New Perovskite Perovskite Materials Materials as as Components - - PowerPoint PPT Presentation

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New Perovskite Perovskite Materials Materials as as Components Components New of Electrochemical Devices Devices for for Energy Energy of Electrochemical Generation. . Generation Susana Garc a a- -Mart Mart n n Susana

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SLIDE 1

New New Perovskite Perovskite Materials Materials as as Components Components

  • f
  • f

Electrochemical Electrochemical Devices Devices for for Energy Energy Generation Generation. .

Susana Garc Susana Garcí ía a-

  • Mart

Martí ín n Departamento de Qu Departamento de Quí ímica Inorg mica Inorgá ánica, Facultad de nica, Facultad de C.C C.C. Qu . Quí ímicas, micas, Universidad Complutense, Madrid Universidad Complutense, Madrid-

  • 28040, (

28040, (Spain Spain) )

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SLIDE 2

Materials Science

Design and synthesis

  • f materials

Characterization of the crystal structure and microstructure of materials Electrical and electrochemical characterization of materials

Materials Technology

Performance of materials in devices for energy production IT-SOFC Li/Air batteries

slide-3
SLIDE 3

Why perovskite-type materials?

Zr1-xYxO2- La1-xSrxMnO3-δ

Electrolyte Anode Cathode

Cermet

Ba0.5Sr0.5Co0.8Fe0.2O3-δ

Sha o Z., Ha ile S. M., Nature 431, (2004)

BaGdCo2O6-δ

T a ra nc ó n A. e t a l. J. Mater. Chem. 17, (2007)

BaGdMn2O6-δ a nd BaGdCo2O6-δ T

a skin A. A., e t a l. Progress in Solid State

Chemistry 35, (2007), 481. PrBaCo2O6-δ K

im e t a l. J. Mater. Chem. 17, (2007), 2500.

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SLIDE 4

REAM2O5.5

Ba Ba RE RE RE

AA AA’ ’M M2

2O

O6

6-

Layered Layered perovskites perovskites: A : A-

  • cation

cation ordering

  • rdering

A A’ A’

AA’M2O6

  Higher Higher oxygen

  • xygen diffusion

diffusion than than LSM LSM   Better Better catalytical catalytical properties properties than than LSM LSM

slide-5
SLIDE 5
  • rdering
  • rdering effects

effects in in perovskites perovskites SAED, HRTEM SAED, HRTEM and and EELS EELS BaGdCo BaGdCo2

2O

O6

6-

  • δ

δ

BaGdMn BaGdMn2

2O

O6

6-

  • δ

δ

slide-6
SLIDE 6

Ideal Ideal perovskite perovskite ABX ABX3

3

2ap× 2ap × 2ap 2ap× 2ap × 2ap ap× ap × ap

001p 000 111p 100p 110p 010p 011p 001p 000 111p 100p 110p 010p 011p

000

001p 110p 111p

000

001p 110p 111p

slide-7
SLIDE 7

Layered Layered A A-

  • site

site ordering

  • rdering A

AA A’ ’B B2

2O

O6

6

Rock Rock-

  • sal

salt B t B-

  • site

site ordering

  • rdering A

A2

2(

(B BB B’ ’)O )O6

6

ap× ap × 2ap

001p 000 111p 100p 110p 010p 011p 001p 000 111p 100p 110p 010p 011p

000

001p 110p 111p

000

001p 110p 111p 2ap× 2ap × 2ap 2ap× 2ap × 2ap

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SLIDE 8

[ 1 1 ]

p

[001]p

Layered Layered A A-

  • site

site ordering

  • rdering A

AA A’ ’B B2

2O

O6

6

000

001p 110p 111p

ap× ap × 2ap

slide-9
SLIDE 9

BaGdCo BaGdCo2

2O

O6

6-

  • δ

δ

SAED SAED and and HRTEM HRTEM

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SLIDE 10

GdBaCo2O6-

ASR=0.50 Ω/cm2 ASR=1 Ω/cm2 ASR=0.17 Ω/cm2 ASR=0.29 Ω/cm2 ASR=0.047 Ω/cm2 ASR=0.072 Ω/cm2 ASR=0.024 Ω/cm2 ASR=0.039 Ω/cm2

slide-11
SLIDE 11

001p 100p 001p 110p 100p 011p 100p 010p 110p

  • 101p
  • [101]p

[001]p

5 nm

2ap

a ap

p×

× a ap

p ×

× 2a 2ap

p

Ba Ba/ /Gd Gd ordering

  • rdering

GdBaCo2O6- prepared in Ar

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SLIDE 12

3ap 3ap

[001]p

100p 010p 001p 010p 010p 100p

3ap 2ap

a ap

p×

× 3a 3ap

p ×

× 2a 2ap

p

Ba Ba/ /Gd Gd ordering

  • rdering

Anion Anion vacancies vacancies ordering

  • rdering

GdBaCo2O6- prepared in Air

slide-13
SLIDE 13

BaGdMn BaGdMn2

2O

O6

6-

  • δ

δ

SAED, HRTEM SAED, HRTEM and and EELS EELS Powder Powder Neutron Neutron Diffraction Diffraction

slide-14
SLIDE 14

GdBaMn GdBaMn2

2O

O6

6-

  • δ

δ

001p 100p 001p 110p 110p

  • 100p

110p 110p

▬

010p

[100]p [010]p

5 nm 4d110p

[110]p [110]p

  • 4d110p
slide-15
SLIDE 15

GdBaMn GdBaMn2

2O

O6

6-

  • δ

δ

001p 100p 001p 110p 110p

  • 100p

110p 110p

▬

010p

111p 100p 001p 000p 100p 110p 110p

▬ ▬

111p 010p

▬

2ap× 22ap × 4ap P212121

Ba Ba/ /Gd Gd ordering

  • rdering,

, CO (Mn CO (Mn3+

3+/Mn

/Mn4+

4+),

), anion anion vacancies vacancies ordering

  • rdering
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SLIDE 16

630 640 650 660 670 680 690 700

Mn-L2

Intensity (a.u.)

