WO2016114474A1 - Slurry composition for electrode, electrode, and secondary battery - Google Patents

Slurry composition for electrode, electrode, and secondary battery Download PDF

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Publication number
WO2016114474A1
WO2016114474A1 PCT/KR2015/011068 KR2015011068W WO2016114474A1 WO 2016114474 A1 WO2016114474 A1 WO 2016114474A1 KR 2015011068 W KR2015011068 W KR 2015011068W WO 2016114474 A1 WO2016114474 A1 WO 2016114474A1
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electrode
binder
nbr
slurry composition
electrodes
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PCT/KR2015/011068
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French (fr)
Korean (ko)
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정도화
이현원
최상훈
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주식회사 엘지화학
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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
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H01M4/623—Binders being polymers fluorinated polymers
    • 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
    • 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

Definitions

  • the present invention relates to a slurry composition for an electrode, an electrode manufactured using the same, and a secondary battery including the electrode.
  • lithium ion secondary batteries and lithium ion capacitors are expected as power storage devices having high voltage and high energy density.
  • the electrode used for such an electrical storage device is manufactured by apply
  • the characteristics required for such an electrode binder include increasing the binding properties between the active substance and between the electrode active material and the current collector, or the resistance of the active substance from the active material layer due to the scratch resistance in the step of winding the electrode, subsequent cutting, and the like. Separation resistance such as fine powder does not occur, reduction of internal resistance of the battery, and the like.
  • N-methylolpi which is an organic solvent is generally used as a binder of the slurry for lithium secondary battery electrodes.
  • PVDF polyvinylidene fluoride
  • NMP ralidone
  • SBR styrene-butadiene rubber
  • CMC carboxymethylcellulose
  • the above-mentioned PVDF binder (for example, Japanese Patent No. 3966570) has low binding properties between electrode active materials and between electrode active materials and current collectors, and requires a large amount of binders for practical use, resulting in the use of lithium ion secondary batteries. There is a disadvantage that the capacity is lowered.
  • the SBR-based binder is used for a wide range of applications as a binder for an aqueous lithium ion secondary battery electrode in that the electrode active materials, the electrode active material, and the current collector can be bound together well (for example, Japanese Patent No.3562197). report).
  • the electrode active materials and the electrode active material and the current collector cannot be bound well, and thus the charge and discharge cycle characteristics of the lithium ion secondary battery are deteriorated.
  • the drag line 11 when forming the electrode pattern using the electrode slurry prepared using a conventional electrode binder, such as the PVDF binder or SBR-based binder, as shown in Figure 1, the drag line (Drag line 11)
  • the balcony 10 is formed, which is a problem.
  • safety problems such as an internal short circuit occur, and even when welding such as tab, the slurry hardens at a portion where the slurry should not be formed, which causes problems in welding.
  • the balcony 10 when the balcony 10 is formed, the balcony 10 causes capacity reduction due to thickness irregularity and taping of the battery.
  • the present invention has been made to solve the problems of the prior art as described above, the formation of the drag line (drag line) or balcony when forming the electrode pattern is minimized, resulting in short-circuit welding, such as tap, the thickness of the battery It is an object of the present invention to provide a slurry composition for electrodes, characterized in that the problem of capacity reduction due to unevenness and taping is minimized.
  • an object of this invention is to provide the slurry composition for electrodes which is excellent in binding power between an electrode active material and between an electrode active material and an electrical power collector, and reduces the internal resistance of a battery.
  • an object of the present invention is to provide a secondary battery including the electrode, and the electrode to reduce the defective rate of the battery, improve the charge and discharge cycle characteristics and capacity characteristics of the battery by being manufactured using the slurry composition for the electrode. .
  • the present invention provides a slurry composition for electrodes comprising a binder comprising an electrode active material, a PVdF binder and an NBR binder, and a solvent.
  • the NBR binder may include 1 to 100 wt% of H-NBR binder based on the total weight of the NBR binder.
  • the PVdF binder and the NBR binder may be included in a weight ratio of 2: 8 to 8: 2.
  • the binder including the electrode active material, the PVdF binder, and the NBR binder may be included in a weight ratio of 9.0: 1.0 to 9.9: 0.1.
  • the electrode slurry composition may further include a conductive material.
  • the H-NBR binder may remain at 60 mol% or less of a double bond of NBR by hydrogenation.
  • the H-NBR may include 40 to 85% by weight of hydrogenated butadiene and 15 to 60% by weight of acrylonitrile based on the total weight of H-NBR.
  • the viscosity of the slurry composition for the electrode may be 4,000 to 30,000 cps.
  • the present invention also provides an electrode produced using the slurry composition for the electrode and a secondary battery comprising the electrode.
  • the electrode may include a binder including an electrode active material, a polyvinylidene fluoride (PVF) binder, and a nitrile butadiene rubber (NBR) binder.
  • a binder including an electrode active material, a polyvinylidene fluoride (PVF) binder, and a nitrile butadiene rubber (NBR) binder.
  • PVF polyvinylidene fluoride
  • NBR nitrile butadiene rubber
  • the slurry composition for electrodes of the present invention includes an NBR binder, thereby minimizing the formation of a drag line or a balcony when forming an electrode pattern. It provides the effect of minimizing capacity reduction problem due to unevenness and taping.
  • the slurry composition for electrodes of the present invention provides an excellent binding force between the electrode active material and between the electrode active material and the current collector, and also provides an effect of reducing the internal resistance of the battery.
  • the electrode of the present invention is prepared using the slurry composition for the electrode to lower the defective rate of the battery, and provides an effect of improving the charge and discharge cycle characteristics and capacity characteristics of the battery.
  • the secondary battery of the present invention has a low defect rate by including the electrode, and is excellent in charge and discharge cycle characteristics and capacity characteristics.
  • FIG. 1 is a diagram schematically illustrating a drag line and a balcony generated when an electrode pattern is formed using a conventional slurry for electrodes.
  • (a) is a plan view of the electrode pattern
  • (b) is an ideally coated side cross section of the electrode pattern
  • (c) is an actual coated side cross section of the electrode pattern.
  • Figure 2 is a graph evaluating the characteristics of the lithium ion secondary battery (Example 1) manufactured using the electrode of the present invention.
  • FIG. 3 is a graph evaluating the characteristics of a lithium ion secondary battery (Comparative Example 1) manufactured using a conventional electrode.
  • the present invention relates to a binder composition comprising an electrode active material, a PVdF binder and an NBR binder, and a slurry composition for electrodes comprising a solvent.
  • the slurry composition for the electrode is not particularly limited as long as it is used for the production of the electrode, and may be used, for example, in secondary batteries such as lithium ion secondary batteries, storage batteries, and the like.
  • the PVdF binder refers to a binder including polyvinylidene fluoride or polyvinylidene difluoride as a binder generally used in the art.
  • the NBR (Nitrile Butadiene Rubber) binder refers to a binder including a copolymer of acrylonitrile and butadiene.
  • the NBR binder used in the present invention those known in the art may be used.
  • the NBR binder is a concept including a H-NBR binder prepared by hydrogenation reaction to NBR.
  • the NBR binder may include 1 to 100 wt% of a H-NBR (Hydrogenated-Nitrile Butadiene Rubber) binder based on the total weight of the NBR binder, preferably 40 to 80 wt%. Since the general NBR binder has a higher resistance than the H-NBR binder, a general NBR binder and an H-NBR binder may be used in combination, or only an H-NBR binder may be selected and used.
  • H-NBR Hydrophilidiene Rubber
  • the H-NBR binder used in the present invention may preferably be used to include H-NBR in which double bonds originally contained in the NBR remain at 60 mol% or less by hydrogenation.
  • the H-NBR may include 40 to 85% by weight of hydrogenated butadiene and 15 to 60% by weight of acrylonitrile, preferably 50 to 60% by weight of hydrogenated butadiene, based on the total weight of H-NBR. 75 wt% and acrylonitrile at 25-50 wt%.
  • the resistance may be increased to decrease the capacity, and when the content of the hydrogenated butadiene is greater than 85% by weight, the adhesion with the current collector may be reduced.
  • the PVdF binder and the NBR binder are preferably contained in a weight ratio of 2: 8 to 8: 2, more preferably 2: 8 to 3: 7.
