Surat Keterangan Kontributor
Surat Keterangan Kontributor
Yang bertanda tangan di bawah ini menyatakan bahwa untuk capaian berikut:
Indeksasi ini hanya memuat Jurnal ilmiah terindeks global bereputasi tinggi, Jurnal ilmiah terindeks global bereputasi menengah, Jurnal ilmiah
terindeks global bereputasi, Jurnal ilmiah terindeks lainnya, dan Prosiding ilmiah terindeks global bereputasi
Select an item
Tahun Terbit
A R T I C LE I N FO A B S T R A C T
Keywords: In spite of its high potential, the electrochemical performance of lithium titanate (LTO) has rarely been in-
Lithium titanate vestigated as an anode material in lithium ion capacitor (LIC). This study is aimed to probe the effect of low
Al-doped LTO concentration Al doping on the properties of LTO as well as its electrochemical performance for lithium ion
Electrochemical performance capacitor application. In this work, a facile sol gel reaction is employed to synthesize Li4Ti5-xO12Alx (x = 0,
LIC
0.025, 0.05, and 0.075). The starting materials were stoichiometrically dissolved in ethanol and mixed, followed
by calcination at 800 °C for three hours. XRD pattern of the samples demonstrate the peak shifting of LTO
structure, as Al content increases to some extent. The LTOA 0.025 sample has smaller and more uniform particles
than that of pristine LTO. The half-cell performance shows that LTOA 0.025 has higher current peak and ca-
pacity, 154.5 mAh.g−1 than that of pristine LTO. Meanwhile, the performance of full-cell LIC also demonstrate
the increase of its specific capacitance at various scan rate and the excellent retention stability, which can sustain
83.9% of its initial performance after 800 cycles.
1. Introduction charging [6]. Another attractive property of LTO is its spinel structure,
which enable an extremely narrow-volume change during insertion or
These days, the research on improving the performance of storage de-insertion process. However, the cycle stability of LTO are inferior
devices has been attracting many researchers due to the demand of than other materials such as graphite and Li3VO4 [7,8]. Several at-
high-performance electronic equipment in our daily life. As an excellent tempts to optimize the nature of LTO have been reported, including
combination system between electrical double layer capacitor (EDLC) carbon coating, surface area modification, structural modification, and
and lithium ion battery (LIB) system [1,2], lithium ion capacitor (LIC) is modification of particle size [9].
considered as a promising technology device which have intensively Another approach is metal ion doping which is intended to improve
been expanded for a few years. LIC consists of activated carbon (AC) as the properties of LTO. This approach is generally proposed to enhance
a cathode and metal oxide as an anode. The device has a high power the stability performance of LTO by substituting metal ions, such as
density as well as energy density adopted from EDLC and LIB proper- Mg2+, Cu2+, Ni5+, and Br−, into Li, Ti, and O sites of the spinel-LTO
ties, respectively. Some references mentioned that the working voltage structure [10–13]. Carrillo et al. managed to insert Fe3+ metal ions into
of LIC can exceed 3.8 V, which is higher than that of typical EDLC, i.e. Ti site. The effect of Fe3+ doping causes smaller resistance and in-
2.8–3.0V [3–5]. There are two important parameters which LIC should creases lithium diffusion within the structure. However, the electro-
have in order to have good performance, i.e. (a) higher reversible ca- chemical tests indicated that higher Fe3+ doping lowers its capacity
pacity and lower irreversible capacity; (b) fast lithium ion diffusion. and capability rate [14]. Another metal ion, Zr4+, was successfully
Herein, the selection of anode material is one of the key points to obtain inserted into Ti site [15]. The results demonstrate that Zr4+ substituted-
rapid lithium-ion diffusion. LTO possess smaller particle size than that of pristine LTO, due to lattice
Lithium titanium oxide, Li4Ti5O12 (LTO), is the best candidate for distortion inhibiting the agglomeration and particle growth. Al3+
replacing graphite as an anode material, due to its ability to avoid the doped-LTO were successfully synthesized at various Al3+ atomic con-
formation of solid electrolyte interface (SEI) layer during the first centration (Li4Ti5-xO12Alx x = 0, 0.1, 0.15, and 0.2) using similar
⁎
Corresponding author.
E-mail address: wahy012@lipi.go.id (W.B. Widayatno).
https://doi.org/10.1016/j.est.2020.101480
Received 31 December 2019; Received in revised form 20 April 2020; Accepted 21 April 2020
2352-152X/ © 2020 Elsevier Ltd. All rights reserved.
