JPH09199132A - Electrode and secondary battery using it - Google Patents
Electrode and secondary battery using itInfo
- Publication number
- JPH09199132A JPH09199132A JP8008608A JP860896A JPH09199132A JP H09199132 A JPH09199132 A JP H09199132A JP 8008608 A JP8008608 A JP 8008608A JP 860896 A JP860896 A JP 860896A JP H09199132 A JPH09199132 A JP H09199132A
- Authority
- JP
- Japan
- Prior art keywords
- electrode
- binder
- weight
- current collector
- carboxylic acid
- 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、改良された電極および
それを用いた二次電池に関する。かかる二次電池として
は、ポータブル機器などに使用されるリチウム二次電池
がある。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an improved electrode and a secondary battery using the same. As such a secondary battery, there is a lithium secondary battery used in portable devices and the like.
【０００２】[0002]
【従来の技術】近年、携帯電話、ビデオカメラ、ノート
型パソコン等のポータブル機器の普及に伴い、小型で高
容量、長寿命の二次電池に対する需要が高まっている。
特に、現在、注目されている二次電池として、リチウム
二次電池がある。2. Description of the Related Art In recent years, with the widespread use of portable devices such as mobile phones, video cameras, and notebook computers, there has been an increasing demand for compact, high-capacity, long-life secondary batteries.
In particular, a lithium secondary battery is currently receiving attention as a secondary battery.
【０００３】リチウム二次電池の負極活性物質として
は、リチウムイオンをドーピング、脱ドーピングするコ
ークスやグラファイト等の炭素質材料を用いることが提
案されているが（特開昭６２−９０８６３号公報）、こ
の場合、通常、粉体状の炭素材料に結着剤を適当量添加
した混合物に溶媒を混ぜてペースト状にしたものを集電
体に塗布、乾燥後圧着させて電極が得られる。As a negative electrode active material for a lithium secondary battery, it has been proposed to use a carbonaceous material such as coke or graphite for doping and dedoping lithium ions (Japanese Patent Laid-Open No. 62-90863). In this case, usually, a mixture of a powdery carbon material and an appropriate amount of a binder is mixed with a solvent to form a paste, which is applied to a current collector, dried and then pressure-bonded to obtain an electrode.
【０００４】また、リチウム二次電池の正極活性物質と
しては、マンガン酸化物、五酸化バナジウムのような遷
移金属酸化物、硫化鉄、硫化チタンのような遷移金属酸
化物、さらにこれらとリチウムとの複合化合物（例え
ば、リチウムコバルト複合酸化物、リチウムコバルトニ
ッケル複合酸化物、リチウムマンガン酸化物）などが提
案されている。これらの材料を正極に組み込む場合も、
粉体状の正極活性物質に導電体（カーボンを用いること
が多い）と結着剤を適量添加した混合物に溶媒を混ぜて
ペースト状にしたものを集電体に塗布、乾燥後圧着させ
て電極が得られる。Further, as a positive electrode active material of a lithium secondary battery, manganese oxide, transition metal oxides such as vanadium pentoxide, transition metal oxides such as iron sulfide and titanium sulfide, and further, these and lithium are used. Composite compounds (for example, lithium cobalt composite oxide, lithium cobalt nickel composite oxide, lithium manganese oxide) and the like have been proposed. When incorporating these materials into the positive electrode,
A mixture of a powdered positive electrode active material with an appropriate amount of a conductor (carbon is often used) and a binder is mixed with a solvent to form a paste, which is applied to a current collector, dried, and then pressure-bonded to form an electrode. Is obtained.
【０００５】このような二次電池の電極に用いる結着剤
には、強い耐溶剤性と耐薬品性が要求されるため、多く
の場合、フッ素系の樹脂が用いられる。しかしながら、
フッ素系の樹脂は元来金属との接着性が悪く、負極と正
極いずれの場合も、活性物質を集電体に圧着させた後、
集電体と活性物質との接着力が十分でないために、活性
物質が集電体から剥離し易く、電池のサイクル特性が悪
くなるという問題があった。これを改善する方法とし
て、集電体表面を粗面化することが提案されたが（特開
平５−６７６６号公報）、これにおいても接着性は十分
とは言えず、さらなる改良が求められている。Since a strong solvent resistance and chemical resistance are required for the binder used for the electrode of such a secondary battery, a fluorine resin is often used. However,
Fluorine-based resin originally has poor adhesion to metal, and in both cases of negative electrode and positive electrode, after pressing the active substance onto the current collector,
Since the adhesive force between the current collector and the active substance is not sufficient, there is a problem that the active substance is easily peeled from the current collector and the cycle characteristics of the battery are deteriorated. As a method for improving this, it has been proposed to roughen the surface of the current collector (JP-A-5-6766), but even in this case, the adhesiveness is not sufficient and further improvement is required. There is.
