in situ studies of hydrogen desorption from metallic ... scie… · in situ studies of hydrogen...
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In s
itu
stud
ies
of h
ydro
gen
deso
rpti
onfr
om m
etal
lic h
ydri
des
by n
eutr
on d
iffr
acti
on
M. L
atro
che,
V. P
aul-B
onco
ur, F
. Cue
vas
Inst
itut
de C
him
ieet
des
Mat
éria
uxde
Par
is E
stIC
MPE
-U
MR
7182
-CN
RSTh
iais
, Fra
nce
Shor
t in
trod
ucti
on t
o m
etal
lic h
ydri
des
(MH
)
Neu
tron
dif
frac
tion
for
MH
inve
stig
atio
n
oSt
eady
sta
te s
truc
tura
l ana
lysi
s
oO
ut o
f eq
uilib
rium
stu
dy b
y co
uple
d TD
S/N
D
The
pecu
liar
case
s of
TiN
iHx
and
YFe 2
Hx
Conc
lusi
ons
Out
line
Neu
tron
s fo
r M
HIn
trod
uction
Case
of
TiNiH
xCa
se o
f YF
e 2H
xCo
nclusion
s
Solid
gas
rou
te (
P eq
, C(x
) , T
)
M +
x /2
H2
MH
x
Shor
t intr
oduc
tion
to
met
allic
hyd
ride
sM
etal
lic h
ydri
de f
or s
olid
gas
sto
rage
ln(P
H2)
ln(P
H2)
T 4 T c T 3
T 2 T 1
+
x(H
/M)
min
max
P eq3
P eq1
P eq2
ln(P
H2) =
H
/RT
- S/
R
1/T
Neu
tron
s fo
r M
HIn
trod
uction
Case
of
TiNiH
xCa
se o
f YF
e 2H
xCo
nclusion
s
300
250
200
150
100
50
0,30
0,25
0,20
0,15
0,10
0,05
0,00
-0,0
5
E (V) vs Cd/Cd(OH)2
Q(m
Ah.g
-1)
Non
aqu
eous
ele
ctro
chem
ical
rou
te
MH
x+
x Li
++
x e-
M +
x L
iH
0
1000
2000
3000
4000
050
010
0015
0020
00
Ah/L
Ah/K
g
grap
hite
AB5H
5
MgH
2
TiH
2
TiFe
H2
ZrV
2H4.
9
Mg 2
NiH
4
040
00
Li
Y. O
umellal,
W. Za
ïdi,
J-P
Bonn
et,F
. Cu
evas
, M
. La
troc
he, J.
Zha
ng,
J-L
Bobe
t, A
. Ro
ugier
and
L. A
ymar
d. I
JHE,
37
(201
2) 7
831-
7835
Hg/
HgO
v
sV
in
92
6.0
ln2
PE
Heq M
HnFRT
x
Elec
troc
hem
ical
rou
te (
E eq,Q
(x),
T)
M +
xH
2O +
x e
-M
Hx
+ xO
H-
Shor
t intr
oduc
tion
to
met
allic
hyd
ride
sM
etal
lic h
ydri
de f
or e
lect
roch
emic
al s
tora
ge
Neu
tron
s fo
r M
HIn
trod
uction
Case
of
TiNiH
xCa
se o
f YF
e 2H
xCo
nclusion
s
NiM
H t
ract
ion
batt
erie
s fo
r N
ice
tram
s
Some
succ
essf
ul a
pplic
ations
of
hydr
ides
…
HEV
Toy
ota
Priu
s
Oth
er a
pplic
atio
ns-
emer
genc
y lig
ht u
nits
, tel
ecom
mun
icat
ions
, cor
dles
s va
cuum
...
