508857 五、發明説明（1 ) [技術領域] 本發明係相關具備有配豈於正極板與負極板、及二極板 間之由隔板所構成的極板群；與容納該極板群並儲存電解 液的電解槽之密閉型鉛蓄電池。特別係相關提昇充放電特 性，且可抑制並防止正負二極間產生析出硫酸鉛PbS〇4離 子性結晶體之所謂硫酸鹽化作用的硫化現象之密閉型鉛蓄 電池。 [技術背景] 按，此種密閉型鉛蓄電池係廣泛的使用於備用電源、攜 帶型機器用電源、汽車、電動機車、電動腳踏車、或高爾 夫球車等方面上。/此種密閉型鉛蓄電池係具備有在正極板 與負極板間夾置隔板而形成極板群，並將此極板群容納於 特定數量的電解槽內，同時注入電解液的構造，因爲充電 時，由正極板所產生的氧氣，將移動至負極板，並與負極 板表面上所產生的氫氣產生反應，而再生出水，所以可密 閉化。 因此，上述隔板並不僅止於保持電解液及該正極板與該 負極板間/的絕緣，亦需講求提昇由正極板移往負極板的氧 氣移動性，及使負極板上所產生的氫氣與該氧氣進行反應 而所生成之水，充分擴散於電解液中的功能。 此類密閉型鉛蓄電池用隔板；過去，習知係使用在親水 性聚酯纖維與玻璃纖維中，混入矽石粉末者（日本特開平 4 - 8 2 1 5 5號公報），或在表面層採用直徑1 // m以下之極細 玻璃纖維，而內面層則採用高吸水性樹脂中摻入S i、A 1、 508857508857 V. Description of the invention (1) [Technical Field] The present invention relates to an electrode plate group composed of a separator that is arranged between a positive electrode plate, a negative electrode plate, and a second electrode plate; A sealed lead-acid battery for electrolytic cells that store electrolyte. In particular, it is a sealed lead-acid battery that improves the charge and discharge characteristics, and can suppress and prevent the sulfurization phenomenon of the so-called sulfation phenomenon of lead sulfate PbS04 ion crystals generated between the positive and negative diodes. [Technical background] According to this, such sealed lead-acid batteries are widely used in backup power sources, power sources for portable machines, automobiles, electric vehicles, electric bicycles, or golf carts. / This type of sealed lead-acid battery has a structure in which an electrode group is formed by sandwiching a separator between a positive electrode plate and a negative electrode plate, and the electrode plate group is accommodated in a specific number of electrolytic cells, and an electrolyte solution is simultaneously injected, During charging, the oxygen generated by the positive plate will move to the negative plate and react with the hydrogen generated on the surface of the negative plate to regenerate water, so it can be sealed. Therefore, the separator is not limited to maintaining the electrolyte and the insulation between the positive electrode plate and the negative electrode plate. It also needs to improve the mobility of oxygen moving from the positive electrode plate to the negative electrode plate and the hydrogen generated on the negative electrode plate. The function of water generated by reacting with this oxygen is sufficient to diffuse in the electrolyte. This type of separator for sealed lead-acid batteries; conventionally, it has been used in hydrophilic polyester fibers and glass fibers, and mixed with silica powder (Japanese Patent Application Laid-Open No. 4-8 2 1 5 5), or on the surface The layer uses ultra-fine glass fibers with a diameter of 1 // m or less, and the inner layer uses super absorbent resin with S i, A 1, 508857
五、發明説明（2 ) Τ1、Mg氧化物微粉末者（日本特開平7 _ 6 5 8丨3號公報），或 採用編織入丙烯酸系、聚酯系、聚乙烯系合成樹脂抄紙 狀’與直徑1 8〜20 // m玻璃長纖維的板狀者，或將顆粒狀 砂石填充於正負極面與電極間者.；此外，加在溶融附著矽 石粉末的板片陶瓷纖維中，與超吸水性纖維形成一體化而 將電解液維持凝膠化者（日本特開昭63 _ 25656丨號公報）， 或使用陶瓷纖維與凝膠化電解液者（日本特開昭6 1 - 2 5 0 9 6 8 號公報）亦爲眾所周知者。 