KR101439068B1 - Negative electrode material of electrode and preparing method therefor - Google Patents
Negative electrode material of electrode and preparing method therefor Download PDFInfo
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Abstract
본 발명은 전극 음극재료 및 그의 제조방법에 관한 것이고, 해결하고자하는 기술적 과제는 리튬이온전지의 안전성을 높이고, 생산원가를 절감하는 것이다. 본 발명의 전극 음극재료는 기체 및 상기 기체를 코팅한 코팅층을 포함하는 복합재료이고, 기체는 탄소 함량이 99.9% 이상인 흑연류 재료이고, 기체는 나노미세구멍 또는 나노공극을 함유하고, 코팅층은 탄소재료이다. 본 발명의 전극 음극재료의 제조방법은 이하의 단계를 포함한다:
흑연류 재료를 산화/환원처리하고, 이흑연화 연질 탄소 또는 유기물 열분해 탄소를 고상 코팅 또는 액상 코팅한다. 본 발명과 종래기술을 서로 비교하면, 전극 음극재료의 표면에서 처리층 및/또는 코팅층의 표면 관능기를 제어하며, 처리층 및 코팅층은 얇고 균일하며, 전해액 중에서 안정성 및 열전도성을 높이고, 리튬이온전지의 안전성을 높이며, 전극 음극재료는 용량이 높고 효율이 높은 장점을 가지고, 제조공정이 간단하며, 음극재료의 원가를 절감시킨다.The present invention relates to an electrode material for an anode and a method for manufacturing the same, and a technical problem to be solved is to increase the safety of a lithium ion battery and reduce a production cost. The electrode negative electrode material of the present invention is a composite material including a gas and a coating layer coated with the gas, the gas is a graphite material having a carbon content of 99.9% or more, the gas contains nano-pores or nano voids, Material. A method for manufacturing an electrode cathode material of the present invention includes the following steps:
The graphite material is subjected to oxidation / reduction treatment, and the soft carbon soft carbon or the pyrolysis carbon of the organic material is solid-coated or liquid-coated. By comparing the present invention with the conventional art, it is possible to control the surface functional groups of the treatment layer and / or the coating layer on the surface of the electrode negative electrode material, and the treatment layer and the coating layer are thin and uniform, improve the stability and thermal conductivity in the electrolyte, And the electrode cathode material has advantages of high capacity and high efficiency, and the manufacturing process is simple, and the cost of the anode material is reduced.
Description
본 발명은 전지의 전극재료 및 그의 제조방법, 특히 리튬이온전지의 음극재료 및 그의 제조방법에 관한 것이다.The present invention relates to an electrode material for a battery and a method for manufacturing the same, particularly to a negative electrode material of a lithium ion battery and a method for manufacturing the same.
국민경제의 빠른 발전 및 국민생활 수준의 향상에 따라, 중국의 원유 의존도는 날로 증가하고 있으며, 중국 에너지 안전에 직접적인 위협이 되고 있다. 또한, 원유 가격 파동 역시 국민경제의 발전에 직접적인 영향을 미치고, 사람들이 신에너지를 찾고 개발할 수 밖에 없도록 한다. 동력 전지 및 전동 자동차의 발전은 점점 더 중요한 위치에 놓이고 있으며, 전동 자동차의 대규모 응용에 제약이 되는 주요 원인은 동력 전지이다. 리튬이온전지는 그의 고에너지밀도, 고전압, 무공해, 500회가 넘는 순환을 가지는 긴 순환 수명, 빠른 충방전 등의 방면에서의 우수한 성능 및 나날이 절감되는 생산원가로 인하여, 점차 향후 10~20년 내에 전동 자동차에 선호되는 전지가 될 것이다. 그러나, 리튬이온전지는 가격이 비싸다는 단점을 가진다. 또한, 동력형 리튬이온전지는 부피가 비교적 크고, 이에 상응하여 안정성 또한 떨어진다. 따라서, 가격 및 안전성은 리튬이온전지를 동력 전지로서 사용하는 것을 제약하는 주요 장애가 된다. 음극재료는 리튬이온전지의 주요 재료 중 하나로, 이것의 가격은 전지의 최종 가격에 중요한 영향을 끼치며, 전해액 중에서의 안정성 및 열전도성은 또한 전지의 안전성에 큰 영향을 끼친다. 종래기술은 리튬이온전지 음극재료 제조에 있어 종종 복잡한 개질처리가 요구되고, 생산원가가 비교적 높기 때문에, 리튬이온 동력전지의 개발에 제약이 되었다. With the rapid development of the national economy and the improvement of people's standard of living, China's dependence on crude oil is increasing day by day, and it poses a direct threat to China's energy security. In addition, the wave of crude oil prices also has a direct impact on the development of the national economy, making it necessary for people to find and develop new energy. The development of motor-driven batteries and electric vehicles is becoming increasingly important, and motor-driven batteries are the main limiting factor for large-scale applications of electric vehicles. Because of its high energy density, high voltage, no pollution, long circulation life with over 500 cycles, excellent performance in fast charging and discharging, and everyday production cost, the lithium ion battery will gradually become the next battery in the next 10 to 20 years It will be the battery of choice for electric cars. However, lithium ion batteries are disadvantageous in that they are expensive. Further, the power type lithium ion battery has a relatively large volume, and correspondingly, the stability is also lowered. Therefore, price and safety become major impediments to the use of lithium ion batteries as power cells. The cathode material is one of the main materials of the lithium ion battery, and its price has a significant influence on the final price of the battery, and the stability and the thermal conductivity in the electrolyte also greatly affect the safety of the battery. The prior art has been limited in the development of a lithium ion battery cell because a complicated reforming process is often required in manufacturing a lithium ion battery anode material and the production cost is relatively high.
본 발명의 목적은 전극 음극재료 및 그의 제조방법을 제공하는 것이고, 해결하고자 하는 기술적 과제는 리튬이온전지의 안전성을 높이고, 생산원가를 절감시키는 것이다. An object of the present invention is to provide an electrode material for an electrode and a method for manufacturing the same, and the technical problem to be solved is to increase the safety of a lithium ion battery and reduce the production cost.
