KR102617270B1 - Positive electrode and secondary battery comprsing the same - Google Patents
Positive electrode and secondary battery comprsing the same Download PDFInfo
- Publication number
- KR102617270B1 KR102617270B1 KR1020230090281A KR20230090281A KR102617270B1 KR 102617270 B1 KR102617270 B1 KR 102617270B1 KR 1020230090281 A KR1020230090281 A KR 1020230090281A KR 20230090281 A KR20230090281 A KR 20230090281A KR 102617270 B1 KR102617270 B1 KR 102617270B1
- Authority
- KR
- South Korea
- Prior art keywords
- positive electrode
- active material
- current collector
- secondary battery
- flame retardant
- Prior art date
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—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
본 발명은 집전체, 및 리튬철 인산화물계 활물질을 포함하는 양극 활물질층을 포함하며, 상기 집전체는 기공을 포함하며, 상기 집전체 전체 부피 대비 상기 기공의 총 부피는 30 % 내지 80 %이며, 상기 집전체의 적어도 일 표면에 난연제를 포함하는 난연층이 형성된 양극 및 이를 포함하는 이차 전지를 제공한다.The present invention includes a current collector and a positive electrode active material layer containing a lithium iron phosphate-based active material, wherein the current collector includes pores, and the total volume of the pores is 30% to 80% compared to the total volume of the current collector, A positive electrode having a flame retardant layer containing a flame retardant formed on at least one surface of the current collector and a secondary battery including the same are provided.
Description
본 발명은 양극 및 이를 포함하는 이차 전지에 관한 것이다.The present invention relates to a positive electrode and a secondary battery including the same.
전자, 통신 및 우주 산업이 발전됨에 따라, 에너지 동력원으로서 이차전지(secondary battery)의 수요가 급격히 증대되고 있다. 특히, 글로벌 친환경 정책의 중요성이 강조됨에 따라 전기 자동차 시장이 비약적으로 성장 중이며, 국내외에서 이차전지에 관한 연구 개발이 활발히 이루어지고 있다.As the electronics, communications, and space industries develop, the demand for secondary batteries as an energy power source is rapidly increasing. In particular, as the importance of global eco-friendly policies is emphasized, the electric vehicle market is growing rapidly, and research and development on secondary batteries is being actively conducted at home and abroad.
다양한 이차전지 중에서도 높은 방전 전압 및 에너지 밀도를 가진 리튬 이차전지는 각종 모바일 기기 및 다양한 전자제품의 에너지원으로 널리 사용되고 있다. Among various secondary batteries, lithium secondary batteries with high discharge voltage and energy density are widely used as an energy source for various mobile devices and various electronic products.
리튬 이차전지의 양극 활물질로는 리튬 전이금속 복합 산화물이 이용되고 있으며, 이중에서도 작용전압이 높고 용량 특성이 우수한 LiCoO2의 리튬코발트 복합금속 산화물이 주로 사용되고 있다. 그러나, LiCoO2는 안정성이 낮고 고가이기 때문에, 리튬 이차전지를 대량 생산하기 어려운 문제점이 있다.Lithium transition metal composite oxide is used as a positive electrode active material for lithium secondary batteries, and among these, lithium cobalt composite metal oxide of LiCoO 2 , which has a high operating voltage and excellent capacity characteristics, is mainly used. However, because LiCoO 2 has low stability and is expensive, it is difficult to mass-produce lithium secondary batteries.
이에 LiCoO2를 대체하기 위한 재료로서, 리튬망간 복합금속 산화물, 리튬철 인산화물, 리튬니켈 복합금속 산화물 등이 개발되었다. 이중에서 올리빈 구조를 갖는 리튬철 인산화물(LiFePO4)은 3.6g/cm3의 높은 체적 밀도를 가지며 이론 용량은 약 170mAh/g을 나타낸다. Accordingly, as materials to replace LiCoO 2 , lithium manganese composite metal oxide, lithium iron phosphate, and lithium nickel composite metal oxide were developed. Among these, lithium iron phosphate (LiFePO 4 ) with an olivine structure has a high volume density of 3.6 g/cm 3 and a theoretical capacity of about 170 mAh/g.
다만, 리튬철 인산화물(LiFePO4)은 낮은 전기 전도성으로 인해, LiFePO4를 양극 활물질로서 사용하는 경우 전지의 내부 저항이 증가되며, 이로 인해 방전 용량 및 수명 특성이 저하되는 문제가 발생하였다. However, due to the low electrical conductivity of lithium iron phosphate (LiFePO 4 ), when LiFePO 4 is used as a positive electrode active material, the internal resistance of the battery increases, which causes the problem of deterioration of discharge capacity and lifespan characteristics.
특히, 최근에는 하이브리드 자동차나 전기 자동차의 구동용 전원으로서, 리튬 이차전지를 적용하고 있는 바, 리튬 이차전지의 향상된 방전 용량 및 우수한 수명 특성을 가지는 것이 요구되고 있다.In particular, in recent years, lithium secondary batteries have been used as a power source for driving hybrid vehicles and electric vehicles, and there is a demand for lithium secondary batteries to have improved discharge capacity and excellent lifespan characteristics.
본 발명은 전류의 밀도를 낮추고, 안정성이 향상되어, 방전 용량 및 수명 특성이 증가된 양극 및 이를 포함하는 이차 전지를 제공한다.The present invention provides a positive electrode with reduced current density, improved stability, and increased discharge capacity and lifespan characteristics, and a secondary battery including the same.
본 발명에 따른 양극은 집전체, 및 리튬철 인산화물계 활물질을 포함하는 양극 활물질층을 포함하며, 상기 집전체는 기공을 포함하며, 상기 집전체 전체 부피 대비 상기 기공의 총 부피는 30 % 내지 80 %이며, 상기 집전체의 적어도 일 표면에 난연제를 포함하는 난연층이 형성된다.The positive electrode according to the present invention includes a current collector and a positive electrode active material layer containing a lithium iron phosphate-based active material, wherein the current collector includes pores, and the total volume of the pores relative to the total volume of the current collector is 30% to 80%. %, and a flame retardant layer containing a flame retardant is formed on at least one surface of the current collector.
본 발명의 일 실시예에 있어서, 상기 양극 활물질층은 상기 리튬철 인산화물계 활물질 상에 코팅된 나트륨(Na) 원소를 포함할 수 있다.In one embodiment of the present invention, the positive electrode active material layer may include sodium (Na) element coated on the lithium iron phosphate-based active material.
본 발명의 일 실시예에 있어서, 상기 양극 활물질층은 폴리아크릴아마이드(Polyacrylamide), 폴리우레탄(polyurethane), 및 폴리아크릴로나이트릴(polyacrylonitrile)로 이루어진 군에서 선택되는 1종 이상의 수평균 분자량 30,000 g/mol 내지 80,000 g/mol를 가지는 바인더 응집제를 포함할 수 있다.In one embodiment of the present invention, the positive electrode active material layer is one or more materials selected from the group consisting of polyacrylamide, polyurethane, and polyacrylonitrile, with a number average molecular weight of 30,000 g. /mol to 80,000 g/mol of a binder coagulant.
본 발명의 일 실시예에 있어서, 상기 난연제는 지방족 할로겐 화합물을 포함할 수 있다.In one embodiment of the present invention, the flame retardant may include an aliphatic halogen compound.
본 발명에 따른 이차 전지는 양극, 음극, 상기 양극 및 음극 사이에 개재된 분리막을 포함하며, 상기 양극은 집전체, 및 리튬철 인산화물계 활물질을 포함하는 양극 활물질층을 포함하며, 상기 집전체는 기공을 포함하며, 상기 집전체 전체 부피 대비 상기 기공의 총 부피는 30 % 내지 80 %이며, 상기 집전체의 적어도 일 표면에 난연제를 포함하는 난연층이 형성된다.A secondary battery according to the present invention includes a positive electrode, a negative electrode, and a separator interposed between the positive electrode and the negative electrode, wherein the positive electrode includes a current collector and a positive electrode active material layer containing a lithium iron phosphate-based active material, and the current collector includes It includes pores, and the total volume of the pores is 30% to 80% of the total volume of the current collector, and a flame retardant layer containing a flame retardant is formed on at least one surface of the current collector.
