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Synthesis and Characterization of Lithium Titanate (Li Ti O) Nanopowder For Battery Applications
Synthesis and Characterization of Lithium Titanate (Li Ti O) Nanopowder For Battery Applications
Synthesis and Characterization of Lithium Titanate (Li Ti O) Nanopowder For Battery Applications
https://doi.org/10.1007/s10854-018-9895-1
Abstract
Nanostructured lithium titanate (Li4Ti5O12) nanopowder was successfully synthesized by simple peroxide route using titanium
oxysulphate and lithium hydroxide. The structural properties of the as-prepared and sintered powders were characterized
by using powder X-ray diffraction, Fourier transform infrared spectroscopy, Raman spectroscopy. Surface morphological
property was studied by scanning electron microscope. Compositional analysis was studied using X-ray photo electron
spectroscopy. The thermal degradation behavior of the as-synthesized materials was analyzed by thermo gravimetric analy-
sis (TG–DTA). The electrochemical properties of the Li4Ti5O12 nanopowders were examined using galvanostatic charge/
discharge test. The effect of sintering temperature on its various physical properties and the electrochemical performances
of Li4Ti5O12 was investigated. The storage capacity value obtained for Li4Ti5O12 and L i4Ti5O12/graphite composite anode
was 83.52 and 91.33 mAhg−1 in 1 M LiPF6 at 0.1 mA.
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[15–19] which is higher reduction potential of most organic technique in the range of 4000–400 cm−1. The particle size
electrolytes, showing good capacity preservation potential was measured by Microtrac S3500 particle size analyzer.
compared with other graphite based anode materials. How- Micro Raman analysis of our samples was carried out using
ever, owing to its low electrical conductivity, the lithium the Princeton Acton SP250, Raman spectrometer wave
titanate anodes exhibit a poor rate capability. The invention length 532 nm. Thermogravimetric analysis (TG/DTA) was
of Li4Ti5O12 anode material is inexpensive environment- carried out using a Rigaku Thermo plus TG8120 analyzer
friendly to the society [20–26]. The lithium titanate have under air flow condition with a ramping rate of 10 °C min−1.
been prepared by several methods such as hydrothermal, The SEM–EDX was observed using JEOL JSM-6360LV at
electrospinning, sol–gel process [27–29], spray pyrolysis an accelerating voltage of 30.0 kV. X-ray photoelectron
water burning [30], microwave synthesis [31–33], solid sate spectroscopic analysis (XPS) (VG Scientific ESCALAB
reaction [34, 35], solvothermal process [36] and computa- 210; Mg-Ka, 15 kV, 18 mA) was also carried out for the
tional methods [37, 38]. In this study, we report the prepara- sintered samples.
tion of lithium titanate nanopowder by peroxide route. The
reported method is promising alternate to prepare materials 2.3 Fabrication of electrodes
for large scale applications.
1.3504 g of lithium titanate and 0.9079 g of carboxyme-
thyl cellulose (CMC) were taken in the porcelain dish and
2 Experimental section mixed well with few drops of distilled water. 0.0966 g of
polyvinyldene fluoride (PVDF) binder was also added into
2.1 Material preparation the above mixer and then the mixture was homogeneously
mixed manually with the aid of spatula. The paste is coated
All chemicals were of analytical grade and used without any on the aluminum foil substrate using the doctor blade tech-
further purification. The chemicals used during synthesis nique. Then the electrode was dried in oven at 75 °C for 1 h.
