KR20050087245A - Conductive agent for rechargeable lithium battery and rechargeable lithium battery comprising same - Google Patents
Conductive agent for rechargeable lithium battery and rechargeable lithium battery comprising same Download PDFInfo
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- KR20050087245A KR20050087245A KR1020040012957A KR20040012957A KR20050087245A KR 20050087245 A KR20050087245 A KR 20050087245A KR 1020040012957 A KR1020040012957 A KR 1020040012957A KR 20040012957 A KR20040012957 A KR 20040012957A KR 20050087245 A KR20050087245 A KR 20050087245A
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Abstract
본 발명은 리튬 이차 전지용 도전재 및 이를 포함하는 리튬 이차 전지에 관한 것으로서, 상기 도전재는 도전성 물질을 포함하는 코어 및 상기 코어 표면에 형성된 비정질 화합물을 포함하는 코팅층을 포함한다.The present invention relates to a conductive material for a lithium secondary battery and a lithium secondary battery including the same, wherein the conductive material includes a core including a conductive material and a coating layer including an amorphous compound formed on the surface of the core.
본 발명의 산화물 처리 도전재를 사용한 전지는 사이클 수명이 우수하다.The battery using the oxide-treated conductive material of the present invention is excellent in cycle life.
Description
[산업상 이용 분야][Industrial use]
본 발명은 리튬 이차 전지용 도전재 및 이를 포함하는 리튬 이차 전지에 관한 것으로서, 보다 상세하게는 사이클 수명 특성이 우수한 전지를 제공할 수 있는 리튬 이차 전지용 도전재 및 이를 포함하는 리튬 이차 전지에 관한 것이다.The present invention relates to a conductive material for a lithium secondary battery and a lithium secondary battery including the same, and more particularly, to a lithium secondary battery conductive material and a lithium secondary battery including the same, which can provide a battery having excellent cycle life characteristics.
[종래 기술][Prior art]
최근 전자 제품, 전자 기기, 통신 기기의 소형화, 경량화 및 고성능화가 급속히 진전됨에 따라 이들 제품의 전원으로 사용될 이차 전지의 성능 개선이 크게 요구되고 있다. 이러한 요구를 만족시키는 이차 전지로 리튬 이차 전지가 있으며, 상기 리튬 이차 전지는 크게 황계 물질을 양극 활물질로 사용하는 리튬 설퍼 전지와 리티에이티드 전이 금속 산화물을 양극 활물질로 사용하는 리튬 이온 전지로 크게 분류할 수 있다. Recently, as the miniaturization, weight reduction, and high performance of electronic products, electronic devices, and communication devices have rapidly progressed, there is a great demand for improving the performance of secondary batteries to be used as power sources for these products. A secondary battery that satisfies these requirements is a lithium secondary battery, and the lithium secondary battery is largely classified into a lithium sulfur battery using a sulfur-based material as a cathode active material and a lithium ion battery using a lithium transition metal oxide as a cathode active material. can do.
