KR102643130B1 - Manufacturing methods of electrode material for lithium secondary batteries and eletrode material manufactured by the method - Google Patents
Manufacturing methods of electrode material for lithium secondary batteries and eletrode material manufactured by the method Download PDFInfo
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- KR102643130B1 KR102643130B1 KR1020160154296A KR20160154296A KR102643130B1 KR 102643130 B1 KR102643130 B1 KR 102643130B1 KR 1020160154296 A KR1020160154296 A KR 1020160154296A KR 20160154296 A KR20160154296 A KR 20160154296A KR 102643130 B1 KR102643130 B1 KR 102643130B1
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- lithium secondary
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- secondary battery
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 56
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 239000007772 electrode material Substances 0.000 title claims abstract description 43
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 28
- 239000000463 material Substances 0.000 title description 3
- 150000002736 metal compounds Chemical class 0.000 claims abstract description 29
- 229910021426 porous silicon Inorganic materials 0.000 claims abstract description 28
- 238000001694 spray drying Methods 0.000 claims abstract description 18
- 230000003647 oxidation Effects 0.000 claims abstract description 11
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims description 22
- 238000005530 etching Methods 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 13
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 11
- 229910052710 silicon Inorganic materials 0.000 claims description 11
- 239000010703 silicon Substances 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- 239000011777 magnesium Substances 0.000 claims description 6
- 239000011817 metal compound particle Substances 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 230000001976 improved effect Effects 0.000 abstract description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 18
- 229910019018 Mg 2 Si Inorganic materials 0.000 description 13
- 239000000395 magnesium oxide Substances 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 230000008569 process Effects 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 230000002427 irreversible effect Effects 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 229910003481 amorphous carbon Inorganic materials 0.000 description 2
- 239000006183 anode active material Substances 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229910000765 intermetallic Inorganic materials 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910002981 Li4.4Si Inorganic materials 0.000 description 1
- 229910002980 Li4.4Sn Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 229910007070 SnP0.94 Inorganic materials 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000002388 carbon-based active material Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 230000001684 chronic effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000003311 flocculating effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 238000006713 insertion reaction Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000011834 metal-based active material Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/06—Metal silicides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/02—Silicon
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F5/00—Compounds of magnesium
- C01F5/02—Magnesia
-
- 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
- H01M4/134—Electrodes based on metals, Si 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
-
- 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
- H01M4/386—Silicon or alloys based on silicon
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/50—Agglomerated particles
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- 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 2차 전지용 전극물질의 제조방법 및 그에 의해 제조된 리튬 2차 전지용 전극물질에 관한 것으로, 상세하게는 분무건조법을 이용하여 금속화합물을 응집시킨 후 공기 산화 탈마그네슘화 방법을 통해 멀티 다공성 실리콘을 제조하여 상기 멀티 다공성 실리콘을 리튬 2차 전지용 전극에 적용시킴으로써, 충방전 용량 및 사이클 특성이 향상된 리튬 2차 전지용 전극물질의 제조방법 및 그에 의해 제조된 리튬 2차 전지용 전극물질에 관한 것이다. The present invention relates to a method for manufacturing an electrode material for lithium secondary batteries and an electrode material for lithium secondary batteries produced thereby. In detail, the present invention relates to a method of agglomerating a metal compound using a spray drying method and then using an air oxidation demagnesization method to form a multi-layer metal compound. The present invention relates to a method of manufacturing an electrode material for a lithium secondary battery with improved charge/discharge capacity and cycle characteristics by manufacturing porous silicon and applying the multi-porous silicon to an electrode for a lithium secondary battery, and to an electrode material for a lithium secondary battery produced thereby. .
Description
본 발명은 리튬 2차 전지용 전극물질의 제조방법 및 그에 의해 제조된 리튬 2차 전지용 전극물질에 관한 것으로, 상세하게는 멀티 다공성 실리콘의 제조방법과 상기 제조방법에 의해 제조된 멀티 다공성 실리콘을 리튬 2차 전지용 전극에 적용시킴으로써, 충방전 용량 및 사이클 특성이 향상된 리튬 2차 전지용 전극물질의 제조방법 및 그에 의해 제조된 리튬 2차 전지용 전극물질에 관한 것이다. The present invention relates to a method for manufacturing an electrode material for a lithium secondary battery and an electrode material for a lithium secondary battery manufactured thereby. In particular, it relates to a method for manufacturing multi-porous silicon and the method for producing multi-porous silicon produced by the method as lithium 2. It relates to a method of manufacturing an electrode material for lithium secondary batteries with improved charge/discharge capacity and cycle characteristics by applying it to electrodes for secondary batteries, and to an electrode material for lithium secondary batteries manufactured thereby.
리튬 이차 전지는 가역적으로 리튬 이온의 삽입 및 탈리가 가능한 물질을 양극 및 음극으로 사용하고, 상기 양극과 음극 사이에 유기 전해액 또는 폴리머 전해액을 충전시켜 제조하며, 리튬 이온이 양극 및 음극에서 삽입/탈리될 때의 산화, 환원 반응에 의하여 전기 에너지를 생성한다.Lithium secondary batteries are manufactured by using materials capable of reversibly inserting and desorbing lithium ions as the anode and cathode, and filling an organic electrolyte or polymer electrolyte between the anode and the cathode, and inserting/desorbing lithium ions into and out of the anode and cathode. Electrical energy is generated through oxidation and reduction reactions.
리튬 이차 전지의 음극 활물질로는 리튬 금속을 사용하였으나, 리튬 금속을 사용할 경우 덴드라이트(dendrite)의 형성으로 인한 전지 단락에 의해 폭발 위험성이 있으며 충방전의 낮은 효율에 대한 문제점이 있다. 이와 같은 문제점을 극복하고자 리튬 금속을 대체하는 음극 활물질로서 비정질 탄소 또는 결정질 탄소 등의 탄소계 물질이 제시되어 음극 재료로 이용되고 있다.Lithium metal is used as a negative electrode active material for lithium secondary batteries, but when lithium metal is used, there is a risk of explosion due to battery short circuit due to the formation of dendrites and there is a problem with low charging and discharging efficiency. To overcome these problems, carbon-based materials such as amorphous carbon or crystalline carbon have been proposed as anode active materials to replace lithium metal and are being used as anode materials.