MgH
2
Mg
Neu
tron
s fo
r M
HIn
trod
uction
Case
of
TiNiH
xCa
se o
f YF
e 2H
xCo
nclusion
s
Crys
tal s
truc
ture
det
erm
inat
ion
-Q
uant
ific
atio
n an
d lo
cati
on o
f H
(D) c
onte
nt
-Evi
denc
e of
pha
se t
rans
itio
ns a
s a
func
tion
of
H(D
) con
tent
Prac
tica
l adv
anta
ges
of u
sing
ND
as
diff
ract
ion
tool
:
-Bu
lk a
naly
sis
(hig
h pe
netr
atio
n de
pth
of n
eutr
ons)
-A
dapt
able
sam
ple
envi
ronm
ent
(fur
nace
, cry
osta
t, e
lect
roch
emic
al c
ell…
)
-A
dapt
ed t
ime
reso
luti
on f
or t
herm
al d
esor
ptio
n
Inne
r N
i cou
nter
-ele
ctro
deIn
ner
Ni c
ount
er-e
lect
rode
Hyd
ride
ele
ctro
deH
ydri
de e
lect
rode
oute
r N
i cou
nter
-ele
ctro
deou
ter
Ni c
ount
er-e
lect
rode
Silic
a c
ell
Silic
a c
ell
time
2La
troc
he e
t al. JA
LCOM
293
-295
(19
99) 67
3
Exam
ple:
In-
situ
ND
of
LaN
i 5-ty
pe e
lect
rode
s
Neu
tron
diffr
action
for
MH inv
estiga
tion
Neu
tron
s fo
r M
HIn
trod
uction
Case
of
TiNiH
xCa
se o
f YF
e 2H
xCo
nclusion
s
Gas
rele
ase
mea
sure
men
t (H
2) w
hile
hea
ting
in a
low
pres
sure
atm
osph
ere
Pote
ntia
l ene
rgy
diag
ram
s
T (K)
t (s
)
b (K
/s)
Hea
ting
ram
p
T
Ther
mal d
esor
ption
spec
tros
copy
(TD
S)
TDS
Spec
trum
dn/dt(P)
T (K
)
Neu
tron
s fo
r M
HIn
trod
uction
Case
of
TiNiH
xCa
se o
f YF
e 2H
xCo
nclusion
s
Var
iatio
n of
P in
th
e ch
ambe
rR
emov
al o
f gas
by
pum
pingP
KTS
dtdPK
TVdtdn
TDS:
Exp
erim
enta
l met
hod
P
Pum
p
SV,
T
dn/d
t
(QM
S)
Neu
tron
s fo
r M
HIn
trod
uction
Case
of
TiNiH
xCa
se o
f YF
e 2H
xCo
nclusion
s
Ther
mal d
esor
ption
spec
tros
copy
(TD
S)
Var
iatio
n of
P in
th
e ch
ambe
rR
emov
al o
f gas
by
pum
pingP
KTS
dtdPK
TVdtdn
TDS:
Exp
erim
enta
l met
hod
P
Pum
p
SV,
T
dn/d
t
(QM
S)
Smal
l vol
ume
(V)
Hig
h pu
mpi
ng r
ate
(S)
Pdtdn
TDS
Spec
trum
dn/dtP
T (K
)
Neu
tron
s fo
r M
HIn
trod
uction
Case
of
TiNiH
xCa
se o
f YF
e 2H
xCo
nclusion
s
Ther
mal d
esor
ption
spec
tros
copy
(TD
S)
Tem
pera
ture
ass
essm
ent
of d
iscr
ete
deso
rpti
on “s
tate
s”(T
DS
peak
s)
Popu
lati
ons
(inte
grat
ed a
reas
) and
rel
ated
act
ivat
ion
ener
gies
(Kis
sing
er p
lots
)
Det
erm
inat
ion
of r
ate
limit
ing
step
s (s
urfa
ce, t
rapp
ing,
dif
fusi
on, p
hase
tr
ansf
orm
atio
n) w
ith
a va
lid k
inet
ic m
odel
: fu
ll sp
ectr
a de
scri
ptio
n.
c) H/M
Mea
sure
dSi
mul
ated
PCT
isot
herm
s fo
r si
mul
atio
n
Ster
n et
al.
J. P
hys.
F:
Met
. Ph
ys. 14
(198
4)16
25Ex
ampl
e: T
DS
from
PdH
x
+
+
TDS:
wha
t info
rmat
ion
can
be o
btaine
d ?
