WO2015133692A1 - 양극 활물질, 그를 갖는 리튬이차전지 및 그의 제조 방법 - Google Patents
양극 활물질, 그를 갖는 리튬이차전지 및 그의 제조 방법 Download PDFInfo
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Definitions
- lithium cobalt oxide such as LiCoO 2 having a layered structure is the most commonly used cathode material.
- Lithium cobalt oxide has high cost of Co, and toxic problems and deterioration of structural stability due to phase deformation due to lithium desorption during charging are problematic.
- NCM523 N is Ni, C is Co, M is Mn, 523 means Ni, Co, Mn content. That is, “NCM523” means "LiNi 0.5 Co 0.2 Mn 0.3 O 2 ".
- NCM material composed of NCM7 having a Ni content of 65% or more in order to achieve high capacity is actively underway.
- Another object of the present invention is to provide a cathode active material, a lithium secondary battery having the same, and a method of manufacturing the same, which can be commercialized by improving battery characteristics and thermal stability in a high temperature environment even when the Ni content is increased to 65% or more.
- the present invention is coated with a dissimilar metal (M) on the surface of the transition metal precursor containing Ni, Co and Mn and heat-treated with a lithium source, the dissimilar metal is part of the Ni, Co and Mn Substituted with to provide a cathode active material for a lithium secondary battery represented by the formula (1) below.
- M dissimilar metal
- M is Ti, Al, Mg, Fe, Cu, Ag, Ca, Na, K, In, Ga, Ge, V , At least one metal element selected from the group consisting of Mo, Nb, Si and Zr)
- the transition metal precursor may be a nickel-based transition metal hydroxide or a nickel-based transition metal carbonate prepared by a coprecipitation method.
- the content (a) of the nickel in Formula 1 may be 0.65 or more.
- the dissimilar metal may be Ti.
- the present invention is also coated with a dissimilar metal (M) on the surface of the transition metal precursor containing Ni, Co and Mn, and then heat treated with a lithium source to displace the dissimilar metal with some of the Ni, Co and Mn to the formula It provides a lithium secondary battery comprising a positive electrode active material represented by 1.
- M dissimilar metal
- the positive electrode active material exhibits a peak of an exothermic temperature at 275 ° C. or higher during DSC evaluation under a 4.3 V state of charge.
- the present invention also provides a step of coating a dissimilar metal compound on the surface of the transition metal precursor by adding a transition metal precursor including Ni, Co and Mn to a dissimilar metal (M) compound coating solution, followed by stirring and drying.
- a transition metal precursor coated with a metal compound together with a lithium source to produce a cathode active material represented by Chemical Formula 1 by displacing the dissimilar metal with some of the Ni, Co, and Mn to form a cathode active material for a lithium secondary battery. It provides a method for producing.
- the coating step comprises the steps of preparing a Ti compound coating solution comprising at least one Ti compound selected from the group consisting of nano-sized Ti oxide and its precursor, and the Ti Injecting the transition metal precursor in a compound coating solution, it may comprise the step of coating a Ti compound on the surface of the transition metal precursor by stirring and drying.
- the Ti compound may include 0.1 to 5 wt% based on the weight of the transition metal precursor.
- the transition metal precursor may be represented by the formula (2) below.
- the present invention by substituting a small amount of dissimilar metals (M) in the Ni-rich positive electrode active material, even when the Ni content is increased to 65% or more, structural stability may be provided to improve battery characteristics. That is, by coating a dissimilar metal (M) on the surface of the transition metal precursor including Ni, Co, and Mn, and heat-treating with a lithium source, the dissimilar metal is replaced with some of the Ni, Co, and Mn, whereby the Ni content in the positive electrode active material is increased. Increasing above 65% can improve battery characteristics and thermal stability in high temperature environments.
- the improved battery properties and thermal stability in the high temperature environment is due to the increase in temperature of the main exothermic peak and the exothermic temperature peak at 275 ° C. or higher in the DSC evaluation of the cathode active material according to the present invention. It is remarkably improved and it can be seen that the strength of the particles is remarkably improved.
- the transition metal precursor prepared by the coprecipitation method is added to the dissimilar metal compound coating solution, stirred and dried to coat the dissimilar metal compound on the surface of the transition metal precursor, and then the transition metal precursor coated with the dissimilar metal compound is coated with a lithium source.
