JPH1064522A - Manufacture of sheet-like electrode plate and nonaqueous electrolyte battery - Google Patents
Manufacture of sheet-like electrode plate and nonaqueous electrolyte batteryInfo
- Publication number
- JPH1064522A JPH1064522A JP8212586A JP21258696A JPH1064522A JP H1064522 A JPH1064522 A JP H1064522A JP 8212586 A JP8212586 A JP 8212586A JP 21258696 A JP21258696 A JP 21258696A JP H1064522 A JPH1064522 A JP H1064522A
- Authority
- JP
- Japan
- Prior art keywords
- electrode
- sheet
- battery
- electrode plate
- electrode mixture
- 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.)
- Granted
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
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、シート状極板の製
造方法、およびそのシート状極板から作製した電極をロ
ール状に巻回して備えた非水電解質電池に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing a sheet-shaped electrode plate and a non-aqueous electrolyte battery provided with electrodes formed from the sheet-shaped electrode plate wound in a roll.
【０００２】[0002]
【従来の技術】負極活物質としてリチウムを用いた非水
電解質電池が、高エネルギー密度電池として注目されて
おり、特に正極活物質に二酸化マンガン、フッ化炭素、
塩化チオニルなどを用いた一次電池は、電卓、時計の電
源やメモリのバックアップ電池として多用されている。2. Description of the Related Art A non-aqueous electrolyte battery using lithium as a negative electrode active material has attracted attention as a high energy density battery. In particular, manganese dioxide, fluorocarbon,
A primary battery using thionyl chloride or the like is widely used as a power source for calculators and watches, and as a backup battery for memories.
【０００３】さらに近年、カメラ一体型ＶＴＲ、ラップ
トップパソコン、携帯電話などの各種の電子機器の小型
化、軽量化に伴い、それらの電源として高エネルギー密
度の二次電池の要求が高まり、炭素材料を負極活物質と
するリチウム二次電池の研究が盛んに行われている。In recent years, as various electronic devices such as a camera-integrated VTR, a laptop personal computer, and a mobile phone have become smaller and lighter, a demand for a secondary battery having a high energy density as a power source for the electronic devices has been increased. Research on a lithium secondary battery using as a negative electrode active material has been actively conducted.
【０００４】しかしながら、リチウム電池に代表され
る、有機電解液を主成分とする非水電解質を用いる電池
（非水電解質電池）では、非水電解質の電気伝導度が水
系電解質に比べて低いので、電極板を薄くする必要があ
る。また、大電流を取り出すには反応面積を大きくする
必要があるため、正、負の電極板をシート状にし、これ
らの電極をセパレータを介してロール状に巻回した渦巻
式構造が採用されている。 そして、従来からこのよう
な電極用のシート状極板を製造する方法としては、電極
活物質に導電剤、結着剤を混練した電極合剤をロール圧
延しながら支持体（導電性基材）に圧入充填する方法
や、混練した電極合剤を支持体の両側に押出し形成する
方法（特開平4-282558号公報参照）、あるいは、引き上
げ方式（特開昭 62-256365号公報および特開昭 63-1140
58号公報参照）、引き下げ方式（特開平1-267953号公報
および特開平1-194265号公報参照）、リバースロール方
式、グラビアロール方式、ドクターブレード方式、スロ
ットノズルを有するエクストルージョン型注液器を用い
る方式（特開平 7-65816号公報参照）により、それぞれ
電極合剤を支持体上に塗布する方法などが提案されてい
る。However, in a battery using a non-aqueous electrolyte containing an organic electrolyte as a main component (a non-aqueous electrolyte battery) represented by a lithium battery, the electric conductivity of the non-aqueous electrolyte is lower than that of an aqueous electrolyte. It is necessary to make the electrode plate thin. In order to extract a large current, it is necessary to increase the reaction area. Therefore, a spiral structure is adopted in which the positive and negative electrode plates are formed into a sheet shape, and these electrodes are wound in a roll shape via a separator. I have. Conventionally, as a method of manufacturing such a sheet-shaped electrode plate for an electrode, a support (conductive base material) is prepared by rolling an electrode mixture obtained by kneading a conductive agent and a binder into an electrode active material. Into the support, press-fit the kneaded electrode mixture on both sides of the support (see JP-A-4-282558), or pull up (see JP-A-62-256365 and JP-A-62-256365). 63-1140
No. 58), a pull-down method (see JP-A 1-267953 and JP-A 1-194265), a reverse roll method, a gravure roll method, a doctor blade method, and an extrusion type liquid injector having a slot nozzle. Depending on the method used (see Japanese Patent Application Laid-Open No. 7-65816), a method of applying an electrode mixture on a support has been proposed.
【０００５】[0005]
【発明が解決しようとする課題】しかしながら、これら
はいずれも支持体上に表裏両面で同じ量の電極合剤を塗
工する方法であるため、これらの方法で製造されたシー
ト状極板を使用した電池では、長時間の充放電サイクル
において性能の劣化が起こり易かった。However, since each of these methods is a method in which the same amount of the electrode mixture is coated on both the front and back surfaces of the support, the sheet-shaped electrode plate manufactured by these methods is used. In the battery thus obtained, the performance was easily deteriorated in a long charge / discharge cycle.
【０００６】すなわち、これらの方法で製造されたシー
ト状極板は、円筒形、角形などの電池１ケ分の長さに裁
断しロール状に巻回して使用されるが、表裏両面で電極
合剤の塗工量が同じ場合には、電池の各部例えば巻芯部
と外周部とで、セパレータを介して対向する正極と負極
の活物質密度のバランスが崩れる。そのため、充放電に
よる電解液の出入りが異なったり、あるいは特に正極の
活物質が過剰なときには、金属リチウムの析出などの現
象が起こり、長時間の充放電サイクルにおいて性能の劣
化が起こり易かった。That is, the sheet-shaped electrode plate manufactured by these methods is cut into a length of one battery, such as a cylinder or a square, and is used by winding it into a roll. When the coating amounts of the agents are the same, the balance of the active material densities of the positive electrode and the negative electrode facing each other via the separator in each part of the battery, for example, the core and the outer peripheral part, is lost. Therefore, when the inflow and outflow of the electrolyte due to charge and discharge differ, or particularly when the active material of the positive electrode is excessive, phenomena such as deposition of metallic lithium occur, and the performance tends to deteriorate in a long charge and discharge cycle.
