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硅碳复合材料及化合物结合了硅的高储锂性能及碳的结构优异性，然而，其复杂的电化学行为和充放电过程中的体积变化为亟待解决的问题。第一性原理计算作为一种有效的理论工具，在预测和揭示电极材料特性、理解原子尺度电化学机理等方面发挥着重要作用。首先概述第一性原理计算方法，并结合学者近年来利用第一性原理对典型硅碳复合材料及化合物锂离子电池负极材料的研究成果，然后提出锂离子电池硅碳负极材料扩散动力学、界面反应、力学性能和热力学稳定性规律。再从密度泛函理论、算法结合和实验结合3方面对锂离子电池硅碳负极材料第一性原理计算进行了展望，期待开发出性能更优的新型硅碳负极材料，助力新能源领域发展。
Abstract：Silicon-carbon composite materials and compounds combine the high lithium storage performances of silicon with the structural excellence of carbon.However,their complex electrochemical behavior and volume changes during charging and discharging are urgent issues to be addressed.As an effective theoretical tool,first-principles calculation plays a crucial role in predicting,revealing the characteristics of electrode materials and understanding electrochemical mechanisms in atomic scale.In this review,the first-principles calculation methods were summarized,and recent research results on first-principles calculations of typical silicon-carbon composite materials and compounds as lithium-ion battery anode materials were represented.The laws of diffusion kinetics,interface reactions,mechanical properties and thermodynamic stabilities of silicon-carbon anode materials for lithium-ion batteries were proposed.Furthermore,the first-principles calculations for silicon-carbon anode materials in lithium-ion batteries were outlooked based on three perspectives like density functional theory (DFT),algorithm integration and experimental integration.The development of novel silicon-carbon anode materials with superior performances were anticipated,thereby contributing to the development of the new energy sector.Summary and prospects In this review,the first-principles calculation methods and the research progress of the first-principles calculations on typical silicon-carbon anode materials for lithium-ion batteries were elaborated.The diffusion kinetics,interfacial reactions,mechanical properties and thermodynamic stability laws of silicon-carbon anode materials for lithium-ion batteries were revealed.1) From the perspective of lithium-ion diffusion kinetics,the diffusion mechanism of lithium ions in silicon-carbon anode materials is complex,which is affected by material structure and chemical composition.In silicon/graphite composite materials,lithium ions are prone to first intercalating between graphite layers and then diffusing into silicon,which is regarded as a two-dimensional diffusion.Lithium ions in silicon/carbon nanotube composite materials undergo an one-dimensional diffusion,primarily along the walls or gaps between carbon nanotubes.The two-dimensional structure in silicon/graphene composite materials facilitates a rapid diffusion of lithium ions.Lithium ions in silicon carbide exhibit bulk and interfacial diffusion,which are influenced by charge transfer and electric field effects.2) From the perspective of interface reaction,the formation of the SEI film is crucial for the performance of silicon-carbon anode materials.Meanwhile,cycle life and efficiency of the batteries are affected by stability and uniformity of SEI film.The volume expansion of silicon in silicon/graphite composite materials can damage the adjacent SEI film,leading to the continued generation of new SEI film.In silicon/carbon nanotube composite materials,more active sites for lithium ions are provided for the unique tubular structure and high specific surface area of carbon nanotubes,making the SEI film more stable.Silicon/graphene composite materials have a layered structure that promotes the uniform dispersion of electrolyte on the surface for the composite materials,resulting in a more uniform SEI film.Silicon carbide has a great hardness and a wear resistance,which enhances its ability to resist mechanical stress during charging and discharging,effectively protecting the SEI film.3) From the perspective of mechanical properties,different types of carbon materials have different buffering effects on the volume expansion of silicon.Volume expansion problems of silicon are alleviated because of impurities and defect structure of microcrystalline graphite in silicon/graphite composite materials.In silicon/carbon nanotube composite materials,the flexibility of carbon nanotubes helps to withstand greater structural deformation and enhance the structural stability of silicon.In silicon/graphene composite materials,core–shell structures are more conducive to suppressing the volume expansion of silicon.The decrease in electrochemical performance caused by volume expansion is alleviated by the tight interface bonding between silicon carbide and the matrix material,which also helps to improve the fatigue resistance of materials.4) From the perspective of thermodynamic stability,the thermodynamic stability is assessed through calculations of formation energy,binding energy,reactivity,and changes in free energy.Silicon/graphite composites,benefiting from the layered structure of graphite,exhibit a good thermodynamic