- the manufacturing method of the positive electrode active material which can substitute a part of transition metal with a part of transition metal easily can be provided.
- the present invention can provide a positive electrode active material for a lithium secondary battery having a high uniformity through the process of immersing the transition metal precursor in a coating solution in which dissimilar metals are dispersed for the uniform coating of dissimilar metals, followed by mixing and drying.
- FIG. 1 is a flowchart illustrating a method of manufacturing a cathode active material for a lithium secondary battery according to an embodiment of the present invention.
- FIG. 2 to 4 are SEM images of the positive electrode active materials according to Comparative Example 1, Example 1, and Example 2.
- FIG. 2 to 4 are SEM images of the positive electrode active materials according to Comparative Example 1, Example 1, and Example 2.
- Example 5 is a graph showing the XRD patterns of the positive electrode active material according to Comparative Example 1, Example 1 and Example 2.
- FIG. 6 and 7 illustrate SEM images and EDS linear mapping results of the cathode active materials according to Examples 1 and 2.
- FIG. 6 and 7 illustrate SEM images and EDS linear mapping results of the cathode active materials according to Examples 1 and 2.
- Example 8 is a graph showing the life characteristics at room temperature of the lithium secondary battery using the positive electrode active material of Comparative Example 1, Example 1 and Example 2.
- Example 9 is a graph showing the life characteristics at high temperatures of the lithium secondary battery using the positive electrode active material of Comparative Example 1, Example 1 and Example 2.
- the cathode active material for a lithium secondary battery according to the present invention is a Ni-rich cathode active material represented by Chemical Formula 1 below.
- M is Ti, Al, Mg, Fe, Cu, Ag, Ca, Na, K, In, Ga, Ge, V , At least one metal element selected from the group consisting of Mo, Nb, Si and Zr)
- the cathode active material according to the present invention is a nickel-based transition metal oxide substituted with dissimilar metal (M), and after coating dissimilar metal (M) on the surface of a transition metal precursor including Ni, Co, and Mn, a lithium source and
- the heat treatment (calcination; calcining or calcining) may be formed by substituting a heterometal (M) with some of Ni, Co, and Mn.
- the transition metal precursor may be nickel-based transition metal hydroxide or nickel-based transition metal carbonate prepared by coprecipitation.
- the transition metal precursor may be represented by Formula 2 below.
- Ti As the dissimilar metal (M), Ti, Al, Mg, Fe, Cu, Ag, Ca, Na, K, In, Ga, Ge, V, Mo, Nb, Si or Zr may be used, and embodiments of the present invention In Ti was used.
- the raw material of Ti nano-sized Ti oxide or a precursor thereof may be used.
- the content (a) of nickel is preferably 0.65 or more, and more preferably 0.7 or more.
- a small amount of dissimilar metal (M) is substituted for a high Ni content of the cathode active material, thereby providing structural stability even when the Ni content is increased to 65% or more, thereby improving battery characteristics. That is, by coating a dissimilar metal (M) on the surface of the transition metal precursor including Ni, Co, and Mn, and heat-treating with a lithium source, dissimilar metal (M) is replaced with some of Ni, Co and Mn, Ni in the positive electrode active material Even if the content is increased to more than 65% can improve the battery characteristics and thermal stability in high temperature environment.
- FIG. 1 is a flowchart illustrating a method of manufacturing a cathode active material for a lithium secondary battery according to an embodiment of the present invention.
- a transition metal precursor including Ni, Co, and Mn is added to a dissimilar metal compound coating solution in S100, and then stirred and dried to coat a dissimilar metal compound on the surface of the transition metal precursor.
- a transition metal precursor coated with a dissimilar metal compound may be heat-treated with a lithium source to prepare a cathode active material represented by Chemical Formula 1 by displacing a dissimilar metal (M) with a portion of Ni, Co, and Mn.
- the coating of the dissimilar metal compound according to step S100 may be performed as follows.
- a Ti compound coating solution including one or more Ti compounds selected from the group consisting of nano-sized Ti oxides and precursors thereof is prepared.
- TiO 2 nanopowder is added to a solvent such as isopropyl alcohol (IPA) and stirred to prepare a Ti compound coating solution in which TiO 2 is uniformly dispersed.