본 발명은 이하의 기술적 방안을 사용한다:The present invention uses the following technical measures:
전극 음극재료는, 기체(基體) 및 상기 기체를 코팅한 코팅층을 포함하는 복합재료이고, 상기 기체는 탄소 함량이 99.9% 이상인 흑연류 재료이고, 형상이 구형, 종횡비(aspect ratio)가 1.0~4.5인 구형에 가까운, 괴상 및 편상 중 1종 이상이고, 기체는 나노미세구멍 또는 나노공극을 함유하고, 나노미세구멍 또는 나노공극의 크기는 10~500 nm이고, 공극률은 0.5~20%, 진밀도(true density)는 2.0~2.26 g/cm3이고; 상기 코팅층은 비흑연 탄소재료이고, 코팅층의 질량은 기체 질량의 0 초과 내지 20%이며; 상기 복합재료의 평균입도(D50)는 3.0~50.0 μm, 비표면적은 1.0~20.0 m2/g, 복합재료 분말 압축밀도는 1.50~2.15 g/cm3；상기 흑연류 재료는 천연 인상 흑연(natural flake graphite), 천연 미정질 흑연(natural microcrystalline graphite), 천연 결정질 맥상 흑연(natural crystalline vein graphite), 인조 흑연, 탄소 미립자 및 전도성 흑연 중 1종 이상이고; 상기 비흑연 탄소재료는 이흑연화 연질 탄소, 유기물 열분해 탄소 또는 기상증착 탄소이며; 상기 이흑연화 연질 탄소는 연화점이 30~300 ℃인 석탄 역청, 석유 역청, 콜 타르, 석유공업 중질유 및 중질 방향족 탄화수소 중 1종 이상이고, 상기 유기물은 폴리비닐알코올, 폴리비닐 클로라이드, 폴리에틸렌 글리콜, 폴리(에틸렌옥시드), 폴리비닐리덴 플루오라이드, 아크릴수지 및 폴리아크릴로니트릴 중 1종 이상의 고분자 중합물, 또는 폴리티오펜, 폴리아닐린, 폴리아세틸렌, 폴리피롤, 폴리아센, 폴리페닐렌, 폴리페닐렌 비닐렌 및 폴리디아세틸렌 중 1종 이상의 고분자 전도성 중합물이다.The electrode cathode material is a composite material comprising a substrate and a coating layer coated with the substrate, wherein the gas is a graphite material having a carbon content of 99.9% or more, a spherical shape, an aspect ratio of 1.0 to 4.5 Wherein the gas contains nano-pores or nano-pores, the size of the nano-pores or nano-pores is 10 to 500 nm, the porosity is 0.5 to 20%, the true density the true density is 2.0 to 2.26 g / cm < 3 >; The coating layer is a non-graphitic carbon material and the mass of the coating layer is more than 0 to 20% of the gas mass; The composite material has an average particle size (D 50 ) of 3.0 to 50.0 μm, a specific surface area of 1.0 to 20.0 m 2 / g, a composite material powder compact density of 1.50 to 2.15 g / cm 3, at least one of natural flake graphite, natural microcrystalline graphite, natural crystalline vein graphite, artificial graphite, carbon fine particles and conductive graphite; The non-graphite carbon material is graphitized soft carbon, organic pyrolytic carbon or vapor deposited carbon; The soft carbon soft carbon is at least one of coal bitumen, petroleum bitumen, coal tar, petroleum heavy oil and heavy aromatic hydrocarbon having a softening point of 30 to 300 DEG C, and the organic material is at least one selected from the group consisting of polyvinyl alcohol, polyvinyl chloride, polyethylene glycol, (Ethylene oxide), polyvinylidene fluoride, an acrylic resin and polyacrylonitrile, or a polymeric polymer of at least one polymer selected from the group consisting of polythiophene, polyaniline, polyacetylene, polypyrrole, polyacene, polyphenylene, polyphenylene vinylene And poly-diacetylene.
전극 음극재료의 제조방법은 이하의 단계를 포함한다:A method of manufacturing an electrode cathode material includes the following steps:
1. 흑연류 재료를 산화/환원처리하는 단계; 흑연류 재료를 0.1~100 ℃/분의 속도로 승온시키고, 동시에 0.05~10 m3/h의 유량으로 산화 기체, 환원 기체, 산화 기체와 환원 기체의 혼합 기체, 산화 기체와 비활성 기체의 혼합 기체, 환원 기체와 비활성 기체의 혼합 기체, 또는 산화 기체와 환원 기체와 비활성 기체의 혼합 기체를 주입하고, 온도를 100~1000 ℃으로 한다; 상기 흑연류 재료는 천연 인상 흑연, 천연 미정질 흑연, 천연 결정질 맥상 흑연, 인조 흑연, 탄소 미립자 및 전도성 흑연 중 1종 이상이다;1. Oxidizing / reducing the graphite material; The graphite material is heated at a rate of 0.1 to 100 캜 / min, and at the same time, a mixed gas of an oxidizing gas, a reducing gas, an oxidizing gas and a reducing gas, a mixed gas of an oxidizing gas and an inert gas at a flow rate of 0.05 to 10 m 3 / , A mixed gas of a reducing gas and an inert gas, or a mixed gas of an oxidizing gas, a reducing gas and an inert gas is introduced and the temperature is set to 100 to 1000 ° C; Wherein the graphite material is at least one of natural graphite, natural microcrystalline graphite, natural crystalline graphite, artificial graphite, carbon fine particles and conductive graphite;
2. 100 ℃ 이하까지 강온하고, 산화 기체, 환원 기체, 산화 기체와 환원 기체의 혼합 기체, 산화 기체와 비활성 기체의 혼합 기체, 환원 기체와 비활성 기체의 혼합 기체, 또는 산화 기체와 환원 기체와 비활성 기체의 혼합 기체의 주입을 정지하는 단계;2. A method for reducing the temperature to 100 DEG C or lower, comprising the steps of: oxidizing gas, a reducing gas, a mixed gas of an oxidizing gas and a reducing gas, a mixed gas of an oxidizing gas and an inert gas, a mixed gas of a reducing gas and an inert gas, Stopping the injection of the mixed gas of the gas;
3. 산화/환원처리한 흑연류 재료를 흑연 기체로 하고, 이흑연화 연질 탄소 또는 유기물 열분해 탄소를 고상 코팅 또는 액상 코팅하고, 비흑연 탄소재료로 열분해시켜 전극 음극재료를 얻는 단계; 코팅층의 질량은 흑연 기체 질량의 0 초과 내지 20%이고; 이흑연화 연질 탄소는 연화점이 30~300 ℃인 석탄 역청, 석유 역청, 콜 타르, 석유공업 중질유 및 중질 방향족 탄화수소 중 1종 이상이며; 상기 유기물은 폴리비닐알코올, 폴리비닐 클로라이드, 폴리에틸렌 글리콜, 폴리(에틸렌옥시드), 폴리비닐리덴 플루오라이드, 아크릴수지 및 폴리아크릴로니트릴 중 1종 이상의 고분자 중합물, 또는 폴리티오펜, 폴리아닐린, 폴리아세틸렌, 폴리피롤, 폴리아센, 폴리페닐렌, 폴리페닐렌 비닐렌 및 폴리디아세틸렌 중 1종 이상의 고분자 전도성 중합물이다. 3. A method for producing an electrode cathode material, comprising the steps of: preparing a graphite material by oxidation / reduction treatment as a graphite gas; subjecting graphitized soft carbon or organic pyrolytic carbon to solid phase coating or liquid phase coating; The mass of the coating layer is more than 0 to 20% of the graphite gas mass; The graphitized soft carbon is at least one of coal bituminous, petroleum bitumen, coal tar, petroleum heavy oil and heavy aromatic hydrocarbons having a softening point of 30 to 300 ° C; Wherein the organic material is at least one polymeric polymer selected from the group consisting of polyvinyl alcohol, polyvinyl chloride, polyethylene glycol, poly (ethylene oxide), polyvinylidene fluoride, acrylic resin and polyacrylonitrile, or polythiophene, polyaniline, , Polypyrrole, polyacene, polyphenylene, polyphenylene vinylene, and polydiacetylene.
