KR100570617B1 - Negative active material for lithium secondary battery, method of preparing same, and lithium secondary battery comprising same - Google Patents
Negative active material for lithium secondary battery, method of preparing same, and lithium secondary battery comprising same Download PDFInfo
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- KR100570617B1 KR100570617B1 KR1020040012774A KR20040012774A KR100570617B1 KR 100570617 B1 KR100570617 B1 KR 100570617B1 KR 1020040012774 A KR1020040012774 A KR 1020040012774A KR 20040012774 A KR20040012774 A KR 20040012774A KR 100570617 B1 KR100570617 B1 KR 100570617B1
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- active material
- silicon oxide
- negative electrode
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- 239000007773 negative electrode material Substances 0.000 title claims abstract description 45
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims description 33
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 39
- 239000000203 mixture Substances 0.000 claims abstract description 32
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 19
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 30
- 150000001875 compounds Chemical class 0.000 claims description 19
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims description 15
- 238000009792 diffusion process Methods 0.000 claims description 11
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 238000010791 quenching Methods 0.000 claims description 9
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- 229910010238 LiAlCl 4 Inorganic materials 0.000 description 1
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- E—FIXED CONSTRUCTIONS
- E05—LOCKS; KEYS; WINDOW OR DOOR FITTINGS; SAFES
- E05B—LOCKS; ACCESSORIES THEREFOR; HANDCUFFS
- E05B63/00—Locks or fastenings with special structural characteristics
- E05B63/0052—Locks mounted on the "frame" cooperating with means on the "wing"
-
- E—FIXED CONSTRUCTIONS
- E05—LOCKS; KEYS; WINDOW OR DOOR FITTINGS; SAFES
- E05C—BOLTS OR FASTENING DEVICES FOR WINGS, SPECIALLY FOR DOORS OR WINDOWS
- E05C21/00—Arrangements or combinations of wing fastening, securing, or holding devices, not covered by a single preceding main group; Locking kits
-
- E—FIXED CONSTRUCTIONS
- E05—LOCKS; KEYS; WINDOW OR DOOR FITTINGS; SAFES
- E05Y—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES E05D AND E05F, RELATING TO CONSTRUCTION ELEMENTS, ELECTRIC CONTROL, POWER SUPPLY, POWER SIGNAL OR TRANSMISSION, USER INTERFACES, MOUNTING OR COUPLING, DETAILS, ACCESSORIES, AUXILIARY OPERATIONS NOT OTHERWISE PROVIDED FOR, APPLICATION THEREOF
- E05Y2800/00—Details, accessories and auxiliary operations not otherwise provided for
- E05Y2800/26—Form or shape
- E05Y2800/33—Form or shape having protrusions
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- Engineering & Computer Science (AREA)
- Structural Engineering (AREA)
- Mechanical Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
본 발명은 실리콘옥사이드에 Mg, Ca 또는 이들의 혼합물로 이루어진 군에서 선택되는 원소가 도핑되어 있는 실리콘 옥사이드 및 탄소물질을 포함하는 리튬 이차 전지용 음극 활물질을 제공한다. 본 발명의 음극 활물질은 리튬 이차 전지의 수명특성과 고율 충방전 특성을 우수하게 개선할 수 있다.The present invention provides a negative electrode active material for a lithium secondary battery including silicon oxide and a carbon material doped with an element selected from the group consisting of Mg, Ca or a mixture thereof in silicon oxide. The negative electrode active material of the present invention can improve the life characteristics and high rate charge and discharge characteristics of the lithium secondary battery excellently.
도핑,실리콘옥사이드,음극활물질,리튬이차전지Doping, silicon oxide, cathode active material, lithium secondary battery
Description
도 1은 본 발명의 실시형태인 리튬 이차 전지의 일예를 표시한 사시도이다.1 is a perspective view showing an example of a lithium secondary battery according to an embodiment of the present invention.
<도면의 주요부분에 대한 부호의 설명><Description of Symbols for Main Parts of Drawings>
1: 리튬 이차 전지 2: 음극1: lithium secondary battery 2: negative electrode
3: 양극 4: 세퍼레이터3: anode 4: separator
5: 전지 용기 6: 봉입부재5: battery container 6: sealing member
[산업상 이용 분야][Industrial use]
본 발명은 리튬 이차 전지용 음극 활물질, 그의 제조 방법 및 그를 포함하는 리튬 이차 전지에 관한 것으로서, 보다 상세하게는, 수명 특성과 고율 충방전 특성이 우수한 리튬 이차 전지용 음극 활물질, 그의 제조 방법 및 그를 포함하는 리튬 이차 전지에 관한 것이다.The present invention relates to a negative electrode active material for a lithium secondary battery, a method for manufacturing the same, and a lithium secondary battery including the same. More specifically, a negative electrode active material for a lithium secondary battery excellent in lifespan characteristics and high rate charge-discharge characteristics, a method for producing the same, and the same It relates to a lithium secondary battery.
