irmantas barnackas, prof. l. pranevičius lithuanian energy institute 2006 02 03 destabilization of...
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Irmantas Barnackas, prof. L. PranevičiusLithuanian Energy Institute
2006 02 03
Destabilization of Mg-based hydrogen storage materials: experimental results
To synthesize destabilized MgHTo synthesize destabilized MgH22 hydride and to investigate the hydride and to investigate the
hydride propertieshydride properties
The main goal of the workThe main goal of the work
Experimental technique: Experimental technique:
• to produce nanocrystalline Mg, Mg-Ti thin film materials using magnetron sputtering;
• to hydrogenate Mg, Mg-Ti thin films in high hydrogen pressure and temperature (p,T);
• to study Mg, Mg-Ti thin films de-hydrogenation kinetics using GDOES techniques;
• to analyze Mg, Mg-Ti thin films properties of as-deposited, after hydrogenation and de-hydrogenation using XRD, SEM and GDOES methods.
Quartz substrate
Mg film
Ti layer
Quartz substrate
Ti layer
Mg film
Quartz substrate
Mg + Ti film
UUTiTi = 490 V, I = 490 V, ITi Ti = 0.5 A, t = 5 sec.= 0.5 A, t = 5 sec.
UUMgMg = 420 V, I = 420 V, IMg Mg = 1 A, t = 5 min.= 1 A, t = 5 min.
UUTiTi = 480 V, I = 480 V, ITi Ti = 0.5 A, t = 5 sec.= 0.5 A, t = 5 sec.
UUMgMg = 405 V, I = 405 V, IMg Mg = 1 A, t = 5 min.= 1 A, t = 5 min.
UMg = 410 V, IMg = 1 AUTi = 440 V, ITi = 0.5 A t = 5 min.
Parameters of as-deposited Mg and MgTi films :Parameters of as-deposited Mg and MgTi films :
Quartz substrate
Mg film UUMgMg = 420 V, I = 420 V, IMg Mg = 1 A, t = 5 min.= 1 A, t = 5 min.
Pressure (Ar) – 0.4 PaPressure (Ar) – 0.4 Pa U UBIASBIAS = -100 V, = -100 V,
I IBIASBIAS = 10-60 mA = 10-60 mA
Parameters of hydrogenation/dehydrogenation of Mg, MgTi thin films Parameters of hydrogenation/dehydrogenation of Mg, MgTi thin films in high hydrogen pressure and temperature (p,T)in high hydrogen pressure and temperature (p,T)
Parameters of hydrogenation: Pressure (H2) – 8-11 bar
Temperature – RT – 320 0CHydrogenation duration – 6 hour
Parameters of dehydrogenation: Temperature – RT – 450 0CDehydrogenation duration – 60 min.
As-deposited Mg film: - XRD and SEM analysis
XRD diffractogram of as-deposited Mg film on quartz substrate
SEM micrograph of as-deposited Mg film on quartz substrate
10 20 30 40 50 60 700
500
1000
1500
2000
2500
3000
DMg 1-1
h-Mg(103)h-Mg(102)h-Mg(101)
h-Mg(002)
P(Ar) = 0.4 PaU
pries = -100 V, I
pries = 10 mA
Uznesimo schema : UMg
= 420 V, IMg
= 1 A
t = 5 min.
M g d a n g a
K v a r c a s
Inte
nsi
ty, a
rb.u
.
Diffraction angle, 2 theta
Hydrogenation/dehydrogenation kinetics of Mg film: Hydrogenation/dehydrogenation kinetics of Mg film: - XRD and SEM analysis
SEM micrograph of Mg film: (a) after hydrogenation; (b) after dehydrogenation
10 20 30 40 50 60 700
500
1000
1500
2000
2500
3000
3500
4000
DMg 1-1 VHG
h-Mg(101)
t-MgH2(211)
t-MgH2(101)
h-Mg(102)h-Mg(101)
h-Mg(002)
h-Mg(103)
DMg 1-1
c-MgO(220)
c-MgO(200)
T = 450 0C, t = 6 hDehidrinimo parametrai:
Hidrinimo parametrai:
c-MgO(220)
c-MgO(200)
P(H2) = 8-11 bar
T = 320 0C, t = 6 h
DMg 1-1 VH
t-MgH2(110)
Inte
nsy
vum
as, s
ant.
v.
Difrakcijos kampas, 2 teta
XRD analysis of XRD analysis of Mg film after hydrogenation/dehydrogenation processes
b
a
DMG 1-1VH
0
5
10
15
20
25
30
35
40
45
0 500 1000 1500 2000 2500 3000 3500 4000
Time, s
Inte
ns
ity
, a
rb.u
.
