Effect of Synthesis Temperature on Structure and Electrochemical Performance of Spinel-Layered Li_1.33MnTiO_4+z in Li-Ion Batteries

Abstract

Herein, the spinel-layered cathode material Li_1.33MnTiO_4+z (0.8LiMnTiO₄•0.2Li₂Mn_0.5Ti_0.5O₃) is investigated for the purpose of developing a high-capacity, low-cost, and environmentally friendly cathode for Li-ion batteries. Sol-gel synthesis is conducted and the relationships between synthesis temperature, structure, and electrochemical performance of the cathodes are studied. The effects of size and purity on the capacities of these cathodes are discussed. The samples fired at 500 and 600 °C contain an impurity phase of TiO₂, thus delivering capacities of 208 and 210 mAh g⁻¹ at C/10, respectively. The sample fired at 700 °C without the impurity phase of TiO₂ shows a high capacity of 222 mAh g⁻¹ at C/10 and capacity retention of 90.5% after 100 cycles at 1C.

1. Introduction

Although the spinel LiMn₂O₄ cathode material has a lot of advantages such as its low cost, eco-friendliness, and ease of synthesis, it exhibits a low capacity (<148 mAh g⁻¹) and a narrow working voltage range (3–4.5 V) because of its structural instability caused by Mn dissolution at low voltages and Jahn–Teller distortion. Therefore, many efforts have been made to stabilize its structure by substituting Mn with Ti, Al, Ni, or Li [1,2,3,4,5]. In the work done by Wang et al., the capacity retention of spinel LiMn_2−xTixO₄ was increased from 76% to 83% after 80 cycles when x increased from 0.5 to 1 [6]. When half of Mn is substituted by Ti in LiMn₂O₄, a new spinel phase of LiMnTiO₄ is formed [7]. In this phase, the oxidation states of Mn and Ti are +3 and +4, respectively. From a crystal structure point of view, the O²⁻ ions form a cubic close-packed array, and the Li⁺ ions occupy tetrahedral 8a sites as in LiMn₂O₄, whereas the Mn³⁺ and Ti⁴⁺ ions alternatively occupy octahedral 16d sites. The high binding energy of Ti–O (662 kJ mol⁻¹) can suppress the Jahn–Teller distortion and the cathode material can be used in a wide range of voltages (2–4.8 V). Consequently, the capacity is improved because more than one Li⁺ can be extracted or inserted, which is associated with the oxidation or reduction of the Mn⁴⁺/Mn³⁺ and Mn³⁺/Mn²⁺ redox couples [8]. Ti⁴⁺ is electrochemically inactive in this voltage range, and thus decreases the capacity of LiMnTiO₄ to less than 180 mAh g⁻¹. The introduction of a layered phase of Li₂Mn_0.5Ti_0.5O₃ can increase the quantity of Li available for intercalation, leading to increased capacity [9]. Moreover, the layered phase can stabilize the spinel phase at low voltages, resulting in improvement in cycling stability [10]. Therefore, a strategy to study composite (1 − x)LiMnTiO₄•xLi₂Mn_0.5Ti_0.5O₃ has potential for identifying new cathode materials for Li-ion batteries (LIBs).

Synthesis methods have a significant effect on the electrochemical performance of electrode materials [11,12]. Among them, the sol-gel method has many advantages, such as mixing precursors at the atomic scale, synthesizing at low temperatures and in a short time, and uniform particle size in the nanometer range. Nano-sized materials can provide short diffusion lengths for Li⁺. Zhang et al. [13] used the sol-gel method and heat treatment at 700 °C to prepare a 120 mAh g⁻¹ LiMnTiO₄ cathode material. By contrast, Chen et al. [8] reported a low-temperature sol-gel route at 500 °C to synthesize high-capacity LiMnTiO₄ up to 200 mAh g⁻¹. The increased capacity may be a result of the higher surface area of nanoparticles synthesized at lower temperatures. However, in comparison to micromaterials, nanomaterials have many disadvantages, such as low volumetric energy density and poor cycle life, caused by high surface energy, which increases the undesirable surface reaction. Additionally, at a low firing temperature of 500 °C, the TiO₂ impurity phases cannot be removed. The synthesis temperature affects not only particle size and purity but also the phase content, as well as the phase properties, of cathode materials [10].

