KR100793604B1 - Electrode with enhanced safety and performance and lithium secondary battery comprising the same - Google Patents

Electrode with enhanced safety and performance and lithium secondary battery comprising the same Download PDF

Info

Publication number
KR100793604B1
KR100793604B1 KR1020050012324A KR20050012324A KR100793604B1 KR 100793604 B1 KR100793604 B1 KR 100793604B1 KR 1020050012324 A KR1020050012324 A KR 1020050012324A KR 20050012324 A KR20050012324 A KR 20050012324A KR 100793604 B1 KR100793604 B1 KR 100793604B1
Authority
KR
South Korea
Prior art keywords
electrode
lithium secondary
secondary battery
dielectric constant
lithium
Prior art date
Application number
KR1020050012324A
Other languages
Korean (ko)
Other versions
KR20060091442A (en
Inventor
김석구
이상영
안순호
용현항
석정돈
Original Assignee
주식회사 엘지화학
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to KR1020050012324A priority Critical patent/KR100793604B1/en
Publication of KR20060091442A publication Critical patent/KR20060091442A/en
Application granted granted Critical
Publication of KR100793604B1 publication Critical patent/KR100793604B1/en

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • H01M4/36—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
    • 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 (a) 전극활물질; 및 (b) Pb(Zr,Ti)O3 (PZT), Pb1-xLaxZr1-yTiyO3 (PLZT), PB(Mg3Nb2/3)O3-PbTiO3 (PMN-PT), hafnia (HfO2), SrTiO3, SnO2, CeO2, MgO, CaO 및 Y2O3으로 이루어진 군으로부터 선택된 1종 이상의 무기물 입자를 포함하는 전극 슬러리로부터 제조된 것을 특징으로 하는 전극 및 상기 전극을 포함하는 리튬 이차 전지를 제공한다. The present invention (a) an electrode active material; And (b) Pb (Zr, Ti) O 3 (PZT), Pb 1-x La x Zr 1-y Ti y O 3 (PLZT), PB (Mg 3 Nb 2/3 ) O 3 -PbTiO 3 (PMN -PT), hafnia (HfO 2 ), SrTiO 3 , SnO 2 , CeO 2 , MgO, CaO and electrode electrode comprising an electrode slurry comprising at least one inorganic particle selected from the group consisting of Y 2 O 3 And it provides a lithium secondary battery comprising the electrode.

본 발명에 따른 리튬 이차 전지는 전극 성분으로 고유전율 무기물 입자를 사용함으로써, 전지의 안전성 및 성능을 향상시킬 수 있다. The lithium secondary battery according to the present invention can improve safety and performance of the battery by using high dielectric constant inorganic particles as an electrode component.

유전율, 무기물, 전극, 안전성, 리튬 이차 전지 Dielectric constant, inorganic material, electrode, safety, lithium secondary battery

Description

성능 및 안전성이 향상된 전극 및 이를 포함하는 리튬 이차 전지{ELECTRODE WITH ENHANCED SAFETY AND PERFORMANCE AND LITHIUM SECONDARY BATTERY COMPRISING THE SAME} ELECTRODE WITH ENHANCED SAFETY AND PERFORMANCE AND LITHIUM SECONDARY BATTERY COMPRISING THE SAME

본 발명은 전극 성분으로 고유전율 무기물 입자를 사용하여 제조된 전극 및 상기 전극을 포함하여 안전성 및 성능이 향상된 리튬 이차 전지에 관한 것이다.The present invention relates to an electrode manufactured using high dielectric constant inorganic particles as an electrode component, and to a lithium secondary battery having improved safety and performance, including the electrode.

최근 휴대용 컴퓨터, 휴대용 전화기, 캠코더 등의 휴대용 전자기기에 대한 소형화, 경량화를 위한 개발이 꾸준히 진행되고 있으며, 이와 함께 이들 전자기기의 전원으로 사용되는 리튬 2차 전지 역시 고용량화, 소형화, 경량화, 박리화가 요구되고 있다.Recently, development for miniaturization and weight reduction of portable electronic devices such as portable computers, portable telephones, camcorders, etc. has been steadily being progressed. In addition, lithium secondary batteries used as power sources for these electronic devices also have high capacity, miniaturization, light weight, and exfoliation. It is required.

