KR102114229B1 - Positive active material for rechargeable lithium battery, method of preparing the same, and rechargeable lithium battery including the same - Google Patents
Positive active material for rechargeable lithium battery, method of preparing the same, and rechargeable lithium battery including the same Download PDFInfo
- Publication number
- KR102114229B1 KR102114229B1 KR1020160026500A KR20160026500A KR102114229B1 KR 102114229 B1 KR102114229 B1 KR 102114229B1 KR 1020160026500 A KR1020160026500 A KR 1020160026500A KR 20160026500 A KR20160026500 A KR 20160026500A KR 102114229 B1 KR102114229 B1 KR 102114229B1
- Authority
- KR
- South Korea
- Prior art keywords
- active material
- positive electrode
- electrode active
- secondary battery
- lithium secondary
- Prior art date
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 62
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 32
- 239000011247 coating layer Substances 0.000 claims abstract description 30
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 24
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 23
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 17
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 15
- 229910052796 boron Inorganic materials 0.000 claims abstract description 14
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 14
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 8
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 7
- -1 Al (OH) 3 Inorganic materials 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 20
- 238000004519 manufacturing process Methods 0.000 claims description 13
- 239000007773 negative electrode material Substances 0.000 claims description 11
- 239000003792 electrolyte Substances 0.000 claims description 10
- 238000010304 firing Methods 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 3
- 229910017119 AlPO Inorganic materials 0.000 claims description 3
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- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims 1
- 229910052749 magnesium Inorganic materials 0.000 abstract description 7
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- 230000000052 comparative effect Effects 0.000 description 14
- 239000010936 titanium Substances 0.000 description 13
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 10
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- 239000011149 active material Substances 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
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- 159000000002 lithium salts Chemical class 0.000 description 4
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Classifications
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- 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
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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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
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/582—Halogenides
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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Abstract
하기 화학식 1로 표시되는 화합물을 포함하는 코어; 및 코어의 표면에 위치한 코팅층을 포함하는 리튬 이차 전지용 양극 활물질을 제공한다.
[화학식 1]
Li[LizA(1-z-a)Da]EbO2 -b
(상기 화학식 1에서 A는 NiαCoβMnγ이고, D는 Mg, Al, B, Zr, Mo, Nb 및 Ti로 이루어진 군에서 선택된 1종 이상의 원소이고, E는 P, F 및 S로 이루어진 군에서 선택된 1종 이상의 원소이고, -0.05 ≤ z ≤ 0.1, 0 ≤ a ≤ 0.05, 0 ≤ b ≤ 0.05, 0.3 ≤ α ≤ 0.9, 0.05≤ β≤0.4 및 0.05≤ γ≤0.4 이다.) Core comprising a compound represented by the formula (1); And it provides a positive electrode active material for a lithium secondary battery comprising a coating layer located on the surface of the core.
[Formula 1]
Li [Li z A (1-za) D a ] E b O 2 -b
(In Formula 1, A is Ni α Co β Mn γ , D is one or more elements selected from the group consisting of Mg, Al, B, Zr, Mo, Nb, and Ti, and E is composed of P, F, and S One or more elements selected from the group, -0.05 ≤ z ≤ 0.1, 0 ≤ a ≤ 0.05, 0 ≤ b ≤ 0.05, 0.3 ≤ α ≤ 0.9, 0.05 ≤ β ≤ 0.4 and 0.05 ≤ γ ≤ 0.4.)
Description
리튬 이차 전지용 양극 활물질, 리튬 이차 전지용 양극 활물질의 제조 방법 및 리튬 이차전지용 양극 활물질에 관한 것이다. It relates to a positive electrode active material for a lithium secondary battery, a method for producing a positive electrode active material for a lithium secondary battery, and a positive electrode active material for a lithium secondary battery.
최근 휴대용 전자기기의 소형화 및 경량화 추세와 관련하여 이들 기기의 전원으로 사용되는 전지의 고성능화 및 대용량화에 대한 필요성이 높아지고 있다.Recently, in connection with the trend of miniaturization and weight reduction of portable electronic devices, there is an increasing need for high performance and high capacity of batteries used as power sources for these devices.
전지는 양극과 음극에 전기 화학 반응이 가능한 물질을 사용함으로써 전력을 발생시키는 것이다. 이러한 전지 중 대표적인 예로는 양극 및 음극에서 리튬 이온이 인터칼레이션/디인터칼레이션될 때의 화학전위(chemical potential)의 변화에 의하여 전기 에너지를 생성하는 리튬 이차 전지가 있다.The battery is to generate electric power by using a material capable of electrochemical reaction on the positive electrode and the negative electrode. A representative example of such a battery is a lithium secondary battery that generates electrical energy by changing a chemical potential when lithium ions are intercalated / deintercalated at the positive electrode and the negative electrode.
상기 리튬 이차 전지는 리튬 이온의 가역적인 인터칼레이션/디인터칼레이션이 가능한 물질을 양극과 음극 활물질로 사용하고, 상기 양극과 음극 사이에 유기 전해액 또는 폴리머 전해액을 충전시켜 제조한다.The lithium secondary battery is manufactured by using a material capable of reversible intercalation / deintercalation of lithium ions as a positive electrode and a negative electrode active material, and charging an organic electrolyte solution or a polymer electrolyte solution between the positive electrode and the negative electrode.
리튬 이차 전지의 양극 활물질로는 리튬 복합금속 화합물이 사용되고 있으며, 그 예로 LiCoO2, LiMn2O4, LiNiO2, LiMnO2 등의 복합금속 산화물들이 연구되고 있다. A lithium composite metal compound is used as a cathode active material of a lithium secondary battery, and examples thereof include composite metal oxides such as LiCoO 2 , LiMn 2 O 4 , LiNiO 2 , and LiMnO 2 .
상기 양극 활물질 중 LiMn2O4, LiMnO2 등의 Mn계 양극 활물질은 합성하기도 쉽고, 값이 비교적 싸며, 과충전시 다른 활물질에 비하여 열적 안정성이 가장 우수하고, 환경에 대한 오염이 낮아 매력이 있는 물질이기는 하나, 용량이 적다는 단점을 가지고 있다.Among the positive electrode active materials, Mn-based positive electrode active materials such as LiMn 2 O 4 and LiMnO 2 are also easy to synthesize, relatively inexpensive, have the best thermal stability compared to other active materials when overcharged, and have low environmental pollution, making them attractive. Wins, but has the disadvantage of low capacity.
LiCoO2는 양호한 전기 전도도와 약 3.7V 정도의 높은 전지 전압을 가지며, 사이클 수명 특성, 안정성 또한 방전 용량 역시 우수하므로, 현재 상업화되어 시판되고 있는 대표적인 양극 활물질이다. 그러나 LiCoO2는 가격이 비싸기 때문에 전지 가격의 30% 이상을 차지하므로 가격 경쟁력이 떨어지는 문제점이 있다.LiCoO 2 has good electrical conductivity and a high battery voltage of about 3.7V, and has excellent cycle life characteristics and stability and discharge capacity, and thus is a representative positive electrode active material commercially available and commercially available. However, since LiCoO 2 is expensive, it occupies more than 30% of the battery price, so there is a problem that the price competitiveness is low.
또한 LiNiO2는 위에서 언급한 양극 활물질 중 가장 높은 방전 용량의 전지 특성을 나타내고 있으나, 합성하기 어려운 단점이 있다. 또한 니켈의 높은 산화상태는 전지 및 전극 수명 저하의 원인이 되며, 자기 방전이 심하고 가역성이 떨어지는 문제가 있다. 아울러, 안정성 확보가 완전하지 않아서 상용화에 어려움을 겪고 있다.In addition, LiNiO 2 shows the battery characteristics of the highest discharge capacity among the positive electrode active materials mentioned above, but it is difficult to synthesize. In addition, the high oxidation state of nickel causes a decrease in battery and electrode life, and there is a problem in that self-discharge is severe and reversibility is poor. In addition, it is difficult to commercialize because stability is not completely secured.
본 발명의 일 구현예는 수명 특성이 우수한 리튬 이차 전지용 양극 활물질, 이의 제조방법 및 이를 포함하는 리튬 이차 전지를 제공하는 것이다.One embodiment of the present invention is to provide a lithium secondary battery comprising a positive electrode active material for a lithium secondary battery having excellent life characteristics, a manufacturing method thereof, and the same.
본 발명의 일 구현예에서는, 하기 화학식 1로 표시되는 화합물을 포함하는 코어; 및 코어의 표면에 위치한 코팅층을 포함하는 리튬 이차 전지용 양극 활물질을 제공한다.In one embodiment of the present invention, a core comprising a compound represented by Formula 1 below; And it provides a positive electrode active material for a lithium secondary battery comprising a coating layer located on the surface of the core.
