KR100553736B1 - Composition of active material for lithium secondary batteries - Google Patents
Composition of active material for lithium secondary batteries Download PDFInfo
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- KR100553736B1 KR100553736B1 KR1019990037102A KR19990037102A KR100553736B1 KR 100553736 B1 KR100553736 B1 KR 100553736B1 KR 1019990037102 A KR1019990037102 A KR 1019990037102A KR 19990037102 A KR19990037102 A KR 19990037102A KR 100553736 B1 KR100553736 B1 KR 100553736B1
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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
- 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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- 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
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- 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
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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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
- 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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
본 발명은 리튬 2차 전지용 활물질 조성물에 관한 것으로서, 활물질, 도전제, 결합제 및 캐스팅 용매를 포함하는 리튬 2차 전지용 활물질 조성물에 있어서, 스테아르산나트륨, 스테아르산칼륨 및 스테아르산의 황산 에스테르로 이루어진 군에서 선택되는 어느 하나를 조성물 총중량을 기준으로 1 내지 3중량% 더 포함하는 것을 특징으로 하는 활물질 조성물을 제공한다. 본 발명에 따른 활물질 조성물은 별도로 집전체를 전처리하지 않고도 집전체 상의 활물질층의 형성이 가능하므로 집전체의 전처리에 따르는 문제점이 발생되지 않고, 집전체 전처리공정을 거치지 않으므로 리튬 2차 전지의 제조원가를 낮출 수 있게 된다.The present invention relates to an active material composition for a lithium secondary battery, the active material composition for a lithium secondary battery comprising an active material, a conductive agent, a binder, and a casting solvent, the group consisting of sodium stearate, potassium stearate and sulfuric acid ester of stearic acid It provides an active material composition comprising any one selected from 1 to 3% by weight based on the total weight of the composition. Since the active material composition according to the present invention can form the active material layer on the current collector without pretreatment of the current collector separately, there is no problem caused by the pretreatment of the current collector, and the current cost is not increased. Can be lowered.
Description
본 발명은 리튬 2차 전지용 활물질 조성물에 관한 것으로서, 상세하게는 집전체를 전처리하지 않고도 집전체 상에 활물질층의 형성이 가능한 활물질 조성물에 관한 것이다. The present invention relates to an active material composition for a lithium secondary battery, and more particularly, to an active material composition capable of forming an active material layer on a current collector without pretreating the current collector.
리튬 2차 전지는 통상적으로 양극, 세퍼레이타 및 음극를 포함하여 이루어진다. 이 때 상기 양극와 음극는 각각의 집전체 상부에 활물질 조성물을 도포하여 활물질층을 형성함으로써 제조된다. 이렇게 얻어진 양극, 음극 및 세퍼레이타를 열 또는 압력을 이용하여 라미네이팅함으로써 형성된다.Lithium secondary batteries typically comprise a positive electrode, a separator and a negative electrode. In this case, the positive electrode and the negative electrode are manufactured by coating an active material composition on each current collector to form an active material layer. The positive electrode, negative electrode, and separator thus obtained are formed by laminating using heat or pressure.
일반적으로 활물질 조성물은 결합제, 도전제, 활물질 및 캐스팅용매로 이루어져 있다. 이 활물질 조성물을 집전체 상부에 직접 도포하는 방법에 따르면, 집전체에 대한 활물질층의 결합력이 약하고, 집전체와 활물질층간의 계면저항이 상승되어 여러 가지 문제점을 발생시킨다. 이러한 문제점을 해결하기 위하여 집전체의 양 면에 통상적인 결합제와 도전제를 포함하는 조성물을 코팅 및 건조한 다음, 열처리하여 표면처리막을 형성하는 방법이 제안되었다. 그러나 이러한 전처리를 하는 경 우에는 리튬 2차 전지의 제조공정이 복잡해지고 제조단가를 상승시키는 문제가 있으므로 집전체의 전처리가 필요없는 활물질 조성물이 요구된다. Generally, the active material composition consists of a binder, a conductive agent, an active material, and a casting solvent. According to the method of directly applying the active material composition on the current collector, the bonding strength of the active material layer to the current collector is weak, and the interface resistance between the current collector and the active material layer is increased, causing various problems. In order to solve this problem, a method of coating and drying a composition including a conventional binder and a conductive agent on both sides of a current collector and then heat-treating it has been proposed to form a surface treatment film. However, the pretreatment requires an active material composition that does not require pretreatment of the current collector because of a problem in that the manufacturing process of the lithium secondary battery is complicated and the manufacturing cost is increased.