그러나 탄소계 활물질로는 천연 흑연과 인조흑연등의 결정성 탄소와 소프트 카본 및 하드 카본 등의 비결정성 탄소가 있다. 흑연의 경우 한계 용량이 372 mAh/g으로서 제한적이므로 고용량화가 어렵다는 단점을 가지고 있으며, 이러한 탄소계 물질은 초기 수 사이클 동안 5 내지 30 %의 비가역 특성을 나타내며, 이러한 비가역 용량은 리튬 이온을 소모시켜 최소 1개 이상의 활물질을 완전히 충전 또는 방전하지 못하게 함으로써, 전지의 에너지 밀도면에서 불리하게 작용한다. 나아가서 차세대 리튬 이차 전지용 고용량 음극 소재로서 주목을 받고 있는 Si, Sn계 금속계 활물질의 경우 열역학적으로 Li4.4Si, Li4.4Sn 등의 금속간 화합물 형성 반응에 근거하여 약 3,500 ~ 4,200 mAh/g의 전기화학적 충/방전 용량이 실험적으로 구현되지만 이와 동시에 Li과의 반응이 진행될수록 생성되는 새로운 금속간 화합물상에 기인한 급격한 격자 부피 변화(300 ~ 400 %)에 의하여 전극 수명 열세 현상 등의 극복되기 어려운 기술적 문제점을 안고 있으며, 특히 Si, Sn 등의 금속 음극 활물질은 비가역 특성이 더욱 큰 문제가 된다.However, carbon-based active materials include crystalline carbon such as natural graphite and artificial graphite, and amorphous carbon such as soft carbon and hard carbon. In the case of graphite, the limiting capacity is limited to 372 mAh/g, so it has the disadvantage of being difficult to achieve high capacity. These carbon-based materials exhibit irreversible characteristics of 5 to 30% during the initial few cycles, and this irreversible capacity consumes lithium ions, resulting in a minimum By preventing one or more active materials from being fully charged or discharged, it has a disadvantage in terms of energy density of the battery. Furthermore, in the case of Si and Sn-based metal-based active materials, which are attracting attention as high-capacity anode materials for next-generation lithium secondary batteries, the electrochemical value is about 3,500 to 4,200 mAh/g based on the thermodynamic reaction of forming intermetallic compounds such as Li4.4Si and Li4.4Sn. The charge/discharge capacity is implemented experimentally, but at the same time, it is difficult to overcome technical difficulties such as the electrode life inferiority phenomenon due to the rapid lattice volume change (300 ~ 400%) due to the new intermetallic compound phase that is created as the reaction with Li progresses. There are problems, and in particular, metal anode active materials such as Si and Sn have irreversible characteristics, which is an even bigger problem.
금속계 음극 소재의 Li과의 전기화학적 반응 시에 급격한 격자 부피 팽창에 기인한 전극 퇴화 현상을 개선하기 위하여 다공성 나노 소재 및 해당 전극 설계를 통하여 가역성 증대 및 부피 팽창 현상을 효과적으로 해결할 수 있는 방법 등이 제시되고 있지만 이론적인 에너지 밀도에 비하여 실제 전극 레벨에서의 에너지 밀도 등이 상용화된 기존 음극 소재와 비교하여 그다지 높지 않으며 또한 고질적인 퇴화 현상은 아직 완벽하게 제어되기 어려운 실정이다.In order to improve the phenomenon of electrode degradation caused by rapid lattice volume expansion during the electrochemical reaction of metallic cathode materials with Li, methods to increase reversibility and effectively solve the volume expansion phenomenon through porous nanomaterials and corresponding electrode design are presented. However, compared to the theoretical energy density, the energy density at the actual electrode level is not that high compared to existing commercially available cathode materials, and the chronic deterioration phenomenon is still difficult to completely control.
이러한 문제를 해결하기 위해서, MX (M=Si,Sn,Al,V,Mn,Co.., X=S,P,N,O) 타입(type)의 금속계 소재 중에서 MnP, SnP0.94 등의 층구조(layered structure)를 가진 일부 화합물이 Li과의 반응시에 기존 합금(alloying) 또는 전이(conversion) 반응이 아닌 부분적으로 편입(insertion)되는 반응을 하는 것으로 보고되고 있다.To solve this problem, among the MX (M=Si,Sn,Al,V,Mn,Co.., X=S,P,N,O) type metal materials, MnP, SnP0.94, etc. It has been reported that some compounds with a layered structure undergo a partial insertion reaction rather than a conventional alloying or conversion reaction when reacting with Li.
하지만 여전히 높은 Li 반응 전위와 초기 싸이클이 진행되는 동안 가역 효율이 100 % 근접하게 도달하는데 20싸이클(cycle) 이상이 소요되는 느린 활성화 속도가 문제가 되고, 또한 일정량 이상의 Li이 충전될 경우 전이(conversion) 반응으로 변환되어 전극 수명에 치명적인 영향을 미치므로 제한적인 충방전 전위 범위에서 작동되어야 하는 단점이 있다.However, the still high Li reaction potential and the slow activation speed that takes more than 20 cycles to reach 100% reversible efficiency during the initial cycle are problems, and conversion occurs when a certain amount of Li is charged. ) It is converted into a reaction and has a fatal impact on the lifespan of the electrode, so it has the disadvantage of having to be operated in a limited charge/discharge potential range.
본 발명은 상기와 같은 문제를 해결하기 위한 것으로, 분무건조법을 이용하여 금속화합물을 응집시킨 후 공기 산화 탈마그네슘화 방법을 통해 멀티 다공성 실리콘을 제조하여 상기 멀티 다공성 실리콘을 리튬 2차 전지용 전극에 적용시킴으로써, 충방전 용량 및 사이클 특성이 향상되도록 하는 리튬 2차 전지용 전극물질의 제조방법 및 그에 의해 제조된 리튬 2차 전지용 전극물질을 제공하는데 목적이 있다. The present invention is intended to solve the above problems, by flocculating a metal compound using a spray drying method, manufacturing multi-porous silicon through an air oxidation demagnesization method, and applying the multi-porous silicon to an electrode for a lithium secondary battery. The purpose of the present invention is to provide a method for manufacturing an electrode material for a lithium secondary battery that improves charge/discharge capacity and cycle characteristics, and an electrode material for a lithium secondary battery manufactured thereby.