【０００７】本発明は、このような問題を解決するため
になされたもので、安全性に優れかつ高容量であり、さ
らに充放電のサイクル性が向上した電池を得ることがで
きるシート状極板の製造方法、ならびにそのようなシー
ト状極板から作製される電極をロール状に巻回した渦巻
式構造を有する非水電解質電池を提供することを目的と
する。The present invention has been made in order to solve such a problem, and a sheet-shaped electrode plate capable of obtaining a battery having excellent safety, high capacity, and improved charge / discharge cyclability. It is an object of the present invention to provide a nonaqueous electrolyte battery having a spiral structure in which an electrode produced from such a sheet-shaped electrode plate is wound in a roll shape.
【０００８】[0008]
【課題を解決するための手段】本発明のシート状極板の
製造方法は、導電性基材上に電極合剤を塗布した後、塗
布層を乾燥し次いで加圧して圧縮するシート状極板の製
造方法において、前記導電性基材の表裏両面で、単位面
積当りの電極合剤の塗布量を異ならせることを特徴とす
る。According to the present invention, there is provided a method for producing a sheet-shaped electrode plate, which comprises applying an electrode mixture onto a conductive substrate, drying the coated layer, and pressing and compressing the electrode mixture. The manufacturing method of (1) is characterized in that the application amount of the electrode mixture per unit area is changed on both the front and back surfaces of the conductive substrate.
【０００９】また、本発明の非水電解質電池は、このよ
うな方法により製造したシート状極板から作製した電極
を、正極および／または負極として有し、セパレータお
よび電解質を備えたことを特徴とする。A nonaqueous electrolyte battery according to the present invention is characterized in that it has an electrode made from a sheet-shaped electrode plate manufactured by such a method as a positive electrode and / or a negative electrode, and is provided with a separator and an electrolyte. I do.
【００１０】本発明において、導電性基材上への電極合
剤の塗布は、以下に示すようなダイノズルを用いて行な
われる。すなわち、本発明に使用するダイノズルは、例
えば２つのリップが適当な間隙を保って対向配置されて
ランドが形成され、このランドに連通した液溜め用マニ
ホールドを内部に備えた構造を有し、電極合剤（電極材
料）塗布液は、外部に設けられた塗布液供給システムに
よりマニホールドに供給された後、ランドを経てリップ
先端部から吐出され、走行する導電性基材の表裏両面
に、逐次または同時に塗布されるようになっている。In the present invention, the application of the electrode mixture onto the conductive substrate is performed using a die nozzle as described below. That is, the die nozzle used in the present invention has a structure in which, for example, two lips are arranged opposite to each other with an appropriate gap therebetween to form a land, and a liquid reservoir manifold communicating with the land is provided inside the die nozzle. After the mixture (electrode material) coating liquid is supplied to the manifold by a coating liquid supply system provided outside, it is discharged from the tip of the lip through the land, and sequentially or on the front and back surfaces of the traveling conductive base material. They are applied at the same time.
【００１１】ここで、このようなダイノズルによる塗布
は、導電性基材の面全体への連続塗布でも良いが、導電
性基材の長手方向、幅方向のいずれかの方向に沿って一
定間隔ごとに未塗布部を設けても良い。未塗布部は、導
電性基材の表裏両面の同じ位置でも多少ずれた位置で
も、どちらの位置に形成しても良い。Here, the coating by the die nozzle may be continuous coating on the entire surface of the conductive substrate, but may be performed at regular intervals along the longitudinal direction or the width direction of the conductive substrate. May be provided with an uncoated portion. The uncoated portion may be formed at the same position on the front and back surfaces of the conductive substrate or at a position slightly shifted, or at any position.
【００１２】また本発明においては、導電性基材の表裏
両面で単位面積当りの電極合剤の塗布量を変えることに
より、加圧処理後の極板の両面で、電極合剤層中の活物
質密度を変え、それにより、シート状電極をロール状に
巻回して成る非水電解質電池において、正極と負極の電
極合剤（電極活物質）のバランスが最適に保たれるよう
になっている。ここで、導電性基材の表裏両面における
電極合剤の塗布量の差は、少量側の面の塗布量に対して
2〜10％の割合であることが望ましい。両面の塗布量の
差が 2％未満では、両面で塗布量を変えた効果がほとん
どなく、反対に10％を越える場合には、正負の電極合剤
（電極活物質）量がアンバランスで電解液のしみ込み性
が悪い部分が生じ、電池の容量が低下するばかりでな
く、サイクル寿命も短くなり好ましくない。例えばリチ
ウム二次電池において、正極活物質としてＬｉＣｏＯ2
を用い、正負の電極活物質量のバランスが正極過剰の場
合、正極から発生するＬｉイオンが負極で全てはインタ
ーカレートされなくなり、その結果負極表面にＬｉ金属
が析出し、安全性に問題が生じるばかりでなく、サイク
ル性も悪化する。Further, in the present invention, by changing the application amount of the electrode mixture per unit area on both the front and back surfaces of the conductive substrate, the active material in the electrode mixture layer on both surfaces of the electrode plate after the pressure treatment is changed. By changing the material density, in a non-aqueous electrolyte battery in which a sheet-like electrode is wound in a roll shape, the balance between the electrode mixture (electrode active material) of the positive electrode and the negative electrode can be kept optimal. . Here, the difference in the coating amount of the electrode mixture on both the front and back surfaces of the conductive base material is smaller than the coating amount on the smaller surface.
