JP3104226B2 - End plate electrode manufacturing method - Google Patents

End plate electrode manufacturing method

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Publication number
JP3104226B2
JP3104226B2 JP63160502A JP16050288A JP3104226B2 JP 3104226 B2 JP3104226 B2 JP 3104226B2 JP 63160502 A JP63160502 A JP 63160502A JP 16050288 A JP16050288 A JP 16050288A JP 3104226 B2 JP3104226 B2 JP 3104226B2
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JP
Japan
Prior art keywords
glass fiber
frame
frame material
end plate
electrode
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
Application number
JP63160502A
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Japanese (ja)
Other versions
JPH0210661A (en
Inventor
明彦 広田
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Meidensha Corp
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Meidensha Corp
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Priority to JP63160502A priority Critical patent/JP3104226B2/en
Publication of JPH0210661A publication Critical patent/JPH0210661A/en
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Publication of JP3104226B2 publication Critical patent/JP3104226B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/96—Carbon-based electrodes
    • 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
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Inert Electrodes (AREA)
  • Hybrid Cells (AREA)

Description

【発明の詳細な説明】 A.産業上の利用分野 本発明は、亜鉛臭素二次電池等に使用する端板電極の
改良された製造法に関するものである。The present invention relates to an improved method for producing an end plate electrode used for a zinc bromine secondary battery or the like.

B.発明の概要 本発明は、それぞれグラスファイバーを含有させた２
枚のポリオレフィン製枠材の間にこの枠材より稍々小さ
いサイズのカーボンプラスチック基板を挟み込み、この
基板の周囲にグラスファイバーを含有させた中枠材を当
てがって板周囲の面を合わせたものを加圧成形してグラ
スファイバーを含有させた平板枠つき中間電極とすると
共に、この枠つき中間電極の２枚の間にリード取出し金
属メッシュを挟みグラスファイバーを含有させたポリオ
レフィン製背板上に載置して加圧成形することからなる
端板電極の製造法に関するものである。B. Summary of the Invention The present invention relates to a glass fiber-containing two
A carbon plastic substrate of a size slightly smaller than this frame material was sandwiched between two polyolefin frame materials, and a glass frame-containing medium frame material was applied to the periphery of this substrate, and the surfaces around the plate were matched. An intermediate electrode with a flat plate frame containing glass fiber by press molding was used, and a lead mesh was inserted between two of the intermediate electrodes with a frame, and a polyolefin backing plate containing glass fiber was used. And a method of manufacturing an end plate electrode, which is formed by press-mounting the end plate electrode.

C.従来の技術 亜鉛−臭素電池における端板電極の作製は、従来では
第８図に示すように、その構成物であるポリエチレン製
中枠材１、ポリエチレン製枠材２、カーボンプラスチッ
ク基板３、リード取出し用金属製メッシュ４、端板用背
板５と、陽極の場合は、さらに接液面に表面処理材６を
積み重ねてこれらを一括してコンプレッションモールド
用金型に入れ、ヒートプレス成形していた。C. Prior Art The end plate electrode in a zinc-bromine battery is conventionally manufactured by using a polyethylene frame member 1, a polyethylene frame member 2, a carbon plastic substrate 3, as shown in FIG. In the case of an anode, a metal mesh 4 for taking out a lead, a back plate 5 for an end plate, and in the case of an anode, a surface treatment material 6 is further stacked on the liquid contact surface, and these are collectively put into a compression mold and subjected to heat press molding. I was

この方法によると、材料を一括して金型に入れるので
コンプレッション作業そのものが一度で済むという利点
を有するものであり、この種の成形技術としては非常に
多用されているものであった。According to this method, since the materials are put into a mold all at once, there is an advantage that the compression operation itself can be performed only once, and this type of molding technique has been very frequently used.

D.発明が解決しようとする課題 ところが、構成材料の種類や固数が極めて多く、従っ
て作業が煩雑であるうえにヒートプレスするまでに時間
を要するという問題があった。D. Problems to be Solved by the Invention However, there were problems that the types and constituents of the constituent materials were extremely large, so that the work was complicated and time was required until heat pressing.

さらに上述のように、構成物の数が多いことから、金
型内ないしは構成材料間の空気を除去しきれずに空気が
残っていることから、成形品の表面にはそれが原因とみ
られる凹凸の不均一さがしばしば認められた。Further, as described above, since the number of components is large, air cannot be completely removed in the mold or between the constituent materials, and air remains, so that unevenness of the surface of the molded article due to the unevenness is considered to be caused by the air. Was often observed.

また、陽極端板用電極においては、基板電極の表面処
理材であるカーボンプラスチックと電極との付き具合が
重要なポイントとなるが、従来の方法であると枠材へリ
ード取出し用金属メッシュ等とカーボンプラスチックと
の密着具合や成形状態を中心にプレス条件を決定してい
たために、必ずしも陽極表面処理材が後で電極特性を向
上させるに十分な状態で成型されているということが言
えず、特性のうえでも問題点があった。In the electrode for the anode end plate, the degree of attachment between the electrode and carbon plastic which is a surface treatment material of the substrate electrode is an important point. Since the pressing conditions were determined based on the degree of close contact with the carbon plastic and the molding state, it cannot be said that the anode surface treatment material was necessarily molded in a state sufficient to improve the electrode characteristics later. On top of that, there was a problem.

