JPH10116626A - Manufacture of nickel hydrogen secondary battery - Google Patents
Manufacture of nickel hydrogen secondary batteryInfo
- Publication number
- JPH10116626A JPH10116626A JP8270062A JP27006296A JPH10116626A JP H10116626 A JPH10116626 A JP H10116626A JP 8270062 A JP8270062 A JP 8270062A JP 27006296 A JP27006296 A JP 27006296A JP H10116626 A JPH10116626 A JP H10116626A
- Authority
- JP
- Japan
- Prior art keywords
- negative electrode
- winding
- electrode group
- nickel
- secondary battery
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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、ニッケル水素二次
電池の製造方法に関し、特に電極群の作製工程を改良し
たニッケル水素二次電池の製造方法に係わる。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing a nickel-metal hydride secondary battery, and more particularly to a method for manufacturing a nickel-metal hydride secondary battery in which an electrode group manufacturing process is improved.
【０００２】[0002]
【従来の技術】円筒型ニッケル水素二次電池は、携帯電
話やノート型パソコンの電源等に用いられている。この
円筒型ニッケル水素二次電池は、一般に水酸化ニッケル
を含む正極と水素吸蔵合金を含む負極とをセパレータを
介して渦巻状に巻回した電極群を備えた構造になってい
る。2. Description of the Related Art Cylindrical nickel-metal hydride secondary batteries are used as power sources for mobile phones and notebook computers. This cylindrical nickel-metal hydride secondary battery generally has a structure including an electrode group in which a positive electrode containing nickel hydroxide and a negative electrode containing a hydrogen storage alloy are spirally wound via a separator.
【０００３】ところで、円筒型ニッケル水素二次電池は
近年の大量需要に伴って製造速度を高めることが急務に
なっている。その１つの方法として、従来より電極群を
一対の電極群保持ブロック内で作製、保持することが行
われている。すなわち、この方法は耐アルカリ性金属多
孔体に水酸化ニッケルを含む正極層を被覆した正極とパ
ンチドメタル基板に水素吸蔵合金を含む負極層を被覆し
た負極との間にセパレータを介在して積層した後、この
積層物を互いに水平方向に対向して配置された一対の電
極群保持ブロック内で前記負極が外側に位置するように
渦巻き状に巻回し、前記一対のブロックで渦巻状の電極
群の外周面を保持して電極群を作製するものである。By the way, there is an urgent need to increase the production speed of cylindrical nickel-metal hydride secondary batteries in response to recent large demand. As one of the methods, conventionally, an electrode group is manufactured and held in a pair of electrode group holding blocks. That is, in this method, a separator was interposed between a positive electrode coated with a positive electrode layer containing nickel hydroxide on an alkali-resistant metal porous body and a negative electrode coated with a negative electrode layer containing a hydrogen storage alloy on a punched metal substrate. After that, the laminate is spirally wound so that the negative electrode is located outside in a pair of electrode group holding blocks arranged horizontally facing each other, and the spirally wound electrode group is formed by the pair of blocks. The electrode group is produced while holding the outer peripheral surface.
【０００４】前述した電極群の作製における巻回後期工
程において、前記電極群の巻終わり端部とこれと対向す
る外周面部分が前記一対のブロックにそれぞれ摺接する
が、渦巻状の電極群の構造上、巻終わり端部の方が前記
ブロックに対する摺接力が大きくなる。このような電極
群の作製に際し、前記電極群の外側に配置される負極は
パンチドメタル基板全体に水素吸蔵合金を含む負極層を
被覆した構造を有するため、前記ブロックと大きな力で
摺接する巻終わり端部で負極層が剥離・脱落する不良が
多発するという問題があった。[0004] In the latter winding step in the above-described fabrication of the electrode group, the winding end end of the electrode group and the outer peripheral surface facing the sliding end are in sliding contact with the pair of blocks, respectively. The sliding contact force with respect to the block is greater at the upper end and at the end of the winding. In manufacturing such an electrode group, the negative electrode disposed outside the electrode group has a structure in which the entire punched metal substrate is covered with a negative electrode layer containing a hydrogen storage alloy, and thus the negative electrode is slid in contact with the block with a large force. There has been a problem that the defect that the negative electrode layer peels off and falls off at the end end frequently occurs.
【０００５】また、前記電極群の作製に際して巻始め端
部は曲率半径が小さく、その折れ曲りがパンチドメタル
基板の穴に沿ってなされるため、前記折り曲げられた穴
に位置する前記負極層部分が浮いた状態になって剥離す
る。前記巻始め端部から剥離した負極材料（主に水素吸
蔵合金）は、電極群の作製時には巻き芯等により前記パ
ンチド基板に保持されるが、負極端子を兼ねる有底円筒
型容器内に前記電極群を収納する際の電極群の巻き状態
の緩みにより前記容器底部に脱落する。容器底部に負極
材料が脱落すると、電極群の正極と接触して内部短絡の
要因になる。[0005] Further, in manufacturing the electrode group, the winding start end portion has a small radius of curvature and is bent along the hole of the punched metal substrate, so that the negative electrode layer portion located in the bent hole is bent. Comes off and peels off. The negative electrode material (mainly a hydrogen storage alloy) peeled off from the winding start end is held on the punched substrate by a winding core or the like at the time of forming an electrode group, but the electrode material is placed in a bottomed cylindrical container also serving as a negative electrode terminal. The electrode group drops off to the bottom of the container due to loosening of the wound state of the electrode group when the group is housed. When the negative electrode material falls off at the bottom of the container, the negative electrode material comes into contact with the positive electrode of the electrode group and causes an internal short circuit.
【０００６】[0006]
【発明が解決しようとする課題】本発明は、一対の電極
群保持ブロック内での電極群の作製工程において負極の
巻始め端部および巻終わり端部側の負極層の剥離に起因
する不良発生を低減したニッケル水素二次電池の製造方
法を提供しようとするものである。SUMMARY OF THE INVENTION According to the present invention, in the process of forming an electrode group in a pair of electrode group holding blocks, a defect caused by peeling of a negative electrode layer at a winding start end and a winding end end side of a negative electrode occurs. It is an object of the present invention to provide a method for manufacturing a nickel-metal hydride secondary battery in which the number of cells is reduced.