리튬 이차 전지에서 양극에 사용되는 양극 활물질은 부도체이므로 전기 화학 반응으로 생성된 전자의 이동을 위해서는 도전재 사용이 요구된다. 즉 전기 화학 반응을 활발하게 발생시키기 위해서는 도전재의 역할이 중요하다. 특히 리튬 설퍼 전지의 경우에 첫 방전 이후 고상의 설퍼가 액상인 폴리설파이드로 상변화하여 존재하기 때문에 이러한 폴리설파이드를 극판내에 잘 잡아주는 기술이 필요하다. 그 방법 중 하나는 흡착제를 이용하는 것이다. 이런 목적을 위한 흡착제로 일본 특허 공개 평 9-147868호(공개일 1997. 6. 6.)에서는 활성 섬유 탄소(active carbon fiber)를 사용하였고, 미국 특허 제 5,919,587 호에서는 다공성이 높고 섬유형 및 미세 스폰지형(highly porous, fibrous and ultra fine sponge like) 구조를 지니는 전이 금속 칼코게나이드를 이용하여 양극 활물질을 집어넣거나(embed), 이들로 양극 활물질을 코팅처리(encapsulate)하는 방법이 기술되어 있다. 또한 WO/33125호에는 알루미나나 실리카 등의 강한 흡착력을 지닌 미세 분말로 양극판을 감싸거나 양극합제에 첨가하는 방법, 또는 WO 99/33127호에는 4급 암모늄염 군을 포함하는 양이온성 폴리머(cationic polymer comprising quaternary ammonium salt group)을 이용하여 폴리설파이드 음이온들을 양이온성 폴리머 주위에 머물도록 하는 기술들이 있다. Since the positive electrode active material used for the positive electrode in the lithium secondary battery is a non-conductor, the use of a conductive material is required for the movement of electrons generated by the electrochemical reaction. In other words, the role of the conductive material is important to actively generate the electrochemical reaction. In particular, in the case of lithium sulfur batteries, since the solid sulfur exists after the first discharge phase changes into a liquid polysulfide, a technique for holding such polysulfide in the plate is required. One way is to use an adsorbent. As an adsorbent for this purpose, Japanese Patent Application Laid-open No. Hei 9-147868 (published June 6, 1997) used active carbon fiber. A method of embedding a positive electrode active material using a transition metal chalcogenide having a highly porous, fibrous and ultra fine sponge like structure or encapsulating the positive electrode active material is described. In addition, WO / 33125 discloses a method of wrapping a positive electrode plate with a fine powder having strong adsorption power such as alumina or silica, or adding it to a cathode mixture, or WO 99/33127, a cationic polymer comprising a quaternary ammonium salt group. There are techniques to keep polysulfide anions around cationic polymers using quaternary ammonium salt groups.
그러나 이러한 방법들로는 양극 활물질을 극판 내에 충분하게 잡아주기에 다소 어려움이 있어 이에 관한 연구가 계속 요구되고 있다.However, these methods are somewhat difficult to sufficiently hold the positive electrode active material in the electrode plate, and there is a continuous need for research.
본 발명은 상술한 문제점을 해결하기 위한 것으로서, 본 발명의 목적은 양극 활물질을 극판 내에 충분하게 잡아줄 수 있어 전지의 성능을 향상시킬 수 있는 리튬 이차 전지용 도전재를 제공하는 것이다.SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and an object of the present invention is to provide a conductive material for a lithium secondary battery that can sufficiently hold a positive electrode active material in the electrode plate, thereby improving the performance of the battery.
본 발명의 다른 목적은 전지 사이클 수명 특성을 향상시킬 수 있는 리튬 이차 전지용 도전재를 제공하는 것이다.Another object of the present invention is to provide a conductive material for a lithium secondary battery that can improve battery cycle life characteristics.
본 발명의 또 다른 목적은 상술한 도전재를 포함하는 리튬 이차 전지를 제공하는 것이다.Still another object of the present invention is to provide a lithium secondary battery including the conductive material described above.
상기 목적을 달성하기 위하여, 본 발명은 도전성 물질을 포함하는 코어; 및 상기 코어 표면에 형성된 비정질 화합물을 포함하는 코팅층을 포함하는 리튬 이차 전지용 도전재를 제공한다.In order to achieve the above object, the present invention comprises a core comprising a conductive material; And it provides a conductive material for a lithium secondary battery comprising a coating layer comprising an amorphous compound formed on the surface of the core.
본 발명은 또한 도전성 물질을 포함하는 코어 및 상기 코어 표면에 형성된 비정질 화합물을 포함하는 코팅층을 포함하는 도전재 및 양극 활물질을 포함하는 양극; 음극 활물질을 포함하는 음극; 및 전해액을 포함하는 리튬 이차 전지를 제공한다.The present invention also includes a positive electrode comprising a conductive material and a positive electrode active material including a core comprising a conductive material and a coating layer comprising an amorphous compound formed on the surface of the core; A negative electrode including a negative electrode active material; And it provides a lithium secondary battery comprising an electrolyte solution.
이하 본 발명을 보다 상세하게 설명한다.Hereinafter, the present invention will be described in more detail.
