m請委明承.月%日所提之 #.τ-,本有無變更實質内容是否准予咖羼〇 五、發明説明（i ) 03923 發明範圖 本發明係一種鋁電解電容器陰極箔的蝕刻方法，本發 明不但改進了傳統化學蝕刻方法之缺失亦克服了電化學蝕 刻方法硬體設備昂貴、蝕刻箔製造成本高之缺點，並且更 大幅提高了製程速率。 發明背景 鋁電解電容器內主要包括扮演陽極角色的蝕刻陽極箔 及扮演陰極角色的電解液及陰極端電子傳導作用的蝕刻陰 極箔’陽極箔有化成皮膜處理，作爲介電層，陰極箔則 否’但是實際使用上’陰極箔也會有一層天然的氧化皮 膜，產生如陽極箱一般的介電作用；因此鋁電解電容器的 電容量爲陽極箔電容量與陰極箔電容量之串聯合成電容 量，關係式如下·’ l/C=l/Ci + I/ C2 C :合成電容量 C i :陽極箔電容量 :陰極箔電容量 合成電容量主要取決於有化成處理的陽極箔上，所以 陰極箔的電容量越高、越穩定，對合成電容量C的影響越 小，尤其在須耐高溫的低電壓用電容器，陰極箔除了電容 本纸張尺度適用中國國家標率（CNS)A4洗格（2丨0X297公釐） (請先閏讀背面之注意事項再填寫本頁) 、-° 經濟部中央揉準局貝工消費合作社印裝 83· 3· 1〇,〇〇〇 m請委明承.月%日所提之 #.τ-,本有無變更實質内容是否准予咖羼〇 五、發明説明（i ) 03923 發明範圖 本發明係一種鋁電解電容器陰極箔的蝕刻方法，本發 明不但改進了傳統化學蝕刻方法之缺失亦克服了電化學蝕 刻方法硬體設備昂貴、蝕刻箔製造成本高之缺點，並且更 大幅提高了製程速率。 發明背景 鋁電解電容器內主要包括扮演陽極角色的蝕刻陽極箔 及扮演陰極角色的電解液及陰極端電子傳導作用的蝕刻陰 極箔’陽極箔有化成皮膜處理，作爲介電層，陰極箔則 否’但是實際使用上’陰極箔也會有一層天然的氧化皮 膜，產生如陽極箱一般的介電作用；因此鋁電解電容器的 電容量爲陽極箔電容量與陰極箔電容量之串聯合成電容 量，關係式如下·’ l/C=l/Ci + I/ C2 C :合成電容量 C i :陽極箔電容量 :陰極箔電容量 合成電容量主要取決於有化成處理的陽極箔上，所以 陰極箔的電容量越高、越穩定，對合成電容量C的影響越 小，尤其在須耐高溫的低電壓用電容器，陰極箔除了電容 本纸張尺度適用中國國家標率（CNS)A4洗格（2丨0X297公釐） (請先閏讀背面之注意事項再填寫本頁) 、-° 經濟部中央揉準局貝工消費合作社印裝 83· 3· 1〇,〇〇〇 403923 A7 B7 五、發明説明（2 ) 量要高之外’對環境改變的穩定度也要好，因此，鋁電解 電容器陰極箔材料的主要要求條件如下： 1. 高電容量：陰極箔電容量越高，則合成電容量主要來 自陽極箔的貢獻，能使電容器更符合輕、薄、短、小的 趨勢。 2. 高機械強度：電容器素子的捲繞彎曲加工時，足夠的 拉力與彎曲強度是必須的。 3. 高穩定度：封裝完成的電容器因使用及環境的改變， 陰極箔的電容量會發生改變，使得電容器品質不穩定。 ' 因此’陰極箔的蝕刻品質影響電容器的品質至鉅，如 何提高品質及降低成本乃是此一產業所想要解決的問題。 * 習知技術的問題= 目前鋁電解電容器陰極箔的蝕刻方法主要爲下列兩種 方法： (一） 電化學蝕刻方法 利用鋁箔在電解液中藉電流之作用，於電流由鋁向溶 液流通之瞬間使鋁溶入電解液中，於是在鋁箔表面形成蝕 孔，鋁之溶出量減去化學溶解量與物理溶解量後之剩餘量 恰與電流與時間之乘積成正比，鋁溶解速度之大小可藉由 電流大小加以調整，在配合溶液之溫度及濃度的控制，能 夠達到預期之擴面率。 (二） 化學蝕刻方法 本纸張尺度適用中國國家標準（CNS) A4说格（210X297公釐） (請先閏讀背面之注意事項再填寫本頁) 訂 經濟部中央揉準局属工消费合作社印策 83· 3.10,000 4- 403923 A7 B7 五、發明説明（3 ) 鋁金屬在酸液中，特別是於氫鹵酸及其鹽類中，都具 有侵入鋁表面氧化物缺點部位造成腐蝕之起始點，而進行 強烈腐蝕，舉鹽酸爲例，即鹽酸中之氯離子與鋁結合生成 A1C13溶於溶液中，而氫離子變成氫氣逸入空氣中，隨 著HC1之遞減與 A1C13之遞增，反應速率改變頗 大，造成蝕刻品質不穩定，爲了得到穩定且較佳之蝕刻品 質，除了提升溶液的管理外，亦可摻入各種添加劑，以改 善蝕刻效果。 然而，電化學蝕刻方法雖然具有（1 )可任意調整電 流大小，控制溶解速率、（2 )可改變電源型態，控制蝕 孔一致及（3 )溶液管理容易之優點，但仍然存在（1 ) 設備昂貴、（2)蝕刻箔之製造成本高及（3)無法提高 製程速率之缺點；化學鈾刻方法具有（1 )設備低廉，所 需空間小、（2 )蝕刻速率可達電化學蝕刻方法的數倍及 (4)蝕刻成本低之優點，但是仍然存在無法使業者接受 的缺點：（1 )反應狀態不穩定，不易掌控、（2 )起始 溶解速率慢，反應無法一氣呵成，係經過一段長時間慢慢 作用之後才會急遽發生反應，即有所謂反應前導期、 (3)反應前導期之後反應急遽發生，使得蝕刻不易控 制、（4 )較薄的陰極箔，容易鈾刻穿孔及（5 )電容量 提升不易。 美國專利案號4 4 3 2 8 4 6，係爲完整的電化學蝕刻製 程，利用A C/ D C電源，在鹽酸水溶液中對鋁箔表面進行 電化學蝕刻，並針對蝕刻後電容量的穩定性及殘餘氯離子 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） I I n n j ϊ (諳先閏讀背面之注意^^項再填寫本頁) 經濟部中央橾準局貝工消费合作社印氧 83.3.10,000 經濟部令央揉準局貝工消費合作社印«. 403923 五、發明説明（4 ) 的去除，作了一些後處理步驟；但蝕刻步驟太長，電化學 蝕刻效率不佳，而且後處理中使用鉻酸，增加廢液處理問 題及成本爲其缺點。 日本專利案號6 3 2 6 8 2 3 8，係利用鹽酸水溶液中添加 適量的鋁離子，在6 5 - 9 5 °C的蝕刻溫度下，對鋁箔進行 D C電源電化學蝕刻，增加鋁箔表面積及對蝕刻溫度的穩 定度；但DC電源電化學蝕刻方法對於高純度的鋁箔而 言，很難達到高擴面率的效果，並且較低總酸濃度的蝕刻 液中，蝕刻液溫度對電化學蝕刻擴面率的影響不甚明顯是 其缺點。 日本專利案號1 〇 3 1 9 9 2 4，其特點爲蝕刻後之鋁箔， 在含有磷酸根離子的水溶液中施加1 - 5 V的直流電源，使 鋁蝕刻箔表面產生一層酸化皮膜，增加蝕刻箔的穩定性， 降低電容量衰退；但單純磷酸根離子系列所產生的氧化膜 在高溫、高電壓時會產生分解而使電容器不穩定。 曰本專利案號2 0 1 1 7 1 2 2，係在鋁箔表面形成硼化物 的蒸著皮膜，作爲陰極箔的粗化及電子傳導的表面，改善 電容量衰退的現象，增加穩定性。但其缺點爲陰極箔以蒸 著皮膜所得的擴面率有限，而且蒸著設備及費用太高。 日本專利案號2 0 2 4 4 7 0 5，係利用親水性氟素樹脂多 孔膜抑制電解時陰極產生氣泡所造成的溶液濃度差異，使 改善鋁箔表面蝕孔的均勻與緻密性。但其缺失爲氟素樹脂 係一耗材，增加成本及必須定期保養更換。 曰本專利案號5 0 2 4 3 0 9 9，係利用磷酸系列之偶合劑 作爲蝕刻陰極箔的後處理液*使生成一層磷酸化的氧化皮 本纸張尺度通用中國國家揉準（CNS ) A4規格（210X297公釐） 83.3.10,000 -6- (請先KI讀背面之注意事項再填寫本頁) -5 竣 403923 A7 __ B7 五、發明説明（5 ) 膜’增加陰極箔的耐水穩定性；其缺失爲在高溫下的穩定 度較差。 本發明欲解決的問題與方法： 經濟部中央樣準局属工消费合作社印裝 本發明主要係利用化學蝕刻法在製程上的優勢並改進 其缺點且能實際運用於生產工作的化學蝕刻製程步驟，較 簡易及精確地製造出預期電容量及機械強度的蝕刻鋁箔， 因爲鋁浸漬在禽濃度酸液中，反應會有前導時間，其原因 在於鋁表面有氧化膜或氫氧化膜的存在，而氧化膜或氫氧 化膜一般都比鋁金屬更具耐酸性，但是，此類皮膜通常都 具有孔穴及龜裂存在，使酸液得以滲入與鋁金屬開始反 應，但在保護皮膜完全溶解或脫落之前，酸液與鋁金屬無 法急速反應，此乃前導期，如果酸液中具有促進鋁金屬氧 化之性質或加入氧化性添加劑，則化學蝕刻反應會形成一 方面想加以溶解一方面想生成皮膜保護鋁金屬的拉鋸戰， 可使蝕刻達到擴te的目的，並有助於反應穩定性之提升； 急遽反應發生後，可調整電解液的濃度琴溫度來控制反應 速度，就價格競爭激烈的鋁電解電容器而言，不但省卻許 多電化學蝕刻所須的電源供應器及極板等昂貴的設備，而 且製程生產速率提升、品質穩定，增加產品競爭力，亦解 決了長期以來傳統的化學蝕刻方法所無法克服的問題。 發明目的 83. 3.10,000 (請先Μ讀背西之注意事項再填寫本頁) 本紙伕尺度逍用中國國家揉準（CNS ) Α4規格（2丨0Χ297公釐） 403923 A7 B7__ 五、發明説明（6 ) (請先閲讀背面之注意容•項再填寫本頁) 本發明之主要目的，係在提供高電容量及高穩定度鋁 電解電容器用蝕刻陰極箔之製程方法，針對先前所述之電 化學蝕刻方法及傳統化學蝕刻方法的缺失進行改進’運用 較低的設備費用、較少的製造成本、更有效率的製程速度 及較不具環境傷害的化學物質，製造具有高電容量及高穩 定鹿特性的陰極箱。 本發明之次要目的，係在提供高電容量及高穩定度鋁 電解電容器用蝕刻陰極箔之製程方法，運用較低的設備費 用、較少的嚷造成本、更有效率的製程速度及較不具環境 傷害的化學物質，製造品質高且成本低的陰極箔。 本發明之詳細說明 以下，藉由本發明之實施例配合附圖，說明本發明詳 細內容。 圖式說明 圖一爲本發明之流程不意圖。 經濟部中央梂準局負工消費合作社印裝 請參閱圖一本發明之流程示意圖’本發明係爲一製造 鋁電解電容器用蝕刻陰極箔的完整製程方法，利用簡單且 能實際運用於生產工作的化學蝕刻製程步驟’較簡易及精 確地製造出預期電容量及機械強度的蝕刻陰極箔’就價格 競爭激烈的鋁電解電容器而言’此發明省卻許多電化學蝕 83. 3.10,000 本纸張尺度逍用中國國家樣率（CNS)八4说格（210X297公釐） 403923 A7 B7 五、發明説明（7 ) 刻所須的電源供應器及極板等昂貴的設備，而且製程生產 速率提升、品質穩定，增加產品競爭力。 