JP3515286B2 - Electrodes for secondary batteries - Google Patents
Electrodes for secondary batteriesInfo
- Publication number
- JP3515286B2 JP3515286B2 JP16741896A JP16741896A JP3515286B2 JP 3515286 B2 JP3515286 B2 JP 3515286B2 JP 16741896 A JP16741896 A JP 16741896A JP 16741896 A JP16741896 A JP 16741896A JP 3515286 B2 JP3515286 B2 JP 3515286B2
- Authority
- JP
- Japan
- Prior art keywords
- active material
- composition
- nickel
- cobalt
- hydroxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、ニッケルー水素蓄
電池やニッケルーカドミウム蓄電池等のアルカリ蓄電池
や、リチウムイオン二次電池に使用される二次電池用電
極に関し、特に電気自動車などの大電流下で使用される
電池に使用されるものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an alkaline storage battery such as a nickel-hydrogen storage battery or a nickel-cadmium storage battery, or an electrode for a secondary battery used in a lithium ion secondary battery, particularly under a large current such as an electric vehicle. It is used for batteries used.
【０００２】[0002]
【従来の技術】従来、ニッケルー水素蓄電池やニッケル
ーカドミウム蓄電池等のアルカリ蓄電池のニッケル極と
しては、ニッケル金属の多孔体等からなる集電体に活物
質(水酸化ニッケル)を塗着させてなる非焼結式ニッケル
極がよく知られている。このような電極では、一般に、
電極全体の活物質塗着部が均質なものが使用されてい
る。この理由は、民生用の二次電池は一般に小型であ
り、せいぜい瞬間的に数アンペアー程度の電流が導出さ
れる程度のものであるので、充放電時の発熱という問題
に着目する必要がないからである。2. Description of the Related Art Conventionally, as a nickel electrode of an alkaline storage battery such as a nickel-hydrogen storage battery or a nickel-cadmium storage battery, an active material (nickel hydroxide) is applied to a current collector composed of a porous body of nickel metal. Non-sintered nickel electrodes are well known. With such electrodes, in general,
A uniform active material coating on the entire electrode is used. The reason for this is that the secondary battery for consumer use is generally small in size, and at most momentary, a current of several amperes is derived, so it is not necessary to pay attention to the problem of heat generation during charging and discharging. Is.
【０００３】ところが、近年、この種の二次電池により
電気自動車を駆動させるという試みがなされている。電
気自動車の電源として、二次電池を使用するためには、
かかる二次電池を電気自動車用に改良する必要が出てく
る。この種の電気自動車用の二次電池は、自動車のモー
ターへ電気を供給するとき、数アンペアー以上の大きな
電流を必要とすることが多い。However, in recent years, attempts have been made to drive an electric vehicle by means of this type of secondary battery. To use a secondary battery as a power source for an electric vehicle,
There is a need to improve such secondary batteries for electric vehicles. Secondary batteries for electric vehicles of this type often require a large current of several amperes or more when supplying electricity to the motor of the vehicle.
【０００４】この結果、電気自動車用の大型の二次電池
と、民生用の小型の二次電池との根本的な差異は、数ア
ンペアー以上の大電流が、短時間ではない時間にわたっ
て電池を介して導出されるか否かという点である。As a result, the fundamental difference between the large secondary battery for electric vehicles and the small secondary battery for consumer use is that a large current of several amperes or more passes through the battery for a short time, not a short time. The point is whether or not it is derived.
【０００５】[0005]
【発明が解決しようとする課題】本発明は、かかる問題
点を解決すべくなされたものであって、大電流を長時間
に取り出しても問題を生じない、電気自動車などに使用
される大電流用途の二次電池用正極を提案するものであ
る。ここで、大電流用途とは、５アンペアー以上の電流
が数分間以上持続して流れることを意味する。SUMMARY OF THE INVENTION The present invention has been made to solve the above problems, and a large current used in an electric vehicle or the like that does not cause a problem even if a large current is taken out for a long time. The present invention proposes a positive electrode for a secondary battery for use. Here, the high current application means that a current of 5 amperes or more continuously flows for several minutes or more.
