JPH08306354A - Electrode and nonaqueous solvent type secondary battery using the electrode - Google Patents
Electrode and nonaqueous solvent type secondary battery using the electrodeInfo
- Publication number
- JPH08306354A JPH08306354A JP7113335A JP11333595A JPH08306354A JP H08306354 A JPH08306354 A JP H08306354A JP 7113335 A JP7113335 A JP 7113335A JP 11333595 A JP11333595 A JP 11333595A JP H08306354 A JPH08306354 A JP H08306354A
- Authority
- JP
- Japan
- Prior art keywords
- electrode
- powder
- conductive powder
- carbonaceous material
- secondary battery
- 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、炭素質材料を用いた電
極、およびそれを用いた非水溶媒系二次電池に関するも
のである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrode using a carbonaceous material and a non-aqueous solvent secondary battery using the same.
【０００２】[0002]
【従来の技術】近年、ビデオカメラやノート型パソコン
などのポータブル機器の普及に伴い、小型高容量の二次
電池に対する需要が高まっている。現在使用されている
二次電池のほとんどはアルカリ電解液を用いたニッケル
−カドミウム電池であるが、電池電圧が約１．２Ｖと低
く、エネルギー密度の向上は困難である。そのため、負
極に最も卑な金属であるリチウム金属を使用して、高エ
ネルギー二次電池の検討が行われてきた。2. Description of the Related Art In recent years, with the widespread use of portable devices such as video cameras and notebook computers, demand for small and high capacity secondary batteries has increased. Most of the secondary batteries currently used are nickel-cadmium batteries using an alkaline electrolyte, but the battery voltage is low at about 1.2 V, and it is difficult to improve the energy density. Therefore, high-energy secondary batteries have been studied using lithium metal, which is the base metal, as the negative electrode.
【０００３】ところが、リチウム金属を負極に使用する
二次電池では、充放電の繰り返しによってリチウムが樹
枝状（デンドライト）に成長し、短絡を起こして発火す
る危険性がある。また、活性の高い金属リチウムを使用
するので、本質的に危険性が高く、民生用として使用す
るには問題が多い。近年、このような安全性の問題を解
決し、かつリチウム電極特有の高エネルギーが可能なも
のとして、各種炭素質材料を用いたリチウムイオン二次
電池が考案されている。この方法は、充電時、炭素質材
料に、リチウムイオンがドーピングされ、金属リチウム
と同電位になるので、金属リチウムの変わりに負極に使
用することができることを利用したものである。また、
放電時には、ドープされたリチウムイオンが負極から脱
ドーピングされて、もとの炭素質材料に戻る。このよう
な、リチウムイオンがドーピングされた炭素質材料を負
極として用いた場合には、デンドライト生成の問題もな
く、また金属リチウムが存在しないため、安全性にも優
れていると言う特徴があり、現在、研究開発が活発に行
われている。However, in a secondary battery in which lithium metal is used for the negative electrode, there is a risk that lithium will grow into dendrites due to repeated charging and discharging, causing a short circuit and igniting. In addition, since highly active metallic lithium is used, it is inherently dangerous, and there are many problems in using it for consumer use. In recent years, a lithium ion secondary battery using various carbonaceous materials has been devised as a device that solves such a safety problem and enables high energy peculiar to a lithium electrode. This method utilizes the fact that the carbonaceous material is doped with lithium ions during charging and has the same potential as metallic lithium, so that it can be used for the negative electrode instead of metallic lithium. Also,
During discharge, the doped lithium ions are dedoped from the negative electrode and return to the original carbonaceous material. When such a carbonaceous material doped with lithium ions is used as the negative electrode, there is no problem of dendrite formation, and since there is no metallic lithium, there is a feature that it is also excellent in safety, Currently, research and development are actively carried out.
【０００４】上記の炭素質材料へのリチウムイオンのド
ーピングを利用した電極を用いた二次電池としては、特
開昭５７−２０８０７９号公報、特開昭５８−９３１７
６号公報、特開昭５８−１９２２６６号公報、特開昭６
２−９０８６３号公報、特開昭６２−１２２０６６号公
報、特開平２−６６８５６号公報等が公知である。Secondary batteries using an electrode utilizing the above-mentioned carbonaceous material doped with lithium ions are disclosed in JP-A-57-208079 and JP-A-58-9317.
6, JP-A-58-192266, JP-A-6-
No. 2-90863, Japanese Patent Laid-Open No. 62-122066, Japanese Patent Laid-Open No. 2-66856 and the like are known.
