Article

Sol-Gel Synthesis of Silicon-Doped Lithium

Manganese Oxide with Enhanced Reversible
Capacity and Cycling Stability
Hongyuan Zhao 1,2,*, Dongdong Li 2, Yashuang Wang 2, Fang Li 2, Guifang Wang 3,*,
Tingting Wu 1,2, Zhankui Wang 1, Yongfeng Li 1 and Jianxiu Su 1,*
1 School of Mechanical & Electrical Engineering, Henan Institute of Science and Technology, Xinxiang
453003, China; [email protected] (T.W.); [email protected] (Z.W.); [email protected]
(Y.L.)
2 Research Branch of Advanced Materials & Green Energy, Henan Institute of Science and Technology,

Xinxiang 453003, China; [email protected] (D.L.); [email protected] (Y.W.);

[email protected] (F.L.)
3 School of Resources, Environment and Materials, Guangxi University, Nanning 530004, China

* Correspondence: [email protected] (H.Z.); [email protected] (G.W.); [email protected] (J.S.);

Tel.: +86-182-3613-1721 (H.Z.)

Received: 12 July 2018; Accepted: 14 August 2018; Published: 16 August 2018

Abstract: A series of silicon-doped lithium manganese oxides were obtained via a sol-gel process.
XRD characterization results indicate that the silicon-doped samples retain the spinel structure of
LiMn2O4. Electrochemical tests show that introducing silicon ions into the spinel structure can have
a great effect on reversible capacity and cycling stability. When cycled at 0.5 C, the optimal
Si-doped LiMn2O4 can exhibit a pretty high initial capacity of 140.8 mAh g−1 with excellent retention
of 91.1% after 100 cycles, which is higher than that of the LiMn 2O4, LiMn1.975Si0.025O4, and
LiMn1.925Si0.075O4 samples. Moreover, the optimal Si-doped LiMn2O4 can exhibit 88.3 mAh g−1 with
satisfactory cycling performance at 10 C. These satisfactory results are mainly contributed by the
more regular and increased MnO6 octahedra and even size distribution in the silicon-doped
samples obtained by sol-gel technology.

Keywords: lithium-ion batteries; LiMn2O4; sol-gel method; Si-doping; electrochemical properties

1. Introduction
As green energy, the application of lithium-ion batteries has been extended to various fields in
our life [1–3]. At present, an increasing number of countries are publishing timetables and road
maps for forbidding the sale of traditional fuel vehicles. Against this backdrop, the research and
development of lithium-ion batteries is receiving more and more attention at home and abroad. It is
generally known that the cathode materials greatly influence the electrochemical performance of
lithium-ion batteries. Among appropriate cathode materials, LiMn2O4 possesses the distinct
advantages of low price, mature production technology and non-pollution characteristic, and is
conducive to sustainable development and large-scale application [4,5]. However, it is a great pity
that the poor cycling life cannot satisfy the needs of commercial application of LiMn 2O4. This
unwelcome fact is related to Jahn-Teller distortion, manganese dissolution and non-uniform
particle-size distribution [6–8].
Until now, a large number of optimization strategies have been developed to enhance the
electrochemical performance of LiMn2O4 [7,9–14]. According to the reported works [7,15], the surface
coating treatment can improve the cycling performance to some degree by inhibiting the dissolution