  • the loading variation may be increased during the electrode coating process, and the fairness may be worsened.
  • the loading variation may be increased during the electrode coating process. And the adhesion with the current collector can be lowered.
  • the performance of the lithium ion secondary battery may be degraded.
  • the electrode active material used in the slurry composition for electrodes of this invention is not specifically limited, It can select suitably according to the kind of battery and a capacitor.
  • a lithium ion secondary battery positive electrode active material is, for example, LiCoO 2, LiNiO 2, lithium-containing composite metal oxides such as LiMnO 2, LiMn 2 O 4; Transition metal sulfides such as TiS 2 , TiS 3 , and amorphous MoS 3 ; Transition metal oxides such as Cu 2 V 2 O 3 , amorphous V 2 OP 2 O 5 , MoO 3 , V 2 O 5 , V 6 O 13, and the like.
  • Examples of the negative electrode active material include amorphous carbon, graphite, natural graphite, carbonaceous materials such as mesocarbon microbeads (MCMB) and pitch-based carbon fibers, conductive polymers such as polyacene, and the like.
  • MCMB mesocarbon microbeads
  • pitch-based carbon fibers conductive polymers such as polyacene, and the like.
  • a binder including an electrode active material, a PVdF binder, and an NBR binder may be included in a weight ratio of 9.0: 1.0 to 9.9: 0.1.
  • the content of the binder exceeds the above range, the charge / discharge performance and capacity of the device using the electrode may decrease, and when the content of the binder is less than the above range, a problem of insufficient binding force of the electrode may occur.
  • the solvent is not particularly limited as long as it can dissolve the PVdF binder and the NBR binder, and those known in the art may be used.
  • amides such as N-methylpyrrolidone, N, N-dimethylacetoamide, and N, N-dimethylformamide may be used, and among these, N-methylpyrrolidone may be applied to a current collector. Since it is good, it can be used preferably.
  • the amount of the solvent used may be determined to be a viscosity suitable for coating depending on the type of the electrode active material, the binder, and the conductive material described later.
  • concentration of the solid content of the electrode active material, the binder, and the conductive material described later may be adjusted to 50 to 95% by weight, more preferably 70 to 90% by weight.
  • the slurry composition for electrodes of the present invention may further include a conductive material.
  • the conductive material is not particularly limited and may be appropriately selected according to the type of battery and capacitor.
  • carbon such as graphite and activated carbon may be used.
  • nickel hydrogen secondary battery cobalt oxide may be used, and in the negative electrode, nickel powder, cobalt oxide, titanium oxide, and carbon may be used.
  • Examples of the carbon include acetylene black, furnace black, graphite, carbon fiber, and fullerenes.
  • the amount of the conductive material is usually 1 to 20 parts by weight, preferably 2 to 10 parts by weight based on 100 parts by weight of the electrode active material.
  • Viscosity modifiers, glidants, etc. may be further added to the slurry composition for electrodes as needed.
  • the viscosity of the slurry composition for the electrode may be 4,000 to 30,000 cps, preferably 8000 to 19000 cps.
  • the viscosity of the slurry composition for the electrode is less than 4,000 cps, high loading of the slurry for the electrode may be difficult, and when the viscosity of the electrode composition exceeds 30,000 cps, the coating of the slurry for the electrode may be uneven.
  • the slurry composition for electrodes of the present invention can be prepared by mixing the above components by methods known in the art.
  • the electrode may include a binder including an electrode active material, a polyvinylidene fluoride (PVDF) binder, and a nitrile butadiene rubber (NBR) binder.
  • PVDF polyvinylidene fluoride
  • NBR nitrile butadiene rubber
  • the electrode can be prepared by a method known in the art. That is, the electrode of the present invention can be prepared by applying the slurry composition for electrode of the present invention to a current collector and drying it.
  • the coating method to the collector of the said slurry composition for electrodes is not specifically limited. For example, methods, such as a doctor blade method, a dip method, the reverse roll method, the direct roll method, the gravure method, the extrusion method, the brush coating method, are mentioned.
  • the amount of the slurry to be applied is also not particularly limited, but an amount such that a mixed layer made of an active material, a binder, and the like formed after drying and removing the liquid medium is usually 0.005 to 5 mm, preferably 0.01 to 2 mm is common.
  • the drying method is not particularly limited, and examples thereof include drying by warm air, hot air and low humidity, vacuum drying, and drying by irradiation of (far) infrared rays and electron beams.
  • the drying rate is usually adjusted so that the liquid medium can be removed as soon as possible within a speed range such that cracks do not form in the mixed layer due to stress concentration or the mixed layer does not peel off from the current collector.
  • the density of the active material of the electrode can be increased by pressing the current collector after drying.
  • a press method methods, such as a metal mold
  • the current collector is not particularly limited as long as it is made of a conductive material.
  • a conductive material for example, in the case of a lithium ion secondary battery, one made of metal such as iron, copper, aluminum, nickel, stainless, or the like may be used.
  • the present invention also relates to a secondary battery comprising the electrode.
  • the secondary battery of the present invention includes the electrode and the electrolyte and can be manufactured according to a known method using a component such as a separator. Therefore, description thereof will be omitted.
  • LiCoO 2 , PVdF (trade name: KF1100, manufacturer: Kureha), and H-NBR (brand name: BM-730H, manufacturer: zeon) were mixed in a weight ratio of 8: 2, and acetylene black was used as a conductive material.
  • a slurry was prepared by mixing with N-methylpyrrolidone in a weight ratio of 2: 2, a slurry was applied to an aluminum (Al) foil current collector using a slot die coater, and dried to prepare a positive electrode.
  • a positive electrode was manufactured in the same manner as in Example 1, except that only a PVdF (trade name: KF1100, manufacturer: Kureha) binder was used as the binder.
  • PVdF trade name: KF1100, manufacturer: Kureha
  • a negative electrode was prepared in the same manner as in Example 1.
  • a binder of the water-based positive electrode as the positive electrode active material SBR (trade name: BM-L301, Manufacturer: zeon) binder, CMC (trade name: BG-L01, Manufacturer: GL-Chem), the conductive material, acetylene black 96 as: 2: 1
  • a slurry was prepared by mixing with N-methylpyrrolidone in a weight ratio of 1, and then applied to an aluminum (Al) foil current collector using a slot die coater, followed by drying to prepare a positive electrode.
  • a negative electrode was prepared in the same manner as in Example 1.
  • FIG. 2 A scanning electron microscope (SEM) image of the anode prepared in Example 1 is shown in FIG. 2 of Korean Patent Application No. 10-2015-0006905 (filed date: January 14, 2015) of the present invention. As confirmed in the photograph, it was confirmed that no drag line occurred in the anode of Example 1.
  • FIG. 3 A scanning electron microscope (SEM) image of the anode prepared in Comparative Example 1 is shown in FIG. 3 of Korean Patent Application No. 10-2015-0006905 (Application Date: January 14, 2015), which is the original application of the present invention. As confirmed in the above photograph, a drag line was confirmed at the anode of Comparative Example 1.
  • FIG. 4 An image photographing the appearance of the anode of Comparative Example 2 is shown in FIG. 4 of Korean Patent Application No. 10-2015-0006905 (Application Date: January 14, 2015), which is the original application of the present invention.
  • FIG. 4 As can be seen in the photo, in the positive electrode of Comparative Example 2, grains occurred during mixing and line defects occurred during coating.
  • the discharge capacity was measured to confirm the performance of the batteries produced in the above Examples and Comparative Examples.
  • the charge was charged at room temperature with CC / CV C-rate 0.5C 4.2V, 1 / 20C cut-off and the discharge was cut 2.5V with room temperature CC 0.2C.
  • the results are shown in FIGS. 2 and 3.
  • the present invention relates to a slurry composition for an electrode, an electrode prepared using the same, and a secondary battery including the electrode, wherein the slurry composition for the electrode includes an electrode active material, a polyvinylidene fluoride (PVDF) binder, and a nitrile butadiene rubber (NBR) binder. It includes.
  • the slurry composition for the electrode includes an electrode active material, a polyvinylidene fluoride (PVDF) binder, and a nitrile butadiene rubber (NBR) binder. It includes.