were titanium oxysulfate (TiOSO4·xH2O, > 29% Sigma- Lithium foil was used as counter electrode and polypropyl-
Aldrich, USA), lithium hydroxide monohydrate (LiOH·H2O, ene was used as the separator. 1 mol l−1 LiPF6 was dissolved
99% Himedia, Mumbai, India), hydrogen peroxide [H2O2, in a mixture of ethylene carbonate, dimethyl carbonate and
30–32% Nice Chemical (P) Ltd, Kerala, India]. The lithium diethyl carbonate (EC: DMC: DC = 1:1:1 v/v) and used as
titanate was prepared by solution growth technique. Firstly, the electrolyte. The cell was assembled inside the glove box
the titanium oxysulfate (TiOSO4·xH2O) was dissolved in 1:1 under the argon atmosphere. Galvanostatic charge/discharge
ratio (20 ml) double distilled water and ethanol solution. cycle test was carried out for all the assembled cells at ambi-
The lithium hydroxide monohydrate (LiOH·H2O) solution ent temperature with constant current mode (0.1 mA) up to
was prepared by dissolving it in the similar ratio of water 1.5 V for charging and up to 2 V for discharging.
and ethanol. Then, the lithium hydroxide solution was added
into the prepared titanium oxysulfate solution. The reaction
mixture was continuously stirred for 2 h and subsequently 3 Results and discussion
a white color colloidal mixture was obtained. Further, one
drop of assay 30% H2O2 was added into the colloidal mix- 3.1 Thermogravimetric analysis
ture and it ultimately end up with a formation of yellow
color precipitate. Then, the obtained yellow precipitate was The dehydration process of the lithium titanate nanopow-
washed with deionized water for several times to remove the der was monitored by Thermogravimetric analysis. Figure 1
unreacted chemical species in the mixture. The precipitate shows TG/DTA curve of as prepared sample. From the TG
was collected and dried at 80 °C for 6 h in hot air oven. curve, the first weight loss about 15.8% occurred between
Finally, synthesized powders were sintered at 700 °C for 1 h, room temperature and 185 °C, presenting endothermic peak
2 h, 3 h, and 4 h and the samples are denoted as LT1, LT2, at 72.47% (DTA). The weight loss was mainly attributed due
LT3 and LT4, respectively. to the removal of moisture/water molecules from the sample.
In the temperature range from 185 °C to 345 °C, a further
2.2 Materials characterization weight loss about 11% corresponding to the exothermic peak
at 120 °C in the DTA curve, is due to the volatilization of
The X-ray diffraction (XRD) studies of all the samples were carbon present in the ethanol. Further, progressive phase
analysed using (Xpert-PRO PANalytical) X-ray diffractom- transformation from orthorhombic to cubic spinel LTO was
eter with monochromatic CuKα—radiation (λ = 1.5406 Å). accompanied by 5% of weight loss which is associated with
FT-IR spectra of the sample was recorded on a (Thermo an exothermic peak at 440 °C in the DTA curve. A weight
Nicolet 380, USA) spectrometer using a KBr pellet loss (6%) of L
i4Ti5O12 by solid state reactions was observed
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Journal of Materials Science: Materials in Electronics
Fig. 2 XRD patterns of samples calcined at 700 °C for (a) 1 h, (b) Fig. 3 FT-IR spectra of samples calcined at 700 °C for (a) 1 h, (b)
2 h, (c) 3 h and (d) 4 h 2 h, (c) 3 h and (d) 4 h
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Journal of Materials Science: Materials in Electronics
(–OH) in the samples [42]. It should be indicated that the shows that the particles are arranged homogeneously. Fig-
appearance of peak corresponds to OH group may be due to ure 5b–d shows the SEM micrographs of LT2, LT3and LT4
the presence of moisture in the sample. samples and it clearly evinces the formation of nanospheres
morphologies. EDX spectra of lithium titanate nanopowder
3.4 Raman spectra were shown in Fig. 6. It clearly point out the presence of
titanium (Ti) and oxygen in an appreciable percentage. The
Figure 4 shows the Raman spectra of the synthesized element of lithium (Li) was not observed, because lithium
Li4Ti5O12 (LTO) samples sintered at 700 °C for 1 h, 2 h, 3 h is light weight metal and it is not possible to detect the pres-
and 4 h. The Raman intensity was gradually increased while ence by EDX spectra. However, the XPS studies clearly
increasing the sintering time from 1 to 4 h. There are four demonstrate the presence of all elements including lithium
vibration peaks observed in the Raman spectrum of lithium metal shown as shown in Fig. 7.