Desirably, the ratio is 2 to 10%. If the difference between the coating amounts on both sides is less than 2%, there is almost no effect of changing the coating amount on both sides. Conversely, if it exceeds 10%, the amount of positive and negative electrode mixture (electrode active material) is unbalanced and Some portions have poor liquid permeation properties, which not only reduces the capacity of the battery but also shortens the cycle life, which is not preferable. For example, in a lithium secondary battery, LiCoO 2 is used as a positive electrode active material.
If the balance of the positive and negative electrode active materials is excessive in the positive electrode, all of the Li ions generated from the positive electrode are not intercalated at the negative electrode, and as a result, Li metal is deposited on the negative electrode surface, which poses a problem in safety. Not only does it occur, but also the cyclability deteriorates.
【００１３】本発明において塗布される電極合剤の塗布
液は、電極活物質、導電剤、結着剤、溶媒などを含むこ
とができる。電極活物質としては、Ｈ+ 、Ｌｉ+ 、Ｎａ
+ 、Ｋ+ が挿入および／または放出できる化合物であれ
ば、どのような化合物でも良いが、なかでも遷移金属酸
化物、遷移金属カルコゲナイド、炭素質材料等を用いる
ことができ、特にリチウム含有遷移金属酸化物または炭
素質材料の使用が好ましい。なお、遷移金属としては、
Ｃｏ、Ｍｎ、Ｎｉ、Ｖ、Ｆｅを主体とするものが好まし
く、このような遷移金属酸化物として、具体的には、Ｌ
ｉＣｏＯ2 、ＬｉＮｉＯ2 、ＬｉＭｎ2 Ｏ4 、ＬｉＣｏ
ＶＯ4 、ＬｉＮｉＶＯ4 、ＬｉＣｏ0.9Ｓｎ0.1 Ｏ2 、
Ｆｅ3 Ｏ4 、Ｖ2 Ｏ5 などが挙げられる。また、炭素材
料としては、 002面の面間隔が 0.335〜0.38nm、密度が
1.1〜 2.3g/cm3 のものの使用が好ましく、具体的に
は、黒鉛、石油コークス、クレゾール樹脂焼成炭素、フ
ラン樹脂焼成炭素、ポリアクリロニトリル繊維焼成炭
素、気相成長炭素、メソフェーズピッチ焼成炭素などを
挙げることができる。The coating solution of the electrode mixture applied in the present invention can contain an electrode active material, a conductive agent, a binder, a solvent and the like. As the electrode active material, H + , Li + , Na
+ And K + may be any compounds as long as they can insert and / or release them. Among them, transition metal oxides, transition metal chalcogenides, carbonaceous materials and the like can be used. The use of oxides or carbonaceous materials is preferred. In addition, as a transition metal,
Those mainly composed of Co, Mn, Ni, V and Fe are preferable. As such a transition metal oxide, specifically, L
iCoO 2 , LiNiO 2 , LiMn 2 O 4 , LiCo
VO 4 , LiNiVO 4 , LiCo 0.9 Sn 0.1 O 2 ,
Fe 3 O 4 , V 2 O 5 and the like. In addition, as a carbon material, the plane spacing of the 002 plane is 0.335 to 0.38 nm, and the density is
The use of 1.1 to 2.3 g / cm 3 is preferred, specifically, graphite, petroleum coke, cresol resin fired carbon, furan resin fired carbon, polyacrylonitrile fiber fired carbon, vapor grown carbon, mesophase pitch fired carbon, and the like. Can be mentioned.
【００１４】導電剤としては、構成された電池において
化学変化を起こさない電子伝導性材料であれば、どのよ
うなものでも使用することができる。通常、天然黒鉛
（鱗状黒鉛、鱗片状黒鉛など）、人工黒鉛、カーボンブ
ラック、アセチレンブラック、ケッチェンブラック、炭
素繊維、金属粉、金属繊維あるいはポリフェニレン誘導
体等の導電性材料を、１種単独でまたは２種以上混合し
て使用することができ、特に黒鉛とアセチレンブラック
との併用が好ましい。As the conductive agent, any material can be used as long as it does not cause a chemical change in the constructed battery. Usually, conductive materials such as natural graphite (scale graphite, flaky graphite, etc.), artificial graphite, carbon black, acetylene black, ketjen black, carbon fiber, metal powder, metal fiber or polyphenylene derivative are used alone or alone. Two or more kinds can be used as a mixture, and in particular, a combination of graphite and acetylene black is preferable.
【００１５】結着剤としては、非水電解質電池に使用す
る有機電解液に溶解または膨潤しにくい多糖類、熱可塑
性樹脂、あるいはゴム弾性を有するポリマーを、１種ま
たは２種以上混合して用いることができる。具体的に
は、でんぷん、カルボキシメチルセルロース、ヒドロキ
シプロピルセルロース、ポリビニルアルコール、ポリビ
ニルクロリド、ポリテトラフルオロエチレン、ポリフッ
化ビニリデン、フッ素ゴム、エチレン−プロピレン−ジ
エンタ−ポリマー（ＥＰＤＭ）、スチレンブタジエンゴ
ム、ポリブタジエン、ポリエチレンオキシド等を挙げる
ことができる。これらの結着剤は、溶媒に溶解しても良
いし、分散または懸濁などのようにエマルジョン状態で
あっても良い。As the binder, a polysaccharide, a thermoplastic resin, or a polymer having rubber elasticity, which hardly dissolves or swells in the organic electrolyte used for the non-aqueous electrolyte battery, is used alone or as a mixture of two or more. be able to. Specifically, starch, carboxymethylcellulose, hydroxypropylcellulose, polyvinyl alcohol, polyvinyl chloride, polytetrafluoroethylene, polyvinylidene fluoride, fluororubber, ethylene-propylene-diene-polymer (EPDM), styrene-butadiene rubber, polybutadiene, poly Examples include ethylene oxide. These binders may be dissolved in a solvent or may be in an emulsion state such as dispersion or suspension.
