KR20190084616A - Manufacturing method for Ni-Co-Mn composite precursor using recycled seed material - Google Patents
Manufacturing method for Ni-Co-Mn composite precursor using recycled seed material Download PDFInfo
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Abstract
Description
본 발명은 니켈-코발트-망간 복합전구체의 제조 방법에 관한 기술로서, 더욱 구체적으로는 리튬이차전지용 양극 활물질 전구체인 니켈-코발트-망간 복합전구체 NixCoyMn1-x-y(OH)2 (여기서, 0<x<1, 0<y<1, 0<x+y<1)의 제조 시 발생하는 폐수로부터 미반응 중금속인, Ni, Co, Mn 등을 분리한 후 상기에서 얻어진 중금속을 후속 공침 반응에서 시드로 재활용하여, 다시 공침 반응을 통해 니켈-코발트-망간 복합전구체를 제조하는 기술에 관한 것이다. 즉, 본 발명은 니켈-코발트-망간 복합전구체의 제조 시 발생하는 폐수를 재활용할 수 있는 기술에 관한 것이다.More particularly, the present invention relates to a nickel-cobalt-manganese composite precursor Ni x Co y Mn 1-xy (OH) 2 , which is a precursor of a cathode active material for a lithium secondary battery , Ni, Co, Mn, etc., which are unreacted heavy metals, are separated from the wastewater generated in the production of 0 <x <1, 0 <y <1, 0 <x + y < Cobalt-manganese composite precursor through a coprecipitation reaction by recycling it as a seed in the reaction. That is, the present invention relates to a technique for recycling wastewater generated in the production of a nickel-cobalt-manganese composite precursor.
휴대용의 소형 전기ㆍ전자기기의 보급 확산에 따라 니켈수소전지나 리튬이차전지와 같은 신형 이차전지 개발이 활발하게 진행되고 있다. 이 중 리튬이차전지는 흑연 등의 카본을 음극 활물질로 사용하고, 리튬이 포함되어 있는 금속 산화물을 양극 활물질로 사용하며, 비수 용매를 전해액으로 사용하는 전지이다. 리튬은 이온화 경향이 매우 큰 금속으로 고전압 발현이 가능하여 에너지 밀도가 높은 전지에 각광을 받고 있는 물질이다. Development of new secondary batteries such as a nickel hydride battery and a lithium secondary battery is progressing actively due to the spread of portable small electric and electronic devices. Among them, the lithium secondary battery uses carbon such as graphite as an anode active material, a metal oxide containing lithium as a cathode active material, and a non-aqueous solvent as an electrolyte. Lithium is a metal that has a very high ionization tendency, and is capable of high voltage generation, and is a material that is attracted to high energy density batteries.
리튬이차전지에 사용되는 양극 활물질로는 리튬을 함유하고 있는 리튬 전이금속산화물이 주로 사용되고 있으며, 코발트계, 니켈계, 삼성분계(코발트, 니켈 및 망간이 공존) 등의 층상계 리튬 전이금속 복합산화물이 90% 이상 사용되고 있다. 예를 들어, Li2CO3와 NixCoyMn1-x-y(OH)2계 전구체를 혼합 소성 가공하여 양극 소재로 사용하고 있다. 통상 NixCoyMn1-x-y(OH)2 전구체는 공침법을 이용하여 제조되는데, 니켈염, 망간염 및 코발트염을 증류수에 용해한 후, 암모니아 수용액(킬레이팅제), NaOH 수용액(염기성 수용액)과 함께 반응기에 투입하면 NixCoyMn1-x-y(OH)2이 고상으로 합성된 후 침전된다.Lithium transition metal oxides containing lithium are mainly used as the positive electrode active material used in the lithium secondary battery, and layered lithium transition metal complex oxides such as cobalt, nickel, ternary system (coexisting cobalt, nickel and manganese) Have been used for more than 90%. For example, Li 2 CO 3 and Ni x Co y Mn 1-xy (OH) 2 precursors are mixed and calcined to be used as a cathode material. In general, the Ni x Co y Mn 1-xy (OH) 2 precursor is prepared by coprecipitation. After the nickel salt, manganese salt and cobalt salt are dissolved in distilled water, an aqueous ammonia solution (chelating agent), aqueous NaOH solution ), The Ni x Co y Mn 1-xy (OH) 2 is synthesized as a solid phase and precipitated.