본 발명의 상기 전극에 대한 음극재료는 100 ℃ 이하로 가열 또는 진공 건조방법을 사용하여 전극 음극재료 수분함량이 0.1% 이하가 되게 한다. The negative electrode material for the electrode of the present invention has a moisture content of the electrode negative electrode material of 0.1% or less by using a heating or vacuum drying method at 100 ° C or less.
본 발명의 상기 전극 음극재료에 대하여 자성을 제거하는데, 1~20 회 자성을 제거하고, 자기감응 강도는 3000~30000 Gs, 처리온도는 10~80 ℃, 전자해머 타격 주기는 3~180 회/초로 하고, 이후 체질을 하여, 평균입도(D50)가 3.0~50.0 μm인 전극 음극재료를 얻는다.In order to remove the magnetic property of the electrode material of the present invention, the magnetic force is removed from 1 to 20 times, the magnetic susceptibility is 3000 to 30000 Gs, the treatment temperature is 10 to 80 占 폚, the electron hammer strike period is 3 to 180 times / And then sieved to obtain an electrode cathode material having an average particle size (D 50 ) of 3.0 to 50.0 μm.
본 발명의 흑연류 재료를 산화/환원처리할 때, 0 초과 내지 20 rpm의 회전속도로 산화/환원 흑연류 재료의 로(furnace) 체임버를 회전시킨다.When the graphite material of the present invention is oxidized / reduced, the furnace chamber of the oxidized / reduced graphite material is rotated at a rotational speed of more than 0 to 20 rpm.
본 발명의 흑연류 재료를 산화/환원처리할 때, 온도가 100~1000 ℃에 도달하면 0 초과 내지 6 시간 보온한다.When the graphite material of the present invention is subjected to oxidation / reduction treatment, it is kept at 0 to 6 hours when the temperature reaches 100 to 1000 占 폚.
본 발명의 강온은 로 벽 및 로 벽 내의 열전도층 사이에서 압축공기를 주입하는 방식 또는 로 내에서의 자연 강온 방식을 이용한다. The cooling method of the present invention uses a natural cooling method in a furnace or a furnace to inject compressed air between the furnace wall and the thermal conductive layer in the furnace wall.
본 발명의 고상 코팅의 코팅재료는 흑연 기체 질량의 1~20%이고, 혼합속도는 100~500 r/분(rpm), 혼합코팅은 5~180 분, 또는 융합 회전속도는 500~3000 r/분, 간극은 0.01~1.0 cm, 융합온도는 20~80 ℃, 융합코팅은 10~200 분으로 하여, 실온까지 자연 강온한다. The coating material of the solid coating of the present invention is 1 to 20% of the graphite gas mass, the mixing speed is 100 to 500 r / min (rpm), the mixed coating is 5 to 180 minutes or the fusing rotation speed is 500 to 3000 r / Min and gap of 0.01 to 1.0 cm, the fusion temperature is 20 to 80 ° C, and the fusion coating is 10 to 200 minutes.
본 발명의 액상 코팅은, 흑연 기체 및 흑연 기체 질량 0.1~20%의 가용성 유기물 액상 혼합을, 2000~8000 r/분의 속도로 10~120 분 혼합교반시키고, 상기 액상 혼합용 용제는 물 또는 유기 용제이고, 용제 질량은 흑연 기체 질량의 0.8~2.0 배이며, 혼합온도는 10~90 ℃이고, 80~300 ℃의 조건하에서 1~30 시간 건조처리한다.In the liquid coating of the present invention, a soluble organic liquid phase mixture of graphite gas and graphite gas in a mass of 0.1 to 20% is mixed and agitated at a speed of 2000 to 8000 r / min for 10 to 120 minutes, And the solvent mass is 0.8 to 2.0 times the mass of the graphite gas and the mixing temperature is 10 to 90 ° C and the drying is performed at 80 to 300 ° C for 1 to 30 hours.
전극 음극재료의 제조방법은 이하의 단계를 포함한다:A method of manufacturing an electrode cathode material includes the following steps:
1. 흑연류 재료를 산화/환원처리하는 단계: 흑연류 재료를 0.1~100 ℃/분의 속도로 승온시키고, 동시에 0.05~10 m3/h의 유량으로 산화 기체, 환원 기체, 산화 기체와 환원 기체의 혼합 기체, 산화 기체와 비활성 기체의 혼합 기체, 환원 기체와 비활성 기체의 혼합 기체, 또는 산화 기체와 환원 기체와 비활성 기체의 혼합 기체를 주입하고, 온도가 100~1000 ℃에 도달하면, 0 초과 내지 6 시간 보온한다;1. The steps of the flow graphite material processing / reduction oxidation: the temperature was raised to a graphite material flow 0.1 ~ 100 ℃ / min, at the same time 0.05 ~ 10 m 3 / h flow rate of the oxidizing gas, reducing gas, an oxidizing gas and a reduction of the A mixed gas of a gaseous mixed gas, an oxidizing gas and an inert gas, a mixed gas of a reducing gas and an inert gas, or a mixed gas of an oxidizing gas and a reducing gas and an inert gas is injected. When the temperature reaches 100 to 1000 ° C, Keep warm for more than 6 hours;
2. 기상코팅하는 단계: 탄소 함유성 기체를 주입하고, 주입량을 0.05~15 m3/h으로 하고, 0.1~5 시간 유지한 후 로 내를 100 ℃ 이하로 강온하며, 산화 기체, 환원 기체, 산화 기체와 환원 기체의 혼합 기체, 산화 기체와 비활성 기체의 혼합 기체, 환원 기체와 비활성 기체의 혼합 기체, 또는 산화 기체와 환원 기체와 비활성 기체의 혼합 기체의 주입을 정지한다; 상기 탄소 함유성 기체는 메탄, 아세틸렌, 에틸렌, CO2, 천연가스, 액화석유가스, 벤젠 및 티오펜 중 1종 이상이다.2. Vapor-coating step: The carbon-containing gas is injected, the injection amount is set to 0.05 to 15 m 3 / h, the temperature is lowered to 100 ° C or less, and the oxidizing gas, reducing gas, Stopping the injection of the mixed gas of the oxidizing gas and the reducing gas, the mixed gas of the oxidizing gas and the inert gas, the mixed gas of the reducing gas and the inert gas, or the mixed gas of the oxidizing gas and the reducing gas and the inert gas; The carbon-containing gas is at least one of methane, acetylene, ethylene, CO 2 , natural gas, liquefied petroleum gas, benzene and thiophene.
