Ni0.05Ti1.95Nb10O29: an advanced anode material for high-performance lithium-ion storage

doi:10.21203/rs.3.rs-3786761/v1

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Research Article

Ni_0.05Ti_1.95Nb₁₀O₂₉: an advanced anode material for high-performance lithium-ion storage

https://doi.org/10.21203/rs.3.rs-3786761/v1

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published 24 Apr, 2024

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Ti₂Nb₁₀O₂₉ (TNO) has garnered significant research attention due to its high specific capacity and excellent safety features, positioning it as a promising anode material for lithium-ion batteries (LIBs). Nevertheless, its rate capability is significantly hampered by poor electronic and ionic conductivity. In this paper, Ni²⁺ doping has been first applied to address these issues. A series of Ni²⁺ doped TNO (Ni_x-TNO (x = 0.03, 0.05, 0.07) electrode materials have been prepared to unveil the effects of Ni²⁺ content. The experimental results unveil that Ni²⁺ doping maintains the Wadsley-Roth shear structure of TNO while augmenting the single-cell volume and introducing additional oxygen vacancies in TNO. This generates a wider diffusion path and more active sites for lithium ions (Li⁺). Besides, the introduction of Ni²⁺ can alter the conductive field distribution of TNO, giving rise to a much higher electronic conductivity of Ni_x-TNO. Among the synthesized Ni_x-TNO, Ni_0.05-TNO shows the best electrochemical performance, demonstrating a reversible capacity of 306 mAh g^–1 with a Coulombic efficiency of 91.46% in the first cycle at 0.1 C and 146.19 mAh g^–1 at 10 C after 500 cycles.

Lithium-ion batteries

Ti2Nb10O29

Ni2+ doping

high-rate capability

To meet the urgent needs of human beings for higher energy density and safety performance of lithium-ion batteries, there are higher requirements for electrode materials[1, 2]. The safety concern related to graphite, arising from the formation and growth of lithium dendrites at low working potentials, has yet to be adequately addressed[3, 4]. Therefore, the research on high-voltage new anode materials is crucial to the development of lithium-ion batteries [5, 6]. Previous studies showed that metal oxides are promising anode materials for LIBs since they can maintain structural stability during Li⁺ intercalation/deintercalation [7–10]. Recently, Ti₂Nb₁₀O₂₉ (TNO) has gained significant attention as a high-voltage intercalation anode material [11, 12]. Monoclinic TNO has a 3×4×∞ ReO₃-type phase structure built by octahedrons of NbO₆ and TiO₆, which can provide an open channel and stable structure for Li⁺ intercalation[13]. Beyond that, TNO has three pairs of redox couples (Ti⁴⁺/Ti³⁺, Nb⁵⁺/Nb⁴⁺, and Nb⁴⁺/Nb³⁺), which can contribute 22 electrons transfer per unit of chemistry, resulting in a theoretical specific capacity of 396 mAh g^–1[14, 15]. However, the electrochemical performance of TNO is constrained by its intrinsic issues of poor electronic conductivity and a low Li-ion (Li⁺) diffusion coefficient [16]. To address these issues, considerable research endeavors have been focused on designing and synthesizing nanostructures exhibiting various morphologies. The nanostructures with large specific surface areas and short distances of ion transport can facilitate the electrochemical reactions kinetics[17–21]. Besides, coating with other conductive materials was also applied to improve the electronic conductivity. Unfortunately, this method only enhances inter-particle conductivity and cannot alter the poor intrinsic electronic conductivity of TNO[22]. In addition, it lowers both the bulk and capacity densities of the material[23]. Moreover, the synthesis process of nanoparticles is intricate and requires significant time investment, making it hard to industrialization[24]. In contrast, micron particles are cheaper to synthesize and more feasible to produce.

Up to now, some studies have been done on micron-sized TNO from the perspective of structural modification. Oxygen vacancies are common means to improve the crystal structure, Lin[25] synthesized a defective TNO (Ti₂Nb₁₀O_27.1) which shows high Li⁺ diffusion coefficients far exceeding the original samples by a factor of six. In addition, ion doping is also an effective way to improve the electrochemical properties[23]. Wu[26] found that replacing a portion of Nb⁵⁺ ions with Ti⁴⁺ and W⁶⁺ in TNO could lower the crystallinity and induce the generation of an amorphous phase. These can enhance ion transport and give rise to an isotropic Li⁺ diffusion. Zheng[27] used Fe substitution to regulate the entropy, which could effectively lower the particle size and broaden the ion transport path. Nevertheless, the effect of other dopant ions on TNO has been rarely studied.

