Facile controlled synthesis of hierarchically structured mesoporous Li₄Ti₅O₁₂/C/rGO composites as high-performance anode of lithium-ion batteries

Abstract

In this paper, a facile strategy is proposed to controllably synthesize mesoporous Li₄Ti₅O₁₂/C nanocomposite embedded in graphene matrix as lithium-ion battery anode via the co-assembly of Li₄Ti₅O₁₂ (LTO) precursor, GO, and phenolic resin. The obtained composites, which consists of a LTO core, a phenolic-resin-based carbon shell, and a porous frame constructed by rGO, can be denoted as LTO/C/rGO and presents a hierarchical structure. Owing to the advantages of the hierarchical structure, including a high surface area and a high electric conductivity, the mesoporous LTO/C/rGO composite exhibits a greatly improved rate capability as the anode material in contrast to the conventional LTO electrode.

Graphical abstract

Keywords

Li₄Ti₅O₁₂ / phenolic-resin-based carbon / mesoporous composite / graphene

References

[1] Jung H G, Jang M W, Hassoun J, A high-rate long-life Li₄Ti₅O₁₂/Li[Ni_0.45Co_0.1Mn_1.45]O₄ lithium-ion battery. Nature Communications, 2011, 2(1): 516

[2] Dedryvère R, Foix D, Franger S, Electrode/electrolyte interface reactivity in high-voltage spinel LiMn_1.6Ni_0.4O₄/Li₄Ti₅O₁₂ lithium-ion battery. Journal of Physical Chemistry C, 2010, 114(24): 10999–11008

[3] Yu H, Cao Y, Chen L, Surface enrichment and diffusion enabling gradient-doping and coating of Ni-rich cathode toward Li-ion batteries. Nature Communications, 2021, 12(1): 4564

[4] Deng Z, Jiang H, Li C. 2D metal chalcogenides incorporated into carbon and their assembly for energy storage applications. Small, 2018, 14(22): 1800148

[5] Chen L, Liu Y, Deng Z, Edge-enriched MoS₂@C/rGO film as self-standing anodes for high-capacity and long-life lithium-ion batteries. Science China Materials, 2021, 64(1): 96–104

[6] Chen W, Jiang H, Hu Y, Mesoporous single crystals Li₄Ti₅O₁₂ grown on rGO as high-rate anode materials for lithium-ion batteries. Chemical Communications: Cambridge, England, 2014, 50(64): 8856–8859

[7] Huang J, Jiang Z. The preparation and characterization of Li₄Ti₅O₁₂/carbon nano-tubes for lithium ion battery. Electrochimica Acta, 2008, 53(26): 7756–7759

[8] Liu J, Song K, van Aken P A, Self-supported Li₄Ti₅O₁₂-C nanotube arrays as high-rate and long-life anode materials for flexible Li-ion batteries. Nano Letters, 2014, 14(5): 2597–2603

[9] Yan H, Zhang D, Qilu , A review of spinel lithium titanate (Li₄Ti₅O₁₂) as electrode material for advanced energy storage devices. Ceramics International, 2021, 47(5): 5870–5895

[10] Pohjalainen E, Rauhala T, Valkeapää M, Effect of Li₄Ti₅O₁₂ particle size on the performance of lithium ion battery electrodes at high C-rates and low temperatures. Journal of Physical Chemistry C, 2015, 119(5): 2277–2283

[11] Liu G, Zhang R, Bao K, Synthesis of nano-Li₄Ti₅O₁₂ anode material for lithium ion batteries by a biphasic interfacial reaction route. Ceramics International, 2016, 42(9): 11468–11472

[12] Zhu K, Gao H, Hu G, Scalable synthesis of hierarchical hollow Li₄Ti₅O₁₂ microspheres assembled by zigzag-like nanosheets for high rate lithium-ion batteries. Journal of Power Sources, 2017, 340: 263–272

