JPH06342655A - Electrode and battery provided therewith - Google Patents
Electrode and battery provided therewithInfo
- Publication number
- JPH06342655A JPH06342655A JP15440593A JP15440593A JPH06342655A JP H06342655 A JPH06342655 A JP H06342655A JP 15440593 A JP15440593 A JP 15440593A JP 15440593 A JP15440593 A JP 15440593A JP H06342655 A JPH06342655 A JP H06342655A
- Authority
- JP
- Japan
- Prior art keywords
- electrode
- battery
- fluoride
- fullerene
- fluorene
- 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
-
- Y02E60/12—
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、例えばリチウム電池な
どに使用できる電極、およびこれを備えた電池に関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrode that can be used in, for example, a lithium battery, and a battery including the electrode.
【０００２】[0002]
【従来の技術】フラーレンはカーボンクラスターとも称
され、黒鉛構造とは異なる３次元的な構造を有し、中心
部に空隙部を有する特殊な炭素同素体である。前記フラ
ーレンのうち、Ｃ60は、炭素原子６０個で構成され、フ
ットボール状の構造を有し、クロト（Ｋｒｏｔｏ）らに
より、黒鉛へのレーザ照射により生成したスス中から見
出だされた質量数７２０の物質である。また、１９９１
年４月には、ヘバート（Ｈｅｂａｒｄ）らにより、前記
Ｃ60にカリウムをドープすると、絶対温度１８°Ｋで超
電導を示すことが報告されている。このように、フラー
レンは特殊な構造及び特性を有することから、新たなフ
ラーレン誘導体とその用途の開発が期待されている。2. Description of the Related Art Fullerenes, which are also called carbon clusters, are special carbon allotropes having a three-dimensional structure different from the graphite structure and having a void portion in the center. Among the fullerenes, C 60 is composed of 60 carbon atoms and has a football-like structure, and the mass number found in the soot generated by laser irradiation of graphite by Kroto et al. 720 substances. Also, 1991
In April 2013, Hebard et al. Reported that C 60 doped with potassium exhibited superconductivity at an absolute temperature of 18 ° K. As described above, since fullerenes have special structures and properties, development of new fullerene derivatives and their uses is expected.
【０００３】一方、リチウム、マグネシウムなどの軽金
属を活物質として用いる電池は、高エネルギー密度が得
られるとして注目されている。例えば、リチウムを負極
活物質として用いるリチウム電池においては、正極活物
質として二酸化イオウ、フッ化黒鉛、硫化銅、二酸化マ
ンガンなどを、また、電解液として高誘電率をもつ有機
溶媒又は無機非水溶媒を用いた各種の電池が開発されて
いる。On the other hand, a battery using a light metal such as lithium or magnesium as an active material has been attracting attention because of its high energy density. For example, in a lithium battery using lithium as a negative electrode active material, sulfur dioxide, fluorinated graphite, copper sulfide, manganese dioxide, etc. are used as a positive electrode active material, and an organic solvent or an inorganic nonaqueous solvent having a high dielectric constant is used as an electrolytic solution. Various types of batteries have been developed.
【０００４】これらのうち、特に、フッ化黒鉛を正極活
物質とする電池は、比較的安定した放電電圧が得られる
と共に、貯蔵性の点でも優れている。しかし、この電池
は、放電初期において、過電圧が大きいため、放電電圧
が放電中期に比べて低いという問題点を有する。Among these, the battery using fluorinated graphite as the positive electrode active material is particularly excellent in terms of storability as well as obtaining a relatively stable discharge voltage. However, this battery has a problem that the discharge voltage is lower than that in the middle stage of discharge because the overvoltage is large at the initial stage of discharge.
【０００５】この問題点を解決する方法として、電池の
使用前にある程度放電させる方法が提案されている。し
かし、この方法では、放電容量を無駄に消費することに
なる。また、他の方法として、γ線照射により、一部の
フッ素を離脱させたフッ化黒鉛を正極活物質として用い
る方法が提案されている。しかし、この方法では、工程
が煩雑化するため工業的に有利な方法とはいえない。As a method of solving this problem, a method of discharging the battery to some extent before use has been proposed. However, this method wastes the discharge capacity. Further, as another method, a method has been proposed in which fluorinated graphite in which a part of fluorine is released by γ-ray irradiation is used as a positive electrode active material. However, this method cannot be said to be industrially advantageous because the process becomes complicated.
