[논문]입자 크기 및 탄소 코팅에 따른 리튬이온배터리용 SiOx 음극활물질의 전기화학적 특성

박안나; 나병기

doi:10.9713/kcer.2024.62.1.19

입자 크기 및 탄소 코팅에 따른 리튬이온배터리용 SiOx 음극활물질의 전기화학적 특성
Electrochemical Properties of SiOx Anode for Lithium-Ion Batteries According to Particle Size and Carbon Coating 원문보기

Korean chemical engineering research = 화학공학, v.62 no.1, 2024년, pp.19 - 26

초록
AI-Helper

본 연구에서는 리튬이온배터리용 고용량 음극활물질인 실리콘의 부피팽창을 완화하고 사이클 안정성을 향상시키기 위해 SiOx@C 복합소재를 제조하였다. Stӧber 법을 통해 입자 크기가 각각 100, 200, 500 nm인 SiO₂를 합성하였고, 마그네슘 열환원을 통해 SiOx (0≤x≤2)를 제조하였다. 그 후 SiOx에 PVC를 탄화시켜 SiOx와 C의 비율에 따라 SiOx@C 음극활물질을 합성하였다. 제조된 SiOx와 SiOx@C 음극활물질의 물리적 특성은 XRD, SEM, TGA, 라만분광법, XPS, BET를 사용해 분석하였다. 그리고 사이클 테스트, 율속특성, CV, EIS 테스트를 통해 전기화학적 특성을 조사하였다. 입자 크기가 가장 작은 100 nm SiOx에 SiOx:C=70:30으로 탄소를 코팅하여 제조된 SiOx@C-7030은 100 사이클에서 1055 mAh/g의 방전용량과 81.9%의 용량을 유지하여 가장 우수한 전기화학적 특성을 보여주었다. 이는 SiOx 음극활물질 입자의 크기를 줄이고, 탄소를 코팅하여 사이클 안정성을 향상시킬 수 있다는 것을 의미한다.

Abstract ▼ AI-Helper

In this study, the electrochemical properties of SiOx@C composite materials were prepared to alleviate volume expansion and cycle stability of silicon and to increase the capacity of anode material for LIBs. SiO2 particles of 100, 200, and 500 nm were synthesized by the Stӧber method, and reduced to SiOx (0≤x≤2) through the magnesiothermic reduction method. Then, SiOx@C anode materials were synthesized by carbonization of PVC on SiOx. The physical properties of prepared SiOx and SiOx@C anode materials were analyzed by XRD, SEM, TGA, Raman spectroscopy, XPS and BET. The electrochemical properties were investigated by cycling performance, rate performance, CV and EIS test. As a result, the SiOx@C-7030 manufactured by coating carbon at SiOx : C = 70 : 30 on a 100 nm SiOx with the smallest particle size showed the best electrochemical properties with a discharge capacity of 1055 mAh/g and a capacity retention rate of 81.9% at 100 cycles. It was confirmed that cycle stability was impoved by reducing particle size and carbon coating.

주제어

표/그림 (12)

그림 Fig. 1. Process diagram for the synthesis of SiOx and SiOx@C anode materials.
$Fig. 2. X-ray diffraction patterns of 100, 200, 500 nm SiOx and SiOx@C-7030.$ 그림 Fig. 2. X-ray diffraction patterns of 100, 200, 500 nm SiOx and SiOx@C-7030.
그림 Fig. 3. Raman spectra of 100 nm SiOx and SiOx@C-7030.
그림 Fig. 4. SEM images of (a) 100 nm SiO₂, (b) 200 nm SiO₂, (c) 500 nm SiO₂, (d) 100 nm SiOx, (b) 200 nm SiOx, (c) 500 nm SiOx and (g) EDS images of SiOx@C-7030.
그림 Fig. 5. Si 2p XPS spectra of 100 nm SiO₂, SiOx and SiOx@C-7030.
그림 Fig. 6. TGA curves of SiOx@C anode materials.
그림 Fig. 7. CV curves of (a) 100 nm SiOx and (b) SiOx@C-7030 anode materials.
그림 Fig. 8. Cycle performance of SiOx and SiOx@C anode materials at (a) 0.1 A/g and (b) 1 A/g.
표 Table 1. BET specific surface area and pore volume of SiO₂, SiOx and SiOx@C
그림 Fig. 9. Rate performance of 100 nm SiOx and SiOx@C anode materials.
그림 Fig. 10. Nyquist plots of 100 nm SiOx and SiOx@C anode materials after 5 cycles.
표 Table 2. Fitted EIS parameters for 100 nm SiOx and SiOx@C anode materials