또한, 본 발명의 제조방법에 의해 제조된 멀티 다공성 실리콘은 충방전 과정에서 부피팽창으로 인한 열화를 억제하여 리튬 2차 전지의 성능을 향상시키도록 하는 리튬 2차 전지용 전극물질의 제조방법 및 그에 의해 제조된 리튬 2차 전지용 전극물질을 제공하는데 목적이 있다.In addition, the multi-porous silicon manufactured by the manufacturing method of the present invention is a method of manufacturing an electrode material for lithium secondary batteries that improves the performance of lithium secondary batteries by suppressing deterioration due to volume expansion during the charging and discharging process, and thereby The purpose is to provide electrode materials for manufactured lithium secondary batteries.
본 발명의 일 측면에 따른 리튬 2차 전지용 전극물질의 제조방법은 30 ~ 50 ㎛의 입경 크기를 가진 실리콘과 200 ~ 500 ㎛의 입경 크기를 가진 마그네슘을 혼합하여 금속 혼합물을 수득하는 단계(S10)와, 상기 혼합물을 1차 열처리하여 금속 화합물을 수득하는 단계(S20)와, 상기 금속 화합물을 분무건조 처리하여 금속 화합물의 입자를 응집시키는 단계(S30)와, 상기 응집된 금속 화합물을 2차 열처리하는 단계(S40), 및 상기 2차 열처리 후 에칭 용액으로 1 ~ 10 시간 동안 에칭하는 단계(S50)를 포함할 수 있다. A method of manufacturing an electrode material for a lithium secondary battery according to an aspect of the present invention includes mixing silicon with a particle size of 30 to 50 ㎛ and magnesium with a particle size of 200 to 500 ㎛ to obtain a metal mixture (S10). A step of obtaining a metal compound by first heat treating the mixture (S20), a step of spray drying the metal compound to agglomerate the particles of the metal compound (S30), and secondary heat treatment of the agglomerated metal compound. It may include a step (S40), and a step (S50) of etching with an etching solution for 1 to 10 hours after the secondary heat treatment.
상기 1차 열처리는 아르곤, 헬륨, 및 질소로 이루어진 군으로부터 선택된 어느 하나의 비활성 기체 분위기하에 수행되는 것을 특징으로 한다. The first heat treatment is characterized in that it is performed under an inert gas atmosphere selected from the group consisting of argon, helium, and nitrogen.
상기 1차 열처리는 400 ~ 900 ℃에서 3 ~ 8 시간 동안 수행되는 것을 특징으로 한다.The first heat treatment is characterized in that it is performed at 400 to 900 ° C. for 3 to 8 hours.
상기 분무건조는 150 ~ 250 ℃에서 20 ~ 80 cc의 드라이 유량으로 수행되는 것을 특징으로 한다. The spray drying is characterized in that it is performed at a dry flow rate of 20 to 80 cc at 150 to 250 ° C.
상기 2차 열처리는 공기 산화 탈마그네슘 반응(air oxidation demagnesiation)으로 수행되는 것을 특징으로 한다.The secondary heat treatment is characterized in that it is performed by air oxidation demagnesiation.
상기 2차 열처리는 공기 분위기하에 500 ~ 900 ℃에서 5 ~ 24 시간 동안 수행되는 것을 특징으로 한다. The secondary heat treatment is characterized in that it is performed for 5 to 24 hours at 500 to 900 ° C. in an air atmosphere.
상기 에칭 용액은 염산, 황산, 인산, 질산, 및 아세트산으로 이루어진 군으로부터 선택된 어느 하나인 것이 바람직하다.The etching solution is preferably any one selected from the group consisting of hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, and acetic acid.
본 발명의 다른 측면에 따른 리튬 2차 전지용 전극물질은 상기 제조방법에 의해 제조된 다공성 실리콘을 포함할 수 있다. An electrode material for a lithium secondary battery according to another aspect of the present invention may include porous silicon manufactured by the above manufacturing method.
상기와 같이 본 발명에 따른 리튬 2차 전지용 전극물질의 제조방법 및 그에 의해 제조된 리튬 2차 전지용 전극물질은 분무건조법을 이용하여 금속화합물을 응집시킨 후 공기 산화 탈마그네슘화 방법을 통해 멀티 다공성 실리콘을 제조하여 상기 멀티 다공성 실리콘을 리튬 2차 전지용 전극에 적용시킴으로써, 충방전 용량 및 사이클 특성이 향상되는 효과가 있다. As described above, the method for producing an electrode material for a lithium secondary battery according to the present invention and the electrode material for a lithium secondary battery manufactured thereby are made by agglomerating a metal compound using a spray drying method and then forming multi-porous silicon through an air oxidation demagnesization method. By manufacturing and applying the multi-porous silicon to electrodes for lithium secondary batteries, charge/discharge capacity and cycle characteristics are improved.
또한, 본 발명에 의해 제조된 멀티 다공성 실리콘은 충방전 과정에서 부피팽창으로 인한 열화를 억제하여 리튬 2차 전지의 성능이 향상되는 효과가 있다.In addition, the multi-porous silicon manufactured by the present invention has the effect of improving the performance of lithium secondary batteries by suppressing deterioration due to volume expansion during the charging and discharging process.
도 1은 본 발명의 일 측면에 따른 리튬 2차 전지용 전극질의 제조방법을 나타내는 플로우 차트이다.
도 2는 본 발명의 일 측면에 따른 리튬 2차 전지용 전극물질의 제조방법을 나타내는 개념도이다.