리튬 이차 전지는 양극, 음극, 전해액으로 구성되며, 첫번째 충전에 의해 양극 활물질로부터 나온 리튬 이온이 음극활물질, 예컨대 카본 입자 내에 삽입되고 방전시 다시 탈리되는 등의 양 전극을 왕복하면서 에너지를 전달하는 역할을 하기 때문에 충방전이 가능하게 된다.The lithium secondary battery is composed of a positive electrode, a negative electrode, and an electrolyte, and transfers energy while reciprocating both electrodes such that lithium ions from the positive electrode active material are inserted into a negative electrode active material, such as carbon particles, and are detached again when discharged by the first charge. Since it is possible to charge and discharge.

상기한 리튬 이차 전지가 정해진 작동 전압 범위를 넘어 과충전이 진행되거나 또는 고온에서 장시간 보존되어 충전된 전극과 전해액의 발열반응이 진행되는 경 우, 양극과 전해액의 반응성이 증가하여 양극 표면의 분해(degradation) 및 전해액의 산화반응이 일어나게 된다. 또한 리튬 덴드라이트 성장(dendrite growth) 및 이로 인한 분리막 파괴, 급격한 발열 반응, 폭발 등과 같은 전지 안정성 결여의 문제점이 발생하게 된다. When the lithium secondary battery is overcharged beyond the specified operating voltage range, or when the exothermic reaction between the charged electrode and the electrolyte is carried out at a high temperature for a long time, the reactivity of the positive electrode and the electrolyte increases, resulting in degradation of the surface of the positive electrode. ) And the oxidation of the electrolyte occurs. In addition, there is a problem of lack of battery stability, such as lithium dendrite growth and the resulting membrane destruction, rapid exothermic reaction, explosion.

이와 같은 문제점을 해결하기 위해서, 대한민국 특허공개 제2000-0031096호에서는 리튬 이온 전지의 전극 또는 전해액에 분자 시브(molecular sieve)나 흄드 실리카 미분 등을 첨가하여 전지를 안정화하고자 하였다. 그러나 투입되는 첨가제의 양이 증가할수록 전해액 입장에서는 반응성이 없는 물질이 더해진 것과 같은 영향을 받게 되어 전지의 성능이 저하되는 문제점이 발생하였다.In order to solve such a problem, Korean Patent Publication No. 2000-0031096 attempts to stabilize a battery by adding molecular sieve or fumed silica fine powder to an electrode or electrolyte of a lithium ion battery. However, as the amount of the additive added increases, the electrolyte is affected by the addition of a non-reactive substance, resulting in a problem of deterioration of the battery performance.

본 발명은 종래의 문제점들을 고려하여, 전극 성분으로 고유전율 무기 산화물을 일정량 포함시키면 리튬 이차 전지의 안정성 및 성능을 향상시킨다는 것을 발견하였다.In view of the conventional problems, the present invention has been found to include a certain amount of a high dielectric constant inorganic oxide as an electrode component to improve the stability and performance of a lithium secondary battery.

이에 본 발명은 전지의 안전성 및 성능이 향상된 전극 및 상기 전극을 구비하는 리튬 이차 전지를 제공하는 것을 목적으로 한다.Accordingly, an object of the present invention is to provide an electrode having improved battery safety and performance and a lithium secondary battery having the electrode.

본 발명은 (a) 전극활물질; 및 (b) Pb(Zr,Ti)O3 (PZT), Pb1-xLaxZr1-yTiyO3 (PLZT), PB(Mg3Nb2/3)O3-PbTiO3 (PMN-PT), hafnia (HfO2), SrTiO3, SnO2, CeO2, MgO, CaO 및 Y2O3으로 이루어진 군으로부터 선택된 1종 이상의 무기물 입자를 포함하는 전극 슬러리로부터 제조된 것을 특징으로 하는 전극 및 상기 전극을 포함하는 리튬 이차 전지를 제공한다.The present invention (a) an electrode active material; And (b) Pb (Zr, Ti) O 3 (PZT), Pb 1-x La x Zr 1-y Ti y O 3 (PLZT), PB (Mg 3 Nb 2/3 ) O 3 -PbTiO 3 (PMN -PT), hafnia (HfO 2 ), SrTiO 3 , SnO 2 , CeO 2 , MgO, CaO and electrode electrode comprising an electrode slurry comprising at least one inorganic particle selected from the group consisting of Y 2 O 3 And it provides a lithium secondary battery comprising the electrode.

