TW200934879A

TW200934879A - Method of recovering valuable metal from lithium battery residue containing Co, Ni and Mn

Info

Publication number: TW200934879A
Application number: TW97141955A
Authority: TW
Inventors: Yosuke Yamaguchi; Jyunzo Hino
Original assignee: Nippon Mining Co
Priority date: 2008-02-13
Filing date: 2008-10-31
Publication date: 2009-08-16
Also published as: JP4865745B2; CN101509071B; TWI392745B; KR101036407B1; CN101509071A; KR20090087801A; JP2009193778A

Abstract

The purpose of the present invention is to recover valuable metals such as Mn, Co, Ni and Li from ternary system lithium salts in lithium battery residues. The technical means of the invention resides in stirring and pickling lithium battery residues containing the lithium-acid metal salts(containing roughly equal amount of Co, Ni and Mn) with a hydrochloric acid solution of concentration of 250 g/l or more; or stirring and pickling with a sulfuric acid solution of concentration of 200 g/l or more while heating to 65to80 degrees Celcius; or stirring and pickling with a mixed solution that contains a sulfuric acid solution of concentration of 200 g/l or more and a hydrogen peroxide solution of concentration of 20 g/l or more; then solvent extracting the pickled solution with an acidic extracting agent to extract 98% or more of three metals, i.e. Mn, Co and Ni and generating solutions containing respective metals, and then recovering valuable metals such as Mn, Co, Ni and Li from the solutions and the extracted remaining liquid that contains Li.

Description

200934879 九、發明說明：【發明所屬之技術領域】本發明係關於一種自含有Co ’ Ni，Μη之鋰電池殘渣回收有價金屬之方法。含有c〇，Ni，Μη之鋰電池殘渣，係指由三元系鋰金屬鹽與碳、Ν-曱基-2-呲咯烷酮、聚乙烯醇等之溶劑所構成之漿狀物質，於鋰二次電池製造步驟將各物質填充於電池之既定部分時，因無法填充等之理由所發生之殘渣。存在於此等之電池殘渣中，含有有價金屬之 © 金屬酸鋰之處理，從回收有價金屬的觀點來看，係非常重要。【先前技術】曰本特開平6-251805號公報（專利文獻^ ，雖然在其申請時（1993年），鋰二次電池尚未被開發，但是卻率先在開發前，研究鋰二次電池之回收再利用。此方法，係以水刀將使用過的鋰電池加以切斷，然後再將藉由過濾自液體所分離之固體分選於隔板、集電體及正極材。說明可 ® 將此等加以熔融或粉碎，然後再根據材料進行再利用。另，使用作為正極材之金屬氧化物之金屬，可為Ni、c〇、Ti、 Fe、V、Μη、Mo、Cr、W等多種之金屬，但此等金屬並非全部皆有在使用’目前一般最被使用的金屬為Co。曰本特開2006-33 17〇7號公報（專利文獻2)，係提出一種由多階段所構成之鋰電池回收再利用法，係於正極物質回收前後之階段中，將捲繞體、正極、負極及隔板機械性地加以分離’並將正極浸洗於硝酸水溶液，以將正極 5 200934879 基材（鋁）與正極活性物質加以分離，然後將正極活性物質浸洗於鹽酸溶液使其溶解後，再對該溶液進行過濾，藉此付到Li、Ni等之金屬離子混合溶液。接著使用離子交換、電解、沈澱分離等之方法，從該混合溶液回收各金屬。 ❹ 曰本特許第3450684號公報（專利文獻3)，係於1997 年所申請之將鋰二次電池搭載於各種電子機器之申請案，其提出一種從使用過之鋰電池之正極活性物質回收M〇、 Co Ni、Sn等之方法。具體而言，係在不將使用過之鋰電池拆解下，與鐵殼一起進行焙燒，然後再將焙燒物加以粉碎進行1次磁分離，及對非磁性物施行2次磁分離。由於正極所使用之co價格昂貴，故最近係進行開發使用含有大致等量之c。、Ni及Μη之鐘酸金屬鹽作為正極活性物質的技術。例如’專利文獻4 (日本特開則7_侧2 號公報），係提出-種如下述之技術，亦即，將二氧化猛、氧化録、氧化錄及碳酸鐘加以抨量’使Ni: Mn: c〇之比為1 : 1: i (Ni、Mn、c〇)之比為丨〇6:丨，再將此等之化合物與聚乙烯醇溶液混合，然後進行造粒、乾燥、燒成。將此燒成三元系金屬鋰複合氧化物與黏合劑及溶劑混合’來調製漿狀正極活性物質。鎳-氫化物電池之正極活性物f為經基氧化鎳 (Ni〇〇H )，而非鐘雷、、小夕X杠：, 觅池之正極活性物質之鋰酸金屬。關於從該鎳-氫化物電池回收今屬夕古.土 ^ 叹金屬之方法，專利文獻5(日本特表平10-510878號公報）係摇屮视 >> 係徒出如下之方法。亦即（切碎機將廢電池加以粉碎，彳囍 ^ (2)藉由對所得之廢料進行磁分 6 200934879 2以將Fe、Ni加以分離，（3)以硫酸將非磁性材料加以 :解，⑷藉由調整pH’以將Fe加以分離，⑸以過遽、^分離後’對該滤液進行有機溶劑萃取，藉此將Zn、Cd、 Μη、AI萃取出。右與正極物質相較，則負極物質所含之Li、C、Al、si 卜為有價金屬，回收成本較原料成本高。另，此等之負極物質有時亦會包含於電池殘渣中。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for recovering valuable metals from a lithium battery residue containing Co'Ni, Μη. A lithium battery residue containing c〇, Ni, Μη refers to a slurry material composed of a ternary lithium metal salt and a solvent such as carbon, fluorenyl-fluorenyl-2-pyrrolidone or polyvinyl alcohol. In the lithium secondary battery manufacturing step, when each substance is filled in a predetermined portion of the battery, the residue generated due to the inability to fill or the like may be caused. Among the battery residues present, the treatment of lithium metal phosphate containing a valuable metal is very important from the viewpoint of recovering valuable metals. [Prior Art] Unexamined Japanese Patent Publication No. 6-251805 (patent document ^, although at the time of its application (1993), lithium secondary batteries have not been developed, but they are the first to study the recovery of lithium secondary batteries before development. In this method, the used lithium battery is cut with a water jet, and then the solid separated by the filtration is separated into the separator, the current collector and the positive electrode. After being melted or pulverized, and then reused according to the material, the metal used as the metal oxide of the positive electrode material may be Ni, c〇, Ti, Fe, V, Μη, Mo, Cr, W, or the like. Metal, but not all of these metals are used. The current most commonly used metal is Co. 曰本特开 2006-33 17〇7 (Patent Document 2), which is proposed to be composed of multiple stages. The lithium battery recycling method is to mechanically separate the wound body, the positive electrode, the negative electrode and the separator in the stage before and after the recovery of the positive electrode material, and to immerse the positive electrode in an aqueous solution of nitric acid to form the positive electrode 5 200934879 substrate. (aluminum) and positive The active material is separated, and then the positive electrode active material is immersed in a hydrochloric acid solution to be dissolved, and then the solution is filtered to thereby supply a metal ion mixed solution of Li, Ni, etc., followed by ion exchange, electrolysis, and precipitation separation. In the method of the above-mentioned method, the metal is recovered from the mixed solution. 曰特许特许 patrol No. 3450684 (patent document 3) is an application for mounting a lithium secondary battery to various electronic devices, which was filed in 1997, and proposes a method. A method of recovering M〇, Co Ni, Sn, or the like from a positive electrode active material of a used lithium battery. Specifically, it is calcined together with an iron shell without disassembling the used lithium battery, and then the calcined product is further removed. The pulverization is carried out once for magnetic separation, and the magnetic separation is performed twice for the non-magnetic material. Since the co used in the positive electrode is expensive, it has recently been developed to use a sulphuric acid metal salt containing substantially equal amounts of c, Ni and Μη. As a technique of a positive electrode active material, for example, 'Patent Document 4 (Japanese Laid-Open Patent Publication No. Hei No. No. 2), the following is a technique, that is, a sulphur dioxide, oxygen Recording, oxidation recording, and carbonation of the carbon dioxide to make the ratio of Ni: Mn: c〇 to 1: 1: i (Ni, Mn, c〇) ratio is 丨〇6: 丨, and then these compounds and The polyvinyl alcohol solution is mixed, and then granulated, dried, and calcined. The ternary metal lithium composite oxide is mixed with a binder and a solvent to prepare a slurry positive electrode active material. The positive electrode of the nickel-hydride battery The active material f is a nickel-based nickel oxide (Ni〇〇H), not a lithium-metal oxide of the positive electrode active material of the Dianchi, and the Xiaoxi X-bar: the recovery of the nickel-hydride battery from the nickel-hydride battery. The method of sighing the metal, the patent document 5 (Japanese Patent Publication No. Hei 10-510878) is a method of swaying >> That is, (the shredder pulverizes the waste battery, 彳囍^ (2) by separating the Fe and Ni by magnetic separation of the obtained scrap 6 200934879 2, and (3) adding the non-magnetic material with sulfuric acid: (4) Separating Fe by adjusting pH', (5) extracting Zn, Cd, Μ, AI by extracting the filtrate by organic solvent extraction after separation, and separating right from the positive electrode material. The Li, C, Al, and Si contained in the negative electrode material are valuable metals, and the recovery cost is higher than the raw material cost. Further, such a negative electrode material may be included in the battery residue.

