硅储量丰富,低放电电压和高理论比容量使其成为新一代锂离子电池负极材料的有力竞争者。但是硅负极在锂离子嵌入脱出的过程中极易粉化,导致容量快速衰减。通过调控硅与氧化石墨烯的比例,采用静电自组装法制备了柔性自支撑氮掺杂还原氧化石墨烯/硅(N-rGO@Si)复合材料。透射电子显微镜和X射线光电子能谱分析表明纳米硅颗粒被还原氧化石墨烯(rGO)片层包裹同时被氮掺杂。相比于纯硅电极,柔性自支撑复合电极的电化学性能明显提升,其中N-rGO@Si-2表现最优,在电流密度100mA/g条件下经过100次循环后可逆比容量仍保持1090.92mAh/g,这得益于碳包覆和氮掺杂,氮掺杂提高了复合材料的导电性,薄膜型石墨烯约束了纳米硅颗粒的体积变化,维持了结构和界面稳定性,并为界面提供了有效保护,使其具有优异的储锂性能。
The abundance of silicon reserves,low discharge voltage and high theoretical specific capacity make it a strong contender for the new generation of anode materials for lithium-ion batteries.However,silicon anode is highly susceptible to pulverisation during the process of lithium ion embedding and detachment,leading to rapid capacity degradation.Flexible self-supported nitrogen-doped reduced graphene oxide/silicon (N-rGO@Si) composites were prepared via an electrostatic self-assembly method by modulating the ratio of silicon to graphene oxide.The silicon nanoparticles were encapsulated by reduced graphene oxide (rGO) lamellae simultaneously doped with nitrogen as analyzed by transmission electron microscopy and X-ray photoelectron spectroscopy.Compared with the pure silicon electrode,the electrochemical performance of the flexible self-supported composite electrode was significantly improved,among which N-rGO@Si-2 performed the best,and the reversible specific capacity remained 1090.92mAh/g after 100 cycles at a current density of 100mA/g.This was attributed to the carbon coating and nitrogen doping,which improved the electrical conductivity of the composite material,and the thin film-type graphene constrained the volume change of silicon nanoparticles,maintained the structural and interfacial stability,and provided effective protection for the interface,resulting in excellent lithium storage performance.
[1] Dai X,Liu H,Liu X,et al.Silicon nanoparticles encapsulated in multifunctional crosslinked nano-silica/carbon hybrid matrix as a high-performance anode for Li-ion batteries[J].Chemical Engineering Journal,2021,418:129468.
[2] Zhang X,Weng J,Ye C,et al.Strategies for controlling or releasing the influence due to the volume expansion of silicon inside Si—C composite anode for high-performance lithium-ion batteries[J].Materials,2022,15(12):4264.
[3] Han J,Johnson I,Chen M.3D continuously porous graphene for energy applications[J].Advanced Materials,2022,34(15):2108750.
[4] Wei W,Yang S,Zhou H,et al.3D graphene foams cross-linked with pre-encapsulated Fe3O4 nanospheres for enhanced lithium storage[J].Advanced Materials,2013,25(21):2909-2914.
[5] Zhao X,Hayner C M,Kung M C,et al.In-plane vacancy-enabled high-power Si-graphene composite electrode for lithium-ion batteries[J].Advanced Energy Materials,2011,1(6):1079-1084.
[6] Fan Z,Wang Y,Zheng S,et al.A submicron Si@C core-shell intertwined with carbon nanowires and graphene nanosheet as a high-performance anode material for lithium ion battery[J].Energy Storage Materials,2021,39:1-10.
[7] Zhu B,Jin Y,Tan Y,et al.Scalable production of Si nanoparticles directly from low grade sources for lithium-ion battery anode[J].Nano Letters,2015,15(9):5750-5754.
[8] Ye X,Wang C,Wang L,et al.DLP printing of a flexible micropattern Si/PEDOT∶PSS/PEG electrode for lithium-ion batteries[J].Chemical Communications,2022,58(55):7642-7645.
