JP2001155739A - Positive electrode for secondary cell, and secondary cell - Google Patents
Positive electrode for secondary cell, and secondary cellInfo
- Publication number
- JP2001155739A JP2001155739A JP33332299A JP33332299A JP2001155739A JP 2001155739 A JP2001155739 A JP 2001155739A JP 33332299 A JP33332299 A JP 33332299A JP 33332299 A JP33332299 A JP 33332299A JP 2001155739 A JP2001155739 A JP 2001155739A
- Authority
- JP
- Japan
- Prior art keywords
- aluminum
- secondary battery
- positive electrode
- nonwoven fabric
- battery according
- 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.)
- Withdrawn
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
- Cell Electrode Carriers And Collectors (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】この発明は、リチウム二次電
池やリチウムイオン二次電池などに好適に使用できる二
次電池用正極と、これを用いた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 a positive electrode for a secondary battery which can be suitably used for a lithium secondary battery or a lithium ion secondary battery, and a secondary battery using the same.
【０００２】[0002]
【従来の技術】従来、リチウム二次電池やリチウムイオ
ン二次電池などの二次電池の正極として、ステンレスス
チール薄板、アルミニウム薄板などの金属板を集電体と
し、集電体に活物質がコーティングされたものが用いら
れていた。活物質としては、ＭｎＯ２、ＣｏＯ２、Ｔｉ
Ｏ２などの金属酸化物やＴｉＳ２、ＭｏＳ３などの金属
カルコゲン化物などが一般に用いられ、これらの活物質
を黒鉛、カーボンなどの導電剤とともに結着剤で混錬
し、集電体にコーティングすることにより正極を得るこ
とができる。2. Description of the Related Art Conventionally, as a positive electrode of a secondary battery such as a lithium secondary battery or a lithium ion secondary battery, a metal plate such as a stainless steel thin plate or an aluminum thin plate is used as a current collector, and the current collector is coated with an active material. Was used. As the active material, MnO 2 , CoO 2 , Ti
Metal oxides such as O 2 and metal chalcogenides such as TiS 2 and MoS 3 are generally used, and these active materials are kneaded with a conductive agent such as graphite and carbon with a binder to coat the current collector. By doing so, a positive electrode can be obtained.
【０００３】リチウム二次電池は、このような構成の正
極をリチウムを主体とした負極にセパレーターを介して
積層し、あるいはこの積層物をさらに巻き、正負両極間
に電解液を介在させることによって得ることができる。
また、リチウムイオン二次電池は、正極上にＬｉＣｏＯ
２やＬｉＭｎＯ２などのリチウム系複合金属酸化物を担
持させ、銅シート上に炭素を担持させたものを負極と
し、これら正負極間に電解液とセパレーターを介在させ
ることによって得ることができる。[0003] A lithium secondary battery is obtained by laminating a positive electrode having such a structure on a negative electrode mainly composed of lithium via a separator, or by further winding this laminate, and interposing an electrolyte between the positive and negative electrodes. be able to.
In addition, a lithium ion secondary battery has a LiCoO
A negative electrode can be obtained by supporting a lithium-based composite metal oxide such as 2 or LiMnO 2 and supporting carbon on a copper sheet, and interposing an electrolytic solution and a separator between these positive and negative electrodes.
【０００４】このような構成のリチウム二次電池やリチ
ウムイオン二次電池はすでに実用化されており、さら
に、サイクル寿命、放電電気容量、電気出力などの性能
を向上させることが検討されている。The lithium secondary battery and the lithium ion secondary battery having such a configuration have already been put to practical use, and further studies are being made on improving the performance such as cycle life, discharge electric capacity, and electric output.
【０００５】そこで、上記の正極に代えて、集電体とし
て、ポリエチレン、ポリプロピレン、ポリエステルなど
からなる不織布に、スパッタリング、真空蒸着、イオン
プレーティング、溶射などによりアルミニウム薄膜を形
成した正極を用いることが提案されている。Therefore, instead of the above-described positive electrode, a positive electrode obtained by forming an aluminum thin film on a non-woven fabric made of polyethylene, polypropylene, polyester, or the like by sputtering, vacuum deposition, ion plating, thermal spraying, or the like is used as a current collector. Proposed.
【０００６】また、上記の正極に代えて、集電体とし
て、アルミニウム薄膜で被覆された不織布を大気中また
は還元雰囲気下にて焼成し、有機成分を分解除去した正
極を用いることが提案されている。It has also been proposed to use, as a current collector, a positive electrode obtained by firing a nonwoven fabric coated with an aluminum thin film in the air or in a reducing atmosphere to decompose and remove organic components, instead of the above positive electrode. I have.
