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A new model to describe absorption kinetics of Mg-based hydrogen storage alloys

Guangxin Wu a,*, Jieyu Zhang a,*, Qian Li a, Kuochih Chou a,b
a b

School of Materials Science and Engineering, Shanghai University, Shanghai 200072, PR China Department of Physical Chemistry, University of Science and Technology Beijing, Beijing 100083, PR China

article info
Article history: Received 15 May 2011 Received in revised form 7 July 2011 Accepted 11 July 2011 Available online 10 August 2011 Keywords: Hydrogen storage materials Mixed rate controlling kinetic model

abstract
Based on Chou model and unreacted-core model, a new mixed rate controlling kinetic model has been derived in this paper to investigate the adsorption reaction time t for Mgbased hydrogen storage materials as a function of temperature T, particle radius R0 and reaction fraction z. This new model could be predigested into individual single step and mixed two-connection step equations. The characters of this new model have also been discussed. Moreover, the new model is successfully applied for a real case and results indicate that this new model works very well and could reasonably deal with complex kinetics mechanism. Copyright 2011, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.

1.

Introduction

Magnesium alloy is an ideal clean carrier for hydrogen storage due to their high hydrogen storage capacity by weight (7.6 wt.%) and low cost. However, the main disadvantage of Mg-based alloys as a hydrogen store is the high temperature of hydrogen discharge and slow adsorption/desorption kinetics [1]. Therefore, the key problem now for the Mg-based storage materials is how to improve the kinetic property of hydriding/ dehydriding reaction. In order to solve this problem, a theoretical quantitative description for storage process is required. Numerous kinetics studies on gasesolid in hydriding/dehydriding reactions of powder metallic samples have been presented during the last two decades. Table 1 lists the reaction model from literatures [2,3]. In the most general case, all these steps contribute to the overall reaction rate. However, it is more convenient to assume that the rate of hydrogen absorption is actually controlled by only one of the above steps [4e6]. For a practical hydrogen storage system, sometimes the situation is more complex than

that expected. It is possible that for a system there might exist more controlling steps in the whole process [7]. For example, the results of investigation on hydrogenation kinetics on Mge5 wt.% Nie10 wt.%Ti19Cr50V22Mn9 system [8] in our research group showed that the tted curves are not according with experimental points using Chou model, especially for the low temperature period (423 Ke473 K). This means the process is not simply controlled by single rate controlling step. In this case, a combination of controlling steps should be considered and treated. Meanwhile, Martin et al. [4] investigated hydrogenation of Mg 2wt.%Ni system and the results showed that for the hydrogen absorption process a more complex mechanism must be employed, based on a combination of nucleation of hydride islands on the surface and the shrinking core model as suggested by Vigeholm et al. [9]. Hu et al. [10] combinated chemical reaction and mass transfer process to describe interfacial kinetics of oxidation transfer. The tted result is in good accordance with experiments. However, activation energy and diffusion rate could not be obtained from Hus model, which is signicantly important for us to investigate the gasesolid reactions.

* Corresponding authors. Tel./fax: 86 021 56337920. E-mail addresses: gxwu@shu.edu.cn (G. Wu), zjy6162@staff.shu.edu.cn (J. Zhang). 0360-3199/$ e see front matter Copyright 2011, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved. doi:10.1016/j.ijhydene.2011.07.026

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Table 1 e Set of reaction models to describe the reaction kinetics from the literatures. Mechanism
One-dimensional diffusion One-dimensional diffusion (Jande equation and Chou model) Second order kinetics (Chou model) Two-dimensional diffusion (bidimensional particle shape) Three-dimensional diffusion (GislingeBraunshtein equation) First order kinetics Two-dimensional phaseeboundary reaction Three-dimensional phaseeboundary reaction Zero order Random nucleation and growth of nuclei (AvramieErofeev equation) Random nucleation and growth of nuclei (AvramieErofeev equation) Phase-boundary controlled reaction (n 0, 1/2, and 2/3) Three-dimensional diffusion (KrogereZiegler equation) Three-dimensional diffusion (modied Jander relation)
2

Equation
x kt [1(1x)1/3]2 kt

Ref.
[2, 11] [2, 7, 11e14] [7, 14] [2, 11]

[1(1x)1/3] kt (1x)ln(1x)x kt

12x/3(1x)2/3 kt

[2, 13, 15]

ln(1x) kt 1(1x)1/2 kt 1(1x)1/3 kt x kt [ln(1x)]1/2 kt

[2, 11] [2, 11] [2, 11] [2] [2, 16]

Fig. 1 e Schematic representation of unreacted core model.