[9] Kim K H,Moon D B,Jo M H,et al.Carbon nanotube-interlocked Si/CNF self-supporting electrode using continuable spraying architecture system for flexible lithium-ion batteries[J].Applied Surface Science,2024,656:159663.
[10] Xu W,Zhao K,Zhang L,et al.SnS2@Graphene nanosheet arrays grown on carbon cloth as freestanding binder-free flexible anodes for advanced sodium batteries[J].Journal of Alloys and Compounds,2016,654:357-362.
[11] 周颖,姜磊,阎景旺,等.石墨烯纸的制备及电容特性[J].高等学校化学学报,2014,35(3):619-625.
[12] Tao H,Xiong L,Zhu S,et al.Flexible binder-free reduced graphene oxide wrapped Si/carbon fibers paper anode for high-performance lithium ion batteries[J].International Journal of Hydrogen Energy,2016,41(46):21268-21277.
[13] Zhang Y,Cheng Y,Song J,et al.Functionalization-assistant ball milling towards Si/graphene anodes in high performance Li-ion batteries[J].Carbon,2021,181:300-309.
[14] Wang F,Hu Z,Mao L,et al.Nano-silicon@soft carbon embedded in graphene scaffold:high-performance 3D free-standing anode for lithium-ion batteries[J].Journal of Power Sources,2020,450:227692.
[15] Qiao B,Wang T J,Gao H,et al.High density silanization of nano-silica particles using γ-aminopropyltriethoxysilane (APTES)[J].Applied Surface Science,2015,351:646-654.
[16] Bao J,Wang J,Zhou Y,et al.Anchoring ultrafine PtNi nano-particles on N-doped graphene for highly efficient hydrogen evolution reaction[J].Catalysis Science & Technology,2019,9(18):4961-4969.
[17] Xie X,Xiao P,Pang L,et al.Facile synthesis of yolk-shell Si@void@C nanoparticles with 3D conducting networks as free-standing anodes in lithium-ion batteries[J].Journal of Alloys and Compounds,2023,931:167473.
[18] Song J,Ke S,Sun P,et al.High-performance Si@C anode for lithium-ion batteries enabled by a novel structuring strategy[J].Nanoscale,2023,15(33):13790-13808.
[19] Jin D,Yang X,Ou Y,et al.Thermal pyrolysis of Si@ZIF-67 into Si@N-doped CNTs towards highly stable lithium storage[J].Science Bulletin,2020,65(6):452-459.
[20] Luan Y,Yang B,Zhu K,et al.Silicon nanoparticles embedded in N-doped few-layered graphene:facile synthesis and application as an effective anode for lithium ion batteries[J].ChemPlusChem,2019,84(10):1519-1524.
[21] Tang X,Wen G,Song Y.Stable silicon/3D porous N-doped graphene composite for lithium-ion battery anodes with self-assembly[J].Applied Surface Science,2018,436:398-404.
[22] Li Q,Chen D,Li K,et al.Electrostatic self-assembly bmSi@C/rGO composite as anode material for lithium ion battery[J].Electrochimica Acta,2016,202:140-146.
[23] Wang L,Zheng X,Yu Y,et al.Scalable synthesis of high-performance Si/CNTs/C anodes for lithium-ion batteries based on recycling of silicon cutting waste[J].Journal of Electroanalytical Chemistry,2024,952:117942.
[24] Baltazar J,Sojoudi H,Paniagua S A,et al.Facile formation of graphene P-N junctions using self-assembled monolayers[J].The Journal of Physical Chemistry C,2012,116(36):19095-19103.
基金资助
国家自然科学基金(51402030);重庆市技术创新与应用发展专项重点项目(CSTB2022TIAD-KPX0031);重庆市级引导区县科技发展专项资金(JSYY2023010);重庆市研究生导师团队建设项目(JDDSTD2022006)
PDF