전술한 바와 같이, 위와 같은 리튬이차전지를 구성하는 양극 활물질을 제조하기 위한 일반적인 방법으로는 공침법을 사용하는데, 공침 과정에서 발생하는 폐수에는 니켈(Ni), 망간(Mn), 코발트(Co) 등의 중금속이 수십 ~ 수백 ppm까지 포함되어 있으며, 암모니아와 수산화나트륨의 사용으로 인해 pH 10 이상의 강알칼리성을 나타내며, (NH4)2SO4, NH4OH 등의 총질소는 8,000~10,000ppm, Na2SO4 등의 무기염은 전체 폐수의 중량에 대하여 10 중량% 정도 포함되게 된다. 이러한 폐수를 적절히 처리하지 않고 외부로 방출할 경우, 심각한 환경 오염을 유발할 수 있다.As described above, as a general method for producing the positive electrode active material constituting the lithium secondary battery as described above, coprecipitation is used. Nickel (Ni), manganese (Mn), cobalt (Co) (NH 4 ) 2 SO 4 , NH 4 OH, and the like are in the range of 8,000 to 10,000 ppm, and the total nitrogen such as (NH 4 ) 2 SO 4 and NH 4 OH is in the range of 8,000 to 10,000 ppm, And inorganic salts such as Na 2 SO 4 are contained in an amount of about 10% by weight based on the weight of the total wastewater. If these wastewater are discharged to the outside without proper treatment, serious environmental pollution may occur.
상기와 같은 공침 반응 후의 폐수의 처리 방법으로서, 대한민국 특허등록 제10-1137251호는 응집, 여과, 총질소 제거, 농축 단계를 포함하는 니켈-코발트-망간 양극활물질 제조 시 발생하는 폐수의 처리 방법을 제시하고 있으나, 상기 특허에서는 폐수 중 중금속, 총질소 등을 제거하기 위한 방법만을 제시하고 있을 뿐, 폐수 내의 고가의 재료인 니켈, 코발트, 망간의 재활용 방안을 제시하지 못하고 있는 단점이 있다.As a method for treating wastewater after the above coprecipitation reaction, Korean Patent Registration No. 10-1137251 discloses a method for treating wastewater generated in the production of a nickel-cobalt-manganese cathode active material including coagulation, filtration, total nitrogen removal, However, the above patent only discloses a method for removing heavy metals and total nitrogen in wastewater, and disadvantageously fails to suggest recycling methods of nickel, cobalt and manganese, which are expensive materials in wastewater.
본 발명은 상기와 같은 종래 기술의 문제점을 해결하기 위한 것으로서, 리튬이차전지용 양극 활물질 전구체 제조 시 발생하는 중금속을 효과적으로 제거한 후, 상기 분리된 중금속을 재활용하는 방법을 제공하는 것을 목적으로 한다.Disclosure of Invention Technical Problem [8] Accordingly, the present invention has been made to solve the above problems, and it is an object of the present invention to provide a method for effectively removing heavy metals generated during the production of a precursor of a cathode active material for lithium secondary batteries, and recycling the separated heavy metals.
특히, 본 발명은 공침 반응 후의 폐수 속의 중금속을 시드로 재활용하여 니켈-코발트-망간 복합전구체를 제조하는 방법을 제공하는 것을 목적으로 한다.Particularly, the object of the present invention is to provide a method for producing a nickel-cobalt-manganese composite precursor by recycling a heavy metal in a wastewater after a coprecipitation reaction as a seed.
