KR20040071510A - The high efficiency lithium secondary battery - Google Patents
The high efficiency lithium secondary battery Download PDFInfo
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- KR20040071510A KR20040071510A KR1020030007518A KR20030007518A KR20040071510A KR 20040071510 A KR20040071510 A KR 20040071510A KR 1020030007518 A KR1020030007518 A KR 1020030007518A KR 20030007518 A KR20030007518 A KR 20030007518A KR 20040071510 A KR20040071510 A KR 20040071510A
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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
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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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- 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
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- 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
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Abstract
Description
본 발명은 음극 활물질 및 고체 전해질 계면(Solid Electrolyte Interface, SEI) 피막(film) 성분을 포함하는 음극 활물질 조성물 및 이를 포함하여 제조된 리튬 이차 전지에 관한 것이다.The present invention relates to a negative electrode active material composition comprising a negative electrode active material and a solid electrolyte interface (SEI) film component, and a lithium secondary battery prepared by using the same.
근래, 전자 기술의 진보에 따라 휴대전화 또는 랩 톱 컴퓨터 등의 포터블 전자 기기가 널리 보급되고 있으며, 포터블 전자 기기의 소형화 및 경량화가 도모되고 있다. 이러한 포터블 전자 기기의 구동 전원으로 경량이면서 고전압, 고용량, 고출력을 내는 전지, 특히 비수용성 전해질을 사용하는 리튬 이차 전지에 대한 연구 개발이 활발히 진행되고 있다. 일반적으로 리튬 이차 전지는 양극 활물질로 리튬 함유 전이 금속 산화물을 사용하며, 예를 들면 LiCoO2, LiNiO2, LiMn2O4, LiMnO2, LiNi1-XCoXMYO2(여기에서, M=Al, Ti, Mg, Zr, 0<X≤1, 0≤Y≤0.2) 및 LiNiXCoYMn1-X-YO2(여기에서, 0<X≤0.5, 0<Y≤0.5)로 이루어진 군으로부터 1종 이상 선택되어진다. 또한, 음극 활물질로 탄소, 리튬 금속 또는 합금을 사용하며, 기타 리튬을 흡장 방출할 수 있고 리튬에 대한 전위가 2V 미만인 TiO2, SnO2와 같은 금속 산화물도 가능하다.In recent years, with the progress of electronic technology, portable electronic devices such as mobile phones and laptop computers have been widely used, and miniaturization and weight reduction of portable electronic devices have been achieved. As a driving power source of such portable electronic devices, research and development on a light-weight, high-voltage, high-capacity, high-output battery, especially a lithium secondary battery using a non-aqueous electrolyte, is being actively conducted. In general, a lithium secondary battery uses a lithium-containing transition metal oxide as a positive electrode active material, for example, LiCoO 2 , LiNiO 2 , LiMn 2 O 4 , LiMnO 2 , LiNi 1-X Co X M Y O 2 (here, M = Al, Ti, Mg, Zr, 0 <X≤1, 0≤Y≤0.2) and LiNi X Co Y Mn 1-X- YO 2 (where 0 <X≤0.5, 0 <Y≤0.5) At least one selected from the group consisting of. In addition, carbon, lithium metal or an alloy is used as the negative electrode active material, and other metal oxides such as TiO 2 and SnO 2 capable of occluding and releasing lithium and having a potential for lithium of less than 2 V are also possible.
초기 충전시 리튬이온과 전해액의 부반응에 의해 상기 음극 활물질 표면에는 고체 전해질 계면(Solid Electrolyte Interface, SEI) 피막이라고 불리는 부동태막(passivation film) 이 형성된다. 이러한 SEI 피막의 형성 반응은 비가역적인 리튬 소비 반응으로 초기 효율의 감소 및 용량 감소 등 전지의 제반 성능을 저하시키게 된다.During initial charging, a passivation film called a solid electrolyte interface (SEI) film is formed on the surface of the negative electrode active material due to side reaction between lithium ions and an electrolyte. The formation reaction of the SEI film is an irreversible lithium consumption reaction, which decreases overall performance of the battery, such as decreasing initial efficiency and decreasing capacity.