According Chou model [7,14], a general mechanism of hydriding reaction for a particle can be described as the following seven steps (shown in Fig. 2), they are: (i) Hydrogen in the bulk gas phase transfers to the surface of the metal particle H2 gas phase H2 gas; near particle surface (2)

[ln(1x)]

1/3

kt

[2, 16]

[1(1x)1n]/(1n) kt [17] [1(1x)1/3]2 klnt [(1/(1x))1/3e1]2 kt [13] [13]

(ii) Hydrogen diffusion through the boundary layer between gas phase and solid particle H2 gas; near particle surface H2 gas; surface of near particle (3)

In this work, a new model based on Chou model and unreacted-core model will be presented which could deal with more complex kinetics mechanism and is simple enough to be solved analytically with a personal computer. Furthermore, our new model will be performed to obtain activation energy and reaction time in practical hydrogen storage alloys.

(iii) Physisorption of hydrogen molecules on the solid surface

kpa kb pa
f

H2 gas; surface of near particle Wpa % H2 pa

(4)

where W ( pa) is the empty physisorption site on the surfaces. (iv) Dissociation of hydrogen molecules and chemisorption

2.

Derivation of formulae
H2 pa 2Wca % 2Hca Wpa
kb ca kca
f

Fig. 1 shows the schematic diagram of the unreacted core model presented in this study [18]. Diffusing through a lm covering the solid particle of radius R, the reactant gas reaches at the surface of the particle and reacts with the solid. When reaction of solid production is faster than reaction of gas production, the layer of the hydride is produced and the interface between the hydride and the unreacted core moves toward the center of the particle. It is assumed that this movement of the interface occurs uniformly, so that the radius of the core rc decreases as reaction while the radius of the particle keep constant with the progress of reaction. It is also assumed that all reactions are the rst-order reaction and occur at the surfaces of the unreacted core and the particle itself, respectively. Let us consider a gasesolid reaction of hydrogen storage alloys represented by aAg bBs cCs (1)

(5)

where W (ca) is the empty chemisorption site on the surfaces.

Fig. 2 e A schematic diagram of mechanism of reaction between hydrogen gas and metal particle [7,14].

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(v) Surface penetration of hydrogen atoms 2Hca % Hg=b; r R0 Wca

kb sp ksp
f

respectively. qca denotes the percentage of absorbed hydrogen in the particle surface. (6) 2) Surface penetration step The total rate of surface penetration Vsp can be expressed as Eq. (12) h i f b f b Vsp Vsp Vsp 4pR2 0 ksp qca ksp CH g=b; r R0
f

where Hg=b; r R0 denotes the hydrogen atoms in the hydride phase just underneath the particle surface at radius R0. (vi) Diffusion of hydrogen atoms through the hydride product layer to the hydride/metal interface. Hg=b; r R0 % Ha=b; r r
kb sp ksp
f

(12)

(7)

(vii) Chemical reaction and nucleus formation producing hydride Ha=b; r r Mea % MeHa=b
kb r kr
f

Where ksp and kb sp represent the rate constant for the surface penetration in the direction of forward and backward, respectively. CH g=b; r R0 denotes the concentration of hydrogen atoms in layer of R0.

(8)

3) Diffusion step The total rate of diffusion Vd can be expressed as Eq. (13) Vd 4pR0 rDb H   Ca=b; r r Cg=b; r R0 R0 r (13)

First let us assume that, all powders of metal or alloy could be regarded as spherical balls with the same density and radius as shown in Fig. 1 where a represents metal phase with radius of r, b is hydride layer with thickness of x. The whole particle is a ball of radius R0. When hydrogen reacts with metal, a hydride layer b is formed outside of the particle. It can be seen from Fig. 1 that the transferred (or reacted) fraction of hydride x at radius r and time t can be calculated in the light of the following equation:  x1 r R0 3 (9)

Where Db H represent the diffusion coefcient, CH g=b; r r denotes the concentration of hydrogen atoms in layer of r.