본 발명은 리튬 이차 전지에서 양극 제조시 전기전도도를 확보하기 위하여 첨가하는 도전재를 산화물 처리하여 도전재 표면을 개질하고, 이를 통하여 전지 성능을 향상시키기 위한 것이다. 기존의 리튬 이온 전지의 경우 도전재로 카본 블랙이 일반적으로 사용되고 있고, 리튬 설퍼 전지의 경우도 설퍼가 전도성을 갖고 있지 않기 때문에 도전재의 역할이 매우 중요하다. 또한 방전 후 설퍼가 액상으로 존재하기 때문에 양극판은 도전재와 바인더로 구성되게 되며, 그 도전재들 사이에 액상의 설퍼(폴리설파이드)가 함침되어있는 형상이다. 따라서 이들 폴리설파이드가 극판내에 충분히 함침되어 있도록 하여 전지성능 향상에 기여하도록 하는 것이 본 발명의 목적이다. The present invention is to modify the surface of the conductive material by the oxide treatment of the conductive material added in order to secure the electrical conductivity during the production of the positive electrode in the lithium secondary battery, thereby improving the battery performance. In conventional lithium ion batteries, carbon black is generally used as a conductive material, and in the case of lithium sulfur batteries, the role of the conductive material is very important because sulfur does not have conductivity. In addition, since the sulfur exists in the liquid phase after discharge, the positive electrode plate is composed of a conductive material and a binder, and the liquid sulfur (polysulfide) is impregnated between the conductive materials. Therefore, it is an object of the present invention to make these polysulfides be sufficiently impregnated in the electrode plate to contribute to battery performance improvement.
본 발명의 리튬 이차 전지용 도전재는 기존에 사용되던 도전성 물질을 산화물 처리한 것으로서, 도전성 물질을 포함하는 코어와 이 코어에 형성된 비정질 화합물을 포함하는 코팅층을 포함한다. The conductive material for a lithium secondary battery of the present invention is an oxide treatment of a conventionally used conductive material, and includes a core containing a conductive material and a coating layer containing an amorphous compound formed on the core.
상기 산화물 처리 공정은 상기 도전성 물질과 산화물 용액을 혼합하고, 이 혼합물을 건조하는 공정으로 구성된다. 상기 도전성 물질은 도전성을 나타내며, 일반적으로 리튬 이온 전지 또는 리튬 설퍼 전지와 같이 리튬 이차 전지에서 도전재로 사용하였던 물질은 어떠한 것도 사용가능하며, 그 대표적인 예로 카본 블랙, 카본 나노 튜브, 카본 파이버, 그라파이트, 그라파이트 파이버, 구리, 니켈, 알루미늄, 은 등의 금속 분말 또는 금속 섬유 등을 사용할 수 있다. The oxide treatment step comprises a step of mixing the conductive material and the oxide solution and drying the mixture. The conductive material exhibits conductivity, and in general, any material used as a conductive material in a lithium secondary battery such as a lithium ion battery or a lithium sulfur battery may be used, and representative examples thereof include carbon black, carbon nanotube, carbon fiber, and graphite. Metal powders such as graphite fibers, copper, nickel, aluminum, silver, metal fibers, and the like can be used.
상기 산화물은 B, Al, Si, Ba, Ti 및 V로 이루어진 군에서 선택되는 원소의 산화물을 하나 이상 포함하며, 그 대표적인 예로 B2O3, Al2O3 , SiO2, BaTiO3, TiO2 및 V2O5로 이루어진 군에서 선택되는 산화물을 하나 이상 포함한다.The oxide includes at least one oxide of an element selected from the group consisting of B, Al, Si, Ba, Ti, and V, and representative examples thereof include B 2 O 3 , Al 2 O 3 , SiO 2 , BaTiO 3 , TiO 2 And V 2 O 5 at least one oxide selected from the group consisting of.
