5 ）4 ＰＢＦ4 を電解質に用いることにより高温保
存特性が大幅に改良されたことがわかる。[Comparative Example] 1.0 mol / l in the electrolytic solution
A battery was assembled in the same manner as in Example except that a propylene carbonate solution of (C 2 H 5 ) 4 NBF 4 was used, and the high temperature storage characteristics were measured. The battery voltage at the time of making the battery is 0V and is 1k
The AC impedance at Hz was 2.0Ω. When the battery was charged and discharged in the same manner as in Example, the discharge time was 1.26 hours and the initial characteristics did not depend on the electrolytic solution. Next, the sample was stored at high temperature in the same manner as in the example and the AC impedance after storage was measured to be 26.5Ω.
It was more than 10 times that of the initial period. (C
It can be seen that the use of 2 H 5 ) 4 PBF 4 as the electrolyte significantly improved the high temperature storage characteristics.
【図１】本発明の実施態様の一例を示すコイン型電池の
説明図である。FIG. 1 is an explanatory diagram of a coin-type battery showing an example of an embodiment of the present invention.
【符号の説明】 １ 負極缶 ２ 負極 ３ セパレーター ４ 正極 ５ 正極缶 ６ 絶縁パッキン[Explanation of reference numerals] 1 negative electrode can 2 negative electrode 3 separator 4 positive electrode 5 positive electrode can 6 insulating packing
Claims (1)
る有機半導体から成る電極と、セパレーターと、正極缶
と、有機電解液とを構成部材として含むコイン型有機電
解質電池であって、有機電解液が下記式で示されるテト
ラアルキルホスホニウム塩の有機溶媒溶液であることを
特徴とする有機電解質電池。 【化１】 （ただし、式中Ｒ1 ，Ｒ2 ，Ｒ3 及びＲ4 はアルキル基
を表わし、これらは同一であっても異なっていてもよ
い）1. A coin-type organic electrolyte battery comprising a negative electrode can, an electrode made of an organic semiconductor containing a polyacene-based skeleton structure, a separator, a positive electrode can, and an organic electrolytic solution as its constituent members. Is an organic solvent solution of a tetraalkylphosphonium salt represented by the following formula: [Chemical 1] (In the formula, R 1 , R 2 , R 3 and R 4 represent an alkyl group, and these may be the same or different)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4038743A JP2619845B2 (en) | 1992-01-28 | 1992-01-28 | Organic electrolyte battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4038743A JP2619845B2 (en) | 1992-01-28 | 1992-01-28 | Organic electrolyte battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05205745A true JPH05205745A (en) | 1993-08-13 |
| JP2619845B2 JP2619845B2 (en) | 1997-06-11 |
Family
ID=12533800
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4038743A Expired - Fee Related JP2619845B2 (en) | 1992-01-28 | 1992-01-28 | Organic electrolyte battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2619845B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007058445A1 (en) | 2005-11-15 | 2007-05-24 | Lg Chem, Ltd. | Electrolyte for lithium secondary battery of improved low-temperature property and secondary battery containing the same |
| EP2929587A4 (en) * | 2012-12-05 | 2016-07-20 | Esionic Corp | Phosphonium ionic liquids, salts, compositions, methods of making and devices formed there from |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02239571A (en) * | 1989-03-14 | 1990-09-21 | Hitachi Maxell Ltd | Battery of organic electrolyte |
-
1992
- 1992-01-28 JP JP4038743A patent/JP2619845B2/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02239571A (en) * | 1989-03-14 | 1990-09-21 | Hitachi Maxell Ltd | Battery of organic electrolyte |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007058445A1 (en) | 2005-11-15 | 2007-05-24 | Lg Chem, Ltd. | Electrolyte for lithium secondary battery of improved low-temperature property and secondary battery containing the same |
| EP1949486A1 (en) * | 2005-11-15 | 2008-07-30 | LG Chem, Ltd. | Electrolyte for lithium secondary battery of improved low-temperature property and secondary battery containing the same |
| EP1949486A4 (en) * | 2005-11-15 | 2010-01-20 | Lg Chemical Ltd | Electrolyte for lithium secondary battery of improved low-temperature property and secondary battery containing the same |
| US8067114B2 (en) | 2005-11-15 | 2011-11-29 | Lg Chem, Ltd. | Electrolyte for lithium secondary battery of improved low-temperature property and secondary battery containing the same |
| EP2929587A4 (en) * | 2012-12-05 | 2016-07-20 | Esionic Corp | Phosphonium ionic liquids, salts, compositions, methods of making and devices formed there from |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2619845B2 (en) | 1997-06-11 |
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