Upload
dangxuyen
View
221
Download
0
Embed Size (px)
Citation preview
AgI
1 1
1
2
3
1
3
3
2 4
1
2
3
Debye
4
11
12
3 15
1
2
3
AgI
15
15
16
4 20
5 X 24
6 25
1
2
25
29
7 30
1
2
3
4
5
6
AgI X
ColeCole
-AgI
-AgI
-AgI
-AgIX
30
33
34
35
36
37
8 39
40
41
1
1
framework
framework
Fig.1-1
Li+ framework
Fig.1-1 framework
2
Poly ethylene terephthalate (PET)
PET
PET
(1) Poly ethylene terephthalate (PET)
(2)
-AgI
3
2
1961B. S. H. ROYCEK+
KCl[1]B. S. H. ROYCE
KCl 10 0.2 eV
2000S. FurusawaK+KTiOPO4 (;KTP)
S. FurusawaKTP
GPa
KTPc-
framework
[2]
[3-10]
frameworkframework
2
framework
-AgI
4
()
mobile ion
thermal activated
barrierU(x)
a
ZZe
0
P
hopping
T1P
Pk TB
exp
(2-1)
kB
[s-1]0
0 0P
k TBexp (2-2)
xx
5
Fig.2-1-1 HollanditeK+
Ze0
a
x
U(x)
Fig.2-1-2 E=0
site
1hopping1
10attempt
frequencyhopping
rate
6
xE
U'(x)U(x)
(x)
U'(x)=U(x)+Ze(x)=U(x)ZeEx+k k(2-3)
x
U(x)
Ze0
+Zea
2E
Zea
2E
E
Fig.2-1-3 E0
x
EZea
2
x
EZea
2
E
xhoppingx(2-2)
Tk
ZeaE
B
0x
/2exp
Tk
ZeaE(
B
/2exp (2-4)
1v(2-4)hopping rate +xa
av x
Tk
ZeaE
Tk
ZeaE
Tk
a
BBB
02
exp2
expexp
7
Tk
ZeaE
Tk
a
BB
02
sinh2exp (2-5)
EakBT
12
Tk
ZeaE
B
Tk
ZeaE
Tk
ZeaE
BB 22sinh
(2-6)
Tk
Tk
Zeav
BB
exp2
0 (2-7)
ZeNi
ETk
Tk
ZeaNvNZei
BB
exp
2
0(2-8)
i
Ei = (2-9)
(2-8)(2-9)
Tk
Tk
aZeN
BB
22
exp0 (2-10a)
(2-10a)f
Tk
f
Tk
aZeN
BB
22
exp0 (2-10b)
(2-10)
(2-10b)T
T
ek
T
1logloglog
B
0
fk
aZN 0
B
22
0
e
(2-11)
T
e
k
T
3
3
B
0
10
10
logloglog
(2-12)
8
log(
ek
B
log10 3
Arrenius plot
log(
T)
1000/T
kB10-3log10e
Fig.2-1-4
[11]
(1)
Li 1
9
(2)
(1)(2)
(3)(7)
(3)
(4)
Li
AgI
Table 2-1-1 [12,13]
Table 2-1-1 e=Pe/E
ion e=Pe/E [cm3] ion e=Pe/E [cm
3]
Li+ 0.0310-24 O2- 0.53.210-24
Na+ 0.4110-24 I- 6.4310-24
K+ 1.3310-24 Si4+ 0.0210-24
Rb+ 1.9810-24 Sn4+ 3.410-24
Cs+ 3.3410-24 Ge4+ 1.0010-24
Ag+ 2.410-24
(5)
(6)
(7)
10
D*=fDrandom f
Haven ratio1/31
11
Debye
0
12
Fig.2-1-6
Z'
RB
RB
CB
max
-Z" (a)
Fig.2-1-6 Cole-Cole
RB CB
Z*()
BB
B
RCi
RZ
1)(* (2-15a)
2
BB
B
RC
RZZ
)(1)('Re *
(2-15b)
2
2*
)(1)("Im
BB
BB
RC
RCZZ
(2-15c)
(1-b)(1-c)
2
2
2
2"
2'
BB R
ZR
Z (2-16)
(2-16) ZZCole-Cole
(RB/2, 0) RB/2
Z RBCole-Cole
Z0=RB
max 1/(RB CB) RBmax
13
CB
RB
14
RB
CB
Rg
Cg-Z"
Z'
RB
(c)
Rb
Cb
Re
Ce
or
RB+Rgor
RB+Re
Fig.2-1-8 Cole-Cole
2
2 Ri
Ci
Z'
RB
RB
CB
max
-Z" (f)
RB
Fig.2-1-9
15
1 AgI
AgI
PET (Ag)(Fig.3-2 )
(I2)(Ag)(I2) 2
X -AgI
2
-AgI 3D (OLYMPUS OLS4000 LEXT)
Ag2 mAg -AgI 8.5 m
16
3
Ag Ag
Fig.3-1 Table 3-1