Materials 2018, 11, 1455; doi:10.3390/ma11081455 www.mdpi.com/journal/materials

Materials 2018, 11, 1455 2 of 11

of manganese in the electrolyte. Unfortunately, this strategy cannot fundamentally reduce the
negative impacts of the Jahn-Teller distortion effect, and also decreases the discharge capacity [12].
These facts indicate that surface modification is not a top-priority optimization method to enhance
the comprehensive performance of LiMn2O4. Therefore, lots of researchers choose to use the doping
strategy to avoid the shortcoming of the surface coating treatment [11,16,17]. Yu et al. [17] prepared
Li1+xMn2−xO4 samples by a solid-state sintering method. The obtained Li 1.06Mn1.94O4 sample presents
better cycling performance because the introduction of lithium ions can weaken the ordering of
lithium ions and enhance the structure stability. Xu et al. [18] reported the synthesis of LiZnxMn2−xO4
by a solution combustion method. The research results showed that Zn-doping can enhance the
cycling performance by reducing the negative impacts of the Jahn-Teller distortion effect.
Furthermore, the LiAlxMn2−xO4 samples synthesized by solution combustion technique present
better cycling life, which benefits from the effective inhibition of the Jahn-Teller distortion by
Al-doping [19]. These analyses indicate that introducing other cations can actually enhance the
cycling life of LiMn2O4. It should be noted, however, that introducing some monovalent cations,
bivalent cations or trivalent cations can produce certain negative effects on reversible capacity
because of the decrease of Mn3+ ions, which has previously been confirmed [11,20–22]. Based on all
of the above studies, the introduction of some tetravalent cations has been proposed to effectively
enhance the electrochemical performance of LiMn2O4 because this modification strategy can avoid
the decrease of Mn3+ ions [23,24].
Herein, we have successfully obtained a series of silicon-doped lithium manganese oxides
(LiMn2−xSixO4, x ≤ 0.10) by sol-gel technology. The effect of silicon doping content on the structures,
morphologies and electrochemical properties of the LiMn2−xSixO4 samples obtained by sol-gel
technology is discussed. The results indicate that the optimal silicon-doped sample prepared by
sol-gel technology shows pretty high reversible capacity and outstanding cycling life.

2. Materials and Methods

The silicon-doped lithium manganese oxides (LiMn2−xSixO4, x ≤ 0.10) were obtained via a sol-gel
process with tetraethoxysilane (TEOS, Sinopharm Chemical Reagent Co., Ltd., Shanghai, China) as
the dopant. Firstly, stoichiometric lithium hydroxide (0.8812 g) and citric acid (4.4129 g) were
dissolved in deionized water (20 mL). Under vigorous stirring, the manganese acetate solution (1.5
M) and mixed solution of TEOS (0.2083 g) and ethanol solution (3.0 mL) were added dropwise into
the above-mentioned solution at 50 °C. Then, a certain amount of NH 3·H2O (Sinopharm Chemical
Reagent Co., Ltd., Shanghai, China) was added dropwise into the mixed solution to adjust the pH
value to 7–8, and the temperature was adjusted to 70 °C. After continuous stirring for a few hours, a
reddish-brown sol was formed, which was then dried at 110 °C. The obtained dried gel was sintered
at 450 °C for 4 h and then further sintered at 750 °C for 18 h at a heating and cooling speed of 5
°C·min−1. To investigate the influence of the Si-doping, an undoped LiMn2O4 spinel was prepared
under the same conditions.
The crystal structures of the obtained silicon-doped LiMn2O4 samples were studied by X-ray
diffraction technique (XRD, Bruker DX-1000, Karlsruhe, Germany) with Cu K radiation ( = 0.15406
nm). Both transmission electron microscopy (TEM, JEOL JEM-3010, Tokyo, Japan) and scanning
electron microscopy (SEM, JEOL JSM-6360LV, Tokyo, Japan) analytical techniques were used to
study the surface morphologies and microstructures.
The active electrode consisted of the obtained silicon-doped LiMn2O4 samples, conductive
acetylene black and polyvinylidene fluoride (Weight Ratio = 85:10:5). The anode material and
diaphragm were lithium foil and Celgard 2400 polymer (Charlotte, NA, USA), respectively. The
mixture of 1 M LiPF6, ethyl methyl carbonate (EMC), ethylene carbonate (EC) and dimethyl
carbonate (DMC) was used as electrolyte (EMC: EC: DMC = 1:1:1) (Guangzhou Tinci Materials
Technology Co., Ltd., Guagnzhou, China). The electrochemical measurement was executed on
NEWARE battery testing system. The cyclic voltammogram results and electrochemical impedance
spectroscopy (EIS) were tested by CS-350 electrochemical workstation (Wuhan Corrtest Instruments
Crop., Ltd., Wuhan, China).
Materials 2018, 11, 1455 3 of 11

