Preparation and electrochemical properties of Li4Ti5O12/Si3N4 composites as anode materials for high-performance lithium-ion batteries
Introduction
Environmental pollution and energy crisis have recently become significant challenges faced by society [[1], [2], [3], [4]]. Shortages in terms of oil resources and the pollution caused by automobiles are urgent issues to be solved [5,6]. In this context, rechargeable lithium-ion batteries (LIBs) have attracted significant research attention on account of their ultralong cycle life, high gravimetric energy density, and environmental friendliness [[7], [8], [9], [10]]. As the most important component of the batteries, the anode materials play a crucial role in the electrochemical process of LIBs. The typical anode materialāspinel-type lithium titanate (Li4Ti5O12, LTO), with a unique āzero strainā structure whereby the volume remains almost unchanged during the charge and discharge processācan meet the requirements of modern electronic products in terms of its excellent electrochemical performance [[11], [12], [13]]. Furthermore, LTO's advantages of high operating voltage, high charge-discharge rate, safety, and specific capacity of LTO (175 mAh/g) make it an ideal anode material for LIBs [11,[14], [15], [16]]. However, LTO is essentially an insulating material with relatively low electrical conductivity, and its capacity decays at a high rate owing to polarization [17,18]. Therefore, several strategies have been proposed to rationally design and modulate electrode materials to facilitate oxygen electrode reaction and enhance the electrochemical properties of LIBs.
Many studies have demonstrated that surface coating, ion doping, and morphology modification strategies of LTO can significantly improve the electronic conductivity, ion diffusion rate, and electrochemical performance of LTO-based LIBs [6,19,20]. For example, Liu et al. prepared carbon nanoparticle-coated LTO materials as LIB anode materials and found that the conductive structure of the designed LTO/C nanoflake arrays had superior high-rate capabilities and longer cycle life span than the LTO array counterparts [17]. Similarly, Zhu et al. reported the preparation of different contents of Li2Oā2B2O3-coated LTOs, which enhanced the capacity retention rate and cycle stability of the electrodes at high current densities [21]. In light of the issues involving the low conductivity of LTO materials and the polarization problem [22], this study proposed use silicon nitride (Si3N4) to coat the surface of LTOs to enhance their conductivity [23]. Recently, Si3N4 has received significant research attention owing to its high electrical performance, toughness (>7.0Ā MPa m1/2), and strength, which helps to achieve good cycle stability and considerable specific capacity without any obvious shortcomings [24,25]. Therefore, Si3N4 can act as conductive particles in LTO to further improve the electrochemical performance of LIBs [26].
In this study, pure LTO and LTO/Si3N4 samples were prepared through the hydrothermal method as anode materials for LIBs. The effects of the amount of Si3N4 coating on the morphology and electrochemical performance of LTO were investigated. The experimental results showed that Li4Ti5O12/Si3N4-based anode materials exhibit superior electrochemical performance in terms of oxygen redox processes in LIBs. As a result, the LIB using Li4Ti5O12 with a 2% Si3N4 coating exhibited a superior discharge capacity (198.4 mAh/g at 1C), and the capacity retention rate reached 88.96% after 200 charge-discharge cycles.
Section snippets
Sample synthesis
Pure LTO and LTO/Si3N4 samples were obtained using a hydrothermal method. Tetrabutyl titanate (Ti(OC4H9)4, AR), lithium hydroxide (LiOHĀ·H2O, AR), and hydrogen peroxide (H2O2, 30%) were used as raw materials. Lithium hydroxide was added to 60Ā ml of deionized water and stirred evenly to form solution I, and 4Ā ml of H2O2 was added to tetrabutyl titanate to form solution II under continuous stirring. Then, solution I and solution II were mixed and then transferred to an autoclave with a Teflon
Results and discussion
Fig. 1(a) displays the XRD patterns of all LTO/SN composites. The diffraction peaks of the samples are distinct and sharp, indicating that all samples have high crystallinity. The diffraction peaks of all LTO and LTO/SN samplesāwith different Si3N4 coatings sintered at 700Ā Ā°Cāare completely consistent with those of the standard structure (JCPDS No. 49ā0207) of LTO. It can be clearly seen that among all XRD patterns, the LTO/SN2 and LTO/SN3 samples have relatively high diffraction peak
Conclusion
In summary, pure LTO and LTO coated with various amounts of Si3N4 (1%ā5%) as negative electrode materials for LIBs were prepared through a hydrothermal method. The morphology and structure of the LTO/SN composites were studied, and the morphology of the samples changed with the coating of Si3N4, which revealed a kind of chemical component and element distribution. The Si3N4 coating forms a conductive network between the LTO particles, and the good chemical stability of Si3N4 further improves
Declaration of competing interest
The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.
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Synthesis and electrochemical characteristics of flower-like Ca-doped Li<inf>4</inf>Ti<inf>5</inf>O<inf>12</inf> as anode material for lithium-ion batteries
2022, Powder TechnologyCitation Excerpt :Finally, the LTO-CA anode material was expected to have a better electrochemical performance for LIBs application. All samples were prepared via a hydrogen peroxide-assisted hydrothermal method as the previous report [38], and the synthesis process was presented in Fig. 1. Typically, LiOHĀ·H2O was dissolved in deionized water (60 ml) under magnetic stirring for 25 min to form solution A, and hydrogen peroxide (4 ml) was added into C16H36O4Ti under magnetic stirring for 25 min to form solution B. Then, solution A was added drop-wise into solution B under continuous stirring to form a uniform yellow transparent solution.
Enhancing the electrochemical performance of Li<inf>4</inf>Ti<inf>5</inf>O<inf>12</inf> anode materials by codoping with Na and Br
2022, Journal of Alloys and CompoundsCitation Excerpt :To improve the comprehensive performance of LTO, a series of modification strategies have been proposed, among which surface coating and element doping are considered to be the most effective optimization methods. Surface coatings, such as Si3N4 [26], Er2O3 [27], polythiophene [28], SiO2 [29], and carbon [30], can inhibit the continuous erosion of the electrode material by the electrolyte; however, a uniform coating layer is difficult to form during the preparation process, and the layer is constantly consumed during prolonged contact with the electrolyte. In contrast, doping modification is more effective and convenient.