Energy-Loss (eV) Mn-L3

Mn Mn oxidation

  • xidation state

state: 3.24 : 3.24 ± ± 0.06 0.06

BaGdMn BaGdMn2

2O

O5

5.74 .74

BaGd BaGd(0,25Mn (0,25Mn4+

4+0,75Mn

0,75Mn3+

3+)

)2

2O

O5.75

5.75

2.0 2.5 3.0 3.5 4.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5

MnO4 Mn2O3 Mn3O4

Mn L3/L2

Oxidation State

MnO

EELS

2

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SLIDE 17

SmBaMn2O6, TbBaMn2O6

  • M. Uc hida , D. Aka ho shi, R. K

uma i, Y. T

  • mio ka , T

. Arima , T . T

  • kura , Y. Ma tsui, Jo urna l o f the Physic a l

So c ie ty o f Ja pa n, 71, 2002, 2605; T . Arima , D. Aka ho shi, K . Oika wa , T . Ka miya ma , M. Uc hida , Y. Ma tsui, T . T

  • kura , Physic a l Re v. B 66, 2002, 140408

YBaMn2O6

  • H. K

AGE YAMA, T . NAK AJI MA, M. I CHI HARA, Y. UE DA, H. YOSHI ZAWA AND K . OHOYAMA Jo urna l o f the Physic a l So c ie ty o f Ja pa n, 72, 2003, 241.

2ap× 22ap × 4ap

Ba/Gd ordering and COO

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SLIDE 18

New Type of Charge/Orbital Ordering in the GdBaMn2O5.75 Perovskite

[-110]p [110]p

2d110p

[110]p [110]p

= 22ap

Mn4+ Mn3+ Mn4+ Mn3+

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SLIDE 19

New Type of Charge/Orbital Ordering in the GdBaMn2O5.75 Perovskite

001p 110p

Mn4+ Mn3+ Mn4+ Mn3+ Mn3+ Ba2+ Ba2+ Gd3+ Gd3+

[ 1 1 ]

p

[001]p

001p 100p

Mn4+ Mn3+ Mn4+ Mn3+ Mn4+ Ba2+ Ba2+ Gd3+ Gd3+

[100]p [001]p

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SLIDE 20

The NPD pattern collected on the 153° backscattering bank of HIPD (black circles), the fit using the P4/mmm aristotype model (red), and the difference (beneath). The tick marks show the allowed hkl positions of for the aristotype structure. The insert shows some of the weak unfit reflections.

TbBaMn TbBaMn2

2O

O6

6-

  • δ

δ

2ap× 22ap × 4ap P212121

Ba Ba/ /Gd Gd ordering

  • rdering;

; octahedra

  • ctahedra tilting

tilting, , CO (Mn CO (Mn3+

3+/Mn

/Mn4+

4+),

), anion anion vacancies vacancies ordering

  • rdering
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SLIDE 21

TbBaMn TbBaMn2

2O

O6

6-

  • δ

δ

EWR analysis EWR analysis 2ap× 22ap × 4ap P212121

anion anion vacancies vacancies within within the the Tb Tb planes planes and and associated associated to to the the Mn Mn3+

3+

ions ions

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SLIDE 22

CONCLUSIONS CONCLUSIONS

Mn4+Mn3+

Crystal Crystal Structure Structure Electronic Electronic Structure Structure Physical and chemical properties SAED SAED and and HHRTEM HHRTEM EELS EELS HAADF HAADF-

  • STEM (

STEM (Aberration Aberration correction correction) ) BF BF-

  • STEM

STEM EWR EWR

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SLIDE 23

Acknowledgements Acknowledgements: :

  • Prof. Emilio Mor
  • Prof. Emilio Morá

án n Migu Migué élez lez Prof.

  • Prof. Nobuyuki

Nobuyuki Imanishi Imanishi

  • Prof. Miguel
  • Prof. Miguel Á

Ángel ngel Alario Alario Franco Prof. Franco

  • Prof. Yuichi

Yuichi Shimakawa Shimakawa

  • Dr. Juan Pe
  • Dr. Juan Peñ

ña Mart a Martí ínez Dr. nez Dr. Noriyuchi Noriyuchi Sonoyama Sonoyama Subakti Subakti Alejandro G Alejandro Gó ómez P mez Pé érez rez Daniel Mu Daniel Muñ ñoz Gil

  • z Gil

Prof.

  • Prof. Flaviano

Flaviano Garc Garcí ía Alvarado a Alvarado

  • Prof. Ulises Amador
  • Prof. Ulises Amador Elizondo

Elizondo Funding PIB2010JP-00181 (MICINN) MAT2010-19837 (MICINN)