[화학식 1][Formula 1]
Li[LizA(1-z-a)Da]EbO2 -b Li [Li z A (1-za) D a ] E b O 2 -b
(상기 화학식 1에서 A는 NiαCoβMnγ이고, D는 Mg, Al, B, Zr, Mo, Nb 및 Ti로 이루어진 군에서 선택된 1종 이상의 원소이고, E는 P, F 및 S로 이루어진 군에서 선택된 1종 이상의 원소이고, -0.05 ≤ z ≤ 0.1, 0 ≤ a ≤ 0.05, 0 ≤ b ≤ 0.05, 0.3 ≤ α ≤ 0.9, 0.05≤ β≤0.4 및 0.05≤ γ≤0.4 이다.)(In Formula 1, A is Ni α Co β Mn γ , D is one or more elements selected from the group consisting of Mg, Al, B, Zr, Mo, Nb, and Ti, and E is composed of P, F, and S One or more elements selected from the group, -0.05 ≤ z ≤ 0.1, 0 ≤ a ≤ 0.05, 0 ≤ b ≤ 0.05, 0.3 ≤ α ≤ 0.9, 0.05 ≤ β ≤ 0.4 and 0.05 ≤ γ ≤ 0.4.)
화학식 1에서, -0.05 ≤ z ≤ 0.05, 0.6 ≤ α ≤ 0.9, 0.05≤ β≤0.2 및 0.05≤ γ≤0.2일 수 있다.In Formula 1, -0.05 ≤ z ≤ 0.05, 0.6 ≤ α ≤ 0.9, 0.05 ≤ β ≤ 0.2 and 0.05 ≤ γ ≤ 0.2.
화학식 1에서 D는 Mo, Nb, Zr, Ti 또는 이들의 조합일 수 있다.D in Formula 1 may be Mo, Nb, Zr, Ti, or a combination thereof.
화학식 1에서 D는 Mo, Nb 또는 이들의 조합일 수 있다.D in Formula 1 may be Mo, Nb, or a combination thereof.
화학식 1에서 D의 몰 도핑비율은 0.001 내지 0.01일 수 있다.The molar doping ratio of D in Chemical Formula 1 may be 0.001 to 0.01.
코팅층은 Al, B 또는 이들의 조합을 포함할 수 있다.The coating layer may include Al, B, or a combination thereof.
양극 활물질의 총 중량에 대하여 코팅층의 함량은 0.05 내지 1.0 중량%가 될 수 있다.The content of the coating layer relative to the total weight of the positive electrode active material may be 0.05 to 1.0% by weight.
코팅층은 코어의 표면에 부분적으로 위치되는 아일랜드(Island) 형태일 수 있다.The coating layer may be in the form of an island partially located on the surface of the core.
코팅층은 F를 더 포함할 수 있다.The coating layer may further include F.
본 발명의 다른 일 구현예에서는, 하기 화학식 1로 표시되는 화합물을 포함하는 코어를 준비하는 단계; 코어와 코팅층을 형성하는 원료 화합물을 혼합하여 혼합물을 제조하는 단계; 및 혼합물을 소성하는 단계를 포함하는 리튬 이차 전지용 양극 활물질의 제조 방법을 제공한다.In another embodiment of the present invention, preparing a core comprising a compound represented by Formula 1 below; Preparing a mixture by mixing a core and a raw material compound forming a coating layer; And it provides a method for producing a positive electrode active material for a lithium secondary battery comprising the step of firing the mixture.
[화학식 1][Formula 1]
Li[LizA(1-z-a)Da]EbO2 -b Li [Li z A (1-za) D a ] E b O 2 -b
(상기 화학식 1에서 A는 NiαCoβMnγ이고, D는 Mg, Al, B, Zr, Mo, Nb 및 Ti로 이루어진 군에서 선택된 1종 이상의 원소이고, E는 P, F 및 S로 이루어진 군에서 선택된 1종 이상의 원소이고, -0.05 ≤ z ≤ 0.1, 0 ≤ a ≤ 0.05, 0 ≤ b ≤ 0.05, 0.3 ≤ α ≤ 0.9, 0.05≤ β≤0.4 및 0.05≤ γ≤0.4 이다.)(In Formula 1, A is Ni α Co β Mn γ , D is one or more elements selected from the group consisting of Mg, Al, B, Zr, Mo, Nb, and Ti, and E is composed of P, F, and S One or more elements selected from the group, -0.05 ≤ z ≤ 0.1, 0 ≤ a ≤ 0.05, 0 ≤ b ≤ 0.05, 0.3 ≤ α ≤ 0.9, 0.05 ≤ β ≤ 0.4 and 0.05 ≤ γ ≤ 0.4.)
화학식 1에서 -0.05 ≤ z ≤ 0.05, 0.6 ≤ α ≤ 0.9, 0.05≤ β≤0.2 및 0.05≤ γ≤0.2일 수 있다.In Formula 1, -0.05 ≤ z ≤ 0.05, 0.6 ≤ α ≤ 0.9, 0.05 ≤ β ≤ 0.2 and 0.05 ≤ γ ≤ 0.2.
화학식 1에서 D는 Mo, Nb, Zr, Ti 또는 이들의 조합일 수 있다.D in Formula 1 may be Mo, Nb, Zr, Ti, or a combination thereof.
화학식 1에서 D는 Mo, Nb 또는 이들의 조합일 수 있다.D in Formula 1 may be Mo, Nb, or a combination thereof.
화학식 1에서 D의 몰 도핑비율은 0.001 내지 0.01일 수 있다.The molar doping ratio of D in Chemical Formula 1 may be 0.001 to 0.01.
혼합물을 제조하는 단계에서, 원료 화합물은 알루미늄 공급원, 붕소 공급원 또는 이들의 조합일 수 있다.In the step of preparing the mixture, the raw material compound may be an aluminum source, a boron source, or a combination thereof.
혼합물을 제조하는 단계에서, 원료 화합물은 Al2O3, Al(OH)3, AlPO4, Al(NO3)3, B2O3, H3BO4, B(OH)3, Li2B4O7 또는 이들의 조합일 수 있다.In the step of preparing the mixture, the raw material compound is Al 2 O 3 , Al (OH) 3 , AlPO 4 , Al (NO 3 ) 3 , B 2 O 3 , H 3 BO 4 , B (OH) 3 , Li 2 B 4 O 7 or a combination thereof.
혼합물을 소성하는 단계에서, 소성 온도는 300 내지 450℃가 될 수 있다.In the step of firing the mixture, the firing temperature may be 300 to 450 ° C.
본 발명의 또 다른 일 구현예에서는, 전술한 본 발명의 일 구현예에 따른 리튬 이차 전지용 양극 활물질을 포함하는 양극; 음극 활물질을 포함하는 음극; 및 전해질;을 포함하는 리튬 이차 전지를 제공한다. In another embodiment of the present invention, the positive electrode comprising a positive electrode active material for a lithium secondary battery according to an embodiment of the present invention described above; A negative electrode comprising a negative electrode active material; And electrolyte; provides a lithium secondary battery comprising a.
우수한 전지 특성을 갖는 양극 활물질 및 이를 포함하는 리튬 이차 전지를 제공할 수 있다.It is possible to provide a positive electrode active material having excellent battery characteristics and a lithium secondary battery comprising the same.
도 1은 리튬 이차 전지의 개략도이다. 1 is a schematic diagram of a lithium secondary battery.
이하, 본 발명의 구현예를 상세히 설명하기로 한다. 다만, 이는 예시로서 제시되는 것으로, 이에 의해 본 발명이 제한되지는 않으며 본 발명은 후술할 청구범위의 범주에 의해 정의될 뿐이다.Hereinafter, embodiments of the present invention will be described in detail. However, this is presented as an example, and the present invention is not limited thereby, and the present invention is only defined by the scope of claims to be described later.
본 발명의 일 구현예에서는, 하기 화학식 1로 표시되는 화합물을 포함하는 코어; 및 코어의 표면에 위치한 코팅층을 포함하는 리튬 이차 전지용 양극 활물질을 제공한다.In one embodiment of the present invention, a core comprising a compound represented by Formula 1 below; And it provides a positive electrode active material for a lithium secondary battery comprising a coating layer located on the surface of the core.
[화학식 1][Formula 1]
Li[LizA(1-z-a)Da]EbO2 -b Li [Li z A (1-za) D a ] E b O 2 -b
(상기 화학식 1에서 A는 NiαCoβMnγ이고, D는 Mg, Al, B, Zr, Mo, Nb 및 Ti로 이루어진 군에서 선택된 1종 이상의 원소이고, E는 P, F 및 S로 이루어진 군에서 선택된 1종 이상의 원소이고, -0.05 ≤ z ≤ 0.1, 0 ≤ a ≤ 0.05, 0 ≤ b ≤ 0.05, 0.3 ≤ α ≤ 0.9, 0.05≤ β≤0.4 및 0.05≤ γ≤0.4 이다.)(In Formula 1, A is Ni α Co β Mn γ , D is one or more elements selected from the group consisting of Mg, Al, B, Zr, Mo, Nb, and Ti, and E is composed of P, F, and S One or more elements selected from the group, -0.05 ≤ z ≤ 0.1, 0 ≤ a ≤ 0.05, 0 ≤ b ≤ 0.05, 0.3 ≤ α ≤ 0.9, 0.05 ≤ β ≤ 0.4 and 0.05 ≤ γ ≤ 0.4.)
화학식 1에서, -0.05 ≤ z ≤ 0.05, 0.6 ≤ α ≤ 0.9, 0.05≤ β≤0.2 및 0.05≤ γ≤0.2일 수 있다.In Formula 1, -0.05 ≤ z ≤ 0.05, 0.6 ≤ α ≤ 0.9, 0.05 ≤ β ≤ 0.2 and 0.05 ≤ γ ≤ 0.2.