【０００７】[0007]
【課題を解決するための手段】本発明に係わるニッケル
水素二次電池の製造方法は、耐アルカリ性金属多孔体に
水酸化ニッケルを含む正極層を被覆した正極とパンチド
メタル基板に水素吸蔵合金を含む負極層を被覆した負極
との間にセパレータを介在し積層する工程と、互いに水
平方向に対向して配置された一対の電極群保持ブロック
内で前記積層物を前記負極が外側に位置するように渦巻
き状に巻回し、前記一対のブロックで渦巻状の電極群の
外周面を保持する工程と、前記電極群を有底円筒状の容
器内に収納する工程とを具備したニッケル水素二次電池
の製造方法において、前記負極は、巻始め端部および巻
終わり端部に穴あけされていない無地部が形成されたパ
ンチドメタル基板に水素吸蔵合金を含む負極層を前記無
地部のうち少なくとも巻終わり端部側の無地部の一部も
しくは全部を除いて被覆することにより形成されること
を特徴とするものである。According to the present invention, there is provided a method for manufacturing a nickel-metal hydride secondary battery, comprising the steps of: forming a positive electrode in which a positive electrode layer containing nickel hydroxide is coated on a porous alkali-resistant metal; A step of interposing a separator between the negative electrode coated with the negative electrode layer including the negative electrode layer, and laminating the laminate in a pair of electrode group holding blocks arranged to face each other horizontally so that the negative electrode is located outside. A nickel-hydrogen secondary battery, comprising: a step of spirally winding the electrode group and holding the outer peripheral surface of the spiral electrode group by the pair of blocks; and a step of storing the electrode group in a bottomed cylindrical container. In the manufacturing method of the negative electrode, the negative electrode layer containing a hydrogen storage alloy in the punched metal substrate on which a solid portion that is not perforated at the winding start end and the winding end end is formed in the uncoated portion. Is characterized in that is also formed by coating with the exception of some or all of the non-coating portion of the winding end portion.
【０００８】前記パンチドメタル基板の前記無地部のト
ータル面積は、前記基板全体の面積に対して１５〜２５
％占め、巻始め端部および巻終わり端部側の前記無地部
は前記基板に対してそれぞれ３〜２０％の面積を占める
ことが好ましい。The total area of the uncoated portion of the punched metal substrate is 15 to 25 with respect to the entire area of the substrate.
Preferably, the uncoated portions on the side of the winding start end and the winding end end occupy an area of 3 to 20% with respect to the substrate.
【０００９】[0009]
【発明の実施の形態】以下、本発明のニッケル水素二次
電池の製造方法を図１〜図４を参照して説明する。 （第１工程）まず、水素吸蔵合金、導電材、結着剤およ
び水と共に混練してペーストを調製する。つづいて、巻
始め端部および巻終わり端部側に穴のあいていない無地
部を有するパンチドメタル基板に前記ペーストを塗布し
た後、乾燥することにより図１に示すように巻始め端部
および巻終わり端部側に帯状の無地部１、２を有するパ
ンチドメタル基板３に水素吸蔵合金を含む負極層４が前
記無地部１、２の一部（端部側）を除いて被覆された負
極５を作製した。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS A method for manufacturing a nickel-metal hydride secondary battery according to the present invention will be described below with reference to FIGS. (First Step) First, a paste is prepared by kneading with a hydrogen storage alloy, a conductive material, a binder and water. Then, after applying the paste to a punched metal substrate having a solid portion without a hole on the side of the winding start end and the winding end, the paste is dried as shown in FIG. A negative electrode layer 4 containing a hydrogen storage alloy was coated on a punched metal substrate 3 having strip-shaped uncoated portions 1 and 2 on the winding end end side except for a part (end side) of the uncoated portions 1 and 2. A negative electrode 5 was produced.
【００１０】前記前記水素吸蔵合金は、格別制限される
ものではなく、電解液中で電気化学的に発生させた水素
を吸蔵でき、かつ放電時にその吸蔵水素を容易に放出で
きるものであればよい。例えば、ＬａＮｉ5 、ＭｍＮｉ
5 （Ｍｍはミッシュメタル）、ＬｍＮｉ5 （ＬｍはＬａ
を含む希土類元素から選ばれる少なくとも一種）、これ
ら合金のＮｉの一部をＡｌ、Ｍｎ、Ｃｏ、Ｔｉ、Ｃｕ、
Ｚｎ、Ｚｒ、Ｃｒ、Ｂのような元素で置換した多元素系
のもの、またはＴｉＮｉ系、ＴｉＦｅ系のものを挙げる
ことができる。特に、一般式ＬｍＮｉw Ｃｏx Ｍｎy Ａ
ｌz （原子比ｗ，ｘ，ｙ，ｚの合計値は５．００≦ｗ＋
ｘ＋ｙ＋ｚ≦５．５０である）で表される組成の水素吸
蔵合金は充放電サイクルの進行に伴う微粉化を抑制して
充放電サイクル寿命を向上できるための好適である。[0010] The hydrogen storage alloy is not particularly limited, and may be any alloy capable of storing hydrogen electrochemically generated in an electrolyte and easily releasing the stored hydrogen during discharge. . For example, LaNi 5 , MmNi
5 (Mm is misch metal), LmNi 5 (Lm is La
At least one element selected from the group consisting of rare earth elements containing Al), Mn, Co, Ti, Cu,
Examples thereof include a multi-element-based material substituted with an element such as Zn, Zr, Cr, and B, a TiNi-based material, and a TiFe-based material. In particular, the general formula LmNi w Co x Mn y A
l z (the total value of the atomic ratios w, x, y, z is 5.00 ≦ w +
(x + y + z ≦ 5.50) The hydrogen storage alloy having the composition represented by the formula (1) is preferable because it suppresses the pulverization accompanying the progress of the charge / discharge cycle and can improve the charge / discharge cycle life.