4) Chemical reaction step The total rate of chemical reaction Vr can be expressed as Eq. (14) h i f b b Vr Vr Vr 4pr2 kf r CH a=b; r r kr
f

When considering chemisorption, surface penetration, diffusion and chemical reaction will be the overall rate controlling step while physisorption rate will so quickly that the local equilibrium was obtained. Therefore, the essential limiting rate can be expressed as follows: (1) Step 1: Physisorption

(14)

Where kr and kb r represent the rate constant for the chemical reaction in the direction of forward and backward, respectively. (3) Step 3: Mixed rate controlling step

The equilibrium constant of physisorption reaction can be expressed as Eq. (10): Kpa
f kpa kb pa

qpa 1 qpa PH2

f

(10)

According to the shrinking core model [18]if the reaction is stable, the rates of individual steps should be equal to each other. Therefore, it can be obtained: Vca Vsp Vd Vr rA (15)

Where kpa and kb pa represent the rate constant for the physisorption in the direction of forward and backward, respectively. qpa denotes the percentage of absorbed hydrogen in the particle surface. W( pa) is the empty physisorption site on the surfaces, the hydrogen concentration of which should be equal to (1 qpa ). (2) Step 2: The rest individual steps 1) Chemisorption step The total rate of chemisorption Vca can be expressed as Eq. (11): h i f b f b Vca Vca Vca 4pR2 (11) 0 kca qpa kca qca Where kca and kb ca represent the rate constant for the chemisorption in the direction of forward and backward,
f

Where rA represent the consume rate of reactant. In the research of gasesolid reaction kinetics, rB usually represent the consume rate of solid reactant:   a ar d 4pr3 ar 4pr2 dr rA rB B B b b b dt 3 dt (16)

Also, it is well known that r=R0 1 x1=3 , thus the Eq. (16) will be reduced to ! x i 1 h 1 1 x2=3 b 2DH 17

1 Ksp 1 1 b b k 3 R0 kb R D 0 ca sp H

2 3 b bKsp Kca Kpa PH2 1 1 4 Kr 35 t 1 1 x f R2 R0 kr 0 arB

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Where the rst, second and third items mean contribution of mass transport, diffusion and chemical reaction to reaction time, respectively. This basic formula was used to describe the relationship between reaction time t and reaction fraction z. And more details about the rate controlling express of different types are all deduced from this equation. According to the denition in Chou model [7,14], when t tc, we obtain z 1, therefore, the physical meaning of the characteristic hydriding absorption time is that, it is the required time at which the whole particle is completely hydrogenated. The smaller the tc is, the faster the hydriding reaction will be one may use this quantity to measure the reaction rate for substance.

three-dimensional diffusion model proposed by GislingeBraunshtein [15] and three-dimensional phase-boundary reaction proposed by Budrugeac [11], respectively.

3.2.

The end of curve

According the deducibility procedure above, one obtains: ! Ksp 1 R0 2 r kb kb Db ca sp H Where r R0 1 x3 Substituting Eqs. (19) into Eq. (18) yields
1

bR0 !! bR2 0 Ksp Kca qpa R2 Kr 0 r d r dt b arB DH

(18)

(19)

3.
3.1.

Discussion
Morphology of curves

0 @ Ksp 1 1 R0 kb R0 kb Db ca sp H b bKsp Kca qpa Kr dt R2 0 arB

1 !   1 1 1 A 3 dx 1 x 3 Db H

For the mixed rate controlling step of surface penetration, diffusion and chemical reaction, it is difcult to discuss the complicated kinetics mechanism. Therefore, we do not consider here. A schematic diagram of all rate-controlling step is shown in Fig. 3. After predigested the basic formula, the simple equation was compared with previous works listed in Table 1. It can be seen that single rate controlling steps of chemisorption/ surface penetration, diffusion and chemical reaction are similar with zero-reaction model proposed by Budrugeac [11],

(20)

