JPH11323593A - Porous current collector for battery, electrode, their production and apparatus for production therefor - Google Patents
Porous current collector for battery, electrode, their production and apparatus for production thereforInfo
- Publication number
- JPH11323593A JPH11323593A JP10145150A JP14515098A JPH11323593A JP H11323593 A JPH11323593 A JP H11323593A JP 10145150 A JP10145150 A JP 10145150A JP 14515098 A JP14515098 A JP 14515098A JP H11323593 A JPH11323593 A JP H11323593A
- Authority
- JP
- Japan
- Prior art keywords
- drum
- metal
- plating layer
- peeling
- roll
- 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
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、主には鉄、銅、ア
ルミニウム等の金属を素材とする電池用多孔集電体、そ
れを用いた電極、それらを製造するための製造方法及び
製造装置に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a porous current collector for a battery mainly made of a metal such as iron, copper or aluminum, an electrode using the same, a manufacturing method and a manufacturing apparatus for manufacturing the same. About.
【０００２】[0002]
【従来の技術】従来、めっき浴から金属メッシュ箔を製
造する方法として、不導体部を設けた導電ドラムにめっ
きし、それを剥離する等、数多くの特許が出されてお
り、この観点からは公知の事実である。最近の特許の例
として、特開平８−１００２８８号公報に提示されてい
る方法がある。この製造方法は、外周面に絶縁性材料を
所定のパターンで埋設した金属製ドラムに電気めっきに
よりめっき層を形成し、このめっき層がめっき液中から
空気中に出た所から剥離界面までの範囲を０℃〜１５℃
の冷水でめっき層及び表面を洗浄することを特徴とす
る。また、この製造方法によってもたらされる効果とし
て、冷水をめっき層にかけることによって、金属めっき
層と絶縁性材料との密着力が減少し、埋設された絶縁性
材料が金属製ドラムから抜け落ちることがなく、長尺の
安価な金属メッシュ箔が連続的に製造できる旨記載され
ている。2. Description of the Related Art Conventionally, a number of patents have been issued as a method for producing a metal mesh foil from a plating bath, such as plating on a conductive drum provided with a non-conductive portion and peeling it off. This is a known fact. As an example of a recent patent, there is a method disclosed in JP-A-8-100288. In this manufacturing method, a plating layer is formed by electroplating on a metal drum in which an insulating material is buried in a predetermined pattern on the outer peripheral surface, and the plating layer is exposed from the plating solution to the air to the peeling interface. Range from 0 ° C to 15 ° C
The plating layer and the surface are washed with cold water. In addition, as an effect brought by this manufacturing method, by applying cold water to the plating layer, the adhesion between the metal plating layer and the insulating material is reduced, and the buried insulating material does not fall off the metal drum. It is described that a long and inexpensive metal mesh foil can be manufactured continuously.
【０００３】[0003]
【発明が解決しようとする課題】しかし、上記した金属
メッシュ箔の製造方法は、未だ、以下の解決すべき課題
を有していた。即ち、本発明者の研究によって、同製造
方法を用いて製造される金属メッシュ箔はきわめて薄く
かつ多孔であるため、適正な剥離位置や剥離角度以外の
剥離角度で剥離した場合、例えその前段階で冷却して
も、箔に破れを生じる場合が多く安定生産が困難であ
る。また、該方法は冷却水がめっき槽に落ちめっき液の
濃度が低下し、目的とする金属箔が得られないという問
題点に考慮が払われておらず、実用性に乏しいものであ
った。However, the above-described method for producing a metal mesh foil still has the following problems to be solved. That is, according to the research of the present inventor, since the metal mesh foil manufactured using the same manufacturing method is extremely thin and porous, when peeled at a peel angle other than a proper peel position and peel angle, for example, the previous stage Even when cooled, the foil often breaks, making stable production difficult. Further, this method does not take into account the problem that the cooling water falls into the plating tank and the concentration of the plating solution decreases, and the desired metal foil cannot be obtained.
【０００４】一方、近年リチウムイオン二次電池やニッ
ケル水素二次電池、あるいはリチウム系のポリマー二次
電池等の集電体として多孔化した金属箔が望まれてきて
いる。金属板の多孔化は例えばニッケル水素の負極集電
体として用いられている機械的方法で金属板に孔を開け
たパンチングメタルがあるが、近年の薄板多孔化要求に
は応じきれなくなっているのが実情である。機械的方法
による安定多孔化は箔の厚みが４０μｍが限度と言われ
ており、現在使用されている２０μｍ以下のＣｕ箔やＡ
ｌ箔の機械的方法による安定多孔化は困難であるばかり
でなく、箔の製造と孔開けの二工程を要すばかりでな
く、孔を開けた部分の金属は無駄になる等、経済的にも
改良の余地が多い。On the other hand, in recent years, a porous metal foil has been desired as a current collector for a lithium ion secondary battery, a nickel hydride secondary battery, or a lithium-based polymer secondary battery. For example, there is a punching metal in which a metal plate is perforated by a mechanical method used as a negative electrode current collector of nickel-metal hydride. Is the actual situation. It is said that the thickness of the foil is limited to 40 μm for the stabilization of pores by a mechanical method.
l Not only is it difficult to stabilize the foil by a mechanical method, but it also requires two steps, foil production and drilling, and wastes the metal in the drilled area. There is much room for improvement.