【００１１】前記導電材としては、例えばカーボンブラ
ック、黒鉛等を挙げることができる。前記結着剤として
は、例えばポリアクリル酸ソーダ、ポリアクリル酸カリ
ウムなどのポリアクリル酸塩、ポリテトラフルオロエチ
レン（ＰＴＦＥ）などのフッ素系樹脂、またはカルボキ
シメチルセルロース（ＣＭＣ）等を挙げることができ
る。[0011] Examples of the conductive material include carbon black and graphite. Examples of the binder include polyacrylates such as sodium polyacrylate and potassium polyacrylate, fluorine-based resins such as polytetrafluoroethylene (PTFE), and carboxymethyl cellulose (CMC).
【００１２】前記パンチドメタル基板３の無地部１、２
は、前記基板３全体に対して１０〜２５％の面積を占
め、かつ巻始め端部および巻終わり端部側の前記無地部
は前記基板に対してそれぞれ３〜２０％の面積を占める
ることが好ましい。前記無地部の面積比率を限定したの
は、次のような理由によるものである。前記無地部１、
２の全体の面積比率を１０％未満で、個々の無地部の面
積比率を３％未満にすると、電極群を作製する際の巻始
め端部および巻終わり端部での負極層の脱落を生じる恐
れがある。前記無地部１、２全体の面積比率が２５％を
越えると、電極反応の寄与度の低い負極部分が多くなっ
て容量低下を招く恐れがある。The uncoated portions 1 and 2 of the punched metal substrate 3
Occupies an area of 10 to 25% with respect to the entire substrate 3, and the uncoated portions at the winding start end and the winding end end occupy an area of 3 to 20% with respect to the substrate, respectively. Is preferred. The reason for limiting the area ratio of the uncoated portion is as follows. The plain part 1,
If the area ratio of the whole of No. 2 is less than 10% and the area ratio of the individual uncoated portions is less than 3%, the negative electrode layer will fall off at the winding start end and the winding end when manufacturing the electrode group. There is fear. If the total area ratio of the uncoated portions 1 and 2 exceeds 25%, the negative electrode portion having a low degree of contribution to the electrode reaction increases, and the capacity may be reduced.
【００１３】前記負極層４は、前記無地部１、２に６０
％以下（０％を含む）の範囲で被覆することを許容す
る。前記パンチドメタル基板３の巻始め端部側の無地部
１は、全体が負極層４で被覆されもよい。The negative electrode layer 4 has a 60
% Or less (including 0%). The uncoated portion 1 on the winding start end side of the punched metal substrate 3 may be entirely covered with a negative electrode layer 4.
【００１４】（第２工程）水酸化ニッケル粉末、導電
剤、結着剤および水を含むペーストを調製し、このペー
ストを耐アルカリ性金属多孔体に充填し、これを乾燥、
加圧成形した後、所望のサイズに切断することによりペ
ースト式正極を作製する。(Second step) A paste containing nickel hydroxide powder, a conductive agent, a binder and water is prepared, and the paste is filled in an alkali-resistant metal porous body, and dried.
After pressure molding, the paste is cut into a desired size to produce a paste-type positive electrode.
【００１５】前記水酸化ニッケル粉末としては、例えば
単一の水酸化ニッケル粉末、または亜鉛および／または
コバルトが金属ニッケルと共沈された水酸化ニッケル粉
末を用いることができる。後者の水酸化ニッケル粉末を
含む正極は、高温状態における充電効率を更に向上する
ことが可能になる。As the nickel hydroxide powder, for example, a single nickel hydroxide powder or a nickel hydroxide powder in which zinc and / or cobalt are coprecipitated with metallic nickel can be used. The latter positive electrode containing nickel hydroxide powder can further improve the charging efficiency in a high temperature state.
【００１６】前記導電剤としては、例えば一酸化コバル
ト、三酸化二コバルト、水酸化コバルト等のコバルト化
合物を挙げることができる。前記結着剤としては、例え
ばポリテトラフルオロエチレン、カルボキシメチルセル
ロース、メチルセルロース、ポリアクリル酸ナトリウ
ム、ポリビニルアルコールを挙げることができる。Examples of the conductive agent include cobalt compounds such as cobalt monoxide, dicobalt trioxide and cobalt hydroxide. Examples of the binder include polytetrafluoroethylene, carboxymethyl cellulose, methyl cellulose, sodium polyacrylate, and polyvinyl alcohol.
【００１７】前記耐アルカリ性金属多孔体としては、例
えばニッケル、ステンレス等の金属や、ニッケルメッキ
が施された樹脂などからなるスポンジ状、繊維状、フェ
ルト状の多孔質構造を有するものを挙げることができ
る。Examples of the alkali-resistant porous metal include those having a sponge-like, fibrous, or felt-like porous structure made of a metal such as nickel or stainless steel, or a nickel-plated resin. it can.
【００１８】（第３工程）図２に示すように前記負極５
を２枚折りしたセパレータ６の間に配置し、これら負極
５およびセパレータ６を前述した方法で作製した正極７
に重ねる。この時、前記２枚折りされたセパレータ６は
前記正極７側に位置する長さが反対側に位置する長さよ
り短くなっている。つまり、前記正極７側に位置する前
記セパレータ６部分は切欠されて前記負極５が露出して
いる。また、前記セパレータ６で挟み込まれた前記負極
５は後述する渦巻状の電極群を作製する際に外側に前記
負極５が配置されるように前記電極群の最外周の長さに
相当する分、前記正極７より長くしてある。(Third Step) As shown in FIG.
Are disposed between the separators 6 folded into two, and the negative electrode 5 and the separator 6 are connected to the positive electrode 7 manufactured by the method described above.
Layer on. At this time, the length of the two-folded separator 6 located on the positive electrode 7 side is shorter than the length located on the opposite side. That is, the part of the separator 6 located on the side of the positive electrode 7 is notched, and the negative electrode 5 is exposed. Further, the negative electrode 5 sandwiched between the separators 6 corresponds to the length of the outermost periphery of the electrode group so that the negative electrode 5 is arranged outside when a spiral electrode group described later is manufactured. It is longer than the positive electrode 7.