0
100
200
300
400
500
600
Te
mp
era
ture
, C
Desosiation curveTemperature curve
78°C
33°C
168°C
298°C
438°C
Studies of deStudies of de--hydrhydrogenationogenation kinetics of Mg thin films kinetics of Mg thin films
As-deposited Mg-Ti film: - XRD and SEM analysis
10 20 30 40 50 60 700
500
1000
1500
2000
2500
3000
h-Mg(102)h-Mg(101)
h-Mg(002)h-Mg(103)
P(Ar) = 0.4 PaU
pries = -100 V, I
pries = 10 mA
UMg
= 420 V, IMg
= 1 A
t = 5 min.
UTi = 490 V, I
Ti = 0.5 A
t = 5 sek.Uznesimo schema :
Mg danga
T i d an g a
K v a rc a s
DMg 13-1
Ti etalonas
Mg etalonas
Inte
nsy
vum
as, s
ant.
v.
Difrakcijos kampas, 2 teta
XRD diffractogram of as-deposited MgTi film on quartz substrate
SEM micrograph of as-deposited MgTi
film on quartz substrate
Hydrogenation/dehydrogenation kinetics of Mg-Ti film: Hydrogenation/dehydrogenation kinetics of Mg-Ti film: - XRD and SEM analysis
10 20 30 40 50 60 700
500
1000
1500
2000
2500
3000
P(H2) = 8-11 bar
T = 320 0Ct = 6 h
c-MgO(220)c-MgO(200)
DMg 13-1 VH
h-Mg(102)h-Mg(101)
h-Mg(002)h-Mg(103)
DMg 13-1
Inte
nsy
vum
as, s
ant.
v.
Difrakcijos kampas, 2 teta
XRD analysis of XRD analysis of Mg-Ti film after hydrogenation process
SEM micrograph of MgTi film after hydrogenation
As-deposited Mg-Ti film: - XRD and SEM analysis
10 20 30 40 50 60 700
500
1000
1500
2000
2500
3000
h-Mg(002) h-Mg(103)
P(Ar) = 0.4 PaU
pries = -100 V, I
pries = 10 mA
UMg
= 405 V, IMg
= 1 A
t = 5 min.
UTi = 480 V, I
Ti = 0.5 A
t = 5 sek.
Uznesimo schema : Mg danga
T i d a n g a
K v a rc a s
DMg 18-2
Ti etalonas
Mg etalonas
Inte
nsyvu
mas, san
t.v.
Difrakcijos kampas, 2 teta
XRD diffractogram of as-deposited MgTi film on quartz substrate
SEM micrograph of as-deposited MgTi film on quartz substrate
10 20 30 40 50 60 700
500
1000
1500
2000
2500
3000
3500
4000
h-Mg(102)h-Mg(101)
h-Mg(002)h-Mg(103)
Mg danga
c-MgO(220)c-MgO(200)
T = 450 0C, t = 6 hDehidrinimo parametrai:
Hidrinimo parametrai:
DMg 18-2 VHG
c-MgO(220)c-MgO(200)
P(H2) = 8-11 bar
T = 320 0C, t = 6 h
DMg 18-2 VH
h-Mg(002) h-Mg(103)
DMg 18-2Inte
nsyv
um
as, san
t.v.
Difrakcijos kampas, 2 teta
Hydrogenation/dehydrogenation kinetics of Mg-Ti film: Hydrogenation/dehydrogenation kinetics of Mg-Ti film: - XRD and SEM analysis
a
b
XRD analysis of XRD analysis of MgTi film after hydrogenation/dehydrogenation processes
SEM micrograph of MgTi film: (a) after hydrogenation; (b) after
dehydrogenation
DMg 18-2VH
0
10
20
30
40
50
60
0 500 1000 1500 2000 2500 3000 3500 4000
Time, s
Inte
nsit
y, arb
. u
.
0.00
50.00
100.00
150.00
200.00
250.00
300.00
350.00
400.00
450.00
500.00
Te
mp
era
ture
, C
Disosiation curveTemperature curve
35.5°C
68°C
200°C 265°C
378°C
380°C
390°C
400°C
Studies of deStudies of de--hydrhydrogenationogenation kinetics of Mg-Ti thin films kinetics of Mg-Ti thin films
As-deposited Mg-Ti film: - XRD and SEM analysis
10 20 30 40 50 60 700
500
1000
1500
2000
2500
3000
?? Ti arba Mg
xTi
y faze
t = 5 min. Mg + Ti danga
Kvarco padėklas
P(Ar) = 0.4 PaU
pries = -100 V, I
pries = 40 mA
UMg
= 410 V, IMg
= 1 A
UTi = 440 V, I
Ti = 0.5 A
Uznesimo schema :
DMg 21-2
Ti etalonas
Mg etalonas
Inte
nsy
vum
as, s
ant.
v.