Based on the above investigation, in this work, we studied the effects of synthesis temperature and the sol–gel method on the electrochemical performance of Li_1.33MnTiO_4+z (0.8LiMnTiO₄•0.2 Li₂Mn_0.5Ti_0.5O₃). This work aims to increase the capacity and cycling stability of LiMnTiO₄ while taking advantage of its unique qualities, including low cost, thermal stability, and nontoxicity.

2. Materials and Methods

2.1. Preparation of Cathode Materials

LiCH₃COO·2H₂O, Mn(CH₃COO)₂·4H₂O, and citric acid with a molar ratio of 1.33:1:2.33, respectively, were dissolved in a mixed solvent of distilled water and ethylene glycol. Then, titanium (IV) isopropoxide with a molar amount equal to that of Mn(CH₃COO)₂·4H₂O was added dropwise. The sol was stirred for 5 h and then heated to 140 °C for 12 h. The obtained xerogel was fired in the air at 500, 600, and 700 °C (ramping rate: 2 °C min⁻¹) for 14 h and then cooled naturally. The resulting Li_1.33MnTiO_4+z nanoparticles are denoted as S500, S600, and S700, respectively.

2.2. Structural, Physical, and Electrochemical Characterization

X-ray diffraction measurements (Rigaku X-ray diffractometer with Cu-Kα radiation at 45 kV and 200 mA with a scanning step of 0.02°) were conducted to analyze the phase of the samples in the range of 10° ≤ 2θ ≤ 100°. Rietveld refinement was conducted using the General Structure Analysis System (GSAS) program [14]. A scanning electron microscope (SEM, Nova NanoSEM 450) and a high-resolution transmission electron microscope (HRTEM, JOEL JEM-2100F) were used to determine the morphologies of the particles. X-ray photon spectroscopy (XPS, K-Alpha+ Thermo Scientific) was used to determine the oxidation state of the elements. The Brunauer–Emmett–Teller method was used to determine the surface area of particles (BET, BEL JAPAN Inc., Japan).

Coin cells were fabricated to evaluate the electrochemical properties of the cathodes (reference electrode is Li metal). The working electrodes comprised the active material, Ketjen black, and teflonrized acetylene black (TAB) as a binder, in a mass ratio of 70:10:20, respectively. These materials were mixed thoroughly and pressed onto a stainless steel mesh, and dried under vacuum at 120 °C for 12 h. The mass loading of cathodes was 3.57 mg/cm². A 2032 coin-type cell, which consisted of the cathode, a separator, and Li metal, was assembled in an Ar-filled glovebox. The electrolyte was a 1 M LiPF₆ solution in a 1:1 mixture of ethylene carbonate and dimethyl carbonate. The cell was aged for 12 h prior and whose electrochemical properties were tested by a NAGANO BTS-2004H battery charger between 0.1 and 3 V vs. Li⁺/Li. Electrochemical impedance spectroscopy (EIS) measurements were taken with an Autolab electrochemical workstation over a frequency range of 10⁶ to 10⁻² Hz with a voltage of 10 mV amplitude.