stability due to their low formation energy,high binding energy,and low reactivity.Silicon/carbon nanotube composites have a high binding energy due to their unique structure,but their thermodynamic stability is significantly affected by free energy under high-temperature and high-pressure conditions.Silicon/graphene composite materials,leveraging the two-dimensional structure of graphene,have a moderate formation energy and a high binding energy,resulting in a stable thermodynamic performance.Silicon carbide has a high formation energy,and the covalent bonds between silicon and carbon atoms contribute to its high structural stability and good thermodynamic stability.Conventional DFT method struggles to accurately simulate intermolecular forces due to its lack of description of nonlocal electron correlations,resulting in significant errors in calculating material structural parameters,mechanical properties and energetic properties.To overcome this problem,the van der Waals Density Functional method is introduced.The Becke 86 exchange functional is incorporated by a named optB86b method,enabling effective corrections to the Generalized Gradient Approximation.The excessively strong repulsive interaction of the exchange functional at short distances is reduced,and the accuracy of DFT method is enhanced.To enhance the computational efficiency of first-principles calculations and have deeper insights into the lithium storage mechanism of silicon–carbon anode materials in lithium-ion batteries,the first-principles calculations and machine learning,phase-field methods,multiscale simulation techniques are integrated.The data analysis and model optimization are accelerated via machine learning.The evolution of microstructures is captured cross phase-field methods.The macroscopic reaction mechanisms of lithium-ion batteries from a microscopic perspective are revealed based on molecular dynamics and finite element analysis.The precision and efficiency of material development are significantly improved via interdisciplinary integration,expanding the application of silicon–carbon anode materials in the field of new energy.The first-principles calculations and experimental research should be combined due to some factors such as high experimental costs,stringent experimental condition and low data reproducibility.The accuracy of first-principles calculation methods can be validated via comparing computational predictions with experimental results,promoting the coordinated development of theoretical calculations and experimental research.It is expected that this will lead to the development of new silicon-carbon anode materials with a higher specific capacity,a better cycle stability,and a faster charge/discharge rate,facilitating their application in sodium-ion batteries and other fields and bringing greater breakthroughs to the development of the new energy field.
[1] SCHMUCH R, WAGNER R, H?RPEL G, et al. Performance and cost of materials for lithium-based rechargeable automotive batteries[J]. Nat Energy, 2018, 3:267–278.
[2] LU Y, ZHANG Q, CHEN J. Recent progress on lithium-ion batteries with high electrochemical performance[J]. Sci China Chem, 2019,62(5):533–548.
[3] ZHAN X, LI M, LI S, et al. Challenges and opportunities towards silicon-based all-solid-state batteries[J]. Energy Storage Mater, 2023,61:102875.
[4] MICHAN A L, DIVITINI G, PELL A J, et al. Solid electrolyte interphase growth and capacity loss in silicon electrodes[J]. J Am Chem Soc, 2016, 138(25):7918–7931.
[5] MA J, SUNG J, HONG J, et al. Towards maximized volumetric capacity via pore-coordinated design for large-volume-change lithium-ion battery anodes[J]. Nat Commun, 2019, 10(1):475.
[6] WU M, CAI G K, LI Z, et al. Structures and properties of carbon-doped silicon as anode material for lithium ions battery:A first-principles study[J]. Vacuum, 2024, 225:113222.
[7] OUYANG Z Y, XU X D, CHE C R, et al. First principles investigations on the carbon-related defects in silicon[J]. Phys Status Solidi B:, 2024:2400254.
[8] QIN G Q, JIA Z T, SUN S Y, et al. Carbon-coated Si nanosheets as anode materials for high-performance lithium-ion batteries[J]. ACS Appl Nano Mater, 2024, 7(7):7595–7604.
[9] XU X T, MU X, HUANG T, et al. Robust silicon/carbon composite anode materials with high tap density and excellent cycling performance for lithium-ion batteries[J]. J Power Sources, 2024, 614:234992.
[10] YANG L, LI S N, ZHANG Y M, et al. Multi-scale design of silicon/carbon composite anode materials for lithium-ion batteries:A review[J]. J Energy Chem, 2024, 97:30–45.
[11] SADDIQUE J, WU M J, ALI W, et al. Opportunities and challenges of nano Si/C composites in lithium ion battery:A mini review[J]. J Alloys Compd, 2024, 978:173507.
[12]张培新,陈建华,魏群,等.掺杂材料分子模拟与计算[M].北京:科学出版社, 2012.
[13] NIEVES-PíREZ I, MU?OZ A, ALMEIDA F, et al. Energy efficiency and performance analysis of a legacy atomic scale materials modeling simulator(VASP)[J]. J Supercomput, 2024, 80(11):16679–16702.