본 발명은, 이차 전지용 양극활물질 전구체인 니켈-코발트-망간 복합전구체의 제조시 발생하는 폐수를 상기 복합전구체로부터 분리하는 단계(1); 상기 분리된 폐수에 알칼리용액을 주입하여 중금속을 수산화착물로 제조하는 단계(2); 상기 수산화착물을 여과하는 단계(3); 및 상기 단계(3)에서 얻은 중금속 수산화착물을 시드로 하여 공침 반응을 위한 알칼리용액 및 킬레이팅제를 추가 주입하여, 공침을 통해 니켈-코발트-망간 복합전구를 제조하는 단계(4)를 포함하여 이루어지는, 재활용 시드를 사용한 니켈―코발트―망간 복합전구체의 제조 방법을 제공한다.The present invention relates to a method for producing a nickel-cobalt-manganese composite precursor, comprising the steps of: (1) separating wastewater generated from the nickel-cobalt-manganese composite precursor, which is a precursor of a cathode active material for a secondary battery, from the complex precursor; (2) injecting the alkaline solution into the separated wastewater to prepare a heavy metal as a hydroxide complex; (3) filtering the hydroxide complex; And (4) preparing a nickel-cobalt-manganese composite bulb through coprecipitation by further injecting an alkaline solution and a chelating agent for the coprecipitation reaction using the heavy metal hydroxide complex obtained in the step (3) as a seed, Cobalt-manganese composite precursor using a recycled seed.
특히, 상기 단계(2)의 알칼리용액은 NaOH일 수 있다.In particular, the alkali solution of step (2) may be NaOH.
특히, 상기 단계(3)의 수산화착물은 Ni(OH)2, Co(OH)2, Mn(OH)2, NiCoMn(OH)2 중 어느 하나 이상일 수 있다.In particular, the hydroxide complex of step (3) may be any one or more of Ni (OH) 2 , Co (OH) 2 , Mn (OH) 2 and NiCoMn (OH) 2 .
특히, 상기 단계(4)에 추가로 니켈, 코발트, 망간 원료를 더 주입하여 공침 을 진행할 수 있다. Particularly, in addition to the step (4), the coprecipitation can be further performed by further injecting nickel, cobalt and manganese raw materials.
본 발명에 따른 니켈-코발트-망간 공침 반응에 의해 발생하는 폐수의 처리 방법은 폐수 중에 포함되어 있는 중금속을 효과적으로 분리한 후, 이를 다시 재활용하여 니켈-코발트-망간 복합전구체의 제조에 사용할 수 있는바, 고가의 중금속을 폐수로부터 제거함으로써 환경 보호 효과와 더불어 니켈-코발트-망간 복합전구체의 제조 시 소요되는 재료비 절감 효과를 동시에 얻을 수 있는 이중효과가 있다.The method of treating wastewater generated by the nickel-cobalt-manganese coprecipitation reaction according to the present invention can effectively recover the heavy metals contained in the wastewater and recycle the heavy metals to prepare nickel-cobalt-manganese composite precursor , The expensive heavy metals are removed from the wastewater, and there is a double effect of simultaneously obtaining the environmental protection effect and the material cost reduction effect in manufacturing the nickel-cobalt-manganese composite precursor.
도 1 및 2는 비교예에 의해 제조된 니켈-코발트-망간 복합전구체의 배율을 달리한 SEM 측정 사진이다.
도 3 및 4는 실시예에 의해 제조된 니켈-코발트-망간 복합전구체의 배율을 달리한 SEM 측정 사진이다.
도 5 및 도 6은 각각 비교예 및 실험예의 복합전구체의 입도분포도이다.FIGS. 1 and 2 are SEM photographs showing magnifications of the nickel-cobalt-manganese composite precursor produced by the comparative example.
FIGS. 3 and 4 are SEM photographs showing magnifications of nickel-cobalt-manganese composite precursors prepared by the examples.
5 and 6 are particle size distribution diagrams of the composite precursors of Comparative Examples and Experimental Examples, respectively.
