Journal of Chemical Sciences

Composite of Li4Ti5O12-SnO2 using Solid State Method for Anode of Lithium Ion
Battery
--Manuscript Draft--

Manuscript Number: JCSC-D-23-00639

Full Title: Composite of Li4Ti5O12-SnO2 using Solid State Method for Anode of Lithium Ion
Battery

Article Type: Regular Article

Keywords: Anode; Composite; Li4Ti5O12; SnO2; Solid-State

Corresponding Author: slamet priyono

Badan Riset dan Inovasi Nasional
KOTA TANGERANG SELATAN, BANTEN INDONESIA

Corresponding Author Secondary

Information:

Corresponding Author's Institution: Badan Riset dan Inovasi Nasional

Corresponding Author's Secondary

Institution:

First Author: SLAMET PRIYONO

First Author Secondary Information:

Order of Authors: SLAMET PRIYONO

DHEVANDA NIKEN ANDIANI

NANDA JULISTIO RAHMADI

SUDARYANTO SUDARYANTO

EDUARDUS BUDI NURSANTO

Order of Authors Secondary Information:

Funding Information: Rumah Program BRIN Dr SLAMET PRIYONO

(X)

Abstract: A composite of Li4Ti5O12-SnO2 for anode material was synthesized using the solid-
state reaction method, with four different SnO2 compositions (0%, 2.5%, 5%, and
10%). The synthesis involved milling and sintering the Li4Ti5O12-SnO2 mixtures at
850°C for 4 hours. The characterizations were carried out using X-ray Diffraction
(XRD), Scanning Electron Microscopy/ Energy Dispersive X-ray (SEM)/EDX),
Electrochemical Impedance Spectroscopy (EIS), Cyclic Voltammetry (CV), and
Charge-Discharge (CD). The XRD analysis identified multiple phases within the
materials, including Lithium Titanate (Li4Ti5O12), rutile (TiO2), and Tin (IV) Oxide
(SnO2). SEM/EDX data reveal that SnO2 content hinders grain growth and decreases
the particle size. The addition of SnO2 2.5% can avoid rutile formation and improve
electrochemical performance. It possesses a high Li4Ti5O12 phase of 97.1%, low ionic
resistance of 194.6 Ω, and a specific capacity of 247 mAh/g. However, the higher
content of SnO2 decreases the crystallinity and ionic diffusion coefficient of
Li4Ti5O12while increasing the resistance. In summary, the study highlights the
successful synthesis of a Li4Ti5O12-SnO2 composite anode material using the solid-
state reaction method, showing the potential of the 2.5% SnO2 composition to improve
electrochemical performance.

Suggested Reviewers: Bambang Priyono

University of Indonesia: Universitas Indonesia
bambpriyono@ui.ac.id
Lecturer on Lithium Ion Battery

Nofrijohn Sofyan
University of Indonesia: Universitas Indonesia

Powered by Editorial Manager® and ProduXion Manager® from Aries Systems Corporation
 nsofyan@ui.ac.id
Lecturer on material

agus Sukarto
national agency for research and Inovation
agussukarto@gmail.com
Senior researcher

Ramlan Purba
Sriwijaya University: Universitas Sriwijaya
ramlan041066@gmail.com
Lecturer

Gerald Ensang Timuda

National Agency for Research and Innovation: Agencia Nacional de Investigacion e
Innovacion
gerald.e.timuda@gmail.com
Senior researcher on photovoltaic device

Powered by Editorial Manager® and ProduXion Manager® from Aries Systems Corporation
Cover Letter

October 25th, 2023

Subject:

Dear Editor of Journal of Chemical Sciences,

Please kindly check the enclosed manuscript for Editor of Journal of Chemical Sciences
“Composite of Li4Ti5O12-SnO2 Using Solid State Method for Anode of Lithium Ion Battery”.
In this manuscript, we present our investigation on the performance of composite of
Li4Ti5O12 (LTO)-SnO2 for lithium battery anode. The pristine LTO was prepared as a control
using titanium oxide and lithium hydroxide via solid-state process, while the SnO2 powders
were added of 1%, 5%, and 10%. The crystal structure, morphology, conductivity, and
electrochemical performance of the samples were examined using X-ray diffraction (XRD),
scanning electron microscopy (SEM), , Electrochemical Impedance Spectroscopy (EIS), and
Cyclic Voltammetry/Charge-discharge (CV/CD), respectively.
We have found that The addition of SnO2 2.5% can avoid rutile formation and improve
electrochemical performance. However, the higher content of SnO2 decreases the crystallinity and
ionic diffusion coefficient of Li4Ti5O12while increasing the resistance. the study highlights the
successful synthesis of a Li4Ti5O12-SnO2 composite anode material using the solid-state reaction
method, showing the potential of the 2.5% SnO2 composition to improve electrochemical
performance
We hope our paper contribute to knowledge and is up to standard for publication in
Journal of Chemical Sciences.

