TWI392745B - A method for recovering a valuable metal from a lithium battery residue containing Co, Ni, and Mn - Google Patents

A method for recovering a valuable metal from a lithium battery residue containing Co, Ni, and Mn Download PDF

Info

Publication number
TWI392745B
TWI392745B TW97141955A TW97141955A TWI392745B TW I392745 B TWI392745 B TW I392745B TW 97141955 A TW97141955 A TW 97141955A TW 97141955 A TW97141955 A TW 97141955A TW I392745 B TWI392745 B TW I392745B
Authority
TW
Taiwan
Prior art keywords
metal
solution
lithium battery
recovering
sulfuric acid
Prior art date
Application number
TW97141955A
Other languages
Chinese (zh)
Other versions
TW200934879A (en
Inventor
Yosuke Yamaguchi
Jyunzo Hino
Original Assignee
Jx Nippon Mining & Metals Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to JP2008031800A priority Critical patent/JP4865745B2/en
Application filed by Jx Nippon Mining & Metals Corp filed Critical Jx Nippon Mining & Metals Corp
Publication of TW200934879A publication Critical patent/TW200934879A/en
Application granted granted Critical
Publication of TWI392745B publication Critical patent/TWI392745B/en

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/04Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • C22B3/06Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
    • C22B3/10Hydrochloric acid, other halogenated acids or salts thereof
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B23/00Obtaining nickel or cobalt
    • C22B23/04Obtaining nickel or cobalt by wet processes
    • C22B23/0407Leaching processes
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B26/00Obtaining alkali, alkaline earth metals or magnesium
    • C22B26/10Obtaining alkali metals
    • C22B26/12Obtaining lithium
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/44Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B47/00Obtaining manganese
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006Wet processes
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/54Reclaiming serviceable parts of waste accumulators
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/20Recycling
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00Technologies for solid waste management
    • Y02W30/50Reuse, recycling or recovery technologies
    • Y02W30/84Recycling of batteries or fuel cells