【０００６】また、従来、大電流を導出した場合、活物
質から導電タブを介して、電極端子へ電力が供給される
が、この時に導電タブ近傍では温度が上昇し、正極の活
物質を劣化させ、電極の特性の低下をひきおこす。本発
明では、このような熱の影響を低く抑え、優れた電極特
性を発揮させるものである。Further, conventionally, when a large current is derived, electric power is supplied from the active material to the electrode terminals through the conductive tabs, but at this time, the temperature rises near the conductive tabs and the active material of the positive electrode deteriorates. This causes deterioration of the electrode characteristics. In the present invention, such an influence of heat is suppressed to a low level and excellent electrode characteristics are exhibited.
【０００７】[0007]
【課題を解決するための手段】本発明は、導電タブを有
する二次電池用正極であって、前記導電タブ近傍の第１
組成の活物質と、第２組成の活物質とが、集電体に塗着
充填されており、前記第１組成の活物質が、水酸化コバ
ルトで表面を被覆された水酸化ニッケル、または、水酸
化コバルトを水酸化ナトリウム水溶液で処理することに
より得られるナトリウム含有コバルトで表面を被覆され
た水酸化ニッケルであり、前記第２組成の活物質が、導
電剤としての水酸化コバルトが混合された水酸化ニッケ
ルであることを特徴とするものである。SUMMARY OF THE INVENTION The present invention is a positive electrode for a secondary battery having a conductive tab, wherein the first battery is provided near the conductive tab.
An active material having a composition and an active material having a second composition are coated and filled in a current collector, and the active material having the first composition is a coke hydroxide.
Nickel hydroxide or hydroxy acid coated on the surface
To treat cobalt oxide with sodium hydroxide solution
The surface is coated with the sodium-containing cobalt obtained from
Nickel hydroxide, the active material of the second composition is
Nickel hydroxide mixed with cobalt hydroxide as an electric agent
It is characterized by being
【０００８】また、本発明は、具体的には、集電体と、
導電タブと、活物質塗着部とから構成される二次電池用
正極であって、 前記導電タブに近接した集電体には第
１組成の活物質が配置され、前記配置された第１組成の
活物質に対して前記導電タブとは反対側の集電体には第
２組成の活物質が配置され、前記第１組成の活物質と前
記第２組成の活物質とが前記活物質塗着部を構成し、前
記第１組成の活物質が、水酸化コバルトで表面を被覆さ
れた水酸化ニッケル、または、水酸化コバルトを水酸化
ナトリウム水溶液で処理することにより得られるナトリ
ウム含有コバルトで表面を被覆された水酸化ニッケルで
あり、前記第２組成の活物質が、導電剤としての水酸化
コバルトが混合された水酸化ニッケルであることを特徴
とするものである。The present invention also specifically includes a current collector,
For secondary battery consisting of conductive tab and active material coating part
An active material having a first composition is disposed on a current collector that is a positive electrode and is in the vicinity of the conductive tab, and the current collector on the side opposite to the conductive tab with respect to the disposed active material having the first composition. active material of the second composition is disposed on, the active material of the first composition and the active material of the second composition constitutes the active material application portion, before
The active material of composition No. 1 has a surface coated with cobalt hydroxide.
Hydroxide of nickel hydroxide or cobalt hydroxide
Natri obtained by treatment with an aqueous sodium solution
With nickel hydroxide coated on the surface with cobalt containing um
And the active material of the second composition is hydroxylated as a conductive agent.
It is characterized in that it is nickel hydroxide mixed with cobalt .
【０００９】ここで、前記第１組成の活物質の塗布量
と、前記第２組成の活物質の塗布量との重量比率として
は、１：９〜１：４程度が好ましい。Here, the active material of the first compositionApplication amount of
And an active material of the second compositionApplication amount ofAs a weight ratio with
Is preferably about 1: 9 to 1: 4.
【００１０】[0010]
【００１１】[0011]
【発明の実施の形態】以下、本発明を実施例に基づいて
詳細に説明するが、本発明は下記実施例に何ら限定され
るものではなく、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。
（実験例）この実験例では、正極において、導電タブ近
傍の活物質即ち第１組成の活物質を導電性の高いものと
して電極を作製し、大型の角型電池を組立てて評価を行
っている。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail based on Examples, but the present invention is not limited to the following Examples, and is appropriately modified and implemented within the scope not changing the gist thereof. It is possible to do. (Experimental example) In this experimental example, in the positive electrode, an active material near the conductive tab, that is, an active material having the first composition is used as a material having high conductivity to fabricate an electrode, and a large rectangular battery is assembled and evaluated. .
