KR102615856B1 - Lithium secondary battery anode material - Google Patents
Lithium secondary battery anode material Download PDFInfo
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- KR102615856B1 KR102615856B1 KR1020210076945A KR20210076945A KR102615856B1 KR 102615856 B1 KR102615856 B1 KR 102615856B1 KR 1020210076945 A KR1020210076945 A KR 1020210076945A KR 20210076945 A KR20210076945 A KR 20210076945A KR 102615856 B1 KR102615856 B1 KR 102615856B1
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- silicon oxide
- aluminum
- lithium
- natural graphite
- lithium titanate
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 86
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 239000010405 anode material Substances 0.000 title abstract description 22
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 51
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 44
- 229910021382 natural graphite Inorganic materials 0.000 claims abstract description 42
- 239000002131 composite material Substances 0.000 claims abstract description 33
- 239000007773 negative electrode material Substances 0.000 claims abstract description 30
- 229910021470 non-graphitizable carbon Inorganic materials 0.000 claims description 16
- 229910052782 aluminium Inorganic materials 0.000 claims description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 23
- 239000003575 carbonaceous material Substances 0.000 description 14
- 229910052799 carbon Inorganic materials 0.000 description 13
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 10
- 229910001416 lithium ion Inorganic materials 0.000 description 8
- 229910052710 silicon Inorganic materials 0.000 description 8
- 239000010703 silicon Substances 0.000 description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 239000002028 Biomass Substances 0.000 description 6
- 239000010406 cathode material Substances 0.000 description 6
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- 229910002804 graphite Inorganic materials 0.000 description 5
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- 239000000843 powder Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 4
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229920001410 Microfiber Polymers 0.000 description 2
- 241000156302 Porcine hemagglutinating encephalomyelitis virus Species 0.000 description 2
- 239000006183 anode active material Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
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- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910020216 SiOx-Si Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000002388 carbon-based active material Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
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- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
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- 238000002844 melting Methods 0.000 description 1
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- 239000011259 mixed solution Substances 0.000 description 1
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- 238000005457 optimization Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
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- 150000003839 salts Chemical class 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical group [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 239000011863 silicon-based powder Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
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- 229920001187 thermosetting polymer Polymers 0.000 description 1
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- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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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
- H01M4/58—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
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
본 발명은 리튬 이차전지 음극재에 관한 것으로서, 상세하게는 리튬티타네이트가 코팅된 천연흑연을 알루미늄이 도핑된 실리콘 산화물 복합체로 피복하여, 충전 및 방전 사이클 안정성과 방전용량을 향상시켜 음극재로서 용이하게 사용할 수 있도록 한 것을 특징으로 하는, 리튬 이차전지 음극재에 관한 것이다.The present invention relates to a negative electrode material for lithium secondary batteries, and specifically, covers natural graphite coated with lithium titanate with an aluminum-doped silicon oxide composite to improve charge and discharge cycle stability and discharge capacity, making it easy to use as a negative electrode material. It relates to a lithium secondary battery anode material, characterized in that it can be used easily.
Description
본 발명은 리튬 이차전지 음극재에 관한 것으로서, 상세하게는 리튬티타네이트가 코팅된 천연흑연을 알루미늄이 도핑된 실리콘 산화물 복합체로 피복하여, 충전 및 방전 사이클 안정성과 방전용량을 향상시켜 음극재로서 용이하게 사용할 수 있도록 한 것을 특징으로 하는, 리튬 이차전지 음극재에 관한 것이다.The present invention relates to a negative electrode material for lithium secondary batteries, and specifically, covers natural graphite coated with lithium titanate with an aluminum-doped silicon oxide composite to improve charge and discharge cycle stability and discharge capacity, making it easy to use as a negative electrode material. It relates to a lithium secondary battery anode material, characterized in that it can be used easily.
리튬이차전지는 에너지 밀도가 향상됨에 따라 전지의 소형화, 경량화가 가능하여 휴대용 기기의 전원뿐 아니라 전기 자전거, 전동 공구 등의 기존 시장 외에 최근에는 HEV, PHEV, EV, 등 수송용 응용 분야 및 녹색 성장의 핵심 분야로 스마트 그리드 적용 전력 저장 장치까지 확대되고 있다.As the energy density of lithium secondary batteries improves, batteries can be made smaller and lighter, so in addition to existing markets such as electric bicycles and power tools as well as power sources for portable devices, they have recently been used in transportation applications such as HEV, PHEV, EV, and green growth. It is expanding to include smart grid-applied power storage devices as a core field of.
이러한 리튬이차전지는 4대 소재인 양극활물질(Cathode), 음극활물질(Anode), 분리막(Separator) 및 전해질(Electrolyte)로 구성되어 있며, 이들의 구성 성분에 의해 그 성능에 차이를 나타낸다.These lithium secondary batteries are composed of four major materials: cathode, anode, separator, and electrolyte, and their performance varies depending on their components.
그 중, 음극활물질은 충전시 리튬 이온과 전자(Electron)를 흡수하며, 방전 시 리튬 이온과 전자를 방출하는 물질로 양극활물질과 더불어 리튬이차전지의 용량, 출력, 안전성 등을 결정하는 주요 소재이다.Among them, the negative electrode active material is a material that absorbs lithium ions and electrons when charging and releases lithium ions and electrons when discharging. Along with the positive electrode active material, it is a major material that determines the capacity, output, and safety of lithium secondary batteries. .
