JP3429448B2 - Battery porous current collector, electrode, method and apparatus for producing them - Google Patents
Battery porous current collector, electrode, method and apparatus for producing themInfo
- Publication number
- JP3429448B2 JP3429448B2 JP14515098A JP14515098A JP3429448B2 JP 3429448 B2 JP3429448 B2 JP 3429448B2 JP 14515098 A JP14515098 A JP 14515098A JP 14515098 A JP14515098 A JP 14515098A JP 3429448 B2 JP3429448 B2 JP 3429448B2
- Authority
- JP
- Japan
- Prior art keywords
- drum
- metal
- roll
- peeling
- current collector
- 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.)
- Expired - Fee Related
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Cell Electrode Carriers And Collectors (AREA)
- Battery Electrode And Active Subsutance (AREA)
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。TECHNICAL FIELD The present invention relates to a porous current collector for a battery, which is 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 them. Regarding
【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, as a method for producing a metal mesh foil from a plating bath, many patents have been issued, such as plating a conductive drum provided with a non-conductive portion and peeling it off. From this viewpoint, This is a known fact. As an example of a recent patent, there is a method presented in Japanese Patent Laid-Open No. 8-100288. In this manufacturing method, a plating layer is formed by electroplating on a metal drum in which an insulating material is embedded in a predetermined pattern on the outer peripheral surface, and the plating layer is extended from the plating solution into the air to the peeling interface. The range is 0 ℃ to 15 ℃
It is characterized in that the plating layer and the surface are washed with cold water. In addition, as an effect brought about 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 embedded insulating material does not fall off from the metal drum. It is described that a long and inexpensive metal mesh foil can be continuously manufactured.
【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-mentioned method for producing a metal mesh foil still has the following problems to be solved. That is, according to the research conducted by the present inventor, the metal mesh foil manufactured using the same manufacturing method is extremely thin and porous, and therefore, when peeled at an appropriate peeling position or a peeling angle other than the peeling angle, for example, the preceding step Even if it is cooled with, the foil often breaks and stable production is difficult. Further, this method is not practical because the cooling water falls into the plating tank and the concentration of the plating solution decreases, and the intended 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 hydrogen secondary battery, a lithium polymer secondary battery, or the like. For the porosity of the metal plate, for example, there is a punching metal in which a hole is made in the metal plate by a mechanical method used as a negative electrode collector of nickel hydrogen, but it is not possible to meet the recent demand for thin plate porosity. Is the reality. It is said that the limit of the stable porosity by mechanical method is the foil thickness of 40 μm. Currently used Cu foil of 20 μm or less or A
l It is not only difficult to stabilize the porosity of the foil by a mechanical method, it also requires two steps of manufacturing the foil and making holes, and the metal in the holes is wasted. However, 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。The present invention has been made on the basis of such knowledge and enables stable production, and batteries (mainly lithium secondary batteries,
It was devised in order to provide a highly economical porous current collector or electrode suitable for a nickel-hydrogen secondary battery). That is, a manufacturing apparatus and a product for obtaining a metal strip having a hole area and a total hole area suitable as a current collector for a battery, and further by a method such as peeling a plating layer at a proper peeling position and a peeling angle. A porous metal strip capable of continuously producing a long porous metal foil at a low cost, or a method and an apparatus for producing an electrode using the porous metal strip as a current collector are provided. It is a highly effective and novel technology because it cannot be achieved.
