JPH11283629A - Organic electrolyte battery - Google Patents
Organic electrolyte batteryInfo
- Publication number
- JPH11283629A JPH11283629A JP10100037A JP10003798A JPH11283629A JP H11283629 A JPH11283629 A JP H11283629A JP 10100037 A JP10100037 A JP 10100037A JP 10003798 A JP10003798 A JP 10003798A JP H11283629 A JPH11283629 A JP H11283629A
- Authority
- JP
- Japan
- Prior art keywords
- positive electrode
- conductive agent
- organic electrolyte
- active material
- electrode active
- 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]
【発明の属する技術分野】本発明はポータブル機器の駆
動用電源や電気自動車等の動力としての有機電解質電池
の正極の導電剤の改良に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an improvement in a conductive agent for a positive electrode of an organic electrolyte battery used as a power source for driving a portable device or a power source for an electric vehicle.
【０００２】[0002]
【従来の技術】近年、ラップトップコンピューター、ワ
ープロ等の携帯情報機器、カメラ一体型ＶＴＲ、液晶テ
レビ等のＡＶ機器や携帯電話等の移動通信機器さらには
電気自動車用動力電源としての電池に対し大電流、大出
力を要求する機器が多種多様に発達し、より高エネルギ
ー密度の電池が要望されており、その要望に応えるべ
く、有機電解質電池が提案され、実用化に至っている。
しかしながらこれらの電池はまだ満足するには至ってお
らず、さらなる高出力、長寿命が要求されている。2. Description of the Related Art In recent years, portable information devices such as laptop computers and word processors, AV devices such as camera-integrated VTRs and liquid crystal televisions, mobile communication devices such as mobile phones, and batteries as power sources for electric vehicles have become increasingly important. Devices that require high current and large output have been developed in various ways, and batteries with higher energy density have been demanded. To meet the demand, organic electrolyte batteries have been proposed and have been put to practical use.
However, these batteries are not yet satisfactory, and higher output and longer life are required.
【０００３】一般に、有機電解質電池の正極活物質には
コバルト酸リチウムが用いられているが、資源、コスト
の観点から、マンガン酸リチウムが有望視されている。In general, lithium cobaltate is used as a positive electrode active material of an organic electrolyte battery, but lithium manganate is considered promising from the viewpoint of resources and cost.
【０００４】[0004]
【発明が解決しようとする課題】しかし、このマンガン
酸リチウムはコバルト酸リチウムに比較し、電子伝導性
が低く、それ故、高率放電特性に劣り、機器の要求に十
分に応えられないのいが現状である。また、高率放電特
性を高めるには導電剤を多く用いればよいが、そうする
ことにより、正極合剤中に占める活物質量が減るため、
放電容量が減少する。本発明は、従来技術に見られる前
記問題を解決し、高率放電特性に優れた正極を提供する
ことを課題とする。However, this lithium manganate has a lower electron conductivity than lithium cobalt oxide, and therefore has a poor high-rate discharge characteristic and cannot sufficiently meet the demands of equipment. Is the current situation. In addition, a high amount of conductive agent may be used to enhance the high-rate discharge characteristics, but by doing so, the amount of active material in the positive electrode mixture is reduced,
The discharge capacity decreases. An object of the present invention is to solve the above-mentioned problems found in the prior art and to provide a positive electrode having excellent high-rate discharge characteristics.
【０００５】[0005]
【課題を解決するための手段】本発明有機電解質電池
は、正極活物質と導電剤とバインダーを備えた合剤層が
金属の基材に形成されてなる正極１と、負極２と有機電
解質よりなり、この正極活物質がマンガンを主体とする
リチウム複合酸化物である有機電解質電池において、導
電剤がカーボンナノチューブであること、また、カーボ
ンナノチューブの割合が正極活物質と導電剤とバインダ
ーの合計重量に対して２重量部以上１５重量部以下であ
ることを特徴とする。The organic electrolyte battery of the present invention comprises a positive electrode 1 in which a mixture layer comprising a positive electrode active material, a conductive agent and a binder is formed on a metal substrate, a negative electrode 2 and an organic electrolyte. In the organic electrolyte battery in which the positive electrode active material is a lithium composite oxide mainly composed of manganese, the conductive agent is a carbon nanotube, and the ratio of the carbon nanotube is the total weight of the positive electrode active material, the conductive agent, and the binder. Is not less than 2 parts by weight and not more than 15 parts by weight.