3. Results and Discussion

3.1. Structural Characterization of Cathodes

Figure 1 illustrates the comparison of the XRD patterns of three samples. As can be seen, with increasing synthesis temperature, the full-width at half-maximum peaks decreased, indicating an increase in particle size. The pattern of LiMn₂O₄, PDF# 35-0782 (d_cell = 8.2472) standard with the cubic spinel structure and space group of Fd3m, was used to index these peaks. The S500 exhibited an impurity phase of anatase (A, peak located at 2θ = 25.2°) and rutile (R, a peak located at 2θ = 27.4°) TiO₂, which was similar to the results reported in Ref. [8]. The anatase phase transforms into the rutile phase at 600 °C. Therefore, in the S600 sample, only the peak of the rutile phase was present. The low synthesis temperature did not provide sufficient energy to complete the reaction. At this temperature, if the amount of Li was increased, the reaction would be completed with no impurity phase of rutile and with an increase in the layered content in the composite [9,15,16]. For the S700 sample, no impurity phase was observed. All peaks could be indexed with LiMn₂O₄ and the space group of Fd3m. From the selected region, the strongest peaks of the (111) plane in the S500 and S600 samples shifted to a higher angle, caused by the formation of the spinel phase of Li_1+xMn_2−x−yTi_yO₄. With increasing synthesis temperature, this phase decomposed to the spinel LiMnTiO₄ and layered Li₂Mn_0.5Ti_0.5O₃, which is similar to Li₂TiO₃ [17]. This reaction can be defined using the following equations:

$$\mathrm{Li}-\mathrm{Mn}-\mathrm{Ti}\mathrm{citrate}\mathrm{salt}\stackrel{500 °C }{\to }{\mathrm{Li}}_{1+x}{\mathrm{Mn}}_{2-x-y}{\mathrm{Ti}}_y{\mathrm{O}}_4(\mathrm{anatase}+\mathrm{rutile})\stackrel{600 °C }{\to }{\mathrm{Li}}_{1+x}{\mathrm{Mn}}_{2-x-y}{\mathrm{Ti}}_y{\mathrm{O}}_4+{\mathrm{TiO}}_2\left(\mathrm{rutile}\right)\stackrel{700 °C }{\to }{\mathrm{LiMnTiO}}_4+{\mathrm{Li}}_2{\mathrm{Mn}}_{0.5}{\mathrm{Ti}}_{0.5}{\mathrm{O}}_3+{\mathrm{O}}_2$$

(1)

In the selected region from 19° to 33°, the intensity of the (020)_L peak in the layered phase at ~20.5° and the (220) peak increased, moving from the S500 sample to the S700 sample. In the S700 sample, they could be clearly observed. The (020)_L peak belongs to the ordering of the LiMn(Ti)₆ units in the Li₂Mn_0.5Ti_0.5O₃ component and can be attributed to the Li and Mn (Ti) cation ordering in the transition metal layers. This peak was weaker in the S600 and S500 samples because of the disordering of Li and Mn (Ti). Conversely, the (220) peak caused by the substitution of Ti induced heavy atoms, especially Mn, to occupy the Li-occupied 8a sites [2,18,19,20,21].

Rietveld refinements were performed to evaluate the phase fraction and position of atoms in the phases of the three samples. The results are presented in

Table 1. Rietveld refinement and crystal data obtained from the XRD data.

Sample		S500	S600	S700
Space Group
Fd3m	Phase	Li1.15Mn1.05Ti0.8O4	Li1.1Mn1.1Ti0.8O4	LiMnTiO4
	Phase content (%)	50	71	83
	Lattice parameter (Å)	8.212	8.247	8.264
C2/m (S500) or C2/c (S600 and S700)	Phase	Li2Mn0.9Ti0.1O3	Li2Mn0.5Ti0.5O3	Li2Mn0.5Ti0.5O3
	Phase content (%)	32	24	17
	Lattice parameter (Å)	a = 4.989 b = 8.647 c = 4.999 β = 109.49°	a = 4.850 b = 8.936 c = 9.776 β = 99.187°	a = 4.850 b = 8.936 c = 9.729 β = 99.187°
I41/amd	Phase	TiO2 anatase
	Phase content (%)	10	0	0
	Lattice parameter (Å)	a = b = 3.791 c = 9.466
P42/mnm	Phase	TiO2 rutile	TiO2 rutile
	Phase content (%)	8	5	0
	Lattice parameter (Å)	a = b = 4.610 c = 3.126	a = b = 4.629 c = 2.950
Fitting quality	Rwp (%) Rp (%) χ2 (%)	5.34 3.99 4.91	5.43 4.04 3.55	6.49 4.61 2.95