本發明主要分成三大部份，第一部份爲前處理，可利 用磷酸根離子、鉻酸根離子、過氯酸根離子、碳酸根離 子、硫.酸根離子及硝酸根離子等氧化酸水溶液淸除鋁原箔 表面的污染物，並提供均勻蝕刻的適合表面，爲後續蝕刻 處理作準備；第二部份爲蝕刻處理，目的是將前處理完成 後的銘原范表面，利用化學触刻（chemical etching)方法，鈾 刻出均勻、緻密且大小適當的有效蝕孔，以增加鋁原箔有 效表面積，化學蝕刻方法是不須藉助外在電源供應的蝕刻 方法，利用局部電池（local cell)原理，調整適當的蝕刻液 (含鹽酸、硝酸、硫酸、磷酸、醋酸、檸檬酸及鋁離子） 成份、適當的蝕刻溫度與時間，達到有效面積增大的目 的；第三部份爲後處理，後處理步驟在陰極箔的製程上有 重要的地位，可將殘餘的蝕刻液淸洗乾淨，共包括三個階 段，第一段後處理係將鈾刻處理後的殘餘氯離子淸洗乾 淨，此時可使用的淸洗液爲硝酸水溶液，第二段後處理係 再把蝕刻孔洞內的雜質吸附物淸除掉，避免雜質吸附物之 影響而降低電容量，並在陰極箔上作好長出氧化膜的準 備，此時可使用的淸洗液爲磷酸、硫酸及醋酸水溶液，第 三段後處理爲表面穩定化的處理，即在陰極箔上穩定成長 氧化膜，此時所使用的淸洗液爲己二酸銨、磷酸根系列及 硫酸根系列等水溶液並配合適當的電流，後處理步驟依序 增加可使陰極箔電容量因放置時間的變化依序降低’即只 進行第一段後處理之鋁電解電容器陰極箔則必需放置一段 ^纸張尺度逍用中國國家搮準（〇奶）八4说格（2丨0父297公釐） (請先閏讀背*之注意事項再填寫本頁) 訂 令，i · 經濟部中央橾準局身工消費合作杜印裂 83. 3. !0,〇〇〇 9- A7 B7 403823 五、發明説明（8 ) 時間才能達到穩定電容，如果進行第--三段後處埋之鋁 電解電容器陰極箔則不必儲放即可達到穩定電容。 接著，舉附本發明之實施例四端，相信本發明之其他 目的、特徵及優點，當可由之而獲得更淸晰具體之了解。 (實施例一） 純度99.4%以上，厚度20uin-60um的鋁原箔，在 成份比例爲10ml磷酸及O.lg鉻酸溶解成100ml、65 °C的前處理水溶液，浸泡6 0 s e c後，以純水充份沖洗表 面後，進行化學蝕刻處理，蝕熟水溶液成份如下：鹽酸、 硫酸及磷酸的混酸總酸度爲4 . 8 m ο 1 / 1 (適當的成份比 例爲鹽酸：3 5 0 - 5 8 0 m 1 / 1、硫酸：5 - 1 8 m 1 / 1及磷 酸：5-20ml/l)，添加適量鋁離子：10~15g/ 1，蝕刻 液溫度控制在7 5 °C，浸泡2 5 s e c後，以純水充份沖洗 之，準備進行後處理步驟，第一段後處理以濃度2 5 m 1 / 1 的硝酸水溶液，常溫下，泡4 0 s e c之後，純水充份沖洗 之，第二段後處理以混酸總酸度2 . 6 m ο 1 / 1 (適當的成 份比例爲磷酸：3 8 - 5 5 m 1 / 1、硫酸：6 - 1 7 m 1 / 1及醋 酸：5 - 1 3 m 1 / 1 )，在痛溫6 0 t浸泡3 0 s e c後，純水充 份沖洗乾淨，第三段後處理以成份1 0 0 g / 1的己二〜酸銨 及1 5 g / 1的次亞磷酸銨混酸水声液8.5 r下，施加5 V的 直流電源6 0 s e c後，純水沖洗乾淨並烘乾即成。 (實施例二） 純度99.4%以上，厚度20um-60um的鋁原箔’在 本紙張尺度通用中國國家標隼（CNS ) A4g ( 210X297公釐） ' -10 (请先E讀背面之注意事項再填寫本頁) -10 經濟部令央搮準局貞工消费合作社印装 83.3.10,000 經濟部中央橾準局貝工消費合作杜印敦 403^23 五、發明説明（9 ) 成份比例爲1 0 m 1磷酸及0 . 1 g鉻酸溶解成1 0 0 m 1、6 5 。(：的前處理水溶液，浸泡6 0 s e c後，以市水充份沖洗表 面後，進行化學蝕刻處理。每升蝕刻水溶液成份如下：鹽 酸、硫酸及磷酸的混酸總酸度爲4. 8m〇l/l (適當的成 份比例爲鹽酸：350-580ml/l、硫酸：5-18ml/l及磷 酸：5-20ml/l)，添加適量鋁離子· 10~15g/l，蝕刻 液溫度控制在7 5 °C，浸泡2 5 s e c後’以純水充份沖洗 之，準備進行後處理步驟。第一段後處理以濃度2 5 m 1 / 1 的硝酸水溶液，常溫下浸泡4 0 s e c之後，純水充份沖洗 之。 (實施例三） 純度99.4%以上，厚度20\1111-6〇11111的銘原箱，在 成份比例爲10ml磷酸及O.lg鉻酸溶解成100ml、6 5 °C的前處理水溶液，浸泡6 0 s e c後，以純水充份沖洗表 面後，進行化學蝕刻處理，蝕刻水溶液成份如下：鹽酸、 硫酸及磷酸的混酸總酸度爲4 . 8 m ο 1 / 1 (適當的成份比 例爲鹽酸：350-580ml/l、硫酸及磷 酸：5 - 2 0 m 1 / 1 )，添加適量鋁離子:10〜15gM，蝕刻 4. > 液溫度控制在7 5 °C，浸泡2 5 s e c後，以純水充份沖洗 之，準備進行後處理步驟。第一段後處理以濃度2 5 m 1 / 1 的硝酸水溶液，常溫下浸泡4 0 s e c之後，純水充份沖洗 之，第二段後處理以混酸總酸度2. 6mol/l (適當的成 份比例爲磷酸：3 8 - 5 5 m 1 / 1 、硫酸：6 - 1 7 m 1 / 1及醋 酸：5 - I 3 m丨/ 1 )，在液溫6 0 °C浸泡3 0 s e c後，純水充 本纸張尺度速用中國國家搮準（CNS) Μ说格（210X297公釐） 83.3.10,000 -11-Please ask Mingming Cheng. ## τ- mentioned in the month% day, whether there is any change in the substance of whether the content is approved. 05. Description of the invention (i) 03923 Invention model The invention is an etching method for the cathode foil of aluminum electrolytic capacitors. The invention not only improves the defect of the traditional chemical etching method, but also overcomes the disadvantages of expensive hardware equipment and high manufacturing cost of the etching foil of the electrochemical etching method, and greatly improves the process rate. BACKGROUND OF THE INVENTION Aluminum electrolytic capacitors mainly include an etched anode foil that functions as an anode, and an etched cathode foil that functions as an electrolyte for the cathode and for the conduction of electrons on the cathode side. 'The anode foil is chemically treated as a dielectric layer, and the cathode foil is not.' But in actual use, the cathode foil will also have a layer of natural oxide film, which will produce a dielectric effect like the anode box; therefore, the capacitance of the aluminum electrolytic capacitor is the serially combined capacitance of the anode foil capacitance and the cathode foil capacitance. The formula is as follows: 'l / C = l / Ci + I / C2 C: Composite capacitance C i: Anode foil capacitance: Cathode foil capacitance The composite capacitance mainly depends on the anode foil with chemical treatment. The higher and more stable the capacitance, the smaller the impact on the combined capacitance C, especially for low-voltage capacitors that must withstand high temperatures. In addition to the capacitance of the cathode foil, this paper applies the Chinese National Standard (CNS) A4 washing grid (2丨 0X297 mm) (Please read the precautions on the back before filling in this page),-° Printed by the Bayer Consumer Cooperative of the Central Bureau of the Ministry of Economic Affairs 83. 