본 발명의 일 구현예에 따른 양극 활물질은 리튬 이차 전지의 전지적 특성을 향상시킬 수 있다. 보다 구체적으로, 본 발명의 일 구현예에 따르면, 향상된 수명 특성을 가지는 양극 활물질을 제공할 수 있다.The positive electrode active material according to an embodiment of the present invention may improve the battery characteristics of a lithium secondary battery. More specifically, according to one embodiment of the present invention, a positive electrode active material having improved life characteristics can be provided.
화학식 1에서 D는 Mo, Nb, Zr, Ti 또는 이들의 조합일 수 있다. 구체적으로 화학식 1에서 D는 Mo, Nb 또는 이들의 조합일 수 있다. 더욱 구체적으로 D는 Mo 및 Nb로 구성되고, Zr 또는 Ti가 도핑된 것일 수 있다.D in Formula 1 may be Mo, Nb, Zr, Ti, or a combination thereof. Specifically, D in Formula 1 may be Mo, Nb, or a combination thereof. More specifically, D is composed of Mo and Nb, and Zr or Ti may be doped.
화학식 1에서 D의 몰 도핑비율은 0.001 내지 0.01일 수 있다.The molar doping ratio of D in Chemical Formula 1 may be 0.001 to 0.01.
몰리브덴은 전지특성에서 안전성, 열안정성을 향상시킨다. 몰리브덴의 함유량이, 너무 적으면 그 효과가 충분히 발휘되지 않고, 함유량이 너무 많으면 극도로 수명 특성이 악화된다.Molybdenum improves safety and thermal stability in battery characteristics. If the content of molybdenum is too small, the effect is not sufficiently exhibited, and if the content is too large, the lifespan characteristics deteriorate extremely.
니오브는 몰리브덴의 수명 특성이 악화 되는 것을 억제하며, 니오브의 함유량은 너무 적으면 그 효과가 충분히 발휘되지 않는다.Niobium suppresses deterioration of the life characteristics of molybdenum, and if the content of niobium is too small, the effect is not sufficiently exhibited.
또한, 몰리브덴 및 니오브 뿐 아니라 지르코늄 또는 티타늄을 더 포함 할 경우 다른 원소에 의한 특성 개선을 방해하는 일 없이 수명 특성을 더 개선시킬 수 있다.In addition, when molybdenum and niobium as well as zirconium or titanium are further included, the lifespan properties can be further improved without disturbing the improvement of properties by other elements.
본 발명의 일 구현예에 따른 양극 활물질은 코어 표면에 코팅층을 포함하며, 코어 표면 개질을 통하여 전해액과의 부반응을 억제하여 전지특성을 더욱 향상시킨다.The positive electrode active material according to one embodiment of the present invention includes a coating layer on the core surface, and further suppresses side reactions with the electrolyte through the modification of the core surface, thereby further improving battery characteristics.
코팅층은 Al, B 또는 이들의 조합을 포함할 수 있다. 코팅층은 F를 더 포함할 수 있다. 코팅층에 F를 더 포함하여 전해액과의 젖음성을 떨어뜨려 부반응을 억제하는 역할을 수행하여 표면 안정화를 더 시킬 수 있다. F는 코어 내에 포함되는 F에서 유래될 수 있다.The coating layer may include Al, B, or a combination thereof. The coating layer may further include F. By further including F in the coating layer, the wettability with the electrolytic solution is reduced to perform a role of suppressing side reactions to further stabilize the surface. F can be derived from F included in the core.
양극 활물질의 총 중량에 대하여 코팅층의 함량은 0.05 내지 1.0 중량%가 될 수 있다. 코팅층의 중량비가 너무 적은 경우 코팅층의 역할이 감소할 수 있으며, 코팅층의 중량비가 너무 많은 경우 초기용량 감소 및 충방전 효율의 감소가 나타날 수 있다. 다만, 이에 제한되는 것은 아니다.The content of the coating layer relative to the total weight of the positive electrode active material may be 0.05 to 1.0% by weight. When the weight ratio of the coating layer is too small, the role of the coating layer may decrease, and when the weight ratio of the coating layer is too large, initial capacity reduction and charge / discharge efficiency may decrease. However, it is not limited thereto.
본 발명의 다른 일 구현예에서는, 하기 화학식 1로 표시되는 화합물을 포함하는 코어를 준비하는 단계; 코어와 코팅층을 형성하는 원료 화합물을 혼합하여 혼합물을 제조하는 단계; 및 혼합물을 소성하는 단계를 포함하는 리튬 이차 전지용 양극 활물질의 제조 방법을 제공한다.In another embodiment of the present invention, preparing a core comprising a compound represented by Formula 1 below; Preparing a mixture by mixing a core and a raw material compound forming a coating layer; And it provides a method for producing a positive electrode active material for a lithium secondary battery comprising the step of firing the mixture.
[화학식 1][Formula 1]
Li[LizA(1-z-a)Da]EbO2 -b Li [Li z A (1-za) D a ] E b O 2 -b
(상기 화학식 1에서 A는 NiαCoβMnγ이고, D는 Mg, Al, B, Zr, Mo, Nb 및 Ti로 이루어진 군에서 선택된 1종 이상의 원소이고, E는 P, F 및 S로 이루어진 군에서 선택된 1종 이상의 원소이고, -0.05 ≤ z ≤ 0.1, 0 ≤ a ≤ 0.05, 0 ≤ b ≤ 0.05, 0.3 ≤ α ≤ 0.9, 0.05≤ β≤0.4 및 0.05≤ γ≤0.4 이다.)(In Formula 1, A is Ni α Co β Mn γ , D is one or more elements selected from the group consisting of Mg, Al, B, Zr, Mo, Nb, and Ti, and E is composed of P, F, and S One or more elements selected from the group, -0.05 ≤ z ≤ 0.1, 0 ≤ a ≤ 0.05, 0 ≤ b ≤ 0.05, 0.3 ≤ α ≤ 0.9, 0.05 ≤ β ≤ 0.4 and 0.05 ≤ γ ≤ 0.4.)
이하에서는 리튬 이차전지용 양극 활물질의 제조 방법을 각 단계별로 구체적으로 설명한다.Hereinafter, a method of manufacturing a positive electrode active material for a lithium secondary battery will be described in detail for each step.
먼저, 화학식 1로 표시되는 화합물을 포함하는 코어를 준비한다. 화학식 1로 표시되는 화합물에 대해서는 전술하였으므로, 반복되는 설명은 생략한다.First, a core including a compound represented by Chemical Formula 1 is prepared. Since the compound represented by Formula 1 has been described above, repeated description is omitted.
다음으로, 코어와 코팅층을 형성하는 원료 화합물을 혼합하여 혼합물을 제조한다.Next, a mixture is prepared by mixing a core and a raw material compound forming a coating layer.
원료 화합물은 알루미늄 공급원, 붕소 공급원 또는 이들의 조합일 수 있다. 구체적으로 알루미늄 공급원은 Al2O3, Al(OH)3, AlPO4, Al(NO3)3 또는 이들의 조합일 수 있다. 또한 붕소 공급원은 B2O3, H3BO4, B(OH)3, Li2B4O7 또는 이들의 조합일 수 있다.The raw compound can be an aluminum source, a boron source, or a combination thereof. Specifically, the aluminum source may be Al 2 O 3 , Al (OH) 3 , AlPO 4 , Al (NO 3 ) 3 or a combination thereof. In addition, the boron source may be B 2 O 3 , H 3 BO 4 , B (OH) 3 , Li 2 B 4 O 7 or a combination thereof.
다음으로, 혼합물을 소성한다. 이 때, 소성 온도는 300 내지 450℃가 될 수 있다. 소성 온도가 너무 낮은 경우에는 코팅층과 코어 간의 반응성이 떨어져 코팅층의 유리(遊離) 등 코팅의 효과를 기대하기 어렵다. 또한, 소성 온도가 너무 높은 경우에는 Al 및 B 공급 물질이 코어에 과도하게 부착됨으로써 전지의 초기 용량의 감소와 함께 상온, 고온 및 저온에서의 수명 특성 저하가 일어날 수 있다.Next, the mixture is calcined. At this time, the firing temperature may be 300 to 450 ° C. When the firing temperature is too low, the reactivity between the coating layer and the core is poor, so it is difficult to expect the effect of coating such as glass of the coating layer. In addition, when the firing temperature is too high, the Al and B feed materials are excessively attached to the core, so that the initial capacity of the battery may decrease and the life characteristics at room temperature, high temperature, and low temperature may deteriorate.
제조된 양극 활물질에 대한 설명은 앞서 설명된 본 발명의 일 구현예와 동일하므로 구체적인 설명은 생략하도록 한다.Description of the prepared positive electrode active material is the same as one embodiment of the present invention described above, so a detailed description thereof will be omitted.
본 발명의 또 다른 일 구현예에서는, 양극, 음극 및 전해질을 포함하는 리튬 이차 전지며, 양극은 전류 집전체 및 전류 집전체 상에 형성된 양극 활물질층을 포함하며, 양극 활물질층은, 전술한 양극 활물질을 포함하는 것인 리튬 이차 전지를 제공한다. In another embodiment of the present invention, a lithium secondary battery including a positive electrode, a negative electrode, and an electrolyte, the positive electrode includes a current collector and a positive electrode active material layer formed on the current collector, and the positive electrode active material layer includes the positive electrode described above It provides a lithium secondary battery containing an active material.