【００１６】さらに、これらの電極活物質、導電剤、結
着剤を混練する際の溶媒としては、水あるいは１種また
は２種以上の有機溶剤の混合物を用いることができる。
有機溶剤の種類は特に限定されないが、Ｎ−メチルピロ
リドン、キシレン、トルエン、アセトン、メチルエチル
ケトン、メチルイソブチルケトン、シクロヘキサノン、
エタノール、メタノール、酢酸エチル、酢酸ブチル、メ
チレンクロライド、エチレンクロライド、エチルセロソ
ルブ等の使用が好ましい。Further, as a solvent for kneading the electrode active material, the conductive agent and the binder, water or a mixture of one or more organic solvents can be used.
Although the type of the organic solvent is not particularly limited, N-methylpyrrolidone, xylene, toluene, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone,
It is preferable to use ethanol, methanol, ethyl acetate, butyl acetate, methylene chloride, ethylene chloride, ethyl cellosolve and the like.
【００１７】本発明において、電極合剤塗布液の組成は
特に限定されないが、通常、電極活物質 100重量部に対
し、導電剤 1〜50重量部、結着剤 0.1〜50重量部、およ
び溶媒30〜 600重量部を含んで構成される。また、塗布
液の温度は、必要に応じて制御することができるが、塗
布時において15〜30℃（特に20〜25℃）の範囲とするこ
とが好ましい。In the present invention, the composition of the electrode mixture coating solution is not particularly limited, but usually 1 to 50 parts by weight of a conductive agent, 0.1 to 50 parts by weight of a binder, and solvent for 100 parts by weight of an electrode active material. It comprises 30 to 600 parts by weight. The temperature of the coating solution can be controlled as needed, but is preferably in the range of 15 to 30 ° C. (particularly 20 to 25 ° C.) during coating.
【００１８】本発明において使用される導電性基材は、
特に限定されるものではないが、アルミニウム、銅、ニ
ッケル、ステンレス等の金属箔や、無機酸化物、有機高
分子材料、炭素等の導電性フィルムを用いることができ
る。また、このような導電性基材の形態は、連続シー
ト、穴あきシート、ネット（網）状シートなど、いろい
ろな形態とすることができるが、特に連続シートとする
ことが好ましい。さらに、導電性基材の厚さは 1〜30μ
m とすることが好ましい。The conductive substrate used in the present invention comprises:
Although not particularly limited, a metal foil such as aluminum, copper, nickel, and stainless steel, or a conductive film such as an inorganic oxide, an organic polymer material, and carbon can be used. The form of such a conductive substrate can be various forms such as a continuous sheet, a perforated sheet, a net (net) sheet, etc., but a continuous sheet is particularly preferable. In addition, the thickness of the conductive substrate is 1-30μ
m is preferable.
【００１９】本発明においては、このような導電性基材
の表裏両面に電極材料塗布液が塗布された後、乾燥室に
搬送されて、塗布層中の溶媒が除去され、次いでプレス
ローラー間を通す等の方法で加圧圧縮される。乾燥方法
としては、熱風乾燥、赤外線乾燥、接触ドラムなどの方
法があり、これらを単独でまたは組合せて用いることが
できる。熱風乾燥の場合の乾燥温度は、塗布液の組成に
よって設定されるが、通常50〜 160℃（特に90〜 150
℃）とすることが好ましい。また、加圧処理の際の圧力
は、線圧で 200〜 1000kg/cmとすることが好ましい。In the present invention, after the coating solution for the electrode material is applied to both the front and back surfaces of such a conductive substrate, the solution is conveyed to a drying chamber to remove the solvent in the coating layer. It is pressurized and compressed by a method such as passing through. Examples of the drying method include methods such as hot air drying, infrared drying, and contact drum, and these can be used alone or in combination. The drying temperature in the case of hot air drying is set depending on the composition of the coating solution, but is usually 50 to 160 ° C (particularly 90 to 150 ° C).
C). Further, the pressure at the time of the pressure treatment is preferably 200 to 1000 kg / cm in linear pressure.
【００２０】本発明では、こうして製造されたシート状
極板から作製した電極を、正極と負極のどちらか一方ま
たは両方として用い、円筒形、角形などの一次電池また
は２次電池を作製することができる。ここで、正極シー
トと負極シートとを分離するセパレータとしては、例え
ば、ポリエチレンフィルム、微孔性ポリプロピレンフィ
ルム、ガラス繊維フィルムなどが挙げられる。また電解
質としては、有機溶媒として、例えばプロピレンカーボ
ネート、エチレンカーボネート、ブチレンカーボネー
ト、ジメチルカーボネート、ジエチルカーボネート、γ
−ブチロラクトン、1,2-ジメトキシエタン、テトラヒド
ロキシフランなどの非プロトン性有機溶媒の少なくとも
１種以上を混合した溶媒と、その溶媒に溶けるリチウム
塩、例えばＬｉＣｌＯ4 、ＬｉＢＦ4 、ＬｉＰＦ6 、Ｌ
ｉＣＦ3 ＳＯ3 、ＬｉＣＦ3 ＣＯ2、ＬｉＡｓＦ6 など
の１種以上の塩から構成された溶液が挙げられる。In the present invention, the electrode manufactured from the sheet electrode thus manufactured is used as one or both of the positive electrode and the negative electrode to manufacture a primary battery or a secondary battery such as a cylindrical or rectangular battery. it can. Here, examples of the separator for separating the positive electrode sheet and the negative electrode sheet include a polyethylene film, a microporous polypropylene film, and a glass fiber film. As the electrolyte, as an organic solvent, for example, propylene carbonate, ethylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, γ
-A solvent in which at least one kind of aprotic organic solvent such as butyrolactone, 1,2-dimethoxyethane, tetrahydroxyfuran is mixed, and a lithium salt soluble in the solvent, for example, LiClO 4 , LiBF 4 , LiPF 6 , L
Examples include a solution composed of one or more kinds of salts such as iCF 3 SO 3 , LiCF 3 CO 2 , and LiAsF 6 .