Inspired by Fe substitution, Ni and Fe are in the same group of the periodic table. Following the pattern observed with Fe, the ionic radius of Ni²⁺ (0.69 Å) is larger than that of Nb⁵⁺ (0.64 Å) and Ti⁴⁺ (0.61 Å) ions. Thus, the introduction of Ni²⁺ might increase the cell volume which may offer an expanded pathway for Li⁺ diffusion. Due to the empty 3d/4d orbitals of Ti/Nb, TNO demonstrates poor intrinsic electronic conductivity, Ni²⁺ (t⁶_2ge²_g) has two unpaired free electrons in the 3d orbitals which can introduce free electrons for the crystal, thus may contribute to the electronic conductivity. In addition, more oxygen vacancies may be generated to keep the structure electrically neutral, which can provide more lattice channels for ion transport, thus contributing to the Li⁺ diffusion[3, 20].

Here, we prepared Ni²⁺ doped TNO (Ni_x-TNO, x = 0, 0.03, 0.05, and 0.07) materials using a simple one-step solid-state reaction approach. Various in-depth analysis was carried out to systematically explore the beneficial impacts of Ni doping on the crystal structure and electrochemical properties. The results show that Ni²⁺ can widen the ion transport channel and improve the diffusion coefficient of Li⁺ in the matrix material. Among the various Ni_x-TNO materials, Ni_0.05-TNO displayed superior rate performance (181.76 mAh g^–1 at 30 C) and outstanding durability, maintaining a substantial capacity of 146.19 mAh g^–1 after 500 cycles, with an extremely low capacity decay of only 0.04% per cycle.

2.1 Materials Synthesis

The Ni_x-TNO samples were synthesized via a conventional one-step solid-state reaction with Nb₂O₅ powder, anatase TiO₂ and NiO. To obtain Ni_x-TNO, stoichiometric amounts of the raw materials were ball-milled in the planetary mill at a rotational speed of 400 rpm for 8 h. Ultimately, the obtained powder was subjected to heating at 1000 ℃ with a heating rate of 5 ℃/min, maintained for 10 hours in air, and then naturally cooled to room temperature. The Ti₂Nb₁₀O₂₉ material was prepared by using the same process.

2.2 Materials Characterization

As-calcined powder crystal structures were characterized by powder X-ray diffraction (XRD) (Bruker D8 Advance, Germany, Cu K radiation source = 1.541 Å). Raman spectra were obtained from a Raman spectrometer (LabRAM HR, Horiba jobinyvon). Using transmission electron microscopy (SEM) and high-resolution transmission electron microscopy (HRTEM, JEM-2100F), the morphologies (sizes and microstructures) were evaluated. The elemental distribution of the sample was detected using energy-dispersive X-ray spectroscopy (EDS) combined with high-resolution transmission electron microscopy. X-ray photoelectron spectroscopy (XPS, Thermo VG Scientific, VG MultiLab 2000) was utilized to analyze the surface chemical composition and valence state.

2.3 Electrochemical Measurement

CR2025-type coin cells were assembled in a glove box filled with dry argon for the evaluation of electrochemical performances. A homogeneous slurry was prepared by thoroughly mixing 70wt% calcined powder, 10wt% polyvinylidene fluoride (PVDF), and 20wt% calcined powder in N-methyl-2-pyrrolidone (NMP). The slurry was uniformly cast onto copper foil and dried at 65°C for 10 hours, resulting in a loading density of approximately 1.0 mg cm^− 2 for the electrode. Lithium foil served as the reference electrode for the battery. A microporous polypropylene film (Celgard 2500) was employed as the separator. The electrolyte comprised a 1 M LiPF₆ (DAN VEC) solution in a 1:1 weight ratio of ethylene carbonate (EC) to diethyl carbonate (DEC). Electrostatic discharge-charge tests were conducted using a multi-channel battery testing system (Neware CT-3008, China) at various current rates within the potential range of 3.0–1.0 V. Measurements of cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) were conducted using the electrochemical workstation (Chenhua, ChI660E, China).

