????????? ??????????????? ??????????? ??. ?.?. ????????

1
????????? ??????????????? ??????????? ??. ?.?.
???????? ???? ?????????????? ? ?????????????
????????? ?????????? ?????????
??????? ?????????? ?????
?.?. ????
??????? ? ???????? ????????????? ????????
??????????
???????????? 2008
2
?????????????? ????????? ???? (SOFC)
3
SOFC ????????? ?????? (??????????? ???)
4
??????? ???????? ???????? ?? ??????????????-?????
????? ????????????? ??? ?????????? ???????
SyngasCOH2 pO210-20atm
AirpO20.21atm
O2-
Oxygen lean air
CH4Steam
h
e-
O2(gas)4e2O2-(ads)
CH4O2COH2
5
?????????
6
PEROVSKITE STRUCTURE ABO3
B-cation
A-cation
O2- ion
7
PEROVSKITE STRUCTURE ABO3
B-cation
A-cation
O2- ion
8
DIMENSIONAL MODEL OF CHEMICAL EXPANSION OF OXIDES
BASED ON AN AVERAGE CHANGE OF IONIC RADIUS

• GENERAL ASSUMPTIONS
• A CLOSELY PACKED LATTICE OF OXIDE IS FORMED BY
  IONS WITH RIGID SPHERES
• EXPANSION IN EACH OF THREE SPACE DIRECTIONS IS
  OF EQUAL VALUE
• OXYGEN VACANCY HAS THE RADIUS, WHICH IS
  IDENTICAL TO THAT OF OXYGEN ION

9
EXPERIMENTAL SETUP FOR THE CHEMICAL EXPANSION
MEASURING

1. FURNACE
2. OXYGEN PUMP SENSOR
3. SAMPLE
4. ALUMINA ROD
5. THERMOCOUPLE
6. WATER COOLING
7. EXPANSION SENSOR(0.01 µm)
8. GAS CIRCULATION SYSTEM

10
EXPERIMENTAL SETUP FOR THE COULOMETRIC TITRATION

1. BUFFER CHAMBER
2. COULOMETRIC CELL
3. OXYGEN PUMPS
4. OXYGEN SENSORS
5. CONTROLLER OF T PO2
6. THERMOCOUPLE
7. GAS CIRCULATION SYSTEM
8. FURNACE

