JP2000228189A - Negative electrode for alkaline storage battery and alkaline storage battery using it - Google Patents
Negative electrode for alkaline storage battery and alkaline storage battery using itInfo
- Publication number
- JP2000228189A JP2000228189A JP11028243A JP2824399A JP2000228189A JP 2000228189 A JP2000228189 A JP 2000228189A JP 11028243 A JP11028243 A JP 11028243A JP 2824399 A JP2824399 A JP 2824399A JP 2000228189 A JP2000228189 A JP 2000228189A
- Authority
- JP
- Japan
- Prior art keywords
- negative electrode
- pressing
- storage battery
- core material
- hydrogen storage
- Prior art date
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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
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- 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、アルカリ蓄電池お
よびアルカリ蓄電池用負極に関し、詳しくは大電流放電
時の放電特性に優れたアルカリ蓄電池の提供に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an alkaline storage battery and a negative electrode for the alkaline storage battery, and more particularly to the provision of an alkaline storage battery having excellent discharge characteristics when discharging a large current.
【０００２】[0002]
【従来の技術】近年、高容量のアルカリ二次電池として
ニッケル−水素蓄電池が使用されている。ニッケル−水
素蓄電池は、水素を電気化学的に吸蔵・放出できる水素
吸蔵合金を集電体に保持してなる負極と、水酸化ニッケ
ルを同じく集電体に保持してなる正極とを電気絶縁性の
セパレータを介して構成、ケース内に収容し、さらに所
定量のアルカリ電解液を注液した後、全体を密閉構造に
して組み立てられる。2. Description of the Related Art In recent years, nickel-hydrogen storage batteries have been used as high capacity alkaline secondary batteries. Nickel-hydrogen storage batteries have an electrical insulation property between a negative electrode that holds a hydrogen storage alloy capable of electrochemically storing and releasing hydrogen on a current collector and a positive electrode that also holds nickel hydroxide on the current collector. After being housed in a case through a separator and injecting a predetermined amount of an alkaline electrolyte, the whole is assembled in a closed structure.
【０００３】この電池に組み込まれる水素吸蔵合金電極
は、一般に次のように製造される。[0003] The hydrogen storage alloy electrode to be incorporated in this battery is generally manufactured as follows.
【０００４】水素吸蔵合金と、カーボン粉末やニッケル
粉末に代表される導電材、メチルセルロース、カルボキ
シメチルセルロースに代表される増粘剤、スチレン−ブ
タジエンゴム、ポリエチレンに代表される結着剤、イオ
ン交換水や蒸留水を混合、練合し、所定粘度の合剤ペー
ストを調製する。そして、パンチングメタル（多孔板）
やエキスパンドメタル（ネット）のような集電芯材の両
面に、上記した合剤ペーストを塗布した後、乾燥し、全
体をロールプレスして所定の厚みに調整することによっ
て水素吸蔵合金電極が得られる。A hydrogen storage alloy, a conductive material represented by carbon powder and nickel powder, a thickener represented by methylcellulose and carboxymethylcellulose, a binder represented by styrene-butadiene rubber and polyethylene, ion-exchanged water, Distilled water is mixed and kneaded to prepare a mixture paste having a predetermined viscosity. And punching metal (perforated plate)
The above-mentioned mixture paste is applied to both sides of a current collector core material such as metal or expanded metal (net), dried, roll-pressed as a whole and adjusted to a predetermined thickness to obtain a hydrogen storage alloy electrode. Can be
【０００５】[0005]
【発明が解決しようとする課題】しかしながら、このよ
うな方法により製造した水素吸蔵合金電極は、従来のニ
ッケル−カドミウム蓄電池に用いられているカドミウム
電極と比較して、高率放電時の分極が大きいという課題
を有していた。このため、電動工具、電気自動車用電源
などの大電流での放電特性が要求される分野では放電電
圧の低下が著しくなるため、十分な特性を発揮すること
が難しいと考えられていた。However, the hydrogen storage alloy electrode manufactured by such a method has a larger polarization at the time of high-rate discharge than the cadmium electrode used in the conventional nickel-cadmium storage battery. There was a problem that. For this reason, it has been considered that it is difficult to exhibit sufficient characteristics in a field such as a power tool or a power supply for an electric vehicle, which requires discharge characteristics at a large current, since the discharge voltage is significantly reduced.
【０００６】本発明は、前記のような問題点に鑑みてな
されたものであり、高率放電時の放電特性に優れたアル
カリ蓄電池並びにアルカリ蓄電池用負極を提供すること
を本発明の目的とする。The present invention has been made in view of the above-mentioned problems, and an object of the present invention is to provide an alkaline storage battery and a negative electrode for the alkaline storage battery which are excellent in discharge characteristics at high rate discharge. .