3 · 10, 00m承 # 月% 日 的 # .τ-, whether there is any change in the substance of whether or not the content is allowed. 05. Description of the Invention (i) 03923 Invention Model The invention is an etching method for the cathode foil of aluminum electrolytic capacitors. The improvement of the traditional chemical etching method has also overcome the shortcomings of expensive hardware equipment and high manufacturing cost of the etching foil of the electrochemical etching method, and has greatly improved the process rate. BACKGROUND OF THE INVENTION Aluminum electrolytic capacitors mainly include an etched anode foil that functions as an anode, and an etched cathode foil that functions as an electrolyte for the cathode and for the conduction of electrons on the cathode side. 'The anode foil is chemically treated as a dielectric layer, and the cathode foil is not.' But in actual use, the cathode foil will also have a layer of natural oxide film, which will produce a dielectric effect like the anode box; therefore, the capacitance of the aluminum electrolytic capacitor is the serially combined capacitance of the anode foil capacitance and the cathode foil capacitance. The formula is as follows: 'l / C = l / Ci + I / C2 C: Composite capacitance C i: Anode foil capacitance: Cathode foil capacitance The composite capacitance mainly depends on the anode foil with chemical treatment. The higher and more stable the capacitance, the smaller the impact on the combined capacitance C, especially for low-voltage capacitors that must withstand high temperatures. In addition to the capacitance of the cathode foil, this paper applies the Chinese National Standard (CNS) A4 washing grid (2丨 0X297 mm) (Please read the precautions on the back before filling in this page),-° Printed by the Central Consumers Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperative, 83. 3 · 10, 〇〇403403 A7 B7 V. Description of the invention (2) Beyond the high volume, the stability to environmental changes is also good. Therefore, the main requirements for the cathode foil material of aluminum electrolytic capacitors are as follows: 1. High capacitance: The higher the capacitance of the cathode foil, The composite capacitance mainly comes from the contribution of the anode foil, which can make the capacitor more in line with the trend of light, thin, short and small. 2. High mechanical strength: When winding the capacitor element, sufficient tensile force and bending strength are necessary. 3. High stability: The capacitance of the cathode foil will change due to the use of the packaged capacitor and environmental changes, making the quality of the capacitor unstable. Therefore, the etching quality of the cathode foil greatly affects the quality of the capacitor. How to improve the quality and reduce the cost is a problem that this industry wants to solve. * Problems with conventional technology = At present, the etching methods of cathode foils of aluminum electrolytic capacitors are mainly the following two methods: (1) The electrochemical etching method uses the effect of aluminum foil to borrow the current in the electrolyte, and the moment the current flows from aluminum to the solution The aluminum is dissolved in the electrolyte, and thus etched pores are formed on the surface of the aluminum foil. The residual amount of the aluminum dissolution minus the chemical and physical dissolution amounts is directly proportional to the product of current and time. The size of the aluminum dissolution rate can be borrowed. It can be adjusted by the magnitude of the current, and the expected expansion rate can be achieved by controlling the temperature and concentration of the solution. (II) Chemical etching method This paper size applies the Chinese National Standard (CNS) A4 scale (210X297 mm) (Please read the precautions on the back before filling out this page) Impression 83 · 3.10,000 4- 403923 A7 B7 V. Description of the invention (3) Aluminum acid in the acid solution, especially in the halogen acid and its salts, has the disadvantage of invading the surface of the aluminum and causing corrosion. The starting point is strong corrosion. Take hydrochloric acid as an example. That