Solid State Ionics 344 (2020) 115132

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Solid State Ionics

journal homepage: www.elsevier.com/locate/ssi

Li4Ti5O12-TiO2/C hollow microspheres derived from nanoporous biomass T

carbon as anode materials for lithium ion batteries
⁎
Wenhan Zhanga,b, Jinjin Aia, Yike Leia, Yong Lib, Chunyan Laia, , Jingying Xieb
a
Shanghai Key Laboratory of Materials Protection and Advanced Materials in Electric Power, Shanghai University of Electric Power, Shanghai 200090, China
b
State Key Laboratory of Space Power-Sources Technology, Shanghai Institute of Space Power Sources, Shanghai 200245, China

A R T I C LE I N FO A B S T R A C T

Keywords: A flower-like Li4Ti5O12-TiO2/C hollow microsphere derived from biomass carbon is successfully fabricated and
Li4Ti5O12-TiO2 used as anode for lithium ion battery. The results show that the biomass carbons derived from mulberry leaves
Microsphere are uniformly compounded on the Li4Ti5O12-TiO2 microspheres. The Li4Ti5O12-TiO2/C1 microsphere sample
Biomass carbon shows perfect electrochemical performance due to its smaller grain size and larger specific surface area, it
Lithium ion battery
displays a discharge capacity of 174.3 mAh g−1 at 1 C in the first cycle and still maintains above 90% after
1000 cycles, even the current is increased to 40 C, the discharge capacity can still up to 125.8 mAh g−1.
Excellent electrochemical performance of Li4Ti5O12-TiO2/C can be attributed to the dual action of biomass
carbon and produced Ti3+ which enhances the conductivity of the material, and the biomass carbon also pro-
vides a convenient and efficient channel for lithium ion transport.

1. Introduction polypyrrole [17], and polythiophene [18] are good choices for carbon
precursors. In addition, some one-dimensional and two-dimensional
As a new chemical energy storage device, lithium ion battery has carbon materials with unique structure are also used in combination
become the most important and advanced battery due to its long cycle with lithium titanate, such as grapheme [19], carbon fibers [20] and
life, high energy density and no memory effect [1–3]. At present, carbon nanotubes [21].
carbon materials are the most common used commercial anode mate- Recent years, researchers have reported and proved that biomass
rials for lithium-ion batteries. However, because of the phenomenon of carbon also can be used in lithium-ion batteries. V. Selvamani [22] used
“lithium precipitation” and the safety problems caused by volume ex- fish scales as nitrogen-doped biomass carbon for lithium ion battery
pansion during charging and discharging of carbon materials, the de- anode materials. The electrode has an extra-large specific surface area
velopment of lithium-ion batteries urgently needs some new anode (1980 m2 g−1) and shows steady state reversible capacities of 480 mAh
materials that are safe, reliable and long-lived to replace the carbon g−1 at a current density of 75 mA g−1. Sun [23] used grapefruit peels as
anode [4–7]. biomass carbon for lithium ion battery anode materials and this anode
Lithium titanate (Li4Ti5O12), a kind of spinel crystal with Fd3m material can provide a capacity of 452 mAh g−1 at a current density of
space group and cubic symmetry, is such a promising anode material 90 mA g−1. Xia [24] used butterfly wings as template to synthesize
for its notable “no volume change” characteristic. During charging and LTO-TO2 materials with periodic 3-dimensional nanostructures and this
discharging, the volume of unit-cell changes only 0.2%. What's more, material exhibits excellent performance at high rates. Yao [25] used
lithium titanate has a relatively high potential (1.55 V vs Li/Li+) which crab shells to prepare biotemplate of hollow carbon nanofibers and the
can avoid the generation of lithium dendrite. However, due to the lack product was used to encapsulate sulfur and silicon to form the elec-
of electron of the 3d electron layer in Ti atom, Li4Ti5O12 has very poor trodes for lithium ion battery. The resulting nanostructured electrode
electrical conductivity (10−13 S cm−1) and low lithium diffusion coef- shows a high specific capacity (1230 mAh g−1 sulfur and 3060 mAh
ficient (10−9–10−13 cm2 s−1) which limit its electrochemical perfor- g−1 silicon). In addition, many different types of leaves are also used as
mances at high charge/discharge rate [8–14]. A lot of research work biomass carbon for electrode materials, such as maple leaves, ginkgo
has been done to improve its performance, for example, adding dif- leaves, and green tea leaves. [26–28] All in all, biomass carbon has
ferent high conductive materials into the electrode materials. Polymeric become very popular for electrode materials.
organic compound such as polyaniline [15], polydopamine [16], Mulberry leaves are widely produced from most parts of China.

