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KR20080018734A - Separation and Extraction Method of Cobalt from Lithium Battery Cathode Active Material - Google Patents

Separation and Extraction Method of Cobalt from Lithium Battery Cathode Active Material Download PDF

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KR20080018734A
KR20080018734A KR20060081317A KR20060081317A KR20080018734A KR 20080018734 A KR20080018734 A KR 20080018734A KR 20060081317 A KR20060081317 A KR 20060081317A KR 20060081317 A KR20060081317 A KR 20060081317A KR 20080018734 A KR20080018734 A KR 20080018734A
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cobalt
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lithium battery
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이화영
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한국과학기술연구원
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/54—Reclaiming serviceable parts of waste accumulators
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B23/00—Obtaining nickel or cobalt
    • C22B23/04—Obtaining nickel or cobalt by wet processes
    • C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B23/0461—Treatment or purification of solutions, e.g. obtained by leaching by chemical methods
    • C—CHEMISTRY; METALLURGY
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    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working 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
    • C22B7/006—Wet processes
    • C22B7/008—Wet processes by an alkaline or ammoniacal leaching
    • Y—GENERAL 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/84—Recycling of batteries or fuel cells

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Abstract

본 발명은 폐리튬전지 양극활물질로부터 코발트를 선택적으로 용출하여 분리추출하는 방법에 관한 것으로서, 상세하게는 본 발명은 암모니아수를 용출액으로 사용하고 환원제인 히드라진하이드레이트를 소량 첨가하여 코발트를 용출시키는 것을 특징으로 하는 리튬전지 양극활물질로부터 코발트의 분리회수방법에 관한 것이다. 본 발명의 방법에 의할 경우 종래 무기산에 의한 용출 공정이나 암모니아수에 의한 고압 용출 공정에 비해 코발트 만의 선택적 용출이 가능하며, 또한 용출액으로부터 코발트를 분리하기 위한 복잡한 후공정이 별도로 요구되지 않으며, 무기산을 사용하는 종래 공정에 비해 주변환경오염을 최소화할 수 있어 경제적이면서도 친환경적으로 코발트를 분리할 수 있다.The present invention relates to a method of selectively eluting cobalt from a lithium battery positive electrode active material by separating and extracting, in detail, the present invention is characterized in that the cobalt is eluted by using ammonia water as eluent and adding a small amount of hydrazine hydrate as a reducing agent. The present invention relates to a method for separating and recovering cobalt from a lithium battery cathode active material. According to the method of the present invention, cobalt-only eluting is possible as compared with a conventional eluting process using an inorganic acid or a high-pressure eluting process using ammonia water, and a complicated post process for separating cobalt from an eluate is not required. Compared to the conventional process used, the environmental pollution can be minimized, so that the cobalt can be separated economically and environmentally.

Description

리튬전지 양극활물질로부터 코발트의 분리추출방법{A METHOD OF EXTRACTING COBALT FROM CATHODIC ACTIVE MATERIAL OF LITHIUM BATTERY}Separation and Extraction Method of Cobalt from Lithium Battery Cathode Active Material {A METHOD OF EXTRACTING COBALT FROM CATHODIC ACTIVE MATERIAL OF LITHIUM BATTERY}

본 발명은 리튬전지 양극활물질로부터 암모니아수를 용출액으로 사용하고 환원제로서 히드라진하이드레이트를 소량 첨가하여 코발트를 선택적으로 용출시키기 위한 리튬전지 양극활물질로부터 코발트의 분리추출 방법에 관한 것이다.The present invention relates to a method for separating and extracting cobalt from a lithium battery cathode active material for selectively eluting cobalt by using ammonia water as an eluent from a lithium battery cathode active material and adding a small amount of hydrazine hydrate as a reducing agent.

