Synergistic photothermal engineering enables superior high-rate capability of Li₄Ti₅O₁₂

Abstract

The preparation of Li₄Ti₅O₁₂ (LTO) by the sol-gel method often requires a uniform distribution of metal ions in the precursor so as to obtain a uniform and fine particle feature. It can be realized via chelation and condensation reactions in the sol and gel stages. However, the molecular structure of the metal ion chelate or condensation polymer in the precursors does not easily decompose during thermal decomposition, and the LTO grains formed after calcination are relatively large and nonuniform. Herein, we propose a novel photothermal decomposition process with ultraviolet (UV) light irradiation, which could cause the cracking of the stable chelating or polymerizing structure during thermal decomposition and facilitate the formation of small and uniform LTO grains after calcination. After the UV irradiation, the Zr-doped Li₄Ti_5-xZr_xO₁₂ (LTZO) exhibits a smaller grain size and larger lattice parameters. As a consequence, the Li⁺ ion diffusion coefficient of the photothermally treated LTO with the optimum Zr dopant amount of x = 0.15 (UV-0.15LTZO) is twice that of the 0.15-LTZO sample prepared by the traditional process. The UV-0.15LTZO anode presents a specific capacity of 129 mAh·g^-1 at a discharge rate of 10 C and still exhibits a capacity retention rate of 99.4% after 100 cycles, which are higher than that of the 0.15LTZO sample (95 mAh·g^-1, 94.8%). The photothermal decomposition strategy proposed in this paper refines grain and expands the lattice of LTO electrodes and offers a valuable reference for controlling the properties of other electrode materials and nanomaterials.

Keywords

Lithium titanate / UV irradiation / photochemical reaction / lithium-ion batteries / rate capability

References

[1] Khan A.,Al Rashid H.,Roy P. K.,Chowdhury S. I.,Sathi S. A.. Challenges and the way to improve lithium‐ion battery technology for next‐generation energy storage Energy. Environ. Mater. 2025 8 e70088

[2] Thackeray M. M.,Amine K.. Li₄Ti₅O₁₂ spinel anodes Nat. Energy 2021 6 683

[3] Xia Y.,Zhao T.,Zhu X..et al. Inorganic-organic competitive coating strategy derived uniform hollow gradient-structured ferroferric oxide-carbon nanospheres for ultra-fast and long-term lithium-ion battery Nat. Commun. 2021 12 2973 PMC8137936

[4] Wu F.,Maier J.,Yu Y.. Guidelines and trends for next-generation rechargeable lithium and lithium-ion batteries Chem. Soc. Rev. 2020 49 1569 614

[5] Yan H.,Zhang D.,Qilu X.,Duo X.,Sheng X.. A review of spinel lithium titanate (Li₄Ti₅O₁₂) as electrode material for advanced energy storage devices Ceram. Int. 2021 47 5870 95

[6] Wu H. B.,Chen J. S.,Hng H. H.,Lou X. W.. Nanostructured metal oxide-based materials as advanced anodes for lithium-ion batteries Nanoscale 2012 4 2526 42

[7] Nzereogu P.,Omah A.,Ezema F.,Iwuoha E.,Nwanya A.. Anode materials for lithium-ion batteries: a review Appl. Surf. Sci. Adv. 2022 9 100233

[8] Dong C.,Dong W.,Lin X.,Zhao Y.,Li R.,Huang F.. Recent progress and perspectives of defective oxide anode materials for advanced lithium ion battery EnergyChem 2020 2 100045

[9] Ohzuku T.,Ueda A.,Yamamoto N.. Zero‐strain insertion material of Li [Li_1/3Ti_5/3]O₄ for rechargeable lithium cells J. Electrochem. Soc. 2019 142 1431 5

[10] Zhang Y.,Teeter G.,Dutta N. S.,Frisco S.,Han S.. Mechanistic understanding of aging behaviors of critical-material-free Li₄Ti₅O₁₂//LiNi_0.9Mn_0.1O₂ cells with fluorinated carbonate-based electrolytes for safe energy storage with ultra-long life span Chem. Eng. J. 2023 460 141239

[11] Zhang H.,Yang Y.,Xu H.,Wang L.,Lu X.,He X.. Li₄Ti₅O₁₂ spinel anode: fundamentals and advances in rechargeable batteries InfoMat 2021 4 e12228