참고문헌 (40)

Tang, H., Zhang, J., Zhang, Y. J., Xiong, Q. Q., Tong, Y. Y., Li,？Y., Wang, X. L. Gu, C. D. and Tu, J. P., "Porous Reduced？Graphene Oxide Sheet Wrapped Silicon Composite Fabricated？by Steam Etching for Lithium-Ion Battery Application," J. Power？Sources, 286, 431-437(2015).

상세보기
Wu, L., Yang, J., Zhou, X., Zhang, M., Ren, Y. and Nie, Y., "Silicon Nanoparticles Embedded in a Porous Carbon Matrix as a？High-Performance Anode for Lithium-Ion Batteries," J. Mater.？Chem. A, 4(29), 11381-11387(2016).

상세보기
Hsieh, C. C., Lin, Y. G., Chiang, C. L. and Liu, W. R., "CarbonCoated Porous Si/C Composite Anode Materials via Two-step？Etching/Coating Processes for Lithium-Ion Batteries," Ceram.？Int., 46(17), 26598-26607(2020).

상세보기
Wang, D., Zhou, C., Cao, B., Xu, Y., Zhang, D., Li, A., Zhou, J.,？Ma, Z., Chen, X. and Song, H., "One-Step Synthesis of Spherical Si/C Composites with Onion-like Buffer Structure as HighPerformance Anodes for Lithium-Ion Batteries," Energy Stor.？Mater., 24, 312-318(2020).
Chen, S., Gordin, M. L., Yi, R., Howlett, G., Sohn, H. and Wang,？D., "Silicon Core-Hollow Carbon Shell Nanocomposites with？Tunable Buffer Voids for High Capacity Anodes of Lithium-Ion？Batteries," Phys. Chem. Chem. Phys., 14(37), 12741-12745(2012).

상세보기
Su, X., Wu, Q., Li, J., Xiao, X., Lott, A., Lu, W., Sheldon, B. W.？and Wu, J., "Silicon-Based Nanomaterials for Lithium-Ion Batteries: A Review," Adv. Energy Mater., 4(1), 1300882(2014).

상세보기
Preman, A. N., Lim, Y. E., Lee, S., Kim, S., Kim, I. T. and Ahn,？S. K. "Facile Synthesis of Polynorbornene-based Binder through？ROMP for Silicon Anode in Lithium-ion Batteries," Korean J.？Chem. Eng., 40(10), 2529-2537(2023).

상세보기
Liu, M. P., Li, C. H., Du, H. B. and You, X. Z., "Facile Preparation of Silicon Hollow Spheres and Their Use in Electrochemical？Capacitive Energy Storage," Chem. Comm., 48(41), 4950-4952(2012).
Entwistle, J., Rennie, A. and Patwardhan, S., "A Review of？Magnesiothermic Reduction of Silica to Porous Silicon for LithiumIon Battery Applications and Beyond," J. Mater. Chem. A, 6(38),？18344-18356(2018).

상세보기
Zhou, C., Liu, J., Gong, X. and Wang, Z., "Optimizing the Function？of SiOx in the Porous Si/SiOx Network via a Controllable Magnesiothermic Reduction for Enhanced Lithium Storage," J. Alloys？Compd., 874, 159914(2021).

