201241243 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種藉由鍍鋁而在樹脂表面形成鋁結構 體之方法，尤其是關於一種於各種過濾器或電池用電極等 用途中可適用作為金屬多孔體之鋁結構體及其製造方法。 【先前技術】 具有三維網孔結構之金屬多孔體被應用於各種過濾 器、催化劑載體、電池用電極等多方面。例如，由鎳構成 之Celmet (住友電氣工業股份有限公司製造，註冊商標） 破使用作為鎳氫電池或鎳鎘電池等電池的電極材料^ Celmd 係具有連通氣孔的金屬多孔體’相較於金屬不織布等其他 多孔體1有孔隙率較高（9㈣以上）的特徵。其係藉由 如下方式獲得：於發泡胺曱酸乙酯等具有連通氣孔之多孔 體樹脂的骨架表面形成㈣吏’進行熱處理使發泡樹脂成 形體分解’再進—步對錄進行還原處理。錄層之形成係藉 由將碳粉末等塗佈於發泡樹脂成形體的骨架表面並進行導 電化處理後，再利用電鍍析出鎳來進行。 鋁具有導電性、耐腐蝕性、輕量等優異特徵。於電池 :途令’例如使用銘箱表面塗佈有姑酸鐘等活性物質者作 為鐘離子電池的正極。為 ^ ^ ^ 為了 k同正極之容量，可考慮將鋁 體以擴大表面積’然後亦於銘内部填充活性物 質如此一來’即使增厚電極，亦可利用活性物 質，母早位面積的活性物質利用率會獲得提高。 作為銘多孔體之劁#古、土 U方法，於專利文獻1中記載有如 201241243 下方法：對具有内部連通空間之三維網狀塑膠基體，藉由 電弧離子被覆法（arc ion plating meth〇d )實施蒸鍍鋁處理， 以形成2〜20从m的金屬鋁層。又，於專利文獻2中記載 有如下方法：於具有三維網孔狀結構之發泡樹脂成形體的 骨架，形成於鋁的熔點以下會形成共晶合金之金屬（銅等） 所構成的被膜後’塗佈鋁糊，並於非氧化性環境下以550 C以上7 5 0 C以下的溫度進行熱處理，藉此進行有機成分 (發泡樹脂）之消除及鋁粉末之燒結，獲得金屬多孔體。 另一方面，由於鋁對氧之親和力大，電位比氫低，故 鋁之鍵敷難以於水溶液系之艘敷浴中進行電鍍。因此，自 先前以來，對於鋁之電鍍之研究，一直是在非水溶液系之 鍍敷浴中進行。例如，作為以防止金屬表面氧化等為目的 而進行鍍鋁的技術，於專利文獻3中揭示有一種電鍍鋁方 法，其特徵在於：使用混合熔融有鏽鹵化物（〇nium halide ) 與鋁ii化物之低熔點組成物作為鍍敷浴，一面將浴中的水 刀量維持在2wt%以下，一面使鋁析出於陰極。 專利文獻1 :曰本特許第34丨3662號公報 專利文獻2 .日本特開平8— 170126號公報 專利文獻3:曰本特許第32〇2〇72號公報 【發明内容】 若使用上述專利文獻i之方法，雖可獲得厚度為2〜 20以m之鋁多孔體，但是其係藉由氣相法而獲得因此難以 進订大面積之製造’且由於基體之厚度或孔隙率的原因而 難以形成均勻之層至内部。並且由於鋁層之形成速度慢、 4 201241243 設備價格高昂等，因此存在製造成本增大等問題點。並且， 於形成厚骐之情形時，會有膜產生龜裂或發生鋁脫落之 虞。若使用專利文獻2之方法，則會得到形成鋁與共晶合 金之層’無法形成純度高之鋁層。另—方面，雖然已知鋁 電鑛法本身，但是僅可對金屬表面進行㈣，而對樹脂成 =體表面進行電鑛，尤其於具有三維網孔結構之多孔質樹 脂成形體表面進行電鍵之方法並不為人所知。係認為鑛敷 浴中之多孔質樹脂的溶解等問題會造成影響。 因此，本發明的目的在於提供一種即使是具有三維網 孔結構之多孔質樹脂成形體，亦可對其表面㈣，且均句 地形成厚膜’藉此形成純度高之鋁結構體的方法，以及特 別是可獲得大面積之鋁多孔體的方法。 為了解決上述課題，本案發明人等想到了將紹電鑛於 «甲酸酿或三聚氰胺樹脂等具有三維網孔結構之樹脂成 形體表面的方法。亦即本發明為一種鋁結構體之製造方 法，具有下述步驟：在熔鹽浴中將鋁鍍敷於至少表面經導 電化之具有三維網孔結構的樹脂成形體，該炫鹽為氯化鋁 與有機鹽之混合鹽，使該熔鹽浴之溫度在45t以上i〇(rc 以下進行鍍敷（請求項1 )。 本發明人等發現在為有機鹽與氣化銘之混合鹽的炫鹽 浴中鍵敷㈣方*，可有效作為對具有三維結構之樹 脂成形體表面鍍敷紹的方法。由於味唾鏽鹽（imidazolium salt)等有機鹽與氣化狀混合鹽在常溫下為液體，因此通 常使鍍敷浴的溫度為室溫附近的溫度 '然而在常溫附近之 201241243 溫度’熔鹽的黏度高，故對於如具有三維網孔結構之樹脂 成形體此種具有複雜骨架結構者而言，視鍍敷的條件有時 會無法進行良好的鍍敷。尤其是在製造大面積之鋁多孔體 時必須提高電流密度，但是若熔鹽的黏度低，則可進行鍍 敷的電流密度範圍將會變小。若將熔鹽浴的溫度設在4 5 以上1 001：以下，則可降低熔鹽浴的黏度，可充分地將熔鹽 擴及到具有三維網孔結構之樹脂成形體（多孔體）的内部。 因此可進行多孔體表面部與内部之鍍敷厚度差小的均勻鑛 敷。且藉由可形成均勻厚度之鍍敷’而可得到鋁層強度變 強’即使是在去除樹脂成形體後骨架結構斷裂亦少的鋁結 構體。 ° 於前述熔鹽中，若進一步含有濃度在0.25g/l以上7g 以下之丨，1〇一啡啉，則可提升鍍敷表面的平滑性而較佳 (响求項2)。藉由在將熔鹽浴之溫度設於一定範圍降低黏 度後添加1，10-啡啉，兩者之相乘效果可將骨架表面之鍍 敷從粒狀（凹凸大，進行表面觀察時看㈣以粒狀物） 改善成平坦形狀’藉此可得到即使是厚度薄且細之骨架亦 強健不易彎折的鋁結構體。 、 述有機鹽較佳為含有氮之熔鹽，其中較佳 鏘鹽（請求項3 ) „ w米唾鑷鹽與氣化鋁 且導電率一 < 屁D皿由於會在較低的溫度； 含有第二位因於作為炼鹽浴。^坐鏽鹽較佳可僅 化】— 八有烷基之味座鏘陽離子之鹽，特別是 C*基 九 rn -/7 3 甲咪唑鑕 1 — ethyl — 3 6 201241243 methylimidaz〇lium chloride )與氣化鋁之混合鹽（A1Ci3 — EMIC )，因穩定性高且難以分解，故可最佳地進行使用。 另，由於咪唑鏽鹽浴厭惡水分和氧之存在，因此較佳於密 閉環境下進行氬或氮等惰性氣體環境下的鍍敷。 發泡胺甲酸乙酯及發泡三聚氰胺由於孔隙率高、具有 氣孔連通性且熱分解性優異’因此可較佳地使用作為樹脂 多孔體（請求項4)。發泡胺甲酸乙g旨在氣孔均勻性及 容易度等方面較佳’而發泡三聚氰胺則是在可得到氣孔徑 小者的方面較佳。 ㈣夕孔體表面之導電化方法，可在已知方法中加以 « ° (non-electrolytic plating) ^ 相法形成紹、錦等金屬層，或者利用導電性塗料形成金屬 ^層。藉由氣相法形成㈣或以碳進行導電化，由於錄 :之紹結構體不會混入紹以外的金屬，因： 金屬之形態實質上僅由紹構成的結構體。 “以 藉由以上之步驟，可得到具有表面具備金 :形體的紹結構體。根據各種過遽器或 = 旨 途，亦可直接作為樹脂與金屬之複合體使用，又載=等用 用環境之限料，因此當作為不含樹脂 由於使 時，亦可將樹脂去除（請求項5 )。 〜構體使用 藉由上述不易彎折且鍍敷厚度内 於對完成之链多孔體進行加壓的情形^個特徵’ 體不易蠻折均等受到加遂的多孔體。字=得到骨架整 池等之電極材料使用時，會在電極填:^孔體作為電 具兄電極活性物質並藉 201241243 由加壓提升密度，在活性拍j哲夕+古+ w «又隹布往物頁之填充步驟及加壓時由於骨 架容易彎折，因此在此種用途上極為有效。 根據本發明，可提供-種能對尤其是具有三維網孔結 構之多孔質樹脂成形體的表面進行鍍紹，並能以大致均一 之厚膜形成純度高且大面積之鋁結構體的方法及鋁結構 體。 【實施方式】 以下，以製造鋁多孔體之步驟為代表例並參照適當的 圖式來說明本發明之實施形態。以下所參照之圖式中，編 有相同編號之部分係相同或與其相當之部分。另，本發明 並不限定於此’係以中請專利範圍表示，射請專利範圍 均等之含意及範圍内之所有變更均包含在内。 (鋁結構體之製造步驟） 第1圖係表示本發明之鋁結構體的製造步驟之流程 圖。又，第2圖對應於流程圖而示意性地表示以樹脂多孔 體為芯材來形成鋁結構體的情況。參照兩圖式說明製造步 驟整體之流程。首先進行基體樹脂成形體之準備1〇1。第2 圖之（a )部分係以基體樹脂成形體之例，將具有三維網孔 結構之樹脂多孔體（發泡樹脂成形體）表面放大觀察而得 的放大示意圖。以發泡樹脂成形體丨為骨架而形成有氣孔。 繼而進行樹脂成形體表面之導電化1 〇2。藉由此步驟，如第 2圖之（b)部分所示，於發泡樹脂成形體丨之表面，薄薄 地形成由導電體構成之導電層2。接著，進行熔鹽中之錢鋁 103’在形成有導電層之樹脂成形體的表面形成鍍鋁層3(第 8 201241243 2圖之（c)部分）。藉此’可獲得以樹脂成形體為基材且 在表面形成有鑛紹層3之铭結構體。進而，亦可進行基體 樹脂成形體之去除1〇4。藉由對發泡樹脂成形體1進行分解 等而使其消失’可獲得僅殘留金屬層之銘結構體（多孔體） (第2圖之（d )部分）。以下按順序說明各步驟。 (樹脂多孔體之準備） 準備具有三維網孔結構之樹脂多孔體。樹脂多孔體之 素材可選擇任意樹脂。素材可例示：聚胺甲酸酯、三聚氰 胺樹脂、聚丙烯、聚乙烯等發泡樹脂成形體。若是具有連 續之氣孔（連通氣孔）者，則可選擇任意形狀之樹脂多孔 體。例如’亦可使用纏繞著纖維狀樹脂並具有如不織布之 形狀者作為樹脂多孔體。樹脂多孔體之孔隙率較佳為⑽％ 〜98%，氣孔徑較佳為5〇 a m〜5〇〇以m。發泡胺甲酸乙酯 及發泡三聚氰胺之孔隙率高，並具有氣孔連通性，且熱分 解性亦優異，因此可較佳地使用作為樹脂多孔體。發泡胺 曱酸乙酯（胺曱酸乙酯發泡體）在氣孔均勻性及取得之容 易程度等方面較佳，而發泡三聚氰胺則是在獲得小氣孔徑 者方面較佳。 於樹脂多孔體經常會有發泡體製造過程中的發泡劑或 未反應之單體等殘留物，為了後續步驟，較佳進行清洗處 理。作為樹脂多孔體之例，將發泡胺曱酸乙酿經作為前處 理之清洗處理者示於第3圖。樹脂成形體藉由構成三維網 孔作為骨架，而於整體上構成連續的氣孔。發泡胺甲酸乙 酉旨之骨架在與其延伸方向垂直之剖面上略呈三角形。此 201241243 處，孔隙率由下式定義。 孔*隙率=(1 一 的體積[cm3]x素材密 (多孔質材料的重量[g]/度）））χΐοο[%] 多孔質材料 又:氣孔徑係利用顯微鏡照片《放大樹脂成形體表 面，以每英寸（25.4mm)之氣孔數作為單元數進行計數， 按平均孔徑= 25.4mm/單元數來求出平均值。 (樹脂多孔體表面之導電化：碳塗佈） 準備作為導電性塗料的碳塗料。作為導電性塗料之懸 浮液較佳為含有碳粒子、黏結劑、分散劑及分 $均勾地塗佈導電性粒子，必須將懸浮液維持在均勻的懸 浮狀態。因此，懸浮液較佳維持在2〇<t〜贼。其理由在 於：懸浮液之溫度未達抓之情形時，均句的懸浮狀態會 瓦解’於樹脂多孔體之呈網狀結構之骨架表面僅有黏結劑 集中而形成層。此情形時，戶斤塗佈之碳粒 難以形成牢固密合之金屬鑛敷。另一方面，懸浮液二 超過贼之情形時，分散劑之蒸發量大，隨著塗佈處理時 間的流逝，懸浮液發生濃縮，碳之塗佈量容易發生變動。 又，碳粒子之粒徑為〇·01〜5" m ,較佳為〇 〇1〜〇 ⑺。 若粒徑大，則會導致堵塞樹脂多孔體之空孔或阻礙平滑之 鍍敷，若粒徑過小，則難以確保充分的導電性。 對樹脂多孔體塗佈碳粒子，可藉由將對象樹脂多孔體 浸潰於上述懸浮液，並進行擠壓與乾燥來實施。第4圖示 意性地表示對作為骨架之帶狀樹脂多孔體進行導電化的處 理裝置構成例，作為實用上製造步驟之一例。如圖所示， 201241243 ι裝置具備有.供給帶狀樹脂11的供應捲軸12、裝有導電 塗料懸浮液14的槽15、配置於槽15上方的1對擠壓輥 相尉向設置在行進之帶狀樹脂i i後方的複數個熱風喷 嘴备及捲取處理後之帶狀樹脂11的捲取捲軸18。又， 適當配置有用於引導帶狀樹脂"的導輥⑴於如上述般構 裝置中，具有二維網狀結構之帶狀樹脂1會自供應捲 車 捲回，爻導輥丨3引導而浸潰於槽15内之懸浮液中。 槽15内浸潰於懸浮液14之帶狀樹脂n，改變為朝向上方， 行進於懸浮液14液面上方的擠壓帛17之間。此時，擠壓 之間隔小於帶狀樹脂11之厚度，帶狀樹脂1 1受到壓 縮因此，含改於帶狀樹脂11之過剩的懸浮液會被擠出而 返回至槽15内。 繼而，帶狀樹脂1 1再次改變行進方向。此處，藉由複 =個喷嘴構成之熱風喷嘴16喷射的熱風去除懸浮液之分散 "質等，充分乾燥後，帶狀樹脂丨丨被捲取至捲取捲軸1 8。 另，熱風噴嘴16喷出之熱風的溫度較佳為4(rc〜8〇ec之範 圍。右使用上述裝置，則可自動且連續地實施導電化處理， 形成具有無堵塞之網孔結構且具備均勻導電層之骨架，因 此可順利地進行下一步驟之鍍金屬。 (銘層之形成：熔鹽鍍敷） 繼而於熔鹽中進行電鍍，於樹脂多孔體表面形成鍍鋁 層。以表面經導電化之樹脂多孔體為陰極，以純度為99 99 %之鋁板為陽極，於熔鹽中施加直流電流。使用氣化鋁與 有機鹽之混合鹽（共晶鹽）作為熔鹽。若使用於相對低溫 201241243 下會熔融之有機熔鹽浴，則能夠在不會使作為基材之樹脂 多孔體分解的情況下進行鍍敷，故較佳。有機鹽可使用咪 唑鏽鹽、吡啶鏽鹽（pyridinium sah )等。其中，較佳為氣 化1—乙基一3—甲咪唑钂（ EMIC)、氣化丁基吡啶鏽（Βρ〇β 為了降低熔鹽的黏度，熔鹽浴的溫度設在4 5。〇以上 以下。當溫度低於45t:時，無法使黏度充分降低。又 當溫度高於loot時，則有可能會使有機鹽分解。更佳之溫 度為以上8G°C以下。若於㈣中混人水分或氧，則由 於會導致熔鹽劣化，因此較佳於氮、氬等惰性氣體環境下 且於密閉環境下進行鍵敷。 若於熔鹽浴添加1，1 0 一啡啉，則表面會變得平滑，故 較佳。1，1〇—啡啉的添加量較佳在O hg/!以上7g/l以 下。若添加量少於0.25g/丨，則難以得到使表面呈平滑的效 果雖然1，1〇 -啡琳的添加量越多，使表面呈平滑的效果 越高，但是即使較7g/l多，效果亦不太會改變。更佳之添 加量的範圍在2.5g/l以上5g/l以下。 若為將有機溶劑等添加於熔鹽浴以降低黏度的方法， 則需要用於防止有機溶劑揮發的設備或用於防止由有機溶 劑弓丨起之著火的安全設備，但是於本發明中，由於使溫度 在p定範圍以降低熔鹽浴的黏度，因此可使用簡便的設備 進仃鑛敷》且由於！，！〇_啡琳在价〜1()(rc的範圍亦不會 揮發’因此具有同樣的效果。 第5圖係示意性地表示用於對上述帶狀樹脂連續進行 金屬處理之裝置的構成之圓。係表示將表面經導電化之 12 201241243 帶狀樹脂22自圖的左邊輸送至右邊之構成。第丨鍍敷槽2u 係由圓筒狀電極24、設置於容器内壁之陽極25及鍍敷浴 23構成。藉由使帶狀樹脂22沿圓筒狀電極24通過鍍敷浴 23之中，可使得電流易均勻地流經於整個樹脂多孔體，獲 得均勻之鍍敷。第2鍍敷槽21b係用於進一步較厚且均勻 地進仃鍍敷之槽，構成為於複數個槽中重複進行鍍敷。一 邊藉由兼用作輸送輥與槽外供電陰極之電極輥26來依次輸 j表面經導電化之帶狀樹脂22，一邊使其通過鍍敷浴28, 糟此進行《 i複數個槽时陽極27，該陽極隔著鑛 敷液28設置於樹脂多孔體兩面之對向面，可對樹脂多孔體 之兩面進行更均勻的鍍敷。 藉由以上步驟’可獲得具有樹脂多孔體作為骨架芯之 紹結構體（紹多孔體）。根據各種過遽器或催化劑載體等 用途’亦可直接作為樹脂與金屬之複合體使用。又，由於 使用環境之限制等’因此當作為沒有樹脂之金屬結構體使 :夺、亦可將樹月曰去除。樹脂之去除，可藉由利用有機溶 音方“ 解）、加熱分解等任 忍方法進仃。