본 발명은 종래 기술의 문제점을 고려하여, 리튬 이차 전지 음극의 초기 비가역 반응을 제어하여 고효율, 고용량의 리튬 이차 전지를 제공하는 것을 목적으로 한다.SUMMARY OF THE INVENTION An object of the present invention is to provide a high efficiency, high capacity lithium secondary battery by controlling an initial irreversible reaction of a lithium secondary battery negative electrode in consideration of the problems of the prior art.
상기 목적을 달성하기 위하여, 본 발명은 리튬 이온 전지, 또는 리튬 폴리머 전지의 음극 활물질에 Li2CO3, Li2O, LiCH3CO2, LiF, LiOH 와 같은 SEI 피막을 구성하는 성분과 동일한 성분을 첨가 또는 이러한 성분으로 음극 활물질을 코팅함으로써 초기 비가역 반응을 제어하여 가역성을 높이고, 또한 탄소재료 주변에서 전해액에 대한 흡수 성질이 우수한 알루미늄, 규소, 지르코늄, 마그네슘, 칼슘, 스트론튬 및 희토류 원소로 된 군 중의 적어도 1종의 원소를 포함한 산화물을 함께 첨가하여전해액에 대한 탄소 재료 자체의 흡수성을 향상시켜 가역성을 증대하여 고효율, 고용량의 전지를 제공하고자 한다.In order to achieve the above object, the present invention is the same component as the components constituting the SEI film such as Li 2 CO 3 , Li 2 O, LiCH 3 CO 2 , LiF, LiOH in the negative electrode active material of a lithium ion battery or a lithium polymer battery Group of aluminum, silicon, zirconium, magnesium, calcium, strontium, and rare earth elements that improve reversibility by controlling the initial irreversible reaction by adding N or coating the negative electrode active material with such a component, and having excellent absorption property of electrolyte around the carbon material It is intended to provide a high efficiency, high capacity battery by adding together an oxide containing at least one element of the above to improve the absorption of the carbon material itself to the electrolyte, thereby increasing the reversibility.
도 1은 실시예 및 비교예에서 제조된 음극 코인형 반전지의 충방전 그래프이다.1 is a charge and discharge graph of the negative electrode coin-type half-cell prepared in Examples and Comparative Examples.
본 발명은 음극 활물질 및 고체 전해질 계면(SEI) 피막 성분을 포함하는 음극 활물질 조성물 및 이를 포함하여 제조된 리튬 이차 전지를 제공한다.The present invention provides a negative electrode active material composition comprising a negative electrode active material and a solid electrolyte interface (SEI) coating component, and a lithium secondary battery prepared by using the same.
SEI 피막은 주로 초기 충전시 카르보닐기를 포함하고 있는 용매의 분해 생성물인 CO3 2-등의 탄산가스가 전해질 용액 속에 포화되어 있는 리튬 이온들과 반응하여 형성되고, 이러한 SEI 피막 형성에 리튬이 비가역적으로 소비된다. 따라서, 음극 활물질에 Li2CO3, Li2O, LiCH3CO2, LiF, LiOH 등과 같은 SEI 피막을 구성하는 성분과 동일한 성분을 첨가 또는 이러한 성분으로 음극 활물질을 코팅하면, 초기 충전시에 이러한 SEI 피막을 형성하기 위해 리튬이 소비되는 비가역적인 반응을 제어할 수 있다.The SEI film is mainly formed by reaction of carbon dioxide gas such as CO 3 2- , which is a decomposition product of a solvent containing a carbonyl group, upon initial charging with lithium ions saturated in an electrolyte solution, and lithium is irreversible in forming the SEI film. Is consumed. Therefore, if the same components as those constituting the SEI film such as Li 2 CO 3 , Li 2 O, LiCH 3 CO 2 , LiF, LiOH, etc. are added to the negative electrode active material or the negative electrode active material is coated with such a component, such an initial charge It is possible to control the irreversible reaction in which lithium is consumed to form the SEI film.