Neu
tron
s fo
r M
HIn
trod
uction
Case
of
TiNiH
xCa
se o
f YF
e 2H
xCo
nclusion
s
TDS
vs.
ND
TDS
ND
Am
ount
of
deso
rbed
H2
Am
ount
and
loca
tion
of
H in
bul
k
Des
orpt
ion
mec
hani
sm
Surf
ace
reco
mbi
nati
on
H –
Dif
fusi
on
Phas
e tr
ansf
orm
atio
n
Crys
tal s
truc
ture
Phas
e tr
ansf
orm
atio
n vs
H-c
onte
nt
Ord
er-d
isor
der
tran
siti
ons
Am
orph
isat
ion
Neu
tron
s fo
r M
HIn
trod
uction
Case
of
TiNiH
xCa
se o
f YF
e 2H
xCo
nclusion
s
Combi
ned
mea
sure
men
ts T
DS
–ND
Silic
a co
ntai
ner
Vacu
um a
nd T
con
nect
ions
Neu
tron
bea
m li
ne I
LL –
D1B
MH
sam
ple
Neu
tron
bea
mFu
rnac
e
4OO
Det
ecto
rs
Ther
moc
oupl
e Neu
tron
s fo
r M
HIn
trod
uction
Case
of
TiNiH
xCa
se o
f YF
e 2H
xCo
nclusion
s
Neu
tron
s fo
r M
HIn
trod
uction
Case
of
TiNiH
xCa
se o
f YF
e 2H
xCo
nclusion
s
The
case
of
TiNi-
H2
Sorp
tion
pro
pert
ies
of t
he T
iNi-
H2sy
stem
Burc
h an
d M
ason
, J.
Che
m. So
c. F
arad
ay T
rans
. I
75 (19
79) 56
1
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
0.1110
Tem
pera
ture
(°C
)
5277
102
127
152
y(
)
PH2 (bar)
H /
TiN
i-pha
se
-pha
se
PCT
Ti Ni
Abs
orpt
ion
by s
olid
gas
rea
ctio
n: T
= 1
50°C
, PD
2=
4 M
Pa, t
= 2
wee
ks
Mea
sure
d co
ncen
trat
ion:
TiN
iD1.3
5
Neu
tron
s fo
r M
HIn
trod
uction
Case
of
TiNiH
xCa
se o
f YF
e 2H
xCo
nclusion
s
Pm
mVo
l/Ti
Ni=
27
Å3
Pm
mD
/TiN
i= 0
.29
Vol/
TiN
i= 2
8.7
Å3
3.05
7 Å
3.057 Å
Stru
ctur
al p
rope
rties
of t
he
phas
e
Neu
tron
s fo
r M
HIn
trod
uction
Case
of
TiNiH
xCa
se o
f YF
e 2H
xCo
nclusion
s
Ti Ni
H(D
)
I4/m
mm
D/T
iNi=
1.14
3.12
2 Å
3.093 Å
Ti Ni
H(D
)
Stru
ctur
al p
rope
rties
of t
he
phas
e
Neu
tron
s fo
r M
HIn
trod
uction
Case
of
TiNiH
xCa
se o
f YF
e 2H
xCo
nclusion
s
Soub
eyro
uxet
al.,
JAL
COM
196
(19
93) 12
7
TDS
One
–ste
p de
sorp
tion
010
020
030
040
050
0-0
.3
-0.2
-0.10.0
Heat flow (W/g)
T(°C
)
Exo
DSC
Thre
e–st
ep d
esor
ptio
n
tran
sfor
mat
ion
?Neu
tron
s fo
r M
HIn
trod
uction
Case
of
TiNiH
xCa
se o
f YF
e 2H
xCo
nclusion
s
Hyd
roge
n de
sorp
tion
fro
m T
iNiH
1.4
300
400
500
600
700
0123456789
P (bar)T(
K)
300
400
500
600
700
0123456789
P (bar)
T(K
)
Coup
led
TDS-
ND e
xper
imen
t
TDS T
(K)
ND
Neu
tron
s fo
r M
HIn
trod
uction
Case
of
TiNiH
xCa
se o
f YF
e 2H
xCo
nclusion
s
-TiN
iH1.4
-TiN
i
Am
orph
isat
ion
Inte
rmed
iate
phas
e (
)
Crys
talli
zati
on
Neu
tron
s fo
r M
HIn
trod
uction
Case
of
TiNiH
xCa
se o
f YF
e 2H
xCo
nclusion
s
Resu
lts
of R
ietv
eld
refine
men
t
300
350
400
450
500
550
020406080100
Phase content (wt% )
T (K
)
pha
se p
hase
pha
se
Neu
tron
s fo
r M
HIn
trod
uction
Case
of
TiNiH
xCa
se o
f YF
e 2H
xCo
nclusion
s
P4/m
mm
D/T
iNi=
0.7
Vol/
TiN
i= 2
9.4
Å3
Pmm
D/T
iNi=
0.2
9Vo
l/Ti
Ni=
28.