In order to obtain the maximum of curve, we have dx x0 dt bR2 0 bR2 0 Ksp Kca qpa Kr 0 1 ! !   1 Ksp 1 1 1 1 A @ 3 1 x arB b b b R0 kb k R 3 D D 0 ca sp H H

(21)

0 0 2 12 bR0 2 bR K K q sp ca pa 0 B Kr C C x00 3B @ A 0 arB @ @ 1 Db H

1 !  4 1 A 1 x 3 3 ! 13 ! 1 1 A 3 1 x Db H (22)

Ksp 1 1 b b R0 kb k R D 0 ca sp H

When x00 0, we obtain x 1. However, x 1 is not the inexion point of basic formula. Therefore, in tting process using our new model, the end of curve will persistent in a horizontal direction as shown in Fig. 4. The reason is that with reaction carrying on, reaction fraction will close to 1 which is consistent well with kinetic experiments.

3.3.

Other properties

Fig. 3 e A schematic diagram of rate-controlling step.

a) Our new model is derived from Chou model in our group. Thus similar to Chou model, parameters of our new model have specic physical signicance. Meanwhile, our new basic model could be deduced into different single and mixed rate controlling steps, which could be applied to practice system conveniently. b) It is worthwhile to mention that Jander equation [12] is based on the incorrect assumption that the radius of the spherical shrinking core obeys a square-root time

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dependence, similar to the diffusion-controlled planar case. Evidently, the utilization of planar kinetics to the spherical geometry is not justied [19]. In our new model, 3D reaction rate was considered for the spherical particles. This assumption improves the Jander model and makes a closer connection to the real case [9,19e21]. c) It is known that the volume of the sphere consists of the unreacted part of solid component B. If the reaction product is not equal to the initial volume of component B, unreacted core model should be modied, such as the volume exchange VMgH2 =VMg 1:31. In fact, it has been proposed that the effect becomes signicant only for volume exchange greater than 2 [21]. Therefore, we do not consider the effect of volume exchange on the tting results. d) It may be noticed that the energy term appearing in the exponent sign is not a simple activation energy but a sum of activation energy and enthalpy, therefore, the term activation energy called by a lot of foregoing researchers actually is an apparent activation energy not a simple activation energy. For example, there are exits activaf tion energie DE1 Dsp and apparent activation energy 0 DE2 DHsp Dd for the mixed rate controlling step.

are 0.8932 and 0.9971, respectively. On the contrary, these experimental data cannot be tted by the model with other rate-controlling step. From these results, the chemisorption/ surface penetration step can be considered as the rate controlling step. Meanwhile, our results show that the calculated activation energy and characteristic time are about 299.0 1.6 kJ/mol and 755,427 s, respectively, for the unmilled Mg powder while those are 199.6 8.4 kJ/mol and 119,589 s for the milled Mg powder. The reason is that after ball milling treatment the surface of the particles becomes much rougher and forms more fresher surface during the process. And the hydrogen absorption mechanism cannot be changed by ballmilling treatment at temperature of 423 K.

4.2.

Application of diffusion formula

4.

Application to practical systems

4.1. Application of chemisorption/surface penetration formula

Huot et al. [22] presented a systematic study of structural modications and hydrogen absorption-desorption kinetics of ball-milled magnesium hydride. The milling was carried out with a Spex 8000 model shaker mill and a vial and balls of stainless steel with a ball to powder weight ratio of 10:1. Milling times for up to 20 h were used. Fig. 5 shows the hydrogen absorption curves of unmilled and milled MgH2 at temperature of 423 K. The relationship between x and t is modeled by tting the experimental data with the rate equations of each step using the least squares. For the chemisorption/surface penetration step, the corresponding R2 of the linear regression equations for the unmilled and milled MgH2

Fig. 6 shows the hydrogen absorption curves of Mg powder [22] at temperature of 573 K and 673 K. The relationship between x and t is modeled by tting the experimental data with the rate equations of each step using the least squares. For the diffusion step, the corresponding R2 of the linear regression equations is 0.9892. And it can be shown that the calculated activation energy is about 78.1 0.4 kJ/mol, which consists well with experimental results of Fernandez (90 10 kJ/mol [23]) and Johansson (72 15 kJ/mol [24]). Meanwhile, the calculated characteristic time is 1953 s and 22,311 s at the temperature 673 K and 573 K, respectively. All above results indicate that the hydrogen absorption mechanism is diffusion of hydrogen atoms and there is a signicant effect of temperature on hydrogenation reaction for Mg powder. With the temperature increasing, the motion rate of hydrogen atoms will be expedited and therefore the time of completive reaction will be reduced remarkably.