Description

自含有Co、Ni、Mn之鋰電池殘渣回收有價金屬之方法Method for recovering valuable metals from lithium battery residues containing Co, Ni, and Mn
本發明係關於一種自含有Co,Ni,Mn之鋰電池殘渣回收有價金屬之方法。含有Co,Ni,Mn之鋰電池殘渣,係指由三元系鋰金屬鹽與碳、N-甲基-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。The present invention relates to a method for recovering valuable metals from a lithium battery residue containing Co, Ni, Mn. A lithium battery residue containing Co, Ni, and Mn means a slurry material composed of a ternary lithium metal salt and a solvent such as carbon, N-methyl-2-pyrrolidone or polyvinyl alcohol. In the 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 such as these, the treatment of lithium metal oxide containing a valuable metal is very important from the viewpoint of recovering valuable metals.
日本特開平6-251805號公報(專利文獻1),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、Co、Ti、Fe、V、Mn、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。Japanese Patent Laid-Open No. Hei 6-251805 (Patent Document 1), although a lithium secondary battery has not been developed at the time of its application (1993), it is the first to investigate the recycling and recycling of lithium secondary batteries before development. In this method, a used lithium battery is cut with a water jet, and then the solid separated by the filtration is separated into a separator, a current collector, and a positive electrode. It is stated that these may be melted or pulverized and then reused according to the materials. Further, the metal used as the metal oxide of the positive electrode material may be a metal such as Ni, Co, Ti, Fe, V, Mn, Mo, Cr, W, etc., but not all of these metals are used at present. The most used metal is Co.
日本特開2006-331707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 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,藉此得到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。JP-A-2006-331707 (Patent Document 2) proposes a lithium battery recovery and reuse method composed of a plurality of stages, in which a wound body, a positive electrode, a negative electrode, and a separator are placed in a stage before and after recovery of a positive electrode material. The plate is mechanically separated, and the positive electrode is immersed in an aqueous solution of nitric acid to pass the positive electrode The substrate (aluminum) is separated from the positive electrode active material, and then the positive electrode active material is immersed in a hydrochloric acid solution to be dissolved, and then the solution is filtered to obtain a metal ion mixed solution of Li, Ni or the like. Next, each metal is recovered from the mixed solution by a method such as ion exchange, electrolysis, precipitation separation or the like.
日本特許第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Mo、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。Japanese Patent No. 3,450,684 (Patent Document 3) is an application for mounting a lithium secondary battery to various electronic devices, which was applied for in 1997, and proposes to recover Mo, Co, and a positive electrode active material from a used lithium battery. Ni, Sn, etc. methods. Specifically, the lithium battery is disassembled without being used, and calcined together with the iron shell, and then the calcined product is pulverized, magnetic separation is performed once, and magnetic separation is performed twice for the non-magnetic material.
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Co、Ni及Mn之鋰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2007-48692號公報),係提出一種如下述之技術,亦即,將二氧化錳、氧化鈷、氧化鎳及碳酸鋰加以秤量,使Ni:Mn:Co之比為1:1:1,Li:(Ni、Mn、Co)之比為1.06:1,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。Since the Co used in the positive electrode is expensive, a technique of using a lithium metal oxide salt containing approximately equal amounts of Co, Ni, and Mn as a positive electrode active material has recently been developed. For example, Patent Document 4 (JP-A-2007-48692) proposes a technique in which manganese dioxide, cobalt oxide, nickel oxide, and lithium carbonate are weighed so that Ni:Mn:Co The ratio is 1:1:1, and the ratio of Li:(Ni, Mn, Co) is 1.06:1, and these compounds are mixed with a polyvinyl alcohol solution, and then granulated, dried, and fired. This calcined ternary metal lithium composite oxide is mixed with a binder and a solvent to prepare a slurry positive electrode active material.
鎳-氫化物電池之正極活性物質為羥基氧化鎳(NiOOH),而非鋰電池之正極活性物質之鋰酸金屬。關於從該鎳-氫化物電池回收金屬之方法,專利文獻5(日本特表平10-510878號公報)係提出如下之方法。亦即(1)以切碎機將廢電池加以粉碎,(2)藉由對所得之廢料進行磁分 離,以將Fe、Ni加以分離,(3)以硫酸將非磁性材料加以溶解,(4)藉由調整pH,以將Fe加以分離,(5)以過濾將Fe分離後,對該濾液進行有機溶劑萃取,藉此將Zn、Cd、Mn、Al萃取出。The positive electrode active material of the nickel-hydride battery is nickel oxyhydroxide (NiOOH) instead of the lithium acid metal of the positive electrode active material of the lithium battery. In the method of recovering a metal from the nickel-hydride battery, the following method is proposed in the patent document 5 (Japanese Patent Publication No. Hei 10-510878). That is, (1) crushing the waste battery with a chopper, and (2) magnetically dividing the obtained waste Separate to separate Fe and Ni, (3) dissolve non-magnetic material with sulfuric acid, (4) separate Fe by adjusting pH, (5) separate Fe by filtration, and then carry out the filtrate. Extraction with an organic solvent, whereby Zn, Cd, Mn, and Al are extracted.
若與正極物質相較,則負極物質所含之Li、C、Al、Si等非為有價金屬,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。When compared with the positive electrode material, Li, C, Al, Si, and the like contained in the negative electrode material are not valuable metals, and the recovery cost is higher than the raw material cost. In addition, such negative electrode materials are sometimes included in the battery residue.
本案申請人於專利文獻6(日本特願2007-74089號,2007年3月22日申請)中,如第0001段所說明般,提出一種回收方法。惟,在此方法中,於有機溶劑中所萃取之金屬僅為Mn及Co。In the case of Patent Document 6 (Japanese Patent Application No. 2007-74089, filed on March 22, 2007), the present applicant proposes a recovery method as described in the paragraph 0001. However, in this method, the metals extracted in the organic solvent are only Mn and Co.
[專利文獻1]日本特開平6-251805號公報[專利文獻2]日本特開2006-331707號公報[專利文獻3]日本特許第3450684號公報[專利文獻4]日本特開2007-48692號公報[專利文獻5]日本特表平10-510878號公報[專利文獻6]日本特願2007-74089(2007年3月22日申請)[Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. 2007-48. [Patent Document 5] Japanese Patent Publication No. 10-510878 (Patent Document 6) Japanese Patent Application No. 2007-74089 (filed on March 22, 2007)
[非專利文獻1]「資源與材料」,1997,12,Vol.113,回收再利用特別企畫,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[Non-Patent Document 1] "Resources and Materials", 1997, 12, Vol. 113, Special Recycling and Recycling, p. 941 [Non-Patent Document 2] Lecture. Modern Metallurgy, Refining 2, Non-Iron Metals, July 10, 1982, Metal Society, pp. 240-241
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1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。In the method of recovering and recycling a battery, as in Patent Documents 3 and 5, and a method of decomposing a battery into constituent members or materials and then recovering it, as disclosed in Patent Documents 1 and 2 . The present invention is a method for recycling and reusing a slurry battery residue containing the above-mentioned positive electrode material generated in a battery manufacturing step, and is different from the above methods.