- IPA isopropyl alcohol
- a nano-sized Ti oxide was used as the dissimilar metal compound.
- the content of the Ti compound may be 0.1 to 5 wt% with respect to the weight of the transition metal precursor.
- the Ti compound may be coated on the surface of the transition metal precursor according to step S200.
- the transition metal precursor may be nickel-based transition metal hydroxide or nickel-based transition metal carbonate prepared by coprecipitation.
- the nickel content of the transition metal precursor may be at least 0.65.
- step S310 a lithium source is added to the transition metal precursor coated with the Ti compound.
- step S320 the mixture of the transition metal precursor coated with the Ti compound and the lithium source is heat-treated at 850 ° C. for 10 hours to prepare a Ni-containing positive electrode active material in which Ti is added (substituted) according to the present embodiment according to step S330. It can manufacture. That is, in the heat treatment process, Ti is substituted with some of Ni, Co, and Mn to prepare a cathode active material according to Chemical Formula 1.
- the cathode active material according to Example 1, Example 2 and Comparative Example 1 was prepared.
- a nickel-based transition metal hydroxide precursor having a composition of Ni 0.7 Co 0.15 Mn 0.15 (OH) 2 prepared by coprecipitation was used as a base material.
- TiO 2 powder in the form of nano particles was used.
- a nickel-based transition metal hydroxide precursor was added to a coating solution in which 1 wt% of TiO 2 powder was dispersed in IPA relative to 10 g of the nickel-based transition metal hydroxide precursor mass, and then stirred at 60 ° C. for 3 hours.
- IPA is removed by evaporation, and TiO 2 is adsorbed on the surface of the nickel-based transition metal hydroxide precursor to obtain a coated precursor.
- Ti-coated precursor is mixed with a lithium source and heat-treated, thereby preparing a cathode active material according to Example 1 substituted with Ti.
- lithium carbonate Li 2 CO 3
- the ratio Li / Me of the lithium source to the transition metal was 1.05.
- Heat treatment was performed in an oxygen atmosphere at 850 ° C. for 10 hours using a tube furnace.
- a positive electrode active material according to Example 2 in which Ti was substituted under the same conditions as in Example 1, except that 2 wt% of TiO 2 powder was used relative to 10 g of the nickel-based transition metal hydroxide precursor to coat the Ti compound.
- a cathode active material according to Comparative Example 1 in which Ti was not substituted under the same conditions as in Example 1, was prepared. That is, a cathode active material according to Comparative Example 1 was prepared by heat-treating a nickel-based transition metal hydroxide precursor having a composition of Ni 0.7 Co 0.15 Mn 0.15 (OH) 2 prepared by the coprecipitation method.
- FIG. 5 is a graph showing X-ray diffraction (XRD) patterns of cathode active materials according to Comparative Example 1, Example 1, and Example 2.
- FIG. Table 1 is a table showing the 003 peak (ti) with increasing Ti substitution.
- FIG. 1 and Example 2 illustrate SEM images and EDS linear mapping results of the cathode active materials according to Examples 1 and 2.
- FIG. Table 2 and Table 3 show the results of chemical composition according to the EDS analysis of the positive electrode active material according to Examples 1 and 2, showing the results of the composition analysis from the particle surface (Line 1) to the particle center (Line 5) .
- the positive electrode active material according to Examples 1 and 2 has Ti uniformly substituted therein. It can be confirmed that it is made of the positive electrode active material to be distributed.
- Example 2 After using the positive electrode active material according to Example 1, Example 2 and Comparative Example 1 to prepare a lithium secondary battery capable of evaluating the electrochemical performance of the positive electrode active material in the following manner, the battery performance evaluation was performed.
- the lithium secondary battery includes a cathode including a cathode active material, a cathode including an anode active material capable of inserting / desorbing lithium ions, a separator existing between the cathode and the anode, and a non-aqueous electrolyte.
- a lithium secondary battery was manufactured with a coin-type half cell, and lithium metal foil was used as a counter electrode, and the discharge voltage was 3.0 V and the charge voltage was 4.3 V.
