KR20000074958A - Positive active material for lithium secondary battery and lithium secondary by using the same - Google Patents
Positive active material for lithium secondary battery and lithium secondary by using the same Download PDFInfo
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- KR20000074958A KR20000074958A KR1019990019247A KR19990019247A KR20000074958A KR 20000074958 A KR20000074958 A KR 20000074958A KR 1019990019247 A KR1019990019247 A KR 1019990019247A KR 19990019247 A KR19990019247 A KR 19990019247A KR 20000074958 A KR20000074958 A KR 20000074958A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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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
- 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
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- Y02E60/10—Energy storage using batteries
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Abstract
Description
[산업상 이용 분야][Industrial use]
본 발명은 리튬 이차 전지용 양극 활물질에 관한 것으로서, 더욱 상세하게는 고온 사이클 수명 특성이 우수한 리튬 이차 전지용 양극 활물질에 관한 것이다.The present invention relates to a positive electrode active material for lithium secondary batteries, and more particularly, to a positive electrode active material for lithium secondary batteries having excellent high temperature cycle life characteristics.
[종래 기술][Prior art]
현재 리튬 이차 전지는 휴대폰, 캠코더 및 노트북 컴퓨터에 적용이 급격하게 증가되고 있는 추세이다. 이들 전지들의 용량을 좌우하는 인자는 양극 활물질이고 이들 물질들의 전기 화학적 특성에 의해 고율에서 장시간 사용가능한지 아니면 많은 충반전 사이클을 지나도록 초기의 용량을 유지하는 특성이 결정된다. 다른 중요한 특성 요인은 고온에서의 용량 감소율이다. 예를 들면 휴대폰인 경우 높은 온도(50℃)에 장시간 방치시 용량 저하가 급격하며 이 원인은 고온에서 양극 활물질을 구성하는 원소가 전해액으로 용출되기 때문이다.Currently, lithium secondary batteries are rapidly increasing in application to mobile phones, camcorders, and notebook computers. The factor that determines the capacity of these batteries is the positive electrode active material and the electrochemical properties of these materials determine whether they can be used at high rates for a long time or maintain their initial capacity over many charge and discharge cycles. Another important characteristic factor is the rate of capacity reduction at high temperatures. For example, in the case of a mobile phone, the capacity decreases rapidly when left at a high temperature (50 ° C.) for a long time.
상기 리튬 이차 전지용 양극 활물질로 사용되고 있는 물질 중에서 LiMn2O4, LiMnO2등의 망간계 활물질은 합성이 용이하며, 제조 비용이 비교적 저렴하고, 환경에 대한 오염도 적다는 장점이 있다. 그 중에서도 LiMn2O4는 전지 시스템의 안정성 등으로 전기 자동차(electric vehicle)에 적용 가능성이 가장 높은 양극 활물질로 부각되고 있다.Among the materials used as the cathode active material for lithium secondary batteries, manganese-based active materials such as LiMn 2 O 4 and LiMnO 2 are easy to synthesize, have a relatively low manufacturing cost, and have low environmental pollution. Among them, LiMn 2 O 4 is emerging as a cathode active material having the highest applicability to electric vehicles due to the stability of a battery system.
LiMn2O4는 상온 사이클 수명은 우수하지만, 고온에서 연속적인 충방전시 용량이 급격히 감소하는 문제점이 있다. LiMn2O4에서 Mn의 원자가는 3.5로써, 실질적으로는 Mn이 Mn3+와 Mn4+의 형태로 존재한다. 이때, 온도가 증가하면, Mn4+는 안정하나, Mn3+는 불안정하여, 고온 충방전시 Mn3+가 Mn4+와 Mn2+로 되는 불균형화(disproportionation) 반응이 일어나서, 고온 충방전시 용량이 급격히 감소하는 것으로 알려져 있다. 또한, LiMn2O4를 사용한 전지는 초기 10 사이클 이내에 용량이 급격하게 감소하는 현상이 발생되는 문제점이 있다.LiMn 2 O 4 has excellent cycle life at room temperature, but has a problem in that capacity decreases rapidly during continuous charge and discharge at high temperatures. The valence of Mn in LiMn 2 O 4 is 3.5, substantially Mn is present in the form of Mn 3+ and Mn 4+ . At this time, when the temperature is increased, Mn 4+ is stable, but Mn 3+ is unstable, and a disproportionation reaction occurs in which Mn 3+ becomes Mn 4+ and Mn 2+ during high temperature charge and discharge, and thus, high temperature charge and discharge It is known that the dose decreases rapidly. In addition, a battery using LiMn 2 O 4 has a problem in that a phenomenon in which capacity decreases rapidly within an initial 10 cycle occurs.
