JPH08287949A - Lithium-polymer battery and its manufacture - Google Patents
Lithium-polymer battery and its manufactureInfo
- Publication number
- JPH08287949A JPH08287949A JP7082233A JP8223395A JPH08287949A JP H08287949 A JPH08287949 A JP H08287949A JP 7082233 A JP7082233 A JP 7082233A JP 8223395 A JP8223395 A JP 8223395A JP H08287949 A JPH08287949 A JP H08287949A
- Authority
- JP
- Japan
- Prior art keywords
- positive electrode
- cyclic ether
- polymer battery
- lithium polymer
- 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.)
- 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
Landscapes
- Primary Cells (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明はポリマー電解質を用いる
リチウム・ポリマー電池に関するものである。FIELD OF THE INVENTION The present invention relates to a lithium polymer battery using a polymer electrolyte.
【０００２】[0002]
【従来の技術】電池用電解質へのポリマー材料の導入
は、ポリマーの軽量、形状柔軟性、薄膜形成可能という
特徴に加え、固体としての機能が活かせるため、高信頼
性電池の製造を可能にする。特に、金属リチウムを負極
に用いるリチウム・ポリマー二次電池の場合、液体電解
質使用時に問題となるリチウムデンドライト析出が抑制
されるため、内部短絡による発熱・発火が起こらず十分
な安全性の確保が可能となる。2. Description of the Related Art Introducing a polymer material into a battery electrolyte makes it possible to manufacture a highly reliable battery because the polymer functions as a solid in addition to the features such as light weight, shape flexibility and thin film formation. To do. In particular, in the case of a lithium polymer secondary battery that uses metallic lithium for the negative electrode, lithium dendrite deposition, which is a problem when using a liquid electrolyte, is suppressed, so heat generation and ignition due to internal short circuit do not occur and sufficient safety can be secured. Becomes
【０００３】上記リチウム・ポリマー二次電池に使用さ
れるポリマー電解質は、通常の電池系におけるセパレー
タの役割も果たす。さらに、液体電解質と同様にイオン
を輸送し、電極内の活物質と接触して電気化学界面を形
成する。しかし、ポリマー電解質は通常流動性のない固
体であり、これを外部から正極内部へ浸透させることは
不可能である。従って、あらかじめその内部にポリマー
電解質を含有させた複合正極を作製し、良好な界面形成
を図る必要がある。The polymer electrolyte used in the above lithium polymer secondary battery also functions as a separator in an ordinary battery system. Further, like the liquid electrolyte, it transports ions and makes contact with the active material in the electrode to form an electrochemical interface. However, the polymer electrolyte is usually a non-flowable solid, and it is impossible to penetrate this into the positive electrode from the outside. Therefore, it is necessary to prepare a composite positive electrode having a polymer electrolyte contained therein in advance to achieve good interface formation.
【０００４】複合正極は、例えば特公昭６３−３４２２
号公報記載の以下の方法で作製される。まず、活物質で
ある硫化チタン７５重量％、導電剤であるグラファイト
粉末１０重量％、ポリマー電解質であるポリエチレンオ
キシドとヨウ化ナトリウムの錯体１５重量％を、メタノ
ールもしくはアセトニトリルに懸濁した液を調整する。
次いで、この懸濁液を、ポリテトラフルオロエチレンシ
ートの上に流し、有機溶媒を蒸発させることによりシー
ト状の複合正極が得られる。本正極中にはポリマー電解
質が均一に分散しており、活物質と良好な電気化学界面
を形成している。The composite positive electrode is, for example, Japanese Patent Publication No. 63-3422.
It is produced by the following method described in the publication. First, a solution is prepared by suspending 75% by weight of titanium sulfide as an active material, 10% by weight of graphite powder as a conductive agent, and 15% by weight of a complex of polyethylene oxide and sodium iodide as a polymer electrolyte in methanol or acetonitrile. .
Next, this suspension is poured onto a polytetrafluoroethylene sheet, and the organic solvent is evaporated to obtain a sheet-shaped composite positive electrode. The polymer electrolyte is uniformly dispersed in the positive electrode and forms a good electrochemical interface with the active material.
