SnO₂ Particles Embedded into Carbon Coated Mesoporous SiO_x Rod as High Volumetric Capacity Anode for Lithium-Ion Batteries

Abstract

Due to the high capacity and moderate volume expansion of silicon protoxide SiO_x (160%) compared with that of Si (300%), reducing silicon dioxide SiO₂ into SiO_x while maintaining its special nano-morphology makes it attractive as an anode of Li-ion batteries. Herein, through a one-pot facile high-temperature annealing route, using SBA15 as the silicon source, and embedding tin dioxide SnO₂ particles into carbon coated SiO_x, the mesoporous SiO_x-SnO₂@C rod composite was prepared and tested as the anode material. The results revealed that the SnO₂ particles were distributed uniformly in the wall, which could further improve their volume energy densities. The coated carbon plays a role in maintaining structural integrality during lithiation, and the rich mesopores structure can release the expanded volume and enhance Li-ion transfer. At 0.1 A·g^-1, the gravimetric and volumetric capacities of the composite were as high as 1271 mAh·g^-1and 1573 mAh·cm^-3, respectively. After 200 cycles, the 95% capacity could be retained compared with that upon the 2nd cycle at 0.5 A·g^-1. And the rod morphology was well kept, except that the diameter of the rod was 3 times larger than its original size after the cell was discharged into 0.01 V.

Keywords

Carbon coating / Mesoporous SiO_x / Anode / Li-ion battery

References

[1] Pendashteh A, Tomey R, Vilatela J. Nanotextile 100% Si anodes for the next generation energy-dense Li-ion batteries[J]. Adv. Energy Mater., 2024, 14(16): 2304018.

[2] Lu B, Ma B J, Deng X L, Li W W, Wu Z Y, Shu H B, Wang X Y. Cornlike ordered mesoporous silicon particles modified by nitrogen-doped carbon layer for the application of Li-ion battery[J]. ACS Appl. Mater. Interfaces, 2017, 9(38): 32829-32839.

[3] Xu G L, Xiao L, Sheng T, Liu J, Hu Y X, Ma T, Amine R, Xie Y, Zhang X, Liu, Y. Electrostatic self-assembly enabling integrated bulk and interfacial sodium storage in 3D titania-graphene hybrid[J]. Nano Lett., 2018, 18(1): 336-346.

[4] Kalluri S, Yoon M, Jo M, Park S, Myeong S, Kim J, Dou S X, Guo Z, Cho J. Surface engineering strategies of layered LiCoO₂ cathode material to realize high-energy and high-voltage Li-ion cells[J]. Adv. Energy Mater., 2017, 7(1): 1601507.

[5] Meng B C, Yu J, Peng J X, Wei Y B, Zhu F, Chen T X, Yang N X, Chuan X, Li L B. Combine natural stibnite with bio-carbon: A high-capacity composite anode material for lithium-ion battery[J]. JOM, 2023, 75(7): 2626-2635.

[6] Ma Y, Zheng Y, Xu M, Huang S, Yuan G H. One-step binding and wrapping fragmented natural microcrystalline graphite via phenolic resin into secondary particles for high-performance lithium-ion battery anode[J]. JOM, 2023, 75(12): 5321-5330.

[7] Xia X, Qian X Y, Chen C, Li W Y, He D F, He G Y, Chen H Q. Recent progress of Si-based anodes in the application of lithium-ion batteries[J]. J. Energy Storage, 2023, 72: 108715.

[8] Liu Y B, Liu X Y, Zhu Y L, Wang J W, Ji W W, Liu X Z. Scalable synthesis of pitch-coated nanoporous Si/graphite composite anodes for lithium-ion batteries[J]. Energy Fuels, 2023, 37(6): 4624-4631.

[9] Li Y F, Li Q M, Chai J L, Wang Y T, Du J K, Chen Z Y, Rui Y C, Jiang L, Tang B H J. Si-based Anode Lithium-Ion Batteries: A Comprehensive Review of Recent Progress[J]. ACS Mater. Lett., 2023, 5(11): 2948-2970.

[10] Ming H, Qiu J Y, Zhang S T, Li M, Zhu X Y, Wang L M, Ming J. Constructing dense SiO_x@carbon nanotubes versus spinel cathode for advanced high-energy lithium-ion batteries[J]. ChemElectroChem, 2017, 4(5): 1165-1171.

[11] Liu Q, Cui Z, Zou R J, Zhang J H, Xu K B, Hu J Q. Surface coating constraint induced anisotropic swelling of silicon in Si-void@SiO_x nanowire anode for lithium-ion batteries[J]. Small, 2017, 13(13): 1603754.

[12] Fu R S, Zhang K L, Zaccaria R P, Huang H R, Xia Y G, Liu Z P. Two-dimensional silicon suboxides nanostructures with Si nanodomains confined in amorphous SiO₂ derived from siloxene as high performance anode for Li-ion batteries[J]. Nano Energy, 2017, 39: 546-553.

[13] Chen P H, Wu H, Huang S S, Zhang Y. Template synthesis and lithium storage performances of hollow spherical LiMn₂O₄ cathode materials[J]. Ceram. Int., 2016, 42(8): 10498-10505.

