JP2003317723A - Electrode substrate and electrode - Google Patents
Electrode substrate and electrodeInfo
- Publication number
- JP2003317723A JP2003317723A JP2002119359A JP2002119359A JP2003317723A JP 2003317723 A JP2003317723 A JP 2003317723A JP 2002119359 A JP2002119359 A JP 2002119359A JP 2002119359 A JP2002119359 A JP 2002119359A JP 2003317723 A JP2003317723 A JP 2003317723A
- Authority
- JP
- Japan
- Prior art keywords
- substrate
- electrode
- active material
- nickel
- burr
- 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.)
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Classifications
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- 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)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、ニッケル箔を用い
た電極用基板、より詳しくは二次電池、特にニッケル水
素電池やニッケルカドミウム電池の電極用基板として好
適な基板とこの基板を用いた二次電池に用いて好適な電
極に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a substrate for an electrode using a nickel foil, more specifically, a substrate suitable for a secondary battery, particularly an electrode substrate for a nickel hydrogen battery or a nickel cadmium battery, and a substrate using this substrate. The present invention relates to an electrode suitable for use in a secondary battery.
【０００２】[0002]
【従来の技術】近年、小型の二次電池は、携帯電話、コ
ードレスフォーン、デジタルカメラ、ノートパソコン、
ＰＤＡ等の携帯用電子機器、電動工具および電気自動車
（ＨＥＶ，ＭＥＶ）等に使用されている。2. Description of the Related Art In recent years, small secondary batteries have been used in mobile phones, cordless phones, digital cameras, notebook computers,
It is used in portable electronic devices such as PDAs, electric tools, electric vehicles (HEV, MEV), and the like.
【０００３】従来、前記ニッケル水素電池の正極用基板
には、発泡樹脂に導電処理およびニッケルめっきを施し
た後、樹脂のみを加熱除去して多孔質化させた発泡ニッ
ケル（以後、発泡ニッケル基板という）、負極用基板に
は、普通鋼箔にポンチを用いて多数の孔を穿った後にニ
ッケルめっきを施したパンチングメタル（以後、パンチ
ングメタル基板という）が多用されている。Conventionally, for the positive electrode substrate of the nickel-hydrogen battery, a foamed resin is subjected to a conductive treatment and nickel plating, and then only the resin is removed by heating to make the foamed nickel (hereinafter referred to as a foamed nickel substrate). ), A punching metal (hereinafter referred to as a punching metal substrate) in which a large number of holes are punched in a plain steel foil and then nickel plating is performed is often used as the negative electrode substrate.
【０００４】また、ニッケルカドミウム電池の正極用基
板には、前記の発泡ニッケル、またはパンチングメタル
基板面にニッケル粉の多孔質な焼結処理層を形成させた
基板（以後、パンチングメタル焼結基板という）、負極
用基板には前記のパンチングメタルまたはパンチングメ
タル焼結基板が多用されている。Further, as a positive electrode substrate of a nickel-cadmium battery, a substrate having a porous sintered treatment layer of nickel powder or nickel powder formed on the surface of a punching metal substrate (hereinafter referred to as a punching metal sintered substrate). ), The punching metal or punching metal sintered substrate is often used as the negative electrode substrate.
【０００５】なお、ニッケル水素電池の正極用の発泡ニ
ッケル基板には、酸化コバルトまたは金属コバルト等を
添加した活物質の水酸化ニッケルを充填、乾燥処理して
担持させ、負極用のパンチングメタル基板には、活物質
の水素吸蔵合金を塗布、乾燥処理して担持させている。A nickel foam metal substrate for a positive electrode of a nickel-hydrogen battery is filled with nickel hydroxide, which is an active material containing cobalt oxide or metallic cobalt, and dried to be supported to form a punching metal substrate for a negative electrode. Is coated with a hydrogen storage alloy as an active material, dried, and supported.
【０００６】一方、ニッケルカドミウム電池の正極用の
発泡ニッケル基板には、酸化コバルトまたは金属コバル
ト等を添加した活物質の水酸化ニッケルを充填、乾燥処
理して担持させ、パンチングメタル焼結基板には、硝酸
コバルトを添加した硝酸ニッケルの水溶液を含浸させた
後、アルカリ処理を施し、硝酸ニッケルを活物質の水酸
化ニッケルに変化させて担持させている。また、負極用
のパンチングメタル基板には、ペースト状の酸化カドミ
ウムを塗布後、還元処理を施し、酸化カドミウムを活物
質の金属カドミウムに変化させて担持させ、パンチング
メタル焼結基板には、硝酸カドミウムを含浸させた後、
アルカリ処理と還元処理を施して硝酸カドミウムを活物
質の金属カドミウムに変化させて担持させている。On the other hand, a foamed nickel substrate for a positive electrode of a nickel-cadmium battery is filled with nickel hydroxide, which is an active material containing cobalt oxide or metallic cobalt, and dried to be supported. After impregnating an aqueous solution of nickel nitrate to which cobalt nitrate is added, alkali treatment is performed to convert nickel nitrate to nickel hydroxide as an active material and carry it. In addition, the punching metal substrate for the negative electrode is coated with paste-like cadmium oxide and then subjected to a reduction treatment to change the cadmium oxide into the metal cadmium of the active material and carry it.The punching metal sintered substrate has cadmium nitrate. After impregnating
Cadmium nitrate is converted to metal cadmium as an active material by carrying out alkali treatment and reduction treatment and carried.
【０００７】上記のような二次電池には、より一層の小
型、軽量化、高性能（高容量、高出力、高寿命）化、低
価格化の要求が高まっている。また、昨今はリサイクル
性も重要視されるようになっている。For the secondary battery as described above, there are increasing demands for smaller size, lighter weight, higher performance (high capacity, high output, long life) and lower price. Also, recently, recyclability has become more important.
【０００８】これらの要求を満たすためには、使用する
電極用基板のさらなる薄肉化、高電導率化、活物質の充
填、含浸、塗布性と密着性、所定の電極形状に成形する
際の加工性、電極成形後における活物質の密着性の向上
に加えて、基板が溶解液に溶出せず、しかも組立て後の
電池使用時に短絡が生じることのない電極を得ることが
できる安価な基板であることが必要である。In order to meet these requirements, the thickness of the electrode substrate to be used is further increased, the electrical conductivity is increased, the active material is filled and impregnated, the coatability and the adhesion are improved, and the processing for forming into a predetermined electrode shape is performed. In addition to improving the electrical conductivity and the adhesion of the active material after forming the electrode, it is an inexpensive substrate that can obtain an electrode that does not elute the substrate into the solution and does not cause a short circuit during use of the battery after assembly. It is necessary.
【０００９】特に、電動工具に使用されている従来のニ
ッケルカドミウム電池およびニッケル水素電池は満足の
いくものでなく、さらなる高容量化、高出力化および高
寿命化の要求が強い。In particular, the conventional nickel-cadmium battery and nickel-hydrogen battery used for electric power tools are not satisfactory, and there is a strong demand for higher capacity, higher output and longer life.
【００１０】また、電気自動車（ＨＥＶ，ＭＥＶ）に
は、ニッケル水素電池が使われているが、小型化、高性
能化および低価格化の要求が特に強い。Although nickel-metal hydride batteries are used in electric vehicles (HEV, MEV), there are particularly strong demands for downsizing, higher performance and lower prices.
【００１１】しかし、従来のニッケル水素電池やニッケ
ルカドミウム電池に使用されている電極用基板には以下
の問題がある。すなわち、発泡ニッケル基板は、その製
造工程が複雑なため、コストが高い。活物質を充填、乾
燥、加圧圧縮加工して担持させると硬くなって脆くな
り、所定形状の電極への成形加工が困難で小型化対応が
難しい。また、この基板は比較的高容量であるが、発泡
形状であるため、ニッケル箔に比べて電気抵抗が大き
く、高出力化に限界がある。さらに、繊維状であるた
め、所定の形状に成形後の電極表面に発泡ニッケルの一
部が露出して電池組立後の使用時に短絡が発生しやす
い。However, the electrode substrate used in the conventional nickel-hydrogen battery or nickel-cadmium battery has the following problems. That is, the cost of the foamed nickel substrate is high because the manufacturing process is complicated. When the active material is filled, dried, pressed and compressed, and carried, it becomes hard and brittle, and it is difficult to form an electrode having a predetermined shape and it is difficult to reduce the size. Further, although this substrate has a relatively high capacity, since it has a foamed shape, it has a large electric resistance as compared with nickel foil, and there is a limit to achieving high output. Furthermore, since it is fibrous, a part of the nickel foam is exposed on the surface of the electrode after being formed into a predetermined shape, and a short circuit is likely to occur during use after battery assembly.