또한, 본 발명은 탄소재료 주변에서 전해액에 대한 흡수 성질이 우수한 알루미늄, 규소, 지르코늄, 마그네슘, 칼슘, 스트론튬 및 희토류 원소로 된 군 중의 적어도 1종의 원소를 포함한 산화물을 함께 첨가시킴으로써 전해액에 대한 탄소 재료 자체의 흡수성을 향상시켜 가역성을 증가시킨다. 따라서, 본 발명은 고효율, 고용량의 리튬 이차전지를 구현할 수 있다.In addition, the present invention is a carbon to the electrolyte by adding together the oxide containing at least one element of the group consisting of aluminum, silicon, zirconium, magnesium, calcium, strontium and rare earth elements with excellent absorption properties of the electrolyte around the carbon material Increase the reversibility by improving the absorbency of the material itself. Therefore, the present invention can implement a high efficiency, high capacity lithium secondary battery.
하기에서는 본 발명을 더욱 구체적으로 설명한다.Hereinafter, the present invention will be described in more detail.
1. 음극 활물질 조성물1. Anode active material composition
본 발명은 음극 활물질 및 고체 전해질 계면 피막 성분을 포함하는 음극 활물질 조성물을 제공한다.The present invention provides a negative electrode active material composition comprising a negative electrode active material and a solid electrolyte interface coating component.
상기 고체 전해질 계면 피막 성분은 Li2CO3, Li2O, LiCH3CO2, LiF, LiOH 로 구성된 군에서 1종 이상 선택된 것이 바람직하다.The solid electrolyte interface coating component is preferably at least one selected from the group consisting of Li 2 CO 3 , Li 2 O, LiCH 3 CO 2 , LiF, LiOH.
또, 고체 전해질 계면 피막 성분은 음극 활물질 조성물 내에 0.01 중량% 내지 10 중량% 포함하는 것이 바람직하며, 0.01중량% 미만에서는 초기 충전시 SEI 피막을 형성하는 비가역반응을 제어하지 못하며, 10% 중량% 초과 첨가시에는 음극활물질의 첨가량이 상대적으로 저하되어 전지의 충방전 용량이 저하되기 때문에 바람직하지 않다.In addition, the solid electrolyte interfacial coating component is preferably included in the negative electrode active material composition 0.01% to 10% by weight, less than 0.01% by weight does not control the irreversible reaction to form the SEI film during the initial charge, more than 10% by weight In addition, since the addition amount of a negative electrode active material falls comparatively and the charge / discharge capacity of a battery falls, it is unpreferable.
음극 활물질 조성물에서 고체 전해질 계면 피막 성분은 분말(powder) 형태로 혼합 사용할 수 있다.In the negative electrode active material composition, the solid electrolyte interface coating component may be mixed and used in powder form.
또한, 음극 활물질 조성물에서 고체 전해질 계면 피막 성분은 음극 활물질을 코팅하여 사용할 수 있다. 일 실시태양으로 고체 전해질 계면 피막 성분을 물 또는 알코올 등에 용해시킨 후, 음극 활물질을 넣고 교반하여 열처리함으로써 고체 전해질 계면 피막 성분으로 음극 활물질을 코팅할 수 있다.In addition, in the negative electrode active material composition, the solid electrolyte interface coating component may be used by coating the negative electrode active material. In one embodiment, after dissolving the solid electrolyte interfacial film component in water or alcohol, the negative electrode active material may be added, stirred, and heat treated to coat the negative electrode active material with the solid electrolyte interfacial film component.