【００１９】次いで、図２に示す積層物を図３に示すよ
うに互いに水平方向に対向して配置、固定された一対の
電極群保持ブロック２１1 、２１2 内で図示しない巻き
芯を用いて渦巻状に巻回して外側に負極５が配置される
電極群８を作製する。なお、この電極群８の作製に際し
ての巻回操作は巻終わり端部が前記ブロック２１1 、２
１2 の一方（例えば右側のブロック２１1 ）の湾曲面に
当接されると共に、前記電極群８は前記一対のブロック
２１1 、２１2 により保持される。また、前記電極群８
の外径寸法は後述する有底円筒状容器の内径寸法より僅
かに小さくなるように作製する。[0019] Then, using a winding core (not shown) stacked structure shown in FIG. 2 arranged facing the horizontal direction from each other as shown in FIG. 3, a fixed pair of electrodes holding blocks 21 1, 21 within 2 An electrode group 8 in which the negative electrode 5 is arranged spirally is formed. The winding operation for producing the electrode group 8 is such that the winding end ends are the blocks 21 1 , 2
While it is abutted against the curved surface of a second one (e.g., the right block 21 1), the electrode group 8 is held by the pair of blocks 21 1, 21 2. The electrode group 8
Is manufactured so as to have a slightly smaller outer diameter than an inner diameter of a bottomed cylindrical container described later.
【００２０】前記セパレータ６としては、例えばポリア
ミド繊維製不織布、ポリエチレンやポリプロピレンなど
のポリオレフィン繊維製不織布に親水性官能基を付与し
たもの等から形成される。The separator 6 is made of, for example, a nonwoven fabric made of a polyamide fiber or a nonwoven fabric made of a polyolefin fiber such as polyethylene or polypropylene provided with a hydrophilic functional group.
【００２１】（第４工程）前記電極群ないの巻き芯を引
き抜いた後、有底円筒状容器を前述した図３の電極群８
の直下に移動させ、図示しないプッシャにより前記一対
のブロック２１1、２１2 で保持された電極群８を下方
に押圧して前記容器内に収納する。つづいて、常法に従
って正極リードが取り付けられた円板状の封口板をリン
グ状の絶縁ガスケットを介して前記有底円筒状容器の上
部開口部にカシメ固定し、ゴム製の安全弁が収納された
帽子形状をなす正極端子を前記封口板上に配置し、押え
板で前記正極端子を押さえた後、前記容器底部中央付近
を除く全体を外装チューブで被覆することにより図４に
示す構造のニッケル水素二次電池を製造する。(Fourth Step) After the core of the electrode group is pulled out, the bottomed cylindrical container is removed from the electrode group 8 of FIG.
Moved directly under the, by pressing the electrode group 8 held by the pusher (not shown) in the pair of blocks 21 1, 21 2 downward is housed in the container. Subsequently, a disk-shaped sealing plate to which a positive electrode lead was attached was fixed by caulking to the upper opening of the bottomed cylindrical container via a ring-shaped insulating gasket according to a conventional method, and a rubber safety valve was housed. A positive electrode terminal having a hat shape is arranged on the sealing plate, the positive electrode terminal is pressed by a pressing plate, and the entire surface except for the vicinity of the center of the bottom of the container is covered with an outer tube. Manufacture secondary batteries.
【００２２】図４に示す二次電池において、有底円筒状
容器９内には前述した正極７とセパレータ６と負極５と
の積層物を渦巻状に捲回することにより作製された電極
群８が収納されている。アルカリ電解液は、前記容器９
内に収容されている。中央に穴１０を有する円形の封口
板１１は、前記容器９の上部開口部に配置されている。
リング状の絶縁性ガスケット１２は、前記封口板１１の
周縁と前記容器９の上部開口部内面の間に配置され、前
記上部開口部を内側に縮径するカシメ加工により前記容
器９に前記封口板１１を前記ガスケット１２を介して気
密に固定している。正極リード１３は、一端が前記正極
７に接続、他端が前記封口板１２の下面に接続されてい
る。帽子形状をなす正極端子１４は、前記封口板１２上
に前記穴１０を覆うように取り付けられている。ゴム製
の安全弁１５は、前記封口板１２と前記正極端子１４で
囲まれた空間内に前記穴１０を塞ぐように配置されてい
る。中央に穴を有する絶縁材料からなる円形の押え板１
６は、前記正極端子１４上に前記正極端子１４の突起部
がその押え板１６の前記穴から突出されるように配置さ
れている。外装チューブ１７は、前記押え板１６の周
縁、前記容器９の側面及び前記容器９の底部周縁を被覆
している。In the secondary battery shown in FIG. 4, an electrode group 8 formed by spirally winding a laminate of the above-described positive electrode 7, separator 6 and negative electrode 5 in a cylindrical container 9 having a bottom. Is stored. The alkaline electrolyte is supplied to the container 9
Housed within. A circular sealing plate 11 having a hole 10 in the center is arranged at the upper opening of the container 9.
The ring-shaped insulating gasket 12 is disposed between the peripheral edge of the sealing plate 11 and the inner surface of the upper opening of the container 9, and the sealing plate is attached to the container 9 by caulking to reduce the diameter of the upper opening inward. 11 is hermetically fixed via the gasket 12. One end of the positive electrode lead 13 is connected to the positive electrode 7, and the other end is connected to the lower surface of the sealing plate 12. The hat-shaped positive electrode terminal 14 is attached on the sealing plate 12 so as to cover the hole 10. A rubber safety valve 15 is disposed so as to cover the hole 10 in a space surrounded by the sealing plate 12 and the positive electrode terminal 14. Circular holding plate 1 made of insulating material with a hole in the center
Numeral 6 is arranged on the positive electrode terminal 14 such that the projection of the positive electrode terminal 14 projects from the hole of the holding plate 16. The outer tube 17 covers the periphery of the holding plate 16, the side surface of the container 9, and the periphery of the bottom of the container 9.
【００２３】前記アルカリ電解液は、水酸化カリウム
（ＫＯＨ）単独、水酸化カリウムと水酸化ナトリウムの
混合液、水酸化カリウムと水酸化リチウムの混合液、ま
たは水酸化カリウムと水酸化ナトリウムと水酸化リチウ
ムの混合液からなる組成を有する。The alkaline electrolyte may be potassium hydroxide (KOH) alone, a mixture of potassium hydroxide and sodium hydroxide, a mixture of potassium hydroxide and lithium hydroxide, or a mixture of potassium hydroxide, sodium hydroxide and hydroxide. It has a composition consisting of a mixture of lithium.