본 발명과 종래기술을 서로 비교하면, 전극 음극재료의 표면은 종래의 표면 코팅공정을 이용하지 않고, 표면에서 처리층 및/또는 코팅층의 표면 관능기를 제어하며, 처리층 및 코팅층은 얇고 균일하고, 전해액 중에서 안정성 및 열전도성을 높이며, 리튬이온전지의 안전성을 높이고, 전극 음극재료는 또한 용량이 높고 효율이 높은 장점을 가지며, 제조공정이 간단하고, 음극재료의 원가를 절감시킨다. In comparison between the present invention and the prior art, the surface of the electrode cathode material controls the surface functional groups of the treatment layer and / or the coating layer on the surface without using a conventional surface coating process, and the treatment layer and the coating layer are thin and uniform, The stability of the electrolyte and the thermal conductivity are enhanced, the safety of the lithium ion battery is enhanced, and the electrode cathode material has the advantages of high capacity and high efficiency, and the manufacturing process is simple and the cost of the cathode material is reduced.
도 1은 실시예 1의 전극 음극재료의 SEM 도면이다.
도 2는 실시예 2의 전극 음극재료의 충방전 비용량-전압 곡선도이다.BRIEF DESCRIPTION OF DRAWINGS FIG. 1 is an SEM diagram of an electrode cathode material of Example 1; FIG.
2 is a charge-discharge specific capacity-voltage curve diagram of the electrode negative electrode material of Example 2. Fig.
하기 첨부된 도면 및 실시예는 본 발명에 대해 더욱 상세한 설명을 제시한다. 본 발명의 전극 음극재료는 기체 및 상기 기체를 코팅한 코팅층이 복합재료로 쓰이고, 기체는 탄소 함량이 99.9% 이상인 흑연류 재료이고, 형상이 구형, 종횡비가 1.0~4.5인 구형에 가까운, 괴상 및 편상 중 1종 이상이고, 기체는 나노미세구멍 또는 나노공극을 함유하고, 나노미세구멍 또는 나노공극의 크기는 10~500 nm이고, 공극률 (나노미세구멍 또는 나노공극 부피/기체의 단위부피)은 0.5~20%, 진밀도는 2.0~2.26 g/cm3이고; 코팅층은 비흑연 탄소재료이고, 코팅층의 질량은 기체 질량의 0 초과 내지 20%이며; 복합재료의 평균입도(D50)는 3.0~50.0 μm, 비표면적은 1.0~20.0 m2/g, 복합재료 분말 압축밀도는 1.50~2.15 g/cm3이다.BRIEF DESCRIPTION OF THE DRAWINGS The accompanying drawings and embodiments are provided to illustrate the present invention further. The electrode cathode material of the present invention is a graphite material having a carbon content of 99.9% or more and a spherical shape, a spherical shape having an aspect ratio of 1.0 to 4.5, And the gas contains nano-pores or nano-pores, the size of nano-pores or nano-pores is 10 to 500 nm, and the porosity (unit volume of nano-pores or nano-pore volume / gas) 0.5 to 20% and a true density of 2.0 to 2.26 g / cm < 3 >; The coating layer is a non-graphitic carbon material, and the mass of the coating layer is between 0 and 20% of the gas mass; The average particle size (D 50 ) of the composite material is 3.0 to 50.0 μm, the specific surface area is 1.0 to 20.0 m 2 / g, and the composite material powder compacted density is 1.50 to 2.15 g / cm 3 .
상기 흑연류 재료는 천연 인상 흑연, 천연 미정질 흑연, 천연 결정질 맥상 흑연, 인조 흑연, 탄소 미립자 및 전도성 흑연 중 1종 이상이다.The graphite material may be at least one of natural graphite, natural microcrystalline graphite, natural crystalline graphite, artificial graphite, carbon fine particles and conductive graphite.
상기 비흑연 탄소재료는 이흑연화 연질 탄소, 유기물 열분해 탄소 또는 기상증착 탄소이다.The non-graphite carbon material is graphitized soft carbon, organic pyrolytic carbon or vapor deposited carbon.
상기 이흑연화 연질 탄소는 연화점이 30~300 ℃인 석탄 역청, 석유 역청, 콜 타르, 석유공업 중질유 및 중질 방향족 탄화수소 중 1종 이상이다.The graphitized soft carbon is at least one of coal bitumen, petroleum bitumen, coal tar, petroleum heavy oil and heavy aromatic hydrocarbons having a softening point of 30 to 300 ° C.
상기 유기물은 고분자 중합물 및 고분자 전도성 중합물이다. 상기 고분자 중합물은 폴리비닐알코올, 폴리비닐 클로라이드, 폴리에틸렌 글리콜, 폴리(에틸렌옥시드), 폴리비닐리덴 플루오라이드, 아크릴수지 및 폴리아크릴로니트릴 중 1종 이상이다. 상기 고분자 전도성 중합물은 폴리티오펜, 폴리아닐린, 폴리아세틸렌, 폴리피롤, 폴리아센, 폴리페닐렌, 폴리페닐렌 비닐렌 및 폴리디아세틸렌 중 1종 이상이다.The organic material is a polymeric polymer and a polymeric conductive polymer. The polymeric polymer is at least one of polyvinyl alcohol, polyvinyl chloride, polyethylene glycol, poly (ethylene oxide), polyvinylidene fluoride, acrylic resin and polyacrylonitrile. The polymer conductive polymer is at least one of polythiophene, polyaniline, polyacetylene, polypyrrole, polyacene, polyphenylene, polyphenylene vinylene and polydiacetylene.