[14] Wu G L, Jia Z R, Cheng Y H, Zhang H X, Zhou X F, Wu H J. Easy synthesis of multi-shelled ZnO hollow spheres and their conversion into hedgehog-like ZnO hollow spheres with superior rate performance for lithium ion batteries[J]. Appl. Surf. Sci., 2019, 464: 472-478.

[15] Liu Y, Haridas A. K., Lee Y., Cho K K, Ahn J H. Freestanding porous sulfurized polyacrylonitrile fiber as a cathode material for advanced lithium sulfur batteries[J]. Appl. Surf. Sci., 2019, 472: 135-142.

[16] Ma T Y, Yu X N, Li H Y, Zhang W G, Cheng X L, Zhu W T, Qiu X P. High volumetric capacity of hollow structured SnO₂@Si nanospheres for lithium-ion batteries[J]. Nano Lett., 2017, 17(6): 3959-3964.

[17] Zhou Z W, Liu Y T, Xie X M, Ye X Y. Constructing novel Si@SnO₂ core-shell heterostructures by facile self-assembly of SnO₂ nanowires on silicon hollow nanospheres for large, reversible lithium storage[J]. Appl. Surf. Sci., 2016, 8(11): 7092-7100.

[18] Lei Y, Li S, Du M, Mi J, Gao D C, Hao L, Jiang L J, Luo M, Jiang W Q, Li F, Wang S H. Preparation of double-shell Si@SnO₂@C nanocomposite as anode for lithium-ion batteries by hydrothermal method[J]. Rare Met., 2023, 42(9): 2972-2981.

[19] Ji X L, Lee K T, Monjauze M, Nazar L F. Strategic synthesis of SBA-15 nanorods[J]. Chem. Commun., 2008, 36: 4288-4290.

[20] Zhang N, Zhao Q, Han X P, Yang J G, Chen J. Pitaya-like Sn@C nanocomposites as high-rate and long-life anode for lithium-ion batteries[J]. Nanoscale, 2014, 6(5): 2827-2832.

[21] Ren D Z, Huang H, Qi J G, Zheng P. One-pot template-free cross-linking synthesis of SiOx-SnO₂@C hollow spheres as a high volumetric capacity anode for lithium-ion batteries[J]. Energy Technol., 2020, 8(7): 2000314.

[22] Liu Y H, Xu Y H, Zhu Y J, Culver J N, Lundgren C A, Xu K, Wang C S. Tin-coated viral nanoforests as sodium-ion battery anodes[J]. ACS Nano, 2013, 7(4): 3627-3634.

[23] Chang P, Liu X X, Zhao Q J, Huang Y Q, Huang Y H, Hu X L. Constructing three-dimensional honeycombed graphene/silicon skeletons for high-performance Li-ion batteries[J]. ACS Appl. Mater. Interfaces, 2017, 9(37): 31879-31886.

[24] Murugesan S, Harris J T, Korgel B A, Stevenson K J. Copper-coated amorphous silicon particles as an anode material for lithium-ion batteries[J]. Chem. Mater., 2012, 24(7): 1306-1315.

[25] Zheng P, Liu T, Guo S W. Micro-nano structure hard carbon as a high performance anode material for sodium-ion batteries[J]. Sci. Rep., 2016, 6: 35620.

[26] Zheng P, Liu T, Yuan X Y, Zhang L F, Liu Y, Huang J F, Guo S W. Enhanced performance by enlarged nano-pores of holly leaf-derived lamellar carbon for sodium-ion battery anode[J]. Sci. Rep., 2016, 6: 26246.

[27] Michelson A, Zhang H H, Xiang S T, Gang O. Engineered silicon carbide three-dimensional frameworks through DNA-prescribed assembly[J]. Nano Lett., 2021, 21(4): 1863-1870.

[28] Ren Y R, Li M Q. Facile synthesis of SiOx@C composite nanorods as anodes for lithium ion batteries with excellent electrochemical performance[J]. J. Power Sources, 2016, 306: 459-466.

[29] Hu Y S, Demir-Cakan R, Titirici M M, Müller J O, Schlögl R, Antonietti M, Maier J. Superior storage performance of a Si@SiOx/C nanocomposite as anode material for lithium-ion batteries[J]. Angew. Chem., Int. Ed., 2008, 47(9): 1645-1649.

[30] Zheng P, Su J X, Wang Y B, Zhou W, Song J J, Su Q M, Reeves-McLaren N, Guo S W. A high-performance primary nanosheet heterojunction cathode composed of Na_0.44MnO₂ tunnels and layered Na₂Mn₃O₇ for Na-ion batteries[J]. ChemSusChem, 2020, 13(7): 1793-1799.

[31] Liu Z H, Yu Q, Zhao Y L, He R H, Xu M, Feng S H, Li S D, Zhou L, Mai L Q. Silicon oxides: a promising family of anode materials for lithium-ion batteries. Chem. Soc. Rev. 2019, 48(1): 285-309.