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Li 4 Ti 5 O 12  via Electrospinning Antonio Susanna 25/03/11
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Yukinori Koyama, Timothy E. Chin, Urs Rhyner, Richard K. Holman, Steven R. Hall. Advance functional material.  2006 .  16 , 492–498   Why does L 4 Ti 5 O 12  use? Cycling-life of 5000 0.4 V +53 % +260 % Li 4.4 Sn β-Sn 0.3 V +60 % +311 % Li 4.4 Si Si 1.5 V 0.0 – 0.1 % 0.0 – 0.3 % Li 7 Ti 5 O 12 Li 4 Ti 5 O 12 0.1 V +4.2 % +13.1 % 1/6 LiC 6 C (graphite) Li-insertion 3.8 V -0.9% -2.8 % Li 0.5 NiO 2 LiNiO 2 4.0 V -2.5 % -7.3 % Mn 2 O 4 LiMn 2 O 4 3.4 V -2.2 % -6.5 % FePO 4 LiFePO 4 4.0 V 0.6 % +1.9 % Li 0.5 CoO 2 LiCoO 2 Li-extraction Potential  vs. Li/Li + Linear strain [a] ∆ L/L 0 Volume strain  ∆ V/V 0 Limiting composition Lithium-storage compound
Li 4 Ti 5 O 12  (Fd-3m) cubic, spinel phase Martin Wilkening, Wojciech Iwaniak,Jessica Heine. Phys. Chem. Chem. Phys.,  2007 , 9, 6199–6202 | 6199.   16d 8a 16c
Erin M. Sorensen Chem. Mater., Vol. 16, No. 26,  2004 [Li (1+x/3) ] 8a/16c [Li 1/3 Ti 5/3 ] 16d O 4 32e  {0 ≤ x ≤ 3} Li 4 Ti 5 O 12  {x = 0} ↔ Li 7 Ti 5 O 12  {x = 3} Ti 4+  ↔ Ti 3+ Li 7 Ti 5 O 12  became a metallic electron structure (Ti-3d )
Li 4 Ti 5 O 12  ↔ Li 7 Ti 5 O 12  ↔ Li 8.5 Ti 5 O 12  ↔ Li 10 Ti 5 O 12 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 [Li 1/3 Ti 5/3 ] 16d O 4 32e
Electrospinning set-up 12.31 Needle voltage [KV] -1.68 Collector voltage [KV] ** Distance needle-collector [cm] 35 Feeding rate [ml/h] valour Parameters
 
 
 
****:EtOH=6.6:15 wt % BzOH:****=77:0.92 wt % ****** CH 3 -O-CH 3   **** (MtOH) 3- 4% + 1. 2. Centrifugation  (7000 rpm for 5 min.) Powder Dissolution in **** 3. I method by *********.
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  Drying up  Drying up   II Holder *****/HOiPr/ ****(10wt%) Advantage: stoichiometric ratio. II method . Calcination at 800 °C for 8 h .
calculated from ICSD using POWD-12++ ( 1997 )   (800 °C) Unit cell volume 577  Å 3
A 1g  +E g  +3F 2g   Guofeng Yana, Haisheng Fanga, Huijuan Zhaob,  Journal of Alloys and  Compounds 470 ( 2009 ) 544–547  b) Raman spectroscopy 200 400 600 800 1000 1200 1400 (273) (741) (672) (432) (353) Intensity [a.u.] Raman shift [cm -1 ] (233) a) F 2g A 1g E g F 2g F 2g
M. Ganesan & M. V. T. Dhananjeyan & K. B. Sarangapani & N. G.Renganathan J Electroceram ( 2007 ) 18:329–337 Cyclic voltammmetry (0.1 mVs -1 )
Thank you for attention.
[object Object]
[object Object],Cubic-Li 2 TiO 3 Cubic-Li 2 TiO 3  + monoclinic-Li 2 TiO 3 Cubic-Li 2 TiO 3  + monoclinic- Li 2 TiO 3 Cubic-Li2TiO3 + monoclinic-Li 2 TiO 3 75:35 Rutile + monoclinic Li 2 TiO 3 Rutile + monoclinic-Li 2 TiO 3 Rutile + monoclinic-Li 2 TiO 3 Anatase + monoclinic-Li 2 TiO 3 50:50 Rutile + Li 4 Ti 5 O 12 Rutile + Li 4 Ti 5 O 12 Rutile + Li 4 Ti 5 O 12 Brookite 25:75 800 °C 600 °C 500 °C 400 °C Powder  [Li:Ti(mol%mol%)]