【０００６】[0006]
【発明が解決しようとする課題】従って、本発明の目的
は、単位体積当りの放電容量が大きく、しかも、過電圧
が小さく、安定した放電電圧を維持できる電極、および
この電極を用いた電池を提供することにある。SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide an electrode which has a large discharge capacity per unit volume, a small overvoltage and can maintain a stable discharge voltage, and a battery using this electrode. To do.
【０００７】[0007]
【発明の構成】前記目的を達成するため、本発明者らは
鋭意研究を重ねた結果、電極の活物質として、フッ化黒
鉛と、フラーレンをフッ素化して得られるフッ化フラー
レンとを併用すると、フッ化黒鉛のみを活物質とした場
合にみられる放電初期における電圧降下を顕著に抑制で
きることを見いだし、本発明を完成した。In order to achieve the above object, the inventors of the present invention have conducted extensive studies, and as a result, when fluorinated graphite and a fluorinated fullerene obtained by fluorinating fullerene are used in combination as an electrode active material, The inventors have found that the voltage drop at the initial stage of discharge, which is observed when only fluorinated graphite is used as the active material, can be remarkably suppressed and the present invention has been completed.
【０００８】すなわち、本発明は、フッ化黒鉛と、式
Ｃx Ｆy （式中、Ｃはフラーレン骨格を構成する炭素原
子、Ｆは前記炭素原子に結合しているフッ素原子を示
し、ｘは２８〜１０００の整数、ｙは０．０１ｘ〜１．
８ｘを示す）で表される少なくとも一種のフッ化フラー
レンとを含む電極を提供する。That is, the present invention relates to a fluorinated graphite and a formula
C x F y (wherein, C represents the carbon atoms constituting the fullerene skeleton, F is a fluorine atom bonded to the carbon atoms, x is an integer of 28-1,000, y is 0.01X～1.
8x) and at least one fluorinated fullerene.
【０００９】また、本発明は、前記電極を備えている電
池を提供する。The present invention also provides a battery including the electrode.
【００１０】前記フッ化黒鉛は、慣用の方法、例えば、
黒鉛とフッ素ガスとを２５０〜６５０℃程度の温度で反
応させることにより得ることができる。フッ化黒鉛のＦ
／Ｃは、例えば０．４５〜１．３０程度である。The fluorinated graphite is prepared by a conventional method, for example,
It can be obtained by reacting graphite and fluorine gas at a temperature of about 250 to 650 ° C. Fluorinated graphite F
/ C is, for example, about 0.45 to 1.30.
【００１１】前記フッ化フラーレンにおいては、フッ素
原子１〜３個が共有結合により結合している炭素原子を
含んでいる。フラーレン骨格を構成する炭素原子には、
通常１個のフッ素原子が結合するが、フラーレン骨格が
部分的に欠落した部位では、炭素原子に、フッ素原子が
２〜３個結合する場合がある。The fluorinated fullerene contains carbon atoms having 1 to 3 fluorine atoms bonded by a covalent bond. The carbon atoms that make up the fullerene skeleton include
Usually, one fluorine atom is bonded, but at the site where the fullerene skeleton is partially missing, two or three fluorine atoms may be bonded to the carbon atom.
【００１２】前記式において、好ましいｘは６０〜１１
０程度である。特に好ましいｘには６０、７０、７６、
７８、８２、８４、９０、９６、１０２、１０６、１１
０等が含まれる。また、前記フッ化フラーレンにおける
Ｆ／Ｃ原子比は、例えば０．０１〜１．８、好ましくは
０．５〜１．８程度である。Ｆ／Ｃ原子比の小さい、例
えば０．０１〜０．５程度のフッ化フラーレンを用いて
も、フッ化黒鉛を正極活物質とする電池に特徴的な前記
電圧降下の問題を解消することができる。In the above formula, preferred x is 60 to 11
It is about 0. Particularly preferred x is 60, 70, 76,
78, 82, 84, 90, 96, 102, 106, 11
0 and the like are included. The F / C atomic ratio in the fluorinated fullerene is, for example, 0.01 to 1.8, preferably about 0.5 to 1.8. Even if a fluorinated fullerene having a small F / C atomic ratio, for example, about 0.01 to 0.5 is used, the voltage drop problem characteristic of a battery using fluorinated graphite as a positive electrode active material can be solved. it can.