鋁與鎳等不同，芒一 用氬理m ., y —氧化，則難以進行還 原處理，因此，例如當作為雷 ^ β 乍為電池等之電極材料使用時，較 佳以不易引起鋁氧化之方法來去 下㈣夕益士 h 來去除树月曰。例如較佳使用以 下說明之藉由在熔鹽中的熱分解將樹脂去除之方法。 (樹脂之去除：熔鹽中之熱分解） 炼鹽中之熱分解係以下述方法進行 紹層之樹脂多孔體浸潰於炫鹽 （成有鍍 进對鋁層施加負電位一 13 201241243 邊進行加熱，以分解樹脂多孔體《若於浸潰在熔鹽之狀態 下施加負電位’則能夠在不使鋁氧化的情況下分解樹脂多 孔體。加熱溫度可配合樹脂多孔體之種類適當選擇，但為 了不使鋁熔化，必須於鋁之熔點（660。(：）以下的溫度進行 處理。較佳之溫度範圍係500t以上600°C以下。又，所施 加之負電位之量，與鋁的還原電位相比，為負側，且與熔 鹽中之陽離子的還原電位相比，為正側。 用於樹脂熱分解之熔鹽，可使用如鋁之電極電位為低 之驗金屬或鹼土金屬的鹵化物之鹽或硝酸鹽。具體而言， 較佳為包含選自由氣化鋰（LiCl )、氯化鉀（KC1 )、氣化鈉 (NaCl )、氣化鋁（A丨Cl3 )、硝酸鋰（UN〇3 )、亞硝酸鋰 (lino2 )、硝酸鉀（KN〇3)、亞硝酸鉀（kn〇2 )、硝酸鈉 (NaN〇3 )、及亞硝酸鈉（NaN〇2 )構成之群中的1種以上。 藉由此種方法，可獲得表面之氧化層薄、氧量少的鋁多孔 體。 (鋰離子電池） 接著說明使用鋁多孔體之電池用電極材料及電池。當 用於例如鋰離子電池之正極的情形時，使用鈷酸鋰 (LiC〇〇2)、錳酸鋰（LiMn204 )、鎳酸鋰（LiNi〇2)等作 為活性物質。活性物質係與導電助劑（c〇nductive aid )及 黏合劑組合使用。以往的鋰離子電池用正極材料，於鋁箔 表面塗佈有活性物質。為了提高每單位面積之電池容量， 大了活I·生物質之塗佈厚度。又，為了有效利用活性物質， 鋁’泊與活性物質必須電性接觸，因此，活性物質係與導電 201241243 助劑混合使用。相對 τ於此’本發明之鋁多孔體的孔隙率高 且每單位面積之表面 土 & 槓大。因此’即使於多孔體表面載持 較薄的活性物質，亦 Γ 了有效利用活性物質，提高電池容量， 且可減少導電助劑之人θ ^ w 尾合1。鋰離子電池係以上述正極材 料為正極，負極伸田：密 吏用石墨’電解質則使用有機電解液。此 種鐘離子電池即使雷 之電極面積小亦可提高容量，因此，盥以 往之鋰離子電池相比， ’ 了提间電池之能量密度。 (熔鹽電池） 銘多孔體亦可体田 吏用作為熔鹽電池用之電極材料。於使 用銘多孔體作為正極材 夺材科之情形時，會使用亞鉻酸鈉 (NaCr02)、二硫化叙 & 一 化鈦（TlS2 )等可插入（intercalation ) 作為電解質之熔鹽的陽離 勿雕于之金屬化合物，來作為活性物 質0活性物質係與導雷 、導電助劑及黏合劑組合使用。導電助劑 引吏用乙快碳等。又’黏合劑可使用聚四氟乙烯（PTFE ) * ;使用亞鉻酸納作為活性物f且使用乙快碳作為導電 助劑之情形時，PTFET更牢固地固定這兩者，因此較佳。 紹多孔體亦可使用作為熔鹽電池用之負極材料。於使 用銘多孔體作為負極材粗夕，降π 枓之清形時，活性物質可使用鈉單 萨1 、其他金屬之合金、碳等。鈉的熔點為❸98。。，且 =溫度上升金屬會軟化，因此，較佳將納與其他金屬⑶、201241243 VI. Description of the Invention: [Technical Field] The present invention relates to a method for forming an aluminum structure on a resin surface by aluminum plating, and more particularly to a use in various filters or electrodes for batteries and the like. An aluminum structure as a porous metal body and a method for producing the same. [Prior Art] A porous metal body having a three-dimensional mesh structure is applied to various filters, catalyst carriers, electrodes for batteries, and the like. For example, Celmet (manufactured by Sumitomo Electric Industries Co., Ltd., registered trademark) made of nickel is used as an electrode material for batteries such as nickel-hydrogen batteries or nickel-cadmium batteries. ^ Celmd is a metal porous body having interconnected pores compared to metal non-woven fabrics. Other porous bodies 1 have characteristics of high porosity (9 (four) or more). It is obtained by forming a surface of a skeleton of a porous body resin having interconnected pores such as a foaming amine decanoic acid ethyl ester, and performing heat treatment to decompose the foamed resin molded body to carry out reduction treatment. . The formation of the recording layer is carried out by applying carbon powder or the like to the surface of the skeleton of the foamed resin molded body and conducting a conductive treatment, followed by depositing nickel by plating. Aluminum has excellent characteristics such as electrical conductivity, corrosion resistance, and light weight. For the battery: the order, for example, the surface of the name box is coated with an active material such as a sorrel clock as the positive electrode of the ion battery. For ^ ^ ^ In order to calculate the capacity of the positive electrode, it is considered to enlarge the surface area of the aluminum body and then fill the active material inside the inside. Thus, even if the electrode is thickened, the active material can be used as the active material in the mother early area. Utilization will increase. As an example of the 多孔# ancient and soil U method of the porous body, Patent Document 1 describes a method as follows: 201241243: a three-dimensional mesh plastic substrate having an internal communication space, by arc ion plating method (arc ion plating meth〇d) An aluminum deposition treatment is performed to form a metal aluminum layer of 2 to 20 m. Further, Patent Document 2 describes a method of forming a skeleton of a foamed resin molded body having a three-dimensional mesh structure and forming a film composed of a metal (copper or the like) of a eutectic alloy below the melting point of aluminum. The aluminum paste is applied and heat-treated at a temperature of 550 C or more and 750 C or less in a non-oxidizing atmosphere to remove the organic component (foaming resin) and to sinter the aluminum powder to obtain a porous metal body. On the other hand, since aluminum has a large affinity for oxygen and a potential lower than that of hydrogen, it is difficult to perform plating in an aqueous solution bath in an aqueous solution. Therefore, research on the electroplating of aluminum has been carried out in a non-aqueous plating bath since the beginning. For example, as a technique for performing aluminum plating for the purpose of preventing oxidation of a metal surface or the like, Patent Document 3 discloses a method of electroplating aluminum characterized by using a mixture of molten rust halides and aluminum ii compounds. The low melting point composition is used as a plating bath, and aluminum is deposited on the cathode while maintaining the amount of water in the bath at 2 wt% or less. Patent Document 1: Japanese Patent Application Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. In the method, although an aluminum porous body having a thickness of 2 to 20 m can be obtained, it is obtained by a vapor phase method, and thus it is difficult to make a large-area manufacturing ' and it is difficult to form due to the thickness or porosity of the substrate. Evenly layer to the inside. Moreover, due to the slow formation speed of the aluminum layer and the high price of the equipment of 201241243, there are problems such as an increase in manufacturing cost. Further, in the case where a thick crucible is formed, there is a possibility that the film is cracked or aluminum is peeled off. When the method of Patent Document 2 is used, a layer forming aluminum and a eutectic alloy is obtained, and an aluminum layer having a high purity cannot be formed. On the other hand, although the aluminum electrowinning method itself is known, only the metal surface can be subjected to (4), and the surface of the resin forming body is subjected to electric ore, particularly to the surface of the porous resin molded body having a three-dimensional mesh structure. The method is not known. It is considered that the dissolution of the porous resin in the mineral bath causes problems such as dissolution. Therefore, an object of the present invention is to provide a method of forming a thick resin film on the surface (4) even if it has a three-dimensional mesh structure, thereby forming a high-purity