본 발명의 전극 음극재료의 제조방법은 흑연류 재료에 대하여 산화/환원, 개질 코팅, 자성 제거, 체질 단계를 통하여 전극 음극재료를 얻는 것으로, 이하의 단계를 포함한다:The method for producing an electrode cathode material of the present invention includes obtaining an electrode cathode material through oxidation / reduction, modification coating, magnetic removal, and sieving steps with respect to a graphite material, and comprises the following steps:
1. 흑연류 재료를 산화/환원처리한다; 입도가 2.8~45.0 μm인 흑연류 재료를 회전식 로의 로 체임버에 두고, 0 초과 내지 20 rpm의 회전속도로 로 체임버를 회전시키며, 0.1~100 ℃/분의 속도로 승온시키고, 동시에 0.05~10 m3/h의 유량으로 산화 기체, 환원 기체, 산화 기체와 환원 기체의 혼합 기체, 산화 기체와 비활성 기체의 혼합 기체, 환원 기체와 비활성 기체의 혼합 기체, 또는 산화 기체와 환원 기체와 비활성 기체의 혼합 기체를 주입하고, 온도가 100~1000 ℃에 도달하면 0 초과 내지 6 시간 보온하고, 흑연류 재료에 대해 산화/환원처리를 한다.1. Oxidize / reduce graphite materials; A graphite material having a particle size of 2.8 to 45.0 μm is placed in a rotary furnace chamber and the furnace chamber is rotated at a rotation speed of more than 0 to 20 rpm and the temperature is raised at a rate of 0.1 to 100 ° C / A mixed gas of an oxidizing gas, a reducing gas, a mixed gas of an oxidizing gas and a reducing gas, a mixed gas of an oxidizing gas and an inert gas, a mixed gas of a reducing gas and an inert gas or a mixed gas of a reducing gas and an inert gas at a flow rate of 3 / When the temperature reaches 100 to 1000 占 폚, gas is kept at a temperature of more than 0 to 6 hours, and the graphite material is oxidized / reduced.
상기 흑연류 재료는 천연 인상 흑연, 천연 미정질 흑연, 천연 결정질 맥상 흑연, 인조 흑연, 탄소 미립자 및 전도성 흑연 중 1종 이상이다; Wherein the graphite material is at least one of natural graphite, natural microcrystalline graphite, natural crystalline graphite, artificial graphite, carbon fine particles and conductive graphite;
상기 산화 및/또는 환원 기체는 산소, 공기, 염소기체(Cl2), 브롬기체(Br2), 불소기체(F2)이고, 상기 비활성 기체는 질소기체 또는 아르곤기체이다.The oxidizing and / or reducing gas is oxygen, air, chlorine gas (Cl 2 ), bromine gas (Br 2 ), fluorine gas (F 2 ), and the inert gas is nitrogen gas or argon gas.
2. 로 벽 및 로 벽 내의 열전도층 사이에서 압축공기를 주입하여 강온하는 방식 또는 로 내에서의 자연 강온 방식을 이용하여 100 ℃ 이하까지 강온하고, 산화 기체, 환원 기체, 산화 기체와 환원 기체의 혼합 기체, 산화 기체와 비활성 기체의 혼합 기체, 환원 기체와 비활성 기체의 혼합 기체, 또는 산화 기체와 환원 기체와 비활성 기체의 혼합 기체의 주입을 정지하여 흑연 기체를 얻는다.2. Lowering the temperature down to 100 ° C or less by injecting compressed air between the thermally conductive layers in the furnace wall and the furnace wall, or by using a natural cooling method in the furnace to oxidize the oxidizing gas, the reducing gas, the oxidizing gas and the reducing gas A gas mixture of a mixed gas, an oxidizing gas and an inert gas, a mixed gas of a reducing gas and an inert gas, or a mixed gas of an oxidizing gas and a reducing gas and an inert gas is stopped to obtain a graphite gas.
3. 산화/환원처리한 흑연 기체에 대하여 고상, 액상 또는 기상 코팅을 하여 복합재료를 얻는다. 코팅재료 전구물 질량은 흑연 기체 질량의 0 초과 내지 20%이고, 100 ℃이하로 가열, 진공 건조 또는 기타 종래기술을 이용하여 음극재료의 수분함량을 0.1% 이하로 조절한다.3. The graphite gas subjected to oxidation / reduction treatment is subjected to solid phase, liquid phase or vapor phase coating to obtain a composite material. The coating material precursor mass is from more than 0 to 20% of the graphite gas mass, and the moisture content of the cathode material is adjusted to 0.1% or less by heating to 100 DEG C or less, vacuum drying or other conventional techniques.
1) 고상 코팅: 코팅재료 전구물은 흑연 기체 질량의 1%~20%이고, 종래기술의 정밀혼합기를 사용하며, 혼합회전속도는 100~500 r/분, 5~180 분 혼합코팅하거나, 또는 혼합물을 종래기술의 융합기에 넣어, 융합 회전속도는 500~3000 r/분, 간극은 0.01~1.0 cm, 융합온도는 20~80 ℃로 10~200 분 융합코팅하고, 실온까지 자연 강온한다. 종래기술에 따라 100~3000 ℃의 조건하에서 열처리하여, 비흑연 탄소재료로 열분해시킨다. 코팅재료 전구물은 이흑연화 연질 탄소를 사용하고, 이흑연화 연질 탄소는 연화점 30~300 ℃의 석탄 역청, 석유 역청, 콜 타르, 석유공업 중질유 및 중질 방향족 탄화수소 중 1종 이상이다.1) Solid-state coating: The coating material precursor is 1% to 20% of the graphite gas mass, using a precision mixer of the prior art, mixing rotation speed of 100-500 r / min for 5-180 minutes, The mixture is put into a fusing machine of the prior art and fused at a fusing rotation speed of 500 to 3000 r / min, a gap of 0.01 to 1.0 cm and a fusing temperature of 20 to 80 캜 for 10 to 200 minutes. Treated according to the prior art under the conditions of 100 to 3000 ° C to pyrolyze the non-graphite carbon material. The coating material precursor uses graphitized soft carbon, and graphitized soft carbon is at least one of coal bitumen, oil bitumen, coal tar, petroleum heavy oil and heavy aromatic hydrocarbon having a softening point of 30 to 300 ° C.
