KR101950202B1 - Manufacturing method for Ni-Co-Mn composite precursor with high specific surface area - Google Patents
Manufacturing method for Ni-Co-Mn composite precursor with high specific surface area Download PDFInfo
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Abstract
본 발명은 니켈-코발트-망간의 3성분계 복합전구체(NixCoyMn1-x-y)의 제조 방법에 관한 기술로서, 더욱 구체적으로는 pH가 다른 조건에서 2번의 공침을 통해 비표면적이 높은 니켈-코발트-망간 3성분계 복합전구체를 제조하는 기술에 관한 것이다.The present invention relates to a method for producing a three-component complex precursor of nickel-cobalt-manganese (Ni x Co y Mn 1-xy ), and more specifically, -Cobalt-manganese three-component complex precursor.
Description
본 발명은 니켈―코발트―망간의 3성분계 복합전구체[NixCoyMn1-x-y(OH)2]의 제조 방법에 관한 기술로서, 더욱 구체적으로는 리튬이차전지용 양극 활물질에 적합한 비표면적이 높은 니켈-코발트-망간 3성분계 복합전구체의 제조 방법에 관한 기술이다.TECHNICAL FIELD The present invention relates to a process for producing a three-component complex precursor of nickel-cobalt-manganese [Ni x Co y Mn 1-xy (OH) 2 ], and more specifically to a process for producing a lithium- Nickel-cobalt-manganese three-component complex precursor.
휴대용의 소형 전기ㆍ전자기기의 보급이 확산에 따라 니켈수소전지나 리튬 이차전지와 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. 2. Description of the Related Art [0002] With the spread of portable small-sized electric and electronic devices, development of new secondary batteries such as nickel-metal hydride batteries and lithium secondary batteries is actively under way. 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.
리튬이차전지에 사용되는 양극 활물질로는 리튬 단독이 아닌 니켈, 코발트, 망간 등을 혼합하여 양극 활물질로 제조함으로써 에너지밀도 및 전기전도성 등의 양극 물성을 만족시키고 있다. 예를 들어, Li2CO3와 니켈-코발트-망간 복합전구체[NixCoyMn1-x-y(OH)2]를 혼합 소성 가공하여 양극 활물질로 사용하고 있다. 통상 상기 복합전구체는 공침법을 이용하여 제조되는데, 니켈염, 망간염 및 코발트염을 증류수에 용해한 후, 암모니아 수용액(킬레이팅제) 및 NaOH 수용액(염기성 수용액)과 함께 반응기에 투입하면 상기 전구체의 침전이 일어난다.As a cathode active material used for a lithium secondary battery, nickel, cobalt, and manganese are mixed with lithium rather than lithium alone to prepare a cathode active material, thereby satisfying the anode properties such as energy density and electrical conductivity. For example, Li 2 CO 3 and a nickel-cobalt-manganese composite precursor Ni x Co y Mn 1-xy (OH) 2 are mixed and calcined to be used as a cathode active material. Generally, the complex precursor is prepared by coprecipitation. When a nickel salt, a manganese salt and a cobalt salt are dissolved in distilled water and then added to a reactor together with an aqueous ammonia solution (chelating agent) and an aqueous NaOH solution (basic aqueous solution) Precipitation occurs.
종래 기술에서는 니켈-코발트-망간 전구체의 비표면적을 향상시키는 방법이 제시된 바가 없으며, 주로 니켈-코발트-망간 복합전구체의 크기 제어에 관한 기술이 종래 기술의 대부분을 차지하고 있다.In the prior art, a method for improving the specific surface area of a nickel-cobalt-manganese precursor has not been proposed, and a technique for controlling the size of a nickel-cobalt-manganese composite precursor mainly occupies most of the prior art.
본 발명은 충방전 효율이 우수한 니켈-코발트-망간의 3성분계 복합전구체의 제조방법을 제공하는 것을 목적으로 한다.An object of the present invention is to provide a process for producing a three-component complex precursor of nickel-cobalt-manganese which is excellent in charging / discharging efficiency.