4.3.

Application of chemical reaction formula

Pal [25] had investigated the hydriding property of La2Mg17x wt% LaNi5 composite, which was synthesized by melting the La2Mg17 and LaNi5 with the proper stoichiometric ratios in a radiofrequency induction furnace. The hydrogen absorption

Fig. 4 e A schematic diagram of inexion point for our new model.

Fig. 5 e Hydrogen absorption curves and tted curves under temperature 423 K of unmilled and milled Mg powders.

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Fig. 6 e Hydrogen absorption curves and tted curves under temperature 573 K and 673 K of Mg powders.

Fig. 8 e Hydrogen absorption kinetics curves of Mg-5 wt.% Ni-10 wt.%Ti19Cr50V22Mn9 composites at 573 K, 553 K, 523 K, 473 K, 423 K and 323 K.

data of La2Mg175 wt%LaNi5 at temperature of 623 K, 648 K and 678 K are shown in Fig. 7. Utilizing the same tting method, the plots of x and t are also shown in this gure. For the chemical reaction step, the corresponding R2 of the linear regression equations is 0.9827. And the calculated activation energy is about 54.2 1.8 kJ/mol. In ref. [3], it has been show that the hydrogen absorption rate-limiting step is or chemical reaction or surface penetration of hydrogen atoms and could not be changed with the increase of LaNi5. Furthermore, it could be concluded in this paper that temperature also could not change the hydrogen adsorption mechanism during 623 K to 678 K. And the tting result shows that our new modal can be applied in chemical reaction rate controlling situation.

is about 0.3 0.1 kJ/mol and 52.9 7.5 kJ/mol for diffusion and chemical reaction step, respectively. This means the chemical reaction process is the major rate controlling step. However, when compared the tting results with different rate controlling formulae during 523 Ke573 K temperature, it is shown that diffusion process rather than other processes is the rate controlling step. This result indicates that as the temperature increasing, the rate controlling step changes

4.4.

Application of mixed rate controlling formula

Li et al. [8] prepared the composite 85wt.%Mg-5wt.%Ni-10wt.% Ti19Cr50V22Mn9 by mechanical alloying. The hydrogen absorption curves of Mge5 wt.%Nie10 wt.%Ti19Cr50V22Mn9 at temperature of 323 Ke573 K are shown in Fig. 8. Compared the tting results with different rate controlling formulae during temperature of 323 Ke473 K, it is shown that mixed diffusion and chemical reaction process rather than other processes is the rate controlling step. And the calculated activation energy

Fig. 7 e Hydrogen absorption curves and tted curves under temperature 623 K, 648 K and 678 K of La2Mg17L5wt %LaNi5.

Fig. 9 e Hydriding data at 473 K and under 4.0 MPa H2 for La1.8Ca0.2Mg14Ni3 alloys milled for different times together with the tted curves (solid curves: surface penetration step; dotted curves: diffusion step).