【００１２】パンチングメタルは、孔が「バリなし孔」
であるために活物質の密着力が十分でなく、所定形状の
電極への成形時に活物質の一部が剥離脱落し、高い電池
性能が確保できない。これにはニッケルめっきが施され
ているが、導電性が小さいため、高出力化に限界があ
る。また、電解質の水酸化カリウム水溶液中に鉄イオン
が溶出し、電池寿命が低下するという危険性が高い。近
年、電池性能の向上、軽量化要求に対応するために薄肉
化が進められているが、圧延法による鋼箔の製造では、
圧延途中での軟化処理が必須なため、薄肉化するほどコ
ストが高くなる。The punching metal has a "burr-free hole".
Therefore, the adhesion of the active material is not sufficient, and a part of the active material peels off during molding into an electrode having a predetermined shape, and high battery performance cannot be ensured. Although this is nickel-plated, it has a limit to increase the output because of its low conductivity. Further, there is a high risk that iron ions will be eluted into the aqueous potassium hydroxide solution of the electrolyte and the battery life will be shortened. In recent years, in order to meet demands for improved battery performance and weight reduction, thinning has been promoted, but in the production of steel foil by the rolling method,
Since softening treatment is essential during rolling, the cost increases as the wall thickness decreases.
【００１３】パンチングメタル焼結基板は、表面がニッ
ケル粉の多孔質な焼結処理層（Ｆｅ−Ｎｉ合金層）であ
るため、パンチングメタルよりも活物質の密着性は高い
ものの、導電性が悪い。Since the surface of the punched metal sintered substrate is a porous sintered layer (Fe-Ni alloy layer) of nickel powder on the surface, the active material has higher adhesiveness than the punched metal, but the conductivity is poor. .
【００１４】活物質の密着性を向上させるようにした実
用に供しうる電極用基板としては、厚さ２５〜１６０μ
ｍのニッケル等の金属板または金属箔からなり、孔のな
い集電部と周囲にバリを有する多数の孔を穿った多孔部
とからなる電極用基板が提案されている（例えば、特開
平７−１３０３７０号公報、同７−３３５２０８号公
報、同７−３３５２０９号公報および同９−１２０８１
９号公報、参照）。A practical electrode substrate for improving the adhesion of the active material has a thickness of 25 to 160 μm.
There has been proposed an electrode substrate made of a metal plate or metal foil of nickel or the like having a diameter of m and having a current collecting portion having no holes and a porous portion having a large number of holes having burrs in the periphery (for example, Japanese Patent Laid-Open Publication No. 7-58242). -130370 publication, 7-335208 publication, 7-335209 publication, and 9-12081 publication.
No. 9, gazette).
【００１５】しかし、上記の各公報に示される電極用基
板は、いずれも、多孔部の全ての孔の間隔が均一であ
る。このため、穿孔加工の際に孔部と集電部の境界近傍
に座屈や亀裂が生じやすく、特に孔部の幅が３０ｍｍ以
上の場合には加工歩留が低く、実用上問題のあることが
わかった。However, in all of the electrode substrates shown in the above publications, the intervals of all the holes in the porous portion are uniform. Therefore, during drilling, buckling or cracks are likely to occur near the boundary between the hole and the current collector, and especially when the width of the hole is 30 mm or more, the processing yield is low and there is a practical problem. I understood.
【００１６】[0016]
【発明が解決しようとする課題】本発明の課題は、穿孔
加工時に孔部と集電部の境界部分に座屈や亀裂が生じに
くく、加工歩留を向上させることが可能で、安価かつ高
性能な電極用基板と電極を提供することにある。The object of the present invention is to prevent buckling or cracking at the boundary between the hole and the current collecting portion during drilling, to improve the processing yield, and to reduce the cost and cost. It is to provide a high-performance electrode substrate and electrode.
【００１７】[0017]
【課題を解決するための手段】本発明の要旨は、下記
（１）の電極用基板、および下記（２）の電極にある。
（１）電解析出法で製造された厚さ８〜３０μｍのニッ
ケル箔であって、孔のない集電部、多孔部およびこれら
両部の間の中間部を有し、中間部の開孔率が多孔部の開
孔率Ｘから開孔率ゼロの集電部にかけて漸減しており、
前記多孔部および中間部の孔は穿孔時のバリを残した電
極用基板。
（２）上記（１）の電極用基板の両面に、活物質を担持
させた電極。The gist of the present invention resides in the following electrode substrate (1) and the following electrode (2). (1) A nickel foil having a thickness of 8 to 30 μm produced by an electrolytic deposition method, which has a current collecting part without holes, a porous part and an intermediate part between these parts, and has an opening in the intermediate part. The porosity gradually decreases from the porosity X of the porous portion to the current collector where the porosity is zero,
The porous substrate and the hole in the middle portion are electrode substrates in which burrs are left during drilling. (2) An electrode in which an active material is supported on both surfaces of the electrode substrate of (1) above.
【００１８】上記（１）に記載した本発明の電極用基板
は、孔の穿孔加工前または穿孔加工後の表面にニッケル
粉の多孔質な焼結処理層を形成させたものであるこのが
好ましい。The electrode substrate of the present invention described in (1) above is preferably one in which a porous sintered layer of nickel powder is formed on the surface before or after perforation processing of holes. .
【００１９】また、上記（２）に記載した本発明の電極
は、片面側に担持させた活物質の厚さＴ（ｍｍ）とバリ
の高さｈ（ｍｍ）との関係が下記（ａ）式を満たすか、
または／および活物質を担持させる直前の電極用基板の
引張強さが５００ＭＰａ以下であることが好ましい。
ｈ＜Ｔ≦２．５×ｈ ・・・・・（ａ）。Further, in the electrode of the present invention described in the above (2), the relationship between the thickness T (mm) of the active material supported on one side and the height h (mm) of the burr is as follows (a). Satisfies the formula,
Or / and the tensile strength of the electrode substrate immediately before supporting the active material is preferably 500 MPa or less. h <T ≦ 2.5 × h (a).
【００２０】[0020]
【発明の実施の形態】以下、本発明の電極用基板と二次
電池用電極について詳細に説明する。最初に、本発明の
電極用基板について説明する。BEST MODE FOR CARRYING OUT THE INVENTION The electrode substrate and secondary battery electrode of the present invention will be described in detail below. First, the electrode substrate of the present invention will be described.
【００２１】本発明において、素材として電解析出法で
製造された厚さ８〜３０μｍのニッル箔を用いることと
したのは次の理由による。In the present invention, the reason why the Ni foil having a thickness of 8 to 30 μm manufactured by the electrolytic deposition method is used as the material is as follows.
【００２２】素材の材質は、導電性がよいこと、すなわ
ち電気抵抗が小さいことが必要である。ニッケルは、表
１に示すように、純鉄、ステンレス鋼等の鋼やＦｅ−Ｎ
ｉ合金よりも電気抵抗が小さく、金や銀よりも安価であ
り、銅のように電解液の水酸化カリウム水溶液に溶出す
る恐れがなく、またその箔の電気抵抗は発泡ニッケルよ
りも小さい。It is necessary that the material of the material has good conductivity, that is, has a low electric resistance. As shown in Table 1, nickel is steel such as pure iron or stainless steel or Fe-N.
It has a lower electric resistance than the i alloy, is cheaper than gold and silver, does not have the risk of being eluted into an aqueous potassium hydroxide solution of the electrolytic solution like copper, and has a lower electric resistance than foamed nickel.