【０００５】[0005]
【発明が解決しようとする課題】通常の有機電解液系電
池の場合、活物質、導電剤および結着剤からなる混合粉
体を加圧成型した正極を使用し、その内部に微細に形成
された隙間に電解液が浸透して活物質との電気化学界面
を形成する。このとき各粒子は密接に接触して電子伝導
のパスを保持するため、正極内部での電子伝導に基づく
インピーダンスは小さい。In the case of an ordinary organic electrolyte type battery, a positive electrode obtained by pressure molding a mixed powder consisting of an active material, a conductive agent and a binder is used, and finely formed inside the positive electrode. The electrolytic solution penetrates into the gap to form an electrochemical interface with the active material. At this time, the particles are in intimate contact with each other and hold an electron conduction path, so that the impedance due to electron conduction inside the positive electrode is small.
【０００６】しかし、ポリマー電解質複合正極の場合、
粒子間に電解質が存在しやすく、そのため粒子間の伝導
性が劣りインピーダンスは前記の正極に比べて大きく、
電池作動時のＩＲ損増大の要因となる。インピーダンス
を低減させるためには導電剤の増加が必要であるが、そ
の増加分、正極中の活物質量が減少し、結果として正極
容量の低下を招く。However, in the case of the polymer electrolyte composite positive electrode,
Electrolyte is likely to exist between particles, so conductivity between particles is poor and impedance is larger than that of the positive electrode,
This causes an increase in IR loss when the battery is operating. In order to reduce the impedance, it is necessary to increase the conductive agent, but the amount of the active material in the positive electrode decreases by the increase, and as a result, the positive electrode capacity decreases.
【０００７】以上のように、電池特性の向上という観点
から判断すると、従来の複合正極は必ずしも適切な構造
を有しているとはいえず、低インピーダンスで高容量の
複合正極の出現が待たれていた。本発明は、このような
課題を解決するものであり、新規のリチウム・ポリマー
電池を提案することを目的とする。As described above, from the viewpoint of improving the battery characteristics, it cannot be said that the conventional composite positive electrode has an appropriate structure, and the appearance of a composite positive electrode with low impedance and high capacity is awaited. Was there. The present invention solves such a problem, and an object thereof is to propose a novel lithium polymer battery.
【０００８】[0008]
【課題を解決するための手段】前記の問題を解決するた
めに、本発明では環状エーテルの重合体からなるポリマ
ー電解質を利用する。In order to solve the above problems, the present invention utilizes a polymer electrolyte composed of a polymer of cyclic ether.
【０００９】本電解質は環状エーテルの開環重合によっ
て得られたポリマーを基本骨格とする固体電解質であ
り、重合前の電解質は少なくとも環状エーテルに支持塩
が溶解した通常の有機電解液である。この液体を正極に
注液し、次いでこれを化学的手法あるいは電気化学的手
法で重合硬化することでポリマー電解質複合正極が得ら
れる。The present electrolyte is a solid electrolyte having a polymer as a basic skeleton obtained by ring-opening polymerization of cyclic ether, and the electrolyte before polymerization is a normal organic electrolyte solution in which at least a supporting salt is dissolved in cyclic ether. A polymer electrolyte composite positive electrode is obtained by injecting this liquid into the positive electrode and then polymerizing and curing the liquid by a chemical method or an electrochemical method.
【００１０】前記の手段により、低インピーダンスかつ
高容量の複合正極が製造可能となり、より高性能のリチ
ウム・ポリマー電池の開発が促進される。By the means described above, a composite positive electrode having a low impedance and a high capacity can be manufactured, and the development of a higher performance lithium polymer battery is promoted.
【００１１】[0011]
【作用】重合前の電解質は粘性の低い液体であり、減圧
含浸処理によって正極内部に注入することができる。注
入された液体は、以下に記す２つのいずれかの方法で重
合硬化して、正極と複合化させる。The electrolyte before polymerization is a liquid having a low viscosity and can be injected into the positive electrode by the impregnation treatment under reduced pressure. The injected liquid is polymerized and cured by one of the two methods described below to form a composite with the positive electrode.
【００１２】（１）化学的手法による電解質の重合硬化 ジオキソランのような環状エーテルに、３フッ化ホウ素
ジエチルエーテル錯体ＢＦ3・Ｏ（Ｃ2Ｈ5）2のような酸
触媒を添加すると、環状エーテルが開環重合してポリエ
ーテルが得られる。(1) Polymerization and curing of electrolyte by chemical method When a cyclic ether such as dioxolane is added with an acid catalyst such as boron trifluoride diethyl ether complex BF 3 .O (C 2 H 5 ) 2 , Ring-opening polymerization of ether gives polyether.