Difrakcijos kampas, 2 teta
XRD diffractogram of as-deposited MgTi film on quartz substrate
SEM micrograph of MgTi film after hydrogenation
Hydrogenation/dehydrogenation kinetics of Mg-Ti film: Hydrogenation/dehydrogenation kinetics of Mg-Ti film: - XRD and SEM analysis
10 20 30 40 50 60 700
500
1000
1500
2000
2500
3000
3500
4000
4500
5000
h-Mg(101)
r-Ti2O
3(116)
h-Ti(002) c-MgO(220)c-MgO(200)
T = 450 0C, t = 1 hDehidrinimo parametrai:
Hidrinimo parametrai:
Gryna Mg danga
h-Mg(103)h-Mg(102)h-Mg(101)h-Mg(002)
DMg 21-2 VHG
DMg 21-2 VH
? Mg, Ti, MgH2, TiH
2, TiO...
c-MgO(220)c-MgO(200)
P(H2) = 8-11 bar
T = 320 0Ct = 6 h
? Ti arba MgxTi
y faze
DMg 21-2
Inte
nsy
vum
as, s
ant.
v.
Difrakcijos kampas, 2 teta
XRD analysis of XRD analysis of MgTi film after hydrogenation/dehydrogenation processes
a
b
SEM micrograph of MgTi film: (a) after hydrogenation; (b) after
dehydrogenation
DMg 21-2VH
0
1
2
3
4
5
6
7
8
0 500 1000 1500 2000 2500 3000 3500 4000
Time, s
Inte
nsi
ty, a
rb. u
.
0
50
100
150
200
250
300
350
400
450
500
Tem
per
atu
re, C
Disosiation curveTemperature curve
23°C
60°C
163°C
175°C
210°C
330°C
365°C
405°C
Studies of deStudies of de--hydrhydrogenationogenation kinetics of Mg-Ti thin films kinetics of Mg-Ti thin films
10 20 30 40 50 60 700
10000
20000
30000
40000
? (TiO2 arba Mg
xTi
y fazes)
h-Mg(101)
t = 5 min. Mg + Ti danga
Kvarco padėklas
P(Ar) = 0.4 PaBe priesitampio !!!
UMg
= 410 V, IMg
= 1 A
UTi = 500 V, I
Ti = 1 A
Uznesimo schema :
DMg 20-1
Inte
nsy
vum
as, s
ant.
v.
Difrakcijos kampas, 2 teta
XRD diffractogram of as-deposited MgTi film on quartz substrate
As-deposited Mg-Ti film: - XRD and SEM analysis
SEM micrograph of MgTi film after hydrogenation
Hydrogenation/dehydrogenation kinetics of Mg-Ti film: Hydrogenation/dehydrogenation kinetics of Mg-Ti film: - XRD and SEM analysis
10 20 30 40 50 60 700
10000
20000
30000
c-MgO(200)
? (MgxTi
y phase)
c-MgO(220)h-Ti(101)
T = 450 0C, t = 1 hDehidrinimo parametrai:
Hidrinimo parametrai:
DMg 20-1 VHG
P(H2) = 8-11 bar
T = 320 0C, t = 6 h
h-Mg(002)
h-MgH2(102)
DMg 20-1 VH
? MgxTi
y phase
h-Mg(101)
DMg 20-1
Inte
nsy
vum
as, s
ant.
v.
Difrakcijos kampas, 2 teta
XRD analysis of XRD analysis of MgTi film after hydrogenation/dehydrogenation processes
a
b
SEM micrograph of MgTi film: (a) after hydrogenation; (b) after dehydrogenation
Studies of deStudies of de--hydrhydrogenationogenation kinetics of Mg-Ti thin films kinetics of Mg-Ti thin filmsDMg 20-1 VH
0
10
20
30
40
50
60
70
0 500 1000 1500 2000 2500 3000 3500 4000
Time, s
Inte
nsi
ty, a
rb. u
.
0
50
100
150
200
250
300
350
400
450
500
Tem
per
atu
re, C
Disosiation curveTemperature curve
23°C
90°C
165°C
235°C
273°C
295°C
410°C
ConclusionsConclusions
1. 2 µm Mg and MgxTiy thin films were successfully deposited on the quartz substrates using magnetron sputtering.
2. After the hydrogenation of pure Mg thin films in hydrogen atmosphere, in high pressure and high temperature, MgH2 thin films were successfully formed.
3. The MgTi thin film deposited without bias voltage and hydrided in high pressure and high temperature (p,T) at 320 0C for 6 hour transforms to MgH2.