【００２１】[0021]
【発明の実施の形態】以下、本発明の実施の形態を、図
面に基づいて説明する。Embodiments of the present invention will be described below with reference to the drawings.
【００２２】図１は、本発明のシート状極板の製造方法
に使用する塗布装置を概略的に示す図である。FIG. 1 is a diagram schematically showing a coating apparatus used in the method for producing a sheet-shaped electrode plate of the present invention.
【００２３】この塗布装置においては、導電性基材１が
回転するバックアップロール２のロール面に密着して連
続的に走行し、この導電性基材１に対してリップ３先端
部が一定間隔を保つように、ダイノズル４が設置されて
いる。ダイノズル４は、適当な間隙を保つように対峙し
た２つのリップ３（入口側リップ３ａと出口側リップ３
ｂ）を有し、これらのリップ３によりランド５が形成さ
れ、またランド５に連通した液溜めのためのマニホール
ド６を内部に有している。電極合剤塗布液７は、ダイノ
ズル４の外部に設けられた塗布液供給システム（図示を
省略。）によってマニホールド６に供給され、ランド５
を経て、リップ３先端部に開口形成された出口部から吐
出され、導電性基材１上に塗布される。In this coating apparatus, the conductive base material 1 runs continuously in close contact with the roll surface of the rotating backup roll 2, and the tip of the lip 3 is spaced from the conductive base material 1 by a constant distance. A die nozzle 4 is provided so as to maintain the temperature. The die nozzle 4 has two lips 3 (an inlet lip 3a and an outlet lip 3) facing each other so as to maintain an appropriate gap.
The lip 3 forms a land 5 and has a manifold 6 communicating with the land 5 for a liquid reservoir therein. The electrode mixture application liquid 7 is supplied to the manifold 6 by an application liquid supply system (not shown) provided outside the die nozzle 4, and is supplied to the land 5.
Through the outlet formed at the tip of the lip 3, and is applied onto the conductive substrate 1.
【００２４】このような塗布装置により、導電性基材１
の表裏両面で単位面積当りの塗布量すなわち塗布厚を変
えて、電極合剤塗布液７が塗布される。そして、得られ
た塗布シートを熱風などで加熱乾燥した後、１対または
複数対のプレスローラー間を通し、所定の圧力で加圧し
て圧縮する。こうして、電極合剤塗布液７の塗布量に比
例して表裏両面の電極合剤層の厚さが異なり、したがっ
て層中に存在する活物質密度が異なる電極が形成され
る。With such a coating device, the conductive substrate 1
The electrode mixture application liquid 7 is applied by changing the application amount per unit area, that is, the application thickness on both the front and back surfaces. Then, the obtained application sheet is dried by heating with hot air or the like, and then passed between one or more pairs of press rollers, and is compressed by applying a predetermined pressure. In this way, electrodes having different thicknesses of the electrode mixture layers on the front and back surfaces in proportion to the application amount of the electrode mixture application liquid 7 and thus having different densities of active materials existing in the layers are formed.
【００２５】[0025]
【実施例】次に具体的に実施例を挙げて本発明をさらに
詳しく説明するが、本発明の主旨から外れない限り、以
下の実施例に限定されるものではない。EXAMPLES Next, the present invention will be described in more detail with reference to specific examples. However, the present invention is not limited to the following examples unless departing from the gist of the present invention.
【００２６】実施例１ 正極活物質としてＬｉＣｏＯ2 を90重量部、導電剤とし
てアセチレンブラックを 5重量部の割合でそれぞれ混合
し、さらに結着剤としてフッ素ゴム系バインダーを 5重
量部の割合で加え、溶媒として酢酸エチルを添加し混練
して得られた固形分濃度60重量％のスラリー状の塗布液
を、厚さ20μm のアルミニウム箔の両面に、図１に示す
塗布装置を用い、かつ表１に示すように表裏両面で同じ
塗布量（単位面積当り）で、片面ずつ塗布した。次い
で、得られた塗布シートを熱風乾燥した後、プレスロー
ラーにより圧縮し、厚さ 200μm の正極シートを作製し
た。 また、負極活物質としてメソフェーズピッチカー
ボンファイバーを85重量部、導電剤としてアセチレンブ
ラックを 5重量部、グラファイトを 5重量部の割合でそ
れぞれ混合し、さらに結着剤としてスチレンブタジエン
ゴムを 5重量部の割合で加え、溶媒として水を添加し混
練して得られた固形分濃度60重量％のスラリー状の塗布
液を、厚さ20μm の銅箔の表面に、前記した正極合剤塗
布液と同様の方法で、表１に示すように表裏両面で塗布
量を 4.9％（表面の塗布量に対して）変えて、片面ずつ
塗布した。得られた塗布シートを熱風乾燥した後、プレ
スローラーにより圧縮し、厚さ 200μm の負極シートを
作製した。Example 1 90 parts by weight of LiCoO 2 as a positive electrode active material and 5 parts by weight of acetylene black as a conductive agent were mixed, and a fluororubber binder was added as a binder at a ratio of 5 parts by weight. Then, a slurry-like coating solution having a solid content of 60% by weight obtained by adding and kneading ethyl acetate as a solvent was applied to both surfaces of a 20 μm-thick aluminum foil using the coating apparatus shown in FIG. As shown in (1), the same amount of coating (per unit area) was applied to both sides. Next, the obtained coated sheet was dried with hot air, and then compressed with a press roller to produce a positive electrode sheet having a thickness of 200 μm. Also, 85 parts by weight of mesophase pitch carbon fiber as a negative electrode active material, 5 parts by weight of acetylene black as a conductive agent, and 5 parts by weight of graphite were mixed, and 5 parts by weight of styrene butadiene rubber as a binder. A slurry-like coating solution having a solid content concentration of 60% by weight, obtained by adding and kneading water as a solvent and kneading, was coated on the surface of a copper foil having a thickness of 20 μm in the same manner as the above-mentioned positive electrode mixture coating solution. As shown in Table 1, the coating amount was changed by 4.9% (based on the coating amount on the front surface) on both the front and back surfaces by the method. After the obtained coated sheet was dried with hot air, it was compressed with a press roller to prepare a negative electrode sheet having a thickness of 200 μm.