is, the chloride ion in hydrochloric acid combines with aluminum to form A1C13 and dissolve in the solution. The hydrogen ion becomes hydrogen and escapes into the air. As HC1 decreases and A1C13 increases, The reaction rate changes greatly, causing unstable etching quality. In order to obtain stable and better etching quality, in addition to improving solution management, various additives can be added to improve the etching effect. However, although the electrochemical etching method has the advantages of (1) that the current can be adjusted arbitrarily, the dissolution rate can be controlled, (2) the power supply type can be changed, the etch holes can be controlled uniformly, and (3) the solution management is easy, but there are still (1) The equipment is expensive, (2) the manufacturing cost of the etching foil is high, and (3) the disadvantages of not being able to increase the process rate; the chemical uranium engraving method has (1) the equipment is cheap, the required space is small, and (2) the etching rate can reach the electrochemical etching method Several times and (4) the advantages of low etching cost, but there are still disadvantages that cannot be accepted by the industry: (1) the reaction state is unstable and difficult to control, (2) the initial dissolution rate is slow, and the reaction cannot be completed in one go. After a long period of time, the reaction will occur rapidly, that is, the so-called reaction lead period, (3) the reaction occurs rapidly after the reaction lead period, making etching difficult to control, (4) thin cathode foils, and easy uranium engraving and ( 5) It is not easy to increase the capacity. U.S. Patent No. 4 4 3 2 8 4 6 is a complete electrochemical etching process. The AC / DC power supply is used to electrochemically etch the surface of aluminum foil in an aqueous solution of hydrochloric acid. Chloride This paper is sized according to the Chinese National Standard (CNS) A4 (210X297 mm) II nnj ϊ (谙 Please read the note on the back ^^ before filling this page) Printed oxygen by the Central Laboratories Bureau of the Ministry of Economic Affairs 83.3.10,000 Printed by the Order of the Ministry of Economic Affairs of the Central Bureau of the Zhuhai Bureau Shellfish Consumer Cooperative «. 403923 5. The description of the invention (4) was removed and some post-processing steps were made; but the etching step was too long, the electrochemical etching efficiency was not good, and The use of chromic acid in the treatment increases the problem of waste liquid treatment and the cost is its disadvantage. Japanese patent case No. 6 3 2 6 8 2 3 8 is the use of a suitable amount of aluminum ions in an aqueous hydrochloric acid solution, and the DC power electrochemical etching of aluminum foil at an etching temperature of 6 5-95 ° C, increasing the surface area of aluminum foil and The stability of the etching temperature; however, the DC power supply electrochemical etching method is difficult to achieve the effect of high expansion ratio for high-purity aluminum foil, and in the etching solution with a lower total acid concentration, the etching solution temperature affects the electrochemical etching. The effect of the enlargement rate is not obvious is its disadvantage. Japanese Patent No. 103 1 9 9 2 4 is characterized by etched aluminum foil. A DC power supply of 1-5 V is applied to an aqueous solution containing phosphate ions to produce an acidified film on the surface of the aluminum etched foil to increase etching. The stability of the foil reduces the decline in capacitance; however, the oxide film produced by the simple phosphate ion series will decompose at high temperatures and high voltages, making the capacitor unstable. The patent case No. 20 1 1 7 1 2 2 is a vaporized film that forms a boride on the surface of aluminum foil, and serves as a surface for roughening and electron conduction of a cathode foil to improve the phenomenon of capacitance degradation and increase stability. However, the disadvantages are that the surface expansion of the cathode foil by evaporation of the film is limited, and the evaporation equipment and cost are too high. Japanese Patent Case No. 2 0 2 4 4 7 0 5 is to use a hydrophilic fluororesin porous