【０００６】[0006]
【発明の実施の形態】本発明による有機電解質電池で
は、導電剤としてカーボンナノチューブを使用し、ま
た、その添加量を２重量部以上１５重量部以下とする。
このようにすることにより、正極活物質同士の導電性を
改良し、高率放特性や充放電サイクル特性に優れた有機
電解質電池を実現することができる。BEST MODE FOR CARRYING OUT THE INVENTION In an organic electrolyte battery according to the present invention, carbon nanotubes are used as a conductive agent, and the addition amount is 2 to 15 parts by weight.
By doing so, it is possible to improve the conductivity between the positive electrode active materials and realize an organic electrolyte battery having excellent high rate discharge characteristics and charge / discharge cycle characteristics.
【０００７】[0007]
【実施例】以下、本発明の具体的な実施例について説明
するが、本発明がこれらの実施例に限定されるものでな
いことは言うまでもない。EXAMPLES Hereinafter, specific examples of the present invention will be described, but it goes without saying that the present invention is not limited to these examples.
【０００８】本実施例は正極活物質にＬｉＭｎ2 Ｏ4 、
負極に天然黒鉛、正極および負極のバインダーとしてポ
リフッ化ビニリデン樹脂を用いた円筒型有機電解質電池
に適用したものである。In this embodiment, LiMn 2 O 4 ,
The present invention is applied to a cylindrical organic electrolyte battery using natural graphite as a negative electrode and polyvinylidene fluoride resin as a binder for the positive and negative electrodes.
【０００９】図１は本発明有機電解質電池の一実施例を
示す構造図である。図１において、正極１と負極２とを
セパレータ３を介して渦巻状に巻いてなる電極群を、内
径１５．３ｍｍのニッケルメッキを施した鉄製の有底円
筒型電池ケース４に挿入している。ここで、電池ケース
に鉄製を用いるため、この電池ケースが負極側に相当す
ることになる。FIG. 1 is a structural view showing one embodiment of the organic electrolyte battery of the present invention. In FIG. 1, an electrode group formed by spirally winding a positive electrode 1 and a negative electrode 2 through a separator 3 is inserted into a nickel-plated iron bottomed cylindrical battery case 4 having an inner diameter of 15.3 mm. . Here, since the battery case is made of iron, the battery case corresponds to the negative electrode side.
【００１０】５は正極１と負極２とをセパレータ３を介
して巻き取る際のセンターピンで外径３ｍｍ、長さ２６
ｍｍのアルミニウムよりなる。セパレータ３は、厚さ２
５μｍのポリエチレン製微多孔膜を用いた。Reference numeral 5 denotes a center pin for winding the positive electrode 1 and the negative electrode 2 through the separator 3 and has an outer diameter of 3 mm and a length of 26 mm.
mm of aluminum. The separator 3 has a thickness of 2
A 5 μm polyethylene microporous membrane was used.
【００１１】正極１には厚み２０μｍのアルミニウム箔
の両面に、ＬｉＭｎ2 Ｏ4 に結着剤であるポリフッ化ビ
ニリデン樹脂と、導電剤としてカーボンナノチューブ
（Ｈｙｐｅｒｉｏｎ Ｃａｔａｌｙｓｉｓ Ｉｎｔｅｒ
ｎａｔｉｏｎａｌ製 外径約０．０１μ 長さ１〜１０
μ 比表面積２５０ｍ2 ／ｇ）を表１に示す割合で加
え、ペースト状に混合し、塗布、乾燥、圧延後、長さ４
７０ｍｍ、幅２４ｍｍに切断したものを用いた。The cathode 1 has a 20 μm-thick aluminum foil on both sides, a polyvinylidene fluoride resin as a binder for LiMn 2 O 4 , and carbon nanotubes (Hyperion Catalyst Interference) as a conductive agent.
made by national, outer diameter about 0.01μ, length 1-10
μ specific surface area of 250 m 2 / g) at a ratio shown in Table 1, mixed in a paste, applied, dried and rolled, and
A piece cut to 70 mm and a width of 24 mm was used.