A. Sohib, et al. Journal of Energy Storage 29 (2020) 101480
method [16]. The decrease of the agglomeration rate was observed as assembled in CR2023 coin cell to observe the electrochemical perfor-
Al3+ concentration increases to some extent. The obtained particle sizes mance of both half-cell dan full-cell LIC. The half cells consisted of the
were around 1 um, with approximately 3.86% capacity loss and co- anode disk and lithium metal (as a counter electrode), which were
lumbic efficiency around 99.8% at the 30th cycle. It is also said that the sandwiched and separated with Celgard as a porous separator. Before
capacity loss was attributed due to the excessive aluminum content. crimped into the coin cell, the array was dropped by aqueous electro-
Lin, et.al once tried to synthesize Li4Ti5-xO12Alx at x = 0.05 through lyte, 1 M LiPF6 dissolved in ethyl carbonate (EC) and ethyl methyl
sol-gel method [17]. The cubic structure morphology with uniformly carbonate (EMC) with ratio 1:1 (v/v). The cell assembling was entirely
fine distributions and high surface area was obtained, with particle size processed in a glove-box fulfilled by Argon gas. For the full cell, anode
of around 300–500 nm. and cathode disks were assembled with the same electrolyte and se-
Indeed, Al-doped LTO has been used successfully for LIB devices and parator.
demonstrated better performances than that of pristine LTO.
Nevertheless, to the best of author knowledge, the study on Al-doped
2.2. Characterisation and electrochemical measurement
LTO synthesis via sol-gel method with low Al concentration for LIC
devices has rarely been discussed. In this article, we report a study on
To analyze the phase formation of the acquired powders, X-Ray
the electrochemical performance of low concentrationAl-doped LTO in
Diffraction (XRD) measurement was conducted using CuKα radiation
order to enhance the performance of LIC. Through the sol-gel method,
with a scanning rate of 0.06°/second. The morphology of the powders
micron-size particles may be attained to adsorb/desorb more Li+and
was probed using Field Emission Scanning Electron Microscope
create more grain boundary in the particles, enabling better Li+ dif-
(FESEM) JEOL 4610, Japan) at 20,000 magnifications. The electro-
fusion. In addition introducing Al3+ into Ti site of LTO may also shrink
chemical performances of half-cell and full-cell LIC were examined by
its structure, which induces higher cycle stability during the full-cell
observing the cyclic voltammetry (CV) and charge-discharge (CD)
performance test.
profile (WBCS 3000 WonATech). The CV of half-cell LICs was con-
ducted at the scan rate of 0.1 - 0.5 mV.s−1 with the cut-off voltage of
2. Experiment
0–2 V, while Charge discharge (CD) at 0.1 C at the same voltage range.
The CV tests were also performed using voltage range of 0.5 – 2.0 V at
2.1. Synthesis of Li4Ti5-xO12Alx (x = 0, 0.025, 0.05, and 0.075) and
various scan rates (1 mV.s−1, 5 mV.s−1, and 10 mV.s−1), while the CD
activated carbon
tests were managed with verified current densities (8, 10, 50, and
100 mA.g−1) at the same voltage range. The cycle stability and co-
In this study, Al-doped lithium titanate, Li4Ti5-xO12Alx (x = 0,
lumbic efficiency of full-cell LIC was observed for 800 cycles at
0.025, 0.05, and 0.075) were synthesized via sol-gel method and la-
50 mA.g−1.