Yours sincerely

Corresponding authors
Dr. Slamet Priyono
e-mail: slam021@brin.go.id
Graphical Abstract

Li2CO
3
TiO2
SnO2
Mixin
g
Planetary Ball Mill
Sintering

The addition of SnO2 to LTO is believed that it can overcome the problem such as low energy density, lower electronic conductivity, and ionic diffusion
coefficient. It can change lattice parameters and cause defects in the atomic arrangement and lead to the increasing of ionic conductivity. SnO2
can also be useful for improving Li+ diffusion and buffering volume expansion/shrinkage during the charge-discharge process. These
enhancements make LTO a promising anode material in high-power and high energy density.
Manuscript Click here to
access/download;Manuscript;JCSC_SlametPriyono.docx

1
2
3 Composite of Li4Ti5O12-SnO2 using Solid State Method for Anode of Lithium Ion
4
5
Battery
6
7
8
SLAMET PRIYONO 1*, NANDA JULISTIO RAHMADI2, EDUARDUS
9
BUDI NURSANTO3, SUDARYANTO1 , and DHEVANDA NIKEN
10 ANDIANI 3
1
11 National Agency for Research and Innovation, Tangerang Selatan 15310,
12 Indonesia
2
13 Department of Chemical Physics, Faculty of Production and Industrial
14 Technology, Sumatra Institute of Technology, Lampung 35365, Indonesia
3
15 Department of Chemical Engineering, Faculty of Industrial Technology,
16 Pertamina University, South Jakarta 12220, Indonesia
17 *For correspondence (slam021@brin.go.id)
18 MS received
19
20
21 Email: xxx Tel.: xxxx Mobile: xxxx
22
23
24 Abstract. A composite of Li4Ti5O12-SnO2 for anode material was synthesized using the
25 solid-state reaction method, with four different SnO2 compositions (0%, 2.5%, 5%, and
26 10%). The synthesis involved milling and sintering the Li4Ti5O12-SnO2 mixtures at 850°C
27 for 4 hours. The characterizations were carried out using X-ray Diffraction (XRD),
28
29
Scanning Electron Microscopy/ Energy Dispersive X-ray (SEM)/EDX), Electrochemical
30 Impedance Spectroscopy (EIS), Cyclic Voltammetry (CV), and Charge-Discharge (CD).
31 The XRD analysis identified multiple phases within the materials, including Lithium
32 Titanate (Li4Ti5O12), rutile (TiO2), and Tin (IV) Oxide (SnO2). SEM/EDX data reveal that
33 SnO2 content hinders grain growth and decreases the particle size. The addition of SnO2
34
35 2.5% can avoid rutile formation and improve electrochemical performance. It possesses a
36 high Li4Ti5O12 phase of 97.1%, low ionic resistance of 194.6 Ω, and a specific capacity of
37 247 mAh/g. However, the higher content of SnO2 decreases the crystallinity and ionic
38 diffusion coefficient of Li4Ti5O12while increasing the resistance. In summary, the study
39
highlights the successful synthesis of a Li4Ti5O12-SnO2 composite anode material using the
40
41 solid-state reaction method, showing the potential of the 2.5% SnO2 composition to improve
42 electrochemical performance.
43
44
45
46 Keywords. Anode; Composite; Li4Ti5O12; SnO2; Solid-State
47
48
49
1. Introduction
50
51 The use of fossil fuels in the long term will deplete the supply of fossil fuel
52
53 sources. One solution is the utilization of batteries to store energy from renewable sources
54 like solar and wind. Batteries are electrochemical cells that convert chemical energy into
55
56 electrical energy in everyday life, for example, electrical vehicles and electronic
57
58 devices.1,2 The preparation of Li-Ion batteries involves several components, namely
59
60 electrodes (anode and cathode), electrolytes, and separators. In lithium-ion batteries, the
61
62 electrolyte is composed of lithium salts in organic solvents, while separators are
63 constructed of porous polymer materials.3 Cathodes are typically made of transition metal
64
65 oxides, and the anode is generally made of carbon based material, like graphite. However,
 graphite has very low working potential which can lead the safety problem such as
1 dentrite lithium and solid electrolyte intherphase (SEI).4,5 To overcome this challenge,
2
3 one material commonly used in anodes is spinel lithium titanium oxide (LTO) or
4
5 L4Ti5O12. This material has "zero strain" property because the Li4Ti5O12 particles do not
6
7 undergo significant changes in lattice parameters during charge-discharge process.6 It has
8