[종래 기술][Prior art]
최근 휴대전자 기기의 소량 경량화 및 고성능화에 대응하기 위하여 리튬 이차 전지의 고용량화가 시급한 과제로 대두되고 있다. 그러나, 리튬 이차 전지의 음극 활물질의 하나인 흑연은 372 mAh/g의 이론용량을 가지지만, 이것보다도 고용량인 음극 활물질을 얻고자 하기 위해서는 비정질 탄소재 또는 탄소재료를 대체할 수 있는 신규재료의 개발을 진행시킬 필요가 있다. Recently, in order to cope with small weight and high performance of portable electronic devices, high capacity of lithium secondary batteries has emerged as an urgent problem. However, graphite, which is one of the negative electrode active materials of a lithium secondary battery, has a theoretical capacity of 372 mAh / g, but in order to obtain a higher capacity negative electrode active material, development of a new material that can replace amorphous carbon materials or carbon materials. It is necessary to proceed.
흑연을 대체할 수 있는 신규재료로서는 종래부터 규소나 그 화합물이 검토되어 오고 있다. 규소나 그 화합물은 규소자체가 리튬과 합금을 형성하고, 흑연보다도 큰 전기용량을 나타내는 것으로 알려져 있다.Silicon and its compound have been examined conventionally as a novel material which can replace graphite. Silicon and its compounds are known to form an alloy with lithium and exhibit a larger capacitance than graphite.
그래서 최근에는 리튬 이차 전지의 음극 재료로서, (1)흑연에 규소화합물의 분말을 단순히 혼합한 재료, (2)실란커플링제 등을 이용하여 흑연표면에 미분발의 규소화합물 등을 화학적으로 고정한 재료, (3)흑연계탄소물질과 Si 등의 금속물질을 비정질인 탄소물질로 결합 또는 피복한 재료가 제안되고 있다.Therefore, recently, as a negative electrode material of a lithium secondary battery, (1) a material in which a silicon compound powder is simply mixed with graphite, (2) a fine powder silicon compound or the like is chemically fixed on the graphite surface by using a silane coupling agent or the like, (3) A material in which a graphite carbon material and a metal material such as Si is bonded or coated with an amorphous carbon material has been proposed.
그러나, 상기한 (1)흑연에 규소화합물의 분말을 단순히 혼합한 재료는 흑연과 규소화합물이 반드시 밀착되어 있지 않기 때문에, 충방전 사이클이 진행됨에 따라 흑연이 팽창 또는 수축했을 때에 규소화합물이 흑연으로부터 유리되며, 이 규소화합물 자체가 전자전도성이 낮기 때문에, 규소화합물이 음극 활물질로서 충분히 이용되지 않게 되어, 리튬 이차 전지의 사이클특성이 저하된다는 문제점이 있다.However, since the graphite and the silicon compound are not necessarily in close contact with each other in the above-mentioned material (1) in which the powder of the silicon compound is simply mixed, the silicon compound is separated from the graphite when the graphite expands or contracts as the charge and discharge cycle proceeds. Since the silicon compound itself has low electron conductivity, there is a problem that the silicon compound is not sufficiently used as the negative electrode active material and the cycle characteristics of the lithium secondary battery are lowered.
또한 상기한 (2)실란커플링제 등을 이용하여 흑연표면에 미분발의 규소화합물 등을 화학적으로 고정한 재료는 충방전 사이클이 초기중에는 흑연에 규소화합물이 밀착된 상태로 유지되어 규소화합물이 흑연과 같이 음극 활물질로서 기능하지 만, 충방전 사이클이 진행됨에 따라 리튬과의 합금형성에 따라 규소화합물 자체가 팽창하여, 이에 따라 실란커플링제에 의한 결합을 파괴하여 규소화합물이 흑연으로부터 유리되어, 규소화합물이 음극 활물질로서 충분히 이용될 수 없어서, 리튬 이차 전지의 사이클특성이 저하된다는 문제점이 있다. 또한 음극 재료 제조시에 실란커플링 처리가 균질하게 행해지지 않는 경우가 있어, 안정된 품질의 음극 재료를 용이하게 제조할 수 없다는 문제점이 있다.In addition, the above-mentioned material (2) chemically fixing finely powdered silicon compound on the graphite surface by using a silane coupling agent or the like is maintained in a state in which the silicon compound is in close contact with the graphite during the initial charge and discharge cycle. It functions as a negative electrode active material, but as the charge and discharge cycle progresses, the silicon compound itself expands as the alloy with lithium forms, thereby destroying the bond by the silane coupling agent, thereby releasing the silicon compound from graphite, There is a problem that the cycle characteristics of the lithium secondary battery may be lowered because it cannot be sufficiently used as a negative electrode active material. In addition, the silane coupling treatment may not be performed homogeneously at the time of manufacturing the negative electrode material, and there is a problem that a negative electrode material of stable quality cannot be easily produced.