【０００５】炭素質材料としては、天然黒鉛、人工黒
鉛、各種のコークス粉末、メソフェーズ炭素、気相成長
炭素繊維、ピッチ系炭素繊維、ＰＡＮ系炭素繊維、各種
の樹脂焼成体などが知られている。さらに、これらの炭
素質材料について、非晶性のものから高結晶性のものま
でリチウムイオンのドーピング、脱ドーピングが可能で
あることが知られている。このような炭素質材料は、一
般には粉末の形状をとっており、電極成型のためにはテ
フロンやフッ化ビニリデン等のポリマの結着剤を加えた
シート状成型体として電極に用いられている。Known carbonaceous materials include natural graphite, artificial graphite, various coke powders, mesophase carbon, vapor grown carbon fiber, pitch carbon fiber, PAN carbon fiber and various resin fired bodies. . Furthermore, it is known that these carbonaceous materials can be doped with lithium ions and dedoped from amorphous ones to highly crystalline ones. Such a carbonaceous material is generally in the form of powder, and is used as an electrode as a sheet-shaped molded body to which a polymer binder such as Teflon or vinylidene fluoride is added for electrode molding. .
【０００６】[0006]
【発明が解決しようとする課題】しかしながら、このよ
うな炭素質材料の粉末を活物質として用いた場合、リチ
ウム金属を用いた場合と比べて重量当りのイオン濃度が
低いので、充放電容量がリチウム金属の場合と比べまだ
低いという問題がある。また、リチウム金属を用いた場
合に比べて改善されたとはいえ、サイクル特性も満足で
きるものではなく、さらなる改善が望まれている。However, when such a carbonaceous material powder is used as the active material, the ion concentration per weight is lower than that in the case where lithium metal is used, so that the charge / discharge capacity is higher than that of lithium. There is a problem that it is still lower than that of metal. Further, although it is improved as compared with the case where lithium metal is used, the cycle characteristics are not satisfactory, and further improvement is desired.
【０００７】本発明は、かかる従来技術の欠点を解消し
ようとするものであり、高容量でサイクル特性に優れた
電極およびそれを用いた非水溶媒系二次電池を提供する
ことを目的とする。The present invention is intended to solve the drawbacks of the prior art, and an object thereof is to provide an electrode having a high capacity and excellent cycle characteristics, and a non-aqueous solvent secondary battery using the same. .
【０００８】[0008]
【課題を解決するための手段】本発明は、上記課題を解
決するために以下の構成を有するものである。The present invention has the following constitution in order to solve the above problems.
【０００９】「(1) 炭素質材料からなる粉末と、少なく
とも１種の導電性粉末とを含む電極。(2) 上記(1) 記載
の電極を用いた非水溶媒系二次電池。」 炭素質材料を用いた電極は、一般には、上述したように
炭素質材料の粉末にテフロンやフッ化ビニリデンなどの
ポリマを結着剤として添加してシート状に成型した形態
で使用されている。導電性の低い活物質を使用する場合
には結着剤に加えて導電剤を添加することが一般的であ
るが、炭素質材料からなる電極の場合にはそれ自身が高
い導電性を示すため、導電剤を添加するということはこ
れまで試みられていなかった。本発明者らは、上記課題
について鋭意検討した結果、炭素質材料からなる粉末に
それよりも平均粒径の小さな導電性粉末を添加してシー
ト状に成型することにより、容量が向上し、サイクル特
性が飛躍的に向上することを見いだした。この理由につ
いては明らかではないが、導電性粉末を添加しない場合
は、炭素質材料粉末間の接触抵抗が大きいかあるいは遊
離した状態で存在する粒子があるのに対し、導電性粉末
を添加することにより、それらの充放電に関与しない粒
子が少なくなるために容量が向上するものと考えられ
る。また、導電性粉末を添加しない場合は、リチウムイ
オンのドーピング、脱ドーピングに伴う炭素質材料自身
の膨脹収縮により、上述の充放電に関与しない粒子が生
成し、サイクル劣化を引き起こしていたのに対し、導電
性粉末を添加することにより充放電に関与しない粒子の
生成を抑制できたためにサイクル特性が向上したものと
考えられる。また、特開昭６２−９０８６３号公報に
は、炭素質材料からなる活物質への導電補助剤の添加を
示唆する記載はあるが、かかる技術では、酸化物を活物
質に用いる場合に顕著な効果が見い出されると記載され
ており、実施例にも炭素質材料に導電補助剤として導電
性粉末を添加することの記載はなく、炭素質材料に導電
性粉末を添加することの効果の記載もない。"(1) An electrode containing a powder made of a carbonaceous material and at least one kind of conductive powder. (2) A non-aqueous solvent secondary battery using the electrode described in (1) above." Carbon An electrode using a high quality material is generally used in the form of a sheet formed by adding a polymer such as Teflon or vinylidene fluoride as a binder to a powder of a carbonaceous material as described above. When an active material with low conductivity is used, it is common to add a conductive agent in addition to the binder, but in the case of an electrode made of carbonaceous material, it shows high conductivity itself. However, adding a conductive agent has not been attempted so far. As a result of intensive studies on the above problems, the inventors of the present invention added a conductive powder having a smaller average particle size to a powder made of a carbonaceous material and molding the powder into a sheet shape, thereby improving the capacity and the cycle. We have found that the characteristics are dramatically improved. Although the reason for this is not clear, when the conductive powder is not added, there are particles that have a large contact resistance between the carbonaceous material powders or exist in a free state, whereas the conductive powder should be added. Therefore, it is considered that the capacity is improved because the number of particles that do not participate in the charge and discharge is reduced. In addition, in the case where the conductive powder was not added, the particles not involved in the charge and discharge described above were generated due to the expansion and contraction of the carbonaceous material itself accompanying the doping and dedoping of lithium ions, which caused cycle deterioration. It is considered that the cycle characteristics were improved because the addition of the conductive powder could suppress the generation of particles not involved in charging / discharging. Further, Japanese Patent Application Laid-Open No. 62-90863 discloses the addition of a conductive auxiliary agent to an active material made of a carbonaceous material, but such a technique is remarkable when an oxide is used as the active material. It is described that an effect is found, and there is no description of adding conductive powder to the carbonaceous material as a conductive auxiliary agent even in the examples, and there is also description of the effect of adding conductive powder to the carbonaceous material. Absent.