도 3은 본 발명의 일 측면에 따른 리튬 2차 전지용 전극물질의 제조방법의 단계별 XRD 패턴을 나타낸 그래프이다((a) 분무건조 후, (b) 공기 산화 탈마그네슘화 후, (c) 에칭 후).
도 4는 본 발명의 일 측면에 따른 리튬 2차 전지용 전극물질의 제조방법의 단계별 주사 전자 현미경(SEM) 이미지이다((a) 분무건조 후, (b) 에칭 후).
도 5는 본 발명의 일 측면에 따른 리튬 2차 전지용 전극물질에 따른 초기 화성 사이클의 충방전 전위에 따른 충방전 용량의 변화를 나타낸 그래프(a) 및 충방전 사이클 특성을 측정한 그래프(b)이다.1 is a flow chart showing a method of manufacturing an electrode material for a lithium secondary battery according to one aspect of the present invention.
Figure 2 is a conceptual diagram showing a method of manufacturing an electrode material for a lithium secondary battery according to one aspect of the present invention.
Figure 3 is a graph showing step-by-step ).
Figure 4 is a step-by-step scanning electron microscope (SEM) image of the method for manufacturing an electrode material for a lithium secondary battery according to one aspect of the present invention ((a) after spray drying, (b) after etching).
Figure 5 is a graph showing the change in charge/discharge capacity according to the charge/discharge potential of the initial chemical cycle according to the electrode material for a lithium secondary battery according to an aspect of the present invention (a) and a graph (b) measuring charge/discharge cycle characteristics. am.
본 발명은 다양한 변경을 가할 수 있고 여러 가지 실시예를 가질 수 있는 바, 특정 실시예들을 도면에 예시하고 상세한 설명에 상세하게 설명하고자 한다. 그러나, 이는 본 발명을 특정한 실시 형태에 대해 한정하려는 것이 아니며, 본 발명의 사상 및 기술 범위에 포함되는 모든 변경, 균등물 내지 대체물을 포함하는 것으로 이해되어야 한다.Since the present invention can make various changes and have various embodiments, specific embodiments will be illustrated in the drawings and described in detail in the detailed description. However, this is not intended to limit the present invention to specific embodiments, and should be understood to include all changes, equivalents, and substitutes included in the spirit and technical scope of the present invention.
본원 명세서 전체에서, 어떤 부분이 어떤 구성요소를 "포함" 한다고 할 때, 이는 특별히 반대되는 기재가 없는 한 다른 구성요소를 제외하는 것이 아니라 다른 구성 요소를 더 포함할 수 있는 것을 의미한다. Throughout the specification of the present application, when a part is said to “include” a certain element, this means that it may further include other elements rather than excluding other elements, unless specifically stated to the contrary.
이하, 본 발명의 일 측면에 따른 리튬 2차 전지용 전극물질의 제조방법은 첨부한 도면을 참조로 하여 상세히 설명한다. 본 발명은 이하에서 개시되는 실시예에 한정되는 것이 아니라 서로 다른 다양한 형태로 구현될 수 있으며, 단지 본 실시예는 본 발명의 개시가 완전하도록 하며 통상의 지식을 가진 자에게 발명의 범주를 완전하게 알려주기 위하여 제공되는 것이다.Hereinafter, a method for manufacturing an electrode material for a lithium secondary battery according to one aspect of the present invention will be described in detail with reference to the attached drawings. The present invention is not limited to the embodiments disclosed below, but may be implemented in various different forms. However, the present embodiments only serve to complete the disclosure of the present invention and to fully convey the scope of the invention to those skilled in the art. It is provided for information purposes only.
도 1은 본 발명의 일 측면에 따른 리튬 2차 전지용 전극질의 제조방법을 나타내는 플로우 차트이고, 도 2는 본 발명의 일 측면에 따른 리튬 2차 전지용 전극물질의 제조방법을 나타내는 개념도이다. FIG. 1 is a flow chart showing a method of manufacturing an electrode material for a lithium secondary battery according to an aspect of the present invention, and FIG. 2 is a conceptual diagram showing a method of manufacturing an electrode material for a lithium secondary battery according to an aspect of the present invention.
본 발명의 일 측면에 따른 리튬 2차 전지용 전극물질의 제조방법은 30 ~ 50 ㎛의 입경 크기를 가진 실리콘과 200 ~ 500 ㎛의 입경 크기를 가진 마그네슘을 혼합하여 금속 혼합물을 수득하는 단계(S10)와, 상기 혼합물을 1차 열처리하여 금속 화합물을 수득하는 단계(S20)와, 상기 금속 화합물을 분무건조 처리하여 금속 화합물의 입자를 응집시키는 단계(S30)와, 상기 응집된 금속 화합물을 2차 열처리하는 단계(S40), 및 상기 2차 열처리 후 에칭 용액으로 1 ~ 10 시간 동안 에칭하는 단계(S50)를 포함한다.A method of manufacturing an electrode material for a lithium secondary battery according to an aspect of the present invention includes mixing silicon with a particle size of 30 to 50 ㎛ and magnesium with a particle size of 200 to 500 ㎛ to obtain a metal mixture (S10). A step of obtaining a metal compound by first heat treating the mixture (S20), a step of spray drying the metal compound to agglomerate the particles of the metal compound (S30), and secondary heat treatment of the agglomerated metal compound. A step (S40), and a step (S50) of etching with an etching solution for 1 to 10 hours after the secondary heat treatment.
본 발명의 제조방법을 각 단계별로 나누어서 설명하면 다음과 같다.The manufacturing method of the present invention is explained in each step as follows.
우선, 30 ~ 50 ㎛의 입경 크기를 가진 실리콘과 200 ~ 500 ㎛의 입경 크기를 가진 마그네슘을 혼합하여 금속 혼합물을 수득하는 단계(S10)를 수행한다. First, a step (S10) is performed to obtain a metal mixture by mixing silicon with a particle size of 30 to 50 ㎛ and magnesium with a particle size of 200 to 500 ㎛.
상기 실리콘과 마그네슘은 2 : 1 중량비로 혼합하여 임의의 교반기(stirrer)에서 500 ~ 2,000 rpm의 속도로 교반하여 금속 혼합물을 수득한다. The silicon and magnesium are mixed at a weight ratio of 2:1 and stirred at a speed of 500 to 2,000 rpm in a stirrer to obtain a metal mixture.