【００２３】[0023]
【表１】 [Table 1]
【００２４】代表的な箔の製造方法には、圧延法と電解
析出法がある。圧延法で薄くするためには、軟化焼鈍を
介在させた圧延を繰り返すことが必要で、箔厚が薄いも
のほどその繰り返し回数の増大が必須となり、製造コス
トが嵩む。このため、小型、軽量化を安価に達成する素
材として不適切である。Typical foil manufacturing methods include a rolling method and an electrolytic deposition method. In order to reduce the thickness by the rolling method, it is necessary to repeat the rolling with the softening annealing interposed, and the thinner the foil thickness, the more the number of times of repetition is required, which increases the manufacturing cost. For this reason, it is unsuitable as a material that achieves small size and light weight at low cost.
【００２５】これに対して、電解析出法は、半円弧状に
成形された陽極に対向して配置された陰極を兼ねる回転
ドラムとの間隙部分に電解液を供給し、回転ドラムの表
面に順次析出付着するニッケル箔を連続して剥ぎ取る方
法であり、箔厚が薄いものほど安価に製造できる。この
ため、小型、軽量化を安価に達成する素材として最適で
ある。On the other hand, in the electrolytic deposition method, the electrolytic solution is supplied to the surface of the rotary drum by supplying the electrolytic solution to the gap between the anode formed in the shape of a semicircle and the rotary drum which also functions as the cathode. This is a method of continuously peeling off nickel foil that is deposited and adhered one by one, and the thinner the foil is, the cheaper it can be manufactured. Therefore, it is most suitable as a material that can be made small and lightweight at low cost.
【００２６】ただし、箔厚が８μｍ未満では、剛性が不
足し、箔の製造ラインおよび後述する穿孔加工を施す基
板製造ラインでの取り扱いが困難である。また、箔厚が
３０μｍを超えると、穿孔加工に用いる針の寿命が短く
なるだけでなく、圧延法とのコスト差が小さくなって経
済的な優位性を失う。However, if the foil thickness is less than 8 μm, the rigidity is insufficient, and it is difficult to handle it on the foil production line and the substrate production line for carrying out the perforation processing described later. Further, if the foil thickness exceeds 30 μm, not only the life of the needle used for the punching process is shortened, but also the cost difference from the rolling method becomes small, and the economical advantage is lost.
【００２７】以上の理由から、本発明では素材として電
解析出法で製造された厚さ８〜３０μｍのニッケル箔を
用いることとした。好ましい箔厚は１０〜２５μｍであ
る。For the above reasons, in the present invention, the nickel foil having a thickness of 8 to 30 μm manufactured by the electrolytic deposition method is used as the material. A preferable foil thickness is 10 to 25 μm.
【００２８】次に、本発明の電極用基板の形状について
説明する。Next, the shape of the electrode substrate of the present invention will be described.
【００２９】図１は、本発明の電極用基板の左半分（左
右対称）を示す平面図で、図に示すように、幅Ｌのニッ
ケル箔１のうち、端部Ｌ１ の領域は孔のない集電部
２、中央部のＬ３ の領域は孔５の穿孔ピッチが幅方向
に一定で開孔率（％）がＸの多孔部４、集電部２と多孔
部４の間のＬ２ の領域は孔５の穿孔ピッチが集電部２
に向かって増大する全体の開孔率（％）がＹの中間部３
に成形されている。FIG. 1 is a plan view showing the left half (left-right symmetry) of the electrode substrate of the present invention. As shown in the drawing, in the nickel foil 1 having a width L, the region at the end L 1 is a hole. no collector portion 2, porosity at a constant perforation pitch in the width direction of the region of L 3 of the central part hole 5 (%) is X porous portion 4, L between the collector portion 2 and the porous part 4 In the region 2 of FIG.
The total open area ratio (%) increases toward Y.
Is molded into.
【００３０】すなわち、本発明の電極用基板の最大の特
徴は、集電部２と多孔部４の間に、孔５の穿孔ピッチが
集電部２に向かって順次増大する、言い換えれば、その
幅方向の開孔率が多孔部４の開孔率Ｘから開孔率ゼロの
集電部にかけて漸減する中間部３があることである。こ
の中間部３では、全体の開孔率Ｙが前記多孔部４の開孔
率Ｘよりも小さい。That is, the greatest feature of the electrode substrate of the present invention is that the pitch of the holes 5 between the current collecting portion 2 and the porous portion 4 gradually increases toward the current collecting portion 2, in other words, That is, there is an intermediate portion 3 whose porosity in the width direction gradually decreases from the porosity X of the porous portion 4 to the current collecting portion where the porosity is zero. In the intermediate portion 3, the overall porosity Y is smaller than the porosity X of the porous portion 4.
【００３１】このように、集電部２と多孔部４の間に中
間部３を設けた場合には、孔がなくて強度の高い集電部
２と、孔５が多くて強度の低い多孔部４の間に、両者の
強度の中間強度帯域が形成される。その結果、孔のない
集電部２とその近傍の孔明き部分の剛性が増し、集電部
２と孔明き部分との境界部分に座屈が生じるのが効果的
に抑制され、破断しなくなる。As described above, when the intermediate portion 3 is provided between the current collecting portion 2 and the porous portion 4, the current collecting portion 2 having no holes and having high strength, and the porous portion having many holes 5 and having low strength. An intermediate intensity band of both intensities is formed between the parts 4. As a result, the rigidity of the current collecting portion 2 having no hole and the perforated portion in the vicinity thereof is increased, buckling is effectively suppressed at the boundary portion between the current collecting portion 2 and the perforated portion, and no fracture occurs. .
【００３２】図２は、中間部３における開孔率Ｙの漸減
パターンの代表的な例を示す図である。開孔率の変化
は、同図（ａ）のＰ１、同（ｂ）のＰ２、同（ｃ）のＰ
３および同（ｄ）のＰ４のいずれのパターンであっても
よい。しかし、穿孔工具の作製容易性の面からすると、
Ｐ４のパターンとするのが好ましい。FIG. 2 is a diagram showing a typical example of the gradual decrease pattern of the aperture ratio Y in the intermediate portion 3. The change in porosity is as follows: P1 in the same figure, P2 in the same figure, P in the same figure,
3 or P4 of the same (d) may be used. However, in terms of the ease of making a drilling tool,
The pattern of P4 is preferable.
【００３３】上記Ｐ１、Ｐ２、Ｐ３およびＰ４のパター
ンは、多孔部４の開孔率Ｘが小さい場合はいずれのパタ
ーンを適用しても何ら問題ないが、開孔率Ｘが大きなも
のにＰ４のパターンを適用する場合には、その分割段数
を多くすることが肝要で、例えば、開孔率Ｘが３０％を
超えるようなものの場合、隣り合う段の間の開孔率差を
およそ１０％以下にすることが望ましい。With respect to the patterns P1, P2, P3 and P4, there is no problem in applying any pattern when the porosity X of the porous portion 4 is small. When applying a pattern, it is important to increase the number of division stages. For example, when the aperture ratio X exceeds 30%, the difference in aperture ratio between adjacent stages is about 10% or less. Is desirable.
【００３４】多孔部４の開孔率Ｘは１０〜５０％、中間
部３の平均開孔率Ｙは開孔率Ｘの０．３〜０．７倍とす
るのが望ましい。多孔部４の開孔率Ｘが１０％未満の場
合には、活物質の密着性が低く、正極に用いた場合には
集電性が低下し、負極に用いた場合には、イオンの移動
抵抗が増大してその通過性が悪化する。逆に、５０％を
超える場合には孔同士が互いにくっついて正常な配列パ
ターンにならないことがあり、基板としての強度が低下
する。また、正極用としては断面積が小さくなりすぎ、
高出力時に基板が部分的に溶損するという危険性が大き
くなる。なお、より望ましい開孔率Ｘは２０〜４０％で
ある。The porosity X of the porous portion 4 is preferably 10 to 50%, and the average porosity Y of the intermediate portion 3 is preferably 0.3 to 0.7 times the porosity X. When the porosity X of the porous portion 4 is less than 10%, the adhesion of the active material is low, when the positive electrode is used, the current collecting property is reduced, and when it is used for the negative electrode, the migration of ions is reduced. The resistance increases and the passability deteriorates. On the other hand, if it exceeds 50%, the holes may stick to each other and a normal array pattern may not be formed, and the strength as a substrate decreases. Also, the cross-sectional area becomes too small for the positive electrode,
There is a greater risk that the substrate will partially melt at high power. The more desirable porosity X is 20 to 40%.