⁎
Corresponding author.

https://doi.org/10.1016/j.ssi.2019.115132
Received 31 August 2019; Received in revised form 21 October 2019; Accepted 31 October 2019
0167-2738/ © 2019 Elsevier B.V. All rights reserved.
W. Zhang, et al. Solid State Ionics 344 (2020) 115132

Fig. 1. (a) TGA curves of LTO-TO2/C1 and LTO-TO2/C2. (b) XRD patterns of LTO-TO2，LTO-TO2/C1, LTO-TO2/C2 and C. (c) Raman spectra of LTO-TO2，LTO-TO2/
C1 and LTO-TO2/C2. (d) Nitrogen adsorption curve of LTO-TO2，LTO-TO2/C1 and LTO-TO2/C2.

They have been used for sericulture or medicine since ancient times. 2.2. Synthesis of hollow Li4Ti5O12-TiO2 microspheres
Due to their medicinal value and edible value, the annual output of
mulberry leaves in China is huge. As we know, mulberry leaves contain First, 2 ml tetrabutyltitanate (TBT), 1.0288 g LiOH.H2O and 3.5 ml
a large amount of cellulose and cellulose is a kind of good carbon source H2O2 (30%) were added into 70 ml deionized water and stirred for
[26–28]. As an extremely inexpensive and fairly readily available bio- 30 min. Then, the prepared solution was transferred to a 100 ml teflon-
mass carbon source, it is tried to be used as energy storage materials. lined stainless-steel autoclave and reacted at 150 °C for 5 h. After hy-
Herein, we report a work using mulberry leaves as biomass carbon drothermal process, the product was rinsed with deionized water for
precursor and compound with Li4Ti5O12-TiO2. The modified material several times and dried in a vacuum oven at 80 °C for 2 h. Finally, the
presents a discharge capacity of 174.3 mAh g−1 in the first cycle at 1C samples were placed in a tube furnace and heated to 550 °C with a
and maintains above 90% after 1000 cycles. Additionally, the reversible heating rate of 3 °C/min for 5 h under air atmosphere. The final product
specific capacities can still reach 125.8 mAh g−1 at 40 C. This work was named as LTO-TO2.
proves that biomass carbon can be used as a good kind of carbon source
for the modification of electrode materials. 2.3. Synthesis of LTO-TO2/C1 and LTO-TO2/C2

In method I, the precursor was prepared by using one-step hydro-

2. Experiment thermal. First, the MLC was added to 70 ml deionized water and ul-
trasonic treated for 1.5 h. Subsequent steps are similar to the appeal
2.1. Preparation of biomass carbon method of LTO-TO2, and the final sample was named as LTO-TO2/C1.
In method II, the product was obtained by simple mixing and secondary
Mulberry leaves collected from campus were used as biomass pre- calcination. The obtained LTO-TO2 microspheres were dissolved in
cursor in this work. Typically, the obtained mulberry leaves were rinsed deionized water and CTAB (2 mg) was added as surfactant, then the
repeatedly with deionized water to remove impurities on the leaves, MLC was added and stirred for 2 h. The product was rinsed with
then it was ground and added to 500 ml of potassium hydroxide solu- deionized water for several times to remove excess CTAB and then dried
tion (10 g KOH) and stirred for 1 h. After stirring, the obtained mate- in a vacuum oven at 80 °C for 12 h. Finally, the sample was placed in a
rials were dried in a convection oven at 80 °C for 12 h. After that, the tube furnace for 550 °C for 5 h with a heating rate of 3 °C/min under Ar
leaves were pyrolyzed in tube furnace at 800 °C for 2 h with a heating atmosphere, and it was named as LTO-TO2/C2. The content percentages
rate of 3 °C/min under nitrogen atmosphere. Finally, the obtained of MLC powders are 3 wt% in both of two methods.
materials were soaked in 30% nitric acid and stirred for 3 h，then
washed several times with deionized water and ethanol. The final
product was named as MLC. 2.4. Materials characterization

The crystal structure of samples was investigated by X-ray

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W. Zhang, et al. Solid State Ionics 344 (2020) 115132

Fig. 2. XPS survey of LTO-TO2/C1 (a) and LTO-TO2/C2(c), XPS spectra of Ti 2p of LTO-TO2/C1 (b) and Ti 2p of LTO-TO2/C2 (d).