특히, 본 발명은 니켈-코발트-망간의 3성분계 복합전구체의 제조를 위한 공침 반응시, 비표면적이 큰 복합전구체를 제조하는 방법을 제공하는 것을 목적으로 한다.In particular, it is an object of the present invention to provide a method for preparing a complex precursor having a large specific surface area during a coprecipitation reaction for preparing a three-component complex precursor of nickel-cobalt-manganese.
특히, 본 발명은 간단한 공정 조건의 변화만으로 비표면적이 큰 니켈-코발트-망간의 3성분계 복합전구체를 제조하는 방법을 제공하는 것을 목적으로 한다.In particular, it is an object of the present invention to provide a method for producing a three-component complex precursor of nickel-cobalt-manganese having a large specific surface area by simply changing process conditions.
본 발명은 니켈-코발트-망간 복합전구체[NixCoyMn1-x-y(OH)2, 여기서, 0＜x<1, 0＜y<1, 0＜x+y<1]를 동시공침에 의해 제조하는 방법에 있어서, pH 9.0 ~ 9.5 조건의 반응기 내에 황산니켈, 황산코발트 및 황산망간의 전이금속 수용액을 공침법에 의하여 복합전구체를 제조하는 제1공침단계; 및 pH 10.5 ~ 11.0으로 pH를 상승한 후 공침을 더 진행하는 제2공침단계를 포함하여 이루어지는 것을 특징으로 하는 고비표면적의 니켈-코발트-망간 복합전구체의 제조방법을 제공한다.The present invention relates to a nickel-cobalt-manganese composite precursor Ni x Co y Mn 1-xy (OH) 2 wherein 0 <x <1, 0 <y <1, 0 <x + y < A first coprecipitation step of preparing a complex precursor by coprecipitation of a transition metal aqueous solution of nickel sulfate, cobalt sulfate and manganese sulfate in a reactor having a pH of 9.0 to 9.5; And a second coprecipitation step of further increasing coprecipitation after the pH is raised to a pH of 10.5 to 11.0. The present invention also provides a method for preparing a high specific surface area nickel-cobalt-manganese composite precursor.
특히, 상기 pH를 맞추기 위하여 염기성 수용액으로 NaOH 수용액을 사용하는 것이 바람직하다.Particularly, it is preferable to use an aqueous NaOH solution as a basic aqueous solution to adjust the pH.
특히, 상기 제2공침단계에서 황산니켈, 황산코발트 및 황산망간을 포함하는 전이금속 수용액의 농도가 제1단계에서의 전이금속 수용액의 농도보다 높게 할 수 있다.In particular, in the second coprecipitation step, the concentration of the transition metal aqueous solution containing nickel sulfate, cobalt sulfate and manganese sulfate may be higher than the concentration of the transition metal aqueous solution in the first step.
특히, 상기 제1공침단계 및 제2공침단계는 배치식 반응기 또는 쿠에트 테일러 반응기 내에서 이루어질 수 있다.In particular, the first coprecipitation step and the second coprecipitation step may be performed in a batch reactor or a Quattro Taylor reactor.
본 발명의 방법에 의해 제조된 니켈-코발트-망간 복합전구체는 종래 기술과 같이 단일 pH 조건에서 한 번의 공침 단계로 제조된 복합전구체에 비해 비표면적이 증가할 뿐만 아니라, 니켈과 소성하여 양극재로 제조하여 충방전 테스트를 한 결과 충방전 효율 역시 종래 기술에 비해 우수함을 알 수 있다.The nickel-cobalt-manganese composite precursor produced by the method of the present invention has a specific surface area that is increased as compared with the complex precursor prepared by one coprecipitation step under a single pH condition as in the prior art, Discharging test was conducted. As a result, it was found that the charging and discharging efficiency was also superior to that of the prior art.
