JP4963792B2 - Manufacturing method of paste type electrode plate and alkaline storage battery using the same - Google Patents
Manufacturing method of paste type electrode plate and alkaline storage battery using the same Download PDFInfo
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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
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Description
本発明は、多孔シートに活物質を充填塗布してなるペースト式極板およびそれを用いたアルカリ蓄電池に関するものである。 The present invention relates to a paste type electrode plate obtained by filling a porous sheet with an active material and an alkaline storage battery using the same.
ニッケル・カドミウム蓄電池などのアルカリ蓄電池は、正極板と負極板のそれぞれ複数枚をセパレータを介して互いに積層し、これを電槽に収納して製造される。カドミウム極としてペースト式極板が広く使用されており、カドミウム極の製造方法として次の方法が知られている。まず、酸化カドミウムを主体とする活物質粉末などを有機粘結剤、ナイロン繊維などの補強材、エチレングリコールなどの有機溶媒と共に混練して、ペースト状とする。次に、このペーストを、ニッケルめっきを施した長尺の有孔薄鋼板などの多孔シートの両面に塗着・乾燥し、電池種別に応じて所望の寸法に切断してペースト状負極板を形成する。 An alkaline storage battery such as a nickel-cadmium storage battery is manufactured by laminating a plurality of positive and negative electrode plates with a separator interposed between them and storing them in a battery case. Paste electrode plates are widely used as cadmium electrodes, and the following methods are known as methods for producing cadmium electrodes. First, an active material powder mainly composed of cadmium oxide is kneaded with an organic binder, a reinforcing material such as nylon fiber, and an organic solvent such as ethylene glycol to obtain a paste. Next, this paste is applied to both sides of a porous sheet such as a long perforated thin steel sheet plated with nickel, dried, and cut into desired dimensions according to the battery type to form a paste-like negative electrode plate To do.
ニッケル・カドミウム蓄電池に使用されているペースト式負極板のように、多孔シートに活物質ペーストを単に塗布した構造である極板は、活物質の接着強度が弱く、非常に剥離や脱落が起き易い。特に、ベント形蓄電池に使用する場合、充電末期に負極板からガスの発生が起きるため、使用中に活物質が多孔シートより剥離や脱落し、早期寿命に至ってしまっていた。 Like the paste-type negative electrode plate used in nickel-cadmium storage batteries, the electrode plate with a structure in which the active material paste is simply applied to the porous sheet has a low active material adhesive strength, and is very easy to peel off or drop off. . In particular, when used in a bent storage battery, gas is generated from the negative electrode plate at the end of charging, so that the active material is peeled off or dropped from the porous sheet during use, leading to an early life.
そこで、ホットメルト溶液が貯留された溶液層を備えた転写ロールを用いて、極板の端部をコ字状のホットメルトで薄く均一に覆う方法（特許文献１）が行われている。 In view of this, a method (Patent Document 1) in which an end portion of an electrode plate is thinly and uniformly covered with a U-shaped hot melt using a transfer roll having a solution layer in which a hot melt solution is stored is performed.
特許文献１記載の方法は、極板の端部にコ字状にホットメルトを被覆するもので、活物質の剥離や脱落防止についての一応の効果は認められたが、十分な接着強度を得るに至らなかった。また、端部にコ字状に樹脂を被覆するため、樹脂を薄く形成しても樹脂の厚みにより極板とセパレータの間に隙間が生じてしまうという問題があった。 In the method described in Patent Document 1, hot melt is coated on the end of the electrode plate in a U-shape, and a temporary effect for preventing the active material from peeling and falling off is recognized, but sufficient adhesive strength is obtained. It did not lead to. Further, since the end portion is coated with a resin in a U shape, there is a problem that even if the resin is formed thin, a gap is generated between the electrode plate and the separator due to the thickness of the resin.
極板とセパレータの間に隙間が生じるということは、両者の密着性が低下し、蓄電池の内部抵抗の上昇と蓄電池容量の低下を引き起こすことになってしまう。 If a gap is generated between the electrode plate and the separator, the adhesion between the two is reduced, leading to an increase in the internal resistance of the storage battery and a decrease in the storage battery capacity.