상기 산화물 용액에서 산화물의 농도는 0.2 내지 10 중량%가 바람직하다. 산화물의 농도가 0.2 중량% 미만인 경우에는 산화물의 사용량이 너무 적어 도전재 코팅 효과(폴리설파이드 흡착 능력)를 얻기 힘들고, 10 중량%를 초과하는 경우에는 도전재의 양이 상대적으로 감소하여야 하므로 전도도 측면에서 좋지 않게 된다. 산화물 용액의 용매로는 에틸알콜, 메틸알콜, 이소프로필알콜 등의 알코올류, 또는 물 또는 이들의 혼합물을 사용할 수 있다.The concentration of the oxide in the oxide solution is preferably 0.2 to 10% by weight. When the concentration of the oxide is less than 0.2% by weight, the amount of oxide is too small to obtain a conductive coating effect (polysulfide adsorption capacity). When the concentration of the oxide is more than 10% by weight, the amount of the conductive material should be relatively reduced. Not good. As the solvent of the oxide solution, alcohols such as ethyl alcohol, methyl alcohol, isopropyl alcohol, water or a mixture thereof can be used.
상기 건조 공정은 60℃ 이하에서 실시하는 것이 바람직하다. 건조 공정을 60℃보다 높은 온도에서 실시하는 경우 산화물 용액의 용매 끓는 점이 다소 낮기 때문에 너무 빨리 증발되어 코팅이 제대로 되지 않는 문제점이 있다. 상기 건조 공정은 용매가 완전히 없어질 때까지 실시하여 미건조된 부분에 잔존하는 용매가 극판 제조시 슬러리 물성에 악영향을 미치지 않게 않는 것이 바람직하다. It is preferable to perform the said drying process at 60 degrees C or less. When the drying process is carried out at a temperature higher than 60 ℃ there is a problem that the coating is not evaporated too quickly because the solvent boiling point of the oxide solution is somewhat low. The drying process is preferably carried out until the solvent is completely gone so that the solvent remaining in the undried portion does not adversely affect the slurry properties during electrode plate production.
상기 공정에 따라 도전재의 표면에는 비정질 화합물을 포함하는 코팅층이 형성된다. 상기 비정질 화합물은 상기 산화물 처리 공정에 따라 산화물로부터 유도된 비정질 화합물이다. According to the above process, a coating layer containing an amorphous compound is formed on the surface of the conductive material. The amorphous compound is an amorphous compound derived from an oxide according to the oxide treatment process.
본 발명의 도전재는 리튬 이온 전지 또는 리튬 설퍼 전지 등 리튬 이차 전지에 모두 사용가능하며, 본 발명의 도전재를 포함하는 리튬 이차 전지의 대표적인 구조를 도 1에 나타내었다. 도 1에 나타낸 것과 같이, 본 발명의 리튬 이차 전지는 양극(2), 음극(3) 및 상기 양극(2)과 음극(3) 사이에 위치하는 세퍼레이터(4)를 포함하고, 상기 양극(2) 및 상기 음극(3) 사이에 전해액(미도시)이 위치하는 케이스(5)를 포함하는 각형 타입의 리튬 이온 전지(1)를 나타낸 것이다. 물론, 본 발명의 리튬 이차 전지가 이 형상으로 한정되는 것은 아니며, 본 발명의 도전재를 포함하며 전지로서 작동할 수 있는 원통형, 파우치 등 어떠한 형성도 가능함은 당연하다. The conductive material of the present invention can be used both in a lithium secondary battery such as a lithium ion battery or a lithium sulfur battery, and a typical structure of a lithium secondary battery including the conductive material of the present invention is shown in FIG. 1. As shown in FIG. 1, the lithium secondary battery of the present invention includes a positive electrode 2, a negative electrode 3, and a separator 4 positioned between the positive electrode 2 and the negative electrode 3, and the positive electrode 2 ) And a rectangular type lithium ion battery 1 including a case 5 in which an electrolyte solution (not shown) is positioned between the negative electrode 3. Of course, the lithium secondary battery of the present invention is not limited to this shape, it is natural that any formation such as a cylindrical, pouch, etc., including the conductive material of the present invention can operate as a battery.