9
high thermal stability, long cycle life,7 high rate capability, good safety, and compatible
10 with both conventional and low temperature electrolytes.8,9 Futhermore, Li4Ti5O12 has a
11
12 stable and high working voltage of 1.55V against Li+/Li. This high voltage prevent the
13
14 formation of Solid-Electrolyte Interphase (SEI) layer and dendrite of lithium-ion.10
15
16 However, Li4Ti5O12 still faces certain-challenges include its lower capacity (175
17
18 mAh/g),11 in contrast with graphite (372 mAh/g),12 as well as its lower energy density,13
19
20 lower electronic conductivity (in the range of 10-8 to 10-13 S/cm),14 and a relatively low
21 lithium ion diffusion coefficient raging from 10-8 to10-13 cm2/s.15 These factors lead this
22
23 material to have limited ability to high-rate conditions during the charge-discharge
24
25 process. One such approach involves enhancing its ionic conductivity and capacity is by
26
27 composited other material such as Li4Ti5O12/SnO2 using solid-state reaction method. It
28
29 can change lattice parameters and cause defects in the atomic arrangement. This, thereby
30
increases ionic conductivity. SnO2 can also useful for improving Li+ diffusion and
31
32 buffering volume expansion/shrinkage during the charge-discharge process. These
33
34 enhancements make Li4Ti5O12 a promising for anode material in high-power and long-
35
36 lasting lithium ion batteries.16
37
38 According to previous research, various concentration of SnO2 (10%, 20%, and
39
40 30%) were added using the sol-gel method. The EIS testing in the study yielded the
41
42 following results of 75 Ω, 66 Ω, and 87 Ω for Li4Ti5O12-SnO2 10%, 20%, and 30%
43 respectively. The optimal concentration was found to be 20% SnO2, as it has the lowest
44
45 resistance, indicating the highest conductivity. The results show that the addition of SnO2
46
47 increases the conductivity of Li4Ti5O12. In term of capacity obtained from the charge-
48
49 discharge results, the Li4Ti5O12-SnO2 10% sample showed a capacity of 151.59 mAh/g,
50
51 Li4Ti5O12-SnO2 20% exhibited a capacity of 169.90 mAh/g, and Li4Ti5O12-SnO2 30%
52 demonstrated a capacity of 133.83 mAh/g. Notably, Li4Ti5O12-SnO2 samples that have
53
54 the highest capacity was found to be the one having 20% SnO2.17 Even though samples
55
56 with a concentration of 20% show the best performance, research for concentrations
57
58 below 10% is still rarely carried out. In this study, we synthesize Li4Ti5O12-SnO2
59
60 composite for low concentration using solid state reaction method to improve the
61 electrochemical performance of Li4Ti5O12. This method is more facile, simple, and non-
62
63 toxic than sol-gel.18
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65
 2. Experimental
1 2.1 Synthesis of Li4Ti5O12
2
3
4
Some raw materials such as Lithium Carbonate (Li2CO3, Sigma Aldrich), Titanium
5 Dioxide (TiO2, Sigma Aldrich), and Tin (IV) Oxide (SnO2, Sigma Aldrich) were carefully
6
7 weighed in stoichiometric proportions using analytical balances. These raw materials were
8
9 mixed and ground manually using mortar and pestle. Subsequently, the samples were
10
11 milled using a planetary ball milling with a material to ball ratio of 1: 5 at a frequency of
12
13
20 Hz for a duration of 2 h. The results were sintered using a furnace at a temperature of
14 850°C for 4 hours in an air atmosphere. After sintering, the samples were processed by
15
16 grinding them with a mortar and pestle to make it smooth. Subsequently, they were filtered
17
18 through a 200-mesh sieve for material characterization (XRD and SEM/EDX) as well as
19
20 for anode preparation.
21
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23 2.2 Electrode Preparation
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25 Electrode manufacturing was done by mixing active material (Li4Ti5O12-SnO2) with
26
27 acetylene black (AB) and PVDF in a ratio of 8: 1: 1 wt.% using DMAC as solvent. The
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29
resulting slurry was coated onto Cu foil with a thickness of 150 μm and then dried in an
30 oven. The electrodes were then cut into circle shapes with a diameter of 16 mm, and their
31