도 1은 본 발명의 제1공침단계에 의해 제조된 니켈-코발트-망간 복합전구체의 SEM 사진이다.
도 2는 본 발명의 제2공침단계에 의해 제조된 니켈-코발트-망간 복합전구체의 SEM 사진이다.
도 3은 단일 공침을 통해 제조된 비교예의 복합전구체의 SEM 사진이다.
도 4는 실시예의 복합전구체의 TEM 측정 이미지이며, 도 5는 비교예의 복합전구체의 TEM 측정 이미지이다.
도 6 및 7은 실험예와 비교예의 양극재의 충방전 테스트 결과이다.1 is a SEM photograph of a nickel-cobalt-manganese composite precursor produced by the first coprecipitation step of the present invention.
2 is a SEM photograph of the nickel-cobalt-manganese composite precursor produced by the second coprecipitation step of the present invention.
3 is a SEM photograph of a composite precursor of Comparative Example prepared through a single coprecipitation.
4 is a TEM measurement image of a composite precursor of the embodiment, and Fig. 5 is an TEM measurement image of a composite precursor of a comparative example.
6 and 7 are the charge / discharge test results of the cathode material of the experimental example and the comparative example.
본 발명은 비표면적이 높은 니켈-코발트-망간 복합전구체[NixCoyMn1-x-y(OH)2,여기서, 0＜x<1, 0＜y<1, 0＜x+y<1]를 제조하기 위한 방법으로서, pH가 다른 조건에서 총 2번의 공침을 통해 니켈-코발트-망간 복합전구체를 제조하는 것을 특징으로 한다.The present invention relates to a nickel-cobalt-manganese composite precursor having a high specific surface area [Ni x Co y Mn 1-xy (OH) 2 , where 0 <x <1, 0 <y < Characterized in that a nickel-cobalt-manganese composite precursor is produced through a total of two coprecipitations under different pH conditions.
본 발명은 상기 목적을 구현하기 위하여, 본 발명은 니켈-코발트-망간 복합전구체를 동시공침에 의해 제조하는 방법에 있어서, pH 9.0 ~ 9.5 조건의 반응기 내에 황산니켈, 황산코발트 및 황산망간의 전이금속 수용액을 공침법에 의하여 복합전구체를 제조하는 제1공침단계; 및 pH 10.5 ~ 11.0으로 pH를 상승한 후 공침을 더 진행하는 제2공침단계를 포함하여 이루어지는 것을 특징으로 하는 고비표면적의 니켈-코발트-망간 복합전구체의 제조방법을 제공한다. In order to accomplish the above object, the present invention provides a method for preparing a nickel-cobalt-manganese composite precursor by coextrusion, comprising the steps of: transferring nickel sulfate, cobalt sulfate and manganese sulfate into a reactor at a pH of 9.0 to 9.5; A first coprecipitation step of preparing a complex precursor by coprecipitation with a metal aqueous solution; And a second coprecipitation step of further increasing coprecipitation after the pH is raised to a pH of 10.5 to 11.0. The present invention also provides a method for preparing a high specific surface area nickel-cobalt-manganese composite precursor.
상기 제1공침단계에서는 pH 9.0 ~ 9.5로 상대적으로 낮은 pH 조건에서 공침을 진행한다. 이러한 pH가 낮은 조건에서는 상대적으로 표면적이 큰 전구체가 형성된다. 대신 비표면적이 큰 입자가 생성되지만 입자 크기는 작기 때문에 입자 크기를 키우기 위해서 후술하는 제2공침단계를 더 거쳐야 한다. 예를 들어, 제1공침단계에 의해 제조되는 복합전구체의 평균입경은 1 ㎛ 내외로 제조될 수 있다.In the first coprecipitation step, coprecipitation proceeds at a relatively low pH of 9.0 to 9.5. Under these low pH conditions, a relatively large surface area precursor is formed. Instead, particles having a large specific surface area are produced, but since the particle size is small, a second coprecipitation step described later is required in order to increase the particle size. For example, the average particle diameter of the composite precursor produced by the first coprecipitation step may be about 1 탆 or less.