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Mn的鋰酸金屬鹽,回收有價金屬之方法。An object of the present invention is to provide a method for recovering a valuable metal from a lithium metal acid salt containing Co, Ni and Mn contained in a battery residue of a lithium battery.
本發明之第一方法,係一種從含有Co、Ni、Mn之鋰電池殘渣回收有價金屬之方法,其特徵在於,以250g/l以上之濃度的鹽酸溶液,將含有鋰酸金屬鹽(含有Co、Ni及Mn)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;第二方法,為一種從含有Co、Ni、Mn之鋰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;第三方法,為一種從含有Co、Ni、Mn之鋰電池殘渣回收有價金屬之方法,其特徵在於,以混合有200g/l以上之濃度之硫酸溶液與20g/l以上之過氧化氫溶液的溶液, 將含有鋰酸金屬鹽(含有Co、Ni及Mn)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。The first method of the present invention is a method for recovering a valuable metal from a lithium battery residue containing Co, Ni, and Mn, characterized in that a hydrochloric acid solution having a concentration of 250 g/l or more contains a lithium metal phosphate (containing Co The lithium battery residue of Ni, Mn) is stirred and immersed, and then the solvent is extracted with an acid extractant, and 98% or more of Mn, Co and Ni are extracted to form three kinds of solutions containing each metal, and then from this. The solution recovers the metal; the second method is a method for recovering a valuable metal from a lithium battery residue containing Co, Ni, Mn, characterized in that a sulfuric acid solution having a concentration of 200 g/l or more is used to contain a lithium metal phosphate salt. The lithium battery residue (containing Co, Ni and Mn) is heated and stirred, and then the solvent is extracted with an acid extractant, and 98% or more of Mn, Co and Ni are extracted to form three kinds of solutions containing each metal. And recovering the metal from the solution; the third method is a method for recovering a valuable metal from a lithium battery residue containing Co, Ni, Mn, characterized in that a sulfuric acid solution having a concentration of 200 g/l or more is mixed with a solution of 20 g/l or more of a hydrogen peroxide solution, The lithium battery residue containing lithium metal phosphate (containing Co, Ni, and Mn) is stirred and immersed, and then the solvent is extracted with an acid extractant, and 98% or more of Mn, Co, and Ni are extracted to form a content. Three solutions of each metal are then recovered from the solutions.
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Mn、Co及Ni之鋰酸金屬鹽(以下,稱為三元系鋰金屬鹽)者將持續在市場上市。此時,鋰電池殘渣之Co相對量將變多。對於此種電池殘渣,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。In addition, a person who uses a Co-based compound as a positive electrode active material of a battery of an electronic component and a lithium metal oxide salt (hereinafter, referred to as a ternary lithium metal salt) containing substantially the same amount of Mn, Co, and Ni will be considered. Continue to market on the market. At this time, the relative amount of Co of the lithium battery residue will increase. For such a battery residue, 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.
以下,詳細說明本發明。Hereinafter, the present invention will be described in detail.
電池殘渣,係由三元系鋰金屬鹽與碳、N-甲基-2-吡咯烷酮,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渣。其金屬組成,一般為10~12質量%之Co、10~12質量%之Ni、10~12質量%之Mn、4~5質量%之Li。The battery residue is a residue which is produced in a lithium secondary battery manufacturing step by a slurry material composed of a ternary lithium metal salt and a solvent such as carbon, N-methyl-2-pyrrolidone or polyvinyl alcohol. The metal composition is generally 10 to 12% by mass of Co, 10 to 12% by mass of Ni, 10 to 12% by mass of Mn, and 4 to 5% by mass of 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Co、Ni、Mn、Li之全部的浸洗皆為有效。The inventors of the present invention immersed the battery residue 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, and the mixed solution of sulfuric acid and hydrogen peroxide were used for Co, Ni, Mn, and Li. All dipping is effective.
(1)電池殘渣:於【先前技術】中第4段所説明者,200g。(1) Battery residue: 200 g as described in paragraph 4 of [Prior Art].
(2)浸洗液:表1所示之濃度之各種酸,容量2000ml。(2) Dipping liquid: various acids having a concentration shown in Table 1, having a capacity of 2000 ml.
(3)浸洗時間:4h~8h。(3) Dipping time: 4h~8h.
(4)溫度:加熱至常溫或65~80℃。(4) Temperature: Heat to normal temperature or 65~80 °C.
(5)攪拌:有。(5) Stirring: Yes.
測試之結果示於表1。The results of the test are shown in Table 1.
關於三元系鋰金屬鹽之浸洗,可知下列事項。Regarding the immersion of the ternary lithium metal salt, the following matters are known.
(1)若一邊以70~80℃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100%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300g/l之硫酸水溶液,若以65~70℃進行8小時之硫酸浸洗,則亦可達成相同之浸洗率。(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, 100% of Co, Ni, Mn, and Li may be immersed. Although the temperature is above 80 ° C, it can also be dipped out, but it is necessary to evaporate the sulfuric acid purification equipment. Further, if the aqueous solution of sulfuric acid of 300 g/l is subjected to sulfuric acid immersion at 65 to 70 ° C for 8 hours, the same immersion rate can be achieved.
(2)僅有攪拌之浸洗時,則若為250g/l以上之濃度之鹽酸水溶液、及200g/l以上之濃度之硫酸與20g/l以上之濃度之過氧化氫的混合水溶液的話,則Co、Ni、Mn、Li之浸洗率皆為100%。(2) In the case of immersion only with stirring, 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/l or more and hydrogen peroxide having a concentration of 20 g/l or more, The leaching rates of Co, Ni, Mn, and Li are all 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。As described above, when the heat immersion is carried out with a sulfuric acid aqueous solution having a concentration of 200 g/l or more, a immersion rate of 100% can be achieved.
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、及含有200g/l以上之濃度之硫酸與20g/l以上之濃度之過氧化氫的水溶液的話,則可達成100%之浸洗率。Secondly, if only the agitation is carried out, if it is an aqueous solution of hydrochloric acid having a concentration of 250 g/l or more, and an aqueous solution containing sulfuric acid having a concentration of 200 g/l or more and hydrogen peroxide having a concentration of 20 g/l or more, it can be attained. 100% immersion rate.
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。Further, in the case where the aqueous hydrochloric acid solution is immersed or the sulfuric acid or hydrogen peroxide mixed solution is immersed, the heating of the immersion liquid is not hindered.
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100噸之電池殘渣時,加上秤量之誤差,可達成98~100%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 酸、鹽酸,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。Further, the immersion rate of 100% in the above Table 1 is the data in the laboratory. In the case of industrial scale implementation, when 100 tons of battery residue is recycled and recovered in monthly production, the immersion rate of 98 to 100% can be achieved by adding the error of weighing. The immersion liquid formed as a result of the immersion contains ternary metal ions, and the residue is mainly composed of carbon in an organic or inorganic state. The carbon system is insoluble in sulfur Acid or hydrochloric acid remains in the form of solid matter. Since carbon or the like does not have a value for recovery, the residue after immersion is discarded or incinerated.
攪拌,可以旋轉葉片等任意之手段來進行,以使漿狀電池殘渣均勻地分散於浸洗液中。Stirring can be carried out by any means such as rotating a blade to uniformly disperse the slurry battery residue in the immersion liquid.