  • PVDF polyvinylidene fluoride
  • NBR nitrile butadiene rubber
  • the slurry composition for the electrode includes an NBR binder, thereby minimizing the formation of a drag line or a balcony when forming an electrode pattern, such as an internal short circuit due to the drag line or a balcony, difficulty in welding such as a tap, uneven thickness of a battery, and the like. It minimizes the capacity reduction problem caused by taping.

Abstract

The present invention provides: a slurry composition for an electrode, comprising an electrode active material, a binder including a PVdF binder and an NBR binder, and a solvent; an electrode manufactured using the slurry composition for an electrode; and a secondary battery including the electrode.

Description

전극용 슬러리 조성물, 전극 및 이차전지Slurry Composition for Electrodes, Electrodes and Secondary Batteries
본 발명은, 전극용 슬러리 조성물, 이를 사용하여 제조된 전극 및 상기 전극을 포함하는 이차전지에 관한 것이다. The present invention relates to a slurry composition for an electrode, an electrode manufactured using the same, and a secondary battery including the electrode.
최근에 전자 기기의 구동용 전원으로서 고전압, 고에너지 밀도를 갖는 축전디바이스가 요구되고 있다. 특히 리튬이온 이차전지나 리튬이온 캐패시터는 고전압, 고에너지 밀도를 갖는 축전 디바이스로서 기대되고 있다.Recently, power storage devices having high voltage and high energy density have been demanded as power sources for driving electronic devices. In particular, lithium ion secondary batteries and lithium ion capacitors are expected as power storage devices having high voltage and high energy density.
이러한 축전 디바이스에 사용되는 전극은 전극 활물질과 전극용 바인더의 혼합물을 집전체에 도포·건조함으로써 제조된다. 이러한 전극용 바인더에 요구되는 특성으로는, 활성질 사이 및 전극 활물질과 집전체 사이의 결착성을 높이는 것이나, 전극을 권취하는 공정에서의 내찰성, 그 후의 재단 등에 의해서 활성 물질층으로부터 활성 물질의 미세 분말 등이 발생하지 않는 내 분락적성(粉落適性), 전지의 내부저항 저감 등이 있다. The electrode used for such an electrical storage device is manufactured by apply | coating and drying the mixture of an electrode active material and the binder for electrodes to an electrical power collector. The characteristics required for such an electrode binder include increasing the binding properties between the active substance and between the electrode active material and the current collector, or the resistance of the active substance from the active material layer due to the scratch resistance in the step of winding the electrode, subsequent cutting, and the like. Separation resistance such as fine powder does not occur, reduction of internal resistance of the battery, and the like.
예를 들어, 리튬 이차전지 전극용 슬러리를 구리박, 알루미늄박 등에 도포 시공하여, 리튬이온 이차전지용 전극을 제조하는 경우, 일반적으로 리튬 이차전지 전극용 슬러리의 바인더로는 유기 용제인 N-메틸올피롤리돈(NMP)을 용제로 한 폴리불화비닐리덴(PVDF)이나 증점제로서 카르복시메틸셀룰로오스(CMC)를 병용하는 스티렌-부타디엔 고무(SBR) 등이 사용되고 있다.For example, when the slurry for lithium secondary battery electrodes is apply | coated to copper foil, an aluminum foil, etc., and an electrode for lithium ion secondary batteries is manufactured, N-methylolpi which is an organic solvent is generally used as a binder of the slurry for lithium secondary battery electrodes. Polyvinylidene fluoride (PVDF) using a ralidone (NMP) solvent, and styrene-butadiene rubber (SBR) which uses carboxymethylcellulose (CMC) together as a thickener are used.
상기 PVDF 바인더(예를 들어, 일본 특허 제3966570호 공보)는 전극 활물질 사이 및 전극 활물질과 집전체 사이의 결착성이 낮고, 실제로 사용하기에는 다량의 바인더를 필요로 하여, 결과적으로 리튬이온 이차전지의 용량이 저하되는 결점이 있다.The above-mentioned PVDF binder (for example, Japanese Patent No. 3966570) has low binding properties between electrode active materials and between electrode active materials and current collectors, and requires a large amount of binders for practical use, resulting in the use of lithium ion secondary batteries. There is a disadvantage that the capacity is lowered.
상기 SBR계 바인더는 전극 활물질끼리 및 전극 활물질과 집전체를 양호하게 결착할 수 있는 점에서, 수계의 리튬이온 이차전지 전극용 바인더로서 폭넓은 용도로 사용되고 있다(예를 들어, 일본 특허 제3562197호 공보). 그러나, 전지의 고용량화를 위하여 바인더 사용량을 감량한 슬러리에서는 전극 활물질끼리 및 전극 활물질과 집전체를 양호하게 결착시킬 수 없어, 리튬이온 이차전지의 충방전 사이클 특성이 저하되는 단점을 갖는다.The SBR-based binder is used for a wide range of applications as a binder for an aqueous lithium ion secondary battery electrode in that the electrode active materials, the electrode active material, and the current collector can be bound together well (for example, Japanese Patent No.3562197). report). However, in the slurry in which the amount of binder used is reduced to increase the capacity of the battery, the electrode active materials and the electrode active material and the current collector cannot be bound well, and thus the charge and discharge cycle characteristics of the lithium ion secondary battery are deteriorated.
특히, 상기 PVDF 바인더나 SBR계 바인더 등 종래의 전극용 바인더를 사용하여 제조된 전극용 슬러리를 사용하여 전극 패턴을 형성하는 경우, 도 1에 도시된 바와 같이, 드레그 라인(Drag line)(11)이나 발코니(10)가 형성되어 문제가 되고 있다. 상기 드레그 라인(11)이 발생하면 내부단락 등의 안전성 문제가 발생하며, Tab 등의 용접시에도 슬러리가 없어야 할 부분에 슬러리가 굳어 있어 용접이 잘 되지 않는 문제가 발생한다. 또한, 상기 발코니(10)가 형성된 경우 상기 발코니(10)로 인하여 전지의 두께 불균일 및 Taping으로 인한 용량 감소가 발생한다. In particular, when forming the electrode pattern using the electrode slurry prepared using a conventional electrode binder, such as the PVDF binder or SBR-based binder, as shown in Figure 1, the drag line (Drag line 11) However, the balcony 10 is formed, which is a problem. When the drag line 11 occurs, safety problems such as an internal short circuit occur, and even when welding such as tab, the slurry hardens at a portion where the slurry should not be formed, which causes problems in welding. In addition, when the balcony 10 is formed, the balcony 10 causes capacity reduction due to thickness irregularity and taping of the battery.
[선행기술문헌] [Preceding technical literature]
[특허문헌][Patent Documents]
일본 특허 제3966570호 공보Japanese Patent No. 3966570
일본 특허 제3562197호 공보Japanese Patent No. 3552397
본 발명은 상기와 같은 종래기술의 문제점을 해결하기 위하여 안출된 것으로서, 전극 패턴의 형성시 드레그 라인(Drag line)이나 발코니의 형성이 최소화되어 그로 인한 내부단락, Tap 등의 용접곤란, 전지의 두께 불균일 및 Taping으로 인한 용량 감소 문제가 최소화되는 것을 특징으로 하는 전극용 슬러리 조성물을 제공하는 것을 목적으로 한다.The present invention has been made to solve the problems of the prior art as described above, the formation of the drag line (drag line) or balcony when forming the electrode pattern is minimized, resulting in short-circuit welding, such as tap, the thickness of the battery It is an object of the present invention to provide a slurry composition for electrodes, characterized in that the problem of capacity reduction due to unevenness and taping is minimized.
또한, 본 발명은 전극 활물질 사이 및 전극 활물질과 집전체의 사이의 결착력 우수하며, 전지의 내부저항을 저감시키는 전극용 슬러리 조성물을 제공하는 것을 목적으로 한다.Moreover, an object of this invention is to provide the slurry composition for electrodes which is excellent in binding power between an electrode active material and between an electrode active material and an electrical power collector, and reduces the internal resistance of a battery.
또한, 본 발명은 상기 전극용 슬러리 조성물을 사용하여 제조됨으로써 전지의 불량률을 낮추며, 전지의 충방전 사이클 특성 및 용량 특성을 향상시키는 전극, 및 상기 전극을 포함하는 이차전지를 제공하는 것을 목적으로 한다.In addition, an object of the present invention is to provide a secondary battery including the electrode, and the electrode to reduce the defective rate of the battery, improve the charge and discharge cycle characteristics and capacity characteristics of the battery by being manufactured using the slurry composition for the electrode. .