상기 양극(2)에서 양극 활물질로는 리튬 이온 전지에서 일반적으로 사용되는 리티에이티드 인터칼레이션 산화물을 사용할 수도 있고, 리튬 설퍼 전지에서 일반적으로 사용되는 무기황(S8) 또는 황 계열 화합물을 포함한다. 상기 황 계열 화합물은 Li2Sn(n ≥1), 유기 황 화합물 및 탄소-황 폴리머((C2Sx )n: x=2.5 내지 50, n ≥2)로 이루어진 군에서 선택되는 것을 사용할 수 있다.The positive electrode active material in the positive electrode 2 may be a thiolated intercalation oxide generally used in lithium ion batteries, and includes inorganic sulfur (S 8 ) or sulfur-based compounds commonly used in lithium sulfur batteries. do. The sulfur-based compound may be selected from the group consisting of Li 2 S n (n ≧ 1), an organic sulfur compound and a carbon-sulfur polymer ((C 2 S x ) n : x = 2.5 to 50, n ≧ 2) Can be.
또한 상기 음극(3)에서 음극 활물질로는 리튬 이온을 인터칼레이션 및 디인터칼레이션할 수 있는 결정질 또는 비정질 탄소, 탄소 복합체, 리튬 금속 또는 리튬 합금을 사용할 수 있다.In addition, as the negative electrode active material in the negative electrode 3, crystalline or amorphous carbon, carbon composite, lithium metal, or lithium alloy capable of intercalating and deintercalating lithium ions may be used.
상기 전해액은 비수성 유기 용매와 리튬염을 포함하며, 이들의 종류는 리튬 이차 전지의 종류에 따라 적절하게 선택하면 되며 이는 당해 분야에 널리 알려진 내용이므로 본 명세서에서 자세한 설명은 생략하기로 한다. The electrolyte solution includes a non-aqueous organic solvent and a lithium salt, and the type thereof may be appropriately selected according to the type of the lithium secondary battery, which is well known in the art, and thus detailed description thereof will be omitted.
상기 세퍼레이터(4)는 양극 및 음극 사이에 단락을 방지하는 역할을 하는 물질로서, 이러한 세퍼레이터로는 폴리올레핀, 폴리프로필렌, 폴리에틸렌 등의 고분자막 또는 이들의 다중막, 미세다공성 필름, 직포 및 부직포와 같은 공지된 것을 사용할 수 있다.The separator 4 is a material that serves to prevent a short circuit between the positive electrode and the negative electrode. As the separator, a polymer membrane such as polyolefin, polypropylene, polyethylene, or a multi-layered film thereof, a microporous film, a woven fabric, and a nonwoven fabric are known. Can 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)
카본 분말 100g에 5 중량% 농도의 B2O3 에틸 알콜 용액 20g을 넣고 1시간 동안 스터링하였다. 이 혼합물을 110℃ 오븐에서 건조하여 도전재를 제조하였다.20 g of B 2 O 3 ethyl alcohol solution having a concentration of 5 wt% was added to 100 g of carbon powder, and then stirred for 1 hour. The mixture was dried in an 110 ° C. oven to prepare a conductive material.
상기 제조된 도전재와, 원소 황(S8) 양극 활물질과 폴리에틸렌 옥사이드 바인더를 중량비로 11.4:67.5:21.1의 비율로 이소프로필 알콜 용매 중에서 혼합하여 양극 활물질 슬러리를 제조하고 이 슬러리를 이용하여 통상의 방법으로 양극을 제조하였다. 제조된 양극과 리튬 메탈 음극을 사용하여 통상의 방법으로 리튬 설퍼 전지를 제조하였다.The conductive material, the elemental sulfur (S 8 ) positive electrode active material, and the polyethylene oxide binder were mixed in an isopropyl alcohol solvent at a ratio of 11.4: 67.5: 21.1 by weight to prepare a positive electrode active material slurry, and using this slurry, a conventional A positive electrode was prepared by the method. A lithium sulfur battery was manufactured by a conventional method using the prepared cathode and the lithium metal anode.