このような背景の下、樹脂と極板端面との十分な接着強度が得られ、樹脂による極板とセパレータ間の隙間を無くし、且つ、極板の端面から活物質の剥離・脱落防止を無くす極板を提供することを目的としたものである。 Under such a background, sufficient adhesion strength between the resin and the end face of the electrode plate can be obtained, and there is no gap between the electrode plate and the separator due to the resin, and the active material is prevented from peeling off or falling off from the end face of the electrode plate. The purpose is to provide an electrode plate.
本発明は、多孔シートに活物質層を塗着・乾燥して構成されたペースト式極板において、金型成形により極板の切断端面にのみ樹脂を固着することを特徴としたものである。 The present invention is characterized in that, in a paste-type electrode plate configured by applying an active material layer to a porous sheet and drying, a resin is fixed only to a cut end surface of the electrode plate by molding.
本発明は、金型成形により極板の切断端面のみに樹脂を固着することができるので、樹脂による極板とセパレータ間の隙間を無くすことができると共に、樹脂と極板との密着強度を向上することができ、活物質の剥離や脱落を無くすことが可能である。 Since the present invention can fix the resin only to the cut end face of the electrode plate by molding, it can eliminate the gap between the electrode electrode plate and the separator and improve the adhesion strength between the resin and the electrode plate. It is possible to eliminate peeling and dropping of the active material.
極板は活物質粉末を有機粘結剤、補強材、有機溶媒とともに混練してペースト状とし、このペーストをニッケルめっきを施した有孔薄鋼板などの多孔シートの両面に塗着した後、乾燥・加圧プレスして所望の寸法に切断して作製される。 The electrode plate is made by kneading the active material powder together with an organic binder, reinforcing material, and organic solvent into a paste, and applying this paste on both sides of a porous sheet such as a perforated thin steel sheet plated with nickel, followed by drying・ Pressurized and cut into desired dimensions.
そして、コの字状に形成された金型にホットメルト樹脂を流し込み、極板の切断端面にのみ樹脂を固着し、乾燥させる。ホットメルト樹脂はポリプロピレンを主成分とした樹脂であり、１００〜１８０℃で加熱溶融され流動性となり、常温では固体状となっている。図１は金型成形によりホットメルト樹脂を極板に固着させる一実施の形態である。１は極板で多孔シート１１とこの多孔シート１１の両面に充填塗布された活物質層１２からなる。２は極板１の切断端部周囲に配した金型、３はホットメルト樹脂の固着部、ｂは該固着部 ３の固着厚みである。金型２には注入口２１が形成され、該注入口２１からホットメルト樹脂が加圧注入されて、極板１の切断端部のみにホットメルト樹脂が施され固着する。 Then, a hot melt resin is poured into a U-shaped mold, and the resin is fixed only to the cut end face of the electrode plate and dried. The hot melt resin is a resin whose main component is polypropylene, is heated and melted at 100 to 180 ° C., becomes fluid, and is solid at room temperature. FIG. 1 shows an embodiment in which a hot melt resin is fixed to an electrode plate by molding. Reference numeral 1 denotes an electrode plate comprising a porous sheet 11 and an active material layer 12 filled and applied on both surfaces of the porous sheet 11. 2 is a mold disposed around the cut end of the electrode plate 1, 3 is a fixing portion of the hot melt resin, and b is a fixing thickness of the fixing portion 3. An injection port 21 is formed in the mold 2, and hot melt resin is pressurized and injected from the injection port 21, and the hot melt resin is applied only to the cut end portion of the electrode plate 1 and fixed.