다음으로, 상기 혼합물을 1차 열처리하여 금속 화합물을 수득하는 단계(S20)를 수행한다. Next, a step (S20) of first heat treating the mixture to obtain a metal compound is performed.
상기 1차 열처리는 아르곤, 헬륨, 및 질소로 이루어진 군으로부터 선택된 어느 하나의 비활성 기체 분위기하에 400 ~ 900 ℃에서 3 ~ 8 시간 동안 수행된다.The first heat treatment is performed at 400 to 900° C. for 3 to 8 hours under an inert gas atmosphere selected from the group consisting of argon, helium, and nitrogen.
상기 단계(S10)에서 수득된 금속 혼합물은 1차 열처리 과정을 거치게 되면 Mg2Si 형태의 금속 화합물이 수득되며, 상기 금속 화합물의 구조가 치밀해진다.When the metal mixture obtained in step (S10) undergoes a first heat treatment process, a metal compound in the form of Mg 2 Si is obtained, and the structure of the metal compound becomes dense.
그 다음, 상기 금속 화합물을 분무건조 처리하여 금속 화합물의 입자를 응집시키는 단계(S30)를 수행한다. Next, a step (S30) is performed to agglomerate particles of the metal compound by spray drying the metal compound.
상기 단계(S20)에서 수득된 금속 화합물은 증류수 또는 유기 용매와 혼합하여 150 ~ 250 ℃에서 20 ~ 80 cc의 드라이 유량으로 분무건조 처리를 한다. 도 2와 도 4(a)에서 보는 바와 같이, 상기 분무건조에 의해 금속 화합물의 입자가 응집된다. 상기 분무건조는 다공성 실리콘을 제조하기 위한 전처리 과정으로, 상기 분무건조에 의해 금속 화합물이 조밀하게 응집되어 후술하게 되는 에칭 과정을 통해 균일한 다공성 실리콘을 수득할 수 있다. The metal compound obtained in step (S20) is mixed with distilled water or an organic solvent and subjected to spray drying at 150 to 250°C at a dry flow rate of 20 to 80 cc. As shown in Figures 2 and 4(a), the particles of the metal compound are aggregated by the spray drying. The spray drying is a pretreatment process for producing porous silicon. The metal compound is densely aggregated through the spray drying, and uniform porous silicon can be obtained through an etching process to be described later.
상기 유기 용매는 메탄올, 에탄올, 프로판올, 아세톤, 글리세린, 및 에틸렌 글리콜으로 이루어진 군으로부터 선택된 어느 하나인 것이 바람직하다. 상기 유기 용매는 휘발성이 높은 용매로 분무건조시 용매가 빠르게 증발되면서 금속 화합물이 빠르게 응집되도록 하는 역할을 한다. The organic solvent is preferably any one selected from the group consisting of methanol, ethanol, propanol, acetone, glycerin, and ethylene glycol. The organic solvent is a highly volatile solvent, and during spray drying, the solvent quickly evaporates and serves to quickly coagulate the metal compound.
그 다음, 상기 응집된 금속 화합물을 2차 열처리하는 단계(S40)를 수행한다. Next, a secondary heat treatment step (S40) is performed on the aggregated metal compound.
상기 2차 열처리는 공기 산화 탈마그네슘 반응(air oxidation demagnesiation)으로, 공기 분위기하에 500 ~ 900 ℃에서 5 ~ 24 시간 동안 수행되는 것을 특징으로 한다. The secondary heat treatment is air oxidation demagnesiation and is characterized in that it is performed at 500 to 900 ° C. for 5 to 24 hours in an air atmosphere.
즉, 하기 반응식에서 보는 바와 같이, 상기 공기 산화 탈마그네슘 반응을 통해 응집된 금속 화합물이 실리콘과 산화 마그네슘으로 생성된다.That is, as shown in the reaction equation below, the aggregated metal compound is produced into silicon and magnesium oxide through the air oxidation demagnesium reaction.
[반응식][Reaction formula]
Mg2Si + O2 (air) → Si + MgOMg 2 Si + O 2 (air) → Si + MgO
마지막으로, 상기 2차 열처리 후 에칭 용액으로 1 ~ 10 시간 동안 에칭하는 단계(S50)를 수행한다. Finally, after the secondary heat treatment, a step (S50) of etching with an etching solution for 1 to 10 hours is performed.
상기 에칭 용액은 염산, 황산, 인산, 질산, 및 아세트산으로 이루어진 군으로부터 선택된 어느 하나인 것이 바람직하다.The etching solution is preferably any one selected from the group consisting of hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, and acetic acid.
상기 단계(S40)에서 금속 화합물로부터 산화 마그네슘이 분해되면서 실리콘에 기공이 형성되지만, 상기 기공은 불균일하게 형성되어 있으며, 도 3(b)에서 보는 바와 같이, 금속 화합물에 여전히 산화 마그네슘이 남아있다. 이에 단계(S50)에서 에칭 용액으로 1 ~ 10 시간 동안 에칭함으로써, 금속 화합물에 존재하는 산화 마그네슘이 완전하게 제거되면서, 도 4(b)에서 보는 바와 같이, 기공이 균일하게 형성된 멀티 다공성 실리콘을 수득하게 된다. In step S40, pores are formed in silicon as magnesium oxide is decomposed from the metal compound, but the pores are formed non-uniformly, and as shown in FIG. 3(b), magnesium oxide still remains in the metal compound. Accordingly, by etching with an etching solution for 1 to 10 hours in step S50, the magnesium oxide present in the metal compound is completely removed, and as shown in FIG. 4(b), multi-porous silicon with uniformly formed pores is obtained. I do it.
에칭 시간이 1 시간 미만이면 산화 마그네슘이 원활하게 제거되지 않아 다공성 실리콘의 생성이 어려우며, 10 시간 초과이면 금속 화합물이 과도하게 에칭되어 전극물질의 기계적 물성이 저하되는 문제가 있다.If the etching time is less than 1 hour, magnesium oxide is not smoothly removed, making it difficult to create porous silicon. If the etching time is more than 10 hours, the metal compound is excessively etched, which reduces the mechanical properties of the electrode material.