membrane to suppress the difference in solution concentration caused by the cathode bubble generated during electrolysis, so as to improve the uniformity and compactness of etched holes on the surface of aluminum foil. However, its lack is a consumable of fluorine resin, which increases costs and must be regularly replaced. The patent No. 5 0 2 4 3 0 9 9 is a coupling agent of phosphoric acid series used as a post-treatment solution for etching the cathode foil * to produce a layer of phosphorylated oxide scale. The paper size is in accordance with China National Standards (CNS) A4 specification (210X297 mm) 83.3.10,000 -6- (Please read the precautions on the back before filling in this page) -5 403403 A7 __ B7 V. Description of the invention (5) The membrane increases the water resistance stability of the cathode foil ; Its lack is poor stability at high temperatures. Problems and methods to be solved by the present invention: Printed by the Central Samples and Standards Bureau of the Ministry of Economic Affairs, which belongs to the Industrial and Consumer Cooperatives. The present invention is mainly a chemical etching process step that uses the advantages of the chemical etching method in the manufacturing process and improves its shortcomings, and can be actually applied to production work. It is easier and more accurate to produce etched aluminum foil with expected capacitance and mechanical strength. Because aluminum is immersed in a bird ’s acid solution, the reaction will have a lead time. The reason is that there is an oxide film or a hydroxide film on the aluminum surface. Oxide film or hydroxide film are generally more acid-resistant than aluminum metal. However, such films usually have holes and cracks, so that the acid can penetrate into the metal and start to react, but before the protective film is completely dissolved or detached The acid solution and aluminum metal cannot react quickly. This is the leading stage. If the acid solution has the property of promoting the oxidation of aluminum metal or the addition of oxidizing additives, the chemical etching reaction will form on the one hand. The metal sawing war can make the etching achieve the purpose of expanding te and help improve the stability of the reaction; After the reaction occurs, the concentration of the electrolyte can be adjusted to control the reaction speed. As for aluminum electrolytic capacitors with fierce price competition, not only are many expensive equipment such as power supplies and plates required for electrochemical etching eliminated, but also the manufacturing process The production rate is increased, the quality is stable, and the product competitiveness is increased. It also solves the problems that cannot be overcome by traditional chemical etching methods for a long time. Object of the invention 83. 3.10,000 (please read the precautions of the West first and then fill in this page) The standard of this paper is to use the Chinese National Standard (CNS) A4 specification (2 丨 0 × 297 mm) 403923 A7 B7__ 5. Description of the invention (6) (Please read the notes and items on the back before filling this page) The main purpose of the present invention is to provide a method for etching cathode foil for aluminum electrolytic capacitors with high capacitance and high stability. Improvements in the lack of electrochemical etching methods and traditional chemical etching methods' Use of lower equipment costs, less manufacturing costs, more efficient process speeds and less environmentally harmful chemicals to produce high-capacitance and high-stability Cathode box with deer characteristics. A secondary object of the present invention is to provide a process method for etching a cathode foil for a high-capacitance and high-stability aluminum electrolytic capacitor, which uses a lower equipment cost, less cost, more efficient process speed, and Non-environmentally harmful chemicals, manufacture high quality and low cost cathode foil. Detailed description of the present invention In the following, embodiments of the present invention will be described in detail with reference to the accompanying drawings. Description of the drawings Figure 1 is not intended to illustrate the process of the present invention. Please refer to Figure 1 for a schematic diagram of the process of the present invention. The present invention is a complete process method for manufacturing etched cathode foil for aluminum electrolytic capacitors. It uses a simple and practical application of production The chemical etching process step 'easier and more accurate to produce an etched cathode foil with expected capacitance and mechanical strength' In the case of highly competitive aluminum electrolytic capacitors' this invention saves a lot of electrochemical etching 83. 