본 발명은 리튬이차전지용 양극 활물질 전구체인 니켈-코발트-망간 양극활물질 제조 시 발생하는 폐수로부터 중금속을 제거한 후 얻어지는 Ni, Co, Mn 입자를 재활용하여, 상기 폐수로부터 분리된 중금속을 원료로 하여 공침 반응을 통해 니켈-코발트-망간 복합전구체를 제조하는 방법을 제공하는 것을 특징으로 한다.The present invention relates to a nickel-cobalt-manganese cathode active material precursor which is a precursor of a lithium secondary battery, which comprises recycled Ni, Co, and Mn particles obtained after removing heavy metals from wastewater generated from the wastewater, Cobalt-manganese composite precursor through a nickel-cobalt-manganese composite precursor.
즉, 본 발명은, 이차 전지용 양극활물질 전구체인 니켈-코발트-망간 복합전구체의 제조시 발생하는 폐수를 상기 복합전구체로부터 분리하는 단계(1); 상기 분리된 폐수에 알칼리용액을 주입하여 중금속을 수산화착물로 제조하는 단계(2); 상기 수산화착물을 여과하는 단계(3); 및 상기 단계(3)에서 얻은 중금속 수산화착물을 시드로 하여 공침 반응을 위한 알칼리용액 및 킬레이팅제를 추가 주입하여, 공침을 통해 니켈-코발트-망간 복합전구를 제조하는 단계(4)를 포함하여 이루어지는, 재활용 시드를 사용한 니켈―코발트―망간 복합전구체의 제조 방법을 제공한다.That is, the present invention provides a method for producing a nickel-cobalt-manganese composite precursor, comprising: (1) separating wastewater generated from a nickel-cobalt-manganese composite precursor, which is a precursor of a cathode active material for a secondary battery, from the complex precursor; (2) injecting the alkaline solution into the separated wastewater to prepare a heavy metal as a hydroxide complex; (3) filtering the hydroxide complex; And (4) preparing a nickel-cobalt-manganese composite bulb through coprecipitation by further injecting an alkaline solution and a chelating agent for the coprecipitation reaction using the heavy metal hydroxide complex obtained in the step (3) as a seed, Cobalt-manganese composite precursor using a recycled seed.
이하에서는 각 단계별로 설명하기로 한다.Hereinafter, each step will be described.
단계(1)Step (1)
Ni, Co, Mn과 공침을 위한 킬레이팅제 및 알칼리용액을 혼합 반응하여 니켈-코발트-망간 복합전구체를 제조하는 공침 공정에서 제조된 복합전구체와 폐수를 분리하는 단계로서, 상기 공침 과정은 종래 잘 알려진 기술이므로 본 발명에서는 구체적인 설명을 생략하기로 한다. 이러한 공침 과정에서 발생하는 폐수에는 니켈, 코발트, 망간 등의 중금속이 수십 ~ 수백 ppm까지 포함되어 있어, 폐수 내의 중금속을 재활용하지 않는다고 하더라고 폐수 내 중금속 함량은 각 5 ppm 미만이어야 방류할 수 있기 때문에 방류 자체도 불가능하다. A step of separating the composite precursor and the wastewater produced in the coprecipitation step of preparing a nickel-cobalt-manganese composite precursor by mixing and reacting a chelating agent and an alkaline solution for co-precipitation with Ni, Co and Mn, And thus a detailed description thereof will be omitted in the present invention. Since heavy metals such as nickel, cobalt and manganese are contained in the wastewater generated in the process of coprecipitation, the heavy metals in the wastewater are less than 5 ppm, even if they do not recycle the heavy metals in the wastewater. It is impossible in itself.
상기 공침 과정에서 생산된 복합전구체를 여과 분리한 후, 미반응 중금속이 다량 함유된 폐수를 다음 단계(2)에서 이용한다.After the complex precursor produced in the coprecipitation process is separated by filtration, wastewater containing a large amount of unreacted heavy metals is used in the next step (2).