【００２７】次いで、こうして得られた正負電極シート
を所定のサイズに裁断したものを、セパレータとして微
孔性ポリプロピレンフィルムを介し、それぞれ箔の表面
を内側、裏面を外側としてロール状に巻回し、円筒形電
池を作製した。Next, the thus obtained positive and negative electrode sheets cut into a predetermined size are wound in a roll shape with a foil surface inside and a back surface outside through a microporous polypropylene film as a separator. A battery was fabricated.
【００２８】実施例２ 正負電極とも、実施例１と同じ電極合剤塗布液と同じ手
段を用い、表１に示すように、正極における塗布量を表
裏両面で 4.9％異ならせて、正負の電極シートをそれぞ
れ作製した。次いで、これらの電極シートを、微孔性ポ
リプロピレンフィルムのセパレータを介して実施例１と
同様にロール状に巻回し、円筒形電池を作製した。Example 2 For the positive and negative electrodes, the same electrode mixture coating solution as used in Example 1 was used and the same means was used. Sheets were produced. Next, these electrode sheets were wound in a roll shape in the same manner as in Example 1 with a microporous polypropylene film separator interposed therebetween, to produce a cylindrical battery.
【００２９】実施例３ 正負電極とも、実施例１と同じ電極合剤塗布液と同じ手
段を用い、表１に示すように、正極における塗布量を
2.6％、負極における塗布量を 2.5％、それぞれ表裏両
面で異ならせて電極シートを作製し、これらの電極シー
トを、微孔性ポリプロピレンフィルムのセパレータを介
して実施例１と同様にロール状に巻回し、円筒形電池を
作製した。Example 3 For both the positive and negative electrodes, the same electrode mixture coating solution as in Example 1 was used, and as shown in Table 1, the coating amount on the positive electrode was
An electrode sheet was prepared by changing the coating amount on the front and back sides to 2.6% and the coating amount on the negative electrode to 2.5%, respectively, and these electrode sheets were wound into a roll shape in the same manner as in Example 1 through a microporous polypropylene film separator. It was turned to produce a cylindrical battery.
【００３０】実施例４ 正負電極とも、実施例１と同じ電極合剤塗布液と同じ手
段を用い、表１に示すように、正極における塗布量を
7.1％、負極における塗布量を 7.2％、それぞれ表裏両
面で異ならせて電極シートを作製した。次いで、これら
の電極シートを、微孔性ポリプロピレンフィルムのセパ
レータを介して実施例１と同様にロール状に巻回し、円
筒形電池を作製した。Example 4 For the positive and negative electrodes, the same electrode mixture coating solution as in Example 1 was used, and the coating amount on the positive electrode was adjusted as shown in Table 1.
An electrode sheet was prepared with a coating amount of 7.1% and a coating amount of the negative electrode of 7.2%, which were different on both front and back surfaces. Next, these electrode sheets were wound in a roll shape in the same manner as in Example 1 with a microporous polypropylene film separator interposed therebetween, to produce a cylindrical battery.
【００３１】比較例１ 正負電極とも、実施例１と同じ電極合剤塗布液と同じ手
段を用い、表１に示すように、正極、負極ともに表裏両
面で同一塗布量として電極シートを作製し、これらの電
極シートを、微孔性ポリプロピレンフィルムのセパレー
タを介して実施例１と同様にロール状に巻回し、円筒形
電池を作製した。COMPARATIVE EXAMPLE 1 For the positive and negative electrodes, the same electrode mixture coating solution as in Example 1 was used and the same means was used. These electrode sheets were wound in a roll shape in the same manner as in Example 1 through a microporous polypropylene film separator, to produce a cylindrical battery.
【００３２】比較例２ 正負電極とも、実施例１と同じ電極合剤塗布液と同じ手
段を用い、表１に示すように、負極における塗布量を表
裏両面で14.0％異ならせて、正負の電極シートをそれぞ
れ作製した。次いで、これらの電極シートを、微孔性ポ
リプロピレンフィルムのセパレータを介して実施例１と
同様にロール状に巻回し、円筒形電池を作製した。COMPARATIVE EXAMPLE 2 For both positive and negative electrodes, the same electrode mixture coating solution as in Example 1 was used, and the coating amount on the negative electrode was changed by 14.0% on both the front and back surfaces as shown in Table 1 to obtain the positive and negative electrodes. Sheets were produced. Next, these electrode sheets were wound in a roll shape in the same manner as in Example 1 with a microporous polypropylene film separator interposed therebetween, to produce a cylindrical battery.
【００３３】比較例３ 正負電極とも、実施例１と同じ電極合剤塗布液と同じ手
段を用い、表１に示すように、正極における塗布量を表
裏両面で14.2％異ならせて、正負の電極シートをそれぞ
れ作製した。次いで、これらの電極シートを、微孔性ポ
リプロピレンフィルムのセパレータを介して実施例１と
同様にロール状に巻回し、円筒形電池を作製した。Comparative Example 3 For the positive and negative electrodes, the same electrode mixture coating solution as in Example 1 was used, and as shown in Table 1, the coating amount on the positive electrode was changed by 14.2% on both the front and back sides. Sheets were produced. Next, these electrode sheets were wound in a roll shape in the same manner as in Example 1 with a microporous polypropylene film separator interposed therebetween, to produce a cylindrical battery.