초기의 리튬이차전지는 음극재(음극활물질)로서 리튬금속을 사용하였으나, 충전 및 방전이 반복됨에 따라 리튬금속의 이온화에 의한 용해 또는 석출(dendrite)되는 현상이 일어나 전지의 내부 단락이 초래되어 전지의 안전성 문제로 상용화에 실패하였다. 그러나, 1970년대부터 약 20년간의 연구개발 끝에 리튬금속을 탄소재료로 대체함으로써 전지의 안전성 문제를 해결하면서 상품화되었으며, 상품화 이래 리튬이차전지는 전지 내부공간의 최적화 및 설계로 인해 비약적으로 전지의 성능을 향상시켰다.Early lithium secondary batteries used lithium metal as a negative electrode material (negative electrode active material), but as charging and discharging were repeated, the lithium metal dissolved or precipitated (dendrite) due to ionization, resulting in an internal short circuit of the battery. Commercialization failed due to safety issues. However, after about 20 years of research and development starting in the 1970s, it was commercialized by resolving the safety issue of batteries by replacing lithium metal with carbon materials. Since commercialization, lithium secondary batteries have dramatically improved battery performance due to optimization and design of the internal space of the battery. improved.
즉, 리튬이차전지의 탄소계 음극재는 리튬 금속의 전극 전위에 근접한 전위를 가지며, 리튬이온의 삽입 및 탈리 과정 동안 결정구조의 변화가 작아 전극에서의 지속적이고 반복적인 산화환원 반응을 가능하게 함으로써 리튬 이차전지가 높은 용량 및 우수한 수명을 나타낼 수 있는 기반을 제공한 것으로, 일 예로, LIB에 사용되는 탄소계 음극에서 충전 및 방전 반응은 다음과 같이 진행된다.In other words, the carbon-based negative electrode material of a lithium secondary battery has a potential close to the electrode potential of lithium metal, and the change in crystal structure during the insertion and desorption process of lithium ions is small, enabling continuous and repetitive redox reactions at the electrode. It provides the basis for secondary batteries to exhibit high capacity and excellent lifespan. For example, in the carbon-based anode used in LIB, the charging and discharging reactions proceed as follows.
LiXC ↔ C +XLi+ +Xe- (→:방전, ←: 충전) Li _ _ _
충전반응 동안 음극재료인 탄소재료는 환원반응이 진행되어 Li 이온이 탄소재료 내부로 삽입되어 LiXC의 화합물을 형성하며, 방전반응 동안에는 산화반응이 일어나 탄소재료로부터 Li 이온이 탈리되어 결과적으로 상기 탄소소재 음극재료는 충전과정에서 리튬이온을 저장하게 되고, 방전과정에서는 리튬이온을 방출하게 되어, 이차전지의 기본적인 성능 특성들인 용량, 출력 및 수명특성에 크게 영향을 미친다. During the charging reaction, the carbon material, which is the cathode material, undergoes a reduction reaction and Li ions are inserted into the carbon material to form a compound of Li Carbon anode materials store lithium ions during the charging process and release lithium ions during the discharging process, greatly affecting the basic performance characteristics of secondary batteries: capacity, output, and lifespan.
그러나, 현재는 보다 고도화된 고용량화 및 고출력화 기술이 요구됨에 따라 기존의 방법에 더 이상 의존할 수 없는 실정으로, 새로운 음극소재 개발이 요구된다.However, as more advanced high-capacity and high-output technologies are currently required, existing methods can no longer be relied upon, and the development of new cathode materials is required.
따라서, 현재는 최적의 성능을 갖는 음극재료 개발을 위하여 탄소재료 제조 조건을 최적화하는 연구가 진행되고 있다. 이는 탄소재료는 원료 및 열처리 과정에 따라 결정성, 미세구조 및 입자 형상 등이 상이한 구조를 가지는데, 이들 구조에 따라 상기 탄소재료는 음극재료로 사용될 시 리튬의 저장용량 및 저장 기구가 서로 다르게 나타기 때문으로, 관련하여 한국 등록특허공보 제 10-0345295호(2002.07.08)는 리튬전지음극재용 탄소재료의 제조방법에 관한 것으로서, 탄소질 원료를 유기용매에 용해시켜 만든 혼합용액을 흑연분말 표면에 피복한 후, 탄화하는 것을 특징으로 하고, 이에 따라 제조된 리튬전지 음극재용 탄소재료는 흑연계와 카본계의 탄소재료가 혼합되어 탄소재료 또는 흑연만을 음극재로 구성하였을 때 갖는 문제점을 보완하고 있다.Therefore, research is currently underway to optimize carbon material manufacturing conditions to develop anode materials with optimal performance. This means that carbon materials have different structures in terms of crystallinity, microstructure, and particle shape depending on the raw materials and heat treatment process. Depending on these structures, the carbon materials have different lithium storage capacities and storage mechanisms when used as anode materials. Because of burning, related Korean Patent Publication No. 10-0345295 (July 8, 2002) relates to a method of manufacturing carbon materials for lithium battery anode materials, and applies a mixed solution made by dissolving carbonaceous raw materials in an organic solvent to the surface of graphite powder. It is characterized in that it is carbonized after being coated, and the carbon material for lithium battery negative electrode material produced according to this method is a mixture of graphite-based and carbon-based carbon materials to complement the problems of using only carbon material or graphite as the negative electrode material. there is.