活物質として酸化カドミウム粉末を用い、これを有機粘結剤としてのポリビニルアルコールと補強材としてのナイロン短繊維と有機溶媒としてのエチレングリコールと共に混練してペースト状とし、このペースト状活物質をニッケルめっきした有孔薄鋼板からなる長尺の多孔シートの長尺方向の両面に塗布乾燥して該多孔シートに活物質層と活物質を塗布しない無地部を形成し、その長さ方向を適当な寸法に切断し、無地部の一部を除いて切り欠き、該残った一部を耳部としたペースト式カドミウム負極板を作製した。 Cadmium oxide powder is used as an active material, and this is kneaded with polyvinyl alcohol as an organic binder, nylon short fibers as a reinforcing material, and ethylene glycol as an organic solvent to form a paste. This paste-like active material is nickel-plated. The porous material is coated and dried on both sides in the longitudinal direction of a long porous sheet made of perforated thin steel sheet to form a solid part where the active material layer and the active material are not applied to the porous sheet, and the length direction is set to an appropriate dimension. Then, a paste type cadmium negative electrode plate was produced with the remaining part cut out except for a part of the plain part.
作製した負極板の切断された活物質の存在する両切断端面にのみ金型成形によりポリプロピレンを主成分としたホットメルト樹脂を固着させて、図２に示す様に切断端面に厚み０．５ｍｍの樹脂の固着部３を有するペースト式カドミウム負極板１を得た。図中図１と同じ部材は同じ符号で示した。１３は切断端面、１４は耳部である。なお、ホットメルト樹脂を固着させる部分は活物質層の両切断端面のみで良いが、本実施例では活物質層の塗布幅のバラツキを考慮して無地部にも金型の空間がかかるようにしので、図１に示す様に無地部にもホットメルト樹脂が固着される。 A hot melt resin mainly composed of polypropylene was fixed by die molding only to both the cut end surfaces where the cut active material of the prepared negative electrode plate was present, and the cut end surface had a thickness of 0.5 mm as shown in FIG. A paste type cadmium negative electrode plate 1 having a resin fixing portion 3 was obtained. In the figure, the same members as those in FIG. 1 are denoted by the same reference numerals. Reference numeral 13 denotes a cut end face, and reference numeral 14 denotes an ear. Note that the hot melt resin may be fixed only on both cut end faces of the active material layer. However, in this embodiment, in consideration of variations in the coating width of the active material layer, a space for the mold is also applied to the plain portion. Therefore, as shown in FIG. 1, the hot melt resin is also fixed to the plain portion.
（比較例１）
比較例１として図３に示す様に、極板１の切断端面１３のみならずその表裏面を含む周縁部に樹脂の固着部３が形成される様にした金型２を用いた以外は実施例１と同様にしてペースト式カドミウム負極板を作製した。この時の樹脂固着部の切断端面における厚みｂは０．５ｍｍ、極板の表裏面における樹脂固着部の厚みａは０．０５ｍｍ、該表裏面における固着部の幅ｃは３ｍｍとした。
(Comparative Example 1)
As Comparative Example 1, as shown in FIG. 3, the embodiment was performed except that a mold 2 in which a resin fixing portion 3 was formed not only on the cut end surface 13 of the electrode plate 1 but also on the peripheral portion including the front and back surfaces thereof was used. A paste-type cadmium negative electrode plate was produced in the same manner as in Example 1. At this time, the thickness b of the cut end surface of the resin fixing portion was 0.5 mm, the thickness a of the resin fixing portion on the front and back surfaces of the electrode plate was 0.05 mm, and the width c of the fixing portion on the front and back surfaces was 3 mm.
（比較例２）
次に比較例２として、ホットメルト樹脂を公知のローラー転写方式により負極板の切断端面のみならず表裏面を含む周縁部をコの字状に被覆した以外は実施例1と同様にてペースト式カドミウム負極板を作製した。なお、ホットメルト樹脂の固着厚みおよび固着幅は比較例１と同様に、切断面側の固着厚み０．５ｍｍ、極板表面側の固着厚み０.０５ｍｍ、極板表面側の固着幅３ｍｍとした。
(Comparative Example 2)
Next, as Comparative Example 2, a hot melt resin was pasted in the same manner as in Example 1 except that the peripheral portion including the front and back surfaces as well as the cut end surface of the negative electrode plate was coated in a U-shape by a known roller transfer method. A cadmium negative electrode plate was prepared. The fixing thickness and fixing width of the hot melt resin were set to 0.5 mm on the cut surface side, 0.05 mm on the electrode plate surface side, and 3 mm on the electrode plate surface side, as in Comparative Example 1. .