【０００６】また、フッ化ビニリデンとカルボン酸基を
有するモノマーとの共重合体（特開平６−１７２４５２
号公報）が提案されたが、通常、フッ素系モノマーとカ
ルボン酸基を有する他のモノマーとの共重合は容易でな
く、量産化が困難で実用的とは言えない．Further, a copolymer of vinylidene fluoride and a monomer having a carboxylic acid group (JP-A-6-172452).
However, it is usually not practical to copolymerize a fluorinated monomer with another monomer having a carboxylic acid group, and mass production is difficult.
【０００７】[0007]
【発明が解決しようとする課題】本発明は、簡便な方法
で電極活性物質と集電体との接着性を向上させ、サイク
ル特性が改善された電池用電極および二次電池を提供す
ることを目的とする。DISCLOSURE OF THE INVENTION The present invention provides a battery electrode and a secondary battery in which the adhesion between the electrode active material and the current collector is improved by a simple method and the cycle characteristics are improved. To aim.
【０００８】[0008]
【課題を解決するための手段】本発明者らは、電池用電
極の結着剤にカルボン酸基あるいはカルボン酸無水物基
を有するアクリル系樹脂を少量添加することにより電極
活性物質と集電体との接着強度を大きく改善させ得るこ
とを見いだし本発明に到達した。Means for Solving the Problems The present inventors have added a small amount of an acrylic resin having a carboxylic acid group or a carboxylic acid anhydride group to a binder of an electrode for a battery to obtain an electrode active substance and a current collector. The inventors have found that the adhesive strength with can be greatly improved and have reached the present invention.
【０００９】すなわち、本発明は、集電体の表面に少な
くとも電極活性物質と結着剤からなる電極構成物質層が
形成されている電池用電極において、結着剤が、（ａ）
カルボン酸基あるいはカルボン酸無水物基を有する単量
体とアクリル酸エステルおよびメタクリル酸エステルか
ら選ばれる少なくとも１種類の単量体からなるアクリル
系共重合体および（ｂ）ポリフッ化ビニリデン系樹脂か
ら構成されることを特徴とする電極およびそれを用いた
二次電池に関する。That is, according to the present invention, in a battery electrode in which an electrode constituent substance layer comprising at least an electrode active substance and a binder is formed on the surface of a current collector, the binder is (a).
Consists of an acrylic copolymer composed of a monomer having a carboxylic acid group or a carboxylic acid anhydride group, and at least one monomer selected from acrylic acid esters and methacrylic acid esters, and (b) a polyvinylidene fluoride resin. The present invention relates to an electrode and a secondary battery using the same.
【００１０】電極の集電体としては、金属箔、金属メッ
シュ、三次元多孔体等があるが、この集電体に用いる金
属としては、リチウムと合金ができ難い金属が望まし
く、特に、鉄、ニッケル、コバルト、銅、アルミニウ
ム、チタン、バナジウム、クロム、マンガンが単独、あ
るいはこれらの合金で用いられる。The electrode current collector may be a metal foil, a metal mesh, a three-dimensional porous body, or the like. The metal used for this current collector is preferably a metal that is difficult to alloy with lithium, and particularly iron, Nickel, cobalt, copper, aluminum, titanium, vanadium, chromium and manganese are used alone or in alloys thereof.
【００１１】電極活性物質のうち負極活性物質として
は、リチウムイオンをドーピング、脱ドーピングし得る
材料であればよい。このような材料として、石油系コー
クスや炭素系コークスなどのコークス材料、アセチレン
ブラックなどのカーボンブラック類、グラファイト、ガ
ラス状炭素、活性炭、炭素繊維、有機高分子を非酸化性
雰囲気中で焼成して得られる有機高分子焼成体等の炭素
質材料がある。また、酸化銅を添加する場合もある。The negative electrode active material among the electrode active materials may be any material capable of doping and dedoping lithium ions. As such materials, coke materials such as petroleum coke and carbon coke, carbon blacks such as acetylene black, graphite, glassy carbon, activated carbon, carbon fiber, and organic polymers are fired in a non-oxidizing atmosphere. There is a carbonaceous material such as a fired organic polymer obtained. In some cases, copper oxide is added.
【００１２】また、正極活性物質としては、上述の一般
に使用されるものであり、特に限定されない。さらに、
これに導電体を添加してもよい。Further, the positive electrode active material is one that is generally used and is not particularly limited. further,
A conductor may be added to this.