본 발명의 음극 활물질 조성물 중 음극 활물질은 탄소, 리튬 금속 또는 합금인 것이 바람직하다. 기타 리튬을 흡장 방출할 수 있고, 리튬에 대한 전위가 2V 미만인 TiO2, SnO2와 같은 금속 산화물도 가능하다.It is preferable that the negative electrode active material in the negative electrode active material composition of this invention is carbon, lithium metal, or an alloy. Other metals such as TiO 2 and SnO 2 capable of occluding and releasing lithium and having a potential for lithium of less than 2 V are also possible.
더욱이, 본 발명의 음극 활물질 조성물은 알루미늄, 규소, 지르코늄, 마그네슘, 칼슘, 스트론튬 및 희토류 원소로 된 군 중의 적어도 1종의 원소를 포함한 산화물을 더 포함하는 것이 바람직하다.Furthermore, the negative electrode active material composition of the present invention preferably further includes an oxide containing at least one element of the group consisting of aluminum, silicon, zirconium, magnesium, calcium, strontium and rare earth elements.
또한 이러한 산화물은 음극 활물질 조성물 내에 0.1 중량% 내지 30 중량% 포함하는 것이 바람직하며, 0.1 중량% 미만에서는 전극의 전해액 지지능을 충분히 높이는 것이 가능하지 않으며, 30% 중량% 초과 첨가시에는 음극활물질의 첨가량이 상대적으로 저하되어 전지의 충방전 용량이 저하되기 때문에 바람직하지 않다.In addition, the oxide is preferably included in the negative electrode active material composition 0.1% to 30% by weight, less than 0.1% by weight is not possible to sufficiently increase the electrolyte support capacity of the electrode, when added more than 30% by weight of the negative electrode active material It is not preferable because the added amount is relatively lowered and the charge / discharge capacity of the battery is lowered.
음극 활물질 조성물에서 상기 산화물은 전해질 계면 피막 성분과 같은 방식으로 분말 형태로 혼합 사용할 수 있다.In the negative electrode active material composition, the oxide may be mixed and used in the same manner as the electrolyte interface coating component.
2. 음극용 슬러리2. Cathode Slurry
본 발명의 슬러리는 상술한 본 발명의 음극 활물질 조성물에 필요에 따라 바인더를 포함한 첨가물을 혼합한 것이다.The slurry of this invention mixes the additive containing the binder as needed with the negative electrode active material composition of this invention mentioned above.
바인더의 예로는 폴리 불화 비닐리덴(PVdF), 폴리 테트라 플루오로 에틸렌(PTFE), 스티렌 부타디엔 고무(SBR) 등이 있다.Examples of binders include polyvinylidene fluoride (PVdF), polytetrafluoroethylene (PTFE), styrene butadiene rubber (SBR), and the like.
그외 첨가물로 도전제와 점도 조절제, 보조결착제 등이 있다. 점도 조절제로는 카르복실메틸셀룰로오즈, 카르복실에틸셀룰로오즈, 에틸셀룰로오즈, 히드록시메틸셀룰로오즈, 히드록시프로필셀룰로오즈, 카르복실에틸메틸셀룰로오즈, 폴리에틸렌옥사이드, 에틸렌글리콜 등의 수용성 고분자를 사용할 수 있다.Other additives include conductive agents, viscosity regulators, and auxiliary binders. As the viscosity modifier, water-soluble polymers such as carboxymethyl cellulose, carboxyethyl cellulose, ethyl cellulose, hydroxymethyl cellulose, hydroxypropyl cellulose, carboxyethyl methyl cellulose, polyethylene oxide, and ethylene glycol can be used.
3. 리튬 이차 전지용 음극3. Anode for Lithium Secondary Battery
본 발명의 음극은, 본 발명의 음극 활물질 조성물을 포함한 음극용 슬러리를 집전체에 도포하고, 용매나 분산매를 건조 등의 방법으로 제거하여, 집전체에활물질을 결착시킴과 아울러 활물질끼리를 결착시켜서 제조한 것이다.In the negative electrode of the present invention, the negative electrode slurry containing the negative electrode active material composition of the present invention is applied to a current collector, and a solvent or a dispersion medium is removed by drying or the like to bind the active material to the current collector and to bind the active materials to each other. It is manufactured.