Fig. 3. SEM images of LTO-TO2 (a, b), LTO-TO2/C1 (c, d) and LTO-TO2/C2 (e, f).

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W. Zhang, et al. Solid State Ionics 344 (2020) 115132

Fig. 4. SEM images of LTO-TO2/C1 (a) and LTO-TO2/C2 (e), Elemental mapping of LTO-TO2/C1 (b–d) and LTO-TO2/C2 (f–h).

Fig. 5. Schematic illustration of the formation of LTO-TO2/C1.

spectroscopy (XPS Thermo K-Alpha XPS spectrometer). The mor-

phology of the samples was obtained by scanning electron microscope
(SEM JSM7610F) and transmission electron microscope (TEM PHILIPS,
FEGCM200). Energy-dispersive X-ray spectroscopy (EDS) mapping was
used to investigate the distribution of element.

2.5. Electrochemical test

The anode electrodes were formed by a mixture of 80% active

material, 10% acetylene black and 10% polyvinylidene fluoride
(PVDF). At first, the mixture was dispersed in N-methyl-2-pyrrolidone
to form homogeneous slurry. Then, the formed slurry was coated on
copper foil and dried in oven at 80 °C for 10 h. After that, the electrodes
were pressed into slice (diameter = 14 mm, the mass of active material
on each electrode is approximately 1.3–1.6 mg). The Celgard 2400
Fig. 6. HRTEM image of LTO-TO2/C1. polyethylene was used as separators and Li metal as the counter elec-
trode to assemble the CR2016-type coin cells in glove box. 1 M LiPF6
dissolved in DMC、EC and EMC (volume ratio of 1:1:1) was used as the
diffraction (XRD Rigaku D/max 2500 using Cu Kα radiation, 2θ ranges
electrolyte. Charge-discharge cycling was performed at different rates
from 10° to 80°). Thermogravimetric analysis (TGA) was carried out
(1 C = 175 mA g−1) between 1.0 V and 2.5 V at 25 °C with Land
from 30 °C to 600 °C in air (NETZSCH STA 449F3, Germany). Raman
CT2001A tester. The CV (0.1 mV s−1, 1–2.5 V) and EIS (10−2 Hz to
spectroscopy was carried out using Raman spectroscope (HORIBA
105 Hz) test was conducted by CHI660E electrochemical workstation.
Scientific Instruments Division). The specific surface area (SSA) of
samples was analyzed by Brunauer–Emmett–Teller (BET, ASAP2460).
XPS analysis results were obtained from X-ray photoelectron

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W. Zhang, et al. Solid State Ionics 344 (2020) 115132

Fig. 7. Cycle performances of LTO-TO2, LTO-TO2/C1 and LTO-TO2/C2 over 1–2.5 V (versus Li+/Li) at 1C (a), rate performances of LTO-TO2, LTO-TO2/C1 and LTO-
TO2/C2 (b), charge–discharge profiles over the voltage range of 1–2.5 V (versus Li+/Li) at 1C of LTO-TO2 (c) and LTO-TO2/C1 (d).