그러나 상기 특허의 경우, 흑연계와 카본계의 탄소재료를 혼합되었을 뿐이어서, 음극재의 기능성 향상을 기대하기 어려운 문제점이 있다.However, in the case of the above patent, graphite-based and carbon-based carbon materials are only mixed, so there is a problem in that it is difficult to expect improvement in the functionality of the anode material.
이외에도 음극소재로 탄소에 실리콘을 함유시킨 고용량 음극활물질에 관한 연구가 이루어지고 있다. 실리콘계 음극활물질은 충ㆍ방전을 통해 전지가 부풀게 되는 Swelling 으로 인해 수명 저하를 유발할 수 있으나 이를 탄소와 조합하여 부푸는 현상을 억제하면서 고용량의 음극재로 개발하고 있다.In addition, research is being conducted on high-capacity anode active materials containing silicon and carbon as an anode material. Silicone-based anode active materials can reduce the lifespan due to swelling, which causes the battery to swell during charging and discharging, but by combining it with carbon, the swelling phenomenon is suppressed and high-capacity anode materials are being developed.
한국 등록특허공보 제 10-1446617호(2014.09.25)는 고용량 실리콘계 음극재의 제조방법에 관한 것으로서, 산소의 함량(x)이 0<x<2의 범위 내인 일반식 SiOx로 표현되는 실리콘산화물 분말과 상기 실리콘산화물 분말과 결합된 금속실리콘 분말로 이루어진 SiOx-Si 복합분말에 그래핀 분말을 결합시켜 음극재의 부피팽창을 억제하면서 고용량 및 고수명의 실리콘계 음극재를 제공하는 것을 특징으로 한다.Korean Patent Publication No. 10-1446617 (2014.09.25) relates to a method of manufacturing a high-capacity silicon-based anode material, comprising a silicon oxide powder expressed by the general formula SiOx with an oxygen content (x) within the range of 0<x<2, and It is characterized by providing a silicon-based anode material with high capacity and long service life while suppressing volume expansion of the anode material by combining graphene powder with a SiOx-Si composite powder made of metal silicon powder combined with the silicon oxide powder.
그러나 상기 선행문헌의 경우, 실리콘산화물 및 금속실리콘으로 형성된 복합분말에 그래핀이 단지 0.1 내지 10 중량부로 포함되어 있어, 그래핀은 실리콘의 부피팽창을 억제할 수 있으나, 음극재로서의 기능성이 높지 않은 단점이 있다.However, in the case of the prior literature, the composite powder formed of silicon oxide and metal silicon contains only 0.1 to 10 parts by weight of graphene, so graphene can suppress the volume expansion of silicon, but does not have high functionality as a negative electrode material. There is a downside.
또한, 기존 탄소계 활물질처럼 충·방전 시 리튬과의 삽입/탈리 반응을 통해 용량을 구현할 수 있으면서도 반응 시 부피변화가 거의 발생하지 않을 뿐만 아니라 리튬의 출입에 따른 구조 변화도 일어나지 않으며 높은 사이클 안정성을 갖는 리튬티타네이트를 음극활물질로서 활용하는 연구개발이 진행되고 있다. 한국 등록특허공보 제 10-1128860호(2012.03.14)는 리튬티타네이트 나노입자의 제조방법에 관한 것으로서, 리튬 및 티타늄을 포함하는 반응원료를 반응기에 주입하여 분자 수준으로 혼합한 후, 화학반응시킴으로써 결정핵을 생성하는 것을 특징으로 한다.In addition, like existing carbon-based active materials, capacity can be realized through insertion/desorption reactions with lithium during charging and discharging, but not only does little change in volume occur during the reaction, but no structural changes occur due to the entry and exit of lithium, resulting in high cycle stability. Research and development is underway to utilize lithium titanate as a negative electrode active material. Korean Patent Publication No. 10-1128860 (2012.03.14) relates to a method for producing lithium titanate nanoparticles, by injecting reaction raw materials containing lithium and titanium into a reactor, mixing them at the molecular level, and then chemically reacting. It is characterized by generating crystal nuclei.
상기 선행문헌의 경우, 리튬티타네이트 나노입자를 제조하는 방법과 함께 리튬티타네이트는 리튬 이차전지의 음극 활물질로서 사용될 수 있음을 개시하고 있으나, 상기 리튬티타네이트에 탄소물질이 결합 또는 리튬티타네이트 제조 공정에 있어서 탄소물질이 포함됨에 대해서는 전혀 개시하고 있지 않다. 이에, 상기 선행문헌을 통해서는 리튬티타네이트가 갖는 단점을 보완할 수 없어, 이를 음극재로서 사용할 시 낮은 전기 전도도로 인한 용량 및 출력의 전기 화학적 특성에서의 한계가 있다.In the case of the prior literature, it is disclosed that lithium titanate can be used as a negative electrode active material for lithium secondary batteries along with a method for producing lithium titanate nanoparticles, but a carbon material is bonded to the lithium titanate or lithium titanate is produced. There is no disclosure whatsoever about the inclusion of carbon materials in the process. Accordingly, the disadvantages of lithium titanate cannot be compensated for through the above prior literature, and when it is used as a negative electrode material, there are limitations in electrochemical characteristics of capacity and output due to low electrical conductivity.