[13] Yuan T, Cai R, Wang K, Combustion synthesis of high-performance Li₄Ti₅O₁₂ for secondary Li-ion battery. Ceramics International, 2009, 35(5): 1757–1768

[14] Wu R, Shen S, Xia G, Soft-templated self-assembly of mesoporous anatase TiO₂/carbon composite nanospheres for high-performance lithium ion batteries. ACS Applied Materials & Interfaces, 2016, 8(31): 19968–19978

[15] Wu R, Xia G, Shen S, Soft-templated LiFePO₄/mesoporous carbon nanosheets (LFP/meso-CNSs) nanocomposite as the cathode material of lithium ion batteries. RSC Advances, 2014, 4(41): 21325–21331

[16] Meng Y, Gu D, Zhang F, Ordered mesoporous polymers and homologous carbon frameworks: amphiphilic surfactant templating and direct transformation. Angewandte Chemie, 2005, 117(43): 7215–7221

[17] Chen P, Cheng C, Li T, Significantly improved dielectric properties of TiO₂ ceramics through acceptor-doping and Ar/H₂ annealing. Ceramics International, 2021, 47(2): 1551–1557

[18] Shen L, Zhang X, Uchaker E, Li₄Ti₅O₁₂ nanoparticles embedded in a mesoporous carbon matrix as a superior anode material for high rate lithium ion batteries. Advanced Energy Materials, 2012, 2(6): 691–698

[19] Sorensen E M, Barry S J, Jung H K, Three-dimensionally ordered macroporous Li₄Ti₅O₁₂: effect of wall structure on electrochemical properties. Chemistry of Materials, 2006, 18(2): 482–489

[20] McCafferty E, Wightman J P. Determination of the concentration of surface hydroxyl groups on metal oxide films by a quantitative XPS method. Surface and Interface Analysis, 1998, 26(8): 549–564

[21] Wang B, Liu T, Liu A, A hierarchical porous C@LiFePO₄/carbon nanotubes microsphere composite for high-rate lithium-ion batteries: combined experimental and theoretical study. Advanced Energy Materials, 2016, 6(16): 1600426

[22] Wang B, Al Abdulla W, Wang D, A three-dimensional porous LiFePO₄ cathode material modified with a nitrogen-doped graphene aerogel for high-power lithium ion batteries. Energy & Environmental Science, 2015, 8(3): 869–875

[23] Wu R, Xia G, Shen S, In-situ growth of LiFePO₄ nanocrystals on interconnected carbon nanotubes/mesoporous carbon nanosheets for high-performance lithium ion batteries. Electrochimica Acta, 2015, 153: 334–342

[24] Sun Z, Sun B, Qiao M, A general chelate-assisted co-assembly to metallic nanoparticles-incorporated ordered mesoporous carbon catalysts for Fischer–tropsch synthesis. Journal of the American Chemical Society, 2012, 134(42): 17653–17660

[25] Shen L, Yuan C, Luo H, Facile synthesis of hierarchically porous Li₄Ti₅O₁₂ microspheres for high rate lithium ion batteries. Journal of Materials Chemistry, 2010, 20(33): 6998

[26] Ma Y, Ding B, Ji G, Carbon-encapsulated F-doped Li₄Ti₅O₁₂ as a high rate anode material for Li⁺ batteries. ACS Nano, 2013, 7(12): 10870–10878

[27] Liu J, Song K, van Aken P A, Self-supported Li₄Ti₅O₁₂-C nanotube arrays as high-rate and long-life anode materials for flexible Li-ion batteries. Nano Letters, 2014, 14(5): 2597–2603

[28] Ding Y, Li G R, Xiao C W, Insight into effects of graphene in Li₄Ti₅O₁₂/carbon composite with high rate capability as anode materials for lithium ion batteries. Electrochimica Acta, 2013, 102: 282–289

RIGHTS & PERMISSIONS

Higher Education Press