【０００７】[0007]
【課題を解決するための手段】上記目的を達成するため
に本発明では、水素吸蔵合金、結着剤および導電剤を含
むペーストを導電性芯材に塗着し、乾燥、プレスして形
成した負極とニッケル正極と、前記負極と正極との間に
介在されるセパレータと、アルカリ電解液からなるアル
カリ蓄電池において、前記負極のプレス後の多孔度を
Ｚ、前記負極のプレス後の見かけ体積をＶ、前記塗着さ
れた水素吸蔵合金の真体積をＶｍ、前記導電性芯材の真
体積をＶｓとするとき、Ｚ＝（Ｖ−Ｖｍ−Ｖｓ）／Ｖの
関係式で示される前記負極のプレス後の多孔度Ｚの値が
０．１０≦Ｚ≦０．３０となることを特徴とするアルカ
リ蓄電池としたものである。According to the present invention, a paste containing a hydrogen storage alloy, a binder and a conductive agent is applied to a conductive core material, dried and pressed. In an alkaline storage battery comprising a negative electrode, a nickel positive electrode, a separator interposed between the negative electrode and the positive electrode, and an alkaline electrolyte, the porosity of the negative electrode after pressing is Z, and the apparent volume of the negative electrode after pressing is V. When the true volume of the coated hydrogen storage alloy is Vm and the true volume of the conductive core material is Vs, the negative electrode press represented by the relational expression of Z = (V−Vm−Vs) / V An alkaline storage battery is characterized in that the value of the porosity Z satisfies 0.10 ≦ Z ≦ 0.30.
【０００８】[0008]
【発明の実施の形態】本発明の請求項１に記載の発明
は、水素吸蔵合金、結着剤および導電剤を含むペースト
を導電性芯材に塗着し、乾燥、プレスして形成したアル
カリ蓄電池用負極において、前記負極のプレス後の多孔
度をＺ、前記負極のプレス後の見かけ体積をＶ、前記塗
着された水素吸蔵合金の真体積をＶｍ、前記導電性芯材
の真体積をＶｓとするとき、Ｚ＝（Ｖ−Ｖｍ−Ｖｓ）／
Ｖの関係式で示される前記負極のプレス後の多孔度Ｚの
値が０．１０≦Ｚ≦０．３０となることを特徴とするも
のである。BEST MODE FOR CARRYING OUT THE INVENTION The invention according to claim 1 of the present invention relates to an alkali formed by applying a paste containing a hydrogen storage alloy, a binder and a conductive agent to a conductive core material, drying and pressing. In the negative electrode for a storage battery, the porosity of the negative electrode after pressing is Z, the apparent volume of the negative electrode after pressing is V, the true volume of the coated hydrogen storage alloy is Vm, and the true volume of the conductive core material is Vm. Vs, Z = (V−Vm−Vs) /
The value of the porosity Z of the negative electrode after pressing represented by the relational expression V is 0.10 ≦ Z ≦ 0.30.
【０００９】また、上記の負極を用いてアルカリ蓄電池
を構成したものである。Further, an alkaline storage battery is constituted by using the above-mentioned negative electrode.
【００１０】本発明では、負極のプレス後の多孔度Ｚと
アルカリ蓄電池の放電特性との関係に着目し、０．１０
≦Ｚ≦０．３０の関係式を満たしている場合に電池の高
率放電特性が向上することを見いだした。また、この多
孔度Ｚは、０．１５≦Ｚ≦０．２５の範囲が最も好まし
く、アルカリ蓄電池の高率放電特性がより向上する。The present invention focuses on the relationship between the porosity Z of the negative electrode after pressing and the discharge characteristics of the alkaline storage battery.
It has been found that when the relational expression of ≦ Z ≦ 0.30 is satisfied, the high rate discharge characteristics of the battery are improved. The porosity Z is most preferably in the range of 0.15 ≦ Z ≦ 0.25, and the high-rate discharge characteristics of the alkaline storage battery are further improved.
【００１１】すなわち、負極の多孔度Ｚが０．１より小
さい場合は、負極内部への電解液の拡散性が阻害される
ため、水素吸蔵合金と電解液との反応性が低下し、電池
としての反応抵抗が増大する。また、負極の多孔度Ｚが
０．３より大きい場合は、活物質同士の密着性が低下す
るため活物質粒子間の導電性が低下する。That is, when the porosity Z of the negative electrode is smaller than 0.1, the diffusivity of the electrolytic solution into the negative electrode is hindered, so that the reactivity between the hydrogen storage alloy and the electrolytic solution decreases, and Reaction resistance increases. When the porosity Z of the negative electrode is larger than 0.3, the adhesion between the active materials decreases, and the conductivity between the active material particles decreases.
