Journal of Alloys and Compounds 722 (2017) 229e234

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Journal of Alloys and Compounds

journal homepage: http://www.elsevier.com/locate/jalcom

Preparation and electrochemical performance of Li4
xMgxTi5O12 as

anode materials for lithium-ion battery
Qi Cheng a, 1, Shun Tang a, 1, Chang Liu a, Qian Lan a, Jinxing Zhao a, Jiyuan Liang a, Ji Yan a,
Zuqi Liu b, Yuan-Cheng Cao a, *
a
Key Laboratory of Optoelectronic Chemical Materials and Devices, Ministry of Education, School of Chemical and Environmental Engineering, Jianghan
University, Wuhan 430056, China
b
Department of Chemistry and Biochemistry, Ohio State University, Columbus, OH 43210, USA

a r t i c l e i n f o a b s t r a c t

Article history: Li4-xMgxTi5O12 (0 & X & 0.2) anode material was synthesized by a solid-state method using Li2CO3, MgO
Received 6 April 2017 and anatase TiO2. The effects of Mg element doping on the crystal structure, phase composition,
Received in revised form morphology and electrochemical properties of Li4-xMgxTi5O12 were investigated by XRD, SEM and EDX.
25 May 2017
The electrochemical properties of Li4-xMgxTi5O12 were characterized through Cyclic voltammetry and AC
Accepted 4 June 2017
Available online 7 June 2017
impedance experiments. The results indicated that when x ¼ 0.10, the resultants show better electro-
chemical performance in higher rates cycle stability and the polarization degree. The initial discharge
capacity reaches 122.5 mAh/g at 2 C, and the discharge capacity still remains 119.3 mAh/g after 100
Keywords:
Lithium titanium oxide
cycles.
Mg doping © 2017 Elsevier B.V. All rights reserved.
Conductivity
Magnification
Lithium ion batteries
Anode

1. Introduction diffusion coefficient of lithium ions in Li4Ti5O12 is 2  10
8 cm2/s,

With the development of lithium ion batteries (LIBs) in electric
vehicles and hybrid vehicles, more attention is paid to safety per-
formance, cycle performance and capacity of LIBs [1,2]. Now the
conventional carbonaceous materials used as anodes in commercial
LIBs have safety issues owing to a low Li-intercalation potential
approaching almost 0 V (vs. Li/Liþ). The matrix of carbon electrode
is easy to expand in the processes of Liþ extraction and intercala-
tion, which affects the cycle life of the system [2e4]. Li4Ti5O12 (LTO)
as a composite oxide of transition metal belongs to the AB2X4 se-
ries. It shows a kind of defect spinel structure, thus the insertion
and deinsertion of Liþ in Li4Ti5O12 has no influence on the crystal
structure, which is known as “zero strain” electrode material [3]. As
a result, the spinel LTO has been viewed as a promising alternative
to carbonaceous material due to its high insertion potential at
around 1.55 V (vs. Li/Liþ), which can avoid the dendritic lithium
growth on the anode surface at high charging rate [4]. The chemical
* Corresponding author.
E-mail addresses: yuancheng.cao@jhun.edu.cn, caosome@126.com (Y.-C. Cao).
1
These authors contributed equally to this work.
which is larger than that of graphite anode. However, the con-
ductivity of Li4Ti5O12 material is low and thus it often results in
large polarization which seriously hinders its high rate perfor-
mance. Studies showed LTO produces Ti3þ/Ti4þ when it is doped
with metal ions (such as Ca2þ [5], Al3þ [6], W6þ [7], La2þ [8]), which
leads to the improvement of the conductivity and the rate perfor-
mance of the material. X. Li and Y Wang et al. reported the Ca2þ
doped LTO for the anode materials and results showed s novel
Li3.9Ca0.1Ti5O12 material was promising as a high-rate anode ma-
terial for the lithium-ion batteries [9]. Mg2þ radius (0.072 nm) is
close to that of Liþ (0.076 nm) and the substitution of 8a at the
position of Liþ has little effect on the integrity of the crystal lattice
and the doping of Mg2þ can reduce the electrode potential, increase
the specific capacity of the battery, improve the conductivity of the
electrode material, and reduce the impedance and polarization
[10e13].
In this paper, Li4-xMgxTi5O12 (0 & X & 0.2) anode material was
synthesized by solid-state method using Li2CO3, MgO and anatase
TiO2 and the effects of Mg2þ doping on the structure and electro-
chemical properties of LTO were studied. This study provides
alternative approach for developing the high rate anode materials