【００１３】前記フッ化フラーレンは、通常、白色乃至
黄白色もしくは褐色の固体であり、撥水性に優れると共
に、空気中で安定である。フッ化フラーレンの構造は、
元素分析、マススペクトル、核磁気共鳴スペクトル、Ｘ
線回折、ラマン吸収スペクトルなどの分析手段により解
析できる。The fluorinated fullerene is usually a white to yellowish white or brown solid, has excellent water repellency, and is stable in air. The structure of fullerene fluoride is
Elemental analysis, mass spectrum, nuclear magnetic resonance spectrum, X
It can be analyzed by analysis means such as line diffraction and Raman absorption spectrum.
【００１４】このようなフッ化フラーレンは、例えば、
フラーレンとフッ素とを、減圧、常圧又は加圧下に反応
させることにより得られる。Such fluorinated fullerenes are, for example,
It can be obtained by reacting fullerene with fluorine under reduced pressure, normal pressure or increased pressure.
【００１５】反応に用いるフラーレンとしては、Ｃ60、
Ｃ70、Ｃ76、Ｃ78、Ｃ82、Ｃ84、Ｃ90、Ｃ96、Ｃ102 、
Ｃ106 、Ｃ110 、Ｃ240 、Ｃ540 等が例示できる。好ま
しいフラーレンはｘ＝６０〜１１０の炭素原子で構成さ
れる。The fullerene used in the reaction includes C 60 ,
C 70 , C 76 , C 78 , C 82 , C 84 , C 90 , C 96 , C 102 ,
Examples include C 106 , C 110 , C 240 , C 540 and the like. Preferred fullerenes are composed of x = 60 to 110 carbon atoms.
【００１６】前記フラーレンの形態は、３次元的でしか
も中心部に空隙部を有する限り、球状、卵状やラグビー
ボール状などであってもよく、３次元構造の頂点や面を
構成する炭素原子が部分的に欠落した篭状であってもよ
い。また、フラーレンの製造に際して副生する炭素数１
００以上の不完全な篭状であってもよい。これらのフラ
ーレンは、単独で又は二種以上の混合物として使用でき
る。The form of the fullerene may be spherical, egg-shaped, rugby ball-shaped or the like as long as it has a three-dimensional shape and has a void in the central portion, and carbon atoms constituting the vertices or faces of the three-dimensional structure. It may have a basket-like shape in which is partially missing. In addition, carbon number of 1 by-product in the production of fullerene
It may be an incomplete basket of 00 or more. These fullerenes can be used alone or as a mixture of two or more kinds.
【００１７】前記反応において、フッ素圧としては、例
えば０．０７〜１．５気圧の範囲が一般に用いられる。
フッ素ガスはそのまま用いてもよく、窒素、ヘリウム、
アルゴン、ネオンなどの不活性ガスで希釈して用いても
よい。In the above reaction, the fluorine pressure is generally in the range of 0.07 to 1.5 atm.
Fluorine gas may be used as it is, nitrogen, helium,
It may be diluted with an inert gas such as argon or neon before use.
【００１８】フッ素の使用量は、フラーレン１モルに対
して、例えば０．１〜１０００モル、好ましくは１〜１
００モル程度である。反応温度は、例えば０〜３５０
℃、好ましくは常温〜３００℃程度である。The amount of fluorine used is, for example, 0.1 to 1000 mol, preferably 1 to 1 mol, relative to 1 mol of fullerene.
It is about 100 mol. The reaction temperature is, for example, 0 to 350.
C., preferably room temperature to about 300.degree.
【００１９】反応温度、反応時間、フッ素の使用量等に
より、生成するフッ化フラーレンのＦ／Ｃ原子比を調整
することができる。The F / C atomic ratio of the resulting fluorinated fullerene can be adjusted by the reaction temperature, the reaction time, the amount of fluorine used, and the like.
【００２０】こうして得られるフッ化フラーレンは、通
常、原料として用いたフラーレンに対応する形態を有し
ている。The fluorinated fullerene thus obtained usually has a form corresponding to the fullerene used as the raw material.
【００２１】本発明の特色は、フッ化黒鉛とフッ化フラ
ーレンとを併用することにより、過電圧を小さくし、初
期電圧降下を抑制する点にある。A feature of the present invention is that the combined use of fluorinated graphite and fluorinated fullerene reduces overvoltage and suppresses initial voltage drop.