이에, 본 발명은 상기와 같은 문제점을 해결하기 위하여, 리튬티타네이트가 코팅된 천연흑연; 및 알루미늄이 도핑된 실리콘 산화물 복합체;를 포함하고, 상기 리튬티타네이트가 코팅된 천연흑연은 알루미늄이 도핑된 실리콘 산화물 복합체로 피복되며, 상기 알루미늄이 도핑된 실리콘 산화물 복합체는 난흑연화성 탄소와 실리콘 산화물이 결합된 복합체 100 중량부에 알루미늄이 1 내지 10 중량부 도핑된 것을 특징으로 하는 리튬 이차전지 음극재를 제공하는 것을 그 해결과제로 한다.Accordingly, in order to solve the above problems, the present invention includes natural graphite coated with lithium titanate; and an aluminum-doped silicon oxide composite; wherein the lithium titanate-coated natural graphite is covered with an aluminum-doped silicon oxide composite, and the aluminum-doped silicon oxide composite includes non-graphitizable carbon and silicon oxide. The problem to be solved is to provide a lithium secondary battery negative electrode material characterized in that 1 to 10 parts by weight of aluminum is doped with 100 parts by weight of this combined composite.
또한, 본 발명은 상기와 같은 문제점을 해결하기 위하여, 상기 음극재를 포함하여 제조되는 리튬 이차전지를 제공하는 것을 그 해결과제로 한다.In addition, in order to solve the above problems, the present invention aims to provide a lithium secondary battery manufactured including the anode material.
상기 과제를 해결하기 위한 일 측면으로, 리튬티타네이트가 코팅된 천연흑연; 및 알루미늄이 도핑된 실리콘 산화물 복합체;를 포함하여, 상기 리튬티타네이트가 코팅된 천연흑연은 상기 알루미늄이 도핑된 실리콘 산화물 복합체로 피복되며, 상기 알루미늄이 도핑된 실리콘 산화물 복합체는 난흑연화성 탄소와 실리콘 산화물이 결합된 복합체 100 중량부에 알루미늄이 1 내지 10 중량부 도핑된 것을 특징으로 하는 리튬 이차전지 음극재를 제공한다.As an aspect of solving the above problem, natural graphite coated with lithium titanate; and an aluminum-doped silicon oxide composite; including, the lithium titanate-coated natural graphite is covered with the aluminum-doped silicon oxide composite, and the aluminum-doped silicon oxide composite includes non-graphitizable carbon and silicon. Provided is a lithium secondary battery negative electrode material characterized in that 1 to 10 parts by weight of aluminum is doped into 100 parts by weight of the oxide-bonded composite.
일 실시예로 상기 알루미늄이 도핑된 실리콘 산화물 복합체는 리튬티타네이트가 코팅된 천연흑연 100중량부에 대해 1 내지 40중량부로 피복될 수 있다.In one embodiment, the aluminum-doped silicon oxide complex may be coated in an amount of 1 to 40 parts by weight based on 100 parts by weight of lithium titanate-coated natural graphite.
일 실시예로 상기 리튬티타네이트가 코팅된 천연흑연에 있어서, 리튬티타네이트는 천연흑연 100중량부에 대해 0.1 내지 10 중량부로 코팅될 수 있다.In one embodiment, in the natural graphite coated with lithium titanate, lithium titanate may be coated in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of natural graphite.
상기 과제를 해결하기 위한 다른 일 측면으로, 본 발명은 상기 음극재를 포함하여 제조되는 리튬이차 전지를 제공한다.In another aspect to solve the above problem, the present invention provides a lithium secondary battery manufactured including the anode material.
본 발명, 리튬 이차전지 음극재는 리튬티타네이트가 코팅된 천연흑연을 포함하여 리튬티타네이트에 의해 충전 및 방전 사이클 안정성과 열적 부하 용량을 향상시키고, 천연흑연에 의해 리튬티타네이트 에너지 밀도를 보완한다.In the present invention, the lithium secondary battery negative electrode material includes natural graphite coated with lithium titanate, improves charge and discharge cycle stability and thermal load capacity by lithium titanate, and complements the energy density of lithium titanate by natural graphite.
또한, 본 발명의 음극재에 있어서 알루미늄이 도핑된 실리콘 산화물 복합체는 알루미늄이 난흑연화성 탄소와 실리콘 산화물이 결합된 복합체에 도핑된 것으로 실리콘 및 탄소의 팽창 및 탈리의 문제점을 개선하면서도 음극재로서의 성능을 향상시킬 수 있다. In addition, in the anode material of the present invention, the aluminum-doped silicon oxide composite is made by doping aluminum into a composite of non-graphitizable carbon and silicon oxide, improving the problems of expansion and detachment of silicon and carbon while improving the performance as a cathode material. can be improved.
따라서, 리튬티타네이트가 코팅된 천연흑연은 알루미늄이 도핑된 실리콘 산화물 복합체로 피복되어 이러한 효과를 극대화할 수 있다.Therefore, natural graphite coated with lithium titanate can be coated with an aluminum-doped silicon oxide complex to maximize this effect.
본 발명은 리튬 이차전지 음극재에 관한 것으로서, 상세하게는 리튬티타네이트가 코팅된 천연흑연을 알루미늄이 도핑된 실리콘 산화물 복합체로 피복하여, 충전 및 방전 사이클 안정성과 방전용량을 향상시켜 음극재로서 용이하게 사용할 수 있도록 한 것을 특징으로 하는, 리튬 이차전지 음극재에 관한 것이다.The present invention relates to a negative electrode material for lithium secondary batteries, and specifically, covers natural graphite coated with lithium titanate with an aluminum-doped silicon oxide composite to improve charge and discharge cycle stability and discharge capacity, making it easy to use as a negative electrode material. It relates to a lithium secondary battery anode material, characterized in that it can be used easily.