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from mixed diffusion and chemical reaction to single diffusion. Therefore, it is deduced that below 323 K temperature, Mg-5 wt.%Ni-10 wt.%Ti19Cr50V22Mn9 system may be controlled by chemical reaction. In could be concluded that temperature not only to improve the hydriding kinetics, but also change the hydrogen absorption rate-limiting step from diffusion mixed with chemical reaction to the diffusion of hydrogen atoms through the hydride layer. Gao et al. [26] studied the hydriding behaviors of La1.8Ca0.2Mg14Ni3 alloy modied by ball-milling under argon. The relationship between x and t is modeled by tting the experimental data with the rate equations of each step using the least squares. Then, the hydrogen absorption curves of La1.8Ca0.2Mg14Ni3 at temperature of 423 K with different ball milling time are shown in Fig. 9. Our results show that with 0 h ball milling treatment, the kinetics of system is controlled by chemical reaction while with 10 h ball milling treatment, the kinetics of system is controlled by mixed diffusion and chemical reaction. In order to illuminate the tting results clearly, the tting details of other formulae are showed in Fig. 9(b). It could be seen clearly that for the diffusion mixed with chemical reaction step, the corresponding R2 of the linear regression equations for La1.8Ca0.2Mg14Ni3 alloys with milled of 10 h treatment is 0.9953. However, these experimental data cannot be tted by the model with other rate-controlling step. Therefore, the diffusion mixed with chemical reaction step can be considered as the rate controlling step. Then with the time of ball milling increasing to 15 h and 20 h, the system is controlled by diffusion equation. So, it could be concluded that ball-milling treatment will change the hydrogen absorption rate-limiting step from chemical reaction to the diffusion mixed with chemical reaction step and nal to diffusion step. And ne crystallite size and possible high level of structural defects introduced by ball milling treatment contribute to the change of mechanism.

Acknowledgments
This work is supported by the National Natural Science Foundation of China (50804029, 50974084, 51074103), Shanghai Rising-Star Program (11QH1400900), and the Program for Changjiang Scholars and Innovative Research Team in University (IRT0739).

Appendix A. Different single and mixed rate controlling steps

The formulae expressions of reaction rate for different kinds of steps in hydriding process are derived below. 1) Rate controlling step of chemisorption/surface penetration We will use chemisorption as an illustration to illuminate the deduce procedure. In this situation, the basic formula can be expressed as: ! x bKca Kpa PH2 R2 0 arB b Ksp Kr

1 1 3 R0 kf ca

(A-1)

In right formula, Kpa is constant due to the single rate controlling step. However, in left formula kf ca
f k0 ca exp f

Dca RT

! (A-2)

Where Dca is the activation energy of chemisorption or surface penetration reaction in forward direction. Therefore, equation will become b C B bKca Kpa PH2 C Kr K 1B 1 sp B !C t 2 Cx f 3B R a r B A @ D 0 ca 0f R0 kca exp RT 0 1

(A-3)

5.

Conclusion
For rate controlling step of chemisorption/surface penetration, the characteristic time should be equal to tcca  3 bKca Kpa PH2 R0 arB !  f b Dca 0f k exp RT Ksp Kr ca (A-4)

In order to treat the complex adsorption reactions of practical Mg-based hydrogen storage materials, a new model based on Chou model in our group and unreacted-core model has been proposed in this work. This new model could be utilized to describe reaction time t as a function of temperature T, particle radius R0 and reaction fraction z. Especially, our new basic model could be deduced into different single and mixed rate controlling steps, which could be applied to practice system conveniently. 3D reaction rate has been considered in this new model for the spherical particles and this assumption improves the Jander model and therefore makes a closer connection to the real case. Furthermore, the new model is successfully applied for a real case, such as Mg powder, La2Mg175wt%LaNi5, Mg-5wt.%Ni-10wt.%Ti19Cr50V22Mn9 and La1.8Ca0.2Mg14Ni3. All results indicate that this new model works very well and could reasonably deal with complex kinetics mechanism. It should be emphasized that this new model could be used to describe adsorption reaction only. And we will illuminate the treatment of desorption reaction in anther publication.

2) Rate controlling step of diffusion ! b Kr

1 1 b 3 DH

i 1 h x b 1 1 x2=3 2DH

bKsp Kca Kpa PH2 R2 0 arB

(A-5)

In order to display the formula more regular, this equation should be change into another form !& ' 2bKsp Kca Kpa PH2 R2 0 arB 2b Kr t

1 Db H

2 1 x 1 x2=3 3

(A-6)

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Where Db H represents the diffusion coefcient   Dd 0 Db D exp H H RT kf sp (A-7)

f k0 sp exp

Dsp RT

! (A-15) !