7 Å
3
I4/m
mm
D/T
iNi=
1.14
Vol/
TiN
i= 3
0.1
Å3
3.12
2 Å
3.093 Å
3.12
9 Å
3.001 Å
3.05
7 Å
3.057 ÅTi Ni
H(D
)
Neu
tron
s fo
r M
HIn
trod
uction
Case
of
TiNiH
xCa
se o
f YF
e 2H
xCo
nclusion
s
300
400
500
600
700
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
TD
S (s
pect
rum
inte
grat
ion)
ND
(D
-occ
upan
cies
)Deuterium content (D/TiNi)
T(K
)
Neu
tron
s fo
r M
HIn
trod
uction
Case
of
TiNiH
xCa
se o
f YF
e 2H
xCo
nclusion
s
Compa
riso
n of
ND a
nd T
DS
H-c
onte
nts
100
200
300
400
500
-0.6
-0.4
-0.20.0
0.2
Heat Flow (W/g)
T(°C
)
Exo
Des
orpt
ion
H2
300
400
500
600
700
0123456789
P (bar)
T(K
)
TDS
Crys
talli
sati
on
ND
Neu
tron
s fo
r M
HIn
trod
uction
Case
of
TiNiH
xCa
se o
f YF
e 2H
xCo
nclusion
s
Compa
riso
n of
ND,
TDS
and
DSC
DSC
The
case
of
YFe 2
-H2
Neu
tron
s fo
r M
HIn
trod
uction
Case
of
TiNiH
xCa
se o
f YF
e 2H
xCo
nclusion
s
Mul
ti-p
eak
TDS
spec
tra
of L
aves
C15
hydr
ides
att
ribu
ted
to
H-d
esor
ptio
n fr
om e
nerg
etic
ally
dif
fere
nt in
ters
titi
al s
ites
Mot
ivat
ion
Ster
n et
al.
JALC
OM
88
(198
2) 4
31Pa
rk e
t al.
Scr.
Met
all.
23 (19
89) 15
25
HfV
2Er
Fe2
AB 2
Dx
A2B
2x
3
AB 3
x >
3
A B
ND
: Onl
y 2
type
s of
sit
e oc
cupi
ed !
Neu
tron
s fo
r M
HIn
trod
uction
Case
of
TiNiH
xCa
se o
f YF
e 2H
xCo
nclusion
s
300
350
400
450
500
550
600
650
0.0
5.0x
10-5
1.0x
10-4
1.5x
10-4
2.0x
10-4
2.5x
10-4
3.0x
10-4
3.5x
10-4
4.0x
10-4
-dx/dt (H u.f.-1
s-1
)
T(K
)
Coup
led
TDS-
ND e
xper
imen
t fo
r YF
e 2D
4.2
Neu
tron
s fo
r M
HIn
trod
uction
Case
of
TiNiH
xCa
se o
f YF
e 2H
xCo
nclusion
s
380K
Ord
er-d
isor
der
tran
siti
ons
Phas
e tr
ansf
orm
atio
ns
mon
oclin
ic
C15
Neu
tron
s fo
r M
HIn
trod
uction
Case
of
TiNiH
xCa
se o
f YF
e 2H
xCo
nclusion
s
Coup
led
TDS-
ND e
xper
imen
t fo
r YF
e 2D
4.2
01
23
4
10-3
10-2
10-1
100
101
' 3 /
' 4
' 2 /
' 3
' 1 /
' 2
/ ' 1
408
K37
3 K
473
K
P (bar)
x (D
/YFe
2)
01
23
45
400
450
500
550
600
CubicC15
Tetragonal
cubic2a Tetragonal
CubicC15
triclinic
monoclinic
Orthorhombic
T=30
0 K
V (Å3)
x (D
/f.u.