【０００７】[0007]
【発明が解決しようとする課題】しかし、金属板からな
る集電体上に活物質を担持させた正極は、集電体と活物
質との密着性が必ずしも良好ではないため、このような
構成の正極を用いた二次電池では、活物質の劣化が不均
一となってリサイクル特性が低下するという問題があっ
た。また、集電体と活物質との密着性や通電性を向上さ
せるために結着剤と導電剤を増量すると、二次電池の放
電電気容量と電気出力が低下するという問題があった。However, a positive electrode in which an active material is supported on a current collector made of a metal plate does not always have good adhesion between the current collector and the active material. In the secondary battery using the positive electrode, there is a problem that the deterioration of the active material becomes non-uniform and the recyclability is deteriorated. Further, when the amount of the binder and the amount of the conductive agent are increased in order to improve the adhesion between the current collector and the active material and the electric conductivity, there is a problem that the discharge electric capacity and the electric output of the secondary battery decrease.
【０００８】また、不織布にアルミニウム薄膜を被覆し
た集電体上に活物質を担持させた正極は、集電体と活物
質との密着性は良好であるが、集電体において不織布の
繊維の占める割合が大きいため集電体の性能が金属板の
場合と比較して劣り、金属板並みの導電性を得るのが困
難であるという問題があった。A positive electrode in which an active material is supported on a current collector in which a non-woven fabric is coated with an aluminum thin film has a good adhesion between the current collector and the active material, but the non-woven fabric of the non-woven fabric in the current collector has a good adhesion. Due to the large proportion, the performance of the current collector is inferior to that of the metal plate, and there is a problem that it is difficult to obtain the same conductivity as the metal plate.
【０００９】また、アルミニウム薄膜で被覆された不織
布の有機成分を分解除去した集電体上に活物質を担持さ
せた正極は、集電体として必要な強度、つまり活物質な
どをコーティングする際に必要な引っ張り強度を有さな
いという問題があった。A positive electrode having an active material supported on a current collector obtained by decomposing and removing organic components of a non-woven fabric covered with an aluminum thin film has a strength required as a current collector, that is, when the active material is coated. There was a problem that it did not have the necessary tensile strength.
【００１０】したがって、この発明は、集電体と活物質
との密着性に優れ、導電剤や結着剤の使用量を減少させ
ることができる二次電池用正極と、サイクル寿命、放電
電気容量、電気出力などの性能が向上した二次電池を提
供することを目的とする。Accordingly, the present invention provides a positive electrode for a secondary battery which has excellent adhesion between a current collector and an active material and can reduce the amount of a conductive agent and a binder, and has a cycle life and a discharge capacity. It is an object of the present invention to provide a secondary battery with improved performance such as electric output.
【００１１】[0011]
【課題を解決するための手段】この発明の成形同時絵付
シートは、以上の目的を達成するために、つぎのように
構成した。Means for Solving the Problems In order to achieve the above object, the sheet with simultaneous painting according to the present invention is constituted as follows.
【００１２】つまり、この発明の二次電池用正極は、ア
ルミニウムを主成分とする金属繊維が溶融紡糸されて三
次元の網目構造を有するように形成されたアルミニウム
不織布を集電体とするように構成した。That is, the positive electrode for a secondary battery according to the present invention uses an aluminum nonwoven fabric formed by melt-spinning a metal fiber containing aluminum as a main component and having a three-dimensional network structure as a current collector. Configured.
【００１３】また、上記の発明において、アルミニウム
不織布の金属繊維が、アルミニウムあるいはアルミニウ
ム−カーボン、アルミニウム−銀、アルミニウム−マグ
ネシウム、アルミニウム−コバルト、アルミニウム−チ
タン、アルミニウム−モリブデン、アルミニウム−銅の
いずれかからなるように構成してもよい。In the above invention, the metal fibers of the aluminum nonwoven fabric may be made of aluminum or any of aluminum-carbon, aluminum-silver, aluminum-magnesium, aluminum-cobalt, aluminum-titanium, aluminum-molybdenum, and aluminum-copper. You may comprise so that it may become.
【００１４】また、上記の発明において、アルミニウム
不織布が、熱圧着あるいは超音波振動により金属繊維の
結着がされて製造されたものであるように構成してもよ
い。Further, in the above invention, the aluminum nonwoven fabric may be manufactured by bonding metal fibers by thermocompression bonding or ultrasonic vibration.
【００１５】また、上記の発明において、アルミニウム
不織布が、金属繊維の結着剤としてポリエチレン、ポリ
プロピレン、ポリエステルの単独あるいは混合物を用い
て製造されたものであるように構成してもよい。[0015] In the above invention, the aluminum nonwoven fabric may be made of polyethylene, polypropylene or polyester alone or as a mixture as a binder for metal fibers.