Table 1

The detailed refined structural parameters for TNO and Ni_0.05-TNO.
Product	a/Å	b/Å	c/Å	α/°		β/°	γ/°	Volume/Å³			wRp	Rp
TNO	15.518	3.813	20.542		90	113.05	90		1117.59	0.062		0.045
Ni_0.05-TNO	15.566	3.818	20.559		90	113.24	90		1123.63	0.061		0.042

Firstly, we investigate the crystal structure of Ni_x-TNO (x = 0.03, 0.05, and 0.07). As shown in Fig. 1a, the diffraction peaks observed in Ni_x-TNO index well to monoclinic phase TNO (space: A/2m, PDF#72–0159), without impurity phases of TiO₂ or Nb₂O₅. This indicates the successful synthesis of TNO and Ni doping does not change the space group. With Ni content increasing from 0 to 0.07, the position of the diffraction peak of the (020) crystal surface moves to smaller angles (Fig. 1b), which suggests an increase of interplanar spacing at a higher Ni doping content. Besides, with the increase of Ni²⁺ content, the diffraction peak intensity also decreases, indicating that Ni²⁺ doping can effectively reduce the crystallinity of the material, which might reduce the Li⁺ diffusion barrier[26]. However, excessive doping gives rise to the variation of crystal structure, as unveiled from the disappeared (11$\stackrel{\text{-}}{\text{1}}$) peak of Ni_0.07-TNO in Fig. 1c. More specifically, Fig. 1d-e presents the refinement results of the XRD patterns for TNO and Ni_0.05-TNO using the Rietveld method, accompanied by comprehensive structural parameters provided in Table 1. It is seen that Ni_0.05-TNO (1123.63 Å³) has a larger volume of unit cells than TNO (1117.59 Å³). This can be attributed to the fact that Ni²⁺ has a larger ionic radius when compared to Ti⁴⁺ and Nb⁵⁺. The larger volume of the unit cell can provide a wider diffusion channel for Li⁺ diffusion (Fig. 1h and 1i).

Further, Raman spectroscopy was applied to get insight into the bonding characteristics of the crystal structures. As shown in Fig. 1f, the bands occurring at 896 and 1000 cm^–1 correspond to the tensile vibration of NbO₆[28]. The bands of 544 and 646 cm^–1 refer to the vibration of the Ti − O bonds of TiO₆[26]. As for the bands at 270 and 349 cm^–1, they are associated with symmetric and asymmetric bending motions of O-Ti-O and O-Nb-O bridge bonds, respectively[7]. However, the Ti–O vibrational peak of Ni_0.05-TNO exhibits a slight blue shift, providing evidence for changes in the internal chemical environment, maybe attributed to increased cation-oxygen bonding and the development of oxygen vacancies[3].

The morphologies and particle sizes of each sample are examined through scanning electron microscopy (SEM). As depicted in Fig. 2a-h, all samples present irregularly reunion particles, and the particle size ranges from 0.2 to 1 µm. Compared to the original sample, Ni_x-TNO particles are more dispersed. To further reveal the morphological structures of Ni_x-TNO, TEM characterizations were conducted (Fig. 3a-i). The diffraction patterns in Fig. 3b and 3f unveil that TNO and Ni_0.05-TNO are typical single-crystals. The different orientations of the crystal surfaces can be seen from Fig. 3c and 3g. After further amplification and analysis, the specific parameters of the crystal surface can be obtained (Fig. 3d and 3h). From the lattice fringes of (400) and (600) crystal planes of TNO and Ni_0.05-TNO, their interlayer spacings are 0.354 and 0.237 nm respectively, which agrees well with the findings from XRD analyses. The homogeneous distribution of Ti, Nb, O, and Ni can be seen from the TEM-EDS elemental mapping (Fig. 3i), suggesting the successful introduction of Ni²⁺ into TNO.