또한 상기한 (3)흑연계 탄소물질과 Si 등의 금속물질을 비정질인 탄소물질로 결합 또는 피복한 재료는 (2)실란커플링제 등을 이용하여 흑연표면에 미분발의 규소화합물 등을 화학적으로 고정한 재료의 상기 문제점과 동일한 문제점이 있다. 즉, 충방전 사이클이 진행되면, 리튬과의 합금형성에 따른 금속물질 자체의 팽창에 의해 비정질 탄소물질에 의한 결합이 파괴되어 금속물질이 흑연계 탄소물질로부터 유리되어, 금속물질이 음극 활물질로서 충분히 이용되지 않게 되어, 사이클특성이 저하된다는 문제점이 있었다.In addition, (3) the material which combines or coats the graphite-based carbon material and metal materials such as Si with an amorphous carbon material is (2) chemically fixing finely divided silicon compounds or the like on the graphite surface using a silane coupling agent or the like. There is the same problem as the above problem of the material. That is, as the charge and discharge cycle proceeds, the bond by the amorphous carbon material is broken by the expansion of the metal material itself due to the alloy formation with lithium, and the metal material is released from the graphite carbon material, so that the metal material is sufficiently used as the negative electrode active material. There was a problem that it was not used and the cycle characteristics were lowered.
본 발명은 상기 문제점을 해결하기 위한 것으로서, 수명특성과 고율 충방전 특성이 우수한 리튬 이차 전지용 음극 활물질 및 이의 제조방법을 제공하기 위한 것이다.The present invention is to solve the above problems, to provide a negative electrode active material for a lithium secondary battery excellent in life characteristics and high rate charge-discharge characteristics and a method of manufacturing the same.
본 발명은 또한 상기 음극 활물질을 포함하는 리튬 이차 전지를 제공하기 위한 것이다.The present invention also provides a lithium secondary battery comprising the negative electrode active material.
본 발명은 실리콘 옥사이드에 Mg, Ca 또는 이들의 혼합물로 이루어진 군에서 선택되는 원소가 도핑되어 있는 실리콘 옥사이드 및 탄소물질을 포함하는 리튬 이차 전지용 음극 활물질을 제공한다. The present invention provides a negative electrode active material for a lithium secondary battery including silicon oxide and a carbon material doped with an element selected from the group consisting of Mg, Ca or a mixture thereof in silicon oxide.
본 발명은 또한 SiO2, Si 및 Mg-함유 화합물, Ca-함유 화합물 및 이들의 혼합물로 이루어진 군에서 선택되는 도핑원소-함유 화합물을 혼합하는 단계; 상기 혼합물을 열처리하여 Mg, Ca 또는 이들의 혼합물로 도핑된 실리콘 옥사이드를 제조하는 단계; 상기 열처리한 실리콘 옥사이드를 급냉시키는 단계; 및 상기 급냉시킨 실리콘 옥사이드 물질과 탄소물질을 혼합하는 단계를 포함하는 리튬 이차 전지용 음극 활물질의 제조방법을 제공한다.The invention also comprises the steps of mixing a doping element-containing compound selected from the group consisting of SiO 2 , Si and Mg-containing compounds, Ca-containing compounds and mixtures thereof; Heat treating the mixture to produce silicon oxide doped with Mg, Ca or a mixture thereof; Quenching the heat-treated silicon oxide; And it provides a method for producing a negative electrode active material for a lithium secondary battery comprising the step of mixing the quenched silicon oxide material and carbon material.
본 발명은 또한 상기 음극 활물질을 포함하는 음극; 리튬의 가역적인 인터칼레이션/디인터칼레이션이 가능한 양극 활물질을 포함하는 양극; 및 전해액을 포함하는 리튬 이차 전지를 제공한다.The present invention also includes a negative electrode comprising the negative electrode active material; A positive electrode including a positive electrode active material capable of reversible intercalation / deintercalation of lithium; And it provides a lithium secondary battery comprising an electrolyte solution.
이하 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.
본 발명의 음극 활물질은 실리콘 옥사이드에 Mg, Ca 또는 이들의 혼합물로 이루어진 군에서 선택되는 원소가 도핑되어 있는 실리콘 옥사이드와 탄소물질의 혼합물로 이루어진다. 상기 Mg, Ca 또는 이들의 혼합물이 도핑된 실리콘 옥사이드는 하기 화학식 1과 같이 표시된다. The negative electrode active material of the present invention consists of a mixture of silicon oxide and carbon material doped with an element selected from the group consisting of Mg, Ca or a mixture thereof in silicon oxide. The silicon oxide doped with the Mg, Ca or a mixture thereof is represented by the following
[화학식 1][Formula 1]
(MO)y(SiOx) (MO) y (SiO x )
(상기 식에서, 2.2≤y≤5.5, 0<x≤1 이며, M은 Mg, Ca 또는 이들의 혼합물임.)(Wherein, 2.2≤y≤5.5, 0 <x≤1, and M is Mg, Ca or a mixture thereof.)