【００３４】こうして実施例１〜４および比較例１〜３
でそれぞれ作製された電池において、セパレータを介し
て対向する正極と負極の電極合剤塗布量の比を、表２に
示す。なお、平板状態でのこのような塗布量の比の最適
値は、比較例１における比に相当する2.50（正極／負
極）である。Thus, Examples 1-4 and Comparative Examples 1-3
Table 2 shows the ratio of the amount of the electrode mixture applied between the positive electrode and the negative electrode opposed to each other with the separator interposed therebetween in each of the batteries prepared in the above. The optimum value of the ratio of the coating amount in the flat plate state is 2.50 (positive electrode / negative electrode) corresponding to the ratio in Comparative Example 1.
【００３５】[0035]
【表１】 [Table 1]
【表２】 また、実施例および比較例でそれぞれ作製された電池に
ついて、過充電試験（3C− 15V）を行なうとともに、放
電容量試験を行ない、放電容量を調べた。また、充放電
サイクル試験を行ない、容量が初期の80％となるまでの
充放電回数（サイクル寿命）を測定した。なお、過充電
試験の結果は、極めて良好を◎、良好を○、やや不良を
△、不良を×としてそれぞれ示した。また、放電容量
は、比較例１で得られた電池の容量を基準として表わし
た。これらの試験結果を、それぞれ表３に示す。[Table 2] In addition, the batteries prepared in Examples and Comparative Examples were each subjected to an overcharge test (3C-15V) and a discharge capacity test to check the discharge capacity. Further, a charge / discharge cycle test was performed, and the number of charge / discharge cycles (cycle life) until the capacity reached 80% of the initial value was measured. In addition, the results of the overcharge test were marked with 良好 for extremely good, ○ for good, △ for slightly poor, and × for bad. Further, the discharge capacity was expressed based on the capacity of the battery obtained in Comparative Example 1. Table 3 shows the results of these tests.
【００３６】[0036]
【表３】 表３から明らかなように、表裏両面で単位面積当りの電
極合剤の塗布量を 2〜10％の範囲で異ならせたシート状
電極を、正極と負極のどちらか一方または両方として用
いた実施例１〜４では、両面の塗布量が等しい電極板を
使用した比較例１と比べて、セパレータを介して対向す
る正負電極の電極合剤塗布量の比が、各部分（巻芯部と
外周部）でバランス良く保たれており、過充電に対する
安全性が向上するとともに、放電容量が増大している。
また、充放電サイクル特性も向上し、サイクル寿命が大
幅に延びている。[Table 3] As is evident from Table 3, a sheet-like electrode in which the coating amount of the electrode mixture per unit area on both the front and back surfaces was varied in the range of 2 to 10% was used as one or both of the positive electrode and the negative electrode. In Examples 1 to 4, the ratio of the applied amount of the electrode mixture of the positive and negative electrodes facing each other with the separator therebetween was smaller than that of Comparative Example 1 in which the electrode plates having the same applied amount on both surfaces were used. Part), a good balance is maintained, the safety against overcharge is improved, and the discharge capacity is increased.
In addition, the charge / discharge cycle characteristics have been improved, and the cycle life has been significantly extended.
【００３７】これに対して、表裏両面の塗布量の差が10
％を越える電極板が、正極または負極として使用された
比較例２および３では、セパレータを介して対向する正
負電極の塗布量の比が、各部で大きく異なり、充放電に
よる電解液のしみ込み性が悪い部分が生じるため、過充
電に対する安全性並びに容量が低下し、サイクル寿命も
短くなっている。On the other hand, the difference between the coating amounts on the front and back sides is 10
% In Comparative Examples 2 and 3 in which the electrode plate exceeding% was used as the positive electrode or the negative electrode, the ratio of the coating amounts of the positive and negative electrodes facing each other via the separator was greatly different in each part, and the penetration of the electrolytic solution by charging and discharging was observed. However, the safety and capacity against overcharge are reduced, and the cycle life is shortened.
【００３８】[0038]
【発明の効果】以上の説明から明らかなように、本発明
により、表裏両面で単位面積当りの電極合剤の塗布量、
すなわち電極活物質の密度の異なるシート状極板を得る
ことができ、こうして得られたシート状極板から作製さ
れた電極をセパレータを介してロール状に巻回し、正極
および／または負極して使用することで、安全性に優れ
高容量であり、さらに充放電のサイクル特性が向上した
非水電解質電池を得ることができる。As is clear from the above description, according to the present invention, the coating amount of the electrode mixture per unit area on both the front and back surfaces is improved.
That is, a sheet-shaped electrode plate having a different density of the electrode active material can be obtained, and an electrode produced from the sheet-shaped electrode plate thus obtained is wound into a roll shape through a separator, and used as a positive electrode and / or a negative electrode. By doing so, it is possible to obtain a non-aqueous electrolyte battery which is excellent in safety, has high capacity, and further has improved charge / discharge cycle characteristics.
【図１】本発明のシート状極板の製造方法に使用する塗
布装置の一実施例を概略的に示す図。FIG. 1 is a view schematically showing an embodiment of a coating apparatus used in the method for producing a sheet-shaped electrode plate of the present invention.
１………導電性基材 ２………バックアップロール ３………リップ ４………ダイノズル ５………ランド ６………マニホールド ７………電極合剤塗布液 DESCRIPTION OF SYMBOLS 1 ... Conductive base material 2 ... Backup roll 3 ... Lip 4 ... Die nozzle 5 ... Land 6 ... Manifold 7 ... Electrode mixture application liquid
───────────────────────────────────────────────────── フロントページの続き (72)発明者 松本 浩一 東京都品川区南品川３丁目４番10号 東芝 電池株式会社内 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Koichi Matsumoto 3-4-10 Minamishinagawa, Shinagawa-ku, Tokyo Toshiba Battery Corporation
Claims (3)
塗布層を乾燥し次いで加圧して圧縮するシート状極板の
製造方法において、 前記導電性基材の表裏両面で、単位面積当りの電極合剤
の塗布量を異ならせることを特徴とするシート状極板の
製造方法。After applying an electrode mixture on a conductive substrate,
A method for producing a sheet-shaped electrode plate in which the coating layer is dried and then pressed and compressed, wherein the front and back surfaces of the conductive base material have different application amounts of the electrode mixture per unit area. Manufacturing method of electrode plate.
