US 20050112018A1

(19) United States

(12) Patent Application Publication (10) Pub. No.: US 2005/0112018 A1
Schulz et al. (43) Pub. Date: May 26, 2005

(54) CA-MG-NI CONTAINING ALLOYS, Publication Classi?cation

METHOD FOR PREPARING THE SAME AND
USE THEREOF FOR GAS PHASE ...... .. C22C 19/03
HYDROGEN STORAGE (51)
(52) Int.Cl.7
Us. 01. .......................................... .. 420/455; 420/900
(75) Inventors: Robert Schulz, Ste Julie (CA); (57) ABSTRACT
GuoXian Liang, Longueuil (CA)
Disclosed are neW Ca, Mg and Ni-containing alloys of the
Correspondence Address: general formula:
HAYNES AND BOONE, LLP (CacMgdMe)b(Ni17zTz)a
901 MAIN STREET, SUITE 3100 Where:
DALLAS, TX 75202 (US)
M is at least one metal selected from the group consisting
(73) Assignee: HERA, Hydrogen Storage Systems, of Y, Ce, La, Pr, Nd, Th, Nd, Ti, V, Zr, Ta, Hf, Sr, Ba
Inc., Longueuil (CA) and Misch metals;
(21) Appl. No.: 10/926,578 T is at least one element selected from the group consist
ing of Al, Zn, Cu, Fe, Co, Mn, Cr, Mo, W, Si, Ga, Ge,
(22) Filed: Aug. 26, 2004 In, Sn, Ag, C and B;
a is an integer equal to 2 or 5;
Related US. Application Data
Z is a number ranging from 0 to 0.5; and
(63) Continuation-in-part of application No. PCT/CA03/
00058, ?led on Jan. 17, 2003. When a is equal to 2, then 0.9ébé 1.1; and
When a is equal to 5, then either 1.75§b§2.25 or
(60) Provisional application No. 60/497,554, ?led on Aug. 0.75§b§1.31.
26, 2003.
These alloys Which are of the AB2, A2B5 or AB5 types, may
(30) Foreign Application Priority Data be single phase or multiphase and are useful for reversibly
absorbing hydrogen from a gas phase. Also disclosed is a
Feb. 27, 2002 (CA) ................................. .. CA 2,373,553 method for preparing the above alloys.
Patent Application Publication May 26, 2005 Sheet 1 0f 65 US 2005/0112018 A1

Fig. 1-1

C30.4Mg0.6Ni2
I_Ni
§__CaNi2 type

A.B5ECQE _
_

Two theta (°)

Patent Application Publication May 26, 2005 Sheet 2 0f 65 US 2005/0112018 A1

Figl-z

CaXMg1_xNi2

(Inate.usity),
“A MgMCaMNi2
MgNi2

Two theta (°)

Patent Application Publication May 26, 2005 Sheet 3 0f 65 US 2005/0112018 A1

Fig.1-s

Ca0.3Mg0.7Ni2

1000C

(Inat.eusity), L
809C
,J ULM-A-JLJL
A J 600C

AM I l T I I I I I T I

20 3O , 40 50 6O 7O _ 80

Two theta (°)

Patent Application Publication May 26, 2005 Sheet 4 0f 65 US 2005/0112018 A1

Fig.1-4.

After 1h annealing at 1000C

CaXMgI-XNiZ

‘‘ x=0.0
x=0.2 '

(Inate.suity),
{LX203 A. ,“L JL L A L

lFOAAJin/LL
l L ‘tiny
‘_I‘l'l‘l'i
2O 3O 4O 50 6O 7O 80

Two theta (°)

Patent Application Publication May 26, 2005 Sheet 5 0f 65 US 2005/0112018 A1

Figl-S

100 . , I i ‘ I ' I '

ll

Ill LI

l lIl Il Il
Paretsmuvre, _L

llllllI llllll

l I

011 ' I ' s l‘

0,0 0,3 - 0,6 0,9 1,2
Hydrogen content, wt.%
Patent Application Publication May 26, 2005 Sheet 6 0f 65 US 2005/0112018 A1

_ Fig.1-6

Zn substitution on the B site

Ca0.4Mgo.6Ni1.9ZIl0.1

.1 L 1M. it L A L
(lnayt.eusiy), C30.4Mg0.6Ni2

IL JLJLLLAhLJL
C30.4Mg0.sMm0.1Ni2
Mm substitution on the A

Two theta (°)

Patent Application Publication May 26, 2005 Sheet 7 0f 65 US 2005/0112018 A1

Fig.1-7

Ca0.3M_g0.7Ni1.sC 110.2

O (NisFe)

(Inate.usity), B Site

_ t m OHM
C30.3Mg0.'/Ni1.sFe0.2

pt 0»
A site (i _ (:aQJMgOJMmOJNiZ
J A‘ 1j L A‘ L L 4 L

LL Ca0-3Mg0JNi2
i in J L A____\ k A L
I I i l ‘ I I I I I I

20 30 4O 50 60 7O 80

Two theta (°)