【００１２】［正極の作製］まず、ここで使用した正極
について説明する。この正極においては、導電タブ近傍
の活物質を導電性の高いものとしている。この正極、即
ち二次電池用電極の形状を、図１に示す。電極は、縦10
cm、幅30cmの寸法を有した活物質塗着部と、導電タブか
らなる。この導電タブは、電極の長辺の一端側に形成さ
れている。この導電タブの寸法は、高さが１cm、幅が10
cmである。活物質塗着部の内部には、厚さ0.1mmのパン
チングメタルからなるニッケル多孔体(集電体)が配置さ
れており、導電タブは厚さ0.1mmの無孔のニッケル板で
構成されている。尚、上記ニッケル多孔体は、発泡ニッ
ケル体から構成してもよい。この場合には、舌片状のニ
ッケル板からなる導電タブが溶接されてもよい。[Production of Positive Electrode] First, the positive electrode used here will be described. In this positive electrode, the active material near the conductive tab has high conductivity. The shape of this positive electrode, that is, the secondary battery electrode is shown in FIG. The electrode is vertical 10
It is composed of an active material coated portion having a size of cm and a width of 30 cm, and a conductive tab. The conductive tab is formed on one end side of the long side of the electrode. This conductive tab measures 1 cm in height and 10 in width.
cm. Inside the active material coating part, a nickel porous body (current collector) made of punching metal with a thickness of 0.1 mm is arranged, and the conductive tab is composed of a non-porous nickel plate with a thickness of 0.1 mm. There is. The nickel porous body may be a foamed nickel body. In this case, a conductive tab made of a tongue-shaped nickel plate may be welded.
【００１３】この電極において、活物質塗着部は、第１
組成の活物質部Ａと、第２組成の活物質部Ｂとから構成
されている。この領域Ａには第１組成の活物質、領域Ｂ
には第２組成の活物質が塗着充填されている。第１組成
の活物質部Ａは、導電タブが配置されたところから近い
ところに形成されている。この第１組成の活物質部Ａ
は、一片が導電タブに接するように、また一片が電極の
側辺と共通するように、そして残る一片が第２組成の活
物質部Ｂに接するよう形成される。一方、第２組成の活
物質部Ｂは、導電タブに対して、第１組成の活物質部Ａ
を介して、配置形成されている。尚、第１組成の活物質
部Ａと第２組成の活物質部Ｂに塗着される各活物質の重
量比率は、各活物質の密度が同程度であるから、その塗
着面積によって決定される。因みに、図１の場合は、第
１組成の活物質と第２組成の活物質の重量比率は、１：
７となっている。In this electrode, the active material coating portion is the first
It is composed of an active material part A having a composition and an active material part B having a second composition. In this region A, the active material of the first composition, region B
Is coated and filled with the active material of the second composition. The active material portion A of the first composition is formed at a position close to where the conductive tab is arranged. Active material part A of this first composition
Are formed so that one piece contacts the conductive tab, one piece is common to the side of the electrode, and the remaining piece contacts the active material portion B of the second composition. On the other hand, the active material portion B of the second composition is different from the active material portion A of the first composition with respect to the conductive tab.
Are arranged and formed through. It should be noted that the weight ratio of each active material applied to the active material portion A of the first composition and the active material portion B of the second composition is determined by the application area because the density of each active material is about the same. To be done. Incidentally, in the case of FIG. 1, the weight ratio of the active material of the first composition and the active material of the second composition is 1:
It is 7.
【００１４】ここで、使用した第１組成の活物質(図１
のＡの領域)、第２組成の活物質(図１のＢの領域)は、
表１の組み合わせに基づいて配置している。Here, the active material of the first composition used (see FIG. 1)
A region), the active material of the second composition (B region in FIG. 1),
It is arranged based on the combination of Table 1.
【００１５】[0015]
【表１】 [Table 1]
【００１６】尚、上記表１において示した各活物質は、
ベース活物質を出発物質として、次のとおり準備したも
のである。The active materials shown in Table 1 above are
It was prepared as follows using the base active material as the starting material.