본 발명에 따른 양극은 특정 기공도를 가진 집전체를 사용하여 전류의 밀도를 낮추며, 상기 집전체의 표면에 난연제를 포함하는 난연층이 형성됨으로써 안정성이 향상됨으로써, 이차 전지의 방전 용량 및 수명 특성이 향상될 수 있다. The positive electrode according to the present invention uses a current collector with a specific porosity to lower the current density, and the stability is improved by forming a flame retardant layer containing a flame retardant on the surface of the current collector, thereby improving the discharge capacity and lifespan characteristics of the secondary battery. This can be improved.
본 명세서 또는 출원에 개시되어 있는 실시예들에 대한 구조적 또는 기능적 설명들은 단지 본 발명의 기술적 사상에 따른 실시예들을 설명하기 위한 목적으로 예시된 것으로, 본 발명의 기술적 사상에 따른 실시예들은 본 명세서 또는 출원에 개시되어 있는 실시예들 이외에도 다양한 형태로 실시될 수 있으며, 본 발명의 기술적 사상이 본 명세서 또는 출원에 설명된 실시예들에 한정되는 것으로 해석되지 않는다.The structural or functional descriptions of the embodiments disclosed in the present specification or application are merely illustrative for the purpose of explaining embodiments according to the technical idea of the present invention, and the embodiments according to the technical idea of the present invention are described in this specification. Alternatively, it may be implemented in various forms other than the embodiments disclosed in the application, and the technical idea of the present invention is not to be construed as being limited to the embodiments described in this specification or application.
이하에서, 본 발명에 따른 양극 및 이차 전지에 대하여 설명한다.Below, the positive electrode and secondary battery according to the present invention will be described.
<양극><Anode>
본 발명에 따른 양극은 집전체, 및 리튬철 인산화물계 활물질을 포함하는 양극 활물질층을 포함하며, 상기 집전체는 기공을 포함하며, 상기 집전체 전체 부피 대비 상기 기공의 총 부피는 30 % 내지 80 %이며, 상기 집전체의 적어도 일 표면에 난연제를 포함하는 난연층이 형성된다.The positive electrode according to the present invention includes a current collector and a positive electrode active material layer containing a lithium iron phosphate-based active material, wherein the current collector includes pores, and the total volume of the pores relative to the total volume of the current collector is 30% to 80%. %, and a flame retardant layer containing a flame retardant is formed on at least one surface of the current collector.
본 발명에 따른 양극은 집전체를 포함한다. 상기 집전체는 스테인레스 스틸, 알루미늄, 니켈, 티탄, 소성 탄소, 또는 알루미늄일 수 있다.The positive electrode according to the present invention includes a current collector. The current collector may be stainless steel, aluminum, nickel, titanium, fired carbon, or aluminum.
상기 집전체의 두께는 요구되는 제품에 따라 조절될 수 있고, 예를 들어 10㎛ 내지 500㎛, 10㎛ 내지 300㎛, 또는 20㎛ 내지 300㎛일 수 있다.The thickness of the current collector may be adjusted depending on the required product, and may be, for example, 10 μm to 500 μm, 10 μm to 300 μm, or 20 μm to 300 μm.
상기 집전체는 기공을 포함한다. 상기 집전체 전체 부피 대비 상기 기공의 총 부피는 10 % 내지 90 %, 15 % 내지 90 %, 20 % 내지 90 %, 20 % 내지 85 %, 25 % 내지 85 %, 25 % 내지 80 %, 또는 30 % 내지 80 %일 수 있다. 상기 범위를 만족하는 경우, 기계적 물성 저하 없이, 전류 밀도를 낮출 수 있어 이차 전지의 방전 용량 및 수명 특성이 향상될 수 있다.The current collector includes pores. The total volume of the pores relative to the total volume of the current collector is 10% to 90%, 15% to 90%, 20% to 90%, 20% to 85%, 25% to 85%, 25% to 80%, or 30%. It can be from % to 80%. When the above range is satisfied, the current density can be lowered without deteriorating mechanical properties, and the discharge capacity and life characteristics of the secondary battery can be improved.
상기 집전체의 적어도 일 표면에 난연제를 포함하는 난연층이 형성된다. 상기 난연층에 의해 방염성이 확보되어 이차 전지의 단락, 과충전, 과방전 등에 의한 화재의 확산이 억제될 수 있다. A flame retardant layer containing a flame retardant is formed on at least one surface of the current collector. Flame retardancy is secured by the flame retardant layer, and the spread of fire due to short circuit, overcharge, and overdischarge of the secondary battery can be suppressed.
상기 난연제는 할로겐계 난연제, 인계 난연제, 또는 무기화합물 난연제를 포함할 수 있다. 바람직하게는, 상기 난연제는 지방족 할로겐 화합물을 포함할 수 있다. 상기 난연제가 상기 지방족 할로겐 화합물을 포함하는 경우 난연성능이 더욱 향상되며, 양극 활물질층간의 상용성이 증가되어, 이차 전지의 방전 용량 및 수명 특성이 저하를 최소화할 수 있다.The flame retardant may include a halogen-based flame retardant, a phosphorus-based flame retardant, or an inorganic compound flame retardant. Preferably, the flame retardant may include an aliphatic halogen compound. When the flame retardant includes the aliphatic halogen compound, flame retardant performance is further improved, compatibility between positive electrode active material layers is increased, and deterioration in discharge capacity and lifespan characteristics of the secondary battery can be minimized.
본 발명에 따른 양극은 상기 집전체 상에 형성되며 회합성 우레탄계 증점제 및 바인더를 포함하는 코팅층을 포함할 수 있다. 상기 코팅층은 상기 집전체 및 상기 난연층 사이에 형성될 수 있다.The positive electrode according to the present invention is formed on the current collector and may include a coating layer containing an associative urethane-based thickener and a binder. The coating layer may be formed between the current collector and the flame retardant layer.
상기 코팅층은 상기 집전체와 상기 난연층 사이에서의 계면 접착력을 향상시킬 수 있다. 상기 코팅층은 전극 표면에 핀홀이 발생되는 것을 억제하기 위해 회합성 우레탄계 증점제를 포함할 수 있다. 상기 회합성 우레탄계 증점제는 양극 활물질 간 응집력을 강화시킬 수 있다.The coating layer can improve interfacial adhesion between the current collector and the flame retardant layer. The coating layer may include an associative urethane-based thickener to prevent pinholes from forming on the electrode surface. The associative urethane-based thickener can enhance cohesion between positive electrode active materials.
상기 회합성 우레탄 증점제는 폴리알킬렌 글리콜 화합물로서, 예를 들어, 폴리이소시아네이트 및 소수성 말단기로 이루어진 알킬, 아릴 또는 아릴알킬 유형의 회합성으로 지칭되는 단량체 또는 축합물 사이의 합성으로 생성된 공중합체로 지칭될 수 있다.The associative urethane thickeners are polyalkylene glycol compounds, for example copolymers produced by synthesis between polyisocyanates and monomers or condensates, referred to as associative, of the alkyl, aryl or arylalkyl type consisting of hydrophobic end groups. It may be referred to as .
상기 회합성 우레탄계 증점제의 중량평균 분자량은 200,000 g/mol 내지 500,000 g/mol, 250,000 g/mol 내지 500,000 g/mol, 250,000 g/mol 내지 450,000 g/mol, 300,000 g/mol 내지 450,000 g/mol, 350,000 g/mol 내지 450,000 g/mol, 또는 350,000 g/mol 내지 400,000 g/mol일 수 있다.The weight average molecular weight of the associative urethane-based thickener is 200,000 g/mol to 500,000 g/mol, 250,000 g/mol to 500,000 g/mol, 250,000 g/mol to 450,000 g/mol, 300,000 g/mol to 450,000 g/mol, It may be 350,000 g/mol to 450,000 g/mol, or 350,000 g/mol to 400,000 g/mol.
상기 코팅층은 코팅층 조성물로부터 제조될 수 있고, 상기 코팅층 조성물 전체 중량 대비, 상기 회합성 우레탄계 증점제는 0.01 중량% 내지 3.00 중량%, 0.01 중량% 내지 1.00 중량%, 또는 0.1 중량% 내지 1.00 중량%로 포함될 수 있다.The coating layer may be manufactured from a coating layer composition, and the associative urethane-based thickener may be included in an amount of 0.01 wt% to 3.00 wt%, 0.01 wt% to 1.00 wt%, or 0.1 wt% to 1.00 wt%, based on the total weight of the coating layer composition. You can.