beled as pristine LTO and LTOA 0.025, LTOA 0.05, and LTOA 0.075
respectively. Analytical materials such as CH3COOLi (lithium acetate,
Sigma Aldrich), titanium (IV) butoxide (TBT), and CH3COOAl (alu- 3. Result and discussions
minum acetate, Sigma Aldrich) with the purity of 99.95%, 97%, and
98%, respectively, were used as raw materials. Citric acid (Sigma 3.1. XRD analysis
Aldrich) was utilized as a chelating agent as well. To prepare 5 g of Al-
doped LTO, each raw material was stoichiometrically weighed, dis- The structure of the synthesized powders was initially confirmed
solved, and stirred (250 rpm) in 15 mL ethanol (Merck, 98%) at room using XRD. Fig. 1 displays the diffraction patterns of (a) pristine LTO,
temperature for 45 min. The lithium acetate, citric acid, and aluminum (b) LTOA 0.025, (c) LTOA 0.05, and (d) LTOA 0.075, obtained with
acetate solutions were then poured into the TBT solution and stirred scan speed of 2.0°/min using CuKa wavelength (1.541862 Å). The peaks
continuously to obtain a gel phase. The wet gel was then dried at 80 °C of spinel-LTO structure in Fd3m group appear at 2θ around 18.34°,
for 12 h. Afterward, the dried gels were calcined at 800 °C for three 35.58°, 43.23°, 47.36°, 57.20°, 62.83°, and 66.07° which is equivalent
hours with a heating rate of 5 °C/min in atmospheric environment to with (111), (311), (400), (331), (333), (440), and (531) crystal planes,
obtain the LTO powder. respectively (PDF Card No.: 00–049–0207). However, impurity as ob-
In order to get full cell assembly, the activated carbon (AC) from served in pristine LTO and LTOA 0.025 samples are perceived through
corncob was utilized as the cathode. The corncobs were initially washed peaks at 2θ angles around 27.4°, 36.03°, 41.36°, and 54.28°, which is
and dried in order to remove the impurities as well as decrease the indexed to rutile-TiO2 (PDF Card No.: 00–021–1276).
water content, which then followed by grinding process. The corncob Further investigations were also conducted at the highest peak, at
powders were then carbonized at 600 °C with a heating rate of 10 °C/ 18°−18.5°, which is correlated to the (111) crystal plane. It is clearly
min for 30 min in the Argon atmosphere (flow rate of 200sccm). The
carbon cob was impregnated using 2 M KOH at room temperature for
24 h. Afterward, the mixture was evaporated at 120 °C and activated at
700 °C with a heating rate of 10 °C /min for 1 h in the nitrogen at-
mosphere (flow rate of 350 sccm). The process was continued by the
washing process using diluted HCl and water and drying at 100 °C. The
obtained AC possesses a surface area of 667.84 m2.g−1 (measured by
N2-physisorption test).
The anode (LTO or Al-doped LTO) and cathode (activated carbon)
films were fabricated by mixing the active material, binder
(Polyvinylidene Fluoride, PVDF), and Super-P (conducting agent), re-
spectively with the ratio of 8:1:1. The materials were blended into N,N
Dimethyl Acetamide (DMAC) until forming a slurry. By utilizing the
Automatic Coater Film machine, the slurry was cast with 200 µm in
thickness on current collectors, namely Cu-foil for anode and Al-foil for
the cathode. The coated films, both anode and cathode, were dried at
80 °C for 12 h and shaped into 16 mm-diametric disks. The active Fig. 1. The diffraction pattern of pristine LTO and LTOA featured with peak
materials (LTO/LTOA powder and AC) in the disk form were then magnification at 18.0°–18.5°.
2
A. Sohib, et al. Journal of Energy Storage 29 (2020) 101480
Table 1 at secondary electron image (SEI) modes. From the images, it can be
Lattice parameter of pristine LTO LTOA 0.025, LTOA 0.05, seen that LTO and LTOA 0.025 have significantly different particles.
and LTOA 0.075. LTOA 0.025 has homogeneous particle distribution with size of ap-
Sample Lattice Parameter (Å) proximately 140 nm, which is much smaller than that of pristine LTO.
These results have similarities to the LTO sample synthesized using the
LTO 8.3620 same method by Lin, et.al. [17]. The smaller particles of LTOA 0.025
LTOA 0.025 8.3570
sample may be established through a reaction among the high-acidity
LTOA 0.05 8.3520
LTOA 0.075 8.3530 mixture solution and chelating agent suggesting faster kinetic reactions.
Moreover, the aluminium environment in the reaction may affect fast
grain formation [22]. These submicron particles of LTOA samples leads
observed that the peaks of LTOA 0.025, LTOA 0.05, and LTOA 0.075 more grain boundary which facilitate Li+ to diffuse.
samples shift to higher angle than that of pristine LTO. These shifts are
the effect of the Al substitution on Ti site even more some references 3.3. The effect of doping Al3+ on half-cell performance
state that this phenomenon can be an indication that Al3+ doping has
been successfully substituted into LTO structure [9,18]. In addition to Electrochemical performance analysis of the half cells was carried
the peak shift, the substitution of Al can cause the lattice parameters of out using cyclic voltammetry measurement in the voltage range of 0.5 -
the LTO structure become smaller than that of pristine LTO, as listed in 2.5 V at a scan rate of 0.1 mV.s−1. Fig. 4 represents the electrochemical
Table 1 and schematically shown in Fig. 2. profile of each cell. From the voltammogram, the pairs of oxidation and
In the spinel LTO structure, lithium, titanium, and oxygen respec- reduction peaks can be observed that each sample possesses a reversible
tively infest 1/6 of 16d sites, 5/6 of 16d sites, and 32e sites [18]. system. The oxidation peaks are established at the voltage of 1.7–1.8 V,
Nevertheless, the amount of titanium in LTOA sample is diminished as while the reduction peaks are in the voltage range of 1.3–1.4 V voltage.