aluminum structure. And in particular, a method of obtaining a large-area aluminum porous body. In order to solve the above problems, the inventors of the present invention have thought of a method of depositing a surface of a resin molded body having a three-dimensional mesh structure such as formic acid brewing or melamine resin. That is, the present invention is a method for producing an aluminum structure, which comprises the steps of: plating aluminum in a molten salt bath on a resin molded body having a three-dimensional mesh structure in which at least a surface is electrically conductive, the dashed salt being chlorinated a mixed salt of aluminum and an organic salt, and the temperature of the molten salt bath is plated at a temperature of 45 rpm or more (rectification 1). The present inventors have found that it is a mixed salt of an organic salt and a vaporized salt. The salt bath (4) square* can be effectively used as a method for plating the surface of a resin molded body having a three-dimensional structure. The organic salt and the gasified mixed salt such as imidazolium salt are liquid at normal temperature. Therefore, the temperature of the plating bath is usually set to a temperature near room temperature 'however, the viscosity of the molten salt of the 201241243 temperature near the normal temperature is high, so that it has a complicated skeleton structure such as a resin molded body having a three-dimensional mesh structure. In other words, depending on the conditions of plating, good plating may not be performed. Especially in the production of a large-area aluminum porous body, the current density must be increased, but if the viscosity of the molten salt is low, the current density of the plating can be performed. If the temperature of the molten salt bath is set to be 4 5 or more and 1 001 or less, the viscosity of the molten salt bath can be lowered, and the molten salt can be sufficiently expanded to a resin molded body having a three-dimensional mesh structure ( Therefore, a uniform mineral having a small difference in plating thickness between the surface of the porous body and the inside can be performed, and the strength of the aluminum layer can be obtained by forming a plating of uniform thickness 'even if it is removed An aluminum structure in which the skeletal structure is less broken after the resin molded body. ° In the above molten salt, if the cerium is further contained in a concentration of 0.25 g/l or more and 7 g or less, 1 〇-morpholine can improve the smoothness of the plating surface. Sexually and better (Responding to Item 2). By adding the 1,10-morpholine after setting the temperature of the molten salt bath to a certain range to reduce the viscosity, the synergistic effect of the two can be used to plate the surface of the skeleton from the particles. The shape is large (the unevenness is observed, and when the surface is observed, the grain is shaped as a granular material), and the aluminum structure is hardened and bent, and the organic salt is preferably made even if the thickness is thin and the skeleton is thin. a molten salt containing nitrogen, preferably a phosphonium salt (request 3) „ w m sputum salt and vaporized aluminum and conductivity one < fart D dish will be at a lower temperature; contain the second place as a salt bath. ^ rust salt is better to be condensed] - eight a salt of an alkyl group having a ruthenium cation, particularly a mixed salt of a C* group of nine rn -/7 3 mebendazole 锧 1 - ethyl - 3 6 201241243 methylimidaz 〇lium chloride ) and a vaporized aluminum (A1Ci3 - EMIC ), Since it is highly stable and difficult to decompose, it can be used optimally. Further, since the imidazole rust salt bath is detrimental to the presence of moisture and oxygen, it is preferable to perform plating in an inert gas atmosphere such as argon or nitrogen in a closed environment. The foamed urethane and the foamed melamine are preferably used as a resin porous body because of high porosity, pore connectivity, and excellent thermal decomposition property (Requirement 4). The foaming amine ethane g is preferable in terms of stomatal uniformity and easiness, and foamed melamine is preferable in that a small pore diameter can be obtained. (4) The method of conducting the surface of the celestial body can be formed by a non-electrolytic plating method in a known method to form a metal layer such as sho, jin or the like, or a conductive coating to form a metal layer. By forming (4) by vapor phase method or conducting electricity by carbon, since the structure is not mixed with a metal other than the one, the form of the metal is substantially only a structure composed of the structure. "With the above steps, it is possible to obtain a structure having a gold-like surface on the surface. It can also be used directly as a composite of resin and metal according to various types of filters or =, and it can also be used in environments where it is used. The material is limited, so that the resin can be removed as the resin is not contained (claim 5). The structure is used to pressurize the completed chain porous body by the above-mentioned non-bending and plating thickness. In the case of the case, the body is not easily deformed and is uniformly twisted. The word = when the electrode material such as the skeleton is used, the electrode is filled in the electrode: the hole body is used as the electrode active material of the electric device and is used by 201241243 Pressurization to increase the density, and it is extremely effective in such a use because it is easy to bend in the filling step and pressurization of the active sheeting j 夕 夕+古古 w. According to the present invention, it is provided. A method and an aluminum structure capable of plating a surface of a porous resin molded body having a three-dimensional mesh structure, and capable of forming a high-purity and large-area aluminum structure with a substantially uniform thick film. the way Hereinafter, an embodiment of the present invention will be described with reference to a typical example of a step of producing an aluminum porous body. In the following drawings, the same reference numerals are used for the same or equivalent parts. The present invention is not limited to the scope of the invention, and all modifications within the scope and scope of the invention are included. (Manufacturing Procedure of Aluminum Structure) FIG. 1 shows the present invention. A flow chart of a manufacturing step of the aluminum structure. Fig. 2 