따라서, 본 발명이 이루고자 하는 기술적 과제는 집전체를 전처리하지 않고 활물질층의 형성이 가능한 활물질 조성물을 제공하는 것이다.Accordingly, the technical problem to be achieved by the present invention is to provide an active material composition capable of forming an active material layer without pretreating the current collector.
상기 기술적 과제를 달성하기 위하여 본 발명은, 활물질, 도전제, 결합제 및 캐스팅용매를 포함하는 리튬 2차 전지용 활물질 조성물에 있어서,In order to achieve the above technical problem, the present invention, in the active material composition for lithium secondary battery comprising an active material, a conductive agent, a binder and a casting solvent,
스테아르산나트륨, 스테아르산칼륨 및 스테아르산의 황산 에스테르로 이루어진 군에서 선택되는 어느 하나를 조성물의 총 중량을 기준으로 1 내지 3중량% 더 포함하는 것을 특징으로 하는 활물질 조성물을 제공한다.It provides an active material composition characterized in that it further comprises 1 to 3% by weight based on the total weight of the composition any one selected from the group consisting of sodium stearate, potassium stearate and sulfuric acid ester of stearic acid.
본 발명에 있어서, 상기 활물질이 리튬 복합 산화물인 경우에는 상기 활물질 조성물은 양극 형성용 활물질 조성물이다.In the present invention, when the active material is a lithium composite oxide, the active material composition is an active material composition for forming a positive electrode.
본 발명에 있어서, 상기 활물질이 리튬 및 리튬 이온 흡착 물질인 경우에는 상기 활물질 조성물은 음극 형성용 활물질 조성물이다. In the present invention, when the active material is a lithium and lithium ion adsorption material, the active material composition is an active material composition for forming a negative electrode.
본 발명에 있어서, 상기 결합제는 본 발명이 속하는 기술분야에서 통상 그 용도로 사용되는 것은 특별한 제한없이 사용가능한데, 폴리비닐알콜, 메틸 셀룰로오즈, 카르복시메틸 셀룰로오즈, 폴리에틸렌글리콜 및 폴리비닐리덴플루오라이드 등과 같은 불소계 폴리머를 들 수 있다. In the present invention, the binder may be used without particular limitation in the art to which the present invention pertains, and may be used without limitation, including fluorine-based compounds such as polyvinyl alcohol, methyl cellulose, carboxymethyl cellulose, polyethylene glycol, and polyvinylidene fluoride. And polymers.
본 발명에 있어서, 상기 도전제는 본 발명이 속하는 기술분야에서 통상 그 용도로 사용되는 것은 특별한 제한 없이 사용가능한데, 그 예로는 카본블랙을 들 수 있다.In the present invention, the conductive agent may be used without particular limitation in the technical field to which the present invention belongs, and examples thereof include carbon black.
본 발명에 있어서, 상기 캐스팅 용매는 본 발명이 속하는 기술분야에서 통상 그 용도로 사용되는 것은 특별한 제한없이 사용가능한데, 그 예로는 N-메틸-2-피롤리돈, 아세톤 또는 그 혼합물을 들 수 있으며, N-메틸-2-피롤리돈과 아세톤의 10:90 내지 90:10 혼합용매가 많이 사용된다.In the present invention, the casting solvent can be used without particular limitation that is commonly used for the purpose in the technical field to which the present invention belongs, and examples thereof include N-methyl-2-pyrrolidone, acetone or mixtures thereof. , 10:90 to 90:10 mixed solvents of N-methyl-2-pyrrolidone and acetone are frequently used.