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Li4Ti5O12 via electrospinning

  • 1. Li 4 Ti 5 O 12 via Electrospinning Antonio Susanna 25/03/11
  • 2.
  • 3. Yukinori Koyama, Timothy E. Chin, Urs Rhyner, Richard K. Holman, Steven R. Hall. Advance functional material. 2006 . 16 , 492–498 Why does L 4 Ti 5 O 12 use? Cycling-life of 5000 0.4 V +53 % +260 % Li 4.4 Sn β-Sn 0.3 V +60 % +311 % Li 4.4 Si Si 1.5 V 0.0 – 0.1 % 0.0 – 0.3 % Li 7 Ti 5 O 12 Li 4 Ti 5 O 12 0.1 V +4.2 % +13.1 % 1/6 LiC 6 C (graphite) Li-insertion 3.8 V -0.9% -2.8 % Li 0.5 NiO 2 LiNiO 2 4.0 V -2.5 % -7.3 % Mn 2 O 4 LiMn 2 O 4 3.4 V -2.2 % -6.5 % FePO 4 LiFePO 4 4.0 V 0.6 % +1.9 % Li 0.5 CoO 2 LiCoO 2 Li-extraction Potential vs. Li/Li + Linear strain [a] ∆ L/L 0 Volume strain ∆ V/V 0 Limiting composition Lithium-storage compound
  • 4. Li 4 Ti 5 O 12 (Fd-3m) cubic, spinel phase Martin Wilkening, Wojciech Iwaniak,Jessica Heine. Phys. Chem. Chem. Phys., 2007 , 9, 6199–6202 | 6199. 16d 8a 16c
  • 5. Erin M. Sorensen Chem. Mater., Vol. 16, No. 26, 2004 [Li (1+x/3) ] 8a/16c [Li 1/3 Ti 5/3 ] 16d O 4 32e {0 ≤ x ≤ 3} Li 4 Ti 5 O 12 {x = 0} ↔ Li 7 Ti 5 O 12 {x = 3} Ti 4+ ↔ Ti 3+ Li 7 Ti 5 O 12 became a metallic electron structure (Ti-3d )
  • 6. Li 4 Ti 5 O 12 ↔ Li 7 Ti 5 O 12 ↔ Li 8.5 Ti 5 O 12 ↔ Li 10 Ti 5 O 12 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 [Li 1/3 Ti 5/3 ] 16d O 4 32e
  • 7. Electrospinning set-up 12.31 Needle voltage [KV] -1.68 Collector voltage [KV] ** Distance needle-collector [cm] 35 Feeding rate [ml/h] valour Parameters
  • 8.  
  • 9.  
  • 10.  
  • 11. ****:EtOH=6.6:15 wt % BzOH:****=77:0.92 wt % ****** CH 3 -O-CH 3 **** (MtOH) 3- 4% + 1. 2. Centrifugation (7000 rpm for 5 min.) Powder Dissolution in **** 3. I method by *********.
  • 12. 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 Drying up Drying up II Holder *****/HOiPr/ ****(10wt%) Advantage: stoichiometric ratio. II method . Calcination at 800 °C for 8 h .
  • 13. calculated from ICSD using POWD-12++ ( 1997 ) (800 °C) Unit cell volume 577 Å 3
  • 14. A 1g +E g +3F 2g Guofeng Yana, Haisheng Fanga, Huijuan Zhaob, Journal of Alloys and Compounds 470 ( 2009 ) 544–547 b) Raman spectroscopy 200 400 600 800 1000 1200 1400 (273) (741) (672) (432) (353) Intensity [a.u.] Raman shift [cm -1 ] (233) a) F 2g A 1g E g F 2g F 2g
  • 15. M. Ganesan & M. V. T. Dhananjeyan & K. B. Sarangapani & N. G.Renganathan J Electroceram ( 2007 ) 18:329–337 Cyclic voltammmetry (0.1 mVs -1 )
  • 16. Thank you for attention.
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  • 18.