【００１２】したがって、アルカリ蓄電池の高率放電特
性は負極板の多孔度に依存し、上記の多孔度Ｚの関係式
を満たす多孔度の負極を用いた電池を構成した場合に高
率放電特性が最適化されたアルカリ蓄電池を提供するこ
とができる。Therefore, the high-rate discharge characteristics of the alkaline storage battery depend on the porosity of the negative electrode plate, and when a battery using a negative electrode having a porosity satisfying the above relational expression of the porosity Z is formed, the high-rate discharge characteristics become poor. An optimized alkaline storage battery can be provided.
【００１３】また、負極は、水素吸蔵合金の芯材片面へ
のプレス後の塗着厚みをｔ、導電性芯材の厚みをＴとす
るとき、ｔ／Ｔ＜２．２の関係式を満たしている場合に
は芯材から活物質全体に至るまでの集電性が向上するた
め、アルカリ蓄電池の高率放電特性をより向上させるこ
とができる。The negative electrode satisfies the relational expression of t / T <2.2, where t is the coating thickness of the hydrogen storage alloy on one side of the core after pressing, and T is the thickness of the conductive core. In this case, the current collection from the core material to the entire active material is improved, so that the high-rate discharge characteristics of the alkaline storage battery can be further improved.
【００１４】また、水素吸蔵合金粉末を予め、ｐＨ２．
０〜４．０程度の弱酸中に浸漬し、合金表面に生成する
絶縁性の希土類水酸化物層を除去することによって負極
の活性化処理を行うことでき、これにより、さらにアル
カリ蓄電池の高率放電特性を向上させることができる。In addition, the hydrogen storage alloy powder is prepared in advance at pH 2.
The negative electrode can be activated by immersing it in a weak acid of about 0 to 4.0 to remove the insulating rare earth hydroxide layer formed on the surface of the alloy. Discharge characteristics can be improved.
【００１５】[0015]
【実施例】以下に本発明を実施例に基づいてさらに詳細
に説明するが、本発明は下記実施例に限定されるもので
なく、その要旨を変更しない範囲において適宜変更して
実施することが可能なものである。EXAMPLES The present invention will be described below in more detail with reference to examples, but the present invention is not limited to the following examples and can be carried out by appropriately changing the scope of the invention without changing its gist. It is possible.
【００１６】（実施例１）組成がＭｍＮｉ4.0Ｃｏ0.4Ａ
ｌ0.3Ｍｎ0.3である水素吸蔵合金を機械粉砕して２００
メッシュ以下とした水素吸蔵合金粉末を８０℃の６Ｎの
ＫＯＨ水溶液に２時間浸漬して、この合金表面をアルカ
リエッチングし、その後、水洗、乾燥後、ＣＭＣ（カル
ボキシメチルセルロース）２重量％の水溶液をこの合金
重量に対して１５重量％、カーボンを０．５重量％加え
て攪拌し、ペースト１を調製した。Example 1 The composition is MmNi 4.0 Co 0.4 A
l 0.3 Mn 0.3 hydrogen storage alloy is mechanically pulverized to 200
The hydrogen-absorbing alloy powder having a mesh size or less is immersed in a 6N KOH aqueous solution at 80 ° C. for 2 hours to alkali-etch the surface of the alloy, washed with water and dried. Paste 1 was prepared by adding 15% by weight and 0.5% by weight of carbon with respect to the alloy weight and stirring.
【００１７】次にこのペースト１を導電性芯材２である
厚さ３０μｍもしくは６０μｍのパンチングメタル（鉄
製芯材の表面にニッケルメッキを行ったもの）の両面に
塗布し、９０〜１１０℃で乾燥した後、ロールプレスし
て負極３を作製する。このときの負極３の圧延強度を調
整することにより、（表１）に示すようなプレス後の多
孔度Ｚの異なる負極３ａ〜３ｐを作製した。負極３ａ〜
３ｐを所定の寸法に切断し、理論容量２８００ｍＡｈを
有するニッケル−水素蓄電池のＫＲ２３／４３サイズ用
の負極３ａ〜３ｐを作製した。Next, this paste 1 is applied to both surfaces of a 30 μm or 60 μm thick punched metal (iron core material whose surface is nickel-plated), which is a conductive core material 2, and dried at 90 to 110 ° C. After that, the roll is pressed to produce the negative electrode 3. By adjusting the rolling strength of the negative electrode 3 at this time, negative electrodes 3a to 3p having different porosity Z after pressing as shown in (Table 1) were produced. Negative electrode 3a-
3p was cut into a predetermined size to produce negative electrodes 3a to 3p for a KR23 / 43 size nickel-hydrogen storage battery having a theoretical capacity of 2800 mAh.