【００２２】本発明の電極におけるフッ化フラーレンの
添加量は、前記電圧降下の抑制効果を発現する範囲で適
宜選択できる。一般に、前記電圧降下は、少量のフッ化
フラーレンの添加によって著しく抑制されるため、多量
のフッ化フラーレンを要しない。例えば、前記フッ化フ
ラーレンの添加量は、フッ化黒鉛１００重量部に対し
て、０．１〜５０重量部、好ましくは０．３〜１０重量
部、さらに好ましくは１〜８重量部程度である。前記フ
ッ化フラーレンの添加量が０．１重量部未満では、前記
電圧降下の抑制効果が得られにくく、５０重量部を越え
る場合には、成形性が低下し易く、経済性の点でも好ま
しくない。The addition amount of the fullerene fluoride in the electrode of the present invention can be appropriately selected within the range where the effect of suppressing the voltage drop is exhibited. Generally, since the voltage drop is significantly suppressed by adding a small amount of fluorinated fullerenes, a large amount of fluorinated fullerenes is not required. For example, the addition amount of the fluorinated fullerene is 0.1 to 50 parts by weight, preferably 0.3 to 10 parts by weight, and more preferably 1 to 8 parts by weight with respect to 100 parts by weight of fluorinated graphite. . If the amount of the fluorinated fullerene added is less than 0.1 parts by weight, the effect of suppressing the voltage drop is difficult to obtain, and if it exceeds 50 parts by weight, the moldability is likely to decrease, which is not preferable in terms of economy. .
【００２３】本発明の電極は、前記フッ化黒鉛およびフ
ッ化フラーレン以外の物質を含んでいてもよい。例え
ば、成形性、導電性を高めるため、粘結材料や導電材料
を含有していてもよい。前記粘結材料としては、ポリ酢
酸ビニル、アクリル系樹脂、ポリ塩化ビニル、ポリスチ
レン、ポリエチレン、ポリアミド、ポリエステル、ポリ
テトラフルオロエチレン等のフッ素樹脂などの熱可塑性
樹脂；アミノ樹脂、フェノール樹脂、エポキシ樹脂、ウ
レタン樹脂などの熱硬化性樹脂等が挙げられる。前記導
電材料としては、アセチレンブラックなどのカーボンブ
ラック、黒鉛、金属等が挙げられる。前記粘結材料及び
導電材料の含有量は、それぞれ、活物質１００重量部に
対して、例えば１０〜１０００重量部、好ましくは２０
〜３００重量部程度である。The electrode of the present invention may contain a substance other than the fluorinated graphite and the fullerene fluoride. For example, a caking material or a conductive material may be contained in order to improve moldability and conductivity. Examples of the binder include thermoplastic resins such as polyvinyl acetate, acrylic resin, polyvinyl chloride, polystyrene, polyethylene, polyamide, polyester, and fluororesin such as polytetrafluoroethylene; amino resin, phenol resin, epoxy resin, Thermosetting resin such as urethane resin may, for example, be mentioned. Examples of the conductive material include carbon black such as acetylene black, graphite, metal and the like. The content of each of the binder material and the conductive material is, for example, 10 to 1000 parts by weight, preferably 20 parts by weight, relative to 100 parts by weight of the active material.
It is about 300 parts by weight.
【００２４】本発明の電極は、例えば、フッ化黒鉛およ
びフッ化フラーレンを含む正極活物質に、必要に応じ
て、前記導電材料などの添加剤を混合し、慣用の方法で
成形することにより、容易に得ることができる。The electrode of the present invention is prepared, for example, by mixing a positive electrode active material containing fluorinated graphite and fluorinated fullerene with an additive such as the conductive material, if necessary, and molding the mixture by a conventional method. Can be easily obtained.
【００２５】本発明の電池は、前記電極を備えている。
このような電池として、例えば、前記電極を正極とし、
負極及び非水系電解質を備えた一次電池等が挙げられ
る。The battery of the present invention comprises the above electrode.
As such a battery, for example, the electrode is a positive electrode,
Examples thereof include a primary battery provided with a negative electrode and a non-aqueous electrolyte.