【０００５】本発明は、このような知見に基づいてなさ
れ安定生産可能で且つ電池（主にリチウム系二次電池、
ニッケル水素二次電池）に適した経済性に優れた多孔集
電体あるいは電極を提供するために考案されたものであ
る。即ち、電池用集電体として適した孔面積及び総孔部
面積を有する金属帯を得る製造装置及び製造物、さらに
はめっき層を適正な剥離位置と剥離角度で剥離すること
等の方法により、長尺の多孔金属箔を安価に連続的に製
造することができる多孔金属帯、あるいは該多孔金属帯
を集電体とした電極の製造方法及び製造装置を提供する
ものであり、従来技術では決して達成出来ないことか
ら、非常に有効性の高い、新規性を有する技術である。[0005] The present invention has been made based on such knowledge, is capable of stable production, and has a battery (mainly a lithium secondary battery,
The present invention has been devised in order to provide a porous current collector or electrode which is suitable for use in a nickel-metal hydride secondary battery and has excellent economic efficiency. That is, a manufacturing apparatus and a product for obtaining a metal band having a hole area and a total hole area suitable as a battery current collector, and further, by a method such as peeling the plating layer at an appropriate peeling position and peeling angle, It is intended to provide a method and an apparatus for producing a porous metal band capable of continuously producing a long porous metal foil at low cost, or an electrode using the porous metal band as a current collector. Since it cannot be achieved, it is a highly effective and novel technology.
【０００６】[0006]
【課題を解決するための手段】上記目的を達成するた
め、本発明の多孔集電体製造装置は、電池用集電体とし
て、多数の適正範囲の面積の不導体部を表面に不導体部
全体の総面積が適正範囲となる様に設けた導電ドラム上
に金属を析出させて、そのめっき層を剥離して、多孔金
属帯を製造する装置である。不導体部は金属帯を得た
時、応力集中により、ゆがみが発生しない様に巾方向、
長手方向に各々同じピッチで配列させる等の考慮を払わ
なければならない。In order to achieve the above object, a porous current collector manufacturing apparatus according to the present invention comprises, as a battery current collector, a large number of non-conductive portions having an appropriate area on the surface. This is a device for producing a porous metal strip by depositing a metal on a conductive drum provided so that the total area of the whole becomes an appropriate range, and peeling a plating layer thereof. In the non-conductive part, when a metal band is obtained, stress concentration causes a distortion in the width direction so that distortion does not occur.
Care must be taken to arrange them at the same pitch in the longitudinal direction.
【０００７】さらに詳しくは、多数の不導体部を表面に
設けた導電ドラム上に金属を析出させて、そのめっき層
を剥離して、多孔金属帯を製造する装置であって、前記
ドラム上に設けられた不導体部の一つの面積が２．５＊
１０-5ｍｍ2〜３０ｍｍ2であり、かつドラム上に形成さ
れた不導体部の面積の総和と導体部の面積の総和との比
が０．１〜９である導電ドラムと、ドラムを浸せきして
ドラム上に金属をめっきさせるためのめっき浴槽と、さ
らに好ましくは、ドラムからめっき層を剥離するための
剥離位置決めロールと、ドラムから剥離するめっき層の
剥離角度を調整する剥離角度調整ロールと、からなる。More specifically, there is provided an apparatus for producing a porous metal strip by depositing a metal on a conductive drum provided with a large number of non-conductive portions on its surface and peeling off a plating layer thereof, wherein the apparatus comprises: The area of one of the provided nonconductors is 2.5 *
10-5 is mm 2 ~30mm 2, and dipping a conductive drum ratio of the total area of the sum and the conductor portion of the area of the non-conductors that are formed on the drum is 0.1 to 9, the drum And a plating bath for plating metal on the drum, and more preferably, a peeling positioning roll for peeling the plating layer from the drum, and a peeling angle adjusting roll for adjusting the peeling angle of the plating layer to be peeled from the drum. , Consisting of
【０００８】上記の製造装置には安定連続生産の観点か
ら、ドラム上に、不導体部に付着した金属を除去する付
着金属除去装置を設けること、さらには剥離角度調整ロ
ールの後工程に、めっき液残渣付着による腐食あるいは
汚れの防止の観点から金属帯の表面を単なる水洗→乾燥
でも良いが、水洗→酸洗→水洗等の方法による清浄化す
るための表面清浄化装置と、表面清浄化後の金属帯を乾
燥するための乾燥装置を設けることが好ましい。From the viewpoint of stable and continuous production, the above-mentioned manufacturing apparatus is provided with an attached metal removing device for removing the metal attached to the nonconductive portion on the drum. From the viewpoint of preventing corrosion or dirt due to adhesion of liquid residue, the surface of the metal strip may be simply washed with water and dried, but a surface cleaning device for cleaning with a method such as washing with water → pickling → washing with water, and after cleaning the surface. It is preferable to provide a drying device for drying the metal strip.
【０００９】また、このような装置の導体部の平均表面
粗さ（Ｒａ）が０．１〜３μｍであることが金属帯とし
た時、集電体に適用する場合の重要な特性の一つである
活物質との密着性の観点から好ましい。Ｒａが０．１μ
ｍ未満では活物質との密着性向上効果が認められず、３
μｍを超えるとめっき金属の剥離時に破断する危険性が
あり好ましくない。[0009] Further, when the metal band is such that the average surface roughness (Ra) of the conductor portion of such a device is 0.1 to 3 µm, one of the important characteristics when applied to a current collector. It is preferable from the viewpoint of adhesion to the active material. Ra is 0.1μ
If less than m, the effect of improving the adhesion to the active material is not recognized, and 3
If it exceeds μm, there is a risk of breaking when the plated metal is peeled off, which is not preferable.
【００１０】電池用多孔集電体にも適用できる金属帯の
種類としては、鉄、銅、ニッケル又はアルミニウムある
いはそれらの合金、複層が挙げられる。The types of metal bands applicable to the porous current collector for batteries include iron, copper, nickel or aluminum, alloys thereof, and multiple layers.
【００１１】さらに、工程の簡略化、巻取り時のテンシ
ョンによる多孔集電体破断の危険性回避の観点から、電
池用多孔集電体上に引続き多孔集電体製造と同一工程で
結着剤を含んだ活物質を積層する積層装置と、その積層
した活物質を乾燥する乾燥装置と、乾燥後に活物質を集
電体に圧着し、主に活物質を圧縮する圧着圧縮装置とを
設けることが好ましい。Further, from the viewpoint of simplifying the process and avoiding the risk of breakage of the porous current collector due to tension during winding, the binder is continuously formed on the porous current collector for the battery in the same process as the production of the porous current collector. A stacking device for stacking active materials containing, a drying device for drying the stacked active material, and a press-compression device for pressing the active material onto the current collector after drying and mainly compressing the active material. Is preferred.