【００１３】重合機構は以下の通りである。まず、ジオ
キソラン分子中で電子リッチな酸素ＯにカチオンＣ2Ｈ5
+が攻撃し、対アニオン-ＢＦ3ＯＣ2Ｈ5と錯体を形成す
る（化１）。The polymerization mechanism is as follows. First, cation C 2 H 5 is added to oxygen-rich oxygen O in the dioxolane molecule.
+ Attacks and forms a complex with the counter anion - BF 3 OC 2 H 5 (chemical formula 1).
【００１４】[0014]
【化１】 Embedded image
【００１５】錯体中のＯ+は近傍のＣ−Ｏ結合から電子
を奪うため、結合が切断されて開環反応が起こる。そし
て、末端に生起したカチオンが新たなジオキソランと結
合して、再び錯体を形成する（化２）。Since O + in the complex robs an electron from a nearby C—O bond, the bond is broken and a ring-opening reaction occurs. Then, the cation generated at the terminal is combined with a new dioxolane to form a complex again (Chemical Formula 2).
【００１６】[0016]
【化２】 Embedded image
【００１７】以上の反応が連鎖的に進行して、ポリエー
テルが成長する（化３）。The above reaction proceeds in a chain to grow polyether (Chemical Formula 3).
【００１８】[0018]
【化３】 Embedded image
【００１９】ここで、酸触媒の添加前にあらかじめリチ
ウム塩を溶解しておけば、ポリマーエーテルにリチウム
塩が分散・解離したポリマー電解質が得られる。If the lithium salt is dissolved in advance before the addition of the acid catalyst, a polymer electrolyte in which the lithium salt is dispersed / dissociated in the polymer ether can be obtained.
【００２０】重合反応は瞬時には完了しないので、酸触
媒を添加した直後であれば、前記液体を正極内部に注液
することができ、複合正極が作製可能となる。Since the polymerization reaction is not completed instantaneously, the liquid can be poured into the positive electrode immediately after the acid catalyst is added, and the composite positive electrode can be manufactured.
【００２１】（２）電気化学的手法による電解質の重合
硬化 ジオキソランのような環状エーテルにホウフッ化リチウ
ムＬｉＢＦ4のようなリチウム塩を溶解した液体を電気
化学的に分解すると、アノード上にポリマー電解質が得
られる。(2) Polymerization and curing of electrolyte by electrochemical method When a liquid obtained by dissolving a lithium salt such as lithium borofluoride LiBF 4 in a cyclic ether such as dioxolane is electrochemically decomposed, a polymer electrolyte is formed on the anode. can get.
【００２２】重合前の前記液体は、Ｌｉ+とＢＦ4 -の２
つのイオンが解離した非水電解液であるが、この液体に
リチウム対極基準で５Ｖ程度の高電圧を印加すると、正
極上でＢＦ4 -が酸化分解してＢＦ3を生成する。ルイス
酸であるＢＦ3は前記（１）化学的手法による電解質の
重合硬化の場合と同様に環状エーテルの開環重合を促進
するので、ポリエーテルが得られ正極と複合化する。[0022] The liquid prior polymerization, Li + and BF 4 - 2
Although this is a non-aqueous electrolytic solution in which two ions are dissociated, when a high voltage of about 5 V based on the lithium counter electrode is applied to this liquid, BF 4 − is oxidized and decomposed on the positive electrode to generate BF 3 . BF 3, which is a Lewis acid, promotes ring-opening polymerization of a cyclic ether in the same manner as in the case of (1) polymerization and curing of an electrolyte by the chemical method described above, and thus a polyether is obtained to form a composite with a positive electrode.
【００２３】前記の方法は、（１）の方法と比べて、重
合開始の時期を電圧印加で制御できるという利点を有す
る。The above method has an advantage over the method (1) in that the timing of initiation of polymerization can be controlled by applying a voltage.
【００２４】[0024]
【実施例】以下、本発明の実施例を説明する。Embodiments of the present invention will be described below.
【００２５】（実施例１）図１に本発明により製造され
るポリマー電解質複合正極の縦断面図を示す。図におい
て、１は活物質であるＶ6Ｏ13+y（０≦ｙ≦０．１６）
１００重量％と導電剤であるアセチレンブラック３重量
％と結着剤であるポリテトラフルオロエチレン７重量％
からなる混合粉体を加圧成形した正極である。Example 1 FIG. 1 shows a vertical cross-sectional view of a polymer electrolyte composite positive electrode manufactured by the present invention. In the figure, 1 is an active material V 6 O 13 + y (0 ≦ y ≦ 0.16)
100% by weight, acetylene black 3% by weight as a conductive agent, and polytetrafluoroethylene 7% by weight as a binder
Is a positive electrode obtained by pressure molding a mixed powder of.