【００１２】[0012]
【表１】 負極２には厚み１４μｍの銅箔の両面に、天然黒鉛と結
着剤であるポリフッ化ビニリデンを９０：１０重量部
（固形分比）の割合でペースト状に混合し、塗布、乾
燥、圧延後、長さ４９０ｍｍ、幅２６ｍｍに切断したも
のを用いた。[Table 1] The negative electrode 2 was prepared by mixing natural graphite and polyvinylidene fluoride as a binder in a paste form at a ratio of 90:10 parts by weight (solid content ratio) on both sides of a copper foil having a thickness of 14 μm, coating, drying and rolling. 490 mm in length and 26 mm in width were used.
【００１３】６は蓋体で、ガスケット７を介して電池ケ
ース４にかしめ封口されている。なお、この蓋体６の内
面には正極１と接続されている正極リード８が溶接され
ている。電解質にはＬｉＰＦ6 を１mol/l 含むエチレン
カーボネート：ジエチルカーボネート＝１：１（体積
比）の混合液を用いた。９は負極リード、１０はＰＣＴ
素子、１１は安全弁である。Reference numeral 6 denotes a lid which is swaged and sealed in the battery case 4 via a gasket 7. A positive electrode lead 8 connected to the positive electrode 1 is welded to the inner surface of the lid 6. As the electrolyte, a mixed solution of ethylene carbonate: diethyl carbonate = 1: 1 (volume ratio) containing 1 mol / l of LiPF 6 was used. 9 is a negative electrode lead, 10 is PCT
Element 11 is a safety valve.
【００１４】以上により、外径１５．９ｍｍ、高さ３３
ｍｍの円筒型電池Ａ〜電池Ｉを組み立てた。また、比較
例として、導電剤にカーボンナノチューブの代わりにグ
ラファイト（日本黒鉛工業製ＳＰ−２０）を１０％添加
したことを除き、全て実施例と同じ条件の円筒型有機電
解質電池を組み立てた。この電池を比較例電池Ｊとす
る。As described above, the outer diameter is 15.9 mm and the height is 33
mm cylindrical batteries A to I were assembled. In addition, as a comparative example, a cylindrical organic electrolyte battery was assembled under the same conditions as in the example except that 10% of graphite (SP-20 manufactured by Nippon Graphite Industries) was added to the conductive agent instead of the carbon nanotube. This battery is referred to as Comparative Example Battery J.
【００１５】これらの電池Ａ〜電池Ｊについて放電試験
を行った。A discharge test was performed on these batteries A to J.
【００１６】試験方法として、充電電流１Ａ，充電上限
電圧４．１Ｖの定電流・定電圧で５時間充電を行い、
０．１Ａの電流で２．７５Ｖまで放電し、次に、充電電
流１Ａ，充電上限電圧４．１Ｖの定電流・定電圧で５時
間充電を行い、１Ａの電流で２．７５Ｖまで放電し、
０．１Ａ放電に対する、１Ａ放電での容量保持率を求め
た。試験数量はそれぞれ５個である。As a test method, charging was performed for 5 hours at a constant current and a constant voltage of a charging current of 1 A and a charging upper limit voltage of 4.1 V.
Discharging at a current of 0.1 A to 2.75 V, then charging at a constant current and a constant voltage of 1 A of charging current and a charging upper limit voltage of 4.1 V for 5 hours, and discharging at a current of 1 A to 2.75 V;
The capacity retention at 1A discharge with respect to 0.1A discharge was determined. The test quantity is five each.
【００１７】表２に０．１Ａと１Ａで放電した場合の放
電容量と容量保持率［（１Ａ放電時の放電容量／０．１
Ａ放電時の放電容量）×１００）］の結果を示した。Table 2 shows the discharge capacity and the capacity retention when discharging at 0.1 A and 1 A [(discharge capacity at 1 A discharge / 0.1
A) (discharge capacity during A discharge) × 100)].