【００１８】上記の負極３の模式断面図を図１に示す。
図１中、ｔは水素吸蔵合金ペースト１の芯材片面へのプ
レス後の塗着厚みを、Ｔは導電性芯材２の厚みを示す。FIG. 1 shows a schematic sectional view of the above-mentioned negative electrode 3.
In FIG. 1, t indicates the coating thickness of the hydrogen storage alloy paste 1 after pressing one surface of the core material, and T indicates the thickness of the conductive core material 2.
【００１９】負極３ａを一対の焼結式ニッケル極４と共
に親水化処理を施したポリプロピレン製不織布からなる
セパレータ５を介して捲回し、電極群を作製した。この
ような電極群と６ＮのＫＯＨと１ＮのＬｉＯＨからなる
アルカリ電解液を円筒状ケース６に収納し、ケース６の
上部を封口板７で密閉して理論容量２０００ｍＡｈのＫ
Ｒ２３／４３サイズの円筒型ニッケル−水素蓄電池Ａを
組み立てた。この電池の半裁断面図を図２に示す。The negative electrode 3a was wound together with a pair of sintered nickel electrodes 4 via a separator 5 made of a nonwoven fabric made of polypropylene which had been subjected to a hydrophilic treatment to prepare an electrode group. Such an electrode group and an alkaline electrolyte composed of 6N KOH and 1N LiOH are housed in a cylindrical case 6, the upper part of the case 6 is sealed with a sealing plate 7, and a theoretical capacity of 2000 mAh K
An R23 / 43 size cylindrical nickel-hydrogen storage battery A was assembled. FIG. 2 shows a half sectional view of this battery.
【００２０】負極３ａの代わりに負極３ｂ〜３ｐのそれ
ぞれを用いた以外は電池Ａと同様な構成とした電池Ｂ〜
Ｐをそれぞれ作製した。Batteries B to B having the same structure as battery A except that each of the anodes 3b to 3p was used instead of the anode 3a.
P was produced respectively.
【００２１】（実施例２）実施例２では、水素吸蔵合金
に対する酸による活性化処理の効果について評価を行
う。(Embodiment 2) In Embodiment 2, the effect of the activation treatment with an acid on the hydrogen storage alloy is evaluated.
【００２２】実施例１における水素吸蔵合金のアルカリ
エッチング工程の後に、水素吸蔵合金を合金１ｇに対し
て３０ｃｃ程度のｐＨ値が４．０である酢酸水溶液中に
３０分間浸漬し、純水で十分な水洗を行った。その後、
実施例１に示した方法と同様に乾燥後、ＣＭＣ水溶液を
加えて攪拌し、ペーストを調製した。After the hydrogen storage alloy alkali etching step in Example 1, the hydrogen storage alloy was immersed in an aqueous acetic acid solution having a pH value of about 30 cc and 4.0 for 1 g of the alloy for 30 minutes. Washing was performed. afterwards,
After drying in the same manner as in Example 1, a CMC aqueous solution was added and stirred to prepare a paste.
【００２３】得られたペーストを実施例１と同様に厚さ
６０μｍのパンチングメタルの両面に塗布し、乾燥後、
ロールプレスによる圧延条件を変化させることにより
（表２）に示すような多孔度Ｚの異なる理論容量２８０
０ｍＡｈの負極３ｋ〜３ｍのそれぞれを作製した。The obtained paste is applied to both sides of a punching metal having a thickness of 60 μm in the same manner as in Example 1, dried, and
By changing the rolling conditions by the roll press, the theoretical capacity 280 having different porosity Z as shown in (Table 2)
Each of 0 mAh negative electrodes 3 k to 3 m was produced.
【００２４】負極３ａの代わりに負極３ｋ〜３ｍのそれ
ぞれを用いた以外は実施例１に示した電池Ａと同様な電
池構成とした理論容量２０００ｍＡｈでＫＲ２３／４３
サイズのニッケル−水素蓄電池Ｋ〜Ｍのそれぞれを作製
した。A battery was constructed in the same manner as the battery A shown in Example 1 except that each of the negative electrodes 3k to 3m was used instead of the negative electrode 3a.
Each of the nickel-hydrogen storage batteries K to M having a size was produced.
【００２５】次に負極のプレス後の見かけ体積をＶ、水
素吸蔵合金の真体積をＶｍ、導電性芯材の真体積をＶｓ
および負極のプレス後の多孔度をＺとし、Ｚ＝（Ｖ−Ｖ
ｍ−Ｖｓ）／Ｖの式を用いて実施例１と実施例２で作製
した負極３ａ〜３ｍのプレス後の多孔度Ｚを算出し、そ
の結果を（表１）に示す。Next, the apparent volume of the negative electrode after pressing is V, the true volume of the hydrogen storage alloy is Vm, and the true volume of the conductive core material is Vs.