3. Results and discussion The Raman spectroscopy of LTO-TO2/C1 and LTO-TO2/C2 were
analyzed and shown in Fig. 1c. Two different Raman peaks of carbon
Carbon contents in LTO-TO2/C1 and LTO-TO2/C2 were evaluated can be observed in Fig. 1c, the G band appearing at 1590 cm−1 is re-
by thermogravimetric analysis and the results are shown in Fig. 1a. The lated to the sp2 graphite structure, while the peak of the D band around
mass loss from room temperature to 100 °C can be attributed to the 1340 cm−1 is related to defects in the graphite structure [27]. The ratio
reduction of water in the samples, and LTO-TO2/C2 contains less water of D-band to the G-band peak intensity (ID: IG) of the LTO-TO2/C1 and
because it was obtained by secondary calcination. The mass loss from LTO-TO2/C2 is 1.27 and 1.38 respectively, which means that the gra-
220 °C to 500 °C can be attributed to the reduction of carbon content in phitization degree of LTO-TO2/C1 material obtained by one-step hy-
the sample. It can be seen that the carbon content in LTO-TO2/C1 is drothermal is higher than that of LTO-TO2/C2 material.
about 2.8%, and the carbon content in LTO-TO2/C2 is about 2.2%. The nitrogen adsorption-desorption isotherms of samples were ob-
X-ray diffraction (XRD) patterns of samples are shown in Fig. 1b. All tained by BET test and the results are shown in Fig. 1d. The specific
the strong diffraction peaks of the three samples can be perfectly in- surface area of LTO-TO2 is calculated to be 56.56 m2/g while the LTO-
dexed to spinel Li4Ti5O12 [29,30], the weak peaks at 25° and 55° cor- TO2/C2 and LTO-TO2/C1 is 81.52 m2/g and 108.34 m2/g respectively.
respond to a small amount of TiO2. In addition, a small peak near 21° in There is no doubt that larger specific surface area can provide larger
LTO-TO2/C1 and LTO-TO2/C2 can be considered as carbon peak. When contact area with the electrolyte and leads to high li-ion flux across the
further enlarge the peak at 43°, it can be seen that the modified ma- electrolyte/electrode interface [31–33].
terials' peak has a certain left shift phenomenon relative to the pure XPS analysis was carried out and the results are shown in the Fig. 2.
phase, which may be due to the fact that the carbonization process Fig. 2a and c show the full-spectrum scan results of LTO-TO2/C1 and
further provides a small amount powerful reducing inert gas, and some LTO-TO2/C2 and there are three elements Ti, O and C in both of LTO-
of the Ti4+ was reduced to Ti3+ which has a larger diameter, resulting TO2/C1 and LTO-TO2/C2. To further analyze the valence state of the Ti
in a larger overall lattice constant of the material [12,31]. It was further element, a high-resolution spectrum of Ti 2p was carried out and the
confirmed by the calculation of the cell parameters, the 2θ of the (111) results are shown in Fig. 2b and d. It can be seen that two samples have
planes of LTO-TO2, LTO-TO2/C1, and LTO-TO2/C2 are 18.33°, 18.22°, obvious peak positions at the binding energies of 463.8 eV and 458.1 eV
and 18.02°, respectively. According to the formula 2dsin θ = nλ and which correspond to 2p1/2 and 2p3/2 of Ti4+. In addition, a small
d = a/√h2 + k2 + l2, where d is the interplanar spacing, θ is the dif- shoulder peak corresponding to Ti3+ appeared at a binding energy of
fraction half angle, n is the diffraction order, λ is the wavelength of the 457.2 eV, indicating some Ti4+ in the material was reduced to Ti3+,
copper target, a represents the cell parameter and the calculated values and it further verifies the speculation that the XRD peak was shifted to
of a are 0.42, 0.426 and 0.431, respectively. Increased cell parameters the left. According to previous reports, the presence of Ti3+ can further
can further prove the existence of Ti3+. enhance the conductivity of Li4Ti5O12 [12].

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W. Zhang, et al. Solid State Ionics 344 (2020) 115132

Fig. 8. (a) CV curves of LTO-TO2 and LTO-TO2/C1 for the 1st cycle at a scanning rate of 0.1 mV s−1 between 1.0 and 2.5 V (vs. Li+/Li), (b) Nyquist plots of C, LTO-
TO2, LTO-TO2/C1 and LTO-TO2/C2 electrodes before cycling, (c) high rate performances of LTO-TO2/C1, (d) Long cycle performance of LTO-TO2/C1 at 1 C.