본 발명은 전극 활물질, PVdF 바인더 및 NBR 바인더를 포함하는 바인더, 및 용제를 포함하는 전극용 슬러리 조성물을 제공한다. The present invention provides a slurry composition for electrodes comprising a binder comprising an electrode active material, a PVdF binder and an NBR binder, and a solvent.
상기 NBR 바인더는 NBR 바인더 총 중량을 기준으로 H-NBR 바인더가 1 내지 100 중량%로 포함될 수 있다.The NBR binder may include 1 to 100 wt% of H-NBR binder based on the total weight of the NBR binder.
상기 PVdF 바인더 및 NBR 바인더는 2:8 내지 8:2의 중량비로 포함될 수 있다.The PVdF binder and the NBR binder may be included in a weight ratio of 2: 8 to 8: 2.
상기 전극 활물질과 상기 PVdF 바인더 및 NBR 바인더를 포함하는 바인더는 9.0:1.0 내지 9.9:0.1의 중량비로 포함될 수 있다.The binder including the electrode active material, the PVdF binder, and the NBR binder may be included in a weight ratio of 9.0: 1.0 to 9.9: 0.1.
상기 전극용 슬러리 조성물은 도전재를 더 포함할 수 있다.The electrode slurry composition may further include a conductive material.
상기 H-NBR 바인더는 수소첨가에 의해 NBR의 이중결합이 60 몰% 이하로 잔존할 수 있다.The H-NBR binder may remain at 60 mol% or less of a double bond of NBR by hydrogenation.
상기 H-NBR은 상기 H-NBR 전체 중량에 대하여 수소화된 부타디엔(hydrogenated buradiene)을 40 내지 85 중량% 및 아크릴로니트릴을 15 내지 60 중량%로 포함할 수 있다.The H-NBR may include 40 to 85% by weight of hydrogenated butadiene and 15 to 60% by weight of acrylonitrile based on the total weight of H-NBR.
상기 전극용 슬러리 조성물의 점도는 4,000 내지 30,000cps일 수 있다.The viscosity of the slurry composition for the electrode may be 4,000 to 30,000 cps.
또한 본 발명은 상기 전극용 슬러리 조성물을 사용해서 제조된 전극 및 상기 전극을 포함하는 이차전지를 제공한다.The present invention also provides an electrode produced using the slurry composition for the electrode and a secondary battery comprising the electrode.
상기 전극은 전극 활물질, PVdF(Polyvinylidene fluoride) 바인더 및 NBR(Nitrile Butadiene Rubber) 바인더를 포함하는 바인더를 포함할 수 있다.The electrode may include a binder including an electrode active material, a polyvinylidene fluoride (PVF) binder, and a nitrile butadiene rubber (NBR) binder.
본 발명의 전극용 슬러리 조성물은 NBR 바인더를 포함하여 전극 패턴의 형성시 드레그 라인(Drag line)이나 발코니의 형성을 최소화시킴으로써, 드레그 라인이나 발코니로 인한 내부단락, Tap 등의 용접곤란, 전지의 두께 불균일 및 Taping으로 인한 용량 감소 문제를 최소화하는 효과를 제공한다. The slurry composition for electrodes of the present invention includes an NBR binder, thereby minimizing the formation of a drag line or a balcony when forming an electrode pattern. It provides the effect of minimizing capacity reduction problem due to unevenness and taping.
또한, 본 발명의 전극용 슬러리 조성물은 전극 활물질 사이 및 전극 활물질과 집전체의 사이에 우수한 결착력을 제공하며, 전지의 내부저항도 저감시키는 효과를 제공한다. In addition, the slurry composition for electrodes of the present invention provides an excellent binding force between the electrode active material and between the electrode active material and the current collector, and also provides an effect of reducing the internal resistance of the battery.
본 발명의 전극은 상기 전극용 슬러리 조성물을 사용하여 제조됨으로써 전지의 불량률을 낮추며, 전지의 충방전 사이클 특성 및 용량 특성을 향상시키는 효과를 제공한다.The electrode of the present invention is prepared using the slurry composition for the electrode to lower the defective rate of the battery, and provides an effect of improving the charge and discharge cycle characteristics and capacity characteristics of the battery.
본 발명의 이차전지는 상기 전극을 포함함으로써 불량률이 낮으며, 충방전 사이클 특성 및 용량 특성이 우수하다.The secondary battery of the present invention has a low defect rate by including the electrode, and is excellent in charge and discharge cycle characteristics and capacity characteristics.
도 1은 종래의 전극용 슬러리를 사용하여 전극 패턴을 형성하는 경우 발생하는 드레그 라인(Drag line) 및 발코니를 모식적으로 도시한 도면이다. 상기 도 1에서 (a)는 상기 전극 패턴의 평면도이고, (b)는 상기 전극 패턴의 이상적으로 코팅된 측단면이고, (c)는 상기 전극 패턴의 실제 코팅된 측단면이다.FIG. 1 is a diagram schematically illustrating a drag line and a balcony generated when an electrode pattern is formed using a conventional slurry for electrodes. In FIG. 1, (a) is a plan view of the electrode pattern, (b) is an ideally coated side cross section of the electrode pattern, and (c) is an actual coated side cross section of the electrode pattern.
도 2는 본 발명의 전극을 사용하여 제조된 리튬이온 이차전지(실시예 1)의 특성을 평가한 그래프다.Figure 2 is a graph evaluating the characteristics of the lithium ion secondary battery (Example 1) manufactured using the electrode of the present invention.
도 3은 종래의 전극을 사용하여 제조된 리튬이온 이차전지(비교예 1)의 특성을 평가한 그래프다. 3 is a graph evaluating the characteristics of a lithium ion secondary battery (Comparative Example 1) manufactured using a conventional electrode.
이하, 본 발명이 속하는 기술 분야에서 통상의 지식을 가진 자가 용이하게 실시할 수 있도록 본 발명의 실시예에 대하여 첨부한 도면을 참고로 하여 상세히 설명한다. 그러나 본 발명은 여러 가지 상이한 형태로 구현될 수 있으며 여기에서 설명하는 실시예에 한정되지 않는다.Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those skilled in the art may easily implement the present invention. As those skilled in the art would realize, the described embodiments may be modified in various different ways, all without departing from the spirit or scope of the present invention.
본 발명은 전극 활물질, PVdF 바인더 및 NBR 바인더를 포함하는 바인더, 및 용제를 포함하는 전극용 슬러리 조성물에 관한 것이다.The present invention relates to a binder composition comprising an electrode active material, a PVdF binder and an NBR binder, and a slurry composition for electrodes comprising a solvent.
상기 전극용 슬러리 조성물은 전극의 제조에 사용되는 것이라면 용도가 특별히 한정되는 것은 아니며, 예를 들면, 리튬이온 이차전지 등의 이차전지, 축전지 등에 사용될 수 있다. The slurry composition for the electrode is not particularly limited as long as it is used for the production of the electrode, and may be used, for example, in secondary batteries such as lithium ion secondary batteries, storage batteries, and the like.
상기 PVdF 바인더는 이 분야에서 일반적으로 사용되는 바인더로서 폴리비닐리덴플루오라이드(Polyvinylidene fluoride) 또는 폴리비닐리덴디플루오라이드를 포함하는 바인더를 의미한다.The PVdF binder refers to a binder including polyvinylidene fluoride or polyvinylidene difluoride as a binder generally used in the art.
상기 NBR(Nitrile Butadiene Rubber) 바인더는 아크릴로니트릴과 부타디엔의 공중합체를 포함하는 바인더를 의미한다. The NBR (Nitrile Butadiene Rubber) binder refers to a binder including a copolymer of acrylonitrile and butadiene.
본 발명에서 사용되는 NBR 바인더는 이 분야에서 공지된 것이 사용될 수 있다. 특히, 상기 NBR 바인더는 NBR에 수소 첨가 반응을 시켜 제조되는 H-NBR 바인더도 포함하는 개념이다. As the NBR binder used in the present invention, those known in the art may be used. In particular, the NBR binder is a concept including a H-NBR binder prepared by hydrogenation reaction to NBR.