상세보기
Moon, D. B., Kim, K. H. and Ahn, H. J., "Effect of Hierarchically？Reduced SiOx on Anode Performance of Li-Ion Batteries," Korean？J. Chem. Eng., 40(2), 3046-3051(2023).
Cui, J., Zhang, H., Liu, Y., Li, S., He, W., Hu, J. and Sun, J.,？"Facile, Economical and Environment-Friendly Synthesis Process？of Porous N-Doped Carbon/SiOx Composite from Rice Husks？as High-property Anode for Li-Ion Batteries," Electrochim. Acta,？334, 135619(2020).

상세보기
Liu, Y., Ruan, J., Liu, F., Fan, Y. and Wang, Pu., "Synthesis of？SiOx/C Composite with Dual Interface as Li-Ion Battery Anode？Material," J. Alloys Compd., 802, 704-711(2019).
Yu, B. C., Hwa, Y., Kim, J. H. and Sohn, H. J., "A New Approach？to Synthesis of Porous SiOx Anode for Li-Ion Batteries via Chemical Etching of Si Crystallites," Electrochim. Acta, 177, 426-430？(2014).
Nulu, A., Nulu, V. and Sohn, K. Y., "Silicon and Porous MWCNT？Composite as High Capacity Anode for Lithium-ion Batteries,"？Korean J. Chem. Eng., 37(10), 1795-1802(2020).

상세보기
Zhang, J., Ma, P., Zhang, X., Liu, Z., Zheng, J., Zuo, Y., Xue, C.,？Cheng, B. and Li, C., "Core-Shell Structured SiOx-C Composite？for Lithium Ion Battery Anodes," Energy Techno., 7(4), 1800800？(2019).
Dong, H., Fu, X., Wang, J., Wang, P., Ding, H., Song, R., Wang, S.,？Li, R. and Li, S., "In-situ Construction of Porous Si@C Composites with LiCl Template to Provide Silicon Anode Expansion？Buffer," Carbon, 173, 687-695(2021).

상세보기
Green, D. L., Jayasundara, S., Lam, Y. F. and Harris, M. T., "Chemical Reaction Kinetics Leading to the First Stober Silica Nanoparticles - NMR and SAXS Investigation," J. Non-Cryst. Solids,？315, 166-179(2003).

상세보기
Rao, K. S., El-Hami, K., Kodaki, T., Matsushige, K. and Makino,？K., "A Novel Method for Synthesis of Silica Nanoparticles," J.？Colloid Interface Sci., 289(1), 125-131(2005).

상세보기
Jiang, X., Tang, X., Tang, L., Zhang, B. and Mao, H., "Synthesis？and Formation Mechanism of Amorphous Silica Particles via？Sol-Gel Process with Tetraethylorthosilicate," Ceram. Int., 45(6),？7673-7680(2019).

상세보기
Yin, S., Zhao, D., Ji, Q., Xia, Y., Xia, S., Wang, X., Wang, M.,？Ban, J., Zhang, Y., Metwalli, E., Wang, X., Xiao, Y., Zuo, X., Xie,？S., Fang, K., Liang, S., Zheng, L., Qiu, B., Yang, Z., Lin, Y., Chen,？L., Wang, C., Liu, Z., Zhu, J., Muller-Buschbaum, P. and Cheng,？Y. J., "Si/Ag/C Nanohybrids with in Situ Incorporation of SuperSmall Silver Nanoparticles: Tiny Amount, Huge Impact," ACS？Nano, 12(1), 861-875(2018).
Jin, C., Dan, J., Zou, Y., Xu, G., Yue, Z., Li, X., Sun, F., Zhou, L.？and Wang, L., "Carbon-Coated Nitrogen Doped SiOx Anode Material for High Stability Lithium Ion Batteries," Ceram. Int., 47(20),？29443-29450(2021).

