KR20130046423A - Negative electrode material of electrode and preparing method therefor - Google Patents

Negative electrode material of electrode and preparing method therefor Download PDF

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KR20130046423A
KR20130046423A KR1020137000662A KR20137000662A KR20130046423A KR 20130046423 A KR20130046423 A KR 20130046423A KR 1020137000662 A KR1020137000662 A KR 1020137000662A KR 20137000662 A KR20137000662 A KR 20137000662A KR 20130046423 A KR20130046423 A KR 20130046423A
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graphite
gas
carbon
electrode
temperature
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KR101439068B1 (en
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민 위에
후이칭 얜
밍화 덩
유유안 황
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썬쩐 비티아르 뉴 에너지 머티어리얼스 아이엔씨이
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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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

본 발명은 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 anode material and a method for manufacturing the same, the technical problem to be solved is to increase the safety of the lithium ion battery, and to reduce the production cost. The electrode cathode material of the present invention is a composite material comprising 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-fine pores or nano-pores, the coating layer is carbon Material. The method for producing an electrode cathode material of the present invention includes the following steps:
The graphite materials are oxidized / reduced and solid graphite or liquid coated with digraphitized soft carbon or organic pyrolytic carbon. Comparing the present invention with the prior art, the surface functional groups of the treatment layer and / or coating layer are controlled on the surface of the electrode anode material, the treatment layer and the coating layer are thin and uniform, increase the stability and thermal conductivity in the electrolyte, lithium ion battery To increase the safety of the electrode material has the advantages of high capacity and high efficiency, the manufacturing process is simple, and the cost of the cathode material is reduced.

Description

전극 음극재료 및 그의 제조방법 {NEGATIVE ELECTRODE MATERIAL OF ELECTRODE AND PREPARING METHOD THEREFOR}Electrode cathode material and its manufacturing method {NEGATIVE ELECTRODE MATERIAL OF ELECTRODE AND PREPARING METHOD THEREFOR}

본 발명은 전지의 전극재료 및 그의 제조방법, 특히 리튬이온전지의 음극재료 및 그의 제조방법에 관한 것이다.TECHNICAL FIELD The present invention relates to an electrode material of a battery and a method of manufacturing the same, in particular, a cathode material of a lithium ion battery and a method of 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 the standard of living, China's dependence on oil is increasing day by day, which is a direct threat to China's energy safety. In addition, oil price fluctuations also have a direct impact on the development of the national economy, and force people to find and develop new energy. The development of power cells and electric vehicles is in an increasingly important position, and the main reason for limiting large-scale application of electric vehicles is power cells. Lithium-ion battery is gradually increasing within the next 10-20 years due to its high energy density, high voltage, pollution-free, long cycle life with more than 500 cycles, excellent performance in fast charging and discharging, etc. It will be the preferred battery for electric vehicles. However, lithium ion batteries have a disadvantage of high price. In addition, the power type lithium ion battery is relatively large in volume, and correspondingly inferior in stability. Thus, cost and safety are major obstacles to the restriction of using lithium ion batteries as power cells. Negative electrode material is one of the main materials of the lithium ion battery, its price has a significant influence on the final price of the battery, and stability and thermal conductivity in the electrolyte also has a great effect on the safety of the battery. The prior art has often been a limitation in the development of lithium ion power cells because of the complicated reforming required in the production of anode materials for lithium ion batteries and the relatively high production cost.

본 발명의 목적은 전극 음극재료 및 그의 제조방법을 제공하는 것이고, 해결하고자 하는 기술적 과제는 리튬이온전지의 안전성을 높이고, 생산원가를 절감시키는 것이다. It is an object of the present invention to provide an electrode anode material and a method of manufacturing the same, and a technical problem to be solved is to increase the safety of the lithium ion battery, and to reduce the production cost.