【００２４】以上説明した本発明に係わるニッケル水素
二次電池の製造方法は、耐アルカリ性金属多孔体に水酸
化ニッケルを含む正極層を被覆した正極とパンチドメタ
ル基板に水素吸蔵合金を含む負極層を被覆した負極との
間にセパレータを介在し積層する工程と、互いに水平方
向に対向して配置された一対の電極群保持ブロック内で
前記積層物を前記負極が外側に位置するように渦巻き状
に巻回し、前記一対のブロックで渦巻状の電極群の外周
面を保持する工程と、前記電極群を有底円筒状の容器内
に収納する工程とを具備し、前記負極を巻始め端部およ
び巻終わり端部側に穴あけされていない無地部を有する
パンチドメタル基板に水素吸蔵合金を含む負極層を前記
無地部のうち少なくとも巻終わり端部側の無地部の一部
もしくは全部を除いて被覆することにより形成するもの
である。The method of manufacturing a nickel-metal hydride secondary battery according to the present invention described above comprises a positive electrode in which a positive electrode layer containing nickel hydroxide is coated on a porous alkali-resistant metal, and a negative electrode layer containing a hydrogen storage alloy on a punched metal substrate. Interposing and stacking a separator between the negative electrode and the coated negative electrode, and spirally stacking the stacked body in a pair of electrode group holding blocks arranged to face each other horizontally so that the negative electrode is located outside. And a step of holding the outer peripheral surface of the spiral electrode group with the pair of blocks, and a step of housing the electrode group in a bottomed cylindrical container. And a punched metal substrate having a solid portion that is not perforated at the end of the winding end and a negative electrode layer containing a hydrogen storage alloy is removed from at least a part or all of the uncoated portion at the end of the winding end of the uncoated portion. And forms by coating Te.
【００２５】このような本発明の方法によれば、巻始め
端部および巻終わり端部側が無地部であるパンチドメタ
ル基板に水素吸蔵合金を含む負極層を被覆して負極を形
成することによって、前述した一対の電極群保持ブロッ
ク内で前記負極、セパレータおよび正極の積層物を巻回
する際、曲率半径が小さい状態で折れ曲られる巻始め端
部は穴のあいていない無地部であるため、折り曲げに伴
って被覆された負極層が浮いた状態になるらず、その結
果、前記負極層が前記パンチドメタル基板から剥離する
のを防止できる。According to such a method of the present invention, a negative electrode is formed by coating a negative electrode layer containing a hydrogen storage alloy on a punched metal substrate having uncoated portions at the winding start end and the winding end end. When winding the laminate of the negative electrode, the separator, and the positive electrode in the above-described pair of electrode group holding blocks, the winding start end that is bent with a small radius of curvature is a solid portion without a hole. In addition, the coated negative electrode layer does not float due to the bending, and as a result, the negative electrode layer can be prevented from peeling off from the punched metal substrate.
【００２６】また、前述した図３に示す電極群８の作製
における巻回後期工程において、電極群８の最外周部分
（巻終わり端部とこれと対向する部分）が前記一対のブ
ロック２１1 、２１2 にそれぞれ摺接する。この摺接に
おいて、渦巻状の電極群８の構造上、巻終わり端部の方
が前記ブロック（例えば右側のブロック２１1 ）に対す
る摺接力が大きくなる。このような電極群の作製に際
し、図１に示すように前記電極群の外側に配置される負
極５を構成するパンチドメタル基板３は巻終わり端部側
に無地部２を有し、かつ負極層４を前記無地部２が露出
するように被覆しているため、前記ブロック２１1 は負
極層４の存在しない無地部２に摺接させることができ
る。その結果、巻終わり端部で負極層が剥離・脱落する
のを防止できる。Further, in the latter winding step in the production of the electrode group 8 shown in FIG. 3, the outermost peripheral portion of the electrode group 8 (the winding end portion and the portion facing the same) is formed by the pair of blocks 21 1 , respectively 21 2 sliding contact. In this sliding contact, due to the structure of the spiral electrode group 8, the sliding contact force with respect to the block (for example, the right block 21 1 ) is larger at the end portion of the winding. In manufacturing such an electrode group, as shown in FIG. 1, the punched metal substrate 3 constituting the negative electrode 5 disposed outside the electrode group has the uncoated portion 2 on the end side of the winding end, and because the layer 4 is the non-coating portion 2 is covered so as to expose, it said block 21 1 may be in sliding contact with the uncoated portion 2 in the absence of negative electrode layer 4. As a result, it is possible to prevent the negative electrode layer from peeling off or falling off at the end of winding.
【００２７】したがって、電極群の作製工程における負
極の不良発生を低減したニッケル水素二次電池を製造す
ることができる。さらに、パンチドメタル基板への負極
層の被覆面積を縮小できるために、負極の作製コストを
低減することが可能になる。Therefore, it is possible to manufacture a nickel-metal hydride secondary battery in which the occurrence of defects of the negative electrode in the process of forming the electrode group is reduced. Further, since the area of the punched metal substrate covered with the negative electrode layer can be reduced, the manufacturing cost of the negative electrode can be reduced.
【００２８】[0028]
【実施例】以下、本発明の実施例を前述した図１〜図４
を参照して詳細に説明する。 （実施例１）まず、ＬａＮｉ4.0 Ｃｏ0.4 Ｍｎ0.3 Ａｌ
0.3 の組成からなる水素吸蔵合金粉末９５重量部と、カ
ーボン粉末１重量部と、結着剤としてのポリテトラフル
オロエチレン粉末３重量部およびカルボキシメチルセル
ロース１重量部とを水５０重量部と共に混合することに
よって、ペーストを調製した。つづいて、前述した図１
に示すように巻始め端部および巻終わり端部側に帯状の
無地部１、２がそれぞれ１０％の面積率で形成されたパ
ンチドニッケル基板３に前記ペーストをパンチド部を含
み、前記各無地部１、２の５０％の部分が被覆されるよ
うに塗布、乾燥した後、加圧成形することによって負極
を作製した。FIG. 1 to FIG. 4 show an embodiment of the present invention.