양극 활물질과 관련된 설명은 전술한 본 발명의 일 구현예와 동일하기 때문에 중복되는 설명을 생략하도록 한다. Description of the positive electrode active material is the same as the one embodiment of the present invention described above, so a duplicate description will be omitted.
상기 양극 활물질층은 바인더 및 도전재를 포함할 수 있다. The positive electrode active material layer may include a binder and a conductive material.
상기 바인더는 양극 활물질 입자들을 서로 잘 부착시키고, 또한 양극 활물질을 전류 집전체에 잘 부착시키는 역할을 하며, 그 대표적인 예로는 폴리비닐알콜, 카르복시메틸셀룰로즈, 히드록시프로필셀룰로즈, 디아세틸셀룰로즈, 폴리비닐클로라이드, 카르복실화된 폴리비닐클로라이드, 폴리비닐플루오라이드, 에틸렌 옥사이드를 포함하는 폴리머, 폴리비닐피롤리돈, 폴리우레탄, 폴리테트라플루오로에틸렌, 폴리비닐리덴 플루오라이드, 폴리에틸렌, 폴리프로필렌, 스티렌-부타디엔 러버, 아크릴레이티드 스티렌-부타디엔 러버, 에폭시 수지, 나일론 등을 사용할 수 있으나, 이에 한정되는 것은 아니다.The binder serves to adhere the positive electrode active material particles to each other well, and also serves to adhere the positive electrode active material to the current collector, and typical examples thereof include polyvinyl alcohol, carboxymethyl cellulose, hydroxypropyl cellulose, diacetyl cellulose, and polyvinyl. Chloride, carboxylated polyvinylchloride, polyvinylfluoride, polymers containing ethylene oxide, polyvinylpyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, styrene- Butadiene rubber, acrylate-styrene-butadiene rubber, epoxy resin, nylon, etc. may be used, but is not limited thereto.
상기 도전재는 전극에 도전성을 부여하기 위해 사용되는 것으로서, 구성되는 전지에 있어서, 화학변화를 야기하지 않고 전자 전도성 재료이면 어떠한 것도 사용가능하며, 그 예로 천연 흑연, 인조 흑연, 카본 블랙, 아세틸렌 블랙, 케첸블랙, 탄소섬유 등의 탄소계 물질; 구리, 니켈, 알루미늄, 은 등의 금속 분말 또는 금속 섬유 등의 금속계 물질; 폴리페닐렌 유도체 등의 도전성 폴리머; 또는 이들의 혼합물을 포함하는 도전성 재료를 사용할 수 있다.The conductive material is used to impart conductivity to the electrode, and in the battery to be constructed, any material can be used as long as it is an electronically conductive material without causing chemical changes. Examples include natural graphite, artificial graphite, carbon black, acetylene black, and ketjen. Carbon-based materials such as black and carbon fibers; Metal powders such as copper, nickel, aluminum, silver, or metal fibers; Conductive polymers such as polyphenylene derivatives; Alternatively, a conductive material containing a mixture of these can be used.
상기 음극은 집전체 및 상기 집전체 위에 형성된 음극 활물질층을 포함하며, 상기 음극 활물질층은 음극 활물질을 포함한다.The negative electrode includes a current collector and a negative electrode active material layer formed on the current collector, and the negative electrode active material layer includes a negative electrode active material.
상기 음극 활물질로는 리튬 이온을 가역적으로 인터칼레이션/디인터칼레이션할 수 있는 물질, 리튬 금속, 리튬 금속의 합금, 리튬을 도프 및 탈도프할 수 있는 물질, 또는 전이 금속 산화물을 포함한다. The negative active material includes a material capable of reversibly intercalating / deintercalating lithium ions, a lithium metal, an alloy of lithium metal, a material capable of doping and dedoping lithium, or a transition metal oxide.
상기 리튬 이온을 가역적으로 인터칼레이션/디인터칼레이션할 수 있는 물질로는 탄소 물질로서, 리튬 이온 이차 전지에서 일반적으로 사용되는 탄소계 음극 활물질은 어떠한 것도 사용할 수 있으며, 그 대표적인 예로는 결정질 탄소, 비정질 탄소 또는 이들을 함께 사용할 수 있다. 상기 결정질 탄소의 예로는 무정형, 판상, 린편상(flake), 구형 또는 섬유형의 천연 흑연 또는 인조 흑연과 같은 흑연을 들 수 있고, 상기 비정질 탄소의 예로는 소프트 카본(soft carbon: 저온 소성 탄소) 또는 하드 카본(hard carbon), 메조페이스 피치 탄화물, 소성된 코크스 등을 들 수 있다.As a material capable of reversibly intercalating / deintercalating the lithium ions, a carbon-based negative active material commonly used in lithium-ion secondary batteries can be used, and representative examples thereof include crystalline carbon , Amorphous carbon or a combination of these. Examples of the crystalline carbon include graphite such as amorphous, plate-like, lean flake, spherical or fibrous natural graphite or artificial graphite, and examples of the amorphous carbon include soft carbon (low temperature calcined carbon). Or hard carbon, mesophase pitch carbide, calcined coke, and the like.
상기 리튬 금속의 합금으로는 리튬과 Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Si, Sb, Pb, In, Zn, Ba, Ra, Ge, Al 및 Sn으로 이루어진 군에서 선택되는 금속의 합금이 사용될 수 있다.The lithium metal alloy is lithium and Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Si, Sb, Pb, In, Zn, Ba, Ra, Ge, Al and Sn. The alloy of the metal of choice can be used.
상기 리튬을 도프 및 탈도프할 수 있는 물질로는 Si, SiOx(0 < x < 2), Si-Y 합금(상기 Y는 알칼리 금속, 알칼리 토금속, 13족 원소, 14족 원소, 전이금속, 희토류 원소 및 이들의 조합으로 이루어진 군에서 선택되는 원소이며, Si은 아님), Sn, SnO2, Sn-Y(상기 Y는 알칼리 금속, 알칼리 토금속, 13족 원소, 14족 원소, 전이금속, 희토류 원소 및 이들의 조합으로 이루어진 군에서 선택되는 원소이며, Sn은 아님) 등을 들 수 있고, 또한 이들 중 적어도 하나와 SiO2를 혼합하여 사용할 수도 있다. 상기 원소 Y로는 Mg, Ca, Sr, Ba, Ra, Sc, Y, Ti, Zr, Hf, Rf, V, Nb, Ta, Db, Cr, Mo, W, Sg, Tc, Re, Bh, Fe, Pb, Ru, Os, Hs, Rh, Ir, Pd, Pt, Cu, Ag, Au, Zn, Cd, B, Al, Ga, Sn, In, Ti, Ge, P, As, Sb, Bi, S, Se, Te, Po, 및 이들의 조합으로 이루어진 군에서 선택될 수 있다.Materials capable of doping and dedoping the lithium include Si, SiO x (0 <x <2), and Si-Y alloys (where Y is an alkali metal, alkaline earth metal, group 13 element, group 14 element, transition metal, Rare earth elements and elements selected from the group consisting of a combination thereof, not Si), Sn, SnO 2 , Sn-Y (Y is an alkali metal, alkaline earth metal, group 13 element, group 14 element, transition metal, rare earth) An element and a combination of these, and not Sn), and the like, and SiO 2 may be mixed with at least one of them. The elements Y are Mg, Ca, Sr, Ba, Ra, Sc, Y, Ti, Zr, Hf, Rf, V, Nb, Ta, Db, Cr, Mo, W, Sg, Tc, Re, Bh, Fe, Pb, Ru, Os, Hs, Rh, Ir, Pd, Pt, Cu, Ag, Au, Zn, Cd, B, Al, Ga, Sn, In, Ti, Ge, P, As, Sb, Bi, S, Se, Te, Po, and combinations thereof.
상기 전이 금속 산화물로는 바나듐 산화물, 리튬 바나듐 산화물 등을 들 수 있다.Examples of the transition metal oxide include vanadium oxide and lithium vanadium oxide.
상기 음극 활물질 층은 또한 바인더를 포함하며, 선택적으로 도전재를 더욱 포함할 수도 있다.The negative active material layer also includes a binder, and may optionally further include a conductive material.
상기 바인더는 음극 활물질 입자들을 서로 잘 부착시키고, 또한 음극 활물질을 전류 집전체에 잘 부착시키는 역할을 하며, 그 대표적인 예로 폴리비닐알콜, 카르복시메틸셀룰로즈, 히드록시프로필셀룰로즈, 폴리비닐클로라이드, 카르복실화된 폴리비닐클로라이드, 폴리비닐플루오라이드, 에틸렌 옥사이드를 포함하는 폴리머, 폴리비닐피롤리돈, 폴리우레탄, 폴리테트라플루오로에틸렌, 폴리비닐리덴 플루오라이드, 폴리에틸렌, 폴리프로필렌, 스티렌-부타디엔 러버, 아크릴레이티드 스티렌-부타디엔 러버, 에폭시 수지, 나일론 등을 사용할 수 있으나, 이에 한정되는 것은 아니다.The binder adheres the negative electrode active material particles to each other well, and also serves to adhere the negative electrode active material to the current collector well. Representative examples thereof include polyvinyl alcohol, carboxymethyl cellulose, hydroxypropyl cellulose, polyvinyl chloride, and carboxylation. Polyvinyl chloride, polyvinyl fluoride, polymer containing ethylene oxide, polyvinylpyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, styrene-butadiene rubber, acryl Tited styrene-butadiene rubber, epoxy resin, nylon, etc. may be used, but is not limited thereto.