【００１３】本発明でいうポリフッ化ビニリデン（ＰＶ
ＤＦ）系樹脂とは、フツ化ビニリデン単独重合体（ホモ
ポリマー）に限定されずフツ化ビニリデンと共重合可能
な他のモノマーとの共重合体も含み、共重合体中のフッ
化ビニリデン成分比率が５０重量％以上であればよく、
さらに望ましくは、７５重量％以上である。ここで共重
合可能な他のモノマーとしては、四フッ化エチレン、六
フッ化プロピレン、三フッ化エチレン、三フッ化塩化エ
チレン、フッ化ビニル等のフッ素系モノマーが挙げら
れ、これらの１種又は２種以上を用いることが出来る。
これらのＰＶＤＦ系樹脂は、耐溶剤性と耐薬品性に優れ
ているため、電極活性物質の結着材として用いた時、高
性能で安定な電極が得られる。In the present invention, polyvinylidene fluoride (PV
The DF) -based resin is not limited to vinylidene fluoride homopolymer (homopolymer) and includes copolymers of vinylidene fluoride with other copolymerizable monomers, and the ratio of vinylidene fluoride component in the copolymer Is 50% by weight or more,
More preferably, it is 75% by weight or more. Examples of the other copolymerizable monomer here include fluorine-based monomers such as tetrafluoroethylene, hexafluoropropylene, trifluoroethylene, trifluoroethylene chloride, and vinyl fluoride. Two or more kinds can be used.
Since these PVDF resins have excellent solvent resistance and chemical resistance, a high-performance and stable electrode can be obtained when used as a binder for an electrode active substance.
【００１４】これらのＰＶＤＦ系樹脂は、フッ化ビニリ
デンおよび上述のフッ素系モノマーを懸濁重合法あるい
は乳化重合法等で重合することにより得られ、２３０
℃、２．１６ｋｇ荷重下でのメルトフローレート（ＭＦ
Ｒ）が０．０１〜３００ｇ／１０分のものが好んで用い
られる。These PVDF-based resins are obtained by polymerizing vinylidene fluoride and the above-mentioned fluorine-based monomers by a suspension polymerization method or an emulsion polymerization method.
Melt flow rate under 2.16 kg load at ℃ (MF
R) of 0.01 to 300 g / 10 minutes is preferably used.
【００１５】また、アクリル系共重合体に使用されるカ
ルボン酸基あるいはカルボン酸無水物基を有する単量体
としては、アクリル酸、メタクリル酸、クロトン酸、マ
レイン酸、フマル酸、アルケニルコハク酸、アクリルア
ミドグリコール酸、１，２−シクロヘキサンジカルボン
酸アリル等の不飽和カルボン酸、および無水マレイン
酸、無水アルケニルコハク酸などの不飽和カルボン酸無
水物がある。As the monomer having a carboxylic acid group or a carboxylic acid anhydride group used in the acrylic copolymer, acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, alkenylsuccinic acid, There are unsaturated carboxylic acids such as acrylamidoglycolic acid and allyl 1,2-cyclohexanedicarboxylate, and unsaturated carboxylic acid anhydrides such as maleic anhydride and alkenylsuccinic anhydride.
【００１６】アクリル酸エステル、メタクリル酸エステ
ルとしては、アクリル酸、メタクリル酸のアルキルエス
テル、例えば、アクリル酸メチル、アクリル酸エチル、
メタクリル酸メチル、メタクリル酸エチル、メタクリル
酸ブチル等が例示される。Examples of acrylic acid esters and methacrylic acid esters include acrylic acid and methacrylic acid alkyl esters such as methyl acrylate and ethyl acrylate.
Methyl methacrylate, ethyl methacrylate, butyl methacrylate, etc. are exemplified.
【００１７】このアクリル系共重合体は、アクリル酸エ
ステルおよびメタクリル酸エステルから選ばれる少なく
とも１種類のモノマー１００重量部に対して、カルボン
酸基あるいはカルボン酸無水物基を有する単量体０．５
〜２０重量部、さらに望ましくは２〜１５重量部が共重
合されたものである。This acrylic copolymer comprises 0.5 parts of a monomer having a carboxylic acid group or a carboxylic acid anhydride group with respect to 100 parts by weight of at least one kind of monomer selected from acrylic acid ester and methacrylic acid ester.
˜20 parts by weight, more preferably 2 to 15 parts by weight are copolymerized.