【００１２】請求項９に記載の多孔金属帯の製造方法
は、多数の不導体部を表面に設けた導電ドラム上に金属
を析出させて、そのめっき層を剥離して、多孔金属帯を
製造する方法であって、前記ドラム上に設けられた不導
体部の一つの面積が２．５＊１０-5ｍｍ2〜３０ｍｍ2で
あり、かつドラム上に形成された不導体部の面積の総和
と導体部の面積の総和との比が０．１〜９である導電ド
ラムをめっき浴槽に浸せきしてドラム上にめっき層を形
成させ、剥離位置決めロールを前記ドラムに当接させ金
属帯の適正剥離角度を剥離角度調整ロールで設定後、め
っき層をドラムから剥離させて多孔金属帯を形成し、そ
の後、金属帯の表面を清浄化し、表面清浄した金属帯を
乾燥することを特徴とする。[0012] According to a ninth aspect of the present invention, there is provided a method for manufacturing a porous metal strip, comprising: depositing a metal on a conductive drum having a large number of non-conductive portions on its surface; a method of one of the area of the non-conductors provided on the drum a is 2.5 * 10 -5 mm 2 ~30mm 2 , and the total sum of the areas of the non-conductors that are formed on the drum A conductive drum having a ratio of 0.1 to 9 to the sum of the areas of the conductors is immersed in a plating bath to form a plating layer on the drum, and a peeling positioning roll is brought into contact with the drum to adjust the metal band. After setting the peeling angle with a peeling angle adjusting roll, the plating layer is peeled from the drum to form a porous metal band, and thereafter, the surface of the metal band is cleaned and the surface-cleaned metal band is dried.
【００１３】また、めっき金属の種類やめっき厚によっ
ては金属帯の剥離時破断する危険性があり、より容易に
安定して金属帯をドラムから剥離するには、冷却ロール
装置をドラムの外周面に付着するめっき層に直接押し当
てることが好ましい。Further, there is a risk that the metal strip may be broken when the metal strip is peeled off depending on the type of the plating metal or the plating thickness. It is preferable to press directly on the plating layer adhering to the substrate.
【００１４】冷却ロール装置は、単に表面温度調節機能
を有したロールでも良いがめっき層に直接接するゴムロ
ールと、ゴムロールに当接されると共に内部に冷却水を
通水する等の表面温度の調節可能な金属ロールから形成
され、金属ロールでゴムロールの表面を適正温度に冷却
することによってゴムの弾性により均一にめっき層を冷
却するようにすることが好ましい。The cooling roll device may be a roll having merely a surface temperature control function, but it is possible to control the surface temperature by directly contacting the plating layer with a rubber roll and passing cooling water through the rubber roll while contacting the rubber roll. It is preferable that the plating layer is formed of a suitable metal roll, and the surface of the rubber roll is cooled to an appropriate temperature by the metal roll so that the plating layer is uniformly cooled by the elasticity of the rubber.
【００１５】さらに請求項１４に記載の電池用電極の製
造方法は、前記した様に、先の方法で得られた電池用多
孔集電体上に、引続き結着剤を含んだ活物質を積層する
工程と、積層した活物質を乾燥する工程と、積層された
活物質と集電体とを圧着し、主に活物質を圧縮して電極
とする工程とを同一工程により行い、工程の簡略化及び
多孔集電体巻取り時のテンションによる破断の危険性や
集電体の貯蔵時の腐食を回避することを特徴とする。Further, in the method for manufacturing a battery electrode according to a fourteenth aspect, as described above, the active material containing the binder is continuously laminated on the porous current collector for a battery obtained by the above method. And the step of drying the laminated active material, the step of pressing the laminated active material and the current collector, and the step of mainly compressing the active material to form an electrode are performed in the same process, thereby simplifying the process. It is characterized by avoiding the danger of breaking due to tension during winding and winding of the porous current collector and corrosion during storage of the current collector.
【００１６】請求項１５に記載の電池用電極は、請求項
１４の製造方法で形成された電極であることを特徴とす
る。According to a fifteenth aspect of the present invention, the battery electrode is an electrode formed by the manufacturing method of the fourteenth aspect.
【００１７】[0017]
【発明の実施の形態】以下、添付図に示す一実施の形態
を参照して、本発明を具体的に説明する。なお、本実施
の形態は、本発明に係る多孔金属帯の製造方法によって
製造される多孔金属帯が、一般的にリチウムイオン二次
電池やポリマー電池の負極に用いられている銅箔に代替
可能な多孔銅箔の場合を取り挙げて説明する。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail with reference to an embodiment shown in the accompanying drawings. In this embodiment, the porous metal band manufactured by the method for manufacturing a porous metal band according to the present invention can be replaced with a copper foil generally used for a negative electrode of a lithium ion secondary battery or a polymer battery. A case of a porous copper foil will be described.
【００１８】（１）まず、図１〜図３に示すように、導
体部１０からなる外周面に不導体部１１を所定のパター
ンで設けた導電ドラム１２をタンク１３中のホウフッ化
銅浴からなるめっき浴１４に浸漬する。ここで、導体部
１０はステンレス鋼やチタン等から形成することができ
ると共に、不導体部１１は前記金属に多数の孔を散在し
た状態で設け、その孔内に絶縁性の高い合成樹脂片を埋
設すると共に、その表面を導体部１０と同一つら面ある
いは不導体部を若干高くすることによって形成すること
ができる。(1) First, as shown in FIGS. 1 to 3, a conductive drum 12 provided with a non-conductor portion 11 in a predetermined pattern on an outer peripheral surface formed of a conductor portion 10 is formed from a copper borofluoride bath in a tank 13. Immersion in a plating bath 14. Here, the conductor portion 10 can be formed of stainless steel, titanium, or the like, and the nonconductor portion 11 is provided in a state where a large number of holes are scattered in the metal, and a synthetic resin piece having high insulating properties is provided in the holes. It can be formed by embedding and making the surface the same flat surface as the conductor portion 10 or slightly increasing the non-conductor portion.