Then, XPS is utilized to investigate the surface composition and valence states of Ni_0.05-TNO and TNO. As seen in Fig. 4a, the full XPS spectrum of Ni_0.05-TNO indicates the existence of Ti, Nb, O, and Ni, revealing that Ni has been successfully doped in Ni₀.₀₅-TNO. This can also be verified from the characteristic peaks of Ni²⁺ in Ni₀.₀₅-TNO (Fig. 4b). Similar results can be observed from TNO excluding the absence of the Ni element. As seen in Fig. 4c-d, for the TNO, a couple of peaks located at 464.02 and 458.26 eV of the Ti spectrum originate from Ti 2p_1/2 and Ti 2p_3/2, suggesting the existence of Ti⁴⁺. The Nb spectrum of TNO at 209.55 and 206.8 eV are indexed into Nb 3d_5/2 and Nb 3d_3/2 of Nb⁵⁺, separately. Specifically, the peaks of both Ti 2p and Nb 3d shift towards lower binding energy positions following Ni doping, which unveils more Ti³⁺ and Nb⁴⁺ in Ni_0.05-TNO[5]. The presence of Ti³⁺ and Nb⁴⁺ can be attributed to the charge distribution caused by Ni²⁺ doping[16]. From Fig. 4e, Ni_0.05-TNO shows a broader oxygen-deficient region in comparison with TNO, unveiling the more missing lattice O in Ni_0.05-TNO[29]. This can also be reflected from the electron paramagnetic resonance (EPR). As illustrated in Fig. 4f, both TNO and Ni_0.05-TNO display an EPR signal at g = 2.0 (typical signal of oxygen vacancies) and Ni_0.05-TNO demonstrates a stronger peak intensity than that of TNO, which indicates the existence of an increased number of oxygen vacancies in Ni_0.05-TNO.

The cyclic voltammetry (CV) was used to investigate the kinetic properties during the corresponding redox process in the voltage range of 1.0‒3.0 V for the first three cycles with the sweep of 0.2 mV s^–1. As shown in Fig. 5a and 5b, for each cell, the locations of cathodic peaks in the CV during the first cycle deviate from those observed in the subsequent two cycles, which is due to the change of electronic structure of TNO electrode induced by the distortion of TiO₆ or NbO₆ octahedra and the irreversible consumption of Li⁺ during the process of Li⁺ insertion[3, 30]. The CV curves consistently display substantial sharp redox peaks at 1.55‒1.75 V, associated with the Nb⁵⁺/Nb⁴⁺ redox couple, and small gentle peaks near 1.9 V, corresponding to the Ti⁴⁺/Ti³⁺ redox couple. The broad peak at 1.0‒1.5 V refers to the Nb⁴⁺/Nb³⁺ redox couple. Ni_0.05-TNO exhibits reduced redox potential differences compared to pure TNO, demonstrating superior kinetic reversibility after Ni doping[39]. Figure 5c illustrates the charge and discharge profiles of the initial cycle of all samples at a constant current density of 0.1 C. The charge and discharge curves can be divided into three regions according to the inflection point, which are consistent with the redox changes observed during the CV experiments. The regions of A and C correspond to the solid solution of Li⁺ in TNO[32]. The plateau in region B involves a phase of two-phase transition corresponding to a redox reaction in 1.65v[27, 33]. In this region, a longer reaction plateau in Ni_0.05-TNO implies more capacity contribution, most likely originating from the more active sites brought about by oxygen vacancies. It is seen that the discharge capacity and Coulombic efficiency of the doped sample at small Ni content (x = 0.03 and 0.05) are superior to those of the original sample. Ni_0.05-TNO exhibits the most superior electrochemical performance, with the first discharge capacity and Coulombic efficiency of 306 mAh g^–1 and 91.46%, respectively. This could be attributed to the fact that the doped samples exhibit smaller average particle sizes and higher (ionic and electronic) conductivities[31]. Thus, Ni²⁺ doping has a positive effect on the surface reaction kinetics of Li⁺.