❹ 本案申凊人於專利文獻6 (日本特願2007-74089號， 2〇07年3月22日申請）中，如第0001段所說明般，提出 -種回收方法。惟，在此方法中，於有機溶劑中所萃取之金屬僅為Μη及Co。 [專利文獻I]曰本特開平6-251805號公報 [專利文獻2]日本特開2〇〇6_33 17〇?號公報 [專利文獻3]曰本特許第345〇684號公報 [專利文獻4]日本特開2〇〇7_48692號公報 [專利文獻5]日本特表平10-510878號公報 [專利文獻6]曰本特願2007-74089(2007年3月22曰中請） [非專利文獻丨]「資源與材料」，1997,12，Vol.l 13，回收再利用特別企晝，第941頁 [非專利文獻2]講座·現代之金屬學，精鍊編2，非鐵金屬冶練，1982年7月10日金屬學會出版，第240〜241 頁【發明内容】 7 200934879 電池之回收再利用，具有如專利文獻3及5般，直接將電池進行回收再利用之方法、以及專利文獻丨及2所提出般，將電池分解為各構成構件或材料然後再加以回收之方法。本發明，則是一種於電池製造步驟中所產生之包含上述正極物質之漿狀電池殘渣之回收再利用法，與此等之方法皆不相同。本發明，目的在於提供一種從鋰電池之電池殘渣所含有之含Co、Ni及Μη的鋰酸金屬鹽，回收有價金屬之方法。本發明之第一方法，係一種從含有c〇、Ni、Μη之鋰電池殘渣回收有價金屬之方法，其特徵在於，以25〇g/1以上之濃度的鹽酸溶液’將含有鋰酸金屬鹽（含有C〇、Ni 及Μη )之鋰電池殘渣加以攪拌浸洗，然後對浸洗液以酸性萃取劑進行溶劑萃取’萃取出98%以上之Mn、Co及Ni，生成含有各金屬之三種溶液’然後從此等之溶液回收該金屬；第一方法’為一種從含有Co、Ni、Μη之鋰電池殘渣回收有價金屬之方法，其特徵在於，以2〇〇g/1以上之濃度之硫酸溶液，對含有鋰酸金屬鹽（含有c〇、Ni及Mn)之鋰電池殘渣進行加熱攪拌浸洗，然後對浸洗液以酸性萃取劑進行溶劑萃取，萃取出98%以上之Mn、Co及Ni，生成含有各金屬之三種溶液，然後從此等之溶液回收該金屬；第二方法’為一種從含有Co、Ni、Μη之鋰電池殘渣回收有價金屬之方法，其特徵在於，以混合有2〇〇g/1以上之濃度之硫疲;谷液與2〇g/l以上之過氧化氫溶液的溶液， 200934879 將含有锂酸金屬鹽（含有c〇、Ni& Μη)之鐘電池殘渣加以擾捽浸洗’然後對浸洗液以酸性萃取劑進行萃取出98%以上之Mn、c。及州，生成含有各金屬之三插溶液’然後從此等之溶液回收該金屬。檀 Ο❹ In the patent document 6 (Japanese Patent Application No. 2007-74089, filed March 22, 2007), the method of recycling is proposed as described in paragraph 0001. However, in this method, the metals extracted in the organic solvent are only Μη and Co. [Patent Document 1] Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. [Patent Document 5] Japanese Patent Publication No. Hei 10-510878 (Patent Document 6) Japanese Patent Application No. 2007-74089 (March 22, 2007) [Non-Patent Document 丨"Resources and Materials", 1997, 12, Vol.l 13, Special Recycling and Recycling, p. 941 [Non-Patent Document 2] Lectures, Modern Metals, Refining 2, Non-Iron Metals, 1982 July 10th, the Institute of Metals, pp. 240~241 [Invention] 7 200934879 Recycling of batteries, as in Patent Documents 3 and 5, methods for directly recycling and reusing batteries, and patent documents and As proposed in 2, the battery is decomposed into constituent members or materials and then recycled. The present invention is a method for recycling and reusing a slurry battery residue containing the above-mentioned positive electrode material which is produced in a battery manufacturing step, and is different from the above methods. SUMMARY OF THE INVENTION An object of the present invention is to provide a method for recovering valuable metals from a lithium metal acid salt containing Co, Ni and Mn contained in a battery residue of a lithium battery. The first method of the present invention is a method for recovering a valuable metal from a lithium battery residue containing c〇, Ni, and Μη, characterized in that a hydrochloric acid solution having a concentration of 25 〇g/1 or more will contain a lithium metal phosphate salt. The lithium battery residue (containing C〇, Ni, and Μη) is stirred and immersed, and then solvent extraction of the immersion liquid with an acid extractant extracts 98% or more of Mn, Co, and Ni to form three solutions containing each metal. 'The metal is then recovered from such a solution; the first method' is a method for recovering a valuable metal from a lithium battery residue containing Co, Ni, and Mn, characterized by a sulfuric acid solution having a concentration of 2 〇〇g/1 or more The lithium battery residue containing lithium metal phosphate (containing c〇, Ni and Mn) is heated and stirred, and then the solvent is extracted with an acid extractant to extract more than 98% of Mn, Co and Ni. Forming three solutions containing each metal and then recovering the metal from the solutions; the second method is a method for recovering valuable metals from a lithium battery residue containing Co, Ni, and Mn, characterized in that Sulfur fatigue at a concentration of 2〇〇g/1 or more; a solution of a solution of a solution of 25% g/l or more of a hydrogen peroxide solution, 200934879 containing a battery residue of a lithium metal silicate (containing c〇, Ni& Μη) It is irritated and dipped and then extracted with 98% or more of Mn and c from the immersion liquid with an acidic extractant. And the state, generating a three-plug solution containing each metal' and then recovering the metal from such a solution. Tan