상기 코팅층은 바인더를 포함할 수 있다. 상기 바인더는 스티렌 부타디엔 고무(SBR)를 포함할 수 있다. 상기 바인더는 폴리불화비닐리덴, 폴리비닐알코올, 전분, 히드록시프로필셀룰로우즈, 재생 셀룰로우즈, 폴리비닐피롤리돈, 테트라플루오로에틸렌, 폴리에틸렌, 폴리프로필렌, 에틸렌-프로필렌-디엔 테르 폴리머(EPDM), 술폰화 EPDM, 스티렌 브티렌 고무, 불소 고무, 스티렌(styrene monomer: SM), 부타디엔 (butadiene: BD) 및 부틸 아크릴레이트(butyl acrylate: BA)로 이루어진 군에서 선택되는 하나 이상을 더 포함할 수 있다.The coating layer may include a binder. The binder may include styrene butadiene rubber (SBR). The binder is polyvinylidene fluoride, polyvinyl alcohol, starch, hydroxypropylcellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene, polyethylene, polypropylene, ethylene-propylene-diene terpolymer ( EPDM), sulfonated EPDM, styrene butyrene rubber, fluorine rubber, styrene (styrene monomer: SM), butadiene (BD), and butyl acrylate (BA). can do.
본 발명에 따른 양극은 리튬철 인산화물계 활물질을 포함한다. 상기 리튬철 인산화물계 활물질은 하기 화학식 1로 표시되는 화합물일 수 있다. The positive electrode according to the present invention includes a lithium iron phosphate-based active material. The lithium iron phosphate-based active material may be a compound represented by the following formula (1).
[화학식 1][Formula 1]
Li1+aFe1-xMx(PO4-b)Yb Li 1+a Fe 1-x M x (PO 4-b )Y b
상기 화학식 1에서, M은 Ni, Co, Mn, Ti, Ga, Cu, V, Nb, Zr, Ce, In 및 Cu로 이루어진 군에서 선택되는 어느 하나 이상의 원소이며, Y는 F, S 및 N로 이루어진 군에서 선택되는 어느 하나 이상의 원소이고, a, b, x는 -0.5≤a≤0.5, 0≤b≤0.1, 0≤x≤0.5이다.In Formula 1, M is one or more elements selected from the group consisting of Ni, Co, Mn, Ti, Ga, Cu, V, Nb, Zr, Ce, In, and Cu, and Y is represented by F, S, and N. It is one or more elements selected from the group consisting of, and a, b, and x are -0.5≤a≤0.5, 0≤b≤0.1, 0≤x≤0.5.
상기 리튬철 인산화물계 활물질은 LiFePO4일 수 있다.The lithium iron phosphate-based active material may be LiFePO 4 .
본 발명에 따른 양극 활물질층은 상기 리튬철 인산화물계 활물질 상에 코팅된 나트륨(Na) 원소를 포함할 수 있다. 상기 리튬철 인산화물계 활물질 상에 나트륨(Na) 원소가 코팅되는 경우, 상기 리튬철 인산화물계 활물질 표면의 화학적 안정성이 향상되어, 상기 리튬철 인산화물계 활물질의 구조적 붕괴가 억제될 수 있다.The positive electrode active material layer according to the present invention may include sodium (Na) element coated on the lithium iron phosphate-based active material. When sodium (Na) element is coated on the lithium iron phosphate-based active material, the chemical stability of the surface of the lithium iron phosphate-based active material is improved, and structural collapse of the lithium iron phosphate-based active material can be suppressed.
또한, 상기 리튬철 인산화물계 활물질에 포함된 금속 대비 상기 나트륨 원소 가 먼저 산화되어, 상기 리튬철 인산화물계 활물질과 전해액과의 부반응이 억제될 수 있어, 리튬 이온의 이동에 따른 저항 상승이 방지될 수 있다.In addition, the sodium element is oxidized first compared to the metal contained in the lithium iron phosphate-based active material, so side reactions between the lithium iron phosphate-based active material and the electrolyte can be suppressed, and an increase in resistance due to the movement of lithium ions can be prevented. there is.
상기 나트륨 원소가 형성되기 위한 전구체로서 NaOH, Ba(OH)2, Na2CO3, NaCl, CH3COONa, Na2SO4, 및 NaNO2으로 이루어진 군에서 선택된 1종 이상이 사용될 수 있다.As a precursor for forming the sodium element, one or more species selected from the group consisting of NaOH, Ba(OH) 2 , Na 2 CO 3 , NaCl, CH 3 COONa, Na 2 SO 4 , and NaNO 2 may be used.
상기 양극 활물질층은 상기 리튬철 인산화물계 활물질 상에 코팅된 알루미늄(Al) 원소를 포함할 수 있다. 상기 알루미늄 원소가 상기 리튬철 인산화물계 활물질 상에 형성됨으로써, 상기 리튬철 인산화물계 활물질 표면의 화학적 안정성이 향상되어, 상기 리튬철 인산화물계 활물질의 구조적 붕괴가 억제될 수 있고, 기계적 특성이 향상될 수 있다.The positive electrode active material layer may include aluminum (Al) element coated on the lithium iron phosphate-based active material. By forming the aluminum element on the lithium iron phosphate-based active material, the chemical stability of the surface of the lithium iron phosphate-based active material is improved, structural collapse of the lithium iron phosphate-based active material can be suppressed, and mechanical properties can be improved. there is.
상기 알루미늄 원소가 형성되기 위한 전구체로서 Al2O3, Al(OH)3, AlF3, AlBr3, AlPO4, AlCl3, Al(NO)3, Al(H2PO4)3, 및 C2H5O4Al으로 이루어진 군에서 선택된 1종 이상이 사용될 수 있다.As a precursor for forming the aluminum element, Al 2 O 3 , Al(OH) 3 , AlF 3 , AlBr 3 , AlPO 4 , AlCl 3 , Al(NO) 3 , Al(H 2 PO 4 ) 3 , and C 2 One or more types selected from the group consisting of H 5 O 4 Al may be used.
상기 리튬철 인산화물계 활물질 내에 질소(N) 원소가 도핑된 구조를 포함할 수 있다. 상기 질소 원소는 이차 전지의 전기 전도도를 향상시켜, 이차 전지의 초기 효율이 저하되는 현상이 최소화될 수 있다.The lithium iron phosphate-based active material may include a structure doped with a nitrogen (N) element. The nitrogen element improves the electrical conductivity of the secondary battery, thereby minimizing the decrease in initial efficiency of the secondary battery.
상기 양극 활물질층 전체 중량 대비, 상기 질소 원소의 함량은 300 ppm 내지 10,000 ppm, 500 ppm 내지 5,000 ppm, 500 ppm 내지 4,000 ppm, 500 ppm 내지 3,000 ppm, 500 ppm 내지 2,000 ppm, 또는 500 ppm 내지 1,500 ppm으로 포함될 수 있다. 상기 범위를 만족하는 경우, 이차 전지의 전기 전도도가 향상되며, 초기 효율이 저하되는 현상이 최소화될 수 있다.Compared to the total weight of the positive active material layer, the content of the nitrogen element is 300 ppm to 10,000 ppm, 500 ppm to 5,000 ppm, 500 ppm to 4,000 ppm, 500 ppm to 3,000 ppm, 500 ppm to 2,000 ppm, or 500 ppm to 1,500 ppm. may be included. When the above range is satisfied, the electrical conductivity of the secondary battery is improved, and the phenomenon of initial efficiency reduction can be minimized.
상기 리튬철 인산화물계 활물질은 전도성 코팅층을 포함할 수 있다. The lithium iron phosphate-based active material may include a conductive coating layer.