본 발명은 상기한 문제점을 해결하기 위한 것으로서, 본 발명의 목적은 고온 사이클 수명 특성이 우수한 망간계 리튬 이차 전지용 양극 활물질을 제공하는 것이다.The present invention is to solve the above problems, an object of the present invention is to provide a positive electrode active material for manganese-based lithium secondary battery excellent in high temperature cycle life characteristics.
도 1은 본 발명의 실시예 및 비교예의 방법으로 제조된 리튬 이차 전지의 고온 사이클 수명 특성을 나타낸 그래프.1 is a graph showing the high temperature cycle life characteristics of the lithium secondary battery prepared by the method of the Examples and Comparative Examples of the present invention.
상기한 목적을 달성하기 위하여, 본 발명은 하기 화학식 1의 리튬 이차 전지용 양극 활물질을 제공한다.In order to achieve the above object, the present invention provides a cathode active material for a lithium secondary battery of the formula (1).
[화학식 1][Formula 1]
Li1+aMn2-yMyO4-zSz Li 1 + a Mn 2-y M y O 4-z S z
(상기 식에서, -0.1 ≤ a ≤ 0.2, 0 ≤ y ≤ 0.2, -0.1 ≤ z ≤ 0.2이고, M은 전이 금속이다.)(In the above formula, -0.1 <a <0.2, 0 <y <0.2, -0.1 <z <0.2, and M is a transition metal.)
또한, 상기 화학식 1의 리튬 이차 전지용 양극 활물질을 포함하는 양극; 리튬 이온의 탈삽입이 가능한 음극 활물질을 포함하는 음극; 상기 양극과 음극 사이에 존재하는 세퍼레이터; 및 상기 비수용액 전해질을 포함하는 리튬 이차 전지를 제공한다.In addition, the positive electrode including a positive active material for a lithium secondary battery of Formula 1; A negative electrode including a negative electrode active material capable of deintercalation of lithium ions; A separator present between the anode and the cathode; And it provides a lithium secondary battery comprising the non-aqueous electrolyte.
이하 본 발명을 더욱 상세하게 설명한다.Hereinafter, the present invention will be described in more detail.
본 발명자들은 LiMn2O4에서 O의 일부를 S로 치환하고, Mn의 일부를 전이 금속(transition metal)로 치환함으로써, 고온에서의 사이클 수명이 우수한 망간계 리튬 이차 전지용 양극 활물질을 제공할 수 있음을 발견하고 본 발명을 완성하였다.The present inventors can provide a positive electrode active material for manganese-based lithium secondary batteries having excellent cycle life at high temperature by replacing a portion of O with S in LiMn 2 O 4 and a portion of Mn with a transition metal. And the present invention was completed.
O의 일부를 S로 치환하고, Mn의 일부를 전이 금속을 치환한 본 발명의 양극 활물질은 하기 화학식 1을 갖는다.The positive electrode active material of the present invention in which a part of O is substituted with S and a part of Mn is substituted with a transition metal has the following formula (1).
[화학식 1][Formula 1]
Li1+aMn2-yMyO4-zSz Li 1 + a Mn 2-y M y O 4-z S z
(상기 식에서, -0.1 ≤ a ≤ 0.2, 0 ≤ y ≤ 0.2, -0.1 ≤ z ≤ 0.2이고, M은 전이 금속이며, 예를 들면, Sc, Ti, V, Cr, Cu, Zn, Ga, Ge, Ag, Cd 등의 전이 금속이다.(Wherein, -0.1 ≦ a ≦ 0.2, 0 ≦ y ≦ 0.2, −0.1 ≦ z ≦ 0.2, M is a transition metal, for example Sc, Ti, V, Cr, Cu, Zn, Ga, Ge And transition metals such as Ag and Cd.
상기 화학식 1에 나타낸 것과 같이, 본 발명의 양극 활물질은 O의 일부를 S로 치환하고, Mn의 일부를 전이 금속으로 치환하고 Li의 양을 일부 조절하여 형성된 양극 활물질이다.As shown in Formula 1, the cathode active material of the present invention is a cathode active material formed by substituting part of O with S, substituting part of Mn with a transition metal, and partially controlling the amount of Li.