惟’由上述習知材料及構造所形成並配設的密閉型鉛蓄 電池，在充電時將產生下式電化學反應：V. Description of the invention (2) T1, Mg oxide fine powder (Japanese Unexamined Patent Publication No. 7 _ 6 5 8 丨 3), or weaving into acrylic, polyester, polyethylene synthetic resin paper-like shape and Plates with a length of 8 ~ 20 // m glass long fiber, or those filled with granular sandstone between the positive and negative electrode surfaces and the electrode. In addition, it is added to the plate ceramic fiber that melts and adheres the silica powder, and Superabsorbent fibers are integrated to maintain the gelation of the electrolyte (Japanese Patent Application Laid-Open No. 63 _ 25656 丨), or those using ceramic fibers and gelled electrolyte (Japanese Patent Application Laid-Open No. 6 1-2 5 0 9 6 8) is also well known. However, the sealed lead-acid battery formed and configured from the above-mentioned conventional materials and structures will generate an electrochemical reaction of the following type when charged:
PbSO.+ 2H2O+ PbS〇4-^ Pb+ 2H2SO4+ Pb〇2 反之’在放電時則將產生下式電化學反應：PbSO. + 2H2O + PbS〇4- ^ Pb + 2H2SO4 + Pb〇2 On the contrary, when the discharge occurs, an electrochemical reaction of the following formula will occur:
Pb+ 2H2SO4+ Pb〇2-> PbS〇4+ 2H2O+ PbS〇4 因此正極在放電時便產生H2O，而在充電時則產生H2S〇4 ，所以若重複循環放電使用的話，此所產生的H2S〇4與 H2〇便無法分布於整體極板上，將產生H2S〇4因比重而集 中於極板下方的成層化現象。 隨此種成層化現象，即便施行充電，在電極下方亦將轉 變成較不易產生充電反應，同時，因爲儲存著PbS〇4，所 以在電極活性物質與電解液間的電分解將不均勻，而產生 極板劣化與耐久性短縮化的問題。 在爲防止此種成層化現象的產生，便必須將極板極板群 加壓並容納於電解槽內，俾使各極板與隔板均勻的密接’ 但是若採用此種構造的話，則存在有於組裝電池時的作業 -4- 508857 五、發明説明（3 ) 性將降低，且電解槽需要高強度者的缺點。) 再者，因爲在蓄電池充放電中，正負極板中的活性物質 將產生體積變化，所以配設於正極板與負極板間的隔板， 因爲在充放電時將重複被壓迫，所以必須具備可吸收電極 體積變化的足夠壓縮性與柔軟性。 再者，密閉型鉛蓄電池於重複充放電之後，在正極與負 極聚電體格子表面上，將析出硫酸鉛pbSCU的離子性結晶 體，此所析出的結晶體，便將阻塞構成正極與負極之海綿 狀多孔性構造的活性物質，而造成阻礙極板內部的硫酸離 子傳送與擴散。特別係當電解液濃度較高，且析出結晶較 小之情況時，因爲正負極表面將被硫酸鉛結晶粒子所覆蓋 ，所以便產生放電時間縮短（即放電容量降低），且在正負 極板內，亦持產生活性物質將由聚電體格子上脫落或缺損 的現象，所以即便施行充電，亦較不易產生化學反應。因 此，蓄電量將顯著減少並縮短壽命，依情況亦可產生無法 充電或電極間短路的現象。 [發明揭示] 本發明有鑑於上述諸點，其目的在於提供一種可防止隔 板與電極間的密接性不均勻，與隨電解液流動而不致產生 比重甚至濃度不均勻的成層化現象發生，同時可抑制甚至 防止在正負二極中所生成析出之硫酸鉛PbS〇4離子性結晶 體之所謂硫酸鹽化作用的硫化現象的密閉型鉛蓄電池0 緣是，本發明者爲解決上述課題，遂經各種探討，結果 便發現若隔板係採用： 508857 五、發明説明（4 ) (1 )屬於將複數片由多孔性陶瓷纖維織物所形成的薄片 疊層而成的陶瓷薄片疊層體，且吸水率100%以上，表面積 較大，耐酸性較優，離子吸附性較高的陶瓷薄片疊層體； (2)此陶瓷薄片疊層體二側面，疊層上通氣性佳且具細 微網孔狀構造之合成樹脂纖維薄片者； 而且，此合成樹脂纖維薄片部分係依接觸於正負極板海棉 狀活性物質之方式進行配置的話，便可解決上述問題點， 遂完成本發明。 換句話說，本發明之密閉型鉛蓄電池，其特徵在於： 在具備有由配設於正極板與負極板、以及二極板間之隔 板所構成的極板群；及容納該極板群且儲存電解液的電 解槽之密閉型鉛蓄電池；其中，該隔板係使用： (1 )屬於將複數片由多孔性陶瓷纖維織物所形成的薄 片豐層而成的陶瓷薄片豐層體’且吸水率100%以上’表 面積較大，耐酸性較優，離子吸附性較高的陶瓷薄片疊 層體； (2 )此陶瓷薄片疊層體二側面，疊層上通氣性佳且具細 微網孔狀構造之合成樹脂纖維薄片者； 而且’此合成樹脂纖維薄片部分係依接觸於正負極板海 棉狀活性物質之方式進行配置。 再者’本發明乃構成該隔板的合成樹脂纖維，係爲以丙 烯與乙烯爲原材料，且纖維徑在數V m以下，最好在1〜2 // m之細微纖維結晶性聚丙烯織物。 再者’本發明乃構成陶瓷薄片疊層體之陶瓷纖維，係以 508857 五、發明説明（5 ) 氧化鋁及矽石爲主成分的多孔性纖維’且纖維徑在5 # m 以下，最好在2〜3/z m以下。 [圖式簡單說明] 第1圖係構成本發明密閉型鉛蓄電池之極板群中其之 一的分解剖面示意圖。 第2圖係第1圖所示陶瓷薄片疊層體1 3的分解剖面不意 圖。 第3圖係採用由聚酯纖維板與玻璃纖維所構成作爲隔板 之比較例1的其中一極板群分解剖面示意圖。 第4圖係採用由固體狀陶瓷多孔體與玻璃纖維所構成 作爲隔板之比較例2的其中一極板群分解剖面示意圖。 [實施發明較佳態樣] 本發明之密閉型鉛蓄電池，係如第1圖所示，疊層複數 由多孔性陶瓷纖維織物所構成之薄片的陶瓷薄片疊層體1 3 ，並將此陶瓷薄片疊層體1 3二側面，疊層上通氣性佳且具 細微網孔狀構造的合成樹脂纖維薄片14，並以此爲隔板10 ，將此隔板1 0配置於負極11與正極1 2之間，而形成一極 板群，且配合所需的電壓與容量，將特定數量的極板群容 納於電解槽（未圖示）中，並注入電解液後而製得。 此陶瓷薄片疊層體13係如第2圖所示，將由多孔性陶瓷 纖維織物所形成的薄片21，疊層上特定片數後，再以適當 壓力壓縮而形成。 此外，在本發明中，多孔性陶瓷纖維織雖採用將以氧化 鋁Al2〇3與S 202爲主成分的多鋁紅柱石系者，施行電加熱 -7- 508857 五、發明説明（6 ) 溶解，並吹入高速空氣流，而所形成的多孔質纖維狀者， 但並不僅限於此，以了適當選擇採用依週知的陶瓷纖維製 造方法，而所獲得的多孔質纖維。 本發明中所採用的陶瓷纖維係屬多孔性，且纖維徑在約 5 // ΙΏ以下者。若陶瓷纖維的直徑超過5 # m的話，因爲所獲 得隔板將喪失柔軟性，所以係爲不佳；反之，若過細的話 ，則因爲在製造上將產生困難，所以最好纖維徑在2〜3 // m範圍內。若陶瓷纖維本身無多孔性的話，則電解液的 吸收性將變小，且雜質離子的吸附性亦將劣化，所以屬較 不佳狀況。 在本發明中，將編織上述陶瓷纖維並當作陶瓷薄片21 (第2圖）者，疊層複數片之後，再加壓壓縮，而形成陶瓷 薄片疊層體13(第1圖）。陶瓷薄片疊層體13的厚度，雖最 好採用約1.5im左右者，但配合所需要電解液的浸漬量等 ，可適當的變更。 