SiOx는 비가역 용량이 높고, 수명이 짧으며, 고율 충방전 효율이 좋지 않다. 이는 충방전시 구조적인 안정성이 낮고 Li 원자의 확산속도가 낮기 때문인 것으로 생각된다. 본 발명에서는 Mg, Ca 또는 이들의 혼합물을 실리콘 옥사이드(SiOx)에 도핑함으로써 실리콘 옥사이드의 비정질화도를 높이고 실리콘 옥사이드의 환원시 형성될 수 있는 Si 금속 응집체의 성장을 억제하며, Li 원자의 확산속도를 향상시킨다. SiO x has a high irreversible capacity, short lifetime, and poor high rate charge / discharge efficiency. This is thought to be due to the low structural stability during charging and discharging and the low diffusion rate of Li atoms. In the present invention, doping Mg, Ca or a mixture thereof to silicon oxide (SiO x ) increases the degree of amorphousness of silicon oxide and inhibits the growth of Si metal aggregates that may be formed upon reduction of silicon oxide, and the diffusion rate of Li atoms. To improve.
본 발명의 음극 활물질의 비정질화도는 70 % 이상이며, 바람직하게는 70 내지 99 % 이다. 또한, 상기 음극활물질은 GITT(Galvanic Intermitant time technique) 방법에 따라 Li의 확산속도를 측정할 경우 10-8 cm2/sec이상, 바람직하게는 10-8 내지 10-6 cm2/sec의 확산속도를 가진다. 상기 비정질화도는 하기 계산식 1과 같이 정의된다. Amorphization degree of the negative electrode active material of the present invention is 70% or more, preferably 70 to 99%. In addition, the negative electrode active material is 10 -8 cm 2 / sec or more, preferably 10 -8 to 10 -6 cm 2 / sec when measuring the diffusion rate of Li according to the Galvanic Intermitant time technique (GITT) method Has The degree of amorphousness is defined as in
[계산식 1][Calculation 1]
비정질화도(%) = ((급냉 처리후 주요 XRD 피크 강도)/(급냉 처리전 주요 XRD 피크 강도))*100% Amorphous = = ((major XRD peak intensity after quench) / (major XRD peak intensity after quench)) * 100
상기 실리콘 옥사이드는 SiOx로 나타내어지며, x의 범위는 1 이하로 조절하는 것이 바람직하고, 0.5 내지 1인 것이 더 바람직하다. x의 범위가 1을 초과하는 경우에는 리튬과 반응시 비가역용량이 차지하는 부분이 증가하여 초기 효율을 떨어뜨릴 염려가 있다.The silicon oxide is represented by SiO x , the range of x is preferably adjusted to 1 or less, more preferably 0.5 to 1. If the range of x exceeds 1, the portion of the irreversible capacity when reacting with lithium increases, which may lower initial efficiency.
상기 도핑원소인 Mg, Ca 또는 이들의 혼합물의 도핑양은 실리콘 옥사이드 100 중량부에 대하여 50 중량부 이하, 바람직하게는 20 내지 50 중량부이다. 상기 도핑양이 50 중량부를 초과하는 경우에는 에너지밀도 및 비가역 용량이 증가되는 문제점이 있다. The doping amount of the doping element Mg, Ca or a mixture thereof is 50 parts by weight or less, preferably 20 to 50 parts by weight based on 100 parts by weight of silicon oxide. When the doping amount exceeds 50 parts by weight, there is a problem in that energy density and irreversible capacity are increased.
상기 실리콘 옥사이드와 혼합되는 탄소물질로는 결정질 탄소이나 비정질 탄소가 사용될 수 있다. 상기 결정성 탄소로는 판상, 구형 또는 섬유형의 천연 흑연 또는 인조 흑연 등이 있다. 상기 비정질 탄소의 예로는 이흑연화성 탄소(소프트 카본(soft carbon), 저온 소성 탄소) 또는 난흑연화성 탄소(하드 카본(hard carbon))를 들 수 있다. 상기 소프트 카본은 석탄계 핏치, 석유계 핏치, 타르(tar), 저분자량의 중질유를 약 1000℃ 로 열처리하여 얻을 수 있으며, 상기 하드 카본은 페놀 수지, 나프탈렌 수지, 폴리비닐알콜 수지, 우레탄 수지, 폴리이미드수지, 퓨란 수지, 셀룰로오스 수지, 에폭시 수지, 폴리스티렌 수지 등을 약 1000℃ 로 열처리하여 얻을 수 있다. 또한, 석유계, 석탄계 탄소 원료 또는 수지계 탄소를 300 내지 600℃ 로 열처리한 메조페이스 피치, 원료 코크스(raw cokes) 및 탄소 원료를 불융화처리한 후 또는 불융화처리하지 않고 600 내지 1500℃ 로 열처리한 메조페이스 핏치 탄화물, 소성된 코크스 등의 비정질 탄소를 사용할 수도 있다. As the carbon material mixed with the silicon oxide, crystalline carbon or amorphous carbon may be used. Examples of the crystalline carbon include plate-like, spherical or fibrous natural graphite or artificial graphite. Examples of the amorphous carbon include digraphitizable carbon (soft carbon, low temperature calcined carbon) or nongraphitizable carbon (hard carbon). The soft carbon may be obtained by heat treating coal-based pitch, petroleum-based pitch, tar, and low molecular weight heavy oil at about 1000 ° C., and the hard carbon may be a phenol resin, naphthalene resin, polyvinyl alcohol resin, urethane resin, poly Mid resin, furan resin, a cellulose resin, an epoxy resin, a polystyrene resin, etc. can be obtained by heat-processing at about 1000 degreeC. In addition, after mesophase pitch, raw cokes, and carbon raw materials obtained by heat-treating petroleum, coal-based carbon raw materials, or resin-based carbons at 300 to 600 ° C., or after being heat-treated at 600 to 1500 ° C. without infusible treatment It is also possible to use amorphous carbon such as one mesophase pitch carbide, calcined coke, or the like.
