Corresponding Author

Shi-gang LU(lusg8867@163.com)


In this paper, the effects of additives on the cycling performance of silicon nanoparticles in LiFSI-(PC)3 based concentrated electrolytes were systematically studied. The structures of silicon nanoparticle electrodes and the evolution of solid-electrolyte-interphase were characterized by scanning electron microscopy (SEM), attenuated total reflection Flourier transformed infrared spectroscopy (ATR-FTIR) and X-ray photoelectron spectroscopy (XPS). The results indicated that the additives can efficiently improve the cycling performance of silicon nanoparticle electrodes. In LiFSI-(PC)3 concentrated electrolyte, the capacity became 574.8 mAh·g-1 after 300 cycles with the initial capacity of 3296.1 mAh·g-1. In contrast, the 3% LiDFOB, 3% FEC and 3% TMSB-containing systems reached 1142.9, 1863.6 and 1852.2 mAh·g-1 after 300 cycles, respectively. The comprehensive analysis indicates that the reduction of LiFSI takes priority over PC on the surface of silicon nanoparticles in LiFSI-(PC)3 concentrated electrolyte, and the SEI film is composed of an inner layer dominated by inorganic products and an outer layer dominated by organic products. While in the concentrated electrolyte containing additives, the additives and LiFSI participate in the formation of SEI inner layer synergistically, and the SEI inner layer can suppress the reduction of PC which contribute to the formation of SEI outer layer. The SEI film formed on this mechanism could suppress the excessive growth of the SEI film, mitigate the pulverization of silicon nanoparticles, and enhance the structure stability of the silicon nanoparticle electrode, thus, the silicon nanoparticle electrodes exhibited better cycling performance.

Graphical Abstract


lithium-ion batteries, silicon nanoparticle electrode, concentrated electrolyte, additive

Publication Date


Online Available Date


Revised Date


Received Date



[1] Horowitz Y, Han H L, Soto F A, et al. Fluoroethylene carbonate as a directing agent in amorphous silicon anodes: electrolyte interface structure probed by sum frequency vibrational spectroscopy and ab initio molecular dynamics[J]. Nano Letters, 2018,18(2):1145-1151.
URL pmid: 29251510

[2] Veith G M, Doucet M, Sacci R L, et al. Determination of the solid electrolyte interphase structure grown on a silicon electrode using a fluoroethylene carbonate additive[J]. Scientific Reports, 2017,7(1):1-15.
URL pmid: 28127051

[3] Schiele A, Breitung B, Hatsukade T, et al. The critical role of fluoroethylene carbonate in the gassing of silicon anodes for lithium-ion batteries[J]. ACS Energy Letters, 2017,2(10):2228-2233.

[4] Choi N S, Yew K H, Kim H, et al. Surface layer formed on silicon thin-film electrode in lithium bis(oxalato) borate-based electrolyte[J]. Journal of Power Sources, 2007,172(1):404-409.

[5] Song H Y, Jeong S K. Surface film formation on graphite in propylene carbonate solution containing lithium bis (oxalate) borate[J]. Journal of Nanoscience & Nanotechnology, 2016,16(10):10583-10587.

[6] Lee S J, Han J G, Lee Y, et al. A bi-functional lithium difluoro(oxalato) borate additive for lithium cobalt oxide/lithium nickel manganese cobalt oxide cathodes and silicon/graphite anodes in lithium-ion batteries at elevated temperatures[J]. Electrochimica Acta, 2014,137:1-8.

[7] Dalavi S, Guduru P, Lucht B L. Performance enhancing electrolyte additives for lithium ion batteries with silicon anodes[J]. Journal of The Electrochemical Society, 2012,159(5):A642-A646.

[8] 上田敦史, 岩本和也, 芳泽浩司. 非水电解质电池和非水电解液: 中国专利, CN1316791A[P/OL]. 2001-10-10.

[9] Chang Z H, Wang J T, Wu Z H, et al. The electrochemical performance of silicon nanoparticles in concentrated electrolyte[J]. ChemSusChem, 2018,11(11):1787-1796.
doi: 10.1002/cssc.201800480 URL pmid: 29673129

[10] Chang Z H, Li X, Yun F L, et al. Effect of dual-salt concentrated electrolytes on the electrochemical performance of silicon nanoparticles[J]. ChemElectroChem, 2020,7(5):1135-1141.

[11] Chen L B, Wang K, Xie X H, et al. Enhancing electrochemical performance of silicon film anode by vinylene carbonate electrolyte additive[J]. Electrochemical and Solid State Letters, 2006,9(11):A512-A515.