本發明中所採用的合成樹脂纖維薄片1 4係僅需要爲通氣 性佳且具細微網孔狀構造之合成樹脂纖維薄片的話便可， 可採用任何種類者，但最好採用以丙烯與乙烯爲.原材料之 細微結晶性聚丙烯纖維織物。此纖維徑在數// m以下，最 好在1〜2//m範圍內者。 在本發明中，將上述陶瓷薄片疊層體丨3二側面，依位 於上述合成樹脂纖維薄片1 4位置處方式進行配置，而形 成隔板1 0。此隔板1 0之合成樹脂纖維薄片1 4的部分，係 依接觸於負極板1 1與正極板1 2之海綿狀活性物質之方 508857 五、發明説明（7 ) 式，進行配置而形成極板群。 本發明之鉛蓄電池，係將特定片數的上述極板群容納 於電解槽中，然後再注入電解液（稀硫酸）而製得。 (實施例） 以下，針對實施本發明之較佳實施態樣，採用實施例與 比較例進行詳細說明。 在此實施例中，電極係採用將習知正負極活性物質Pb〇2 、Pb，形成具細微孔海綿狀，且供保持活性物質的聚電體 格子則在Pb-Ca合金中，混摻微量Sn (約1.5重量％)、Ag (約1重量％)，而強化活性物質與格子之接合者。 此外，多孔性陶瓷纖維係將純度較高的氧化鋁Al2〇3約 4 7%、矽石Si〇2約52%、及氧化亞鐵Fe2〇3、氧化鈦Ti〇2、 氧化鈣CaO、氧化鎂MgO、鹼R2〇、無水硝酸B2〇3總計約 1 %，予以混合並電加熱溶解，且以高速空氣流噴塗，而形 成平均粒徑2〜3 // m之纖維狀，然後將其進行編織便形成 如第2圖所示符號21之薄面狀。纖維密度爲0.25g/cm2。 將此陶瓷薄片2 1疊層複數片，並經加壓壓縮後，便可 獲得柔軟的紙狀陶瓷薄片疊層體1 3。厚度約1 . 5mm。 接著，編織以丙烯與乙烯爲原材料之纖維徑1 . 5 // m的結 晶性聚丙烯纖維，而獲得網孔15〜20g/m2、通氣度360cc /cm2/Sec的合成樹脂纖維薄片。 將此合成樹脂纖維薄片，如第1圖中符號1 4所示般，依 覆蓋上述陶瓷薄片疊層體1 3二側的方式進行配置，而形成 隔板1 0，並將此隔板1 0配置於負極1 1與正極1 2之間，而 508857 五、發明説明（8 ) 形成一個極板群，採用6個此種極板群，並串聯連接，然 後經注入普通所採用的稀硫酸電解液，便組裝成額定電壓 12V(2V/1格）、定額容量38Ah/20小時率的密閉型鉛蓄電 池。 此密閉型鉛蓄電池的充放電特性，係如下進行測量。 (a )將上述電池豈放於-3 °C環境中。 (b) 連接上放電電流l〇A的定電流負荷。 (c) 測量電池的端子電壓在放電結束後的終止電壓，變 爲1 0 . 2 V爲止時所需的放電時間’將放電負荷設定成連接 狀態，並持續流通電流，於電池的端子電壓變成IV以下時 ，將正、負極端子形成短路後放置1小時。 (d) 在電池充電初期階段中，流通0.7500(20.5八）之一 定充電電流1小時，而施行急速充電。但，此時控制電流 ，使充電時的電池端子電壓在14.7V以下。 (e )測量在各循環的（b )程序中，電池電壓變成1 〇 . 2 V 爲止的時間（分），並將此設定爲此循環的放電時間。 本發明之電池充放電循環試驗結果，如表1所示。 (比較例1 ) 另，在比較例1中，除採用習知例之隔板的玻璃纖維與 潦J旨纖維板之外，其餘均採用如同實施例者，而形成密閉 型鉛蓄電池。 此比較例1的極板群構造，如第3圖中所示。在第3圖 中，30係指極板群，3 1係指負極板，32係指正極板，33 係指聚酯纖維板，34係指玻璃纖維薄片。聚酯纖維板33與 -10- 508857 五、發明説明（ ） 玻璃纖維薄片3 4的厚度，分別對應實施例中的陶瓷薄片疊 層體1 3與合成樹脂纖維薄片1 4厚度，調整爲約略相同狀 態。 採用此比較例1的電池，如同實施例1，施行循環試驗 ，將結果與實施例結果同時整理於表1中。 (比較例2) 另，在比較例2中，除取代實施例1之陶瓷薄片疊層體 13，而改用固體多孔性多鋁紅柱石（3Ah〇3 · 2Si〇2)板之外 ，其餘均採用如同實施例者，而形成密閉型鉛蓄電池。 此比較例2的極板群構造，如第4圖中所示。在第4圖 中，40係指極板群，4 1係指負極板，42係指正極板，43 係指多孔性多鋁紅柱石板，44係指玻璃纖維薄片。多孔性 多銘紅柱石板4 3與玻璃纖維薄片4 4的厚度，分別對應實 施例中的陶瓷薄片疊層體1 3與合成樹脂纖維薄片丨4厚度 ，調整爲約略相同狀態。 採用此比較例2的電池，如同實施例般施行循環試驗， 將結果與實施例結果同時整理於表1中。 由表1結果明顯得知，本發明之密閉型鉛蓄電池，相對 於比較例1及2之電池循環壽命僅爲3〜4次之下，本發明 之密閉型鉛蓄電池即便重複充電24吹，亦幾乎無劣化現 象產生，可達極優越的效果。 比較例1之習知例隔板構造電池的急速充電、放電之循 環試驗結果’在表1中所示的第4次循環中，負極板之海 綿狀Pb活性物質表面上，將可目測到通稱收縮（s h r i n g ) -11- 508857 五、發明説明（1()) 的活性物質收縮，或由聚電體格子產生脫落缺損的其情 形。但是，採用本發明隔板構造之電池的負極板活性物 質表面上，即便在施行24次的急速充電後，目測結果亦 無收縮或硫酸鹽化作用（硫酸鉛之析出結晶體及粒子）的 產生現象，相較於其他隔板構造例子，得知具極優越的 電極板劣化抑制效果，與提昇循環壽命的功效。 放電時間相較於習知例之下，本發明之隔板構造所衍 生出結果的原因雖未必明確，但可認爲因爲陶瓷纖維之 疊層薄片的纖維間及多孔性陶瓷纖維本身的孔之中儲存 著離子，所以化學反應與離子釋出速度平衡較佳，而提 昇電池充放電時的利用率（通常爲3 5〜5 0%)所致。 -12- 508857 五、發明説明（11 ) [表1 ]Pb + 2H2SO4 + Pb〇2- > PbS〇4 + 2H2O + PbS〇4 Therefore, H2O is generated when the positive electrode is discharged, and H2S〇4 is generated when charged, so if the cycle discharge is used repeatedly, the H2S〇4 generated by this It cannot be distributed on the whole electrode plate with H2〇, and H2S04 will be layered under the plate because of the specific gravity. With this layering phenomenon, even if charging is performed, the charging reaction will be less likely to occur under the electrode. At the same time, because PbS04 is stored, the electrolysis between the electrode active material and the electrolyte will be uneven, and Problems such as deterioration of the electrode plate and shortening of durability occur. In order to prevent such a layering phenomenon, it is necessary to pressurize the electrode plate group and store it in an electrolytic cell, so that