상기 실리콘 옥사이드와 탄소물질은 95:5 내지 50:50의 중량비로 혼합되는 것이 바람직하며, 80:20 내지 60:40의 중량비로 혼합되는 것이 더 바람직하다. The silicon oxide and the carbon material are preferably mixed in a weight ratio of 95: 5 to 50:50, and more preferably in a weight ratio of 80:20 to 60:40.
이하에서는 본 발명의 음극 물질을 구성하는 실리콘 옥사이드의 제조공정을 설명한다. 먼저 SiO2와 Si의 혼합물에 Mg-함유 화합물, Ca-함유 화합물 또는 이들의 혼합물을 첨가하여 함께 열처리한다. SiO2와 Si는 1:1 내지 1:3의 몰비로 혼합되는 것이 바람직하다.Hereinafter, a manufacturing process of the silicon oxide constituting the negative electrode material of the present invention will be described. First, an Mg-containing compound, a Ca-containing compound, or a mixture thereof is added to a mixture of SiO 2 and Si, and heat treated together. SiO 2 and Si are preferably mixed in a molar ratio of 1: 1 to 1: 3.
상기 도핑원소-함유 화합물은 유리질 형성 전구체(Glass network former)인 것이 바람직하다. 상기 Mg-함유 화합물의 예로는 MgO 등이 있으며 Ca-함유 화합물의 예로는 CaO 등이 있다. 이들 화합물은 SiO2와 Si의 혼합물 100 중량부에 대하여 20 내지 50 중량부로 첨가되는 것이 바람직하다.The doping element-containing compound is preferably a glass network former. Examples of the Mg-containing compound include MgO and the like, and examples of the Ca-containing compound include CaO and the like. These compounds are preferably added in an amount of 20 to 50 parts by weight based on 100 parts by weight of a mixture of SiO 2 and Si.
상기 열처리 온도는 600 내지 1000℃인 것이 바람직하고, 800 내지 1000℃인 것이 더 바람직하다. 열처리 온도가 600℃ 미만이면 열확산 현상의 저하로 균일한 실리콘 옥사이드(SiOx)가 형성되기 어렵고, Mg, Ca 또는 이들의 혼합물이 도핑된 균일한 실리콘 옥사이드(SiOx)를 형성하기 어렵다. 또한, 1000℃를 초과하면 Si의 분해반응 가능성이 있어 바람직하지 않다. 상기 열처리 분위기는 불활성 분위기 또는 진공분위기인 것이 바람직하다. 이러한 열처리 공정에 의하여 Mg, Ca 또는 이들 두원소 모두가 실리콘 옥사이드에 도핑되어 실리콘 옥사이드의 비정질화도와 Li의 확산속도를 향상시킬 수 있다. It is preferable that it is 600-1000 degreeC, and, as for the said heat processing temperature, it is more preferable that it is 800-1000 degreeC. When the heat treatment temperature is less than 600 ° C., it is difficult to form uniform silicon oxide (SiO x ) due to a decrease in thermal diffusion phenomenon, and it is difficult to form uniform silicon oxide (SiO x ) doped with Mg, Ca or a mixture thereof. Moreover, when it exceeds 1000 degreeC, since there exists a possibility of decomposition reaction of Si, it is unpreferable. The heat treatment atmosphere is preferably an inert atmosphere or a vacuum atmosphere. By such a heat treatment process, Mg, Ca, or both of these elements may be doped into silicon oxide to improve amorphousness of silicon oxide and diffusion rate of Li.
상기 열처리 공정 후에 급냉 공정을 거침으로써 유리(glass)화 된다. 상기 급냉 공정의 방식은 특정 방법에 한정되지는 않으나, 수냉식, 또는 용융 방사(melt-spinning) 방식 등을 이용할 수 있다. 상기 용융 방사 방식이란, 용해(鎔解)된 용해물을 특정 압력의 가스에 의하여 미세한 노즐을 통하여 상온 이하의 표면온도를 갖고 고속 회전하는 Cu-roll위에 분사시켜 급속 응고시키는 방법을 말 한다. 상기 급냉시 냉각속도는 102 내지 107 K/sec인 것이 바람직하다. After the heat treatment step is subjected to a quenching process to glass. The method of the quenching process is not limited to a specific method, but may be water-cooled or melt-spinning. The melt spinning method refers to a method of rapidly solidifying the dissolved melt by spraying it on a Cu-roll rotating at a high speed with a surface temperature below room temperature through a fine nozzle by a gas of a specific pressure. The cooling rate during the quench is preferably 10 2 to 10 7 K / sec.