32 weight and thickness were measured. For electrochemical performance testing, the
33
34 electrodes were assembled into CR 2032-type coin cells along with a separator, lithium
35
36 metal, and LiPF6 1M as electrolytes. This assembly was conducted within a glove box
37 filled with argon gas to ensure the inert atmosphere. Electrochemical testing is performed
38
39 by Electrochemical Impedance Spectroscopy (EIS), cyclic Voltammetry (CV), and
40
41 Charge-Discharge (CD).
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 3. Results and Discussion
1
2
3.1 Crystal Structure and Phase Identification
3
4 Figure 1 shows the analysis results conducted using HighScore Plus software, which
5
6
indicates that the sample has three phases: Li4Ti5O12, rutile known as the TiO2 phase, and
7 SnO2 phase. These phases were matched with diffraction databases with ICDD No. 98-
8
9 016-0655, No. 98-005-3601, and No. 98-008-4973, respectively. Additionally Figure 1
10
11 shows that the presence of SnO2 can effectively eliminate the rutile TiO2 phase, as
12
13 evidenced by the XRD pattern. The analysis of XRD suggests that the SnO2 atom do not
14
15 enter the crystal structure of Li4Ti5O12, but they they exist independently, forming a
16
17
composite of Li4Ti5O12-SnO2. The peak intensity in the XRD pattern increases with the
18 addition of 2.5% SnO2, enhancing the crystallinity of Li4Ti5O12. However, higher SnO2
19
20 content can lead to decreased crystallinity and elimination of the rutile phase.
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46 Figure 1. Sample plot of Li4Ti5O12-SnO2 with variations of 0%, 2.5%, 5%, and 10%
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49
Table 1. The Percentage of Phases Existing in the Samples
50
51
52 Sample Li4Ti5O12 (%) Rutile TiO2 (%) SnO2 (%)
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54 Li4Ti5O12-SnO2 0% 78.7 21.3
55
56 Li4Ti5O12-SnO2 2.5% 91.7 - 8.3
57
58 Li4Ti5O12-SnO2 5% 75.9 - 24.1
59 Li4Ti5O12-SnO2 10% 55.7 - 44.3
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 1
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3
Table 2. Crystallite size, lattice parameters and lattice volume of Li4Ti5O12-SnO2
4
5
6 Sample Crystallite Size Lattice Parameters Lattice Volume
7
8
(Å) (Å3)
9 Li4Ti5O12-SnO2 0% 78.7 8.3657 585.4658
10
11 Li4Ti5O12-SnO2 2.5% 91.7 8.3596 584.2033
12
13 Li4Ti5O12-SnO2 5% 75.9 8.3619 584.6819
14
15
Li4Ti5O12-SnO2 10% 55.7 8.3681 585.9732
16
17
18
19 Table 1 shows that the addition of SnO2 at a 2.5%, lead to an increase in the percentage
20
21 composition of the Li4Ti5O12 phase. However, when the addition of Sn is excessive
22 (Li4Ti5O12-SnO2 5% and 10%), the percentage of Li4Ti5O12 phase decreases. This indicates
23
24 that an excessive amount of SnO2 can disrupt the Li4Ti5O12 phase composition, eliminate
25
26 the rutile TiO2 phase and increase the percentage of the SnO2 phase.
27
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29
Table 2 shows the results of the crystallite size, lattice parameters and volume. The
30 crystallite size (D) of Li4Ti5O12 is estimated from the broadening of the x-ray diffraction
31
32 peak which can be calculated using the Williamson-Hall method as follows :19
33
𝐾𝜆
34 β cos 𝜃 = + 4𝜖 sin 𝜃 …… (1)
35 𝐷
36 where D is the crystallite size (nm), k is the crystal form constant (0.89), λ is the
37
38 wavelength (0.15406 nm), β is the peak broadening, θ is the diffraction angle, and ε is the
39
40 lattice strain. The calculation gives an estimated crystallite size of Li4Ti5O12 of 59.613 nm,
41
42 57.1291 nm, 47.2793, and 45.7033 nm for 0% Li4Ti5O12-SnO2, 2.5% Li4Ti5O12 -SnO2, 5%
43
44 Li4Ti5O12-SnO2, and Li4Ti5O12-SnO2, respectively. The crystallite size of Li4Ti5O12 tends
45
46 to decrease as the composition of SnO2 in the Li4Ti5O12 sample increases. Therefore, this
47 decrease in crystallite size can inhibit particle growth.20
48
49
50 Regarding the parameter values and lattice volume, the addition of SnO2 at a 2.5%
51
52 variation resulted in a decreased. However, when SnO2 (0.25% and 0.5%) was added the
53
54
value of the parameters and lattice volume increased. Thus, it can be deduced that the
55 addition of SnO2 in Li4Ti5O12 samples affects the value of parameters and lattice volume.