【００３５】中間部３の平均開孔率Ｙが多孔部４の開孔
率Ｘの０．３倍未満の場合には、中間部に対する活物質
の密着性が劣るとともに、塗布した場合における集電部
の活物質の密着性も低下しやすい。逆に、０．７倍を超
えると、集電部と孔部（中間部）の境界で座屈や亀裂が
発生しやすく、その結果電池性能の不良を招く。When the average porosity Y of the intermediate portion 3 is less than 0.3 times the porosity X of the porous portion 4, the adhesion of the active material to the intermediate portion is poor, and the current collection when applied is large. The adhesiveness of the active material in some parts is also likely to decrease. On the other hand, if it exceeds 0.7 times, buckling or cracking is likely to occur at the boundary between the current collecting portion and the hole portion (intermediate portion), resulting in poor battery performance.
【００３６】中間部３の幅Ｌ２ は特に制限しないが、
最低でも多孔部４の幅Ｌ３の０．１倍以上とし、最大１
０ｍｍ以下とするのが望ましい。これは、幅Ｌ２ が幅
Ｌ３の０．１倍に満たない場合には前記の効果がほとん
ど得られず、中間部３を設ける意味がなく、１０ｍｍを
超えるほど広くしても前記の効果は変わらず、かえって
電池性能の低下を招く恐れがあるからである。The width L 2 of the intermediate portion 3 is not particularly limited,
At least 0.1 times the width L 3 of the porous portion 4 and at most 1
It is desirable to set it to 0 mm or less. This is because if the width L 2 is less than 0.1 times the width L 3 , the above-mentioned effect is hardly obtained, and there is no point in providing the intermediate portion 3, and even if the width is wider than 10 mm, the above-mentioned effect is obtained. This is because there is a possibility that the battery performance may be deteriorated.
【００３７】多孔部４および中間部３の孔５の配列パタ
ーンは、図１の（ａ）のように並列配列、同じく図１の
（ｂ）のように千鳥状配列のいずれであってもよいが、
高い開孔率とする場合は後者の千鳥状配列とするのが好
ましい。The arrangement pattern of the porous portions 4 and the holes 5 of the intermediate portion 3 may be either a parallel arrangement as shown in FIG. 1 (a) or a staggered arrangement as shown in FIG. 1 (b). But,
In the case of high porosity, the latter staggered arrangement is preferred.
【００３８】図３は、孔５の断面を示す図である。図示
のように、孔５は周囲にバリ６を有している。この周囲
にバリ６を有する孔５は、先端形状が例えば円錐状の所
定長さの針等を用いて明けることができる。すなわち、
上記Ｌ２ およびＬ３ の領域に相当する部分に所定の
穿孔ピッチをもってニッケル箔１の長手方向（図１の上
下方向）に複数列配置して保持させた治具を用いて穿孔
加工するのである。FIG. 3 is a view showing a cross section of the hole 5. As shown, the hole 5 has a burr 6 on its periphery. The hole 5 having the burr 6 on the periphery thereof can be opened by using, for example, a needle having a conical tip and a predetermined length. That is,
Punching is performed using a jig that is arranged and held in a plurality of rows in the longitudinal direction (vertical direction in FIG. 1) of the nickel foil 1 with a predetermined punching pitch in a portion corresponding to the region of L 2 and L 3 . .
【００３９】バリ６を有する孔５は、図３の（ａ）のよ
うにニッケル箔１の片面側のみから穿孔したもの、同じ
く図３の（ｂ）のように両面側から穿孔したもののいず
れであってもよい。しかし、電極成形に先立ってその両
面に担持させる活物質の密着性を高める観点からは両面
側から穿孔した孔である方が好ましい。The hole 5 having the burr 6 is formed by piercing only one surface side of the nickel foil 1 as shown in FIG. 3A or is similarly pierced by both surface sides as shown in FIG. 3B. It may be. However, from the viewpoint of enhancing the adhesiveness of the active material to be supported on both surfaces of the electrode prior to forming the electrode, it is preferable that the holes are perforated from both sides.
【００４０】孔５をニッケル箔１の両面側から穿孔する
場合には、前記針の配設ピッチをニッケル箔１の幅方向
または長手方向に、例えば上記穿孔ピッチの２倍のピッ
チで配置した治具を２つ準備し、治具相互の針が干渉し
ないようにニッケル箔１を挟んで対向配置して穿孔すれ
ばよい。When the holes 5 are drilled from both sides of the nickel foil 1, the needles are arranged in the width direction or the longitudinal direction of the nickel foil 1 at, for example, a pitch twice the above pitch. Two tools may be prepared, and the nickel foil 1 may be sandwiched between the jigs so that the needles of the jigs do not interfere with each other.
【００４１】孔５の穿孔加工は、ニッケル箔１に対す針
の押し込み量の制御等によりバリ６の先端部が周方向に
少なくとも４つ以上に割れるように加工するのが望まし
い。これは、バリ６の先端部が割れている場合、活物質
に対する集電部位面積が増大するとともに、その密着性
も向上するからである。It is desirable that the holes 5 be drilled so that the tip of the burr 6 is broken into at least four or more pieces in the circumferential direction by controlling the pushing amount of the needle with respect to the nickel foil 1. This is because when the tip portion of the burr 6 is broken, the area of the current collecting site with respect to the active material is increased and its adhesion is also improved.
【００４２】孔５の径ｄは０．２〜１．０ｍｍ、厚さが
ｔのニッケル箔１の薄厚中央からバリ６の先端までの高
さｈ（以下、単に「バリの高さｈ」という…図３参照）
は０．１〜０．５ｍｍとするのが望ましい。その理由は
次のとおりである。The diameter d of the hole 5 is 0.2 to 1.0 mm, and the height h from the thin center of the nickel foil 1 having a thickness t to the tip of the burr 6 (hereinafter, simply referred to as "burr height h"). (See Figure 3)
Is preferably 0.1 to 0.5 mm. The reason is as follows.
【００４３】孔５の径ｄが０．２ｍｍ未満であると、穿
孔加工が難しいだけでなく、望ましいバリ６の高さｈお
よび多孔部４の開孔率Ｘの確保が困難になる。逆に、
１．０ｍｍを超える場合は、バリ６の高さｈが望ましい
高さ以上に高くなりやすい。孔５のより望ましい径ｄは
０．３〜０．７ｍｍである。If the diameter d of the hole 5 is less than 0.2 mm, not only is it difficult to form a hole, but also it is difficult to secure the desired height h of the burr 6 and the aperture ratio X of the porous portion 4. vice versa,
If it exceeds 1.0 mm, the height h of the burr 6 tends to be higher than the desired height. The more desirable diameter d of the hole 5 is 0.3 to 0.7 mm.
【００４４】また、バリ６の高さｈが０．１ｍｍ未満で
あると、活物質の密着性が低く、正極に使用した場合、
活物質の電子電導性が低下する。逆に、０．５ｍｍを超
えると、後述する活物質７を担持させた状態での基板の
厚さが厚くなりすぎ、電池の成形時に基板を所定の長さ
分だけ巻き込むことができなくなることがある。より望
ましいバリ６の高さｈは０．１５〜０．３５ｍｍであ
る。When the height h of the burr 6 is less than 0.1 mm, the adhesion of the active material is low, and when used for the positive electrode,
The electron conductivity of the active material is reduced. On the other hand, when the thickness exceeds 0.5 mm, the thickness of the substrate in which the active material 7 described later is carried becomes too thick, and the substrate cannot be wound by a predetermined length during the molding of the battery. is there. The more desirable height h of the burr 6 is 0.15 to 0.35 mm.
【００４５】図４は、先端部がニッケル箔１の面に対面
する先端曲折バリ６ａを模式的に示した断面図である。
この先端曲折バリ６ａは、孔５の穿孔加工後にロール圧
延等すること等で容易に得られる。このように、バリを
先端曲折バリ６ａにした場合には、バリの高さｈが均一
になり、基板表面に活物質を担持させた際、一部のバリ
が活物質の表面に露出する恐れがほとんどなく、短絡の
問題を容易に解決できる。また、バリ先端部の内径が大
きくなってその断面形状が円弧状となるので、先端の曲
折部分との相乗作用により、活物質の密着性が一段と向
上する。このため、バリは先端が曲折したバリにする方
が好ましい。FIG. 4 is a cross-sectional view schematically showing a tip bending burr 6a whose tip portion faces the surface of the nickel foil 1.