Figure 5d illustrates the rate capabilities of Ni_x-TNO (x = 0, 0.03, 0.05 and 0.07) at varied current densities. The capacities of Ni_0.05-TNO at 0.5, 1, 2, 5, 10, 20, and 30 C are 265.68, 251.16, 239.78, 223.61, 204.89, 185.63, and 181.76 mAh g^–1, respectively, which significantly elevated in comparison to TNO (202.70, 189.90, 180.52, 170.09, 158.89, 147.43, and 138.62 mAh g^–1). Moreover, the cyclic stability of Ni_x-TNO at a large current rate of 10 C was evaluated (Fig. 5e). It is seen that Ni_0.05-TNO displays the highest cycling stability among the four samples. The reversible capacity of Ni_0.05-TNO after 500 cycles is 146.19 mA h g^–1, with a capacity loss of only 0.04% per cycle, while the reversible capacities of other Ni_x-TNO samples (x = 0, 0.03 and 0.07) are 85.31, 125.95, and 81.96 mAh g^–1. The outstanding cyclic stability may be due to the wider Li⁺ diffusion pathway after Ni²⁺ doping, which helps stabilize the structure during repeated cycles[3]. The reason for the poor cycling performance of Ni_0.07-TNO might be that excessive Ni²⁺ doping results in excessive lattice distortion (see Fig. 1c), which leads to a significant decrease in structural stability.

Table 2

Impedance parameters and Li⁺ diffusion coefficients of TNO and Ni_x-TNO
Product	R_ct (Ω)	σ (Ω s^–0.5)	D×10^–14 (cm² s^–1)
TNO	168.00	132.64	3.51
Ni_0.03-TNO	55.35	96.32	32.3
Ni_0.05-TNO	51.42	110.85	37.5
Ni_0.07-TNO	69.15	37.99	20.7

In order to investigate the nature of ion transport during the charge and discharge processes, we further performed the impedance analysis test (A.C. impedance technique) on the battery. Figure 6 illustrates the Nyquist plots for both TNO and Ni_x-TNO after cycling three times at 0.1 C with the fitted equivalent circuit inserted. In Fig. 6a, a semicircular feature is present in the high-frequency region, which refers to the reactive process of electron transfer during Li⁺ desolvation/adsorption (R_ct). The low-frequency region is an inclined straight line, the slope of this line is related to the diffusion of Li⁺ in the bulk crystals (Warburg resistance)[34, 35]. The specific fitting parameters can be seen in Table 2, the doped samples demonstrate much smaller R_ct (55.35, 51.42 and 69.15 Ω for Ni_0.03-TNO, Ni_0.05-TNO and Ni_0.07-TNO, respectively) than that (168.0 Ω) of the pristine samples. The reason might be that Ni²⁺ could optimize the electronic structure of TNO, which facilitates the internal electron transfer, thus contributing to the electronic conductivity [36]. This can be verified from the obtained conductivity via the four-probe conductivity test. The electronic conductivity (2.2 × 10^–7 s cm^–1) of Ni_0.05-TNO is two orders of magnitude higher than that (1 × 10^–9 s cm^–1) of TNO [25]. These results unveil that Ni doping is effective in tuning the electronic conductivity of TNO.

Then, we explore the diffusion coefficient of Li⁺ via the impedance analysis. The Li⁺ diffusion coefficient is mainly related to the slope of the straight line in the low-frequency region, and the specific diffusion process can be obtained according to the following equation:

$${D}_{{\text{L}\text{i}}^{+}}=\frac{{R}^{2}{T}^{2}}{2{A}^{2}{n}^{4}{F}^{4}{C}^{2}{\sigma }^{2}}$$

In the given expression, R represents the gas constant, T stands for the absolute temperature, A denotes the surface area of the active electrode, n is the number of electrons per molecule, F represents the Faraday constant, C is the molar concentration of Li⁺, and σ represents the Warburg factor. σ can be estimated based on the plot of the linear fit between Z and the inverse square root of the lower angular frequency (Fig. 6b). It can be expressed by the following equation:

$${\text{Z}}^{{\prime }}\text{ = }{\text{R}}_{\text{s}}\text{+}{\text{R}}_{\text{ct}}\text{+}{\text{σω}}^{\text{-}\text{1/2}}$$

The Li⁺ diffusion coefficients of Ni_x-TNO and TNO are tabulated in Table 2. The Li⁺ diffusion coefficients of Ni_0.03-TNO, Ni_0.05-TNO and Ni_0.07-TNO are 3.23×10^–13, 3.75×10^–13, and 2.07×10^–13 cm² s^–1, respectively, which are markedly higher than that (3.51×10^–14 cm² s^–1) of the pristine one. The Ni_0.05-TNO displays the highest Li⁺ diffusion coefficient. The reason for this phenomenon may be that the lattice distortion caused by Ni²⁺ doping gives rise to an increase in the cell volume, which provides a wider channel for Li⁺ diffusion.