【００２６】２は、正極中の微細な空孔に充填されたポ
リマー電解質である。本電解質は、環状エーテルである
ジオキソランを溶媒とし、リチウム塩であるＬｉＢＦ4
を溶質とする液体を、化学的あるいは電気化学的手法に
より重合硬化して得られた固体電解質である。ここで、
ＬｉＢＦ4濃度は１モル／リットルである。電解質の重
合は、重合前の前記液体を正極の細孔内に減圧含浸した
後に行い、以下２つのいずれかの方法に従った。Reference numeral 2 is a polymer electrolyte filled in fine pores in the positive electrode. This electrolyte uses dioxolane which is a cyclic ether as a solvent and LiBF 4 which is a lithium salt.
It is a solid electrolyte obtained by polymerizing and curing a liquid containing solute as a solute by a chemical or electrochemical method. here,
The LiBF 4 concentration is 1 mol / liter. Polymerization of the electrolyte was performed after impregnating the pores of the positive electrode with the liquid before polymerization under reduced pressure, and either of the following two methods was performed.
【００２７】（１）重合前の前記液体に、酸触媒である
ＢＦ3・Ｏ（Ｃ2Ｈ5）2を０．１〜１重量％溶解して、直
後にこの溶液を正極に減圧注入する。次いで、この正極
を−１０℃で２４時間乾燥空気中に放置すると、電解質
が重合硬化して図１記載の複合正極が得られる。(1) 0.1 to 1% by weight of BF 3 .O (C 2 H 5 ) 2 which is an acid catalyst is dissolved in the liquid before polymerization, and immediately after that, this solution is injected under reduced pressure into the positive electrode. . Next, when this positive electrode is left in dry air at -10 ° C for 24 hours, the electrolyte is polymerized and cured to obtain the composite positive electrode shown in Fig. 1.
【００２８】（２）前記液体が注液された正極を作用極
とし、対極にリチウム金属、参照極にＬｉ／Ｌｉ+を用
いた電気化学セルをセットする。次いで、この正極を５
Ｖｖｓ．Ｌｉ／Ｌｉ+の一定電位で１時間保持すると、
注液された液体が重合硬化して図１記載の正極が得られ
る。(2) An electrochemical cell using the positive electrode into which the liquid is injected as a working electrode, lithium metal as a counter electrode, and Li / Li + as a reference electrode is set. Then, this positive electrode
Vvs. Holding at a constant potential of Li / Li + for 1 hour,
The injected liquid is polymerized and cured to obtain the positive electrode shown in FIG.
【００２９】本実施例では（２）の方法を採用し、複合
正極を作製した。得られた正極を、ポリマー電解質とリ
チウム負極と組み合わせ、図２記載のリチウム・ポリマ
ー二次電池を構成した。図において３は図１で示したポ
リマー電解質複合正極である。In this example, the method (2) was adopted to produce a composite positive electrode. The obtained positive electrode was combined with a polymer electrolyte and a lithium negative electrode to form a lithium polymer secondary battery shown in FIG. In the figure, 3 is the polymer electrolyte composite positive electrode shown in FIG.
【００３０】４はポリマー電解質層である。本電解質
は、紫外線硬化性モノマーと光重合開始剤と非水電解液
を含む液体に紫外線を照射して得たゲル電解質である。
まず、前記液体を３の複合正極上に２５〜５０μｍの厚
さで塗布する。次いで、これに最大出力波長３６５ｎｍ
の紫外線を不活性雰囲気下で３分間照射する。このとき
前記モノマーが重合硬化して、非水電解液を含んだ薄膜
のゲル電解質が得られる。この電解質はポリマー電解質
複合正極３と密着して固体状の半電池となる。ここで非
水電解液にはジオキソランにＬｉＢＦ4を１モル／リッ
トル溶解したものを用いた。また、紫外線硬化性モノマ
ーにはポリエチレンオキシドジアクリレートを用い、光
重合開始剤にはベンジルジメチルケタールを用いた。こ
こで用いる液体中のポリエチレンオキシドジアクリレー
トの含量は５〜５０重量％であり、ベンジルジメチルケ
タールの含量は０．１〜５重量％である。Reference numeral 4 is a polymer electrolyte layer. The present electrolyte is a gel electrolyte obtained by irradiating a liquid containing an ultraviolet curable monomer, a photopolymerization initiator and a non-aqueous electrolytic solution with ultraviolet rays.