상기 도전재는 전극에 도전성을 부여하기 위해 사용되는 것으로서, 구성되는 전지에 있어서, 화학변화를 야기하지 않고 전자 전도성 재료이면 어떠한 것도 사용가능하며, 그 예로 천연 흑연, 인조 흑연, 카본 블랙, 아세틸렌 블랙, 케첸블랙, 탄소섬유 등의 탄소계 물질; 구리, 니켈, 알루미늄, 은 등의 금속 분말 또는 금속 섬유 등의 금속계 물질; 폴리페닐렌 유도체 등의 도전성 폴리머; 또는 이들의 혼합물을 포함하는 도전성 재료를 사용할 수 있다.The conductive material is used to impart conductivity to the electrode, and in the battery to be constructed, any material can be used as long as it is an electronically conductive material without causing chemical changes. Examples include natural graphite, artificial graphite, carbon black, acetylene black, and ketjen. Carbon-based materials such as black and carbon fibers; Metal powders such as copper, nickel, aluminum, silver, or metal fibers; Conductive polymers such as polyphenylene derivatives; Alternatively, a conductive material containing a mixture of these can be used.
상기 집전체로는 구리 박, 니켈 박, 스테인레스강 박, 티타늄 박, 니켈 발포체(foam), 구리 발포체, 전도성 금속이 코팅된 폴리머 기재, 및 이들의 조합으로 이루어진 군에서 선택되는 것을 사용할 수 있다.The current collector may be selected from the group consisting of copper foil, nickel foil, stainless steel foil, titanium foil, nickel foam, copper foam, a polymer substrate coated with a conductive metal, and combinations thereof.
상기 전류 집전체로는 Al을 사용할 수 있으나 이에 한정되는 것은 아니다.Al may be used as the current collector, but is not limited thereto.
상기 음극과 양극은 활물질, 도전재 및 결착제를 용매 중에서 혼합하여 활물질 조성물을 제조하고, 이 조성물을 전류 집전체에 도포하여 제조한다. 이와 같은 전극 제조 방법은 당해 분야에 널리 알려진 내용이므로 본 명세서에서 상세한 설명은 생략하기로 한다. 상기 용매로는 N-메틸피롤리돈 등을 사용할 수 있으나 이에 한정되는 것은 아니다.The negative electrode and the positive electrode are prepared by mixing an active material, a conductive material, and a binder in a solvent to prepare an active material composition, and applying the composition to a current collector. Since such an electrode manufacturing method is widely known in the art, detailed descriptions thereof will be omitted. N-methylpyrrolidone or the like may be used as the solvent, but is not limited thereto.
상기 전해질은 비수성 유기 용매와 리튬염을 포함한다. The electrolyte contains a non-aqueous organic solvent and a lithium salt.
상기 비수성 유기 용매는 전지의 전기화학적 반응에 관여하는 이온들이 이동할 수 있는 매질 역할을 한다. The non-aqueous organic solvent serves as a medium through which ions involved in the electrochemical reaction of the battery can move.
상기 비수성 유기용매로는 카보네이트계, 에스테르계, 에테르계, 케톤계, 알코올계, 또는 비양성자성 용매를 사용할 수 있다. 상기 카보네이트계 용매로는 디메틸 카보네이트(DMC), 디에틸 카보네이트(DEC), 디프로필 카보네이트(DPC), 메틸프로필 카보네이트(MPC), 에틸프로필 카보네이트(EPC), 메틸에틸 카보네이트(MEC), 에틸렌 카보네이트(EC), 프로필렌 카보네이트(PC), 부틸렌 카보네이트(BC) 등이 사용될 수 있으며, 상기 에스테르계 용매로는 메틸 아세테이트, 에틸 아세테이트, n-프로필 아세테이트, 디메틸아세테이트, 메틸프로피오네이트, 에틸프로피오네이트, γ-부티로락톤, 데카놀라이드(decanolide), 발레로락톤, 메발로노락톤(mevalonolactone), 카프로락톤(caprolactone), 등이 사용될 수 있다. 상기 에테르계 용매로는 디부틸 에테르, 테트라글라임, 디글라임, 디메톡시에탄, 2-메틸테트라히드로퓨란, 테트라히드로퓨란 등이 사용될 수 있으며, 상기 케톤계 용매로는 시클로헥사논 등이 사용될 수 있다. 또한 상기 알코올계 용매로는 에틸알코올, 이소프로필 알코올 등이 사용될 수 있으며, 상기 비양성자성 용매로는 R-CN(R은 탄소수 2 내지 20의 직쇄상, 분지상, 또는 환 구조의 탄화수소기이며, 이중결합 방향 환 또는 에테르 결합을 포함할 수 있다) 등의 니트릴류 디메틸포름아미드 등의 아미드류, 1,3-디옥솔란 등의 디옥솔란류 설포란(sulfolane)류 등이 사용될 수 있다. As the non-aqueous organic solvent, a carbonate-based, ester-based, ether-based, ketone-based, alcohol-based, or aprotic solvent may be used. The carbonate-based solvent includes dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC), methylpropyl carbonate (MPC), ethylpropyl carbonate (EPC), methylethyl carbonate (MEC), and ethylene carbonate ( EC), propylene carbonate (PC), butylene carbonate (BC), etc. can be used, and the ester solvents include methyl acetate, ethyl acetate, n-propyl acetate, dimethyl acetate, methyl propionate, and ethyl propionate. , γ-butyrolactone, decanolide, valerolactone, mevalonolactone, caprolactone, and the like can be used. Dibutyl ether, tetraglyme, diglyme, dimethoxyethane, 2-methyltetrahydrofuran, tetrahydrofuran, etc. may be used as the ether-based solvent, and cyclohexanone may be used as the ketone-based solvent. have. In addition, ethyl alcohol, isopropyl alcohol, etc. may be used as the alcohol-based solvent, and the aprotic solvent is R-CN (R is a straight-chain, branched, or ring hydrocarbon group having 2 to 20 carbon atoms. , May include a double bond aromatic ring or an ether bond) amides such as nitrile dimethylformamide, dioxolanes such as 1,3-dioxolane, and sulfolanes.
상기 비수성 유기 용매는 단독으로 또는 하나 이상 혼합하여 사용할 수 있으며, 하나 이상 혼합하여 사용하는 경우의 혼합 비율은 목적하는 전지 성능에 따라 적절하게 조절할 수 있고, 이는 당해 분야에 종사하는 사람들에게는 널리 이해될 수 있다.The non-aqueous organic solvent may be used alone or in combination of one or more, and the mixing ratio when used in combination with one or more can be appropriately adjusted according to the desired battery performance, which is widely understood by those skilled in the art. Can be.
또한, 상기 카보네이트계 용매의 경우 환형(cyclic) 카보네이트와 사슬형(chain) 카보네이트를 혼합하여 사용하는 것이 좋다. 이 경우 환형 카보네이트와 사슬형 카보네이트는 1:1 내지 1:9의 부피비로 혼합하여 사용하는 것이 전해액의 성능이 우수하게 나타날 수 있다. In addition, in the case of the carbonate-based solvent, it is preferable to use a mixture of cyclic carbonate and chain carbonate. In this case, the mixture of the cyclic carbonate and the chain carbonate in a volume ratio of 1: 1 to 1: 9 may be used to exhibit excellent electrolyte performance.
본 발명의 일 구현예에 따른 비수성 유기용매는 상기 카보네이트계 용매에 방향족 탄화수소계 유기용매를 더 포함할 수도 있다. 이때 상기 카보네이트계 용매와 방향족 탄화수소계 유기용매는 1:1 내지 30:1의 부피비로 혼합될 수 있다.The non-aqueous organic solvent according to an embodiment of the present invention may further include an aromatic hydrocarbon-based organic solvent in the carbonate-based solvent. At this time, the carbonate-based solvent and the aromatic hydrocarbon-based organic solvent may be mixed in a volume ratio of 1: 1 to 30: 1.