is a view schematically showing a case where an aluminum structure is formed by using a resin porous body as a core material, and the flow of the entire manufacturing step will be described with reference to the two drawings. First, the preparation of the base resin molded body is carried out. The part (a) of the second drawing is an example of a base resin molded body, and the surface of the resin porous body (foamed resin molded body) having a three-dimensional mesh structure is enlarged and observed. An enlarged view is obtained. The foamed resin molded body is used as a skeleton to form pores. Then, the surface of the resin molded body is electrically conductive 1 〇 2. By this step, as shown in Fig. 2 As shown in part b), the conductive layer 2 composed of a conductor is formed thinly on the surface of the foamed resin molded body 。. Next, the surface of the resin molded body in which the conductive layer is formed is performed on the molten aluminum 103' in the molten salt. The aluminum-plated layer 3 is formed (part 8(c) of Fig. 8 201241243 2). By this, it is possible to obtain a structure in which a resin molded body is used as a base material and a mineral layer 3 is formed on the surface. Further, a base body can be formed. Removal of the resin molded body 1〇4. The foamed resin molded body 1 is decomposed or the like to be removed, and the in-form structure (porous body) in which only the metal layer remains is obtained (part (d) of Fig. 2) Each step is described in the following order. (Preparation of Resin Porous Body) A resin porous body having a three-dimensional mesh structure is prepared. The material of the resin porous body may be any resin selected from the group consisting of polyurethane, melamine resin, and poly A foamed resin molded body such as propylene or polyethylene. In the case of a continuous pore (connecting pore), a resin porous body of any shape can be selected. For example, a resin porous body may be used in which a fibrous resin is wound and has a shape such as a non-woven fabric. The porosity of the resin porous body is preferably from (10)% to 98%, and the pore diameter is preferably from 5 〇 a m to 5 〇〇 in m. The foamed urethane and the foamed melamine have high porosity, good pore connectivity, and excellent thermal decomposition property, and thus can be preferably used as a resin porous body. The foaming amine ethyl decanoate (ethylamine phthalate foam) is preferred in terms of stomatal uniformity and ease of handling, and foamed melamine is preferred in obtaining a small pore size. In the resin porous body, there are often residues such as a foaming agent or an unreacted monomer in the production process of the foam, and it is preferred to carry out a cleaning treatment for the subsequent steps. As an example of the resin porous body, the foaming amine phthalic acid is shown in Fig. 3 as a cleaning treatment for the pretreatment. The resin molded body constitutes a continuous pore as a whole by constituting a three-dimensional mesh as a skeleton. The skeleton of the foaming urethane is slightly triangular in cross section perpendicular to the direction in which it extends. At 201241243, the porosity is defined by the following formula. Hole *gap ratio = (1 volume [cm3] x material density (weight of porous material [g] / degree))) χΐοο [%] porous material: pore size system using a microscope photograph "magnification resin molded body The surface was counted by the number of pores per inch (25.4 mm) as the number of cells, and the average value was determined by the average pore diameter = 25.4 mm / unit number. (Electrification of Surface of Resin Porous Body: Carbon Coating) A carbon coating material as a conductive coating material was prepared. The suspension of the conductive paint preferably contains carbon particles, a binder, a dispersant, and a conductive particle, and the suspension must be maintained in a uniform suspended state. Therefore, the suspension is preferably maintained at 2 〇 < t thief. The reason is that when the temperature of the suspension is not caught, the suspension state of the uniform sentence collapses. On the skeleton surface of the resin porous body, only the binder is concentrated to form a layer. In this case, it is difficult for the carbon particles coated by the household to form a tightly bonded metal ore. On the other hand, when the suspension 2 exceeds the thief, the amount of evaporation of the dispersant is large, and as the coating treatment time elapses, the suspension concentrates, and the amount of carbon coating tends to fluctuate. Further, the particle diameter of the carbon particles is 〇·01 to 5" m , preferably 〇 〇1 to 〇 (7). When the particle diameter is large, the pores of the porous resin body are blocked or the smooth plating is inhibited. If the particle diameter is too small, it is difficult to ensure sufficient conductivity. The application of the carbon particles to the resin porous body can be carried out by immersing the target resin porous body in the above suspension, followed by extrusion and drying. The fourth diagram is an example of a configuration of a processing apparatus for conducting electric current on a strip-shaped resin porous body as a skeleton, and is an example of a practical manufacturing step. As shown in the figure, the 201241243 ι device is provided with a supply reel 12 for supplying the strip resin 11, a groove 15 containing the conductive coating suspension 14, and a pair of squeezing rollers disposed above the groove 15 in the direction of travel. A plurality of hot air nozzles behind the strip resin ii and a take-up reel 18 of the strip resin 11 after the winding process are prepared. Further, a guide roller (1) for guiding the strip-shaped resin is appropriately disposed in the apparatus as described above, and the strip-shaped resin 1 having a two-dimensional network structure is wound back from the supply reel, and the crucible guide roller 3 is guided. Dip into the suspension in tank 15. The strip-shaped resin n impregnated in the suspension 14 in the groove 15 is changed to face upward, and travels between the extruded crucibles 17 above the liquid level of the suspension 14. At this time, the interval between the pressing is smaller than the thickness of the strip-shaped resin 11, and the strip-shaped resin 11 is compressed, so that the excess suspension containing the modified resin 11 is extruded and returned to the tank 15. Then, the strip resin 1 1 changes the traveling direction again. Here, the dispersion