li4ti5o12 via electrospinning
TRANSCRIPT
1
Li4Ti5O12 via Electrospinning
Antonio Susanna25/03/11
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Li4Ti5O12 (LTO) performances.
Structure and intercalation behaviour of LTO.
LTO production by electrospinning.
•Redox reaction ***** and LiNO3
•****** of starting solution with the help of ****.
Results and discussion.
Outlook.
Index.
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0.4 V+53 %+260 %Li4.4Snβ-Sn
0.3 V+60 %+311 %Li4.4SiSi
1.5 V0.0 – 0.1 %0.0 – 0.3 %Li7Ti5O12Li4Ti5O12
0.1 V+4.2 %+13.1 %1/6 LiC6C (graphite)
Li-insertion
3.8 V-0.9%-2.8 %Li0.5NiO2LiNiO2
4.0 V-2.5 %-7.3 %Mn2O4LiMn2O4
3.4 V-2.2 %-6.5 %FePO4LiFePO4
4.0 V0.6 %+1.9 %Li0.5CoO2LiCoO2
Li-extraction
Potential vs. Li/Li+
Linear strain[a]
∆L/L0
Volume strain ∆V/V0
Limitingcomposition
Lithium-storagecompound
Yukinori Koyama, Timothy E. Chin, Urs Rhyner, Richard K. Holman, Steven R. Hall. Advance functional material. 2006. 16, 492–498
Why does L4Ti5O12 use?
Cycling-life of 5000
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Li4Ti5O12 (Fd-3m) cubic, spinel phase
Martin Wilkening, Wojciech Iwaniak,Jessica Heine. Phys. Chem. Chem. Phys., 2007, 9, 6199–6202 | 6199.
16d
8a16c
5Erin M. Sorensen Chem. Mater., Vol. 16, No. 26, 2004
[Li(1+x/3)]8a/16c[Li1/3Ti5/3]16dO432e {0 ≤ x ≤ 3}
Li4Ti5O12 {x = 0} ↔ Li7Ti5O12 {x = 3}
Ti4+ ↔ Ti3+
Li7Ti5O12 became a metallic electron structure (Ti-3d )
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Li4Ti5O12 ↔ Li7Ti5O12 ↔ Li8.5Ti5O12 ↔ Li10Ti5O12
x = 0 → x = 3 → x = 4.5 → x = 6
8a sites full → 16c sites full → 16c sites full and 8a half full → 16c and 8a completed
Martin Wilkening, Wojciech Iwaniak,Jessica Heine. Phys. Chem. Chem. Phys., 2007, 9, 6199–6202 | 6199.
Further intercalation
175 mAh/g (0.3 %)
260 mAh/g (0.4 %)
[Li(1+x/3)]8a/16c[Li1/3Ti5/3]16dO432e
712.31Needle voltage [KV]
-1.68Collector voltage [KV]
**Distance needle-collector [cm]
35Feeding rate [ml/h]
valourParameters
Electrospinning set-up
8
9
10
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****:EtOH=6.6:15 wt % BzOH:****=77:0.92 wt %
****** CH3-O-CH3
**** (MtOH) 3- 4%
+
1.
2.
Centrifugation (7000 rpm for 5 min.)
Powder Dissolution in ****
3.
I method by *********.
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I Holder****/HOiPr
Drying up
Calcination at 800 °C for 8 h.Calcination at 800 °C for 8 h.Calcination at 800 °C for 8 h.
Drying up
Calcination at 800 °C for 8 h.
Drying up Drying up
II Holder*****/HOiPr/ ****(10wt%)
Advantage: stoichiometric ratio.
II method.
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1 5 20 25 30 35 40 45 5 0 55 60 65 70 75 80 85 90
0
1 0000
2 0000
30000
40000
5 0000
60000
70000
80000
(551
)(4
44)
(533
)
(531
)
(311)
(440)
(511)
(331)
(400)
(222
)
(311)
Inte
nsit
y
Theta (°)
Li4Ti
5O
12 (111)
calculated from ICSD using POWD-12++ (1997)
(800 °C)
Unit cell volume 577 Å3
Position [°2Theta] (Copper (Cu))20 30 40 50 60 70 80
Peak List
Li1.333 Ti1.667 O4
Ti O2
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A1g +Eg +3F2g
Guofeng Yana, Haisheng Fanga, Huijuan Zhaob, Journal of Alloys and Compounds 470 (2009) 544–547
b)
200 400 600 800 1000 1200 1400
(273
)
(741
)
(672
)
(432
)
(353
)
Inte
nsity
[a.u
.]
Raman shift [cm-1]
(233
)a)
F2g
A1gEgF2g
F2g
Raman spectroscopy
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0.6 0.8 1 .0 1 .2 1 .4 1 .6 1 .8 2 .0 2 .2 2 .4
-0.2
-0.1
0.0
0.1
0.2
0.3
0.4
0.5
I cycle
C e ll vo ltage (V vs . L i)
Cu
rre
nt
(mA
/g)
1.65
1.63
1.38
1.36
1.53
II cycle
M. Ganesan & M. V. T. Dhananjeyan & K. B. Sarangapani & N. G.Renganathan J Electroceram (2007) 18:329–337
Cyclic voltammmetry (0.1 mVs-1)
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Thank you for attention.
17•M.R. Mohammadi, D. J. Fray. Sol-gel Technol., 2010, 55 19-25.
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Cubic-Li2TiO3
Cubic-Li2TiO3 +
monoclinic-Li2TiO3
Cubic-Li2TiO3 +
monoclinic- Li2TiO3
Cubic-Li2TiO3 + monoclinic-Li2TiO3
75:35
Rutile + monoclinic
Li2TiO3
Rutile + monoclinic-Li2TiO3
Rutile + monoclinic-Li2TiO3
Anatase + monoclinic-Li2TiO3
50:50
Rutile + Li4Ti5O12
Rutile + Li4Ti5O12Rutile + Li4Ti5O12Brookite25:75
800 °C600 °C500 °C400 °CPowder
[Li:Ti(mol%mol%)]
• M.R. Mohammadi, D. J. Fray. Sol-gel Technol., 2010, 55 19-25.