리튬 전지는 에너지 밀도가 높고 무게가 가벼운 장점을 갖고 있기 때문에 이차 전지 가운데에서도 가장 주목을 받고 있으며, 특히 휴대폰 및 노트북과 같은 휴대용 전자제품에 많이 이용되고 있다. 국내외의 지속적인 IT 산업의 발달로 인하여 향후 리튬 전지 수요는 급속하게 증가할 것으로 예상되고 있으며, 이에 따라 국내 전자 회사들도 해마다 생산량을 증가시키고 있기도 하다. 리튬 전지는 크게 리튬 이온 전지와 리튬 폴리머 전지로 구분되며, 두 경우 모두 양극활물질(cathodic active material)로써 LiCoO2를 주성분으로 하고 있다. 최근에는 전지 성능 향상을 목적으로 주성분인 LiCoO2에 Ni, Mn 등의 금속원소들을 첨가하여 사용하기도 한다.Lithium batteries have received the most attention among secondary batteries because of their high energy density and light weight, and are particularly used in portable electronic products such as mobile phones and laptops. Due to the continuous development of domestic and foreign IT industry, the demand for lithium battery is expected to increase rapidly in the future, and domestic electronic companies are also increasing their production every year. Lithium batteries are largely divided into lithium ion batteries and lithium polymer batteries. In both cases, LiCoO 2 is used as a cathode active material. Recently, metal elements such as Ni and Mn have been added to LiCoO 2 as a main component to improve battery performance.

상기 리튬전지의 양극활물질인 LiCoO2에 함유되어 있는 코발트(Co)는 매우 고가의 금속으로써 국내 생산은 거의 되지 않으며, 전량 해외에서 수입하여 사용하고 있다. 따라서, 우리나라와 같이 부존자원이 없는 국가는 리튬 전지 제조 공정에서 발생하는 양극활물질 폐스크랩 혹은 사용 후 폐기되는 리튬 전지 양극활물질로부터 코발트를 회수하여 재사용하는 것이 반드시 필요한 실정이다. Cobalt (Co) contained in LiCoO 2 , a cathode active material of the lithium battery, is a very expensive metal and is hardly produced in Korea, and is entirely imported and used overseas. Therefore, in the absence of resources such as Korea, it is essential to recover and reuse cobalt from the cathode scrap of the cathode active material generated in the lithium battery manufacturing process or the lithium battery cathode active material disposed of after use.

리튬 전지 양극활물질로부터 코발트를 용출시키는 방법으로는 폐리튬전지로부터 양극활물질을 떼어낸 다음 염산(HCl)으로 용출시키고 수산화코발트(Co(OH)3)로 침전시켜 회수하는 공정을 사용하거나 과산화수소(H2O2)의 존재 하에서 황산(H2SO4) 또는 질산(HNO3)으로 양극활물질로부터 코발트와 리튬을 용출한 뒤 중화침전법으로 코발트를 분리회수하는 공정을 사용하는 것이 일반적이다. 또한, 최근에는 양극활물질 용출액으로부터 용매추출법을 사용하여 코발트를 분리하기도 한다. Cobalt is eluted from the lithium battery positive electrode active material by using a process of removing the positive electrode active material from the waste lithium battery, eluting with hydrochloric acid (HCl), precipitated with cobalt hydroxide (Co (OH) 3 ) and recovered. In the presence of 2 O 2 ), cobalt and lithium are eluted from the positive electrode active material with sulfuric acid (H 2 SO 4 ) or nitric acid (HNO 3 ), and cobalt is recovered by neutralization precipitation. In recent years, cobalt is also separated from the positive electrode active material eluate using a solvent extraction method.