56
57 The decrease in the value of lattice parameters may indicate the shrinkage or compression
58
59 of the crystal structure due to the interaction between SnO2 atoms with Li4Ti5O12. Whereas
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61 the increase in parameter values and lattice volume indicates that the interaction between
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63 SnO2 and Li4Ti5O12 does not result in significant shrinkage in the crystal structure.
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65
 3.2 Morphology of Li4Ti5O12 samples
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58 Figure 2. SEM and particle size histogram results of Li4Ti5O12-SnO2 0% (a dan e), Li4Ti5O12-
59
60 SnO2 2.5% (b and f), Li4Ti5O12-SnO2 5% (c and g), and Li4Ti5O12-SnO2 10% (d and h)
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27 Figure 3. Mapping results from Li4Ti5O12-SnO2 of (a) 0%, (b) 2.5%, (c) 5%, and (d)
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29 10%.
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32 Table 3. Percentage of Ti, O, and Sn components using SEM-EDX
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34
35 Sample Ti (wt.%) O (wt.%) Sn (wt.%)
36 Li4Ti5O12-SnO2 0% 34.52 65.48 -
37
38 Li4Ti5O12-SnO2 2.5% 35.76 62.32 1.92
39
40 Li4Ti5O12-SnO2 5% 35.84 59.54 4.62
41
42 Li4Ti5O12-SnO2 10% 28.35 61.84 9.82
43
44
45 Figure 2 displays the paraticle size of composite Li4Ti5O12 -SnO2 at various concentration
46
47 (0%, 2.5%, 5%, and 10%), which measured 0.60 μm, 0.45 μm, 0.37 μm, and 0.32 μm,
48 respectively. These finding indicate a greater degree of inhomogeneity in the sample.
49
50 Additionally, the addition of SnO2 tends to decrease the particle size of Li4Ti5O12 because
51
52 it can inhibit grain growth and avoid agglomeration. While Figure 3 provides a presence
53
54 of mulyiplr components including titanium (Ti), Oxygen (O), and Tin (Sn). The green
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56 color indicates the distribution area of the Oxygen (O), yellow color indicates the
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58
distribution area of Tin (Sn), and red color indicates the distribution area of Titanium (Ti).
59 The mapping results suggest that the SnO2 particle seems to exist independently.
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 The results of SEM/EDX analysis of samples are presented in Table 3, showing that the Li
1 (lithium) component is not detected by EDX because Li is a very light element. EDX has
2
3 detection limits for heavy elements, and light elements such as Li require higher sensitivity
4
5 to be detected by this technique. It can also be seen that the content of Sn increases with
6
7 the increase of SnO2 content in the sample.
8
9
10 3.3 Impedance of samples
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12
13
14 Figure 4 shows a plot of that combines a semicircle and a straight line, spanning from high
15
16 to low frequency. The semicircle represents the conductivity of the sample, while the
17
18 straight line known as Warburg region shows the diffusion process of lithium into the
19
20
Li4Ti5O12 structure. In batteries, the diffusion process occurs during charging and
21 discharging, as lithium ions move between the electrodes to allow the flow of electric
22
23 charge. The intersection point between the semicircle and the x-axis at higher and
24
25 intermediate frequencies reflects the contact resistance and charge transfer resistance
26
27 between the electrodes and the electrolyte. This resistance reflects how well electric charge
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29 can flow through the interface between the electrode and the electrolyte. The resistance
30
31
value plays a critical role in assessing charge transfer efficiency and the overall battery
32 performance. Among the samples, Li4Ti5O12-SnO2 5% exhibits the smallest semicircle
33
34 size and has the lowest resistance of 138.6 Ω compared to the others. However, it does not
35
36 have a long Warburg, indicating that the lithium ion diffusion process takes place slowly
37