【００１７】［ベース活物質(水酸化ニッケル活物質)］
このベース活物質は、次のようにして準備した。即ち、
硫酸ニッケル、硫酸コバルトの各水溶液を、硫酸ニッケ
ル：硫酸コバルトの重量比が98：２となるように混合し
て得たニッケル液を準備する。また、20重量％のアンモ
ニア水と20重量％水酸化ナトリウム水溶液とを５：１で
混合して得たアルカリ水溶液を準備する。上記ニッケル
液とアルカリ水溶液を、水を張った水槽中に同時に添加
し、沈殿物を生成させる。その後この沈殿物をろ過し、
水で洗浄後、真空乾燥を行い、ベース活物質を得る。[Base active material (nickel hydroxide active material)]
This base active material was prepared as follows. That is,
A nickel solution is prepared by mixing respective aqueous solutions of nickel sulfate and cobalt sulfate so that the weight ratio of nickel sulfate: cobalt sulfate is 98: 2. Further, an alkaline aqueous solution obtained by mixing 20% by weight aqueous ammonia and a 20% by weight aqueous sodium hydroxide solution at a ratio of 5: 1 is prepared. The nickel solution and the alkaline aqueous solution are simultaneously added to a water tank filled with water to form a precipitate. Then this precipitate is filtered,
After washing with water, vacuum drying is performed to obtain a base active material.
【００１８】［別添加コバルト活物質］この活物質は、
次のようにして準備した。上記ベース活物質90重量％
と、水酸化コバルト10重量％を混合して活物質を得、別
添加コバルト活物質と称する。尚、水酸化コバルトは導
電剤として作用するものである。[Separately Added Cobalt Active Material] This active material is
Prepared as follows. 90% by weight of the above base active material
And 10% by weight of cobalt hydroxide are mixed to obtain an active material, which will be referred to as a separately added cobalt active material. Cobalt hydroxide acts as a conductive agent.
【００１９】［コバルト被覆活物質］この活物質は、次
のようにして準備した。即ち、硫酸コバルトを16.7ｇを
水２リットルに溶解する。水酸化ニッケル活物質90ｇを
この水溶液に懸濁させる。水酸化ナトリウムでpH11に調
整し、水酸化ニッケル活物質の表面に水酸化コバルトを
析出させる。この操作を繰り返して必要量の活物質を
得、コバルト被覆活物質と称する。[Cobalt-Coated Active Material] This active material was prepared as follows. That is, 16.7 g of cobalt sulfate is dissolved in 2 liters of water. 90 g of nickel hydroxide active material is suspended in this aqueous solution. The pH is adjusted to 11 with sodium hydroxide, and cobalt hydroxide is deposited on the surface of the nickel hydroxide active material. This operation is repeated to obtain a required amount of active material, which is referred to as a cobalt-coated active material.
【００２０】［ナトリウム含有コバルト被覆活物質］こ
の活物質は、次のようにして準備した。即ち、上記コバ
ルト被覆活物質に、水酸化ナトリウム水溶液を噴霧し、
気流中80℃で乾燥させる。この乾燥させたものを、ナト
リウム含有コバルト被覆活物質と称する。[Sodium-Containing Cobalt-Coated Active Material] This active material was prepared as follows. That is, the cobalt-coated active material, by spraying an aqueous sodium hydroxide solution,
Dry in air at 80 ° C. This dried product is referred to as a sodium-containing cobalt-coated active material.
【００２１】上述のとおり、得られた各活物質を、図１
に示すとおり、各領域に分けて、充填している。ここ
で、図１のＡ領域とＢ領域とは、一方の領域をマスキン
グテープで目隠しした後に、他方の領域に活物質を塗着
充填し、その後マスキングテープを剥離して、他の活物
質を塗着充填して、形成される。また、充填方法は、次
のとおりである。即ち、上記各活物質80重量％、結着剤
としてのメチルセルロース(１重量％含有)水溶液20重量
％とを混練してペーストを得る。このペーストを、上述
したニッケル多孔体に塗着、充填する。その後乾燥、成
形している。このようにして、各正極A1、A2、a1、a2、
a3を構成した。As described above, each of the obtained active materials was converted into FIG.
As shown in, each area is divided and filled. Here, in the areas A and B in FIG. 1, after covering one area with a masking tape, the other area is coated and filled with an active material, and then the masking tape is peeled off to remove another active material. It is formed by applying and filling. The filling method is as follows. That is, 80% by weight of each of the above active materials and 20% by weight of a methylcellulose (containing 1% by weight) aqueous solution as a binder are kneaded to obtain a paste. This paste is applied and filled on the above-mentioned nickel porous body. After that, it is dried and molded. In this way, each positive electrode A1, A2, a1, a2,
configured a3.