The tip bending burr 6a can be easily obtained by rolling the hole 5 after the boring process. In this way, when the burr is formed by the tip bending burr 6a, the height h of the burr becomes uniform, and when the active material is carried on the substrate surface, a part of the burr may be exposed on the surface of the active material. The problem of short circuit can be easily solved. Further, since the inner diameter of the burr tip portion becomes large and its cross-sectional shape becomes an arc shape, the synergistic action with the bent portion of the tip further improves the adhesion of the active material. Therefore, it is preferable that the burr has a bent tip.
【００４６】なお、孔５の平面形状は図示例の円形に限
らず、例えば、楕円形、正方形、長方形、三角形、その
他の多角形のいずれであってもよい。しかし、穿孔用の
針の製作性等を考慮した場合、円形とするのが好まし
い。なお、円形以外の孔とする場合、その孔の断面積が
径ｄの円形の孔の断面積と実質的に同じ大きさの孔とす
ることが肝要である。また、楕円形や長方形の孔の場
合、長径（辺）／短径（辺）比が大きすぎるものは好ま
しくないので、その比が２．０以下の孔とすることが望
ましい。The planar shape of the hole 5 is not limited to the circular shape shown in the drawing, but may be any of an elliptical shape, a square shape, a rectangular shape, a triangular shape and other polygonal shapes. However, considering the manufacturability of the needle for punching, etc., it is preferable to make it circular. When the hole has a non-circular shape, it is important that the cross-sectional area of the hole is substantially the same as the cross-sectional area of the circular hole having the diameter d. In the case of an elliptical or rectangular hole, it is not preferable that the ratio of major axis (side) / minor axis (side) is too large, so that the ratio is preferably 2.0 or less.
【００４７】以上に説明した本発明の電極用基板は、常
法に従って、その表面にニッケル粉の多孔質な焼結処理
層を形成させたものとする方が好ましい。これは、前記
の焼結処理層を形成させた場合には、その表面に担持さ
せる活物質の含浸性および充填性がよくなって密着性が
格段に向上するからである。その結果、活物質を担持さ
せた基板を所定形状の電極に加工する際の活物質の剥離
脱落量が大幅に減少する。また、従来のパンチングメタ
ル焼結基板のように、その表層部分にＦｅ−Ｎｉ合金層
が生成することがない。このため、その表面にニッケル
粉の焼結処理層を形成させた基板とする場合には、格段
に高性能な電池の提供が可能となる。It is preferable that the electrode substrate of the present invention described above has a porous sintered treatment layer of nickel powder formed on its surface according to a conventional method. This is because, when the above-mentioned sintered treatment layer is formed, the impregnation property and filling property of the active material supported on the surface are improved, and the adhesion property is remarkably improved. As a result, the amount of peeling and dropping of the active material when the substrate supporting the active material is processed into the electrode having a predetermined shape is significantly reduced. Further, unlike the conventional punched metal sintered substrate, no Fe—Ni alloy layer is formed on the surface layer portion. Therefore, when a substrate having a nickel powder sintering treatment layer formed on the surface thereof is used, it is possible to provide a battery with significantly high performance.
【００４８】なお、ニッケル粉の焼結処理層は、孔の穿
孔加工前のニッケル箔１に予め形成させてもよいし、穿
孔加工を行った後の基板に形成させてもよい。しかし、
活物質の密着性および電池性能を高める観点から、基板
の全ての表面にニッケル粉の焼結処理層を形成させたも
のの方が好ましいので、穿孔加工後の基板に形成させる
のがよい。The nickel powder sintering layer may be formed in advance on the nickel foil 1 before perforating the holes, or may be formed on the substrate after perforating. But,
From the viewpoint of enhancing the adhesiveness of the active material and the battery performance, it is preferable to form a sintered treatment layer of nickel powder on the entire surface of the substrate, and therefore it is preferable to form it on the substrate after perforation processing.
【００４９】本発明の電極は、図５に示すように、以上
に説明した電極用基板の表面に、厚さがＴ（ｍｍ）の所
望の活物質７を担持させたものである。担持させる活物
質７の厚さＴとバリ６の高さｈ（ｍｍ）とは、式「ｈ＜
Ｔ≦２．５×ｈ」を満たすものであることが望ましい。
また、活物質７を担持させる直前の基板（ニッケル箔
１）の引張強さは５００ＭＰａ以下であることが望まし
い。その理由は次のとおりである。ここで、上記の厚さ
Ｔとは、基板の表面に後に例示するような工程によって
処理して担持させた後の厚さのことである。As shown in FIG. 5, the electrode of the present invention is obtained by supporting a desired active material 7 having a thickness of T (mm) on the surface of the electrode substrate described above. The thickness T of the active material 7 to be carried and the height h (mm) of the burr 6 are expressed by the formula “h <
It is desirable that T ≦ 2.5 × h ”is satisfied.
The tensile strength of the substrate (nickel foil 1) immediately before supporting the active material 7 is preferably 500 MPa or less. The reason is as follows. Here, the above-mentioned thickness T is the thickness after the substrate is processed and carried by a process as exemplified later.
【００５０】活物質の厚さＴがバリの高さｈの２．５倍
以下、言いかえれば、バリの高さｈが活物質の厚さＴの
０．４倍以上でない場合には、活物質の基板に対する密
着性が十分でない。また、Ｔがｈより薄いと活物質の表
面にバリが露出して短絡を招くだけでなく、活物質がバ
リの先端部まで十分に入らず、所望の電池性能を確保す
ることが困難になる。When the thickness T of the active material is 2.5 times or less the height h of the burr, in other words, when the height h of the burr is not 0.4 times or more the thickness T of the active material, the activity is The adhesion of the substance to the substrate is not sufficient. If T is thinner than h, burrs are exposed on the surface of the active material to cause a short circuit, and the active material does not sufficiently enter the tip of the burrs, which makes it difficult to secure desired battery performance. .
【００５１】なお、Ｔは特に制限しないが、１．２５ｍ
ｍ以下とするのが望ましい。これは、Ｔを１．２５ｍｍ
よりも厚くすると、前述したように、活物質を担持させ
た状態での基板の厚さが厚くなりすぎて電池の成形時に
基板を所定の長さ分だけ巻き込むことができなくなる場
合があるからである。Ｔの好ましい上限は１．００ｍｍ
である。Although T is not particularly limited, it is 1.25 m.
It is desirable that the thickness is m or less. This is T 1.25mm
If it is thicker than the above, as described above, the thickness of the substrate with the active material supported becomes too thick, and it may not be possible to wrap the substrate for a predetermined length during molding of the battery. is there. The preferable upper limit of T is 1.00 mm
Is.
【００５２】また、バリ６を片面側のみに形成させた場
合における他方面に担持させる活物質の厚さＴ１ （図
５の（ａ）参照）は、特に制限しないが、Ｔの０．２〜
１倍とするのがよい。The thickness T 1 (see FIG. 5A) of the active material carried on the other surface when the burr 6 is formed on only one surface is not particularly limited, but is 0.2 of T. ~
It is better to multiply by 1.
【００５３】さらに、活物質を担持させる直前の基板
（ニッケル箔１）の引張強さとして５００ＭＰａ以下が
望ましいのは、５００ＭＰａを超えると、活物質の密着
性が低下して層間抵抗が増大し、所望の電池性能を確保
することが困難になるためである。好ましいのは４００
ＭＰａ以下である。なお、下限は特に制限しないが、あ
まり弱いと、穿孔加工時に幅方向の両端部分を板押さ等
でクランプした際、箔の形状が不良になったり、場合に
よっては破断する恐れがあるので、５０ＭＰａ以上であ
ることがよい。Further, the tensile strength of the substrate (nickel foil 1) immediately before supporting the active material is preferably 500 MPa or less. When it exceeds 500 MPa, the adhesion of the active material is lowered and the interlayer resistance is increased. This is because it becomes difficult to secure desired battery performance. 400 is preferred
It is below MPa. The lower limit is not particularly limited, but if it is too weak, the shape of the foil may become defective or may be broken in some cases when the widthwise end portions are clamped by plate pressing or the like. The above is preferable.