- Lithium metal foil punched to 16 mm in diameter was used as the counter electrode, polypropylene (PP) film was used as the separator, and EC / DMC / DEC 1: 2: 1 v / of 1M LiPF 6 was used as the electrolyte. A mixed solution of v was used. After the electrolyte was impregnated into the separator, the separator was sandwiched between the working electrode and the counter electrode, and a lithium secondary battery for electrochemical characterization was manufactured using a 2032 coin cell.
- PP polypropylene
- Example 8 is a graph showing the life characteristics at room temperature of the lithium secondary battery using the positive electrode active material of Comparative Example 1, Example 1 and Example 2.
- Table 4 is a table showing the horizontal characteristics at room temperature as the Ti substitution amount increases.
- FIG. 8 illustrates the 0.5C life characteristics at room temperature (25 ° C.), and the capacity and initial retention with respect to the cycle increase are shown in Table 4.
- Comparative Example 1 is 172.3 mAh / g compared to Example 1 and Example 2 substituted for Ti can be confirmed that the initial capacity is somewhat reduced to 170 mAh / g. there was. This is expected to occur as the fraction of Ni decreases as Ti is substituted.
- Table 5 is a table showing the horizontal characteristics in the design according to the increase in the amount of Ti substitution.
- FIG. 9 illustrates the 0.5C life characteristics at high temperature (60 ° C.), and the capacity and the retention ratio with respect to the initial capacity are shown in Table 5 as the cycle increases.
- Comparative Example 1 which does not substitute Ti, shows that the capacity retention rate is greatly reduced. While the capacity retention rate after 40 cycles was 79.8% in Comparative Example 1, it was confirmed that Example 1 and Example 2 in which Ti was substituted showed excellent capacity retention rates of 94.2% and 95.3%, respectively.
- the positive electrode active material substituted with Ti is an effective method for increasing the high temperature life characteristics.
- DSC differential scanning calorimetry
- Example 1 Although the Ni content is 70%, the temperature at which the exothermic peak appears at the same level as the exothermic temperature peak of LiNi 0.6 Co 0.2 Mn 0.2 O 2 having a Ni composition of 60% was improved.
- Example 1 and Example 2 had high thermal stability when compared to the cathode active materials according to Comparative Example 1.
Abstract
Description
003 peak (2 theta / degree) | |
비교예 1 | 18.77 |
실시예 1 | 18.75 |
실시예 2 | 18.74 |
Ni | Co | Mn | Ti | Total | |
Line 1 | 70.81 | 15.80 | 12.91 | 0.48 | 100 |
Line 2 | 69.42 | 16.42 | 13.56 | 0.60 | 100 |
Line 3 | 69.50 | 15.53 | 14.30 | 0.67 | 100 |
Line 4 | 69.11 | 15.90 | 14.27 | 0.72 | 100 |
Line 5 | 70.18 | 15.23 | 13.79 | 0.80 | 100 |
Ni | Co | Mn | Ti | Total | |
Line 1 | 70.48 | 14.93 | 13.19 | 1.40 | 100 |
Line 2 | 68.82 | 15.37 | 14.12 | 1.69 | 100 |
Line 3 | 69.03 | 15.48 | 13.81 | 1.68 | 100 |
Line 4 | 68.28 | 15.52 | 14.27 | 1.93 | 100 |
Line 5 | 68.96 | 15.27 | 13.96 | 1.81 | 100 |
Claims (15)
- Ni, Co 및 Mn을 포함하는 전이금속 전구체의 표면에 이종금속(M)을 코팅한 후 리튬 소스와 열처리하여 상기 이종금속(M)이 상기 Ni, Co 및 Mn 중 일부와 치환되어 아래의 화학식1로 표현되는 리튬이차전지용 양극 활물질.[화학식 1]LiNiaCobMncMdO2(0.6<a≤0.9, 0<d≤0.1, a+b+c+d=1, M은 Ti, Al, Mg, Fe, Cu, Ag, Ca, Na, K, In, Ga, Ge, V, Mo, Nb, Si 및 Zr로 이루어진 군에서 선택된 1종 이상의 금속 원소)
- 제1항에 있어서,상기 전이금속 전구체는 공침법으로 제조된 니켈계 전이금속 수산화물 또는 니켈계 전이금속 탄산화물인 것을 특징으로 하는 리튬이차전지용 양극 활물질.
