Ionics

https://doi.org/10.1007/s11581-019-03084-4

ORIGINAL PAPER

High electrochemical performance of Li4Ti5O12/C synthesized by ball

milling and direct flaming of acetylene gas as anode for lithium-ion
battery
Lukman Noerochim 1 & Amalia Ma’rifatul Maghfiroh 1 & Widyastuti 1 & Diah Susanti 1 & Slamet Priyono 2 &
Bambang Prihandoko 2

Received: 14 January 2019 / Accepted: 21 May 2019

# Springer-Verlag GmbH Germany, part of Springer Nature 2019

Abstract
Li4Ti5O12/C has been successfully synthesized by a solid-state reaction method of Li2CO3 and TiO2 followed by direct flaming of
acetylene gas. Li4Ti5O12 with 2-h milling time is indexed as single-phase crystal structure of Li4Ti5O12 (JCPDS 04-0477). The
SEM results show particle sizes between 0.192 and 0.360 μm with a spherical shape, but there is agglomeration due to high
temperature when the direct flaming of acetylene gas process is applied. The desired carbon content by direct flaming of
acetylene gas is still very low at 0.6% for 10 min and 0.9% for 20 min. Li4Ti5O12 with 10 min of direct flaming of acetylene
gas has the highest specific discharge capacity of 210.61 mAh/g. This is attributed to the pure single phase and the higher
conductivity of the sample. This result shows that Li4Ti5O12/C synthesized by ball milling and direct flaming of acetylene gas
could be a good candidate as anode for lithium-ion battery.

Keywords Li4Ti5O12/C . Ball milling . Direct flaming . Anode . Lithium-ion battery

Introduction
Graphite is generally applied as an anode in a commercial
lithium-ion battery. However, one of the disadvantages of this
graphite is unable to be applied under high current density
which will cause serious problems related to safety [1]. In
addition, graphite has anisotropic structures which inhibit in
the process of transportation and diffusion of lithium ions in
the graphite structure which results in a low rate of capability
[2]. The interlayer distance between layers of graphite in-
creases to undergo volume expansion due to the insertion of
lithium into the graphite structure [3, 4]. Although the specific
discharge capacity of graphite is large (300 mAh/g), however,
the electron flow will not be able to be taken in large enough
quantities (> 4C). This is because the cell potential will drop
* Lukman Noerochim
lukman@mat-eng.its.ac.id
1
Department of Materials and Metallurgical Engineering, Sepuluh
Nopember Institute of Technology, Surabaya 60111, Indonesia
2
Research Center of Physics, Indonesian Institute of Science,
Serpong, Indonesia
below the battery cut off voltage when the current is in high
density [5]. The capacity becomes unstable and tends to ex-
perience current/potential declination which will reduce bat-
tery capacity [6]. The ability of battery discharging becomes
unbalanced when charged with a discharge rate of more than
4C. This is due to the phenomenon of pulveration and dendrite
growth of lithium metal at the anode due to high-rate current
density. Therefore, for applications that require high power, a
compatible negative electrode is currently needed that can
supply large currents (> 4C) without occurring, both a drastic
voltage drop (flat voltage) and a decrease in capacity.
Some candidate anodes include silicon-based materials, but
despite being capable of high-discharge conditions, silicon
experiences a volume change of up to 400% during insertion
and extraction of lithium-ions which affect pulverization (col-
lapse of surface structures) and loss of capacity [7, 8]. One of
the anode materials becoming a lot of attention is Li4Ti5O12
(lithium titanate) or LTO. Li4Ti5O12 has the potential as a
substitute for graphite for anodes. This is because Li4Ti5O12
has a voltage stable operation of Li+/Li which does not cause
lithium-ion dendrites at the anode during the intercalation pro-
cess [9]. LTO also has a high capacity, high charging-
discharging rate, and zero-strain material because it has a
strong spinel crystal structure [10, 11]. However, the low
 Ionics

(111)
* TiO2 * TiO2 anatase

(111)

(400)
(400)

(311)
(311)

(440)
(440)

(622)
(533)

(511)
(511)

(533)
(531)

(622)
(331)
(222)
(531)

Intensity (a.u)
Intensity (a.u)