VPC-260F
ROUGH
FORE
Fig. 3-1 VPC-260F
17
Table 3-1 VPC-260F
110-5 Torr1.310-3 Pa
310-5 Torr4.010-3 Pa20
100 V 5060 Hz 1.2 kW
010 VMax 150 A
200 V 5060 Hz 1.5 kW
Fig. 3-2 (Ag)
Ag AgI
Ag AgI
1 AgI
AgIAg
AgIAg
Fig. 3-2
18
Fig. 3-3 (a),(b)
Fig. 3-3 (b)
Fig. 3-3 (b) Table 3-2
Fig. 3-3
(a) (b)
Table 3-2 Fig. 3-3(b)
PET film AgI thin film
x [mm] 20 17
y [mm] 60 10
z [m] 100 8.5 8.7
(a) (b)
19
d l d/l1 E
l l=1.0 mm
d=9 m d/l= 910-31
[][film ][Sample ](Fig. 3-4)
S = d W
W
S
l
sample film
d ()
= filmsample
E
A
AA
A
A
d
l
10 mm17 mm 8
Fig. 3-4
20
4
Fig. 4-1
LCB04K150K Table 4-1 LOAD CELL
Fig. 4-2
Fig. 4-3
Fig. 4-1 (a)(b) (
(a)
(b)
21
Fig. 4-2
-
+
0 V
+12 V
Fig. 4-3
Table 4-1 LOAD CELL
LCB04K150L
1.5 kN
2 mV/V10 %
DC12 V
100 ][ L
L (4-1)
L L
22
1878
Tomlinson
[14]
LOAD CELL
LOAD CELL 12 V 2 mV/V
24 mV 1.5 kN
1.5 kN 24mV 2mV/V mV2
1 mV F0[N] 24
1500 [N/mV]
measureVFF 0 measureV LOAD CELL [mV]
23
PET
Fig. 4-4 0 ~ 20 N
20 N
0 ~ 20 N PET
20 N
PET PET
0 N 0
PET
PET
0
20
40
60
80
100
0 0.2 0.4 0.6 0.8 1
[%]
F [
N]
Fig. 4-4 PET
24
5 X
Fig. 5-1
Table 5-1
X
X
X
()
(R185mm)
2
2
Fig.5-1 X
Table 5-1 X
RIGAKU RINT2000
CuK= 1.5406 )
-2
40 kV
20 mA
-2
2390
0.010
25
6
.
1
HP4194A Impedance/Gain-Phase
AnalyzerHEWLETT PACKARDHP4194A
RDUTDevice Under Test
IDUTFig. 6-1-1L(
=0)Fig. 6-1-1
L
DUTZx
IRZx
V1V2IRV2=RI
V1V2
2
1
2
11
V
VR
R
V
V
I
VZx
(6-1-1)
ZxV1
V212
1111111 sincose 1
iVVVVi
(6-1-2)
2222222 sincose 2
iVVVVi
(6-1-3)
21212
1
2
1
2
1 sincosee
e21
2
1
i
V
VR
V
VR
V
VRZ
i
i
i
x (6-1-4)
26
LFHF20 Hz110 MHz
Fig. 6-1-2
()
HP4194A 50
31440A
HP4194A 31440A GP-IB 1)
PC-9821V13
IANAZ
1GP-IB
IEEE 488 HP-IB (Hewlett-Packard Instrument Bus)GP-IB
V1 V2
H L
DUT
Zx R
Fig. 6-1-1
27
Fig. 6-1-2 Table. 6-1-1
Fig. 6-1-2
28
Table 6-1-1
HP4194A ImpedanceGain-Phase AnalyzerHEWLETT PACKARD
100 Hz 15 MHz( 1 m)
1 mHz
20 ppm(235 )
|Z |, |Y |, , R, X, G, B, L, C, D, Q
10 m100 M
100
31440AAgilent
Alumel Chromel
PC-9821V13NEC
IANAZ
OS MS-DOS N88BASIC
29
2
Table 6-2-1
Table 6-2-1
0120 N (5 N )
290325 K
100 Hz10 MHz
N2
Ag
AgI S l
Table 6-2-2 -AgI S l
l [mm] S [mm2]
OHP Film (PET) 1.0 0.69
30
7
1 AgI X
AgI X
Fig.7-1-1 Fig.7-1-1
Table 7-1-1 -AgI PDF (No. 01-078-1613) -AgI
-AgI
PDF -AgI
(002)(102)(110)(103)(112)
26
PET
0 10 20 30 40 50 60 70 80 90
2 [deg]
102
103
112
-AgI thin film
Substrate:PET
Thickness 2 m
CuK
PDF2Plus No.01-078-1613