이하, 본 발명을 상세히 설명하도록 한다.Hereinafter, the present invention will be described in detail.
본 발명을 상세하게 설명함에 있어 관련된 공지 기능 또는 구성에 대한 구체적인 설명이 본 발명의 요지를 불필요하게 흐릴 수 있다고 판단되는 경우에는 그 상세한 설명을 생략한다.In describing the present invention in detail, if it is determined that a detailed description of a related known function or configuration may unnecessarily obscure the gist of the present invention, the detailed description will be omitted.
다른 식으로 정의되지 않는 한, 본 명세서에서 사용된 모든 기술적 및 과학적 용어들은 본 발명이 속하는 기술 분야에서 숙련된 전문가에 의해서 통상적으로 이해되는 것과 동일한 의미를 가진다.Unless otherwise defined, all technical and scientific terms used in this specification have the same meaning as commonly understood by a person skilled in the art to which the present invention pertains.
일반적으로, 본 명세서에서 사용된 명명법은 본 기술 분야에서 잘 알려져 있고, 통상적으로 사용되는 것이다.In general, the nomenclature used herein is well known and commonly used in the art.
본 발명의 일 측면에 따르면, 리튬티타네이트가 코팅된 천연흑연; 및According to one aspect of the present invention, natural graphite coated with lithium titanate; and
알루미늄이 도핑된 실리콘 산화물 복합체;를 포함하여, Including aluminum-doped silicon oxide complex,
상기 리튬티타네이트가 코팅된 천연흑연은 상기 알루미늄이 도핑된 실리콘 산화물 복합체로 피복되며,The lithium titanate-coated natural graphite is covered with the aluminum-doped silicon oxide complex,
상기 알루미늄이 도핑된 실리콘 산화물 복합체는 난흑연화성 탄소와 실리콘 산화물이 결합된 복합체 100 중량부에 알루미늄이 1 내지 10 중량부 도핑된 것을 특징으로 하는, 리튬 이차전지 음극재를 제공한다.The aluminum-doped silicon oxide composite provides a lithium secondary battery negative electrode material, characterized in that 1 to 10 parts by weight of aluminum is doped per 100 parts by weight of the composite of non-graphitizable carbon and silicon oxide.
본 발명의 리튬 이차전지 음극재는 리튬티타네이트가 코팅된 천연흑연이 알루미늄이 도핑된 실리콘 산화물 복합체로 피복된 것으로, 상기 리튬티타네이트가 코팅된 천연흑연은, 천연흑연 100중량부에 대해 리튬티타네이트가 0.1 내지 10 중량부로 코팅된다.The lithium secondary battery negative electrode material of the present invention is made by covering natural graphite coated with lithium titanate with a silicon oxide complex doped with aluminum. The natural graphite coated with lithium titanate is lithium titanate relative to 100 parts by weight of natural graphite. is coated in an amount of 0.1 to 10 parts by weight.
천연흑연은 인조흑연에 비해 흑연화도가 높고 저가이며, 높은 리튬이온 저장용량을 나타내는 이점이 있으나, 반면 천연흑연은 입자 형상이 침상 혹은 판상구조(flaky structure)를 보이며 불규칙한 구조로 인해 표면적이 크고 edge면이 그대로 노출이 되기 때문에 전지에 적용 시 전해질의 침투나 분해반응에 의해 edge면이 박리나 파괴되어 비가역 반응이 크게 일어나는 문제점을 갖고 있다.Compared to artificial graphite, natural graphite has a higher degree of graphitization, is cheaper, and has the advantage of high lithium ion storage capacity. However, natural graphite has a needle-like or flaky particle shape and has a large surface area and edges due to its irregular structure. Because the surface is exposed as is, when applied to a battery, there is a problem in that the edge surface is peeled or destroyed due to electrolyte penetration or decomposition reaction, resulting in a large irreversible reaction.
또한, 천연흑연의 판상의 입자는 집전체상에서 평면상으로 배향하기 쉽기 때문에 전해액과의 습윤성이 좋지 않음은 물론이고 낮은 전극밀도를 가지게 된다.In addition, since the plate-shaped particles of natural graphite tend to be oriented in a plane on the current collector, they not only have poor wettability with the electrolyte solution but also have a low electrode density.
한편, 리튬티타네이트는 사이클 안정성(cycle stability), 열적 부하 용량(thermal load capacity) 및 작동 신뢰성이 높고, 리튬에 대하여 상대적으로 일정한 1.55V의 전위차를 가지고 있으며, 20% 미만의 용량 손실로 수천 번의 충전 및 방전 사이클(charge and discharge cycles)을 행할 수 있는 반면에 낮은 전압과 함께 흑연의 372mAh/g(이론치)에 비하여 175mAh/g의 감소된 용량 및 이에 따른 낮은 에너지 밀도를 갖는다.Meanwhile, lithium titanate has high cycle stability, thermal load capacity and operational reliability, has a relatively constant potential difference of 1.55V with respect to lithium, and can be used thousands of times with a capacity loss of less than 20%. While capable of performing charge and discharge cycles, it has a reduced capacity of 175 mAh/g compared to graphite's 372 mAh/g (theoretical value) along with a lower voltage and thus lower energy density.