従って上記のような問題点を解消する新たな成形方法
や成形条件を見出す必要があった。Therefore, it is necessary to find a new molding method and molding conditions that solve the above problems.

特に電極面積が大きくなり構成物の重量等も増える方
向に移行すると、この問題に対する解決策は重要な課題
であった。In particular, when the electrode area is increased and the weight of the components is increased, a solution to this problem has been an important issue.

このような従来技術における問題点を解決するため
に、本発明に到る過程として、先ず平板枠付き中間電極
を成形し、次にこの枠付き中間電極の２枚の間にリード
取出し用金属メッシュを挟みポリオレフィン製背板上に
載置して加圧成形することからなる端板電極の予備の製
造方法が考えられる。In order to solve the problems in the prior art, as a process leading to the present invention, first, an intermediate electrode with a flat frame is formed, and then a metal mesh for taking out a lead is provided between the two intermediate electrodes with the frame. A preliminary production method of an end plate electrode, which is formed by placing the substrate on a polyolefin back plate and press-molding it, can be considered.

すなわち従来は端板電極を作製する場合、カーボンプ
ラスチック電極、ポリエチレン製枠材、同背板等の構成
材料を一括して重ね合わせ、コンプレッションモールド
用金型に投入していたが、その工程のうち、先ず第６図
に示したように、２枚のポリエチレン製枠材２の間にカ
ーボンプラスチック基板３およびポリエチレン製中枠材
１を挟み込んで形成して、第７図に示すように、平板枠
付き中間電極10を形成しておき、この平板枠付き中間電
極10の２枚を用意してその間にリード取出し用金属メッ
シュ４を挟み、かつポリエチレン製背板５と重合して全
体を加圧成形するという二段の工程を採用して最終成型
品を作製するものである。That is, conventionally, when manufacturing an end plate electrode, constituent materials such as a carbon plastic electrode, a polyethylene frame material, and a back plate were collectively overlapped and charged into a compression mold. First, as shown in FIG. 6, a carbon plastic substrate 3 and a polyethylene medium frame 1 are sandwiched between two polyethylene frames 2 to form a flat frame, as shown in FIG. An intermediate electrode 10 with a plate is formed, and two intermediate electrodes 10 with a flat plate frame are prepared, a metal mesh 4 for taking out a lead is sandwiched between them, and the whole is pressure-formed by polymerization with a back plate 5 made of polyethylene. The final molded product is manufactured by adopting a two-step process of performing the above.

このような予備の方法を採用することにより、従来法
を実施していた場合に生じていた問題、すなわち構成物
が多いために金型への材料投入時における構成材料の乱
れや構成物を整える手間が大幅に解消され、また構成材
料が多いために生じるプレス時の残存空気による電極お
よび枠材面の凹凸等が解消され得るのである。By adopting such a preliminary method, the problem that occurs when the conventional method is performed, that is, since there are many components, the components are disturbed at the time of material input into the mold and the components are arranged. The time and labor can be greatly reduced, and the unevenness of the electrode and the frame material surface due to the residual air at the time of pressing caused by the large amount of constituent materials can be eliminated.

従って、上記予備の方法を実施すると最終成形時で
は、ヒートプレスの作業内容は、実質的に従来方法より
も大幅に簡素化させるに至った。Therefore, when the above-mentioned preliminary method is performed, the work content of the heat press at the time of final molding has been substantially greatly simplified as compared with the conventional method.

しかしながら、上記本発明に到る予備の製造方法にお
いても、なおかつ枠材部分とカーボンプレス基板（電
極）との密着性や枠部分の成形性はコンプレッション機
械の操作に依存し、金型内に残る残留ガス抜きの操作
や、加熱温度，時間，プレス圧等の条件が悪いと、上記
の密着性や成形性が悪くなる傾向がある。したがって同
じ製造条件でも歩留りが悪く、端板電極一枚当たりの製
造時間も長くなるのが現状であった。However, even in the preliminary manufacturing method according to the present invention, the adhesion between the frame material portion and the carbon press substrate (electrode) and the moldability of the frame portion depend on the operation of the compression machine and remain in the mold. If the operation of removing residual gas, or conditions such as heating temperature, time, and press pressure are poor, the above-mentioned adhesion and moldability tend to be poor. Therefore, even under the same manufacturing conditions, the yield is poor, and the manufacturing time per one end plate electrode is long.

本発明は前述した各問題点を解決したもので、その目
的は前述の予備の製造方法を生かし、なおかつ成型性や
密着性を良くするために、使用する枠材料ポリエチレン
樹脂にグラスファイバーを含有するものを用いるか、又
はグラスファイバーを、使用する樹脂とともに挿入して
成形することにより、成形性に優れかつ枠部材とカーボ
ンプラスチックとの密着性も優れて歩留りの向上を図る
ことである。The present invention has solved the above-mentioned problems, and the object is to utilize the above-mentioned preliminary manufacturing method, and to further improve moldability and adhesion, to use glass fiber in a frame material polyethylene resin used. By using a material or by inserting glass fiber together with a resin to be used and molding, the yield is improved due to excellent moldability and excellent adhesion between the frame member and the carbon plastic.