3.10,000 paper size Free use of China National Sample Rate (CNS) 8 4 grid (210X297 mm) 403923 A7 B7 V. Description of the invention (7) Expensive equipment such as power supplies and plates required, and the production rate of the process is improved, quality Stability and increase product competitiveness. The present invention is mainly divided into three parts. The first part is pretreatment, which can be used to remove phosphoric acid ions, chromate ions, perchlorate ions, carbonate ions, sulfur, acid ions, and nitrate ions. Contaminants on the surface of the original aluminum foil, and provide a suitable surface for uniform etching, in preparation for subsequent etching treatment; the second part is the etching treatment, the purpose is to use the chemical touch engraving etching) method, uranium etches uniform, dense and appropriately sized effective etched holes to increase the effective surface area of the aluminum foil. The chemical etching method is an etching method that does not require external power supply and uses the principle of local cells. Adjust the composition of the appropriate etching solution (including hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, acetic acid, citric acid and aluminum ions), appropriate etching temperature and time to achieve the purpose of increasing the effective area; the third part is post-processing, post-processing The step plays an important role in the manufacturing process of the cathode foil. The remaining etching solution can be washed and cleaned. It consists of three stages. Rinse the residual chloride ions after the uranium etching treatment. At this time, the cleaning solution that can be used is an aqueous nitric acid solution. The second stage of post-processing is to remove the impurities adsorbed in the etching holes to avoid the effects of impurities adsorbed. Reduce the capacitance and prepare for the formation of an oxide film on the cathode foil. At this time, the cleaning solution that can be used is phosphoric acid, sulfuric acid and acetic acid aqueous solution, and the third stage of post-treatment is surface stabilization treatment, that is, the cathode An oxide film is stably grown on the foil. At this time, the cleaning solution used is an aqueous solution of ammonium adipate, phosphate series and sulfate series, and an appropriate current is applied. The sequential increase of the post-processing steps can make the cathode foil capacitance due to placement. The change in time decreases in sequence, that is, the cathode foil of the aluminum electrolytic capacitor that is only subjected to the first stage of post-treatment must be placed for a period of ^ paper scale. Chinese national standard (0 milk) 8 4 grid (2 丨 0 parent 297 public) (%) (Please read the notes on the back * before filling out this page) Order, i · Industrial and consumer cooperation cooperation between the Central and Standard Bureau of the Ministry of Economic Affairs 83. 3.! 0, 〇〇〇09- A7 B7 403823 V. Description of Invention (8) Time Talent The stabilizing capacitor, if the second - after three sections burying the aluminum electrolytic capacitor cathode foil is not necessary to store stable capacitance. Next, with reference to the four ends of the embodiment of the present invention, it is believed that other objects, features, and advantages of the present invention can be obtained with a clearer and more specific understanding. (Example 1) The original aluminum foil with a purity of 99.4% or more and a thickness of 20uin-60um was dissolved in a pretreatment solution containing 100ml of phosphoric acid and 0.1g of chromic acid into 100ml of 65 ° C, soaked for 60 sec. After the surface is thoroughly washed with pure