为缓解硅基负极的体积效应以改善其循环性能,采用球磨法制备了具有包覆形貌的铜硅复合粉末作为电极材料。结果表明:增加铜组分的比例和铜粉的粒度有利于形成包覆结构和Cu-Si合金,5种不同粒度的磨球混合球磨时磨球和粉末温度最高。将不同球磨时间样品的X射线衍射(XRD)谱图进行定量分析,1h就有少量的Cu3Si和Cu15Si4生成,球磨时间增加,Cu3Si和Cu15Si4含量不断增多,Cu和Si单质相应减少,球磨8h后,各相含量变化不大,趋于稳定。电化学性能测试表明,相比纯Si电极,Cu100-xSix电极具有优良的循环性能,但随着铜含量的增加,反应动力学减慢。
In order to alleviate the volume effect of silicon-based anode and improve its cycling performance,copper silicon composite powder with coating morphology was prepared as electrode material by ball milling method.The results showed that increasing the proportion of copper components and the particle size of copper powder were beneficial to the formation of coating structure and Cu-Si alloy.The temperature of the grinding ball and the powder was the highest when five grinding balls with different particle sizes were mixed for ball milling.Quantitative analysis of XRD spectra of samples with different milling time revealed that a small amount of Cu3Si and Cu15Si4 were formed within 1h.With the increase of milling time,the content of Cu3Si and Cu15Si4 increased continuously,and the content of Cu and Si decreased correspondingly.After 8h of ball milling,the content of each phase changed little and tended to be stable.The electrochemical performance test showed that Cu100-xSix electrode had excellent cycling performance compared with pure Si electrode,but the reaction kinetics slowed down with the increase of copper content.
[1] Tomaszewska A,Chu Z,Feng X,et al.Lithium-ion battery fast charging:review[J].ETransportation,2019,1:100011.a
[2] Amrouche S O,Rekioua D,Rekioua T,et al.Overview of energy storage in renewable energy systems[J].International Journal of Hydrogen Energy,2016,41(45):20914-20927.
[3] Xiao X,Zhou W,Kim Y,et al.Regulated breathing effect of silicon negative electrode for dramatically enhanced performance of Li-ion battery[J].Advanced Functional Materials,2015,25(9):1426-1433.
[4] Kumar R,Tokranov A,Sheldon B W,et al.In situ and operando investigations of failure mechanisms of the solid electrolyte interphase on silicon electrodes[J].ACS Energy Letters,2016,1(4):689-697.
[5] Feng K,Li M,Liu W,et al.Silicon-based anodes for lithium-ion batteries:from fundamentals to practical applications[J].Small,2018,14(8):1702737.
[6] 谭毅,王凯.高比能量锂离子电池硅基负极材料研究进展[J].无机材料学报,2019,34(4):249-357.
[7] 宋俊,楚晓婉,张琦,等.锂离子电池硅基复合负极制备方法[J].化工进展,2021,40(7):3664-3678.
[8] Li X,Zhang M,Yuan S,et al.Research progress of silicon/carbon anode materials for lithium-ion batteries:structure design and synthesis method[J].ChemElectroChem,2020,7(21):4289-4302.
[9] Song H,Wang H X,Lin Z,et al.Highly connected silicon-copper alloy mixture nanotubes as high-rate and durable anode materials for lithium-ion batteries[J].Advanced Functional Materials,2016,26(4):524-531.
[10] Ma B,Luo J,Deng X,et al.Hollow silicon-tin nanospheres encapsulated by N-doped carbon as anode materials for lithium-ion batteries[J].ACS Applied Nano Materials,2018,1(12):6989-6999.
[11] Song C,Zhao B,Chen S,et al.Nickel-assisted one-pot preparation of graphenic carbon matrices embedded with silicon nanoparticles as anode materials for lithium ion batteries[J].Carbon,2021,179:266-274.
[12] Liu C,Zhao Y,Yi R,et al.Alloyed Cu/Si core-shell nanoflowers on the three-dimensional graphene foam as an anode for lithium-ion batteries[J].Electrochimica Acta,2019,306:45-53.
[13] Lu H,Chen W,Liu Q,et al.Si/Cu3Si@C composite encapsulated in CNTs network as high performance anode for lithium ion batteries[J].Journal of Wuhan University of Technology-Materials Science Edition,2019,34(5):1055-1061.
[14] Yoon S,Lee S I,Kim H,et al.Enhancement of capacity of carbon-coated Si-Cu3Si composite anode using metal-organic compound for lithium-ion batteries[J].Journal of Power Sources,2006,161(2):1319-1323.
[15] Zuo P,Yin G,Hao X,et al.Synthesis and electrochemical performance of Si/Cu and Si/Cu/graphite composite anode[J].Materials Chemistry and Physics,2007,104(2-3):444-447.
[16] Du Z,Liu H,Ellis S N,et al.Electrochemistry of CuxSi1-x alloys in Li cells[J].Journal of the Electrochemical Society,2016,163(7):A1275.
[17] Yang Y,Yang H X,Wu Y Q,et al.Graphene caging core-shell Si@Cu nanoparticles anchored on graphene sheets for lithium-ion battery anode with enhanced reversible capacity and cyclic performance[J].Electrochimica Acta,2020,341:136037.
[18] Kim I C,Byun D,Lee J K.Electrochemical characteristics of silicon-metals coated graphites for anode materials of lithium secondary batteries[J].Journal of Electroceramics,2006,17(2):661-665.
[19] Chae S,Ko M,Park S,et al.Micron-sized Fe-Cu-Si ternary composite anodes for high energy Li-ion batteries[J].Energy & Environmental Science,2016,9(4):1251-1257.
[20] Liu Y,Scott B,Obrovac M N.Ball milled Si-W alloys:part I.microstructural and phase evolution during ball milling[J].Journal of the Electrochemical Society,2019,166(6):A1170.
[21] Lee K M,Lee Y S,Kim Y W,et al.Electrochemical characterization of Ti-Si and Ti-Si-Al alloy anodes for Li-ion batteries produced by mechanical ball milling[J].Journal of Alloys and Compounds,2009,472(1-2):461-465.
[22] Hatchard T D,Dahn J R.In situ XRD and electrochemical study of the reaction of lithium with amorphous silicon[J].Journal of the Electrochemical Society,2004,151(6):A838.
[23] Xie J,Wang G,Huo Y,et al.Nanostructured silicon spheres prepared by a controllable magnesiothermic reduction as anode for lithium ion batteries[J].Electrochimica Acta,2014,135:94-100.
[24] Du F H,Ni Y,Wang Y,et al.Green fabrication of silkworm cocoon-like silicon-based composite for high-performance Li-ion batteries[J].ACS Nano,2017,11(9):8628-8635.
基金资助
国家自然科学基金(51906229);河南省科技攻关项目(212102210235);河南省高等学校重点科研项目(21B470013)
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