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1 Li 4 Ti 5 O 12 via Electrospinning Antonio Susanna 25/03/11

Li4Ti5O12 via electrospinning

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Page 1: Li4Ti5O12 via electrospinning

1

Li4Ti5O12 via Electrospinning

Antonio Susanna25/03/11

Page 2: Li4Ti5O12 via electrospinning

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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.

Page 3: Li4Ti5O12 via electrospinning

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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

Page 4: Li4Ti5O12 via electrospinning

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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

Page 5: Li4Ti5O12 via electrospinning

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 )

Page 6: Li4Ti5O12 via electrospinning

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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

Page 7: Li4Ti5O12 via electrospinning

712.31Needle voltage [KV]

-1.68Collector voltage [KV]

**Distance needle-collector [cm]

35Feeding rate [ml/h]

valourParameters

Electrospinning set-up

Page 8: Li4Ti5O12 via electrospinning

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Page 9: Li4Ti5O12 via electrospinning

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Page 11: Li4Ti5O12 via electrospinning

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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 *********.

Page 12: Li4Ti5O12 via electrospinning

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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.

Page 13: Li4Ti5O12 via electrospinning

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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

Page 14: Li4Ti5O12 via electrospinning

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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.

Page 17: Li4Ti5O12 via electrospinning

17•M.R. Mohammadi, D. J. Fray. Sol-gel Technol., 2010, 55 19-25.

Page 18: Li4Ti5O12 via electrospinning

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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.