3. Results and Discussion

To investigate the influence of Si-doping content on the crystalline phase of LiMn2O4, XRD was
performed on the obtained samples. As shown in Figure 1, the characteristic diffraction peaks of all
the LiMn2−xSixO4 samples obtained by sol-gel technology agree with that of LiMn2O4 (JCPDS No.
35-0782), suggesting the silicon-doped lithium manganese oxides obtained by sol-gel technology
possess the cubic spinel structure, with lithium and manganese ions located at tetrahedral sites (8a)
and octahedral sites (16d), respectively [25]. In addition, the (220) characteristic diffraction peak will
be observed if the tetrahedral sites are occupied by other cations [26]. However, note that the (220)
peak does not appear in the XRD patterns of the silicon-doped LiMn2O4 samples, indicating the
substitution of silicon ions for manganese ions.

Figure 1. XRD patterns of the LiSixMn2−xO4 (x = 0, 0.025, 0.05, 0.075 and 0.10) samples.

Table 1. Crystal parameters of the LiSixMn2−xO4 (x = 0, 0.025, 0.05, 0.075 and 0.10) samples.

Sample Space a (nm) Volume (nm3) I311/I400 FWHM400

LiMn2O4 Fd-3m 0.82325 0.55795 0.8992 0.291
LiSi0.025Mn1.975O4 Fd-3m 0.82328 0.55801 0.9274 0.278
LiSi0.05Mn1.95O4 Fd-3m 0.82335 0.55815 0.9645 0.243
LiSi0.075Mn1.925O4 Fd-3m 0.82344 0.55834 0.9587 0.258
LiSi0.10Mn1.90O4 Fd-3m 0.82360 0.55866 0.9453 0.265

Table 1 presents the relevant parameters of the LiMn2−xSixO4 samples obtained by sol-gel
technology. It is clear from the data that all the LiMn2−xSixO4 samples belong to Fd-3m space group.
As the silicon doping content increases, the lattice parameter of these samples gradually increases.
According to the reported results [24], the silicon-doped spinel presents longer Mn−O bond length
and larger MnO6 octahedra. Moreover, the O−Mn−O angle in the Si-doped spinel presents values
closer to 90. These results suggest that introducing some silicon ions leads to the more regular and
increased MnO6 octahedra, which could explain the increase of lattice parameter and cell volume. In
addition, Si-doping showed a great influence on the (400) FWHM value and the (311)/(400) intensity
ratio. Among all the silicon-doped spinels, the LiMn1.95Si0.05O4 sample shows a smaller (400) FWHM
value and (311)/(400) intensity ratio than the other samples, which is consistent with the results of
previous research [27], suggesting higher crystallinity and longer cycling life.
The SEM images of the LiMn2−xSixO4 samples are shown in Figure 2. The undoped LiMn2O4
particles shown in Figure 2a present an uneven size distribution. The corresponding range of
particle size is from 0.1 to 1.6 μm. For the Si-doped LiMn2O4, the introduction of some silicon ions
can optimize the mean diameter and size distribution. When the silicon doping content increases,
the mean diameter of the LiMn2−xSixO4 (0.025 ≤ x ≤ 0.10) has a decreasing tendency, which may be
interpreted as the nucleation rate of silicon-doped samples exceeding the growth of particles with
Materials 2018, 11, 1455 4 of 11

the silicon doping [5,29]. In particular, the LiMn1.95Si0.05O4 particles shown in Figure 2c present the
most uniform size distribution, which is conducive to the enhancement of cycling life [28,29]. The
above-mentioned results suggest that introducing some silicon ions can effectively improve the
crystallinity and optimize the size distribution. Figure 3a,b shows the TEM and HRTEM images of
the representative LiMn1.95Si0.05O4 sample. It can be observed that the growth of sample particles
matches the (111) direction, and the lattice fringes of 0.478 nm correspond to the spinel lattice
structure [30].