상기 전도성 코팅층은 탄소계 물질을 포함할 수 있다. 상기 탄소계 물질은 카본 블랙, 탄소 섬유 또는 금속 섬유, 금속 분말, 도전성 위스커, 도전성 금속, 활성 카본(activated carbon) 폴리페닐렌 유도체, 천연 흑연, 인조 흑연, 슈퍼 피(Super-P), 아세틸렌 블랙, 케첸 블랙, 채널 블랙, 피네이스 블랙, 램프 블랙, 서머 블랙, 덴카 블랙, 알루미늄 분말, 니켈 분말, 산화아연, 티탄산 갈륨 및 산화 티탄으로 이루어진 군으로부터 선택된 1종 이상이 사용될 수 있다. The conductive coating layer may include a carbon-based material. The carbon-based material includes carbon black, carbon fiber or metal fiber, metal powder, conductive whisker, conductive metal, activated carbon, polyphenylene derivative, natural graphite, artificial graphite, Super-P, and acetylene black. , Ketjen Black, Channel Black, Phineas Black, Lamp Black, Summer Black, Denka Black, aluminum powder, nickel powder, zinc oxide, gallium titanate, and titanium oxide may be used.
상기 전도성 코팅층의 두께는 1 nm 내지 500 nm, 1 nm 내지 300 nm, 1 nm 내지 250 nm, 1 nm 내지 200 nm, 5 nm 내지 200 nm, 5 nm 내지 100 nm, 또는 5 nm 내지 50 nm일 수 있다. 상기 범위를 만족하는 경우, 리튬 이온의 이동에 장애가 되지 않으며, 전기 전도도가 상승될 수 있다.The thickness of the conductive coating layer may be 1 nm to 500 nm, 1 nm to 300 nm, 1 nm to 250 nm, 1 nm to 200 nm, 5 nm to 200 nm, 5 nm to 100 nm, or 5 nm to 50 nm. there is. When the above range is satisfied, there is no obstacle to the movement of lithium ions, and electrical conductivity can be increased.
상기 전도성 코팅층에 포함된 탄소의 함량은 상기 양극 활물질층 총 중량 기준 1 중량% 내지 3 중량%, 1 중량% 내지 2.5 중량%, 1 중량% 내지 2 중량%일 수 있다. 상기 범위를 만족하는 경우, 전기 전도도 저하에 따른 저항 증가 문제를 야기하지 않으며, 양극 제조 시 양극 활물질이 탈리되는 현상을 최소화할 수 있다.The content of carbon included in the conductive coating layer may be 1% to 3% by weight, 1% to 2.5% by weight, or 1% to 2% by weight based on the total weight of the positive electrode active material layer. When the above range is satisfied, there is no problem of increased resistance due to a decrease in electrical conductivity, and the phenomenon of detachment of the positive electrode active material during production of the positive electrode can be minimized.
상기 리튬철 인산화물계 활물질의 평균 입경(D50)은 0.3㎛ 내지 10.0㎛, 0.3㎛ 내지 9.0㎛, 또는 0.6㎛ 내지 9.0㎛일 수 있다. 평균 입경(D50)은 양극 활물질 입경 분포의 50% 기준에서의 입경으로 정의할 수 있다. 또한, 평균 입경(D50)은 레이저 회절법(laser diffraction method)을 이용하여 측정할 수 있다. 상기 범위를 만족하는 경우, 도전재 및 바인더와 균일한 혼합이 가능하며, 공정 효율성이 증가될 수 있다.The average particle diameter (D 50 ) of the lithium iron phosphate-based active material may be 0.3 ㎛ to 10.0 ㎛, 0.3 ㎛ to 9.0 ㎛, or 0.6 ㎛ to 9.0 ㎛. The average particle diameter (D 50 ) can be defined as the particle size based on 50% of the particle size distribution of the positive electrode active material. Additionally, the average particle diameter (D 50 ) can be measured using a laser diffraction method. When the above range is satisfied, uniform mixing with the conductive material and binder is possible, and process efficiency can be increased.
상기 리튬철 인산화물계 활물질의 비표면적(BET)은 30m2/g 이하, 20m2/g 이하, 또는 5m2/g 내지 15m2/g일 수 있다. 비표면적(BET)은 BEL Japan사의 BELSORP-mino II를 이용하여 액체 질소 온도 하(77K)에서의 질소가스 흡착량으로부터 산출할 수 있다. 상기 범위를 만족하는 경우, 양극 집전체와의 접착력 저하를 야기하지 않을 수 있다.The specific surface area (BET) of the lithium iron phosphate-based active material may be 30 m 2 /g or less, 20 m 2 /g or less, or 5 m 2 /g to 15 m 2 /g. Specific surface area (BET) can be calculated from the amount of nitrogen gas adsorption under liquid nitrogen temperature (77K) using BELSORP-mino II from BEL Japan. When the above range is satisfied, adhesion to the positive electrode current collector may not be reduced.
상기 리튬철 인산화물계 활물질의 탭 밀도(tap density)는 0.5g/cm3 이상, 0.6g/cm3 이상, 또는 0.6g/cm3 내지 1.5g/cm3일 수 있다. 탭밀도는 상기 리튬철 인산화물계 활물질 분말의 겉보기 밀도를 의미하며, Seishin 社의 KYT-5000를 이용하여 측정할 수 있다. 상기 범위를 만족하는 경우, 양극의 충진밀도가 향상되어, 양극의 두께가 얇게 개선되며, 양극 활물질의 깨짐 현상을 개선할 수 있다.The tap density of the lithium iron phosphate-based active material is 0.5 g/cm 3 or more, 0.6 g/cm 3 or more, or 0.6 g/cm 3 or more. It may be 1.5g/cm 3 . Tap density refers to the apparent density of the lithium iron phosphate-based active material powder, and can be measured using Seishin's KYT-5000. When the above range is satisfied, the packing density of the positive electrode is improved, the thickness of the positive electrode can be improved to be thinner, and the cracking phenomenon of the positive electrode active material can be improved.
상기 양극 활물질층은 도전재 및 바인더를 포함할 수 있다. 상기 바인더는 상기 리튬철 인산화물계 활물질 및 도전재 간의 결합력과 양극 활물질층 및 양극 집전체 간의 결합력을 향상시킬 수 있다. 상기 바인더는 상기 리튬철 인산화물계 활물질 100 중량부 기준 1 내지 30 중량부, 1 내지 20 중량부, 또는 1 내지 15 중량부로 첨가될 수 있다. 상기 바인더의 종류는 특별히 제한되지 않으나, 예를 들어 폴리비닐리덴플로라이드(PVDF), 폴리테트라플루오로에틸렌(PTFE), 불소 고무, 스티렌 부타디엔 고무(SBR, 셀룰로오스계 수지 등이 사용될 수 있다.The positive active material layer may include a conductive material and a binder. The binder can improve the bonding force between the lithium iron phosphate-based active material and the conductive material and the bonding force between the positive electrode active material layer and the positive electrode current collector. The binder may be added in an amount of 1 to 30 parts by weight, 1 to 20 parts by weight, or 1 to 15 parts by weight based on 100 parts by weight of the lithium iron phosphate-based active material. The type of the binder is not particularly limited, but for example, polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), fluorine rubber, styrene butadiene rubber (SBR), cellulose resin, etc. can be used.
상기 도전재는 상기 리튬철 인산화물계 활물질의 도전성을 향상시킬 수 있다. 상기 도전재는 상기 리튬철 인산화물계 활물질 100 중량부 기준 1 내지 40 중량부, 1 내지 20 중량부, 또는 1 내지 10 중량부로 첨가될 수 있다. 상기 도전재의 종류는 특별히 제한되지 않으나, 예를 들어 슈퍼-비(Super-P), 흑연, 아세틸렌 블랙 등이 사용될 수 있다. The conductive material can improve the conductivity of the lithium iron phosphate-based active material. The conductive material may be added in an amount of 1 to 40 parts by weight, 1 to 20 parts by weight, or 1 to 10 parts by weight based on 100 parts by weight of the lithium iron phosphate-based active material. The type of the conductive material is not particularly limited, but for example, Super-P, graphite, acetylene black, etc. may be used.
상기 양극 활물질층은 폴리아크릴아마이드(Polyacrylamide), 폴리우레탄(polyurethane), 및 폴리아크릴로나이트릴(polyacrylonitrile)로 이루어진 군에서 선택되는 1종 이상의 수평균 분자량 30,000 g/mol 내지 80,000 g/mol를 가지는 바인더 응집제를 포함할 수 있다. 상기 바인더 응집제는 상기 바인더의 분산성을 적절히 조절하여, 상기 집전체 상에 상기 바인더가 집중적으로 분포되어 전기 전도도가 저하되는 현상이 억제될 수 있다.The positive electrode active material layer is one or more selected from the group consisting of polyacrylamide, polyurethane, and polyacrylonitrile, and has a number average molecular weight of 30,000 g/mol to 80,000 g/mol. Binder may contain a coagulant. The binder coagulant can appropriately control the dispersibility of the binder, thereby suppressing a phenomenon in which the binder is intensively distributed on the current collector, thereby reducing electrical conductivity.