【００１６】また、上記の発明において、アルミニウム
不織布が、金属繊維の結着剤として酸化ケイ素、酸化ア
ルミニウム、酸化ジルコニウムの単独あるいは混合物を
用いて製造されたものであるように構成してもよい。Further, in the above invention, the aluminum nonwoven fabric may be constituted by using silicon oxide, aluminum oxide or zirconium oxide alone or as a mixture as a binder for metal fibers.
【００１７】また、上記の発明において、アルミニウム
不織布が、還元雰囲気下で溶融紡糸されたものであるよ
うに構成してもよい。In the above invention, the aluminum nonwoven fabric may be configured to be melt-spun under a reducing atmosphere.
【００１８】また、上記の発明において、アルミニウム
不織布の金属繊維の平均直径が１０〜１００μｍである
ように構成してもよい。In the above invention, the average diameter of the metal fibers of the aluminum nonwoven fabric may be 10 to 100 μm.
【００１９】また、上記の発明において、アルミニウム
不織布の平均孔径が１〜２００μｍであるように構成し
てもよい。In the above invention, the aluminum nonwoven fabric may be configured so that the average pore size is 1 to 200 μm.
【００２０】また、上記の発明において、アルミニウム
不織布の厚さが１０〜２００μｍであるように構成して
もよい。In the above invention, the thickness of the aluminum nonwoven fabric may be 10 to 200 μm.
【００２１】また、上記の発明において、アルミニウム
不織布の平均開口率が３０〜９５％であるように構成し
てもよい。In the above invention, the aluminum nonwoven fabric may be configured so that the average opening ratio is 30 to 95%.
【００２２】また、この発明の二次電池は、上記の二次
電池用正極を用いるように構成した。Further, a secondary battery of the present invention is configured to use the above-mentioned positive electrode for a secondary battery.
【００２３】[0023]
【発明の実施の形態】この発明の実施の形態について詳
しく説明する。DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will be described in detail.
【００２４】この発明の二次電池用正極は、アルミニウ
ムを主成分とする金属繊維が溶融紡糸されて三次元の網
目構造を有するように形成されたアルミニウム不織布を
集電体としたものである。The positive electrode for a secondary battery of the present invention is a current collector using an aluminum nonwoven fabric formed by melting and spinning metal fibers containing aluminum as a main component so as to have a three-dimensional network structure.
【００２５】この発明でいうアルミニウム不織布とは、
アルミニウムを主成分とする金属繊維が溶融紡糸されて
三次元の網目構造を有するように形成されたものをい
う。The aluminum nonwoven fabric referred to in the present invention is:
A metal fiber mainly composed of aluminum is melt-spun and formed to have a three-dimensional network structure.
【００２６】金属繊維としては、アルミニウムを主成分
とするものを用いる。主成分がアルミニウムであればそ
の導電性を損なわない程度に他の物質を添加してもよ
い。具体的には、アルミニウム−カーボン、アルミニウ
ム−銀、アルミニウム−マグネシウム、アルミニウム−
コバルト、アルミニウム−チタン、アルミニウム−モリ
ブデン、アルミニウム−銅などが挙げられる。通常アル
ミニウムの融点は６６０℃前後であるが、他の物質を添
加することによって融点の低下が期待でき、アルミニウ
ム不織布の製造工程上有利である。また、二次電池のサ
イクル特性の向上や充放電特性の向上が期待できる。As the metal fibers, those containing aluminum as a main component are used. If the main component is aluminum, another substance may be added to the extent that the conductivity is not impaired. Specifically, aluminum-carbon, aluminum-silver, aluminum-magnesium, aluminum-
Cobalt, aluminum-titanium, aluminum-molybdenum, aluminum-copper and the like can be mentioned. Usually, the melting point of aluminum is around 660 ° C., but the addition of other substances can be expected to lower the melting point, which is advantageous in the production process of aluminum nonwoven fabric. In addition, improvement in cycle characteristics and charge / discharge characteristics of the secondary battery can be expected.
【００２７】アルミニウム不織布における金属繊維の結
着は、結着剤を用いずに、接触する部分を熱圧着あるい
は超音波などの振動により接着することにより行うこと
ができる。また、別の方法としては、有機の結着剤とし
てポリエチレン、ポリプロピレン、ポリエステルの単独
あるいは混合物を用いて金属繊維を圧着して接着するこ
とができる。また、無機の結着剤として酸化ケイ素、酸
化アルミニウム、酸化ジルコニウムの単独あるいは混合
物を用いて金属繊維を圧着して接着することができる。
このように金属繊維の結着を行うことにより、金属繊維
の脱落を防止し、正極を折り曲げた際のけば立ちを防止
できる。The binding of the metal fibers in the aluminum nonwoven fabric can be performed by bonding the contacting portions by vibration such as thermocompression bonding or ultrasonic waves without using a binder. As another method, metal fibers can be pressure-bonded and bonded using an organic binder alone or a mixture of polyethylene, polypropylene and polyester. Further, metal fibers can be bonded by pressure bonding using silicon oxide, aluminum oxide, or zirconium oxide alone or as a mixture as an inorganic binder.