11
RAW TRACE OF THE CHEMICAL EXPANSION OF LaCoO3-d
12
THE CHEMICAL EXPANSION OF LaMnO3-d VERSUS OXYGEN
PARTIAL PRESSURE
13
COMPOSITIONS AND MODELS OF THE DEFECT STRUCTURE
FORLANTHANUM CHROMITES
14
COMPOSITIONS AND MODELS OF THE DEFECT STRUCTURE
FORLANTHANUM COBALTITES AND CHROMITES
15
?????????? ??????? ? ???????? ????????
16
?????????? ??????? ? ???????? ????????
17
?????????? ??????? ? ???????? ????????
18
?????????? ??????? ? ???????? ????????
19
????????? ??????? ??? ABO3 c ?????????
??????????, ????????? ? ???????????
???????????????? ??????? ??????????? ?????????
20
DEFECT STRUCTURE MODEL FOR LANTHANUM MANGANITES
IN OXYGEN EXCESS REGION
21
DEFECT STRUCTURE MODEL FOR LANTHANUM MANGANITES
IN OXYGEN EXCESS REGION
22
DEFECT STRUCTURE MODEL FOR LANTHANUM MANGANITES
IN OXYGEN EXCESS REGION
23
DEFECT STRUCTURE MODEL FOR LANTHANUM MANGANITES
IN OXYGEN DEFICIT REGION
24
DEFECT STRUCTURE MODEL FOR LANTHANUM MANGANITES
IN OXYGEN EXCESS REGION
25
DEFECT STRUCTURE MODEL FOR LANTHANUM COBALTITES
AND MANGANITES IN OXYGEN DEFICIENCY REGION
26
DEFECT STRUCTURE MODEL FOR CERIA
27
MODELING ANALYSIS RESULTS FORLa0.80Sr0.20CrO3-?
? La0.80Sr0.20Cr0.97V0.03O3-? at 1000 C
A. Zuev et al. Solid State Ionics 147 (2002) 1
28
CALCULATED CONCENTRATION OF DIFFERENT DEFECT
SPECIES AS A FUNCTION OF P?2 at 1000C FOR
La0.8Sr0.2Cr0.97V0.03O3-d
29
MODELING ANALYSIS RESULTS FOR LANTHANUM COBALTITES
A.Yu. Zuev et al. J. Mat. Sci 42 (2007) 1901
30
MODELING ANALYSIS RESULTS FOR LANTHANUM COBALTITES
M. H. R. Lankhorst et al. J. Solid St. Chem 133
(1997) 555
31
MODELING ANALYSIS RESULTS FOR LANTHANUM MANGANITE
J. Mizusaki et al. Solid State Ionics 129 (2000)
163
32
MODELING ANALYSIS RESULTS FOR LANTHANUM MANGANITE
Original data of Zuev et al. in press
33
MODELING ANALYSIS RESULTS FOR CERIA
M. Mogensen et al. Solid State Ionics 129
(2000) 63
34
MODELING ANALYSIS RESULTS FOR CERIA
M. Mogensen et al. Solid State Ionics 129
(2000) 63
35
MODELING ANALYSIS RESULTS FOR CERIA
M. Mogensen et al. Solid State Ionics 129
(2000) 63
36
CHEMICAL EXPANSION MODEL FOR LANTHANUM CHROMITES
CHEMICAL EXPANSION MODEL FOR LANTHANUM CHROMITES
La1-xMxCrO3-d Original model of A.Yu. Zuev et al.
CHEMICAL EXPANSION MODEL FOR LANTHANUM CHROMITES
La1-xMxCrO3-dS. Miyoshi et al. Solid State
Ionics 161 (2003) 209
37
CHEMICAL EXPANSION OF La1-xCaxCr(Mg)O3-d
38
CHEMICAL EXPANSION OF La1-xSrxCr(V)O3-d
39
CHEMICAL EXPANSION MODEL FOR LANTHANUM
MANGANITESAND COBALTITES
S. Miyoshi et al. Solid State Ionics 161 (2003)
209
40
CHEMICAL EXPANSION OF LaMnO3-d
41
CHEMICAL EXPANSION OF LaMnO3-d
Original data of Zuev et al. in press
42
CHEMICAL EXPANSION OF LaCoO3-d
Zuev et al. Solid State Ionics (2008)
doi10.1016/j.ssi.2008.06.001
43
CHEMICAL EXPANSION OF LaCo0.7Cr0.3O3-d
Zuev et al. Original data, unpublished
44
CHEMICAL EXPANSION OF La1-xSrxCoO3-d
45
CHEMICAL EXPANSION OF La0.8Sr0.2CoO3-d
46
CHEMICAL EXPANSION OF CeO2-d
M. Mogensen et al. Solid State Ionics 129 (2000)
63
47
CHEMICAL EXPANSION OF CeO2-d
48
CHEMICAL EXPANSION OF FeO1d (Fe1- dO)
49
CONCLUSIONS

• MODELING ANALYSIS WAS CARRIED OUT FOR SEVERAL
  FLUORITE, NaCl, AND PEROVSKITE STRUCTURED OXIDES
• CHEMICAL EXPANSION MODEL BASED ON THE RELATIVE
  CHANGE OF THE MEAN IONIC RADIUS WAS EVOLVED
• EXPERIMENTAL DATA ON CHEMICAL EXPANSION AND
  THOSE CALCULATED ON THE BASIS OF THE MODEL WERE
  SHOWN TO COINCIDE WITH EACH OTHER VERY GOOD FOR
  La1-xMxCr(Mg,V)O3, LaCo1-xCrxO3, LaMnO3,
  La0.8Sr0.2CoO3 , CeO2-x, AND FeO1d
• DISCREPANCY BETWEEN EXPERIMENT AND MODEL GROWS
  ALONE WITH ACCEPTOR IMPURITY IN La1-xSrxCoO3-d
  AND SIMULTANEOUS INCREASE ITS OXYGEN
  NONSTOICHIOMETRY

50
Future prospect