【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-mentioned object, the porous current collector manufacturing apparatus of the present invention has a large number of non-conducting portions on the surface of a non-conducting portion as a current collector for a battery. This is an apparatus for producing a porous metal band by depositing a metal on a conductive drum provided so that the total area of the whole is within an appropriate range and peeling off the plating layer. When the metal strip is obtained in the non-conductor part, the stress concentration causes the distortion in the width direction,
It must be taken into consideration that they are arranged 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, it is an apparatus for producing a porous metal strip by depositing a metal on a conductive drum having a large number of non-conductive parts on its surface and peeling off the plating layer thereof, which is provided on the drum. The area of one of the non-conductive parts provided 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 the metal on the drum, 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 peeled from the drum. Consists 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 continuous production, the above-mentioned manufacturing apparatus is provided with an adhering metal removing device for removing the metal adhering to the non-conductor portion on the drum, and further, in the subsequent step of the peeling angle adjusting roll, plating From the viewpoint of preventing corrosion or dirt due to liquid residue adhesion, the surface of the metal strip may be simply washed with water → dried, but with a surface cleaning device for cleaning by such methods as water cleaning → pickling → water cleaning, and after surface cleaning 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。Further, when the average surface roughness (Ra) of the conductor portion of such a device is 0.1 to 3 μm as a metal band, 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 it is 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。Examples of the type of metal strip applicable to the porous current collector for batteries include iron, copper, nickel or aluminum, their alloys, 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 breaking the porous current collector due to tension during winding, the binder is continuously applied onto the porous current collector for a battery in the same process as in the production of the porous current collector. A stacking device for stacking the active material containing the above, a drying device for drying the stacked active material, and a compression and compression device for compressing the active material to the current collector after drying and mainly compressing the active material are provided. Is preferred.
【0012】請求項8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*10-5mm
2〜30mm2であり、かつ前記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前記
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、該めっき層を前記ドラムから剥離
させて多孔金属帯を形成し、その後、該金属帯の表面を
清浄化し、表面清浄した該金属帯を乾燥することを特徴
とする。The preparation method of the porous metal strip according to claim 8, a number of non-conductor section metal to precipitate on the conductive drum provided on the surface, and peeled off the plating layer, forming a number of holes The method for manufacturing a metal strip according to claim 1, wherein the area of one of the non-conductor portions provided on the drum is 2.5 * 10 −5 mm.
2 ~30Mm is 2 and the ratio of the total area of the sum and the conductor portion of the area of the non-conductors formed on the drum 0.
By immersing the a 1-9 conductive drum plating bath to form a plating layer on the <br/> drum, a proper peel angle of the metal strip is brought into contact with the peeling positioning rolls on the drum at a peel angle adjustment roll after setting, by peeling the plated layer from the drum to form a porous metal strip, after which the surface of the metal strip is cleaned, characterized by drying the metal strip and surface cleaning.
【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, depending on the type of plating metal and the plating thickness, there is a risk of breaking the metal strip when it is peeled off. In order to peel the metal strip from the drum more easily and stably, the cooling roll device is attached to the outer peripheral surface of the drum. It is preferable to directly press against the plating layer attached to.
【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 simply having a surface temperature adjusting function, but it is possible to adjust the surface temperature such as a rubber roll which is in direct contact with the plating layer and a rubber roll which is in contact with the rubber roll and through which cooling water is passed inside. It is preferable that the plating layer is formed of a different metal roll, and the surface of the rubber roll is cooled to an appropriate temperature by the metal roll to uniformly cool the plating layer due to the elasticity of the rubber.
【0015】さらに請求項13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 producing a battery electrode according to claim 13 , as described above, the active material containing a binder is subsequently laminated on the porous battery current collector obtained by the above method. The steps of drying the laminated active material, pressing the laminated active material and the current collector, and mainly compressing the active material to form an electrode in the same step. The present invention is characterized by avoiding the risk of breakage due to tension during winding of the porous collector and the current collector and corrosion during storage of the collector.
【0016】請求項14に記載の電池用電極は、請求項
13の製造方法で形成された電極であることを特徴とす
る。The battery electrode according to claim 14 is the following:
13 is an electrode formed by the manufacturing method of 13 .
【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。BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below with reference to an embodiment shown in the accompanying drawings. In this embodiment, the porous metal strip manufactured by the method for producing a porous metal strip 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. An explanation will be given by taking up the case of a porous copper foil.