따라서, 본 발명은 리튬티타네이트의 장점을 가지면서도 단점은 흑연에 의해 보완될 수 있도록 리튬티타네이트가 코팅된 천연흑연을 음극재로서 포함하며, 상기 리튬티타네이트가 코팅된 천연흑연은 천연흑연 100 중량부에 대해 리튬티타네이트는 0.1 내지 10 중량부로 코팅된다.Therefore, the present invention includes natural graphite coated with lithium titanate as a negative electrode material so that it can have the advantages of lithium titanate while complementing the disadvantages with graphite, and the natural graphite coated with lithium titanate is natural graphite 100. Lithium titanate is coated in an amount of 0.1 to 10 parts by weight.
상기 리튬티타네이트가 코팅된 천연흑연에 있어서, 리튬티타네이트가 0.1 중량부 미만으로 포함될 시, 리튬티타네이트에 의한 효과가 거의 나타나지 않으며, 10 중량부를 초과할 시에는 천연흑연을 둘러싼 코팅층의 두께가 두꺼워져 외부와의 접촉이 용이하게 이뤄지지 않아 음극재로서의 효과가 저하될 수 있다. In the natural graphite coated with lithium titanate, when lithium titanate is included in an amount of less than 0.1 parts by weight, the effect of lithium titanate is almost non-existent, and when it exceeds 10 parts by weight, the thickness of the coating layer surrounding the natural graphite increases. As it becomes thick, contact with the outside does not occur easily, which may reduce its effectiveness as a cathode material.
따라서 본 발명은 천연흑연 100 중량부에 대해 리튬티타네이트를 0.1 내지 10 중량부로 코팅하여, 천연흑연 및 리튬티타네이트의 장점을 극대화하면서도 단점을 보완하여 초기 충전 및 방전 효율을 향상시킨다.Therefore, the present invention coats 0.1 to 10 parts by weight of lithium titanate with respect to 100 parts by weight of natural graphite, thereby improving initial charge and discharge efficiency by maximizing the advantages of natural graphite and lithium titanate while complementing their disadvantages.
이때, 리튬티타네이트가 코팅된 천연흑연은, TiO2와 천연흑연을 고상법, 졸겔법(Sol-Gel), 화염분무열분해(flame spray pyrolysis) 또는 무수매질에서의 열수방법(hydrothermal methods)에 의해 제조될 수 있다.At this time, natural graphite coated with lithium titanate is obtained by combining TiO 2 and natural graphite by solid-phase method, sol-gel method, flame spray pyrolysis, or hydrothermal methods in an anhydrous medium. can be manufactured.
본 발명에 있어서, 상기 알루미늄이 도핑된 실리콘 산화물 복합체는 난흑연화성 탄소와 실리콘 산화물이 결합된 복합체에 알루미늄이 도핑된 것으로서, 이때 난흑연화성 탄소와 실리콘 산화물이 결합된 복합체 100중량부에 대해 알루미늄이 1 내지 10중량부로 도핑된다.In the present invention, the aluminum-doped silicon oxide composite is a composite of non-graphitizable carbon and silicon oxide doped with aluminum. In this case, aluminum is added to 100 parts by weight of the composite of non-graphitizable carbon and silicon oxide. It is doped in an amount of 1 to 10 parts by weight.
이는, 상기 알루미늄이 1 중량부 미만으로 도핑될 시, 전기전도성 및 용량 향상의 효과를 얻을 수 없으며, 10 중량부를 초과할 시에는 알루미늄에 따른 효과 증대가 이뤄지지 않음은 물론이고, 구조적인 결합을 야기할 수 있기 때문이다.This means that when the aluminum is doped in less than 1 part by weight, the effect of improving electrical conductivity and capacity cannot be obtained, and when it exceeds 10 parts by weight, the effect due to the aluminum is not increased and causes structural bonding. Because you can.
또한, 상기 알루미늄이 도핑된 실리콘 산화물 복합체에 있어서, 난흑연화성 탄소 100 중량부를 기준으로 실리콘 산화물은 10 내지 100 중량부 포함된다. 이는, 상기 난흑연화성 탄소와 실리콘 산화물은 상기 성분 비율로 복합체를 형성할 때, 실리콘 및 탄소의 팽창 및 탈리의 문제점을 개선하면서도 음극재로서의 성능을 향상시킬 수 있기 때문이다.Additionally, in the aluminum-doped silicon oxide composite, 10 to 100 parts by weight of silicon oxide is included based on 100 parts by weight of non-graphitizable carbon. This is because, when the non-graphitizable carbon and silicon oxide form a composite at the above component ratio, the problems of expansion and detachment of silicon and carbon can be improved while improving performance as a negative electrode material.
상기 난흑연화성 탄소는 하나 이상의 입자 상태로 존재하며, 고온 열처리에 의해서도 흑연화가 되지 않은 비정질의 난흑연성 탄소물질로서, 레진, 목재, 열매의 껍질, 용융단계를 거지지 않는 석탄재료 또는 열경화성 고분자를 탄화시켜 제조될 수 있다.The non-graphitizable carbon is an amorphous non-graphitizable carbon material that exists in the form of one or more particles and is not graphitized even by high-temperature heat treatment, such as resin, wood, fruit peel, coal materials that do not undergo a melting step, or thermosetting polymer. It can be manufactured by carbonizing.
본 발명의 난흑연화성 탄소는 입자크기가 1 내지 100㎛, 바람직하게는 1 내지 20㎛인 바이오매스 유래 탄소인 것을 특징으로 한다.The non-graphitizable carbon of the present invention is characterized as being biomass-derived carbon with a particle size of 1 to 100 ㎛, preferably 1 to 20 ㎛.