[12] Aurbach D, Weissman I, Zaban A, et al. Correlation between surface chemistry, morphology, cycling efficiency and interfacial properties of Li electrodes in solutions containing different Li salts[J]. Electrochimica Acta, 1994,39(1):51-71.

[13] Yoon T, Milien M S, Parimalam B S, et al. Thermal decomposition of the solid electrolyte interphase (SEI) on silicon electrodes for lithium ion batteries[J]. Chemistry of Materials, 2017,29(7):3237-3245.

[14] Zhuang G V, Ross P N. Analysis of the chemical composition of the passive film on Li-ion battery anodes using attentuated total reflection infrared spectroscopy[J]. Electrochemical and Solid-State Letters, 2003,6(7):A136-A139.

[15] Huang J, Hollenkamp A F. Thermal behavior of ionic liquids containing the FSI anion and the Li+ cation[J]. Journal of Physical Chemistry C, 2010,114(49):21840-21847.

[16] Budi A, Basile A, Opletal G, et al. Study of the initial stage of solid electrolyte interphase formation upon chemical reaction of lithium metal and n-methyl-n-propyl-pyrrolidinium-bis(fluorosulfonyl) imide[J]. Journal of Phy-sical Chemistry C, 2012,116(37):19789-19797.

[17] Diao Y, Xie K, Xiong S Z, et al. Insights into Li-S battery cathode capacity fading mechanisms: irreversible oxidation of active mass during cycling[J]. Journal of The Ele-ctrochemical Society, 2012,159(11):A1816-A1821.

[18] Nguyen C C, Woo S W, Song S W. Understanding the interfacial processes at silicon-copper electrodes in ionic liquid battery electrolyte[J]. Journal of Physical Chemistry C, 2012,116(28):14764-14771.

[19] Ota H, Sakata Y, Wang X M, et al. Characterization of lithium electrode in lithium imides/ethylene carbonate and cyclic ether electrolytes[J]. Journal of the Electrochemical Society, 2004,151(3):A437-A446.

[20] Howlett P C, Brack N, Hollenkamp A F, et al. Characterization of the lithium surface in n-methyl-n-alkylpyrrolidinium bis(trifluoromethanesulfonyl) amide room-temper-ature ionic liquid electrolytes[J]. Journal of the Electrochemical Society, 2006,153(3):A595-A606.

[21] Deepa M, Agnihotry S A, Gupta D, et al. Ion-pairing effects and ion-solvent-polymer interactions in LiN(CF3SO2)2-PC-PMMA electrolytes: a FTIR study[J]. Electrochimica Acta, 2004,49(3):373-383.

[22] Aurbach D, Pollak E, Elazari R, et al. On the surface chemical aspects of very high energy density, rechargeable Li-sulfur batteries[J]. Journal of The Electrochemical Society, 2009,156(8):A694-A702.

[23] Lee H, Lee D J, Lee J N, et al. Chemical aspect of oxygen dissolved in a dimethyl sulfoxide-based electrolyte on lithium metal[J]. Electrochimica Acta, 2014,123:419-425.

[24] Nguyen C C, Song S W. Characterization of SEI layer formed on high performance Si-Cu anode in ionic liquid battery electrolyte[J]. Electrochemistry Communications, 2010,12(11):1593-1595.

[25] Xiao A, Yang L, Lucht B L, et al. Examining the solid electrolyte interphase on binder-free graphite electrodes[J]. Journal of The Electrochemical Society, 2009,156(4):A318-A327.

[26] Etacheri V, Haik O, Goffer Y, et al. Effect of fluoroethylene carbonate (FEC) on the performance and surface chemistry of Si-nanowire Li-ion battery anodes[J]. Langmuir, 2012,28(1):965-976.
doi: 10.1021/la203712s URL pmid: 22103983

[27] Michan A L, Parimalam B S, Leskes M, et al. Fluoroethylene carbonate and vinylene carbonate reduction: understanding lithium-ion battery electrolyte additives and solid electrolyte interphase formation[J]. Chemistry of Materials, 2016,28(22):8149-8159.
doi: 10.1021/acs.chemmater.6b02282 URL

[28] Zhang X Q, Cheng X B, Chen X, et al. Fluoroethylene carbonate additives to render uniform Li deposits in lithium metal batteries[J]. Advanced Functional Materials, 2017,27(10):1605989.



To view the content in your browser, please download Adobe Reader or, alternately,
you may Download the file to your hard drive.

NOTE: The latest versions of Adobe Reader do not support viewing PDF files within Firefox on Mac OS and if you are using a modern (Intel) Mac, there is no official plugin for viewing PDF files within the browser window.