And the porosity of the negative electrode after pressing is Z, and Z = (V−V
The porosity Z of the negative electrodes 3a to 3m produced in Examples 1 and 2 after pressing was calculated using the equation of (m−Vs) / V, and the results are shown in Table 1.
【００２６】[0026]
【表１】 [Table 1]
【００２７】実施例１および実施例２で作製したニッケ
ル−水素蓄電池Ａ〜Ｍをそれぞれについて、２５℃の雰
囲気下で、０．２Ａの電流値で１５ｈ充電した後、２Ａ
の電流値で電池電圧１．０Ｖ至るまで放電することによ
り初充放電を行い、その後、２Ａの電流値で１．５ｈ充
電後、２Ａの電流値で１．０Ｖまで放電する充放電を１
０サイクル繰り返し、それぞれの電池の初期活性化を行
った。Each of the nickel-metal hydride storage batteries A to M manufactured in Example 1 and Example 2 was charged at a current value of 0.2 A for 15 hours in an atmosphere of 25 ° C., and then charged at 2 A.
The battery is initially charged and discharged by discharging to a battery voltage of 1.0 V at a current value of 1 A, and thereafter, is charged for 1.5 h at a current value of 2 A, and then charged and discharged at a current value of 2 A to 1.0 V.
Zero cycles were repeated to perform initial activation of each battery.
【００２８】活性化処理後のそれぞれの電池について以
下に示す高率放電特性の評価を行った。The following high-rate discharge characteristics of the batteries after the activation treatment were evaluated.
【００２９】上記の電池Ａ〜Ｍについて、まず２５℃の
雰囲気下で２Ａの電流値で１．２ｈ充電し、１ｈ休止さ
せた後、２Ａの電流値で電池電圧が１．０Ｖに達するま
で放電させた場合の放電容量（Ｄａ）と放電時の平均電
池電圧（Ｖａ）を算出した。The batteries A to M were charged at a current value of 2 A for 1.2 hours in an atmosphere of 25 ° C., paused for 1 hour, and then discharged at a current value of 2 A until the battery voltage reached 1.0 V. The discharge capacity (Da) and the average battery voltage (Va) at the time of discharge were calculated.
【００３０】続いて、電池を１ｈ休止させて電池電圧を
復帰させた後、上記と同様に２５℃の雰囲気下で２Ａの
電流値で１．２ｈ充電し、１ｈ休止させた後、１０Ａの
電流値で電池電圧が１．０Ｖに達するまで放電させた場
合の放電容量（Ｄｂ）と放電時の平均電池電圧（Ｖｂ）
を算出した。Subsequently, after the battery was suspended for 1 hour to recover the battery voltage, the battery was charged at a current value of 2 A in an atmosphere of 25 ° C. for 1.2 hours in the same manner as described above, suspended for 1 hour, and then discharged for 10 A. Discharge capacity (Db) when the battery is discharged until the battery voltage reaches 1.0 V in value and average battery voltage (Vb) at the time of discharge
Was calculated.
【００３１】高率放電特性は、このときの（放電容量の
比（％））＝（（Ｄｂ）／（Ｄａ））×１００と（放電
時の平均電池電圧の差）＝（Ｖａ）−（Ｖｂ）の値によ
り評価を行い、放電容量の比が大きく、放電時の平均電
池電圧の差が小さいほど、大電流放電時の容量低下や電
池電圧低下の少ない高率放電特性に優れた電池であると
判断でき、これらの算出した結果と負極のプレス後の多
孔度Ｚを（表２）に示す。The high rate discharge characteristics are as follows: (discharge capacity ratio (%)) = ((Db) / (Da)) × 100 and (difference in average battery voltage during discharge) = (Va) − ( Vb) was evaluated based on the value of the battery. The larger the discharge capacity ratio and the smaller the difference in the average battery voltage during discharge, the smaller the battery capacity and the battery voltage during large current discharge. It can be determined that there is, and the calculated results and the porosity Z of the negative electrode after pressing are shown in (Table 2).
【００３２】[0032]
【表２】 [Table 2]
【００３３】（表２）より明らかなように高率放電特性
は、負極のプレス後の多孔度Ｚに依存し、多孔度Ｚが
０．１〜０．３の範囲が好ましく、０．１５〜０．２５
の場合に最も高率放電特性が向上する。As is clear from Table 2, the high rate discharge characteristics depend on the porosity Z of the negative electrode after pressing, and the porosity Z is preferably in the range of 0.1 to 0.3, and is preferably in the range of 0.15 to 0.35. 0.25
In the case of (1), the highest rate discharge characteristics are most improved.