이하 본 발명에 대하여 상세히 설명한다.Hereinafter, the present invention will be described in detail.

본 발명은 유전율이 탁월하게 높은 무기물 입자들을 전극 성분으로 사용하는 것을 특징으로 한다.The present invention is characterized by using inorganic particles having an excellent dielectric constant as an electrode component.

상기 무기물 입자, 즉 Pb(Zr,Ti)O3 (PZT), Pb1-xLaxZr1-yTiyO3 (PLZT), PB(Mg3Nb2/3)O3-PbTiO3 (PMN-PT), hafnia (HfO2), SrTiO3, SnO2, CeO2, MgO, CaO, Y2O3들은 기존의 무반응성(inert); 또는 유전율 상수 5 이하인 저유전율 무기물 입자에 비해 유전율 상수가 100 이상인 고유전율 특성을 가질 뿐만 아니라, 종래 전지, 예컨대 리튬 이차 전지의 전극 첨가제 용도로 사용되지 않은 무기물 입자이다. The inorganic particles, namely Pb (Zr, Ti) O 3 (PZT), Pb 1-x La x Zr 1-y Ti y O 3 (PLZT), PB (Mg 3 Nb 2/3 ) O 3 -PbTiO 3 ( PMN-PT), hafnia (HfO 2 ), SrTiO 3 , SnO 2 , CeO 2 , MgO, CaO, Y 2 O 3 are conventional inerts; Or inorganic particles having a high dielectric constant of 100 or more relative to low dielectric constant inorganic particles having a dielectric constant of 5 or less, and which have not been used for electrode additives in conventional batteries such as lithium secondary batteries.

특히, Pb(Zr,Ti)O3 (PZT), Pb1-xLaxZr1-yTiyO3 (PLZT), PB(Mg3Nb2/3)O3-PbTiO3 (PMN-PT), hafnia (HfO2)들은 압전성(piezoelectricity), 즉 일정 압력을 인가하여 인장 또는 압축되는 경우 전하가 발생하여 한 면은 양으로, 반대편은 음으로 각각 대전됨으로써, 양쪽 면 간에 전위차가 발생하는 기능을 갖는다. Specifically, Pb (Zr, Ti) O 3 (PZT), Pb 1-x La x Zr 1-y Ti y O 3 (PLZT), PB (Mg 3 Nb 2/3 ) O 3 -PbTiO 3 (PMN-PT ), hafnia (HfO 2 ) are piezoelectricity, i.e., a charge is generated when it is stretched or compressed by applying a constant pressure, so that one side is positively charged and the other side is negatively charged, thereby generating a potential difference between both surfaces. Has

따라서, 본 발명의 리튬 이차 전지는 상기 무기물 입자의 첨가로 인해, 안전성 및 성능 향상을 도모할 수 있다.Therefore, the lithium secondary battery of the present invention can improve safety and performance due to the addition of the inorganic particles.

첫째로, 본 발명의 고유전율 무기물 입자가 첨가된 전극은 과충전시 또는 장시간 고온 보존시 전해액과 전극과의 부반응을 억제시킴으로써 전지의 열적 안전성을 향상시킬 수 있다. 즉, 충전된 전극과 전해액과의 고온에서의 발열 반응은 전극 표 면에서의 전해액 양에 크게 의존하게 되는데, 상기 고유전율 무기물 입자를 전극 구성 성분으로 첨가하는 경우, 충전 전극 내의 전해액 양이 상대적으로 감소하게 되어 전극과 전해액의 부반응이 억제된다. First, the electrode to which the high dielectric constant inorganic particles of the present invention are added may improve thermal safety of a battery by suppressing side reactions between the electrolyte and the electrode during overcharging or during high temperature storage for a long time. That is, the exothermic reaction at a high temperature between the charged electrode and the electrolyte is highly dependent on the amount of the electrolyte at the electrode surface. When the high dielectric constant inorganic particles are added as an electrode component, the amount of the electrolyte in the charged electrode is relatively high. This reduces the side reaction between the electrode and the electrolyte.