【００１９】一つの不導体部１１の面積は、２．５＊１
０-5ｍｍ2〜３０ｍｍ2 とし、不導体部１１の面積の総
和と導体部１０の面積の総和の比を０．１〜９とするこ
とが必要不可欠である。一つの不導体部１１の面積は
２．５＊１０-5ｍｍ2 未満では、連続して安定した孔径
を得ることが困難で、場所により密着性向上等の集電体
の多孔効果が大きく異なる。The area of one nonconductive portion 11 is 2.5 * 1
0 -5 mm 2 and ~30mm 2, it is essential to a 0.1 to 9 the ratio of the sum of the areas of the total sum and the conductor portion 10 of the area of the non-conductors 11. If the area of one nonconductive portion 11 is less than 2.5 * 10 -5 mm 2 , it is difficult to continuously obtain a stable hole diameter, and the porosity of the current collector, such as improvement in adhesion, differs greatly depending on the location. .
【００２０】一方、３０ｍｍ2 を超えると、孔を開けた
ことによるアンカー効果が乏しく、密着性向上への寄与
が薄弱となる。ここでいう密着性とは、活物質と集電体
間の密着性をいい、曲げ等によって活物質が集電体から
剥離しない効果をいう。また、不導体部１１の面積の総
和と導体部１０の面積の総和の比を０．１〜９とする理
由は、０．１未満では集電体の多孔化による密着性向上
がみられず、９を超えるとめっき層ドラムからの安定剥
離が困難となるばかりか、集電体の強度が弱くなり、め
っき層の剥離から巻取り間で破断が多発する危険性があ
るからである。On the other hand, if it exceeds 30 mm 2 , the anchor effect due to the perforation is poor, and the contribution to the improvement of the adhesion is weak. The term “adhesion” as used herein refers to the adhesion between the active material and the current collector, and refers to an effect that the active material is not separated from the current collector due to bending or the like. The reason that the ratio of the sum of the areas of the non-conductor portions 11 to the sum of the areas of the conductor portions 10 is 0.1 to 9 is that if the ratio is less than 0.1, the improvement in adhesion due to the porosity of the current collector is not observed. If the number exceeds 9, the stable peeling from the plating layer drum becomes difficult, and the strength of the current collector is weakened, and there is a danger that breakage occurs frequently between peeling of the plating layer and winding.
【００２１】不導体部１１は、それぞれ円形、楕円形、
六角形、四角形などの対称形が好ましく、その配列は金
属帯を得た時、応力集中が発生しない様に、巾方向、長
手方向に各々同じピッチにする等の考慮が必要である。
一例として、１ｍｍ径の円形の不導体部が縦方向及び横
方向のピッチ間隔が各々一定であるものが好適である
が、あるいは、中心部は前記同様であるが、その外側の
ほんの数ｃｍのみ０．１ｍｍ径の円形である不導体部が
縦方向及び横方向のピッチ間隔が各々一定であるものも
好適である。The nonconductive portions 11 are circular, elliptical,
Symmetrical shapes such as hexagons and squares are preferable, and the arrangement thereof must be considered to have the same pitch in the width direction and the longitudinal direction so that stress concentration does not occur when a metal band is obtained.
As an example, it is preferable that the circular non-conductive portion having a diameter of 1 mm has a constant pitch interval in the vertical direction and the horizontal direction, or the central portion is the same as the above, but only a few cm outside thereof. It is also preferable that the non-conductive portion having a circular shape having a diameter of 0.1 mm has a constant pitch interval in the vertical and horizontal directions.
【００２２】一方、導体部１０の表面粗度は、粗面効果
を得るため、好ましくは、０．１〜３μｍとする。０．
１μｍ未満では、密着性に対する粗面化効果は認められ
ず、３μｍを超えると効果は飽和するばかりでなく、め
っき金属の剥離時に破断する危険性が生じる。On the other hand, the surface roughness of the conductor 10 is preferably 0.1 to 3 μm in order to obtain a rough surface effect. 0.
If the thickness is less than 1 μm, the effect of roughening the adhesion is not recognized. If the thickness exceeds 3 μm, the effect is not only saturated, but also there is a risk that the plating metal is broken when peeled off.
【００２３】（２）次に、導電ドラム１２を回転させ
て、導電ドラム１２の外周面に多孔めっき層１５を形成
する。この導電ドラム１２をさらに回転して多孔めっき
層１５を、導電ドラム１２の外周面に付着した状態でめ
っき浴１４から取り出す。ここで、多孔めっき層１５の
厚みは、電池用集電体としての軽量性及び経済性を考慮
すると一般的には、５〜７０μｍが好適である。また、
多孔めっき層としては、鉄、銅、ニッケル、アルミニウ
ムあるいはその合金、複層物などが好適に用いられる
が、鉄の場合は、さびやすいので剥離後ニッケルめっき
等を施すのが好ましい。(2) Next, the conductive drum 12 is rotated to form a porous plating layer 15 on the outer peripheral surface of the conductive drum 12. The conductive drum 12 is further rotated to take out the porous plating layer 15 from the plating bath 14 in a state of being adhered to the outer peripheral surface of the conductive drum 12. Here, the thickness of the porous plating layer 15 is generally preferably from 5 to 70 μm in consideration of lightness and economy as a battery current collector. Also,
As the porous plating layer, iron, copper, nickel, aluminum or an alloy thereof, a multi-layered material, or the like is suitably used. In the case of iron, it is preferable to apply nickel plating or the like after peeling since iron is easily rusted.