在將浸洗後之液體所含有之Co、Ni、Mn、Li加以回收方面,若對Mn、Co、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1(資源與材料,1997,12,Vol.113,「回收再利用特別企畫」)第941頁表1之公知酸性萃取劑。In the case of recovering Co, Ni, Mn, and Li contained in the liquid after immersion, Li can be separated by solvent extraction of three metals of Mn, Co, and Ni. An extractive agent for solvent extraction of such a metal, for example, a known acid extraction of Table 1 on page 941 of Non-Patent Document 1 (Resources and Materials, 1997, 12, Vol. 113, "Special Recycling and Recycling") can be used. Agent.
Mn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Mn萃取劑。PC-88A係(2-乙基己)(2-乙基己)膦酸酯系,該資訊可由1202884345093_1.pdf獲得。As the Mn extractant, D2EHPA manufactured by LANXESS Co., Ltd., and an extractant of Co and Ni are preferably used, and PC-88A manufactured by Daiba Chemical Co., Ltd. is preferably used. D2EHPA is bis(2-ethylhexyl)phosphoric acid, and is a well-known Mn extractant in Non-Patent Document 1. PC-88A is a (2-ethylhexyl) (2-ethylhexyl) phosphonate system available from 1202884345093_1.pdf.
從萃取後之溶液回收金屬的方法,可藉由下述目前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。The method for recovering metal from the extracted solution can be recovered by the methods currently carried out as described below, or sold as a resource containing a valuable metal, and then used in a known wet refining step for recovering such metals. The secondary material is processed to recover the metal.
Co:氯化鈷之電解提煉法。Co: electrolytic refining method of cobalt chloride.
Mn:硫酸錳之電解提煉法。Mn: electrolytic refining method of manganese sulfate.
Ni:氯浸洗之Ni電解法。Ni: Ni electrolysis of chlorine leaching.
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 沈澱,然後藉由過濾,以固體成分之形態來回收金屬鹽的方法。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中之濃度濃縮至數倍,然後藉由電解提煉來加以回收時,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收再利用。Ni、Co、Mn之電解提煉,例如,可以非專利文獻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頁所記載之條件來進行。Other methods of metal recovery may be carried out by neutralizing the acidic solution of sulfuric acid in the liquid after the solvent extraction to obtain a metal salt. A method of precipitating and then recovering the metal salt in the form of a solid component by filtration. 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 in the liquid after solvent extraction, and then recovered by electrolytic refining, it can be recycled and reused from the recovery of the battery residue to the reuse of the metal. . Electrolytic refining of Ni, Co, and Mn, for example, can be found in Non-Patent Document 2 (Lecture. Modern Metallography, Refining 2, Non-Iron Metallurgy, published by the Society of Metals on July 10, 1982), pages 240-241. The conditions described are carried out.
接著,參照圖1、圖2、圖3,具體說明藉由DE2HPA及PC-88A,分別對Mn、Co及Ni進行溶劑萃取之方法。Next, a method of solvent extraction of Mn, Co, and Ni by DE2HPA and PC-88A will be specifically described with reference to FIGS. 1, 2, and 3.
[Mn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。[Extraction of Mn] The kerosene (lamp oil) mixture of DE2HPA and the Co-Ni-Mn-Li solution (i.e., the liquid after immersion, see Fig. 1) were mixed in a liquid separation tank equipped with a flow divider and a stirrer to perform solvent extraction. Add caustic soda and adjust the pH to 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10g/l之H2 S04 將Co加以洗淨。Then, extraction with a solvent is further performed, whereby only the Co-Ni-Li 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 Mn extraction also contained a slight amount of Co, Co was washed with 10 g/l of H 2 S0 4 .
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(「Mn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Mn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,以Mn(OH)2 、MnCO3 的形態來回收Mn。洗淨液則加入萃取前之Co-Ni-Mn-Li溶液。Next, reverse extraction was carried out with a 50 g/l aqueous sulfuric acid solution to concentrate Mn in an aqueous sulfuric acid solution ("Mn solution"). The reverse extraction is carried out in two stages, and the solvent is reused in extraction 3. The caustic soda or sodium carbonate is added to the Mn solution for neutralization, and the neutralized liquid and the precipitate are filtered to recover Mn in the form of Mn(OH) 2 or MnCO 3 . The cleaning solution was added to the Co-Ni-Mn-Li solution before extraction.
[Co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)混合液與Co-Ni-Li溶液(即Mn萃取後之液體,參照圖2)加以混合,進行溶劑萃取。添加苛性鈉,將pH值調整為4~5。[Co extraction] The mixture of the kerosene (lamp oil) of PC-88A and the Co-Ni-Li solution (i.e., the liquid after Mn extraction, see Fig. 2) was mixed in a liquid separation tank equipped with a flow divider and a stirrer to perform solvent extraction. Add caustic soda and adjust the pH to 4~5.
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Co萃取後之溶劑中,亦含有些微之Ni,因此以10g/l之H2 SO4 將Ni加以洗淨。Then, extraction with a solvent is further performed, whereby only the 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 Co extraction also contained a slight amount of Ni, Ni was washed with 10 g/l of H 2 SO 4 .
接著,以50g/l之硫酸水溶液進行逆萃取,使Co濃縮於硫酸水溶液中(「Co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Co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,以Co(OH)2 、CoCO3 的形態來回收Co。洗淨液則加入萃取前之Co-Ni-Li溶液。Next, reverse extraction was carried out with a 50 g/l aqueous sulfuric acid solution to concentrate Co in an aqueous sulfuric acid solution ("Co solution"). The reverse extraction is carried out in two stages, and the solvent is reused in extraction 3. The caustic soda or sodium carbonate is added to the Co solution for neutralization, and the neutralized liquid and the precipitate are filtered to recover Co in the form of Co(OH) 2 or CoCO 3 . The cleaning solution was added to the Co-Ni-Li solution before extraction.
[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)混合液與Ni-Li溶液(即Co萃取後之液體,參照圖3)加以混合,進行溶劑萃取。添加苛性鈉,將pH值調整為6~7。[Ni extraction] The mixture of the kerosene (lamp oil) of PC-88A and the Ni-Li solution (i.e., the liquid after Co extraction, see Fig. 3) was mixed in a liquid separation tank equipped with a flow divider and a stirrer to perform solvent extraction. Add caustic soda and adjust the pH to 6~7.
然後,進一步進行利用溶劑之萃取,藉此,使溶液僅 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1(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/l之H2 SO4 將Li加以洗淨。Then, extraction with a solvent is further performed, whereby only Li 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 Ni extraction also contained a slight amount of Li, Li was washed with 10 g/l of H 2 SO 4 .
接著,以50g/l之硫酸水溶液進行逆萃取,使Ni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,以Ni(OH)2 、NiCO3 的形態來回收Ni。洗淨液則加入萃取前之Ni-Li溶液。Next, reverse extraction was carried out with a 50 g/l aqueous sulfuric acid solution, and Ni was concentrated in an aqueous sulfuric acid solution ("Ni solution"). The reverse extraction is carried out in two stages, and the solvent is reused in extraction 3. The caustic soda or sodium carbonate is added to the Ni solution for neutralization, and the neutralized liquid and the precipitate are filtered to recover Ni in the form of Ni(OH) 2 or NiCO 3 . The cleaning solution was added to the Ni-Li solution before extraction.