제2공침단계에서는 pH 10.5 ~ 11.0으로 상대적으로 제1공침단계보다 높은 pH 조건에서 공침을 하며, 제1공침단계에서의 전구체를 시드(seed)로 하여 전구체의 크기를 키운다. 예를 들어, 제2공침단계를 통해 복합전구체의 평균입경을 8 ㎛ 이상으로 성장시킬 수 있다. 이때 제2공침단계에서는 상기 전이금속 수용액의 농도를 더 증가시킴으로써 생성되는 복합전구체를 짧은 시간 안에 크게 키울 수 있다. In the second coprecipitation step, coprecipitation is performed at a pH of 10.5-11.0 relative to the first coprecipitation step, and the size of the precursor is increased using the precursor in the first coprecipitation step as a seed. For example, the average particle diameter of the composite precursor can be increased to 8 탆 or more through the second coprecipitation step. At this time, in the second coprecipitation step, the complex precursor produced by further increasing the concentration of the transition metal aqueous solution can be raised in a short time.
본 발명에서는 pH의 범위가 다른 2번의 공침 단계를 통해 원하는 사이즈의 전구체 입자를 제조하되, 비표면적이 큰 전구체를 제조할 수 있는 것을 기술적 특징으로 한다. In the present invention, a precursor having a large specific surface area can be produced by preparing precursor particles of desired size through two co-precipitation steps having different pH ranges.
이하에서는 실험예를 통해 본 발명에 대해 설명하기로 한다.Hereinafter, the present invention will be described with reference to experimental examples.
실시예Example
pH 9.0 ~ 9.5로 맞춘 후 통상의 방법과 같이 황산니켈, 황산코발트, 황산망간을 0.8 : 0.1 : 0.1의 몰비로 혼합하여, 1.0 M과 2.5 M 농도의 전이금속 수용액을 준비하였다. 염기성 수용액으로서 50% 농도의 NaOH 수용액을 준비하였다. After the pH was adjusted to 9.0 to 9.5, nickel sulfate, cobalt sulfate and manganese sulfate were mixed in a molar ratio of 0.8: 0.1: 0.1 as a conventional method to prepare a 1.0 M and 2.5 M transition metal aqueous solution. A 50% NaOH aqueous solution was prepared as a basic aqueous solution.
상기 1.0 M 전이금속 수용액을 50 ~ 60℃로 유지되는 이온제거수가 포함된 이중수조 구조인 100 L 공침반응기에 6.5 ~ 7.0 L/hr의 속도로 20분간 공급하였고, 공침반응기 내부의 pH가 9.0 ~ 9.5이 유지되도록 NaOH 수용액을 가하였다. 첨가제로서 28% 농도의 암모니아 수용액(킬레이팅제)은 상기 1.0 M 전이금속 수용액을 투입하기 전에 3 L를 공급하였다.The 1.0 M transition metal aqueous solution was supplied to a 100 L coprecipitated reactor having a dual tank structure containing ion-removing water maintained at 50 to 60 ° C at a rate of 6.5 to 7.0 L / hr for 20 minutes, NaOH aqueous solution was added so that 9.5 was maintained. An aqueous ammonia solution (chelating agent) having a concentration of 28% as an additive was supplied with 3 L before the 1.0 M transition metal aqueous solution was introduced.
도 1은 상기 반응에 의해 제조된 니켈-코발트-망간 복합전구체의 SEM 사진으로, 전구체의 평균입경이 약 1.0 ㎛였다.FIG. 1 is a SEM photograph of a nickel-cobalt-manganese composite precursor produced by the above reaction, and the average particle size of the precursor was about 1.0 μm.