【００２２】［負極の作製］この実験１で組み立てられ
たニッケル−水素アルカリ蓄電池に使用される、負極
を、次の様にして作製している。平均粒径20μmの水素
吸蔵合金（組成式MmNi3 .1Co0.9Al0.2Mn0.5、Mmはミッシ
ュメタルであって、希土類元素の混合物）89重量％に導
電剤としてのニッケル粉末10重量％と、結着剤としての
ポリエチレンオキサイド１重量％とを加え均一に混合
し、さらに水を加えペーストを得た。このペーストを、
ニッケルメッキが施されたパンチングメタル芯体(集電
体)の両面に、塗着、乾燥し、更に所定の寸法に切断し
た。このようにして、幅10cm、長さ30cmの負極を作製し
た。[Preparation of Negative Electrode] A negative electrode used in the nickel-hydrogen alkaline storage battery assembled in Experiment 1 is prepared as follows. The average particle size 20μm of the hydrogen storage alloy (composition formula MmNi 3 .1 Co 0.9 Al 0.2 Mn 0.5, Mm is a misch metal, a mixture of rare earth elements) and 10 wt% nickel powder as a conductive agent to 89 wt%, 1% by weight of polyethylene oxide as a binder was added and mixed uniformly, and water was further added to obtain a paste. This paste
The nickel-plated punched metal core (current collector) was coated on both surfaces, dried, and further cut into a predetermined size. In this way, a negative electrode having a width of 10 cm and a length of 30 cm was produced.
【００２３】［電池の構成］上記各正極(二次電池用電
極)及び負極を使用した、電池の概略を説明する。図２
は、角型ニッケル−水素アルカリ蓄電池の部分断面斜視
図である。電池缶１内では、非焼結式ニッケル正極２
と、水素吸蔵合金を含む負極３とを、それぞれ複数枚使
用している。これらは、セパレータ４を介して相対抗さ
せて配置され、電極群５を構成している。この電極群５
は、絶縁シート６に囲まれている。前記電池缶１の上面
11には、前記正極２と接続される正極端子７と、安全弁
８と、前記負極３に接続された負極端子９とが、設けら
れている。この負極３と負極端子９とは、導電タブ13を
介して電気接続されている。前記安全弁８はネジ構造で
あるため、電池缶１から取り外すことができる。電解液
は、安全弁を取り外したときに生じる注液孔10から、電
池缶１内に注液される。尚、ここで使用したアルカリ電
解液は、30重量％ＫＯＨ水溶液である。この電池の理論
容量は、100Ahである。また、この電池の外形寸法は、
幅３cm、高さ12cm、長さ32cmであり、各端子は直径１cm
の円柱状のボルトを通して外部負荷と接続される。[Constitution of Battery] An outline of a battery using each of the above positive electrodes (secondary battery electrodes) and negative electrodes will be described. Figure 2
FIG. 3 is a partial cross-sectional perspective view of a prismatic nickel-hydrogen alkaline storage battery. In the battery can 1, a non-sintered nickel positive electrode 2
And a plurality of negative electrodes 3 each containing a hydrogen storage alloy are used. These are arranged so as to be opposed to each other via the separator 4, and constitute the electrode group 5. This electrode group 5
Is surrounded by the insulating sheet 6. Upper surface of the battery can 1
At 11, a positive electrode terminal 7 connected to the positive electrode 2, a safety valve 8, and a negative electrode terminal 9 connected to the negative electrode 3 are provided. The negative electrode 3 and the negative electrode terminal 9 are electrically connected via the conductive tab 13. Since the safety valve 8 has a screw structure, it can be removed from the battery can 1. The electrolytic solution is injected into the battery can 1 through the injection hole 10 generated when the safety valve is removed. The alkaline electrolyte used here is a 30 wt% KOH aqueous solution. The theoretical capacity of this battery is 100 Ah. The external dimensions of this battery are
The width is 3 cm, the height is 12 cm, and the length is 32 cm. Each terminal is 1 cm in diameter.
It is connected to an external load through a cylindrical bolt.
【００２４】尚、正極としての本発明電極A1、本発明電
極A2、比較電極a1、比較電極a2、比較電極a3が各々使用
されて、各電池が組み立てられ、それぞれ準備されてい
る。Each of the batteries is assembled and prepared by using the electrode A1 of the present invention as the positive electrode, the electrode A2 of the present invention, the comparison electrode a1, the comparison electrode a2, and the comparison electrode a3.