藉由上述之溶劑萃取所得之Co、Ni、Mn、Li濃度之一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MnCO3 、Co(OH)2 或CoCO3 、Ni(OH)2 或NiCO3 、及Li(OH)2 或LiCO3 之形態來加以回收。The general range of the concentrations of Co, Ni, Mn, and Li obtained by solvent extraction described above and the concentrations of the examples are shown in Table 2. The metal can be neutralized by Mn(OH) 2 or MnCO 3 , Co(OH) 2 or CoCO 3 , Ni(OH) 2 or NiCO 3 , and Li(OH) 2 or LiCO 3 , respectively. Recycling.
綜上所述,本發明之較佳實施態樣如下。In summary, the preferred embodiment of the present invention is as follows.
(1)對Mn、Co及Ni進行酸性溶劑萃取之方法。(1) A method of extracting Mn, Co and Ni by acidic solvent extraction.
(2)藉由調整逆萃取後之溶液、及將Co、Ni、Mn回收後之含有Li之溶液的pH值,使Mn、Co、Ni、Li沈澱, 並進行過濾,藉此以固體成分之形態,來分離金屬之方法。(2) Precipitating Mn, Co, Ni, and Li by adjusting the pH of the solution after reverse extraction and the solution containing Li after recovering Co, Ni, and Mn. Filtration is carried out to separate the metal in the form of a solid component.
(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。(3) The method according to (2), wherein the solid metal is redissolved in the electrolytic solution to perform electrolytic refining.
(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。(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)Co、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。(2) Co, Ni, Mn and Li can be fully washed out. On the other hand, carbon or the like other than this is a residue and is separated from the above four metals.
(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。(3) Due to the use of diluted sulfuric acid or diluted hydrochloric acid, the burden on the environment is less.
(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Ni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。(4) Although Li is dissolved in the immersion liquid, it can be separated from other valuable metals by extracting and separating other valuable metals (the Ni may also remain in the liquid after being extracted from the Ni solution). In the solvent extraction, Mn, Co, and Ni are separated, and Li remains and is separated into the filtrate.
對100kg之含有三元系金屬鋰鹽之膠漿(Co:11%、Ni:11%、Mn:11%、Li:4.3%,以下僅稱之為「膠漿」),進行浸洗及溶劑萃取。於以下所說明之測試中,萃取時間係攪拌10分鐘,逆萃取時間係攪拌10分鐘,洗淨則是攪拌10分鐘來進行。100 kg of a ternary metal lithium salt-containing paste (Co: 11%, Ni: 11%, Mn: 11%, Li: 4.3%, hereinafter simply referred to as "glue"), immersion and solvent extraction. In the test described below, the extraction time was stirred for 10 minutes, the reverse extraction time was stirred for 10 minutes, and the washing was carried out by stirring for 10 minutes.
(1)浸洗(1) Dipping
將膠漿投入300g/l之硫酸水溶液1000L中,一邊以70~80℃進行加熱,一邊攪拌4小時,然後進行過濾後,在 乾燥後之狀態下,殘留有10g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。The slurry was placed in 1000 L of a 300 g/l sulfuric acid aqueous solution, and while stirring at 70 to 80 ° C, the mixture was stirred for 4 hours, and then filtered. After drying, 10 g of residue remained. The metal concentration in the 1000 L filtrate can be 100% dip as shown in the table below.
(2)Mn萃取 以25% NaOH溶液對濾液進行中和後,進行Mn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(O/A比=1/1)。溶劑萃取之結果,得到Mn萃取液1290L與Co-Ni-Li溶液1340L。以10g/l之H2 SO4 將Mn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Mn濃縮於硫酸水溶液中(Mn溶液)。得到Co-Ni-Li溶液1340L(金屬濃度示於表4)與Mn溶液250L(金屬濃度示於表5)。(2) Mn extraction After neutralizing the filtrate with a 25% NaOH solution, solvent extraction of Mn was carried out. The solution after neutralization was 1290 L. The solvent extractant was 1290 L of a D2EHPA kerosene solution manufactured by LANXESS Co., Ltd., and after stirring with the neutralized solution, the pH was adjusted to 2.5 (O/A ratio = 1/1) with a 25% NaOH solution. As a result of solvent extraction, 1,290 L of a Mn extract and 1340 L of a Co-Ni-Li solution were obtained. The Mn extract (slightly containing Co) was washed with 10 g/l of H 2 SO 4 , followed by back extraction with 50 g/l of a sulfuric acid aqueous solution to concentrate Mn in an aqueous sulfuric acid solution (Mn solution). 1340 L of a Co-Ni-Li solution (metal concentration is shown in Table 4) and 250 L of a Mn solution (metal concentration are shown in Table 5) were obtained.
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(O/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H2 SO4 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Co濃縮於硫酸水溶液中(Co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)。The Co, Ni, Li solutions shown in Table 4 were subjected to solvent extraction of Co. 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 25% NaOH solution (O/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 H 2 SO 4 , followed by back extraction with 50 g/l of a sulfuric acid aqueous solution to concentrate Co in an aqueous sulfuric acid solution (Co 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.
對表6所示之Ni、Li溶液進行Ni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1390L,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6.5(O/A比=1/1)。溶劑萃取之結果,得到Ni萃取液1390L與Li溶液1410L。以10g/l之H2 SO4 將Ni萃取液(稍微含有Li)加以洗淨,接著以50g/l之硫酸水溶液進行逆萃取,使Ni濃縮於硫酸水溶液中(Ni溶液)。得到Li溶液1410L(金屬濃度示於表8)與Ni溶液250L(金屬濃度示於表9)。The Ni and Li solutions shown in Table 6 were subjected to solvent extraction of Ni. The solvent extractant was 1390 L of PC-88A kerosene solution manufactured by Da Ba Chemical Co., Ltd., and after stirring with the neutralized solution, the pH was adjusted to 6.5 with a 25% NaOH solution (O/A ratio = 1). /1). As a result of solvent extraction, 1390 L of a Ni extract and 1410 L of a Li solution were obtained. The Ni extract (slightly containing Li) was washed with 10 g/l of H 2 SO 4 , followed by back extraction with 50 g/l of a sulfuric acid aqueous solution, and Ni was concentrated in an aqueous sulfuric acid solution (Ni solution). A Li solution of 1410 L (metal concentration is shown in Table 8) and a Ni solution of 250 L (metal concentration are shown in Table 9) were obtained.
如以上所示,可將Mn、Co、Ni、Li全部分離出來。此外,雖以硫酸浸洗來作說明,但由於以鹽酸浸洗亦可將金屬全量浸洗出,因此其後之溶劑萃取亦為相同之結果。As described above, all of Mn, Co, Ni, and Li can be separated. Further, although the description was carried out by leaching with sulfuric acid, since the entire amount of the metal can be immersed by immersion in hydrochloric acid, the subsequent solvent extraction is also the same.
[產業上之可利用性][Industrial availability]
以往由於沒有以三元系金屬鋰鹽作為正極活性物質之 電池殘渣的回收再利用法,因此只能保管於倉庫等,但若藉由本發明之方法,以硫酸或鹽酸來浸洗電池殘渣,則可來進行有價金屬之回收。使用非為漿狀之含有Co、Ni、Mn的鋰電池殘渣進行相同的測試,亦可得到相同的結果。又,於本發明之方法中,由於採用的是溶劑萃取法,因此例如於電池殘渣有混入Co系正極活性物質,亦不會發生問題,依然可回收有價金屬,故可使回收再利用事業之發展容易。In the past, the ternary metal lithium salt was not used as the positive electrode active material. Since the battery residue is recycled and reused, it can be stored only in a warehouse or the like. However, if the battery residue is immersed in sulfuric acid or hydrochloric acid by the method of the present invention, the valuable metal can be recovered. The same test was carried out using a lithium battery residue containing no Co, Ni, Mn in a slurry form, and the same result was obtained. Further, in the method of the present invention, since the solvent extraction method is employed, for example, the Co-based positive electrode active material is mixed in the battery residue, and no problem occurs, and the valuable metal can be recovered, so that the recycling and recycling business can be used. Development is easy.
圖1,係顯示Mn之溶劑萃取步驟之流程圖。Figure 1 is a flow chart showing the solvent extraction step of Mn.
圖2,係顯示Co之溶劑萃取步驟之流程圖。Figure 2 is a flow chart showing the solvent extraction step of Co.
圖3,係顯示Ni之溶劑萃取步驟之流程圖。Figure 3 is a flow chart showing the solvent extraction step of Ni.