E.課題を解決するための手段 本発明は上記目的を達成するために、第１図に示した
ように、２枚のグラスファイバーよりなるグラスファイ
バーシート７間にポリオレフィン製枠材２を挿入して枠
材とするか、ポリオレフィン樹脂枠材２でグラスファイ
バーシート７を挟み加圧一体化して枠材とする工程と、
前記２つの何れかの枠材の間に該枠材よりも僅かに小さ
いサイズのカーボンプラスッチク基板３を挟み込み、こ
の基板の周囲に、２枚のグラスファイバーよりなるグラ
スファイバーシート７間にポリオレフィン製中枠材１を
挿入した中枠材あるいはポリオオレフィン樹脂中枠材で
グラスファイバーマットを挟み加圧一体化して形成され
た中枠材を当てがって板周囲の面を合わせたものを加圧
成型して、第２図に示すように、平板枠付き中間電極10
9とする工程、および この中間枠付き中間電極２枚の
間にリード取り出し用金属メッシュ４を挟みグラスファ
イバーより成るグラスファイバーシート７間にポリオレ
フィン製背板5aでグラスファイバーマット７を挟み加圧
一体化して形成された背板上に載置して加圧成形する工
程、からなることを特徴とする。E. Means for Solving the Problems In order to achieve the above object, the present invention inserts a polyolefin frame material 2 between two glass fiber sheets 7 as shown in FIG. A process of forming a frame material by sandwiching the glass fiber sheet 7 with the polyolefin resin frame material 2 and pressing and integrating the frame material;
A carbon plastic substrate 3 having a size slightly smaller than the frame material is sandwiched between any one of the two frame materials, and around the substrate, a glass substrate made of polyolefin is placed between glass fiber sheets 7 made of two glass fibers. A medium frame material in which the frame material 1 is inserted or a glass fiber mat is sandwiched by a polyolefin resin medium frame material and a medium frame material formed by press-integration is applied and the surface around the plate is pressed and molded. Then, as shown in FIG.
9 and a glass fiber mat 7 is sandwiched between glass fiber sheets 7 made of glass fiber with a metal mesh 4 for taking out lead between two intermediate electrodes with an intermediate frame, and a glass fiber mat 7 is sandwiched with a polyolefin back plate 5a. Mounting on a back plate formed in a pressurized manner.

この工程を具体的に示したのが第４図であり、第３図
は本発明によるグラスファイバー入りポリエチレンシー
トの製作例を示す。FIG. 4 specifically shows this step, and FIG. 3 shows a production example of a polyethylene sheet containing glass fibers according to the present invention.

このような方法を採用することにより、従来法を実施
していた場合に生じていた問題、すなわち構成物が多い
ために金型への材料投入時における構成材料のみ乱れや
構成物を整える手間が大幅に解消され、また構成材料が
多いために生じるプレス時の残存空気による電極および
枠材面の凹凸等が本発明により解消され得るのである。By adopting such a method, the problem that occurred when the conventional method was performed, that is, since there are many components, the disturbance of only the component material at the time of material input into the mold and the trouble of preparing the component are reduced. The present invention can largely eliminate the unevenness of the surface of the electrode and the frame material due to the residual air at the time of pressing caused by the large amount of constituent materials.

従って、本発明を実施すると最終成形時では、ヒート
プレスの作業内容は、実質的に従来方法よりも大幅に簡
素化されると共に、成形性の良い状態で歩留りが向上
し、かつ枠部材とカーボンプラスチックとの密着性も向
上した。Therefore, when the present invention is carried out, at the time of final molding, the work content of the heat press is substantially greatly simplified as compared with the conventional method, the yield is improved in a state of good moldability, and the frame member and the carbon The adhesion to plastic has also been improved.

F.作用 本発明における第１段階の構成物である中間電極の成
型方法は、従来のコンプレッション法による平板中間と
同様であり、構成材料自体にも変更はない。F. Function The method of molding the intermediate electrode, which is the first-stage component in the present invention, is the same as the conventional flat plate intermediate by the compression method, and there is no change in the constituent material itself.