집전체는, 도전성 재료로 된 것이면 특별히 제한되지 않지만, 보통 구리 등의 금속제인 것을 사용한다. 형상도 특별히 제한되지 않지만, 보통 두께 0.001∼0.5㎜ 정도의 시이트 형상인 것을 사용한다.The current collector is not particularly limited as long as the current collector is made of a conductive material, but a metal such as copper is usually used. The shape is also not particularly limited, but usually a sheet having a thickness of about 0.001 to 0.5 mm is used.
슬러리를 집전체에 도포하는 방법도 특별히 제한되지 않는다. 예컨대, 닥터블레이드, 침지, 솔칠 등에 의해서 도포된다. 도포하는 양도 특별히 제한되지 않지만, 용매나 분산매를 제거한 후에 형성되는 활물질 층의 두께가 보통 0.005∼5㎜, 바람직하게는 0.05∼2㎜가 되는 정도의 양으로 한다. 용매 또는 분산매를 제거하는 방법도 특별히 제한되지 않지만, 통상은 응력집중이 발생하여 활물질 층에 균열이 생기거나, 활물질층이 집전체로부터 박리되지 않는 정도의 속도범위 중에서 되도록 신속하게 용매 또는 분산매가 휘발하도록 조정하여 제거한다.The method of applying the slurry to the current collector is also not particularly limited. For example, it is apply | coated by doctor blade, dipping, brushing, etc. The amount to be applied is not particularly limited either, but the thickness of the active material layer formed after removing the solvent or the dispersion medium is usually 0.005 to 5 mm, preferably about 0.05 to 2 mm. The method of removing the solvent or the dispersion medium is not particularly limited, but usually, the solvent or dispersion medium is volatilized so as to be within a speed range in which stress concentration occurs and cracks occur in the active material layer or the active material layer does not peel off from the current collector. Adjust to remove it.
4. 리튬 이차 전지4. lithium secondary battery
본 발명의 리튬 이차 전지는 본 발명에 따라 제조된 음극을 사용한 리튬 이차 전지이다. 리튬 이차 전지로는, 리튬 금속 이차 전지, 리튬 이온 이차 전지, 리튬 폴리머 이차 전지, 리튬 이온 폴리머 이차 전지 등을 들 수 있다.The lithium secondary battery of the present invention is a lithium secondary battery using a negative electrode produced according to the present invention. As a lithium secondary battery, a lithium metal secondary battery, a lithium ion secondary battery, a lithium polymer secondary battery, a lithium ion polymer secondary battery, etc. are mentioned.
본 발명의 리튬 이차 전지는Lithium secondary battery of the present invention
a) 리튬이온을 흡장 방출할 수 있는 양극;a) a cathode capable of storing and releasing lithium ions;
b) 리튬이온을 흡장 방출할 수 있는 음극;b) a negative electrode capable of storing and releasing lithium ions;
c) 다공성 분리막; 및c) a porous separator; And
d)ⅰ) 리튬 염;d) iii) lithium salts;
ⅱ) 전해액 화합물Ii) electrolyte compound
을 포함하는 비수전해액Non-aqueous electrolyte solution containing
을 포함한다.It includes.
본 발명의 비수전해액은 비제한적으로 환형 카보네이트와 선형 카보네이트를 포함한다. 상기 환형 카보네이트의 예를 들면 에틸렌 카보네이트(EC), 프로필렌 카보네이트(PC), 감마부티로락톤(GBL) 등이 있다. 상기 선형 카보네이트의 예를 들면 디에틸 카보네이트(DEC), 디메틸 카보네이트(DMC), 에틸메틸카보네이트(EMC), 및 메틸 프로필 카보네이트(MPC) 등이 있다.The nonaqueous electrolyte of the present invention includes, but is not limited to, cyclic carbonates and linear carbonates. Examples of the cyclic carbonates include ethylene carbonate (EC), propylene carbonate (PC), gamma butyrolactone (GBL), and the like. Examples of the linear carbonates include diethyl carbonate (DEC), dimethyl carbonate (DMC), ethylmethyl carbonate (EMC), methyl propyl carbonate (MPC), and the like.