상기 열처리 공정 및 급냉 공정에 의하여 도핑원소를 포함하는 실리콘 옥사이드를 제조한다. 그런 다음 상기 실리콘 옥사이드와 탄소물질을 혼합하여 본 발명의 음극 활물질을 제조한다.The silicon oxide containing the doping element is manufactured by the heat treatment process and the quenching process. Then, the silicon oxide and the carbon material are mixed to prepare the anode active material of the present invention.
본 발명의 리튬 이차 전지는 상기 음극 활물질로 제조된 음극을 포함한다. 상기 음극은 본 발명에 따른 음극 활물질을 도전재 및 바인더와 혼합하여 제조된 음극 합제를 구리 등의 집전체에 도포하여 음극으로 제조될 수 있다.The lithium secondary battery of the present invention includes a negative electrode made of the negative electrode active material. The negative electrode may be prepared as a negative electrode by applying a negative electrode mixture prepared by mixing the negative electrode active material according to the present invention with a conductive material and a binder to a current collector, such as copper.
상기 도전재의 예로는, 니켈 분말, 산화 코발트, 산화 티탄, 카본 등이 있으며, 상기 도전재로 사용되는 카본의 예로는, 케첸 블랙, 아세틸렌 블랙, 퍼니스 블랙, 흑연, 탄소 섬유, 플러렌 등이 있으며, 바람직하게는 흑연을 사용할 수 있다.Examples of the conductive material include nickel powder, cobalt oxide, titanium oxide and carbon, and examples of carbon used as the conductive material include ketjen black, acetylene black, furnace black, graphite, carbon fiber, and fullerene. Preferably graphite can be used.
도 1은 본 발명의 실시 형태인 리튬 이차 전지(1)를 나타낸 것이다. 리튬 이차 전지(1)는 음극(2), 전극(3), 상기 음극(2)과 양극(3) 사이에 배치된 세퍼레이터(4), 상기 음극(2), 양극(3) 및 세퍼레이터(4)에 함침된 전해액과, 전지 용기(5)와, 전지 용기(5)를 봉입하는 봉입부재(6)를 주된 부분으로 하여 구성되어 있다. 도 1에 도시된 리튬 이차 전지의 형태는 원통형이나 이외에 원통형, 각형, 코인형, 또는 쉬트형 등의 다양한 형상으로 될 수 있다.1 shows a lithium
상기 양극은 양극 활물질, 도전재 및 바인더로 이루어진 양극 합제를 구비하여 된 것이다. 양극 활물질로는 리튬을 가역적으로 인터칼레이션/디인터칼레이션 할 수 있는 화합물로 LiMn2O4, LiCoO2, LiNiO2, LiFeO2 , V2O5, TiS, MoS 등이 있다. 세퍼레이터로는 폴리에틸렌, 폴리프로필렌 등의 올레핀계 다공질 필름을 사용할 수 있다.The positive electrode is provided with a positive electrode mixture composed of a positive electrode active material, a conductive material and a binder. The positive electrode active material is a compound capable of reversibly intercalating / deintercalating lithium, such as LiMn 2 O 4 , LiCoO 2 , LiNiO 2 , LiFeO 2 , V 2 O 5 , TiS, MoS, and the like. As the separator, an olefin porous film such as polyethylene or polypropylene can be used.
전해액으로는 프로필렌 카보네이트, 에틸렌 카보네이트, 부틸렌 카보네이트, 벤조니트릴, 아세토니트릴, 테트라히드로퓨란, 2-메틸 테트라히드로퓨란, γ-부티로락톤, 디옥솔란, 4-메틸디옥솔란, N,N-디메틸포름아미드, 디메틸아세토아미드, 디메틸설폭사이드, 디옥산, 1,2-디메톡시에탄, 설포란, 디클로로에탄, 클로로벤젠, 니트로벤젠, 디메틸 카보네이트, 메틸에틸 카보네이트, 디에틸 카보네이트, 메틸프로필 카보네이트, 메틸이소프로필 카보네이트, 에틸부틸 카보네이트, 디프로필 카보네이트, 디이소프로필카보네이트, 디부틸 카보네이트, 디에틸렌글리콜, 디메틸에테르 등의 비프로톤성 용매, 또는 이들 용매 중 2종 이상을 혼합한 혼합 용매에, LiPF6, LiBF4, LiSbF6, LiAsF6, LiClO4, LiCF3SO3, Li(CF3SO2)2N, LiC4F9SO3, LiSbF6, LiAlO4, LiAlCl4, LiN(CmF2m+1SO2)(CnF2n+1SO2)(단, m과 n은 자연수), LiCl, LiI 등의 리튬염으로 이루어진 전해질 1종 또는 2종 이상을 혼합시킨 것을 용해한 것을 사용할 수 있다. As electrolyte, propylene carbonate, ethylene carbonate, butylene carbonate, benzonitrile, acetonitrile, tetrahydrofuran, 2-methyl tetrahydrofuran, γ-butyrolactone, dioxolane, 4-methyldioxolane, N, N-dimethyl Formamide, dimethylacetoamide, dimethyl sulfoxide, dioxane, 1,2-dimethoxyethane, sulfolane, dichloroethane, chlorobenzene, nitrobenzene, dimethyl carbonate, methylethyl carbonate, diethyl carbonate, methylpropyl carbonate, methyl LiPF 6 to an aprotic solvent such as isopropyl carbonate, ethylbutyl carbonate, dipropyl carbonate, diisopropyl carbonate, dibutyl carbonate, diethylene glycol, dimethyl ether, or a mixed solvent of two or more of these solvents. , LiBF 4 , LiSbF 6 , LiAsF 6 , LiClO 4 , LiCF 3 SO 3 , Li (CF 3 SO 2 ) 2 N, LiC 4 F 9 SO 3 , LiSbF 6 , LiAlO 4 , LiAlCl 4 , LiN (C m F 2m + 1 SO 2 ) (C n F 2n + 1 SO 2 ) (where m and n are natural waters), and one or two or more electrolytes composed of lithium salts such as LiCl and LiI can be used. have.