)0
12
34
5
400
450
500
550
600
CubicC15
Tetragonal
cubic2a Tetragonal
CubicC15
triclinic
monoclinic
Orthorhombic
T=30
0 K
V (Å3)
x (D
/f.u.
)0
12
34
5
400
450
500
550
600
CubicC15
Tetragonal
cubic2a Tetragonal
CubicC15
triclinic
monoclinic
Orthorhombic
T=30
0 K
V (Å3)
x (D
/f.u.
)
-M
ulti
-pla
teau
isot
herm
s
Ther
mod
ynam
ic &
cry
stal s
truc
ture
for
YFe
2–D
2
V. P
aul-
Bonc
our,
JSS
C 14
2 (1
999)
120
Neu
tron
s fo
r M
HIn
trod
uction
Case
of
TiNiH
xCa
se o
f YF
e 2H
xCo
nclusion
s
Succ
essi
ve p
hase
tra
nsfo
rmat
ion:
Joh
nson
-Meh
l-Avr
ami(
JMA
) equ
atio
n
i
ii
iE
RTk
F)
(ex
p1
2
ii
ii
ii
iF
Fk
dtdF/)1
( )1
ln(
)1(
dtdFx
dtdxi
i
n i1
it
kF
ii
)(
exp
1RTE
kk
io
iex
p,
, K o
~ hT
/K ~
10-1
3s-
1
J. F
arja
s, P
. Ro
ura,
"M
odificat
ion
of t
he
Kolm
ogor
ov-J
ohns
on-M
ehl-
Avra
mir
ate
equa
tion
for
no
n-isot
herm
al e
xper
imen
ts a
nd it
s an
alyt
ical
solution
", A
cta
Mat
er.,
54
(200
6) 5
573-
5579
Fit
of T
DS
spec
trum
to
i-pha
se t
rans
form
atio
ns
Simulat
ion
of t
he T
DS
spec
trum
Neu
tron
s fo
r M
HIn
trod
uction
Case
of
TiNiH
xCa
se o
f YF
e 2H
xCo
nclusion
s
Peak
Ea
(kJ/
mol
)n
x (D
/f.u
.)1
123.
41.5
0.34
212
7.5
1.10.
73
313
3.5
1.10.
78
413
9.8
0.7
0.40
514
8.1
0.7
0.35
615
8.9
0.7
0.37
717
1.40.
71.2
2
300
350
400
450
500
550
600
650
0.0
1.0x
10-4
2.0x
10-4
3.0x
10-4
4.0x
10-4
TP i
Fit
TPi
Dat
a
1
-dx/dt (H f.u-1
s-1
)
T (K
)
32
45
6
7
Neu
tron
s fo
r M
HIn
trod
uction
Case
of
TiNiH
xCa
se o
f YF
e 2H
xCo
nclusion
s
Fit
of t
he T
DS
spec
trum
01
23
45
400
450
500
550
600
CubicC15
Tetragonal
cubic2a Tetragonal
CubicC15
triclinic
monoclinic
Orthorhombic
T=30
0 K
V (Å3)
x (D
/f.u.
)0
12
34
5
400
450
500
550
600
CubicC15
Tetragonal
cubic2a Tetragonal
CubicC15
triclinic
monoclinic
Orthorhombic
T=30
0 K
V (Å3)
x (D
/f.u.