상기 제1공침단계가 완료되면, 2.5 M 농도의 전이금속 수용액을 6.5 ~ 7.0 L/hr의 속도로 상기 공침반응기에 공급하였다. 배치식 타입의 공침법으로 12시간 반응을 진행하였다. When the first coprecipitation step was completed, a 2.5 M concentration transition metal aqueous solution was supplied to the coprecipitation reactor at a rate of 6.5 to 7.0 L / hr. The reaction was carried out for 12 hours by the batch type coprecipitation method.
반응이 완료된 후, 12시간 동안 반응하여 제조된 니켈-코발트-망간 복합전구체를 이온제거수로 여러 번 세척하고, 120℃ 항온건조기에서 24시간 건조하여, 니켈-코발트-망간 복합전구체를 수득하였다. 도 2는 제2공침단계를 통해 제조된 본 발명의 복합전구체의 SEM 측정사진으로서, 전구체의 평균입경이 약 8.2 ㎛였다.After completion of the reaction, the nickel-cobalt-manganese composite precursor prepared by reacting for 12 hours was washed several times with deionized water and dried in a constant temperature drier at 120 ° C for 24 hours to obtain a nickel-cobalt-manganese composite precursor. 2 is a SEM photograph of the composite precursor of the present invention prepared through the second coprecipitation step, wherein the average particle size of the precursor was about 8.2 탆.
비교예 Comparative Example
다른 조건은 상기 실시예와 동일하게 하되, 본 발명과 같이 pH를 2단계로 조정하지 않고, pH 10.5 ~ 11.0, 전이금속 수용액의 농도 1.0 M의 조건에서 복합전구체를 제조하였으며, 도 3은 비교예의 복합전구체의 SEM 측정사진으로서, 전구체의 평균입경이 약 8.7 ㎛였다. Other conditions were the same as those of the above example except that the pH was adjusted to 2 steps and the pH was 10.5 to 11.0 and the concentration of the transition metal aqueous solution was 1.0 M as in the present invention. As an SEM photograph of the composite precursor, the average particle size of the precursor was about 8.7 탆.
실험예 1 : 실시예 및 비교예의 복합전구체 샘플의 단면 측정 실험EXPERIMENTAL EXAMPLE 1 Cross-sectional Experiment of Composite Precursor Samples of Examples and Comparative Examples
상기에서 제조한 실시예 및 비교예의 복합전구체 샘플에 대하여 단면을 확인하기 위하여 TEM 측정을 하였으며, 도 4는 실시예의 복합전구체의 TEM 측정 이미지이며, 도 5는 비교예의 복합전구체의 TEM 측정 이미지이다. The TEM images of the composite precursor samples of the Examples and Comparative Examples prepared above are shown in FIG. 4, and TEM images of the composite precursors of Comparative Examples are shown in FIG.
도 4 및 도 5를 참고하면, 실시예의 복합전구체 샘플에서는 표면 및 내부에 공극들이 더 많이 존재함을 확인할 수 있으며, 이를 통해 비교예의 복합전구체에 비해 본 발명의 방법으로 제조된 복합전구체의 비표면적이 증가하였음을 확인할 수 있었다.Referring to FIGS. 4 and 5, it can be seen that the composite precursor sample of the present embodiment has more voids on the surface and inside thereof, and thus the specific surface area of the composite precursor produced by the method of the present invention Which is the number of cases.
실험예 2 : 양극재의 물성 실험Experimental Example 2: Physical property test of cathode material
실시예와 비교예에서 제조한 니켈-코발트-망간 복합전구체 수산화물을 전이금속에 대한 리튬이온의 비가 1.02가 되도록 건식 혼합하여 산소 분위기의 소성로에서 800℃의 온도로 24시간 소성하여 양극재료를 제조하였다. The nickel-cobalt-manganese composite precursor hydroxide prepared in Examples and Comparative Examples was dry-mixed so as to have a lithium ion ratio of 1.02 to the transition metal and fired at 800 ° C for 24 hours in an oxygen atmosphere furnace to prepare a cathode material .