【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 having a non-conductor portion 11 provided in a predetermined pattern on an outer peripheral surface of a conductor portion 10 is removed from a copper borofluoride bath in a tank 13. It is immersed in the plating bath 14. Here, the conductor portion 10 can be formed of stainless steel, titanium, or the like, and the non-conductor portion 11 is provided in a state in which a large number of holes are scattered in the metal, and synthetic resin pieces with high insulation are provided in the holes. It can be formed by embedding it and making its surface flush with the conductor portion 10 or slightly elevating the nonconductor 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 non-conductor 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 non-conductor portion 11 is less than 2.5 * 10 −5 mm 2 , it is difficult to obtain a continuous and stable pore size, and the porosity effect of the current collector, such as the improvement of adhesion, greatly differs 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, when it exceeds 30 mm 2 , the anchor effect due to the opening of holes is poor and the contribution to the improvement of adhesion is weakened. The term "adhesion" as used herein refers to the adhesion between the active material and the current collector, and the effect that the active material is not separated from the current collector due to bending or the like. In addition, the reason why the ratio of the total area of the non-conductive portion 11 to the total area of the conductive portion 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 it exceeds 9, it is not only difficult to stably peel from the plating layer drum, but also the strength of the current collector is weakened, and there is a risk of frequent breakage 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 non-conductor portions 11 are circular, oval, and
A symmetric shape such as a hexagon or a quadrangle is preferable, and it is necessary to consider that the arrangement has the same pitch in the width direction and the longitudinal direction so that stress concentration does not occur when a metal strip is obtained.
As an example, it is preferable that the circular non-conductor part having a diameter of 1 mm has a constant pitch interval in the vertical direction and the horizontal direction, or the center part is the same as the above, but only a few cm outside thereof. It is also preferable that the circular non-conductor parts having a diameter of 0.1 mm have a constant pitch interval in the vertical direction and a constant pitch interval in the horizontal direction.
【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 portion 10 is preferably 0.1 to 3 μm in order to obtain the roughening effect. 0.
If it is less than 1 μm, the effect of roughening the adhesion is not observed, and if it exceeds 3 μm, the effect is not only saturated, but there is a risk of breaking when the plated metal is 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 the 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 attached to the outer peripheral surface of the conductive drum 12. Here, the thickness of the porous plating layer 15 is generally preferably 5 to 70 μm in consideration of lightness and economy as a current collector for a battery. Also,
As the porous plating layer, iron, copper, nickel, aluminum or an alloy thereof, a multi-layered product or the like is preferably used. However, in the case of iron, it is preferable to apply nickel plating or the like after peeling since it 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 taking out 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 that is in direct 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 is passed. Therefore, first, by the rubber roll 17 whose surface is cooled by the metal roll 18, the porous plating layer 15 is uniformly cooled by utilizing the elasticity of rubber, and by utilizing the difference in expansion coefficient due to the temperature difference from the drum surface, The 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, since the cooling water is not directly applied to the porous plating layer 15 to cool it, the plating layer 15 can be cooled via the cooled metal roll 18 and the rubber roll 17, so that the cooling water is plated. Since there is no danger of dropping into the bath 14 and it is possible to prevent work safety and to prevent changes in the concentration of the plating bath, it is possible to stably manufacture the desired porous metal strip.
【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。Further, in order to prevent foreign matters such as plating sludge in the plating bath from adhering to the drum and the porous plating layer, it is preferable to provide a scraping jig A in contact with the conductive drum 12. As a matter of course, the adhered substance scraped off needs to be provided with a rubber roll or a saucer having an adhesive property so as to prevent the adhered substance from re-adhering or entering the plating bath to remove the 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 in a stable manner, it is important to remove as much as possible the adhered substances that cause pore shape defects and breakage 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, the peeling positioning roll 19 is provided on the outer surface of the conductive drum 12 at a position separated from the cooling roll device 16 by a predetermined distance, and The conductive drum 12 is provided via a pair of peeling angle adjusting rolls 20 and 21 which are spaced apart from the peeling positioning roll 19 by a predetermined distance.