又，充分考量使用Co系化合物作為電子元件之電池之正極活性物質者、及使用含有大致等量之Μη、。及犯之鐘酸金屬鹽（以下’稱為三元系鐘金屬鹽）者將持續在市場上市。此時’鋰電池殘潰之c〇相對量將變多。對於此種電池錢’亦可藉由本發明，進行酸洗，然後再進行溶劑萃取，來回收有價金屬。然而，以下之説明，主要係說明三元系鋰金屬鹽之處理。以下’詳細說明本發明。電池殘渣，係由三元系鋰金屬鹽與碳、Ν·甲基j吡咯烷_ ’聚乙烯醇等之溶劑等所構成之漿狀物質，於鋰二次電池製造步驟上所產生之殘逢。其金屬組成，一般為1〇〜 12質量％之C〇、10〜12質量％之犯、10〜12質量％2Μη、 4〜5質量％之Li。本發明人等’以下述之條件來浸洗三元系鋰金屬鹽之電池殘、渣’其結果，可確認硫酸溶液、鹽墜溶液、硫酸與過氧化氫混合溶液對c〇、Ni、Mn、Li之全部的浸洗皆為有效。 (1 )電池殘渣：於【先前技術】中第4段所説明者， 2〇〇g 〇 (2 )浸洗液·表1所示之濃度之各種酸，容量2〇〇〇ml。 200934879Further, the use of a Co-based compound as a positive electrode active material of a battery of an electronic component and the use of a substantially equivalent amount of Μη are sufficiently considered. And the sulphuric acid metal salt (hereinafter referred to as the ternary bell metal salt) will continue to be listed on the market. At this time, the relative amount of c〇 of the lithium battery collapse will increase. For such a battery, the valuable metal can also be recovered by the present invention, pickling, and then solvent extraction. However, the following description mainly describes the treatment of the ternary lithium metal salt. The present invention will be described in detail below. The battery residue is a slurry substance composed of a ternary lithium metal salt and a solvent such as carbon, ruthenium methylpyrrolidine or polyvinyl alcohol, and is produced in a lithium secondary battery manufacturing step. . The metal composition is generally 1 〇 to 12% by mass of C 〇, 10 to 12% by mass, 10 to 12% by mass of 2 Μη, and 4 to 5% by mass of Li. The present inventors have immersed the battery residue and slag of the ternary lithium metal salt under the following conditions. As a result, it was confirmed that the sulfuric acid solution, the salt falling solution, the mixed solution of sulfuric acid and hydrogen peroxide, c, Ni, Mn All of Li's dip is effective. (1) Battery residue: As described in paragraph 4 of the [Prior Art], 2 〇〇 g 〇 (2) immersion liquids, various acids at the concentrations shown in Table 1, and having a capacity of 2 〇〇〇 ml. 200934879

(3 )浸洗時間：4h〜8h。 (4)溫度：加熱至常溫或65〜8〇°C。 (5 )攪拌：有。測試之結果示於表1。 10 200934879(3) Dipping time: 4h~8h. (4) Temperature: Heat to normal temperature or 65 to 8 °C. (5) Stirring: Yes. The results of the test are shown in Table 1. 10 200934879