Claims (7)

  1. 一種自含有Co、Ni、Mn之鋰電池殘渣回收有價金屬之方法,於250g/l以上之濃度的鹽酸溶液,以相對於該鹽酸溶液中之鹽酸質量比在0.4以下之比例,混合含有鋰酸金屬鹽(含有Co、Ni及Mn)之鋰電池殘渣並加以攪拌,藉此分別以98~100%之浸洗率浸洗出Co、Ni及Mn,然後對浸洗液以酸性萃取劑對Co、Ni及Mn進行溶劑萃取,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。 A method for recovering valuable metals from a lithium battery residue containing Co, Ni, and Mn, wherein a hydrochloric acid solution having a concentration of 250 g/l or more is mixed with a lithium acid in a ratio of 0.4 or less with respect to a mass ratio of hydrochloric acid in the hydrochloric acid solution; The lithium battery residue of the metal salt (containing Co, Ni, and Mn) is stirred and immersed in Co, Ni, and Mn at a immersion rate of 98 to 100%, respectively, and then the acid extractant is applied to the immersion liquid. Solvent extraction of Ni and Mn produces three solutions containing each metal, and then recovers the metal from such solutions.
  2. 一種自含有Co、Ni、Mn之鋰電池殘渣回收有價金屬之方法,於200g/l以上之濃度之硫酸溶液,以相對於該硫酸溶液中之硫酸質量比在0.5以下之比例,混合含有鋰酸金屬鹽(含有Co、Ni及Mn)之鋰電池殘渣,並於65~80℃的範圍進行加熱攪拌,藉此分別以98~100%之浸洗率浸洗出Co、Ni及Mn,然後對浸洗液以酸性萃取劑對Co、Ni及Mn進行溶劑萃取,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。 A method for recovering valuable metals from a lithium battery residue containing Co, Ni, Mn, wherein a sulfuric acid solution having a concentration of 200 g/l or more is mixed with a lithium acid in a ratio of 0.5 or less with respect to a mass ratio of sulfuric acid in the sulfuric acid solution; A lithium battery residue of a metal salt (containing Co, Ni, and Mn) is heated and stirred at a temperature of 65 to 80 ° C, thereby immersing Co, Ni, and Mn at a immersion rate of 98 to 100%, respectively, and then The immersion liquid is subjected to solvent extraction of Co, Ni and Mn with an acid extractant to form three solutions containing each metal, and then the metal is recovered from the solutions.
  3. 一種自含有Co、Ni、Mn之鋰電池殘渣回收有價金屬之方法,於硫酸濃度在200g/l以上且過氧化氫濃度在20g/l以上之硫酸-過氧化氫混合溶液,以相對於該硫酸-過氧化氫混合溶液中之硫酸質量比在0.5以下之比例,混合含有鋰酸金屬鹽(含有Co、Ni及Mn)之鋰電池殘渣並加以攪拌,藉此分別以98~100%之浸洗率浸洗出Co、Ni及Mn,然後對浸洗液以酸性萃取劑對Co、Ni及Mn進行溶劑萃取,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。 A method for recovering valuable metals from a lithium battery residue containing Co, Ni, Mn, a sulfuric acid-hydrogen peroxide mixed solution having a sulfuric acid concentration of 200 g/l or more and a hydrogen peroxide concentration of 20 g/l or more, relative to the sulfuric acid - the ratio of the mass ratio of sulfuric acid in the hydrogen peroxide mixed solution is 0.5 or less, and the lithium battery residue containing the lithium metal phosphate (containing Co, Ni, and Mn) is mixed and stirred, thereby being washed with 98 to 100%, respectively. Rate the Co, Ni and Mn, then extract the Co, Ni and Mn from the dip solution with an acid extractant to form three solutions containing each metal, and then recover the gold from the solution. Genus.
  4. 如申請專利範圍第1或3項之自含有Co、Ni、Mn之鋰電池殘渣回收有價金屬之方法,其以常溫進行浸洗。 A method of recovering a valuable metal from a lithium battery residue containing Co, Ni, or Mn as claimed in claim 1 or 3, which is immersed at a normal temperature.
  5. 如申請專利範圍第1至3項中任一項之自含有Co、Ni、Mn之鋰電池殘渣回收有價金屬之方法,其中,係在溶劑萃取後藉由進行pH值之調整,使Co、Ni、Mn沈澱,然後藉由過濾,以固態物之形態來加以回收。 A method for recovering a valuable metal from a lithium battery residue containing Co, Ni, or Mn according to any one of claims 1 to 3, wherein the pH is adjusted after solvent extraction to make Co and Ni Mn is precipitated and then recovered by filtration in the form of a solid.
  6. 如申請專利範圍第5項之自含有Co、Ni、Mn之鋰電池殘渣回收有價金屬之方法,其中,係將該固態物再溶解於電解液,進行電解提煉。 A method for recovering a valuable metal from a lithium battery residue containing Co, Ni, or Mn according to the fifth aspect of the patent application, wherein the solid matter is redissolved in an electrolytic solution to perform electrolytic refining.
  7. 如申請專利範圍第1至3項中任一項之自含有Co、Ni、Mn之鋰電池殘渣回收有價金屬之方法,其中,對藉由溶劑萃取將Co、Ni、Mn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。A method for recovering a valuable metal from a lithium battery residue containing Co, Ni, or Mn according to any one of claims 1 to 3, wherein the liquid remaining after extracting Co, Ni, and Mn by solvent extraction The pH was adjusted to precipitate Li, which was then recovered by filtration in the form of a solid.
TW97141955A 2008-02-13 2008-10-31 A method for recovering a valuable metal from a lithium battery residue containing Co, Ni, and Mn TWI392745B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2008031800A JP4865745B2 (en) 2008-02-13 2008-02-13 Method for recovering valuable metals from lithium batteries containing Co, Ni, Mn