<이차 전지><Secondary battery>
본 발명에 따른 이차 전지는 양극, 음극, 상기 양극 및 음극 사이에 개재된 분리막을 포함하며, 상기 양극은 집전체, 및 리튬철 인산화물계 활물질을 포함하는 양극 활물질층을 포함하며, 상기 집전체는 기공을 포함하며, 상기 집전체 전체 부피 대비 상기 기공의 총 부피는 30 % 내지 80 %이며, 상기 집전체의 적어도 일 표면에 난연제를 포함하는 난연층이 형성된다.A secondary battery according to the present invention includes a positive electrode, a negative electrode, and a separator interposed between the positive electrode and the negative electrode, wherein the positive electrode includes a current collector and a positive electrode active material layer containing a lithium iron phosphate-based active material, and the current collector includes It includes pores, and the total volume of the pores is 30% to 80% of the total volume of the current collector, and a flame retardant layer containing a flame retardant is formed on at least one surface of the current collector.
상기 양극은 전술한 양극과 관련하여 기재된 집전체, 양극 활물질층 등과 동일하게 사용할 수 있다.The positive electrode can be used in the same manner as the current collector, positive electrode active material layer, etc. described in relation to the positive electrode described above.
상기 이차 전지는 본 발명의 양극 외에, 음극 및 분리막을 포함할 수 있다. 상기 음극은 음극 집전체 및 음극 집전체 상에 형성된 음극 활물질층을 포함할 수 있다. The secondary battery may include a negative electrode and a separator in addition to the positive electrode of the present invention. The negative electrode may include a negative electrode current collector and a negative electrode active material layer formed on the negative electrode current collector.
상기 음극 집전체는 당해 이차 전지에 화학적 변화를 유발하지 않으면서 도전성을 가진 것이라면 특별히 제한되는 것은 아니며, 예를 들어, 구리, 스테인레스 스틸, 알루미늄, 니켈, 티탄, 소성 탄소, 구리나 스테인레스 스틸의 표면에 카본, 니켈, 티탄, 은 등으로 표면처리한 것, 알루미늄-카드뮴 합금 등이 사용될 수 있다. 또한, 표면에 미세한 요철을 형성하여 음극 활물질의 결합력을 강화시킬 수도 있으며, 필름, 시트, 호일, 네트, 다공질체, 발포체, 부직포체 등 다양한 형태로 사용될 수 있다.The negative electrode current collector is not particularly limited as long as it has conductivity without causing chemical changes in the secondary battery, for example, copper, stainless steel, aluminum, nickel, titanium, fired carbon, the surface of copper or stainless steel. Surface treatment with carbon, nickel, titanium, silver, etc., aluminum-cadmium alloy, etc. can be used. In addition, the bonding power of the negative electrode active material can be strengthened by forming fine irregularities on the surface, and it can be used in various forms such as films, sheets, foils, nets, porous materials, foams, and non-woven fabrics.
상기 음극 활물질층은 음극 활물질을 포함할 수 있다. The negative electrode active material layer may include a negative electrode active material.
상기 음극 활물질의 종류는 인조흑연, 천연흑연, 흑연화 탄소섬유, 비정질탄소, 고결정성 탄소 등의 탄소질 재료; Si, Al, Sn, Pb, Zn, Bi, In, Mg, Ga, Cd, Si합금, Sn합금 또는 Al합금 등 리튬과 합금화가 가능한 금속질 화합물을 사용할 수 있다. 저결정성 탄소로는 연화탄소(soft carbon) 및 경화탄소(hard carbon)를 들 수 있으며, 고결정성 탄소로는 천연 흑연, 키시흑연(kish graphite), 열분해 탄소(pyrolytic carbon), 액정치피계 탄소섬유(mesophase pitch based carbon fiber), 탄소 미소구체(meso-carbon microbeads), 액정피치(mesophase pitches) 및 석유와 석탄계 코크스(petroleum or coal tar pitch derived cokes) 등의 고온 소성탄소를 들 수 있다. 음극 활물질은 필요에 따라 금속질 화합물과 탄소질 재료를 포함하는 복합물 등을 사용할 수도 있다. Types of the negative electrode active material include carbonaceous materials such as artificial graphite, natural graphite, graphitized carbon fiber, amorphous carbon, and highly crystalline carbon; Metallic compounds that can be alloyed with lithium, such as Si, Al, Sn, Pb, Zn, Bi, In, Mg, Ga, Cd, Si alloy, Sn alloy, or Al alloy, can be used. Low-crystalline carbon includes soft carbon and hard carbon, and high-crystalline carbon includes natural graphite, kish graphite, pyrolytic carbon, and liquid crystalline carbon. Examples include high-temperature calcined carbon such as mesophase pitch based carbon fiber, meso-carbon microbeads, mesophase pitches, and petroleum or coal tar pitch derived cokes. The negative electrode active material may be a composite containing a metallic compound and a carbonaceous material, if necessary.
바람직하게는, 상기 음극 활물질은 리튬 덴트라이드 발생을 억제하고, 상기 이차 전지의 수명 특성을 향상시키기 위해, 상기 음극 활물질은 니오비움(niobium)이 도핑된 티타늄-틴-옥사이드(titanium-tin-oxide) 및 상기 니오비움이 도핑된 티타늄-옥사이드(titanium-oxide)중 적어도 하나를 포함할 수 있다. Preferably, in order to suppress the generation of lithium dentride and improve the lifespan characteristics of the secondary battery, the negative electrode active material is titanium-tin-oxide doped with niobium. ) and the niobium-doped titanium-oxide (titanium-oxide).
상기 분리막은 음극 및 양극 사이에 개재될 수 있다. 상기 분리막은 음극과 양극 간 전기적 단락을 방지하고, 이온의 흐름이 발생되도록 구성된다. 상기 분리막은 다공성 고분자 필름 또는 다공성 부직포를 포함할 수 있다. 상기 다공성 고분자 필름은 에틸렌(ethylene) 중합체, 프로필렌(propylene) 중합체, 에틸렌/부텐(ethylene/butene) 공중합체, 에틸렌/헥센(ethylene/hexene) 공중합체, 및 에틸렌/메타크릴레이트(ethylene/methacrylate) 공중합체 등과 같은 폴리올레핀계 고분자를 포함한 단일층 혹은 다중층으로 구성될 수 있다. 상기 다공성 부직포는 고융점의 유리 섬유, 폴리에틸렌테레프탈레이트(polyethylene terephthalate) 섬유를 포함할 수 있다. 다만, 이에 한정되는 것이 아니며, 실시 형태에 따라 분리막은 세라믹(ceramic)을 포함한 고내열성 분리막(CCS; Ceramic Coated Separator)일 수 있다. The separator may be interposed between the cathode and the anode. The separator is configured to prevent electrical short-circuiting between the cathode and the anode and to generate a flow of ions. The separator may include a porous polymer film or a porous non-woven fabric. The porous polymer film includes ethylene polymer, propylene polymer, ethylene/butene copolymer, ethylene/hexene copolymer, and ethylene/methacrylate. It may be composed of a single layer or multiple layers containing polyolefin-based polymers such as copolymers. The porous nonwoven fabric may include high melting point glass fibers and polyethylene terephthalate (polyethylene terephthalate) fibers. However, it is not limited to this, and depending on the embodiment, the separator may be a highly heat-resistant separator (CCS; Ceramic Coated Separator) containing ceramic.
상기 양극, 음극 및 분리막은 권취(winding), 적층(lamination), 접음(folding), 또는 지그재그 스태킹(Zigzag stacking) 공정에 의해 전극 조립체로 제조될 수 있다. 상기 전극 조립체는 전해액과 함께 제공되어 본 발명에 따른 이차 전지로 제조될 수 있다. 상기 이차 전지는 캔을 사용한 원통형, 각형, 파우치(pouch)형, 및 코인(coin)형 중 어느 하나일 수 있으나, 이에 한정되는 것은 아니다.The anode, cathode, and separator may be manufactured into an electrode assembly by a winding, lamination, folding, or zigzag stacking process. The electrode assembly is provided with an electrolyte solution and can be manufactured into a secondary battery according to the present invention. The secondary battery may be any one of a cylindrical, square, pouch, or coin type using a can, but is not limited thereto.