또한 상기 전해액 대신에 고분자 고체 전해질을 사용하여도 좋으며, 이 경우는 리튬이온에 대한 이온도전성이 높은 고분자를 사용하는 것이 바람직하고, 폴리에틸렌옥사이드, 폴리프로필렌옥사이드, 폴리에틸렌이민 등을 사용할 수 있고, 또한 이것의 고분자에 상기 용매와 용질을 첨가하여 겔상으로 한 것을 사용할 수 도 있다.In addition, a polymer solid electrolyte may be used instead of the electrolyte solution. In this case, it is preferable to use a polymer having high ion conductivity with respect to lithium ions, and polyethylene oxide, polypropylene oxide, polyethyleneimine and the like can be used. It is also possible to use a gel in which the solvent and the solute are added to the polymer of.
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
SiO2와 Si를 1:1의 몰비로 혼합한 혼합물 100 중량부에 대하여 MgO 40 중량부를 첨가한 혼합물을 900℃에서 감압열처리한 다음 107 K/sec의 속도로 급냉하여 Mg가 17 중량% 도핑된 SiOx(x=1)를 제조하였다. 상기 도핑된 SiOx와 흑연을 1:1의 중량비로 혼합하여 음극 활물질을 제조하였다.MgO doped by 17% by weight of a mixture of 40 parts by weight of MgO was added to 100 parts by weight of a mixture of SiO 2 and Si in a 1: 1 molar ratio, and then quenched at a speed of 10 7 K / sec. SiO x (x = 1) was prepared. The doped SiO x and graphite were mixed at a weight ratio of 1: 1 to prepare a negative electrode active material.
[실시예 2]Example 2
SiO2와 Si를 1:1의 몰비로 혼합한 혼합물 100 중량부에 대하여 CaO 40 중량부를 첨가한 혼합물을 900℃에서 감압열처리한 다음 107 K/sec의 속도로 급냉하여 Ca가 17 중량% 도핑된 SiOx(x=1)를 제조하였다. 상기 도핑된 SiOx와 흑연을 1:1의 중량비로 혼합하여 음극 활물질을 제조하였다.To 100 parts by weight of a mixture of SiO 2 and Si in a 1: 1 molar ratio, 40 parts by weight of CaO was added to the mixture, followed by heat treatment under reduced pressure at 900 ° C., followed by quenching at a rate of 10 7 K / sec, thereby doping Ca by 17% by weight. SiO x (x = 1) was prepared. The doped SiO x and graphite were mixed at a weight ratio of 1: 1 to prepare a negative electrode active material.
[비교예 1]Comparative Example 1
SiO2와 Si를 1:1의 몰비로 혼합한 혼합물을 900℃에서 감압 열처리한 다음 107 K/sec의 속도로 급냉하여 SiOx(x=1)를 제조하였다. 상기 SiOx와 흑연을 1:1의 중량비로 혼합하여 음극 활물질을 제조하였다.SiO 2 and Si were mixed at a molar ratio of 1: 1, and the mixture was heat-treated under reduced pressure at 900 ° C. and quenched at a rate of 10 7 K / sec to prepare SiO x (x = 1). The SiO x and graphite were mixed at a weight ratio of 1: 1 to prepare a negative electrode active material.
[충방전 시험용 테스트셀 작성][Create test cell for charge / discharge test]
실시예 1 및 비교예 1의 음극 활물질과 폴리불화비닐리덴을 90:10의 비율로 N-메틸피롤리돈에서 혼합하여 음극 슬러리를 제조하였다. 이 슬러리를 닥터 블레이드 법으로 두께 18㎛의 구리 집전체에 도포하고, 진공 분위기 중에서 100℃, 24시간 건조하여 N-메틸피롤리돈을 휘발시켰다. 이와 같이 하여 두께 120㎛의 음극 활물질층을 구리 집전체에 적층한 다음 직경 13㎜의 원형으로 구멍을 뚫어 잘라 음극으로 하였다.A negative electrode slurry was prepared by mixing negative active materials of Example 1 and Comparative Example 1 with polyvinylidene fluoride in N-methylpyrrolidone in a ratio of 90:10. This slurry was applied to a copper current collector having a thickness of 18 µm by a doctor blade method, dried at 100 ° C. for 24 hours in a vacuum atmosphere, and volatilized N-methylpyrrolidone. In this manner, a negative electrode active material layer having a thickness of 120 μm was laminated on the copper current collector, and then a hole was cut in a circular shape having a diameter of 13 mm to form a negative electrode.
