Sandwich-like structure C/SiO _x@graphene anode material with high electrochemical performance for lithium ion batteries

Abstract

Silicon suboxide (SiO _x, 0 < x < 2) is recognized as one of the next-generation anode materials for high-energy-density lithium ion batteries (LIBs) due to its high theoretical specific capacity and abundant resource. However, the severe mechanical instability arising from large volume variation upon charge/discharge cycles frustrates its electrochemical performance. Here we propose a well-designed sandwichlike structure with sandwiched SiO _x nanoparticles between graphene sheets and amorphous carbon-coating layer so as to improve the structural stability of SiO _x anode materials during cycling. Graphene sheets and carbon layer together construct a three-dimensional conductive network around SiO _x particles, which not only improves the electrode reactions kinetics, but also homogenizes local current density and thus volume variation on SiO _x surface. Moreover, Si−O−C bonds between SiO _x and graphene endow the strong particle adhesion on graphene sheets, which prevents SiO _x peeling from graphene sheets. Owing to the synergetic effects of the structural advantages, the C/SiO _x@graphene material exhibits an excellent cyclic performance such as 890 mAh/g at 0.1 C rate and 73.7% capacity retention after 100 cycles. In addition, it also delivers superior rate capability with a capacity recovery of 886 mAh/g (93.7% recovery rate) after 35 cycles of ascending steps at current range of 0.1–5 C and finally back to 0.1 C. This study provides a novel strategy to improve the structural stability of high-capacity anode materials for lithium/sodium ion batteries.

Keywords

sandwich-like structure / silicon suboxide / electrochemical performance / anode / lithium-ion battery

References

[1] H.Y. Li, H.D. Li, Z.W. Yang, et al., SiO_x anode: From fundamental mechanism toward industrial application, Small, 17(2021), No. 51, art. No. 2102641.

[2] L. Sun, Y.X. Liu, J. Wu, et al., A review on recent advances for boosting initial Coulombic efficiency of silicon anodic lithium ion batteries, Small, 18(2022), No. 5, art. No. 2102894.

[3] Chen T, Wu J, Zhang QL, Su X. Recent advancement of SiO_x based anodes for lithium-ion batteries. J. Power Sources, 2017, 363, 126.

[4] Zhang JY, Zhang CQ, Liu Z, et al. High-performance ball-milled SiO_x anodes for lithium ion batteries. J. Power Sources, 2017, 339, 86.

[5] J.G. Guo, W. Zhai, Q. Sun, et al., Facilely tunable core-shell Si@SiO_x nanostructures prepared in aqueous solution for lithium ion battery anode, Electrochim. Acta, 342(2020), art. No. 136068.

[6] J. Peng, J. Luo, W.W. Li, et al., Insight into the performance of the mesoporous structure SiO_x nanoparticles anchored on carbon fibers as anode material of lithium-ion batteries, J. Electroanal. Chem, 880(2021), art. No. 114798.

[7] Q. Xu, J.K. Sun, Y.X. Yin, and Y.G. Guo, Facile synthesis of blocky SiO_x/C with graphite-like structure for high-performance lithium-ion battery anodes, Adv. Funct. Mater., 28(2018), No. 8, art. No. 1705235.

[8] Liu ZH, Guan DD, Yu Q, et al. Monodisperse and homogeneous SiO_x/C microspheres: A promising high-capacity and durable anode material for lithium-ion batteries. Energy Storage Mater., 2018, 13, 112.

[9] Guo WL, Yan X, Hou F, et al. Flexible and free-standing Si−O_x/CNT composite films for high capacity and durable lithium ion batteries. Carbon, 2019, 152, 888.

[10] Wu MR, Gao MY, Zhang SY, et al. High-performance lithium-sulfur battery based on porous N-rich g-C₃N₄ nanotubes via a self-template method. Int. J. Miner. Metall. Mater., 2021, 28(10): 1656.

[11] Wang YR, Zhang L, Gao XH, Mao LY, Hu Y, Lou XW. One-pot magnetic field induced formation of Fe₃O₄/C composite microrods with enhanced lithium storage capability. Small, 2014, 10(14): 2815.

[12] Cheng DL, Yang LC, Hu RZ, et al. Sn−C and Se−C co-bonding SnSe/few-layered graphene micro-nano structure: Route to a densely compacted and durable anode for lithium/sodium-ion batteries. ACS Appl. Mater. Interfaces, 2019, 11(40): 36685.