http://dx.doi.org/10.1016/j.jallcom.2017.06.040
0925-8388/© 2017 Elsevier B.V. All rights reserved.
230 Q. Cheng et al. / Journal of Alloys and Compounds 722 (2017) 229e234
for LIBs.
2. Experimental
2.1. Synthesis of Li4-xMgxTi5O12 materials
Li4-xMgxTi5O12(x ¼ 0.00, 0.05, 0.10, 0.20) were synthesized by a
solid-state reaction. Stoichiometric Li2CO3, TiO2 and MgO were
used as raw materials which were mixed by ball milling for 30 min
in acetone slurry, which was followed by drying at 100  C for 1 h.
Finally, the products were calcined at 800  C for 12 h in the argon
atmosphere to obtain the samples. The synthesis equation was
showed in (1):
5TiO2 þ 2Li2CO3 / Li4Ti5O12 þ 2CO2
2.2. Preparation of the batteries
The Li4-xMgxTi5O12, PVDF, acetylene black were mixed in mass
ratio of 8:1:1 and ground for 3 h, and then N-Methyl pyrrolidone
was added as solvent, stirring for 5 h to prepare slurry. The slurry
was coated on the copper foil, and the electrode was placed in oven
at 120  C for 10 h. Lithium foil was used as counter and reference
electrode, and Celgard 2400 was used as separator. 1 M LiPF6 in EC/
DMC/EMC (1:1:1 by volume) was used as electrolyte. Cell assembly
was carried out in an Ar-filled glove box (O2, H2O < 1 ppm). Cyclic
voltammetry (CV) was conducted on an Autolab electrochemical
workstation at a scanning rate of 0.5 mV/s between 0.8 and 2.8 V.
Electrochemical impedance spectroscopy (EIS) was carried out in
the frequency range from 100 kHz to 10 mHz with 5 mV amplitude.
Galvanostatic charge/discharge cycling test was conducted on a
multichannel battery test system (Wuhan LAND Electronics Co.
Ltd).
3. Results and discussion
3.1. Structure and morphology characterization
XRD tests were carried out for the samples of Li4-xMgxTi5O12
(x ¼ 0.00, 0.05, 010, 0.20) and the results are showed in Fig. 1. As we
Fig. 1. XRD patterns of Li4
xMgxTi5O12 (x ¼ 0.00, 0.50, 0.10, 0.2).
can see from the XRD pattern, the diffraction peaks of all samples
keep consistence with the standard diffraction peaks of LTO (JCPDS
No. 49-0207) [14]. At the same time, EDX results in Fig. 2 show that
there were Ti, Mg, and O elements signal. By comparing with the
x ¼ 0.00 sample, we can see that the Mg2þ doping in the LTO did not
change the spinel structure.
For clear observation, the peak positions of (111) of the samples
were magnified and shown in Fig. 3. As the rates of Mg2þ doping
increase, the sharpness of the XRD spectrum decreases. The sharp
diffraction peaks were observed for all samples, suggesting the
good crystallinity. The peak intensity of x ¼ 0.20 is weakened and
broadened, which is attributed to the small lattice distortion caused
by the addition of too much Mg2þ [15]. It also can be observed that
the (111) peaks of the Li4Ti5
xMgxO12 shift to smaller angles after
(1) Mg doping, which suggests the lattice parameters increase after
Mg2þ doping. It may be ascribable to the substitution of Mg2þ
(0.072 nm) for Ti4þ (0.0605 nm) sites. It shows that Mg entered the
LTO lattice structure and occupied the position of Liþ in the part of
8a. It indicates that the lattice regularity of the doped Li4Ti5O12
decreases gradually.
Fig. 4 shows SEM images of Li4-xMgxTi5O12 samples with
different proportions of Mg2þ (x ¼ 0.00, 0.05, 010, 0.20). It clearly
shows that, under the same condition, the uniformity and homo-
geneity of sample (x ¼ 0.20) were poor, and there was an obvious
agglomeration phenomenon. The agglomeration of particles affects
the diffusion process of Liþ during charging/discharging. For
x ¼ 0.10 sample, it showed a uniform distribution with the average
size of 200 nm. This kind of uniform particles can improve the
discharge capacity and voltage platform. The small, loose particle
with good void distribution can increase the contact area between
electrode and electrolyte, which can improve the lithium insertion
depth of the active material [16]. The path of the migration of
lithium ions and electrons in the crystal can be shortened, and the
polarization of the electrode material during the charging and