stoichiometric calculation, thereby it permits some vacancies on certain The voltages approach the theoretical LTO voltage around 1.55 V [18].
titanium sites to which Aluminium ion may replace. The replacement Some literatures reported that these peak pairs address to the process of
can cause the shorter lattice parameter LTO due to the radius of Al3+ intercalation and deintercalation of Li+within the cells [12,23,24]. The
(0.053 nm) which is smaller than that of Ti4+ (0.0605 nm). Shorter half-cell based LTOA 0.025 perform the sharpest peak, as shown in inset
lattice parameters facilitate the movement of lithium ions during the Fig. 4(a). The sharpness of reduction and oxidation peaks reveal the
intercalation and de-intercalation process [19]. In other words, this electrochemical kinetic in the electrode [25]. From this measurement, it
property enables such a shorter path way for Li+ mobility that Li+ can be concluded that the substitution of Al3+ at Ti site does not change
could deeply transmigrate into structure of LTO, suggesting increase its the electrochemical reversibility of the cell. In addition, small amount
capacity. The lattice compression due to the existence of Al3+ within of Al3+ doping (i.e. 0.025 mol) can increase cell storage capacity.
the structure is correlated to the high energy bonding of the structure To further probe the performance comparison, the LTO and LTOA
[20]. This mechanism is also confirmed by the simulation and calcu- 0.025, half-cell were selected for CV test at various scan rates, 0.1 -
lation results of Tsai et.al., which demonstrated that the introduction of 0.4 mV.s−1 in the voltage range of 0.5 −2.0 V, as displayed in
Al doping into Ti 16d exhibits higher reaction energy than that of other Figs. 4(b) and (c). It is clearly shown that the current response of re-
metals doping such as Na, K, Mg, Ca, and Sr [21]. This property may duction peaks at both LTO and LTOA 0.025 cell is linearly reinforcing as
avoid the structure degradation during charging-discharging process. the increasing scan rate. These measurements provide the kinetic-re-
action information of Li+during the intercalation and de-intercalation
3.2. Morphology of pristine LTO and LTOA 0.025 process. Furthermore, the charge-discharge (CD) testing was carried out
at current rate of 0.1 C in voltage range of 0.5–2.5 V, as displayed in
In addition to the phase analysis of the synthesized powders, the Fig. 4(d). The plateau voltage of each cells is about 1.55 V, which is
morphology of LTO and LTOA 0.025 powders were captured using Field similar with that of LTO working voltage [18]. The LTOA 0.025 half-
Emission Scanning Electron Microscope (FESEM, JIB-4610F Multi Beam cell possess the highest capacity in this study (154.5 mAh/g) while the
System) with magnification of 20,000 times. Fig. 3(a) and (b), respec- capacity of LTO, LTOA 0.05, and LTOA 0.075 half-cells are
tively display the morphology of pristine LTO and LTOA 0.025 powder 139.7 mAh.g-1, 130.5 mAh.g-1, and 82.1 mAh.g-1, respectively.
3
A. Sohib, et al. Journal of Energy Storage 29 (2020) 101480
Fig. 3. Morphology of (a) LTO and (b) LTOA 0.025 in 20,000 magnification.
Fig. 4. Electrochemical profile of LTO and LTOA half-cell, (a–c) CV measurement at different scan rate of 0.1 – 0.5 mVs−1, and (d) charge-discharge performance at
