Abstract:Silicon/carbon composite materials were widely considered as the next generation and the most potential anode materials. In order to reduce the huge expansion of silicon, avoid silicon nanoparticle powder and improve the electrochemical performance of silicon based lithium ion battery, a microporous structure paper of multiwalled carbon nanotubes(MWCNTs) was prepared, and the Si/MWCNTs/cellulose composite flexible lithium ion battery anode was prepared by embedding nanoscale silicon. FESEM shows that the nano-silicons are evenly inserted in the three-dimensional conductive network constructed by MWCNTs. This results in decreased interface resistance owing to increasing contact area between silicon and MWCNTs. The high hole of the anode provides enough space for expansion of silicon in cycles. So, the structural stability and chemical stability of the electrodes significantly are guaranteed. Electrochemical tests demonstrate that the first discharge capacity reaches 2024 mAh/g, and the capacity is still maintained at 850 mAh/g after 30 cycles, which shows good cyclic stability and high specific capacity. The unique electrodes show excellent electrochemical performance. The fabrication process of the electrode is much simpler than traditional coating process, strong maneuverability and a satisfactory prospect for industrial applications.
[1] BEAULIEU L Y,HATCHARD T D,BONAKDARPOUR A,et al. Reaction of Li with alloy thin films studied by in situ AFM[J]. Journal of the Electrochemical Society,2003,150(11):1457-1464.
[2] TAKESHI W,TETSU I,KUNIO Y,et al. Bulk-nanoporous-silicon negative electrode with extremely high cyclability for lithium-ion batteries prepared using a top-down process[J]. Nano Letters,2014,14:4505-4510.
[3] 宋磊,陈纪强,范汶鑫,等. 电化学处理对碳纤维表面加载碳纳米管的影响机理[J]. 材料工程,2017,45(11):19-26. SONG L,CHEN J Q,FAN W X,et al. Influencing mechanism of electrochemical treatment on preparation of CNTs-grafted on carbon fibers[J]. Journal of Materials Engineering,2017,45(11):19-26.
[4] LV Q L,LIU Y,MAT Y,et al. Hollow structured silicon anodes with stabilized solid electrolyte interphase film for lithium-ion batteries[J]. ACS Applied Materials & Interfaces,2015,7(42):23501-23506.
[5] CAO X,CHUAN X,LI S,et al. Hollow silica spheres embedded in a porous carbon matrix and its superior performance as the anode for lithium-ion batteries[J]. Particle & Particle Systems Characterization,2016,33(2):110-117.
[6] MA T,YU X,LI H,et al. High volumetric capacity of hollow structured SnO2@Si nanospheres for lithium-ion batteries[J]. Nano Letters,2017,17(6):3959-3964.
[7] HUANG X,YANG J,MAO S,et al. Controllable synthesis of hollow Si anode for long-cycle-life lithium-ion batteries[J]. Advanced Materials,2014,26(25):4326-4332.
[8] MA H,CHENG F,CHEN J,et al. Nest-like silicon nanospheres for high-capacity lithium storage[J]. Advanced Materials,2010,19(22):4067-4070.
[9] ZHOU X Y,TANG J J,YANG J,et al. Silicon@carbon hollow core-shell heterostructures novel anode materials for lithium ion batteries[J]. Electrochimica Acta,2013,87(1):663-668.
[10] FOWLER C E,KHUSHALANI D,MANN S. Interfacial synthesis of hollow microspheres of mesostructured silica[J]. Chemical Communications,2001,19(19):2028-2029.
[11] LUO F,CHU G,XIA X,et al. Thick solid electrolyte interphases grown on silicon nanocone anodes during slow cycling and their negative effects on the performance of Li-ion batteries[J]. Nanoscale,2015,7(17):7651-7658.
[12] WANG B,LI X,LUO B,et al. Approaching the downsizing limit of silicon for surface-controlled lithium storage[J]. Advanced Materials,2015,27(9):1526-1532.
[13] XIA Y,JUN L,GUO Y. Silicon-based nanomaterials for lithium-ion batteries[J]. Chinese Science Bulletin, 2012,57(32):4104-4110.
[14] DIMOV N,XIA Y,YOSHIO M. Practical silicon-based composite anodes for lithium-ion batteries:fundamental and technological features[J]. Journal of Power Sources,2007,171(2):886-893.
[15] MAROM R,AMALRAJ S F,LEIFER N,et al. A review of advanced and practical lithium battery materials[J]. Journal of Materials Chemistry,2011,21(27):9938-9954.
[16] BABAR A A,WANG X,IQBAL N,et al. Tailoring differential moisture transfer performance of nonwoven/polyacrylonitrile-SiO2 nanofiber composite membranes[J]. Advanced Materials Interfaces,2017,4(15):1700062.
[17] 杨旭东,陈亚军,师春生,等. 球磨工艺对原位合成碳纳米管增强铝基复合材料微观组织和力学性能的影响[J]. 材料工程, 2017,45(9):93-100. YANG X D,CHEN Y J,SHI C S,et al. Effect of ball-milling process on the microstructure and mechanical properties of in-situ synthesized carbon nanotube reinforced aluminum composites[J]. Journal of Materials Engineering,2017,45(9):93-100.
[18] YANG Y,WANG Z,ZHOU Y,et al. Synthesis of porous Si/graphite/carbon nanotubes@C composites as a practical high-capacity anode for lithium-ion batteries[J]. Materials Letters,2017,199:84-87.
[19] SALAJKOVA M,VALENTINI L,ZHOU Q,et al. Tough nanopaper structures based on cellulose nanofibers and carbon nanotubes[J]. Composites Science & Technology,2013,87(9):103-110.
[20] GAO H,HOU F,ZHENG X,et al. Electrochemical property studies of carbon nanotube films fabricated by CVD method as anode materials for lithium-ion battery applications[J]. Vacuum,2015,112:1-4.
[21] KIM Y L,SUN Y K,LEE S M. Enhanced electrochemical performance of silicon-based anode material by using current collector with modified surface morphology[J]. Electrochimica Acta,2008,53(13):4500-4504.
[22] 刘珍红,孙晓刚,陈珑,等. 碳纳米管纸/纳米硅复合电极的锂离子电池性能[J]. 材料工程,2018,46(1):99-105. LIU Z H,SUN X G,CHEN L,et al. Performance of lithium ion batteries with carbon nanotube paper/nano silicon composite electrode[J]. Journal of Materials Engineering,2018,46(1):99-105.
[23] 易健宏,杨平,沈韬. 碳纳米管增强金属基复合材料电学性能研究进展[J]. 复合材料学报,2016,33(4):689-703. YI J H,YANG P,SHEN T. Research progress of electrical properties for carbon nanotubes reinforce metal matrix composites[J]. Acta Materiae Compositae Sinica,2016,33(4):689-703.
[24] ZHOU Z,XU Y,LIU W,et al. High capacity Si/DC/MWCNTs nanocomposite anode materials for lithium ion batteries[J]. Journal of Alloys & Compounds,2010,493(1/2):636-639.
[25] ZHAO T K, JI X L, BI P,et al. In situ synthesis of interlinked three-dimensional graphene foam/polyaniline nanorod supercapacitor[J]. Electrochimica Acta,2017,230:342-349.