본 발명에 있어서, 상기 활물질이 리튬 복합 산활물인 경우에는 상기 활물질 조성물은 양극 형성용이 되는데, 상기 리튬 복합 산화물은 본 발명이 속하는 기술분야에서 통상 그 용도로 사용되는 것은 특별한 제한없이 사용가능하며, 그 예로는 LiMn2O4, LiNiO2, LiCoO2 등을 들 수 있다. In the present invention, when the active material is a lithium composite active material, the active material composition is used for forming a positive electrode, and the lithium composite oxide may be used without particular limitation in the technical field to which the present invention pertains. Examples thereof include LiMn 2 O 4 , LiNiO 2 , LiCoO 2 , and the like.
본 발명에 있어서, 상기 활물질이 리튬 및 리튬 이온 흡착물질인 경우에는 상기 활물질 조성물이 음극 형성용이 되는데, 상기 리튬 및 리튬 이온 흡착물질은 본 발명에 속하는 기술분야에서 통상 그 용도로 사용되는 것은 특별한 제한없이 사용가능하며, 그 예로는 카본, 그래파이트 등을 들 수 있다.In the present invention, when the active material is a lithium and lithium ion adsorption material, the active material composition is used for the formation of a negative electrode, the lithium and lithium ion adsorption material is usually used for that purpose in the technical field belonging to the present invention is a special limitation It can be used without, and examples thereof include carbon, graphite and the like.
본 발명에 따른 활물질 조성물은 스테아르산나트륨, 스테아르산칼륨 또는 스테아르산의 황산 에스테르를 포함하는 것은 특징이다.The active material composition according to the present invention is characterized in that it comprises a sulfate ester of sodium stearate, potassium stearate or stearic acid.
일반적으로, 리튬 2차 전지용 전극의 제조 시 활물질 조성물을 집전체 상에 캐스팅하여 제조하며, 상기 집전체 중 양극 집전체로는 알루미늄으로 이루어진 익스팬디드(expanded) 메탈, 펀치드(punched) 메탈, 호일이 사용되고, 음극 집전체로는 구리로 이루어진 익스팬디드 메탈, 펀치드 메탈, 호일이 사용된다. In general, when manufacturing an electrode for a lithium secondary battery, the active material composition is manufactured by casting on a current collector. Among the current collectors, an anode current collector, an expanded metal, a punched metal, Foil is used and expanded metal, punched metal, and foil which consist of copper are used as a negative electrode collector.
상기 집전체로 사용되는 구리와 알루미늄은 친수성을 나타내고, 상기 결합제로 사용되는 폴리머는 소수성을 나타내므로 상기 결합제를 포함하는 활물질 조성물을 집전체상에 직접 도포하는 경우에 결합력이 약하여 집전체상에 활물질층의 형성이 어려운 것이다.Copper and aluminum used as the current collector exhibit hydrophilicity, and the polymer used as the binder exhibits hydrophobicity, so that when the active material composition including the binder is directly applied onto the current collector, the bonding strength is weak. Formation of layers is difficult.
그러나, 본 발명에 따른 활물질 조성물은 스테아르산나트륨, 스테아르산칼륨 또는 스테아르산의 황산 에스테르를 포함하고 있어 집전체와 활물질 조성물 사이의 결합력이 향상되어 집전체 상에 활물질층을 형성시킬 수 있는 것이다.However, the active material composition according to the present invention contains a sulfate ester of sodium stearate, potassium stearate or stearic acid, thereby improving the bonding strength between the current collector and the active material composition, thereby forming an active material layer on the current collector.
상기 스테아르산나트륨, 스테아르산칼륨 또는 스테아르산의 황산 에스테르는 음이온성 계면활성제로서 친수성기와 소수성기를 모두 포함하고 있어서 활물질 조성물과 집전체와의 결합력을 향상시킬 수 있다. The sulfate ester of sodium stearate, potassium stearate or stearic acid includes both hydrophilic and hydrophobic groups as an anionic surfactant, thereby improving the binding strength between the active material composition and the current collector.
상기 스테아르산나트륨, 스테아르산칼륨 또는 스테아르산의 황산에스테르의 함량은 활물질 조성물의 중량에 대해 1 내지 3중량% 포함되게 하는 것이 바람직하다. The content of the sulfate ester of sodium stearate, potassium stearate or stearic acid is preferably 1 to 3% by weight based on the weight of the active material composition.