【００１８】本発明で使用される結着剤において、アク
リル系共重合体の含有率は当該結着剤の０．５〜２０重
量％の範囲であり、望ましくは０．５〜１０重量％、さ
らに望ましくは１〜５重量％である。アクリル系重合体
の添加量が少なすぎる場合、集電体と結着剤との接着性
が悪くなり、これが多すぎる場合、結着剤の耐薬品性が
低下し、いずれの場合も、本発明の電極や二次電池の寿
命に悪影響を及ぼす。In the binder used in the present invention, the content of the acrylic copolymer is in the range of 0.5 to 20% by weight, preferably 0.5 to 10% by weight of the binder. More preferably, it is 1 to 5% by weight. If the amount of the acrylic polymer added is too small, the adhesion between the current collector and the binder will be poor, and if this is too large, the chemical resistance of the binder will decrease, and in any case, the present invention It adversely affects the life of the electrodes and secondary battery.
【００１９】本発明において、電極集電体に塗布するス
ラリーを得るために用いられる溶媒は、Ｎ−メチルピロ
リドン、Ｎ，Ｎ−ジメチルホルムアミド、テトラヒドロ
フラン、ジメチルアセトアミド、ジメチルスルホキシ
ド、ヘキサメチルスルホルアミド、テトラメチル尿素、
アセトン、メチルエチルケトン等の有機溶媒や水であれ
ばよく、これらを単独で用いても、混合して用いてもよ
い。これらのうち、Ｎ−メチルピロリドンが特に好んで
用いられる。また、必要に応じて分散剤を添加してもよ
い。この場合、ノニオン系の分散剤が好んで用いられ
る。In the present invention, the solvent used to obtain the slurry applied to the electrode current collector is N-methylpyrrolidone, N, N-dimethylformamide, tetrahydrofuran, dimethylacetamide, dimethylsulfoxide, hexamethylsulfolamide, Tetramethylurea,
Any organic solvent such as acetone and methyl ethyl ketone and water may be used, and these may be used alone or in combination. Of these, N-methylpyrrolidone is particularly preferably used. Moreover, you may add a dispersing agent as needed. In this case, a nonionic dispersant is preferably used.
【００２０】本発明において、電極活性物質に添加する
結着剤の量は、電極活性物質１００重量部に対して、１
〜３０重量部であることが望ましく、さらに望ましくは
３〜１５重量部である。この添加量が多すぎても少なす
ぎても高性能な電池を得ることができない。さらに、電
極構成物質層には、必要に応じて、導電性付与剤やその
他添加剤（酸化銅等）等を添加してもよい。In the present invention, the amount of the binder added to the electrode active substance is 1 with respect to 100 parts by weight of the electrode active substance.
The amount is preferably ˜30 parts by weight, more preferably 3 to 15 parts by weight. If the added amount is too large or too small, a high performance battery cannot be obtained. Further, a conductivity-imparting agent or other additives (such as copper oxide) may be added to the electrode constituent material layer as needed.
【００２１】本発明においては、所定量の電極活性物
質、および結着剤を溶媒の存在下で混練して得られたス
ラリーを電極集電体に塗布した後、乾燥後、必要に応じ
てプレスして電極が得られる。この場合、スラリーを塗
布後、必要に応じて、６０〜２５０℃、さらに望ましく
は８０〜２００℃で、１分間〜１０時間、加熱処理する
ことが望ましい。こうして得られる帯状電極を、帯状セ
パレータとともにロール状（渦巻状）に巻回し、巻回電
極体としてもよい。In the present invention, a slurry obtained by kneading a predetermined amount of an electrode active substance and a binder in the presence of a solvent is applied to an electrode current collector, dried, and then pressed if necessary. Then, an electrode is obtained. In this case, after applying the slurry, it is desirable to perform heat treatment at 60 to 250 ° C., and more desirably 80 to 200 ° C. for 1 minute to 10 hours, if necessary. The strip-shaped electrode obtained in this way may be wound in a roll (or spiral) together with the strip-shaped separator to form a wound electrode body.
【００２２】以下、実施例により本発明を説明するが、
本発明は実施例により何ら限定されるものではない。The present invention will be described below with reference to examples.
The present invention is not limited at all by the examples.