상기 전해액은 비수 전해액일 수 있다. 전해액은 리튬염과 유기 용매를 포함할 수 있다. 상기 유기 용매는 프로필렌 카보네이트(PC), 에틸렌 카보네이트(EC), 디에틸 카보네이트(DEC), 디메틸 카보네이트(DMC), 에틸메틸 카보네이트(EMC), 메틸프로필 카보네이트(MPC), 디프로필 카보네이트(DPC), 비닐렌 카보네이트(VC), 디메틸 설포사이드(dimethyl sulfoxide), 아세토니트릴(acetonitrile), 디메톡시에탄(dimethoxyethane), 디에톡시에탄(diethoxyethane), 설포란(sulfolane), 감마-부티로락톤(gamma-butyrolactone), 프로필렌 설파이드(propylene sulfide), 또는 테트라하이드로퓨란(tetrahydrofuran) 중 적어도 어느 하나를 포함할 수 있다.The electrolyte may be a non-aqueous electrolyte. The electrolyte solution may include a lithium salt and an organic solvent. The organic solvent includes propylene carbonate (PC), ethylene carbonate (EC), diethyl carbonate (DEC), dimethyl carbonate (DMC), ethylmethyl carbonate (EMC), methylpropyl carbonate (MPC), dipropyl carbonate (DPC), Vinylene carbonate (VC), dimethyl sulfoxide, acetonitrile, dimethoxyethane, diethoxyethane, sulfolane, gamma-butyrolactone ), propylene sulfide, or tetrahydrofuran.
이하에서, 실시예 및 비교예를 바탕으로 본 발명을 더욱 구체적으로 설명한다. 다만, 다음의 실시예 및 비교예는 본 발명을 더욱 상세히 설명하기 위한 예시일 뿐, 본 발명이 다음의 실시예 및 비교예에 의해 한정되는 것은 아니다.Below, the present invention will be described in more detail based on examples and comparative examples. However, the following examples and comparative examples are only examples to explain the present invention in more detail, and the present invention is not limited by the following examples and comparative examples.
실시예Example
실시예 1Example 1
<양극 집전체 제조><Manufacturing of anode current collector>
유기 용매에 트리알킬 포스페이트(trialkyl phosphate)를 고형분 3 중량%가 되도록 혼합하여 난연층 조성물을 제조하였다. 상기 난연층 조성물을 15 ㎛ 두께의 알루미늄(기공도 50%)의 양면에 코팅한 후, 75 ℃에서 2시간 동안 건조하여 난연층이 형성된 양극 집전체를 제조하였다. 상기 기공도는 상기 알루미늄 전체 부피 대비 상기 알루미늄에 형성된 기공의 총 부피를 의미한다.A flame retardant layer composition was prepared by mixing trialkyl phosphate in an organic solvent to a solid content of 3% by weight. The flame retardant layer composition was coated on both sides of 15 ㎛ thick aluminum (porosity 50%) and then dried at 75°C for 2 hours to prepare a positive electrode current collector with a flame retardant layer. The porosity refers to the total volume of pores formed in the aluminum compared to the total volume of the aluminum.
<양극 활물질 제조><Manufacture of positive electrode active material>
황산철(FeSO4ㆍ7H2O), 인산(H3PO4), 및 산화 방지제를 포함한 수용액과 리튬 수용액(LiOHㆍH2O)의 혼합물에 pH 6이 되도록 암모니아수를 첨가하여 양극 슬러리를 제조하였다. 이후, 연속 공정 초임계 반응기에서 400 ℃ 및 270 bar의 조건하에 상기 양극 슬러리를 일정 속도로 투입하여 LiFePO4 용액을 제조하였으며, 상기 LiFePO4 용액을 수세 및 여과하여 LiFePO4 입자를 수득하였다. Prepare a positive electrode slurry by adding aqueous ammonia to a mixture of an aqueous solution containing iron sulfate (FeSO 4 ㆍ7H 2 O), phosphoric acid (H 3 PO 4 ), and antioxidants, and lithium aqueous solution (LiOHㆍH 2 O) to pH 6. did. Afterwards, a LiFePO 4 solution was prepared by adding the anode slurry at a constant rate under the conditions of 400 ° C. and 270 bar in a continuous process supercritical reactor, and the LiFePO 4 solution was washed and filtered to obtain LiFePO 4 particles .
상기 LiFePO4 입자, Super-P, 폴리비닐리덴플로오라이드를 95:2.5:2.5의 중량비로 N-메틸 피롤리돈 용매 중에서 혼합하여 양극 활물질을 제조하였다.A positive electrode active material was prepared by mixing the LiFePO 4 particles, Super-P, and polyvinylidene fluoride in N-methyl pyrrolidone solvent at a weight ratio of 95:2.5:2.5.
<양극 제조><Anode manufacturing>
상기 양극 집전체 상에 상기 양극 활물질을 도포한 후 건조하였다. 이후, 상기 양극 활물질을 압연하여 상기 양극 집전체 상에 양극 활물질층이 형성된 양극을 제조하였다. The positive electrode active material was applied on the positive electrode current collector and then dried. Thereafter, the positive electrode active material was rolled to manufacture a positive electrode in which a positive active material layer was formed on the positive electrode current collector.
<이차 전지 제조><Secondary battery manufacturing>
음극 활물질로서 TiNb2O7(TNO)을 포함하는 음극 및 상기 제조된 양극 사이에 두께 25 ㎛의 폴리에틸렌 소재의 분리막을 개재하여 전극 조립체를 제조한 후, 상기 전극 조립체를 케이스에 수납하고, 케이스 내부에 에틸렌 카보네이트:메틸에틸카보네이트가 2:1의 부피비로 혼합된 용매에 LiPF6 1M 및 비닐카보네이트 2.5 중량%로 혼합된 전해액을 투입하여 이차 전지를 제조하였다. After manufacturing an electrode assembly by interposing a separator made of polyethylene with a thickness of 25 ㎛ between a negative electrode containing TiNb 2 O 7 (TNO) as a negative electrode active material and the manufactured positive electrode, the electrode assembly is stored in a case, and the inside of the case is A secondary battery was manufactured by adding an electrolyte solution containing 1M LiPF 6 and 2.5% by weight of vinyl carbonate to a solvent containing ethylene carbonate:methylethylcarbonate mixed at a volume ratio of 2:1.
실시예 2Example 2
<양극 집전체 제조><Manufacturing of anode current collector>
유기 용매에 트리브로모네오펜틸알콜(tribromo neopentyl alcohol)을 고형분 3 중량%가 되도록 혼합하여 난연층 조성물을 제조하였다. 상기 난연층 조성물을 15 ㎛ 두께의 알루미늄(기공도 50%)의 양면에 코팅한 후, 75 ℃에서 2시간 동안 건조하여 난연층이 형성된 양극 집전체를 제조하였다.A flame retardant layer composition was prepared by mixing tribromo neopentyl alcohol in an organic solvent to a solid content of 3% by weight. The flame retardant layer composition was coated on both sides of 15 ㎛ thick aluminum (porosity 50%) and then dried at 75°C for 2 hours to prepare a positive electrode current collector with a flame retardant layer.