상기 코발트의 용출 방법 가운데 염산 등의 무기산(mineral acid)을 사용하여 이루어지는 방법은 용출 공정 시에 강산을 사용하여야 하기 때문에 대기중으로 증발되는 산 냄새에 의하여 심각한 환경오염을 유발시키고, 특히 산에 의한 설비 부식 등의 문제가 매우 심각하다. 또한, 비선택적인 용출 방법이기 때문에 코발트 뿐만 아니라 리튬 및 양극활물질에 존재하는 다른 금속원소들도 동시에 용출되어 용출액으로부터 코발트를 분리하는 까다로운 후공정을 거쳐야만 한다. Among the cobalt elution methods, a method using inorganic acid such as hydrochloric acid causes strong environmental pollution due to acid odor evaporated into the air, since strong acid must be used during the elution process. Problems such as corrosion are very serious. In addition, since it is a non-selective elution method, not only cobalt but also other metal elements present in lithium and cathode active materials must be eluted at the same time to undergo a difficult post-process to separate cobalt from the eluate.

또 다른 코발트 용출 방법의 하나로써, 암모니아수(NH4OH)를 사용하는 방법이 있으나 양극활물질중의 코발트는 산화물로 존재하기 때문에 단순히 암모니아수로는 용출이 되지 않으며 150℃ 이상의 고압반응기(autoclave)에서 장시간 용출시 키거나 혹은 800℃ 이상의 고온에서 미리 환원 과정을 거친 후에 암모니아수로 용출시켜야만 하는 번거로움이 있었다.As another cobalt elution method, there is a method using ammonia water (NH 4 OH), but because cobalt in the positive electrode active material is present as an oxide, it is not simply eluted with ammonia water. There was a hassle of eluting or eluting with ammonia water after a reduction process in advance at a high temperature of more than 800 ℃.

이에 따라, 본 발명자들은 종래 코발트의 용출방법의 단점을 최소화시키면서 경제적이고 친환경적인 코발트 분리방법을 연구한 결과, 리튬 전지의 양극활물질로부터 암모니아수를 용출액으로 사용하고, 환원제로 히드라진하이드레이트를 소량 첨가할 경우 코발트의 선택적 분리 회수가 가능하고 수율이 현저히 증가됨을 확인함으로써 리튬 전지 양극활물질로부터 코발트를 분리추출하는 방법을 완성하였다.Accordingly, the present inventors have studied the economical and environmentally friendly cobalt separation method while minimizing the disadvantages of the conventional cobalt elution method, when using ammonia water as the eluent from the positive electrode active material of a lithium battery, and a small amount of hydrazine hydrate as a reducing agent The method of separating and extracting cobalt from the lithium battery cathode active material was completed by confirming that selective separation recovery of cobalt was possible and the yield was significantly increased.

본 발명의 목적은 암모니아수를 용출액으로 사용하고 코발트 용출을 촉진시키기 위하여 히드라진하이드레이트(hydrazine hydrate, N2H4·H2O)를 소량 첨가함으로써 100℃ 이하에서 코발트를 선택적으로 용출시킬 수 있는 리튬 전지 양극활물질로부터 코발트를 분리추출하는 방법을 제공하는 것이다.An object of the present invention is to use ammonia water as eluent and add a small amount of hydrazine hydrate (hydrazine hydrate (N 2 H 4 · H 2 O) to promote cobalt elution lithium battery capable of selectively eluting cobalt below 100 ℃ It is to provide a method for separating and extracting cobalt from the positive electrode active material.

상기 목적을 달성하기 위하여, 본 발명은 암모니아수를 용출액으로 사용하고 환원제로 히드라진하이드레이트를 첨가하여 코발트만을 선택적으로 분리용출하는 것을 특징으로 하는 리튬전지 양극활물질로부터 코발트의 분리추출방법을 제공한다.In order to achieve the above object, the present invention provides a method for separating and extracting cobalt from a lithium battery cathode active material, characterized in that the cobalt is selectively separated and eluted by using ammonia water as the eluent and adding hydrazine hydrate as a reducing agent.

상기 용출액으로 농암모니아수를 양극활물질 1g에 대하여 5 내지 20 ㎖ 범위로 첨가함을 특징으로 한다.The ammonia water is added to the eluate in a range of 5 to 20 ml with respect to 1 g of the positive electrode active material.