しかし、最終的に端板電極を成型した後での、特に陽
極となる表面処理材接着部分の状態やその特性を左右す
る要因が、この表面処理平板中間電極の作製時点にある
ということを考慮すると、その成形条件には特に注意を
払うことが必要で、平板中間電極成形時のヒートプレス
の温度およびプレス圧力として、例えばプレス温度150
℃程度、材料投入時の金型温度をおよそ135〜137℃、圧
力50〜60kg/cm2Gまでの間に２回のガス抜きを行い、次
いでこの圧力を維持したまま所定時間成形を実施したの
ち冷却を始め金型温度が115〜113℃にまで低下したとこ
ろで材料をとり出すという操作を行うことにより最も好
ましい結果が得られやすい。However, after the end plate electrode is finally formed, it is necessary to consider that the factors that affect the state and characteristics of the surface treatment material adhesion part, especially the anode, are at the time of production of this surface treatment plate intermediate electrode. Then, it is necessary to pay particular attention to the molding conditions, and as the temperature and press pressure of the heat press at the time of forming the plate intermediate electrode, for example, a press temperature of 150
C., the mold temperature at the time of material input was about 135 to 137 ° C., and degassing was performed twice between 50 and 60 kg / cm 2 G, and then molding was performed for a predetermined time while maintaining this pressure. The most favorable result is likely to be obtained by performing the operation of taking out the material when the mold temperature has dropped to 115 to 113 ° C. after the start of cooling.

なお、ここで言う表面処理材とは、導電性シート（例
えばフッソ系導電性シート、炭素繊維等）であり、特に
前記のような成形条件を実施する際にはクロス形態の炭
素繊維を使用するのが好ましい。The surface treatment material referred to here is a conductive sheet (for example, a fluorine-based conductive sheet, carbon fiber, or the like). In particular, when performing the above-described molding conditions, a cloth-shaped carbon fiber is used. Is preferred.

また、最終成型品である端板電極の成形プレス条件
は、陽極電極を成形する場合には、表面処理を施してい
る中間電極を用い温度を130℃に維持しているプレスに
より60kg/cm2Gで１分間プレスを行いその後冷却をして
金型が115〜113℃程度になった時点で成形品を取出すよ
うにする。In addition, when the anode electrode is formed, the pressing conditions for forming the end plate electrode, which is the final molded product, are 60 kg / cm 2 by a press that maintains the temperature at 130 ° C. using a surface-treated intermediate electrode. Press for 1 minute at G, then cool and remove the molded product when the mold temperature reaches about 115-113 ° C.

一方、陰極電極を成形する時は、表面処理を施してい
ない中間電極を130℃に設定しているプレスにおき、２
回のガス抜きを行いながら60kg/cm2G迄昇圧してこの圧
力下で５分間維持した後、冷却を行い、金型温度が115
〜113℃程度になった時点で成形品を取出すようにする
のである。On the other hand, when forming the cathode electrode, place the intermediate electrode, which has not been subjected to surface treatment, on a press set to 130 ° C.
The pressure was increased to 60 kg / cm 2 G while degassing was performed and maintained at this pressure for 5 minutes.
When the temperature reaches about 113 ° C., the molded product is taken out.

G.実施例 次に種々のプレス条件で作成した陽極端板についての
実施例を示す。G. Examples Next, examples of anode end plates prepared under various pressing conditions will be described.

実施例 第１図に示した構成の材料についてと前記した端板用
平板枠付電極プレス条件で、端板用平板枠付電極（表面
処理材有り）を４枚、表面処理材無しの端板用平板枠付
電極を３枚作り、また第２図に示したような構成と前述
の陽極端板成形条件（但し、成形圧力のみは次の通り）
で３種の陽極端板を作製した。EXAMPLE With the material having the configuration shown in FIG. 1 and under the above-mentioned electrode pressing conditions with a flat plate for an end plate, four plates with a flat plate for an end plate (with a surface treatment material), and an end plate without a surface treatment material Three electrodes with a flat plate frame are prepared, and the configuration as shown in FIG. 2 and the above-described anode end plate molding conditions (however, only the molding pressure is as follows)
Produced three types of anode end plates.

これら３種の陽極端板と残った表面処理材有りの端板
用平板枠付電極について、それぞれ対極をカーボンプラ
スチックにしてハーフセルを構成し、銀−塩化銀電極を
参照電極として放電々位特性を検討した。 For these three types of anode end plates and the electrode with a flat plate frame for the end plate having the remaining surface treatment material, a half cell is constituted by using carbon plastic as a counter electrode, and a discharge potential characteristic is obtained using a silver-silver chloride electrode as a reference electrode. investigated.

なお、この測定では、電解液として３モル／臭化亜
鉛溶液に臭素を溶解させたもの（Br2濃度0.4〜1.0モル
／）を使用し、25℃の液温条件のもとで定電流でのＶ
−Ｉ特性についてテストを行った。In this measurement, 3 mol / zinc bromide solution obtained by dissolving bromine as an electrolyte solution using (Br 2 concentration 0.4 to 1.0 mol /), a constant current under the liquid temperature conditions 25 ° C. V
A test was conducted for the -I characteristic.

放電々位Φ（VVsAG−AgCl）および過電圧Ｕ（mV）と
それぞれの体積抵抗（Ω−cm）および電極部分の厚みを
次表にまとめた。The following table summarizes the discharge potential Φ (V Vs AG-AgCl), the overvoltage U (mV), the respective volume resistance (Ω-cm), and the thickness of the electrode portion.

なお、表中、電流密度はＪ（mA/cm2）、電極厚さＤ
（mm）で表した。In the table, the current density is J (mA / cm 2 ) and the electrode thickness D
(Mm).