상기 NBR 바인더는 NBR 바인더 총 중량을 기준으로 H-NBR(Hydrogenated-Nitrile Butadiene Rubber) 바인더를 1 내지 100 중량%로 포함할 수 있고, 바람직하게 40 내지 80 중량%로 포함할 수 있다. 일반적인 NBR 바인더는 H-NBR 바인더와 비교하여 저항이 더 크기 때문에 일반적인 NBR 바인더와 H-NBR 바인더를 혼합하여 사용하거나, H-NBR 바인더만을 선택하여 사용할 수 있다.The NBR binder may include 1 to 100 wt% of a H-NBR (Hydrogenated-Nitrile Butadiene Rubber) binder based on the total weight of the NBR binder, preferably 40 to 80 wt%. Since the general NBR binder has a higher resistance than the H-NBR binder, a general NBR binder and an H-NBR binder may be used in combination, or only an H-NBR binder may be selected and used.
본 발명에서 사용되는 H-NBR 바인더는 수소첨가에 의해 원래 NBR에 포함되어 있던 이중결합이 60 몰% 이하로 잔존하는 H-NBR을 포함하는 것이 바람직하게 사용될 수 있다.The H-NBR binder used in the present invention may preferably be used to include H-NBR in which double bonds originally contained in the NBR remain at 60 mol% or less by hydrogenation.
상기 H-NBR은 상기 H-NBR 전체 중량에 대하여 수소화된 부타디엔(hydrogenated buradiene)을 40 내지 85 중량% 및 아크릴로니트릴을 15 내지 60 중량%로 포함할 수 있고, 바람직하게 수소화된 부타디엔을 50 내지 75 중량% 및 아크릴로니트릴을 25 내지 50 중량%로 포함할 수 있다.The H-NBR may include 40 to 85% by weight of hydrogenated butadiene and 15 to 60% by weight of acrylonitrile, preferably 50 to 60% by weight of hydrogenated butadiene, based on the total weight of H-NBR. 75 wt% and acrylonitrile at 25-50 wt%.
상기 H-NBR 전체 중량에 대하여 상기 수소화된 부타디엔의 함량이 40 중량% 미만인 경우 저항이 커져 용량이 감소할 수 있고, 85 중량%를 초과하는 경우 집전체와의 접착력이 저하될 수 있다. When the content of the hydrogenated butadiene is less than 40% by weight based on the total weight of H-NBR, the resistance may be increased to decrease the capacity, and when the content of the hydrogenated butadiene is greater than 85% by weight, the adhesion with the current collector may be reduced.
본 발명의 전극용 슬러리 조성물에 있어서, 상기 PVdF 바인더 및 NBR 바인더는 2:8 내지 8:2의 중량비, 더욱 바람직하게는 2:8 내지 3:7의 중량비로 포함되는 것이 바람직하다. In the slurry composition for electrodes of the present invention, the PVdF binder and the NBR binder are preferably contained in a weight ratio of 2: 8 to 8: 2, more preferably 2: 8 to 3: 7.
PVdF 바인더가 상기 범위를 벗어나서 부족하게 포함되는 경우에는 전극 코팅 공정시 로딩 편차가 커져서 공정성이 악화될 수 있고, 상기 범위를 초과하여 포함되는 경우에는 전극 코팅 공정시 로딩 편차가 커져서 공정성이 악화될 수 있고 집전체와의 접착력이 저하될 수 있다.In the case where the PVdF binder is insufficiently included outside the above range, the loading variation may be increased during the electrode coating process, and the fairness may be worsened. When the PVdF binder is included in the above range, the loading variation may be increased during the electrode coating process. And the adhesion with the current collector can be lowered.
또한, NBR 바인더가 상기 범위를 벗어나서는 경우 리튬이온 이차전지의 성능이 저하될 수 있다. In addition, when the NBR binder is out of the above range, the performance of the lithium ion secondary battery may be degraded.
본 발명의 전극용 슬러리 조성물에서 사용되는 전극 활물질은 특별히 한정되지 않으며, 전지 및 축전기의 종류에 따라 적절히 선택될 수 있다. 예를 들어, 리튬이온 이차전지용 양극 활물질로는, 예컨대 LiCoO2, LiNiO2, LiMnO2, LiMn2O4 등의 리튬 함유 복합 금속 산화물; TiS2, TiS3, 비결정질 MoS3 등의 전이 금속 황화물; Cu2V2O3, 비결정질 V2O-P2O5, MoO3, V2O5, V6O13 등의 전이 금속 산화물 등이 사용될 수 있다. The electrode active material used in the slurry composition for electrodes of this invention is not specifically limited, It can select suitably according to the kind of battery and a capacitor. For example, a lithium ion secondary battery positive electrode active material is, for example, LiCoO 2, LiNiO 2, lithium-containing composite metal oxides such as LiMnO 2, LiMn 2 O 4; Transition metal sulfides such as TiS 2 , TiS 3 , and amorphous MoS 3 ; Transition metal oxides such as Cu 2 V 2 O 3 , amorphous V 2 OP 2 O 5 , MoO 3 , V 2 O 5 , V 6 O 13, and the like.
또한, 음극 활물질로는, 예컨대 무정형 카본, 그래파이트, 천연 흑연, 메조카본마이크로비즈(MCMB), 피치(pitch)계 탄소 섬유 등의 탄소질 재료, 폴리아센 등의 도전성 고분자 등을 들 수 있다. Examples of the negative electrode active material include amorphous carbon, graphite, natural graphite, carbonaceous materials such as mesocarbon microbeads (MCMB) and pitch-based carbon fibers, conductive polymers such as polyacene, and the like.
본 발명의 전극용 슬러리 조성물에서 있어서, 전극 활물질과 PVdF 바인더 및 NBR 바인더를 포함하는 바인더는 9.0:1.0 내지 9.9:0.1의 중량비로 포함될 수 있다. 바인더의 함량이 상기 범위를 초과하면 상기 전극을 사용하는 소자의 충방전 성능 및 용량이 저하될 수 있으며, 상기의 범위 미만으로 포함되면 전극의 결착력 부족한 문제가 발생할 수 있다. In the slurry composition for electrodes of the present invention, a binder including an electrode active material, a PVdF binder, and an NBR binder may be included in a weight ratio of 9.0: 1.0 to 9.9: 0.1. When the content of the binder exceeds the above range, the charge / discharge performance and capacity of the device using the electrode may decrease, and when the content of the binder is less than the above range, a problem of insufficient binding force of the electrode may occur.
본 발명의 전극용 슬러리 조성물에서 있어서, 용제로는 PVdF 바인더 및 NBR 바인더를 용해할 수 있는 것이라면 특별히 한정되지 않으며, 이 분야에서 공지된 것이 사용될 수 있다. 예를 들면, N-메틸피롤리돈, N,N-디메틸아세토아미드, N,N-디메틸포름아미드 등의 아미드류가 사용될 수 있으며, 이들 중에서도 N-메틸피롤리돈이 집전체로의 도포성이 양호하기 때문에 바람직하게 사용될 수 있다.In the slurry composition for electrodes of the present invention, the solvent is not particularly limited as long as it can dissolve the PVdF binder and the NBR binder, and those known in the art may be used. For example, amides such as N-methylpyrrolidone, N, N-dimethylacetoamide, and N, N-dimethylformamide may be used, and among these, N-methylpyrrolidone may be applied to a current collector. Since it is good, it can be used preferably.
상기 용제의 사용량은 전극 활물질, 바인더 및 후술하는 도전재의 종류에 따라 도포에 바람직한 점도가 되도록 결정될 수 있다. 예를 들어, 전극 활물질, 바인더 및 후술하는 도전재를 합한 고형분의 농도는 50 내지 95중량%, 더욱 바람직하게는 70 내지 90중량%로 조절될 수 있다. The amount of the solvent used may be determined to be a viscosity suitable for coating depending on the type of the electrode active material, the binder, and the conductive material described later. For example, the concentration of the solid content of the electrode active material, the binder, and the conductive material described later may be adjusted to 50 to 95% by weight, more preferably 70 to 90% by weight.