본 발명은 이하의 기술적 방안을 사용한다:The present invention uses the following technical solutions:

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 결정질 흑연, 천연 은정질(cryptocrystalline) 흑연, 천연 결정맥상 흑연, 인조 흑연, 카본 마이크로스피어 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, 폴리티오펜, 폴리페닐렌, 폴리페닐렌 비닐렌 및 폴리디아세틸렌 중 1종 이상의 고분자 전도성 중합물이다.The electrode cathode material is a composite material including a base and a coating layer coated with the base, the base is a graphite material having a carbon content of 99.9% or more, and is spherical in shape and has an aspect ratio of 1.0 to 4.5. At least one of a block and flakes close to the spherical shape, the gas contains nano-pores or nanopores, the size of the nano-pores or nanopores is 10-500 nm, the porosity is 0.5-20%, true density (true density) is 2.0-2.26 g / cm 3 ; The coating layer is a non-graphite carbon material, and the mass of the coating layer is greater than 0 to 20% of the mass of the gas; Average particle size (D 50 ) of the composite material is 3.0 ~ 50.0 μm, specific surface area is 1.0 ~ 20.0 m 2 / g, composite powder compact density is 1.50 ~ 2.15 g / cm 3 ; The graphite material is natural crystalline graphite, At least one of natural cryptocrystalline graphite, natural crystalline graphite, artificial graphite, carbon microspheres, and conductive graphite; The non-graphite carbonaceous material is digraphitized soft carbon, organic pyrolysis carbon or vapor deposition carbon; The digraphitized soft carbon is at least one of coal bitumen, petroleum bitumen, coal tar, petroleum industry heavy oil and heavy aromatic hydrocarbons having a softening point of 30 to 300 ° C., and the organic material is polyvinyl alcohol, polyvinyl chloride, polyethylene glycol, poly (Ethylene oxide), polyvinylidene fluoride, at least one polymer polymer of acrylic resin and polyacrylonitrile, or polythiophene, polyaniline, polyacetylene, polypyrrole, polyacene, polythiophene, polyphenylene, poly At least one polymer conductive polymer of phenylene vinylene and polydiacetylene.

전극 음극재료의 제조방법은 이하의 단계를 포함한다:The manufacturing method of the 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/환원기체(gas) 또는 산화/환원기체 및 비활성기체의 혼합기체를 주입하고, 온도를 100~1000 ℃으로 한다; 상기 흑연류 재료는 천연 결정질 흑연, 천연 은정질 흑연, 천연 결정맥상 흑연, 인조 흑연, 카본 마이크로스피어 및 전도성 흑연 중 1종 이상이다;1. oxidizing / reducing the graphite materials; The graphite material is heated at a rate of 0.1 to 100 ° C./min, and at the same time, an oxidizing / reducing gas or a mixture of oxidizing / reducing gas and inert gas is injected at a flow rate of 0.05 to 10 m 3 / h, and the temperature is To 100 to 1000 ° C; The graphite material is at least one of natural crystalline graphite, natural silver crystalline graphite, natural crystalline graphite, artificial graphite, carbon microspheres and conductive graphite;

2. 100 ℃ 이하까지 강온하고, 산화/환원기체 또는 산화/환원기체 및 비활성기체의 혼합기체의 주입을 정지하는 단계;2. The temperature is lowered to 100 ° C. or lower, and the injection of the oxidizing / reducing gas or the mixed gas of the oxidizing / reducing gas and the inert gas is stopped;

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, 폴리티오펜, 폴리페닐렌, 폴리페닐렌 비닐렌 및 폴리디아세틸렌 중 1종 이상의 고분자 전도성 중합물이다. 3. Oxidation / reduction treatment of graphite materials as graphite gas, solid graphite coating or liquid phase coating of digraphitized soft carbon or organic pyrolysis carbon, and pyrolysis to non-graphite carbon material to obtain an electrode anode material; The mass of the coating layer is greater than 0 to 20% of the mass of the graphite gas; Digraphitized soft carbon is at least one of coal bitumen, petroleum bitumen, coal tar, petroleum industry heavy oil and heavy aromatic hydrocarbons having a softening point of 30 to 300 ° C; The organic material is at least one polymer polymer of polyvinyl alcohol, polyvinyl chloride, polyethylene glycol, poly (ethylene oxide), polyvinylidene fluoride, acrylic resin and polyacrylonitrile, or polythiophene, polyaniline, polyacetylene , Polypyrrole, polyacene, polythiophene, 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 is a moisture content of the electrode negative electrode material to less than 0.1% using a heating or vacuum drying method to 100 ℃ 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.To remove the magnetism with respect to the electrode negative electrode material of the present invention, to remove the magnetism 1 to 20 times, the magnetic sensitive strength is 3000 ~ 30000 Gs, the treatment temperature is 10 ~ 80 ℃, the electron hammer blow cycle is 3 ~ 180 times / It is made into seconds, and then sieved to obtain an electrode anode 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 oxidizing / reducing the graphite material of the present invention, the furnace chamber of the oxidation / reducing 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 oxidized / reduced, if the temperature reaches 100 to 1000 ° C, the graphite material is kept warm for more than 0 to 6 hours.