By binding the metal fibers in this manner, it is possible to prevent the metal fibers from falling off and to prevent fuzz when the positive electrode is bent.
【００２８】また、アルミニウム不織布の製造工程にお
いて、少なくとも吐出ノズルから溶融金属を吐出する工
程からプレス工程に至るまでの間、窒素ガスなどの還元
雰囲気下であることが望ましい。還元雰囲気下とするこ
とによってアルミニウム不織布の酸化を防止することが
でき、金属繊維表面に酸化皮膜が形成されてその導電性
が妨げられ二次電池の内部抵抗として働くという問題が
生じないようにすることができる。Further, in the manufacturing process of the aluminum nonwoven fabric, it is desirable that the process is performed under a reducing atmosphere such as nitrogen gas at least from the step of discharging the molten metal from the discharge nozzle to the pressing step. By setting the atmosphere in a reducing atmosphere, the oxidation of the aluminum nonwoven fabric can be prevented, and the problem that an oxide film is formed on the surface of the metal fiber to prevent its conductivity and function as an internal resistance of the secondary battery does not occur. be able to.
【００２９】また、アルミニウム不織布の金属繊維の平
均直径は、１０〜１００μｍであるのが好ましい。金属
繊維の平均直径が１０μｍに満たないと、活物質をコー
ティングする際の引っ張り強度が不足し、断裂するおそ
れがある。また、金属繊維の平均直径が１００μｍを越
えると、正極の厚みが大きくなり、二次電池の厚みを薄
くするのに不適当なものとなる。The average diameter of the metal fibers of the aluminum nonwoven fabric is preferably from 10 to 100 μm. If the average diameter of the metal fiber is less than 10 μm, the tensile strength at the time of coating the active material may be insufficient, and the metal fiber may be broken. On the other hand, when the average diameter of the metal fibers exceeds 100 μm, the thickness of the positive electrode increases, which is inappropriate for reducing the thickness of the secondary battery.
【００３０】また、アルミニウム不織布の平均孔径は、
１〜２００μｍであるのが好ましい。平均孔径が１μｍ
に満たないと、活物質が十分にコーティングされず、所
望の二次電池特性が得られない。一方、平均孔径が２０
０μｍを越えると、活物質の脱落などの問題が発生する
ため好ましくない。The average pore size of the aluminum nonwoven fabric is as follows:
It is preferably from 1 to 200 μm. Average pore size is 1μm
If less, the active material is not sufficiently coated, and desired secondary battery characteristics cannot be obtained. On the other hand, when the average pore diameter is 20
When the thickness exceeds 0 μm, problems such as falling off of the active material occur, which is not preferable.
【００３１】また、アルミニウム不織布の厚さは、１０
〜２００μｍであるのが好ましい。厚さが１０μｍに満
たないと、活物質などをコーティングする際の引っ張り
強度が不十分となる。また、厚さが２００μｍを越える
と、活物質をコーティングする際、コーティング装置に
おけるアルミニウム不織布の良好な走行が期待できな
い。さらに、二次電池の厚みを薄くするのに不適当なも
のとなる。The thickness of the aluminum nonwoven fabric is 10
Preferably it is ~ 200 μm. If the thickness is less than 10 μm, the tensile strength when coating an active material or the like becomes insufficient. On the other hand, if the thickness exceeds 200 μm, good running of the aluminum nonwoven fabric in the coating apparatus cannot be expected when coating the active material. Furthermore, it becomes inappropriate for reducing the thickness of the secondary battery.
【００３２】また、アルミニウム不織布の平均開口率
は、３０〜９５％の範囲にあるのが好ましい。平均開口
率が３０％に満たないと、活物質と集電体との接触面積
が不足し所望の特性が得られない。また、平均開口率が
９５％を越えると、アルミニウム不織布の強度が不足
し、活物質のコーティングの際に亀裂やけば立ちが発生
し、後工程において短絡の原因となる危険性がある。The average opening ratio of the aluminum nonwoven fabric is preferably in the range of 30 to 95%. If the average aperture ratio is less than 30%, the contact area between the active material and the current collector is insufficient, and desired characteristics cannot be obtained. On the other hand, if the average aperture ratio exceeds 95%, the strength of the aluminum nonwoven fabric is insufficient, and cracks and fuzzing occur when coating the active material, which may cause a short circuit in a later step.