【００２３】[0023]
【実施例１】負極活性物質担持体として石炭ピッチコー
クスをボールミルで粉砕したもの９０重量部を、結着剤
としてのポリフッ化ビニリデン（エルフ・アトケム社
製、カイナー５００）１０重量部、およびメタクリル酸
メチル１００重量部と無水マレイン酸１０重量部とから
なるアクリル系共重合体（２３０℃、３．８ｋｇ荷重下
でのメルトフローレートが２．４ｇ／１０ｍｉｎ）０．
１重量部とをＮ−メチルピロリドンに溶解してなる溶液
に添加してスラリー（ペースト）状にした。このスラリ
ーを、厚さ２０μｍの銅箔の両面に塗布し、１２０℃で
１時間放置した後、減圧乾燥、プレスを行い厚さ１４５
μｍ、幅２０ｍｍの負極を得た。Example 1 90 parts by weight of coal pitch coke crushed by a ball mill as a negative electrode active material supporting material, 10 parts by weight of polyvinylidene fluoride (Kainer 500 manufactured by Elf Atchem) as a binder, and methacrylic acid. Acrylic copolymer consisting of 100 parts by weight of methyl and 10 parts by weight of maleic anhydride (at 230 ° C., melt flow rate under a load of 3.8 kg is 2.4 g / 10 min).
1 part by weight was added to a solution prepared by dissolving N-methylpyrrolidone into a slurry (paste). This slurry was applied to both sides of a copper foil having a thickness of 20 μm, left at 120 ° C. for 1 hour, dried under reduced pressure and pressed to a thickness of 145.
A negative electrode having a thickness of 20 μm and a width of 20 mm was obtained.
【００２４】次に、正極を次のようにして得た。正極活
性物質としてのＬｉＣｏＯ2９０重量部、導電剤として
のグラファイト６重量部、結着剤としてのポリフッ化ビ
ニリデン１０重量部、および上記と同じメタクリル酸メ
チル−無水マレイン酸共重合体０．１重量部を混合し、
これをＮ−メチルピロリドン中に分散させてスラリー
（ペースト）状にした。このスラリーを、厚さ２０μｍ
のアルミニウム箔の両面に塗布し、１２０℃で１時間放
置した後、減圧乾燥、プレスを行い、厚さ１６０μｍ、
幅２０ｍｍの正極を得た。Next, a positive electrode was obtained as follows. 90 parts by weight of LiCoO 2 as a positive electrode active material, 6 parts by weight of graphite as a conductive agent, 10 parts by weight of polyvinylidene fluoride as a binder, and 0.1 part by weight of the same methyl methacrylate-maleic anhydride copolymer as described above. Mix the parts,
This was dispersed in N-methylpyrrolidone to form a slurry (paste). This slurry has a thickness of 20 μm
Applied to both sides of the aluminum foil of, and left at 120 ° C. for 1 hour, then dried under reduced pressure and pressed to a thickness of 160 μm,
A positive electrode having a width of 20 mm was obtained.
【００２５】これらの電極表面の電極活性物質をカッタ
ーナイフにて剥がしたところ、集電体上にかなりの電極
活性物質の付着残留物が認められ、電極活性物質と集電
体との接着性が良好であることが確認された。When the electrode active substance on the surface of these electrodes was peeled off with a cutter knife, a considerable amount of the electrode active substance residue remained on the current collector, and the adhesiveness between the electrode active substance and the current collector was confirmed. It was confirmed to be good.
【００２６】また、得られた負極、正極、およびセパレ
ータとしての厚さ２５μｍの多孔性ポリプロピレンフィ
ルムを用い、セパレータ、負極、セパレータ、正極、セ
パレータの順に積層した後、この積層体を渦巻状に巻回
することにより渦巻式の電極体を作製した。ついでこの
電極体のそれぞれの極にリード線を付けた後、ステンレ
スの缶に収容し、これに電解液としてプロピレンカーボ
ネートと１，２−ジメトキシエタンとの等容量混合溶媒
中にＬｉＰＦ6を１Ｍ溶解した溶液を注入した。Using the obtained negative electrode, positive electrode, and porous polypropylene film having a thickness of 25 μm as the separator, the separator, the negative electrode, the separator, the positive electrode, and the separator were laminated in this order, and then the laminated body was spirally wound. A spiral electrode body was produced by turning. Then, after attaching a lead wire to each electrode of the electrode body, the electrode body was housed in a stainless steel can, and 1 M of LiPF 6 was dissolved in an equal volume mixed solvent of propylene carbonate and 1,2-dimethoxyethane as an electrolytic solution. The injected solution was injected.
【００２７】充放電試験は、炭素１ｇあたり３０ｍＡの
電流密度で、初めに４．１Ｖまで充電を行い、続いて同
じ電流で２．５Ｖまで放電を行った。２回目以降もこれ
と同じ条件で充放電を繰り返し、放電容量にて電池の評
価を行った。その結果、１００サイクル目の放電容量
は、１０サイクル目のそれの９０％であった。In the charge / discharge test, a current density of 30 mA / g of carbon was used to initially charge the battery to 4.1 V, and then the same current was discharged to 2.5 V. After the second time, charging and discharging were repeated under the same conditions, and the battery was evaluated by the discharge capacity. As a result, the discharge capacity at the 100th cycle was 90% of that at the 10th cycle.