이 음극을 작용극으로 하고 같은 직경의 원형으로 잘라낸 금속 리튬박을 대극으로 하여, 작용극과 대극 사이에 다공질 폴리프로필렌 필름으로 이루어진 세퍼레이터를 삽입하고, 전해액으로서 프로필렌 카보네이트(PC), 디에틸 카보네이트(DEC)와 에틸렌 카보네이트(EC)의 혼합 용매(PC : DEC : EC = 1 : 1 : 1)에 LiPF6가 1(몰/L)의 농도가 되도록 용해시킨 것을 사용하여 코인형 셀을 작성하였다.A separator made of a porous polypropylene film is inserted between the working electrode and the counter electrode by using a metal lithium foil cut into a circular shape having the same diameter as the working electrode as a counter electrode, and propylene carbonate (PC) and diethyl carbonate ( Coin-type cells were prepared using a solution in which LiPF 6 was dissolved at a concentration of 1 (mol / L) in a mixed solvent of DEC) and ethylene carbonate (EC) (PC: DEC: EC = 1: 1: 1).
그런 다음 충방전류 밀도를 0.2C으로 하고, 충전 종지 전압을 0V(Li/Li+), 방전 종지 전압을 2.0V(Li/Li+)로 하여 충방전 실험을 실시하였다. 실시예 1, 2 및 비교예 1에 의해 제조된 음극활물질을 포함하는 전지의 전기화학적 특성을 하기 표 1에 기재하였다. Then, charging and discharging experiments were carried out with a charging and discharging current density of 0.2C, a charging end voltage of 0 V (Li / Li + ), and a discharging end voltage of 2.0 V (Li / Li + ). The electrochemical characteristics of the battery including the negative electrode active material prepared by Examples 1 and 2 and Comparative Example 1 are shown in Table 1 below.
[표 1]TABLE 1
본 발명의 기술 범위는 상기 실시 형태에 한정되지 않고, 본 발명의 사상을 일탈하지 않는 범위 내에 다양한 변경을 가하는 것이 가능하다. The technical scope of the present invention is not limited to the above embodiments, and various changes can be made without departing from the spirit of the present invention.
이상 상세하게 설명한 것과 같이 본 발명의 리튬 이차 전지용 음극 활물질은 Mg, Ca 또는 이들의 혼합물을 실리콘 옥사이드(SiOx)에 도핑함으로써 실리콘 옥사이드의 비정질화도를 높이고 Li 원자의 확산속도를 향상시킬 수 있어 리튬 이차 전지의 수명특성과 고율 충방전 특성을 우수하게 개선할 수 있다. As described in detail above, the anode active material for a lithium secondary battery of the present invention can increase the amorphousness of silicon oxide and improve the diffusion rate of Li atoms by doping Mg, Ca, or a mixture thereof to silicon oxide (SiO x ). It is possible to excellently improve the life characteristics and high rate charge / discharge characteristics of the secondary battery.
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| KR20170008056A (en) | 2015-07-13 | 2017-01-23 | 강원대학교산학협력단 | Negative active material for lithium secondary battery, method for preparing the same and lithium secondary battery comprising thereof |
| KR101986680B1 (en) | 2017-12-22 | 2019-06-07 | 강원대학교산학협력단 | Negative active material for lithium secondary battery, method for preparing the same and lithium secondary battery including the same |
| KR20200083808A (en) | 2018-12-28 | 2020-07-09 | 강원대학교산학협력단 | Silicon-carbon composite negative active material for lithium secondary battery, method for preparing the same and lithium secondary battery including the same |
| KR20210027328A (en) | 2021-03-02 | 2021-03-10 | 강원대학교산학협력단 | Negative active material for lithium secondary battery, method for preparing the same and lithium secondary battery comprising thereof |
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- 2004-02-25 KR KR1020040012774A patent/KR100570617B1/en active IP Right Grant
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| KR20170008056A (en) | 2015-07-13 | 2017-01-23 | 강원대학교산학협력단 | Negative active material for lithium secondary battery, method for preparing the same and lithium secondary battery comprising thereof |
| KR101986680B1 (en) | 2017-12-22 | 2019-06-07 | 강원대학교산학협력단 | Negative active material for lithium secondary battery, method for preparing the same and lithium secondary battery including the same |
| KR20200083808A (en) | 2018-12-28 | 2020-07-09 | 강원대학교산학협력단 | Silicon-carbon composite negative active material for lithium secondary battery, method for preparing the same and lithium secondary battery including the same |
| KR20210031218A (en) | 2019-09-11 | 2021-03-19 | 강원대학교산학협력단 | Negative active material for lithium secondary battery, method for preparing the same and lithium secondary battery including the same |
| KR20210027328A (en) | 2021-03-02 | 2021-03-10 | 강원대학교산학협력단 | Negative active material for lithium secondary battery, method for preparing the same and lithium secondary battery comprising thereof |
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| KR20050087148A (en) | 2005-08-31 |
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