다음으로, 본 발명에 따른 활물질 조성물을 이용하여 전극 및 리튬 2차 전지의 제조방법을 살펴보기로 한다. 특히 리튬 2차 전지 중 리튬 폴리머 전지를 중심으로 설명하겠다.Next, a method of manufacturing an electrode and a lithium secondary battery using the active material composition according to the present invention will be described. In particular, a description will be given of a lithium polymer battery among lithium secondary batteries.
일반적으로, 리튬 폴리머 전지의 제조방법은 활물질 조성물을 집전체에 코팅하여 전극을 제조하는 단계, 고분자 매트릭스를 제조하는 단계, 상기 전극과 고분자 매트릭스를 라미네팅하여 전지구조체를 제조하는 단계, 고분자 매트릭스에 공극을 형성하는 단계 및 전해액을 함침하는 단계로 나눌 수 있는데, 이에 따라 설명하 겠다.In general, a method of manufacturing a lithium polymer battery includes coating an active material composition on a current collector to produce an electrode, preparing a polymer matrix, laminating the electrode and the polymer matrix to prepare a battery structure, It can be divided into the step of forming voids and the step of impregnating the electrolyte, which will be described accordingly.
1. 전극의 제조1. Preparation of Electrode
전극은 양극과 음극으로 나눌 수 있고, 활물질 조성물을 집전체 상에 캐스팅한 다음 건조하여 제조한다.The electrode can be divided into a positive electrode and a negative electrode, and is prepared by casting the active material composition on a current collector and then drying.
활물질 조성물은 캐스팅 용매에 결합제를 용해시키고, 이와 별도로 스테아르산나트륨, 스테아르산칼륨 또는 스테아르산의 황산 에스테르 중 어느 하나와 활물질 및 도전제를 건식 혼합하여 얻은 혼합물을 상기의 용액에 가하고 균일하게 혼합하여 제조할 수 있다.The active material composition dissolves the binder in a casting solvent, and separately adds a mixture obtained by dry mixing the active material and the conductive agent with any one of sodium stearate, potassium stearate, or sulfuric acid ester of stearic acid to the solution and uniformly It can manufacture.
활물질 조성물에 사용되는 물질 및 집전체는 상술한 바와 같다. Materials and current collectors used in the active material composition are as described above.
2. 고분자 매트릭스의 제조2. Preparation of Polymer Matrix
고분자 매트릭스는 결합제, 무기충진제, 캐스팅 용매 및 가소제로 이루어진 고분자 매트릭스 조성물을 지지체 상에 캐스팅하고 건조한 다음 형성된 매트릭스를 지지체로부터 분리함으로써 제조된다.The polymer matrix is prepared by casting a polymer matrix composition consisting of a binder, an inorganic filler, a casting solvent and a plasticizer on a support, drying and separating the formed matrix from the support.
상기 결합제, 무기 충진제, 가소제 및 캐스팅 용매는 본 발명이 속하는 기술분야에서 그 용도로서 통상 사용되는 물질이라면 특별하게 제한되지 않으며, 예를 들어 결합제로는 비닐클로라이드, 헥사플루오로프로필렌, 퍼플루오로알콕시, 헥사플루오로이소부텐 및 아크릴로니트릴로부터 선택된 단량체의 호모폴리머 또는 코폴리머, 또는 그의 혼합물을 사용할 수 있고, 무기 충진제로는 실리카와 알루미나 등을 사용할 수 있고, 가소제로는 에틸렌 카보네이트, 프로필렌 카보네이트, 디메틸 카보네이트, 디에톡시에탄, 디부틸 프탈레이트, 디메톡시에탄, 디에틸 카보네이트, 디메톡시에탄, 디프로필 카보네이트 및 이들의 혼합물을 사용할 수 있고, 캐스팅 용매로는 아세톤과 테트라하이드로퓨란을 사용할 수 있다. The binder, the inorganic filler, the plasticizer and the casting solvent are not particularly limited as long as they are materials commonly used in the art to which the present invention pertains. For example, the binder may be vinyl chloride, hexafluoropropylene, perfluoroalkoxy. , Homopolymers or copolymers of monomers selected from hexafluoroisobutene and acrylonitrile, or mixtures thereof. Silica and alumina may be used as the inorganic filler, and ethylene carbonate, propylene carbonate, Dimethyl carbonate, diethoxyethane, dibutyl phthalate, dimethoxyethane, diethyl carbonate, dimethoxyethane, dipropyl carbonate and mixtures thereof can be used, and acetone and tetrahydrofuran can be used as a casting solvent.