본 발명의 비수전해액에는 리튬 염을 포함하며, 구체적 예를 들면 LiClO4, LiCF3SO3, LiPF6, LiBF4, LiAsF6, 및 LiN(CF3SO2)2로 이루어진 군으로부터 선택되는 것이 바람직하다.The non-aqueous electrolyte of the present invention includes a lithium salt, and specifically selected from the group consisting of LiClO 4 , LiCF 3 SO 3 , LiPF 6 , LiBF 4 , LiAsF 6 , and LiN (CF 3 SO 2 ) 2 . Do.
본 발명에서는 양극 활물질로 리튬 함유 전이 금속 산화물을 사용하며, 예를 들면 LiCoO2, LiNiO2, LiMn2O4, LiMnO2, LiNi1-XCoXMYO2(여기에서, M=Al, Ti, Mg, Zr, 0<X≤1, 0≤Y≤0.2) 및 LiNiXCoYMn1-X-YO2(여기에서, 0<X≤0.5, 0<Y≤0.5)로 이루어진 군으로부터 1종 이상 선택되는 것이 바람직하다. MnO2와 같은 금속 산화물 혹은 이들의 조합으로 이루어진 양극도 무방하다.In the present invention, a lithium-containing transition metal oxide is used as the positive electrode active material. For example, LiCoO 2 , LiNiO 2 , LiMn 2 O 4 , LiMnO 2 , LiNi 1-X Co X M Y O 2 (where M = Al, 1 from the group consisting of Ti, Mg, Zr, 0 < X ≦ 1 , 0 ≦ Y ≦ 0.2) and LiNi X Co Y Mn 1-XY O 2 (where 0 <X ≦ 0.5, 0 <Y ≦ 0.5) It is preferable to select more than a species. An anode made of a metal oxide such as MnO 2 or a combination thereof may be used.
또한, 본 발명은 리튬 이차 전지의 제조에 사용되는 다공성 분리막을 사용하며, 예를 들면 폴리올레핀계 다공성 분리막을 사용할 수 있다.In addition, the present invention uses a porous separator used in the production of a lithium secondary battery, for example, a polyolefin-based porous separator can be used.
본 발명의 리튬 이온 이차 전지는 통상적인 방법으로 음극과 양극 사이에 다공성의 분리막을 넣고, 상기한 LiPF6등의 리튬 염과 첨가제를 포함하는 비수전해액을 투입하여 제조할 수 있다.The lithium ion secondary battery of the present invention can be prepared by inserting a porous separator between the negative electrode and the positive electrode in a conventional manner, and by adding a non-aqueous electrolyte containing a lithium salt and additives such as LiPF 6 described above.
이하의 실시예를 통하여 본 발명을 더욱 상세하게 설명한다. 단 실시예는 본 발명을 예시하기 위한 것이지 본 발명을 한정하는 것은 아니다.The present invention will be described in more detail with reference to the following examples. However, the examples are only for illustrating the present invention and not for limiting the present invention.