【００２４】（３）多孔めっき層１５をめっき浴１４か
ら取り出した直後に、剥離を容易にするため、冷却ロー
ル装置１６を用いて、多孔めっき層１５を冷却する。具
体的には、冷却ロール装置１６は、図１及び図２に示す
ように、多孔めっき層１５に直接接するゴムロール１７
と、ゴムロール１７に当接されると共に内部に冷却水を
通水した金属ロール１８とから形成されている。従っ
て、まず、金属ロール１８で表面を冷却されたゴムロー
ル１７により、多孔めっき層１５をゴムの弾性を利用し
て均一に冷却し、ドラム表面との温度差による膨張係数
の相違を利用して、その後の剥離を容易にすることがで
きる。(3) Immediately after removing the porous plating layer 15 from the plating bath 14, the porous plating layer 15 is cooled using a cooling roll device 16 in order to facilitate peeling. Specifically, as shown in FIGS. 1 and 2, the cooling roll device 16 includes a rubber roll 17 directly in contact with the porous plating layer 15.
And a metal roll 18 which is in contact with the rubber roll 17 and through which cooling water flows. Therefore, first, the porous plating layer 15 is uniformly cooled by the rubber roll 17 whose surface is cooled by the metal roll 18 by utilizing the elasticity of rubber, and by utilizing the difference in the expansion coefficient due to the temperature difference from the drum surface, Subsequent peeling can be facilitated.
【００２５】また、冷却水を多孔めっき層１５に直接か
けて冷却するのではなく、冷却された金属ロール１８及
びゴムロール１７を介して、めっき層１５を冷却するこ
とができるので、冷却水がめっき浴１４中に落下するお
それがなく、作業の安全性とめっき浴濃度変化を防止出
来るため、目的とする多孔金属帯の安定した製造が可能
である。Further, the plating layer 15 can be cooled via the cooled metal roll 18 and the rubber roll 17 instead of directly cooling the cooling water onto the porous plating layer 15 and cooling. Since there is no danger of falling into the bath 14 and the safety of the work and the change of the plating bath concentration can be prevented, the target porous metal strip can be stably manufactured.
【００２６】また、ドラム及び多孔めっき層に、めっき
浴中のめっきスラッジ等の異物を付着させないようにす
るため、導電ドラム１２に接して掻き落とし治具Ａを設
けておくことも好ましい。当然ながら掻き落とした付着
物質は、再付着したりめっき浴に入ったりしない様に粘
着性を有したゴムロールや受け皿等を設けて、異物除去
する必要がある。It is also preferable to provide a scraping jig A in contact with the conductive drum 12 in order to prevent foreign substances such as plating sludge in the plating bath from adhering to the drum and the porous plating layer. Naturally, it is necessary to provide a sticky rubber roll, a tray, or the like so as to prevent the adhered substance scraped off from re-adhering or entering the plating bath to remove foreign matter.
【００２７】多孔集電体を安定して得るには、孔形状不
良及びめっき層剥離時等に破断の原因となる付着物質は
出来るだけ除去しておくことが重要となる。In order to obtain a porous current collector stably, it is important to remove as much as possible the adhering substance which causes a defective shape of the hole and breaks when the plating layer is peeled off.
【００２８】（４）冷却ロール装置１６によって多孔め
っき層１５を冷却後、導電ドラム１２の外表面上であっ
て冷却ロール装置１６から所定距離離隔した位置に配設
した剥離位置決めロール１９、及び、剥離位置決めロー
ル１９から所定距離離隔して空間中に配設した一対の剥
離角度調整ロール２０、２１を介して、導電ドラム１２
の外周面から図４に示すような多孔金属帯１５ａとして
剥離する。(4) After the porous plating layer 15 is cooled by the cooling roll device 16, a peeling positioning roll 19 disposed on the outer surface of the conductive drum 12 and at a predetermined distance from the cooling roll device 16, and The conductive drum 12 is separated via a pair of peeling angle adjusting rolls 20 and 21 disposed in the space at a predetermined distance from the peeling positioning roll 19.
From the outer peripheral surface as a porous metal band 15a as shown in FIG.
【００２９】ここで、図２に示すように、剥離位置決め
ロール１９の適正な剥離位置Ｐ、及び、剥離位置Ｐにお
ける接線Ｌ1 と、剥離位置決めロール１９の外周面と一
対の剥離角度調整ロール２０、２１のクランプ面とを結
ぶ剥離線Ｌ2 とのなす適正な剥離角度θは、めっき浴１
４中のめっき液の内容や孔形状及び総孔面積、金属箔の
厚みによって実験的に決定されることになる。Here, as shown in FIG. 2, an appropriate peeling position P of the peeling positioning roll 19, a tangent line L1 at the peeling position P, an outer peripheral surface of the peeling positioning roll 19 and a pair of peeling angle adjusting rolls 20, The proper peeling angle θ formed by the peeling line L2 connecting to the clamping surface of the plating bath 21 is
4 is experimentally determined by the contents of the plating solution, the hole shape and the total hole area, and the thickness of the metal foil.
【００３０】従って、多孔めっき層１５を、その特性に
最も適した剥離位置Ｐと剥離角度θで剥離することがで
き、多孔金属帯１５ａを、破ることなく、長尺物として
剥離することができる。また、図には特に記してない
が、剥離した金属帯に多量に付着しためっき液を表面清
浄化処理装置に入る前にリンガーロール等でほとんど除
去することや、表面清浄化処理装置の各タンクの出側に
同じくリンガーロール等を設け付着した液をほとんど除
去することが好ましいのは言うまでもない。Therefore, the porous plating layer 15 can be peeled at the peeling position P and the peeling angle θ that are most suitable for the characteristics, and the porous metal band 15a can be peeled as a long object without breaking. . Although not particularly shown in the figure, a large amount of the plating solution adhering to the stripped metal strip is almost removed by a ringer roll or the like before entering the surface cleaning apparatus, and each tank of the surface cleaning apparatus is removed. It is needless to say that it is preferable to provide a ringer roll or the like on the outlet side to almost remove the adhering liquid.