【００２８】[0028]
【実施例２】実施例１において、アクリル系共重合体と
してポリメタクリル酸メチルブロックとメタクリル酸メ
チルとアクリル酸の共重合体ブロックからなるブロック
共重合体（アクリル酸含量、５重量％））を用い、ＰＶ
ＤＦ系樹脂としてフッ化ビニリデンと六フッ化プロピレ
ンからなる共重合体（エルフ・アトケム社製、カイナー
２８００）を用いた他は実施例１同様に、正と負の電極
を作製した。Example 2 A block copolymer (acrylic acid content, 5% by weight) comprising a polymethylmethacrylate block and a copolymer block of methylmethacrylate and acrylic acid was used as the acrylic copolymer in Example 1. Used, PV
Positive and negative electrodes were prepared in the same manner as in Example 1 except that a copolymer of vinylidene fluoride and propylene hexafluoride (Kainer 2800 manufactured by Elf Atchem) was used as the DF resin.
【００２９】これらの電極表面の電極活性物質層をカッ
ターナイフにて剥がしたところ、集電体上にかなりの電
極活性物質の付着残留物が認められ、電極活性物質と集
電体との接着性が良好であることが確認された。さら
に、得られた電極を用い、実施例１と同様の方法で電池
を作製し、充放電試験を行ったところ、１００サイクル
目の放電容量は１０サイクル目のそれの８５％であっ
た。When the electrode active material layer on the surface of these electrodes was peeled off with a cutter knife, a considerable amount of the electrode active material adhering residue was observed on the current collector, and the adhesiveness between the electrode active material and the current collector was found. Was confirmed to be good. Further, using the obtained electrode, a battery was prepared in the same manner as in Example 1 and a charge / discharge test was carried out. As a result, the discharge capacity at the 100th cycle was 85% of that at the 10th cycle.
【００３０】[0030]
【比較例１】実施例１において、負極と正極を作製する
際、アクリル系共重合体を負極および正極活性物質のス
ラリーに添加しなかった他は実施例１と同様にして正と
負の電極を作製した。これらの電極表面の電極活性物質
層をカッターナイフにて剥がしたところ、電極活性物質
層は容易に剥がれ集電体表面には電極活性物質はほとん
ど残らなかった。得られた電極を用い、実施例１に記載
された方法で電池を作製し、充放電試験を行ったとこ
ろ、１００サイクル目の放電容量は１０サイクル目のそ
れの５０％であった。Comparative Example 1 Positive and negative electrodes were prepared in the same manner as in Example 1 except that the acrylic copolymer was not added to the slurry of the negative electrode and the positive electrode active material when the negative electrode and the positive electrode were prepared. Was produced. When the electrode active substance layer on the surface of these electrodes was peeled off with a cutter knife, the electrode active substance layer was easily peeled off, and almost no electrode active substance remained on the surface of the current collector. Using the obtained electrode, a battery was prepared by the method described in Example 1 and a charge / discharge test was conducted. The discharge capacity at 100th cycle was 50% of that at 10th cycle.
【００３１】[0031]
【発明の効果】本発明により、電極活性物質と集電体と
の接着強度が強い電極の作製が可能となる。これを二次
電池に適用すれば、充放電の繰り返しにより放電容量が
劣化しない二次電池が得られ、特に、リチウム二次電池
に有用である。EFFECTS OF THE INVENTION According to the present invention, it is possible to manufacture an electrode in which the adhesive strength between the electrode active substance and the current collector is high. When this is applied to a secondary battery, a secondary battery whose discharge capacity does not deteriorate due to repeated charging and discharging can be obtained, and it is particularly useful for a lithium secondary battery.
Claims (4)
結着剤からなる電極構成物質層が形成されている電池用
電極において、結着剤が、（ａ）カルボン酸基あるいは
カルボン酸無水物基を有する単量体０．５〜２０重量部
とアクリル酸エステルおよびメタクリル酸エステルから
選ばれる少なくとも１種類の単量体１００重量部からな
るアクリル系共重合体および（ｂ）ポリフッ化ビニリデ
ン系樹脂から構成され、（ａ）の含有率が当該結着剤の
０．５〜２０重量％であることを特徴とする電極。1. In a battery electrode in which an electrode constituent substance layer comprising at least an electrode active substance and a binder is formed on the surface of a current collector, the binder is (a) a carboxylic acid group or a carboxylic acid anhydride. Acrylic copolymer comprising 0.5 to 20 parts by weight of a monomer having a physical group and 100 parts by weight of at least one kind of monomer selected from acrylic acid ester and methacrylic acid ester, and (b) polyvinylidene fluoride-based copolymer An electrode comprising a resin, wherein the content of (a) is 0.5 to 20% by weight of the binder.