The porous metal strip 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 the clamp surface of 21 is the plating bath 1
It will be experimentally determined by the content of the plating solution in 4, the hole shape, 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 which are most suitable for the characteristics, and the porous metal band 15a can be peeled as a long product without breaking. . Although not particularly shown in the figure, most of the plating solution adhered to the peeled metal strip is removed by a ringer roll before entering the surface cleaning device, and each tank of the surface cleaning device is removed. It is needless to say that it is preferable that a ringer roll or the like is also provided on the outlet side of the to remove almost all 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 reversing roll 22 into the water 25 filled in the water tank 24 having the reversing roll 23. To perform surface cleaning treatment. The surface cleaning treatment here includes not only washing with water but also combined treatments such as washing with water → pickling → washing with water, and refers to removing the plating solution residue adhering to the 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。The surface cleaning treatment may be performed simply by washing with water after peeling off the plating layer and then drying. More preferably, in order to almost completely remove the residue of the plating solution adhering to the plating layer, after washing with water, acid treatment with dilute sulfuric acid or the like is carried out. It is desirable to wash and then wash with water. For example, when obtaining a porous current collector in a copper borofluoride bath,
With just washing with water, dark spots may appear on the plated surface if it is left at room temperature for one day. It is considered that the cause of this is that the fluorine in the residue of the plating solution, which could not be sufficiently removed by washing with water, reacts with the moisture in the air to form HF, which is highly corrosive, 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 strip 15a to be the porous current collector is dried by the first dryer 27 through the reversing roll 26, and then the binder and graphite are added. After immersing the mixed active material 28 in the active material tank 29,
Excessive active material is removed with a knife coater to 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) The laminated porous metal strip 15b is dried by the second drying device 30, and then the compression compression roll 31 is used.
After compressing the active material 28 with a compression ratio of about 50%, it is wound on the reel 33 as the 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。When the porous current collector and the active material are laminated in the same step and then compression-compressed, the following merits occur.・ Simplified process and improved economy. Since the active material is applied under the condition that surface oxidation or corrosion of the porous metal strip hardly occurs, it is possible to manufacture an electrode having a more stable porous current collector.・ To properly wind up the porous current collector, it is necessary to apply tension to some extent, and there is a risk that the porous current collector, which is originally low in strength, will break, but the electrode obtained by laminating and pressing the active material has low strength. It becomes stronger and does not break even if tension is applied,
You will be able to wind up stably and cleanly.
【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 being cut to an appropriate size, the battery electrode 32 is preferably used as the negative electrode 37 of a card-shaped lithium polymer battery 34 which is expected to grow rapidly in the future as shown in FIG. 5, for example. Can be used. Note that FIG.
In the figure, 36 indicates a gel-like polymer electrolyte substance, and 3
5 indicates a positive electrode using an active material mainly composed of lithium nickel oxide, 38 indicates an exterior material made of a composite foil, 39,
40 indicates a lead wire. It can also be applied to lithium-ion secondary batteries and the like that 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, in the apparatus of the present invention, the individual area and the total area of the non-conductor 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 conductor portion. Since the development was focused on the current collector for batteries, economically obtaining a porous metal band (current collector) with good adhesion to the active material, which is an important property of the current collector. Became possible. Further, since the porous plating layer is peeled from the outer peripheral surface of the conductive drum via a peeling positioning roll and a pair of peeling angle adjusting rolls, and then the porous metal strip is manufactured by washing, thus forming the porous plating layer, Peeling can be performed at a peeling position and a peeling angle most suitable for the characteristics, and a long product can be peeled without breaking the porous metal band.
【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 producing a porous current collector of the present invention, the plating layer is peeled off by cooling the plating layer by directly pressing the cooling roll device against the plating layer attached to the outer peripheral surface of the conductive drum. It is possible to easily prevent the cooling water from falling into the plating bath, and it is possible to stably manufacture the porous metal strip to be the porous current collector.
【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。Further, in the manufacturing method of the present invention, since the cooling roll device cools the plating layer from the water-cooled metal roll through the rubber roll, the elasticity of the rubber can uniformly cool the plating layer, and Even if water accidentally leaks from the metal roll, the cooling water can be surely prevented from falling 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。Further, in the present invention, the porous metal strip can be manufactured at low cost by using copper, nickel, aluminum or the like as the plating metal used in the 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 a positional relationship between 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 band.