また端板電極（Ｉ）〜（III）については、プレス圧
力と各特性について第５図に示した。For the end plate electrodes (I) to (III), the pressing pressure and each characteristic are shown in FIG.

メッシュおよび背板の厚さを含む。 Includes mesh and backboard thickness.

前表の結果から明らかなように、端板電極II以外は、
プレス圧が作用して成形後の形状に異常が発生してい
る。As is clear from the results in the preceding table, except for the end plate electrode II,
The shape after molding is abnormal due to the press pressure.

また表および第５図から、プレス圧が高いと電極の厚
みが小さくなるとともに比抵抗も小さくなるが、過電圧
は逆に増加し放電特性の挙動は悪くなることが判る。From the table and FIG. 5, it can be seen that when the press pressure is high, the thickness of the electrode is reduced and the specific resistance is also reduced, but the overvoltage is conversely increased and the behavior of the discharge characteristics is deteriorated.

これは、２枚の中間電極とその間のリード取り出し用
金属メッシュとのプレス圧力による密着度と、陽極面と
なる表面処理材の形状変形との兼合いによる結果であ
る。This is the result of the combination of the degree of adhesion between the two intermediate electrodes and the metal mesh for lead extraction between them by pressing pressure, and the shape deformation of the surface treatment material serving as the anode surface.

放電特性のみを考慮すれば、プレス圧力が小さい方が
良いが、成形品の出来具合を見ると、プレス圧が小さ過
ぎても、逆に大きすぎても良くないことが判る。Considering only the discharge characteristics, the smaller the press pressure is, the better it is. However, the quality of the molded product shows that the press pressure is not too small or conversely too large.

従来法によって電池極板を製造するときは、製品の大
きさが800cm2以下（およそ1kw級の電池サイズに相当す
る）の場合にはそれぼどの不都合は起こらないが、それ
以上に能力を発揮させるための大型の電池用電極を形成
させようとする場合には、構成材料が多いために材料間
の不揃いや成形中に生じる残存エアの問題など成形物お
よびその作業性に種々の問題が生じていたが、本発明の
方法によるとこのような問題は完全に解決され、生産性
を一段と向上させ得るものである。When manufacturing a battery electrode plate by the conventional method, if the product size is 800 cm 2 or less (corresponding to a battery size of about 1 kW class), almost no inconvenience will occur, but the ability will be demonstrated more When a large battery electrode is formed, various problems arise in the molding and its workability, such as irregularities between the materials and the problem of residual air generated during molding due to the large number of constituent materials. However, according to the method of the present invention, such a problem is completely solved and productivity can be further improved.

前述と同様な成形圧条件のもとで、成形に使用する中
枠材に、（Ａ）ポリエチレン樹脂のみを用いた本発明に
到るもの、（Ｂ）ポリエチレン樹脂と約1mm厚さのグラ
スファイバーマットを重ねて用いた本発明の第１の方法
によるもの、（Ｃ）本発明の第２の方法によりポリエチ
レン樹脂中枠材２枚にグラスファイバーマットをはさみ
加圧成形して１体としたグラスファイバー入りポリエチ
レン樹脂中枠材（厚みは（Ａ）と同じ）を用いて、それ
ぞれ端板電極を作製し、作製した端板電極の成形状態，
枠部分とカーボンプラスチックの密着性（かみつき強
度）、作製に要した時間及びヒートプレスのみの所要時
間を比較した。第１表はその結果を示したものである。
中枠材にポリエチレン樹脂のみを用いた（Ａ）の方法の
ものは枠材とカーボンプラスチックとのかみつき部分の
密着強度は、あまり高くなく、そのうえ成形状態も、枠
部分の表面に時おり金型の残存エアが残り、気泡状のふ
くれや樹脂流れの跡等が発生することがあって不十分で
ある。さらに、その様な成形状態を解消して良い状態に
保つためには、ヒートプレス工程において、保持時間，
エア抜き操作，予備加熱等に時間をかけるため、端板電
極１枚を製造するのに多くの時間が費やされるのが現状
である。Under the same molding pressure conditions as above, the present invention uses only (A) a polyethylene resin for the inner frame material used for molding, (B) polyethylene resin and glass fiber having a thickness of about 1 mm. Glass according to the first method of the present invention using mats stacked on top of each other, (C) Glass formed by pressing and molding a glass fiber mat between two polyethylene resin inner frame members according to the second method of the present invention to form a single body. Each end plate electrode was manufactured using a fiber-filled polyethylene resin inner frame material (having the same thickness as that of (A)), and the molded state of the manufactured end plate electrode was determined.
The adhesion (biting strength) between the frame portion and the carbon plastic, the time required for production, and the time required only for the heat press were compared. Table 1 shows the results.
In the case of the method (A) using only the polyethylene resin as the middle frame material, the adhesion strength of the biting portion between the frame material and the carbon plastic is not very high, and the molding state is sometimes a mold on the surface of the frame portion. This is insufficient because residual air may remain and bubble-like blisters and traces of resin flow may occur. Further, in order to eliminate such a molding state and maintain a good state, in the heat press process, the holding time,
At present, much time is required to manufacture one end plate electrode because it takes time to perform an air bleeding operation, preheating, and the like.