둘째로, 전해액에서 염의 해리도는 전해액 구성 성분의 유전율 상수에 의존하기 때문에, 상기 무기물 입자의 유전율 상수가 높을수록 전해액에서의 염 해리도를 향상시킬 수 있다. 상기 무기물 입자는 전술한 바와 같이 유전율 상수가 100 이상인 고유전율 특성을 보유함으로써, 종래 무반응성; 또는 저유전율 무기물 입자와는 달리 리튬 이온 해리를 향상시켜 전지의 성능 향상을 도모할 수 있다.Second, since the dissociation degree of the salt in the electrolyte depends on the dielectric constant of the constituent of the electrolyte, the higher the dielectric constant of the inorganic particles, the higher the salt dissociation in the electrolyte. As described above, the inorganic particles have a high dielectric constant characteristic having a dielectric constant of 100 or more, and thus, are conventionally non-reactive; Alternatively, unlike the low dielectric constant inorganic particles, lithium ion dissociation can be improved to improve battery performance.

상기 무기물 입자의 크기는 특별히 제한되지 않으며, 당분야에 알려진 통상적인 범위내에서 조절할 수 있다. The size of the inorganic particles is not particularly limited and may be adjusted within the conventional range known in the art.

또한, 전극에 첨가될 고유전율 무기물 입자의 양으로는 특별한 제한이 없으나, 특히 전극활물질 대비 0.01 내지 10 중량%가 바람직하다. 0.01 중량% 미만일 경우, 고유전율 무기물 입자의 첨가로 인해 발생되는 전지의 안전성 및 성능 향상 효과가 미미하며, 10 중량%를 초과할 경우, 첨가제의 첨가로 인한 전지의 용량 및 성능 저하가 야기된다.In addition, the amount of the high dielectric constant inorganic particles to be added to the electrode is not particularly limited, in particular 0.01 to 10% by weight relative to the electrode active material is preferred. If less than 0.01% by weight, the effect of improving the safety and performance of the battery caused by the addition of the high dielectric constant inorganic particles is insignificant, and if more than 10% by weight, the capacity and performance of the battery due to the addition of additives is caused.

상기 고유전율 무기물 입자가 첨가될 본 발명의 전극은 당 분야에 알려져 있는 통상적인 방법에 따라 각각 상기한 전극활물질 즉, 양극활물질 및/또는 음극활물질 및 상기 전극 첨가제를 혼합하여 전극 슬러리를 제조하고, 제조된 전극 슬러리를 각 전류 집전체에 도포한 후 용매나 분산매를 건조 등으로 제거하고, 집전체에 활물질을 결착시킴과 더불어 활물질간을 결착시켜 제조할 수 있다. 이때 선택적으로 도전제 및/또는 바인더를 소량 첨가할 수 있다. In the electrode of the present invention to which the high dielectric constant inorganic particles are added, an electrode slurry is prepared by mixing the electrode active material, that is, the positive electrode active material and / or the negative electrode active material, and the electrode additive according to a conventional method known in the art, After applying the prepared electrode slurry to each current collector, the solvent or dispersion medium may be removed by drying, and the active material may be bound to the current collector, and the active material may be bound to each other. In this case, a small amount of a conductive agent and / or a binder may be optionally added.

본 발명의 양극활물질은 리튬을 흡장 및 방출할 수 있는 리튬 전이금속 복합산화물이 사용 가능하며, 이의 비제한적인 예로는 리튬망간산화물(lithiated magnesium oxide), 리튬코발트산화물(lithiated cobalt oxide), 리튬니켈산화물 (lithiated nickel oxide), 리튬철산화물 (lithiated iron phosphate) 또는 이들의 조합에 의해서 형성된 복합산화물 등과 같은 리튬 흡착 물질(lithium intercalation material) 등이 있다.The cathode active material of the present invention may be used a lithium transition metal composite oxide capable of occluding and releasing lithium, non-limiting examples of lithium manganese oxide (lithiated magnesium oxide), lithium cobalt oxide (lithiated cobalt oxide), lithium nickel Lithium intercalation materials such as oxides (lithiated nickel oxide), lithium iron oxide (lithiated iron phosphate), or composite oxides formed by a combination thereof.

본 발명의 음극활물질은 리튬을 흡장 및 방출할 수 있는 리튬 합금, 카본(carbon), 석유코크(petroleum coke), 활성화 카본(activated carbon), 그래파이트(graphite), 또는 여타 카본류 등과 같은 리튬 흡착 물질을 사용할 수 있으며, 기타 리튬을 흡장 및 방출할 수 있고 리튬에 대한 전위가 2V 미만인 TiO2, SnO2, Li4Ti5O12 등과 같은 금속 산화물도 사용 가능하다The negative electrode active material of the present invention is a lithium adsorption material such as lithium alloy, carbon, petroleum coke, activated carbon, graphite, or other carbons capable of occluding and releasing lithium. And other metal oxides such as TiO 2 , SnO 2 , Li 4 Ti 5 O 12 , which can occlude and release lithium, and have a potential for lithium of less than 2V.