each electrode plate and the separator are evenly and closely contacted. However, if such a structure is adopted, it exists There is a disadvantage in the work of assembling a battery -4- 508857 V. Description of the invention (3) The disadvantages are that the property will be reduced and the electrolytic cell needs high strength. ) Furthermore, since the active material in the positive and negative plates changes in volume during the charge and discharge of the battery, the separator disposed between the positive and negative plates must be repeatedly pressed during charge and discharge. Sufficient compressibility and flexibility to absorb changes in electrode volume. Furthermore, after the sealed lead-acid battery is repeatedly charged and discharged, ionic crystals of lead sulfate pbSCU will be precipitated on the surface of the grid of the positive electrode and the negative electrode. The precipitated crystals will block and form a sponge shape of the positive electrode and the negative electrode. Porous structure of the active material, which hinders the transport and diffusion of sulfate ions inside the plate. Especially when the electrolyte concentration is high and the precipitated crystals are small, the surface of the positive and negative electrodes will be covered with lead sulfate crystal particles, so that the discharge time will be shortened (that is, the discharge capacity will be reduced), and the It also holds the phenomenon that the active material will fall off or be missing from the grid of the polymer, so even if charging is performed, it is less likely to produce a chemical reaction. As a result, the amount of stored power will be significantly reduced and the life will be shortened. Depending on the situation, it will not be able to charge or short-circuit between the electrodes. [Invention of the Invention] The present invention has been made in view of the foregoing points, and an object thereof is to provide a layering phenomenon that can prevent uneven adhesion between a separator and an electrode, and cause the occurrence of a layering phenomenon that does not cause specific gravity or even uneven concentration as the electrolyte flows. A sealed lead-acid battery capable of suppressing or even preventing the sulfurization of the so-called sulfation effect of the lead sulfate PbS04 ionic crystals formed in the positive and negative poles. After discussion, it was found that if the separator is used: 508857 V. Description of the invention (4) (1) It is a ceramic sheet laminate formed by laminating a plurality of sheets made of porous ceramic fiber fabric, and the water absorption rate Above 100%, ceramic sheet laminate with large surface area, excellent acid resistance, and high ion adsorption; (2) The ceramic sheet laminate has two sides with good air permeability and fine mesh structure. The synthetic resin fiber sheet; In addition, if the synthetic resin fiber sheet is arranged in contact with the sponge-like active material on the positive and negative electrode plates, the problem can be solved. As mentioned above, the present invention has been completed. In other words, the sealed lead-acid battery of the present invention is characterized by comprising: an electrode plate group composed of a