상기한 구성을 갖는 양극 활물질은 O의 일부를 S로 치환하고, Mn의 일부를 전이 금속으로 치환함에 따라 고온 사이클 수명 특성이 우수한 전지를 제공할 수 있었다. 또한, Li의 양을 조절함에 따라, Mn의 원자가를 조절할 수 있으므로, Mn3+가 Mn4+와 Mn2+로 되는 불균형화 현상에 따른 고온에서 급격한 용량 감소를 방지할 수 있다.The positive electrode active material having the above-described structure was able to provide a battery having excellent high temperature cycle life characteristics by replacing part of O with S and part of Mn with a transition metal. In addition, by controlling the amount of Li, the valence of Mn can be adjusted, so that a sudden decrease in capacity at high temperatures due to an unbalanced phenomenon in which Mn 3+ becomes Mn 4+ and Mn 2+ can be prevented.
본 발명에 따른 양극 활물질은 리튬염, 망간염, 황화염 및 코발트염을 적정 비율로 혼합한 후, 이를 약 750∼800℃에서 소성함으로써 제조될 수 있다. 상기 리튬염으로는 리튬 카보네이트, 리튬 나이트레이트, 리튬 하이드록사이드 등이 사용될 수 있으며, 상기 망간염으로는 망간 아세테이트, 망간 디옥사이드 등이 사용될 수 있다. 또한, 상기 황화염으로는 망간 설파이드, 리튬 설파이드 등을 사용할 수 있고, 상기 코발트염으로는 코발트 하이드록사이드, 코발트 나이트레이트 또는 코발트 카보네이트 등을 사용할 수 있다. 상기 리튬염, 망간염, 불화염, 황화염 및 코발트염이 상술한 화합물에 한정되는 것은 아니다.The cathode active material according to the present invention may be prepared by mixing lithium salts, manganese salts, sulfide salts and cobalt salts in an appropriate ratio, and then baking them at about 750 to 800 ° C. Lithium carbonate, lithium nitrate, lithium hydroxide, etc. may be used as the lithium salt, and manganese acetate, manganese dioxide, and the like may be used as the manganese salt. In addition, manganese sulfide, lithium sulfide, or the like may be used as the sulfide salt, and cobalt hydroxide, cobalt nitrate or cobalt carbonate may be used as the cobalt salt. The lithium salt, manganese salt, fluoride salt, sulfide salt and cobalt salt are not limited to the above-mentioned compounds.
본 발명의 양극 활물질을 이용한 리튬 이차 전지는 음극으로 리튬 이온의 탈삽입(deintercalation-intercalation)이 가능한 그라파이트, 카본 등의 일반적으로 리튬 이차 전지의 음극 활물질로 사용되는 물질인 탄소재 활물질로 제조된 것을 사용할 수 있다. 전해질로는 일반적으로 리튬 이차 전지의 전해질로 사용되는 비수용액계 액체 전해질, 폴리머 전해질 등을 사용할 수 있다. 세퍼레이터로는 일반적으로 리튬 이차 전지에서 사용되는 고분자 필름이 사용될 수 있다.The lithium secondary battery using the positive electrode active material of the present invention is made of a carbon-based active material that is a material that is generally used as a negative electrode active material of lithium secondary batteries, such as graphite and carbon, which can deintercalation-intercalation of lithium ions as a negative electrode. Can be used. As the electrolyte, a non-aqueous liquid electrolyte, a polymer electrolyte, or the like, which is generally used as an electrolyte of a lithium secondary battery, can be used. As the separator, a polymer film generally used in a lithium secondary battery may be used.
이하 본 발명의 바람직한 실시예 및 비교예를 기재한다. 그러나 하기한 실시예는 본 발명의 바람직한 일 실시예일 뿐 본 발명이 하기한 실시예에 한정되는 것은 아니다.Hereinafter, preferred examples and comparative examples of the present invention are described. However, the following examples are only one preferred embodiment of the present invention and the present invention is not limited to the following examples.
(실시예 1)(Example 1)
Li2CO3, MnS, CoOH 및 MnO2를 Li1.03Mn1.97Co0.03O3.9975S0.0025의 몰비가 되도록 균일하게 혼합한 후, 이 혼합물을 750℃에서 24시간 동안 소성 후 상온까지 서냉하여, 리튬 이차 전지용 양극 활물질을 제조하였다.After mixing Li 2 CO 3 , MnS, CoOH and MnO 2 homogeneously in a molar ratio of Li 1.03 Mn 1.97 Co 0.03 O 3.9975 S 0.0025 , the mixture was calcined at 750 ° C. for 24 hours and then cooled slowly to room temperature to obtain a lithium secondary. A battery positive electrode active material was prepared.