본 발명의 강온은 로 벽 및 로 벽 내의 열전도층 사이에서 압축공기를 주입하는 방식 또는 로 내에서의 자연 강온 방식을 이용한다. The temperature reduction of the present invention utilizes a method of injecting compressed air between the furnace wall and the heat conduction layer in the furnace wall or a natural temperature reduction method in the furnace.

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 mass of the graphite gas, the mixing speed is 100 ~ 500 r / min (rpm), the mixing coating is 5 ~ 180 minutes, or the fusion rotation speed is 500 ~ 3000 r / The minute and gap are 0.01-1.0 cm, the fusion temperature is 20-80 ° C, the fusion coating is 10-200 minutes, and the temperature is naturally lowered to room temperature.

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, the stirring and stirring of the liquid mixture of the graphite gas and the soluble organic substance having a graphite gas mass of 0.1 to 20% at a rate of 2000 to 8000 r / min is carried out for 10 to 120 minutes, and the liquid mixing solvent is water or organic It is a solvent, the solvent mass is 0.8-2.0 times the mass of graphite gas, the mixing temperature is 10-90 degreeC, and it drys for 1 to 30 hours on 80-300 degreeC conditions.

전극 음극재료의 제조방법은 이하의 단계를 포함한다:The manufacturing method of the 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/환원기체 또는 산화/환원기체 및 비활성기체의 혼합기체를 주입하고, 온도가 100~1000 ℃에 도달하면, 0 초과 내지 6 시간 보온한다;1. Oxidation / reduction treatment of the graphite material: the graphite material is heated at a rate of 0.1 ~ 100 ℃ / min, at the same time oxidation / reduction gas or oxidation / reduction gas and at a flow rate of 0.05 ~ 10 m 3 / h and Inject a mixed gas of inert gas, and when the temperature reaches 100 ~ 1000 ℃, keep warm for more than 0 to 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/환원기체 또는 산화/환원기체 및 비활성기체의 혼합기체의 주입을 정지한다; 상기 탄소 함유성 기체는 메탄, 아세틸렌, 에틸렌, CO2, 천연가스, 액화석유가스, 벤젠 및 티오펜 중 1종 이상이다.2. Vapor phase coating step: Injecting a carbon-containing gas, the injection amount is 0.05 ~ 15 m 3 / h, maintained for 0.1 ~ 5 hours, the temperature in the furnace is lowered to 100 ℃ or less, oxidation / reduction gas or oxidation / Stop the injection of the mixture gas of reducing gas and 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. Comparing the present invention with the prior art, the surface of the electrode cathode material controls the surface functional groups of the treatment layer and / or coating layer on the surface without using a conventional surface coating process, the treatment layer and the coating layer are thin and uniform, It improves stability and thermal conductivity in the electrolyte, increases the safety of the lithium ion battery, the electrode anode material also has the advantages of high capacity and high efficiency, the manufacturing process is simple, and the cost of the anode material is reduced.