This will be described in detail with reference to FIG. (Example 1) First, LaNi 4.0 Co 0.4 Mn 0.3 Al
95 parts by weight of a hydrogen storage alloy powder having a composition of 0.3 , 1 part by weight of carbon powder, 3 parts by weight of polytetrafluoroethylene powder as binder and 1 part by weight of carboxymethyl cellulose are mixed together with 50 parts by weight of water. To prepare a paste. Next, FIG.
As shown in FIG. 5, the paste is punched on a punched nickel substrate 3 having band-shaped uncoated portions 1 and 2 formed at an area ratio of 10% at the winding start end and the winding end end, respectively. After applying and drying so that 50% of the parts 1 and 2 were covered, the negative electrode was produced by pressure molding.
【００２９】また、水酸化ニッケル粉末９０重量部およ
び一酸化コバルト粉末１０重量部からなる混合粉末にカ
ルボキシメチルセルロース０．３重量％およびポリテト
ラフルオロエチレン２．０重量％を添加し、さらにこの
混合物に水３５重量％を添加、混練してペーストを調製
した。このペーストを耐アルカリ性金属多孔体としての
多孔度９５％のニッケルメッキ繊維基板に充填し、乾燥
した後、ローラプレスして圧延成形することにより正極
を作製した。Further, 0.3% by weight of carboxymethylcellulose and 2.0% by weight of polytetrafluoroethylene were added to a mixed powder composed of 90 parts by weight of nickel hydroxide powder and 10 parts by weight of cobalt monoxide powder. A paste was prepared by adding and kneading 35% by weight of water. This paste was filled in a nickel-plated fiber substrate having a porosity of 95% as an alkali-resistant metal porous body, dried, and then roll-pressed to form a positive electrode.
【００３０】次いで、前述した図２に示すように前記負
極５を２枚折りしたポリプロピレン製不織布からなるセ
パレータ６の間に配置し、これら負極５およびセパレー
タ６を前述した方法で作製した正極７に重ねた。この
時、前記２枚折りされたセパレータ６は前記正極７側に
位置する長さが反対側に位置する長さより短くした。ま
た、前記セパレータ６で挟み込まれた前記負極５は後述
する渦巻状の電極群を作製する際に外側に前記負極５が
配置されるように前記電極群の最外周の長さに相当する
分、前記正極７より長くした。Next, as shown in FIG. 2 described above, the negative electrode 5 is disposed between separators 6 made of folded polypropylene nonwoven fabric, and these negative electrodes 5 and separator 6 are attached to the positive electrode 7 manufactured by the above-described method. Stacked. At this time, the length of the two-folded separator 6 on the positive electrode 7 side was shorter than the length on the opposite side. The negative electrode 5 sandwiched between the separators 6 corresponds to the length of the outermost periphery of the electrode group so that the negative electrode 5 is arranged outside when a spiral electrode group described later is manufactured. It was longer than the positive electrode 7.
【００３１】次いで、前述した図３に示すように互いに
水平方向に対向して配置、固定された一対の電極群保持
ブロック２１1 、２１2 内で図示しない巻き芯を用いて
渦巻状に巻回して外側に負極５が配置され、後述する有
底円筒状容器の内径寸法より僅かに小さい外径寸法を有
する電極群８を作製した。なお、この電極群８の作製に
際しての巻回操作は巻終わり端部が前記ブロック２１
1 、２１2 の一方（例えば右側のブロック２１1 ）の湾
曲面に当接されると共に、前記電極群８は前記一対のブ
ロック２１1 、２１2 により保持された。つづいて、前
記巻き芯を前記電極群から引き抜いた後、ステンレス製
の有底円筒状容器を前述した図３の電極群８の直下に移
動させ、図示しないプッシャにより前記一対のブロック
２１1 、２１2 で保持された前記電極群８を下方に押圧
して前記容器内に収納した。この後、常法に従って正極
リードが取り付けられた円板状の封口板をリング状の絶
縁ガスケットを介して前記有底円筒状容器の上部開口部
にカシメ固定し、ゴム製の安全弁が収納された帽子形状
をなす正極端子を前記封口板上に配置し、押え板で前記
正極端子を押さえた後、前記容器底部中央付近を除く全
体を外装チューブで被覆することにより前述した図４に
示す構造のニッケル水素二次電池を製造した。[0031] Subsequently, arranged facing the horizontal direction from each other as shown in FIG. 3 described above, winding spirally with winding core (not shown) at a fixed pair of electrodes holding blocks 21 1, 21 within 2 The negative electrode 5 was disposed on the outside of the electrode group, and an electrode group 8 having an outer diameter slightly smaller than an inner diameter of a bottomed cylindrical container described later was produced. The winding operation for producing the electrode group 8 is such that the winding end end is the block 21.
1, 21 2 of one (e.g., the right block 21 1) while being abutted against the curved surface of the electrode group 8 is held by the pair of blocks 21 1, 21 2. Subsequently, after the core is pulled out from the electrode group, the bottomed cylindrical container made of stainless steel is moved directly below the electrode group 8 in FIG. 3 described above, and the pair of blocks 21 1 , 21 is pushed by a pusher (not shown). The electrode group 8 held in 2 was pressed downward and housed in the container. Thereafter, a disc-shaped sealing plate to which a positive electrode lead was attached was fixed to the upper opening of the bottomed cylindrical container via a ring-shaped insulating gasket according to a conventional method, and a rubber safety valve was housed. After disposing a positive electrode terminal having a hat shape on the sealing plate, pressing the positive electrode terminal with a pressing plate, and covering the whole except for the vicinity of the bottom center of the container with an outer tube, the structure shown in FIG. A nickel-metal hydride secondary battery was manufactured.