【００５４】以下、本発明の代表的な電極とその製造工
程を例示する。
(Ａ)ニッケル水素電池用電極；
(1)正極（活物質は水酸化ニッケル）：本発明の基板
（ニッケル粉の焼結処理層形成基板を含む）に、水酸化
ニッケルを金属コバルトまたは酸化コバルトとの混合物
として含浸、充填、あるいは塗布後、乾燥、加圧圧縮加
工して担持させる。
(2)負極（活物質は水素吸蔵合金）：正極と同様の基板
に、水素吸蔵合金を含浸、充填、あるいは塗布後、乾
燥、加圧圧縮加工して担持させる。
(Ｂ) ニッケルカドミウム電池用電極；
(1)正極（活物質は水酸化ニッケル）：本発明の基板の
うち、ニッケル粉の焼結処理層形成基板に、硝酸コバル
トと硝酸ニッケルとの水溶液を含浸後アルカリ処理を施
し、活物質化（水酸化ニッケルにする）させて担持させ
る。
(2)負極（活物質は金属カドミウム）その１：正極と同
様のニッケル粉の焼結処理層形成基板に、硝酸カドミウ
ムを含浸後、アルカリ処理と還元処理を施し、活物質化
（金属カドミウムにする）させて担持させる。
(3)負極（活物質は金属カドミウム）その２：本発明の
基板のうち、ニッケル粉の焼結処理層を有しない基板
に、酸化カドミウムのペーストを塗布後還元処理を施
し、活物質化（金属カドミウムにする）させて担持させ
る。The representative electrodes of the present invention and the manufacturing process thereof will be illustrated below. (A) Electrode for nickel-hydrogen battery; (1) Positive electrode (active material is nickel hydroxide): Nickel hydroxide is added to metallic cobalt or cobalt oxide on the substrate of the present invention (including a substrate for forming a sintered layer of nickel powder). After being impregnated, filled, or applied as a mixture with, the product is dried, pressure-compressed, and supported. (2) Negative electrode (active material is hydrogen storage alloy): The same substrate as the positive electrode is impregnated with, filled with, or coated with a hydrogen storage alloy, dried, and pressed and processed to be supported. (B) Electrode for nickel-cadmium battery; (1) Positive electrode (active material is nickel hydroxide): Among the substrates of the present invention, a substrate for forming a sintered layer of nickel powder is impregnated with an aqueous solution of cobalt nitrate and nickel nitrate. After that, it is subjected to an alkali treatment to be an active material (made into nickel hydroxide) and supported. (2) Negative electrode (metal cadmium is the active material) Part 1: The same nickel powder sintered treatment layer forming substrate as the positive electrode is impregnated with cadmium nitrate and then subjected to alkali treatment and reduction treatment to become the active material (metal cadmium). To be carried. (3) Negative electrode (active material is metallic cadmium) Part 2: Of the substrates of the present invention, a substrate not having a sintering treatment layer of nickel powder is coated with a paste of cadmium oxide and then subjected to a reduction treatment to become an active material ( Metal cadmium) to support.
【００５５】[0055]
【実施例】全幅Ｌが３９ｍｍで、厚さｔが種々異なる電
解Ｎｉ箔を準備した。そして、集電部の幅Ｌ１ がいず
れも２ｍｍ（両側で４ｍｍ）で、他の条件（孔の径ｄ、
中間部の幅Ｌ２ と開孔率Ｙ、多孔部の幅Ｌ３ と開孔
率Ｘ、バリの高さｈ、バリ先端部の分割数と屈曲の有
無、活物質を担持させる直前の引張強さ）が、表２〜５
に示すように、種々異なる２１種類の基板（試験番号１
〜５、７〜１１、１３、１５、１６、１８および２０〜
２６）と、比較のための中間部を有しない基板（試験番
号６、１２、１４、１７、１９および２７）および孔部
がない基板（試験番号２８）を製作した。EXAMPLE Electrolytic Ni foils having a total width L of 39 mm and different thickness t were prepared. The width L 1 of the current collector is 2 mm (4 mm on both sides), and other conditions (diameter d of the hole,
Width L 2 and porosity Y of the intermediate portion, width L 3 and porosity X of the porous portion, height h of the burr, the number of divisions of the burr tip and the presence or absence of bending, and the tensile strength immediately before supporting the active material. Is Tables 2-5
21 different types of substrates (Test No. 1
~ 5, 7-11, 13, 15, 16, 18 and 20-
26), and a substrate having no intermediate portion (test numbers 6, 12, 14, 17, 19, and 27) and a substrate having no hole portion (test number 28) for comparison.
【００５６】なお、中間部の孔のパターンは、図２に示
すパターンＰ４とし、幅Ｌ２ を３等分するとともに、
各部間の開孔率の差をいずれも△Ｙにし、集電部に近い
部分の開孔率を（Ｙ−△Ｙ）、中央部分の開孔率をＹ、
多孔部に近い部分の開孔率を（Ｙ＋△Ｙ）とすることに
より、平均の開孔率がＹになるように穿孔加工した。The pattern of the holes in the middle portion is the pattern P4 shown in FIG. 2, and the width L 2 is divided into three equal parts.
The difference in the open area ratio between the respective parts is ΔY, the open area ratio of the part close to the current collecting part is (Y−ΔY), the open area ratio of the central part is Y,
By setting the open area ratio of the portion close to the porous portion to (Y + ΔY), punching was performed so that the average open area ratio was Y.
【００５７】穿孔加工後の基板は、長さ４００ｍｍの短
冊状の基板に切断した後、これを目視観察して座屈の有
無、孔と孔との間の亀裂や割れの有無を調べ、その穿孔
性を次の基準により評価するとともに、製作コスト比較
も行った。
〔穿孔性の評価基準〕
○：亀裂や割れおよび座屈が全く認められなかったも
の、
△：亀裂や割れおよび座屈の発生箇所が１〜５箇所のも
の、
×：亀裂や割れおよび座屈の発生箇所が５箇所を超える
もの。
〔製作コスト比較〕
１：発泡Ｎｉと同等、
２：発泡Ｎｉの０．７〜１倍、
３：発泡Ｎｉの０．７倍未満。The substrate after perforation processing was cut into a strip-shaped substrate having a length of 400 mm, and then visually observed to check for buckling, cracks between holes, and cracks. The piercing property was evaluated according to the following criteria, and the manufacturing costs were also compared. [Evaluation Criteria for Perforability] ◯: No cracks, cracks and buckling were observed at all, Δ: 1-5 cracks, cracks and buckling occurrence points, ×: Cracks, cracks and buckling The number of occurrences of exceeds 5. [Production cost comparison] 1: Equivalent to foamed Ni, 2: 0.7 to 1 times that of foamed Ni, 3: Less than 0.7 times that of foamed Ni.
【００５８】前記した以外にも、比較のための基板とし
て、全幅Ｌと集電部の幅Ｌ１ が前記の寸法と同じで、
他の条件が異なる基板、即ち、箔の製造時に多孔部が形
成された電解Ｎｉ孔箔からなる基板（試験番号２９）
と、従来のパンチングメタルからなる基板（試験番号３
０〜３２）も準備した。また更に、発泡ニッケルからな
る基板（試験番号３３）も準備した。In addition to the above, as a substrate for comparison, the total width L and the width L 1 of the current collector are the same as the above dimensions,
Substrate under other conditions, that is, a substrate made of electrolytic Ni-perforated foil in which a porous portion was formed during foil production (Test No. 29)
And a conventional punching metal substrate (test number 3
0-32) was also prepared. Further, a substrate made of foamed nickel (Test No. 33) was also prepared.
【００５９】製作および比較のために準備した基板は、
試験番号１１と３３の基板を除き、その表面に、厚さが
いずれも２μｍのニッケル粉の多孔質な焼結処理層を形
成させた。この焼結処理層は、主成分が３０質量％のカ
ーボニルＮｉ粉末と、１質量％の増粘剤（カルボキシメ
チルセルロース）である水系ペーストを所定の厚みに塗
布した後、水素ガス雰囲気中で焼鈍することにより形成
させた。その際、焼結温度は９５０℃とした。The substrates prepared for fabrication and comparison were:
Except for the substrates of Test Nos. 11 and 33, a porous sintered treatment layer of nickel powder having a thickness of 2 μm was formed on each surface. The main component of this sintered layer is 30% by mass of carbonyl Ni powder and 1% by mass of a water-based paste, which is a thickener (carboxymethylcellulose), applied to a predetermined thickness and then annealed in a hydrogen gas atmosphere. Formed by. At that time, the sintering temperature was 950 ° C.