3. 전지구조체의 제조3. Fabrication of Battery Structure
전지구조체는 앞서 고분자 매트릭스를 양극판과 음극판 사이에 위치하도록 라미네이팅 한 후에 가열 또는 가압하여 제조한다. 가열 또는 가압의 방법과 조건은 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자에게 잘 알려져 있는 방법 및 조건에 따른다.The battery structure is prepared by laminating the polymer matrix so as to be positioned between the positive electrode plate and the negative electrode plate before heating or pressing. Methods and conditions of heating or pressurization are in accordance with methods and conditions well known to those skilled in the art.
4. 전해액의 함침4. Impregnation of electrolyte
리튬 폴리머 전지는 추출용매를 사용하여 상기 전지구조체로부터 가소제를 추출한 후 비수계 유기용매 및 무기염을 포함하는 전해액을 상기 전지구조체에 주입함으로써 제조된다. The lithium polymer battery is manufactured by extracting a plasticizer from the battery structure using an extraction solvent and then injecting an electrolyte solution containing a non-aqueous organic solvent and an inorganic salt into the battery structure.
상기 가소제 추출용매로는 고분자 매트릭스에 사용되는 결합제에 대해서는 불용성이며, 저비점인 용매를 사용하는데, 통상 에틸에테르 또는 헥산이 사용된다. As the plasticizer extracting solvent, a solvent which is insoluble to the binder used in the polymer matrix and has a low boiling point is used. Usually, ethyl ether or hexane is used.
또한, 상기 전해액에 포함되는 비수계 유기용매와 무기염은 본 발명이 속하는 기술분야에서 그 용도로서 통상 사용되는 것이라면 특별한 제한을 받지 않으며, 구체적으로는 비수계 유기용매로는 프로필렌 카보네이트, 에틸렌 카보네이트, γ-부티로락톤, 1,3-디옥솔란, 디메톡시에탄, 디메틸 카보네이트, 디에틸카보네이트, 테트라하이드로퓨란, 디메틸설폭사이드 및 폴리에틸렌글리콜 디메틸에테르 중에서 선택된 적어도 1종의 용매를 사용할 수 있고, 무기염으로는 용매중에서 해리되어 리튬 이온을 내는 리튬 화합물을 사용할 수 있다. 무기염의 구체적인 예로는 과염 소산 리튬(lithium perchlorate, LiClO4), 사불화붕산 리튬(lithium tetrafluoroborate, LiBF4), 육불화인산 리튬(lithium hexafluorophosphate, LiPF6), 삼불화메탄술폰산 리튬(lithium trifluoromethansulfonate, LiCF3SO3) 및 리튬 비스트리플루오로메탄술포닐아미드(lithium bistrifluoromethansulfonylamide. LiN(CF3SO2)2)가 있다.In addition, the non-aqueous organic solvent and the inorganic salt included in the electrolyte solution is not particularly limited as long as it is commonly used as its use in the technical field to which the present invention belongs, specifically, as the non-aqueous organic solvent, propylene carbonate, ethylene carbonate, At least one solvent selected from γ-butyrolactone, 1,3-dioxolane, dimethoxyethane, dimethyl carbonate, diethyl carbonate, tetrahydrofuran, dimethyl sulfoxide and polyethylene glycol dimethyl ether can be used, and an inorganic salt As a lithium compound that dissociates in a solvent to give lithium ions. Specific examples of the inorganic salts include lithium perchlorate (LiClO 4 ), lithium tetrafluoroborate (LiBF 4 ), lithium hexafluorophosphate (LiPF 6 ), and lithium trifluoromethansulfonate (LiCF). 3 SO 3 ) and lithium bistrifluoromethansulfonylamide.LiN (CF 3 SO 2 ) 2 ).
이하, 본 발명을 하기 실시예를 들어 설명하기로 하되, 본 발명이 하기 실시예로만 한정되는 것은 아니다.Hereinafter, the present invention will be described with reference to the following examples, but the present invention is not limited only to the following examples.