상기 활물질, 바인더로서 폴리비닐리덴, 도전제로서 카본 블랙을 92 : 4 : 4의 중량%로 혼합한 다음, 일정량의 N-메틸 피롤리돈을 첨가하면서 균일한 페이스트가 될 때까지 섞었다. 이 페이스트를 닥터-블레이드(doctor-blade)기를 이용하여 300 미크론(micron)의 두께로 알루미늄 호일에 코팅한 후 150℃에서 N-메틸 피롤리돈을 완전히 날려 보낸 다음 일정한 압력으로 압축하였다. 대극으로 리튬 호일도 양극과 같은 크기로 자른 다음, 코인 전지 캡의 Ni 호일에 압축하여 붙였다. 세퍼레이터는 셀가드 사(celgard) 제품을 사용하였으며, 전해질은 LiPF6가 용해된 에틸렌 카보네이트/디메틸 카보네이트의 혼합물을 사용하였다.Polyvinylidene as the active material, binder, and carbon black as the conductive agent were mixed at a weight ratio of 92: 4: 4, followed by mixing until a uniform paste was added while adding a certain amount of N-methyl pyrrolidone. The paste was coated on aluminum foil to a thickness of 300 microns using a doctor-blade machine and then completely blown N-methyl pyrrolidone at 150 ° C. and then compressed to constant pressure. As a counter electrode, the lithium foil was also cut to the same size as the positive electrode, and then pressed to Ni foil of the coin battery cap. The separator used was celgard, and the electrolyte used was a mixture of ethylene carbonate / dimethyl carbonate in which LiPF 6 was dissolved.
(실시예 2)(Example 2)
Li2CO3, MnS, CoOH 및 MnO2를 Li1.03Mn1.97Co0.03O3.995S0.005의 몰비가 되도록 균일하게 혼합한 후, 이 혼합물을 750℃에서 24시간 동안 소성 후 상온까지 서냉하여, 리튬 이차 전지용 양극 활물질을 제조하였다. 상기 활물질을 이용하여 상기 실시예 1과 같이 코인 전지를 제조하였다.After mixing Li 2 CO 3 , MnS, CoOH and MnO 2 homogeneously to a molar ratio of Li 1.03 Mn 1.97 Co 0.03 O 3.995 S 0.005 , the mixture was calcined at 750 ° C. for 24 hours and then cooled slowly to room temperature to obtain a lithium secondary. A battery positive electrode active material was prepared. A coin battery was manufactured as in Example 1 using the active material.
(실시예 3)(Example 3)
Li2CO3, MnS, CoOH 및 MnO2를 Li1.03Mn1.97Co0.03O3.99S0.01의 몰비가 되도록 균일하게 혼합한 후, 이 혼합물을 750℃에서 24시간 동안 소성 후 상온까지 서냉하여, 리튬 이차 전지용 양극 활물질을 제조하였다. 상기 양극 활물질을 이용하여, 상기 실시예 1과 동일하게 실시하여 코인 전지를 제조하였다.After uniformly mixing Li 2 CO 3 , MnS, CoOH and MnO 2 to a molar ratio of Li 1.03 Mn 1.97 Co 0.03 O 3.99 S 0.01 , the mixture was calcined at 750 ° C. for 24 hours and then cooled slowly to room temperature to obtain a lithium secondary. A battery positive electrode active material was prepared. Using the positive electrode active material, a coin battery was manufactured in the same manner as in Example 1.
(비교예 1)(Comparative Example 1)
Li2CO3및 MnO2를 LiMn2O4의 몰비가 되도록 균일하게 혼합한 후, 이 혼합물을 790℃에서 24시간 동안 소성하고, 상온까지 서냉하여 리튬 이차 전지용 양극 활물질을 제조하였다. 상기 양극 활물질을 이용하여 상기 실시예 1과 동일하게 실시하여 코인 전지를 제조하였다.After uniformly mixing Li 2 CO 3 and MnO 2 to a molar ratio of LiMn 2 O 4 , the mixture was calcined at 790 ° C. for 24 hours, and cooled slowly to room temperature to prepare a cathode active material for a lithium secondary battery. A coin battery was prepared in the same manner as in Example 1 using the cathode active material.