of the suspension is removed by the hot air jet 16 formed by the hot air nozzle 16 composed of a plurality of nozzles, and after sufficient drying, the strip-shaped resin crucible is taken up to the take-up reel 18. Further, the temperature of the hot air blown by the hot air nozzle 16 is preferably in the range of 4 (rc to 8 〇 ec.) When the device is used right, the conductive treatment can be automatically and continuously performed to form a mesh structure having no clogging and The skeleton of the conductive layer is uniform, so that the metallization of the next step can be smoothly performed. (Formation of the ingot layer: molten salt plating) Then electroplating is performed in the molten salt to form an aluminized layer on the surface of the porous resin body. The conductive resin porous body is a cathode, and an aluminum plate having a purity of 99 99 % is used as an anode, and a direct current is applied to the molten salt. A mixed salt of a vaporized aluminum and an organic salt (eutectic salt) is used as a molten salt. The organic molten salt bath which is melted at a relatively low temperature of 201241243 can be plated without decomposing the porous resin body as a substrate. The organic salt can be an imidazolium salt or a pyridinium salt (pyridinium). Sah), etc. Among them, it is preferred to vaporize 1-ethyl-3-imidazolium (EMIC), gasified butylpyridinium rust (Βρ〇β in order to reduce the viscosity of the molten salt, the temperature of the molten salt bath is set at 4 5. 〇 above or below. When When the temperature is lower than 45t:, the viscosity cannot be sufficiently reduced. When the temperature is higher than the loot, the organic salt may be decomposed. The temperature is preferably below 8G ° C. If the water or oxygen is mixed in (4), Since the molten salt is deteriorated, it is preferably subjected to bonding under an inert gas atmosphere such as nitrogen or argon in a sealed environment. If 1,10-morpholine is added to the molten salt bath, the surface becomes smooth. Therefore, it is preferred that the amount of 1,1〇-phenoline added is 7 g/l or less above 0 hg/! If the amount added is less than 0.25 g/丨, it is difficult to obtain a smooth surface effect although 1,1 The more the amount of 〇-morphine added, the higher the surface smoothing effect, but even if it is more than 7g/l, the effect will not change much. The added amount is more than 2.5g/l and below 5g/l. In order to reduce the viscosity by adding an organic solvent or the like to the molten salt bath, a device for preventing volatilization of the organic solvent or a safety device for preventing ignition by the organic solvent is required, but in the present invention, Can be used because the temperature is set in p to reduce the viscosity of the molten salt bath The equipment is in the ore deposit and because of!,! 〇 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ The circle of the device for continuously performing metal treatment of the strip resin is a structure in which the surface of the 12 201241243 strip resin 22 which is electrically conductive is transported from the left side of the drawing to the right side. The second plating bath 2u is composed of a cylindrical electrode. 24. The anode 25 and the plating bath 23 are disposed on the inner wall of the container. By passing the strip-shaped resin 22 through the plating bath 23 along the cylindrical electrode 24, the current can be easily and uniformly flowed through the entire resin porous body. The uniform plating is obtained. The second plating tank 21b is used to further thicken and uniformly feed the plating grooves, and is configured to repeatedly perform plating in a plurality of grooves. The strip-shaped resin 22 which is electrically conductive on the surface is sequentially fed by the electrode roller 26 which serves as both the transport roller and the outer-supply cathode, and passes through the plating bath 28, thereby performing "i" a plurality of slots at the anode 27 The anode is provided on the opposite faces of both sides of the resin porous body via the ore-laying liquid 28, and more uniform plating can be performed on both surfaces of the resin porous body. By the above step, a structure having a resin porous body as a skeleton core (a porous body) can be obtained. It can also be used directly as a composite of a resin and a metal according to various applications such as a filter or a catalyst carrier. Further, due to restrictions in the use environment, etc., it is also possible to remove the tree scorpion as a metal structure without a resin. The removal of the resin can be carried out by any method such as "solution" by organic sound solution, heat decomposition, etc. Aluminum is different from nickel, and the awning is difficult to carry out the reduction treatment by using argon, m, and y. For example, when it is used as an electrode material such as a battery, it is preferable to remove the tree sputum by a method which does not easily cause aluminum oxidation. For example, it is preferable to use the following description by melting The method of removing the resin by thermal decomposition in the salt. (Removal of the resin: thermal decomposition in the molten salt) The thermal decomposition in the salt is carried out by the following method: the resin porous body is immersed in the sulphate salt By applying a negative potential to the aluminum layer 13 201241243, it is heated to decompose the porous resin body. If a negative potential is applied in the molten salt state, the porous resin body can be decomposed without oxidizing aluminum. The type of the resin porous body can be appropriately selected. However, in order not to melt the aluminum, it is necessary to carry out the treatment at a temperature lower than the melting point of aluminum (660 ° (:)). The preferred temperature range is 500 t or more and 600 ° C or less. The amount of the negative potential applied is the negative side compared with the reduction potential of aluminum, and is the positive side compared with the reduction potential of the cation in the molten salt. The molten salt for thermal decomposition of the resin can be used, for example, aluminum. a salt or a nitrate of a halide of a metal or alkaline earth metal having a low electrode potential. Specifically, it preferably comprises a selected one selected from the group consisting of lithium sulfide (LiCl), potassium chloride (KC1), and sodium carbonate (NaCl). Gasified aluminum (A丨Cl3), lithium nitrate (UN〇3), lithium nitrite (lino2), potassium nitrate (KN〇3), potassium nitrite (kn〇2), sodium nitrate (NaN〇3), and One or more of the group consisting of sodium nitrite (NaN〇2). By such a method, an aluminum porous body having a thin oxide layer on the surface and a small amount of oxygen can be obtained. (Lithium Ion Battery) Next, an aluminum porous body will be described. Electrode material for battery and battery. When used in a positive electrode such as a lithium ion battery, lithium cobaltate (LiC〇〇2), lithium manganate (LiMn204), lithium nickelate (LiNi〇2), or the like is used as an active material. The active material is used in combination with a conductive additive (c〇nductive aid) and a binder. The polar material is coated with an active material on the surface of the aluminum foil. In order to increase the battery capacity per unit area, the coating thickness of the living I·biomass is increased. In addition, in order to effectively utilize the active material, the aluminum 'pore and active material must be electrically Contact, therefore, the active material is mixed with the conductive 201241243 auxiliary. The aluminum porous body of the present invention has a high porosity and a large surface area per unit area. Therefore, even on the surface of the porous body Holding a thin active material, it also effectively utilizes the active material, increases the battery capacity, and reduces the θ ^ w tail of the conductive additive. The lithium ion battery uses the above positive electrode material as the positive electrode and the negative electrode extends the field: dense An organic electrolyte is used for the graphite 'electrolyte. This kind of ion battery can increase the capacity even if the area of the electrode of the lightning is small, so the energy density of the battery is compared with that of the lithium ion battery. (Molten salt battery) Ming porous body can also be used as an electrode material for molten salt batteries. In the case where the porous body is used as the material of the positive electrode material, the intercalation of molten salt such as sodium chromite (NaCrO 2 ), disulfide & titanium oxide (TlS2 ) is used as the molten salt of the electrolyte. A metal compound that is not engraved is used as an active material. The active material is used in combination with a lightning guide, a conductive additive, and a binder. Conductive auxiliaries Use B fast carbon and so on. Further, when a binder is used, polytetrafluoroethylene (PTFE)* can be used. When sodium chromite is used as the active material f and B-carbon is used as the conductive auxiliary agent, PTFET is more firmly fixed, and therefore it is preferable. The porous body can also be used as a negative electrode material for a molten salt battery. When using the porous body as the negative electrode material, when the shape is reduced by π 枓, the active material may be sodium soda 1 , an alloy of other metals, carbon or the like. The melting point of sodium is ❸98. . And = the temperature rises the metal will soften, therefore, it is better to compare with other metals (3),
Sn In等）加以合金化。其中’牲免丨β收仏t 再T特別疋將鈉與Sn加以合金 化而成者因易於處理，因此較佳。可藉由電鑛、 方法將納或納合金載持於銘多孔體之表面。又，亦、可藉由 鑛敷等方法將納與要合金化之金屬⑺等）附著於銘多孔 15 201241243 體後，在熔鹽電池中進行充電，藉此製成鈉合金。 第6圖係顯示使用上述電池用電極材料之熔鹽電池一 例的剖面示意圖。熔鹽電池，係將鋁多孔體之鋁骨架部表 面載持有正極用活性物質的正極12卜鋁多孔體之鋁骨架部 表面載持有負極用活性物質的負極122、及含浸有作為電解 質之熔鹽的分隔件123收納於殼體127内而成者。在殼體 127的上面與負極之間配置有按壓構件126，該按壓構件^6 係由壓板124及對壓板進行按壓之彈簧125構成。藉由設 置按壓構件，即使於正極121、負極122及分隔件123的體 積發生變化之情形時，亦可均勻按壓使各構件接觸。正極 121的集電器（鋁多孔體）及負極122的集電器（鋁多孔體） 分別以導線130連接至正極端子128及負極端子129。 作為電解質之熔鹽可使用於運作溫度下會熔化的各種 無機鹽或有機鹽。熔鹽的陽離子可使用選自鋰（Li)、納 (Na)、鉀（K)、铷（Rb)及铯（Cs)等鹼金屬、鈹（Be)、 鎂（Mg)、鈣（Ca)、锶（Sr)及鋇（Ba)等鹼土金屬中 的1種以上。 為了降低熔鹽的熔點，較佳將2種以上之鹽混合使用。 例如若將雙（敗磺醯基）醯胺鉀（p〇tassium bis(flUorosulfonyl)amide，KFSA)與雙（氟磺醯基）醯胺鈉 (sodiumbis(fluorosulfonyl)amide，NaFSA)組合使用，則 可使電池之運作溫度在90t以下。 將溶鹽含浸於分隔件後使用。分隔件係用於防止正極 與負極接觸’可使用玻璃不織布或多孔質樹脂多孔體等。 16 201241243 將上述正極、負極、含浸有熔鹽之 内，作為電池使用。 1 +積層收納於殼體 電容器（一…。一〜—） 於使用㉝#可使用作為電雙層電容器用之電極材料。 、吏用鋁多孔體作為電雙層 時，會佶爾μ ^ 电谷器用之電極材料的情形 二會使用活性碳等作為電極活性物質。 助劑或點合劑組合使用。導電助劑可使用石墨、奈 等。又’黏合劑可使用聚四敗乙烯（PTFE)、苯 — 二烯橡膠等。 丁 第7 g係顯示使用上述電雙層電容器用電極材料 雙層電容器一例的剖面示意圖。於藉由分隔件142分隔之 有機電解& 143中，配置有將電極活性物質載持於銘多孔 體之電極材料作為極化性電極14卜電極材料i4i連接於導 線144’該等全部收納於殼體145巾。藉由將鋁多孔體使用 作為集電3 ’可使集電器的表面積增大，即使較薄地塗佈 作為活性物質之活性碳，亦可獲得可高輸出 的電雙層電容器。 (導電層之形成：碳塗佈） 以下具體說明鋁多孔體之製造例。準備厚度lmm、孔 隙率95%、氣孔徑300 e m之胺甲酸乙酯發泡體作為樹脂多 孔體，切成80mmx50mm見方。將胺甲酸乙酯發泡體浸潰於 碳懸洋液然後進行乾燥’藉此形成表面整體附著有碳粒子 之導電層。懸浮液之成分，係含有25%之石墨+碳黑且含 有樹脂黏合劑、滲透劑、消泡劑。碳黑之粒徑為〇 5 # m。 17 201241243 (導電層之形成：鋁蒸鑛） 準備與碳塗佈之情形時相同的樹脂多孔體，將鋁蒸鍍 在表面’形成厚度0.7“^之銘導電層。 (熔鹽鍍敷） 將表面形成有導電層之胺曱酸乙酯發泡體作為工件安 裝於具有供電功能之治具後，放入設為氬環境且低水分（露 點為一30°C以下）之套手工作箱内，浸潰於表i、表2所示 之溫度的熔鹽浴（33mol%EMIC_67mol%AlCl3)中。另， 於熔鹽浴中添加有表卜表2所示之濃度的丨，丨〇 _啡啉。將 安裝有工件之治具連接於整流器的陰極側，將鋁板（純度 為9 9 · 9 9 % )連接於對極之陽極側。施加表1所示之電流密 度的直流電流當2 A/cm2 (以下，將「A/cm2」稱為ASD )時 施加90分鐘’ 6ASD時施加30分鐘，15ASD時則施加1〇 分鐘鍍敷鋁。攪拌係使用鐵氟龍（註冊商標）製之轉子藉 由攪拌器進行。此處，電流密度係以胺曱酸乙酯發泡體的 表觀面積算出之值。 (樹脂多孔體之分解） 將形成有鍍鋁層之各樹脂多孔體浸潰於溫度5〇(TC之 LiCl 一 KC1共晶熔鹽，施加—iv之負電位5分鐘將聚胺甲 酸酯分解去除，得到鋁多孔體。 對所得之鋁多孔體内部的鍍敷性進行評價。内部鐘敷 之評價，係將多孔體内部之鍍敷厚度薄且在去除胺甲酸乙 西旨發泡體後剝離成2片者評價為X，多孔體内部亦有鍍敷且 未發生樣品之剝離者則評價為〇。又剖面之評價，係抽樣 18 201241243 "孔體内部亦有鍍敷且未發生樣品之剝離者，於表面部 分及垂直於骨架延伸方向之剖面切斷，埋入樹脂經研磨 後’觀察剖面。將内部之鍍敷厚度為外部之鍍敷厚度的 %以上者評價為〇，5〇%以上但未達7〇%者評價為△，未 達50%者則評價為χ。進一步為了對鍍敷之表面平滑性（於 各表十係s己载為「表面」）進行評價，而使用掃描電子顯 微鏡對鋁多孔體進行觀察，在倍率為1000倍下將表面呈平 滑者評價為◦，凹凸很明顯者則評價為X。以上之結果示於 表1、表2。 [表1] (形成有鋁導電層之樣品的結果） 啡啉濃度（g/l) 0.25 2.5 5 (電流密度） 室溫 2ASD 内部鍍敷：X 表面：〇 剖面：X 6ASD 内部鍍敷：X 表面：X 剖面：X 15ASD 内部鍍敷：X 表面：X 剖面：X 6ASD 内部鍍敷：X 表面：〇 剖面：X 6ASD 内部鍍敷：X 表面：〇 剖面：X 溫 度 (電流密度） 60°C 2ASD 内部鍍敷：〇 表面：〇 剖面：X 6ASD 内部鍍敷：〇 表面：X 剖面：X 15ASD 内部鍍敷：〇 表面：X 剖面：X 6ASD 内部鍍敷：〇 表面：〇 剖面：X 6ASD 内部鍍敷：〇 表面：〇 剖面：〇 (電流密度） 80°C 2ASD 内部鍍敷：〇 表面：〇 剖面：X 6ASD 内部鍍敷：〇 表面：X 剖面：X 15ASD 内部鍍敷：〇 表面：X 剖面：X 6ASD 内部鍍敷：〇 表面：〇 剔面：△ 19 201241243 [表2] j形成有碳導電層之彳的結果） 啡啉濃度（g/1) 0.25 1.25 2.5 5 溫 度 (電流密度） 室溫 6ASD 内部鍍敷：X 表面：X 剖面：X 6ASD 内部鍍敷：X 表面：〇 剖面：X 6ASD 内部鍍敷：X 表面：〇 Λ|| if, ； X (電流密度） 60°C 6ASD 内部鍍敷：〇 表面：X 剖面：X ' -6ASD 内部鍍敷：〇 表面：〇 剖面：X 6ASD 内部鍍敷：〇 表面：〇 奋|而；〇 (電流密度） 6ASD 6ASD 内部鍍敷：〇 内部鍍敷：〇 80 C 表面：X 表面：〇 剖面：X 剖面：△ 如表1及表2所示，鍍敷溫度為室溫之情形，内部之 鍍敷性差，去除胺曱酸乙酯發泡體後剝離成2片。而鍍敷 溫度為6(TC、8〇。〇之情形，則沒有發生剝離，内部亦可鍍 敷。其中，對鍍敷狀態詳細觀察所得之剖面評價及表面評 價，於啡啉濃度為心25g/ 1之條件下，評價大多為χ。尤 其是電流密度越南，評價結果越差，當啡啉之添加量少的 情形時，為了使鍍敷的表面平滑性良好，必須降低電流密 度慢慢地鍍敷。 圖8係使用掃描電子顯微鏡觀察對形成有鋁導電層之 樣品以啡啉濃度0.25g/卜電流密度6aSd、鍍敷溫度6(rc 的條件進行鋁鍍敷所製得之鋁結構體的照片。又圖9則是 使用掃描電子顯微鏡觀察對形成有鋁導電層之樣品以啡琳 濃度5g/卜電流密度6ASD、鍍敷溫度6〇〇c的條件進行紹 20 201241243 鍍敷所製知·之鋁結構體的照片。可知啡啉濃度較高的圖9， 鋁鍍敷的表面較為平滑，而啡啉濃度較低的圖8則在鍍敷 的表面產生凹凸。 [產業上之可利用性] 如上述，根據本發明，可得到樹脂成形體表面鍍敷有 鋁之結構體及將樹脂成形體去除之鋁結構體，因此例如能 以鋁多孔體之形態廣泛應用於電池用電極等電氣材料或各 種過濾用過濾器、催化劑載體等中利用鋁特性的情形。 【圖式簡單說明】 圖1，係顯示本發明之鋁結構體製造步驟的流程圖。 圖2，係說明本發明之鋁結構體製造步驟的剖面示意 圖。 圖3，係顯示作為多孔質樹脂成形體一例之發泡胺甲酸 乙6旨樹脂結構的表面放大照片。 