技術会議資料

Size: px

Start display at page:

Download "技術会議資料"

きみえゆのもと
5 years ago
Views:

1 La-Mg-Ni

2 2 H 2 O e - e - H OH - H + e - H H 2 O OH - H + e - O H O Ni Ni O H O H

3 3 La, Pr, Nd, etc. Ni, Co, Mn, Al, etc H/M Equilibrium Hydrogen Pressure MPa (MPa) La Ni Ni + Ni H x + xoh - + xh 2 O + x e-

4 4 AA Energy density (Wh/l) Year 2008

5 La-Mg-Ni Kadir, Sakai 1997 : AB 3.0 -AB 4.0 (A:La, Mg, B:Ni) 1-2 wt.% (CaCu 5 -) La La, Mg Ni Ni + Ni c c c c A 2 B 4 (Laves ) 2:7H (AB 3.5 ) 5:19R (AB 3.8 ) 5 5:19H (AB 3.8 ) 1:4R (AB 4.0 )

6 La-Mg-Ni Voltage (V) La-Mg-Ni La-Pr-Mg-Ni-based alloy MmNi -based alloy (conventional) Discharge capacity (mah/g) M. Kanemoto et al., ECS 208th Meeting, Abstract number 852, Los Angeles (2005). T. Ozaki, M. Kanemoto,T. Kakeya, Y. Kitano, M. Kuzuhara, M. Watada, S. Tanase, and T. Sakai, J. Alloys Compds., , 620 (2007). 6 Discharge capacity (mah/g) La-Mg-Ni-based La-Mg-Ni alloy Conventional AB5 alloy Cycle number

7 7 La-Mg-Ni LaNi La 1-x Mg x Ni y (x = , y = ) Ce, Pr, Nd Co, Mn, Al X

8 8 ( C) X (SPring8 BL19B2 ) XRD : 0.7Å 0.75Å) XAFS ) Rietveld : RIETAN-2000) EPMA

9 Mn,Al La-Mg-Ni La 0.8 Mg 0.2 Ni 3.4-x Co 0.3 (MnAl) x Mass fraction 0% 20% 40% 60% 80% 100% x = 0 x = 0.1 x = :7H 5:19R 5:19H x = 0.2 1:4R x = 0.25 x = 0.4 AB 2 x = 0.15, 0.2 5:19H, 1:4R 9

10 10 Mn,Al La-Mg-Ni La 0.8 Mg 0.2 Ni 3.4-x Co 0.3 (MnAl) x Discharge capacity (mah/g) Cycle number x=0 x=0.15 x=0.25 x=0.4 5:19H x = 0.15

11 11 Mn,La,Ni,Co La 0.8 Mg 0.2 Ni 3.25 Co 0.3 (MnAl) 0.15 Co K Mn K FT Ni K La K R Mn La NiCo Mn NiCo

12 12 La La 0.8 Mg 0.2 Ni 3.25 Co 0.3 (MnAl) 0.15 FT R

13 Ni La 0.8 Mg 0.2 Ni 3.25 Co 0.3 (MnAl) 0.15 FT R 13

14 XAFS LaNiCo La La-Mg-Ni LaNi 5 Ni La LaNi5 La Ni Ni La 14

15 15 La La 0.64 RE 0.2 Mg 0.16 Ni 3.45 Co 0.2 Al 0.15 Potential / V (Hg/HgO) , : 0.2 I t A RE': La RE': Ce RE': Nd RE': Pr Capacity / mah

16 16 La Discharge capacity (mah/g) La 0.64 RE 0.2 Mg 0.16 Ni 3.45 Co 0.2 Al 0.15 RE':La RE':Ce RE':Nd Cycle number RE':Pr 0.1 I t A, 15h 0.2 I t A cut off voltage -0.6V vs. Hg/HgO Pr, Nd- : 50 96% Ce- :

17 17 La La 0.64 RE 0.2 Mg 0.16 Ni 3.45 Co 0.2 Al 0.15 Phase abundancemass% 0% 20% 40% 60% 80% 100% RE': La 2:7H AB2 RE': Ce RE': Pr 5:19R 1:4R 2:7H 5:19R 5:19H 1:4R AB5 RE': Nd 5:19H Pr, Nd :, 2:7H. 5:19H, 5:19R

Pr, Nd Al 5:19R phase A 2 B 4 A 2 B 4 A 2 B 4 RE RE, Mg Ni,Co,Mn,Al 18h1 site M / Al = 0.89 / 0.11 18h2 site M / Al = 0.

18 Pr, Nd Al 5:19R phase A 2 B 4 A 2 B 4 A 2 B 4 RE RE, Mg Ni,Co,Mn,Al 18h1 site M / Al = 0.89 / h2 site M / Al = 0.95 / 0.05 RE = (La, Pr) M=(Ni,Co,Mn) Ni La Ni Ni Ni Al Ni Ni Nd Ni La: Nd: Ni: Al: La Pr Nd c Al Ni 18

19 19 Pr, Nd Pr, Nd Al-poor Al-rich Al Al

20 20 Pr, Nd La-Mg-Ni Particle size after cycle test (µm) (um) Abundance of of ABAB5 5 phase (%) Pr, Nd

21 Ce Ce-LIII XANES Normalized absorption La 0.64 Ce 0.2 Mg 0.16 Ni 3.45 Co 0.2 Al Before hydriding Ce metal 0.8 CeCl CeO After hydriding Energy (ev) : CeO 2 CeCl 3 : Ce 4+ Ce 3+ 21

22 22 La 0.64 RE 0.2 Mg 0.16 Ni 3.45 Co 0.2 Al 0.15 Intensity (a.u.) RE : Nd RE : Ce SPring8 BL19B2 :0.75Å θ (degree) RE' Phases Volume increase V /V (%) Ce :4R :19H :19R :7H Pr 5:19H :19R Nd 5:19H :19R 20.9

23 23 La-Mg-Ni HRTEM 3 c A 2 B 4 3 A 2 B 4 3 A 2 B 4 4 A 2 B 4 4 5:19 1:4 c

24 24 Ce Ce 4+ - Ce :7H 2:7H 2:7H 2:7H 5:19H 5:19H Ce5:19R 1:4R 1:4R 1:4R 1:4R

25 25 La-Mg-Ni Ni Mn,Al 5:19H 350 mah/g La Ni Ni La La Pr,Nd Ce Ce Ce(III) Ce(IV) XRD XAFS

26 26 XRD XAFS SPring8 TEM

PowerPoint プレゼンテーション

PowerPoint プレゼンテーション立命館 SR センター公開シンポジウム軟 X 線分光を用いた二次電池研究の最先端 016.11.11 Li MnO 正極材料の酸素による電荷補償の直接観察大石昌嗣 / Masatsugu Oishi 徳島大学大学院理工学研究部機械科学系エネルギーシステム分野 1 Energy 次世代 LIB: 高電位, 高容量の理解 V (V) W (Wh/kg) Q (Ah/kg) V : 高電位での電気化学