(331)
(222)
*
BM 4 *
LTO2 DF20

BM 3

LTO2 DF10
BM 2

JCPDS No. 49-0207 LTO2 DF0

10 20 30 40 50 60 70 80 90 10 20 30 40 50 60 70 80 90

2 (Degree) 2 (Degree)
Fig. 1 XRD pattern of LTO samples with a variation of ball milling Fig. 2 Comparison of XRD pattern of LTO BM2 with a variation of
duration direct flaming for 0, 10, and 20 min

electrical conductivity (10−13 S/cm) and the low diffusion of
lithium-ions are one of the disadvantages of the Li4Ti5O12
electrode [12]. It can cause a low rate of release and diffusion
of lithium ions in a charge-discharge process.
Two major strategies to improve the conductivity of LTO
are by coating with conductive agents such carbon and by
reducing particle to nanosize. There are several methods used
to synthesize Li4Ti5O12/C which include solid-state reaction
[13], hydrothermal [14], sol-gel [15], biphasic interfacial re-
action [16], electrospinning [17], and spray-drying method
[18]. In a previous study [19], synthesis of Li4Ti5O12/C was
carried out with the sol-gel method which then used tempera-
ture variations during calcination. In addition, they compared
LTO/C and pure LTO in terms of electrochemical perfor-
mance. It turned out that the results of the study showed that
LTO/C had better electrochemical performance compared to
pure LTO. This proves that the presence of carbon is very
influential on the performance of lithium-ion batteries.
Carbon sources that can be used include polyvinyl alcohol
(PVA) [20], citric acid [21], sucrose [22], glucose [23], and
polyacrylic acid [24]. This carbon not only increases the con-
ductivity value but also controls particle size by reducing
agglomeration.
Another method for carbon coating process is employed by
in situ pyrolysis process using acetylene gas as a carbon
source [25]. It is reported that LiFePO4/C with 10-min C2H2
Table 1 Crystal size calculation of LTO using the Debye Scherer
equation with variations of ball milling 2, 3, and 4 h without acetylene gas
BM(h) 2θ (°) θ (°) FWHM Cos θ
2 43.568 21.784 0.117 0.928
3 43.487 21.743 0.117 0.928
4 43.45 21.725 0.133 0.929
treatment showed high specific discharge capacity of
144 mAh/g and the amount of carbon of 3.98 wt.% [26].
This method typically is carried out in protective gas at high
temperature (more than 600 °C). Therefore, complex equip-
ment is required to ensure no air-trapped inside the furnace
chamber.
In this research, Li4Ti5O12/C is prepared by solid-state
reaction method with the ball milling process. While the
carbon coating process uses a new method, namely the di-
rect flaming technique of acetylene gas. The effect of direct
flaming will be discussed and studied systematically based
on the electrochemical performance of the LTO electrode. In
this work is expected to produce a pure spinel LTO phase
with the desired carbon content and grain size which can
increase the conductivity of the LTO electrode for better
battery performance.
Experimental method
Preparation of LTO/C
In a typical synthesis, a stoichiometric amount of all precur-
sors such as 1.5 g of Li2CO3 (Merck, 98%) and 4.0 g of TiO2
(Merck, 98%) was wet milled using a planetary ball mill.
Precursors were milled at 150 rpm for effective 2, 3, and 4 h
in ethanol, keeping the ratio of the ball to powder as 5:1. Then,
the samples were labeled as LTO BM2, LTO BM3, and LTO
BM4, respectively. The resulting solid powder was then dried
in air at 50 °C and ground to a fine powder using agate mortar
D (Å) D (nm)
and pestle. Subsequently, the precursors were calcined at tem-
12.751 1.275 peratures 750 °C for 6 h with a heating rate of 10 °C min−1 in
12.747 1.274 the atmosphere, and then cooled naturally to room tempera-
11.155 1.115 ture in the furnace. The carbon coating process by direct flam-
ing of acetylene gas is carried out by using an oxy-acetylene
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Fig. 3 SEM images of LTO BM2

sample a without direct flaming,
b direct flaming 10 min, and c
direct flaming 20 min