실시예 1Example 1
결합제로 폴리비닐리덴플루오르 123g을 아세톤 1107g에 용해시키고, 별도로 양극 활물질로 LiNi0.8Co0.2O2(상품명: FYPH0004, 제조사:NIPPON chem) 1000g, 도전제로 도전성 카본(상품명:SUPER-P, 제조사:MMM. carbon Belblurn) 50g 및 스테아르산나트륨 15g을 건식 혼합한 혼합물을 상기 용액에 균일하게 분산시켜 양극활물질 조성물을 형성하고, 이 양극 활물질 조성물을 알루미늄 호일에 캐스팅하고 건조하여 양극을 제조하였다.123 g of polyvinylidene fluorine was dissolved in 1107 g of acetone as a binder, and 1000 g of LiNi 0.8 Co 0.2 O 2 (trade name: FYPH0004, manufacturer: NIPPON chem) was used as a cathode active material, and conductive carbon (trade name: SUPER-P, manufacturer: MMM. A dry mixture of 50 g of carbon Belblurn) and 15 g of sodium stearate was uniformly dispersed in the solution to form a positive electrode active material composition, and the positive electrode active material composition was cast on aluminum foil and dried to prepare a positive electrode.
결합제로 폴리비닐리덴플루오르 153.8g을 아세톤 1385g에 용해시키고, 별도로 음극 활물질로 메조카본파이버(상품명: MCF, 제조사: Petoca, Japan) 1000g, 도전제로 도전성 카본 50g 및 스테아르산나트륨 15g을 건식 혼합한 혼합물을 상기 용액에 균일하게 분산시켜 양극활물질 조성물을 형성하고, 이 양극 활물질 조성물을 구리 호일에 캐스팅하고 건조하여 양극판을 제조하였다.153.8 g of polyvinylidene fluoride was dissolved in 1385 g of acetone as a binder, and a dry mixture of 1000 g of mesocarbon fiber (trade name: MCF, manufacturer: Petoca, Japan) as a negative electrode active material, 50 g of conductive carbon and 15 g of sodium stearate as a conductive agent It was uniformly dispersed in the solution to form a positive electrode active material composition, and the positive electrode active material composition was cast on copper foil and dried to prepare a positive electrode plate.
다음으로, 아세톤 294ml에 비닐리덴플루오라이드/헥사플루오로프로필렌 공중합체(상품명: Kynar2801, 제조사: elf-atochem) 60g 용해시킨 후 실리카 50g과 디부틸프탈레이트 80g을 가하여 2시간 동안 교반하면서 균일하게 혼합하여 고분자 매트릭스 조성물을 제조하였다. 이 고분자 매트릭스 조성물을 지지체 상에 캐스팅하고 60℃에서 건조하여 고분자 매트릭스를 제조하였다.Next, 60 g of vinylidene fluoride / hexafluoropropylene copolymer (trade name: Kynar2801, manufacturer: elf-atochem) was dissolved in 294 ml of acetone, and then 50 g of silica and 80 g of dibutyl phthalate were added thereto, followed by uniform mixing with stirring for 2 hours. A polymer matrix composition was prepared. This polymer matrix composition was cast on a support and dried at 60 ° C. to prepare a polymer matrix.
이어서, 제조된 양극판, 고분자 매트릭스 및 음극판을 순차적으로 라미네이탕하여 전지구조체를 제조하였다. 다음으로, 전지구조체에서 에틸에테르로 가소제를 추출한 후에 에틸카보네이트, 디메틸카보네이트 및 에틸메틸카보네이트의 혼합용매에 LiPF6가 1.3M의 농도로 포함된 전해액(상품명: UBE3A 제조사: UBE, Japan)에 침지시켜 전지구조체 내로 전해액이 함습되도록 함으로써 리튬 폴리머 전지를 완성하였다.Subsequently, the positive electrode plate, the polymer matrix, and the negative electrode plate were sequentially laminated to prepare a battery structure. Next, the plasticizer was extracted from the battery structure with ethyl ether, and then immersed in an electrolyte solution (trade name: UBE3A manufacturer: UBE, Japan) containing LiPF 6 at a concentration of 1.3 M in a mixed solvent of ethyl carbonate, dimethyl carbonate, and ethyl methyl carbonate. The lithium polymer battery was completed by allowing the electrolyte solution to be moistened into the battery structure.