[12] Zhang E.,Zhang H.. Hydrothermal synthesis of Li₄Ti₅O₁₂-TiO₂ composites and Li₄Ti₅O₁₂ and their applications in lithium-ion batteries Ceram. Int. 2019 45 7419 26

[13] Yuan T.,Tan Z.,Ma C.,Yang J.,Ma Z. F.,Zheng S.. Challenges of spinel Li₄Ti₅O₁₂ for lithium-ion battery industrial applications Adv. Energy Mater. 2017 7 1601625

[14] Bhatti H. S.,Jabeen S.,Mumtaz A.,Ali G.,Qaisar S.,Hussain S.. Effects of cobalt doping on structural, optical, electrical and electrochemical properties of Li₄Ti₅O₁₂ anode J. Alloys Compd. 2022 890 161691

[15] Yin Y.,Luo X.,Xu B.. In-situ self-assembly synthesis of low-cost, long-life, shape-controllable spherical Li₄Ti₅O₁₂ anode material for Li-ion batteries J. Alloys Compd. 2022 904 164026

[16] Haridas A. K.,Sharma C. S.,Rao T. N.. Donut-shaped Li₄Ti₅O₁₂ structures as a high performance anode material for lithium ion batteries Small 2015 11 290 4

[17] Roh H.,Lee G.,Haghighat-Shishavan S.,Chung K. Y.,Kim K.. Polyol-mediated carbon-coated Li₄Ti₅O₁₂ nanoparticle/graphene composites with long-term cycling stability for lithium and sodium ion storages Chem. Eng. J. 2020 385 123984

[18] Cáceres-Murillo J.,Díaz-Carrasco P.,Kuhn A.,Rodríguez-Castellón E.,García-Alvarado F.. Improvement of the rate capability of the Li₄Ti₅O₁₂ anode material by modification of the surface composition with lithium polysulfide J. Alloys Compd. 2024 976 173051

[19] Lakshmi-Narayana A.,Dhananjaya M.,Julien C. M.,Joo S. W.,Ramana C. V.. Enhanced electrochemical performance of rare-earth metal-ion-doped nanocrystalline Li₄Ti₅O₁₂ electrodes in high-power Li-ion batteries ACS Appl. Mater. Interfaces 2023 15 20925 45

[20] Ezhyeh Z. N.,Khodaei M.,Torabi F.. Review on doping strategy in Li₄Ti₅O₁₂ as an anode material for Lithium-ion batteries Ceram. Int. 2023 49 7105 41

[21] Zhang Y. H.,Nie Z. H.,Du C. Q.,Zhang J. W.,Zhang J. W.. Ultrahigh lithiation dynamics of Li₄Ti₅O₁₂ as an anode material with open diffusion channels induced by chemical presodiation Rare Metals 2022 42 471 83

[22] Kim J. G.,Park M. S.,Hwang S. M..et al. Zr⁴⁺ doping in Li₄Ti₅O₁₂ anode for lithium-ion batteries: open Li⁺ diffusion paths through structural imperfection ChemSusChem 2014 7 1451 7

[23] Nithya V. D.,Sharmila S.,Vediappan K.,Lee C. W.,Vasylechko L.,Kalai Selvan R.. Electrical and electrochemical properties of molten-salt-synthesized 0.05 mol Zr- and Si-doped Li₄Ti₅O₁₂ microcrystals J. Appl. Electrochem. 2014 44 647 54

[24] Wang Z.,Wang Z.,Peng W.,Guo H.,Li X.. An improved solid-state reaction to synthesize Zr-doped Li₄Ti₅O₁₂ anode material and its application in LiMn₂O₄/ Li₄Ti₅O₁₂ full-cell Ceram. Int. 2014 40 10053 9

[25] Seo I.,Lee C.,Kim J.. Zr doping effect with low-cost solid-state reaction method to synthesize submicron Li₄Ti₅O₁₂ anode material J. Phys. Chem. Solids 2017 108 25 9

[26] Hou L.,Qin X.,Gao X.,Guo T.,Li X.,Li J.. Zr-doped Li₄Ti₅O₁₂ anode materials with high specific capacity for lithium-ion batteries J. Alloys Compd. 2019 774 38 45