圆4 ’係說明以導電性塗料進行樹脂成形體表面連續導 電化步驟一例之圖。 潤5 ’係說明以熔鹽鍍敷進行鋁連續鍍敷步驟一例 圖。 11 6 ’係顯示將鋁多孔體應用於熔鹽電池之結構例的剖 面示意圖。 圆7 ’係顯示將鋁多孔體應用於電雙層電容器之結構例 的剖面示意圖。 ® 8 ’係實施例之鋁結構體的表面放大照片》 圖9 ’係實施例之鋁結構體的表面放大照片。 21 201241243 【主要元件符號說明】 1 發泡樹脂成形體 2 導電層 3 鍍鋁層 11 帶狀樹脂 12 供應捲軸 13 導輥 14 懸浮液 15 槽 16 熱風噴嘴 17 擠壓輥 18 捲取捲軸 21a ，21b 锻敷槽 22 帶狀樹脂 23， 28 鍍敷浴 24 圓筒狀電極 25， 27 正電極 26 電極輥 121 正極 122 負極 123 分隔件 124 壓板 125 彈簧 126 按壓構件 22 201241243 127 殼體 128 正極端子 129 負極端子 130 導線 141 極化性電極 142 分隔件 143 有機電解液 144 導線 145 殼體 23Sn In, etc.) is alloyed. Among them, it is preferable that the alloy is alloyed with Sn and the alloy is easily treated. The nano or nano alloy can be carried on the surface of the porous body by means of an electric ore. Further, the metal (7) or the like to be alloyed may be adhered to the porous body 15 201241243 by a method such as mineral depositing, and then charged in a molten salt battery to prepare a sodium alloy. Fig. 6 is a schematic cross-sectional view showing an example of a molten salt battery using the above electrode material for a battery. In the molten salt battery, the surface of the aluminum skeleton portion of the aluminum porous body is provided with the positive electrode 12 for the active material for the positive electrode, and the surface of the aluminum skeleton portion of the aluminum porous body is provided with the negative electrode 122 carrying the negative electrode active material and impregnated with the electrolyte. The separator 123 of the molten salt is housed in the casing 127. A pressing member 126 is disposed between the upper surface of the casing 127 and the negative electrode, and the pressing member 26 is composed of a pressure plate 124 and a spring 125 that presses the pressure plate. By providing the pressing member, even when the volume of the positive electrode 121, the negative electrode 122, and the separator 123 is changed, the members can be uniformly pressed to bring the members into contact. The current collector (aluminum porous body) of the positive electrode 121 and the current collector (aluminum porous body) of the negative electrode 122 are connected to the positive electrode terminal 128 and the negative electrode terminal 129 by wires 130, respectively. The molten salt as the electrolyte can be used for various inorganic salts or organic salts which melt at operating temperatures. The cation of the molten salt may be selected from alkali metals such as lithium (Li), sodium (Na), potassium (K), ruthenium (Rb) and cesium (Cs), beryllium (Be), magnesium (Mg), and calcium (Ca). One or more kinds of alkaline earth metals such as strontium (Sr) and barium (Ba). In order to lower the melting point of the molten salt, it is preferred to use two or more kinds of salts in combination. For example, if a combination of p〇tassium bis (flUorosulfonyl) amide (KFSA) and sodium bis(fluorosulfonyl)amide (NaFSA) is used, The operating temperature of the battery is below 90t. Use the dissolved salt in the separator and use it. The separator is used to prevent the positive electrode from coming into contact with the negative electrode. A glass nonwoven fabric or a porous porous body of porous resin or the like can be used. 16 201241243 The above positive electrode, negative electrode, and impregnated molten salt are used as batteries. 1 + laminated layer is housed in the case of a capacitor (a... one to -). The use of 33# can be used as an electrode material for an electric double layer capacitor. When an aluminum porous body is used as the electric double layer, the electrode material for the electrode is used, and activated carbon or the like is used as the electrode active material. Auxiliaries or point combinations are used in combination. As the conductive auxiliary agent, graphite, naphthalene, or the like can be used. Further, as the binder, polytetracycline (PTFE), benzene-diene rubber or the like can be used. D. 7 g shows a schematic cross-sectional view showing an example of a double layer capacitor using the electrode material for an electric double layer capacitor. In the organic electrolysis & 143 separated by the separator 142, an electrode material for carrying the electrode active material on the porous body is disposed as the polarizing electrode 14 and the electrode material i4i is connected to the wire 144'. The housing 145 is a towel. By using the aluminum porous body as the current collector 3', the surface area of the current collector can be increased, and even if the activated carbon as the active material is applied thinly, an electric double layer capacitor having a high output can be obtained. (Formation of Conductive Layer: Carbon Coating) Hereinafter, a production example of the aluminum porous body will be specifically described. An urethane foam having a thickness of lmm, a porosity of 95%, and a pore diameter of 300 m was prepared as a resin porous body, and cut into 80 mm x 50 mm square. The urethane foam was immersed in a carbon suspension and then dried to thereby form a conductive layer having carbon particles adhered to the entire surface. The composition of the suspension contains 25% graphite + carbon black and contains a resin binder, a penetrating agent, and an antifoaming agent. The particle size of carbon black is 〇 5 # m. 17 201241243 (Formation of Conductive Layer: Aluminum Evaporation) Prepare the same porous resin body as in the case of carbon coating, and evaporate aluminum on the surface to form a conductive layer of thickness 0.7. (Fused salt plating) The amine phthalate foam having a conductive layer formed on the surface thereof is mounted as a workpiece on a jig having a power supply function, and placed in a handle box which is set to an argon atmosphere and has low moisture (with a dew point of 30 ° C or less). , immersed in a molten salt bath (33 mol% EMIC_67 mol% AlCl3) at the temperatures shown in Table i and Table 2. In addition, a concentration of bismuth, 丨〇-morphine shown in Table 2 was added to the molten salt bath. The ligature is attached to the cathode side of the rectifier, and the aluminum plate (purity of 9 9 · 9 9 %) is connected to the anode side of the counter electrode. The DC current of the current density shown in Table 1 is applied as 2 A. /cm2 (hereinafter, when "A/cm2" is called ASD), it is applied for 90 minutes at 6 ASD, and at 15 ASD, aluminum is applied for 1 minute. The stirring was carried out by using a stirrer using a rotor made of Teflon (registered trademark). Here, the current density is a value calculated from the apparent area