（従来例）
従来例としては、ホットメルト等の樹脂を負極板の切断端部に固着させない以外は実施例と同様にペースト式カドミウム負極板を作製した。
(Conventional example)
As a conventional example, a paste-type cadmium negative electrode plate was produced in the same manner as in the example except that a resin such as hot melt was not fixed to the cut end of the negative electrode plate.
上記の実施例および比較例１、２で作製した各ペースト式カドミウム負極板を、環境温度２５℃、ＫＯＨ水溶液中において、対極としてニッケル板を用いて、−１．６５Ｖ（対ニッケル板）になるまで充電し、１．５Ｖ（対ニッケル板）になるまで放電する充放電を５０回繰り返し、活物質の剥離や脱落の有無を観察した。その結果を表１に示した。 Each paste type cadmium negative electrode plate produced in the above-mentioned Examples and Comparative Examples 1 and 2 is −1.65 V (vs. nickel plate) using a nickel plate as a counter electrode in an aqueous KOH solution at an environmental temperature of 25 ° C. Charging / discharging was performed 50 times, and discharging until 1.5 V (vs. nickel plate) was repeated 50 times, and the presence or absence of peeling or dropping of the active material was observed. The results are shown in Table 1.
表１に示すように金型成形により樹脂を固着させた本実施例および比較例１においては樹脂の剥離や脱落不良は見られなかった。実施例のように極板の端部にのみ固着させた場合でも樹脂の剥離や脱落不良は確認されなかった。これは、樹脂に圧力をかけて金型に送り込むため、基板表面より僅かであるが内部まで樹脂が入り込み固着することで、樹脂と負極板との接着強度が向上したためである。なお、ローラー転写方式を用いた比較例２では樹脂の剥離や脱落不良が確認された。 As shown in Table 1, in this Example and Comparative Example 1 in which the resin was fixed by molding, no resin peeling or dropping failure was observed. Even when it was fixed only to the end portion of the electrode plate as in the example, no peeling or dropping of the resin was confirmed. This is because the resin is fed into the mold while applying pressure to the resin, but the resin enters the inside and is fixed slightly, but the adhesive strength between the resin and the negative electrode plate is improved. In Comparative Example 2 using the roller transfer method, it was confirmed that the resin was peeled off or dropped out.
次に、実施例および比較例１、２、従来例で作製した各ペースト式カドミウム負極板を公知の方法で作製した焼結式ニッケル正極板とセパレータを介して交互に積層した極板群を電槽に収納して公称容量４０Ａｈの開放形ニッケル・カドミウムアルカリ蓄電池（本発明電池、比較電池１、２、従来電池）を作製し、各蓄電池を、環境温度２５℃において、放電深度６０％で充放電を繰り返したときの寿命に至るまでの回数を測定した。なお、充放電とも０・２５ＣＡの電流で行い、充電量は放電量の１．４倍とし、定格容量の６０％に低下した時を寿命とし、５０回毎に容量を確認した。 Next, an electrode plate group in which each paste-type cadmium negative electrode plate prepared in Examples and Comparative Examples 1 and 2 and the conventional example is alternately laminated via a separator and a sintered nickel positive electrode plate manufactured by a known method is electrically connected. An open-type nickel-cadmium alkaline storage battery (invention battery, comparative batteries 1, 2 and conventional batteries) having a nominal capacity of 40 Ah is prepared in a tank, and each storage battery is charged at an environmental temperature of 25 ° C. with a discharge depth of 60%. The number of times until the life when the discharge was repeated was measured. The charge / discharge was performed at a current of 0.25 CA, the charge amount was 1.4 times the discharge amount, the life was when it was reduced to 60% of the rated capacity, and the capacity was confirmed every 50 times.