또한, 상기 히드라진하이드레이트를 양극활물질 1g에 대하여 0.1 내지 0.5㎖의 범위로 첨가함을 특징으로 한다.In addition, the hydrazine hydrate is characterized in that the addition of 0.1 to 0.5ml with respect to 1g of the positive electrode active material.

또한, 코발트 용출 온도는 40 내지 70℃ 범위로 하여 이루어지는 것을 특징으로 한다.In addition, the cobalt elution temperature is characterized in that it is in the range of 40 to 70 ℃.

이하, 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.

리튬전지 양극활물질을 분쇄한 원료를 콘덴서가 장착된 용기에 넣은 다음 농암모니아수(NH3 기준 28% 암모니아수)를 양극활물질 1g에 대하여 5 내지 20㎖의 비율로 채운 다음 교반기를 사용하여 적당한 세기로 교반한다. Put the raw material of the lithium battery cathode active material into a container equipped with a condenser, and fill with ammonia water (28% NH3 based on NH 3 ) at a rate of 5 to 20 ml with respect to 1 g of the positive electrode active material, and then stir at an appropriate strength using a stirrer. do.

상기 코발트 원료로는 리튬 이온 전지의 제조 공정에서 발생하는 폐양극활물질 또는 사용 후 폐기되는 폐리튬전지로부터 떼어낸 코발트 함유 양극활물질로써 본 발명에서는 용출하기에 앞서 이들 원료를 리튬전지로부터 채취하는 방법이나 분쇄하는 방법에 대해 특별한 제한을 하지는 않는다. The cobalt raw material is a cobalt-containing positive electrode active material that is separated from a waste positive electrode active material generated in a lithium ion battery manufacturing process or a waste lithium battery that is disposed of after use. There is no particular limitation on the grinding method.

상기 암모니아 용액의 첨가 범위보다 적게 첨가되면 코발트 용출율이 떨어져 회수율이 낮아지는 문제가 발생하고, 또한 상기 범위보다 많이 첨가하면 불필요하게 암모니아 용액이 소모되는 단점이 있다. 한편, 농암모니아수를 적절히 물에 희석하여 용출 공법을 수행하는 경우도 있으나 이 경우 용액 중의 암모니아 농도가 낮아지게 되어 용출 속도가 저하되는 단점이 발생한다. 그러나, 본 발명에서는 농암모니아수를 희석하여 사용하는 것에 대해 특별한 제한을 하지는 않는다. If less than the addition range of the ammonia solution, the cobalt dissolution rate is lowered, there is a problem that the recovery rate is lowered, and if more than the above range there is a disadvantage that unnecessary consumption of the ammonia solution. On the other hand, there is a case in which the concentrated ammonia water is properly diluted in water to perform the elution method, but in this case, the ammonia concentration in the solution is lowered, so that the elution rate is lowered. However, in the present invention, there is no particular limitation on diluting the concentrated ammonia water.

상기와 같이 분쇄된 양극활물질 원료와 암모니아 용액을 투입한 후 환원제인 히드라진하이드레이트를 양극활물질 1g에 대하여 0.1 내지 0.5㎖의 비율로 용기 내에 첨가한다. 환원제인 히드라진하이드레이트 첨가량이 상기 범위보다 적으면 코발트 산화물을 충분히 환원시키기가 곤란한 문제점을 발생되고, 상기 범위보다 많으면 히드라진하이드레이트 약품 비용이 증가하는 단점이 있다. 만약 히드라진하이드레이트가 첨가되지 않게 되면 암모니아 용액에 의한 코발트 용출율이 30% 미만으로 떨어져 상업적으로 바람직하지 못하게 된다.After pulverizing the cathode active material raw material and ammonia solution as described above, hydrazine hydrate as a reducing agent is added to the container at a ratio of 0.1 to 0.5 ml with respect to 1 g of the cathode active material. If the amount of the hydrazine hydrate that is the reducing agent is less than the above range, it is difficult to sufficiently reduce the cobalt oxide. If the amount of the hydrazine hydrate is more than the above range, the cost of the hydrazine hydrate drug is increased. If hydrazine hydrate is not added, the cobalt dissolution rate by the ammonia solution drops to less than 30%, which is not commercially desirable.