titanate at 672, 423, 235 and 353 cm−1. The first three strong
bands are 672, 423 and 235 cm−1 could be assigned to the
characteristics of A1g, Eg and F2g modes, respectively. The 3.6 XPS spectroscopy
fourth weak intensity peak at 353 cm−1 could be assigned
to the characteristics of F 2g mode. It can be concluded from Figure 7 shows the XPS spectrum of Li4Ti5O12 nanopowder
the above results that the synthesized Li4Ti5O12 is exist in sintered at 700 °C for 4 h. The XPS peaks were observed
the form of spinel structure (A1g + Eg + 2F2g). The charac- at 60.0, 288.3, 462.4, 467.8 and 535.7 eV which are cor-
teristic peak appears at 672 cm−1 indicates the presence of respond to the Li 1 s, Ti 2p, C 1 s and O 1 s, respectively.
the vibrations of Ti–O bonds in octahedral T iO6. The peak XPS result clearly indicates the presence of Li, Ti, C and
at 423 cm−1 indicates the presence of Li–O bonds in the Oxygen elements in LT4 sample. The previous reports
tetrahedral unit of LiO4 and octahedral unit of LiO6. The clearly pointed out the binding energy of Li 1 s, C 1 s cor-
characteristic peaks at 353 and 235 cm−1 could be assigned responds to the peaks at 60.0 eV, 288.3 eV respectively [48,
to the O–Ti–O bending vibration in octahedron TiO6 and 49]. The peak for Ti 2p doublet was observed in the range of
Li–O stretching vibration in LiO6 octahedron unit [43–48]. 462.4–467.8 eV with a spin orbit splitting of 5.4 eV, which
is in excellent concurrence with the results expected for
3.5 SEM and EDX the Ti4+ oxidation state. The spin orbit splitting is 5.5 eV
because Ti 2p doublet peak was observed in the range of
Figure 5 shows SEM micrographs of the synthesized 458.2–467.7 eV which is one of the conformation for the
Li4Ti5O12 samples. Figure 5a shows the SEM micrograph of Ti4+ oxidation state [50, 51]. The presence of oxygen-con-
LT1. Figure 3b shows the SEM image of LT2 and it reveals taining groups on the surface of lithium titanate sample was
the formation of nanospheres with agglomerateted particles. confirmed from the appearance of peak at 535.7 eV which
The sample sintered for 1 h does not show the formation of corresponds to the oxygen. The all elements including Li
nanospheres. Figure 5c shows the SEM image of LT3 and were detected from XPS analysis. Hence, it can be con-
it is clearly shows the nanoporous morphologies. Figure 5d cluded that the formation of lithium titanate is possible from
the simple peroxo solution growth route.
3.7 Cyclic voltammetry
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3.8 Conductivity studies
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Fig. 7 XPS spectrum of L
i4Ti5O12 (i) survey scan (ii) core spectra of (a) Li 1s, (b) Ti 2p, (c) O 1s and (d) C 1s
0.3
0.2
0.1
Current / mA
0.0
-0.1
-0.2
-0.3
-0.4
1.0 1.2 1.4 1.6 1.8 2.0
Potential / V
Fig. 8 Cyclic voltagrametric curve of lithium titanate nanopowder Fig. 9 AC impedance spectrum of lithium titanate nanopowder cal-
calcined at 700 °C for 4 h cined at 700 °C for 4 h
the area of electrodes induced by constant expansion and l is the thickness of the electrode, a is the area of the
contraction during the cycles. It is seen that the increase of electrode, Rb is the bulk resistance of the electrode. The
both Rs and Rct is not severe through the cycling process. conductivity of 2.62 × 10−8 S cm−1 was achieved for the
The conductivity of the L i4Ti5O12 can be calculated from Li4Ti5O12 electrode. This is acceptable value; it may pos-
the following Eq. (1): sible to achieve the better storage capacity for Li4Ti5O12
electrode in LiPF6 medium.