본 발명의 전극용 슬러리 조성물은 도전재를 더 포함할 수 있다. 상기 도전재는 특별히 한정되지 않으며, 전지 및 축전기의 종류에 따라 적절히 선택될 수 있다. 예를 들어, 리튬이온 이차전지의 경우에는 그래파이트, 활성탄 등의 카본이 사용되며, 니켈 수소 이차전지의 경우에는 산화 코발트, 음극에는 니켈 분말, 산화 코발트, 산화 티탄, 카본 등이 사용될 수 있다.The slurry composition for electrodes of the present invention may further include a conductive material. The conductive material is not particularly limited and may be appropriately selected according to the type of battery and capacitor. For example, in the case of a lithium ion secondary battery, carbon such as graphite and activated carbon may be used. In the case of a nickel hydrogen secondary battery, cobalt oxide may be used, and in the negative electrode, nickel powder, cobalt oxide, titanium oxide, and carbon may be used.
상기 카본으로서는 아세틸렌 블랙, 퍼니스 블랙(furnace black), 흑연, 탄소 섬유, 플러렌류를 들 수 있다. Examples of the carbon include acetylene black, furnace black, graphite, carbon fiber, and fullerenes.
상기 도전재의 사용량은 전극 활성질 100중량부를 기준으로 통상 1 내지 20중량부, 바람직하게는 2 내지 10중량부이다.The amount of the conductive material is usually 1 to 20 parts by weight, preferably 2 to 10 parts by weight based on 100 parts by weight of the electrode active material.
상기 전극용 슬러리 조성물에는 기타 필요에 따라 점도 조정제, 유동화제 등이 더 첨가될 수 있다.Viscosity modifiers, glidants, etc. may be further added to the slurry composition for electrodes as needed.
상기 전극용 슬러리 조성물의 점도는 4,000 내지 30,000cps일 수 있고, 바람직하게 8000 내지 19000cps일 수 있다. 상기 전극용 슬러리 조성물의 점도가 4,000cps 미만인 경우 상기 전극용 슬러리의 고(高) 로딩(loading)이 어려울 수 있고, 30,000cps를 초과하는 경우 상기 전극용 슬러리의 코팅이 불균일해 질 수 있다.The viscosity of the slurry composition for the electrode may be 4,000 to 30,000 cps, preferably 8000 to 19000 cps. When the viscosity of the slurry composition for the electrode is less than 4,000 cps, high loading of the slurry for the electrode may be difficult, and when the viscosity of the electrode composition exceeds 30,000 cps, the coating of the slurry for the electrode may be uneven.
본 발명의 전극용 슬러리 조성물은 이 분야에 공지된 방법에 의해 상기 각 성분을 혼합하여 제조될 수 있다. The slurry composition for electrodes of the present invention can be prepared by mixing the above components by methods known in the art.
또한, 본 발명은 상기 전극용 슬러리 조성물을 사용해서 제조되는 전극에 관한 것이다. 이에 따라, 상기 전극은 전극 활물질, PVdF(Polyvinylidene fluoride) 바인더 및 NBR(Nitrile Butadiene Rubber) 바인더를 포함하는 바인더를 포함할 수 있다. Moreover, this invention relates to the electrode manufactured using the said slurry composition for electrodes. Accordingly, the electrode may include a binder including an electrode active material, a polyvinylidene fluoride (PVDF) binder, and a nitrile butadiene rubber (NBR) binder.
상기 전극은 이 분야에 공지된 방법에 의하여 제조될 수 있다. 즉, 본 발명의 전극은 집전체에 본 발명의 전극용 슬러리 조성물을 도포하여 건조시켜서 제조될 수 있다. 상기 전극용 슬러리 조성물의 집전체로의 도포 방법은 특별히 제한되지 않는다. 예컨대, 닥터 블레이드법, 딥법, 리버스 롤법, 디렉트 롤법, 그라비아법, 압출법, 브러쉬 도포법 등의 방법을 들 수 있다. 도포하는 슬러리 양도 특별히 제한되지 않지만, 액상 매체를 건조시켜 제거한 후에 형성되는 활성 물질, 바인더 등으로 이루어진 혼합층의 두께가 통상 0.005 내지 5㎜, 바람직하게는 0.01 내지 2㎜가 되는 양이 일반적이다. 건조 방법도 특별히 제한되지 않고, 예컨대 온풍, 열풍, 저습풍에 의한 건조, 진공 건조, (원)적외선 및 전자선 등의 조사에 의한 건조법을 들 수 있다. 건조 속도는 통상 응력 집중에 의해 혼합층에 균열이 생기거나 혼합층이 집전체로부터 박리되지 않을 정도의 속도 범위 내에서 가능한 한 빨리 액상 매체를 제거할 수 있도록 조정한다.The electrode can be prepared by a method known in the art. That is, the electrode of the present invention can be prepared by applying the slurry composition for electrode of the present invention to a current collector and drying it. The coating method to the collector of the said slurry composition for electrodes is not specifically limited. For example, methods, such as a doctor blade method, a dip method, the reverse roll method, the direct roll method, the gravure method, the extrusion method, the brush coating method, are mentioned. The amount of the slurry to be applied is also not particularly limited, but an amount such that a mixed layer made of an active material, a binder, and the like formed after drying and removing the liquid medium is usually 0.005 to 5 mm, preferably 0.01 to 2 mm is common. The drying method is not particularly limited, and examples thereof include drying by warm air, hot air and low humidity, vacuum drying, and drying by irradiation of (far) infrared rays and electron beams. The drying rate is usually adjusted so that the liquid medium can be removed as soon as possible within a speed range such that cracks do not form in the mixed layer due to stress concentration or the mixed layer does not peel off from the current collector.
또한, 건조 후 집전체를 프레스함으로써 전극의 활성 물질의 밀도를 높일 수도 있다. 프레스 방법으로는 금형 프레스 및 롤 프레스 등의 방법을 들 수 있다.In addition, the density of the active material of the electrode can be increased by pressing the current collector after drying. As a press method, methods, such as a metal mold | die press and a roll press, are mentioned.
상기 집전체는 도전성 재료로 이루어진 것이면 특별히 제한되지 않는다. 예컨대, 리튬이온 이차전지의 경우는 철, 구리, 알루미늄, 니켈, 스테인레스 등의 금속으로 제조된 것이 사용될 수 있다.The current collector is not particularly limited as long as it is made of a conductive material. For example, in the case of a lithium ion secondary battery, one made of metal such as iron, copper, aluminum, nickel, stainless, or the like may be used.
또한, 본 발명은 상기 전극을 포함하는 이차전지에 관한 것이다.The present invention also relates to a secondary battery comprising the electrode.
상기 이차전지에 있어서, 상기 전극을 음극 및/또는 양극에 사용하는 것을 제외하고 다른 구성요소 및 제조방법은 이 분야에서 공지된 것들이 제한 없이 사용될 수 있다. 즉, 본 발명의 이차전지는 상기 전극 및 전해액을 포함하고 세퍼레이터 등의 부품을 이용하여 공지의 방법에 따라 제조될 수 있다. 그러므로, 이들에 대한 설명은 생략하기로 한다.In the secondary battery, other components and manufacturing methods except those using the electrode for the negative electrode and / or the positive electrode may be used without limitation those known in the art. That is, the secondary battery of the present invention includes the electrode and the electrolyte and can be manufactured according to a known method using a component such as a separator. Therefore, description thereof will be omitted.
이하, 발명의 이해를 돕기 위하여 바람직한 실시예들을 제시한다. 그러나 하기의 실시예들은 발명을 예시하기 위한 것일 뿐, 발명을 이들만으로 한정하는 것은 아니다.Hereinafter, preferred embodiments will be presented to aid in understanding the invention. However, the following examples are only to illustrate the invention, not limited to the invention only.