상기와 같이 준비된 상태에서 용기 내부의 온도를 40 내지 70℃ 범위로 조정하여 용출을 실시한다. 용출이 진행되는 동안 증발된 증기는 냉각수가 흐르는 콘덴서를 통해 재응축시켜 용기 내로 되돌린다. 코발트 용출시간은 2시간이면 충분하며, 용출이 완료되면 잔류물질을 여과하고 코발트를 함유한 용출액을 분리한다.Elution is carried out by adjusting the temperature inside the vessel in the prepared state as described above to 40 to 70 ℃ range. The vapor evaporated during the elution is recondensed through the condenser flowing coolant and returned to the vessel. The cobalt elution time is sufficient for 2 hours. When the elution is completed, the residue is filtered and the eluate containing cobalt is separated.

상기의 방법에 의하여 리튬전지 양극활물질로부터 코발트를 용출하는 경우 코발트 회수율 96% 이상을 달성할 수 있으며, 특히 종래의 무기산이나 고압반응기를 사용하는 방법에 비해 코발트만의 선택적인 용출이 가능하여 용출액으로부터 코발트를 분리하기 위한 복잡한 후공정을 거치지 않아도 된다는 특징이 있다. 또한, 무기산을 사용하는 종래 공정에 비해 주변환경오염을 최소화함은 물론 별도의 오염방지시설이 필요 없기 때문에 공정비용을 크게 줄일 수 있다는 장점이 있다.When the cobalt is eluted from the lithium battery cathode active material by the above method can achieve a cobalt recovery of more than 96%, especially compared to the conventional method using an inorganic acid or a high pressure reactor is possible to selectively elute the cobalt only from the eluate It is characterized by not having to go through complicated post-process to separate cobalt. In addition, compared to the conventional process using an inorganic acid as well as minimizing the environmental pollution, as well as the need for a separate pollution prevention facility has the advantage that can significantly reduce the process cost.

이하, 본 발명은 하기의 실시예에 의하여 더욱 상세히 설명한다. 그러나 하기의 실시예는 본 발명의 예시일 뿐, 본 발명의 권리범위가 이에 의하여 한정되지는 않는다.Hereinafter, the present invention will be described in more detail by the following examples. However, the following examples are merely illustrative of the present invention, and the scope of the present invention is not limited thereto.

실시예Example 1  One 폐리튬전지Waste lithium battery 양극활물질로부터From cathode active materials 코발트의 용출 1 Elution of cobalt 1

폐리튬전지 양극활물질(코발트 함량 60.2wt%)을 채취하여 분말로 분쇄한 원료 5g을 콘덴서가 장착된 250㎖ 용기에 넣었다. 농암모니아수(NH3 기준 28% 암모니아수)를 25㎖ 취하여 용기 내에 넣고, 환원제인 히드라진하이드레이트 2.5㎖를 용기 내에 첨가하였다. 상기와 같이 준비된 상태에서 용기 내부의 온도를 70℃로 가열하고 교반기를 사용하여 교반을 실시하였다. 코발트 용출이 진행되는 동안 증발된 증기는 냉각수가 흐르는 콘덴서를 통해 재응축시켜 용기 내로 되돌렸다. 상기 코발트 용출을 2시간 동안 수행하고, 잔류 물질을 여과하고 코발트를 함유한 용출액을 회수하였다.The waste lithium battery positive electrode active material (cobalt content 60.2wt%) was taken and pulverized into powder 5g into a 250ml container equipped with a condenser. 25 ml of concentrated ammonia water (28% ammonia water based on NH 3 ) was taken into a container, and 2.5 ml of hydrazine hydrate as a reducing agent was added to the container. In the state prepared as above, the temperature inside the vessel was heated to 70 ° C. and stirred using a stirrer. The vapor evaporated during the cobalt elution was recondensed through a condenser with cooling water and returned to the vessel. The cobalt elution was carried out for 2 hours, the residual material was filtered off and the eluate containing cobalt was recovered.