また、各蓄電池を環境温度２５℃において、充電電流を０.１ＣＡで１５時間充電した後、放電電流を１ＣＡで１Ｖまで放電した時の持続時間を確認した。表２には、寿命に至った充放電回数と持続時間を示した。なお、持続時間は従来電池を１００とした時の従来電池に対する相対比で表したものである。 In addition, after charging each storage battery at an environmental temperature of 25 ° C. for 15 hours with a charging current of 0.1 CA, the duration when the discharging current was discharged to 1 V with 1 CA was confirmed. Table 2 shows the number of charge / discharge cycles and the duration of the lifetime. The duration is expressed as a relative ratio with respect to the conventional battery when the conventional battery is 100.
本発明電池は比較電池２および従来電池に比し長寿命であることが分かる。また持続時間は、本発明電池において従来電池と同等の結果を得ることができたが、比較電池１や２において若干低下している。これはホットメルトを極板表面にも固着させているため、活物質と電解液との反応面積が少なくなり利用率が低下したものと考えられる。 It can be seen that the battery of the present invention has a longer life than the comparative battery 2 and the conventional battery. The duration time of the battery of the present invention was the same as that of the conventional battery, but the comparison batteries 1 and 2 slightly decreased. This is presumably because the hot melt was fixed to the surface of the electrode plate, so that the reaction area between the active material and the electrolytic solution was reduced and the utilization rate was lowered.
以上の結果より、金型成形により極板の切断端面にのみ樹脂を固着することで樹脂による極板とセパレータ間の隙間を無くすことができると共に、樹脂と極板との密着強度を向上することができ、活物質の剥離や脱落を無くすことが可能である。 From the above results, by fixing the resin only to the cut end face of the electrode plate by molding, the gap between the electrode electrode plate and the separator can be eliminated, and the adhesion strength between the resin and the electrode plate can be improved. It is possible to eliminate the peeling and dropping of the active material.
１ 極板
１１ 多孔シート
１２ 活物質層
２ 金型
３ 固着部
３１ 注入口
ａ 極板表面側塗布厚み
ｂ 極板端面側の塗布厚み
ｃ 極板表面側塗布幅
DESCRIPTION OF SYMBOLS 1 Electrode plate 11 Porous sheet 12 Active material layer 2 Mold 3 Adhering part 31 Inlet a Electrode plate surface side coating thickness b Electrode plate end surface side coating thickness c Polar plate surface side coating width
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| Application Number | Priority Date | Filing Date | Title |
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| JP2005052035A JP4963792B2 (en) | 2005-02-25 | 2005-02-25 | Manufacturing method of paste type electrode plate and alkaline storage battery using the same |
| CN2006100549457A CN1828984B (en) | 2005-02-25 | 2006-02-27 | Paste type plate manufacturing method and alkaline accumulator using same |
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| JP4963792B2 true JP4963792B2 (en) | 2012-06-27 |
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| CN102208604A (en) * | 2010-03-30 | 2011-10-05 | 江苏伊思达电池有限公司 | Preparation method of electrode sheet without external tab of coiled lithium ion battery |
| WO2013168980A1 (en) * | 2012-05-07 | 2013-11-14 | 주식회사 엘지화학 | Battery pack having amorphous structure |
| CN104981923B (en) | 2013-02-01 | 2018-09-11 | 株式会社日本触媒 | electrode precursor, electrode and battery |
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| JP3585854B2 (en) * | 2001-03-02 | 2004-11-04 | 京セラ株式会社 | Injection molding method |
| JP2004281312A (en) * | 2003-03-18 | 2004-10-07 | Matsushita Electric Ind Co Ltd | Method of manufacturing electrode plate for battery |
| JP4498772B2 (en) * | 2003-04-22 | 2010-07-07 | パナソニック株式会社 | Alkaline storage battery and its manufacturing method |
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2005
- 2005-02-25 JP JP2005052035A patent/JP4963792B2/en active Active
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| CN1828984B (en) | 2010-12-15 |
| JP2006236865A (en) | 2006-09-07 |
| CN1828984A (en) | 2006-09-06 |
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