【００３３】このような構成の集電体に活物質をコーテ
ィングして正極を得る。The positive electrode is obtained by coating the current collector having such a structure with an active material.
【００３４】活物質としては、ＭｎＯ２、ＣｏＯ２、Ｔ
ｉＯ２などの金属酸化物やＴｉＳ２、ＭｏＳ３などの金
属カルコゲン化物などを用いることができる。また、活
物質を、黒鉛、カーボンなどの導電剤や、ポリビニルア
ルコール（ＰＶＡ）などの結着剤を混合して用いること
ができる。As the active material, MnO 2 , CoO 2 , T
A metal oxide such as iO 2 or a metal chalcogenide such as TiS 2 or MoS 3 can be used. Further, the active material can be used by mixing a conductive agent such as graphite or carbon, or a binder such as polyvinyl alcohol (PVA).
【００３５】活物質のコーティング方法としては、上記
した組成の活物質を集電体にドクターブレード法などの
方法により塗布し、次いでロールなどによって圧着し、
さらに、熱風乾燥あるいは真空乾燥するとよい。As a method of coating the active material, the active material having the above-described composition is applied to a current collector by a method such as a doctor blade method, and then pressed by a roll or the like.
Further, hot air drying or vacuum drying is preferable.
【００３６】このようにして二次電池用正極を得ること
ができる。このようにして得られた二次電池用正極は、
平板状で用いる場合のほか、巻いた形状など種々の形状
に加工して使用することが可能である。Thus, a positive electrode for a secondary battery can be obtained. The positive electrode for a secondary battery thus obtained is
In addition to the use in the form of a flat plate, it can be used after being processed into various shapes such as a rolled shape.
【００３７】この発明の二次電池用正極は、特にリチウ
ム二次電池とリチウムイオン二次電池の正極として好適
に使用できるものである。The positive electrode for a secondary battery of the present invention can be suitably used particularly as a positive electrode for a lithium secondary battery and a lithium ion secondary battery.
【００３８】リチウム二次電池は、活物質としてＭｎＯ
２、ＣｏＯ２、ＴｉＯ２などの金属酸化物やＴｉＳ２、
ＭｏＳ３などの金属カルコゲン化物などを用いた二次電
池用正極と、リチウム金属やリチウムと黒鉛の層間化合
物やリチウム金属間化合物などの負極活物質を用いた負
極と、プロピレンカーボネート（ＰＣ）やエチレンカー
ボネート（ＥＣ）などの電解液と、ポリエチレンフィル
ムなどのセパレーターとによって構成することができ
る。A lithium secondary battery uses MnO as an active material.
2 , metal oxides such as CoO 2 and TiO 2 , TiS 2 ,
A secondary battery positive electrode using a metal chalcogenide such as MoS 3; a negative electrode using a negative electrode active material such as lithium metal, an intercalation compound of lithium and graphite or a lithium intermetallic compound; propylene carbonate (PC) or ethylene It can be composed of an electrolyte such as carbonate (EC) and a separator such as a polyethylene film.
【００３９】また、リチウムイオン二次電池は、岩塩構
造を有したＬｉＣｏＯ２、ＬｉＮｉＯ２やスピネル構造
を有したＬｉＭｎ２Ｏ４などの遷移金属を含んだリチウ
ム酸化物を活物質として用いた二次電池用正極と、負極
活物質として天然黒鉛、活性炭素繊維などを用いた負極
と、イオン伝導度が高く電気化学的安定性と熱安定性に
優れた電解液、たとえばＬｉＰＦ６やＬｉＢＦ４などの
電解質とＰＣ、ＥＣなどの環状の炭酸エステルと低粘度
な溶媒としてジエチルカーボネート（ＤＥＣ）、ＤＭ
Ｃ、エチルメチルカーボネート（ＥＭＣ）などの鎖状の
炭酸エステルと混合した有機溶媒とからなる電解液と、
微多孔質なポリオレフィンフィルムなどのセパレーター
とによって構成することができる。A lithium ion secondary battery uses a lithium oxide containing a transition metal such as LiCoO 2 or LiNiO 2 having a rock salt structure or LiMn 2 O 4 having a spinel structure as an active material. A positive electrode for a battery, a negative electrode using natural graphite, activated carbon fiber, or the like as a negative electrode active material, and an electrolyte having high ionic conductivity and excellent electrochemical stability and thermal stability, such as LiPF 6 and LiBF 4 . Electrolyte, cyclic carbonate such as PC and EC, and low viscosity solvent such as diethyl carbonate (DEC), DM
C, an electrolytic solution comprising an organic solvent mixed with a chain carbonate such as ethyl methyl carbonate (EMC);
It can be constituted by a separator such as a microporous polyolefin film.