상기 실험 수행의 결과, 용출액 중의 코발트 농도는 105.8gr/ℓ로, 코발트 회수율은 초기 원료 중의 코발트 함량을 기준으로 96.7%에 달함을 확인할 수 있었다.As a result of the experiment, it was confirmed that the cobalt concentration in the eluate was 105.8 gr / l, and the cobalt recovery rate was 96.7% based on the cobalt content in the initial raw material.

실시예Example 2  2 폐리튬전지Waste lithium battery 양극활물질로부터From cathode active materials 코발트의 용출 2 Cobalt Elution 2

실시예 1과 동일한 폐리튬전지 양극활물질의 분말원료 5g을 취하여 실시예 1 과 동일한 장치 내에 넣었다. 농암모니아수(NH3 기준 28% 암모니아수)를 100㎖ 취하여 용기 내에 넣고, 환원제인 히드라진하이드레이트 0.5㎖를 용기 내에 첨가하였다. 상기와 같이 준비된 상태에서 용기 내부의 온도를 40℃로 가열하고 교반기를 사용하여 교반을 실시하였. 코발트 용출이 진행되는 동안 증발된 증기는 냉각수가 흐르는 콘덴서를 통해 재응축시켜 용기 내로 되돌렸다. 상기 코발트 용출을 2시간 동안 수행하고, 실시예 1과 동일한 방법으로 잔류물질을 여과하고 코발트를 함유한 용출액을 회수하였다.5 g of a powder raw material of the same lithium battery positive electrode active material as in Example 1 was taken and placed in the same apparatus as in Example 1. 100 ml of concentrated ammonia water (28% ammonia water based on NH 3 ) was taken into a container, and 0.5 ml of hydrazine hydrate as a reducing agent was added to the container. In the state prepared as above, the temperature inside the vessel was heated to 40 ° C. and stirred using a stirrer. The vapor evaporated during the cobalt elution was recondensed through a condenser with cooling water and returned to the vessel. The cobalt elution was performed for 2 hours, the residual material was filtered in the same manner as in Example 1, and the eluate containing cobalt was recovered.

상기 실험 수행의 결과, 용출액 중의 코발트 농도는 29.44gr/ℓ로, 코발트 회수율은 초기 원료 중의 코발트 함량을 기준으로 98.3%에 달함을 확인할 수 있었다.As a result of the experiment, it was confirmed that the cobalt concentration in the eluate was 29.44 gr / l, and the cobalt recovery rate was 98.3% based on the cobalt content in the initial raw material.

상기에서와 같이, 본 발명의 방법을 이용하여 폐리튬전지의 양극활물질로부터 코발트를 분리용출하는 경우, 코발트 회수율 96% 이상으로 현저히 높은 회수율을 갖는다. 특히 종래의 무기산이나 고압반응기를 사용하는 방법으로는 불가능하였던 코발트만의 선택적인 용출이 가능하여 용출액으로부터 코발트를 분리하기 위한 복잡한 후공정을 거치지 않아도 된다는 이점을 갖는다. 또한, 무기산을 사용하는 종래 공정에 비해 주변환경오염을 최소화함은 물론 별도의 오염방지시설이 필요 없기 때문에 공정비용을 크게 줄일 수 있으며 환경친화적으로 코발트 분리회수가 가 능한 효과를 갖는다.As described above, when the cobalt is separated and eluted from the positive electrode active material of the waste lithium battery using the method of the present invention, the cobalt recovery rate is 96% or more, which is a remarkably high recovery rate. In particular, it is possible to selectively elute cobalt, which was not possible using a conventional inorganic acid or a high pressure reactor, and thus has the advantage of not having to undergo a complicated post-process for separating cobalt from the eluate. In addition, compared to the conventional process using an inorganic acid, as well as minimizing the environmental pollution, and does not require a separate pollution prevention facility, the process cost can be greatly reduced and environmentally friendly cobalt separation recovery is possible.