[27] Liu Z.,Cao L.,He F..et al. Study on the possibility of diagonal line rule in elemental doping effects in Li₄Ti₅O₁₂ by mechanochemical method Electrochim. Acta 2022 422 140485

[28] Gu F.,Chen G.,Wang Z.. Synthesis and electrochemical performances of Li₄Ti_4.95Zr_0.05O₁₂/C as anode material for lithium-ion batteries J. Solid State Electrochem. 2011 16 375 82

[29] Han J.,Zhang B.,Bai X..et al. Li 4 Li₄Ti₅O₁₂ composited with Li₂ZrO₃ revealing simultaneously meliorated ionic and electronic conductivities as high performance anode materials for Li-ion batteries J. Power Sources 2017 354 16 25

[30] Wang B.,Gu L.,Zhang D.,Wang W. A.. High-throughput production of Zr-doped Li₄Ti₅O₁₂ Modified by mesoporous Libaf₃ nanoparticles for superior lithium and potassium storage Chem. Asian J. 2019 14 3181 7

[31] Lu P.,Huang X.,Ren Y..et al. Na⁺ and Zr⁴⁺ co-doped Li₄Ti₅O₁₂ as anode materials with superior electrochemical performance for lithium ion batteries RSC Adv. 2016 6 90455 61

[32] Li X.,Tang S.,Qu M.,Huang P.,Li W.,Yu Z.. A novel spherically porous Zr-doped spinel lithium titanate (Li₄Ti_5-xZr_xO₁₂) for high rate lithium ion batteries J. Alloys Compd. 2014 588 17 24

[33] Li X.,Qu M.,Yu Z.. Structural and electrochemical performances of Li₄Ti_5-xZr_xO₁₂ as anode material for lithium-ion batteries J. Alloys Compd. 2009 487 L12 7

[34] Yi T.,Chen B.,Shen H.,Zhu R.,Zhou A.,Qiao H.. Spinel Li₄Ti_5-xZr_xO₁₂ (0 ≤ x ≤ 0.25) materials as high-performance anode materials for lithium-ion batteries J. Alloys Compd. 2013 558 11 7

[35] Li Y.,Chen Q.,Meng Q.,Lei S.,Song F.,Ma J.. Synergy of a hierarchical porous morphology and anionic defects of nanosized Li₄Ti₅O₁₂ toward a high-rate and large-capacity lithium-ion battery J. Energy Chem. 2021 54 699 711

[36] Wu C.,Wang Y.,Ma G.,Zheng X.. Enhanced rate capability of Li₄Ti₅O₁₂ anode material by a photo-assisted sol-gel route for lithium-ion batteries Electrochem. Commun. 2021 131 107119

[37] Pope C. G.. X-ray diffraction and the bragg equation J. Chem. Educ. 1997 74 129

[38] Bai X.,Li T.,Bai Y.. Dual-modified Li₄Ti₅O₁₂ anode by copper decoration and carbon coating to boost lithium storage ACS Sustain. Chem. Eng. 2020 8 17177 84

[39] Jiang X.,Ma G.,Ke Y.,Deng L.,Chen Q.. Cost-effective Li₄Ti₅O₁₂/C-S prepared by industrial H₂TiO₃ under a carbon reducing atmosphere as a superior anode for Li-ion batteries Ceram. Int. 2023 49 625 34

[40] Zhou S.,Barnes I.,Zhu T.,Bejan I.,Albu M.,Benter T.. Atmospheric chemistry of acetylacetone Environ. Sci. Technol. 2008 42 7905 10

[41] Rinaman J. E.,Murray C.. Acetylacetone photolysis at 280 nm studied by velocity-map ion imaging J. Phys. Chem. A. 2023 127 6687 96 PMC10440790

[42] Lei L.,Liu Y.,Chen X..et al. Micropatterning of LaCoO₃ thin films through a novel photosensitive sol-gel lithography technique and their magnetic properties Ceram. Int. 2024 50 44671 7

[43] Shen Y.,Søndergaard M.,Christensen M.,Birgisson S.,Iversen B. B.. Solid state formation mechanism of Li₄Ti₅O₁₂ from an anatase TiO₂ source Chem. Mater. 2014 26 3679 86

[44] Wang G.,Wang H.,Ma G..et al. Investigation on process mechanism of a novel energy-saving synthesis for high performance Li₄Ti₅O₁₂ anode material J. Energy Chem. 2022 70 266 75