본 발명의 다른 측면에 따른 리튬 2차 전지용 전극물질은 상기 제조방법에 의해 제조된 다공성 실리콘을 포함한다.An electrode material for a lithium secondary battery according to another aspect of the present invention includes porous silicon manufactured by the above manufacturing method.
즉, 본 발명의 제조방법에 의해 제조된 다공성 실리콘을 포한하는 리튬 2차 전지용 전극물질은 충방전시 발생되는 구조적 변화와 부피팽창을 효율적으로 억제시킬 수 있으며, 이로 인해 충방전 용량 및 사이클 특성이 향상되는 효과를 얻을 수 있다.In other words, the electrode material for lithium secondary batteries containing porous silicon manufactured by the manufacturing method of the present invention can efficiently suppress structural changes and volume expansion that occur during charging and discharging, thereby improving charge/discharge capacity and cycle characteristics. Improved effects can be achieved.
이하, 본 발명의 실시예 및 실험예에 의해 상세히 설명한다.Hereinafter, the present invention will be described in detail through examples and experimental examples.
하기 실시예 및 실험예는 본 발명을 예시하는 것 일뿐, 본 발명이 하기 실시예 및 실험예에 한정되는 것이 아니다.The following examples and experimental examples are merely illustrative of the present invention, and the present invention is not limited to the following examples and experimental examples.
< < 실시예Example > 본 발명에 따른 리튬 2차 전지용 전극물질의 제조 > Manufacture of electrode material for lithium secondary battery according to the present invention
(S10) : 40 ㎛의 입경 크기를 가진 실리콘과 300 ㎛의 입경 크기를 가진 마그네슘은 2 : 1 중량비로 교반기(stirrer)에서 1,000 rpm의 속도로 교반 및 혼합하여 금속 혼합물을 수득하였다.(S10): Silicon with a particle size of 40 ㎛ and magnesium with a particle size of 300 ㎛ were stirred and mixed in a 2:1 weight ratio in a stirrer at a speed of 1,000 rpm to obtain a metal mixture.
(S20) : 상기 금속 혼합물을 아르곤 기체 분위기하에 500 ℃에서 5 시간 동안 1차 열처리하여 금속 화합물을 수득하였다. 이때, 수득된 금속 화합물은 Mg2Si로 생성되었다. (S20): The metal mixture was subjected to primary heat treatment at 500° C. for 5 hours in an argon gas atmosphere to obtain a metal compound. At this time, the obtained metal compound was produced as Mg 2 Si.
(S30) : 상기 Mg2Si는 증류수와 혼합하여 180 ℃에서 40 cc의 드라이 유량으로 분무건조 처리하여 Mg2Si을 응집시켰다.(S30): The Mg 2 Si was mixed with distilled water and spray-dried at 180°C at a dry flow rate of 40 cc to aggregate Mg 2 Si.
(S40) : 상기 응집된 Mg2Si는 공기 산화 탈마그네슘 반응(air oxidation demagnesiation)으로, 공기 분위기하에 600 ℃에서 10 시간 동안 2차 열처리를 하였다. 상기 공기 산화 탈마그네슘 반응을 통해 응집된 Mg2Si는 실리콘과 산화 마그네슘이 생성되었다(반응식 참조). (S40): The aggregated Mg 2 Si was subjected to secondary heat treatment at 600° C. for 10 hours in an air atmosphere through air oxidation demagnesiation. Mg 2 Si aggregated through the air oxidation demagnesium reaction produced silicon and magnesium oxide (see reaction formula).
[반응식][Reaction formula]
Mg2Si + O2 (air) → Si + MgOMg 2 Si + O 2 (air) → Si + MgO
(S50) : 상기 2차 열처리 후 2M 염산으로 5 시간 동안 에칭하여 순수한 멀티 다공성 실리콘을 제조하였다. (S50): After the secondary heat treatment, pure multi-porous silicon was prepared by etching with 2M hydrochloric acid for 5 hours.
< < 실험예Experiment example 1 > 본 발명의 일 측면에 따른 리튬 2차 전지용 전극물질의 제조방법의 단계별 1 > Step-by-step of the manufacturing method of an electrode material for a lithium secondary battery according to an aspect of the present invention XRDXRD 패턴 분석 pattern analysis
도 3은 본 발명의 일 측면에 따른 리튬 2차 전지용 전극물질의 제조방법의 단계별 XRD 패턴을 나타낸 그래프이다((a) 분무건조 후, (b) 공기 산화 탈마그네슘화 후, (c) 에칭 후).Figure 3 is a graph showing step-by-step ).
도 3(a)는 실시예의 단계(S30)에서 분무건조된 Mg2Si를 XRD 패턴을 분석한 것으로, JCPDS에 등재된 No 35-0773 Mg2Si와 비교한 결과, 단계(S30)에서 조밀하게 응집된 Mg2Si만이 생성되었음을 확인하였고, 도 3(b)는 실시예의 단계(S40)에서 공기 산화 탈마그네슘화를 한 후 생성된 물질을 XRD 패턴을 분석한 것으로, JCPDS에 등재된 No 89-4248 MgO 및 No 27-1402 Si과 비교한 결과, 단계(S40)에서 Mg2Si으로부터 Si과 MgO로 분해된 것을 확인하였으며, 도 3(c)는 실시예의 단계(S50)에서 에칭 후 XRD 패턴을 분석한 것으로, JCPDS에 등재된 No 27-1402 Si과 비교한 결과, 단계(S40)에서 아직 실리콘에 붙어있는 MgO이 완전하게 제거되어 순수한 멀티 다공성 실리콘만 생성되었음을 확인하였다. Figure 3(a) is an XRD pattern analysis of Mg 2 Si spray-dried in step (S30) of the example. As a result of comparing it with No 35-0773 Mg 2 Si listed in JCPDS, it was found that in step (S30), it was densely It was confirmed that only aggregated Mg 2 Si was produced, and Figure 3(b) shows the XRD pattern analysis of the material produced after air oxidation demagnesization in step S40 of the example, No 89- listed in JCPDS. As a result of comparison with 4248 MgO and No 27-1402 Si, it was confirmed that Mg 2 Si was decomposed into Si and MgO in step (S40), and Figure 3(c) shows the XRD pattern after etching in step (S50) of the example. As a result of the analysis and comparison with No 27-1402 Si listed in JCPDS, it was confirmed that MgO still attached to the silicon was completely removed in step (S40) and only pure multi-porous silicon was created.