상기 방향족 탄화수소계 유기용매로는 하기 화학식 2의 방향족 탄화수소계 화합물이 사용될 수 있다.As the aromatic hydrocarbon-based organic solvent, an aromatic hydrocarbon-based compound of
[화학식 2][Formula 2]
(상기 화학식 2에서, R1 내지 R6는 각각 독립적으로 수소, 할로겐, C1 내지 C10 알킬기, 할로알킬기 또는 이들의 조합이다.)(In
상기 방향족 탄화수소계 유기용매는 벤젠, 플루오로벤젠, 1,2-디플루오로벤젠, 1,3-디플루오로벤젠, 1,4-디플루오로벤젠, 1,2,3-트리플루오로벤젠, 1,2,4-트리플루오로벤젠, 클로로벤젠, 1,2-디클로로벤젠, 1,3-디클로로벤젠, 1,4-디클로로벤젠, 1,2,3-트리클로로벤젠, 1,2,4-트리클로로벤젠, 아이오도벤젠, 1,2-디아이오도벤젠, 1,3-디아이오도벤젠, 1,4-디아이오도벤젠, 1,2,3-트리아이오도벤젠, 1,2,4-트리아이오도벤젠, 톨루엔, 플루오로톨루엔, 1,2-디플루오로톨루엔, 1,3-디플루오로톨루엔, 1,4-디플루오로톨루엔, 1,2,3-트리플루오로톨루엔, 1,2,4-트리플루오로톨루엔, 클로로톨루엔, 1,2-디클로로톨루엔, 1,3-디클로로톨루엔, 1,4-디클로로톨루엔, 1,2,3-트리클로로톨루엔, 1,2,4-트리클로로톨루엔, 아이오도톨루엔, 1,2-디아이오도톨루엔, 1,3-디아이오도톨루엔, 1,4-디아이오도톨루엔, 1,2,3-트리아이오도톨루엔, 1,2,4-트리아이오도톨루엔, 자일렌, 및 이들의 조합으로 이루어진 군에서 선택되는 것이다.The aromatic hydrocarbon-based organic solvent is benzene, fluorobenzene, 1,2-difluorobenzene, 1,3-difluorobenzene, 1,4-difluorobenzene, 1,2,3-trifluorobenzene , 1,2,4-trifluorobenzene, chlorobenzene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,4-dichlorobenzene, 1,2,3-trichlorobenzene, 1,2, 4-trichlorobenzene, iodobenzene, 1,2-diiodobenzene, 1,3-diiodobenzene, 1,4-diiodobenzene, 1,2,3-triiodobenzene, 1,2,4 -Triiodobenzene, toluene, fluorotoluene, 1,2-difluorotoluene, 1,3-difluorotoluene, 1,4-difluorotoluene, 1,2,3-trifluorotoluene, 1,2,4-trifluorotoluene, chlorotoluene, 1,2-dichlorotoluene, 1,3-dichlorotoluene, 1,4-dichlorotoluene, 1,2,3-trichlorotoluene, 1,2,4 -Trichlorotoluene, iodotoluene, 1,2-diaiodotoluene, 1,3-diaiodotoluene, 1,4-diaiodotoluene, 1,2,3-triiodotoluene, 1,2,4- Triiodotoluene, xylene, and combinations thereof.
상기 비수성 전해질은 전지 수명을 향상시키기 위하여 비닐렌 카보네이트 또는 하기 화학식 3의 에틸렌 카보네이트계 화합물을 더욱 포함할 수도 있다.The non-aqueous electrolyte may further include vinylene carbonate or an ethylene carbonate-based compound of
[화학식 3][Formula 3]
(상기 화학식 3에서, R7 및 R8는 각각 독립적으로 수소, 할로겐기, 시아노기(CN), 니트로기(NO2) 또는 C1 내지 C5 플루오로알킬기이고, 상기 R7과 R8중 적어도 하나는 할로겐기, 시아노기(CN), 니트로기(NO2) 또는 C1 내지 C5의 플루오로알킬기이다.)(In the
상기 에틸렌 카보네이트계 화합물의 대표적인 예로는 디플루오로 에틸렌카보네이트, 클로로에틸렌 카보네이트, 디클로로에틸렌 카보네이트, 브로모에틸렌 카보네이트, 디브로모에틸렌 카보네이트, 니트로에틸렌 카보네이트, 시아노에틸렌 카보네이트 또는 플루오로에틸렌 카보네이트 등을 들 수 있다. 이러한 수명 향상 첨가제를 더욱 사용하는 경우 그 사용량은 적절하게 조절할 수 있다.Representative examples of the ethylene carbonate-based compound include difluoro ethylene carbonate, chloroethylene carbonate, dichloroethylene carbonate, bromoethylene carbonate, dibromoethylene carbonate, nitroethylene carbonate, cyanoethylene carbonate or fluoroethylene carbonate. Can be. When further using such a life-enhancing additive, the amount thereof can be appropriately adjusted.
상기 리튬염은 유기 용매에 용해되어, 전지 내에서 리튬 이온의 공급원으로 작용하여 기본적인 리튬 이차 전지의 작동을 가능하게 하고, 양극과 음극 사이의 리튬 이온의 이동을 촉진하는 역할을 하는 물질이다. 이러한 리튬염의 대표적인 예로는 LiPF6, LiBF4, LiSbF6, LiAsF6, LiC4F9SO3, LiClO4, LiAlO2, LiAlCl4, LiN(CxF2x+1SO2)(CyF2y+1SO2)(여기서, x 및 y는 자연수임), LiCl, LiI 및 LiB(C2O4)2(리튬 비스옥살레이토 보레이트(lithium bis(oxalato) borate; LiBOB)로 이루어진 군에서 선택되는 하나 또는 둘 이상을 지지(supporting) 전해염으로 포함한다. 리튬염의 농도는 0.1 내지 2.0M 범위 내에서 사용하는 것이 좋다. 리튬염의 농도가 상기 범위에 포함되면, 전해질이 적절한 전도도 및 점도를 가지므로 우수한 전해질 성능을 나타낼 수 있고, 리튬 이온이 효과적으로 이동할 수 있다.The lithium salt is a material that dissolves in an organic solvent, acts as a source of lithium ions in the battery, enables basic lithium secondary battery operation, and promotes movement of lithium ions between the positive electrode and the negative electrode. LiPF 6 , LiBF 4 , LiSbF 6 , LiAsF 6 , LiC 4 F 9 SO 3 , LiClO 4 , LiAlO 2 , LiAlCl 4 , LiN (C x F 2x + 1 SO 2 ) (C y F 2y) +1 SO 2 ) (where x and y are natural numbers), LiCl, LiI and LiB (C 2 O 4 ) 2 (lithium bis (oxalato) borate; LiBOB) It contains one or two or more as a supporting electrolytic salt, and the concentration of the lithium salt is preferably used within the range of 0.1 to 2.0 M. When the concentration of the lithium salt is included in the above range, the electrolyte has an appropriate conductivity and viscosity. It can exhibit excellent electrolyte performance, and lithium ions can effectively move.
리튬 이차 전지의 종류에 따라 양극과 음극 사이에 세퍼레이터가 존재할 수 도 있다. 이러한 세퍼레이터로는 폴리에틸렌, 폴리프로필렌, 폴리비닐리덴 플루오라이드 또는 이들의 2층 이상의 다층막이 사용될 수 있으며, 폴리에틸렌/폴리프로필렌 2층 세퍼레이터, 폴리에틸렌/폴리프로필렌/폴리에틸렌 3층 세퍼레이터, 폴리프로필렌/폴리에틸렌/폴리프로필렌 3층 세퍼레이터 등과 같은 혼합 다층막이 사용될 수 있음은 물론이다.Depending on the type of lithium secondary battery, a separator may exist between the positive electrode and the negative electrode. As the separator, polyethylene, polypropylene, polyvinylidene fluoride, or a multilayer film of two or more layers thereof may be used, a polyethylene / polypropylene two-layer separator, a polyethylene / polypropylene / polyethylene three-layer separator, polypropylene / polyethylene / poly It goes without saying that a mixed multilayer film such as a propylene three-layer separator can be used.
리튬 이차 전지는 사용하는 세퍼레이터와 전해질의 종류에 따라 리튬 이온 전지, 리튬 이온 폴리머 전지 및 리튬 폴리머 전지로 분류될 수 있고, 형태에 따라 원통형, 각형, 코인형, 파우치형 등으로 분류될 수 있으며, 사이즈에 따라 벌크 타입과 박막 타입으로 나눌 수 있다. 이들 전지의 구조와 제조방법은 이 분야에 널리 알려져 있으므로 상세한 설명은 생략한다.The lithium secondary battery may be classified into a lithium ion battery, a lithium ion polymer battery, and a lithium polymer battery according to the type of separator and electrolyte used, and may be classified into a cylindrical shape, a square shape, a coin shape, and a pouch shape according to the shape, It can be divided into bulk type and thin film type depending on the size. The structure and manufacturing method of these batteries are well known in the art, so detailed descriptions thereof are omitted.
도 1에 본 발명의 리튬 이차 전지의 대표적인 구조를 개략적으로 나타내었다. 도 1에 나타낸 것과 같이 상기 리튬 이차 전지(1)는 양극(3), 음극(2) 및 상기 양극(3)과 음극(2) 사이에 존재하는 세퍼레이터(4)에 함침된 전해액을 포함하는 전지 용기(5)와, 상기 전지 용기(5)를 봉입하는 봉입 부재(6)를 포함한다.1 schematically shows a representative structure of the lithium secondary battery of the present invention. As illustrated in FIG. 1, the lithium secondary battery 1 is a battery including an
이하 본 발명의 실시예 및 비교예를 기재한다. 그러나 하기의 실시예는 본 발명의 일 실시예 일 뿐 본 발명이 하기한 실시예에 한정되는 것은 아니다.Hereinafter, examples and comparative examples of the present invention will be described. However, the following examples are only examples of the present invention, and the present invention is not limited to the following examples.