【００１０】以下、本発明の電極について具体例を挙げ
ながら詳述する。Hereinafter, the electrode of the present invention will be described in detail with reference to specific examples.
【００１１】本発明に用いられる炭素質材料としては、
特に限定されるものではなく、リチウムイオンをドーピ
ング、脱ドーピング可能なものが用いられる。好ましく
は、リチウムイオンの充放電容量が２００ｍＡｈ／ｇ以
上のものが用いられる。具体的には、天然黒鉛、人工黒
鉛、各種のコークス粉末、メソフェーズ炭素、気相成長
炭素繊維、ピッチ系炭素繊維、ＰＡＮ系炭素繊維、各種
の樹脂焼成体などが使用可能であり、それぞれ非晶性の
ものから高結晶性のものまで使用可能である。これらの
粉末は、平均粒径５〜５０μｍのものが好ましく使用さ
れる。平均粒径５０μｍを越えるものは成型性が不十分
となる傾向がある。また、平均粒径５μｍ未満のもの
は、これらの炭素質材料の粉末が粉砕しにくいために入
手が困難であり、粉砕した場合でもコスト高になった
り、不純物の混入が避けられないため、実際には採用し
難いからである。The carbonaceous material used in the present invention includes:
The material is not particularly limited, and one capable of doping and dedoping lithium ions is used. Preferably, lithium ion charge / discharge capacity of 200 mAh / g or more is used. Specifically, natural graphite, artificial graphite, various coke powders, mesophase carbon, vapor grown carbon fiber, pitch-based carbon fiber, PAN-based carbon fiber, various resin fired bodies and the like can be used, and each is amorphous. It is possible to use from crystalline to highly crystalline ones. These powders preferably have an average particle size of 5 to 50 μm. If the average particle size exceeds 50 μm, the moldability tends to be insufficient. In addition, if the average particle size is less than 5 μm, it is difficult to obtain these carbonaceous material powders because it is difficult to pulverize them, and even if they are pulverized, the cost is high and the inclusion of impurities is unavoidable. This is because it is difficult to adopt for.
【００１２】本発明に用いられる導電性粉末では、体積
固有抵抗が１Ω・ｃｍを越えると導電性粉末の添加に抵
抗の低減効果が小さくなる。なお、導電性粉末の体積固
有抵抗は、試料を円筒状の容器につめ、５０±１ｋｇ／
ｃｍ2 の圧力で圧縮し、試料の高さが１０±０．５ｍｍ
になるように調整した圧縮試料の両端の電圧・電流を測
定して、次式から求められる。In the electroconductive powder used in the present invention, when the volume resistivity exceeds 1 Ω · cm, the effect of reducing the resistance becomes small when the electroconductive powder is added. The volume resistivity of the conductive powder is 50 ± 1 kg /
Compressed with a pressure of cm 2 , the sample height is 10 ± 0.5 mm
The voltage and current at both ends of the compressed sample adjusted so that
【００１３】 体積固有抵抗( Ω・cm)={ 断面積（cm2 )/資料の高さ(cm)｝×（電圧／電流） 具体的にはニッケル、銅などの金属粉末、酸化インジウ
ム、酸化スズ等の導電性セラミックス粉末などが挙げら
れるが、炭素粉末が電解液に対する化学的安定性などの
点から特に好ましく用いられる。また、２種以上粉末を
使用してもよい。導電性粉末としては、炭素質材料から
なる粉末の平均粒径Ａと導電性粉末の平均粒径ＢがＡ／
Ｂ≧２の関係にあるものが好ましく用いられ、好ましく
はＡ／Ｂ≧５の関係にあるものが用いられる。Ａ／Ｂ＜
２の場合は、導電性粉末の粒径が相対的に大きくなるた
め、活物質粒子の空隙を埋めるという導電剤としての役
割が低下する。Volume resistivity (Ω · cm) = {cross-sectional area (cm 2 ) / height of material (cm)} × (voltage / current) Specifically, metal powder such as nickel or copper, indium oxide, oxidation Conductive ceramic powders such as tin can be used, but carbon powders are particularly preferably used from the viewpoint of chemical stability with respect to an electrolytic solution. Moreover, you may use 2 or more types of powder. As the conductive powder, the average particle size A of the powder made of carbonaceous material and the average particle size B of the conductive powder are A /
Those having a relationship of B ≧ 2 are preferably used, and those having a relationship of A / B ≧ 5 are preferably used. A / B <
In the case of 2, since the particle size of the conductive powder becomes relatively large, the role of the conductive agent of filling the voids of the active material particles is reduced.