Table 1 with a radius of 500 nm. However, as shown in Fig. 3e the LTO-TO2/C2
Impedance parameters and calculated DLi+ of the samples. sample particles are significantly enlarged with a radius of about
Rs(Ω) Rct(Ω) Σw (Ω cm2·s−1) DLi+ (cm2 s−1)
1.5 μm, this may be due to the fact that the secondary calcination causes
the particle agglomeration to be more serious. To prove the distribution
C 3.64 43.12 and composition of the elements, the EDS mapping of the materials was
LTO-TO2 7.36 81.84 6.58 1.99 × 10−13 also carried out. Fig. 4a and e show the SEM images of selected regions
LTO-TO2/C1 5.17 23.74 3.04 10.14 × 10−13
LTO-TO2/C2 4.37 33.75 4.23 5.23 × 10−13
of LTO-TO2/C1 and LTO-TO2/C2 respectively. Fig. 4b–d and f–h prove
the uniform distribution of C, O and Ti on the surface of the material
which proves the uniform compounding of MLC.
Fig. 3 and Fig. S1 show the representative SEM images of the In order to further clarify the effect of biomass carbon, the sche-
samples. Fig. S1 shows the typical morphology of the MLC and many matic illustration of the formation of LTO-TO2/C1 is given. As shown in
small holes with diameter of 500–800 nm can be observed.，this con- Fig. 5, the LTO-TO2/C1 precursor is formed by a hydrothermal reaction,
firms that the prepared biomass carbon is nanoporous. What's more, it and LTO-TO2/C1 is formed by subsequent calcination. The carboniza-
can be seen from Fig. 3b, d and f that the LTO, LTO-TO2/C1 and LTO- tion process further provides a small amount powerful reducing inert
TO2/C2 are all hollow spheres composed of dense nanosheets, and the gas, and some of the Ti4+ was reduced to Ti3+. More importantly, after
composite of MLC did not change the general morphology of the LTO- calcination, the biomass carbon is compounded on the surface of LTO-
TO2 material. Fig. 3c shows that the LTO-TO2/C1 sample has a particle TO2 microspheres, forming a convenient bridge for lithium ion trans-
radius of about 700 nm which is not much different from the pure phase port and accelerating the transport of lithium ions between the

Table 2
Rate capacities for modified Li4Ti5O12 at various rate from 1 to 40 C (mAh/g).
Materials Methods 1C 2C 5C 10C 20C 40C Ref.

3+
LTO-TO2/C1 Carbon coated Ti Li4Ti5O12-TiO2 174.3 165.8 159.8 153.7 147.8 125.8 This work
LTO-TO/C N doped Carbon coated Li4Ti5O12-TiO2 170 155 150 141 122 – [40]
0.15Co-LTO Co doped Ti 3+
LTO 172 164 155 152 138 – [41]
LTO-TO Li4Ti5O12-TiO2 143 – 120 – – – [42]
LTO-5:5 carbon-coated Li4Ti5O12-TiO2 165 155 147 125 100 – [43]
LTO/TiO2 H2O2-assisted Li4Ti5O12-TiO2 157 142 129 117 102 – [44]
F-LTO F doped Ti3+ LTO 163.4 157.8 148.9 124.8 – – [12]

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W. Zhang, et al. Solid State Ionics 344 (2020) 115132

microspheres. DLi + = R2T 2/2A2n4C2F 4σ 2 (1)