도 1은 실시예 1의 전극 음극재료의 SEM 도면이다.
도 2는 실시예 2의 전극 음극재료의 충방전 비용량-전압 곡선도이다.1 is an SEM diagram of an electrode cathode material of Example 1. FIG.
2 is a charge-discharge specific-voltage curve 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.The accompanying drawings and examples which follow provide a more detailed description of the invention. The electrode cathode material of the present invention is a gas and a coating layer coated with the gas is used as a composite material, the gas is a graphite material having a carbon content of more than 99.9%, the shape is spherical, the shape is close to the sphere having a 1.0 to 4.5 aspect ratio, and At least one of the phases, the gas contains nano- or nano-pores, the size of the nano-pores or nano-pores is 10-500 nm, the porosity (nano micro-pores or nanopore volume / unit volume of gas) 0.5-20%, true density is 2.0-2.26 g / cm 3 ; The coating layer is a non-graphite carbon material, and the mass of the coating layer is greater than 0 to 20% of the mass of the gas; The average particle size (D 50 ) of the composite is 3.0-50.0 μm, the specific surface area is 1.0-20.0 m 2 / g, and the composite powder compact density is 1.50-2.15 g / cm 3 .

상기 흑연류 재료는 천연 결정질 흑연, 천연 은정질 흑연, 천연 결정맥상 흑연, 인조 흑연, 카본 마이크로스피어 및 전도성 흑연 중 1종 이상이다.The graphite materials are at least one of natural crystalline graphite, natural silver crystalline graphite, natural crystalline graphite, artificial graphite, carbon microspheres and conductive graphite.

상기 비흑연 탄소재료는 이흑연화 연질 탄소, 유기물 열분해 탄소 또는 기상증착 탄소이다.The non-graphite carbonaceous material is digraphitized soft carbon, organic pyrolysis carbon, or vapor deposition 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 digraphitized soft carbon is at least one of coal bitumen, petroleum bitumen, coal tar, petroleum industry 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, 폴리티오펜, 폴리페닐렌, 폴리페닐렌 비닐렌 및 폴리디아세틸렌 중 1종 이상이다.The organic material is a polymer polymer and a polymer conductive polymer. The polymer 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, polythiophene, 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 preparing the electrode anode material of the present invention is to obtain the electrode cathode material through oxidation / reduction, reforming coating, magnetic removal, and sieving step for the graphite material, including 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/환원기체 또는 산화/환원기체 및 비활성기체의 혼합기체를 주입하고, 온도가 100~1000 ℃에 도달하면 0 초과 내지 6 시간 보온하고, 흑연류 재료에 대해 산화/환원처리를 한다.1. Oxidize / reduce the graphite materials; A graphite material having a particle size of 2.8 to 45.0 μm is placed in a furnace chamber of a rotary furnace, the furnace chamber is rotated at a rotation speed of more than 0 to 20 rpm, and the temperature is increased at a speed of 0.1 to 100 ° C./min, and at the same time 0.05 to 10 m. Oxidation / reduction gas or a mixture of oxidation / reduction gas and inert gas is injected at a flow rate of 3 / h, and when the temperature reaches 100-1000 ° C., it is kept warm for more than 0 to 6 hours, and oxidation / reduction for graphite materials Do the processing.

상기 흑연류 재료는 천연 결정질 흑연, 천연 은정질 흑연, 천연 결정맥상 흑연, 인조 흑연, 카본 마이크로스피어 및 전도성 흑연 중 1종 이상이다; The graphite material is at least one of natural crystalline graphite, natural silver crystalline graphite, natural crystalline graphite, artificial graphite, carbon microspheres and conductive graphite;

상기 산화 및/또는 환원기체는 산소, 공기, 염소기체(Cl2), 브롬기체(Br2), 불소기체(F2)이고, 상기 비활성기체는 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/환원기체 또는 산화/환원기체 및 비활성기체의 혼합기체의 주입을 정지하여 흑연 기체를 얻는다.2. The temperature is reduced to 100 ° C. or lower using a method of injecting compressed air between the furnace wall and the heat conduction layer in the furnace wall or by using a natural temperature reduction method in the furnace, and the oxidation / reduction gas or the oxidation / reduction gas and the inert gas. Injection of the mixture 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. A composite material is obtained by solid, liquid or vapor phase coating of the oxidized / reduced graphite gas. The coating material precursor mass is greater than 0 to 20% of the mass of the graphite gas, and the moisture content of the negative electrode material is controlled to 0.1% or less using heating, vacuum drying or other conventional techniques below 100 ° C.