[14]许真铭,刘庆生,陈江安. Materials Studio软件在计算化学和计算材料学课程教学中的应用[J].大学化学, 2024, 39(1):332–339.XU Zhenming, LIU Qingsheng, CHEN Jiang?an. China Ind Econ, 2024,39(1):332–339.
[15] TARDIO S, CUMPSON P J. Practical estimation of XPS binding energies using widely available quantum chemistry software[J]. Surf Interface Anal, 2018, 50(1):5–12.
[16] ROMERO A H, ALLAN D C, AMADON B, et al. ABINIT:Overview and focus on selected capabilities[J]. J Chem Phys, 2020, 152(12):124102.
[17] CARNIMEO I, AFFINITO F, BARONI S, et al. Quantum ESPRESSO:One further step toward the exascale[J]. J Chem Theory Comput, 2023,19(20):6992–7006.
[18] GARCíA A, PAPIOR N, AKHTAR A, et al. Siesta:Recent developments and applications[J]. J Chem Phys, 2020, 152(20):204108.
[19] SMITH M, TAMERUS A, HASNIP P. Portable acceleration of materials modeling software:CASTEP, GPUs, and OpenACC[J].Comput Sci Eng, 2022, 24(1):46–55.
[20]温亚娟.典型热电材料的第一原理计算[D].杭州:杭州电子科技大学, 2014.WEN Yajuan. First-principles study of several typical thermoelectric materials[D]. Hangzhou:Hangzhou Dianzi University, 2014.
[21] CALLOW T J, HANSEN S B, KRAISLER E, et al. First-principles derivation and properties of density-functional average-atom models[J].Phys Rev Research, 2022, 4(2):023055.
[22] PARK J, JUNG J H, JUNG K W, et al. Ab initio potential energy surfaces calculation via restricted Hartree–Fock for molecular dynamics simulation:A comprehensive review[J]. J Korean Phys Soc,2024, 84(7):550–565.
[23]宋刘斌,黎安娴,肖忠良,等.第一性原理在锂离子电池电极材料中的应用研究[J].化工学报, 2019, 70(6):2051–2059.SONG Liubin, LI Anxian, XIAO Zhongliang, et al. CIESC Journal,2019, 70(6):2051–2059.
[24] SODEYAMA K, USHIROGATA K, OKUNO Y, et al. SEI film formation mechanism based on aggregation configurations of electrolyte decomposed products:DFT-MD study[J]. Meet Abstr, 2016,MA2016–02(4):570.
[25] MAN Q Y, AN Y L, LIU C K, et al. Interfacial design of silicon/carbon anodes for rechargeable batteries:A review[J]. J Energy Chem, 2023,76:576–600.
[26] QIU T, LIANG L H. Research on the thickness effect and micro-fracture mechanism of graphite sheets with layered structures[J].Diam Relat Mater, 2024, 143:110908.
[27] DOSE W M, PIERNAS-MU?OZ M J, MARONI V A, et al. Capacity fade in high energy silicon-graphite electrodes for lithium-ion batteries[J]. Chem Commun, 2018, 54(29):3586–3589.
[28] YANG C, ZHANG Y L, ZHOU J H, et al. Hollow Si/SiOx nanosphere/nitrogen-doped carbon superstructure with a double shell and void for high-rate and long-life lithium-ion storage[J]. J Mater Chem A, 2018, 6(17):8039–8046.
[29] LIU B, HUANG P, LIU M Q, et al. Utilization of impurities and carbon defects in natural microcrystalline graphite to prepare silicon-graphite composite anode for high-performance lithium-ion batteries[J]. J Mater Sci, 2021, 56(31):17682–17693.
[30] OLOU’OU GUIFO S B, MUELLER J E, HENRIQUES D, et al.First-principles calculations of bulk, surface and interfacial phases and properties of silicon graphite composites as anode materials for lithium ion batteries[J]. Phys Chem Chem Phys, 2022, 24(16):9432–9448.
[31] GUO X B, YANG Z T, WANG W, et al. Silicon/carbon nanotubes anode for lithium-ion batteries:Synthesis, interface and electrochemical performance[J]. Surf Interfaces, 2024, 48:104223.
[32]张迎晓,周帆,赖陈,等.碳纳米管材料的制备及其应用研究进展[J].稀有金属材料与工程, 2024, 53(6):1781–1796.ZHANG Yinxin, ZHOU Fan. LAI Chen, et al. Rare Metal Mater Eng,2024, 53(6):1781–1796..
[33] CHEN Y F, DU N, ZHANG H, et al. Facile synthesis of uniform MWCNT@Si nanocomposites as high-performance anode materials for lithium-ion batteries[J]. J Alloys Compd, 2015, 622:966–972.