First, the liquid is applied on the composite positive electrode 3 in a thickness of 25 to 50 μm. Then, the maximum output wavelength is 365nm
Irradiate the ultraviolet ray of 3 for 3 minutes in an inert atmosphere. At this time, the monomer is polymerized and hardened to obtain a thin film gel electrolyte containing a non-aqueous electrolyte. This electrolyte comes into close contact with the polymer electrolyte composite positive electrode 3 to form a solid half-cell. The non-aqueous electrolyte used here was a solution of LiBF 4 dissolved in dioxolane at 1 mol / liter. Polyethylene oxide diacrylate was used as the ultraviolet curable monomer, and benzyl dimethyl ketal was used as the photopolymerization initiator. The content of polyethylene oxide diacrylate in the liquid used here is 5 to 50% by weight, and the content of benzyl dimethyl ketal is 0.1 to 5% by weight.
【００３１】最後に、この半電池に５の金属リチウム箔
を積層し、リチウム・ポリマー二次電池を構成した。Finally, a metal lithium foil of 5 was laminated on this half battery to form a lithium polymer secondary battery.
【００３２】（実施例２）図１において２のポリマー電
解質には、ジオキソランとエチレンカーボネートとの混
合溶媒に、リチウム塩であるＬｉＢＦ4を１モル／リッ
トル溶解した液体を化学的あるいは電気化学的手法によ
り重合硬化して得た固体電解質を用いる。Example 2 In FIG. 1, as the polymer electrolyte 2 shown in FIG. 1, a liquid prepared by dissolving 1 mol / liter of lithium salt LiBF 4 in a mixed solvent of dioxolane and ethylene carbonate was chemically or electrochemically used. A solid electrolyte obtained by polymerization and curing according to is used.
【００３３】また図２において４のポリマー電解質層に
含有される非水電解液には、ジオキソランとエチレンカ
ーボネートとの混合溶媒に、ＬｉＢＦ4を１モル／リッ
トル溶解した液体を用いる。As the non-aqueous electrolyte contained in the polymer electrolyte layer 4 in FIG. 2, a liquid obtained by dissolving LiBF 4 at 1 mol / liter in a mixed solvent of dioxolane and ethylene carbonate is used.
【００３４】上記以外の条件は、実施例１と同じであ
る。 （比較例１）正極の製造法において、実施例１、２とは
異なり以下の方法を用いる。まず、活物質であるＶ6Ｏ
13+y（０≦ｙ≦０．１６）１００重量％、導電剤である
アセチレンブラック３重量％、ポリマー電解質であるポ
リエチレンオキシドとＬｉＢＦ4の錯体７重量％を、ア
セトニトリルに懸濁した液を調整する。次いで、この懸
濁液をアルミニウム箔上に流し、アセトニトリルを蒸発
させ、シート状の複合正極を得る。The conditions other than the above are the same as those in the first embodiment. (Comparative Example 1) In the method for producing a positive electrode, the following method is used, unlike Examples 1 and 2. First, the active material V 6 O
13 + y (0 ≦ y ≦ 0.16) 100% by weight, conductive agent acetylene black 3% by weight, polymer electrolyte polyethylene oxide and LiBF 4 complex 7% by weight were suspended in acetonitrile to prepare a solution. To do. Next, this suspension is flown on an aluminum foil to evaporate acetonitrile to obtain a sheet-shaped composite positive electrode.
【００３５】上記以外の条件は実施例１と同じである。
比較例１および実施例１、２で得られた正極についてそ
の比抵抗と放電容量を（表１）に示す。The conditions other than the above are the same as those in the first embodiment.
The specific resistance and discharge capacity of the positive electrodes obtained in Comparative Example 1 and Examples 1 and 2 are shown in (Table 1).
【００３６】[0036]
【表１】 [Table 1]
【００３７】なお、本実施例１、２では、環状エーテル
にジオキソランを用いたが、これはテトラヒドロフラン
であってもよい。Although dioxolane was used as the cyclic ether in Examples 1 and 2, it may be tetrahydrofuran.