[제조예: 리튬이온 이차전지의 제조]Preparation Example: Fabrication of Li-ion Secondary Battery
(실시예 1)(Example 1)
1) 양극의 제조1) Preparation of Anode
양극 활물질로서 LiCoO2 , PVdF(상품명: KF1100, 제조사: Kureha)와 H-NBR(상품명: BM-730H, 제조사: zeon)를 8:2의 중량비로 혼합한 바인더, 도전재로서 아세틸렌 블랙을 96 : 2 : 2 의 중량비로 N-메틸피롤리돈과 혼합하여 슬러리를 제조한 후, 슬롯다이 코터(Slot die coater)를 사용하여 알루미늄(Al) 호일 집전체에 도포하고, 건조하여 양극을 제조하였다.As a cathode active material, LiCoO 2 , PVdF (trade name: KF1100, manufacturer: Kureha), and H-NBR (brand name: BM-730H, manufacturer: zeon) were mixed in a weight ratio of 8: 2, and acetylene black was used as a conductive material. After the slurry was prepared by mixing with N-methylpyrrolidone in a weight ratio of 2: 2, a slurry was applied to an aluminum (Al) foil current collector using a slot die coater, and dried to prepare a positive electrode.
2) 음극의 제조2) Preparation of Cathode
음극 활물질로서 인조 흑연, CMC(상품명: BG-L01, 제조사: 지엘켐), SBR(상품명: BM-L301, 제조사: zeon), 도전재로서 아세틸렌 블랙을 95 : 2 : 1 : 2의 중량비로 N-메틸피롤리돈과 혼합하여 슬러리를 제조한 후, 콤마 코터(commacoater)를 사용하여 구리(Cu) 호일 집전체에 도포하여, 음극을 제조하였다.Artificial graphite, CMC (brand name: BG-L01, manufacturer: GEL Chem), SBR (brand name: BM-L301, manufacturer: zeon) as a negative electrode active material, acetylene black as a conductive material in a weight ratio of 95: 2: 1: 1 A slurry was prepared by mixing with methylpyrrolidone and then applied to a copper (Cu) foil current collector using a commacoater to prepare a negative electrode.
3) 리튬이온 이차전지의 제조3) Manufacture of Lithium Ion Secondary Battery
상기에서 제조된 양극 및 음극의 사이에 폴리에틸렌 다공성 막을 개재시켜 만든 스택형 전극조립체를 파우치형 전지 케이스에 투입하고, 전해액으로 3.0M LiTFSI(lithium trifluoromethanesulfonimide, Li(N(SO2CF3)2)과 DME(dimethoxyethane):DOL(dioxolane)=1:1을 1:1로 주입하여 파우치형 리튬이온 이차전지를 제조하였다.A stack-type electrode assembly prepared by interposing a polyethylene porous membrane between the positive electrode and the negative electrode prepared above was introduced into a pouch-type battery case, and 3.0M LiTFSI (lithium trifluoromethanesulfonimide, Li (N (SO 2 CF 3 ) 2 ) and DME (dimethoxyethane): DOL (dioxolane) = 1: 1 was injected to prepare a pouch type lithium ion secondary battery.
(비교예 1)(Comparative Example 1)
1) 양극의 제조1) Preparation of Anode
바인더로서 PVdF(상품명: KF1100, 제조사: Kureha) 바인더만을 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 양극을 제조하였다.A positive electrode was manufactured in the same manner as in Example 1, except that only a PVdF (trade name: KF1100, manufacturer: Kureha) binder was used as the binder.
2) 음극의 제조2) Preparation of Cathode
실시예 1과 동일한 방법으로 음극을 제조하였다.A negative electrode was prepared in the same manner as in Example 1.
3) 리튬이온 이차전지의 제조3) Manufacture of Lithium Ion Secondary Battery
상기에서 제조된 양극 및 음극의 사이에 폴리에틸렌 다공성 막을 개재시켜 만든 스택형 전극조립체를 파우치형 전지 케이스에 투입하고, 전해액으로 1.0M LiTFSI(lithium trifluoromethanesulfonimide, Li(N(SO2CF3)2)과 DME(dimethoxyethane):DOL(dioxolane)=1:1을 1:1로 주입하여 파우치형 리튬이온 이차전지를 제조하였다.A stack-type electrode assembly prepared by interposing a polyethylene porous membrane between the positive electrode and the negative electrode prepared above was introduced into a pouch-type battery case, and 1.0M LiTFSI (lithium trifluoromethanesulfonimide, Li (N (SO 2 CF 3 ) 2 ) and DME (dimethoxyethane): DOL (dioxolane) = 1: 1 was injected to prepare a pouch type lithium ion secondary battery.
(비교예 2)(Comparative Example 2)
1) 양극의 제조1) Preparation of Anode
양극 활물질로서 LiCoO2 , 수계 양극의 바인더인 SBR(상품명: BM-L301, 제조사: zeon) 바인더, CMC(상품명: BG-L01, 제조사: 지엘켐), 도전재로서 아세틸렌 블랙을 96 : 2 : 1 : 1의 중량비로 N-메틸피롤리돈과 혼합하여 슬러리를 제조한 후, 슬롯다이 코터(Slot die coater)를 사용하여 알루미늄(Al) 호일 집전체에 도포하고, 건조하여 양극을 제조하였다.Of LiCoO 2, a binder of the water-based positive electrode as the positive electrode active material, SBR (trade name: BM-L301, Manufacturer: zeon) binder, CMC (trade name: BG-L01, Manufacturer: GL-Chem), the conductive material, acetylene black 96 as: 2: 1 A slurry was prepared by mixing with N-methylpyrrolidone in a weight ratio of 1, and then applied to an aluminum (Al) foil current collector using a slot die coater, followed by drying to prepare a positive electrode.
2) 음극의 제조2) Preparation of Cathode
실시예 1과 동일한 방법으로 음극을 제조하였다.A negative electrode was prepared in the same manner as in Example 1.
3) 리튬이온 이차전지의 제조3) Manufacture of Lithium Ion Secondary Battery
상기에서 제조된 양극 및 음극의 사이에 폴리에틸렌 다공성 막을 개재시켜 만든 스택형 전극조립체를 파우치형 전지 케이스에 투입하고, 전해액으로 3.0M LiTFSI(lithium trifluoromethanesulfonimide, Li(N(SO2CF3)2)과 DME(dimethoxyethane):DOL(dioxolane)=1:1을 1:1로 주입하여 파우치형 리튬이온 이차전지를 제조하였다.A stack-type electrode assembly prepared by interposing a polyethylene porous membrane between the positive electrode and the negative electrode prepared above was introduced into a pouch-type battery case, and 3.0M LiTFSI (lithium trifluoromethanesulfonimide, Li (N (SO 2 CF 3 ) 2 ) and DME (dimethoxyethane): DOL (dioxolane) = 1: 1 was injected to prepare a pouch type lithium ion secondary battery.
[시험예 1: 전극의 외관 평가]Test Example 1: Evaluation of Appearance of Electrode
실시예 및 비교예에서 제조된 전극들의 외관을 육안으로 평가하였다. 그 결과 실시예의 전극들에서는 드레그 라인(Drag line)이나 발코니가 발생하지 않았으나, 비교예의 전극들에서는 드레그 라인(Drag line) 및 발코니의 발생이 관찰되었다. Visually the appearance of the electrodes prepared in Examples and Comparative Examples Evaluated. As a result, a drag line or a balcony did not occur in the electrodes of the example, but the occurrence of a drag line and a balcony was observed in the electrodes of the comparative example.
상기 실시예 1에서 제조된 양극의 주사전자현미경(SEM) 이미지를 본 발명의 원출원인 한국 특허 출원 제10-2015-0006905호(출원일: 2015년 1월 14일)의 도 2에 나타내었다. 상기 사진에서 확인되는 바와 같이, 실시예 1의 양극에서는 드래그 라인이 발생하지 않았음이 확인되었다.A scanning electron microscope (SEM) image of the anode prepared in Example 1 is shown in FIG. 2 of Korean Patent Application No. 10-2015-0006905 (filed date: January 14, 2015) of the present invention. As confirmed in the photograph, it was confirmed that no drag line occurred in the anode of Example 1.
상기 비교예 1에서 제조된 양극의 주사전자현미경(SEM) 이미지를 본 발명의 원출원인 한국 특허 출원 제10-2015-0006905호(출원일: 2015년 1월 14일)의 도 3에 나타내었다. 상기 사진에서 확인되는 바와 같이, 비교예 1의 양극에서는 드래그 라인이 확인되었다. A scanning electron microscope (SEM) image of the anode prepared in Comparative Example 1 is shown in FIG. 3 of Korean Patent Application No. 10-2015-0006905 (Application Date: January 14, 2015), which is the original application of the present invention. As confirmed in the above photograph, a drag line was confirmed at the anode of Comparative Example 1.