0.1 C in the voltage range of 0.5–2.5 V.
3.4. Full-cell electrochemical performance rate in the range of 1–10 mV.s−1. By considering the area inside the
curve line, the LIC capacitance can be mathematically calculated using
In addition of the half-cell performances, the electrochemical per- Eq. (1) and (2) [26],
formance of full cell LIC is carried out by using CV and CD measure-
ment. The lithium ion capacitors (LICs) consist of activated carbon (AC) Ce (F ) = (1/ΔV ) v ∫ I (V ) dV (1)
as cathode, LTO and LTOA 0.025 as the anode, as well as LiPF6 as the
electrolyte. Figs. 5(a) and (b) respectively present CV profiles of full-cell Ccell = (Ce / mA) + (Ce / mC ) (2)
LIC with LTO and LTOA 0.025 as an anode at room temperature mea-
Where Ce, ΔV, v, and I respectively represent electrode capacitance
surement, with a voltage range of 0.5 - 2.00 volt V, and various scan
(F), voltage (V), scan rate (V.s−1), and current (A), while Ccell, mA, and
rate of 1 mV.s−1, 5 mV.s1, and 10 mV.s1. The oxidation and reduction
mC respectively expresses LIC cell specific capacitance (F.g−1), anode-
peak cannot be observed in the voltammogram, indicating that the cell
material weight (g), and cathode-material weight (g). Fig. 5(c) reveals
is no longer resembles the typical performance curve of lithium ion
that the specific capacitances of LIC based LTO and LTOA 0.025 at
batteries as stated by other references. The current responses of each
various scan rate, 1 mV.s−1, 5 mV.s−1, and 10 mV.s−1, respectively.
cells are slightly enhanced, suggesting the fast reactions [8], and the
The calculated specific capacitances of LIC based LTO are presented as
areas between forward and reverse scan are expanded as various scan
17.3 F.g−1, 9.6 F.g−1, and 8.4 F.g−1, while the specific capacitances of
4
A. Sohib, et al. Journal of Energy Storage 29 (2020) 101480
Fig. 5. (a) and (b) Voltammogram full LIC based AC//LTO and LTOA 0.025 respectively with scan rate 1 mV.s−1, 5 mV.s−1, and 10 mV.s−1, (c) Specific capacitance
LIC at various scan rate, (e) Charge-Discharge profile of the full cell LIC at various specific current of 8 mA.g−1 - 100 mA.g−1, and (f) Capacity retention and
Columbic efficiency with specific current of 50 mA.g−1.
LIC based LTOA 0.025 are 20.7 F.g−1, 15.5 F.g−1, and 12.8 F.g−1. During charging-discharging process, all samples have a significant
Doping 2.5% Al3+ into Ti site can provide higher specific capacitance increase and decrease in voltage range 0.5–1.5 V, in which the inter-
than that of LTO. However, the capacity of each cell has been declined calation and de-intercalation process of Li+ ions come out/into the LTO
as the scan rate is increasing. At slow scan rate, the ion moves quite structure in the voltage 1.5 V [28]. The other mechanism is observed at
slowly during the charging process, suggesting the ions enable to 1.5–2.0 V, in which Li+/PF6− adsorption-desorption on the electrode
transmigrate into the deepest site on the electrode structure. Con- surface, especially on the porous carbon surface. This phenomenon
versely, at fast scan rate, the ion will move quickly and be inconvenient indicate an imbalance of reaction kinetic between Li+ and capacitive
to reach the profound pore in the electrode structure. These may affect electrode intercalation [29]. To investigate the retention stability, LICs
the cell storage capacity at higher scan rates compared to the one at low based anode LTO and LTOA 0.025 are also tested for charge-discharge
scan rates [27]. at current rate of 50 mA.g−1 in the voltage range 0.5–2.0 V for 800
Fig. 5(d) and (e) shows other performance analysis of the LIC, cycles as well. Fig. 5(f) shows retention and columbic efficiency, where
namely charge-discharge analysis at various current densities, the sample LTOA 0.025 loses capacitance 16.1% after 800 cycles while
8 mA.g−1, 10 mA.g−1, 50 mA.g−1, and 100 mA.g−1 in voltage range the LTO cell loses 70.9%. It can be noted that the cell based LTOA 0.025
0.5–2.0 V. The charge-discharge profile exhibit that the charging-dis- has a much better life cycle performance than that of cell based LTO.
charge time of each cell decreases with increasing current rate that is Better LIC reversibility during the cycling process refers to the cell
loaded during measurement. Besides, the profile also delivers diverse based 0.025 LTOA, designated from stable columbic efficiency which
mechanism in voltage range of 0.5–2.0 V. It represents two mechan- close to 100% starting from the first cycle to the last cycle.
isms, intercalation and de-intercalation as well as adsorption-deso-
rption, that occur inside of LIC during charging-discharging process.
5
A. Sohib, et al. Journal of Energy Storage 29 (2020) 101480