【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 10 ... Conductor 11 ... Non-conductor part 12 ... Conductive drum 14 ... Plating bath 15 ... Porous plating layer 15a ... Porous metal band 15b ... Laminated porous metal strip 19 ... Peeling positioning roll 20 ... Peeling angle adjusting roll 21 ... Peeling angle adjusting roll
フロントページの続き (56)参考文献 特開 昭63−128192(JP,A) 特開 昭62−205296(JP,A) 特開 昭54−62128(JP,A) 特開 昭51−110444(JP,A) 特開 平10−195689(JP,A) 特開 平8−236120(JP,A) 特開 平8−100288(JP,A) (58)調査した分野(Int.Cl.7,DB名) C25D 1/20 C25D 1/08 H01M 4/04 H01M 4/64 Continuation of the front page (56) Reference JP-A-63-128192 (JP, A) JP-A-62-205296 (JP, A) JP-A-54-62128 (JP, A) JP-A-51-110444 (JP , A) JP-A-10-195689 (JP, A) JP-A-8-236120 (JP, A) JP-A-8-100288 (JP, A) (58) Fields investigated (Int.Cl. 7 , DB) Name) C25D 1/20 C25D 1/08 H01M 4/04 H01M 4/64
Claims (14)
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
ラムが、その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、 かつ前記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であり、 前記ドラムを 連続的に回転させて導体部に金属をめっき
するためのめっき浴槽と、 前記ドラム上の めっき金属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、 多孔集電体を形成するための電池用多孔集電体製造装
置。1. A large number of non-conductor portion by depositing a metal on the conductive drum provided on the surface, and peeled off the plating layer, there is provided an apparatus for producing a metal strip formed with many holes, the Do
Ram, is one of the area is 2.5 * 10 -5 mm 2 ~30mm 2 nonconductor portion provided thereon, and the sum and the conductor portion of the area of the non-conductors formed on the drum The ratio of the area to the total area is 0.1 to 9, and the drum is continuously rotated to plate the conductor with metal.
Plating bath and the peeling position for peeling the plated metal on the drum.
Adjust the peeling angle between the coating roll and the plating layer peeled from the drum
An apparatus for manufacturing a porous current collector for a battery , which is provided with a peeling angle adjusting roll, for forming a porous current collector.
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記載の装置。2. A surface cleaning device for cleaning the surface of the metal strip and a drying device for drying the metal strip after the surface cleaning are provided in the subsequent step of the peeling angle adjusting roll. 1. The device according to 1 .
1〜3μmである請求項1又は2に記載の装置。3. The average surface roughness (Ra) of the conductor portion is 0.
The device according to claim 1 or 2 having a size of 1 to 3 µm.
を除去する付着金属除去装置を設けた請求項1〜3のい
ずれかに記載の装置。To wherein said drum apparatus according to any one of claims 1 to 3 provided the deposited metal removing device for removing metal adhered to the non-conductors.
ミニウムである請求項1〜4のいずれかに記載の装置。Wherein said metal band, iron, copper, apparatus according to any one of claims 1 to 4, which is a nickel or aluminum.
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1〜5のいずれか記載の装置。6. A cooling roll device capable of preferentially and rapidly cooling the plating layer on the drum which has come out of the plating bath in order to facilitate the peeling of the plating layer from the drum. The device according to any one of 1 to 5 .
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。7. A stacking device for successively stacking an active material containing a binder on the porous current collector obtained by the device according to any one of claims 1 to 6, and the stacked active material. An electrode manufacturing apparatus for a battery, comprising: a drying device for drying; and a compression / compression device for compressing the active material onto the porous current collector after drying and mainly compressing the active material to form an electrode.
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*1
0-5mm2〜30mm2であり、かつ前記ドラム上に形成
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
して前記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、該めっき層を前記ドラム
から剥離させて多孔金属帯を形成し、その後、該金属帯
の表面を清浄化し、表面清浄した該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。8. A method for producing a metal strip having a large number of holes by depositing a metal on a conductive drum having a large number of non-conductive portions on the surface and peeling off the plated layer. The area of one non-conductor part on the drum is 2.5 * 1
0 -5 mm 2 is ~30mm 2, and the conductive drum ratio is 0.1 to 9 and sum of the areas of the sum and the conductor portion of the area of the non-conductors formed on the drum plating bath immersed to form a plating layer on the drum, after setting the proper peel angle of the metal strip is brought into contact with the peeling positioning rolls on the drum at a peel angle adjustment roll, by peeling the plating layer from said drum perforated metal to form a band, then the surface of the metal strip is cleaned, the production method of the porous metal strip, characterized in that drying the metal strip and surface cleaning.