【００４０】[0040]
【実施例】以下実施例を用いてこの発明を具体的に説明
する。なお、この発明は下記の実施例に制限されるもの
ではない。DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be specifically described below with reference to embodiments. The present invention is not limited to the following embodiments.
【００４１】（実施例１） 金属繊維の平均直径が８０
μｍとなるように純金属のアルミニウムを溶融紡糸し、
熱圧着により厚さ１００μｍのシート状に加工してアル
ミニウム不織布を得た。その後、アルカリによる化成処
理をして酸化皮膜を除去し、集電体を得た。Example 1 The average diameter of the metal fibers was 80.
melt spinning pure metal aluminum to a thickness of μm,
The sheet was processed into a sheet having a thickness of 100 μm by thermocompression bonding to obtain an aluminum nonwoven fabric. Thereafter, a chemical conversion treatment with an alkali was performed to remove the oxide film, thereby obtaining a current collector.
【００４２】次いで、活物質としてＬｉＣｏＯ２を用
い、これにＰＶＡ２重量％とカーボン粉体７重量％を加
えて混錬し、ドライエアー中にて上記集電体に厚さ約１
５０μｍに塗布、圧着して二次電池用正極を得た。Next, LiCoO 2 was used as an active material, 2 % by weight of PVA and 7% by weight of carbon powder were added thereto, and the mixture was kneaded.
It was applied to 50 μm and pressure-bonded to obtain a positive electrode for a secondary battery.
【００４３】次いで、二次電池用正極を５０×２００ｍ
ｍの大きさに裁断し、ポリエステル製不織布からなるセ
パレーターを介して金属リチウム板からなる負極と積層
して巻き上げた。そして、エチレンカーボネート（Ｅ
Ｃ）と１，２ジメトキシエタン（ＤＭＥ）との混合溶媒
にＬｉＣｌＯ４を１０重量％溶解した電解液を正負極間
に介在させ、円筒形のリチウム二次電池を得た。Next, the positive electrode for a secondary battery was
m, and the resultant was laminated with a negative electrode made of a metal lithium plate via a separator made of a nonwoven fabric made of polyester and wound up. And ethylene carbonate (E
An electrolytic solution in which 10% by weight of LiClO 4 was dissolved in a mixed solvent of C) and 1,2-dimethoxyethane (DME) was interposed between the positive and negative electrodes to obtain a cylindrical lithium secondary battery.
【００４４】このようにして得た二次電池用正極につい
て、市販のセロハンテープを用いて９０゜のテープ剥離
テストを行い、集電体と活物質との密着性を確認したと
ころ、まったくはがれが生じないものであった。The positive electrode for a secondary battery thus obtained was subjected to a 90 ° tape peeling test using a commercially available cellophane tape, and the adhesion between the current collector and the active material was confirmed. Did not occur.
【００４５】（比較例１） 比較例として、正極の集電
体として厚さ８０μｍのアルミニウム箔を用いたこと以
外は実施例１と同様にしてリチウム二次電池を作製し、
テープ剥離テストを行ったところ、部分的に約１０％程
度の剥離が生じた。このように、実施例１と比較例１と
を比較した結果から明らかなように、従来の二次電池用
正極に比べ、この発明の二次電池用正極は、集電体と活
物質の密着性が非常に良好であることが確認できた。Comparative Example 1 As a comparative example, a lithium secondary battery was manufactured in the same manner as in Example 1 except that an aluminum foil having a thickness of 80 μm was used as a current collector for the positive electrode.
When the tape peeling test was performed, peeling of about 10% occurred partially. As is clear from the comparison between Example 1 and Comparative Example 1, the positive electrode for a secondary battery according to the present invention has a better adhesion between the current collector and the active material than the conventional positive electrode for a secondary battery. It was confirmed that the properties were very good.
【００４６】また、リチウム二次電池の放電電気容量と
電気出力を、比較例１における放電電気容量を１００
％、電気出力を１００％として測定したところ、実施例
１における放電電気容量は１１５％、電気出力は１２０
％であった。このように、実施例１と比較例１とを比較
した結果から明らかなように、従来の二次電池に比べ、
この発明の二次電池は、優れた放電電気特性と電気出力
を有することが確認できた。The discharge electric capacity and electric output of the lithium secondary battery were compared with those of Comparative Example 1 by 100.
% And the electric output as 100%, the discharge electric capacity in Example 1 was 115%, and the electric output was 120%.