torch. A certain amount of LTO sample was put in an alumina
crucible. Then, the oxy-acetylene torch is directed to inside
alumina crucible for 10 and 20 min. The as-prepared samples
are identified as DF10 and DF20 according to the time for
LTO was exposed to acetylene gas.
Physical and electrochemical measurements
The Li4Ti5O12 powder was analyzed by XRD to identify its
phase and crystal structure (PANalytical, CuKα radiation).
SEM (Phillips, FEI Inspect 250) was employed to observe
the morphology particle of Li4Ti5O12. The CR2032 coin cell
is used for testing of anode Li4Ti5O12. The as-prepared elec-
trodes consisted of active ingredients (85 wt.%), acetylene
black (10 wt.%), and poly vinylidene fluoride as binders
in a glove box with Ar gas using lithium foil as a counter
electrode, micropore polypropylene membrane (Celgard
2400) as a separator. Electrolytes are a 1 M LiPF6 solution
in ethylene carbonate (EC):diethyl carbonate (DEC):ethyl
methyl carbonate (EMC) with a volume ratio of 1:1:1. A cy-
clic voltammetry of the LTO/C samples was measured by an
electrochemistry workstation (WonATech WBCS 2000) with
a sweep scan rate of 0.1 mV/s and potential range of 1.0–
2.5 V. The charge-discharge test is carried out on a recycler
battery system (WonATeCH WBCS 2000) with C-rate varia-
tion of 0.4C, 1C, 2C, and 5C at potentials range from 1.0 to
2.5 V (vs. Li+/Li). Electrochemical impedance spectroscopy
1.5
BM2 DF0
1.0 BM2 DF10
Current (mA/g)

(5 wt.%) dissolved in N-methylpyrrolidone solvents, which

BM2 DF20
were evenly pasted on a Cu foil and dried at 110 °C overnight
0.5
to remove residual solvents. The coin cells are then assembled
0.0
Table 2 Results of carbon analyzer LTO with direct flaming 10 and
20 min
-0.5
Sample Weight (gr) C (%) Percentage (%)
-1.0
LTO BM2 DF10 0.1088 0.612 Average 0.629
0.1516 0.609
0.1517 0.631 -1.5
0.5 1.0 1.5 2.0 2.5 3.0 3.5
LTO BM2 DF20 0.1198 0.946 Average 0.963 +
0.0769 0.969 Potential (V vs. Li/Li )
0.1540 0.975 Fig. 4 Cyclic voltammetry of Li4Ti5O12 with direct flaming for 0, 10, and
20 min
 Ionics

Table 3 The detail of reduction and oxidation peaks of LTO samples Figure 2 shows the XRD of LTO BM 2 with the direct
Sample Ea (V) Ia (mA) Ec (V) Ic (mA) ΔE (V) flaming of 0, 10, and 20 min. All LTO samples are still
indexed as Li4Ti5O12 without significant change. The differ-
BM2 DF0 1.64 0.75 1.44 − 0.41 0.20 ence between the LTO samples is the intensity magnitude of
BM2 DF10 1.64 1.24 1.47 − 1.12 0.17 the diffraction peak. It is clearly observed that the longer the
BM2 DF20 1.64 0.92 1.46 − 0.53 0.18 time of direct flaming, the higher the intensity of the peaks
attributed to increasing crystallinity of the materials. The LTO
sample with direct flaming for 10 and 20 min is found with
(EIS) measurements are carried out on electrochemical work- impurity as the second phase, namely TiO2 anatase. The TiO2
stations (CorrTest) in the frequency range 0.01 Hz to 100 kHz anatase is indexed at 2θ around 25.4° with low intensity.
by giving them an AC signal of 5 mV. All electrochemical Figure 3 shows the SEM images of LTO without treatment
measurements are carried out at room temperature (25 °C). of direct flaming and after the direct flaming process. The
particles of the LTO samples with and without direct flaming
are seem agglomerated and moreover, both of LTO with direct
Results and discussion flaming seem more severe agglomeration. The shape of LTO
particles is granules with different sizes in the range from
The phase identification of LTO sample of BM 2, BM3, and 0.192 to 0.360 μm. The longer the time of direct flaming,
BM4 (Fig. 1) shows that all diffraction peaks are characterized the larger the obtained particle diameter. It is also found that
as Li4Ti5O12 with cubic spinel structure and space group Fd- the particle of LTO BM2 DF20 sample tends to be more ag-
3m (JCPDS card no 49-0207) [27]. All samples present a high glomerated in form.
intensity of diffraction peak attributing high crystallinity. The carbon content in LTO was measured by a carbon
However, the XRD pattern of LTO BM4 is observed at 1- analyzer as shown in Table 2 for direct flaming of 10 and
weak peaks with low intensity at a 2θ angle of 25.4° belong- 20 min, respectively. It is clear that the carbon content of
ing to TiO2 anatase phase. This could be the longest time of LTO is quite homogeneous for all samples. The highest car-
ball milling producing excess energy that will stimulate TiO2 bon content is reached up to 0.963% for direct flaming of
anatase formation. To determine the effect of the ball milling 20 min. The amount of this carbon content is quite low for
duration, the Debye Scherrer equation is applied to calculate completely coating the LTO sample compared to other works
the crystal size of the LTO sample. [29–31]. This is confirmed that the direct flaming of acetylene
Table 1 shows that the smallest crystal size is found at LTO gas is good for purposing low carbon coating process.
BM4 sample with a crystal size of 1.115 nm, then tends to Figure 4 shows the cyclic voltammetry (CV) for the
increase when the duration of ball milling is reduced. This first cycle of LTO samples. All samples of LTO show
result is in high agreement with the previous report [28, 29]. high and sharp oxidation and reduction peaks. It is well
However, the LTO BM4 has an extra peak of TiO2 anatase that known that the sharp and well-resolved redox peak usu-
it is not preferred for electrode materials. Therefore, based on ally signifies that the insertion/de-insertion of Li+ takes
the XRD results for the next experiment, the LTO BM2 was place quickly, while a broad peak shows a slow process
chosen for direct flaming of acetylene gas process. [32]. The LTO BM2 DF10 has the highest reduction
2.5
and oxidation peak. It is indicated that the LTO BM2
DF10 has the highest conductivity than other samples.
BM2 DF0 Furthermore, the ΔE polarization of LTO BM2 DF10 of
2.0 BM2 DF10 direct flaming is the smallest than other samples. The
BM2 DF20
low ΔE polarization indicates the fast transfer of the Li-
Voltage (V)