separator disposed between the positive electrode plate, the negative electrode plate, and the second electrode plate; and a storage space for the electrode plate group. And a sealed lead-acid battery of an electrolytic cell storing an electrolytic solution; wherein the separator is used: (1) a ceramic thin layered body made of a plurality of thin layered layers formed of a porous ceramic fiber fabric; and Water absorption rate of 100% or more 'Ceramic flake laminate with larger surface area, better acid resistance, and higher ion adsorption; (2) Two sides of this ceramic flake laminate, with good air permeability and fine mesh on the stack A synthetic resin fiber sheet having a structure like this; and 'this synthetic resin fiber sheet portion is arranged so as to be in contact with a positive and negative electrode plate sponge-like active material. Furthermore, the present invention is a synthetic resin fiber constituting the separator, which is made of propylene and ethylene, and the fiber diameter is a few micrometers, preferably 1 to 2 // m. . Furthermore, the present invention is a ceramic fiber constituting a ceramic sheet laminate, which is a porous fiber mainly composed of 508857 V. Description of the Invention (5) Alumina and silica, and the fiber diameter is 5 # m or less, preferably Below 2 ~ 3 / zm. [Brief description of the drawings] Fig. 1 is a schematic exploded cross-sectional view of one of the electrode plate groups constituting the sealed lead-acid battery of the present invention. Fig. 2 is an exploded cross-sectional view of the ceramic sheet laminate 13 shown in Fig. 1 and is not intended. Fig. 3 is a schematic exploded cross-sectional view of one of the electrode plate groups of Comparative Example 1 using a polyester fiber plate and glass fiber as a separator. Fig. 4 is a schematic cross-sectional view of one electrode plate group of Comparative Example 2 using a solid ceramic porous body and glass fibers as a separator. [Preferred Aspect of Implementing the Invention] As shown in FIG. 1, the sealed lead storage battery of the present invention is a ceramic sheet laminate 1 3 laminated with a plurality of sheets made of porous ceramic fiber fabric, and the ceramic The sheet laminate 1 3 has two sides, and a synthetic resin fiber sheet 14 having a fine air permeability and a fine mesh structure is laminated, and this is used as a separator 10. This separator 10 is arranged on the negative electrode 11 and the positive electrode 1. 2 to form an electrode plate group, and according to the required voltage and capacity, a specific number of electrode plate groups are accommodated in an electrolytic cell (not shown), and the electrolyte is injected to obtain the electrode plate group. This ceramic sheet laminate 13 is formed by laminating a specific number of sheets 21 made of a porous ceramic fiber fabric as shown in Fig. 2 and then compressing them with an appropriate pressure. In addition, in the present invention, although the porous ceramic fiber weave adopts a polyalusite system composed mainly of alumina Al203 and S 202, electric heating is performed. 