-AgI
110
002
002
102
110 103
112
PET
Inte
nsi
ty [
Arb
. U
nit
s]
100
101
203
213
Fig.7-1-1 -AgI X
31
Table 7-1-1 -AgI PDF
01-078-1613 QM=*
AgI
Silver Iodide
Rad: CuKa1 Lambda: 1.5406 Filter: d-sp: Calculated
Cutoff: Int: Calculated I/Icor: 6.81
Ref. Anharmonic thermal vibrations in wurtzite-type Ag I., Yoshiasa, A., Koto,
K., Kanamaru, F., Emura, S., Horiuchi, H., Acta Crystallogr., Sec. B:
Struct. Sci., 43, 434 (1987), Calculated from ICSD using POWD-12++
Sys: Hexagonal S.G.: P63mc(186) Aspect:
a: 4.591(1) b: c: 7.511(4) A: C: 1.636027
A: B: C: Z: 2.00
mp:
Ref. Ibid.
Dx: 5.687 Dm: SS/FOM: F30=1000(.000,32)
ANX: AX. Analysis: Ag1 I1. Formula from original source: Ag I. Delete
duplicate: Delete: see 01-078-1614, JMB 7/00. ICSD Collection Code: 62789.
Temperature of Data Collection: 123 K. Wyckoff Sequence: b2 (P63MC). Unit
Cell Data Source: Single Crystal. Peak height intensities. Single-crystal
data used.
2 [de] Int h k l 2 [de] Int h k l
22.34241 100 100 92.94596 7 215
23.67217 57 002 93.29958 1 206
25.32536 63 101 93.44423 2 312
32.77674 34 102 96.07385 1 107
39.21436 77 110 99.51207 6 313
42.64136 73 103 101.6038 1 305
45.59591 12 200 102.8368 1 401
46.31888 44 112 103.7345
32
63.03395 6 211 114.9206 1 108
64.00974
33
2 -AgI Cole-Cole
Fig. 7-2-1 -AgI 0.0 %Cole-Cole (at 300 K)
0
5000
1 104
1.5 104
0 5000 1 104
1.5 104
2 104
-Z''
[cm
]
Z' [cm]
-AgI thin film
Thickness 8.7 m
0.0 %
300 K
Fig. 7-2-1-AgI 0.0 %Cole-Cole
i
1
ZZZZ 0* (2-13)
Z0 Z
Z=0
34
3 -AgI
Fig. 7-3-1 -AgI
0
1 10-5
2 10-5
3 10-5
4 10-5
5 10-5
6 10-5
7 10-5
0 0.2 0.4 0.6 0.8 1
[%]
-AgI thin film
thickness 8.7 m
at 300 K
[
-1cm
-1]
Fig. 7-3-1-AgI
PET -AgI
-AgI
X
35
4 -AgI
-AgI
Fig. 7-4-1
0.001
0.01
0.1
3.1 3.2 3.3 3.4
T
[
-1cm
-1K
]
1000/T [K-1]
-AgI thin film
Thickness 8.7 m
0.00% 0.19% 0.44% 0.69% 0.94%
Fig. 7-4-1 -AgI
Tk
TB
exp0 (7-4-1)
fk
aZeN
B
0
22
0
)( (7-4-2)
fittingN
a
fittingfitting2
36
5 -AgI
Fig. 7-5-1 -AgI
0.2
0.25
0.3
0.35
0.4
0.45
0.5
102
103
104
105
106
0 0.2 0.4 0.6 0.8 1
[
eV]
0 [
-1cm-1]
[%]
1000/T=3.27-3.4 [K-1]
1000/T=3.1-3.4 [K-1]
1000/T=3.1-3.27 [K-1]
-AgI thin film
Thickness 8.7 m
Fig. 7-5-1 AgI
framework
framework X
X
37
6 -AgI X
X
( EXTRA4020)
2
-AgIXFig.7-6-1
2 = 22.524.5 Fig. 7-6-3
20 30 40 50
(b)
2[deg]
(a)Inte
nsi
ty [
Arb
. U
nit
s]
00
2
10
2
11
0
10
3
11
2
1.0 %
0.0 %
Fig. 7-6-1 -AgI X