i -S 8 Ο ^-Η Ο 8 τ-Η 〇 In 8 S »*-Η 8 i a ^ Ο ^Η Ο 8 s Τ—Η 8 8 i Cs 8 ι—Η Ο 8 Ο 泠〇 8 没 Ο r—Η ο f~H 〇 »—Η ο ι—Ι JQ $ 8 δ % CO cn rn rn r〇 <N (Ν cn cn Γ〇 00 〇^ ρ »—Η r-H ρ τ^ ρ ρ r-H «—Η 00 Ν 〇〇 ρ ρ /—s • 一卜〇 ρ »-Η τ—Η ρ ρ Ο »-Η ON CN 〇〇 ρ r—Η y-^ ρ 1—^ /—N o 〇 τ-^ ρ tr—Η ρ r—< ρ 1-^ Ο ι—Ι 1—Η 00 (Ν ρ ρ »—Η ρ /^\ + 〇。 g 1 〇 /^Ν 茭 % + 0。 g l ο r^s + 矣 P S X 〇 /^Ν 'w/ + P 〇 T /~ν 4 % + ii Ρ § 1 ο r~s g /-N % /-Ν m /^-Ν 跦 m 盤 W S ^n r-H 键 % ο (Ν W | r〇盤 | m 毽〇 ^η 盤 § 1 键额 | (Μ 讕 S »〇 (N η % 谗赫 Is CN 200934879 關於三元系鐘金屬鹽之浸洗，可知下列事項。 (1) 若一邊以70〜80°C加熱，一邊進行8小時之攪拌浸洗，則即使為200g/l之硫酸水溶液，皆亦可浸洗出1 〇〇% 之Co、Ni、Mn、Li。溫度在80。(：以上雖亦可浸洗出，但需要蒸發硫酸之淨化設備等。並且’若為3〇〇g/l之硫酸水溶液’若以65〜70°C進行8小時之硫酸浸洗，則亦可達成相同之浸洗率。 (2) 僅有授摔之浸洗時，則若為25Og/Ι以上之濃度之越 ❸ 酸水溶液、及200g/l以上之濃度之硫酸與2〇g/l以上之濃度之過氧化氫的混合水溶液的話，則C〇、Ni、Mn、Li之浸洗率皆為100%。如以上所述，若以200g/l以上之濃度之硫酸水溶液進行加熱浸洗，則可達成100%之浸洗率。其次’僅有攪拌之浸洗，則若為250g/l以上之濃度之鹽酸水溶液、及200gA以上之濃度之硫酸與2〇g/1以上之遭度之過氧化氫的混合水溶液的話，則可達成1 00%之浸洗率。另’在此等之鹽酸水溶液浸洗或硫酸、過氧化氫混合溶液浸洗的情形’亦不會妨礙浸洗液之加熱。又’上述表1中浸洗率100%係實驗室中的數據。若為工業規模之實施，則在月產量回收再利用1〇〇嘲之電池殘渣時’加上秤量之誤差，可達成98〜1〇〇%之浸洗率。浸洗之結果所生成之浸洗液，係含有三元系金屬離子，殘渣主要係由有機或無機狀態之碳所構成。該碳係難溶於硫 12 200934879 ，而以固態物之形態殘留，由於碳等不具回收之價值因此浸洗後之殘渣係將其廢棄或加以焚化。半可以旋轉葉片等任意之手段來進行，以使漿狀電池殘逢均勾地分散於浸洗液中。在將浸洗後之液體所含有《c〇、Ni、Mn、Li加以回i -S 8 Ο ^-Η Ο 8 τ-Η 〇In 8 S »*-Η 8 ia ^ Ο ^Η Ο 8 s Τ—Η 8 8 i Cs 8 ι—Η Ο 8 Ο 泠〇8 No Ο r —Η ο f~H 〇»—Η ο ι—Ι JQ $ 8 δ % CO cn rn rn r〇<N (Ν cn cn Γ〇00 〇^ ρ »—Η rH ρ τ^ ρ ρ rH «— Η 00 Ν 〇〇ρ ρ /—s • 一卜〇ρ »-Η τ—Η ρ ρ Ο »-Η ON CN 〇〇ρ r—Η y-^ ρ 1—^ /—N o 〇τ-^ ρ tr—Η ρ r—< ρ 1-^ Ο ι—Ι 1—Η 00 (Ν ρ ρ »—Η ρ /^\ + 〇. g 1 〇/^Ν 茭% + 0. gl ο r^ s + 矣PSX 〇/^Ν 'w/ + P 〇T /~ν 4 % + ii Ρ § 1 ο r~sg /-N % /-Ν m /^-Ν 跦m disk WS ^n rH key% ο (Ν W | r〇盘 | m 毽〇^η § 1 key amount | (Μ 谰S »〇(N η % 谗赫 Is CN 200934879 About the immersion of the ternary bell metal salt, the following items are known. (1) If the mixture is stirred and heated at 70 to 80 ° C for 8 hours, even if it is a 200 g/l sulfuric acid aqueous solution, 1% by mass of Co, Ni, Mn, and Li may be eluted. The temperature is 80. (: Although it can also be dipped However, it is necessary to evaporate the sulfuric acid purification equipment, etc., and if the aqueous solution of sulfuric acid of 3 〇〇g/l is immersed in sulfuric acid at 65 to 70 ° C for 8 hours, the same immersion rate can be achieved. 2) In the case of only immersion washing, if it is a concentration of 25 Og/Ι or more of an aqueous solution of citric acid, and a mixture of sulfuric acid having a concentration of 200 g/l or more and hydrogen peroxide having a concentration of 2 〇g/l or more or more In the case of an aqueous solution, the leaching rates of C 〇, Ni, Mn, and Li are all 100%. As described above, if the immersion is performed by a hot sulphuric acid aqueous solution having a concentration of 200 g/l or more, 100% immersion can be achieved. Next, if there is only a stirred immersion, if it is a hydrochloric acid aqueous solution having a concentration of 250 g/l or more, and a mixed aqueous solution of sulfuric acid having a concentration of 200 g or more and hydrogen peroxide having a concentration of 2 〇g/1 or more, Then, a immersion rate of 100% can be achieved. In addition, the case where the aqueous hydrochloric acid solution is immersed or the sulfuric acid or hydrogen peroxide mixed solution is immersed does not hinder the heating of the immersion liquid. Further, the immersion rate of 100% in Table 1 above is the data in the laboratory. In the case of industrial scale implementation, when the monthly production is recycled and reused, the battery residue is added, and the impregnation rate of 98 to 1% is achieved by adding the error of the weighing. The immersion liquid formed as a result of the immersion contains ternary metal ions, and the residue mainly consists of carbon in an organic or inorganic state. The carbon system is insoluble in sulfur 12 200934879, and remains in the form of solid matter. Since carbon is not recovered, the residue after dipping is discarded or incinerated. It can be carried out by any means such as rotating the blade, so that the slurry battery residue is uniformly dispersed in the immersion liquid. After the dipping liquid contains "c〇, Ni, Mn, Li back

=面’若對Μη、C。、Ni之三種金屬進行溶劑萃取，則可分離出Li。對此等金屬進行溶劑萃取之萃取劑，例如，可使用非專利文獻i (資源與材料，1997,12, ν〇1 ιι3，「回收再利用特別企畫」）帛94 i頁表i之公知酸性萃取劑。 Μη萃取劑，較佳為使用LANXESS公司製的D2EHpA，又Co及Ni之萃取劑，較佳為使用大八化學股份有限公司製的PC-88A。D2EHPA係二（2_乙基己）磷酸，於非專利文獻1中為公知的Μη萃取劑。PC_88A係（2_乙基己）（2_ 乙基己）膦酸酯系，該資訊可由1202884345〇93一l.pdf獲得。從萃取後之溶液回收金屬的方法，可藉由下述目剪所進行的方法來加以回收，或者是作為含有有價金屬之資源來販賣，然後於回收此等金屬之公知濕式精鍊步驟中，作為副原料來處理，以回收金屬。= face 'if Μη, C. Li, the three metals of Ni are solvent-extracted to separate Li. For extracting agents for solvent extraction of such metals, for example, Non-Patent Document i (Resources and Materials, 1997, 12, ν〇1 ιι3, "Recycling and Special Planning") can be used. Acidic extractant. The Μη extracting agent is preferably D2EHpA manufactured by LANXESS Co., Ltd., and an extractant of Co and Ni, preferably PC-88A manufactured by Daiba Chemical Co., Ltd. D2EHPA is bis(2-ethylhexyl)phosphoric acid, which is a well-known Μη extractant in Non-Patent Document 1. PC_88A is a (2-ethylhexyl) (2-ethylhexyl) phosphonate system, and the information can be obtained from 1202884345〇93-l.pdf. The method for recovering metal from the extracted solution can be recovered by the following method, or sold as a resource containing a valuable metal, and then in a known wet refining step for recovering the metal, It is treated as an auxiliary material to recover metal.

Co :氣化姑之電解提煉法。 Μη :硫酸錳之電解提煉法。Co: Gasification and electrolysis. Μη: electrolytic refining method of manganese sulfate.