7-508857 V. Explanation of the invention (6) Dissolution The porous fibrous material formed by blowing a high-speed air stream is not limited to this, and the porous fiber obtained by adopting a known ceramic fiber manufacturing method is appropriately selected. The ceramic fiber used in the present invention is porous, and the fiber diameter is less than about 5 // 1Ώ. If the diameter of the ceramic fiber exceeds 5 # m, the obtained separator will lose its flexibility, so it is not good. On the other hand, if it is too thin, it will cause difficulties in manufacturing, so the fiber diameter is preferably 2 ~ 3 // m range. If the ceramic fiber itself is non-porous, the absorption of the electrolytic solution will be reduced, and the adsorption of impurity ions will also be deteriorated. In the present invention, the ceramic fiber is woven as the ceramic sheet 21 (Fig. 2), and a plurality of sheets are laminated and then pressed and compressed to form a ceramic sheet laminate 13 (Fig. 1). Although the thickness of the ceramic sheet laminate 13 is preferably about 1.5 μm, it can be appropriately changed in accordance with the amount of the electrolyte to be impregnated. The synthetic resin fiber sheet 1 to 4 used in the present invention need only be a synthetic resin fiber sheet having excellent air permeability and a fine mesh structure. Any type may be used, but propylene and ethylene are preferred. . Fine crystalline polypropylene fiber fabric for raw materials. The fiber diameter is below the number of // m, and preferably within the range of 1 to 2 // m. In the present invention, the two side surfaces of the ceramic sheet laminate 3 are arranged so as to be positioned at the position of the synthetic resin fiber sheet 14 to form a separator 10. The part of the synthetic resin fiber sheet 14 of this separator 10 is based on the sponge-like active material that is in contact with the negative plate 11 and the positive plate 12 2 508857 V. Description of the invention (7), the electrode is formed to form an electrode Board group. The lead storage battery of the present invention is prepared by accommodating the above-mentioned electrode plate group of a specific number in an electrolytic cell, and then injecting an electrolytic solution (dilute sulfuric acid). (Examples) Hereinafter, preferred embodiments of the present invention will be described in detail using examples and comparative examples. In this embodiment, the electrode system uses the conventional positive and negative active materials Pb02 and Pb to form a sponge with fine pores, and the grid of the polymer for holding the active material is in a Pb-Ca alloy, mixed in a small amount Sn (approximately 1.5% by weight) and Ag (approximately 1% by weight) strengthen the bonding of the active material and the lattice. In addition, the porous ceramic fiber system has a high purity of about 4 7% of aluminum oxide Al2O3, about 52% of silica SiO2, and ferrous oxide Fe203, titanium oxide Ti02, calcium oxide CaO, and oxidation. Magnesium MgO, alkali R2O, anhydrous nitric acid B2O3 total about 1%, mixed and dissolved by electric heating, and sprayed with high-speed air flow to form a fibrous shape with an average particle diameter of 2 to 3 // m, and then carried out Knitting results in a thin surface like 21 shown in FIG. The fiber density was 0.25 g / cm2. A plurality of these ceramic sheets 21 are laminated and compressed under pressure