【００３１】（５）次に、図１に示すように、多孔金属
帯１５ａの表面を、反転ロール２２を介して反転ロール
２３を具備する水タンク２４内に満たした水２５内を通
過させることにより表面清浄化処理を行う。なお、ここ
でいう表面清浄化処理とは、水洗のみでなく、水洗→酸
洗→水洗などの複合した処理も含み、めっき層に付着し
ためっき液残渣を除去することをさす。(5) Next, as shown in FIG. 1, the surface of the porous metal band 15a is passed through the water 25 filled in the water tank 24 having the reversing roll 23 via the reversing roll 22. To perform a surface cleaning treatment. The surface cleaning treatment mentioned here includes not only washing with water but also a combined treatment such as washing with water, pickling, and washing with water, and refers to removing a plating solution residue attached to a plating layer.
【００３２】表面清浄化処理はめっき層剥離後水洗し乾
燥するだけでよいが、より好ましくはめっき層に付着し
ているめっき液残査をほぼ完全に除去するため、水洗後
希硫酸等で酸洗しさらに水洗することが望ましい。例え
ばホウフッ化銅浴にて多孔集電体を得る場合において、
水洗だけでは室温に一日放置するだけでめっき面に茶褐
色の斑点が生じる場合がある。この原因は水洗では充分
取れなかっためっき液残査中のフッ素が空気中の水分と
反応して腐食性の強いＨＦとなり、局部的に銅を腐食し
たものと考えられ、前記酸洗を行うことにより、このよ
うな斑点は生じなくなる。In the surface cleaning treatment, it is only necessary to wash and dry after peeling off the plating layer. More preferably, in order to almost completely remove the plating solution residue adhering to the plating layer, after washing with water, acidify with dilute sulfuric acid or the like. It is desirable to wash and then wash with water. For example, when obtaining a porous current collector in a copper borofluoride bath,
Simply washing with water may leave brown spots on the plated surface after only one day at room temperature. It is considered that the reason for this is that fluorine in the plating solution residue, which could not be sufficiently removed by water washing, reacts with moisture in the air to form highly corrosive HF, and locally corroded copper. As a result, such spots do not occur.
【００３３】（６）図１に示すように、洗浄後、反転ロ
ール２６を介して多孔集電体となる多孔金属帯１５ａを
第１の乾燥装置２７で乾燥した後、結着剤とグラファイ
トを混合した活物質２８を活物質タンク２９に浸漬後、
所定厚みとなる様にナイフコーターで余分の活物質を除
去し、多孔金属帯１５ａの両面に積層して積層多孔金属
帯１５ｂを製造する。(6) As shown in FIG. 1, after washing, the porous metal band 15a to be a porous current collector is dried by the first drying device 27 via the reversing roll 26, and then the binder and graphite are removed. After immersing the mixed active material 28 in the active material tank 29,
Excess active material is removed with a knife coater so as to have a predetermined thickness, and laminated on both sides of the porous metal strip 15a to produce a laminated porous metal strip 15b.
【００３４】（７）前記積層多孔金属帯１５ｂを第２の
乾燥装置３０によって乾燥した後、圧着圧縮ロール３１
を用いて、約５０％の圧縮率で活物質２８を圧縮した
後、電池用電極３２として、リール３３に巻き取る。(7) After drying the laminated porous metal band 15b by the second drying device 30, the pressure-compression roll 31
Then, the active material 28 is compressed at a compression ratio of about 50% by using, and wound on a reel 33 as a battery electrode 32.
【００３５】同一工程で多孔集電体と活物質とを積層し
引き続き圧着圧縮すると以下のメリットが生ずる。 ・工程簡略化、経済性向上。 ・多孔金属帯の表面酸化や腐食がほとんど生じない条件
で活物質を適用するため、より安定化した多孔集電体を
有する電極を製造することが出来る。 ・多孔集電体をきちんと巻き取るには、ある程度テンシ
ョンを掛ける必要があり、元々強度の低い多孔集電体は
破断する危険性があるが、活物質を積層圧着して得た電
極は強度が強くなり、テンションを掛けても破断せず、
安定してきれいに巻き取ることが出来る様になる。In the same step, when the porous current collector and the active material are laminated and then pressed and compressed, the following advantages are obtained.・ Simplification of process and improvement of economy. -Since the active material is applied under conditions that hardly cause surface oxidation or corrosion of the porous metal strip, an electrode having a more stabilized porous current collector can be manufactured. -To properly wind the porous current collector, it is necessary to apply some tension.There is a risk that the porous current collector, which originally has low strength, may break, but the electrode obtained by laminating and pressing the active material has a low strength. It becomes strong and does not break even when tension is applied,
It becomes possible to wind up stably and neatly.
【００３６】（８）この電池用電極３２は適当な寸法に
切断された後、例えば図５に示すような、今後急速な伸
びが期待されるカード状のリチウムポリマー電池３４の
負極３７として好適に用いることができる。なお、図５
において、３６はゲル状のポリマー電解物質を示し、３
５はニッケル酸リチウムを主体とした活物質を用いた正
極を示し、３８は複合箔からなる外装材を示し、３９、
４０はリード線を示す。また、市場に盛んに出回ってい
るリチウムイオン二次電池等にも適用可能である。(8) After this battery electrode 32 is cut into an appropriate size, it is preferably used as a negative electrode 37 of a card-shaped lithium polymer battery 34 expected to grow rapidly in the future, for example, as shown in FIG. Can be used. FIG.
In 36, 36 denotes a gel-like polymer electrolyte,
Reference numeral 5 denotes a positive electrode using an active material mainly composed of lithium nickelate, 38 denotes an exterior material made of a composite foil,
Numeral 40 indicates a lead wire. Further, the present invention is also applicable to lithium ion secondary batteries and the like which are widely available on the market.