< < 실험예Experiment example 2 > 본 발명의 일 측면에 따른 리튬 2차 전지용 전극물질의 제조방법의 단계별 표면 형태학 분석 2 > Step-by-step surface morphology analysis of the manufacturing method of electrode material for lithium secondary battery according to one aspect of the present invention
도 4는 본 발명의 일 측면에 따른 리튬 2차 전지용 전극물질의 제조방법의 단계별 주사 전자 현미경(SEM) 이미지이다((a) 분무건조 후, (b) 에칭 후).Figure 4 is a step-by-step scanning electron microscope (SEM) image of the method for manufacturing an electrode material for a lithium secondary battery according to one aspect of the present invention ((a) after spray drying, (b) after etching).
도 4(a)는 도 3(a)와 관련하여, 실시예의 단계(S30)에서 조밀하게 응집된 Mg2Si이 생성되었음을 확인하였고, 도 4(b)는 도 3(c)와 관련하여, 실시예의 단계(S50)에서 에칭을 함으로써, 단계(S40)에서 아직 실리콘에 붙어있는 MgO이 완전하게 제거되어 기공이 균일하게 형성된 멀티 다공성 실리콘만이 생성되었음을 확인하였다. Figure 4(a), in relation to Figure 3(a), confirms that densely aggregated Mg 2 Si was produced in step S30 of the example, and Figure 4(b) shows, in relation to Figure 3(c), By etching in step S50 of the example, it was confirmed that MgO still attached to the silicon in step S40 was completely removed and only multi-porous silicon with uniformly formed pores was created.
< < 실험예Experiment example 3 > 3 > 리튬 lithium 2차 전지 특성 평가 Evaluation of secondary battery characteristics
실시예에서 제조된 다공성 실리콘으로 전극을 제조하였다. 활물질, 도전재료 및 바인더가 중량비로 6 : 2 : 2인 도포액을 Cu 전극 기판 상에 도포하고 약 100℃의 온도에서 건조하여 전극을 제조하였다. 도전 재료로는 Super P 카본 블랙 분말을 사용하였고, 바인더로는 PAA(Polyacrylic acid)를 사용하였다. An electrode was manufactured from the porous silicon prepared in the examples. An electrode was manufactured by applying a coating solution containing an active material, a conductive material, and a binder in a weight ratio of 6:2:2 on a Cu electrode substrate and drying it at a temperature of about 100°C. Super P carbon black powder was used as a conductive material, and PAA (polyacrylic acid) was used as a binder.
EC(ethylene carbonate)/DEC(diethyl carbonate)/EMC(ethylmethyl carbonate)가 부피비로 3 : 5 : 2로 함유되고, 10 wt%의 FEC(fluoroethylene carbonate)가 포함된 혼합물에 1M LiPF6인 전해액을 제조하였다.An electrolyte solution containing 1M LiPF 6 was prepared in a mixture containing EC (ethylene carbonate)/DEC (diethyl carbonate)/EMC (ethylmethyl carbonate) in a volume ratio of 3:5:2 and 10 wt% of FEC (fluoroethylene carbonate). did.
제조된 전극셀과 전해액을 사용하여 전기화학적 특성을 측정하였다. 도요(Toyo)사의 T-3100를 사용하여, 충방전 용량 및 사이클 특성을 측정하였다.Electrochemical properties were measured using the manufactured electrode cell and electrolyte solution. Charge/discharge capacity and cycle characteristics were measured using Toyo's T-3100.
0.005 ~ 2.0 V의 전압 범위에서 초기 화성단계의 사이클(1 ~ 5 사이클)은 0.1 C-rate 정전류 방식(CC)으로 충전(리튬 삽입)과 방전(리튬 탈리)을 진행하였으며, 그 이후의 싸이클(6 ~ 45 사이클)은 0.5 C-rate 정전류 방식(CC)으로 0.005 ~ 1.5 V의 전압 범위에서 충/방전을 진행하였다.In the voltage range of 0.005 ~ 2.0 V, the cycle (1 ~ 5 cycles) of the initial formation stage was charged (lithium insertion) and discharge (lithium detachment) using a 0.1 C-rate constant current (CC) method, and the subsequent cycles ( 6 to 45 cycles) were charged/discharged in a voltage range of 0.005 to 1.5 V using a 0.5 C-rate constant current method (CC).
< < 충방전charge/discharge 특성 및 사이클 특성 평가 > Evaluation of characteristics and cycle characteristics >
도 5는 본 발명의 일 측면에 따른 리튬 2차 전지용 전극물질에 따른 초기 화성 사이클의 충방전 전위에 따른 충방전 용량의 변화를 나타낸 그래프(a) 및 충방전 사이클 특성을 측정한 그래프(b)이다. 그리고, 표 1은 측정 결과값을 정리하여 나타냈었다.Figure 5 is a graph showing the change in charge/discharge capacity according to the charge/discharge potential of the initial chemical cycle according to the electrode material for a lithium secondary battery according to an aspect of the present invention (a) and a graph (b) measuring charge/discharge cycle characteristics. am. And Table 1 summarizes the measurement results.
횟수cycle
number
(mAh/g)charge
(mAh/g)
(mAh/g)Discharge
(mAh/g)
(%)klong efficiency
(%)
(%)cycle efficiency
(%)
다공성 실리콘example
porous silicon
다공성 실리콘comparative courtesy
porous silicon
비교예의 다공성 실리콘은 실시예의 단계(S30)인 분무건조를 하지 않고 제조되었다. The porous silicon of the comparative example was manufactured without spray drying, which is step (S30) of the example.