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 coating: The coating material precursor is 1% ~ 20% of the mass of graphite gas, using the precision mixer of the prior art, mixing rotation speed is 100 ~ 500 r / min, 5 ~ 180 min mixing coating, or The mixture is placed in a fusion apparatus of the prior art, the fusion rotation speed is 500 ~ 3000 r / min, the gap is 0.01 ~ 1.0 cm, the fusion temperature is 20 ~ 80 ℃ fusion coating for 10 to 200 minutes, the temperature is naturally lowered to room temperature. According to the prior art, heat treatment is performed under conditions of 100 to 3000 ° C. to thermally decompose 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, 폴리티오펜, 폴리페닐렌, 폴리페닐렌 비닐렌 및 폴리디아세틸렌 중 1종 이상이다.2) Liquid coating: Mixing and stirring the mixture of graphite gas and soluble organic liquid with a graphite gas mass of 0.1-20% at a speed of 2000-8000 r / min for 10-120 minutes using a high speed stirring vessel of the prior art. Get Water or organic solvent is used as solvent, the mass of solvent is 0.8 ~ 2.0 times the mass of graphite gas, mixing temperature is 10 ~ 90 ℃, and 1 ~ 30 hours under the condition of 80 ~ 300 ℃ using dry box. Dry. According to the prior art, heat treatment is performed under conditions of 100 to 3000 ° C. to thermally decompose the non-graphite carbon material. As the coating material, an organic polymer polymer and a polymer conductive polymer are used. The polymer 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, polythiophene, 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/환원기체 또는 산화/환원기체 및 비활성기체의 혼합기체의 주입을 정지하며, 기상코팅의 전구물, 즉 탄소 함유성 기체는 메탄, 아세틸렌, 에틸렌, CO2, 천연가스, 액화석유가스, 벤젠 및 티오펜 중 1종 이상이다.3) Vapor phase coating: After oxidation / reduction treatment of graphite materials, carbon-containing gas is directly injected, and the injection amount is maintained at 0.05-15 m 3 / h, and after 0.1-5 hours, it is naturally lower than 100 ℃. Lowering the temperature, stopping the injection of the oxidizing / reducing gas or a mixture of oxidizing / reducing gas and inert gas, and the precursor of the gas phase coating, i.e. the carbon-containing gas, is methane, acetylene, ethylene, CO 2 , natural gas, liquefied petroleum At least one of 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) Demagnetization of composite material: Remove magnetism 1 ~ 20 times, magnetic sensitivity is 3000 ~ 30000 Gs, treatment temperature is 10 ~ 80 ℃, electron hammer blow cycle is 3 ~ 180 times / sec, and then sieved. The electrode negative electrode material having an average particle size (D 50 ) of 3.0 to 50.0 μm is obtained.

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 oxidizing / reducing the graphite materials, when the temperature reaches 100-1000 ° C., the temperature is maintained for more than 0 to 6 hours, and nanopores or nanofine pores are formed in the gaseous material. The conductivity of the material can be enhanced.

히타치(Hitachi) S4800형 주사 전자 현미경(SEM)을 사용하여 실시예에서 얻어진 전극 음극재료를 관찰한다. The electrode negative electrode material obtained in the Example was observed using the 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. The negative electrode of the experimental battery was fabricated using the electrode negative electrode material prepared in the present invention, and the electrode negative electrode material, polyvinylidene fluoride, and conductive carbon black were mixed at a mass ratio of 98: 2 and dissolved in N-methylpyrrolidone. The mixture of 10% of the obtained mass concentration is then uniformly applied to a 10 μm thick copper foil, compressed into pieces, a carbon film 1 cm in diameter, and dried in a drying box at 120 ° C. for 12 hours. The electrode prepared from the prepared electrode flakes, the auxiliary electrode and the reference electrode made of a metal lithium piece, the concentration produced by using the EC, DMC, EMC solvent mixed in a volume ratio of 1: 1: 1 is 1 mol / L Using LiPF 6 as the electrolyte, a simulated battery having an inner diameter of Φ12 mm was prepared in a glove box filled with argon gas. The charge / discharge measurement of the battery is performed on the CT2001C of Wuhan Kumnak Electronics Co., Ltd.'s NAND battery measurement system. The charge and discharge voltage range is 0.01 V to 2.0 V, and the current is 0.2 C. Capacity and efficiency are measured according to the measurement method of GB / T 24533-2009 lithium ion battery graphite anode material.