Publications (2)

Publication Number Publication Date
TW200934879A TW200934879A (en) 2009-08-16
TWI392745B true TWI392745B (en) 2013-04-11

Family

ID=41001602

Family Applications (1)

Application Number Title Priority Date Filing Date
TW97141955A TWI392745B (en) 2008-02-13 2008-10-31 A method for recovering a valuable metal from a lithium battery residue containing Co, Ni, and Mn

Country Status (4)

Country Link
JP (1) JP4865745B2 (en)
KR (1) KR101036407B1 (en)
CN (1) CN101509071B (en)
TW (1) TWI392745B (en)

Families Citing this family (44)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5014394B2 (en) 2009-09-29 2012-08-29 Jx日鉱日石金属株式会社 Method for separating and recovering nickel and lithium
KR100975317B1 (en) * 2009-11-20 2010-08-12 주식회사 에코닉스 Method for preparing manganese sulfate and zinc sulfate from waste batteries containing manganese and zinc
KR101089519B1 (en) * 2009-11-30 2011-12-05 한국지질자원연구원 Method for Producing CMB Catalyst recycled with Lithium Ion Battery and Ternary Cathode Materials
CN101831548B (en) * 2010-03-31 2012-01-04 奇瑞汽车股份有限公司 Method for recovering valuable metals from waste lithium manganese oxide battery
CN101871048B (en) * 2010-06-25 2012-05-23 浙江华友钴业股份有限公司 Method for recovering cobalt, nickel and manganese from waste lithium cells
JP5254407B2 (en) * 2010-08-30 2013-08-07 Jx日鉱日石金属株式会社 Cathode active material leaching method
JP5501180B2 (en) * 2010-09-29 2014-05-21 株式会社日立製作所 Lithium extraction method and metal recovery method
KR101201947B1 (en) * 2010-10-12 2012-11-16 엘에스니꼬동제련 주식회사 Method for recovering valuable metals from lithium secondary battery wastes
KR101220149B1 (en) * 2011-02-17 2013-01-11 한국지질자원연구원 Method for making sulfate solution of valuable metal from used battery and for making cathode active material
JP5675452B2 (en) * 2011-03-15 2015-02-25 三井金属鉱業株式会社 Manufacturing method of recycled materials
CN102162034A (en) * 2011-04-07 2011-08-24 常州今创博凡能源新材料有限公司 Process for recovering valuable metals from waste lithium batteries
CN102340046B (en) * 2011-06-14 2015-04-22 安徽亚兰德新能源材料有限公司 Method of recovering and treating edge scraps of cobalt-coated spherical nickel hydroxide
JP5406260B2 (en) * 2011-09-29 2014-02-05 Jx日鉱日石金属株式会社 Method for separating aluminum and manganese
CN102363839A (en) * 2011-11-21 2012-02-29 郴州雄风稀贵金属材料股份有限公司 Process for recovering silver, lead and bismuth from silver-bearing soot comprehensively
KR101210983B1 (en) * 2012-05-25 2012-12-11 한국지질자원연구원 Methods of seperating and collecting manganese from cobalt and nickel with high selectivity using screening effect of an extractant mixture
KR101247224B1 (en) * 2012-10-11 2013-03-25 주식회사 대일이앤씨 Method for remediating soil contaminated with zinc using solvent extraction and thereof system
KR101429647B1 (en) 2012-12-21 2014-08-14 주식회사 포스코 Mothod for recovery resource from scrap of positive active material
KR101497041B1 (en) * 2013-04-24 2015-03-02 타운마이닝캄파니(주) Method for recovering valuable metals from cathodic active material of used lithium battery
CN103334009B (en) * 2013-06-14 2015-02-04 山东青龙山有色金属有限公司 Method for recycling valuable metal from waste lithium batteries
CN104419834B (en) * 2013-08-20 2017-05-03 加尔各答大学 Regeneration of cathode material of lithium-ion batteries
CN105541043B (en) * 2013-11-12 2019-05-31 天津卡特化工技术有限公司 Based on MBR and A2The waste lithium cell electrolyte of/O and the processing method of electrolyte waste water
KR101420117B1 (en) 2014-01-29 2014-07-17 한국지질자원연구원 Leaching method of rare-earth metals using hydrochloric acid from manganese nodule
WO2016052569A1 (en) * 2014-09-30 2016-04-07 Jx金属株式会社 Leaching method for lithium ion battery scrap and method for recovering metal from lithium ion battery scrap
KR101584120B1 (en) * 2015-05-22 2016-01-13 성일하이텍(주) Manufacturing method of pure nickel sulfate from leaching residue being removed cobalt of lithium secondary battery
JP6483569B2 (en) * 2015-08-13 2019-03-13 Jx金属株式会社 Lithium-ion battery processing method
TWI551731B (en) * 2015-11-30 2016-10-01 朝陽科技大學 Method of metal recovering by electrodialysis synergized solvent extraction and apparatus thereof
CN105633500A (en) * 2016-02-22 2016-06-01 四川天齐锂业股份有限公司 Method for preparing ternary cathode material precursor by recycling lithium-ion battery material
CN106834680B (en) * 2017-01-04 2018-07-10 北京科技大学 A kind of separation method of Li, Co, Ni, Cu, Mn mixed metal ion
CN106684489B (en) * 2017-03-24 2019-01-29 赣南师范大学 A method of recycling valuable metal from waste and old polynary lithium ion battery
JP6599396B2 (en) * 2017-03-30 2019-10-30 Jx金属株式会社 Lithium recovery method
TWI644468B (en) * 2017-10-13 2018-12-11 國立中山大學 Method for recycling cobalt in waste lithium battery
CN108193050B (en) * 2017-11-27 2019-10-18 中国人民解放军陆军防化学院 Metal material recovery method in a kind of waste and old ternary power battery
CN108069447B (en) * 2017-12-13 2019-11-29 长沙矿冶研究院有限责任公司 Utilize the method for lithium ion cell positive Active Waste preparation LITHIUM BATTERY lithium hydroxide
CN108172925A (en) * 2017-12-27 2018-06-15 浙江中金格派锂电产业股份有限公司 A kind of nickle cobalt lithium manganate ter-polymers cell anode waste recovery method
CN110013822B (en) * 2018-01-07 2020-02-14 中南大学 Method for recycling waste lithium ion batteries and co-producing lithium adsorbent
KR102064668B1 (en) 2018-04-24 2020-01-09 (주)이엠티 A Method of Recycling Material for Precursor of Anode Active Material, Precursor of Anode Active Material, Anode Active Material, Anode, and Lithium Ion Secondary Battery Using The Same
CN109022810B (en) * 2018-08-24 2019-10-25 肇庆市珈旺环境技术研究院 A method of separating and recovering valuable metal iron, manganese and scandium from tungsten slag
CN109020001A (en) * 2018-09-10 2018-12-18 青海瑞能新型燃料科技有限公司 Alcohol-containing waste liquid comprehensive recovering process in a kind of Production Process of Lithium Battery
KR20200066990A (en) 2018-12-03 2020-06-11 동우 화인켐 주식회사 Manufacturing method of precursor for cathode active material from waste lithium secondary battery
JP2020105598A (en) * 2018-12-27 2020-07-09 Jx金属株式会社 Valuable metal recovery method
CN110066925A (en) * 2019-04-28 2019-07-30 浙江天能新材料有限公司 The recovery method of valuable metal in a kind of waste and old nickel-cobalt-manganese ternary lithium battery
KR102154599B1 (en) * 2019-04-30 2020-09-10 코스모에코켐(주) Method for Separation and Recovery of Valuable Metals from Cathode Active Material
CN110184455B (en) * 2019-06-20 2021-01-01 东北大学 Leaching method of refractory cobalt ore
CN110724818A (en) * 2019-09-29 2020-01-24 湖南雅城新材料有限公司 Full-wet recovery process of waste lithium battery