and Table S1. In the three samples, there were two main phases: The spinel phase (in the Fd3m space group) and the layered phase (in the C2/m space group for S500 or C2/c for S600 and S700). For the spinel phase, the lattice parameter increased because of the replacement of Ti⁴⁺ ions with a larger radius in the spinel frame. It exhibited a value of 8.267 in S700 and 8.212 in S500, similar to a report in Ref. [11]. When less Ti was substituted for Mn (S500), the layered phase was similar to Li₂MnO₃ (belonging to the C2/m space group), whereas it converted to C2/c similar to Li₂TiO₃ in S600 and S700 when large quantities of Ti were substituted for Mn. The total impurity of TiO₂ in S500 was the highest, at 18% (in Ref. [8] it was 15%). When the synthetic temperature increased, the TiO₂ impurity phase decreased and was respectively 5% and 0% for S600 and S700.

Figure 2 depicts the SEM images of the three samples. It was apparent that S500 exhibited the smallest particle size (Figure S1). The particles grew larger with increasing synthesis temperature. The primary nanoparticles in the S500 and S600 samples aggregated into secondary particles as a result of their large surface areas (Figure 2b,d). The S700 sample exhibited particle sizes of 100–300 nm. In the S700 sample, the octahedral shape of the particles was clear. This indicates the high crystallinity of this sample, consistent with the XRD data. The particle size and the crystallinity both affected the electrochemical performance of the cathode; the former enhanced the rate ability, whereas the latter enhanced the capacity and cycling stability.

We further analyzed the S700 sample using HRTEM because it had no impurity phase of TiO₂ The results were shown in Figure 3. The lattice fringe spacing was determined to be 0.487 nm, which belonged to the (111) plane of the spinel phase or the (002) plane of the layered phase. The composite structure was clear in the marked region. Moreover, the FFT of the selected region confirmed the co-existence of the spinel and layered phases.

The oxidation states of Mn and Ti were determined by XPS measurements for all samples, as depicted in Figure 4. Accordingly, the Mn 2p peaks of all samples exhibited significantly split spin-orbit components (the splitting values were all greater than 11.5 eV), which were allocated for Mn 2p_3/2 and Mn 2p_1/2 [22]. The Mn 2p_3/2 peak shifted to lower binding energy as the synthesis temperature increased because of the co-existence of Mn⁴⁺ and Mn³⁺. The values were 642.09, 641.98, and 641.81 eV for S500, S600, and S700, respectively. The XPS spectra of Mn 2p_3/2 were deconvoluted to quantify the percentage of each ion, as depicted in Figure S2. The Mn³⁺ content increased, moving from S500 to S700, whereas the Mn⁴⁺ content decreased in this direction. To further confirm the existence of both Mn⁴⁺ and Mn³⁺ in these samples, the Mn 3s spectra were analyzed. The coupling of 3s electrons and 3d electrons could induce peak splitting in the Mn 3s spectrum, and its magnitude (ΔE) could be used to recognize the oxidation state of Mn. In general, ΔE values for MnO₂ (Mn⁴⁺), Mn₂O₃ (Mn³⁺), and MnO (Mn²⁺) are 4.7, ≥5.3, and 6.0 eV, respectively [23]. The existence of a lower oxidation state of Mn causes an increase in ΔE. The values of ΔE for S500, S600, and S700 were 4.5, 4.53, and 4.56, respectively. These values were lower than those in MnO₂ because of the effects of Li and Ti in the structure. However, these values indicate that most of the Mn in the three samples is in the +4 oxidation state. Additionally, the amount of Mn⁴⁺ in the S500 was the highest, and the amount of Mn³⁺ increased for S600 and S700. This result was consistent with the XRD analysis and the mechanism proposed above. For Ti, the Ti 2p in the three samples was also split into two peaks, similar to that of Mn 2p, which is a typical characteristic for a 3d transition metal. The Ti 2p_3/2 binding energies increased in the following sequence: S500 > S600 > S700. The value for S700 was 457.66 eV, in agreement with the Ti⁴⁺ of the Li₂TiO₃ [24]. However, S500 and S600 exhibited Ti 2p_3/2 binding energies of 457.8 and 457.7 eV because of the presence of the impurity phases of TiO₂.