실시예 2Example 2
스테아르산나트륨 대신에 스테아르산칼륨 15g을 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 리튬 폴리머 전지를 제조하였다.A lithium polymer battery was manufactured in the same manner as in Example 1, except that 15 g of potassium stearate was used instead of sodium stearate.
실시예 3Example 3
스테아르산나트륨 대신에 스테아르산의 황산 에스테르 15g을 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 리튬 폴리머 전지를 제조하였다.A lithium polymer battery was manufactured in the same manner as in Example 1, except that 15 g of sulfuric acid ester of stearic acid was used instead of sodium stearate.
비교예Comparative example
스테아르산나트륨, 스테아르산칼륨 및 스테아르산의 황산 에스테르를 사용하지 않는 종래의 활물질 조성물을 이용하여 실시예 1, 2 및 3과 동일한 방법으로 리 튬 폴리머 전지를 제조하였다.A lithium polymer battery was prepared in the same manner as in Examples 1, 2, and 3 using a conventional active material composition that did not use sodium stearate, potassium stearate, and sulfuric acid esters of stearic acid.
상기 실시예 1-3 및 비교예에 따라 제조된 리튬 폴리머 전지에 있어서, 이온전도도, 고율 방전용량 및 수명 특성을 측정하였는데 거의 유사한 것으로 나타났다.In the lithium polymer battery prepared according to Examples 1-3 and Comparative Examples, the ion conductivity, the high rate discharge capacity, and the lifetime characteristics were measured, and found to be almost similar.
본 발명에 따른 활물질 조성물은 별도로 집전체를 전처리하지 않고도 집전체 상의 활물질층의 형성이 가능하므로 집전체의 전처리에 따르는 문제점이 발생되지 않고, 집전체 전처리공정을 거치지 않으므로 리튬 2차 전지의 제조원가를 낮출 수 있게 된다.Since the active material composition according to the present invention can form the active material layer on the current collector without pretreatment of the current collector separately, there is no problem caused by the pretreatment of the current collector, and the current cost is not increased. Can be lowered.
본 발명은 실시예를 참고로 설명되었으나 이는 예시적인 것에 불과하며, 본 발명의 기술분야의 통상의 지식을 가진 자라면 이로부터 다양한 변형 및 균등한 타 실시예가 가능하단는 점을 이해할 것이다. 따라서, 본 발명의 진정한 기술적 보호범위는 첨부된 특허청구범위의 기술적 사상에 의해 정해져야 할 것이다. Although the present invention has been described with reference to the embodiments, these are merely exemplary, and those skilled in the art will understand that various modifications and equivalent other embodiments are possible therefrom. Therefore, the true technical protection scope of the present invention will be defined by the technical spirit of the appended claims.
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| US5284722A (en) * | 1991-03-13 | 1994-02-08 | Sony Corporation | Non-aqueous electrolyte secondary battery |
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| JPH09199132A (en) * | 1996-01-22 | 1997-07-31 | Elf Atochem Japan Kk | Electrode and secondary battery using it |
| KR20000062304A (en) * | 1996-12-23 | 2000-10-25 | 디로 트라딩 아크티엔게젤샤프트 | Method and anode for improving the power density of lithium secondary batteries |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US4804596A (en) * | 1988-01-21 | 1989-02-14 | Honeywell Inc. | Electrode material/electrolyte system for non-aqueous cells |
| US5284722A (en) * | 1991-03-13 | 1994-02-08 | Sony Corporation | Non-aqueous electrolyte secondary battery |
| JPH09190819A (en) * | 1996-01-05 | 1997-07-22 | Fuji Photo Film Co Ltd | Nonaqueous secondary battery |
| JPH09199132A (en) * | 1996-01-22 | 1997-07-31 | Elf Atochem Japan Kk | Electrode and secondary battery using it |
| KR20000062304A (en) * | 1996-12-23 | 2000-10-25 | 디로 트라딩 아크티엔게젤샤프트 | Method and anode for improving the power density of lithium secondary batteries |
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