도전제로는 구성된 전지 내에서 화학변화를 일으키지 않는 전자전도성 재료이면 무엇이든지 사용 가능하다. 예를 들면 아세틸렌블랙, 케첸블랙, 파네스블랙, 서멀블랙 등의 카본블랙; 천연흑연, 인조흑연, 도전성 낱소섬유 등을 사용할 수 있다. 특히 카본블랙, 흑연분말, 탄소섬유가 바람직하다.As the conductive agent, any electronically conductive material which does not cause chemical change in the battery constructed can be used. For example, carbon black, such as acetylene black, Ketjen black, Farnes black, and thermal black; Natural graphite, artificial graphite, conductive yarn fibers, and the like can be used. Carbon black, graphite powder and carbon fiber are particularly preferable.

바인더로는 열가소성 수지, 열경화성 수지 중 어느 하나를 사용하더라도 좋으며, 이들을 조합하여 사용할 수도 있다. 이들 중에서는 폴리불화비닐리덴 (PVdF) 또는 폴리테트라플루오로에틸렌 (PTFE)이 바람직하며, 특히 PVdF가 더욱 바람직하 다. As the binder, any one of a thermoplastic resin and a thermosetting resin may be used, or a combination thereof may be used. Among these, polyvinylidene fluoride (PVdF) or polytetrafluoroethylene (PTFE) is preferable, and PVdF is particularly preferable.

전류 집전체는 도전성 재료로 된 것이면 특별히 제한되지 않으나, 양극일 경우 알루미늄, 니켈 또는 이들의 조합에 의해 제조된 호일이 바람직하며, 음극일 경우 구리, 금, 니켈, 구리 합금 또는 이들의 조합에 의해 제조된 호일이 바람직하다. The current collector is not particularly limited as long as it is made of a conductive material, but a foil made of aluminum, nickel or a combination thereof is preferable for the positive electrode, and copper, gold, nickel, a copper alloy, or a combination thereof for the negative electrode. Preferred foils are preferred.

또한 본 발명은 양극, 음극, 양 전극 사이에 개재된 분리막 및 전해질을 포함하는 리튬 이차 전지에 있어서, 상기 양극, 음극 또는 두 전극 모두가 상기와 같은 고유전율 특성을 갖는 전극 첨가제를 포함하는 전극 슬러리로부터 제조된 전극인 것을 특징으로 하는 리튬 이차 전지를 제공한다. In addition, the present invention is a lithium secondary battery comprising a separator and an electrolyte interposed between the positive electrode, the negative electrode, both electrodes, the positive electrode, the negative electrode or both electrodes comprises an electrode slurry comprising an electrode additive having the above high dielectric constant characteristics It provides a lithium secondary battery characterized in that the electrode manufactured from.

본 발명의 리튬 이차 전지는 당 기술 분야에 알려져 있는 통상적인 방법으로 상기 양극과 음극 사이에 다공성의 분리막을 넣고 전해질을 투입하여 제조할 수 있다Lithium secondary battery of the present invention can be prepared by inserting a porous separator between the positive electrode and the negative electrode in a conventional manner known in the art.

상기 전해질은 리튬염과 전해액 화합물을 포함하는 비수전해액으로서, 리튬염으로는 LiClO4, LiCF3SO3, LiPF6, LiBF4, LiAsF6 및 LiN(CF3SO2)2로 이루어진 군으로부터 선택된 1종 이상의 화합물이 바람직하다. 또한 전해액 화합물은 에틸렌 카보네이트(EC), 프로필렌 카보네이트(PC), 감마부티로락톤(GBL), 디에틸 카보네이트(DEC), 디메틸 카보네이트(DMC), 에틸메틸카보네이트 (EMC) 및 메틸 프로필 카보네이트(MPC)로 이루어진 군으로부터 선택된 1 종 이상이 바람직하다.The electrolyte is a non-aqueous electrolyte containing a lithium salt and an electrolyte compound, wherein the lithium salt is 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 . Preference is given to compounds of species or more. In addition, the electrolyte compounds include ethylene carbonate (EC), propylene carbonate (PC), gamma butyrolactone (GBL), diethyl carbonate (DEC), dimethyl carbonate (DMC), ethylmethyl carbonate (EMC) and methyl propyl carbonate (MPC). At least one selected from the group consisting of is preferable.