3.2. Electrochemical Properties

Figure 5a,c,e depict the charge-discharge profiles of the three cathodes at C/10 (1C = 154 mA g⁻¹). In the initial charging process, these cathodes exhibited similar profiles, with a plateau at ~4.1 V. This plateau was attributed to the extraction of Li⁺ from the tetrahedral 8a site in the spinel cathode, with simultaneous oxidation of Mn³⁺ to Mn⁴⁺. The capacity of S700 (106 mAh g⁻¹) was higher than those of S600 and S500 (88 mAh g⁻¹) because of the absence of a TiO₂ impurity phase. During the discharge process, the three cathodes exhibited two plateaus, located at ~4.07 and ~2.8 V. The first one corresponded to the formation of the LiMnTiO₄ phase, in which Li⁺ was inserted back to the 8a site, similar to what occurred in LiMn₂O₄. The second one was related to the formation of Li₂MnTiO₄, in which Li⁺ was inserted into the 16c site.

The discharge capacities of the S500 and S600 cathodes were similar (~205 mAh g⁻¹), whereas that of the S700 cathode was the highest (218 mAh g⁻¹). There are three effects that contribute to the discharge capacity, including size effect, structure effect, and purity effect. The S500 and S600 samples exhibited lower particle sizes, thereby increasing their surface areas and further enhancing their discharge capacities (the surface area of S500 and S600 is 13.8 and 8.81 m² g⁻¹, respectively). However, they also exhibited an impurity phase of TiO₂, thus reducing the amount of active material. The S700 sample exhibited larger particle sizes (its surface area is 4.19 m² g⁻¹); however, there was no impurity phase of TiO₂, thus providing maximum active material. Additionally, the disordering structure in S500 and S600 was higher than that in S700, thereby increasing the capacity of the cathodes [25]. The S600 and S700 cathodes exhibited a layered phase at the 3 V region, which was not clear in the S500 sample. This is clearly observed in the dQ/dV plot and is discussed later. However, in the subsequent cycle, the activation of the layered phase was apparent in the three cathodes by increasing the working voltage over the 3 V region. The first Coulombic efficiency (CE) was over 100%, which is characteristic of the spinel phase. In the subsequent cycle, the capacity of the three cathodes increased because of the activation of the layered phase. This activation caused the CE to increase with cycling. After five cycles, the discharge capacity of the S700 sample was the highest, at 222 mAh g⁻¹ (specific energy ~679 Wh kg⁻¹, which is higher than that of LiMn₂O₄, ~480 Wh kg⁻¹), whereas it was 208 and 210 mAh g⁻¹ for S500 and S600, respectively.

The corresponding dQ/dV plots of the three cathodes at the 1st, 2nd, and 5th cycle are depicted in Figure 5b,d,f, respectively, for a better understanding of the electrochemical performance of these samples. For the 1st charge–discharge process, these cathodes exhibited peaks at ∼4.1 V, which was related to the extraction/insertion of Li⁺ from the 8a sites of the spinel structure and the oxidation/reduction of the redox couple Mn³⁺/Mn⁴⁺. These peaks matched the voltage plateau (Figure 5a,c,e). The activation peak of the layered phase at ~4.5 V for the first charging was absent because there were fewer layered phase components in the composite. However, the activation of the layered phase was evident by the peak at ∼3 V that stemmed from the reduction reaction of Mn⁴⁺ to Mn³⁺ [26]. The last peak at ~2.2 V in the three cathodes was attributed to the reduction of Mn³⁺ and the rearrangement of the structure. This peak disappeared in the next cycles of the S600 and S700 cathodes, whereas it was still observed in the S500 cathode. The capacity contribution in the 4 V region originated from the anion redox couple because of the disordering in the structure synthesized at low temperatures for the S500 and S600 samples. By contrast, for the S700 cathode, the capacity in the 4 V region decreased because of the higher crystallinity and ordering.