【００３８】また、活物質にはＶ6Ｏ13+y（０≦ｙ≦
０．１６）を用いたが、これはＬｉＣｏＯ2、ＬｉＮｉ
Ｏ2、Ｖ2Ｏ5、ＬｉＭｎＯ2、ＬｉxＭｎ2Ｏ4（０．１＜
ｘ＜０．５）等の他の活物質であってもよい。The active material is V 6 O 13 + y (0 ≦ y ≦
0.16) was used, which was LiCoO 2 , LiNi
O 2 , V 2 O 5 , LiMnO 2 , Li x Mn 2 O 4 (0.1 <
Other active materials such as x <0.5) may be used.
【００３９】また、導電剤にはアセチレンブラックを用
いたが、これはグラファイト等の他のカーボンあるいは
それらの混合物であってもよい。Although acetylene black was used as the conductive agent, other carbon such as graphite or a mixture thereof may be used.
【００４０】また、紫外線硬化性モノマーにはポリエチ
レンオキシドジアクリレートを用いたが、これはポリエ
チレンオキシドジメタクリレート等の他のモノマーであ
ってもよい。Although polyethylene oxide diacrylate was used as the ultraviolet curable monomer, it may be another monomer such as polyethylene oxide dimethacrylate.
【００４１】また、非水電解液の溶質にはＬｉＢＦ4を
用いたが、これはＬｉＣＦ3ＳＯ3、ＬｉＣｌＯ4、Ｌｉ
Ｎ（ＣＦ3ＳＯ2）2、ＬｉＡｓＦ6、ＬｉＰＦ6等の他の
リチウム塩であってもよい。LiBF 4 was used as the solute of the non-aqueous electrolyte, which was LiCF 3 SO 3 , LiClO 4 , Li.
Other lithium salts such as N (CF 3 SO 2 ) 2 , LiAsF 6 and LiPF 6 may be used.
【００４２】また、光重合開始剤にはベンジルジメチル
ケタールを用いたが、これはベンゾインイソプロピルエ
ーテル、ベンゾフェノン、ジメチルアミノアセトフェノ
ン、４，４′−ビス（ジメチルアミノ）ベンゾフェノ
ン、２−クロロチオキサントン、（Ｃ6Ｈ5）2ＩＰＦ6、
（ＣＨ3）2Ｎ（Ｃ6Ｈ5）Ｎ2ＰＦ6、（Ｃ6Ｈ5）3ＳＰＦ6
等の他の開始剤であってもよい。Benzyl dimethyl ketal was used as the photopolymerization initiator, which was benzoin isopropyl ether, benzophenone, dimethylaminoacetophenone, 4,4'-bis (dimethylamino) benzophenone, 2-chlorothioxanthone, (C 6 H 5 ) 2 IPF 6 ,
(CH 3) 2 N (C 6 H 5) N 2 PF 6, (C 6 H 5) 3 SPF 6
Other initiators such as
【００４３】また、負極には金属リチウムを用いたが、
これはリチウムを含む化合物、例えばＬｉ−Ａｌのよう
な合金、あるいはＣxＬｉ（リチウム化した炭素あるい
は黒鉛）であってもよい。Although metallic lithium was used for the negative electrode,
This may be a compound containing lithium, for example, alloys such as Li-Al or C x Li, (lithiated carbon or graphite).
【００４４】なお、本実施例ではリチウム・ポリマー二
次電池で説明したが、リチウム・ポリマー一次電池にお
いても同様の効果が得られる。Although the lithium polymer secondary battery has been described in this embodiment, the same effect can be obtained also in the lithium polymer primary battery.
【００４５】[0045]
【発明の効果】以上のように本発明は、ポリマー電解質
を用いるリチウム電池において、環状エーテルをその構
成材料に利用することで、複合正極のインピーダンスの
低減および高容量化を達成し、電池の性能向上に寄与す
るものである。INDUSTRIAL APPLICABILITY As described above, according to the present invention, in a lithium battery using a polymer electrolyte, by using cyclic ether as a constituent material thereof, the impedance of the composite positive electrode can be reduced and the capacity can be increased, thereby improving the battery performance. It contributes to the improvement.
【図１】ポリマー電解質複合正極の縦断面図FIG. 1 is a vertical sectional view of a polymer electrolyte composite positive electrode.
【図２】リチウム・ポリマー二次電池の縦断面図FIG. 2 is a vertical cross-sectional view of a lithium polymer secondary battery
【符号の説明】 １ 正極 ２ ポリマー電解質 ３ ポリマー電解質複合正極 ４ ポリマー電解質層 ５ 金属リチウム箔[Explanation of symbols] 1 positive electrode 2 polymer electrolyte 3 polymer electrolyte composite positive electrode 4 polymer electrolyte layer 5 metallic lithium foil
───────────────────────────────────────────────────── フロントページの続き (72)発明者 江田 信夫 大阪府門真市大字門真1006番地 松下電器 産業株式会社内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Nobuo Eda 1006 Kadoma, Kadoma City, Osaka Prefecture Matsushita Electric Industrial Co., Ltd.