【００２６】前記負極は、負極活物質のみで形成されて
いてもよく、また、負極活物質が炭素材などの負極材に
担持されて形成されていてもよい。負極の活物質とし
て、例えば、リチウム、ナトリウム、マグネシウムなど
のアルカリ金属又はアルカリ土類金属が挙げられる。好
ましい負極活物質には、リチウム、ナトリウムなどのア
ルカリ金属が含まれる。特に好ましい負極活物質はリチ
ウムである。The negative electrode may be formed of only the negative electrode active material, or may be formed by supporting the negative electrode active material on a negative electrode material such as a carbon material. Examples of the negative electrode active material include alkali metals or alkaline earth metals such as lithium, sodium and magnesium. Preferred negative electrode active materials include alkali metals such as lithium and sodium. A particularly preferred negative electrode active material is lithium.
【００２７】電解液としては、高誘電率を有する種々の
有機溶媒等が用いられる。前記有機溶媒としては、プロ
ピレンカーボネート、エチレンカーボネート、γ−ブチ
ロラクトン、テトラヒドロフラン、２−メチルテトラヒ
ドロフラン、ジオキソラン、４−メチルジオキソラン、
スルホラン、１，２−ジメトキシエタン、ジメチルスル
ホキシド、アセトニトリル、Ｎ，Ｎ−ジメチルホルムア
ミド、ジエチレングリコールジメチルエーテルなどの非
プロトン性溶媒等が挙げられる。As the electrolytic solution, various organic solvents having a high dielectric constant are used. Examples of the organic solvent include propylene carbonate, ethylene carbonate, γ-butyrolactone, tetrahydrofuran, 2-methyltetrahydrofuran, dioxolane, 4-methyldioxolane,
Examples thereof include aprotic solvents such as sulfolane, 1,2-dimethoxyethane, dimethyl sulfoxide, acetonitrile, N, N-dimethylformamide, and diethylene glycol dimethyl ether.
【００２８】なお、電解液としては、一種又は二種以上
の前記溶媒に、ＬｉＣｌＯ4 、ＬｉＢＦ4 、ＬｉＣｌＦ
4 、ＬｉＡｓＦ6 、ＬｉＳｂＦ6 、ＬｉＡｌＯ4 、Ｌｉ
ＡｌＣｌ4 、ＬｉＰＦ6 、ＬｉＣｌ、ＬｉＢｒ、ＬｉＩ
などの、溶媒和しにくいアニオンを生成する塩を溶解し
た溶液が繁用される。As the electrolytic solution, LiClO 4 , LiBF 4 , LiClF may be added to one or more of the above solvents.
4 , LiAsF 6 , LiSbF 6 , LiAlO 4 , Li
AlCl 4 , LiPF 6 , LiCl, LiBr, LiI
A solution in which a salt that produces an anion that is difficult to solvate is dissolved is often used.
【００２９】電池の形状は、円筒型、角型又はボタン型
等のいずれの形態であってもよい。本発明の電池は、各
種電子機器の電源等の広い用途に使用できる。The shape of the battery may be any shape such as a cylindrical shape, a square shape or a button shape. The battery of the present invention can be used in a wide variety of applications such as a power source for various electronic devices.
【００３０】[0030]
【発明の効果】本発明の電極及び電池は、活物質として
フッ化黒鉛とフッ化フラーレンとを含むため、単位体積
当りの放電容量が大きく、しかも、過電圧が小さく放電
初期における電圧降下が顕著に抑制されるため、安定し
た放電電圧を維持できる。EFFECTS OF THE INVENTION Since the electrodes and batteries of the present invention contain fluorinated graphite and fullerene fluoride as active materials, the discharge capacity per unit volume is large, and the overvoltage is small and the voltage drop at the initial stage of discharge is remarkable. Since it is suppressed, a stable discharge voltage can be maintained.
【００３１】[0031]
【実施例】以下に、実施例に基づいて本発明をより詳細
に説明する。EXAMPLES The present invention will be described in more detail based on the following examples.
【００３２】実施例１ Ｃ70の含有量が２０重量％以下のフラーレン（Ｃ60／Ｃ
70混合物、米国ＭＥＲ社製）を、２００℃で約１０時間
真空排気し、不純物として含まれている有機溶媒を除去
した。Example 1 Fullerene having a C 70 content of 20% by weight or less (C 60 / C
The 70 mixture (manufactured by MER, USA) was evacuated at 200 ° C. for about 10 hours to remove the organic solvent contained as an impurity.