[13] Wang GQ, Wen ZS, Yang YE, et al. Ultra-long life Si@rGO/g-C₃N₄ with a multiply synergetic effect as an anode material for lithium-ion batteries. J. Mater. Chem. A, 2018, 6(17): 7557.

[14] Khavryuchenko VD, Khavryuchenko OV, Lisnyak VV. Quantum chemical insight on vibration spectra of silica systems. Mol. Simul., 2007, 33(6): 531.

[15] Chen YF, Lai FF, Li JL. Effect of B₂O₃ on structure of glassy F-free CaO−SiO₂−B₂O₃ systems by ²⁹Si MAS NMR and Raman spectroscopy. JOM, 2020, 72(3): 1414.

[16] Prasath A, Sharma AS, Elumalai P. Nanostructured SiO₂@NiO heterostructure derived from laboratory glass waste as anode material for lithium-ion battery. Ionics, 2019, 25(3): 1015.

[17] Z.L. Li, H.L. Zhao, P.P. Lv, et al., Watermelon-like structured SiO_x−TiO₂@C nanocomposite as a high-performance lithium-ion battery anode, Adv. Funct. Mater., 28(2018), No. 31, art. No. 1605711.

[18] Azimov F, Markova I, Stefanova V, Sharipov K. Synthesis and characterization of SBA-15 and Ti-SBA-15 nanoporous materials for DME catalysts. J. Univ. Chem. Technol. Metall., 2012, 47(3): 333

[19] Wang DS, Gao MX, Pan HG, Wang JH, Liu YF. High performance amorphous-Si@SiO_x/C composite anode materials for Li-ion batteries derived from ball-milling and in situ carbonization. J. Power Sources, 2014, 256, 190.

[20] F.F. Wang, S. Lin, X.S. Lu, R.Y. Hong, and H.Y. Liu, Polydopamine carbon-coated stable silicon/graphene/CNT composite as anode for lithium ion batteries, Electrochim. Acta, 404(2022), art. No. 139708.

[21] Cao YD, Hans S, Liese J, et al. Si(CO)_y negative electrodes for Li-ion batteries. Chem. Mater., 2021, 33(18): 7386.

[22] M.Y. Gao, Z.H. Tang, M.R. Wu, et al., Self-supporting N, P doped Si/CNTs/CNFs composites with fiber network for high-performance lithium-ion batteries, J. Alloys Compd., 857(2021), art. No. 157554.

[23] Ramezanzadeh B, Ahmadi A, Mahdavian M. Enhancement of the corrosion protection performance and cathodic delamination resistance of epoxy coating through treatment of steel substrate by a novel nanometric sol-gel based silane composite film filled with functionalized graphene oxide nanosheets. Corros. Sci., 2016, 109, 182.

[24] Xie HM, Dai JH, Zhou D. Tribological behaviors of graphene oxide partly substituted with nano-SiO₂ as lubricant additives in water for magnesium alloy/steel interfaces. Int. J. Miner. Metall. Mater., 2022, 29(7): 1425.

[25] Zhao H, Wang ZH, Lu P, et al. Toward practical application of functional conductive polymer binder for a high-energy lithium-ion battery design. Nano Lett., 2014, 14(11): 6704.

[26] J. Zhao, Z.D. Lu, N. Liu, H.W. Lee, M.T. McDowell, and Y. Cui, Dry-air-stable lithium silicide-lithium oxide core-shell nanoparticles as high-capacity prelithiation reagents, Nat. Commun., 5(2014), No. 1, art. No. 5088.

[27] Cao ZY, Xu PY, Zhai HW, et al. Ambient-air stable lithiated anode for rechargeable Li-ion batteries with high energy density. Nano Lett., 2016, 16(11): 7235.

[28] Duan MT, Wu MR, Xue K, et al. Preparation of CoO/SnO₂@NC/S composite as high-stability cathode material for lithium-sulfur batteries. Int. J. Miner. Metall. Mater., 2021, 28(10): 1647.

[29] Fu LJ, Liu H, Zhang HP, et al. Novel TiO₂/C nanocomposites for anode materials of lithium ion batteries. J. Power Sources, 2006, 159(1): 219.