【００３７】[0037]
【発明の効果】以上説明したように、本発明の装置で
は、多孔金属帯の特性及び製造上、大きな影響を及ぼす
めっきドラムの不導体部の個々の面積、及び総面積、導
体部の表面粗度を電池用集電体に焦点を絞り、開発を行
ったので、集電体の重要な特性である活物質との密着性
が良好な多孔金属帯（集電体）を経済的に得ることが可
能となった。また、多孔めっき層を、剥離位置決めロー
ル及び一対の剥離角度調整ロールを介して導電ドラムの
外周面から剥離し、その後洗浄することによって多孔金
属帯を製造するようにしたので、多孔めっき層を、その
特性に最も適した剥離位置と剥離角度で剥離することが
でき、多孔金属帯を破ることなく、長尺物として剥離す
ることができる。As described above, according to the apparatus of the present invention, the individual area and the total area of the non-conductive portion of the plating drum, which has a great influence on the characteristics and production of the porous metal strip, and the surface roughness of the conductive portion. Focusing on the current collector for batteries, the development has been carried out, so that it is possible to economically obtain a porous metal band (current collector) with good adhesion to the active material, which is an important characteristic of the current collector Became possible. Further, since the porous plating layer is peeled off from the outer peripheral surface of the conductive drum via a peeling positioning roll and a pair of peeling angle adjusting rolls, and then washed to produce a porous metal band, the porous plating layer, Peeling can be performed at a peeling position and a peeling angle most suitable for the characteristics, and the porous metal strip can be peeled as a long object without breaking.
【００３８】また、本発明の多孔集電体の製造方法で
は、めっき層の冷却を、冷却ロール装置を導電ドラムの
外周面に付着するめっき層に直接押し当てて行うことに
より、めっき層の剥離を容易に行うことができると共
に、冷却水がめっき浴中に落下するのを確実に防止する
ことができ、多孔集電体となる多孔金属帯を安定して製
造することができる。In the method for manufacturing a porous current collector according to the present invention, the plating layer is cooled by directly pressing the cooling roll device against the plating layer adhered to the outer peripheral surface of the conductive drum. Can be easily performed, cooling water can be reliably prevented from dropping into the plating bath, and a porous metal strip serving as a porous current collector can be stably manufactured.
【００３９】また、本発明の製造方法では、冷却ロール
装置は、水冷の金属ロールからゴムロールを介してめっ
き層を冷却するようにしているので、ゴムの弾力により
均一にめっき層を冷却出来、また金属ロールから誤って
水が漏れた場合も、冷却水がめっき浴中に落下するのを
確実に防止することが出来るため、多孔金属帯をより安
定して製造することができる。In the production method of the present invention, the cooling roll device cools the plating layer from the water-cooled metal roll via the rubber roll, so that the plating layer can be cooled uniformly by the elasticity of the rubber. Even when water accidentally leaks from the metal roll, the cooling water can be reliably prevented from dropping into the plating bath, so that the porous metal strip can be manufactured more stably.
【００４０】また、本発明では、めっき浴に用いるめっ
き金属として銅、ニッケル又はアルミニウムなどを用い
ることによって、多孔金属帯を安価に製造することがで
きる。In the present invention, a porous metal strip can be manufactured at low cost by using copper, nickel, aluminum, or the like as a plating metal for a plating bath.
【図１】本発明の一実施の形態に係る多孔金属帯の製造
方法の工程を示すブロック図である。FIG. 1 is a block diagram showing steps of a method for manufacturing a porous metal strip according to an embodiment of the present invention.
【図２】導電ドラムに対する剥離位置決めロール及び剥
離角度調整ロールの配置関係を示す説明図である。FIG. 2 is an explanatory diagram showing an arrangement relationship of a peeling positioning roll and a peeling angle adjusting roll with respect to a conductive drum.
【図３】導電ドラムの斜視図である。FIG. 3 is a perspective view of a conductive drum.
【図４】多孔金属帯の斜視図である。FIG. 4 is a perspective view of a porous metal strip.
【図５】多孔金属帯を負極として用いたポリマー電池の
平面図である。FIG. 5 is a plan view of a polymer battery using a porous metal band as a negative electrode.
１０・・・導体部 １１・・・不導体部 １２・・・導電ドラム １４・・・めっき浴 １５・・・多孔めっき層 １５ａ・・・多孔金属帯 １５ｂ・・・積層多孔金属帯 １９・・・剥離位置決めロール ２０・・・剥離角度調整ロール ２１・・・剥離角度調整ロール DESCRIPTION OF SYMBOLS 10 ... Conductor part 11 ... Non-conductive part 12 ... Conductive drum 14 ... Plating bath 15 ... Porous plating layer 15a ... Porous metal band 15b ... Laminated porous metal band 19 ... -Peeling positioning roll 20 ... Peeling angle adjusting roll 21 ... Peeling angle adjusting roll
Claims (15)
ム上に金属を析出させて、そのめっき層を剥離して、多
くの孔を形成した金属帯を製造する装置であって、前記
ドラム上に設けられた不導体部の一つの面積が２．５＊
１０-5ｍｍ2〜３０ｍｍ2であり、かつドラム上に形成さ
れた不導体部の面積の総和と導体部の面積の総和との比
が０．１〜９であるドラムを、連続的に回転させて導体
部に金属をめっきした後、めっき金属を剥離し多孔集電
体とすることを特徴とする電池用多孔集電体製造装置。An apparatus for producing a metal strip having a large number of holes by depositing a metal on a conductive drum provided with a large number of non-conductive portions on a surface thereof and peeling a plating layer of the metal. The area of one of the non-conductive parts provided on the drum is 2.5 *
10-5 is mm 2 ~30mm 2, and the ratio is 0.1 to 9 drum with the total sum of the areas of the sum and the conductor portion of the area of the non-conductors that are formed on the drum, rotates continuously The method for manufacturing a porous current collector for a battery according to claim 1, wherein the metal is plated on the conductor portion, and then the plated metal is peeled off to form a porous current collector.
めっきさせるためのめっき浴槽と、前記ドラムからめっ
き層を剥離するための剥離位置決めロールと、前記ドラ
ムから剥離するめっき層の剥離角度を調整する剥離角度
調整ロールを設けた請求項１記載の装置。2. A plating bath for dipping the drum and plating a metal on the drum, a peeling positioning roll for peeling a plating layer from the drum, and a peeling angle of the plating layer peeling from the drum. 2. The apparatus according to claim 1, further comprising a peeling angle adjusting roll for adjusting.