【００３３】このフラーレン０．０４ｇを、ニッケル製
反応器に仕込み、系内を真空排気し、アルゴンガスで満
たした。次いで、室温でフッ素ガスを２ｃｃ／分で流通
し、４時間反応させた。その結果、０．０８ｇのフッ化
フラーレンが得られた。元素分析を行ったところ、組成
式はＣ60Ｆ41であった。また、得られたフッ化フラーレ
ンの結晶をＸ線回折法により分析した。その測定条件お
よび測定結果を以下に示す。0.04 g of this fullerene was charged into a reactor made of nickel, the system was evacuated and filled with argon gas. Then, at room temperature, a fluorine gas was passed at 2 cc / min and reacted for 4 hours. As a result, 0.08 g of fluorinated fullerene was obtained. As a result of elemental analysis, the composition formula was C 60 F 41 . The crystals of the obtained fullerene fluoride were analyzed by the X-ray diffraction method. The measurement conditions and measurement results are shown below.
【００３４】測定条件 管球：Ｃｕ、管電圧：５０ＫＶ、管電流：８０ｍＡ、ゴ
ニオメータ：広角ゴニオメータ、サンプリング幅：０．
０１０゜、走査速度：５．０００゜／ｍｉｎ、発散スリ
ット：１゜、散乱スリット：１゜、受光スリット：０．
３０ｍｍ、アタッチメント：標準試料ホルダー、フィル
タ：Ｎｉ 測定結果 ピークＮｏ．１：２θ＝８．９５０、面間隔 ９．８７
２３５、強度値４３８８、半値幅 １．１７８、Ｉ／Ｉ
0 ＝１００ ピークＮｏ．２：２θ＝１４．７７０、面間隔 ５．９
９２７３、強度値３６６８、Ｉ／Ｉ0 ＝８４ フッ化黒鉛（Ｆ／Ｃ＝１．０１）１００重量部と、上記
で得られたフッ化フラーレン５重量部を混合した。これ
に、さらに、アセチレンブラック及びポリエチレンをそ
れぞれ１０５重量部ずつ加えて混合した。得られた混合
物のうち約３０ｍｇを濾紙にはさみ、直径０．９ｃｍの
円盤状のペレットに成型した。次いで、円盤状ペレット
のエッジ部に炭素繊維を巻き、ポリエチレンで融着する
ことにより導通をとり正極を得た。Measurement conditions Tube: Cu, Tube voltage: 50 KV, Tube current: 80 mA, Goniometer: Wide-angle goniometer, Sampling width: 0.
010 °, scanning speed: 5.000 ° / min, divergence slit: 1 °, scattering slit: 1 °, light receiving slit: 0.
30 mm, attachment: standard sample holder, filter: Ni measurement result Peak No. 1: 2θ = 8.950, surface spacing 9.87
235, intensity value 4388, half width 1.178, I / I
0 = 100 Peak No. 2: 2θ = 14.770, surface spacing 5.9
9273, strength value 3668, I / I 0 = 84 100 parts by weight of fluorinated graphite (F / C = 1.01) were mixed with 5 parts by weight of the fluorinated fullerene obtained above. To this, 105 parts by weight of acetylene black and 105 parts by weight of polyethylene were added and mixed. About 30 mg of the obtained mixture was sandwiched between filter papers and molded into disc-shaped pellets having a diameter of 0.9 cm. Next, carbon fibers were wound around the edge portion of the disk-shaped pellet and fused with polyethylene to obtain continuity to obtain a positive electrode.
【００３５】一方、負極は、直径１ｃｍのリチウム板に
リード線を接続して得た。On the other hand, the negative electrode was obtained by connecting a lead wire to a lithium plate having a diameter of 1 cm.
【００３６】電解液として１モル／リットルの濃度の過
塩素酸リチウムを溶解したプロピレンカーボネートを用
いた。As an electrolytic solution, propylene carbonate in which lithium perchlorate having a concentration of 1 mol / liter was dissolved was used.
【００３７】こうして得られた正極、負極及び電解液か
ら一次電池を作製し、図１に示すような装置を用いて、
電流密度０．５ｍＡ／ｃｍ2 で放電させた。なお、以上
の操作は、正極の製造を除き、すべてアルゴン雰囲気下
で行った。参照極の電極にはリチウムを用いた。A primary battery was prepared from the positive electrode, the negative electrode and the electrolytic solution thus obtained, and the apparatus as shown in FIG.