- 제1항에 있어서,상기 화학식1에서 상기 니켈의 함량(a)은 0.65 이상인 것을 특징으로 하는 리튬이차전지용 양극 활물질.
- 제1항에 있어서,상기 이종금속(M)은 Ti인 것을 특징으로 하는 리튬이차전지용 양극 활물질.
- Ni, Co 및 Mn을 포함하는 전이금속 전구체의 표면에 이종금속(M)을 코팅한 후 리튬 소스와 열처리하여 상기 이종금속(M)이 상기 Ni, Co 및 Mn 중 일부와 치환되어 아래의 화학식1로 표현되는 양극 활물질을 포함하는 리튬이차전지.[화학식 1]LiNiaCobMncMdO2(0.6<a≤0.9, 0<d≤0.1, a+b+c+d=1, M은 Ti, Al, Mg, Fe, Cu, Ag, Ca, Na, K, In, Ga, Ge, V, Mo, Nb, Si 및 Zr로 이루어진 군에서 선택된 1종 이상의 금속 원소)
- 제5항에 있어서,상기 화학식1에서 상기 니켈의 함량(a)은 0.65 이상인 것을 특징으로 하는 리튬이차전지.
- 제6항에 있어서,상기 이종금속(M)은 Ti인 것을 특징으로 하는 리튬이차전지.
- 제7항에 있어서,상기 양극 활물질은 4.3 V 충전상태에서 DSC(differential scanning calorimetry) 평가 시 발열 온도의 피크가 275℃ 이상에서 나타나는 것을 특징으로 하는 리튬이차전지.
- 이종금속(M) 화합물 코팅 용액에 Ni, Co 및 Mn을 포함하는 전이금속 전구체를 투입한 후 교반 및 건조하여 상기 전이금속 전구체의 표면에 이종금속 화합물을 코팅하는 단계;이종금속 화합물이 코팅된 전이금속 전구체를 리튬 소스와 함께 열처리하여 상기 이종금속(M)이 상기 Ni, Co 및 Mn 중 일부와 치환되어 아래의 화학식1로 표현되는 양극 활물질을 제조하는 단계;를 포함하는 리튬이차전지용 양극 활물질의 제조 방법.[화학식 1]LiNiaCobMncMdO2(0.6<a≤0.9, 0<d≤0.1, a+b+c+d=1, M은 Ti, Al, Mg, Fe, Cu, Ag, Ca, Na, K, In, Ga, Ge, V, Mo, Nb, Si 및 Zr로 이루어진 군에서 선택된 1종 이상의 금속 원소)
- 제9항에 있어서,상기 전이금속 전구체는 공침법으로 제조된 니켈계 전이금속 수산화물 또는 니켈계 전이금속 탄산화물인 것을 특징으로 하는 리튬이차전지용 양극 활물질의 제조 방법.
- 제9항에 있어서,상기 화학식1에서 상기 니켈의 함량(a)은 0.65 이상인 것을 특징으로 하는 리튬이차전지용 양극 활물질의 제조 방법.
- 제9항에 있어서,상기 이종금속(M)은 Ti인 것을 특징으로 하는 리튬이차전지용 양극 활물질의 제조 방법.
- 제12항에 있어서, 상기 코팅하는 단계에서,나노 크기의 Ti 산화물 및 그의 전구체로 이루어진 군에서 선택된 1종 이상의 Ti 화합물을 포함하는 Ti 화합물 코팅 용액을 제조하는 단계;상기 Ti 화합물 코팅 용액에 상기 전이금속 전구체를 투입한 후 교반 및 건조하여 상기 전이금속 전구체의 표면에 Ti 화합물을 코팅하는 단계;를 포함하는 리튬이차전지용 양극 활물질의 제조 방법.
- 제13항에 있어서,상기 Ti 화합물은 상기 전이금속 전구체의 무게 대비 0.1 내지 5 wt%가 포함되는 것을 특징으로 하는 리튬이차전지용 양극 활물질의 제조 방법.
- 제9항에 있어서,상기 전이금속 전구체는 아래의 화학식2로 표현되는 것을 특징으로 하는 리튬이차전지용 양극 활물질의 제조 방법.[화학식 2]NiaCobMncO2(0.6<a≤0.9, a+b+c=1)
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