【００２５】これらの各電池を用いて、電池特性を比較
した。この時の実験条件は、電池を１Ｃの電流値で1.2
時間充電し、１時間休止後、１Ｃの電流値で放電終止電
圧１Ｖまで放電させ、１時間休止させるという、充放電
サイクルを行うというものである。このテストにより、
平均作動電圧を算出し、サイクル寿命を実測した。この
結果を、併せて上記表１に示す。The battery characteristics were compared using each of these batteries. The experimental conditions at this time were 1.2C at a current value of 1C.
A charging / discharging cycle is performed in which the battery is charged for one hour, stopped for one hour, discharged at a current value of 1C to a discharge end voltage of 1 V, and rested for one hour. By this test,
The average operating voltage was calculated and the cycle life was measured. The results are also shown in Table 1 above.
【００２６】この結果から、本発明電極A1と比較電極a1
との対比により、導電タブ付近は電極中で最も電流が集
中するところであり、導電タブ付近に、導電性の高いナ
トリウム含有コバルト被覆活物質を用いると作動電圧が
高くなっていることが理解できる。また、導電タブ付近
に、導電性の高いコバルト被覆活物質を用いると、本発
明電極A2と比較電極a1との対比により、作動電圧が高く
なることが分かる。尚、電極全てをナトリウム含有コバ
ルト被覆活物質(比較電極a2)、コバルト被覆活物質(比
較電極a3)にすると、電池のサイクル寿命が低下してし
まう。From these results, the electrode A1 of the present invention and the comparative electrode a1
From the comparison, it can be understood that the current is concentrated most near the conductive tab in the electrode, and the operating voltage is increased when the sodium-containing cobalt-coated active material having high conductivity is used near the conductive tab. Further, it can be seen that when a cobalt-coated active material having high conductivity is used in the vicinity of the conductive tab, the operating voltage becomes higher due to the comparison between the electrode A2 of the present invention and the comparative electrode a1. If all electrodes are made of a sodium-containing cobalt-coated active material (comparative electrode a2) or a cobalt-coated active material (comparative electrode a3), the cycle life of the battery will be reduced.
【００２７】尚、上記電池のテストでは充電、放電条件
が設定されているが、実使用において電流を0.2Ｃ以下
で使用した時は、放電開始から２℃温度の上昇が観察さ
れた時点で、電池の残存容量が残りわずかであると判断
することができた。そのために、電池には温度センサー
12が配置されている。この方法によれば、電池の残存容
量検知が可能となる。上記0.2Ｃの電流値は、実験例の
電池では20Ａの電流値に相当する。この残存容量検知
は、電流値と環境温度を補償することにより、上述した
２℃という値を若干変更してもよい。また、温度変化
は、単位時間当りの変化率で検出してもよい。Although the charging and discharging conditions were set in the above battery test, when a current of 0.2 C or less was used in actual use, when a temperature rise of 2 ° C. was observed from the start of discharging, It was possible to determine that the remaining capacity of the battery was very low. Therefore, the battery has a temperature sensor.
Twelve are arranged. According to this method, the remaining capacity of the battery can be detected. The current value of 0.2 C corresponds to a current value of 20 A in the battery of the experimental example. In this state of charge detection, the value of 2 ° C. described above may be slightly changed by compensating the current value and the environmental temperature. Further, the temperature change may be detected by a rate of change per unit time.
【００２８】上記実験例では、導電タブ近傍の第１組成
の活物質を三角形状としたが、図３に示すとおり、第１
組成の活物質を帯状としてもよい。また、図４に示すと
おり、第１組成の活物質を一部帯状としてもよい。この
場合、図１に示す電極と同じサイズとすれば、一部帯状
のサイズは３cm×15cm程度とすればよい。In the above experimental example, the active material of the first composition in the vicinity of the conductive tab was formed into a triangular shape, but as shown in FIG.
The active material of the composition may be strip-shaped. Further, as shown in FIG. 4, the active material of the first composition may be partly band-shaped. In this case, if the size is the same as that of the electrode shown in FIG. 1, the size of a part of the band may be about 3 cm × 15 cm.