38 in the material. In contrast, lithium ion transfer becomes more efficient in Li4Ti5O12-SnO2
39
40 2.5% because there are fewer obstacles for lithium ions to pass through when moving
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63 Figure 4. Nyquist plot of Li4Ti5O12-SnO2 of (a) 0%, (b) 2.5%, (c) 5%, and (d) 10%
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65
 1
Table 4. The resistance value of Li4Ti5O12-SnO2
2
3 Sample Rs (Ω) Rct (Ω) Rct - Rs (Ω)
4
5 Li4Ti5O12-SnO2 0% 5.4005 339.76 334.3595
6
7 Li4Ti5O12-SnO2 2.5% 2.4074 194.6 192.1926
8
9 Li4Ti5O12-SnO2 5% 9.7702 138.6 128.8298
10 Li4Ti5O12-SnO2 10% 3.2415 230.86 227.6185
11
12
13
14 between the electrode and the electrolyte.21 This leads to an increase in the diffusion
15
16 coefficient of lithium ions because lithium ions can move faster. The sample of Li4Ti5O12-
17
18 SnO2 10% shows a high Rct (charge transfer resistance) value due to the large SnO 2
19
20
content. SnO2 is a ceramic material and is insulative, contributing to the higher resistance.
21 In summary, that the addition of a small amount of 2.5% SnO2 effectively reduce the ionic
22
23 resistance in the sample.
24
25
26 Table 4 shows that samples with low Rct values can exhibit low charge transfer resistance
27 at the electrode surface. This means that lithium ions (Li+) have a better ability to transfer
28
29 between the electrode surface and the electrolyte. As charge transfer takes place more
30
31 efficiently, the diffusion coefficient of lithium ions also tends to increase.
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33
34
Materials with low Rct values possess enhaced lithium-ion diffusion capabilities. The Rct-
35 Rs ratio is the ratio between the charge transfer resistance (Rct) and the internal resistance
36
37 (Rs) within an electrochemical cell. When the value of Rct exceeds that of Rs, the Rct-Rs
38
39 ratio is positive, indicating that the charge transfer resistance plays a more dominant role
40
41 in influencing the electrochemical response of the cell. This may suggest that the
42
43 electrochemical reaction at the electrode surface progresses more more slowly than the
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45
total resistance in the cell, and an increase in charge transfer may be necessary to improve
46 cell performance.
47
48
49 Meanwhile, when the value of Rs is greater than Rct, then Rct-Rs ration becomes negative.
50
51 This indicates that series resistance predominates influencing the electrochemical response
52 of the cell. However, this phenomenon can result from various factors such as electrolyte
53
54 resistance, connectivity among cell components, and other contributing elements.
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57 3.4 Oxidation and reduction of half cell
58
59 To evaluate the intercalation and de-intercalation of Li-ion in battery cells, cyclic
60
61 voltammetry (CV) measurements were performed at various scan rates, covering a voltage
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63 range of 0.8 to 2.5 V, with a scan rate of 0.1 mV/s for all samples. CV curves depict the
64
65 electrochemical response of a sample at various voltage levels. The oxidation (charging)
 and reduction (discharging) peaks in the CV curves reflect the redox reactions that occur
1 during the intercalation (insertion) and de-intercalation (extraction) processes of lithium
2
3 ions in the sample cell.22 At the oxidation peak, an electrochemical reaction occurs where
4
5 lithium ions are inserted into the electrode, resulting in a potential change. While at the
6
7 reduction peak, an electrochemical reaction occurs in which lithium ions are extracted from
8
9 the electrode, again resulting in a change in potential. The shifting of redox peaks towards
10
higher or lower potentials in CV can occur due to electrochemical polarization. 23
11
12 Electrochemical polarity is caused by the potential difference between the electrode and
13
14 the electrolyte during the electrochemical process.
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40 Figure 5. Cyclic voltametric curve Li4Ti5O12-SnO2 with various variations of Sn using a
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42 scan rate of 0.1 mV/s