본 발명의 전지 제조시에는 분리막(seperator)으로서 다공성 분리막을 사용하는 것이 바람직하며, 비제한적인 예로는 폴리프로필렌계, 폴리에틸렌계 또는 폴리 올레핀계 다공성 분리막 등이 있다.In manufacturing the battery of the present invention, it is preferable to use a porous separator as a separator, and non-limiting examples include a polypropylene-based, polyethylene-based or polyolefin-based porous separator.

본 발명의 리튬 이차 전지는 외형에 제한이 없으나, 캔을 사용한 원통형, 각형, 파우치(pouch)형 또는 코인(coin)형 등이 될 수 있다. The lithium secondary battery of the present invention is not limited in appearance, but may be cylindrical, square, pouch type, or coin type using a can.

이하 실시예 및 비교예를 들어 본 발명을 보다 자세히 설명할 것이다. 그러나 본 발명이 이로써 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, the present invention is not limited thereto.

실시예 1. 리튬 이차 전지 제조Example 1. Lithium Secondary Battery Preparation

1-1. 양극1-1. anode

양극 활물질로 LiCoO2 89 중량%, 고유전율 전극 첨가제로 PMN-PT 3중량%, 도전제로 카본 블랙 (carbon black) 4 중량%, 결합제로 PVDF 4 중량%를 용제인 N-메틸-2 피롤리돈(NMP)에 첨가하여 양극 혼합물 슬러리를 제조한다. 상기 양극 혼합물 슬러리를 두께가 20㎛인 양극 집전체의 알루미늄(Al) 박막에 도포 및 건조를 통하여 양극을 제조한 후, 롤 프레스(roll press)를 실시한다. 89% by weight of LiCoO 2 as a positive electrode active material, 3% by weight of PMN-PT as a high dielectric constant electrode additive, 4% by weight of carbon black as a conductive agent, and 4% by weight of PVDF as a binder, N-methyl-2 pyrrolidone as a solvent (NMP) is added to form a positive electrode mixture slurry. The positive electrode mixture slurry is coated on a thin film of aluminum (Al) of a positive electrode current collector having a thickness of 20 μm and manufactured to produce a positive electrode, followed by a roll press.

1-2. 음극1-2. cathode

음극 활물질로 탄소 분말, 결합재로 폴리비닐리덴플로라이드(PVdF), 도전재로 카본 블랙 (carbon black)을 각각 96 중량%, 3 중량%, 1 중량%로 하여 용제인 N-메틸-2 피롤리돈(NMP)에 첨가하여 음극 혼합물 슬러리를 제조한다. 상기 음극 혼합물 슬러리를 두께가 10 ㎛인 음극 집전체인 구리(Cu) 박막에 도포, 건조를 통하여 음극을 제조한 후 롤 프레스(roll press)를 실시한다. N-methyl-2 pyrroli as a solvent by using carbon powder as a negative electrode active material, polyvinylidene fluoride (PVdF) as a binder, and carbon black as a conductive material at 96% by weight, 3% by weight, and 1% by weight, respectively. Add to NMP to prepare a negative electrode mixture slurry. The negative electrode mixture slurry is applied to a copper (Cu) thin film, which is a negative electrode current collector having a thickness of 10 μm, to prepare a negative electrode through drying, and then roll press is performed.

1-3. 전해액 제조1-3. Manufacture of electrolyte

1몰의 리튬헥사플로로포스페이트 (LiPF6)이 용해된 에틸렌카보네이트 / 프로필렌카보네이트 / 디에틸카보네이트(EC:PC:DEC=30:20:50 중량%) 의 혼합 용액을 사용한다.A mixed solution of ethylene carbonate / propylene carbonate / diethyl carbonate (EC: PC: DEC = 30: 20: 50% by weight) in which 1 mol of lithium hexafluorophosphate (LiPF 6 ) is dissolved is used.

1-4. 전지 제조1-4. Battery manufacturing

제조된 양 전극을 폴리프로필렌/폴리에틸렌/폴리프로필렌(PP/PE/PP)으로 구성된 분리막을 함께 조립한 후, 상기 전해액을 투입하여 최종적으로 전지를 완성한다.After the assembled positive electrode is assembled with a separator consisting of polypropylene / polyethylene / polypropylene (PP / PE / PP) together, the electrolyte is added to finally complete the battery.