To further unveil the change of crystal structure during the (de)lithiation process of Ni_0.05-TNO, the non-in situ XRD tests were conducted for the pole pieces by discharging or charging them to specific voltages at current densities of 0.2 C. Here, four points were respectively selected for the initial charging and discharging processes (Fig. 7a). As shown in Fig. 7b, all the samples match well with the monoclinic Ti₂Nb₁₀O₂₉ and the crystal diffraction peaks are relatively sharp, which suggest a good stability of the crystal structure during the charging and discharging process. Figure 7c-d illustrates the enlarged (21$\stackrel{\text{-}}{\text{5}}$), (41$\stackrel{\text{-}}{\text{1}}$), and (020) crystal planes, and it is seen that the (020) crystal plane shifts to a low angle during discharging and returns to the initial position in the charging process. This unveils the good structural stability of Ni_0.05-TNO during (de)lithiation. However, the lattice parameters of (21$\stackrel{\text{-}}{\text{5}}$) and (41$\stackrel{\text{-}}{\text{1}}$) crystal planes do not change significantly, which is due to that these crystal planes are not the preferential diffusion paths of Li⁺ in Ni_0.05-TNO[37–39].

In this paper, Ni_x-TNO samples were synthesized using a simple solid-state method. The influence of Ni²⁺ on the structure, morphology and valence distribution of the material was explored through a series of characterizations. According to the experimental results, Ni_0.05-TNO is the most ideal electrode material. While the crystal structure remains unaffected by a moderate amount of Ni²⁺ doping, an increase in cell parameters occurs, creating more extensive diffusion channels and active sites for Li⁺ transport. In addition, the introduction of Ni alters the electronic environment of TNO, greatly improving the conductivity of the material and generating a certain amount of oxygen vacancies. Based on these advantages, Ni_0.05-TNO exhibits the most favorable electrochemical performance among all samples. A large reversible capacity of 306 mAh g^–1 and a high Coulombic efficiency of 91.46% can be reached at 0.1 C. Besides, there is still 146.19 mAh g^–1 after 500 cycles at a discharge current of 10 C. The findings in our research offer a fresh perspective on enhancing niobium-based oxide materials for novel lithium-ion anodes.

Conflict of Interest

The authors declare no competing financial interest.

Author Contribution

Xiuli Chen: conceptualization, methodology, investigation, writing - original draft, and data curation. Mingru Su: formal analysis and resources. Xueli Chen: data curation and methodology. Pei Cui: methodology and formal analysis. Yu Zhou: formal analysis. Yunxuan Ji: data curation. Panpan Zhang: validation, supervision, writing - review & editing. Yunjian Liu: visualization, supervision, and funding acquisition.

Acknowledgments

This research was sponsored by the National Natural Science Foundation of China (52004103, 51974137 and 52304328), the Natural Science Foundation of Jiangsu Province (BK20220534), Jiangsu Double-Innovation PhD Program in 2022 (JSSCBS20221241) and China Postdoctoral Science Foundation (2023M733189).