Claims (4)

폐리튬전지 양극활물질에 용출액으로 암모니아수를 사용하고 환원제로서 히드라진하이드레이트를 첨가하여 코발트만을 선택적으로 용출시키는 것을 특징으로 하는 폐리튬전지 양극활물질로부터 코발트의 분리회수방법.A method for separating and recovering cobalt from a waste lithium battery cathode active material, characterized in that only lithium cobalt is eluted by using ammonia water as an eluent and a hydrazine hydrate as a reducing agent. 제 1 항에 있어서, 상기 암모니아수는 농암모니아수(NH3 기준 28% 암모니아수)를 양극활물질 1g에 대하여 5 내지 20㎖ 범위로 첨가함을 특징으로 하는 폐리튬전지 양극활물질로부터 코발트의 분리회수방법.The method of claim 1, wherein the ammonia water is concentrated ammonium water (28% ammonia water based on NH 3 ) in the range of 5 to 20 ml with respect to 1 g of the positive electrode active material. 제 1 항에 있어서, 상기 히드라진하이드레이트를 양극활물질 1g에 대하여 0.1 내지 0.5㎖의 범위로 첨가함을 특징으로 하는 폐리튬전지 양극활물질로부터 코발트의 분리회수방법.The method of claim 1, wherein the hydrazine hydrate is added in an amount of 0.1 to 0.5 ml based on 1 g of the positive electrode active material. 제 1 항에 있어서, 상기 방법은 코발트 용출 온도를 40 내지 70℃ 범위로 하는 것을 특징으로 하는 폐리튬전지 양극활물질로부터 코발트의 분리회수방법.The method of claim 1, wherein the cobalt elution temperature is in the range of 40 to 70 ° C.
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KR20170033787A (en) 2015-09-17 2017-03-27 주식회사 에코프로비엠 Precursor Synthetic method for lithium-ion secondary battery cathode active material from waste battery material, and manufacturing method of the cathode active material made by the same
US9643846B2 (en) 2013-03-14 2017-05-09 Korea Institute Of Science And Technology Recycling method of olivine-based cathode material for lithium secondary battery, cathode material fabricated therefrom, and cathode and lithium secondary battery including the same

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US5256306A (en) 1991-10-07 1993-10-26 Griffin Gus M Continuous treatment of chromium bearing waste water
JP3532640B2 (en) * 1994-12-08 2004-05-31 株式会社三徳 Method for recovering positive electrode material from nickel-hydrogen secondary battery and method for recovering raw material for recovering effective metal from negative electrode

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US9199850B2 (en) 2012-05-25 2015-12-01 Korea Institute Of Science And Technology Method of fabricating LiFePO4 cathode electroactive material by recycling, and LiFePO4 cathode electroactive material, LiFePO4 cathode, and lithium secondary battery fabricated thereby
US9643846B2 (en) 2013-03-14 2017-05-09 Korea Institute Of Science And Technology Recycling method of olivine-based cathode material for lithium secondary battery, cathode material fabricated therefrom, and cathode and lithium secondary battery including the same
KR20170033787A (en) 2015-09-17 2017-03-27 주식회사 에코프로비엠 Precursor Synthetic method for lithium-ion secondary battery cathode active material from waste battery material, and manufacturing method of the cathode active material made by the same

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