단계(2)Step (2)
상기 폐수에서 Ni, Co, Mn 등의 중금속이 다량 포함되어 있으며, 본 발명에서는 알칼리 용액, 예를 들어, NaOH와 상기 폐수 내의 중금속을 반응하도록 함으로써 상기 중금속을 수산화착물, 예를 들어, Ni(OH)2, Co(OH)2, Mn(OH)2로 침전하여 파우더 형태로 존재하게 한다.The waste water contains a large amount of heavy metals such as Ni, Co, Mn. In the present invention, the heavy metal is reacted with an alkaline solution, for example, NaOH and a heavy metal in the wastewater, ) 2 , Co (OH) 2 , Mn (OH) 2 , and exist in powder form.
또한, 단계(1)에서의 폐수 내에 Ni, Co, Mn의 잔류량에 따라 수산화착물이 Ni(OH)2, Co(OH)2, Mn(OH)2 모두가 될 수도 있으며, 이중 어느 하나의 수산화착물만이 생성될 수도 있다. 만일 어느 하나의 수산화착물만이 생성되는 경우 단계(4)에서는 부족한 중금속은 별도로 보충해주어야 하는데, 예를 들어, 황산니켈, 황산코발트, 황산망간 등을 공침 반응에 더 주입할 수 있다.The hydroxide complex may be Ni (OH) 2 , Co (OH) 2 or Mn (OH) 2 depending on the residual amount of Ni, Co or Mn in the wastewater in step (1) Only complexes may be generated. If only one hydroxide complex is formed, the heavy metals that are insufficient in step (4) must be supplemented separately. For example, nickel sulfate, cobalt sulfate, and manganese sulfate may be further added to the coprecipitation reaction.
단계(3)Step (3)
상기 침전된 중금속 수산화착물을 용액으로부터 분리하기 위하여 필터링을 거친다. 회수된 중금속 수산화착물 파우더는 아래 단계(4)에서 공침을 위한 시드(seed)로 사용된다.The precipitated heavy metal hydroxide complex is filtered to separate it from the solution. The recovered heavy metal hydroxide complex powder is used as a seed for coprecipitation in step (4) below.
단계(4)Step (4)
상기 단계(3)에서 수득한 Ni(OH)2, Co(OH)2, Mn(OH)2 등의 소립자를 시드로 하여, 킬레이팅제 및 알칼리용액을 추가하여 공침 반응을 통해 NiCoMn(OH)2를 형성한다. 전술한 바와 같이, 만일 단계(2)에서 제조된 중금속 수산화착물 중 일정 중금속만이 다량 함유되어 있고 다른 중금속의 함량이 적은 경우, 함량이 적은 중금속은 단계(4)의 공침 반응을 위해 추가하여야 한다.A chelating agent and an alkali solution are added as seeds to the Ni (OH) 2 , Co (OH) 2 and Mn (OH) 2 obtained in step (3) 2 . As described above, if the heavy metal hydroxide complex produced in step (2) contains only a large amount of heavy metals and the content of other heavy metals is small, a heavy metal having a low content should be added for the coprecipitation reaction in step (4) .
이하에서는 실시예 및 비교예를 통해 본 발명에 대하여 자세히 설명하기로 한다.Hereinafter, the present invention will be described in detail with reference to examples and comparative examples.
실시예Example
통상의 공침 과정을 통해 니켈-코발트-망간 복합전구체를 제조한 후 발생하는 폐수를 분리하였다. 상기 폐수를 분석한 결과, Co 및 Mn은 극미량이었으며, Ni 성분이 100 ppm 내외로 검출되었다. The wastewater generated after nickel - cobalt - manganese complex precursor was prepared through ordinary coprecipitation process was separated. As a result of the analysis of the wastewater, Co and Mn were trace amounts, and Ni component was detected to be about 100 ppm.
상기 폐수에 NaOH(98%) 수용액 및 킬레이팅제를 첨가하여 중금속 수산화물, 특히, Ni(OH)2를 침전시켰다. 이 착물은 슬러리 형태의 미립자이며, 여과한 뒤 폐기하지 않고 니켈-코발트-망간 복합전구체를 제조하기 위한 공침 반응 시 소립자를 만들기 위한 시드로 재활용하여, 실시예의 니켈-코발트-망간 복합전구체를 제조하였다.NaOH (98%) aqueous solution and chelating agent were added to the wastewater to precipitate heavy metal hydroxides, especially Ni (OH) 2 . The complex was a slurry-like fine particle, and after the filtration, the nickel-cobalt-manganese composite precursor of the example was prepared by recycling it as a seed for making fine particles in a coprecipitation reaction for preparing a nickel-cobalt-manganese composite precursor .