It was discharged at a current density of 0.5 mA / cm 2 . The above operations were all performed under an argon atmosphere except for the production of the positive electrode. Lithium was used for the electrode of the reference electrode.
【００３８】その結果、放電初期における電圧の降下は
見られなかった。開回路電圧は３．３Ｖ、放電電位は
２．１Ｖ、放電容量の利用率は９８％であった。As a result, no voltage drop was observed at the initial stage of discharge. The open circuit voltage was 3.3V, the discharge potential was 2.1V, and the discharge capacity utilization rate was 98%.
【００３９】比較例 フッ化フラーレンを用いなかった他は、実施例１と同様
にして、フッ化黒鉛のみを活物質とする正極を作製し
た。さらに、この正極を用いた以外は実施例１と同様に
して一次電池を作製し、放電実験を行った。Comparative Example A positive electrode using only fluorinated graphite as an active material was prepared in the same manner as in Example 1 except that fluorinated fullerene was not used. Further, a primary battery was prepared in the same manner as in Example 1 except that this positive electrode was used, and a discharge experiment was conducted.
【００４０】その結果、放電初期に０．１Ｖの電圧降下
が見られた。なお、開回路電圧は３．３Ｖ、放電容量の
利用率は９８％であった。As a result, a voltage drop of 0.1 V was observed at the initial stage of discharge. The open circuit voltage was 3.3 V and the discharge capacity utilization rate was 98%.
【図１】図１は実施例で用いた実験装置を示す概略図で
ある。FIG. 1 is a schematic diagram showing an experimental apparatus used in Examples.
１、２…負極 ３…正極 ４…参照極 ５…電解液 ６…定電流発生装置 ７…ボルテージフォロワー ８…レコーダー 1, 2 ... Negative electrode 3 ... Positive electrode 4 ... Reference electrode 5 ... Electrolyte solution 6 ... Constant current generator 7 ... Voltage follower 8 ... Recorder
Claims (4)
はフラーレン骨格を構成する炭素原子、Ｆは前記炭素原
子に結合しているフッ素原子を示し、ｘは２８〜１００
０の整数、ｙは０．０１ｘ〜１．８ｘを示す）で表され
る少なくとも一種のフッ化フラーレンとを含む電極。1. A fluorinated graphite and a formula C x F y (wherein C
Is a carbon atom constituting the fullerene skeleton, F is a fluorine atom bonded to the carbon atom, and x is 28 to 100.
An integer of 0, y is 0.01x to 1.8x) and an electrode containing at least one kind of fluorinated fullerene.
４、９０、９６、１０２、１０６又は１１０である少な
くとも一種のフッ化フラーレンを含む請求項１記載の電
極。2. x is 60, 70, 76, 78, 82, 8
The electrode of claim 1, comprising at least one fluorinated fullerene that is 4, 90, 96, 102, 106 or 110.
る電池。3. A battery comprising the electrode according to claim 1 or 2.
む負極と、非水系電解質とを備えている電池であって、
正極として請求項１又は２に記載の電極を用いる請求項
３記載の電池。4. A battery comprising a positive electrode, a negative electrode containing an alkali metal as an active material, and a non-aqueous electrolyte,
The battery according to claim 3, wherein the electrode according to claim 1 or 2 is used as the positive electrode.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15440593A JPH06342655A (en) | 1993-05-31 | 1993-05-31 | Electrode and battery provided therewith |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15440593A JPH06342655A (en) | 1993-05-31 | 1993-05-31 | Electrode and battery provided therewith |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH06342655A true JPH06342655A (en) | 1994-12-13 |
Family
ID=15583435
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15440593A Pending JPH06342655A (en) | 1993-05-31 | 1993-05-31 | Electrode and battery provided therewith |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH06342655A (en) |
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| WO2004032262A1 (en) * | 2002-10-04 | 2004-04-15 | Mitsubishi Chemical Corporation | Additive to negative electrode material for lithium secondary battery, negative electrode material for lithium secondary battery and, using the negative electrode material for lithium secondary battery, negative electrode and lithium secondary battery |
| WO2004040678A1 (en) * | 2002-10-31 | 2004-05-13 | Mitsubishi Chemical Corporation | Additive to positive electrode material for lithium secondary battery, positive electrode material for lithium secondary battery and, prepared from the positive electrode material, positive electrode and lithium secondary battery |