%Met. Thus, as is clear from the result of comparison between Example 1 and Comparative Example 1, compared with the conventional secondary battery,
It was confirmed that the secondary battery of the present invention had excellent discharge electric characteristics and electric output.
【００４７】（実施例２） 金属繊維の平均直径が５０
μｍとなるように純金属のアルミニウムを溶融紡糸し、
熱圧着により厚さ１００μｍのシート状に加工してアル
ミニウム不織布を得た。その後、アルカリによる化成処
理をして酸化皮膜を除去し、集電体を得た。Example 2 The average diameter of the metal fibers was 50.
melt spinning pure metal aluminum to a thickness of μm,
The sheet was processed into a sheet having a thickness of 100 μm by thermocompression bonding to obtain an aluminum nonwoven fabric. Thereafter, a chemical conversion treatment with an alkali was performed to remove the oxide film, thereby obtaining a current collector.
【００４８】次いで、活物質としてＬｉＭｎ２Ｏ４を用
い、これにＰＶＡ２重量％とカーボン粉体７重量％を加
えて混錬し、ドライエアー中にて上記集電体に厚さ約１
５０μｍに塗布、圧着して二次電池用正極を得た。Next, LiMn 2 O 4 was used as an active material, 2 % by weight of PVA and 7% by weight of carbon powder were added thereto, and the mixture was kneaded.
It was applied to 50 μm and pressure-bonded to obtain a positive electrode for a secondary battery.
【００４９】次いで、負極として厚さ２００μｍの銅箔
を用い、活物質としてグラファイトを使用し、セパレー
ターとして微細孔を有したポリオレフィンフィルムを使
用し、電解液として、プロピレンカーボネート（ＰＣ）
と１，２ジメトキシエタン（ＤＭＥ）との混合溶媒にＬ
ｉＰＦ６を８重量％溶解した溶液を用いてリチウムイオ
ン二次電池を得た。Next, a copper foil having a thickness of 200 μm was used as a negative electrode, graphite was used as an active material, a polyolefin film having fine pores was used as a separator, and propylene carbonate (PC) was used as an electrolyte.
And a mixture of 1,2 dimethoxyethane (DME) with L
A lithium ion secondary battery was obtained using a solution in which iPF 6 was dissolved at 8% by weight.
【００５０】（比較例２） 比較例として、正極の集電
体として厚さ８０μｍのアルミニウム箔を用いたこと以
外は実施例２と同様にしてリチウムイオン二次電池を作
製した。Comparative Example 2 As a comparative example, a lithium ion secondary battery was fabricated in the same manner as in Example 2 except that an aluminum foil having a thickness of 80 μm was used as a current collector for the positive electrode.
【００５１】このようにして得たリチウムイオン二次電
池の放電電気容量と電気出力を、比較例２における放電
電気容量を１００％、電気出力を１００％として測定し
たところ、実施例２における放電電気容量は１０８％、
電気出力は１１２％であった。このように、実施例２と
比較例２とを比較した結果から明らかなように、従来の
二次電池に比べ、この発明の二次電池は、優れた放電電
気特性と電気出力を有することが確認できた。The discharge electric capacity and electric output of the lithium ion secondary battery thus obtained were measured with the discharge electric capacity in Comparative Example 2 being 100% and the electric output being 100%. 108% capacity,
The electrical output was 112%. As is apparent from the comparison between Example 2 and Comparative Example 2, the secondary battery of the present invention has excellent discharge electric characteristics and electric output as compared with the conventional secondary battery. It could be confirmed.
【００５２】[0052]
【発明の効果】この発明の二次電池用正極および二次電
池は、上記のように構成されたものであるので、次のよ
うな優れた効果を有する。The positive electrode for a secondary battery and the secondary battery according to the present invention are configured as described above, and therefore have the following excellent effects.
【００５３】この発明の二次電池用正極は、アルミニウ
ムを主成分とする金属繊維が溶融紡糸されて三次元の網
目構造を有するように形成されたアルミニウム不織布を
集電体としたものであり、集電体が三次元の網目構造を
有しているため、集電体と活物質との密着性に優れ、活
物質と集電体との接触面積が増大し、導電剤や結着剤の
使用量を減少させることができるものである。The positive electrode for a secondary battery of the present invention has a current collector made of an aluminum nonwoven fabric formed by melting and spinning metal fibers containing aluminum as a main component so as to have a three-dimensional network structure. Because the current collector has a three-dimensional network structure, it has excellent adhesion between the current collector and the active material, increases the contact area between the active material and the current collector, The amount used can be reduced.