【００６０】ニッケル粉の焼結処理層を形成させた基板
は、その表面に水酸化ニッケル（Ni(OH)２）からなる種
々の厚さＴの活物質を担持させてニッケル正極用の板と
した後、以下に述べる種々の試験に供してその諸性能を
調べる一方、これらを負極がいずれも下記の負極である
電解液が飽和水酸化カリウム溶液の単２型円筒電池の正
極に組み込み、その電池性能を調べた。なお、ニッケル
正極用の板としての製作コスト比較も行った。
《負極》
基 板；材質：Ni電解箔、厚さ：20μm、全幅：39mm、
集電部の幅：２mm（両側で４mm）、多孔部の開孔率：30
％、孔径：1.5mm。
活物質；水素吸蔵合金｛MmNi５−Ｘ（Mm：Ce-La-Nd-P
r、x：Co,Mn,Al）｝、担持厚さ：両面とも0.4mm。The substrate on which the sintering treatment layer of nickel powder was formed was used as a plate for a nickel positive electrode by supporting an active material having various thicknesses T made of nickel hydroxide (Ni (OH) 2 ) on the surface thereof. After that, while performing various tests described below to investigate its various performances, these were incorporated into the positive electrode of a C2 cylindrical battery in which the electrolytic solution whose negative electrode was the following negative electrode was a saturated potassium hydroxide solution. The battery performance was examined. In addition, the manufacturing cost comparison as a plate for a nickel positive electrode was also performed. 《Negative electrode》 Base plate; Material: Ni electrolytic foil, Thickness: 20 μm, Overall width: 39 mm,
Width of current collector: 2 mm (4 mm on both sides), porosity of porous part: 30
%, Pore diameter: 1.5 mm. Active material: Hydrogen storage alloy {MmNi5 -X (Mm: Ce-La-Nd-P
r, x: Co, Mn, Al)}, supported thickness: 0.4 mm on both sides.
【００６１】水酸化ニッケル（Ni(OH)２）からなる種々
の厚さＴの活物質は、次のようにして担持させた。水酸
化ニッケル粉末１００ｇに対して、黒煙粉末１０ｇ、ニ
ッケル粉末５ｇ、コバルト粉末１０ｇ、カルボキシメチ
ルセルロースの３質量％水溶液５５ｇ、およびスチレン
−ブタジエンラバーの４８質量％水分散液５ｇを練り合
わせてペースト状にして容器に収容する。次いで、基板
をこの容器内を通過させてその両面にペーストを塗布し
た後、鋼製のスリットに通してペーストの厚さを均一に
してから乾燥処理し、その後ローラプレスすることで所
定の厚さＴにした。
〔活物質の密着性試験とその評価基準〕密着性試験は、
活物質を担持させた後の基板を曲げ角度１８０゜で曲げ
−曲げ戻す試験を５回繰り返し、試験後、活物質の脱落
面積を求め、下記の基準で評価した。
１：脱落面積が１０％を超えるもの、
２：脱落面積が２〜１０％のもの、
３：脱落面積が２％未満のもの。
〔導電性の試験とその評価基準〕導電性の試験は、
製作した単２電池について、０．１Ｃで１２時間充電
し、１時間の休止後、０．２Ｃで電圧が１Ｖになるまで
放電する操作を１サイクルとする試験を３サイクル行
い、３サイクル後の正極の活物質利用率を調べ、下記の
基準で評価した。なお、正極の活物質利用率(％)は式
「（実測放電容量／正極の活物質量から求められる理論
放電容量）×１００」により求めた。The active material made of nickel hydroxide (Ni (OH) 2 ) having various thicknesses T was supported as follows. To 100 g of nickel hydroxide powder, 10 g of black smoke powder, 5 g of nickel powder, 10 g of cobalt powder, 55 g of 3 mass% aqueous solution of carboxymethyl cellulose, and 5 g of 48 mass% aqueous dispersion of styrene-butadiene rubber were kneaded to form a paste. And put it in a container. Then, after passing the substrate through this container and applying the paste on both sides, it is passed through a slit made of steel to make the thickness of the paste uniform and then dried, and then roller-pressed to the desired thickness. I chose T. [Active material adhesion test and its evaluation criteria]
A test in which the substrate on which the active material was supported was bent and bent back at a bending angle of 180 ° was repeated 5 times. After the test, the area where the active material was dropped was obtained and evaluated according to the following criteria. 1: Dropout area exceeds 10%, 2: Dropout area is 2 to 10%, 3: Dropout area is less than 2%. [Conductivity test and its evaluation criteria] Conductivity test,
The produced AA battery is charged at 0.1C for 12 hours, after a rest of 1 hour, discharged at 0.2C until the voltage becomes 1V. One cycle is a test for 3 cycles. The utilization rate of the active material of the positive electrode was examined and evaluated according to the following criteria. The positive electrode active material utilization rate (%) was determined by the formula “(measured discharge capacity / theoretical discharge capacity determined from positive electrode active material amount) × 100”.
【００６２】１：活物質の利用率が８０％未満のもの、
２：活物質の利用率が８０〜９０％のもの、
３：活物質の利用率が９０％を超えるもの。
〔導電性の試験とその評価基準〕導電性の試験は、
上記の導電性の試験に引き続いて、０．３Ｃで４時間
充電し、１時間休止後、０．５Ｃで電圧が１Ｖになるま
で放電する操作を１サイクルとする試験を１００サイク
ル行い、１００サイクル後の正極の活物質利用率を導電
性の試験の場合と同様の方法により調べ、下記の基準
で評価した。1: Utilization rate of active material is less than 80%, 2: Utilization rate of active material is 80 to 90%, 3: Utilization rate of active material is more than 90%. [Conductivity test and its evaluation criteria] Conductivity test,
Following the above conductivity test, 100 cycles of a test in which charging is performed at 0.3C for 4 hours, after 1 hour of rest, discharge at 0.5C until the voltage becomes 1V is 100 cycles, and 100 cycles are performed. The utilization rate of the active material of the subsequent positive electrode was examined by the same method as in the case of the conductivity test, and evaluated according to the following criteria.
【００６３】１：活物質の利用率が６０％未満のもの、 ２：活物質の利用率が６０〜８０％のもの、 ３：活物質の利用率が８０％を超えるもの。1: The utilization rate of the active material is less than 60%, 2: The utilization rate of the active material is 60 to 80%, 3: Utilization rate of active material exceeds 80%.
【００６４】以上の試験結果を、基板の諸元等と併せ
て、表２〜表５に示した。The above test results are shown in Tables 2 to 5 together with the specifications of the substrate.
【００６５】[0065]
【表２】 [Table 2]
【００６６】[0066]
【表３】 [Table 3]
【００６７】[0067]
【表４】 [Table 4]
【００６８】[0068]
【表５】 [Table 5]
【００６９】表２〜表５に示すように、本発明の基板お
よびこれを用いた電極（試験番号２〜４、７〜１１、１
３、１５、１６、１８および２０〜２６）は、いずれも
良好な結果が得られている。中でも、箔の厚さが本発明
で規定する範囲内であり、孔の径ｄ、中間部の幅Ｌ２
と開孔率Ｙ、多孔部の幅Ｌ３ と開孔率Ｘ、バリの高さ
ｈ、バリ先端部の分割数と屈曲の有無、活物質を担持さ
せる直前の引張強さ、活物質の厚さＴとバリの高さｈと
の関係のいずれもが本発明で望ましいとする範囲内にあ
るもの（試験番号２〜４、７、１１、１３、１５、２０
および２２〜２５）は特に良好である。これに対し、比
較例の試験番号１、５、６、１２、１４、１７、１９お
よび２７は、孔の穿孔加工性、活物質の密着性等が劣
る。As shown in Tables 2 to 5, the substrates of the present invention and electrodes using them (test numbers 2 to 4, 7 to 11 and 1).