)0
12
34
5
400
450
500
550
600
CubicC15
Tetragonal
cubic2a Tetragonal
CubicC15
triclinic
monoclinic
Orthorhombic
T=30
0 K
V (Å3)
x (D
/f.u.
)
0
1.2
1.751.95
3.3
2.5
Peak
x (D
/f.u
.)A
ssig
ned
Phas
e Tr
ansf
orm
atio
n1
0.34
YFe 2
D4.
2YF
e 2D
3.85
20.
73YF
e 2D
3.85
YFe 2
D3.
15
30.
78YF
e 2D
3.15
YFe 2
D2.
35
40.
40YF
e 2D
2.35
YFe 2
D1.9
5
50.
35YF
e 2D
1.95
YFe 2
D1.6
0
60.
37YF
e 2D
1.60
YFe 2
D1.2
0
71.2
2YF
e 2D
1.20
YFe 2
3.5
4.2
Neu
tron
s fo
r M
HIn
trod
uction
Case
of
TiNiH
xCa
se o
f YF
e 2H
xCo
nclusion
s
350
400
450
500
550
600
650
400
420
440
460
480
500
01234
C15
-Vol
ume
V (Å3)
T (K
)
Deuterium content (D/f.u.)
Supe
rstru
ctur
e xPD
(D
-occ
upan
cies
) x
TDS (s
pect
rum
inte
grat
ion)
T. L
eblond
et a
l., I
JHE,
34(
2009
) 22
78
Neu
tron
s fo
r M
HIn
trod
uction
Case
of
TiNiH
xCa
se o
f YF
e 2H
xCo
nclusion
s
Compa
riso
n of
ND a
nd T
DS
H-c
onte
nts
Conc
lusion
s (I
)
Ther
mal
des
orpt
ion
from
TiN
iD1.4
hydr
ide
occu
rs t
hrou
gh a
n
inte
rmed
iate
d hy
drid
e ph
ase
of m
ediu
m H
-con
tent
: -T
iNiD
0.7.
phas
e tr
ansf
orm
atio
n ge
nera
tes
com
poun
d am
orph
isat
ion.
DSC
mea
sure
men
ts a
re e
xpla
ined
by
the
com
bine
d ef
fect
s of
endo
ther
mic
hyd
roge
n de
sorp
tion
and
exo
ther
mic
allo
y
crys
talli
zati
on. Neu
tron
s fo
r M
HIn
trod
uction
Case
of
TiNiH
xCa
se o
f YF
e 2H
xCo
nclusion
s
Mul
ti-p
eak
TDS
spec
trum
for
YFe
2hy
drid
e is
wel
l-des
crib
ed b
y
cons
ecut
ive
phas
e tr
ansf
orm
atio
ns.
Mul
tipl
e C1
5 La
ves
phas
es h
ave
been
evi
denc
ed b
y N
D a
nd X
RD
diff
ract
ion
mea
sure
men
ts .
Sam
e de
scri
ptio
n m
ay a
ccou
nt f
or m
ulti
-pea
k TD
S sp
ectr
a
obse
rved
for
man
y C1
5 La
ves
phas
es.
Neu
tron
s fo
r M
HIn
trod
uction
Case
of
TiNiH
xCa
se o
f YF
e 2H
xCo
nclusion
s
Conc
lusion
s (I
I)
TDS
set-
up c
an b
e ea
sily
impl
emen
ted
in N
D b
eam
-line
Coup
ling
of T
DS
-N
D t
echn
ique
s is
a v
ery
powe
rful
tool
to
char
acte
rize
hyd
roge
n de
sorp
tion
fro
m s
olid
s,
part
icul
arly
whe
n ph
ase
tran
sfor
mat
ions
tak
e pl
ace
Neu
tron
s fo
r M
HIn
trod
uction
Case
of
TiNiH
xCa
se o
f YF
e 2H
xCo
nclusion
s
Conc
lusion
s (I
II)
Ack
nowl
edgm
ents
F. C
ueva
s
V. P
aul-
Bonc
our
T.
Lebl
ond
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