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10287864A (en) * 1997-04-14 1998-10-27 Nippon Chem Ind Co Ltd Recovery of valuable metal from active material of positive electrode for lithium ion secondary battery
JP2005149889A (en) * 2003-11-14 2005-06-09 Ind Technol Res Inst Recovery method of metal from waste secondary battery

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4445496A1 (en) * 1994-12-20 1996-06-27 Varta Batterie Process for the recovery of metals from used nickel-metal hydride accumulators
JP3546912B2 (en) * 1997-04-30 2004-07-28 住友金属鉱山株式会社 Purification method of nickel sulfate by acidic organic extractant
JP2002198103A (en) * 2000-12-22 2002-07-12 Toshiba Corp Recovery method of electrode-constituting metals
CN1287481C (en) * 2003-11-11 2006-11-29 财团法人工业技术研究院 Method for recovering valuable metal from waste secondary cell
JP4815763B2 (en) * 2004-07-09 2011-11-16 住友金属鉱山株式会社 Method for dissolving lithium-containing positive electrode active material
JP4388091B2 (en) * 2007-03-22 2009-12-24 日鉱金属株式会社 Noble metal recovery method from Co, Ni, Mn containing battery

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10287864A (en) * 1997-04-14 1998-10-27 Nippon Chem Ind Co Ltd Recovery of valuable metal from active material of positive electrode for lithium ion secondary battery
JP2005149889A (en) * 2003-11-14 2005-06-09 Ind Technol Res Inst Recovery method of metal from waste secondary battery

Also Published As

Publication number Publication date
CN101509071B (en) 2011-08-03
JP2009193778A (en) 2009-08-27
KR101036407B1 (en) 2011-05-23
JP4865745B2 (en) 2012-02-01
KR20090087801A (en) 2009-08-18
CN101509071A (en) 2009-08-19
TW200934879A (en) 2009-08-16

Similar Documents

Publication Publication Date Title
Yao et al. Hydrometallurgical processes for recycling spent lithium-ion batteries: a critical review
Meshram et al. Hydrometallurgical processing of spent lithium ion batteries (LIBs) in the presence of a reducing agent with emphasis on kinetics of leaching
Huang et al. Recycling of lithium-ion batteries: Recent advances and perspectives
CN107017443B (en) A method of the comprehensively recovering valuable metal from waste and old lithium ion battery
Jha et al. Recovery of lithium and cobalt from waste lithium ion batteries of mobile phone
Fernandes et al. Separation of nickel (II), cobalt (II) and lanthanides from spent Ni-MH batteries by hydrochloric acid leaching, solvent extraction and precipitation
Dutta et al. Close loop separation process for the recovery of Co, Cu, Mn, Fe and Li from spent lithium-ion batteries
Ferreira et al. Hydrometallurgical separation of aluminium, cobalt, copper and lithium from spent Li-ion batteries
Shin et al. Development of a metal recovery process from Li-ion battery wastes
Innocenzi et al. Recovery of rare earths and base metals from spent nickel-metal hydride batteries by sequential sulphuric acid leaching and selective precipitations
Ordoñez et al. Processes and technologies for the recycling and recovery of spent lithium-ion batteries
Innocenzi et al. A review of the processes and lab-scale techniques for the treatment of spent rechargeable NiMH batteries
Chagnes et al. A brief review on hydrometallurgical technologies for recycling spent lithium‐ion batteries
Zhu et al. Recovery of Co and Li from spent lithium-ion batteries by combination method of acid leaching and chemical precipitation
Yang et al. Rare earth element recycling from waste nickel-metal hydride batteries
Nan et al. Recovery of metal values from spent lithium-ion batteries with chemical deposition and solvent extraction
US6110433A (en) Process for the recovery of metals from used nickel/metal/rare earth hydride storage batteries
CN107267759B (en) A kind of comprehensive recovering process of anode material for lithium-ion batteries
US9677152B2 (en) Method for recovering lithium
CN107653378A (en) The recovery method of valuable metal in a kind of waste and old nickel cobalt manganese lithium ion battery
CN106319228B (en) A kind of method of synchronous recycling nickel cobalt manganese in manganese waste slag from nickel and cobalt containing
Nayl et al. Acid leaching of mixed spent Li-ion batteries
WO2014042136A1 (en) Method for recycling lithium-ion batteries and device therefor
US9312581B2 (en) Method for recycling lithium batteries and/or electrodes of such batteries
CN101599563B (en) Method for efficiently recovering active materials of positive poles in waste lithium batteries