43
44 Figure 5 illustrates the oxidation and reduction values of different Li4Ti5O12-SnO2
45
46 compositions. Li4Ti5O12-SnO2 0% exhibits peak oxidation and reduction values of 1.6955
47
48 mA and 1.4934 mA, respectively. Li4Ti5O12-SnO2 2.5% records values of 1.6897 mA for
49
50 oxidation and 1.3235 mA for reduction. In the case of Li4Ti5O12-SnO2 5%, the values
51
52 are 1.6758 mA for oxidation and 1.3814 mA for reduction. Lastly, Li4Ti5O12-SnO2 10%
53
54
displays oxidation and reduction values of 1.6764 mA and 1.3918 mA, respectively.
55
56 Among the Li4Ti5O12-SnO2 compositions, Li4Ti5O12-SnO2 2.5% exhibits the highest and
57
58 sharpest peak. This high curve shape indicates rapid intercalation, where lithium ions (Li+)
59
60 can be smoothly and effectively intercalate into the Li4Ti5O12 structure. The result in a
61
sharp voltametric response with a prominent peak indicates a fast and efficient reaction
62
63 rate between the Li4Ti5O12 anode electrode and lithium ions. Fast intercalation is a highly
64
65 desirable characteristic in lithium-ion battery anode materials, including Li4Ti5O12, as it
 contributes to high capacity and excellent battery performance. An efficient intercalation
1 process enables the battery to charge and discharge energy quickly and consistently charge
2
3 and discharge energy during its charge and discharge cycles. While Li4Ti5O12-SnO2 10%
4
5 exhibits a low and broadened redox peak, indicating slow intercalation. Slow intercalation
6
7 can occur when the sample structure experiences resistance in accepting and releasing Li
8
9 ions. It can be seen in Figure 5 that the reduction peak has a varying voltage shift. A shift
10
to the left or right may indicate a change in the potential at which the reaction occurs or a
11
12 change in the reaction rate. A shift to the left indicates that the de-intercalation reaction
13
14 occurs at a lower potential, which may contribute to battery performance with high
15
16 capacity or a more effective discharge rate. A shift to the right indicates a de-intercalation
17
18 reaction at a higher potential, which could lead to improved charging efficiency or battery
19
20 cell stability. The increase in capacity caused by the structure of adding SnO2 with a
21 concentration of 2.5% may occur due to the interaction between SnO2 and Li4Ti5O12 which
22
23 forms a new structure that facilitates the storage of lithium ions. Meanwhile, the voltage
24
25 shift in the cyclic voltammetry curve indicating the presence of microalloying also shows
26
27 that there is an interaction between SnO2 and Li4Ti5O12 that affects the electrochemical
28
29 reaction potential.24 Microalloying can cause structural changes or chemical reactions
30
31 resulting in better voltage during the intercalation and de-intercalation process of lithium
32 ions.
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59 Figure 6. Linear cyclic graph of Li4Ti5O12-SnO2 with variation SnO2 (a) 0%, (b) 2.5%, (c)
60
61 5%, and (d) 10%.
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63
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65
 Figure 6 shows the gradient value created by the relationship between the current and the
1 speed of the scan rate, which can be interpreted as a diffusion control method in the
2
3 oxidation/reduction process. The Ip (v1/2) relationship can be described using the Randles-
4
5 Sevcik equation to obtain an electrochemical process that can be formulated as follows:25
6 1
7 𝑛2 𝐹 3 2
8 𝐼𝑝 = 0.4463 ( 𝑣𝐷) 𝐴𝐶 ………. (2)
𝑅𝑇
9
10
11
12 Where Ip is the peak current (Amperes), n is the number of electrons involved in an
13
14 electrochemical reaction, F is the Faraday constant (C/mol), R is the gas constant
15
16 (J/mol.K), T is the absolute temperature (K), A represents the electrode surface area (cm2),
17
18 D is the diffusion coefficient of lithium ions in Li4Ti5O12 (cm2/s), C is the molar
19
20 concentration of lithium ions in the Li4Ti5O12 crystal (mol/cm3), and v is the scan rate (V/s).
21
22
23
24 Table 5. The Value of The Diffusion Coefficient of Li4Ti5O12 with The Variation of SnO2
25
26 Sample Diffusion Coefficient (cm-2s-1)
27
28 Li4Ti5O12-SnO2 0% 3,64021 x 10-10