属帯の表面を清浄化するための表面清浄化装置と、表面
清浄化後の金属帯を乾燥するための乾燥装置を設けた請
求項１又は２記載の装置。3. A post-process of the peeling angle adjusting roll, wherein a surface cleaning device for cleaning the surface of the metal band and a drying device for drying the metal band after the surface cleaning are provided. 3. The device according to 1 or 2.
０．１〜３μｍである請求項１〜３のいずれかに記載の
装置。4. The apparatus according to claim 1, wherein the conductor has an average surface roughness (Ra) of 0.1 to 3 μm.
属を除去する付着金属除去装置を設けた請求項１〜４の
いずれかに記載の装置。5. The apparatus according to claim 1, further comprising an attached metal removing device provided on said drum for removing metal attached to said non-conductive portion.
ルミニウムである請求項１〜５のいずれかに記載の装
置。6. The device according to claim 1, wherein the metal strip is iron, copper, nickel or aluminum.
とするために、めっき浴槽から出たドラム上のめっき層
を優先的且つ急速に冷却することが可能な冷却ロール装
置を設けた請求項１〜６のいずれか記載の装置。7. A cooling roll device capable of rapidly and preferentially cooling the plating layer on the drum coming out of the plating bath so as to facilitate the peeling of the plating layer from the drum. The apparatus according to any one of claims 1 to 6.
置によって得られた多孔集電体上に引続き結着剤を含ん
だ活物質を積層する積層装置と、その積層した活物質を
乾燥する乾燥装置と、乾燥後に活物質を多孔集電体に圧
着し、主に活物質を圧縮して電極とする圧着圧縮装置と
を有することを特徴とする電池用電極製造装置。8. A laminating apparatus for continuously laminating an active material containing a binder on a porous current collector obtained by the apparatus according to any one of claims 1 to 6, and An electrode manufacturing apparatus for a battery, comprising: a drying device for drying; and a compression / compression device for pressing an active material onto a porous current collector after drying and compressing the active material to form an electrode.
ム上に金属を析出させて、そのめっき層を剥離して、多
くの孔を形成した金属帯を製造する方法であって、前記
ドラム上に設けられた不導体部の一つの面積が２．５＊
１０-5ｍｍ2〜３０ｍｍ2であり、かつドラム上に形成さ
れた不導体部の面積の総和と導体部の面積の総和との比
が０．１〜９である導電ドラムをめっき浴槽に浸せきし
てドラム上にめっき層を形成させ、剥離位置決めロール
を前記ドラムに当接させ金属帯の適正剥離角度を剥離角
度調整ロールで設定後、めっき層をドラムから剥離させ
て多孔金属帯を形成し、その後、金属帯の表面を清浄化
し、表面清浄した金属帯を乾燥することを特徴とする多
孔金属帯の製造方法。9. A method for producing a metal strip having a large number of holes by depositing a metal on a conductive drum provided with a large number of non-conductive portions on a surface thereof and peeling off a plating layer thereof. The area of one of the non-conductive parts provided on the drum is 2.5 *
10-5 is mm 2 ~30mm 2, and dipping the ratio of the total area of the sum and the conductor portion of the area of the non-conductors formed on the drum in a plating bath of conductive drum is 0.1 to 9 Then, a plating layer is formed on the drum, a peeling positioning roll is brought into contact with the drum, and an appropriate peeling angle of the metal band is set with a peeling angle adjusting roll. Then, the plating layer is peeled from the drum to form a porous metal band. And thereafter, cleaning the surface of the metal band and drying the surface-cleaned metal band.
ール装置を前記ドラムの外周面に付着する前記めっき層
に直接押し当てることにより行うことを特徴とする請求
項９記載の製造方法。10. The manufacturing method according to claim 9, wherein the stripping of the metal band is performed by directly pressing a cooling roll device against the plating layer attached to the outer peripheral surface of the drum.
に直接接するゴムロールと、該ゴムロールに当接される
と共に内部に冷却水を通水する等の方法による温度が調
節可能な金属ロールから形成され、該金属ロールで前記
ゴムロールの表面を適正温度に冷却することによって前
記めっき層を冷却するようにしたことを特徴とする請求
項１０記載の製造方法。11. The cooling roll device is formed of a rubber roll that is in direct contact with the plating layer, and a metal roll that is in contact with the rubber roll and whose temperature can be adjusted by, for example, passing cooling water through the rubber roll. The method according to claim 10, wherein the plating layer is cooled by cooling the surface of the rubber roll to an appropriate temperature with the metal roll.
アルミニウムである請求項９〜１１のいずれかに記載の
製造方法。12. The method according to claim 9, wherein the metal strip is made of iron, copper, nickel, or aluminum.
造方法により製造された電池用多孔集電体。13. A porous current collector for a battery manufactured by the manufacturing method according to claim 9.
体上に、引続き結着剤を含んだ活物質を積層後、積層し
た活物質を乾燥し、積層された活物質と集電体とを圧着
圧縮することを一工程で行い電極を製造することを特徴
とする電池用電極の製造方法。14. An active material containing a binder is successively laminated on the porous current collector for a battery obtained in claim 13, the laminated active material is dried, and the laminated active material and the current collector are collected. A method for producing an electrode for a battery, comprising compressing and compressing a body in one step to produce an electrode.
電極。15. An electrode for a battery formed by the method according to claim 14.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14515098A JP3429448B2 (en) | 1998-05-12 | 1998-05-12 | Battery porous current collector, electrode, method and apparatus for producing them |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14515098A JP3429448B2 (en) | 1998-05-12 | 1998-05-12 | Battery porous current collector, electrode, method and apparatus for producing them |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH11323593A true JPH11323593A (en) | 1999-11-26 |
| JP3429448B2 JP3429448B2 (en) | 2003-07-22 |
Family
ID=15378586
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14515098A Expired - Fee Related JP3429448B2 (en) | 1998-05-12 | 1998-05-12 | Battery porous current collector, electrode, method and apparatus for producing them |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3429448B2 (en) |
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