【００１４】導電性粉末の大きさとしては、平均粒径４
μｍ以下、好ましくは２μｍ以下であることが好まし
い。平均粒径４μｍを越えると、活物質粒子の空隙を埋
めるという導電剤の役割が果たしにくくなる。なお、粉
末の粒径は電子顕微鏡による観察から求められる上記導
電性粉末としては、具体的には、人工黒鉛粉末やアセチ
レンブラック、各種のカーボンブラックなどが挙げられ
る。その中でも、アセチレンブラックが、微粒子である
こと、化学的にも安定であることから、好ましく用いら
れる。また、導電性粉末として添加する炭素粉末は、そ
れ自身がリチウムイオンをドーピング、脱ドーピング可
能で活物質として作用するものでも、そうでないもので
も構わない。As the size of the conductive powder, the average particle size is 4
It is preferably not more than μm, preferably not more than 2 μm. When the average particle size exceeds 4 μm, it becomes difficult to fulfill the role of the conductive agent of filling the voids of the active material particles. As the conductive powder whose particle diameter is determined by observation with an electron microscope, specifically, artificial graphite powder, acetylene black, various carbon blacks and the like can be mentioned. Among them, acetylene black is preferably used because it is fine particles and is chemically stable. The carbon powder added as the conductive powder may or may not itself be capable of doping and dedoping with lithium ions and acting as an active material.
【００１５】添加する導電性粉末は、多すぎると活物質
の効果が相対的に低下する傾向があり、少なすぎると本
発明にいう容量の向上やサイクル特性の向上の点で、効
果が低くなる傾向がある。好ましくは、電極合剤中０．
１重量％以上、４０重量％以下、より好ましくは０．１
重量％以上、２０重量％以下の割合で使用される。If the amount of the conductive powder added is too large, the effect of the active material tends to be relatively lowered, and if it is too small, the effect is lowered in terms of the improvement of the capacity and the cycle characteristics in the present invention. Tend. Preferably, it is 0.
1% by weight or more and 40% by weight or less, more preferably 0.1
It is used in a proportion of not less than 20% by weight and not more than 20% by weight.
【００１６】本発明の電極は、通常、上記炭素質材料か
らなる粉末と導電性粉末に結着剤としてポリマを添加
し、シート状に成型して使用される。結着剤としては、
テフロン樹脂やポリフッ化ビニリデンなどに代表される
フッ素系樹脂、カルボキシメチルセルロースに代表され
るセルロース類等の熱可塑性樹脂や、ポリイミド、エポ
キシ樹脂、フェノール樹脂、不飽和ポリエステル樹脂な
どの熱硬化性樹脂、およびそれらの混合物が好ましく用
いられる。その添加量は０．１〜３０重量％であること
が好ましい。The electrode of the present invention is usually used by adding a polymer as a binder to the powder made of the above-mentioned carbonaceous material and the conductive powder and molding it into a sheet. As a binder,
Fluorine-based resins typified by Teflon resin and polyvinylidene fluoride, thermoplastic resins such as celluloses typified by carboxymethyl cellulose, and thermosetting resins such as polyimide, epoxy resin, phenol resin, and unsaturated polyester resin, and A mixture thereof is preferably used. The addition amount is preferably 0.1 to 30% by weight.
【００１７】これらは、一般には、溶媒に分散したスラ
リーの形で集電体の金属箔上に塗布し、シート状に成型
される。集電体の金属箔としては、特に限定されるもの
ではないが、金、銀、銅、白金、アルミニウム、鉄、ニ
ッケル、クロム、マンガン、鉛、タングステン、チタン
などが挙げられ、さらにステンレスなど上記金属の合金
などを用いても良い。金属箔の厚さが厚くなると、電池
内に収納できる活物質の量が減少するため、箔の厚さは
薄いものが好ましい。電気伝導度、金属箔の厚さやコス
トから、銅箔が好ましく用いられる。These are generally applied in the form of a slurry dispersed in a solvent onto a metal foil of a current collector and molded into a sheet. The metal foil of the current collector is not particularly limited, but examples thereof include gold, silver, copper, platinum, aluminum, iron, nickel, chromium, manganese, lead, tungsten, titanium, and the like. A metal alloy or the like may be used. Since the amount of active material that can be stored in the battery decreases as the thickness of the metal foil increases, the thickness of the foil is preferably thin. Copper foil is preferably used in terms of electrical conductivity, thickness of metal foil, and cost.