【００３４】また、水素吸蔵合金の塗着厚み（ｔ）と芯
材厚み（Ｔ）がｔ／Ｔ＜２．２の関係を満たす３ｊ〜３
ｎは３ｂ〜３ｆと比較してより高率放電特性が優れてい
る。Further, the coating thickness (t) of the hydrogen storage alloy and the core material thickness (T) satisfy the relationship of t / T <2.2.
n is superior in high-rate discharge characteristics as compared with 3b to 3f.
【００３５】さらに、水素吸蔵合金に酢酸水溶液による
酸処理を実施した３ｑ、３ｒ、３ｓは酸処理を行ってい
ない３ｋ、３ｌ、３ｍと比較してそれぞれさらに高率放
電特性が向上していることが確認できる。Furthermore, 3q, 3r, and 3s obtained by subjecting the hydrogen storage alloy to an acid treatment with an acetic acid aqueous solution show that the high-rate discharge characteristics are further improved as compared with 3k, 3l, and 3m not subjected to the acid treatment. Can be confirmed.
【００３６】上記実施例では、水素吸蔵合金としてＭｍ
Ｎｉ4.0Ｃｏ0.4Ａｌ0.3Ｍｎ0.3の組成で示される合金を
用いたが、使用される水素吸蔵合金はこれに限定される
ものではない。In the above embodiment, the hydrogen storage alloy was Mm
Although an alloy represented by the composition of Ni 4.0 Co 0.4 Al 0.3 Mn 0.3 was used, the hydrogen storage alloy used is not limited to this.
【００３７】また、上記実施例では、ニッケル−水素蓄
電池に用いる正極として焼結式ニッケル極を用いたが、
スポンジ状ニッケル多孔性基体に活物質である水酸化ニ
ッケルを充填した構造に代表される非焼結式ニッケル極
を用いても同様の効果が得られる。In the above embodiment, the sintered nickel electrode was used as the positive electrode used in the nickel-hydrogen storage battery.
Similar effects can be obtained by using a non-sintered nickel electrode typified by a structure in which a nickel sponge-like porous substrate is filled with nickel hydroxide as an active material.
【００３８】さらに、上記実施例では活性化処理に用い
る酸として酢酸を使用したが、塩酸、シュウ酸、オキソ
酸などの他の酸を用いても同様の効果が得られる。Further, in the above embodiment, acetic acid was used as the acid used for the activation treatment. However, similar effects can be obtained by using other acids such as hydrochloric acid, oxalic acid and oxo acid.
【００３９】[0039]
【発明の効果】以上述べたように本発明によれば、電動
工具や電気自動車用電源などの大電流放電が求められる
用途に適した高率放電特性に優れたアルカリ蓄電池用負
極およびこれを用いたアルカリ蓄電池を得ることができ
る。As described above, according to the present invention, a negative electrode for an alkaline storage battery having excellent high-rate discharge characteristics suitable for an application requiring a large current discharge, such as a power tool or a power supply for an electric vehicle, and the use of the same. The obtained alkaline storage battery can be obtained.
【図１】本発明の実施例における負極のプレス後の模式
断面図FIG. 1 is a schematic cross-sectional view after a negative electrode is pressed in an example of the present invention.
【図２】同ニッケル−水素蓄電池の半裁断面図FIG. 2 is a half sectional view of the nickel-hydrogen storage battery.