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8
記載の製造方法。9. The method of claim 8, characterized in that when separation of the metal strip, by pressing a cooling roll device directly to the plated layer which adheres to the outer peripheral surface of the drum
The manufacturing method described.
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
9記載の製造方法。10. The cooling roll device comprises a rubber roll which is in direct contact with the plating layer and a metal roll which is in contact with the rubber roll and whose temperature can be adjusted by a method such as passing cooling water inside. The plating layer is cooled by cooling the surface of the rubber roll to an appropriate temperature with the metal roll.
9. The manufacturing method according to 9 .
ルミニウムである請求項8〜10のいずれかに記載の製
造方法。11. The process according to the metal band, iron, copper, any of claims 8-10 is nickel or aluminum.
方法により製造された電池用多孔集電体。12. A porous current collector for a battery, which is manufactured by the manufacturing method according to any one of claims 8 to 11 .
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。13. The active material containing a binder is subsequently laminated on the porous current collector for battery obtained in claim 12 , and the laminated active material is dried to form a laminated active material and a current collector. A method of manufacturing an electrode for a battery, which comprises pressing and compressing a body in one step to manufacture an electrode.
極。14. A battery electrode formed by the method of claim 13 .
Priority Applications (1)
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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 |
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JPH11323593A JPH11323593A (en) | 1999-11-26 |
JP3429448B2 true JP3429448B2 (en) | 2003-07-22 |
Family
ID=15378586
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JP14515098A Expired - Fee Related JP3429448B2 (en) | 1998-05-12 | 1998-05-12 | Battery porous current collector, electrode, method and apparatus for producing them |
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Families Citing this family (12)
Publication number | Priority date | Publication date | Assignee | Title |
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AU2002330396A1 (en) | 2002-09-12 | 2004-04-30 | Matsushita Electric Industrial Co., Ltd. | Metal foil for current collector of secondary battery and method for producing the same |
JP5134785B2 (en) * | 2006-06-20 | 2013-01-30 | 川崎重工業株式会社 | Method for producing active material-containing molded body and apparatus for producing the same |
JP5117808B2 (en) * | 2007-09-28 | 2013-01-16 | プライムアースEvエナジー株式会社 | Cleaning device and cleaning method for core material for electrode plate, and method for producing alkaline storage battery using the cleaning method |
JP5929000B2 (en) * | 2011-03-28 | 2016-06-01 | 日立金属株式会社 | Method for producing porous aluminum foil |
KR101390507B1 (en) * | 2011-08-30 | 2014-04-30 | 니시 코교 가부시키가이샤 | Apparatus for electolytic deposition of porous foil |
US10276873B2 (en) | 2012-05-09 | 2019-04-30 | Korea Institute Of Machinery & Materials | Current collector for battery comprising metal mesh layer and manufacturing method therefor |
KR101630979B1 (en) * | 2014-12-12 | 2016-06-16 | 주식회사 포스코 | Apparatus for continuous electroforming |
JP6376112B2 (en) * | 2015-11-30 | 2018-08-22 | トヨタ自動車株式会社 | Electrode plate manufacturing method |
KR101696118B1 (en) * | 2015-12-22 | 2017-01-13 | 주식회사 포스코 | Apparatus for continuous electroforming |
JP2020152933A (en) * | 2019-03-18 | 2020-09-24 | 日立金属株式会社 | Electrolytic aluminum foil manufacturing apparatus and electrolytic aluminum foil manufacturing method |
CA3137941A1 (en) * | 2019-04-26 | 2020-10-29 | Ppg Industries Ohio, Inc. | Electrodes having conformal coatings deposited onto porous electrical current collectors |
KR102372707B1 (en) | 2021-08-23 | 2022-03-10 | 와이엠티 주식회사 | Carrier material for forming perforated metal foil and perforated metal foil with carrier material |
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1998
- 1998-05-12 JP JP14515098A patent/JP3429448B2/en not_active Expired - Fee Related
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