【００１８】本発明の電極は、各種電池の活電極として
利用可能であり、一次電池、二次電池など、どのような
電池に利用されるかは特に限定されるものではない。こ
の中で、二次電池の負極に好ましく用いられる。特に好
ましい二次電池としては、過塩素酸リチウム、硼フッ化
リチウム、６フッ化リン・リチウムのようにアルカリ金
属塩を含む非水溶媒電解液を用いた二次電池を挙げるこ
とができる。The electrode of the present invention can be used as an active electrode of various batteries, and what kind of battery such as a primary battery or a secondary battery is used is not particularly limited. Among these, it is preferably used as a negative electrode of a secondary battery. As a particularly preferable secondary battery, a secondary battery using a nonaqueous solvent electrolytic solution containing an alkali metal salt such as lithium perchlorate, lithium borofluoride, and phosphorus hexafluoride / lithium can be mentioned.
【００１９】本発明の電極をアルカリ金属塩を含む非水
電解液二次電池に用いる場合には、炭素質材料へのカチ
オンあるいはアニオンのドーピングを利用したものであ
り、カチオンがドープされる炭素質材料を負極に、アニ
オンがドープされる炭素質材料を正極に用いることとな
る。これらは、炭素質材料の各種特性によって、正極あ
るいは負極に使用され得るべきものであるが、必ずしも
両極を本発明の電極にする必要はなく、本発明の炭素質
材料と導電性粉末より構成される電極を負極に、炭素質
材料以外の活物質を含む電極を正極にすることも好まし
い実施態様となる。When the electrode of the present invention is used in a non-aqueous electrolyte secondary battery containing an alkali metal salt, the carbonaceous material is doped with cations or anions. The material is used for the negative electrode, and the carbonaceous material doped with anions is used for the positive electrode. These should be able to be used for the positive electrode or the negative electrode depending on various characteristics of the carbonaceous material, but it is not always necessary to use both electrodes as the electrodes of the present invention, and it is composed of the carbonaceous material of the present invention and conductive powder. It is also a preferred embodiment to use the electrode as the negative electrode and the electrode containing the active material other than the carbonaceous material as the positive electrode.
【００２０】他の正極物質の具体例としては、人造ある
いは天然の黒鉛粉末、フッ化カーボン、金属あるいは金
属酸化物などの無機化合物や有機高分子化合物などが挙
げられる。この場合、金属あるいは金属酸化物などの無
機化合物を用いた場合、正極では、カチオンのドープと
脱ドープを利用した充放電反応が生じる。有機高分子化
合物を用いた場合には、アニオンのドープと脱ドープに
より充放電反応が生じる。このように、物質により様々
な充放電反応様式を採るものであり、これらは必要とさ
れる電池の正極特性に応じて適宜選択されるものであ
る。具体的な正極材料としては、アルカリ金属を含む遷
移金属酸化物や遷移金属カルコゲンなどの無機化合物、
ポリアセチレン、ポリパラフェニレン、ポリフェニレン
ビニレン、ポリアニリン、ポリピロール、ポリチオフェ
ンなどの共役系高分子、ジスルフィド結合を有する架橋
高分子、塩化チオニルなど、通常の二次電池において用
いられる正極を挙げることができる。これらの中で、リ
チウム塩を含む非水電解液を用いた二次電池の場合に
は、コバルト、マンガン、モリブデン、バナジウム、ク
ロム、鉄、銅、チタンなどの遷移金属酸化物や遷移金属
カルコゲンが好ましく用いられる。Specific examples of other positive electrode materials include artificial or natural graphite powder, fluorinated carbon, inorganic compounds such as metal or metal oxide, and organic polymer compounds. In this case, when an inorganic compound such as a metal or a metal oxide is used, a charge / discharge reaction utilizing cation doping and dedoping occurs in the positive electrode. When an organic polymer compound is used, a charge / discharge reaction occurs due to anion doping and undoping. As described above, various charging / discharging reaction modes are adopted depending on the substance, and these are appropriately selected according to the required positive electrode characteristics of the battery. Specific positive electrode materials include inorganic compounds such as transition metal oxides and transition metal chalcogens containing alkali metals,
Examples of the positive electrode used in ordinary secondary batteries include conjugated polymers such as polyacetylene, polyparaphenylene, polyphenylene vinylene, polyaniline, polypyrrole, and polythiophene, crosslinked polymers having a disulfide bond, and thionyl chloride. Among these, in the case of a secondary battery using a non-aqueous electrolytic solution containing a lithium salt, transition metal oxides and transition metal chalcogens such as cobalt, manganese, molybdenum, vanadium, chromium, iron, copper and titanium are It is preferably used.