１ 水素吸蔵合金ペースト ２ 導電性芯材 ３ 負極 ４ 焼結式ニッケル正極 ５ セパレータ ６ 電池ケース ７ 封口板 DESCRIPTION OF SYMBOLS 1 Hydrogen storage alloy paste 2 Conductive core material 3 Negative electrode 4 Sintered nickel positive electrode 5 Separator 6 Battery case 7 Sealing plate
───────────────────────────────────────────────────── フロントページの続き (72)発明者 飯田 琢磨 大阪府門真市大字門真1006番地 松下電器 産業株式会社内 (72)発明者 吉井 史彦 大阪府門真市大字門真1006番地 松下電器 産業株式会社内 Ｆターム(参考） 5H016 AA02 AA05 AA10 BB02 BB05 BB08 CC03 EE01 EE09 HH02 HH06 HH08 HH13 5H028 AA02 AA05 BB03 BB04 BB05 EE01 EE06 HH01 HH03 HH05 HH06 ──────────────────────────────────────────────────の Continuing on the front page (72) Inventor Takuma Iida 1006 Kazuma Kadoma, Osaka Pref. Matsushita Electric Industrial Co., Ltd. Terms (reference) 5H016 AA02 AA05 AA10 BB02 BB05 BB08 CC03 EE01 EE09 HH02 HH06 HH08 HH13 5H028 AA02 AA05 BB03 BB04 BB05 EE01 EE06 HH01 HH03 HH05 HH06
Claims (12)
むペーストを導電性芯材の両面に塗着し、乾燥、プレス
して形成したアルカリ蓄電池用負極において、前記負極
のプレス後の多孔度をＺ、前記負極のプレス後のみかけ
体積をＶ、前記塗着された水素吸蔵合金の真体積をＶ
ｍ、前記導電性芯材の真体積をＶｓとするとき、 Ｚ＝（Ｖ−Ｖｍ−Ｖｓ）／Ｖ の関係式で示される前記負極のプレス後の多孔度Ｚの値
が０．１０≦Ｚ≦０．３０となることを特徴とするアル
カリ蓄電池用負極。1. A negative electrode for an alkaline storage battery formed by applying a paste containing a hydrogen storage alloy, a binder and a conductive agent to both surfaces of a conductive core material, and drying and pressing the same. The porosity is Z, the apparent volume of the negative electrode after pressing is V, and the true volume of the coated hydrogen storage alloy is V
m, when the true volume of the conductive core material is Vs, the value of the porosity Z of the negative electrode after pressing represented by the relational expression of Z = (V−Vm−Vs) / V is 0.10 ≦ Z ≦ 0.30, the negative electrode for an alkaline storage battery.
ス後の塗着厚みをｔ、導電性芯材の厚みをＴとすると
き、 ｔ／Ｔ＜２．２ の関係式を満たしていることを特徴とする請求項１記載
のアルカリ蓄電池用負極。2. The negative electrode satisfies the relational expression of t / T <2.2, where t is the thickness of the coated hydrogen storage alloy on one surface of the core material after pressing, and T is the thickness of the conductive core material. The negative electrode for an alkaline storage battery according to claim 1, wherein
酸中に浸漬して活性化処理が行われることを特徴とする
請求項１記載のアルカリ蓄電池用負極。3. The negative electrode for an alkaline storage battery according to claim 1, wherein the hydrogen storage alloy is activated by immersing it in a weak acid having a pH of 2.0 to 4.0.
むペーストを導電性芯材の両面に塗着し、乾燥、プレス
して形成したアルカリ蓄電池用負極において、前記負極
のプレス後の多孔度をＺ、前記負極のプレス後のみかけ
体積をＶ、前記塗着された水素吸蔵合金の真体積をＶ
ｍ、前記導電性芯材の真体積をＶｓとするとき、Ｚ＝
（Ｖ−Ｖｍ−Ｖｓ）／Ｖの関係式で示される前記負極の
プレス後の多孔度Ｚの値が０．１５≦Ｚ≦０．２５とな
ることを特徴とするアルカリ蓄電池用負極。4. A negative electrode for an alkaline storage battery formed by applying a paste containing a hydrogen storage alloy, a binder and a conductive agent on both surfaces of a conductive core material, and drying and pressing the same. The porosity is Z, the apparent volume of the negative electrode after pressing is V, and the true volume of the coated hydrogen storage alloy is V
m, when the true volume of the conductive core material is Vs, Z =
A negative electrode for an alkaline storage battery, wherein a value of a porosity Z of the negative electrode after pressing represented by a relational expression of (V−Vm−Vs) / V is 0.15 ≦ Z ≦ 0.25.
ス後の塗着厚みをｔ、導電性芯材の厚みをＴとすると
き、 ｔ／Ｔ＜２．２ の関係式を満たしていることを特徴とする請求項４記載
のアルカリ蓄電池用負極。5. The negative electrode satisfies the relational expression of t / T <2.2, where t is the coating thickness of the hydrogen storage alloy on one surface of the core material after pressing, and T is the thickness of the conductive core material. The negative electrode for an alkaline storage battery according to claim 4, wherein:
酸中に浸漬して活性化処理が行われることを特徴とする
請求項４記載のアルカリ蓄電池用負極。6. The negative electrode for an alkaline storage battery according to claim 4, wherein the hydrogen storage alloy is activated by being immersed in a weak acid having a pH of 2.0 to 4.0.