discharging process of the high rate can be reduced, and the rate
performance of the material can be improved. In order to investi-
gate the distribution of elements in doped samples, the mapping is
used. As shown in Fig. 5, the EDX test results showed that the
presence of magnesium, titanium, and oxygen in the bright spot
indicates that the Mg2þ is uniformly distributed in the Li4-
xMgxTi5O12 crystal structure.
Fig. 2. EDX spectrum of the Li4
xMgxTi5O12(x ¼ 0.10) powder.
 Q. Cheng et al. / Journal of Alloys and Compounds 722 (2017) 229e234
Fig. 3. (111) peaks of Li4
xMgxTi5O12 (x ¼ 0.00, 0.50, 0.10, 0.20).
3.2. Electrochemical performance
Cyclic voltammograms of Li4Ti5
xMgxO12(x ¼ 0.00, 0.05, 0.10,
0.20) electrodes were obtained at a scan rate of 0.5 mV/s between
0.8 V and 2.8 V as showed in Fig. 6. It demonstrated that there was a
pair of sharp and reversible redox peaks for each sample, which are
the result of two-phase reaction based on the redox couple of Ti4þ/
Ti3þ in the spinel structure [17], according to equation (2) of
discharge of Li4Ti5O12 as anode material:
Li4Ti5O12 þ 3Liþ þ 3e
 / Li7Ti5O12, E ¼ 1.5 V
According to the results in Fig. 6, it clearly shows that with the
increase of doping ratio, the voltage difference between oxidation
and reduction decreases gradually. The voltage differences between
anodic and cathodic peaks reflect the polarization degree of the
Fig. 4. SEM photograph of Li4
xMgxTi5O12 (x ¼ 0.00 (a), x ¼ 0.05 (b), x ¼ 0.10 (c), x ¼ 0.20(d)).
231
electrode: x ¼ 0.00 is 0.35 V, and x ¼ 0.10 is 0.26 V. It indicated that
the Mg2þ doping reduced the phenomenon of polarization. Besides,
x ¼ 0.10 shows the least potential difference among all the doped
samples. Thus, the optimal ratio of Mg-doping is 0.1, which exhibits
the lowest electrode polarization. However, when x ¼ 0.20, the
voltage difference between oxidation and reduction is 0.41 V,
which may be caused by excessive doping of Mg2þ, which destroys
the crystal structure. This conclusion is consistent with the results
of SEM which suggested that too high amount of doping is adverse
[18].
Fig. 7 shows the rate capacity of the Li4Ti5
xMgxO12 (x ¼ 0.00,
0.05, 0.10, 0.20) electrodes at different rates of 0.1 C, 0.5 C, 1 C, 2 C,
5 C. For each rate, the charge/discharge processes of the samples
were running for 5 cycles. It can be clearly seen that the capacity
quickly decreased with the increasing of doping rate. At 5 C, the
specific capacity of pure LTO (Li4Ti5O12) decreased severely,; the
capacity (55 mA h/g) was only 33% of the initial discharge capacity
of 163.1 mA h/g at 0.1 C. In contrast, the Mg2þ doped
Li4Ti5
xMgxO12 (x ¼ 0.05, 0.10, 0.15, 0.20) electrodes displayed no
differences at 0.1 C. However, under the condition of 1 C, 2 C, 5 C,
the capacity retention rate of x ¼ 0.10 was the best, and the
retention rate at 5 C was 59.43%, which was much higher than that
of undoped Li4Ti5O12. The specific capacitance of undoped Li4Ti5O12
was higher than that of x ¼ 0.20, which is due to the fact that the
excessive Mg2þ doping destroys the regularity and morphology of
Li4Ti5O12 particles. These results could be explained that the doping
of Mg2þ can increase the conductivity of Li4Ti5O12, which can
reduce the polarization of charge-discharge process [18,19]. It is
beneficial for insertion and extraction reaction of Liþ. From above
discussion, under the high rate, a small amount of Mg2þ doping is
beneficial for the stability of the material; it can improve the
electrochemical performance of Li4Ti5O12 at high current density.
Excessive doping of Mg2þ may have negative effects on the uni-
(2) formity of the morphology and structure of Li4Ti5O12, which leads
to the deterioration of electrochemical performance.
Fig. 8 shows the initial charge/discharge curves of Li4
xMgx-
Ti5O12 (x ¼ 0.00, 0.05, 0.10, 0.20) electrodes at 2 C rate. From Fig. 8
we can clearly see that, the voltage difference between charging
and discharging platform of x ¼ 0.00 and x ¼ 0.20 was obvious
232 Q. Cheng et al. / Journal of Alloys and Compounds 722 (2017) 229e234