【００２９】[0029]
【００３０】[0030]
【００３１】[0031]
【００３２】[0032]
【発明の効果】 上述した如く、大電流を長時間に
取り出しても問題を生じない、電気自動車などに使用さ
れる大電流用途の二次電池用正極を提供でき、大電流充
放電が可能となる。また、正極における導電タブ近傍で
の温度上昇を抑え、優れた電極特性を発揮させることが
でき、その工業的価値は極めて大きい。As described above, it is possible to provide a positive electrode for a secondary battery used in an electric vehicle or the like, which does not cause a problem even if a large current is taken out for a long time, and can be charged and discharged with a large current. Become. Further, it is possible to suppress the temperature rise in the vicinity of the conductive tab in the positive electrode and to exhibit excellent electrode characteristics, and its industrial value is extremely large.
【図１】本発明の一実施例である二次電池用電極の説明
用平面図である。FIG. 1 is a plan view for explaining an electrode for a secondary battery that is an embodiment of the present invention.
【図２】本発明の電極を用いた電池の一断面を示す斜視
説明図である。FIG. 2 is a perspective explanatory view showing a cross section of a battery using the electrode of the present invention.
【図３】本発明の他の実施例である二次電池用電極の平
面図である。FIG. 3 is a plan view of a secondary battery electrode that is another embodiment of the present invention.
【図４】本発明の他の実施例である二次電池用電極の平
面図である。FIG. 4 is a plan view of a secondary battery electrode that is another embodiment of the present invention.
１ 電池缶 ２ 正極 ３ 負極 ４ セパレータ ５ 電極群 ６ 絶縁シート ７ 正極端子 ８ 安全弁 ９ 負極端子 １０ 注液孔 １１ 上面 １２ 温度センサー １３ 導電タブ Ａ 第１組成の活物質部 Ｂ 第２組成の活物質部 1 battery can 2 positive electrode 3 Negative electrode 4 separator 5 electrode group 6 Insulation sheet 7 Positive terminal 8 safety valve 9 Negative electrode terminal 10 Injection hole 11 upper surface 12 Temperature sensor 13 Conductive tab A Active material part of the first composition B Active material part of the second composition
───────────────────────────────────────────────────── フロントページの続き (72)発明者 矢野 睦 大阪府守口市京阪本通２丁目５番５号 三洋電機株式会社内 (72)発明者 野上 光造 大阪府守口市京阪本通２丁目５番５号 三洋電機株式会社内 (72)発明者 米津 育郎 大阪府守口市京阪本通２丁目５番５号 三洋電機株式会社内 (72)発明者 西尾 晃治 大阪府守口市京阪本通２丁目５番５号 三洋電機株式会社内 (56)参考文献 特開 平６−290806（ＪＰ，Ａ) 特開 平６−325759（ＪＰ，Ａ) 特開 平９−320631（ＪＰ，Ａ) 特開 平９−45372（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) H01M 4/00 - 4/04 H01M 4/14 - 4/62 H01M 10/00 - 10/40 ─────────────────────────────────────────────────── ─── Continued Front Page (72) Inventor Mutsumi Yano 2-5-5 Keihan Hondori, Moriguchi City, Osaka Prefecture Sanyo Electric Co., Ltd. (72) Kozo Nogami 2-5- Keihan Hondori, Moriguchi City, Osaka Prefecture No. 5 In Sanyo Electric Co., Ltd. (72) Inventor Ichiro Yonezu 2-5-5 Keihan Hondori, Moriguchi City, Osaka Prefecture Sanyo Electric Co., Ltd. (72) Koji Nishio 2-5 Keihan Hondori, Moriguchi City, Osaka Prefecture No. 5 within Sanyo Electric Co., Ltd. (56) Reference JP-A-6-290806 (JP, A) JP-A-6-325759 (JP, A) JP-A-9-320631 (JP, A) JP-A-9- 45372 (JP, A) (58) Fields investigated (Int.Cl. 7 , DB name) H01M 4/00-4/04 H01M 4/14-4/62 H01M 10/00-10/40
Claims (3)
用正極であって、 前記導電タブ近傍の第１組成の活物
質と、第２組成の活物質とが、集電体に塗着充填されて
おり、 前記第１組成の活物質が、水酸化コバルトで表面を被覆
された水酸化ニッケル、または、水酸化コバルトを水酸
化ナトリウム水溶液で処理することにより得られるナト
リウム含有コバルトで表面を被覆された水酸化ニッケル
であり、前記第２組成の活物質が、導電剤としての水酸
化コバルトが混合された水酸化ニッケルであることを特
徴とするニッケル−水素蓄電池用正極。 1. A nickel-hydrogen storage battery having a conductive tab.