Figure 6 depicts the performance of the three cathodes with different C-rates. Their rate capabilities are depicted in Figure 6a. As can be seen, S500 exhibited the smallest particle size; thus, its capacity was slightly higher than that of S600 at a high C-rate. Moreover, the S500 exhibited an anatase phase of TiO₂, demonstrating remarkable electrochemical properties in comparison to the rutile phase. The S700 cathode exhibited the highest performance at all C-rates. The lowest impurity phase, intermediate particle size, and contribution of the layered phase could be the reason for this behavior. In particular, the S700 cathode delivered the highest capacities of 222, 212, 196, 180, 162, 124, and 85 mAh g⁻¹ at C/10, C/5, C/2, 1C, 2C, 5C, and 10C, respectively. The S700 cathode exhibited a capacity that was 141% higher than those of S500 and S600 at 5C.

The cycling stability of the cathodes in the voltage range of 2.0–4.8 V at 1C is depicted in Figure 6b (all cathodes were activated at C/10 for three cycles). Similar to rate capability, the capacities of the cathodes decreased in the following sequence: S700 > S500 > S600. The values were 170, 135, and 130 mAh g⁻¹ at the 20th cycle for S700, S600, and S500, respectively. The capacity of the S700 cathode was superior (13% higher) in comparison to that for LiMnTiO₄ reported in the literature [6]. The higher capacity of the S700 cathode is explained by the absent impurity phase and the highest Mn³⁺ content, which improves conductivity. The capacity retention values for S500, S600, and S700 after 100 cycles were 82%, 84.02%, and 90.6%, respectively. The poor cycling stability of S500 may be caused by the small particle size, facilitating the decomposition of the electrolyte, or due to impurities and poor crystallinity. For S700, the inherent property of the layered phase that transformed into the spinel phase during cycling was the main reason for the capacity loss. However, the layered phase could be stabilized to the spinel phase at low voltages, resulting in an improvement in cycling stability. The CE values of all samples were close to 100%, exhibiting insignificant energy loss during the charge and discharge processes.

The electrochemical behavior of these cathodes was further investigated by EIS, as depicted in Figure 7. The Nyquist plots of the three cathodes depicted in Figure 7b include two parts, representing two features. The charge-transfer resistance (R_ct) is characterized by a semicircle in the medium-frequency region, whereas the Li⁺ diffusion through the cathode (Warburg diffusion) is characterized by a sloped line in the low-frequency region. The R_ct values of S500, S600, and S700 were 49.86, 51.32, and 58 Ω, respectively. A lower value of R_ct caused an increase in the capacity of the cathode. Additionally, the Li⁺ diffusion coefficients of the three cathodes, which are presented in Table S2, were 4.11 × 10⁻¹¹, 3.16 × 10⁻¹¹, and 1.66 × 10⁻¹¹ for S500, S600, and S700, respectively. S500 exhibited the highest Li⁺ diffusion coefficient and the lowest R_ct; however, its capacity was lower than that of S700 because of the presence of a large impurity phase. The diffusion coefficient of S700 was higher than that of LiMn₂O₄ reported in the literature [27] due to the effects of the layered phase.

4. Conclusions

The low-cost spinel-layered cathode material 0.8LiMnTiO₄•0.2Li₂Mn_0.5Ti_0.5O₄ was successfully synthesized by a sol–gel method. The effects of synthesis temperature on the electrochemical properties of the cathodes were investigated. Based on XRD and Rietveld refinement analysis, the synthesis temperature not only affected the impurity phase of TiO₂, but also affected the ratio and composition of the spinel and layered phases. Moreover, the XPS analysis confirmed the existence of Mn⁴⁺, Mn³⁺, and Ti⁴⁺ in the three samples and a decrease in Mn⁴⁺ content when increasing the synthesis temperature. Consequently, it affected the electrochemical behavior. The optimized sample, which was synthesized at 700 °C, could deliver a high capacity of 222 and 170 mAh g⁻¹ at C/10 and 1C, respectively. The capacity retention was 90.5% after 100 cycles. Understanding the relationship between synthesis temperature and the structure of this system can contribute to the development of inexpensive and non-toxic cathode materials for LIBs.