Claims (13)
した電池であって、正極は活物質を主成分として成型さ
れていて、その空隙に環状エーテルを含む電解液が含浸
され、重合硬化されてなるリチウム・ポリマー電池。1. A battery having a polymer electrolyte layer between a positive electrode and a negative electrode, wherein the positive electrode is formed by molding an active material as a main component, and the voids are impregnated with an electrolytic solution containing a cyclic ether to polymerize. A cured lithium polymer battery.
ドロフランのうち少なくとも１つを含む請求項１記載の
リチウム・ポリマー電池。2. The lithium polymer battery according to claim 1, wherein the cyclic ether contains at least one of dioxolane and tetrahydrofuran.
環状エーテル、電解質塩と環状エーテルおよび非プロト
ン性有機溶媒からなる群より選ばれた請求項１記載のリ
チウム・ポリマー電池。3. The lithium polymer battery according to claim 1, wherein the electrolytic solution containing a cyclic ether is selected from the group consisting of an electrolyte salt and a cyclic ether, an electrolyte salt and a cyclic ether, and an aprotic organic solvent.
６）である請求項１記載のリチウム・ポリマー電池。4. The positive electrode active material is V 6 O 13 + y (0 ≦ y ≦ 0.1
The lithium polymer battery according to claim 1, which is 6).
した電池の製造法であって、活物質を主成分として成型
された正極に環状エーテルを含む電解液を含浸させ、そ
の後これを重合硬化せしめてなるリチウム・ポリマー電
池の製造法。5. A method for producing a battery having a polymer electrolyte layer between a positive electrode and a negative electrode, wherein a positive electrode molded with an active material as a main component is impregnated with an electrolytic solution containing a cyclic ether, and then this is applied. A method for producing a lithium polymer battery that is polymerized and cured.
請求項５記載のリチウム・ポリマー電池の製造法。6. The method for producing a lithium polymer battery according to claim 5, wherein a chemical method is used for polymerizing the cyclic ether.
チオン重合法を用いる請求項５記載のリチウム・ポリマ
ー電池の製造法。7. The method for producing a lithium polymer battery according to claim 5, wherein an acid catalyst is used for the polymerization of the cyclic ether, and a cationic polymerization method is used.
いる請求項５記載のリチウム・ポリマー電池の製造法。8. The method for producing a lithium polymer battery according to claim 5, wherein an electrochemical method is used for polymerizing the cyclic ether.
請求項５記載のリチウム・ポリマー電池の製造法。9. The method for producing a lithium polymer battery according to claim 5, wherein an electrolytic oxidation method is used for polymerizing the cyclic ether.
ヒドロフランのうち少なくとも１つを含む請求項５記載
のリチウム・ポリマー電池の製造法。10. The method for producing a lithium polymer battery according to claim 5, wherein the cyclic ether contains at least one of dioxolane and tetrahydrofuran.
と環状エーテル、電解質塩と環状エーテルおよび非プロ
トン性有機溶媒からなる群から選ばれた請求項５記載の
リチウム・ポリマー電池の製造法。11. The method for producing a lithium polymer battery according to claim 5, wherein the electrolytic solution containing a cyclic ether is selected from the group consisting of an electrolyte salt and a cyclic ether, an electrolyte salt and a cyclic ether, and an aprotic organic solvent.
１６）である請求項５記載のリチウム・ポリマー電池の
製造法。12. The positive electrode active material is V 6 O 13 + y (0 ≦ y ≦ 0.
16) The method for producing a lithium polymer battery according to claim 5.
有した電池であって、正極はＶ6Ｏ13+y（０≦ｙ≦０．
１６）を主成分として成型されていて、その空隙にジオ
キソラン，テトラヒドロフランのうち少なくとも１つを
含む電解液が含浸され、重合硬化されてなるリチウム・
ポリマー電池。13. A battery having a polymer electrolyte layer between a positive electrode and a negative electrode, wherein the positive electrode is V 6 O 13 + y (0 ≦ y ≦ 0.