A positive electrode for use in a positive electrode, wherein an active material having a first composition and an active material having a second composition in the vicinity of the conductive tab are coated and filled on a current collector.
And the active material of the first composition covers the surface with cobalt hydroxide.
Hydrolyzed nickel hydroxide or cobalt hydroxide
Nato obtained by treatment with an aqueous sodium chloride solution
Nickel hydroxide coated on the surface with cobalt containing cobalt
And the active material of the second composition is hydroxy as a conductive agent.
It is nickel hydroxide mixed with cobalt oxide.
Positive electrode for nickel-metal hydride storage battery.
から構成されるニッケル−水素蓄電池用正極であって、
前記導電タブに近接した集電体には第１組成の活物質
が配置され、前記配置された第１組成の活物質に対して
前記導電タブとは反対側の集電体には第２組成の活物質
が配置され、前記第１組成の活物質と前記第２組成の活
物質とが前記活物質塗着部を構成しており、 前記第１組成の活物質が、水酸化コバルトで表面を被覆
された水酸化ニッケル、または、水酸化コバルトを水酸
化ナトリウム水溶液で処理することにより得られるナト
リウム含有コバルトで表面を被覆された水酸化ニッケル
であり、前記第２組成の活物質が、導電剤としての水酸
化コバルトが混合された水酸化ニッケルであることを特
徴とするニッケル−水素蓄電池用正極。 2. A positive electrode for a nickel-hydrogen storage battery, comprising a current collector, a conductive tab, and an active material coating portion,
An active material having a first composition is disposed on the current collector adjacent to the conductive tab, and a second composition is disposed on the current collector on the opposite side of the disposed active material having the first composition. is the active material is disposed of, the first active material composition and said active material of the second composition constitutes the active material application portion, the active material of the first composition, surface cobalt hydroxide Covered
Hydrolyzed nickel hydroxide or cobalt hydroxide
Nato obtained by treatment with an aqueous sodium chloride solution
Nickel hydroxide coated on the surface with cobalt containing cobalt
And the active material of the second composition is hydroxy as a conductive agent.
It is nickel hydroxide mixed with cobalt oxide.
Positive electrode for nickel-metal hydride storage battery.
第２組成の活物質の塗布量との重量比率が、１：９〜The weight ratio to the coating amount of the active material of the second composition is 1: 9 to
１：４であることを特徴とする請求項２記載のニッケルNickel according to claim 2, characterized in that it is 1: 4.
−水素蓄電池用正極。-A positive electrode for a hydrogen storage battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16741896A JP3515286B2 (en) | 1996-06-27 | 1996-06-27 | Electrodes for secondary batteries |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16741896A JP3515286B2 (en) | 1996-06-27 | 1996-06-27 | Electrodes for secondary batteries |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH1021897A JPH1021897A (en) | 1998-01-23 |
| JP3515286B2 true JP3515286B2 (en) | 2004-04-05 |
Family
ID=15849338
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16741896A Expired - Fee Related JP3515286B2 (en) | 1996-06-27 | 1996-06-27 | Electrodes for secondary batteries |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3515286B2 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002063889A (en) * | 2000-08-15 | 2002-02-28 | Asahi Kasei Corp | Nickel hydride secondary battery |
| KR100384044B1 (en) * | 2001-07-09 | 2003-05-14 | 현대자동차주식회사 | Ni-MH Battery |
| JP5317507B2 (en) * | 2008-03-26 | 2013-10-16 | 三洋電機株式会社 | Cylindrical alkaline storage battery |
| JP2010015852A (en) * | 2008-07-04 | 2010-01-21 | Hitachi Vehicle Energy Ltd | Secondary battery |
| JP2010080231A (en) * | 2008-09-25 | 2010-04-08 | Sanyo Electric Co Ltd | Precursor for positive electrode active material, method of manufacturing the same, positive electrode active material, method of manufacturing positive electrode active material, and nonaqueous electrolyte secondary battery |
| US10541453B2 (en) * | 2016-10-31 | 2020-01-21 | Grst International Limited | Battery module for starting a power equipment |
-
1996
- 1996-06-27 JP JP16741896A patent/JP3515286B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH1021897A (en) | 1998-01-23 |
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