1.5 ion and the electrons during charge-discharge process.

The redox reaction during charge-discharge process is
described below [33, 34].
1.0
Reduction:

0.5 Li4 Ti5 O12 þ αLiþ þ αe− →Li4þα Ti5 O12 ð1Þ

Oxidation:
0.0
0 50 100 150 200 250
Specific Discharge Capacity (mAh/g) Li4þα Ti5 O12 →Li4 Ti5 O12 þ αLiþ
Fig. 5 Charge-discharge curve of LTO BM2 without direct flaming and þ αe− Li4þα Ti5 O12 →Li4 Ti5 O12 þ αLiþ þ αe− ð2Þ
with direct flaming of acetylene gas for 10 and 20 min
Ionics

100
140 (a) (b)

Specific Discharge Capacity (mAh/g)

Specific Discharge Capacity (mAh/g)

90
0.4 C 0.4 C
120 80

100
1C 70

60
80 2C
50
BM2 DF0
60 40 BM2 DF10
BM2 DF0
BM2 DF10 5C BM2 DF20
30
40 BM2 DF20
20
20
10

0 0
0 10 20 30 40 50 0 10 20 30 40 50 60 70 80 90 100
Cycle Number Cycle Number
Fig. 6 a Rate capabilities and b cycle performances of LTO BM2 without direct flaming and with direct flaming of acetylene gas for 10 and 20 min