제조된 양극재료는 도전재인 카본블랙과 결착제인 PVdF를 95 : 2 : 3 wt.%의 비율로 N-methyl-2-pyrrolidone를 용매로 하여 슬러리를 제조하였다. 이 슬러리를 두께가 10 ㎛인 알루미늄 호일에 도포하여 건조 후 프레스로 압밀화시켜, 120℃로 10시간 건조하여 직경이 14 mm인 전극을 제조하였다.The prepared cathode material was prepared by slurrying carbon black as a conductive material and PVdF as a binder in a ratio of 95: 2: 3 wt.% With N-methyl-2-pyrrolidone as a solvent. This slurry was applied to an aluminum foil having a thickness of 10 탆, dried, and compacted by a press, followed by drying at 120 캜 for 10 hours to prepare an electrode having a diameter of 14 mm.
제조된 전극은 상대극을 리튬금속박을 사용하여 코인셀로 하여 평가하였다. 도 6 및 7은 실험예와 비교예의 양극재의 충방전 테스트 결과이다. 본 발명의 방법으로 제조한 전구체를 적용한 양극재의 경우 초기용량(mAh/g)이 215.2이었으나, 기존의 공침법을 통해 제조한 전구체를 적용한 양극재에서는 초기용량이 210.1로서 본 발명의 양극재가 우수함을 알 수 있었다. 또한, 출력효율(2C/0.1C)을 비교하면, 본 발명의 양극재는 83.0이고 비교예의 양극재의 경우 81.3로 본 발명의 양극재가 우수함을 알 수 있었다.The prepared electrode was evaluated as a coin cell using a lithium metal foil as a counter electrode. 6 and 7 are the charge / discharge test results of the cathode material of the experimental example and the comparative example. The initial capacity (mAh / g) of the cathode material applied with the precursor prepared by the method of the present invention was 215.2, but the initial capacity of the cathode material using the precursor prepared by the conventional coprecipitation method was 210.1, Could know. Further, when the output efficiency (2C / 0.1C) was compared, it was found that the cathode material of the present invention was 83.0, and the cathode material of the comparative example was 81.3.
Claims (4)
pH 9.0 ~ 9.5 조건의 공침반응기 내에 황산니켈, 황산코발트 및 황산망간의 전이금속 수용액을 공침에 의해 복합전구체로 제조하는 제1공침단계; 및
pH 10.5 ~ 11.0으로 pH를 상승한 후 공침을 더 진행하는 제2공침단계를 포함하여 이루어지는 것을 특징으로 하는 고비표면적의 니켈-코발트-망간 복합전구체의 제조방법.
Nickel-cobalt-manganese composite precursor [Ni x Co y Mn 1-xy (OH) 2 , Wherein 0 <x <1, 0 <y <1, 0 <x + y <1]
a first coprecipitation step of preparing a complex precursor by coprecipitation of a transition metal aqueous solution of nickel sulfate, cobalt sulfate and manganese sulfate in a coprecipitation reactor under the conditions of pH 9.0 to 9.5; And
and a second coprecipitation step of raising the pH to pH 10.5 to 11.0 and then further coprecipitating the nickel-cobalt-manganese composite precursor.
The method for producing a nickel-cobalt-manganese composite precursor according to claim 1, wherein an aqueous NaOH solution is used as a basic aqueous solution for adjusting the pH.
The method according to claim 1, wherein the concentration of the transition metal aqueous solution containing nickel sulfate, cobalt sulfate and manganese sulfate in the second coprecipitation step is higher than the concentration of the transition metal aqueous solution in the first coprecipitation step - cobalt-manganese composite precursor.
2. The method of claim 1, wherein the first coprecipitation and the second coprecipitation are in a batch reactor or a Quattro Taylor reactor.
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