【００２１】ＬｉＣｏＯ2 またはＬｉＮｉＯ2 、および
これらに他の金属元素を添加した組成のリチウム複合酸
化物は、電圧が高く、エネルギー密度も大きいために、
最も好ましく使用される。LiCoO 2 or LiNiO 2 and a lithium composite oxide having a composition obtained by adding another metal element to these have a high voltage and a large energy density.
Most preferably used.
【００２２】本発明の電極を用いた二次電池の電解液と
しては、特に限定されることなく従来の電解液が用いら
れ、例えば酸あるいはアルカリ水溶液、または非水溶媒
などが挙げられる。この中で、上述のアルカリ金属塩を
含む非水溶媒電解液からなる二次電池の電解液として
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、Ｎ- メチルピロリドン、アセトニ
トリル、Ｎ，Ｎ−ジメチルホルムアミド、ジメチルスル
フォキシド、テトラヒドロフラン、１，３−ジオキソラ
ン、ギ酸メチル、スルホラン、オキサゾリドン、塩化チ
オニル、１，２−ジメトキシエタン、ジエチレンカーボ
ネートや、これらの誘導体や混合物などが好ましく用い
られる。電解液に含まれる電解質としては、アルカリ金
属、特にリチウムのハロゲン化物、過塩素酸塩、チオシ
アン塩、ホウフッ化塩、リンフッ化塩、砒素フッ化塩、
アルミニウムフッ化塩、トリフルオロメチル硫酸塩など
が好ましく用いられる。The electrolytic solution of the secondary battery using the electrode of the present invention is not particularly limited, and a conventional electrolytic solution may be used, and examples thereof include an acid or alkaline aqueous solution or a non-aqueous solvent. Among these, as an electrolyte solution of a secondary battery comprising a non-aqueous solvent electrolyte solution containing the above-mentioned alkali metal salt, propylene carbonate, ethylene carbonate,
γ-butyrolactone, N-methylpyrrolidone, acetonitrile, N, N-dimethylformamide, dimethylsulfoxide, tetrahydrofuran, 1,3-dioxolane, methyl formate, sulfolane, oxazolidone, thionyl chloride, 1,2-dimethoxyethane, diethylene carbonate Alternatively, derivatives and mixtures of these are preferably used. As the electrolyte contained in the electrolytic solution, an alkali metal, particularly a lithium halide, a perchlorate, a thiocyanate, a borofluoride, a phosphorus fluoride, an arsenic fluoride,
Aluminum fluoride, trifluoromethyl sulfate and the like are preferably used.
【００２３】本発明の電極を用いた二次電池の用途とし
ては、軽量かつ高容量で、高エネルギー密度であるとい
う特徴を利用して、ビデオカメラ、パソコン、ワープ
ロ、ラジカセ、携帯電話などの携帯用小型電子機器など
に広く利用可能である。The secondary battery using the electrode of the present invention can be used in mobile phones such as a video camera, a personal computer, a word processor, a radio-cassette, and a mobile phone by utilizing the features of being lightweight, having a high capacity, and having a high energy density. It can be widely used for small electronic devices.
【００２４】[0024]
【実施例】本発明の具体的実施態様を以下に実施例をも
って述べるが、本発明はこれに限定されるものではな
い。EXAMPLES Specific embodiments of the present invention will be described below with reference to examples, but the present invention is not limited thereto.
【００２５】実施例１ 市販のメソカーボンマイクロビーズ粉末（大阪ガス製、
平均粒径６μｍ）８０重量％、導電性粉末として、アセ
チレンブラック（電気化学工業製、平均粒径０．０４μ
ｍ、体積固有抵抗０．２Ω・ｃｍ）５重量％、結着剤と
してポリフッ化ビニリデン（呉羽化学製）１５重量％を
混合し、これにＮ−メチルピロリドンを加えて、スラリ
ーとした。このスラリーを銅箔に塗布乾燥後プレスして
シート状の電極を得た。Example 1 Commercially available mesocarbon microbead powder (manufactured by Osaka Gas,
80% by weight of an average particle size of 6 μm, and as conductive powder, acetylene black (manufactured by Denki Kagaku Kogyo, average particle size of 0.04 μm).
m, volume resistivity 0.2 Ω · cm) 5% by weight, and polyvinylidene fluoride (manufactured by Kureha Chemical Co., Ltd.) 15% by weight as a binder were mixed, and N-methylpyrrolidone was added thereto to form a slurry. This slurry was applied to a copper foil, dried and pressed to obtain a sheet-shaped electrode.