【００１８】[0018]
【表２】 試験結果より、本発明のカーボンナノチューブを添加し
た電池は高率放電特性が優れていることがわかる。特
に、その添加量が２重量部以上であればその効果は著し
く、４％以上であれば高率放電特性の容量保持率に有意
差はなくなるが、２０％添加した場合は、比較例電池Ｊ
に比べ放電容量が少なくなるため、好ましくは添加量が
１５％以下がよい。[Table 2] The test results show that the battery to which the carbon nanotube of the present invention is added has excellent high-rate discharge characteristics. In particular, when the addition amount is 2 parts by weight or more, the effect is remarkable. When the addition amount is 4% or more, there is no significant difference in the capacity retention of the high-rate discharge characteristics.
Since the discharge capacity is smaller than that of the above, the addition amount is preferably 15% or less.
【００１９】また、実施例電池Ｄのように、導電剤の添
加量が２重量部であるにも関わらず、導電剤を１０重量
部添加した実施例電池Ｊとほぼ同程度の容量保持率があ
るため、本発明電池は高容量化を図ることができる。As in Example Battery D, the capacity retention was almost the same as that of Example Battery J in which 10 parts by weight of the conductive agent was added, although the amount of the conductive agent was 2 parts by weight. Therefore, the battery of the present invention can achieve high capacity.
【００２０】表３に寿命試験を行った場合の５００サイ
クル時の放電容量と初期放電容量に対する容量保持率
［（５００サイクル時の放電容量／初期放電容量）×１
００）］を示した。試験方法として、充電電流１Ａ，充
電上限電圧４．１Ｖの定電流・定電圧で５時間充電を行
い、１Ａの電流で２．７５Ｖまで放電した。試験数量は
それぞれ５個である。Table 3 shows the capacity retention ratio with respect to the discharge capacity at 500 cycles and the initial discharge capacity when the life test was performed [(discharge capacity at 500 cycles / initial discharge capacity) × 1].
00)]. As a test method, the battery was charged at a constant current and a constant voltage of a charging current of 1 A and a charging upper limit voltage of 4.1 V for 5 hours, and discharged at a current of 1 A to 2.75 V. The test quantity is five each.
【００２１】[0021]
【表３】 試験結果より、本発明のカーボンナノチューブを添加し
た電池は寿命特性が優れていることがわかる。また、そ
の添加量が２重量部以上であればその効果は認められ
る。[Table 3] From the test results, it is understood that the battery to which the carbon nanotube of the present invention is added has excellent life characteristics. If the amount is 2 parts by weight or more, the effect is recognized.
【００２２】[0022]
【発明の効果】本発明により、導電剤としてカーボンナ
ノチューブを使用することにより、高率放電特性が改善
され、また、少量の導電剤で効果があるため、電池容量
を多くすることができ、その工業的価値は極めて大であ
る。According to the present invention, by using carbon nanotubes as the conductive agent, the high-rate discharge characteristics are improved, and since a small amount of the conductive agent is effective, the battery capacity can be increased. The industrial value is extremely large.
【００２３】さらに本発明でわかったことに、このカー
ボンナノチューブは繊維状になっているため、正極活物
質の充電および放電での体積の膨張または収縮によって
生ずる正極活物質粒子同士の分離がもたらす電子の導電
パスの分断を防ぎ、高率放電のみならず、寿命特性の改
善もはかることができる。Further, it has been found in the present invention that since the carbon nanotubes are in a fibrous form, the electrons generated by the separation of the positive electrode active material particles caused by the expansion or contraction of the volume during charging and discharging of the positive electrode active material. Of the conductive path can be prevented, and not only the high-rate discharge but also the life characteristics can be improved.