Xie F, Xu J, Liao Q, et al (2023) Progress in niobium-based oxides as anode for fast-charging Li-ion batteries [J]. Energy Reviews 2: 100027
Jiang T, Ma S, Deng J, et al (2022) Partially reduced titanium niobium oxide: a high-performance lithium-storage material in a broad temperature range [J]. Adv Sci 9: 2105119
Yu G, Zhang Q, Jing J, et al (2023) Bulk modification of porous TiNb₂O₇ microsphere to achieve superior lithium-storage properties at low temperature [J]. Small 19: 2303087
Aghamohammadi H, Hassanzadeh N, Eslami-Farsani R (2022) A comprehensive review study on pure titanium niobium oxide as the anode material for Li-ion batteries [J]. J Alloys Compd 911: 165117
Shi S, Tang Y, Wang G, et al (2022) Multiple reinforcement effect induced by gradient carbon coating to comprehensively promote lithium storage performance of Ti₂Nb₁₀O₂₉ [J]. Nano Energy 96: 107132
Lin C, Deng S, Kautz D J, et al (2017) Intercalating Ti₂Nb₁₄O₃₉ anode materials for fast-charging, high-capacity and safe lithium–ion batteries [J]. Small 13: 1702903
Lou S, Cheng X, Gao J, et al (2018) Pseudocapacitive Li⁺ intercalation in porous Ti₂Nb₁₀O₂₉ nanospheres enables ultra-fast lithium storage [J]. Energy Stor Mater 11: 57–66
Yang C, Ma D, Yang J, et al (2023) Crystallographic insight of reduced lattice volume expansion in mesoporous Cu²⁺-doped TiNb₂O₇ microspheres during Li⁺ insertion [J]. Adv Funct Mater 33: 2212854
Qi W, Shapter J G, Wu Q, et al (2017) Nanostructured anode materials for lithium-ion batteries: principle, recent progress and future perspectives [J]. J Mater Chem A 5: 19521–19540
Zheng R, Li Y, Yu H, et al (2020) Rational construction and decoration of Fe_0.5Nb_24.5O_62–x@C nanowires as superior anode material for lithium storage [J]. Chem Eng J 384: 123314
Yang L, Zeng J, Zhou L, et al (2021) Orderly defective superstructure for enhanced pseudocapacitive storage in titanium niobium oxide [J]. Nano Re 15: 1570–1578
Wang C H, Huang L, Zhong Y, et al (2021) Ti₂Nb₁₀O₂₉ anchored on aspergillus oryzae spore carbon skeleton for advanced lithium ion storage [J]. SM&T 28: e00272
Hu L, Luo L, Tang L, et al (2018) Ti₂Nb_2xO_4 + 5x anode materials for lithium-ion batteries: a comprehensive review [J]. J Mater Chem A 6: 9799–97815
Qi M, Hu M, Xu J, et al (2021) Smart construction of Ti₂Nb₁₀O₂₉ /carbon nanofiber core-shell composite arrays as anode materials for lithium-ion batteries [J]. J Alloys Compd 886: 161146
Zeng J, Yang L, Shao R, et al (2021) Mesoscopic Ti₂Nb₁₀O₂₉ cages comprised of nanorod units as high-rate lithium-ion battery anode [J]. J Colloid Interface Sci 600: 111–117
Zhang Y, Kang C, Zhao W, et al (2022) Crystallographic engineering to reduce diffusion barrier for enhanced intercalation pseudocapacitance of TiNb₂O₇ in fast-charging batteries [J]. Energy Stor Mater 47: 178–186
Lian Y, Zheng Y, Wang Z, et al (2023) Hollow ppy@Ti₂Nb₁₀O_29-x@NC bowls: A stress–release structure with vacancy defects and coating interface for Li capacitor [J]. Chem Eng J 454: 140287
Li H, Cai X, Li J, et al (2022) Ti₂Nb₁₀O₂₉@C hollow submicron ribbons for superior lithium storage [J]. Ceram Int 48: 23334–23340
Yao Z, Xia X, Zhang S, et al (2020) Oxygen defect boosted N-doped Ti₂Nb₁₀O₂₉ anchored on core-branch carbon skeleton for both high-rate liquid & solid-state lithium ion batteries [J]. Energy Stor Mater 25: 555–562
Deng S, Zhang Y, Xie D, et al (2019) Oxygen vacancy modulated Ti₂Nb₁₀O_29-x embedded onto porous bacterial cellulose carbon for highly efficient lithium ion storage [J]. Nano Energy 58: 355–364
Deng S, Zhu H, Liu B, et al (2020) Synergy of Ion Doping and spiral array architecture on Ti₂Nb₁₀O₂₉: a new way to achieve high-power electrodes [J]. Adv Funct Mater 30: 2002665