リデン単独重合体である請求項１記載の電極。2. The electrode according to claim 1, wherein the polyvinylidene fluoride resin is a vinylidene fluoride homopolymer.
エチレン、六フッ化プロピレン、三フッ化エチレン、お
よび三フッ化塩化エチレンから選ばれる少なくとも１種
類のモノマーとフッ化ビニリデンとの共重合体であり、
該共重合体中のフッ化ビニリデン成分の比率が５０重量
％以上である請求項１記載の電極。3. A copolymer of a vinylidene fluoride resin and at least one monomer selected from ethylene tetrafluoride, propylene hexafluoride, ethylene trifluoride, and ethylene trifluoride chloride. And
The electrode according to claim 1, wherein the proportion of the vinylidene fluoride component in the copolymer is 50% by weight or more.
なる電極構成物質層が形成されている電極を具備する二
次電池において、結着剤が、（ａ）カルボン酸基あるい
はカルボン酸無水物基を有する単量体０．５〜２０重量
部とアクリル酸エステルおよびメタクリル酸エステルか
ら選ばれる少なくとも１種類の単量体１００重量部から
なるアクリル系共重合体および（ｂ）ポリフッ化ビニリ
デン系樹脂から構成され、（ａ）の含有率が当該結着剤
の０．５〜２０重量％であることを特徴とする二次電
池。4. A secondary battery comprising an electrode having an electrode constituent substance layer comprising an electrode active substance and a binder formed on the surface of a current collector, wherein the binder is (a) a carboxylic acid group or An acrylic copolymer comprising 0.5 to 20 parts by weight of a monomer having a carboxylic acid anhydride group and 100 parts by weight of at least one monomer selected from acrylic acid ester and methacrylic acid ester, and (b) a polyfluoride. A secondary battery comprising a vinylidene chloride-based resin, wherein the content of (a) is 0.5 to 20% by weight of the binder.
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8008608A JPH09199132A (en) | 1996-01-22 | 1996-01-22 | Electrode and secondary battery using it |
| EP97901079A EP0876439A1 (en) | 1996-01-22 | 1997-01-22 | Method for the adhesion of fluorinated resins to metals |
| CA002243354A CA2243354A1 (en) | 1996-01-22 | 1997-01-22 | Method for the adhesion of fluorinated resins to metals |
| KR1019980705576A KR19990081865A (en) | 1996-01-22 | 1997-01-22 | Attachment method of fluorinated resin to metal |
| PCT/EP1997/000313 WO1997027260A1 (en) | 1996-01-22 | 1997-01-22 | Method for the adhesion of fluorinated resins to metals |
| AU14448/97A AU1444897A (en) | 1996-01-22 | 1997-01-22 | Method for the adhesion of fluorinated resins to metals |
| CN97193081A CN1213393A (en) | 1996-01-22 | 1997-01-22 | Method for adhesion of fluorinated resins to metals |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8008608A JPH09199132A (en) | 1996-01-22 | 1996-01-22 | Electrode and secondary battery using it |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH09199132A true JPH09199132A (en) | 1997-07-31 |
Family
ID=11697684
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8008608A Pending JPH09199132A (en) | 1996-01-22 | 1996-01-22 | Electrode and secondary battery using it |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH09199132A (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5972056A (en) * | 1994-11-29 | 1999-10-26 | Aktsionernoe Obschestvo Zakrytogo Tipa "Elit" | Method of manufacturing a battery electrode |
| JP2002134113A (en) * | 2000-10-30 | 2002-05-10 | Matsushita Electric Ind Co Ltd | Nonaqueous secondary battery |
| KR100340952B1 (en) * | 1999-07-22 | 2002-06-20 | 윤덕용 | Porous Polymeric Electrolytes Comprising Vinylidenefluoride and Polyacrylate Polymers and Process for Preparing the Same |
| KR100553736B1 (en) * | 1999-09-02 | 2006-02-20 | 삼성에스디아이 주식회사 | Composition of active material for lithium secondary batteries |
| JP2006107767A (en) * | 2004-09-30 | 2006-04-20 | Dainippon Printing Co Ltd | Coating composition for active substance layer, electrode plate for nonaqueous electrolyte solution secondary battery, and nonaqueous electrolyte solution secondary battery |
| JP2007063513A (en) * | 2005-09-02 | 2007-03-15 | Denki Kagaku Kogyo Kk | Method for adjusting electrostatic charge characteristic |