(a)( 0.0 %) (b)( 1.0 %)
22.5 23 23.5 24 24.5
1.0 %
2[deg]
00
2
Inte
nsi
ty [
Arb
. U
nit
s]
0.0 %
Fig. 7-6-2 Fig. 7-6-1 2 = 22.524.5
Fig. 7-6-1 Fig. 7-6-2
Table 7-6-1
38
-AgI -AgI
framework
Table 7-6-1 -AgI
dhkl []
h k l *0.0 *1.0 [%]
002 3.766 3.748 0.499
102 2.736 2.728 0.297
110 2.300 2.295 0.196
103 2.120 2.118 0.134
112 1.961 1.958 0.163
*
39
8
-AgI
(1) -AgI
(2) -AgI
(3) XRD
-AgI-AgI framework
-AgI
(Fig.
3-3(b) x )(Fig. 3-3(b) z )
(Fig. 8-1(a))(Fig. 8-1(b), 8-1(c))
AgI
(1)(Fig. 3-3(b) x )(Fig. 3-3(b) z )
(2)(Fig. 8-1(a))(Fig. 8-1(b),8-1(c))
(3)
(4)
Fig. 8-1 (a) (b) (c)
(b)
(c)
(a)
40
[1] B. S. H. ROYCE, R. SMOLUCNOWSKI, Effect of Plastic Deformation on the
Low-Temperature Ionic Conductivity of Potassium Chloride, Physical Review Vol. 122, No.4,
(1961) pp.1125-1128
[2] S. Furusawa, H. Sugiyama, F. Itoh, A. Miyamoto and T. Sasaki; Ionic Conductivity of
Quasi-One-Dimensional Ionic Conductor KTiOPO4 (KTP) Single Crystal at High Pressure J. Phys.
Soc Jpn., 69 (2000) pp. 2087-2091
[3] B. Morosin and P. S. Peercy; Physcs Letters A, Vol.53 (1975) pp. 147-148.
[4] G.A. Samara; Pressure and temperature dependences of the ionic conductivities of cubic and
orthorhombic lead fluoride (PbF2) Journal of Physics and Chemistry of Solids, Volume 40, Issue 7,
1979, Pages 509522
[5] G.A. Samara; High-Pressure Studies of Ionic Conductivity in Solids Solid State Physics, Vol38,
(1984) pp. 180
[6] J. Zhang, J. Ko, R. M. Hazen, C. T. Prewitt; High-pressure crystal chemistry of KAlSi3O8
hollandite American Mineralogist, Vol.78 (1993) pp. 493-499
[7] A. Yagi, T. Suzuki, M. Akaogi; High Pressure Transitions in the System KAlSi3O8-NaAlSi3O8
Phys Chem Minerals 21 (1994) pp. 12-17
[8] Aimin Hao et al.; Conductivity of AgI under high pressure J. Appl. Phys. 101 (2007) pp.
053701
[9] T. Katsumata, Y. Inaguma, M. Itoh, and K. Kawamura; Influence of Covalent Character on High
Li Ion Conductivity in a Perovskite-Type Li Ion Conductor: Prediction from a Molecular Dynamics
Simulation of La0.6Li0.2TiO3 Chem. Mater. 2002, 14, 3930-3936
[10] Fabrice Bruneta, Nikolai Bagdassarov, Ronald Miletich Na3Al2(PO4)3, a fast sodium conductor
at high pressure Solid State Ionics 159 (2003) 35 47
[11] JME
[12] p.212e=Pe/E
[13]p.8 11
[14] ,
http://www.aandd.co.jp/adhome/products/loadcell/introduction/cell_intro02_01.html
41
29 3 6