| JP2005285440A (en) * | 2004-03-29 | 2005-10-13 | Matsushita Electric Ind Co Ltd | Nonaqueous electrolyte battery |
| CN1333478C (en) * | 2002-10-04 | 2007-08-22 | 三菱化学株式会社 | Additive for anode material for lithium secondary battery, anode material for lithium secondary battery, anode and lithium secondary battery using the anode material for lithium secondary battery |
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| US7531273B2 (en) * | 2001-05-29 | 2009-05-12 | Itt Manufacturing Enterprises, Inc. | Fullerene-based secondary cell electrodes |
| KR100917286B1 (en) * | 2001-05-29 | 2009-09-11 | 아이티티 메뉴펙터링 엔터프라이지즈 인코포레이티드 | Fullerene-based secondary cell electrodes |
| US7879260B2 (en) | 2002-10-04 | 2011-02-01 | Mitsubishi Chemical Corporation | Additive for anode material for lithium secondary battery, anode material for lithium secondary battery, anode and lithium secondary battery using the anode material for lithium secondary battery |
| JP2016536743A (en) * | 2013-10-04 | 2016-11-24 | トヨタ モーター エンジニアリング アンド マニュファクチャリング ノース アメリカ，インコーポレイティド | Fullerene cathode for rechargeable magnesium battery |
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1993
- 1993-05-31 JP JP15440593A patent/JPH06342655A/en active Pending
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|---|---|---|---|---|
| US7531273B2 (en) * | 2001-05-29 | 2009-05-12 | Itt Manufacturing Enterprises, Inc. | Fullerene-based secondary cell electrodes |
| KR100917286B1 (en) * | 2001-05-29 | 2009-09-11 | 아이티티 메뉴펙터링 엔터프라이지즈 인코포레이티드 | Fullerene-based secondary cell electrodes |
| WO2004032262A1 (en) * | 2002-10-04 | 2004-04-15 | Mitsubishi Chemical Corporation | Additive to negative electrode material for lithium secondary battery, negative electrode material for lithium secondary battery and, using the negative electrode material for lithium secondary battery, negative electrode and lithium secondary battery |
| KR100733753B1 (en) * | 2002-10-04 | 2007-06-29 | 미쓰비시 가가꾸 가부시키가이샤 | Additive to negative electrode material for lithium secondary battery, negative electrode material for lithium secondary battery and, using the negative electrode material for lithium secondary battery, negative electrode and lithium secondary battery |
| CN1333478C (en) * | 2002-10-04 | 2007-08-22 | 三菱化学株式会社 | Additive for anode material for lithium secondary battery, anode material for lithium secondary battery, anode and lithium secondary battery using the anode material for lithium secondary battery |
| US7879260B2 (en) | 2002-10-04 | 2011-02-01 | Mitsubishi Chemical Corporation | Additive for anode material for lithium secondary battery, anode material for lithium secondary battery, anode and lithium secondary battery using the anode material for lithium secondary battery |
| WO2004040678A1 (en) * | 2002-10-31 | 2004-05-13 | Mitsubishi Chemical Corporation | Additive to positive electrode material for lithium secondary battery, positive electrode material for lithium secondary battery and, prepared from the positive electrode material, positive electrode and lithium secondary battery |
| KR100793659B1 (en) * | 2002-10-31 | 2008-01-10 | 미쓰비시 가가꾸 가부시키가이샤 | Additive to positive electrode material for lithium secondary battery, positive electrode meterial for lithium secondary battery and, prepared from the positive electrode material, positive electrode and lithium secondary battery |
| GB2413319B (en) * | 2003-10-27 | 2008-10-15 | Itt Mfg Enterprises Inc | Fullerene-based secondary cell electrodes |
| KR101251635B1 (en) * | 2003-10-27 | 2013-04-05 | 아이티티 매뉴팩츄어링 엔터프라이지스 엘엘씨 | Fullerene-based secondary cell electrodes |
| JP2005285440A (en) * | 2004-03-29 | 2005-10-13 | Matsushita Electric Ind Co Ltd | Nonaqueous electrolyte battery |
| JP2016536743A (en) * | 2013-10-04 | 2016-11-24 | トヨタ モーター エンジニアリング アンド マニュファクチャリング ノース アメリカ，インコーポレイティド | Fullerene cathode for rechargeable magnesium battery |
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