それに比べると中枠材にグラスファイバーを挿入した
り、グラスファイバー入りポリエチレン樹脂を用いる
と、成形性，かみつき強度，製造時間，ヒートプレス時
間が改善され、特性及び作業性が向上されていることが
判る。これは、特にヒートプレス工程において中枠材に
グラスファイバーを加えることによって、金型内に残っ
ている残存エアが吸収され、ポリエチレン樹脂表面の成
形性が良くなると、同時にカーボンプラスチックとのか
みつき強度も増加されることによるものである。Compared to that, when glass fiber is inserted into the middle frame material or polyethylene resin containing glass fiber is used, moldability, biting strength, manufacturing time, heat press time are improved, and characteristics and workability are improved. I understand. This is because, in particular, by adding glass fiber to the middle frame material in the heat press process, the residual air remaining in the mold is absorbed, the moldability of the polyethylene resin surface improves, and at the same time, the biting strength with carbon plastic It is due to being increased.

なお、ここで用いられるグラスファイバーは樹脂補強
用の市販品であればいずれでも使用可能であり、例えば
日本バイリーン（株）製キュムラスVH−5075の様なシー
ト、又はマット状のものが良い。特にポリエチレン樹脂
に含有させて一体化させて使用する場合においては、
（Ａ）の中枠材と同じ厚みで使用する必要が有るので、
例えば（Ａ）中枠材の厚み0.6mmである場合、第３図に
示すように0.3mm厚の２枚のポリエチレンシート1aに、
その厚み以下のグラスファイバーシート又はマット７を
はさみ、120℃以上の温度でヒートプレスすると、圧力
を調節することによって0.6mm厚のグラスファイバー入
りポリエチレンシートが成形出来る。また、あらかじめ
上記の様に一体化したシートを用いて端板作製する方法
では、グラスファイバーシート又はマットをポリエチレ
ン中枠材に挿入して成形する場合よりも、中枠材同志又
は中枠材と他の材料との相様性が良く、より良好に成形
される場合が多い。In addition, any glass fiber used here can be used as long as it is a commercially available product for resin reinforcement. For example, a sheet such as Cumulus VH-5075 manufactured by Japan Vilene Co., Ltd. or a mat-like one is preferable. In particular, when used by being integrated with polyethylene resin,
(A) Since it is necessary to use the same thickness as the middle frame material,
For example, when (A) the thickness of the middle frame material is 0.6 mm, as shown in FIG.
When a glass fiber sheet or mat 7 having a thickness less than that thickness is sandwiched and heat-pressed at a temperature of 120 ° C. or more, a 0.6 mm thick glass fiber-containing polyethylene sheet can be formed by adjusting the pressure. In addition, in the method of manufacturing an end plate using a sheet integrated as described above in advance as described above, compared with a case where a glass fiber sheet or a mat is inserted and molded into a polyethylene medium frame material, the medium frame material or the medium frame material is used. It has good compatibility with other materials and is often molded better.

次に、（Ａ）と（Ｃ）の方法でそれぞれ端板電極を50
枚ずつ作製し、それらの成形状態を観察して使用可能か
否かを判断し、歩留りを比較した。第２表はその結果を
示したものである。（Ｃ）の方法によれば成形性が悪
く、使用不可になった枚数が（Ａ）の方法の場合よりも
減り、歩留りは著しく向上した。 Next, each of the end plate electrodes is set to 50 by the methods (A) and (C).
The sheets were manufactured one by one, and their molding states were observed to determine whether they could be used, and the yields were compared. Table 2 shows the results. According to the method (C), the moldability was poor, the number of unusable sheets was reduced as compared with the method (A), and the yield was significantly improved.

すなわち本発明によれば、端板電極の構成材料の中枠
材において、グラスファイバーシート又はマットを挿入
するか又はグラスファイバーを含有したポリエチレン樹
脂を用いたところ、グラスファイバーがヒートプレス工
程で金型内に残存するエアを吸収するために、ポリエチ
レン樹脂、又はカーボンプラスチック自体へエアが残っ
て気泡状のふくれが発生する現象が解消され、従来より
も成形性が良くなった。それと同時に枠部分とカーボン
プラスチック部分のかみつき強度が増加した。 That is, according to the present invention, when a glass fiber sheet or a mat is inserted or a polyethylene resin containing glass fiber is used in the middle frame material of the constituent material of the end plate electrode, the glass fiber is molded by a heat press process. In order to absorb the air remaining inside, the phenomenon in which air remains in the polyethylene resin or carbon plastic itself to generate bubble-like blisters has been eliminated, and the moldability has been improved as compared with the related art. At the same time, the bite strength of the frame portion and the carbon plastic portion increased.