to obtain a soft paper-like ceramic sheet laminate 1 3. The thickness is about 1.5mm. Next, a crystalline polypropylene fiber having a fiber diameter of 1.5 // m using propylene and ethylene as raw materials was woven to obtain a synthetic resin fiber sheet having a mesh size of 15 to 20 g / m2 and an air permeability of 360 cc / cm2 / Sec. This synthetic resin fiber sheet is arranged as shown by the reference numeral 14 in FIG. 1 so as to cover both sides of the ceramic sheet laminate 13 to form a separator 10, and the separator 10 It is arranged between the negative electrode 11 and the positive electrode 12, and 508857 V. Description of the invention (8) A group of electrode plates is formed, and 6 such electrode plate groups are used, connected in series, and then injected into the ordinary dilute sulfuric acid electrolysis Liquid, then assembled into a sealed lead-acid battery with a rated voltage of 12V (2V / 1 grid) and a rated capacity of 38Ah / 20 hours. The charge-discharge characteristics of this sealed lead-acid battery were measured as follows. (a) Should the above batteries be placed at -3 ° C? (b) Connect a constant current load with a discharge current of 10A. (c) Measure the terminal voltage of the battery's terminal voltage after the discharge is completed. The discharge time required until the terminal voltage becomes 10.2 V. Set the discharge load to the connected state and continue to flow current. The terminal voltage of the battery becomes When the voltage is below IV, the positive and negative terminals are shorted and left for 1 hour. (d) In the initial stage of battery charging, one of the charging currents of 0.7500 (20.5) is circulated for one hour, and rapid charging is performed. However, at this time, the current is controlled so that the battery terminal voltage during charging is below 14.7V. (e) Measure the time (minutes) until the battery voltage becomes 10.2 V in the (b) program of each cycle, and set this as the discharge time of this cycle. The results of the battery charge-discharge cycle test of the present invention are shown in Table 1. (Comparative Example 1) In Comparative Example 1, a sealed lead-acid battery was formed as in the example except that the glass fiber of the conventional example and the 潦 J purpose fiberboard were used. The structure of the plate group of Comparative Example 1 is shown in FIG. 3. In Figure 3, 30 is the electrode plate group, 31 is the negative plate, 32 is the positive plate, 33 is the polyester fiber board, and 34 is the glass fiber sheet. Polyester fiber board 33 and -10- 508857 5. Description of the invention () The thickness of the glass fiber sheet 34 corresponds to the thickness of the ceramic sheet laminate 1 3 and the synthetic resin fiber sheet 14 in the examples, and is adjusted to approximately the same state. . The battery of Comparative Example 1 was subjected to a cycle test in the same manner as in Example 1. The results are summarized in Table 1 together with the results of the examples. (Comparative Example 2) In Comparative Example 2, except that instead of the ceramic sheet laminate 13 of Example 1, a solid porous mullite (3Ah03 · 2Si〇2) plate was used instead. All adopt the same as in the embodiment to form a sealed lead-acid battery. The