상기 실시예 1-3 및 비교예 1의 전지를 이용하여 전지의 고온(50℃) 사이클 수명 특성을 측정하여 그 결과를 도 1에 나타내었다. 도 1에 나타낸 것과 같이, 실시예 1-3 및 비교예 1의 전지의 초기 용량을 측정한 결과, 실시예 1은 115mAh/g, 실시예 2는 112mAh/g, 실시예 3은 105mAh/g로 나타났으며, 비교예 1은 117mAh/g이었다. 또한, 실시예 1-3 및 비교예 1의 전지를 0.2C로 20회 충방전시켰을 때, 초기 용량 대비 용량 유지율이 실시예 1은 90%, 실시예 2는 93%, 실시예 3은 96%를 나타내었으며, 비교예 1은 70%를 나타내었다. 즉, 비교예 1의 전지가 초기 용량은 다소 높으나, 충방전 사이클을 진행함에 따라 용량 감소가 급격하게 일어남을 알 수 있다. 따라서, 실시예 1-3의 전지가 초기 용량은 비교예 1의 전지에 비하여 다소 낮으나, 충방전 사이클에 따른 용량 유지율이 비교예 1의 전지에 비해 매우 높으므로, 고온 사이클 수명이 우수함을 알 수 있다.The high temperature (50 ° C) cycle life characteristics of the battery were measured using the batteries of Examples 1-3 and Comparative Example 1, and the results are shown in FIG. 1. As shown in FIG. 1, the initial capacities of the batteries of Examples 1-3 and Comparative Example 1 were measured. As a result, Example 1 was 115 mAh / g, Example 2 was 112 mAh / g, and Example 3 was 105 mAh / g. It appeared, and Comparative Example 1 was 117mAh / g. In addition, when the batteries of Examples 1-3 and Comparative Example 1 were charged and discharged 20 times at 0.2C, the capacity retention ratio of the initial capacity was 90% in Example 1, 93% in Example 2, and 96% in Example 3, respectively. In Comparative Example 1, 70% was indicated. That is, although the initial capacity of the battery of Comparative Example 1 is slightly higher, it can be seen that the capacity decreases rapidly as the charge and discharge cycle proceeds. Therefore, although the initial capacity of the battery of Examples 1-3 is slightly lower than that of Comparative Example 1, the capacity retention rate according to the charge / discharge cycle is much higher than that of Comparative Example 1, indicating that the high temperature cycle life is excellent. have.
상술한 바와 같이, 본 발명의 리튬 이차 전지용 양극 활물질은 고온 사이클 수명 특성이 LiMn2O4에 비해 25% 이상 향상되었다.As described above, the high temperature cycle life characteristics of the cathode active material for lithium secondary batteries of the present invention are improved by 25% or more compared to LiMn 2 O 4 .
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| US10155441B2 (en) | 2016-02-24 | 2018-12-18 | Hyundai Motor Company | Fuel door opener |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4159962A (en) * | 1977-06-27 | 1979-07-03 | Bell Telephone Laboratories, Incorporated | Method of preparing layered chalcogenides |
| JPH08250120A (en) * | 1995-03-08 | 1996-09-27 | Sanyo Electric Co Ltd | Lithium secondary battery |
| JPH08250119A (en) * | 1995-03-08 | 1996-09-27 | Sanyo Electric Co Ltd | Lithium secondary battery |
| KR20000059655A (en) * | 1999-03-06 | 2000-10-05 | 김순택 | A positive active material for a lithium secondary battery and a method of preparing the same |
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1999
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4159962A (en) * | 1977-06-27 | 1979-07-03 | Bell Telephone Laboratories, Incorporated | Method of preparing layered chalcogenides |
| JPH08250120A (en) * | 1995-03-08 | 1996-09-27 | Sanyo Electric Co Ltd | Lithium secondary battery |
| JPH08250119A (en) * | 1995-03-08 | 1996-09-27 | Sanyo Electric Co Ltd | Lithium secondary battery |
| KR20000059655A (en) * | 1999-03-06 | 2000-10-05 | 김순택 | A positive active material for a lithium secondary battery and a method of preparing the same |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10155441B2 (en) | 2016-02-24 | 2018-12-18 | Hyundai Motor Company | Fuel door opener |
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