【００３２】（実施例２）まず、巻始め端部および巻終
わり端部側に帯状の無地部がそれぞれ４％、１６％の面
積率で形成されたパンチドニッケル基板に実施例１と同
様なペーストを塗布した。この時、前記ペーストは前記
巻始め端部側の無地部を除いてパンチング部を含む巻終
わり端部側の無地部の５０％の部分が被覆されるように
塗布した。この後、前記ペースト塗布パンチドニッケル
基板を乾燥し、加圧成形することによって負極を作製し
た。次いで、前記負極を用いた以外、実施例１と同様な
方法によりニッケル水素二次電池を製造した。Example 2 First, a punched nickel substrate having band-shaped uncoated portions formed at the winding start end and the winding end end with an area ratio of 4% and 16%, respectively, was the same as in Example 1. The paste was applied. At this time, the paste was applied so as to cover 50% of the uncoated portion on the winding end end including the punched portion except for the uncoated portion on the winding start end side. Thereafter, the paste-coated punched nickel substrate was dried and pressed to form a negative electrode. Next, a nickel-hydrogen secondary battery was manufactured in the same manner as in Example 1 except that the above-described negative electrode was used.
【００３３】（実施例３）まず、巻始め端部および巻終
わり端部側に帯状の無地部がそれぞれ１６％、４％の面
積率で形成されたパンチンドニッケル基板に実施例１と
同様なペーストを塗布した。この時、前記ペーストは前
記巻終わり端部側の無地部を除いてパンチド部を含む巻
始め端部側の無地部の５０％の部分が被覆されるように
塗布した。この後、前記ペースト塗布パンチンドニッケ
ル基板を乾燥し、加圧成形することによって負極を作製
した。次いで、前記負極を用いた以外、実施例１と同様
な方法によりニッケル水素二次電池を製造した。(Embodiment 3) First, a punched nickel substrate having band-shaped uncoated portions formed at the winding start end and the winding end end with an area ratio of 16% and 4%, respectively, is the same as that of the first embodiment. The paste was applied. At this time, the paste was applied so as to cover 50% of the uncoated portion on the winding start end including the punched portion except for the uncoated portion on the winding end end. Thereafter, the paste-coated punched nickel substrate was dried and pressed to form a negative electrode. Next, a nickel-hydrogen secondary battery was manufactured in the same manner as in Example 1 except that the above-described negative electrode was used.
【００３４】（比較例１）まず、全体が穴あけ加工され
たパンチドニッケル基板に実施例１と同様なペーストを
塗布し、乾燥した後、加圧成形することによって負極を
作製した。次いで、この負極を用いた以外、実施例１と
同様な方法によりニッケル水素二次電池を製造した。(Comparative Example 1) First, a paste similar to that of Example 1 was applied to a punched nickel substrate which had been entirely punched, dried, and then pressed to form a negative electrode. Next, a nickel-hydrogen secondary battery was manufactured in the same manner as in Example 1 except that this negative electrode was used.
【００３５】実施例１〜３および比較例１において、１
０００個のニッケル水素二次電池をそれぞれ製造し、負
極の巻始め端部側の負極層の剥離および巻終わり端部側
の負極層の剥離を調べた。その結果を下記表１に示す。
なお、負極の巻始め端部側の負極層の剥離および巻終わ
り端部側の負極層の剥離は、次のような試験により行っ
た。In Examples 1 to 3 and Comparative Example 1, 1
000 nickel-metal hydride secondary batteries were manufactured, and the peeling of the negative electrode layer on the winding start end side and the peeling of the negative electrode layer on the winding end end side of the negative electrode were examined. The results are shown in Table 1 below.
In addition, peeling of the negative electrode layer on the winding start end side and peeling of the negative electrode layer on the winding end end side of the negative electrode were performed by the following test.
【００３６】１）負極の巻始め端部側の負極層の剥離 電極群の巻回時には、巻始め端部側に巻き芯が存在する
ため、電極群の作製直後ではその個所での剥離の有無を
調べることができない。しかしながら、有底円筒状容器
内に収納する直前に前記巻き芯を引き抜くために、前記
巻始め端部で負極層の剥離が発生すれば、その剥離片は
脱落して前記容器底部に落下する。このため、電池の組
み立て後に封口板等を除去し、さらに前記容器内の電極
群を除去した後、Ｘ線粉末回折法により前記容器底部内
の主に水素吸蔵合金からなる剥離片を有無を調べた。1) Peeling of the negative electrode layer at the winding start end of the negative electrode At the time of winding the electrode group, there is a core at the winding start end side. Can not find out. However, if the negative electrode layer is peeled off at the winding start end in order to pull out the winding core immediately before being housed in the bottomed cylindrical container, the peeled piece falls off and falls to the container bottom. For this reason, after assembling the battery, after removing the sealing plate and the like, and further removing the electrode group in the container, the presence or absence of a peeled piece mainly made of a hydrogen storage alloy in the bottom of the container is examined by X-ray powder diffraction. Was.
【００３７】２）負極の巻終わり端部側の負極層の剥離 電池の組み立て後に封口板等を除去し、さらに前記容器
内の電極群を取り出し、電極群表面を目視して負極層の
剥離によるパンチドニッケル基板が露出している場合を
不良と評価した。2) Peeling of the negative electrode layer at the end of the negative electrode winding end After the battery was assembled, the sealing plate and the like were removed, the electrode group in the container was taken out, and the negative electrode layer was peeled off by visually observing the electrode group surface. The case where the punched nickel substrate was exposed was evaluated as defective.
【００３８】[0038]
【表１】 [Table 1]
【００３９】前記表１から明らかなように巻始め端部お
よび巻終わり端部側の穴あけされていない無地部を有す
るパンチドニッケル基板の所定部位に水素吸蔵合金を含
む負極層を被覆して形成された負極を用いて製造された
実施例１〜３の二次電池は、巻始め端部および巻終わり
端部側の負極層の剥離に起因する不良率の発生が３個以
下であり、全体が穴あけ加工されたパンチドニッケル基
板に水素吸蔵合金を含む負極層を被覆して形成された負
極を用いて製造された比較例１の二次電池に比べて不良
率の発生頻度が著しく低減されることがわかる。As is apparent from Table 1, a predetermined portion of a punched nickel substrate having an unperforated uncoated portion at the winding start end and the winding end end is formed by coating a negative electrode layer containing a hydrogen storage alloy. The secondary batteries of Examples 1 to 3 manufactured using the obtained negative electrode have a defect rate of 3 or less due to peeling of the negative electrode layer at the winding start end and the winding end end, and the total is 3 or less. The occurrence rate of the defective rate is remarkably reduced as compared with the secondary battery of Comparative Example 1 manufactured using a negative electrode formed by coating a punched nickel substrate having a perforated punched nickel substrate with a negative electrode layer containing a hydrogen storage alloy. You can see that
【００４０】[0040]
【発明の効果】以上詳述したように本発明によれば、一
対の電極群保持ブロック内での電極群の作製工程におい
て負極の巻始め端部および巻終わり端部側の負極層の剥
離に起因する不良発生を低減した高歩留まりで量産性の
優れたニッケル水素二次電池の製造方法を提供ことがで
きる。As described above in detail, according to the present invention, in the step of forming the electrode group in the pair of electrode group holding blocks, the negative electrode layer at the winding start end and the winding end end is peeled off. It is possible to provide a method of manufacturing a nickel-metal hydride secondary battery with high yield and excellent mass productivity, which reduces the occurrence of defects caused by the generation.