비교예 1. 리튬 이차 전지 제조Comparative Example 1. Manufacture of Lithium Secondary Battery

무기물 입자를 사용하지 않고 전극을 제조한 것을 제외하고는, 상기 실시예 1과 동일하게 리튬 이차 전지를 제조한다.A lithium secondary battery was manufactured in the same manner as in Example 1, except that the electrode was manufactured without using the inorganic particles.

실험예 1. 리튬 이차 전지의 과충전 실험Experimental Example 1. Overcharge Experiment of Lithium Secondary Battery

본 발명에 따라 고유전율 무기물 입자가 첨가된 전극을 구비한 리튬 이차 전지의 안전성 평가를 하기와 같이 실시한다.According to the present invention, safety evaluation of a lithium secondary battery provided with an electrode to which high dielectric constant inorganic particles are added is carried out as follows.

실시예 1, 비교예 1에서 제조된 리튬 이차 전지를 사용하고, 각 전지를 충방전 전압범위는 0 내지 6V(vs. Li/Li+), 전류는 1C(1A)의 조건하에서 실시한다. Using a lithium secondary battery prepared in Example 1, Comparative Example 1, each battery is carried out under the conditions of charge and discharge voltage range of 0 to 6V ( vs. Li / Li + ), current 1C (1A).

본 발명은 전극 성분으로 고유전율 무기물 입자를 사용함으로써 리튬 이차 전지의 안전성 및 성능을 향상시킬 수 있다. The present invention can improve the safety and performance of the lithium secondary battery by using a high dielectric constant inorganic particles as the electrode component.

Claims (3)

(a) 전극활물질; 및(a) an electrode active material; And (b) Pb(Zr,Ti)O3 (PZT), Pb1-xLaxZr1-yTiyO3 (PLZT), PB(Mg3Nb2/3)O3-PbTiO3 (PMN-PT), hafnia (HfO2), SrTiO3, SnO2, CeO2, MgO, CaO 및 Y2O3으로 이루어진 군으로부터 선택된 1종 이상의 무기물 입자(b) Pb (Zr, Ti) O 3 (PZT), Pb 1-x La x Zr 1-y Ti y O 3 (PLZT), PB (Mg 3 Nb 2/3 ) O 3 -PbTiO 3 (PMN- PT), hafnia (HfO 2) , SrTiO 3, SnO 2, CeO 2, MgO, CaO and Y 2 O at least one selected from the group consisting of inorganic particles 3 를 포함하는 전극 슬러리로부터 제조된 것을 특징으로 하는 전극.Electrode, characterized in that prepared from the electrode slurry comprising a. 제 1항에 있어서, 상기 무기물 입자의 함량은 전극활물질 대비 0.01 내지 10 중량%인 전극.The electrode of claim 1, wherein the content of the inorganic particles is 0.01 to 10 wt% based on the electrode active material. a) 양극, a) anode, b) 음극; b) a cathode; c) 분리막; 및 c) membrane; And d) 전해질d) electrolyte 을 포함하는 리튬 이차 전지에 있어서, 상기 양극, 음극 또는 양 전극은 제 1항 또는 제 2항의 전극인 것을 특징으로 하는 리튬 이차 전지.The lithium secondary battery comprising a, wherein the positive electrode, the negative electrode or the positive electrode is a lithium secondary battery, characterized in that the electrode of claim 1 or 2.
KR1020050012324A 2005-02-15 2005-02-15 Electrode with enhanced safety and performance and lithium secondary battery comprising the same KR100793604B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
KR1020050012324A KR100793604B1 (en) 2005-02-15 2005-02-15 Electrode with enhanced safety and performance and lithium secondary battery comprising the same

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
KR1020050012324A KR100793604B1 (en) 2005-02-15 2005-02-15 Electrode with enhanced safety and performance and lithium secondary battery comprising the same

Publications (2)

Publication Number Publication Date
KR20060091442A KR20060091442A (en) 2006-08-21
KR100793604B1 true KR100793604B1 (en) 2008-01-10

Family

ID=37593201

Family Applications (1)

Application Number Title Priority Date Filing Date
KR1020050012324A KR100793604B1 (en) 2005-02-15 2005-02-15 Electrode with enhanced safety and performance and lithium secondary battery comprising the same