[실시예]EXAMPLE
실시예 1Example 1
먼저, 인조흑연을 93.5중량%, 도전재로 Super_P를 1중량%, 결착제로서는 폴리 불화 비닐리덴을 5중량%, Li2CO3를 0.5중량%의 비율로 각각 혼합하여 얻은 음극 활물질 슬러리를 구리 동박 위에 코팅하여 음극을 제조하였다. 이렇게 제조한 음극을 작동 전극(working electrode)으로 사용하고, 상대 전극(counter electrode)으로 리튬 금속을 사용하여 코인형 반전지(coin half cell)를 제작하였다. 전해액으로 EC: DEC = 1: 1의 조성을 가지는 1M LiPF6용액을 사용하였다. 이후 0.0V에서 1.5V 의 전위 범위에서 0.2C의 속도(rate)로 충방전을 진행하였다.First, the negative electrode active material slurry obtained by mixing 93.5% by weight of artificial graphite, 1% by weight of Super_P as a conductive material, 5% by weight of polyvinylidene fluoride and 0.5% by weight of Li 2 CO 3 as a binder was copper The negative electrode was prepared by coating on copper foil. The cathode thus prepared was used as a working electrode, and a coin-type half cell was manufactured using lithium metal as a counter electrode. As an electrolyte, a 1M LiPF 6 solution having a composition of EC: DEC = 1: 1 was used. Since charging and discharging was carried out at a rate of 0.2C in the potential range of 0.0V to 1.5V.
실시예 2Example 2
인조흑연을 93.5중량%, 도전재로 Super_P를 1중량%, 결착제로서는 폴리 불화 비닐리덴을 5중량%, Al2O3를 0.5중량%의 비율로 각각 혼합하여 얻은 음극 활물질 슬러리를 구리 동박 위에 코팅하여 음극을 제조하고, 실시예 1과 동일한 방법으로 코인형 반전지(coin half cell)를 제작하여 충방전을 진행하였다.A negative electrode active material slurry obtained by mixing 93.5% by weight of artificial graphite, 1% by weight of Super_P as a conductive material, 5% by weight of polyvinylidene fluoride and 0.5% by weight of Al 2 O 3 as a binder was coated on copper copper foil. The negative electrode was prepared by coating, and a coin-type half cell was prepared and charged and discharged in the same manner as in Example 1.
실시예 3Example 3
인조흑연을 93중량%, 도전재로 Super_P를 1중량%, 결착제로서는 폴리 불화 비닐리덴을 5중량%, Li2CO3를 0.5중량%, Al2O3를 0.5중량%의 비율로 각각 혼합하여 얻은 음극 활물질 슬러리를 구리 동박 위에 코팅하여 음극을 제조하고, 실시예 1과 동일한 방법으로 코인형 반전지(coin half cell)를 제작하여 충방전을 진행하였다.93% by weight of artificial graphite, 1% by weight of Super_P as a conductive material, 5% by weight of polyvinylidene fluoride, 0.5% by weight of Li 2 CO 3 and 0.5% by weight of Al 2 O 3 as a binder The negative electrode active material slurry was coated on a copper copper foil to prepare a negative electrode, and a coin-type half cell was produced in the same manner as in Example 1 to perform charge and discharge.
비교예 1Comparative Example 1
인조흑연을 94중량%, 도전재로 Super_P를 1중량%, 결착제로서는 폴리 불화 비닐리덴을 5중량%의 비율로 각각 혼합하여 얻은 음극 활물질 슬러리를 구리 동박 위에 코팅하여 음극을 제조하고, 실시예 1과 동일한 방법으로 코인형 반전지(coin half cell)를 제작하여 충방전을 진행하였다.A negative electrode was prepared by coating a negative electrode active material slurry obtained by mixing 94% by weight of artificial graphite, 1% by weight of Super_P as a conductive material, and 5% by weight of polyvinylidene fluoride as a binder on a copper copper foil. In the same manner as in 1, a coin-type half cell was prepared to charge and discharge.
(충방전 반응)(Charge and discharge reaction)
앞에서 제작한 음극 코인형 반전지(coin half cell)를 충전시에는 0.2C의 속도로 CC-CV(constant current constant voltage) 방식으로 0.005V까지 정전류를 인가한 후 0.005V에서 정전압으로 전류를 제어하였고, 방전시에는 0.2C의 속도로 CC(constant current) 방식으로 1.5V에서 cut-off 시켜, 그 결과를 표 1 과 도 1 에 나타내었다.When charging the negative electrode coin-type half cell, the constant current was applied to 0.005V by CC-CV (constant current constant voltage) method at 0.2C, and then the current was controlled by 0.005V to constant voltage. At the time of discharge, cut-off at 1.5V by CC (constant current) method at a rate of 0.2C, the results are shown in Table 1 and FIG.