H.発明の効果 本発明方法によれば、従来にみられた種々の不都合を
解消し、最終成形品の出来具合が従来方法によるものよ
りも良くなった。H. Effects of the Invention According to the method of the present invention, various inconveniences observed in the past have been solved, and the quality of the final molded article has become better than that of the conventional method.

陽極端板においては、その特性を左右する表面処理材
の電極基板とのハリ付き具合が問題になるが、本発明方
法によれば中間電極作製段階で特性をチェックすること
によって作製条件を規定し、その中間電極を用いて最終
成形品を製造する段階で再び陽極端板としての特性をチ
ェックすることが可能であるため、結果として最も良い
条件で陽極端板を得ることができる。In the anode end plate, the degree of firmness between the surface treatment material and the electrode substrate that affects its characteristics is a problem, but according to the method of the present invention, the production conditions are defined by checking the characteristics in the intermediate electrode production stage. Since the characteristics of the anode end plate can be checked again at the stage of producing a final molded product using the intermediate electrode, the anode end plate can be obtained under the best conditions.

【図面の簡単な説明】[Brief description of the drawings]

第１図は本発明による端板用平板枠付き中間電極の構成
を示す斜視図、第２図は本発明による端板用平板枠付き
中間電極を用いて端板電極を形成させる際の構成を示す
斜視図、第３図は本発明によるグラスファイバー入りポ
リエチレンシートの製作例を示す斜視図、第４図は端板
成形の順序を説明するための工程図、第５図は本発明方
法により形成した陽極電極板のプレス圧力条件に対する
各種特性の存在度を示したグラフ、第６図は本発明に到
る過程における端板用平板枠付き中間電極の構成を示す
斜視図、第７図は本発明に到る過程における端板用平板
枠付き中間電極を用いて端板電極を形成させる際の構成
を示す斜視図、第８図は従来法による端板電極の製造を
行うときの構成を示した斜視図である。 １……ポリエチレン製中枠材、２……ポリエチレン製枠
材、３……カーボンプラスチック基板、４……リード取
出し用金属メッシュ、5a……グラスファイバーを含有す
るポリエチレン製背板、６……陽極表面処理材、７……
グラスファイバーシート、10a……グラスファイバーを
含有する平板枠付中間電極、11……グラスファイバー入
りポリエチレンシート。FIG. 1 is a perspective view showing the configuration of an intermediate electrode with a flat plate frame for an end plate according to the present invention, and FIG. 2 is a configuration when an end plate electrode is formed using the intermediate electrode with a flat plate frame for an end plate according to the present invention. FIG. 3 is a perspective view showing a production example of the glass fiber-containing polyethylene sheet according to the present invention, FIG. 4 is a process diagram for explaining an end plate forming sequence, and FIG. 5 is formed by the method of the present invention. FIG. 6 is a graph showing the existence of various characteristics with respect to the pressing pressure conditions of the anode electrode plate, FIG. 6 is a perspective view showing the configuration of an intermediate electrode with a flat plate frame for an end plate in the process leading to the present invention, and FIG. FIG. 8 is a perspective view showing a configuration when an end plate electrode is formed using an intermediate electrode with a flat plate frame for an end plate in a process leading to the invention, and FIG. 8 shows a configuration when manufacturing an end plate electrode by a conventional method. FIG. DESCRIPTION OF SYMBOLS 1 ... Polyethylene medium frame material 2 ... Polyethylene frame material 3 ... Carbon plastic substrate 4 ... Metal mesh for lead extraction, 5a ... Polyethylene back plate containing glass fiber, 6 ... Anode Surface treatment material, 7 ...
Glass fiber sheet, 10a: Intermediate electrode with flat plate frame containing glass fiber, 11: Polyethylene sheet containing glass fiber.

Claims (7)