Country Status (1)

Country Link
KR (1) KR100793604B1 (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101287106B1 (en) 2011-03-02 2013-07-17 삼성에스디아이 주식회사 Negative electrode for rechargeable lithium battery, method of preparing same and rechargeable lithium battery including same
KR102356240B1 (en) * 2014-12-09 2022-01-26 에스케이온 주식회사 Anode composition for lithium secondary battery, anode for lithium secondary battery and lithium secondary battery using the same
CN106935859B (en) * 2017-02-17 2021-07-27 中国科学院西安光学精密机械研究所 Novel rare earth magnesium-rich lithium ion power battery

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5169736A (en) 1990-08-09 1992-12-08 Varta Batterie Aktiengesellschaft Electrochemical secondary element
JPH05225981A (en) * 1991-11-22 1993-09-03 Honda Motor Co Ltd Positive electrode material for lithium battery and manufacture thereof
JP2001202960A (en) 2000-01-14 2001-07-27 Sony Corp Positive electrode material and secondary battery using the same
KR100570637B1 (en) 2003-05-21 2006-04-12 삼성에스디아이 주식회사 Negative active material for lithium secondary battery and method of preparing same

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5169736A (en) 1990-08-09 1992-12-08 Varta Batterie Aktiengesellschaft Electrochemical secondary element
JPH05225981A (en) * 1991-11-22 1993-09-03 Honda Motor Co Ltd Positive electrode material for lithium battery and manufacture thereof
JP2001202960A (en) 2000-01-14 2001-07-27 Sony Corp Positive electrode material and secondary battery using the same
KR100570637B1 (en) 2003-05-21 2006-04-12 삼성에스디아이 주식회사 Negative active material for lithium secondary battery and method of preparing same

Also Published As

Publication number Publication date
KR20060091442A (en) 2006-08-21

Similar Documents

Publication Publication Date Title
KR100826814B1 (en) Solid electrolyte cell
JP4757861B2 (en) Lithium secondary battery with improved safety and performance
JP4752574B2 (en) Negative electrode and secondary battery
US20070082261A1 (en) Lithium rechargeable battery
KR20180036600A (en) Anode for lithium secondary battery with double protective layer and lithium secondary battery comprising the same
CN111384399B (en) Protective coating for lithium metal electrodes
US20060240290A1 (en) High rate pulsed battery
KR20100094363A (en) Nonaqueous electrolyte secondary battery
JP2006294282A (en) Manufacturing method of lithium-ion secondary battery
JP2008097879A (en) Lithium ion secondary battery
KR20180006054A (en) Positive electrode for lithium secondary battery having improved capacity and safety and lithium secondary battery comprising the same
JP4686852B2 (en) Non-aqueous electrolyte battery
US20180198120A1 (en) Lithium secondary battery
US10957936B2 (en) Lithium ion secondary battery
JP4741526B2 (en) Nonaqueous electrolyte secondary battery
KR100793604B1 (en) Electrode with enhanced safety and performance and lithium secondary battery comprising the same
KR20210034985A (en) Method for manufacturing secondary battery
JP2007172947A (en) Nonaqueous electrolyte secondary battery
JP2004228010A (en) Manufacturing method of lithium ion secondary battery
JP2007103198A (en) Anode and battery
KR20200065625A (en) Lithium secondary battery, and method for preparing the same
US20220255150A1 (en) Method of manufacturing secondary battery
KR20060063371A (en) Electrode added with polyethyleneglycol and lithium secondary batteries using the same
JP2002260726A (en) Nonaqueous electrolyte secondary battery
KR20210109896A (en) Method for manufacturing secondary battery

Legal Events

Date Code Title Description
A201 Request for examination
E701 Decision to grant or registration of patent right
GRNT Written decision to grant
FPAY Annual fee payment

Payment date: 20130102

Year of fee payment: 6

FPAY Annual fee payment

Payment date: 20140102

Year of fee payment: 7

FPAY Annual fee payment

Payment date: 20141231

Year of fee payment: 8

FPAY Annual fee payment

Payment date: 20151229

Year of fee payment: 9

FPAY Annual fee payment

Payment date: 20180102

Year of fee payment: 11

FPAY Annual fee payment

Payment date: 20190102

Year of fee payment: 12

FPAY Annual fee payment

Payment date: 20200102

Year of fee payment: 13