바이오매스는 주요성분으로 셀룰로스를 포함하며, 미세섬유가 되도록 정렬되는데, 리그닌 및 헤미셀룰로스와 같은 바인더 매트릭스의 종류와 양에 따라 미세섬유 내 셀룰로스의 정렬도가 달라질 수 있다. Biomass contains cellulose as a major component and is aligned to form microfibers, but the degree of alignment of cellulose within microfibers can vary depending on the type and amount of binder matrix such as lignin and hemicellulose.
이에, 본 발명의 난흑연화성 탄소는 바이오매스 유래 탄소가 리그닌을 80% 이상 포함하는 것을 특징으로 한다.Accordingly, the non-graphitizable carbon of the present invention is characterized in that the biomass-derived carbon contains more than 80% of lignin.
이는, 상기 바이오매스 유래 탄소가 리그닌을 80% 이상 포함할 때, 탄화 시에도 셀룰로스의 미세구조를 유지할 수 있어, 상기 바이오매스 유래 탄소로 제조된 난흑연화성 탄소가 구조적 안정성을 가질 수 있기 때문이다.This is because, when the biomass-derived carbon contains 80% or more of lignin, the microstructure of cellulose can be maintained even during carbonization, and the non-graphitizable carbon manufactured from the biomass-derived carbon can have structural stability. .
또한, 바람직하게는 상기 난흑연화성 탄소는 내부 공극률이 10% 미만인 것을 특징으로 한다.In addition, preferably, the non-graphitizable carbon has an internal porosity of less than 10%.
본 발명의 리튬 이차전지 음극재는 이러한 알루미늄이 도핑된 실리콘 산화물 복합체로 리튬티타네이트가 코팅된 천연흑연이 피복된 것으로, 상기 리튬티타네이트가 코팅된 천연흑연 100 중량부에 대해 알루미늄이 도핑된 실리콘 산화물 복합체는 1 내지 40중량부 피복된다.The lithium secondary battery negative electrode material of the present invention is a composite of aluminum-doped silicon oxide coated with lithium titanate-coated natural graphite, and is obtained by mixing aluminum-doped silicon oxide with respect to 100 parts by weight of the lithium titanate-coated natural graphite. The composite is coated in an amount of 1 to 40 parts by weight.
이는, 상기 알루미늄이 도핑된 실리콘 산화물 복합체가 1 중량부 미만으로 포함될 시, 방전용량 향상의 효과가 미미하게 나타나며, 40 중량부를 초과할 시에는 피복이 용이하게 이뤄지지 않음은 물론이고, 리튬티타네이트가 코팅된 천연흑연과 알루미늄이 도핑된 실리콘 산화물 복합체의 구조적 안정성이 깨어져 음극재로서의 효과가 저하되기 때문이다.This means that when the aluminum-doped silicon oxide complex is contained in an amount of less than 1 part by weight, the effect of improving discharge capacity appears slightly, and when it exceeds 40 parts by weight, coating is not easily achieved, and lithium titanate This is because the structural stability of the coated natural graphite and aluminum-doped silicon oxide composite is broken, reducing its effectiveness as a cathode material.
상술한 바와 같이, 본 발명의 음극재는 알루미늄이 도핑된 실리콘 산화물 복합체로 리튬티타네이트가 코팅된 천연흑연이 피복되어, 리튬티타네이트에 의한 충전 및 방전 사이클 안정성과 열적 부하 용량을 향상시킴은 물론이고, 알루미늄이 도핑된 실리콘 산화물 복합체에 의해 방전용량을 향상시킬 수 있다.As described above, the anode material of the present invention is a silicon oxide composite doped with aluminum and covered with natural graphite coated with lithium titanate, thereby improving charge and discharge cycle stability and thermal load capacity by lithium titanate. , discharge capacity can be improved by aluminum-doped silicon oxide complex.
이에, 본 발명의 다른 일 측면에 따르면, 상기 음극재를 포함하여 제조되는 리튬이온 전지를 제공한다.Accordingly, according to another aspect of the present invention, a lithium ion battery manufactured including the anode material is provided.
이하, 본 발명의 보다 구체적인 설명을 위하여 실시예를 들어 설명한다. 그러나, 하기 실시예는 본 발명의 발마직한 실시예일 뿐 본 발명이 하기 실시예에 한정되는 것은 아니다.Hereinafter, for a more detailed description of the present invention, examples will be given. However, the following examples are merely exemplary examples of the present invention and the present invention is not limited to the following examples.
<실시예><Example>
1. 음극재 제조1. Anode material manufacturing
<실시예 1><Example 1>
천연흑연 100 중량부에 리튬티타네이트를 5 중량부로 코팅하여, 리튬티타네이트가 코팅된 천연흑연을 제조하였다.Natural graphite coated with lithium titanate was prepared by coating 5 parts by weight of lithium titanate on 100 parts by weight of natural graphite.
다음으로 입자크기가 10㎛인 바이오매스 유래의 난흑연화성 탄소 100 중량부에 실리콘 산화물 30 중량부가 결합된 복합체 100중량부에 대해 알루미늄이 3 중량부 도핑된, 알루미늄이 도핑된 실리콘 산화물 복합체를 제조하여, 상기 리튬티타네이트가 코팅된 천연흑연 100 중량부에 대해 상기 알루미늄이 도핑된 실리콘 산화물 복합체를 30 중량부 피복하여 음극재를 제조하였다. Next, an aluminum-doped silicon oxide composite was prepared in which 3 parts by weight of aluminum was doped with 100 parts by weight of silicon oxide combined with 100 parts by weight of non-graphitizable carbon derived from biomass with a particle size of 10 ㎛. Thus, a negative electrode material was manufactured by coating 30 parts by weight of the aluminum-doped silicon oxide composite with 100 parts by weight of the lithium titanate-coated natural graphite.