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 under high temperature of 45 ° C. The higher the capacity retention, 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 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, the graphite gas (D 50 = 19.2 μm) material was subjected to surface oxidation / reduction, followed by liquid coating with 0.5% of polypyrrole, and the specific surface area of the material obtained after heat treatment at 150 ° C. was 5.26 m 2 / g. The powder compression density is 1.90 g / cm 3 , and as shown in the SEM, the graphite gas granules are spherical and nearly spherical in shape, and the surface oxidation and / or reduction and coating layers are uniform, and the surface is oxidized and / or reduced. Because of the treatment, the surface functional groups decreased, the reaction under low potential was decreased, the thermal stability fixed in the electrolyte solution was good, the side reactions of the electrolyte solution and the oxidation and / or reduction layer and the coating layer were small, and the SEI film was stable, and the solid was The high temperature circulation of the battery was excellent. 100 weeks capacity retention rate is 95% under 45 ℃.

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 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 the advantage that the treatment process is simple, but as can be seen in Table 2, the electrode anode material produced by the method of the present invention has the features of high capacity and high efficiency.

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Claims (10)

기체(基體) 및 상기 기체를 코팅한 코팅층을 포함하는 복합재료인 전극 음극재료이며,
상기 기체는 탄소 함량이 99.9% 이상인 흑연류 재료이고, 형상이 구형, 종횡비가 1.0~4.5인 구형에 가까운, 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 결정질 흑연, 천연 은정질(cryptocrystalline) 흑연, 천연 결정맥상 흑연, 인조 흑연, 카본 마이크로스피어 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, 폴리티오펜, 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 including a base and a coating layer coated with the base,
The gas is a graphite material having a carbon content of at least 99.9%, at least one of a block and a flake having a spherical shape and a spherical shape with a aspect ratio of 1.0 to 4.5, the gas containing nano fine pores or nano pores, and nano The size of the micropores or nanopores is 10-500 nm, the porosity is 0.5-20%, and the true density is 2.0-2.26 g / cm 3 ; The coating layer is a non-graphite carbon material, and the mass of the coating layer is greater than 0 to 20% of the mass of the gas; The average particle size (D 50 ) of the composite material is 3.0-50.0 μm, the specific surface area is 1.0-20.0 m 2 / g, and the composite powder compact density is 1.50-2.15 g / cm 3 ; The graphite material is at least one of natural crystalline graphite, natural crystalline graphite, natural crystalline graphite, artificial graphite, carbon microspheres, and conductive graphite; The non-graphite carbonaceous material is digraphitized soft carbon, organic pyrolysis carbon or vapor deposition carbon; The digraphitized soft carbon is at least one of coal bitumen, petroleum bitumen, coal tar, petroleum industry heavy oil and heavy aromatic hydrocarbons having a softening point of 30 to 300 ° C; The organic material is at least one polymer polymer of polyvinyl alcohol, polyvinyl chloride, polyethylene glycol, poly (ethylene oxide), polyvinylidene fluoride, acrylic resin and polyacrylonitrile, or polythiophene, polyaniline, polyacetylene And at least one polymer conducting polymer of polypyrrole, polyacene, polythiophene, polyphenylene, polyphenylene vinylene and polydiacetylene. 이하의 단계를 포함하는 전극 음극재료의 제조방법:
1. 흑연류 재료를 산화 및/또는 환원처리하는 단계; 흑연류 재료를 0.1~100 ℃/분의 속도로 승온시키고, 동시에 0.05~10 m3/h의 유량으로 산화/환원기체 또는 산화/환원기체 및 비활성기체의 혼합기체를 주입하고, 온도를 100~1000 ℃으로 한다; 상기 흑연류 재료는 천연 결정질 흑연, 천연 은정질 흑연, 천연 결정맥상 흑연, 인조 흑연, 카본 마이크로스피어 및 전도성 흑연 중 1종 이상이다;
2. 100 ℃ 이하까지 강온하고, 산화/환원기체 또는 산화/환원기체 및 비활성기체의 혼합기체의 주입을 정지하는 단계;
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 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, 폴리티오펜, 폴리페닐렌, 폴리페닐렌 비닐렌 및 폴리디아세틸렌 중 1종 이상의 고분자 전도성 중합물이다. Method for producing an electrode cathode material comprising the following steps:
1. oxidizing and / or reducing the graphite material; The graphite material is heated at a rate of 0.1 to 100 ° C./min, and at the same time, an oxidizing / reducing gas or a mixture of oxidizing / reducing gas and inert gas is injected at a flow rate of 0.05 to 10 m 3 / h, and the temperature is 100 to At 1000 ° C .; The graphite material is at least one of natural crystalline graphite, natural silver crystalline graphite, natural crystalline graphite, artificial graphite, carbon microspheres and conductive graphite;
2. The temperature is lowered to 100 ° C. or lower, and the injection of the oxidizing / reducing gas or the mixed gas of the oxidizing / reducing gas and the inert gas is stopped;
3. Obtaining an electrode cathode material by using the graphite / oxidized graphite material as a graphite gas, solid phase coating of digraphitized soft carbon, or liquid phase coating of organic pyrolysis carbon, and pyrolysis to a non-graphite carbon material; The mass of the coating layer is greater than 0 to 20% of the mass of the graphite gas; Digraphitized soft carbon is at least one of coal bitumen, petroleum bitumen, coal tar, petroleum industry heavy oil and heavy aromatic hydrocarbons having a softening point of 30 to 300 ° C; The organic material is at least one polymer polymer of polyvinyl alcohol, polyvinyl chloride, polyethylene glycol, poly (ethylene oxide), polyvinylidene fluoride, acrylic resin and polyacrylonitrile, or polythiophene, polyaniline, polyacetylene , Polypyrrole, polyacene, polythiophene, polyphenylene, polyphenylene vinylene and polydiacetylene. 제2항에 있어서, 상기 전극 음극재료에 대하여 100 ℃이하로 가열 또는 진공 건조방법을 사용하여 전극 음극재료 수분함량이 0.1% 이하가 되게 하는 것을 특징으로 하는, 전극 음극재료의 제조방법. The method of manufacturing an electrode anode material according to claim 2, wherein the moisture content of the electrode cathode material is 0.1% or less by using a heating or vacuum drying method at 100 ° C or less with respect to the electrode cathode material. 제2항에 있어서, 상기 전극 음극재료에 대하여 건조 후 체질하고 자성을 제거하는데, 1~20회 자성을 제거하고, 자기감응 강도는 3000~30000 Gs, 처리온도는 10~80 ℃, 전자해머 타격 주기는 3~180회/초로 하고, 이후 체질을 하여, 평균입도(D50)가 3.0~50.0 μm인 전극 음극재료를 얻는 것을 특징으로 하는, 전극 음극재료의 제조방법. The method according to claim 2, wherein the electrode cathode material is sieved after drying and the magnetism is removed, the magnetism is removed 1 to 20 times, the magnetic sensitive strength is 3000 to 30000 Gs, the treatment temperature is 10 to 80 ℃, the electron hammer blow The cycle is 3 to 180 times / second, and then sieved to obtain an electrode anode material having an average particle size (D 50 ) of 3.0 to 50.0 μm. 