Ni :氣浸洗之Ni電解法。金屬回收的其他方法’可以採用在溶劑萃取後，藉由將經逆萃取之液體的硫酸酸性溶液加以中和，以使金屬鹽 13 200934879 沈澱，然後藉由過濾，以固體成分之形態來回收金鹽的方法。接著’該金屬鹽，亦可將作為金屬原料販賣至金屬精鍊公司。或者，若將金屬鹽之濃度較溶劑萃取後液體之濃度濃縮至數倍，然後藉由電解提煉來加 w叹flf，則可從電池殘渣之回收至金屬再利用為止進行一貫化地回再利用。Ni、Co、Μη之電解提煉，例如，可以非專利獻2 (講座•現代之金屬學，精鍊編2 ,非鐵金屬冶練，190Ni: Ni electrolytic method for gas immersion. The other method of metal recovery can be carried out by neutralizing the acidic solution of sulfuric acid in the liquid after the solvent extraction to precipitate the metal salt 13 200934879, and then filtering to recover the gold in the form of a solid component. The method of salt. The metal salt can then be sold as a metal raw material to a metal refining company. Alternatively, if the concentration of the metal salt is concentrated several times more than the concentration of the liquid after solvent extraction, and then the alloy is extracted by electrowinning, the flf can be re-used from the recovery of the battery residue to the reuse of the metal. . Electrolytic refining of Ni, Co, and Μη, for example, can be non-patented 2 (Lecture • Modern Metallurgy, Refining 2, Non-Iron Metals, 190

年7月10曰金屬學會出版）第24〇〜241頁所記載之條件2 來進行。 ' 接著，參照圖1、圖2、圖3，具體說明藉由DE2HpA 及PC-88A，分別對Μη、Co及Ni進行溶劑萃取之方法 [Μη之萃取] 於附有側流器及攪拌機之分液槽，將DE2HPa之煤油 (燈油）混合液與Co-Ni-Mn-Li溶液（即浸洗後之液體，參照圖1)加以混合，進行溶劑萃取。添加苛性鈉，將pH值調整為2〜3。然後，進一步進行利用溶劑之萃取，藉此，使溶液僅殘留Co-Ni-Li。溶劑，係與溶液為相反方向地流至萃取3、萃取2、萃取1(逆流多階段萃取)。由於Mn萃取後之溶劑中，亦含有些微之Co,因此以1〇g/1之仏別4將c〇加以洗淨。接著’以50g/l之硫酸水溶液進行逆萃取，使Mn濃縮於硫酸水溶液中（「Μη溶液」）。逆萃取係以2階段進行，溶劑則於萃取3加以再利用。於Μη溶液添加苛性納、或 14 200934879 碳酸鈉以進行中和，對中和後之液體及沈澱物進行過濾，以Mn(OH)2、MnC03的形態來回收Μη。洗淨液則加入萃 * 取刖之Co_Ni-Mn-Li溶液。 [Co之萃取] 於附有侧流器及攪拌機之分液槽，將PC_88A之煤油（燈油）混合液與Co-Ni-Li溶液（即Μη萃取後之液體，參照圖 2)加以混σ，進行溶劑萃取。添加苛性納，將pH值調整為4〜5 〇〇然後，進一步進行利用溶劑之萃取，藉此，使溶液僅殘留Ni。溶劑，係與溶液為相反方向地流至萃取3、萃取 2、萃取1(逆流多階段萃取）。由於c〇萃取後之溶劑中，亦含有些微之Ni，因此以1〇g/l之HJ04將Ni加以洗淨。接著，以50g/l之硫酸水溶液進行逆萃取，使c〇濃縮於硫酸水溶液中（rc〇溶液」）。逆萃取係以2階段進行， /合劑則於萃取3加以再利用。於c〇溶液添加苛性鈉、或碳k納以進行中和，對中和後之液體及沈殺物進行過遽，以Co(OH)2、coc〇3的形態來回收c〇。洗淨液則加入萃取月il之Co-Ni-Li溶液。 [Ni之萃取] 於附有側流器及攪拌機之分液槽，將pc_88A之煤油（燈油^合液與Ni_U溶液（即Co萃取後之液體，參照圖3)加 ^混σ，進行溶劑萃取。添加苛性納，將pH值調整為6〜然後，進一步進行利用溶劑之萃取，藉此，使溶液僅 15 200934879 殘留Li。溶劑，係與溶液為相反方向地流至萃取3、萃取 2、萃取丨（逆流多階段萃取）。由於Ni萃取後之溶劑中，亦含有些微之Li’因此以10g/1iH2S〇4BU加以洗淨。接著，以50g/l之硫酸水溶液進行逆萃取，使恥濃縮於硫酸水溶液中（「Ni溶液」）。逆萃取係以2階段進行' 溶劑則於萃取3加以再利用。於Ni溶液添加苛性鈉、或碳酸鈉以進行中和，對中和後之液體及沈澱物進行過濾，In July, the 10th Metal Society published) Conditions 2 as described on pages 24 to 241. ' Next, referring to Fig. 1, Fig. 2, Fig. 3, the method of solvent extraction of Μη, Co and Ni by DE2HpA and PC-88A, respectively [Extraction of Μη] is attached to a side streamer and a mixer. In the liquid tank, the kerosene (lamp oil) mixture of DE2HPa and the Co-Ni-Mn-Li solution (that is, the liquid after immersion, refer to FIG. 1) were mixed and subjected to solvent extraction. Add caustic soda and adjust the pH to 2~3. Then, extraction with a solvent is further carried out, whereby only the Co-Ni-Li remains in the solution. The solvent flows in the opposite direction to the solution to extract 3, extract 2, and extract 1 (countercurrent multistage extraction). Since the solvent after the extraction of Mn also contains a slight amount of Co, c〇 is washed with a discrimination of 1〇g/1. Subsequently, the mixture was back-extracted with a 50 g/l aqueous sulfuric acid solution to concentrate Mn in an aqueous sulfuric acid solution ("?" solution). The reverse extraction is carried out in two stages, and the solvent is reused in extraction 3. The caustic soda or 14 200934879 sodium carbonate was added to the Μη solution for neutralization, and the neutralized liquid and the precipitate were filtered to recover Μη in the form of Mn(OH)2 and MnC03. The cleaning solution is added to the Co*Ni-Mn-Li solution. [Co extraction] In a liquid separation tank equipped with a flow divider and a mixer, the PC_88A kerosene (lamp oil) mixture and the Co-Ni-Li solution (ie, the liquid extracted after Μη, see FIG. 2) are mixed σ. Solvent extraction was carried out. The caustic soda is added, and the pH is adjusted to 4 to 5 〇〇 Then, extraction with a solvent is further carried out, whereby only Ni remains in the solution. The solvent flows to the extraction 3, the extraction 2, and the extraction 1 in the opposite direction to the solution (countercurrent multistage extraction). Since the solvent after the extraction of c〇 also contained a slight amount of Ni, Ni was washed with 1 〇g/l of HJ04. Next, reverse extraction was carried out with a 50 g/l aqueous sulfuric acid solution to concentrate c 〇 in an aqueous sulfuric acid solution (rc 〇 solution). The reverse extraction is carried out in two stages, and the / mixture is reused in extraction 3. The caustic soda or carbon k-ne was added to the c〇 solution for neutralization, and the liquid and the precipitate after the neutralization were subjected to hydrazine, and c〇 was recovered in the form of Co(OH)2 and coc〇3. The cleaning solution was added to a Co-Ni-Li solution of the extraction month il. [Extraction of Ni] In the liquid separation tank with a flow divider and a mixer, the kerosene of the PC_88A (the lamp oil and the Ni_U solution (ie, the liquid after Co extraction, refer to FIG. 3) is mixed and σ is used for solvent extraction. Adding caustic soda, adjusting the pH to 6~, and then further extracting with a solvent, thereby leaving the solution only 15 200934879 Residual Li. The solvent flows in the opposite direction to the solution to extract 3, extract 2, extract丨 (countercurrent multi-stage extraction). Since the solvent after Ni extraction also contains a little Li', it is washed with 10g/1iH2S〇4BU. Next, reverse extraction is carried out with 50g/l aqueous sulfuric acid solution to concentrate In aqueous sulfuric acid solution ("Ni solution"). The reverse extraction is carried out in two stages. The solvent is reused in extraction 3. The caustic soda or sodium carbonate is added to the Ni solution for neutralization, and the liquid and precipitate after neutralization. Filtration,