Where Dd is the activation energy of diffusion reaction. Substituting Eqs. (A-7) into Eq. (A-6) yields 0 1 2b ' 2bKsp Kca Kpa PH2 B C& 1 2 Kr B 2=3 C  t B C 1 x 1 x Dd A @ 0 3 R2 0 arB DH exp RT (A-8) For rate controlling step of diffusion, the characteristic time should be equal to    tcd  b Dd D0 6 bKsp Kca Kpa PH2 exp H RT Kr R2 0 arB (A-9)

0 Ksp Db H Ksp exp

  Dd D0 H exp RT RT ! 0 DHsp Dd 0 K0 sp DH exp RT DH0 sp

(A-16)

Substituting Eqs. (A-15) and (A-16) into Eq. (A-14) yields 1 3R0 ksp exp
0f f Dsp

!x

1
0 2K0 sp DH exp

DH0 sp Dd

RT

  bKca Kpa PH2 2 1 x 1 x2=3 3 R2 0 arB

RT b Ksp Kr t

(A-17)

For mixed rate controlling step of surface penetration and diffusion, the characteristic time should be equal to tcsp d 3R0  R2 0 arB !  f Dsp b f bKca Kpa PH2 k0 exp RT Ksp Kr sp R2 0 arB !  DH0 b sp Dd 0 K0 D exp RT Ksp Kr sp H (A-18)

3) Rate controlling step of chemical reaction 2 3 b Kr

1 1 4 1 1 x3 5 f R0 kr

bKsp Kca Kpa PH2 R2 0 arB

(A-10)

 6 bKca Kpa PH2

It should be noticed that in order to decrease the tting parameters and improve the result, in right formula, Kr is evaluated to a constant.
0f kf r kr exp f

Dr RT

! (A-11)

Where Dr is the activation energy of chemical reaction in forward direction. Substituting Eqs. (A-11) into Eq. (A-10) yields 2 1 R0 kr exp
0f 1

In this formula, it should be noticed that two activation energies can be obtained. Activation energy of surface penetraf tion DE1 Dsp and activation energy of diffusion 0 DE2 DHsp Dd . However, the major disadvantage in this formula has 4 parameters to be tted and the result may not be well. 5) Rate controlling step of diffusion and chemical reaction 1 1 b 3 DH ! 2 3 i 1 1 h 1 4 2=3 x b 1 1 x 1 1 x3 5 f 2DH R0 kr b Kr

Dr RT

!41 1 x3 5 f

bKsp Kca Kpa PH2 R2 0 arB

b Kr

(A-12)

bKsp Kca Kpa PH2 R2 0 arB

(A-19)

For rate controlling step of chemical reaction, the characteristic time should be equal to tcr R0 arB !   f b Dr 0f exp kr bKsp Kca Kpa PH2 RT Kr (A-13) kf r

In the right formula

f k0 r exp

Dr RT

! (A-20)

4) Rate controlling step of surface penetration and diffusion

  Dd 0 Db H DH exp RT

(A-21)

Substituting Eqs. (A-20) and (A-21) into Eq. (A-19) yields 0 1 1 1 b 3 R0 kf K sp DH sp ! x 1 2Ksp Db H h 1 1 x2=3 i 1  B C 1 2 1 B 2=3 ! C  B C 1 x 1 x f Dd A @ 0 3 Dr 0 f 2DH exp k exp R 0 r RT RT (A-14) 2
1

bKca Kpa PH2 R2 0 arB

b Ksp Kr

41 1 x3 5

bKsp Kca Kpa PH2 R2 0 arB

b Kr

(A-22)

Due to this formula describe the mixed rate controlling step of surface penetration and diffusion, thus in the right formula, Kca Kpa is a constant. However, in the left formula

For mixed rate controlling step of diffusion and chemical reaction, the characteristic time should be equal to