Table 3 shows that the LTO for 10-min direct flaming has LTO BM2 DF10 has the superior of specific discharge
the highest of both an oxidation peak intensity of 1.42 mA and capacity than other sample even higher than the theoretical
a reduction of 0.85 mA. LTO BM2 DF20 has an oxidation discharge capacity of Li4Ti5O12 (175 mAh/g). This result is
peak intensity of 0.92 mA and a reduction of 0.53 mA. While also similarly reported by other works that LTO-coated graph-
the lowest intensity of the oxidation peak is LTO BM2 without ite prepared by ball milling method shows superior rate capa-
direct flaming of acetylene gas. LTO BM2 DF10 has the low- bility and cycling performance over than the theoretical dis-
est polarization energy of 0.17 V, followed by 20 min of charge capacity of Li4Ti5O12 with high initial discharge ca-
0.18 V and LTO BM2 without direct flaming of acetylene pacity of 324 mAh/g at 0.2C [35]. It could be attributed to high
gas. The results show that the LTO BM2 DF10 has the highest crystalinity of single phase and the lowest ΔE polarization.
Li-ion diffusion rate and low internal resistance. Typically, the The rate capability for LTO BM2 samples as a function of
combination of these two properties will increase the electro- current density from 0.4 to 5C is shown in Fig. 6a. Although
chemical process in the Li-ion intercalation/de-intercalation all LTO BM2 samples with and without direct flaming show a
reaction. drastic reduction in discharge capacity when increasing cur-
Figure 5 shows the initial charge-discharge curve of LTO rent density from 1 to 5C, the initial discharge capacity at 0.4C
BM2 at 0.1C. The LTO BM2 DF10 showed a specific dis- from the LTO BM2 DF10 can still survive ~ 34% at a high
charge capacity of 210.61 mAh/g, whereas LTO BM2 DF20 density of 5C and can be restored up to more than 90% when
showed a specific discharge capacity of 193.67 mAh/g and the current density returns to 0.4C. This high capability of
LTO BM2 DF0 has a specific discharge capacity of LTO BM2 DF10 could be attributed to the formation of
133.26 mAh/g. single-phase LTO with a spinel structure and smaller crystal-
lite size. The smaller crystallite size of LTO BM2 DF10 par-
ticles and the homogeneous distribution of LTO BM2 DF10
particles should more enhance the electrochemical perfor-
mance [35].
Figure 6b shows the cycle stability of all LTO BM2 without
direct flaming and with direct flaming of acetylene gas at 1C
for 100 cycles. It is clearly observed that the LTO BM2 DF10
sample has the highest cycle stability with a capacity fading of
5.2% and the specific discharge capacity of 88.3 mAh/g at the
100th cycle. Meanwhile, the LTO BM2 DF20 and DF0

Table 4 Rs, Rct, and DLi for all LTO BM2 samples

Sample Rs (Ω) Rct (Ω) σw (Ωs-0.5) DLi (cm-2 s-1)

BM2 DF0 19.11 340.89 485.66 1.06 × 10−12

BM2 DF10 6.53 93.47 151.05 1.22 × 10−11
Fig. 7 Nyquist Plot of LTO BM2 for 0, 10, and 20 min direct flaming. BM2 DF20 7.72 192.27 615.41 1.50 × 10−12
Insert the equivalent circuit