以Ni(OH)2、Ναό;的形態來回收N卜洗淨液則加入萃取前之Ni-Li溶液。藉由上述之溶劑萃取所得之c〇、Ni、Mn、u濃度之 -般範圍及實施例之濃度示於表2。金屬，可藉由中和，分別以 Mn(OH)2 或 MnC〇3、c〇(〇H)2 或 Co%、叫〇耶或NiC03、及Li(OH)2或UC03之形態來加以回收。 [表2] Co 濃度（g/1) 含Co之溶液含Ni之溶液含Li之溶液The N-wash solution was recovered in the form of Ni(OH)2, Ναό; and the Ni-Li solution before extraction was added. The range of the concentrations of c〇, Ni, Mn, and u obtained by solvent extraction described above and the concentrations of the examples are shown in Table 2. Metals can be recovered by neutralization, in the form of Mn(OH)2 or MnC〇3, c〇(〇H)2 or Co%, 〇耶 or NiC03, and Li(OH)2 or UC03, respectively. . [Table 2] Co concentration (g/1) solution containing Co solution containing Ni solution containing Li

〇表 τ、上所述，本發明之較佳實施態樣如下。 ⑴對Mn、Co及Ni進行酸性溶劑萃取之方法。 ,(2)藉由調整逆萃料之溶液、及將cG、Ni、Mn回收後之含有U之溶液的阳值，使Mn、c〇、Ni、Li沈殿， 16 200934879 並進仃過濾，藉此以固體成分之形態，來分離金屬之方法。 (3)如（2)之方法，係將固體金屬再溶解於電解液，進行電解提煉。 (1) 由於可以漿體狀態來回收三元系金屬鋰鹽系正極活性物質，因此毋須用以將鋰電池殘渣固體化之能量。並且，漿體中之三元系金屬鋰鹽呈微粒子狀態，因此與浸洗液之接觸面積較大，浸洗效率較高。 (2) C〇、Ni、Mn及Li各別可全量浸洗出。另一方面，除此以外之碳等則成為殘渣，與上述四種金屬分離。 (3) 由於使用稀釋硫酸或稀釋鹽酸，因此對環境所造成之負擔較少。 (4)Li雖會溶解於浸洗液，但可藉由對其他之有價金屬進行萃取分離，以使與其他之有價金屬分離（自犯溶液將 Ni萃取後，亦會殘留於液體中）。於溶劑萃取時，將Mn、 Co、Ni加以分離後，Li殘留而分離於濾液中。【實施方式】〇 Table τ, as described above, preferred embodiments of the present invention are as follows. (1) A method of extracting Mn, Co and Ni by acidic solvent extraction. (2) by adjusting the solution of the reverse stripping material and the positive value of the solution containing U after recovering cG, Ni, and Mn, so that Mn, c〇, Ni, and Li are dissolved, 16 200934879 A method of separating metals in the form of a solid component. (3) The method according to (2), wherein the solid metal is redissolved in the electrolytic solution to carry out electrolytic refining. (1) Since the ternary metal lithium salt-based positive electrode active material can be recovered in a slurry state, energy for solidifying the lithium battery residue is not required. Further, since the ternary metal lithium salt in the slurry is in the form of fine particles, the contact area with the immersion liquid is large, and the leaching efficiency is high. (2) C〇, Ni, Mn and Li can be fully immersed in each case. On the other hand, carbon or the like other than this is a residue and is separated from the above four metals. (3) Due to the use of diluted sulfuric acid or diluted hydrochloric acid, the burden on the environment is less. (4) Although Li dissolves in the immersion liquid, it can be separated from other valuable metals by extraction and separation of other valuable metals (the self-injection solution will also remain in the liquid after extraction of Ni). In the solvent extraction, Mn, Co, and Ni are separated, and Li remains and is separated into the filtrate. [Embodiment]

11% ' Ni ：膠漿」），，萃取時間洗淨則是攪對100g之含有三元系金屬鐘鹽之膠聚 11 %、Μη : 11%、Li : 4.3 %，以下僅稱之為「進行浸洗及溶劑萃取。於以下所説明之測試中係攪拌10分鐘’逆萃取時間係攪拌分鐘，拌10分鐘來進行。 (1)浸洗 1〇〇〇L中，一邊以70 然後進行過濾後，在將膠漿投入300g/l之硫酸水溶液 8 01進行加熱，一邊擾摔4小時， 17 200934879 乾燥後之狀態下，殘留有1 0g之殘渣。1000L之濾液中之金屬濃度如下表所示，可進行100%之浸洗。 [表3] 濾液 Co Ni Μη Li 濃度（g/1) 11 11 11 4.3 分配率（％) 100 100 100 100 (2)Mn萃取 @ 以25 % NaOH溶液對濾液進行中和後，進行Μη之溶劑萃取。中和後之溶液為1290L。溶劑萃取劑為LANXESS 公司製的D2EHPA之煤油溶液1290L，將其與中和後之溶液一起攪拌後，以25%NaOH溶液將pH值調整為2.5( 0/A 比=1/1 )。溶劑萃取之結果，得到Μη萃取液1290L與 Co-Ni-Li溶液1340L。以1 Og/Ι之H2S04將Μη萃取液（稍微含有Co)加以洗淨，接著以50g/l之硫酸水溶液進行逆萃取，使Μη濃縮於_硫酸水溶液中（Μη溶液）。得到Co-Ni-Li ❹ 溶液1340L(金屬濃度示於表4)與Μη溶液250L(金屬濃度示於表5)。 [表4]11% 'Ni : glue'), , the extraction time is washed with 100g of ternary metal bell salt glue 11%, Μη: 11%, Li: 4.3%, hereinafter referred to as " Dip and solvent extraction. Stir for 10 minutes in the test described below. 'Reverse extraction time is stirred for 10 minutes. (1) Dip 1 〇〇〇L, side with 70 and then filter Thereafter, the slurry was poured into a 300 g/l aqueous sulfuric acid solution 801 for heating, and the mixture was disturbed for 4 hours. After the drying of 17 200934879, 10 g of the residue remained. The concentration of the metal in the 1000 L filtrate was as shown in the following table. 100% immersion can be performed. [Table 3] Filtrate Co Ni Μη Li Concentration (g/1) 11 11 11 4.3 Distribution ratio (%) 100 100 100 100 (2) Mn extraction @ 25% NaOH solution to the filtrate After neutralization, solvent extraction of Μη was carried out. The neutralized solution was 1290 L. The solvent extractant was 1290 L of D2EHPA kerosene solution manufactured by LANXESS Co., Ltd., and stirred with the neutralized solution, followed by 25% NaOH solution. The pH was adjusted to 2.5 (0/A ratio = 1/1). The result of solvent extraction gave Μη. Take 1290L and 1340L of Co-Ni-Li solution. Wash the Μη extract (slightly containing Co) with 1 Og/ΙH2S04, then carry out reverse extraction with 50g/l aqueous sulfuric acid solution to concentrate Μ _ sulphuric acid. In an aqueous solution (Μη solution), 1340 L of a Co-Ni-Li ❹ solution (metal concentration is shown in Table 4) and 250 L of a Μη solution (metal concentration are shown in Table 5) were obtained.