표 1에서 실시예 1과 2는 고체 전해질 계면 피막 성분, 전해액 흡수성이 우수한 금속 산화물 각각의 첨가물들이 초기 충전시의 비가역 반응을 제어하여 각각 0.9%의 초기효율 상승 효과를 나타내었다. 또 두 첨가물을 함께 첨가한 실시예 3에서는 1.8%의 초기효율 상승효과를 보여줘 각각의 첨가물이 시너지(synergy) 효과를 보여주고 있음을 알 수 있다. 또한 도 1에서 표시된 부분에서와 같이 실시예 1, 2, 3 모두 상기 첨가물들을 첨가하지 않은 비교예 1에 비하여 탄소재료 표면과 전해액 간의 비가역 반응이 제어되었음을 확인할 수 있다.In Table 1, Examples 1 and 2 exhibited an initial efficiency increase effect of 0.9% by controlling the irreversible reaction during the initial charging of the additives of the solid electrolyte interface coating component and the metal oxide having excellent electrolyte absorbency. In addition, in Example 3, in which the two additives were added together, an initial efficiency increase of 1.8% was shown, indicating that each additive showed a synergy effect. In addition, as shown in the portion shown in Figure 1, Examples 1, 2, 3 can be confirmed that the irreversible reaction between the surface of the carbon material and the electrolyte compared to Comparative Example 1 without the addition of the additives.
이상에서 설명한 바와 같이, 본 발명에 따르면 리튬 이온 전지, 또는 리튬 폴리머 전지의 음극 재료에 Li2CO3, Li2O, LiCH3CO2, LiF, LiOH 와 같은 SEI 피막을 구성하는 성분과 동일한 성분을 첨가 또는 이러한 성분으로 음극 활물질을 코팅하여 초기 비가역 반응을 제어하여 가역성을 높이고, 또한 탄소재료 주변에서 전해액에 대한 흡수 성질이 우수한 알루미늄, 규소, 지르코늄, 마그네슘, 칼슘, 스트론튬 및 희토류 원소로 된 군 중의 적어도 1종의 원소를 포함한 산화물을 함께 첨가하여 가역성을 증대시켜 고효율, 고용량의 전지를 구현할 수 있다.As described above, according to the present invention, the same components as the components constituting the SEI film, such as Li 2 CO 3 , Li 2 O, LiCH 3 CO 2 , LiF, LiOH, in the negative electrode material of a lithium ion battery or a lithium polymer battery Group of aluminum, silicon, zirconium, magnesium, calcium, strontium, and rare earth elements which improve reversibility by controlling the initial irreversible reaction by adding N or coating the negative electrode active material with such a component and having excellent absorption property of electrolyte around the carbon material An oxide containing at least one of the elements may be added together to increase reversibility, thereby implementing a battery having high efficiency and high capacity.
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KR20190057967A (en) * | 2017-11-21 | 2019-05-29 | 주식회사 엘지화학 | Negative electrode slurry composition for lithium secondary battery, and preparing method thereof |
US11489191B2 (en) | 2017-12-14 | 2022-11-01 | Lg Energy Solution, Ltd. | Continuous manufacturing method of lithium rechargeable battery forming passive film on surface of lithium metal electrode and lithium rechargeable battery manufactured therefrom |
WO2020242095A1 (en) * | 2019-05-24 | 2020-12-03 | 주식회사 엘지화학 | Method for manufacturing negative electrode for all-solid-state battery |
CN113826243A (en) * | 2019-05-24 | 2021-12-21 | 株式会社Lg新能源 | Method of manufacturing negative electrode for all-solid battery |
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