<양극 활물질 제조><Manufacture of positive electrode active material>
황산철(FeSO4ㆍ7H2O), 인산(H3PO4), 및 산화 방지제를 포함한 수용액과 리튬 수용액(LiOHㆍH2O)의 혼합물에 pH 6이 되도록 암모니아수를 첨가하여 양극 슬러리를 제조하였다. 이후, 연속 공정 초임계 반응기에서 400 ℃및 270 bar의 조건하에 상기 양극 슬러리를 일정 속도로 투입하여 LiFePO4 용액을 제조하였으며, LiFePO4 용액을 수세 및 여과하여 LiFePO4 입자를 수득하였다. 상기 LiFePO4 입자와 코팅 물질로서 Na2CO3을 혼합한 후, 700 ℃에서 5시간 동안 열처리하여 상기 LiFePO4 입자에 Na가 코팅된 양극 활물질을 수득하였다. Prepare a positive electrode slurry by adding aqueous ammonia to a mixture of an aqueous solution containing iron sulfate (FeSO 4 ㆍ7H 2 O), phosphoric acid (H 3 PO 4 ), and antioxidants, and lithium aqueous solution (LiOHㆍH 2 O) to pH 6. did. Afterwards, a LiFePO 4 solution was prepared by adding the positive electrode slurry at a constant rate under the conditions of 400° C. and 270 bar in a continuous process supercritical reactor, and the LiFePO 4 solution was washed and filtered to obtain LiFePO 4 particles. After mixing the LiFePO 4 particles with Na 2 CO 3 as a coating material, heat treatment was performed at 700° C. for 5 hours to obtain a positive electrode active material in which Na was coated on the LiFePO 4 particles.
상기 LiFePO4 입자, Super-P, 폴리비닐리덴플로오라이드를 95:2.5:2.5의 중량비로 N-메틸 피롤리돈 용매 중에서 혼합하여 양극 활물질을 제조하였다.A positive electrode active material was prepared by mixing the LiFePO 4 particles, Super-P, and polyvinylidene fluoride in N-methyl pyrrolidone solvent at a weight ratio of 95:2.5:2.5.
<양극 제조 및 이차 전지 제조><Anode manufacturing and secondary battery manufacturing>
상기 양극 집전체 및 상기 양극 활물질을 사용하는 것을 제외하고는, 상기 실시예 1과 동일한 공정에 의해 양극 및 이차 전지를 제조하였다.A positive electrode and a secondary battery were manufactured through the same process as Example 1, except for using the positive electrode current collector and the positive electrode active material.
실시예 3Example 3
실시예 1의 양극 집전체 제조 공정에서 기공도 50%인 알루미늄을 사용하는 대신 기공도가 30%인 알루미늄을 사용하는 것을 제외하고는, 실시예 1과 동일한 공정에 의해 이차 전지를 제조하였다.A secondary battery was manufactured in the same process as Example 1, except that aluminum with a porosity of 30% was used instead of aluminum with a porosity of 50% in the positive electrode current collector manufacturing process of Example 1.
실시예 4Example 4
실시예 1의 양극 집전체 제조 공정에서 기공도 50%인 알루미늄을 사용하는 대신 기공도가 40%인 알루미늄을 사용하는 것을 제외하고는, 실시예 1과 동일한 공정에 의해 이차 전지를 제조하였다.A secondary battery was manufactured in the same process as Example 1, except that aluminum with a porosity of 40% was used instead of aluminum with a porosity of 50% in the positive electrode current collector manufacturing process of Example 1.
실시예 5Example 5
실시예 1의 양극 집전체 제조 공정에서 기공도 50%인 알루미늄을 사용하는 대신 기공도가 70%인 알루미늄을 사용하는 것을 제외하고는, 실시예 1과 동일한 공정에 의해 이차 전지를 제조하였다.A secondary battery was manufactured through the same process as Example 1, except that aluminum with a porosity of 70% was used instead of aluminum with a porosity of 50% in the positive electrode current collector manufacturing process of Example 1.
실시예 6Example 6
실시예 1의 양극 집전체 제조 공정에서 기공도 50%인 알루미늄을 사용하는 대신 기공도가 80%인 알루미늄을 사용하는 것을 제외하고는, 실시예 1과 동일한 공정에 의해 이차 전지를 제조하였다.A secondary battery was manufactured through the same process as Example 1, except that aluminum with a porosity of 80% was used instead of aluminum with a porosity of 50% in the positive electrode current collector manufacturing process of Example 1.
실시예 7Example 7
실시예 2의 양극 집전체 제조 공정에서 기공도 50%인 알루미늄을 사용하는 대신 기공도가 30%인 알루미늄을 사용하는 것을 제외하고는, 실시예 2와 동일한 공정에 의해 이차 전지를 제조하였다.A secondary battery was manufactured in the same process as Example 2, except that aluminum with a porosity of 30% was used instead of aluminum with a porosity of 50% in the positive electrode current collector manufacturing process of Example 2.
실시예 8Example 8
실시예 1의 양극 집전체 제조 공정에서 기공도 50%인 알루미늄을 사용하는 대신 기공도가 80%인 알루미늄을 사용하는 것을 제외하고는, 실시예 1과 동일한 공정에 의해 이차 전지를 제조하였다.A secondary battery was manufactured through the same process as Example 1, except that aluminum with a porosity of 80% was used instead of aluminum with a porosity of 50% in the positive electrode current collector manufacturing process of Example 1.
비교예 1Comparative Example 1
실시예 1의 양극 집전체를 사용하는 대신, 기공 및 난연층이 형성되지 않은 15 ㎛ 두께의 알루미늄을 양극 집전체로 사용하며, 음극 활물질로서 TiNb2O7(TNO) 대신 탄소계 물질을 사용하는 것을 제외하고는, 실시예 1과 동일한 공정에 의해 이차 전지를 제조하였다.Instead of using the positive electrode current collector of Example 1, 15 ㎛ thick aluminum without pores and flame retardant layer was used as the positive electrode current collector, and a carbon-based material was used instead of TiNb 2 O 7 (TNO) as the negative electrode active material. Except for this, a secondary battery was manufactured through the same process as Example 1.
비교예 2Comparative Example 2
실시예 1의 양극 집전체 제조 공정에서 난연층이 형성된 양극 집전체를 사용하는 대신 난연층이 형성되지 않은 양극 집전체를 사용하며, 음극 활물질로서 TiNb2O7(TNO) 대신 탄소계 물질을 사용하는 것을 제외하고는, 실시예 1과 동일한 공정에 의해 이차 전지를 제조하였다.In the positive electrode current collector manufacturing process of Example 1, instead of using the positive electrode current collector with a flame retardant layer, a positive electrode current collector without a flame retardant layer is used, and a carbon-based material is used instead of TiNb 2 O 7 (TNO) as the negative electrode active material. A secondary battery was manufactured through the same process as Example 1, except that.
비교예 3Comparative Example 3
실시예 1의 양극 집전체 제조 공정에서 기공도 50%인 알루미늄을 사용하는 대신 기공도가 20%인 알루미늄을 사용하며, 음극 활물질로서 TiNb2O7(TNO) 대신 탄소계 물질을 사용하는 것을 제외하고는, 실시예 1과 동일한 공정에 의해 이차 전지를 제조하였다.In the positive electrode current collector manufacturing process of Example 1, aluminum with a porosity of 20% was used instead of aluminum with a porosity of 50%, and a carbon-based material was used instead of TiNb 2 O 7 (TNO) as the negative electrode active material. Then, a secondary battery was manufactured through the same process as Example 1.
비교예 4Comparative Example 4
실시예 1의 양극 집전체 제조 공정에서 기공도 50%인 알루미늄을 사용하는 대신 기공도가 90%인 알루미늄을 사용하며, 음극 활물질로서 TiNb2O7(TNO) 대신 탄소계 물질을 사용하는 것을 제외하고는, 실시예 1과 동일한 공정에 의해 이차 전지를 제조하였다.In the positive electrode current collector manufacturing process of Example 1, aluminum with a porosity of 90% is used instead of aluminum with a porosity of 50%, and a carbon-based material is used instead of TiNb 2 O 7 (TNO) as the negative electrode active material. Then, a secondary battery was manufactured through the same process as Example 1.
실험예Experiment example
실험예 1 - 고율 특성 평가Experimental Example 1 - High rate characteristic evaluation
상기 실시예 1 내지 8 및 비교예 1 내지 4에서 제조된 각각의 이차 전지를 상온에서 리튬 금속 대비 2.5V 내지 4.1V의 전압 범위에서 0.1C rate의 정전류로 충전시키면서, 방전시의 전류밀도가 증가함에 따른 방전용량을 얻고 이로부터 율별 충방전 효율을 계산하였다. 방전시의 전류밀도는 각각 0.1C, 0.2C, 0.5C, 1C 및 2C rate였다. 2C에서의 충방전 효율은 하기 식 1에 의해 계산하였으며, 그 결과를 하기 표 1에 나타내었다.Each of the secondary batteries manufactured in Examples 1 to 8 and Comparative Examples 1 to 4 were charged at a constant current of 0.1C rate in a voltage range of 2.5V to 4.1V relative to lithium metal at room temperature, and the current density during discharging increased. The discharge capacity was obtained and the charge/discharge efficiency for each rate was calculated from this. The current densities during discharge were 0.1C, 0.2C, 0.5C, 1C, and 2C rates, respectively. The charge/discharge efficiency at 2C was calculated using Equation 1 below, and the results are shown in Table 1 below.