<비교예 1><Comparative Example 1>
상기 알루미늄이 도핑된 실리콘 산화물을 복합체를 코팅하지 않은 것을 제외하고는 실시예 1과 동일한 방법으로 음극재를 제조하였다.A negative electrode material was manufactured in the same manner as in Example 1, except that the aluminum-doped silicon oxide composite was not coated.
<비교예 2><Comparative Example 2>
상기 알루미늄이 도핑된 실리콘 산화물을 복합체만으로 이루어진 것을 제외하고는 실시예 1과 동일한 방법으로 음극재를 제조하였다.A negative electrode material was manufactured in the same manner as in Example 1, except that it consisted only of the aluminum-doped silicon oxide composite.
2. 실험예2. Experimental example
상기 제조된 음극재에 대한 전기화학적 특성을 측정하기 위하여, 산소와 수분을 제거한 아르곤 박스에서 코인 셀을 제작하였다.In order to measure the electrochemical properties of the manufactured anode material, a coin cell was manufactured in an argon box from which oxygen and moisture were removed.
상기 코인셀은 상기 제조된 음극재를 포함하여, 상대 전극으로 Li 금속, 분리막으로 폴리프로필렌, 전해질로서 1M의 LiPF6 염과 1:1의 부피비로 혼합된 에틸 메틸 카보네이트와 디메틸 카보네이트 용매로 구성된 전해액을 사용하였다.The coin cell includes the cathode material prepared above, Li metal as a counter electrode, polypropylene as a separator, and an electrolyte consisting of 1M LiPF 6 salt and ethyl methyl carbonate and dimethyl carbonate solvent mixed in a volume ratio of 1:1 as an electrolyte. was used.
상기 샘플마다 제작한 코인 셀을 0.05C의 정전류로 전압이 0.01V가 될 때까지 충전하고 0.05C의 정전류로 전압이 1.5V가 될 때까지 방전하여 초기 효율을 구하였으며, 이후 사이클 특성은 0.2C의 정전류로 위와 동일한 전압범위에서 실시하여 용량유지율 시험을 진행하고 그 결과를 하기 표 1에 나타내었다.The coin cell manufactured for each sample was charged at a constant current of 0.05C until the voltage reached 0.01V and discharged at a constant current of 0.05C until the voltage reached 1.5V to obtain the initial efficiency, and the subsequent cycle characteristics were 0.2C. The capacity retention rate test was conducted in the same voltage range as above at a constant current of , and the results are shown in Table 1 below.
(방전용량/충전용량)Initial efficiency (%)
(discharge capacity/charge capacity)
(30 cycle)Capacity maintenance rate (%)
(30 cycles)
상기 표 1을 통해, 상기 실시예 1의 음극재를 포함한 경우는 초기효율 및 용량 유지율 모두 우수하게 나타나는 반면, 비교예 1 및 2는 초기효율 및 용량 유지율 모두에서 실시예 1에 비해 감소된 효율을 내었다.Through Table 1, when the anode material of Example 1 was included, both initial efficiency and capacity maintenance rate were excellent, while Comparative Examples 1 and 2 showed reduced efficiency compared to Example 1 in both initial efficiency and capacity maintenance rate. I paid it.
Claims (4)
알루미늄이 도핑된 실리콘 산화물 복합체;를 포함하여,
상기 리튬티타네이트가 코팅된 천연흑연은 상기 알루미늄이 도핑된 실리콘 산화물 복합체로 피복되며,
상기 알루미늄이 도핑된 실리콘 산화물 복합체는 난흑연화성 탄소와 실리콘 산화물이 결합된 복합체 100 중량부에 알루미늄이 1 내지 10 중량부 도핑된 것을 특징으로 하는 리튬 이차전지 음극재.
Natural graphite coated with lithium titanate; and
Including aluminum-doped silicon oxide complex,
The lithium titanate-coated natural graphite is covered with the aluminum-doped silicon oxide complex,
The aluminum-doped silicon oxide composite is a lithium secondary battery negative electrode material, characterized in that 1 to 10 parts by weight of aluminum is doped to 100 parts by weight of a composite of non-graphitizable carbon and silicon oxide.
상기 알루미늄이 도핑된 실리콘 산화물 복합체는 리튬티타네이트가 코팅된 천연흑연 100중량부에 대해 1 내지 40중량부로 피복되는 것을 특징으로 하는 리튬 이차전지 음극재.
According to claim 1,
A lithium secondary battery negative electrode material, characterized in that the aluminum-doped silicon oxide composite is covered in an amount of 1 to 40 parts by weight based on 100 parts by weight of natural graphite coated with lithium titanate.
상기 리튬티타네이트가 코팅된 천연흑연에 있어서, 리튬티타네이트는 천연흑연 100중량부에 대해 0.1 내지 10 중량부로 코팅되는 것을 특징으로 하는 리튬 이차전지 음극재.
According to claim 1,
In the lithium titanate-coated natural graphite, lithium titanate is coated in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of natural graphite.
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| KR102228654B1 (en) | 2019-08-29 | 2021-03-17 | 한양대학교 산학협력단 | Anode active material, method for preparing the same, and rechargeable lithium battery comprising the same |
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