Figure 2. SEM images of the LiSixMn2−xO4 samples: (a) x = 0, (b) x = 0.025, (c) x = 0.05, (d) x = 0.075, (e)
x = 0.10.

Figure 3. (a) TEM image and (b) HRTEM image of the LiSi0.05Mn1.95O4 sample.
Materials 2018, 11, 1455 5 of 11

Figure 4. XPS spectra of Li1s (a), Si2p (b), Mn2p (c) and O1s (d) in the LiSi0.05Mn1.95O4 sample.

The XPS spectra of Li1s, Si2p, Mn2p and O1s in the LiMn1.95Si0.05O4 sample are shown in Figure
4. According to these results, we can obtain information regarding the chemical and electronic state.
As shown in Figure 4a,c–d, the oxidation states of Li1s, Mn2p and O1s can be inferred from the
binding energy peaks, which are consistent with the existing results [31]. it is important to note that
the binding energies of Mn2p3/2 correspond to the Mn3+ ions (641.7 eV) and Mn4+ ions (643.1 eV),
respectively [32]. However, the Mn2p3/2 binding energy shown in Figure 4c is at 642.6 eV, suggesting
the mixture situation of Mn3+ and Mn4+ in the silicon-doped sample obtained by sol-gel technology.
Figure 4b presents the XPS spectra of Si2p. We can deduce that the corresponding oxidation state is
at 102.1 eV, which is in good agreement with the reported results [24].
Materials 2018, 11, 1455 6 of 11

Figure 5. (a) Initial charge-discharge curves and (b) Cycling performance of the LiSixMn2−xO4 (x = 0,
0.025, 0.05, 0.075 and 0.10) samples; (c) Comparison plots of the initial discharge capacities and
capacity retentions; (d) Long Cycling performance of the LiSixMn2−xO4 (x = 0, 0.025, 0.05, 0.075)
samples.

Figure 5a presents the first discharge curves of the LiMn2−xSixO4 (x = 0, 0.025, 0.05, 0.075 and
0.10) samples. All these silicon-doped samples present characteristic discharge curves, showing two
distinct voltage platforms around 4.10–4.15 V and 3.95–4.00 V, suggesting that introducing silicon
ions did not change the electrochemical redox reaction mechanism, and that all these Si-doped
LiMn2O4 sample processes comprise two extraction/insertion processes of lithium ions [33]. Figure
5b presents the cycling life of the LiMn2−xSixO4 (x = 0, 0.025, 0.05, 0.075 and 0.10) samples. The
reversible capacity and cycling life of the LiMn2−xSixO4 (x = 0, 0.025, 0.05) samples were remarkably
enhanced as the silicon doping content increased, due to the more regular and increased MnO 6
octahedra, which is conducive to the lithium ion diffusion in the electrochemical redox process [24].
However, it should be noted that the introduction of more silicon ions has great negative impact on
the reversible capacities of the LiMn2−xSixO4 (x = 0.075, 0.10) samples despite the improvement of
cycling life (Figure 5c). These unsatisfying results are principally because introducing more silicon
ions can cause a reduction in the tetravalent manganese ions, which is unfavorable to
Mn(III)−Mn(IV) interconversion. When the silicon doping content is 0.075 and 0.10, the adverse
effect exceeds the positive influence from the more regular and increased MnO 6 octahedra.
Therefore, the electrochemical performance the LiMn2−xSixO4 (x = 0.075, 0.10) samples will deteriorate
to some extent.
Materials 2018, 11, 1455 7 of 11

Figure 6. (a) Rate performance of the LiSixMn2−xO4 (x = 0, 0.025, 0.05, 0.075) samples; (b) Cycling
performance of the LiSixMn2−xO4 (x = 0, 0.025, 0.05, 0.075) samples at the higher discharge rate of 10 C;
Representative charge-discharge curves of the LiMn2O4 (c) and LiSi0.05Mn1.95O4 (d) samples at varying
rates of 0.2–5.0 C.