【００５４】また、この発明の二次電池は、上記の構成
の三次元の網目構造を有した集電体を用いるため、正負
極間に介在する電解液の流動性が向上し、二次電池のサ
イクル寿命、放電電気容量、電気出力などの性能を向上
させることができるものである。Further, since the secondary battery of the present invention uses the current collector having the three-dimensional network structure having the above structure, the flowability of the electrolyte interposed between the positive and negative electrodes is improved, And the performance such as cycle life, discharge electric capacity, electric output, etc. can be improved.
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 5H014 AA04 AA06 BB00 BB01 BB05 EE05 HH02 HH06 5H017 AA03 AS10 BB00 BB01 BB06 BB11 BB17 CC00 CC25 EE05 EE09 HH01 HH02 HH03 5H029 AJ02 AJ03 AJ05 AK02 AK03 AK05 AL07 AL12 AM03 AM05 AM07 BJ02 BJ14 CJ01 CJ02 CJ03 CJ05 CJ28 DJ07 DJ15 EJ01 EJ12 HJ04 HJ06 HJ09 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) CJ01 CJ02 CJ03 CJ05 CJ28 DJ07 DJ15 EJ01 EJ12 HJ04 HJ06 HJ09
Claims (11)
溶融紡糸されて三次元の網目構造を有するように形成さ
れたアルミニウム不織布を集電体としたことを特徴とす
る二次電池用正極。1. A positive electrode for a secondary battery, wherein a current collector is an aluminum nonwoven fabric formed by melt-spinning a metal fiber containing aluminum as a main component and having a three-dimensional network structure.
ミニウムあるいはアルミニウム−カーボン、アルミニウ
ム−銀、アルミニウム−マグネシウム、アルミニウム−
コバルト、アルミニウム−チタン、アルミニウム−モリ
ブデン、アルミニウム−銅のいずれかからなる請求項１
に記載の二次電池用正極。2. The method according to claim 1, wherein the metal fibers of the aluminum nonwoven fabric are aluminum or aluminum-carbon, aluminum-silver, aluminum-magnesium, aluminum-
2. The method according to claim 1, wherein the material is any one of cobalt, aluminum-titanium, aluminum-molybdenum, and aluminum-copper.
4. The positive electrode for a secondary battery according to 1.
超音波振動により金属繊維の結着がされて製造されたも
のである請求項１に記載の二次電池用正極。3. The positive electrode for a secondary battery according to claim 1, wherein the aluminum nonwoven fabric is manufactured by binding metal fibers by thermocompression bonding or ultrasonic vibration.
剤としてポリエチレン、ポリプロピレン、ポリエステル
の単独あるいは混合物を用いて製造されたものである請
求項１に記載の二次電池用正極。4. The positive electrode for a secondary battery according to claim 1, wherein the aluminum nonwoven fabric is manufactured using polyethylene, polypropylene or polyester alone or as a mixture as a binder for metal fibers.
剤として酸化ケイ素、酸化アルミニウム、酸化ジルコニ
ウムの単独あるいは混合物を用いて製造されたものであ
る請求項１に記載の二次電池用正極。5. The positive electrode for a secondary battery according to claim 1, wherein the aluminum nonwoven fabric is manufactured using silicon oxide, aluminum oxide, or zirconium oxide alone or as a mixture as a binder for metal fibers.
溶融紡糸されたものである請求項１に記載の二次電池用
正極。6. The positive electrode for a secondary battery according to claim 1, wherein the aluminum nonwoven fabric is melt-spun under a reducing atmosphere.
径が１０〜１００μｍである請求項１に記載の二次電池
用正極。7. The positive electrode for a secondary battery according to claim 1, wherein the average diameter of the metal fibers of the aluminum nonwoven fabric is 10 to 100 μm.
００μｍである請求項１に記載の二次電池用正極。8. An aluminum nonwoven fabric having an average pore size of 1 to 2
The positive electrode for a secondary battery according to claim 1, which has a thickness of 00 µm.
０μｍである請求項１に記載の二次電池用正極。9. The thickness of the aluminum nonwoven fabric is from 10 to 20.
The positive electrode for a secondary battery according to claim 1, which has a thickness of 0 µm.
０〜９５％である請求項１に記載の二次電池用正極。10. An aluminum nonwoven fabric having an average opening ratio of 3
The positive electrode for a secondary battery according to claim 1, wherein the content is 0 to 95%.
極を用いたことを特徴とする二次電池。11. A secondary battery comprising the positive electrode for a secondary battery according to claim 1.
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|---|---|---|---|
| JP33332299A JP2001155739A (en) | 1999-11-24 | 1999-11-24 | Positive electrode for secondary cell, and secondary cell |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33332299A JP2001155739A (en) | 1999-11-24 | 1999-11-24 | Positive electrode for secondary cell, and secondary cell |
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