2) 액상 코팅: 흑연 기체 및 흑연 기체 질량 0.1~20%의 가용성 유기물 액상 혼합을, 종래기술의 고속 교반통을 이용하여 2000~8000 r/분의 속도로 10~120 분 동안 혼합교반하여 혼합물을 얻는다. 용제로는 물 또는 유기 용제를 사용하고, 용제의 질량은 흑연 기체 질량의 0.8~2.0 배이며, 혼합온도는 10~90 ℃이고, 건조박스를 이용하여 80~300 ℃의 조건하에서 1~30 시간 건조처리한다. 종래기술을 따라 100~3000 ℃의 조건하에서 열처리하여, 비흑연 탄소재료로 열분해시킨다. 코팅재료로는 유기물 고분자 중합물 및 고분자 전도성 중합물을 사용한다. 상기 고분자 중합물은 폴리비닐알코올, 폴리비닐 클로라이드, 폴리에틸렌 글리콜, 폴리(에틸렌옥시드), 폴리비닐리덴 플루오라이드, 아크릴수지 및 폴리아크릴로니트릴 중 1종 이상이다. 상기 고분자 전도성 중합물은 폴리티오펜, 폴리아닐린, 폴리아세틸렌, 폴리피롤, 폴리아센, 폴리페닐렌, 폴리페닐렌 비닐렌 및 폴리디아세틸렌 중 1종 이상이다.2) Liquid Coating: The soluble organic liquid phase mixture of graphite gas and graphite gas in a mass of 0.1 to 20% is mixed and stirred for 10 to 120 minutes at a speed of 2000 to 8000 r / min using a high-speed stirring vessel of the prior art, . Water or an organic solvent is used as the solvent. The mass of the solvent is 0.8 to 2.0 times the mass of the graphite gas, the mixing temperature is 10 to 90 ° C and the temperature is 80 to 300 ° C for 1 to 30 hours And dried. Treated according to the prior art under the conditions of 100 to 3000 ° C to pyrolyze the non-graphite carbon material. As the coating material, an organic polymeric polymer and a polymeric conductive polymeric material are used. The polymeric polymer is at least one of polyvinyl alcohol, polyvinyl chloride, polyethylene glycol, poly (ethylene oxide), polyvinylidene fluoride, acrylic resin and polyacrylonitrile. The polymer conductive polymer is at least one of polythiophene, polyaniline, polyacetylene, polypyrrole, polyacene, polyphenylene, polyphenylene vinylene and polydiacetylene.
3) 기상코팅: 흑연류 재료에 대하여 산화/환원처리를 진행한 후, 직접 탄소 함유성 기체를 주입하고, 주입량을 0.05~15 m3/h으로 유지하고 0.1~5 시간 후 100 ℃ 이하로 자연 강온시키고, 산화 기체, 환원 기체, 산화 기체와 환원 기체의 혼합 기체, 산화 기체와 비활성 기체의 혼합 기체, 환원 기체와 비활성 기체의 혼합 기체, 또는 산화 기체와 환원 기체와 비활성 기체의 혼합 기체의 주입을 정지하며, 기상코팅의 전구물, 즉 탄소 함유성 기체는 메탄, 아세틸렌, 에틸렌, CO2, 천연가스, 액화석유가스, 벤젠 및 티오펜 중 1종 이상이다.3) Meteorological Coating: Graphite material is oxidized / reduced and then directly injected with carbon-containing gas. The injection amount is maintained at 0.05 to 15 m 3 / h, and after 0.1 to 5 hours, The mixture is cooled, and the mixed gas of an oxidizing gas, a reducing gas, a mixed gas of an oxidizing gas and a reducing gas, a mixed gas of an oxidizing gas and an inert gas, a mixed gas of a reducing gas and an inert gas or a mixed gas of an oxidizing gas and a reducing gas And the precursor of the gas phase coating, i.e. the carbon-containing gas, is at least one of methane, acetylene, ethylene, CO 2 , natural gas, liquefied petroleum gas, benzene and thiophene.
4) 복합재료에 대하여 자성 제거: 1~20회 자성을 제거하고, 자기감응 강도는 3000~30000 Gs, 처리온도는 10~80 ℃, 전자해머 타격 주기는 3~180 회/초로 하고, 이후 체질을 하여, 평균입도(D50)가 3.0~50.0 μm인 전극 음극재료를 얻는다. 4) Magnetic removal for composite material: The magnetism was removed from 1 to 20 times, the magnetic susceptibility was 3000 to 30000 Gs, the treatment temperature was 10 to 80 ° C, the electron hammer strike period was 3 to 180 times / sec, To obtain an electrode cathode material having an average particle size (D 50 ) of 3.0 to 50.0 μm.
흑연류 재료에 대하여 산화/환원처리할 때, 온도가 100~1000 ℃에 도달하면 0 초과 내지 6 시간 보온하고 기체 재료 중 나노공극 또는 나노미세구멍을 형성하고, 이러한 종류의 미세구멍 또는 공극은 전극재료의 도전성을 높일 수 있다. When the graphite material is subjected to oxidation / reduction treatment, when the temperature reaches 100 to 1000 ° C, it is kept at 0 to 6 hours to form nano-pores or nano-pores in the base material. The conductivity of the material can be increased.
히타치(Hitachi) S4800형 주사 전자 현미경(SEM)을 사용하여 실시예에서 얻어진 전극 음극재료를 관찰한다. The electrode cathode material obtained in Examples is observed using a Hitachi S4800-type scanning electron microscope (SEM).
본 발명에서 제조된 전극 음극재료를 사용하여 실험 전지의 음극을 제작하고, 전극 음극재료와 폴리비닐리덴 플루오라이드 및 전도성 카본블랙을 98:2의 질량비로 혼합하고 N-메틸피롤리돈에 용해시킨 후 얻어진 질량 농도 10%의 혼합을, 10 μm 두께의 구리호일에 균일하게 도포하고, 압축하여 편상으로 만들고, 직경 1 cm의 탄소막을 만들며, 건조박스에서 120 ℃하에 12 시간 건조 대기한다. 상기 제조된 전극 박편으로 전극을 제조하고, 금속 리튬 조각으로 보조전극 및 참조전극을 만들며, 1:1:1의 부피비로 혼합한 EC, DMC, EMC 용제를 이용하여 제작한 농도가 1 몰/L인 LiPF6을 전해액으로 하고, 아르곤 기체가 완전히 충전된 글러브박스에서 내경이 Φ12 mm인 모의전지를 제작한다. 무한(Wuhan) 금낙전자 유한회사의 남전(NAND) 전지 측정시스템 CT2001C상에서 전지의 충방전 측정을 한다. 충방전 전압 범위는 0.01 V~2.0 V, 전류는 0.2 C로 하며, GB/T 24533-2009 리튬이온전지 흑연류 음극재료의 측정방법에 따라, 용량 및 효율을 측정한다. A negative electrode of an experimental cell was prepared using the electrode negative electrode material prepared in the present invention, and an electrode negative electrode material, polyvinylidene fluoride, and conductive carbon black were mixed in a mass ratio of 98: 2 and dissolved in N-methylpyrrolidone The resulting mixture having a mass concentration of 10% is uniformly applied to a copper foil having a thickness of 10 μm, compressed and flattened, and a carbon film having a diameter of 1 cm is prepared. An electrode was prepared from the prepared electrode flakes, an auxiliary electrode and a reference electrode were made of a metal lithium slice, and a concentration of 1 mol / L was prepared using an EC, DMC, or EMC solvent mixed at a volume ratio of 1: 1: LiPF 6 as an electrolytic solution, a simulated battery having an inner diameter of? 12 mm is manufactured in a glove box fully filled with argon gas. Charging and discharging measurement of the battery is performed on the NAND battery measuring system CT2001C of Wuhan Kunkuk Electronics Co., Ltd. The charge and discharge voltage ranges from 0.01 V to 2.0 V and the current is 0.2 C, and the capacity and efficiency are measured according to GB / T 24533-2009 lithium ion battery graphite anode material measurement method.