상세보기
Cong, R., Park, H. H., Jo, M., Lee, H. and Lee, C. S., "Synthesis？and Electrochemical Performance of Electrostatic Self-Assembled？Nano-Silicon@N-Doped Reduced Graphene Oxide/Carbon Nanofibers Composite as Anode Material for Lithium-Ion Batteries,"？Molecules, 26(16), 4831(2021).

상세보기
Yu, Q., Ge, P., Liu, Z., Xu, M., Yang, W., Zhou, L., Zhao, D. and？Mai, L., "Ultrafine SiOx/C Nanospheres and Their Pomegranatelike Assemblies for High-Performance Lithium Storage," J. Mater.？Chem. A, 6(30), 14903-14909(2018).

상세보기
Luo, W., Wang, X., Meyers, C., Wannenmacher, N., Sirisakssontorn,？W., Lerner, M. M. and Ji, X., "Efficient Fabrication of Nanoporous？Si and Si/Ge Enabled by a Heat Scavenger in Magnesiothermic？Reactions," Sci. Rep., 3(1), 2222(2013).
Lakhonchai, A., Chingsungnoen, A., Poolcharuansin, P., Chanlek,？N., Tunmee, S. and Rittihong, U., "Improvement of Corrosion？Resistance and Mechanical Properties of Chrome Plating by Diamond-like Carbon Coating with Different Silicon-Based Interlayers," Mater. Res. Express., 9(5), 055604(2022).
Liu, S. F., Kuo, C. H., Lin, C. C., Lin, H. Y., Lu, J. C. Z., Kang,？W., Fey, G. T. K. and Chen, H. Y., "Biowaste-Derived Si@SiOx/C？Anodes for Sustainable Lithium-Ion Batteries," Electrochim. Acta,？403, 139580(2022).

상세보기
Bashouti, M. Y., Sardashti, K., Ristein, J. and Christiansen, S.？H., "Early Stages of Oxide Growth in H-Terminated Silicon Nanowires: Determination of Kinetic Behavior and Activation Energy,"？Phys. Chem. Chem. Phys., 14(34), 11877-11881(2012).

상세보기
Yao, Y., Xu, X., Zhao, H., Tong, Y. and Li, Y., "Multilayer Si@SiOx@Void@C Anode Materials Synthesized via Simultaneously Carbonization and Redox for Li-Ion Batteries," Ceram. Int., 48(9),？12217-12227(2022).

상세보기
Hu, G., Yu, R., Liu, Z., Yu, Q., Zhang, Y., Chen, Q., Wu, J., Zhou,？L. and Mai, L., "Surface Oxidation Layer-Mediated Conformal？Carbon Coating on Si Nanoparticles for Enhanced Lithium Storage," ACS Appl. Mater. Interfaces, 13(3), 3991-3998(2021).

상세보기
Tao, H. C., Huang, M., Fan, L. Z. and Qu, X., "Interweaved Si@SiOx/C Nanoporous Spheres as Anode Materals for Li-Ion Batteries,"？Solid State Ion, 220, 1-6(2012).
Lee, E. H., Jeong, B. O., Jeong, S. H., Kim, T. J., Kim, Y. S. and？Jung, Y., "Effect of Carbon Matrix on Electrochemical Performance？of Si/C Composites for Use in Anodes of Lithium Secondary？Batteries," Bull. Korean Chem. Soc., 34(5), 1435-1440(2013).

원문보기 상세보기
Zhu, M., Yang, J., Yu, Z., Chen, H. and Pan, F., "Novel Hybrid Si？Nanocrystals Embedded in a Conductive SiOx@C Matrix from？One Single Precursor as a High Performance Anode Material？For Lithium-Ion Batteries," J. Mater. Chem. A, 5(15), 7026-7034？(2017).

상세보기
Li, Y., Wang, R., Zhang, J., Chen, J., Du, C., Sun, T., Liu, J.,？Gong, C., Guo, J., Yu, L. and Zhang, J., "Sandwich Structure of？Carbon-Coated Silicon/Carbon Nanofiber Anodes for LithiumIon Batteries," Ceram. Int., 45(13), 16195-16201(2019).