Co-Ni-Li 溶液 Co Ni Μη Li 濃度（g/1) 8.0 8.1 <0.01 3.1 分配率（％) 99 100 0 100 18 200934879 [表5] Μη溶液 Co Ni Μη Li 濃度（g/1) <0.01 <0.01 44 <0.01 分配率（％) 0 0 99 0 對表4所示之Co、Ni、Li溶液進行Co之溶劑萃取。溶劑萃取劑為大八化學股份有限公司製的PC-88A之煤油溶液1340L，將其與中和後之溶液一起攪拌後，以25%NaOH 溶液將pH值調整為4.2( Ο/A比=1/1 )。溶劑萃取之結果，得到Co萃取液1340L與Ni-Li溶液1390L。以10g/l之H2S04 將Co萃取液（稍微含有Ni)加以洗淨，接著以50g/l之硫酸水溶液進行逆萃取，使C 〇濃縮於硫酸水溶液中（C 〇溶液）。得到Ni-Li溶液1390L(金屬濃度示於表 6)與Co溶液 250L(金屬濃度示於表7)。Co Ni Ni Ni Ni Ni Ni ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ; 0.01 < 0.01 44 < 0.01 Distribution ratio (%) 0 0 99 0 The solvent extraction of Co was carried out on the Co, Ni, and Li solutions shown in Table 4. The solvent extractant was 1340 L of PC-88A kerosene solution manufactured by Daeba Chemical Co., Ltd., and after stirring with the neutralized solution, the pH was adjusted to 4.2 with a 25% NaOH solution (Ο/A ratio = 1). /1 ). As a result of solvent extraction, 1340 L of a Co extract and 1390 L of a Ni-Li solution were obtained. The Co extract (slightly containing Ni) was washed with 10 g/l of H2SO4, followed by back extraction with 50 g/l of a sulfuric acid aqueous solution to concentrate C oxime in an aqueous sulfuric acid solution (C 〇 solution). 1390 L of a Ni-Li solution (metal concentration is shown in Table 6) and 250 L of a Co solution (metal concentration are shown in Table 7) were obtained.

[表6][Table 6]

Ni-Li溶液 Co Ni Μη Li 濃度（g/1) <0.01 7.8 <0.01 3.0 分配率（％) 0 99 0 100 [表7]Ni-Li solution Co Ni Μη Li Concentration (g/1) <0.01 7.8 <0.01 3.0 Distribution ratio (%) 0 99 0 100 [Table 7]

Co溶液 Co Ni Mn Li 濃度（g/1) 43 <0.01 <0.01 <0.01 分配率（％) 98 0 0 0 19 200934879 對表6所不之Νι、Li溶液進行犯之溶劑萃取。溶劑萃取劑為大八化學股份有限公司製的pc_88A之煤油溶液 13 90L ’將其與中和後之溶液—起攪拌後以25%Na〇H 溶液將PH值調整為6.5(0/八比；=1/1)〇溶劑萃取之結果，得到Ni萃取液1390L與Li溶液Ul〇L。以i〇g/iiH2S〇4 將Ni萃取液（稍微含有U)加以洗淨，接著以5〇g/1之硫酸水溶液進行逆萃取，使Ni濃縮於硫酸水溶液中（犯溶液）。得到Li溶液1410L(金屬濃度示於表8)與川溶液25〇l(金屬濃度示於表9)。Co solution Co Ni Mn Li Concentration (g/1) 43 < 0.01 < 0.01 < 0.01 Distribution ratio (%) 98 0 0 0 19 200934879 Solvent extraction of the ι and Li solutions which are not shown in Table 6. The solvent extractant is a kerosene solution of PC_88A manufactured by Daeba Chemical Co., Ltd. 13 90L ', and the solution after neutralization is stirred, and the pH is adjusted to 6.5 (0/8 ratio) with a 25% Na〇H solution; =1/1) As a result of solvent extraction, 1390 L of Ni extract and Ul solution of Li solution were obtained. The Ni extract (slightly containing U) was washed with i〇g/iiH2S〇4, followed by back extraction with a 5 〇g/1 aqueous solution of sulfuric acid to concentrate Ni in an aqueous solution of sulfuric acid (solution). A Li solution of 1410 L (metal concentration shown in Table 8) and a solution of 25 μl (metal concentration are shown in Table 9) were obtained.

GG

[表9] Ni溶液 Co 濃度（g/1) <0.01 分配率（％) 0[Table 9] Ni solution Co concentration (g/1) <0.01 Distribution ratio (%) 0

[表8][Table 8]

Li溶液 Co Ni Μη Τ ί 濃度（g/1) <0.01 <0.01 — 0 <0.01_ 0 2.9 99 分配率（％) 0 — 如以上所示，可將Mn、c〇、Ni、τ .入Li solution Co Ni Μη Τ ί Concentration (g/1) <0.01 <0.01 - 0 <0.01_ 0 2.9 99 Distribution ratio (%) 0 - Mn, c〇, Ni, τ can be obtained as shown above .