[식 1][Equation 1]
2C에서의 충방전 효율(%)=[2C 방전용량/0.1C 충전용량]Х100Charge/discharge efficiency at 2C (%)=[2C discharge capacity/0.1C charge capacity]Х100
실험예 2 - 수명 특성 평가Experimental Example 2 - Evaluation of lifespan characteristics
상기 실시예 1 내지 8 및 비교예 1 내지 4에서 제조된 각각의 이차 전지를 상온에서 리튬 금속 대비 2.5V 내지 4.1V의 전압 범위에서 1C rate의 정전류로 충방전시키면서 용량유지율 및 500번째 사이클에서의 방전용량을 측정하였다. 상온에서 용량유지율은 하기 식 2에 의해 계산하였으며, 그 결과를 하기 표 1에 나타내었다.Each of the secondary batteries prepared in Examples 1 to 8 and Comparative Examples 1 to 4 were charged and discharged at a constant current of 1C rate in a voltage range of 2.5V to 4.1V relative to lithium metal at room temperature, and the capacity retention rate and Discharge capacity was measured. The capacity retention rate at room temperature was calculated using Equation 2 below, and the results are shown in Table 1 below.
[식 2][Equation 2]
용량유지율(%) = [500번째 사이클에서의 방전용량/1번째 사이클에서의 방전용량]Х100Capacity maintenance rate (%) = [discharge capacity at 500th cycle/discharge capacity at 1st cycle]Х100
실험예 3 - 안정성 평가Experimental Example 3 - Stability Evaluation
상기 실시예 1 내지 8 및 비교예 1 내지 4의 이차 전지를 각각 20개씩 제조하였다. 상기 20개의 각각의 이차 전지에 대해, 상기 이차 전지의 수직 방향에서 무게 10 kg, 직경 20 mm의 스테인레스 봉을 높이 100 cm에서 수직 낙하시켜 이차 전지의 전극 대면 부위의 단락을 유발시킨 후 하기 기준으로 안정성을 평가하였으며, 그 결과를 하기 표 1에 나타내었다.Twenty secondary batteries each of Examples 1 to 8 and Comparative Examples 1 to 4 were manufactured. For each of the 20 secondary batteries, a stainless steel rod weighing 10 kg and having a diameter of 20 mm was dropped vertically from a height of 100 cm in the vertical direction of the secondary battery to cause a short circuit in the area facing the electrode of the secondary battery. Then, according to the following criteria: Stability was evaluated, and the results are shown in Table 1 below.
- ○: 발화된 이차 전지 없음- ○: No ignited secondary battery
- △: 3개 이하의 이차 전지에서 발화가 발생됨- △: Ignition occurs in 3 or less secondary batteries.
- ×: 3개 초과의 이차 전지에서 발화가 발생됨- ×: Ignition occurred in more than 3 secondary batteries
부피2) pore
Volume 2)
여부3) Flame retardant layer formation
3) Whether
충방전 효율(%)in 2C
Charge/discharge efficiency (%)
유지율
(%)Volume
retention rate
(%)
(mAh/g)Discharge capacity at 500th cycle
(mAh/g)
2) 기공 부피: 양극 집전체 전체 부피 대비 기공의 총 부피
3) 난연층 형성 여부: 양극 집전체의 적어도 일 표면에 난연제를 포함하는 난연층 형성 여부1) Whether pores are formed: Whether pores are formed on the positive electrode current collector.
2) Pore volume: Total volume of pores compared to the total volume of the positive electrode current collector.
3) Whether a flame retardant layer is formed: Whether a flame retardant layer containing a flame retardant is formed on at least one surface of the positive electrode current collector.
상기 표 1에서 확인할 수 있는 바와 같이, 양극 집전체가 특정 범위의 기공도를 가지며, 양극 집전체 상에 난연층이 형성된 실시예 1 내지 8은 비교예 1 내지 4 대비 안정성이 향상되며, 고율 특성이 우수하고, 방전속도(C-rate)의 증가에 따른 용량 유지율이 우수한 것을 확인할 수 있었다. 또한, 실시예 1 내지 8은 비교예 1 내지 4 대비 수명 특성 및 방전 용량이 현저히 향상된 것을 확인할 수 있었다. 즉, 본 발명에 따른 양극을 포함하는 실시예 1 내지 8은 안정성이 향상되며, 고율 특성이 우수한 동시에 수명 특성 및 방전 용량도 향상된 것을 확인할 수 있었다.As can be seen in Table 1, Examples 1 to 8, in which the positive electrode current collector has a porosity in a specific range and a flame retardant layer is formed on the positive electrode current collector, have improved stability compared to Comparative Examples 1 to 4, and have high rate characteristics It was confirmed that this was excellent and that the capacity maintenance rate was excellent as the discharge rate (C-rate) increased. In addition, it was confirmed that Examples 1 to 8 had significantly improved lifespan characteristics and discharge capacity compared to Comparative Examples 1 to 4. That is, it was confirmed that Examples 1 to 8 containing the positive electrode according to the present invention had improved stability and excellent high rate characteristics, while also improving life characteristics and discharge capacity.
Claims (5)
상기 양극은,
집전체; 및
LiFePO4 입자에 나트륨(Na) 원소가 코팅된 활물질을 포함하는 양극 활물질층을 포함하며,
상기 음극은 음극 활물질로서 TiNb2O7(TNO)를 포함하며,
상기 집전체는 기공을 포함하며, 상기 집전체 전체 부피 대비 상기 기공의 총 부피는 30 % 내지 80 %이며,
상기 집전체의 적어도 일 표면에 난연제를 포함하는 난연층이 형성된 것인 이차 전지.A secondary battery comprising an anode, a cathode, and a separator interposed between the anode and the cathode,
The anode is,
house collector; and
It includes a positive electrode active material layer containing an active material coated with sodium (Na) elements on LiFePO 4 particles,
The negative electrode includes TiNb 2 O 7 (TNO) as a negative electrode active material,
The current collector includes pores, and the total volume of the pores is 30% to 80% of the total volume of the current collector,
A secondary battery in which a flame retardant layer containing a flame retardant is formed on at least one surface of the current collector.
상기 양극 활물질층은 폴리아크릴아마이드(Polyacrylamide), 폴리우레탄(polyurethane), 및 폴리아크릴로나이트릴(polyacrylonitrile)로 이루어진 군에서 선택되는 1종 이상의 수평균 분자량 30,000 g/mol 내지 80,000 g/mol를 가지는 바인더 응집제를 포함하는 것인 이차 전지.According to paragraph 1,
The positive electrode active material layer is one or more selected from the group consisting of polyacrylamide, polyurethane, and polyacrylonitrile, and has a number average molecular weight of 30,000 g/mol to 80,000 g/mol. A secondary battery containing a binder coagulant.
상기 난연제는 지방족 할로겐 화합물을 포함하는 것인 이차 전지.According to paragraph 1,
A secondary battery wherein the flame retardant includes an aliphatic halogen compound.
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| KR20230042267A (en) * | 2021-09-18 | 2023-03-28 | 컨템포러리 엠퍼렉스 테크놀로지 씨오., 리미티드 | Electrode and its manufacturing method, battery and electric device |
| KR20230060294A (en) * | 2021-10-27 | 2023-05-04 | 에스케이온 주식회사 | Electrode current collector, electrode comprising the same and secondary battery comprising the same |
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| KR20230042267A (en) * | 2021-09-18 | 2023-03-28 | 컨템포러리 엠퍼렉스 테크놀로지 씨오., 리미티드 | Electrode and its manufacturing method, battery and electric device |
| KR20230060294A (en) * | 2021-10-27 | 2023-05-04 | 에스케이온 주식회사 | Electrode current collector, electrode comprising the same and secondary battery comprising the same |
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