3, 15, 16, 18 and 20 to 26) have good results. Among them, the thickness of the foil is within the range defined by the present invention, the diameter d of the hole, and the width L 2 of the intermediate portion.
And the porosity Y, the width L 3 of the porous portion and the porosity X, the height h of the burr, the number of divisions of the burr tip and the presence or absence of bending, the tensile strength immediately before supporting the active material, and the thickness of the active material. Any of the relationship between the height T and the height h of the burr is within the range that is desirable in the present invention (test numbers 2 to 4, 7, 11, 13, 15, 20).
And 22 to 25) are particularly good. On the other hand, the test numbers 1, 5, 6, 12, 14, 17, 19 and 27 of the comparative examples are inferior in the perforation workability of pores and the adhesion of the active material.
【００７０】[0070]
【発明の効果】本発明の電極用基板は、集電部と多孔部
の間に中間部を設けたので、集電部近傍の剛性が大き
く、集電部と孔明き部の境界での座屈や破断が生じな
い。その結果、電極への成形加工を円滑に行うことがで
き、その電極を組込んだ電池は電極破損を生じる恐れが
ない。また、基板として厚さを従来以上に薄くした安価
な電解析出ニッケル箔を採用したので、活物質を多く担
持させることができ、高性能で、しかも小型、軽量で安
価な電池の提供が可能になる。In the electrode substrate of the present invention, since the intermediate portion is provided between the current collecting portion and the porous portion, the rigidity in the vicinity of the current collecting portion is large, and the seat at the boundary between the current collecting portion and the perforated portion is large. No buckling or breaking. As a result, the molding process for the electrode can be smoothly carried out, and the battery incorporating the electrode is free from the possibility of electrode damage. In addition, since a cheaper electrolytically deposited nickel foil with a thinner thickness than before was used as the substrate, it is possible to support a large amount of active material, and it is possible to provide a high-performance, compact, lightweight and inexpensive battery. become.
【図１】本発明の電極用基板例の左半分を示す平面図で
ある。FIG. 1 is a plan view showing a left half of an electrode substrate example of the present invention.
【図２】中間部の開孔率の漸減パターン例を示す図であ
る。FIG. 2 is a diagram showing an example of a gradual reduction pattern of the open area ratio of an intermediate portion.
【図３】バリの断面形状の一例を示す断面図である。FIG. 3 is a sectional view showing an example of a sectional shape of a burr.
【図４】バリの他の断面形状の一例を示す断面図であ
る。FIG. 4 is a sectional view showing an example of another sectional shape of a burr.
【図５】本発明の電極例を示す断面図である。FIG. 5 is a cross-sectional view showing an electrode example of the present invention.
１：ニッケル箔、 ２：集電部、 ３：中間部、 ４：多孔部、 ５：孔、 ６：バリ、 ６ａ：先端曲折バリ、 ７：活物質。 1: nickel foil, 2: Current collector, 3: Middle part, 4: Porous part, 5: hole, 6: Bali, 6a: tip bending burr, 7: Active material.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 瀬戸 宏久 兵庫県尼崎市扶桑町１番21号 住友金属建 材株式会社内 (72)発明者 末永 哲 兵庫県尼崎市扶桑町１番21号 住友金属建 材株式会社内 Ｆターム(参考） 5H017 AA02 AS02 BB11 BB16 CC03 DD08 EE04 HH00 HH02 HH03 ─────────────────────────────────────────────────── ─── Continued front page (72) Inventor Hirohisa Seto Sumitomo Metal Construction 1-21 Fusocho Amagasaki City Hyogo Prefecture Material Co., Ltd. (72) Inventor Satoshi Suenaga Sumitomo Metal Construction 1-21 Fusocho Amagasaki City Hyogo Prefecture Material Co., Ltd. F-term (reference) 5H017 AA02 AS02 BB11 BB16 CC03 DD08 EE04 HH00 HH02 HH03
Claims (6)
ｍのニッケル箔であって、孔のない集電部、多孔部およ
びこれら両部の間の中間部を有し、中間部の開孔率が多
孔部の開孔率Ｘから開孔率ゼロの集電部にかけて漸減し
ており、上記多孔部および中間部の孔は穿孔時のバリを
残したものであることを特徴とする電極用基板。1. The thickness produced by the electrolytic deposition method is 8 to 30 μm.
A nickel foil of m having a current collecting part without pores, a porous part and an intermediate part between these parts, and the porosity of the intermediate part is from the porosity X of the porous part to zero. A substrate for an electrode, which is gradually reduced toward the current collecting portion, and the holes in the porous portion and the intermediate portion are left with burrs at the time of punching.
とを特徴とする請求項１に記載の電極用基板。2. The electrode substrate according to claim 1, which has a sintering treatment layer of nickel powder on both surfaces.
されたものであることを特徴とする請求項２に記載の電
極用基板。3. The substrate for electrodes according to claim 2, wherein the sintering treatment layer of nickel powder is applied after perforation of the holes.
極用基板の両面に、活物質を担持させたことを特徴とす
る電極。4. An electrode characterized in that an active material is carried on both surfaces of the electrode substrate according to any one of claims 1 to 3.
ｍ）とバリの高さｈ（ｍｍ）との関係が下記（ａ）式を
満たすことを特徴とする請求項４に記載の電極。 ｈ＜Ｔ≦２．５×ｈ ・・・・・（ａ）5. The thickness T (m of the active material supported on one surface side
The electrode according to claim 4, wherein the relationship between m) and the height h (mm) of the burr satisfies the following expression (a). h <T ≦ 2.5 × h (a)
張強さが５００ＭＰａ以下であることを特徴とする請求
項４または５に記載の電極。6. The electrode according to claim 4, wherein the tensile strength of the electrode substrate immediately before supporting the active material is 500 MPa or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002119359A JP4016703B2 (en) | 2002-04-22 | 2002-04-22 | Electrode substrate and electrode |
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| JP2002119359A JP4016703B2 (en) | 2002-04-22 | 2002-04-22 | Electrode substrate and electrode |
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| JP2010238680A (en) * | 2009-03-13 | 2010-10-21 | Jm Energy Corp | Electrode for electric storage device, method of manufacturing the same, and lithium ion capacitor |
| WO2011052122A1 (en) * | 2009-10-26 | 2011-05-05 | パナソニック株式会社 | Collector and electrode for use in nonaqueous electrolyte secondary cell, nonaqueous electrolyte secondary cell, and manufacturing method thereof |
| CN109273720A (en) * | 2017-07-18 | 2019-01-25 | 福田金属箔粉工业株式会社 | Open-porous metal foil |
| JPWO2021033537A1 (en) * | 2019-08-22 | 2021-02-25 |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010238680A (en) * | 2009-03-13 | 2010-10-21 | Jm Energy Corp | Electrode for electric storage device, method of manufacturing the same, and lithium ion capacitor |
| WO2011052122A1 (en) * | 2009-10-26 | 2011-05-05 | パナソニック株式会社 | Collector and electrode for use in nonaqueous electrolyte secondary cell, nonaqueous electrolyte secondary cell, and manufacturing method thereof |
| CN102246337A (en) * | 2009-10-26 | 2011-11-16 | 松下电器产业株式会社 | Collector and electrode for use in nonaqueous electrolyte secondary cell, nonaqueous electrolyte secondary cell, and manufacturing method thereof |
| CN109273720A (en) * | 2017-07-18 | 2019-01-25 | 福田金属箔粉工业株式会社 | Open-porous metal foil |
| JP2019021495A (en) * | 2017-07-18 | 2019-02-07 | 福田金属箔粉工業株式会社 | Perforated metal foil |
| JPWO2021033537A1 (en) * | 2019-08-22 | 2021-02-25 | ||
| WO2021033537A1 (en) * | 2019-08-22 | 2021-02-25 | 富士フイルム株式会社 | Aluminum foil |
| CN114270576A (en) * | 2019-08-22 | 2022-04-01 | 富士胶片株式会社 | Aluminum foil |
| JP7190582B2 (en) | 2019-08-22 | 2022-12-15 | 富士フイルム株式会社 | aluminum foil |
| US12002965B2 (en) | 2019-08-22 | 2024-06-04 | Fujifilm Corporation | Aluminum foil |
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| JP4016703B2 (en) | 2007-12-05 |
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