전지의 열안정성은 고온 45 ℃의 조건하에서 1 C 충방전 용량 보존율로 조사하였다. 용량 보존율이 높을수록 열안정성은 더 좋다. The thermal stability of the battery was investigated at 1 C charge-discharge capacity retention rate at a high temperature of 45 ° C. The higher the capacity retention rate, the better the thermal stability.
실시예 1-6 및 비교예 1의 공정 파라미터를 표 1에 나타내었고, 비교의 편의를 위하여 실시예 1-6 및 비교예 1의 자성 제거 공정 파라미터를 서로 같게 하였다. 실시예 1-6 및 비교예 1의 전기적 성능 측정 결과는 표 2에 나타내었다.The process parameters of Example 1-6 and Comparative Example 1 are shown in Table 1, and the magnetic removal process parameters of Example 1-6 and Comparative Example 1 were made the same for convenience of comparison. The electrical performance measurement results of Example 1-6 and Comparative Example 1 are shown in Table 2.
도 1에 나타난 바와 같이, 흑연 기체 (D50=19.2 μm) 재료를 표면 산화/환원처리한 후 0.5%의 폴리피롤로 액상코팅하고, 150 ℃ 열처리 후 얻어진 재료의 비표면적은 5.26 m2/g이고, 분말압축밀도는 1.90 g/cm3이며, SEM에 보이듯이, 흑연 기체 과립은 구형 및 구형에 가까운 형상이고, 표면 산화 및/또는 환원처리층 및 코팅층은 균일하고, 표면은 산화 및/또는 환원처리하였기 때문에, 표면 관능기가 감소하였고, 낮은 전위 하의 반응이 감소하였으며, 전해액 중에 고정된 열안정성이 좋고, 전해액 및 산화 및/또는 환원처리층 및 코팅층 표면의 부반응이 적고, SEI 막이 안정하고, 고체 전지의 고온 순환이 우수하였다. 45 ℃ 하에서 100 주 용량 보존율은 95%이다.As shown in Fig. 1, graphite gas (D 50 = 19.2 μm) was subjected to surface oxidation / reduction treatment and then liquid-coated with 0.5% polypyrrole. The specific surface area of the material obtained after heat treatment at 150 ° C. was 5.26 m 2 / g , And the powder compact density is 1.90 g / cm 3. As shown in the SEM, the graphite gas granules are spherical and spherical in shape, and the surface oxidation and / or reduction treatment layer and the coating layer are uniform and the surface is oxidized and / The surface functional group was decreased and the reaction under the low electric potential was reduced and the thermal stability fixed in the electrolytic solution was good and the side reaction of the surface of the electrolytic solution and the oxidized and / or reduced treatment layer and the coating layer was small and the SEI film was stable, The high temperature circulation of the battery was excellent. The 100-week capacity retention at 45 ° C is 95%.
도 2에 나타난 바와 같이, 실시예 1 처리를 거친 흑연류 재료는, 용량이 364.69 mAh/g, 효율이 90.18%이었다.As shown in Fig. 2, the graphite material subjected to the treatment of Example 1 had a capacity of 364.69 mAh / g and an efficiency of 90.18%.
본 발명의 방법은 처리공정이 간단하다는 장점을 가질 뿐만 아니라, 표 2에서 볼 수 있듯이, 본 발명의 방법으로 제조한 전극 음극재료는 용량이 높고 효율이 높은 특장점을 갖는다.The method of the present invention not only has a merit that the processing is simple, but also, as shown in Table 2, the electrode cathode material produced by the method of the present invention has a feature of high capacity and high efficiency.
Claims (10)
상기 기체는 탄소 함량이 99.9% 이상인 흑연류 재료이고, 형상이 구형, 종횡비가 1.0~4.5인, 괴상 및 편상 중 1종 이상이고, 기체가 나노미세구멍 또는 나노공극을 함유하고, 나노미세구멍 또는 나노공극의 크기는 10~500 nm이고, 공극률은 0.5~20%, 진밀도는 2.0~2.26 g/cm3이고; 상기 코팅층은 비흑연 탄소재료이고, 코팅층의 질량은 기체 질량의 0 초과 내지 20%이며; 상기 복합재료의 평균입도(D50)는 3.0~50.0 μm, 비표면적은 1.0~20.0 m2/g, 복합재료 분말 압축밀도는 1.50~2.15 g/cm3이고; 상기 흑연류 재료는 천연 인상 흑연(natural flake graphite), 천연 미정질 흑연(natural microcrystalline graphite), 천연 결정질 맥상 흑연(natural crystalline vein graphite), 인조 흑연, 탄소 미립자 및 전도성 흑연 중 1종 이상이고; 상기 비흑연 탄소재료는 이흑연화 연질 탄소, 유기물 열분해 탄소 또는 기상증착 탄소이며; 상기 이흑연화 연질 탄소는 연화점이 30~300 ℃인 석탄 역청, 석유 역청, 콜 타르, 석유공업 중질유 및 중질 방향족 탄화수소 중 1종 이상이고; 상기 유기물은 폴리비닐알코올, 폴리비닐 클로라이드, 폴리에틸렌 글리콜, 폴리(에틸렌옥시드), 폴리비닐리덴 플루오라이드, 아크릴수지 및 폴리아크릴로니트릴 중 1종 이상의 고분자 중합물, 또는 폴리티오펜, 폴리아닐린, 폴리아세틸렌, 폴리피롤, 폴리아센, 폴리페닐렌, 폴리페닐렌 비닐렌 및 폴리디아세틸렌 중 1종 이상의 고분자 전도성 중합물인 것을 특징으로 하는 전극 음극재료.An electrode cathode material which is a composite material comprising a substrate and a coating layer coated with the substrate,
The gas is a graphite material having a carbon content of 99.9% or more, and is spherical in shape, 1.0 to 4.5 in aspect ratio, at least one of massive and flaky, the gas contains nano-pores or nano-pores, The size of the nanopore is 10 to 500 nm, the porosity is 0.5 to 20% and the true density is 2.0 to 2.26 g / cm < 3 >; The coating layer is a non-graphitic carbon material and the mass of the coating layer is more than 0 to 20% of the gas mass; The composite material has an average particle size (D 50 ) of 3.0 to 50.0 μm, a specific surface area of 1.0 to 20.0 m 2 / g, and a composite material powder compact density of 1.50 to 2.15 g / cm 3 ; Wherein the graphite material is at least one of natural flake graphite, natural microcrystalline graphite, natural crystalline vein graphite, artificial graphite, carbon fine particles and conductive graphite; The non-graphite carbon material is graphitized soft carbon, organic pyrolytic carbon or vapor deposited carbon; The graphitized soft carbon is at least one of coal bitumen, petroleum bitumen, coal tar, petroleum heavy oil and heavy aromatic hydrocarbons having a softening point of 30 to 300 ° C; Wherein the organic material is at least one polymeric polymer selected from the group consisting of polyvinyl alcohol, polyvinyl chloride, polyethylene glycol, poly (ethylene oxide), polyvinylidene fluoride, acrylic resin and polyacrylonitrile, or polythiophene, polyaniline, , Polypyrrole, polyacene, polyphenylene, polyphenylene vinylene, and polydiacetylene.