실시예Example
실시예Example 1 One
믹서에 NCM 복합 전이 금속수산화물(몰비는 Ni:Co:Mn = 60:20:20)과 분산된 MoO2 분말과 Nb2O5 분말, Li2CO3 분말을 건식 혼합하였다. 그리고, 건식 혼합된 분말을 890℃에서 8시간 동안 열처리하여 Li1 .01Ni0 .60Co0 .20Mn0 .20Mo0 .01Nb0 .005O2 로 표시되는 리튬 복합 화합물을 제조하였다.In the mixer, NCM composite transition metal hydroxide (molar ratio of Ni: Co: Mn = 60:20:20) and dispersed MoO 2 powder, Nb 2 O 5 powder, and Li 2 CO 3 powder were dry mixed. And, to the dry mixed powder heat treated at 890 ℃ for 8 hours, the lithium composite compound represented by Li 1 .01 Ni 0 .60 Co 0 .20 Mn 0 .20 Mo 0 .01 Nb 0 .005
또한, 제조된 리튬 복합 화합물을 리튬 복합 화합물 : Al(OH)3 분말 : B2O3 분말 = 100:0.4:0.2의 중량비율로 건식 혼합한 후 소성하여, 분산된 Al(OH)3 분말과 B2O3 분말이 상기 리튬 복합 화합물 표면에 균일하게 부착되도록 하였다. 그리고, 건식 혼합된 분말을 400 ℃에서 6시간 동안 열처리하여 양극 활물질을 제조하였다.In addition, the prepared lithium composite compound is a lithium composite compound: Al (OH) 3 powder: B 2 O 3 powder = 100: 0.4: 0.2 by dry mixing at a weight ratio and calcined to disperse the Al (OH) 3 powder. The B 2 O 3 powder was uniformly attached to the surface of the lithium composite compound. Then, the dry-mixed powder was heat-treated at 400 ° C. for 6 hours to prepare a positive electrode active material.
실시예Example 2 2
실시예 1에서 Li1 .01Ni0 .60Co0 .20Mn0 .20Mo0 .01Nb0 .005Zr0 .005O2로 표시되는 리튬 복합 화합물을 제조한 것을 제외하고 동일하게 양극 활물질을 제조하였다.Example 1 In the Li 1 .01 Ni 0 .60 Co 0 .20 Mn 0 .20 Mo 0 .01 Nb 0 .005 Zr 0 .005 O and the same positive electrode active material, except that the prepared lithium composite compounds represented by the 2 Was prepared.
실시예Example 3 3
실시예 1에서 Li1 .01Ni0 .60Co0 .20Mn0 .20Mo0 .01Nb0 .005Ti0 .005O2로 표시되는 리튬 복합 화합물을 제조한 것을 제외하고 동일하게 양극 활물질을 제조하였다.Example 1 In the Li 1 .01 Ni 0 .60 Co 0 .20 Mn 0 .20 Mo 0 .01 Nb 0 .005 Ti 0 .005 O and the same positive electrode active material, except that the prepared lithium composite compounds represented by the 2 Was prepared.
비교예Comparative example 1 One
믹서에 NCM 복합 전이 금속수산화물(몰비는 Ni:Co:Mn = 60:20:20) 1몰에 대해 Li2CO3이 1.01몰이 되는 비율(Li/Metal=1.01)로 Li2CO3을 넣고 건식 혼합하였다. 그리고, 건식 혼합된 분말을 890℃에서 8시간 동안 열처리하여 양극 활물질을 제조하였다.NCM composite transition metal hydroxide in the mixer (a molar ratio of Ni: Co: Mn = 60:20:20) of about 1 mol Li 2 CO 3 1.01 Li 2 CO 3 to be put into the mole ratio (Li / Metal = 1.01) dry Mixed. Then, the dry-mixed powder was heat treated at 890 ° C. for 8 hours to prepare a positive electrode active material.
비교예Comparative example 2 2
믹서에 NCM 복합 전이 금속수산화물(몰비는 Ni:Co:Mn = 60:20:20)과 분산된 MoO2 분말과 Nb2O5 분말, Li2CO3 분말을 건식 혼합하였다. 그리고, 건식 혼합된 분말을 890℃에서 8시간 동안 열처리하여 Li1 .01Ni0 .60Co0 .20Mn0 .20Mo0 .01Nb0 .005O2 로 표시되는 리튬 복합 화합물을 제조하였다.In the mixer, NCM composite transition metal hydroxide (molar ratio of Ni: Co: Mn = 60:20:20) and dispersed MoO 2 powder, Nb 2 O 5 powder, and Li 2 CO 3 powder were dry mixed. Then, the dry mixed powder at 890 ℃ for 8 hours heat treatment by Li 1 .01 Ni 0 .60 Co 0 .20 Mn 0 .20 Mo 0 .01 Nb 0 .005 O 2 A lithium composite compound represented by was prepared.
비교예Comparative example 3 3
비교예 1에서 제조된 리튬 복합 화합물을 상기 리튬 복합 화합물 : Al(OH)3 분말 : B2O3 분말 = 100:0.4:0.2의 중량비율로 건식 혼합한 후 소성하여, 분산된 Al(OH)3 분말과 B2O3 분말이 상기 리튬 복합 화합물 표면에 균일하게 부착되도록 하였다. 그리고, 건식 혼합된 분말을 400 ℃에서 6시간 동안 열처리하여 양극 활물질을 제조하였다.The lithium composite compound prepared in Comparative Example 1 is the lithium composite compound: Al (OH) 3 powder: B 2 O 3 powder = 100: 0.4: 0.2 dry mixed at a weight ratio and calcined to disperse Al (OH). The 3 powder and the B 2 O 3 powder were uniformly attached to the surface of the lithium composite compound. Then, the dry-mixed powder was heat-treated at 400 ° C. for 6 hours to prepare a positive electrode active material.
코인셀의Coin cell 제조 Produce
전술한 실시예 및 비교예에서 제조된 양극 활물질 95 중량%, 도전제로 카본 블랙(carbon black) 2.5 중량%, 결합제로 PVDF 2.5중량% 를 용제(솔벤트)인 N-메틸-2 피롤리돈(NMP) 5.0 중량%에 첨가하여 양극 슬러리를 제조하였다. 상기 양극 슬러리를 두께 20 내지 40㎛의 양극 집전체인 알루미늄(Al) 박막에 도포 및 진공 건조하고 롤 프레스(roll press)를 실시하여 양극을 제조하였다.95% by weight of the positive electrode active material prepared in the above-described examples and comparative examples, 2.5% by weight of carbon black as a conductive agent, and 2.5% by weight of PVDF as a binder as a solvent (solvent), N-methyl-2 pyrrolidone (NMP) ) Was added to 5.0% by weight to prepare a positive electrode slurry. The positive electrode slurry was coated on a thin film of aluminum (Al), which is a positive electrode current collector having a thickness of 20 to 40 μm, dried under vacuum, and roll-pressed to prepare a positive electrode.
음극으로는 Li-금속을 이용하였다.Li-metal was used as the cathode.
이와 같이 제조된 양극과 Li-금속을 대극으로, 전해액으로는 1.15M LiPF6EC:DMC(1:1vol%)을 사용하여 코인 셀 타입의 반쪽 전지를 제조하였다.The positive electrode and the Li-metal thus prepared were used as counter electrodes, and 1.15M LiPF6EC: DMC (1: 1 vol%) was used as an electrolyte to produce a coin cell type half cell.
충방전은 4.5-3.0V 범위에서 실시하였다. 수명의 경우 1.0C 율로 평가하였다.Charging and discharging was performed in the range of 4.5-3.0V. For life, it was evaluated at a rate of 1.0C.
실험예Experimental Example 1: 전지 특성 평가 1: Battery characteristics evaluation
하기 표 1은 상기의 실시예 및 비교예의 4.5V 초기 Formation, 율특성, 1cyle, 20cycle, 30cycle 용량 및 수명특성 데이터이다.Table 1 below is 4.5V initial Formation, rate characteristics, 1cyle, 20cycle, 30cycle capacity and life characteristics data of the above Examples and Comparative Examples.
방전용량1CY
Discharge capacity
방전용량20CY
Discharge capacity
방전용량30CY
Discharge capacity
(20CY/
1CY, %)Life characteristics
(20CY /
1CY,%)
(30CY/
1CY, %)Life characteristics
(30CY /
1CY,%)
표 1에서 나타나듯이, 실시예 1 내지 3은 비교예 1 내지 3 보다 수명특성에서 우수한 전지특성을 나타낸다.As shown in Table 1, Examples 1 to 3 show better battery characteristics in life characteristics than Comparative Examples 1 to 3.
보다 구체적으로, 몰리브덴과 니오브를 포함하는 실시예 1은 포함하지 않는 비교예 3에 비하여 고온 고전압에서 우수한 수명 특성이 확인된다. 또한, 실시예 2 내지 3에서 지르코늄 또는 티타늄을 더 포함 할 경우 더 뛰어난 전지특성을 확인 할 수 있다. 비교예 1 및 비교예 2의 경우, 코팅층이 존재하지 아니하여 전지 특성이 열악함을 확인할 수 있다.More specifically, Example 1 containing molybdenum and niobium is found to have excellent life characteristics at high temperature and high voltage compared to Comparative Example 3 without. In addition, in Examples 2 to 3, when zirconium or titanium is further included, superior battery characteristics can be confirmed. In the case of Comparative Example 1 and Comparative Example 2, it was confirmed that the battery properties were poor because no coating layer was present.