Fig. 5. EDX-mapping of magnesium (a), oxygen (b), titanium (c).

Fig. 6. CV curves of Li4
xMgxTi5O12(x ¼ 0.00, 0.50, 0.10, 0.20).

clear, which indicates that the polarization of the battery is severe
at high charge/discharge rate [20,21]. However, x ¼ 0.10 revealed an
excellent rate capability. The initial discharge specific capacity of
x ¼ 0.10 was as high as 122.5 mA h/g, and the capacity was still
119.3 mA h/g after 100 cycles, with the capacity loss of 2.61%
(Fig. 9a). The initial discharge specific capacity of x ¼ 0.00 was
100.7 mA h/g. After 100 cycles, the specific capacity was 85.9 mA h/
g, with the capacity loss of 14.70%. The initial discharge specific
capacity of x ¼ 0.05 was 110.4 mA h/g, with the capacity loss of
7.61% after 100 cycles, and the capacity attenuation was 102 mA h/g.
The initial discharge specific capacity of x ¼ 0.20 was only
82.1 mA h/g, and the specific capacity was 58.5 mA h/g after 100
cycles, and the capacity degradation was as high as 28.75%.
At 5 C, after 100 cycles, sample (x ¼ 0.10) has the best
Fig. 7. The curves of Li4
xMgxTi5O12(x ¼ 0.00, 0.05, 0.10, 0.20) at different current
rates.
electrochemical performance (Fig. 9b), with the capacity of
89 mA h/g, and 7% of the capacity attenuation. While x ¼ 0.00,
x ¼ 0.05, x ¼ 0.20, the specific capacity attenuation was 19.09%,
8.33% and 29.64%, respectively. It shows that the cyclic performance
of LTO could be improved when x ¼ 0.10.
Electrochemical impedance spectroscopy (EIS) may be consid-
ered as one of the most sensitive tools for studying the changes in
the electrode behavior due to surface modification [22]. To
demonstrate the effect of Mg2þ doping on the electronic conduc-
tivity properties of Li4Ti5
xMgxO12 (x ¼ 0.05, 0.10, 0.15, 0.20), the
EIS measurements were carried out after the cells were charged/
discharged after 5 cycles. The corresponding Nyquist plots of the
 Q. Cheng et al. / Journal of Alloys and Compounds 722 (2017) 229e234 233

Fig. 10. EIS of Li4
xMgxTi5O12(x ¼ 0.00, 0.05, 0.10, 0.20).

Fig. 8. The initial discharge/charge curves of Li4
xMgxTi5O12 electrodes at 2 C

(x ¼ 0.00, 0.05, 0.10, 0.20). spectra were showed in Fig. 10. All the EIS curves are composed of a
depressed semicircle at the high to intermediate frequency range
and there is a straight line at lowest frequency region. The high
frequency semicircle is related to the charge transfer resistance at
the active material interface, while the sloping line at the low fre-
quency indicates the Warburg impedance caused by a semi-infinite
diffusion of Liþ ion in the electrode [23,24]. In the same experi-
mental conditions, with the increasement of Mg2þ doping content,
the charge transfer impedance of Li4Ti5
xMgxO12 decreases first
and then increases. The pure LTO was 300 U, but for the ratio
x ¼ 0.10, the resistance was 156 U. These demonstrate that the
sample of x ¼ 0.10 has the highest electronic conductivity and ex-
hibits the best electrochemical performance. Therefore, the Mg2þ
doping of x ¼ 0.10 is the appropriate amount to get better high rate
performance.

4. Conclusions

Anode materials Li4Ti5
xMgxO12 (x ¼ 0.00, 0.05, 0.10, 0.20) for

lithium-ion batteries were prepared by a simple solid-state
method. The doped Mg2þ entered the lattice structure of LTO and.
The appropriate amount of Mg2þ doping increases the electronic
conductivity of Li4Ti5O12 and enhances the cycle stability. Cyclic
voltammetry and AC impedance experiments show that the
appropriate amount of Mg2þ can reduce the polarization of
Li4Ti5O12 and improve the electronic conductivity of Li4Ti5O12. The
Mg2þ doping of x ¼ 0.10 is the appropriate amount to get excellent
high rate performance. However, the excessive doping of Mg2þ will
cause the Li4Ti5O12 lattice distortion, which will make the electro-
chemical properties of the material worse.

Acknowledgement

This project was supported by the 4th Yellow Crane Talent

Programme of Wuhan City (08010004), Scientific Research Initial
funding for the advanced talent of Janghan University (08010001,
06750001), Basic Research Project of Wuhan City
(2015011701011593), Hubei Province Innovative Young Research
Team in Universities (T201318), Hubei Province the Featured Su-
perior Disciplinary Group of Optoelectronic Chemical Materials and
Devices (10-43001013), and Open fund from Institute of Wuhan
Fig. 9. The cycling performance of the Li4
xMgxTi5O12(x ¼ 0.10) at 2 C (a) and 5 C (b). Studies (IWHS2016348).
234 Q. Cheng et al. / Journal of Alloys and Compounds 722 (2017) 229e234

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