Patent Application Publication May 26, 2005 Sheet 9 0f 65 US 2005/0112018 A1

Fig.1-9

100 ,5 ' l | l ' l | :

g 10 ‘: H Mg0.7ca0.1Mmo1Niz .=
cu : . E
as H Mg0JCa0JSMm0J5N12 I
3 _

g
a:
1 1 Absorption
- - E]
Mg0JcaO1Mrn0JN12 . .
_:
Q. : I
g Desorption D Mg0.7Ca0.25Mm0.o5Ni2 I
Q) - -

5 i -
Q‘ 0-1 - o o ' Mg-Ca-Ni _:

[I I Mg-Ca-Mm-Ni 5

0,01 ' | ' I 1 I ' 1 l l

6,88 6,90 6,92 6,94. 6,96 6,98 7,00

Lattice parameter, X10‘1 nm
Patent Application Publication May 26, 2005 Sheet 10 0f 65 US 2005/0112018 A1

Fig. 2-1

0 I '

I"— CaNiS (Ca0.4Mg0.6)2Ni5

§_MgNi2
, . M ' = -
+ Q a2N17 I g/Ca ratio 1 5

(Inate.usity),
20h

20 3O 4O ' ' 5O ‘ 60

Two theta (°) I

Patent Application Publication May 26, 2005 Sheet 11 0f 65 US 2005/0112018 A1

Fig. 2-2

(Ca0.4Mg0.6)bNiS

AB3 A/B = b/S = 0.35

i ' .
E type = = 0.4

‘g .
{:3 AB2+A2B5 A/B = b/5 = 0.45

ABZ A/B = b/5 =0.5

I I ' l ‘ | i I b ‘ |

70
Two theta (°)
Patent Application Publication May 26, 2005 Sheet 12 0f 65 US 2005/0112018 A1

Fig. 2-3

(Ca0.375Mg0.62s)2N15 1045C
J4 ‘l 4 4L A_
1000C
3 _/u L
Si
‘2:.
'23
C
9
E > ,

'
M ‘1*-
M -
600C‘
' k J--

Mg/Ca rati0=1.67 ‘ ~'as-mi1led

A >
I | I I ' l ‘ l ' l '

2O 30 4O 5O 6O 7O 80

Two theta (°)‘

Patent Application Publication May 26, 2005 Sheet 13 0f 65 US 2005/0112018 A1

Fig. 24

100 - 1 1 I I ' ' | - - f ;

T=30C :
(Ca0.37sMg0.62s)2Nis _ r5713 43 ‘

h 10 _
m I
.Q :
93'
D
‘I
.

g -o— as-milled _
0*- 1 —III— 600°C
—A— 800°C '3
----- 900°C 5
—><— 1000°C '
o o -
—5l€— 1045 C
011 | - | F I I | I I T I

- 0,0 0,3 0,6 0,9 1,2' 1,5

Hydrogen content, wt.% '
Patent Application Publication May 26, 2005 Sheet 15 0f 65 US 2005/0112018 A1

Fig. 2-6

Mg/Ca = 1-79 (C3u.3sMgo.62s)2Nis

‘ 1p éJL .

'7 ‘ Mg/Ca = 1-67 (Ca0.375Mg0.625)2Ni5

3
£5,
a“
g Mg/Ca : 1-5 (C3o.4Mg0.6)2Nis 3

E E = kl...‘
.2 JL i ' _ Lh I

Mg/Ca 1 (Ca0;46Mg0.ss)2Nls 3

' | ' I I l ‘ 1 I I -

- 2O 3O 4O 50 60 ' 70 80

Two theta (°)

Patent Application Publication May 26, 2005 Sheet 16 0f 65 US 2005/0112018 A1

Fig. 2-7

6E5362a
- --~-
-<i-
0,1 I 1 l r l l I
0,0 0,2 0,4 0,6 0,8 1,0 . 1,2 1,4 1,6 1,8
Hydroge'n content, wt.% '
Patent Application Publication May 26, 2005 Sheet 17 0f 65 US 2005/0112018 A1

Fig. 2-8 - Substitution on the A site

(almfs-xMgo.625-yMmx+3)2Ni5
(e) (C3o37sMg0._sMm0.12s)2Nis _
I . . L _

'53
3
r2: w (d) ' it I .ML
L Y~ (Ca0.sMgo.3-/sMmo.12s)2Nis
(Ca0.25Mg0.625Mm0.125)2Ni5
* ‘LL 4

E .20Ju ‘ (a)
(b)ah I 4'0 " sio(C2103125Mg0_625Mm0_0625)2Ni5
(catmsMgomshNis
‘ 6'0 I 7‘0
_ L I so

Two theta (°)

Patent Application Publication May 26, 2005 Sheet 18 0f 65 US 2005/0112018 A1

Fig. 2-9

100

.Cwba56mgl

l
0 0,6 1, 1,5 1,8
Hydrogen content, wt.%
Patent Application Publication May 26, 2005 Sheet 19 0f 65 US 2005/0112018 A1

Fig. 240

(Ca0.5Mg0.375Mm0.125)2Ni5Hx

(Inate.usity),
_ _ (Ca0.5Mg0.375Mm0.12s)2Nis

2O 4O 6O 80

Two theta (°)