상기 비교예 2의 양극의 외관을 촬영한 이미지를 본 발명의 원출원인 한국 특허 출원 제10-2015-0006905호(출원일: 2015년 1월 14일)의 도 4에 나타내었다. 상기 사진에서 확인되는 바와 같이, 비교예 2의 양극에서는 믹싱시 알갱이가 발생하며 코팅시 line 불량이 발생하였다. An image photographing the appearance of the anode of Comparative Example 2 is shown in FIG. 4 of Korean Patent Application No. 10-2015-0006905 (Application Date: January 14, 2015), which is the original application of the present invention. As can be seen in the photo, in the positive electrode of Comparative Example 2, grains occurred during mixing and line defects occurred during coating.
[시험예 2: 리튬이온 이차전지의 성능 평가]Test Example 2: Performance Evaluation of Lithium Ion Secondary Battery
상기 실시예 및 비교예에서 제작된 전지의 성능을 확인하기 위해 방전 용량을 측정하였다. 충전은 CC/CV C-rate 0.5C 4.2V, 1/20C cut-off로 상온에서 충전하였고 방전은 상온 CC 0.2C 로 2.5V cut-off 하였다. 그 결과를 도 2 및 도 3에 나타냈다.The discharge capacity was measured to confirm the performance of the batteries produced in the above Examples and Comparative Examples. The charge was charged at room temperature with CC / CV C-rate 0.5C 4.2V, 1 / 20C cut-off and the discharge was cut 2.5V with room temperature CC 0.2C. The results are shown in FIGS. 2 and 3.
도 2(실시예 1의 전지) 및 도 3(비교예 1의 전지)에서 확인되는 바와 같이, 실시예 1 및 비교예 1에서 제조된 전지는 성능상 특별한 차이를 나타나지 않았다. 이러한 결과는 본 발명에서 전극의 제조시 바인더로서 더 첨가되는NBR 바인더가 전지의 성능에는 나쁜 영향을 끼치지 않음을 나타낸다.As confirmed in FIG. 2 (cell of Example 1) and FIG. 3 (cell of Comparative Example 1), the batteries prepared in Example 1 and Comparative Example 1 did not show any particular difference in performance. These results indicate that the NBR binder further added as a binder in the manufacture of the electrode in the present invention does not adversely affect the performance of the battery.
비교예 2의 경우 믹싱시 알갱이가 발생하며 코팅시 line불량이 발생하여 방전 용량 측정은 진행하지 않았다.In the case of Comparative Example 2, granules were generated during mixing and line defects occurred during coating, and thus, the discharge capacity was not measured.
이상에서 본 발명의 바람직한 실시예에 대하여 상세하게 설명하였지만 본 발명의 권리범위는 이에 한정되는 것은 아니고 다음의 청구범위에서 정의하고 있는 본 발명의 기본 개념을 이용한 당업자의 여러 변형 및 개량 형태 또한 본 발명의 권리범위에 속하는 것이다.Although the preferred embodiments of the present invention have been described in detail above, the scope of the present invention is not limited thereto, and various modifications and improvements of those skilled in the art using the basic concepts of the present invention defined in the following claims are also provided. It belongs to the scope of rights.
본 발명은, 전극용 슬러리 조성물, 이를 사용하여 제조된 전극 및 상기 전극을 포함하는 이차전지에 관한 것으로서, 상기 전극용 슬러리 조성물은 전극 활물질, PVdF(Polyvinylidene fluoride) 바인더 및 NBR(Nitrile Butadiene Rubber) 바인더를 포함한다.The present invention relates to a slurry composition for an electrode, an electrode prepared using the same, and a secondary battery including the electrode, wherein the slurry composition for the electrode includes an electrode active material, a polyvinylidene fluoride (PVDF) binder, and a nitrile butadiene rubber (NBR) binder. It includes.
상기 전극용 슬러리 조성물은 NBR 바인더를 포함하여 전극 패턴의 형성시 드레그 라인(Drag line)이나 발코니의 형성을 최소화시킴으로써, 드레그 라인이나 발코니로 인한 내부단락, Tap 등의 용접곤란, 전지의 두께 불균일 및 Taping으로 인한 용량 감소 문제를 최소화하는 효과를 제공한다.The slurry composition for the electrode includes an NBR binder, thereby minimizing the formation of a drag line or a balcony when forming an electrode pattern, such as an internal short circuit due to the drag line or a balcony, difficulty in welding such as a tap, uneven thickness of a battery, and the like. It minimizes the capacity reduction problem caused by taping.

Claims (11)

  1. 전극 활물질, PVdF(Polyvinylidene fluoride) 바인더 및 NBR(Nitrile Butadiene Rubber) 바인더를 포함하는 바인더, 및 용제를 포함하는 전극용 슬러리 조성물.Slurry composition for electrodes comprising an electrode active material, a polyvinylidene fluoride (PVD) binder and a Nitrile Butadiene Rubber (NBR) binder, and a solvent.
  2. 제1항에 있어서,The method of claim 1,
    상기 NBR 바인더는 NBR 바인더 총 중량을 기준으로 H-NBR 바인더가 1 내지 100 중량%로 포함되는 것인 전극용 슬러리 조성물.The NBR binder is a slurry composition for an electrode containing 1 to 100% by weight of H-NBR binder based on the total weight of the NBR binder.
  3. 제1항에 있어서,The method of claim 1,
    상기 PVdF 바인더 및 NBR 바인더는 2:8 내지 8:2의 중량비로 포함되는 것인 전극용 슬러리 조성물.The PVdF binder and NBR binder is a slurry composition for an electrode is included in a weight ratio of 2: 8 to 8: 2.
  4. 제1항에 있어서,The method of claim 1,
    전극 활물질과 PVdF 바인더 및 NBR 바인더를 포함하는 바인더는 9.0:1.0 내지 9.9:0.1의 중량비로 포함되는 것인 전극용 슬러리 조성물.A binder comprising an electrode active material, a PVdF binder, and an NBR binder is included in a weight ratio of 9.0: 1.0 to 9.9: 0.1.
  5. 제1항에 있어서,The method of claim 1,
    상기 전극용 슬러리 조성물은 도전재를 더 포함하는 것인 전극용 슬러리 조성물.Slurry composition for electrodes that the electrode composition further comprises a conductive material.
  6. 제2항에 있어서,The method of claim 2,
    상기 H-NBR 바인더는 수소첨가에 의해 NBR의 이중결합이 60 몰% 이하로 잔존하는 것인 전극용 슬러리 조성물.The H-NBR binder has 60 double bonds of NBR by hydrogenation. Slurry composition for electrodes remaining in mol% or less.
  7. 제2항에 있어서,The method of claim 2,
    상기 H-NBR은 상기 H-NBR 전체 중량에 대하여 수소화된 부타디엔(hydrogenated buradiene)을 40 내지 85 중량% 및 아크릴로니트릴을 15 내지 60 중량%로 포함하는 것인 전극용 슬러리 조성물.The H-NBR is a slurry composition for an electrode comprising 40 to 85% by weight of hydrogenated butadiene (hydrogenated buradiene) and 15 to 60% by weight of acrylonitrile relative to the total weight of the H-NBR.
  8. 제1항에 있어서,The method of claim 1,
    상기 전극용 슬러리 조성물의 점도는 4,000 내지 30,000cps인 것인 전극용 슬러리 조성물.The viscosity of the slurry composition for electrodes is 4,000 to 30,000cps slurry composition for electrodes.
  9. 제1항 내지 제8항 중 어느 한 항의 전극용 슬러리 조성물을 사용해서 제조된 전극.The electrode manufactured using the slurry composition for electrodes of any one of Claims 1-8.
  10. 제9항에 있어서,The method of claim 9,
    상기 전극은 전극 활물질, 그리고 The electrode is an electrode active material, and
    PVdF(Polyvinylidene fluoride) 바인더 및 NBR(Nitrile Butadiene Rubber) 바인더를 포함하는 바인더를 포함하는 것인 전극.An electrode comprising a binder comprising a polyvinylidene fluoride (PVDF) binder and a Nitrile Butadiene Rubber (NBR) binder.
  11. 제9항의 전극을 포함하는 이차전지.A secondary battery comprising the electrode of claim 9.
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