Figure 5d presents the long cycling life of the LiMn2−xSixO4 (x = 0, 0.025, 0.05 and 0.075) samples.
For the LiMn1.95Si0.05O4 sample, the reversible capacity peaked at 140.8 mAh g−1, which is higher than
that of the LiMn2−xSixO4 (x = 0, 0.025 and 0.075) samples. Even more importantly, the LiMn1.95Si0.05O4
sample exhibited 128.3 mAh g−1 after 100 cycles, with an outstanding retention of 91.1%.
Unfortunately, the LiMn2−xSixO4 (x = 0, 0.025 and 0.075) samples showed a lower capacity with worse
cycling life. In particular, the undoped spinel only delivered 132.7 mAh g−1 with low retention of
62.5% after 100 cycles. These analyses indicate that the introduction of silicon ions dramatically
enhances the electrochemical performance of LiMn2O4.
Figure 6a shows the rate performance of the LiMn2−xSixO4 (x = 0, 0.025, 0.05 and 0.075) samples.
For all these samples, the increased rate has a great negative impact on the reversible capacity
because the high rate seriously interferes with the diffusion process of lithium ions [26]. Among
these samples, the LiMn1.95Si0.05O4 sample showed relatively good rate capability with that of the
LiMn2−xSixO4 (x = 0, 0.025 and 0.075) samples at a high rate. When cycled at 0.2 C, the capacities of the
LiMn2O4, LiMn1.975Si0.025O4, LiMn1.95Si0.05O4 and LiMn1.925Si0.075O4 samples reached 133.4, 135.9, 139.2
and 142.5 mAh·g−1, respectively. However, it is important to note that the discharge capacities of
these Si-doped samples show more and more obvious difference at 5.0 C. The LiMn 1.95Si0.05O4 sample
could show 102.1 mAh·g−1, while the LiMn2O4, LiMn1.975Si0.025O4 and LiMn1.925Si0.075O4 samples showed
lower discharge capacities of 62.8, 72.8 and 87.7 mAh·g−1. The above discussion indicates that the
optimal Si-doping amount can produce the best improvement effect on the electrochemical
performance on the premise that all the silicon-doped samples involved a small amount of Si 4+ ions.
To further explore the rate performance at high rates, the LiMn2−xSixO4 (x = 0, 0.025, 0.05 and
0.075) samples were tested at 10 C, and the corresponding test results are presented in Figure 6b. For
Materials 2018, 11, 1455 8 of 11

the LiSi0.05Mn1.95O4 sample, the reversible capacity of the first cycle could exhibit 88.3 mAh·g−1, which
is much higher than that of the LiMn2O4, LiMn1.975Si0.025O4 and LiMn1.925Si0.075O4 samples. Moreover,
the LiMn1.95Si0.05O4 sample showed a satisfactory reversible capacity of 80.4 mAh·g−1 after 30 cycles
with an outstanding retention of 91.2%. For the LiMn2−xSixO4 (x = 0, 0.025 and 0.075) samples, a lower
reversible capacity with worse cycling stability was presented. The above results further confirmed
that the best improvement effect was obtained by introducing an optimal amount of Si4+ ions.
Figure 6c,d present the representative discharge curves of the undoped LiMn2O4 and the
LiMn1.95Si0.05O4 samples at varying rates. As shown here, there are two obvious voltage platforms at
0.2 C and 0.5 C, suggesting the diffusion process of lithium ions [33]. When the rate was further
increased, these two potential plateaus gradually show ambiguous boundaries and shift toward
lower voltage as the discharge rate increases. This result has a lot to do with the ohmic drop and the
polarization effect [9]. Compared with the LiMn1.95Si0.05O4 sample, the undoped LiMn2O4 sample
showed a lower platform at high rate and a more obvious reduction in capacity. The above analysis
indicates that the introduction of some silicon ions can have a positive effect on high rate
performance.