【００２６】次に、該電極を用いて充放電評価を行っ
た。電解液は１Ｍ四ホウフッ化リチウムを含むプロピレ
ンカーボネート、ジメチルカーボネートの混合溶液を、
対極および参照極には、金属リチウム箔を用いる３極式
セルで評価した。重量当たりの電流密度として４０ｍＡ
／ｇの定電流で、０Ｖ（ｖｓ．Ｌｉ+ ／Ｌｉ）まで充電
した後、１．５Ｖ（ｖｓ．Ｌｉ+ ／Ｌｉ）まで放電し
た。このときの放電容量は、２５０ｍＡｈ／ｇであっ
た。また、同じ充放電条件で１０回サイクルさせた後の
放電容量は、初回の９５％であった。Next, charge / discharge evaluation was performed using the electrode. The electrolytic solution is a mixed solution of propylene carbonate and dimethyl carbonate containing 1M lithium tetrafluoroborate,
The counter electrode and the reference electrode were evaluated with a three-electrode cell using a metallic lithium foil. 40mA as current density per weight
The battery was charged to 0 V (vs. Li + / Li) at a constant current of / g and then discharged to 1.5 V (vs. Li + / Li). The discharge capacity at this time was 250 mAh / g. The discharge capacity after 10 cycles under the same charge / discharge conditions was 95% of the initial value.
【００２７】比較例１ 市販のメソカーボンマイクロビーズ粉末（大阪ガス製、
平均粒径６μ）８５重量％、結着剤としてポリフッ化ビ
ニリデン（呉羽化学製）１５重量％とした以外は、実施
例１と同様の方法で電極を作製した。実施例１と同様の
方法で測定した該電極の放電容量は２２０ｍＡｈ／ｇで
あった。また、１０回サイクルさせた後の放電容量は、
初回の５０％であった。Comparative Example 1 Commercially available mesocarbon microbead powder (manufactured by Osaka Gas,
An electrode was produced in the same manner as in Example 1 except that the average particle size was 85 μ% and the binder was polyvinylidene fluoride (Kureha Chemical Co., Ltd.) 15% by weight. The discharge capacity of the electrode measured by the same method as in Example 1 was 220 mAh / g. The discharge capacity after 10 cycles was
It was 50% of the first time.
【００２８】実施例２ 市販のＬｉＣｏＯ2 （関西触媒化学製）に導電剤として
人工黒鉛、結着剤としてポリフッ化ビニリデン（ＰＶｄ
Ｆ）、溶媒としてＮ−メチルピロリドンを用い、重量比
でＬｉＣｏＯ2 ／人工黒鉛／ＰＶｄＦ＝９０／５／５と
なるように混合し正極スラリーを調製し、このスラリー
をアルミ箔に塗布乾燥後プレスして正極を得た。Example 2 Commercially available LiCoO 2 (manufactured by Kansai Catalyst Co., Ltd.) was used as artificial graphite as a conductive agent, and polyvinylidene fluoride (PVd) as a binder.
F), using N-methylpyrrolidone as a solvent, and mixing so as to have a weight ratio of LiCoO 2 / artificial graphite / PVdF = 90/5/5 to prepare a positive electrode slurry, which is applied to an aluminum foil and dried, followed by pressing. The positive electrode was obtained.
【００２９】実施例１にて作製して電極を負極とし、多
孔質ポリプロピレンフィルム（セルガード＃２５００、
ヘキスト・セラニーズ社製）のセパレータを介して、上
記にて作製した正極と重ね合わせて、単３型の電池を作
製した。電解液は、１Ｍ四ホウフッ化リチウムを含むプ
ロピレンカーボネート、ジメチルカーボネートの混合溶
液を用いた。A porous polypropylene film (Celgard # 2500, manufactured by Example 1 and using the electrode as a negative electrode)
An AA battery was produced by stacking the positive electrode produced above through a separator (Hoechst Celanese Co., Ltd.). As an electrolytic solution, a mixed solution of propylene carbonate and dimethyl carbonate containing 1M lithium tetrafluoroborate was used.
【００３０】上記にて作製した二次電池の充放電評価を
行った。最大電流８０ｍＡで４．２Ｖ定電位充電を行っ
た後、８０ｍＡの定電流で２．７５まで放電を行った。
この時の放電容量は３８０ｍＡｈであった。また、１０
０回サイクル後の放電容量は、初回の８０％であった。The secondary battery produced as described above was evaluated for charge and discharge. After performing 4.2V constant-potential charging with a maximum current of 80 mA, discharging was performed up to 2.75 with a constant current of 80 mA.
The discharge capacity at this time was 380 mAh. Also, 10
The discharge capacity after 0 cycles was 80% of the initial value.