| JP2007128660A (en) * | 2005-11-01 | 2007-05-24 | Matsushita Electric Ind Co Ltd | Manufacturing method of cathode plate for lithium secondary battery, and lithium secondary battery using the cathode |
| CN100431204C (en) * | 2005-09-22 | 2008-11-05 | 松下电器产业株式会社 | Negative electrode for lithium ion secondary battery and lithium ion secondary battery prepared by using the same |
| WO2010092977A1 (en) * | 2009-02-12 | 2010-08-19 | ダイキン工業株式会社 | Electrode mixture slurry for lithium secondary batteries, and electrode and lithium secondary battery that use said slurry |
| JP2013069555A (en) * | 2011-09-22 | 2013-04-18 | Fujikura Kasei Co Ltd | Positive electrode material for lithium ion secondary battery, and lithium ion secondary battery |
| CN110100337A (en) * | 2016-12-20 | 2019-08-06 | 索尔维特殊聚合物意大利有限公司 | Aqueous electrode adhesive for lithium ion battery |
-
1996
- 1996-01-22 JP JP8008608A patent/JPH09199132A/en active Pending
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5972056A (en) * | 1994-11-29 | 1999-10-26 | Aktsionernoe Obschestvo Zakrytogo Tipa "Elit" | Method of manufacturing a battery electrode |
| KR100340952B1 (en) * | 1999-07-22 | 2002-06-20 | 윤덕용 | Porous Polymeric Electrolytes Comprising Vinylidenefluoride and Polyacrylate Polymers and Process for Preparing the Same |
| KR100553736B1 (en) * | 1999-09-02 | 2006-02-20 | 삼성에스디아이 주식회사 | Composition of active material for lithium secondary batteries |
| JP2002134113A (en) * | 2000-10-30 | 2002-05-10 | Matsushita Electric Ind Co Ltd | Nonaqueous secondary battery |
| JP2006107767A (en) * | 2004-09-30 | 2006-04-20 | Dainippon Printing Co Ltd | Coating composition for active substance layer, electrode plate for nonaqueous electrolyte solution secondary battery, and nonaqueous electrolyte solution secondary battery |
| JP4712494B2 (en) * | 2005-09-02 | 2011-06-29 | 電気化学工業株式会社 | Charging characteristics adjustment method |
| JP2007063513A (en) * | 2005-09-02 | 2007-03-15 | Denki Kagaku Kogyo Kk | Method for adjusting electrostatic charge characteristic |
| CN100431204C (en) * | 2005-09-22 | 2008-11-05 | 松下电器产业株式会社 | Negative electrode for lithium ion secondary battery and lithium ion secondary battery prepared by using the same |
| JP2007128660A (en) * | 2005-11-01 | 2007-05-24 | Matsushita Electric Ind Co Ltd | Manufacturing method of cathode plate for lithium secondary battery, and lithium secondary battery using the cathode |
| WO2010092977A1 (en) * | 2009-02-12 | 2010-08-19 | ダイキン工業株式会社 | Electrode mixture slurry for lithium secondary batteries, and electrode and lithium secondary battery that use said slurry |
| JPWO2010092977A1 (en) * | 2009-02-12 | 2012-08-16 | ダイキン工業株式会社 | Slurry for electrode mixture of lithium secondary battery, electrode using the slurry, and lithium secondary battery |
| JP5625917B2 (en) * | 2009-02-12 | 2014-11-19 | ダイキン工業株式会社 | Slurry for electrode mixture of lithium secondary battery, electrode using the slurry, and lithium secondary battery |
| JP2013069555A (en) * | 2011-09-22 | 2013-04-18 | Fujikura Kasei Co Ltd | Positive electrode material for lithium ion secondary battery, and lithium ion secondary battery |
| US9577262B2 (en) | 2011-09-22 | 2017-02-21 | Fujikura Kasei Co., Ltd. | Positive electrode material for lithium ion secondary cell and lithium ion secondary cell |
| EP2760066B1 (en) * | 2011-09-22 | 2017-08-30 | Fujikura Kasei Co., Ltd. | Positive electrode material for lithium-ion secondary battery and lithium-ion secondary battery |
| CN110100337A (en) * | 2016-12-20 | 2019-08-06 | 索尔维特殊聚合物意大利有限公司 | Aqueous electrode adhesive for lithium ion battery |
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