2. 100 ℃ 이하까지 강온하고, 산화 기체, 환원 기체, 산화 기체와 환원 기체의 혼합 기체, 산화 기체와 비활성 기체의 혼합 기체, 환원 기체와 비활성 기체의 혼합 기체, 또는 산화 기체와 환원 기체와 비활성 기체의 혼합 기체의 주입을 정지하는 단계; 및
3. 산화/환원처리한 흑연류 재료를 흑연 기체로 하고, 이흑연화 연질 탄소를 고상 코팅하거나 또는 유기물 열분해 탄소를 액상 코팅하고, 비흑연 탄소재료로 열분해시켜 전극 음극재료를 얻는 단계로서, 코팅층의 질량은 흑연 기체 질량의 0 초과 내지 20%이고, 이흑연화 연질 탄소는 연화점이 30~300 ℃인 석탄 역청, 석유 역청, 콜 타르, 석유공업 중질유 및 중질 방향족 탄화수소 중 1종 이상이며, 상기 유기물은 폴리비닐알코올, 폴리비닐 클로라이드, 폴리에틸렌 글리콜, 폴리(에틸렌옥시드), 폴리비닐리덴 플루오라이드, 아크릴수지 및 폴리아크릴로니트릴 중 1종 이상의 고분자 중합물, 또는 폴리티오펜, 폴리아닐린, 폴리아세틸렌, 폴리피롤, 폴리아센, 폴리페닐렌, 폴리페닐렌 비닐렌 및 폴리디아세틸렌 중 1종 이상의 고분자 전도성 중합물인 단계
를 포함하는 전극 음극재료의 제조방법. 1. the method comprising the graphite material processing stream oxidizing and / or reducing the graphite material flow for 0.1 ~ 100 ℃ / min the temperature was raised at a rate of, at the same time 0.05 ~ 10 m in the oxidation gas flow rate of 3 / h, a reducing gas, an oxidizing A mixed gas of a gas and a reducing gas, a mixed gas of an oxidizing gas and an inert gas, a mixed gas of a reducing gas and an inert gas, or a mixed gas of an oxidizing gas, a reducing gas and an inert gas, , Said graphite material being at least one of natural graphite, natural microcrystalline graphite, natural crystalline graphite, artificial graphite, carbon microparticles and conductive graphite;
2. A method for reducing the temperature to 100 DEG C or lower, comprising the steps of: oxidizing gas, a reducing gas, a mixed gas of an oxidizing gas and a reducing gas, a mixed gas of an oxidizing gas and an inert gas, a mixed gas of a reducing gas and an inert gas, Stopping the injection of the mixed gas of the gas; And
3. A step of obtaining an electrode cathode material by using a graphite material which is oxidized / reduced as a graphite gas, solidifying the soft carbon soft carbon or liquid-coating the organic pyrolytic carbon and pyrolyzing the carbon black by a non-graphite carbon material, Wherein the mass of the soft carbon is at least one kind selected from the group consisting of coal bitumen, petroleum bitumen, coal tar, petroleum heavy oil and heavy aromatic hydrocarbons having a softening point of 30 to 300 DEG C, At least one polymeric polymeric material selected from the group consisting of polyvinyl alcohol, polyvinyl chloride, polyethylene glycol, poly (ethylene oxide), polyvinylidene fluoride, acrylic resin and polyacrylonitrile, or polythiophene, polyaniline, polyacetylene, polypyrrole, Polyacene, polyphenylene, polyphenylene vinylene, and polydiacetylene.
Wherein the electrode is made of a metal.
2. 기상코팅하는 단계로서, 탄소 함유성 기체를 주입하고, 주입량을 0.05~15 m3/h으로 하고, 0.1~5 시간 유지한 후 로 내를 100 ℃ 이하로 강온하며, 산화 기체, 환원 기체, 산화 기체와 환원 기체의 혼합 기체, 산화 기체와 비활성 기체의 혼합 기체, 환원 기체와 비활성 기체의 혼합 기체, 또는 산화 기체와 환원 기체와 비활성 기체의 혼합 기체의 주입을 정지하며, 상기 탄소 함유성 기체는 메탄, 아세틸렌, 에틸렌, CO2, 천연가스, 액화석유가스, 벤젠 및 티오펜 중 1종 이상인 단계
를 포함하는 전극 음극재료의 제조방법.1. the method comprising the graphite material processing stream oxidizing and / or reducing the graphite material flow for 0.1 ~ 100 ℃ / min the temperature was raised at a rate of, at the same time 0.05 ~ 10 m in the oxidation gas flow rate of 3 / h, a reducing gas, an oxidizing A mixed gas of a gas and a reducing gas, a mixed gas of an oxidizing gas and an inert gas, a mixed gas of a reducing gas and an inert gas, or a mixed gas of an oxidizing gas and a reducing gas and an inert gas, , Maintaining a temperature of more than 0 to 6 hours; And
2. A vapor-phase coating process comprising the steps of: injecting a carbon-containing gas; injecting the coating at a rate of 0.05 to 15 m 3 / h; maintaining the coating for 0.1 to 5 hours; lowering the furnace temperature to 100 ° C or lower; , A mixture of an oxidizing gas and a reducing gas, a mixed gas of an oxidizing gas and an inert gas, a mixed gas of a reducing gas and an inert gas, or a mixed gas of an oxidizing gas and a reducing gas and an inert gas, The gas is at least one of methane, acetylene, ethylene, CO 2 , natural gas, liquefied petroleum gas, benzene and thiophene
Wherein the electrode is made of a metal.
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