제2항에 있어서, 상기 흑연류 재료를 산화/환원처리할 때, 0 초과 내지 20 rpm의 회전속도로 산화/환원 흑연류 재료의 로 체임버를 회전시키는 것을 특징으로 하는, 전극 음극재료의 제조방법.The method of manufacturing an electrode anode material according to claim 2, wherein when the graphite material is oxidized / reduced, the furnace chamber of the oxidation / reduced graphite material is rotated at a rotational speed of more than 0 to 20 rpm. . 제2항에 있어서, 상기 흑연류 재료를 산화/환원처리할 때, 온도가 100~1000 ℃에 도달하면 0 초과 내지 6 시간 보온하는 것을 특징으로 하는, 전극 음극재료의 제조방법.The method for producing an electrode anode material according to claim 2, wherein when the graphite material is oxidized / reduced, the temperature is maintained at 0 to 6 hours when the temperature reaches 100 to 1000 ° C. 제2항에 있어서, 상기 강온은 로 벽 및 로 벽 내의 열전도층 사이에서 압축공기를 주입하는 방식 또는 로 내에서의 자연 강온 방식을 이용하는 것을 특징으로 하는, 전극 음극재료의 제조방법. The method of claim 2, wherein the temperature drop is a method of injecting compressed air between the furnace wall and the heat conduction layer in the furnace wall or using a natural temperature reduction method in the furnace. 제2항에 있어서, 상기 고상 코팅의 코팅재료는 흑연 기체 질량의 1~20%이고, 혼합속도는 100~500 r/분, 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 강온하는 것을 특징으로 하는, 전극 음극재료의 제조방법. The coating material of the solid coating is 1 to 20% of the mass of the graphite gas, the mixing speed is 100 to 500 r / min, the mixing coating is 5 to 180 minutes, or the fusion rotation speed is 500 to 3000 r / Minute, the gap is 0.01 ~ 1.0 cm, the fusion temperature is 20 ~ 80 ℃, the fusion coating is 10 to 200 minutes, characterized in that the temperature is naturally lowered to room temperature. 제2항에 있어서, 상기 액상 코팅이 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 건조처리하는 것을 특징으로 하는, 전극 음극재료의 제조방법.The liquid coating according to claim 2, wherein the liquid coating mixes and stirs the graphite gas and the soluble organic liquid liquid mixture having a graphite gas mass of 0.1 to 20% at a rate of 2000 to 8000 r / min for 10 to 120 minutes. It is water or an organic solvent, the solvent mass is 0.8-2.0 times the mass of graphite gas, the mixing temperature is 10-90 degreeC, and it drys for 1 to 30 hours on conditions of 80-300 degreeC, The electrode negative electrode material characterized by the above-mentioned. Manufacturing method. 이하의 단계를 포함하는 전극 음극재료의 제조방법:
1. 흑연류 재료를 산화 및/또는 환원처리하는 단계; 흑연류 재료를 0.1~100 ℃/분의 속도로 승온시키고, 동시에 0.05~10 m3/h의 유량으로 산화/환원기체 또는 산화/환원기체 및 비활성기체의 혼합기체를 주입하고, 온도가 100~1000 ℃에 도달하면, 0 초과 내지 6 시간 보온한다;
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/환원기체 또는 산화/환원기체 및 비활성기체의 혼합기체의 주입을 정지한다; 상기 탄소 함유성 기체는 메탄, 아세틸렌, 에틸렌, CO2, 천연가스, 액화석유가스, 벤젠 및 티오펜 중 1종 이상이다.Method for producing an electrode cathode material comprising the following steps:
1. oxidizing and / or reducing the graphite material; The graphite materials are heated at a rate of 0.1 to 100 ° C./minute, and at the same time, an oxidizing / reducing gas or a mixture of oxidizing / reducing gas and inert gas is injected at a flow rate of 0.05 to 10 m 3 / h, and the temperature is 100 to When it reaches 1000 ° C., it is kept warm over 0 to 6 hours;
2. vapor phase coating; Injecting a carbon-containing gas, the injection amount is 0.05 ~ 15 m 3 / h, maintained for 0.1 to 5 hours, the temperature inside the furnace is lowered to 100 ℃ or less, and the oxidation / reduction gas or oxidation / reduction gas and inert gas Stop the injection of the mixed gas; The carbon-containing gas is at least one of methane, acetylene, ethylene, CO 2 , natural gas, liquefied petroleum gas, benzene and thiophene.
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