(실시예 2)(Example 2)
카본 분말 100g에 5 중량% B2O3 에틸 알콜 용액을 40g 넣고 스터링한 것을 제외하고는 상기 실시예 1과 동일하게 실시하였다.The same procedure as in Example 1 was carried out except that 40 g of 5 wt% B 2 O 3 ethyl alcohol solution was added to 100 g of carbon powder and stirred.
(실시예 3)(Example 3)
카본 분말 100g에 5 중량% B2O3 에틸 알콜 용액을 80g 넣고 스터링한 것을 제외하고는 상기 실시예 1과 동일하게 실시하였다.The same procedure as in Example 1 was carried out except that 80 g of a 5 wt% B 2 O 3 ethyl alcohol solution was added to 100 g of carbon powder and stirred.
(실시예 4)(Example 4)
카본 분말 100g에 5 중량% B2O3 에틸 알콜 용액을 160g 넣고 스터링한 것을 제외하고는 상기 실시예 1과 동일하게 실시하였다.100 g of carbon powder was added in the same manner as in Example 1 except that 160 g of 5 wt% B 2 O 3 ethyl alcohol solution was added and stirred.
(비교예 1)(Comparative Example 1)
B2O3 에틸 알콜 용액을 첨가하지 않고 카본 분말을 도전재로 사용한 것을 제외하고는 상기 실시예 1과 동일하게 실시하였다.The same process as in Example 1 was carried out except that carbon powder was used as the conductive material without adding the B 2 O 3 ethyl alcohol solution.
상기 실시예 1 내지 3 및 비교예 1의 방법으로 제조된 전지의 사이클 수명 특성을 측정하고, 그 결과를 도 1에 나타내었다. 도 1에 나타낸 것과 같이, 80회 충방전을 실시한 후, 실시예 1 내지 3의 전지는 설계 용량 대비 약 80% 이상의 용량을 유지하고 있는 것에 반하여, 비교예 1의 전지는 수명 80회의 용량이 약 40%수준으로 실시예 1 내지 3에 비하여 절반 정도밖에 유지하지 못하고 있음을 알 수 있다.Cycle life characteristics of the batteries prepared by the methods of Examples 1 to 3 and Comparative Example 1 were measured, and the results are shown in FIG. 1. As shown in FIG. 1, after 80 charge / discharge cycles, the batteries of Examples 1 to 3 maintained a capacity of about 80% or more relative to the designed capacity, whereas the battery of Comparative Example 1 had a capacity of about 80 cycles of life. It can be seen that only about half compared to Examples 1 to 3 at the 40% level.
상술한 것과 같이, 본 발명의 산화물 처리 도전재를 사용한 전지는 사이클 수명이 우수하다.As described above, the battery using the oxide-treated conductive material of the present invention is excellent in cycle life.
도 1은 본 발명의 리튬 이차 전지를 나타낸 도면.1 is a view showing a lithium secondary battery of the present invention.
도 2는 본 발명의 실시예 1 내지 3 및 비교예 1에 따라 제조된 도전재를 사용한 전지의 사이클 수명 특성을 나타낸 그래프.2 is a graph showing the cycle life characteristics of the battery using a conductive material prepared according to Examples 1 to 3 and Comparative Example 1 of the present invention.
Claims (19)
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| KR101108446B1 (en) * | 2006-09-18 | 2012-01-31 | 주식회사 엘지화학 | Conductive Agent for Surface Treatment for Hydrophobic Property and Secondary Battery Containing the Same |
| WO2012086939A2 (en) * | 2010-12-21 | 2012-06-28 | 주식회사 엘지화학 | Cathode active material and secondary battery using same |
| WO2012086940A2 (en) * | 2010-12-21 | 2012-06-28 | 주식회사 엘지화학 | Cathode active material and secondary battery using same |
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| WO2012091301A3 (en) * | 2010-12-27 | 2012-09-07 | 주식회사 엘지화학 | Negative electrode active material, and secondary battery using same |
| US8974961B2 (en) | 2010-12-27 | 2015-03-10 | Lg Chem, Ltd. | Anode active material and secondary battery comprising the same |
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