Liu K, Wang J-A, Yang J, et al (2021) Interstitial and substitutional V⁵⁺-doped TiNb₂O₇ microspheres: a novel doping way to achieve high-performance electrodes [J]. Chem Eng J 407: 127190
Utetiwabo W, Khurram Tufail M, Zeng C, et al (2022) Graphite foam as carbon-based footprint for in-situ fabrication of Ti³⁺-doped titanium niobium oxide (Ti₂Nb₁₀O₂₉) nanocrystal for high-rate performance lithium-ion batteries [J]. J Colloid Interface Sci 623: 1015–1026
Xia R, Zhao K, Kuo L-Y, et al (2022) Nickel niobate anodes for high rate lithium-ion batteries [J]. Adv Energy Mater 12: 2102972
Lin C, Yu S, Zhao H, et al (2015) Defective Ti₂Nb₁₀O_27.1: an advanced anode material for lithium-ion batteries [J]. Sci Rep 5: 17836
Wu Z, Guo M, Yan Y, et al (2021) Reducing crystallinity of micrometer-sized titanium–niobium oxide through cation substitution for high-rate lithium storage [J]. ACS Sustain Chem Eng 9: 7422–7430
Zheng J, Xia R, Sun C, et al (2023) Fast and durable lithium storage enabled by tuning entropy in wadsley–roth phase titanium niobium oxides [J]. Small 19: 2301967
Xia X, Deng S, Feng S, et al (2017) Hierarchical porous Ti₂Nb₁₀O₂₉ nanospheres as superior anode materials for lithium ion storage [J]. J Mater Chem A 5: 21134–21139
Deng S, Zhang Y, Xie D, et al (2019) Oxygen vacancy modulated Ti₂Nb₁₀O_29-x embedded onto porous bacterial cellulose carbon for highly efficient lithium ion storage [J]. Nano Energy 58: 355–364
Lu X, Jian Z, Fang Z, et al (2011) Atomic-scale investigation on lithium storage mechanism in TiNb₂O₇ [J]. Energy Environ Sci 4: 2638–2644
Yang C, Yu S, Ma Y, et al (2017) Cr³⁺ and Nb⁵⁺ co-doped Ti₂Nb₁₀O₂₉ materials for high-performance lithium-ion storage [J]. J Power Sources 360: 470–479
Yuan T, Luo S, Soule L, et al (2021) A hierarchical Ti₂Nb₁₀O₂₉ composite electrode for high-power lithium-ion batteries and capacitors [J]. Materials Today 45: 8–19
Wu X, Miao J, Han W, et al (2012) Investigation on Ti₂Nb₁₀O₂₉ anode material for lithium-ion batteries [J]. Electrochem Commun 25: 39–42
Muruganantham R, Lin M-C, Wang P K, et al (2022) Highly effective Al-doped titanium niobate porous anode material for rechargeable high-rate Li-ion storage performance [J]. J Taiwan Inst Chem Eng 131: 104187
Yang C, Lin C, Lin S, et al (2016) Cu_0.02Ti_0.94Nb_2.04O₇: an advanced anode material for lithium-ion batteries of electric vehicles [J]. J Power Sources 328: 336–344
Gao J, Cheng X, Lou S, et al (2017) Self-doping Ti_1-xNb_2+xO₇ anode material for lithium-ion battery and its electrochemical performance [J]. J Alloys Compd 728: 534–540
Griffith KJ, Seymour ID, Hope M A, et al (2019) Ionic and electronic conduction in TiNb₂O₇ [J]. Journal of the American Chemical Society 141: 16706–16725
Griffith KJ, Harada Y, Egusa S, et al (2020) Titanium niobium oxide: from discovery to application in fast-charging lithium-ion batteries [J]. Chem Mater 33: 4–18
Cui P, Zhang P, Chen X, et al (2023) Oxygen defect and Cl-doped modulated TiNb₂O₇ compound with high rate performance in lithium-ion batteries [J]. ACS Appl Mater Interfaces 15: 43745–43755

No competing interests reported.

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Ni_0.05Ti_1.95Nb₁₀O₂₉: an advanced anode material for high-performance lithium-ion storage

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1. Introduction

2. Experimental details

2.1 Materials Synthesis

2.2 Materials Characterization

2.3 Electrochemical Measurement

3. Results and discussion

4. Conclusions

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Conflict of Interest

Author Contribution

Acknowledgments

References

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