Figure 7. Cyclic voltammogram curves of the LiMn2O4 (a) and LiSi0.05Mn1.95O4 (b) samples at a scan
rate of 0.15 mV s−1; Nyquist plots of the LiMn2O4 (c) and LiSi0.05Mn1.95O4 (d) samples before cycling
and after 100 cycles.

Table 2. Fitting values of the charge transfer resistance (R2) calculated from EIS.

R2 (Ω·cm2) before R2 (Ω·cm2) After 100 Percentage of

Sample
Cycles Cycles Increase
LiMn2O4 92.3 302.7 228.0%
LiSi0.05Mn1.95O4 61.5 90.6 47.3%

Figure 7a,b show the cyclic voltammogram results of the undoped LiMn 2O4 and the
LiMn1.95Si0.05O4 samples. As shown in Figure 7a, the undoped LiMn2O4 possesses two pairs of redox
Materials 2018, 11, 1455 9 of 11

peaks, which correspond to the relevant diffusion process of lithium ions [34]. It is important to note
that the redox peak current decreased significantly after 100 cycles, suggesting that the undoped
LiMn2O4 sample did not show outstanding cycling performance [35]. Figure 7b presents the results
of the LiMn1.95Si0.05O4 sample. We can see that there are few significant changes in the peak currents.
These results suggest that the introduction of some silicon ions plays an effective role in enhancing
lithium ion diffusion.
Figure 7c and d show the Nyquist plots of the undoped LiMn2O4 and the LiMn1.95Si0.05O4
samples. According to the reported results [9,19], the charge transfer resistance (R2) corresponding to
the high-frequency semicircle has much to do with cycling life. Therefore, the influence of
introducing some silicon ions on the cycling life was studied by a thorough analysis of R2 values.
Table 1 lists the relevant fitting values of R2. For the Si-doped spinel, the original R2 value only
reached 61.5 Ω cm2 and increased to 90.6 Ω cm2 with a low growth rate of 47.3% after 100 cycles.
Compared with the Si-doped spinel, the undoped spinel presents a higher original R2 value (92.3
Ω·cm2). After 100 cycles, this value could reach up to 302.7 Ω·cm2 with a very high growth rate of
228.0%. These analyses indicate that introducing some silicon ions can help to decrease the R 2 value,
which can promote lithium ion diffusion [18].

4. Conclusions
Silicon-doped lithium manganese oxides were obtained via a sol-gel process. As the optimal
Si-doped spinel, the LiSi0.05Mn1.95O4 sample possessed a regular surface morphology and an even size
distribution. More importantly, it showed much better electrochemical properties than those of the
other Si-doped LiMn2O4 samples with a small amount of Si4+ ions. When cycled at 0.2 C and 0.5 C,
the LiMn1.95Si0.05O4 sample exhibited 142.5 and 140.8 mAh·g−1, respectively, which are higher values
than those of the LiMn2O4, LiMn1.975Si0.025O4 and LiMn1.925Si0.075O4 samples. After 100 cycles, the
LiMn1.95Si0.05O4 sample could exhibit 128.3 mAh·g−1 with an outstanding retention of 91.1% at 0.5 C.
When cycled at 10 C, the initial discharge capacity of the optimal Si-doped LiMn2O4 sample could
exhibit 88.3 mAh·g−1. All of these results suggest that the optimal Si-doping amount can produce the
best improvement effect on the electrochemical performance on the premise that all the
silicon-doped spinels involved a small amount of Si 4+ ions.
Author Contributions: H.Z., G.W. and J.S. conceived and designed the experiments; H.Z., D.L. and Y.W.
performed the experiments; all authors analyzed the data; H.Z. wrote the paper; all authors discussed the
results and commented on the paper.

Funding: This research was funded by the Landmark Innovation Project of Henan Institute of Science and
Technology (No. 203010916004), High-level Talents Introduction Project of Henan Institute of Science and
Technology (No. 203010617010 and No. 203010617011) and Key Research Project of Education Department of
Henan Province (No. 19A150023).

Conflicts of Interest: The authors declare no conflict of interest.

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