water, a chemical etching treatment is performed. The composition of the etched aqueous solution is as follows: The total acidity of the mixed acid of hydrochloric acid, sulfuric acid and phosphoric acid is 4.8 m ο 1/1 (the appropriate composition ratio is hydrochloric acid: 3 5 0-5 8 0 m 1/1, sulfuric acid: 5-1 8 m 1/1 and phosphoric acid: 5-20ml / l), add appropriate amount of aluminum ion: 10 ~ 15g / 1, the temperature of the etching solution is controlled at 7 5 ° C, soak 2 After 5 sec, rinse thoroughly with pure water and prepare for the post-treatment step. The first stage of post-treatment is with an aqueous nitric acid solution with a concentration of 25 m 1 / 1. After soaking at room temperature for 40 sec, the pure water is fully rinsed. In the second stage of post-treatment, the total acidity of the mixed acid is 2.6 m ο 1/1 (the appropriate composition ratio is phosphoric acid: 3 8-5 5 m 1/1, sulfuric acid: 6-1 7 m 1/1 and acetic acid: 5 -1 3 m 1/1), after soaking for 30 sec at a pain temperature of 60 t, rinse thoroughly with pure water. The third stage of post-treatment is to use ingredients of 100 g / 1 of adipic acid ~ 1 ammonium and 1 5After applying g / 1 ammonium hypophosphite mixed acid water acoustic liquid at 8.5 r, a DC power supply of 5 V for 60 s e c is applied, and the pure water is rinsed and dried. (Example 2) The original aluminum foil with a purity of 99.4% or more and a thickness of 20um-60um is commonly used in the Chinese paper standard (CNS) A4g (210X297mm) -10 (Please read the precautions on the back first) (Fill in this page) -10 Printed by the Order of the Ministry of Economic Affairs of the Central Government Associated Bureau Zhengong Consumer Cooperative 83.3.10,000 The Department of Economic Affairs of the Central Government of the Ministry of Economic Affairs Duan Dun 403 ^ 23 5. Description of the invention (9) The composition ratio is 1 0 m 1 phosphoric acid and 0.1 g chromic acid are dissolved into 100 m 1, 6 5. (: Pre-treatment aqueous solution, after soaking for 60 sec, the surface is fully washed with municipal water, and then subjected to chemical etching treatment. The composition of each liter of etching aqueous solution is as follows: the total acidity of the mixed acid of hydrochloric acid, sulfuric acid and phosphoric acid is 4. 8m〇l / l (appropriate proportion of hydrochloric acid: 350-580ml / l, sulfuric acid: 5-18ml / l and phosphoric acid: 5-20ml / l), add appropriate amount of aluminum ion · 10 ~ 15g / l, control the temperature of the etching solution at 7 5 ° C, after soaking for 2 5 sec, rinse it with pure water and prepare for the post-treatment step. The first post-treatment is a nitric acid solution with a concentration of 25 m 1/1 and soaked at room temperature for 40 sec. (Example 3) The original box with a purity of 99.4% or more and a thickness of 20 \ 1111-6〇11111, before the composition ratio of 10ml phosphoric acid and O.lg chromic acid was dissolved to 100ml, 65 ° C. Treat the aqueous solution. After soaking for 60 sec, rinse the surface with pure water and perform chemical etching treatment. The composition of the etching solution is as follows: The total acidity of the mixed acid of hydrochloric acid, sulfuric acid and phosphoric acid is 4.8 m ο 1/1 (appropriate composition The ratio is hydrochloric acid: 350-580ml / l, sulfuric acid and phosphoric acid: 5-2 0 m 1/1). Amount of aluminum ions: 10 ~ 15gM, etching 4. > The liquid temperature is controlled at 7 5 ° C, after soaking for 2 5 sec, it is rinsed with pure water and prepared for the post-treatment step. The first post-treatment is at a concentration of 2 5 m 1/1 aqueous nitric acid solution, soaked at room temperature for 40 sec, then rinsed with pure water. The second stage of post-treatment is mixed acid total acidity 2. 6mol / l (appropriate proportion of phosphoric acid: 3 8-5 5 m 1/1, sulfuric acid: 6-1 7 m 1/1 and acetic acid: 5-I 3 m 丨 / 1), after soaking at a liquid temperature of 60 ° C for 30 sec, pure water fills the paper at a standard speed. Chinese National Standards (CNS) M scale (210X297 mm) 83.3.10,000 -11-