비교예Comparative Example
비교예의 니켈-코발트-망간 복합전구체는, 황산니켈, 황산코발트, 황산망간의 원료에 NH4OH와 NaOH의 혼합 용액을 이용한 공침을 통해 제조되었다.The nickel-cobalt-manganese composite precursor of Comparative Example was prepared by coprecipitation using a mixed solution of NH 4 OH and NaOH as raw materials for nickel sulfate, cobalt sulfate and manganese sulfate.
실험예 1 : SEM 측정 Experimental Example 1: SEM measurement
도 1 및 2는 비교예에 의해 제조된 니켈-코발트-망간 복합전구체의 배율을 달리한 SEM 측정 사진이며, 도 3 및 4는 실시예에 의해 제조된 니켈-코발트-망간 복합전구체의 배율을 달리한 SEM 측정 사진이다. 실시예 및 비교예의 복합전구체 모두 비교적 균일한 형상의 전구체가 제조되었음을 확인할 수 있었다.FIGS. 1 and 2 are SEM photographs of nickel-cobalt-manganese composite precursors prepared according to the comparative examples at different magnifications, and FIGS. It is a SEM measurement photograph. It was confirmed that both of the complex precursors of Examples and Comparative Examples had a relatively uniform precursor.
실험예 2 : 입도분포도Experimental Example 2: Particle size distribution
도 5 및 도 6은 각각 비교예 및 실험예의 복합전구체의 입도분포도로서 재활용 시드를 사용하여 제조된 복합전구체와 통상의 방법으로 제조된 복합전구체의 입도분포에 큰 차이가 없음을 알 수 있으며, 이를 통해 본 발명의 방법이 현장에서 적용 가능함을 확인할 수 있었다.FIG. 5 and FIG. 6 are particle size distribution diagrams of the composite precursors of Comparative Examples and Experimental Examples, respectively. It can be seen that there is no significant difference in particle size distribution between the composite precursor prepared by using the recycled seed and the composite precursor produced by the conventional method, It can be confirmed that the method of the present invention is applicable in the field.
Claims (4)
상기 분리된 폐수에 알칼리용액을 주입하여 중금속을 수산화착물로 제조하는 단계(2);
상기 수산화착물을 여과하는 단계(3); 및
상기 단계(3)에서 얻은 중금속 수산화착물을 시드로 하여 공침 반응을 위한 알칼리용액 및 킬레이팅제를 추가 주입하여, 공침을 통해 니켈-코발트-망간 복합전구를 제조하는 단계(4)를 포함하여 이루어지는, 재활용 시드를 사용한 니켈―코발트―망간 복합전구체의 제조 방법.
(1) separating wastewater generated in the production of a nickel-cobalt-manganese composite precursor, which is a precursor of a cathode active material for a secondary battery, from the complex precursor;
(2) injecting the alkaline solution into the separated wastewater to prepare a heavy metal as a hydroxide complex;
(3) filtering the hydroxide complex; And
(4) preparing a nickel-cobalt-manganese composite bulb through coprecipitation by further injecting an alkali solution and a chelating agent for the coprecipitation reaction using the heavy metal hydroxide complex obtained in the step (3) as a seed, , A method for producing a nickel-cobalt-manganese composite precursor using a recycled seed.
The method for producing a nickel-cobalt-manganese composite precursor according to claim 1, wherein the alkaline solution of step (2) is NaOH.
In claim 1, wherein the hydroxide complex of the above step (3) is Ni (OH) 2, Co (OH) 2, Mn (OH) nickel with any one of two one or more, recycling seed-cobalt-method of manufacturing a manganese complex precursor .
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