상세보기
Cen, Y., Qin, Q., Sisson, R. D. and Liang, J., "Effect of Particle？Size and Surface Treatment on Si/Graphene Nanocomposite Lithium-Ion Battery Anodes," Electrochim. Acta, 251, 690-698(2017).

상세보기
Koraag, P. Y. E., Firdaus, A. M., Hawari, N. H., Refino, A. D.,？Dempwolf, W., Iskandar, F., Peiner, E., S. Wasisto, H. and Sumboja,？A., "Covalently Bonded Ball-Milled Silicon/CNT Nanocomposite？as Lithium-Ion Battery Anode Material," Batteries, 8(10), 165？(2022).

상세보기
Liu, X. H., Zhong, L., Huang, S., Mao, S. X., Zhu, T. and Huang, J.？Y., "Size-Dependent Fracture of Silicon Nanoparticles During？Lithiation," ACS Nano, 6(2), 1522-1531(2012).

상세보기
Wu, L., Zhou, H., Yang, J., Zhou, X., Ren, Y., Nie, Y. and Chen,？S., "Carbon Coated Mesoporous Si Anode Prepared by a Partial？Magnesiothermic Reduction for Lithium-Ion Batteries," J. Alloys？Compd., 716, 204-209(2017).

상세보기
Zhang, X., Zhou, L., Huang, M., Yang, C., Xu, Y. and Huang,？J., "Synthesis of Porous Si/C by Pyrolyzing Toluene as Anode in？Lithium-Ion Batteries with Excellent Lithium Storage Performance," Ionics, 25, 2093-2102(2019).

상세보기
Cui, H., Chen, K., Shen, Y. and Wang, Z., "Self-Sacrificed Synthesis of Amorphous Carbon-Coatied SiOx as Anode Materials？for Lithium-Ion Batteries," Int. J. Electrochem. Sci., 13, 5474-5487(2018).

저자의 다른 논문 :

표제어: PCR

동의어: Packet Collision Rate

용어 설명 출처 목록 (6)

용어 설명: PCR은 세균 특이성이 있는 primer를 이용하여 적은 수의 세균이 있을지라도 쉽게 검출할 수 있는 유용한 방법이며, 이를 이용하여 구강 내 치면세균막이나 타액에서 직접 세균을 검출할 수 있게 되었다[8].

내보내기 구분	파일저장 인쇄 메일전송
구성항목	기본정보 상세정보 관리번호, 논문명, 저널/프로시딩명, 저자 , 발행년, 권, 호, 시작페이지, 끝페이지, 발행기관 관리번호, 논문명, 대등논문명, 저자 , 저널/프로시딩명, 발행기관, 발행년, 발행언어, 권, 호, 시작페이지, 끝페이지, ISBN, ISSN, 주제분야, 키워드, 초록(한글), 초록(영문), 저자(소속기관)
저장형식	Text(ASCII format) Excel format RefWorks Direct Export RIS format (for Reference Manager, ProCite, EndNote), Scholar's Aids, Mendeley
메일정보	받는사람 (필수) @ 보내는사람 (선택) @ 제목 내용 KISTI 검색결과 이메일 서비스
안내	총 건의 자료가 검색되었습니다. 다운받으실 자료의 인덱스를 입력하세요. (1-10,000) 검색결과의 순서대로 최대 10,000건 까지 다운로드가 가능합니다. 데이타가 많을 경우 속도가 느려질 수 있습니다.(최대 2~3분 소요) 다운로드 파일은 UTF-8 형태로 저장됩니다. 파일의 내용이 제대로 보이지 않을실 때는 웹브라우저 상단의 보기 -> 인코딩 -> 자동선택 여부를 확인하십시오. ~ Text(ASCII format) Excel format

연합인증