16) formed as a main component, the voids of which are impregnated with an electrolytic solution containing at least one of dioxolane and tetrahydrofuran, and polymerization-cured lithium
Polymer battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7082233A JPH08287949A (en) | 1995-04-07 | 1995-04-07 | Lithium-polymer battery and its manufacture |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7082233A JPH08287949A (en) | 1995-04-07 | 1995-04-07 | Lithium-polymer battery and its manufacture |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH08287949A true JPH08287949A (en) | 1996-11-01 |
Family
ID=13768698
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7082233A Pending JPH08287949A (en) | 1995-04-07 | 1995-04-07 | Lithium-polymer battery and its manufacture |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH08287949A (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0922707A (en) * | 1995-07-07 | 1997-01-21 | Yuasa Corp | Electrolyte for battery and battery |
| WO1999038225A1 (en) * | 1998-01-27 | 1999-07-29 | Yuasa Corporation | Lithium secondary battery of flat type |
| WO2000001026A1 (en) * | 1998-06-26 | 2000-01-06 | Sanyo Electric Co., Ltd. | Gelled polymer electrolyte lithium secondary cell |
| KR100424256B1 (en) * | 2001-10-20 | 2004-03-22 | 삼성에스디아이 주식회사 | Process for preparing an polymer electolyte by electrochemical polymerization and lithium battery employing such process |
| US8405957B2 (en) | 2005-12-08 | 2013-03-26 | Hitachi Maxell, Ltd. | Separator for electrochemical device and method for producing the same, and electrochemical device and method for producing the same |
| JP2015018759A (en) * | 2013-07-12 | 2015-01-29 | 三菱瓦斯化学株式会社 | Polymer electrolyte |
| JP2015153452A (en) * | 2014-02-10 | 2015-08-24 | セイコーエプソン株式会社 | Method for manufacturing electrode complex, electrode complex and battery |
| US9166250B2 (en) | 2006-09-07 | 2015-10-20 | Hitachi Maxell, Ltd. | Separator for battery, method for manufacturing the same, and lithium secondary battery |
| US10930975B2 (en) | 2016-06-28 | 2021-02-23 | Lg Chem, Ltd. | Electrolyte for lithium-sulfur battery and lithium-sulfur battery comprising same |
| US11050095B2 (en) | 2004-12-08 | 2021-06-29 | Maxell Holdings, Ltd. | Separator for electrochemical device, and electrochemical device |
-
1995
- 1995-04-07 JP JP7082233A patent/JPH08287949A/en active Pending
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0922707A (en) * | 1995-07-07 | 1997-01-21 | Yuasa Corp | Electrolyte for battery and battery |
| US6444369B1 (en) | 1998-01-08 | 2002-09-03 | Sanyo Electric Co., Ltd. | Gelled polymer electrolyte lithium secondary cell |
| WO1999038225A1 (en) * | 1998-01-27 | 1999-07-29 | Yuasa Corporation | Lithium secondary battery of flat type |
| WO2000001026A1 (en) * | 1998-06-26 | 2000-01-06 | Sanyo Electric Co., Ltd. | Gelled polymer electrolyte lithium secondary cell |
| KR100424256B1 (en) * | 2001-10-20 | 2004-03-22 | 삼성에스디아이 주식회사 | Process for preparing an polymer electolyte by electrochemical polymerization and lithium battery employing such process |
| US11050095B2 (en) | 2004-12-08 | 2021-06-29 | Maxell Holdings, Ltd. | Separator for electrochemical device, and electrochemical device |
| US8405957B2 (en) | 2005-12-08 | 2013-03-26 | Hitachi Maxell, Ltd. | Separator for electrochemical device and method for producing the same, and electrochemical device and method for producing the same |
| US9166250B2 (en) | 2006-09-07 | 2015-10-20 | Hitachi Maxell, Ltd. | Separator for battery, method for manufacturing the same, and lithium secondary battery |
| JP2015018759A (en) * | 2013-07-12 | 2015-01-29 | 三菱瓦斯化学株式会社 | Polymer electrolyte |
| JP2015153452A (en) * | 2014-02-10 | 2015-08-24 | セイコーエプソン株式会社 | Method for manufacturing electrode complex, electrode complex and battery |
| US10056616B2 (en) | 2014-02-10 | 2018-08-21 | Seiko Epson Corporation | Manufacturing method of electrode assembly, electrode assembly and battery |
| US10930975B2 (en) | 2016-06-28 | 2021-02-23 | Lg Chem, Ltd. | Electrolyte for lithium-sulfur battery and lithium-sulfur battery comprising same |
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