Ll全部分離出來。此外，雖以硫酸浸洗來作說明，作由私…故 1一由於U鹽酸浸洗亦可將金屬全量浸洗出，目此其後之溶劑萃取亦為相同之結果。 [產業上之可利用性] 以往由於沒有以三兀系金屬鋰鹽作钓止極活性物質之 20 200934879 電池殘渣的回收再利用法，因此只能保管於倉庠等藉由本發明之方法，以硫酸或鹽酸來浸洗電池但若 A /置，則來進行有價金屬之回收。使用非為漿狀之含有c〇、. Ν ΐ > Λ/fr» 的鋰電池殘渣進行相同的測試，亦可得到相同的結果。又，η 於本發明之方法中，由於採用的又，疋，谷劑卒取法，因此例如於電池殘渣有混入Co系正極活性物物賈’亦不會發生問題，依然可回收有價金屬，故可使易。使口收再利用事業之發展容Ll is completely separated. In addition, although it is described by the leaching of sulfuric acid, it can be used as a private one. Therefore, the entire amount of metal can be immersed by immersion of U hydrochloric acid, and the subsequent solvent extraction is also the same result. [Industrial Applicability] In the past, there was no recycling method for the use of the triterpene metal lithium salt as a fishing-stopping active material, and therefore it can only be stored in a warehouse or the like by the method of the present invention. Sulfuric acid or hydrochloric acid is used to dip the battery, but if A/set, the recovery of valuable metals is carried out. The same test results were obtained using the non-paste lithium battery residue containing c〇, . Ν ΐ > Λ/fr». Further, η is in the method of the present invention, and since it is used, the strontium and the granules are taken up, so that, for example, if the battery residue is mixed with the Co-based positive electrode active material, there is no problem, and the valuable metal can be recovered. Can make it easy. Develop the development of the recycling business

【圖式簡單說明】驟之流程圖驟之流程圖驟之流程圖圖1 ’係顯示Μη之溶劑萃取步圖2，係顯示Co之溶劑萃取步圖3，係顯示Ni之溶劑萃取步【主要元件符號說明】無[Simple diagram of the flow chart] Flow chart of the flow chart of the flow chart Figure 1 shows the solvent extraction step of Fig. 2, showing the solvent extraction step of Co. Figure 3 shows the solvent extraction step of Ni [mainly Component symbol description]

21twenty one

Claims

200934879 十、申請專利範圍： ' 1.—種自含有c〇、Ni、Mn之鋰電池殘渣回收有價金 - 屬之方法，其特徵在於：乂 25 Og/l以上之濃度的鹽酸溶液’將含有鋰酸金屬鹽 (含有Co、Νι及Μη )之鋰電池殘渣加以攪拌浸洗，然後對浸洗液以酸性萃取劑進行溶劑萃取，萃取出98%以上之 Mn、Co及Ni ’生成含有各金屬之三種溶液，然後從此等之溶液回收該金屬。 © 2· 一種自含有C〇、Ni、Μη之裡電池殘渣回收有價金屬之方法’其特徵在於：以200g/l以上之濃度之硫酸溶液’對含有鋰酸金屬鹽 (含有Co、Ni及Μη )之鋰電池殘渣進行加熱攪拌浸洗，然後對浸洗液以酸性萃取劑進行溶劑萃取，萃取出98%以上之Mn、Co及Ni’生成含有各金屬之三種溶液，然後從此等之溶液回收該金屬 3 · —種自含有Co、Ni、Μη之鋰電池殘渣回收有價金 © 屬之方法，其特徵在於：以混合有200gA以上之濃度之硫酸溶液與2〇g/1以上之過氧化氣溶液的溶液’將含有裡酸金屬鹽（含有C〇、Ni 及Μη )之鋰電池殘渣加以攪拌浸洗，然後對浸洗液以酸性萃取劑進行溶劑萃取，萃取出98%以上之Mn、Co及Ni，生成含有各金屬之三種溶液’然後從此等之溶液回收該金屬。 4.如申凊專利範圍第1至3項中任一項之自含有c〇、 22 200934879 Ni、Μη之鋰電池殘么队有價金屬之方萃取劑來溶劑萃取出Μη、“及犯。去其係以酸性200934879 X. Patent application scope: ' 1. - A method for recovering valuable gold from a lithium battery residue containing c〇, Ni, Mn, which is characterized by: a hydrochloric acid solution of 乂25 Og/l or more will contain Lithium battery residues (containing Co, Νι, and Μη) are stirred and immersed in a solvent, and then the solvent is extracted with an acid extractant to extract more than 98% of Mn, Co, and Ni'. The three solutions are then recovered from the solution. © 2· A method for recovering valuable metals from battery residues containing C〇, Ni, and 'η' is characterized by: a sulfuric acid solution containing a concentration of 200 g/l or more, containing a lithium metal silicate (containing Co, Ni, and Μη) Lithium battery residue is heated and stirred for dipping, and then solvent extraction is performed on the immersion liquid with an acid extractant to extract 98% or more of Mn, Co and Ni' to form three solutions containing each metal, and then recover from the solution. The metal 3 is a method for recovering valuable gold from a lithium battery residue containing Co, Ni, and Μη, characterized in that: a sulfuric acid solution having a concentration of 200 gA or more and a peroxic gas having a concentration of 2 〇g/1 or more are mixed. Solution of solution 'The lithium battery residue containing metal citrate (containing C〇, Ni and Μη) is stirred and dipped, and then the solvent is extracted with an acid extractant to extract more than 98% of Mn and Co. And Ni, to form three solutions containing each metal' and then recover the metal from such solutions. 4. As claimed in any one of claims 1 to 3 of the patent scope, the extracting agent of the valuable metal from the lithium battery containing c〇, 22 200934879 Ni, Μη is solvent extracted and extracted. It is acidic

5.如申請專利範圍第4項之自含有電池殘渣回收有價金屬之方法，其中由進行PH值之調整，使Mn、Cq'、& 濾’以固態物之形態來加以回收。 6·如申請專利範圍第5項之自含有電池殘渣回收有價金屬之方法，其中，解於電解液，進行電解提煉。 C〇、Ni、Mn 之鋰係在溶劑萃取後藉沈澱，然後藉由過 Co、Ni、Μη 之鐘係將該固態物再溶 7.如申請專利範圍第4項之自含有電池殘渣回收有價金屬之方法，其中， Co、Ni、Μη 之鐘對藉由溶劑萃取將 C〇、Ni、Μη 萃取後所殘留之液體進行pH值調整，使Li 沈澱’然後藉由過濾’以固態物之形態來加以回收。5. A method for recovering valuable metals from a battery residue according to item 4 of the patent application, wherein Mn, Cq', & filtration is recovered in the form of a solid by adjusting the pH. 6. A method for recovering valuable metals from a battery residue according to item 5 of the patent application scope, wherein the electrolyte solution is used for electrolytic refining. The lithium of C〇, Ni, and Mn is precipitated by solvent extraction, and then the solid is re-dissolved by a clock system of Co, Ni, and 7. 7. The content of the battery residue is recovered from the fourth item of the patent application. a metal method in which a clock of Co, Ni, and Μη is subjected to pH adjustment of a liquid remaining after extraction of C〇, Ni, and Μ by solvent extraction, so that Li is precipitated and then filtered to form a solid form. Come and recycle it.

十、圖式：如次頁 23X. Schema: as the next page 23