본 발명은 상기 실시예들에 한정되는 것이 아니라 서로 다른 다양한 형태로 제조될 수 있으며, 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자는 본 발명의 기술적 사상이나 필수적인 특징을 변경하지 않고서 다른 구체적인 형태로 실시될 수 있다는 것을 이해할 수 있을 것이다. 그러므로 이상에서 기술한 실시예들은 모든 면에서 예시적인 것이며 한정적이 아닌 것으로 이해해야만 한다.The present invention is not limited to the above embodiments, but may be manufactured in various different forms, and those skilled in the art to which the present invention pertains have other specific forms without changing the technical spirit or essential features of the present invention. It will be understood that can be carried out. Therefore, it should be understood that the embodiments described above are illustrative in all respects and not restrictive.
1: 리튬 이차 전지 2: 음극
3: 양극 4: 세퍼레이터
5: 전지 용기 6: 봉입 부재1: lithium secondary battery 2: negative electrode
3: anode 4: separator
5: battery container 6: sealing member
Claims (18)
상기 코어의 표면에 위치한 코팅층을 포함하고,
상기 코팅층은 적어도 2이상의 코팅 원소를 포함하는 리튬 이차 전지용 양극 활물질:
[화학식 1]
Li[LizA(1-z-a)Da]EbO2-b
(상기 화학식 1에서 A는 NiαCoβMnγ이고, D는 Mo 및 Nb를 포함하거나, Mo, Nb 및 Zr를 포함하거나, Mo, Nb 및 Ti를 포함하며, E는 P, F 및 S로 이루어진 군에서 선택된 1종 이상의 원소이고, -0.05 ≤ z ≤ 0.1, 0 ≤ a ≤ 0.05, 0 ≤ b ≤ 0.05, 0.3 ≤ α ≤ 0.9, 0.05≤ β≤0.4 및 0.05≤ γ≤0.4 이다.)Core comprising a compound represented by the formula (1); And
It includes a coating layer located on the surface of the core,
The coating layer is a cathode active material for a lithium secondary battery comprising at least two coating elements:
[Formula 1]
Li [Li z A (1-za) D a ] E b O 2-b
(In Formula 1, A is Ni α Co β Mn γ , D includes Mo and Nb, or includes Mo, Nb and Zr, or includes Mo, Nb and Ti, and E is P, F and S One or more elements selected from the group consisting of -0.05 ≤ z ≤ 0.1, 0 ≤ a ≤ 0.05, 0 ≤ b ≤ 0.05, 0.3 ≤ α ≤ 0.9, 0.05 ≤ β ≤ 0.4 and 0.05 ≤ γ ≤ 0.4.)
상기 화학식 1에서 -0.05 ≤ z ≤ 0.05, 0.6 ≤ α ≤ 0.9, 0.05≤ β≤0.2 및 0.05≤ γ≤0.2인 리튬 이차 전지용 양극 활물질.According to claim 1,
In the formula 1 -0.05 ≤ z ≤ 0.05, 0.6 ≤ α ≤ 0.9, 0.05 ≤ β ≤ 0.2 and 0.05 ≤ γ ≤ 0.2 positive electrode active material for a lithium secondary battery.
상기 화학식 1에서 D의 몰 도핑비율은 0.001 내지 0.01 인 리튬 이차 전지용 양극 활물질.According to claim 1,
The positive electrode active material for a lithium secondary battery having a molar doping ratio of D in Formula 1 is 0.001 to 0.01.
상기 코팅층은 Al, B 또는 이들의 조합을 포함하는 리튬 이차 전지용 양극 활물질.According to claim 1,
The coating layer is a positive electrode active material for a lithium secondary battery comprising Al, B or a combination thereof.
전체 양극 활물질의 총 중량에 대하여 상기 코팅층의 함량은 0.05 내지 1.0 중량%인 리튬 이차 전지용 양극 활물질.According to claim 1,
The positive electrode active material for a lithium secondary battery, the content of the coating layer relative to the total weight of the total positive electrode active material is 0.05 to 1.0% by weight.
상기 코팅층은 상기 코어의 표면에 부분적으로 위치되는 아일랜드(Island) 형태인 리튬 이차 전지용 양극 활물질.According to claim 1,
The coating layer is a positive electrode active material for a lithium secondary battery in the form of an island (Island) partially located on the surface of the core.
상기 코팅층은 F를 더 포함하는 코팅층인 것인 리튬 이차 전지용 양극 활물질.The method of claim 6,
The coating layer is a positive electrode active material for a lithium secondary battery that is a coating layer further comprising F.
상기 코어와 코팅층을 형성하는 원료 화합물을 혼합하여 혼합물을 제조하는 단계; 및
상기 혼합물을 소성하는 단계를 포함하고,
상기 코팅층은 형성하는 원료 화합물은 적어도 2종 이상인 리튬 이차 전지용 양극 활물질의 제조 방법:
[화학식 1]
Li[LizA(1-z-a)Da]EbO2-b
(상기 화학식 1에서 A는 NiαCoβMnγ이고, D는 Mo 및 Nb를 포함하거나, Mo, Nb 및 Zr를 포함하거나, Mo, Nb 및 Ti를 포함하며, E는 P, F 및 S로 이루어진 군에서 선택된 1종 이상의 원소이고, -0.05 ≤ z ≤ 0.1, 0 ≤ a ≤ 0.05, 0 ≤ b ≤ 0.05, 0.3 ≤ α ≤ 0.9, 0.05≤ β≤0.4 및 0.05≤ γ≤0.4 이다.)Preparing a core comprising a compound represented by Formula 1 below;
Preparing a mixture by mixing the core and a raw material compound forming a coating layer; And
Calcining the mixture,
The coating layer is a method of manufacturing a positive electrode active material for a lithium secondary battery of at least two or more kinds of raw material compounds to form:
[Formula 1]
Li [Li z A (1-za) D a ] E b O 2-b
(In Formula 1, A is Ni α Co β Mn γ , D includes Mo and Nb, or includes Mo, Nb and Zr, or includes Mo, Nb and Ti, and E is P, F and S One or more elements selected from the group consisting of -0.05 ≤ z ≤ 0.1, 0 ≤ a ≤ 0.05, 0 ≤ b ≤ 0.05, 0.3 ≤ α ≤ 0.9, 0.05 ≤ β ≤ 0.4 and 0.05 ≤ γ ≤ 0.4.)
상기 화학식 1에서 -0.05 ≤ z ≤ 0.05, 0.6 ≤ α ≤ 0.9, 0.05≤ β≤0.2 및 0.05≤ γ≤0.2인 리튬 이차 전지용 양극 활물질의 제조 방법.The method of claim 10,
In the formula (1) -0.05 ≤ z ≤ 0.05, 0.6 ≤ α ≤ 0.9, 0.05 ≤ β ≤ 0.2 and 0.05 ≤ γ ≤ 0.2 Method for producing a positive electrode active material for a lithium secondary battery.
상기 화학식 1에서 D의 몰 도핑비율은 0.001 내지 0.01 인 리튬 이차 전지용 양극 활물질의 제조 방법.The method of claim 10,
A method of manufacturing a positive electrode active material for a lithium secondary battery having a molar doping ratio of D in Formula 1 of 0.001 to 0.01.
상기 혼합물을 제조하는 단계에서, 상기 원료 화합물은 알루미늄 공급원, 붕소 공급원 또는 이들의 조합인 리튬 이차 전지용 양극 활물질의 제조 방법.The method of claim 10,
In the step of preparing the mixture, the raw material compound is an aluminum source, a boron source, or a combination thereof, a method for producing a positive electrode active material for a lithium secondary battery.
상기 혼합물을 제조하는 단계에서, 상기 원료 화합물은 Al2O3, Al(OH)3, AlPO4, Al(NO3)3, B2O3, H3BO4, B(OH)3, Li2B4O7 또는 이들의 조합인 리튬 이차 전지용 양극 활물질의 제조 방법.The method of claim 10,
In the step of preparing the mixture, the raw material compound is Al 2 O 3 , Al (OH) 3 , AlPO 4 , Al (NO 3 ) 3 , B 2 O 3 , H 3 BO 4 , B (OH) 3 , Li 2 B 4 O 7 or a combination thereof, a method for producing a positive electrode active material for a lithium secondary battery.
상기 혼합물을 소성하는 단계에서, 소성 온도는 300 내지 450℃ 인 리튬 이차 전지용 양극 활물질의 제조 방법.The method of claim 10,
In the step of firing the mixture, the firing temperature is 300 to 450 ℃ method for producing a positive electrode active material for a lithium secondary battery.
음극 활물질을 포함하는 음극; 및
전해질;
을 포함하는 리튬 이차 전지.A positive electrode comprising the positive electrode active material for a lithium secondary battery according to any one of claims 1, 2 and 5 to 9;
A negative electrode comprising a negative electrode active material; And
Electrolyte;
Lithium secondary battery comprising a.
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