of the amine phthalate foam. (Decomposition of Resin Porous Body) Each resin porous body in which an aluminum plating layer was formed was immersed in a LiCl-KC1 eutectic molten salt of TC (TC), and a negative potential of -iv was applied for 5 minutes to decompose the polyurethane. The aluminum porous body was removed, and the plating property inside the obtained aluminum porous body was evaluated. The inner bell coating was evaluated by thinning the plating inside the porous body and peeling off after removing the amine urethane foam. Two persons were evaluated as X, and the inside of the porous body was also plated and the sample was not peeled off, and the evaluation was evaluated as 〇. The evaluation of the profile was performed on the sample 18 201241243 "The inside of the hole was also plated and no sample occurred. For the peeling, the surface portion and the cross section perpendicular to the direction in which the skeleton extends are cut, and the embedded resin is polished to observe the cross section. The plating thickness of the inner portion is equal to or greater than the outer plating thickness, and is evaluated as 〇, 5〇%. The above is less than 7〇%, and it is evaluated as △. If it is less than 50%, it is evaluated as χ. Further, in order to evaluate the surface smoothness of plating (the surface of each table is “surface”), it is used. Scanning electron microscope to observe aluminum porous body When the magnification was 1000 times, the surface was evaluated as smooth, and the unevenness was evaluated as X. The above results are shown in Tables 1 and 2. [Table 1] (Results of samples in which an aluminum conductive layer was formed) Morphine concentration (g/l) 0.25 2.5 5 (current density) Room temperature 2ASD Internal plating: X Surface: 〇 Profile: X 6ASD Internal plating: X Surface: X Profile: X 15ASD Internal plating: X Surface: X section: X 6ASD Internal plating: X Surface: 〇 Section: X 6ASD Internal plating: X Surface: 〇 Section: X Temperature (current density) 60 ° C 2ASD Internal plating: 〇 Surface: 〇 Section: X 6ASD Internal Plating: 〇 Surface: X Profile: X 15ASD Internal plating: 〇 Surface: X Profile: X 6ASD Internal plating: 〇 Surface: 〇 Section: X 6ASD Internal plating: 〇 Surface: 〇 Section: 〇 (current density) 80°C 2ASD Internal plating: 〇 Surface: 〇 Section: X 6ASD Internal plating: 〇 Surface: X Section: X 15ASD Internal plating: 〇 Surface: X Section: X 6ASD Internal plating: 〇 Surface: 〇 〇 :△ 19 201241243 [Table 2] j is formed with carbon conduction Results of )) Phenanthine concentration (g/1) 0.25 1.25 2.5 5 Temperature (current density) Room temperature 6ASD Internal plating: X Surface: X Profile: X 6ASD Internal plating: X Surface: 〇 Section: X 6ASD Internal Plating: X Surface: 〇Λ|| if, ; X (current density) 60°C 6ASD Internal plating: 〇 Surface: X Profile: X ' -6ASD Internal plating: 〇 Surface: 〇 Section: X 6ASD Internal plating Application: 〇 surface: 〇 | | and; 〇 (current density) 6ASD 6ASD internal plating: 〇 internal plating: 〇 80 C surface: X surface: 〇 section: X section: △ as shown in Table 1 and Table 2, When the plating temperature is room temperature, the internal plating property is poor, and the amine amide foam is removed and then peeled off into two pieces. The plating temperature is 6 (TC, 8 〇. In the case of 〇, no peeling occurs, and the inside can be plated. Among them, the profile evaluation and surface evaluation obtained by detailed observation of the plating state, the concentration of morphine is 25 g. Under the condition of /1, the evaluation is mostly χ. Especially in the current density of Vietnam, the evaluation result is worse. When the amount of morpholine added is small, in order to make the surface smoothness of the plating good, it is necessary to reduce the current density slowly. Fig. 8 is a view showing an aluminum structure obtained by performing aluminum plating on a sample having an aluminum conductive layer and having a morphine concentration of 0.25 g/b current density of 6aSd and a plating temperature of 6 (rc) using a scanning electron microscope. Photograph 9 shows that the sample formed with the aluminum conductive layer was observed by scanning electron microscopy at a concentration of 5 g/b current density of 6 ASD and a plating temperature of 6 〇〇c. A photograph of the aluminum structure. It can be seen that the surface of the aluminum plating is relatively smooth in Fig. 9, and the surface of the plating having a low phenanthroline concentration is uneven on the surface of the plating. Sex as above, according to According to the present invention, an aluminum structure in which a surface of a resin molded body is plated with aluminum and an aluminum structure in which a resin molded body is removed can be obtained. For example, it can be widely applied to an electric material such as a battery electrode or various filtration filters in the form of an aluminum porous body. Fig. 1 is a flow chart showing a manufacturing step of the aluminum structure of the present invention. Fig. 2 is a cross section showing the manufacturing steps of the aluminum structure of the present invention. Fig. 3 is a surface enlarged photograph showing the structure of a foamed urethane for the resin molded body as an example of a porous resin molded body. The circle 4' shows an example of a step of continuously conducting a surface of a resin molded body with a conductive paint. Run 5 ' is an example of a continuous aluminum plating step by molten salt plating. 11 6 ' shows a schematic cross-sectional view of a structural example in which an aluminum porous body is applied to a molten salt battery. The round 7 ' shows an aluminum porous body. A schematic cross-sectional view of a structural example applied to an electric double layer capacitor. A surface enlargement photograph of an aluminum structure of the embodiment of the present invention. 21 201241243 [Description of main component symbols] 1 Foamed resin molded body 2 Conductive layer 3 Aluminized layer 11 Striped resin 12 Supply reel 13 Guide roller 14 Suspension 15 Slot 16 Hot air nozzle 17 Squeeze roller 18 take-up reel 21a, 21b forging groove 22 strip resin 23, 28 plating bath 24 cylindrical electrode 25, 27 positive electrode 26 electrode roller 121 positive electrode 122 negative electrode 123 separator 124 platen 125 spring 126 pressing member 22 201241243 127 Housing 128 Positive terminal 129 Negative terminal 130 Conductor 141 Polarizing electrode 142 Separator 143 Organic electrolyte 144 Conductor 145 Housing 23