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C B C B R2 1 1 B 0 arB !C   t C B f C bB 0 Dd Dr A 0f bKsp Kca Kpa PH2 @6DH exp k exp R 0 r RT Kr RT (A-23)

references

[1] Sakintuna B, Lamari-Darkrim F, Hirscher M. Metal hydride materials for solid hydrogen storage: a review. Int J Hydrogen Energ 2007;32(9):1121e40. [2] Hancock JD, Sharp JH. Method of comparing solid-state kinetic data and its application to the decomposition of Kaolinite, Brucite, and BaCO3. J Am Ceram Soc 1972;55(2):74e7. [3] Liu J, Zhang X, Li Q, Chou KC, Xu KD. Investigation on kinetics mechanism of hydrogen absorption in the La2Mg17based composites. Int J Hydrogen Energ 2009;34(4):1951e7. [4] Martin M, Gommel C, Borkhart C, Fromm E. Absorption and desorption kinetics of hydrogen storage alloys. J Alloys Compd 1996;238(1e2):193e9. [5] Schweppe F, Martin M, Fromm E. Model on hydride formation describing surface control, diffusion control and transition regions. J Alloys Compd 1997;261(1e2):254e8. [6] Bloch J. The kinetics of a moving metal hydride layer. J Alloys Compd 2000;312(1e2):135e53. [7] Chou K-C, Xu K. A new model for hydriding and dehydriding reactions in intermetallics. Intermetallics 2007;15(5e6): 767e77. [8] Li Q, Jiang LJ, Lu XG, Liu XP, Chou KC, Xu KD. Study on the structure and hydrogenation kinetics of the composite MgeNieTi19Cr50V22Mn9. Rare Metal Mater Eng 2006;35(12): 1859e63. [9] Vigeholm B, Jensen K, Larsen B, Pedersen AS. Elements of hydride formation mechanisms in nearly spherical magnesium powder particles. J Less Common Metals 1987; 131(1e2):133e41. [10] Hu XJ, Matsuura H, Tsukihashi H, Chou KC. Kinetic study on non-equilibrium oxygen transfer in interfacial process. Acta Metall Sinica 2007;43(8):829e33.

[11] Budrugeac P, Segal E. On the use of Diefallahs composite integral method for the non-isothermal kinetic analysis of heterogeneous solid-gas reactions. J Therm Anal Calorim 2005;82(3):677e80. [12] Jander W. Reactions in the solid state at high temperature: I. Z Anorg Allgem Chem 1927;163(1):1e30. [13] Hulbert SF. Models for solid-state reactions in powdered compacts: a review. J Br Ceram Soc 1967;6(1):11e20. [14] Chou KC, Li Q, Lin Q, Jiang LJ, Xu KD. Kinetics of absorption and desorption of hydrogen in alloy powder. Int J Hydrogen Energ 2005;30(3):301e9. [15] Ginstling AM, Brounshtein BI. Concerning the diffusion kinetics of reaction in spherical particles. J Appl Chem USSR 1950;23(12):1327e38. [16] Avrami M. Kinetics of phase change. I general theory. J Chem Phys 1939;7(12):1103e12. [17] Ortega A. A simulation of the mass-transfer effects on the kinetics of solid-gas reactions. Int J Chem Kinet 2008;40(4): 217e22. [18] Levenspiel O. Chemical reaction engineering. 2nd ed. New York: Wiley; 1972. [19] Mintz MH, Zeiri Y. Hydriding kinetics of powders. J Alloys Compds 1995;216(2):159e75. [20] Carter RE. Kinetic model for solid-state reactions. J Chem Phys 1961;34(6):2010e5. [21] Carter RE. Addendum: kinetic model for solid-state reactions. J Chem Phys 1961;35(3):1137e8. [22] Huot J, Liang G, Boily S, Van Neste A, Schulz R. Structural study and hydrogen sorption kinetics of ball-milled magnesium hydride. J Alloys Compd 1999;293e295:495e6. [23] Fernandez JF, Sanchez CR. Rate determining step in the absorption and desorption of hydrogen by magnesium. J Alloys Compd 2002;340(1e2):189e98. [24] Johansson M, Ostenfeld CW, Chorkendorff I. Adsorption of hydrogen on clean and modied magnesium lms. Phys Rev B 2006;74(19):193408e12. [25] Pal K. Synthesis characterization and hydrogen absorption studies of the composite materials La2Mg17x wt% LaNi5. J Mater Sci 1997;32(18):5177e8. [26] Gao L, Chen C, Chen L, Wang X, Zhang J, Xiao X, et al. Hydriding/dehydriding behaviors of La1.8Ca0.2Mg14Ni3 alloy modied by mechanical ball-milling under argon. J Alloys Compd 2005;399(1e2):178e82.