【図１】本発明に係るニッケル水素二次電池の製造に用
いられる負極を示す部分切欠した平面図。FIG. 1 is a partially cutaway plan view showing a negative electrode used for manufacturing a nickel-metal hydride secondary battery according to the present invention.
【図２】本発明に係るニッケル水素二次電池の製造に用
いられる負極、セパレータおよび正極からなる積層物を
示す斜視図。FIG. 2 is a perspective view showing a laminate comprising a negative electrode, a separator, and a positive electrode used for manufacturing a nickel-metal hydride secondary battery according to the present invention.
【図３】本発明に係るニッケル水素二次電池の製造にお
ける電極群の作製工程を示す断面図。FIG. 3 is a cross-sectional view showing a step of manufacturing an electrode group in the manufacture of a nickel-metal hydride secondary battery according to the present invention.
【図４】本発明方法により製造されたニッケル水素二次
電池の部分分解斜視図。FIG. 4 is a partially exploded perspective view of a nickel-metal hydride secondary battery manufactured by the method of the present invention.
１、２…無地部 ３…パンチドメタル基板、 ５…負極、 ６…セパレータ、 ７…正極、 ８…電極群、 ９…有底円筒状容器、 １１…封口板、 １４…正極端子、 ２１1 、２１2 …電極群保持ブロック。1, 2 uncoated portion 3 punched metal substrate, 5 negative electrode, 6 separator, 7 positive electrode, 8 electrode group, 9 bottomed cylindrical container, 11 sealing plate, 14 positive electrode terminal, 21 1 , 21 2 ... electrode group holding block.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 佐藤 努 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 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Tsutomu Sato 3-4-1-10 Minamishinagawa, Shinagawa-ku, Tokyo Inside Toshiba Battery Corporation
Claims (2)
ルを含む正極層を被覆した正極とパンチドメタル基板に
水素吸蔵合金を含む負極層を被覆した負極との間にセパ
レータを介在し積層する工程と、互いに水平方向に対向
して配置された一対の電極群保持ブロック内で前記積層
物を前記負極が外側に位置するように渦巻き状に巻回
し、前記一対のブロックで渦巻状の電極群の外周面を保
持する工程と、前記電極群を有底円筒状の容器内に収納
する工程とを具備したニッケル水素二次電池の製造方法
において、 前記負極は、巻始め端部および巻終わり端部側に穴あけ
されていない無地部を有するパンチドメタル基板に水素
吸蔵合金を含む負極層を前記無地部のうち少なくとも巻
終わり端部側の無地部の一部もしくは全部を除いて被覆
することにより形成されることを特徴とするニッケル水
素二次電池の製造方法。1. A process in which a separator is interposed between a positive electrode in which a positive electrode layer containing nickel hydroxide is coated on a porous alkali-resistant metal and a negative electrode in which a negative electrode layer containing a hydrogen storage alloy is coated on a punched metal substrate. And, in a pair of electrode group holding blocks arranged to face each other in a horizontal direction, the laminate is spirally wound such that the negative electrode is located outside, and the spirally wound electrode group is formed by the pair of blocks. In a method for manufacturing a nickel-metal hydride secondary battery, comprising: a step of holding an outer peripheral surface; and a step of storing the electrode group in a bottomed cylindrical container, wherein the negative electrode has a winding start end and a winding end. A negative electrode layer containing a hydrogen storage alloy is coated on a punched metal substrate having a solid portion that is not perforated on the side except for at least a part or all of the solid portion on the winding end end side of the solid portion. Method for manufacturing a nickel-hydrogen secondary battery, characterized in that it further formed.
トータル面積は、前記基板全体の面積に対して１５〜２
５％占め、巻始め端部および巻終わり端部側の前記無地
部は前記基板に対してそれぞれ３〜２０％の面積を占め
ることを特徴とする請求項１記載のニッケル水素二次電
池の製造方法。2. The total area of the uncoated portion of the punched metal substrate is 15 to 2 with respect to the entire area of the substrate.
The nickel-metal hydride secondary battery according to claim 1, wherein the uncoated portion at the winding start end and the winding end end occupies an area of 3 to 20% with respect to the substrate. Method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8270062A JPH10116626A (en) | 1996-10-11 | 1996-10-11 | Manufacture of nickel hydrogen secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8270062A JPH10116626A (en) | 1996-10-11 | 1996-10-11 | Manufacture of nickel hydrogen secondary battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH10116626A true JPH10116626A (en) | 1998-05-06 |
Family
ID=17480995
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8270062A Pending JPH10116626A (en) | 1996-10-11 | 1996-10-11 | Manufacture of nickel hydrogen secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH10116626A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010192193A (en) * | 2009-02-17 | 2010-09-02 | Sanyo Electric Co Ltd | Sealed alkaline storage battery |
| US9028995B2 (en) | 2009-11-17 | 2015-05-12 | Samsung Sdi Co., Ltd. | Secondary battery including electrode assembly having excellent jelly roll structure |
-
1996
- 1996-10-11 JP JP8270062A patent/JPH10116626A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010192193A (en) * | 2009-02-17 | 2010-09-02 | Sanyo Electric Co Ltd | Sealed alkaline storage battery |
| US9028995B2 (en) | 2009-11-17 | 2015-05-12 | Samsung Sdi Co., Ltd. | Secondary battery including electrode assembly having excellent jelly roll structure |
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