[34] WANG Y, WANG R S, ZHU H Z, et al. Atomic layer deposition of ultrathin Al2O3 layer on carbon nanotube anodes for potassium ion batteries with high initial coulombic efficiency and electrochemical performance[J]. Adv Mater Technol, 2023, 8(17):2300435.
[35] KAROUSIS N, TAGMATARCHIS N, TASIS D. Current progress on the chemical modification of carbon nanotubes[J]. Chem Rev, 2010,110(9):5366–5397.
[36] KANG H E, KO J, SONG S G, et al. Recent progress in utilizing carbon nanotubes and graphene to relieve volume expansion and increase electrical conductivity of Si-based composite anodes for lithium-ion batteries[J]. Carbon, 2024, 219:118800.
[37] HE Z Y, XIAO Z X, YUE H J, et al. Single-walled carbon nanotube film as an efficient conductive network for Si-based anodes[J]. Adv Funct Materials, 2023, 33(26):2300094.
[38] NAJIM A, BAJJOU O, BAKOUR A, et al. Electronic and optical properties of SWCNTs and spin-orbit coupling effect on their electronic structures:First-principle computing[J]. J Electron Spectrosc Relat Phenom, 2023, 265:147321.
[39] WANG H L, CHAO Y F, LI J Z, et al. What is the real origin of single-walled carbon nanotubes for the performance enhancement of Si-based anodes?[J]. J Am Chem Soc, 2024, 146(25):17041–17053.
[40] HE Z Y, ZHANG C X, ZHU Y K, et al. The acupuncture effect of carbon nanotubes induced by the volume expansion of silicon-based anodes[J]. Energy Environ Sci, 2024, 17(10):3358–3364.
[41] ZHANG Z W, LI Y Z, XU R, et al. Capturing the swelling of solid-electrolyte interphase in lithium metal batteries[J]. Science, 2022,375(6576):66–70.
[42] WANG M, YANG C X, LENG X Y, et al. The interface effect on the lithiation of silicon/graphene composites:The first principles study[J].Int J Quantum Chem, 2024, 124(3):27343.
[43] CHOU C Y, HWANG G S. Role of interface in the lithiation of silicon-graphene composites:A first principles study[J]. J Phys Chem C, 2013, 117(19):9598–9604.
[44] WANG G Q, XU B, SHI J, et al. Confined Li ion migration in the silicon-graphene complex system:An ab initio investigation[J]. Appl Surf Sci, 2018, 436:505–510.
[45] GAO X, LU W Q, XU J. Insights into the Li diffusion mechanism in Si/C composite anodes for lithium-ion batteries[J]. ACS Appl Mater Interfaces, 2021, 13(18):21362–21370.
[46]吴江滨,钱耀,郭小杰,等.硅纳米团簇与石墨烯复合结构储锂性能的第一性原理研究[J].物理学报, 2012, 61(7):145–151.WU Jiangbin, QIAN Yao, GUO Xiaojie, et al. Acta Phys Sin, 2012,61(7):145–151.
[47]张园园,吕燕伍.石墨烯中嵌入硅纳米线的第一性原理研究[J].人工晶体学报, 2018, 47(1):77–85.ZHANG Yuanyuan, LV Yanwu. J Synthetic Crystals, 2018, 47(1):77–85.
[48] CHEN H, HUA Y R, LUO N J, et al. Lithiation abilities of SiC bulks and surfaces:A first-principles study[J]. J Phys Chem C, 2020, 124(13):7031–7038.
[49] MAJID A, FATIMA S A, UD-DIN KHAN S, et al. Assessment of2H–SiC based intercalation compound for use as anode in lithium ion batteries[J]. Ceram Int, 2020, 46(4):5297–5305.
[50] SHARIF M N, YANG J S, ZHANG X K, et al. Tailoring electronic properties of 6H-SiC with different composition of silicon by first-principles calculations[J]. Adv Theory Simul, 2024, 7(6):2400245.
[51] SAKAI Y, OSHIYAMA A. Electron doping through lithium intercalation to interstitial channels in tetrahedrally bonded SiC[J]. J Appl Phys, 2015, 118(17):175704.
基本信息:
DOI：10.14062/j.issn.0454-5648.20240518
中图分类号:TB332;TM912
引用信息:
[1]杨森,郑康,赵宁.第一性原理计算在锂离子电池硅碳负极材料中的研究进展[J].硅酸盐学报,2025,53(01):148-160.DOI:10.14062/j.issn.0454-5648.20240518.
基金信息:
辽宁省教育厅科研项目(JYTMS20230800)
2024-08-08
2024
2024-10-29
2024
1
2024-11-20
2024-11-20
2024-11-20