l
𝜎= (1)
Rba
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Journal of Materials Science: Materials in Electronics
a b
2.1 2.2
2.0
2.0 th
----- 4 Cycle
rd
1.9 th ----- 3 Cycle
Voltage (V)
----- 4 Cycle
Voltage (V)
nd
rd
----- 3 Cycle 1.8 ----- 2 Cycle
st
1.8 nd
----- 2 Cycle ----- 1 Cycle
st
----- 1 Cycle
1.7 1.6
1.6
1.4
1.5
0 20 40 -1
60 80 0 20 40 60 80 100
Capacity (mAh g ) Capacity (mAh g )
-1
Fig. 10 Charge –discharge curves of a lithium titanate (calcined at 700 °C for 4 h), b Lithium titanate/graphite modified anodes in LiPF6 electro-
lyte
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14. P.V. Braun, J. Cho, J.H. Pikul, W.P. King, H. Zhang, Curr. Opin. 35. C.Y. Wu, Y.X. Wang, J. Xie, G.S. Cao, T.J. Zhu, X.B. Zhao, J.
Solid State and Mater. Sci. 16, 186 (2012) Solid State Electrochem. 16, 3915 (2012)
15. E.H. Chung, H.J. Han, F.N. Khan, T.E. Hong, H.G. Kim, J.S. 36. Q. Yang, H. Zhao, J. Wang, J. Wang, C. Wang, X. Hou, Mater.
Bae, O.S. Jung, H. Jung, J.P. Kim, J.S. Jin, E.D. Jeong, J. Ceram. Renew. Sustain. Energy. 3, 1 (2014)
Process. Res. 14, 304 (2013) 37. J. Qiu, C. Lai, E. Gray, S. Li, S. Qiu, E. Strounina, C. Sun, H.
16. R. Dhilip Kumar, S. Karuppuchamy, J. Mater. Sci. Mater. Elec- Zhaoa, S. Zhang, J. Mater. Chem. 2, 6353 (2014)
tron. 26, 3256 (2015) 38. T. Kawahara, T. Kuroda, H. Matsui, M. Mishima, S. Karuppu-
17. L.L. Xie, Y.D. Xu, J.J. Zhang, X.Y. Cao, B. Wang, X.Y. Yan, L.B. chamy, Y. Seguchi, M. Yoshihara, J. Mater. Sci. 42, 3708 (2007)
Qu, J. Electro chem. Sci. 8, 1701 (2013) 39. Y. Xia, B. Sun, Y. Wei, B. Tao, Y. Zhao, J. Alloy. Compd. 705, 58
18. H. Matsui, K. Kira, S. Karuppuchamy, M. Yoshihara, Curr. Appl. (2017)
Phys. 9, 592 (2009) 40. Z.H. Asadov, A.H. Tantawy, I.A. Zarbaliyeva, R.A. Rahimov,
19. B. Tian, H. Xiang, L. Zhang, Z. Li, H. Wang, Electrochim. Acta. G.A. Ahmadova, J. Chem. 2, 136 (2012)
55, 5453 (2010) 41. Y. Ren, J. Zhang, Y. Liu, H. Li, H. Wei, B. Li, X. Wang, ACS
20. H. Matsui, T. Kuroda, K. Otsuki, K. Yokoyama, T. Kawahara, Appl. Mater. Interfaces. 4, 4776 (2012)
Tanso. 222, 114 (2006) 42. R. Xu, J. Li, A. Tan, Z. Tang, Z. Zhang, J. Power Sources 196,