structure of the plate group of Comparative Example 2 is shown in FIG. 4. In Figure 4, 40 refers to the electrode plate group, 41 refers to the negative electrode plate, 42 refers to the positive electrode plate, 43 refers to the porous polyalusite plate, and 44 refers to the glass fiber sheet. The thickness of the porous Dolomite slate 4 3 and the glass fiber sheet 4 4 correspond to the thickness of the ceramic sheet laminate 13 and the synthetic resin fiber sheet 4 in the embodiment, and are adjusted to approximately the same state. The battery of this comparative example 2 was subjected to a cycle test as in the example, and the results and the results of the example are arranged in Table 1 at the same time. From the results in Table 1, it is clear that the sealed lead-acid battery of the present invention has a cycle life of only 3 to 4 times compared to the batteries of Comparative Examples 1 and 2. Even if the sealed lead-acid battery of the present invention is repeatedly charged for 24 hours, There is almost no deterioration, and excellent results can be achieved. Comparative example 1 of the conventional example of a separator structure battery for rapid charge and discharge cycle test results' In the fourth cycle shown in Table 1, on the surface of the sponge-like Pb active material of the negative plate, a general name can be visually observed Shrinking -11- 508857 V. Description of the invention (1 ()) The shrinkage of the active material, or the shedding defect caused by the polymer grid. However, on the surface of the negative electrode active material of the battery using the separator structure of the present invention, even after 24 times of rapid charging, there was no phenomenon of shrinkage or sulfation (precipitated crystals and particles of lead sulfate) observed by visual inspection. Compared with other examples of separator structure, it is known that it has an excellent effect of suppressing the deterioration of the electrode plate and the effect of improving the cycle life. Compared with the conventional example, the reason for the discharge time of the separator structure of the present invention is not necessarily clear, but it can be considered that it is because of the interfibers of the laminated sheet of ceramic fibers and the pores of the porous ceramic fiber itself. The ions are stored in the medium, so the chemical reaction and the ion release speed have a better balance, which improves the utilization rate of the battery during charging and discharging (usually 35 to 50%). -12- 508857 V. Description of the invention (11) [Table 1]
-13- 508857 五、發明説明（12 ) 符號之說明 10.. ..隔板 11.. ..負極板 12.. ..正極板 13 . · ..陶瓷薄片疊層體 14.. .·合成樹脂纖維薄片 21 ·. ..陶瓷薄片 3〇.· ..極板群 31 .. ..負極板 33 .. ..聚酯纖維板 34 .. ..玻璃纖維薄片 40 .. ..極板群 41 .. ..負極板 42 .. ..正極板 43 .. • •多孔性多鋁紅柱石板 44.. ..玻璃纖維薄片 -14--13-508857 V. Explanation of the invention (12) Symbols 10 .... separator 11 .... negative electrode plate 12 ...... positive electrode plate 13 ... Synthetic resin fiber sheet 21 ··· ceramic sheet 30 ··· electrode group 31 ··· negative electrode plate 33 ··· polyester fiber plate 34 ··· glass fiber sheet 40 ··· electrode plate Group 41 .... Negative plate 42 .... Positive plate 43 .. • • Porous polyalusite plate 44 ... Glass fiber sheet-14-