표 2와 도 5에서 보는 바와 같이, 실시예의 다공성 실리콘이 비교예보다 초기 충전 용량(1748.9 mAh/g), 방전 용량(1720.5 mAh/g), 및 싸이클 효율(86.6 %)이 우수한 것을 확인하였다. 이는 실시예의 다공성 실리콘은 분무건조의 전처리 과정을 거쳤기 때문에 균일하면서 조밀한 기공이 형성되어 충방전 과정 중에 원래의 구조를 변화시키지 않으면서, 다공성 실리콘의 부피 팽창을 억제시켜 충방전 용량 및 사이클 특성이 향상되는 것을 알 수 있다.As shown in Table 2 and Figure 5, it was confirmed that the porous silicon of the Example was superior to the Comparative Example in initial charge capacity (1748.9 mAh/g), discharge capacity (1720.5 mAh/g), and cycle efficiency (86.6%). This is because the porous silicon of the example has undergone a pretreatment process of spray drying, so that uniform and dense pores are formed, and the volume expansion of the porous silicon is suppressed without changing the original structure during the charge/discharge process, thereby improving charge/discharge capacity and cycle characteristics. You can see the improvement.
이제까지 본 발명에 대하여 그 바람직한 실시예들을 중심으로 살펴보았다. 본 발명이 속하는 기술 분야에서 통상의 지식을 가진 자는 본 발명이 본 발명의 본질적인 특성에서 벗어나지 않는 범위에서 변형된 형태로 구현될 수 있음을 이해할 수 있을 것이다. 그러므로 개시된 실시예들은 한정적인 관점이 아니라 설명적인 관점에서 고려되어야 한다. 본 발명의 범위는 전술한 설명이 아니라 특허청구범위에 나타나 있으며, 그와 동등한 범위 내에 있는 모든 차이점은 본 발명에 포함된 것으로 해석되어야 할 것이다.So far, the present invention has been examined focusing on its preferred embodiments. A person skilled in the art to which the present invention pertains will understand that the present invention may be implemented in a modified form without departing from the essential characteristics of the present invention. Therefore, the disclosed embodiments should be considered from an illustrative rather than a restrictive perspective. The scope of the present invention is indicated in the claims rather than the foregoing description, and all differences within the equivalent scope should be construed as being included in the present invention.
Claims (9)
상기 혼합물을 1차 열처리하여 금속 화합물을 수득하는 단계(S20);
상기 금속 화합물을 분무건조 처리하여 금속 화합물의 입자를 응집시키는 단계(S30);
상기 응집된 금속 화합물을 2차 열처리하는 단계(S40); 및
상기 2차 열처리 후 에칭 용액으로 1 ~ 10 시간 동안 에칭하는 단계(S50);를 포함하는 리튬 2차 전지용 전극물질의 제조방법.
Obtaining a metal mixture by mixing silicon (Si) with a particle size of 30 to 50 ㎛ and magnesium with a particle size of 200 to 500 ㎛ (S10);
Obtaining a metal compound by first heat treating the mixture (S20);
Spray drying the metal compound to agglomerate particles of the metal compound (S30);
Secondary heat treatment of the aggregated metal compound (S40); and
A method of manufacturing an electrode material for a lithium secondary battery, comprising: etching with an etching solution for 1 to 10 hours after the secondary heat treatment (S50).
상기 1차 열처리는 아르곤, 헬륨, 및 질소로 이루어진 군으로부터 선택된 어느 하나의 비활성 기체 분위기하에 수행되는 것을 특징으로 하는 리튬 2차 전지용 전극물질의 제조방법.
According to claim 1,
A method of producing an electrode material for a lithium secondary battery, wherein the first heat treatment is performed under an inert gas atmosphere selected from the group consisting of argon, helium, and nitrogen.
상기 1차 열처리는 400 ~ 900 ℃에서 3 ~ 8 시간 동안 수행되는 것을 특징으로 하는 리튬 2차 전지용 전극물질의 제조방법.
According to claim 1,
A method of manufacturing an electrode material for a lithium secondary battery, characterized in that the first heat treatment is performed at 400 to 900 ° C. for 3 to 8 hours.
상기 분무건조는 150 ~ 250 ℃에서 20 ~ 80 cc의 드라이 유량로 수행되는 것을 특징으로 하는 리튬 2차 전지용 전극물질의 제조방법.
According to claim 1,
A method of producing an electrode material for a lithium secondary battery, characterized in that the spray drying is performed at 150 to 250 ° C. and a dry flow rate of 20 to 80 cc.
상기 2차 열처리는 공기 산화 탈마그네슘 반응(air oxidation demagnesiation)으로 수행되는 것을 특징으로 하는 리튬 2차 전지용 전극물질의 제조방법.
According to claim 1,
A method of manufacturing an electrode material for a lithium secondary battery, characterized in that the secondary heat treatment is performed by air oxidation demagnesiation.
상기 2차 열처리는 공기 분위기하에 500 ~ 900 ℃에서 5 ~ 24 시간 동안 수행되는 것을 특징으로 하는 리튬 2차 전지용 전극물질의 제조방법.
According to claim 1,
A method of manufacturing an electrode material for a lithium secondary battery, characterized in that the secondary heat treatment is performed for 5 to 24 hours at 500 to 900 ° C. in an air atmosphere.
상기 에칭 용액은 염산, 황산, 인산, 질산, 및 아세트산으로 이루어진 군으로부터 선택된 어느 하나인 것을 특징으로 하는 리튬 2차 전지용 전극물질의 제조방법.
According to claim 1,
A method of manufacturing an electrode material for a lithium secondary battery, wherein the etching solution is any one selected from the group consisting of hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, and acetic acid.
An electrode material for a lithium secondary battery manufactured by the manufacturing method of any one of claims 1 to 7.
상기 전극물질은 다공성 실리콘을 포함하는 리튬 2차 전지용 전극물질.According to claim 8,
The electrode material is an electrode material for a lithium secondary battery containing porous silicon.
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