ペーストを導電性芯材に塗着し、乾燥、プレスして形成
した負極とニッケル正極と、前記負極と正極との間に介
在されるセパレータと、アルカリ電解液からなるアルカ
リ蓄電池において、前記負極のプレス後の多孔度をＺ、
前記負極のプレス後の見かけ体積をＶ、前記塗着された
水素吸蔵合金の真体積をＶｍ、前記導電性芯材の真体積
をＶｓとするとき、 Ｚ＝（Ｖ−Ｖｍ−Ｖｓ）／Ｖ の関係式で示される前記負極のプレス後の多孔度Ｚの値
が０．１０≦Ｚ≦０．３０となることを特徴とするアル
カリ蓄電池。7. A negative electrode and a nickel positive electrode formed by applying a paste containing a hydrogen storage alloy, a binder, and a conductive agent to a conductive core material, drying and pressing, and interposed between the negative electrode and the positive electrode. Separator, in an alkaline storage battery comprising an alkaline electrolyte, the porosity of the negative electrode after pressing Z,
When the apparent volume of the negative electrode after pressing is V, the true volume of the coated hydrogen storage alloy is Vm, and the true volume of the conductive core material is Vs, Z = (V−Vm−Vs) / V Wherein the value of the porosity Z of the negative electrode after pressing represented by the following relationship is 0.10 ≦ Z ≦ 0.30.
ス後の塗着厚みをｔ、導電性芯材の厚みをＴとすると
き、 ｔ／Ｔ＜２．２ の関係式を満たしていることを特徴とする請求項７記載
のアルカリ蓄電池。8. The negative electrode satisfies the relational expression of t / T <2.2, where t is the thickness of the coated hydrogen storage alloy on one surface of the core material after pressing, and T is the thickness of the conductive core material. The alkaline storage battery according to claim 7, wherein:
酸中に浸漬して活性化処理が行われることを特徴とする
請求項７記載のアルカリ蓄電池。9. The alkaline storage battery according to claim 7, wherein the activation treatment is performed by immersing the hydrogen storage alloy in a weak acid having a pH of 2.0 to 4.0.
むペーストを導電性芯材に塗着し、乾燥、プレスして形
成した負極とニッケル正極と、前記負極と正極との間に
介在されるセパレータと、アルカリ電解液からなるアル
カリ蓄電池において、前記負極のプレス後の多孔度を
Ｚ、前記負極のプレス後の見かけ体積をＶ、前記塗着さ
れた水素吸蔵合金の真体積をＶｍ、前記導電性芯材の真
体積をＶｓとするとき、 Ｚ＝（Ｖ−Ｖｍ−Ｖｓ）／Ｖ の関係式で示される前記負極のプレス後の多孔度Ｚの値
が０．１５≦Ｚ≦０．２５となることを特徴とするアル
カリ蓄電池。10. A negative electrode and a nickel positive electrode formed by applying a paste containing a hydrogen storage alloy, a binder, and a conductive agent to a conductive core material, drying and pressing, and interposed between the negative electrode and the positive electrode. Separator, in an alkaline storage battery comprising an alkaline electrolyte, the porosity of the negative electrode after pressing Z, the apparent volume of the negative electrode after pressing V, the true volume of the coated hydrogen storage alloy Vm, When the true volume of the conductive core material is Vs, the value of the porosity Z of the negative electrode after pressing represented by the relational expression of Z = (V−Vm−Vs) / V is 0.15 ≦ Z ≦ 0. 25. An alkaline storage battery, characterized in that:
レス後の塗着厚みをｔ、導電性芯材の厚みをＴとすると
き、 ｔ／Ｔ＜２．２ の関係式を満たしていることを特徴とする請求項１０記
載のアルカリ蓄電池。11. The negative electrode satisfies the relational expression of t / T <2.2, where t is the thickness of the coated hydrogen storage alloy on one surface of the core material after pressing, and T is the thickness of the conductive core material. The alkaline storage battery according to claim 10, wherein:
弱酸中に浸漬して活性化処理が行われることを特徴とす
る請求項１０記載のアルカリ蓄電池。12. The alkaline storage battery according to claim 10, wherein the hydrogen storage alloy is activated by immersing it in a weak acid having a pH of 2.0 to 4.0.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11028243A JP2000228189A (en) | 1999-02-05 | 1999-02-05 | Negative electrode for alkaline storage battery and alkaline storage battery using it |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11028243A JP2000228189A (en) | 1999-02-05 | 1999-02-05 | Negative electrode for alkaline storage battery and alkaline storage battery using it |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2000228189A true JP2000228189A (en) | 2000-08-15 |
Family
ID=12243154
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
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| Country | Link |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110419138A (en) * | 2017-03-23 | 2019-11-05 | 松下知识产权经营株式会社 | Nickel-metal hydride battery and its manufacturing method |
-
1999
- 1999-02-05 JP JP11028243A patent/JP2000228189A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110419138A (en) * | 2017-03-23 | 2019-11-05 | 松下知识产权经营株式会社 | Nickel-metal hydride battery and its manufacturing method |
| CN110419138B (en) * | 2017-03-23 | 2022-05-24 | 松下知识产权经营株式会社 | Nickel-metal hydride battery and method for manufacturing same |
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