The high resolution TEM is shown in Fig. 6, a large number of lattice
fringes with a pitch of 0.48 nm can be observed which correspond to the ZRs = K + σω−1/2 (2)
(111) plane of the spinel Li4Ti5O12, and a small number of lattice −1 −1
R, T represent gas constant (8.314 J·mol ·K ) and Kelvin tem-
fringes with a pitch of 0.35 nm can also be observed which correspond perature (298.15 K), A, n, represent the area of electrode and electrons
to the (101) plane of anatase TiO2. This proves that the sample is a transfer moles, F represent Faraday constant (9.65 × 104C·mol−1) C
mixed phase of Li4Ti5O12 and TiO2, the results are consistent with the represent the concentration of Li+ and σ is the line slope of ω−1/2 and
XRD patterns well. In addition, some areas without lattice fringes can Z'. The results are shown in Fig. S3 and Table 1, the DLi+ of LTO-TO2 is
be found in the lower right corner of the picture which correspond to 1.99 × 10−13, less than 10.14 × 10−13 of LTO-TO2/C1 and
amorphous carbon, this can further prove the successful compounding 5.23 × 10−13 of LTO-TO2/C2. The improved Li-ion diffusion coefficient
of MLC. can indicate faster electrochemical reaction kinetics [39].
The electrochemical performances of all samples are shown in Fig. 7 To further illustrate the excellent electrochemical performance of
and S2. As shown in Fig. 7a, the LTO-TO2/C1 and LTO-TO2/C2 have LTO-TO2/C1, the higher rates performance and longer cycles perfor-
better cycle performance and higher discharge capacity than that of mance were tested, and the results are shown in Fig. 8c and d. When the
LTO-TO2. After 500 cycles, the discharge capacity of LTO reduced from current was increased to 40 C, the discharge capacity of LTO-TO2/C1
156.2 mAh g−1 to 137.5 mAh g−1, while the discharge capacities of can still up to 125.8 mAh g−1, which is higher than those published
LTO-TO2/C1 and LTO-TO2/C2 reduced from 174.3 mAh g−1 to 159.2 papers (Table 2). Fig. 8d shows the long-cycle performance，after 1000
mAh g−1 and 162.7 mAh g−1 to 147.5 mAh g−1. Excellent performance charge-discharge cycles at 1 C, the discharge capacity of LTO-TO2/C1
can be due to the successful compounding of MLC, it reduces the Li+ can still reach 157.1 mAh/g, and the capacity retention rate is over
diffusion pathway and improves the electron conductivity of LTO-TO2 90%.
[34]. To further demonstrate their advantages for high-rate LIB appli-
cations, the rate performance were tested from 1 to 20 C and the results 4. Conclusions
are shown in Fig. 7b. Obviously, the discharge capacity of LTO-TO2/C1
and LTO-TO2/C2 is higher than that of LTO-TO2 at all current density, In summary, the LTO-TO2/C hollow microspheres derived from
in particular, the discharge capacity of LTO-TO2/C1 is 170.2, 165.9, mulberry leaves were obtained by two different methods. Biomass
159.8, 153.7, 147.8 mAh g−1 at 1, 2, 5, 10 and 20 C respectively, which carbon provides a convenient and efficient channel for lithium ion, and
indicates that the LTO-TO2/C1 electrode has the best electrochemical the composite of biomass carbon increases the specific surface area of
performance. Fig. S2 shows the cycle curve of MLC at 1C. It can be seen the material which provides a large contact area with the electrolyte
that the discharge capacity of the first circle is only 75 mAh g−1, and it and leads to high li-ion flux across the electrolyte/electrode interface.
drops rapidly to 52 mAh g−1 after one cycle. This further proves the What's more, the dual role of biomass carbon and Ti3+ greatly enhances
main role of biomass carbon is improving the conductivity of the ma- the conductivity of the material. The LTO-TO2/C1 has the best perfor-
terial and providing a convenient and efficient channel for lithium ion mance for its larger specific surface area and smaller particle size and
rather than providing additional capacity. the discharge capacity can reach 174.3 mAh g−1 in the first cycle at 1C
Fig. 7c and d show the charge and discharge curves of LTO-TO2 and and the capacity can still maintain above 90% after 1000 cycles, even
LTO-TO2/C1 at 1C. The long platform of about 1.55 V corresponds to the current was increased to 40 C the discharge capacity can still up to
the lithium insertion/delithiation process of Li4Ti5O12. A small platform 125.8 mAh g−1. This work provides a simple and cost-effective method
observed at about 1.75 V corresponds to the delithiation from LixTiO2 for battery materials.
[35], which obviously adds additional capacity at a low current rate.
Meanwhile, compared to LTO-TO2, LTO-TO2/C1 exhibits higher charge Declaration of competing interest
and discharge capacity, which was attributed to the synergistic effects
of the MLC and the LTO-TO2 microsphere [21]. The authors declare that they have no known competing financial
Fig. 8a shows the CV curves of LTO-TO2 and LTO-TO2/C1. The interests or personal relationships that could have appeared to influ-
characteristic peaks around 1.55 V (vs. Li/Li+) corresponding to the ence the work reported in this paper.
process of Li+ insert into and extract from the spinel Li4Ti5O12. A pair
of characteristic peaks can be observed around 1.75 V (vs. Li/Li+), Acknowledgements
corresponding to anatase TiO2. What's more, the potential difference
(△V) of LTO-TO2/C1 is lower than that of LTO-TO2, suggesting that This work was supported by Science and Technology Commission of
LTO-TO2/C1 has higher reversibility. The anode and cathode peaks of Shanghai Municipality (16020500800) and Natural Science Foundation
LTO-TO2/C1 are sharper than that of LTO-TO2 sample, which corre- of China (51402187).
sponds to better electrochemical Li+ insertion/deintercalation kinetics.
Therefore, it is reasonable to believe that the composite of MLC is Appendix A. Supplementary data
beneficial to further improve the electrochemical performance of LTO-
TO2 material. Supplementary data to this article can be found online at https://
Fig. 8b shows the EIS curves of all samples. All Nyquist plots consist doi.org/10.1016/j.ssi.2019.115132.
of a high frequency concave semicircle and a low frequency oblique
line. Specifically, the intercept represents the ohmic resistance, the References
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