【００２４】なお、本実施例では正極の活物質にＬｉＭ
ｎ2 Ｏ4 を用いたが、マンガンの一部を鉄、マグネシウ
ム、クロム、アルミで置換したＬｉＭｎ1.9 Ｆｅ0.1 Ｏ
2 、ＬｉＭｎ1.9 Ｍｇ0.1 Ｏ2 、ＬｉＭｎ1.9 Ｃｒ0.1
Ｏ2 等を用いても同様の効果が得られる。In this embodiment, the active material of the positive electrode is LiM
n 2 O 4 was used, but LiMn 1.9 Fe 0.1 O in which part of manganese was replaced with iron, magnesium, chromium, and aluminum
2 , LiMn 1.9 Mg 0.1 O 2 , LiMn 1.9 Cr 0.1
The same effect can be obtained by using O 2 or the like.
【図１】本発明有機電解質電池の一実施例を示す構造図FIG. 1 is a structural view showing one embodiment of the organic electrolyte battery of the present invention.
１ 正極 ２ 負極 ３ セパレータ ４ 電池ケース ５ センターピン ６ 蓋体 ７ ガスケット ８ 正極リード ９ 負極リード １０ ＰＴＣ素子 １１ 安全弁 DESCRIPTION OF SYMBOLS 1 Positive electrode 2 Negative electrode 3 Separator 4 Battery case 5 Center pin 6 Lid 7 Gasket 8 Positive electrode lead 9 Negative electrode lead 10 PTC element 11 Safety valve
Claims (2)
た合剤層が金属の基材に形成されてなる正極（１）と、
負極（２）と有機電解質よりなり、該正極活物質がマン
ガンを主体とするリチウム複合酸化物である有機電解質
電池において、該導電剤がカーボンナノチューブである
有機電解質電池。1. A positive electrode (1) comprising a mixture layer comprising a positive electrode active material, a conductive agent and a binder formed on a metal substrate;
An organic electrolyte battery comprising a negative electrode (2) and an organic electrolyte, wherein the positive electrode active material is a lithium composite oxide mainly composed of manganese, wherein the conductive agent is a carbon nanotube.
物質と導電剤とバインダーの合計重量に対して２重量部
以上１５重量部以下である請求項１記載の有機電解質電
池。2. The organic electrolyte battery according to claim 1, wherein the ratio of the carbon nanotubes is 2 to 15 parts by weight based on the total weight of the positive electrode active material, the conductive agent, and the binder.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10100037A JPH11283629A (en) | 1998-03-27 | 1998-03-27 | Organic electrolyte battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10100037A JPH11283629A (en) | 1998-03-27 | 1998-03-27 | Organic electrolyte battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH11283629A true JPH11283629A (en) | 1999-10-15 |
Family
ID=14263338
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10100037A Pending JPH11283629A (en) | 1998-03-27 | 1998-03-27 | Organic electrolyte battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH11283629A (en) |
Cited By (20)
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|---|---|---|---|---|
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| KR20040009381A (en) * | 2002-07-23 | 2004-01-31 | 한국과학기술원 | The fabrication of cathode with carbon nanotubes for rechargeable Li/S cell |
| 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 |
| KR100444140B1 (en) * | 2000-11-24 | 2004-08-09 | 주식회사 동운인터내셔널 | Conducting materials for high quality secondary battery and secondary batteries using them |
| JP2004273433A (en) * | 2003-02-19 | 2004-09-30 | Matsushita Electric Ind Co Ltd | Electrode for battery and manufacturing method of the same |
| WO2003067699A3 (en) * | 2002-02-08 | 2005-02-10 | Electrovaya | Carbon fibre containing negative electrode for lithium battery |
| JP2005521563A (en) * | 2002-03-25 | 2005-07-21 | ザ ユニバーシティ オブ ノース カロライナ アット チャペル ヒル | How to collect nano objects |
| JP2005285572A (en) * | 2004-03-30 | 2005-10-13 | Nikko Materials Co Ltd | Precursor for lithium-ion secondary battery anode material, its manufacturing method, and manufacturing method of anode material using it |
| JP2006004724A (en) * | 2004-06-17 | 2006-01-05 | Nikko Materials Co Ltd | Precursor for positive electrode material for lithium ion secondary battery, its manufacturing method, and manufacturing method of positive electrode material using it |
| KR100590113B1 (en) | 2005-01-24 | 2006-06-14 | 삼성에스디아이 주식회사 | Positive electrode for rechargeable lithium battery and rechargeable lithium battery comprising same |
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