1200
1100
BM2 DF0
BM2 DF10
1000 BM2 DF20
900
800
Z'(Ohm)
700
600
500
400
300
200
100
0.4 0.6 0.8 1.0 1.2
-0.5 -0.5
(s )
Fig. 8 Diffusion Li-ion curve at low frequencies for direct flaming of
acetylene gas
samples have a capacity decline of 10.6% and 21.1% with
specific discharge capacity of 78.1 and 64.3 mAh/g at 100th
cycle, respectively. The high cycle stability in the LTO BM2
DF10 sample could be the high crystallinity of LTO BM2
DF10 which enhances the Li-ion transfer during the lithiation
and de-lithiation process of lithium ions [35]. Furthermore, the
optimal composition of the carbon layer on the surface of the
LTO particles facilitates the electron transfer process in the
electrode.
Figure 7 shows the Nyquist plot of all LTO BM2
samples and the equivalent circuit of the curve. The
R 1 (Rs) shows the characteristics of electrolyte resis-
tance, while the R 2 (Rct) shows the charge transfer
resistance, and constant phase angle element (CPE)
represents the capacitive grain boundary [36–38].
The Rct determines the ability of electron transfer of
the sample. The higher the Rct, the more difficult the
electron transfer process. Figure 7 shows that LTO
BM2 without direct flaming of acetylene gas has a
high Rct but when direct flaming of acetylene gas is
applied, the Rct gradually decreased. All values of Rs
and Rct are tabulated in Table 4. This shows that the
direct flaming of acetylene gas will reduce the charge
transfer electron of the LTO BM2 DF10 and DF20
samples. When the direct flaming of acetylene gas is
20 min, the semicircle is obtained bigger than the
DF10 sample. This could be the temperature during
direct flaming producing the growth of particles of
the LTO BM2 DF20 sample.
Figure 8 shows the plot relationship between real
impedance (Z′) and reciprocal square root from angular
frequency (ω−0.5) in the low-frequency region. The dif-
fusion coefficient of Li (DLi) ions from the sample is
calculated by Eqs. (3) and (4) [39–41]. Then the calcu-
lation results are listed in Table 4.
Ionics
R2 T 2
D¼ ð3Þ
2A2 n4 F 4 c2 σ2w
where D is the diffusion coefficient of lithium-ion
(cm2 s−1), R is the gas constant (8314 J mol−1 K−1), T is the
absolute temperature (K), A is the electrode area (cm2), n is the
number of electrons involved in the redox process (in this
case), C is the concentration of lithium-ion (7.69 ×
10−3 mol cm−3), F is the Faraday constant (96,486 C mol−1),
and σw is the Warburg Factor, which is related to Z′ with the
following equation:
1.4 0
Z ¼ Rs þ Rct þ σw ω1=2 ð4Þ
Based on Eq. (4), the Warburg impedance coefficient
is calculated and then used in Eq. (3) to obtain the
diffusion coefficient of lithium-ions from the synthe-
sized sample as shown in Table 4.
It shows that the Li-ion diffusion of LTO BM2 DF10
has a lower Li-ion diffusion than other samples. The
low diffusion of Li-ion indicates that Li-ion will be
easier to intercalate and de-intercalate which it would
be able to improve the electrochemical performance of
the lithium-ion battery.
Conclusion
Li4Ti5O12/C was successfully synthesized by the solid-state
method with ball milling process of 2.3 and 4 h and followed
by direct flaming of acetylene gas of 0, 10, and 20 min. The
XRD results showed a single phase of Li4Ti5O12 phase with
JCPDS 04-0477. SEM results show that the particle size is
between 0.192 and 0.360 μm with a round particle shape but
there is still an agglomeration due to high temperatures when
the direct flaming of acetylene gas is applied. The carbon
analyzer shows that the desired carbon coating is still very
low, which is around 0.6% for the 10 min of acetylene gas
and 0.9% for 20 min of acetylene gas. The LTO BM2 DF10
has the highest specific discharge capacity of 210.61 mAh/g.
The LTO BM2 DF10 sample also has the highest cycle stabil-
ity with a capacity fading of 5.2% and specific discharge ca-
pacity of 88.3 mAh/g at the 100th cycle. It is attributed to a
single phase of the LTO BM2 DF10 electrode and the low of
ΔE polarization. The high of crystallinity enhances the Li-ion
transfer during the lithiation and de-lithiation process of lith-
ium-ion. Furthermore, the optimal composition of the carbon
layer on the surface of the LTO particles facilitates the electron
transfer process in the electrode. It is also enhanced by the
lower diffusion of the Rct and the higher diffusion Li-ion of
LTO BM2 DF10 compared to other samples.
Ionics
Funding information This work was financially supported by Penelitian
Dana Lokal ITS Surabaya (No/PKS/ITS/2019) and partially funded by
the Research Grant of National Innovation System Consortium
(INSINAS) IRPK-2018-148 Ministry of Research, Technology and
Higher Education of the Republic of Indonesia (Kemenristek DIKTI).
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 SURAT PERNYATAAN

Yang bertandatangan di bawah ini kami tim penulis dari publikasi ilmiah bersama dengan judul :

" High electrochemical performance of Li 4 Ti 5 O 12/C synthesized by ball milling and

direct flaming of acetylene gas as anode for lithium-ion battery",

Lukman Noerochim, Amalia Ma’rifatul Maghfiroh, Diah Susanti, Slamet Priyono, Bambang
Prihandoko, Ionics volume 25, pages 5315–5322 (2019)

menerangkan bahwa kontribusi masing- masing penulis adalah sebagai berikut:

Lukman Noerochim (Kontributor Utama)
Bambang Prihandoko (Kontributor Utama- Peneliti)
Slamet Priyono (Kontributor Utama- Peneliti)
Diah Susanti (Kontributor Anggota )
Amalia Ma’rifatul Maghfiroh (Kontributor Anggota)

Demikian surat pernyataan ini kami buat dengan sebenar-benarnya.

Tangerang Selatan, 8 Juni 2021

Yang menyatakan,

(Lukman Noerochim) ( Slamet Priyono )

(Bambang Prihandoko) (Diah Susanti) (Amalia Ma’rifatul Maghfiroh)