の面の塗布量に対して 2〜10％の割合であることを特徴
とする請求項１記載のシート状極板の製造方法。2. The production of a sheet-like electrode plate according to claim 1, wherein the difference in the amount of application between the front and back surfaces is 2 to 10% of the amount of application on the small surface. Method.
製造したシート状極板から作製した電極を、正極および
／または負極として有し、セパレータおよび電解質を備
えたことを特徴とする非水電解質電池。3. A non-aqueous electrolyte comprising an electrode produced from the sheet-shaped electrode plate produced by the method according to claim 1 as a positive electrode and / or a negative electrode, and comprising a separator and an electrolyte. battery.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21258696A JP3697324B2 (en) | 1996-08-12 | 1996-08-12 | Sheet electrode manufacturing method and non-aqueous electrolyte battery |
| CA002207801A CA2207801C (en) | 1996-06-19 | 1997-06-17 | Nonaqueous electrolyte battery |
| US08/878,104 US6284405B2 (en) | 1996-06-19 | 1997-06-18 | Nonaqueous electrolyte battery, electrode plate for nonaqueous electrolyte battery, and method for manufacturing electrode plate for nonaqueous electrolyte battery |
| EP97304309A EP0814525A3 (en) | 1996-06-19 | 1997-06-19 | Electrode plate for nonaqueous electrolyte battery, method of manufacture and apparatus |
| KR1019970026986A KR100269819B1 (en) | 1996-06-19 | 1997-06-19 | Nonaqueous electrolyte battery, electrode plate for nonaqueous electrolyte battery, method for manufacturing electrode plate for nonaqueous electrolyte battery, and apparatus for manufacturing electrode plate for nonaqueous electrolyte battery |
| US09/247,619 US6314638B1 (en) | 1996-06-19 | 1999-02-10 | Apparatus for manufacturing electrode plate for nonaqueous electrolyte battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21258696A JP3697324B2 (en) | 1996-08-12 | 1996-08-12 | Sheet electrode manufacturing method and non-aqueous electrolyte battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH1064522A true JPH1064522A (en) | 1998-03-06 |
| JP3697324B2 JP3697324B2 (en) | 2005-09-21 |
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| Application Number | Title | Priority Date | Filing Date |
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| JP21258696A Expired - Fee Related JP3697324B2 (en) | 1996-06-19 | 1996-08-12 | Sheet electrode manufacturing method and non-aqueous electrolyte battery |
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| JP (1) | JP3697324B2 (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001015103A (en) * | 1999-06-29 | 2001-01-19 | Matsushita Electric Ind Co Ltd | Negative electrode plate and nonaqueous electrolyte secondary battery using negative electrode plate |
| JP2007109512A (en) * | 2005-10-13 | 2007-04-26 | Nec Tokin Corp | Non-aqueous electrolytic liquid secondary battery |
| WO2008029719A1 (en) * | 2006-09-07 | 2008-03-13 | Panasonic Corporation | Nonaqueous electrolytic secondary cell |
| JP2011181438A (en) * | 2010-03-03 | 2011-09-15 | Sanyo Electric Co Ltd | Nonaqueous electrolyte secondary battery |
| US8460812B2 (en) | 2009-12-17 | 2013-06-11 | Toyota Jidosha Kabushiki Kaisha | Lithium secondary battery |
| JP2013225440A (en) * | 2012-04-23 | 2013-10-31 | Toyota Motor Corp | Lithium ion secondary battery and method of manufacturing lithium ion secondary battery |
| CN114270592A (en) * | 2019-08-28 | 2022-04-01 | 三洋电机株式会社 | Nonaqueous electrolyte secondary battery and method for manufacturing nonaqueous electrolyte secondary battery |
-
1996
- 1996-08-12 JP JP21258696A patent/JP3697324B2/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001015103A (en) * | 1999-06-29 | 2001-01-19 | Matsushita Electric Ind Co Ltd | Negative electrode plate and nonaqueous electrolyte secondary battery using negative electrode plate |
| JP2007109512A (en) * | 2005-10-13 | 2007-04-26 | Nec Tokin Corp | Non-aqueous electrolytic liquid secondary battery |
| WO2008029719A1 (en) * | 2006-09-07 | 2008-03-13 | Panasonic Corporation | Nonaqueous electrolytic secondary cell |
| JP4831075B2 (en) * | 2006-09-07 | 2011-12-07 | パナソニック株式会社 | Nonaqueous electrolyte secondary battery |
| US8313862B2 (en) | 2006-09-07 | 2012-11-20 | Panasonic Corporation | Non-aqueous battery with columnar active material |
| US8460812B2 (en) | 2009-12-17 | 2013-06-11 | Toyota Jidosha Kabushiki Kaisha | Lithium secondary battery |
| JP2011181438A (en) * | 2010-03-03 | 2011-09-15 | Sanyo Electric Co Ltd | Nonaqueous electrolyte secondary battery |
| JP2013225440A (en) * | 2012-04-23 | 2013-10-31 | Toyota Motor Corp | Lithium ion secondary battery and method of manufacturing lithium ion secondary battery |
| CN114270592A (en) * | 2019-08-28 | 2022-04-01 | 三洋电机株式会社 | Nonaqueous electrolyte secondary battery and method for manufacturing nonaqueous electrolyte secondary battery |
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|---|---|
| JP3697324B2 (en) | 2005-09-21 |
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