29 Li4Ti5O12-SnO2 2.5% 6,08859 x 10-8
30
31 Li4Ti5O12-SnO2 5% 5,46535 x 10-8
32
33 Li4Ti5O12-SnO2 10% 1,43585 x 10-8
34
35
36
37
38 Table 5 presents the calculated values, revealing that the anode Li4Ti5O12-SnO2 2.5% has
39
40
the highest value of 6.08859 x 10-8 cm-2s-1 and the anode Li4Ti5O12-SnO2 0% has the
41 lowest diffusion coefficient value of 3.64021 x 10-10 cm-2s-1. This shows that addition
42
43 SnO2 2.5% can significantly enhance the rate of intercalation and de-intercalation of
44
45 lithium ions within the Li4Ti5O12 structure. Therefore, the intercalation and de-intercalation
46
47 of lithium ions can occur rapidely. Batteries that use the Li4Ti5O12-SnO2 2.5% have the
48
49 potential to provide better capacity and performance in charge and discharge. In contrast,
50
an excessive amount of SnO2 can lead to a decrease in the diffusion coefficient, indicating
51
52 that too much SnO2 ay hinder the lithium ion diffusion process.
53
54
55 3.5 Capacity and rate capability of half cell
56
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58
59
60
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65
 Figure 7 shows the initial charge/discharge capacity in the Li4Ti5O12-SnO2 0% sample,
1 which is 205.15/212.68 mAh/g. The Li4Ti5O12-SnO2 2.5% sample has increased capacity
2
3 with a charge/discharge value of 247.26/236.94 mAh/g. The Li4Ti5O12-SnO2 5% sample
4
5 has decreased capacity with a charge/discharge value of 181.51/206.9 mAh/g. While the
6
7 capacity of Li4Ti5O12-SnO2 10% has decreased with a charge/discharge value of
8
9 165.95/170.26 mAh/g. Increases and decreases in capacity in batteries can be affected by
10
a variety of factors, including changes in material composition and cell condition. The
11
12 addition of SnO2 2.5% to Li4Ti5O12 can improve electrochemical reactions and increase
13
14 capacity due to the crystallinity of Li4Ti5O12 and the diffusion coefficient in the XRD and
15
16 CV test results have a high value and phase concentration of Li4Ti5O12. This allows more
17
18 lithium ions to be intercalated during the charge-discharge process. While samples with
19
20 SnO2 5% and 10% produce unstable graphs and decreased capacity, which is related to a
21 decrease in the percentage of Li4Ti5O12 phase composition that can be seen from the XRD
22
23 test. Higher concentrations of SnO2 can disrupt the material structure and electrochemical
24
25 reactions in the battery. Complex chemical reactions between Li4Ti5O12 and higher SnO2
26
27 content can slow down reaction kinetics, resulting in decreased capacity. The addition of
28
29 higher SnO2 can also lead to cycle instability and poor battery performance.
30
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58 Figure 7. Charge-Discharge capacity graph Li4Ti5O12-SnO2 with variation SnO2 (a)
59
60 0%, (b) 2.5%, (c) 5%, and (d) 10%.
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63
4. Conclusions
64
65
 Composite of Li4Ti5O12-SnO2 was successfully synthesized by solid state method using
1 Lithium Carbonate (Li2CO3) and Titanium Dioxide (TiO2), as well as SnO2 (Tin dioxide)
2
3 at 850°C. Among the various composition, the Li4Ti5O12-SnO2 2.5% composite exhibited
4
5 the highest percentage of Lithium Titanium Oxide phase of 96.9%. While the SEM
6
7 analysis revealed that the addition of SnO2 led to a reduction in particle size and altered
8
9 particle morphology. Furthermore, the addition of 2.5% SnO2 significantly increased the
10
diffusion coefficient and enhanced the specific capacity. However, it should be noted that
11
12 the addion of higher amount of SnO2 leads to negative impact on the electrochemical
13
14 performance. Therefore, the Li4Ti5O12-SnO2 composite material, particularly with a 2.5%
15
16 SnO2 content, has great potential for the development of high-performance Lithium-ion
17
18 batteries, particularly in application liker electric vehicles.
19
20
21 Acknowledgments
22
23 The authors wish to express their thanks for the financial support from Rumah Program -
24
25 Research Organization of Nanotechnology and Material -National Agency for Research
26
27 and Innovation (BRIN) 2023.
28
29
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