(57)【特許請求の範囲】(57) [Claims] 【請求項１】２枚のグラスファイバーよりなるグラスフ
ァイバーシート間にポリオレフィン製枠材を挿入して枠
材とするか、ポリオレフィン樹脂枠材でグラスファイバ
ーシートを挟み加圧一体化して枠材とする工程と、 前記２つの何れかの枠材の間に該枠材よりも僅かに小さ
いサイズのカーボンプラスッチク基板を挟み込み、この
基板の周囲に、２枚のグラスファイバーよりなるグラス
ファイバーシート間にポリオレフィン製中枠材を挿入し
た中枠材あるいはポリオオレフィン樹脂中枠材でグラス
ファイバーマットを挟み加圧一体化して形成された中枠
材を当てがって板周囲の面を合わせたものを加圧成型し
て平板枠付き中間電極とする工程、および この平板枠付き中間電極２枚の間にリード取り出し用金
属メッシュを挟みグラスファイバーより成るグラスファ
イバーシート間にポリオレフィン製背板でグラスファイ
バーマットを挟み加圧一体化して形成された背板上に載
置して加圧成形する工程、 からなることを特徴とする端板電極の製造法。1. A frame material by inserting a polyolefin frame material between two glass fiber sheets made of glass fibers, or by pressing and integrating a glass fiber sheet with a polyolefin resin frame material to form a frame material. And a step of sandwiching a carbon plastic substrate having a size slightly smaller than the frame material between any one of the two frame materials, and forming a polyolefin material between glass fiber sheets made of two glass fibers around the substrate. The middle frame material with the middle frame material inserted or a polyolefin resin middle frame material is sandwiched between the glass fiber mats and press-molded. To form an intermediate electrode with a flat plate frame, and a glass fiber in which a metal mesh for lead extraction is sandwiched between the two intermediate electrodes with a flat frame. A step of placing the glass fiber mat between the glass fiber sheets comprising a polyolefin back plate and placing the glass fiber mat on a back plate formed by press-integration and press-molding the end plate electrode. Manufacturing method. 【請求項２】枠材、中枠材、背板の材質をグラスファイ
バーを含有するポリエチレンとしたことからなる特許請
求の範囲第１項に記載の端板電極の製造法。2. The method for producing an end plate electrode according to claim 1, wherein the material of the frame member, the middle frame member, and the back plate is made of polyethylene containing glass fiber. 【請求項３】中間電極および端板電極製造の際の成形圧
をおよそ50〜60kg/cm2としたことからなる特許請求の範
囲第１項に記載の端板電極の製造法。3. The method for producing an end plate electrode according to claim 1, wherein the molding pressure for producing the intermediate electrode and the end plate electrode is approximately 50 to 60 kg / cm 2 . 【請求項４】２枚のグラスファイバーよりなるグラスフ
ァイバーシート間にポリオレフィン製枠材を挿入して枠
材とするか、ポリオレフィン樹脂枠材でグラスファイバ
ーシートを挟み加圧一体化して枠材とする工程と、 前記２つの何れかの枠材の間に該枠材よりも僅かに小さ
いサイズのカーボンプラスッチク基板を挟み込み、この
基板の周囲に、２枚のグラスファイバーよりなるグラス
ファイバーシート間にポリオレフィン製中枠材を挿入し
た中枠材あるいはポリオオレフィン樹脂中枠材でグラス
ファイバーマットを挟み加圧一体化して形成された中枠
材を当てがってグラスファイバーからなるグラスファイ
バーシートを接合するか又はグラスファイバーを含有す
る平板枠付き中間電極とする工程、および この平板枠つき中間電極２枚の間にリード取出し用金属
メッシュを挟みグラスファイバーからなるグラスファイ
バーシートを、接合するか又はグラスファイバーを含有
するポリオレフィン製背板上に載置し、かつ該ポリオレ
フィン製背板に当接しない平板枠つき中間電極面に表面
処理材を当てがう工程、 からなる端板電極の製造法。4. A frame material is formed by inserting a polyolefin frame material between two glass fiber sheets made of glass fibers, or by pressing and integrating the glass fiber sheet with a polyolefin resin frame material to form a frame material. And a step of sandwiching a carbon plastic substrate having a size slightly smaller than the frame material between any one of the two frame materials, and forming a polyolefin sheet between two glass fiber sheets formed of two glass fibers around the substrate. The glass fiber mat is sandwiched between the middle frame material inserted with the middle frame material or the polyolefin resin middle frame material, and the glass frame mat formed by pressing and integrating is applied to join the glass fiber sheet made of glass fiber, or Step of forming an intermediate electrode with a flat plate frame containing glass fiber, and between the two intermediate electrodes with a flat plate frame A glass fiber sheet made of glass fiber sandwiching a metal mesh for lead extraction, bonded or placed on a polyolefin back plate containing glass fiber, and an intermediate electrode with a flat plate frame not in contact with the polyolefin back plate A process of applying a surface treatment material to the surface, comprising: 【請求項５】枠材、中枠材、背板の材質をグラスファイ
バーを含有するポリエチレンとしたことからなる特許請
求の範囲第４項に記載の端板電極の製造法。5. The method for producing an end plate electrode according to claim 4, wherein the material of the frame material, the middle frame material and the back plate is made of polyethylene containing glass fiber. 【請求項６】中間電極および端板電極製造の際の成形圧
をおよそ50〜60kg/cm2としたことからなる特許請求の範
囲第４項に記載の端板電極の製造法。6. The method for producing an end plate electrode according to claim 4, wherein the molding pressure for producing the intermediate electrode and the end plate electrode is approximately 50 to 60 kg / cm 2 . 【請求項７】表面処理材としてフッ素系導電性シートま
たは炭素繊維を使用することからなる特許請求の範囲第
４項に記載の端板電極の製造法。7. The method for manufacturing an end plate electrode according to claim 4, wherein a fluorine-based conductive sheet or carbon fiber is used as the surface treatment material.
JP63160502A 1988-06-28 1988-06-28 End plate electrode manufacturing method Expired - Fee Related JP3104226B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP63160502A JP3104226B2 (en) 1988-06-28 1988-06-28 End plate electrode manufacturing method

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP63160502A JP3104226B2 (en) 1988-06-28 1988-06-28 End plate electrode manufacturing method

Publications (2)

Publication Number Publication Date
JPH0210661A JPH0210661A (en) 1990-01-16
JP3104226B2 true JP3104226B2 (en) 2000-10-30

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