【００３１】比較例２ 比較例１で作製した電極を負極とした以外は、実施例２
と同様の方法により電池を作製した。実施例２と同様の
方法により測定したこの電池の放電容量は３２０ｍＡｈ
であり、１００回サイクル後の放電容量は、初回の５０
％であった。Comparative Example 2 Example 2 was repeated except that the electrode prepared in Comparative Example 1 was used as the negative electrode.
A battery was produced in the same manner as in. The discharge capacity of this battery measured by the same method as in Example 2 was 320 mAh.
The discharge capacity after 100 cycles is 50
%Met.
【００３２】[0032]
【発明の効果】本発明により、高容量でサイクル特性に
優れた電極およびそれを用いた非水溶媒系二次電池を提
供することができた。According to the present invention, it is possible to provide an electrode having a high capacity and excellent cycle characteristics and a non-aqueous solvent secondary battery using the electrode.
Claims (12)
種の導電性粉末とを含む電極。1. A powder comprising a carbonaceous material, and at least 1.
An electrode comprising a seed conductive powder.
該導電性粉末の平均粒径ＢがＡ／Ｂ≧２の関係にある請
求項１記載の電極。2. The electrode according to claim 1, wherein the average particle size A of the powder made of the carbonaceous material and the average particle size B of the conductive powder have a relationship of A / B ≧ 2.
と、該導電性粉末の平均粒径ＢがＡ／Ｂ≧５の関係にあ
る請求項１または２記載の電極。3. The average particle size A of the powder made of the carbonaceous material.
And the average particle size B of the conductive powder is A / B ≧ 5.
ることを特徴とする請求項１〜３のいずれかに記載の電
極。4. The electrode according to claim 1, wherein the conductive powder has an average particle diameter of 4 μm or less.
以下である請求項１〜４のいずれかに記載の電極。5. The volume resistivity of the conductive powder is 1 Ω · cm.
The electrode according to any one of claims 1 to 4, which is as follows.
１重量％以上、４０重量％以下である請求項１〜５のい
ずれかに記載の電極。6. The content of the conductive powder in the electrode mixture is 0.
The electrode according to claim 1, which is 1% by weight or more and 40% by weight or less.
１重量％以上、２０重量％以下である請求項１〜６のい
ずれかに記載の電極。7. The content of the conductive powder in the electrode mixture is 0.
The electrode according to claim 1, which is 1% by weight or more and 20% by weight or less.
ン充放電容量が２００ｍＡｈ／ｇ以上である請求項１〜
７のいずれかに記載の電極。8. The lithium ion charge / discharge capacity of the powder made of the carbonaceous material is 200 mAh / g or more.
7. The electrode according to any one of 7.
〜８のいずれかに記載の電極。9. The conductive powder is carbon powder.
The electrode according to any one of to 8.
用いた非水溶媒系二次電池。10. A non-aqueous solvent secondary battery using the electrode according to claim 1.
して請求項１〜９のいずれかに記載の電極を用いたこと
を特徴とする請求項１０記載の非水溶媒系二次電池。11. A non-aqueous solvent secondary battery according to claim 10, wherein a transition metal oxide is used as a positive electrode material and the electrode according to any one of claims 1 to 9 is used as a negative electrode material.
ｉＮｉＯ2 およびこれらに他の金属元素を添加した組成
物から選ばれる請求項１０記載の非水溶媒系二次電池。12. The transition metal oxide is LiCoO 2 , L
The non-aqueous solvent secondary battery according to claim 10, which is selected from iNiO 2 and a composition obtained by adding another metal element to them.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7113335A JPH08306354A (en) | 1995-05-11 | 1995-05-11 | Electrode and nonaqueous solvent type secondary battery using the electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7113335A JPH08306354A (en) | 1995-05-11 | 1995-05-11 | Electrode and nonaqueous solvent type secondary battery using the electrode |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH08306354A true JPH08306354A (en) | 1996-11-22 |
Family
ID=14609642
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7113335A Pending JPH08306354A (en) | 1995-05-11 | 1995-05-11 | Electrode and nonaqueous solvent type secondary battery using the electrode |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH08306354A (en) |
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| US6677074B2 (en) | 1998-06-25 | 2004-01-13 | Mitsubishi Denki Kabushiki Kaisha | Cell and method of producing the same |
| US6696203B2 (en) | 1999-06-10 | 2004-02-24 | Mitsubishi Denki Kabushiki Kaisha | Battery and electrode including an active material, an electrically conductive material and a conducting agent |
| EP1128451A1 (en) * | 1999-06-10 | 2001-08-29 | Mitsubishi Denki Kabushiki Kaisha | Cell |
| WO2000077867A1 (en) * | 1999-06-10 | 2000-12-21 | Mitsubishi Denki Kabushiki Kaisha | Cell |
| EP1128451A4 (en) * | 1999-06-10 | 2007-05-02 | Mitsubishi Electric Corp | Cell |
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