21. T. Kawahara, H. Miyazaki, S. Karuppuchamy, H. Matsui, M. Ito, 2283 (2011)
M. Yoshihara, Vacuum 81, 680 (2007) 43. D. Ghosh, S. Giri, S. Sahoo, C.K. Das, Polym. Plast. Technol.
22. H. Matsui, K. Santhi, S. Sugiyama, M. Yoshihara, S. Karuppu- Eng. 52, 213 (2013)
chamy, Ceram. Int. 40, 2169 (2014) 44. W. Liu, Y. Wang, X. Jia, B. Xia, J. Chem. 9, 497654 (2013)
23. W. Wang, J. Tu, S. Wang, J. Hou, H. Zhu, S.S. Jiao, Electrochem. 45. Y. Tang, F. Huang, W. Zha, Z. Liua, D. Wana, J. Mater. Chem. 22,
Acta. 68, 254 (2012) 11257 (2012)
24. M.R. Giuliano, S.G. Advani, A.K. Prasad, J. Power Sources 196, 46. L. Aldon, P. Kubiak, M.C. Womes, J. Jumas, J.O. Fourcade, J.L.
6517 (2011) Tirado, J.I. Corredor, C.P. Vicente, Chem. Mater. 16, 5721 (2004)
25. R. Dhilip Kumar, S. Karuppuchamy, J. Mater. Sci. Mater. Elec- 47. I.A. Leonidov, O.N. Leonidova, L.A. Perelyaeva, R.F. Samigul-
tron. 26, 6439 (2015) lina, S.A. Kovyazina, M.V. Patrakeev, Phys. Solid State 45, 2183
26. H. Matsui, S. Yamamoto, Y. Izawa, S. Karuppuchamy, M. Yoshi- (2003)
hara, Mater. Chem. Phys. 103, 127 (2007) 48. R. Dedryve`re, D. Foix, S. Franger, S. Patoux, L. Daniel, D. Gon-
27. S. Maensiri, W. Nuansing, J. Klinkaewnarong, P. Laokul, J. Khem- beau, J. Phys. Chem. 114, 10999 (2001)
prasit, J. Coll. Int. Sci. 297, 578 (2006) 49. C. Zhang, D. Shao, Q. Gao, Y. Lu, Z. Liu, X. Yu, Y. Fang, D.
28. J.Y. Lin, C.C. Hsua, H.P. Hoa, S. Wu, Electrochem. Acta. 87, 126 Chen, J. Solid State Electrochem. 19, 1859 (2015)
(2013) 50. Z. Ali, S.N. Cha, J.I. Sohn, I. Shakir, C. Yan, J.M. Kim, D.J. Kang,
29. B. Tian, H. Xiang, L. Zhang, H. Wang, J.Solid State. Electrochem. J. Mater. Chem. 22, 17625 (2012)
16, 20 (2012) 51. S. Chen, Y. Xin, Y. Zhou, Y. Ma, H. Zhou, L. Qi, Energy Environ.
30. T. Ogihara, T. Kodera, Materials 6, 2285 (2013) Sci. 7, 1924 (2014)
31. S.L. Chou, J.Z. Wang, H.K. Liu, S.X. Dou, J. Phys. Chem. 115, 52. X. Lou, C. Lin, Q. Luo, J. Zhao, B. Wang, J. Li, Q. Shao, X.
16220 (2011) Guo, N. Wang, Z. Guo, ChemElectroChem. (2017). https://doi.
32. C.T. Hsieh, B.S. Chang, J.Y. Lin, R.S. Juang, J. Alloy.Compd. org/10.1002/celc.201700816
513, 393 (2012) 53. B. Sun, S.J. Bao, J.L. Xie, C.M. Li, RSC Adv. 4, 36815 (2014)
33. R. Dhilip Kumar, S. Karuppuchamy, Ceram. Int. 40, 12397 (2014) 54. B. Sun, S. Mao, S. Zhu, G. Zhou, Y. Xia, Y. Zhao, ACS Appl.
34. J.W. Shin, J.H. Ryu, J. Jeong, D.H. Yoon, J. Electroceram. 28, 178 Nano Mater. 1, 1291 (2018)
(2012)
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