In In n ---1 If n I I n I n - n T n I I I I n ^ I 、va (請先s讀背s之注意審‘項再填寫本X ) 經濟部中央橾準局負工消费合作社印装 403923 A7 _B7___ 五、發明説明（10 ) 份沖洗乾淨》 (實施例四） 純度99.4%以上，厚度2〇11111-6〇11111的鋁原箔，在 成份比例爲10ml磷酸及O.lg鉻酸溶解成100ml、65 °C的前處理水溶液，浸泡6 0 s e c後，以純水充份沖洗表 面後，進行化學蝕刻處理，蝕刻水溶液成份如下：鹽酸' 硫酸及磷酸的混酸總酸度爲4 . 8 m ο 1 / 1 (適當的成份比 例爲鹽酸：350-580ml/l '硫酸：5-18ml/l及磷 酸：5-20ml/l)，添加適量鋁離子：10~15g/l，蝕刻 液溫度控制在6 0 ± 1 t，浸泡3 0 s e c後，以純水充份沖 洗之，準備進行後處理步驟。第一段後處理以濃度 2 5 m 1 / 1的硝酸水溶液，常溫下浸泡4 0 s e c之後，純水 充份沖洗之。第二段後處理以混酸總酸度2 . 6 m ο 1 / 1 (適當的成份比例爲磷酸：3 8 - 5 5 m 1 / 1、硫酸：6-1 7 m 1 / 1及醋酸：5 - 1 3 m 1 / 1 )，在液溫6 0 °C浸泡 3 0 s e c後，純水充份沖洗乾淨。第三段後處理以成份 100g/l的己二酸銨及15g/l的次亞磷酸銨混酸水溶液 8 5 °C下，施加5 V的直流電源6 0 s e c後，純水沖洗乾淨 並烘乾即成" 本發明之前述和其他目的及特徵經由以上針對較佳實 施例的敘述，將更爲顯著，該敘述僅係用於例示說明本發 明於較佳狀況下之操作結果，而非企圖以之對發明範圍作 任何限制，其他在不脫離發明精神下所作之修飾及變更， 皆屬本發明之保護範圍。 本紙張適用中DU家梯準（CNS )鐵^ ( 2丨〇x2_廣) 83. 3.10,000' -12- ----------------.玎^------^ I (請先K讀背面之注意¾‘項再填寫本頁) 403923 at B7 五、發明説明（U ) 表一、實施例實驗結果 實施例 厚度 _ 電容量（/zF/cm2) 衰減比率 (%) 拉力 (kgf/cm) 彎曲度 (cycles) 初期値 穩定値 — 50 471+24 423+21 10.2 2.45 265 二， 50 642+32 512+26 20.2 2.23 292 ' 三 50 724+36 578+29 20.2 2.31 281 四 50 347+17 315+16 9.2 2.48 287 I- n n n n - n - n n I - - I HI T _ n n n _ _ ^ I τ°Λ-. - 事 (請先閲讀背面之注意事項再填寫本頁) 經潦部中央揉準局属工消费合作社印裝 本紙張尺度適用中國國家標隼（CNS ) A4規格（210X297公釐） 83.3.10,000 -13 -In In n --- 1 If n II n I n-n T n IIII n ^ I, va (please read the item “Notes for review” and then fill out this X) Central Government Procurement Bureau, Ministry of Economic Affairs Printed 403923 A7 _B7___ V. Description of the invention (10) Rinse out (Example 4) Aluminum original foil with a purity of more than 99.4% and a thickness of 2011111-6〇11111. The composition ratio is 10ml phosphoric acid and O.lg chromium The acid is dissolved into a 100ml, 65 ° C pre-treatment aqueous solution. After soaking for 60 sec, the surface is rinsed with pure water and then chemically etched. The composition of the etching solution is as follows: The total acidity of the mixed acid of hydrochloric acid, sulfuric acid and phosphoric acid is 4. 8 m ο 1/1 (appropriate proportion of hydrochloric acid: 350-580ml / l 'sulfuric acid: 5-18ml / l and phosphoric acid: 5-20ml / l), add appropriate amount of aluminum ion: 10 ~ 15g / l, etching solution The temperature is controlled at 60 ± 1 t. After soaking for 30 sec, rinse thoroughly with pure water to prepare for the post-processing step. In the first stage of post-treatment, an aqueous nitric acid solution with a concentration of 25 m 1/1 was immersed at room temperature for 40 s e c and then rinsed with pure water. The second stage of post-treatment is to mix the total acidity of the acid with 2.6 m ο 1/1 (appropriate proportions of phosphoric acid: 3 8-5 5 m 1/1, sulfuric acid: 6-1 7 m 1/1 and acetic acid: 5- 1 3 m 1/1), soak in pure water for 30 sec at 60 ° C. The third stage of post-treatment is to mix 100 g / l of ammonium adipate and 15 g / l of ammonium hypophosphite mixed acid aqueous solution at 85 ° C, after applying 5 V DC power for 60 sec, rinse with pure water and dry. The aforementioned and other objects and features of the present invention will be more prominent through the above description of the preferred embodiment, which is only for the purpose of illustrating the operation results of the present invention in a better condition, and is not intended. Therefore, any limitation on the scope of the invention is made, and other modifications and changes made without departing from the spirit of the invention belong to the protection scope of the invention. This paper is suitable for DU home ladder (CNS) iron ^ (2 丨 〇x2_ 广) 83. 3.10,000 '-12- ----------------. 玎 ^- ----- ^ I (please read the note on the back ¾ 'and fill in this page first) 403923 at B7 V. Description of the invention (U) Table I. Example experimental results Example thickness _ capacitance (/ zF / cm2) Attenuation ratio (%) Pulling force (kgf / cm) Curvature (cycles) Initially stable 値 — 50 471 + 24 423 + 21 10.2 2.45 265 II, 50 642 + 32 512 + 26 20.2 2.23 292 'Three 50 724+ 36 578 + 29 20.2 2.31 281 four 50 347 + 17 315 + 16 9.2 2.48 287 I- nnnn-n-nn I--I HI T _ nnn _ _ ^ I τ ° Λ-.-Things (please read the first Please fill in this page for the matters needing attention.) The paper size printed by the Ministry of Economic Affairs and the Central Government Bureau of Industrial and Consumer Cooperatives is applicable to China National Standard (CNS) A4 (210X297 mm) 83.3.10,000 -13-